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Engineering Materials

Heat Treatments of Ferrous Alloys

Annealing Processes

The term annealing refers to a heat treatment in which a material is exposed to an

elevated temperature for an extended time period and then slowly cooled.
Ordinarily, annealing is carried out to (1) relieve stresses; (2) increase softness,
ductility, and toughness; and/or (3) produce a specific microstructure.

Internal residual stresses may develop in metal pieces in response to the following:
(1) plastic deformation processes such as machining and grinding; (2) non-uniform
cooling of a piece that was processed or fabricated at an elevated temperature, such
as a weld or a casting; and (3) a phase transformation that is induced upon cooling
wherein parent and product phases have different densities. Distortion and warpage
may result if these residual stresses are not removed.

A variety of annealing heat treatments are possible; they are characterized by the
changes that are induced, which many times are microstructural and are
responsible for the alteration of the mechanical properties. Any annealing process
consists of three stages: (1) heating to the desired temperature, (2) holding or
―soaking‖ at that temperature, and (3) cooling, usually to room temperature.

Process Annealing is a heat treatment that is used to negate the effects of cold
work—that is, to soften and increase the ductility of a previously strain-hardened
metal. It is commonly utilized during fabrication procedures that require extensive
plastic deformation, to allow a continuation of deformation without fracture or
excessive energy consumption. Recovery and recrystallization processes are
allowed to occur. Ordinarily a fine-grained microstructure is desired, and therefore,
the heat treatment is terminated before appreciable grain growth has occurred.
Surface oxidation or scaling may be prevented or minimized by annealing at a
relatively low temperature (but above the recrystallization temperature) or in a
non-oxidizing atmosphere.

Stress Relief annealing heat treatment in which the piece is heated to the
recommended temperature, held there long enough to attain a uniform temperature,
and finally cooled to room temperature in air. The annealing temperature is
ordinarily a relatively low one such that effects resulting from cold working and
other heat treatments are not affected.

Annealing of Ferrous Alloys

Several different annealing procedures are employed to enhance the properties of

steel alloys. However, before they are discussed, some comment relative to the
labeling of phase boundaries is necessary. Figure (1) shows the portion of the iron–
carbon phase diagram in the vicinity of the eutectoid. The horizontal line at the
eutectoid temperature, conventionally labeled A1, is termed the lower critical
temperature, below which, under equilibrium conditions, all austenite will have
transformed into ferrite and cementite phases. The phase boundaries denoted as A3
and Acm represent the upper critical temperature lines, for hypoeutectoid and
hypereutectoid steels, respectively. For temperatures and compositions above these
boundaries, only the austenite phase will prevail. Note that other alloying elements
(if exist) will shift the eutectoid and the positions of these phase boundary lines.

Figure (1). The iron–carbon phase diagram in the vicinity of the eutectoid, indicating heat-
treating temperature ranges for plain carbon steels.

Steels that have been plastically deformed by, for example, a rolling operation,
consist of grains of pearlite (and most likely a proeutectoid phase), which are
irregularly shaped and relatively large, but vary substantially in size. An annealing
heat treatment called normalizing is used to refine the grains (i.e., to decrease the
average grain size) and produce a more uniform and desirable size distribution;
fine-grained pearlitic steels are tougher than coarse-grained ones. Normalizing is
accomplished by heating at least (55°C) above the upper critical temperature—that
is, above A3 for compositions less than the eutectoid, and above Acm for
compositions greater than the eutectoid as represented in Figure(1). After sufficient

time has been allowed for the alloy to completely transform to austenite — a
procedure termed austenitizing — the treatment is terminated by cooling in air.

Full Anneal

A heat treatment known as full annealing is often utilized in low- and medium
carbon steels that will be machined or will experience extensive plastic
deformation during a forming operation. In general, the alloy is treated by heating
to a temperature of about (55°C) above the A3 line (to form austenite) for
compositions less than the eutectoid, or, for compositions in excess of the
eutectoid, (55°C) above the A1 line (to form austenite and Fe3C phases)., as noted
in Figure (1). The alloy is then furnace cooled; that is, the heat-treating furnace is
turned off and both furnace and steel cool to room temperature at the same rate,
which takes several hours. The microstructural product of this anneal is coarse
pearlite (in addition to any proeutectoid phase) that is relatively soft and ductile.

