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Fundamental Characteristics of Alloy Steel t

ABSTRACT
is necessary if s ~ e e l sare to be selected and used intelligently over the v.ery wide range of conditions of actual
service. The most innportant of these principles are outlined and illustrated; few specific applications are mentioned, although it is hoped that the discussion will be
found applicable to some of the current metallurgical
problems of the industry.

The elements of the metallurgy of alloy steels are


discussed .briefly, in as simple terms as possible. Technical terms are defined in the test, and heat-treating
terms are defined in an appendix. The author believes
that there are a small number of fairly siniple basic
principles which determine the behavior and properties
of any steel, and that a proper grasp of these principles

INTRODUCTION
In common with most of our basic industries, the
petroleum industry is a large consumer of steel; perhaps, on a tonnage basis, next in importance only to
the automobile and railroad industries. Steel is, without ,
doubt, the industry's most important structural material, and there is no phase of the vast and manifold
activities involved in petroleum technology in which
ferrous alloys in one form or another do not play a vital
part.
The growth and development of petroleum technology
has been rapid, particularly since the invention of the
internal-combustion engine and the exploitation of the
motor car. The crude equipment of the early days was
soon found inadequate for the demands put upon it,
and the introduction of iron and steel structures began
a t a n early date. Plain-carbon steel, in its various
grades, was employed during this period-largely because i t was the only material of its kind economically
available in the tonnages required. With the rapid ex-.
pansion of the auton~otive industry a corresponding
development occurred in petroleum technology; the increased demand for motor fuels and lubricants led to
the drilling of deeper and deeper wells and the opening
up of new oil fields-involving, in many locations, corrosive, briny waters and the more corrosive " sour "
crudes. At about the same time refinery methods were
undergoing radical changes a s a result of the development of various " cracking " processes, practically all
of which employ either higher operating temperatures
or pressures than previously had been found necessary.
This trend toward increasingly severe operating conditions, in both the production and refining divisions of
the industry, soon began to t a x the capacity of plaincarbon-steel equipment and to reveal its inherent limitations. The drilling of deeper wells demanded higherstrength
steels capable of being used in lighter sections
-

with resultant saving in weight; the " sour " crudes and
corrosive brines required materials with increased resistance to corrosion for both production and refinery
equipment; increased temperatures and pressures in
distillation processes demanded structural materials
which possessed not only increased resistance to oxidation and corrosion, but improved strength and resistance
to " creep " a t elevated temperatures.
Hence, for the past several years the engineers and
metallurgists of the petroleum industry have been
searching for; and adopting, structural materials which
are better suited to modern operating conditions than
carbon steel. These new materials are, of course, alloy
steels-many
of which have been so successfully employed in the automotive, railroad, and aviation industries. I t is not to be inferred t h a t plain-carbon steel
has no place in petroleum technology; on the contrary,
for many applications i t is eminently well suited to the
requirements, both from a n economic and a metallurgical standpoint. However, for certain purposes, alloy
steels have been found sufficiently better fitted to meet
the increased demands of present-day service a s to
justify their higher initial cost. That this trend toward
the introduction and use of alloy steels will be continued
and extended is allnost beyond question.', '"
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THE METALLURGY OF ALLOY STEELS

Although in this review no attempt is made t o cover


the various aspects of the manufacture of alloy steels,
i t may be advisable, before discussing the' metallurgy
of these materials, t o make a rather arbitrary distinction between alloying elements present in steel a s a
result of the de-oxidation or refining practices and those
gresent a s a result of intentional alloy additions. I n
; h ~c t v i r t ~ c tsense all steels. with the e ~ ~ e n t i nnf
n nure

ing review of the effects of alloying elements in steel is


to be considered, a s applying to elements deliberately
added for the definite purpose of influencing the properties, mechanical- or otherwise, of the finished product.
Out of some 40 possible elements which might be intentionally added to iron or steel, there is a surprisingly
small .number which, up t o the present time a t least,
has been found to have sufficiently beneficial effects
a t a reasonable cost to warrant investigation and commercial development; without regard to relative importance, these a r e manganese, silicon, chromium, nickel,
molybdenum, tungsten, vanadium, titanium, aluminum,
zirconium, copper, cobalt, and the non-metallic elements,
phosphorus, nitrogen, and oxygen. Carbon is not included in this list a s a n alloying element, since i t is
invariably present to a greater or lesser extent-and,
except in the instance of certain grades. of the highlyspecialized stainless alloys, is a s essential a constituent
of steel a s iron itself.

iron-carbon alloys, a r e alloy steels-since they all con.tain some proportion of such elements a s manganese,
silicon, aluminum, chromium, nickel, copper, phosphorus,
etc., either a s impurities from the raw materials or a s
"residuals " from the furnace, ladle or mold additions
made during the finishing of the heat or the casting of
the ingots. With the exception of manganese and possibly silicon, these "residual " elements are present in
very small quantities-usually under 0.1 per c e n t a n d
their effects in a true alloying sense may be disregarded.
In certain instances, however, these "residuals," particularly when they a r e present in the form of oxides,
silicates, carbides, o r other non-metallic compounds,
may play an important r81e in determining the behavior
of the finished product, chiefly with respect to its characteristic grain size, hardenability, and response to heat
treatment; this aspect of the effect of very small quantities of certain special elements will be touched upon
later in connection with the discussion of hardenability
and heat treatment. Unless otherwise stated, the follow-

1. WHY ALLOYING ELEME:NTS ARE ADDED TO STEEL


A perusal of the metallurgical literature, both technical and promotional, might lead one to suspect that the
reasons ,for the addition of alloying elements to steel
are practically infinite in number. The flood of claims
for this or that alloying element or combination of elements is, to say the least, somewhat confusing; i t frequently happens that users of.alloy steels are forced to
select a steel for a given part from literally dozens of
nominal compositions. This state of affairs works a
hardship not only on the consumer, who often may not
be able to select the particular steel which provides
the most service per dollar, but also on the steel manufacturer, who must stand ready to furnish this large
variety of compositions-many of which are, in effect,
duplicates insofar a s actual performance is concerned.
I t may be advisable, therefore, to inquire into this situation in a general way, and to attempt to outline briefly
some of the more important reasons for the addition of
alloying elements to steel; in short, t o point out which
alloys a r e most effective in producing certain desired
results in the light of modern metallurgical knowledge.
The complexities and ramifications of the subject are
such that in the present state of our knowledge we cannot hope t o arrive a t a complete and satisfying philosophy of alloy steels. However, certain well-defined trends
in this field of metallurgy are gradually gaining recognition, and we can a t least organize our thinking along
these lines to the end t h a t eventually, a s more data are
accumulated, a rational explanation will be a t hand for
many of the observed facts which a t present seem rather
obscure and unrelated to one another. E. C. Bain ' has
already made a valuable and clarifying contribution to
this field of metallurgical thought; and his paper, together with other publications emanating from the research laboratory of the United States Steel Corporation, has been drawn upon freely in the preparation
of this paper.

Alloying elements, properly so-called, a r e usually incorporated in steel for one or more of the following
reasons :
1. To increase resistance to chemical attack (corrosion) and to elevated-temperature oxidation
(scaling).
2. To improve mechanical properties a t atmospheric
temperatures through control of the factors which
influence hardenability and related phenomena.
3. To improve mechanical properties a t elevated or a t
low temperatures.
4. To influence other special properties.
This order, used in what follows, was chosen for convenience of discussion-and
implies nothing a s t o the
relative importance of the several factors-which, indeed, differs from one application to another.

1. ELEMENTS WHICH INCREASE RESISTANCE TO CORROSION AND TO ELEVATED-TEMPERATURE OXIDATION

Corrosion
The effect of chrbmium, with or without, the addition
of nickel, in increasing the resistance of iron alloys to
many forms of chemical attack is too well known to
require extended discussion; its use is exemplified in
the wide variety of comnlercial stainless steels an.d other
ferrous alloys designed to possess increased resistance
to corrosion-ranging in chromium content all the way
from about 5-30 per cent, or higher in some instances.
In the absence of nickel these chronlium alloys are of
the so-called ferritic * type, i.e., they are magnetic a t
atmospheric temperatures-and, when they contain sufficient carbon, may be hardened by quenching from
* T h e constituents, ferrite nnrl n~ist~:nite,\\.ill be discossed
more f r ~ l l yi n n s u b s e r l ~ ~ e ns te c t i o l ~ .

