CHAPTER 4 : METALLURGY, PROPERTIES AND USES OF FERROUS METALS AND ALLOYS I -The manufacture of iron and steel-

Silicon . . . . . . . . . . . . . . . . . . . . 27.5 Aluminum Iron . . . . . . . . . . . . . . . . . 8.0 5.0 3.5 3.0

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Calcium . . . . . . . . . . . . . . . . . . . . Metallurgy - is the science which deals with the preparation and application of metals and alloys. Classes of Metallurgy Sodium . . . . . . . . . . . . . . . . . . . .

Potassium . . . . . . . . . . . . . . . . . . . 2.5 Factors Determining the Price of Metals Three Principal Factors 1.The degree of concentration of the mineral deposits (depends upon the manner in which the ore occurs in nature; upon the type of mineral.) 2.The costs, per ton of ore handled, of reducing or otherwise recovering the metal (depends upon the economical efficiency.) 3.The law of supply and demand, which is influenced largely by need and which seems to defy human control. Ore is a combination of minerals which can be profitably mined. Gangue secondary minerals consist of impurities of an earthy nature, such as rock, sand, clay. Chemical Nature of Ores

1.Chemical metallurgy -deals with the reduction of metals from their minerals and the refining and alloying of those metals. 2. Physical metallurgy - deals with the nature, structure, and physical properties of metals and alloys. 3. Mechanical metallurgy -deals with the working and shaping of metals and alloys, such as casting, forging, rolling, and drawing. Occurrence of Metals in Nature Three kingdoms; animal, vegetable, and mineral old-fashioned method of which the earth is made up. The geologist considers the earth to be made up of : Central sphere - includes the interior of the earth. Lithosphere - includes the earths crust. Hydrosphere - includes the water on the surface of the earth. Atmosphere - the air above the earth. From a study of chemist, all matter is made up of various combination of one or more of the 101 elements. Organic and Inorganic Compounds 101 elements may be classified as : metals, non-metals, and metalloids Elements of Earths Crust Percent 46.5

Acid Ores those ores which contains the predominance of silica or silicate in the gangue. Basic Ores those with a predominance of limestone and magnesia. Primary Metals -are metals produced directly from ore, in contrast to secondary metals that are reclaimed from scrap. Ore Dressing - the mechanical treatments by which the concentration of ores is increased. The operation may be accomplished by : magnetic separation, crushing, flotation, or screening.

Oxygen . . . . . . . . . . . . . . . . . . . .

Gravity Separation- may be employed as a method of concentration by the simple process of panning. Flotation Process - concentration of some ores in which reagents are added to the ore to form a film on certain types of minerals. Purification Purification Processes -involve some change in chemical character. Drying - by which a certain degree of purification of the ore can be secured. -whereby some of the water of crystallization is removed by heating. Calcining - in which the character of the ore is changed without oxidation. Roasting - is another method of purification involving a process of oxidation in which sulfides are converted to oxides. Sintering -purification process to assist in the separation of the gauge from the ore. It involves melting of the ore. Distillation -method of purification prior to the process of reduction. Leaching - process in which the valuable mineral is dissolved away from the gangue. Digestion - if the leaching operation is accomplished at high temperature. Reduction of Ores Pyrometallurgical - reduction processes which employ heat. Hydrometallurgical - those processes which involve the reduction of the metal from aqueous solutions by replacement or by electrolysis Electrometallurgical - those processes that involve electrolytic methods Smelting - application of heat and the use of reducing agents.

Cementation - the displacement of the metal from a liquid solution. Electrodeposition - reduction of metals by from aqueous solution or from fused anhydrous salts by the use of electrolysis. Refining of Metals Following the reduction of metals from their ores, it is usually necessary to refine them to improve purity. Fire refining - one of the most common methods of purifying metals by the oxidation of impurities in furnaces. Oxygen or oxides are not the sole materials that are used in this process. Cupellation- the refinement of precious metals by exposing them to an air blast so that any included base metals are oxidized and swept away in that blast or sink into the porous cupel Liquation/Sweating- the impurities that are not soluble in the metal being refined separate from the solid at temperature at which the impurities are liquid and not soluble in the liquid state in the metal being refined. Zinc may be refined by the process of distillation in which the zinc vaporizes leaving the impurities behind. Nickel may be refined by a distillation process by forming a nickel carbonyl. The carbonyl is produced by a reaction of the finely divided impure nickel with purified carbon monoxide at atmospheric pressure and at a temperature between 80 F and 150 F. This reaction occurs in the following manner: Ni + 4 CO Ni (CO) 4. The Ni (CO) 4 is called nickel carbonyl and is a gas. Electrolysis - very common method of purifying metals. The impure metal forms the anode of an electrolytic cell. Chemical Strength Chemical Strength - refers to the chemical activity of the element; that is, to its affinity for negative ions. The elements may be arranged in a table of decreasing order of chemical strength, known as the electromotive series of metals, as given in table below:

