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Brazing & Soldering

Aggragated By: Paul Morrissette

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Contents
Brazing Filler metal Capillary action Liquidus Soldering Inert Phosphide Nickel Lead Zinc Brass Silver Copper Alloy Tin Solder Ductility Gold Iron Redox Aluminium Ore Carbon Steel Chemical element Isotope Atomic number Half-life Oxygen Sopormetal List of brazing alloys Induction brazing Amorphous brazing foil Pin brazing Flux (metallurgy) CuproBraze 1 17 18 21 22 35 36 38 50 64 85 96 110 128 137 151 163 166 187 205 215 230 235 251 263 281 292 296 301 323 324 375 377 378 379 389

Filler List of welding codes Welding Procedure Specification List of DIN standards Mokume-gane NanoFoil

395 396 402 404 442 444

References
Article Sources and Contributors Image Sources, Licenses and Contributors 446 458

Article Licenses
License 465

Brazing

Brazing
Brazing is a metal-joining process whereby a filler metal is heated above melting point and distributed between two or more close-fitting parts by capillary action. The filler metal is brought slightly above its melting (liquidus) temperature while protected by a suitable atmosphere, usually a flux. It then flows over the base metal (known as wetting) and is then cooled to join the workpieces together.[] It is similar to soldering, except the temperatures used to melt the filler metal are higher.

Fundamentals
In order to obtain high-quality brazed joints, parts must be closely fitted, and the base metals must be exceptionally clean and free of oxides. In most cases, joint clearances of 0.03 to 0.08 mm (0.0012 to 0.0031 in) are recommended for the best capillary action and joint strength.[] However, in some brazing operations it is not uncommon to Brazing practice have joint clearances around 0.6mm (0.024in). Cleanliness of the brazing surfaces is also important, as any contamination can cause poor wetting (flow). The two main methods for cleaning parts, prior to brazing are chemical cleaning, and abrasive or mechanical cleaning. In the case of mechanical cleaning, it is important to maintain the proper surface roughness as wetting on a rough surface occurs much more readily than on a smooth surface of the same geometry.[] Another consideration that cannot be overlooked is the effect of temperature and time on the quality of brazed joints. As the temperature of the braze alloy is increased, the alloying and wetting action of the filler metal increases as well. In general, the brazing temperature selected must be above the melting point of the filler metal. However, there are several factors that influence the joint designer's temperature selection. The best temperature is usually selected so as to: (1) be the lowest possible braze temperature, (2) minimize any heat effects on the assembly, (3) keep filler metal/base metal interactions to a minimum, and (4) maximize the life of any fixtures or jigs used.[] In some cases, a higher temperature may be selected to allow for other factors in the design (e.g. to allow use of a different filler metal, or to control metallurgical effects, or to sufficiently remove surface contamination). The effect of time on the brazed joint primarily affects the extent to which the aforementioned effects are present; however, in general most production processes are selected to minimize brazing time and the associated costs. This is not always the case, however, since in some non-production settings, time and cost are secondary to other joint attributes (e.g. strength, appearance).

Flux
In the case of brazing operations not contained within an inert or reducing atmosphere environment (i.e. a furnace), flux is required to prevent oxides from forming while the metal is heated. The flux also serves the purpose of cleaning any contamination left on the brazing surfaces. Flux can be applied in any number of forms including flux paste, liquid, powder or pre-made brazing pastes that combine flux with filler metal powder. Flux can also be applied using brazing rods with a coating of flux, or a flux core. In either case, the flux flows into the joint when applied to the heated joint and is displaced by the molten filler metal entering the joint. Excess flux should be removed when the cycle is completed because flux left in the joint can lead to corrosion, impede joint inspection, and prevent further surface finishing operations. Phosphorus-containing brazing alloys can be self-fluxing when joining copper to copper.[1] Fluxes are generally selected based on their performance on particular base metals. To be effective, the

Brazing flux must be chemically compatible with both the base metal and the filler metal being used. Self-fluxing phosphorus filler alloys produce brittle phosphides if used on iron or nickel.[] As a general rule, longer brazing cycles should use less active fluxes than short brazing operations.[2]

Filler materials
A variety of alloys are used as filler metals for brazing depending on the intended use or application method. In general, braze alloys are made up of 3 or more metals to form an alloy with the desired properties. The filler metal for a particular application is chosen based on its ability to: wet the base metals, withstand the service conditions required, and melt at a lower temperature than the base metals or at a very specific temperature. Braze alloy is generally available as rod, ribbon, powder, paste, cream, wire and preforms (such as stamped washers).[] Depending on the application, the filler material can be pre-placed at the desired location or applied during the heating cycle. For manual brazing, wire and rod forms are generally used as they are the easiest to apply while heating. In the case of furnace brazing, alloy is usually placed beforehand since the process is usually highly automated.[] Some of the more common types of filler metals used are Aluminum-silicon Copper Copper-silver Copper-zinc (brass) Gold-silver Nickel alloy Silver[][3] Amorphous brazing foil using nickel, iron, copper, silicon, boron, phosphorus, etc.

Atmosphere
As brazing work requires high temperatures, oxidation of the metal surface occurs in an oxygen-containing atmosphere. This may necessitate the use of an atmospheric environment other than air. The commonly used atmospheres are[4][5] Air: Simple and economical. Many materials susceptible to oxidation and buildup of scale. Acid cleaning bath or mechanical cleaning can be used to remove the oxidation after work. Flux tends to be employed to counteract the oxidation, but it may weaken the joint. Combusted fuel gas (low hydrogen, AWS type 1, "exothermic generated atmospheres"): 87% N2, 1112% CO2, 5-1% CO, 5-1% H2. For silver, copper-phosphorus and copper-zinc filler metals. For brazing copper and brass. Combusted fuel gas (decarburizing, AWS type 2, "endothermic generated atmospheres"): 7071% N2, 56% CO2, 910% CO, 1415% H2. For copper, silver, copper-phosphorus and copper-zinc filler metals. For brazing copper, brass, nickel alloys, Monel, medium carbon steels. Combusted fuel gas (dried, AWS type 3, "endothermic generated atmospheres"): 7375% N2, 1011% CO, 1516% H2. For copper, silver, copper-phosphorus and copper-zinc filler metals. For brazing copper, brass, low-nickel alloys, Monel, medium and high carbon steels. Combusted fuel gas (dried, decarburizing, AWS type 4): 4145% N2, 1719% CO, 3840% H2. For copper, silver, copper-phosphorus and copper-zinc filler metals. For brazing copper, brass, low-nickel alloys, medium and high carbon steels. Ammonia (AWS type 5, also called forming gas): Dissociated ammonia (75% hydrogen, 25% nitrogen) can be used for many types of brazing and annealing. Inexpensive. For copper, silver, nickel, copper-phosphorus and copper-zinc filler metals. For brazing copper, brass, nickel alloys, Monel, medium and high carbon steels and chromium alloys.

Brazing Nitrogen+hydrogen, cryogenic or purified (AWS type 6A): 7099% N2, 130% H2. For copper, silver, nickel, copper-phosphorus and copper-zinc filler metals. Nitrogen+hydrogen+carbon monoxide, cryogenic or purified (AWS type 6B): 7099% N2, 220% H2, 110% CO. For copper, silver, nickel, copper-phosphorus and copper-zinc filler metals. For brazing copper, brass, low-nickel alloys, medium and high carbon steels. Nitrogen, cryogenic or purified (AWS type 6C): Non-oxidizing, economical. At high temperatures can react with some metals, e.g. certain steels, forming nitrides. For copper, silver, nickel, copper-phosphorus and copper-zinc filler metals. For brazing copper, brass, low-nickel alloys, Monel, medium and high carbon steels. Hydrogen (AWS type 7): Strong deoxidizer, highly thermally conductive. Can be used for copper brazing and annealing steel. May cause hydrogen embrittlement to some alloys. For copper, silver, nickel, copper-phosphorus and copper-zinc filler metals. For brazing copper, brass, nickel alloys, Monel, medium and high carbon steels and chromium alloys, cobalt alloys, tungsten alloys, and carbides. Inorganic vapors (various volatile fluorides, AWS type 8): Special purpose. Can be mixed with atmospheres AWS 15 to replace flux. Used for silver-brazing of brasses. Noble gas (usually argon, AWS type 9): Non-oxidizing, more expensive than nitrogen. Inert. Parts must be very clean, gas must be pure. For copper, silver, nickel, copper-phosphorus and copper-zinc filler metals. For brazing copper, brass, nickel alloys, Monel, medium and high carbon steels chromium alloys, titanium, zirconium, hafnium. Noble gas+hydrogen (AWS type 9A) Vacuum: Requires evacuating the work chamber. Expensive. Unsuitable (or requires special care) for metals with high vapor pressure, e.g. silver, zinc, phosphorus, cadmium, and manganese. Used for highest-quality joints, for e.g. aerospace applications.

Brazing

Common techniques
Torch brazing
Torch brazing is by far the most common method of mechanized brazing in use. It is best used in small production volumes or in specialized operations, and in some countries, it accounts for a majority of the brazing taking place. There are three main categories of torch brazing in use:[] manual, machine, and automatic torch brazing. Manual torch brazing is a procedure where the heat is applied using a gas flame placed on or near the joint being brazed. The torch can either be hand held or held in a fixed position depending on if the operation is completely manual or has some level of automation. Manual brazing is most commonly used on small production volumes or in applications where the part size or configuration makes other brazing methods impossible.[] The main drawback is the high labor cost associated with the method as well as the operator skill required [6] Brazing and soldering processes classification chart to obtain quality brazed joints. The use of flux or self-fluxing material is required to prevent oxidation. Torch brazing of copper can be done without the use of flux if it is brazed with an oxygen & hydrogen gas torch set up vs. oxygen and other flammable gasses. Machine torch brazing is commonly used where a repetitive braze operation is being carried out. This method is a mix of both automated and manual operations with an operator often placing brazes material, flux and jigging parts while the machine mechanism carries out the actual braze.[] The advantage of this method is that it reduces the high labor and skill requirement of manual brazing. The use of flux is also required for this method as there is no protective atmosphere, and it is best suited to small to medium production volumes. Automatic torch brazing is a method that almost eliminates the need for manual labor in the brazing operation, except for loading and unloading of the machine. The main advantages of this method are: a high production rate, uniform braze quality, and reduced operating cost. The equipment used is essentially the same as that used for Machine torch brazing, with the main difference being that the machinery replaces the operator in the part preparation.[]

Brazing

Furnace brazing
Furnace brazing is a semi-automatic process used widely in industrial brazing operations due to its adaptability to mass production and use of unskilled labor. There are many advantages of furnace brazing over other heating methods that make it ideal for mass production. One main advantage is the ease Furnace brazing schematic with which it can produce large numbers of small parts that are easily jigged or self-locating.[] The process also offers the benefits of a controlled heat cycle (allowing use of parts that might distort under localized heating) and no need for post braze cleaning. Common atmospheres used include: inert, reducing or vacuum atmospheres all of which protect the part from oxidation. Some other advantages include: low unit cost when used in mass production, close temperature control, and the ability to braze multiple joints at once. Furnaces are typically heated using either electric, gas or oil depending on the type of furnace and application. However, some of the disadvantages of this method include: high capital equipment cost, more difficult design considerations and high power consumption.[] There are four main types of furnaces used in brazing operations: batch type; continuous; retort with controlled atmosphere; and vacuum. Batch type furnaces have relatively low initial equipment costs and heat each part load separately. It is capable of being turned on and off at will which reduces operating expenses when not in use. These furnaces are well suited to medium to large volume production and offer a large degree of flexibility in type of parts that can be brazed.[] Either controlled atmospheres or flux can be used to control oxidation and cleanliness of parts. Continuous type furnaces are best suited to a steady flow of similar-sized parts through the furnace.[] These furnaces are often conveyor fed, allowing parts to be moved through the hot zone at a controlled speed. It is common to use either controlled atmosphere or pre-applied flux in continuous furnaces. In particular, these furnaces offer the benefit of very low manual labor requirements and so are best suited to large scale production operations. Retort-type furnaces differ from other batch-type furnaces in that they make use of a sealed lining called a "retort". The retort is generally sealed with either a gasket or is welded shut and filled completely with the desired atmosphere and then heated externally by conventional heating elements.[] Due to the high temperatures involved, the retort is usually made of heat resistant alloys that resist oxidation. Retort furnaces are often either used in a batch or semi-continuous versions. Vacuum furnaces is a relatively economical method of oxide prevention and is most often used to braze materials with very stable oxides (aluminum, titanium and zirconium) that cannot be brazed in atmosphere furnaces. Vacuum brazing is also used heavily with refractory materials and other exotic alloy combinations unsuited to atmosphere furnaces. Due to the absence of flux or a reducing atmosphere, the part cleanliness is critical when brazing in a vacuum. The three main types of vacuum furnace are: single-wall hot retort, double-walled hot retort, and cold-wall retort. Typical vacuum levels for brazing range from pressures of 1.3 to 0.13 pascal (unit)pascals (102 to 103 Torr) to 0.00013 Pa (106 Torr) or lower.[] Vacuum furnaces are most commonly batch-type, and they are suited to medium and high production volumes.

Brazing

Silver brazing
Silver brazing, sometimes known as a silver soldering or hard soldering, is brazing using a silver alloy based filler. These silver alloys consist of many different percentages of silver and other metals, such as copper, zinc and cadmium. Brazing is widely used in the tool industry to fasten hardmetal (carbide, ceramics, cermet, and similar) tips to tools such as saw blades. "Pretinning" is often done: the braze alloy is melted onto the hardmetal tip, which is placed next to the steel and remelted. Pretinning gets around the problem that hardmetals are hard to wet. Brazed hardmetal joints are typically two to seven mils thick. The braze alloy joins the materials and compensates for the difference in their expansion rates. In addition it provides a cushion between the hard carbide tip and the hard steel which softens impact and prevents tip loss and damage, much as the suspension on a vehicle helps prevent damage to both the tires and the vehicle. Finally the braze alloy joins the other two materials to create a composite structure, much as layers of wood and glue create plywood. The standard for braze joint strength in many industries is a joint that is stronger than either base material, so that when under stress, one or other of the base materials fails before the joint. One special silver brazing method is called pinbrazing or pin brazing. It has been developed especially for connecting cables to railway track or for cathodic protection installations. The method uses a silver- and flux-containing brazing pin which is melted down in the eye of a cable lug. The equipment is normally powered from batteries.

Braze welding
Braze welding is the use of a bronze or brass filler rod coated with flux to join steel workpieces. The equipment needed for braze welding is basically identical to the equipment used in brazing. Since braze welding usually requires more heat than brazing, acetylene or methylacetylene-propadiene (MAP) gas fuel is commonly used. The name comes from the fact that no capillary action is used. Braze welding has many advantages over fusion welding. It allows the joining of dissimilar metals, minimization of heat distortion, and can reduce the need for extensive pre-heating. Additionally, since the metals joined are not melted in the process, the components retain their original shape; edges and contours are not eroded or changed by the A braze-welded T-joint formation of a fillet. Another effect of braze welding is the elimination of stored-up stresses that are often present in fusion welding. This is extremely important in the repair of large castings. The disadvantages are the loss of strength when subjected to high temperatures and the inability to withstand high stresses. Carbide, cermet and ceramic tips are plated and then joined to steel to make tipped band saws. The plating acts as a braze alloy.

Cast iron "welding"


The "welding" of cast iron is usually a brazing operation, with a filler rod made chiefly of nickel being used although true welding with cast iron rods is also available. Ductile cast iron pipe may be also "cadwelded," a process which connects joints by means of a small copper wire fused into the iron when previously ground down to the bare metal, parallel to the iron joints being formed as per hub pipe with neoprene gasket seals. The purpose behind this operation is to use electricity along the copper for keeping underground pipes warm in cold climates.

Brazing

Vacuum brazing
Vacuum brazing is a material joining technique that offers significant advantages: extremely clean, superior, flux-free braze joints of high integrity and strength. The process can be expensive because it must be performed inside a vacuum chamber vessel. Temperature uniformity is maintained on the work piece when heating in a vacuum, greatly reducing residual stresses due to slow heating and cooling cycles. This, in turn, can significantly improve the thermal and mechanical properties of the material, thus providing unique heat treatment capabilities. One such capability is heat-treating or age-hardening the workpiece while performing a metal-joining process, all in a single furnace thermal cycle. Vacuum brazing is often conducted in a furnace; this means that several joints can be made at once because the whole workpiece reaches the brazing temperature. The heat is transferred using radiation, as many other methods cannot be used in a vacuum.

Dip brazing
Dip brazing is especially suited for brazing aluminum because air is excluded, thus preventing the formation of oxides. The parts to be joined are fixtured and the brazing compound applied to the mating surfaces, typically in slurry form. Then the assemblies are dipped into a bath of molten salt (typically NaCl, KCl and other compounds) which functions both as heat transfer medium and flux.

Heating methods
There are many heating methods available to accomplish brazing operations. The most important factor in choosing a heating method is achieving efficient transfer of heat throughout the joint and doing so within the heat capacity of the individual base metals used. The geometry of the braze joint is also a crucial factor to consider, as is the rate and volume of production required. The easiest way to categorize brazing methods is to group them by heating method. Here are some of the most common:[][7] Torch brazing Furnace brazing Induction brazing Dip brazing Resistance brazing Infrared brazing Blanket brazing Electron beam and laser brazing Braze welding

Advantages and disadvantages


Brazing has many advantages over other metal-joining techniques, such as welding. Since brazing does not melt the base metal of the joint, it allows much tighter control over tolerances and produces a clean joint without the need for secondary finishing. Additionally, dissimilar metals and non-metals (i.e. metalized ceramics) can be brazed. In general, brazing also produces less thermal distortion than welding due to the uniform heating of a brazed piece. Complex and multi-part assemblies can be brazed cost-effectively. Welded joints must sometimes be ground flush, a costly secondary operation that brazing does not require because it produces a clean joint. Another advantage is that the brazing can be coated or clad for protective purposes. Finally, brazing is easily adapted to mass production and it is easy to automate because the individual process parameters are less sensitive to variation.[][8] One of the main disadvantages is: the lack of joint strength as compared to a welded joint due to the softer filler metals used.[]Wikipedia:Disputed statement The strength of the brazed joint is likely to be less than that of the base

Brazing metal(s) but greater than the filler metal.[citation needed] Another disadvantage is that brazed joints can be damaged under high service temperatures.[] Brazed joints require a high degree of base-metal cleanliness when done in an industrial setting. Some brazing applications require the use of adequate fluxing agents to control cleanliness. The joint color is often different from that of the base metal, creating an aesthetic disadvantage.

Filler metals
Some brazes come in the form of trifoils, laminated foils of a carrier metal clad with a layer of braze at each side. The center metal is often copper; its role is to act as a carrier for the alloy, to absorb mechanical stresses due to e.g. differential thermal expansion of dissimilar materials (e.g. a carbide tip and a steel holder), and to act as a diffusion barrier (e.g. to stop diffusion of aluminium from aluminium bronze to steel when brazing these two).

Braze families
Brazing alloys form several distinct groups; the alloys in the same group have similar properties and uses.[9] Pure metals Unalloyed. Often noble metals silver, gold, palladium. Ag-Cu Good melting properties. Silver enhances flow. Eutectic alloy used for furnace brazing. Copper-rich alloys prone to stress cracking by ammonia. Ag-Zn Similar to Cu-Zn, used in jewelry due to high silver content to be compliant with hallmarking. Color matches silver. Resistant to ammonia-containing silver-cleaning fluids. Cu-Zn (brass) General purpose, used for joining steel and cast iron. Corrosion resistance usually inadequate for copper, silicon bronze, copper-nickel, and stainless steel. Reasonably ductile. High vapor pressure due to volatile zinc, unsuitable for furnace brazing. Copper-rich alloys prone to stress cracking by ammonia. Ag-Cu-Zn Lower melting point than Ag-Cu for same Ag content. Combines advantages of Ag-Cu and Cu-Zn. At above 40% Zn the ductility and strength drop, so only lower-zinc alloys of this type are used. At above 25% zinc less ductile copper-zinc and silver-zinc phases appear. Copper content above 60% yields reduced strength and liquidus above 900 C. Silver content above 85% yields reduced strength, high liquidus and high cost. Copper-rich alloys prone to stress cracking by ammonia. Silver-rich brazes (above 67.5% Ag) are hallmarkable and used in jewellery; alloys with lower silver content are used for engineering purposes. Alloys with copper-zinc ratio of about 60:40 contain the same phases as brass and match its color; they are used for joining brass. Small amount of nickel improves strength and corrosion resistance and promotes wetting of carbides. Addition of manganese together with nickel increases fracture toughness. Addition of cadmium yields Ag-Cu-Zn-Cd alloys with improved fluidity and wetting and lower melting point; however cadmium is toxic. Addition of tin can play mostly the same role. Cu-P Widely used for copper and copper alloys. Does not require flux for copper. Can be also used with silver, tungsten, and molybdenum. Copper-rich alloys prone to stress cracking by ammonia. Ag-Cu-P Like Cu-P, with improved flow. Better for larger gaps. More ductile, better electrical conductivity. Copper-rich alloys prone to stress cracking by ammonia.

Brazing Au-Ag Noble metals. Used in jewelry. Au-Cu Continuous series of solid solutions. Readily wet many metals, including refractory ones. Narrow melting ranges, good fluidity.[] Frequently used in jewellery. Alloys with 4090% of gold harden on cooling but stay ductile. Nickel improves ductility. Silver lowers melting point but worsens corrosion resistance; to maintain corrosion resistance gold has to be kept above 60%. High-temperature strength and corrosion resistance can be improved by further alloying, e.g. with chromium, palladium, manganese and molybdenum. Addition of vanadium allows wetting ceramics. Low vapor pressure. Au-Ni Continuous series of solid solutions. Wider melting range than Au-Cu alloys but better corrosion resistance and improved wetting. Frequently alloyed with other metals to reduce proportion of gold while maintaining properties. Copper may be added to lower gold proportion, chromium to compensate for loss of corrosion resistance, and boron for improving wetting impaired by the chromium. Generally no more than 35% Ni is used, as higher Ni/Au ratios have too wide melting range. Low vapor pressure. Au-Pd Improved corrosion resistance over Au-Cu and Au-Ni alloys. Used for joining superalloys and refractory metals for high-temperature applications, e.g. jet engines. Expensive. May be substituted for by cobalt-based brazes. Low vapor pressure. Pd Good high-temperature performance, high corrosion resistance (less than gold), high strength (more than gold). usually alloyed with nickel, copper, or silver. Forms solid solutions with most metals, does not form brittle intermetallics. Low vapor pressure. Ni Nickel alloys, even more numerous than silver alloys. High strength. Lower cost than silver alloys. Good high-temperature performance, good corrosion resistance in moderately aggressive environments. Often used for stainless steels and heat-resistant alloys. Embrittled with sulfur and some lower-melting point metals, e.g. zinc. Boron, phosphorus, silicon and carbon lower melting point and rapidly diffuse to base metals; this allows diffusion brazing and allows the joint to be used above the brazing temperature. Borides and phosphides form brittle phases; amorphous preforms can be made by rapid solidification. Co Cobalt alloys. Good high-temperature corrosion resistance, possible alternative to Au-Pd brazes. Low workability at low temperatures, preforms prepared by rapid solidification. Al-Si for brazing aluminium. Active alloys Containing active metals, e.g. titanium or vanadium. Used for brazing non-metallic materials, e.g. graphite or ceramics.

Brazing

10

Role of elements
element role volatility corrosion resistance volatile cost incompatibility description

Silver

structural, wetting

expensive

Enhances capillary flow, improves corrosion resistance of less-noble alloys, worsens corrosion resistance of gold and palladium. Relatively expensive. High vapor pressure, problematic in vacuum brazing. Wets copper. Does not wet nickel and iron. Reduces melting point of many alloys, including gold-copper. ammonia Good mechanical properties. Often used with silver. Dissolves and wets nickel. Somewhat dissolves and wets iron. Copper-rich alloys sensitive to stress cracking in presence of ammonia. Lowers melting point. Often used with copper. Susceptible to corrosion. Improves wetting on ferrous metals and on nickel alloys. Compatible with aluminium. High vapor tension, produces somewhat toxic fumes, requires ventilation; highly volatile above 500 C. At high temperatures may boil and create voids. Prone to selective leaching in some environments, which may cause joint failure. Traces of bismuth and beryllium together with tin or zinc in aluminium-based braze destabilize oxide film on aluminium, facilitating its wetting. High affinity to oxygen, promotes wetting of copper in air by reduction of the cuprous oxide surface film. Less such benefit in furnace brazing with controlled atmosphere. Embrittles nickel. High levels of [] zinc may result in a brittle alloy. Usual base for brazing aluminium and its alloys. Embrittles ferrous alloys. Excellent corrosion resistance. Very expensive. Wets most metals. Excellent corrosion resistance, though less than gold. Higher mechanical strength than gold. Good high-temperature strength. Very expensive, though less than gold. Makes the joint less prone to fail due to intergranular penetration when brazing [] alloys of nickel, molybdenum, or tungsten. Increases [] high-temperature strength of gold-based alloys. Improves high-temperature strength and corrosion resistance of gold-copper alloys. Forms solid solutions with most engineering metals, does not form brittle intermetallics. High oxidation resistance at high temperatures, especially Pd-Ni alloys. toxic Lowers melting point, improves fluidity. Toxic. Produces toxic fumes, requires ventilation. High affinity to oxygen, promotes wetting of copper in air by reduction of the cuprous oxide surface film. Less such benefit in furnace brazing with controlled atmosphere. Allows reducing silver content of Ag-Cu-Zn alloys. Replaced by tin in more modern alloys. Lowers melting point. Toxic. Produces toxic fumes, requires ventilation.

Copper

structural

Zinc

structural, melting, wetting

volatile

low

cheap

Ni

Aluminium

structural, active structural, wetting structural excellent very expensive very expensive

Fe

Gold

Palladium

excellent

Cadmium

structural, wetting, melting

volatile

Lead

structural, melting

Brazing

11
structural, melting, wetting

Tin

Lowers melting point, improves fluidity. Broadens melting range. Can be used with copper, with which it forms bronze. Improves wetting of many difficult-to-wet metals, e.g. stainless steels and tungsten carbide. Traces of bismuth and beryllium together with tin or zinc in aluminium-based braze destabilize oxide film on aluminium, facilitating its wetting. Low solubility [] in zinc, which limits its content in zinc-bearing alloys. Lowers melting point. May disrupt surface oxides. Traces of bismuth and beryllium together with tin or zinc in aluminium-based braze destabilize oxide film on aluminium, [] facilitating its wetting. Traces of bismuth and beryllium together with tin or zinc in aluminium-based braze destabilize oxide film on aluminium, [] facilitating its wetting. high Zn, S Strong, corrosion-resistant. Impedes flow of the melt. Addition to gold-copper alloys improves ductility and resistance to creep [] at high temperatures. Addition to silver allows wetting of silver-tungsten alloys and improves bond strength. Improves wetting of copper-based brazes. Improves ductility of gold-copper brazes. Improves mechanical properties and corrosion resistance of silver-copper-zinc brazes. Nickel content offsets brittleness induced by diffusion of aluminium when brazing aluminium-containing alloys, e.g. aluminium bronzes. In some alloys increases mechanical properties and corrosion resistance, by a combination of solid solution strengthening, grain refinement, and segregation on fillet surface and in grain boundaries, where it forms a corrosion-resistant layer. Extensive intersolubility with iron, chromium, manganese, and others; can severely erode such alloys. Embrittled by zinc, many other low [] melting point metals, and sulfur. Corrosion-resistant. Increases high-temperature corrosion and strength of gold-based alloys. Added to copper and nickel to [] increase corrosion resistance of them and their alloys. Wets oxides, carbides, and graphite; frequently a major alloy component for high-temperature brazing of such materials. Impairs wetting by gold-nickel alloys, which can be [] compensated for by addition of boron. cheap High vapor pressure, unsuitable for vacuum brazing. In gold-based alloys increases ductility. Increases corrosion [] resistance of copper and nickel alloys. Improves high-temperature strength and corrosion resistance of gold-copper alloys. Higher manganese content may aggravate tendency to liquation. Manganese in some alloys may tend to cause porosity in fillets. Tends to react with graphite molds and jigs. Oxidizes easily, requires flux. Lowers melting point of high-copper brazes. Improves mechanical properties and corrosion resistance of silver-copper-zinc brazes. Cheap, even less expensive than zinc. Part of the Cu-Zn-Mn system is brittle, [] some ratios can not be used. In some alloys increases mechanical properties and corrosion resistance, by a combination of solid solution strengthening, grain refinement, and segregation on fillet surface and in grain boundaries, where it forms a corrosion-resistant layer. Facilitates wetting of cast iron due to its ability to dissolve carbon.

Bismuth

trace additive

Beryllium

trace additive

Nickel

structural, wetting

Chromium

structural

high

Manganese

structural

volatile

good

Brazing

12
good

Molybdenum structural

Increases high-temperature corrosion and strength of gold-based [] alloys. Increases ductility of gold-based alloys, promotes their wetting of refractory materials, namely carbides and graphite. When present in alloys being joined, may destabilize the surface oxide layer (by oxidizing and then volatilizing) and facilitate wetting. Good high-temperature properties and corrosion resistance. In nuclear applications can absorb neutrons and build up cobalt-60, a potent gamma radiation emitter. Addition to aluminium makes the alloy suitable for vacuum brazing. Volatile, though less than zinc. Vaporization promotes wetting by removing oxides from the surface, vapors act as getter for oxygen in the furnace atmosphere. expensive Lowers melting point. Improves wetting of ferrous alloys by copper-silver alloys. Lowers melting point. Can form carbides. Can diffuse to the base metal, resulting in higher remelt temperature, potentially allowing step-brazing with the same alloy. At above 0.1% worsens corrosion resistance of nickel alloys. Trace amounts present in stainless steel may facilitate reduction of surface chromium(III) oxide in vacuum and allow fluxless brazing. Diffusion away from the braze increases its remelt temperature; [] exploited in diffusion brazing. Ni Lowers melting point. Can form silicides. Improves wetting of copper-based brazes. Promotes flow. Causes intergranular embrittlement of nickel alloys. Rapidly diffuses into the base metals. Diffusion away from the braze increases its remelt temperature; exploited in diffusion brazing. Lowers melting point. Expensive. For special applications. May create brittle phases. Ni Lowers melting point. Can form hard and brittle borides. Unsuitable for nuclear reactors. Fast diffusion to the base metals. Can diffuse to the base metal, resulting in higher remelt temperature, potentially allowing step-brazing with the same alloy. Can erode some base materials or penetrate between grain boundaries of many heat-resistant structural alloys, degrading their mechanical properties. Has to be avoided in nuclear applications due to its interaction with neutrons. Causes intergranular embrittlement of nickel alloys. Improves wetting of/by some alloys, can be added to Au-Ni-Cr alloy to compensate for wetting loss by chromium addition. In low concentrations improves wetting and lowers melting point of nickel brazes. Rapidly diffuses to base materials, may lower their melting point; especially a concern when brazing thin materials. Diffusion away from the braze increases its remelt temperature; exploited in diffusion brazing. in amount of about 0.08%, can be used to substitute boron [] where boron would have detrimental effects. in trace quantities, improves fluidity of brazes. Particularly useful for alloys of four or more components, where the other additives compromise flow and spreading. in trace quantities, refines the grain structure of aluminium-based alloys.

Cobalt

structural

good

Magnesium

volatile O2 volatile getter

Indium

melting, wetting melting

Carbon

Silicon

melting, wetting

Germanium

structural, melting melting, wetting

expensive

Boron

Mischmetal

trace additive trace additive

Cerium

Strontium

trace additive

Brazing

13
deoxidizer H2S, SO2, Ni, Fe, Co

Phosphorus

Lowers melting point. Deoxidizer, decomposes copper oxide; phosphorus-bearing alloys can be used on copper without flux. Does not decompose zinc oxide, so flux is needed for brass. Forms brittle phosphides with some metals, e.g. nickel (Ni3P) and iron, phosphorus alloys unsuitable for brazing alloys bearing iron, nickel or cobalt in amount above 3%. The phosphides segregate at grain boundaries and cause intergranular embrittlement. (Sometimes the brittle joint is actually desired, though. Fragmentation grenades can be brazed with phosphorus bearing alloy to produce joints that shatter easily at detonation.) Avoid in environments with presence of sulfur dioxide (e.g. paper mills) and hydrogen sulfide (e.g. sewers, or close to volcanoes); the phosphorus-rich phase rapidly corrodes in presence of sulfur and the joint fails. Phosphorus can be also present as an impurity introduced from [] e.g. electroplating baths. In low concentrations improves wetting and lowers melting point of nickel brazes. Diffusion away from the braze increases its remelt temperature; exploited in diffusion brazing. Deoxidizer. Eliminates the need for flux with some materials. Lithium oxide formed by reaction with the surface oxides is [] easily displaced by molten braze alloy. Most commonly used active metal. Few percents added to [] Ag-Cu alloys facilitate wetting of ceramics, e.g. silicon nitride. Most metals, except few (namely silver, copper and gold), form brittle phases with titanium. When brazing ceramics, like other active metals, titanium reacts with them and forms a complex layer on their surface, which in turn is wettable by the silver-copper braze. Wets oxides, carbides, and graphite; frequently a major alloy component for high-temperature [] brazing of such materials. Wets oxides, carbides, and graphite; frequently a major alloy [] component for high-temperature brazing of such materials.

Lithium

deoxidizer

Titanium

structural, active

Zirconium

structural, active active structural, active impurity

Hafnium Vanadium

Promotes wetting of alumina ceramics by gold-based alloys.

[]

Sulfur

Compromises integrity of nickel alloys. Can enter the joints from residues of lubricants, grease or paint. Forms brittle nickel sulfide (Ni3S2) that segregates at grain boundaries and cause intergranular failure.

Some additives and impurities act at very low levels. Both positive and negative effects can be observed. Strontium at levels of 0.01% refines grain structure of aluminium. Beryllium and bismuth at similar levels help disrupt the passivation layer of aluminium oxide and promote wetting. Carbon at 0.1% impairs corrosion resistance of nickel alloys. Aluminium can embrittle mild steel at 0.001%, phosphorus at 0.01%.[] In some cases, especially for vacuum brazing, high-purity metals and alloys are used. 99.99% and 99.999% purity levels are available commercially. Care has to be taken to not introduce deletrious impurities from joint contaminations or by dissolution of the base metals during brazing.

Brazing

14

Melting behavior
Alloys with larger span of solidus/liquidus temperatures tend to melt through a "mushy" state, where the alloy is a mixture of solid and liquid material. Some alloys show tendency to liquation, separation of the liquid from the solid portion; for these the heating through the melting range has to be sufficiently fast to avoid this effect. Some alloys show extended plastic range, when only a small portion of the alloy is liquid and most of the material melts at the upper temperature range; these are suitable for bridging large gaps and for forming fillets. Highly fluid alloys are suitable for penetrating deep into narrow gaps and for brazing tight joints with narrow tolerances but are not suitable for filling larger gaps. Alloys with wider melting range are less sensitive to non-uniform clearances. When the brazing temperature is suitably high, brazing and heat treatment can be done in a single operation simultaneously. Eutectic alloys melt at single temperature, without mushy region. Eutectic alloys have superior spreading; non-eutectics in the mushy region have high viscosity and at the same time attack the base metal, with correspondingly lower spreading force. Fine grain size gives eutectics both increased strength and increased ductility. Highly accurate melting temperature allows joining process to be performed only slightly above the alloy's melting point. On solidifying, there is no mushy state where the alloy appears solid but is not yet; the chance of disturbing the joint by manipulation in such state is reduced (assuming the alloy did not significantly change its properties by dissolving the base metal). Eutectic behavior is especially beneficial for solders.[] Metals with fine grain structure before melting provide superior wetting to metals with large grains. Alloying additives (e.g. strontium to aluminium) can be added to refine grain structure, and the preforms or foils can be prepared by rapid quenching. Very rapid quenching may provide amorphous metal structure, which possess further advantages.[]

Interaction with base metals


For successful wetting, the base metal has to be at least partially soluble in at least one component of the brazing alloy. The molten alloy therefore tends to attack the base metal and dissolve it, slightly changing its composition in the process. The composition change is reflected in the change of the alloy's melting point and the corresponding change of fluidity. For example, some alloys dissolve both silver and copper; dissolved silver lowers their melting point and increases fluidity, copper has the opposite effect. The melting point change can be exploited. As the remelt temperature can be increased by enriching the alloy with dissolved base metal, step brazing using the same braze can be possible. Alloys that do not significantly attack the base metals are more suitable for brazing thin sections. Nonhomogenous microstructure of the braze may cause non-uniform melting and localized erosions of the base metal. Wetting of base metals can be improved by adding a suitable metal to the alloy. Tin facilitates wetting of iron, nickel, and many other alloys. Copper wets ferrous metals that silver does not attack, copper-silver alloys can therefore braze steels silver alone won't wet. Zinc improves wetting of ferrous metals, indium as well. Aluminium improves wetting of aluminium alloys. For wetting of ceramics, reactive metals capable of forming chemical compounds with the ceramic (e.g. titanium, vanadium, zirconium...) can be added to the braze. Dissolution of base metals can cause detrimental changes in the brazing alloy. For example, aluminium dissolved from aluminium bronzes can embrittle the braze; addition of nickel to the braze can offset this. The effect works both ways; there can be detrimental interactions between the braze alloy and the base metal. Presence of phosphorus in the braze alloy leads to formation of brittle phosphides of iron and nickel, phosphorus-containing alloys are therefore unsuitable for brazing nickel and ferrous alloys. Boron tends to diffuse into the base metals, especially along the grain boundaries, and may form brittle borides. Carbon can negatively influence some steels.

Brazing Care has to be taken to avoid galvanic corrosion between the braze and the base metal, and especially between dissimilar base metals being brazed together. Formation of brittle intermetallic compounds on the alloy interface can cause joint failure. This is discussed more in-depth with solders. The potentially detrimental phases may be distributed evenly through the volume of the alloy, or be concentrated on the braze-base interface. A thick layer of interfacial intermetallics is usually considered detrimental due to its commonly low fracture toughness and other sub-par mechanical properties. In some situations, e.g. die attaching, it however does not matter much as silicon chips are not typically subjected to mechanical abuse.[] On wetting, brazes may liberate elements from the base metal. For example, aluminium-silicon braze wets silicon nitride, dissociates the surface so it can react with silicon, and liberates nitrogen, which may create voids along the joint interface and lower its strength. Titanium-containing nickel-gold braze wets silicon nitride and reacts with its surface, forming titanium nitride and liberating silicon; silicon then forms brittle nickel silicides and eutectic gold-silicon phase; the resulting joint is weak and melts at much lower temperature than may be expected.[] Metals may diffuse from one base alloy to the other one, causing embrittlement or corrosion. An example is diffusion of aluminium from aluminium bronze to a ferrous alloy when joining these. A diffusion barrier, e.g. a copper layer (e.g. in a trimet strip), can be used. A sacrificial layer of a noble metal can be used on the base metal as an oxygen barrier, preventing formation of oxides and facilitating fluxless brazing. During brazing, the noble metal layer dissolves in the filler metal. Copper or nickel plating of stainless steels performs the same function.[] In brazing copper, a reducing atmosphere (or even a reducing flame) may react with the oxygen residues in the metal, which are present as cuprous oxide inclusions, and cause hydrogen embrittlement. The hydrogen present in the flame or atmosphere at high temperature reacts with the oxide, yielding metallic copper and water vapour, steam. The steam bubbles exert high pressure in the metal structure, leading to cracks and joint porosity. Oxygen-free copper is not sensitive to this effect, however the most readily available grades, e.g. electrolytic copper or high-conductivity copper, are. The embrittled joint may then fail catastrophically without any previous sign of deformation or deterioration.[10]

15

Preform
A brazing preform is a high quality, precision metal stamping used for a variety of joining applications in manufacturing electronic devices and systems. Typical brazing preform uses include attaching electronic circuitry, packaging electronic devices, providing good thermal and electrical conductivity, and providing an interface for electronic connections. Square, rectangular and disc shaped brazing preforms are commonly used to attach electronic components containing silicon dies to a substrate such as a printed circuit board. Rectangular frame shaped preforms are often required for the construction of electronic packages while washer shaped brazing preforms are typically utilized to attach lead wires and hermetic feed-throughs to electronic circuits and packages. Some preforms are also used in diodes, rectifiers, optoelectronic devices and components packaging.[11]

Brazing

16

References
[1] Lucas-Milhaupt SIL-FOS 18 Copper/Silver/Phosphorus Alloy (http:/ / www. matweb. com/ search/ datasheet. aspx?matguid=2d38b7e2323d4f33a3916976d6c54375& ckck=1) [4] The Brazing Guide (http:/ / www. inductionatmospheres. com/ pdf/ BrazingGuide. pdf) [6] AWS A3.0:2001, Standard Welding Terms and Definitions Including Terms for Adhesive Bonding, Brazing, Soldering, Thermal Cutting, and Thermal Spraying, American Welding Society (2001), p. 118. ISBN 0-87171-624-0 [11] http:/ / www. coininginc. com/ Preforms. asp

Bibliography
Groover, Mikell P. (2007). Fundamentals Of Modern Manufacturing: Materials Processes, And Systems (2nd ed.). John Wiley & Sons. ISBN978-81-265-1266-9. Schwartz, Mel M. (1987). Brazing. ASM International. ISBN978-0-87170-246-3.

Further reading
Fletcher, M.J. (1971). Vacuum Brazing. London,: Mills and Boon Limited. ISBN0-263-51708-X. P.M. Roberts, "Industrial Brazing Practice", CRC Press, Boca Raton, Florida, 2004. Kent White, "Authentic Aluminum Gas Welding: Plus Brazing & Soldering." Publisher: TM Technologies, 2008. Andrea Cagnetti "Experimental survey on fluid brazing in ancient goldsmith's art" International Journal of Material Research (2009) DOI 10.3139/146.101783 (http://www.ijmr.de/ijmr/o_archiv. asp?o_id=25112811648-50&ausgabe_id=2912131822-237&artikel_id=2912131825-6865&task=03&j=2009& h=01&nav_id=0)

External links
The Brazing Guide (http://www.inductionatmospheres.com/brazing.html) Brazing & Soldering Aluminum, Copper, Brass, etc. (http://www.tinmantech.com/html/faq_brazing.php) European Association for Brazing and Soldering (http://www.brazingandsoldering.org) Braze welding (http://www.tpub.com/content/construction/14250/css/14250_126.htm)

Filler metal

17

Filler metal
A filler metal is a metal added in the making of a joint through welding, brazing, or soldering. Four types of filler metals existcovered electrodes, bare electrode wire or rod, tubular electrode wire, and welding fluxes. Sometimes non-consumable electrodes are included as well, but since these metals are not consumed by the welding process, they are normally excluded.

Usage
Covered electrodes
Covered electrodes are used extensively in shielded metal arc welding and are a major factor in that method's popularity.

Bare electrode wires


Bare electrode wires are used in gas metal arc welding and bare electrode rods are used in gas tungsten arc welding.

Tubular electrode wires


Tubular electrode wire is used in flux-cored arc welding.

Welding fluxes
Welding fluxes are used in submerged arc welding.

References
Cary, Howard B. and Scott C. Helzer (2005). Modern Welding Technology. Upper Saddle River, New Jersey: Pearson Education. ISBN 0-13-599290-7.

Capillary action

18

Capillary action
Capillary action (sometimes capillarity, capillary motion, or wicking) is the ability of a liquid to flow in narrow spaces without the assistance of, and in opposition to, external forces like gravity. The effect can be seen in the drawing up of liquids between the hairs of a paint-brush, in a thin tube, in porous materials such as paper, in some non-porous materials such as liquified carbon fiber, or in a cell. It occurs because of intermolecular forces between the liquid and solid surrounding surfaces. If the diameter of the tube is sufficiently small, then the combination of surface tension (which is caused by cohesion within the liquid) and adhesive forces between the liquid and container act to lift the liquid.[1]

History
Albert Einstein's first paper[2] submitted in 1900 to Annalen der Physik was on capillarity. It was titled Folgerungen aus den Kapillarittserscheinungen, which was translated as Conclusions from the capillarity phenomena, found in volume 4, page 513 (published in 1901).
Capillary action of water compared to mercury, in each case with respect to a polar surface e.g. glass

Phenomena and physics of capillary action


A common apparatus used to demonstrate the first phenomenon is the capillary tube. When the lower end of a vertical glass tube is placed in a liquid such as water, a concave meniscus forms. Adhesion forces between the fluid and the solid inner wall pulls the liquid column up until there is a sufficient mass of liquid for gravitational forces to overcome these intermolecular forces. The contact length (around the edge) between the top of the liquid column and the tube is proportional to the diameter of the tube, while the weight of the liquid column is proportional to the square of the tube's diameter, so a narrow tube will draw a liquid column higher than a wide tube.

Capillary Flow Experiment to investigate capillary flows and phenomena aboard the International Space Station

In plants and trees


The capillary action is enhanced in trees by branching, evaporation at the leaves creating depressurization, and probably by osmotic pressure added at the roots and possibly at other locations inside the plant, especially when gathering humidity with air roots.[3][4]

Capillary action

19

Examples
Capillary action is essential for the drainage of constantly produced tear fluid from the eye. Two canaliculi of tiny diameter are present in the inner corner of the eyelid, also called the lacrimal ducts; their openings can be seen with the naked eye within the lacrymal sacs when the eyelids are everted. Wicking is the absorption of a liquid by a material in the manner of a candle wick. Paper towels absorb liquid through capillary action, allowing a fluid to be transferred from a surface to the towel. The small pores of a sponge act as small capillaries, causing it to absorb a comparatively large amount of fluid. Some textile fabrics are said to use capillary action to "wick" sweat away from the skin. These are often referred to as wicking fabrics, after the capillary properties of candle and lamp wicks. Capillary action is observed in thin layer chromatography, in which a solvent moves vertically up a plate via capillary action. In this case the pores are gaps between very small particles. With some pairs of materials, such as mercury and glass, the intermolecular forces within the liquid exceed those between the solid and the liquid, so a convex meniscus forms and capillary action works in reverse. In hydrology, capillary action describes the attraction of water molecules to soil particles. Capillary action is responsible for moving groundwater from wet areas of the soil to dry areas. Differences in soil potential ( ) drive capillary action in soil.

Height of a meniscus
The height h of a liquid column is given by:[5]

where is the liquid-air surface tension (force/unit length), is the contact angle, is the density of liquid (mass/volume), g is local gravitational field strength (force/unit mass), and r is radius of tube (length). For a water-filled glass tube in air at standard laboratory conditions, = 0.0728 N/m at 20 C, = 0 (cos(0) = 1), is 1000kg/m3, and g = 9.81m/s2. For these values, the height of the water column is

Thus for a 4m (13ft) diameter glass tube in lab conditions given above (radius 2m (6.6ft)), the water would rise an unnoticeable 0.007mm (0.00028in). However, for a 4cm (1.6in) diameter tube (radius 2cm (0.79in)), the water would rise 0.7mm (0.028in), and for a 0.4mm (0.016in) diameter tube (radius 0.2mm (0.0079in)), the water would rise 70mm (2.8in).

Liquid transport in porous media


When a dry porous medium, such as a brick or a wick, is brought into contact with a liquid, it will start absorbing the liquid at a rate which decreases over time. For a bar of material with cross-sectional area A that is wetted on one end, the cumulative volume V of absorbed liquid after a time t is

where S is the sorptivity of the medium, with dimensions m/s1/2 or mm/min1/2. The quantity

Capillary flow in a brick, with a sorptivity of 5.0 mmmin-1/2 and a porosity of 0.25.

Capillary action is called the cumulative liquid intake, with the dimension of length. The wetted length of the bar, that is the distance between the wetted end of the bar and the so-called wet front, is dependent on the fraction f of the volume occupied by liquid. This number f is the porosity of the medium; the wetted length is then

20

Some authors use the quantity S/f as the sorptivity.[6] The above description is for the case where gravity and evaporation do not play a role. Sorptivity is a relevant property of building materials, because it affects the amount of rising dampness. Some values for the sorptivity of building materials are in the table below.
Material Sorptivity Source (mm min-1/2) [7] [7] [7]

Aerated concrete 0.54 Gypsum plaster Clay brick 3.50 1.16

References
[3] [4] [5] [6] Tree physics (http:/ / npand. wordpress. com/ 2008/ 08/ 05/ tree-physics-1/ ) at "Neat, Plausible And" scientific discussion website. Water in Redwood and other trees, mostly by evaporation (http:/ / www. wonderquest. com/ Redwood. htm) article at wonderquest website. G.K. Batchelor, 'An Introduction To Fluid Dynamics', Cambridge University Press (1967) ISBN 0-521-66396-2 C. Hall, W.D. Hoff, Water transport in brick, stone, and concrete. (2002) page 131 on Google books (http:/ / books. google. com/ books?id=q-QOAAAAQAAJ& lpg=PA131& ots=tq5JxlmMUe& pg=PA131#v=onepage& q& f=false) [7] Hall and Hoff, p. 122

Liquidus

21

Liquidus
The liquidus temperature, TL or Tliq, is mostly used for glasses, alloys and rocks. It specifies the maximum temperature at which crystals can co-exist with the melt in thermodynamic equilibrium. Above the liquidus temperature the material is homogeneous and liquid at equilibrium. Below the liquidus temperature more and more crystals may form in the melt if one waits a sufficiently long time, depending on the material. However, even below the liquidus temperature homogeneous glasses can be obtained through sufficiently fast cooling, i.e., through kinetic inhibition of the crystallization process.

The crystal phase that crystallizes first on cooling a substance to its liquidus temperature is termed primary crystalline phase or primary phase. The composition range within which the primary phase remains constant is known as primary crystalline phase field. The liquidus temperature is important in the glass industry because crystallization can cause severe problems during the glass melting and forming processes, and it also may lead to product failure. The liquidus temperature can be contrasted to the solidus temperature. The solidus temperature quantifies the point at which a material completely solidifies (crystallizes). The liquidus and solidus temperatures do not necessarily align or overlap; if a gap exists between the liquidus and solidus temperatures, then within that gap, the material consists of solid and liquid phases simultaneously (like a slurry). For pure substances, e.g. pure metal, pure water, etc. the liquidus and solidus are at the same temperature, and the term "melting point" may be used. For impure substances, e.g. alloys, tap water, coca cola, ice cream, etc. the melting point broadens into a melting interval instead. If the temperature is within the melting interval, one may see "slurries" at equilibrium, i.e. the slurry will neither fully solidify nor melt. This is why new snow of high purity either melts or stays solid, while dirty snow on the ground tend to become slushy at certain temperatures. Weld melt pools containing high levels of sulfur, either from melted impurities from the base metal or from the welding electrode, typically have very broad melting intervals, which leads to increased risk of hot cracking.

Liquidus temperature curve in the binary glass system SiO2-Li2O, [1] based on 91 published data collected in SciGlass ; model fit from [2] Glassproperties.com

Soldering

22

Soldering
Soldering is a process in which two or more metal items are joined together by melting and flowing a filler metal (solder) into the joint, the filler metal having a lower melting point than the workpiece. Soldering differs from welding in that soldering does not involve melting the work pieces. In brazing, the filler metal melts at a higher temperature, but the workpiece metal does not melt. Formerly nearly all solders contained lead, but environmental concerns have increasingly dictated use of lead-free alloys for electronics and plumbing purposes.
Desoldering a contact from a wire.

Origins
There is evidence that soldering was employed as early as 5000 years ago in Mesopotamia.[1] Soldering and brazing are thought to have arisen very early in the history of metal-working, probably before 4000 BC [2]. Sumerian swords from ~3000 BC were assembled using hard soldering. Soldering was historically used to make jewelry items, cooking ware and tools, as well as other uses such as in assembling stained glass.

Applications
Soldering is used in plumbing, in electronics and metalwork from flashing to jewelry. Soldering provides reasonably permanent but reversible connections between copper pipes in plumbing systems as well as joints in sheet metal objects such as food cans, roof flashing, rain gutters and automobile radiators.
Small figurine being created by soldering

Jewelry components, machine tools and some refrigeration and plumbing components are often assembled and repaired by the higher temperature silver soldering process. Small mechanical parts are often soldered or brazed as well. Soldering is also used to join lead came and copper foil in stained glass work. It can also be used as a semi-permanent patch for a leak in a container or cooking vessel. Electronic soldering connects electrical wiring and electronic components to printed circuit boards (PCBs).

Solders
Soldering filler materials are available in many different alloys for differing applications. In electronics assembly, the eutectic alloy of 63% tin and 37% lead (or 60/40, which is almost identical in melting point) has been the alloy of choice. Other alloys are used for plumbing, mechanical assembly, and other applications. Some examples of soft-solder are tin-lead for general purposes, tin-zinc for joining aluminium, lead-silver for strength at higher than room temperature, cadmium-silver for strength at high temperatures, zinc-aluminium for aluminium and corrosion resistance, and tin-silver and tin-bismuth for electronics.

Soldering A eutectic formulation has advantages when applied to soldering: the liquidus and solidus temperatures are the same, so there is no plastic phase, and it has the lowest possible melting point. Having the lowest possible melting point minimizes heat stress on electronic components during soldering. And, having no plastic phase allows for quicker wetting as the solder heats up, and quicker setup as the solder cools. A non-eutectic formulation must remain still as the temperature drops through the liquidus and solidus temperatures. Any movement during the plastic phase may result in cracks, resulting in an unreliable joint. Common solder formulations based on tin and lead are listed below. The fraction represent percentage of tin first, then lead, totaling 100%: 63/37: melts at 183 C (361F) (eutectic: the only mixture that melts at a point, instead of over a range) 60/40: melts between 183190C (361374F) 50/50: melts between 185215C (365419F) For environmental reasons (and the introduction of regulations such as the European RoHS (Restriction of Hazardous Substances Directive)), lead-free solders are becoming more widely used. They are also suggested anywhere young children may come into contact with (since young children are likely to place things into their mouths), or for outdoor use where rain and other precipitation may wash the lead into the groundwater. Unfortunately, most lead-free solders are not eutectic formulations, melting at around 250 C (482F), making it more difficult to create reliable joints with them. Other common solders include low-temperature formulations (often containing bismuth), which are often used to join previously-soldered assemblies without un-soldering earlier connections, and high-temperature formulations (usually containing silver) which are used for high-temperature operation or for first assembly of items which must not become unsoldered during subsequent operations. Alloying silver with other metals changes the melting point, adhesion and wetting characteristics, and tensile strength. Of all the brazing alloys, silver solders have the greatest strength and the broadest applications.[2] Specialty alloys are available with properties such as higher strength, the ability to solder aluminum, better electrical conductivity, and higher corrosion resistance.[]

23

Flux
The purpose of flux is to facilitate the soldering process. One of the obstacles to a successful solder joint is an impurity at the site of the joint, for example, dirt, oil or oxidation. The impurities can be removed by mechanical cleaning or by chemical means, but the elevated temperatures required to melt the filler metal (the solder) encourages the work piece (and the solder) to re-oxidize. This effect is accelerated as the soldering temperatures increase and can completely prevent the solder from joining to the workpiece. One of the earliest forms of flux was charcoal, which acts as a reducing agent and helps prevent oxidation during the soldering process. Some fluxes go beyond the simple prevention of oxidation and also provide some form of chemical cleaning (corrosion). For many years, the most common type of flux used in electronics (soft soldering) was rosin-based, using the rosin from selected pine trees. It was ideal in that it was non-corrosive and non-conductive at normal temperatures but became mildly reactive (corrosive) at the elevated soldering temperatures. Plumbing and automotive applications, among others, typically use an acid-based (muriatic acid) flux which provides cleaning of the joint. These fluxes cannot be used in electronics because they are conductive and because they will eventually dissolve the small diameter wires. Many fluxes also act as a wetting agent in the soldering process,[3] reducing the surface tension of the molten solder and causing it to flow and wet the workpieces more easily. Fluxes for soft solder are currently available in three basic formulations: 1. Water-soluble fluxes - higher activity fluxes designed to be removed with water after soldering (no VOCs required for removal). 2. No-clean fluxes - mild enough to not "require" removal due to their non-conductive and non-corrosive residue.[4] These fluxes are called "no-clean" because the residue left after the solder operation is non-conductive and won't

Soldering cause electrical shorts; nevertheless they leave a plainly visible white residue that resembles diluted bird-droppings. No-clean flux residue is acceptable on all 3 classes of PCBs as defined by IPC-610 provided it does not inhibit visual inspection, access to test points, or have a wet, tacky or excessive residue that may spread onto other areas. Connector mating surfaces must also be free of flux residue. Finger prints in no clean residue is a class 3 defect[5] 3. Traditional rosin fluxes - available in non-activated (R), mildly activated (RMA) and activated (RA) formulations. RA and RMA fluxes contain rosin combined with an activating agent, typically an acid, which increases the wettability of metals to which it is applied by removing existing oxides. The residue resulting from the use of RA flux is corrosive and must be cleaned. RMA flux is formulated to result in a residue which is not significantly corrosive, with cleaning being preferred but optional. Flux performance needs to be carefully evaluated; a very mild 'no-clean' flux might be perfectly acceptable for production equipment, but not give adequate performance for a poorly controlled hand-soldering operation.

24

Processes
There are three forms of soldering, each requiring progressively higher temperatures and producing an increasingly stronger joint strength: 1. Soft soldering, which originally used a tin-lead alloy as the filler metal, 2. silver soldering, which uses an alloy containing silver, 3. brazing which uses a brass alloy for the filler. The alloy of the filler metal for each type of soldering can be adjusted to modify the melting temperature of the filler. Soldering differs from gluing significantly in that the filler metals alloy with the workpiece at the junction to form a gas- and liquid-tight bond.[4] Soft soldering is characterized by having a melting point of the filler metal below approximately 400 C (752F),[7] whereas silver soldering and brazing use higher temperatures, typically requiring a flame or [6] Brazing and soldering processes classification chart carbon arc torch to achieve the melting of the filler. Soft solder filler metals are typically alloys (often containing lead) that have liquidus temperatures below 350C. In this soldering process, heat is applied to the parts to be joined, causing the solder to melt and to bond to the workpieces in an alloying process called wetting. In stranded wire, the solder is drawn up into the wire by capillary action in a process called 'wicking'. Capillary action also takes place when the workpieces are very close together or touching. The joint's tensile strength is dependent on the filler metal used. Soldering produces electrically-conductive, water- and gas-tight joints.

Soldering Each type of solder offers advantages and disadvantages. Soft solder is so called because of the soft lead that is its primary ingredient. Soft soldering uses the lowest temperatures but does not make a strong joint and is unsuitable for mechanical load-bearing applications. It is also unsuitable for high-temperature applications as it softens and melts. Silver soldering, as used by jewelers, machinists and in some plumbing applications, requires the use of a torch or other high-temperature source, and is much stronger than soft soldering. Brazing provides the strongest joint but also requires the hottest temperatures to melt the filler metal, requiring a torch or other high temperature source and darkened goggles to protect the eyes from the bright light produced by the white-hot work. It is often used to repair cast-iron objects, wrought-iron furniture, etc. Soldering operations can be performed with hand tools, one joint at a time, or en masse on a production line. Hand soldering is typically performed with a soldering iron, soldering gun, or a torch, or occasionally a hot-air pencil. Sheetmetal work was traditionally done with "soldering coppers" directly heated by a flame, with sufficient stored heat in the mass of the soldering copper to complete a joint; torches or electrically-heated soldering irons are more convenient. All soldered joints require the same elements of cleaning of the metal parts to be joined, fitting up the joint, heating the parts, applying flux, applying the filler, removing heat and holding the assembly still until the filler metal has completely solidified. Depending on the nature of flux material used, cleaning of the joints may be required after they have cooled. Each alloy has characteristics that work best for certain applications, notably strength and conductivity, and each type of solder and alloy has different melting temperatures. The term silver solder likewise denotes the type of solder that is used. Some soft solders are "silver bearing" alloys used to solder silver-plated items. Lead based solders should not be used on precious metals because the lead dissolves the metal and disfigures it.

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Soldering and brazing


The distinction between soldering and brazing is based on the melting temperature of the filler alloy. A temperature of 450 C is usually used as a practical delineating point between soldering and brazing . Soft soldering can be done with a heated iron whereas the other methods require a higher temperature torch or furnace to melt the filler metal. Different equipment is usually required since a soldering iron cannot achieve high enough temperatures for hard soldering or brazing. Brazing filler metal is stronger than silver solder, which is stronger than lead-based soft solder. Brazing solders are formulated primarily for strength, silver solder is used by jewelers to protect the precious metal and by machinists and refrigeration technicians for its tensile strength but lower melting temperature than brazing, and the primary benefit of soft solder is the low temperature used (to prevent heat damage to electronic components and insulation). Since the joint is produced using a metal with a lower melting temperature than the workpiece, the joint will weaken as the ambient temperature approaches the melting point of the filler metal. For that reason, the higher temperature processes produce joints which are effective at higher temperatures. Brazed connections can be as strong or nearly as strong as the parts they connect,[8][9] even at elevated temperatures.[10]

Silver soldering
"Hard soldering" or "silver soldering" is used to join precious and semi-precious metals such as gold, silver, brass, and copper. The solder is usually referred to as easy, medium, or hard. This refers to its melting temperature, not the strength of the joint. Extra-easy solder contains 56% silver and has a melting point of 1,145 F (618C). Extra-hard solder has 80% silver and melts at 1,370 F (740C). If multiple joints are needed, then the jeweler will start with hard or extra-hard solder and switch to lower temperature solders for later joints. Silver solder is absorbed by the surrounding metal, resulting in a joint that is actually stronger than the metal being joined. The metal being joined must be perfectly flush, as silver solder cannot normally be used as a filler and any gaps will remain.

Soldering Another difference between brazing and soldering is how the solder is applied. In brazing, one generally uses rods that are touched to the joint while being heated. With silver soldering, small pieces of solder wire are placed onto the metal prior to heating. A flux, often made of boric acid and denatured alcohol, is used to keep the metal and solder clean and to prevent the solder from moving before it melts. When silver solder melts, it tends to flow towards the area of greatest heat. Jewelers can somewhat control the direction the solder moves by leading it with a torch; it will even run straight up along a seam.

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Induction soldering
Induction soldering uses induction heating by high-frequency AC current in a surrounding copper coil. This induces currents in the part being soldered, which generates heat because of the higher resistance of a joint versus its surrounding metal (resistive heating). These copper coils can be shaped to fit the joint more precisely. A filler metal (solder) is placed between the facing surfaces, and this solder melts at a fairly low temperature. Fluxes are commonly used in induction soldering. This technique is particularly suited to continuously soldering, in which case these coils wrap around a cylinder or a pipe that needs to be soldered. Some metals are easier to solder than others. Copper, silver, and gold are easy. Iron, mild steel and nickel are next in difficulty. Because of their thin, strong oxide films, stainless steel and aluminium are even more difficult to solder. Titanium, magnesium, cast irons, some high-carbon steels, ceramics, and graphite can be soldered but it involves a process similar to joining carbides: they are first plated with a suitable metallic element that induces interfacial bonding.

Electronic components (PCBs)


Currently, mass-production printed circuit boards (PCBs) are mostly wave soldered or reflow soldered, though hand soldering of production electronics is also still standard practice. In wave soldering, parts are temporarily kept in place with small dabs of adhesive, then the assembly is passed over flowing solder in a bulk container. This solder is shaken into waves so the whole PCB is not submerged in solder, but rather touched by these waves. The end result is that solder stays on pins and pads, but not on the PCB itself. Reflow soldering is a process in which a solder paste (a mixture of prealloyed solder powder and a flux-vehicle that has a peanut butter-like consistency[4]) is used to stick the components to their attachment pads, after which the assembly is heated by an infrared lamp, a hot air pencil, or, more commonly, by passing it through a carefully controlled oven. Since different components can be best assembled by different techniques, it is common to use two or more processes for a given PCB. For example, surface mounted parts may be reflow soldered first, with a wave soldering process for the through-hole mounted components coming next, and bulkier parts hand-soldered last. For hand soldering, the heat source tool should be selected to provide adequate heat for the size of joint to be completed. A 100 watt soldering iron may provide too much heat for printed circuit boards,
A tube of multicore electronics solder used for manual soldering

Soldering

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while a 25 watt iron will not provide enough heat for large electrical connectors, joining copper roof flashing, or large stained-glass lead came. Using a tool with too high a temperature can damage sensitive components, but protracted heating by a tool that is too cool or under powered can also cause extensive heat damage. Hand-soldering techniques require a great deal of skill to use on what is known as fine-pitch soldering of chip packages. In particular ball grid array (BGA) devices are notoriously difficult, if not impossible, to rework by hand. For attachment of electronic components to a PCB, proper selection and use of flux helps prevent oxidation during soldering, which is essential for good wetting and heat transfer. The soldering iron tip must be clean and pre-tinned with solder to ensure rapid heat transfer. Components which dissipate large amounts of heat during operation are sometimes elevated above the PCB to avoid PCB overheating. After inserting a through-hole mounted component, the excess lead is cut off, leaving a length of about the radius of the pad. Plastic or metal mounting clips or holders may be used with large devices to aid heat dissipation and reduce joint stresses. A heat sink may be used on the leads of heat sensitive components to reduce heat transfer to the component. This is especially applicable to Broken solder joints on a circuit board germanium parts. (Note the heat sink will mean the use of more heat to complete the joint.) If all metal surfaces are not properly fluxed and brought above the melting temperature of the solder in use, the result will be an unreliable "cold solder joint". To simplify soldering, beginners are usually advised to apply the soldering iron and the solder separately to the joint, rather than the solder being applied direct to the iron. When sufficient solder is applied, the solder wire is removed. When the surfaces are adequately heated, the solder will flow around the joint. The iron is then removed from the joint. Since non-eutectic solder alloys have a small plastic range, the joint must not be moved until the solder has cooled down through both the liquidus and solidus temperatures. When visually inspected, a good solder joint will appear smooth and shiny, with the outline of the soldered wire clearly visible. A matte gray surface is a good indicator of a joint that was moved during soldering. Other solder defects can be detected visually as well. Too little solder will result in a dry and unreliable joint; too much solder (the familiar 'solder blob' to beginners) is not necessarily unsound, but tends to mean poor wetting. With some fluxes, flux residue remaining on the joint may need to be removed, using water, alcohol or other solvents compatible with the parts in question. Excess solder and unconsumed flux and residue is sometimes wiped from the soldering iron tip between joints. The tip of the iron is kept wetted with solder ("tinned") when hot to minimize oxidation and corrosion of the tip itself. Environmental legislation in many countries, and the whole of the European Community area (see RoHS), has led to a change in formulation of both solders and fluxes. Water soluble non-rosin based fluxes have been increasingly used since the 1980s so that soldered boards can be cleaned with water or water based cleaners. This eliminates hazardous solvents from the production environment, and from factory effluents.

An improperly soldered 'cold' joint

Soldering Hot-bar reflow Hot-bar reflow is a selective soldering process where two pre-fluxed, solder coated parts are heated with heating element (called a thermode) to a sufficient temperature to melt the solder. Pressure is applied through the whole process (usually 15 s) to ensure that components stay in place during cooling. The heating element is heated and cooled for each connection. Up to 4000 W can be used in the heating element allowing fast soldering, good results with connections requiring high energy.[11] Laser Laser soldering is a technique where a ~30-50 W laser is used to melt and solder an electrical connection joint. Diode laser systems based on semiconductor junctions are used for this purpose.[12] Wavelengths are typically 808nm through 980nm. The beam is delivered via an optical fiber to the workpiece, with fiber diameters 800m and smaller. Since the beam out of the end of the fiber diverges rapidly, lenses are used to create a suitable spot size on the workpiece at a suitable working distance. A wire feeder is used to supply solder.[13] Both lead-tin and silver-tin material can be soldered. Process recipes will differ depending on the alloy composition. For soldering 44-pin chip carriers to a board using soldering preforms, power levels were on the order of 10 Watts and solder times approximately 1 second. Low power levels can lead to incomplete wetting and the formation of voids, both of which can weaken the joint.

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Fiber focus infrared soldering


Fiber focus infrared soldering is technique where many infrared sources are led through fibers, then focused onto a single spot at which the connection is soldered.[14]Wikipedia:Verifiability

Pipe soldering
Copper pipe, or 'tube', is commonly joined by soldering. When applied in a plumbing trade context, soldering is more often referred to as sweating and a tubing connection so made is referred to as a sweated joint. Copper tubing conducts heat away much faster than a hand-held soldering iron or gun can provide, so a propane torch is most commonly used to deliver the necessary power; for large tubing sizes and fittings a MAPP-fueled, acetylene-fueled, or propylene-fueled torch is used with atmospheric air as the oxidizer; MAPP/oxygen or acetylene/oxygen are rarely used soldered copper pipes because the flame temperature is much higher than the melting point of copper. Too much heat destroys the temper of hard-tempered copper tubing, and can burn the flux out of a joint before the solder is added, resulting in a faulty joint. For larger tubing sizes, a torch fitted with various sizes of interchangeable swirl tips is employed to deliver the needed power. Most experienced plumbers seldom use propane fuel. In the hands of a skilled tradesman, the hotter flame of acetylene, MAPP, or propylene allows more joints to be completed per hour.

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Solder fittings, also known as capillary fittings, are short sections of smooth pipe designed to slide over the outside of the mating tube, are usually used for copper joints. Commonly used fittings include for straight connectors, reducers, bends, and tees. There are two types of solder fittings: end feed fittings which contain no solder, and solder ring fittings (often known as Yorkshire fittings), in which there is a ring of solder in a small circular recess inside the fitting. As with all solder joints, all parts to be joined must be clean and oxide free. Internal and external wire brushes are available for the common pipe and fitting sizes; emery cloth and wire-wool are frequently used as well, although metal wool products are discouraged, as they can contain oil, which would contaminate the joint. Because of the size of the parts involved, and the high activity and contaminating tendency of the flame, plumbing fluxes are typically much more chemically active, and more acidic, than electronic fluxes. Because plumbing joints may be done at any angle, even upside down, plumbing fluxes are generally formulated as pastes which stay in place better than liquids. Flux should be applied to all surfaces of the joint, inside and out. Flux residues should be removed after the joint is complete or they can, eventually, erode through the copper substrates and cause failure of the joint. Many plumbing solder formulations are available, with different characteristics, such as higher or lower melting temperature, depending on the specific requirements of the job. Building Lead-free Solder codes currently almost universally require the use of lead-free solder for potable water piping, though traditional tin-lead solder is still available. Studies have shown that lead-soldered plumbing pipes can result in elevated levels of lead in drinking water.[15][16] Since copper pipe quickly conducts heat away from a joint, great care must be taken to ensure that the joint is properly heated through to obtain a good bond. After the joint is properly cleaned, fluxed and fitted, the torch flame is applied to the thickest part of the joint, typically the fitting with the pipe inside it, with the solder applied at the gap between the tube and the fitting. When all the parts are heated through, the solder will melt and flow into the joint by capillary action. The torch may need to be moved around the joint to ensure all areas are wetted out. However, the installer must take care to not overheat the areas being soldered. If the tube begins to discolor it means that the tube has been over-heated and is beginning to oxidize, stopping the flow of the solder and causing the soldered joint not to seal properly. Before oxidation the molten solder will follow the heat of the torch around the joint. When the joint is properly wetted out, the solder and then the heat are removed, and while the joint is still very hot, it is usually wiped with a dry rag. This removes excess solder as well as flux residue before it cools down and hardens. With a solder ring joint, the joint is heated until a ring of molten solder is visible around the edge of the fitting and allowed to cool. Solder connections are usually considered the most difficult of the three methods of connecting copper tubing, but soldering copper is a very simple process, provided some basic conditions are provided:

Solder

Soldering The tubing and fittings must be cleaned to bare metal with no tarnish Any pressure which is formed by heating of the tubing must have an outlet The joint must be dry (which makes repairing water pipes by soldering tedious) Copper is only one material that is joined in this manner. Brass fittings are often used for valves or as a connection fitting between copper and other metals. Brass piping is soldered in this manner in the making of brass and some woodwind (saxophone and flute) musical instruments

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Mechanical and aluminium soldering


A number of solder materials, primarily zinc alloys, are used for soldering aluminium metal and alloys and to some lesser extent steel and zinc. This mechanical soldering is similar to a low temperature brazing operation, in that the mechanical characteristics of the joint are reasonably good and it can be used for structural repairs of those materials. The American welding society defines brazing as using filler metals with melting points over 450 C (842F) or, by the traditional definition in the United States, above 800 F (427C). Aluminium soldering alloys generally have melting temperatures around 730 F (388C).[17] This soldering / brazing operation can use a propane torch heat source.[18] These materials are often advertised as "aluminium welding", but the process does not involve melting the base metal, and therefore is not properly a weld. United States Military Standard or MIL-SPEC specification MIL-R-4208 defines one standard for these zinc-based brazing/soldering alloys.[19] A number of products meet this specification.[18][20][21] or very similar performance standards.[17] Resistance soldering is soldering in which the heat required to flow the solder is created by passing an electric current through the solder. When current is conducted through a resistive material a certain level of heat is generated. By regulating the amount of current conducted and the level of resistance encountered, the amount of heat produced can be predetermined and controlled. Electrical resistance (usually described as a material's opposition to the flow of an electric current) is used to convert electric energy into thermal energy as an electric current (I) conducted through a material with resistance (R) releases power (P) equal to: P = I R, where P is the power measured in watts, I is the current measured in amps and R is the resistance measured in ohms.

Resistance soldering
Resistance soldering is unlike using a conduction iron, where heat is produced within an element and then passed through a thermally conductive tip into the joint area. A cold soldering iron requires time to reach working temperature and must be kept hot between solder joints. Thermal transfer may be inhibited if the tip is not kept properly wetted during use. With resistance soldering an intense heat can be rapidly developed directly within the joint area and in a tightly controlled manner. This allows a faster ramp up to the required solder melt temperature and minimizes thermal travel away from the solder joint, which helps to minimize the potential for thermal damage to materials or components in the surrounding area. Heat is only produced while each joint is being made, making resistance soldering more energy efficient. Resistance soldering equipment, unlike conduction irons, can be used for difficult soldering and brazing applications where significantly higher temperatures may be required. This makes resistance comparable to flame soldering in some situations. When the required temperature can be achieved by either flame or resistance methods the resistance heat is more localized because of direct contact, whereas the flame will spread thus heating a potentially larger area.

Soldering

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Stained glass soldering


Historically, stained glass soldering tips were copper, heated by being placed in a charcoal-burning brazier. Multiple tips were used; when one tip cooled down from use, it was placed back in the brazier of charcoal and the next tip was used. More recently, electrically heated soldering irons are used. These are heated by a coil or ceramic heating element inside the tip of the iron. Different power ratings are available, and temperature can be controlled electronically. These characteristics allow longer beads to be run without interrupting the work to change tips. Soldering irons designed for electronic use are often effective though they are sometimes underpowered for the heavy copper and lead came used in stained glass work. Oleic acid is the classic flux material that has been used to improve solderability. Tiffany type stainglass is made by gluing copper foil around the edges of the pieces of glass and then soldering them together. This method makes it possible to create three dimensional stained glass pieces.

Solderability
The solderability of a substrate is a measure of the ease with which a soldered joint can be made to that material.

Desoldering and resoldering


Used solder contains some of the dissolved base metals and is unsuitable for reuse in making new joints. Once the solder's capacity for the base metal has been achieved it will no longer properly bond with the base metal, usually resulting in a brittle cold solder joint with a crystalline appearance. It is good practice to remove solder from a joint prior to resolderingdesoldering braids or vacuum desoldering equipment (solder suckers) can be used. Desoldering wicks contain plenty of flux that will lift the contamination from the copper trace and any device leads that are present. This will leave a bright, shiny, clean junction to be resoldered. The lower melting point of solder means it can be melted away from the base metal, leaving it mostly intact, though the outer layer will be "tinned" with solder. Flux will remain which can easily be removed by abrasive or chemical processes. This tinned layer will allow solder to flow into a new joint, resulting in a new joint, as well as making the new solder flow very quickly and easily.

Lead-free electronic soldering


More recently environmental legislation has specifically targeted the wide use of lead in the electronics industry. The RoHS directives in Europe required many new electronic circuit boards to be lead free by 1 July 2006, mostly in the consumer goods industry, but in some others as well. In Japan lead was phased out prior to legislation by manufacturers due to the additional expense in recycling products containing lead.[22] However, even without the presence of lead, soldering can release fumes that are harmful and/or toxic to humans. It is highly recommended to use a device that can remove the fumes from the work area either by ventilating outside or filtering the air.[23] It is a common misconception that lead free soldering requires higher soldering temperatures than lead/tin solder; the wetting temperature in lead/tin solder is higher than the melting point and is the controlling factor - Wave soldering can proceed at the same temperature as previous lead/tin soldering.[22] Nevertheless many new technical challenges have arisen with this endeavor; to reduce the melting point of tin based solder alloys various new alloys have had to be researched, with additives of copper, silver, bismuth as typical minor additives to reduce melting point and control other properties, additionally tin is a more corrosive metal, and can eventually lead to the failure of solder baths etc.[22]

Soldering Lead-free construction has also extended to components, pins, and connectors. Most of these pins used copper frames, and either lead, tin, gold or other finishes. Tin finishes are the most popular of lead-free finishes. Nevertheless, this brings up the issue of how to deal with tin whiskers. The current movement brings the electronics industry back to the problems solved in the 1960s by adding lead. JEDEC has created a classification system to help lead-free electronic manufacturers decide what provisions to take against whiskers, depending upon their application.

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Soldering defects
In the joining of copper tube, failure to properly heat and fill a joint may lead to a 'void' being formed. This is usually a result of improper placement of the flame. If the heat of the flame is not directed at the back of the fitting cup, and the solder wire applied 180 degrees opposite the flame, then solder will quickly fill the opening of the fitting, trapping some flux inside the joint. This bubble of trapped flux is the void; an area inside a soldered joint where solder is unable to completely fill the fittings' cup, because flux has become sealed inside the joint, preventing solder from occupying that space.

Electronics
Various problems may arise in the soldering process which lead to joints which are nonfunctional either immediately or after a period of use. The most common defect when hand-soldering results from the parts being joined not exceeding the solder's liquidus temperature, resulting in a "cold solder" joint. This is usually the result of the soldering iron being used to heat the solder directly, rather than the parts themselves. Properly done, the iron heats the parts to be connected, which in turn melt the solder, guaranteeing adequate heat in the joined parts for thorough wetting. In electronic hand soldering the flux is embedded in the solder. Therefore heating the solder first may cause the flux to evaporate before it cleans the surfaces being soldered. A cold-soldered joint may not conduct at all, or may conduct only intermittently. Cold-soldered joints also happen in mass production, and are a common cause of equipment which passes testing, but malfunctions after sometimes years of operation. A "dry joint" occurs when the cooling solder is moved, and often occurs because the joint moves when the soldering iron is removed from the joint. An improperly selected or applied flux can cause joint failure. If not properly cleaned, a flux may corrode the joint and cause eventual joint failure. Without flux the joint may not be clean, or may be oxidized, resulting in an unsound joint. In electronics non-corrosive fluxes are often used. Therefore cleaning flux off may merely be a matter of aesthetics or to make visual inspection of joints easier in specialised 'mission critical' applications such as medical devices, military and aerospace. For satellites also to reduce weight slightly but usefully. In high humidity, even non-corrosive flux might remain slightly active, therefore the flux may be removed to reduce corrosion over time. In some applications, the PCB might also be coated in some form of protective material such as a lacquer to protect it and exposed solder joints from the environment. Movement of metals being soldered before the solder has cooled will cause a highly unreliable cracked joint. In electronics' soldering terminology this is known as a 'dry' joint. It has a characteristically dull or grainy appearance immediately after the joint is made, rather than being smooth, bright and shiny. This appearance is caused by crystallization of the liquid solder. A dry joint is weak mechanically and a poor conductor electrically. In general a good looking soldered joint is a good joint. As mentioned it should be smooth, bright and shiny. If the joint has lumps or balls of otherwise shiny solder the metal has not 'wetted' properly. Not being bright and shiny suggests a weak 'dry' joint. However, technicians trying to apply this guideline when using lead-free solder formulations may experience frustration, because these types of solders readily cool to a dull surface even if the joint is good. The solder looks shiny while molten, and suddenly hazes over as it solidifies even though it has not been disturbed during cooling.

Soldering In electronics a 'concave' fillet is ideal. This indicates good wetting and minimal use of solder (therefore minimal heating of heat sensitive components). A joint may be good, but if a large amount of unnecessary solder is used then more heating is obviously required. Excessive heating of a PCB may result in 'delamination', the copper track may actually lift off the board, particularly on single sided PCBs without through hole plating.

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Tools
In principle any type of soldering tool can carry out any work using solder at temperatures it can generate. In practice different tools are more suitable for different applications. Hand-soldering tools widely used for electronics work include the electric soldering iron, which can be fitted with a variety of tips ranging from blunt to very fine, to chisel heads for hot-cutting plastics rather than soldering. The simplest irons do not have temperature regulation; small irons rapidly cool when used to solder to, say, a metal chassis, while large irons have tips too cumbersome for working on PCBs and similar fine work. Temperature-controlled irons have a reserve of power and can maintain temperature over a wide range of work. The soldering gun heats faster but has a larger and heavier body. Gas-powered irons using a catalytic tip to heat a bit, without flame, are used for portable applications. Hot-air guns and pencils allow rework of component packages which cannot easily be performed with electric irons and guns. For non-electronic applications soldering torches use a flame rather than a soldering tip to heat solder. Soldering torches are often powered by butane[24] and are available in sizes ranging from very small butane/oxygen units suitable for very fine but high-temperature jewelry work, to full-size oxy-fuel torches suitable for much larger work such as copper piping. Common multipurpose propane torches, the same kind used for heat-stripping paint and thawing pipes, can be used for soldering pipes and other fairly large objects either with or without a soldering tip attachment; pipes are generally soldered with a torch by directly applying the open flame. A soldering copper is a tool with a large copper head and a long handle which is heated in a blacksmith's forge fire and used to apply heat to sheet metal for soldering. Typical soldering coppers have heads weighing between one and four pounds. The head provides a large thermal mass to store enough heat for soldering large areas before needing re-heating in the fire; the larger the head, the longer the working time. Historically, soldering coppers were standard tools used in auto bodywork, although body solder has been mostly superseded by spot welding for mechanical connection, and non-metallic fillers for contouring. Toaster ovens and hand held infrared lights have been used by hobbyists to replicate production soldering processes on a much smaller scale. Bristle brushes are usually used to apply plumbing paste flux. For electronic work, flux-core solder is generally used, but additional flux may be used from a flux pen or dispensed from a small bottle with a syringe-like needle. Wire brush, wire wool and emery cloth are commonly used to prepare plumbing joints for connection. Electronic joints are usually made between surfaces that have been tinned and rarely require mechanical cleaning, though tarnished component leads and copper traces with a dark layer of oxide passivation (due to aging), as on a new prototyping board that has been on the shelf for about a year or more, may need to be mechanically cleaned. Some fluxes for electronics are designed to be stable and inactive when cool and do not need to be cleaned off, though they still can be if desired, while other fluxes are acidic and must be removed after soldering to prevent corrosion of the circuits. For PCB assembly and rework, either an alcohol or acetone is commonly used with cotton swabs or bristle brushes to remove flux residue after soldering. A heavy rag is usually used to remove flux from a plumbing joint before it cools and hardens. A fiberglass brush can also be used. A heat sink, such as a crocodile clip, can be used to prevent damaging heat-sensitive components while hand-soldering. The heat sink limits the temperature of the component body by absorbing and dissipating heat (reducing the thermal resistance between the component and the air), while the thermal resistance of the leads maintains the temperature difference between the part of the leads being soldered and the component body so that

Soldering the leads become hot enough to melt the solder while the component body remains cooler.

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References
[2] [3] [4] [5] [6] How soldering differs from brazing (http:/ / www. tinmantech. com/ html/ faq_brazing_versus_soldering. php) Solder Flux (http:/ / www. indium. com/ products/ solderfabrications/ fluxes. php) Soldering 101 - A Basic Overview (http:/ / www. indium. com/ _dynamo/ download. php?docid=27) IPC-A-610 revision E section 10.6.4 AWS A3.0:2001, Standard Welding Terms and Definitions Including Terms for Adhesive Bonding, Brazing, Soldering, Thermal Cutting, and Thermal Spraying, American Welding Society (2001), p. 118. ISBN 0-87171-624-0 [8] Brazing tips (http:/ / www. bellmanmelcor. com/ brazing_tips1. htm) [9] Factors that affect joint strength (http:/ / www. wallcolmonoy. com/ TechServices/ NicrobrazNewsArchives/ WCC_Article_Joint_Strength. htm) [10] Properties of Gold-Nickel Alloy Brazed Joints in High Temperature Materials; Prof. Jakob Colbus & Karl Zimmermann. (http:/ / www. goldbulletin. org/ assets/ file/ goldbulletin/ downloads/ Colbus_2_7. pdf) [12] 0204 www.coherent.com [13] 070927 ma-info.de [14] 070927 vincenc.com.tw (mentioned as a technique) [15] (http:/ / www. plumbingpages. com/ featurepages/ Pipeworkfluxsolder. cfm) [16] http:/ / www. askdrsears. com/ html/ 10/ T110211. asp [17] Alumaloy (http:/ / www. alumaloy. net/ alumaloy1. htm), accessed 2009-04-03 [18] Alumiweld FAQ (http:/ / www. alumiweld. com/ faq. html), accessed 2009-04-03 [19] MIL-R-4208 (http:/ / www. tpub. com/ content/ logistics/ 34/ 39/ 10/ 00-580-0585. htm), accessed 2009-04-03 [20] Aladdin 3-in-1 (http:/ / www. aladdin3in1. com/ catalog. htm), accessed 2009-04-03 [21] HTS-2000 (http:/ / www. aluminumrepair. com/ more_info. asp), accessed 2009-03-09 [22] FACT AND FICTION IN LEAD FREE SOLDERING (http:/ / www. dklmetals. co. uk/ PDF Files/ Factorfiction. pdf) from www.dkmetals.co.uk [23] Hazards of Soldering Fumes (http:/ / www. sentryair. com/ solder-fumes. htm) [24] What is the definition of soldering torch? (http:/ / www. toolingu. com/ definition-660130-28677-soldering-torch. html)

External links
Desoldering guide (http://www.epemag.wimborne.co.uk/desolderpix.htm) A short video explanation of how solder works (http://vega.org.uk/video/programme/166) RoHS directive 2002/95/EC (http://europa.eu/eur-lex/pri/en/oj/dat/2003/l_037/l_03720030213en00190023. pdf) - the restriction of the use of certain hazardous substances in electrical and electronic equipment A useful table of various solder alloy liquidus temperatures can be found in an article hosted at the EMPF (http:// www.empf.org/empfasis/jan05/lfaudit.htm).

Inert

35

Inert
In English, to be inert is to be in a state of doing little or nothing.

Chemistry
In chemistry, the term inert is used to describe a substance that is not chemically reactive. The noble gases were previously known as inert gases because of their perceived lack of participation in any chemical reactions. The reason for this is that their outmost electron shells (valence shells) are completely filled, so that they have little tendency to acquire or lose electrons. It is now known that these gases in fact do react to form chemical compounds, such as xenon tetrafluoride. Hence, they have been renamed to noble gases. However, a large amount of energy is required to drive such reactions, usually in the form of heat, pressure, or radiation, often assisted by catalysts. The resulting compounds often need to be kept in moisture-free conditions at low temperatures to prevent rapid decomposition back into their elements. The term inert may also be applied in a relative sense. For example, molecular nitrogen is inert under ordinary conditions, existing as diatomic molecules, N 2. The presence of a strong triple covalent bond in the N 2 molecule renders it unreactive under normal circumstances. Nevertheless, nitrogen gas does react with the alkali metal lithium to form compound lithium nitride (Li3N), even under ordinary conditions. Under high pressures and temperatures and with the right catalysts, nitrogen becomes more reactive; the Haber process uses such conditions to produce ammonia from atmospheric nitrogen. Inert atmospheres consisting of gases such as argon, nitrogen, or helium are commonly used in chemical reaction chambers and in storage containers for air-sensitive or water-sensitive substances, to prevent unwanted side-reactions of these substances with air and water.

Pesticides
The Federal Insecticide, Fungicide, and Rodenticide Act divides the ingredients in pesticides into two groups: active and inert. An inert chemical, under this context, is one that does not have a toxic effect on the species the pesticide is meant to combat, but that does not rule out that it may still have a biological activity on other species, including being toxic to humans. Solvents, propellents, preservatives, among others, are thus considered "inert ingredients"[1] in pesticides.[2] Since 1997, the United States Environmental Protection Agency has recommended that pesticide manufacturers label the non-active ingredients as "other ingredients" rather than "inert" to prevent misinformation to the public.[2]

Number theory
In the branch of mathematics known as algebraic number theory, a prime ideal is said to be inert if it is still prime when considered in an extension field. Such a prime might have instead split as a product of other prime ideals, but by being inert it remains essentially unchanged.

Munitions
In the field of weapons and explosives, an inert munition is one in which all energetic material such as primers, fuses, and the explosive or incendiary materials within them have been removed or otherwise rendered harmless. Inert munitions are used in military and naval training, and they are also collected and displayed by public museums, or by private parties. See also military dummy. Typically, American and NATO inert munitions are painted entirely in light blue and/or have the word "INERT" stenciled on them in prominent locations.

