Steel and Metallurgical Products Wan a * Iron corrodes under drop of water because the covered area is deoxygenated, » major cause of rusting is differential aeration. > 20.5.6, Film Distribution Theory of Corrosion ording to this theory exceedingly thin films of oxides are formed by air on the and these oxides films are generally formed at cathodic areas and are not Continuous films, When immersed in water, these films form secondary hydroxides films Which are also formed at the original cathodic areas and are spread out. Corrosion take Place where these secondary hydroxide films are not formed and so corrosion is controlled by these secondary hydroxide fils 20.6. STEEL AND I'TS MANUFACTURING Stel is an alloy of iron with carbon and traces of manganese, sulphur, silicon and Phosphorus. “An alloy is a homogenous mixture of two or more elements with metallic Properties’. The physical, chemical and mechanical properties of metals are changed by making alloy e.g. stainless steel is corrosion resistant alloy of iron. Sometimes other elements like Cr, Ni, Sn, V, Mo and Mn are also added to achieve special properties in steel. — Composition of Steel 1, Iron, base metal which oxidizes and corroded rapidly. 2. Cas an additive (0.25-2.5%) as FesC cementite), 3. Trace amount of other elements like * Sulphur, phosphorus (< 0.05%) * Mn added during manufacturing as deoxidizer to reduce any FeO. * Si (0.15-0.35%) as FeSi Steel Manufacturing The carbon content in steel is greater than that it is in wrought iron and smaller than in the cast iron. So, steel can be manufactured either by removing a part of carbon content from cast iron or adding some carbon to wrought iron. Various methods of making 1. Cementation Proces: It is an old process. This process consists of heating the iron rods with carbon in the form of charcoal until the carbon penetrates into iron to form steel ee carried out in of stone and the pots are heated by direct heating. The r ataiie aout 1000%C. The process takes about 10 days for completion. resulting steel is known as blister steel which is further heated to red hot and bars tied together and hammered to get shear steel. In this manner steel of isobtained, 4 metal suri462_ Applied Chemistry In this manufacturin, 8, low pho: Process acid. While, sphorus (below 0.09%) pig iron is treated by Bessemer high phos Bessemer process ti phorus (more than 1.5%) pig iron is treated in basic sae Process. In both the Processes steel is made by first blowing cold air through fmulters®, wo" At about 2 atmospheric preasure, oxidizing the impurities and simultaneously Converting pig iron to steel. The process basically differs in the use of 8 of the convertor. ‘d furnace about 6 m high and 3 m in diameter. It is ned inside with silica or magnesia (MgO), depending Present in the pig iron. If the impurities present in the Pig iron are basic, e.g. manganese, a lining of silica brick is used and the process is known as Acid Bessemer Process. If impurities are acidic e.g. sulphur, phosphorus ete. a basic lining of lime (CaO) or magnesia (MgO) is used in the converter and process is known as Basic Bessemer process. The capacity of the converter is from 10-25 tonnes of charge at a time. The converter is mounted on a shafts, one of which is hollow and serves as a wind pipe and upon-which the converter can rotate at any position. The converter is also provided with a number of holes at the bottom through which a hot blast of air can be introduced. acid and basic refractory lining The converter is a pear shape made of steel plates and is li upon the nature of impurities Burning Carbon Mionoxide’Steel and Metallurgical Products 4. Carbon is oxidized to CO which burns with a blue flame at the mouth of converte, ti When the flame dies out, it indicates the complete oxidation pees ea aes Similarly, in Basic process, phosphorus is slagged off as calcium phosp as Thomas slag. 4P + 502 — 2P205 Or Pao 6Ca0 + PsOi) ———> 2Cas(PO,)2 (Thomas slag) After complete oxidation of impurities, Spiegeleisen (an alloy of iron, Mn and carbon) is added and the blast of air continued for a short period to effect thorough mixing. Mn and C acts as deoxidizer in the first instance and reduce any FeO may be Present, The excess of Mn and carbon dissolve in the molten metal, the carbon being the necessary constituent of steel and Mn makes it harder and also increases the tensile strength. Sometimes a small and calculated amount of ferro-silicon and aluminium is added to finish product. It serves as scavenger and reduces any CO dissolved in the metal carbon, thereby producing steel which is free from enclosed bubbles of the gas called blow holes. Al also removes nitrogen forming aluminium nitride. The scavenger elements get oxidized and separated as slag. The slag is held back by a skimmer and Finished Steel is then transferred to a bucket shaped refractory lined steel shell with a hole at-the bottom through which molten metal is allowed to flow into the molds. When the ingots have cooled sufficiently, these are reheated and rolled to various shapes and sizes. After the removal of steel, the converter is turned bottom up so that slag drops into buggies and is removed and disposed. However, in spite of simplicity, Bessemer process involve lose of ‘heat as well as high content of N in end product. 