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Steel-making processes

Abstract: Steel is made by the Bessemer, Siemens Open Hearth, basic oxygen furnace, electric arc, electric high-frequency and crucible processes. In both the Acid Bessemer and Basic Bessemer (or Thomas) processes molten pig iron is refined by blowing air through it in an egg-shaped vessel, known as a converter, of 15-25 tonnes capacity. In the Siemens process, both acid and basic, the necessary heat for melting and working the charge is supplied by oil or gas. Both 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. The high nitrogen content of Bessemer steel is a disadvantage for certain cold forming applications and continental works have, in recent years, developed modified processes in which oxygen replaces air. Steel is made by the Bessemer, Siemens Open Hearth, basic oxygen furnace, electric arc, electric high-frequency and crucible processes. Crucible and high-frequency methods The Huntsman crucible process has been superseded by the high frequency induction furnace in which the heat is generated in the metal itself by eddy currents induced by a magnetic field set up by an alternating current, which passes round water-cooled coils surrounding the crucible. The eddy currents increase with the square of the frequency, and an input current which alternates from 500 to 2000 hertz is necessary. As the frequency increases, the eddy currents tend to travel nearer and nearer the surface of a charge (i.e. shallow penetration). The heat developed in the charge depends on the crosssectional area which carries current, and large furnaces use frequencies low enough to get adequate current penetration. Automatic circulation of the melt in a vertical direction, due to eddy currents, promotes uniformity of analysis. Contamination by furnace gases is obviated and charges from 1 to 5 tonnes can be melted with resultant economy. Consequently, these electric furnaces are being used to produce high quality steels, such as ball bearing, stainless, magnet, die and tool steels.

Figure 1. Furnaces used for making pig iron and steels. RH side of open hearth furnace shows use of oil instead of gas Acid and basic steels The remaining methods for making steel do so by removing impurities from pig iron or a mixture of pig iron and steel scrap. The impurities removed, however, depend on whether an acid (siliceous) or basic (limey) slag is used. An acid slag necessitates the use of an acid furnace lining (silica); a basic slag, a basic lining of magnesite or dolomite, with line in the charge. With an acid slag silicon, manganese and carbon only are removed by oxidation, consequently the raw material must not contain phosphorus and sulphur in amounts exceeding those permissible in the finished steel. In the basic processes, silicon, manganese, carbon, phosphorus and sulphur can be removed from the charge, but normally the raw material contains low silicon and high phosphorus contents. To remove the phosphorus the bath of metal must be oxidised to a greater extent than in the corresponding acid process, and the final quality of the steel depends very largely on the degree of this oxidation, before deoxidisers-ferromanganese, ferro-silicon, aluminium-remove the soluble iron oxide and form other insoluble oxides, which produce non-metallic inclusions if they are not removed from the melt: 2Al + 3FeO (soluble) ↔ 3Fe + Al2O3 (solid) In the acid processes, deoxidation can take place in the furnaces, leaving a reasonable

of 15-25 tonnes capacity (Fig.g. The time for working a charge varies from about 6 to 14 hours. such as large forging ingots and ball bearing steel.5-2% phosphorus in the basic process is normally necessary to supply the heat. two on each side of the furnace. a cheap class of steel. To promote the oxidation of the impurities iron ore is charged into the melt although increasing use is being made of oxygen lancing. 1). mainly due to economic factors which in turn has been ousted by the basic electric arc furnace coupled with vacuum degassing. to 200 tonnes for tilting furnaces (Fig. The Basic Bessemer process is used a great deal on the Continent for making. which is therefore dependent on the composition of the raw material for its heat: 2% silicon in the acid and 1. The introduction of vacuum degassing hastened the decline of the acid processes. leaving only a short time for the deoxidation products to be removed. both acid and basic. the necessary heat for melting and working the charge is supplied by oil or gas. 1). For these reasons acid steel is considered better than basic for certain purposes. takes about 25 minutes and such a short interval makes exact control of the process a little difficult.time for the inclusions to rise into the slag and so be removed before casting. together with lime in the basic process. The oxidation of the impurities raises the charge to a suitable temperature. alternatively heated by the waste gases. But the gas and air are preheated by regenerators. The furnaces have a saucer-like hearth. ship plates. from a very suitable pig iron. The raw materials consist essentially of pig iron (cold or molten) and scrap. with a capacity which varies from 600 tonnes for fixed. deoxidation is rarely carried out in the presence of the slag. The Basic Open Hearth process was used for the bulk of the cheaper grades of steel. but . Bessemer steel In both the Acid Bessemer and Basic Bessemer (or Thomas) processes molten pig iron is refined by blowing air through it in an egg-shaped vessel. Whereas in the basic furnaces. known as a converter. e. and control is therefore much easier than in the case of the Bessemer process. brick and space alternating. The "blowing" of the charge. The regenerators are chambers filled with checker brickwork. which causes an intense flame at the mouth of the converter. Deoxidation of the metal frequently takes place in the ladle. Open-hearth processes In the Siemens process. otherwise phosphorus would return to the metal. The raw material is usually melted in a cupola and weighed amounts charged into the converter. The Acid Bessemer suffered a decline in favour of the Acid Open Hearth steel process. structural sections. in which the air impinges on the surface of the metal from side tuyeres instead of from the bottom. For making steel castings a modification known as a Tropenas converter is used.

