Spheroidizing: Spheroidite forms when carbon steel is heated to approximately 700 C for over 30 hours.

Spheroidite can form at lower temperatures but the time needed drastically increases, as this is a diffusioncontrolled process. The result is a structure of rods or spheres of cementite within primary structure (ferrite or pearlite, depending on which side of the eutectoid you are on). The purpose is to soften higher carbon steels and allow more formability. This is the softest and most ductile form of steel. The image to the right shows where spheroidizing usually occurs.[10] Full annealing: Carbon steel is heated to approximately 40 C above Ac3 or Ac1 for 1 hour; this assures all the ferrite transforms into austenite (although cementite might still exist if the carbon content is greater than the eutectoid). The steel must then be cooled slowly, in the realm of 38C (68.4F) per hour. Usually it is just furnace cooled, where the furnace is turned off with the steel still inside. This results in a coarse pearlitic structure, which means the "bands" of pearlite are thick. Fully annealed steel is soft and ductile, with no internal stresses, which is often necessary for cost-effective forming. Only spheroidized steel is softer and more ductile.[11] Process annealing: A process used to relieve stress in a cold-worked carbon steel with less than 0.3 wt% C. The steel is usually heated up to 550650 C for 1 hour, but sometimes temperatures as high as 700 C. The image rightward shows the area where process annealing occurs. Isothermal annealing: It is a process in which hypoeutectoid steel is heated above the upper critical temperature and this temperature is maintained for a time and then the temperature is brought down below lower critical temperature and is again maintained. Then finally it is cooled at room temperature. This method rids any temperature gradient. Normalizing: Carbon steel is heated to approximately 55 C above Ac3 or Acm for 1 hour; this assures the steel completely transforms to austenite. The steel is then air-cooled, which is a cooling rate of approximately 38 C (68 F) per minute. This results in a fine pearlitic structure, and a more-uniform structure. Normalized steel has a higher strength than annealed steel; it has a relatively high strength and ductility.[12] Quenching: Carbon steel with at least 0.4 wt% C is heated to normalizing temperatures and then rapidly cooled (quenched) in water, brine, or oil to the critical temperature. The critical temperature is dependent on the carbon content, but as a general rule is lower as the carbon content increases. This results in a martensitic structure; a form of steel that possesses a super-saturated carbon content in a deformed bodycentered cubic (BCC) crystalline structure, properly termed body-centered tetragonal (BCT), with much internal stress. Thus quenched steel is extremely hard but brittle, usually too brittle for practical purposes. These internal stresses cause stress cracks on the surface. Quenched steel is approximately three to four (with more carbon) fold harder than normalized steel.[13] Martempering (Marquenching): Martempering is not actually a tempering procedure, hence the term "marquenching". It is a form of isothermal heat treatment applied after an initial quench of typically in a molten salt bath at a temperature right above the "martensite start temperature". At this temperature, residual stresses within the material are relieved and some bainite may be formed from the retained austenite which did not have time to transform into anything else. In industry, this is a process used to control the ductility and hardness of a material. With longer marquenching, the ductility increases with a minimal loss in strength; the steel is held in this solution until the inner and outer temperatures equalize. Then the steel is