Inert

36

References
[1] EPA (2010), Inert Ingredients Eligible for FIFRA 25(b) Pesticide Products Last Updated December 20, 2010 (http:/ / www. epa. gov/ opprd001/ inerts/ section25b_inerts. pdf), Office of prevention, pesticides adn toxic substances [2] Inert ingredients in pesticide products (http:/ / www. epa. gov/ opprd001/ inerts/ ). US Environmental Protection Agency, Office of Pesticide Programs.

Phosphide
In chemistry, a phosphide is a compound of phosphorus with a less electronegative element or elements. Binary compounds are formed with the majority of less electronegative elements with the exception of Hg, Pb, Sb, Bi, Te, Po.[1] Typically there are a range of stoichiometries with each element; for example, potassium has nine phosphides (K3P, K4P3, K5P4, KP, K4P6, K3P7, K3P11, KP10.3, KP15) and nickel has eight (Ni3P, Ni5P2, Ni12P5, Ni2P, Ni5P4, NiP, NiP2, NiP3).[1] Classification of these compounds is difficult.[2] On structural and reactivity grounds they can be broadly classified[1] as: principally ionic with P3 ions. Examples are the group 1 (e.g. Na 3P) and group 2 (e.g. Ca 3P 2) metal phosphides. polyphosphides with, for example, dumbbell P4 2 ions; cluster P3 11 ions; polymeric chain anions (e.g. the helical (P ) n ion) and complex sheet or 3-D anions. compounds with individual P atoms in a metal lattice that can be semiconducting (e.g. GaP) through to metallic (e.g. TaP) in terms of electrical conductance.[3] Two polyphosphide ions, P4 3 found in K 4P 3 and P5 4 found in K P , are radical anions with an odd number of valence electrons making both compounds 5 4 paramagnetic.[1]

Preparation
There are many ways to prepare phosphide compounds. The most general and common way that this is done is through the heating of the metal to be bound to phosphorus and red phosphorus (P) under inert atmospheric conditions or vacuum. In principle, all metal phosphides and polyphosphides can be synthesized from elemental phosphorus and the respective metal element in stoichiometric forms. However, the synthesis is complicated due to several problems. The exothermic reactions are often explosive due to local overheating. Oxidized metals, or even just an oxidized layer on the exterior of the metal, causes extreme and unacceptably high temperatures for beginning phosphorination.[4] Hydrothermal reactions to generate nickel phosphides have produced pure and well crystallized nickel phosphide compounds, Ni2P and Ni12P5. These compounds were synthesized through a solid-liquid reaction between NiCl212H2O and red phosphorus at 200 C for 24 and 48 hours, respectively.[5]

Phosphide

37

Examples
Aluminium phosphide (AlP) Indium phosphide (InP) Calcium phosphide (Ca3P2) Copper phosphide (Cu3P) Magnesium phosphide (Mg3P2)

Natural examples
Schreibersite (Fe,Ni)3P is a common mineral in some meteorites.[6][7]

References
[1] H.G. Von Schnering, W. Hnle Phosphides - Solid-state Chemistry Encyclopedia of Inorganic Chemistry Ed. R. Bruce King (1994) John Wiley & Sons ISBN 0-471-93620-0 [6] Mindat (http:/ / www. mindat. org) [7] Handbook of Mineralogy (http:/ / www. handbookofmineralogy. com)

Nickel

38

Nickel
Nickel Ni 28

cobalt nickel copper

Ni
Pd Nickel in the periodic table Appearance lustrous, metallic, and silver with a gold tinge

General properties Name, symbol, number Pronunciation Element category Group, period, block Standard atomic weight nickel, Ni, 28 /nkl/ NIK-l transition metal 10, 4, d 58.6934(4)(2)

Nickel

39
Electron configuration

[Ar] 4s2 3d8 or [Ar] 4s1 3d9 (see text) 2, 8, 16, 2 or 2, 8, 17, 1

History Discovery First isolation Axel Fredrik Cronstedt (1751) Axel Fredrik Cronstedt (1751) Physical properties Phase Density (near r.t.) Liquid density at m.p. Meltingpoint Boilingpoint Heatoffusion Heat of vaporization Molar heat capacity solid 8.908 gcm3 7.81 gcm3 1728K, 1455C, 2651F 3186K, 2913C, 5275F 17.48 kJmol1 377.5 kJmol1 26.07 Jmol1K1 Vapor pressure P (Pa) 1 10 100 1k 10 k 100 k

at T (K) 1783 1950 2154 2410 2741 3184 Atomic properties Oxidation states 4 , 3, 2, 1 , -1 (mildly basic oxide) 1.91 (Pauling scale) 1st: 737.1 kJmol1 2nd: 1753.0 kJmol1 3rd: 3395 kJmol1 Atomic radius Covalent radius Van der Waals radius 124 pm 1244 pm 163 pm Miscellanea
[1] [2]

Electronegativity Ionization energies (more)

Nickel

40
Crystal structure face-centered cubic

Magnetic ordering Electrical resistivity Thermal conductivity Thermal expansion

ferromagnetic (20C) 69.3 nm 90.9Wm1K1 (25 C) 13.4 mm1K1

Speed of sound (thin rod) (r.t.) 4900ms1 Young's modulus Shear modulus Bulk modulus Poisson ratio Mohs hardness Vickers hardness Brinell hardness CAS registry number 200 GPa 76 GPa 180 GPa 0.31 4.0 638 MPa 700 MPa 7440-02-0 Most stable isotopes Main article: Isotopes of nickel iso
58 59 60 61 62 63 64

NA

half-life

DM DE (MeV) 1.9258 -

DP
58 59

Ni 68.077% >71020 y ++ Ni trace 7.6104 y


60 61 62

Fe

Co

Ni 26.223% Ni 1.14%

Ni is stable with 32 neutrons Ni is stable with 33 neutrons Ni is stable with 34 neutrons 0.0669
63

Ni 3.634% Ni syn

100.1 y
64

Cu

Ni 0.926%

Ni is stable with 36 neutrons

Nickel is a chemical element with the chemical symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel belongs to the transition metals and is hard and ductile. Pure nickel shows a significant chemical activity that can be observed when nickel is powdered to maximize the exposed surface area on which reactions can occur, but larger pieces of the metal are slow to react with air at ambient conditions due to the formation of a protective oxide surface. Even then, nickel is reactive enough with oxygen so that native nickel is rarely found on Earth's surface, being mostly confined to the interiors of larger nickeliron meteorites that were protected from oxidation during their time in space. On Earth, such native nickel is always found in combination with iron, a reflection of those elements' origin as major end products of supernova nucleosynthesis. An ironnickel mixture is thought to compose Earth's inner core.[3] The use of nickel (as a natural meteoric nickeliron alloy) has been traced as far back as 3500 BC. Nickel was first isolated and classified as a chemical element in 1751 by Axel Fredrik Cronstedt, who initially mistook its ore for a

Nickel copper mineral. The element name comes from a mischievous sprite of German miner's mythology, Nickel (similar to Old Nick), that personified the fact that copper-nickel ores resisted refinement into copper. An economically important source of nickel is the iron ore limonite, which often contains 1-2% nickel. Nickel's other important ore minerals include garnierite, and pentlandite. Major production sites include Sudbury region in Canada (which is thought to be of meteoric origin), New Caledonia in the Pacific and Norilsk in Russia. Because of nickel's slow rate of oxidation at room temperature, it is considered corrosion-resistant. Historically this has led to its use for plating metals such as iron and brass, to its use for chemical apparatus, and its use in certain alloys that retain a high silvery polish, such as German silver. About 6% of world nickel production is still used for corrosion-resistant pure-nickel plating. Nickel was once a common component of coins, but has largely been replaced by cheaper iron for this purpose, especially since the metal is a skin allergen for some people. It was reintroduced into UK coins in 2012 despite objections from dermatologists.[] Nickel is one of four elements that are ferromagnetic around room temperature. Alnico permanent magnets based partly on nickel are of intermediate strength between iron-based permanent magnets and rare-earth magnets. The metal is chiefly valuable in the modern world for the alloys it forms; about 60% of world production is used in nickel-steels (particularly stainless steel). Other common alloys, as well as some new superalloys, make up most of the remainder of world nickel use, with chemical uses for nickel compounds consuming less than 3% of production.[] As a compound, nickel has a number of niche chemical manufacturing uses, such as a catalyst for hydrogenation. Enzymes of some microorganisms and plants contain nickel as an active site, which makes the metal an essential nutrient for them.

41

Characteristics
Atomic and physical properties
Nickel is a silvery-white metal with a slight golden tinge that takes a high polish. It is one of only four elements that are magnetic at or near room temperature, the others being iron, cobalt and gadolinium. Its Curie temperature is 355 C, meaning that bulk nickel is non-magnetic above this temperature.[4] The unit cell of nickel is a face centered cube with the lattice parameter of 0.352nm giving an atomic radius of 0.124nm. Nickel belongs to the transition metals and is hard and ductile. Electron configuration dispute The nickel atom has two electron configurations, [Ar] 4s2 3d8 and [Ar] 4s1 3d9, which are very close in energy, where the symbol [Ar] refers to the argon-like core structure. There is some disagreement as to which should be considered the lowest energy configuration.[6] Chemistry textbooks quote the electron configuration of nickel as [Ar] 4s2 3d8,[5] or equivalently as [Ar] 3d8 4s2.[6] This configuration agrees with the Madelung energy ordering rule, which predicts that 4s is filled before 3d. It is supported by the experimental fact that the lowest energy state of the nickel atom is a 4s2 3d8 energy level, specifically the 3d8(3F) 4s2 3F, J=4 level.[7] However each of these two configurations in fact gives rise to a set of states at different energies.[7] The two sets of energies overlap, and the average energy of states having configuration [Ar] 4s1 3d9 is in fact lower than the average energy of states having configuration [Ar] 4s2 3d8. For this reason the research literature on atomic calculations quotes the ground state configuration of nickel as 4s1 3d9.[6]

Nickel

42

Isotopes
Naturally occurring nickel is composed of 5 stable isotopes; 58Ni, 60Ni, 61Ni, 62Ni and 64Ni with 58Ni being the most abundant (68.077% natural abundance). 62Ni is the most stable nuclide of all the existing elements, with binding energy greater than both 56Fe, often incorrectly cited as most stable, and 58Fe.[8] 18 radioisotopes have been characterised with the most stable being 59Ni with a half-life of 76,000 years, 63Ni with a half-life of 100.1 years, and 56Ni with a half-life of 6.077 days. All of the remaining radioactive isotopes have half-lives that are less than 60 hours and the majority of these have half-lives that are less than 30 seconds. This element also has one meta state.[] Nickel-56 is produced by the silicon burning process and later set free in large quantities during type Ia supernovae. The shape of the light curve of these supernovae at intermediate to late-times corresponds to the decay via electron capture of nickel-56 to cobalt-56 and ultimately to iron-56.[] Nickel-59 is a long-lived cosmogenic radionuclide with a half-life of 76,000 years. 59Ni has found many applications in isotope geology. 59Ni has been used to date the terrestrial age of meteorites and to determine abundances of extraterrestrial dust in ice and sediment. Nickel-60 is the daughter product of the extinct radionuclide 60Fe, which decays with a half-life of 2.6 million years. Because 60Fe has such a long half-life, its persistence in materials in the solar system at high enough concentrations may have generated observable variations in the isotopic composition of 60Ni. Therefore, the abundance of 60Ni present in extraterrestrial material may provide insight into the origin of the solar system and its early history. Nickel-62 has the highest binding energy per nucleon of any isotope for any element (8.7946 MeV/nucleon).[9] Isotopes heavier than 62Ni cannot be formed by nuclear fusion without losing energy. 48Ni, discovered in 1999, is the most proton-rich heavy element isotope known. With 28 protons and 20 neutrons 48Ni is "double magic" (like 208Pb) and therefore unusually stable.[][10] The isotopes of nickel range in atomic weight from 48u (48 Ni) to 78u (78 Ni). Nickel-78's half-life was recently measured at 110 milliseconds, and is believed an important isotope in supernova nucleosynthesis of elements heavier than iron.[11]

Occurrence
On Earth, nickel occurs most often in combination with sulfur and iron in pentlandite, with sulfur in millerite, with arsenic in the mineral nickeline, and with arsenic and sulfur in nickel galena.[12] Nickel is commonly found in iron meteorites as the alloys kamacite and taenite. The bulk of the nickel mined comes from two types of ore deposits. The first are laterites where the principal ore minerals are nickeliferous limonite: (Fe, Ni)O(OH) and garnierite (a hydrous nickel silicate): (Ni, Mg)3Si2O5(OH)4. The second are magmatic sulfide deposits where the principal ore mineral is pentlandite: (Ni, Fe)9S8. Australia and New Caledonia have the biggest estimate reserves (45% all together).[]

Widmansttten pattern showing the two forms of nickel-iron, Kamacite and Taenite, in an octahedrite meteorite

In terms of World Resources, identified land-based resources averaging 1% nickel or greater contain at least 130 million tons of nickel (about the double of known reserves). About 60% is in laterites and 40% is in sulfide deposits.[] Based on geophysical evidence, most of the nickel on Earth is postulated to be concentrated in the Earth's outer core and inner core. Kamacite and taenite are naturally occurring alloys of iron and nickel. For kamacite the alloy is usually in the proportion of 90:10 to 95:5 although impurities such as cobalt or carbon may be present, while for taenite the nickel content is between 20% and 65%. Kamacite and taenite occur in nickel iron meteorites.[13]

Nickel

43

Compounds
The most common oxidation state of nickel is +2, but compounds of Ni0, Ni+, and Ni3+ are well known, and Ni4+ has been demonstrated.[]

Nickel(0)
Tetracarbonylnickel (Ni(CO)4), discovered by Ludwig Mond,[] is a volatile, highly toxic liquid at room temperature. On heating, the complex decomposes back to nickel and carbon monoxide: Ni(CO)4
Tetracarbonyl nickel

Ni + 4 CO

This behavior is exploited in the Mond process for purifying nickel, as described above. The related nickel(0) complex bis(cyclooctadiene)nickel(0) is a useful catalyst in organonickel chemistry due to the easily displaced cod ligands.

Nickel(I)
Nickel(I) compounds and complexes are rare. The dark red diamagnetic K4[Ni2(CN)6] is a representative example of Ni(I). It is prepared by reduction of K2[Ni2(CN)6] using sodium amalgam. This compound is unstable and liberates H2 gas from water.[]

Structure of [Ni2(CN)6]2- ion

[]

Nickel(II)
Nickel(II) forms compounds with all common anions, i.e. the sulfide, sulfate, carbonate, hydroxide, carboxylates, and halides. Nickel(II) sulfate is produced in large quantities by dissolving nickel metal or oxides in sulfuric acid. It exists as both a hexaand heptahydrates.[14] This compound is useful for electroplating nickel.

Color of various Ni(II) complexes in aqueous solution. From left to right, [Ni(NH3)6]2+, [Ni(en)3]2+, [NiCl4]2-, [Ni(H2O)6]2+

The four halogens form nickel compounds, all of which adopt octahedral geometries. Nickel(II) chloride is most common, and its behavior is illustrative of the other halides. Nickel(II) chloride is produced by dissolving nickel residues in

Nickel

44 hydrochloric acid. The dichloride is usually encountered as the green hexahydrate, but it can be dehydrated to give the yellow anhydrous NiCl2. Some tetracoordinate nickel(II) complexes form both tetrahedral and square planar geometries. The tetrahedral complexes are paramagnetic and the square planar complexes are diamagnetic. This equilibrium as well as the formation of octahedral complexes contrasts with the behavior of the divalent complexes of the heavier group 10 metals, palladium(II) and platinum(II), which tend to adopt only square-planar complexes.[]

Nickel sulfate crystals

Nickelocene is known; it has an electron count of 20, making it relatively unstable.

Nickel(III) and (IV)


For simple compounds, nickel(III) and nickel(IV) only occurs with fluoride and oxides, with the exception of KNiIO6, which can be considered as a formal salt of the [IO6]5- ion.[] Ni(IV) is present in the mixed oxide BaNiO3, while Ni(III) is present in nickel(III) oxide, which is used as the cathode in many rechargeable batteries, including nickel-cadmium, nickel-iron, nickel hydrogen, and nickel-metal hydride, and used by certain manufacturers in Li-ion batteries.[15] Nickel(III) can be stabilized by -donor ligands such as thiols and phosphines.[]

Nickel(III) antimonide

History
Because the ores of nickel are easily mistaken for ores of silver, understanding of this metal and its use dates to relatively recent times. However, the unintentional use of nickel is ancient, and can be traced back as far as 3500 BC. Bronzes from what is now Syria had contained up to 2% nickel.[16] Further, there are Chinese manuscripts suggesting that "white copper" (cupronickel, known as baitong) was used there between 1700 and 1400 BC. This Paktong white copper was exported to Britain as early as the 17th century, but the nickel content of this alloy was not discovered until 1822.[] In medieval Germany, a red mineral was found in the Erzgebirge (Ore Mountains) that resembled copper ore. However, when miners were unable to extract any copper from it, they blamed a mischievous sprite of German mythology, Nickel (similar to Old Nick), for besetting the copper. They called this ore Kupfernickel from the German Kupfer for copper.[17][][][] This ore is now known to be nickeline or niccolite, a nickel arsenide. In 1751, Baron Axel Fredrik Cronstedt was trying to extract copper from kupfernickeland instead produced a white metal that he named after the spirit that had given its name to the mineral, nickel.[18] In modern German, Kupfernickel or Kupfer-Nickel designates the alloy cupronickel. After its discovery, the only source for nickel was the rare Kupfernickel but, from 1824 on, the nickel was obtained as a byproduct of cobalt blue production. The first large-scale producer of nickel was Norway, which exploited nickel-rich pyrrhotite from 1848 on. The introduction of nickel in steel production in 1889 increased the demand for nickel, and the nickel deposits of New Caledonia, which were discovered in 1865, provided most of the world's supply between 1875 and 1915. The discovery of the large deposits in the Sudbury Basin, Canada in 1883, in Norilsk-Talnakh, Russia in 1920, and in the Merensky Reef, South Africa in 1924 made large-scale production of nickel possible.[]

Nickel

45

Nickel has been a component of coins since the mid-19th century. In the United States, the term "nickel" or "nick" originally applied to the copper-nickel Flying Eagle cent, which replaced copper with 12% nickel 185758, then the Indian Head cent of the same alloy from 18591864. Still later in 1865, the term designated the three-cent nickel, with nickel increased to 25%. In 1866, the five-cent shield nickel (25% nickel, 75% copper) appropriated the designation. Along with the alloy proportion, this term has been used to the present in the United States. Coins of nearly pure nickel were first used in 1881 in Dutch coins made of pure nickel Switzerland, and more notably 99.9% nickel five-cent coins were struck in Canada (the world's largest nickel producer at the time) during non-war years from 19221981, and their metal content made these coins magnetic.[19] During the wartime period 194245, more or all nickel was removed from Canadian and U.S. coins, due to nickel's war-critical use in armor.[][20] Canada switched alloys again to plated steel during the Korean war, but was forced to stop making pure nickel "nickels" in 1981, reserving the pure 99.9% nickel alloy after 1968 only to its higher-value coins. Finally, in the 21st century, with rising nickel prices, most countries that formerly used nickel in their coins have abandoned the metal for cost reasons, and the U.S. five cents remains one of the few coins that still uses the metal for anything other than exterior plating.[21]

World production

World nickel production in metric tons, in 2005. The Russian Federation is the largest producer, followed by Canada.

Mine production and reserves Australia Botswana Brazil Canada China Colombia Cuba Dominican Republic Indonesia Madagascar

[]

2010 170,000 28,000 59,100 158,000 79,000 72,000 70,000 0 232,000 15,000

2011

Reserves

180,000 24,000,000 32,000 83,000 200,000 80,000 72,000 74,000 14,000 230,000 25,000 490,000 8,700,000 3,300,000 3,000,000 720,000 5,500,000 1,000,000 3,900,000 1,600,000

Nickel

46
New Caledonia Philippines Russia South Africa Other countries 130,000 173,000 269,000 40,000 99,000 140,000 12,000,000 230,000 280,000 42,000 100,000 1,100,000 6,000,000 3,700,000 4,600,000

World total (metric tons, rounded) 1,590,000 1,800,000 80,000,000

In 2011, Russia was the largest producer of nickel with about one-fifth world share closely followed by Canada, Australia, and Indonesia and Philippines, as reported by the US Geological Survey.[] The largest deposits of nickel in non-Russian Europe are located in Finland and the second largest in Greece. A nickel deposit in western Turkey had been exploited, with this location being especially convenient for European smelters, steelmakers, and factories. Identified land-based resources averaging 1% nickel or greater contain at least 130 million tons of nickel. About 60% is in laterites and 40% is in sulfide deposits. In addition, extensive deep-sea resources of nickel are in manganese crusts and nodules covering large areas of the ocean floor, particularly in the Pacific Ocean.[] The one locality in the United States where nickel was commercially mined is Riddle, Oregon, where several square miles of nickel-bearing garnierite surface deposits are located. The mine closed in 1987.[22][23] The Eagle mine project is a proposed new nickel mine in Michigan's upper peninsula.

Extraction and purification


Nickel is recovered through extractive metallurgy. Nickel is extracted from its ores by conventional roasting and reduction processes that yield a metal of greater than 75% purity. In many stainless steel applications, 75% pure nickel can be used without further purification, depending on the composition of the impurities. Most sulfide ores have traditionally been processed using pyrometallurgical techniques to produce a matte for further refining. Recent advances in hydrometallurgy have resulted in significant nickel purification using these processes. Most sulfide deposits have traditionally been processed by concentration through a froth flotation process followed by pyrometallurgical extraction. In hydrometallurgical processes, nickel sulfide ores undergo flotation (differential flotation if Ni/Fe ratio is too low) and then smelted. After producing the nickel matte, further processing is done via the Sherritt-Gordon process. First, copper is removed by adding hydrogen sulfide, leaving a concentrate of only cobalt and nickel. Then, solvent extraction is used to separate the cobalt and nickel, with the final nickel concentration greater than 99%.

Electrorefining
A second common form of further refining involves the leaching of the metal matte into a nickel salt solution, followed by the electro-winning of the nickel from solution by plating it onto a cathode as electrolytic nickel.

Electrolytically refined nickel nodule, with visible green, crystallized nickel-electrolyte salts in the pores.

Nickel

47

Mond process
Purification of nickel oxides to obtain the purest metal is performed via the Mond process, which increases the nickel concentrate to greater than 99.99% purity.[24] This process was patented by L. Mond and has been in industrial use since before the beginning of the 20th century. In the process, nickel is reacted with carbon monoxide at around 4080C to form nickel carbonyl in the presence of a sulfur catalyst. Iron gives iron pentacarbonyl too, but this reaction is slow. If necessary, it may be separated by distillation. Dicobalt octacarbonyl is also formed in this process, but it decomposes to tetracobalt dodecacarbonyl at the reaction temperature to give a non-volatile solid.[]

Highly purified nickel spheres made by the Mond process.

Nickel is re-obtained from the nickel carbonyl by one of two processes. It may be passed through a large chamber at high temperatures in which tens of thousands of nickel spheres, called pellets, are constantly stirred. It then decomposes depositing pure nickel onto the nickel spheres. Alternatively, the nickel carbonyl may be decomposed in a smaller chamber at 230C to create fine nickel powder. The resultant carbon monoxide is re-circulated and reused through the process. The highly pure nickel produced by this process is known as "carbonyl nickel".[25]

Metal value
The market price of nickel surged throughout 2006 and the early months of 2007; as of April 5, 2007, the metal was trading at 52,300 USD/tonne or 1.47 USD/oz.[] The price subsequently fell dramatically from these peaks, and as of 19 January 2009 the metal was trading at 10,880 USD/tonne.[] The US nickel coin contains 0.04 oz (1.25 g) of nickel, which at the April 2007 price was worth 6.5 cents, along with 3.75grams of copper worth about 3 cents, making the metal value over 9 cents. Since the face value of a nickel is 5 cents, this made it an attractive target for melting by people wanting to sell the metals at a profit. However, the United States Mint, in anticipation of this practice, implemented new interim rules on December 14, 2006, subject to public comment for 30 days, which criminalize the melting and export of cents and nickels.[26] Violators can be punished with a fine of up to $10,000 and/or imprisoned for a maximum of five years. As of September 16, 2011, the melt value of a U.S. nickel is $0.0600409, which is 20% higher than the face value.[27]

Applications
The fraction of global nickel production presently used for various applications is as follows: 46% for making nickel steels; 34% in nonferrous alloys and superalloys; 14% electroplating, and 6% into other uses.[][] Nickel is used in many specific and recognizable industrial and consumer products, including stainless steel, alnico magnets, coinage, rechargeable batteries, electric guitar strings, microphone capsules, and special alloys. It is also used for plating and as a Nickel superalloy jet engine (RB199) turbine blade green tint in glass. Nickel is preeminently an alloy metal, and its chief use is in the nickel steels and nickel cast irons, of which there are many varieties. It is also widely used in many other alloys, such as nickel brasses and bronzes, and alloys with copper, chromium, aluminium, lead, cobalt, silver, and gold (Inconel, Incoloy, Monel, Nimonic).[28]

Nickel

48 Because of its resistance to corrosion, nickel has been occasionally used historically as a substitute for decorative silver. Nickel was also occasionally used in some countries after 1859 as a cheap coinage metal (see above) but in the later years of the 20th century was largely replaced by cheaper stainless steel (i.e., iron) alloys, except notably in the United States. Nickel is an excellent alloying agent for certain other precious metals, and so used in the so-called fire assay, as a collector of platinum group elements (PGE). As such, nickel is capable of full collection of all 6 PGE elements from ores, in addition to partial collection of gold. High-throughput nickel mines may also engage in PGE recovery (primarily platinum and palladium); examples are Norilsk in Russia and the Sudbury Basin in Canada. Nickel foam or nickel mesh is used in gas diffusion electrodes for alkaline fuel cells.[29][30] Nickel and its alloys are frequently used as catalysts for hydrogenation reactions. Raney nickel, a finely divided nickel-aluminium alloy, is one common form, however related catalysts are also often used, including related 'Raney-type' catalysts.

A "horseshoe magnet" made of alnico nickel alloy. The composition of alnico alloys is typically 812% Al, 1526% Ni, 524% Co, up to 6% Cu, up to 1% Ti, and the balance is Fe. The development of alnico began in 1931 when it was discovered that an alloy of iron, nickel, and aluminum had a coercivity double that of the best magnet steels of the time. Alnico magnets are now being replaced by rare earth magnets in many applications

Nickel is a naturally magnetostrictive material, meaning that, in the presence of a magnetic field, the material undergoes a small change in length.[31] In the case of nickel, this change in length is negative (contraction of the material), which is known as negative magnetostriction and is on the order of 50ppm. Nickel is used as a binder in the cemented tungsten carbide or hardmetal industry and used in proportions of six to 12% by weight. Nickel can make the tungsten carbide magnetic and adds corrosion-resistant properties to the cemented tungsten carbide parts, although the hardness is lower than those of parts made with cobalt binder.[32]

Biological role
Although not recognized until the 1970s, nickel plays important roles in the biology of microorganisms and plants.[33][34] The plant enzyme urease (an enzyme that assists in the hydrolysis of urea) contains nickel. The NiFe-hydrogenases contain nickel in addition to iron-sulfur clusters. Such [NiFe]-hydrogenases characteristically oxidise H2. A nickel-tetrapyrrole coenzyme, Cofactor F430, is present in the methyl coenzyme M reductase, which powers methanogenic archaea. One of the carbon monoxide dehydrogenase enzymes consists of an Fe-Ni-S cluster.[35] Other nickel-containing enzymes include a rare bacterial class of superoxide dismutase[36] and glyoxalase I enzymes in bacteria and several parasitic eukaryotic trypanosomal parasites [37] (this enzyme in higher organisms, including yeast and mammals, uses divalent zinc, Zn2+).[][][38][39][40]

Toxicity
In the US, the minimal risk level of nickel and its compounds is set to 0.2g/m3 for inhalation during 15364 days.[41] Nickel sulfide fume and dust are believed carcinogenic, and various other nickel compounds may be as well.[42][43] Nickel carbonyl, [Ni(CO)4], is an extremely toxic gas. The toxicity of metal carbonyls is a function of both the toxicity of the metal as well as the carbonyl's ability to give off highly toxic carbon monoxide gas, and this one is no exception; nickel carbonyl is also explosive in air.[44][45] Sensitized individuals may show an allergy to nickel, affecting their skin, also known as dermatitis. Sensitivity to nickel may also be present in patients with

Nickel pompholyx. Nickel is an important cause of contact allergy, partly due to its use in jewellery intended for pierced ears.[46] Nickel allergies affecting pierced ears are often marked by itchy, red skin. Many earrings are now made nickel-free due to this problem. The amount of nickel allowed in products that come into contact with human skin is regulated by the European Union. In 2002, researchers found amounts of nickel being emitted by 1 and 2 Euro coins far in excess of those standards. This is believed due to a galvanic reaction.[47] Nickel was voted Allergen of the Year in 2008 by the American Contact Dermatitis Society.[48] Reports also showed that both the nickel-induced activation of hypoxia-inducible factor (HIF-1) and the up-regulation of hypoxia-inducible genes are due to depleted intracellular ascorbate levels. The addition of ascorbate to the culture medium increased the intracellular ascorbate level and reversed both the metal-induced stabilization of HIF-1- and HIF-1-dependent gene expression.[49][50]

49

References
[5] G.L. Miessler and D.A. Tarr, "Inorganic Chemistry" (2nd ed., PrenticeHall 1999) p.38 [6] R.H. Petrucci et al General Chemistry (8th ed., PrenticeHall 2002) p.950 [7] NIST Atomic Spectrum Database (http:/ / physics. nist. gov/ PhysRefData/ ASD/ levels_form. html) To read the nickel atom levels, type Ni I in the Spectrum box and click on Retrieve data. [8] Fewell, M. P.. The atomic nuclide with the highest mean binding energy. American Journal of Physics 63 (7): 65358. . URL:http:/ / adsabs. harvard. edu/ abs/ 1995AmJPh. . 63. . 653F. Accessed: 2011-03-22. (Archived by WebCite at http:/ / www. webcitation. org/ 5xNHry2gq) [12] National Pollutant Inventory Nickel and compounds Fact Sheet (http:/ / www. npi. gov. au/ substances/ nickel/ index. html). Npi.gov.au. Retrieved on 2012-01-09. [14] Keith Lascelles, Lindsay G. Morgan, David Nicholls, Detmar Beyersmann Nickel Compounds in Ullmann's Encyclopedia of Industrial Chemistry 2005, Wiley-VCH, Weinheim. [17] Chambers Twentieth Century Dictionary, p888, W&R Chambers Ltd, 1977. [20] Canada used nickel plating on its five-cent coins in 1945 [21] (http:/ / realcent. forumco. com/ topic. asp?TOPIC_ID=15946) Partial list of world coins that used nickel. [26] United States Mint Moves to Limit Exportation & Melting of Coins (http:/ / www. usmint. gov/ pressroom/ index. cfm?action=press_release& ID=724), The United States Mint, press release, December 14, 2006 [31] UCLA Magnetostrictive Materials Overview (http:/ / aml. seas. ucla. edu/ research/ areas/ magnetostrictive/ overview. htm). Aml.seas.ucla.edu. Retrieved on 2012-01-09. [34] electronic-book ISBN 978-94-007-5561-1 electronic[41] ToxGuideTM for Nickel (http:/ / www. atsdr. cdc. gov/ toxguides/ toxguide-15. pdf). U.S. Department of Health and Human Services. Agency for Toxic Substances and Disease Registry

External links
Nickel (http://www.periodicvideos.com/videos/028.htm) at The Periodic Table of Videos (University of Nottingham) CDC Nickel NIOSH Workplace Safety and Health Topic (http://www.cdc.gov/niosh/topics/nickel/) An occupational hygiene assessment of dermal nickel exposures in primary production industries (http://www. iom-world.org/pubs/IOM_TM0405.pdf) by GW Hughson. Institute of Occupational Medicine Research Report TM/04/05 An occupational hygiene assessment of dermal nickel exposures in primary production and primary user industries. Phase 2 Report (http://www.iom-world.org/pubs/IOM_TM0506.pdf) by GW Hughson. Institute of Occupational Medicine Research Report TM/05/06 Norilsk Nickel, Norilsk, Russia (http://www.nornik.ru/en/) Vale Nickel, Sudbury, Ontario, Canada (formerly known as INCO) (http://nickel.vale.com/countries/canada/ sudbury/default.aspx) Xstrata Nickel, Sudbury Operations (formerly known as Falconbridge) (http://www.xstratanickel.com/EN/ Operations/Pages/SudburyOperations.aspx)

Lead

50

Lead
Lead Pb 82

thallium lead bismuthSn

Pb
Fl Lead in the periodic table Appearance metallic gray

General properties Name, symbol, number Pronunciation Element category Group, period, block Standard atomic weight lead, Pb, 82 /ld/ LED poor metal 14, 6, p 207.2

Lead

51
Electron configuration

[Xe] 4f14 5d10 6s2 6p2 2, 8, 18, 32, 18, 4

History Discovery Middle Easterns (7000 BC) Physical properties Phase Density (near r.t.) Liquid density at m.p. Meltingpoint Boilingpoint Heatoffusion Heat of vaporization Molar heat capacity solid 11.34 gcm3 10.66 gcm3 600.61K, 327.46C, 621.43F 2022K, 1749C, 3180F 4.77 kJmol1 179.5 kJmol1 26.650 Jmol1K1 Vapor pressure P (Pa) 1 10 100 1k 10 k 100 k

at T (K) 978 1088 1229 1412 1660 2027 Atomic properties Oxidation states Electronegativity Ionization energies 4, 3, 2, 1 (Amphoteric oxide) 1.87 (Pauling scale) 1st: 715.6 kJmol1 2nd: 1450.5 kJmol1 3rd: 3081.5 kJmol1 Atomic radius Covalent radius Van der Waals radius 175 pm 1465 pm 202 pm Miscellanea

Lead

52
Crystal structure face-centered cubic

Magnetic ordering Electrical resistivity Thermal conductivity Thermal expansion

diamagnetic (20C) 208 nm 35.3Wm1K1 (25 C) 28.9 mm1K1

Speed of sound (thin rod) (r.t.) (annealed) 1190ms1 Young's modulus Shear modulus Bulk modulus Poisson ratio Mohs hardness Brinell hardness CAS registry number 16 GPa 5.6 GPa 46 GPa 0.44 1.5 5.0 HB = 38.3 MPa 7439-92-1 Most stable isotopes Main article: Isotopes of lead iso
204 205 206 207 208 210

NA

half-life

DM DE (MeV) 1.972 0.051

DP
200

Pb 1.4% Pb syn

>1.41017 y 1.53107 y
206 207

Hg Tl

205

Pb 24.1% Pb 22.1% Pb 52.4% Pb trace

Pb is stable with 124 neutrons Pb is stable with 125 neutrons 0.5188 3.792 0.064
204 206

>21019 y 22.3 y

Hg Hg Bi

210

Lead is a chemical element in the carbon group with symbolPb (from Latin: plumbum) and atomic number82. Lead is a soft and malleable metal, which is regarded as a heavy metal and poor metal. Metallic lead has a bluish-white color after being freshly cut, but it soon tarnishes to a dull grayish color when exposed to air. Lead has a shiny chrome-silver luster when it is melted into a liquid. Lead is used in building construction, lead-acid batteries, bullets and shot, weights, as part of solders, pewters, fusible alloys, and as a radiation shield. Lead has the highest atomic number of all of the stable elements, although the next higher element, bismuth, has a half-life that is so long (much longer than the age of the universe) that it can be considered stable. Its four stable isotopes have 82 protons, a magic number in the nuclear shell model of atomic nuclei. Lead, at certain contact degrees, is a poisonous substance to animals, including humans. It damages the nervous system and causes brain disorders. Excessive lead also causes blood disorders in mammals. Like the element

Lead mercury, another heavy metal, lead is a neurotoxin that accumulates both in soft tissues and the bones. Lead poisoning has been documented from ancient Rome, ancient Greece, and ancient China.

53

Characteristics
Lead is a bright and silvery metal with a very slight shade of blue in a dry atmosphere.[1] Upon contact with air, it begins to tarnish by forming a complex mixture of compounds depending on the conditions. The color of the compounds can vary. The tarnish layer can contain significant amounts of carbonates and hydroxycarbonates.[2][3] It has a few characteristic properties: high density, softness, ductility and malleability, poor electrical conductivity compared to other metals, high resistance to corrosion, and ability to react with organic chemicals.[1] Various traces of other metals change its properties significantly: the addition of small amounts of antimony or copper to lead increases the A sample of freshly solidified lead (from molten state) alloy's hardness and improves corrosion resistance from sulfuric acid.[1] A few other metals also improve only hardness and fight metal fatigue, such as cadmium, tin, or tellurium; metals like sodium or calcium also have this ability, but they weaken the chemical stability.[1] Finally, zinc and bismuth simply impair the corrosion resistance (0.1% bismuth content is the industrial usage threshold).[1] In return, lead impurities mostly worsen the quality of industrial materials, although there are exceptions: for example, small amounts of lead improve the ductility of steel.[1] Lead has only one common allotrope, which is face-centered cubic, with the leadlead distance being 349pm.[4] At 327.5C (621.5F),[5] lead melts; the melting point is above that of tin (232C, 449.5F),[5] but significantly below that of germanium (938C, 1721F).[6] The boiling point of lead is 1749C (3180F),[7] which is below those of both tin (2602C, 4716F)[5] and germanium (2833C, 5131F).[6] Densities increase down the group: the Ge and Sn values (5.23[8] and 7.29gcm3,[9] respectively) are significantly below that of lead: 11.32gcm3.[8] A lead atom has 82 electrons, having an electronic configuration of [Xe]4f145d106s26p2. In its compounds, lead (unlike the other group 14 elements) most commonly loses its two and not four outermost electrons, becoming lead(II) ions, Pb2+. Such unusual behavior is rationalized by considering the inert pair effect, which occurs because of the stabilization of the 6s-orbital due to relativistic effects, which are stronger closer to the bottom of the periodic table.[10] Tin shows a weaker such effect: tin(II) is still a reducer.[10] The figures for electrode potential show that lead is only slightly easier to oxidize than hydrogen. Lead thus can dissolve in acids, but this is often impossible due to specific problems (such as the formation of insoluble salts).[11] Powdered lead burns with a bluish-white flame. As with many metals, finely divided powdered lead exhibits pyrophoricity.[12] Toxic fumes are released when lead is burned.

Isotopes
Lead occurs naturally on Earth exclusively in the form of four isotopes: lead-204, -206, -207, and -208.[13] All four can be radioactive as the hypothetical alpha decay of any would be exothermic, but the lower half-life limit has been put only for lead-204: over 1.41017years.[] This effect is, however, so weak that natural lead poses no radiation hazard. Three isotopes are also found in three of the four major decay chains: lead-206, -207 and -208 are final decay products of uranium-238, uranium-235, and thorium-232, respectively. Since the amounts of them in nature depend also on other elements' presence, the isotopic composition of natural lead varies by sample: in particular, the relative amount of lead-206 varies between 20.84% and 27.78%.[13] Aside from the stable ones, thirty-four radioisotopes have been synthesized: they have mass numbers of 178215.[] Lead-205 is the most stable radioisotope of lead, with a half-life of over 107years. 47 nuclear isomers (long-lived

Lead excited nuclear states), corresponding to 24 lead isotopes, have been characterized. The most long-lived isomer is lead-204m2 (half-life of about 1.1hours).[]

54

Chemical reactivity
Lead is classified as a post-transition metal and is also a member of the carbon group. Lead only forms a protective oxide layer although finely powdered highly purified lead can ignite in air. Melted lead is oxidized in air to lead monoxide. All chalcogens oxidize lead upon heating.[14] Fluorine does not oxidize cold lead. Hot lead can be oxidized, but the formation of a protective halide layer lowers the intensity of the reaction above 100C (210F). The reaction with chlorine is similar: thanks to the chloride layer, lead persistence against chlorine surpasses those of copper or steel up to 300C (570F).[14] Water in the presence of oxygen attacks lead to start an accelerating reaction. The presence of carbonates or sulfates results in the formation of insoluble lead salts, which protect the metal from corrosion. So does carbon dioxide, as the insoluble lead carbonate is formed; however, an excess of the gas leads to the formation of the soluble bicarbonate; this makes the use of lead pipes dangerous.[11] Lead dissolves in organic acids (in the presence of oxygen) and concentrated (80%) sulfuric acid thanks to complexation; however, it is only weakly affected by hydrochloric acid and is stable against hydrofluoric acid, as the corresponding halides are weakly soluble. Lead also dissolves in quite concentrated alkalis (10%) because of the amphoteric character and solubility of plumbites.[11]

Compounds
Lead compounds exist mainly in two main oxidation states, +2 and +4. The former is more common. Inorganic lead(IV) compounds are typically strong oxidants or exist only in highly acidic solutions.[10]

Oxides and sulfides


Three oxides are known: lead(II) oxide or lead monoxide (PbO), lead tetroxide (Pb3O4) (sometimes called "minium"), and lead dioxide (PbO2). The monoxide exists as two allotropes: -PbO and -PbO, both with layer structure and tetracoordinated lead. The alpha polymorph is red-colored and has the PbO distance of 230pm; the beta polymorph is yellow-colored and has the PbO distance of 221 and 249pm (due to asymmetry).[15] Both polymorphs can exist under standard conditions (beta with small (105 relative) impurities, such as Si, Ge, Mo, etc.). PbO reacts with acids to form salts, and with alkalis to give plumbites, [Pb(OH)3] or [Pb(OH)4]2.[16] The monoxide oxidizes in air to trilead tetroxide, which at 550C (1020F) degrades back into PbO. The dioxide may be prepared by, for example, halogenization of lead(II) salts. Regardless the polymorph, it has a black-brown color. The alpha allotrope is rhombohedral, and the beta allotrope is tetragonal.[16] Both allotropes are black-brown in color and always contain some water, which cannot be removed, as heating also causes decomposition (to PbO and Pb3O4). The dioxide is a powerful oxidizer: it can oxidize hydrochloric and sulfuric acids. It does not react with alkaline solution, but reacts with solid alkalis to give hydroxyplumbates, or with basic oxides to give plumbates.[16] Reaction of lead salts with hydrogen sulfide yields lead monosulfide. The solid has the rocksalt-like simple cubic structure, which it keeps up to the melting point, 1114C (2037F). When heated in air, it oxidizes to the sulfate and then the monoxide.[17] Lead monosulfide is almost insoluble in water, weak acids, and (NH4)2S/(NH4)2S2 solution is the key for separation of lead from analytical groups I to III ions, tin, arsenic, and antimony. However, it dissolves in nitric and hydrochloric acids, to give elemental sulfur and hydrogen sulfide, respectively.[17] Upon heating under high pressures with sulfur, it gives the disulfide. In the compound, the lead atoms are linked octahedrally with the sulfur atoms.[18] It is also a semiconductor.[19] A mixture of the monoxide and the monosulfide when heated forms the metal.[] 2 PbO + PbS 3 Pb + SO2

Lead

55

Halides and other salts


Heating lead carbonate with hydrogen fluoride yields the hydrofluoride, which decomposes to the difluoride when it melts. This white crystalline powder is more soluble than the diiodide, but less than the dibromide and the dichloride.[20] The tetrafluoride, a yellow crystalline powder, is unstable. Other dihalides are obtained upon heating lead(II) salts with the halides of other metals; lead dihalides precipitate to give white orthorhombic crystals (diiodide forms yellow hexagonal crystals). They can also be A 3kg lead weight used on a scuba diving weight obtained by direct reaction of their constituent elements at temperature belt. exceeding melting points of dihalides. Their solubility increases with temperature; adding more halides first decreases the solubility, but then increases due to complexation, with the maximum coordination number being 6. The complexation depends on halide ion numbers, atomic number of the alkali metal, the halide of which is added, temperature and solution ionic strength.[21] The tetrachloride is obtained upon dissolving the dioxide in hydrochloric acid; to prevent the exothermic decomposition, it is kept under concentrated sulfuric acid. The tetrabromide may not, and the tetraiodide definitely does not exist.[22] The diastatide has also been prepared.[23] The metal is not attacked by sulfuric or hydrochloric acids. It dissolves in nitric acid with the evolution of nitric oxide gas to form dissolved Pb(NO3)2.[20] It is a well-soluble solid in water; it is thus a key to receive the precipitates of halides, sulfate, chromate, carbonate, and basic carbonate Pb3(OH)2(CO3)2 salts of lead.[] |

Organolead
The best-known compounds are the two simplest plumbane derivatives: tetramethyllead (TML) and tetraethyllead (TEL). The homologs of these, as well as hexaethyldilead (HEDL), are of lesser stability. The tetralkyl derivatives contain lead(IV), where the PbC bonds are covalent. They thus resemble typical organic compounds.[24] Lead readily forms an equimolar alloy with sodium metal that reacts with alkyl halides to form organometallic compounds of lead such as tetraethyllead.[25] The PbC bond energies in TML and TEL are only 167 and 145kJ/mol; the compounds thus decompose upon heating, with first signs of TEL composition seen at 100C (210F). The pyrolysis yields of elemental lead and alkyl radicals; their interreaction causes the synthesis of HEDL.[24] TML and TEL also decompose upon sunlight or UV light.[26] In presence of chlorine, the alkyls begin to be replaced with chlorides; the R2PbCl2 in the presence of HCl (a by-product of the previous reaction) leads to the complete mineralization to give PbCl2. Reaction with bromine follows the same principle.[26]

History
Lead has been commonly used for thousands of years because it is widespread, easy to extract and easy to work with. It is highly malleable as well as easy to smelt. Metallic lead beads dating back to 6400 BCE have been found in atalhyk in modern-day Turkey.[27] In the early Bronze Age, lead was used with antimony and arsenic.[28]
World lead production peaking in the Roman [] period and the rising Industrial Revolution

The largest preindustrial producer of lead was the Roman economy, with an estimated annual output of 80,000 tonnes, which was typically won as a by-product of extensive silver smelting.[][][29] Roman mining

Lead

56 activities occurred in Central Europe, Roman Britain, the Balkans, Greece, Asia Minor and Hispania which alone accounted for 40% of world production.[] Roman lead pipes often bore the insignia of Roman emperors (see Roman lead pipe inscriptions). Lead plumbing in the Latin West may have been continued beyond the age of Theoderic the Great into the medieval period.[30] Many Roman "pigs" (ingots) of lead figure in Derbyshire lead mining history and in the history of the industry in other English centers. The Romans also used lead in molten form to secure iron pins that held together large limestone blocks in certain monumental buildings.[31] In alchemy, lead was thought to be the oldest metal and was associated with the planet Saturn. Alchemists accordingly used Saturn's symbol (the scythe, ) to refer to lead.[32] Up to the 17th century, tin was often not distinguished from lead: lead was called plumbum nigrum (literally, "black lead"), while tin was called plumbum candidum (literally, "bright lead").[33] Their inherence through history can also be seen in other languages: the word "olovo" means lead in Czech, but in Russian it ("") means tin.[34] Lead's symbol Pb is an abbreviation of its Latin name plumbum for soft metals; the English words "plumbing", "plumber", "plumb", and "plumb-bob" also derive from this Latin root.[35]

Lead ingots from Roman Britain on display at the Wells and Mendip Museum

Lead mining in the upper Mississippi River region of the US in 1865

Lead production in the US commenced as early as the late 1600s by Indians in the The Southeast Missouri Lead District, commonly called the Lead Belt, is a lead mining district in the southeastern part of Missouri. Significant among Missouri's lead mining concerns in the district was the Desloge Family and Desloge Consolidated Lead Company in Desloge, Missouri and Bonne Terre having been active in lead trading, mining and lead smelting from 1823 in Potosi to 1929.

Occurrence
Metallic lead does occur in nature, but it is rare. Lead is usually found in ore with zinc, silver and (most abundantly) copper, and is extracted together with these metals. The main lead mineral is galena (PbS), which contains 86.6% lead by weight. Other common varieties are cerussite (PbCO3) and anglesite (PbSO4).[]
Lead and zinc bearing carbonate and clastic deposits. Source: USGS

Lead

57

Ore processing
Most ores contain less than 10% lead, and ores containing as little as 3% lead can be economically exploited. Ores are crushed and concentrated by froth flotation typically to 70% or more. Sulfide ores are roasted, producing primarily lead oxide and a mixture of sulfates and silicates of lead and other metals contained in the ore.[36] Lead oxide from the roasting process is reduced in a coke-fired blast furnace to the metal.[] Additional layers separate in the process and float to the top of the metallic lead. These are slag (silicates containing 1.5% lead), matte (sulfides containing 15% lead), and speiss (arsenides of iron and copper). These wastes contain concentrations of copper, zinc, cadmium, and bismuth that can be recovered economically, as can their content of unreduced lead.[36] Metallic lead that results from the roasting and blast furnace processes still contains significant contaminants of arsenic, antimony, bismuth, zinc, copper, silver, and gold. The melt is treated in a reverberatory furnace with air, steam, and sulfur, which oxidizes the contaminants except silver, gold, and bismuth. The oxidized contaminants are removed by drossing, where they float to the top and are skimmed off.[36][] Since lead ores contain significant concentrations of silver, the smelted metal also is commonly contaminated with silver. Metallic silver as well as gold is removed and recovered economically by means of the Parkes process.[][36][] Desilvered lead is freed of bismuth according to the Betterton-Kroll process by treating it with metallic calcium and magnesium, which forms a bismuth dross that can be skimmed off.[36][] Very pure lead can be obtained by processing smelted lead electrolytically by means of the Betts process. The process uses anodes of impure lead and cathodes of pure lead in an electrolyte of silica fluoride.[36][]
Galena, lead ore

Production and recycling


Production and consumption of lead is increasing worldwide. Total annual production is about 8million tonnes; about half is produced from recycled scrap. The top lead producing countries, as of 2008, are Australia, China, USA, Peru, Canada, Mexico, Sweden, Morocco, South Africa and North Korea.[] Australia, China and the United States account for more than half of primary production.[] In 2010[37], 9.6 million tonnes of lead were produced, of which 4.1 million tonnes came from mining.[37] At current use rates, the supply of lead is estimated to run out in 42 years.[38] Environmental analyst Lester Brown has suggested lead could run out within 18 years based on an extrapolation of 2% growth per year.[] This may need to be reviewed to take account of renewed interest in recycling, and rapid progress in fuel cell technology. According to the International Resource Panel's Metal Stocks in Society report, the global per capita stock of lead in use in society is 8kg. Much of this is in more-developed countries (20150kg per capita) rather than less-developed countries (14kg per capita).[39]

Lead

58

Applications
Elemental form
Contrary to popular belief, pencil leads in wooden pencils have never been made from lead. The term comes from the Roman stylus, called the penicillus, a small brush used for painting.[40] When the pencil originated as a wrapped graphite writing tool, the particular type of graphite being used was named plumbago (lit. act for lead, or lead mockup).[41][42] Lead is used in applications where its low melting point, ductility and high density are advantageous. The low melting point makes casting of lead easy, and therefore small arms ammunition and shotgun pellets can be cast with minimal technical equipment. It is also inexpensive and denser than other common metals.[43]

Lead bricks are commonly used as radiation shielding.

Because of its high density and resistance from corrosion, lead is used for the ballast keel of sailboats.[44] Its high density allows it to counterbalance the heeling effect of wind on the sails while at the same time occupying a small volume and thus offering the least underwater resistance. For the same reason it is used in scuba diving weight belts to counteract the diver's natural buoyancy and that of his equipment.[45] It does not have the weight-to-volume ratio of many heavy metals, but its low cost increases its use in these and other applications. More than half of the US lead production (at least 1.15 million tonnes in 2000) is used for automobiles, mostly as electrodes in the leadacid battery, used extensively as a car battery.[46] Cathode (reduction) PbO2 + 4 H+ + SO2 4 + 2e PbSO + 2 H O 4 2 Anode (oxidation) Pb + SO2 [47][48] 4 PbSO + 2e 4
Roman lead water pipes with taps

Lead is used as electrodes in the process of electrolysis. It is used in solder for electronics, although this usage is being phased out by some countries to reduce the amount of environmentally hazardous waste, and in high voltage power cables as sheathing material to prevent water diffusion into insulation. Lead is one of three metals used in the Oddy test for museum materials, helping detect organic acids, aldehydes, and acidic gases. It is also used as shielding from radiation (e.g., in X-ray rooms).[49] Molten lead is used as a coolant (e.g., for lead cooled fast reactors).[50] Lead is added to brass to reduce machine tool wear. In the form of strips, or tape, lead is used for the customization of tennis rackets. Tennis rackets of the past sometimes had lead added to them by the manufacturer to increase weight.[51] It is also used to form glazing bars for stained glass or other multi-lit windows. The practice has become

Lead

59 less common, not for danger but for stylistic reasons. Lead, or sheet-lead, is used as a sound deadening layer in some areas in wall, floor and ceiling design in sound studios where levels of airborne and mechanically produced sound are targeted for reduction or virtual elimination.[52][53] It is the traditional base metal of organ pipes, mixed with varying amounts of tin to control the tone of the pipe.[54][55] Lead has many uses in the construction industry (e.g., lead sheets are used as architectural metals in roofing material, cladding, flashing, gutters and gutter joints, and on roof parapets). Detailed lead moldings are used as decorative motifs used to fix lead sheet. Lead is still widely used in statues and sculptures. Lead is often used to balance the wheels of a car; this use is being phased out in favor of other materials for environmental reasons. Owing to its half-life of 22.20 years, the radioactive isotope 210Pb is used for dating material from marine sediment cores by radiometric methods.[56][57][58]

Lead pipe in Roman baths

Compounds
Lead compounds are used as a coloring element in ceramic glazes, notably in the colors red and yellow.[59] Lead is frequently used in polyvinyl chloride (PVC) plastic, which coats electrical cords.[60][61] Lead is used in some candles to treat the wick to ensure a longer, more even burn. Because of the dangers, European and North American manufacturers use more expensive alternatives such as zinc.[62][63] Lead glass is composed of 1228% lead oxide. It changes the optical characteristics of the glass and reduces the transmission of radiation.[64] Some artists using oil-based paints continue to use lead carbonate white, citing its properties in comparison with the alternatives. Tetra-ethyl lead is used as an anti-knock additive for aviation fuel in piston-driven aircraft. Lead-based semiconductors, such as lead telluride, lead selenide and lead antimonide are finding applications in photovoltaic (solar energy) cells and infrared detectors.[] Lead, in either pure form or alloyed with tin, or antimony is the traditional material for bullets and shot in firearms use.

Multicolor lead-glazing in a Tang dynasty Chinese sancai ceramic cup dating from the 8th century CE

Punched lead cast in a Venice bridge wall fixing the hard-metal connecting bar

Lead

60

Former applications
Lead pigments were used in lead paint for white as well as yellow, orange, and red. Most uses have been discontinued due of the dangers of lead poisoning. Beginning April 22, 2010, US federal law requires that contractors performing renovation, repair, and painting projects that disturb more than six square feet of paint in homes, child care facilities, and schools built before 1978 must be certified and trained to follow specific work practices to prevent lead contamination. Lead chromate is still in industrial use. Lead carbonate (white) is the traditional pigment for the priming medium for oil painting, but it has been largely displaced by the zinc and titanium oxide pigments. It was also quickly replaced in water-based painting mediums. Lead carbonate white was used by the Japanese geisha and in the West for face-whitening make-up, which was detrimental to health.[65][66][67] Lead was the principal component of the alloy used in hot metal typesetting. It was used for plumbing (hence the name) as well as a preservative for food and drink in Ancient Rome. Until the early 1970s, lead was used for joining cast iron water pipes and used as a material for small diameter water pipes.[68] Tetraethyllead was used in leaded fuels to reduce engine knocking, but this practice has been phased out across many countries of the world in efforts to reduce toxic pollution that affected humans and the environment.[69][70][][71] Lead was used to make bullets for slings. Lead was used for shotgun pellets in the US until about 1992 when it was outlawed (for waterfowl hunting only) and replaced by non-toxic shot, primarily steel pellets. In the Netherlands, the use of lead shot for hunting and sport shooting was banned in 1993, which caused a large drop in lead emission, from 230 tonnes in 1990 to 47.5 tonnes in 1995, two years after the ban.[72] Lead was a component of the paint used on children's toys now restricted in the United States and across Europe (ROHS Directive). Lead was used in car body filler, which was used in many custom cars in the 1940s60s. Hence the term Leadsled. Lead is a superconductor with a transition temperature of 7.2K, and therefore IBM tried to make a Josephson effect computer out of a lead alloy.[73] Lead was also used in pesticides before the 1950s, when fruit orchards were treated especially against the codling moth.[74] A lead cylinder attached to a long line was used by sailors for the vital navigational task of determining water depth by heaving the lead at regular intervals. A soft tallow insert at its base allowed the nature of the sea bed to be determined, further aiding position finding.[75]

Health effects
Lead is a highly poisonous metal (regardless if inhaled or swallowed), affecting almost every organ and system in the body. The main target for lead toxicity is the nervous system, both in adults and children. Long-term exposure of adults can result in decreased performance in some tests that measure functions of the nervous system.[76] Long-term exposure to lead or its salts (especially soluble salts or the strong oxidant PbO2) can cause nephropathy, and colic-like abdominal pains. It may also cause weakness in fingers, wrists, or ankles. Lead exposure also causes small increases in blood pressure, particularly in middle-aged and older people and can cause anemia. Exposure to high lead levels can severely damage the brain and kidneys in adults or children and ultimately cause death. In pregnant women, high levels of exposure to lead may cause miscarriage. Chronic, high-level exposure have shown to reduce fertility in males.[77] Lead also damages nervous connections (especially in young children) and cause blood and brain disorders. Lead poisoning typically results from ingestion of food or water contaminated with lead; but may also occur after accidental ingestion of contaminated soil, dust, or lead-based paint.[78] It is rapidly absorbed into the bloodstream and is believed to have adverse effects on the central nervous system, the cardiovascular system, kidneys, and the immune system.[79] The component limit of lead (1.0 g/g) is a test benchmark for pharmaceuticals, representing the maximum daily intake an individual should have. However, even at this low level, a prolonged intake can be hazardous to human beings.[80][81] The treatment for lead poisoning consists of dimercaprol and succimer.[82]

Lead

61

NFPA 704

"Fire diamond" for lead granules

The concern about lead's role in cognitive deficits in children has brought about widespread reduction in its use (lead exposure has been linked to learning disabilities).[83] Most cases of adult elevated blood lead levels are workplace-related.[84] High blood levels are associated with delayed puberty in girls.[85] Lead has been shown many times to permanently reduce the cognitive capacity of children at extremely low levels of exposure.[86] During the 20th century, the use of lead in paint pigments was sharply reduced because of the danger of lead poisoning, especially to children.[87][88] By the mid-1980s, a significant shift in lead end-use patterns had taken place. Much of this shift was a result of the U.S. lead consumers' compliance with environmental regulations that significantly reduced or eliminated the use of lead in non-battery products, including gasoline, paints, solders, and water systems. Lead use is being further curtailed by the European Union's RoHS directive.[89] Lead may still be found in harmful quantities in stoneware,[90] vinyl[] (such as that used for tubing and the insulation of electrical cords), and Chinese brass. Older houses may still contain substantial amounts of lead paint.[] White lead paint has been withdrawn from sale in industrialized countries, but the yellow lead chromate is still in use. Old paint should not be stripped by sanding, as this produces inhalable dust.[91] Lead salts used in pottery glazes have on occasion caused poisoning, when acidic drinks, such as fruit juices, have leached lead ions out of the glaze.[92] It has been suggested that what was known as "Devon colic" arose from the use of lead-lined presses to extract apple juice in the manufacture of cider. Lead is considered to be particularly harmful for women's ability to reproduce. Lead(II) acetate (also known as sugar of lead) was used in the Roman Empire as a sweetener for wine, and some consider this a plausible explanation for the dementia of many Roman emperors, and, that chronic lead poisoning contributed to the empire's gradual decline. (see Decline of the Roman Empire#Lead poisoning)[93]

Biochemistry of poisoning
In the human body, lead inhibits porphobilinogen synthase and ferrochelatase, preventing both porphobilinogen formation and the incorporation of iron into protoporphyrin IX, the final step in heme synthesis. This causes ineffective heme synthesis and subsequent microcytic anemia.[94] At lower levels, it acts as a calcium analog, interfering with ion channels during nerve conduction. This is one of the mechanisms by which it interferes with cognition. Acute lead poisoning is treated using disodium calcium edetate: the calcium chelate of the disodium salt of ethylene-diamine-tetracetic acid (EDTA). This chelating agent has a greater affinity for lead than for calcium and so the lead chelate is formed by exchange. This is then excreted in the urine leaving behind harmless calcium.[95] According to the Agency for Toxic Substance and Disease Registry, a small amount of ingested lead (1%) will store itself in bones, and the rest will be excreted by an adult through urine and feces within a few weeks of exposure. However, only about 32% of lead will be excreted by a child.[96] Exposure to lead and lead chemicals can occur through inhalation, ingestion and dermal contact. Most exposure occurs through ingestion or inhalation; in the U.S. the skin exposure is unlikely as leaded gasoline additives are no longer used. Lead exposure is a global issue as lead mining and lead smelting are common in many countries. Most countries have stopped using lead-containing gasoline by 2007.[] Lead exposure mostly occurs through ingestion. Lead paint is the major source of lead exposure for children. As lead paint deteriorates, it peels, is pulverized into dust and then enters the body through hand-to-mouth contact or through contaminated food, water or alcohol.

Lead Ingesting certain home remedy medicines may also expose people to lead or lead compounds.[] Lead can be ingested through fruits and vegetables contaminated by high levels of lead in the soils they were grown in. Soil is contaminated through particulate accumulation from lead in pipes, lead paint and residual emissions from leaded gasoline that was used before the Environment Protection Agency issue the regulation around 1980.[97] The use of lead for water pipes is problematic in areas with soft or (and) acidic water. Hard water forms insoluble layers in the pipes while soft and acidic water dissolves the lead pipes.[98] Inhalation is the second major pathway of exposure, especially for workers in lead-related occupations. Almost all inhaled lead is absorbed into the body, the rate is 2070% for ingested lead; children absorb more than adults.[] Dermal exposure may be significant for a narrow category of people working with organic lead compounds, but is of little concern for general population. The rate of skin absorption is also low for inorganic lead.[]

62

References
[1] [4] [5] [6] [7] [8] Polyanskiy 1986, p.18. Polyanskiy 1986, p.14. Lide 2004, p.12-220. Lide 2004, p.4-13. Lide 2004, p.12-219. Lide 2004, p.12-35.

[9] Lide 2004, p.12-37. [10] Polyanskiy 1986, pp.1415. [11] Polyanskiy 1986, p.20. [13] Polyanskiy 1986, p.16. [14] Polyanskiy 1986, p.19. [15] Polyanskiy 1986, p.21. [16] Polyanskiy 1986, p.22. [17] Polyanskiy 1986, p.28. [20] Polyanskiy 1986, p.32. [21] Polyanskiy 1986, p.33. [22] Polyanskiy 1986, p.34. [24] Polyanskiy 1986, p.43. [26] Polyanskiy 1986, p.44. [29] see 1170f. [33] Polyanskiy 1986, p.8. [36] Charles A. Sutherland, Edward F. Milner, Robert C. Kerby, Herbert Teindl, Albert Melin Hermann M. Bolt "Lead" in Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH, Weinheim. [37] "Mine Production: 4,117,000 tonnes; Metal Production: 9,604,000 tonnes; Metal Usage: 9,569,000 tonnes" from (See also their definitions of terms (http:/ / www. ilzsg. org/ static/ generaldef. aspx).) [46] Getting the Lead Out: Impacts of and Alternatives For Automotive Lead Uses (http:/ / www. ecocenter. org/ sites/ default/ files/ publications/ docs/ GettingLeadOut. pdf), A report by Environmental Defense, Ecology Center, Clean Car Campaign (July 2003) [56] http:/ / www. nrcresearchpress. com/ doi/ abs/ 10. 1139/ f83-069 [80] Heavy Metals Testing By Usp (http:/ / www. caspharma. com/ Heavy-Metals-Testing-USP/ ). Caspharma.com. Retrieved on 2012-01-23. [81] pharmaceutical Britannica Online Encyclopedia (http:/ / www. britannica. com/ EBchecked/ topic/ 455151/ pharmaceutical). Britannica.com. Retrieved on 2012-01-23.

Lead

63

Bibliography
Lide, D. R., ed. (2004). CRC Handbook of Chemistry and Physics (84th ed.). Boca Raton (FL): CRC Press. ISBN978-0-8493-0484-2. Polyanskiy, N. G. (1986). Fillipova, N. A, ed. : [Analytical Chemistry of the Elements: Lead] (in Russian). Nauka.

Further reading
Keisch, B.; Feller, R. L.; Levine, A. S.; Edwards, R. R. (1967). "Dating and Authenticating Works of Art by Measurement of Natural Alpha Emitters". Science 155 (3767): 12381242. Bibcode: 1967Sci...155.1238K (http:/ /adsabs.harvard.edu/abs/1967Sci...155.1238K). doi: 10.1126/science.155.3767.1238 (http://dx.doi.org/ 10.1126/science.155.3767.1238). PMID 17847535 (http://www.ncbi.nlm.nih.gov/pubmed/17847535). Keisch, B (1968). "Dating Works of Art Through their Natural Radioactivity: Improvements and Applications". Science 160 (3826): 413415. Bibcode: 1968Sci...160..413K (http://adsabs.harvard.edu/abs/1968Sci...160.. 413K). doi: 10.1126/science.160.3826.413 (http://dx.doi.org/10.1126/science.160.3826.413). PMID 17740234 (http://www.ncbi.nlm.nih.gov/pubmed/17740234). Keisch, B (1968). "Discriminating Radioactivity Measurements of Lead: New Tool for Authentication". Curator 11 (1): 4152. doi: 10.1111/j.2151-6952.1968.tb00884.x (http://dx.doi.org/10.1111/j.2151-6952.1968. tb00884.x). Casas, Jose S.; Sordo, Jose, eds. (2006). Lead Chemistry, Analytical Aspects. Environmental Impacts and Health Effects (http://www.google.com/books?id=D9nYWCv_FE4C&printsec=frontcover). Elsevier. ISBN0-444-52945-4.

External links
Lead (http://www.dmoz.org/Science/Chemistry/Elements/Lead//) at the Open Directory Project Chemistry in its element podcast (http://www.rsc.org/chemistryworld/podcast/element.asp) (MP3) from the Royal Society of Chemistry's Chemistry World: Lead (http://www.rsc.org/images/ CIIE_lead_48kbps_tcm18-126010.mp3) Lead (http://www.periodicvideos.com/videos/082.htm) at The Periodic Table of Videos (University of Nottingham) Lead-Free Wheels (http://www.leadfreewheels.org/) National Lead Free Wheel Weight Initiative| Waste Minimization|Wastes|US EPA (http://www.epa.gov/waste/ hazard/wastemin/nlfwwi.htm) CDC - NIOSH Pocket Guide to Chemical Hazards - Lead (http://www.cdc.gov/niosh/npg/npgd0368.html)

Zinc

64

Zinc
Zinc Zn 30

copper zinc gallium

Zn
Cd Zinc in the periodic table Appearance silver-gray

General properties Name, symbol, number Pronunciation Element category Group, period, block Standard atomic weight zinc, Zn, 30 /zk/ ZINGK transition metal alternatively considered a post-transition metal 12, 4, d 65.38(2)

Zinc

65
Electron configuration

[Ar] 3d10 4s2 2, 8, 18, 2

History Discovery First isolation Indian metallurgists (before 1000 BC) Andreas Sigismund Marggraf (1746)

Recognized as a unique metal by Rasaratna Samuccaya (800) Physical properties Phase Density (near r.t.) Liquid density at m.p. Meltingpoint Boilingpoint Heatoffusion Heat of vaporization Molar heat capacity solid 7.14 gcm3 6.57 gcm3 692.68K, 419.53C, 787.15F 1180K, 907C, 1665F 7.32 kJmol1 123.6 kJmol1 25.470 Jmol1K1 Vapor pressure P (Pa) 1 10 100 1 k 10 k 100 k

at T (K) 610 670 750 852 990 1179 Atomic properties Oxidation states Electronegativity Ionization energies (more) +2, +1, 0 (amphoteric oxide) 1.65 (Pauling scale) 1st: 906.4 kJmol1 2nd: 1733.3 kJmol1 3rd: 3833 kJmol1 Atomic radius Covalent radius Van der Waals radius 134 pm 1224 pm 139 pm

Zinc

66
Miscellanea Crystal structure hexagonal close-packed

Magnetic ordering Electrical resistivity Thermal conductivity Thermal expansion Speed of sound (thin rod) Young's modulus Shear modulus Bulk modulus Poisson ratio Mohs hardness Brinell hardness CAS registry number

diamagnetic (20C) 59.0 nm 116Wm1K1 (25 C) 30.2 mm1K1 (r.t.) (rolled) 3850ms1 108 GPa 43 GPa 70 GPa 0.25 2.5 412 MPa 7440-66-6 Most stable isotopes Main article: Isotopes of zinc

iso
64 65

NA

half-life

DM DE (MeV) 1.096 1.3519 1.1155

DP
64 65

Zn 48.6% >2.31018 y ++ Zn syn 243.8 d

Ni

Cu -

66 67 68 69

Zn 27.9% Zn 4.1%

66 67 68

Zn is stable with 36 neutrons Zn is stable with 37 neutrons Zn is stable with 38 neutrons 0.906 0.906 0.998 2.82 2.82 0.458
69 69 70 71 71 72

Zn 18.8% Zn Zn syn syn

56 min 13.76 h

Ga Ga Ge Ga Ga Ga

69m 70 71

Zn Zn Zn

0.6% >1.31016 y syn syn syn 2.4 min 3.97 d 46.5 h

71m 72

Zn

Zinc, in commerce also spelter, is a metallic chemical element; it has the symbol Zn and atomic number 30. It is the first element of group 12 of the periodic table. Zinc is, in some respects, chemically similar to magnesium, because its ion is of similar size and its only common oxidation state is +2. Zinc is the 24th most abundant element in the Earth's crust and has five stable isotopes. The most common zinc ore is sphalerite (zinc blende), a zinc sulfide

Zinc mineral. The largest mineable amounts are found in Australia, Asia, and the United States. Zinc production includes froth flotation of the ore, roasting, and final extraction using electricity (electrowinning). Brass, which is an alloy of copper and zinc, has been used since at least the 10thcenturyBC. Zinc metal was not produced in large scale until the 12th century in India, while the metal was unknown to Europe until the end of the 16th century. The mines of Rajasthan have given definite evidence of zinc production going back to 6th Century BC.[1] To date the oldest evidence of pure zinc comes from Zawar, Rajasthan as early as 9th century AD, when distilation process was employed to make pure zinc.[2]Alchemists burned zinc in air to form what they called "philosopher's wool" or "white snow." The element was probably named by the alchemist Paracelsus after the German word Zinke. German chemist Andreas Sigismund Marggraf is normally given credit for discovering pure metallic zinc in 1746. Work by Luigi Galvani and Alessandro Volta uncovered the electrochemical properties of zinc by 1800. Corrosion-resistant zinc plating of iron (hot-dip galvanizing) is the major application for zinc. Other applications are in batteries, small non-structural castings, and alloys, such as brass. A variety of zinc compounds are commonly used, such as zinc carbonate and zinc gluconate (as dietary supplements), zinc chloride (in deodorants), zinc pyrithione (anti-dandruff shampoos), zinc sulfide (in luminescent paints), and zinc methyl or zinc diethyl in the organic laboratory. Zinc is an essential mineral of "exceptional biologic and public health importance".[] Zinc deficiency affects about two billion people in the developing world and is associated with many diseases.[] In children it causes growth retardation, delayed sexual maturation, infection susceptibility, and diarrhea, contributing to the death of about 800,000 children worldwide per year.[] Enzymes with a zinc atom in the reactive center are widespread in biochemistry, such as alcohol dehydrogenase in humans.[3] Consumption of excess zinc can cause ataxia, lethargy and copper deficiency.

67

Characteristics
Physical properties
Zinc, also referred to in nonscientific contexts as spelter,[4] is a bluish-white, lustrous, diamagnetic metal,[] though most common commercial grades of the metal have a dull finish.[] It is somewhat less dense than iron and has a hexagonal crystal structure.[] The metal is hard and brittle at most temperatures but becomes malleable between 100 and 150C.[][] Above 210C, the metal becomes brittle again and can be pulverized by beating.[5] Zinc is a fair conductor of electricity.[] For a metal, zinc has relatively low melting (419.5C, 787.1F) and boiling points (907C).[] Its melting point is the lowest of all the transition metals aside from mercury and cadmium.[] Many alloys contain zinc, including brass, an alloy of copper and zinc. Other metals long known to form binary alloys with zinc are aluminium, antimony, bismuth, gold, iron, lead, mercury, silver, tin, magnesium, cobalt, nickel, tellurium and sodium.[6] While neither zinc nor zirconium are ferromagnetic, their alloy ZrZn [] 2 exhibits ferromagnetism below 35K.

Zinc

68

Occurrence
Zinc makes up about 75ppm(0.0075%) of the Earth's crust, making it the 24th most abundant element. Soil contains 5770ppm of zinc with an average of 64ppm. Seawater has only 30ppb zinc and the atmosphere contains 0.14g/m3.[] The element is normally found in association with other base metals such as copper and lead in ores.[7] Zinc is a chalcophile, meaning the element has a low affinity for oxides and prefers to bond with sulfides. Chalcophiles formed as the crust solidified under the reducing conditions of the early Earth's atmosphere.[] Sphalerite, which is a form of zinc sulfide, is the most heavily mined zinc-containing ore because its concentrate contains 6062% zinc.[7] Other minerals from which zinc is extracted include smithsonite (zinc carbonate), hemimorphite (zinc silicate), wurtzite (another zinc sulfide), and sometimes hydrozincite (basic zinc carbonate).[] With the exception of wurtzite, all these other minerals were formed as a result of weathering processes on the primordial

Sphalerite (ZnS)

zinc sulfides.[] Identified world zinc resources total about 1.9 billion tonnes.[] Large deposits are in Australia, Canada and the United States with the largest reserves in Iran.[][8][9] At the current rate of consumption, these reserves are estimated to be depleted sometime between 2027 and 2055.[10][11] About 346 million tonnes have been extracted throughout history to 2002, and one estimate found that about 109 million tonnes of that remains in use.[12]

Isotopes
Five isotopes of zinc occur in nature. 64Zn is the most abundant isotope (48.63% natural abundance).[] This isotope has such a long half-life, at 4.31018a,[13] that its radioactivity can be ignored.[] Similarly, 70 Zn (0.6%), with a half-life of 1.31016a is not usually considered to be radioactive. The other isotopes found in nature are 66 Zn (28%), 67 Zn (4%) and 68 Zn (19%). Several dozen radioisotopes have been characterized. 65 Zn, which has a half-life of 243.66days, is the most long-lived radioisotope, followed by 72 Zn with a half-life of 46.5hours.[] Zinc has 10 nuclear isomers. 69mZn has the longest half-life, 13.76 h.[] The superscript m indicates a metastable isotope. The nucleus of a metastable isotope is in an excited state and will return to the ground state by emitting a photon in the form of a gamma ray. 61 Zn has three excited states and 73 Zn has two.[14] The isotopes 65 Zn, 71 Zn, 77 Zn and 78 Zn each have only one excited state.[] The most common decay mode of a radioisotope of zinc with a mass number lower than 66 is electron capture. The decay product resulting from electron capture is an isotope of copper.[]
n 30Zn + e n 29Cu

Zinc The most common decay mode of a radioisotope of zinc with mass number higher than 66 is beta decay (), which produces an isotope of gallium.[]
n 30Zn n 31Ga + e + e

69

Compounds and chemistry


Reactivity
Zinc has an electron configuration of [Ar]3d104s2 and is a member of the group 12 of the periodic table. It is a moderately reactive metal and strong reducing agent.[] The surface of the pure metal tarnishes quickly, eventually forming a protective passivating layer of the basic zinc carbonate, Zn 5(OH) 6(CO ) 3 [15] 2, by reaction with atmospheric carbon dioxide. This layer helps prevent further reaction with air and water. Zinc burns in air with a bright bluish-green flame, giving off fumes of zinc oxide.[] Zinc reacts readily with acids, alkalis and other non-metals.[16] Extremely pure zinc reacts only slowly at room temperature with acids.[] Strong acids, such as hydrochloric or sulfuric acid, can remove the passivating layer and subsequent reaction with water releases hydrogen gas.[] The chemistry of zinc is dominated by the +2 oxidation state. When compounds in this oxidation state are formed the outer shell s electrons are lost, which yields a bare zinc ion with the electronic configuration [Ar]3d10.[17] In aqueous solution an octahedral complex, [Zn(H 2O) ]2+ 6 is the predominant species.[18] The volatilization of zinc in combination with zinc chloride at temperatures above 285C indicates the formation of Zn 2Cl [] 2, a zinc compound with a +1 oxidation state. No compounds of zinc in oxidation states other than +1 or +2 are known.[19] Calculations indicate that a zinc compound with the oxidation state of +4 is unlikely to exist.[20] Zinc chemistry is similar to the chemistry of the late first-row transition metals nickel and copper, though it has a filled d-shell, so its compounds are diamagnetic and mostly colorless.[] The ionic radii of zinc and magnesium happen to be nearly identical. Because of this some of their salts have the same crystal structure[21] and in circumstances where ionic radius is a determining factor zinc and magnesium chemistries have much in common.[] Otherwise there is little similarity. Zinc tends to form bonds with a greater degree of covalency and it forms much more stable complexes with N- and S- donors.[] Complexes of zinc are mostly 4- or 6- coordinate although 5-coordinate complexes are known.[] See also Clemmensen reduction.

Zinc(I) compounds
Zinc(I) compounds are rare, and requires bulky ligands to stabilize the low oxidation state. Most zinc(I) compounds contains formally the [Zn2]2+ core, which is analogous to the [Hg2]2+ dimeric cation present in mercury(I) compounds. The diamagnetic nature of the ion confirms its dimeric structure. The first zinc(I) compound containing the ZnZn bond, (5-C5Me5)2Zn2, is also the first dimetallocene. The [Zn2]2+ ion rapidly disproportionates into zinc metal and zinc(II), and has only been obtained as a yellow glass formed by cooling a solution of metallic zinc in molten ZnCl2.[22]

Zinc

70

Zinc (II) compounds


Binary compounds of zinc are known for most of the metalloids and all the nonmetals except the noble gases. The oxide ZnO is a white powder that is nearly insoluble in neutral aqueous solutions, but is amphoteric, dissolving in both strong basic and acidic solutions.[] The other chalcogenides (ZnS, ZnSe, and ZnTe) have varied applications in electronics and optics.[23] Pnictogenides (Zn 3N 2, Zn 3P 2, Zn 3As 2 and Zn 3Sb [24][25] 2), the peroxide (ZnO 2), the hydride (ZnH 2), and the carbide (ZnC [26] 2) are also known. Of the four halides, ZnF 2 has the most ionic character, whereas the others (ZnCl

Zinc acetate

Zinc chloride
2, 2,

ZnBr and ZnI [] 2) have relatively low melting points and are considered to have more covalent character. In weak basic solutions containing Zn2+ ions, the hydroxide Zn(OH) 2 forms as a white precipitate. In stronger alkaline solutions, this hydroxide is dissolved to form zincates ([Zn(OH)4]2 ).[] The nitrate Zn(NO3) 2, chlorate Zn(ClO ) 3 2, sulfate ZnSO 4, phosphate Zn 3(PO ) 4 2, molybdate ZnMoO 4, cyanide Zn(CN) 2, arsenite Zn(AsO ) 2 2, arsenate Zn(AsO ) 4 28H 2O and the chromate ZnCrO [27][] 4 (one of the few colored zinc compounds) are a few examples of other common inorganic compounds of zinc. One of the simplest examples of an organic compound of zinc is the acetate (Zn(O 2CCH ) 3 2). Organozinc compounds are those that contain zinccarbon covalent bonds. Diethylzinc ((C 2H ) 5 2Zn) is a reagent in synthetic chemistry. It was first reported in 1848 from the reaction of zinc and ethyl iodide, and was the first compound known to contain a metalcarbon sigma bond.[28]

Zinc

71

History
Ancient use
Various isolated examples of the use of impure zinc in ancient times have been discovered. Zinc ores were used to make the zinccopper alloy brass many centuries prior to the discovery of zinc as a separate element. Judean brass from the 14th to 10th centuriesBC contains 23% zinc.[] Knowledge of how to produce brass spread to Ancient Greece by the 7thcenturyBC but few varieties were made.[29] Ornaments made of alloys that contain 8090% zinc with lead, iron, antimony, and other metals making up the remainder, have been found that are 2500 years old.[7] A possibly prehistoric statuette containing 87.5% zinc was found in a Dacian archaeological site.[] The manufacture of brass was known to the Romans by about 30BC.[] They made brass by heating powdered calamine (zinc silicate or carbonate), charcoal and copper together in a crucible.[] The resulting calamine brass was then either cast or hammered into shape and was used in weaponry.[30] Some coins struck by Romans in the Christian era are made of what is probably calamine brass.[]

Late Roman brass bucket the Hemmoorer Eimer from Warstade, Germany, second to third century AD

Strabo, in a passage taken from an earlier writer of the 4th century BC,Wikipedia:Avoid weasel words mentions "drops of false silver", which when mixed with copper make brass. This may refer to small quantities of zinc by-product of smelting sulfide ores.[31] Zinc in such remnants in melting ovens was usually discarded, as it was thought to be worthless.[] The Berne zinc tablet is a votive plaque dating to Roman Gaul made of an alloy that is mostly zinc.[32] The Charaka Samhita, thought to have been written in 500 BC or before,Wikipedia:Disputed statement mentions a metal which, when oxidized, produces pushpanjan, thought to be zinc oxide.[33] Zinc mines at Zawar, near Udaipur in India, have been active since the Mauryan period. The smelting of metallic zinc here however appears to have begun around the 12th century AD.[34][32] One estimate is that this location produced an estimated million tonnes of metallic zinc and zinc oxide from the 12th to 16th centuries.[] Another estimate gives a total production of 60,000 tonnes of metallic zinc over this period.[34] The Rasaratna Samuccaya, written in approximately the 13th century AD, mentions two types of zinc-containing ores; one used for metal extraction and another used for medicinal purposes.[32]

Early studies and naming


Zinc was distinctly recognized as a metal under the designation of Yasada or Jasada in the medical Lexicon ascribed to the Hindu king Madanapala and written about the year 1374.[35] Smelting and extraction of impure zinc by reducing calamine with wool and other organic substances was accomplished in the 13th century in India.[][] The Chinese did not learn of the technique until the 17th century.[] Alchemists burned zinc metal in air and collected the resulting zinc oxide on a condenser. Some alchemists called this zinc oxide lana philosophica, Latin for "philosopher's wool", because it collected in wooly tufts while others thought it looked like white snow and named it nix album.[36] The name of the metal was probably first documented by Paracelsus, a Swiss-born German alchemist, who referred to the metal as "zincum"

Various alchemical symbols attributed to the element zinc

or "zinken" in his book Liber Mineralium II, in the 16th century.[][37] The word is probably derived from the German zinke, and supposedly meant "tooth-like, pointed or jagged" (metallic zinc crystals have a needle-like

Zinc appearance).[38] Zink could also imply "tin-like" because of its relation to German zinn meaning tin.[39] Yet another possibility is that the word is derived from the Persian word seng meaning stone.[40] The metal was also called Indian tin, tutanego, calamine, and spinter.[7] German metallurgist Andreas Libavius received a quantity of what he called "calay" of Malabar from a cargo ship captured from the Portuguese in 1596.[41] Libavius described the properties of the sample, which may have been zinc. Zinc was regularly imported to Europe from the Orient in the 17th and early 18th centuries,[] but was at times very expensive.[42]

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Isolation
The isolation of metallic zinc in the West may have been achieved independently by several people. Postlewayt's Universal Dictionary, a contemporary source giving technological information in Europe, did not mention zinc before 1751 but the element was studied before then.[32][43] Flemish metallurgist P.M. de Respour reported that he extracted metallic zinc from zinc oxide in 1668.[] By the start of the 18th century, tienne Franois Geoffroy described how zinc oxide condenses as yellow crystals on bars of iron placed above zinc ore being smelted.[] In Britain, John Lane is said to have carried out experiments to smelt zinc, probably at Landore, prior to his bankruptcy in 1726.[44] In 1738, William Champion patented in Great Britain a process to extract zinc from calamine in a vertical retort style smelter.[45] His technology was somewhat similar to that used at Zawar zinc mines in Rajasthan but there is no evidence that he visited the Orient.[46] Champion's process was used through 1851.[]
Andreas Sigismund Marggraf is given credit for first isolating pure zinc

German chemist Andreas Marggraf normally gets credit for discovering pure metallic zinc even though Swedish chemist Anton von Swab distilled zinc from calamine four years before.[] In his 1746 experiment, Marggraf heated a mixture of calamine and charcoal in a closed vessel without copper to obtain a metal.[] This procedure became commercially practical by 1752.[47]

Later work
William Champion's brother, John, patented a process in 1758 for calcining zinc sulfide into an oxide usable in the retort process.[7] Prior to this only calamine could be used to produce zinc. In 1798, Johann Christian Ruberg improved on the smelting process by building the first horizontal retort smelter.[48] Jean-Jacques Daniel Dony built a different kind of horizontal zinc smelter in Belgium, which processed even more zinc.[] Italian doctor Luigi Galvani discovered in 1780 that connecting the spinal cord of a freshly dissected frog to an iron rail attached by a brass hook caused the frog's leg to twitch.[] He incorrectly thought he had discovered an ability of nerves and muscles to create electricity and called the effect "animal electricity".[] The galvanic cell and the process of galvanization were both named for Luigi Galvani and these discoveries paved the way for electrical batteries, galvanization and cathodic protection.[]

Galvanization was named after Luigi Galvani.

Zinc Galvani's friend, Alessandro Volta, continued researching this effect and invented the Voltaic pile in 1800.[] The basic unit of Volta's pile was a simplified galvanic cell, which is made of a plate of copper and a plate of zinc connected to each other externally and separated by an electrolyte. These were stacked in series to make the Voltaic cell, which in turn produced electricity by directing electrons from the zinc to the copper and allowing the zinc to corrode.[] The non-magnetic character of zinc and its lack of color in solution delayed discovery of its importance to biochemistry and nutrition.[] This changed in 1940 when carbonic anhydrase, an enzyme that scrubs carbon dioxide from blood, was shown to have zinc in its active site.[] The digestive enzyme carboxypeptidase became the second known zinc-containing enzyme in 1955.[]

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Production
Mining and processing Top zinc output countries 2010[]
Rank 1 2 3 4 5 6 Country China Peru Australia India United States Canada Tonnes 3,500,000 1,520,000 1,450,000 750,000 720,000 670,000

Zinc is the fourth most common metal in use, trailing only iron, aluminium, and copper with an annual production of about 12 million tonnes.[] The world's largest zinc producer is Nyrstar, a merger of the Australian OZ Minerals and the Belgian Umicore.[49] About 70% of the world's zinc originates from mining, while the [] remaining 30% comes from recycling Percentage of zinc output in 2006 by countries [50] secondary zinc. Commercially pure zinc is known as Special High Grade, often abbreviated SHG, and is 99.995% pure.[51] Worldwide, 95% of the zinc is mined from sulfidic ore deposits, in which sphalerite ZnS is nearly always mixed with the sulfides of copper, lead and iron.[] There are zinc mines throughout the world, with the main mining areas being China, Australia and Peru. China produced 29% of the global zinc output in 2010.[] Zinc metal is produced using extractive metallurgy.[] After grinding the ore, froth flotation, which selectively separates minerals from gangue by taking advantage of differences in their hydrophobicity, is used to get an ore concentrate.[] A final concentration of zinc of about 50% is reached by this process with the remainder of the concentrate being sulfur (32%), iron (13%), and SiO [] 2 (5%). Roasting converts the zinc sulfide concentrate produced during processing to zinc oxide:[]

Zinc 2 ZnS + 3 O 2 2 ZnO + 2 SO


2

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The sulfur dioxide is used for the production of sulfuric acid, which is necessary for the leaching process. If deposits of zinc carbonate, zinc silicate or zinc spinel, like the Skorpion Deposit in Namibia are used for zinc production the roasting can be omitted.[] For further processing two basic methods are used: pyrometallurgy or electrowinning. Pyrometallurgy processing reduces zinc oxide with carbon or carbon monoxide at 950 C (1,740F) into the metal, which is distilled as zinc vapor.[52] The zinc vapor is collected in a condenser.[] The below set of equations demonstrate this process:[] 2 ZnO + C 2 Zn + CO
2

ZnO + CO Zn + CO
2

Electrowinning processing leaches zinc from the ore concentrate by sulfuric acid:[53] ZnO + H 2SO 4 ZnSO 4+ H 2O After this step electrolysis is used to produce zinc metal.[] 2 ZnSO 4+ 2 H 2O 2 Zn + 2 H 2SO 4+ O
2

The sulfuric acid regenerated is recycled to the leaching step.