Usually. Oxygen lancing is often used for removing carbon in the presence of chromium and enables scrap stainless steel to be used. 2b). Electric arc process The heat required in this process is generated by electric arcs struck between carbon electrodes and the metal bath (Fig.01-0. in recent years.0020. . heatresisting and high-speed steels. Oxygen processes The high nitrogen content of Bessemer steel is a disadvantage for certain cold forming applications and continental works have. This process is used extensively for making highly alloyed steel such as stainless.there is a growing tendency to replace the OH furnace by large arc furnaces using a single slag process especially for melting scrap and coupled with vacuum degassing in some cases. A second limey slag is used to remove sulphur and to deoxidise the metal in the furnace.002%). 1). a charge of graded steel scrap is melted under an oxidising basic slag to remove the phosphorus. A further modification of the process is to add lime powder to the oxygen jet (OLP process) when higher phosphorus pig is used.008% in open hearth steels. Figure 2. High quality steel is produced with low hydrogen and nitrogen (0. In Austria the LID process (Linz-Donawitz) converts low phosphorus pig iron into steel by top blowing with an oxygen lance using a basic lined vessel (Fig. To avoid excessive heat scrap or ore is added. The impure slag is removed by tilting the furnace. developed modified processes in which oxygen replaces air. so long as gas absorption due to excessively high temperatures is avoided.25% compared with about 0. The nitrogen content of steels made by the Bessemer and electric arc processes is about 0. This results in a high degree of purification and high quality steel can be made.

the large surface to mass ratio provided in this way giving extremely rapid chemical refining and conversion to steel. S. which are quite competitive with open hearth quality. FOS process. This problem . The use of oxygen allows the simultaneous removal of carbon and phosphorus from the (P. ladle. Pb. reduces metal oxides by the C – O reaction and eliminates the oxides from normal deoxidisers and allows control of alloy composition to close limits. Figure 3. Fig. 2a). Cu. Sb). mould and circulation (e. The German Rotor process uses a rotary furnace with two oxygen nozzles. Al. The aircraft designer has continually called for new alloy steels of greater uniformity and reproducibility of properties with lower oxygen and sulphur contents.The Kaldo (Swedish) process uses top blowing with oxygen together with a basic lined rotating (30 rev/min) furnace to get efficient mixing (Fig. 1. The use of oxygen with steam (to reduce the temperature) in the traditional basic Bessemer process is also now widely used to produce low nitrogen steel. 3.g. and spray steelmaking which consists in pouring iron through a ring. one in the metal and one above it (Fig. The vacuum largely removes hydrogen. the periphery of which is provided with jets through which oxygen and fluxes are blown in such a way as to "atomise" the iron. These new techniques produce steel with low percentages of N. DH and RH) degassing methods. Complex alloy steels have a greater tendency to macro-segregation. Other processes which are developing are the Fuel-oxygen-scrap. atmospheric and volatile impurities (Sn. Some 14 processes can be grouped as stream. Lime and ore are added. and considerable difficulty exists in minimising the non-metallic inclusions and in accurately controlling the analysis of reactive elements such as Ti. Bearing steels have greatly improved fatigue life and stainless steels can be made to lower carbon contents. The clean metal produced is of a consistent high quality. Methods of degassing molten steel Vacuum melting and ESR. with good properties in the transverse direction of rolled products. B.85%) pig iron. P. 2c). Vacuum degassing is also gaining ground for special alloys.

The improvement of steel cleanliness has therefore become a more and more important subject in the . Figure 4. toughness and freedom from hydrogen and tramp elements. uniformity of properties. such as phosphorus.led to the use of three processes of melting. 5). 4) originally used for titanium. sulphur. Pure materials are used and volatile tramp elements can be removed. nitrogen. re-melts a preformed electrode of alloy into a water-cooled crucible. (c) Electroslag refining (ESR) This process. (a) Vacuum induction melting within a tank for producing super alloys (Ni and Co base). Typical vacuum arc remelting furnace Figure 5. The moving parts in aircraft engines are made by this process. hydrogen (including carbon sometimes) and inclusions are very low. total oxygen. in some cases for further remelting for investment casting. which is a larger form of the original welding process. Tramp elements are not removed and lead may be picked up from the slag. This is due to the mode of solidification. the A and V segregates and also the large silicate inclusions. The so-called clean steel generally is the steel in which the content of impurity elements. due to the need for high strength cleanness. Electroslag remelting furnace Clean Steel: Part One Abstract: Steel cleanliness is an important factor of steel quality and the demand for cleaner steels increases every year. was found to eliminate hydrogen. The layer of slag around the ingot maintains vertical unidirectional freezing from the base. (b) Consumable electrode vacuum arc re-melting process (Fig. utilising the electrical resistance heating in a molten slag pool for the heat source (Fig.

