2.

1 Fundamentals of Heat Treating Metals and Alloys

MK Banerjee, Malaviya National Institute of Technology, Jaipur, India
r 2017 Elsevier Inc. All rights reserved.

2.1.1 Introduction 2
2.1.1.1 Stages of Heat Treatment 2
2.1.1.2 Heating Step 2
2.1.1.2.1 Heating rate 3
2.1.1.2.2 Heating temperature 3
2.1.1.3 Soaking Stage 4
2.1.2 Heat Treatment of Steel 4
2.1.2.1 Production of Homogeneous Austenite 8
2.1.2.2 Effect of Excess Heating Beyond Homogenization 8
2.1.2.3 Common Heat Treating Processes 9
2.1.3 Heat Treatment Process Variables 9
2.1.3.1 Austenitization 10
2.1.4 Introduction of Alloying 11
2.1.4.1 Classification of Alloying Elements 11
2.1.4.2 Effect of Alloying Elements 12
2.1.4.2.1 Effect of individual alloying elements in summarized form 14
2.1.4.3 Effect of Alloying Elements on TTT and CCT Curves 15
2.1.5 Annealing 20
2.1.5.1 Full Annealing 20
2.1.5.2 Isothermal Annealing 20
2.1.5.2.1 Patenting 21
2.1.5.3 Incomplete Annealing or Intercritical Annealing 22
2.1.5.4 Spheroidizing Annealing 23
2.1.5.5 Homogenization or Diffusion Annealing 24
2.1.5.6 Recrystallization Annealing 24
2.1.5.7 Subcritical Annealing 27
2.1.6 Normalizing 27
2.1.6.1 Distinctions between Annealing and Normalizing Purpose 28
2.1.7 Hardening 29
2.1.7.1 Factors Influencing Hardening Process 31
2.1.7.1.1 Adequate carbon content to produce hardening 31
2.1.7.1.2 Austenite decomposition to produce pearlite, bainite, and martensite structures 31
2.1.7.1.3 Temperature of heating, rate of heating, and the time of holding 32
2.1.7.1.3.1 Temperature 32
2.1.7.1.3.2 Heating rate and soaking time 32
2.1.8 Heat Treatment Fundamentals of Nonferrous Alloys 32
2.1.8.1 Age-Hardening Treatment 32
2.1.8.2 Annealing of Nonferrous Alloys 34
2.1.8.3 Martesite Formation in Nonferrous Alloys 34
2.1.8.3.1 Heat-treat principles of nonferrous alloys exhibiting polymorphic transition 35
2.1.8.3.2 Application of heat treatment principles in Mg-alloys 36
2.1.9 Quenching and Quenching Medium 36
2.1.10 Tempering 39
2.1.10.1 Stages of Tempering 40
2.1.10.2 Formation of Bainite in Steels 42
2.1.10.2.1 Mechanism of bainite formation 42
2.1.10.3 Martempering 43
2.1.10.4 Austempering 44
2.1.11 Retained Austenite 45
2.1.11.1 Subzero Treatment 46
2.1.12 Heat Treatment Defects 47
2.1.12.1 Quench Cracks 47
2.1.12.2 Overheating 48

Comprehensive Materials Finishing, Volume 2 doi:10.1016/B978-0-12-803581-8.09185-2 1

2 Fundamentals of Heat Treating Metals and Alloys
References
Further Reading
Relevant Website
2.1.1 Introduction
Heat treatment is essentially a process of heating and cooling a
material to achieve a desired set of physical and mechanical
properties. The properties of materials are dependent upon their
structural aspects. The structures may be of different scales of
magnitude viz. macrostructure, microstructure, nanostructure,
crystal structure, or atomic structure. In general, heat treatment
of metals and alloys concerns the change in microstructure.
Planned thermal treatment may affect desired changes in
the defects structure of metallic crystals; this in turn alters the
mechanical properties of the metals and alloys. During the
course of heat treatment, the metals and alloys may undergo
change in crystal structure (polymorphic transformation),
change in chemical composition and change in the degree of
order; depending upon the system, these changes may take
place either singularly or in combination. However these
changes have direct bearing on the final properties of the
material. Also it will be seen that without any of the above
three changes, heat treatment may enable to obtain desired
properties of materials by way of changing its substructure.
In a nutshell, heat treatment of metals and alloys envisages:
• Polymorphic change with or without change in local
composition with in a system. The average composition
however remains the same. This type of change is very
common and Fe–C system is a classic example.
• Overall change in chemical composition at the surface of a
component followed by above mentioned polymorphic
change as stated above. This type of change is realized in
surface hardening of metals and alloys.
• Change in local composition at a very fine scale of mag-
nitude. Age hardening in alloy exemplifies such incidence.
• Dissolution of unwanted second phase particles, and for-
mation of clean single phase alloy.
• Grain refinement of a pure metal or a single phase alloy
which is previously subjected to mechanical working at a
low temperature.
It is to be understood that changes stated above are brought
about by previously chosen thermal treatment with an eye to
achieving a predefined set of properties. Thus the purposes of
heat treatment of metals and alloys are:
• To improve strength, hardness, and wear resistance prop-
erties.
• To increase toughness and ductility.
• To obtain fine grain size.
• To remove internal stresses induced by differential defor-
mation by cold working, nonuniform cooling from high
temperature during casting and welding.
• To improve machineability.
• To improve cutting properties of tool steels.
• To improve surface properties of materials especially in
respect of wear and corrosion resistance.
48
49
49
• To improve physical properties viz. electrical and magnetic
properties.
• To induce such other unique material functionalities as
are possible due to specific phase transformation; some
examples are transformation induced plasticity, metamag-
netic shape memory effect, etc.
2.1.1.1 Stages of Heat Treatment
The heat treatment as a process is accomplished in the fol-
lowing three stages:
• Heating to a high temperature to obtain homogeneous
single phase. In a multiphase alloy system, the homoge-
neous single phase can be obtained at high temperatures
only with special care, as described later.
• Holding at the high temperature for preselected time
period.
• Cooling the object under treatment to room temperature
or below.
Again, it may be required to repeat the same three stages
with different process parameters. It is necessary to know, how
to select the heating temperature. Equally important is to acquire
the knowledge about the criteria of selecting the rate of heating
to reach the selected temperature and the duration of time one
needs to spend at the heating temperature. During cooling
operation knowledge about the cooling rate to use is also
required. If the cooling rate is very slow, equilibrium micro-
structure in accordance with the prediction of phase diagram of
the concerned system is possible to achieve. It is pertinent to
remember that, attainment of equilibrium during cooling of a
multicomponent system undergoing phase changes may be
possible only if infinitesimal rate of cooling is practiced; it is very
difficult to impose such a slow cooling rate in practice, although
it is not impossible in today’s technological scenario. The prac-
tice of heat treatment at such slowest possible cooling rate to aim
at achieving the equilibrium microstructure is called annealing.
If an iron–carbon alloy contains equilibrium phases in its
microstructure, the alloy is said to reach its softest state. This
is why annealing of iron–carbon alloy is quite often considered
as a softening process, whereas all other processes leading to
deviation from equilibrium structures may be looked as hard-
ening process. However this behavior is not generic and is not
authenticated in many alloy systems, where the nonequilibrium
phase is softer than its equilibrium counterpart. One such
example is Cu–Zn–Al alloy, which when rapidly cooled from a
high temperature is seen to produce softer phase than that
present in annealed condition.
2.1.1.2 Heating Step
One of the main objectives in the heating stage is to obtain a
homogeneous single phase unless otherwise dictates of com-
pulsions are there; for example, hypereutectoid steels are

deliberately heated to a two-phase region for accruing certain
specific benefits, as narrated in later sections. Another target of
heating stage is to attain uniform temperature throughout the
cross-section of the object being heat treated. Rapid heating
may allow one part of the object to expand faster than another
and as a result distortion or warpage may take place. However
the heating rate depends on several factors. One important
factor is the heat conductivity of the component. A metal with
a high-heat conductivity heats at a faster rate than one with a
low conductivity. The size of the stock to heat treat and its
initial structural condition determine the rate at which it
should be heated. A slower heating helps to get rid of thermal
shock due to differential heating at surface and at the center. A
component with higher cross-sectional area should be sub-
jected to a slower heating rate in order to minimize the dif-
ference in temperature between surface and center of the stock.
This helps to minimize the chance of warpage and distortion.
Parts with nonuniform cross-sections experience uneven tem-
perature rise across the section and hence a slower heating rate
must be used to avoid cracking or warpage.
2.1.1.2.1 Heating rate
Whenever there is a phase transformation involving a change
in crystal structure, volume change ought to occur. In a heat
treatment process, the heating step comes across two different
types of stresses: one is the thermal stress due to the existence
of temperature differential between surface and center of the
object being heat treated. This stress is consequential to ther-
mal expansion of the material.
The other type of stress originates from the volume change
accompanying the phase transformation. These two stresses
make the component vulnerable to distortion or warpage. In
extreme cases cracking may also occur for an otherwise intricate
geometry. Difference in magnitude of thermal expansion at the
surface and the center of the component depends upon the dif-
ference in temperature between the two at any instant of heating.
This temperature difference is further dependent on the thermal
conductivity, specific heat, and the section size of the object.
The rate of heating is therefore decided by both the thermal and
the transformational stresses. As previously mentioned, thermal
stresses may be managed by a slower heating rate, whereas
magnitude of transformational stresses is fixed for a definite
phase transformation. However phase transformation takes place
within specific range of temperature and so special care is taken
in heating the material through this range of temperature. Quite
often at temperature near to, where phase transformation is likely
to occur, a short holding time is recommended. The purpose of
this holding time is to equalize the temperatures at the surface
and center of the stock. Thus there is no thermal stress, only the
transformation stress is to be taken care.
There are a number of constraints to come across during
heating. These are:
• Thermal properties of the material are functions of tem-
perature and these are not accurately known for all metal
and alloys under all conditions of heating. This leads to the
problem of unpredictable and nonuniform thermal stresses
to take care by manipulation of heating cycle.
• The flow stress of the material decreases at elevated tem-
perature and if a phase transformation takes place at a high
Fundamentals of Heat Treating Metals and Alloys 3
temperature with appreciable volume change, the stress
due to transformation may lead to plastic deformation of
the component being heated. Thus distortion or warpage
becomes inevitable. In such cases manipulation in heating
rate is of little use.
• Beyond the temperature of transformation only thermal
stress is important and a slower rate of heating might
appear to be a solution. However, it is certainly not because
a slower heating implies a higher time to reach the soaking
temperature. In many alloy systems there is ample chance
of chemical degradation due to heating at high tempera-
ture. A slower rate of heating leaves a greater scope for
chemical degradation, as the total residence time at the
elevated temperature is quite high. So, it is desirable to
employ a higher heating rate to reach the soaking tem-
perature as soon as possible. The chemical degradation may
be due to reaction with aerial gases in the furnace envir-
onment (as in titanium alloys), internal oxidation by
entrapped oxygen in aluminium alloys, etc. Further a fast
heating across the transformation temperature will raise the
transformation temperature due to hysteresis effect and this
results in higher degree of superheat and enhancement of
driving energies for transformation. A controlled soaking
time and temperature envisage the formation of fine-
grained single phase alloy. However for cases of heating to
subcritical temperature for specific heat treatment types
(stress relieving, second stage graphitization in cast iron), a
slower heating rate is preferred.
2.1.1.2.2 Heating temperature
The microstructure of the heat-treated component may follow
from the dictates of equilibrium phase diagrams; sufficient time
at the transformation temperature is available for diffusion
processes to take place. Near-equilibrium state is normally
attained in case of extremely slow cooling. With increasing
cooling rate, availability of time to attain equilibrium at each
stage of transformation is a constraint. This leads to a none-
quilibrium situation. Thus quantitative estimation of phases by
the usual technique of applying lever rule is not tenable. Even
under deviation from equilibrium a system may undergo dif-
fusional transformation, and can form phases qualitatively
similar to what are predicted by the phase diagrams.
However, the phases so formed will increasingly differ in
composition, morphology, and amounts with increasing
cooling rate. This aspect is quite prevalent in case of iron–
carbon system where normal cooling in air called normalizing,
leads to significant difference in structure and property of the
alloy. Faster cooling leads to a lower transformation tem-
perature as compared to that of the annealed samples. In such
cases it is prudent to study the isothermal transformation
behavior of the samples at lower transformation temperatures.
However diffusional transformation in solid state is limited by
certain critical cooling rate (CCR), beyond which the system
can no longer undergo diffusional transformation; rather it
tends to produce supersaturated solid solution. Depending
upon the system, where polymorphic transformation is una-
voidable, crystal structure of the product phase changes
through diffusionless shear transformation, where large-scale
atomic movement is not required. Such kind of transforma-
tion is called martensitic transformation and it is observed in
4 Fundamentals of Heat Treating Metals and Alloys

rapidly cooled iron–carbon alloy. On the contrary, there are

many systems, like a number of aluminum alloys, where there
is no possibility of polymorphic transition and hence rapid
cooling simply produces supersaturated solid solutions. In
either case super saturation may be relieved by gently heating
the supersaturated solid solution above room temperature so
that the solute atoms gather appreciable mobility. Such pro-
cess of getting rid of supersaturation through rejection of
solute-rich phase is called precipitation.

2.1.1.3 Soaking Stage

When the preselected temperature is reached the component
undergoing heat treatment is required to be kept at that tem-
perature until the desired degree of structural homogenization
take place. This process is generally termed ‘Soaking.’ The length
of time the object is kept at the soaking temperature is known
Figure 1 Temperature differential between surface and center.
as ‘Soaking period.’ The soaking period depends upon the che-
mical composition of the material being heat treated, its thermal
history, initial microstructure, maximum section size, and the
weight of the component. In parts having different cross-sections
the soaking period is decided by the largest cross-sectional area.
As mentioned earlier, the temperature at the center of finite-sized
workpiece lags behind the temperature at its surface.
Therefore the center of the stock will reach the soaking
temperature at a later time than the surface. Hence the soaking
time has two components: one is the time required for
equalization of temperature at the surface and the center while
the other one is the time for the structural homogenization to
take place. The homogenization process may be simple dis-
solution of solute-rich phase into the matrix phase or a com-
bination of both phase transformation with crystal structure
change and second phase dissolution.
Figure 1 qualitatively shows the temperature differential to
exist between surface and center of the heat treating stock. In
most of the practical and industrial operation a time of 15 min
is considered sufficient to make the temperature uniform
across the section. Taking homogenization time in considera-
tion, a thumb rule of 1 h per 25 mm of section size is normally
employed for soaking at the high temperature. However in an
industrial situation when a number of components are to be
heated together, the thumb rule of 1 h per 25 mm thickness Figure 2 A complex heat cycle.
may not work out. In every such case, it is needed to under-
stand the temperature profile within a furnace, and based on Different types of heat treatment processes applicable to
this knowledge, the time to be taken for all the items to attain various material systems are shown in Figure 3.
the heat treatment temperature need to be deduced. However Majority of the aforementioned heat treatment practices are
the general approach must be to keep the holding time to its implemented in different types of steel. Therefore to elucidate
minimum possible value. Too high a holding time may lead to the fundamentals of these heat treatment processes, the fol-
grain coarsening and chemical degradation, whereas an lowing discussion is made with reference to steel panel of
inadequate soaking time may not yield homogeneous single iron–carbon alloys.
phase everywhere within the workpiece.
As shown in Figure 2, sometimes the metal is brought from
room temperature to the soaking temperature in more than 2.1.2 Heat Treatment of Steel
one step; the workpiece is first heated slowly to a temperature
where phase transformation is likely to take place and then it The steel is an alloy of iron and carbon with a maximum
is held at that temperature for some predefined period of carbon content of 2 wt.%. The steel panel of Fe–C phase dia-
time so that the temperature of the workpiece is equalized gram as shown in Figure 4 is extended up to the extremum of
throughout its cross section. This action is called ‘preheating.’ eutectic isotherm.
Following preheating the workpiece should be finally heated The present discussion is confined to the metastable phase
to the required heating temperature at a faster rate. diagram of the system, because of the obvious reason that

Figure 3 Different types of heat treatment processes.
a very long time is taken by the system to attain the
stable state. The information about the different phases pre-
sent at different temperature–composition combination may
be obtained from the above equilibrium diagram. It may be
noted that, A1, the lower critical temperature denotes the
minimum temperature up to which austenite(g) can be pre-
sent; A3, is the upper critical temperature describing the
equilibrium between g and ferrite(a); whereas Acm, is the line
describing the solubility of carbon in g. Quite often the suffixes
c, e, and r are used with the critical temperatures. For example,
Ac1 denotes the temperature at which g forms from ferrite
during heating. Its equilibrium counterpart is written as Ae1,
whereas Ar1 stands for g to ferrite transformation during
cooling. Similar meanings are assigned to Ac3, Ae3, Ar3, Accm,
Aecm, and Arcm. Addition of alloying elements tend to alter
the position of A1 and A3 lines; at the same time it changes
the eutectoid composition which is 0.8 wt.%C in pure binary
Fundamentals of Heat Treating Metals and Alloys 5
Fe–C alloy. The alloying elements added in iron–carbon sys-
tem are classified broadly in to two types:
One group of alloying elements is known to stabilize fer-
rite; these alloying elements are called ferrite stabilizers and
in general the crystal structure of ferrite stabilizing elements
is body centered cubic (BCC). Cr, Mo, W, Nb, etc. are some
examples of ferrite stabilizer.
Similarly, the elements stabilizing austenite are called
austenite stabilizer. The austenite stabilizers are mainly those
with face centered cubic (FCC) crystal structure; Cu, Mn, Ni, C,
etc. are austenite stabilizers.
If ferrite stabilizing elements are added to steel, there will be
rise in A1 and A3 temperatures, which restrict the austenite
phase field; on the other hand the addition of g stabilizing
elements will depress A3 and A1 lines in the equilibrium dia-
gram. The effect of commonly used alloying elements on A1
temperature and eutectoid carbon content is shown in Figure 5.
6 Fundamentals of Heat Treating Metals and Alloys

Figure 4 Combined iron–graphite and Fe–Fe3C phase diagram showing steel panel up to 2.11 wt.% carbon.

Figure 5 Effect of alloying element on the carbon content of the eutectoid composition.

As stated earlier the prediction of equilibrium phase dia- microconstituents. The heat treatment practices in general take
gram is of limited use in practical heat treatment processes resort to finite cooling rate causing deviation from equili-
except for annealing, which attempts to achieve equilibrium brium. As discussed previously that up to a certain degree of

