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PHASE DIAGRAM-II
Dr. Aneela Wakeel
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Volume fractions of phases

• For multiphase alloys, it is often more convenient to
specify relative phase amount in terms of volume fraction
rather than mass fraction.
• Phase volume fractions are preferred because they
(rather than mass fractions) may be determined from
examination of the microstructure; furthermore, the
properties of a multiphase alloy may be estimated on the
basis of volume fractions.
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Conversion from mass fraction to volume fraction and

vice verse

Composition
in wt%

Composition
in at%
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Example
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solution
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Example
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SOLUTION
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Volume fraction
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Solution(9.15)
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Development of microstructure in Eutectic

alloys
First case (C1)

Alloy of composition
2wt%Sn-98wt%Pb
at 350℃ slowly
cooled down – shown
by dashed vertical line
ww′.
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The second case considered is for compositions that range between the room
temperature solubility limit and the maximum solid solubility at the eutectic
temperature. For the lead–tin system (Figure 9.8), these compositions extend from
about 2 wt% Sn to 18.3 wt% Sn (for lead-rich alloys) and from 97.8 wt% Sn to
approximately 99 wt% Sn (for tin-rich alloys).
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Microstructural development
Second Case (C2)

Examine an alloy of composition

as it is cooled along the vertical
line in Figure (XX′).
Upon crossing the solvus line, the
solid solubility is exceeded, which
results in the formation of small -
phase particles; these are
indicated in the microstructure
inset at point g. With continued
cooling, these particles will grow
in size because the mass fraction
of the phase increases
slightly with decreasing
temperature.
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Microstructural development
Third case (C3)

Consider an alloy
having this
composition that
is cooled from
a temperature
within the liquid-
phase region
(e.g.250℃, )
down the vertical
line yy′.
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Eutectic structure
Solidification at the eutectic composition

Compositions of αand βphases

are very different →the
eutectic reaction involves
redistribution of Pb and Sn
atoms by atomic diffusion.
This simultaneous formation of
α and β phases result in a
layered (lamellar) Photomicrograph showing
microstructure that is the microstructure of a lead–tin alloy of
called the eutectic structure eutectic composition. This microstructure
consists of alternating layers of a lead rich
-phase solid solution (dark layers),
and a tin-rich -phase solid solution(light
layers)
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Eutectic structure
The microstructural change that accompanies this eutectic transformation is
represented schematically in Figure 9.15; here is shown the layered eutectic
growing into and replacing the liquid phase

The arrows indicate the directions of

diffusion of lead and tin atoms; lead
atoms diffuse toward the α -phase layers
since this phase is lead-rich (18.3 wt%Sn
–81.7 wt% Pb); conversely, the direction of
diffusion of tin is in the direction of
the β, tin-rich (97.8 wt%Sn –2.2 wt% Pb)
layers. The eutectic structure forms in
these alternating layers because, for this
lamellar configuration, atomic diffusion of
lead and tin need only occur over relatively Figure 9.15 Schematic representation of
short distances. the formation of the eutectic structure
for
the lead–tin system. Directions of
diffusion
of tin and lead atoms are indicated by
blue and red arrows, respectively.
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Microstructural development
L →α+ L →α+β
Fourth Case (C4)

To distinguish one from the

other, that which resides in
the eutectic
structure is called eutectic
while the other that formed
prior to crossing the
eutectic isotherm is termed
primary both are labeled in
Figure 9.16.
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Primary and eutectic alpha

The photomicrograph in Figure 9.17 is of a lead–tin alloy in which both primary
and eutectic structures are shown.

The eutectic structure is a microconstituent even though it is a mixture of two

phases, because it has a distinct lamellar structure, with a fixed ratio of the
two phases.
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How to calculate relative amount of

microconstituent
The fraction of
the eutectic
microconstituent is just
the same as the fraction
of liquid from
which it transforms, or
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Relative amount of microconstituent

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Binary eutectic System

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Problem 9.32

Cα Ce Co Cβ
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Solution
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Problem 9.13
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Solution

C0
Cγ
Cβ
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Solution
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Problem 9.33
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Solution
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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