Coarse and Fine Pearlite

The thickness ratio of the ferrite and cementite layers in pearlite is approximately 8
to 1. However, the absolute layer thickness depends on the temperature at which
the isothermal transformation is allowed to occur. At temperatures just below the
eutectoid, relatively thick layers of both the α-ferrite and Fe3C phases are
produced; this microstructure is called coarse pearlite, and the region at which it
forms is indicated to the right of the completion curve on figure (2). At these
temperatures, diffusion rates are relatively high, such that during the
transformation from austenite to pearlite the atoms of carbon can diffuse relatively
long distances, which results in the formation of thick lamellae.

With decreasing temperature, the carbon diffusion rate decreases, and the layers
become progressively thinner. The thin-layered structure produced in the vicinity
of 450°C is termed fine pearlite; this is also indicated in figure (2).


Medium- and high-carbon steels having a microstructure containing even coarse

pearlite may still be too hard to conveniently machine or plastically deform. These
steels, and in fact any steel, may be heat treated or annealed to develop the
spheroidite structure. Spheroidized steels have a maximum softness and ductility
and are easily machined or deformed. The spheroidizing heat treatment, during

which there is a coalescence of the Fe3C to form the spheroid particles, can take
place by several methods, as follows:

• Heating the alloy at a temperature just below the eutectoid [line A1, or at about
(700° C)], spheroidizing times will ordinarily range between 15 and 25 h.

• Heating to a temperature just above the eutectoid temperature, and then either
cooling very slowly in the furnace, or holding at a temperature just below the
eutectoid temperature.

• Heating and cooling alternately within about ±50° C of the A1 line of Figure (1).

To some degree, the rate at which spheroidite forms depends on prior

microstructure. For example, it is slowest for pearlite, and the finer the pearlite, the
more rapid the rate. Also, prior cold work increases the spheroidizing reaction rate.

Quenching of Steels

Martensite is formed when austeniteized iron–carbon alloys are rapidly cooled (or
quenched) to a relatively low temperature (in the vicinity of the ambient).
Martensite is a non-equilibrium single-phase structure that results from a
diffusionless transformation of austenite. It may be thought of as a transformation
product that is competitive with pearlite and bainite. The martensitic
transformation occurs when the quenching rate is rapid enough to prevent carbon
diffusion. Any diffusion whatsoever will result in the formation of ferrite and
cementite phases.

Large numbers of atoms experience cooperative movements, in that there is only a

slight displacement of each atom relative to its neighbors. This occurs in such a
way that the FCC austenite experiences a polymorphic transformation to a body-

centered tetragonal (BCT) martensite. A unit cell of this crystal structure (figure
3.A) is simply a body-centered cube that has been elongated along one of its
dimensions; this structure is distinctly different from that for BCC ferrite. All the
carbon atoms remain as interstitial impurities in martensite; as such, they constitute
a supersaturated solid solution that is capable of rapidly transforming to other
structures if heated to temperatures at which diffusion rates become appreciable.

Martensite grains take on a plate-like or needle-like appearance, as indicated in

figure (3.B). The white phase in the micrograph is austenite (retained austenite)
that did not transform during the rapid quench. As already mentioned, martensite
as well as other microconstituents (e.g., pearlite) can coexist.

Being a nonequilibrium phase, martensite does not appear on the iron–carbon
phase diagram. The austenite-to-martensite transformation is, however, represented
on the isothermal transformation diagram [time–temperature–transformation
(or T–T–T) plots]. Since the martensitic transformation is diffusionless and
instantaneous, it is not depicted in this diagram as the pearlitic and bainitic
reactions are. The beginning of this transformation is represented by a horizontal
line designated M (start), figure (4).