cooled at a moderate speed to keep the temperature gradient minimal. Not only does this process reduce internal stresses and stress cracks, but it also increases the impact resistance.[14] Quench and tempering: This is the most common heat treatment encountered, because the final properties can be precisely determined by the temperature and time of the tempering. Tempering involves reheating quenched steel to a temperature below the eutectoid temperature then cooling. The elevated temperature allows very small amounts of spheroidite to form, which restores ductility, but reduces hardness. Actual temperatures and times are carefully chosen for each composition.[15] Austempering: The austempering process is the same as martempering, except the steel is held in the molten salt bath through the bainite transformation temperatures, and then moderately cooled. The resulting bainite steel has a greater ductility, higher impact resistance, and less distortion. The disadvantage of austempering is it can only be used on a few steels, and it requires a special salt bath.[16] At room temperature, the most stable form of iron is the body-centered cubic (BCC) structure -ferrite. It is a fairly soft metallic material that can dissolve only a small concentration of carbon, no more than 0.021 wt% at 723 C (1,333 F), and only 0.005% at 0C (32 F). If steel contains more than 0.021% carbon at steelmaking temperatures then 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% (Ashby and Jones, 1992) carbon at 1,148 C (2,098 F), which reflects the upper carbon content of steel. When steels with less than 0.8% carbon, known as a hypoeutectoid steel, are cooled from an austenitic phase 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 cementite to precipitate out of the mix, leaving behind iron that is pure enough to take the form of ferrite, resulting in a cementite-ferrite mixture. 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 after 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. Perhaps the most important polymorphic form is martensite, a metastable phase which is significantly stronger than other steel phases. When the steel is in an austenitic phase and then quenched it forms into martensite, because 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 higher carbon contents take 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

Martensite has a lower density than austenite does, so that 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 water quenched, although they may not always be visible.

BOF Pollution Sources and Prevention Opportunities Different types of pollution result from the different steps in steel production. Below, the pollution sources and the possible pollution prevention opportunities are discussed for each process. Pollution Sources and Prevention for Cokemaking Coke production is one of the major pollution sources from steel production. Air emissions such as coke oven gas, naphthalene, ammonium compounds, crude light oil, sulfur and coke dust are released from coke ovens. Emissions control equipment can be used to capture some of the gases. Some of the heat can be captured for reuse in other heating processes. Other gases may escape into the atmosphere. Figure 1: The Steel Making Process (EPA, 1995) Water pollution comes from the water used to cool coke after it has finished baking. Quenching water becomes contaminated with coke breezes and other compounds. While the volume of contaminated water can be great, quenching water is fairly easy to reuse. Coke breezes and other solids can usually be removed by filtration. The resulting water can be reused in other manufacturing processes or released. Reducing Coke Oven Emissions Pollution associated with coke production is best reduced by decreasing the amount of coke used in the iron melting process. The smaller the volume of coke produced, the smaller the volume of air and water emissions. However, process modifications in actual coke production are not widely available and are very expensive. One fairly economical method of reducing coke oven pollution is to reduce the levels of coke used in blast furnaces. A portion of the coke can be replaced with other fossil fuels without retrofitting the furnace. Pulverized coal can be substituted for coke at nearly a 1:1 and can replace 25 - 40% of coke traditionally used in furnaces (USEPA, 1995). Pulverized coal injection is used worldwide to reduce coke use and, thus, coke emissions (Chatterjee, 1995). Pulverized coal injection may affect the final steel products. Pulverized coal may reduce gas permeability of the metal and unburnt coal particles may accumulate in the furnace, decreasing efficiency. Thus, it may not be possible to substitute pulverized coal for coke in the production of high quality steel. Other alternative fuels such as natural gas, oil or tar/pitch can be used to replace coke using similar process modifications. The reduction in emissions is proportional to the reduction in coke use.

Air and water emissions may also be reduced by using a non-recovery coke battery. In traditional plants, byproducts are recovered from the blast furnace. In non-recovery batteries, coke oven slag and other by-products are sent to the battery where they are combusted. This technique consumes the by-products, eliminating much of the air and water pollution. Non-recovery coke batteries do require replacement or retrofitting of traditional coke ovens. This process modification does reduce pollution, but can be expensive. A third method for reducing coke oven emissions is the Davy Still Autoprocess. The process uses water to remove ammonia and hydrogen sulfide from coke oven emissions prior to cleaning of the oven.