rapid cooling, it is possible to effect diffusional transformation
and thus realizing the microconstituents qualitatively similar
to what are presented in the corresponding equilibrium dia-
gram. To understand this situation it is important to review
the isothermal transformation behavior of steel at temperature
below the equilibrium isotherm. This isothermal transforma-
tion behavior is described by time–temperature–transformation
(TTT) diagram as shown in Figure 6.
It is clear from the diagram that for transformation of steel
at any temperature less than the equilibrium one needs some
time to start the diffusional transformation and this gets
completed after some more time as seen in the TTT diagram.
The nature of TTT diagram is generic and is applicable for any
diffusional transformation. As can be seen from the diagram,
it is a C-shaped curve. As the transformation temperature is
lower:
• the driving energy for phase transformation, i.e., diffusional
decomposition of austenite to ferrite and carbide (pearlite)
increases;
• the diffusional transformation of g is due to nucleation and
growth mechanism (readers may consult any text book of
physical metallurgy of steel for details of diffusional
decomposition of austenite); and
• the increase in driving force for phase transformation tends
to lower the critical nucleus size and energy of nucleation.
Thus a higher number of nuclei are formed at lower
transformation temperature. This phenomenon accelerates the
overall transformation kinetics so long as the growth rate due to
lowering of transformation temperature is not reduced to any
objectionable value. It is for this reason, the time required to
start the transformation called ‘incubation period’ decreases
with decreasing transformation temperature, i.e., with increasing
degree of undercooling. The reduction in incubation time con-
tinues till a particular temperature is reached. Below this critical
Figure 6 Hypothetical cooling path on isothermal transformation of
eutectoid steel.
Fundamentals of Heat Treating Metals and Alloys 7
temperature, the time required to start the diffusional transfor-
mation is seen to increase. This retardation of transformation
kinetics below a critical transformation temperature describes
the overriding influence of the diminution of rate of growth
of the product phase. The growth of a nucleus is accomplished
by continuous attachment of the atoms through long-range
migration. The mobility or the diffusivity of atoms are strongly
dependent on the temperature. Below a certain critical value
of temperature, the diffusivity of atoms becomes so low as to
stop the growth of nuclei; as a result there is a net increase in the
time to start transformation, thereby making the TTT diagram
C-shaped.
This is supported by the curve in Figure 7, which shows
the variation of rate of nucleation and rate of growth with
temperature.
The point, at which incubation period is minimum, is
known as the nose of TTT diagram. Incidentally, the portion of
the curve below the nose of TTT diagram of 0.8 wt.%C steel
does not represent same type of transformation as it is above
the nose of the curve. It is evident from the equilibrium diagram
shown in Figure 4 that austenite of 0.8 wt.%C completely
transforms to pearlite below the eutectoid isotherm. Taking
this steel as a reference, the transformation of g till the nose of
TTT diagram represent the transformation of austenite to pear-
lite and below the nose of plain 0.8 wt.%C steel, austenite
decomposes to the aggregate of ferrite and carbide through a
different mode of phase transformation known as ‘bainitic
transformation’ (please refer to book Physical Metallurgy Princi-
ples authored by Robert E. Reed-Hill or any other text book).1
The TTT diagram of a plain carbon 0.8 wt.%C steel is con-
tinuous, and so it is difficult to distinguish the exact point of
transition from a pearlitic reaction to a mechanistically different
bainitic reaction. It is quite certain that above the nose of TTT
diagram, at about 550 1C, only pearlitic reaction takes place; it
is also clear that transformation at any temperature below
450 1C austenite undergoes bainitic transformation. It is pre-
sumed that from around 550 1C till 450 1C both pearlite and
bainite reaction may take place. Isothermal transformation of
Figure 7 Variation of nucleation and growth rate for eutectoid steel
with temperature. Mehl, R. F.; Dube, A. Phase Transformation in Solids;
John Wiley and Sons, Inc.: New York, NY, 1951; p. 545. © 1951.
8 Fundamentals of Heat Treating Metals and Alloys
austenite indicates several important aspects of phase transfor-
mation in steel. It describes the transformation of austenite
to pearlite above the nose of TTT diagram; it also helps to
understand the bainitic reaction in plain C-steel below the nose
of TTT diagram. It is obvious that continuous cooling cannot
give rise to the formation of bainite in plain C-steel. If cooling
rate is such high, as to bypass the nose of TTT diagram, neither
pearlite nor bainite can form; instead, metastable austenite
transforms by diffusionless shear mechanism to form a super-
saturated solid solution of BCT structure called ‘martensite.’ In
this context it is important to note that equilibrium diagram is
of limited use in actual heat treatment operation, as it cannot
provide any information about the product of transformation
when in industrial heat treatment the cooling rate deviates from
equilibrium.
In case of annealing a steel, care is taken to effect the
decomposition of austenite at a low supercooling such that the
transformation takes place in near-equilibrium condition.
Since austenite decomposition envisages diffusion of partici-
pating atom species, the alloy steel with higher stability of
austenite is required to be annealed at a considerably slower
cooling rate, 10 1C h
1. The cooling rate can be effectively
controlled at a low value by providing suitable means of
power input marginally less than what is required during
the soaking period to maintain the constancy of temperature.
Incidentally annealing of chromium bearing steels encounters
the probability of embrittlement at a temperature around
550 1C. Therefore after transformation of austenite to ferrite
and carbide as near to equilibrium temperature as possible,
the steel is cooled rapidly to avoid the precipitation of chro-
mium carbide. Whenever stress relieving during annealing is
an important issue as is the case of intricate shaped casting, the
slow cooling should continue till room temperature.
2.1.2.1 Production of Homogeneous Austenite
As a first step of heat treatment the workpiece is required to be
heated to a temperature high enough to produce a homo-
genous single phase alloy. However there are exceptions like
hypereutectoid steel where heating is carried out quite often
to a temperature having a two-phase microstructure. In all
cases, the final temperature is selected on the basis of infor-
mation provided by the equilibrium diagram of the concerned
system. In many cases (as in steels), achieving a single phase at
high temperatures involves both polymorphic transformation
and dissolution of the second phase constituent. In such cases,
the first formed single phase alloy is compositionally inho-
mogeneous requiring a special attention to make the system
homogeneous. In some other cases the initial microstructure
may be of multiphase structure, needing dissolution of solute
reach second phase without any phase transformation under-
going in between. In those cases heating temperature is to
be decided by the equilibrium diagram which shows the
temperature at which a single phase solid solution may be
obtained. Only in case of subcritical heating, the kinetic aspect
of the target activity is to be paid attention to. For an example,
when second stage graphitization is envisaged, that is, when
the pearlitic cementite is required to decompose into graphite,
temperature of heating is decided by the kinetics of the
process.
The fixing of ideal soaking temperature is a critical job. The
soaking temperature is always fixed above the critical tem-
perature describing the formation of single phase. For an
example, temperature above Ac3 line in iron cementite dia-
gram. Increasing the soaking temperature has the advantage
of making the system homogenous at an earlier time and
thereby saving time and energy in the process. But unlimited
enhancement of the soaking temperature to take advantage of
achievable higher productivity is constrained by the chance of
grain coarsening. Many systems require a dissolution of solute
rich second phase and subsequent homogenization of these
high temperature phases. This is essentially a thermally acti-
vated process and is time dependent. Higher is the tempera-
ture, shorter is the time requirement to achieve identical result.
However large reduction in soaking time is restricted due to
the fact that soaking temperature is limited by its greater
vulnerability to chemical degradation and higher chance of
grain coarsening. Hence optimization of heating temperature
is very important. Normally the temperature of soaking is kept
50–75 1C higher than the equilibrium temperature.
2.1.2.2 Effect of Excess Heating Beyond Homogenization
Grain coarsening takes place if heating temperature is made
excessively high. Coarsening of grains also results if holding
time is unnecessarily prolonged even when homogeneous
austenite has been formed. The initial grain size of austenite
depends upon the number of nuclei formed due to super-
heating.
The grain coarsening is a thermally activated process and
requires movement of grain boundaries. So long as there are
constraints for grain boundary movement in presence of pre-
cipitates or compositional heterogeneity, the grain boundary
movement is restricted; under such circumstances, once
homogenized such barriers are no longer existent.
Any further holding at high temperature will cause, grain
coarsening to set in, because coarse grains are thermo-
dynamically stable. Grain coarsening leads to reduction in
grain boundary area and thus the surface free energy and hence
the total energy of system decreases. It may be noted that there
are grains which are inherently fine and can remain so, even if
heated to as high as 1000 1C or more. Rapid grain growth in
these steels can take place only upon heating to 1050 1C or
beyond. In contrast inherently coarse-grained steels exhibit
rapid grain growth much earlier. The different tendency for
grain growth is ascribed to the internal deoxidation practice.
The air melted aluminum-killed steels are known to produce
aluminum nitrides which are uniformly distributed within the
matrix. These fine precipitates of aluminum nitride inhibit
grain coarsening. Likewise many alloying elements, viz. tita-
nium, vanadium, niobium, or other strong carbide formers,
retard grain growth till they are not completely dissolved
during austenitization. However inherently fine-grained steels
do not mean that their grain sizes will always be less than
those of the inherently coarse-grained steels; as shown in
Figure 8, the initial rate of grain growth in inherently fine-
grained steel is much slow as compared to that of the inher-
ently coarse-grained steels which start growing appreciably
quite early in the heating stage with a nearly constant rate of
grain growth.

The inherently fine-grained steels experience an initial slow
grain growth, which becomes much rapid at higher temperature
and the ultimate grain size can be higher than its inherently
coarse-grained counterpart. Quite often alloy steels containing
strong carbide forming tendency are required to be austenitized
at much higher temperature due the fact the alloy carbides do
not go in solution so easily and take longer time or higher
asaturated at high temperature
! asupersaturated
! asaturated at room temperature þ b
quench
temperature to completely dissolve. As a result, they behave
as inherently fine-grained steels because grain coarsening can
take place only after complete dissolution of all the carbide
particles which finally remove the barriers to grain boundaries
movement. It is pertinent to remember the importance of
achieving small grain size after heat treatment. Hall–Petch
relation is given by
ky
sy ¼ so þ pffiffiffi
d reduction in ductility. Its purpose is to refine grain structure, to
where,
sy ¼ yield stress,
so ¼ material constant for starting stress for dislocation
movement,
ky ¼ strengthening coefficient, and
d ¼ average grain diameter.
In accordance with above, yield strength of a single phase
alloy is enhanced by its decreasing grain size. In general, struc-
tural fineness of a material gives rise to higher strength and
toughness of the same; therefore wherever structural fineness
is described by grain size, the prediction of Hall–Petch rela-
tionship holds good. In order to gain more insight into it, the
readers may consult the text book Mechanical Metallurgy authored
by Dieter.2
2.1.2.3 Common Heat Treating Processes
The heat treating practices most commonly employed for
commercially important metals and alloys are cited below:
Age hardening is the process where a supersaturated solid
solution is formed by heating the material in single phase region
Figure 8 Austenitic grain growth in inherently fine- and coarse-
grained steels.
Fundamentals of Heat Treating Metals and Alloys 9
and holding there for sufficient time to make up a homogeneous
solid solution. Following this, the alloy is rapidly cooled to
produce the supersaturated solution. This supersaturated solid
solution is heated in a controlled manner; super saturation of
solid solution is relieved by precipitation of solute reach phase.
If a is the solid solution of B in A and b is a B-rich phase
age-hardening process is described by:
aging ðcontrolled heatingÞ
Annealing is generally a softening process in which the
metals are heated to form the equilibrium high temperature
phase and then allowed to cool very slowly. The purpose of
annealing is to obtain the equilibrium microstructure; it aims to
improve machinability, formability, and sometimes magnetic
properties.
Normalizing is a process of natural cooling in still air from
a preselected high temperature where the required single phase
is formed. This results in increase in strength with a little
improve mechanical properties, and to relieve internal and
surface stresses.
Stress relieving is a process of heating to a relatively
low temperature to reduce the level of residual stresses in a
material.
Quenching is a process of rapid cooling of a material from
its homogeneous state at high temperature. The different
media may be used to quench the material; it may vary from
forced air, oil, water with or without addition of salt, and
polymers. Steel is hardened by heating to austenitic phase and
then quenching it to room temperature; this results in the
formation of martensite which is a very hard and brittle con-
stituent in iron–carbon system.
Tempering involves gentle heating of hardened steel and
allowing it to cool slowly so that brittleness of the hardened
material is reduced. Tempering of steel refers to softening by
decomposition of iron–carbon martensite which is very hard
and brittle. Tempering of martensites in steel leads to relieve
of its supersaturation through various structural changes
as described in later section. Also for nonferrous alloys, tem-
pering brings about precipitation of different phases intra-
granularly at the internal faults within martensites and also in
intercrystalline manner at the lath/plate boundaries of mar-
tensite crystals.
2.1.3 Heat Treatment Process Variables
On the basis of previous discussion it is evident that the major
process parameters influencing the quality of heat treatments
are holding temperature, holding time, and rate of heating and
cooling. The required magnitudes of these variables are deci-
ded by the chemical composition, size, and shape of the object
along with the desired properties in the metals/alloys. If the
chemical composition of the alloy to be heat treated is such
that the material is highly prone to oxidation or is inherently
coarse-grained material having a high tendency toward grain
growth, the heat treatment of the same may result in poor
mechanical properties unless special precautions are taken.
10 Fundamentals of Heat Treating Metals and Alloys
In order to minimize the problem of oxidation or grain
growth, two salt bath heat treatment furnaces are sometimes
employed. In one furnace, the object is heated to a tempera-
ture up to which there is no appreciable oxidation or grain
growth. The object is then transferred to the second furnace,
heated rapidly for a short time, and maintained at heat treat-
ment temperature for minimum period. This practice reduces
the total time of holding at the higher heat treatment tem-
perature and thus the above mentioned problems are reduced.
The temperature–time relationship for such a heating cycle is
shown in Figure 2.
In addition to the mode of heating up to heat treatment
temperature, the rate of heating is also of significance. The
heating rate depends on the size and shape of the object and
the thermal conductivity of the alloy. Almost all metallic alloys
have good thermal conductivity and thus, in general, these
parameters play only a marginal role. However, in the case of
alloys like stainless steels, thermal conductivity is an important
factor to consider while deciding the employable rate of
heating. Secondly, low heating rates ensure better homo-
geneity of the structure and reduce the holding time at the heat
treatment temperature. Complicated shapes, sharp cornered
objects, and objects with variable sections are also heated
slowly. Some alloys, such as high carbon steels and austenitic
stainless steels, are subjected to slow heating rates. Smaller and
simple shaped objects can be heated with higher heating rates
and homogeneity of the structure can be ensured in such cases
by increasing the holding time. Also, for the alloys that are
prone to oxidation at high temperatures of heat treatment,
faster rates of heating are recommended at high temperature
range. Heat treatment temperature is governed mainly by
chemical composition of the alloy, prior heat treatment, if any,
and the final properties required. Heat treatment of steel is
accomplished by heating it above upper critical temperature
(Ac3). This is known as austenitizing temperature, and can be
determined from the iron–carbon equilibrium diagram. For
plain carbon steel, Ac3 temperature decreases with increasing
carbon content. During heating, actual austenitizing tem-
perature is raised above the equilibrium temperature. Similarly
upon cooling the transformation temperature is depressed.
Hence, during heat treatment practice, temperatures in excess
of equilibrium temperature are employed. The austenite pro-
duced at these temperatures is homogeneous. In case of alloy
steel, some alloying elements or their compounds do not
dissolve easily in austenite and so they need to be austenitized
for longer time at higher temperature. Unlike cementite which
dissolves readily in austenite, the dissolution of alloy carbides
is rather slow. For an object having variable section size,
the soaking time is determined on the basis of largest section
size. Lowering of heat treatment temperature has the impli-
cation of higher holding time. Generally soaking time of alloy
steels is kept higher than plain carbon steels of low carbon
content and the thinly enriched alloys. Heavy sections, com-
plicated shapes, objects with variable section thickness, and
highly enriched alloys should be cooled slowly. Extremely
slow cooling results in the development of a structure as evi-
dent from the equilibrium diagram. The size, shape, distribu-
tion, and relative proportions of microconstituents can be
controlled over a wide range by way of varying the cooling
rates. Up to a certain limits, higher cooling rate results in a
structure which is qualitatively similar to that in the equili-
brium diagram. By increasing the cooling rate beyond this
limit, structures produced will consist of either nonequilibrium
transformation products or the high temperature phases re-
tained by sudden quenching.
2.1.3.1 Austenitization
Austenitization is the first step of heat treatment of steel.
Avoidance of microstructural gradient in the heat-treated part
is very much necessary; else the final property will be different
in different portion of the heat-treated part. The same strategy
as discussed in the preceding section is applied during auste-
nitization process. Formation of austenite from the initial
microstructure of ferrite and cementite is a nucleation and
growth process. It may be recalled that the austenitization
process involves a polymorphic transition of BCC-ferrite to
FCC-austenite and subsequent dissolution of cementite in
austenite. The initial composition of austenite is the weighted
average of those of ferrite and austenite in the intercritical
region and the entire austenitization process is controlled
by diffusion. The first nucleus of austenite will form above
A1 temperature at the high energy interphase boundaries (like
ferrite–ferrite and ferrite–cementite) as available within the
initial structural configuration. If the initial microstructure is
lamellar pearlitic, the formation of austenite is quite rapid. Its
nucleation will start at the ferrite–cementite boundaries as
shown in the Figure 9.
On the contrary if initial microstructure contains globular
cementite embedded in the ferritic matrix, nucleation of aus-
tenite will generally takes place in ferrite–ferrite boundaries,
although cementite–ferrite interfaces are not excluded from
being the potential nucleation sites. Evidently such situations
of dispersed cementite within the ferrite matrix will take a
longer time for the formation of homogenous austenite.
Figure 9 demonstrates the stages of formation of austenite
from pearlite upon isothermal holding at a particular tem-
perature. The time–temperature plot for such process is shown
in Figure 10.
It is evident from the above isothermal transformation
diagram that initiation of austenite formation from pearlite
takes a definite incubation time which is a function of tem-
perature. Upon formation of initial nuclei of austenite on
ferrite boundary, the nuclei of austenite will gradually grow;
concurrently cementite will dissolve in newly formed auste-
nite as a demand of equilibrium. However equilibrium is not
attained and dissolution of cementite lags behind the for-
mation of austenite by polymorphic change of ferrite. A stage
may be visualized when partially transformed austenite coexist
Figure 9 Stages in austenitization.

Figure 10 Time–temperature relationship in forming homogeneous
austenite.
with pearlite. Upon further holding at the transformation
temperature the entire pearlitic ferrite is converted to auste-
nite with some cementite still remaining to dissolve in aus-
tenite. This cementite dissolution is a diffusional process and
it takes some time to produce 100% austenite in the micro-
structure. However even after completion of austenite for-
mation it does not immediately become homogenous. This is
because the regions where the dissolution of cementite took
place last will be of higher carbon concentration than else-
where. Further holding for some more time will produce
homogenous austenite, ready for subsequent heat treatment
steps.
This process of achieving a homogenous single phase alloy
is generic in the sense that for any initial multiphase micro-
structure, the sequence described above is followed by other
systems, as for example, solutionizing of age hardenable alloy
at elevated temperature.
2.1.4 Introduction of Alloying
Plain carbon steels are of limited use because of its deficiencies
on many counts. They are unsuitable for applications where
considerably higher strength and toughness properties are
required. These steels are incapable to withstand highly cor-
rosive environment, neither they are useful for high temperature
or cryogenic applications. Plain carbon steels can be hardened
only to a limited section and exhibit a marked tendency for
softening at higher temperature. The above limitations of plain
carbon steel are overcome by alloying steels with other ele-
ments. By definition, the elements that are deliberately added
to achieve desirable properties in a metallic system are called
alloying elements, whereas those elements that are inevitably
present in steel without any deliberate intention to serve addi-
tional purposes are known as impurities. For example, the steel
making operation cannot fully remove sulfur and therefore
some amount of sulfur is always present in steel. Sulfur in such
situation is called an impurity. Again the same sulfur when
present in appreciable amount has the capacity to make chips
brittle during machining. A particular variety of steel, known as
free-cutting steel contains deliberately added sulfur. In this case
Fundamentals of Heat Treating Metals and Alloys 11
sulfur, is an alloying element, even though in majority of cases
sulfur is considered an unwanted element in steel due to its
adverse effect on the properties of steel, for example, inducing
hot-shortness to steel. Steels containing alloying element are
called alloy steels. So long as the total alloying element content
is less than 5 wt.%, the steels are considered as low alloy steels
whereas the steels with alloying elements in excess of 5 wt.% is
called high alloy steels.
2.1.4.1 Classification of Alloying Elements
The alloying elements in steel are classified in to two broad
types. Some alloying elements stabilize the higher temperature
phase austenite, which is of FCC crystal structure. The crystal
structure of these austenite stabilizing elements is FCC. The
other class of alloying elements is those which stabilize ferrite
phase. These ferrite stabilizing elements are in general of BCC
crystal structure. The majority of ferrite stabilizers are seen to
be strong carbide formers. However at room temperature any
alloying element in steel has to be present either in solution in
ferrite or in carbide. The austenite formers do not in general
form carbides. It is to be recalled that any element added to
steel is partitioned between the two phases, carbide and ferrite.
The austenite formers which partition to ferrite are not gen-
erally found in carbide. The austenite stabilizing elements are
appreciably soluble in austenite by being of FCC crystal
structure; these elements delay austenite to ferrite transfor-
mation, i.e., the basic lattice transformation in Fe–C system.
However when austenite to ferrite transformation takes place,
an austenite stabilizer can have altogether two options: either
it goes in solution within ferrite or it gets precipitated in ele-
mental form. Whether the austenite stabilizing alloying ele-
ment will remain in solution within ferrite will depend upon
how the concerned solute obeys the other rules of alloying.
In the case of nickel, it is observed that nickel partitions to
ferrite. The atomic radius of iron and nickel are very near to
each other, as a result nickel goes in solution in ferrite at ease.
On the contrary, one would find that copper with FCC struc-
ture is not soluble in ferrite. Moreover it is not carbide former;
hence it is left with the lone option of being precipitated in
element form. The precipitates of copper lead to hardening
of steel.
Majority of austenite formers being non carbide formers
are either present in ferrite or get precipitated depending upon
the solubility of the concerned element in BCC ferrite. Man-
ganese is the exceptional austenite stabilizer, which forms
isomorphous carbide with cementite. Thus manganese gets
partitioned between ferried and carbide, forming (Fe,Mn)3C
type of carbide.
On the contrary, the ferrite stabilizers like Cr, Mo, Nb, etc.
are generally carbide formers. In steel containing more than
one carbide formers, the formation of carbides and partition-
ing between ferrite and carbide depend upon their relative
affinities for carbon and solubility in ferrite.
The alloying elements have significant influence on the
phase transformation behavior of steels. All the alloying ele-
ments influence the decomposition behavior of austenite and
in the process, the alloying elements exert their characteristics
effects on the equilibrium phase diagram, TTT or continuous
cooling transformation (CCT) diagrams.
12 Fundamentals of Heat Treating Metals and Alloys
Some of the important purposes of alloying are:
1. To enhance strength and toughness at room temperature.
2. To improve strength, ductility, and impact properties at
high as well as very low temperature.
3. To improve resistance to degradation under aggressive
service condition.
4. To develop wear resistant steel for employment at ambient
and elevated temperatures.
5. To develop magnetic properties with minimum hysteresis
loss.
6. To improve the strength of steel without aid of quenching.
However, alloying elements cannot change the structure
insensitive properties like stiffness of the steel. The stiffness is
dependent on the elastic modulus, which is the slope of true
stress–true strain (s–e) curve within elastic limit. Although
alloying elements can improve elastic limit, it cannot appre-
ciably change the modulus of elasticity which is a structure
insensitive properties.
2.1.4.2 Effect of Alloying Elements
Alloying elements bring about changes in the Fe–Fe3C equi-
librium diagram. It is to be understood that by the addition of
alloying elements, it is possible to alter the composition and
properties of phases, without giving rise to the formation of
entirely new phases in general. Since alloying elements are
responsible for change in transformation temperature and
the rate of decomposition of austenite, the properties of plain
C-steel can be modified by alloying.
Addition of alloying elements changes the free energy of
participating phases in phase transformation, either diffusional
or diffusionless. Therefore the transformation temperature of
austenite is changed by the addition of alloying elements.
The diffusional decomposition of alloyed austenite neces-
sitates adequate movement of the atoms of alloying elements.
Since such movement is generally sluggish the alloying ele-
ment influences the kinetics of diffusional decomposition.
Solubility of C in austenite as well as in ferrite is modified by
the addition of alloying elements. This is because the alloying
elements dissolved in austenite or ferrite tend to induce lattice
Figure 11 Effects of various alloying elements on hardness of steel.
strain due to difference in size of solvent and solute; this directly
influences the solubility of C in austenite as well as in ferrite.
The diffusionless shear transformation proceeds through
stacking shifts of atoms on the habit planes. The presence of
alloying elements changes the strain field distribution on the
habit plane and thus influences the stacking shifts required for
martensitic transformation. This leads to the stabilization of
either the parent or the product phase and is characterized
by depression or elevation of the characteristic transformation
temperature. The general microstructure of steel at room tem-
perature is comprised of ferrite and carbides. Alloying elements
like Ni, Si, Al, Zr, P, S, and Cu dissolve at ease in austenite and
also in ferrite at different degrees. Some of these elements like
Si, Al, and Zr may form oxides and be present in steel in
the form of nonmetallic inclusions. Similarly Mn and Zr may
form sulfide inclusions. These elements however do not have
appreciable tendency toward formation of carbides. The other
elements like Cr, W, V, Mo, Ti, Nb, and Mn have tendencies for
forming carbides. In the absence of carbon to react with, these
elements should be in a ferrite solution. The increasing order
of carbide forming tendency is Mn, Cr, W, Mo, V, and Ti. The
alloying elements dissolved in ferrite increase the hardness
due to solid solution effect and it is schematically shown in
Figure 11.
As stated earlier, addition of alloying elements not only
modifies the transformation temperature of austenite to ferrite,
but also the eutectoid point. Thus both A1 and A3 tempera-
tures are altered due to the addition of alloying elements.
Figure 12 shows the effect of alloying addition on the eutectoid
transformation temperature. From the diagram, it can be seen
that those alloying elements that are known to stabilize aus-
tenite would lower the A1 temperature. Whenever ferrite sta-
bilizers are added by a large amount, the austenite loop
gradually becomes narrower due to the increase in upper cri-
tical temperature; beyond some specific concentration of fer-
rite stabilizers like Cr, the austenite may not form at all and the
steel remains ferritic at both elevated and room temperature.
All the alloying elements except cobalt shift the TTT- and
CCT-diagrams toward right. Austenite forming elements
stabilize the metastable austenite and delay its diffusional
decomposition. Therefore it is easy to understand that all