Two other horizontal and dashed lines, labeled M(50%) and M(90%), indicate
percentages of the austenite-to-martensite transformation. The temperatures at
which these lines are located vary with alloy composition but, nevertheless, must
be relatively low because carbon diffusion must be virtually nonexistent. The
horizontal and linear character of these lines indicates that the martensitic
transformation is independent of time; it is a function only of the temperature to
which the alloy is quenched or rapidly cooled. A transformation of this type is
termed an athermal transformation.

The presence of alloying elements other than carbon (e.g., Cr, Ni, Mo, and W) may
cause significant changes in the positions and shapes of the curves in the
isothermal transformation diagrams. These include (1) shifting to longer times the
nose of the austenite-to-pearlite transformation (and also a proeutectoid phase
nose, if such exists), and (2) the formation of a separate bainite nose. These
alterations may be observed by comparing figures (4) and (5), which are isothermal
transformation diagrams for carbon and alloy steels, respectively.

Tempered Martensite

In the as-quenched state, martensite, in addition to being very hard, is so brittle that
it cannot be used for most applications; also, any internal stresses that may have
been introduced during quenching have a weakening effect. The ductility and
toughness of martensite may be enhanced and these internal stresses relieved by a
heat treatment known as tempering.

Tempering is accomplished by heating a martensitic steel to a temperature below
the eutectoid for a specified time period. Normally, tempering is carried out at
temperatures between 250 and 650°C; internal stresses, however, may be relieved
at temperatures as low as 200°C. This tempering heat treatment allows, by
diffusional processes, the formation of tempered martensite, according to the

where the single-phase BCT martensite, which is supersaturated with carbon,

transforms to the tempered martensite, composed of the stable ferrite and cementite
phases, as indicated on the iron–carbon phase diagram. The microstructure of
tempered martensite consists of extremely small and uniformly dispersed cementite
particles embedded within a continuous ferrite matrix. This is similar to the
microstructure of spheroidite except that the cementite particles are much, much
smaller. An electron micrograph showing the microstructure of tempered
martensite at a very high magnification is presented in Figure (6).

Tempered martensite may be nearly as hard and strong as martensite, but with
substantially enhanced ductility and toughness. The dependence of tensile and
yield strength and ductility on tempering temperature for an alloy steel is shown in
figure (7).

Bainitic Steel

In addition to pearlite, other microconstituents that are products of the austenitic

transformation exist; one of these is called bainite. The microstructure of bainite is
composed of a ferrite matrix and elongated particles of Fe3C, and thus diffusional
processes are involved in its formation; the microstructural details of bainite are
very fine that it can be seen only using electron microscopy, not an optical

microscopy. Because bainitic steels have a finer structure, they are generally
stronger and harder than pearlitic ones; yet they exhibit a desirable combination of
strength and ductility.

The time–temperature dependence of the bainite transformation may also be

represented on the isothermal transformation diagram (figure 1). It occurs at
temperatures below those at which pearlite forms; begin-, end-, and half-reaction
curves are just extensions of those for the pearlitic transformation, as shown in
figure (1), the isothermal transformation diagram for an iron–carbon alloy of
eutectoid composition that has been extended to lower temperatures. All three

curves are C-shaped and have a ―nose‖, where the rate of transformation is a
maximum. As may be noted, whereas pearlite forms above the nose (i.e., over the
temperature range of about 540 727°C to), at temperatures between about 215 and
540°C, bainite is the transformation product.

It should also be noted that pearlitic and bainitic transformations are really
competitive with each other, and once some portion of an alloy has transformed to
either pearlite or bainite, transformation to the other microconstituent is not
possible without reheating to form austenite.

Review of Phase Transformations for Iron-Carbon Alloys

Figure (8) summarizes the transformation paths that produce these various
microstructures. Here, it is assumed that pearlite, bainite, and martensite result
from continuous cooling treatments; furthermore, the formation of bainite is only
possible for alloy steels (not plain carbon ones).

Furthermore, microstructural characteristics and mechanical properties of the

several microconstituents for iron–carbon alloys are summarized in Table 1.

