1.

2 EFFECTS OF ALLOYING ELEMENTS
Steels contain alloying elements and impurities that must be associated with austenite, ferrite, and cementite. The combined effects of alloying elements and heat treatment produce an enormous variety of microstructures and properties. Given the limited scope of this chapter, it would be difficult to include a detailed survey of the effects of alloying elements on the iron –carbon equilibrium diagram, allotropic transformations, and forming of new phases. This complicated subject, which lies in the domain of ferrous physical metallurgy, has been revie wed extens ively in Chapt er 2 of this handb ook an d elsewh ere in the literat ure [4,5 ,8 –12]. In this section, the effects of various elements on steelmaking (deoxidation) practices and steel characteristics will be briefly outlined. It should be noted that the effects of a single alloying element on either practice or characteristics is modified by the influence of other elements. The interaction of alloying elements must be considered [5]. According to the effect on matrix, alloying elements can be divided into two categories: 1. By expending the g-field, and encouraging the formation of austenite, such as Ni, Co, Mn, Cu, C, and N (these elements are called austenite stabilizers) 2. By contracting the g-field, and encouraging the formation of ferrite, such as Si, Cr, W, Mo, P, Al, Sn, Sb, As, Zr, Nb, B, S, and Ce (these elements are called ferrite stabilizers) Alloying elements can be divided into two categories according to the interaction with carbon in steel: 1. Carbide-forming elements, such as Mn, Cr, Mo, W, V, Nb, Ti, and Zr. They go into solid solution in cementite at low concentrations. At higher concentrations, they formmore stable alloy carbides, though Mn only dissolves in cementite. 2. Noncarbide-forming elements, such as Ni, Co, Cu, Si, P, and Al. They are free from carbide in steels, and normally found in the matrix [5,11,12]. To simplify the discussion, the effects of various alloying elements listed below are summarized separately.

1.2.1 CARBON
The amount of carbon (C) required in the finished steel limits the type of steel that can be made. As the C content of rimmed steels increases, surface quality deteriorates. Killed steels in the approximate range of 0.15–0.30% C may have poorer surface quality and require special processing to attain surface quality comparable to steels with higher or lower C contents. Carbon has a moderate tendency for macrosegregation during solidification, and it is often more significant than that of any other alloying elements. Carbon has a strong tendency to segregate at the defects in steels (such as grain boundaries and dislocations). Carbide forming elements may interact with carbon and form alloy carbides. Carbon is the main hardening element in all steels except the austenitic precipitation hardening (PH) stainless steels, managing steels, and interstitial-free (IF) steels. The strengthening effect of C in steels consists of solid solution strengthening and carbide dispersion strengthening. As the C content in steel increases, strength increases, but ductility and weldability decrease [4,5].

1.2.2 MANGANESE
Manganese (Mn) is present in virtually all steels in amounts of 0.30% or more [13]. Manganese is essentially a deoxidizer and a desulfurizer [14]. It has a lesser tendency for macrosegregation than any of the common elements. Steels above 0.60% Mn cannot be readily rimmed. Manganese is beneficial to surface quality in all carbon ranges (with the exception of extremely low-carbon rimmed steels) and reduction in the risk of red-shortness. Manganese favorably affects forgeability and weldability. Manganese is a weak carbide former, only dissolving in cementite, and forms alloying cementite in steels [5]. Manganese is an austenite former as a result of the open g-phase field. Large quantities (>2% Mn) result in an increased tendency toward cracking and distortion during quenching [4,5,15]. The presence of alloying element Mn in steels enhances the impurities such as P, Sn, Sb, and As segregating to grain boundaries and induces temper embrittlement [5].

1.2.3 SILICON
Silicon (Si) is one of the principal deoxidizers used in steelmaking; therefore, silicon content also determines the type of steel produced. Killed carbon steels may contain Si up to a maximum of 0.60%. Semikilled steels may contain moderate amounts of Si. For example, in rimmed steel, the Si content is generally less than 0.10%. Silicon dissolves completely in ferrite, when silicon content is below 0.30%, increasing its strength without greatly decreasing ductility. Beyond 0.40% Si, a marked decrease in ductility is noticed in plain carbon steels [4]. If combined with Mn or Mo, silicon may produce greater hardenability of steels [5]. Due to the addition of Si, stress corrosion can be eliminated in Cr–Ni austenitic steels. In heat treated steels, Si is an important alloy element, and increases hardenability, wear resistance, elastic limit and yield strength, and scale resistance in heat-resistant steels [5,15]. Si is a noncarbide former, and free from cementite or carbides; it dissolves in martensite and retards the decomposition of alloying martensite up to 3008C.