TERISTJCS OF

temperatures above the transformation-temperature


range which, for most of these alloys, lies in the vicinity
of 1,400-1,600 deg. F.; however, temperatures a s high
a s 1,850 deg. F. a r e often used for hardening these
alloys. The chief effect of nickel, when added in sufficient amount to these chromiunl alloys, is to render
them austenitic * a t atmospheric temperatures, i.e., it
tends to retain the high temperature, non-magnetic
form of iron (austenite) a t room temperature. Although these austenitic alloys are not hardenable by
heat treatment like some of the straight-chron~ium
steels, they have many desirable nlechanical properties,
such a s high strength and great toughness, in addition
to corrosion resistance. The contribution of nickel to
the stainless characteristics of these alloys is small in
comparison to that of chromium. Additions of molybdenum or tungsten a r e often made to these stainless
steels, partly for the purpose of enhancing corrosion
resistance and partly for the improvement they impart
to the mechanical properties a t elevated temperatures;
titanium, or more rarely columbium, is added in small
amounts for its beneficial effect in fixing the carbon and
thus preventing inter-granular corrosion-which otherwise is likely to be troublesome in welded structures.
Leaving the ferrous alloys of the so-called stainless
type and turning to those with only moderate, although
still noteworthy, resistance to milder types of corrosion
(such a s atmospheric corrosion) we find copper a s the
in combioutstanding alloying element '-'-frequently
nation with molybdenum, chromium, silicon, or phosphorus. In low- or medium-carbon steels the presence
of copper in amounts usually under 0.5 per cent results
in a n appreciable increase in resistance to atmospheric
corrosion, and these steels have been developed commercially on a n extensive scale. More recently the highstrength steels containing copper, chromium, silicon,
and phosphorus, developed particularly for transportation equipment ' have shown excellent resistance to
certain types of corrosion, in addition to possessing attractive mechanical properties.
No attempt will be made to discuss in detail here the
mechanism by which the above-mentioned alloying elements impart increased corrosion resistance to ironbase alloys. I t is fairly well established that these elements promote the formation of a n extremely thin, impervious, surface film of oxide or similar substance
which protects the metal beneath from further attack.
The corrosion resistance of the steel depends, to a large
extent, upon the continuity and successful maintenance
of this protective surface film.
In connection with the subject of corrosion resistance,
i t should be kept in mind that no single alloy or combination of elements has yet been found which is resistant
to all corroding environments; in other words, a universal corrosion- and heat-resisting alloy has not a s yet
been devised-and probably never will be. Each alloy
has its limitations; each new application should be
investigated thoroughly, and the alloy best suited to
the purpose selected on the basis of tests intelligently
applied and interpreted; in general, these should be
nothing short of actual service tests. Moreover, care
must be taken to insure t h a t the alloy finally selected

ALLOYSTEEL

211

has had the proper conditioning treatment, be i t thermal


or niechanical, before installation; otherwise, disastrous
and costly failures may be the result. It may be worth
pointing out, in connection with both the stainless and
the low-alloy steels, that difficulties are frequently encountered because of the fact t h a t steel specifications
a r e often drawn up by engineers rather than by steelproducing metallurgists; such specifications often limit
the steel' manufacturer unnecessarily by attempting to
define the properties of the product in terms of chemical
composition o r steel-making methods instead of in terms
of ultimate service requirements which the material
will have to meet. The sooner we get away from specifications which do not really specify, the better i t will be
for both producer and consumer.

'

Oxidation
In general, the elements which impart corrosion resistance to iron alloys also contribute increased resistance to elevated-temperature oxidation, or scaling.
Chromium is particularly effective in this respect a s
exemplified in the high-chromium ferritic alloys containing upwards of 25-30 per cent chromium, and in
the various austenitic alloys carrying 25 per cent
chromium and 12 per cent nickel, or thereabouts. A
chromium .content even a s low a s 5 per cent results
in considerably increased resistance to corrosion and
scaling a s compared to plain-carbon steels; a s an
example of this, we have the 4-6-per-cent chroiniuin
steel now extensively employed in many oil refinerie'S.
As mentioned above under the subject of corrosion resistance, molybdenum, tungsten, titanium, columbium,
or other elements may be added to the oxidation-resistant alloys for certain specific effects. Copper has not
been widely exploited a s a n alloying element f o r increasing resistance to elevated-temperature oxidation, although i t undoubtedly contributes something in this
respect-and
several practical applications of copperbearing steels have been made with this feature in
mind.' Aluminum seems to be a n element which, when
present in sufficie~ltquantities, is effective in increas-'
ing oxidation resistance; but its practical application
has been more or less limited to the addition of aluminum to the surface of articles and parts subject to
exposure to high temperatures. Aluminum is one of
the more difficult alloying elements to incorporate satisfactorily into steel.
The mechanism of oxidation resistance is essentially
the same a s that of corrosion resistance; it undoubtedly
involves the formation of a tight, impervious, protective,
surface oxide layer which resists attack and protects
the metal beneath it. Indeed, oxidation or scaling a t
elevated temperatures is only a particular form of
chemical attack, and there is no reason for suspecting
that quite different mechanisms a r e involved in the processes of corrosion and oxidation of metal or in their
prevention.
The high-alloy stainless and' austenitic steels .have
been discussed first merely a s a matter of convenience;
but this arrangement does not imply that they are
necessarily of first importance.

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'

'

so that it occurs a t a lower temperature than would


be the case with carbon steels, and that this lowering
of transformation temperature results in the finer carbide distribution. Manganese, chromium, nickel, silicon,
molybdenum, tungsten, vanadium, and various combinations of these elements a r e particularly effective in
this respect. These same elements, when they a r e in
true solution in the austenite, act in another very important capacity, viz., to increase hardenability * on
rapid cooling or quenching; for this reason they a r e
sometimes referred t o a s " deep-hardening " elements.
This effect permits the attainment of uniformly high
strength throughout much heavier sections than would
be possible with carbon steels, and forms the basis for
much of the demand for alloy steels in the automotive
industry.

2. ELEMENTS WHICH IMPROVE MECHANICAL PROPERTIES AT ATMOSPHERIC


TEMPERATURES THROUGH CONTROL
OF THE FACTORS WHICH INFLUENCE
HARDENABILITY ,AND RELATED PHENOMENA
For the practical purposes of this discussion, most
plain-carbon and low-alloy steels may be considered
a s consisting, a t atmospheric temperatures, of only two
major structural constituents: ferrite and carbideferrite being the metallographic term for the so-called
"alpha" or low-temperature magnetic form of iron,
stable a t temperatures below the transformation (or
so-called critical) range; carbide or " cementite " being
the metallographic name applied to the chemical compound, iron carbide (Fe3C) formed by union of iron and
carbon. Ferrite is relatively soft, ductile, and of low
strength; whereas the carbide is glass-hard, brittle, and
presumably of very high strength. As will be discussed
later in more detail, such steels may consist, a t atmospheric temperatures, partly or wholly of two other constituents : martensite and austenite; martensite (an
essentially unstable solution of carbon in iron) is the
characteristic constituent of fully quench-hardened
steel, while austenite is the high-temperature, or socalled " gamma," nonmagnetic form of iron, stable a t
temperatures above the transformation range. Most
carbon and low-alloy steels, a s ready for service, consist
merely of ferrite and carbide; and i t is the distribution
of these two constituents-the
one soft and' tough, the
other hard and strong-which,
to a large extent, determines the useful mechanical properties, strength,
toughness, ductility, hardness, etc., of the product. I t
is becoming increasingly evident that alloying elements
in low-alloy steels may bring about improvement in the
physical properties of the metal in one or more of the
four following ways :
a. by changing the distribution of the carbide in the
ferrite matrix;
b. by changing the properties of the ferrite;
c. by changing the constitution and, hence, the properties of the carbide;
d. by forming finely-divided oxides or similar nonmetallic con~poundsdispersed through the metal.

a. Carbide
Distribution
-

With one or two possible exceptions, almost any alloying element which can be put into solution in austenite
can be expected to change the distribution of the carbide
in ferrite a s compared to plain-carbon steel. This
change is toward a finer dispersion of the carbide, and
it results in a n ilicrease in hardness and strength, with
less sacrifice of toughness and ductility, than is the case
with carbon steels. The nlechanism by which this effect
is accomplished need not be treated in detail here; it
will be sufficient for the moment to state that a t a given
slow, or moderately slow, rate of cooling from the
austenitic condition these elements retard the reaction :

