Binary Phase Diagrams

BINARY PHASE DIAGRAMS
Dr. Guna Selvaduray

Materials Engineering Program
San Jose State University
San Jose, CA 95192-0086
G. Selvaduray - SJSU
Utility of Phase Diagrams
Soldering
Brazing
Electromigration
Diffusion Problems
Kirkendahl Voiding
Corrosion
Electrical Resistivity
Limitations to use of Phase
Diagrams
Phase Diagrams are also known as
Equilibrium Diagrams
Rate of Transformation is missing
TTT (Time-Temperature-
Transformation) diagrams are a
complement to Phase Diagrams
Approach
Approach taken during this course will
be phenomenological
No chemical thermodynamics will be
used for derivations
Useful References
1. M. Hansen & K. Anderko, Constitution of Binary Alloys, McGraw-
Hill, 1958
2. R.P. Elliot, Constitution of Binary Alloys, First Supplement,
McGraw-Hill, 1965
3. F.A. Shunk, Constitution of Binary Alloys, Second Supplement,
McGraw-Hill,1969
4. ASM International, ASM Handbook Volume 3: Alloy Phase
Diagrams, 1992
5. R. Hultgren, P.D. Desai, et al, Selected Values of the
Thermodynamic Properties of Binary Alloys, ASM International,
1973
Useful References (cont’d)
6. E.M. Levine, C.R. Robbins & H.F. McMurdie, Phase Diagrams for
Ceramists, The American Ceramic Society, 1964
7. A. Reisman, Phase Equilibria-Basic Principles, Applications,
Experimental Techniques, Academic Press, 1970
8. A. Findlay, The Phase Rule and its Applications, Dover
Publications, 1951
9. G. Humpston & D.M. Jacobson, Principles of Soldering and Brazing,
ASM International, 1993
What is a “Phase”?
Sand and Salt
Coffee and Sugar
Oil and Vinegar
How many phases in each?
What is a “Phase”? (cont’d)
A phase is a homogenous, physically distinct and
mechanically separable portion of the material with a
given chemical composition and structure.
For solids: Chemically and structurally distinct

For liquids: Miscibility
For gases: Always 1 phase
One Component Phase Diagram
The simplest case-Water
Also known as a P-T diagram
Sign of [dP/dT] for:
Solid-Liquid
Liquid-Gas
Gas-Solid
equilibria
P-T Diagram for Water
Source: Barret, Nix & Tetelman, The Principles of Engineering

G. Selvaduray - SJSU Materials, 1973. p 118
One Component Phase Diagram
Region Number of Phases Degrees of Freedom
The Gibbs Phase Rule
P+F=C+2
The Quasi-Chemical Approach
Understanding interactions on bond energies
Interaction between 2 species: A and B
A-A and B-B bonds
Thermodynamic Parameter: Melting Point (T)
How does mixing of A-A and B-B bonds affect T?
The Ideal Case
(A-B) = x(A-A) + (1-x) (B-B)
Where x is the mole fraction of A in B

TAlloy = TA + x ( TB - TA)
Examples:
Copper – Nickel
Silicon – Germanium
Nickel-Copper Phase Diagram
G. Selvaduray - SJSU Source: ??

Germanium-Silicon Phase
Diagram

Hume Rothery Rules
1. Relative Size Ratio ±15%
2. Crystal Structure-must be the same
3. Electronegativity Difference – within
± 0.4 e.u.
4. Valence must be the same
Eutectic Behavior
A-B < 0.5 (A-A + B-B)
TAlloy < TA , TB
Examples:
Lead - Tin
Gold - Silicon
Tin-Lead Phase Diagram

Gold-Silicon Phase Diagram
Hansen & Anderko, Constitution of Binary

G. Selvaduray - SJSU Alloys, 1958. p. 232
Gold-Germanium Phase Diagram

Intermetallic Compound
Formation
A-B > 0.5 (A-A + B-B)
TAlloy > TA , TB
Example:
Gallium -Arsenic
Arsenic-Gallium Phase Diagram

Working with Phase Diagrams
Overall Composition
Solidus
Liquidus
Limits of Solid Solubility
Chemical Composition of Phases at any temperature
Amount of Phases at any temperature
Invariant Reactions
Development of Microstructure
Chemical Activity
Copper-Silver Phase Diagram
Source: Callister, Materials Science and Engineering:

