Phase Equilibria

Introduction to Materials
Science and Engineering
Module 7: Phase Equilibria

Thomas H. Sanders, Jr.
Regents’ Professor
Lesson 1: Introduction
School of Material Science and Engineering

Introduction 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
– Liquidius and solidus boundaries
– Deviations from ideal behavior
– The eutectic phase diagram
– The peritectic phase diagram
– The monotectic phase diagram
– Complex diagrams
– Phase equilibria involving solid-to-solid reactions
2

Lesson 2: One Component Phase Diagrams and Gibbs

Phase Rule

One Component Phase Diagrams and Gibbs Phase Rule
F=C–P+2
Phase Diagram of water C- Components
100 s/l
Liquid P- Number of phases
Pressure (atm)
F- Degrees of freedom
mp bp
1
Solid l/v
P1
0.1 Vapor
s/v tp
-20 0 20 40 T1 60 80 100
Temperature (oC)
11
F=C–P+2
Phase Diagram of Water C- Components
100 s/l
Liquid P- Number of phases
F=1
Pressure (atm)
F=2 F- Degrees of freedom

F = 2, single phase field
1 F = 1, two phase field
Solid l/v F = 0, three phase field
F=0
F=2 F=1
0.1 F=1 Vapor
s/v tp F=2
-20 0 20 40 60 80 100
Temperature (oC)
9
Phase Diagram of water Psat the saturated vapor

100
Liquid pressure at temperature T1
Pressure (atm)
Solid
1
l/v
T1 Isotherm
P1 Psat
0.1 Vapor Region of two phase
tp equilibrium
-20 0 20 40 T1 60 80 100 Vl Vv
Temperature (oC) Volume
10

Lesson 3: Region of Two Phase Equilibrium

Region of Two Phase Equilibrium
Compressing the gas at temperature

T1 along the PV isotherm results in an
increase of the pressure in the cylinder.
T1
P P1, sat
L+V T1
V
Vl V VV
4
Continuing to decrease volume of the gas
beyond the two phase boundary results in
the appearance of water droplets on the
surface of the cylinder.
T1
P P1, sat
L+V T1
Vl V VV
4
Continuing to decrease the volume until
only liquid phase is present results in a
dramatic increase in pressure since the
liquid phase is incompressible.
T1
P P1, sat
L+V T1
Vl V VV
4
Path 2 Critical point

P
P2 L Path 1 T2
P1 S Psat
L+V T1
T T1 T2 Vl VV
V
4

Lesson 4: Additional One Component Phase Diagrams

Additional One Component Phase Diagrams
150
 Iron
Pressure (kbars)
100
- Iron
50 Iron
- Iron
Liquid
- Iron
400 800 1200 1600

Temperature (oC) 3
Additional One Component Phase Diagrams
- Crystobalite
Liquid
1
2- Tridymite
Pressure (atm)
-Quartz
1713 oC
1470 oC
Vapor
-Quartz
870 oC
573 oC
Temperature (oC) 5

Lesson 5: Binary Isomorphous Phase Diagrams

Binary Isomorphous Phase Diagrams
Isomorphous F=C–P+1
TA F=1 Liquidus Liquid In a single phase field
T F=2 both the composition of
Two phase region The phase and the
L+ temperature must be
S
specified.
In a two phase field
Solidus need to specify either
TB the temperature or
the composition of
F=2
one of the phases.
Solid Solution
A XB s XB l B
XB 11
In a single-phase field
Isomorphous the composition of the phase
TA is the composition of the alloy
Liquid In a two-phase field, the
amount of each phase and
L+
S the composition of each
phase can be determined
using a tie line and the
lever rule
TB
In a single-phase field
the composition of the phase
Solid Solution is the composition of the alloy
A XB B
5
Equilibrium Isomorphous
TA Cooling
Freezing range
of the alloy
L+
S
Equilibrium
Heating TB
A XB s XBo XB l B
XB 9