4 Linz Donawitz (Id) Process This process was developed in Australia in 1951 and is used in many places throughout the Asia, Europe and other Places. This is a modification of Basic Bessemer Process. The converter has a basic lining of tarred magnesite (MgCO;). The converter hhas no tuyeres, as the molten charge is treated with high purity oxygen (99.5-99.7%) stream at a pressure of 150 psi which comes from the top of the converter through a water cooled ing in a nozzle. The converter is brought to the charging position for the introduction of charge i ig i i Pressure of 150 psi at a supersonic velocity surface of hot metal. The jet of oxygen at a high pressure strikes the surface of iron and creates intense heating rising the hot spot to a very high temperature Oxygen. ging upon the charge rapidly oxidizes carbon, silicon, Mn and P 0 by the formation of slag. Since the purifier metal has allowing unrefined or impure metal to come to the464 Applied Chemistry Gas slag-metal emulsion Hot spot Fig.20.5.Linz-Donawitz converter in steel manufacturing Advantages of the Process . The steel obtained by this process is better than obtained by basic Bessemer process, because of low FeO and Ne contents. Better control of temperature and composition in the furnace. It requires low energy. * Greater variety of products can be manufactured. 5. Open Hearth Process The open hearth process is based on the regenerative. principle of heat economy proposed by William Siemens (1857). This process is also of two types: * Acid Open Hearth Proce Ek Basic Open Hearth . E hearth is lined inside lining material dependsSteel and Metatturgica: Proditciaamm Alternate burner Checker chamber Slag pot Steelladle — Checker chamber Fig.20.6.Open hearth process The iron is placed in the hearth H and the producer gas is passed through the generator Gi which is previously heated and air is passed through the generator Gz which is also heated. Thus during the first phase of cycle, producer gas and air are separately Passed through previously heated generator or chambers Gi and Gz, while the products of combustion flow through the checker work Ga and Gx, The combustion takes place rapidly because the gasses are reheated to high temperature. Subsequently the cycle is reversed 0 flue gasses are passed through Gi and Gz and air and producer gas are being preheated in Gs and Gs respectively. In this way cycle is repeated in an alternative manner. Every few minutes the direction of gases is reversed so incoming gases are always preheated Due to the burning of producer gas, charge-melts and impurities of S, P, Si, and C are oxidized by haematite. 4Fe + 3SOQ2 (S removed) 10Fe + 3P20s 4Fe + 3Si02. 2Fe + 3Mn0 - ___ 4Fe + 3COz (Carbon removed) _ Cas(PO.)2( Phosphorus removed) _ CaSiOs (Silicon removed) a psc _ (Mn removed) " 2Fe203+3Stat steer ast semen” There is a be 6. Electrical Furnace Method In this process, the steel i temperature without tter control of composition and temperature in the furnace. 8 obtained by heating the materials to a very high high purity and nr 7usine the undesired impurities. Thus steel obtained is of Steel obese than the steel obtained by Bessemer and open hearth Process. Steel obtained by this Process is free from S, P and gas bubbles and contains fe non-metallic impurities. The heating is done in arc furnace to facilitate Tapid steel production. Furnaces are of two types: © Are Furnace * Induction furnace In the case of arc furnace, the arc can be between two between carbon and molten charge. In th of induction, currents. One commonly used arc furnace is Heroult Arc F S-phase single transformer type furnace. The furna lining. The basic lining permits the use of the basi removal of sulphur and phosphorus while, the acidic lining is asso does not remove the S and P. The furnace is provided with one c hole. The graphite or baked carbon electrodes are commonly used the electrodes and surface of the charge may be adjust to get desired tempe: The charge is usually scrap steel but also contains cast iron, pig iron ( open hearth process) or iron ore mixed with requisite amount of lime. The char; in between the electrodes. When is furnace has charged, current is passed and as an arc is produced. The high temperature of the arc melts the charge and forms a molten metal. The added lime and ore breakdown and remove the oxidisible such as C, Mn, S etc. Excess carbon in the iron is also oxidized to CO. Coke also reacts with lime to form the