G. Selvaduray - SJSU An Introduction, 2000. p. 256
Solidus and Liquidus
Solidus
Temperature at which alloy is completely
solid
Temperature at which liquefaction begins
Liquidus
Temperature at which alloy is completely
liquid
Temperature at which solidification begins
Overall Composition
Concentration: Relative amounts of each
constituent
It is the horizontal axis in all binary
phase diagrams
The scale can be in weight %, atomic %
or mole %
Chemical Composition of Phases
It is the chemical composition of each
phase in the system
In a system having more than one phase,
each phase will have a unique chemical
composition which will be different from
each other, and will also be different from
the overall composition
Not to be confused with overall
composition
Solid Solutions
What is a solid solution?
When foreign atoms are incorporated into a crystal structure,

whether in substitutional or interstitial sites, the resulting
phase is a solid solution of the matrix material (solvent) and
the foreign atoms (solute)
Substitutional Solid Solution: Foreign (solute) atoms occupy

“normal” lattice sites occupied by matrix (solvent) atoms,
e.g. Cu-Ni;Ge-Si
Interstitial Solid Solutions: Foreign (solute) atoms occupy

interstitial sites, e.g., Fe-C
Types of Solid Solubility
Unlimited Solid Solubility: Solute and solvent are mutually
soluble at all concentrations, e.g., Cu-Ni system
Meets the requirements of the Hume-Rothery Rules
Result is a “single phase alloy”
Limited or Partial Solid Solubility: There is a limit to how much

of the solute can dissolve in the solvent before “saturation” is
reached, e.g., Pb-Sn and most other systems
Does not meet the requirements of the Hume-Rothery Rules
Results in a “multi-phase alloy”
Amount of each phase
Dependent on the Overall Composition
and Temperature
The (Inverse) Lever Rule
Tie-Lines
Lever Rule - 1
Source: Smith, Principles of Materials Science

G. Selvaduray - SJSU And Engineering, 1996, p.440
Cu-Ni Phase Diagram

Example Problem 1
One kilogram of an alloy of 70% Pb and 30% Sn is
slowly cooled from 300ºC. Calculate the
following:
a) Weight % of liquid and α at 250ºC
b) Chemical composition of the liquid and α at 250ºC
c) Weight % of the liquid and α just above the eutectic
temperature
d) Chemical composition of the liquid and α at just above
the eutectic temperature
Pb-Sn Phase Diagram

Invariant Reactions
Eutectic: L = α (s) + β (s); e.g., Pb-Sn

Peritectic: α (s) + L = β (s); e.g., Pb-In
Monotectic: L1 = α (s) + L2; e.g., Cu-Pb
Syntectic: L1 + L2 = α (s); e.g., Na-Zn
Metatectic: β (s) + α (s) = L1 e.g., U-Mn
Pb-In Phase Diagram

Cu-Pb Phase Diagram

Microstructure Development
The microstructure developed depends on

the overall composition and the cooling
rate
Composition dependence of
microstructure
Source: Askeland, The Science & Engineering

Of Materials, 1984, p 246
microstructure

G. Selvaduray - SJSU Of Materials, 1984, p 249
microstructure

microstructure

Example Problem 2
For the 70% Pb and 30% Sn alloy, calculate:
(a) The weight percent of alpha and beta phases
at 100ºC
(b) The chemical composition of the α and β
phases at 100ºC
(c) Amount of primary and secondary α
(d) Amount of α formed during the eutectic reaction
Chemical Activity
What is activity?
A measure of the “escaping tendency”
Activity = 1 if species is in its standard
state (pure, most stable form, at
temperature of interest)
What is the activity of a species in a
solution?
Activity (a) =Activity Coefficient x Mole
Fraction
Activity Determinations
IDEAL CASE: Activity Coefficient = 1
Therefore: Activity = Mole Fraction; e.g., Cu-Ni
NON-IDEAL CASE:
Positive Deviation: a>aid, i.e., activity coefficient>1
e.g. Pb-Sn
Negative Deviation: a<aid, i.e., activity coefficient<1
e.g. Ga-As
Source: Gaskell, Introduction to Thermodynamics
G. Selvaduray - SJSU Of Materials, 1973
Example Problem 3
Draw an activity-composition diagram for
the Cu-Ni system at 1200ºC
Draw an activity-composition diagram for

the Ga-As system at 400ºC
G. Selvaduray - SJSU SJSU-Selvaduray

Intermetallic Compounds
Line compounds
Stoichiometric Ratio
Stoichiometric Range

Au-Sn Phase Diagram

Ag-Sn Phase Diagram

Using Phase Diagrams to
determine Heat Treatability
Heat Treatment is based on
“controlling” the solid state
transformation rate
Heat treatment of steels: control of the
eutectoid reaction
Age hardening (precipitation strengthening)
of aluminum alloys: control of precipitation
reaction
Heat Treatment of Steels
The eutectoid reaction
Martensite
Austenite
Pearlite
TTT diagrams
Fe-C Phase Diagram