total oxygen and inclusions should be as low as possible in order to get good flexibility. but may be less harmful or even useful to another steel grades. Due to the vague nature of the term "clean steel". low total oxygen content and a certain ratio of Ca/S. nitrogen. steel cleanliness depends on the amount. the content of carbon. reduction of area and bendability) Cold forgeability. The demand for better mechanical properties of steels was urging steel producers to improve cleanliness of their final products. and also an important task for the iron and steel producers. hardenability  Strain aging (enhanced). The improvement of steel cleanliness has therefore become a more and more important subject in the development of ferrous metallurgical technology. weldability. secondary metallurgy treatments. Steel cleanliness is an important factor of steel quality and the demand for cleaner steels increases every year. ductility and toughness (lowered)  Dispersion (enhanced).) in steel can have a remarkable influence on steel properties.development of ferrous metallurgical technology. For examples for IF steels. shrouding systems and casting practice. cracking-resistance. hardenability (enhanced)  Temper brittleness  Separation. clean steel requires control of non-metallic oxide inclusions and controlling their size distribution. hydrogen (including carbon sometimes) and inclusions are very low. grain refining (enhanced). etc. In other hands the high quality pipeline steel requires ultra low sulphure. sulphur [S]. Element Form      Mechanical Properties Affected Ductility. phosphorus [P]. O Sulfide and oxide inclusions Solid solution Settled dislocation C. nitrogen [N]. ductility and toughness (lowered)  Precipitation. Charpy impact value. hydrogen [H] and total oxygen (T. total oxygen.and alloy additions. formability. sulphur. secondary work embrittlement Table 1: Influence of typical impurities on mechanical properties As we mentioned before. some authors imply that it is more precise to refer to: • • steels with low levels of solutes as "high purity steels" steels with low levels of impurities that originate from the re-melting scrap as "low residual steels" steels with a low frequency of product defects that can be related to the presence oxides as "clean steels". morphology and composition. fatigueresistance. morphology and size distribution of nonmetallic inclusions. such as tensile strength. It has been well known that the individual or combined effect of carbon [C]. corrosion-resistance. and also an important task for the iron and steel producers. The inclusions generate many defects and many applications restrict the maximum size of inclusions so the size distribution of inclusions in steel products is also important. In order to obtain the satisfactory cleanliness of steel it is necessary to control and improve a wide range of operating practices throughout the steelmaking processes like deoxidant. The control of the elements mentioned above is different for different performance demands. N Pearlite and cementite  Solid solubility (enhanced). perfect surface quality etc. low nitrogen. anisotropy Formability (elongation. For certain applications where . low phosphorus. Also. The so-called clean steel generally is the steel in which the content of impurity elements. nitrogen. toughness. Those impurity elements also vary with different grades of steel. toughness Carbide and nitride precipitates (enhanced)  Embrittlement by intergranular precipitation P Solid solution  Solid solubility (enhanced). Table 1 lists the influence of common steel impurities on steel mechanical properties which means that some element is harmful to certain steel grades. such as phosphorus. high "r" value.O. drawability Low temperature toughness Fatigue strength S.

and casting practices. [N]≤50 ppm. total oxygen is not only needed below 20 ppm.O. nitrogen [N]. T. T.5 ppm T. [N]≤30 ppm [C]≤30 ppm. in steel has to be below 10 ppm and the size of non-metallic inclusions has to be less than 15 µm. T. in order to improve their fatigue-resistance properties.stringent mechanical properties are required the internal cleanliness of steel is very important. T. T. carbon [C].O. [N]≤20 ppm. the absorption capacity of the various metallurgical fluxes. the sulphur [S] content in steel has to be extremely low.O. For ball bearings. Steel cleanliness is controlled by a wide range operating practices throughout the steelmaking processes. and total oxygen (T. Maximum allowed inclusion size Steel product IF steels Automotive and deep-drawing Sheets Drawn and Ironed cans Alloy steel for Pressure vessels Alloy steel bars HIC resistant steel sour gas tubes Line pipes Sheets for continuous annealing Plates for welding Bearings Tire cord Non-grain-orientated Magnetic Sheets Heavy plate steels Wires Maximum allowed impurity fraction [C]≤30 ppm.O.≤40 ppm [C]≤10 ppm.≤30 ppm [N]≤20 ppm [H]≤1. the extent and sequence of secondary metallurgy treatments. Table 2 shows the cleanliness requirements for various steel grades. For sheets for tin plate application. [N]≤40 ppm.≤20 ppm [P]≤70 ppm [H]≤2 ppm.≤30 ppm 100 µm 20 µm 100 µm 15 µm 10 µm Single inclusion 13 µm Cluster 200 µm 20 µm Table 2: Cleanliness requirements for various steel grades As Table 2 shows for sheets used for car body. stirring and transfer operations.O.≤20 ppm [N]≤60 ppm. shrouding systems. . [N]=30-40 ppm. T. These include the time and location of deoxidant and alloy additions. [N]≤40 ppm. For meeting the specification of increasingly improved toughness for petroleum pipeline and of Hydrogen Induced Cracking (HIC) resistance for the transport of sour natural gas.O.≤10 ppm [P]≤50 ppm. A one of the steelmaking process routes for the production of clean steels is outlined in Figure 1.≤15 ppm [N]≤30 ppm [H]≤2 ppm. [S] ≤10 ppm [S]≤30 ppm.O. less than 10 ppm. T.≤10 ppm [H]≤2 ppm.) are each required to be very low. the size of non-metallic inclusions in steel has to be less than 10 μm and even smaller (5 µm) for TV shadow masks. [N]≤50 ppm [C]≤30 ppm.O. For steel cord used in tires. tundish geometry and practices. [N]≤40 ppm.O.O. but the size of the non-metallic inclusions in steel has to be less than 20 µm. T.

According to definition. Controlling inclusions in steel is closely connected with the concept of “clean steel”. play an important role with respect to their effect on the steel properties. The improvement in steel properties by control of non-metallic inclusions plays an important part in defending the applications of steel against newer competitive materials. oxide and sulphide inclusions have been thought harmful for common steels. The type and appearance of these non-metallic inclusions depends on factors such as grade of steel. From the viewpoint of “cleanness” all steels are “dirty”. Among various types of nonmetallic inclusions. secondary metallurgy treatments and casting of steel. Non-metallic inclusions. play an important role with respect to their effect on the steel properties. the non-metallic . since even steel with only 1 ppm each of oxygen and sulfide will still contains 109 -1012 non-metallic inclusions per ton. The improvement in steel properties by control of non-metallic inclusions plays an important part in defending the applications of steel against newer competitive materials. Controlling inclusions in steel is closely connected with the concept of "clean steel". The term steel cleanness is relative one. Generally. The aims of the metallurgist are to eliminate undesirable inclusions and control the nature and distribution of the remainder to optimize the properties of the final product. it is of particular significance to determine how pure the steel is. Because of this. However.Figure 1: The process route for the production of clean steels Clean Steel: Part Two Abstract: Non-metallic inclusions. melting process. which are undesirable components of all steels. non-metallic inclusions in steel normally have a negative contribution to the mechanical properties of steel. some of these inclusions can also have a beneficial effect on steels properties by nucleating acicular ferrite during the austenite to ferrite phase transformation especially in low carbon steels. which are undesirable components of all steels. since they can initiate ductile and brittle facture. Non metallic inclusions in steel are the cause for dangerous and serious material defects such as brittleness and a vide variety of crack formations. All steels contain non-metallic inclusions to a greater or less extent.

