ALLOYING ELEMENTS AND THEIR EFFECTS

Alloy Steels by Definition

A PLAIN carbon steel is iron combined with small amounts of carbon where the carbon content can vary
between 0.008% and approximately 2.0% A plain carbon steel can also contain limited amounts of manganese
(1.65% max ), silicon (0.60% max ), and copper (0.60% max ) and still be classified as a carbon steel. The more
common carbon steels are the standard types such as C1005 with approximately 0.05%C up through the C1095
type with approximately 0.95%C. The C1100 steels are resulfurized and the C1200 steels are resulfurized and
rephosphorized.

By simple definition, an alloy steel is a type of steel to which one or more alloying elements have been added to
give it special properties that cannot be obtained in carbon steel. The constructional alloy steels are those
generally considered to be AISI 1300 through the AISI 9800 series, although modifications of these types are
also used in special applications. The chemical limitations of an alloy steel, as defined by the American Iron
and Steel Institute (AISI), are as follows:

"Steel is considered to be alloy steel when the maximum of the range given for the content of alloying elements
exceeds one or more of the following limits: manganese, 1.65%; silicon, 0.60%; copper, 0.60%; or in which a
definite range or a definite minimum quantity of any of the following elements is specified or required within
the limits of the recognized field of constructional alloy steels: aluminium ,boron, chromium up to 3.99%,
cobalt, columbium' molybdenum, nickel, titanium, tungsten, vanadium, zirconium, or any other alloying
element added to obtain a desired alloying effect."

To simplify the designation of alloy steels specified to chemical composition limits, a four-numeral series has
been established by the Society of Automotive Engineers (SAE) and the American Iron and Steel Institute
(AISI). The last two digits of the four-numeral series are intended to indicate the approximate middle of the
carbon range. In some cases, five digits are given and the last three represent the carbon content as in the high
carbon-chromium bearing steels. The first two digits represent the alloy or alloys present. The various types of
alloy steel and their numerical designations are shown on the opposite page.

Functions of Alloying Elements in Constructional Alloy Steels

As a general rule, alloy steels are specified when more strength, ductility, and toughness are required than can
be obtained in carbon steel in the section or part under consideration. Alloy steels are also used when specific
properties such as wear resistance, corrosion resistance, heat resistance, and special low temperature impact
properties are desired.

Engineering reasons for the acceptance of any material can usually be justified, but it is often easy to lose sight
of the fact that there must also be an economic reason for the widespread use of alloy steels. It is interesting to
note that some of the largest users of alloy steels include the most cost-conscious industries who primarily use
alloy steels because of their net advantages over carbon steels. There must, of course, be a mating of the
economic and engineering factors in any given application. From a designer's viewpoint, alloy steels give
greater latitudes in design, greater safety with larger payloads, and less maintenance.

Large tonnages of the alloying elements -nickel, chromium, molybdenum, manganese, vanadium, and
others-are now used annually. They are generally furnished as ferroalloys, or in some cases as the pure element,
such as nickel, or as oxide compounds of the element, as with nickel and molybdenum. In these forms, they are
added to molten steel in specified amounts to produce the modern constructional alloy steels.

Alloying elements are incorporated in steel for one or more of the following reasons, of which the first two are
more important:

1. To improve mechanical properties through control of the factors, which influence hardenability, and to
permit higher tempering temperature while maintaining high strength and improved ductility
2. To improve mechanical properties at elevated or low temperatures
3. To increase resistance to chemical attack and to elevated temperature oxidation
4. To influence other special properties such as magnetic permeability and neutron absorption.

Microstructure of steel can be considered as being composed of two phases:

1. Ferrite, the magnetic alpha modification of iron possessing high ductility, but poor tensile strength
2. Cementite, the iron-carbide phase, a hard, brittle constituent. The carbide phase in alloy steel is not
generally pure iron carbide, hut rather a complex combination of iron and alloy carbides.

