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

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 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 3: No abrupt liquid-to-solid
Example: Chip-Solder-Joint-Failure
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)

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 One-Component Phase Diagrams
# of state variables (e.g. two: P and T)

Gibbs Phase rule: F=CP+2

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

F=1

F=0

Two-Component Phase Diagrams

Isomorphous system
( complete solubility over the
F=1 composition range)

T F=CP+1

If pressure is fixed (1 atm)

In a two-phase field need to

specify either the temperature
or the composition of one of the
F=2 phases.

Hume-Rothery Rules for

substitutional solution:
The size < ~15%.
The electronegativities and valance
similar
Xs Xl The crystal structures of the two species
must be the same to form a continuous
series of solid solutions.

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 Two-Component Phase Diagrams
fl + f s = 1
X o = X l fl + X s f s
fl = 1 f s
X o = X l (1 f s ) + X s f s
Temperature

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

fs =
( Xo Xl )
( Xs Xl )
fl =
( Xs Xo )
( Xs Xl )
Composition, XB

The Lever Rule in a Two-Component System

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 Two-Component
Phase Diagrams

Two-Component Phase Diagrams

Temperature, C

Time Time
Composition, XB

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 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

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 Eutectic Phase Diagrams

TA F=2
Xs Xl TB
T T
Xl Xs
F=1 F = 2, must
specify temperature
F=1 and composition
Temperature

F=2 F = 1, must
F=2 X F=0 X
specify temperature
or the composition
F=1 Solvus of one of the phases
F = 0, temperature
T X and compositions
X of the phase are
fixed.
A X1 XE X2 B
Composition, XB

Cooling Curves and Phase Boundaries

Alloy 1
Temperature

Time

Composition, XB

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 Cooling Curves and Phase Boundaries
Alloy 2
Temperature

Time

Composition, XB

Cooling Curves and Phase Boundaries

Alloy 3
Temperature

Time

Composition, XB

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Various physical
properties and their
relationship to a
eutectic phase
diagram

Eutectic Phase Diagrams

1. For the alloy composition of

0.27 % B calculate the fraction of
Temperature

solid and the fraction of liquid that

forms under equilibrium cooling at
the eutectic T

Composition, in % B

2. Calculate the amount of and 3. Calculate the amount of in the

that will form from the liquid just alloy at temperature just below the
below the eutectic isotherm eutectic T

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 Eutectic Phase Diagrams
Just above the eutectic
temperature the fraction
of liquid and solid are:
Temperature

0.27 0.20 0.37 0.27

fl f
0.37 0.20 0.37 0.20
fl 0.41 f 0.59

The first solid that forms

is called primary
Just below the eutectic temperature
Composition, in % B
the microstructure is composed of
This liquid becomes the primary that formed above the
eutectic mixture of and eutectic temperature and from
when the temperature the eutectic mixture
drops just below the eutectic
ftotal = f primary + feutectic
temperature which is composed
of: 0.73 0.37 0.37 0.20 ftotal = 0.59 + (0.41)(0.68) = 0.87
f f
0.73 0.20 0.73 0.20 0.73 0.27 f = 0.87
or f =
f 0.68 f 0.32 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 primary

Decreasing eutectic Increasing eutectic

Deviation from Hume-Rotherys Rules

Temperature

Increasing deviation leads to decrease

in the maximum solid solubility of B in .

A Composition, XB

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 Eutectic Phase Diagram, No Solid Solubility

Temperature

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

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 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 + =
TA
Temperature

TL

TP

X2 XP X2
Composition, XB Time

Analysis of a Peritectic Phase Diagram

Alloy 1 Alloy 2 Alloy 3

Alloy 3 at T2
Temperature

0.88 0.60
fl =
0.88 0.3
f l = 0.48

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

Composition

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 Monotectic Phase Diagrams

L1 L2 A region of immiscibility (non-

mixing) develops in the L phase
example: oil and water
Liquid1 = Liquid2 + (solid)
L2

L2

XM

Review of Invariant Binary Reactions

Eutectic Type

Eutectic l Al-Si, Fe-C

l +

Eutectoid
Fe-C
+

Monotectic l1
l2 Cu-Pb
l1 + l2

Monotectoid 2
1 Al-Zn, Ti-V
2 1 +

On cooling one phase going to two phases

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 Review of Invariant Binary Reactions
Peritectic Type

Peritectic Fe-C
l
l+

Peritectoid 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

TB

1. Label all
phase fields.
2. Identify all
invariant
Temperature

reactions.

TA

A Composition, XB B

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 Labeling Complex Phase Diagrams

Eutectic
Eutectic l = +
Peritectic
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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