MnO.N). They affect on the properties of the final products by their deformation during the steel working process. AlN. tool steels) which have elements with a strong affinity for nitrogen (e.. Cr2O3. TiO2. in liquid steel non-metallic inclusions are in solid or liquid condition. aluminum and tungsten oxides and also crystalline silicates. MgOAl2O3.) Phosphides (Fe3P. by stableness/stability and origin. nitrides are present in special steels (stainless steels. Among various types of nonmetallic inclusions.15% S. According to analysis based on the steel ingots containing 0. cerium etc. FeOCr2O3 etc.) Nitrides (simple: TiN. MgS. chromium. Figure 1: Non-metallic inclusion in steel: oxides-dark gray and sulfides-light gray By mineralogical content oxygen inclusions are divided into the following groups: • • • Free oxides – FeO. As mentioned above the majority of inclusions in steels are oxides and sulfides. Figure 1 shows sulfides and oxides of non metallic inclusion in steel. especially their morphology has a significant effect on the steel properties.) Sulphides (FeS. Al2O3 etc. By chemical content non-metallic inclusions are divided into the following groups: • • • • Oxides (simple: FeO. MnO. compound: Nb(C. Fe2P etc. vanadium. which create nitrides.N) etc. chrome. CaS. Spinels-compound oxides which are formed by bi. 2) Type II has a dendritic structure and is often called grain-boundary sulfide because it is distributed as chain-like formation or thin precipitates in primary ingot grain boundaries. SiO2. Silicates which are presented in steel like a glass formed with pure SiO 2 or SiO2 with admixture of iron. compound: FeSFeO. which can be found in alloyed steels and has strong nitride-generative elements in its content: titanium. the morphology of MnS can be classified into three types: 1) Type I is a globular . ZrN.. Cr2O3. vanadium). Sulfides in steel have been paid much attention because their treatment is an important problem in the steelmaking process. FeOAl2O3. oxide and sulphide inclusions have been thought harmful for common steels. MnSMnO etc.01-0.) The majority of inclusions in steels are oxides and sulphides. manganese. CeN etc. aluminum. .g.inclusions are chemical compounds of metal with nonmetal which are present in steel and alloys like separated parts. MnS. compound: FeOFe2O3. Al2O3 (corundum) etc. Al2S3 etc.and tri-valent elements as a ferrites. Classification of non-metallic inclusions Non-metallic inclusions are divided by chemical and mineralogical content. SiO2 (quartz). V(C.. Depending on the melting temperature. Usually. chromites and aluminates. and is often duplex with oxides.MnS with a wide range of sizes.

Recently. the Widmanstätten plate-like MnS2. . Three regions of strain concentration (red) can be seen and a trihedral void (white region) close to the round inclusion is formed. the sulfides in the modern commercial steel are usually formed on solidification process or in solid steel during the subsequent cooling process. Most of the above mentioned sulfides are formed both during the process of secondary metallurgy or the solidification process. This trend agrees with the existing experimental results.3) Type III is angular sulfide and always forms as monophase inclusion. An attempt by using program ABACUS was performed to model the behavior of slag inclusions and their surrounding matrix material during hot rolling and hot forging of hardenable steels. including the globular duplex oxide–sulfide (particle A. The difference in mechanical properties between the matrix and the inclusion is found to be the primary reason to create a void. Figure 3 shows the effective strain contour during plastic deformation. the continuous casting technology of steels with higher cooling rate than the ingot casting almost replaced the ingot casting. The aims of the metallurgist are to eliminate undesirable inclusions and control the nature and distribution of the remainder to optimize the properties of the final product. the sulfur concentration in steel was lowered drastically. It is shown that it can be helpful for studying the behavior of inclusions. For example. The relative plasticity index of inclusion increases while the rolling temperature rises. Figure 4 shows the effect of rolling temperature on the relative plasticity index during hot rolling of steels. which is difficult or even impossible to obtain from a conventional experiment. Figure 2: Typical duplex oxide–sulfide inclusion (particle A. B and C) and plate-like MnS (particle D) in conventional continuous casting silicon steel. Another interested thing is that two edges of the pore tend to emerge and a bonding is formed. The strain concentrations arise at the inner surface of the matrix. There exists a transition region. is formed in solid steel and Figure 2 shows the common morphology of MnS in conventional continuously casting steel. with the development of steelmaking technology. Also. So. where the relative plasticity index changes rapidly. The weak bonding at the interface between the matrix and the inclusion seems to facilitate to open the void. Numerous examples of the effect of non-metallic inclusions on steel properties show the importance of the behavior of the inclusions as well as of surrounding metal matrix during plastic working of steels. B and C) and the Widmanstätten plate-like MnS (particle D).

Figure 4: Effects of rolling temperature on the relative plasticity index. .Figure 3: Void formation close to the inclusion.

