Chapter 7 Phase Equilibria and Phase

Diagrams
The one-component phase diagram
Gibbs Phase Rule

Phase equilibria in a two-component system

The isomorphous diagram
The lever rule
Equilibrium solidification and microstructure of
isomorphous alloys
Liquidius and solidus boundaries
Deviations from ideal behavior

Chapter 7 Phase Equilibria and Phase

Diagrams, Continued
Phase equilibria in a two-component system

The eutectic phase diagram

The peritectic phase diagram
The monotectic phase diagram
Complex diagrams
Phase equilibria involving solid-to-solid reactions

Why important ?
Some properties that might be difficult to predict using a
common sense without the knowledge of the phase diagrams
example 1: Melting temperature of a
mixture AB (solution) of two components A
and B could be either lower or higher than
the melting point of each component (!).
This could be a failure mechanism in
electronic or mechanical components. But
could also be used to your advantage.
example 2: Upon cooling to a lower
temperature a phase transformation of a
material could cause expansion, which
could cause internal stresses and failure
(e.g. tin food cans will crumble at low T)

Example: Chip-Solder-Joint-Failure

example 3: No abrupt liquid-to-solid

transformation when two components are
present (solid + liquid in a temperature range)

Why important ?
Some properties that might be difficult to predict using a
common sense without the knowledge of the phase diagrams
example 4: Tmelt (Sn) = 232 C, Tmelt (Pb) = 327 C
but Tmelt(Sn0.62Pb0.38) = 183 C, so this is a common soldering alloy
example 5: Tmelt (Au) = 1064 C, Tmelt (Si) = 2550 C
but Tmelt(Au0.97Si0.03) = 363 C, so thin layer of gold is used to attach Si chip
to a ceramic substrate (shock protection)
example 6: Mechanical properties (hardness and tensile strength) of an
alloy could be substantially higher than that of the individual components
(e.g. hardness (AgCu) about twice the harness of Ag or Cu)

One-Component Phase Diagrams

# of state variables (e.g. two: P and T)

F=CP+2
C- Components
P- Number of phases
F- Degrees of freedom

Gibbs Phase rule:

F=2

F=1

F=0

Two-Component Phase Diagrams

Isomorphous system
( complete solubility over the
composition range)

F=1

F=CP+1
If pressure is fixed (1 atm)

F=2

In a two-phase field need to

specify either the temperature
or the composition of one of the
phases.
Hume-Rothery Rules for
substitutional solution:

Xs

Xl

The size < ~15%.

The electronegativities and valance
similar
The crystal structures of the two species
must be the same to form a continuous
series of solid solutions.

Two-Component Phase Diagrams

fl + f s = 1
X o = X l fl + X s f s
fl = 1 f s

Temperature

X o = X l (1 f s ) + X s f s
X o = X l X l fs + X s fs

X o X l = fs ( X s X l )

( Xo Xl )
( Xs Xl )
( Xs Xo )
fl =
( Xs Xl )
fs =

Composition, XB

The Lever Rule in a Two-Component System

Two-Component
Phase Diagrams

Temperature, C

Two-Component Phase Diagrams

Time

Time

Composition, XB

Two-Component Phase Diagrams

Congruent melting maximum
EAB > 0.5 (EAA + EBB)

Deviation from ideal behavior

Two-Component Phase Diagrams

EAB > 0.5 (EAA + EBB)

Deviation from
ideal behavior

Congruent melting
minimum

Eutectic Phase Diagrams

TA

F=2

Temperature

F=1

Xs

Xl

F = 2, must
specify temperature
and composition

F=1
F=2

F=0

F=2

Solvus

F=1
T X

TB

Xl

Xs

X1

XE

Composition, XB

X2

F = 1, must
specify temperature
or the composition
of one of the phases
F = 0, temperature
and compositions
of the phase are
fixed.

Cooling Curves and Phase Boundaries

Temperature

Alloy 1

Time

Composition, XB

Cooling Curves and Phase Boundaries

Temperature

Alloy 2

Time

Composition, XB

Cooling Curves and Phase Boundaries

Temperature

Alloy 3

Time

Composition, XB

Various physical
properties and their
relationship to a
eutectic phase
diagram

Eutectic Phase Diagrams

Temperature

1. For the alloy composition of

0.27 % B calculate the fraction of
solid and the fraction of liquid that
forms under equilibrium cooling at
the eutectic T

Composition, in % B

2. Calculate the amount of and

that will form from the liquid just
below the eutectic isotherm

3. Calculate the amount of in the

alloy at temperature just below the
eutectic T

Eutectic Phase Diagrams

Temperature

Just above the eutectic

temperature the fraction
of liquid and solid are:
0.37 0.27
0.27 0.20
f
fl
0.37 0.20
0.37 0.20
f