Alloying elements have definite effects on the properties of the ferrite and carbide phases present. They
improve the mechanical properties in two ways:

1. By changing the state of dispersion of the carbide in the ferrite

2. By changing the properties of the ferrite and carbide phases.
The alloying elements can be classified according to their specific influence on either the ferrite or carbide
phase. Some alloying elements, notably manganese, chromium, molybdenum, and vanadium, dissolve in the
ferrite phase and also form carbides. Such elements as nickel, copper, and silicon do not form carbides in steel.
When present in the amounts usually found in alloy steels, they dissolve in and strengthen the ferrite.

The highest mechanical properties of the constructional alloy steels are developed principally by quenching and
tempering. If an alloy steel has been well quenched, maximum surface hardness will be developed. It is
important to remember that carbon is responsible for the maximum attainable surface hardness in the section
being quenched, but practical considerations necessitate the use of alloys to get maximum surface hardness and
depth of hardening as section sizes increase. Alloying elements such as nickel or chromium do not, in the
constructional alloy steels, make the steel surface any harder, but rather improve the hardenability and the
mechanical properties of the heat treated alloy steel by influencing the rate of austenite transformation so that
deep-hardening characteristics are obtained. In hardening 0.30% carbon steel, a quenching speed of 1800' F per
second through the 1300' F temperature level on cooling must be maintained to secure the greatest hardness.
Alloying elements reduce the value of this critical quenching speed to 100' F per second or less, thus permitting
the steel to be cooled to temperatures of 400 to 500' F before any transformation occurs. In this range,
hardening can occur completely through much heavier sections of alloy steel than could possibly be the case
with the carbon steels. Depending on alloy content, sections 2, 3, 4 in., and over can be through-hardened by
quenching.

The depth of hardness can be determined by direct readings on transverse sections through various diameter
bars or can be estimated from the end-quench hardenability test.

Even when heat is extracted from alloy steels at slower rates, maximum hardness can be attained because the
reaction rates involved in the decomposition of austenite on cooling are slower in the presence of the alloying
elements. In practice, this means that a less drastic quench can be employed, and that heavier sections will
develop full hardness. The slower quench creates a lower thermal gradient and minimizes quench cracking and
warping.

In the practical application of the constructional alloy steels, it has been desirable, in order to obtain the best
combination of strength and ductility in the heat treated condition, to have a steel containing both a ferrite
strengthener such as nickel and the carbide forming elements chromium and molybdenum, The latter elements
allow higher temperatures to be used for tempering while maintaining high tensile strength and a good degree
of ductility in addition to their function of promoting full-hardening at slower cooling rates.

Specific Effects of Alloying Elements in the

Constructional Alloy Steels
Manganese

Manganese is normally present in all commercial steels. It is essential to steel production, not only in melting
but also in rolling and other processing operations. In hot-working operations, the action of manganese on
sulphur improves hot working characteristics and contributes to better surface on the product.
Manganese is soluble in both alpha and gamma iron, and also forms a carbide, Mn3C. Under certain conditions
the eutectoid percentage of carbon is lowered, and at 2.0% manganese, becomes 0.67%C. Manganese also
lowers the critical points effectively, in a manner similar to that of nickel, and causes a pronounced hysteresis
effect between the heating and cooling transformations.
In the constructional alloy steels, manganese very markedly decreases the critical cooling rate and contributes
thereby to deep hardening.
With a manganese content of 11.0 to 14.0% and with a carbon content of 1.00 to 1.40%, the alloy is austenitic.
This analysis is particularly resistant to wear and abrasion under high impact stresses.

Silicon

Additions of silicon raise the critical temperature on heating by amounts varying with the carbon content.
Heating temperatures for quenching treatments are therefore increased. Silicon is not a carbide-forming element
in steel, but enters into solution in the ferrite. It increases the strength of the ferrite without loss of ductility
when added in amounts up to 2.500/0. In these large quantities, however, it introduces processing difficulties,
such as poor machinability, and increases susceptibility to decarburization.
One of the most important applications of silicon is its use as a deoxidizer and in molten steel. Silicon is usually
present in fully deoxidized constructional alloy steels in amounts up to 0.35%, insuring the production of sound,
dense ingots. Silicon increases hardenability and strengthens low alloy steels. In larger amounts it increases
resistance to scaling at elevated temperatures and also raises the 500ºF embrittlement range for ultra high
strength applications.
Nickel