Austenite+ferrite+carbide

h. Ferrite Properties
The ferrite matrix in which the carbides a r e imbedded
in the so-called pearlitic (defined later, p. 215) or in the
quenched and drawn steels is somewhat strengthened
and toughened by the presence of alloying elements in
solid solution. This solid-solution strengthening effect
is slight in comparison with that which can be obtained
through manipulation of carbide distribution a s outlined above. Silicon, nickel, aluminum, cobalt, copper,
manganese, and chromium are probably the elements
which are most effective i n bringing about this solidsolution type of strengthening of the ferrite; these elements a r e effective in this r61e only insofar a s they are
dissolved in the ferrite itself, and not combined with
the carbon in the form of a carbide.

c. Carbide Properties

'

The property of certain alloying elements t o form


relatively stable carbides which a r e reluctant to go into
solution in austenite is now well recognized; the socalled " carbide-forming " elements molybdenum, tuagsten, vanadium, titanium, and chromium a r e the best
examples of this behavior. I n the presence of sufficient
carbon, these elements-through
the relative inertness
of their special carbides-may act in one or more of
several ways. A t ordinary quenching temperatures, the
alloy carbides, being less soluble than iron carbide
(FaC)do not go into solution readily in the austenite,
but remain undissolved-and may act a s grain-growth
inhibitors 011 heating or a s transformation nuclei on
cooling; this results in a fine-grained austenite of both
low-alloy and low-carbon content with accompanying
Iow hardenability; this condition may or may not be
a desirable one. A t higher 'quenching temperatures
some of the alloy carbide goes into solution, the alloy
and carbon contents become effective, and hardenability
is increased-still without excessive coarsening of the
austenite grain. Another effect of these reluctantly-solu-.
ble carbides is that of retarding the rate of softening

* Hnrdennbility is a term r~serl t o designate t h a t property


wliicli reflects itself i n t h c t l e p t l ~ l o wl~icli n steel nlnp be
I~nrdened when quenchecl fro111 n sr~itnhle tcmyprnture i n t o a
m e ~ l i ~ ~ofn i sufficient h e a t - w i t l ~ t l r i ~ pnlver
g
to tlevelop f u l l
(mnrtensitic) l ~ n r d n e s so r e r t h e s u r f a c e of t h e piece.

in tempering or of drawing after quenching; this is


a matter of carbide precipitation, and of its diffusion
and coalescence in the ferrite matrix-and there is undeniable evidence that, in this respect, the alloy steels
a r e much more sluggish than carbon steels. This results
in the possibility of employing higher tempering temperatures for the alloy steels-thus dissipating internal
stresses resulting from the quenching process, and a t
the same time of improving ductility, fatigue, .and impact properties without serious loss of strength. This
carbide behavior also has a n important bearing on the
highstrength of steel a t elevated temperatures-since
teinperature strength and resistance to creep are undoubtedly related in some way to the distribution and
stability of the finely-dispersed carbides.

cl. Oxide-forming Elements


The oxide compounds of aluminum, zirconium, vanadium, titanium, and silicon, when present in the form
of finely-dispersed particles, appear t o act both a s graingrowth inhibitors and transformation nuclei-resulting
in decreased hardenability. As in the case of the reluctantly-soluble caisbides, this dec~easein hardenability
may, in*certain applications, be undesirable; on the
other hand, for many purposes an extremely deep-hardening steel is to be avoided because of its tendency
toward cracking '--particularly when the deep-hardening characteristics a r e realized through a coarse austenitic grain size.. Therefore, the fine-grained steels
are, for the majority of applications, more desirable;
and the control of austenite grain groivth, through the
action of finely-dispersed carbides and oxides, is one of
the major developments of modern ferrous metallurgy.
As further examples of the effect of alloying elements
on nlechanical properties a t atmospheric temperatures,
we have the austenitic steels, of which the chromenickel stainless steels' have already been mentioned in
connection with corrosion and oxidation; the high
strength and ductility of these materials a t room temperature a r e two of their outstanding characteristics.
Another example of the austenitic type is the so-called
Hadfield high-manganese steel, which is characterized
by great toughness and resistance to wear and abrasion.

3. ELEMENTS WHICH IMPROVE MECHANICAL PROPERTIES AT TEMPERATURES


OTHER THAN ATMOSPHERIC
Elevated-Temperature Properties
As pointed out earlier, there is an,increasing demand
in the oil industry for steels which not only resist corrosion and oxidation, but also have mechanical properties superior to those of carbon steel a t elevated temperatures. This involves not only i~nprovedstrength
a s measured by short-time tests a t elevated temperatures, but also better creep-resisting properties-creep
being the tern1 applied to the gradual cleformation
which takes place over a n extended period under substantially constant load. . . ..
:

Intensive investigation of this phase of ferrous metallurgy is of rather recent origin, and all of the factors
are not yet thoroughly understood. I t is becoming apparent, however, t h a t the carbide-forming elements
molybdenum, tungsten, vanadium, titanium, chromium,
and combinations thereof a r e most effective in retaining
strength and. imparting creep resistance a t elevated
temperatures; this is entirely consistent with what has
been stated in the previous section on the tempering
behavior of the alloy carbides. It is reasonable to expect
that a steel which retains its hardness and strength
a f t e r tempering a t high temperatures would, by the
same token, possess high strength, hardness, and resistance to creep when actually used at these elevated
temperatures; high-speed steel, used f o r tools, is a
familiar and practical example of this type of behavior.
Manganese and nickel, a s incorporated in the austenitic
steels, a r e elements which contribute ductility, but very
little strength, a t elevated temperatures.

Low-Temperature Properties
An increasing amount of attention is being paid to
the properties of steels a t sub-zero temperatures; and,
since impact strength is a rather sensitive means of
detecting low-temperature embrittlement, i t is the property which is usually measured. All ferrous materials,
except possibly the austenitic chromium steels, become
more or less brittle if the temperature is carried low
enough; however, in the presence of suitable amounts
of nickel, chromium, manganese, zirconium, vanadium,
molybdenum, aluminum, copper, or certain combinations of these elements, the embrittlement range is
forced to lower temperatures and the steel is, in effect,
endowed with a wider range of sub-zero temperatures
over which satisfactory impact properties may be obtained.' The exact mechanism by which the alloy addition effects this improvement in low-temperature properties is not thoroughly understood a s yet, but appears
to relate to the ratio of the shear resistance to the inherent cohesion of the metal.''

4. ELEMENTS

INFLUENCE OTHER
SPECIAL PROPERTIES

The various esalnples of the addition of alloying elements to iron-base materials for the purpose of influencing some particular o r highly-specialized property are
too numerous to record in detail; only a few 'typical
cases will be mentioned. I n most of these instances the
alloy content .is relatively high in comparison with the
steels which we have been discussing in the foregoing
pages.
The effect of nickel on the thermal-expansion characteristics of ferrous alloys is well known, and is exemplified by alloys of the Invar and related types; likewise the magnetic and other elect~icalproperties are
materially influenced by large amounts of nickel as, for
example, in permalloy. Other elenlents which influence
magnetic and electrical properties are cobalt, tungsten,

molybdenum, chromium, and manganese, a s exemplified


in the special steels for permanent magnets. High-silicon
transformer sheet steel constitutes another example of
a class of materials to which specific and useful proper-

ties are imparted by a n alloying element. The various


types of stainless steels, a s well a s Hadfield manganese
and high-speed steel, have already been mentioned a s
typical examples of particular alloying effects.

