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PHASE DIAGRAM-Ⅳ
Dr. Aneela Wakeel
02-01-2018
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Equilibrium Diagrams Having Intermediate Phases Or

Compounds

The eutectic copper–silver and lead–tin phase diagrams have only

two solid phases, α and β these are sometimes termed terminal solid
solutions, because they exist over composition ranges near the
concentration extremities of the phase diagram.
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Copper-Zinc Phase Diagram

For other alloy systems, intermediate solid solutions (or intermediate phases)
may be found at other than the two composition extremes. Such is the case for
the copper–zinc system.
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Intermediate solid solution

There are some invariant points and reactions similar to the eutectic

In addition, there are

six different solid
solutions—two terminal
(α and η) and four
intermediate (β, γ, 𝛿
and ε ). (The 𝛽ሖ phase
is termed an ordered
solid solution, one in
which the copper and
zinc atoms are situated
in a specific and
ordered arrangement
within each unit cell.)

Some phase boundary lines near the bottom of Figure 9.19 are dashed to indicate that their
positions have not been exactly determined. The reason for this is that at low temperatures,
diffusion rates are very slow and in ordinately long times are required to attain equilibrium.
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Intermetallic Compounds
For some systems, discrete intermediate compounds rather than solid solutions
may be found on the phase diagram, and these compounds have distinct
chemical formulas; for metal–metal systems, they are called intermetallic
compounds.

Mg2Pb has a composition of

19 wt% Mg–81 wt% Pb (33
at% Pb), and is represented
as a vertical line on the
diagram, rather than as a
phase region of finite width;
hence,Mg2Pb can exist by
itself only at this precise
composition.

First, the compound Mg2Pb

melts at approximately 550℃
(1020F), as indicated by point
M in Figure 9.20.
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Characteristic of magnesium–lead system

The solubility of lead in
magnesium is rather
extensive, as indicated by
the relatively large
composition span for the α-
phase field. On the other
hand, the solubility of
magnesium in lead is
extremely limited. This is
evident from the very
narrow β terminal solid-
solution region on the right
or lead-rich side of the
diagram.

Finally, this phase diagram may be thought of as two simple eutectic diagrams joined
back to back, one for the Mg–Mg2Pb system and the other for Mg2Pb–Pb; as such,
the compound Mg2Pb is really considered to be a component.
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Eutectoid and peritectic reactions

In addition to the eutectic, other invariant points involving three different phases are
found for some alloy systems. One of these occurs for the copper–zinc system
(Figure 9.19) at 560C (1040F) and 74 wt% Zn–26 wt% Cu. A portion of the phase
diagram in this vicinity appears enlarged in Figure 9.21. Upon cooling,
a solid phase transforms into two other solid phases according to the
reaction

The reverse reaction occurs

upon heating. It is called a
eutectoid (or eutectic-like)
reaction, and the invariant point
(point E, Figure 9.21) and the
horizontal tie line
at 560C are termed the eutectoid
and eutectoid isotherm,
respectively.
The feature distinguishing “eutectoid” from “eutectic” is that one solid phase
instead of a liquid transforms into two other solid phases at a single temperature.
A eutectoid reaction is found in the iron–carbon system (Section 9.18) that is very
important in the heat treating of steels.
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Peritectic reaction
The peritectic reaction is yet another invariant reaction involving
three phases at equilibrium. With this reaction, upon heating,
one solid phase transforms into a liquid phase and another solid
phase.

A peritectic exists for

the copper–zinc
system (Figure 9.21,
point P) at 598℃
(1108F) and 78.6 wt%
Zn–21.4 wt% Cu; this
reaction is as follows:
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One of the latter peritectics exists at about 97 wt% Zn and 435C (815F) (see
Figure 9.19), where in the η phase, when heated, transforms to εand liquid
phases.

Three other
peritectics are
found for the Cu–
Zn system, the
reactions of which
involve β,𝛿 𝑎𝑛𝑑 γ
intermediate solid
solutions as the
low-temperature
phases that
transform upon
heating.
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CLASSIFICATION OF THREE-PHASE EQUILIBRIA

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Congruent phase transformation

Phase transformations may be classified according to whether there is any
change in composition for the phases involved.