Environmental impact
The production for sulfidic zinc ores produces large amounts of sulfur dioxide and cadmium vapor. Smelter slag and other residues of process also contain significant amounts of heavy metals. About 1.1 million tonnes of metallic zinc and 130 thousand tonnes of lead were mined and smelted in the Belgian towns of La Calamine and Plombires between 1806 and 1882.[] The dumps of the past mining operations leach significant amounts of zinc and cadmium, and, as a result, the sediments of the Geul River contain significant amounts of heavy metals.[] About two thousand years ago emissions of zinc from mining and smelting totaled 10 thousand tonnes a year. After increasing 10-fold from 1850, zinc emissions peaked at 3.4 million tonnes per year in the 1980s and declined to 2.7 million tonnes in the 1990s, although a 2005 study of the Arctic troposphere found that the concentrations there did not reflect the decline. Anthropogenic and natural emissions occur at a ratio of 20to1.[] Levels of zinc in rivers flowing through industrial or mining areas can be as high as 20ppm.[] Effective sewage treatment greatly reduces this; treatment along the Rhine, for example, has decreased zinc levels to 50ppb.[] Concentrations of zinc as low as 2ppm adversely affects the amount of oxygen that fish can carry in their blood.[54]

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Historically responsible for high heavy metal levels in the Derwent River,[55] the zinc works at Lutana is the largest exporter in Tasmania, generating 2.5% of the state's GDP, and producing over 250 thousand tonnes of zinc per year.[56] Soils contaminated with zinc through the mining of zinc-containing ores, refining, or where zinc-containing sludge is used as fertilizer, can contain several grams of zinc per kilogram of dry soil. Levels of zinc in excess of 500ppm in soil interfere with the ability of plants to absorb other essential metals, such as iron and manganese. Zinc levels of 2000ppm to 180,000ppm (18%) have been recorded in some soil samples.[]

Applications
Major applications of zinc include (numbers are given for the US)[] 1. 2. 3. 4. Galvanizing (55%) Alloys (21%) Brass and bronze (16%) Miscellaneous (8%)

Anti-corrosion and batteries


The metal is most commonly used as an anti-corrosion agent.[] Galvanization, which is the coating of iron or steel to protect the metals against corrosion, is the most familiar form of using zinc in this way. In 2009 in the United States, 55% or 893 thousand tonnes of the zinc metal was used for galvanization.[] Zinc is more reactive than iron or steel and thus will attract almost all local oxidation until it completely corrodes away.[] A protective surface layer of oxide and carbonate (Zn 5(OH) Hot-dip handrail galvanized crystalline surface 6(CO 3) [] 2) forms as the zinc corrodes. This protection lasts even after the zinc layer is scratched but degrades through time as the zinc corrodes away.[] The zinc is applied electrochemically or as molten zinc by hot-dip galvanizing or spraying. Galvanization is used on chain-link fencing, guard rails, suspension bridges, lightposts, metal roofs, heat exchangers, and car bodies.[] The relative reactivity of zinc and its ability to attract oxidation to itself makes it an efficient sacrificial anode in cathodic protection (CP). For example, cathodic protection of a buried pipeline can be achieved by connecting anodes made from zinc to the pipe.[] Zinc acts as the anode (negative terminus) by slowly corroding away as it passes electric current to the steel pipeline.[][57] Zinc is also used to cathodically protect metals that are exposed to sea water from corrosion.[58] A zinc disc attached to a ship's iron rudder will slowly corrode while the rudder stays unattacked.[] Other similar uses include a plug of zinc attached to a propeller or the metal protective guard for the keel of the ship. With a standard electrode potential (SEP) of 0.76 volts, zinc is used as an anode material for batteries. (More reactive lithium (SEP 3.04 V) is used for anodes in lithium batteries ). Powdered zinc is used in this way in alkaline batteries and sheets of zinc metal form the cases for and act as anodes in zinccarbon batteries.[59][60] Zinc is used as the anode or fuel of the zinc-air battery/fuel cell.[61][62][63]

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Alloys
A widely used alloy which contains zinc is brass, in which copper is alloyed with anywhere from 3% to 45% zinc, depending upon the type of brass.[] Brass is generally more ductile and stronger than copper and has superior corrosion resistance.[] These properties make it useful in communication equipment, hardware, musical instruments, and water valves.[] Other widely used alloys that contain zinc include nickel silver, typewriter metal, soft and aluminium solder, and commercial bronze.[] Zinc is also used in contemporary pipe organs as a substitute for the traditional lead/tin alloy in pipes.[64] Alloys of 8588% zinc, 410% copper, and 28% aluminium find limited use in certain types of machine bearings. Zinc is the primary metal used in making American one cent coins since 1982.[] The zinc core is coated with a thin layer of copper to give the impression of a copper coin. In 1994, 33,200 tonnes (36,600 short tons) of zinc were used to produce 13.6 billion pennies in the United States.[]

Cast brass microstructure at magnification 400x

Alloys of primarily zinc with small amounts of copper, aluminium, and magnesium are useful in die casting as well as spin casting, especially in the automotive, electrical, and hardware industries.[] These alloys are marketed under the name Zamak.[65] An example of this is zinc aluminium. The low melting point together with the low viscosity of the alloy makes the production of small and intricate shapes possible. The low working temperature leads to rapid cooling of the cast products and therefore fast assembly is possible.[][66] Another alloy, marketed under the brand name Prestal, contains 78% zinc and 22% aluminium and is reported to be nearly as strong as steel but as malleable as plastic.[][67] This superplasticity of the alloy allows it to be molded using die casts made of ceramics and cement.[] Similar alloys with the addition of a small amount of lead can be cold-rolled into sheets. An alloy of 96% zinc and 4% aluminium is used to make stamping dies for low production run applications for which ferrous metal dies would be too expensive.[36] In building facades, roofs or other applications in which zinc is used as sheet metal and for methods such as deep drawing, roll forming or bending, zinc alloys with titanium and copper are used.[] Unalloyed zinc is too brittle for these kinds of manufacturing processes.[] As a dense, inexpensive, easily worked material, zinc is used as a lead replacement. In the wake of lead concerns, zinc appears in weights for various applications ranging from fishing[68] to tire balances and flywheels.[] Cadmium zinc telluride (CZT) is a semiconductive alloy that can be divided into an array of small sensing devices.[] These devices are similar to an integrated circuit and can detect the energy of incoming gamma ray photons.[] When placed behind an absorbing mask, the CZT sensor array can also be used to determine the direction of the rays.[]

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Other industrial uses


Roughly one quarter of all zinc output in the United States (2009), is consumed in the form of zinc compounds;[] a variety of which are used industrially. Zinc oxide is widely used as a white pigment in paints, and as a catalyst in the manufacture of rubber. It is also used as a heat disperser for the rubber and acts to protect its polymers from ultraviolet radiation (the same UV protection is conferred to plastics containing zinc oxide).[] The semiconductor properties of zinc oxide make it useful in varistors and photocopying products.[69] The zinc zinc-oxide cycle is a two step thermochemical process based on zinc and zinc oxide for hydrogen production.[70] Zinc chloride is often added to lumber as a fire retardant[] and can be used as a wood preservative.[71] It is also used to make other chemicals.[] Zinc methyl (Zn(CH3) [72] 2) is used in a number of organic syntheses. Zinc sulfide (ZnS) is used in luminescent pigments such as on the hands of clocks, X-ray and television screens, and luminous paints.[] Crystals of ZnS are used in lasers that operate in the mid-infrared part of the spectrum.[73] Zinc sulfate is a chemical in dyes and pigments.[] Zinc pyrithione is used in antifouling paints.[74] Zinc powder is sometimes used as a propellant in model rockets.[] When a compressed mixture of 70% zinc and 30% sulfur powder is ignited there is a violent chemical reaction.[] This produces zinc sulfide, together with large amounts of hot gas, heat, and light.[] Zinc sheet metal is used to make zinc bars.[75]
64

Zinc oxide is used as a white pigment in paints.

Zn, the most abundant isotope of zinc, is very susceptible to neutron activation, being transmuted into the highly radioactive 65 Zn, which has a half-life of 244 days and produces intense gamma radiation. Because of this, Zinc Oxide used in nuclear reactors as an anti-corrosion agent is depleted of 64 Zn before use, this is called depleted zinc oxide. For the same reason, zinc has been proposed as a salting material for nuclear weapons (cobalt is another, better-known salting material).[] A jacket of isotopically enriched 64 Zn would be irradiated by the intense high-energy neutron flux from an exploding thermonuclear weapon, forming a large amount of 65 Zn significantly increasing the radioactivity of the weapon's fallout.[] Such a weapon is not known to have ever been built, tested, or used.[] 65 Zn is also used as a tracer to study how alloys that contain zinc wear out, or the path and the role of zinc in organisms.[76] Zinc dithiocarbamate complexes are used as agricultural fungicides; these include Zineb, Metiram, Propineb and Ziram.[77] Zinc naphthenate is used as wood preservative.[78] Zinc, in the form of ZDDP, is also used as an anti-wear additive for metal parts in engine oil.[79]

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Dietary supplement
Zinc is included in most single tablet over-the-counter daily vitamin and mineral supplements.[] Preparations include zinc oxide, zinc acetate, and zinc gluconate.[] It is believed to possess antioxidant properties, which may protect against accelerated aging of the skin and muscles of the body; studies differ as to its effectiveness.[] Zinc also helps speed up the healing process after an injury.[] It is also suspected of being beneficial to the body's immune system. Indeed, zinc deficiency may have effects on virtually all parts of the human immune system.[80] The efficacy of zinc compounds when used to reduce the duration or severity of cold symptoms is controversial.[81] A 2011 systematic review concludes that supplementation yields a mild decrease in duration and severity of cold symptoms.[82]Optimum dosing and formulation have not been determined. The studies included in the 2011 review used a variety of forms and doses of zinc, including zinc gluconate or zinc acetate lozenges and zinc sulfate syrup. The doses ranged from 30 to 160 milligrams per day. The researchers noted the following: Given the variability in the populations studied (no studies from low- or middle-income countries), dose, formulation and duration GNC zinc 50 mg tablets (AU) of zinc used in the included studies, more research is needed to address these variabilities and determine the optimal duration of treatment as well as the dosage and formulations of zinc that will produce clinical benefits without increasing adverse effects, before making a general recommendation for zinc in treatment of the common cold. Zinc serves as a simple, inexpensive, and critical tool for treating diarrheal episodes among children in the developing world. Zinc becomes depleted in the body during diarrhea, but recent studies suggest that replenishing zinc with a 10- to 14-day course of treatment can reduce the duration and severity of diarrheal episodes and may also prevent future episodes for up to three months.[83] The Age-Related Eye Disease Study determined that zinc can be part of an effective treatment for age-related macular degeneration.[84] Zinc supplementation is an effective treatment for acrodermatitis enteropathica, a genetic disorder affecting zinc absorption that was previously fatal to babies born with it.[]

Gastroenteritis is strongly attenuated by ingestion of zinc, and this effect could be due to direct antimicrobial action of the zinc ions in the gastrointestinal tract, or to the absorption of the zinc and re-release from immune cells (all granulocytes secrete zinc), or both.[85][86][87] In 2011, researchers at John Jay College of Criminal Justice reported that dietary zinc supplements can mask the presence of drugs in urine. Similar claims have been made in web forums on that topic.[88] Although not yet tested as a therapy in humans, a growing body of evidence indicates that zinc may preferentially kill prostate cancer cells. Because zinc naturally homes to the prostate and because the prostate is accessible with relatively non-invasive procedures, its potential as a chemotherapeutic agent in this type of cancer has shown promise.[89] However, other studies have demonstrated that chronic use of zinc supplements in excess of the recommended dosage may actually increase the chance of developing prostate cancer, also likely due to the natural buildup of this heavy metal in the prostate.[90]

Zinc gluconate is one compound used for the delivery of zinc as a dietary supplement.

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79

Topical use
Topical administration of zinc preparations include ones used on the skin, often in the form of zinc oxide. Zinc preparations can protect against sunburn in the summer and windburn in the winter.[] Applied thinly to a baby's diaper area (perineum) with each diaper change, it can protect against diaper rash.[] Zinc lactate is used in toothpaste to prevent halitosis.[91] Zinc pyrithione is widely applied in shampoos because of its anti-dandruff function.[92] Zinc ions are effective antimicrobial agents even at low concentrations.[93]

Organic chemistry
There are many important organozinc compounds. Organozinc chemistry is the science of organozinc compounds describing their physical properties, synthesis and reactions.[94][95][96][97] Among important applications is the Frankland-Duppa Reaction in which an oxalate ester(ROCOCOOR) reacts with an alkyl halide R'X, zinc and hydrochloric acid to the -hydroxycarboxylic esters RR'COHCOOR,[98] the Reformatskii reaction which converts -halo-esters and aldehydes to -hydroxy-esters, the Addition of diphenylzinc to an aldehyde SimmonsSmith reaction in which the carbenoid (iodomethyl)zinc iodide reacts with alkene(or alkyne) and converts them to cyclopropane, the Addition reaction of organozinc compounds to carbonyl compounds. The Barbier reaction (1899) which is the zinc equivalent of the magnesium Grignard reaction and is better of the two. In presence of just about any water the formation of the organomagnesium halide will fail whereas the Barbier reaction can even take place in water. On the downside organozincs are much less nucleophilic than Grignards, are expensive and difficult to handle. Commercially available diorganozinc compounds are dimethylzinc, diethylzinc and diphenylzinc. In one study[99][100] the active organozinc compound is obtained from much cheaper organobromine precursors: The Negishi coupling is also an important reaction for the formation of new carbon carbon bonds between unsaturated carbon atoms in alkenes, arenes and alkynes. The catalysts are nickel and palladium. A key step in the catalytic cycle is a transmetalation in which a zinc halide exchanges its organic substituent for another halogen with the palladium (nickel) metal center. The Fukuyama coupling is another coupling reaction but this one with a thioester as reactant forming a ketone.

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Biological role
Zinc is an essential trace element, necessary for plants,[] animals,[101] and microorganisms.[102] Zinc is found in nearly 100 specific enzymes[] (other sources say 300), serves as structural ions in transcription factors and is stored and transferred in metallothioneins.[] It is "typically the second most abundant transition metal in organisms" after iron and it is the only metal which appears in all enzyme classes.[] In proteins, Zn ions are often coordinated to the amino acid side chains of aspartic acid, glutamic acid, cysteine and histidine. The theoretical and computational description of this zinc binding in proteins (as well as that of other transition metals) is difficult.[103] There are 2-4grams of zinc[] distributed throughout the human body. Most zinc is in the brain, muscle, bones, kidney, and liver, with the highest concentrations in the prostate and parts of the eye.[104] Semen is particularly rich in zinc, which is a key factor in prostate gland function and reproductive organ growth.[] In humans, zinc plays "ubiquitous biological roles".[] It interacts with "a wide range of organic ligands",[] and has roles in the metabolism of RNA and DNA, signal transduction, and gene expression. It also regulates apoptosis. A 2006 study estimated that about 10% of human proteins (2800) potentially bind zinc, in addition to hundreds which transport and traffic zinc; a similar in silico study in the plant Arabidopsis thaliana found 2367 zinc-related proteins.[] In the brain, zinc is stored in specific synaptic vesicles by glutamatergic neurons[] and can "modulate brain excitability".[] It plays a key role in synaptic plasticity and so in learning.[105] However it has been called "the brain's dark horse"[] since it also can be a neurotoxin, suggesting zinc homeostasis plays a critical role in normal functioning of the brain and central nervous system.[]

Enzymes
Zinc is an efficient Lewis acid, making it a useful catalytic agent in hydroxylation and other enzymatic reactions.[] The metal also has a flexible coordination geometry, which allows proteins using it to rapidly shift conformations to perform biological reactions.[106] Two examples of zinc-containing enzymes are carbonic anhydrase and carboxypeptidase, which are vital to the processes of carbon dioxide (CO [] 2) regulation and digestion of proteins, respectively. In vertebrate blood, carbonic anhydrase converts CO 2 into bicarbonate and the same enzyme transforms the bicarbonate Ribbon diagram of human carbonic anhydrase II, back into CO [107] with zinc atom visible in the center 2 for exhalation through the lungs. Without this enzyme, this [] conversion would occur about one million times slower at the normal blood pH of 7 or would require a pH of 10 or more.[] The non-related -carbonic anhydrase is required in plants for leaf formation, the synthesis of indole acetic acid (auxin) and alcoholic fermentation.[108] Carboxypeptidase cleaves peptide linkages during digestion of proteins. A coordinate covalent bond is formed between the terminal peptide and a C=O group attached to zinc, which gives the carbon a positive charge. This helps to create a hydrophobic pocket on the enzyme near the zinc, which attracts the non-polar part of the protein being digested.[]

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81

Other proteins
Zinc serves a purely structural role in zinc fingers, twists and clusters.[] Zinc fingers form parts of some transcription factors, which are proteins that recognize DNA base sequences during the replication and transcription of DNA. Each of the nine or ten Zn2+ ions in a zinc finger helps maintain the finger's structure by coordinately binding to four amino acids in the transcription factor.[] The transcription factor wraps around the DNA helix and uses its fingers to accurately bind to the DNA sequence.

Zinc fingers help read DNA sequences.

In blood plasma, zinc is bound to and transported by albumin (60%, low-affinity) and transferrin (10%).[] Since transferrin also transports iron, excessive iron reduces zinc absorption, and vice-versa. A similar reaction occurs with copper.[] The concentration of zinc in blood plasma stays relatively constant regardless of zinc intake.[] Cells in the salivary gland, prostate, immune system and intestine use zinc signaling as one way to communicate with other cells.[109] Zinc may be held in metallothionein reserves within microorganisms or in the intestines or liver of animals.[] Metallothionein in intestinal cells is capable of adjusting absorption of zinc by 1540%.[] However, inadequate or excessive zinc intake can be harmful; excess zinc particularly impairs copper absorption because metallothionein absorbs both metals.[]

Dietary intake
In the U.S., the Recommended Dietary Allowance (RDA) is 8mg/day for women and 11mg/day for men.[] Median intake in the U.S. around 2000 was 9mg/day for women and 14mg/day in men.[] Oysters, lobster[] and red meats, especially beef, lamb and liver have some of the highest concentrations of zinc in food.[] The concentration of zinc in plants varies based on levels of the element in soil. When there is adequate zinc in the soil, the food plants that contain the most zinc are wheat (germ and bran) and various seeds (sesame, poppy, alfalfa, celery, mustard).[] Zinc is also found in beans, nuts, almonds, whole grains, pumpkin seeds, sunflower seeds and blackcurrant.[] Other sources include fortified food and dietary supplements, which come in various forms. A 1998 review concluded that zinc oxide, one of the most common supplements in the United States, and zinc carbonate are nearly Foods & spices containing zinc insoluble and poorly absorbed in the body.[] This review cited studies which found low plasma zinc concentrations after zinc oxide and zinc carbonate were consumed compared with those seen after consumption of zinc acetate and sulfate salts.[] However, harmful excessive supplementation is a problem among the relatively affluent, and should probably not exceed 20mg/day in healthy people,[110] although the U.S. National Research Council set a Tolerable Upper Intake of 40mg/day.[111] For fortification, however, a 2003 review recommended zinc oxide in cereals as cheap, stable, and as easily absorbed as more expensive forms.[112] A 2005 study found that various compounds of zinc, including oxide and sulfate, did not show statistically significant differences in absorption when added as fortificants to maize tortillas.[113] A 1987 study found that zinc picolinate was better absorbed than zinc gluconate or zinc citrate.[114] However, a study

Zinc published in 2008 determined that zinc glycinate is the best absorbed of the four dietary supplement types available.[115]

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Deficiency
Zinc deficiency is usually due to insufficient dietary intake, but can be associated with malabsorption, acrodermatitis enteropathica, chronic liver disease, chronic renal disease, sickle cell disease, diabetes, malignancy, and other chronic illnesses.[] Symptoms of mild zinc deficiency are diverse.[] Clinical outcomes include depressed growth, diarrhea, impotence and delayed sexual maturation, alopecia, eye and skin lesions, impaired appetite, altered cognition, impaired host defense properties, defects in carbohydrate utilization, and reproductive teratogenesis.[] Mild zinc deficiency depresses immunity,[116] although excessive zinc does also.[] Animals with a diet deficient in zinc require twice as much food in order to attain the same weight gain as animals given sufficient zinc.[] Groups at risk for zinc deficiency include the elderly, children in developing countries, and those with renal insufficiency. The zinc chelator phytate, found in seeds and cereal bran, can contribute to zinc malabsorption.[] Despite some concerns,[117] western vegetarians and vegans have not been found to suffer from overt zinc deficiencies any more than meat-eaters.[118] Major plant sources of zinc include cooked dried beans, sea vegetables, fortified cereals, soyfoods, nuts, peas, and seeds.[117] However, phytates in many whole-grains and fiber in many foods may interfere with zinc absorption and marginal zinc intake has poorly understood effects. There is some evidence to suggest that more than the US RDA (15mg) of zinc daily may be needed in those whose diet is high in phytates, such as some vegetarians.[117] These considerations must be balanced against the fact that there is a paucity of adequate zinc biomarkers, and the most widely used indicator, plasma zinc, has poor sensitivity and specificity.[119] Diagnosing zinc deficiency is a persistent challenge.[] Nearly two billion people in the developing world are deficient in zinc.[] In children it causes an increase in infection and diarrhea, contributing to the death of about 800,000 children worldwide per year.[] The World Health Organization advocates zinc supplementation for severe malnutrition and diarrhea.[] Zinc supplements help prevent disease and reduce mortality, especially among children with low birth weight or stunted growth.[] However, zinc supplements should not be administered alone, since many in the developing world have several deficiencies, and zinc interacts with other micronutrients.[120] Agriculture Zinc deficiency is crop plants' most common micronutrient deficiency; it is particularly common in high-pH soils.[121] Zinc-deficient soil is cultivated in the cropland of about half of Turkey and India, a third of China, and most of Western Australia, and substantial responses to zinc fertilization have been reported in these areas.[] Plants that grow in soils that are zinc-deficient are more susceptible to disease. Zinc is primarily added to the soil through the weathering of rocks, but humans have added zinc through fossil fuel combustion, mine waste, phosphate fertilizers, limestone, manure, sewage sludge, and particles from galvanized surfaces. Excess zinc is toxic to plants, although zinc toxicity is far less widespread.[]

Precautions
Toxicity
Although zinc is an essential requirement for good health, excess zinc can be harmful. Excessive absorption of zinc suppresses copper and iron absorption.[] The free zinc ion in solution is highly toxic to plants, invertebrates, and even vertebrate fish.[122] The Free Ion Activity Model is well-established in the literature, and shows that just micromolar amounts of the free ion kills some organisms. A recent example showed 6 micromolar killing 93% of all Daphnia in water.[123]

Zinc The free zinc ion is a powerful Lewis acid up to the point of being corrosive. Stomach acid contains hydrochloric acid, in which metallic zinc dissolves readily to give corrosive zinc chloride. Swallowing a post-1982 American one cent piece (97.5% zinc) can cause damage to the stomach lining due to the high solubility of the zinc ion in the acidic stomach.[124] There is evidence of induced copper deficiency at low intakes of 100300mg Zn/day; a recent trial had higher hospitalizations for urinary complications compared to placebo among elderly men taking 80mg/day.[125] The USDA RDA is 11 and 8mg Zn/day for men and women, respectively.[] Even lower levels, closer to the RDA, may interfere with the utilization of copper and iron or adversely affect cholesterol.[] Levels of zinc in excess of 500ppm in soil interfere with the ability of plants to absorb other essential metals, such as iron and manganese.[] There is also a condition called the zinc shakes or "zinc chills" that can be induced by the inhalation of freshly formed zinc oxide formed during the welding of galvanized materials.[] Zinc is a common ingredient of denture cream which may contain between 17 and 38mg of zinc per gram. There have been cases of disability or even death due to excessive use of these products.[126] The U.S. Food and Drug Administration (FDA) has stated that zinc damages nerve receptors in the nose, which can cause anosmia. Reports of anosmia were also observed in the 1930s when zinc preparations were used in a failed attempt to prevent polio infections.[127] On June 16, 2009, the FDA said that consumers should stop using zinc-based intranasal cold products and ordered their removal from store shelves. The FDA said the loss of smell can be life-threatening because people with impaired smell cannot detect leaking gas or smoke and cannot tell if food has spoiled before they eat it.[] Recent research suggests that the topical antimicrobial zinc pyrithione is a potent heat shock response inducer that may impair genomic integrity with induction of PARP-dependent energy crisis in cultured human keratinocytes and melanocytes.[128]

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Poisoning
In 1982, the United States Mint began minting pennies coated in copper but made primarily of zinc. With the new zinc pennies, there is the potential for zinc toxicosis, which can be fatal. One reported case of chronic ingestion of 425 pennies (over 1kg of zinc) resulted in death due to gastrointestinal bacterial and fungal sepsis, while another patient, who ingested 12grams of zinc, only showed lethargy and ataxia (gross lack of coordination of muscle movements).[129] Several other cases have been reported of humans suffering zinc intoxication by the ingestion of zinc coins.[130][131] Pennies and other small coins are sometimes ingested by dogs, resulting in the need for medical treatment to remove the foreign body. The zinc content of some coins can cause zinc toxicity, which is commonly fatal in dogs, where it causes a severe hemolytic anemia, and also liver or kidney damage; vomiting and diarrhea are possible symptoms.[132] Zinc is highly toxic in parrots and poisoning can often be fatal.[133] The consumption of fruit juices stored in galvanized cans has resulted in mass parrot poisonings with zinc.[]

Notes
[1] http:/ / www. infinityfoundation. com/ mandala/ t_es/ t_es_agraw_zinc_frameset. htm [2] http:/ / www. ancient-asia-journal. com/ article/ view/ aa. 06112/ 23 [3] electronic-book ISBN 978-94-007-5561-1 electronic[34] p. 46, Ancient mining and metallurgy in Rajasthan, S. M. Gandhi, chapter 2 in Crustal Evolution and Metallogeny in the Northwestern Indian Shield: A Festschrift for Asoke Mookherjee, M. Deb, ed., Alpha Science Int'l Ltd., 2000, ISBN 1-84265-001-7. [35] (public domain text) [42] An East India Company ship carrying a cargo of nearly pure zinc metal from the Orient sank off the coast Sweden in 1745. [57] Electric current will naturally flow between zinc and steel but in some circumstances inert anodes are used with an external DC source. [87] In clinical trials, both zinc gluconate and zinc gluconate glycine (the formulation used in lozenges) have been shown to shorten the duration of symptoms of the common cold. The amount of glycine can vary from two to twenty moles per mole of zinc gluconate. One review of the research found that out of nine controlled experiments using zinc lozenges, the results were positive in four studies, and no better than placebo in five. This review also suggested that the research is characterized by methodological problems, including differences in the dosage amount

Zinc
used, and the use of self-report data. The evidence suggests that zinc supplements may be most effective if they are taken at the first sign of cold symptoms. [100] In this one-pot reaction bromobenzene is converted to phenyllithium by reaction with 4 equivalents of n-butyllithium, then transmetalation with zinc chloride forms diphenylzinc which continues to react in an asymmetric reaction first with the MIB ligand and then with 2-naphthylaldehyde to the alcohol. In this reaction formation of diphenylzinc is accompanied by that of lithium chloride, which unchecked, catalyses the reaction without MIB involvement to the racemic alcohol. The salt is effectively removed by chelation with tetraethylethylene diamine (TEEDA) resulting in an enantiomeric excess of 92%. [102] Zinc's role in microorganisms is particularly reviewed in: [117] "Position of the American Dietetic Association and Dietitians of Canada: Vegetarian diets". Journal of the American Dietetic Association, 2003, 06. Retrieved 4 January 2007.

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References Bibliography
Chambers, William and Robert (1901). Chambers's Encyclopaedia: A Dictionary of Universal Knowledge (http:// books.google.com/?id=Rz8oAAAAYAAJ&printsec=toc) (Revised ed.). London and Edinburgh: J. B. Lippincott Company. Cotton, F. Albert; Wilkinson, Geoffrey; Murillo, Carlos A.; Bochmann, Manfred (1999). Advanced Inorganic Chemistry (6th ed.). New York: John Wiley & Sons, Inc. ISBN0-471-19957-5. CRC contributors (2006). David R. Lide, ed. Handbook of Chemistry and Physics (http://books.google.com/ ?id=WDll8hA006AC&pg=PT893) (87th ed.). Boca Raton, Florida: CRC Press, Taylor & Francis Group. ISBN0-8493-0487-3. Emsley, John (2001). "Zinc" (http://books.google.com/?id=j-Xu07p3cKwC). Nature's Building Blocks: An A-Z Guide to the Elements. Oxford, England, UK: Oxford University Press. pp.499505. ISBN0-19-850340-7. Greenwood, N. N.; Earnshaw, A. (1997). Chemistry of the Elements (2nd ed.). Oxford: Butterworth-Heinemann. ISBN0-7506-3365-4. Heiserman, David L. (1992). "Element 30: Zinc" (http://books.google.com/?id=24l-Cpal9oIC). Exploring Chemical Elements and their Compounds. New York: TAB Books. ISBN0-8306-3018-X. Lehto, R. S. (1968). "Zinc". In Clifford A. Hampel. The Encyclopedia of the Chemical Elements. New York: Reinhold Book Corporation. pp.822830. ISBN0-442-15598-0. LCCN 68-29938 (http://lccn.loc.gov/ 68-29938). United States National Research Council, Institute of Medicine. (2000). Dietary Reference Intakes for Vitamin A, Vitamin K, Arsenic, Boron, Chromium, Copper, Iodine, Iron, Manganese, Molybdenum, Nickel, Silicon, Vanadium, and Zinc (http://www.nap.edu/catalog.php?record_id=10026). National Academies Press. pp.442455. Stwertka, Albert (1998). "Zinc". Guide to the Elements (Revised ed.). Oxford University Press. ISBN0-19-508083-1. Weeks, Mary Elvira (1933). "III. Some Eighteenth-Century Metals". The Discovery of the Elements. Easton, PA: Journal of Chemical Education. ISBN0-7661-3872-0.

Zinc

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External links
Zinc Fact Sheet (http://ods.od.nih.gov/factsheets/zinc/) from the U.S. National Institutes of Health History & Etymology of Zinc (http://elements.vanderkrogt.net/element.php?sym=Zn) Statistics and Information from the U.S. Geological Survey (http://minerals.usgs.gov/minerals/pubs/ commodity/zinc/index.html) Reducing Agents > Zinc (http://www.organic-chemistry.org/chemicals/reductions/zinc-zn.shtm) American Zinc Association (http://www.zinc.org) Information about the uses and properties of zinc. Outline safety data for zinc (http://ptcl.chem.ox.ac.uk/MSDS/ZI/zinc.html) International Society for Zinc Biology (http://www.iszb.org) Founded in 2008, an international. nonprofit organization bringing together scientists working on the biological actions of zinc. Zinc-UK (http://zinc-uk.org) Founded in 2010 to bring together scientists in the United Kingdom working on zinc. Zinc (http://www.periodicvideos.com/videos/030.htm) at The Periodic Table of Videos (University of Nottingham)

Brass
Brass is an alloy of copper and zinc; the proportions of zinc and copper can be varied to create a range of brasses with varying properties.[1] By comparison, bronze is principally an alloy of copper and tin.[2] Bronze does not necessarily contain tin, and a variety of alloys of copper, including alloys with arsenic, phosphorus, aluminium, manganese, and silicon, are commonly termed "bronze". The term is applied to a variety of brasses and the distinction is largely historical,[3] both terms having a common antecedent in the term latten.

Brass die, along with zinc and copper samples.

Brass is a substitutional alloy. It is used for decoration for its bright gold-like appearance; for applications where low friction is required such as locks, gears, bearings, doorknobs, ammunition casings and valves; for plumbing and electrical applications; and extensively in musical instruments such as horns and bells for its acoustic properties. It is also used in zippers. Brass is often used in situations where it is important that sparks not be struck, as in fittings and tools around explosive gases.[4]

Properties

Brass

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The malleability and acoustic properties of brass have made it the metal of choice for musical instruments such as the trombone, tuba, trumpet, cornet, baritone horn, euphonium, tenor horn, and French horn which are collectively known as the brass within an orchestra. Even though the saxophone is classified as a woodwind instrument and the harmonica is a free reed aerophone, both are also often made from brass. In organ pipes of the reed family, brass strips (called tongues) are used as the reeds, which beat against the shallot (or beat "through" the shallot in the case of a "free" reed). Although not part of the brass section, snare drums are also sometimes made of brass.

Microstructure of rolled and annealed brass (400X magnification)

Brass has higher malleability than bronze or zinc. The relatively low melting point of brass (900 to 940C, 1652 to 1724F, depending on composition) and its flow characteristics make it a relatively easy material to cast. By varying the proportions of copper and zinc, the properties of the brass can be changed, allowing hard and soft brasses. The density of brass is approximately .303lb/cubic inch, 8.4 to 8.73grams per cubic centimetre.[5] Today almost 90% of all brass alloys are recycled.[6] Because brass is not ferromagnetic, it can be separated from ferrous scrap by passing the scrap near a powerful magnet. Brass scrap is collected and transported to the foundry where it is melted and recast into billets. Billets are heated and extruded into the desired form and size. Aluminium makes brass stronger and more corrosion resistant. Aluminium also causes a highly beneficial hard layer of aluminium oxide (Al2O3) to be formed on the surface that is thin, transparent and self-healing. Tin has a similar effect and finds its use especially in seawater applications (naval brasses). Combinations of iron, aluminium, silicon and manganese make brass wear and tear resistant.[7]

Lead content
To enhance the machinability of brass, lead is often added in concentrations of around 2%. Since lead has a lower melting point than the other constituents of the brass, it tends to migrate towards the grain boundaries in the form of globules as it cools from casting. The pattern the globules form on the surface of the brass increases the available lead surface area which in turn affects the degree of leaching. In addition, cutting operations can smear the lead globules over the surface. These effects can lead to significant lead leaching from brasses of comparatively low lead content.[8] Silicon is an alternative to lead; however, when silicon is used in a brass alloy, the scrap must never be mixed with leaded brass scrap because of contamination and safety problems.[9] In October 1999 the California State Attorney General sued 13 key manufacturers and distributors over lead content. In laboratory tests, state researchers found the average brass key, new or old, exceeded the California Proposition 65 limits by an average factor of 19, assuming handling twice a day.[10] In April 2001 manufacturers agreed to reduce lead content to 1.5%, or face a requirement to warn consumers about lead content. Keys plated with other metals are not affected by the settlement, and may continue to use brass alloys with higher percentage of lead content.[11][12] Also in California, lead-free materials must be used for "each component that comes into contact with the wetted surface of pipes and pipe fittings, plumbing fittings and fixtures." On January 1, 2010, the maximum amount of lead in "lead-free brass" in California was reduced from 4% to 0.25% lead. The common practice of using pipes for electrical grounding is discouraged, as it accelerates lead corrosion.[13][14]

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Corrosion-resistant brass for harsh environments


The so-called dezincification resistant (DZR or DR) brasses are used where there is a large corrosion risk and where normal brasses do not meet the standards. Applications with high water temperatures, chlorides present, or deviating water qualities (soft water) play a role. DZR-brass is excellent in water boiler systems. This brass alloy must be produced with great care, with special attention placed on a balanced composition and proper production temperatures and parameters to avoid long-term failures.

Germicidal and antimicrobial applications

Brass sampling cock with stainless steel handle.

The copper in brass makes brass germicidal. Depending upon the type and concentration of pathogens and the medium they are in, brass kills these microorganisms within a few minutes to hours of contact.[15][][] The bactericidal properties of brass have been observed for centuries and were confirmed in the laboratory in 1983.[16] Subsequent experiments by research groups around the world reconfirmed the antimicrobial efficacy of brass, as well as copper and other copper alloys (see Antimicrobial copper-alloy touch surfaces).[15][][] Extensive structural membrane damage to bacteria was noted after being exposed to copper. In 2007, U.S. Department of Defenses Telemedicine and Advanced Technology Research Center (TATRC) began to study the antimicrobial properties of copper alloys, including four brasses (C87610, C69300, C26000, C46400) in a multi-site clinical hospital trial conducted at the Memorial Sloan-Kettering Cancer Center (New York City), the Medical University of South Carolina, and the Ralph H. Johnson VA Medical Center (South Carolina).[13][17] Commonly touched items, such as bed rails, over-the-bed tray tables, chair arms, nurse's call buttons, IV poles, etc. were retrofitted with antimicrobial copper alloys in certain patient rooms (i.e., the coppered rooms) in the Intensive Care Unit (ICU). Early results disclosed in 2011 indicate that the coppered rooms demonstrated a 97% reduction in surface pathogens versus the non-coppered rooms. This reduction is the same level achieved by terminal cleaning regimens conducted after patients vacate their rooms. Furthermore, of critical importance to health care professionals, the preliminary results indicated that patients in the coppered ICU rooms had a 40.4% lower risk of contracting a hospital acquired infection versus patients in non-coppered ICU rooms.[13][18][19] The U.S. Department of Defense investigation contract, which is ongoing, will also evaluate the effectiveness of copper alloy touch surfaces to prevent the transfer of microbes to patients and the transfer of microbes from patients to touch surfaces, as well as the potential efficacy of copper-alloy based components to improve indoor air quality. In the U.S., the Environmental Protection Agency regulates the registration of antimicrobial products. After extensive antimicrobial testing according to the Agencys stringent test protocols, 355 copper alloys, including many brasses, were found to kill more than 99.9% of methicillin-resistant Staphylococcus aureus (MRSA), E. coli O157:H7, Pseudomonas aeruginosa, Staphylococcus aureus, Enterobacter aerogenes, and vancomycin-resistant Enterococci (VRE) within two hours of contact.[15][] Normal tarnishing was found to not impair antimicrobial effectiveness. Antimicrobial tests have also revealed significant reductions of MRSA as well as two strains of epidemic MRSA (EMRSA-1 and EMRSA-16) on brass (C24000 with 80% Cu) at room temperature (22 C) within three hours. Complete kills of the pathogens were observed within 4 12 hours. These tests were performed under wet exposure conditions. The kill timeframes, while impressive, are nevertheless longer than for pure copper, where kill timeframes ranged between 45 to 90 minutes.[] A novel assay that mimics dry bacterial exposure to touch surfaces was developed because this test method is thought to more closely replicate real world touch surface exposure conditions. In these conditions, copper alloy

Brass surfaces were found to kill several million Colony Forming Units of Escherichia coli within minutes.[] This observation, and the fact that kill timeframes shorten as the percentage of copper in an alloy increases, is proof that copper is the ingredient in brass and other copper alloys that kills the microbes.[20] The mechanisms of antimicrobial action by copper and its alloys, including brass, is a subject of intense and ongoing investigation.[][][] It is believed that the mechanisms are multifaceted and include the following: 1) Potassium or glutamate leakage through the outer membrane of bacteria; 2) Osmotic balance disturbances; 3) Binding to proteins that do not require or utilize copper; 4) Oxidative stress by hydrogen peroxide generation. Research is being conducted at this time to determine whether brass, copper, and other copper alloys can help to reduce cross contamination in public facilities and reduce the incidence of nosocomial infections (hospital acquired infections) in healthcare facilities. Also, owing to its antimicrobial/algaecidal properties that prevent biofouling, in conjunction with its strong structural and corrosion-resistant benefits for marine environments, brass alloy netting cages are currently being deployed in commercial-scale aquaculture operations in Asia, South America, and the USA.

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Season cracking
Brass is susceptible to stress corrosion cracking, especially from ammonia or substances containing or releasing ammonia. The problem is sometimes known as season cracking after it was first discovered in brass cartridge cases used for rifle ammunition during the 1920s in the Indian Army. The problem was caused by high residual stresses from cold forming of the cases Cracking in brass caused by ammonia attack during manufacture, together with chemical attack from traces of ammonia in the atmosphere. The cartridges were stored in stables and the ammonia concentration rose during the hot summer months, thus initiating brittle cracks. The problem was resolved by annealing the cases, and storing the cartridges elsewhere.

Brass types
Admiralty brass contains 30% zinc, and 1% tin which inhibits dezincification in many environments. Aich's alloy typically contains 60.66% copper, 36.58% zinc, 1.02% tin, and 1.74% iron. Designed for use in marine service owing to its corrosion resistance, hardness and toughness. A characteristic application is to the protection of ships' bottoms, but more modern methods of cathodic protection have rendered its use less common. Its appearance resembles that of gold.[21] Alpha brasses with less than 35% zinc, are malleable, can be worked cold, and are used in pressing, forging, or similar applications. They contain only one phase, with face-centered cubic crystal structure. Prince's metal or Prince Rupert's metal is a type of alpha brass containing 75% copper and 25% zinc. Due to its beautiful yellow color, it is used as an imitation of gold.[22] The alloy was named after Prince Rupert of the Rhine. Alpha-beta brass (Muntz metal), also called duplex brass, is 3545% zinc and is suited for hot working. It contains both and ' phase; the '-phase is body-centered cubic and is harder and stronger than . Alpha-beta brasses are usually worked hot. Aluminium brass contains aluminium, which improves its corrosion resistance. It is used for seawater service[23] and also in Euro coins (also known as "Nordic gold") - (see also "Nordic gold" below).

Brass Arsenical brass contains an addition of arsenic, and frequently aluminium, and is used for boiler fireboxes. Beta brasses, with 4550% zinc content, can only be worked hot, and are harder, stronger, and suitable for casting. Cartridge brass is a 30% zinc brass with good cold working properties. Used for ammunition cases. Common brass, or rivet brass, is a 37% zinc brass, cheap and standard for cold working. DZR brass is dezincification resistant brass with a small percentage of arsenic. Gilding metal is the softest type of brass commonly available. An alloy of 95% copper and 5% zinc, gilding metal is typically used for ammunition bullet "jackets", e.g. full metal jacket bullets. High brass contains 65% copper and 35% zinc, has a high tensile strength and is used for springs, screws, and rivets. Leaded brass is an alpha-beta brass with an addition of lead. It has excellent machinability. Lead-free brass as defined by California Assembly Bill AB 1953 contains "not more than 0.25 percent lead content".[13] Low brass is a copper-zinc alloy containing 20% zinc with a light golden color and excellent ductility; it is used for flexible metal hoses and metal bellows. Manganese brass is a brass most notably used in making golden dollar coins in the United States. It contains roughly 70% copper, 29% zinc, and 1.3% manganese.[24] Muntz metal is about 60% copper, 40% zinc, and a trace of iron, used as a lining on boats. Naval brass, similar to admiralty brass, is 40% zinc, and 1% tin. Nickel brass is composed of 70% copper, 24.5% zinc, and 5.5% nickel used to make pound coins in the pound sterling currency. Nordic gold, used in 10, 20, and 50 cents euro coins, contains 89% copper, 5% aluminium, 5% zinc, and 1% tin. Red brass is both an American term for the copper-zinc-tin alloy known as gunmetal, and an alloy which is considered both a brass and a bronze. It typically contains 85% copper, 5% tin, 5% lead, and 5% zinc.[25][] Red brass is also an alternative name for copper alloy C23000, which is composed of 1416% zinc, 0.05% iron and lead, and the remainder copper.[26] It may also refer to ounce metal, another copper-zinc-tin alloy. Rich low brass (Tombac) is 15% zinc. It is often used in jewelry applications. Tonval brass (also called CW617N or CZ122 or OT58) is a copper-lead-zinc alloy. It is not recommended for seawater use, being susceptible to dezincification.[27][28] White brass contains more than 50% zinc and is too brittle for general use. The term may also refer to certain types of nickel silver alloys as well as Cu-Zn-Sn alloys with high proportions (typically 40%+) of tin and/or zinc, as well as predominantly zinc casting alloys with copper additive. Yellow brass is an American term for 33% zinc brass.

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History
Although forms of brass have been in use since prehistory,[29] its true nature as a copper-zinc alloy was not understood until the post medieval period because the zinc vapor which reacted with copper to make brass was not recognised as a metal.[30] The King James Bible makes many references to "brass".[31] The Shakespearean English form of the word 'brass' can mean any bronze alloy, or copper, rather than the strict modern definition of brass. [citation needed] The earliest brasses may have been natural alloys made by smelting zinc-rich copper ores.[32] By the Roman period brass was being deliberately produced from metallic copper and zinc minerals using the cementation process and variations on this method continued until the mid-19th century.[33] It was eventually replaced by speltering, the direct alloying of copper and zinc metal which was introduced to Europe in the 16th century.[32]

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Early copper zinc alloys


In West Asia and the Eastern Mediterranean early copper zinc alloys are now known in small numbers from a number of third Millennium BC sites in the Aegean, Iraq, the United Arab Emirates, Kalmykia, Turkmenistan and Georgia and from 2nd Millennium BC sites in West India, Uzbekistan, Iran, Syria, Iraq and Israel.[34] However, isolated examples of copper-zinc alloys are known in China from as early as the 5th Millennium BC.[] The compositions of these early "brass" objects are very variable and most have zinc contents of between 5% and 15% wt which is lower than in brass produced by cementation.[35] These may be "natural alloys" manufactured by smelting zinc rich copper ores in redox conditions. Many have similar tin contents to contemporary bronze artefacts and it is possible that some copper-zinc alloys were accidental and perhaps not even distinguished from copper.[35] However the large number of copper-zinc alloys now known suggests that at least some were deliberately manufactured and many have zinc contents of more than 12% wt which would have resulted in a distinctive golden color.[35][36] By the 8th7th century BC Assyrian cuneiform tablets mention the exploitation of the "copper of the mountains" and this may refer to "natural" brass.[37] Oreichalkos, the Ancient Greek translation of this term, was later adapted to the Latin aurichalcum meaning "golden copper" which became the standard term for brass.[38] In the 4th century BC Plato knew oreichalkos as rare and nearly as valuable as gold[] and Pliny describes how aurichalcum had come from Cypriot ore deposits which had been exhausted by the 1st century AD.[39]

Brass making in the Roman World


During the later part of first millennium BC the use of brass spread across a wide geographical area from Britain[] and Spain[40] in the west to Iran, and India in the east.[41] This seems to have been encouraged by exports and influence from the Middle-East and eastern Mediterranean where deliberate production of brass from metallic copper and zinc ores had been introduced.[42] The 4th century BC writer Theopompus, quoted by Strabo, describes how heating earth from Andeira in Turkey produced "droplets of false silver", probably metallic zinc, which could be used to turn copper into oreichalkos.[43] In the 1st century BC the Greek Dioscorides seems to have recognised a link between zinc minerals and brass describing how Cadmia (zinc oxide) was found on the walls of furnaces used to heat either zinc ore or copper and explaining that it can then be used to make brass.[44] By the first century BC brass was available in sufficient supply to use as coinage in Phrygia and Bithynia,[45] and after the Augustan currency reform of 23 BC it was also used to make Roman dupondii and sestertii.[46] The uniform use of brass for coinage and military equipment across the Roman world may indicate a degree of state involvement in the industry,[47][] and brass even seems to have been deliberately boycotted by Jewish communities in Palestine because of its association with Roman authority.[] Brass was produced by the cementation process where copper and zinc ore are heated together until zinc vapor is produced which reacts with the copper. There is good archaeological evidence for this process and crucibles used to produce brass by cementation have been found on Roman period sites including Xanten[] and Nidda[] in Germany, Lyon in France[48] and at a number of sites in Britain.[49] They vary in size from tiny acorn sized to large amphorae like vessels but all have elevated levels of zinc on the interior and are lidded.[48] They show no signs of slag or metal prills suggesting that zinc minerals were heated to produce zinc vapor which reacted with metallic copper in a solid state reaction. The fabric of these crucibles is porous, probably designed to prevent a build up of pressure, and many have small holes in the lids which may be designed to release pressure[48] or to add additional zinc minerals near the end of the process. Dioscorides mentioned that zinc minerals were used for both the working and finishing of brass, perhaps suggesting secondary additions.[50] Brass made during the early Roman period seems to have varied between 20% to 28% wt zinc.[51] The high content of zinc in coinage and brass objects declined after the first century AD and it has been suggested that this reflects zinc loss during recycling and thus an interruption in the production of new brass.[52] However it is now thought this was probably a deliberate change in composition[] and overall the use of brass increases over this period making up

Brass around 40% of all copper alloys used in the Roman world by the 4th century AD.[53]

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Brass making in the medieval period


Little is known about the production of brass during the centuries immediately after the collapse of the Roman Empire. Disruption in the trade of tin for bronze from Western Europe may have contributed to the increasing popularity of brass in the east and by the 6th7th centuries AD over 90% of copper alloy artefacts from Egypt were made of brass.[54] However other alloys such as low tin bronze were also used and they vary depending on local cultural attitudes, the purpose of the metal and access to zinc, especially between the Baptism of Christ on the 12th-century baptismal font at St Bartholomew's Church, Islamic and Byzantine world.[] Conversely Lige. the use of true brass seems to have declined in Western Europe during this period in favour of gunmetals and other mixed alloys[55] but by the end of the first Millennium AD brass artefacts are found in Scandinavian graves in Scotland,[56] brass was being used in the manufacture of coins in Northumbria[57] and there is archaeological and historical evidence for the production of brass in Germany[58] and The Low Countries[59] areas rich in calamine ore which would remain important centres of brass making throughout the medieval period,[60] especially Dinant brass objects are still collectively known as dinanterie in French. The baptismal font at St Bartholomew's Church, Lige in modern Belgium (before 1117) is an outstanding masterpiece of Romanesque brass casting. The cementation process continued to be used but literary sources from both Europe and the Islamic world seem to describe variants of a higher temperature liquid process which took places in open-topped crucibles.[61] Islamic cementation seems to have used zinc oxide known as tutiya or tutty rather than zinc ores for brass making resulting in a metal with lower iron impurities.[62] A number of Islamic writers and the 13th century Italian Marco Polo describe how this was obtained by sublimation from zinc ores and condensed onto clay or iron bars, archaeological examples of which have been identified at Kush in Iran.[63] It could then be used for brass making or medicinal purposes. In 10th century Yemen al-Hamdani described how spreading al-iglimiya, probably zinc oxide, onto the surface of molten copper produced tutiya vapor which then reacted with the metal.[64] The 13th century Iranian writer al-Kashani describes a more complex process whereby tutiya was mixed with raisins and gently roasted before being added to the surface of the molten metal. A temporary lid was added at this point presumably to minimise the escape of zinc vapor.[65] In Europe a similar liquid process in open-topped crucibles took place which was probably less efficient than the Roman process and the use of the term tutty by Albertus Magnus in the 13th century suggests influence from Islamic technology.[66] The 12th century German monk Theophilus described how preheated crucibles were one sixth filled with powdered calamine and charcoal then topped up with copper and charcoal before being melted, stirred then filled again. The final product was cast, then again melted with calamine. It has been suggested that this second melting may have taken place at a lower temperature to allow more zinc to be absorbed.[67] Albertus Magnus noted that the "power" of both calamine and tutty could evaporate and described how the addition of powdered glass could create a film to bind it to the metal.[68] German brass making crucibles are known from Dortmund dating to the 10th century AD and from Soest and Schwerte in Westphalia dating to around the 13th century confirm Theophilus' account, as they are open-topped, although ceramic discs from Soest may have served as loose lids which may have

Brass been used to reduce zinc evaporation, and have slag on the interior resulting from a liquid process.[69]

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Brass making in Renaissance and post-medieval Europe


The Renaissance saw important changes to both the theory and practice of brassmaking in Europe. By the 15th century there is evidence for the renewed use of lidded cementation crucibles at Zwickau in Germany.[70] These large crucibles were capable of producing c.20kg of brass.[71] There are traces of slag and pieces of metal on the interior. Their irregular composition suggesting that this was a lower temperature not entirely liquid process.[72] The crucible lids had small holes which were blocked with clay plugs near the end of the process presumably to maximise zinc absorption in the final stages.[73] Triangular crucibles were then used to melt the brass for casting.[74] 16th-century technical writers such as Biringuccio, Ercker and Agricola described a variety of cementation brass making techniques and came closer to understanding the true nature of the process noting that copper became heavier as it changed to brass and that it became more golden as additional calamine was added.[75] Zinc metal was also becoming more commonplace By 1513 metallic zinc ingots from India and China were arriving in London and pellets of zinc condensed in furnace flues at the Rammelsberg in Germany were exploited for cementation brass making from around 1550.[76] Eventually it was discovered that metallic zinc could be alloyed with copper to make brass; a process known as speltering[77] and by 1657 the German chemist Johann Glauber had recognised that calamine was "nothing else but unmeltable zinc" and that zinc was a "half ripe metal."[78] However some earlier high zinc, low iron brasses such as the 1530 Wightman brass memorial plaque from England may have been made by alloying copper with zinc and include traces of cadmium similar those found in some zinc ingots from China.[77] However the cementation process was not abandoned and as late as the early 19th century there are descriptions of solid-state cementation in a domed furnace at around 900950 C and lasting up to 10 hours.[79] The European brass industry continued to flourish into the post medieval period buoyed by innovations such as the 16th century introduction of water powered hammers for the production of battery wares.[80] By 1559 the Germany city of Aachen alone was capable of producing 300,000 cwt of brass per year.[80] After several false starts during the 16th and 17th centuries the brass industry was also established in England taking advantage of abundant supplies of cheap copper smelted in the new coal fired reverberatory furnace.[81] In 1723 Bristol brass maker Nehemiah Champion patented the use of granulated copper, produced by pouring molten metal into cold water.[82] This increased the surface area of the copper helping it react and zinc contents of up to 33% wt were reported using this new technique.[83] In 1738 Nehemiah's son William Champion patented a technique for the first industrial scale distillation of metallic zinc known as distillation per descencum or "the English process."[84][] This local zinc was used in speltering and allowed greater control over the zinc content of brass and the production of high-zinc copper alloys which would have been difficult or impossible to produce using cementation, for use in expensive objects such as scientific instruments, clocks, brass buttons and costume jewellery.[85] However Champion continued to use the cheaper calamine cementation method to produce lower-zinc brass[85] and the archaeological remains of bee-hive shaped cementation furnaces have been identified at his works at Warmley.[] By the mid-to-late 18th century developments in cheaper zinc distillation such as John-Jaques Dony's horizontal furnaces in Belgium and the reduction of tariffs on zinc[86] as well as demand for corrosion-resistant high zinc alloys increased the popularity of speltering and as a result cementation was largely abandoned by the mid-19th century.[87]

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References
[1] Engineering Designer 30(3): 69, MayJune 2004 [2] Machinery Handbook, Industrial Press Inc, New York, Edition 24, p. 501 [4] OSH Answers: Non-sparking tools (http:/ / www. ccohs. ca/ oshanswers/ safety_haz/ hand_tools/ nonsparking. html). Ccohs.ca (2011-06-02). Retrieved on 2011-12-09. [9] Chase Brass & Copper Company, Inc (https:/ / www. chasebrass. com/ productline/ index_greendot. jsp). Chasebrass.com. Retrieved on 2011-12-09. [10] News & Alerts California Dept. of Justice Office of the Attorney General (http:/ / ag. ca. gov/ newsalerts/ print_release. php?id=529), October 12, 1999 [11] News & Alerts California Dept. of Justice Office of the Attorney General (http:/ / ag. ca. gov/ newsalerts/ print_release. php?id=1077), April 27, 2001 [12] San Francisco Superior Court, People v. Ilco Unican Corp., et a. (No. 307102) and Mateel Environmental Justice Foundation v. Ilco Unican Corp., et al. (No. 305765) [13] AB 1953 Assembly Bill Bill Analysis (http:/ / info. sen. ca. gov/ pub/ 05-06/ bill/ asm/ ab_1951-2000/ ab_1953_cfa_20060818_134053_sen_floor. html). Info.sen.ca.gov. Retrieved on 2011-12-09. [14] Requirements for Low Lead Plumbing Products in California (http:/ / www. dtsc. ca. gov/ PollutionPrevention/ upload/ Lead-in-Plumbing-Fact-Sheet. pdf), Fact Sheet, Department of Toxic Substances Control, State of California, February 2009 [15] EPA registers copper-containing alloy products (http:/ / www. epa. gov/ opp00001/ factsheets/ copper-alloy-products. htm), May 2008 [16] Kuhn, Phyllis J. (1983) Doorknobs: A Source of Nosocomial Infection? (http:/ / members. vol. at/ schmiede/ MsgverSSt. html) Diagnostic Medicine [17] Copper Touch Surfaces. Congress Funds Testing of Copper's Ability to Kill Harmful Pathogens (http:/ / www. coppertouchsurfaces. org) [18] TouchSurfaces Clinical Trials: Research Proves (http:/ / www. coppertouchsurfaces. org/ press/ releases/ 20110701. html). Coppertouchsurfaces.org. Retrieved on 2011-12-09. [19] World Health Organizations 1st International Conference on Prevention and Infection Control (ICPIC) in Geneva, Switzerland on July 1st, 2011 [20] Michels, H.T., Wilks, S.A., Noyce, J.O., and Keevil, C.W., 2005, Copper Alloys for Human Infectious Disease Control, Materials Science and Technology Conference: Copper for the 21st Century Symposium, September 2528, Pittsburgh, P.A. [21] Simons, E.N. (1970). A Dictionary of Alloys, Cornell University [22] National Pollutant Inventory Copper and compounds fact sheet (http:/ / www. npi. gov. au/ database/ substance-info/ profiles/ 27. html). Npi.gov.au. Retrieved on 2011-12-09. [23] Material Properties Data: Aluminum Brass (http:/ / www. makeitfrom. com/ data/ ?material=Aluminum_Brass). Makeitfrom.com. Retrieved on 2011-12-09. [24] manganese brass: Definition from (http:/ / www. answers. com/ topic/ manganese-brass). Answers.com. Retrieved on 2011-12-09. [28] Print Layout 1 (http:/ / www. aquafax. co. uk/ aquafax_v2/ html/ images/ aceimages/ TechData. pdf). (PDF) . Retrieved on 2011-12-09. [29] Thornton, C. P. (2007) "Of brass and bronze in prehistoric southwest Asia" in La Niece, S. Hook, D. and Craddock, P.T. (eds.) Metals and mines: Studies in archaeometallurgy London: Archetype Publications. ISBN 1-904982-19-0 [30] de Ruette, M. (1995) "From Contrefei and Speauter to Zinc: The development of the understanding of the nature of zinc and brass in Post Medieval Europe" in Hook, D.R. and Gaimster, D.R.M (eds) Trade and Discovery: The Scientific Study of Artefacts from Post Medieval Europe and Beyond London: British Museum Occasional Papers 109 [31] Cruden's Complete Concordance p. 55 [32] Craddock, P.T. and Eckstein, K (2003) "Production of Brass in Antiquity by Direct Reduction" in Craddock, P.T. and Lang, J. (eds) Mining and Metal Production Through the Ages London: British Museum pp. 2267 [33] Rehren and Martinon Torres 2008, pp. 1705 [34] Thornton 2007, pp. 189201 [35] Craddock and Eckstein 2003 p. 217 [36] Thornton, C.P and Ehlers, C.B. (2003) "Early Brass in the ancient Near East" in IAMS Newsletter 23 pp. 2736 [37] Bayley 1990, p. 8 [38] Rehren and Martinon Torres 2008, p. 169 [39] Pliny the Elder Historia Naturalis XXXIV 2 [40] Montero-Ruis, I and Perea, A (2007) "Brasses in the early metallurgy of the Iberian Peninsula" in La Niece, S. Hook, D. and Craddock, P.T. (eds.) Metals and mines: Studies in archaeometallurgy London: Archetype: pp. 13640 [41] Craddock and Eckstein 2003, pp. 2167 [42] Craddock and Eckstein 2003, p. 217 [43] Bayley 1990, p. 9 [44] Craddock and Eckstein 2003, pp. 2224. Bayley 1990, p. 10. [45] Craddock, P.T. Burnett, A and Preston K. (1980) "Hellenistic copper-based coinage and the origins of brass" in Oddy, W.A. (ed) Scientific Studies in Numismatics British Museum Occasional Papers 18 pp. 5364 [46] Caley, E.R. (1964) Orichalcum and Related Ancient Alloys New York; American Numismatic Society

Brass
[47] Bayley 1990, p. 21 [48] Rehren and Martinon Torres 2008, pp. 1701 [49] Bayley 1990 [50] Craddock and Eckstein 2003, p. 224 [51] Craddock and Eckstein 2003, 224 [52] Caley 1964 [53] Craddock 1978, p. 14 [54] Craddock, P.T. La Niece, S.C and Hook, D. (1990) "Brass in the Medieval Islamic World" in Craddock, P.T. (ed.) 2000 Years of Zinc and Brass London: British Museum p. 73 [55] Bayley 1990, p. 22 [56] Eremin, K Graham-Campbell, J. and Wilthew, P. (2002) "Analysis of Copper alloy artefacts from Pagan Norse Graves in Scotland" in Biro, K.T and Eremin, K. (eds) Proceedings of the 31st International Symposium on Archaeometry Oxford: Archaeopress BAR pp. 3429 [57] Gilmore, G.R. and Metcalf, D.M (1980) "The alloy of the Northumbrian coinage in the mid-ninth century" in Metcalf, D and Oddy, W. Metallurgy in Numismatics 1 pp. 8398 [58] Rehren 1999 [59] Day 1990, pp. 123150 [60] Day 1990, pp. 12433 [61] Craddock and Eckstein 2003, pp. 2245 [62] Craddock et al 1990, 78 [63] Craddock et al 1990, pp. 736 [64] Craddock et al 1990, p. 75 [65] Craddock et al 1990, p. 76 [66] Rehren, T (1999) "The same...but different: A juxtaposition of Roman and Medieval brass making in Europe" in Young, S.M.M. (ed.) Metals in antiquity Oxford: Archaeopress pp. 2527 [67] Craddock and Eckstein 2003, 226 [68] Rehren and Martinon Torres 2008, pp. 1768 [69] Rehren and Martinon Torres 2008, pp. 1735 [70] Martinon Torres and Rehren 2002, pp. 95111 [71] Martinon Torres and Rehren 2002, pp. 1056 [72] Martinon Torres and Rehren 2002, p. 103 [73] Martinon Torres and Rehren 2002, p. 104 [74] Martinon Torres and Rehren 2002, p. 100 [75] Martinon Torres and Rehren 2008, 1812, de Ruette 1995 [76] de Ruette 1995, 198 [77] Craddock and Eckstein 2003, 228 [78] de Ruette 1995, 1989 [79] Craddock and Eckstein 2003, 2267. [80] Day 1990, p. 131 [81] Day 1991, pp. 13544 [82] Day 1990, p. 138 [83] Craddock and Eckstein 2003, p. 227 [84] Day 1991, pp. 17981 [85] Day 1991, p. 183 [86] Day 1991, pp. 1869 [87] Day 1991, pp. 1923, Craddock and Eckstein 2003, p. 228

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Bibliography
Bayley, J. (1990) "The Production of Brass in Antiquity with Particular Reference to Roman Britain" in Craddock, P.T. (ed.) 2000 Years of Zinc and Brass London: British Museum Craddock, P.T. and Eckstein, K (2003) "Production of Brass in Antiquity by Direct Reduction" in Craddock, P.T. and Lang, J. (eds) Mining and Metal Production Through the Ages London: British Museum Day, J. (1990) "Brass and Zinc in Europe from the Middle Ages until the 19th century" in Craddock, P.T. (ed.) 2000 Years of Zinc and Brass London: British Museum Day, J (1991) "Copper, Zinc and Brass Production" in Day, J and Tylecote, R.F (eds) The Industrial Revolution in Metals London: The Institute of Metals Martinon Torres, M. and Rehren, T. (2002). Historical Metallurgy 36 (2): 95111.

Brass Rehren, T. and Martinon Torres, M. (2008) "Naturam ars imitate: European brassmaking between craft and science" in Martinon-Torres, M and Rehren, T. (eds) Archaeology, History and Science Integrating Approaches to Ancient Material: Left Coast Press

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External links
Brass.org (http://www.brass.org)

Silver

96

Silver
Silver Ag 47

palladium silver cadmiumCu

Ag
Au Silver in the periodic table Appearance lustrous white metal

Electrolytically refined silver General properties Name, symbol, number Pronunciation Element category Group, period, block Standard atomic weight silver, Ag, 47 /slvr/ transition metal 11, 5, d 107.8682

Silver

97
Electron configuration

[Kr] 4d10 5s1 2, 8, 18, 18, 1

History Discovery before 5000 BC Physical properties Phase Density (near r.t.) Liquid density at m.p. Meltingpoint Boilingpoint Heatoffusion Heat of vaporization Molar heat capacity solid 10.49 gcm3 9.320 gcm3 1234.93K, 961.78C, 1763.2F 2435K, 2162C, 3924F 11.28 kJmol1 250.58 kJmol1 25.350 Jmol1K1 Vapor pressure P (Pa) 1 10 100 1k 10 k 100 k

at T (K) 1283 1413 1575 1782 2055 2433 Atomic properties Oxidation states Electronegativity Ionization energies 1, 2, 3 (amphoteric oxide) 1.93 (Pauling scale) 1st: 731.0 kJmol1 2nd: 2070 kJmol1 3rd: 3361 kJmol1 Atomic radius Covalent radius Van der Waals radius 144 pm 1455 pm 172 pm Miscellanea

Silver

98
Crystal structure face-centered cubic

Magnetic ordering Electrical resistivity Thermal conductivity Thermal diffusivity Thermal expansion

diamagnetic

[1]

(20C) 15.87 nm 429Wm1K1 (300 K) 174mm/s (25 C) 18.9 mm1K1

Speed of sound (thin rod) (r.t.) 2680ms1 Young's modulus Shear modulus Bulk modulus Poisson ratio Mohs hardness Vickers hardness Brinell hardness CAS registry number 83 GPa 30 GPa 100 GPa 0.37 2.5 251 MPa 206 MPa 7440-22-4 Most stable isotopes Main article: Isotopes of silver iso
105

NA syn

half-life DM DE (MeV) 41.2 d 0.344, 0.280, 0.644, 0.443 0.511, 0.717, 1.045, 0.450

DP
105

Ag

Pd

106m

Ag

syn

8.28 d

106

Pd

107

Ag 51.839% Ag syn

107

Ag is stable with 60 neutrons IT 0.109 0.433, 0.614, 0.722


108 108

108m

418 y

Pd

Ag

109 111

Ag 48.161% Ag syn

109

Ag is stable with 62 neutrons 1.036, 0.694 0.342


111

7.45 d

Cd

Silver Silver is a chemical element with the chemical symbol Ag (Greek: rguros, Latin: argentum, both from the Indo-European root *arg- for "grey" or "shining") and atomic number 47. A soft, white, lustrous transition metal, it possesses the highest electrical conductivity of any element and the highest thermal conductivity of any metal. The metal occurs naturally in its pure, free form (native silver), as an alloy with gold and other metals, and in minerals such as argentite and chlorargyrite. Most silver is produced as a byproduct of copper, gold, lead, and zinc refining. Silver has long been valued as a precious metal, used in currency coins, to make ornaments, jewelry, high-value tableware and utensils (hence the term silverware) and as an investment in the forms of coins and bullion. Silver metal is used industrially in electrical contacts and conductors, in mirrors and in catalysis of chemical reactions. Its compounds are used in photographic film and dilute silver nitrate solutions and other silver compounds are used as disinfectants and microbiocides (oligodynamic effect). While many medical antimicrobial uses of silver have been supplanted by antibiotics, further research into clinical potential continues.

99

Characteristics
Silver is produced from lighter elements in the Universe through the r-process, a form of nuclear fusion believed to take place during certain types of supernova explosions. This produces many elements heavier than iron, of which silver is one.[2] Silver is a very ductile, malleable (slightly harder than gold), monovalent coinage metal, with a brilliant white metallic luster that can take a high degree of Silver 1000oz t (~31kg) bullion bar polish. It has the highest electrical conductivity of all metals, even higher than copper, but its greater cost has prevented it from being widely used in place of copper for electrical purposes. An exception to this is in radio-frequency engineering, particularly at VHF and higher frequencies, where silver plating to improve electrical conductivity of parts, including wires, is widely employed. During World War II in the US, 13,540tons were used in the electromagnets used for enriching uranium, mainly because of the wartime shortage of copper.[3][4][5] Among metals, pure silver has the highest thermal conductivity (the nonmetal carbon in the form of diamond and superfluid helium II are higher) and one of the highest optical reflectivities.[] (Aluminium slightly outdoes silver in parts of the visible spectrum, and silver is a poor reflector of ultraviolet). Silver is the best conductor of heat and electricity of any metal on the periodic table. Silver also has the lowest contact resistance of any metal. Silver halides are photosensitive and are remarkable for their ability to record a latent image that can later be developed chemically. Silver is stable in pure air and water, but tarnishes when it is exposed to air or water containing ozone or hydrogen sulfide, the latter forming a black layer of silver sulfide which can be cleaned off with dilute hydrochloric acid.[3] The most common oxidation state of silver is +1 (for example, silver nitrate, AgNO3); the less common +2 compounds (for example, silver(II) fluoride, AgF2), and the even less common +3 (for example, potassium tetrafluoroargentate(III), KAgF4) and even +4 compounds (for example, potassium hexafluoroargentate(IV), K2AgF6)[6] are also known.

Isotopes
Naturally occurring silver is composed of two stable isotopes, 107Ag and 109Ag, with 107Ag being slightly more abundant (51.839% natural abundance). Silver's isotopes are almost equal in abundance, something which is rare in the periodic table. Silver's atomic weight is 107.8682(2) g/mol.[7][8] Twenty-eight radioisotopes have been characterized, the most stable being 105Ag with a half-life of 41.29days, 111Ag with a half-life of 7.45days, and 112 Ag with a half-life of 3.13hours. This element has numerous meta states, the most stable being 108mAg (t1/2 = 418years), 110mAg (t1/2 = 249.79days) and 106mAg (t1/2 = 8.28days). All of the remaining radioactive isotopes have half-lives of less than an hour, and the majority of these have half-lives of less than three minutes.

Silver Isotopes of silver range in relative atomic mass from 93.943 (94Ag) to 126.936 (127Ag);[9] the primary decay mode before the most abundant stable isotope, 107Ag, is electron capture and the primary mode after is beta decay. The primary decay products before 107Ag are palladium (element 46) isotopes, and the primary products after are cadmium (element 48) isotopes. The palladium isotope 107Pd decays by beta emission to 107Ag with a half-life of 6.5million years. Iron meteorites are the only objects with a high-enough palladium-to-silver ratio to yield measurable variations in 107Ag abundance. Radiogenic 107Ag was first discovered in the Santa Clara meteorite in 1978.[10] The discoverers suggest the coalescence and differentiation of iron-cored small planets may have occurred 10million years after a nucleosynthetic event. 107Pd107Ag correlations observed in bodies that have clearly been melted since the accretion of the solar system must reflect the presence of unstable nuclides in the early solar system.[11]

100

Compounds
Silver metal dissolves readily in nitric acid (HNO 3) to produce silver nitrate (AgNO 3), a transparent crystalline solid that is photosensitive and readily soluble in water. Silver nitrate is used as the starting point for the synthesis of many other silver compounds, as an antiseptic, and as a yellow stain for glass in stained glass. Silver metal does not react with sulfuric acid, which is used in jewelry-making to clean and remove copper oxide firescale from silver articles after silver soldering or annealing. Silver reacts readily with sulfur or hydrogen sulfide H 2S to produce silver sulfide, a dark-colored compound familiar as the tarnish on silver coins and other objects. Silver sulfide Ag 2S also forms silver whiskers when silver electrical contacts are used in an atmosphere rich in hydrogen sulfide. 4 Ag + O2 + 2 H2S 2 Ag2S + 2 H2O Silver chloride (AgCl) is precipitated from solutions of silver nitrate in the presence of chloride ions, and the other silver halides used in the manufacture of photographic emulsions are made in the same way, using bromide or iodide salts. Silver chloride is used in glass electrodes for pH testing and potentiometric measurement, and as a transparent cement for glass. Silver iodide has been used in attempts to seed clouds to produce rain.[3] Silver halides are highly insoluble in aqueous solutions and are used in gravimetric analytical methods.
Cessna210 equipped with a silver iodide generator for cloud seeding

Silver oxide (Ag 2O), produced when silver nitrate solutions are treated with a base, is used as a positive electrode (anode) in watch batteries. Silver carbonate

(Ag 2CO 3) is precipitated when silver nitrate is treated with sodium carbonate (Na 2CO [] 3). 2 AgNO3 + 2 OH Ag2O + H2O + 2 NO3 2 AgNO3 + Na2CO3 Ag2CO3 + 2 NaNO3 Silver fulminate (AgONC), a powerful, touch-sensitive explosive used in percussion caps, is made by reaction of silver metal with nitric acid in the presence of ethanol (C 2H 5OH). Other dangerously explosive silver compounds are silver azide (AgN

Silver
3),

101

formed by reaction of silver nitrate with sodium azide (NaN 3), and silver acetylide, formed when silver reacts with acetylene gas.
[12]

Latent images formed in silver halide crystals are developed by treatment with alkaline solutions of reducing agents such as hydroquinone, metol (4-(methylamino)phenol sulfate) or ascorbate, which reduce the exposed halide to silver metal. Alkaline solutions of silver nitrate can be reduced to silver metal by reducing sugars such as glucose, and this reaction is used to silver glass mirrors and the interior of glass Christmas ornaments. Silver halides are soluble in solutions of sodium thiosulfate (Na 2S 2O 3) which is used as a photographic fixer, to remove excess silver halide from photographic emulsions after image development.[] Silver metal is attacked by strong oxidizers such as potassium permanganate (KMnO 4) and potassium dichromate (K 2Cr 2O 7), and in the presence of potassium bromide (KBr); these compounds are used in photography to bleach silver images, converting them to silver halides that can either be fixed with thiosulfate or redeveloped to intensify the original image. Silver forms cyanide complexes (silver cyanide) that are soluble in water in the presence of an excess of cyanide ions. Silver cyanide solutions are used in electroplating of silver.[]

Applications
Many well-known uses of silver involve its precious metal properties, including currency, decorative items, and mirrors. The contrast between its bright white color and other media makes it very useful to the visual arts. It has also long been used to confer high monetary value as objects (such as silver coins and investment bars) or make objects symbolic of high social or political rank. Silver salts have been used since the Middle Ages to produce a yellow or orange colours to stained glass, and more complex decorative colour reactions can be produced by incorporating silver metal in blown, kilnformed or torchworked glass.[13]

Currency
Silver, in the form of electrum (a goldsilver alloy), was coined to produce money around 700BC by the Lydians. Later, silver was refined and coined in its pure form. Many nations used silver as the basic unit of monetary value. In the modern world, silver bullion has the ISO currency code XAG. The name of the pound sterling () reflects the fact it originally represented the value of one pound Tower weight of sterling silver; other historical currencies, such as the French livre, have similar etymologies. During the 19th century, the bimetallism that prevailed in most countries was undermined by the discovery of large deposits of silver in the Americas; fearing a sharp decrease in the value of silver and thus the currency, most states switched to a gold standard by 1900. In some languages, such as Sanskrit, Spanish, French, and Hebrew, the same word means both silver and money. The 20th century saw a gradual movement to fiat currency, with most of the world monetary system losing its link to precious metals after Richard Nixon took the United States dollar off the gold standard in 1971; the last currency backed by gold was the Swiss franc, which became a pure fiat currency on 1 May 2000. During this same period, silver gradually ceased to be used in circulating coins. In 1964, the United States stopped minting their silver dime and quarter. They minted their last circulating silver coin in 1970 in its 40% half-dollar.[] In 1968, Canada minted their last circulating silver coins which were the 50% dime and the 50% quarter. The Royal Canadian Mint still makes many collectible silver coins with various dollar denominations.

Silver Silver is used as a currency by many individuals, and is legal tender in the US state of Utah.[14] Silver coins and bullion are also used as an investment to guard against inflation and devaluation.

102

Jewelry and silverware


Jewelry and silverware are traditionally made from sterling silver (standard silver), an alloy of 92.5% silver with 7.5% copper. In the US, only an alloy consisting of at least 90.0% fine silver can be marketed as "silver" (thus frequently stamped 900). Sterling silver (stamped 925) is harder than pure silver, and has a lower melting point (893C) than either pure silver or pure copper.[3] Britannia silver is an alternative, hallmark-quality standard containing 95.8% silver, often used to make silver tableware and wrought plate. With the addition of germanium, the patented modified alloy Argentium Sterling silver is formed, with improved properties, including resistance to firescale. Sterling silver jewelry is often plated with a thin coat of .999fine silver to give the item a shiny finish. This process is called "flashing". Silver jewelry can also be plated with rhodium (for a bright, shiny look) or gold (to produce silver gilt). Silver is a constituent of almost all colored carat gold alloys and carat gold solders, giving the alloys paler color and greater hardness.[] White 9carat gold contains 62.5% silver and 37.5% gold, while 22carat gold contains a minimum of 91.7% gold and 8.3% silver or copper or other metals.[] Historically, the training and guild organization of goldsmiths included silversmiths, as well, and the two crafts remain largely overlapping. Unlike blacksmiths, silversmiths do not shape the metal while it is red-hot, but instead, work it at room temperature with gentle and carefully placed hammer blows. The essence of silversmithing is to take a flat piece of metal and to transform it into a useful object using different hammers, stakes and other simple tools.[15]

Shallow silver bowl, Persian, 6th century BC (Achaemenid). The deeper depressions reperesent lotus buds, an Egyptian motif. Walters Art Museum collections.

Silver plate with goddess Minerva from the Hildesheim Treasure, 1st century BC

While silversmiths specialize in, and principally work silver, they also work with other metals, such as gold, copper, steel, and brass. They make jewelry, silverware, armor, vases, and other artistic items. Because silver is such a malleable metal, silversmiths have a large range of choices with how they prefer to work the metal. Historically, silversmiths are mostly referred to as goldsmiths, which was usually the same guild. In the western Canadian silversmith tradition, guilds do not exist; however, mentoring through colleagues becomes a method of professional learning within a community of craftspeople.[16] Traditionally, silversmiths mostly made "silverware" (cutlery, tableware, bowls, candlesticks and such). Only in more recent times has silversmithing become mainly work in jewelry, as much less solid silver tableware is now handmade.

Silver

103

Dentistry
Silver can be alloyed with mercury at room temperature to make amalgams that are widely used for dental fillings. To make dental amalgam, a mixture of powdered silver and other metals such as tin and gold is mixed with mercury to make a stiff paste that can be adapted to the shape of a cavity. The dental amalgam achieves initial hardness within minutes, and sets hard in a few hours.

Photography and electronics


Photography used 30.98% of the silver consumed in 1998 in the form of silver nitrate and silver halides. In 2001, 23.47% was used for photography, while 20.03% was used in jewelry, 38.51% for industrial uses, and only 3.5% for coins and medals. The use of silver in photography has rapidly declined, due to the lower demand for consumer color film from the advent of digital technology; since 2007, of the 907million ounces of silver in supply, just 117.6million ounces (13%) were consumed by the photographic sector, about 50% of the amount used in photography in 1998. By 2010, the supply had increased by about 10% to 1056.8million ounces, of which 72.7million ounces were used in the photographic sector, a decline of 38% compared with 2007.[17] Some electrical and electronic products use silver for its superior conductivity, even when tarnished. The primary example of this is in high quality RF connectors. The increase in conductivity is also taken advantage of in RF engineering at VHF and higher frequencies, where conductors often cannot be scaled by 6%, due to tuning requirements, e.g. cavity filters. As an additional example, printed circuits and RFID antennas can be made using silver paints,[3][18] and computer keyboards use silver electrical contacts. Silver cadmium oxide is used in high-voltage contacts because it can withstand arcing. Some manufacturers produce audio connector cables, speaker wires, and power cables using silver conductors, which have a 6% higher conductivity than ordinary copper ones of identical dimensions, but cost much more. Though debatable, many hi-fi enthusiasts believe silver wires improve sound quality.[citation needed] Small devices, such as hearing aids and watches, commonly use silver oxide batteries due to their long life and high energy-to-weight ratio. Another usage is high-capacity silver-zinc and silver-cadmium batteries.

Mirrors and optics


Mirrors which need superior reflectivity for visible light are commonly made with silver as the reflecting material in a process called silvering, though common mirrors are backed with aluminium. Using a process called sputtering, silver, along with other optically transparent layers, is applied to glass, creating low emissivity coatings used in high-performance insulated glazing. The amount of silver used per window is small because the silver layer is only 1015 nanometers thick.[19] However, the amount of silver-coated glass worldwide is hundreds of millions of square meters per year, leading to silver consumption on the order of 10 cubic meters or 100 metric tons/year. Silver color seen in architectural glass and tinted windows on vehicles is produced by sputtered chrome, stainless steel or other alloys. Silver is seldom used as the reflector in telescope mirrors, where aluminum is generally preferred because it is cheaper and less susceptible to tarnishing and corrosion.[20] Silver is the reflective coating of choice for solar reflectors.[21]

Silver

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Other industrial and commercial applications


Silver and silver alloys are used in the construction of high-quality musical wind instruments of many types.[22] Flutes, in particular, are commonly constructed of silver alloy or silver plated, both for appearance and for the frictional surface properties of silver.[23] Silver's catalytic properties make it ideal for use as a catalyst in oxidation reactions, for example, the production of formaldehyde from methanol and air by means of silver screens or crystallites containing a minimum 99.95weight-percent silver. Silver (upon some suitable support) is probably the only catalyst available today to convert ethylene to ethylene oxide (later hydrolyzed to ethylene glycol, used for making polyesters) an important industrial reaction. It is also used in the Oddy test to detect reduced sulfur compounds and carbonyl sulfides.

This Yanagisawa A9932J alto saxophone has a solid silver bell and neck with a solid phosphor bronze body. The bell, neck, and key-cups are extensively engraved. It was manufactured in 2008.

Because silver readily absorbs free neutrons, it is commonly used to make control rods to regulate the fission chain reaction in pressurized water nuclear reactors, generally in the form of an alloy containing 80% silver, 15% indium, and 5% cadmium. Silver is used to make solder and brazing alloys, and as a thin layer on bearing surfaces can provide a significant increase in galling resistance and reduce wear under heavy load, particularly against steel.

Biology
Silver stains are used in biology to increase the contrast and visibility of cells and organelles in microscopy. Camillo Golgi used silver stains to study cells of the nervous system and the Golgi apparatus.[24] Silver stains are used to stain proteins in gel electrophoresis and polyacrylamide gels, either as primary stains or to enhance the visibility and contrast of colloidal gold stain.[25]

Medicine
The medical uses of silver include its incorporation into wound dressings, and its use as an antibiotic coating in medical devices. Wound dressings containing silver sulfadiazine or silver nanomaterials may be used to treat external infections. Silver is also used in some medical applications, such as urinary catheters and endotracheal breathing tubes, where there is tentative evidence that it is effective in reducing catheter-related urinary tract infections and ventilator-associated pneumonia respectively.[26] The silver ion (Ag+ ) is bioactive and in sufficient concentration readily kills bacteria in vitro. Silver and silver nanoparticles are used as an antimicrobial in a variety of industrial, healthcare and domestic applications.[27]

Investing
Silver coins and bullion are used for investing. Mints sell a wide variety of silver products for investors and collectors. Various institutions provide safe storage for large physical silver investments, and various types of silver investments can be made on the stock markets, including mining stocks. Silver bullion bars are sold in a wide range of ounces, provided by various mints and mines around the world. Silver coins and bullion bars are generally 99.9% pure, and labeled with ".999".

Silver

105

Clothing
Silver inhibits the growth of bacteria and fungi on clothing, such as socks, so is sometimes added to reduce odors and the risk of bacterial and fungal infections. It is incorporated into clothing or shoes either by integrating silver nanoparticles into the polymer from which yarns are made or by coating yarns with silver.[28][29] The loss of silver during washing varies between textile technologies, and the resultant effect on the environment is not yet fully known.[30][31]

History
Silver has been used for thousands of years for ornaments and utensils, trade, and as the basis for many monetary systems. Its value as a precious metal was long considered second only to gold. The word "silver" appears in Anglo-Saxon in various spellings, such as seolfor and siolfor. A similar form is seen throughout the Germanic languages (compare Old High German silabar and silbir). The chemical symbol Ag is from the Latin word for "silver", argentum (compare Greek , rgyros), from the Indo-European root *arg-, meaning "white" or "shining". Silver has been known since ancient times. Mentioned in the Book of Genesis, slag heaps found in Asia Minor and on the islands of the Aegean Sea indicate silver was being separated from lead as early as the 4th millennium BC using surface mining.[3]

The crescent moon has been used since ancient times to represent silver.

The stability of the Roman currency relied to a high degree on the supply of silver bullion, which Roman miners produced on a scale unparalleled before the discovery of the New World. Reaching a peak production of 200 t per year, an estimated silver stock of 10,000 t circulated in the Roman economy in the middle of the second century AD, five to ten times larger than the combined amount of silver available to medieval Europe and the Caliphate around 800 AD.[32][33] Financial officials of the Roman Empire worried about the loss of silver to pay for highly demanded silk from Sinica (China). Mines were made in Laureion during 483 BC.[34] In the Gospels, Jesus' disciple Judas Iscariot is infamous for having taken a bribe of 30 coins of silver from religious leaders in Jerusalem to turn Jesus of Nazareth over to soldiers of the High Priest Caiaphas.[35] The Chinese Empire during most of its history primarily used silver as a means of exchange. In the 19th century, the threat to the balance of payments of the United Kingdom from Chinese merchants demanding payment in silver in exchange for tea, silk, and porcelain led to the Opium War because Britain had to find a way to address the imbalance in payments, and they decided to do so by selling opium produced in their colony of British India to China.[36] Recorded use of silver to prevent infection dates to ancient Greece and Rome; it was rediscovered in the Middle Ages, when it was used for several purposes, such as to disinfect water and food during storage, and also for the treatment of burns and wounds as wound dressing. In the 19th century, sailors on long ocean voyages would put silver coins in barrels of water and wine to keep the liquid potable. Pioneers in America used the same idea as they made their journey from coast to coast. Silver solutions were approved in the 1920s by the US Food and Drug Administration for use as antibacterial agents.[citation needed] In certain circumstances, Islam permits Muslim men to wear silver jewelry.[citation needed] Muhammad himself wore a silver signet ring.[37] In the Americas, high temperature silver-lead cupellation technology was developed by pre-Inca civilizations as early as CE 60120.[38]

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Folklore
In European folklore, silver was considered a mystical element, and much like Cold Iron, was considered something of an anathema towards aspects of the supernatural. The myth of silver's mystical properties goes deep into human history. Silver is believed to have purifying effects, a belief that likely arose from the observation that water kept in a silver pitcher took longer to go scummy; in modern times, silver has been shown to have antibacterial properties. As a noble metal akin to gold, this is often attributed to something along the lines of silver's "Incorruptible Pure Pureness". Due to the above, silver is almost always considered to be on the good end of magic (and items formed of it may also be "Made of Good"). In some traditions of Neopaganism, silver is the metal associated with the powers of the Moon, symbolizes the light of the moon, representing the feminine energies of the Triple Goddess. In Francis Barret's The Magus, it is said to make the bearer "amiable, pleasent, cheerful and honoured, removing all malice and ill-will; it causes security in a journey, increases the riches, and health of body drives away enemies..." In rituals, silver is said to encourage a harmonious energy and a sense of peace. In folklore, and now later in fiction, the metal is said to do many things, from channel magic, to stopping evil (including warding off or harming vampires and werewolves), making magic mirrors, to turning water into a "Healing Potion". Throughout mythology and subsequent fiction, silver has been a common ward against evil. Silver, especially if blessed, was thought to ward off or harm certain supernatural beings (including vampires) since the Middle Ages.