11. THE ELEMENTARY METAL1 bGRAPHY OF FERROUS ALLOYS

Allotropy of Iron; Carbon Solubility


What peculiar property or combination of properties
is it that makes iron (or steel) the most useful and
economically important of all the common metals? There
can be no doubt that the supremacy of iron among
metals is, in large part, indirectly attributable to the
fact that i t is one of the few metals which is capable
of existing in more than one crystalline form-the two
forms in which we a r e interested a t the moment being
the so-called "alpha," or low-temperature, magnetic
form, stable a t temperatures below about 1,650 deg. F.
(900 deg. C.) and the so-called " gamma," or hightemperature, non-magnetic form, stable above 1,650
deg. F. (900 deg. C.). I n the presence of carbon, or
alloying elements in solution, the alpha form is known
to the metallographer a s "ferrite," and the gamma
form a s " austenite." A third form, known a s " delta "
iron, exists a t temperatures close to the melting point;
however, this form need not concern us for the moment,
since its crystalline structure is the same a s that of the
" alpha " form-and for the purposes of this discussion
i t has no practical significance except in connection with
the hot working of some of the, high-alloy stainless steels
a t very high temperatures.
The existence of the two allotropic forms of iron,
" alpha " and " gamma "-ferrite and austenite, respectively-!~,
perhaps, not nearly a s important from a
metallurgical viewpoint a s the fact that these two forms
have very different solvent powers for other atoms, particularly carbon; it is upon this difference in the properties of alpha- and gamma-iron that the whole a r t and
science of heat treatment of ferrous materials is based.
The heavy line in Fig. 1 illustrates schen~aticallythe
solubility of carbon in alpha- and gamma-iron a t various
temperatures, under substantially equilibrium conditions; the broken thin lines in Fig. 1 indicate how the
temperature of the gamma $ alpha change or transformation is lowered by carbon; but, for the moment,
we may disregard these lines, and focus our attention
on the carbon-solubility feature. Fig. 1 is applicable
to
iro,l-carbon alloys and plain-carbon steels.
For
purposes, it
be considered that in
plain-carbon steels the alpha-iron or ferritic forin
exists a t all temperatures below about 1,350 deg. F.
(730 deg. C.) and the gamma-iron or austenitic form
a t higher temperatures. This temperature (1,350 deg.
F.) (730 deg. C.) is known a s the lower critical or
transformation temperature, i.e., i t is the temperature
a t which ferrite begins to transform to austenite on
heating and a t which austenite completes its transformation to ferrite on very slow cooling. The addition of an alloying element may raise or lower this

transformation temperature, depending upon the particular element involved; moreover, such additions may
alter the carbon-solubility relationships considerablybut these effects will not be discussed in detail, except
a s they have a bearing on the practical aspects of the
subject a s i t is developed hereinafter. It will be noted
from Fig. 1 t h a t ferrite is.capable of dissolving only
very small amounts of carbon-a maximum of perhaps

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PER C E N T CARBON

Solubility of Carbon in Alpha-Iron and Gamma-Iron at


Va,riousTemperatures.

FIG. 1
O.O3-0.04 Per cent a t 1,350 deg. F. (730 deg. C.) and
only about 0.01 Per cent a t room temperature; whereas
austenite can dissolve upwards of 0.85 per cent carbon.

Effect of Cooling Rate


Now when a carbon 'steel of about 0.80 per cent
carbon is heated to 1,700 deg. F. (925 deg. C.) all of the
carbon will go into solid solution in the austenite; if the
steel is then cooled to some temperature below the equilibrium transformation temperature (1,350 deg. F.)
(730 deg. C.) the austenite will transform to ferrite and
the carbon will be forced out of solution, since ferrite
has relatively no solvent power for carbon. This carbon

precipitates in the form of iron carbide (FesC), a glasshard compound. If the cooling from the austenitic condition is very slow, a s in furnace cooling, t.he austenite
+ferrite transformation will take place a t or near the
equilibrium transformation temperature, the carbide
will be rejected in a pattern of thin plates or lamellae
separated by ferrite, and the steel will be quite ductile.
This structure, a s viewed in the metallurgical microscope, is known to the metallographer a s " pearlite," and
is illustrated in Fig. 2. If the cooling from austenite is
somewhat more rapid, the austenite + ferrite change
will be depressed below the 1,350-deg.-F. (730-deg.-C.)
equilibrium temperature; in other words, the austenite

Fig. 2

are the carbide laminations rendered visible. A correlation between hardness and actual spacing of the carbide
plates in pearlitic steels has been made by 0.V. Greene,=
as illustrated in Fig. 5.
At a certain critical rate of cooling from the austenitic
condition, and a t all faster rates, the carbide i s not
rejected at the time of the austenite +ferrite reaction, but is retained in solid solution a t temperatures
even a s low as atmospheric; the austenite +ferrite
transformation does take place, however, in these
quenching treatments-and,
since alpha-iron is relatively incapable of dissolving carbon under equilibrium
conditions, this solid solution formed on quenching is

Fig. 3

Fig. 4
Hardness

Cooling
Figure
Product
Rate
No.
2 . ........ .Very slow ........... .Very coarse pearlite. ........... 5
163
3 . .........Slow ................ .Medium coarse pearlite. ........ 15
207
4. ........ .Moderately rapid ..... .Fine pearlite .................. 38
363
Structural Differences Resulting When the Same Steel Is Cooled at Different Rates, with Consequent Differences
in Actual Transformation Temperature (Original Magnification 2,500X ; Picric-Acid Etch).
FIG. 2, 3, AND 4
will be under-cooled; the carbide will .precipitate in
the form of thinner and more closely-spaced plates than
in the instance of slow cooling, due to the fact that the
rejection takes place a t a lower temperature; the steel
will be harder, stronger, and less ductile a s compared
to the very slowly-cooled product. The structure is of
the pearlitic type, but of a fine variety, as illustrated in
Fig. 3. At still faster rates of cooling of the austenite,
the transformation and accompanying rejection of carbide is depressed to still lower temperatures with increased closeness of spacing of the carbide plates and
consequent hardening and strengthening of the metal
with decrease in its ductility. The microstructure is
still of the pearlitic type, but of such a degree of fineness that i t is not completely resolved by lenses of the
highest power; a n example of this very fine pearlite is
shown in Fig. 4, and i t is seen that only in a few places

1
1

unstable, or super-saturated, and carbide tends to precipitate from i t on the slightest provocation. This
unstable solid solution of carbon in alpha-iron, which
is known to the metallographer a s " martensite," is the
chief constituent of fully-hardened steel; i t is glass-hard
and brittle, and its microscopic appearance is shown in
Fig. 6. At intermediate cooling rates, mixtures of the
two structures (pearlitic and martensitic) may be
formed as a result of part of the transformation taking
place a t the higher temperatures (to pearlite) during
cooling and part a t the lower temperatures (to martensite) ; this is known as the " split transformation."
The foregoing discussion of the effect of cooling rate
upon the gamma + alpha transformation and the resulting pearlitic and martensitic structures is well
summarized in Fig. 7, taken from one of E. C. Bain's
publications.

The rejection of carbide from the unstable alpha-iron


solid solution (martensite) is the reaction which takes
place upon tempering or drawing back a piece of fyllyhardened steel, with consequent softening and recovery
of ductility and toughness. However, the carbide precipitated during the tempering of martensite does not
take the form of plates or lamellae as in the case of the
pearlitic structures formed directly out of austenite;
rather, the carbide is rejected as a fine dispersion of
more or less spheroidal particles, the size of which depends upon the tempering temperature and time; the

F/NENESS OF PEARL ITE. .


L AMEL L AE PER INCH. THOUSANDS.

The Hardness of Pearlite as Dependent Upon Fineness


of the Lamellae (0. V. Greene).
FIG. 5

Influence of Cooling Rate Upon the Temperature and


Product of Austenite Transformation in an 0.85-Per-Cent
Carbon Steel (E. C. Bain).
FIG. 7

Hardness: Rockwell, C-66; Brinell, 712. Typical


Martensite (Original Magnification 2,500 X ; Picric-Acid
Etch).
FIG. 6

higher the tempering temperature, the coarser the particles of carbide and the softer and more ductile the
steel.
I t should be apparent from the foregoing discussion
that the existence of the two forms of iron and the
action of carbon in forming the hard carbide, Fe3C, a r e
of almost equal importance in giving rise to the useful
properties of steel. Without the 'two allotropic forms
of iron-gamma and alpha, austenite and f e r r i t e w e
could not vary a t will the distribution of carbide in the
ferrite matrix and thereby attain the wide variety of
mechanical properties which make ferrous materials
so valuable; on the other hand, without carbon we

could make little practical use of these two crystalline


forms of iron, and we would have no such substance as
steel in the modern sense of the word. I t is evident that
the mechanical properties of steel are largely determined by its structure, i.e., the distribution of the
phases or constituents out of which i t is composed or
built-in short, its architecture. We have discussed the
effect of varying the cooling rate upon this architecture;
now let us inquire into the effect of alloying elements
on this vital characteristic of ferrous materials.

