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PHASE DIAGRAM-IV
Phase transformation in metals
Dr. Aneela Wakeel
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Iron-Iron Carbide system

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The influence of other alloying elements

Additions of other alloying elements (Cr, Ni, Ti, etc.)
bring about rather dramatic changes in the binary
iron–iron carbide phase diagram.
One of the important changes is the shift in position
of the eutectoid with respect to temperature and to
carbon concentration.

Alloy additions alter not

only the temperature of
the eutectoid reaction but
also the relative fractions
of pearlite and the
proeutectoid phase that
form. Steels are normally
alloyed for other reasons,
however—usually
either to improve their
corrosion resistance or to
render them amenable to
heat treatment
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Isothermal transformation diagram

which is fundamental to the development of microstructure in steel alloys. Upon

cooling, austenite, having an intermediate carbon concentration, transforms to a
ferrite phase, having a much lower carbon content, and also cementite, with a
much higher carbon concentration. Pearlite is one microstructural product of this
transformation (Figure 9.27
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Role of temperature in Austenite-Pearlite

transformation
Temperature plays an important role in the rate of the austenite-to-pearlite
transformation.
The temperature dependence for an iron–carbon alloy of eutectoid
composition is indicated in Figure 10.12, which plots S-shaped curves of the
percentage transformation versus the logarithm of time at three different
temperatures.

For each curve, data were collected after rapidly cooling a specimen composed of
100% austenite to the temperature indicated; that temperature was maintained constant
throughout the course of the reaction
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Isothermal transformation diagram

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Rate of transformation
According to equation, the transformation rate at
some particular temperature is inversely
proportional to the time required for the reaction to
proceed to 50% completion (to the dashed line in
Figure 10.13).

That is, the shorter this time, the higher is the rate.

Thus, from Figure 10.13, at temperatures just below the eutectoid (corresponding
to just a slight degree of undercooling) very long times (on the order of 10 5 s) are
required for the 50% transformation, and therefore the reaction rate is very slow.

The transformation rate increases with decreasing temperature such that at

540℃(only about 3 s is required for the reaction to go to 50% completion
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Constrains on using Isothermal transformation

diagram

 First, this particular plot is valid only for an iron–carbon alloy of eutectoid
composition; for other compositions, the curves will have different configurations.
 In addition, these plots are accurate only for transformations in which the
temperature of the alloy is held constant throughout the duration of the reaction.
Conditions of constant temperature are termed isothermal; thus, plots such as
Figure10.13 are referred to as isothermal transformation diagrams, or
sometimes as time–temperature–transformation (or T–T–T) plots.
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Time Temperature Transformation (TTT) Diagram:

 TTT diagram is a plot of temperature versus the logarithm of time for a
steel alloy of definite composition.
 It is used to determine when
transformations begin and
end for an isothermal heat
treatment of a previously
austenitized alloy.

 TTT diagram indicates when

a specific transformation
starts and ends and it also
shows what percentage of
transformation of austenite
at a particular temperature
is achieved.
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3.5sec 15sec
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Absolute layer thickness of ferrite and cementite

The absolute layer thickness depends on the temperature at which the
isothermal transformation is allowed to occur.

Coarse pearlite:
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 10.14.

At these temperatures,
diffusion rates are relatively
high, such that during the
transformation carbon atoms
can diffuse relatively long
distances, which results in
the formation of thick
lamellae.
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Layer thickness-Fine pearlite

With decreasing temperature, the

carbon diffusion rate decreases,
and the layers become
progressively thinner. The
thin-layered structure produced in
the vicinity of is termed fine
Photomicrographs of fine pearlite
for a eutectoid composition are
shown in Figure 10.15.
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Isothermal transformation diagram for a 1.13 wt% C

iron–carbon alloy:
In addition to pearlite, other
microconstituents that are products of the
austenitic transformation exist; one of these
is called bainite.

Bainite:
The microstructure of bainite
consists of ferrite and cementite
phases, and thus diffusional processes
are involved in its formation.
 Bainite forms as needles or plates,
depending on the temperature of A, austenite; C,
the transformation. proeutectoid cementite;
P, pearlite.
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Microstructural details of Bainite