Lesson 6: The Lever Rule

The Lever Rule
fl  fs  1
X Bo  X Bl fl  X Bs fs
Alloy
fl  1  fs
Temperature
XBo
X Bo  X Bl  1  fs   X Bs fs
T1 L S X Bo  X Bl  X l fs  X Bs fs
Tie line
X Bo  X Bl  fs  X Bs  X Bl 
L+S
fs 
 X o
B  X Bl   Xs  Xo 
fl 
X s
B  X Bl   Xs  Xl 
A XBl XBo XBs B
XB
9
The Lever Rule
The Lever Rule
Composition of the
liquid for each alloy
Alloy 1- 0.2
T1 Alloy 2- 0.2
Alloy 3- 0.2
Temperature
Alloy 4- 0.2
Alloy 5- 0.2
Composition of the
solid for each alloy
Alloy 1- 0.8
Alloy 2- 0.8
Alloy 3- 0.8
Alloy 4- 0.8
Alloy 5- 0.8
A 0.2 XB 0.8 B 5
The Lever Rule
Isomorphous Alloy
Equilibrium TB
Temperature
Cooling
Freezing range
of the alloy
Liquid S
L +
Solid
TA
A XB l XBo XB s B
XB
7

Lesson 7: Phase Fractions

Phase Fractions
1 1
0.9 0.9
0.8 0.8
Fraction of liquid, f l
Fraction solid, fs
0.7 0.7
0.6 0.6
0.5 0.5
0.4 0.4
0.3 0.3
0.2 0.2
0.1 0.1
0 0
1000 1020 1040 1060 1080 1000 1020 1040 1060 1080
Temperature, C Temperature, C
Temp Xl Xs Xo fl fs Temp
1060 0.6 0.7 0.6 1 0 1060
1050 0.57 0.68 0.6 0.72727 0.272727 1050
1040 0.55 0.65 0.6 0.5 0.5 1040
1030 0.52 0.63 0.6 0.27273 0.727273 1030
1010 0.48 0.6 0.6 0 1 1010
3
Phase Fractions
T>T1 T1
T2 T3
T4 T5 T<T5
8

Lesson 8: Equilibrium Cooling Curves

Equilibrium Cooling Curves
G l  s   H l  s  T  S l  s
Sample Slope =
Inert reference G l  s  0
Furnace cooling rate
material H l  s  T S l  s
Temperature
S l  s  0
H l  s  0
T
Solidification of a The transformation
pure substance is exothermic
Time
6
Equilibrium Cooling Curves
Temperature, C
Time Time
Composition, XB
3

Lesson 9: Equilibrium Isomorphous Diagrams

Equilibrium Isomorphous Phase Diagrams
Liquid
Solid
Continuous solid
solution
Average
FCC FCC
6
Solid Solutions- Substitutional
Guidelines for solid solubility-Hume-Rothery’s Rules
• The size difference between the solute and
solvent must be no greater than ~15%.
• The electronegativities of the two atomic species
must be comparable.
• The valence of the two species must be similar.
• The crystal structures of the two species must
be the same. This is required if the alloy are to
form a continuous series of solid solutions.
Examples would be Cu-Ni and Si-Ge.
6
Equilibrium Isomorphous Phase Diagrams
Continuous solid solution
Sodium chloride structure

FCC unit cell with two ions
per lattice point
4

Lesson 10: Analysis of a Phase Diagram

Analysis of a Phase Diagram
TB
Liquid
Liquidus- Boundary that separates
dus
Temperature
qu i the single phase liquid from the

Li
L+S two phase liquid + solid region
Solidus- Boundary that separates
us
li d the single phase solid from the
So
two phase liquid + solid region
Solid
TA
A 20 40 60 80 B
Composition, %B
6
Temperature fl xl fs Xs
T1 1 0.6 0 0.85
Liquid T2 0.63 0.5 0.37 0.77
.85 T1 T3 0.44 0.45 0.56 0.72
T2
.45 .77 T3 T4 0.29 0.4 0.71 0.68
T4 .72
.68 T5 0 0.3 1 0.6
T5
Solid
0.40 0.60 0.80