Effect of Alloying Elements


As stated above, some alloying elements tend to raise
the transformation or critical temperature of steel,
while others lower it. Elements which raise i t are referred to a s "ferrite stabilizers," since they tend to
widen the range of temperatures in which the ferrite
phase is stable a s compared to iron-carbon alloys; while
elements which lower the transformation temperature
are known a s " austenite stabilizers," for the obvious
reason that, in the process of lowering the transformation temperature, they widen the range of stability of
austenite. I n a subsequent section the common alloying
elements a r e classified with respect to these two effects,
as well a s to other specific effects which lend themselves
. t o tabulation. Certain of the ferrite-stabilizing elements, when present in ,sufficient quantity, have the
effect of obliterating the austenite phase entirely; the
high-chromium alloys, which a r e ferritic a t all temperatures u p to the melting point, constitute one practical
example of this behavior. On the other hand, some of
the austenite stabilizers, such a s manganese in Hadfield
steel, o r nickel in the chrome-nickel 18-8 and the Invar
alloys, depress the transformation temperature to such
a n extent that, a t least for all practical purposes, the
ferritic form does not exist a t atmospheric temperatures under ordinary conditions of treatment or service.
These behaviors, although they have no bearing on the
structural architecture of the alloys in connection with
carbide-distribution effects, a r e mentioned because they
constitute typical examples of alloying effects in the
increasingly important high-alloy, ferritic, and austenitic steels.
In the presence of sufficient amounts of carbon in lowalloy steels, the general effect of alloy additions which
enter into true solution in the austenite is to render
the reaction :
austenite += ferrite+carbide
more sluggish or more reluctant to take p l a ~ e ~ t h e r e b y
depressing i t to lower temperatures for any given rate
of cooling a s compared to plain-carbon steel. This action may manifest itself in one or more of three principal ways:
1. In heat treatments involving slower cooling rates,
the alloy-bearing steels yield finer pearlitic structures, with consequent increased hardness and
strength, a s compared to carbon steels.
2. In quench-hardening treatments a greater depth of
hardening may be achieved with the alloy steels,

and sections can be hardened all the way through


-which, with carbon steel, would have a soft
pearlitic core.
3. In the fully-hardened (martensitic) condition, the
softening action on tempering will be more sluggish in the alloy steels-and
higher tempering
temperatures may be employed to dissipate quenching stresses more effectively with less sacrifice of
hardness and strength than would be the case with
plain-carbon steels.
The first effect-that of the change in distribution
of carbides in the pearlitic structures-is illustrated in
Fig. 8 and 9, in which is shown a comparison of the
pearlite produced in a plain-carbon steel and a lowalloy steel of comparable carbon content, both cooled.
a t the same rate from 1,600 deg. F. (870 deg. C.). The
SAE-1040 steel (0.35-0.45 per cent C.; no other alloying
elements) of Fig. 8 shows a much coarser type of
pearlite than the SAE-4135 steel (0.30-0.40 per cent C.;
with chromium and molybdenum) of Fig. 9.
The second effect--the increased depth of hardening
induced by alloy additions-is
illustrated in Fig. 10,
which shows the hardness distribution across the section of 1%-in.-diameterrounds of three steels identically
quenched. The effectiveness of the alloys in augmenting
depth of hardening a s compared to the plain-carbon
steel (0.74 per cent C.) is quite evident, particularly
in the instance of the chrome-nickel steel which hardened throughout the 1%-in.section.
The third principal effect-that of retarding the softening on tempering-is shown in the comparisons hereinafter, in which the hardness, tempering time, and
tempering-temperature relationships are given for a
plain-carbon steel and several chromium-molybdenun~
compositions of similar carbon content (see Table 1)."
All the steels were tempered from the martensitic condition (oil quenched from 1,650 deg. F. (900 deg. C.) ) .
From these data it is evident that alloy additions, particularly those of the carbide-forming elements, have a
potent effect 'in retarding the reactions involved in
softening during tempering. The probable significance
of this behavior in relation to creep resistance has already been mentioned in the discussion of carbide-forming elements.
The effect of alloying elements in strengthening and
toughening the ferrite matrix itself, through simple
solid-solution hardening, has been alluded to elsewhere.
This is typically illustrated in Fig. 11, which depicts
the increase in hardness imparted to low-carbon and
carbon-free alloys by the addition of nickel, manganese,
or chromium. These alloys were tested in the annealed
condition, i.e., the structure was constant throughout the
comparison; and, since the carbon content is either low
or practically nil, it is the hardening due to the alloy
addition alone which is recorded; manganese is more
powerful than chromium in this respect, while nickel
occupies a n intermediate position.
Another effect of alloying elements which has been
briefly referred to is that of contributing to increased
hardenability without undesirable coarsening of the
austenite grains. Hardenability of plain-carbon steels

SAE-1040 steel (0.35-0.45 per cent carbon; no other


alloying elements).

SAE-4135 steel (0.30-0.40 per cent carbon; 0.80-1.10


per cent chromium; 0.15-0.25 per cent
molybdenum).

Microstructure of Two Steels of Approximately the Same Carbon Content, Both Furnace-cooled from 1,600 Deg. F.,
Showing Influence of Alloy Addition (Original Magnification 1,000 X ).
FIG. 8 AND 9

""

Shallow-Carbon Steel.
Medium-Chromium Steel.
Deep-Chrome-Nickel Steel.
Deeper Hardenability Contributed by Alloying Elements.
(E. C. Bain)
FIG. 10

7 8 9 1 0 / / / Z
PER CENT AAL LOYING ELEMENT, N/,CR.MN

Typical Examples of the Solid-Solution Hardening


Effects, of Alloying Elements in Ferrite.
FIG. 11

TABLE 1
Effect of Alloying Elements on Tempering Behavior

Analysis of Steel
I

Carbon
(Per Cent)
0.36
0.32
0.35
0.32
0.41

Chromium
(Per Cent)

Molybdenum
(Per Cent)

0.56

0.56
2.11
5.06
5.08

...

...

...
...

1.88
Analysis of Steel
h

Chro+um
(Per Cent)

Carbon.
(Per Cent)
0.36
0.38
0.37

...

...

.3.60
4.48

r
'

. .

Carbon
(Per Cent)
0.36
0.33
0.35
0.32

...

0.59
.

Molybdenum
(Per Cent)

Analysis of, Steel


A '

Chromium
(Per Cent)

...

1.94
2.02

...

Molybdenum
(Per Cent)

...
...

0.52
5.06

may be increased by quenching from higher and higher


temperatures ' through the agency of the coarse
austenite grains induced a t these higher temperatures;
however, this method of attaining increased depth of
hardening results in a n increased tendency to gross
and microscopic cracking, both associated with coarse
austenitic grain size. The addition of alloying elements,
particularly those of the carbide-forming type, is effective in restraining austenitic grain growth without
simultaneous sacrifice of hardenability ; in other words,
i t puts a t our disposal a class of steels which, a t the
proper heat-treating temperatures, are both fine-grained
and relatively deep-hardening. The principles involved
in this behavior a r e illustrated schematically in Fig. 12,
which is a n attempt to depict the probable relationship
between austenitic grain size, depth of hardening, and
dissolved-alloy content. The exact location and form of
the curves would, of course, vary with the particular
alloy or alloy conlbinations involved, and also with
carbon content; a constant carbon content is assumed for
the chart a s drawn.
The action of the oxide-forming elements in contributing to shallow hardening, through mechanical obstruction to austenitic grain growth on heating and nucleation
effects on cooling, is now reasonably well understood and
widely utilized in the production of steels of controlled
hardenability. This behavior and the principles involved
a r e employed largely in connection with the shallowhardening types of steel.

'

Hardness After Tempering for 1.75 Hours


a t 840 Deg. F. (450 Deg. C.)
A

Rockwell C :
33.9
41.6
45.7
47.0
51.3

Converted Brine11
321
401
444
.
461.
.
495

Tempering Time Required a t 1,020 Deg. F.


(550 Deg. C.) to Reduce Hardness to
Approximate Rockwell C 37-39,
Brine11 352-363
10 sec.
105 min.
43 hours

'

Tempering Temperature Required to Reduce


Hardness to Approximate Rockwell C 40,
Brinell 375, a t a Constant Tempering
.
Time of 20 Min.
660 deg. F. (350 deg. C.)
840 deg. F. (450 deg. C.)
1,020 deg. F. (550 deg. C.)
1,200 deg. F. (650 deg. C.)

A . S . Z M. G R A I N S I Z E N U M B E R

Schematic Representation of Relationship Between


Austenitic Grain Size, Depth of Hardening,
and Dissolved-Alloy Content.
FIG. 12

.
.