Figure 12 Effect of alloying element on eutectoid temperature of steel.
Figure 13 Diagram showing shift of TTT diagram due to alloying with nickel and chromium.
austenite stabilizers should cause a rightward shift of TTT- or
CCT-diagrams. The ferrite stabilizers are in general carbide
formers. It is known that nucleation of pearlite from austenite is
initialized by the formation of Fe3C. In the presence of strong
carbide formers, the formation of Fe3C at prior grain bound-
aries becomes more difficult. Strong carbide formers prefer to
neighbor the C-atoms in austenite; the formation of cementite
requires free C-atoms to react with iron. However getting away
from the attraction of the neighboring atoms of carbide formers
is a thermally activated process and hence time dependent. Thus
more time is required for the carbon atoms to make them
available for iron atoms to form cementite. This implies a shift
of CCT- or TTT-diagrams toward right. The shift of TTT and CCT
due to Ni and Cr is shown in Figure 13.
It is clear that diffusional decomposition of austenite is
delayed due to the addition of alloying elements. The alloying
Fundamentals of Heat Treating Metals and Alloys 13
elements influence the kinetics of both pearlitic and bainitic
transformation. Any specific alloying element is liable to shift
pearlitic reaction and bainitic reaction to larger times but by
different magnitudes. A carbide forming element is expected to
shift the pearlitic reaction to a larger extent than the bainitic
reaction due to difference in the mechanism of these two
transformations.
As seen from Figure 13 both nickel and chromium shift the
TTT diagram toward right, but to different extent. If equal
amount of chromium and nickel are added, it is expected that
the shift of TTT diagram will be more toward right; the mag-
nitude of shift may appear to be additive. However the actual
shift of TTT diagram is more than the summed up shifts due to
addition of either elements. This effect is called ‘Synergism.’
Chromium and nickel are known to shift TTT and CCT dia-
gram synergistically toward right. Several such synergisms are
14 Fundamentals of Heat Treating Metals and Alloys
observed in Fe–C system and examples may be cited of
molybdenum–boron and copper–boron, which depress the
austenite to ferrite transformation temperature synergestically.
However effect of each element on pearlitic and bainitic
reaction is different and so the pearlitic and bainitic bays get
retarded differently due to addition of alloying elements.
2.1.4.2.1 Effect of individual alloying elements in
summarized form
• Manganese (Mn): manganese has got very high solubility in
austenite because of its FCC structure, but its solubility in
BCC-iron is less than 3%. Manganese is a medium carbide
former, forming isomorphous (Fe, Mn)3C carbides. Man-
ganese is a very good hardenability raiser, and is of highest
multiplying factor in determining the hardenability of
steels. It reduces hot-shortness by binding sulfur as MnS.
Manganese is an austenite stabilizer.
• Molybdenum (Mo): it is a ferrite stabilizer, and is extremely
soluble in BCC-iron, having solubility greater than 35%
whereas it is soluble only up to 3 wt.% in FCC-iron.
The solubility of Mo in FCC-iron is increased if carbon
is added to the system. It forms intermetallic compound
with iron and therefore causes precipitation hardening in
Mo–Fe system. It is a strong hardenability raiser, stronger
than most of other alloying elements. It gives rise to
appreciable secondary hardening. As the dissolution of
molybdenum carbide in austenite is a slow process, the
grain coarsening temperature of austenite is significantly
increased by molybdenum. It increases the high tempera-
ture strength and red hardness of steel. Molybdenum
imparts resistance to pitting corrosion in stainless steels;
further molybdenum increases abrasion resistance by
forming hard molybdenum carbide particles in ferrite
matrix. Molybdenum reduces temper embrittlement in a
chromium bearing steel. It is not capable to inhibit the
formation of chromium carbides, but slows down the
kinetics of precipitation of chromium carbide, thereby
putting a constraint to embrittlement.
• Nickel (Ni): nickel with FCC structure is an austenite sta-
bilizer, with unlimited solubility in FCC-iron. Its solubility
in BCC-iron is limited to 10 wt.%, irrespective of whether
there is any carbon or not. Nickel strengthens and toughens
iron by solid solution hardening. It is a moderate hard-
enability raiser but in combination with Cr and Mo, it
increases hardenability significantly. Nickel is not carbide
former but is a weak graphitizer. Nickel does not increase
tempering resistance of steel to any appreciable extent.
Nickel promotes grain coarsening at elevated temperature.
• Cobalt (Co): cobalt is soluble in FCC-iron, with unlimited
solubility. It is extensively soluble in BCC-iron with the
limit of solubility being 75 wt.%. It improves hardness of
iron by solid solution hardening and is a significant con-
tributor to raise hardness by way of hardening ferrite. Its
carbide forming tendency is similar to that of iron and is
the only alloying element which decreases the hard-
enability when dissolved in iron.
• Chromium (Cr): chromium is a ferrite stabilizer and has
got unlimited solid solubility in BCC-iron. Limit of its
solubility in FCC-iron is about 13 wt.%; however, this may
be extended up to 20 wt.% with addition of carbon up to
0.5%. It is a strong carbide former; its carbide forming
tendency is greater than Mn but less than W. Chromium
increases the resistance to oxidation by forming a very thin
layer of chromium oxide. Chromium is a moderate hard-
enability raiser; however, Cr and Ni increase the hard-
enability of steel synergistically. It imparts very good
abrasion and wear resistance by forming chromium carbide
in the microstructure.
• Silicon (Si): silicon is least soluble in FCC-iron, with
solubility up to 2 wt.%. Silicon increases the activity of C in
ferrite. Its solubility in BCC-iron is about 18 wt.%. Silicon
hardens steels with loss in plasticity. Silicon is a very strong
oxidizing element. Silicon segregates at basal plane of
graphite crystal to prohibit inherent growth form of gra-
phite. Thus silicon leads to the formation of graphite flakes.
It increases the hardenability but quite moderately. Silicon
influences tempering in low carbon steels through solid
solution hardening. Silicon is generally used as a deox-
idizer; however silicon as an alloying element up to 4 wt.%
is capable of grain orientation. This makes the steel useful
for transformers. Silicon improves the oxidation resistance
of steel.
• Titanium (Ti): titanium is mildly soluble in austenite, with
solubility less than 1%. However its solubility in BCC-iron is
higher and around 6 wt.%. It is a hardenability raiser but it is
generally added to steel in very low concentration for the
formation of titanium carbide which enhances the material
properties during thermo-mechanical treatment. It prevents
formation of austenite containing high amount of chro-
mium. It also inhibits sensitization in austenitic stainless
steel by way of forming distributed titanium carbide.
• Vanadium (V): vanadium is very little soluble in FCC-iron,
with solubility up to 1 wt.% whereas its solubility in BCC-
iron is unlimited. It acts as hardenability raiser. It is strong
carbide former but its carbide forming tendency is less than
titanium and niobium. Vanadium is excellent in giving rise
to secondary hardening. Similar to molybdenum, vana-
dium enhances the grain coarsening temperature of auste-
nite, because the dissolution of vanadium carbide in
austenite takes a longer time.
• Tungsten (W): tungsten is weakly soluble in FCC-iron;
however its solubility in BCC-iron is quite high, around
33 wt.%. Tungsten is a strong hardenability raiser, and
is also strong carbide former. Tungsten is capable of pro-
viding secondary hardening during tempering. Tungsten
is able to provide very high wear resistance due to forma-
tion of hard particles of carbide in microstructure. It
also improves the elevated temperature strength property
of steel.
• Phosphorous (P): phosphorus is very weakly soluble in
austenite (Avner),3 whereas it is around 3 wt.% in alpha
iron (maximum solubility in a iron at 950 1C). Phosphorus
leads to hardening of steel by solid solution strengthening.
It is also known to improve hardenability. It improves
machinability of free-cutting steels, by way of making the
chip brittle. It also improves corrosion resistance.
• Aluminum (Al): aluminum is extremely soluble in BCC-
iron up to 36 wt.%, whereas its solubility in FCC-iron is
around 1 wt.% (Avner).3 It strengthens ferrite by solid

solution hardening. However it is a graphitizer. Aluminum
is a very good grain refiner by way of dispersing its oxides
and nitrides throughout the matrix of ferrite. Aluminum is
alloyed in steels to be subjected to nitriding, because
strengthening of nitrided steel is realized by the formation
of aluminum nitride.
2.1.4.3 Effect of Alloying Elements on TTT and CCT Curves
Shift of pearlite reaction curve and that of bainite reaction
curve are different due to addition of a single alloying element.
This is because the pearlitic and bainitic reactions are mechan-
istically different; hence the same alloying element should
be responsive to two reactions in different ways. Taking the
instance of addition of a strong carbide former like molybde-
num, it is recognized that initiation of pearlitic reaction is
conditioned by carbon atom being freed from the influence of
molybdenum atoms, which have high affinity for carbon atoms.
Since this depends upon diffusion of molybdenum atoms and
also since such movement is quite sluggish, the reaction is
shifted to longer times. The same element will delay upper
bainitic reaction in a different way. Upper bainite formation is
conditioned by taking away carbon atom from the vicinity of
iron atoms, so that the carbon-depleted austenite transforms
martensitically to bainitic ferrite. The presence of molybdenum
itself aids to this as it removes some carbon atoms from the
influence of iron atoms by way of neighboring the carbon
atoms it has affinity with.
Figure 14 T–T diagram of a 0.33 wt.% carbon, 0.45 wt.% manganese, and 1.97 wt.% chromium steel (Austenitized at 870 1C).
Fundamentals of Heat Treating Metals and Alloys 15
Thus iron atoms populated regions, relatively free of carbon
atoms, are now made available. So martensitic transformation
of austenite to upper bainitic ferrite is accentuated. Therefore
the addition of such alloying elements brings about differential
shifts in pearlitic and bainitic bays, thereby separating the two
bays; hence the alloy systems become amenable to bainitic
transformation by continuous cooling. This is not possible for a
plain carbon steel, where TTT curve is continuous with super-
imposition of pearlitic and bainitic bay as shown in Figure 14.
However, when the cooling rate is so fast as to bypass the
nose of CCT diagram, neither pearlite nor bainite is possible to
form; rather a diffusionless martensitic reaction takes place,
else the metastable austenite phase remains as it is.
It is to be recalled that austenite undergoes phase transition
only when it attains a finite degree of metastability. This
means that stable austenite above A3 or above A1 for eutectoid
steel does not undergo any transformation.
Supercooling of austenite below equilibrium temperature
makes it metastable; this then acquires driving energy for
transformation to product phase (for elaborate understanding
any text book of physical metallurgy may be consulted).
In normal circumstances, finite cooling rate is applied to
gain sufficient driving force for transformation to takes place.
Thus as previously mentioned, the equilibrium phase diagram
is of limited use in practical heat treatment. Equilibrium
cooling is not generally practiced; nevertheless knowledge of
equilibrium diagram of a system is extremely important to
understand its heat treatment behavior. Equilibrium diagram
16 Fundamentals of Heat Treating Metals and Alloys
provides information about which phase is stable at what
temperature–composition combination.
From the information one can decide the temperature of
heating to get a single phase alloy at higher temperature.
Equilibrium diagram denotes the stability of different
phases at various temperature–composition combinations. It
provides information of possible polymorphic transition, limit
of solubility of a solute in a solvent as a function of tem-
perature and also the amount of different phases present in an
alloy at any particular temperature. However all these infor-
mation are true only if equilibrium state exists all through. In
practice equilibrium is not maintained in most of the time;
at any finite cooling rate there is factually a deviation from
equilibrium. A fast cooling puts constraints to attainment of
equilibrium in a diffusional transformation which depends
upon time. So, transformation must take place at temperature
lower than the equilibrium temperature. It is also known that
a phase transformation takes place only with a finite under-
cooling; the number of nuclei available for transformation
depends upon the degree of supercooling and hence the
temperature at which transformation is given to take place.
This information however is not available from equilibrium
diagram. Hence it is very important to get the information
about the transformation characteristics at temperature lower
than the equilibrium one. This necessitates the construction
of isothermal transformation diagram; these are essentially
temperature–time plot for various amounts of transformation,
say transformation start, its finish or any other percentage of
transformation. Such diagram for eutectoid steel is shown in
Figure 6. It is found that pearlite and bainite transformation
overlap and from the nose of the TTT curve at about 550 1C
upward, pearlitic reaction takes place; below 450 1C, bainitic
transformation is certain. From the very nature of TTT diagram
it is apparent that if cooling rate is such that the time required
Figure 15 Arbitrary time–temperature paths on the isothermal diagram of a hypoeutectoid steel.1
to reach the temperature of the nose is less than or equal to its
incubation time, diffusional decomposition of austenite is
completely suppressed.
The time required to start the transformation at a temperature
is the incubation time required by the system to overcome the
activation barrier of the concerned diffusional transformation.
The TTT diagram of hypoeutectoid steel shows its similarity
with that of eutectoid steel in the sense that:
1. The curves are ‘C’ shaped characterizing diffusional trans-
formation.
2. Being asymptotic to the critical temperatures at long time,
hint that undercooling is must for transformation to take
place, else infinite time will be required to effect a trans-
formation which is impossible.
However the dissimilarity between the two is the presence of
a line ‘ab’ lying above and to the left of lines describing
the austenite to pearlite transformation. This line ‘ab’ is
asymptotic to A3 temperature at infinite time and defines the
formation of proeutectoid ferrite. From the cooling paths
imposed on the TTT diagram of hypoeutectoid steel, it is
apparent for path 1 that the proeutectoid ferrite forms between
A3 and A1 temperature and holding for a long time it simply
equilibrates to produce ferrite and unreacted austenite. However
for path 2, the proeutectoid ferrite formation is followed by the
complete transformation of remaining austenite to pearlite. In
contrast cooling path 3 passes through the lines of TTT diagram
below its nose and leads to the formation of bainite. Although
isothermal transformation behavior is understandable by fol-
lowing the cooling paths drawn in Figure 15, these cooling
paths are not possible to be realized in practice.
Superimposition of cooling curves on to an isothermal
transformation diagram may be made to avoid the imaginary
cooling path envisaged in the preceding paragraph. Cooling

curves are essentially a temperature–time recording con-
tinuous change of temperature of a cooling object with time.
This superimposition is demonstrated in Figure 16. For a very
slow cooling rate aiming to resemble full annealing, it is found
that transformation is completed within a narrow temperature
band just below the critical temperature A1; the microstructure
simulates that of annealed steel and consists of pearlite of large
interlamellar spacing. The cooling path is however the one that
demonstrates the entire transformation to take place at con-
stant temperature due to isothermal holding for sufficient
period of time. Relatively faster cooling rate (as in cooling path
3) has led to transformation occurring at lower temperature to
yield fine pearlite. Cooling path 4 represents the CCR which
when employed disallows diffusional transformation of aus-
tenite to pearlite. Any rate of cooling higher than the CCR will
retain metastable austenite till a different mechanism of phase
transformation without the aid of diffusion is realized by the
system. A diffusionless shear transformation has to take place
unless the metastability of austenite is enhanced so much so
by alloying, that the temperature of martensite formation, Ms,
goes below room temperature (readers may check up with text
books on phase transformation). In that case metastable aus-
tenite will remain at room temperature as in the case with
austenitic stainless steel.
Unfortunately superimposition of continuous cooling
curve on a TTT diagram is not scientifically justified, although
it gives a rough estimate of phase transformation in steel under
nonequilibrium cooling (Figure 17).
Figure 16 Superimposed cooling curve on TTT diagram.
Fundamentals of Heat Treating Metals and Alloys 17
That is why TTT diagram cannot be directly used for
describing the transformation of austenite in practical situa-
tion. For this purpose CCT diagrams are needed to be con-
structed. Incidentally it is possible to derive the CCT diagram
from the corresponding TTT diagram.
As evident from Figure 18 the supercooled austenite under
a state of continuous cooling transforms over a range tem-
perature. On the contrary TTT diagrams are drawn by mon-
itoring time dependent austenite decomposition at constant
temperatures.
The approximate CCR from a TTT diagram is obtainable by
the use of Grange–Kiefer formula:
CCR ¼ ðA 1
T nose Þ=1:5t min
where, tmin ¼ minimum incubation period at the nose of the
TTT diagram, Tnose ¼ temperature at the nose where incubation
period is minimum.
Moreover commercial heat treatment is hardly accom-
plished isothermally at constant temperature. Therefore one
needs to understand the difference between TTT and CCT
diagram. From Figure 18, it is noticed that continuous cooling
from a temperature above eutectoid temperature reaches the
line for austenite–pearlite transformation after a time say t1
second. Let it be taken that after a lapse of t1 second while
cooling the stock at the cooling rate C1, the temperature
attained by the stock is T11C. It may now be presumed that
entire stock had been at T11C for a time of t1 second with in
18 Fundamentals of Heat Treating Metals and Alloys
Figure 17 Superimposition of cooling curves on a TTT curve
(austenite decomposition). Cooling rates V1oV2oV3oV4oV5.
Figure 18 The relationship of the continuous cooling diagram to the isothermal diagram for an eutectoid steel (schematic). After Atlas of
Isothermal Transformation Diagram; United States Steel Corporation: Pittsburgh, 1951.
the metastable austenite region. This is as tenable as at any
temperature higher than T11C; the stock requires more than t1
second to reach the line for pearlite start temperature. The
continuously cooled sample is not ready to form pearlite after
t1 seconds, rather it will take a slightly higher time to initiate
the reaction. Thus the point ‘a’ is shifted toward right. Again
higher time implies a greater drop in temperature. This means
the actual position of pearlite start point ‘b’ is toward right of
‘a’ as well as depressed. Similarly at the g-pearlite finish point
may be found lie at ‘d’ to mean that the ‘c’ point on TTT
diagram is shifted toward right and downward.
TTT diagram is therefore quite useful in predicting the cool-
ing rate required to avoid soft pearlitic transformation of aus-
tenite. From the foregoing discussion it is very clear that if a rate
of cooling is faster than the CCR in accordance with TTT dia-
gram, it is certain that in actual case of prediction made on the
basis of corresponding CCT diagram, the same cooling rate will
always give rise to non-diffusional products of transformation.
CCT diagram can be obtained quite accurately by a number
of techniques. Differential dilatometric technique is generally
employed to construct the CCT diagram of any steel under
preprogramed cooling schedule. Figure 19 shows the CCT
diagram drawn in Gleeble machine which makes use of dila-
tometry to accomplish the task.
From the curve in Figure 19, it is clear that transformation
under continuous cooling takes place over a range of tem-
perature. Since structure and morphology of phases formed