2Al 2O3 compound is first exceeded at 1600°C. The addition of calcium to steel which contains such inclusions changes the composition of these inclusions from pure alumina to CaO-containing calcium aluminates. size and chemical composition of the inclusions it is possible to obtain a final product of good quality. depending on the silicon specification. The control of the formation of non-metallic inclusions and the identification of their constituent phases are of extreme importance for the obtaining of clean steels. The change in inclusion composition and shape is known as the inclusion morphology control. Generally. During calcium treatment. such liquid calcium aluminates may be present in liquid form until. products resulting from reactions between the melt and atmosphere. This treatment is made after trim additions and argon rinsing. The increasing demand in recent years for high-quality steel products has led to the continuous improvement of steelmaking practices. the. i. or refractory (exogenous or macro inclusions). melting point of the calcium aluminates will decrease as the CaO content increases. these alumina inclusions are present in a solid state in liquid steel. inclusions degrade the mechanical properties of the steel and thereby reduce the ductility of the cast metal and increase the risk for mechanical and/or corrosion failure of the final product.. Alumina inclusions occur as deoxidation products in the aluminum-based deoxidation of steel. Oxide inclusions originate from two sources: • • residual products resulting from intentionally added alloying elements to deoxidize the molten steel after oxygen treatment (endogenous or micro inclusions). until liquid oxide phases occur at about 22% of CaO. the alumina and silica inclusions are converted to molten calcium aluminates and silicate which are globular in shape because of the surface tension effect.e. In most melt shops the cored wire containing Ca-Si or Ca-Fe(Ni) injection system is used in the calcium treatment of steel. or even after. slag. As it can be see from Figure 1. the steel solidifies.e. i. inclusions degrade the mechanical properties of the steel and thereby reduce the ductility of the cast metal and increase the risk for mechanical and/or corrosion failure of the final product. Among various types of nonmetallic inclusions. The melting and boiling points of calcium are 839°C and 1500°C respectively.. Through the control of the amount. The liquid phase content continues to increase as CaO content rises further and is 100% at 35% of CaO. The minimum melting temperature for the liquid calcium aluminates is around 1400°C. The presence of non-metallic oxide inclusions is a major cause of incompatibility between the attainable and desirable level of cleanliness in many grades of commercial steel.. There is a special interest in the control of non-metallic inclusions due to their harmful effect on the subsequent stages and their great influence on the properties of the final product. oxide and sulphide inclusions have been thought harmful for common steels. Most grades of steel are treated with calcium using either a Ca-Si alloy or a Ca-Fe(Ni) mixture. .e. Pure alumina has a melting point above 2000°C. i.Clean Steel: Part Three Abstract: The presence of non-metallic oxide inclusions is a major cause of incompatibility between the attainable and desirable level of cleanliness in many grades of commercial steel. Generally. when the CaO.

Figure 1: Binary system CaO-Al2O3 The calcium aluminates inclusions retained in liquid steel suppress the formation of MnS stringers during solidification of steel. i.e. This change in the composition and mode of precipitation of sulphide inclusion during solidification of steel is known as sulphide morphology or sulphide shape control. bloom and slab castings To improve steel machinability at high cutting speeds and prolong the carbide tool life To minimize the susceptibility of steel to re-heat cracking. as in the heat-affected zones (HAZ) of welds To prevent lamellar tearing in large restrained welded structures To minimize the susceptibility of high-strength low alloy (HSLA) linepipe steels to hydrogen-induced cracking (HIC) in sour gas or sour oil environments. Several metallurgical advantages are brought about with the modification of composition and morphology of oxide and sulphide inclusions by calcium treatment of steel. minimize nozzle blockage To minimize inclusion related surface defects in billet. the following series of reactions are expected to occur to varying extents in Al-killed steels containing alumina inclusions: Ca + O = CaO (1) . The Ca content in the final product can be controlled within the range of 15 to 20 ppm To increase both tensile ductility and impact energy in the transverse and through-thickness directions in steels with tensile strengths below 1400 MPa When calcium is injected deep into the melt. as for instance: • • • • • • • To improve steel castability in continuous casting.

. Since calcium has higher affinity for oxygen than for sulfur. or if Al 2O3 inclusions are present in steel. the conversion of alumina into calcium aluminates occurs until all the inclusions in the steel are present only in liquid form. As can be observed from the Figure 2. Thermodynamically. there will be variations in the conversion of alumina inclusions to aluminates inclusions. the smaller inclusions will be converted to molten calcium aluminates more readily than the larger inclusions.Ca + S = CaS (2) (3) Ca + (x+1/3)Al2O3 = CaO·x Al2O3 + 2/3[Al] Depending on the steel composition. One of the critical questions is whether or not calcium added to steel will react with sulfur by reaction (2) and form CaS or modify Al 2O3 to liquid calcium aluminates by reaction (3). Calcium sulfides are solid at steelmaking temperatures and result in nozzle clogging similar to that caused by alumina. if sulfur or oxygen is dissolved in the steel at moderate levels. the manner of calcium adding in steel bath and other process variables. the addition of calcium initially results in a more or less pronounced conversion of the alumina into calcium aluminates until the formation of calcium sulfides starts as the addition of calcium continues. The formation of calcium sulfide can occur if calcium and sulfur contents are sufficiently high. calcium will react with oxygen or sulfur until the contents of reactants are very low (< 2ppm).

which could clog up the continuous casting nozzle. when calcium is added to steel. However. calcium will react with sulfur forming solid CaS. it will also react with oxygen and sulfur and modify the sulfide inclusions. If the sulfur content of the steel is high.Figure 2: Change of inclusions composition during calcium additions To prevent nozzle clogging in continuous casting by solid inclusions. . calcium is added to steel to modify inclusions and desulfurize the steel. which will help prevent the clogging of the casting nozzles. The Figure 3 shows influence of calcium treatment on the type of inclusions formed and its relationship with nozzle clogging. Calcium will convert solid alumina (Al2O3) inclusions into lower melting point calcium aluminates.