Electromotive Series of Metal Metal Potassium.. Calcium. Sodium.. Magnesium. Aluminum. Manganese. Zinc Chromium.. Iron... Cadmium.. Cobalt. Nickel.. Tin.. Lead. Hydrogen. Antimony.. Bismuth Arsenic. Copper. Silver. Mercury.. Platinum.. Gold. K Ca Na Mg Al Mn Zn Cr Fe Cd Co Ni Sn Pb H Sb Bi As Cu Ag Hg Pt Au Potential value 2.92 2.87* 2.71 2.40* 1.70* 1.10 0.762 0.557 0.441 0.401* 0.278 0.231 0.136 0.122 0.000 -0.10* -0.226* -0.30* -0.344 -0.798 -0.799 -0.863* -0.360*

Fluxes The gangue which remains in the ore after dressing must be removed in the furnace. Usually the furnace temperatures are not high enough to melt this gangue. Fusion can be obtained by the addition of some material that will react with the gangue to produce a substance having a lower fusion temperature. The materials which are added for this purpose are called fluxes.

Fig. 4.1 Blast Furnaces In reducing processes the flux has a chemical nature to that of the gangue. If the ore in nature, then limestone will be added; if the ore is basic, silicates or silica will be used as a flux. The flux and gangue, when in proper proportions, will have a melting temperature considerably lower than of either one, and the resulting combination is called slag. The flux serves the functions in the reducing processes: 1. It fuses the gangue. 2. It absorbs the impurities which are oxidized. 3. It protects the reduced metal from oxidation. Furnaces There are many kinds of furnaces in which melting and smelting operations may be carried out. Probably the simplest of these is a simple crucible of refractory material about which the heat is applied. For large-scale production, a blast furnace, such as shown in Fig. 4.1 is used. The principal requirement of any furnace is that it withstands the high temperature. The furnace is generally constructed with an outer wall of silica brick, lined with the highest grade of refractory brick, the whole encased in a shell of steel plates which may be

According to the electromotive series, if a piece of zinc is placed in a solution containing is placed in a solution containing silver ions; the zinc will be coated with a layer of silver. In this reaction, zinc has replaced silver in the solution according to the equation Zn + 2Ag+ = Zn++ + 2Ag And metallic silver has been precipitated. This illustrates the fact that any metal will displace another metal from an ionized solution of the latter metal, provided the second metal is below the first in the electromotive series. By a study of metallurgical process processes in relation to the electromotive series, it is known that the oxides of weak metals, up through mercury, can be reduced from their oxides by heating alone; the oxides of the other metals up to manganese are reduced by heating in the presence of a reducing agent such as carbon; the strong metals down through manganese can be reduced only by electrolytic methods, usually in molten salts of the metal.

water-cooled. In the blast furnace, the fuel is introduced into the furnace with the ore and flux, whereas in the reverberatory furnace, the fuel is burned in a separate compartment, the flame and hot gases passing over the charge before passing out of the stack. Refractory Materials Refractory - nonmetallic materials of high melting temperature, used in the construction of furnaces, crucibles, and so forth. A refractory must satisfy certain requirements: 1. It must not melt or disintegrate from the action of the heat 2. It must not enter into chemical combinations with the furnace charge. 3. It must resists oxidation and reduction 4. It must withstand the mechanical wear by the furnace charge A refractory may classified chemically as: Acid refractory - are those which are composed principally of silica (SiO2) and aluminum silicate. A Silica brick, which is a common refractory material, contains about 94% SiO2, with the balance, alumna and lime, employed as a binder. Neutral refractory this includes alundum (fused alumina-Al2O3); sillimanite (Al2O3.SiO2); mullite (3Al2O3.2SiO2); chromite (Cr2O3.FeO), a very expensive but valuable refractory in a furnace; and fire clay, which is made up principally of kaolin (Al2O.2SiO2.2H2O). Basic refractory this include dolomite, a mixture of magnesium and calcium and magnesium. Magnesium carbonate (magnesite) makes the best refractory, but its cost prevents its more general use. The melting temperatures of some of the more common refractory are given in table below:

Temperatures of Incipient Fusion for Pure Refractory Melting Temperatur e 3200F 3290F 3300F 3870F 3960F 5230F 3730F 4500F Decomposes at very high temp 5070F 3880F

Refractory Silica Andalusite Sillimanite Mullite Chromic Oxide Chromite Carbon graphite Alumina Lime Dolomite Magnesia Magnesia Spinel

Compositio n SiO2 Al2O3.SiO2 Al2O3.SiO2 3Al2O3.2Si O2 Cr2O3 Cr2O2.FeO Al2O2 CaO CaO.MgO MgO MgO.Al3O3

Class Acid Neutral Neutral Neutral Neutral Neutral Neutral Basic Basic Basic Basic Basic