calcium carbide. Sample of slag taken out which liberates acetylene gas when reacted with water (if calcium carbide is present). Small amount of ferro- manganese, ferro-silicon etc. are added as oxidizer. These ignots are then worked to give” various size and forms by mechanical working that may be cold working (at room temperature) or hot working (at high temperature). ‘The metal from the furnace can also be worked in following manner. The slag is first removed by tilting the furnace and molten steel is covered with a mixture of lime, cand and coke. This mixture metlts into reducing slag which contains calcium silicates or carbide, The slag oxidizes the steel by withdrawing g oxygen from FeO dissolve in the eee izer, such as calcium silicate or Al-silicon may be added.Steel and Metallurgical Products 467 Deoxidation and Desulphurisation 1 th After the removal of the slag, mixture of lime, sand and fluorspar, along with some coke and ferro-silicon is added to the furnace. The added coke removes FeO by reducing it to Fe. FeO +C ee Fe + OO Sulphur present in FeS is removed as CaS. FeS + CaO ——m> FeO + CaS FeO thus formed is reduced to Fe as above. After the removal of sulphur the steel is tapped off from the furnace and converted into ingots. 7. Duplex Process The combination of Bessemer and open hearth process is known as duplex process. The high phosphorus pig iron can be treated by basic Bessemer process. Similarly, pig iron containing less than 1.5% of P cannot be treated by same process because it is the minimum requirement for the basic Bessemer process. So, open hearth process is applied for this charge. To convert this pig iron in steel in half time, the molten pig iron is first treated in an acid Bessemer converter to remove Si, Mn and a part of carbon. The molten iron than transferred to basic hearth furnace to remove P and remaining C. In this method, carbon content is eliminated upto 0.03%. Silicon is almost removed completely. Mnia partially removed. However, P and § are not eliminated. The liquor or melted metal is collected in a mixture and charged in the basic open hearth together with the requisite amount of flux and ore. The removal of S and P by this process has already discussed. 20.7. HEAT TREATMENT OF THE STEEL Heat treating (or heat treatment) is a group of industrial and metalworking processes used to alter the physical and sometimes chemical properties of a material. T! extreme hardness of high carbon steel is modified by these processes. It is the process in which steel is heated and cooled under carefully controlled conditions in such a manner that the physical properties of steel are modified without any change in chemical composition. The heat treatment causes:> Toughness of steel is enhanced | 20.7.2, Annealing | Annealin & involves treating steel up to a high temperature, and then cooling it the resulting microstructure will p high arden There are two types of annealing. These are annealing and full or high tempgrature annealing. In the Process or low temperature annealing, the steel is heated tot temperature fase the critical point and then cooled slowly. ‘This process increases the ductility as well as shock resistance but decreases the hardness of steel. In full or high temperature annealing, steel is heated to temperature about 30°- 50°C above the upper critical temperature and then cooled gradually to room temperature. The approximate critical temperature of > Mild steel 840-870°C » Medium carbon steel —-780-840°C > High carbon steel 760-780 C Annealing is performed by heating a component to the appropriate temperature, soaking it at that temperature, and then shutting off the furnace while the piece is in it. Steel is annealed before being processed by cold forming, to reduce the requirements of load and energy, and to enable the metal to undergo large strains without failure. 20.7.3. Quenching and Hardening Quenching is a process of cooling a metal at a rapid rate. In ferrous alloys, this will often produce a harder metal, while non-ferrous alloys will usually become softer than normal. To harden by quenching, a metal (usually steel or cast iron) must be heated above the upper critical temperature and then quickly cooled. Depending on the alloy and other considerations (such as concern for maximum hardness vs. cracking and distortion), cooling may be done with forced air or other gases, (such .as nitrogen). Liquids may be used, due to their better thermal conductivity such as oil, water, a polymer dissolved in water, or a brine solution. It is very important to know about the critical temperature, because it is not same in case of metals. If steel is heated to unduly high temperature and then quenched, brittleness will be in the material and internal stress created. Main function of hardening and quenching is to increase the hardness and abrasion resistance of the steel. The greater rate of