Cokeless Ironmaking
Cokeless ironmaking procedures are currently being studied and, in some places, implemented. One such procedure is the Japanese Direct Iron Ore Smelting (DIOS) process (Figure 2). The DIOS process produces molten iron from coal and previously melted ores. In this process, coal and other ores can produce enough heat to melt ore, replacing coke completely (USEPA, 1995). In addition to reducing coke use, the DIOS process could cut the costs of molten iron production by about 10%, reduce emissions of carbon dioxide by 5 - 10% and increase flexibility by improving the starting and stopping capabilities of the steel mill (Furukawa, 1994). However, the DIOS process remain very expensive and requires extensive process modification. In 1995, this method was still being tested and economic feasibility will be determined from those tests. The HISmelt process, named after the HISmelt Corporation of Australia, is another cokeless iron melting process being tested. In this process, ore fines and coal are manipulated to melt iron ore. In 1993, the process could produce eight tons of iron ore per hour using ore directly in the smelter. Process modifications are expected to increase the efficiency to 14 tons per hour. Commercial feasibility studies were performed in 1995. Midrex is expected to be the U.S. distributor of the process. A final cokeless iron melting process is the Corex or Cipcor Process. This process also manipulates coke to produce the heat required to melt iron. A Corex plant is operational in South Africa. Posco of Korea has a Corex plant operating at 70% capacity in 1996 and is expected to continue progress (Ritt, 1996). India is also expected to build a plant in 1997. The process integrates coal desulfurization, has flexible coal-type requirements, and generates excess electricity that can be sold to power grids (USEPA, 1995). Further testing is being conducted to determine actual commercial feasibility in the U.S. Figure 2. The DIOS Process (Furukawa, 1994)

Iron Carbide Steel Production Plants

Iron carbide production plants can be an alternative to the Basic Oxide Furnace. These plants use iron carbide, an iron ore that contains 6% carbon rather than 1.5-1.8% of regular iron ore . The additional carbon ignites in the presence of oxygen and contributes heat to the iron melting process, reducing energy requirements (Ritt, 1996). While these types of plants do not reduce pollution on site, they do reduce the electricity requirement for steel production, reducing polution from the power plant.

Pollution Sources and Prevention in Ironmaking

Slag, the limestone and iron ore impurities collected at the top of the molten iron, make up the largest portion of ironmaking by-products. Sulfur dioxide and hydrogen sulfide are volatized and captured in air emissions control equipment and the residual slag is sold to the construction industry. While this is not a pollution prevention technique, the solid waste does not reach landfills. Blast furnace flue gas is also generated during ironmaking. This gas is cleaned to remove particulates and other compounds, allowing it to be reused as heat for coke furnaces or other processes. Cleaning gas for reuse can produce some air pollution control dust and water treatment plant sludge, depending on the method used. The dust can be reused in sintering processes or landfilled. Pollution Sources and Prevention in the BOF Slag is a major component of the waste produced in BOFs. Because of its composition, this slag, unlike that from the blast furnace, is best used as an additive in the sintering process. As its metallic content is lower, it does not make a good raw material for the construction industry. Hot gases are also produced by the BOF. Furnaces are equipped with air pollution control equipment that contains and cools the gas. The gas is quenched and cooled using water and cleaned of suspended solids and metals. This process produces air pollution control dust and water treatment plant sludge. Pollution Sources and Material Recovery Gaseous emissions and metal dust are the most prominent sources of waste from electric arc furnaces. Gaseous emissions are collected and cleaned, producing EAF dust or sludge. The remaining gas contains small quantities of nitrogen oxide and ozone and is usually released. The EAF dust or sludge composition varies depending on the type of steel being manufactured. Common components include iron and iron oxides, flux, zinc, chromium, nickel oxide and other metals used for alloys. If the dust or sludge contains lead or cadmium, it is listed as a hazardous waste (RCRA K061) (USEPA, 1995). In 1996, 500kg of EAF dust were produced for each tonn (UK weight measurements) of crude steel production. In the United Kingdom, 70% of that dust is sold to other companies, 20% is recycled in-plant and 10% is landfilled. Although it is a relatively small proportion of the total volume of waste, the landfilled EAF dust amounts to 50 kg per tonne of crude steel produced (Strohmeier, 1996). Recycling and recovery of EAF dust can be difficult because of the alkalinity and heavy metal (zinc and lead) content. The dust can be landfilled, but, because of the fine nature, it may leach into ground water. Several processes have been developed to recover the zinc, lead and other heavy metals from EAF dust. Although not pollution prevention, metal recovery is almost always profitable if the zinc content of the dust is 15 - 20% of the total volume. It can be marginally profitable with lower levels of zinc. Other metals such as chromium and nickel can also be reclaimed and sold. After the heavy metals have been removed, the dust is composed primarily of iron and iron oxides and may be remelted. If the metal content is sufficient, the dust can be reused in the blast furnaces. If it is not sufficient, the dust can be sold to other industries for use as raw materials in bricks, cement, sandblasting or fertilizers.