World War II
During World War II, the short supply of copper led to the substitution of silver in many industrial applications. The United States government loaned out silver from its massive reserve located in the West Point vaults to a wide range of industrial users. One very important use was for bus bars for new aluminum plants needed to make aircraft. During the war, many electrical connectors and switches were silver plated. Another use was aircraft master rod bearings and other types of bearings. Since silver can replace tin in solder at a lower volume, a large amount of tin was freed up for other uses by substituting government silver. Silver was also used as the reflector in searchlights and other types of lights. One high-tech use of silver was for conductors at Oak Ridge National Laboratory used in calutrons to isolate uranium as part of the Manhattan project. (After the war ended, the silver was returned to the vaults.)[39] Silver was used in nickels during the war to save that metal for use in steel alloys.[]

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Occurrence and extraction


Silver is found in native form, as an alloy with gold (electrum), and in ores containing sulfur, arsenic, antimony or chlorine. Ores include argentite (Ag2S), chlorargyrite (AgCl) which includes horn silver, and pyrargyrite (Ag3SbS3). The principal sources of silver are the ores of copper, copper-nickel, lead, and lead-zinc obtained from Peru, Bolivia, Mexico, China, Australia, Chile, Poland and Serbia.[3] Peru, Bolivia and Mexico have been mining silver since 1546, and are still major world producers. Top silver-producing mines are Cannington (Australia), Fresnillo (Mexico), San Cristobal (Bolivia), Antamina (Peru), Rudna (Poland), and Penasquito (Mexico).[] Top near-term mine development projects through 2015 are Pascua Lama (Chile), Navidad (Argentina), Jaunicipio (Mexico), Malku Khota (Bolivia),[40] and Hackett River (Canada).[]

Time trend of silver production

The metal is primarily produced as a byproduct of electrolytic copper refining, Native silver gold, nickel, and zinc refining, and by application of the Parkes process on lead metal obtained from lead ores that contain small amounts of silver. Commercial-grade fine silver is at least 99.9% pure, and purities greater than 99.999% are available. In 2011, Mexico was the top producer of silver (4,500 tonnes or 19% of the world's total), closely followed by Peru (4,000 t) and China (4,000 t).[41]

Price

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At a July 19, 2013 price of US$19.53 per troy ounce,[42] silver is approximately 1/66 the price of gold. The ratio has varied from 1/15 to 1/100 in the past 100 years.[citation needed] Physical silver bullion prices are higher than the paper prices, with premiums increasing when demand is high and local shortages occur.[43] In 1980, the silver price rose to a peak for modern times of US$49.45pertroy ounce (ozt) due to market manipulation of Nelson Bunker Hunt and Herbert Hunt. Silver price history in 19602011 Inflation-adjusted to 2012, this is approximately US$138 per troy ounce. Some time after Silver Thursday, the price was back to $10/ozt.[44] From 2001 to 2010, the price moved from $4.37 to $20.19 (average London US$/oz).[] According to the Silver Institute, silver's recent gains have greatly stemmed from a rise in investor interest and an increase in fabrication demand.[] In late April 2011, silver reached an all-time high of $49.76/ozt. In earlier times, silver has commanded much higher prices. In the early 15th century, the price of silver is estimated to have surpassed $1,200 per ounce, based on 2011 dollars.[45] The discovery of massive silver deposits in the New World during the succeeding centuries has been stated as a cause for its price to have diminished greatly. The price of silver is important in Judaic law. The lowest fiscal amount a Jewish court, or Beth Din, can convene to adjudicate a case over is a shova pruta (value of a Babylonian pruta coin).[citation needed] This is fixed at .025 grams (0.00088oz) of pure, unrefined silver, at market price. In a Jewish tradition, still continuing today, on the first birthday of a first-born son, the parents pay the price of five pure-silver coins to a Kohen (priest). Today, the Israel mint fixes the coins at 117 grams (4.1oz) of silver. The Kohen will often give those silver coins back as a gift for the child to inherit.[46]

Human exposure and consumption


Silver plays no known natural biological role in humans, and possible health effects of silver are a disputed subject. Silver itself is not toxic to humans, but most silver salts are. In large doses, silver and compounds containing it can be absorbed into the circulatory system and become deposited in various body tissues, leading to argyria, which results in a blue-grayish pigmentation of the skin, eyes, and mucous membranes. Argyria is rare, and although, so far as known, this condition does not otherwise harm a person's health, it is disfiguring and usually permanent. Mild forms of Argyria are sometimes mistaken for cyanosis.[3]

Monitoring exposure
Overexposure to silver can occur in workers in the metallurgical industry, persons taking silver-containing dietary supplements, patients who have received silver sulfadiazine treatment, and individuals who accidentally or intentionally ingest silver salts. Silver concentrations in whole blood, plasma, serum, or urine may be measured to monitor for safety in exposed workers, to confirm the diagnosis in potential poisoning victims, or to assist in the forensic investigation in a case of fatal overdosage.[47]

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Use in food
Silver is used in food coloring; it has the E174 designation and is approved in the European Union. The safety of silver for use in food is disputed.[] Traditional Indian dishes sometimes include the use of decorative silver foil known as vark,[] and in various cultures, silver drage are used to decorate cakes, cookies, and other dessert items.[] The use of silver as a food additive is not approved in the United States.[citation needed]

References
[1] Magnetic susceptibility of the elements and inorganic compounds (http:/ / www-d0. fnal. gov/ hardware/ cal/ lvps_info/ engineering/ elementmagn. pdf) in [14] Utah Law Makes Coins Worth Their Weight in Gold (or Silver) (https:/ / www. nytimes. com/ 2011/ 05/ 30/ us/ 30gold. html), New York Times, May 29, 2011 [19] Hill, Russ (1999). Coated Glass Applications and Markets. Fairfield, CA: BOC Coating Technology. pp. 14. ISBN 0-914289-01-2. [25] Oliver, C. (1994) Use of immunogold with silver enhancement methods in molecular biology. 34, 211-216. doi=10.1385/0-89603285-X:211 [26] Beattie, M; Taylor, J (2011 Aug). "Silver alloy vs. uncoated urinary catheters: a systematic review of the literature". Journal of clinical nursing 20 (1516): 2098108. doi:10.1111/j.1365-2702.2010.03561.x. PMID 21418360. name=Bou2012> [31] Washing nanotextiles: can nanosilver escape from clothes? (http:/ / ec. europa. eu/ environment/ integration/ research/ newsalert/ pdf/ 178na5. pdf), European Commission, 17 December 2009 [34] T Amemiya (p 7) Economy and Economics of Ancient Greece (http:/ / books. google. co. uk/ books?id=DcTj4AUFemAC& printsec=frontcover& dq=ancient+ history+ of+ foreign+ exchange& hl=en#v=onepage& q=ancient history of foreign exchange& f=false) Taylor & Francis, 2007 Retrieved 2012-01-18 [36] White, Matthew The Great Big Book of Horrible Things" New York: 2012 W.W. Norton "The Opium War" Page 285-286 [41] Silver Statistics and Information (http:/ / minerals. usgs. gov/ minerals/ pubs/ commodity/ silver/ ), USGS [42] Retrieved on 2013-07-20 (http:/ / www. kitcosilver. com/ ) [43] Will Precious Metal Premiums One Day Trump the Spot Price? International Business Times (http:/ / www. ibtimes. com/ articles/ 342907/ 20120518/ will-precious-metal-premiums-one-day-trump. htm). Ibtimes.com (2012-05-18). Retrieved on 2012-05-28. [45] Live Silver Prices, Silver Bullion Prices & 650 Years of Silver Prices (http:/ / goldinfo. net/ silver600. html). Goldinfo.net. Retrieved on 2011-05-02. [46] Living Judaism: the complete guide to Jewish belief, tradition, Wayne D. Dosick 1995 "The price was set at five shekalim (the plural of shekel, the monetary unit of the time) for each of the 273 extra firstborn (Numbers 3:47). The money was given to Aaron, the High Priest, the head of the tribe of Levi." [47] Baselt, R. Disposition of Toxic Drugs and Chemicals in Man, 8th edition, Biomedical Publications, Foster City, CA, 2008, ISBN 0-9626523-7-7 pp. 14291431.

External links
Chemistry in its element podcast (http://www.rsc.org/chemistryworld/podcast/element.asp) (MP3) from the Royal Society of Chemistry's Chemistry World: Silver (http://www.rsc.org/images/ CIIE_silver_48kbps_tcm18-118748.mp3) Silver (http://www.periodicvideos.com/videos/047.htm) at The Periodic Table of Videos (University of Nottingham) Society of American Silversmiths (http://www.silversmithing.com/) The Silver Institute (http://www.silverinstitute.org/) A silver industry website A collection of silver items (http://www.theodoregray.com/PeriodicTable/Elements/047/index.html) Samples of silver Transport, Fate and Effects of Silver in the Environment (http://digital.library.wisc.edu/1711.dl/EcoNatRes. Argentum) CDC - NIOSH Pocket Guide to Chemical Hazards - Silver (http://www.cdc.gov/niosh/npg/npgd0557.html) Picture in the Element collection from Heinrich Pniok (http://www.pniok.de/ag.htm)

Copper

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Copper
Copper Cu 29

nickel copper zinc

Cu
Ag Copper in the periodic table Appearance red-orange metallic luster

Native copper (~4 cm in size) General properties Name, symbol, number Pronunciation Element category Group, period, block Standard atomic weight copper, Cu, 29 /kpr/ KOP-r transition metal 11, 4, d 63.546(3)

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Electron configuration

[Ar] 3d10 4s1 2, 8, 18, 1

History Naming Discovery after Cyprus, principal mining place in Roman era (Cyprium) Middle Easterns (9000 BC) Physical properties Phase Density (near r.t.) Liquid density at m.p. Meltingpoint Boilingpoint Heatoffusion Heat of vaporization Molar heat capacity solid 8.96 gcm3 8.02 gcm3 1357.77K, 1084.62C, 1984.32F 2835K, 2562C, 4643F 13.26 kJmol1 300.4 kJmol1 24.440 Jmol1K1 Vapor pressure P (Pa) 1 10 100 1k 10 k 100 k

at T (K) 1509 1661 1850 2089 2404 2834 Atomic properties Oxidation states Electronegativity Ionization energies (more) +1, +2, +3, +4 (mildly basic oxide) 1.90 (Pauling scale) 1st: 745.5 kJmol1 2nd: 1957.9 kJmol1 3rd: 3555 kJmol1 Atomic radius Covalent radius Van der Waals radius 128 pm 1324 pm 140 pm Miscellanea

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112
Crystal structure face-centered cubic

Magnetic ordering Electrical resistivity Thermal conductivity Thermal expansion

diamagnetic

[1]

(20C) 16.78 nm 401Wm1K1 (25 C) 16.5 mm1K1

Speed of sound (thin rod) (r.t.) (annealed) 3810ms1 Young's modulus Shear modulus Bulk modulus Poisson ratio Mohs hardness Vickers hardness Brinell hardness CAS registry number 110128 GPa 48 GPa 140 GPa 0.34 3.0 369 MPa 35 HB = 874 MPa 7440-50-8 Most stable isotopes Main article: Isotopes of copper iso
63 64

NA

half-life DM DE (MeV) DP
63

Cu 69.15% Cu syn

Cu is stable with 34 neutrons 64 64

12.700 h

Ni

Zn

65 67

Cu 30.85% Cu syn

65

Cu is stable with 36 neutrons 67

61.83 h

Zn

Copper is a chemical element with the symbol Cu (from Latin: cuprum) and atomic number 29. It is a ductile metal with very high thermal and electrical conductivity. Pure copper is soft and malleable; a freshly exposed surface has a reddish-orange color. It is used as a conductor of heat and electricity, a building material, and a constituent of various metal alloys. The metal and its alloys have been used for thousands of years. In the Roman era, copper was principally mined on Cyprus, hence the origin of the name of the metal as yprium (metal of Cyprus), later shortened to uprum. Its compounds are commonly encountered as copper(II) salts, which often impart blue or green colors to minerals such as azurite and turquoise and have been widely used historically as pigments. Architectural structures built with copper corrode to give green verdigris (or patina). Decorative art prominently features copper, both by itself and as part of pigments. Copper is essential to all living organisms as a trace dietary mineral because it is a key constituent of the respiratory enzyme complex cytochrome c oxidase. In molluscs and crustacea copper is a constituent of the blood pigment hemocyanin, which is replaced by the iron-complexed hemoglobin in fish and other vertebrates. The main areas

Copper where copper is found in humans are liver, muscle and bone.[2] Copper compounds are used as bacteriostatic substances, fungicides, and wood preservatives.

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Characteristics
Physical
Copper, silver and gold are in group 11 of the periodic table, and they share certain attributes: they have one s-orbital electron on top of a filled d-electron shell and are characterized by high ductility and electrical conductivity. The filled d-shells in these elements do not contribute much to the interatomic interactions, which are dominated by the s-electrons through metallic bonds. Contrary to metals with incomplete d-shells, metallic bonds in copper are lacking a covalent character and are relatively weak. This explains the low hardness and high ductility of single crystals of copper.[] At the macroscopic scale, introduction of extended defects to the crystal lattice, such as grain boundaries, hinders flow of the material under applied stress thereby increasing its hardness. For this reason, copper is usually supplied in a fine-grained polycrystalline form, which has greater strength than monocrystalline forms.[3] The softness of copper partly explains its high electrical conductivity (59.6106S/m) and thus also high thermal conductivity, which are the second highest among pure metals at room temperature.[3] This is because the resistivity to electron transport in metals at room temperature mostly originates from scattering of electrons on thermal vibrations of the lattice, which are relatively weak for a soft metal.[] The maximum permissible current density of copper in open air is approximately 3.1106A/m2 of cross-sectional area, above which it begins to heat excessively.[4] As with other metals, if copper is placed against another metal, galvanic corrosion will occur.[5]

A copper disc (99.95% pure) made by continuous casting and etching.

Copper just above its melting point keeps its pink luster color when enough light outshines the orange incandescence color.

Together with caesium and gold (both yellow), and osmium (bluish), copper is one of only four elemental metals with a natural color other than gray or silver.[6] Pure copper is orange-red and acquires a reddish tarnish when exposed to air. The characteristic color of copper results from the electronic transitions between the filled 3d and half-empty 4s atomic shells the energy difference between these shells is such that it corresponds to orange light. The same mechanism accounts for the yellow color of gold and caesium.[]

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Chemical
Copper forms a rich variety of compounds with oxidation states +1 and +2, which are often called cuprous and cupric, respectively.[93] It does not react with water, but it slowly reacts with atmospheric oxygen forming a layer of brown-black copper oxide. In contrast to the oxidation of iron by wet air, this oxide layer stops the further, bulk corrosion. A green layer of verdigris (copper carbonate) can often be seen on old copper constructions, such as the Statue of Liberty, the largest copper statue in the world built using repouss and chasing.[7] Copper tarnishes when exposed to hydrogen sulfides and other sulfides, which react with it to form various copper sulfides on the surface.[8] Oxygen-containing ammonia solutions give water-soluble complexes with copper, as do oxygen and hydrochloric acid to form copper chlorides and acidified hydrogen peroxide to form copper(II) salts. Copper(II) chloride and copper comproportionate to form copper(I) chloride.[9]

Unoxidized copper wire (left) and oxidized copper wire (right).

Isotopes
There are 29 isotopes of copper. 63Cu and 65Cu are stable, with 63Cu comprising approximately 69% of naturally occurring copper; they both have a spin of 3/2.[] The other isotopes are radioactive, with the most stable being 67Cu with a half-life of 61.83hours.[] Seven metastable isotopes have been characterized, with 68mCu the longest-lived with a half-life of 3.8 minutes. Isotopes with a mass number above 64 decay by -, whereas those with a mass number below 64 decay by +. 64Cu, which has a half-life of 12.7 hours,

The East Tower of the Royal Observatory, Edinburgh. The contrast between the refurbished copper installed in 2010 and the green color of the original 1894 copper is clearly seen.

decays both ways.[10]


62

Cu and 64Cu have significant applications. 64Cu is a radiocontrast agent for X-ray imaging, and complexed with a chelate can be used for treating cancer. 62Cu is used in 62Cu-PTSM that is a radioactive tracer for positron emission tomography.[11]

Occurrence
Copper is synthesized in massive stars[12] and is present in the Earth's crust at a concentration of about 50 parts per million (ppm),[] where it occurs as native copper or in minerals such as the copper sulfides chalcopyrite and chalcocite, copper carbonates azurite and malachite and the copper(I) oxide mineral cuprite.[3] The largest mass of elemental copper discovered weighed 420 tonnes and was found in 1857 on the Keweenaw Peninsula in Michigan, US.[] Native copper is a polycrystal, with the largest described single crystal measuring 4.43.23.2cm.[13]

Native Copper from the Keweenaw Peninsula Michigan about 2.5 inches (6.4 cm) long

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Production
Most copper is mined or extracted as copper sulfides from large open pit mines in porphyry copper deposits that contain 0.4 to 1.0% copper. Examples include Chuquicamata in Chile, Bingham Canyon Mine in Utah, United States and El Chino Mine in New Mexico, United States. According to the British Geological Survey, in 2005, Chile was the top mine producer of copper with at least one-third world share followed by the United States, Indonesia and Peru.[3] Copper can also be recovered through the In-situ leach process. Several sites in the state of Arizona are considered prime candidates for this method.[14] The amount of copper in use is increasing and the quantity available is barely sufficient to allow all countries to reach developed world levels of usage.[15]

Chuquicamata in Chile is one of the world's largest open pit copper mines.

Reserves
Copper has been in use at least 10,000 years, but more than 96% of all copper ever mined and smelted has been extracted since 1900, and more than half was extracted in only the last 24 years. As with many natural resources, the total amount of copper on Earth is vast (around 1014 tons just in the top kilometer of Earth's crust, or about 5 million years worth at the current rate of extraction). However, only a tiny fraction of these reserves is economically viable, given present-day prices and technologies. Various estimates of existing copper reserves available for mining vary from 25 years to 60 years, depending on core assumptions such as the growth rate.[16] Recycling is a major source of copper in the modern world.[] Because of these and other factors, the future of copper production and supply is the subject of much debate, including the concept of Peak copper, analogous to Peak Oil. The price of copper has historically been unstable,[17] and it quintupled from the 60-year low of US$0.60/lb (US$1.32/kg) in June 1999 to US$3.75 per pound (US$8.27/kg) in May 2006. It dropped to US$2.40/lb (US$5.29/kg) in February 2007, then rebounded to US$3.50/lb (US$7.71/kg) in April 2007.[18] In February 2009, weakening global demand and a steep fall in commodity prices since the previous year's highs left copper prices at US$1.51/lb.[19]

World production trend

Copper output in 2005

Copper prices 20032011 in USD per tonne

Methods
The concentration of copper in ores averages only 0.6%, and most commercial ores are sulfides, especially chalcopyrite (CuFeS2) and to a lesser extent chalcocite (Cu2S).[] These minerals are concentrated from crushed ores to the level of 1015% copper by froth flotation or bioleaching.[20] Heating this material with silica in flash smelting removes much of the iron as slag. The process exploits the greater ease of converting iron sulfides into its oxides, which in turn react with the silica to form the silicate slag, which floats on top of the heated mass. The resulting copper matte consisting of Cu2S is then roasted to convert all sulfides into oxides:[] 2 Cu2S + 3 O2 2 Cu2O + 2 SO2

Copper The cuprous oxide is converted to blister copper upon heating: 2 Cu2O 4 Cu + O2 The Sudbury matte process converted only half the sulfide to oxide and then used this oxide to remove the rest of the sulfur as oxide. It was then electrolytically refined and the anode mud exploited for the platinum and gold it contained. This step exploits the relatively easy reduction of copper oxides to copper metal. Natural gas is blown across the blister to remove most of the remaining oxygen and electrorefining is performed on the resulting material to produce pure copper:[21] Cu2+ + 2 e Cu

116

Recycling
Copper, like aluminium, is 100% recyclable without any loss of quality whether in a raw state or contained in a manufactured product. In volume, copper is the third most recycled metal after iron and aluminium. It is estimated that 80% of the copper ever mined is still in use today.[22] According to the International Resource Panel's Metal Stocks in Society report, the global per capita stock of Copper in use in society is 3555kg. Much of this is in more-developed countries (140300kg per capita) rather than less-developed countries (3040kg per capita). The process of recycling copper follows roughly the same steps as is used to extract copper, but requires fewer steps. High purity scrap copper is melted in a furnace and then reduced and cast into billets and ingots; lower purity scrap is refined by electroplating in a bath of sulfuric acid.[23]

Alloys
Numerous copper alloys exist, many with important uses. Brass is an alloy of copper and zinc. Bronze usually refers to copper-tin alloys, but can refer to any alloy of copper such as aluminium bronze. Copper is one of the most important constituents of carat silver and gold alloys and carat solders used in the jewelry industry, modifying the color, hardness and melting point of the resulting alloys.[] The alloy of copper and nickel, called cupronickel, is used in low-denomination coins, often for the outer cladding. The US 5-cent coin called nickel consists of 75% copper and 25% nickel and has a homogeneous composition. The 90% copper/10% nickel alloy is remarkable by its resistance to corrosion and is used in various parts being exposed to seawater. Alloys of copper with aluminium (about 7%) have a pleasant golden color and are used in decorations.[] Some lead-free solders consist of tin alloyed with a small proportion of copper and other metals.[24]

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Compounds
Binary compounds
As for other elements, the simplest compounds of copper are binary compounds, i.e. those containing only two elements. The principal ones are the oxides, sulfides and halides. Both cuprous and cupric oxides are known. Among the numerous copper sulfides, important examples include copper(I) sulfide and copper(II) sulfide. The cuprous halides with chlorine, bromine, and iodine are known, as are the cupric halides with fluorine, chlorine, and bromine. Attempts to prepare copper(II) iodide give cuprous iodide and iodine.[93] 2 Cu2+ + 4 I 2 CuI + I2

A sample of copper(I) oxide.

Coordination chemistry
Copper, like all metals, forms coordination complexes with ligands. In aqueous solution, copper(II) exists as [Cu(H2O)6]2+. This complex exhibits the fastest water exchange rate (speed of water ligands attaching and detaching) for any transition metal aquo complex. Adding aqueous sodium hydroxide causes the precipitation of light blue solid copper(II) hydroxide. A simplified equation is: Cu2+ + 2 OH Cu(OH)2 Aqueous ammonia results in the same precipitate. Upon adding excess ammonia, the precipitate dissolves, forming tetraamminecopper(II): Cu(H2O)4(OH)2 + 4 NH3 [Cu(H2O)2(NH3)4]2+ + 2 H2O + 2 OH

Many other oxyanions form complexes; these include copper(II) acetate, copper(II) nitrate, and copper(II) carbonate. Copper(II) sulfate forms a blue crystalline pentahydrate, which is the most familiar copper compound in the laboratory. It is used in a fungicide called the Bordeaux mixture.[]

Copper(II) gives a deep blue coloration in the presence of ammonia ligands. The one used here is tetramminecopper(II) sulfate.

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118

Polyols, compounds containing more than one alcohol functional group, generally interact with cupric salts. For example, copper salts are used to test for reducing sugars. Specifically, using Benedict's reagent and Fehling's solution the presence of the sugar is signaled by a color change from blue Cu(II) to reddish copper(I) oxide.[25] Schweizer's reagent and related complexes with ethylenediamine and other amines dissolve cellulose.[26] Amino acids form very stable chelate complexes with copper(II). Many wet-chemical tests for copper ions exist, one involving potassium ferrocyanide, which gives a brown precipitate with copper(II) salts.

Organocopper chemistry

Compounds that contain a carbon-copper bond are known as organocopper compounds. They are very reactive towards oxygen to form copper(I) oxide and have many uses in chemistry. They are synthesized by treating copper(I) compounds with Grignard reagents, terminal alkynes or organolithium reagents;[27] in particular, the last reaction described produces a Gilman reagent. These can undergo substitution with alkyl halides to form coupling products; as such, they are important in the field of organic synthesis. Copper(I) acetylide is highly shock-sensitive but is an intermediate in reactions such as the Cadiot-Chodkiewicz coupling[28] and the Sonogashira coupling.[29] Conjugate addition to enones[30] and carbocupration of alkynes[31] can also be achieved with organocopper compounds. Copper(I) forms a variety of weak complexes with alkenes and carbon monoxide, especially in the presence of amine ligands.[32]

Ball-and-stick model of the complex [Cu(NH3)4(H2O)2]2+, illustrating the octahedral coordination geometry common for copper(II).

Copper(III) and copper(IV)


Copper(III) is most characteristically found in oxides. A simple example is potassium cuprate, KCuO2, a blue-black solid. The best studied copper(III) compounds are the cuprate superconductors. Yttrium barium copper oxide (YBa2Cu3O7) consists of both Cu(II) and Cu(III) centres. Like oxide, fluoride is a highly basic anion and is known to stabilize metal ions in high oxidation states. Indeed, both copper(III) and even copper(IV) fluorides are known, K3CuF6 and Cs2CuF6, respectively.[93] Some copper proteins form oxo complexes, which also feature copper(III).[33] With di- and tripeptides, purple-colored copper(III) complexes are stabilized by the deprotonated amide ligands.[34] Complexes of copper(III) are also observed as intermediates in reactions of organocopper compounds.

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History
Copper Age
Copper occurs naturally as native copper and was known to some of the oldest civilizations on record. It has a history of use that is at least 10,000 years old, and estimates of its discovery place it at 9000 BC in the Middle East;[] a copper pendant was found in northern Iraq that dates to 8700 BC.[35] There is evidence that gold and meteoric iron (but not iron smelting) were the only metals used by humans before copper.[] The history of copper metallurgy is thought to have followed the following sequence: 1) cold working of native copper, 2) A corroded copper ingot from Zakros, Crete, annealing, 3) smelting, and 4) the lost wax method. In southeastern shaped in the form of an animal skin typical in Anatolia, all four of these metallurgical techniques appears more or that era. less simultaneously at the beginning of the Neolithic c. 7500 BC.[] However, just as agriculture was independently invented in several parts of the world (including Pakistan, China, and the Americas) copper smelting was invented locally in several different places. It was probably discovered independently in China before 2800 BC, in Central America perhaps around 600 AD, and in West Africa about the 9th or 10th century AD.[36] Investment casting was invented in 45004000 BC in Southeast Asia[] and carbon dating has established mining at Alderley Edge in Cheshire, UK at 2280 to 1890 BC.[37] tzi the Iceman, a male dated from 33003200 BC, was found with an axe Copper ore (chrysocolla) in Cambrian sandstone with a copper head 99.7% pure; high levels of arsenic in his hair from Chalcolithic mines in the Timna Valley, southern Israel. suggest his involvement in copper smelting.[] Experience with copper has assisted the development of other metals; in particular, copper smelting led to the discovery of iron smelting.[] Production in the Old Copper Complex in Michigan and Wisconsin is dated between 6000 and 3000 BC.[38][39] Natural bronze, a type of copper made from ores rich in silicon, arsenic, and (rarely) tin, came into general use in the Balkans around 5500 BC.

Bronze Age
Alloying copper with tin to make bronze was first practiced about 4000 years after the discovery of copper smelting, and about 2000 years after "natural bronze" had come into general use. Bronze artifacts from Sumerian cities and Egyptian artifacts of copper and bronze alloys date to 3000 BC.[] The Bronze Age began in Southeastern Europe around 37003300 BC, in Northwestern Europe about 2500 BC. It ended with the beginning of the Iron Age, 20001000 BC in the Near East, 600 BC in Northern Europe. The transition between the Neolithic period and the Bronze Age was formerly termed the Chalcolithic period (copper-stone), with copper tools being used with stone tools. This term has gradually fallen out of favor because in some parts of the world the Chalcolithic and Neolithic are coterminous at both ends. Brass, an alloy of copper and zinc, is of much more recent origin. It was known to the Greeks, but became a significant supplement to bronze during the Roman Empire.[]

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Antiquity and Middle Ages


In Greece, copper was known by the name chalkos (). It was an important resource for the Romans, Greeks and other ancient peoples. In Roman times, it was known as aes Cyprium, aes being the generic Latin term for copper alloys and Cyprium from Cyprus, where much copper was mined. The phrase was simplified to cuprum, hence the English copper. Aphrodite and Venus represented copper in mythology and alchemy, because of its lustrous beauty, its ancient use in producing mirrors, and its association with Cyprus, which was sacred to the goddess. The seven heavenly bodies known to the ancients were associated with the seven metals known in antiquity, and Venus was assigned to copper.[40] Britain's first use of brass occurred around the 3rd2nd century BC. In North America, copper mining began with marginal workings by Native Americans. Native copper is known to have been extracted from sites on Isle Royale with primitive stone tools between 800 and 1600.[41] Copper metallurgy was flourishing in South America, particularly in Peru around 1000 AD; it proceeded at a much slower rate on other continents. Copper burial ornamentals from the 15th century have been uncovered, but the metal's commercial production did not start until the early 20th century. The cultural role of copper has been important, particularly in currency. Romans in the 6th through 3rd centuries BC used copper lumps as money. At first, the copper itself was valued, but gradually the shape and look of the copper became more important. Julius Caesar had his own coins made from brass, while Octavianus Augustus Caesar's coins were made from Cu-Pb-Sn alloys. With an estimated annual output of around 15,000 t, Roman copper mining and smelting activities reached a scale unsurpassed until the time of the Industrial Revolution; the provinces most intensely mined were those of Hispania, Cyprus and in Central Europe.[42][43] The gates of the Temple of Jerusalem used Corinthian bronze made by depletion gilding. It was most prevalent in Alexandria, where alchemy is thought to have begun.[44] In ancient India, copper was used in the holistic medical science Ayurveda for surgical instruments and other medical equipment. Ancient Egyptians (~2400 BC) used copper for sterilizing wounds and drinking water, and later on for headaches, burns, and itching. The Baghdad Battery, with copper cylinders soldered to lead, dates back to 248 BC to AD 226 and resembles a galvanic cell, leading people to believe this was the first battery; the claim has not been verified.[45]
Chalcolithic copper mine in Timna Valley, Negev Desert, Israel.

In alchemy the symbol for copper was also the symbol for the goddess and planet Venus.

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Modern period
The Great Copper Mountain was a mine in Falun, Sweden, that operated from the 10th century to 1992. It produced two thirds of Europe's copper demand in the 17th century and helped fund many of Sweden's wars during that time.[46] It was referred to as the nation's treasury; Sweden had a copper backed currency.[47] The uses of copper in art were not limited to currency: it was used by Renaissance sculptors, in photographic technology known as the daguerreotype, and the Statue of Liberty. Copper plating and copper sheathing for ships' hulls was widespread; the ships of Christopher Columbus were among the earliest to have this feature.[48] The Norddeutsche Affinerie in Hamburg was the first modern electroplating plant starting its production in 1876.[49] The German scientist Gottfried Osann invented powder metallurgy in 1830 while determining the metal's atomic mass; around then it was discovered that the amount and type of alloying element (e.g., tin) to copper would affect bell tones. Flash smelting was developed by Outokumpu in Finland and first applied at Harjavalta in 1949; the energy-efficient process accounts for 50% of the worlds primary copper production.[50]

Acid mine drainage affecting the stream running from the disused Parys Mountain copper mines

The Intergovernmental Council of Copper Exporting Countries, formed in 1967 with Chile, Peru, Zaire and Zambia, played a similar role for copper as OPEC does for oil. It never achieved the same influence, particularly because the second-largest producer, the United States, was never a member; it was dissolved in 1988.[51]

Applications
The major applications of copper are in electrical wires (60%), roofing and plumbing (20%) and industrial machinery (15%). Copper is mostly used as a pure metal, but when a higher hardness is required it is combined with other elements to make an alloy (5% of total use) such as brass and bronze.[] A small part of copper supply is used in production of compounds for nutritional supplements and fungicides in agriculture.[][] Machining of copper is possible, although it is usually necessary to use an alloy for intricate parts to get good machinability characteristics.

Assorted copper fittings

Wire and cable


Despite competition from other materials, copper remains the preferred electrical conductor in nearly all categories of electrical wiring with the major exception being overhead electric power transmission where aluminium is often preferred.[52][53] Copper wire is used in power generation, power transmission, power distribution, telecommunications, electronics circuitry, and countless types of electrical equipment.[54] Electrical wiring is the most important market for the copper industry.[55] This includes building wire, communications cable, power distribution cable, appliance wire, automotive wire and cable, and magnet wire. Roughly half of all copper mined is used to manufacture electrical wire and cable conductors.[56] Many electrical devices rely on copper wiring because of its multitude of inherent beneficial properties, such as its high electrical conductivity, tensile strength, ductility, creep (deformation) resistance, corrosion resistance, low thermal expansion, high thermal conductivity, solderability,

Copper and ease of installation.

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Electronics and related devices


Integrated circuits and printed circuit boards increasingly feature copper in place of aluminium because of its superior electrical conductivity (see Copper interconnect for main article); heat sinks and heat exchangers use copper as a result of its superior heat dissipation capacity to aluminium. Electromagnets, vacuum tubes, cathode ray tubes, and magnetrons in microwave ovens use copper, as do wave guides for microwave radiation.[57]

Electric motors
Coppers greater conductivity versus other metallic materials enhances the electrical energy efficiency of motors.[58] This is important because motors and motor-driven systems account for 43%-46% of all global electricity consumption and 69% of all electricity used by industry.[59] Increasing the mass and cross section of copper in a coil increases the Copper electrical busbars distributing power to a electrical energy efficiency of the motor. Copper motor rotors, a new large building technology designed for motor applications where energy savings are [60][61] prime design objectives, are enabling general-purpose induction motors to meet and exceed National Electrical Manufacturers Association (NEMA) premium efficiency standards.[62]

Architecture
Copper has been used since ancient times as a durable, corrosion resistant, and weatherproof architectural material.[63][64][65][66] Roofs, flashings, rain gutters, downspouts, domes, spires, vaults, and doors have been made from copper for hundreds or thousands of years. Coppers architectural use has been expanded in modern times to include interior and exterior wall cladding, building expansion joints, radio frequency shielding, and antimicrobial indoor products, such as attractive handrails, bathroom fixtures, and counter tops. Some of coppers other important benefits as an architectural material include its low thermal movement, light weight, lightning protection, and its recyclability.

Copper roof on the Minneapolis City Hall, coated with patina

The metals distinctive natural green patina has long been coveted by architects and designers. The final patina is a particularly durable layer that is highly resistant to atmospheric corrosion, thereby protecting the underlying metal against further weathering.[67][68][69] It can be a mixture of carbonate and sulfate compounds in various amounts, depending upon environmental conditions such as sulfur-containing acid rain.[70][71][72][73][74] Architectural copper and its alloys can also be 'finished' to embark a particular look, feel, and/or color. Finishes include mechanical surface treatments, chemical coloring, and coatings.[75]

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Copper has excellent brazing and soldering properties and can be welded; the best results are obtained with gas metal arc welding.[76]

Antibiofouling applications
Copper has long been used as a biostatic surface to line parts of ships to protect against barnacles and mussels. It was originally used pure, but has since been superseded by Muntz metal. Bacteria will not grow on a copper surface because it is biostatic. Similarly, as discussed in copper alloys in aquaculture, copper alloys have become important netting materials in the aquaculture industry because of the fact that they are antimicrobial and prevent biofouling, even in extreme conditions[77] and have strong structural and corrosion-resistant[78] properties in marine environments.

Old copper utensils in a Jerusalem restaurant

Antimicrobial applications
Numerous antimicrobial efficacy studies have been conducted in the past 10 years regarding coppers efficacy to destroy a wide range of bacteria, as well as influenza A virus, adenovirus, and fungi.[79] Copper-alloy touch surfaces have natural intrinsic properties to destroy a wide range of microorganisms (e.g., E. coli O157:H7, methicillin-resistant Staphylococcus aureus (MRSA), Staphylococcus, Clostridium difficile, influenza A virus, adenovirus, and fungi).[79] Some 355 copper alloys were proven to kill more than 99.9% of disease-causing bacteria within just two hours when cleaned regularly.[80] The United States Environmental Protection Agency (EPA) has approved the registrations of these copper alloys as antimicrobial materials with public health benefits,"[80] which allows manufacturers to legally make claims as to the positive public health benefits of products made with registered antimicrobial copper alloys. In addition, the EPA has approved a long list of antimicrobial copper products made from these alloys, such as bedrails, handrails, over-bed tables, sinks, faucets, door knobs, toilet hardware, computer keyboards, health club equipment, shopping cart handles, etc. (for a comprehensive list of products, see: Antimicrobial copper-alloy touch surfaces#Approved products). Copper doorknobs are used by hospitals to reduce the transfer of disease, and Legionnaires' disease is suppressed by copper tubing in plumbing systems.[81] Antimicrobial copper alloy products are now being installed in healthcare facilities in the U.K., Ireland, Japan, Korea, France, Denmark, and Brazil and in the subway transit system in Santiago, Chile, where copper-zinc alloy handrails will be installed in some 30 stations between 20112014.[82][83][84]

Other uses
Copper compounds in liquid form are used as a wood preservative, particularly in treating original portion of structures during restoration of damage due to dry rot. Together with zinc, copper wires may be placed over non-conductive roofing materials to discourage the growth of moss. Textile fibers use copper to create antimicrobial protective fabrics,[85] as do ceramic glazes, stained glass and musical instruments. Electroplating commonly uses copper as a base for other metals such as nickel. Copper is one of three metals, along with lead and silver, used in a museum materials testing procedure called the Oddy test. In this procedure, copper is used to detect chlorides, oxides, and sulfur compounds.

Copper Copper is commonly used in jewelry, and folklore says that copper bracelets relieve arthritis symptoms.[86] Copper is the principal alloying metal in sterling silver and gold alloys. It may also be used on its own, or as a constituent of brass, bronze, gilding metal and many other base metal alloys. Copper is used as the printing plate in etching, engraving and other forms of intaglio (printmaking) printmaking Copper oxide and carbonate is used in glassmaking and in ceramic glazes to impart green and brown colors.

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Biological role
Copper proteins have diverse roles in biological electron transport and oxygen transportation, processes that exploit the easy interconversion of Cu(I) and Cu(II).[87] [88] [89] The biological role for copper commenced with the appearance of oxygen in earth's atmosphere.[90] The protein hemocyanin is the oxygen carrier in most mollusks and some arthropods such as the horseshoe crab (Limulus polyphemus).[] Because hemocyanin is blue, these organisms have blue blood, not the red blood found in organisms that rely on hemoglobin for this purpose. Structurally related to hemocyanin are the laccases and tyrosinases. Instead of reversibly binding oxygen, these proteins hydroxylate substrates, illustrated by their role in the formation of lacquers.[89]

Copper is also a component of other proteins associated with the processing of oxygen. In cytochrome c oxidase, which is required for aerobic respiration, copper and iron cooperate in the reduction of oxygen. Copper is also found in many superoxide dismutases, proteins that catalyze the decomposition of superoxides, by converting it (by disproportionation) to oxygen and hydrogen peroxide: 2 HO2 H2O2 + O2 Several copper proteins, such as the "blue copper proteins", do not interact directly with substrates, hence they are not enzymes. These proteins relay electrons by the process called electron transfer.[89]

Rich sources of copper include oysters, beef and lamb liver, Brazil nuts, blackstrap molasses, cocoa, and black pepper. Good sources include lobster, nuts and sunflower seeds, green olives, avocados, and wheat bran.

Dietary needs
Copper is an essential trace element in plants and animals, but not some microorganisms. The human body contains copper at a level of about 1.4 to 2.1mg per kg of body mass.[] Stated differently, the RDA for copper in normal healthy adults is quoted as 0.97mg/day and as 3.0mg/day.[91] Copper is absorbed in the gut, then transported to the liver bound to albumin.[92] After processing in the Photosynthesis functions by an elaborate electron transport chain within the thylakoid membrane. A central "link" in this chain is plastocyanin, a blue copper protein. liver, copper is distributed to other tissues in a second phase. Copper transport here involves the protein ceruloplasmin, which carries the majority of copper in blood. Ceruloplasmin also carries copper that is excreted in milk, and is particularly well-absorbed as a copper source.[93] Copper in the body

Copper normally undergoes enterohepatic circulation (about 5mg a day, vs. about 1mg per day absorbed in the diet and excreted from the body), and the body is able to excrete some excess copper, if needed, via bile, which carries some copper out of the liver that is not then reabsorbed by the intestine.[94][95]

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Copper-based disorders
Because of its role in facilitating iron uptake, copper deficiency can produce anemia-like symptoms, neutropenia, bone abnormalities, hypopigmentation, impaired growth, increased incidence of infections, osteoporosis, hyperthyroidism, and abnormalities in glucose and cholesterol metabolism. Conversely, Wilson's disease causes an accumulation of copper in body tissues. Severe deficiency can be found by testing for low plasma or serum copper levels, low ceruloplasmin, and low red blood cell superoxide dismutase levels; these are not sensitive to marginal copper status. The "cytochrome c oxidase activity of leucocytes and platelets" has been stated as another factor in deficiency, but the results have not been confirmed by replication.[]
NFPA 704

Fire diamond for copper metal

Gram quantities of various copper salts have been taken in suicide attempts and produced acute copper toxicity in humans, possibly due to redox cycling and the generation of reactive oxygen species that damage DNA.[96] Corresponding amounts of copper salts (30mg/kg) are toxic in animals.[97] A minimum dietary value for healthy growth in rabbits has been reported to be at least 3 ppm in the diet.[98] However, higher concentrations of copper (100 ppm, 200 ppm, or 500 ppm) in the diet of rabbits may favorably influence feed conversion efficiency, growth rates, and carcass dressing percentages.[99] Chronic copper toxicity does not normally occur in humans because of transport systems that regulate absorption and excretion. Autosomal recessive mutations in copper transport proteins can disable these systems, leading to Wilson's disease with copper accumulation and cirrhosis of the liver in persons who have inherited two defective genes.[]

References
[1] Magnetic susceptibility of the elements and inorganic compounds (http:/ / www-d0. fnal. gov/ hardware/ cal/ lvps_info/ engineering/ elementmagn. pdf) in [14] http:/ / www. azcentral. com/ arizonarepublic/ business/ articles/ 2011/ 06/ 19/ 20110619copper-new-method-fight. html [23] "Overview of Recycled Copper" Copper.org (http:/ / www. copper. org/ publications/ newsletters/ innovations/ 1998/ 06/ recycle_overview. html). Copper.org (2010-08-25). Retrieved on 2011-11-08. [24] Balver Zinn Solder Sn97Cu3 (http:/ / www. balverzinn. com/ downloads/ Solder_Sn97Cu3. pdf). (PDF) . balverzinn.com. Retrieved on 2011-11-08. [25] Ralph L. Shriner, Christine K. F. Hermann, Terence C. Morrill, David Y. Curtin, Reynold C. Fuson "The Systematic Identification of Organic Compounds" 8th edition, J. Wiley, Hoboken. ISBN 0-471-21503-1 [26] Kay Saalwchter, Walther Burchard, Peter Klfers, G. Kettenbach, and Peter Mayer, Dieter Klemm, Saran Dugarmaa "Cellulose Solutions in Water Containing Metal Complexes" Macromolecules 2000, 33, 40944107. [27] "Modern Organocopper Chemistry" Norbert Krause, Ed., Wiley-VCH, Weinheim, 2002. ISBN 978-3-527-29773-3. [38] Pleger, Thomas C. "A Brief Introduction to the Old Copper Complex of the Western Great Lakes: 40001000 BC", Proceedings of the Twenty-seventh Annual Meeting of the Forest History Association of Wisconsin (http:/ / books. google. com/ books?id=6NUQNQAACAAJ), Oconto, Wisconsin, October 5, 2002, pp. 1018. [39] Emerson, Thomas E. and McElrath, Dale L. Archaic Societies: Diversity and Complexity Across the Midcontinent (http:/ / books. google. com/ books?id=awsA08oYoskC& pg=PA709), SUNY Press, 2009 ISBN 1-4384-2701-8.

Copper
[52] Pops, Horace, 2008, Processing of wire from antiquity to the future, Wire Journal International, June, pp 5866 [53] The Metallurgy of Copper Wire, http:/ / www. litz-wire. com/ pdf%20files/ Metallurgy_Copper_Wire. pdf [54] Joseph, Gnter, 1999, Copper: Its Trade, Manufacture, Use, and Environmental Status, edited by Kundig, Konrad J.A., ASM International, pps. 141192 and pps. 331375. [56] Joseph, Gnter, 1999, Copper: Its Trade, Manufacture, Use, and Environmental Status, edited by Kundig, Konrad J.A., ASM International, p.348 [58] IE3 energy-saving motors, Engineer Live, http:/ / www. engineerlive. com/ Design-Engineer/ Motors_and_Drives/ IE3_energy-saving_motors/ 22687/ [59] Energyefficiency policy opportunities for electric motordriven systems, International Energy Agency, 2011 Working Paper in the Energy Efficiency Series, by Paul Waide and Conrad U. Brunner, OECD/IEA 2011 [60] Fuchsloch, J. and E.F. Brush, (2007), Systematic Design Approach for a New Series of UltraNEMA Premium Copper Rotor Motors, in EEMODS 2007 Conference Proceedings, 1015 June,Beijing. [61] Copper motor rotor project; Copper Development Association; http:/ / www. copper. org/ applications/ electrical/ motor-rotor [62] NEMA Premium Motors, The Association of Electrical Equipment and Medical Imaging Manufacturers; http:/ / www. nema. org/ gov/ energy/ efficiency/ premium/ [63] Seale, Wayne (2007). The role of copper, brass, and bronze in architecture and design; Metal Architecture, May 2007 [64] Copper roofing in detail; Copper in Architecture; Copper Development Association, U.K., www.cda.org.uk/arch [65] Architecture, European Copper Institute; http:/ / eurocopper. org/ copper/ copper-architecture. html [66] Kronborg completed; Agency for Palaces and Cultural Properties, Kbenhavn, http:/ / www. slke. dk/ en/ slotteoghaver/ slotte/ kronborg/ kronborgshistorie/ kronborgfaerdigbygget. aspx?highlight=copper [68] Architectural considerations; Copper in Architecture Design Handbook, http:/ / www. copper. org/ applications/ architecture/ arch_dhb/ fundamentals/ arch_considerations. htm [69] Peters, Larry E. (2004). Preventing corrosion on copper roofing systems; Professional Roofing, October 2004, http:/ / www. professionalroofing. net [70] Oxidation Reaction: Why is the Statue of Liberty Blue-Green? Engage Students in Engineering; www.EngageEngineering.org; Chun Wu, Ph.D., Mount Marty College; Funded by the National Science Foundation (NSF) under Grant No. 083306. http:/ / www. wepanknowledgecenter. org/ c/ document_library/ get_file?folderId=517& name=DLFE-2454. pdf [71] Yahoo! Answers What is the patina of an oxidised copper coin made of? http:/ / sg. answers. yahoo. com/ question/ index?qid=20090726064632AAiDf2k [72] K.P. Fitzgerald, J. Nairn, A. Atrens (1998). The chemistry of copper patination; ScienceDirect.com Corrosion Science Volume 40, Issue 12, December 1998, Pages 20292050; http:/ / www. sciencedirect. com/ science/ article/ pii/ S0010938X98000936 [73] Application Areas: Architecture Finishes patina; http:/ / www. copper. org/ applications/ architecture/ finishes. html [74] Glossary of copper terms, Copper Development Association (UK): http:/ / www. copperinfo. co. uk/ resources/ glossary. shtml [75] Finishes natural weathering; Copper in Architecture Design Handbook, Copper Development Association Inc., http:/ / www. copper. org/ applications/ architecture/ arch_dhb/ finishes/ finishes. html [77] Edding, Mario E., Flores, Hector, and Miranda, Claudio, (1995), Experimental Usage of Copper-Nickel Alloy Mesh in Mariculture. Part 1: Feasibility of usage in a temperate zone; Part 2: Demonstration of usage in a cold zone; Final report to the International Copper Association Ltd. [78] Corrosion Behaviour of Copper Alloys used in Marine Aquaculture (http:/ / www. copper. org/ applications/ cuni/ pdf/ marine_aquaculture. pdf). (PDF) . copper.org. Retrieved on 2011-11-08. [79] Copper Touch Surfaces (http:/ / coppertouchsurfaces. org/ antimicrobial/ bacteria/ index. html). Copper Touch Surfaces. Retrieved on 2011-11-08. [80] EPA registers copper-containing alloy products (http:/ / www. epa. gov/ pesticides/ factsheets/ copper-alloy-products. htm), May 2008 [82] Chilean subway protected with Antimicrobial Copper Rail News from (http:/ / www. rail. co/ 2011/ 07/ 22/ chilean-subway-protected-with-antimicrobial-copper). rail.co. Retrieved on 2011-11-08. [83] Codelco to provide antimicrobial copper for new metro lines (Chile) (http:/ / construpages. com. ve/ nl/ noticia_nl. php?id_noticia=3032& language=en). Construpages.com.ve. Retrieved on 2011-11-08. [84] PR 811 Chilean Subway Installs Antimicrobial Copper (http:/ / www. antimicrobialcopper. com/ media/ 149689/ pr811-chilean-subway-installs-antimicrobial-copper. pdf). (PDF). antimicrobialcopper.com. Retrieved on 2011-11-08. [87] electronic-book ISBN 978-94-007-5561-1 electronic[88] electronic-book ISBN 978-94-007-5561-1 electronic[89] S. J. Lippard, J. M. Berg "Principles of bioinorganic chemistry" University Science Books: Mill Valley, CA; 1994. ISBN 0-935702-73-3.

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127

Notes
Pourbaix diagrams for copper

in pure water, or acidic or alkali conditions. Copper in neutral water is more noble than hydrogen.

in water containing sulfide

in 10 M ammonia solution

in a chloride solution

Further reading
Massaro, Edward J., ed. (2002). Handbook of Copper Pharmacology and Toxicology. Humana Press. ISBN0-89603-943-9. "Copper: Technology & Competitiveness (Summary) Chapter 6: Copper Production Technology" (http://www. princeton.edu/~ota/disk2/1988/8808/880808.PDF). Office of Technology Assessment. 2005. Current Medicinal Chemistry, Volume 12, Number 10, May 2005, pp.11611208(48) Metals, Toxicity and Oxidative Stress William D. Callister (2003). Materials Science and Engineering: an Introduction, 6th Ed. Table 6.1, p. 137: Wiley, New York. ISBN0-471-73696-1. Material: Copper (Cu), bulk (http://www.memsnet.org/material/coppercubulk/), MEMS and Nanotechnology Clearinghouse. Kim BE, Nevitt T, Thiele DJ (2008). "Mechanisms for copper acquisition, distribution and regulation" (http:// www.nature.com/nchembio/journal/v4/n3/abs/nchembio.72.html). Nat. Chem. Biol. 4 (3): 17685. doi: 10.1038/nchembio.72 (http://dx.doi.org/10.1038/nchembio.72). PMID 18277979 (http://www.ncbi.nlm. nih.gov/pubmed/18277979). Copper transport disorders (http://www.rsc.org/Publishing/Journals/cb/Volume/2009/1/Copper.asp): an Instant insight from the Royal Society of Chemistry

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External links
Copper (http://www.periodicvideos.com/videos/029.htm) at The Periodic Table of Videos (University of Nottingham) National Pollutant Inventory Copper and compounds fact sheet (http://www.npi.gov.au/substances/copper/ index.html) Copper Resource Page. (http://www.weldaloy.com/resource_center.php) Includes 12 PDF files detailing the material properties of various kinds of copper, as well as various guides and tools for the copper industry. CDC NIOSH Pocket Guide to Chemical Hazards Copper (dusts and mists) (http://www.cdc.gov/niosh/ npg/npgd0150.html) CDC NIOSH Pocket Guide to Chemical Hazards Copper fume (http://www.cdc.gov/niosh/npg/ npgd0151.html) The Copper Development Association (http://www.copper.org) has an extensive site of properties and uses of copper; it also maintains a web site dedicated to [[brass (http://www.brass.org)], a copper alloy. The Third Millennium Online page on Copper (http://www.3rd1000.com/elements/Copper.htm) Price history of copper, according to the IMF (http://www.indexmundi.com/commodities/ ?commodity=copper&months=300)

Alloy
An alloy is a mixture or metallic solid solution composed of two or more elements.[1] An alloy will contain one or more of the three: a solid solution of the elements (a single phase); a mixture of metallic phases (two or more solutions); an intermetallic compound with no distinct boundary between the phases. Solid solution alloys give a single solid phase microstructure, while partial solutions give two or more phases that may or may not be homogeneous in distribution, depending on the thermal (heat treatment) history of the material. An intermetallic compound will have another alloy or pure metal embedded within another pure metal. Alloys are used as their properties are superior to those of the pure component elements. Examples of alloys are solder, brass, pewter, phosphor bronze and amalgam. The alloy constituents are usually measured by mass. Alloys are Wire rope made from steel, which is a metal alloy usually classified as substitutional or interstitial alloys, depending on whose major component is iron, with carbon content between 0.02% and 2.14% by mass. the atomic arrangement that forms the alloy. They can be further classified as homogeneous (consisting of a single phase), or heterogeneous (consisting of two or more phases) or intermetallic (where there is no distinct boundary between phases).

Alloy

129

Introduction
An alloy is a mixture of either pure or fairly pure chemical elements, which forms an impure substance (admixture) that retains the characteristics of a metal. An alloy is distinctive from an impure metal, such as wrought iron, in that, with an alloy, the added impurities are usually desirable and will typically have some useful benefit. Alloys are made by mixing two or more elements; at least one of which being a metal. This is usually called the primary metal or the base metal, and the name of this metal may also be the name of the alloy. The other constituents may or may not be metals but, when mixed with the molten base, they will be soluble, dissolving into the mixture. When the alloy cools and solidifies (crystallizes), its mechanical properties will often be quite different from those of its individual constituents. A metal that is normally very soft and malleable, such as aluminum, can be altered by alloying it with another soft metal, like copper. Although both metals are very soft and ductile, the resulting aluminum alloy will be much harder and stronger. Adding a small amount of non-metallic carbon to iron produces an alloy called steel. Due to its very-high strength and toughness (which is much higher than pure iron), and its ability to be greatly altered by heat treatment, steel is one of the most common alloys in modern use. By adding chromium to steel, its resistance to corrosion can be enhanced, creating stainless steel, while adding silicon will alter its electrical characteristics, producing silicon steel.

Liquid bronze, being poured into molds during casting.

A gate valve, made from Inconel.

Although the elements usually must be soluble in the liquid state, they may not always be soluble in the solid state. If the metals remain soluble when solid, the alloy forms a solid solution, becoming a homogeneous structure consisting of identical crystals, called a phase. If the mixture cools and the constituents become insoluble, they may separate to form two or more different types of crystals, creating a heterogeneous microstructure of different phases. However, in other alloys, the insoluble elements may not separate until after crystallization occurs. These alloys are called intermetallic alloys because, if cooled very quickly, they first crystallizes as a homogenous phase, but they are supersaturated with the secondary constituents. As time passes, the atoms of these supersaturated alloys separate within the crystals, forming intermetallic phases that serve to reinforce the crystals internally. Some alloys occur naturally, such as electrum, which is an alloy that is native to Earth, consisting of silver and gold. Meteorites are sometimes made of naturally-occurring alloys of iron and nickel, but are not native to the Earth. One of the first alloys made by humans was bronze, which is made by mixing the metals tin and copper. Bronze was an extremely useful alloy to the ancients, because it is much stronger and harder than either of its components. Steel was another common alloy. However, in ancient times, it could only be created as an accidental byproduct from the heating of iron ore in fires (smelting) during the manufacture of iron. Other ancient alloys include pewter, brass and pig iron. In the modern age, steel can be created in many forms. Carbon steel can be made by varying only the carbon content, producing soft alloys like mild steel or hard alloys like spring steel. Alloy steels can be made by adding other elements, such as molybdenum, vanadium or nickel, resulting in alloys such as high-speed steel or tool steel. Small amounts of manganese are usually alloyed with most modern-steels because of its ability to remove unwanted impurities, like phosphorus, sulfur and oxygen, which can have detrimental effects on the alloy. However, most alloys were not created until the 1900s, such as various aluminum, titanium, nickel, and magnesium alloys.

Alloy Some modern superalloys, such as incoloy, inconel, and hastelloy, may consist of a multitude of different components.

130

Terminology
The term alloy is used to describe a mixture of atoms in which the primary constituent is a metal. The primary metal is called the base, the matrix, or the solvent. The secondary constituents are often called solutes. If there is a mixture of only two types of atoms, not counting impurities, such as a copper-nickel alloy, then it is called a binary alloy. If there are three types of atoms forming the mixture, such as iron, nickel and chromium, then it is called a ternary alloy. An alloy with four constituents is a quaternary alloy, while a five-part alloy is termed a quinary alloy. Because the percentage of each constituent can be varied, with any mixture the entire range of possible variations is called a system. In this respect, all of the various forms of an alloy containing only two constituents, like iron and carbon, is called a binary system, while all of the alloy combinations possible with a ternary alloy, such as alloys of iron, carbon and chromium, is called a ternary system.[2] Although an alloy is an impure metal, when referring to alloys, the term "impurities" usually denotes those elements which are not desired. These impurities are often found in the base metals or the solutes, but they may also be introduced during the alloying process. For instance, sulfur is a common impurity in steel. Sulfur combines readily with iron to form iron sulfide, which is very brittle, creating weak spots in the steel.[3] Lithium, sodium and calcium are common impurities in aluminum alloys, which can have adverse effects on the structural integrity of castings. Conversely, otherwise pure-metals that simply contain unwanted impurities are often called "impure metals" and are not usually referred to as alloys. Oxygen, present in the air, readily combines with most metals to form metal oxides; especially at higher temperatures encountered during alloying. Great care is often taken during the alloying process to remove excess impurities, using fluxes, chemical additives, or other methods of extractive metallurgy.[4] In practice, some alloys are used so predominantly with respect to their base metals that the name of the primary constituent is also used as the name of the alloy. For example, 14 karat gold is an alloy of gold with other elements. Similarly, the silver used in jewelry and the aluminium used as a structural building material are also alloys. The term "alloy" is sometimes used in everyday speech as a synonym for a particular alloy. For example, automobile wheels made of an aluminium alloy are commonly referred to as simply "alloy wheels", although in point of fact steels and most other metals in practical use are also alloys.

Theory

Alloy

131

Alloying a metal is done by combining it with one or more other metals or non-metals that often enhance its properties. For example, steel is stronger than iron, its primary element. The physical properties, such as density, reactivity, Young's modulus, and electrical and thermal conductivity, of an alloy may not differ greatly from those of its elements, but engineering properties such as tensile strength[5] and shear strength may be substantially different from those of the constituent materials. This is sometimes a result of the sizes of the atoms in the alloy, because larger atoms exert a compressive force on neighboring atoms, and smaller atoms exert a tensile force on their neighbors, helping the alloy resist deformation. Sometimes alloys may exhibit marked differences in behavior even when small amounts of one element are present. For example, impurities in semiconducting ferromagnetic alloys lead to different properties, as first predicted by Bronze doorknocker White, Hogan, Suhl, Tian Abrie and Nakamura.[6][7] Some alloys are made by melting and mixing two or more metals. Bronze, an alloy of copper and tin, was the first alloy discovered, during the prehistoric period now known as the bronze age; it was harder than pure copper and originally used to make tools and weapons, but was later superseded by metals and alloys with better properties. In later times bronze has been used for ornaments, bells, statues, and bearings. Brass is an alloy made from copper and zinc. Unlike pure metals, most alloys do not have a single melting point, but a melting range in which the material is a mixture of solid and liquid phases. The temperature at which melting begins is called the solidus, and the temperature when melting is just complete is called the liquidus. However, for most alloys there is a particular proportion of constituents (in rare cases two)the eutectic mixturewhich gives the alloy a unique melting point.

Substitutional and interstitial alloys

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When a molten metal is mixed with another substance, there are two mechanisms that can cause an alloy to form, called atom exchange and the interstitial mechanism. The relative size of each atom in the mix plays a primary role in determining which mechanism will occur. When the atoms are relatively similar in size, the atom exchange method usually happens, where some of the atoms composing the metallic crystals are substituted with atoms of the other constituent. This is called a substitutional alloy. Examples of substitutional alloys include bronze and brass, in which some of the copper atoms are substituted with either tin or Different atomic mechanisms of alloy formation, showing pure metal, substitutional, zinc atoms. With the interstitial interstitial, and a combination of the two. mechanism, one atom is usually much smaller than the other, so cannot successfully replace an atom in the crystals of the base metal. The smaller atoms become trapped in the spaces between the atoms in the crystal matrix, called the interstices. This is referred to as an interstitial alloy. Steel is an example of an interstitial alloy, because the very small carbon atoms fit into interstices of the iron matrix. Stainless steel is an example of a combination of interstitial and substitutional alloys, because the carbon atoms fit into the interstices, but some of the iron atoms are replaced with nickel and chromium atoms.[8]

Heat-treatable alloys
Alloys are often made to alter the mechanical properties of the base metal, to induce hardness, toughness, ductility, or other desired properties. Most metals and alloys can be work hardened by creating defects in their crystal structure. These defects are created during plastic deformation, such as hammering or bending, and are permanent unless the metal is recrystallized. However, some alloys can also have their properties altered by heat treatment. Nearly all metals can be Allotropes of iron, (alpha iron and gamma iron) softened by annealing, which recrystallizes the alloy and repairs the showing the differences in atomic arrangement. defects, but not as many can be hardened by controlled heating and cooling. Many alloys of aluminium, copper, magnesium, titanium, and nickel can be strengthened to some degree by some method of heat treatment, but few respond to this to the same degree that steel does.[8] At a certain temperature, (usually between 1,500 F (820C) and 1,600 F (870C)), the base metal of steel (iron) undergoes a change in the arrangement of the atoms in its crystal matrix, called allotropy. This allows the small carbon atoms to enter the interstices of the crystal,

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diffusing into the iron matrix. When this happens, the carbon atoms are said to be in solution, or mixed with the iron, forming a single, homogeneous, crystalline phase called austenite. If the steel is cooled slowly, the iron will gradually change into its low temperature allotrope. When this happens the carbon atoms will no longer be soluble with the iron, and will be forced to precipitate out of solution, nucleating into the spaces between the crystals. The steel then becomes heterogeneous, being formed of two phases; the carbon (carbide) phase cementite, and ferrite (iron). This type of heat treatment produces steel that is rather soft and bendable. However, if the steel is cooled quickly the carbon atoms will not have time to precipitate. When rapidly cooled, a diffusionless (martensite) transformation occurs, in which the carbon atoms become trapped in solution. This causes the iron crystals to deform intrinsically when the crystal structure tries to change to its low temperature state, making it very hard and brittle.

Conversely, most heat-treatable alloys are precipitation hardening alloys, which produce the opposite effects that steel does. When heated to form a solution and then cooled quickly, these alloys become much softer than normal, during the diffusionless transformation, and then harden as they age. The solutes in these alloys will precipitate over time, forming intermetallic phases, which are difficult to discern from the base metal. Unlike steel, in which the solid solution separates to form different crystal phases, precipitation hardening alloys separate to form different phases within the same crystal. These intermetallic alloys appear homogeneous in crystal structure, but tend to behave heterogeneous, becoming hard and somewhat brittle.[8]

Photomicrographs of steel. The top photo shows annealed (slowly cooled) steel, which forms a heterogeneous, lamellar microstructure, called pearlite, consisting of the phases cementite (light) and ferrite (dark). The bottom photo is quenched (quickly cooled) steel, in which the carbon remains trapped within the martensite crystals, creating internal stresses.

History
Meteoric iron
The use of alloys by humans started with the use of meteoric iron, a naturally occurring alloy of nickel and iron. As no metallurgic processes were used to separate iron from nickel, the alloy was used as it was.[9] Meteoric iron could be forged from a red heat to make objects such as tools, weapons, and nails. In many cultures it was shaped by cold hammering into knives and arrowheads. They were often used as anvils. Meteoric iron was very rare and valuable, and difficult for ancient people to work.[10]

Bronze and brass

A meteorite is shown below a hatchet that was forged from meteoric iron.

Iron is usually found as iron ore on Earth, except for one deposit of native iron in Greenland, which was used by the Inuit people.[11] Native copper, however, was found worldwide, along with silver, gold and platinum, which were also used to make tools, jewelry, and other objects since Neolithic times. Copper was the hardest of these metals, and the most widely distributed. It became one of the most important

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metals to the ancients. Eventually, humans learned to smelt metals such as copper and tin from ore, and, around 2500 BC, began alloying the two metals to form bronze, which is much harder than its ingredients. Tin was rare, however, being found mostly in Great Britain. In the Middle East, people began alloying copper with zinc to form brass.[12] Ancient civilizations took into account the mixture and the various properties it produced, such as hardness, toughness and melting point, under various conditions of temperature and work hardening, developing much of the information contained in modern alloy constitution diagrams.[13]

Bronze axe 1100BC

Amalgams
Mercury had been smelted from cinnabar for thousands of years. Mercury dissolves many metals, such as gold, silver, and tin, to form amalgams (an alloy in a soft paste, or liquid form at ambient temperature). Amalgams have been used since 200 BC in China for plating objects with precious metals, called gilding, such as armor and mirrors. The ancient Romans often used mercury-tin amalgams for gilding their armor. The amalgam was applied as a paste and then heated until the mercury vaporized, leaving the gold, silver, or tin behind.[14] Mercury was often used in mining, to extract precious metals like gold and silver from their ores.[15]
A brass lamp.

Precious-metal alloys
Many ancient civilizations alloyed metals for purely aesthetic purposes. In ancient Egypt and Mycenae, gold was often alloyed with copper to produce red-gold, or iron to produce a bright burgundy-gold. Silver was often found alloyed with gold. These metals were also used to strengthen each other, for more practical purposes. Quite often, precious metals were alloyed with less valuable substances as a means to deceive buyers.[16] Around 250 BC, Archimedes was commissioned by the king to find a way to check the purity of the gold in a crown, leading to the famous bath-house shouting of "Eureka!" upon the discovery of Archimedes' principle.[17]

Electrum, a natural alloy of silver and gold, was often used for making coins.

Steel and pig iron


The first known smelting of iron began in Anatolia, around 1800 BC. Called the bloomery process, it produced very soft but ductile wrought iron and, by 800 BC, the technology had spread to Europe. Pig iron, a very hard but brittle alloy of iron and carbon, was being produced in China as early as 1200 BC, but did not arrive in Europe until the Middle Ages. Pig iron has a lower melting point than iron, and was used for making cast-iron. However, these metals found little practical use until the introduction of crucible steel around 300 BC. These steels were of poor quality, and the introduction of pattern welding, around the 1st century AD, sought to balance the extreme properties of the alloys by laminating them, to create a tougher metal. Around 700 AD, the Japanese began folding bloomery-steel and cast-iron in alternating layers to increase the strength of their swords, using clay fluxes to remove slag and impurities. This method of Japanese swordsmithing produced one of the purest steel-alloys of ancient times.[13]

Alloy While the use of iron started to become more widespread around 1200 BC, mainly because of interruptions in the trade routes for tin, the metal is much softer than bronze. However, very small amounts of steel, (an alloy of iron and around 1% carbon), was always a byproduct of the bloomery process. The ability to modify the hardness of steel by heat treatment had been known since 1100 BC, and the rare material was valued for use in tool and weapon making. Because the ancients could not produce temperatures high enough to melt iron fully, the production of steel in decent quantities did not occur until the introduction of blister steel during the Middle Ages. This method introduced carbon by heating wrought iron in charcoal for long periods of time, but the penetration of carbon was not very deep, so the alloy was not homogeneous. In 1740, Benjamin Huntsman began melting blister steel in a crucible to even out the carbon content, creating the first process for the mass production of tool steel. Huntsman's process was used for manufacturing tool steel until the early 1900s.[18] With the introduction of the blast furnace to Europe in the Middle Ages, pig iron was able to be produced in much higher volumes than wrought iron. Because pig iron could be melted, people began to develop processes of reducing the carbon in the liquid pig iron to create steel. Puddling was introduced during the 1700s, where molten pig iron was stirred while exposed to the air, to remove the carbon by oxidation. In 1858, Sir Henry Bessemer developed a process of steel-making by blowing hot air through liquid pig iron to reduce the carbon content. The Bessemer process was able to produce the first large scale manufacture of steel.[18] Once the Bessemer process began to gain widespread use, other alloys of steel began to follow. Mangalloy, an alloy of steel and manganese exhibiting extreme hardness and toughness, was one of the first alloy steels, and was created by Robert Hadfield in 1882.[19]

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Precipitation-hardening alloys
In 1906, precipitation hardening alloys were discovered by Alfred Wilm. Precipitation hardening alloys, such as certain alloys of aluminium, titanium, and copper, are heat-treatable alloys that soften when quenched (cooled quickly), and then harden over time. After quenching a ternary alloy of aluminium, copper, and magnesium, Wilm discovered that the alloy increased in hardness when left to age at room temperature. Although an explanation for the phenomenon was not provided until 1919, duralumin was one of the first "age hardening" alloys to be used, and was soon followed by many others. Because they often exhibit a combination of high strength and low weight, these alloys became widely used in many forms of industry, including the construction of modern aircraft.[20]

References
[1] [2] [3] [4] [5] (http:/ / www. thefreedictionary. com/ alloy) Michael Bauccio (2005) ASM metals reference book, ASM International 2005 Steel Metallurgy for the Non-Metallurgist By John D. Verhoeven -- ASM International 2007 Page 56 ASM Specialty Handbook: Aluminum and Aluminum Alloys By Joseph R. Davis -- ASM International Page 211 Adelbert Phillo Mills, (1922) Materials of Construction: Their Manufacture and Properties, John Wiley & sons, inc, originally published by the University of Wisconsin, Madison [8] Jon L. Dossett, Howard E. Boyer (2006) Practical heat treating, ASM International, pp. 1-14 [10] Vagn Fabritius Buchwald Iron and steel in ancient times, Det Kongelige Danske Videnskabernes Selskab 2005 pp. 1322 [11] Vagn Fabritius Buchwald Iron and steel in ancient times, Det Kongelige Danske Videnskabernes Selskab 2005 pp. 35-37 [12] Vagn Fabritius Buchwald Iron and steel in ancient times, Det Kongelige Danske Videnskabernes Selskab 2005 pp. 3941 [13] Cyril Smith (1960) History of metallography, MIT Press, ISBN 0-262-69120-5 pp. 24 [14] George Rapp (2009) Archaeomineralogy (http:/ / books. google. com/ books?id=ed0yC98aAKYC& pg=PA180), Springer, p. 180 ISBN 3-540-78593-0 [15] Harry A. Miskimin (1977) The economy of later Renaissance Europe, 14601600 (http:/ / books. google. com/ books?id=QE04AAAAIAAJ& pg=PA31), Cambridge University Press, ISBN 0-521-29208-5, p. 31 [16] Paul T. Nicholson, Ian Shaw (2000) Ancient Egyptian materials and technology (http:/ / books. google. com/ books?id=Vj7A9jJrZP0C& pg=PA164), Cambridge University Press, ISBN 0-521-45257-0 pp. 164167 [17] Melvyn Kay (2008) Practical Hydraulics (http:/ / books. google. com/ books?id=xCtAV_MCD1EC& pg=PA45), Taylor and Francis, ISBN 0-415-35115-4 p. 45 [18] George Adam Roberts, George Krauss, Richard Kennedy, Richard L. Kennedy (1998) Tool steels (http:/ / books. google. com/ books?id=ScphevR_eP8C& pg=PA2), ASM International, ISBN 0-87170-599-0 pp. 23 [19] Cast steel: Austenitic Manganese Steels (http:/ / www. keytometals. com/ Articles/ Art69. htm)

Alloy
[20] http:/ / www. slideshare. net/ corematerials/ talat-lecture-1204-precipitation-hardening-2318135

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External links
Chisholm, Hugh, ed. (1911). "Alloys". Encyclopdia Britannica (11th ed.). Cambridge University Press. Surface Alloys (http://www.uni-ulm.de/~hhoster/personal/surface_alloys.html)

Tin

137

Tin
Tin Sn 50

indium tin antimonyGe

Sn
Pb Tin in the periodic table Appearance silvery (left, beta) or gray (right, alpha)

General properties Name, symbol, number Pronunciation Element category Group, period, block Standard atomic weight tin, Sn, 50 /tn/ poor metal 14, 5, p 118.710

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138
Electron configuration

[Kr] 4d10 5s2 5p2 2, 8, 18, 18, 4

History Discovery around 3500 BC Physical properties Phase Density (near r.t.) Density (near r.t.) Liquid density at m.p. Meltingpoint Boilingpoint Heatoffusion Heat of vaporization Molar heat capacity solid (white) 7.365 gcm3 (gray) 5.769 gcm3 6.99 gcm3 505.08K, 231.93C, 449.47F 2875K, 2602C, 4716F (white) 7.03 kJmol1 (white) 296.1 kJmol1 (white) 27.112 Jmol1K1 Vapor pressure P (Pa) 1 10 100 1k 10 k 100 k

at T (K) 1497 1657 1855 2107 2438 2893 Atomic properties Oxidation states Electronegativity Ionization energies 4, 3
[1]

, 2, 1

[2]

, -4 (amphoteric oxide)

1.96 (Pauling scale) 1st: 708.6 kJmol1 2nd: 1411.8 kJmol1 3rd: 2943.0 kJmol1

Atomic radius Covalent radius Van der Waals radius

140 pm 1394 pm 217 pm Miscellanea

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139
Crystal structure tetragonal

white diamond cubic

gray Magnetic ordering Electrical resistivity Thermal conductivity Thermal expansion (gray) diamagnetic (0 C) 115 nm 66.8Wm1K1 (25 C) 22.0 mm1K1
[3]

, (white) paramagnetic

Speed of sound (thin rod) (r.t.) (rolled) 2730ms1 Young's modulus Shear modulus Bulk modulus Poisson ratio Mohs hardness Brinell hardness CAS registry number 50 GPa 18 GPa 58 GPa 0.36 1.5 ~350 MPa 7440-31-5 Most stable isotopes Main article: Isotopes of tin iso
112 114 115 116 117 118 119 120 122 124 126

NA

half-life
112 114 115 116 117 118 119 120 122

DM DE (MeV)

DP

Sn 0.97% Sn 0.66% Sn 0.34% Sn 14.54% Sn 7.68% Sn 24.22% Sn 8.59% Sn 32.58% Sn 4.63% Sn 5.79% Sn trace

Sn is stable with 62 neutrons Sn is stable with 64 neutrons Sn is stable with 65 neutrons Sn is stable with 66 neutrons Sn is stable with 67 neutrons Sn is stable with 68 neutrons Sn is stable with 69 neutrons Sn is stable with 70 neutrons Sn is stable with 72 neutrons 2.2870 0.380 +
124 126

>11017 y 2.3105 y

Te

Sb

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140

Tin is a chemical element with symbolSn (for Latin: stannum) and atomic number50. It is a main group metal in group 14 of the periodic table. Tin shows chemical similarity to both neighboring group-14 elements, germanium and lead and has two possible oxidation states, +2 and the slightly more stable +4. Tin is the 49th most abundant element and has, with 10 stable isotopes, the largest number of stable isotopes in the periodic table. Tin is obtained chiefly from the mineral cassiterite, where it occurs as tin dioxide, SnO2. This silvery, malleable post-transition metal is not easily oxidized in air and is used to coat other metals to prevent corrosion. The first alloy, used in large scale since 3000 BC, was bronze, an alloy of tin and copper. After 600 BC pure metallic tin was produced. Pewter, which is an alloy of 8590% tin with the remainder commonly consisting of copper, antimony and lead, was used for flatware from the Bronze Age until the 20th century. In modern times tin is used in many alloys, most notably tin/lead soft solders, typically containing 60% or more of tin. Another large application for tin is corrosion-resistant tin plating of steel. Because of its low toxicity, tin-plated metal is also used for food packaging, giving the name to tin cans, which are made mostly of steel.

Characteristics
Physical properties
Tin is a malleable, ductile and highly crystalline silvery-white metal. When a bar of tin is bent, a crackling sound known as the tin cry can be heard due to the twinning of the crystals.[] Tin melts at a low temperature of about 232C (449.6F), which is further reduced to 177.3C (351F) for 11-nm particles.[4] -tin (the metallic form, or white tin), which is stable at and above room temperature, is malleable. In contrast, -tin (nonmetallic form, or gray tin), which is stable below 13.2C (56F), is brittle. -tin has a diamond cubic crystal structure, similar to diamond, silicon or germanium. -tin has no metallic properties at all because its atoms form a covalent structure where Droplet of solidified molten tin electrons cannot move freely. It is a dull-gray powdery material with no common uses, other than a few specialized semiconductor applications.[] These two allotropes, -tin and -tin, are more commonly known as gray tin and white tin, respectively. Two more allotropes, and , exist at temperatures above 161C (322F) and pressures above several GPa.[5] In cold conditions, -tin tends to transform spontaneously into -tin, a phenomenon known as "tin pest".[6] Although the - transformation temperature is nominally 13.2C, impurities (e.g. Al, Zn, etc.) lower the transition temperature well below 0C (32F), and upon addition of Sb or Bi the transformation may not occur at all, increasing the durability of the tin.[] Commercial grades of tin (99.8%) resist transformation because of the inhibiting effect of the small amounts of bismuth, antimony, lead and silver present as impurities. Alloying elements such as copper, antimony, bismuth, cadmium and silver increase its hardness. Tin tends rather easily to form hard, brittle intermetallic phases, which are often undesirable. It does not form wide solid solution ranges in other metals in general, and there are few elements that have appreciable solid solubility in tin. Simple eutectic systems, however, occur with bismuth, gallium, lead, thallium and zinc.[] Tin becomes a superconductor below 3.72K.[7] In fact, tin was one of the first superconductors to be studied; the Meissner effect, one of the characteristic features of superconductors, was first discovered in superconducting tin crystals.[]

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141

Chemical properties
Tin resists corrosion from water but can be attacked by acids and alkalis. Tin can be highly polished and is used as a protective coat for other metals.[] In this case the formation of a protective oxide layer is used to prevent further oxidation. This oxide layer forms on pewter and other tin alloys.[8] Tin acts as a catalyst when oxygen is in solution and helps accelerate chemical attack.[]

Isotopes
Tin is the element with the greatest number of stable isotopes, ten, being those with atomic masses of 112, 114 to 120, 122 and 124. Of these, the most abundant ones are 120Sn (at almost a third of all tin), 118Sn, and 116Sn, while the least abundant one is 115Sn. The isotopes possessing even mass numbers have no nuclear spin while the odd ones have a spin of +1/2. Tin, with its three common isotopes 115Sn, 117Sn and 119Sn, is among the easiest elements to detect and analyze by NMR spectroscopy, and its chemical shifts are referenced against SnMe [9][10] 4. This large number of stable isotopes is thought to be a direct result of tin possessing an atomic number of 50, which is a "magic number" in nuclear physics. There are 28 additional unstable isotopes that are known, encompassing all the remaining ones with atomic masses between 99 and 137. Aside from 126Sn, which has a half-life of 230,000 years, all the radioactive isotopes have a half-life of less than a year. The radioactive 100Sn is one of the few nuclides possessing a "doubly magic" nucleus and was discovered relatively recently, in 1994.[11] Another 30 metastable isomers have been characterized for isotopes between 111 and 131, the most stable of which being 121mSn, with a half-life of 43.9 years.

Etymology
The English word 'tin' is Germanic; related words are found in the other Germanic languagesGerman Zinn, Swedish tenn, Dutch tin, etc.but not in other branches of Indo-European except by borrowing (e.g. Irish tinne). Its origin is unknown.[12] The Latin name stannum originally meant an alloy of silver and lead, and came to mean 'tin' in the 4th century BCE[13]the earlier Latin word for it was plumbum candidum 'white lead'. Stannum apparently came from an earlier stgnum (meaning the same substance),[12] the origin of the Romance and Celtic terms for 'tin'.[12][14] The origin of stannum/stgnum is unknown; it may be pre-Indo-European.[15] The Meyers Konversationslexikon speculates on the contrary that stannum is derived from Cornish stean, and is proof that Cornwall in the first centuries AD was the main source of tin.

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History
Tin extraction and use can be dated to the beginnings of the Bronze Age around 3000 BC, when it was observed that copper objects formed of polymetallic ores with different metal contents had different physical properties.[16] The earliest bronze objects had tin or arsenic content of less than 2% and are therefore believed to be the result of unintentional alloying due to trace metal content in the copper ore.[] The addition of a second metal to copper increases its hardness, lowers the melting temperature, and improves the casting process by producing a more fluid melt that cools to a denser, less spongy metal.[] This was an important innovation that allowed for the much more complex shapes cast in closed moulds of the Bronze Age. Arsenical bronze objects appear first in the Near East where arsenic is commonly Ceremonial giant bronze dirk of the found in association with copper ore, but the health risks were quickly Plougrescant-Ommerschans type, Plougrescant, France, 15001300 BC. realized and the quest for sources of the much less hazardous tin ores [17] began early in the Bronze Age. This created the demand for rare tin metal and formed a trade network that linked the distant sources of tin to the markets of Bronze Age cultures.[citation
needed]

Cassiterite (SnO2), the tin oxide form of tin, was most likely the original source of tin in ancient times. Other forms of tin ores are less abundant sulfides such as stannite that require a more involved smelting process. Cassiterite often accumulates in alluvial channels as placer deposits due to the fact that it is harder, heavier, and more chemically resistant than the granite in which it typically forms.[18] These deposits can be easily seen in river banks as cassiterite is usually black, purple or otherwise dark in color, a feature exploited by early Bronze Age prospectors. It is likely that the earliest deposits were alluvial in nature, and perhaps exploited by the same methods used for panning gold in placer deposits.[citation needed]

Compounds and chemistry


In the great majority of its compounds, tin has the oxidation state II or IV.

Inorganic compounds
Halide compounds are known for both oxidation states. For Sn(IV), all four halides are well known: SnF4, SnCl4, SnBr4, and SnI4. The three heavier members are volatile molecular compounds, whereas the tetrafluoride is polymeric. All four halides are known for Sn(II) also: SnF2, SnCl2, SnBr2, and SnI2. All are polymeric solids. Of these eight compounds, only the iodides are colored.[] Tin(II) chloride (also known as stannous chloride) is the most important tin halide in a commercial sense. Illustrating the routes to such compounds, chlorine reacts with tin metal to give SnCl4 whereas the reaction of hydrochloric acid and tin gives SnCl2 and hydrogen gas. Alternatively SnCl4 and Sn combine to stannous chloride via a process called comproportionation:[19] SnCl4 + Sn 2 SnCl2 Tin can form many oxides, sulfides, and other chalcogenide derivatives. The dioxide SnO2 (cassiterite) forms when tin is heated in the presence of air.[] SnO2 is amphoteric, which means that it dissolves in both acidic and basic solutions.[20] There are also stannates with the structure [Sn(OH)6]2, like K2[Sn(OH)6], although the free stannic acid H2[Sn(OH)6] is unknown. The sulfides of tin exist in both the +2 and +4 oxidation states: tin(II) sulfide and tin(IV) sulfide (mosaic gold).

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143

Hydrides
Stannane (SnH4), where tin is in the +4 oxidation state, is unstable. Organotin hydrides are however well known, e.g. tributyltin hydride (Sn(C4H9)3H).[] These compound release transient tributyl tin radicals, rare examples of compounds of tin(III).[22]

Organotin compounds

Ball-and-stick models of the structure of solid [21] stannous chloride (SnCl2).

Organotin compounds, sometimes called stannanes, are chemical compounds with tin-carbon bonds.[23] Of the compounds of tin, the organic derivatives are the most useful commercially.[24] Some organotin compounds are highly toxic and have been used as biocides. The first organotin compound to be reported was diethyltin diiodide ((C2H5)2SnI2), reported by Edward Frankland in 1849.[25] Most organotin compounds are colorless liquids or solids that are stable to air and water. They adopt tetrahedral geometry. Tetraalkyl- and tetraaryltin compounds can be prepared using Grignard reagents:[24] SnCl 4 + 4 RMgBr R 4Sn + 4 MgBrCl The mixed halide-alkyls, which are more common and more important commercially than the tetraorgano derivatives, are prepared by redistribution reactions: SnCl 4+ R 4Sn 2 SnCl R 2 2 Divalent organotin compounds are uncommon, although more common than related divalent organogermanium and organosilicon compounds. The greater stabilization enjoyed by Sn(II) is attributed to the "inert pair effect". Organotin(II) compounds include both stannylenes (formula: R2Sn, as seen for singlet carbenes) and distannylenes (R4Sn2), which are roughly equivalent to alkenes. Both classes exhibit unusual reactions.[26]

Occurrence
Tin is generated via the long S-process in low-to-medium mass stars (with masses of 0.6 to 10 times that of Sun). It arises via beta decay of heavy isotopes of indium.[27] Tin is the 49th most abundant element in the Earth's crust, representing 2ppm compared with 75ppm for zinc, 50ppm for copper, and 14ppm for lead.[28] Tin does not occur as the native element but must be extracted from various ores. Cassiterite (SnO2) is the only commercially Sample of cassiterite, the main ore of tin. important source of tin, although small quantities of tin are recovered from complex sulfides such as stannite, cylindrite, franckeite, canfieldite, and teallite. Minerals with tin are almost always associated with granite rock, usually at a level of 1% tin oxide content.[]

Tin

144 Because of the higher specific gravity of tin dioxide, about 80% of mined tin is from secondary deposits found downstream from the primary lodes. Tin is often recovered from granules washed downstream in the past and deposited in valleys or under sea. The most economical ways of mining tin are through dredging, hydraulic methods or open cast mining. Most of the world's tin is produced from placer deposits, which may contain as little as 0.015% tin.[29]

Granular pieces of cassiterite, which are collected by placer mining

World tin mine reserves (tonnes, 2011)[]


Country China Reserves 1,500,000

Malaysia 250,000 Peru 310,000

Indonesia 800,000 Brazil Bolivia Russia Thailand 590,000 400,000 350,000 170,000

Australia 180,000 Other Total 180,000 4,800,000

About 253,000 tonnes of tin have been mined in 2011, mostly in China (110,000 t), Indonesia (51,000 t), Peru (34,600 t), Bolivia (20,700 t) and Brazil (12,000 t).[] Estimates of tin production have historically varied with the dynamics of economic feasibility and the development of mining technologies, but it is estimated that, at current consumption rates and technologies, the Earth will run out of tin that can be mined in 40 years.[30] However Lester Brown has suggested tin could run out within 20 years based on an extremely conservative extrapolation of 2% growth per year.[]

Economically recoverable tin reserves[]


Year Million tonnes 1965 4,265 1970 3,930 1975 9,060 1980 9,100 1985 3,060 1990 7,100 2000 7,100[]

Tin
2010 5,200[]

145

Secondary, or scrap, tin is also an important source of the metal. The recovery of tin through secondary production, or recycling of scrap tin, is increasing rapidly. Whereas the United States has neither mined since 1993 nor smelted tin since 1989, it was the largest secondary producer, recycling nearly 14,000 tonnes in 2006.[] New deposits are reported to be in southern Mongolia,[31] and in 2009, new deposits of tin were discovered in Colombia, South America, by the Seminole Group Colombia CI, SAS.[32][33]

Production
Tin is produced by carbothermic reduction of the oxide ore with carbon or coke. Both reverberatory furnace and electric furnace can be used.[34][35][36]

Industry
The ten largest companies produced most of world's tin in 2007. It is not clear which of these companies include tin smelted from the mine at Bisie, Democratic Republic of the Congo, which is controlled by a renegade militia and produces 15,000 tonnes. Most of the world's tin is traded on the London Metal Exchange (LME), from 8 countries, under 17 brands.[37]

Candlestick made of tin

Largest tin producing companies (tonnes)[38]


Company Yunnan Tin PT Timah Minsur Malay Polity China 2006 2007 %Change

52,339 61,129 16.7

Indonesia 44,689 58,325 30.5 Peru China 40,977 35,940 12.3 52,339 61,129 16.7

Malaysia Smelting Corp Malaysia 22,850 25,471 11.5 Thaisarco Yunnan Chengfeng Liuzhou China Tin EM Vinto Gold Bell Group Thailand China China Bolivia China 27,828 19,826 28.8 21,765 18,000 17.8 13,499 13,193 2.3 11,804 9,448 4,696 8,000 20.0 70.9

Tin

146

Price and exchanges


Tin is unique among other mineral commodities by the complex "agreements" between producer countries and consumer countries dating back to 1921. The earlier agreements tended to be somewhat informal and sporadic; they led to the First International Tin Agreement in 1956, the first of a continuously numbered series that essentially collapsed in 1985. Through this series of agreements, the International Tin Council (ITC) had a considerable effect on tin prices. The ITC supported the price of tin during periods of low prices by World production and price (US exchange) of tin. buying tin for its buffer stockpile and was able to restrain the price during periods of high prices by selling tin from the stockpile. This was an anti-free-market approach, designed to assure a sufficient flow of tin to consumer countries and a decent profit for producer countries. However, the buffer stockpile was not sufficiently large, and during most of those 29 years tin prices rose, sometimes sharply, especially from 1973 through 1980 when rampant inflation plagued many world economies.[39] During the late 1970s and early 1980s, the U.S. Government tin stockpile was in an aggressive selling mode, partly to take advantage of the historically high tin prices. The sharp recession of 198182 proved to be quite harsh on the tin industry. Tin consumption declined dramatically. The ITC was able to avoid truly steep declines through accelerated buying for its buffer stockpile; this activity required the ITC to borrow extensively from banks and metal trading firms to augment its resources. The ITC continued to borrow until late 1985, when it reached its credit limit. Immediately, a major tin crisis followed tin was delisted from trading on the London Metal Exchange for about 3 years, the ITC dissolved soon afterward, and the price of tin, now in a free-market environment, plummeted sharply to $4 per pound and remained around this level through 1990s.[39] It increased again by 2010 due to rebound in consumption following the 200809 world economic crisis, restocking and continued growth in consumption in the worlds developing economies.[] London Metal Exchange (LME) is the principal trading site for tin.[] Other tin contract markets are Kuala Lumpur Tin Market (KLTM) and Indonesia Tin Exchange (INATIN).[40]

Applications
In 2006, about half of tin produced was used in solder. The rest was divided between tin plating, tin chemicals, brass and bronze, and niche uses.[41]

World consumption of refined tin by end use, 2006

Tin

147

Solder
Tin has long been used as a solder in the form of an alloy with lead, tin accounting for 5 to 70% w/w. Tin forms a eutectic mixture with lead containing 63% tin and 37% lead. Such solders are primarily used for solders for joining pipes or electric circuits. Since the European Union Waste Electrical and Electronic Equipment Directive (WEEE Directive) and Restriction of Hazardous Substances Directive came into effect on 1 July 2006, the use of lead in such alloys has decreased. Replacing lead has many problems, including a higher melting point, and the formation of tin whiskers causing electrical problems. Tin pest A coil of lead-free solder wire can occur in lead-free solders, leading to loss of the soldered joint. Replacement alloys are rapidly being found, although problems of joint integrity remain.[42]

Tin plating
Tin bonds readily to iron and is used for coating lead or zinc and steel to prevent corrosion. Tin-plated steel containers are widely used for food preservation, and this forms a large part of the market for metallic tin. A tinplate canister for preserving food was first manufactured in London in 1812.[43] Speakers of British English call them "tins", while speakers of American English call them "cans" or "tin cans". One thus-derived use of the slang term "tinnie" or "tinny" means "can of beer". The tin whistle is so called because it was first mass-produced in tin-plated steel.[44][45]

Specialized alloys
Tin in combination with other elements forms a wide variety of useful alloys. Tin is most commonly alloyed with copper. Pewter is 8599% tin;[46] Bearing metal has a high percentage of tin as well.[47][48] Bronze is mostly copper (12% tin), while addition of phosphorus gives phosphor bronze. Bell metal is also a copper-tin alloy, containing 22% tin. Tin has also sometimes been used in coinage; for example, it once formed a single figure percentage of the American[49] and Canadian[50] pennies. Because copper is often the major metal in such coins, and zinc is sometimes present as well, these could technically be called bronze and/or brass alloys. The niobium-tin compound Nb3Sn is commercially used as wires for superconducting magnets, due to the material's high critical temperature (18K) and critical magnetic field (25T). A superconducting magnet weighing only a couple of kilograms is capable of producing magnetic fields comparable to a conventional electromagnet weighing tons.[] A addition of a few percent tin is commonly used in zirconium alloys for the cladding of nuclear fuel.[51] Most metal pipes in a pipe organ are made of varying amounts of a tin/lead alloy, with 50%/50% being the most common. The amount of tin in the pipe defines the pipe's tone, since tin is the most tonally resonant of all metalsWikipedia:Disputed
Tin plated metal from can

Pewter plate

Tin statement. When a tin/lead alloy cools, the lead cools slightly faster and produces a mottled or spotted effect. This metal alloy is referred to as spotted metal. Major advantages of using tin for pipes include its appearance, its workability, and resistance to corrosion.[52][53]

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Other applications
Punched tin, also called pierced tin, is an artisan technique originating in central Europe for creating housewares that are both functional and decorative. Decorative piercing designs exist in a wide variety, based on geography or the artisan's personal creations. Punched tin lanterns are the most common application of this artisan technique. The light of a candle shining through the pierced design creates a decorative light pattern in the room where it sits. Punched tin lanterns and other punched tin articles were created in the New World from the earliest European settlement. A well-known example is the Revere type lantern, named after Paul Revere.[54] Before the modern era, in some areas of the Alps, a goat or sheep's horn would be sharpened and a tin panel would be punched out using the alphabet and numbers from one to nine. This learning tool was known appropriately as "the horn". Modern reproductions are decorated with such motifs as hearts and tulips.