Nickel as an alloying element in constructional alloy steels is a ferrite strengthener and is soluble in all
proportions in both gamma and alpha iron. It depresses the Ac and Ar critical points. It lowers the carbon
content of the eutectoid, which, with 3.5% nickel steel, is reduced to 0.70% carbon.
Since nickel does not form any carbide compounds in steel, it remains in solution in the ferrite thus
strengthening and toughening the ferrite phase. In either the annealed or untreated condition, nickel will
increase the internal strength and elastic limit over corresponding carbon steel. Nickel steels are easily heat
treated because nickel very effectively lowers the critical cooling rate necessary to produce hardening on
quenching. In heat-treated steel, nickel increases the strength and toughness. Resistance to impact stresses at
sub-zero temperatures is also considerably improved.
In combination with chromium, nickel produces alloy steels with higher elastic ratios, greater hardenability,
higher impact, and fatigue resistance than are possible with carbon steels.

Chromium

Chromium as an alloying element in constructional steels is found to form a solid solution with both the alpha
and gamma phases of iron. With carbon and iron it forms a complex series of carbide compounds of chromium
and iron. It is a strong carbide former, similar in this respect to molybdenum and tungsten. It raises the Ac"
critical point, especially when large amounts of chromium are present. The eutectoid carbon content is found to
be lowered by chromium additions, by an amount varying with the quantity present. At 2.0%, chromium, the
eutectoid forms with 0.62% carbon. With 12.0% chromium, eutectoid carbon drops to under 0.40%.
Complex chromium-iron carbides go into solution in austenite slowly; therefore a sufficient heating time before
quenching is necessary when treating the medium carbon grades. If the chromium is sufficiently dissolved in
austenite, greater depth of hardening on quenching is obtained because the critical cooling rate required is
decreased.
Chromium is essentially a hardening element, and is frequently used with a toughening element such as nickel
to produce superior
mechanical properties. At higher temperatures, chromium contributes increased strength, but it is ordinarily
used for applications of this nature in conjunction with molybdenum.
Two of the most important properties of steels containing chromium are wear resistance and cutting ability.
These effects are primarily due to the high hardness of the chromium carbides.

Molybdenum

Molybdenum as an alloying element in steel can form a solid solution with the ferrite phase and also, depending
on the molybdenum and carbon content, can form a complex carbide. Molybdenum slightly increases the
electrical resistance of low carbon steels. This indicates it is largely in solid solution in ferrite. In high carbon
steels, electrical resistance is decreased, which gives evidence that the molybdenum is largely confined to the
carbide phase when the steel is in the annealed condition. Molybdenum raises the Ac3 critical point when added
in the usual amounts (0.10 to 0.60%) for constructional alloy steels. When molybdenum is in solid solution in
austenite prior to quenching, the reaction rates for the transformation of austenite become considerably slower
as compared with a carbon steel, resulting in deeper hardening steel.
Molybdenum steels in the quenched condition require a higher tempering temperature to attain the same degree
of softness as comparable carbon or alloy steels. This resistance to tempering conferred by molybdenum
contributes to the ability of these steels to retain their strength at elevated temperatures. They show, because of
this effect, a considerable resistance to "creep" under sustained loads below their elastic limit at temperatures up
to 1100 F.
Alloy steels, which contain 0.15 to 0.30%, molybdenum, show a minimum susceptibility to temper
embrittlement. It has been found that some quenched and tempered alloy steels become brittle when slowly
cooled from the tempering temperature. This brittleness is made evident by low resistance to impact. The
susceptibility of such steels to "temper brittleness" is serious when large parts -are being made, for it is difficult
to cool large sections rapidly enough to prevent damage. Molybdenum additions in the amounts noted prevent
temper brittleness and allow usual cooling rates to be used after tempering.