0.59
fl 0.41

The first solid that forms

is called primary
Composition, in % B

This liquid becomes the

eutectic mixture of and
when the temperature
drops just below the eutectic
temperature which is composed
of:
0.37 0.20
0.73 0.37
f
f
0.73 0.20
0.73 0.20
f 0.32
f 0.68

Just below the eutectic temperature

the microstructure is composed of
primary that formed above the
eutectic temperature and from
the eutectic mixture

ftotal = f primary + feutectic

ftotal = 0.59 + (0.41)(0.68) = 0.87
or

f =

0.73 0.27 f = 0.87

0.73 0.20

Microstructure Above and Below the Eutectic

Temperature for an Off-Eutectic Alloy

Just above TE

Just below TE

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Microstructure Above and Below the Eutectic

Temperature for Off-Eutectic Alloys
Just below TE

Increasing primary
Decreasing eutectic

Decreasing primary
Increasing eutectic

Temperature

Deviation from Hume-Rotherys Rules

Increasing deviation leads to decrease

in the maximum solid solubility of B in .

Composition, XB

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Temperature

Eutectic Phase Diagram, No Solid Solubility

Composition, XB

Eutectic Phase Diagrams

Al-Si System

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Methods for Determining a Phase Diagram

Microstructure of an Aluminum-Silicon Alloy

Primary -aluminum

aluminum / silicon eutectic

13

Phase Diagrams Containing Two Eutectics

Line
compound

Possible to have several solid solution regions: e.g. 2 eutectic reactions and 3
solid solutions (, , and )
Note that upon cooling from T max at the alloy composition X there is a phase
change but no composition change (CONGRUENT melting)

Peritectic Phase Diagrams

if both the L and S phases have
a tendency to cluster, the liquidus
temperature increase and the
solidus temperature decreases
In addition, a miscibility gap
(region of non-mixing) appears
A progressive increase in the
clustering tendency leads to the
PERITECTIC phase diagram

l + =

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The Use of Cooling Curves for Determining a

Peritectic Phase Diagram

l + =
Temperature

TA

TL

TP

X2

XP

X2

Composition, XB

Time

Analysis of a Peritectic Phase Diagram

Alloy 1 Alloy 2

Alloy 3

Temperature

Alloy 3 at T2
0.88 0.60
0.88 0.3
f l = 0.48
fl =

Alloy 3 at T5
0.90 0.60
0.90 0.34
f = 0.54
f =

Composition

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Monotectic Phase Diagrams

A region of immiscibility (nonmixing) develops in the L phase

L2

L1

example: oil and water

Liquid1 = Liquid2 + (solid)
L2
L2

XM

Review of Invariant Binary Reactions

Eutectic Type
Eutectic
l +

Eutectoid

Monotectic
l1

+ l2

Monotectoid
2

1 +

l1

Al-Si, Fe-C

Fe-C

l2

Cu-Pb

Al-Zn, Ti-V

On cooling one phase going to two phases

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Review of Invariant Binary Reactions

Peritectic Type

Peritectic
l+

Peritectoid
+

Fe-C

Cu-Al

On cooling two phases going to one phase

HW Questions
1. When a solid melts congruently, the liquid and solid have different /
the same composition(s).
2. At constant temperature the fraction of the phases in a two-phase field
changes / remains the same when the overall composition of the alloy is
changed, but remains in the two-phase field.
3. Why would alloys close to the eutectic composition be suitable for
castings rather than alloy compositions far from the eutectic
composition?
4. On cooling when a two-phase liquid plus solid transforms to a solid
phase the transformation is eutectic / peritectic in nature.
5. On cooling the peritectoid reaction written symbolically has
one phase going to two / two phases going to one.

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HW Questions

At what T an alloy containing

88% B will start melting?

At what T it will completely

transform into liquid?

What is the composition of

phase for this alloy @ T8?

What is the maximum solid solubility of B in a and A in b? Whose rules apply

here?

For an alloy containing 88% B, calculate the fraction of the liquid and solid
phases and their compositions at temperature T3, T4, and T5

At a temperature just below the eutectic temperature, how much is primary ,

what is the total fraction of , and what is the fraction in the eutectic. (Alloy
composition is 88% B)

Labeling Complex Phase Diagrams

Temperature

TB
1. Label all
phase fields.
2. Identify all
invariant
reactions.
TA

Composition, XB

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Labeling Complex Phase Diagrams

Peritectic

Eutectic

Eutectic
l = +
Peritectic
l + =
Eutectic
l = +

Eutectic

Labeling Complex Phase Diagrams

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Summary
One-component phase diagrams with
temperature and pressure as the
experimental variables that affect equilibrium.
Introduction to the Gibbs Phase Rule and its
application to one-component systems.
Two-component systems and the rules that
govern the composition of the phases, the
number of phases and the amount of each
phase at equilibrium.
The applications of these rules to complex,
two-component systems illustrated that
regardless of how complex the phase
diagram appeared, the rules that were
developed could be easily applied.

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