1 ½N2=[N] (1) The equilibrium constant for nitrogen absorption is therefore: . wear and localized corrosion resistance. Nitrogen in Steels: Part One Abstract: All steels contain some nitrogen which is effective in improving the mechanical and corrosion properties of steels if it remains in solid solution or precipitates as very fine and coherent nitrides. wear and localized corrosion resistance. crevice and intergranular corrosion) over their carbon containing counterparts.Figure 3: Influence of calcium treatment on the type of inclusions formed and its relationship with nozzle clogging Calcium treatment cannot be applied to all kinds of steel. All steels contain some nitrogen which is effective in improving the mechanical and corrosion properties of steels if it remains in solid solution or precipitates as very fine and coherent nitrides. protective casting and other measures. For those with high requirement on formability. because this treatment causes the formation of calcium aluminates inclusion which is hard. High nitrogen martensitic stainless steels show improved resistance to localized corrosion (pitting. Through controlling carry-over slag from melting furnace. Because of this. crevice and intergranular corrosion) over their carbon containing counterparts. Because of this. High nitrogen martensitic stainless steels show improved resistance to localized corrosion (pitting. such as automobile sheet. work hardening rate. for those kinds of steel. the method of improving molten steel´s purity is usually taken to optimize castability. When nitrogen is added to austenitic steels it can simultaneously improve fatigue life. Therefore. the high nitrogen steels are being considered a new promising class of engineering materials. calcium treatment is not suitable. purity of steel is guaranteed and total oxygen content in molten steel decreases. work hardening rate. strength. deformation treatment of ladle slag. strength. When nitrogen is added to austenitic steels it can simultaneously improve fatigue life. metallurgy in tundish. Solubility of Nitrogen The nitrogen solubility data are summarized by the following equations and are shown graphically in Fig. the high nitrogen steels are being considered a new promising class of engineering materials.

precipitation of one or more nitride compounds. Other sources may include atmosphere (through ladle slag). the impurity nitrogen in oxygen and the nitrogen used as a stirring gas. the ladle processing and the casting operations. air bubbles are entrained into the steel where the tap stream enters the bath in the ladle. Table 1: Nitrogen content of feed materials used in EAF steelmaking Feed Material Scrap HBI/DRI Liquid iron from the BF Cold pig iron (CPI) Hot heel Coke Oxygen Bottom stirring gas(N2) Bottom stirring gas (Ar) CaO Nitrogen Content 30-120 ppm 20-30 ppm 60 ppm 20-30 ppm 10 ppm 5000-10000 ppm 30-200 ppm > 99. then this concentration can be calculated as: [%N]=KN(pN2)½ (5) Sources of Nitrogen in Steelmaking Numerous sources of nitrogen exist during the melting. to get an impression of the sources of nitrogen during the melting process.K=[ppmN] / (pN2)½ (2) And reaction constant of this equation is related to the free energy. Also during the tapping of steel. solidification of steel may result in three nitrogenrelated phenomena: formation of blowholes. Nitrogen pickup from the atmosphere can occur during reblows in which case the furnace fills up with air. which is then entrained into the metal when the oxygen blow restarts. Table 1 shows the amount of nitrogen present in each of the feed materials typically used in the EAF. However. . (3) which becomes zero in case of equilibrium leading to: (4) If it is assume that the activity of the nitrogen dissolved in the steel is approximately the same as the chemical concentration (Henry's law). The otherwise. coke (carburizers) and various ferro-alloys.9% < 30 ppm 400 ppm Carbon Carrier Gas (Air) 78% Behavior of Nitrogen in Steel While steel is liquid the nitrogen present exists in the solution. and/or the solidification of nitrogen in interstitial solid solution. Sources of nitrogen in oxygen steelmaking include the hot metal. Ladle additions often contain moisture. the scrap.

. even after annealing. This is exploited during steelmaking to avoid excessive nitrogen pickup. the elongation decreases and the r-value increases with increasing nitrogen. the form and quantity of nitrogen present. the presence of dissolved sulfur and oxygen limit the absorption of nitrogen because they are surface-active elements. and the required behavior of the particular steel product. In particular. most steel products require that nitrogen be kept to a minimum. as shown in Figure 1. The presence of significant quantities of other elements in liquid iron affects the solubility of nitrogen. embrittlement of the heat affected zone (HAZ) of welded steels. More importantly. High nitrogen content may result in inconsistent mechanical properties in hot-rolled products. Hence. nitrogen can result in strain ageing and reduced ductility of cold-rolled and annealed LCAK steels.The maximum solubility of nitrogen in liquid iron is approximately 450 ppm. and poor cold formability. Figure 1: Solubility of nitrogen in iron for temperatures of 600-2000°C Effect of Nitrogen on Steel Properties The effect of nitrogen on steel properties can be either detrimental or beneficial. The r-value is the average ratio of the width to thickness strain of strip tensile specimens tested in various orientations. high nitrogen content leads to poor formability of LCAK steels. particularly during tapping. Conversely. It is an inverse measure of formability. In general. and less than 10 ppm at ambient temperature. Effect of Nitrogen on Formability Figure 2 shows that the strength of LCAK steels decreases slightly and then increases with increasing nitrogen. however. depending on the other alloying elements present.

Figure 2: Effect of nitrogen on yield strength. the diagram shows that nitrogen absorbed during the steelmaking process has a more significant impact than that absorbed during batch annealing in a nitrogen-rich atmosphere. tensile strength. both of which increase hardness. . and grain refinement due to the presence of nitride precipitates. Nitrogen absorbed during steelmaking results in interstitial solid solution strengthening and grain refinement. Further. precipitation strengthening by aluminum and other nitrides. r-value and elongation of LCAK steel in the annealed condition The effect of nitrogen on mechanical properties is the result of interstitial solid solution strengthening by the free nitrogen. The Figure 3 shows that hardness increases linearly with increasing nitrogen content. although both have a measurable effect. Effect of Nitrogen on Hardness Hardness is the resistance of a material to surface indentation.