Figure 19 Continuous cooling transformation diagram of a low
carbon steels constructed by dilatometric method.
due to phase transformation depend upon the transformation
temperature, it is imperative that there will be a structural gra-
dient in steels cooled continuously. Moreover it is pertinent
to remember that phase transformation in many steels is
mechanistically transient over a range of temperature, the com-
plete transformation of parent phase takes place. This is parti-
cularly important for low carbon steels, where the mechanisms
of austenite to ferrite transformation are different at different
temperatures. Thus quite often a multiphase microstructure is
obtained by continuous cooling of low carbon steels. However
microstructural gradient is not desirable in respect of deriving
uniform properties in the heat treating object. The shape of the
CCT diagram determines if there will be uniformity of micro-
structure. In some alloy steel it is possible to get flat CCT dia-
gram in both cases of transformation start and finish, which
represent low carbon bainite and hence chances of micro-
structural gradient is least in this case. Whenever a decom-
position of austenite takes place under continuous cooling, a
number of mechanisms are operative for austenite to ferrite
transformation depending upon the temperatures of transfor-
mation. For example, in low carbon high strength low
alloy steel (HSLA) steel, progressively decreasing transforma-
tion temperature or equivalently the increasing cooling rate,
envisages the transformation of austenite in the following
sequence.
AusteniteðgÞ-Equiaxed ferriteðaP Þ-Quasipolygonal ferriteðaq Þ-
Widmanstatten ferriteðaw Þ-Massive ferriteðamassive Þ-
Granular bainiteða0 BÞ-Acicular bainiteðaB Þ-MartensiteðaM Þ
However in the regime of CCT diagram where acicular bai-
nite or martensites are formed, the transformation mechanism is
practically same at all transformation temperatures, viz. martens-
itic transformation. This situation of microstructural gradient
is of much greater concern for finite-sized samples. Whenever a
finite sized sample is cooled from the austenite state to effect
Fundamentals of Heat Treating Metals and Alloys 19
Figure 20 Diagram showing different cooling rates at surface and
center of the workpiece.
phase transformation, the cooling rate at the surface and at the
center of the sample ought to differ as shown in Figure 20.
The temperature difference at each time during cooling is
dependent upon two important factors. One is the material
and other is the external media used to cool the object. For the
same material, cooling from the same austenitizing temperature
but in different media like water and oil will result in different
temperature differential between surface and center of the sam-
ple. So whenever it is required to avoid the nose of a TTT or
CCT diagram in a heat treatment process, it is required to decide
the cooling media for the same due to following reasons:
1. Different cooling media has different heat extracting ability
from a specific stock of definite size, that is different
quenching media have different severity of quench; it is
further important to note that the cooling rate achievable
from a quenching medium varies with the changing tem-
perature of the sample during cooling. Thus severity of
quench is a sole property of the quenching medium.
2. By virtue of heat transfer ability, different materials exhibit
different responses to cooling in various quenching media.
Also each material has its characteristic section sensitivity
(i.e., variation of cooling rate at different places at any
time). This implies that there is a sole material property
which defines the ability of a material to avoid diffusional
decomposition of the metastable parent phase. To get a
reach to this material property, it is necessary to remove the
effect of cooling rate on the ability of material to avoid the
nose of TTT diagram of a material.
This inherent property of steel is called hardenability which
describes the depth up to which a steel component is able to
avoid soft pearlite transformation. The term hardenability
originates from the fact that avoidance of the nose of CCT
curve by a cooling rate higher than the CCR leads to the
hardest possible phase in steel, which is martensite. This
definition of hardenability is not universal. The idea of
increasing the hardness of a material by avoidance of diffu-
sional decomposition of high temperature parent phase is not
generic. It is true that if a metastable solid solution is not
allowed to undergo its due decomposition by way of diffu-
sional means at relatively high temperatures, the solid solution
will take chance to form more thermodynamically feasible
alternative phase, through diffusionless shear transformation
20 Fundamentals of Heat Treating Metals and Alloys
mechanism. This type of transformation, martensitic trans-
formation, takes place in a number of systems. For steel, the
martensites are extremely hard. There are many systems like
Cu–Zn–Al, Cu–Al–Ni, Ni–Ti, In–Th, where the martensite
phase is very soft. The high hardness of iron–carbon marten-
sites is ascribed to (1) solid solution hardening due to it being
a supersaturated solid solution of carbon in body centered
tetragonal structure, (2) dispersion hardening due to fine-scale
precipitation of carbide due to auto tempering, (3) dislocation
hardening due to martensite being internally faulted with
dislocations, (4) hardening due to interaction between dis-
locations and distortion dipole produced in martensite due to
asymmetric alignment of carbon atoms in the unit cell and
finally due to fine crystal size. The suppression of solid state
diffusional transformation by fast quenching is quite common
in many systems; it is true that a rapid cooling to bypass the
diffusional transformation (hence the nose of corresponding
CCT diagram) results in the formation of a supersaturated solid
solution. The supersaturated solid solution in iron–carbon
system is hardest and hence this process is called hardening heat
treatment. In other systems, the supersaturated solid solution
may not be the hardest (e.g., Al–4 wt.%Cu) constituent, but this
may give rise to hardening when heated to slightly higher
temperature and held for preselected period of time.
However hardening of hypoeutectoid steel is carried out
50 1C above A3 temperature and then it is soaked there for
sufficient period of time as discussed earlier. The homo-
geneous austenite is then rapidly cooled with the aim to
produce 100% martensite in the structure. In case of eutectoid
steel, the steel requires a temperature of 780–800 1C for pro-
duction of homogeneous austenite and then it is quenched.
An empirical relationship between the Ms temperature and
alloying element content may be written as,
Ms ð1CÞ ¼ 561
474ðwt: %CÞ
33ðwt: %MnÞ

21ðwt: %MoÞ
17ðwt: %NiÞ
17ðwt: %CrÞ ½1
It is evident that carbon has the maximum effect to lower
the Ms temperature. Thus for high carbon austenite in hyper-
eutectoid steel, the depression of Mf temperature below room
temperature will always yield some retained austenite in the
quenched microstructure. This retained austenite will make the
material softer at specific location, thereby rendering it to an
inferior quality material.
2.1.5 Annealing
Annealing is the process of heating the object to single phase
field followed by equilibrium cooling to aim at achieving
equilibrium microstructures. Depending upon the purpose,
various annealing types are carried out at different tempera-
ture. The temperatures used for various types of annealing
operation are shown in Figure 21.
2.1.5.1 Full Annealing
Full annealing is carried out to achieve a microstructure pre-
dicted by the equilibrium phase diagram of the alloy system. Full
annealing process involves heating hypoeutectoid and eutectoid
steels 50 1C above Ac3 and Ac1 temperatures, respectively. The
Figure 21 Diagram showing temperature ranges of different
annealing process.
component is held for 1 h per 25 mm of section size and then
subjected to very slow cooling. The rate of cooling should be as
slow as possible and an example of industrially acceptable
cooling rate to obtain near-equilibrium structure is 50 1C h
1.
Again, care must be taken to avoid decarburization especially in
case of annealing high carbon steels. The aim of full annealing is
to effect diffusional decomposition of parent phase, viz. auste-
nite in case of steel, at as low an undercooling as is possible to
be provided by the furnace. The microstructure in annealed
hypoeutectoid steel consists of proeutectoid ferrite and pearlite
whereas it is full pearlite in eutectoid steel (Figures 22(a) and
22(b)). Hypereutectoid steels are not ordinarily put to full
annealing. The Acm line is quite steep and full annealing of
hypereutectoid steel attempting to produce completely homo-
geneous austenite necessitates heating the steel to a very high
temperature, with associated risk of grain coarsening and dec-
arburization. However full annealing of hypereutectoid steel is
required if prior hot working is done at a very high temperature
causing overheating and gain coarsening. Under such situation a
judicious full annealing may result in partially refined grain
structure. If cooling rate is high, network of proeutectoid con-
stituents around the grain boundaries is likely to form; a slower
cooling on the other hand may lead to the formation of separate
ferrite regions in full annealed hypoeutectoid steel.
2.1.5.2 Isothermal Annealing
In case of isothermal annealing, steel is heated in the same
manner as that in the case of full annealing. After austeniti-
zation the steel is rapidly cooled at a predetermined tem-
perature and it is held there for sufficient period of time so
that transformation of austenite becomes complete. A prior
knowledge of TTT diagram enables to determine the time of
holding at the isothermal annealing temperature. Isothermal
annealing is advantageous as the total heat treatment time is
considerably reduced yet obtaining comparable microstructure
and properties. Isothermal annealing is particularly suitable
for alloy steels which otherwise require at extremely slow

Figure 22 (a) Ferrite–pearlite microstructure of 1018 carbon steel annealed at 900 1C, (b) fully pearlitic microstructure of 1095 carbon steel
annealed at 900 1C. Courtesy of George Vander Voort, USA.
Figure 23 Isothermal annealing of alloy steel.
cooling in order to effect transformation involving the long
range of migration of slowly moving atoms of the alloying
elements. As evident from the Figure 23, object being heat
treated is cooled rapidly after austenite is completely trans-
formed to the desired phase that is pearlite.
Patenting is a specific isothermal annealing where the
transformation of metastable austenite is effected just at the
nose of the TTT diagram of the material under heat treatment.
Normally patenting is carried to impart high strength to
musical wires. A high carbon steel of nearly eutectoid com-
position is austenitized 15 1C above Ac3 for hypoeutectoid and
above Ac1 for eutectoid composition (0.65–0.80). After pro-
ducing homogeneous austenite rapid cooling is done in a salt
bath kept at about 450–550 1C and held for complete trans-
formation of austenite to fine ferrite–carbide aggregate. In
accordance with the possible mechanism of transformation of
austenite to fine ferrite–carbide aggregate, the microstructure
may comprise of either fine pearlite or a mixture of fine
pearlite and upper bainite. The patented rod is cold drawn to
Fundamentals of Heat Treating Metals and Alloys 21
fine wire, to be used in musical instrument as combined
microstructural and strain-hardening results in a very high
strength of the wire.
2.1.5.2.1 Patenting
‘Patenting’ is a process of annealing which is generally employed
in wire and rod manufacturing process. Patenting is normally
carried out when extra toughening is required in steels con-
taining 0.5 wt.% or higher amount of carbon. The annealing
process in the name of patenting involves isothermal annealing
of steels in a suitable salt bath at temperature near the nose of
the TTT diagram. After austentizing the steel is cooled rapidly to
the isothermal holding temperature viz. 550 1C. The object is
kept at that temperature for sufficiently time so that complete
transformation of austenite to fine pearlite is possible.4 The
objective of patenting is to produce very fine pearlite in the
microstructure (Figure 24); since smaller inter lamellar spacing of
pearlite envisages high toughness of steel it is applied to med-
ium- and higher-carbon grades of steel, rod, or wire products.5
22 Fundamentals of Heat Treating Metals and Alloys
Figure 24 1080 steel isothermally annealed at 482 1C (patenting).
Courtesy of George Vander Voort, USA.
Sometimes drawing and patenting steps are successively
repeated for obtaining the desired size and strength level.
Appropriate tailoring of composition may enable complete
transformation of austenite to fine pearlite by air cooling; this
alleviates with the use of salt bath or molten lead bath which is
health hazardous. Air patenting is less expensive than lead
patenting but results in pearlite of varying inter lamellar spa-
cing which is not desirable. For a less, hardenable steel pos-
sibility of formation of proeutectoid ferrite may not even be
precluded.
The steels to be used for manufacturing suspension bridge
wires demand extra strengthening after patenting; for this
hypereutectoid steel with minor addition of chromium B0.5 wt.
% is now a day’s employed. Chromium induces a higher degree
of refinement in interlamellar spacing of pearlite in hyper-
eutectoid chromium bearing steel, even down to 70 nm.6–8 Also
the carbide lamella becomes shorter and discontinuous. When
steel with such fine pearlitic microstructure is subjected to heavy
deformation during wire drawing cementite particles decom-
pose. The ferrite crystals get supersaturated with carbon. Com-
plete decomposition of cementite is envisaged in chromium
bearing hypereutectoid steel. Excess carbon precipitated on dis-
locations within the resulting ferrite not only increases the
strength of the steels but also its work hardening rate quite sig-
nificantly. This aids in suppression of delamination. Heavy
drawing of such steels reportedly leads to a super saturation of
ferrite up to 0.5 wt.% carbon with consequent UTS being about
1500 MPa. The degree of decomposition of cementite depends
upon the rise in temperature during wire drawing; the adiabatic
heating in heavily drawn wire causes decomposition of cemen-
tite with concurrent deposition of carbon atoms at the disloca-
tions which are pinned by the carbon atoms; as a result of
consequential strain aging effect yield strength of the steel is
significantly increased. The microstructure of a 1080 carbon steel
is in Figure 24.
The decomposition of cementite phase, y during heavy
drawing has been ascribed to elastic interaction between dis-
locations and C-atoms.4,8 It is postulated by one school of
thought that heavy deformation during wiredrawing leads to
refinement of cementite. Upon continued deformation, the
slip steps is formed in y; these two events lead to increase in
interfacial areas and hence the surface free energy. The dictates
of Gibbs–Thomson effect in respect of urge to lower surface
energy results in ultimate decomposition of cementite. The
state of C-atoms in a, may provide clues to such decomposi-
tion of cementite; if carbon is present at dislocations, strain
aging effect will enhance the yield strength quite significantly.
On the contrary, if carbon is assumed to cause super saturation
of ferrite solid solution hardening shall be the chief hardening
mechanism with concurrent change in the lattice parameter.
Equally the other proposals that carbon segregates at the prior
a–y interfaces,5 or that carbon precipitates out in the form of
carbide on to the dislocations9 have grounds to attract due
attention. The observation that no significant change in lattice
parameter in noted in the process may cast doubt on the ferrite
super saturation model.
There are reports10 that heavy deformation during forging
of white cast iron led to collapse of cementite lattice and that
elemental carbon released in huge quantity leads to graphiti-
zation. High carbon steel for wire drawing contains much less
proeutectoid cementite as compared to ledeburitic cementite
in white cast iron grown further in size due to precipitation of
proeutectoid cementite. The author hypothesizes that heavy
deformation during wire drawing leads to collapse of cemen-
tite and the concurrent diffusion of carbon atoms from
cementite–ferrite boundary to intragranular dislocations in
ferrite takes place at high temperature due to local adiabatic
heating. However, being energetically cheaper, the carbon
atoms prefer to segregate at the dislocations in the form of
metastable cementite and not in elemental form. In this case
one will find that carbon content of ferrite is high without
tangible rise in lattice parameter. All observations made so far
are also compatible to the hypothesis. Nevertheless it is of
paramount importance to study the nature of particles present
at the dislocations within ferrite; the possibility of formation
of e-carbide and/or chromium bearing carbide of higher car-
bon content must not be ruled out especially in situation of
high strain rate deformation.
2.1.5.3 Incomplete Annealing or Intercritical Annealing
Incomplete annealing aims at relieving internal stresses thereby
improving machinability of the steel. Normally this type of
annealing is carried out by heating the stock just above Ac1
and then holding there for sufficient time. Finally it is cooled
slowly within the furnace. It must be understood that this
type of annealing does not eliminate proeutectoid ferrite or
cementite from the microstructure at the annealing tempera-
ture. Mainly incomplete annealing of such type is applied to
hyper eutectoid steel. Annealing of hypereutectoid steel pro-
duces the microstructure with cementite network enclosing the
pearlitic region. Whenever incomplete annealing is carried out
in eutectoid steel, the effect of full annealing is realized because
the annealing temperature lies in the austenite phase field.
Intercritical annealing of hypoeutectoid steel followed by
rapid cooling gives rise to a duplex ferrite–martensite structure.
This type of heat treatment for low carbon micro-alloyed steel
is quite popular in recent years. The steel is held at a con-
venient intercritical temperature till the time it is equilibrated
between higher carbon austenite of low volume fraction and
low carbon ferrite. Upon rapid cooling from the intercritical
 Fundamentals of Heat Treating Metals and Alloys 23

Figure 25 (a) Microstructure of intercritcally annealed 4140 alloy steel showing ferrite and martensite (Courtesy of George Vander Voort, USA)
and (b) microstructure of hypereutectoid steel annealed above Acm temperature followed by slow cooling.

annealing temperature, austenite transforms to martensite.

This biphasic structure, where martensitic island are inter-
spersed with in soft ferrite matrix strengthens the material
significantly. Figure 25(a) delineates ferrite–martensite struc-
ture in 4140 steel intercritically annealed at 775 1C within
g þ a phase field followed by water quenching.
The yield–tensile ratio of this steel is about B0.5; this
HSLAs possess excellent deep drawability and is considered to
be a very good automotive material.
Again annealing of hypereutectoid steel is essentially an
intercritical annealing as it is austenitized above A1 tempera-
ture in the two-phase field g þ cementite and then furnace
cooled. This makes the proeutectoid cementite agglomerated
or spheroidized. On the contrary if it is annealed by austeni-
tizing at temperature above Acm and then slow cooled to
room temperature, proeutectoid cementite forms a network
along prior austenite grain boundaries. These types of micro-
structures promote intercrystalline fracture and thus make it
brittle (Figure 25(b)). Annealing of hypereutectoid steel in two-
phase field breaks the continuous cementite network by
agglomeration into spherical carbide particles. The associated
reduction in austenite–cementite interfacial area acts as the
driving force for the process.
2.1.5.4 Spheroidizing Annealing
Spheroidizing annealing is meant for obtaining granular
cementite in a ferrite matrix. The lamellar pearlite of high
carbon steel is converted to granular morphology by way of
heating the steel just above the critical temperature, 740–
750 1C and then holding at that temperature for considerable
period of time. This is followed by a slow cooling of the order
of 25 1C per hour down to a temperature of 600 1C. To obtain
granular cementite the annealing temperature should not
be too high above Ac1 and cooling rate should be so slow as
to allow decomposition of austenite to be completed at a
low degree of supercooling. This enables the cementite parti-
cles to attain globular morpohology. High carbon steels are
conducive to such spheroidizing annealing temperature when
heat treatment is carried at a temperature slightly above Ac1
temperature; however spherodization of cementite particles is
Figure 26 Microstructure of steel after spheroidizing annealing.
Courtesy of George Vander Voort, USA.
also aimed in relatively lower carbon containing alloy steels
as a pretreatment for facilitating production of homogeneous
austenite during the subsequent autenetization. Instead of
holding the steel just above Ac1 temperature, thermal cycling
across Ac1 temperature for a number of times may also give
rise to spheroidization of carbides. During thermal cycling
across Ac1 the steel is held at a temperature just below Ac1 for
predetermined period of time followed by gentle heating.
Repetition of isothermal cycles will produce the desired
spheroidized morphology. In the heating stage of thermal
cycling carbides tend to dissolve but reappear in the following
cooling cycles. Attempts to effect phase transformation with
such a low driving energy entices the system to assume
spheroidal morphology; spheroidization diminishes the spe-
cific surface area and thus overcome the constraint due to
surface free energy term in the target phase transformation.
Implicitly the spheroidal structures are softer with good
machinability. As stated earlier a microstructure with spher-
oidal cementite aids in production of homogeneous austenite.
Figure 26 exhibits spheroidized cementite in hypereutectoid
steel containing 1.05 wt.% carbon steel.
Inter critical annealing of hypereutectoid steel gives rise to
globular cementite and thus leads to the formation of granular
24 Fundamentals of Heat Treating Metals and Alloys
pearlite. Within the intercritical region, undissolved cementite
particles tend to globularise due to prolonged heating at the
annealing temperature. Spheroidization of particles held at
elevated temperature is a natural event. Spheres have mini-
mum specific surface area as compared to other shapes and
hence spherodization of a micro-constituent leads to the
diminution of its surface free energy. Thus the process of
spherodization enables the system to lower its overall energy.
At the temperature of inter critical annealing diffusion is not a
constraint; this favors the kinetics of spheroidization. During
slow cooling the carbon content of austenite will gradually
decrease down the Acm line. So rejection of carbon in the form
of cementite may take place on to the existing cementite par-
ticles as this will reduce the requirement of supply of energy
for nucleation of new phase. When austenite is cooled just
below the Ac1 line, austenite needs to undergo eutectoid
reaction which is essentially a discontinuous precipitation
where cementite is the leading nucleating phase.
Eutectoidal cementite will form mostly through deposition
on the existing cementite particles although nucleation of new
cementite on the prior austenitic grain boundaries is not
excluded. In any case this cementite will have a better scope of
equiaxed growth and hence the overall microstructure will
consist of globular pearlite.
Spheroidization is also carried out by holding the object
under heat treatment just below A1 temperature. Prolonged
holding at this temperature effects spheroidization of cemen-
tite particles, embedded in ferrite matrix. However this
method of spheroidization is rather slow. It is not out of place
to mention than the equilibrium shape of the particle is not
strictly spheroid but ellipsoidal. Particles assume spheroidal
morphology due to the urge to attain low energy state is rea-
soned out by the fact that in solid state transformation strain
energy is equally important.
Maximum reduction in strain energy is not concurrent with
spheroidal growth of the particle. Rather growth of particles
along specific direction reduces the lattice disregistry, and hence
the strain energy. However continued nonspherical growth to
reduce strain energy is in opposition toward attainment of
stability in a system; this is because the nonspherical growth
increases the surface area and hence the surface free energy.
Thus a situation comes, when urge to reduce surface energy
takes over and a spheroidization process sets in. This continues
till strain energy term prohibits spherical growth and thus the
aspect ratio of the particle swings across a value near to but less
than unity.
2.1.5.5 Homogenization or Diffusion Annealing
Homogenization or diffusion annealing is usually carried out
for heavy and intricate castings which are prone to significant
intercrystalline segregation. Homogenization annealing is car-
ried out to remove the inevitably occurring chemical inhomo-
geneity in heavy alloy steel casting. In reality most of steel
casting produced under moderate cooling rate as in sand molds
experience segregation of alloying elements along the cell
boundary of the cellular dendritic structure. To ensure micro-
structural homogeneity diffusion annealing is carried out at
high temperature as 1150 1C so that appreciable diffusion of
atoms of the alloying elements takes place easily. This entails
the possibility of achieving austenite of uniform composition.
However homogenization annealing as demanded to be carried
out at such a high temperature is liable to produce coarse-
grained microstructure along with formation of scales at the
surface of the casting. Therefore homogenization annealing is
followed by subsequent heat treatment process to incorporate
the desired set of properties in the steel castings. These heat
treatments may be conventional full annealing, normalizing or
normalizing followed by tempering depending upon the spe-
cified property requirement.
2.1.5.6 Recrystallization Annealing
Recrystallization annealing is a process of heating cold-worked
steel above the recrystallization temperature, holding at that
temperature for a predetermined time and then followed
by normal air cooling. Recrystallization annealing is carried
out for removing strain-hardening effect of multipass cold-
working operation. In such case, recrystallization annealing is
an intermediate process to facilitate further deformation by
cold working. On the contrary, recrystallization annealing is
also employed as a final heat treatment where removal of cold-
working effect with replacement by fine equiaxed strain-free
grains is derived. Proper selection of time and temperature of
annealing enables to achieve fine-grained uniform micro-
structure comprised of recrystallization. Sometimes a cold-
worked structure is subjected to annealing at a temperature
less than the recrystallization temperature with the purpose of
rearranging dislocations to some low energy configurations.
This is known as a recovery process and is accomplished by
suitable annealing process.
When metals and alloys are cold worked, that is when these
are subjected to plastic deformation at a low temperature, say,
less than 0.4 Tm (Tm is the melting point of the concerned
metal or alloy in degree Kelvin), a portion of energy spent for
cold-working remains stored within the material in the form of
crystal defects. The amount of stored energy ranges from a low
value to around 10% of the total energy spent in a deforma-
tion process. The work of deformation leads to generation of
point defects and dislocations. These crystal defects are asso-
ciated with strain energy and the creation of crystal defects
during deformation is the manifestation of stored energy in
cold-worked materials. Obviously the magnitudes of stored
energy increases with increasing amount of deformation up to
a certain saturation value which is different for different
materials and deformation condition; however in most prac-
tical cases, the maximum of stored energy does not exceed
15% of the energy spent in cold working and the rest energy is
dissipated in the form of heat.
The above stated stored energy drives the relaxation pro-
cesses during subsequent annealing. Upon annealing, the
stored energy is released through different recovery processes
which may occur in steps. The process involved during the
release of stored energy is called recovery, recrystallization, and
grain growth. During recovery process the point defects viz.
vacancies are annihilated at the sinks like grain boundaries, or
it may annihilate at edge dislocation affecting its climb. The
reduction in density of point defects due to recovery process
leads to reduction in resistivity of the metals and alloys.
Resistivity is due to incoherent scattering of electrons at the

