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 0.150.30% 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 CrNi 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, MnSi, CrNi, and CrMn 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].

1.2.5 SULFUR
Increased amounts of sulfur (S) can cause red- or hot-shortness due to the low-melting sulfide eutectics surrounding the grain in reticular fashion [15,16]. Sulfur has a detrimental effect on transverse ductility, notch impact toughness, weldability, and surface quality (particularly in the lower carbon and lower manganese steels), but has a slight effect on longitudinal mechanical properties. Sulfur has a very strong tendency to segregate at grain boundaries and causes reduction of hot ductility in alloy steels. However, sulfur in the range of 0.080.33% is intentionally added to free-machining steels for increased machinability [5,17] . Sulfur improves the fatigue life of bearing steels [18], because (1) the thermal coefficient on MnS inclusion is higher than that of matrix, but the thermal coefficient of oxide inclusions is lower than that of matrix, (2) MnS inclusions coat or cover oxides (such as alumina, silicate, and spinel), thereby reducing the tensile stresses in the surrounding matrix [5,10,19].

1.2.6 ALUMINUM
Aluminum (Al) is widely used as a deoxidizer and a grain refiner [9]. As Al forms very hard nitrides with nitrogen, it is usually an alloying element in nitriding steels. It increases scaling resistance and is therefore often added to heat-resistant steels and alloys. In precipitation hardening stainless steels, Al can be used as an alloying element, causing precipitation hardening reaction. Aluminum is also used in maraging steels. Aluminum increases the corrosion resistance in low-carbon corrosion-resisting steels. Of all the alloying elements, Al is one of the most effective elements in controlling grain growth prior to quenching. Aluminum has the drawback of a tendency to promote graphitization.

1.2.7 NITROGEN
Nitrogen (N) is one of the important elements in expanded g-field group. It can expand and stabilize the austenitic structure, and partly substitute Ni in austenitic steels. If the nitride forming elements V, Nb, and Ti are added to high-strength low-alloy (HSLA) steels, fine nitrides and carbonitrides will form during controlled rolling and controlled cooling. Nitrogen can be used as an alloying element in microalloying steels or austenitic stainless steels, causing precipitation or solid solution strengthening [5]. Nitrogen induces strain aging, quench aging, and blue brittleness in low-carbon steels.

1.2.8 CHROMIUM
Chromium (Cr) is a medium carbide former. In the low Cr/C ratio range, only alloyed cementite (Fe,Cr)3C forms. If the Cr/C ratio rises, chromium carbides (Cr,Fe)7C3 or (Cr,Fe)23C6 or both, would appear. Chromium increases hardenability, corrosion and oxidation resistance of steels, improves high-temperature strength and high-pressure hydrogenation properties, and enhances abrasion resistance in high-carbon grades. Chromium carbides are hard and wear-resistant and increase the edge-holding quality. Complex chromium iron carbides slowly go into solution in austenite; therefore, a longer time at temperature is necessary to allow solution to take place before quenching is accomplished [5,6,14]. Chromium is the most important alloying element in steels. The addition of Cr in steels enhances the impurities, such as P, Sn, Sb, and As, segregating to grain boundaries and induces temper embrittlement.

1.2.9 NICKEL
Nickel (Ni) is a noncarbide-forming element in steels. As a result of the open g-phase field, Ni is an austenite-forming element [5,11,15]. Nickel raises hardenability. In combination with Ni, Cr and Mo, it produce greater hardenability, impact toughness, and fatigue resistance in steels [5,10,11,18]. Nickel dissolving in ferrite improves toughness, decreases FATT 50% (8C), even at the subzero temperatures [20]. Nickel raises the corrosion resistance of Cr Ni austenitic stainless steels in nonoxidizing acid medium.