A 21st-century reproduction barn lantern made of

In America, pie safes and food safes came into use in the days before punched tin. refrigeration. These were wooden cupboards of various styles and sizes either floor standing or hanging cupboards meant to discourage vermin and insects and to keep dust from perishable foodstuffs. These cabinets had tinplate inserts in the doors and sometimes in the sides, punched out by the homeowner, cabinetmaker or a tinsmith in varying designs to allow for air circulation. Modern reproductions of these articles remain popular in North America.[55] Window glass is most often made by floating molten glass on top of molten tin (creating float glass) in order to produce a flat surface. This is called the "Pilkington process".[56] Tin is also used as a negative electrode in advanced Li-ion batteries. Its application is somewhat limited by the fact that some tin surfacesWikipedia:Avoid weasel words catalyze decomposition of carbonate-based electrolytes used in Li-ion batteries.[57] Tin(II) fluoride is added to some dental care products[58] as stannous fluoride (SnF2). Tin(II) fluoride can be mixed with calcium abrasives while the more common sodium fluoride gradually becomes biologically inactive combined with calcium compounds.[59] It has also been shown to be more effective than sodium fluoride in controlling gingivitis.[60]

Organotin compounds
Of all the chemical compounds of tin, the organotin compounds are most heavily used. Worldwide industrial production probably exceeds 50,000 tonnes.[61] PVC stabilizers The major commercial application of organotin compounds is in the stabilization of PVC plastics. In the absence of such stabilizers, PVC would otherwise rapidly degrade under heat, light, and atmospheric oxygen, to give discolored, brittle products. Tin scavenges labile chloride ions (Cl-), which would otherwise initiate loss of HCl from the plastic material.[] Typical tin compounds are carboxylic acid derivatives of dibutyltin dichloride, such as the dilaurate.[62]

Tin Biocides Organotin compounds can have a relatively high toxicity, which is both advantageous and problematic. They have been used for their biocidal effects in/as fungicides, pesticides, algaecides, wood preservatives, and antifouling agents.[] Tributyltin oxide is used as a wood preservative.[63] Tributyltin was used as additive for ship paint to prevent growth of marine organisms on ships, with use declining after organotin compounds were recognized as persistent organic pollutants with an extremely high toxicity for some marine organisms, for example the dog whelk.[64] The EU banned the use of organotin compounds in 2003,[65] while concerns over the toxicity of these compounds to marine life and their effects on the reproduction and growth of some marine species,[] (some reports describe biological effects to marine life at a concentration of 1 nanogram per liter) have led to a worldwide ban by the International Maritime Organization.[66] Many nations now restrict the use of organotin compounds to vessels over 25 meters long.[] Organic chemistry Some tin reagents are useful in organic chemistry. In the largest application, stannous chloride is a common reducing agent for the conversion of nitro and oxime groups to amines. The Stille reaction couples organotin compounds with organic halides or pseudohalides.[67] Li-ion batteries Tin forms several inter-metallic phases with Lithium metal and it makes it a potentially attractive material. Large volumetric expansion of tin upon alloying with Lithium and instability of the Tin-organic electrolyte interface at low electrochemical potentials are the greatest challenges in employing it in commercial cells. The problem was partially solved by Sony. Tin inter-metallic compound with Cobalt, mixed with carbon, has been implemented by Sony in its Nexelion cells released in late 2000's. The composition of the active materials is close to Sn0.3Co0.4C0.3. Recent research showed that only some crystalline facets of tetragonal (beta) Sn are responsible for undesirable electrochemical activity.[68]

149

Precautions
Cases of poisoning from tin metal, its oxides, and its salts are "almost unknown". On the other hand, certain organotin compounds are almost as toxic as cyanide.[24]

Notes
[3] Magnetic susceptibility of the elements and inorganic compounds (http:/ / www-d0. fnal. gov/ hardware/ cal/ lvps_info/ engineering/ elementmagn. pdf), in [4] Ink with tin nanoparticles could print future circuit boards (http:/ / www. physorg. com/ news/ 2011-04-ink-tin-nanoparticles-future-circuit. html), Physorg, April 12, 2011; [6] This conversion is known as tin disease or tin pest. Tin pest was a particular problem in northern Europe in the 18th century as organ pipes made of tin alloy would sometimes be affected during long cold winters. Some sources also say that during Napoleon's Russian campaign of 1812, the temperatures became so cold that the tin buttons on the soldiers' uniforms disintegrated over time, contributing to the defeat of the Grande Arme. [9] Only H, F, P, Tl and Xe have a higher receptivity for NMR analysis for samples containing isotopes at their natural abundance. [12] Oxford English Dictionary, 2nd edition, 1989. [13] Encyclopdia Britannica, 11th Edition, 1911, s.v. 'tin', citing H. Kopp [15] American Heritage Dictionary [20] Inorganic & Theoretical chemistry, F. Sherwood Taylor, Heineman, 6th Edition (1942) [23] Elschenbroich, C. "Organometallics" (2006) Wiley-VCH: Weinheim. ISBN 978-3-527-29390-2 [24] Graf, G. G. (2000) "Tin, Tin Alloys, and Tin Compounds" in Ullmann's Encyclopedia of Industrial Chemistry, 2005 Wiley-VCH, Weinheim [39] Carlin, James F., Jr. (1998). Significant events affecting tin prices since 1958 (http:/ / minerals. usgs. gov/ minerals/ pubs/ commodity/ tin/ 660798. pdf). USGS.

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150

References Bibliography
This article incorporates text from a publication now in the public domain: Carlin, James F., Jr. (1998). "Significant events affecting tin prices since 1958" (http://minerals.usgs.gov/minerals/pubs/commodity/tin/ 660798.pdf). U.S. National Geodetic Survey. CRC contributors (2006). David R. Lide (editor), ed. Handbook of Chemistry and Physics (87th ed.). Boca Raton, Florida: CRC Press, Taylor & Francis Group. ISBN0-8493-0487-3. Emsley, John (2001). "Tin" (http://books.google.com/?id=j-Xu07p3cKwC&printsec=frontcover). Nature's Building Blocks: An AZ Guide to the Elements. Oxford, England, UK: Oxford University Press. pp.445450. ISBN0-19-850340-7. Greenwood, N. N.; Earnshaw, A. (1997). Chemistry of the Elements (2nd ed.). Oxford: Butterworth-Heinemann. ISBN0-7506-3365-4. Heiserman, David L. (1992). "Element 50: Tin". Exploring Chemical Elements and their Compounds. New York: TAB Books. ISBN0-8306-3018-X. MacIntosh, Robert M. (1968). "Tin". In Clifford A. Hampel (editor). The Encyclopedia of the Chemical Elements. New York: Reinhold Book Corporation. pp.722732. LCCN 68-29938 (http://lccn.loc.gov/68-29938).

Stwertka, Albert (1998). "Tin". Guide to the Elements (Revised ed.). Oxford University Press. ISBN0-19-508083-1.

External links
Tin (http://www.periodicvideos.com/videos/050.htm) at The Periodic Table of Videos (University of Nottingham) Theodore Gray's Wooden Periodic Table Table (http://www.theodoregray.com/PeriodicTable/Elements/050/ index.s7.html): Tin samples and castings Base Metals: Tin (http://www.basemetals.com/html/sninfo.htm)

Solder

151

Solder

WARNING: Article could not be rendered - ouputting plain text. Potential causes of the problem are: (a) a bug in the pdf-writer software (b) problematic Mediawiki markup (c) table is too wide A soldered joint used to attach a wire to the pin of a component on the rear of a printed circuit board.Solder (/sold/, /sld/ or sometimes in USA /sdr/Oxford American Dictionary) is a fusible alloyfusible metal alloy used to join together metal workpieces and having a melting point below that of the workpiece(s).Soft solder is typically thought of when solder or soldering is mentioned, with a typical melting range of 90 to 450 C (190to 840F).Frank Oberg, Franklin D. Jones, Holbrook L.Horton, Henry H. Ryffel (ed) Machinery's Handbook 23rd Edition Industrial Press Inc., 1988, ISBN 0-8311-1200-X, page 1203 It is commonly used in electronics, plumbing, and assembly of sheet metal parts. Manual soldering uses a soldering iron or soldering gun. Alloys that melt between 180 and 190 C (360and 370F) are the most commonly used. Soldering performed using alloys with a melting point above 450 C (840F) is called 'hard soldering', 'silver soldering', or brazing. For certain proportions an alloy becomes eutectic and melts at a single temperature; non-eutectic alloys have markedly different solidus (chemistry)solidus and liquidus temperature, and within that range they exist as a paste of solid particles in a melt of the lower-melting phase. In electrical work, if the joint is disturbed in the pasty state before it has solidified totally, a poor electrical connection may result; use of eutectic solder reduces this problem. The pasty state of a non-eutectic solder can be exploited in plumbing as it allows molding of the solder during cooling, e.g. for ensuring watertight joint of pipes, resulting in a so-called 'wiped joint'.For electrical and electronics work solder wire is available in a range of thicknesses for hand-soldering, and with cores containing flux (metallurgy)flux. It is also available as a paste or as a preformed foil shaped to match the workpiece, more suitable for mechanized mass-production. Alloys of lead and tin were universally used in the past, and are still available; they are particularly convenient for hand-soldering. Lead-free solder, somewhat less convenient for hand-soldering, is often used to avoid the environmental effect of lead. Plumbers often use bars of solder, much thicker than the wire used for electrical applications. Jewelers often use solder in thin sheets which they cut into snippets. The word solder comes from the Middle English word soudur, via Old French solduree and soulder, from the Latin solidare, meaning "to make solid".With the reduction of the size of circuit board features, the size of interconnects shrinks as well. Current densities above 104 A/cm2 are often achieved and electromigration becomes a concern. At such current densities the Sn63Pb37 solder balls form hillocks on the anode side and voids on the cathode side; the increased content of lead on the anode side suggests lead is the primary migrating species.Contact with molten solder can cause 'solder embrittlement' of materials, a type of liquid metal embrittlement.[citation needed]Lead solder Sn60Pb40 solderTin/lead solders, also called soft solders, are commercially available with tin concentrations between 5% and 70% by weight. The greater the tin concentration, the greater the solders tensile strengthtensile and shear strengths. Alloys commonly used for electrical soldering are 60/40Tin/lead (Sn/Pb) which melts at 370F or 188C and 63/37Sn/Pb used principally in electrical/electronic work. The 63/37 is a eutectic pointeutectic alloy, which: has the lowest melting point (183C or 361.4F) of all the tin/lead alloys; and the melting point is truly a point not a range.In plumbing, a higher proportion of lead was used, commonly 50/50. This had the advantage of making the alloy solidify more slowly, so that it could be wiped over the joint to ensure watertightness, the pipes being physically fitted together before soldering. Although lead water pipes were displaced by copper when the significance of lead poisoning began to be fully appreciated, lead solder was still used until the 1980s because it was thought that the amount of lead that could leach into water from the solder was negligible from a properly soldered

Solder joint. The electrochemical couple of copper and lead promotes corrosion of the lead and tin, however tin is protected by insoluble oxide. Since even small amounts of lead have been found detrimental to health, lead in plumbing solder was replaced by silver (food grade applications) or antimony, with copper often added, and the proportion of tin was increased (see #Lead-free solderLead-free solder.) The addition of tinmore expensive than leadimproves wetting properties of the alloy; lead itself has poor wetting characteristics. High-tin tin-lead alloys have limited use as the workability range can be provided by a cheaper high-lead alloy.In electronics, components on printed circuit boards (PCBs) are connected to the printed circuit, and hence to other components, by soldered joints. For miniaturized PCB joints with surface mount components, solder paste has largely replaced solid solder. Lead-tin solders readily dissolve gold plating and form brittle intermetallics.Sn60Pb40 solder oxidizes on the surface, forming a complex 4-layer structure: tin(IV) oxide on the surface, below it a layer of tin(II) oxide with finely dispersed lead, followed by a layer of tin(II) oxide with finely dispersed tin and lead, and the solder alloy itself underneath.Lead, and to some degree tin, as used in solder contains small but significant amounts of radioisotope impurities. Radioisotopes undergoing alpha decay are a concern due to their tendency to cause soft errors. Polonium-210 is especially problematic; lead-210 beta decays to bismuth-210 which then beta decays to polonium-210, an intense emitter of alpha particles. Uranium-238 and thorium-232 are other significant contaminants of alloys of lead.Lead-free solderPure tin solder wireSoldering copper pipes using a propane torch and lead-free solder On July 1, 2006 the European Union Waste Electrical and Electronic Equipment Directive (WEEE) and Restriction of Hazardous Substances Directive (RoHS) came into effect prohibiting the intentional addition of lead to most consumer electronics produced in the EU. Manufacturers in the U.S. may receive tax benefits by reducing the use of lead-based solder. Lead-free solders in commercial use may contain tin, copper, silver, bismuth, indium, zinc, antimony, and traces of other metals. Most lead-free replacements for conventional Sn60/Pb40 and Sn63/Pb37 solder have melting points from 5 to 20C higher,Ganesan and Pecht p. 110 though solders with much lower melting points are available. Drop-in replacements for silkscreen with solder paste soldering operations are available. Minor modification to the solder pots (e.g. titanium liners or impellers) used in wave-soldering operations may be desired to reduce maintenance costs associated with the increased tin-scavenging effects of high tin solders. Since the properties of lead-free solders are not as thoroughly known, they may therefore be considered less desirable for critical applications, like certain aerospace or medical projects. "Whisker (metallurgy)Tin whiskers" were a problem with early electronic solders, and lead was initially added to the alloy in part to eliminate them. Sn-Ag-Cu (Tin-Silver-Copper) solders are used by two thirds of Japanese manufacturers for reflow and wave soldering, and by about 75% of companies for hand soldering. The widespread use of this popular lead-free solder alloy family is based on the reduced melting point of the Sn-Ag-Cu ternary eutectic behavior (217 C), which is below the Sn-3.5Ag (wt.%) eutectic of 221C and the Sn-0.7Cu eutectic of 227C (recently revised by P. Snugovsky to Sn-0.9Cu). The ternary eutectic behavior of Sn-Ag-Cu and its application for electronics assembly was discovered (and patented) by a team of researchers from Ames Laboratory, Iowa State University, and from Sandia National Laboratories-Albuquerque. Much recent research has focused on selection of 4th element additions to Sn-Ag-Cu to provide compatibility for the reduced cooling rate of solder sphere reflow for assembly of ball grid arrays, e.g., Sn-3.5Ag-0.74Cu-0.21Zn (melting range of 217220C) and Sn-3.5Ag-0.85Cu-0.10Mn (melting range of 211215C). Tin-based solders readily dissolve gold, forming brittle intermetallics; for Sn-Pb alloys the critical concentration of gold to embrittle the joint is about 4%. Indium-rich solders (usually indium-lead) are more suitable for soldering thicker gold layer as the dissolution rate of gold in indium is much slower. Tin-rich solders also readily dissolve silver; for soldering silver metallization or surfaces, alloys with addition of silvers are suitable; tin-free alloys are also a choice, though their wettability is poorer. If the soldering time is long enough to form the intermetallics, the tin surface of a joint soldered to gold is very dull.Flux-core solder Electrical solder with an integrated rosin core, visible as a dark spot in the cut end of the solder wire.Flux (metallurgy)Flux is a reducing agent designed to help redoxreduce (return oxidized metals to their metallic state) metal oxides at the points of contact to improve the electrical connection and mechanical strength. The two principal types of flux are acid flux, used for metal mending and plumbing, and rosin flux, used in electronics, where the corrosiveness of acid flux and

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Solder vapors released when solder is heated would risk damaging delicate circuitry. Due to concerns over atmospheric pollution and hazardous waste disposal, the electronics industry has been gradually shifting from rosin flux to water-soluble flux, which can be removed with deionized water and detergent, instead of hydrocarbon solvents. In contrast to using traditional bars or coiled wires of all-metal solder and manually applying flux to the parts being joined, much hand soldering since the mid-20th century has used flux-core solder. This is manufactured as a coiled wire of solder, with one or more continuous bodies of non-acid flux embedded lengthwise inside it. As the solder melts onto the joint, it frees the flux and releases that on it as well. Hard solder Hard solders are used for brazing, and melt at higher temperatures. Alloys of copper with either zinc or silver are the most common. In silversmithing or jewelry making, special hard solders are used that will pass Metallurgical assayassay. They contain a high proportion of the metal being soldered and lead is not used in these alloys. These solders vary in hardness, designated as "enameling", "hard", "medium" and "easy". Vitreous enamelEnameling solder has a high melting point, close to that of the material itself, to prevent the joint desoldering during firing in the enameling process. The remaining solder types are used in decreasing order of hardness during the process of making an item, to prevent a previously soldered seam or joint desoldering while additional sites are soldered. Easy solder is also often used for repair work for the same reason. Flux or jeweller's rougerouge is also used to prevent joints from desoldering. Silver solder is also used in manufacturing to join metal parts that cannot be weldingwelded. The alloys used for these purposes contain a high proportion of silver (up to 40%), and may also contain cadmium. Solder alloys Composition Melting pointM.P. CSolidus (chemistry)S/LiquidusL Toxic Eutectic Comments Sn Pb Ag Cu Sb Bi In Zn Cd Au oth. ! Sn50Zn49Cu1 200/300 no Galvanite Lead free galvanizing solder formulation designed specifically for high quality repairs to galvanized Steel surfaces. Simple, effective and easy to use, in both manufacturing and field applications. Metallurgically bonds to the Steel, for a seamless protective barrier. 50 1 49 Sn90Zn7Cu3 200/222 no Kapp Eco-Babbitt Commonly used in capacitor manufacturing as protective coating to shield against electromotive force (EMF) and electromagnetic interference (EMI) with the specified performance of the capacitor, to prevent current and charge leakage out of and within the layers of the capacitor, and to prevent the development of electron flows within the coating material itself, that would dimminish capacitor performance, coating, and capacitor life. 90 3 7 Pb90Sn10 268/302 275/302 Alloy information Pb no Sn10, UNS L54520, ASTM10B. Balls for ceramic ball grid arrayCBGA components, replaced by Sn95.5Ag3.9Cu0.6. Low cost and good bonding properties. Rapidly dissolves gold and silver, not recommended for those. Used for fabrication of car radiator (engine cooling)radiators and fuel tanks, for coating and bonding of metals for moderate service temperatures. Body solder. SOLDER ALLOYS Selection Chart. (PDF) . Retrieved on 2010-07-06. Has low thermal EMF, can be used as an alternative to Cd70 where parasitic thermocouple voltage has to be avoided.http://www.analog.com/library/analogDialogue/archives/39-05/Web_Ch4_final.pdf 10 90 Pb88Sn12 254/296 Pb no Used for fabrication of car radiators and fuel tanks, for coating and bonding of metals for moderate service temperatures. Body solder. 12 88 Pb85Sn15 227/288 Pb no Used for coating tubes and sheets and fabrication of car radiators. Body solder. 15 85 Pb80Sn20 183/280 Pb no Sn20, UNS L54711. Used for coating radiator tubes for joining fins. 20 80 Pb75Sn25 183/266 Pb no Crude solder for construction plumbing works, flame-melted. Used for soldering car engine radiators. Used for machine, dip and hand soldering of plumbing fixtures and fittings. Superior body solder. 25 75 Pb70Sn30 185/255 183/257 Pb no Sn30, UNS L54280, crude solder for construction plumbing works, flame-melted, good for machine and torch soldering. Used for soldering car engine radiators. Used for machine, dip and hand soldering of plumbing fixtures and fittings. Superior body solder. 30 70 Pb68Sn32 253 Pb no "Plumber solder", for construction plumbing works 32 68 Pb68Sn30Sb2 185/243 Pb no Pb68 30 68 2 Sn30Pb50Zn20 177/288 Pb no Kapp GalvRepair Economical solder for repairing & joining most metals including Aluminum and cast Iron. Have been the used for cast Iron and galvanized surface repair. 30 50 20 Sn33Pb40Zn28 230/275 Pb no Economical solder for repairing & joining most metals including Aluminum and cast Iron. Have been the used for cast Iron and galvanized surface repair. 33 40 28 Pb67Sn33 187230 Pb no PM 33, crude solder for construction plumbing works, flame-melted, temperature depends on additives 33 67 Pb65Sn35 183/250 Pb no Sn35. Used as a cheaper alternative of Sn60Pb40 for wiping and sweating joints. 35 65 Pb60Sn40 183/238 183/247 Pb no

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Solder Sn40, UNS L54915. For soldering of brass and car radiators. For bulk soldering, and where wider melting point range is desired. For joining cables. For wiping and joining lead pipes. For repairs of radiators and electrical systems. 40 60 Pb55Sn45 183/227 Pb no For soldering radiator cores, roof seams, and for decorative joints. 45 55 Sn50Pb50 183/216 183212 Pb no Sn50, UNS L55030. "Ordinary solder", for soldering of brass, electricity meters, gas meters, formerly also tin cans. General purpose, for standard tinning and sheetmetal work. Becomes brittle below 150C. Low cost and good bonding properties. Rapidly dissolves gold and silver, not recommended for those. For wiping and assembling plumbing joints for non-potable water. 50 50 Sn50Pb48.5Cu1.5 183/215 3439-00-577-7594 Solder, Tin Alloy. Tpub.com. Retrieved on 2010-07-06. Pb no Savbit, Savbit 1, Sav1. Minimizes dissolution of copper. Originally designed to reduce erosion of the soldering iron tips. About 100 times slower erosion of copper than ordinary tin/lead alloys. Suitable for soldering thin copper platings and very thin copper wires. msl747.PDF. (PDF) . Retrieved on 2010-07-06. 50 48.5 1.5 Sn60Pb40 183/190 183/188 Pb near Sn60, ASTM60A, ASTM60B. Common in electronics, most popular leaded alloy for dipping. Low cost and good bonding properties. Used in both SMT and through-hole electronics. Rapidly dissolves gold and silver, not recommended for those. Slightly cheaper than Sn63Pb37, often used instead for cost reasons as the melting point difference is insignificant in practice. On slow cooling gives slightly duller joints than Sn63Pb37. 60 40 Sn60Pb38Cu2 183/190 Pajky_vkladanylist_Cze_ang_2010.indd. (PDF) . Retrieved on 2010-07-06. Pb Cu2. Copper content increases hardness of the alloy and inhibits dissolution of soldering iron tips and part leads in molten solder. 60 38 2 Sn60Pb39Cu1 Pb no 60 39 1 Sn62Pb38 183 Pb near "Tinman's solder", used for tinplate fabrication work. 62 38 Sn63Pb37 182 183 Balver Zinn Solder Sn63Pb37 Pb yes Sn63, ASTM63A, ASTM63B. Common in electronics; exceptional tinning and wetting properties, also good for stainless steel. One of most common solders. Low cost and good bonding properties. Used in both SMT and through-hole electronics. Rapidly dissolves gold and silver, not recommended for those. Sn60Pb40 is slightly cheaper and is often used instead for cost reasons, as the melting point difference is insignificant in practice. On slow cooling gives slightly brighter joints than Sn60Pb40. 63 37 Sn63Pb37P0.00150.04 183 Balver Zinn Solder Sn63PbP Pb yes Sn63PbP. A special alloy for HASL machines. Addition of phosphorus reduces oxidation. Unsuitable for wave soldering as it may form metal foam. 63 37 P Sn62Pb37Cu1 183 Pb yes Similar to Sn63Pb37. Copper content increases hardness of the alloy and inhibits dissolution of soldering iron tips and part leads in molten solder. 62 37 1 Sn70Pb30 183/193 Pb no Sn70 70 30 Sn90Pb10 183/213 Pb no formerly used for joints in food industry 90 10 Sn95Pb5 238 Pb no plumbing and heating 95 5 Pb92Sn5.5Ag2.5 286/301 Pb no For higher-temperature applications. 5.5 92 2.5 Pb80Sn12Sb8 Pb no Used for soldering iron and steel 12 80 8 Pb80Sn18Ag2 252/260 Pb no Used for soldering iron and steel 18 80 2 Pb79Sn20Sb1 184/270 Pb no Sb1 20 79 1 Pb55Sn43.5Sb1.5 Pb no General purpose solder. Antimony content improves mechanical properties but causes brittleness when soldering cadmium, zinc, or galvanized metals. 43.5 55 1.5 Sn43Pb43Bi14 144/163 Pb no Bi14. Good fatigue resistance combined with low melting point. Contains phases of tin and lead-bismuth. Useful for step soldering. 43 43 14 Sn46Pb46Bi8 120/167 Pb no Bi8 46 46 8 Bi52Pb32Sn16 96 Pb yes? Bi52. Good fatigue resistance combined with low melting point. Reasonable shear strength and fatigue properties. Combination with lead-tin solder may dramatically lower melting point and lead to joint failure. 16 32 52 Bi46Sn34Pb20 100/105 Pb no Bi46 34 20 46 Sn62Pb36Ag2 179 Pb yes Sn62. Common in electronics. The strongest tin-lead solder. Appearance identical to Sn60Pb40 or Sn63Pb37. Crystals of Ag3Sn may be seen growing from the solder. Extended heat treatment leads to formation of crystals of binary alloys. Silver content decreases solubility of silver, making the alloy suitable for soldering silver-metallized surfaces, e.g. SMD capacitors and other silver-metallized ceramics. Not recommended for gold. General-purpose. 62 36 2 Sn62.5Pb36Ag2.5 179 Pb yes 62.5 36 2.5 Pb88Sn10Ag2 268/290 267/299 Indalloy 228 Pb-Sn-Ag Solder Alloy Pb no Sn10, Pb88. Silver content reduces solubility of silver coatings in the solder. Not recommended for gold. Forms a eutectic phase, not recommended for operation above 120 C. 10 88 2 Pb90Sn5Ag5 292 Pb yes 5 90 5 Pb92.5Sn5Ag2.5 287/296 299/304 Pb no Pb93. 5 92.5 2.5 Pb93.5Sn5Ag1.5 296/301 305/306 Pb no Pb94, HMP alloy, HMP. Service temperatures up to 255 C. Useful for step soldering. Also can be used for extremely low temperatures as it remains ductile down to 200 C, while solders with more than 20% tin become brittle below 70 C. Higher strength and

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Solder better wetting than Pb95Sn5. 5 93.5 1.5 Pb95.5Sn2Ag2.5 299/304 Pb no 2 95.5 2.5 In97Ag3 143 Indium Corp. Indalloy 290 In-Ag Solder Alloy yes Wettability and low-temperature malleability of indium, strength improved by addition of silver. Particularly good for cryogenic applications. Used for packaging of photonic devices. 3 97 In90Ag10 143/237 Indalloy 3 In-Ag Solder Alloy no Nearly as wettable and low-temperature malleable as indium. Large plastic range. Can solder silver, fired glass and ceramics. 10 90 In75Pb25 156/165 Pb no Less gold dissolution and more ductile than lead-tin alloys. Used for die attachment, general circuit assembly and packaging closures. 25 75 In70Pb30 160/174 165/175 Indalloy 204 In-Pb Solder Alloy Pb no In70. Suitable for gold, low gold-leaching. Good thermal fatigue properties. 30 70 In60Pb40 174/185 173/181 Pb no In60. Low gold-leaching. Good thermal fatigue properties. 40 60 In50Pb50 180/209 178/210 Pb no In50. Only one phase. Resoldering with lead-tin solder forms indium-tin and indium-lead phases and leads to formation of cracks between the phases, joint weakening and failure. On gold surfaces gold-indium intermetallics tend to be formed, and the joint then fails in the gold-depleted zone and the gold-rich intermetallic. Less gold dissolution and more ductile than lead-tin alloys. Good thermal fatigue properties. 50 50 In50Sn50 118/125 Indalloy 1 Indium-Tin Solder Alloy no Cerroseal 35. Fairly well wets glass, quartz and many ceramics. Malleable, can compensate some thermal expansion differences. Low vapor pressure. Used in low temperature physics as a glass-wetting solder. 50 50 In70Sn15Pb9.6Cd5.4 125 Indalloy 13 Indium Solder Alloy Pb,Cd 15 9.6 70 5.4 Pb75In25 250/264 240/260 Indalloy 10 Pb-In Solder Alloy Pb no In25. Low gold-leaching. Good thermal fatigue properties. Used for die attachment of e.g. GaAs dies. Used also for general circuit assembly and packaging closures. Less dissolution of gold and more ductile than tin-lead alloy. 75 25 Sn70Pb18In12 162154/167 Indalloy 9 Sn-Pb-In Solder Alloy Pb yes General purpose. Good physical properties. 70 18 12 Sn37.5Pb37.5In25 134/181 Pb no Good wettability. Not recommended for gold. 37.5 37.5 25 Pb90In5Ag5 290/310 Pb no 90 5 5 Pb92.5In5Ag2.5 300/310 Pb no UNS L51510. Minimal leaching of gold, good thermal fatigue properties. Reducing atmosphere frequently used.. 92.5 2.5 5 Pb92.5In5Au2.5 300/310 Pb no In5 92.5 5 2.5 Pb94.5Ag5.5 305/364 304/343 94.5Pb-5.5Ag Lead-Silver Solder, ASTM Class 5.5S; UNS L50180 Pb no Ag5.5, UNS L50180 94.5 5.5 Pb95Ag5 305/364 Indalloy 175 Lead Solder Alloy Pb no 95 5 Pb97.5Ag2.5 303 304 304/579 97.5Pb-2.5Ag Lead-Silver Solder, ASTM Class 2.5S UNS L50132 Pb yes no Ag2.5, UNS L50132. Used during World War II to conserve tin. Poor corrosion resistance; joints suffered corrosion in both atmospheric and underground conditions, all had to be replaced with Sn-Pb alloy joints. Torch solder. 97.5 2.5 Sn97.5Pb1Ag1.5 305 Pb yes Important for hybrid circuits assembly. 97.5 1 1.5 Pb97.5Ag1.5Sn1 309 Pb yes Ag1.5, ASTM1.5S. High melting point, used for commutators, armatures, and initial solder joints where remelting when working on nearby joints is undesirable. Silver content reduces solubility of silver coatings in molten solder. Not recommended for gold. Standard PbAgSn eutectic solder, wide use in semiconductor assembly. Reducing protective atmosphere (e.g. 12% hydrogen) often used. High creep resistance, for use at both elevated and cryogenic temperatures. 1 97.5 1.5 Pb54Sn45Ag1 177210 Pb exceptional strength, silver gives it a bright long-lasting finish; ideal for stainless steel 45 54 1 Pb96Ag4 305 Pb high-temperature joints 96 4 Pb96Sn2Ag2 252/295 Pb Pb96 2 96 2 Sn61Pb36Ag3 Pb 61 36 3 Sn56Pb39Ag5 Pb 56 39 5 Sn98Ag2 98 2 Sn65Ag25Sb10 233 yes Very high tensile strength. For die attachment. Very brittle. Old Motorola die attach solder. 65 25 10 Sn96.5Ag3.0Cu0.5 217/220 217/218 Balver Zinn Solder SN97C (SnAg3.0Cu0.5) near SAC305. It is the JEITA recommended alloy for wave and reflow soldering, with alternatives SnCu for wave and SnAg and SnZnBi for reflow soldering. Usable also for selective soldering and dip soldering. At high temperatures tends to dissolve copper; copper buildup in the bath has detrimental effect (e.g. increased bridging). Copper content must be maintained between 0.40.85%, e.g. by refilling the bath with Sn97Ag3 alloy. Nitrogen atmosphere can be used to reduce losses by dross formation. Dull, surface shows formation of dendritic tin crystals. 96.5 3 0.5 Sn95.8Ag3.5Cu0.7 217218 near SN96C-Ag3.5 A commonly used alloy. Used for wave soldering. Usable also for selective soldering and dip soldering. At high temperatures tends to dissolve copper; copper buildup in the bath has detrimental effect (e.g. increased bridging). Copper content must be maintained between 0.40.85%, e.g. by refilling the bath with Sn96.5Ag3.5 alloy (designated e.g. SN96Ce). Nitrogen atmosphere can be used to reduce losses by dross formation. Dull, surface shows formation of dendritic tin crystals. 95.8 3.5 0.7 Sn95.6Ag3.5Cu0.9 217 yes Determined by NIST to be truly eutectic. 95.6 3.5 0.9 Sn95.5Ag3.8Cu0.7

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Solder 217 Balver Zinn Solder SN96C (SnAg3,8Cu0,7) almost SN96C. Preferred by the European IDEALS consortium for reflow soldering. Usable also for selective soldering and dip soldering. At high temperatures tends to dissolve copper; copper buildup in the bath has detrimental effect (e.g. increased bridging). Copper content must be maintained between 0.40.85%, e.g. by refilling the bath with Sn96.2Ag3.8 alloy (designated e.g. SN96Ce). Nitrogen atmosphere can be used to reduce losses by dross formation. Dull, surface shows formation of dendritic tin crystals. 95.5 3.8 0.7 Sn95.25Ag3.8Cu0.7Sb0.25 Preferred by the European IDEALS consortium for wave soldering. 95.25 3.8 0.7 0.25 Sn95.5Ag3.9Cu0.6 217 Indalloy 252 95.5Sn/3.9Ag/0.6Cu Lead-Free Solder Alloy yes Recommended by the US NEMI consortium for reflow soldering. Used as balls for ball grid arrayBGA/chip scale packageCSP and CBGA components, a replacement for Sn10Pb90. Solder paste for rework of BGA boards. Alloy of choice for general SMT assembly. 95.5 3.9 0.6 Sn95.5Ag4Cu0.5 217 Indalloy 246 95.5Sn/4.0Ag/0.5Cu Lead-Free Solder Alloy yes Lead Free, Cadmium Free formulation designed specifically to replace Lead solders in Copper and Stainless Steel plumbing, and in electrical and electronic applications. 95.5 4 0.5 Sn96.5Ag3.5 221 yes Sn96, Sn96.5, 96S. Fine lamellar structure of densely distributed Ag3Sn. Annealing at 125C coarsens the structure and softens the solder. Creeps via dislocation climb as a result of lattice diffusion. Used as wire for hand soldering rework; compatible with SnCu0.7, SnAg3Cu0.5, SnAg3.9Cu0.6, and similar alloys. Used as solder spheres for BGA/CSP components. Used for step soldering and die attachment in high power devices. Established history in the industry. Widely used. Strong lead-free joints. Silver content minimizes solubility of silver coatings. Not recommended for gold. Marginal wetting. Good for step soldering. Used for soldering stainless steel as it wets stainless steel better than other soft solders. Silver content does not suppress dissolution of silver metallizations. High tin content allows absorbing significant amount of gold without embrittlement. Solder selection for photonic packaging 96.5 3.5 Sn96Ag4 221229 no ASTM96TS. "Silver-bearing solder". Food service equipment, refrigeration, heating, air conditioning, plumbing. Widely used. Strong lead-free joints. Silver content minimizes solubility of silver coatings. Not recommended for gold. 96 4 Sn95Ag5 221/254 no Widely used. Strong lead-free joints. Silver content minimizes solubility of silver coatings. Not recommended for gold. Produces strong and ductile joints on Copper and Stainless Steel. The resulting joints have high tolerance to vibration and stress, with tensile strengths to 30,000 psi on Stainless. 95 5 Sn94Ag6 221/279 no Produces strong and ductile joints on Copper and Stainless Steel. The resulting joints have high tolerance to vibration and stress, with tensile strengths to 30,000 psi on Stainless. 94 6 Sn93Ag7 221/302 no Produces strong and ductile joints on Copper and Stainless Steel. The resulting joints have high tolerance to vibration and stress, with tensile strengths to 31,000 psi on Stainless. Audio industry standard for vehicle and home theater speaker installations. Its 7% Silver content requires a higher temperature range, but yields superior strength and vibration resistance. 93 7 Sn95Ag4Cu1 95 4 1 Sn 232 pure Sn99. Good strength, non-dulling. Use in food processing equipment, wire tinning, and alloying. Susceptible to tin pest. 99.99 Sn99.3Cu0.7 227 yes Sn99Cu1. Also designated as Sn99Cu1. Cheap alternative for wave soldering, recommended by the US NEMI consortium. Coarse microstructure with ductile fractures. Sparsely distributed Cu6Sn5.Ganesan and Pecht p. 404 Forms large dendritic -tin crystals in a network of eutectic microstructure with finely dispersed Cu6Sn5. High melting point unfavorable for SMT use. Low strength, high ductility. Susceptible to tin pest. Addition of small amount of nickel increases its fluidity; the highest increase occurs at 0.06% Ni. Such alloys are known as nickel modified or nickel stabilized. The Fluidity of the Ni-Modified Sn-Cu Eutectic Lead Free Solder 99.3 0.7 (Ni) Sn99Cu0.7Ag0.3 217/228 Balver Zinn Solder SCA (SnCu0.7Ag0.3) no SCA, SAC, or SnAgCu. Tin-silver-copper alloy. Relatively low-cost lead-free alloy for simple applications. Can be used for wave, selective and dip soldering. At high temperatures tends to dissolve copper; copper buildup in the bath has detrimental effect (e.g. increased bridging). Copper content must be maintained between 0.40.85%, e.g. by refilling the bath with Sn96.2Ag3.8 alloy (designated e.g. SN96Ce). Nitrogen atmosphere can be used to reduce losses by dross formation. Dull, surface shows formation of dendritic tin crystals. 99 0.3 0.7 Sn97Cu3 227/250 Balver Zinn Solder Sn97Cu3 232/332 For high-temperature uses. Allows removing insulation from an enameled wire and applying solder coating in a single operation. For radiator repairs, stained glass windows, and potable water plumbing. 97 3 Sn97Cu2.75Ag0.25 228/314 High hardness, creep-resistant. For radiators, stained glass windows, and potable

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Solder water plumbing. Excellent high-strength solder for radiator repairs. Wide range of patina and colors. 97 0.25 2.75 Zn100 419 pure For soldering aluminium. Good wettability of aluminium, relatively good corrosion resistance. 100 Bi100 271 pure Used as a non-superconducting solder in low-temperature physics. Does not wet metals well, forms a mechanically weak joint. 100 Sn91Zn9 199 yes KappAloy9 Designed specifically for Aluminum-to-Aluminum and Aluminum-to-Copper soldering. It has good corrosion resistance and tensile strength. Lies between soft solder and silver brazing alloys, thereby avoiding damage to critical electronics and substrate deformation and segregation. Best solder for Aluminum wire to Copper busses or Copper wire to Aluminum busses or contacts. UNS#: L91090 91 9 Sn85Zn15 199/260 no KappAloy15 Designed specifically for Aluminum-to-Aluminum and Aluminum-to-Copper soldering. It has good corrosion resistance and tensile strength. Lies between soft solder and silver brazing alloys, thereby avoiding damage to critical electronics and substrate deformation and segregation. Has a wide plastic range this makes it ideal for hand soldering Aluminum plates and parts, allowing manipulation of the parts as the solder cools. 85 15 Zn95Al5 382 yes For soldering aluminium. Good wetting. 95 Al5 Sn91.8Bi4.8Ag3.4 211/213 Indalloy 249 91.8Sn/3.4Ag/4.8Bi Lead-Free Solder Alloy no Do not use on lead-containing metallizations. U.S. Patent 5,439,639 (ICA Licensed Sandia Patent). 91.8 3.4 4.8 Sn70Zn30 199/316 no KappAloy30 For soldering of aluminium. Good wetting. Used extensively in spray wire form for capacitors and other electronic parts. Higher temperature and higher tensile strength compared to 85Sn/15Zn and 91Sn/9Zn. 70 30 Sn80Zn20 199/288 no KappAloy20 For soldering of aluminium. Good wetting. Used extensively in spray wire form for capacitors and other electronic parts. Higher temperature and higher tensile strength compared to 85Sn/15Zn and 91Sn/9Zn. 80 20 Sn60Zn40 199/343 no KappAloy40 For soldering of aluminium. Good wetting. Used extensively in spray wire form for capacitors and other electronic parts. Higher temperature and higher tensile strength compared to 85Sn/15Zn and 91Sn/9Zn. 60 40 Pb63Sn35Sb2 185/243 Pb no Sb2 35 63 2 Pb63Sn34Zn3 170/256 Pb no Poor wetting of aluminium. Poor corrosion rating. 34 63 3 Pb92Cd8 310? Pb,Cd ? For soldering aluminium. US patent 1,333,666. Composition And Physical Properties Of Alloys. Csudh.edu (2007-08-18). Retrieved on 2010-07-06. 92 8 Sn48Bi32Pb20 140/160 Pb no For low-temperature soldering of heat-sensitive parts, and for soldering in the vicinity of already soldered joints without their remelting. 48 20 32 Sn89Zn8Bi3 191198 Prone to corrosion and oxidation due to its zinc content. On copper surfaces forms a brittle Cu-Zn intermetallic layer, reducing the fatigue resistance of the joint; nickel plating of copper inhibits this. 89 3 8 Sn83.6Zn7.6In8.8 181/187 Indalloy 226 Tin Solder Alloy no High dross due to zinc. Covered by U.S. Patent #5,242,658. 83.6 8.8 7.6 Sn86.5Zn5.5In4.5Bi3.5 174/186 Indalloy 231 Sn-Zn-In-Bi Solder Alloy no Lead-free. Corrosion concerns and high drossing due to zinc content. 86.5 3.5 4.5 5.5 Sn86.9In10Ag3.1 204/205 Indalloy 254 86.9Sn/10.0In/3.1Ag Lead-Free Solder Alloy Potential use in flip-chip assembly, no issues with tin-indium eutectic phase. 86.9 3.1 10 Sn95Ag3.5Zn1Cu0.5 221L no 95 3.5 0.5 1 Sn95Sb5 235/240 232/240 no Sb5, ASTM95TA. The US plumbing industry standard. It displays good resistance to thermal fatigue and good shear strength. Forms coarse dendrites of tin-rich solid solution with SbSn intermetallic dispersed between. Very high room-temperature ductility. Creeps via viscous glide of dislocations by pipe diffusion. More creep-resistant than SnAg3.5. Antimony can be toxic. Used for sealing chip packagings, attaching I/O pins to ceramic substrates, and die attachment; a possible lower-temperature replacement of AuSn. High strength and bright finish. Use in air conditioning, refrigeration, some food containers, and high-temperature applications. Good wettability, good long-term shear strength at 100 C. Suitable for potable water systems. Used for stained glass, plumbing, and radiator repairs. 95 5 Sn97Sb3 232/238 Indalloy 131 97Sn/3Sb Lead-Free Solder Alloy no 97 3 Sn99Sb1 232/235 Indalloy 129 99Sn/1Sb Lead-Free Solder Alloy no 99 1 Sn99Ag0.3Cu0.7 99 0.3 0.7 Sn96.2Ag2.5Cu0.8Sb0.5 217225 217 Ag03A. Patented by AIM alliance. 96.2 2.5 0.8 0.5 Sn88In8.0Ag3.5Bi0.5 197208 Patented by Panasonic CorporationMatsushita/Panasonic. 88 3.5 0.5 8 Bi57Sn42Ag1 137/139 139/140 Indalloy 282 57Bi/42Sn/1Ag Lead-Free Solder Alloy Addition of silver improves mechanical strength. Established history of use. Good thermal fatigue performance. Patented by Motorola. 42 1 57 Bi58Sn42 138 yes Bi58. Reasonable shear strength and fatigue properties. Combination with lead-tin solder may dramatically lower melting point and lead to joint failure. Low-temperature eutectic solder with high strength. Particularly strong, very brittle. Used extensively in

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Solder through-hole technology assemblies in IBM mainframe computers where low soldering temperature was required. Can be used as a coating of copper particles to facilitate their bonding under pressure/heat and creating a conductive metallurgical joint. Sensitive to shear rate. Good for electronics. Used in thermoelectric applications. Good thermal fatigue performance. Indalloy 281 Bi-Sn Solder Alloy Established history of use. Expands slightly on casting, then undergoes very low further shrinkage or expansion, unlike many other low-temperature alloys which continue changing dimensions for some hours after solidification. 42 58 Bi58Pb42 124/126 Indalloy 67 Bismuth-Lead Solder Alloy Pb 42 58 In80Pb15Ag5 142/149149/154 Indalloy 2 In-Pb-Ag Solder Alloy Pb no In80. Compatible with gold, minimum gold-leaching. Resistant to thermal fatigue. Can be used in step soldering. 15 5 80 Pb60In40 195/225 Pb no In40. Low gold-leaching. Good thermal fatigue properties. 60 40 Pb70In30 245/260 Pb no In30 70 30 Sn37.5Pb37.5In26 134/181 Pb no In26 37.5 37.5 26 Sn54Pb26In20 130/154 140/152 Indalloy 532 Tin Solder Alloy Pb no In20 54 26 20 Pb81In19 270/280 260/275 Indalloy 150 Pb-In Solder Alloy Pb no In19. Low gold-leaching. Good thermal fatigue properties. 81 19 In52Sn48 118 yes In52. Suitable for the cases where low-temperature soldering is needed. Can be used for glass sealing. Sharp melting point. Good wettability of glass, quartz, and many ceramics. Good low-temperature malleability, can compensate for different thermal expansion coefficients of joined materials. 48 52 Sn52In48 118/131 no very low tensile strength 52 48 Sn58In42 118/145 Indalloy 87 Indium-Tin Solder Alloy no 58 42 Sn51.2Pb30.6Cd18.2 145 Indalloy 181 Sn-Pb-Cd Solder Alloy Pb,Cd yes General-purpose. Maintains creep strength well. Unsuitable for gold. 51.2 30.6 18.2 Sn77.2In20Ag2.8 175/187 Indalloy 227 Sn-In-Ag Solder Alloy no Similar mechanical properties with Sn63Pb37, Sn62Pb36Ag2 and Sn60Pb40, suitable lead-free replacement. Contains eutectic Sn-In phase with melting point at 118 C, avoid use above 100 C. 77.2 2.8 20 In74Cd26 123 Indalloy 253 Indium Solder Alloy Cd yes 74 26 In61.7Bi30.8Cd7.5 62 Indalloy 18 Indium Solder Alloy Cd yes 30.8 61.7 7.5 Bi47.5Pb25.4Sn12.6Cd9.5In5 57/65 Indalloy 140 Bismuth Solder Alloy Pb,Cd no 12.6 25.4 47.5 5 9.5 Bi48Pb25.4Sn12.8Cd9.6In4 61/65 Indalloy 147 Bismuth Solder Alloy Pb,Cd no 12.8 25.4 48 9.6 Bi49Pb18Sn15In18 58/69 Indalloy 21 Bismuth Solder Alloy Pb no 15 18 49 18 Bi49Pb18Sn12In21 58 Pb yes Cerrolow 136. Slightly expands on cooling, later shows slight shrinkage in couple hours afterwards. Used as a solder in low-temperature physics. 12 18 49 21 Bi50.5Pb27.8Sn12.4Cd9.3 70/73 Indalloy 22 Bismuth Solder Alloy Pb,Cd no 12.4 27.8 50.5 9.3 Bi50Pb26.7Sn13.3Cd10 70 Pb,Cd yes Cerrobend. Used in low-temperature physics as a solder. 13.3 26.7 50 10 Bi44.7Pb22.6In19.1Cd5.3Sn8.3 47 Cd,Pb yes Cerrolow 117. Used as a solder in low-temperature physics. 8.3 22.6 44.7 19.1 5.3 In60Sn40 113/122 no 40 60 In51.0Bi32.5Sn16.5 60.5 yes Field's metal 16.5 32.5 51 Bi49.5Pb27.3Sn13.1Cd10.1 70.9 Pb,Cd yes Lipowitz Metal 13.1 27.3 49.5 10.1 Bi50.0Pb25.0Sn12.5Cd12.5 71 Pb,Cd yes Wood's metal, mostly used for casting. 12.5 25 50 12.5 Bi50.0Pb31.2Sn18.8 97 Pb no Newton's metal 18.8 31.2 50 Bi50Pb28Sn22 109 Pb no Rose's metal. It was used to secure cast iron railings and balusters in pockets in stone bases and steps. Does not contract on cooling. 22 28 50 Cd95Ag5 338/393 Cd no KappTec General purpose solder that will join all solderable metals except Aluminum. High temperature, high strength solder. It is used in applications where alloys melting higher than soft solders are required, but the cost and strength of Silver-brazing alloys is not necessary. 5 95 Cd82.5Zn17.5 265 Cd yes Medium temperature alloy that provide strong, corrosion-resistant joints on most metals. Also for soldering aluminium and die castingdie-cast zinc alloys. Used in cryogenic physics for ataching electrical potential leads to specimens of metals, as this alloy does not become superconductive at liquid helium temperatures. 17.5 82.5 Cd70Zn30 265/300 Cd no Medium temperature alloy that provide strong, corrosion-resistant joints on most metals. Works especially well on Aluminum-to-Aluminum and Aluminum-to-Copper joints, with excellent corrosion resistance and superior strength in high vibration and high stress applications in electronics, lighting and electrical products. 30 70 Cd60Zn40 265/316 Cd no Medium temperature alloy that provide strong, corrosion-resistant joints on most metals. Works especially well on Aluminum-to-Aluminum and Aluminum-to-Copper joints, with excellent corrosion resistance and superior strength in high vibration and high stress applications in electronics, lighting and electrical products. 40 60 Cd78Zn17Ag5 249/316 Cd no KappTecZ High temperature, high strength solder that may be used on most metals, but works extremely well on Aluminum, Copper and Stainless Steel. It has a high tolerance to vibration and stress, and good elongation for use on dissimilar metals. Above its liquidus of 600F, this solder is extremely fluid and will penetrate

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Solder the closest joints. 5 17 78 Sn40Zn27Cd33 176/260 Cd no KappRad Developed specifically to join and repair Aluminum and Aluminum/Copper radiators and heat exchangers. A lower melting point makes delicate repair work easier. 40 27 33 Zn90Cd10 265/399 Cd For soldering aluminium. Good wetting. 90 10 Zn60Cd40 265/335 Cd For soldering aluminium. Very good wetting. 60 40 Cd70Sn30 140/160 Cd no Cd70, thermal-free solder. Produces low thermal EMF joints in copper, does not form parasitic thermocouples. Used in low-temperature physics. 29.56 70.44 Sn50Pb32Cd18 145 Cd,Pb Cd18 50 32 18 Sn40Pb42Cd18 145 Soft Solders. www.cupalloys.co.uk (2009-01-20). Retrieved on 2010-07-06. Cd,Pb Low melting temperature allows repairing pewter and zinc objects, including die-cast toys. 40 42 18 Zn70Sn30 199/376 no For soldering aluminium. Excellent wetting. Good strength. 30 70 Zn60Sn40 199/341 no For soldering aluminium. Good wetting. 40 60 Zn95Sn5 382 yes? For soldering aluminium. Excellent wetting. 5 95 Sn90Au10 217 Indalloy 238 Sn-Au Solder Alloy yes 90 10 Au80Sn20 280 yes Au80. Good wetting, high strength, low creep, high corrosion resistance, high thermal conductivity, high surface tension, zero wetting angle. Suitable for step soldering. The original flux-less alloy, does not need flux. Used for die attachment and attachment of metal lids to semiconductor packages, e.g. kovar lids to ceramic chip carriers. Coefficient of expansion matching many common materials. Due to zero wetting angle requires pressure to form a void-free joint. Alloy of choice for joining gold-plated and gold-alloy plated surfaces. As some gold dissolves from the surfaces during soldering and moves the composition to non-eutectic state (1% increase of Au content can increase melting point by 30C), subsequent desoldering requires higher temperature. Gold Tin The Unique Eutectic Solder Alloy Forms a mixture of two brittle intermetallic compoundintermetallic phases, AuSn and Au5Sn. Brittle. Proper wetting achieved usually by using nickel surfaces with gold layer on top on both sides of the joint. Comprehensively tested through military standard environmental conditioning. Good long-term electrical performance, history of reliability. Low vapor pressure, suitable for vacuum work. Generally used in applications that require a melting temperature over 150C. Indalloy 182 Gold-Tin Solder Paste. Good ductility. Also classified as a braze. 20 80 Au98Si2 370/800 Au98. A non-eutectic alloy used for die attachment of silicon die (integrated circuit)dies. Ultrasonic assistance is needed to scrub the chip surface so a eutectic (3.1% Si) is reached at reflow. 98 Si2 Au96.8Si3.2 370 363 Indalloy 184 Gold Solder Alloy yes Au97. AuSi3.2 is a eutectic with melting point of 363C. AuSi forms a meniscus at the edge of the chip, unlike AuSn, as AuSi reacts with the chip surface. Forms a composite material structure of submicron silicon plates in soft gold matrix. Tough, slow crack propagation. 96.8 Si3.2 Au87.5Ge12.5 361 356 yes Au88. Used for die attachment of some chips. The high temperature may be detrimental to the chips and limits reworkability. 87.5 Ge12.5 Au82In18 451/485 no Au82. High-temperature, extremely hard, very stiff. 18 82 IndiumIn100 157 pure In99. Used for die attachment of some chips. More suitable for soldering gold, dissolution rate of gold is 17 times slower than in tin-based solders and up to 20% of gold can be tolerated without significant embrittlement. Good performance at cryogenic temperatures. Wets many surfaces incl. quartz, glass, and many ceramics. Deforms indefinitely under load. Does not become brittle even at low temperatures. Used as a solder in low-temperature physics, will bond to aluminium. Can be used for soldering to thin metal films or glass with an Ultrasonic weldingultrasonic soldering iron. 99.99 Notes on the above tableTemperature ranges for solidus and liquidus (the boundaries of the mushy state) are listed as solidus/liquidus.In the Sn-Pb alloys, tensile strength increases with increasing tin content. Indium-tin alloys with high indium content have very low tensile strength.For soldering semiconductor materials, e.g. die attachment of silicon, germanium and gallium arsenide, it is important that the solder contains no impurities that could cause doping (semiconductors)doping in the wrong direction. For soldering n-type semiconductors, solder may be doped with antimony; indium may be added for soldering p-type semiconductors. Pure tin and pure gold can be used.Various fusible alloys can be used as solders with very low melting points; examples include Field's metal, Lipowitz's alloy, Wood's metal, and Rose's metal. Properties The thermal conductivity of common solders ranges from 32 to 94 W/(mK) and the density from 9.25 to 15.00g/cm3. Thermal Properties of Metals, Conductivity, Thermal Expansion, Specific Heat Material Thermal conductivity[W/(m*K)] Melting point[C] Sn-37Pb (eutectic) 50.9 183 Sn-2.8Ag-20.0In 53.5 175 186 Sn-2.5Ag-0.8Cu-0.5Sb 57.26 215 217 Pb-5Sn 63 310 Lead (Pb) 35.0 327.3 Tin (Sn) 73.0 231.9 Aluminum (Al) 240 660.1 Copper (Cu) 393 - 401 1083 FR-4 1.7 Solidifying The solidifying behavior depends on the alloy

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Solder composition. Pure metals solidify at a sharply defined temperature, forming crystals of one phase. Eutectic alloys also solidify at a single temperature, all components precipitating simultaneously in so-called coupled growth. Non-eutectic compositions on cooling start to first precipitate the non-eutectic phase; dendrites when it is a metal, large crystals when it is an intermetallic compound. Such a mixture of solid particles in a molten eutectic is referred to as a mushy state. Even a relatively small proportion of solids in the liquid can dramatically lower its fluidity.The temperature of total solidification is the solidus of the alloy, the temperature at which all components are molten is the liquidus. The mushy state is desired where a degree of plasticity is beneficial for creating the joint, allowing filling larger gaps or being wiped over the joint (e.g. when soldering pipes). In hand soldering of electronics it may be detrimental as the joint may appear solidified while it is not yet. Premature handling of such joint then disrupts its internal structure and leads to compromised mechanical integrity. Alloying element roles Different elements serve different roles in the solder alloy: Antimony is added to increase strength without affecting wettability. Prevents tin pest. Should be avoided on zinc, cadmium, or galvanized metals as the resulting joint is brittle.Bismuth significantly lowers the melting point and improves wettability. In presence of sufficient lead and tin, bismuth forms crystals of Sn16Pb32Bi52 with melting point of only 95 C, which diffuses along the grain boundaries and may cause a joint failure at relatively low temperatures. A high-power part pre-tinned with an alloy of lead can therefore desolder under load when soldered with a bismuth-containing solder. Such joints are also prone to cracking. Alloys with more than 47% Bi expand upon cooling, which may be used to offset thermal expansion mismatch stresses. Retards growth of tin whiskers. Relatively expensive, limited availability. Copper lowers the melting point, improves resistance to thermal cycle fatigue, and improves wetting properties of the molten solder. It also slows down the rate of dissolution of copper from the board and part leads in the liquid solder. Forms intermetallic compounds. May promote growth of tin whiskers. Supersaturated (by about 1%) solution of copper in tin may be employed to inhibit dissolution of thin-film under-bump metallization of ball grid arrayBGA chips, e.g. as Sn94Ag3Cu3.King-Ning-Tu Solder Joint Technology - Materials, Properties, and Reliability (Springer 2007)Nickel can be added to the solder alloy to form a supersaturated solution to inhibit dissolution of thin-film under-bump metallization.Indium lowers the melting point and improves ductility. In presence of lead it forms a ternary compound that undergoes phase change at 114C. Very high cost (several times of silver), low availability. Easily oxidizes, which causes problems for repairs and reworks, especially when oxide-removing flux cannot be used, e.g. during GaAs die attachment. Indium alloys are used for cryogenic applications, and for soldering gold as gold dissolves in indium much less than in tin. Indium can also solder many nonmetals (e.g. glass, mica, alumina, magnesia, titania, zirconia, porcelain, brick, concrete, and marble). Prone to diffusion into semiconductors and cause undesired doping. At elevated temperatures easily diffuses through metals. Low vapor pressure, suitable for use in vacuum systems. Forms brittle intermetallics with gold; indium-rich solders on thick gold are unreliable. Indium-based solders are prone to corrosion, especially in presence of chloride ions.Lead is inexpensive and has suitable properties. Worse wetting than tin. Toxic, being phased out. Retards growth of tin whiskers, inhibits tin pest. Lowers solubility of copper and other metals in tin. Silver provides mechanical strength, but has worse ductility than lead. In absence of lead, it improves resistance to fatigue from thermal cycles. Using SnAg solders with HASL-SnPb-coated leads forms SnPb36Ag2 phase with melting point at 179C, which moves to the board-solder interface, solidifies last, and separates from the board. Addition of silver to tin significantly lowers solubility of silver coatings in the tin phase. In eutectic tin-silver (3.5% Ag) alloy it tends to form platelets of Ag3Sn, which, if formed near a high-stress spot, may serve as initiating sites for cracks; silver content needs to be kept below 3% to inhibit such problems.Tin is the usual main structural metal of the alloy. It has good strength and wetting. On its own it is prone to tin pest, tin cry, and growth of tin whiskers. Readily dissolves silver, gold and to less but still significant extent many other metals, e.g. copper; this is a particular concern for tin-rich alloys with higher melting points and reflow temperatures. Zinc lowers the melting point and is low-cost. However it is highly susceptible to corrosion and oxidation in air, therefore zinc-containing alloys are unsuitable for some purposes, e.g. wave soldering, and zinc-containing solder pastes have shorter shelf life than zinc-free. Can form brittle Cu-Zn intermetallic layers in contact with copper. Readily oxidizes which impairs wetting, requires a suitable flux. Germanium in tin-based lead-free solders influences formation of oxides; at below

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Solder 0.002% it increases formation of oxides. Optimal concentration for suppressing oxidation is at 0.005%. Balver Zinn Desoxy RSNImpurities in solders Impurities usually enter the solder reservoir by dissolving the metals present in the assemblies being soldered. Dissolving of process equipment is not common as the materials are usually chosen to be insoluble in solder.Aluminium little solubility, causes sluggishness of solder and dull gritty appearance due to formation of oxides. Addition of antimony to solders forms Al-Sb intermetallics that are segregated into dross. Antimony added intentionally, up to 0.3% improves wetting, larger amounts slowly degrade wetting Arsenic forms thin intermetallics with adverse effects on mechanical properties, causes dewetting of brass surfaces Cadmium causes sluggishness of solder, forms oxides and tarnishes Copper most common contaminant, forms needle-shaped intermetallics, causes sluggishness of solders, grittiness of alloys, decreased wetting Gold easily dissolves, forms brittle intermetallics, contamination above 0.5% causes sluggishness and decreases wetting. Lowers melting point of tin-based solders. Higher-tin alloys can absorb more gold without embrittlement.Iron forms intermetallics, causes grittiness, but rate of dissolution is very low; readily dissolves in lead-tin above 427C.Nickel causes grittiness, very little solubility in Sn-Pb Phosphorus forms tin and lead phosphides, causes grittiness and dewetting, present in electroless nickel plating Silver often added intentionally, in high amounts forms intermetallics that cause grittiness and formation of pimples on the solder surface Sulfur forms lead and tin sulfides, causes dewetting Zinc in melt forms excessive dross, in solidified joints rapidly oxidizes on the surface; zinc oxide is insoluble in fluxes, impairing repairability; copper and nickel barrier layers may be needed when soldering brass to prevent nickel migration to the surface Intermetallics in solders Many different intermetallicsintermetallic compounds are formed during solidifying of solders and during their reactions with the soldered surfaces.The intermetallics form distinct phases, usually as inclusions in a ductile solid solution matrix, but also can form the matrix itself with metal inclusions or form crystalline matter with different intermetallics. Intermetallics are often hard and brittle. Finely distributed intermetallics in a ductile matrix yield a hard alloy while coarse structure gives a softer alloy. A range of intermetallics often forms between the metal and the solder, with increasing proportion of the metal; e.g. forming a structure of Cu-Cu3Sn-Cu6Sn5-Sn. Layers of intermetallics can form between the solder and the soldered material. These layers may cause mechanical reliability weakening and brittleness, increased electrical resistance, or electromigration and formation of voids. The gold-tin intermetallics layer is responsible for poor mechanical reliability of tin-soldered gold-plated surfaces where the gold plating did not completely dissolve in the solder. Gold and palladium readily dissolve in solders. Copper and nickel tend to form intermetallic layers during normal soldering profiles. Indium forms intermetallics as well. Indium-gold intermetallics are brittle and occupy about 4 times more volume than the original gold. Bonding wires are especially susceptible to indium attack. Such intermetallic growth, together with thermal cycling, can lead to failure of the bonding wires.http://nepp.nasa.gov/wirebond/literatures/na-gsfc-2004-01.pdf GSFC NASA Advisory: Indium solder encapsulating gold bonding wire leads to fragile gold-indium compounds and an unreliable condition that results in wire interconnection ruptureCopper plated with nickel and gold is often used. The thin gold layer facilitates good solderability of nickel as it protects the nickel from oxidation; the layer has to be thin enough to rapidly and completely dissolve so bare nickel is exposed to the solder.Lead-tin solder layers on copper leads can form copper-tin intermetallic layers; the solder alloy is then locally depleted of tin and form a lead-rich layer. The Sn-Cu intermetallics then can get exposed to oxidation, resulting in impaired solderability.Two processes play role in a solder joint formation: interaction between the substrate and molten solder, and solid-state growth of intermetallic compounds. The base metal dissolves in the molten solder in an amount depending on its solubility in the solder. The active constituent of the solder reacts with the base metal with a rate dependent on the solubility of the active constituents in the base metal. The solid-state reactions are more complex - the formation of intermetallics can be inhibited by changing the composition of the base metal or the solder alloy, or by using a suitable barrier layer to inhibit diffusion of the metals.TinLeadIndiumCopper Cu4Sn, Cu6Sn5, Cu3Sn, Cu3Sn8 Cu3In, Cu9In4Nickel Ni3Sn, Ni3Sn2, Ni3Sn4 NiSn3 Ni3In, NiIn Ni2In3, Ni3In7Iron FeSn, FeSn2Indium In3Sn, InSn4 In3Pb Antimony SbSn Bismuth BiPb3Silver Ag6Sn, Ag3Sn Ag3In, AgIn2GoldAu5Sn, AuSn AuSn2, AuSn4 Au2Pb, AuPb2 AuIn, AuIn2Palladium Pd3Sn, Pd2Sn, Pd3Sn2, PdSn, PdSn2, PdSn4 Pd3In, Pd2In, PdIn Pd2In3Platinum Pt3Sn, Pt2Sn,

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Solder PtSn, Pt2Sn3, PtSn2, PtSn4 Pt3Pb, PtPb PtPb4 Pt2In3, PtIn2, Pt3In7 Cu6Sn5 common on solder-copper interface, forms preferentially when excess of tin is available; in presence of nickel (Cu,Ni)6Sn5 compound can be formed Cu3Sn common on solder-copper interface, forms preferentially when excess of copper is available, more thermally stable than Cu6Sn5, often present when higher-temperature soldering occurred Ni3Sn4 common on solder-nickel interface FeSn2 very slow formation Ag3Sn- at higher concentration of silver (over 3%) in tin forms platelets that can serve as crack initiation sites. AuSn4 -phase brittle, forms at excess of tin. Detrimental to properties of tin-based solders to gold-plated layers. AuIn2 forms on the boundary between gold and indium-lead solder, acts as a barrier against further dissolution of gold Glass solder Glass solders are used to join glasses to other glasses, ceramics, metals, semiconductors, mica, and other materials, in a process called glass frit bonding. The glass solder has to flow and wet the soldered surfaces well below the temperature where deformation or degradation of either of the joined materials or nearby structures (e.g., metallization layers on chips or ceramic substrates) occurs. The usual temperature of achieving flowing and wetting is between 450 and 550C. Two types of glass solders are used: vitreous, and devitrificationdevitrifying. Vitreous solders retain their amorphous structure during remelting, can be reworked repeatedly, and are relatively transparent. Devitrifying solders undergo partial crystallization during solidifying, forming a glass-ceramic, a composite of glassy and crystalline phases. Devitrifying solders usually create a stronger mechanical bond, but are more temperature-sensitive and the seal is more likely to be leaky; due to their polycrystalline structure they tend to be translucent or opaque. Devitrifying solders are frequently "thermosetting", as their melting temperature after recrystallization becomes significantly higher; this allows soldering the parts together at lower temperature than the subsequent bake-out without remelting the joint afterwards. Devitrifying solders frequently contain up to 25% zinc oxide. In production of cathode ray tubes, devitrifying solders based on PbO-B2O3-ZnO are used. Very low temperature melting glasses, fluid at 200400C, were developed for sealing applications for electronics. They can consist of binary or ternary mixtures of thallium, arsenic and sulfur. Zinc-silicoborate glasses can also be used for passivation of electronics; their coefficient of thermal expansion must match silicon (or the other semiconductors used) and they must not contain alkaline metals as those would migrate to the semiconductor and cause failures.The bonding between the glass or ceramics and the glass solder can be either covalent bondcovalent, or, more often, van der Waals forcevan der Waals. The seal can be leak-tight; glass soldering is frequently used in vacuum technology. Glass solders can be also used as sealants; a vitreous enamel coating on iron lowered its permeability to hydrogen 10 times. Glass solders are frequently used for glass-to-metal seals and glass-ceramic-to-metal seals. Glass solders are available as frit powder with grain size below 60 micrometers. They can be mixed with water or alcohol to form a paste for easy application, or with dissolved nitrocellulose or other suitable binder for adhering to the surfaces until being melted. The eventual binder has to be burned off before melting proceeds, requiring careful pottery firingfiring regime. The solder glass can be also applied from molten state to the area of the future joint during manufacture of the part. Due to their low viscosity in molten state, lead glasses with high lead(II) oxidePbO content (often 7085%) are frequently used. The most common compositions are based on lead borates (leaded borate glass or borosilicate glass). Smaller amount of zinc oxide or aluminium oxide can be added for increasing chemical stability. Phosphate glasses can be also employed. Zinc oxide, bismuth trioxide, and copper(II) oxide can be added for influencing the thermal expansion; unlike the alkali oxides, these lower the softening point without increasing of thermal expansion. Glass solders are frequently used in electronic packaging. CERDIP packagings are an example. Outgassing of water from the glass solder during encapsulation was a cause of high failure rates of early CERDIP integrated circuits. Removal of glass-soldered ceramic covers, e.g., for gaining access to the chip for failure analysis or reverse engineering, is best done by shearing (physics)shearing; if this is too risky, the cover is polished away instead.As the seals can be performed at much lower temperature than with direct joining of glass parts and without use of flame (using a temperature-controlled kiln or oven), glass solders are useful in applications like subminiature vacuum tubes or for joining mica windows to vacuum tubes and instruments (e.g., Geiger tube). Thermal expansion coefficient has to be matched to the materials being joined and often is chosen in between the coefficients of expansion of the materials. In case of having to compromise, subjecting the joint to compression stresses is more desirable than to tensile stresses. The expansion matching is not

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Solder critical in applications where thin layers are used on small areas, e.g., fireable inks, or where the joint will be subjected to a permanent compression (e.g., by an external steel shell) offsetting the thermally introduced tensile stresses.Glass solder can be used as an intermediate layer when joining materials (glasses, ceramics) with significantly different coefficient of thermal expansion; such materials cannot be directly joined by diffusion welding. Evacuated glazing windows are made of glass panels soldered together.A glass solder is used, e.g., for joining together parts of cathode ray tubes and plasma display panels. Newer compositions lowered the usage temperature from 450 to 390C by reducing the lead(II) oxide content down from 70%, increasing the zinc oxide content, adding titanium dioxide and bismuth(III) oxide and some other components. The high thermal expansion of such glass can be reduced by a suitable ceramic filler (material)filler. Lead-free solder glasses with soldering temperature of 450C were also developed. Phosphate glasses with low melting temperature were developed. One of such compositions is phosphorus pentoxide, lead(II) oxide, and zinc oxide, with addition of lithium and some other oxides.Conductive glass solders can be also prepared. Preform A preform is a pre-made shape of solder specially designed for the application where it is to be used. Solder Preforms Many methods are used to manufacture the solder preform, stamping being the most common. The solder preform may include the solder flux needed for the soldering process. This can be an internal flux, inside the solder preform, or external, with the solder preform coated.ReferencesBibliographySanka Ganesan, Michael Pecht (2006). Lead-free electronics. Wiley. International Standard Book NumberISBN0-471-78617-9.External links Physical Properties Table of Solders Lead-free solder alloys Common solder alloys and their melting ranges Phase diagrams of different types of solder alloys Phase diagrams for lead free solders

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Ductility
In materials science, ductility is a solid material's ability to deform under tensile stress; this is often characterized by the material's ability to be stretched into a wire. Malleability, a similar property, is a material's ability to deform under compressive stress; this is often characterized by the material's ability to form a thin sheet by hammering or rolling. Both of these mechanical properties are aspects of plasticity, the extent to which a solid material can be plastically deformed without fracture. Also, these material properties are dependent on temperature and pressure (investigated by Percy Williams Bridgman as part of his Nobel Prize winning work on high pressures). Ductility and malleability are not always coextensive for instance, while gold is both ductile and malleable, lead is only malleable.[1] The word ductility is sometimes used to embrace both types of plasticity.[2]

Tensile test of an AlMgSi alloy. The local necking and the cup and cone fracture surfaces are typical for ductile metals.

Ductility

164

This tensile test of a nodular cast iron demonstrates low ductility.

Materials science
Ductility is especially important in metalworking, as materials that crack or break under stress cannot be manipulated using metal forming processes, such as hammering, rolling, and drawing. Malleable materials can be formed using stamping or pressing, whereas brittle metals and plastics must be molded. High degrees of ductility occur due to metallic bonds, which are found predominantly in metals and leads to the common perception that metals are ductile in general. In metallic bonds valence shell electrons are delocalized and shared between many atoms. The delocalized electrons allow metal atoms to slide past one another without being subjected to strong repulsive forces that would cause other materials to shatter. Ductility can be quantified by the fracture strain

Gold leaf is possible due to gold's malleability.

, which is the engineering strain at which a test specimen .[3]

fractures during a uniaxial tensile test. Another commonly used measure is the reduction of area at fracture

The ductility of steel varies depending on the alloying constituents. Increasing levels of carbon decreases ductility. Many plastics and amorphous solids, such as Play-Doh, are also malleable. The most ductile metal is platinum and the most malleable metal is gold [4][5]

Ductility

165

Ductilebrittle transition temperature


The ductilebrittle transition temperature (DBTT), nil ductility temperature (NDT), or nil ductility transition temperature of a metal represents the point at which the fracture energy passes below a pre-determined point (for steels typically 40 J[6] for a standard Charpy impact test). DBTT is important since, once a material is cooled below the DBTT, it has a much greater tendency to shatter on impact instead of bending or deforming. For example, zamak 3 exhibits good ductility at room temperature but shatters at sub-zero temperatures when impacted. DBTT is a very important consideration in materials selection when the material in question is subject to mechanical stresses. A similar phenomenon, the glass transition temperature, occurs with glasses and polymers, although the mechanism is different in these amorphous materials.

In some materials this transition is sharper than others. For example, the transition is generally sharper in materials with a body-centered cubic (BCC) lattice than those with a face-centered cubic (FCC) lattice. DBTT can also be influenced by external factors such as neutron radiation, which leads to an increase in internal lattice defects and a corresponding decrease in ductility and increase in DBTT. The most accurate method of measuring the BDT or DBT temperature of a material is by fracture testing. Typically, four point bend testing at a range of temperatures is performed on pre-cracked bars of polished material. For experiments conducted at higher temperatures, dislocation activity increases. At a certain temperature, dislocations shield the crack tip to such an extent the applied deformation rate is not sufficient for the stress intensity at the crack-tip to reach the critical value for fracture (KiC). The temperature at which this occurs is the ductilebrittle transition temperature. If experiments are performed at a higher strain rate, more dislocation shielding is required to prevent brittle fracture and the transition temperature is raised.

Schematic appearance of round metal bars after tensile testing. (a) Brittle fracture (b) Ductile fracture (c) Completely ductile fracture

References
[1] . [2] Includes definitions from American Heritage Dictionary of the English Language, Collins English Dictionary: Complete and Unabridged, American Heritage Science Dictionary, and WordNet 3.0. [3] G. Dieter, Mechanical Metallurgy, McGraw-Hill, 1986, ISBN 978-0-07-016893-0 [4] Materials handbook,Mc Graw-Hill handbooks, by John Vaccaro, fifteenth edition, 2002 [5] CRC encyclopedia of materials parts and finishes, second edition, 2002, M.Schwartz [6] John, Vernon. Introduction to Engineering Materials, 3rd ed.(?) New York: Industrial Press, 1992. ISBN 0-8311-3043-1.

External links
Ductility definition at engineersedge.com (http://www.engineersedge.com/material_science/ductility.htm) DoITPoMS Teaching and Learning Package- "The Ductile-Brittle Transition (http://www.doitpoms.ac.uk/ tlplib/ductile-brittle-transition/index.php)

Gold

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Gold
Gold Au 79

platinum gold mercuryAg

Au
Rg Gold in the periodic table Appearance metallic yellow

General properties Name, symbol, number Pronunciation Element category Group, period, block Standard atomic weight gold, Au, 79 /old/ transition metal 11, 6, d 196.966569(4)

Gold

167
Electron configuration

[Xe] 4f14 5d10 6s1 2, 8, 18, 32, 18, 1

History Naming Discovery aurum in Latin, meaning glow of sunrise Middle Easterns (before 6000 BC) Physical properties Phase Density (near r.t.) Liquid density at m.p. Meltingpoint Boilingpoint Heatoffusion Heat of vaporization Molar heat capacity solid 19.30 gcm3 17.31 gcm3 1337.33K, 1064.18C, 1947.52F 3129K, 2856C, 5173F 12.55 kJmol1 324 kJmol1 25.418 Jmol1K1 Vapor pressure P (Pa) 1 10 100 1k 10 k 100 k

at T (K) 1646 1814 2021 2281 2620 3078 Atomic properties Oxidation states Electronegativity Ionization energies 5, 4, 3, 2, 1, 1, 2 (amphoteric oxide) 2.54 (Pauling scale) 1st: 890.1 kJmol1 2nd: 1980 kJmol1 Atomic radius Covalent radius Van der Waals radius 144 pm 1366 pm 166 pm Miscellanea

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168
Crystal structure lattice face centered cubic

Magnetic ordering Electrical resistivity Thermal conductivity Thermal expansion

diamagnetic

[1]

(20C) 22.14 nm 318Wm1K1 (25 C) 14.2 mm1K1

Speed of sound (thin rod) (r.t.) 2030ms1 Tensile strength Young's modulus Shear modulus Bulk modulus Poisson ratio Mohs hardness Vickers hardness Brinell hardness CAS registry number 120 MPa 79 GPa 27 GPa 180[citation needed] GPa 0.44 2.5 216 MPa 25 HB = ?? MPa 7440-57-5 Most stable isotopes Main article: Isotopes of gold iso
195 196

NA syn syn

half-life 186.10 d 6.183 d

DM DE (MeV) 0.227 1.506 0.686

DP
195 196 196

Au Au

Pt Pt

Hg

197 198 199

Au 100% Au Au syn syn

197

Au is stable with 118 neutrons 1.372 0.453


198 199

2.69517 d 3.169 d

Hg Hg

Gold is a chemical element with the symbol Au and atomic number 79. It is a dense, soft, malleable, and ductile metal with a bright yellow color and luster that is considered attractive, which is maintained without tarnishing in air or water. Chemically, gold is a transition metal and a group 11 element. It is one of the least reactive chemical elements, solid under standard conditions. The metal therefore occurs often in free elemental (native) form, as nuggets or grains in rocks, in veins and in alluvial deposits. Less commonly, it occurs in minerals as gold compounds, usually with tellurium.[citation needed] Gold resists attacks by individual acids, but it can be dissolved by the aqua regia (nitro-hydrochloric acid), so named because it dissolves gold. Gold also dissolves in alkaline solutions of cyanide, which have been used in mining. It dissolves in mercury, forming amalgam alloys; is insoluble in nitric acid, which dissolves silver and base metals, a property that has long been used to confirm the presence of gold in items, giving rise to the term acid test.

Gold This metal has been a valuable and highly sought-after precious metal for coinage, jewelry, and other arts since long before the beginning of recorded history. Gold standards have sometimes been monetary policies, but were widely supplanted by fiat currency starting in the 1930s. The last gold certificate and gold coin currencies were issued in the U.S. in 1932. In Europe, most countries left the gold standard with the start of World War I in 1914 and, with huge war debts, did not return to gold as a medium of exchange. A total of 174,100 tonnes of gold have been mined in human history, according to GFMS as of 2012.[2] This is roughly equivalent to 5.6 billion troy ounces or, in terms of volume, about 9261 m3, or a cube 21.0 m on a side. The world consumption of new gold produced is about 50% in jewelry, 40% in investments, and 10% in industry.[] Besides its widespread monetary and symbolic functions, gold has many practical uses in dentistry, electronics, and other fields. Its high malleability, ductility, resistance to corrosion and most other chemical reactions, and conductivity of electricity has led to many uses, including electric wiring, colored-glass production, and gold leafing. Most of the Earth's gold lies at its core, the metal's high density having made it sink there in the planet's youth. Virtually all discovered gold is considered to have been deposited later by meteorites that contained the element,[3][4][5][6][7] with the asteroid that formed Vredefort crater having been implicated in the formation of the largest gold mining region on earth, Witwatersrand basin.[8][9][10][11]

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Etymology
"Gold" is cognate with similar words in many Germanic languages, deriving via Proto-Germanic *gul from Proto-Indo-European *gel- ("yellow/green").[12][13] The symbol Au is from the Latin: aurum, according to some sources meaning "shining dawn",[14] from Sabine ausum "glowing dawn"[15] although according to definitions within Latin dictionaries the meaning of the word aurum extends only to the same as today's reference to the metal.[16] The disagreement between definitions is possibly due to the accumulation of evidence from archaeology of the original anciency of the metal in civilization; in reference to "the dawn of civilization",[17] and in this respect has become the adopted modern meaning, disassociated from the original etymological Latin.[18]

Characteristics
Gold is the most malleable of all metals; a single gram can be beaten into a sheet of 1 square meter, or an ounce into 300 square feet. Gold leaf can be beaten thin enough to become transparent. The transmitted light appears greenish blue, because gold strongly reflects yellow and red.[19] Such semi-transparent sheets also strongly reflect infrared light, making them useful as infrared (radiant heat) shields in visors of heat-resistant suits, and in sun-visors for spacesuits.[20] Gold readily creates alloys with many other metals. These alloys can be produced to modify the hardness and other metallurgical properties, to control melting point or to create exotic colors.[] Gold is a good conductor of heat and electricity and reflects infrared radiation strongly. Chemically, it is unaffected by air, moisture and most corrosive reagents, and is therefore well suited for use in coins and jewelry and as a protective coating on other, more reactive metals. However, it is not chemically inert. Gold is almost insoluble, but can be dissolved in aqua regia. Common oxidation states of gold include +1 (gold(I) or aurous compounds) and +3 (gold(III) or auric compounds). Gold ions in solution are readily reduced and precipitated as metal by adding any other metal as the reducing agent. The added metal is oxidized and dissolves, allowing the gold to be displaced from solution and be recovered as a solid precipitate. In addition, gold is very dense, a cubic meter weighing 19,300 kg. By comparison, the density of lead is 11,340kg/m3, and that of the densest element, osmium, is 22,610kg/m3.

Gold

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Color
Whereas most other pure metals are gray or silvery white, gold is yellow. This color is determined by the density of loosely bound (valence) electrons; those electrons oscillate as a collective "plasma" medium described in terms of a quasiparticle called plasmon. The frequency of these oscillations lies in the ultraviolet range for most metals, but it falls into the visible range for gold due to subtle relativistic effects that affect the orbitals around gold atoms.[21][22] Similar effects impart a golden hue to metallic caesium. Common colored gold alloys such as rose gold can be created by the addition of various amounts of copper and silver, as indicated in the Different colors of Ag-Au-Cu alloys triangular diagram to the left. Alloys containing palladium or nickel are also important in commercial jewelry as these produce white gold alloys. Less commonly, addition of manganese, aluminium, iron, indium and other elements can produce more unusual colors of gold for various applications.[]

Isotopes
Gold has only one stable isotope, 197Au, which is also its only naturally occurring isotope. Thirty-six radioisotopes have been synthesized ranging in atomic mass from 169 to 205. The most stable of these is 195Au with a half-life of 186.1 days. The least stable is 171Au, which decays by proton emission with a half-life of 30 s. Most of gold's radioisotopes with atomic masses below 197 decay by some combination of proton emission, decay, and + decay. The exceptions are 195Au, which decays by electron capture, and 196Au, which decays most often by electron capture (93%) with a minor - decay path (7%).[23] All of gold's radioisotopes with atomic masses above 197 decay by - decay.[] At least 32 nuclear isomers have also been characterized, ranging in atomic mass from 170 to 200. Within that range, only 178Au, 180Au, 181Au, 182Au, and 188Au do not have isomers. Gold's most stable isomer is 198m2Au with a half-life of 2.27 days. Gold's least stable isomer is 177 m2Au with a half-life of only 7 ns. 184 m1Au has three decay paths: + decay, isomeric transition, and alpha decay. No other isomer or isotope of gold has three decay paths.[]

Applications
Monetary exchange
Gold has been widely used throughout the world as a vehicle for monetary exchange, either by issuance and recognition of gold coins or other bare metal quantities, or through gold-convertible paper instruments by establishing gold standards in which the total value of issued money is represented in a store of gold reserves. The first gold coins of the Grecian age were struck in Lydia around 700 BC.[24] The talent coin of gold in use during the periods of Grecian history both before and during the time of the life of Homer Gold is commonly formed into bars for use in monetary exchange. weighed between 8.42 and 8.75grams.[25] From an earlier preference in using silver, European economies re-established the minting of gold as coinage during the thirteenth and fourteenth centuries.[]

Gold However, production has not grown in relation to the world's economies. Today, gold mining output is declining.[26] With the sharp growth of economies in the 20th century, and increasing foreign exchange, the world's gold reserves and their trading market have become a small fraction of all markets and fixed exchange rates of currencies to gold were no longer sustained. At the beginning of World War I the warring nations moved to a fractional gold standard, inflating their currencies to finance the war effort. After World War II gold was replaced by a system of convertible currency following the Bretton Woods system. Gold standards and the direct convertibility of currencies to gold have been abandoned by world governments, being replaced by fiat currency in their stead. Switzerland was the last country to tie its currency to gold; it backed 40% of its value until the Swiss joined the International Monetary Fund in 1999.[27] The gold content of alloys is measured in carats (k). Pure gold is designated as 24k. English gold coins intended for circulation from 1526 into the 1930s were typically a standard 22k alloy called crown gold,[28] for hardness (American gold coins for circulation after 1837 contained the slightly lower amount of 0.900 fine gold, or 21.6 kt).[29] Although the prices of some platinum group metals can be much higher, gold has long been considered the most desirable of precious metals, and its value has been used as the standard for many currencies. Gold has been used as a symbol for purity, value, royalty, and particularly roles that combine these properties. Gold as a sign of wealth and prestige was ridiculed by Thomas More in his treatise Utopia. On that imaginary island, gold is so abundant that it is used to make chains for slaves, tableware, and lavatory seats. When ambassadors from other countries arrive, dressed in ostentatious gold jewels and badges, the Utopians mistake them for menial servants, paying homage instead to the most modestly dressed of their party.

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Investment
Many holders of gold store it in form of bullion coins or bars as a hedge against inflation or other economic disruptions. However, economist Martin Feldstein does not believe gold serves as a hedge against inflation or currency depreciation.[30] The ISO 4217 currency code of gold is XAU. Modern bullion coins for investment or collector purposes do not require good mechanical wear properties; they are Gold prices (US$ per troy ounce), in nominal US$ and inflation adjusted US$. typically fine gold at 24k, although the American Gold Eagle and the British gold sovereign continue to be minted in 22k metal in historical tradition, and the South African Krugerand, first released in 1967, is also 22k.[31] The special issue Canadian Gold Maple Leaf coin contains the highest purity gold of any bullion coin, at 99.999% or 0.99999, while the popular issue Canadian Gold Maple Leaf coin has a purity of 99.99%. Several other 99.99% pure gold coins are available. In 2006, the United States Mint began producing the American Buffalo gold bullion coin with a purity of 99.99%. The Australian Gold Kangaroos were first coined in 1986 as the Australian Gold Nugget but changed the reverse design in 1989. Other modern coins include the Austrian Vienna Philharmonic bullion coin and the Chinese Gold Panda.

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172

Jewelry
Because of the softness of pure (24k) gold, it is usually alloyed with base metals for use in jewelry, altering its hardness and ductility, melting point, color and other properties. Alloys with lower caratage, typically 22k, 18k, 14k or 10k, contain higher percentages of copper or other base metals or silver or palladium in the alloy. Copper is the most commonly used base metal, yielding a redder color.[32] Eighteen-carat gold containing 25% copper is found in antique and Russian jewelry and has a distinct, though not dominant, copper cast, Moche gold necklace depicting feline heads. creating rose gold. Fourteen-carat gold-copper alloy is nearly identical Larco Museum Collection. Lima-Peru in color to certain bronze alloys, and both may be used to produce police and other badges. Blue gold can be made by alloying with iron and purple gold can be made by alloying with aluminium, although rarely done except in specialized jewelry. Blue gold is more brittle and therefore more difficult to work with when making jewelry.[32] Fourteen- and eighteen-carat gold alloys with silver alone appear greenish-yellow and are referred to as green gold. White gold alloys can be made with palladium or nickel. White 18-carat gold containing 17.3% nickel, 5.5% zinc and 2.2% copper is silvery in appearance. Nickel is toxic, however, and its release from nickel white gold is controlled by legislation in Europe.[32] Alternative white gold alloys are available based on palladium, silver and other white metals,[32] but the palladium alloys are more expensive than those using nickel. High-carat white gold alloys are far more resistant to corrosion than are either pure silver or sterling silver. The Japanese craft of Mokume-gane exploits the color contrasts between laminated colored gold alloys to produce decorative wood-grain effects.