scattering centers like point defects. Also during recovery
process, the dislocations generated by cold working either get
annihilated or reorganize themselves into low energy arrays.
Annihilation of dislocations takes place where dislocations of
opposite sign come together either through slip or through
climb. Normally the dislocations remaining in excess after
annihilation would try to reorganize themselves into low
energy array for the purpose of lowering the overall energy of
the system. One example of such process is what is termed as
polygonization. When a crystal is bent, the excess positive edge
dislocation may lie along the active slip planes in disorderly
fashion. When a row of edge dislocation lie on a specific plane,
its total strain field in quite high; if the dislocations lying on
different vertical planes are arranged in disorderly fashion, the
overall strain energy due to dislocations in bent crystal
becomes quite high. However, if the bent crystal is heated, the
dislocation climb is possible and a regular arrangement as
shown in Figure 27 is realized.
When the dislocations are rearranged in the manner as
shown in Figure 27, the tensile and compressive component of
strain field due to adjacent dislocations will tend to cancel
each other; as a result total strain energy of the system will
be reduced. The region of crystal in between any two lines
Figure 27 Recovery of crystal showing rearrangement of dislocations in bent crystal (polygonization); (a) shows irregular arrangement of
dislocations and (b) shows rearrangement to low energy array.
Figure 28 Variation of properties for cold-worked nickel due to recovery annealing. Courtesey of J.E. Indacochea University of Illinois at Chicago, USA.
Fundamentals of Heat Treating Metals and Alloys 25
of dislocations is essentially devoid of dislocations and thus
becomes a strain-free region. These strain-free regions within
the crystal are bound by thin arrays of dislocations, describing
a small degree of misorientation across the regions; con-
sidered as boundary, it is called a sub grain boundary. During
recovery of cold-worked crystals, mechanical and physical
properties are changed. The resistivity decreases with increase
in time or temperature till a saturation value is attained
(Figure 28).
A typical microstructure containing sub grain boundaries is
shown in Figure 29.
When annealing is carried out at temperatures above 0.4
Tm a different recovery process takes place. During this process,
highly strained grain within cold-worked material (character-
ized by high dislocation densities) is replaced by the strain-free
grains. This process of relaxation is called recrystallization.
Recrystallization is a nucleation and growth type process as
initiated by the formation of nuclei of strain-free grains which,
subsequently, grow by migration of its high angle boundaries.
The growth of strain-free crystals continues in all directions
until there is impingement from the surrounding crystals.
Being a thermally activated process, recrystallization is tem-
perature and time dependent; also the process is influenced by
26 Fundamentals of Heat Treating Metals and Alloys
the amount of deformation. The following observations can be
made in any recrystallization process.
1. A minimum amount of deformation is required to effect
recrystallization at a particular temperature.
2. Time required to complete recrystallization increases as the
temperature of recrystallization is lowered.
3. With increasing deformation percent, the temperature to
start recrystallization is decreased.
4. Recrystallized grain size becomes smaller with larger per-
centage of deformation at a particular temperature.
5. New strain-free grains don’t grow into deformed grains.
6. A metal or alloy with fine initial grain produces smaller
recrystallized grain.
The recrystallization kinetics in metals and alloys shows
typical sigmoidal behavior as shown in Figure 30.
The same figure demonstrates that increase in recrystalliza-
tion temperature reduces the time to complete recrystallization.
It also takes less time to initiate the process of recrystallization.
Figure 29 TEM of 0.05C–1.5Cu–1.5Mn steel showing subgrain
boundaries. Courtsey of Material Research Centre, MNIT Jaipur, India.
Figure 30 Sigmoidal curves to show recrystallization kinetics. Courtesey of J.E. Indacochea University of Illinois at Chicago, USA.
Several mechanisms of recrystallization are proposed. There
can be different dislocation density across a grain boundary; the
grain boundary is not strictly planar but it is perturbed with
transient wavy character. A small bulged-type region at grain
boundary may move into region of high dislocation density.
Grain boundary acts as sinks for dislocations and annihilates
them; the creation of such small dislocation free region lowers
the local free energy and hence becomes a stable nucleus. The
nucleus then grows to form a strain-free grain (Figure 31).
The other mechanism of recrystallization is the coalescence of
sub grains to form a region bound by high angle boundary and
hence a strain-free grain is formed under the driving force of
lowering of strain energy due to replacement of a number of sub
grain boundaries by a single boundary of large misorientation.
While recovery process reduces the electrical resistivity,
recrystallization leads to reduction of hardness values with
progressive diminution of dislocation density. For a fine
recrystallized grain structure both strength and ductility are
simultaneously improved. The change in properties of a
heavily cold-worked metal subjected to isothermal annealing
above recrystallization temperature is shown in Figure 32.
Further annealing at still higher temperature leads to grain
growth. The driving force for grain growth is lowering of
Figure 31 Recrystallized structure of IF steel. Courtsey of Material
Research Centre, MNIT Jaipur, India.

Figure 32 Variation of mechanical properties during recrystallization.
Courtesy of J.E. Indacochea University of Illinois at Chicago, USA.
surface free energy. Anything which aids grain boundary
movement shall accelerate grain coarsening.
During recrystallization annealing proper control of
recrystallization temperature and time is required. After the
completion of recrystallization, the process must be stopped;
else grain coarsening will set in.
2.1.5.7 Subcritical Annealing
Subcritical annealing is generally carried out at a temperature
below the lower critical temperature, A1. There are a number of
purposes for which subcritical annealing is considered to be a
useful heat treatment operation. Apparently subcritical
annealing is not liable to cause any phase transformation.
However it will be demonstrated in the following discussion
that in certain cases phase transformation may be realized in
subcritical annealing.
1. Indirect second stage graphitization of cast iron is a sub-
critical annealing process, where cast iron with pearlitic
matrix is heated to an elevated temperature below A1
temperature. Upon holding for a prolonged time, the
pearlitic cementite may undergo decomposition to form
graphite, leaving behind ferrite in the matrix. Thus com-
plete second stage graphitization will lead to the formation
of ferritic cast iron, which is a cast iron where graphite
particles (flakes or other shapes) are contained in a ferrite
matrix; this makes the cast iron soft and ductile.
2. Subcritical annealing is carried out in large and intricate
castings to get rid of internal stresses. It is also carried out
after welding of some steels where there is a chance of for-
mation of martensite at the heat affected zone. The welded
joints are subjected to both thermal stress and stress due to
volume change accompanying martensite transformation.
Subcritical annealing relieves the thermal stress by dis-
location annihilation at the grain boundaries and as well it
removes transformational stress by way of tempering mar-
tensite to make it decompose to fine ferrite–carbide aggregate.
The microstructure of 0.10C–2Mn steel subjected to subcritical
annealing at 710 1C is shown in Figure 33.
Sometimes subcritical annealing is employed to drive away
the dissolved harmful gases within the steel component. For
Fundamentals of Heat Treating Metals and Alloys 27
Figure 33 Microstructure of subcritically annealed steel. Courtesy of
George Vander Voort, USA.
example, in cases where hydrogen is known to remain dissolved
in steel in excess of limit of tolerance, subcritical annealing at
400 1C is carried out. Diffusivity of hydrogen is quite high at
this temperature, and so it diffuses out quite easily; thus chances
of hydrogen embrittlement is greatly reduced.
In certain cases subcritical annealing or high temperature
tempering just below the lower critical temperature is employed
to improve upon the sub-ambient impact strength.
2.1.6 Normalizing
Normalizing is the heat treatment process, which consists of
heating the object to the austenitization temperature, holding
it to produce homogeneous austenite and then allowing to
be cooled in still air. Normalizing tends to imply a normal
cooling of austenite to produce stronger steel in much shorter
time than what can be obtained by full annealing. Due
to the fact that normalizing refines the microstructure of
the steel thereby improving its toughness, it is quite often
employed as the final heat treatment. Normalizing is carried at
a temperature 50 1C above upper critical temperatures (A3 and
Acm). Being austenitized at higher temperature (20 1C) than
annealing, normalizing produces greater homogeneity of
austenite but at a lower temperature than homogenizing an-
nealing and in shorter time. Quite often grain size becomes
rather large after hot working; normalizing of such coarse-
grained hot work material gives rise to formation of fine-
grained austenite which upon air cooling produces small
ferrite grains and fine pearlite in the microstructure of hy-
poeutectoid steels. This type of microstructures of greater
uniformity helps to achieve superior mechanical properties.
For example, when medium carbon steels are forged high
temperature like 1100 1C, the size of recrystallized austenite
grains is quite large due to adiabatic heating; the final micro-
structure is also very coarse (Figure 34(b)). Moreover distribu-
tion of pearlite and ferrite in its microstructures is nonuniform
and thus the forged steel may not possess good and uniform
mechanical properties. Hence it is imperative to suitably heat
treat the forged product for refinement of its microstructure;
28 Fundamentals of Heat Treating Metals and Alloys
Figure 34 Microstructure of (a) 0.4 C–0.6Mn steel under normalized condition (Courtesy of George Vander Voort, USA) and (b) microstructure of
0.5 wt.%C steel forged at 1100 1C and cooled in air.
normalizing of forged steel can lead to desired structural
refinement thereby enabling to produce fine uniform ferrite–
pearlite structure. Due to relatively rapid cooling, the trans-
formation of austenite takes place at a lower temperature,
around 600 1C. The cooling rates superimposed on a CCT
diagram of eutectoid steel qualitatively describe the difference
in transformation behavior between annealing and normal-
izing. The properties of the steel casting are made improved by
normalizing operation. It is used to remove micro-segregation
in steel castings producing thereby a homogeneous structure.
In hypereutectoid steel normalizing is carried out above Acm
temperature; this insures dissolution of carbides which aids in
removal of carbide network which might have developed in
prior processing. Normalized structure is highly responsive to
spheroidizing treatment. Quite often normalizing is used as a
preceding treatment to hardening operation, which requires a
uniformly homogeneous structure without any structural gra-
dient. If there is a structural gradient in steel before being
subjected to hardening operation, the hardened steel will yield
nonuniform hardness consisting of localized soft and hard
spots. Well-normalized steel enables to overcome this difficulty.
Air cooling is faster than furnace cooling and so normalizing
heat treatment envisages austenite decomposition at a lower
temperature. The resultant microstructure is significantly differ-
ent from that obtained by full annealing. A lower temperature
of transformation during normalizing reduces the critical
nucleus size and the energy of nucleation of proeutectoid ferrite.
So grain size of ferrite formed due to normalizing is smaller
than the annealed steel. Again due to faster cooling formation of
equilibrium amount of ferrite is not tenable. Thus the amount
of proeutectoid ferrite is less than its annealed counterpart. In
contrast with furnace cooling, equilibrium is not attained at any
stage of air cooling during normalizing. So ferrite contains
carbon in excess of equilibrium amount. Similar reasoning
applies to austenite to pearlite transformation. Lower transfor-
mation temperature envisages higher density of operating nuclei
for pearlitic transformation. This leads to decrease in the size of
pearlite colonies. At the same time the interlamellar spacing of
pearlite is reduced due to lower transformation temperature.
Since amount of proeutectoid ferrite is reduced, the amount of
pearlite is correspondingly increased as a consequence of shift of
eutectoid point toward left upon faster cooling. Thus when
compared with the achievable microstructure by annealing
hypoeutectoid steel, normalizing results in decrease of ferrite
grain size, increase of carbon content of ferrite, decrease in its
amount. All these factors increase the hardness and strength of
the steel. Again normalizing is liable to produce higher amount
of pearlite with smaller colony size and interlamellar spacing.
All these increases strength and hardness of the steel. Thus
normalized steel is structurally finer than annealed steel and is
stronger than the annealed variety. Strengthening of hypoeu-
tectoid steel due to normalizing improves the machinability.
The microstructure of normalized 1045 carbon steel is shown in
Figure 34.
Low carbon mild steel is quite soft and ductile in the
annealed state. Therefore chips of this ductile material get
adhered to the tool tip making the machining quite difficult.
Higher becomes the depth of cut, more would be the removal
of material and the chances of tool tip jamming with adherent
ductile chip will increase. On the contrary, normalizing
makes the steel strong and relatively less ductile; this
entails the scope of relatively brittle chip formation and chips
can easily get away from tool tip. This ultimately improves
machinability. Steel compositions may be suitably tailored
so that normalized itself can harden the steel or can even
alleviate with the conventional hardening and tempering heat
treatment, yet achieving equivalent or better mechanical
properties. For the advantages which can be accrued from
normalizing steel the recent efforts to make use of normalizing
as the final heat treatment process of new generation steels is
noteworthy.11–13
2.1.6.1 Distinctions between Annealing and Normalizing
Purpose
Annealing is a widely used heat treatment operation and is
generally carried to refine the microstructure of materials and
hence to improve its ductility. Annealing also aims to relieve
internal stress, to eliminate micro-segregation in cast material
for obtaining uniform grain structure, and to suitably modify
the microstructure when needed for a subsequent heat treat-
ment processes.
In case of annealing, cooling rate is extremely slow and
almost equilibrium microstructure is obtained. In contrast,
normalizing heat treatment employs air cooling which also
produces near-equilibrium microstructure but of a smaller grain

size compared to annealing. Thus for the same composition of
steel, normalizing produces stronger and tougher steel than
what can be obtained by annealing. In certain cases of high
hardenability steels, normalizing may lead to the formation of
nonequilibrium martensite phase and in that case, the steel is
said to have been air hardened.
Annealing serves identical purposes for both ferrous and
nonferrous metals and alloys. Air cooling may be done in
nonferrous metals and alloys to avoid the possibility of grain
coarsening due to slow cooling in annealing operation; how-
ever, air cooling of nonferrous materials is not termed nor-
malizing. Air cooling may be carried out in nonferrous alloys
only when there is no chance of precipitation of solute-rich
phase. If an alloy contains high amount of solute dissolved at
elevated temperature, and if the solubility of solute is appre-
ciably lower at room temperature, the alloy ought to be cooled
quite fast after annealing; this is because, the slow cooling say
in air may lead to precipitation at the grain boundaries of
matrix alloy; these grain boundary precipitates, enriched with
solute make the alloy vulnerable to premature intercrystalline
failure.
In case of annealing the cooling rate is extremely slow and
the rate of cooling may be same at all points across various
section of the component under heat treatment. This implies
that annealed material is structurally isotropic. This insures
better uniformity in mechanical properties in annealed com-
ponents. On the contrary, in normalizing the nonequilibrium
cooling rate is experienced and hence in this case, micro-
structure may be different at different locations of the
same component. This in turn results in nonuniformity in
mechanical properties across various sections of the same
component. Annealing employs a slower cooling rate; this
implies higher residence time of the components at higher
temperatures. Therefore the chances of grain coarsening is
rather high during annealing; however, chances of grain
coarsening is relatively less in normalizing due to its higher
cooling rate which insures that less time is available for grain
growth. Hardness of normalized components is higher than its
annealed counterpart; this aids in improving machinability for
very low carbon steel. However medium and high carbon
steels have better machinability in annealed conditions. Due
to discontinuous chip formation in normalized low carbon
steel, the surface finish after machining of normalized com-
ponent is better than when it is annealed. In a nutshell the
similarity and difference between annealing and normalizing
is summarized as:
Similarities
• Both the process are carried out in fully austenite state for
hypoeutectoid and eutectoid steel.
• Heating rate and soaking time for both the process are
identically selected.
• Microstructures consist of diffusional transformation pro-
duct of austenite but finer in normalized steel.
Differences
• For hypereutectoid steel complete austenitization is needed
in normalizing treatment whereas its annealing requires
holding within A1 – Acm but for which cementite network
may form around austenite grain boundary making the
steel very brittle.
Fundamentals of Heat Treating Metals and Alloys 29
• Annealing employs equilibrium cooling whereas cooling
due to normalizing is nonequilibrium.
• Normalizing temperature of hypoeutectoid and eutectoid
steel is 20 1C higher than the corresponding annealing
temperature; this insures structural fineness and composi-
tional uniformity in normalized steels.
Moreover, the microstructural distinction between nor-
malized and annealed plain carbon steels reveals the difference
between mechanical properties achievable in them.
It is understood that when hypo eutectoid steel of low
carbon content, say 0.20 wt.%, is annealed, its microstructure
consists of about 25% pearlite and 75% ferrite; as evident from
equilibrium diagram, the carbon content of ferrite is very
small. When the same steel is subjected to normalizing the
following microstructural changes take place.
1. The grain size of ferrite becomes smaller due to lower tem-
perature of transformation of austenite. This results in higher
magnitude of undercooling; hence less critical nucleus size is
envisaged. This leads to the formation of higher number of
effective nuclei and hence fine-grained ferrite is achieved in
its microstructure.
2. The carbon content of ferrite will be higher than that in the
annealed samples. This is due to the fact that a fast cooling
provides less time for diffusion of carbon. Hence equili-
brium is not attained. This retains more carbon in ferrite.
3. The amount of ferrite is less than that in the annealed
sample owing principally to less time available for the
formation of proeutectoid ferrite, which is a diffusional
process and is time dependent.
4. The amount of pearlite is higher than the annealed sample.
5. The colony size of pearlite is less than that in annealed
sample because a lower transformation temperature aids in
formation of higher number of pearlite nuclei.
6. The interlameller spacing of pearlite is smaller in normal-
ized steel sample than that in annealed sample. The
changes in the microstructures are shown in Figures 35(a)
and 35(b).
Each of the above changes in microstructure is brought about
by faster cooling in normalizing; this results in enhancement of
strength and toughness. Thus normalized component is always
stronger and tougher than the annealed component. The dif-
ference between the properties of annealed and normalized
steels are furnished in Table 1.
2.1.7 Hardening
Hardening is the heat treatment process by which the hardness
and hence the strength of a material is increased. Different
types of hardening processes are employed in different situa-
tions. There are cases of age hardening where the material is
heated to get a homogeneous single phase solid solution
which is cooled very fast from the high temperature and in the
process a supersaturated solid solution is obtained. The super
saturation is relieved by precipitation of solute-rich phase
mostly in certain sequences where coherent GP zone formation
is followed by a series of precipitate formation; the precipitates
in their initial stages of formation are either coherent or semi-
coherent with the matrix. Equilibrium incoherent precipitate is
30 Fundamentals of Heat Treating Metals and Alloys

Figure 35 (a) 1045 Steel annealed from 900 1C and (b) 1045 steel normalized from 900 1C. Courtesy of George Vander Voort, USA.

Table 1 Comparison of mechanical properties of annealed and

normalized steel

Carbon Yield Tensile Elongation Reduction

% point strength in area

MPa MPa % %

Normalized
0.01 179 310 45 71
0.20 310 441 35 60
0.40 351 586 27 43
0.60 413 751 19 28
0.80 482 923 13 18
1.00 689 1048 7 11
1.20 689 1054 3 6
1.40 661 1020 1 3
Figure 36 Diagram showing the hardening and tempering of
Annealed
euctectoid steel.
0.01 124 324 47 71
0.20 248 255 37 64
0.40 303 206 30 48 austenite leads to the formation of martensites as discussed
0.60 337 158 23 33 earlier. This martensite is very hard in steel. So hardening in steel
0.80 358 103 15 22 is a typical quench-hardening process. In this process the steel is
1.00 351 151 22 26 heated to austenitization temperature; the temperature up to
1.20 344 165 24 39 which the steel is to be heated is also decided by whether a
Source: Taken from Brick, R. M.; Gordon, R. B.; Phillips, A. The Structure and homogeneous austenite can be achieved in reasonable period of
Properties of Alloys, 3rd ed.; McGraw-Hill Book Company: New York, NY, 1965. holding or not. Normally, for hypoeutectoid steel the heating
temperature is 50 1C above A3 temperature and that for eutectoid
steel it is 50 1C above A1 temperature. From this high holding
formed only at later stages. The process is halted before that and temperature, the steel sample is quenched at a rapid rate. The rate
the coherent or semi-coherent metastable phases give rise to of cooling which is to be applied without formation of quench
precipitation hardening through dislocation particle interaction. crack is judiciously decided as it is dependent on the composi-
Many aluminum alloys harden by such age-hardening treat- tion of the steel. The severity of quench of individual cooling
ment. So hardening in such situation is a quench-aging process. medium is different and the steel under hardening is cooled
There are many single phase systems like austenitic stainless or from high temperature in water, oil, air, or molten salt baths. The
aluminum magnesium alloys which cannot be hardened by any process of hardening is schematically shown in Figure 36.
method other than cold working where dislocation density The hardening process thus consists of three steps: First step
created due to cold working without recrystallization hardens is the production of homogeneous austenite in hypoeutectoid
the material. This is a typical work hardening process. More and eutectoid steel while austenite plus undissolved carbide in
discussion on the heat treatment of nonferrous systems are case of hypereutectoid steel. The heating temperature may
narrated in later section. range from a very high magnitude for alloy steel B1200 1C to
However in case of steels, hardening is possible by quench- quite a low value like 750 1C for hypereutectoid steel. For
hardening means; in this case rapid cooling of homogeneous hypoeutectoid and eutectoid carbon steels it varies between
 Fundamentals of Heat Treating Metals and Alloys 31

780 and 880 1C. The heating is followed by holding for
predetermined time for dissolution of carbide and production
of homogeneous austenite; in case of hypereutectoid steel,
however, undissolved carbide is deliberately kept in the
microstructures for reasons stated earlier. Finally, the work-
piece is cooled at a cooling rate that produces martensitic
structure with minimum residual stress. The heat treatment is
required to be carried out in a protective atmosphere so that
chemical degradation due to decarburization can be avoided
as far as practicable. Cooling is performed in different media
viz. water, saline water, hardening oils, polymers, salt bath,
and nitrogen or argon gas. Individual cooling medium has
its own characteristic advantages and disadvantages; however,
salt bath quenching reduces chemical degradation as well as
minimizes the chance of warpage due to fact that the objects
immersed in liquid bath experiences Pascal pressure which is
same along all directions. Moreover the inert gas quenching like
nitrogen or argon minimizes oxidation and decarburization.
The hardened steel is extremely brittle and cannot be put to use
unless it is toughened suitably.
Thus the salient features of hardening of steels are:
1. Selection of proper quenching medium should be made so
that thermal stresses can be kept to minimum.
2. Alloy steels having high hardenability and low CCR should
be subjected to air cooling to avoid warpage or cracking.
3. High carbon steels have slightly higher CCR and has to be
hardened by oil quenching.
4. Medium carbon steels with relatively high CCR may require
judicious selection of quenching medium; many a time oil
quenching or polymer quenching is preferred to avoid heat
treatment defects.
0.7 wt.%C lowers the Mf temperature to below room tem-
perature and so, higher carbon steels quenched into water
often contain appreciable amounts of retained austenite in the
microstructure.
2.1.7.1.2 Austenite decomposition to produce pearlite,
bainite, and martensite structures
Steels must have adequate hardenability to avoid soft pearlitic
transformation for producing fully martensitic structure
throughout the section. For this purpose, the alloying elements
having good ability to shift TTT or CCT diagrams toward
right are often added in steels, meant for quench hardening.
The microstructure of hardened steel containing martensite
and some retained austenite is shown in Figure 38. During
martensitic transformation some austenite remains untrans-
formed. The amount of retained austenite depends upon the
chemical composition, cooling rate, and mechanical treatment.
Stabilization of austenite in quenched steel is discussed in
subsequent section.
Another way of forming martensite is by fast cooling in the
softer region, i.e., the pearlitic and the bainitic region and then

2.1.7.1 Factors Influencing Hardening Process

The hardening process of steel is appreciably influenced by the
following:

2.1.7.1.1 Adequate carbon content to produce hardening

As stated earlier the alloying elements with the exception of Co
and Al depress the martensite reaction temperatures and
carbon exerts the strongest effect to lower both Ms and Mf
temperatures. As shown in Figure 37, carbon in excess of Figure 38 Microstructure showing martensite.