XB
8
Temperature fl xl fs Xs At temperature T2
T1 1 0.6 0 0.85 0.77  0.60 0.60  0.50
T2 0.63 0.5 0.37 0.77 fl  fs 
0.77  0.50 0.77  0.50
T3 0.44 0.45 0.56 0.72
T4 0.29 0.4 0.71 0.68
fl  0.63 fs  0.37
T5 0 0.3 1 0.6
At temperature T3 At temperature T4
0.72  0.60 0.60  0.45 0.68  0.60 0.60  0.40
fl  fs  fl  fs 
0.72  0.45 0.72  0.45 0.68  0.40 0.68  0.40
fl  0.44 fs  0.56 fl  0.29 fs  0.71
5

Lesson 11: Deviations from Ideal Behavior

Deviations from Ideal Behavior
Liquidus
Solidus
X Bl  X Bs
Congruent melting
minimum
6
TA Congruent melting minimum
L
F=C–P+1
F=2
+
Liquid F=2
S
TB
F=1
Liquidus F=0
Temperature
S
+
T1 F=1 F=0
L
Solid
F=2
Solidus
Solid
A 20 XBs 40 XBl 60 80 B
9
Liquidus
Solidus
X Bl  X Bs
Congruent melting
maximum
6
3
TA Temperature fl Xl fs Xs
Liquid T1 1 0.3 0 0.1
L
+
T2 0.68 0.37 0.32 0.15

T1 0.1
S
TB T3 0.48 0.41 0.52 0.2

T2 0. 15 0.37 T4 0.25 0.45 0.75 0.25
T3 0. 20 0.41 T5 0 0.5 1 0.3
Temperature
T4 0.45
S
0. 25
0. 50
+
T5 0. 30
L
Solid
A 0.2 0.40 0.6 0.8 B

XB o
XB 9
Temperature fl Xl fs Xs At temperature T2
T1 1 0.3 0 0.1 0.30  0.15 0.37  0.15
T2 0.68 0.37 0.32 0.15 fl  fs 
0.37  0.15 0.37  0.15
T3 0.48 0.41 0.52 0.2
fl  0.68 fs  0.32
T4 0.25 0.45 0.75 0.25
T5 0 0.5 1 0.3
At temperature T3 At temperature T4
0.30  0.20 0.41  0.30 0.30  0.25 0.45  0.30
fl  fs  fl  fs 
0.41  0.20 0.41  0.20 0.45  0.25 0.45  0.25
fl  0.48 fs  0.52 fl  0.25 fs  0.75
5

Lesson 12: Eutectic Phase Diagram

Eutectic Phase Diagram
TA Eutectic from the Greek
meaning low melting point TB
Liq s
So uid i u
ius
lid Liquid iquid Label the phase fields
us L
Temperature
l
dus
l Label the invariant reaction
Soli

Eutectic isotherm  Label the phase boundaries
Solvu
s
lvu
So
s

A 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 B

XB 11
Alloy 1 Alloy 2 Alloy 3 Alloy 4 Alloy 5
T1
T2
T3
T4
T5
T6
T7
T8
T9
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 0.95
0.02 0.15 0.23 0.37 0.65 0.75 0.88 0.98
0.05 0.92
Temperature fl Xl f X f X
T4 1 0.5 0 0.23
T5 0.67 0.6 0.33 0.3
T6 0.47 0.65 0.53 0.37 0 0.9
T6 0 0.65 0.76 0.37 0.24
T7 0.68 0.3 0.32 0.92
T8 0.6 0.2 0.4 0.95
T9 0.55 0.1 0.45 0.98

Alloy 3, XBo = 0.5
3
T6 1 0.65 0 0.37 0 0.9
T7 0 0.44 0.3 0.56 0.92
T8 0.4 0.2 0.6 0.95
1. fl
0 f f 
T8 T7 T6
Alloy 4, XBo = 0.65

3

Lesson 13: Determination of Phase Boundaries

Determination of Phase Boundaries
Alloy 2 Alloy 3 Alloy 4
4
Choose any composition
in the two phase region
Establish thermal equilibrium
Determine the composition

of each phase two establish
the compositions of the
two phases in equilibrium
XB XB
5
Temperature
Increasing deviation from Hume-Rothery’s

rule leads to decrease in the maximum
solid solubility of B in .
A Composition, XB
3
Temperature
Composition, XB

Lesson 14: Eutectic Microstructure Development

Eutectic Microstructure Development
660.4oC
Liquid
Temperature, oC
600 +L
+L

548.2oC 
500 33
+
400
 
SEM image shows the 10 20 30 40 50
lamellar eutectic very clearly. Wt% Cu - Al2Cu
www.doitpoms.ac.uk › Micrograph Library, Prof. W.