cooling the harder will be the steel. Low carbon steel can be hardened or quenched the steel causes » Increase in resistance towear » Makes steel capable of cutting other metals og An increase in strength = 20.7.4. Tempering e Tempering ughness, but low hardni Process or low temperatureSteel ana Meran™ 469 B and ductility gets increaseg ardness are lowered and increased the length and hardness correspondingly 20.7.5, Case Hardening In this process a hard wearing sur carburizing and quenching in water from the tempe carried out. Case hardening is applied for low’ carbon ste‘ the process of quenching. ‘The parts which are to be case containing carburizing material (material rich in carbon), such ¢ areal and a temperature of 900-950°C. The parts are allowed to remain at this temperature the sufficient time (according to the depth of hardening required. So that carbon is absorbed to the require depth. The article is then allowed to cool slowly with in the outer skin of the article is converted into high carbon steel, containing about 0.8-1.2% carbon. Carburized article is reheated to about 900°C and then quenched in oil. As a result, brittleness obtained and the core becomes tough and soft. The article is reheated to about 700°C and quenched so that outer casting, which had been rendered soft during the preceding operation, gets hardened. Regenerative quenching is carried out for refining the carburized parts. This consists in double casing, one for the refinement of the case and the other of the refining of core. 20.7.6. Flame Hardening : It is a type of localized hardening and consists in heating an area to the hardened by the means oxy-acetylene or oxy-hydrogen flame, followed by abrupt cooling by water. The hardened depth is easy to control by adjusting the time of heating, temperature of flame and water spray. 20.7.7. Nitriding This process is used for obtaining super hard surfaces and generally employed effectively in the case of alloy steels. The process consists in heatirig the metal alloy in the presence of ammonia at a temperature of 340-350°C, Nz formed as a result of dissociation is produced on mild steel by surface ature at which processing has been ‘ols, which cannot be produced by hardened are encloSed in a cast fh as small piece of charcoal of NHs, reacts with the consequents of the surface of the alloy and forms extremely hard nitrides, 20.7.8, Cyaniding : This is a type of case-hardening process in which a layer of hard surface is produced in low or medium carbon steels by immersing the metal in a molten salt ning KCN or NaCN at a temperature of about 870°C and then quenched in water oree ae ee ay eo a also Be When cold (cold short). The tensile strength in steels having tonnes peng eins, from 0.2% to 1%, varies almost uniformly from 30 tonnes to 60 We stron tp nct: But above:1% carbon content, the tensile strength decreases, The tensile strength of pure iron is 22 tonnes per sq, inch and that of steel having 0.1% carbon is 25 tonnes per sq. inch, According to the percentage of carbon, steels are of three types: (a) Hypoeutectoid steels, having carbon contents below 0.8%. (b) Eutectoid steels, having carbon contents Just 0.8%. (¢) Hypereutectoid steels having carbon percentage between 0.8 1.7% 20.8.2. Alloy Steels Addition of small amounts of certain metals, such as Ni, Cr, Mo, Mn, Si, V and Al Special properties on steel considerably altering the hardness, tensile strength, resistance to corrosion and coefficient of expansion etc. Such products are, known as special steel, or alloy steels and find extensive use in industry. When alloy steel is to be made, calculated amount of one or more ferro alloys (Ferro-manganese, Ferro-silicon, Ferro-chromium etc.Jare added 20 minutes before tapping the molten steel from the furnace. Deoxidizers are added after the addition of ferro-alloys. Tapping is done carefully so that slag may not pass into the metal. Finally the ingots are made. Alloy steels containing 5% or less of alloying elements are prepared in the open hearth furnace, while those containing more than 5% of alloying elements are prepared in electric arc furnace. Although a large number of elements, such as He, Os, N: Ti, Ca, Cu, Sn, Te, Ba, As, Zn, Mo, Mn, Cr, Ni, W, V and Si ete. have been used as alloying elements, but more important alloying elements are Ni, Cr, Mo; Ma, Si, V and Al. Out of these, some elements increase corrosion resistance, some increase hardness, some are helpful in retaining the ‘hardness at elevated temperatures, while some of them are helpful in making of electromagnets. Alloy steels may be high carbon as-well as low carbon. In the manufacture of alloy steels, Ni and Code usually added as single metals, while other elements are added as ferro alloys (alloy of iron with large. ofalloying element). = Pek © alana ert arene ae, too he eee conferSteel and Metallurgical Products 471 hardenability