Figure 37 Carbon content vs. martensite start (Ms) and martensite finish (Mf) temperatures in unalloyed steels.
32 Fundamentals of Heat Treating Metals and Alloys
a comparatively slow cooling rate can be employed to produce
martensite.
2.1.7.1.3 Temperature of heating, rate of heating, and
the time of holding
2.1.7.1.3.1 Temperature
Proper selection of temperature is essential for successful
hardening operation. For hypereutectoid steels the heating is
done below the Acm line, has the unique benefit of retention of
undissolved cementite in the microstructure which apart from
inhibiting grain growth provides high wear resistance to the
heat-treated parts.
2.1.7.1.3.2 Heating rate and soaking time
The heating rate is so selected that there should not be any
decarburization or grain growth. For this the heating is done in
steps. For an example heating to 800 1C and soaking for some
time to homogenize the structure and then heating the material
rapidly to the peak temperature; this process necessitates a low
soaking period at the high austenitizing temperature. This leads
to complete homogenization of austenite without appreciable
grain growth. The soaking period and heating rate depend on
the size and shape of the part being heat treated.
In order to avoid defects due to hardening of steels the
following guidelines are useful:
• The properties required in the heat-treated part are
obtained without the parts being distorted beyond accep-
table limits.
• The ideal design for a heat treatable part should be such as to
attain the same temperature at its every point with minimal
chances of abrupt change in thermal stresses. This necessi-
tates the avoidance of abrupt change in the section sizes.
• Long thin parts like connecting rods should be as symme-
trical as possible to reduce stresses.
• The holes in a part should be kept centered such that metallic
mass around these holes are nearly same; this insures
balanced mass around and hence less chance of cracking.
• The internal corners in a part should be provided sufficient
fillets and regions prone to lead to stress concentration
should be avoided.
2.1.8 Heat Treatment Fundamentals of Nonferrous
Alloys
A variety of heat treatment processes are practiced to control
the structure and properties of nonferrous alloys. Most of these
processes have their characteristics features that are common
to the alloys undergoing such treatment; the general principles
of individual processes adopted for heat treating nonferrous
alloys are briefly reviewed in this section.
2.1.8.1 Age-Hardening Treatment
A number of nonferrous alloys exhibit sloping solvus in their
phase diagrams. This makes the concerned alloys amenable to
age hardening; age hardening is the heat treatment that envi-
sages formation of a single phase by heating the alloy to a high
temperature which insures complete dissolution of second
phase particles. Upon being quenched to room temperature
the solid becomes supersaturated with respect to solute
concentration. Supersaturation is a state of thermodynamic
instability and hence the system becomes prone to be relieved
of supersaturation through what is called precipitation.
However a homogenous solid solution becomes hetero-
geneous if it is cooled rapidly from a high temperature to the
room temperature. All quenched alloys contain vacancies in
excess of equilibrium number. The presence of excess vacan-
cies entices the solute atoms for small-scale migration. This has
the implication that perceptible chemical heterogeneity is
created in a local scale. If the composition of the alloy lies
within its spinodal points, the alloy decomposes sponta-
neously without regard to chemical potential barrier. This fine
scale solute-rich region created within the system is known
zone, more customarily Guinier–Preston (GP) zones. The
aging sequence in age-hardening alloys can be obtained in text
books on light alloys and in ASM Metal Hand Book Volume 4.14
Quite often the heat treatment cycle is so designed as to
maximize the density of GP zones by a low temperature aging
treatment just after solutionizing followed by quenching.
Following this, a second step of aging treatment is carried out
at a high temperature. The preexisting GP zones dissolve
(above GP solvus) and give way to the formation of a series
intermediate precipitates which are mostly coherent or semi-
coherent with the matrix. The first step of aging at low tem-
perature (below GP solvus) is called natural aging and the
aging at temperatures above GP solvus is known as artificial
aging. The overall aging process is referred to as duplex aging;
duplex aging has the advantage of achieving precipitates of
varying sizes which when suitably designed may lead to the
formation of duplex precipitate structure which is extremely
beneficial in simultaneous improvement of both yield strength
and fracture toughness of the heat-treated alloy. It is to be
noted that during artificial aging a series of metastable phases
are formed and the formation of equilibrium precipitate may
not even occurs in many cases.
A few nonferrous alloys exhibit precipitation hardening
behavior due to the formation of fine coherent precipitates of
the intermetallics during aging. In this way it resembles aging
in maraging steel where coherent precipitates of types Ni3Mo,
Ni3Al are formed. Cu–7.5Ni–1.5Si–1.2Cr is one such alloy
in which the quenched-aged microstructure exhibits nan-
ometer scale precipitates of b-Ni3Si and δ-Ni2Si.15 However it
may be noted that when transition metals like chromium is
alloyed with a full metal like copper, the as solidified alloys are
normally heterogeneous with preferential segregation of chro-
mium.16 In conventionally cast alloys the microstructure exhib-
its large chromium rich phases. The segregation of chromium in
as cast condition is ascribed to high Chromium–Chromium
coordination in the liquid state due to differential mobility of
the solute and solvent atoms at the conventional temperature of
molten alloy.16 This type of micro-segregation is the main rea-
son why these alloys containing appreciable amount of chro-
mium is solution treated for as long a time as 10 h at high
temperatures like 970 1C. In this connection special mention
must be made of nickel-based superalloys like Inconel, Hastalloy,
Nimonic, Udimet, and Waspalloy which are subjected to
quench and aging heat treatment, where diffusion of solute
atoms plays a vital role. These superalloys need to possess high
creep resistance and hence its microstructure should be such
 Fundamentals of Heat Treating Metals and Alloys 33

that it is not only very hard at room temperature but also can
retain its hardness at high temperature. Hard refractory com-
pounds embedded in strong and tough matrix enable the
material to attain good high temperature strength. Thus all the
superalloys are dispersion-strengthened and or precipitation-
hardened alloy. Since these superalloys contains refractory
elements like Mo, W, Cr along with some carbon and alloying
elements the hardened phase are generally intermetallic com-
pounds and carbides of refractory material.17–19 The diffusion
of these high melting refractory metals are very sluggish at the
average tempering temperature of 600–700 1C unless it is aged
for a prolonged period of time. A long holding time at the
aging temperature makes it possible to precipitate all the solute
atoms in the form of refractory intermetallics or carbides.
A sloping solvus in equilibrium diagram of a system is a
necessary but not sufficient condition for any alloy system to
be age hardenable. Example may be cited of Al–Mg system
which possesses a sloping solvus in its equilibrium diagram, Figure 39 Age-hardening curves of Al–6Mg alloy containing 0.2, 0.4,
but does not exhibit age hardening. It is postulated that GP 0.6 wt.%Sc. Dotted curve is for the base alloy.19
zones are not formed in Al–6Mg alloy due to GP solvus lying
below room temperature and that the alloy in solidified
condition contains coarse Mg2Al3-type intermetallic. However
it is found that trace additions of different elements in
several nonferrous alloys impact their aging response quite
significantly.20–23 Different trace element additions exert dif-
ferent types of effects. Some trace additions in some systems
stimulate formation of GP zones; for example, addition of
silver in Al–Mg alloy leads to formation of GP zones in the
alloy; it is not certain if these zones are magnesium atom
dominated zones or are of the same type of zones as is known
to form in binary Al–Ag alloys. Al–Ag alloy forms spherical GP
zones; hence the possibility that stimulation in GP zone for-
mation in Al–Mg alloy is due to silver rich GP zone formation
cannot be over ruled. On the contrary minor addition of
scandium leads to very prominent age-hardening effect in
Al–6Mg alloy.24,25 Scandium in aluminum forms Al3Sc pre-
cipitates and strengthens the alloy. Recent investigation through Figure 40 Variation of hardness with aging temperature for cold-
position annihilation and coincidence Doppler boundary worked Al–Cr (Zr) with trace rare earth addition.23
spectroscopy has confirmed that GP zones are not formed in
Al–Mg (Sc) alloy even though it shows excellent age-hardening become responsive to age hardening due to trace addition are
behavior.26,27 It implies that for precipitation hardening to take those for which cold-working accentuates age hardening. The
place, the formation of GP zone is not mandatory (Figure 39). aging curves in Figure 40 demonstrate that cold-worked Al–Cr
Moreover, the observation that scandium treated Al–Mg alloy is highly age hardenable even though it is otherwise a
alloys age harden but do not form GP zones while silver added quench sensitive alloy. It is described earlier28 that the first
Al–Mg alloy records GP zone formation, raises a doubt on the peak is due to the formation of CrAl7 phase which is the chief
common belief that binary Al–Mg alloy does not exhibit age hardening phase. At high temperature the CrAl7 phase dis-
hardening because its GP solvus lies below room temperature. solves and the new precipitate of Cr2Al11 appears. The volume
There is another class of alloys which have the sloping solvus fraction of this precipitate is less due to paucity of flux
in their phase diagrams but are nonresponsive to age hard- of chromium atoms against the need to form higher alumi-
ening due to quench sensitiveness. The ideal example of this nizes, Cr2Al11. Also recrystallization takes place partially due to
class is aluminum – transition metal alloys viz. Al–Cr alloy high temperature aging and so, the number of dislocations
which is highly quench sensitive. These alloys are highly prone available as nucleation sites for Cr2Al11 becomes quite low. As
to form coarse intermetallics in microstructure and do not a result the extent of age hardening is less after geeing at
exhibit age hardening in general.28 It is surmised that density 350 1C.
difference between solvent and solute leads to prevalence of Quench-sensitive alloy contains coarse insoluble in its
biased neighboring of like atoms. Treating these alloys with quenched state (Figure 41). The incoherent insoluble – matrix
rare earth elements makes the liquid alloy more homogenous interface acts as the sink for vacancy annihilation. As a result,
and as a result homogenous supersaturated solid solution is availability of vacancy in its quenched structure is limited. So
likely to form after solutionizing treatment followed by rapid solute diffusion becomes restricted; neither GP zone formation
quenching. It is further demonstrated that the alloys which nor formation of intermetallic precipitate is encouraged.
34 Fundamentals of Heat Treating Metals and Alloys
Figure 41 SEM micrograph of Al–6Mg–0.6Sc alloy.19
It is known that precipitation phenomenon involves long-
range transport of atoms. Cold-worked alloy provides dis-
locations as the nucleation sites for precipitates and punched
out vacancies from dislocations also make solute diffusion
easy thereby aiding in precipitate formation in many quench
sensitive systems.29 However dislocation-induced precipita-
tion is not generic of age-hardening alloy systems. Vacancy
solute atom complex formation and its easy transportation
to nucleation sites is the chief controlling factor of pre-
cipitation of Al3Sc in Al–6Mg (Sc) alloy. This alloy does show
any benefit in aging response after cold working following
quenching.
2.1.8.2 Annealing of Nonferrous Alloys
The other common heat treatment processes applied to non-
ferrous alloys are homogenizing, conventional annealing and
stress reliving. For example, many copper alloys are single
phase solid solution and therefore can be heat treated only by
the above mentioned processes.
In general the alloy castings are subjected to homogeniza-
tion annealing heat treatment by heating the cast alloys to
a high temperature where rapid diffusion of substitutional
solute atoms is possible. The selected temperature should not
be so high as to promote unwarranted grain growth. The
alloy like Cu–Sn which shows a wide gap between solidus and
liquidus temperature is prone to coring or micro-segregation.
These alloys are normally homogenized at high temperature.
In order to relieve internal stresses and to restore the ori-
ginal structure and properties that are affected during cold
working, the nonferrous alloys are subjected to recrystalliza-
tion annealing as usual. High solute alloy like a brass are
recrystallization annealed appreciably above the recrystalliza-
tion temperature to assist diffusion of solute atoms. Stress
relieving annealing treatment of nonferrous alloys is carried
out as usual to relieve internal residual stresses those are
introduced during the welding, brazing, casting, machining, or
Figure 42 Self accommodating thermoelastic martensite in Cu–Zn–Al
alloy.27
the fabrication processes. Stress relieving treatment may also
be carried out for the purpose of securing partial recovery in
cold drawn alloys. When extremely deformed alloys are sub-
jected to low temperature annealing treatment, point defects
are eliminated in particular and the excess lattice defects in
general. Such stress equalizing treatment as it is called, is
commonly practiced in the case of cold-worked Monel alloys
by annealing it at 300 1C. Sometimes propensity to stress
corrosion cracking as in the season cracking of a brass
(415 wt.%Zn) is minimized by annealing the cold-worked
material below recrystallization temperature. This retains
strain-hardening effect with some loss in hardness. In this
condition, the strain-hardened components do not get sof-
tened. However some hardness drop inevitably accompanies
this process.
2.1.8.3 Martesite Formation in Nonferrous Alloys
Although many nonferrous alloys including a–b brass are
strengthened by precipitation hardening, copper zinc alloys
are not always meant for precipitation hardening. Ternary
addition of aluminum in Cu–Zn alloys produces thermoelastic
martensite,30–33 capable of exhibiting shape memory effect
(Figure 42). If the alloy is deformed in martensitic state to
assume a different shape, the high temperature shape can be
regained by the original article upon being heated beyond a
certain temperature, called recovery temperature.
When Cu–xZn–yAl or Cu–xAl–yNi is quenched from high
temperature in b-phase field, martensites are formed. These
martensites are very soft and are amenable to shape change
with the application of small force.
The volume change ‘ΔV’ accompanying martensitic trans-
formation is quite small and the lattice invariant deformation
mode is either twin or stacking faults (Figure 43).
The reversible internal faults enable the reverse transfor-
mation of martensite to parent phase to take the same path
as that of the forward transformation (b-M). The inherent
reversibility characteristics of martensitic transformation in
Cu–Zn–Al and Cu–Al–Ni alloy are envisaged due to low
thermal hysteresis.34–37
The repetitive use of these shape memory alloys exhibit
degradation in shape memory behavior due to cumulative

Figure 43 Internal twins in Cu–Zn–Al shape memory alloy with trace
Zr add.26
Figure 44 Microstructure of Cu–Zn–Al (Ti) alloy showing fine
precipitates after repeated shape memory cycling.32
aging effect. Repetitive shape recovery cycling leads to pre-
cipitation of inter metallic compounds on to the twin
boundaries and make them immobile. Thus de-twinning
during reverse transformation is inhibited thereby, resulting
in a loss of shape memory effect.38,39 The effect of aging pre-
cipitates on the SME is elaborately studied elsewhere.40,41
Excepting a few cases, formation of precipitates due to aging,
in general degrade shape memory behavior, with concurrent
rise in hardness (Figure 44).
In view of apparent differences in heat treatment of some
technologically important nonferrous systems, a brief review
of fundamentals underlying principles of heat treating a few
such systems is done in the following paragraphs.
2.1.8.3.1 Heat-treat principles of nonferrous alloys
exhibiting polymorphic transition
Unlike aluminum, copper or nickel, titanium undergoes
polymorphic transition at 882.5 1C; high temperature b-phase
is BCC and this phase undergoes phase transition through
formation of hcp a below the transition temperature. This
Fundamentals of Heat Treating Metals and Alloys 35
makes it possible to produce a, b, or a þ b alloy of titanium.
Therefore evolution of different kinds of phases due to various
types phase transformations accompanying heat treatment of
titanium alloys is noticed. This enables to achieve specified set
of properties in titanium alloys suiting the needs of target
applications.42–45 Being low temperature single phase system,
a-alloys are generally cold worked and annealed to achieve
grain refinement while it is in fully a-phase state. However if
fully ‘a’ alloy is quenched from b-phase field, a0 martensite may
form, with very little change in properties. Similar to many
ferrous and nonferrous systems a relatively slower cooling from
b-phase field (say air cooling) produces Widmanstatten a with a
consequent deterioration in fatigue strength. If a-alloy of
approximate composition, Ti–11Sn–2.25Al–5Zr–1Mo–0.2Si is
equilibrated at temperature within a þ b-phase field, evolution
of microstructure takes place in the same way as in duplex
ferrite–martensite steel. When the alloy is annealed at 900 1C
within a þ b-phase field and then cooled fast, the b-phase
transforms to a0 martensite; on the contrary a relatively slow
cooling like air cooling produces fine equiaxed primary a and
Widmanstatten a obtained from b.
In a/b-alloys several heat treatment processes may be
adopted. The most common a/b-alloy is Ti–6Al–4V alloy.
In such a/b-alloy 4–6% b-stabilizing (V) elements are added to
retain some b even after quenching from b- or a þ b-phase.46–48
Annealing of the alloy can be done from b-phase field as well as
from a þ b-phase field. When it is annealed at b-phase and then
cooled to room temperature, Widmanstatten ‘a’ is formed in a
b-matrix or b may partially or wholly transform to a0 martensite
depending upon the cooling rate. When annealed from
a þ b-phase field the microstructure consists of equiaxed a and
transformed b. Transformed b may be Widmanstatten ‘a’ or a0 .
The strength of annealed alloy increases with increasing alloy
content.
b-quenching: the a/b-alloy may be betatised at elevated
temperature, where single phase b is present. The b-phase is then
quenched. In case of dilute alloy, b may convert to a0 (hcp)
martensite; a0 martensite may finally convert to lath martensite
a00 or twinned martensite a000 . However in a concentrated alloy
‘b’ phase is retained as metastable ‘b’ which is then subjected
to aging heat treatment as is done in a typical precipitation-
hardened stainless steel. In dilute alloys b-phase may directly
convert to laths of orthorhombic a0 to a00 martensite and face-
centered orthorhombic a000 martensite. The transition from a0
martensite to a00 martensite takes place with increasing solute
content. Thus,
b-a00 with retained b
i.e., b-b(lean) þ b(rich)-a00 þ b(rich)
When the alloy is very rich in b-stabilizing elements, a fast
quenching from b-phase field may give rise to metastable b.
Aging of metastable b decomposes differently at different
temperature regime.
In a medium alloy aged within 100–500 1C b(metastable)-
b þ o-b þ a
In concentrated alloy b metastable-b þ b1-b þ a
o-phase leads to severe embrittlement of the alloys. For-
mation of o-phase takes place through displacive mode of
transformation; o particles are cuboidal and maintain specific
orientation relationship with b-phase.
36 Fundamentals of Heat Treating Metals and Alloys
Within the group of b-alloys, a relatively lean solute con-
tent produces metastable ‘b’ upon fast cooling; whereas above
a critical value of the concentration of b-stabilizers stable ‘b’
remains present in the microstructure. The alloys are cold
formed and aged to secure high strength.
2.1.8.3.2 Application of heat treatment principles in
Mg-alloys
In view of recent interest in commercial use of magnesium
alloys due to its advantage of low specific weight, more ela-
borate discussion is made to know about the heat treatment of
Mg-alloys. Cast magnesium alloys are quite often subjected to
solutionizing followed by aging. The solutionizing is carried
out to attain a single phase from where it is cooled fast to form
supersaturated solid solution. The cast alloys show micro-
segregation and quite often cast magnesium alloys contain
intermetallic precipitates of the form AB, AB2 (laves phase),
or CaF2 (BCC) in the microstructures. Mg–(8–10)Al–0.5Zn–
0.3Mn alloys are subjected to natural aging after solutionizing
or first solutionizing and then artificial aging to effect intra
granular precipitation of magnesium aluminides. On the
contrary Mg–(4–6)Zn–0.7Zr (RE) is directly subjected to T5
tempering, that is artificial aging49; this leads to the formation
of Mg2Zn type precipitates. In general, magnesium alloys form
three different types of precipitates. These precipitates form at
grain boundaries if the alloys are cooled at moderate cooling
rate as in sand casting. In order to improve strength and cor-
rosion behavior of magnesium alloys, it is required that
these intergranular precipitates are dissolved during solutio-
nizing heat treatment. Subsequent aging to form intragranular
precipitates of intermetallic phases gives rise to significant
improvement in mechanical and mechano-chemical proper-
ties. A large number of magnesium alloys are precipitation
hardenable; the precipitate phases forming in different mag-
nesium alloys with their precipitation sequences in furnished
in the Table 2.
In observance of the aging sequence in important magne-
sium alloys, it may be understood that most of these alloys are
subjected to age-hardening heat treatment and in most of the
cases combined T4 and T6 is recommended so that a duplex
precipitates structure may result in the microstructure. In
Mg–RE system, maximum strengthening is obtained due to the
formation of b00 phase which exhibits DO19 ordering. But aging
at higher temperature till 250 1C leads to loss of coherency and
the semi-coherent b0 -phase with hcp structure forms, mainly on
to the existing dislocation. This drastically reduces creep resis-
tance. Solution treatment temperature for this alloy is judi-
ciously selected and is normally around 420–450 1C for most of
the commercially important alloys because it can avoid both
grain coarsening and chemical degradation.
Table 2 Heat treatment of Mg-alloys
System Precipitates process
Mg–Al SSSS-BCC equilibrium precipitate Mg17Al12 (b-phase) with (011)b//(0002)Mg and faceted with lath morphology
Mg–Zn–(Cu) SSSS-GP zone (coherent, disk)-MgZn2 (rods, coherent)-MgZn2 (disk, semi-coherent)-Mg2Zn3 (incoherent)
Mg–RE SSSS-GP zone (coherent, disk )-b00 MgxNd (x41) (Do19 ordered)-b0 Mg3Nd (semi-coherent)-Mg12Nd (incoherent)
Mg–Y–Nd SSSS-b00 , Mg3Nd, GP zone rods coherent Do19-b0 Mg12NdY globular þ b1 (plates) Mg3(NdY) FCC-incoherent Mg14Nd2Y FCC
Mg–Th SSSS-b00 , Mg3Th coherent (disk) Do19-b0 1 hcp, b0 2 FCC semi-coherent-b Mg23Th6 FCC incoherent
2.1.9 Quenching and Quenching Medium
In case of age hardening the supersaturation is relieved by fine-
scale precipitation through a definite sequence. However the
alloy becomes hardest at particular time and temperature of
aging. As stated earlier in case of the Fe–Fe3C system the
supersaturated solid solution is the strongest phase but is
extremely brittle. Heating it to some elevated temperature
below A1 temperature decomposes the supersaturated solid
solution leading to ductilization of the alloy. As in contrast
with the previously stated age-hardening phenomena, the
decomposition of the alloy leads to toughening of the alloy. As
described earlier hardening of steel is conditioned by a CCR as
defined earlier. It is to be further noted that whether the
cooling rate offered by a particular cooling medium is able to
give rise to the formation of 100% martensite throughout the
section or not depends upon the section size of the stock being
cooled.
Figure 45(a) shows the effect of various cooling medium on
a round-eutectoid steel bar. It is apparent that water having
more severity of quench can bypass the nose of CCT diagram
up to a greater depth then oil and air of lower severity of
quench. Hence to gain idea about the inherent ability of a
material to avoid soft pearlitic transformation, it is required to
alleviate with the influence of severity of quench while deter-
mining the achievable depth of hardening. This is done by
imagining an ideal quenching medium with infinite severity of
quench.
By definition the ideal quenching medium will take away
the heat from the surface at the same rate as it flows to the
surface from inside the bar which is being quenched. The
cooling efficiency of the usual quenching media such as water,
oil, brine, etc., relates with that of the ideal quenching med-
ium. If round bars of varying diameters are quenched in a
medium from an austenitizing temperature, there will be a
particular diameter of which 50% martensite and 50% pearlite
will be formed at the center. Conventionally this diameter is
called critical diameter and is usually taken as the measure of
hardenability. It must be noted that reckoning hardenability of
steel on the basis of existence of 50% martensite and 50%
pearlite in the structure is not mandatory. Depending upon the
design requirement of steel, on the basis of strength and
toughness parameter, it is possible to describe hardenability as
the depth up to which 100% martensite is formed; however
the classical definition of hardenability, as the depth up to
which 50% martensite and 50% pearlite is formed, owes its
origin to the easy identification of a structure with 50% mar-
tensite and 50% pearlite. The fracture of such a material will
show a transition from ductile to brittle type and a plot of
hardness versus the depth from the center shows a point of