Those for which there are no

compositional alterations are said to be
congruent transformations. Examples
of congruent transformations include
allotropic transformations and melting
of pure materials.

Conversely, for incongruent

transformations, at least one of the
phases will experience a change in
composition. Eutectic and eutectoid
reactions, as well as the melting of an
alloy that belongs to an isomorphous
system, all represent incongruent
transformations.
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Gibbs phase rule

The construction of phase diagrams as well as some of the principles
governing the conditions for phase equilibria are dictated by laws of
thermodynamics.
One of these is the Gibbs phase rule, proposed by the nineteenth-
century physicist J. Willard Gibbs. This rule represents a criterion for
the number of phases that will coexist within a system at
equilibrium, and is expressed by the simple equation

where P is the number of phases present.

The parameter F is termed the number of degrees of freedom or the number of externally
controlled variables (e.g., temperature, pressure, composition) which must be specified to
completely define the state of the system or F is the number of these variables that can be
changed independently without altering the number of phases that coexist at equilibrium.

The parameter C in Equation 9.16 represents the number of components in the system.

Finally, N is the number of non compositional variables (e.g., temperature and pressure).
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Example of Gibbs rule for binary phase diagram

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Example of Gibbs rule for binary phase diagram

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The Iron-Carbon System

A portion of the iron–carbon phase diagram is presented in Figure.

Pure iron, upon heating,

experiences two changes in
crystal structure before it melts.

At room temperature the stable

form, called ferrite, or α iron,
has a BCC crystal structure.

Ferrite experiences a
polymorphic transformation to
FCC austenite, or γ iron, at
912℃.

This austenite persists to 1394℃,

at which temperature the FCC
austenite reverts back to a BCC
phase known as δ ferrite, which
finally melts at 1538℃.
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Iron-Iron Carbide
The composition axis in Figure
extends only to 6.70 wt% C; at
this concentration the
intermediate compound iron
carbide, or cementite(Fe3C), is
formed, which is represented by
a vertical line on the phase
diagram.

Thus, the iron–carbon system

may be divided into two parts:
an iron-rich portion, as in
Figure , and the other
(not shown) for compositions
between 6.70 and 100 wt% C
(pure graphite). In practice, all
steels and cast irons have
carbon contents less than
6.70 wt% C; therefore,
we consider only the iron–iron
carbide system
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BCC-α ferrite
Carbon is an interstitial impurity in iron and forms a solid solution with each of α
and δ ferrites, and also with austenite, as indicated by the α,δ and γ single phase
fields in Figure.

❑ In the BCC α ferrite, only small

concentrations of carbon are soluble; the
maximum solubility is 0.022 wt% at 727℃.
❑ The limited solubility is explained by the
shape and size of the BCC interstitial
positions, which make it difficult to
accommodate the carbon atoms. Even
though present in relatively low
concentrations, carbon significantly
influences the mechanical properties of
ferrite.
❑ This particular iron–carbon phase is
relatively soft, may be made magnetic at
temperatures below 768℃, and has a
density of 7.88 g/cm3

Figure is a photomicrograph of α ferrite

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Austenite-γ phase (FCC)

❑ The austenite, or γ phase of iron, when
alloyed with carbon alone, is not stable
below 727℃, as indicated in Figure.
❑ The maximum solubility of carbon in
austenite, 2.14 wt%, occurs at 1147℃.
This solubility is approximately 100 times
greater than the maximum for BCC ferrite,
since the FCC interstitial positions are
larger, therefore, the strains imposed on
the surrounding iron atoms are much
lower.
❑ As the discussions that follow
demonstrate, phase transformations
involving austenite are very important in
the heat treating of steels. In passing, it
should be mentioned that austenite is
nonmagnetic. Figure shows a photomicrograph of
. this austenite phase
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BCC- 𝛿Ferrite
The ferrite is
virtually the same
as ferrite, except
for the range of
temperatures
over which each
exists. Since the
ferrite is stable
only at relatively
high
temperatures, it
is of no
technological
importance and
is not discussed
further.
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Cementite (Fe3C)
Cementite (Fe3C) forms when the
solubility limit of carbon in α ferrite is
exceeded below 727℃ (for
compositions within the Fe3C phase
region).
As indicated in Figure, Fe3C will also
coexist with the γ phase between
727℃ and 1147℃.