Example 1: Microstructural Determinations for Three Isothermal Heat

Using the isothermal transformation diagram for an iron–carbon alloy of eutectoid

composition (figure 4), specify the nature of the final microstructure (in terms of
microconstituents present and approximate percentages) of a small specimen that
has been subjected to the following time–temperature treatments. In each case
assume that the specimen begins at 760°C and that it has been held at this
temperature long enough to have achieved a complete and homogeneous austenitic

(a) Rapidly cool to 350°C, hold for 104 s, and quench to room temperature.

(b) Rapidly cool to 250°C, hold for 100 s, and quench to room temperature.

(c) Rapidly cool to 650°C, hold for 20 s, rapidly cool to 400°C, hold for 103 s, and
quench to room temperature.


The time–temperature paths for all three treatments are shown in figure (9). In each
case the initial cooling is rapid enough to prevent any transformation from

(a) At 350°C austenite isothermally transforms to bainite; this reaction begins after
about 10 s and reaches completion at about 500 s elapsed time. Therefore, by 104 s,
as stipulated in this problem, 100% of the specimen is bainite, and no further
transformation is possible, even though the final quenching line passes through the
martensite region of the diagram.

(b) In this case it takes about 150 s at 250°C for the bainite transformation to
begin, so that at 100 s the specimen is still 100% austenite. As the specimen is
cooled through the martensite region, beginning at about 215°C, progressively
more of the austenite instantaneously transforms to martensite. This transformation
is complete by the time room temperature is reached, such that the final
microstructure is 100% martensite.

(c) For the isothermal line at 650°C, pearlite begins to form after about 7 s; by the
time 20 s has elapsed, only approximately 50% of the specimen has transformed to
pearlite. The rapid cool to 400°C is indicated by the vertical line; during this
cooling, very little, if any, remaining austenite will transform to either pearlite or
bainite, even though the cooling line passes through pearlite and bainite regions of
the diagram. At 400°C, we begin timing at essentially zero time (as indicated in
figure 9); thus, by the time 1000 s have elapsed, all of the remaining 50% austenite
will have completely transformed to bainite. Upon quenching to room temperature,
any further transformation is not possible inasmuch as no austenite remains; and so
the final microstructure at room temperature consists of 50% pearlite and 50%


1- Using the isothermal transformation diagram for an iron–carbon alloy of

eutectoid composition (figure 10), specify the nature of the final microstructure (in
terms of microconstituents present and approximate percentages of each) of a small

specimen that has been subjected to the following time–temperature treatments. In
each case assume that the specimen begins at 760°C and that it has been held at
this temperature long enough to have achieved a complete and homogeneous
austenitic structure.

(a) Cool rapidly to 350°C, hold for 1000 s, then quench to room temperature.

(b) Rapidly cool to 625°C, hold for 10 s, then quench to room temperature.

(c) Rapidly cool to 600°C, hold for 4 s, rapidly cool to 450°C, hold for 10 s, then
quench to room temperature.

(d) Reheat the specimen in part (c) to 700°C for 20 h.

(e) Rapidly cool to 300°C, hold for 20 s, then quench to room temperature in
water. Reheat to 425°C for 1000 s and slowly cool to room temperature.

(f ) Cool rapidly to 665°C, hold for 1000 s, then quench to room temperature.

(g) Rapidly cool to 575°C, hold for 20 s, rapidly cool to 350°C, hold for 100 s,
then quench to room temperature.

(h) Rapidly cool to 350°C, hold for 150 s, then quench to room temperature.

2- Make a copy of the isothermal transformation diagram for an iron–carbon alloy

of eutectoid composition (figure 10) and then sketch and label time–temperature
paths on this diagram to produce the following microstructures:

(a) 100% coarse pearlite

(b) 50% martensite and 50% austenite

(c) 50% coarse pearlite, 25% bainite, and 25% martensite

Figure (10) complete isothermal transformation diagram for an iron–carbon alloy of eutectoid