Figure 45 (a) Effect of cooling medium on microstructure evolution in eutectoid steel and (b) different stages in quenching.
inflexion denoting the change in curvature from positive to
negative. As stated earlier hardenability is an inherent material
property measuring the depth up to which the material can be
hardened with a predefined percentage of martensite in the
microstructure. The critical diameter of steel for a definite
quenching medium of a particular H-value can be made co-
related to the ideal critical diameter quenched in an ideal
quenching medium (the details of hardenability of steel and
methods for its determination can be obtained from physical
metallurgy books of steel).
Fundamentals of Heat Treating Metals and Alloys 37
Once hardenability is defined as the depth to which a
definite percentage of martensite can be formed, it becomes
obvious that all the factors which delay the diffusional
decomposition of austenite will improve hardenability. If
austenite grain size is large, the nucleation sites for pearlite
formation will decrease and hence CCT diagram will shift
more toward right, thereby increasing the hardenability.
Likewise all alloying elements except cobalt shift the CCT
diagram to right and improve hardenability. However indivi-
dual alloying elements has characteristic influence on degree
38 Fundamentals of Heat Treating Metals and Alloys
of shift of CCT diagram and so a multiplying factor is assigned
for each alloying elements to describe the quantitative effect of
individual element in increasing the hardenability of steel.
From the forgoing discussion it is clear that the microstructure
in continuously cooled steel depends on the cooling media
employed for the concerned material.
During the cooling operation, a hot object is immersed in a
quenching medium – this is a complex process consisting of
two major stages:
• Stage 1: vapor blanket stage
The temperature at the surface of the stock is initially
very high and so the cooling medium gets vaporized and
forms a thin layer of vapor around the immersed part.
Under such circumstances the mode of heat transfer is
radiation through vapor blanket which acts as insulating
layer. This insulating layer puts a restraint to rapid flow of
heat and hence cooling of the object. Thickness of vapor
blanket around the object is determined by the quenching
efficiency of the medium. The duration up to which this
vapor blanket stage prevails around the object is different
for different quenching medium. It further depends upon
the ratio of the weight of object being heat treated and that
of the quenching medium being used. Further the specific
surface area and the distance between any two object put
inside the quenching media also influence the vapor
blanket stage. Figure 45(b) shows the formation of vapor
blanket around the bar.
• Stage 2: the boiling stage
In the course of cooling, the temperature at the surface of
the stock becomes low enough to reduce the rate of
radiation, resulting in the loss of vapor blanket stability.
The disappearance of vapor blanket at any region around
the object will immediately supply liquid to come in con-
tact with the hot surface of the object. The liquid start
boiling and the bubbles emanated thereof create turbu-
lence near to the metal surface; this enhances the rate of
heat extraction. Since the quenching media have high latent
heat of vaporization, the boiling stage experiences the
Figure 46 Cooling rate vs. temperature for various quenching media 1-H2O; 2-H2O þ 10%NaCl; 3-H2O þ 50%NaCl.
fastest cooling of the object. After the lapse of some more
time with continued heat extraction from the surface of the
stock, the temperature at the surface goes down below the
boiling temperature of the quenching media. Boiling stops
and the mode of heat transfer at this stage becomes only
convection. Thus the rate of cooling continues to reduce
with falling temperature of the quenching medium. It is
important to note that the progressive lowering of tem-
perature of the heat-treated stock and hence that of the
liquid surrounding the object leads to increase in the
viscosity of cooling medium; this reduces the rate of
convection and hence the cooling rate. These stages of
quenching are shown in Figure 45(b).
Because of the fact that the thermal property of the liquid is
a function of temperature, rate of cooling by any quenching
medium would automatically depend upon its temperature
dependent thermal properties. Qualitative information on
commonly used commercial quenching media is provided in
Figure 46.
From Figure 46 it appears that the major feature of water
quenching is defined by the extended vapor blanket stage over
a wide range of temperature. Its implication is that the cooling
rate at the initial stage where diffusional decomposition of
austenite is supposed to takes place is rather slow. Thus the
formation of diffusional decomposition product takes place
with nonuniformity. The cooling capacity is of water at high
temperature is sharply reduced and with increase of tempera-
ture of water the vapor blanket stage extended. This gives rise
to a very nonuniform cooling rate at high temperature region,
while quenching in water. The curve further shows that water
offers its maximum cooling rate at a temperature between
250 and 300 1C which belongs to the temperature range of
martensite transformation in many commercially important
steels. The high cooling rates within Ms–Mf range is a great
concern for distortion, warpage, and even quench cracks. It
may be noted that increasing the temperature of water cannot
solve the problem by the way of reducing the rate of cooling
during martensite transformation. On the contrary increased

water temperature may increase the cooling rate at certain
temperature. That is why quench cracks are frequently
observed in case of quenching of steel in hot water. In contrast
a brine solution containing 10% NaCl in water appreciably
changes the situation; the cooling capacity is increased to a
high value even with exclusion of first stage of cooling, i.e., the
vapor blanket stage. Moreover the cooling by brine solution is
found to be uniform, although it is expected to decrease with
decrease in temperature. Because of high cooling rate at high
temperature where a vapor blanket is expected to form, the
temperature of the metal surface decreases fast; this causes the
vapor blanket to become unstable and gets destroyed right at
the initial stage of cooling. Moreover, the NaCl salt spalling
out may accentuate the destruction of vapor blankets. The
brine solution is known to be relatively less responsive to
heating. Moreover the cooling rate within the Ms–Mf range can
be brought down to low value by the use of concentrated brine
solution, 40% NaOH in water is a very good quenching
medium which greatly minimizes the warpage and ensure a
clean surface after heat treatment. Unlike brine solution,
NaOH in water is a rapidly degradable quenching medium.
This absorbs CO2 from air and loses its properties within a day
or so. The low cooling rate between Ms and Mf range is an
important consideration in the evaluation of efficacy of
quenching medium. A fast cooling down to Mf temperature
induces high thermal stress, also called macro-stress. Micro-
stress due to martensite transformation is quite severe and is to
be inevitably developed during martensite formation. There-
fore a slow cooling rate within the Ms–Mf temperature range is
always advantageous in terms of reduction in cumulative
stresses developed in the quenched stock. Examples may be
cited of a solution of 5% KMnO4 with 3% glycerin in water
which decreases the cooling rate in the martensite transfor-
mation region to a significant extent. On the average this is
around 50 1C s
1 as against 600 1C with pure water and
100 1C in water with 50% NaOH.
The other important quenching medium is considered to
be mineral oil which has a number of advantages over water as
a quenching medium.
• Boiling point of quenching oil is around 250 1C and this
mineral oil provides a very low cooling rate within the
Ms–Mf range. At a temperature around 200 1C the cooling
rate provided by the oil is at least 25% less than that pro-
vided by water. As evident from Figure 46, the rate of
cooling provided by the oil remains more or less unchan-
ged from 150 1C to room temperature.
• However the oil quenching provides a low cooling rate in
the intermediate range of transformation temperature,
where austenite decomposes in to pearlite. Thus the effec-
tive hardenability significantly decreases due to oil
quenching.
• Most of the commercial quenching oil is highly inflam-
mable and its flash point is around 128 1C. However oil
with higher flash point around 170 1C is also available in
the market.
• The cooling rate provided by the oil is rather small at low
temperature. Oil preheated to 80 1C provides good fluidity
of oil, so that effective convection occurs. Being well below
the flash point of oil at 80 1C does not set to fire and
Fundamentals of Heat Treating Metals and Alloys 39
continuously provide a slow cooling rate within the Ms–Mf
temperature range and thereby reduces the chance of
warpages.
• In the recent time, the new generation steels have been
developed which are hardenable by cooling in the still air.
The air hardening steels are particularly suitable for mini-
mizing the distortion and warpage as the thermal stress
induced during quenching is minimum. Also air–water
mixtures at a pressure of 2–3 atmospheric pressure is
sometimes used for hardening heavy articles made up of
alloy steel and are prone to crack on quenching. On
examination of the values of severity of quench for air and
oil it would appear that air with low moisture contains is
able to provide a cooling rate which is nearly same as oil.
• It is possible to increase the efficiency of hardening alloy
steels for water quenching is generally prohibitive due to
proneness of quench cracking. A leaner alloy steels, which
otherwise cannot avoid the nose of CCT diagram for the
entire section, may first be subjected to more severe
quenching in water down to the level of 450–400 1C
(assuming nose to exist between 500 and 550 1C), and
then quickly withdrawing the same from water and
quenching it in oil which is quite efficient a quenchant
within Ms–Mf range. By this technique it is possible to
make use of lower alloying element content in steel yet
achieving the same strength and toughness properties.
• Apart from what are stated above, proper immersion of
the articles in to quenching medium is very important to
avoid warpage and cracking due to hardening. The general
recommendation in this regard is that longer articles
should be immersed with its main axis perpendicular to the
surface of quenching bars. Flats and sheets are immersed
on their edges. For a better heat transfer it is advisable to
create a relative movement between the article and cooling
liquid. The lighter articles should normally be moved along
the direction in which they are inserted in to the quenching
medium. But the heavy stocks may be held stationary and
creating agitation in the quenching bath.
2.1.10 Tempering
As stated earlier the hardened steels with full martensite in
microstructure cannot be employed for useful purposes
because martensite is extremely brittle; martensite formed by
quenching produces high internal stresses in the hardened
steel. The hardened steel need be heated to higher temperature
to reduce its brittleness; this process is called ‘Tempering.’
Tempering is generally carried out by heating the hardened
steel to temperatures below A1; it is held there for some pre-
selected period of time and then followed by cooling to room
temperature.
The selection of tempering temperature depends upon the
composition of the steel and the final properties desired after
tempering; this however depends upon the exact micro-
structure and the hardness of the component at various points
across its section. High carbon and high alloy steels are nor-
mally tempered at as high temperature range as 550–650 1C
(Figure 47). In order to achieve good combination of strength
and ductility commensurate with the demands of service
40 Fundamentals of Heat Treating Metals and Alloys
Figure 47 Tempered high carbon plate martensite in 0.9C–0.4Mn
steel water quenched from 900 1C and tempered at 538 1C. Courtesy
of George Vander Voort, USA.
conditions, proper selection of process parameters for tem-
pering operation is necessary. The concerned process para-
meters are:
• tempering temperature,
• time to spend at tempering temperature, and
• cooling rate from the tempering temperature.
In some alloy steels, the hardness increases during tem-
pering at high tempering temperature. This is known as sec-
ondary hardening. It occurs due to the formation of transition
phases which are coherent with the matrix.
Secondary hardening is sometimes termed as fifth stage of
tempering as it takes place normally beyond the tempering
temperature for globularization of cementite in plain carbon
steels. Some workers have termed this process of globulariza-
tion during tempering as the fourth stage of tempering and so
secondary hardening in alloy steels are sometimes referred as
fifth stage of tempering. In case of chromium bearing steel the
first formed carbide is cementite at low tempering temperature
when the diffusion of chromium atoms are very slow. However
with increasing tempering temperature the diffusivity of chro-
mium is enhanced and cementite gives way to the formation of
alloy carbides. The equilibrium carbide phase forms through
the formation of a series of transitional carbide phases. In
chromium steel, the sequence is: Fe3C-Cr7C3-Cr23C6.50–52
The situation becomes more complex in case the steel
contains more than single strong carbide formers; in these
cases normally more than one carbide may form and the
sequence and amount of individual carbide phase depends
upon the relative strength in carbide forming ability of the
concerned elements.53–55
The alloying elements effect carbide formation during
tempering at temperatures when their diffusion becomes per-
ceptible. If both molybdenum and tungsten are present,
the sequence of carbide formation may be: Fe3C–M2C
(MBMo&W)–M23C6–M6C.
Since tempering is the process where the hardened steel is
reheated to an intermediate temperature, it must take place in
a number of stages that may overlap considerably with
characteristics reactions occurring simultaneously as the steel is
heated to higher and higher temperatures. The microstructural
changes accompanying tempering at different temperatures
following hardening of a medium carbon steel may be fol-
lowed from Figures 48(a)–48(d).
2.1.10.1 Stages of Tempering
During first stage of tempering, formation of transition car-
bides occur, which can be Z carbide (eta carbide) and/or e
carbide (epsilon carbide). The crystal structure of Z carbide is
orthorhombic and bears composition formula Fe2C. However
no authentic proof about formation of the same has been
presented by researchers. The formation of e carbide of closed
pack hexagonal structure with approximate formula Fe2.4C is
already ascertained. The first stage of tempering experiences
segregation of C atom at the internal fault within martensite.
The carbon in excess of 0.2 wt.% is rejected in the form of e
carbide. This converts high carbon martensite to a low carbon
matensite of about 0.2%C, with a low tetragonality, as char-
acterized by a c/a ratio of 1.02, against 1.08 of a 0.8%C con-
taining martensite. Formation of low carbon martensite is a
softening process, whereas e-carbide formation is a process of
hardening. The opposing action of these two phases results in
the hardness of the quenched steel more or less constant (in
fact, the reduction in hardness if there is any, is only just
marginal).
The second stage of tempering takes place within approx-
imate temperature range of 200–300 1C. During this stage
retained austenite is transformed to bainite. However the
second stage of tempering is not very important in any
ordinary steel, as the quantity of retained austenite present in
microstructure is not appreciable. On the contrary in case of
alloy steel, retained austenite content is quite large and hence
second stage of tempering becomes an important phenom-
enon. It is associated by rise in hardness as bainite is harder
than the austenite.
The third stage of tempering takes place at 300 1C and
above; low carbon martensite reduces its tetragonality by way
of diffusing out the C-atoms, which further leads to the for-
mation of elliptical ferrite of BCC crystal structure.
The e carbides dissolve and low carbon martensite loses
tetragonality be rejecting carbon. Finally in the third stage of
tempering taking place at 300 1C, the microstructure consist of
ferrite and cementite; there is an overall contraction in volume
because low carbon martensite becomes cubic at extreme
rapidity at temperature near 300 1C.
During third stage of tempering the ferrite phase undergoes
recovery; dislocations migrate to grain boundaries, resulting
in the formation of acicular ferrite structure of low dislocation
density. Upon further heating to above 600 1C, acicular ferrite
recrystallizes to equiaxed ferrite. However for high carbon
concentration, the ferrite boundary may be pinned and thus
recrystallization may take place with difficulty. The final
microstructure after third stage of tempering consists of
equiaxed ferrite with dispersed spheroidal cementite particles.
However it is to be remembered that rapid heating to the
third stage tempering temperature range, may allow the
changes to take place in the same sequence as described earlier.
Due to paucity of time, for example, e carbide may not even be
 Fundamentals of Heat Treating Metals and Alloys 41

Figure 48 Changes in microstructures and corresponding hardness during tempering of 4140 steel after oil quenching from 870 1C.
(a) Quenched (55RC), (b) tempered at 204 1C (53RC), (c) tempered at 427 1C (45RC), (d) tempered at 649 1C (26RC) (Courtesy of George
Vander Voort , USA), and (e) tempering curve of AISI H13 steel.