Figure 10.17 is an electron
micrograph that shows a grain of bainite
(positioned diagonally from lower left to
upper right); it is composed of a ferrite
matrix and elongated particles of Fe3C; the
various phases in this micrograph have
been labeled.
In addition, the phase that
surrounds the needle is martensite, the
topic to which a subsequent section is
addressed. Furthermore, no proeutectoid
phase forms with bainite.
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Time- Temperature dependence of bainite

transformation
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 10.18, 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” at point N,
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 to 727℃, at
temperatures between about
215 and 540℃, 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.
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Spheroidite
If a steel alloy having either pearlitic or bainitic
microstructures is heated to, and left at, a
temperature below the eutectoid for a sufficiently
long period of time—for example, at about 700℃
for between 18 and 24 h—yet another
microstructure will form. It is called spheroidite
(Figure 10.19).
Instead of the alternating ferrite and cementite
lamellae (pearlite), or the microstructure
observed for bainite, the Fe3C phase appears as
sphere-like particles embedded in a continuous α
phase matrix.
This transformation has occurred by additional
carbon diffusion with no change in the
compositions or relative amounts of ferrite and
cementite phases. The driving force
for this transformation is the reduction in –Fe3
C phase boundary area.
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Martensite
o Yet another microconstituent or phase
called martensiteis formed when
austenitized iron–carbon alloys are rapidly
cooled (or quenched) to a relatively low
temperature (in the vicinity of the ambient).
o Martensite is a non-equilibrium single-phase
structure that results from a diffusionless
transformation of austenite.
o It may be thought of as a transformation
product that is competitive with pearlite and
bainite.
o 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.
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Martensitic transformation
The martensitic transformation is not well understood. However, 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 10.20)

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.
Many steels, however, retain their martensitic
structure almost indefinitely at room
temperature.
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Austenite-Martensite transformation
The austenite-to-martensite transformation
is, however, represented on the isothermal
transformation diagram.
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 10.22). 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.
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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 a thermal transformation

Consider an alloy of eutectoid composition

that is very rapidly cooled from a
temperature above 727℃ to, say, 165℃.
From the isothermal transformation
diagram (Figure 10.22) it may be noted that
50% of the austenite will immediately
transform to martensite; and as long as this
temperature is maintained, there will be no
further transformation
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Presence of alloying elements

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)
(2) the formation of a separate bainite
nose.
These alterations may be observed by
comparing Figures 10.22 and 10.23,
which are isothermal transformation
diagrams for carbon and alloy steels,
respectively
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Summary
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Time Temperature Transformation (TTT) Diagram:

 Depending on the type of heat treatment, time and temperature, final

microstructure of the steel, or any Iron carbon will be changed and so does
the properties.

Martensite
T Martensite
Strength

Ductility

Bainite
Fine Pearlite
Coarse Pearlite
Spheroidite
General Trends
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Time Temperature Transformation (TTT) Diagram:

Iron-carbon alloy
with Eutectoid
(0.76 % C)
composition.

 A: Austenite
 P: Pearlite
 B: Bainite
 M: Martensite
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Time Temperature Transformation (TTT) Diagram:
Example 1:
c11f23
 Iron-carbon alloy with
eutectoid composition.

 Specify the nature of the

final microstructure (%
bainite, martensite, pearlite
etc) for the alloy that is Bainite,
subjected to the following 100%
time–temperature
treatments:

 Alloy begins at 760˚C and

has been held long enough
to achieve a complete and
homogeneous austenitic
structure.

 Treatment (a)
 Rapidly cool to 350 ˚C
 Hold for 104 seconds
 Quench to room temperature
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Time Temperature Transformation (TTT) Diagram:
Example 2:

c11f23 alloy
 Iron-carbon with
eutectoid composition.

 Specify the nature of the

final microstructure (%
bainite, martensite, pearlite
etc) for the alloy that is
subjected to the following
time–temperature
treatments:
Austenite,
 Alloy begins at 760˚C and 100%
has been held long enough
to achieve a complete and
homogeneous austenitic
structure.

 Treatment (b) Martensite,

 Rapidly cool to 250 ˚C 100%
 Hold for 100 seconds
 Quench to room temperature
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Time Temperature Transformation (TTT) Diagram:
 Example 3:

c11f23
 Iron-carbon alloy with eutectoid
Austenite,
100%
composition. Almost 50% Pearlite,
50% Austenite
 Specify the nature of the final
microstructure (% bainite,
martensite, pearlite etc) for the
alloy that is subjected to the
following time–temperature
treatments: Bainite, 50%
 Alloy begins at 760˚C and has
been held long enough to achieve
a complete & homogeneous
austenitic structure.