Mechanically, cementite is very hard

and brittle; the
strength of some steels is greatly
enhanced by its presence

cementite is only metastable; that

is, it will remain as a compound
indefinitely at room temperature.

However, if heated to between 650 and 700℃ for several years, it will gradually change or
transform into iron and carbon, in the form of graphite, which will remain upon subsequent
cooling to room temperature.
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Eutectic reaction
It may be noted that one eutectic exists for the iron–iron carbide system, at 4.30 wt%
C and ); for this eutectic reaction,

the liquid solidifies to form

austenite and cementite
phases. Of course,
subsequent cooling to room
temperature will promote
additional phase changes.
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Eutectoid reaction
It may be noted that a eutectoid invariant point exists at a composition of 0.76
wt%C and a temperature of 727℃.This eutectoid reaction may be represented
by

or, upon cooling, the solid phase

is transformed into iron and
cementite. The eutectoid phase
changes described by Equation
are very important, being
fundamental to the
heat treatment of steels
The peritectic reaction is yet
another invariant reaction
involving three phases
at equilibrium. With this reaction,
upon heating, one solid phase
transforms into a
liquid phase and another solid
phase. A peritectic exists for the
copper–zinc system
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Classification of ferrous alloy based on Carbon

content
Ferrous alloys are those in which iron is the prime component, but carbon as
well as other alloying elements may be present.

There are three types: iron, steel, and cast iron.

Commercially pure iron contains less than 0.008 wt% C and,
from the phase diagram, is composed almost exclusively of the
ferrite phase at room temperature.

The iron–carbon alloys that contain between 0.008 and 2.14 wt% C are classified
as steels. In most steels the microstructure consists of both α and Fe3C phases.
Upon cooling to room temperature, an alloy within this composition range must
pass through at least a portion of the γ -phase field; distinctive microstructures
are subsequently produced. Although a steel alloy may contain as much
as 2.14 wt% C, in practice, carbon concentrations rarely exceed 1.0 wt%.

Cast irons are classified as ferrous alloys that contain between 2.14 and
6.70 wt% C. However, commercial cast irons normally contain less than
4.5 wt% C.
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Development of microstructure in Fe-C

alloys- Very slow cooling
Microstructure
First case develops depend
on both the carbon
content and heat
treatment
For example, an alloy of
eutectoid composition
(0.76 wt% C) as it is
cooled from a temperature
within the γ phase region,
say, —that is, beginning at
point a, the alloy is
composed entirely of the
austenite phase having
a composition of 0.76 wt%
C and corresponding
microstructure, also
indicated in
Figure
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Pearlite Microstructure
Upon crossing this temperature to point b, the austenite transforms according to
Equation

The microstructure for this eutectoid steel

that is slowly cooled through the
eutectoid temperature consists of
alternating layers or lamellae of the two
phases (α and Fe3C) that form
simultaneously during the transformation.
In this case, the relative layer thickness is
approximately 8 to 1. This microstructure,
represented schematically in Figure, point
b, is called pearlite because it has the
appearance of mother of pearl when
viewed under the microscope at low
magnifications.
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Pearlite Microstructure
Figure 9.27 is a photomicrograph of a eutectoid
steel showing the pearlite.
The pearlite exists as grains, often termed
“colonies”; within each colony the layers
are oriented in essentially the same direction,
which varies from one colony to another.

The thick light layers are the ferrite phase, and the
cementite phase appears as thin lamellae most of
which appear dark.
Many cementite layers are so thin that adjacent
phase boundaries are so close together that they
are indistinguishable at this magnification, and,
therefore, appear dark.