Vanadium

Vanadium is one of the strong carbide-forming elements. It dissolves to some degree in ferrite, imparting
strength and toughness. The complex carbides formed by vanadium additions are quite stable.
Vanadium steels show a much finer structure than steels of a similar composition without vanadium. Grain
growth tendencies are minimized for temperatures in the heat-treating range, thus allowing higher hardening
and normalizing temperatures to be used.
As with other strong carbide-forming elements, vanadium raises the critical points and decreases the carbon
content of the eutectoid. This latter effect is very pronounced.
Vanadium gives other alloying effects of importance, namely: increased hardenability where it is in solution in
the austenite prior to quenching; a secondarv hardening effect upon tempering; and increased hardness at
elevated temperatures.
Boron

Boron is usually added to steel to improve hardenability; that is, to increase the depth of hardening during
quenching. During World War 11 and the Korean conflict, boron supplanted substantial quantities of nickel,
chromium, and molybdenum in a group of alloy steels, primarily to conserve these elements which are
ordinarily used to increase hardenability. Boron treated steels will usually have a boron content in the range of
0.0005 to 0.003%. This small] amount of boron appears to be the optimum range for enhancing the
hardenability of other alloys and because of this effect boron is designated as an alloy "intensifier." Whenever
boron is substituted in part for other alloys, it should be done so only with hardenability in mind because the
lowered alloy content may be harmful on some applications. Boron is very effective when used with low-carbon
alloy steels, but its effect is reduced as the carbon increases. When the carbon content is above 0.60%, the use
of boron is not suggested. Boron appears to be most detrimental to impact resistance in steels with low
transition temperatures; thus, if a nickel steel is to be used for low temperature applications it should not contain
boron, but, conversely, boron steels should contain nickel to offset the detrimental effect of boron on low
temperature transition.
Boron also has a relatively high nuclear cross section and can be used for neutron absorption.

Aluminium

Aluminium is widely used as a deoxidizer and for control of inherent grain size. When added to steel in
controlled amounts, it produces a fine austenitic grain size.
In fact, of all the alloy elements, Aluminium, in prescribed amounts, is the most effective in controlling gram
growth. Titanium, zirconium and vanadium are also effective grain growth inhibitors, but have adverse effects
on hardenability because their carbide compounds are very stable and difficult to dissolve in austenite prior to
quenching.
Aluminium is used as an alloying addition in amounts of 0.95 to 1.30% in the most popular nitriding steel. The
aircraft industry uses the nitriding steel, AISI 7140, because of its high surface hardness after nitriding and its
distortion-free properties up to approximately the nitriding temperature. The extremely high hardness of the
nitrided case is due to the formation of a hard, stable Aluminium nitride compound. The amount of aluminium
present in nitriding steels is considerably in excess of the amount necessary to produce a fine austenitic grain
size in other steels.

Copper

Copper as a metal has been used since antiquity, but its use as an alloy of steel is not so well known. Copper,
like nickel, does not form carbides in steel, but dissolves in and strengthens the ferrite. The use of copper in
certain alloys increases the resistance to atmospheric corrosion and increases the yield strength. Low carbon
alloy steels alloyed with 1.0 to 1.5% copper show precipitation hardening response during aging at
approximately 900' F that markedly increases the yield strength. Copper has been used in some die steel
applications and more specifically in the high-strength low-alloy steels where chemical compositions are
specially developed to impart higher mechanical property values and greater resistance to atmospheric
corrosion than are obtainable from conventional carbon structural steels containing copper.

Columbium

Element 41 of the periodic table has been named "niobium" by several international technical societies;
however, prominent metallurgists in this country prefer to use the name columbium.
Columbium influences the properties of steel by (1) imparting a fine grain size and preventing grain coarsening
as high as 1875' F, (2) by preventing air hardening, (3) by retarding softening during tempering, (4) by
hastening nitriding reactions, and (5) by enabling steel to resist creep and rupture at elevated temperatures.
Columbium enters into the ferrite of very low-carbon steels and strengthens the ferrite by the formation of an
intermetallic compound of limited solid solubility. Alloys containing more than 0.5%, columbium can be age
hardened when the carbon content is very low. In medium carbon steels, age hardening effects may be obtained
if the heat-treating temperature is high enough to effectively dissolve some of the columbium carbides.
One of the advantages of using columbium for grain refinement is that it has a low deoxidizing power and does
not introduce undesirable oxide inclusions into the steel. The A3 temperature is raised by columbium and the
A4, or upper austenite limit, is lowered, thus restricting the austenite temperature ranges.
Columbium decreases the hardenability of steel by carbon impoverishment as well as by grain refinement and
the nucleating effect of the carbides; but columbium can inhibit transformation when in solid solution.
The fine grain size and the decreased hardenability imparted by columbium increase the ductility of steels
slightly and the impact strength markedly. These improvements in properties are more noticeable in the lower
carbon steels.
Titanium