1.2.4 PHOSPHORUS
Phosphorus (P) segregates during solidification, but to a lesser extent than C and S. Phosphorus dissolves in ferrite and increases the strength of steels. As the amount of P increases, the ductility and impact toughness of steels decrease, and raises the cold-shortness [4,5]. Phosphorus has a very strong tendency to segregate at the grain boundaries, and causes the temper embrittlement of alloying steels, especially in Mn, Cr, Mn–Si, Cr–Ni, and Cr–Mn steels. Phosphorus also increases the hardenability and retards the decomposition of martensite-like Si in steels [5]. High P content is often specified in low-carbon free-machining steels to improve machinability. In low-alloy structural steels containing ~0.1% C, P increases strength and atmospheric corrosion resistance. In austenitic Cr –Ni steels, the addition of P can cause precipitation effects and an increase in yield points [15]. In strong oxidizing agent, P causes grain boundary corrosion in austenitic stainless steels after solid solution treatment as a result of the segregation of P at grain boundaries [5].

17] . Aluminum is also used in maraging steels. 1. strongly increasing hardenability. As the content of W increases in alloy steels.2. segregating to grain boundaries and induces temper embrittlement. Chromium carbides are hard and wear-resistant and increase the edge-holding quality. increases hardenability. fine nitrides and carbonitrides will form during controlled rolling and controlled cooling. and can induce secondary hardening during the tempering of quenched steels. Nickel dissolving in ferrite improves toughness. It promotes hot strength and red-hardness and thus cutting ability. It promotes the weldability of heat-treatable steels.19].6. It is therefore used mainly as an additional alloying element in high-speed.10 MOLYBDENUM Molybdenum (Mo) is a pronounced carbide former. improves high-temperature strength and high-pressure hydrogenation properties. but the thermal coefficient of oxide inclusions is lower than that of matrix.11. and enhances abrasion resistance in high-carbon grades. Tungsten slightly dissolves in cementite. Molybdenum increases corrosion resistance and is used to a great extent in high-alloy Cr ferritic stainless steels and with Cr–Ni austenitic stainless steels. Vanadium increases wear resistance. It dissolves in austenite. sulfur in the range of 0. decreases FATT 50% (8C). chromium carbides (Cr. In precipitation hardening stainless steels. Nitrogen induces strain aging.9 NICKEL Nickel (Ni) is a noncarbide-forming element in steels. abrasion-resistant carbides.1. hot-forging.20– 0. Fine vanadium carbides and nitrides give a strong dispersion hardening effect in microalloyed steels after controlled rolling and controlled cooling. and blue brittleness in low-carbon steels. Aluminum has the drawback of a tendency to promote graphitization. Nickel raises hardenability.12 VANADIUM Vanadium (V) is a very strong carbide former. The addition of Cr in steels enhances the impurities. Sb. only alloyed cementite (Fe. Very small amounts of V dissolve in cementite. 1. Alloy steels containing 0. The addition of Mo produces fine-grained steels. Vanadium increases fatigue strength and improves notch sensitivity. In the low Cr/C ratio range. therefore.8 CHROMIUM Chromium (Cr) is a medium carbide former. 1.2. Cr and Mo. (2) MnS inclusions coat or cover oxides (such as alumina. 