Kurz
5
Based on experimental observations
Liquid
XE many eutectic alloys have alternating
structures of - and -lamellae.
 is rich in A and  is rich in B.
X X
At equilibrium the compositions of each of
  the phases are given by the eutectic portion
of the phase diagram
For the interface to advance the composition
XE in the liquid at the -phase must enrich in
component A, and the liquid in front of the
-phase must enrich in component B.
X X
6
This process occurs as the temperature
B
A drops below the eutectic temperature
Liquid/solid and the local compositions in the liquid
interface in front of the s/l interface change by
diffusion. The exact mechanism will be
    described in more details in the next
module covering kinetics.
3
T6 1 0.65 0 0.37 0 0.9
T7 0 0.44 0.3 0.56 0.92
T8 0.4 0.2 0.6 0.95
1. fl
0 f  f
T8 T7 T6
Just above TE Just below TE 4


Lesson 15: Equilibrium Cooling of an Off-Eutectic

Alloy

Hypoeutectic alloys Hypereutectic alloys

XE
l l
 
Eutectic present at the invariant temperature

for all compositions in this range
 is the primary solid  is the primary solid
phase to form phase to form
7
Equilibrium Cooling of an Off-Eutectic Alloy
Alloy 1 Alloy 1
Just above the eutectic
XB E
f 
 X E
B  X Bo 
l l X E
B  X B 
 
fE 
X o
B  X B 
f ,total  f ,primary  f ,eutectic X E
B  X B 
Just below the eutectic, the fraction of
 and  in the eutectic liquid
f 
X 
B  X BE 
X 
B  X B 
X B X BE X B f 
X E
B  X B 
XB o
X 
B  X B 
12
Equilibrium Cooling of an Off-Eutectic Alloy
Primary
Primary 

 from the eutectic
Liquid
 from the eutectic
f ,total  f ,primary  f ,eutectic
Just above TE Just below TE

3

Lesson 16: Equilibrium Cooling of an Off-Eutectic

Alloy- Calculations

Equilibrium Cooling of an Off-Eutectic Alloy-Calculations
Just above the eutectic
temperature the fraction
of liquid and solid are:
Temperature
The first solid that forms

is called primary 
0.27  0.20 0.37  0.27
fl  f 
0.37  0.20 0.37  0.20
Composition, in % B fl  0.41 f  0.59
5
The eutectic liquid becomes the

two phase lamellar eutectic of and 
Temperature
when the temperature drops just

below the eutectic temperature. The
fraction of  and  is:
0.73  0.37 0.37  0.20

f  f 
0.73  0.20 0.73  0.20
Composition, in % B f  0.32
f  0.68
3
Just below the eutectic temperature

Temperature
the microstructure is composed of

primary  that formed above the
eutectic temperature and  from
the eutectic mixture
ftotal  f primary  feutectic
Composition, in % B ftotal  0.59  (0.41)(0.68)  0.87

Alternatively, the fraction of  can
be calculated below the eutectic directly
0.73  0.27
f  f  0.87
0.73  0.20
8
Just above TE Just below TE

2
Increasing primary  Decreasing primary 

Decreasing eutectic Increasing eutectic
Just below TE 6

Lesson 17: Microstructure Development in an Off-

eutectic Alloy

Microstructure Development in an Off-Eutectic Alloy
Al2Cu
- Al
L
Al + 
eutectic
Al
10m
Al-13 % Cu
As-cast
5m
3
For the lamellar eutectic to grow
B
A the two solid phases need to grow
Liquid/solid at the same rate to maintain the
interface coupled diffusion along the liquid
solid interface. In some materials
    like Al-Si alloys the two solid phases
that form the eutectic, -AL and Si,
grow at different rates resulting in an
interface that is no longer planar and
different morphology of the eutectic
results.
3
Primary -aluminum
aluminum / silicon eutectic
4
Al-Si alloy microstructure