formed and the tempering may result into direct formation of
cementite particles.
At the same time it is noted that the retained austenite
present in the microstructure may not undergo isothermal
transformation to bainite, if the tempering is carried out at
temperature 600 1C, by reaching the tempering temperature
through rapid heating. If the tempering temperature lies above
the nose of CCT diagram, the transformation of austenite to
pearlite will occur by diffusional means.
Upon continuation of tempering beyond 600 but below
700 1C, the spheroidal cementite particles grow. The driving
force for particle coarsening is the lowering of free energy due
42 Fundamentals of Heat Treating Metals and Alloys
to overall reduction of surface energy. In alloy steel containing
elements like Cr, Mo a phenomenon called ‘secondary hard-
ening’ takes place at higher tempering temperature. If tem-
pering is carried out at a high temperature, where these
substitutional alloying elements have sufficient mobility, their
carbides are formed at the expense of cementite, which dis-
solves and supplies the flux of carbon atoms for formation of
alloy carbides.
If we follow the tempering curve in Figure 48(e), we observe
that during the first stage of tempering there is no significant
change in the hardness values due to reasons already stated.
Possible hardening of small magnitude in second stage
tempering, due to retained austenite to bainite transformation
is masked by the softening due to loss in tetragonality of
martensite and so there is a continuous softening during third
stage of tempering. Spheroidization followed by coarsening of
cementite called fourth stage of tempering also experiences
softening.
However as the tempering temperature increases to 600 1C
and above, the cementite particles dissolve and alloy carbides
start to emerge. The formation of alloy carbides is a sequential
event, where a number of transitional carbide phases are
formed before the formation of equilibrium carbides.
The transitional carbides are initially coherent with ferrite
matrix thereby making the steel stronger through secondary
hardening. Secondary hardening is essentially an age-hard-
ening phenomenon where sequential change in precipitation
structure and composition occurs; thus secondary hardening
follows mechanism of precipitation hardening. In the case of
secondary hardening initially formed precipitates are coherent
with the matrix and strong interaction between dislocations
and coherency strain gives rise to the strengthening.
2.1.10.2 Formation of Bainite in Steels
It is seen that diffusional transformation of austenite produces
pearlite whereas transformation of austenite under complete
suppression of diffusional process takes place through diffu-
sionless shear transformation mode resulting in supersatured
solid solution of carbon in body centered tetragonal ferrite
that is martensite. However there can be a situation where the
driving energy for martensitic transformation is not available
and diffusional mode of transformation of austenite is also
improbable due to sluggishness of atomic mobility within
the temperature range intermediate to nose of TTT diagram
and the martensite start temperature. Under such circum-
stances a mixed mode of transformation, in the form of bai-
nitic reaction takes place. The character of transformation is
partly diffusional and partly shear. Again depending upon the
transformation temperature and hence the available driving
force the diffusion of solute carbon atoms may take place
before or after the FCC–BCC polymorphic transition through
shear mechanism. Accordingly the transformation products are
called upper or lower bainite.
2.1.10.2.1 Mechanism of bainite formation
Below the nose of TTT diagram, lamellar product of decom-
position of austenite is no longer seen to form; rather discrete
particles of ferrite and cementite with different morphologies
are observed in the microstructure. When austenite is given to
transform at various temperatures below the nose of TTT
diagram, phase transformation of austenite follows different
mechanisms. The evidence of change in the manner of asso-
ciation as well as the composition of carbide and ferrite phases
in the microstructures of low carbon steels under situation of
continuous cooling, has enticed the scientists to advocate for
mechanistically transient character of austenite transformation
down to martensite transformation temperature. Study on the
isothermal decomposition of austenite in these steels, provides
good information about the possible mechanism of phase
transformation. It has long been known that below the nose of
TTT diagram, broadly two different classes of microstructures
are formed. The first one forming just below the nose of TTT
diagram and above 300 1C is called upper bainite; upper
bainite appears feathery under optical microscope. In contrast,
the decomposition product forming below 300 1C looks aci-
cular or needle shaped; this phase mixture is called lower
bainite. In upper bainite the sheaves of fine elongated ferrite
laths are formed. The cementite particles lie along the
boundaries between the laths of ferrite. In case of lower bai-
nite, ferrite becomes more acicular and is appreciably super-
saturated with carbon. This needle-shaped ferrite crystals
exhibited the presence of intra lath carbide particles. The
composition of this carbide phase is also different from that in
upper bainite, which is orthorhombic cementite, Fe3C of
6.67 wt.% carbon. In contrast, the lower bainitic carbide phase
contains 8.4 wt.% carbon with a stoichiometric formula
Fe2.3C. The microstructure of upper bainite in 0.8%C steels is
shown in (Figure 49); the transmission electron microstructure
gives evidence of bainitic ferrite with carbide at the lath
boundaries. A high dislocation density within the ferrite is also
noticed. Ferrite lath in upper bainite also shows evidence of
dislocations generated presumably due to lattice invariant
deformation. Similarly the optical and transmission electron
microstructure of lower bainite formed during isothermal
transformation of austenite in 0.8%C steel show needle-like
ferrite crystals with intra granular carbides (Figure 50).
In case of formation of upper bainite, diffusion of carbon
in austenite takes place at relatively higher transformation
temperature 400 1C; this leads to creation of the localized
carbon-depleted regions within the metastable austenite. The
preceding carbon diffusion followed by the creation of the
above stated carbon-depleted regions result in rise of Ms
temperature and since a highly metastable austenite below the
nose of TTT diagram seeks for a suitable mode to undergo
rapid transformation for its urge to lower overall free energy of
the system, the diffusionless martensitic transformation is
called for just when adequate driving energy commensurate
with martensite formation temperature becomes available.
This behavior is logically consistent with proposed trans-
formation mechanisms of lower bainite; the low transformation
temperature of lower bainite tantamount to a much higher
available driving forces and hence austenite can undergo poly-
morphic transformation without regard to prior diffusion of
carbon. However one school of thought has proposed that
upper bainitic transformation is entirely diffusional and is
nothing more than a nucleation and growth type process where
the ferrite crystal grow by ledge mechanism; bainitic ferrite
sheaves are formed by sympathetic nucleation of new crystals
at the boundary of prior crystals; according to this school of
 Fundamentals of Heat Treating Metals and Alloys 43

Figure 49 TEM and optical photomicrograph of upper bainite (dark) and martensite (white) in 0.6%C–0.85%Mn–0.25%Si–0.8%Cr steel
(austenitized at 830 1C and partially transformed to upper bainite at 530 1C). Courtesy of George Vander Voort, USA. http://cml.postech.ac.kr.

Figure 50 TEM and optical micrograph of lower bainite (dark) and martensite (white) in 0.6%C–0.85%Mn–0.25%Si–0.8%Cr steel (austenitized at
830 1C and partially transformed to lower bainite at 350 1C). Courtesy of George Vander Voort, USA. http://cml.postech.ac.kr.

thought, upper bainite formation can no longer be con-
sidered to be a ‘partly diffusional and partly diffusion less
shear transformation.’ In this context it may be recalled that
transformation of undercooled austenite is mechanistically
transient and different transformation mechanisms operating
at various degree of undercooling are distinguishable in
continuously cooled low carbon steel. As one increases the
degree of under cooling in a pool of transforming austenite,
the phase transformation of austenite to ferrite is reported to
take place in the sequence: polygonal ferrite–widsmanstatten
ferrite–massive ferrite–granular ferrite (bainite)–acicular
bainite–martensite. Each transformation type takes place
within specific temperature region as decided by the chemical
composition and defect structure of the transforming auste-
nite. It has been demonstrated earlier that granular bainite
forms by ledge mechanism; there is therefore reasons to
believe that for any specific condition of under cooling, the
driving force for polymorphic transition of austenite typifies
a definite mode of transformation to operate. In extreme
circumstances the mechanism of basic transition of austenite
to ferrite may be non-diffusional, notwithstanding if diffu-
sion of carbon atoms, required to form bainitic carbides takes
place before (upper bainite) or after transformation (lower
bainite). Although the proposition of ledge mechanism in
formation of some form of bainite must not be reasoned out,
it is wiser to dispense with dogmatic documentation in favor
of fully diffusional nature of any bainitic transformation. The
transient transformation behavior has its origin to the com-
promise between degree of metastability of austenite and
feasibility of any specific transformation mode to operate
within the scope of available driving energy with insurance of
the most favorable transformation kinetics for FCC austenite
to BCC ferrite formation.
2.1.10.3 Martempering
It is stated earlier that hardening of steel gives rise to severe
thermal stresses over and above the inevitable transformational
44 Fundamentals of Heat Treating Metals and Alloys
stresses. These two stresses together, quite often lead to warpage
or cracking of the heat treating stock. ‘Martempering’ is a pro-
cess, which can minimize the chance of cracking during hard-
ening of alloy steels. In this process, the steel after being suitably
austenitized, is rapidly quenched in suitable medium, i.e., pre-
ferably a salt bath, which is maintained at constant temperature
above the Ms temperature and held there for preselected period
of time as shown in Figure 51.
Temperature of holding is decided by the Ms temperature
of the material being quenched that is the chemical compo-
sition of steel. On the contrary, the holding time must com-
mensurate with the time required to equalize the temperatures
between the surface and center of the heat treating stock, which
further is a function of the geometry of the stock. Too low a
holding time will not secure the basic purpose of this process;
again too high holding time will bring about decomposition
of austenite through diffusional means, which the process of
hardening of steel does not aim at. Holding the steel above Ms
temperature for sufficient period of time, equalizes the tem-
perature between center and surface of the stock. Thus the
thermal stresses generated due to differential volume contrac-
tion across the section of the stock are removed; also
quenching from low temp to trigger martensite formation will
eliminate thermal shock and hence reduce overall thermal
stresses. Stresses originated from volume change accompany-
ing martensitic transformation only exist. This leads to mini-
mization of warpage and lessens the chances of formation of
quench cracks. Thermal stresses is dependent on section size
and if there is sharp change in section size in a component,
stress localization may occur at the transition region; failure
may initiate from this weak region. A larger section implies a
higher magnitude of difference in cooling rate between surface
and center; therefore thermal stress becomes quite high. Along
with this, rapid change in cross section aggravates the situation
and tendency to form quench cracks increases.
2.1.10.4 Austempering
Many medium carbon low alloy structural steels achieve their
optimum properties with a microstructure similar to that of
lower bainite. This type of structure can be obtained by a heat
treatment called ‘Austempering.’ ‘Austempering’ is the process
of heat treatment where the steel is heated to austenitizing
Figure 51 Martempering.
temperature, held there for sufficient period of time to produce
homogeneous austenite. The selection of austenitizing tem-
perature and time follows from the same principles as that
in the case of conventional quench-hardening process. After
austenitization the steel is rapidly cooled to a temperature
above Ms temperature and preferably in the region of lower
bainite transformation. The severity of quench must be such as
to be able to overcome the hardenability constraint if any. A
salt bath kept at the quenching temperature say 300 1C, is used
for isothermally holding the component for sufficiently long
period so that complete decomposition of austenite may take
place as shown in Figure 52.
Holding at the austempering temperature eliminates ther-
mal stresses and isothermal transformation of austenite to
lower bainite in a salt bath also protects the steel from oxi-
dation due to neutral atmosphere and from distortion due
to prevailing situation of hydrostatic pressure. Austempering
produces lower bainite which is composed of supersaturated
ferrite and e carbide (Figure 53). Needless to say that after
completion of bainitic transformation no other transforma-
tion takes place during cooling to room temperature from
bainitic reaction temperature.
The low temperature tempering of hardened steel also pro-
duces low carbon martensite (i.e., ferrite of low supersaturation)
and e carbide. However strength and toughness properties of
austempered material are much better than the hardened and
tempered material.
During austempering lower bainitic transformation is
envisaged. This means that quenching to austempering tem-
perature leads to the formation of supersaturated ferrite by
Figure 52 Austempering.
Figure 53 Microstructure showing supersaturated ferrite and e
carbide. Courtesy of George Vander Voort, USA.

diffusionless shear transformation mechanism; but due to the
high temperature and also due to great urge for getting relieved
from super saturation, the ferrite rejects carbon quite quickly in
the form of ɛ carbide of 8.3 wt.%C (Reed-Hill).1 Lower bainitic
ferrite is much lean in carbon content as compared to the
austenite and so excess carbon is rejected by the growing bai-
nitic ferrite crystals ahead of the interface between the product
ferrite phase and the parent austenite phase. Thus austenite
ahead of bainitic ferrite becomes enriched with carbon; this
process of formation of bainitic ferrite and continuous carbon
enrichment of austenite ahead of interface continues, till a time
is reached when high carbon austenite ahead of growing ferrite
crystal cannot give way to the formation of bainite; at this time,
growth of bainitic ferrite stops and there remains high carbon
austenite, which cannot even transform to martensite during
subsequent cooling to room temperature, owing principally
to its increased metastability. Such a large amount of austenite
retained inevitably due to incomplete bainitic reaction provides
adequate ductility to the alloy. Thus austempering enables to
achieve a good combination of high strength and high tough-
ness, which otherwise would not have been possible, if the
same steel was fully hardened and then tempered at the same
austempering temperature (Figure 54). Austempering can hard-
en complicated steel components without causing distortion
and cracking. It can impart excellent toughness and ductility in
thin sections of plain carbon steel. However, the entire cross
section of the steel must be cooled rapidly enough to miss the
nose of the IT curve. It is to note that thicker sections (43 mm)
of plain carbon steels are difficult to be austempered because of
the short incubation period at the nose of TTT diagram. So,
only thin sections are subjected to austempering. However
larger sections of alloy steels can be austempered where the
time to start the transformation is quite high.
2.1.11 Retained Austenite
In majority of cases the transformation of austenite to marten-
site does not go to completion. Presence of some untransformed
austenite called ‘retained austenite’ is inevitable although its
amount and quality depends upon composition of steel and
its initial microstructure. Figure 55, shows that the amount
Figure 54 Microstructure of 0.37C–0.48Mn–1.3Cr austempered steel.56
Fundamentals of Heat Treating Metals and Alloys 45
of martensite formed from austenite increases as the trans-
formation temperature is decreased within the Ms–Mf range.
Martensite starts to form at Ms and its amount increases
with decrease in temperature till the Mf temperature, which
denotes completion of transformation. This follows from
the typical characteristics of athermal transformation. At this
point the transformed phase may contain some retained
austenite. Figure 56 gives evidence of retained austenite in
0.9C steel after water quenching from 900 1C
Retained austenite is highly unstable and can be subse-
quently transformed to bainite or martensite depending upon
the parameters of tempering operation. Sometimes a small
amount of retained austenite is deliberately kept in the final
microstructure. Not only it imparts toughness to the hardened
steel but also if it transforms to martensite during post tem-
pering cooling operation, some residual compressive stresses
may be developed which is quite helpful to improve fatigue
resistance.
Retained austenite is very soft and so if it is present in large
quantity, say, by more than 15–20 vol.% in the microstructure,
there will be a considerable reduction in the hardness of the
quenched steel. As martensite forms, its volume strain is
accommodated both by product martensite by lattice invariant
deformation and by matrix austenite through plastic deforma-
tion. Continued growth of martensite plates lead to small pool
of austenite entrapped between adjacent plates of martensite.
This austenite contains a high density of crystal imperfection
Figure 55 Martensite transformation curve.
Figure 56 Microstructure showing retained austenite in quenched
steel quenched from 900 1C. Courtesy of George Vander Voort, USA.
46 Fundamentals of Heat Treating Metals and Alloys
Figure 57 Effect of the alloying elements on the amount of retained austenite in quenched steel (1 wt.%C).
Figure 58 Effect of alloying addition on martensite range.
viz. dislocation and is not amenable to further martensite
transformation. So they remain present in the microstructure as
retained austenite.
Both Ms and Mf temperature are functions of alloying ele-
ment content. When Mf goes below room temperature, the
amount of retained austenite in the microstructure will
expectedly be higher. The amount of austenite to be retained is
mainly decided by the Ms–Mf temperature range. The effect of
various alloying elements on the amount of retained austenite
formed during quenching of steels is shown in Figure 57. The
alloying elements which depress the Ms temperature are those
which increase the percentage of retained austenite in the
microstructure.
In alloy steels, the martensite start point Ms is lowered by
most of the alloying elements and the martensite range nar-
rows under the influence of carbon. The influence of carbon
on austenite content is stronger than that of other alloying
elements as shown in Figure 58.
In addition to the carbon content and alloying elements,
the other factor which can influence the amount of retained
austenite formed during quenching of steel is the rate of
cooling between the martensite start point Ms and the final
quenching temperature.
However at temperature just below Ms temperature a slow
cooling may affect isothermal transformation of martensite
formation. Here a phenomenon called the stabilization of
austenite takes place. Holding the transforming austenite
after appreciable amount of athermal martensite has formed,
makes it prone to stabilization due to, relaxation of stress.
Austenite stabilization takes place due to stress relaxation
which leads to permanent loss of coherence between parent
and product phase. The longer the holding time, the greater
would be stress relaxation and thus greater will be stabiliza-
tion. If martensitic transformation is interrupted between
Ms–Mf ranges, then for further transformation to take place,
much higher driving force will be required by intensive
cooling.
The effect of quenching temperature is linked to the mag-
nitude of thermal stresses due to transformation of austenite
to martensite. When steel is heated substaintially above A3
temperature, grain coarsening of austenite takes place, which
further results in the formation of larger martensite plates. This
leads to higher volume fraction of retained austenite in the
microstructure. Higher austenitizing temperature lowers the
martensite start temperatures (Ms), due to complete dissolu-
tion of carbide. When hypereutectoid steels are quenched from
the region of pure austenite, i.e., after heating the steel above
the Acm temperature for complete dissolution of carbides
(which is not usual), the quenched microstructure consists
of martensite and retained austenite; the hardness is reduced
due to high amount of retained austenite. The initial retained
austenite amount (after quenching) is dependent on the
austenitizing (hardening) temperature to a large extent. The
higher the hardening temperature, the greater the amount of
retained austenite, but this retained austenite can be made
transformed to martensite by subzero treatment.
2.1.11.1 Subzero Treatment
Subzero treatment consist of cooling the metal to a tempera-
ture below 0 1C, but in general subzero treatment temperature
may range from
130 to
30 1C with holding time around
1 h. In some cases the subzero treatment temperature can be as
low as
190 1C in accordance with the Mf temperature of the
steel which in turn depends on its chemical composition. If
austenite stabilization takes place at room temperature, it will
be difficult to transform retained austenite to martensite by
subzero treatment.
Subzero treatment should to be done in continuation with
the original quenching, without much residence time at room
temperature. If we wish to convert retained austenite to mar-
tensite at room temperature, it must be heated to higher
temperature in a region of metastable austenite. Cooling from
that temperature down to room temperature will enable aus-
tenite to transform to martensite. Multiple tempering may
 Fundamentals of Heat Treating Metals and Alloys 47

effect transformation of retained austenite to martensite dur-

ing post tempering cooling and repetition of the process may
ultimately eliminate the retained austenite from the structure.
Subzero treatment is normally employed in high alloy
steels which are prone to form high amount of retained aus-
tenite after quenching to room temperature. However in case
of industrial scale operation, subzero treated steel is reported
to have suffered from a loss in bending strength. There are
reports confirming the enhancement of wear resistance in
ledeburitic steels. It is also observed that the bending strength
of the steel can be recovered by tempering above the secondary
hardness peak temperature. Reportedly, the three point bending
strength of material undergoing subzero processing is lower
than the non-subzero processed one. However the reason
for this apparently anomalous behavior requires further inves-
tigation.57 It is further reported that accelerated rate of pre-
cipitation due to subzero treatment contributes significantly to Figure 59 State of stresses due to quenching of a round bar.
the enhancement of wear resistance; the high wear resistance of
steel subjected to subzero treatment is ascribed to the formation
of carbides of size less than 0.5 m; also the improvement in wear
resistance outweighs the marginal loss in bending strength.
Because of the fact that the quenched hardness of the subzero
treatment is higher than that of the non-subzero treated steels, a
greater latitude in decrement of hardness due to tempering is
available. This ensures better mechanical property of subzero-
treated steel after low temperature tempering.58

2.1.12 Heat Treatment Defects

2.1.12.1 Quench Cracks

When hardening is accomplished with a martensite transfor-
mation, evolution of large residual stress is inevitable. Such
stress owes its origin to differential thermal contraction of a
material cooled rapidly from a high temperature and stress due
to transformation.
When the steel sample is quenched rapidly from a high
temperature to the room temperature for hardening two types
of stresses are developed; one is due to volume change
accompanying phase transformation and the other is due to
differential coefficient of contraction of different phases pre-
sent in the material. Also thermal stress due to temperature
difference between surface and center of the component is
superimposed. When the cumulative value of these stresses
becomes large enough, plastic deformation of the steel sample
may take place. This plastic deformation may lead to warpage
of the component; whenever plastic deformation is unable to
take care of all the quench stresses, there would be accumu-
lation of the residual stress which when exceeds the fracture
stress of the material will lead to quench crack.
When a round steel bar is quenched, the surface undergoes
martensite transformation before the center. It is known that
martensite transformation leads to expansion whereas rapid
cooling leads to thermal contraction. When expansion at the
surface is larger than thermal contraction, the surface will be in
a state of tension whereas center is at the state of contraction as
shown in Figure 59.
If contraction exceeds expansion at the surface the reverse
stress pattern with surface under residual compressive stress
and center with tension will prevails. Which of these two will
Figure 60 Residual stresses in a steel cylinder quenched to form
martensite as computed by Scott. Scott, H. Origin of Quenching
Cracks. Sci. Pap. Bur. Stand. 1925, 20, 399.
actually be present is decided by the relative cooling rate at
the surface and at the center of the bar; this is a function of
both size of the bar and severity of quench. For large diameter
and fast cooling, the surface will form martensite while the
center is still at high temperature. Under such circumstances
thermal stress will be quite large and it will determine the
pattern of volume change. Usually thermal contraction will
exceed expansion due to martensite transformation. On the
other hand for a thinner object, the difference in cooling rate
between surface and center is small the thermal contraction
after hardening of surface is still smaller as compared to
expansion due to martensite transformation. The variation in
stress due to temperature difference between center and surface
of the bar is shown in Figure 60.
In many cases the tensile stress persists at the surface.
Initially over a large range of specimen diameter tensile stress
is seen to increase with cooling rate differentials. Those steel
which have high carbon content, transform to martensite with
higher degree volume expansion and hence in such case the
tensile stress prevails at surface. Since quench crack is formed
48 Fundamentals of Heat Treating Metals and Alloys
Figure 61 Widmanstatten ferrite in water quenched 1018 steel. Courtesey of George Vander Voort, USA.
as a result of tensile stress high carbon steel with high volume
change put to a very fast quenching, results in quench crack.
2.1.12.2 Overheating
If a steel specimen is heated for a very long time far above the
stipulated temperature, over heating may occur with the result
of getting coarse grains. Structure of the overheated steel
sample with Widmanstätten ferrite is shown in Figure 61. If a
prolonged heating at a temperature is carried out in a furnace
where no control of atmosphere is existent or if the material is
heated to a temperature near to its melting point, the damage
of the specimen is visualized as burning. In this case carbon
atoms segregate at the grain boundaries and lead to inter-
crystalline fracture. A lot of cavities can form including the
formation of iron oxide which will be present as inclusion and
this leads to stone like fracture at a low ductility level. Quite
often in an uncontrolled furnace a high austenitizing tem-
perature leads to decarburization of the surface and the
hardness of the surface is decreased, and it misleads the heat
treater. Excessive decarburization is associated with the for-
mation of thick scale that acts as an insulating blanket and
does not allow heat extraction to desired level. This makes the
entire heat treatment process uncertain and undesirable.
See also: 2.8 Heat Treatment of Commercial Steels for Engineering
Applications
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Further Reading
Gunn, R. N., Ed. Duplex Stainless Steels, Microstructural Properties and
Applications; Abington Publishing: Cambridge, 1997.
Lakhtin, Y. Engineering Physical Metallurgy; Mir Publishers: Moscow and CBS
Publishers and Distributors: India, 1998.
Relevant Website
www.georgevandervoort.com/.../20001270-microstructure-of-ferrous-alloys
George Vander Voort.