Pollution Sources and Prevention from Steel Forming

The primary wastes produced in the metal forming process include contact water, oil, grease, and mill scale. All are collected in holding tanks. The scale settles out and is removed. It can be reused in sintering plants or, if the metal content is sufficient, may be sold as a raw material elsewhere. The remaining liquid leaves the process as waste treatment plant sludge. As the waste results in a small portion of pollution produced by steelmaking, pollution prevention and process modification opportunities are not a priority.
Steel is usually made in a two-step, or "indirect" process. In the first step, Iron oxide is reduced with carbon + carbon monoxide at high temperatures forming crude molten iron, which is known as pig iron. Due to it's solubility in liquid iron, pig iron contains a large amount of carbon (>4%), as well as unacceptable amounts of impurities like sulfur, silicon, and phosphorus; which makes it brittle as glass and useless. So, technically steel is made by *removing* carbon from iron, not by *adding* it! In order to remove the excess carbon and impurities from iron, the Basic Oxygen Process is used. This is fairly straightforward. The molten steel is poured into a special basic oxygen converter. A fluxing material, usually calcium oxide (aka quicklime) is added. Then pure oxygen is blown through the molten iron. Because carbon and impurity elements have a higher affinity for oxygen than does iron, those elements are oxidized and combine with the flux, forming slag, while the iron stays mostly unreacted. By reducing the amount of carbon the pig iron is converted into steel. For carbon, the reaction is the same as simple burning. C(dissolved) + O2 -----> CO2(gas). The silicon reacts in a similar way to carbon: Si(dissolved) +O2 ----> SiO2 In the case of sulfur, I believe the reaction is also similar: S(dissolved) + O2 ----> SO2(gas). Some of the SO2 gas simply bubbles out of the iron along with the CO2 gas. The rest reacts with the calcium oxide flux and more oxygen to form calcium sulfate. 2SO2(gas) + 2CaO + O2(gas) -----> 2CaSO4. Other methods can be used to remove sulfur. One common method is pre-treat the steel by adding a certain amount of powdered magnesium metal before the oxygen treatment. The magnesium reacts vigorously with the sulfur forming magnesium sulfide: S(dissolved) + Mg -----> MgS.

The sulfide floats to the top and combines with the flux. This is more efficient at "scavenging" sulfur than simply burning it off with the oxygen. In the case of phosphorus: 4P(dissolved) + 3O2 ----> P4O6; the phosphorus oxide also reacts with the flux forming calcium phosphate. P4O6 + 4CaO -----> 4CaPO4.

The conventional route for making steel consists of sintering or pelletization plants, coke ovens, blast furnaces, and basic oxygen furnaces. Such plants require high capital expenses and raw materials of stringent specifications. Coking coal is needed to make a coke strong enough to support the burden in the blast furnace. Integrated steel plants of less than one million tons annual capacity are generally not economically viable. The coke ovens and sintering plants in an integrated steel plant are polluting and expensive units. Direct-reduced iron (DRI), also called sponge iron,[1] is produced from direct reduction of iron ore (in the form of lumps, pellets or fines) by a reducing gas produced from natural gas or coal. The reducing gas is a mixture majority of hydrogen (H2) and carbon monoxide (CO) which acts as reducing agent. This process of directly reducing the iron ore in solid form by reducing gases is called direct reduction. The conventional route for making steel consists of sintering or pelletization plants, coke ovens, blast furnaces, and basic oxygen furnaces. Such plants require high capital expenses and raw materials of stringent specifications. Coking coal is needed to make a coke strong enough to support the burden in the blast furnace. Integrated steel plants of less than one million tons annual capacity are generally not economically viable. The coke ovens and sintering plants in an integrated steel plant are polluting and expensive units.