1.2. Ni is an austenite-forming element [5. However. quench aging. However. a longer time at temperature is necessary to allow solution to take place before quenching is accomplished [5. As Al forms very hard nitrides with nitrogen. it produce greater hardenability. In combination with Ni. and improves fatigue strength. and imparts strength and toughness. Sulfur improves the fatigue life of bearing steels [18].15]. High Mo contents reduce the stainless steel’s susceptibility to pitting [5. such as P.11. Vanadium is a grain refiner.15].2. Of all the alloying elements. weldability. would appear. silicate. edge-holding quality. but cannot eliminate it. and As. it is usually an alloying element in nitriding steels. Molybdenum has a very strong solid solution strengthening in austenitic alloys at elevated temperatures. It prevents grain growth at high temperature. Molybdenum can induce secondary hardening during the tempering of quenched steels and improves the creep strength of low-alloy steels at elevated temperatures. and Ti are added to high-strength low-alloy (HSLA) steels. corrosion and oxidation resistance of steels. Molybdenum is a very important alloying element for alloy steels. because (1) the thermal coefficient on MnS inclusion is higher than that of matrix. and fatigue resistance in steels [5.Fe)23C6 or both.Cr)3C forms.33% is intentionally added to free-machining steels for increased machinability [5. causing precipitation or solid solution strengthening [5].2. As a result of the open g-phase field. W forms very hard. Sulfur has a very strong tendency to segregate at grain boundaries and causes reduction of hot ductility in alloy steels. Sn. If the Cr/C ratio rises. It dissolves slightly in cementite. impact toughness. It can expand and stabilize the austenitic structure.08–0. while molybdenum carbides will form when the Mo content in steel is high enough. W and Mo impair scaling resistance. Nitrogen can be used as an alloying element in microalloying steels or austenitic stainless steels.13]. If the nitride forming elements V.18]. and creep-resistant steels. Complex chromium– iron carbides slowly go into solution in austenite. causing precipitation hardening reaction.14]. Al can be used as an alloying element. even at the subzero temperatures [20]. . Vanadium provides a very strong secondary hardening effect on tempering.2. The behavior of W is very similar to Mo in steels. and partly substitute Ni in austenitic steels. Chromium is the most important alloying element in steels.6 ALUMINUM Aluminum (Al) is widely used as a deoxidizer and a grain refiner [9]. 1.or hot-shortness due to the low-melting sulfide eutectics surrounding the grain in reticular fashion [15. notch impact toughness.2. 1. but the undissolved vanadium carbides decrease hardenability [5].10. Nickel raises the corrosion resistance of Cr –Ni austenitic stainless steels in nonoxidizing acid medium.2.10. The presence of V retards the rate of tempering embrittlement in Mo-bearing steels. It increases scaling resistance and is therefore often added to heat-resistant steels and alloys. Al is one of the most effective elements in controlling grain growth prior to quenching. 1. thereby reducing the tensile stresses in the surrounding matrix [5. Chromium increases hardenability. Nb.5 SULFUR Increased amounts of sulfur (S) can cause red. and high-temperature strength.16]. and surface quality (particularly in the lower carbon and lower manganese steels). Sulfur has a detrimental effect on transverse ductility. W and Mo are the main alloying elements in high-speed steels [5.40% Mo or V display a delayed temper embrittlement.7 NITROGEN Nitrogen (N) is one of the important elements in expanded g-field group.11 TUNGSTEN Tungsten (W) is a strong carbide former.Fe)7C3 or (Cr. Aluminum increases the corrosion resistance in low-carbon corrosion-resisting steels. and spinel). but has a slight effect on longitudinal mechanical properties. therefore it raises hot-hardness and thus cutting ability in high-speed steels.