Lesson 18: Invariant Reactions in Two Component

Systems

Invariant Reactions in Two Component Systems
F=C–P+1
F = 0, represents invariant equilibrium
And occurs in a two component system
When three phases are in equilibrium
At least one liquid phase, ic ending
l Eutectic
 
l +
Peritectic
l 
 l +  
l1 Monotectic
 l2 l1  + l2
12
Only solid phases, oid ending
Eutectoid 
 
 +
Peritectoid  

 +  
Monotectoid 
 
  + 
8

Lesson 19: Peritectic Phase Diagrams

Peritectic Phase Diagrams
TB
s
q uidiu Label the phase fields
Liquid Li
l
us
Label the invariant reaction
lid
So
Peritectic Isotherm Label the phase boundaries
ius  
 
ui d
Li q l
lid us
Sol
So
s

Solvu
vus
TA 
10 20 30 40 50 60 70 80 90
Composition, in % B 10
Alloy 1 Alloy 2 Alloy 3
T1
0.88  0.60
fl 
T2 Alloy 3 at T2 0.88  0.3
fl  0.48
T3
T4
0.90  0.60
f 
T5 Alloy 3 at T5 0.90  0.34
f  0.54
T6
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 0.98
0.07 0.16 0.34 0.37 0.82 0.88 0.96
5
Temperature, oC
-brass 5 peritectic reactions
FCC Zn, wt% HCP

Equal atomic radii
6

Lesson 20: Analysis of Complex Phase Diagrams

Complex Eutectic Phase Diagrams
Analysis of Complex Phase Diagrams
TB
Temperature
1. Label all
phase fields.
2. Identify all
invariant
reactions.
TA
A Composition, XB B
2
Peritectic Eutectic l  
Eutectic
Peritectic l    
Eutectic Eutectic l    
7
2
Temperature (oC) Reaction

640 Eutectic
854 Peritectic
1133 Peritectic
1638 Congruent
5

Lesson 21: Monotectic Phase Diagrams

Monotectic Phase Diagrams
F=C–P+1 TA
F = 0, represents invariant equilibrium
And occurs in a two component system
Temperature
When three phases are in equilibrium
TB
l1 Monotectic
 l2 l1  + l2
Composition, XB
5
TA
TA
Temperature
Temperature
TB TB
Composition, XB Composition, XB
3
Copper and tungsten have no mutual
solubility, and hence they are often
referred to as metal matrix composites
TA Mechanically mixed and sintered

to produce a fully dense part
Temperature
TB
Composition, XB
7

Lesson 22: Phase Separation and Critical

Points

Phase Separation and Critical Points
Critical point
Critical point
Temperature
TA
P
L+V
X Bl1 X Bcrit X Bl2
Composition, XB
Vl Vcrit VV
V
5
Phase Separation and Critical Points
TA
Liquid TB
Temperature

Critical Temperature

A 20 40 60 80 B
1 2
X B X crit
B
X B
XB 6
Liquid Phase Separation in Polymer Blends
Two Phases Schematic diagrams of
Temperature
Temperature
Temperature
Two Phases
possible polymer blend phase
Two Phases diagrams, for binary blends
Single Phase
where additional
1
complications that can be
Volume Volume Volume introduced by competing
1
Fraction Fraction Fraction processes (such as
Two Phases crystallization of a
Temperature
Temperature
1 1
component) are absent. The
1 1 diagrams exhibit liquid phase
Two Phases
separation like the process in
the monotectic diagrams
Volume Volume
Fraction Fraction
2
Liquid Phase Separation in Polymer Blends
Two Phases
Temperature
Temperature
Upper Critical Solution
Temperature
Two Phases
Temperature (UCST)
Two Phases
Single Phase
Lower Critical Solution
1 Temperature (LCST)
Volume Volume Volume
1
Fraction Fraction Fraction
Two Phases
Temperature
Temperature
1 1
1 1
Two Phases
Volume Volume
Fraction Fraction
3