Contents
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1 Process 2 Problems 3 History 4 Uses 5 See also 6 References 7 External links

[edit] Process
Direct reduction, an alternative route of iron making, has been developed to overcome some of these difficulties of conventional blast furnaces. DRI is successfully manufactured in various parts of the world through either

natural gas or coal-based technology. Iron ore is reduced in solid state at 800 to 1,050 C (1,472 to 1,922 F) either by reducing gas (H2+CO) or coal. The specific investment and operating costs of direct reduction plants are low compared to integrated steel plants and are more suitable for many developing countries where supplies of coking coal are limited. The direct reduction process is intrinsically more energy efficient than the blast furnace[citation needed] because it operates at a lower temperature, and there are several other factors which make it economical:
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y y y y

Direct-reduced iron has about the same iron content as pig iron, typically 90 94% total iron [2] (depending on the quality of the raw ore) as opposed to about 93% for molten pig iron, so it is an excellent feedstock for the electric furnaces used by mini mills, allowing them to use lower grades of scrap for the rest of the charge or to produce higher grades of steel. Hot-briquetted iron (HBI) is a compacted form of DRI designed for ease of shipping, handling, and storage.[2] Hot Direct Reduced Iron (HDRI) is iron not cooled before discharge from the reduction furnace, immediately transported to a waiting electric arc furnace and charged thereby saving energy. The direct reduction process uses pelletized iron ore or natural "lump" ore. One exception is the fluidized bed process which uses (requires) sized iron ore particles. Select few ores are suitable for direct reduction. The direct reduction process can use natural gas contaminated with inert gases, avoiding the need to remove these gases for other use. However, any inert gas contamination of the reducing gas lowers the effect (quality) of that gas stream and the thermal efficiency of the process. Supplies of powdered ore and raw natural gas are both available in areas such as Northern Australia, avoiding transport costs for the gas. In most cases the DRI plant is located near natural gas source as it is more cost effective to ship the ore rather than the gas.

India is the worlds largest producer of direct-reduced iron, a vital constituent of the steel industry.[3] Many other countries use variants of the process, so providing iron for local engineering industries.

[edit] Problems
Directly reduced iron is highly susceptible to oxidation and rusting if left unprotected, and is normally quickly processed further to steel.[citation needed] The bulk iron can also catch fire since it is pyrophoric.[4]

[edit] History
Main article: Bloomery

Producing sponge iron and then working it was the earliest method used to obtain iron in the Middle East, Egypt, and Europe, where it remained in use until at least the 16th century. There is some evidence that the bloomery method was also used in China, but China had developed blast furnaces to obtain pig iron by 500 BCE. The advantage of the bloomery technique is that iron can be obtained at a lower furnace temperature, only about 1,100C or so. The disadvantage, relatively to using a blast furnace, is that only small quantities can be made at a time.

[edit] Uses
Sponge iron is not useful by itself, but can be processed to create wrought iron. The sponge is removed from the furnace, called a bloomery, and repeatedly beaten with heavy hammers and folded over to remove the slag, oxidise any carbon or carbide and weld the iron together. This treatment usually creates wrought iron with about three percent slag and a fraction of a percent of other impurities. Further treatment may add controlled amounts of carbon, allowing various kinds of heat treatment (e.g. "steeling"). Today, sponge iron is created by reducing iron ore without melting it. This makes for an energy-efficient feedstock for specialty steel manufacturers which used to rely upon scrap metal