Medicine
Conceived of as perhaps the most anciently administered medicine (apparently according to one source by shamanic practitioners)[33] and known of by Dioscorides,[34][35] apparent paradoxes of the actual toxicology of the substance nevertheless suggests the possibility still of serious gaps in understanding of action on physiology.[36] In medieval times, gold was often seen as beneficial for the health, in the belief that something so rare and beautiful could not be anything but healthy. Even some modern esotericists and forms of alternative medicine assign metallic gold a healing power.[37] Some gold salts do have anti-inflammatory properties and are used as pharmaceuticals in the treatment of arthritis and other similar conditions. Gold based injections have been explored as a means to help to reduce the pain and swelling of rheumatoid arthritis and tuberculosis.[] However, only salts and radioisotopes of gold are of pharmacological value, as elemental (metallic) gold is inert to all chemicals it encounters inside the body. Gold alloys are used in restorative dentistry, especially in tooth restorations, such as crowns and permanent bridges. The gold alloys' slight malleability facilitates the creation of a superior molar mating surface with other teeth and produces results that are generally more satisfactory than those produced by the creation of porcelain crowns. The use of gold crowns in more prominent teeth such as incisors is favored in some cultures and discouraged in others. Colloidal gold preparations (suspensions of gold nanoparticles) in water are intensely red-colored, and can be made with tightly controlled particle sizes up to a few tens of nanometers across by reduction of gold chloride with citrate or ascorbate ions. Colloidal gold is used in research applications in medicine, biology and materials science. The technique of immunogold labeling exploits the ability of the gold particles to adsorb protein molecules onto their surfaces. Colloidal gold particles coated with specific antibodies can be used as probes for the presence and position of antigens on the surfaces of cells.[38] In ultrathin sections of tissues viewed by electron microscopy, the immunogold labels appear as extremely dense round spots at the position of the antigen.[39]

Gold Gold, or alloys of gold and palladium, are applied as conductive coating to biological specimens and other non-conducting materials such as plastics and glass to be viewed in a scanning electron microscope. The coating, which is usually applied by sputtering with an argon plasma, has a triple role in this application. Gold's very high electrical conductivity drains electrical charge to earth, and its very high density provides stopping power for electrons in the electron beam, helping to limit the depth to which the electron beam penetrates the specimen. This improves definition of the position and topography of the specimen surface and increases the spatial resolution of the image. Gold also produces a high output of secondary electrons when irradiated by an electron beam, and these low-energy electrons are the most commonly used signal source used in the scanning electron microscope.[40] The isotope gold-198 (half-life 2.7 days) is used, in nuclear medicine, in some cancer treatments and for treating other diseases.[41][42]

173

Food and drink


Gold can be used in food and has the E number 175.[] Gold leaf, flake or dust is used on and in some gourmet foods, notably sweets and drinks as decorative ingredient.[43] Gold flake was used by the nobility in medieval Europe as a decoration in food and drinks, in the form of leaf, flakes or dust, either to demonstrate the host's wealth or in the belief that something that valuable and rare must be beneficial for one's health. Danziger Goldwasser (German: Gold water of Danzig) or Goldwasser (English: Goldwater) is a traditional German herbal liqueur[44] produced in what is today Gdask, Poland, and Schwabach, Germany, and contains flakes of gold leaf. There are also some expensive (~$1000) cocktails which contain flakes of gold leaf.[45] However, since metallic gold is inert to all body chemistry, it has no taste, it provides no nutrition, and it leaves the body unaltered.[46]

Industry
Gold solder is used for joining the components of gold jewelry by high-temperature hard soldering or brazing. If the work is to be of hallmarking quality, gold solder must match the carat weight of the work, and alloy formulas are manufactured in most industry-standard carat weights to color match yellow and white gold. Gold solder is usually made in at least three melting-point ranges referred to as Easy, Medium and Hard. By using the hard, high-melting point solder first, followed by solders with progressively lower melting points, goldsmiths can assemble complex items with several separate soldered joints. Gold can be made into thread and used in embroidery. Gold produces a deep, intense red color when used as a coloring agent in cranberry glass. In photography, gold toners are used to shift the color of silver bromide black-and-white prints towards brown or blue tones, or to increase their stability. Used on sepia-toned prints, gold toners produce red tones. Kodak published formulas for several types of gold toners, which use gold as the chloride.[47] Gold is a good reflector of electromagnetic radiation such as infrared and visible light as well as radio waves. It is used for the

The 220kg gold brick displayed in Jinguashi Gold Museum, Taiwan, Republic of China.

Gold protective coatings on many artificial satellites, in infrared protective faceplates in thermal protection suits and astronauts' helmets and in electronic warfare planes like the EA-6B Prowler. Gold is used as the reflective layer on some high-end CDs. Automobiles may use gold for heat shielding. McLaren uses gold foil in the engine compartment of its F1 model.[48] Gold can be manufactured so thin that it appears transparent. It is used in some aircraft cockpit windows for de-icing or anti-icing by passing electricity through it. The heat produced by the resistance of the gold is enough to deter ice from forming.[]

174

Electronics
The concentration of free electrons in gold metal is 5.901022 cm3. Gold is highly conductive to electricity, and has been used for electrical wiring in some high-energy applications (only silver and copper are more conductive per volume, but gold has the advantage of corrosion resistance). For example, gold electrical wires were used during some of the Manhattan Project's atomic experiments, but large high current silver wires were used in the calutron isotope separator magnets in the project.

The world's largest gold bar has a mass of 250 kg. Toi museum, Japan.

Though gold is attacked by free chlorine, its good conductivity and general resistance to oxidation and corrosion in other environments (including resistance to non-chlorinated acids) has led to its widespread industrial use in the electronic era as a thin layer coating electrical connectors, thereby ensuring good connection. For example, gold is used in the connectors of the more expensive electronics cables, such as audio, video and USB cables. The benefit of using A gold nugget of 5 mm in diameter gold over other connector metals such as tin in these applications has been (bottom) can be expanded through debated; gold connectors are often criticized by audio-visual experts as hammering into a gold foil of about unnecessary for most consumers and seen as simply a marketing ploy. However, 0.5 square meters. Toi museum, Japan. the use of gold in other applications in electronic sliding contacts in highly humid or corrosive atmospheres, and in use for contacts with a very high failure cost (certain computers, communications equipment, spacecraft, jet aircraft engines) remains very common.[49] Besides sliding electrical contacts, gold is also used in electrical contacts because of its resistance to corrosion, electrical conductivity, ductility and lack of toxicity.[50] Switch contacts are generally subjected to more intense corrosion stress than are sliding contacts. Fine gold wires are used to connect semiconductor devices to their packages through a process known as wire bonding.

Commercial chemistry
Gold is attacked by and dissolves in alkaline solutions of potassium or sodium cyanide, to form the salt gold cyanidea technique that has been used in extracting metallic gold from ores in the cyanide process. Gold cyanide is the electrolyte used in commercial electroplating of gold onto base metals and electroforming. Gold chloride (chloroauric acid) solutions are used to make colloidal gold by reduction with citrate or ascorbate ions. Gold chloride and gold oxide are used to make cranberry or red-colored glass, which, like colloidal gold suspensions, contains evenly sized spherical gold nanoparticles.[51]

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Cultural history
Gold artifacts found at the Nahal Kana cave cemetery dated during the 1980s, showed these to be from within the Chalcolithic, and considered the earliest find from the Levant (Gopher et al. 1990).[] Gold artifacts in the Balkans also appear from the 4th millennium BC, such as those found in the Varna Necropolis near Lake Varna in Bulgaria, thought by one source (La Niece 2009) to be the earliest "well-dated" find of gold artifacts.[] Gold artifacts such as the golden hats and the Nebra disk appeared in Central Europe from the 2nd millennium BC Bronze Age. Egyptian hieroglyphs from as early as 2600 BC describe gold, which king Tushratta of the Mitanni claimed was "more plentiful than dirt" in Egypt.[52] Egypt and especially Nubia had the resources to make them major gold-producing areas for much of history. The earliest known map is known as the Turin Papyrus Map and shows the plan of a gold mine in Nubia together with indications of the local geology. The primitive working methods are described by both Strabo and Diodorus Siculus, and included fire-setting. Large mines were also present across the Red Sea in what is now Saudi Arabia. The legend of the golden fleece may refer to the use of fleeces to trap gold dust from placer deposits in the ancient world. Gold is mentioned frequently in the Old Testament, starting with Genesis 2:11 (at Havilah), the story of The Golden Calf and many parts of the temple including the Menorah and the golden altar. In the New Testament, it is included with the gifts of the magi in the first chapters of Matthew. The Book of Revelation 21:21 describes the city of New Jerusalem as having streets "made of pure gold, clear as crystal". Exploitation of gold in the south-east corner of the Black Sea is said to date from the time of Midas, and this gold was important in the establishment of what is probably the world's earliest coinage in Lydia around 610 BC.[53] From the 6th or 5th century BC, the Chu (state) circulated the Ying Yuan, one kind of square gold coin.

The Turin Papyrus Map

Funerary mask of Tutankhamun

In Roman metallurgy, new methods for extracting gold on a large scale were developed by introducing hydraulic mining methods, especially in Hispania from 25 BC onwards and in Dacia from 106 AD onwards. Jason returns with the golden fleece One of their largest mines was at Las Medulas in Len (Spain), where on an Apulian red-figure calyx krater, ca. 340330 BC. seven long aqueducts enabled them to sluice most of a large alluvial deposit. The mines at Roia Montan in Transylvania were also very large, and until very recently, still mined by opencast methods. They also exploited smaller deposits in Britain, such as placer and hard-rock deposits at Dolaucothi. The various methods they used are well described by Pliny the Elder in his encyclopedia Naturalis Historia written towards the end of the first century AD.

Gold

176 During Mansa Musa's (ruler of the Mali Empire from 1312 to 1337) hajj to Mecca in 1324, he passed through Cairo in July 1324, and was reportedly accompanied by a camel train that included thousands of people and nearly a hundred camels where he gave away so much gold that it depressed the price in Egypt for over a decade.[54] A contemporary Arab historian remarked: Gold was at a high price in Egypt until they came in that year. The mithqal did not go below 25 dirhams and was generally above, but from that time its value fell and it cheapened in price and has remained cheap till now. The mithqal does not exceed 22 dirhams or less. This has been the state of affairs for about twelve years until this day by reason of the large amount of gold which they brought into Egypt and spent there [...] Chihab Al-Umari,[55] The Portuguese overseas expansion started in 1415 with the taking of Ceuta, to control the gold trade coming across the desert. Although the caravan trade routes were then diverted, the Portuguese continued expansing southwards along the coast and eventually buying the gold directly (or less indirectly) from the Africans in the Gulf of Guinea.[citation needed]

Ancient Greek golden decorated crown, funerary or marriage material, 370360 BC. From a grave in Armento, Campania

The European exploration of the Americas was fueled in no small part by reports of the gold ornaments displayed in great profusion by Native American peoples, especially in Central America, Peru, Ecuador and Colombia. The Aztecs regarded gold as literally the product of the gods, calling it "god excrement" (teocuitlatl in Nahuatl), and after Montezuma was killed, most of this gold was shipped to Spain.[56] However, for the indigenous peoples of North America gold was considered useless and they saw much greater value in other minerals which were directly related to their utility, such as obsidian, flint, and slate.[57] Gold played a role in western culture, as a cause for desire and of corruption, as told in children's fables like Rumplestiltskin, where the peasant's daughter turns hay into gold, in return for giving up her child when she becomes a princess, and stealing the hen that lays golden eggs in Jack and the beanstalk. The top prize at the Olympic games is the gold medal. There is an age-old tradition of biting gold to test its authenticity. Although this is certainly not a professional way of examining gold, the bite test was not to check if the coin was gold (90% gold coins are fairly strong) but to see if the coin was gold plated lead. A lead coin would be very soft and thus teeth marks would result. Fake gold coins were a common problem before 1932 so weighing a coin and also sliding a coin through a "counterfeit detector" slot was common (making a lead coin thicker would add weight thus why slide it through a measured slot). Most establishments (especially US Western saloons) would never accept a gold (or silver) coin of high value before weighing such an item.[citation needed] 75% of all gold ever produced has been extracted since 1910.[] It has been estimated that all gold ever refined would form a single cube 20m (66ft) on a side (equivalent to 8,000 m3).[] One main goal of the alchemists was to produce gold from other substances, such as lead presumably by the interaction with a mythical substance called the philosopher's stone. Although they never succeeded in this attempt, the alchemists promoted an interest in what can be done with substances, and this laid a foundation for today's chemistry. Their symbol for gold was the circle with a point at its center (), which was also the astrological symbol and the ancient Chinese character for the Sun.

Gold Golden treasures have been rumored to be found at various locations, following tragedies such as the Jewish temple treasures in the Vatican, following the temple's destruction in 70 AD, a gold stash on the Titanic, the Nazi gold train following World War II. The Dome of the Rock on the Jerusalem temple site is covered with an ultra-thin golden glasureWikipedia:Please clarify. The Sikh Golden temple, the Harmandir Sahib, is a building covered with gold. Similarly the Wat Phra Kaew emerald Budha temple in Thailand has ornamental gold statues walls and roofs. Some European king and queen's crowns were made of gold, and gold was used for the bridal crown since antiquity. An ancient Talmudic text circa 100 AD describes Rachel, Rabbi Akiba's wife asking for a "Jerusalem of Gold" (crown). A Greek burial crown made of gold was found in a grave circa 370 BC.

177

Occurrence
Gold's atomic number of 79 makes it one of the higher atomic number elements which occur naturally. Like all elements with atomic numbers larger than iron, gold is thought to have been formed from a supernova nucleosynthesis process,[citation needed] although a newer theory suggests they are made by the collision of neutron stars instead.[58] Either way, the resulting explosions scattered metal-containing dusts (including heavy elements like gold) into the region of space in which they later condensed into our solar system and the Earth.[59] Because the Earth was molten when it was just formed, almost all of the gold present on Earth sank into the core. Most of the gold that is present today in the Earth's crust and mantle was delivered to Earth by asteroid impacts during the late heavy bombardment.[60]

On Earth, gold is found in ores in rock formed from the Precambrian time onward.[] It most often occurs as a native metal, typically in a metal solid solution with silver (i.e. as a gold silver alloy). Such alloys usually have a silver content of 810%. Electrum is elemental gold with more than 20% silver. Electrum's color runs from golden-silvery to silvery, dependent upon the silver content. The more silver, the lower the specific gravity. Native gold occurs as very small to microscopic particles embedded in rock, often together with quartz or sulfide minerals such as "Fool's Gold", which is a pyrite.[61] These are called lode deposits. The metal in a native state is also found in the form of free flakes, grains or larger nuggets[] that have been eroded from rocks and end up in alluvial deposits called placer deposits. Such free gold is always richer at the surface of gold-bearing veinsWikipedia:Please clarify owing to the oxidation of accompanying minerals followed by weathering, and washing of the dust into streams and rivers, where it collects and can be welded by water action to form nuggets.

This 156-troy-ounce (4.9kg) nugget, known as the Mojave Nugget, was found by an individual prospector in the Southern California Desert using a metal detector.

Gold

178 Gold sometimes occurs combined with tellurium as the minerals calaverite, krennerite, nagyagite, petzite and sylvanite, and as the rare bismuthide maldonite (Au2Bi) and antimonide aurostibite (AuSb2). Gold also occurs in rare alloys with copper, lead, and mercury: the minerals auricupride (Cu3Au), novodneprite (AuPb3) and weishanite ((Au, Ag)3Hg2). Recent research suggests that microbes can sometimes play an important role in forming gold deposits, transporting and precipitating gold to form grains and nuggets that collect in alluvial deposits.[62] Another recent study has claimed water in faults vaporizes during an earthquake, depositing gold. When an earthquake strikes, it moves along a fault. Water often lubricates faults, filling in fractures and jogs. About 6 miles (10 kilometers) below the surface, under incredible temperatures and pressures, the water carries high concentrations of carbon dioxide, silica, and gold. During an earthquake, the fault jog suddenly opens wider. The water inside the void instantly vaporizes, flashing to steam and forcing silica, which forms the mineral quartz, and gold out of the fluids and onto nearby surfaces.[63]

Relative sizes of an 860 kg block of gold ore, and the 30 g of gold that can be extracted from it. Toi gold mine, Japan.

Seawater
The world's oceans contain gold. Measured concentrations of gold in Gold left behind after a pyrite cube was oxidized the Atlantic and Northeast Pacific are 50150 fmol/L or 1030 parts to hematite. Note cubic shape of cavity. 3 per quadrillion (about 1030 g/km ). In general, gold concentrations for Atlantic and Pacific samples are the same (~50 fmol/L) but less certain. Mediterranean deep waters contain higher concentrations of gold (100150 fmol/L) attributed to wind-blown dust and/or rivers. At 10 parts per quadrillion the Earth's oceans would hold 15,000 tonnes of gold.[64] These figures are three orders of magnitude less than reported in the literature prior to 1988, indicating contamination problems with the earlier data. A number of people have claimed to be able to economically recover gold from sea water, but so far they have all been either mistaken or acted in an intentional deception. Prescott Jernegan ran a gold-from-seawater swindle in the United States in the 1890s. A British fraudster ran the same scam in England in the early 1900s.[65] Fritz Haber (the German inventor of the Haber process) did research on the extraction of gold from sea water in an effort to help pay Germany's reparations following World War I.[66] Based on the published values of 2 to 64 ppb of gold in seawater a commercially successful extraction seemed possible. After analysis of 4,000 water samples yielding an average of 0.004 ppb it became clear that the extraction would not be possible and he stopped the project.[67] No commercially viable mechanism for performing gold extraction from sea water has yet been identified. Gold synthesis is not economically viable and is unlikely to become so in the foreseeable future.

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179

Specimens of crystalline native gold

Native gold nuggets

"Rope gold" from Lena River, Sakha Republic, Russia. Size: 2.51.20.7cm.

Crystalline gold from Mina Zapata, Santa Elena de Uairen, Venezuela. Size: 3.71.10.4cm.

Gold leaf from Harvard Mine, Jamestown, California, USA. Size 9.33.2 >0.1cm.

Production
At the end of 2009, it was estimated that all the gold ever mined totaled 165,000 tonnes.[2] This can be represented by a cube with an edge length of about 20.28 meters. At $1,600 per ounce,Wikipedia:Please clarify 165,000 metric tonnes of gold would have a value of $8.8 trillion. World production for 2011 was at 2,700 tonnes, compared to 2,260 tonnes for 2008. Since the 1880s, South Africa has been the source for a large proportion of the world's gold supply, with about 50% of all gold ever produced having come from South Africa. Production in 1970 accounted for 79% of the world supply, producing about 1,480 tonnes. In 2007 China (with 276 tonnes) overtook South Africa as the world's largest gold producer, the first time since 1905 that South Africa has not been the largest.[68]
The entrance to an underground gold mine in Victoria, Australia

Mining
The city of Johannesburg located in South Africa was founded as a result of the Witwatersrand Gold Rush which resulted in the discovery of some of the largest gold deposits the world has ever seen. Gold fields located within the basin in the Free State and Gauteng provinces are extensive in strike and dip requiring some of the world's deepest Pure gold precipitate produced by the aqua regia refining process mines, with the Savuka and TauTona mines being currently the world's deepest gold mine at 3,777 m. The Second Boer War of 18991901 between the British Empire and the Afrikaner Boers was at least partly over the rights of miners and possession of the gold wealth in South Africa. Other major producers are the United States, Australia, Russia, and Peru, as well as, Ghana, Burkina Faso, Mali, Indonesia and Uzbekistan. Mines in South Dakota and Nevada supply two-thirds of gold used in the United States.

Gold In South America, the controversial project Pascua Lama aims at exploitation of rich fields in the high mountains of Atacama Desert, at the border between Chile and Argentina. Today about one-quarter of the world gold output is estimated to originate from artisanal or small scale mining.[69]

180

Prospecting
During the 19th century, gold rushes occurred whenever large gold deposits were discovered. The first documented discovery of gold in the United States was at the Reed Gold Mine near Georgeville, North Carolina in 1803.[70] The first major gold strike in the United States occurred in a small north Georgia town called Dahlonega.[71] Further gold rushes occurred in California, Colorado, the Black Hills, Otago in New Zealand, Australia, Witwatersrand in South Africa, and the Klondike in Canada.

Extraction
Gold extraction is most economical in large, easily mined deposits. Ore grades as little as 0.5mg/kg (0.5 parts per million, ppm) can be economical. Typical ore grades in open-pit mines are 15mg/kg (15 ppm); ore grades in underground or hard rock mines are usually at least 3mg/kg (3 ppm). Because ore grades of 30mg/kg (30 ppm) are usually needed before gold is visible to the naked eye, in most gold mines the gold is invisible. The average gold mining and extraction costs were about US$317/oz in 2007, but these can vary widely depending on mining type and ore quality; global mine production amounted to 2,471.1 tonnes.[72]

Refining
After initial production, gold is often subsequently refined industrially by the Wohlwill process which is based on electrolysis or by the Miller process, that is chlorination in the melt. The Wohlwill process results in higher purity, but is more complex and is only applied in small-scale installations.[73][74] Other methods of assaying and purifying smaller amounts of gold include parting and inquartation as well as cupellation, or refining methods based on the dissolution of gold in aqua regia.[75]

Synthesis from other elements


Gold was synthesized from mercury by neutron bombardment in 1941, but the isotopes of gold produced were all radioactive.[76] In 1924, a Japanese physicist, Hantaro Nagaoka, accomplished the same feat.[77] Gold can currently be manufactured in a nuclear reactor by irradiation either of platinum or mercury. Only the mercury isotope 196Hg, which occurs with a frequency of 0.15% in natural mercury, can be converted to gold by neutron capture, and following electron capture-decay into 197Au with slow neutrons. Other mercury isotopes are converted when irradiated with slow neutrons into one another, or formed mercury isotopes which beta decay into thallium. Using fast neutrons, the mercury isotope 198Hg, which composes 9.97% of natural mercury, can be converted by splitting off a neutron and becoming 197Hg, which then disintegrates to stable gold. This reaction, however, possesses a smaller activation cross-section and is feasible only with un-moderated reactors. It is also possible to eject several neutrons with very high energy into the other mercury isotopes in order to form 197 Hg. However such high-energy neutrons can be produced only by particle accelerators.Wikipedia:Please clarify.

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181

Consumption
The consumption of gold produced in the world is about 50% in jewelry, 40% in investments, and 10% in industry.[citation needed] India is the world's largest single consumer of gold, as Indians buy about 25% of the world's gold,[78] purchasing approximately 800 tonnes of gold every year, mostly for jewelry. India is also the largest importer of gold; in 2008, India imported around 400 tonnes of gold.[79] Indian households hold 18,000 tonnes of gold which represents 11% of the global stock and worth more than $950 billion.[80]

Gold jewelry consumption by country in tonnes[81][82]


Country India Greater China United States Turkey Saudi Arabia Russia United Arab Emirates Egypt Indonesia United Kingdom Other Persian Gulf Countries Japan South Korea Vietnam Thailand Total Other Countries World Total 2009 442.37 376.96 150.28 75.16 77.75 60.12 67.60 56.68 41.00 31.75 24.10 21.85 18.83 15.08 7.33 2010 745.70 428.00 128.61 74.07 72.95 67.50 63.37 53.43 32.75 27.35 21.97 18.50 15.87 14.36 6.28 2011 986.3 921.5 199.5 143 69.1 76.7 60.9 36 55 22.6 22 -30.1 15.5 100.8 107.4 2012 864 817.5 161 118 58.5 81.9 58.1 47.8 52.3 21.1 19.9 7.6 12.1 77 80.9

1508.70 1805.60 251.6 1760.3 254.0 390.4 393.5

2059.6 3487.5 3163.6

Pollution
Gold production is associated with contribution to hazardous pollution.[83] The ore, generally containing less than one ppm gold metal, is ground and mixed with sodium cyanide or mercury to react with gold in the ore for gold separation. Cyanide is a highly poisonous chemical, which can kill living creatures when exposed in minute quantities. Many cyanide spills[84] from gold mines have occurred in both developed and developing countries which killed marine life in long stretches of affected rivers. Environmentalists consider these events major environmental disasters.[85][86] When mercury is used in gold production, minute quantity of mercury compounds reach water bodies, causing heavy metal contamination. Mercury can then enter into the human food chain in the form of methyl mercury. Mercury poisoning in humans causes incurable brain function damage and severe retardation. Thirty tonnes of used ore is dumped as waste for producing one 1 ounce (28g) of gold.[87] Gold ore dumps are the source of many heavy elements such as cadmium, lead, zinc, copper, arsenic, selenium and mercury. When sulfide bearing minerals in these ore dumps are exposed to air and water, the sulfide transforms into sulfuric acid which in

Gold turn dissolves these heavy metals facilitating their passage into surface water and ground water. This process is called acid mine drainage. These gold ore dumps are long term, highly hazardous wastes second only to nuclear waste dumps.[87] Gold extraction is also a highly energy intensive industry, extracting ore from deep mines and grinding the large quantity of ore for further chemical extraction requires with 25 kWh of electricity required per gram of gold produced.[88]

182

Chemistry
Although gold is the most noble of the noble metals,[89][90] it still forms many diverse compounds. The oxidation state of gold in its compounds ranges from 1 to +5, but Au(I) and Au(III) dominate its chemistry. Au(I), referred to as the aurous ion, is the most common oxidation state with soft ligands such as thioethers, thiolates, and tertiary phosphines. Au(I) compounds are typically linear. A good example is Au(CN)2, which is the soluble form of gold encountered in mining. Curiously, aurous complexes of water are rare. The binary gold halides, such as AuCl, form zigzag polymeric chains, again featuring linear coordination at Au. Most drugs based on gold are Au(I) derivatives.[91]

Gold (III) chloride solution in water

Au(III) (auric) is a common oxidation state, and is illustrated by gold(III) chloride, Au2Cl6. The gold atom centers in Au(III) complexes, like other d8 compounds, are typically square planar, with chemical bonds that have both covalent and ionic character. Aqua regia, a 1:3 mixture of nitric acid and hydrochloric acid, dissolves gold. Nitric acid oxidizes the metal to +3 ions, but only in minute amounts, typically undetectable in the pure acid because of the chemical equilibrium of the reaction. However, the ions are removed from the equilibrium by hydrochloric acid, forming AuCl4 ions, or chloroauric acid, thereby enabling further oxidation. Some free halogens react with gold.[92] Gold also reacts in alkaline solutions of potassium cyanide. With mercury, it forms an amalgam.

Less common oxidation states


Less common oxidation states of gold include 1, +2, and +5. The 1 oxidation state occurs in compounds containing the Au anion, called aurides. Caesium auride (CsAu), for example, crystallizes in the caesium chloride motif.[] Other aurides include those of Rb+, K+, and tetramethylammonium (CH3)4N+.[93] Gold has the highest Pauling electronegativity of any metal, with a value of 2.54, making the auride anion relatively stable. Gold(II) compounds are usually diamagnetic with AuAu bonds such as [Au(CH2)2P(C6H5)2]2Cl2. The evaporation of a solution of Au(OH) 3 in concentrated H 2SO 4 produces red crystals of gold(II) sulfate, Au (SO ) . Originally thought to be a mixed-valence compound, it has 2 4 2 been shown to contain Au4+ [94][95] 2 cations. A noteworthy, legitimate gold(II) complex is the tetraxenonogold(II) cation, which contains xenon as a ligand, found in [AuXe4](Sb2F11)2.[96] Gold pentafluoride, along with its derivative anion, AuF 6, and its difluorine complex, gold heptafluoride, is the sole example of gold(V), the highest verified oxidation

Gold state.[97] Some gold compounds exhibit aurophilic bonding, which describes the tendency of gold ions to interact at distances that are too long to be a conventional AuAu bond but shorter than van der Waals bonding. The interaction is estimated to be comparable in strength to that of a hydrogen bond.

183

Mixed valence compounds


Well-defined cluster compounds are numerous.[93] In such cases, gold has a fractional oxidation state. A representative example is the octahedral species {Au(P(C6H5)3)}62+. Gold chalcogenides, such as gold sulfide, feature equal amounts of Au(I) and Au(III).

Toxicity
Pure metallic (elemental) gold is non-toxic and non-irritating when ingested[98] and is sometimes used as a food decoration in the form of gold leaf. Metallic gold is also a component of the alcoholic drinks Goldschlger, Gold Strike, and Goldwasser. Metallic gold is approved as a food additive in the EU (E175 in the Codex Alimentarius). Although the gold ion is toxic, the acceptance of metallic gold as a food additive is due to its relative chemical inertness, and resistance to being corroded or transformed into soluble salts (gold compounds) by any known chemical process which would be encountered in the human body. Soluble compounds (gold salts) such as gold chloride are toxic to the liver and kidneys. Common cyanide salts of gold such as potassium gold cyanide, used in gold electroplating, are toxic by virtue of both their cyanide and gold content. There are rare cases of lethal gold poisoning from potassium gold cyanide.[99][100] Gold toxicity can be ameliorated with chelation therapy with an agent such as dimercaprol. Gold metal was voted Allergen of the Year in 2001 by the American Contact Dermatitis Society. Gold contact allergies affect mostly women.[101] Despite this, gold is a relatively non-potent contact allergen, in comparison with metals like nickel.[102]

Price
Like other precious metals, gold is measured by troy weight and by grams. When it is alloyed with other metals the term carat or karat is used to indicate the purity of gold present, with 24 carats being pure gold and lower ratings proportionally less. The purity of a gold bar or coin can also be expressed as a decimal figure ranging from 0 to 1, known as the millesimal fineness, such as 0.995 being very pure. The price of gold is determined through trading in the gold and derivatives markets, Gold price history in 19602011 but a procedure known as the Gold Fixing in London, originating in September 1919, provides a daily benchmark price to the industry. The afternoon fixing was introduced in 1968 to provide a price when US markets are open.[103] Historically gold coinage was widely used as currency; when paper money was introduced, it typically was a receipt redeemable for gold coin or bullion. In a monetary system known as the gold standard, a certain weight of gold was

Gold given the name of a unit of currency. For a long period, the United States government set the value of the US dollar so that one troy ounce was equal to $20.67 ($664.56/kg), but in 1934 the dollar was devalued to $35.00 per troy ounce ($1125.27/kg). By 1961, it was becoming hard to maintain this price, and a pool of US and European banks agreed to manipulate the market to prevent further currency devaluation against increased gold demand.[104] On March 17, 1968, economic circumstances caused the collapse of the gold pool, and a two-tiered pricing scheme was established whereby gold was still used to settle international accounts at the old $35.00 per troy ounce ($1.13/g) but the price of gold on the private market was allowed to fluctuate; this two-tiered pricing system was abandoned in 1975 when the price of gold was left to find its free-market level. Central banks still hold historical gold reserves as a store of value although the level has generally been declining. The largest gold depository in the world is that of the U.S. Federal Reserve Bank in New York, which holds about 3%[] of the gold ever mined, as A Swiss-cast 1 kg gold bar does the similarly laden U.S. Bullion Depository at Fort Knox. In 2005 the World Gold Council estimated total global gold supply to be 3,859 tonnes and demand to be 3,754 tonnes, giving a surplus of 105 tonnes.[105] Sometime around 1970 the price began in trend to greatly increase,[106] and since 1968 the price of gold has ranged widely, from a high of $850/oz ($27,300/kg) on January 21, 1980, to a low of $252.90/oz ($8,131/kg) on June 21, 1999 (London Gold Fixing).[107] The period from 1999 to 2001 marked the "Brown Bottom" after a 20-year bear market.[108] Prices increased rapidly from 2001, but the 1980 high was not exceeded until January 3, 2008 when a new maximum of $865.35 per troy ounce was set.[] Another record price was set on March 17, 2008 at $1023.50/oz ($32,900/kg).[] In late 2009, gold markets experienced renewed momentum upwards due to increased demand and a weakening US dollar. On December 2, 2009, Gold reached a new high closing at $1,217.23.[109] Gold further rallied hitting new highs in May 2010 after the European Union debt crisis prompted further purchase of gold as a safe asset.[110][111] On March 1, 2011, gold hit a new all-time high of $1432.57, based on investor concerns regarding ongoing unrest in North Africa as well as in the Middle East.[112] Since April 2001 the gold price has more than quintupled in value against the US dollar, hitting a new all-time high of $1,913.50 on August 23, 2011,[113] prompting speculation that this long secular bear market has ended and a bull market has returned.[114]

184

Symbolism
Great human achievements are frequently rewarded with gold, in the form of gold medals, golden trophies and other decorations. Winners of athletic events and other graded competitions are usually awarded a gold medal. Many awards such as the Nobel Prize are made from gold as well. Other award statues and prizes are depicted in gold or are gold plated (such as the Academy Awards, the Golden Globe Awards, the Emmy Awards, the Palme d'Or, and the British Academy Film Awards). Aristotle in his ethics used gold symbolism when referring to what is Gold bars at the Emperor Casino in Macau now commonly known as the golden mean. Similarly, gold is associated with perfect or divine principles, such as in the case of the golden ratio and the golden rule.

Gold Gold is further associated with the wisdom of aging and fruition. The fiftieth wedding anniversary is golden. Our precious latter years are sometimes considered "golden years". The height of a civilization is referred to as a "golden age". In some forms of Christianity and Judaism, gold has been associated both with holiness and evil. In the Book of Exodus, the Golden Calf is a symbol of idolatry, while in the Book of Genesis, Abraham was said to be rich in gold and silver, and Moses was instructed to cover the Mercy Seat of the Ark of the Covenant with pure gold. In Byzantine iconography the halos of Christ, Mary and the Christian saints are often golden. Medieval kings were inaugurated under the signs of sacred oil and a golden crown, the latter symbolizing the eternal shining light of heaven and thus a Christian king's divinely inspired authority[citation needed]. According to Christopher Columbus, Those who had something of gold, were in possession of something of great value on Earth and a substance to even help souls to paradise.[115] Wedding rings have long been made of gold. It is long lasting and unaffected by the passage of time and may aid in the ring symbolism of eternal vows before God and/or the sun and moon and the perfection the marriage signifies. In Orthodox Christian wedding ceremonies, the wedded couple is adorned with a golden crown (though some opt for wreaths, instead) during the ceremony, an amalgamation of symbolic rites. In popular culture gold holds many connotations but is most generally connected to terms such as good or great, such as in the phrases: "has a heart of gold", "that's golden!", "golden moment", "then you're golden!" and "golden boy". Gold also still holds its place as a symbol of wealth and through that, in many societies, success.

185

State emblem
In 1965, the California Legislature designated gold "the State Mineral and mineralogical emblem".[116] In 1968, the Alaska Legislature named gold "the official state mineral".[117]

References
[1] Magnetic susceptibility of the elements and inorganic compounds (http:/ / www-d0. fnal. gov/ hardware/ cal/ lvps_info/ engineering/ elementmagn. pdf) in [2] World Gold Council FAQ (http:/ / www. gold. org/ investment/ why_how_and_where/ faqs/ #q022). www.gold.org [3] http:/ / www. bbc. co. uk/ news/ science-environment-14827624 [4] http:/ / www. sciencedaily. com/ releases/ 2011/ 09/ 110907132044. htm [5] http:/ / www. ees. rochester. edu/ ees119/ reading2. pdf [6] http:/ / www. huffingtonpost. com/ 2011/ 09/ 10/ meteor-shower-gold_n_955448. html [7] http:/ / www. nature. com/ nature/ journal/ v477/ n7363/ full/ nature10399. html#/ access [8] http:/ / superiormining. com/ properties/ south_africa/ mangalisa/ geology/ [9] http:/ / articles. adsabs. harvard. edu/ / full/ 1997M%26PS. . . 32. . . 71T/ 0000071. 000. html Original size of the Vredefort Structure: Implications for the geological evolution of the Witwatersrand Basin [10] http:/ / www. cosmosmagazine. com/ news/ 2101/ meteor-craters-may-hold-untapped-wealth Meteor craters may hold untapped wealth. Cosmos Magazine 2008 [11] http:/ / www. sciencedirect. com/ science/ article/ pii/ 004019519090089Q [12] Oxford English Dictionary [13] Hesse, R W. Jewelrymaking Through History: An Encyclopedia (http:/ / books. google. com/ books?id=DIWEi5Hg93gC& pg=PA103), Greenwood Publishing Group, 2007 ISBN 0313335079 [14] Supporting references "shining dawn" Google-scholar (http:/ / scholar. google. co. uk/ scholar?hl=en& q=aurum+ shining+ dawn& btnG=& as_sdt=1,5& as_sdtp=) & Google-books (https:/ / www. google. com/ search?q=Au+ -+ gold+ etymology& btnG=Search+ Books& tbm=bks& tbo=1#hl=en& tbo=1& tbm=bks& sclient=psy-ab& q=etymology+ of+ Au+ chemical+ symbol+ shining+ dawn& oq=etymology+ of+ Au+ chemical+ symbol+ shining+ dawn& aq=f& aqi=& aql=& gs_l=serp. 12. . . 42262. 56773. 2. 58184. 29. 26. 0. 0. 0. 0. 972. 6330. 0j15j8j1j0j1j1. 26. 0. . . 0. 0. eiq2tKECEYY& pbx=1& bav=on. 2,or. r_gc. r_pw. r_cp. r_qf. ,cf. osb& fp=d95a9e9054f7730a& biw=1280& bih=897) Retrieved 2012-06-07 [15] Christie, A and Brathwaite, R. Mineral Commodity Report (http:/ / scholar. googleusercontent. com/ scholar?q=cache:f2hCjL2EyqUJ:scholar. google. com/ + gulth& hl=en& as_sdt=0,5), Institute of geological and Nuclear sciences Ltd Retrieved 2012-06-07

Gold
[16] Notre Dame University Latin Dictionary (http:/ / www. archives. nd. edu/ cgi-bin/ lookup. pl?stem=Aurum& ending=) Retrieved 2012-06-07 [17] Maspero, G and Sayce, A H (1910) The Dawn of Civilization: Egypt and Chalda (http:/ / archive. org/ details/ dawnofcivilizati00masp) [18] Crooks, G R; Ingersley, C F and Schem, A J. A new Latin-English school-lexicon: on the basis of the Latin-German lexicon of Dr. C. F. Ingerslev (http:/ / books. google. com/ books?id=gfQsAAAAYAAJ& pg=PA113), J.B. Lippincott, 1861 Retrieved 2012-06-07 [32] World Gold Council, Jewellery Technology, Jewellery Alloys (http:/ / www. utilisegold. com/ jewellery_technology/ colours/ colour_alloys/ ) [35] Mortier, Tom. An experimental study on the preparation of gold nanoparticles and their properties (https:/ / lirias. kuleuven. be/ bitstream/ 1979/ 254/ 2/ thesis_finaal. pdf), PhD thesis, University of Leuven (May 2006) [45] Guinness Book of World Records 2008 [47] Kodak (2006) Toning black-and-white materials (http:/ / www. kodak. com/ global/ en/ professional/ support/ techPubs/ g23/ g23. pdf). Technical Data/Reference sheet G-23, May 2006. [54] Mansa Musa (http:/ / blackhistorypages. net/ pages/ mansamusa. php). Black History Pages [57] Sierra Nevada Virtual Museum (http:/ / www. sierranevadavirtualmuseum. com/ docs/ galleries/ history/ culture/ shadows. htm). Sierra Nevada Virtual Museum. Retrieved on 2012-05-04. [62] This is doctoral research undertaken by Frank Reith at the Australian National University, published 2004. [65] Plazak, Dan A Hole in the Ground with a Liar at the Top (Salt Lake: Univ. of Utah Press, 2006) ISBN 0-87480-840-5 (contains a chapter on gold-from seawater swindles) [77] A.Miethe, Der Zerfall des Quecksilberatoms, Naturwissenschaften, 12(1924): 597-598 [82] http:/ / www. gold. org/ investment/ research/ regular_reports/ gold_demand_trends/ [83] Summit declaration, Peoples' Gold summit, San Juan Ridge, California in June 1999 (http:/ / www. scribd. com/ doc/ 82418790/ Gold-groduction-and-its-environmental-impact). Scribd.com (2012-02-22). Retrieved on 2012-05-04. [84] Cyanide spills from gold mine compared to Chernobyls nuclear disaster (http:/ / www. deseretnews. com/ article/ 810435/ Cyanide-spill-compared-to-Chernobyls---N-disaster. html). Deseretnews.com (2000-02-14). Retrieved on 2012-05-04. [85] Death of a river (http:/ / news. bbc. co. uk/ 2/ hi/ europe/ 642880. stm). BBC News (2000-02-15). Retrieved on 2012-05-04. [86] Cyanide spill second only to Chernobyl (http:/ / www. abc. net. au/ am/ stories/ s98890. htm). Abc.net.au. 11 February 2000. Retrieved on 2012-05-04. [87] Behind gold's glitter, torn lands and pointed questions (http:/ / www. latrobefinancialmanagement. com/ Research/ Commodities/ Behind Gold's Glitter NYTimes Piece. pdf), New York Times, October 24, 2005. (PDF). Retrieved on 2012-05-04. [93] Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. ISBN 0-12-352651-5. [101] MacNeil, Jane Salodof Henna tattoo ingredient is Allergen of the Year.(Clinical Rounds) (http:/ / www. skinandallergynews. com/ index. php?id=372& cHash=071010& tx_ttnews& #91;tt_news& #93;=559). 3 January 2006. [107] Kitco.com (http:/ / kitco. com/ LFgif/ au75-pres. gif), Gold London PM Fix 1975 present (GIF), Retrieved 2006-07-22. [116] California Government Code selection 420429.8 (http:/ / www. leginfo. ca. gov/ cgi-bin/ displaycode?section=gov& group=00001-01000& file=420-429. 8) (see 425.1) [117] Alaska Statutes (http:/ / www. legis. state. ak. us/ cgi-bin/ folioisa. dll/ stattx08/ query=*/ doc/ {@17998}?) (see 44.09.110)

186

External links
Chemistry in its element podcast (http://www.rsc.org/chemistryworld/podcast/element.asp) (MP3) from the Royal Society of Chemistry's Chemistry World: Gold (http://www.rsc.org/images/ CIIE_Gold_48k_tcm18-118269.mp3) www.rsc.org Gold (http://www.periodicvideos.com/videos/079.htm) at The Periodic Table of Videos (University of Nottingham) Getting Gold 1898 book (http://www.lateralscience.co.uk/gold/auriferous.html), www.lateralscience.co.uk Technical Document on Extraction and Mining of Gold (http://web.archive.org/web/20080307000911/http:// www.epa.gov/epaoswer/other/mining/techdocs/gold.pdf), www.epa.gov Picture in the Element collection from Heinrich Pniok (http://www.pniok.de/au.htm), www.pniok.de The Art of Precolumbian Gold: The Jan Mitchell Collection (http://libmma.contentdm.oclc.org/cdm/ compoundobject/collection/p15324coll10/id/119785/rec/1), an exhibition catalog from The Metropolitan Museum of Art (fully available online as PDF)

Iron

187

Iron
Iron Fe 26

manganese iron cobalt

Fe
Ru Iron in the periodic table Appearance lustrous metallic with a grayish tinge

Spectral lines of iron General properties Name, symbol, number Pronunciation Element category Group, period, block Standard atomic weight iron, Fe, 26 /a.rn/ transition metal 8, 4, d 55.845(2)

Iron

188
Electron configuration

[Ar] 3d6 4s2 2, 8, 14, 2

History Discovery before 5000 BC Physical properties Phase Density (near r.t.) Liquid density at m.p. Meltingpoint Boilingpoint Heatoffusion Heat of vaporization Molar heat capacity solid 7.874 gcm3 6.98 gcm3 1811K, 1538C, 2800F 3134K, 2862C, 5182F 13.81 kJmol1 340 kJmol1 25.10 Jmol1K1 Vapor pressure P (Pa) 1 10 100 1k 10 k 100 k

at T (K) 1728 1890 2091 2346 2679 3132 Atomic properties Oxidation states 6, 5, 4, 3, 2, 1 , -1, -2 (amphoteric oxide) 1.83 (Pauling scale) 1st: 762.5 kJmol1 2nd: 1561.9 kJmol1 3rd: 2957 kJmol1 Atomic radius Covalent radius 126 pm 1323 (low spin), 1526 (high spin) pm Miscellanea
[1] [2]

Electronegativity Ionization energies (more)

Iron

189
Crystal structure body-centered cubic

a=286.65 pm; face-centered cubic

between 11851667 K Magnetic ordering ferromagnetic 1043 K Electrical resistivity Thermal conductivity Thermal expansion Speed of sound (thin rod) (20C) 96.1 nm 80.4Wm1K1 (25 C) 11.8 mm1K1 (r.t.) (electrolytic) 5120ms1 211 GPa 82 GPa 170 GPa 0.29 4 608 MPa 490 MPa 7439-89-6 Most stable isotopes Main article: Isotopes of iron iso
54 55 56 57 58 59 60

Young's modulus Shear modulus Bulk modulus Poisson ratio Mohs hardness Vickers hardness Brinell hardness CAS registry number

NA 5.8% syn

half-life

DM DE (MeV) 0.6800 0.231

DP
54 55

Fe Fe

>3.11022 y ++ 2.73 y
56 57 58

Cr

Mn

Fe 91.72% Fe 2.2%

Fe is stable with 30 neutrons Fe is stable with 31 neutrons Fe is stable with 32 neutrons 1.565 3.978
59 60

Fe 0.28% Fe Fe syn syn

44.503 d 2.6106 y

Co Co

Iron is a chemical element with the symbol Fe (from Latin: ferrum) and atomic number 26. It is a metal in the first transition series. It is the most common element (by mass) forming the planet Earth as a whole, forming much of Earth's outer and inner core. It is the fourth most common element in the Earth's crust. Iron's very common presence

Iron in rocky planets like Earth is due to its abundant production as a result of fusion in high-mass stars, where the production of nickel-56 (which decays to the most common isotope of iron) is the last nuclear fusion reaction that is exothermic. This causes radioactive nickel to become the last element to be produced before collapse of a supernova leads to the explosive events that scatter this precursor radionuclide of iron abundantly into space. Like other group 8 elements, iron exists in a wide range of oxidation states, 2 to +6, although +2 and +3 are the most common. Elemental iron occurs in meteoroids and other low oxygen environments, but is reactive to oxygen and water. Fresh iron surfaces appear lustrous silvery-gray, but oxidize in normal air to give hydrated iron oxides, commonly known as rust. Unlike many other metals which form passivating oxide layers, iron oxides occupy more volume than iron metal, and thus iron oxides flake off and expose fresh surfaces for corrosion. Iron metal has been used since ancient times, though copper alloys, which have lower melting temperatures, were used first in history. Pure iron is soft (softer than aluminium), but is unobtainable by smelting. The material is significantly hardened and strengthened by impurities from the smelting process, such as carbon. A certain proportion of carbon (between 0.002% and 2.1%) produces steel, which may be up to 1000times harder than pure iron. Crude iron metal is produced in blast furnaces, where ore is reduced by coke to pig iron, which has a high carbon content. Further refinement with oxygen reduces the carbon content to the correct proportion to make steel. Steels and low carbon iron alloys with other metals (alloy steels) are by far the most common metals in industrial use, due to their great range of desirable properties and the abundance of iron. Iron chemical compounds, which include ferrous and ferric compounds, have many uses. Iron oxide mixed with aluminium powder can be ignited to create a thermite reaction, used in welding and purifying ores. It forms binary compounds with the halogens and the chalcogens. Among its organometallic compounds is ferrocene, the first sandwich compound discovered. Iron plays an important role in biology, forming complexes with molecular oxygen in hemoglobin and myoglobin; these two compounds are common oxygen transport proteins in vertebrates. Iron is also the metal used at the active site of many important redox enzymes dealing with cellular respiration and oxidation and reduction in plants and animals.

190

Characteristics
Mechanical properties Characteristic values of tensile strength (TS) and Brinell hardness (BH) of different forms of iron.[][]
Material TS BH (MPa) (Brinell) 11000 2930 8501200

Iron whiskers Ausformed (hardened) steel Martensitic steel Bainitic steel Pearlitic steel Cold-worked iron Small-grain iron

2070 1380 1200 690 340

600 400 350 200 100 40 3

Carbon-containing iron 140 Pure, single-crystal iron 10

Iron The mechanical properties of iron and its alloys can be evaluated using a variety of tests, including the Brinell test, Rockwell test and the Vickers hardness test. The data on iron is so consistent that it is often used to calibrate measurements or to compare tests.[][3] However, the mechanical properties of iron are significantly affected by the sample's purity: pure research-purpose single crystals of iron are actually softer than aluminium,[] and the purest industrially produced iron (99.99%) has a hardness of 2030Brinell.[4] An increase in the carbon content of the iron will initially cause a significant corresponding increase in the iron's hardness and tensile strength. Maximum hardness of 65 Rc is achieved with a 0.6% carbon content, although this produces a metal with a low tensile strength.[5]

191

Phase diagram and allotropes


Iron represents an example of allotropy in a metal. There are at least four allotropic forms of iron, known as , , , and ; at very high pressures, some controversial experimental evidence exists for a phase stable at very high pressures and temperatures.[] As molten iron cools down it crystallizes at 1538C into its allotrope, which has a body-centered cubic (bcc) crystal structure. As it cools further its crystal structure changes to face-centered cubic (fcc) at 1394C, when it is known as -iron, or austenite. At 912C the crystal structure again becomes bcc as -iron, or ferrite, is formed, and at 770C (the Curie point, Tc) iron becomes magnetic. As the iron passes through the Curie temperature there is no change in crystalline structure, but there is a change in "domain structure", where each domain contains iron atoms with a particular electronic spin. In unmagnetized iron, all the electronic spins of the atoms within one domain are in the same direction; the neighboring domains point in various directions and thus Low-pressure phase diagram of pure iron cancel out. In magnetized iron, the electronic spins of all the domains are aligned, so that the magnetic effects of neighboring domains reinforce each other. Although each domain contains billions of atoms, they are very small, about 10micrometres across.[] At pressures above approximately 10 GPa and temperatures of a few hundred kelvin or less, -iron changes into a hexagonal close-packed (hcp) structure, which is also known as -iron; the higher-temperature -phase also changes into -iron, but does so at higher pressure. The -phase, if it exists, would appear at pressures of at least 50 GPa and temperatures of at least 1500 K; it has been thought to have an orthorhombic or a double hcp structure.[] Iron is of greatest importance when mixed with certain other metals and with carbon to form steels. There are many types of steels, all with different properties, and an understanding of the properties of the allotropes of iron is key to the manufacture of good quality steels. -iron, also known as ferrite, is the most stable form of iron at normal temperatures. It is a fairly soft metal that can dissolve only a small concentration of carbon (no more than 0.021% by mass at 910C).[6] Above 912C and up to 1400C -iron undergoes a phase transition from bcc to the fcc configuration of -iron, also called austenite. This is similarly soft and metallic but can dissolve considerably more carbon (as much as 2.04% by mass at 1146C). This form of iron is used in the type of stainless steel used for making cutlery, and hospital and food-service equipment.[] The high-pressure phases of iron are important as endmember models for the solid parts of planetary cores. The inner core of the Earth is generally assumed to consist essentially of an iron-nickel alloy with (or ) structure.

Iron The melting point of iron is experimentally well defined for pressures up to approximately 50 GPa. For higher pressures, different studies placed the --liquid triple point at pressures differing by tens of gigapascals and yielded differences of more than 1000 K for the melting point. Generally speaking, molecular dynamics computer simulations of iron melting and shock wave experiments suggest higher melting points and a much steeper slope of the melting curve than static experiments carried out in diamond anvil cells.[]

192

Isotopes
Naturally occurring iron consists of four stable isotopes: 5.845% of 54Fe, 91.754% of 56Fe, 2.119% of 57Fe and 0.282% of 58Fe. Of these stable isotopes, only 57Fe has a nuclear spin (1/2). The nuclide 54Fe is predicted to undergo double beta decay, but this process had never been observed experimentally for these nuclei, and only the lower limit on the half-life was established: t1/2>3.11022 years.
60

Fe is an extinct radionuclide of long half-life (2.6million years).[7] It is not found on Earth, but its ultimate decay product is the stable nuclide nickel-60. Much of the past work on measuring the isotopic composition of Fe has focused on determining 60Fe variations due to processes accompanying nucleosynthesis (i.e., meteorite studies) and ore formation. In the last decade however, advances in mass spectrometry technology have allowed the detection and quantification of minute, naturally occurring variations in the ratios of the stable isotopes of iron. Much of this work has been driven by the Earth and planetary science communities, although applications to biological and industrial systems are beginning to emerge.[8] The most abundant iron isotope 56Fe is of particular interest to nuclear scientists as it represents the most common endpoint of nucleosynthesis. It is often cited, falsely, as the isotope of highest binding energy, a distinction which actually belongs to nickel-62.[9] Since 56Ni is easily produced from lighter nuclei in the alpha process in nuclear reactions in supernovae (see silicon burning process), nickel-56 (14 alpha particles) is the endpoint of fusion chains inside extremely massive stars, since addition of another alpha particle would result in zinc-60, which requires a great deal more energy. This nickel-56, which has a half-life of about 6days, is therefore made in quantity in these stars, but soon decays by two successive positron emissions within supernova decay products in the supernova remnant gas cloud, first to radioactive cobalt-56, and then stable iron-56. This last nuclide is therefore common in the universe, relative to other stable metals of approximately the same atomic weight. In phases of the meteorites Semarkona and Chervony Kut a correlation between the concentration of 60Ni, the daughter product of 60Fe, and the abundance of the stable iron isotopes could be found which is evidence for the existence of 60Fe at the time of formation of the Solar System. Possibly the energy released by the decay of 60Fe contributed, together with the energy released by decay of the radionuclide 26Al, to the remelting and differentiation of asteroids after their formation 4.6billion years ago. The abundance of 60Ni present in extraterrestrial material may also provide further insight into the origin of the Solar System and its early history.[10] Nuclei of iron atoms have some of the highest binding energies per nucleon, surpassed only by the nickel isotope 62 Ni. This is formed by nuclear fusion in stars. Although a further tiny energy gain could be extracted by synthesizing 62Ni, conditions in stars are unsuitable for this process to be favored. Elemental distribution on Earth greatly favors iron over nickel, and also presumably in supernova element production.[11] Iron-56 is the heaviest stable isotope produced by the alpha process in stellar nucleosynthesis; elements heavier than iron and nickel require a supernova for their formation. Iron is the most abundant element in the core of red giants, and is the most abundant metal in iron meteorites and in the dense metal cores of planets such as Earth.

Iron

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Nucleosynthesis
Iron is created by extremely large, extremely hot (over 2.5 billion kelvin) stars through the silicon burning process. It is the heaviest stable element to be produced in this manner. The process starts with the second largest stable nucleus created by silicon burning, which is calcium. One stable nucleus of calcium fuses with one helium nucleus, creating unstable titanium. Before the titanium decays, it can fuse with another helium nucleus, creating unstable chromium. Before the chromium decays, it can fuse with another helium nucleus, creating unstable iron. Before the iron decays, it can fuse with another helium nucleus, creating unstable nickel-56. Any further fusion of nickel-56 consumes energy instead of producing energy, so after the production of nickel-56, the star does not produce the energy necessary to keep the core from collapsing. Eventually, the nickel-56 decays to unstable cobalt-56, which in turn decays to stable iron-56. When the core of the star collapses, it creates a supernova. Supernovas also create additional forms of stable iron via the r-process.

Occurrence
Planetary occurrence Iron is the sixth most abundant element in the Universe, and the most common refractory element.[] It is formed as the final exothermic stage of stellar nucleosynthesis, by silicon fusion in massive stars. Metallic or native iron is rarely found on the surface of the Earth because it tends to oxidize, but its oxides are pervasive and represent the primary ores. While it makes up about 5% of the Earth's crust, both the Earth's inner and outer core are believed to consist largely of an iron-nickel alloy constituting 35% of the mass of the Earth as a whole. Iron is consequently the most abundant element on Earth, but only the Iron meteorites of similar composition of Earth's fourth most abundant element in the Earth's crust.[12][13] Most of the inner and outer core iron in the crust is found combined with oxygen as iron oxide minerals such as hematite and magnetite. Large deposits of iron are found in banded iron formations. These geological formations are a type of rock consisting of repeated thin layers of iron oxides, either magnetite (Fe3O4) or hematite (Fe2O3), alternating with bands of iron-poor shale and chert. The banded iron formations were laid down in the time between 3,700 [14] million years ago and 1,800 [15] million years ago[14][15] About 1 in 20 meteorites consist of the unique iron-nickel minerals taenite (3580% iron) and kamacite (9095% iron). Although rare, iron meteorites are the main form of natural metallic iron on the Earth's surface.[16] It was proven by Mssbauer spectroscopy that the red color of the surface of Mars is derived from an iron oxide-rich regolith.[17] Stocks in use in society According to the International Resource Panel's Metal Stocks in Society report, the global per capita stock of iron in use in society is 2200kg. Much of this is in more-developed countries (700014000kg per capita) rather than less-developed countries (2000kg per capita).

Chemistry and compounds

Iron

194

Oxidation state 2 1 0 1 2 3 4 5 6

Representative compound

Disodium tetracarbonylferrate (Collman's reagent)

Iron pentacarbonyl Cyclopentadienyliron dicarbonyl dimer ("Fp2") Ferrous sulfate, ferrocene Ferric chloride, ferrocenium tetrafluoroborate Barium ferrate(IV)

Potassium ferrate

Iron forms compounds mainly in the +2 and +3 oxidation states. Traditionally, iron(II) compounds are called ferrous, and iron(III) compounds ferric. Iron also occurs in higher oxidation states, an example being the purple potassium ferrate (K2FeO4) which contains iron in its +6 oxidation state. Iron(IV) is a common intermediate in many biochemical oxidation reactions.[18][] Numerous organometallic compounds contain formal oxidation states of +1, 0, 1, or even 2. The oxidation states and other bonding properties are often assessed using the technique of Mssbauer spectroscopy.[19] There are also many mixed valence compounds that contain both iron(II) and iron(III) centers, such as magnetite and Prussian blue (Fe4(Fe[CN]6)3).[] The latter is used as the traditional "blue" in blueprints.[20] The iron compounds produced on the largest scale in industry are iron(II) sulfate (FeSO47H2O) and iron(III) chloride (FeCl3). The former is one of the most readily available sources of iron(II), but is less stable to aerial oxidation than Mohr's salt ((NH4)2Fe(SO4)26H2O). Iron(II) compounds tend to be oxidized to iron(III) compounds in the air.[] Unlike many other metals, iron does not form amalgams with mercury. As a result, mercury is traded in standardized 76 pound flasks (34kg) made of iron.[21]

Binary compounds

Hydrated iron(III) chloride, also known as ferric chloride

Iron reacts with oxygen in the air to form various oxide and hydroxide compounds; the most common are iron(II,III) oxide (Fe3O4), and iron(III) oxide (Fe2O3). Iron(II) oxide also exists, though it is unstable at room temperature. These oxides are the principal ores for the production of iron (see bloomery and blast furnace). They are also used in the production of ferrites, useful magnetic storage media in computers, and pigments. The best known sulfide is iron pyrite (FeS2), also known as fool's gold owing to its golden luster.[] The binary ferrous and ferric halides are well known, with the exception of ferric iodide. The ferrous halides typically arise from treating iron metal with the corresponding binary halogen acid to give the corresponding hydrated salts.[] Fe + 2 HX FeX2 + H2 Iron reacts with fluorine, chlorine, and bromine to give the corresponding ferric halides, ferric chloride being the most common:

Iron 2 Fe + 3 X2 2 FeX3 (X = F, Cl, Br)

195

Coordination and organometallic compounds


Several cyanide complexes are known. The most famous example is Prussian blue, (Fe4(Fe[CN]6)3). Potassium ferricyanide and potassium ferrocyanide are also known; the formation of Prussian blue upon Prussian blue reaction with iron(II) and iron(III) respectively forms the basis of a [] "wet" chemical test. Prussian blue is also used as an antidote for thallium and radioactive caesium poisoning.[22][23] Prussian blue can be used in laundry bluing to correct the yellowish tint left by ferrous salts in water. Several carbonyl compounds of iron are known. The premier iron(0) compound is iron pentacarbonyl, Fe(CO)5, which is used to produce carbonyl iron powder, a highly reactive form of metallic iron. Thermolysis of iron pentacarbonyl gives the trinuclear cluster, triiron dodecacarbonyl. Collman's reagent, disodium tetracarbonylferrate, is a useful reagent for organic chemistry; it contains iron in the 2 oxidation state. Cyclopentadienyliron dicarbonyl dimer contains iron in the rare +1 oxidation state.[24] Ferrocene is an extremely stable complex. The first sandwich compound, it contains an iron(II) center with two cyclopentadienyl ligands bonded through all ten carbon atoms. This arrangement was a shocking novelty when it was first discovered,[25] but the discovery of ferrocene has led to a new branch of organometallic chemistry. Ferrocene itself can be used as the backbone of a ligand, e.g. dppf. Ferrocene can itself be oxidized to the ferrocenium cation (Fc+); the ferrocene/ferrocenium couple is often used as a reference in electrochemistry.[26]
Ferrocene

History
Wrought iron
Iron objects of great age are much rarer than objects made of gold or silver due to the ease of corrosion of iron.[27] Beads made of meteoric iron in 3500BC or earlier were found in Gerzah, Egypt by G. A. Wainwright.[28] The beads contain 7.5% nickel, which is a signature of meteoric origin since iron found in the Earth's crust has very little to no nickel content. Meteoric iron was highly regarded due to its origin in the heavens and was often used to forge weapons and tools or whole specimens placed in churches.[28] Items that were likely The symbol for Mars made of iron by Egyptians date from 2500 to 3000BC.[27] Iron had a distinct advantage over has been used since antiquity to represent bronze in warfare implements. It was much harder and more durable than bronze, although iron. susceptible to rust. However, this is contested. Hittitologist Trevor Bryce argues that before advanced iron-working techniques were developed in India, meteoritic iron weapons used by early Mesopotamian armies had a tendency to shatter in combat, due to their high carbon content.[29] The first iron production started in the Middle Bronze Age but it took several centuries before iron displaced bronze. Samples of smelted iron

Iron

196 from Asmar, Mesopotamia and Tall Chagar Bazaar in northern Syria were made sometime between 2700 and 3000BC.[30] The Hittites appear to be the first to understand the production of iron from its ores and regard it highly in their society. They began to smelt iron between 1500 and 1200BC and the practice spread to the rest of the Near East after their empire fell in 1180BC.[30] The subsequent period is called the Iron Age. Iron smelting, and thus the Iron Age, reached Europe two hundred years later and arrived in Zimbabwe, Africa by the 8th century.[30] In China, iron only appears circa 700500 BC.[31] Iron smelting may have been introduced into China through Central Asia.[32] The earliest evidence of the use of a blast furnace in China dates to the 1st century AD,[] and cupola furnaces were used as early as early as the Warring States period (403221 BC).[33] Usage of the blast and cupola furnace remained widespread during the Song and Tang Dynasties.[]
The Delhi iron pillar is an example of the iron extraction and processing methodologies of India. The iron pillar at Delhi has withstood corrosion for the last 1600years.

Artifacts from smelted iron occur in India from 1800 to 1200 BC,[] and in the Levant from about 1500 BC (suggesting smelting in Anatolia or the Caucasus).[34][35] The Book of Genesis, fourth chapter, verse 22 contains the first mention of iron in the Old Testament of the Bible; "Tubal-cain, an instructor of every artificer in brass and iron."[27] Other verses allude to iron mining (Job 28:2), iron used as a stylus (Job 19:24), furnace (Deuteronomy 4:20), chariots (Joshua 17:16), nails (I Chron. 22:3), saws and axes (II Sam. 12:31), and cooking utensils (Ezekiel 4:3).[36] The metal is also mentioned in the New Testament, for example in Acts chapter 12 verse 10, "[Peter passed through] the iron gate that leadeth unto the city" of Antioch.[37] Iron working was introduced to Greece in the late 11th century BC.[38] The spread of ironworking in Central and Western Europe is associated with Celtic expansion. According to Pliny the Elder, iron use was common in the Roman era.[28] The annual iron output of the Roman Empire is estimated at 84,750 t,[39] while the similarly populous Han China produced around 5,000 t.[40] During the Industrial Revolution in Britain, Henry Cort began refining iron from pig iron to wrought iron (or bar iron) using innovative production systems. In 1783 he patented the puddling process for refining iron ore. It was later improved by others including Joseph Hall.

Cast iron
Cast iron was first produced in China during 5th century BC,[41] but was hardly in Europe until the medieval period.[42][48] The earliest cast iron artifacts were discovered by archaeologists in what is now modern Luhe County, Jiangsu in China. Cast iron was used in ancient China for warfare, agriculture, and architecture.[] During the medieval period, means were found in Europe of producing wrought iron from cast iron (in this context known as pig iron) using finery forges. For all these processes, charcoal was required as fuel.

Iron

197 Medieval blast furnaces were about 10 feet (3.0m) tall and made of fireproof brick; forced air was usually provided by hand-operated bellows.[48] Modern blast furnaces have grown much bigger. In 1709, Abraham Darby I established a coke-fired blast furnace to produce cast iron. The ensuing availability of inexpensive iron was one of the factors leading to the Industrial Revolution. Toward the end of the 18th century, cast iron began to replace wrought iron for certain purposes, because it was cheaper. Carbon content in iron wasn't implicated as the reason for the differences in properties of wrought iron, cast iron and steel until the 18th century.[30]

Coalbrookdale by Night, 1801. Blast furnaces light the iron making town of Coalbrookdale.

Since iron was becoming cheaper and more plentiful, it also became a major structural material following the building of the innovative first iron bridge in 1778.

Steel
Steel (with smaller carbon content than pig iron but more than wrought iron) was first produced in antiquity by using a bloomery. Blacksmiths in Luristan in western Iran were making good steel by 1000BC.[30] Then improved versions, Wootz steel by India and Damascus steel by China were developed around 300 BC and 500 AD respectively. These methods were specialized, and so steel did not become a major commodity until the 1850s.[43] New methods of producing it by carburizing bars of iron in the cementation process were devised in the 17th century AD. In the Industrial Revolution, new methods of producing bar iron without charcoal were devised and these were later applied to produce steel. In the late 1850s, Henry Bessemer invented a new steelmaking process, involving blowing air through molten pig iron, to produce mild steel. This made steel much more economical, thereby leading to wrought iron no longer being produced.[44]

Foundations of modern chemistry


Antoine Lavoisier used the reaction of water steam with metallic iron inside an incandescent iron tube to produce hydrogen in his experiments leading to the demonstration of the mass conservation. Anaerobic oxidation of iron at high temperature can be schematically represented by the following reactions: Fe + H2O FeO + H2 2 Fe + 3 H2O Fe2O3 + 3 H2 3 Fe + 4 H2O Fe3O4 + 4 H2

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Industrial production
The production of iron or steel is a process containing two main stages, unless the desired product is cast iron. The first stage is to produce pig iron in a blast furnace. Alternatively, it may be directly reduced. The second is to make wrought iron or steel from pig iron by a further process. For a few limited purposes like electromagnet cores, pure iron is produced by electrolysis of a ferrous sulfate solution

Blast furnace
Ninety percent of all mining of metallic ores is for the extraction of iron[citation needed]. Industrially, iron production involves iron ores, principally hematite (nominally Fe2O3) and magnetite (Fe3O4) in a carbothermic reaction (reduction with carbon) in a blast furnace at temperatures of about 2000C. In a blast furnace, iron ore, carbon in the form of coke, and a flux such as limestone (which is used to remove silicon dioxide impurities in the ore which would otherwise clog the furnace with solid material) are fed into the top of the furnace, while a massive blast of heated air, about 4 tons per ton of iron,[48] is forced into the furnace at the bottom. In the furnace, the coke reacts with oxygen in the air blast to produce carbon monoxide: 2 C + O2 2 CO The carbon monoxide reduces the iron ore (in the chemical equation below, hematite) to molten iron, becoming carbon dioxide in the process: Fe2O3 + 3 CO 2 Fe + 3 CO2 Some iron in the high-temperature lower region of the furnace reacts directly with the coke: 2 Fe2O3 + 3 C 4 Fe + 3 CO2 The flux is present to melt impurities in the ore, principally silicon dioxide sand and other silicates. Common fluxes include limestone (principally calcium carbonate) and dolomite (calcium-magnesium carbonate). Other fluxes may be used depending on the impurities that need to be removed from the ore. In the heat of the furnace the limestone flux decomposes to calcium oxide (also known as quicklime): CaCO3 CaO + CO2 Then calcium oxide combines with silicon dioxide to form a liquid slag. CaO + SiO2 CaSiO3 The slag melts in the heat of the furnace. In the bottom of the furnace, the molten slag floats on top of the denser molten iron, and apertures in the side of the furnace are opened to run off the iron and the slag separately. The iron, once cooled, is called pig iron, while the slag can be used as a material in road construction or to improve mineral-poor soils for agriculture[48]
How iron was extracted in the 19th century

The fining process of smelting iron ore to make wrought iron from pig iron, with the right illustration displaying men working a blast furnace, from the Tiangong Kaiwu encyclopedia, published in 1637 by Song Yingxing.

Iron

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Direct iron reduction


Since coke is becoming more regulated due to environmental concerns, alternative methods of processing iron have been developed. "Direct iron reduction"[48] reduces iron ore to a powder called "sponge" iron or "direct" iron that is suitable for steelmaking. There are two main reactions that go on in the direct reduction process: Natural gas is partially oxidized (with heat and a catalyst): 2 CH4 + O2 2 CO + 4 H2
This heap of iron ore pellets will be used in steel production.

These gases are then treated with iron ore in a furnace, producing solid sponge iron: Fe2O3 + CO + 2 H2 2 Fe + CO2 + 2 H2O Silica is removed by adding a limestone flux, later.

Further processes
Pig iron is not pure iron, but has 45% carbon dissolved in it with small amounts of other impurities like sulfur, magnesium, phosphorus and manganese. As the carbon is the major impurity, the iron (pig iron) becomes brittle and hard. This form of iron, also known as cast iron, is used to cast articles in foundries such as stoves, pipes, radiators, lamp-posts and rails. Alternatively pig iron may be made into steel (with up to about 2% carbon) or wrought iron (commercially pure iron). Various processes have been used for this, including finery forges, puddling furnaces, Bessemer converters, open hearth furnaces, basic oxygen furnaces, and electric arc Iron-carbon phase diagram, various stable solid solution forms furnaces. In all cases, the objective is to oxidize some or all of the carbon, together with other impurities. On the other hand, other metals may be added to make alloy steels. The hardness of the steel depends upon its carbon content: the higher the percentage of carbon, the greater the hardness and the lesser the malleability. The properties of the steel can also be changed by several methods. Annealing involves the heating of a piece of steel to 700800 C for several hours and then gradual cooling. It makes the steel softer and more workable. Steel may be hardened by cold working. The metal is bent or hammered into its final shape at a relatively cool temperature. Cold forging is the stamping of a piece of steel into shape by a heavy press. Wrenches are commonly made by cold forging. Cold rolling, which involves making a thinner but harder sheet, and cold drawing, which

Iron makes a thinner but stronger wire, are two other methods of cold working. To harden the steel, it is heated to red-hot and then cooled by quenching it in the water. It becomes harder and more brittle. If it is too hardened, it is then heated to a required temperature and allowed to cool. The steel thus formed is less brittle. Heat treatment is another way to harden steel. The steel is heated red-hot, then cooled quickly. The iron carbide molecules are decomposed by the heat, but do not have time to reform. Since the free carbon atoms are stuck, it makes the steel much harder and stronger than before.[48] Sometimes both toughness and hardness are desired. A process called case hardening may be used. Steel is heated to about 900 C then plunged into oil or water. Carbon from the oil can diffuse into the steel, making the surface very hard. The surface cools quickly, but the inside cools slowly, making an extremely hard surface and a durable, resistant inner layer. Iron may be passivated by dipping it into a concentrated nitric acid solution. This forms a protective layer of oxide on the metal, protecting it from further corrosion.[45]

200

Applications
Metallurgical Iron production 2009 (million tonnes)[46]
Country China Australia Brazil Japan India Russia Ukraine 257.4 92.1 65.8 Iron ore Pig iron Direct iron 1,114.9 393.9 305.0 549.4 4.4 25.1 66.9 38.2 43.9 25.7 27.3 20.1 914.0 0.38 64.5 23.4 4.7 0.011 Steel 573.6 5.2 26.5 87.5 63.5 60.0 29.9 48.6 32.7 1,232.4

South Korea 0.1 Germany World 0.4 1,594.9

Iron is the most widely used of all the metals, accounting for 95% of worldwide metal production.[citation needed] Its low cost and high strength make it indispensable in engineering applications such as the construction of machinery and machine tools, automobiles, the hulls of large ships, and structural components for buildings. Since pure iron is quite soft, it is most commonly combined with alloying elements to make steel. Commercially available iron is classified based on purity and the abundance of additives. Pig iron has 3.54.5% carbon[] and contains varying amounts of contaminants such as sulfur, silicon and phosphorus. Pig iron is not a saleable product, but rather an intermediate step in the production of cast iron and steel. The reduction of contaminants in pig iron that negatively affect material properties, such as sulfur and phosphorus, yields cast iron containing 24% carbon, 16% silicon, and small amounts of manganese. It has a melting point in the range of 14201470K, which is lower than either of its two main components, and makes it the first product to be melted when carbon and iron are heated together. Its mechanical properties vary greatly and depend on the form the carbon takes in the alloy. "White" cast irons contain their carbon in the form of cementite, or iron-carbide. This hard, brittle compound dominates the mechanical properties of white cast irons, rendering them hard, but unresistant to shock. The broken

Iron surface of a white cast iron is full of fine facets of the broken iron-carbide, a very pale, silvery, shiny material, hence the appellation. In gray iron the carbon exists as separate, fine flakes of graphite, and also renders the material brittle due to the sharp edged flakes of graphite that produce stress concentration sites within the material. A newer variant of gray iron, referred to as ductile iron is specially treated with trace amounts of magnesium to alter the shape of graphite to spheroids, or nodules, reducing the stress concentrations and vastly increasing the toughness and strength of the material. Wrought iron contains less than 0.25% carbon but large amounts of slag that give it a fibrous characteristic.[] It is a tough, malleable product, but not as fusible as pig iron. If honed to an edge, it loses it quickly. Wrought iron is characterized by the presence of fine fibers of slag entrapped within the metal. Wrought iron is more corrosion resistant than steel. It has been almost completely replaced by mild steel for traditional "wrought iron" products and blacksmithing. Mild steel corrodes more readily than wrought iron, but is cheaper and more widely available. Carbon steel contains 2.0% carbon or less,[] with small amounts of manganese, sulfur, phosphorus, and silicon. Alloy steels contain varying amounts of carbon as well as other metals, such as chromium, vanadium, molybdenum, nickel, tungsten, etc. Their alloy content raises their cost, and so they are usually only employed for specialist uses. One common alloy steel, though, is stainless steel. Recent developments in ferrous metallurgy have produced a growing range of microalloyed steels, also termed 'HSLA' or high-strength, low alloy steels, containing tiny additions to produce high strengths and often spectacular toughness at minimal cost. Apart from traditional applications, iron is also used for protection from ionizing radiation. Although it is lighter than another traditional protection material, lead, it is much stronger mechanically. The attenuation of radiation as a function of energy is shown in the graph. The main disadvantage of iron and steel is that pure iron, and most of its alloys, suffer badly from rust if not protected in some way. Painting, galvanization, passivation, plastic coating and bluing are all used to protect iron from rust by excluding water and oxygen or by cathodic protection.

201

Photon mass attenuation coefficient for iron.

Iron compounds
Although its metallurgical role is dominant in terms of amounts, iron compounds are pervasive in industry as well being used in many niche uses. Iron catalysts are traditionally used in the Haber-Bosch Process for the production of ammonia and the Fischer-Tropsch process for conversion of carbon monoxide to hydrocarbons for fuels and lubricants.[47] Powdered iron in an acidic solvent was used in the Bechamp reduction the reduction of nitrobenzene to aniline.[48] Iron(III) chloride finds use in water purification and sewage treatment, in the dyeing of cloth, as a coloring agent in paints, as an additive in animal feed, and as an etchant for copper in the manufacture of printed circuit boards.[49] It can also be dissolved in alcohol to form tincture of iron. The other halides tend to be limited to laboratory uses. Iron(II) sulfate is used as a precursor to other iron compounds. It is also used to reduce chromate in cement. It is used to fortify foods and treat iron deficiency anemia. These are its main uses. Iron(III) sulfate is used in settling minute sewage particles in tank water. Iron(II) chloride is used as a reducing flocculating agent, in the formation of iron complexes and magnetic iron oxides, and as a reducing agent in organic synthesis.

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202

Biological role
Iron is abundant in biology.[50] Iron-proteins are found in all living organisms, ranging from the evolutionarily primitive archaea to humans. The color of blood is due to the hemoglobin, an iron-containing protein. As illustrated by hemoglobin, iron is often bound to cofactors, e.g. in hemes. The iron-sulfur clusters are pervasive and include nitrogenase, the enzymes responsible for biological nitrogen fixation. Influential theories of evolution have invoked a role for iron sulfides in the iron-sulfur world theory. Iron is a necessary trace element found in nearly all living organisms. Iron-containing enzymes and proteins, often containing heme prosthetic groups, participate in many biological oxidations and in transport. Examples of proteins found in higher organisms include hemoglobin, cytochrome (see high-valent iron), and catalase.[51]

Bioinorganic compounds
The most commonly known and studied "bioinorganic" compounds of iron (i.e., iron compounds used in biology) are the heme proteins: examples are hemoglobin, myoglobin, and cytochrome P450. These compounds can transport gases, build enzymes, and be used in transferring electrons. Metalloproteins are a group of proteins with metal ion cofactors. Some examples of iron metalloproteins are ferritin and rubredoxin. Many enzymes vital to life contain iron, such as catalase, lipoxygenases, and IRE-BP.

Structure of Heme b, in the protein additional ligand(s) would be attached to Fe.

Health and diet


Iron is pervasive, but particularly rich sources of dietary iron include red meat, lentils, beans, poultry, fish, leaf vegetables, watercress, tofu, chickpeas, black-eyed peas, blackstrap molasses, fortified bread, and fortified breakfast cereals. Iron in low amounts is found in molasses, teff and farina. Iron in meat (heme iron) is more easily absorbed than iron in vegetables.[52] Although some studies suggest that heme/hemoglobin from red meat has effects which may increase the likelihood of colorectal cancer,[][] there is still some controversy,[53] and even a few studies suggesting that there is not enough evidence to support such claims.[54] Iron provided by dietary supplements is often found as iron(II) fumarate, although iron sulfate is cheaper and is absorbed equally well. Elemental iron, or reduced iron, despite being absorbed at only one third to two thirds the efficiency (relative to iron sulfate),[55] is often added to foods such as breakfast cereals or enriched wheat flour. Iron is most available to the body when chelated to amino acids[] and is also available for use as a common iron supplement. Often the amino acid chosen for this purpose is the cheapest and most common amino acid, glycine, leading to "iron glycinate" supplements.[] The Recommended Dietary Allowance (RDA) for iron varies considerably based on age, gender, and source of dietary iron (heme-based iron has higher bioavailability).[56] Infants may require iron supplements if they are bottle-fed cow's milk.[57] Blood donors and pregnant women are at special risk of low iron levels and are often advised to supplement their iron intake.[58]

Iron

203

Uptake and storage


Iron acquisition poses a problem for aerobic organisms, because ferric iron is poorly soluble near neutral pH. Thus, bacteria have evolved high-affinity sequestering agents called siderophores.[59][60][61] After uptake, in cells, iron storage is carefully regulated; "free" iron ions do not exist as such. A major component of this regulation is the protein transferrin, which binds iron ions absorbed from the duodenum and carries it in the blood to cells.[62] In animals, plants, and fungi, iron is often the metal ion incorporated into the heme complex. Heme is an essential component of cytochrome proteins, which mediate redox reactions, and of oxygen carrier proteins such as hemoglobin, myoglobin, and leghemoglobin. Inorganic iron contributes to redox reactions in the iron-sulfur clusters of many enzymes, such as nitrogenase (involved in the synthesis of ammonia from nitrogen and hydrogen) and hydrogenase. Non-heme iron proteins include the enzymes methane monooxygenase (oxidizes methane to methanol), ribonucleotide reductase (reduces ribose to deoxyribose; DNA biosynthesis), hemerythrins (oxygen transport and fixation in marine invertebrates) and purple acid phosphatase (hydrolysis of phosphate esters). Iron distribution is heavily regulated in mammals, partly because iron ions have a high potential for biological toxicity.[63]

Regulation of uptake
Iron uptake is tightly regulated by the human body, which has no regulated physiological means of excreting iron. Only small amounts of iron are lost daily due to mucosal and skin epithelial cell sloughing, so control of iron levels is mostly by regulating uptake.[64] Regulation of iron uptake is impaired in some people as a result of a genetic defect that maps to the HLA-H gene region on chromosome 6. In these people, excessive iron intake can result in iron overload disorders, such as hemochromatosis. Many people have a genetic susceptibility to iron overload without realizing it or being aware of a family history of the problem. For this reason, it is advised that people do not take iron supplements unless they suffer from iron deficiency and have consulted a doctor. Hemochromatosis is estimated to cause disease in between 0.3 and 0.8% of Caucasians.[65] MRI finds that iron accumulates in the hippocampus of the brains of those with Alzheimer's disease and in the substantia nigra of those with Parkinson disease.[66]

Permeable reactive barriers


Zero-valent iron is the main reactive material for permeable reactive barriers.[67]

Precautions
NFPA 704

Fire diamond for powdered iron metal

Large amounts of ingested iron can cause excessive levels of iron in the blood. High blood levels of free ferrous iron react with peroxides to produce free radicals, which are highly reactive and can damage DNA, proteins, lipids, and other cellular components. Thus, iron toxicity occurs when there is free iron in the cell, which generally occurs when iron levels exceed the capacity of transferrin to bind the iron. Damage to the cells of the gastrointestinal tract can also prevent them from regulating iron absorption leading to further increases in blood levels. Iron typically damages

Iron cells in the heart, liver and elsewhere, which can cause significant adverse effects, including coma, metabolic acidosis, shock, liver failure, coagulopathy, adult respiratory distress syndrome, long-term organ damage, and even death.[] Humans experience iron toxicity above 20milligrams of iron for every kilogram of mass, and 60milligrams per kilogram is considered a lethal dose.[] Overconsumption of iron, often the result of children eating large quantities of ferrous sulfate tablets intended for adult consumption, is one of the most common toxicological causes of death in children under six.[] The Dietary Reference Intake (DRI) lists the Tolerable Upper Intake Level (UL) for adults as 45mg/day. For children under fourteen years old the UL is 40mg/day. The medical management of iron toxicity is complicated, and can include use of a specific chelating agent called deferoxamine to bind and expel excess iron from the body.[][68]

204

References
[7] G. Rugel, T. Faestermann, K. Knie, G. Korschinek, M. Poutivtsev, D. Schumann, N. Kivel, I. Gnther-Leopold, R. Weinreich, M. Wohlmuther: New Measurement of the 60 Half-Life. In: Physical Review Letters. 103, 2009, S., . [24] . [27] Weeks 1968, p.29. [28] Weeks 1968, p.31. [30] Weeks 1968, p.32. [31] Sawyer, Ralph D. and Mei-chn Sawyer. The Seven Military Classics of Ancient China. Boulder: Westview, (1993), p. 10. [32] Pigott, Vincent C. (1999). p. 8. [33] Pigott, Vincent C. (1999). The Archaeometallurgy of the Asian Old World. Philadelphia: University of Pennsylvania Museum of Archaeology and Anthropology. ISBN 0-924171-34-0, p. 191. [36] Weeks 1968, pp.2930. [37] Weeks 1968, p.30. [38] Riederer, Josef; Wartke, Ralf-B.: "Iron", Cancik, Hubert; Schneider, Helmuth (eds.): Brill's New Pauly, Brill 2009 [39] Craddock, Paul T. (2008): "Mining and Metallurgy", in: Oleson, John Peter (ed.): The Oxford Handbook of Engineering and Technology in the Classical World, Oxford University Press, ISBN 978-0-19-518731-1, p. 108 [40] Wagner, Donald B.: "The State and the Iron Industry in Han China", NIAS Publishing, Copenhagen 2001, ISBN 87-87062-77-1, p. 73 [41] originally published in [42] Giannichedda, Enrico (2007): "Metal production in Late Antiquity" (http:/ / books. google. com/ books?id=LAgxAJNXhFwC& pg=PA200), in Technology in Transition AD 300650 Lavan, L.; Zanini, E. and Sarantis, A.(eds.), Brill, Leiden; ISBN 90-04-16549-5, p. 200. [43] Spoerl, Joseph S. A Brief History of Iron and Steel Production (http:/ / www. anselm. edu/ homepage/ dbanach/ h-carnegie-steel. htm). Saint Anselm College [46] Steel Statistical Yearbook 2010 (http:/ / www. worldsteel. org/ statistics/ statistics-archive/ yearbook-archive. html). World Steel Association [50] electronic-book ISBN 978-94-007-5561-1 electronic[52] Food Standards Agency Eat well, be well Iron deficiency (http:/ / www. eatwell. gov. uk/ healthissues/ irondeficiency/ ). Eatwell.gov.uk (2012-03-05). Retrieved on 2012-06-27.

Bibliography
Weeks, Mary Elvira; Leichester, Henry M. (1968). "Elements Known to the Ancients". Discovery of the Elements. Easton, PA: Journal of Chemical Education. pp.2940. ISBN0-7661-3872-0. LCCN 68-15217 (http:/ /lccn.loc.gov/68-15217).

Further reading
H. R. Schubert, History of the British Iron and Steel Industry to 1775 AD (Routledge, London, 1957) R. F. Tylecote, History of Metallurgy (Institute of Materials, London 1992). R. F. Tylecote, "Iron in the Industrial Revolution" in J. Day and R. F. Tylecote, The Industrial Revolution in Metals (Institute of Materials 1991), 20060.

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External links
It's Elemental Iron (http://education.jlab.org/itselemental/ele026.html) The Most Tightly Bound Nuclei (http://hyperphysics.phy-astr.gsu.edu/hbase/nucene/nucbin2.html) Chemistry in its element podcast (http://www.rsc.org/chemistryworld/podcast/element.asp) (MP3) from the Royal Society of Chemistry's Chemistry World: Iron (http://www.rsc.org/images/ CIIE_iron_48kbps_tcm18-120046.mp3) Iron (http://www.periodicvideos.com/videos/026.htm) at The Periodic Table of Videos (University of Nottingham) Metallurgy for the non-Metallurgist (http://books.google.com/books?id=brpx-LtdCLYC&pg=frontcover& d#v=onepage&q&f=true)

Redox
Redox (reduction-oxidation) reactions include all chemical reactions in which atoms have their oxidation state changedthat is, redox reactions involve the transfer of electrons between species. This can be either a simple redox process, such as the oxidation of carbon to yield carbon dioxide (CO 2) or the reduction of carbon by hydrogen to yield methane (CH4), or a complex process such as the oxidation of glucose (C6H12O6) in the human body through a series of complex electron transfer processes. The term "redox" comes from two concepts involved with electron transfer: reduction and oxidation.[1] It can be explained in simple terms: Oxidation is the loss of electrons or an increase in oxidation state by a molecule, atom, or ion. Reduction is the gain of electrons or a decrease in oxidation state by a molecule, atom, or ion.
The two parts of a redox reaction

Sodium and fluorine bonding ionically to form sodium fluoride. Sodium loses its outer electron to give it a stable electron configuration, and this electron enters the fluorine atom exothermically. The oppositely charged ions are then attracted to each other. The sodium is oxidized, and the fluorine is reduced.

Although oxidation reactions are commonly associated with the formation of oxides from oxygen molecules, these are only specific examples of a more general concept of reactions involving electron transfer. Redox reactions, or oxidation-reduction reactions, have a number of similarities to acidbase reactions. Like acidbase reactions, redox reactions are a matched set, that is, there cannot be an oxidation reaction without a reduction reaction happening simultaneously. The oxidation alone and the reduction alone are each called a half-reaction, because two half-reactions always occur together to form a whole reaction. When writing half-reactions, the gained or lost electrons are typically included explicitly in order that the half-reaction be balanced with respect to electric charge.

Redox Though sufficient for many purposes, these descriptions are not precisely correct. Oxidation and reduction properly refer to a change in oxidation state the actual transfer of electrons may never occur. Thus, oxidation is better defined as an increase in oxidation state, and reduction as a decrease in oxidation state. In practice, the transfer of electrons will always cause a change in oxidation state, but there are many reactions that are classed as "redox" even though no electron transfer occurs (such as those involving covalent bonds).