Fuels In metallurgical processes, fuels may serve the following purposes: 1. To raise the temperature to that necessary to promote chemical reactions 2. To react with the ore as a chemical reagent 3. To soften or to fuse the materials for shaping, as in forging and casting These fuels may be classified as solid, liquid. Or gaseous and the fuels in any of these classes may be either natural or prepared. IRON ORES OXIDES ORES -most common of iron ore -associated with earthy matter -widely used Lake Superior region Most important in the United States Consisting of six distinct ore-bearing formations Ore vary : Physically Chemically Examples : Vermillion range ore Hard Carrying very little moisture Gogebic range ore Soft Carrying form 10 to 15 per cent moisture Menominee range ore Slaty Have a characteristics bluish color Others being reddish brown or yellowish brown Mesabi ore Granular Like the consistency when dry Mining methods That are used in obtaining this ores affects the way they become Example :

Mesabi range

Hematite Most important ore found in the united states Hard lumpy or granular ore Blackish brown to brick red Composed of oxide Fe2O3 Magnetite Magnetic ore , Fe3O4 Found in US in New York district Hard, heavy Gray or black mineral Granular or massive form Associated with phosphorus and sulfur Limonite Or hydrated hematite Less important oxide found throughout US Brown lumpy deposit consisting of Fe2O3 and H2O Siderite Or spathic ore, carbonate FeCO3 Not so important ore Taconite Iron-bearing slate or chest in from of compact siliceous rock Magnetite material but without the silica having been leached out Requires extensive treatment for benefication before it can be utilized in production operations

Two Ways of removing excess oxygen from the molten steel: Deoxidation (Killing) Rimming Deoxidation (Killing) It is the removal of excess oxygen from the molten metal by the use of deoxiders. Deoxidizers: Manganese Silicon Aluminum Titanium Silicon or Aluminum is added to the molten metal. The added element reduces the iron oxide (excess oxygen) or combine with dissolved oxygen to form SiO2 or Al2O3.

Steels can be manufactured through the following processes: Cementation Crucible Bessemer Direst Oxygen Open-hearth Electric

1. Cementation In this process, wrought iron bars were heaped together in large boxes with charcoal and heated at about 1600 F for 7 to 11 days. Carbon diffuses into the iron, producing steel by carburization. These carburized bars are heated, bundled and forged into bars. Until 1742, producing steel was a difficult task. The quality of the steel was often unreliable. The steel was made by heating iron bars which were covered in charcoal. The heating was continued for up to a week. The material produced was called blister steel. No more than about 200 tons of steel were produced each year, using this process. 2. Crucible The process produced uniform high quality steel in reasonably large quantities. Within 100 years of the invention of the process, Sheffield was producing 20000 tons of crucible steel a year. This was 40% of the total amount of steel produced in Europe at this time. Process: The crucible steel process starts with the manufacture of special clay pots or crucibles.

Rimming Another method used in removing excess oxygen Manganese is added to the molten metal, which reacts with some of the iron oxide. The steel then is cast into a mold. There will be a formation of carbon monoxide gas. The bubbles tend to rise to the top of the mold and are given off to the atmosphere.

Limitation of rimming: Rimming cannot be made successfully in steels that contain more than about 0.15% carbon. Capping process used to stop rimming action by placing a cap on the top of the ingot steel. This has a chilling effect causing the top of the steel to freeze more rapidly.

 The crucibles are heated in a fired furnace. When they are at white heat, they are filled with broken bars of steel and a flux to collect impurities. The steel is then melted for about three hours. The pot is lifted out of the furnace using long handled tongs which grip round the outside of the crucible. The molten steel is then poured from the crucible into a cast iron ingot mold. When the steel has solidified and cooled, the mold is opened so that the steel bar can be removed 3. Bessemer Process In 1855, Sir Henry Bessemer in England invented Bessemer process for the mass production of steel from the molten pig iron. Bessemer Converter a pear shaped vessel used for bessemer process.

The air is passing continuously through the tuyeres, comes in contact with the molten metal and oxidizing certain impurities (Mn, Si, C). Slag Formation and burning out of impurities.

4. Direct Oxygen process A process of refining pig iron to produce steel in which the impurities in the pig iron are directly oxidized with pure oxygen. Also known as LD process (Linz-Donawitz) or oxygen converter process Similar in principle to the Bessemer process Process: Oxygen (at least 98% pure) is blown vertically downward onto the molten bath through a water cooled nozzle. Violent circulation on the molten bath is established. The hot metal flows downward at the center to the bottom and outward to the walls of the vessel where it rises.

Process: Bessemer converter is turned into a horizontal position and molten pig iron is poured into it. The converter is then tilted into its vertical position, and air from compressors is blown through the molten metal under a pressure of about 15 lb/in2.

5. Open Hearth process Process: Pig iron and scrap are placed into the furnace with special manipulators.

 The fluorspar is added to make the slag more fluid, and the reactions continue for about 8 to 10 hr. When the melt has reached the proper analysis, the molten metal is run into ladles which carry the metal to the ingot molds The gas and air are preheated by regenerators, two on each side of the furnace, alternatively heated by the waste gases. The regenerators are chambers filled with checker brickwork, brick and space alternating.