220

MATERIALS
111. THE HEAT TREATMENT OF STEEL

I t may be profitable now to review briefly the general


subject of heat treatment of steel in the light of what
has been stated in the foregoing pages, and to outline
the basic factors involved in the various heat-treating
operations.
In most heat-treating processes there a r e two fundamental or essential operations: heating and cooling.
A third factor, time a t one or more temperatures-either
in the heating, cooling, or tempering cycle-is also of
fundamental importance, and must be taken into consideration in devising a heat-treatment schedule for
any given steel. The three questions which must be
answered in .developing any such schedule are: How
hot and a t what rate shall we heat our steel? How long
shall we hold i t a t temperature? At what rate shall
we cool it? It is realized that, in practice, the size and
shape of the p a r t being treated must be taken into
account; but this will be neglected here, a s i t does not
affect the principles discussed.
The first step is to heat to some temperature above
the transformation range in order to put the iron in
the gamma state, so t h a t the carbon and other elements
may form the homogeneous solid-solution austenite;
this is the raw material out of which we build our structure in the subsequent cooling operation. For many
Purposes the rate of heating is not very critical-provided that it is not so excessively rapid that injury is
done to the material; however, i t is now known that the
rate of heating in some instances does have some influence on the size and growth characteristics of the
austenite grains, with consequent effects on hardenability; in these cases, rate of heating must be given
some consideration. The maximum temperature and
the time a t temperature in the austenitic range determine the
carbide which may be put
solution-higher
temperatures or longer periods a t
temperatwe resulting in more complete solution. For
some purposes i t is desirable to have all of the carbide
in solution in order to take full advantage of the hardening effect of the carbon and alloy contents; in other
instances we may wish to leave
of the carbides
undissolved for the purpose of restraining the growth
of the austenite grains. Fronl a practical standpoint,
undissolved carbides are almost always presentto some
estent in the auitenite of those alloy steels containing
the reluctantly-soluble carbides; this is because impractically-high temperatures or long times would have
to be enlployed to put all of these carbides into solution.
The nest step is the cooling of the austenite-slow
for the softer products, and rapid for the harder. I t is
in this step of the heat-treating process that the final

structure of the treated material is, to a large estent,


determined. In the high-alloy materials containing
austenite-stabilizing elements the high-temperatureaustenite solid solution may be retained all the way
down to room temperature, even after moderately slow
codling. In the low-alloy and plain-carbon steels the
pearlitic structures of various degrees of hardness and
strength are formed a t the slower rates of cooling;
while the fully-hard martensitic structure is formed
on rapid cooling, a s in quenching. A t intermediate rates
of cooling, mixtures of the two structures-pearlitic
and martensitic-may be formed a s a result of the socalled " split " transformation. I t should be borne in
mind that the cooling from hot-working operations, such
as rolling or forging, constitutes a heat treatment just
as much a s if a separate heating and cooling operation
were conducted; f o r many purposes, of course, the
structure resulting from such a cooling may not be the
one that is desired.
Many heat-treating processes a r e completed a t the
end of the cooling cycle, particularly those resulting
in the softer pearlitic structures. For the harder structures resulting from more rapid cooling rates, a third
step, consisting of a moderate re-heating (tempering
or draw-back) usually is required. This re-heating is
always carried out a t temperatures below the transformation range, i.e., temperatures a t which the stee]
is in the ferritic condition; i t has for its purpose the
relief of quenching stresses and the recovery of a certain degree of toughness and ductility through precipi~h~
tation and coalescence of the carbide
higher the tempering temperature or the longer the
time, the greater will be the relief of quenching stresses
and the softer the
It is highly desirable to
have at our command steels which can be tempered at
higher temperatures for more complete relief of stresses
without too great a sacrifice in hardness-and
in this
the
lnake a
New methods of heat treatment, involving constant
temperature transforniations in the range between the
temperatures a t which pearlitic and n~artensiticstructures are formed, have been developed recently; but,
since these have been described rather fully elsewhere:
the subject will not be taken up in detail here. It may
be worth mentioning, however, that a n entirely new
series of structures results from these constant temperature transformations, and that some rather attractive combinations of properties have been achievedparticularly in plain-carbon steels-through the use of
these novel methods of controlled heat treatment.

IV. CLASSIFICATION OF ALLOYING ELEMENTS


By way of summary, i t may be helpful to attempt a
rough classification of the various alloying elements
based on certain of their principal effects. Except in
the instances' of the austenitic steels, this classification

is to be construed a s applying only to medium- or highcarbon steels in which there is considerable carbon for
effective combination with the carbide-forming elements.

. .

Principal Effects or Tendencies of Alloying


Elements in Steel
To Stabilize
Austenite
Nickel (strong)
Manganese
Copper
Carbon
Nitrogen
Cobalt

To Form Carbides which


Restrain Grain Growth
and Resist Both Creep
and Softening on
Tempering
Vanadium (very strong)
Titanium (very strong)
Molybdenum (strong)
Tungsten (strong)
Chromium (moderate)
Zirconium (moderate)
Manganese (mild)
Cobalt (very weak)

To Stabilize
Ferrite
Chromium
Tungsten
Molybdenum
Vanadium
Silicon
Phosphorus
Aluminum
Titanium
Zirconiunl
Tin

To Form Oxides which


Restrain Grain
Growth
Aluminum (strong)
Zirconium (strong)
Vanadium (probably
strong)
Titanium (probably
strong)
Silicon (moderate)
Chromium (weak)
Manganese (weak)
Molybdenum (weak, if
a t all)
Tungsten (weak, if a t
all)

To Increase Hardenability

.To Strengthen
Ferrite

Manganese (strong)
Chromium (strong)
Silicon (strong)
Nickel (moderate)
Molybdenum (moderate)
Tungsten (moderate) .
Aluminum (moderate)
Vanadium (nloderate)
Copper (moderate)
Titanium (weak)
.
Cobalt (weak)
Zirconium (probably
weak)
Phosphorus ?
Nitrogen ?
Oxygen ?

Manganese (strong)
Silicon (strong)
Nickel (strong)
Cobalt (strong)
Aluminum (strong)
Chronliuln (moderate)
Copper (moderate)
Molybdenum (weak)
Tungsten (weak)
Vanadium (weak)
Titanium (weak) .
Zirconium (weak)
Phosphoru's ?
Nitrogen ?
Oxygen ?

To Increase Resistance
to Corrosion
Chromium
Copper
Nickel
Aluminum
Silicon
Molybdenunl
Tungsten

To Increase Resistance to
Oxidation (Scaling)
Aluminum
Silicon
Nickel
Copper
Molybdenum
Tungsten '

V. CLASSIFICATION OF ALLOY STEELS


Carrying the classification idea one step further, it
may be worth attempting some sort of a recapitulation
in the form of a classification of alloy steels themselves.
I t seems best to base this classification on broad. composition groupings rather than upon physical properties
o r other engineering characteristics. As pointed out
earlier in, this paper, the multiplicity of compositions
offered, with the attendant duplication of properties,
results in much confusion and a considerable amount
of what would appear to be wasted effort. Therefore,
no attempt will be made to make this scheme of classification complete or inclusive; only the more or less standa r d well-recognized types of alloy steels will be listed;
anything more ambitious than this would make our list
endlessly long. Whenever possible, the widely accepted
S.A.E.* scheme of classification will be f o l l o ~ e d . ' ~
* I n the S.A.E. numeral-indr?s system the 6y:t Jfgit indicates
tlie txpe to which the steel belongs; thus
1- indicates a

A. High-cilloy steels. (Total alloy content generally


in excess of 5 per cent). These a r e listed in Table 2.
B. Low-allog steels. (Total alloy content generally
less than 5 per cent). All the steels of this group are of
the ferritic type; and, therefore, the properties which
may be developed depend, to a large estent, upon the distribution of the carbide and ferrite phases. I n addition
to alloy content and heat treatment, the carbon content
of these steels plays a most important part in determining the lnasimunl physical properties obtainable. These
a r e listed in Table 3.
carbon steel ; " 0-" a nickel steel. nncl " 3- " a nickel-chromium
steel. I n the cn<e of the simple alloy steels, the second digit
generally indicates tlie al~proxiniate percentage of the predominant alloying element. Usually the Iy?t two or three digits indicate tlie average carbon content in points," or hundredths qf
1 per cenc. Thus "23-10" indicates a nickel @tee1 of approxlmnicly 3 per cent nickel (3.25 to 3.75) nnd 0.40 per cent carbon
( 0 . 0 3 to 0.45) ; and " 71260 indicates n tungsten steel of about
1 3 per cent tungsten ( 1 9 0 1 5 ) and 0.60 per cent carbon (0.50
to 0.70).