erbium (Er). Titanium increases creep rupture strength through formation of special nitrides and tends significantly to segregation and banding [15]. a Cu content above 1% results in improved resistance to H2SO4 and HCl and stress corrosion [5. The segregation of B in steels is a non equilibrium segregation. but by addition of Cr. 1.21 TIN Tin (Sn ) in relatively small amounts is harmful to steels. the hardenability of alloy steels may increase strongly due to the presence of Mn and Cr in steels. Niobium is a stabilizer in Cr–Ni austenitic steels to eliminate intergranular corrosion. It decreases hardenability of carbon steels.2.22]. thulium (Tm. fatigue strength. and they also react with the low-melting elements.and medium-carbon steels. ytterbium (Yb). large amounts of B result in brittle. particularly sulfide inclusions. unworkable steels. Nb-. They are scandium(Sc) of the fourth period. and machinability. 1.15]. Niobium is widely used in microalloying steels to obtain high strength and good toughness through controlled rolling and controlled cooling practices. Small amounts of Sn and Cu also de crease the hot ductility of steels in the austenite þ ferrite region [25]. praseodymium (Pr). It ha s a very strong tendency to segregate at grain boundaries and induces temper embrittlement in alloy steels. and creep-resistant and high-temperature materials [13. neodymium (Nd). samarium (Sm). If Cu is present in appreciable amounts.17 COPPER Copper (Cu) addition has a moderate tendency to segregate. 1. 1. terbium (Tb). A 0. dysprosium (Dy).2 –0.30% Cu can cause precipitation hardening. resulting in an increase in tool life. gadolinium (Gd). Lu).1.15].0035%). with no real increase in hardenability above 0. It is detrimental to surface quality and exaggerates the surface defects inherent in resulfurized steels.19 ZIRCONIUM Zircon ium (Zr) is added to killed HSLA steel s to obtain improvement in inclusion characteristics. such as antimony (Sb).14 TITANIUM Titanium (Ti) is a very strong carbide and nitride former. Cu improves the atmospheric corrosion resistance (when in excess of 0. Small amounts of Nb can form fine nitrides or carbonitrides and refine the grains.16 COBALT Cobalt (Co) is a noncarbide former in steels. maraging steels. and V-carbides in steels [5]. The effects of Ti are similar to those of Nb and V. Cobalt promotes the precipitation hardening [5]. It inhibits grain growth at high temperature and significantly improves the retention of temper and high-temperature strength. arsenic (As). intermetallic compounds are formed in maraging steels. REMs tend strongly to segregate at the grain boundaries and increase the hardenability of steels [21. Cobalt raises the martensitic transformation temperature ofMs (8C) and decreases the amount of retained austenite in alloy steels.0005 –0. In austenitic stainless steels. By the addition of Ti. Niobium containing non quenched and tempered steels. 1. However.20%) and the tensile properties in alloy and low-alloy steels. Their chemical and physical properties are similar. Above 0. They generally coexist and are difficult to separate in ore beneficiation and metal extraction so they are usually supplied as a mixture and used in various mixture states in metallurgical industries.15]. 1. and V dissolve in austenite. If Ti.20 LEAD Lead (Pb) is sometime s added (in the range of 0. 1. hot ductility.6% C [14]. in very small amounts (0. The use of Co is generally restricted to high-speed steels. it is detrimental to hot-working operations. it increases hardenability of Cr–Mo alloy steels. Tu). It increases hardenability. The weldability of boron-alloyed steels is another reason for their use. lanthanum (La).2. The beneficial effects of B are only apparent with lower.18 BORON Boron (B). and phosphorus (P). Nb. promethium (Pm). has a starting effect on the hardenability of steels due to the strong tendency to segregate at grain boundaries. where modifications of inclusion shape improve ductility in transverse bending. However. It is widely used in austenitic stainless steels as a carbide former for stabilization to eliminate intergranular corrosion. forming highmelting compounds and preventing them from causing the red-shortness and temper embrittlement [21. and lutecium (or lutecium.2. and V are effective grain inhibitors because their nitrides and carbides are quite stable and difficult to dissolve in austenite.2. holmium (Ho). Ti.22 ANTIMONY . including microalloyed medium-carbon steels and low-carbon bainite (martensite) steels. It increases the life of heat-conducting materials.2. The effects of REM on shape control and modification of inclusions would improve transversal plasticity and toughness.5 %) to carbon and alloy steels through mechanical dispersion during teeming to improve machinability. tin (Sn). offer a greatly improved combination of strength and toughness.15 RARE EARTH METALS Rare earth metals (REMs) constitute the IIIB group of 17 elements in the periodic table. Mn and Cr decrease the stability of Ti-. and reportedly helps the adhesion of paint [6. europium (Eu). It also improves the hardenability of other alloying elements.2.2. 1.14]. hot-forming tool steels.2.13 NIOBIUM AND TANTALUM Niobium (Nb) and tantalum (Ta) are very strong carbide and nitride formers. and the lanthanides of the sixth period. 1. It is used as a very economical substitute for some of the more expensive elements. which include the elements. Nb.03% Nb in austenite can increase the yield strength of medium-carbon steel by 150 MPa.23]. REMs are strong deoxidizers and desulfurizers. but titanium carbides and nitrides are more stable than those of Nb and V. therefore increasing the yield strength of steels. It is also a strong carbide former and produces a contracted austenite phase field [5.2. causing age hardening.2. It has a detrimental effect on the surface quality of continuous cast billets containing small amounts of Cu [24]. cerium (Ce). yttrium(Y) of the fifth period.

and improves machinability. It also has a very strong tendency to segregate at grain boundaries and cause temper embrittlement in alloy steels. Al.Antimony (Sb) has a strong tendency to segregate during the freezing process. The combination of Ca. 1. and has a detrimental effect on the surface quality of continuous cast billets. silicocalcium is used usually in steelmaking. . and Si forms lowmelting oxides in steelmaking.23 CALCIUM Calcium (Ca) is a strong deoxidizer.2.