Mechanically, pearlite has properties intermediate

between the soft, ductile ferrite and the hard, brittle
cementite.
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Carbon diffusion in pearlite

The alternating α and Fe3C layers in pearlite form as such for the same reason
that the eutectic structure forms—because the composition of the parent phase [in
this case austenite (0.76 wt% C)] is different from either of the product phases
[ferrite (0.022 wt% C) and cementite (6.7 wt%C)], and the phase transformation
requires that there be a redistribution of the carbon by diffusion.

Figure 9.28 illustrates schematically

microstructural changes that accompany
this eutectoid reaction; here the directions
of carbon diffusion are indicated by arrows.
Carbon atoms diffuse away from the 0.022
wt% ferrite regions and to the 6.7 wt%
cementite layers, as the pearlite extends
from the grain boundary into the unreacted
austenite grain.
The layered pearlite forms because carbon
atoms need diffuse only minimal distances
with the formation of this structure.
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Hypoeutectoid Alloys
Consider a composition to the left of the eutectoid, between 0.022 and 0.76
wt% C; this is termed a hypoeutectoid (less than eutectoid) alloy.
At point c, the microstructure will
consist entirely of grains of the γ
phase

In cooling to point d, which is

within the α+γ phase region. Most
of the small α particles will form
along the original grain
boundaries.
The compositions determined
using the tie line; these
compositions correspond,
respectively, to about 0.020 and
0.40 wt% C.
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Hypoeutectoid Alloys
Cooling from point d to e, just above
the eutectoid but still in the α+γ
region, will produce an increased
fraction of the α phase and a
microstructure similar to that also
shown: the α particles will have
grown larger.
At this point, the compositions of
the α phase will contain 0.022 wt%
C, while the γ phase will be of the
eutectoid composition, 0.76 wt% C

As the temperature is lowered just

below the eutectoid, to point f, all
the phase that was present at
temperature (and having the
eutectoid composition)
will transform to pearlite.
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Proeutectoid ferrite
The microstructure at point f will appear as the
corresponding schematic inset of Figure. Thus the ferrite
phase will be present both in the pearlite and also as the
phase that formed while cooling through the α +γ phase
region.
The ferrite that is present in the pearlite is called eutectoid
ferrite, whereas the other, that formed above is termed
proeutectoid (meaning pre- or before eutectoid) ferrite, as
labeled in Figure

Figure 9.30 is a photomicrograph of

a 0.38 wt% C steel; large, white
regions correspond to the
proeutectoid ferrite.
For pearlite, the spacing between
the α and Fe3C layers varies
from grain to grain; some of the
pearlite appears dark because the
many close spaced layers are
unresolved at the magnification of
the photomicrograph.
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Relative amounts of proeutectoid α and

pearlite
Fraction of pearlite

Fraction of proeutectoid
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Hypereutectoid alloys
Hypereutectoid alloys are those containing between 0.76 and 2.14 wt% C,
which are cooled from temperatures within the γ phase field.

Consider an alloy of composition

C1, upon cooling as shown by
moves down the line.
At point g only the γ phase will
be present with a composition
having only γ grains.
Upon cooling into the γ +Fe3C
phase field, to point h—the
cementite phase will begin to
form along the initial grain
boundaries.
This cementite is called
proeutectoid cementite— that
which form before the
eutectoid reaction.
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Proeutectoid Cementite
Proeutectoid cementite composition remains
constant (6.70 wt% C) as the temperature changes.
However, the composition of the austenite phase will
move along line PO toward the eutectoid.
As the temperature is lowered through the eutectoid
to point i, all remaining austenite of eutectoid
composition is converted into pearlite; thus, the
resulting microstructure consists of pearlite and
proeutectoid cementite as microconstituents .
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Relative amount of pearlite and

proeutectoid cementite
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Example 9.4
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Problem 9.50
Q:Consider 3.5kg of austenite containing 0.95wt%C, cooled
to below 727degree C(998K).
• What is the proeutectoid phase?
• How many kilograms of each of total ferrite and cementite
form?
• How many kilograms of each of pearlite and proeutectoid
phase form?
• Schematically sketch and label the resulting microstructure.
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Solution
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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