1.2.10 MOLYBDENUM
Molybdenum (Mo) is a pronounced carbide former. It dissolves slightly in cementite, while molybdenum carbides will form when the Mo content in steel is high enough. Molybdenum can induce secondary hardening during the tempering of quenched steels and improves the creep strength of low-alloy steels at elevated temperatures. The addition of Mo produces fine-grained steels, increases hardenability, and improves fatigue strength. Alloy steels containing 0.20 0.40% Mo or V display a delayed temper embrittlement, but cannot eliminate it. Molybdenum increases corrosion resistance and is used to a great extent in high-alloy Cr ferritic stainless steels and with CrNi austenitic stainless steels. High Mo contents reduce the stainless steels susceptibility to pitting [5,15]. Molybdenum has a very strong solid solution strengthening in austenitic alloys at elevated temperatures. Molybdenum is a very important alloying element for alloy steels.

1.2.11 TUNGSTEN
Tungsten (W) is a strong carbide former. The behavior of W is very similar to Mo in steels. Tungsten slightly dissolves in cementite. As the content of W increases in alloy steels, W forms very hard, abrasion-resistant carbides, and can induce secondary hardening during the tempering of quenched steels. It promotes hot strength and red-hardness and thus cutting ability. It prevents grain growth at high temperature. W and Mo are the main alloying elements in high-speed steels [5,13]. However, W and Mo impair scaling resistance.

1.2.12 VANADIUM
Vanadium (V) is a very strong carbide former. Very small amounts of V dissolve in cementite. It dissolves in austenite, strongly increasing hardenability, but the undissolved vanadium carbides decrease hardenability [5]. Vanadium is a grain refiner, and imparts strength and toughness. Fine vanadium carbides and nitrides give a strong dispersion hardening effect in microalloyed steels after controlled rolling and controlled cooling. Vanadium provides a very strong secondary hardening effect on tempering, therefore it raises hot-hardness and thus cutting ability in high-speed steels. Vanadium increases fatigue strength and improves notch sensitivity. Vanadium increases wear resistance, edge-holding quality, and high-temperature strength. It is therefore used mainly as an additional alloying element in high-speed, hot-forging, and creep-resistant steels. It promotes the weldability of heat-treatable steels. The presence of V retards the rate of tempering embrittlement in Mo-bearing steels.

1.2.13 NIOBIUM AND TANTALUM

Niobium (Nb) and tantalum (Ta) are very strong carbide and nitride formers. Small amounts of Nb can form fine nitrides or carbonitrides and refine the grains, therefore increasing the yield strength of steels. Niobium is widely used in microalloying steels to obtain high strength and good toughness through controlled rolling and controlled cooling practices. A 0.03% Nb in austenite can increase the yield strength of medium-carbon steel by 150 MPa. Niobium containing non quenched and tempered steels, including microalloyed medium-carbon steels and low-carbon bainite (martensite) steels, offer a greatly improved combination of strength and toughness. Niobium is a stabilizer in CrNi austenitic steels to eliminate intergranular corrosion.

1.2.14 TITANIUM
Titanium (Ti) is a very strong carbide and nitride former. The effects of Ti are similar to those of Nb and V, but titanium carbides and nitrides are more stable than those of Nb and V. It is widely used in austenitic stainless steels as a carbide former for stabilization to eliminate intergranular corrosion. By the addition of Ti, intermetallic compounds are formed in maraging steels, causing age hardening. Titanium increases creep rupture strength through formation of special nitrides and tends significantly to segregation and banding [15]. Ti, Nb, and V are effective grain inhibitors because their nitrides and carbides are quite stable and difficult to dissolve in austenite. If Ti, Nb, and V dissolve in austenite, the hardenability of alloy steels may increase strongly due to the presence of Mn and Cr in steels. Mn and Cr decrease the stability of Ti-, Nb-, and V-carbides in steels [5].

