Chapter.

6 Alloy Steels

Although plain carbon steels are widely used, they are not adequate for all
engineering applications because of the following limitations:
1. They cannot be strengthened beyond approximately 690 MPa (100 ksi) without a
significant loss in toughness and ductility.
2. They are not hardenable to great depths, thus limiting the maximum cross section that
can be through hardened.
3. Severe quenches, such as brine or water, are often required to produce the desired
hardness, which greatly increases the susceptibility to distortion and cracking.
4. Plain carbon steels have poor corrosion resistance, and they readily oxidize at
elevated temperatures.
Alloy steels are alloys of iron with the addition of carbon and one or more of the following
elements: manganese, chromium, nickel, molybdenum, niobium, titanium, tungsten, cobalt,
copper, vanadium, silicon, aluminum, and boron. Alloy steels exhibit superior mechanical
properties compared to plain carbon steels as a result of alloying additions.

Effects of Alloying Elements

Alloying elements are added to steels for a variety of reasons, including:

1. Deeper hardening of quenched and tempered steels for a given carbon content,
resulting in higher strength and improved mechanical properties. The deeper
hardening is possible because the alloying elements shift the nose of the time-
temperature transformation (TTT) diagram to the right.
2. Higher tempering temperatures are possible while maintaining high strength and
good ductility.
3. Improved mechanical properties at high and low temperatures.
4. Greater corrosion and elevated-temperature oxidation resistance.
5. Formation of hard carbides to provide greater wear resistance. Alloying elements that
are strong carbide formers, such as titanium or vanadium, help in preventing grain
growth at elevated temperatures by pinning the grain boundaries.
A list of important alloying elements and their effects are given in Table -1. The most
important reason for adding alloying elements to steel is to increase hardenability. The most
effective alloying elements for increasing hardenability are manganese, chromium,
molybdenum, and nickel. Generally, the higher the alloy content, the greater the
hardenability, and the higher the carbon content, the greater the strength. By increasing the
depth of hardening, larger sections can be through hardened, providing the strength and
toughness advantage oftempered martensite. Also, by increasing the depth of hardening, a
slower quench rate can be used, which reduces cooling stresses. Oil or air quenching reduces
thermal gradients that can lead to distortion or cracking. Carbide formers, such as
molybdenum and chromium, also retard tempering. By increasing the resistance to softening
during tempering, alloy steels are able to resist softening at elevated temperatures. Thus, a
lower-carbon content alloy steel can be used to obtain the same tempered hardness as a
higher-carbon-content plain carbon steel. A steel with a lower carbon content is usually
tougher than one with a higher carbon content. In addition, the ability to temper at higher
temperatures allows greater relaxation of stresses while maintaining the same hardness.

Table-1 Effects of alloying elements in steel

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 form
more 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.

To simplify the discussion, the effects of various alloying elements listed below are
summarized separately.
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 .
2. MANGANESE
Manganese (Mn) is present in virtually all steels in amounts of 0.30% or more. Manganese is
essentially a deoxidizer and a desulfurizer. 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. 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. 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 .
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. If combined with Mn or Mo, silicon may produce greater hardenability of
steels. 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. Si is a
noncarbide former, and free from cementite or carbides; it dissolves in martensite and retards
the decomposition of alloying martensite up to 300.
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.
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. 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 CrNi steels, the
addition of P can cause precipitation effects and an increase in yield points. 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.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. 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].
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
precipitationhardening
stainless steels, Al can be used as an alloying element, causing precipitationhardening
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.
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
nitrideforming
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.
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 chromiumiron 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.
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 FATT50%
(8C),
even at the subzero temperatures [20]. Nickel raises the corrosion resistance of CrNi
austenitic stainless steels in nonoxidizing acid medium.
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 0.200.40% 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.
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 ofWincreases in alloy steels,Wforms
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.
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.
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.
Niobiumcontaining
nonquenched 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.
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].
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 high-melting 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].
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].
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].
18 BORON
Boron (B), in very small amounts (0.00050.0035%), 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 nonequilibrium 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.
_ 2006 by Taylor & Francis Group, LLC.
19 ZIRCONIUM
Zircon ium (Zr) is add ed to killed HSLA steel s to obtain impr ovement in inclus ion
characteristi
cs, pa rticular ly su lfide inclus ions, wher e modif ications of inclus ion shap e impro ve
duc tility in trans verse be nding. It increa ses the life of he at-cond ucting mate rials. It is also
a
strong carbide form er and produ ces a contrac ted austenite phase field [5,15].
20 LEAD
Lea d (Pb) is sometime s added (in the range of 0.20.5 %) to carbon and alloy steels through
mechanical dispersion during teem ing to impr ove machin ability.
21 T IN
Tin (Sn ) in relative ly small amounts is harmful to steels. It ha s a very strong tenden cy to
segreg ate
at grain bounda ries and induces tempe r embritt lement in alloy steels. It has a detri mental
effect
on the surfa ce qua lity of con tinuous cast billets co ntaining small amounts of Cu [24].
Small
amoun ts of Sn a nd Cu also de crease the hot duc tility of steels in the austenite ferrite
region [25].
22 A NTIMONY
Antimo ny (Sb) has a strong tendency to segreg ate during the freez ing pro cess, and has a
detri mental effect on the surfa ce qua lity of con tinuous cast bill ets. It also has a very strong
tenden cy to segreg ate at grain bounda ries an d cause tempe r embri ttlement in alloy steels.
23 C ALCIUM
Calcium (Ca) is a strong deoxidizer; silicocalcium is used usually in steelmaking. The
combination
of Ca, Al, and Si forms low-melting oxides in steelmaking, and improves machinability.