206

Etymology
"Redox" is a portmanteau of "reduction" "oxidation", more commonly known oxidation-reduction. and as

The word oxidation originally implied reaction with oxygen to form an oxide, since (di)oxygen was historically the first recognized oxidizing agent. Later, the term was expanded to encompass oxygen-like substances that accomplished parallel chemical reactions. Ultimately, the meaning was generalized to include all processes involving loss of electrons. The word reduction originally referred to the loss in weight upon heating a metallic ore such as a metal oxide to extract the metal. In other words, ore was "reduced" to metal. Antoine Lavoisier (1743-1794) showed that this loss of weight was due to the loss of oxygen as a gas. Later, scientists realized that the metal atom gains electrons in this process. The meaning of reduction then became generalized to include all processes involving gain of electrons. Even though "reduction" seems counter-intuitive when speaking of the gain of electrons, it might help to think of reduction as the loss of oxygen, which was its historical meaning.
Rusting iron

A bonfire. Combustion consists of redox reactions involving free The electrochemist John Bockris has used the words radicals.[citation needed] electronation and deelectronation to describe reduction and oxidation processes respectively when they occur at electrodes.[2] These words are analogous to protonation and deprotonation, but they have not been widely adopted by chemists.

The term "hydrogenation" could be used instead of reduction, since hydrogen is the reducing agent in a large number of reactions, especially in organic chemistry and biochemistry. But unlike oxidation, which has been generalized beyond its root element, hydrogenation has maintained its specific connection to reactions which add hydrogen to another substance (e.g., the hydrogenation of unsaturated fats in saturated fats, R-CH=CH-R + H2 R-CH2-CH2-R).

Redox

207

Oxidizing and reducing agents


In redox processes, the reductant transfers electrons to the oxidant. Thus, in the reaction, the reductant or reducing agent loses electrons and is oxidized, and the oxidant or oxidizing agent gains electrons and is reduced. The pair of an oxidizing and reducing agent that are involved in a particular reaction is called a redox pair. A redox couple is a reducing species and its corresponding oxidized form, e.g., Fe2+/Fe3+.

Oxidizers
Substances that have the ability to oxidize other substances (cause them to lose electrons) are said to be oxidative or oxidizing and are known as oxidizing agents, oxidants, or oxidizers. That is, the oxidant (oxidizing agent) removes electrons from another substance, and is thus itself reduced. And, because it "accepts" electrons, the oxidizing agent is also called an electron acceptor. Hence the name, oxygen is the quintessential oxidizer. Oxidants are usually chemical substances with elements in high oxidation states (e.g., H 2O 2, MnO 4, CrO 3, Cr 2O2 7, OsO 4), or else highly electronegative elements (O , F , Cl , Br ) that can gain extra electrons by oxidizing another 2 2 2 2 substance.

Reducers
Substances that have the ability to reduce other substances (cause them to gain electrons) are said to be reductive or reducing and are known as reducing agents, reductants, or reducers. The reductant (reducing agent) transfers electrons to another substance, and is thus itself oxidized. And, because it "donates" electrons, the reducing agent is also called an electron donor. Electron donors can also form charge transfer complexes with electron acceptors. Reductants in chemistry are very diverse. Electropositive elemental metals, such as lithium, sodium, magnesium, iron, zinc, and aluminium, are good reducing agents. These metals donate or give away electrons readily. Hydride transfer reagents, such as NaBH4 and LiAlH4, are widely used in organic chemistry,[3][4] primarily in the reduction of carbonyl compounds to alcohols. Another method of reduction involves the use of hydrogen gas (H2) with a palladium, platinum, or nickel catalyst. These catalytic reductions are used primarily in the reduction of carbon-carbon double or triple bonds.

Standard electrode potentials (reduction potentials)


Each half-reaction has a standard electrode potential (E0cell), which is equal to the potential difference (or voltage) (E0cell) at equilibrium under standard conditions of an electrochemical cell in which the cathode reaction is the half-reaction considered, and the anode is a standard hydrogen electrode where hydrogen is oxidized: H2 H+ + e-. The electrode potential of each half-reaction is also known as its reduction potential E0red, or potential when the half-reaction takes place at a cathode. The reduction potential is a measure of the tendency of the oxidizing agent to be reduced. Its value is zero for H+ + e H2 by definition, positive for oxidizing agents stronger than H+ (e.g., +2.866 V for F2) and negative for oxidizing agents which are weaker than H+ (e.g. 0.763 V for Zn2+).[5] For a redox reaction which takes place in a cell, the potential difference E0cell = E0cathode E0anode Historically, however, the potential of the reaction at the anode was sometimes expressed as an oxidation potential, E0ox = E0. The oxidation potential is a measure of the tendency of the reducing agent to be oxidized, but does not

Redox represent the physical potential at an electrode. With this notation, the cell voltage equation is written with a plus sign E0cell = E0cathode + E0ox (anode)

208

Examples of redox reactions


A good example is the reaction between hydrogen and fluorine in which hydrogen is being oxidized and fluorine is being reduced: H 2+ F 2 2 HF We can write this overall reaction as two half-reactions: the oxidation reaction: H + 2 2H + 2e and the reduction reaction: F
2

Illustration of a redox reaction

+ 2e 2F

Analyzing each half-reaction in isolation can often make the overall chemical process clearer. Because there is no net change in charge during a redox reaction, the number of electrons in excess in the oxidation reaction must equal the number consumed by the reduction reaction (as shown above). Elements, even in molecular form, always have an oxidation state of zero. In the first half-reaction, hydrogen is oxidized from an oxidation state of zero to an oxidation state of +1. In the second half-reaction, fluorine is reduced from an oxidation state of zero to an oxidation state of 1. When adding the reactions together the electrons are canceled:
H 2 H+ + 2 e
2

F 2 F 2+2e H 2 H+ + 2 F
2+F 2

And the ions combine to form hydrogen fluoride: 2 H+ + 2 F 2 HF The overall reaction is: H 2+ F 2 2 HF

Redox Metal displacement In this type of reaction, a metal atom in a compound (or in a solution) is replaced by an atom of another metal. For example, copper is deposited when zinc metal is placed in a copper(II) sulfate solution: Zn(s)+ CuSO4(aq) ZnSO4(aq) + Cu(s) In the above reaction, zinc metal displaces the copper(II) ion from copper sulfate solution and thus liberates free copper metal. The ionic equation for this reaction is: Zn + Cu2+ Zn2+ + Cu Zn Zn2+ + 2 e And the copper is reduced: Cu2+ + 2 e Cu

209

A redox reaction is the force behind an electrochemical cell like the Galvanic cell pictured. The battery is made out of a zinc electrode in a ZnSO4 solution connected with a wire and a porous disk to a copper electrode in a CuSO4 solution.

As two half-reactions, it is seen that the zinc is oxidized:

Other examples
The oxidation of iron(II) to iron(III) by hydrogen peroxide in the presence of an acid: Fe2+ Fe3+ + e H2O2 + 2 e 2 OH Overall equation: 2 Fe2+ + H2O2 + 2 H+ 2 Fe3+ + 2 H2O The reduction of nitrate to nitrogen in the presence of an acid (denitrification): 2 NO3 + 10 e + 12 H+ N2 + 6 H2O The combustion of hydrocarbons, such as in an internal combustion engine, which produces water, carbon dioxide, some partially oxidized forms such as carbon monoxide, and heat energy. Complete oxidation of materials containing carbon produces carbon dioxide. In organic chemistry, the stepwise oxidation of a hydrocarbon by oxygen produces water and, successively, an alcohol, an aldehyde or a ketone, a carboxylic acid, and then a peroxide.
Iron rusting in pyrite cubes

Redox reactions in industry


The primary process of reducing ore at high temperature to produce metals is known as smelting. Oxidation is used in a wide variety of industries such as in the production of cleaning products and oxidizing ammonia to produce nitric acid, which is used in most fertilizers. Redox reactions are the foundation of electrochemical cells.

Redox The process of electroplating uses redox reactions to coat objects with a thin layer of a material, as in chrome-plated automotive parts, silver plating cutlery, and gold-plated jewelry. The production of compact discs depends on a redox reaction, which coats the disc with a thin layer of metal film.Wikipedia:Please clarify

210

Redox reactions in biology

Top: ascorbic acid (reduced form of Vitamin C) Bottom: dehydroascorbic acid (oxidized form of Vitamin C)

Many important biological processes involve redox reactions. Cellular respiration, for instance, is the oxidation of glucose (C6H12O6) to CO2 and the reduction of oxygen to water. The summary equation for cell respiration is: The process of cell respiration also depends heavily on the reduction of NAD+ to NADH and the reverse reaction (the oxidation of NADH to NAD+). Photosynthesis and cellular respiration are complementary, but photosynthesis is not the reverse of the redox reaction in cell respiration: 6 CO2 + 6 H2O + light energy C6H12O6 + 6 O2 Biological energy is frequently stored and released by means of redox reactions. Photosynthesis involves the reduction of carbon dioxide into sugars and the oxidation of water into molecular oxygen. The reverse reaction, respiration, oxidizes sugars to produce carbon dioxide and water. As intermediate steps, the reduced carbon compounds are used to reduce nicotinamide adenine dinucleotide (NAD+), which then contributes to the creation of a proton gradient, which drives the synthesis of adenosine triphosphate (ATP) and is maintained by the reduction of oxygen. In animal cells, mitochondria perform similar functions. See the Membrane potential article. Free radical reactions are redox reactions that occur as a part of homeostasis and killing microorganisms, where an electron detaches from a molecule and then reattaches almost instantaneously. Free radicals are a part of redox molecules and can become harmful to the human body if they do not reattach to the redox molecule or an antioxidant. Unsatisfied free radicals can spur the mutation of cells they encounter and are thus causes of cancer. The term redox state is often used to describe the balance of NAD+/NADH and NADP+/NADPH in a biological system such as a cell or organ. The redox state is reflected in the balance of several sets of metabolites (e.g., lactate and pyruvate, beta-hydroxybutyrate and acetoacetate), whose interconversion is dependent on these ratios. An abnormal redox state can develop in a variety of deleterious situations, such as hypoxia, shock, and sepsis. Redox mechanism also control some cellular processes. Redox proteins and their genes must be co-located for redox regulation according to the CoRR hypothesis for the function of DNA in mitochondria and chloroplasts. C6H12O6 + 6 O2 6 CO2 + 6 H2O

Redox

211

Redox cycling
A wide variety of aromatic compounds are enzymatically reduced to form free radicals that contain one more electron than their parent compounds. In general, the electron donor is any of a wide variety of flavoenzymes and their coenzymes. Once formed, these anion free radicals reduce molecular oxygen to superoxide, and regenerate the unchanged parent compound. The net reaction is the oxidation of the flavoenzyme's coenzymes and the reduction of molecular oxygen to form superoxide. This catalytic behavior has been described as futile cycle or redox cycling. Examples of redox cycling-inducing molecules are the herbicide paraquat and other viologens and quinones such as menadione.[6]

Redox reactions in geology


In geology, redox is important to both the formation of minerals, mobilization of minerals, and in some depositional environments. In general, the redox state of most rocks can be seen in the color of the rock. Red is associated with oxidizing conditions of formation, and green is typically associated with reducing conditions. White can also be associated with reducing conditions. Famous examples of redox conditions affecting geological processes include uranium deposits and Moqui marbles.

Balancing redox reactions


Describing the overall electrochemical reaction for a redox process requires a balancing of the component half-reactions for oxidation and reduction. In general, for reactions in aqueous solution, this involves adding H+, OH, H2O, and electrons to compensate for the oxidation changes.

A uranium mine, near Moab, Utah. Note alternating red and white/green sandstone. This corresponds to oxidized and reduced conditions in groundwater redox chemistry. The rock forms in oxidizing conditions, and is then "bleached" to the white/green state when a reducing fluid passes through the rock. The reduced fluid can also carry uranium-bearing minerals.

Acidic media
In acidic media, H+ ions and water are added to half reactions to balance the overall reaction. For instance, when manganese(II) reacts with sodium bismuthate:
Unbalanced reaction: Mn2+ (aq) + NaBiO 3(s) Bi3+ (aq) + MnO 4 (aq) Oxidation: 4H 2O(l) + Mn2+ (aq) MnO 4(aq) + 8 H+ (aq) + 5 e

Redox

212
Reduction: 2 e + 6 H+ + BiO 3(s) Bi3+ (aq) + 3 H 2O(l)

The reaction is balanced by scaling the two half-cell reactions to involve the same number of electrons (multiplying the oxidation reaction by the number of electrons in the reduction step and vice versa): 8H 2O(l) + 2 Mn2+ (aq) 2 MnO 4(aq) + 16 H+ (aq) + 10 e 10 e + 30 H+ + 5 BiO 3(s) 5 Bi3+ (aq) + 15 H 2O(l) Adding these two reactions eliminates the electrons terms and yields the balanced reaction: 14 H+ (aq) + 2 Mn2+ (aq) + 5 NaBiO 3(s) 7 H 2O(l) + 2 MnO 4(aq) + 5 Bi3+ (aq) + 5 Na+ (aq)

Basic media
In basic media, OH ions and water are added to half reactions to balance the overall reaction. For example, in the reaction between potassium permanganate and sodium sulfite:
Unbalanced reaction: KMnO 4 + Na 2SO 3+H 2O MnO 2 + Na 2SO 4 + KOH Reduction: 3 e + 2 H 2O + MnO 4 MnO 2 + 4 OH

Redox

213
Oxidation:

2 OH + SO 2 3 SO 2 4 +H 2O + 2 e

Balancing the number of electrons in the two half-cell reactions gives: 6 e + 4 H 2O + 2 MnO 4 2 MnO 2 + 8 OH 6 OH + 3 SO 2 3 3 SO 2 4 +3H 2O + 6 e Adding these two half-cell reactions together gives the balanced equation: 2 KMnO 4 + 3 Na 2SO 3+ H 2O 2 MnO 2 + 3 Na 2SO 4 + 2 KOH

Memory aids
The key terms involved in redox are often confusing to students.[][] For example, an element that is oxidized loses electrons; however, that element is referred to as the reducing agent. Likewise, an element that is reduced gains electrons and is referred to as the oxidizing agent.[] Acronyms or mnemonics are commonly used[] to help remember what is happening: "OIL RIG"Oxidation Is Loss of electrons, Reduction Is Gain of electrons.[][][][] "LEO the lion says GER" Loss of Electrons is Oxidation, Gain of Electrons is Reduction.[][][][] "LEORA says GEROA" Loss of Electrons is Oxidation (Reducing Agent) and Gain of Electrons is Reduced (Oxidizing Agent).[]

References
[5] Electrode potential values from

Schring, J., Schulz, H. D., Fischer, W. R., Bttcher, J., Duijnisveld, W. H. (editors)(1999). Redox: Fundamentals, Processes and Applications, Springer-Verlag, Heidelberg, 246 pp.ISBN 978-3-540-66528-1 (pdf 3,6 MB) (http://hdl.handle.net/10013/epic.31694.d001) Tratnyek, Paul G.; Grundl, Timothy J.; Haderlein, Stefan B., eds. (2011). Aquatic Redox Chemistry. ACS Symposium Series 1071. doi: 10.1021/bk-2011-1071 (http://dx.doi.org/10.1021/bk-2011-1071). ISBN9780841226524.

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External links
Chemical Equation Balancer (http://www.berkeleychurchill.com/software/chembal.php) - An open source chemical equation balancer that handles redox reactions. Video - Synthesis of Copper(II) Acetate (http://www.youtube.com/watch?v=rF1ls-v7puQ) 20 Feb. 2009 Redox reactions calculator (http://www.shodor.org/UNChem/advanced/redox/redoxcalc.html) Redox reactions at Chemguide (http://www.chemguide.co.uk/inorganic/redox/definitions.html#top) Online redox reaction equation balancer, balances equations of any half-cell and full reactions (http://www. webqc.org/balance.php)

Aluminium

215

Aluminium
Aluminium Al 13

magnesium aluminium siliconB

Al
Ga Aluminium in the periodic table Appearance silvery gray metallic

Spectral lines of aluminium General properties Name, symbol, number Pronunciation aluminium, Al, 13 UK i/ljmnim/ AL-ew-MIN-ee-m; US -LEW-mi-nm poor metal 13, 3, p 26.9815386(13)
i

/ljumnm/

Element category Group, period, block Standard atomic weight

Aluminium

216
Electron configuration

[Ne] 3s2 3p1 2, 8, 3

History Prediction First isolation Named by Antoine Lavoisier Friedrich Whler Humphry Davy Physical properties Phase Density (near r.t.) Liquid density at m.p. Meltingpoint Boilingpoint Heatoffusion Heat of vaporization Molar heat capacity solid 2.70 gcm3 2.375 gcm3 933.47K, 660.32C, 1220.58F 2792K, 2519C, 4566F 10.71 kJmol1 294.0 kJmol1 24.200 Jmol1K1 Vapor pressure P (Pa) 1 10 100 1k 10 k 100 k
[1]

(1787)

[1]

(1827)

[1]

(1807)

at T (K) 1482 1632 1817 2054 2364 2790 Atomic properties Oxidation states 3, 2 , 1 (amphoteric oxide) 1.61 (Pauling scale) 1st: 577.5 kJmol1 2nd: 1816.7 kJmol1 3rd: 2744.8 kJmol1 Atomic radius Covalent radius 143 pm 1214 pm
[2] [3]

Electronegativity Ionization energies (more)

Aluminium

217
Van der Waals radius 184 pm Miscellanea Crystal structure face-centered cubic

Magnetic ordering Electrical resistivity Thermal conductivity Thermal expansion Speed of sound (thin rod) Young's modulus Shear modulus Bulk modulus Poisson ratio Mohs hardness Vickers hardness Brinell hardness CAS registry number

paramagnetic

[4]

(20C) 28.2 nm 237Wm1K1 (25 C) 23.1 mm1K1 (r.t.) (rolled) 5,000ms1 70 GPa 26 GPa 76 GPa 0.35 2.75 167 MPa 245 MPa 7429-90-5 Most stable isotopes Main article: Isotopes of aluminium

iso
26

NA

half-life

DM DE (MeV) + 1.17 1.8086

DP
26 26

Al trace 7.17105y

Mg Mg -

27

Al 100%

27

Al is stable with 14 neutrons

Aluminium (or aluminum) is a chemical element in the boron group with symbolAl and atomic number13. It is a silvery white, soft, ductile metal. Aluminium is the third most abundant element (after oxygen and silicon), and the most abundant metal, in the Earth's crust. It makes up about 8% by weight of the Earth's solid surface. Aluminium metal is so chemically reactive that native specimens are rare and limited to extreme reducing environments. Instead, it is found combined in over 270 different minerals.[5] The chief ore of aluminium is bauxite. Aluminium is remarkable for the metal's low density and for its ability to resist corrosion due to the phenomenon of passivation. Structural components made from aluminium and its alloys are vital to the aerospace industry and are important in other areas of transportation and structural materials. The most useful compounds of aluminium, at least on a weight basis, are the oxides and sulfates. Despite its prevalence in the environment, aluminium salts are not known to be used by any form of life. In keeping with its pervasiveness, aluminium is well tolerated by plants and animals.[6] Owing to their prevalence, potential beneficial (or otherwise) biological roles of aluminium compounds are of continuing interest.

Aluminium

218

Characteristics
Physical
Aluminium is a relatively soft, durable, lightweight, ductile and malleable metal with appearance ranging from silvery to dull gray, depending on the surface roughness. It is nonmagnetic and does not easily ignite. A fresh film of aluminium serves as a good reflector (approximately 92%) of visible light and an excellent reflector (as much as 98%) of medium and far infrared radiation. The yield strength of pure aluminium is 711 MPa, while aluminium alloys have yield strengths ranging from 200 MPa to 600 MPa.[7] Aluminium has about one-third the density and stiffness of steel. It is easily machined, cast,

Etched surface from a high purity (99.9998%) aluminium bar, size 5537 mm

drawn and extruded. Aluminium atoms are arranged in a face-centered cubic (fcc) structure. Aluminium has a stacking-fault energy of approximately 200 mJ/m2.[8] Aluminium is a good thermal and electrical conductor, having 59% the conductivity of copper, both thermal and electrical, while having only 30% of copper's density. Aluminium is capable of being a superconductor, with a superconducting critical temperature of 1.2 Kelvin and a critical magnetic field of about 100 gauss (10 milliteslas).[9]

Chemical
Corrosion resistance can be excellent due to a thin surface layer of aluminium oxide that forms when the metal is exposed to air, effectively preventing further oxidation. The strongest aluminium alloys are less corrosion resistant due to galvanic reactions with alloyed copper.[7] This corrosion resistance is also often greatly reduced by aqueous salts, particularly in the presence of dissimilar metals. Owing to its resistance to corrosion, aluminium is one of the few metals that retain silvery reflectance in finely powdered form, making it an important component of silver-colored paints. Aluminium mirror finish has the highest reflectance of any metal in the 200400nm (UV) and the 3,00010,000nm (far IR) regions; in the 400700nm visible range it is slightly outperformed by tin and silver and in the 7003000 (near IR) by silver, gold, and copper.[10] Aluminium is oxidized by water to produce hydrogen and heat: 2 Al + 3 H2O Al2O3 + 3 H2 This conversion is of interest for the production of hydrogen. Challenges include circumventing the formed oxide layer which inhibits the reaction and the expenses associated with the storage of energy by regeneration of the Al metal.[11]

Isotopes
Aluminium has many known isotopes, whose mass numbers range from 21 to 42; however, only 27Al (stable isotope) and 26Al (radioactive isotope, t1/2= 7.2105 y) occur naturally. 27Al has a natural abundance above 99.9%. 26 Al is produced from argon in the atmosphere by spallation caused by cosmic-ray protons. Aluminium isotopes have found practical application in dating marine sediments, manganese nodules, glacial ice, quartz in rock exposures, and meteorites. The ratio of 26Al to 10Be has been used to study the role of transport, deposition, sediment storage, burial times, and erosion on 105 to 106 year time scales.[12] Cosmogenic 26Al was first applied in studies of the Moon and meteorites. Meteoroid fragments, after departure from their parent bodies, are exposed to intense cosmic-ray bombardment during their travel through space, causing substantial 26Al production. After falling

Aluminium to Earth, atmospheric shielding drastically reduces 26Al production, and its decay can then be used to determine the meteorite's terrestrial age. Meteorite research has also shown that 26Al was relatively abundant at the time of formation of our planetary system. Most meteorite scientists believe that the energy released by the decay of 26Al was responsible for the melting and differentiation of some asteroids after their formation 4.55 billion years ago.[13]

219

Natural occurrence
Stable aluminium is created when hydrogen fuses with magnesium either in large stars or in supernovae.[14] In the Earth's crust, aluminium is the most abundant (8.3% by weight) metallic element and the third most abundant of all elements (after oxygen and silicon).[] Because of its strong affinity to oxygen, it is almost never found in the elemental state; instead it is found in oxides or silicates. Feldspars, the most common group of minerals in the Earth's crust, are aluminosilicates. Native aluminium metal can only be found as a minor phase in low oxygen fugacity environments, such as the interiors of certain volcanoes.[15] Native aluminium has been reported in cold seeps in the northeastern continental slope of the South China Sea and Chen et al. (2011)[] have proposed a theory of its origin as resulting by reduction from tetrahydroxoaluminate Al(OH)4 to metallic aluminium by bacteria.[] It also occurs in the minerals beryl, cryolite, garnet, spinel and turquoise. Impurities in Al2O3, such as chromium or iron yield the gemstones ruby and sapphire, respectively. Although aluminium is an extremely common and widespread element, the common aluminium minerals are not economic sources of the metal. Almost all metallic aluminium is produced from the ore bauxite (AlOx(OH)32x). Bauxite occurs as a weathering product of low iron and silica bedrock in tropical climatic conditions.[16] Large deposits of bauxite occur in Australia, Brazil, Guinea and Jamaica and the primary mining areas for the ore are in Australia, Brazil, China, India, Guinea, Indonesia, Jamaica, Russia and Suriname.

Production and refinement


Aluminium forms strong chemical bonds with oxygen. Compared to most other metals, it is difficult to extract from ore, such as bauxite, due to the high reactivity of aluminium and the high melting point of most of its ores. For example, direct reduction with carbon, as is used to produce iron, is not chemically possible because aluminium is a stronger reducing agent than carbon. Indirect carbothermic reduction can be carried out using carbon and Al2O3, which forms an intermediate Al4C3 and this can further yield aluminium metal at a temperature of 19002000 C. This process is still under development; Bauxite, a major aluminium ore. The red-brown it requires less energy and yields less CO2 than the Hall-Hroult colour is due to the presence of iron minerals. process, the major industrial process for aluminium extraction.[17] Electrolytic smelting of alumina was originally cost-prohibitive in part because of the high melting point of alumina, or aluminium oxide, (about 2,000 C (3,600F)). Many minerals, however, will dissolve into a second already molten mineral, even if the temperature of the melt is significantly lower than the melting point of the first mineral. Molten cryolite was discovered to dissolve alumina at temperatures significantly lower than the melting point of pure alumina without interfering in the smelting process. In the Hall-Hroult process, alumina is first dissolved into molten cryolite with calcium fluoride and then electrolytically reduced to aluminium at a temperature between 950 and 980 C (1,740 to 1,800 F). Cryolite is a chemical compound of aluminium and sodium fluorides: (Na3AlF6). Although cryolite is found as a mineral in Greenland, its synthetic form is used in the industry. The aluminium oxide itself is obtained by refining bauxite in the Bayer process.

Aluminium The electrolytic process replaced the Whler process, which involved the reduction of anhydrous aluminium chloride with potassium. Both of the electrodes used in the electrolysis of aluminium oxide are carbon. Once the refined alumina is dissolved in the electrolyte, it disassociates and its ions are free to move around. The reaction at the cathode is: Al3+ + 3 e Al Here the aluminium ion is being reduced. The aluminium metal then sinks to the bottom and is tapped off, usually cast into large blocks called aluminium billets for further processing. At the anode, oxygen is formed: 2 O2 O2 + 4 e To some extent, the carbon anode is consumed by subsequent reaction with oxygen to form carbon dioxide. The anodes in a reduction cell must therefore be replaced regularly, since they are consumed in the process. The cathodes do erode, mainly due to electrochemical processes and metal movement. After five to ten years, depending on the current used in the electrolysis, a cell has to be rebuilt because of cathode wear. Aluminium electrolysis with the Hall-Hroult process consumes a lot of energy, but alternative processes were always found to be less viable economically and/or ecologically. The worldwide average specific energy consumption is approximately 150.5 kilowatt-hours per kilogram of aluminium produced (52 to 56 MJ/kg). The most modern smelters achieve approximately 12.8kWh/kg (46.1 MJ/kg). (Compare this to the heat of reaction, 31 MJ/kg, and the Gibbs free energy of reaction, 29 MJ/kg.) Reduction line currents for older technologies are typically 100 to 200 kiloamperes; state-of-the-art smelters operate at about 350 kA. Trials have been reported with 500 kA cells.[citation
needed]

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World production trend of aluminium

The Hall-Heroult process produces aluminium with a purity of above 99%. Further purification can be done by the Hoope process. The process involves the electrolysis of molten aluminium with a sodium, barium and aluminium fluoride electrolyte. The resulting aluminium has a purity of 99.99%.[18][19] Electric power represents about 20% to 40% of the cost of producing aluminium, depending on the location of the smelter. Aluminium production consumes roughly 5% of electricity generated in the U.S.[20] Smelters tend to be situated where electric power is both plentiful and inexpensive, such as the United Arab Emirates with excess natural gas supplies and Iceland and Norway with energy generated from renewable sources. The world's largest smelters of alumina are People's Republic of China, Russia, and Quebec and British Columbia in Canada.[20][21][22] In 2005, the People's Republic of China was the top producer of aluminium with almost a one-fifth world share, followed by Russia, Canada, and the USA, reports the British Geological Survey. Over the last 50 years, Australia has become a major producer of bauxite ore and a major producer and exporter of alumina (before being overtaken by China in 2007).[21][23] Australia produced 68 million tonnes of bauxite in 2010. The Australian deposits have some refining problems, some being high in silica, but have the advantage of being shallow and relatively easy to mine.[24]

Aluminium spot price 1987 2012

Aluminium

221

Recycling
Aluminium is theoretically 100% recyclable without any loss of its natural qualities. According to the International Resource Panel's Metal Stocks in Society report, the global per capita stock of aluminium in use in society (i.e. in cars, buildings, electronics etc.) is 80kg. Much of this is in more-developed countries (350500kg per capita) rather than less-developed countries (35kg per capita). Knowing the per capita stocks and their approximate lifespans is important for planning recycling. Recovery of the metal via recycling has become an important use of the aluminium industry. Recycling was a low-profile activity until the late 1960s, when the growing use of aluminium beverage cans brought it to the public awareness.

Aluminium recycling code

Recycling involves melting the scrap, a process that requires only 5% of the energy used to produce aluminium from ore, though a significant part (up to 15% of the input material) is lost as dross (ash-like oxide).[25] The dross can undergo a further process to extract aluminium. In Europe aluminium experiences high rates of recycling, ranging from 42% of beverage cans, 85% of construction materials and 95% of transport vehicles.[26] Recycled aluminium is known as secondary aluminium, but maintains the same physical properties as primary aluminium. Secondary aluminium is produced in a wide range of formats and is employed in 80% of alloy injections. Another important use is for extrusion. White dross from primary aluminium production and from secondary recycling operations still contains useful quantities of aluminium that can be extracted industrially.[27] The process produces aluminium billets, together with a highly complex waste material. This waste is difficult to manage. It reacts with water, releasing a mixture of gases (including, among others, hydrogen, acetylene, and ammonia), which spontaneously ignites on contact with air;[28] contact with damp air results in the release of copious quantities of ammonia gas. Despite these difficulties, the waste has found use as a filler in asphalt and concrete.[29]

Compounds
Oxidation state +3
The vast majority of compounds, including all Al-containing minerals and all commercially significant aluminium compounds, feature aluminium in the oxidation state 3+. The coordination number of such compounds varies, but generally Al3+ is six-coordinate or tetracoordinate. Almost all compounds of aluminium(III) are colorless.[] Halides All four trihalides are well known. Unlike the structures of the three heavier trihalides, aluminium fluoride (AlF3) features six-coordinate Al. The octahedral coordination environment for AlF3 is related to the compactness of fluoride ion, six of which can fit around the small Al3+ centre. AlF3 sublimes (with cracking) at 1,291 C (2,356F). With heavier halides, the coordination numbers are lower. The other trihalides are dimeric or polymeric with tetrahedral Al centers. These materials are prepared by treating aluminium metal with the halogen, although other methods exist. Acidification of the oxides or hydroxides affords hydrates. In aqueous solution, the halides often form mixtures, generally containing six-coordinate Al centres, which are feature both halide and aquo ligands. When aluminium and fluoride are together in aqueous solution, they readily form complex ions such as [AlF(H 2O) 5]2+

Aluminium , AlF 3(H 2O) 3, and [AlF 6]3 . In the case of chloride, polyaluminium clusters are formed such as [Al13O4(OH)24(H2O)12]7+. Oxide and hydroxides Aluminium forms one stable oxide, known by its mineral name corundum. Sapphire and ruby are impure corundum contaminated with trace amounts of other metals. The two oxide-hydroxides, AlO(OH), are boehmite and diaspore. There are three trihydroxides: bayerite, gibbsite, and nordstrandite, which differ in their crystalline structure (polymorphs). Most are produced from ores by a variety of wet processes using acid and base. Heating the hydroxides leads to formation of corundum. These materials are of central importance to the production of aluminium and are themselves extremely useful. Carbide, nitride, and related materials Aluminium carbide (Al4C3) is made by heating a mixture of the elements above 1,000 C (1,832F). The pale yellow crystals consist of tetrahedral aluminium centres. It reacts with water or dilute acids to give methane. The acetylide, Al2(C2)3, is made by passing acetylene over heated aluminium. Aluminium nitride (AlN) is the only nitride known for aluminium. Unlike the oxides it features tetrahedral Al centres. It can be made from the elements at 800 C (1,472F). It is air-stable material with a usefully high thermal conductivity. Aluminium phosphide (AlP) is made similarly, and hydrolyses to give phosphine: AlP + 3 H2O Al(OH)3 + PH3

222

Organoaluminium compounds and related hydrides


A variety of compounds of empirical formula AlR3 and AlR1.5Cl1.5 exist.[30] These species usually feature tetrahedral Al centers, e.g. "trimethylaluminium" has the formula Al2(CH3)6 (see figure). With large organic groups, triorganoaluminium exist as three-coordinate monomers, such as triisobutylaluminium. Such compounds are widely used in industrial chemistry, despite the fact that they are often highly pyrophoric. Few analogues exist between organoaluminium and organoboron compounds except for large organic groups.
Structure of trimethylaluminium, a compound that features five-coordinate carbon.

The important aluminium hydride is lithium aluminium hydride (LiAlH4), which is used in as a reducing agent in organic chemistry. It can be produced from lithium hydride and aluminium trichloride:

4 LiH + AlCl3 LiAlH4 + 3 LiCl Several useful derivatives of LiAlH4 are known, e.g. sodium bis(2-methoxyethoxy)dihydridoaluminate. The simplest hydride, aluminium hydride or alane, remains a laboratory curiosity. It is a polymer with the formula (AlH3)n, in contrast to the corresponding boron hydride with the formula (BH3)2.

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223

Oxidation states +1 and +2


Although the great majority of aluminium compounds feature Al3+ centers, compounds with lower oxidation states are known and sometime of significance as precursors to the Al3+ species. Aluminium(I) AlF, AlCl and AlBr exist in the gaseous phase when the trihalide is heated with aluminium. The composition AlI is unstable at room temperature with respect to the triiodide:[31] 3 AlI AlI3 + 2 Al A stable derivative of aluminium monoiodide is the cyclic adduct formed with triethylamine, Al4I4(NEt3)4. Also of theoretical interest but only of fleeting existence are Al2O and Al2S. Al2O is made by heating the normal oxide, Al2O3, with silicon at 1,800 C (3,272F) in a vacuum.[31] Such materials quickly disproportionates to the starting materials. Aluminium(II) Very simple Al(II) compounds are invoked or observed in the reactions of Al metal with oxidants. For example, aluminium monoxide, AlO, has been detected in the gas phase after explosion[32] and in stellar absorption spectra.[33] More thoroughly investigated are compounds of the formula R4Al2 where R is a large organic ligand.[34]

Analysis
The presence of aluminium can be detected in qualitative analysis using aluminon.

Applications
General use
Aluminium is the most widely used non-ferrous metal.[35] Global production of aluminium in 2005 was 31.9 million tonnes. It exceeded that of any other metal except iron (837.5 million tonnes).[36] Forecast for 2012 is 4245 million tonnes, driven by rising Chinese output.[37] Aluminium is almost always alloyed, which markedly improves its mechanical properties, especially when tempered. For example, the common aluminium foils and beverage cans are alloys of 92% to 99% aluminium.[38] The main alloying agents are copper, zinc, magnesium, manganese, and silicon (e.g., duralumin) and the levels of these other metals are in the range of a few percent by weight.[39] Some of the many uses for aluminium metal are in: Transportation (automobiles, aircraft, trucks, railway cars, marine vessels, bicycles, etc.) as sheet, tube, castings, etc. Packaging (cans, foil, frame of etc.) Construction (windows, doors, siding, building wire, etc.).[40] A wide range of household items, from cooking utensils to baseball bats, watches.[41] Street lighting poles, sailing ship masts, walking poles, etc. Outer shells of consumer electronics, also cases for equipment e.g. photographic equipment, MacBook Pro's casing Electrical transmission lines for power distribution MKM steel and Alnico magnets Super purity aluminium (SPA, 99.980% to 99.999% Al), used in electronics and CDs.
Household aluminium foil

Aluminium Heat sinks for electronic appliances such as transistors and CPUs. Substrate material of metal-core copper clad laminates used in high brightness LED lighting. Powdered aluminium is used in paint, and in pyrotechnics such as solid rocket fuels and thermite. Aluminium can be reacted with hydrochloric acid or with sodium hydroxide to produce hydrogen gas. A variety of countries, including France, Italy, Poland, Finland, Romania, Israel, and the former Yugoslavia, have issued coins struck in aluminium or aluminium-copper alloys.[42][43] Some guitar models sport aluminium diamond plates on the surface of the instruments, usually either chrome or black. Kramer Guitars and Travis Bean are both known for having produced guitars with necks made of aluminium, which gives the instrument a very distinct sound. Aluminium is usually alloyed it is used as pure metal only when corrosion resistance and/or workability is more important than strength or hardness. A thin layer of aluminium can be deposited onto a flat surface by physical vapour deposition or (very infrequently) chemical vapour deposition or other chemical means to form optical coatings and mirrors.
Aluminium-bodied Austin "A40 Sports" (c. 1951)

224

Aluminium slabs being transported from a smelter

Aluminium compounds
Because aluminium is abundant and most of its derivatives exhibit low toxicity, the compounds of aluminium enjoy wide and sometimes large-scale applications. Alumina Aluminium oxide (Al2O3) and the associated oxy-hydroxides and trihydroxides are produced or extracted from minerals on a large scale. The great majority of this material is converted to metallic aluminium. About 10% of the production capacity is used for other applications. A major use is as an absorbent, for example alumina will remove water from hydrocarbons, to enable subsequent processes that are poisoned by moisture. Aluminium oxides are common catalysts for industrial processes, e.g. the Claus process for converting hydrogen sulfide to sulfur in refineries and for the alkylation of amines. Many industrial catalysts are "supported", meaning generally that an expensive catalyst (e.g., platinum) is dispersed over a high surface area material such as alumina. Being a very hard material (Mohs hardness 9), alumina is widely used as an abrasive and the production of applications that exploit its inertness, e.g., in high pressure sodium lamps. Sulfates Several sulfates of aluminium find applications. Aluminium sulfate (Al2(SO4)3(H2O)18) is produced on the annual scale of several billions of kilograms. About half of the production is consumed in water treatment. The next major application is in the manufacture of paper. It is also used as a mordant, in fire extinguisher, as a food additive, in fireproofing, and in leather tanning. Aluminium ammonium sulfate, which is also called ammonium alum, (NH4)Al(SO4)212H2O, is used as a mordant and in leather tanning.[6] Aluminium potassium sulfate ([Al(K)](SO4)2)(H2O)12 is used similarly. The consumption of both alums is declining.

Aluminium Chlorides Aluminium chloride (AlCl3) is used in petroleum refining and in the production of synthetic rubber and polymers. Although it has a similar name, aluminium chlorohydrate has fewer and very different applications, e.g. as a hardening agent and an antiperspirant. It is an intermediate in the production of aluminium metal. Niche compounds Given the scale of aluminium compounds, a small scale application could still involve thousands of tonnes. One of the many compounds used at this intermediate level include aluminium acetate, a salt used in solution as an astringent. Aluminium borate (Al2O3B2O3) is used in the production of glass and ceramics. Aluminium fluorosilicate (Al2(SiF6)3) is used in the production of synthetic gemstones, glass and ceramic. Aluminium phosphate (AlPO4) is used in the manufacture: of glass and ceramic, pulp and paper products, cosmetics, paints and varnishes and in making dental cement. Aluminium hydroxide (Al(OH)3) is used as an antacid, as a mordant, in water purification, in the manufacture of glass and ceramic and in the waterproofing of fabrics. Lithium aluminium hydride is a powerful reducing agent used in organic chemistry. Organoaluminiums are used as Lewis acids and cocatalysts. For example, methylaluminoxane is a cocatalyst for Ziegler-Natta olefin polymerization to produce vinyl polymers such as polyethene.

225

Aluminium alloys in structural applications


Aluminium alloys with a wide range of properties are used in engineering structures. Alloy systems are classified by a number system (ANSI) or by names indicating their main alloying constituents (DIN and ISO). The strength and durability of aluminium alloys vary widely, not only as a result of the components of the specific alloy, but also as a result of heat treatments and manufacturing processes. A lack of knowledge of these aspects has from time to time led to improperly designed structures and gained aluminium a bad reputation. One important structural limitation of aluminium alloys is their fatigue strength. Unlike steels, aluminium alloys have no well-defined fatigue limit, meaning that fatigue failure eventually occurs, under even very small cyclic loadings. This implies that engineers must assess these loads and design for a fixed life rather than an infinite life. Another important property of aluminium alloys is their sensitivity to Aluminium foam heat. Workshop procedures involving heating are complicated by the fact that aluminium, unlike steel, melts without first glowing red. Forming operations where a blow torch is used therefore require some expertise, since no visual signs reveal how close the material is to melting. Aluminium alloys, like all structural alloys, also are subject to internal stresses following heating operations such as welding and casting. The problem with aluminium alloys in this regard is their low melting point, which make them more susceptible to distortions from thermally induced stress relief. Controlled stress relief can be done during manufacturing by heat-treating the parts in an oven, followed by gradual coolingin effect annealing the stresses. The low melting point of aluminium alloys has not precluded their use in rocketry; even for use in constructing combustion chambers where gases can reach 3500K. The Agena upper stage engine used a regeneratively cooled aluminium design for some parts of the nozzle, including the thermally critical throat region. Another alloy of some value is aluminium bronze (Cu-Al alloy).

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History
Ancient Greeks and Romans used aluminium salts as dyeing mordants and as astringents for dressing wounds; alum is still used as a styptic. In 1761, Guyton de Morveau suggested calling the base alum alumine. In 1808, Humphry Davy identified the existence of a metal base of alum, which he at first termed alumium and later aluminum (see etymology section, below). The metal was first produced in 1825 in an impure form by Danish physicist and chemist Hans Christian rsted. He reacted anhydrous aluminium chloride with potassium amalgam, yielding a lump of metal looking similar to tin.[44] Friedrich Whler was aware of these experiments and cited them, but after redoing the experiments of rsted he concluded that this metal was pure potassium. He conducted a similar experiment in 1827 by mixing anhydrous aluminium chloride with potassium and yielded aluminium.[44] Whler is generally credited with isolating aluminium (Latin alumen, alum). Further, Pierre Berthier discovered aluminium in bauxite ore and successfully extracted it.[45]WP:NOTRS Frenchman Henri Etienne Sainte-Claire The statue of the Anteros (commonly mistaken for either The Angel of Christian Charity or Eros) Deville improved Whler's method in 1846, and described his in Piccadilly Circus, London, was made in 1893 improvements in a book in 1859, chief among these being the and is one of the first statues to be cast in substitution of sodium for the considerably more expensive aluminium. potassium.[46] Deville likely also conceived the idea of the electrolysis of aluminium oxide dissolved in cryolite; Charles Martin Hall and Paul Hroult might have developed the more practical process after Deville. Prior to commercial electrical generation in the early 1880s, and the Hall-Hroult process in the mid 1880s, aluminium was exceedingly difficult to extract from its various ores. This made pure aluminium more valuable than gold.[47] Bars of aluminium were exhibited at the Exposition Universelle of 1855.[48] Napoleon III of France is reputed to have given a banquet where the most honoured guests were given aluminium utensils, while the others made do with gold.[49][50] Aluminium was selected as the material to be used for the 100 ounce (2.8kg) capstone of the Washington Monument in 1884, a time when one ounce (30grams) cost the daily wage of a common worker on the project.[51] The capstone, which was set in place on December 6, 1884, in an elaborate dedication ceremony, was the largest single piece of aluminium cast at the time, when aluminium was as expensive as silver.[51] The Cowles companies supplied aluminium alloy in quantity in the United States and England using smelters like the furnace of Carl Wilhelm Siemens by 1886.[52][53][54] Charles Martin Hall of Ohio in the U.S. and Paul Hroult of France independently developed the Hall-Hroult electrolytic process that made extracting aluminium from minerals cheaper and is now the principal method used worldwide. Hall's process,[55] in 1888 with the financial backing of Alfred E. Hunt, started the Pittsburgh Reduction Company today known as Alcoa. Hroult's process was in production by 1889 in Switzerland at Aluminium Industrie, now Alcan, and at British Aluminium, now Luxfer Group and Alcoa, by 1896 in Scotland.[] By 1895, the metal was being used as a building material as far away as Sydney, Australia in the dome of the Chief Secretary's Building. Many navies have used an aluminium superstructure for their vessels; the 1975 fire aboard USS Belknap that gutted her aluminium superstructure, as well as observation of battle damage to British ships during the Falklands War, led to many navies switching to all steel superstructures. The Arleigh Burke class was the first such U.S. ship, being

Aluminium constructed entirely of steel. Aluminium wire was once widely used for domestic electrical wiring. Owing to corrosion-induced failures, a number of fires resulted.

227

Etymology
Two variants of the metal's name are in current use, aluminium and aluminum (besides the obsolete alumium). The International Union of Pure and Applied Chemistry (IUPAC) adopted aluminium as the standard international name for the element in 1990 but, three years later, recognized aluminum as an acceptable variant. Hence their periodic table includes both.[56] IUPAC prefers the use of aluminium in its internal publications, although nearly as many IUPAC publications use the spelling aluminum.[57] Most countries use the spelling aluminium. In the United States and Canada, the spelling aluminum predominates.[][58] The Canadian Oxford Dictionary prefers aluminum, whereas the Australian Macquarie Dictionary prefers aluminium. In 1926, the American Chemical Society officially decided to use aluminum in its publications; American dictionaries typically label the spelling aluminium as "chiefly British".[59][60] The name aluminium derives from its status as a base of alum. It is borrowed from Old French; its ultimate source, alumen, in turn is a Latin word that literally means "bitter salt".[61] The earliest citation given in the Oxford English Dictionary for any word used as a name for this element is alumium, which British chemist and inventor Humphry Davy employed in 1808 for the metal he was trying to isolate electrolytically from the mineral alumina. The citation is from the journal Philosophical Transactions of the Royal Society of London: "Had I been so fortunate as to have obtained more certain evidences on this subject, and to have procured the metallic substances I was in search of, I should have proposed for them the names of silicium, alumium, zirconium, and glucium."[62][63] Davy settled on aluminum by the time he published his 1812 book Chemical Philosophy: "This substance appears to contain a peculiar metal, but as yet Aluminum has not been obtained in a perfectly free state, though alloys of it with other metalline substances have been procured sufficiently distinct to indicate the probable nature of alumina."[64] But the same year, an anonymous contributor to the Quarterly Review, a British political-literary journal, in a review of Davy's book, objected to aluminum and proposed the name aluminium, "for so we shall take the liberty of writing the word, in preference to aluminum, which has a less classical sound."[65] The -ium suffix conformed to the precedent set in other newly discovered elements of the time: potassium, sodium, magnesium, calcium, and strontium (all of which Davy isolated himself). Nevertheless, -um spellings for elements were not unknown at the time, as for example platinum, known to Europeans since the 16th century, molybdenum, discovered in 1778, and tantalum, discovered in 1802. The -um suffix is consistent with the universal spelling alumina for the oxide (as opposed to aluminia), as lanthana is the oxide of lanthanum, and magnesia, ceria, and thoria are the oxides of magnesium, cerium, and thorium respectively. The spelling used throughout the 19th century by most U.S. chemists was aluminium, but common usage is less clear.[66] The aluminum spelling is used in the Webster's Dictionary of 1828. In his advertising handbill for his new electrolytic method of producing the metal 1892, Charles Martin Hall used the -um spelling, despite his constant use of the -ium spelling in all the patents[55] he filed between 1886 and 1903.[67] It has consequently been suggestedWikipedia:Avoid weasel words that the spelling reflects an easier to pronounce word with one fewer syllable, or that the spelling on the flier was a mistake. Hall's domination of production of the metal ensured that the spelling aluminum became the standard in North America.

Aluminium

228

Health concerns
NFPA 704

Fire diamond for aluminium shot

Despite its natural abundance, aluminium has no known function in biology. It is remarkably nontoxic, aluminium sulfate having an LD50 of 6207mg/kg (oral, mouse), which corresponds to 500grams for a 80kg person.[6] The extremely low acute toxicity notwithstanding, the health effects of aluminium are of interest in view of the widespread occurrence of the element in the environment and in commerce. Some toxicity can be traced to deposition in bone and the central nervous system, which is particularly increased in patients with reduced renal function. Because aluminium competes with calcium for absorption, increased amounts of dietary aluminium may contribute to the reduced skeletal mineralization (osteopenia) observed in preterm infants and infants with growth retardation. In very high doses, aluminium can cause neurotoxicity, and is associated with altered function of the bloodbrain barrier.[68] A small percentage of people are allergic to aluminium and experience contact dermatitis, digestive disorders, vomiting or other symptoms upon contact or ingestion of products containing aluminium, such as deodorants or antacids. In those without allergies, aluminium is not as toxic as heavy metals, but there is evidence of some toxicity if it is consumed in excessive amounts.[69] Although the use of aluminium cookware has not been shown to lead to aluminium toxicity in general, excessive consumption of antacids containing aluminium compounds and excessive use of aluminium-containing antiperspirants provide more significant exposure levels. Studies have shown that consumption of acidic foods or liquids with aluminium significantly increases aluminium absorption,[70] and maltol has been shown to increase the accumulation of aluminium in nervous and osseus tissue.[71] Furthermore, aluminium increases estrogen-related gene expression in human breast cancer cells cultured in the laboratory.[72] The estrogen-like effects of these salts have led to their classification as a metalloestrogen. The effects of aluminium in antiperspirants has been examined over the course of decades with little evidence of skin irritation.[6] Nonetheless, its occurrence in antiperspirants, dyes (such as aluminium lake), and food additives is controversial in some quarters. Although there is little evidence that normal exposure to aluminium presents a risk to healthy adults,[73] some studies point to risks associated with increased exposure to the metal.[74] Aluminium in food may be absorbed more than aluminium from water.[] Some researchers have expressed concerns that the aluminium in antiperspirants may increase the risk of breast cancer,[] and aluminium has controversially been implicated as a factor in Alzheimer's disease.[] The Camelford water pollution incident involved a number of people consuming aluminium sulfate. Investigations of the long-term health effects are still ongoing, but elevated brain aluminium concentrations have been found in post-mortem examinations of victims, and further research to determine if there is a link with cerebral amyloid angiopathy has been commissioned.[75] According to the Alzheimer's Society, the medical and scientific opinion is that studies have not convincingly demonstrated a causal relationship between aluminium and Alzheimer's disease.[76] Nevertheless, some studies, such as those on the PAQUID cohort,[] cite aluminium exposure as a risk factor for Alzheimer's disease. Some brain plaques have been found to contain increased levels of the metal.[] Research in this area has been inconclusive; aluminium accumulation may be a consequence of the disease rather than a causal agent. In any event, if there is any toxicity of aluminium, it must be via a very specific mechanism, since total human exposure to the element in the form of naturally occurring clay in soil and dust is enormously large over a lifetime.[77][78] Scientific consensus does not yet exist about whether aluminium exposure could directly increase the risk of Alzheimer's disease.[76]

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Effect on plants
Aluminium is primary among the factors that reduce plant growth on acid soils. Although it is generally harmless to plant growth in pH-neutral soils, the concentration in acid soils of toxic Al3+ cations increases and disturbs root growth and function.[79][80][81][82] Most acid soils are saturated with aluminium rather than hydrogen ions. The acidity of the soil is therefore a result of hydrolysis of aluminium compounds.[83] This concept of "corrected lime potential"[84] to define the degree of base saturation in soils became the basis for procedures now used in soil testing laboratories to determine the "lime requirement"[85] of soils.[86] Wheat's adaptation to allow aluminium tolerance is such that the aluminium induces a release of organic compounds that bind to the harmful aluminium cations. Sorghum is believed to have the same tolerance mechanism. The first gene for aluminium tolerance has been identified in wheat. It was shown that sorghum's aluminium tolerance is controlled by a single gene, as for wheat.[87] This is not the case in all plants.

References
[2] Aluminium monoxide [3] Aluminium iodide [56] IUPAC Periodic Table of the Elements (http:/ / www. iupac. org/ highlights/ periodic-table-of-the-elements. html). iupac.org [57] IUPAC Web site publication search for 'aluminum' (http:/ / www. google. com/ search?q=aluminum& sitesearch=iupac. org). [58] Bremner, John Words on Words: A Dictionary for Writers and Others Who Care about Words, pp. 2223. ISBN 0-231-04493-3. [62] "alumium", Oxford English Dictionary. Ed. J.A. Simpson and E.S.C. Weiner, second edition Oxford: Clarendon Press, 1989. OED Online Oxford University Press. Accessed 29 October 2006. Citation is listed as "1808 SIR H. DAVY in Phil. Trans. XCVIII. 353". The ellipsis in the quotation is as it appears in the OED citation. [66] , "In the USA, the position was more complicated. Noah Webster's Dictionary of 1828 has only aluminum, though the standard spelling among US chemists throughout most of the 19th century was aluminium; it was the preferred version in The Century Dictionary of 1889 and is the only spelling given in the Webster Unabridged Dictionary of 1913." [73] Gitelman, H. J. "Physiology of Aluminum in Man" (http:/ / books. google. com/ books?id=wRnOytsi8boC& pg=PA90), in Aluminum and Health, CRC Press, 1988, ISBN 0-8247-8026-4, p. 90 [76] Aluminium and Alzheimer's disease (http:/ / alzheimers. org. uk/ site/ scripts/ documents_info. php?documentID=99), The Alzheimer's Society. Retrieved 30 January 2009. [86] Applying lime to soils reduces the Aluminum toxicity to plants.

External links
Aluminium (http://www.periodicvideos.com/videos/013.htm) at The Periodic Table of Videos (University of Nottingham) CDC - NIOSH Pocket Guide to Chemical Hazards - Aluminum (http://www.cdc.gov/niosh/npg/npgd0022. html) Electrolytic production (http://electrochem.cwru.edu/encycl/art-a01-al-prod.htm) World production of primary aluminium, by country (http://www.indexmundi.com/en/commodities/minerals/ aluminum/aluminum_table12.html) Price history of aluminum, according to the IMF (http://www.indexmundi.com/commodities/ ?commodity=aluminum&months=300) History of Aluminium (http://www.world-aluminium.org/About+Aluminium/Story+of/In+history) from the website of the International Aluminium Institute Emedicine Aluminium (http://www.emedicine.com/med/topic113.htm) The short film ALUMINUM (1941) (http://www.archive.org/details/gov.archives.arc.38661) is available for free download at the Internet Archive [more]

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230

Ore
An ore is a type of rock that contains minerals with important elements including metals. The ores are extracted through mining; these are then refined to extract the valuable element(s). The grade or concentration of an ore mineral, or metal, as well as its form of occurrence, will directly affect the costs associated with mining the ore. The cost of extraction must thus be weighed against the metal value contained in the rock to determine what ore can be processed and what ore is of too low a grade to be worth mining. Metal ores are generally oxides, sulfides, silicates, or "native" metals (such as native copper) that are not commonly concentrated in the Earth's crust or "noble" metals (not usually forming compounds) such as gold. The ores must be processed to extract the metals of interest from the waste rock and from the ore minerals. Ore bodies are formed by a variety of geological processes. The process of ore formation is called ore genesis.

Iron ore (Banded iron formation)

Ore deposits
An ore deposit is an accumulation of ore. Now this is distinct from a mineral resource as defined by the mineral resource classification criteria. An ore deposit is one occurrence of a particular ore type. Most ore deposits are named according to either their location (for example, the Witswatersrand, South Africa), or after a discoverer (e.g. the kambalda nickel shoots are named after drillers), or after some whimsy, a historical figure, a prominent person, something from mythology (phoenix, kraken, serepentleopard, etc.) or the code name of the resource company which found it (e.g. MKD-5 is the in-house name for the Mount Keith nickel ).

Manganese ore - psilomelane (size: 6.7 x 5.8 x 5.1 cm)

Classification of ore deposits


Ore deposits are classified according to various criteria developed via the study of economic geology, or ore genesis. The classifications below are typical. Hydrothermal epigenetic deposits Mesothermal lode gold deposits, typified by the Golden Mile, Kalgoorlie Archaean conglomerate hosted gold-uranium deposits, typified by Elliot Lake, Canada and Witwatersrand, South Africa Carlintype gold deposits, including; Epithermal stockwork vein deposits

Lead ore - galena and anglesite (size: 4.8 x 4.0 x 3.0 cm)

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231

Granite related hydrothermal IOCG or iron oxide copper gold deposits, typified by the supergiant Olympic Dam Cu-Au-U deposit Porphyry copper +/- gold +/- molybdenum +/- silver deposits Intrusive-related copper-gold +/- (tin-tungsten), typified by the Tombstone, Arizona deposits Hydromagmatic magnetite iron ore deposits and skarns Skarn ore deposits of copper, lead, zinc, tungsten, etcetera Nickel-cobalt-platinum deposits Magmatic nickel-copper-iron-PGE deposits including Cumulate vanadiferous or platinum-bearing magnetite or chromite Cumulate hard-rock titanium (ilmenite) deposits Komatiite hosted Ni-Cu-PGE deposits Subvolcanic feeder subtype, typified by Noril'sk-Talnakh and the Thompson Belt, Canada Intrusive-related Ni-Cu-PGE, typified by Voisey's Bay, Canada and Jinchuan, China Lateritic nickel ore deposits, examples include Goro and Acoje, (Philippines) and Ravensthorpe, Western Australia. Volcanic-related deposits Volcanic hosted massive sulfide (VHMS) Cu-Pb-Zn including; Examples include Teutonic Bore and Golden Grove, Western Australia Besshi type Kuroko type Metamorphically reworked deposits Podiform serpentinite-hosted paramagmatic iron oxide-chromite deposits, typified by Savage River, Tasmania iron ore, Coobina chromite deposit Broken Hill Type Pb-Zn-Ag, considered to be a class of reworked SEDEX deposits Carbonatite-alkaline igneous related Phosphorus-tantalite-vermiculite (Phalaborwa South Africa) Rare earth elements - Mount Weld, Australia and Bayan Obo, Mongolia Diatreme hosted diamond in kimberlite, lamproite or lamprophyre
Cart for carrying ore from a mine on display at the Historic Archive and Museum of Mining in Pachuca, Mexico.

Gold ore (size: 7.5 x 6.1 x 4.1 cm)

Ore Sedimentary deposits Banded iron formation iron ore deposits, including Channel-iron deposits or pisolite type iron ore Heavy mineral sands ore deposits and other sand dune hosted deposits Alluvial gold, diamond, tin, platinum or black sand deposits Alluvial oxide zinc deposit type: sole example Skorpion Zinc Sedimentary hydrothermal deposits SEDEX Lead-zinc-silver, typified by Red Dog, McArthur River, Mount Isa, etc. Stratiform arkose-hosted and shale-hosted copper, typified by the Zambian copperbelt. Stratiform tungsten, typified by the Erzgebirge deposits, Czechoslovakia Exhalative spilite-chert hosted gold deposits Mississippi valley type (MVT) zinc-lead deposits Hematite iron ore deposits of altered banded iron formation Astrobleme-related ores Sudbury Basin nickel and copper, Ontario, Canada
Close-up of Banded Iron Formation specimen from Upper Michigan. Scale bar is 5.0 mm.

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Extraction
The basic extraction of ore deposits follows the steps below; 1. Prospecting or exploration to find and then define the extent and value of ore where it is located ("ore body") 2. Conduct resource estimation to mathematically estimate the size and grade of the deposit
Some ore deposits in the world

3. Conduct a pre-feasibility study to determine the theoretical economics of the ore deposit. This identifies, early on, whether further investment in estimation and engineering studies is warranted and identifies key risks and areas for further work. 4. Conduct a feasibility study to evaluate the financial viability, technical and financial risks and robustness of the project and make a decision as Some additional ore deposits in the world whether to develop or walk away from a proposed mine project. This includes mine planning to evaluate the economically recoverable portion of the deposit, the metallurgy and ore recoverability, marketability and payability of the ore concentrates, engineering, milling and infrastructure costs, finance and equity requirements and a cradle to grave analysis of the possible mine, from the initial excavation all the way through to reclamation. 5. Development to create access to an ore body and building of mine plant and equipment 6. The operation of the mine in an active sense 7. Reclamation to make land where a mine had been suitable for future use

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233

Trade
Ores (metals) are traded internationally and comprise a sizeable portion of international trade in raw materials both in value and volume. This is because the worldwide distribution of ores is unequal and dislocated from locations of peak demand and from smelting infrastructure. Most base metals (copper, lead, zinc, nickel) are traded internationally on the London Metal Exchange, with smaller stockpiles and metals exchanges monitored by the COMEX and NYMEX exchanges in the United States and the Shanghai Futures Exchange in China.

Ore and metal imports in 2005

Iron ore is traded between customer and producer, though various benchmark prices are set quarterly between the major mining conglomerates and the major consumers, and this sets the stage for smaller participants. Other, lesser, commodities do not have international clearing houses and benchmark prices, with most prices negotiated between suppliers and customers one-on-one. This generally makes determining the price of ores of this nature opaque and difficult. Such metals include lithium, niobium-tantalum, bismuth, antimony and rare earths. Most of these commodities are also dominated by one or two major suppliers with >60% of the world's reserves. The London Metal Exchange aims to add uranium to its list of metals on warrant. The World Bank reports that China was the top importer of ores and metals in 2005 followed by the USA and Japan.[citation needed]

Important ore minerals


Argentite: Ag2S for production of silver Barite: BaSO4 Bauxite Al(OH)3 and AlOOH, dried to Al2O3 for production of aluminium Beryl: Be3Al2(SiO3)6 Bornite: Cu5FeS4 Cassiterite: SnO2 Chalcocite: Cu2S for production of copper Chalcopyrite: CuFeS2 Chromite: (Fe, Mg)Cr2O4 for production of chromium Cinnabar: HgS for production of mercury Cobaltite: (Co, Fe)AsS Columbite-Tantalite or Coltan: (Fe, Mn)(Nb, Ta)2O6 Dolomite: CaMg(CO3)2 Galena: PbS Gold: Au, typically associated with quartz or as placer deposits Hematite: Fe2O3 Ilmenite: FeTiO3 Magnetite: Fe3O4 Malachite: Cu2CO3(OH)2 Molybdenite: MoS2 Pentlandite:(Fe, Ni)9S8 Pyrolusite:MnO2 Scheelite: CaWO4

Sphalerite: ZnS Uraninite (pitchblende): UO2 for production of metallic uranium

Ore Wolframite: (Fe, Mn)WO4

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References Further reading


DILL, H.G. (2010) The chessboard classification scheme of mineral deposits: Mineralogy and geology from aluminum to zirconium, Earth-Science Reviews, Volume 100, Issue 1-4, June 2010, Pages 1-420 (http:/ / www. hgeodill.de/Map-Chessboard-classification-scheme.htm)

Carbon

235

Carbon
Carbon C 6

boron carbon nitrogen

C
Si Carbon in the periodic table Appearance clear (diamond) & black (graphite)

Spectral lines of Carbon General properties Name, symbol, number Pronunciation Element category Group, period, block Standard atomic weight carbon, C, 6 /krbn/ polyatomic nonmetal 14, 2, p 12.011(1)

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236
Electron configuration

[He] 2s2 2p2 2, 4

History Discovery Recognized as an element by Egyptians and Sumerians Antoine Lavoisier Physical properties Phase Density (near r.t.) Density (near r.t.) Density (near r.t.) Sublimationpoint Triplepoint Heatoffusion Molar heat capacity solid amorphous:
[3] [2] [1]

(3750 BC)

(1789)

1.82.1 gcm3

diamond: 3.515 gcm3 graphite: 2.267 gcm3 3915K, 3642C, 6588F 4600K(4327C), 10800 117 (graphite) kJmol1 6.155 (diamond) 8.517 (graphite) Jmol1K1 Atomic properties
[][]

kPa

Oxidation states Electronegativity Ionization energies (more)

4, 3

[4]

, 2, 1

[5]

, 0, 1, 2, 3, 4

[6]

2.55 (Pauling scale) 1st: 1086.5 kJmol1 2nd: 2352.6 kJmol1 3rd: 4620.5 kJmol1

Covalent radius Van der Waals radius

77(sp), 73(sp), 69(sp) pm 170 pm Miscellanea

Crystal structure

diamond

(diamond, clear)

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237
simple hexagonal

(graphite, black) Magnetic ordering Thermal conductivity diamagnetic


[7]

900-2300 (diamond) 119-165 (graphite)Wm1K1 (25 C) 0.8 (diamond)


[8]

Thermal expansion Speed of sound (thin rod) Young's modulus Shear modulus Bulk modulus Poisson ratio Mohs hardness CAS registry number

mm1K1

(20 C) 18350 (diamond) ms1 1050 (diamond) 478 (diamond) 442 (diamond) 0.1 (diamond) 10 (diamond) 1-2 (graphite) 7440-44-0 Most stable isotopes Main article: Isotopes of carbon
[8]

GPa

[8] [8]

GPa GPa

[8]

iso
11 12 13 14

NA syn

half-life DM DE (MeV) DP 20 min


12 13

0.96

11

C 98.9% C 1.1% C trace

C is stable with 6 neutrons C is stable with 7 neutrons

5730 y

0.15 0

14

Carbon (from Latin: carbo "coal") is the chemical element with symbol C and atomic number 6. As a member of group 14 on the periodic table, it is nonmetallic and tetravalentmaking four electrons available to form covalent chemical bonds. There are three naturally occurring isotopes, with 12C and 13C being stable, while 14C is radioactive, decaying with a half-life of about 5,730years.[] Carbon is one of the few elements known since antiquity.[] There are several allotropes of carbon of which the best known are graphite, diamond, and amorphous carbon.[] The physical properties of carbon vary widely with the allotropic form. For example, diamond is highly transparent, while graphite is opaque and black. Diamond is the hardest naturally-occurring material known, while graphite is soft enough to form a streak on paper (hence its name, from the Greek word "" which means "to write"). Diamond has a very low electrical conductivity, while graphite is a very good conductor. Under normal conditions, diamond, carbon nanotube and graphene have the highest thermal conductivities of all known materials. All carbon allotropes are solids under normal conditions with graphite being the most thermodynamically stable form. They are chemically resistant and require high temperature to react even with oxygen. The most common oxidation state of carbon in inorganic compounds is +4, while +2 is found in carbon monoxide and other transition metal carbonyl complexes. The largest sources of inorganic carbon are limestones, dolomites and carbon dioxide, but significant quantities occur in organic deposits of coal, peat, oil and methane clathrates. Carbon forms more

Carbon compounds than any other element, with almost ten million pure organic compounds described to date, which in turn are a tiny fraction of such compounds that are theoretically possible under standard conditions.[] Carbon is the 15th most abundant element in the Earth's crust, and the fourth most abundant element in the universe by mass after hydrogen, helium, and oxygen. It is present in all known life forms, and in the human body carbon is the second most abundant element by mass (about 18.5%) after oxygen.[9] This abundance, together with the unique diversity of organic compounds and their unusual polymer-forming ability at the temperatures commonly encountered on Earth, make this element the chemical basis of all known life.

238

Characteristics
The different forms or allotropes of carbon (see below) include the hardest naturally occurring substance, diamond, and also one of the softest known substances, graphite. Moreover, it has an affinity for bonding with other small atoms, including other carbon atoms, and is capable of forming multiple stable covalent bonds with such atoms. As a result, carbon is known to form almost ten million different compounds; the large majority of all chemical compounds.[] Carbon also has the highest sublimation point of all elements. At atmospheric pressure it has no melting point as its triple point is at 10.8 0.2MPa and 4,600 300 K (~4,330 C or 7,820 F),[][] so it sublimes at about 3,900K.[][10]

Theoretically predicted phase diagram of carbon

Carbon sublimes in a carbon arc which has a temperature of about 5,800 K (5,530 C; 9,980 F). Thus, irrespective of its allotropic form, carbon remains solid at higher temperatures than the highest melting point metals such as tungsten or rhenium. Although thermodynamically prone to oxidation, carbon resists oxidation more effectively than elements such as iron and copper that are weaker reducing agents at room temperature. Carbon compounds form the basis of all known life on Earth, and the carbon-nitrogen cycle provides some of the energy produced by the Sun and other stars. Although it forms an extraordinary variety of compounds, most forms of carbon are comparatively unreactive under normal conditions. At standard temperature and pressure, it resists all but the strongest oxidizers. It does not react with sulfuric acid, hydrochloric acid, chlorine or any alkalis. At elevated temperatures carbon reacts with oxygen to form carbon oxides, and will reduce such metal oxides as iron oxide to the metal. This exothermic reaction is used in the iron and steel industry to control the carbon content of steel: Fe 3O 4+ 4 C 3 Fe(s) + 4 CO(g) (s) with sulfur to form carbon disulfide and with steam in the coal-gas reaction: C(s) + H2O(g) CO(g) + H2(g). Carbon combines with some metals at high temperatures to form metallic carbides, such as the iron carbide cementite in steel, and tungsten carbide, widely used as an abrasive and for making hard tips for cutting tools. As of 2009, graphene appears to be the strongest material ever tested.[] However, the process of separating it from graphite will require some technological development before it is economical enough to be used in industrial processes.[] The system of carbon allotropes spans a range of extremes:

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239

Synthetic nanocrystalline diamond is the hardest material [11] known. Diamond is the ultimate abrasive. [13] Diamond is an excellent electrical insulator, and has the highest breakdown electric field of any known material. Diamond is the best known naturally occurring thermal conductor

Graphite is one of the softest materials known.

Graphite is a very good lubricant, displaying superlubricity. Graphite is a conductor of electricity. [14]

[12]

Some forms of graphite are used for thermal insulation (i.e. firebreaks and heat shields), but some other forms are good thermal conductors. Graphite is opaque. Graphite crystallizes in the hexagonal system. [15]

Diamond is highly transparent. Diamond crystallizes in the cubic system. Amorphous carbon is completely isotropic.

Carbon nanotubes are among the most anisotropic materials ever produced.

Allotropes
Atomic carbon is a very short-lived species and, therefore, carbon is stabilized in various multi-atomic structures with different molecular configurations called allotropes. The three relatively well-known allotropes of carbon are amorphous carbon, graphite, and diamond. Once considered exotic, fullerenes are nowadays commonly synthesized and used in research; they include buckyballs,[][] carbon nanotubes,[] carbon nanobuds[] and nanofibers.[16][17] Several other exotic allotropes have also been discovered, such as lonsdaleite,[] glassy carbon,[] carbon nanofoam[18] and linear acetylenic carbon (carbyne).[] The amorphous form is an assortment of carbon atoms in a non-crystalline, irregular, glassy state, which is essentially graphite but not held in a crystalline macrostructure. It is present as a powder, and is the main constituent of substances such as charcoal, lampblack (soot) and activated carbon. At normal pressures carbon takes the form of graphite, in which each atom is bonded trigonally to three others in a plane composed of fused hexagonal rings, just like those in aromatic hydrocarbons.[19] The resulting network is 2-dimensional, and the resulting flat sheets are stacked and loosely bonded through weak van der Waals forces. This gives graphite its softness and its cleaving properties (the sheets slip easily past one another). Because of the delocalization of one of the outer electrons of each atom to form a -cloud, graphite conducts electricity, but only in the plane of each covalently bonded sheet. This results in a lower bulk electrical conductivity for carbon than for most metals. The delocalization also accounts for the energetic stability of graphite over diamond at room temperature.

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240

At very high pressures carbon forms the more compact allotrope diamond, having nearly twice the density of graphite. Here, each atom is bonded tetrahedrally to four others, thus making a 3-dimensional network of puckered six-membered rings of atoms. Diamond has the same cubic structure as silicon and germanium and because of the strength of the carbon-carbon bonds, it is the hardest naturally occurring substance in terms of resistance to scratching. Contrary to the popular belief that "diamonds are forever", they are in fact thermodynamically unstable under normal conditions and transform into graphite.[] However, due to a high activation energy barrier, the transition into graphite is so extremely slow at room temperature as to be unnoticeable. Under some conditions, carbon crystallizes as lonsdaleite. This form has a hexagonal crystal lattice where all atoms are covalently bonded. Therefore, all properties of lonsdaleite are close to those of diamond.[]

Some allotropes of carbon: a) diamond; b) graphite; c) lonsdaleite; df) fullerenes (C60, C540, C70); g) amorphous carbon; h) carbon nanotube.

Fullerenes have a graphite-like structure, but instead of purely hexagonal packing, they also contain pentagons (or even heptagons) of carbon atoms, which bend the sheet into spheres, ellipses or cylinders. The properties of fullerenes (split into buckyballs, buckytubes and nanobuds) have not yet been fully analyzed and represent an intense area of research in nanomaterials. The names "fullerene" and "buckyball" are given after Richard Buckminster Fuller, popularizer of geodesic domes, which resemble the structure of fullerenes. The buckyballs are fairly large molecules formed completely of carbon bonded trigonally, forming spheroids (the best-known and simplest is the soccerball-shaped C60 buckminsterfullerene).[] Carbon nanotubes are structurally similar to buckyballs, except that each atom is bonded trigonally in a curved sheet that forms a hollow cylinder.[][] Nanobuds were first reported in 2007 and are hybrid bucky tube/buckyball materials (buckyballs are covalently bonded to the outer wall of a nanotube) that combine the properties of both in a single structure.[] Of the other discovered allotropes, carbon nanofoam is a ferromagnetic allotrope discovered in 1997. It consists of a low-density cluster-assembly of carbon atoms strung together in a loose three-dimensional web, in which the atoms are bonded trigonally in six- and seven-membered rings. It is among the lightest known solids, with a density of about 2kg/m3.[20] Similarly, glassy carbon contains a high proportion of closed porosity,[] but contrary to normal graphite, the graphitic layers are not stacked like pages in a book, but have a more random arrangement. Linear acetylenic carbon[] has the chemical structure[] -(C:::C)n-. Carbon in this modification is linear with sp orbital hybridization, and is a polymer with alternating single and triple bonds. This type of carbyne is of considerable interest to nanotechnology as its Young's modulus is forty times that of the hardest known material diamond.[21]

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241

Occurrence
Carbon is the fourth most abundant chemical element in the universe by mass after hydrogen, helium, and oxygen. Carbon is abundant in the Sun, stars, comets, and in the atmospheres of most planets. Some meteorites contain microscopic diamonds that were formed when the solar system was still a protoplanetary disk. Microscopic diamonds may also be formed by the intense pressure and high temperature at the sites of meteorite impacts.[22] In combination with oxygen in carbon dioxide, carbon is found in the Earth's atmosphere (approximately 810gigatonnes of carbon) and dissolved in all water bodies (approximately 36,000gigatonnes of carbon). Around 1,900gigatonnes of carbon are present in the biosphere. Hydrocarbons (such as coal, petroleum, and natural gas) contain carbon as wellcoal "reserves" (not "resources") amount to around 900gigatonnes, and oil reserves around 150gigatonnes. Proven sources of natural gas are about 1751012 cubic metres (representing about 105 gigatonnes carbon), but it is estimated that there are also about 9001012 cubic metres of "unconventional" gas such as shale gas, representing about 540 gigatonnes of carbon.[23] Carbon is also locked up as methane hydrates in polar regions and under the seas. Various estimates of the amount of carbon this represents have been made: 500 to 2500 Gt,[24] or 3000 Gt.[25] (In the past, quantities of hydrocarbons were greater. In the period from 1751 to 2008 about 347 gigatonnes of carbon were released as carbon dioxide to the atmosphere from burning of fossil fuels.[26]) Carbon is a major component in very large masses of carbonate rock (limestone, dolomite, marble and so on). Coal is the largest commercial source of mineral carbon, accounting for 4,000gigatonnes or 80% of fossil carbon fuel.[27] It is also rich in carbon for example, anthracite contains 9298%.[28]
"Present day" (1990s) sea surface dissolved As for individual carbon allotropes, graphite is found in large inorganic carbon concentration (from the quantities in the United States (mostly in New York and Texas), GLODAP climatology) Russia, Mexico, Greenland, and India. Natural diamonds occur in the rock kimberlite, found in ancient volcanic "necks", or "pipes". Most diamond deposits are in Africa, notably in South Africa, Namibia, Botswana, the Republic of the Congo, and Sierra Leone. There are also deposits in Arkansas, Canada, the Russian Arctic, Brazil and in Northern and Western Australia. Diamonds are now also being recovered from the ocean floor off the Cape of Good Hope. However, though diamonds are found naturally, about 30% of all industrial diamonds used in the U.S. are now made synthetically.

Graphite ore

Raw diamond crystal.

Carbon-14 is formed in upper layers of the troposphere and the stratosphere, at altitudes of 915km, by a reaction that is precipitated by cosmic rays.[29] Thermal neutrons are produced that collide with the nuclei of nitrogen-14, forming carbon-14 and a proton.

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242

Isotopes
Isotopes of carbon are atomic nuclei that contain six protons plus a number of neutrons (varying from 2 to 16). Carbon has two stable, naturally occurring isotopes.[] The isotope carbon-12 (12C) forms 98.93% of the carbon on Earth, while carbon-13 (13C) forms the remaining 1.07%.[] The concentration of 12C is further increased in biological materials because biochemical reactions discriminate against 13C.[30] In 1961, the International Union of Pure and Applied Chemistry (IUPAC) adopted the isotope carbon-12 as the basis for atomic weights.[31] Identification of carbon in NMR experiments is done with the isotope 13C. Carbon-14 (14C) is a naturally occurring radioisotope which occurs in trace amounts on Earth of up to 1 part per trillion (0.0000000001%), mostly confined to the atmosphere and superficial deposits, particularly of peat and other organic materials.[32] This isotope decays by 0.158 MeV emission. Because of its relatively short half-life of 5730years, 14C is virtually absent in ancient rocks, but is created in the upper atmosphere (lower stratosphere and upper troposphere) by interaction of nitrogen with cosmic rays.[33] The abundance of 14C in the atmosphere and in living organisms is almost constant, but decreases predictably in their bodies after death. This principle is used in radiocarbon dating, invented in 1949, which has been used extensively to determine the age of carbonaceous materials with ages up to about 40,000years.[34][35] There are 15 known isotopes of carbon and the shortest-lived of these is 8C which decays through proton emission and alpha decay and has a half-life of 1.98739x1021 s.[36] The exotic 19C exhibits a nuclear halo, which means its radius is appreciably larger than would be expected if the nucleus were a sphere of constant density.[37]

Formation in stars
Formation of the carbon atomic nucleus requires a nearly simultaneous triple collision of alpha particles (helium nuclei) within the core of a giant or supergiant star which is known as the triple-alpha process, as the products of further nuclear fusion reactions of helium with hydrogen or another helium nucleus produce lithium-5 and beryllium-8 respectively, both of which are highly unstable and decay almost instantly back into smaller nuclei.[] This happens in conditions of temperatures over 100 megakelvin and helium concentration that the rapid expansion and cooling of the early universe prohibited, and therefore no significant carbon was created during the Big Bang. Instead, the interiors of stars in the horizontal branch transform three helium nuclei into carbon by means of this triple-alpha process.[] In order to be available for formation of life as we know it, this carbon must then later be scattered into space as dust, in supernova explosions, as part of the material which later forms second, third-generation star systems which have planets accreted from such dust.[38] The Solar System is one such third-generation star system. Another of the fusion mechanisms powering stars is the CNO cycle, in which carbon acts as a catalyst to allow the reaction to proceed. Rotational transitions of various isotopic forms of carbon monoxide (for example, 12CO, 13CO, and C18O) are detectable in the submillimeter wavelength range, and are used in the study of newly forming stars in molecular clouds.[39]

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243

Carbon cycle
Under terrestrial conditions, conversion of one element to another is very rare. Therefore, the amount of carbon on Earth is effectively constant. Thus, processes that use carbon must obtain it somewhere and dispose of it somewhere else. The paths that carbon follows in the environment make up the carbon cycle. For example, plants draw carbon dioxide out of their environment and use it to build biomass, as in carbon respiration or the Calvin cycle, a process of carbon fixation. Some of this biomass is eaten by animals, whereas some carbon is exhaled by animals as carbon dioxide. The carbon cycle is considerably more complicated than this short loop; for example, some carbon dioxide is dissolved in the oceans; dead plant or animal matter may become petroleum or coal, which can burn with the release of carbon, should bacteria not consume it.[40][41]

Diagram of the carbon cycle. The black numbers indicate how much carbon is stored in various reservoirs, in billions tonnes ("GtC" stands for gigatonnes of carbon; figures are circa 2004). The purple numbers indicate how much carbon moves between reservoirs each year. The sediments, as defined in this diagram, do not include the ~70million GtC of carbonate rock and kerogen.

Compounds
Organic compounds
Carbon has the ability to form very long chains of interconnecting C-C bonds. This property is called catenation. Carbon-carbon bonds are strong, and stable. This property allows carbon to form an almost infinite number of compounds; in fact, there are more known carbon-containing compounds than all the compounds of the other chemical elements combined except those of hydrogen (because almost all organic compounds contain hydrogen too). The simplest form of an organic molecule is the hydrocarbona large family of organic molecules that are composed of hydrogen atoms bonded to a chain of carbon atoms. Chain length, side chains and functional groups all affect the properties of organic molecules.

Structural formula of methane, the simplest possible organic compound.

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244

Carbon occurs in all known organic life and is the basis of organic chemistry. When united with hydrogen, it forms various hydrocarbons which are important to industry as refrigerants, lubricants, solvents, as chemical feedstock for the manufacture of plastics and petrochemicals and as fossil fuels. When combined with oxygen and hydrogen, carbon can form many groups of important biological compounds including sugars, lignans, chitins, alcohols, fats, and aromatic esters, carotenoids and terpenes. With nitrogen it forms alkaloids, and with the addition of sulfur also it forms antibiotics, amino acids, and rubber products. With the addition of phosphorus to these other elements, it forms DNA and RNA, the chemical-code carriers of life, and adenosine triphosphate (ATP), the most important energy-transfer molecule in all living cells.

Inorganic compounds

Commonly carbon-containing compounds which are associated with minerals or which do not contain hydrogen or fluorine, are treated separately from classical organic compounds; however the definition is not rigid (see reference articles above). Among these are the simple oxides of carbon. The most prominent oxide is carbon dioxide (CO2). This was once the principal constituent of the paleoatmosphere, but is a minor component of the Earth's atmosphere today.[42] Dissolved in water, it forms carbonic acid (H 2CO [43] 3), but as most compounds with multiple single-bonded oxygens on a single carbon it is unstable. Through this intermediate, though, resonance-stabilized carbonate ions are produced. Some important minerals are carbonates, notably calcite. Carbon disulfide (CS 2) is similar. The other common oxide is carbon monoxide (CO). It is formed by incomplete combustion, and is a colorless, odorless gas. The molecules each contain a triple bond and are fairly polar, resulting in a tendency to bind permanently to hemoglobin molecules, displacing oxygen, which has a lower binding affinity.[44][45] Cyanide (CN), has a similar structure, but behaves much like a halide ion (pseudohalogen). For example it can form the nitride cyanogen molecule ((CN)2), similar to diatomic halides. Other uncommon oxides are carbon suboxide (C 3O [46] 2), the unstable dicarbon monoxide (C2O),[47][48] carbon trioxide (CO3),[49][50] cyclopentanepentone (C5O5)[51] cyclohexanehexone (C6O6),[51] and mellitic anhydride (C12O9). With reactive metals, such as tungsten, carbon forms either carbides (C4), or acetylides (C2 2) to form alloys with high melting points. These anions are also associated with methane and acetylene, both very weak acids. With an electronegativity of 2.5,[52] carbon prefers to form covalent bonds. A few carbides are covalent

Correlation between the carbon cycle and formation of organic compounds. In plants, carbon dioxide formed by carbon fixation can join with water in photosynthesis (green) to form organic compounds, which can be used and further converted by both plants and animals.

Carbon lattices, like carborundum (SiC), which resembles diamond.

245

Organometallic compounds
Organometallic compounds by definition contain at least one carbon-metal bond. A wide range of such compounds exist; major classes include simple alkyl-metal compounds (for example, tetraethyllead), 2-alkene compounds (for example, Zeise's salt), and 3-allyl compounds (for example, allylpalladium chloride dimer); metallocenes containing cyclopentadienyl ligands (for example, ferrocene); and transition metal carbene complexes. Many metal carbonyls exist (for example, tetracarbonylnickel); some workers consider the carbon monoxide ligand to be purely inorganic, and not organometallic. While carbon is understood to exclusively form four bonds, an interesting compound containing an octahedral hexacoordinated carbon atom has been reported. The cation of the compound is [(Ph3PAu)6C]2+. This phenomenon has been attributed to the aurophilicity of the gold ligands.[53]

History and etymology


The English name carbon comes from the Latin carbo for coal and charcoal,[54] whence also comes the French charbon, meaning charcoal. In German, Dutch and Danish, the names for carbon are Kohlenstoff, koolstof and kulstof respectively, all literally meaning coal-substance. Carbon was discovered in prehistory and was known in the forms of soot and charcoal to the earliest human civilizations. Diamonds were known probably as early as 2500BCE in China, while carbon in the form of charcoal was made around Roman times by the same chemistry as it is today, by heating wood in a pyramid covered with clay to exclude air.[][55]
Antoine Lavoisier in his youth

In 1722, Ren Antoine Ferchault de Raumur demonstrated that iron was transformed into steel through the absorption of some substance, now known to be carbon.[56] In 1772, Antoine Lavoisier showed that diamonds are a form of carbon; when he burned samples of charcoal and diamond and found that neither produced any water and that both released the same amount of carbon dioxide per gram. In 1779,[57] Carl Wilhelm Scheele showed that graphite, which had been thought of as a form of lead, was instead identical with charcoal but with a small admixture of iron, and that it gave "aerial acid" (his name for carbon dioxide) when oxidized with nitric acid.[58] In 1786, the French scientists Claude Louis Berthollet, Gaspard Monge and C. A. Vandermonde confirmed that graphite was mostly carbon by oxidizing it in oxygen in much the same way Carl Wilhelm Scheele Lavoisier had done with diamond.[59] Some iron again was left, which the French scientists thought was necessary to the graphite structure. However, in their publication they proposed the name carbone (Latin carbonum) for the element in graphite which was given off as a gas upon burning graphite. Antoine Lavoisier then listed carbon as an element in his 1789 textbook.[60] A new allotrope of carbon, fullerene, that was discovered in 1985[61] includes nanostructured forms such as buckyballs and nanotubes.[] Their discoverers Robert Curl, Harold Kroto and Richard Smalley received the Nobel Prize in Chemistry in 1996.[62] The resulting renewed interest in new forms lead to the discovery of further exotic allotropes, including glassy carbon, and the realization that "amorphous carbon" is not strictly amorphous.[]

Carbon

246

Production
Graphite
Commercially viable natural deposits of graphite occur in many parts of the world, but the most important sources economically are in China, India, Brazil and North Korea. Graphite deposits are of metamorphic origin, found in association with quartz, mica and feldspars in schists, gneisses and metamorphosed sandstones and limestone as lenses or veins, sometimes of a meter or more in thickness. Deposits of graphite in Borrowdale, Cumberland, England were at first of sufficient size and purity that, until the 19th century, pencils were made simply by sawing blocks of natural graphite into strips before encasing the strips in wood. Today, smaller deposits of graphite are obtained by crushing the parent rock and floating the lighter graphite out on water.[63] There are three types of natural graphiteamorphous, flake or crystalline flake, and vein or lump. Amorphous graphite is the lowest quality and most abundant. Contrary to science, in industry "amorphous" refers to very small crystal size rather than complete lack of crystal structure. Amorphous is used for lower value graphite products and is the lowest priced graphite. Large amorphous graphite deposits are found in China, Europe, Mexico and the United States. Flake graphite is less common and of higher quality than amorphous; it occurs as separate plates that crystallized in metamorphic rock. Flake graphite can be four times the price of amorphous. Good quality flakes can be processed into expandable graphite for many uses, such as flame retardants. The foremost deposits are found in Austria, Brazil, Canada, China, Germany and Madagascar. Vein or lump graphite is the rarest, most valuable, and highest quality type of natural graphite. It occurs in veins along intrusive contacts in solid lumps, and it is only commercially mined in Sri Lanka.[63] According to the USGS, world production of natural graphite was 1.1million tonnes in 2010, to which China contributed 800,000t, India 130,000 t, Brazil 76,000t, North Korea 30,000t and Canada 25,000 t. No natural graphite was reported mined in the United States, but 118,000 t of synthetic graphite with an estimated value of $998million was produced in 2009.[63]

Diamond
The diamond supply chain is controlled by a limited number of powerful businesses, and is also highly concentrated in a small number of locations around the world (see figure). Only a very small fraction of the diamond ore consists of actual diamonds. The ore is crushed, during which care has to be taken in order to prevent larger diamonds from being destroyed in this process Diamond output in 2005 and subsequently the particles are sorted by density. Today, diamonds are located in the diamond-rich density fraction with the help of X-ray fluorescence, after which the final sorting steps are done by hand. Before the use of X-rays became commonplace, the separation was done with grease belts; diamonds have a stronger tendency to stick to grease than the other minerals in the ore.[64] Historically diamonds were known to be found only in alluvial deposits in southern India.[65] India led the world in diamond production from the time of their discovery in approximately the 9th century BCE[66] to the mid-18th century AD, but the commercial potential of these sources had been exhausted by the late 18th century and at that time India was eclipsed by Brazil where the first non-Indian diamonds were found in 1725.[67] Diamond production of primary deposits (kimberlites and lamproites) only started in the 1870s after the discovery of the Diamond fields in South Africa. Production has increased over time and now an accumulated total of 4.5billion carats have been mined since that date.[] About 20% of that amount has been mined in the last 5 years alone, and during the last ten years 9 new mines have started production while 4 more are waiting to be opened soon. Most of these mines are located in Canada, Zimbabwe, Angola, and one in Russia.[]

Carbon In the United States, diamonds have been found in Arkansas, Colorado and Montana.[][68] In 2004, a startling discovery of a microscopic diamond in the United States[69] led to the January 2008 bulk-sampling of kimberlite pipes in a remote part of Montana.[70] Today, most commercially viable diamond deposits are in Russia, Botswana, Australia and the Democratic Republic of Congo.[71] In 2005, Russia produced almost one-fifth of the global diamond output, reports the British Geological Survey. Australia has the richest diamantiferous pipe with production reaching peak levels of 42 metric tons (41long tons; 46short tons) per year in the 1990s.[] There are also commercial deposits being actively mined in the Northwest Territories of Canada, Siberia (mostly in Yakutia territory; for example, Mir pipe and Udachnaya pipe), Brazil, and in Northern and Western Australia.