1.2.15 RARE EARTH METALS

Rare earth metals (REMs) constitute the IIIB group of 17 elements in the periodic table. They are scandium(Sc) of the fourth period, yttrium(Y) of the fifth period, and the lanthanides of the sixth period, which include the elements, lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm; Tu), ytterbium (Yb), and lutecium (or lutecium, Lu). Their chemical and physical properties are similar. 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. REMs are strong deoxidizers and desulfurizers, and they also react with the low-melting elements, such as antimony (Sb), tin (Sn), arsenic (As), and phosphorus (P), forming highmelting compounds and preventing them from causing the red-shortness and temper embrittlement [21,22]. The effects of REM on shape control and modification of inclusions would improve transversal plasticity and toughness, hot ductility, fatigue strength, and machinability. REMs tend strongly to segregate at the grain boundaries and increase the hardenability of steels [21,23].

1.2.16 COBALT
Cobalt (Co) is a noncarbide former in steels. It decreases hardenability of carbon steels, but by addition of Cr, it increases hardenability of CrMo alloy steels. Cobalt raises the martensitic transformation temperature ofMs (8C) and decreases the amount of retained austenite in alloy steels. Cobalt promotes the precipitation hardening [5]. It inhibits grain growth at high temperature and significantly improves the retention of temper and high-temperature strength, resulting in an increase in tool life. The use of Co is generally restricted to high-speed steels, hot-forming tool steels, maraging steels, and creep-resistant and high-temperature materials [13,15].

1.2.17 COPPER
Copper (Cu) addition has a moderate tendency to segregate. Above 0.30% Cu can cause precipitation hardening. It increases hardenability. If Cu is present in appreciable amounts, it is detrimental to hot-working operations. It is detrimental to surface quality and exaggerates the surface defects inherent in resulfurized steels. However, Cu improves the atmospheric corrosion resistance (when in excess of 0.20%) and the tensile properties in alloy and low-alloy steels, and reportedly helps the adhesion of paint [6,14]. In austenitic stainless steels, a Cu content above 1% results in improved resistance to H2SO4 and HCl and stress corrosion [5,15].

1.2.18 BORON
Boron (B), in very small amounts (0.0005 0.0035%), has a starting effect on the hardenability of steels due to the strong tendency to segregate at grain boundaries. The segregation of B in steels is a non equilibrium segregation. It also improves the hardenability of other alloying elements. It is used as a very economical substitute for some of the more expensive elements. The beneficial effects of B are only apparent with lower- and medium-carbon steels, with no real increase in hardenability above 0.6% C [14]. The weldability of boron-alloyed steels is another reason for their use. However, large amounts of B result in brittle, unworkable steels.

1.2.19 ZIRCONIUM
Zircon ium (Zr) is added to killed HSLA steel s to obtain improvement in inclusion characteristics, particularly sulfide inclusions, where modifications of inclusion shape improve ductility in transverse bending. It increases the life of heat-conducting materials. It is also a strong carbide former and produces a contracted austenite phase field [5,15].

1.2.20 LEAD
Lead (Pb) is sometime s added (in the range of 0.2 0.5 %) to carbon and alloy steels through mechanical dispersion during teeming to improve machinability.

1.2.21 TIN
Tin (Sn ) in relatively small amounts is harmful to steels. It ha s a very strong tendency to segregate at grain boundaries and induces temper embrittlement in alloy steels. It has a detrimental effect on the surface quality of continuous cast billets containing small amounts of Cu [24]. Small amounts of Sn and Cu also de crease the hot ductility of steels in the austenite ferrite region [25].

1.2.22 ANTIMONY

Antimony (Sb) has a strong tendency to segregate during the freezing process, and has a detrimental effect on the surface quality of continuous cast billets. It also has a very strong tendency to segregate at grain boundaries and cause temper embrittlement in alloy steels.

1.2.23 CALCIUM
Calcium (Ca) is a strong deoxidizer; silicocalcium is used usually in steelmaking. The combination of Ca, Al, and Si forms lowmelting oxides in steelmaking, and improves machinability.