 Treatment (c)
 Rapidly cool to 650˚C Final:
 Hold for 20 seconds 50% Bainite,
50% Pearlite
 Rapidly cool to 400˚C
 Hold for 103 seconds
 Quench to room temperature
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solution
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3.2.Continuous Cooling Transformation (CCT)

Superimposition of isothermal and continuous cooling

transformation diagrams for a eutectoid iron–carbon alloy
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3.2.Continuous Cooling Transformation (CCT)

Moderately rapid and slow cooling curves superimposed on a continuous

cooling transformation diagram for a eutectoid iron–carbon alloy.
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3.2.Continuous Cooling Transformation (CCT)

Continuous cooling transformation diagram for a eutectoid iron–carbon

alloy and superimposed cooling curves, demonstrating the dependence of
the final microstructure on the transformations that occur during cooling
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For the continuous

cooling of a steel alloy,
there exists a critical
quenching rate,
which represents the
minimum rate of
quenching that
produces a totally
martensitic
structure.
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Problem
• Name the microstructural products of 4340 alloy steel specimens that are first completely
transformed to austenite, then cooled to room temperature at the following rates: (a) 10°C/s (b)
1°C/s (c) 0.1°C/s (d) 0.01°C/s.
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Problem
Name the microstructural products of 4340 alloy steel specimens that are first
completely transformed to austenite, then cooled to room temperature at the
following rates: (a) 10°C/s (b) 1°C/s (c) 0.1°C/s (d) 0.01°C/s.
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Name the microstructural products of 4340 alloy steel specimens that are first
completely transformed to austenite, then cooled to room temperature at the
following rates: (a) 10°C/s (b) 1°C/s (c) 0.1°C/s (d) 0.01°C/s.
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Mechanical behavior of Iron-Carbon alloy

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Mechanical behavior of Iron-Carbon alloys

Cementite is much harder but more brittle than ferrite. Thus, increasing the fraction
of Cementite in a steel alloy while holding other microstructural elements constant will
result in a harder and stronger material.
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The layer thickness of each of the ferrite and cementite phases in the microstructure
also influences the mechanical behavior of the material. Fine pearlite
is harder and stronger than coarse pearlite, as demonstrated in Figure 10.30a, which
plots hardness versus the carbon concentration.
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The reasons for this behavior relate to phenomena that occur at the α-Fe3C –
phase boundaries.

First, there is a large degree of adherence between the two phases across a
boundary. Therefore, the strong and rigid cementite phase severely restricts
deformation of the softer ferrite phase in the regions adjacent to the boundary;
thus the cementite may be said to reinforce the ferrite.

The degree of this reinforcement is substantially higher in fine pearlite because of

the greater phase boundary area per unit volume of material. In addition, phase
boundaries serve as barriers to dislocation motion in much the same way as grain
boundaries (Section 7.8).

For fine pearlite there are more boundaries through which a dislocation must
pass during plastic deformation. Thus, the greater reinforcement and restriction
of dislocation motion in fine pearlite account for its greater hardness and
strength.

Coarse pearlite is more ductile than fine pearlite, as illustrated in Figure 10.30b,
which plots percentage reduction in area versus carbon concentration for both
microstructure types. This behavior results from the greater restriction to plastic
deformation of the fine pearlite.
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Spheroidite
The cementite phase has distinctly different shapes
and arrangements in the pearlite
and spheroidite microstructures (Figures).
 Alloys containing pearlitic microstructures have
greater strength and hardness than do those
 with spheroidite. This is demonstrated in Figure
10.30a, which compares the hardness as a
function of the weight percent carbon for
spheroidite with both the other pearlite structure
types.

This behavior is again explained

in terms of reinforcement at, and impedance to,
dislocation motion across the
ferrite–cementite boundaries as discussed
above. There is less boundary area per
unit volume in spheroidite, and consequently
plastic deformation is not nearly as
constrained, which gives rise to a relatively soft
and weak material.

In fact, of all steel alloys, those that are softest and

weakest have a spheroidite microstructure.
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Bainite
Bainitic steels have a finer structure (i.e., smaller α -ferrite and Fe3C particles),
they are generally stronger and harder than pearlitic ones; yet they exhibit a
desirable combination of strength and ductility.

Figure 10.31 shows the influence of

transformation temperature on the tensile strength and
hardness for an iron–carbon alloy of eutectoid composition;
temperature ranges over which pearlite and bainite form.
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Martensite
Martensite is the hardest
and strongest and, in
addition, the most brittle;
it has, in fact, negligible
ductility.
Its hardness is dependent
on the carbon content, up
to about 0.6 wt% as
demonstrated in Figure
10.32, which plots the
hardness of martensite
and fine pearlite as a
function of weight percent
carbon.
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Martensite Property

In contrast to pearlitic steels, strength and hardness of martensite are not thought
to be related to microstructure. Rather, these properties are attributed to the
effectiveness of the interstitial carbon atoms in hindering dislocation motion (as a
solid-solution effect, and to the relatively few slip systems (along which dislocations
move) for the BCT structure.

Austenite is slightly denser than martensite, and therefore, during the phase
transformation upon quenching, there is a net volume increase. Consequently,
relatively large pieces that are rapidly quenched may crack as a result of internal
stresses; this becomes a problem especially when the carbon content is greater
than about 0.5 wt%
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