Figure 4 shows that increasing nitrogen results in a higher stain-ageing index.Figure 3: Increase in hardness of aluminum-killed sheet steel with respect to increasing nitrogen content Effect of Nitrogen on Strain Ageing Strain ageing occurs in steels containing interstitial atoms. but it may also result in the appearance of 'fluting' or 'stretcher strains' on the surface of deformed material. This is based on an empirical equation to calculate the increase in yield stress when deformed material is held for 10 days at room temperature. and reduced ductility and toughness. Duckworth and Baird have developed a measure of strain ageing termed 'strain ageing index'. Not only does strain ageing result in increased hardness and strength. . after they have been plastically deformed. After deformation. predominantly nitrogen. and therefore greater propensity for surface defects. the nitrogen segregates to dislocations causing discontinuous yielding when further deformed.

hence improved toughness. This arbitrary temperature is termed the ' ductile-to-brittle' transition temperature. since the weld metal should not be a point of weakness in a welded structure. precipitation strengthening by aluminum and other nitrides. the fracture type will change from fibrous/ductile to crystalline/brittle. limited amounts of nitrogen present as precipitates have a beneficial effect on impact properties. Nitrogen is known to affect the toughness of the heat-affected zone (HAZ) of welded steel. Therefore. the transition temperature increases. and therefore toughness decreases. It is sometimes quantified by measuring the amount of energy that is absorbed by a test piece of known dimensions prior to fracture. vanadium.Figure 4: Effect of nitrogen on strain ageing in mild steels with varying manganese content Effect of Nitrogen on Impact Properties Including Welded Material The ability of a material to withstand impact loading is commonly known as toughness. It is thought this occurs when the nitrides present in the HAZ are dissociated as a result of the elevated temperatures that exist during welding. The absence of precipitates results in grains of larger diameter. in order to optimize impact properties. Figure 5 demonstrates that as free nitrogen increases. since failure via ductile fracture may be less catastrophic than that via brittle failure. Using lower heat input and several passes to prevent dissociation of the nitrides may prevent this. the smaller the grain size the lower the transition temperature. not only the nitrogen content. This is important. Nitrogen absorbed during steelmaking results in interstitial solid solution strengthening and grain refinement. and grain refinement due to the presence of nitride precipitates. This is attributed to solid solution strengthening. Nitrogen in Steels: Part Two Abstract: The effect of nitrogen on mechanical properties is the result of interstitial solid solution strengthening by the free nitrogen. As temperature is decreased. it is necessary to carefully control. This loss in toughness is often referred to as HAZ embrittlement. Figure 5: Effect of free nitrogen on impact properties Conversely. . Further. Also. It is further analyzed by determining the fracture mechanism upon impact over a range of temperatures. which contain high levels of free nitrogen further exacerbating the loss of toughness. but also the form in which it exists. The lower the transition temperature the better the impact properties. Nitrides of aluminum. niobium and titanium result in the formation of fine-grained ferrite. the metal cools quickly producing low toughness martensite or bainite.

Nitrogen absorbed during steelmaking results in interstitial solid solution strengthening and grain refinement. The r-value is the average ratio of the width to thickness strain of strip tensile specimens tested in various orientations. even after annealing. It is an inverse measure of formability. Conversely. Effect of Nitrogen on Hardness Hardness is the resistance of a material to surface indentation. r-value and elongation of LCAK steel in the annealed condition The effect of nitrogen on mechanical properties is the result of interstitial solid solution strengthening by the free nitrogen. high nitrogen content leads to poor formability of LCAK steels. tensile strength. the diagram shows that . Figure 1: Effect of nitrogen on yield strength. the elongation decreases and the r-value increases with increasing nitrogen. The Figure 2 shows that hardness increases linearly with increasing nitrogen content.both of which increase hardness. precipitation strengthening by aluminum and other nitrides. and grain refinement due to the presence of nitride precipitates. Hence. Further. both of which increase hardness. Effect of Nitrogen on Formability Figure 1 shows that the strength of LCAK steels decreases slightly and then increases with increasing nitrogen.

.. Refining Reactions In LD basic oxygen steelmaking process.(5) The Figure 1 represents an idealized diagram. Several types of oxygen steelmaking processes. bottom blowing and combined blowing have been invented.05%.. Several types of oxygen steelmaking processes.(4) [C] + (FeO) ↔ CO2 + Fe . The principal refining reactions is of course the removal of carbon: [C] + [O] ↔ CO2 ..2%. The essential features of conventional steelmaking are the partial oxidation of the carbon. like top blowing. phosphorus and manganese present in pig iron and the accompanying reduction in the sulfur level... P=max 0. S=max 0.(2) 2(FeO) + ½O2(g) ↔ (Fe2O3) .(1) Fe + [O] ↔ (FeO) .. The basic thermodynamic data for these reactions are well established and the equilibrium carbon and oxygen contents may be readily calculated for all the temperatures and pressures encountered in steelmaking. silicon...15% but these solute elements are diluted by the addition scrap which forms some 20-30% of the metallic charge..(3) Carbon The actual distribution of oxygen between slag and metal is not easily determined since it is a function of a number of variables including lance height and oxygen flow rate. the oxygen required for the refining reactions is supplied as a gas and both metal and slag are initially oxidized ½O2(g) ↔ [O] . The oxygen steelmaking process is a generic name given to those processes in which gaseous oxygen is used as the primary agent for autothermic generation of heat as a result of the oxidation of dissolved impurities like carbon... silicon.. Si=max 0. manganese and phosphorus and to a limited extent the oxidation of iron itself.. manganese and phosphorus and to a limited extent the oxidation of iron itself.. Mn=max 0.. showing the changes in concentrations of the elements in LD metal bath during oxygen blowing.. like top blowing.The Oxygen Steelmaking Process: Part One Abstract: The oxygen steelmaking process is a generic name given to those processes in which gaseous oxygen is used as the primary agent for autothermic generation of heat as a result of the oxidation of dissolved impurities like carbon. bottom blowing and combined blowing have been invented..8%.. . Blast furnace hot metal for LD (Basic Oxygen Furnace) steelmaking process ideally contains about C=4.8%. silicon..