Titanium in steel is used primarily as a deoxidizer and an effective grain growth inhibitor; but as an alloying
element, it has the greatest carbide-forming tendency of any of the alloying elements. Its carbide-forming
tendency is so strong that a 0.50% carbon steel will have practically no tendency to quench harden when 1.5 to
2.0% titanium is added. Titanium's contribution to hardenability is usually negligible because it may only
dissolve in minute amounts in the presence of considerable carbon.
Titanium is now being used in some elevated temperature applications where high stress rupture and secondary
hardening effects are required. In very low carbon steels, titanium has a pronounced effect on strengthening the
ferrite by solid solution effects and ranks next to silicon in this respect. Titanium residuals of 0.02% can cause
impairment of impact properties by shifting the transition zone to higher temperatures and may cause increased
susceptibility to temper brittleness in steels fully quenched and drawn at 1200' F.

Zirconium

Zirconium is a grain-growth inhibitor and is a more potent deoxidizer than boron, silicon, titanium, vanadium,
or manganese. It has been considered as a substitute for manganese in combating hot shortness, but has not been
used for economic reasons.
The chief commercial use of zirconium is in low-alloy high-strength steels to improve their hot rolled
properties. Improved low-temperature properties have been reported by some investigators who have shown
that zirconium is more effective than vanadium in raising the low-temperature Izod impact property of certain
steels.
Zirconium has a positive effect on hardenability, but usually it is not sufficiently great enough to use the
element primarily for this purpose.
The elevated temperature properties are generally improved by the presence of zirconium nitrides which
apparently are stable nitrides of low solubility that enable the steel to resist creep.

Cobalt

Cobalt is soluble in all proportions in gamma iron and has nearly 75% solubility in alpha iron. Cobalt hardens
or strengthens the ferrite when it is dissolved in ferrite and thus resists softening under elevated temperature
conditions. The carbide-forming tendency is similar to or slightly higher than iron's carbide-forming tendency.
With respect to hardenability, cobalt has a negative effect for 0.40% carbon steels and hastens the
transformation to softer products rather than retarding transformation and inducing hardenability, as do most
alloying elements. However, in very low-carbon chromium steels, cobalt has been shown to increase
hardenability.

Combination of Alloying Elements

Combinations of the alloys in all possible proportions would, of course, result in a multitude of alloy steels.
However, by careful consideration of the characteristics of various alloy combinations, a relatively small list of
standard alloy steels meets the requirements of steel producers and consumers. In the standard constructional
alloy steels, carbon, manganese, and silicon are elements, which occur normally. A steel containing one
additional alloying element, such as nickel, chromium, or molybdenum, is known as single alloy steel. When
two such alloying elements are added, it is known as a double (binary) alloy steel; when three are added, it
becomes a triple (ternary) alloy steel.

In general, it may be said that the combination of alloys in constructional steels results in no loss of the qualities
which are imparted to the steel when alloying agents are added singly. For instance, if nickel strengthens ferrite
when used alone, it will act to an equivalent degree when used in combination with other elements. When used
in combination, alloys may in fact so complement each other as to give greater overall benefits than when used
singly in much larger quantities. Thus steels of the nickel, chromium, or molybdenum single alloy types are
used generally in smaller sections where through-hardening and suitable mechanical properties can be attained.
When larger sections are to be handled, the double and triple alloy types are preferred because they harden
deeper and offer increased resistance to tempering. The triple alloy types afford an interesting example of more
uniform properties because the common residual elements are specified as alloys so that unexpected effects due
to occasional variations in residual alloys are not encountered. Also, the probability that all specified elements
will occur at the low limit of the specified composition is less than that for single or double alloy compositions.
Closer control of hardenability and resulting mechanical properties is therefore possible.