247

Applications
Carbon is essential to all known living systems, and without it life as we know it could not exist (see alternative biochemistry). The major economic use of carbon other than food and wood is in the form of hydrocarbons, most notably the fossil fuel methane gas and crude oil (petroleum). Crude oil is used by the petrochemical industry to produce, amongst other things, gasoline and kerosene, through a distillation process, in refineries. Cellulose is a natural, carbon-containing polymer produced by plants in the form of cotton, linen, and hemp. Cellulose is mainly used for maintaining structure in plants. Commercially valuable carbon polymers of animal origin include wool, cashmere and silk. Plastics are made from synthetic carbon polymers, often with oxygen and nitrogen atoms included at regular intervals in the main polymer chain. The raw materials for many of these synthetic substances come from crude oil. The uses of carbon and its compounds are extremely varied. It can form alloys with iron, of which the most common is carbon steel. Graphite is combined with clays to form the 'lead' used in pencils used for writing and drawing. It is also used as a lubricant and a pigment, as a molding material in glass manufacture, in electrodes for dry batteries and in electroplating and electroforming, in brushes for electric motors and as a neutron moderator in nuclear reactors. Charcoal is used as a drawing material in artwork, for grilling, and in many other uses including iron smelting. Wood, coal and oil are used as fuel for production of energy and space heating. Gem quality diamond is used in jewelry, and industrial diamonds are used in drilling, cutting and polishing tools for machining metals and stone. Plastics are made from fossil hydrocarbons, and carbon fiber, made by pyrolysis of synthetic polyester fibers is used to reinforce plastics to form advanced, lightweight composite materials. Carbon fiber is made by pyrolysis of extruded and stretched filaments of polyacrylonitrile (PAN) and other organic substances. The crystallographic structure and mechanical properties of the fiber depend on the type of starting
Sticks of vine and compressed charcoal.

Pencil leads for mechanical pencils are made of graphite (often mixed with a clay or synthetic binder).

A cloth of woven carbon filaments

Carbon

248

material, and on the subsequent processing. Carbon fibers made from PAN have structure resembling narrow filaments of graphite, but thermal processing may re-order the structure into a continuous rolled sheet. The result is fibers with higher specific tensile strength than steel.[] Carbon black is used as the black pigment in printing ink, artist's oil paint and water colours, carbon paper, automotive finishes, India ink and laser printer toner. Carbon black is also used as a filler in rubber products such as tyres and in plastic compounds. Activated charcoal is used as an absorbent and adsorbent in filter material in applications as diverse as gas masks, water purification and kitchen extractor hoods and in medicine to absorb toxins, poisons, or gases from the digestive system. Carbon is used in chemical reduction at high temperatures. Coke is used to reduce iron ore into iron. Case hardening of steel is achieved by heating finished steel components in carbon powder. Carbides of silicon, tungsten, boron and titanium, are among the hardest known materials, and are used as abrasives in cutting and grinding tools. Carbon compounds make up most of the materials used in clothing, such as natural and synthetic textiles and leather, and almost all of the interior surfaces in the built environment other than glass, stone and metal.

Silicon carbide single crystal

Diamonds
The diamond industry can be broadly separated into two basically distinct categories: one dealing with gem-grade diamonds and another for industrial-grade diamonds. While a large trade in both types of diamonds exists, the two markets act in dramatically different ways. A large trade in gem-grade diamonds exists. Unlike precious metals such as gold or platinum, gem diamonds do not trade as a commodity: there is a substantial mark-up in the sale of diamonds, and there is not a very active market for resale of diamonds.

The C60 fullerene in crystalline form

Tungsten carbide milling bits

The market for industrial-grade diamonds operates much differently from its gem-grade counterpart. Industrial diamonds are valued mostly for their hardness and heat conductivity, making many of the gemological characteristics of diamond, including clarity and color, mostly irrelevant. This helps explain why 80% of mined diamonds (equal to about 100 million carats or 20tonnes annually), unsuitable for use as gemstones and known as bort, are destined for industrial use.[72] In addition to mined diamonds, synthetic diamonds found industrial applications almost immediately after their invention in the 1950s; another 3billion carats (600tonnes) of synthetic diamond is produced annually for industrial use.[] The dominant industrial use of diamond is in cutting, drilling, grinding, and polishing. Most uses of diamonds in these technologies do not require large diamonds; in fact, most diamonds that are gem-quality except for their small size, can find an industrial use. Diamonds are embedded in drill tips or saw blades, or ground into a powder for use in grinding and polishing applications.[73] Specialized applications include use in laboratories as containment for high pressure experiments (see diamond anvil cell), high-performance bearings, and limited use in specialized windows.[74][75] With the continuing advances being made in the production of synthetic diamonds, future applications are beginning to become feasible. Garnering much excitement is the possible use of diamond as a semiconductor suitable to build microchips from, or the use of

Carbon diamond as a heat sink in electronics.[76]

249

Precautions
Pure carbon has extremely low toxicity to humans and can be handled and even ingested safely in the form of graphite or charcoal. It is resistant to dissolution or chemical attack, even in the acidic contents of the digestive tract, for example. Consequently once it enters into the body's tissues it is likely to remain there indefinitely. Carbon black was probably one of the first pigments to be used for tattooing, and tzi the Iceman was found to have carbon tattoos that survived during his life and for 5200years after his death.[77] However, inhalation of coal dust or soot (carbon black) in large quantities can be dangerous, irritating lung tissues and causing the congestive lung disease coalworker's pneumoconiosis. Similarly, diamond dust used as an abrasive can do harm if ingested or inhaled. Microparticles of carbon are produced in diesel engine exhaust fumes, and may accumulate in the lungs.[78] In these examples, the harmful effects may result from contamination of the carbon particles, with organic chemicals or heavy metals for example, rather than from the carbon itself.

Worker at carbon black plant in Sunray, Texas (photo by John Vachon, 1942)

Carbon generally has low toxicity to almost all life on Earth; however, to some creatures it can still be toxic. For instance, carbon nanoparticles are deadly to Drosophila.[79] Carbon may also burn vigorously and brightly in the presence of air at high temperatures, as in the Windscale fire, which was caused by sudden release of stored Wigner energy in the graphite core. Large accumulations of coal, which have remained inert for hundreds of millions of years in the absence of oxygen, may spontaneously combust when exposed to air, for example in coal mine waste tips. The great variety of carbon compounds include such lethal poisons as tetrodotoxin, the lectin ricin from seeds of the castor oil plant Ricinus communis, cyanide (CN) and carbon monoxide; and such essentials to life as glucose and protein.

Bonding to carbon
CH CLi CBe CB CAl CV CCr CMn CFe CRu COs Hs CCo CRh CIr Mt CNi CC CSi CN CP CO CS CF He Ne

CNa CMg CK CRb CCa CSc CTi CSr CY

CCl CAr

CCu CZn CGa CGe CAs CSn CSb CBi Uup

CSe CBr CKr CTe CI CXe Rn

CZr CNb CMo CTc CHf CTa Rf Db CW Sg CRe Bh

CPd CAg CCd CIn CPt Ds

CCs CBa Fr Ra

CAu CHg CTl CPb Rg Cn Uut Fl

CPo CAt Lv

Uus Uuo

CLa CCe CPr Ac CTh CPa

CNd CPm CSm CEu CU

CGd CTb CDy CHo CEr CTm CYb CLu Cf CEs Fm Md No Lr

CNp CPu CAm CCm CBk

Core organic chemistry Academic research, but no widespread use

Many uses in chemistry Bond unknown

Carbon |+ Chemical bonds to carbon

250

References
[7] Magnetic susceptibility of the elements and inorganic compounds (http:/ / www-d0. fnal. gov/ hardware/ cal/ lvps_info/ engineering/ elementmagn. pdf), in Handbook of Chemistry and Physics 81st edition, CRC press. [8] Properties of diamond (http:/ / www. ioffe. ru/ SVA/ NSM/ Semicond/ Diamond), Ioffe Institute Database [23] "Wonderfuel: Welcome to the age of unconventional gas" (http:/ / www. newscientist. com/ article/ mg20627641. 100-wonderfuel-welcome-to-the-age-of-unconventional-gas. html?full=true) by Helen Knight, New Scientist, 12 June 2010, pp. 447. [24] Ocean methane stocks 'overstated' (http:/ / news. bbc. co. uk/ 2/ hi/ science/ nature/ 3493349. stm), BBC, 17 Feb. 2004. [25] "Ice on fire: The next fossil fuel" (http:/ / www. newscientist. com/ article/ mg20227141. 100) by Fred Pearce, New Scientist, 27 June 2009, pp. 30-33. [26] Calculated from file global.1751_2008.csv in (http:/ / cdiac. ornl. gov/ ftp/ ndp030/ CSV-FILES) from the Carbon Dioxide Information Analysis Center. [29] Carbon-14 formation (http:/ / www. acad. carleton. edu/ curricular/ BIOL/ classes/ bio302/ pages/ carbondatingback. html) [54] Shorter Oxford English Dictionary, Oxford University Press [63] USGS Minerals Yearbook: Graphite, 2009 (http:/ / minerals. usgs. gov/ minerals/ pubs/ commodity/ graphite) and Graphite: Mineral Commodity Summaries 2011 [65] Page 159 discussion on Alluvial diamonds in India and elsewhere as well as earliest finds [66] Ball was a Geologist in British service. Chapter I, Page 1 [72] Internet Archive (http:/ / www. archive. org/ details/ turningmechanica02holtuoft) [79] Carbon Nanoparticles Toxic To Adult Fruit Flies But Benign To Young (http:/ / www. sciencedaily. com/ releases/ 2009/ 08/ 090807103921. htm) ScienceDaily (Aug. 17, 2009)

External links
Carbon (http://www.bbc.co.uk/programmes/p003c1cj) on In Our Time at the BBC. ( listen now (http://www. bbc.co.uk/iplayer/console/p003c1cj/In_Our_Time_Carbon)) Carbon (http://www.periodicvideos.com/videos/006.htm) at The Periodic Table of Videos (University of Nottingham) Carbon on Britannica (http://www.britannica.com/eb/article-80956/carbon-group-element) Extensive Carbon page at asu.edu (http://invsee.asu.edu/nmodules/Carbonmod/everywhere.html) Electrochemical uses of carbon (http://electrochem.cwru.edu/ed/encycl/art-c01-carbon.htm) Carbon Super Stuff. Animation with sound and interactive 3D-models. (http://www.forskning.no/Artikler/ 2006/juni/1149432180.36)

Steel

251

Steel

The steel cable of a colliery winding tower

Ironcarbon alloy phases

Ferrite

Allotropes of ferrite include: -iron (Alpha ferrite) -iron (Delta ferrite) -iron (Beta ferrite) -iron (Hexaferrum) -iron (Gamma ferrite)

Austenite (-iron + carbon in solid solution) Cementite (iron carbide, Fe3C) Graphite (allotrope of carbon) Martensite (metastable phase) -carbon (transitional carbide, Fe C)
24

Microstructures

Spheroidite Pearlite (88% ferrite, 12% cementite) Bainite Ledeburite (austenite-cementite eutectic, 4.3% carbon) Tempered martensite (martensite + ferrite + -carbon or cementite, or both) Steel classes

Crucible steel Carbon steel ( 2.1% carbon; low alloy) Spring steel (low or no alloy) Alloy steel (contains non-carbon elements) Maraging steel (contains nickel) Stainless steel (contains 10.5% chromium) Weathering steel Tool steel (alloy steel for tools) Other iron-based materials

Steel

252
Cast iron (> 2.1% carbon) Ductile iron Gray iron Malleable iron White iron Wrought iron (contains slag)

Steel is an alloy of iron and other elements, including carbon. When carbon is the primary alloying element, its content in the steel is between 0.002% and 2.1% by weight. The following elements are always present in steel: carbon, manganese, phosphorus, sulfur, silicon, and traces of oxygen, nitrogen and aluminum. Alloying elements intentionally added to modify the characteristics of steel include: manganese, nickel, chromium, molybdenum, boron, titanium, vanadium and niobium.[] Carbon and other elements act as a hardening agent, preventing dislocations in the iron atom crystal lattice from sliding past one another. Varying the amount of alloying elements and the form of their presence in the steel (solute elements, precipitated phase) controls qualities such as the hardness, ductility, and tensile strength of the resulting steel. Steel with increased carbon content can be made harder and stronger than iron, but such steel is also less ductile than iron. Alloys with a higher than 2.1% carbon (depending on other element content and possibly on processing) are known as cast iron. Because they are not malleable even when hot, they can be worked only by casting, and they have lower melting point and good castability.[] Steel is also distinguishable from wrought iron, which can contain a small amount of carbon. Though steel had been produced in a blacksmith's forge for thousands of years, its use became more extensive after more efficient production methods were devised in the 17th century. With the invention of the Bessemer process in the mid-19th century, steel became an inexpensive mass-produced material. Further refinements in the process, such as basic oxygen steelmaking (BOS), lowered the cost of production while increasing the quality of the metal. Today, steel is one of the most common materials in the world, with more than 1.3 billion tons produced annually. It is a major component in buildings, infrastructure, tools, ships, automobiles, machines, appliances, and weapons. Modern steel is generally identified by various grades defined by assorted standards organizations.

Steel

253

Material properties
Iron is found in the Earth's crust only in the form of an ore, usually an iron oxide, such as magnetite, hematite etc. Iron is extracted from iron ore by removing the oxygen and combining the ore with a preferred chemical partner such as carbon. This process, known as smelting, was first applied to metals with lower melting points, such as tin, which melts at approximately 250 C (482F) and copper, which melts at approximately 1,100 C (2,010F). In comparison, cast iron melts at approximately 1,375 C (2,507F).[] Small quantities of iron were smelted in ancient times, in the solid state, by heating the ore buried in a charcoal fire and welding the metal together with a hammer, squeezing out Iron-carbon phase diagram, showing the conditions necessary to form different phases. the impurities. With care, the carbon content could be controlled by moving it around in the fire. All of these temperatures could be reached with ancient methods that have been used since the Bronze Age. Since the oxidation rate of iron increases rapidly beyond 800 C (1,470F), it is important that smelting take place in a low-oxygen environment. Unlike copper and tin, liquid or solid iron dissolves carbon quite readily. Smelting results in an alloy (pig iron) that contains too much carbon to be called steel.[] The excess carbon and other impurities are removed in a subsequent step. Other materials are often added to the iron/carbon mixture to produce steel with desired properties. Nickel and manganese in steel add to its tensile strength and make the austenite form of the iron-carbon solution more stable, chromium increases hardness and melting temperature, and vanadium also increases hardness while reducing the effects of metal fatigue.[] To inhibit corrosion, at least 11% chromium is added to steel so that a hard oxide forms on the metal surface; this is known as stainless steel. Tungsten interferes with the formation of cementite, allowing martensite to preferentially form at slower quench rates, resulting in high speed steel. On the other hand, sulfur, nitrogen, and phosphorus make steel more brittle, so these commonly found elements must be removed from the ore during processing.[] The density of steel varies based on the alloying constituents but usually ranges between 7,750 and 8,050 kg/m3 (484 and 503 lb/cu ft), or 7.75 and 8.05 g/cm3 (4.48 and 4.65 oz/cuin).[1] Even in the narrow range of concentrations that make up steel, mixtures of carbon and iron can form a number of different structures, with very different properties. Understanding such properties is essential to making quality steel. At room temperature, the most stable form of iron is the body-centered cubic (BCC) structure -ferrite. It is a fairly soft metal that can dissolve only a small concentration of carbon, no more than 0.021 wt% at 723 C (1,333F), and only 0.005% at 0 C (32F). If steel contains more than 0.021% carbon at steelmaking temperatures it transforms into a face-centered cubic (FCC) structure, called austenite or -iron. It is also soft and metallic but can dissolve considerably more carbon, as much as 2.1%[2] carbon at 1,148 C (2,098F), which reflects the upper carbon content of steel.[3]

Steel When steels with less than 0.8% carbon, known as a hypoeutectoid steel are cooled, the austenitic phase of the mixture attempts to revert to the ferrite phase, resulting in an excess of carbon. One way for carbon to leave the austenite is for it to precipitate out of solution as cementite, leaving behind iron that is low enough in carbon to take the form of ferrite, resulting in a ferrite matrix with cementite inclusions. Cementite is a hard and brittle intermetallic compound with the chemical formula of Fe3C. At the eutectoid, 0.8% carbon, the cooled structure takes the form of pearlite, named for its resemblance to mother of pearl. For steels that have more than 0.8% carbon the cooled structure takes the form of pearlite and cementite.[4] Perhaps the most important polymorphic form of steel is martensite, a metastable phase that is significantly stronger than other steel phases. When the steel is in an austenitic phase and then quenched rapidly, it forms into martensite, as the atoms "freeze" in place when the cell structure changes from FCC to BCC. Depending on the carbon content the martensitic phase takes different forms. Below approximately 0.2% carbon it takes an ferrite BCC crystal form, but at higher carbon content it takes a body-centered tetragonal (BCT) structure. There is no thermal activation energy for the transformation from austenite to martensite. Moreover, there is no compositional change so the atoms generally retain their same neighbors.[5] Martensite has a lower density than does austenite, so that the transformation between them results in a change of volume. In this case, expansion occurs. Internal stresses from this expansion generally take the form of compression on the crystals of martensite and tension on the remaining ferrite, with a fair amount of shear on both constituents. If quenching is done improperly, the internal stresses can cause a part to shatter as it cools. At the very least, they cause internal work hardening and other microscopic imperfections. It is common for quench cracks to form when steel is water quenched, although they may not always be visible.[6]

254

Heat treatment
There are many types of heat treating processes available to steel. The most common are annealing and quenching and tempering. Annealing is the process of heating the steel to a sufficiently high temperature to soften it. This process occurs through three phases: recovery, recrystallization, and grain growth. The temperature required to anneal steel depends on the type of annealing and the constituents of the alloy.[7] Quenching and tempering first involve heating the steel to the austenite phase, then quenching it in water or oil. This rapid cooling results in a hard and brittle martensitic structure.[5] The steel is then tempered, which is just a specialized type of annealing. In this application the annealing (tempering) process transforms some of the martensite into cementite, or spheroidite to reduce internal stresses and defects, which ultimately results in a more ductile and fracture-resistant metal.[8]

Steel production

Steel

255 When iron is smelted from its ore by commercial processes, it contains more carbon than is desirable. To become steel, it must be melted and reprocessed to reduce the carbon to the correct amount, at which point other elements can be added. This liquid is then continuously cast into long slabs or cast into ingots. Approximately 96% of steel is continuously cast, while only 4% is produced as ingots.[9] The ingots are then heated in a soaking pit and hot rolled into slabs, blooms, or billets. Slabs are hot or cold rolled into sheet metal or plates. Billets are hot or Iron ore pellets for the production of steel. cold rolled into bars, rods, and wire. Blooms are hot or cold rolled into structural steel, such as I-beams and rails. In modern steel mills these processes often occur in one assembly line, with ore coming in and finished steel coming out.[10] Sometimes after a steel's final rolling it is heat treated for strength, however this is relatively rare.[11]

History of steelmaking
Ancient steel
Steel was known in antiquity, and may have been produced by managing bloomeries, or iron-smelting facilities, in which the bloom contained carbon.[12] The earliest known production of steel is a piece of ironware excavated from an archaeological site in Anatolia (Kaman-Kalehoyuk) and is about 4,000 years old.[13] Other ancient steel comes from East Africa, dating back to 1400 BC.[14] In the 4th century BC steel weapons like the Falcata were produced in the Iberian Peninsula, while Noric steel was used by the Roman military.[15] Steel was produced in large quantities in Sparta around 650BC.[16][17] The Chinese of the Warring States (403221 BC) had quench-hardened steel,[18] while Chinese of the Han Dynasty (202 BC 220 AD) created steel by melting together wrought iron with cast iron, gaining an ultimate product of a carbon-intermediate steel by the 1st century AD.[][19] The Haya people of East Africa invented a type of furnace they used to make carbon steel at 1,802 C (3,276F) nearly 2,000 years ago.[20]

Bloomery smelting during the Middle Ages.

Wootz steel and Damascus steel


Evidence of the earliest production of high carbon steel in the Indian Subcontinent was found in Samanalawewa area in Sri Lanka.[21] Wootz steel was produced in India by about 300 BC.[22] However, the steel was an old technology

Steel in India when King Porus presented a Steel sword to the Emperor Alexander in 326 BC. The steel technology obviously existed before 326 BC as steel was being exported to the Arab World at that time. Since the technology was acquired from the Tamilians from South India, the origin of steel technology in India can be conservatively estimated at 400-500 BC. Along with their original methods of forging steel, the Chinese had also adopted the production methods of creating Wootz steel, an idea imported into China from India by the 5th century AD.[23] In Sri Lanka, this early steel-making method employed a unique wind furnace, driven by the monsoon winds, capable of producing high-carbon steel.[] Also known as Damascus steel, wootz is famous for its durability and ability to hold an edge. It was originally created from a number of different materials including various trace elements. It was essentially a complicated alloy with iron as its main component. Recent studies have suggested that carbon nanotubes were included in its structure, which might explain some of its legendary qualities, though given the technology available at that time, they were produced by chance rather than by design.[24] Natural wind was used where the soil containing iron was heated by the use of wood. The ancient Sinhalese managed to extract a ton of steel for every 2 tons of soil,[] a remarkable feat at the time. One such furnace was found in Samanalawewa and archaeologists were able to produce steel as the ancients did.[][25] Crucible steel, formed by slowly heating and cooling pure iron and carbon (typically in the form of charcoal) in a crucible, was produced in Merv by the 9th to 10th century AD.[22] In the 11th century, there is evidence of the production of steel in Song China using two techniques: a "berganesque" method that produced inferior, inhomogeneous steel and a precursor to the modern Bessemer process that used partial decarbonization via repeated forging under a cold blast.[26]

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Modern steelmaking
Since the 17th century the first step in European steel production has been the smelting of iron ore into pig iron in a blast furnace.[27] Originally using charcoal, modern methods use coke, which has proven more economical.[28][29][30] Processes starting from bar iron In these processes pig iron was "fined" in a finery forge to produce bar iron (wrought iron), which was then used in steel-making.[27] The production of steel by the cementation process was described in a treatise published in Prague in 1574 and was in use in Nuremberg from 1601. A similar process for case hardening armour and files was described in a book published in Naples in 1589. The process was introduced to England in about 1614 and used to produce such steel by Sir Basil Brooke at Coalbrookdale during the 1610s.[31] The raw material for this process were bars of wrought iron. During the 17th century it was realised that the best steel came from oregrounds iron of a region north of Stockholm, Sweden. This was still the usual raw material source in the 19th century, almost as long as the process was used.[32][]
A Bessemer converter in Sheffield, England

Crucible steel is steel that has been melted in a crucible rather than having been forged, with the result that it is more homogeneous. Most previous furnaces could not reach high enough temperatures to melt the steel. The early modern crucible steel industry resulted from the invention of Benjamin Huntsman in the 1740s. Blister steel (made as above) was melted in a crucible or in a furnace, and cast (usually) into ingots.[][33]

Steel Processes starting from pig iron The modern era in steelmaking began with the introduction of Henry Bessemer's Bessemer process in 1858, the raw material for which was pig iron.[34] His method let him produce steel in large quantities cheaply, thus mild steel came to be used for most purposes for which wrought iron was formerly used.[35] The Gilchrist-Thomas process (or basic Bessemer process) was an improvement to the Bessemer process, made by lining the converter with a basic material to remove phosphorus. Another improvement in steelmaking was the Siemens-Martin process, which complemented the Bessemer process.[] These methods of steel production were rendered obsolete by the Linz-Donawitz process of basic oxygen steelmaking (BOS), developed in the 1950s, and other oxygen steel making methods. Basic oxygen steelmaking is superior to previous steelmaking methods because the oxygen pumped into the furnace limits impurities that previously had entered from the air used.[36] Today, electric arc furnaces (EAF) are a common method of reprocessing scrap metal to create new steel. They can also be used for converting pig iron to steel, but they use a lot of electricity (about 440 kWh per metric ton), and are thus generally only economical when there is a plentiful supply of cheap electricity.[37]
A Siemens-Martin steel oven from the Brandenburg Museum of Industry.

257

White-hot steel pouring out of an electric arc furnace.

Steel industry
It is common today to talk about "the iron and steel industry" as if it were a single entity, but historically they were separate products. The steel industry is often considered an indicator of economic progress, because of the critical role played by steel in infrastructural and overall economic development.[38] In 1980, there were more than 500,000 U.S. steelworkers. By 2000, the number of steelworkers fell to 224,000.[39]
Steel production by country in 2007

Steel

258 The economic boom in China and India has caused a massive increase in the demand for steel in recent years. Between 2000 and 2005, world steel demand increased by 6%. Since 2000, several Indian[40] and Chinese steel firms have risen to prominence like Tata Steel (which bought Corus Group in 2007), Shanghai Baosteel Group Corporation and Shagang Group. ArcelorMittal is however the world's largest steel producer. In 2005, the British Geological Survey stated China was the top steel producer with about one-third of the world share; Japan, Russia, and the US followed respectively.[41]

A steel plant in the United Kingdom.

In 2008, steel began trading as a commodity on the London Metal Exchange. At the end of 2008, the steel industry faced a sharp downturn that led to many cut-backs.[42] The world steel industry peaked in 2007. That year, ThyssenKrupp spent $12 billion to build the two most modern mills in the world, in Calvert, Alabama and Sepetiba, Rio de Janeiro, Brazil. The worldwide Great Recession starting in 2008, however, sharply lowered demand and new construction, and so prices fell. ThyssenKrupp lost $11 billion on its two new plants, which sold steel below the cost of production. Finally in 2013, ThyssenKrupp offered the plants for sale at under $4 billion.[43]

Contemporary steel
Modern steels are made with varying combinations of alloy metals to fulfill many purposes.[] Carbon steel, composed simply of iron and carbon, accounts for 90% of steel production.[] High strength low alloy steel has small additions (usually < 2% by weight) of other elements, typically 1.5% manganese, to provide additional strength for a modest price increase.[44] Low alloy steel is alloyed with other elements, usually molybdenum, manganese, chromium, or nickel, in amounts of up to 10% by weight to improve the hardenability of thick sections.[] Stainless steels and Bethlehem Steel in Bethlehem, Pennsylvania was one of the world's largest manufacturers of steel before its 2003 closure and later surgical stainless steels contain a minimum of 11% conversion into a casino. chromium, often combined with nickel, to resist corrosion (rust). Some stainless steels, such as the ferritic stainless steels are magnetic, while others, such as the austenitic, are nonmagnetic.[45] Corrosion-resistant steels are abbreviated as CRES. Some more modern steels include tool steels, which are alloyed with large amounts of tungsten and cobalt or other elements to maximize solution hardening. This also allows the use of precipitation hardening and improves the alloy's temperature resistance.[] Tool steel is generally used in axes, drills, and other devices that need a sharp, long-lasting cutting edge. Other special-purpose alloys include weathering steels such as Cor-ten, which weather by acquiring a stable, rusted surface, and so can be used un-painted.[46]

Steel Many other high-strength alloys exist, such as dual-phase steel, which is heat treated to contain both a ferritic and martensitic microstructure for extra strength.[47] Transformation Induced Plasticity (TRIP) steel involves special alloying and heat treatments to stabilize amounts of austenite at room temperature in normally austenite-free low-alloy ferritic steels. By applying strain to the metal, the austenite undergoes a phase transition to martensite without the addition of heat.[48] Maraging steel is alloyed with nickel and other elements, but unlike most steel contains almost no carbon at all. This creates a very strong but still malleable metal.[49] Twinning Induced Plasticity (TWIP) steel uses a specific type of strain to increase the effectiveness of work hardening on the alloy.[50] Eglin Steel uses a combination of over a dozen different elements in varying amounts to create a relatively low-cost metal for use in bunker buster weapons. Hadfield steel (after Sir Robert Hadfield) or manganese steel contains 1214% manganese which when abraded forms an incredibly hard skin which resists wearing. Examples include tank tracks, bulldozer blade edges and cutting blades on the jaws of life.[51] Most of the more commonly used steel alloys are categorized into various grades by standards organizations. For example, the Society of Automotive Engineers has a series of grades defining many types of steel.[] The American Society for Testing and Materials has a separate set of standards, which define alloys such as A36 steel, the most commonly used structural steel in the United States.[52] Though not an alloy, galvanized steel is a commonly used variety of steel which has been hot-dipped or electroplated in zinc for protection against rust.[53]

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Uses
Iron and steel are used widely in the construction of roads, railways, other infrastructure, appliances, and buildings. Most large modern structures, such as stadiums and skyscrapers, bridges, and airports, are supported by a steel skeleton. Even those with a concrete structure employ steel for reinforcing. In addition, it sees widespread use in major appliances and cars. Despite growth in usage of aluminium, it is still the main material for car bodies. Steel is used in a variety of other construction materials, such as bolts, nails, and screws.[54] Other common applications include shipbuilding, pipeline transport, A roll of steel wool mining, offshore construction, aerospace, white goods (e.g. washing machines), heavy equipment such as bulldozers, office furniture, steel wool, tools, and armour in the form of personal vests or vehicle armour (better known as rolled homogeneous armour in this role). Steel was the metal of choice for sculptor Jim Gary and a frequent choice for sculpture by many other modern sculptors.

Historical
Before the introduction of the Bessemer process and other modern production techniques, steel was expensive and was only used where no cheaper alternative existed, particularly for the cutting edge of knives, razors, swords, and other items where a hard, sharp edge was needed. It was also used for springs, including those used in clocks and watches.[] With the advent of speedier and thriftier production methods, steel has been easier to obtain and much cheaper. It has replaced wrought iron

A carbon steel knife

Steel for a multitude of purposes. However, the availability of plastics in the latter part of the 20th century allowed these materials to replace steel in some applications due to their lower fabrication cost and weight.[55] Carbon Fiber is replacing steel in some cost insensitive application such as aircraft, sports equipment and high end automobiles.

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Long steel
As reinforcing bars and mesh in reinforced concrete Railroad tracks Structural steel in modern buildings and bridges Wires Input to reforging applications

Flat carbon steel


Major appliances Magnetic cores The inside and outside body of automobiles, trains, and ships.
A steel pylon suspending overhead power lines

Stainless steel
Cutlery Rulers Surgical instruments Watches

Low-background steel
Steel manufactured after World War II became contaminated with radionuclides due to nuclear weapons testing. Low-background steel, steel manufactured prior to 1945, is used for certain radiation-sensitive applications such as Geiger counters and radiation shielding.
A stainless steel gravy boat

References
[2] Sources differ on this value so it has been rounded to 2.1%, however the exact value is rather academic because plain-carbon steel is very rarely made with this level of carbon. See: 2.08%. 2.11%. 2.14%. [3] . [4] . [5] . [7] . [8] . [10] . [15] "Noricus ensis," Horace, Odes, i. 16.9 [19] Gernet, 69. [20] Africa's Ancient Steelmakers (http:/ / www. time. com/ time/ magazine/ article/ 0,9171,912179,00. html?promoid=googlep). Time Magazine, Sept. 25, 1978. [22] Ann Feuerbach, 'An investigation of the varied technology found in swords, sabres and blades from the Russian Northern Caucasus' IAMS 25 for 2005, pp. 2743 (p. 29) (https:/ / www. es. ucl. ac. uk/ iams/ jour_25/ iams25_Feuerbach. pdf), apparently ultimately from the writings of Zosimos of Panopolis. [23] Needham, Volume 4, Part 1, p. 282.

Steel
[27] Tylecote, R. F. A history of metallurgy 2 edn, Institute of Materials, London 1992, pp. 9599 and 102105. [28] Raistrick, A. A Dynasty of Ironfounders (1953; York 1989) [29] Hyde, C. K. Technological Change and the British iron industry (Princeton 1977) [30] Trinder, B. The Industrial Revolution in Shropshire (Chichester 2000) [31] Barraclough, K. C. Steel before Bessemer: I Blister Steel: the birth of an industry (The Metals Society, London, 1984), pp. 4852. [33] K. C. Barraclough, Steel before Bessemer: II Crucible Steel: the growth of technology (The Metals Society, London, 1984). [37] Jones, J.A.T. ; Bowman, B. and Lefrank, P.A. Electric Furnace Steelmaking, in The Making, Shaping and Treating of Steel, pp. 525660. R.J. Fruehan, Editor. 1998, The AISE Steel Foundation: Pittsburgh. [39] " Congressional Record V. 148, Pt. 4, April 11, 2002 to April 24, 2002 (http:/ / books. google. com/ books?id=iOgfSDKecCcC& pg=PA4557& dq& hl=en#v=onepage& q=& f=false)". United States Government Printing Office. [43] John W. Miller and Ike Henning, "Thiessen gets offers for mills: Final bids for steel complexes in Alabama, Brazil will likely fall short of the company's hopes," Wall Street Journal March 1, 2013 [51] Hadfield manganese steel. (http:/ / answers. com/ topic/ hadfield-manganese-steel) Answers.com. McGraw-Hill Dictionary of Scientific and Technical Terms, McGraw-Hill Companies, Inc., 2003. Retrieved on 2007-02-28. [52] Steel Construction Manual, 8th Edition, second revised edition, American Institute of Steel Construction, 1986, ch. 1 page 1-5

261

Bibliography
Ashby, Michael F.; Jones, David Rayner Hunkin (1992). An introduction to microstructures, processing and design. Butterworth-Heinemann. Bugayev, K.; Konovalov, Y.; Bychkov, Y.; Tretyakov, E.; Savin, Ivan V. (2001). Iron and Steel Production (http://books.google.com/?id=MJdIVtmwuUsC). The Minerva Group, Inc. ISBN978-0-89499-109-7. Retrieved 2009-07-19.. Degarmo, E. Paul; Black, J T.; Kohser, Ronald A. (2003). Materials and Processes in Manufacturing (9th ed.). Wiley. ISBN0-471-65653-4. Gernet, Jacques (1982). A History of Chinese Civilization. Cambridge: Cambridge University Press. Smith, William F.; Hashemi, Javad (2006). Foundations of Materials Science and Engineering (4th ed.). McGraw-Hill. ISBN0-07-295358-6.

Further reading
Duncan Burn; The Economic History of Steelmaking, 18671939: A Study in Competition (http://questia.com/ PM.qst?a=o&d=3914930). Cambridge University Press, 1961. Harukiyu Hasegawa, The Steel Industry in Japan: A Comparison with Britain (http://questia.com/PM. qst?a=o&d=108742046). 1996. J. C. Carr and W. Taplin, History of the British Steel Industry (http://questia.com/PM.qst?a=o&d=808791). Harvard University Press, 1962. H. Lee Scamehorn, Mill & Mine: The Cf&I in the Twentieth Century (http://questia.com/PM.qst?a=o& d=94821694). University of Nebraska Press, 1992. Needham, Joseph (1986). Science and Civilization in China: Volume 4, Part 1 & Part 3. Taipei: Caves Books, Ltd. Warren, Kenneth, Big Steel: The First Century of the United States Steel Corporation, 19012001 (http://eh.net/ bookreviews/library/0558). University of Pittsburgh Press, 2001.

Steel

262

External links
World Steel Association (worldsteel) (http://www.worldsteel.org/) steeluniversity.org: Online steel education resources from worldsteel and the University of Liverpool (http:// steeluniversity.org/) Huge archive on steels, Cambridge University (http://www.msm.cam.ac.uk/phase-trans/2005/Fealloys. html) Cooking with Steels (http://www.wastedtalent.ca/comic/cooking-steel) Metallurgy for the Non-Metallurgist from the American Society for Metals (http://books.google.com/ books?id=brpx-LtdCLYC&pg=PA26&lpg=PA26&d#v=onepage&q&f=true,)

Chemical element

263

Chemical element

Top: the periodic table of the chemical elements. Below: Examples of certain chemical elements. From left to right: hydrogen, barium, copper, uranium, bromine, and helium.

A chemical element is a pure chemical substance consisting of one type of atom distinguished by its atomic number, which is the number of protons in its nucleus. Elements are divided into metals, metalloids, and non-metals. Familiar examples of elements include carbon, oxygen (non-metals), silicon, arsenic (metalloids), aluminium, iron, copper, gold, mercury, and lead (metals). The lightest chemical elements, including hydrogen, helium (and smaller amounts of lithium, beryllium and boron), are thought to have been produced by various cosmic processes during the Big Bang and cosmic-ray spallation. Production of heavier elements, from carbon to the very heaviest elements, proceeded by stellar nucleosynthesis, and these were made available for later solar system and planetary formation by planetary nebulae and supernovae, which blast these elements into space.[1] The high abundance of oxygen, silicon, and iron on Earth reflects their common production in such stars, after the lighter gaseous elements and their compounds have been subtracted. While most elements are generally viewed as stable, a small amount of natural transformation of one element to another also occurs at the present time through decay of radioactive elements as well as other natural nuclear processes. The history of the discovery and use of the elements began with primitive human societies that found native elements like copper and gold and extracted (smelted) iron and a few other metals from their ores. Alchemists and chemists subsequently identified many more, with nearly all of the naturally-occurring elements becoming known by 1900. The properties of the chemical elements are often summarized using the periodic table that organizes the elements by increasing atomic number into rows ("periods") in which the columns ("groups") share recurring ("periodic") physical and chemical properties. Save for short-half-life radioactive elements, all of the elements are available industrially, most of them to high degrees of purity. Hydrogen and helium are by far the most abundant elements in the universe. However, iron is the most abundant element (by mass) making up the Earth, and oxygen is the most common element in Earth's crust.[] Although all known chemical matter is composed of these elements, chemical matter itself is hypothesized to constitute only

Chemical element about 15% of the matter in the universe. The remainder is believed to be dark matter, a mysterious substance that is not composed of chemical elements, since it lacks protons, neutrons or electrons.[2] When two or more distinct elements are chemically combined, with the atoms held together by chemical bonds, the result is termed a chemical compound. Two thirds of the chemical elements occur on Earth only as compounds, and in the remaining third, often the compound forms of the element are most common.[citation needed] Chemical compounds may be composed of elements combined in exact whole-number ratios of atoms, as in water, table salt, and minerals such as quartz, calcite, and some ores. However, chemical bonding of many types of elements results in crystalline solids and metallic alloys for which exact chemical formulas do not exist. Relatively pure samples of isolated elements are uncommon in nature. While all of the 98 naturally occurring elements have been identified in mineral samples from Earth's crust, only a small minority of elements are found as recognizable, relatively pure minerals. Among the more common of such "native elements" are copper, silver, gold, carbon (as coal, graphite, or diamonds), sulfur, and mercury. All but a few of the most inert elements, such as noble gases and noble metals, are usually found on Earth in chemically combined form, as chemical compounds. While about 32 of the chemical elements occur on Earth in native uncombined form, most of these occur as mixtures. For example, atmospheric air is primarily a mixture of nitrogen, oxygen, and argon, and native solid elements occur in alloys, such as that of iron and nickel. As of November 2011, 118 elements have been identified, the latest being ununseptium in 2010.[] Of the 118 known elements, only the first 98 are known to occur naturally on Earth; 80 of them are stable, while the others are radioactive, decaying into lighter elements over various timescales from fractions of a second to billions of years. Those elements that do not occur naturally on Earth have been produced artificially as the synthetic products of man-made nuclear reactions.

264

Description
The lightest of the chemical elements are hydrogen and helium, both created by Big Bang nucleosynthesis during the first 20 minutes of the universe[3] in a ratio of around 3:1 by mass (approximately 12:1 by number of atoms).[4][5] Almost all other elements found in nature, including some further hydrogen and helium created since then, were made by various natural or (at times) artificial methods of nucleosynthesis.[6] On Earth, small amounts of new atoms are naturally produced in nucleogenic reactions, or in cosmogenic processes, such as cosmic ray spallation. New atoms are also naturally produced on Earth as radiogenic daughter isotopes of ongoing radioactive decay processes such as alpha decay, beta decay, spontaneous fission, cluster decay, and other rarer modes of decay. Of the 98 naturally occurring elements, those with atomic numbers 1 through 40 are all considered stable. Elements with atomic numbers 41 through 82 are apparently stable (except technetium, element 43 and promethium, element 61, which are unstable) but theoretically unstable, and thus possibly mildly radioactive.[7][8] The half-lives of elements 41 through 82 are so long, however, that their radioactive decay remains undetected by experiment. These "theoretical radionuclides" have half-lives at least 100 million times longer than the estimated age of the universe. Elements with atomic numbers 83 through 98 are unstable to the point that their radioactive decay can be detected. Some of these elements, notably thorium (atomic number 90) and uranium (atomic number 92), have one or more isotopes with half-lives long enough to survive as remnants of the explosive stellar nucleosynthesis that produced the heavy elements before the formation of our solar system. For example, at over 1.91019 years, over a billion times longer than the current estimated age of the universe, bismuth-209 (atomic number 83) has the longest known alpha decay half-life of any naturally occurring element.[][] The very heaviest elements (those beyond californium, atomic number 98) undergo radioactive decay with half-lives so short that they do not occur in nature and must be synthesized. As of 2010, there are 118 known elements (in this context, "known" means observed well-enough, even from just a few decay products, to have been differentiated from any other element).[9][] Of these 118 elements, 98 occur naturally on Earth.[10] Ten of these occur in extreme trace quantities: technetium, atomic number 43; promethium,

Chemical element number 61; astatine, number 85; francium, number 87; neptunium, number 93; plutonium, number 94; americium, number 95; curium, number 96; berkelium, number 97; and californium, number 98. These 98 elements have been detected in the universe at large, in the spectra of stars and also supernovae, where short-lived radioactive elements are newly being made. The first 98 elements have been detected directly on Earth as primordial nuclides present from the formation of the solar system, or as naturally-occurring fission or transmutation products of uranium and thorium. The remaining 24 heavier elements, not found today either on Earth or in astronomical spectra, have been derived artificially. All of the heavy elements that are derived solely through artificial means are radioactive, with very short half-lives; if any atoms of these elements were present at the formation of Earth, they are extremely likely to have already decayed, and if present in novae, have been in quantities too small to have been noted. Technetium was the first purportedly non-naturally occurring element synthesized, in 1937, although trace amounts of technetium have since been found in nature (and also the element may have been discovered naturally in 1925).[11] This pattern of artificial production and later natural discovery has been repeated with several other radioactive naturally-occurring rare elements.[12] Lists of the elements are available by name, by symbol, by atomic number, by density, by melting point, and by boiling point as well as ionization energies of the elements. The nuclides of stable and radioactive elements are also available as a list of nuclides, sorted by length of half-life for those that are unstable. One of the most convenient, and certainly the most traditional presentation of the elements, is in the form of the periodic table, which groups together elements with similar chemical properties (and usually also similar electronic structures).

265

Atomic number
The atomic number of an element is equal to the number of protons that defines the element.[13] For example, all carbon atoms contain 6 protons in their nucleus; so the atomic number of carbon is 6.[14] Carbon atoms may have different numbers of neutrons; atoms of the same element having different numbers of neutrons are known as isotopes of the element.[15] The number of protons in the atomic nucleus also determines its electric charge, which in turn determines the number of electrons of the atom in its non-ionized state. The electrons are placed into atomic orbitals that determine the atom's various chemical properties. The number of neutrons in a nucleus usually has very little effect on an element's chemical properties (except in the case of hydrogen and deuterium). Thus, all carbon isotopes have nearly identical chemical properties because they all have six protons and six electrons, even though carbon atoms may differ in number of neutrons. It is for this reason that atomic number rather than mass number or atomic weight is considered the identifying characteristic of a chemical element. The symbol for atomic number is Z.

Atomic mass and atomic weight


The mass number of an element, A, is the number of nucleons (protons and neutrons) in the atomic nucleus. Different isotopes of a given element are distinguished by their mass numbers, which are conventionally written as a super-index on the left hand side of the atomic symbol (e.g., 238U). The mass number is always a simple whole number and has units of "nucleons." An example of a referral to a mass number is "magnesium-24," which is an atom with 24 nucleons (12 protons and 12 neutrons). Whereas the mass number simply counts the total number of neutrons and protons and is thus a natural (or whole) number, the atomic mass of a single atom is a real number for the mass of a particular isotope of the element, the unit being u. In general, when expressed in u it differs in value slightly from the mass number for a given nuclide (or isotope) since the mass of the protons and neutrons is not exactly 1 u, since the electrons contribute a lesser share to the atomic mass as neutron number exceeds proton number, and (finally) because of the nuclear binding energy. For example, the atomic weight of chlorine-35 to five significant digits is 34.969 u and that of chlorine-37 is 36.966 u.

Chemical element However, the atomic mass in u of pure isotope atoms is quite close to its simple mass number (always within 1%). The only exception to the atomic mass of an isotope atom not being a natural number is 12C, which by definition has a mass of exactly 12, because u is defined as 1/12 of the mass of a free neutral carbon-12 atom in the ground state. The relative atomic mass (historically and commonly also called "atomic weight") of an element is the average of the atomic masses of all the chemical element's isotopes as found in a particular environment, weighted by isotopic abundance, relative to the atomic mass unit (u). This number may be a fraction that is not close to a whole number, due to the averaging process. For example, the relative atomic mass of chlorine is 35.453 u, which differs greatly from a whole number due to being made of an average of 76% chlorine-35 and 24% chlorine-37. Whenever a relative atomic mass value differs by more than 1% from a whole number, it is due to this averaging effect resulting from significant amounts of more than one isotope being naturally present in the sample of the element in question.

266

Isotopes
Isotopes are atoms of the same element (that is, with the same number of protons in their atomic nucleus), but having different numbers of neutrons. Most (66 of 94) naturally occurring elements have more than one stable isotope. Thus, for example, there are three main isotopes of carbon. All carbon atoms have 6 protons in the nucleus, but they can have either 6, 7, or 8 neutrons. Since the mass numbers of these are 12, 13 and 14 respectively, the three isotopes of carbon are known as carbon-12, carbon-13, and carbon-14, often abbreviated to 12C, 13C, and 14C. Carbon in everyday life and in chemistry is a mixture of 12C, 13C, and (a very small fraction of) 14C atoms. Except in the case of the isotopes of hydrogen (which differ greatly from each other in relative massenough to cause chemical effects), the isotopes of a given element are chemically nearly indistinguishable. All of the elements have some isotopes that are radioactive (radioisotopes), although not all of these radioisotopes occur naturally. The radioisotopes typically decay into other elements upon radiating an alpha or beta particle. If an element has isotopes that are not radioactive, these are termed "stable" isotopes. All of the known stable isotopes occur naturally (see primordial isotope). The many radioisotopes that are not found in nature have been characterized after being artificially made. Certain elements have no stable isotopes and are composed only of radioactive isotopes: specifically the elements without any stable isotopes are technetium (atomic number 43), promethium (atomic number 61), and all observed elements with atomic numbers greater than 82. Of the 80 elements with at least one stable isotope, 26 have only one single stable isotope. The mean number of stable isotopes for the 80 stable elements is 3.1 stable isotopes per element. The largest number of stable isotopes that occur for a single element is 10 (for tin, element 50).

Allotropes
Atoms of pure elements may bond to each other chemically in more than one way, allowing the pure element to exist in multiple structures (spacial arrangements of atoms), known as allotropes, which differ in their properties. For example, carbon can be found as diamond, which has a tetrahedral structure around each carbon atom; graphite, which has layers of carbon atoms with a hexagonal structure stacked on top of each other; graphene, which is a single layer of graphite that is very strong; fullerenes, which have nearly spherical shapes; and carbon nanotubes, which are tubes with a hexagonal structure (even these may differ from each other in electrical properties). The ability of an element to exist in one of many structural forms is known as 'allotropy'. The standard state, also known as reference state, of an element is defined as its thermodynamically most stable state at 1 bar at a given temperature (typically at 298.15 K). In thermochemistry, an element is defined to have an enthalpy of formation of zero in its standard state. For example, the reference state for carbon is graphite, because the structure of graphite is more stable than that of the other allotropes.

Chemical element

267

Properties
Several kinds of descriptive categorizations can be applied broadly to the elements, including consideration of their general physical and chemical properties, their states of matter under familiar conditions, their melting and boiling points, their densities, their crystal structures as solids, and their origins. General properties Several terms are commonly used to characterize the general physical and chemical properties of the chemical elements. A first distinction is between metals, which readily conduct electricity, nonmetals, which do not, and a small group, (the metalloids), having intermediate properties and often behaving as semiconductors. A more refined classification is often shown in colored presentations of the periodic table. This system restricts the terms "metal" and "nonmetal" to only certain of the more broadly defined metals and nonmetals, adding additional terms for certain sets of the more broadly viewed metals and nonmetals. The version of this classification used in the periodic tables presented here includes: actinides, alkali metals, alkaline earth metals, halogens, lanthanides, post-transition metals (or "other metals"); metalloids, noble gases, nonmetals (or "other nonmetals"); and transition metals. In this system, the alkali metals, alkaline earth metals, and transition metals, as well as the lanthanides and the actinides, are special groups of the metals viewed in a broader sense. Similarly, the halogens and the noble gases are nonmetals viewed in the broader sense. In some presentations, the halogens are not distinguished, with astatine identified as a metalloid and the others identified as nonmetals. States of matter Another commonly used basic distinction among the elements is their state of matter (phase), whether solid, liquid, or gas, at a selected standard temperature and pressure (STP). Most of the elements are solids at conventional temperatures and atmospheric pressure, while several are gases. Only bromine and mercury are liquids at 0 degrees Celsius (32 degrees Fahrenheit) and normal atmospheric pressure; caesium and gallium are solids at that temperature, but melt at 28.4 C (83.2 F) and 29.8 C (85.6 F), respectively. Melting and boiling points Melting and boiling points, typically expressed in degrees Celsius at a pressure of one atmosphere, are commonly used in characterizing the various elements. While known for most elements, either or both of these measurements is still undetermined for some of the radioactive elements available in only tiny quantities. Since helium remains a liquid even at absolute zero at atmospheric pressure, it has only a boiling point, and not a melting point, in conventional presentations. Densities The density at a selected standard temperature and pressure (STP) is frequently used in characterizing the elements. Density is often expressed in grams per cubic centimeter (g/cm3). Since several elements are gases at commonly encountered temperatures, their densities are usually stated for their gaseous forms; when liquefied or solidified, the gaseous elements have densities similar to those of the other elements. When an element has allotropes with different densities, one representative allotrope is typically selected in summary presentations, while densities for each allotrope can be stated where more detail is provided. For example, the three familiar allotropes of carbon (amorphous carbon, graphite, and diamond) have densities of 1.82.1, 2.267, and 3.515 g/cm3, respectively.

Chemical element Crystal structures The elements studied to date as solid samples have eight kinds of crystal structures: cubic, body-centered cubic, face-centered cubic, hexagonal, monoclinic, orthorhombic, rhombohedral, and tetragonal. For some of the synthetically produced transuranic elements, available samples have been too small to determine crystal structures. Occurrence and origin on Earth Chemical elements may also be categorized by their origin on Earth, with the first 98 considered naturally occurring, while those with atomic numbers beyond 98 have only been produced artificially as the synthetic products of man-made nuclear reactions. Of the 98 naturally occurring elements, 84 are considered primordial and either stable or metastable (apparently stable but theoretically unstable, or radioactive). The remaining 14 naturally occurring elements possess half lives too short for them to have been present at the beginning of the Solar System, and are therefore considered transient elements. Of these 14 transient elements, 7 (polonium, astatine, radon, francium, radium, actinium, and protactinium) are relatively common decay products of thorium, uranium, and plutonium. The remaining 7 transient elements (technetium, promethium, neptunium, americium, curium, berkelium, and californium) occur only rarely, as products of rare nuclear reaction processes involving uranium or other heavy elements. Elements with atomic numbers 1 through 40 are all stable, while those with atomic numbers 41 through 82 (except technetium and promethium) are metastable. The half-lives of these metastable "theoretical radionuclides" are so long (at least 100 million times longer than the estimated age of the universe) that their radioactive decay has yet to be detected by experiment. Elements with atomic numbers 83 through 98 are unstable to the point that their radioactive decay can be detected. Some of these elements, notably thorium (atomic number 90) and uranium (atomic number 92), have one or more isotopes with half-lives long enough to survive as remnants of the explosive stellar nucleosynthesis that produced the heavy elements before the formation of our solar system. For example, at over 1.91019 years, over a billion times longer than the current estimated age of the universe, bismuth-209 (atomic number 83) has the longest known alpha decay half-life of any naturally occurring element.[][] The very heaviest elements (those beyond californium, atomic number 98) undergo radioactive decay with half-lives so short that they do not occur in nature and must be synthesized.

268

The periodic table


Periodic table
4 5 6 7 8 9 10 11 12 13 14 15

Pnictogens

Cha

Boron
5 B

Carbon
6 C

Nitrogen
7 N

Aluminium
13 Al

Silicon
14 Si

Phosphorus
15 P

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269
Chromium
24 Cr

Titanium
22 Ti

Vanadium
23 V

Manganese
25 Mn

Iron
26 Fe

Cobalt
27 Co

Nickel
28 Ni

Copper
29 Cu

Zinc
30 Zn

Gallium
31 Ga

Germanium
32 Ge

Arsenic
33 As

Zirconium
40 Zr

Niobium
41 Nb

Molybdenum Technetium Ruthenium Rhodium


42 Mo 43 Tc 44 Ru 45 Rh

Palladium
46 Pd

Silver
47 Ag

Cadmium
48 Cd

Indium
49 In

Tin
50 Sn

Antimony
51 Sb

Hafnium
72 Hf

Tantalum
73 Ta

Tungsten
74 W

Rhenium
75 Re

Osmium
76 Os

Iridium
77 Ir

Platinum
78 Pt

Gold
79 Au

Mercury
80 Hg

Thallium
81 Tl

Lead
82 Pb

Bismuth
83 Bi

Rutherfordium
104 Rf

Dubnium
105 Db

Seaborgium
106 Sg

Bohrium
107 Bh

Hassium Meitnerium Darmstadtium Roentgenium Copernicium Ununtrium Flerovium Ununpentium Li


108 Hs 109 Mt 110 Ds 111 Rg 112 Cn 113 Uut 114 Fl 115 Uup

Cerium
58 Ce

Praseodymium Neodymium Promethium Samarium Europium


59 Pr 60 Nd 61 Pm 62 Sm 63 Eu

Gadolinium
64 Gd

Terbium
65 Tb

Dysprosium
66 Dy

Holmium
67 Ho

Erbium
68 Er

Thulium
69 Tm

Thorium
90 Th

Protactinium
91 Pa

Uranium
92 U

Neptunium Plutonium Americium


93 Np 94 Pu 95 Am

Curium
96 Cm

Berkelium
97 Bk

Californium Einsteinium
98 Cf 99 Es

Fermium
100 Fm

Mendelevium
101 Md

tate of matter (at 0C and 1atm): black=Solid green=Liquid red=Gas grey=Unknown

he element: Primordial From decay Synthetic

Metal

Metalloid

nner transition metal Transition metal Poor metal

Unknown chemical Polyatomic nonmetal Diatomic nonmetal Noble gas properties

Nonmetal

anthanide Actinide

The properties of the chemical elements are often summarized using the periodic table, which powerfully and elegantly organizes the elements by increasing atomic number into rows ("periods") in which the columns ("groups") share recurring ("periodic") physical and chemical properties. The current standard table contains 118 confirmed elements as of 10 April 2010. Although earlier precursors to this presentation exist, its invention is generally credited to the Russian chemist Dmitri Mendeleev in 1869, who intended the table to illustrate recurring trends in the properties of the elements. The layout of the table has been refined and extended over time as new elements have been discovered and new theoretical models have been developed to explain chemical behavior. Use of the periodic table is now ubiquitous within the academic discipline of chemistry, providing an extremely useful framework to classify, systematize and compare all the many different forms of chemical behavior. The table has also found wide application in physics, geology, biology, materials science, engineering, agriculture, medicine, nutrition, environmental health, and astronomy. Its principles are especially important in chemical engineering.

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270

Nomenclature and symbols


The various chemical elements are formally identified by their unique atomic numbers, by their accepted names, and by their symbols.

Atomic numbers
The known elements have atomic numbers from 1 through 118, conventionally presented as Arabic numerals. Since the elements can be uniquely sequenced by atomic number, conventionally from lowest to highest (as in a periodic table), sets of elements are sometimes specified by such notation as "through", "beyond", or "from ... through", as in "through iron", "beyond uranium", or "from lanthanum through lutetium". The terms "light" and "heavy" are sometimes also used informally to indicate relative atomic numbers (not densities!), as in "lighter than carbon" or "heavier than lead", although technically the weight or mass of atoms of an element (their atomic weights or atomic masses) do not always increase monotonically with their atomic numbers.

Element names
The naming of various substances now known as elements precedes the atomic theory of matter, as names were given locally by various cultures to various minerals, metals, compounds, alloys, mixtures, and other materials, although at the time it was not known which chemicals were elements and which compounds. As they were identified as elements, the existing names for anciently-known elements (e.g., gold, mercury, iron) were kept in most countries. National differences emerged over the names of elements either for convenience, linguistic niceties, or nationalism. For a few illustrative examples: German speakers use "Wasserstoff" (water substance) for "hydrogen", "Sauerstoff" (acid substance) for "oxygen" and "Stickstoff" (smothering substance) for "nitrogen", while English and some romance languages use "sodium" for "natrium" and "potassium" for "kalium", and the French, Italians, Greeks, Portuguese and Poles prefer "azote/azot/azoto" (from roots meaning "no life") for "nitrogen". For purposes of international communication and trade, the official names of the chemical elements both ancient and more recently recognized are decided by the International Union of Pure and Applied Chemistry (IUPAC), which has decided on a sort of international English language, drawing on traditional English names even when an element's chemical symbol is based on a Latin or other traditional word, for example adopting "gold" rather than "aurum" as the name for the 79th element (Au). IUPAC prefers the British spellings "aluminium" and "caesium" over the U.S. spellings "aluminum" and "cesium", and the U.S. "sulfur" over the British "sulphur". However, elements that are practical to sell in bulk in many countries often still have locally used national names, and countries whose national language does not use the Latin alphabet are likely to use the IUPAC element names. According to IUPAC, chemical elements are not proper nouns in English; consequently, the full name of an element is not routinely capitalized in English, even if derived from a proper noun, as in californium and einsteinium. Isotope names of chemical elements are also uncapitalized if written out, e.g., carbon-12 or uranium-235. Chemical element symbols are always capitalized (see below). In the second half of the twentieth century, physics laboratories became able to produce nuclei of chemical elements with half-lives too short for an appreciable amount of them to exist at any time. These are also named by IUPAC, which generally adopts the name chosen by the discoverer. This practice can lead to the controversial question of which research group actually discovered an element, a question that has delayed naming of elements with atomic number of 104 and higher for a considerable time. (See element naming controversy). Precursors of such controversies involved the nationalistic namings of elements in the late 19th century. For example, lutetium was named in reference to Paris, France. The Germans were reluctant to relinquish naming rights to the French, often calling it cassiopeium. Similarly, the British discoverer of niobium originally named it columbium, in reference to the New World. It was used extensively as such by American publications prior to international standardization.

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271

Chemical symbols
Specific chemical elements Before chemistry became a science, alchemists had designed arcane symbols for both metals and common compounds. These were however used as abbreviations in diagrams or procedures; there was no concept of atoms combining to form molecules. With his advances in the atomic theory of matter, John Dalton devised his own simpler symbols, based on circles, to depict molecules. The current system of chemical notation was invented by Berzelius. In this typographical system, chemical symbols are not mere abbreviationsthough each consists of letters of the Latin alphabet. They are intended as universal symbols for people of all languages and alphabets. The first of these symbols were intended to be fully universal. Since Latin was the common language of science at that time, they were abbreviations based on the Latin names of metals. Cu comes from Cuprum, Fe comes from Ferrum, Ag from Argentum. The symbols were not followed by a period (full stop) as with abbreviations. Later chemical elements were also assigned unique chemical symbols, based on the name of the element, but not necessarily in English. For example, sodium has the chemical symbol 'Na' after the Latin natrium. The same applies to "W" (wolfram) for tungsten, "Fe" (ferrum) for iron, "Hg" (hydrargyrum) for mercury, "Sn" (stannum) for tin, "K" (kalium) for potassium, "Au" (aurum) for gold, "Ag" (argentum) for silver, "Pb" (plumbum) for lead, "Cu" (cuprum) for copper, and "Sb" (stibium) for antimony. Chemical symbols are understood internationally when element names might require translation. There are sometimes differences. For example, the Germans have used "J" instead of "I" for iodine, so the character would not be confused with a Roman numeral. The first letter of a chemical symbol is always capitalized, as in the preceding examples, and the subsequent letters, if any, are always lower case (small letters). Thus, the symbols for californium or einsteinium are Cf and Es. General chemical symbols There are also symbols for series of chemical elements, for comparative formulas. These are one capital letter long, and the letters are reserved so they can't be used for names of specific elements. For example, an "X" indicates a variables group amongst a class of compounds (though usually a halogen), while "R" is a radical, meaning a compound structure such as a hydrocarbon chain. The letter "Q" is reserved for "heat" in a chemical reaction. "Y" is also often used as a general chemical symbol, although it is also the symbol of yttrium. "Z" is also frequently used as a general variable group. "L" is used to represent a general ligand in inorganic and organometallic chemistry. "M" is also often used in place of a general metal. At least two additional, two-letter generic chemical symbols are also in informal usage, "Ln" for any lanthanide element and "An" for any actinide element. Isotope symbols Isotopes are distinguished by the atomic mass number (total protons and neutrons) for a particular isotope of an element, with this number combined with the pertinent element's symbol. IUPAC prefers that isotope symbols be written in superscript notation when practical, for example 12C and 235U. However, other notations, such as carbon-12 and uranium-235, or C-12 and U-235, are also used. As a special case, the three naturally occurring isotopes of the element hydrogen are often specified as H for 1H (protium), D for 2H (deuterium), and T for 3H (tritium). This convention is easier to use in chemical equations, replacing the need to write out the mass number for each atom. For example, the formula for heavy water may be written D2O instead of 2H2O.

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272

Origin of the elements


Only about 4% of the total mass of the universe is made of atoms or ions, and thus represented by chemical elements. This fraction is about 15% of the total matter, with the remainder of the matter (85%) being dark matter. The nature of dark matter is unknown, but it is not composed of atoms of chemical elements because it contains no protons, neutrons, or electrons. (The remaining non-matter part of the mass of the universe is composed of the even more mysterious dark energy). The universe's 94 naturally occurring chemical elements are thought to have been produced by at least four cosmic processes. Most of the hydrogen and helium in the universe was produced primordially in the first few minutes of the Big Bang. Three recurrently occurring later processes are thought to have produced the remaining elements. Stellar nucleosynthesis, an ongoing process, produces all elements from carbon through iron in atomic number, but little lithium, beryllium, or boron. Elements heavier in atomic number than iron, as heavy as uranium and plutonium, are produced by explosive nucleosynthesis in supernovas and other cataclysmic cosmic events. Cosmic ray spallation (fragmentation) of carbon, nitrogen, and oxygen is important to the production of lithium, beryllium and boron.

Estimated distribution of dark matter and dark energy in the universe. Only the fraction of the mass and energy in the universe labeled "atoms" is composed of chemical elements.

During the early phases of the Big Bang, nucleosynthesis of hydrogen nuclei resulted in the production of hydrogen-1 (protonium, 1H) and helium-4 (4He), as well as a smaller amount of deuterium (2H) and very minuscule amounts (on the order of 1010) of lithium and beryllium. Even smaller amounts of boron may have been produced in the Big Bang, since it has been observed in some very old stars, while carbon has not.[16] It is generally agreed that no heavier elements than boron were produced in the Big Bang. As a result, the primordial abundance of atoms (or ions) consisted of roughly 75% 1H, 25% 4He, and 0.01% deuterium, with only tiny traces of lithium, beryllium, and perhaps boron.[17] Subsequent enrichment of galactic halos occurred due to stellar nucleosynthesis and supernova nucleosynthesis.[] However, the element abundance in intergalactic space can still closely resemble primordial conditions, unless it has been enriched by some means. On Earth (and elsewhere), trace amounts of various elements continue to be produced from other elements as products of natural transmutation processes. These include some produced by cosmic rays or other nuclear reactions (see cosmogenic and nucleogenic nuclides), and others produced as decay products of long-lived primordial nuclides.[] For example, trace (but detectable) amounts of carbon-14 (14C) are continually produced in the atmosphere by cosmic rays impacting nitrogen atoms, and argon-40 (40Ar) is continually produced by the decay of primordially occurring but unstable potassium-40 (40K). Also, three primordially occurring but radioactive actinides, thorium, uranium, and plutonium, decay through a series of recurrently produced but unstable radioactive elements such as radium and radon, which are transiently present in any sample of these metals or their ores or compounds.

Chemical element Seven other radioactive elements, technetium, promethium, neptunium, americium, curium, berkelium, and californium, occur only incidentally in natural materials, produced as individual atoms by natural fission of the nuclei of various heavy elements or in other rare nuclear processses. Human technology has produced various additional elements beyond these first 98, with those through atomic number 118 now known.

273

Abundance
The following graph (note log scale) shows the abundance of elements in our solar system. The table shows the twelve most common elements in our galaxy (estimated spectroscopically), as measured in parts per million, by mass.[] Nearby galaxies that have evolved along similar lines have a corresponding enrichment of elements heavier than hydrogen and helium. The more distant galaxies are being viewed as they appeared in the past, so their abundances of elements appear closer to the primordial mixture. As physical laws and processes appear common throughout the visible universe, however, scientist expect that these galaxies evolved elements in similar abundance. The abundance of elements in the Solar System is in keeping with their origin from nucleosynthesis in the Big Bang and a number of progenitor supernova stars. Very abundant hydrogen and helium are products of the Big Bang, but the next three elements are rare since they had little time to form in the Big Bang and are not made in stars (they are, however, produced in small quantities by the breakup of heavier elements in interstellar dust, as a result of impact by cosmic rays). Beginning with carbon, elements are produced in stars by buildup from alpha particles (helium nuclei), resulting in an alternatingly larger abundance of elements with even atomic numbers (these are also more stable). In general, such elements up to iron are made in large stars in the process of becoming supernovas. Iron-56 is particularly common, since it is the most stable element that can easily be made from alpha particles (being a product of decay of radioactive nickel-56, ultimately made from 14 helium nuclei). Elements heavier than iron are made in energy-absorbing processes in large stars, and their abundance in the universe (and on Earth) generally decreases with their atomic number. The abundance of the chemical elements on Earth varies from air to crust to ocean, and in various types of life. The abundance of elements in Earth's crust differs from that in the universe (and also in the Sun and heavy planets like Jupiter) mainly in selective loss of the very lightest elements (hydrogen and helium) and also volatile neon, carbon, nitrogen and sulfur, as a result of solar heating in the early formation of the solar system. Aluminum is also far more common in the Earth and Earth's crust than in the universe and solar system, but the composition of Earth's mantle (which has more magnesium and iron in place of aluminum) more closely mirrors that of the universe, save for the noted loss of volatile elements. The composition of the human body, by contrast, more closely follows the composition of seawatersave that the human body has additional stores of carbon and nitrogen necessary to form the proteins and nucleic acids characteristic of living organisms. Certain kinds of organisms require particular additional elements, for example the magnesium in chlorophyll in green plants, the calcium in mollusc shells, or the iron in the hemoglobin in vertebrate animals' red blood cells.

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274

Abundances of the chemical elements in the Solar system. Hydrogen and helium are most common, from the Big Bang. The next three elements (Li, Be, B) are rare because they are poorly synthesized in the Big Bang and also in stars. The two general trends in the remaining stellar-produced elements are: (1) an alternation of abundance in elements as they have even or odd atomic numbers, and (2) a general decrease in abundance as elements become heavier. Iron is especially common because it represents the minimum energy nuclide that can be made by fusion of helium in supernovae.

Elements in our galaxy

Parts per million by mass 739,000 240,000 10,400 4,600 1,340 1,090 960 650 580 440 210 100

Hydrogen Helium Oxygen Carbon Neon Iron Nitrogen Silicon Magnesium Sulfur Potassium Nickel

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275

History
Evolving definitions
The concept of an "element" as an undivisible substance has developed through three major historical phases: Classical definitions (such as those of the ancient Greeks), chemical definitions, and atomic definitions. Classical definitions Ancient philosophy posited a set of classical elements to explain observed patterns in nature. These elements originally referred to earth, water, air and fire rather than the chemical elements of modern science. The term 'elements' (stoicheia) was first used by the Greek philosopher Plato in about 360 BCE in his dialogue Timaeus, which includes a discussion of the composition of inorganic and organic bodies and is a speculative treatise on chemistry. Plato believed the elements introduced a century earlier by Empedocles were composed of small polyhedral forms: tetrahedron (fire), octahedron (air), icosahedron (water), and cube (earth).[18][19]

Mendeleev's 1869 periodic table

Aristotle, c. 350 BCE, also used the term stoicheia and added a fifth element called aether, which formed the heavens. Aristotle defined an element as: Element one of those bodies into which other bodies can decompose, and that itself is not capable of being divided into other.[20] Chemical definitions In 1661, Robert Boyle proposed his theory of corpuscularism which favoured the analysis of matter as constituted by irreducible units of matter (atoms) and, choosing to side with neither Aristotle's view of the four elements nor Paracelsus' view of three fundamental elements, left open the question of the number of elements.[] The first modern list of chemical elements was given in Antoine Lavoisier's 1789 Elements of Chemistry, which contained thirty-three elements, including light and caloric.[21] By 1818, Jns Jakob Berzelius had determined atomic weights for forty-five of the forty-nine then-accepted elements. Dmitri Mendeleev had sixty-six elements in his periodic table of 1869.

Chemical element

276 From Boyle until the early 20th century, an element was defined as a pure substance that could not be decomposed into any simpler substance.[] Put another way, a chemical element cannot be transformed into other chemical elements by chemical processes. Elements during this time were generally distinguished by their atomic weights, a property measurable with fair accuracy by available analytical techniques.

Dmitri Mendeleev

Atomic definitions The 1913 discovery by English physicist Henry Moseley that the nuclear charge is the physical basis for an atom's atomic number, further refined when the nature of protons and neutrons became appreciated, eventually led to the current definition of an element based on atomic number (number of protons per atomic nucleus). The use of atomic numbers, rather than atomic weights, to distinguish elements has greater predictive value (since these numbers are integers), and also resolves some ambiguities in the chemistry-based view due to varying properties of isotopes and allotropes within the same element. Currently, IUPAC defines an element to exist if it has isotopes with a lifetime longer than the 1014 seconds it takes the nucleus to form an electronic cloud.[22] By 1914, seventy-two elements were known, all naturally occurring.[23] The remaining naturally occurring elements were discovered or isolated in subsequent decades, and various additional elements have also been produced Henry Moseley synthetically, with much of that work pioneered by Glenn T. Seaborg. In 1955, element 101 was discovered and named mendelevium in honor of D.I. Mendeleev, the first to arrange the elements in a periodic manner. Most recently, the synthesis of element 118 was reported in October 2006, and the synthesis of element 117 was reported in April 2010.[24]

Discovery and recognition of various elements


Ten materials familiar to various prehistoric cultures are now known to be chemical elements: Carbon, copper, gold, iron, lead, mercury, silver, sulfur, tin, and zinc. Three additional materials now accepted as elements, arsenic, antimony, and bismuth, were recognized as distinct substances prior to 1500 AD. Phosphorus, cobalt, and platinum were isolated before 1750. Most of the remaining naturally occurring chemical elements were identified and characterized by 1900, including: Such now-familiar industrial materials as aluminium, silicon, nickel, chromium, magnesium, and tungsten Reactive metals such as lithium, sodium, potassium, and calcium The halogens fluorine, chlorine, bromine, and iodine Gases such as hydrogen, oxygen, nitrogen, helium, argon, and neon Most of the rare-earth elements, including cerium, lanthanum, gadolinium, and neodymium, and

Chemical element The more common radioactive elements, including uranium, thorium, radium, and radon Elements isolated or produced since 1900 include: The three remaining undiscovered regularly occurring stable natural elements: hafnium, lutetium, and rhenium Plutonium, which was first produced synthetically in 1940 by Glenn T. Seaborg, but is now also known from a few long-persisting natural occurrences The three incidentally occurring natural elements (neptunium, promethium, and technetium), which were all first produced synthetically but later discovered in trace amounts in certain geological samples Three scarce decay products of uranium or thorium, (astatine, francium, and protactinium), and Various synthetic transuranic elements, beginning with americium, curium, berkelium, and californium

277

Recently discovered elements


The first transuranium element (element with atomic number greater than 92) discovered was neptunium in 1940. Since 1999 claims for the discovery of new elements have been considered by the IUPAC/IUPAP Joint Working Party. As of May 2012, only the elements up to 112, copernicium, as well as element 114 Flerovium and element 116 Livermorium have been confirmed as discovered by IUPAC, while claims have been made for synthesis of elements 113, 115, 117[] and 118. The discovery of element 112 was acknowledged in 2009, and the name 'copernicium' and the atomic symbol 'Cn' were suggested for it.[25] The name and symbol were officially endorsed by IUPAC on 19 February 2010.[26] The heaviest element that is believed to have been synthesized to date is element 118, ununoctium, on 9 October 2006, by the Flerov Laboratory of Nuclear Reactions in Dubna, Russia.[][27] Element 117 was the latest element claimed to be discovered, in 2009.[] IUPAC officially recognized flerovium and livermorium, elements 114 and 116, in June 2011 and approved their names in May 2012.[28]

List of the 118 known chemical elements


The following sortable table includes the 118 known chemical elements, with the names linking to the Wikipedia articles on each. Atomic number, name, and symbol all serve independently as unique identifiers. Names are those accepted by IUPAC; provisional names for recently produced elements not yet formally named are in parentheses. Group, period, and block refer to an element's position in the periodic table. State of matter (solid, liquid, or gas) applies at standard temperature and pressure conditions (STP).[citation needed] Occurrence distinguishes naturally occurring elements, categorized as either primordial or transient (from decay), and additional synthetic elements that have been produced technologically, but are not known to occur naturally. Description summarizes an element's properties using the broad categories commonly presented in periodic tables: Actinide, alkali metal, alkaline earth metal, halogen, lanthanide, metal, metalloid, noble gas, non-metal, and transition metal.

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278

List of elements
Atomic no. Name Symbol Group Period Block State at STP Gas Gas Solid Solid Solid Solid Gas Gas Gas Gas Solid Solid Solid Solid Solid Solid Gas Gas Solid Solid Solid Solid Solid Solid Solid Solid Solid Solid Solid Solid Solid Solid Solid Solid Liquid Gas Occurrence Description

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36

Hydrogen Helium Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon Sodium Magnesium Aluminium Silicon Phosphorus Sulfur Chlorine Argon Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton

H He Li Be B C N O F Ne Na Mg Al Si P S Cl Ar K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

1 18 1 2 13 14 15 16 17 18 1 2 13 14 15 16 17 18 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

1 1 2 2 2 2 2 2 2 2 3 3 3 3 3 3 3 3 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4

s s s s p p p p p p s s p p p p p p s s d d d d d d d d d d p p p p p p

Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial

Non-metal Noble gas Alkali metal Alkaline earth metal Metalloid Non-metal Non-metal Non-metal Halogen Noble gas Alkali metal Alkaline earth metal Metal Metalloid Non-metal Non-metal Halogen Noble gas Alkali metal Alkaline earth metal Transition metal Transition metal Transition metal Transition metal Transition metal Transition metal Transition metal Transition metal Transition metal Transition metal Metal Metalloid Metalloid Non-metal Halogen Noble gas

Chemical element

279
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon Caesium Barium Lanthanum Cerium Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe Cs Ba La Ce 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 1 2 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 4 5 6 7 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 s s d d d d d d d d d d p p p p p p s s f f f f f f f f f f f f f f d d d d d Solid Solid Solid Solid Solid Solid Solid Solid Solid Solid Solid Solid Solid Solid Solid Solid Solid Gas Solid Solid Solid Solid Solid Solid Solid Solid Solid Solid Solid Solid Solid Solid Solid Solid Solid Solid Solid Solid Solid Primordial Primordial Primordial Primordial Primordial Primordial Transient Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Transient Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Alkali metal Alkaline earth metal Transition metal Transition metal Transition metal Transition metal Transition metal Transition metal Transition metal Transition metal Transition metal Transition metal Metal Metal Metalloid Metalloid Halogen Noble gas Alkali metal Alkaline earth metal Lanthanide Lanthanide Lanthanide Lanthanide Lanthanide Lanthanide Lanthanide Lanthanide Lanthanide Lanthanide Lanthanide Lanthanide Lanthanide Lanthanide Lanthanide Transition metal Transition metal Transition metal Transition metal

Praseodymium Pr Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium Hafnium Tantalum Tungsten Rhenium Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Hf Ta W Re

Chemical element

280
76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 106 107 108 109 110 111 112 113 114 Osmium Iridium Platinum Gold Mercury Thallium Lead Bismuth Polonium Astatine Radon Francium Radium Actinium Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium Os Ir Pt Au Hg Tl Pb Bi Po At Rn Fr Ra Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr 8 9 10 11 12 13 14 15 16 17 18 1 2 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 4 5 6 7 8 9 10 11 12 13 14 6 6 6 6 6 6 6 6 6 6 6 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 d d d d d p p p p p p s s f f f f f f f f f f f f f f d d d d d d d d d d p p Solid Solid Solid Solid Liquid Solid Solid Solid Solid Solid Gas Solid Solid Solid Solid Solid Solid Solid Solid Solid Solid Solid Solid Solid Solid Solid Solid Solid Primordial Primordial Primordial Primordial Primordial Primordial Primordial Primordial Transient Transient Transient Transient Transient Transient Primordial Transient Primordial Transient Primordial Transient Transient Transient Transient Synthetic Synthetic Synthetic Synthetic Synthetic Synthetic Synthetic Synthetic Synthetic Synthetic Synthetic Synthetic Synthetic Synthetic Synthetic Synthetic Transition metal Transition metal Transition metal Transition metal Transition metal Transition metal Metal Metal Metal Metal Halogen Noble gas Alkali metal Alkaline earth metal Actinide Actinide Actinide Actinide Actinide Actinide Actinide Actinide Actinide Actinide Actinide Actinide Actinide Actinide Actinide Transition metal Transition metal Transition metal Transition metal Transition metal

Rutherfordium Rf Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium Copernicium (Ununtrium) Flerovium Db Sg Bh Hs Mt Ds Rg Cn Uut Fl

Chemical element

281
115 116 117 118 (Ununpentium) Uup Livermorium Lv 15 16 17 18 7 7 7 7 p p p p Synthetic Synthetic Synthetic Synthetic

(Ununseptium) Uus (Ununoctium) Uuo

References
[3] See the timeline on p.10 in [22] Transactinide-2 (http:/ / www. kernchemie. de/ Transactinides/ Transactinide-2/ transactinide-2. html). www.kernchemie.de

Further reading
Ball, P (2004). The Elements: A Very Short Introduction. Oxford University Press. ISBN0-19-284099-1. Emsley, J (2003). Nature's Building Blocks: An A-Z Guide to the Elements. Oxford University Press. ISBN0-19-850340-7. Gray, T (2009). The Elements: A Visual Exploration of Every Known Atom in the Universe. Black Dog & Leventhal Publishers Inc. ISBN1-57912-814-9. Scerri, ER (2007). The Periodic Table, Its Story and Its Significance. Oxford University Press. Strathern, P (2000). Mendeleyev's Dream: The Quest for the Elements. Hamish Hamilton Ltd. ISBN0-241-14065-X.

External links
Videos for each element (http://periodicvideos.com/) by the University of Nottingham

Isotope
Nuclear physics

Nucleus Nucleons(p, n) Nuclear force Nuclear reaction

Isotope

282

Isotopes are variants of a particular chemical element such that, while all isotopes of a given element share the same number of protons and electrons, each isotope differs from the others in its number of neutrons. The term isotope is formed from the Greek roots isos ( "equal") and topos ( "place"), meaning "the same place". Thus, different isotopes of a single element occupy the same position on the The three naturally-occurring isotopes of hydrogen. The fact that each isotope has periodic table. The number of protons one proton makes them all variants of hydrogen: the identity of the isotope is given within the atom's nucleus uniquely identifies by the number of neutrons. From left to right, the isotopes are protium (1H) with zero neutrons, deuterium (2H) with one neutron, and tritium (3H) with two an element, but a given element may in neutrons. principle have any number of neutrons. The number of nucleons (protons and neutrons) in the nucleus is the mass number, and each isotope of a given element has a different mass number. For example, carbon-12, carbon-13 and carbon-14 are three isotopes of the element carbon with mass numbers 12, 13 and 14 respectively. The atomic number of carbon is 6, which means that every carbon atom has 6 protons, so that the neutron numbers of these isotopes are 6, 7 and 8 respectively.

Isotope vs. nuclide


A nuclide is an atom with a specific number of protons and neutrons in the nucleus, for example carbon-13 with 6 protons and 7 neutrons. The nuclide concept (referring to individual nuclear species) emphasizes nuclear properties over chemical properties, while the isotope concept (grouping all atoms of each element) emphasizes chemical over nuclear. The neutron number has drastic effects on nuclear properties, but its effect on chemical properties is negligible in most elements, and still quite small in the case of the very lightest elements, although it does matter in some circumstances (for hydrogen, the lightest of all elements, the isotope effect is large enough to strongly affect biology). Since isotope is the older term, it is better known than nuclide, and is still sometimes used in contexts where nuclide might be more appropriate, such as nuclear technology and nuclear medicine.

Notation
An isotope and/or nuclide is specified by the name of the particular element (this indicates the atomic number implicitly) followed by a hyphen and the mass number (e.g. helium-3, helium-4, carbon-12, carbon-14, uranium-235 and uranium-239).[1] When a chemical symbol is used, e.g., "C" for carbon, standard notation (now known as "AZE notation" because A is the mass number, Z the atomic number, and E for element) is to indicate the number of nucleons with a superscript at the upper left of the chemical symbol and to indicate the atomic number with a subscript at the lower left (e.g. 3 2He, 4 2He, 12 6C, 14 6C, 235 92U, and 239 [2] 92U, respectively). Since the atomic number is implied by the element symbol, it is common to state only the mass number in the superscript and leave out the atomic number subscript (e.g. 3He, 4He, 12C, 14C, 235U, and 239U, respectively). The letter m is sometimes appended after the mass number to indicate a nuclear isomer, a metastable

Isotope or energetically-excited nuclear state (rather than the lowest-energy ground state), for example 180m 73Ta (tantalum-180m).

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Radioactive, primordial, and stable isotopes


Some isotopes are radioactive, and are therefore described as radioisotopes or radionuclides, while others have never been observed to undergo radioactive decay and are described as stable isotopes. For example, 14C is a radioactive form of carbon while 12C and 13C are stable isotopes. There are about 339 naturally occurring nuclides on Earth,[] of which 288 are primordial nuclides, meaning that they have existed since the solar system's formation. Primordial nuclides include 35 nuclides with very long half-lives (over 80 million years) and 254 that are formally considered as "stable isotopes",[] since they have not been observed to decay. In most cases, for obvious reasons, if an element has stable isotopes, those isotopes predominate in the elemental abundance found on Earth and in the solar system. However, in the cases of three elements (tellurium, indium, and rhenium) the most abundant isotope found in nature is actually one (or two) extremely long lived radioisotope(s) of the element, despite these elements having one or more stable isotopes. Many apparently "stable" isotopes are predicted by theory to be radioactive, with extremely long half-lives (this does not count the possibility of proton decay, which would make all nuclides ultimately unstable). Of the 254 nuclides never observed to decay, only 90 of these (all from the first 40 elements) are stable in theory to all known forms of decay. Element 41 (niobium) is theoretically unstable via spontaneous fission, but this has never been detected. Many other stable nuclides are in theory energetically susceptible to other known forms of decay, such as alpha decay or double beta decay, but no decay products have yet been observed, and so these isotopes are described as "observationally stable". The predicted half-lives for these nuclides often greatly exceed the estimated age of the universe, and in fact there are also 27 known radionuclides (see primordial nuclide) with half-lives longer than the age of the universe. Adding in the radioactive nuclides that have been created artificially, there are more than 3100 currently known nuclides.[3] These include 905 nuclides that are either stable or have half-lives longer than 60 minutes. See list of nuclides for details.

History
Radioactive isotopes
The existence of isotopes was first suggested in 1912 by the radiochemist Frederick Soddy, based on studies of radioactive decay chains that indicated about 40 different species described as radioelements (i.e. radioactive elements) between uranium and lead, although the periodic table only allowed for 11 elements from uranium to lead.[4][5] Several attempts to separate these new radioelements chemically had failed.[6] For example, Soddy had shown in 1910 that mesothorium (later shown to be 228Ra), radium (226Ra, the longest-lived isotope), and thorium X (224Ra) are impossible to separate.[] Attempts to place the radioelements in the periodic table led Soddy and Kazimierz Fajans independently to propose their radioactive displacement law in 1913, to the effect that alpha decay produced an element two places to the left in the periodic table, while beta decay emission produced an element one place to the right.[7] Soddy recognized that emission of an alpha particle followed by two beta particles led to the formation of an element chemically identical to the initial element but with a mass four units lighter and with different radioactive properties. Soddy proposed that several types of atoms (differing in radioactive properties) could occupy the same place in the table. For example, the alpha-decay of uranium-235 forms thorium-231, while the beta decay of actinium-230 forms thorium-230[6] The term "isotope", Greek for "at the same place", was suggested to Soddy by Margaret Todd, a

Isotope Scottish physician and family friend, during a conversation in which he explained his ideas to her.[][8][9][][10][11] In 1914 T. W. Richards found variations between the atomic weight of lead from different mineral sources, attributable to variations in isotopic composition due to different radioactive origins.[6][12]

284

Stable isotopes
The first evidence for isotopes of a stable (non-radioactive) element was found by J. J. Thomson in 1913 as part of his exploration into the composition of canal rays (positive ions).[13][14] Thomson channeled streams of neon ions through a magnetic and an electric field and measured their deflection by placing a photographic plate in their path. Each stream created a glowing patch on the plate at the point it struck. Thomson observed two separate patches of light on the photographic plate (see image), which suggested two different parabolas of deflection. Thomson eventually concluded that some of the atoms in the neon gas were of higher mass than the rest.
In the bottom right corner of J. J. Thomson's F. W. Aston subsequently discovered different stable isotopes for photographic plate are the separate impact marks numerous elements using a mass spectrograph. In 1919 Aston studied for the two isotopes of neon: neon-20 and neon with sufficient resolution to show that the two isotopic masses are neon-22. very close to the integers 20 and 22, and that neither is equal to the known molar mass (20.2) of neon gas. This is an example of Aston's whole number rule for isotopic masses, which states that large deviations of elemental molar masses from integers are primarily due to the fact that the element is a mixture of isotopes. Aston similarly showed that the molar mass of chlorine (35.45) is a weighted average of the almost integral masses for the two isotopes Cl-35 and Cl-37.[15]

Variation in properties between isotopes


Chemical and molecular properties
A neutral atom has the same number of electrons as protons. Thus, different isotopes of a given element all have the same number of protons and share a similar electronic structure. Because the chemical behavior of an atom is largely determined by its electronic structure, different isotopes exhibit nearly identical chemical behavior. The main exception to this is the kinetic isotope effect: due to their larger masses, heavier isotopes tend to react somewhat more slowly than lighter isotopes of the same element. This is most pronounced for protium (1H) and deuterium (2H), because deuterium has twice the mass of protium. The mass effect between deuterium and the relatively light protium also affects the behavior of their respective chemical bonds, by means of changing the center of gravity (reduced mass) of the atomic systems. However, for heavier elements, which have more neutrons than lighter elements, the ratio of the nuclear mass to the collective electronic mass is far greater, and the relative mass difference between isotopes is much less. For these two reasons, the mass-difference effects on chemistry are usually negligible.

Isotope

285

In similar manner, two molecules that differ only in the isotopic nature of their atoms (isotopologues) will have identical electronic structure and therefore almost indistinguishable physical and chemical properties (again with deuterium providing the primary exception to this rule). The vibrational modes of a molecule are determined by its shape and by the masses of its constituent atoms. As a consequence, isotopologues will have different sets of vibrational modes. Since vibrational modes allow a molecule to absorb photons of corresponding energies, isotopologues have different optical properties in the infrared range.

Nuclear properties and stability


Atomic nuclei consist of protons and neutrons bound together by the residual strong force. Because protons are positively charged, they repel each other. Neutrons, Isotope half-lives. Note that the plot for stable isotopes diverges from the line Z = N as the element number Z becomes larger which are electrically neutral, stabilize the nucleus in two ways. Their copresence pushes protons slightly apart, reducing the electrostatic repulsion between the protons, and they exert the attractive nuclear force on each other and on protons. For this reason, one or more neutrons are necessary for two or more protons to be bound into a nucleus. As the number of protons increases, so