TABLE 2
A. High-Alloy Steels

(Total alloy content generally in excess of 5 per cent)


Austenitic Type

Chromium-Nickel Stainless Alloys


(SAE 30,000 Series)
18 per cent chromium; 8 per cent nickel
25 per cent chromium; 12 per cent nickel
8 per cent chromium; 20 per cent nickel
Hadfield Manganese Steel
12-14 per cent manganese (high-carbon)

High-Nickel A l l o ~ sof Low Coeficient of Thermal


Expansion
30-50 per cent nickel (low-carbon)

Ferritic Type
Straight-Chromium Stainless Alloys *
(SAE 51,000 Series)
12-14 per cent chromium; 0.25-0.40 per cent carbon
11.5-18 per cent chromium; 0.12 per cent carbon (maximum)
25-30 per cent chromium
4-6 per cent chromium
27 per cent chromium; 3.5 per cent nickel; 1.5 per cent
molybdenum
High-Speed Steels
18 per cent tungsten; 4 per cent chromium; 1 per cent
vanadium
12.5-21 per cent tungsten; 4 per cent'chromium; 0.75-2.0
per cent vanadium; 3.5-13 per cent cobalt; 0.40-0.80
per cent molybdenum
8 per cent molybdenum; 2 per cent tungsten; 4 p e r cent
chromium; 1per cent vanadium
9.5 per cent molybdenum; 3.5 per cent chromium; 1.25
per cent vanadium
High-Silicon Trunsfornzer Steel
4 per cent silicon (low-carbon)
Pernzunent Magnet Steels
Containing various combinations of:
Carbon
(0.40-1.20 per cent)
Manganese
(0.10-4.8 per cent)
Chromium
(0.20-10.0 per cent)
Tungsten
(5.0-9.0 per cent)
Cobalt
(13.0-40.0 per cent)
Molybdenum (2.0-4.0 per cent)
Special 'Tool and Die Steels
Containing various combinations of carbon, chromium,
tungsten, molybdenum, manganese, vanadium, silicon,
cobalt
'

An excellent classification and summar of typical properties of the stainless steels and a l l o ~ shas been published by Wright and
Luger (see bibliography, p. 225, reference 14y.

TABLE 3
B. Low-Alloy Steels
(Total alloy content generally less than 5 per cent)

Free Cutting Steels (with high manganese and sulfur)


1.00-1.65 per cent manganese; 0.075-0.15 per cent sulfur
SAE X1300 series:
Manganese Steels
1.60-1.90 per cent manganese
SAE TI300 series:
Nickel Steels
0.40-0.60 per cent nickel
SAE 2000 series:
1.25-1.75 per cent nickel
SAE 2100 series:
3.25-3.75 per cent nickel
SAE 2300 series:
4.75-5.25 per cent nickel
SAE 2500 series:

TABLE 3-Continued
Nickel-Ckromiz~mSteels
1.00-1.50 per cent nickel; 0.45-0.75 per cent chromium
SAE 3100 series:
1.00-1.50 per cent nickel; 0.60-0.90 per cent chromium
SAE X3140:
1.50-2.00 per cent nickel; 0.90-1.25 per cent chromium
SAE 3200 series:
3.25-3.75 per cent nickel; 1.25-1.75 per cent chro~nium
SAE 3300 series:
2.75-3.25 per cent nickel; 0.60-0.95 per cent chromium
SAE 3400 series:
Molubdenum Steels (Cr-Mo; Cr-Ni-Mo; Ni-Mo)
0.50-0.80 per cent and 0.80-1.10 per cent chromium: 0.15-0.25 per cent molybdenum
SAE 4100 series:
0.50-0.80 per cent chromium; 1.50-2.00 per cent nickel; 0.30-0.40 per cent molybdenum
SAE 4340:
0.60-0.90 per cent chromium; 1.50-2.00 per cent nickel; 0.15-0.25 per cent molybdenum
SAE 4345:
1.65-2.00 per cent nickel; 0.20-0.30 per cent molybdenum
SAE 4600 series:
3.25-3.75 per cent nickel; 0.20-0.30 per cent molybdenum
SAE 4800 series:
Chromiztm Steels
SAE 5120:
0.60-0.90 per cent chromiun~
0.80-1.10 per cent chromiunl
SAE 5140 and 5150:
SAE 52100:
1.20-1.50 per cent chromium
I
CI~romiz~m-Va?xadiu?n
Steels
0.80-1.10 per cent chromium; 0.15 per cent vanadium (minimum)
SAE 6100 series:
T7~ngsten Steels (Chromium)
SAE 71360:
3.0-4.0 per cent ch+onlium; 12.0-15.0 per cent tungsten
SAE 71660:
3.0-4.0 per cent chromium; 15.0-18.0 per cent tungsten
SAE 7260:
0.50-1.0 per cent chromium; 1.5-2.00 per cent tungsten
Silicon-Manganese Steels
0.60-0.90 per cent manganese; 1.80-2.20 per cent silicon
SAE 9200 series:
Miscelluneous Low-Alloy Steels Comn~nerciall~
Ayailable *
1. Copper-cl~romium-silicon-phosphorus
steel (" Cor-Ten ")
0.30-0.50 per cent copper; 0.50-1.50 per cent chromium; 0.50-1.00 per cent silicon; 0.10-0.20 per cent phosphorus; 0.10 per cent carbon
2. Manganese steel (" Man-Ten ")
1.25-1.70 per cent manganese; 0.35 per cent carbon; with or without 0.20 per cent copper
3. Silicon steel (" Sil-Ten ")
0.20-0.30 per cent silicon; 0.70-0.90 per cent manganese; 0.40 per cent carbon; with or without 0.20 per cent
copper
4. Manganese-copper-nickel-molybdenum steel (" Double Strength ")
0.50-1.00 per cent manganese; 0.50-1.50 per cent copper; 0.40-0.80 per cent nickel; 0.20 per cent molybdenum
(maximum)
I n two grades, with carbon 0.12 per cent (maximum) and 0.30 per cent (maximum)
5. Copper-bearing steel
0.15-0.30 per cent copper; carbon usually under 0.15 per cent
6. Copper-molybdenum steel (" Toncan ")
0.40 per cent copper (minimum) ; 0.05 per cent nlolybde~lum(minimum) ; carbon usually under 0.05 per cent
7. Chromium-manganese-silicon steel
0.30-0.70 per cent chromium; 0.90-1.50 per cent manganese; 0.60-0.95 per cent silicon; 0.35 per cent carbon
(maximum)
8. Chromium-manganese-molybdenum steel
0.60-0.90 per cent chromium; 1.20-1.50 per cent manganese; 0.25-0.40 per cent molybdenum; 0.25-0.40 per
cent carbon
9. Chromium-molybdenum-silicon steel
1.50-2.00 per cent chromium; 0.60-0.80 per cent molybdenum; 0.45-0.75 per cent silicon
In two grades, with carbon 0.15-0.20 per cent, and 0.35-0.45 per cent
10. Carbon-mblybdenum steel
0.30-0.80 per cent manganese; 0.40-0.60 per cent molybdenum; 0.35 per cent carbon (maximum)
11. Carbon-molybdenum steel
0.80-1.10 per cent manganese; 0.25 per cent molybdenum; 0.40-0.70 per cent carbon
12. Chromium-molybdenum steel
1.00-1.50 per cent chromium; 0.40-0.60 per cent molybdenum; 0.50-0.80 per cent silicon; 0.40-0.70 per cent
manganese; 0.42-0.50 per cent carbon

* This list

i s ndnlittedly f a r from conlplete: to hare included all the compositions and trade names mould have made it unduly long.