Lesson 23: Solid State Reactions

Only solid phases, oid ending
Eutectoid 
 
 +
Peritectoid  

 +  
Monotectoid 
 
  + 
8
Solid State Invariant Reactions
Eutectoid 
 
 +
Hypoeutectoid Hypereutectoid
5
Fe-C System
Peritectic
Eutectic
Eutectoid
5
-Fe
 Fe3C
Alternate lamellae
of -Fe and Fe3C
make up the structure
of pearlite.
Advancing interface
 C
Fe
6
Eutectoid
   2
Peritectoid
   2  2
7
Monotectoid
1   2  Zn(ss )
4

Lesson 24: Summary of Invariant

Reactions in Two Component Systems

Eutectic Type
Eutectic l
  Al-Si, Fe-C
l +
Eutectoid 
  Fe-C
 +
Monotectic l1
 l2 Cu-Pb
l1  + l2
Monotectoid 
 
  +  Al-Zn, Ti-V
On cooling one phase going to two phases

6
Peritectic Type
Peritectic l  Fe-C
l +   
Peritectoid   Cu-Al
 +   
On cooling two phases going to one phase
4

Lesson 25: Summary

Summary
• One-component phase diagrams were introduced
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 were introduced.
• The applications of these rules to complex, two-
component systems illustrated that regardless of
how complex the phase diagram appears, the
rules that were introduced could be easily applied.

Phase Equilibria

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Phase Equilibria

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Introduction to Materials

Science and Engineering

Module 7: Phase Equilibria

School of Material Science and Engineering

Module 7: Phase Equilibria

Lesson 2: One Component Phase Diagrams and Gibbs

School of Material Science and Engineering

F=2 F- Degrees of freedom

Phase Diagram of water Psat the saturated vapor

Module 7: Phase Equilibria

Lesson 3: Region of Two Phase Equilibrium

School of Material Science and Engineering

Compressing the gas at temperature

Path 2 Critical point

Module 7: Phase Equilibria

Lesson 4: Additional One Component Phase Diagrams

School of Material Science and Engineering

400 800 1200 1600

Module 7: Phase Equilibria

Lesson 5: Binary Isomorphous Phase Diagrams

School of Material Science and Engineering

Module 7: Phase Equilibria

Lesson 6: The Lever Rule

School of Material Science and Engineering

Module 7: Phase Equilibria

Lesson 7: Phase Fractions

School of Material Science and Engineering

Module 7: Phase Equilibria

Lesson 8: Equilibrium Cooling Curves

School of Material Science and Engineering

Module 7: Phase Equilibria

Lesson 9: Equilibrium Isomorphous Diagrams

School of Material Science and Engineering

Continuous solid solution

Sodium chloride structure

Module 7: Phase Equilibria

Lesson 10: Analysis of a Phase Diagram

School of Material Science and Engineering

qu i the single phase liquid from the

0.40 0.60 0.80

Module 7: Phase Equilibria

Lesson 11: Deviations from Ideal Behavior

School of Material Science and Engineering

T2 0.68 0.37 0.32 0.15

TB T3 0.48 0.41 0.52 0.2

A 0.2 0.40 0.6 0.8 B

Module 7: Phase Equilibria

Lesson 12: Eutectic Phase Diagram

School of Material Science and Engineering

A 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 B

T5 0.67 0.6 0.33 0.3

T6 0.47 0.65 0.53 0.37 0 0.9

T6 0 0.65 0.76 0.37 0.24

T7 0.68 0.3 0.32 0.92

T8 0.6 0.2 0.4 0.95

T9 0.55 0.1 0.45 0.98

T7 0 0.44 0.3 0.56 0.92

T8 0.4 0.2 0.6 0.95

Alloy 4, XBo = 0.65

Module 7: Phase Equilibria

Lesson 13: Determination of Phase Boundaries

School of Material Science and Engineering