the reaction of carbon oxidation is self-accelerated and attains a very high rate.. The reaction may be represented by equations (6) and (7)... a slightly reversion. but later.. [Si] + 2[O] ↔ (SiO2) . on the activities of manganese and ferrous oxides.. metal and gas bubbles. the liquid bath becomes an intimate mixture of slag... nitrogen and part of non-metallic inclusions from the metal..(6) [Si] + 2(FeO) ↔ (SiO2) + 2Fe ..(7) Manganese Similar equations can be applied to manganese removal [Mn] + [O] ↔ (MnO) . Owing to the pressure of the oxygen supplied and the evolution of large quantities of gases..Figure 1: The changes of bath composition during the blow in a basic oxygen steelmaking converter (idealized) Oxidation of carbon during the oxygen converter process is most important. since the reaction increases the temperature and evolves a large amount of gases CO and CO2 that cause agitation of metal and slag and remove hydrogen. the removal silicon is usually completed relatively early in the blow. with an enormous contact surface. the bath manganese level falls as a result of oxidation... Because of this.(8) [Mn] + (FeO) ↔ (MnO) + Fe .(9) Initially. Silicon In accordance with thermodynamic predictions.. These changes in the manganese content of the bath are attributed to the combined effects of rising temperature and variable slag composition. ... followed by a second fall occurs..

A limited correlation with the carbon content in the bath has been reported. who concluded that the thermodynamic behavior of phosphorus is best explained by a modified version of the ionic theory first proposed by Flood and Grjotheim..(11) log (%P)/[P] = 22 350/T + 0.... i.suggesting that the reaction is close equilibrium.(10) Healy has expressed the equilibrium distribution of phosphorus by equations that apply to specific concentration ranges in the CaO-SiO2-FeO system. kPS is found to be independent of B. Unfortunately.5 log Fet – 24. In general. the (FeO) level in the slag falls as a consequence of the decarburization process and the dilution that accompanies lime fluxing. towards the end of the blow...(12) Equation (11) is applicable to slag containing over 24%CaO while equation (12) is valid from zero %CaO to saturation..: log (%P)/[P] = 22 350/T + 7 log%CaO + 2.. The distribution of phosphorus between slag and metal has been reviewed by Healy. In the middle part of blow. the (FeO) increases again.0 . the phosphorus distribution is expected to be better than in LD. provided that the slag is sufficiently basic. A parameter kPS is defined as kPS = (%P2O5)/[%P]•(1 + (%SiO2)) = φ ((%FeO).. although other workers have suggested that extensive dephosphorization should be possible at high carbon levels..B) .5. To some extent the manganese loss may be minimized by rising the temperature.. The slag-metal reactions is written in ionic form in equation (10) 2[P] + 5[O] + 3 (O2-) ↔ 2(PO3-)4 .08 log%CaO + 2. as carbon removal becomes less intense and dilution begins to affect the activity of manganese oxide with the result that manganese transfers from bath to slag. the manganese content was found to be 82% of the equilibrium value when lump lime was used and 85% of the equilibrium value when powdered lime is injected. . because the oxygen potential of the slag-metal system is influenced by decarburization. The distribution of phosphorus is also found to be related to the content of carbon in steel at the time of tapping..e.0 . On the other hand. in practice the phosphorus partition ratios are far from the values calculated for equilibrium with carbon-free iron. the dependence of phosphorus distribution on the FeO content of slag in LD and Q-BOP is shown in Figure 2. high basicity and the low temperature of slag (irrespective of the FeO content) favor dephosphorization. owing to lower carbon levels achieved in bottom-blown process.. This view is supported by the observation that at the end of blowing.(13) where B is basicity. However.5 log Fet – 16. Phosphorus The partitioning of phosphorus between the slag and metal is known to be very sensitive to process conditions and so far it has been possible to build a kinetic model based on simple assumptions... for B>2..

when the metal is rich in carbon and silicon.Figure 2: Effect of FeO content of slag on phosphorus distribution and log kPS value Sulfur removal Sulfur transfer takes place through the following reactions: [S] + (O2)g = (SO2)g ... the activity of sulfur is high. . and therefore favors desulphurization. It may be speeded up by improving the bath mixing and increasing the temperature. part of sulfur is removed at the initial stages of the process when the temperature of melt is still relatively low through its reaction with manganese: [Mn] + [S] = (MnS) .... But the secondary and most intensive desulphurization occurs at the end and of the heat when the lime dissolves in the slag with a maximum rate and the slag basicity reaches B=2. fluidity and basicity of the slag.(14) It is found that approximately 15-25% of dissolved sulfur is directly oxidized into the gaseous phase due to the turbulent and oxidizing conditions existing in the jet impact zone. Thus the total desulphurization of the metal is mainly decided by the basicity of the homogeneous final slag which is formed in the oxygen converter process during the last minutes of metal blowing. Besides.(15) A rise in the concentration of iron oxides in the slag promotes dissolution of lime.. At the initial stage of the heat... and the activity of sulfur. In Basic Oxygen Furnace. the metal desulphurization proceeds slowly because it is a diffusion process.8 and more.

The greater the bulk of slag is the largest part of the sulfur will pass into slag at the same sulfur distribution coefficient.13(%FeO) + 0.. the residual concentration of sulfur in metal bath becomes lower. . But it is not beneficial to form a very large bulk of slag. regression equations based on operational data are employed to predict the end point sulfur within acceptable limits.. for example is (%S)/[S] = 1.With an increase of slag basicity.42B – 0. In a steel plant. since this increases the iron loss due to burning.89 ..(16) The equation 16 shows the beneficial influence of slag basicity and the retarding influence of FeO on sulfur distribution. but they are suitable and applicable to a local situation only. causes splashings and rapid wear of the lining. One such equation.. A large number of such correlations are reported in the literature. so that the coefficient of sulfur distribution between slag and metal can be raised up to 10.