of steel. Aluminium controls grain growth. It is used in amounts varying from 0.90%-1.5% in nitriding steels in which the surface is hardened as a result of the formation of hard and stable nitride of aluminium. For developing the mechanical properties, alloy steels are subjected to hammering, pressing or rolling. The aim is to secure fine uniform grain. This is achieved by forging or rolling above the critical temperature (hot worked). As a result, mechanical properties are greatly improved because of refining of crystal-line structure. The pressed sections may also be heat treated inorder to gain a uniform diffusion of carbon and fine grain structure. The heat treatment includes annealing, hardening by quenching, tempering and surface hardening. Low alloy high strength engineering steels contain small amounts of one or-more of alloying elements, such as Ni, Cu, Cr, Mn, Si, Mo, V, Al, Zr ete. Table20.1. Function of Alloying Elements Element Influence on properties Uses of alloys 1. Nickel Fine grains are produced. Coefficient. | For Balance wheels of expansion decreases and corrosion resistance increases. aes 2. Chromium Tensile strength, depth hardening and | For surgical instruments. resistance to.corrosion are increased. _| cutlery, connecting rods etc. 3. Manganese Hot shortness is removed and | For grinding wheels, steering resistance to abrasion is increased. Tensile strength and resistance to abrasion are increased. Reversible spindles and rails. For axles, crank pins, heavy locomotive forgings, piston 4. Vanadium stresses are produced. rods etc. 5. Molybdenum Cutting hardness at high temperature For high speed tools is increased because phases are} _ stabilized. 6. Tungsten Magnetic retentivity as well as cutting | For cutting tools, permanent hardness are increased. Grain | magnets ete. structure is refined. 7. Nickel and | Increase in corrosion resistance and | For making stainless steels. chromium tensile strength 20.8.3. Stainless Steel Stainless steel is a term applied to those iron base alloys which are characterised by their pronounced: resistance to corrosion. These are usually prepared by adding chromium or a combination of chromium and nickel. Stainless steels are oxidisable only to a slight extent and an impervious coating of oxide formed on the surface prevents further progress of the corrosive action. The thickness of the oxide layer is so minute that it does hot affect the colour and appearance of the surface. Stainless steels are usually produced in electric arc furnace. Now rare earth elements in the form of misch metal have been used in the manufacture of stainless steels. ‘There are three types of stainless steels: | ae ( Martensitic stainless steels- The composition of these steels is: Cr 12-17%6, upto 1.2%. These are ferromagnetic and hardened by heat treatment. They ae Tesistant to corrosion by water, weather and chemicals. These are widely used for cutlery and suitable for applications where high strength, hard-ness, resistance to corrosion and abrasion are required.Ferritic stainless steely. 0.25%. These steels are ‘The composition of thos ia; Crx1B-20% and carbon up to Tesistant to corrosion a» well ax oxidation at very bigh temperatures. They are fabricated (not heat treated) by forming, spinning or drawing. These are used for structural purposes, Austenitic stainless steels- The composition of this type of steel is Or--8-20%, Ni=6-20%. They have high ductility and work hardenability. They axe corrosion - resistant and scaling resistant even at very high temperatures. They are tough and can not be hardened by heat treatment, Stainless stecl with the composition C=up to 0.15%, Cr=17-19%, Ni=8-10%, Mn=up to 2% and upto 1% are used in petroleum equipment, food processing equipment, utensils, cvunters and sinks, laundry equipment, flat and hollow wares and low temperature processing equipment etc. Magnetic alloys supply hard as well as soft permanent magnet materials. Co, W and Cr added to carbon steel give perma nt magnet materials. Steel with 35% cobalt is also used as permanent magn 1 Soft mag mostly silicon steels. Silicon decreases eddy current losses and in’ resistivity of steel. QUESTIONS What is metallurgy? Disous its signific What are different ores of iron? Disc’ Write’a detailed note on manufacturing of What is rusting of iron? Discuss various theorie What is steel? Give a brief account of its manuf: How would you classify steel? Write various alloy turil REFERENCES Groggins, P. H. 1995. Unit Processes in Organic Sy Book Company, New York, USA. Sharma, B. K. 2011. Industrial Chemistry, 16% Ed., GEOL Meerut, India. McCab W. et al., 1995. Unit Operations of Chemical E: McGraw-Hill Book Company, New York, USA. Sharma, B. K. 2011. Industrial Chemistry, 16th Ed., GEOL Pu Meerut, India. Austin, G. T. 1984. Shrevie's Chemical Process Indi 1S 5 ad. aw-Hill Book Company, New York, USA. : eee ee eee