VI. DEFINITIONS OF HEAT-TREATIK AND METALLOGRAPHIC TERMS


The following definitions of heat-treating terms were
selected from a list published in the 1935 Handbook of
the Society of Automotive Engineers; this list was taken
from a report of the iron and steel division of the society
(last revision January 1935). These and other definitions
have also appeared in the following publications : ASTM
Specifications A 119-33, ASM National Metals Handbook, 251 (1933).
Heat t r e a t n ) e n t A n operation o r combination of
operations involving the heating and cooling of a metal
o r a n alloy in the solid state f o r the purpose of obtaining certain desirable conditions or properties.
Note: Heating and cooling f o r the sole purpose
of mechanical working a r e excluded from the meaning of this definition.
Quenching-Rapid cooling by immersion.
Note: Immersions may be in liquids, gases, or
solids.
Hardening-Heating and quenching certain iron-base
alloys from a temperature either within or above the
critical-temperature range.
Annealing-Annealing is a heating and cooling operation of a material in the solid state. Annealing usually
implies a relatively slow cooling.
Note: Annealing is a comprehensive term. The
purpose of such a heat treatment may be:
1. To remove stresses.
2. To induce softness.
3. To alter ductility, toughness, electrical, magnetic, or other physical properties.
4. To refine the crystalline structure.
5. To remove gases.
6. To produce a definite microstructure.
In annealing, the temperature of the operation and
the rate of cooling depend upon the material being heattreated and the purpose of the treatment.
Full annealing-Heating
iron-base alloys above the
critical-temperature range, holding above that range
for a proper period of time, followed by slow cooling
through the range.
Note: The annealing temperature is generally
about 100 deg. F. above the upper limit of the critical-temperature range, and the time of holding is
usually not less than 1hour for each inch of section
of the heaviest objects being treated. The objects
being treated a r e ordinarily allowed t o cool slowly
in the furnace. They may, however, be removed
from the furnace and cooled in some medium that
will prolong the time of cooling a s compared to
unrestricted cooling in air.
Process anneali~~g-Heating iron-base alloys to a
temperature below, or close to, the lower limit of the
critical-temperature range, followed by cooling a s
desired.
Note: This heat treatment is commonly applied
in the sheet and wire industries, and the temperatures generally used a r e from 1,020 to 1,200 deg. F.

No~nlalizing-Heating iron-base alloys to above the


critical-temperature range, followed by cooling fairly
rapidly to below t h a t range.
Patenting-Heating iron-base alloys above the critical-temperature range, followed by cooling to below t h a t
range in a i r or in molten lead which is maintained a t
a temperature of about 700 deg. F.
Spheroidizing-Prolonged heating of iron-base alloys
a t a temperature in the neighborhood of, but generally
slightly below, the critical-temperature range-usually
followed by relatively slow cooling.
Note a: In the case of small objects of highcarbon steels, the spheroidizing result is achieved
more rapidly by prolonged heating t o temperatures
alternately within and slightly below the criticaltemperature range.
Note b: The object of this heat treatment is to
produce a globular condition of the carbide.
Tentperiltg (also termed drawing)-Re-heating
ironbase alloys after hardening to some temperature below
the critical-temperature range, followed by a n y desired
rate of cooling.
Note a: Although the terms "tempering" and
" drawing " a r e practically synonymous a s used in
cbmmercial practice, the term "tempering" is
preferred.
Note b: Tempering, meaning the operation of
hardening followed by re-heating, i s a usage which
is illogical and confusing in the present state of
the a r t of heat treating, and should be discouraged.
Carbz~rizing (cementation)-Adding carbon to ironbase alloys by heating the metal below its melting point
in contact with carbonaceous solids, liquids, or gases.
Note: The term " carbonizing " used in this sense
is incorrect, and its use should be discouraged.
Case hardening-Carburizing and subsequently hardening by suitable heat treatment all or part of the
surface portions of a piece of iron-base alloy.
Case-That
portion of a carburized iron-base-alloy
article in which the carbon content has been substantially increased.
Core-That
portion of a carburized iroil-base-alloy
article in which the carbon content has not been substantially increased.
Note: The terms " case" and " core" refer to
both case hardening and carburizing.
Cyaniding-Surface hardening of a n iron-base-alloy
article or portion of it by heating a t a suitable temperature in contact with cyanide salt, folloyed by quenching.
Nitriding-Adding
nitrogen in iron-base alloys by
heating the metal in contact with ammonia gas or other
suitable nitrogenous material.
Note: Nitriding is conducted a t a temperature
below the iron-carbon critical-temperature range,
and produces surface hardening of metal without
quenching.
The following concise definitions of metallographic
terms used in this paper are given for the benefit of

. ,

FUNDAMENTAL
CHARACTERISTICS
OF ALLOYSTEEL
readers who may not be familiar with metallographic
terminology; these terms have also been defined in the
body of the paper where they first occur.
Alcstenite-Gamma-iron
solid solution, stable only a t
temperatures above the transformation or critical
range; capable of dissolving carbon in amounts up to
about 1.7 per cent; crystal structure face-centered cubic.
F e r r i t e A l p h a - i r o n solid solution, stable only a t
temperatures below the transformation or critical
range; capable of dissolving carbon in amounts less
than about 0.04 per cent; crystal structure body-celltered
cubic.
compound, Fe3C, in plain-carbon
Carbide-Chemical
steels or special carbide compound in steels containing
strongly carbide-forming elements.
Pearlite-Aggregate
of ferrite and carbide formed
directly from austenite on cooling, alld consisting ,f
alternate lamellae of the two constituents. The spacing
between the lanlellae of ferrite and carbide is dependent
upon the temperature of transformation from austenite;
the lower the temperature (within limits) the finer the
spacing.
Martensite-Unstable
alpha-iron solid solution with
the carbon in some unstable unrejected form; results
from low-temperature transformation of austenite induced by rapid cooling.

225

BIBLIOGRAPHY
'1'. R . Brnce. " Special Metals in Oil-Field Practice,'' Metals
arid A l l o ~ s ,1S1, Sept. ( 1 0 3 4 ) .
2 " Xletnls Used i n t h e Oil I n d u s t r y , dletal Proyress, 47, Apr.
E. C. Bnjp, " Some ~ 1 ; n r a c t e r i s t i c s Common t o Carbon nnd
Alloy Steels. Tearbook a n t . I ~ O I L .Steel Inst., S6 ( 1 9 3 4 ) .
' J. L. Gregg a n d B. N. Dnniloff, "Blloys of I r o n a n d Copper,"
A,loUs of Iro,l Mo,logra,~l,s ( 1 9 3 4 ) .
C. IT. T ~ r i g "
, Copper Alloyed with Steel," Metal Progress, 53,
e R . F. Jollnston a n d G . N. Schramm. "Cor-Ten--A
HighTensile Corrosion-resisting Steel f o r Railroo(1 Eqnipment," Official
P'OC.,
Clf'b of PittsbtJr!71t, 34 (1). Nov. 32 (1934).
G. N. Schmrnm, E. S. Tnylerson. a n d Albert R. Stuebing.
" New .4lloy
Steels n n d T h e i r Applicntion t o C a r Equipment,"
Dee. (Ig3').
E. S. Davenport. E. 1,. Roff. nnd E. C. Bain. " hlicroscopic
Effects a n d Elimination,"
Cracks i n I-Inrdened Steel-Their
~ ' ~ ( I I LArn.
s.
Roc. Metals, 22, 2S9 ( 1 9 3 4 ) .
E. S. Davcrlport a n d E. (3. Bnin. " G e n e r a l Relations Between
Grnin Size a n d Hnrdenn1)ility a n d t h e Normality of Steels,"
Tr0n.q. Anr. SCC.Mctals, 23. 879 ( 1 9 3 4 ) .
10.Tol~n.I. E g a n , n'alter C r a f t s , nn(l,.A. B. Kinzel. " T o u g h n e s s
of Alloy Steels a t LOW Temperntures, J l e t a l Progress, IS, Sept.

"""

l1 0 . V. Green?, " Some Cllaracteristics of P e a r l i t e in Eotectoid


Steels," T r a ~ r s Btrt.
.
.cjoc. Steel l'rcatirtg, 16, 57, J u l y (1923).
l2 From unpublished work of J. It. Vilella, U. S. Steel Corp.
hboratory ( 1 3 3 5 ) ,
l3 F m n k P . Gilligan, " N e w S B E Steels," Metal Progress, 5 i ,
A I ] ~ .( 1 9 3 5 ) .
14 E. C. W r i g h t a n d I<. E. Lltger, " Where Stainless Alloys S t a n d
i n c l l e ~ n i c a l Construction," G h e n ~ . Alet. ~ n g . ,39, 494, Sept.
(193').
15 I<:, Heincllhofer, " T h e ' P l a s t i c i t y ' of Iron a t Low Temperatures, Ant. I n s t . Alirait~g~ c t E. n g . Tech. Pub. 581, Oet. (1934).