TTT Diagram
Source: Flinn & Trojan, Engineering Materials

G. Selvaduray - SJSU and their Applications, 1986, p 239
Age Hardening/Precipitation
Strengthening
Particularly relevant for aluminum alloys,
e.g., aluminum lines on ICs
Phase diagrams tell us if an alloy system
is age-hardenable, and the composition
range over which the alloy system is
age-hardenable
Al-Cu system
Age Hardening Al Alloys

Al-Cu Phase Diagram
Source: Hansen & Anderko, Constitution

G. Selvaduray - SJSU of Binary Alloys, 1958. p. 85
Heat Treatment vs Strength
Source: ??
Heat Treatment vs Ductility
Source: ??
Coherent & Incoherent
Precipitates
Source: ??
Effect of aging on
Electromigration
Critical parameter: densityppt vs densitymatrix
If densityppt > densitymatrix
Region of compression is created around the ppt
Driving force is for migration of matrix atoms away
from ppt
If densityppt < densitymatrix

Region of tension is created around the ppt
Driving force of for migration of matrix atoms
towards the ppt
Lead Frame Alloys
Alloy 42
Copper alloy lead frames
Kovar
Lead Frame Alloy
Compositions
Source: Electronic Materials Handbook Volume 1:

G. Selvaduray - SJSU Packaging, ASM International, 1989, p. 490
Fe-Ni
Phase
Diagram
Source: Hansen & Anderko,

Constitution of Binary
Alloys, 1958. p. 85
Fe-Cu
Phase
Diagram

Alloys, 1958. p. 581
Cu-Sn
Phase
Diagram

Alloys, 1958. p. 634
Example Problem 4
Will the age hardening process
characteristics affect the electrical
resistivity (or conductivity) of lead
frames?
Will the conductivity increase or decrease
with overaging?
Application of Phase Diagrams
to Diffusion
Fick’s First Law: J = -D [dc/dx]
[dc/dx] is the concentration gradient and
driving force for diffusion
It this were true, multiphase alloys such
as Pb-Sn alloys must “self-homogenize”
over time and transform into a single
phase alloy
Activity: Driving Force for
Diffusion
The driving force for diffusion to occur is
the activity difference
In the case of Pb-Sn alloys, the phases are:
α (Pb rich) and β (Sn rich)
Diffusion of a species from one phase into
another will not occur if:
aSn (beta) = aSn (alpha)
aPb (beta) = aPb (alpha)
Relevance of solid solubility limits
Phase diagrams also tell us the maximum
extent to which one species can diffuse
into another
This is given by the solid solubility limits
at the temperature of interest
The Cu-Ni example in standard
textbooks is most often not applicable
Kirkendahl Voiding
If there is a major difference in solid
solubility limits, voiding can be expected to
occur in the phase that permits less solid
solubility
e.g., the Al-Au system
Interdiffusion does not necessarily occur at

the same rate
Al-Au Phase Diagram

Alloys, 1958. p. 69
Effect of composition on
properties
Mechanical Properties
Electrical Resistivity
Composition vs Strength
Source: ??
Composition vs Resistivity

Determination of Phase
Diagrams
Cooling Curves
Differential Scanning Calorimetry
Thermomechanical Analysis
Differential Thermal Analysis
Metallography/Petrography
Energy Dispersive X-ray Spectroscopy
Electron Microprobe Analyzer
X-ray Diffraction
Transmission Electron Microscopy
Cooling Curves
Source: Smith, Principles of Materials Science

G. Selvaduray - SJSU And Engineering, 1996, p.441
Experimental measurement of
∆Hm from DSC
Mg-Si
Phase
Diagram

Alloys, 1958. p. 917
Al-Si
Phase
Diagram

Alloys, 1958. p. 133
Al-Mg
Phase
Diagram

Alloys, 1958. p. 106
Cr-Mo Phase Diagram

Cr-Ni Phase Diagram

Alloys, 1958. p. 542
Mo-Ni
Phase
Diagram

Alloys, 1958. p. 968
Au-Si Phase Diagram

Alloys, 1958. p. 232
Au-Sn
Phase
Diagram

Alloys, 1958. p. 233
Ternary Phase Diagrams
Three components
Overall composition
Number of phases
Chemical composition of each phase
Amount of each phase
Solidification sequence

Example Problem 5
What is the maximum number of phases

that can exist in a ternary system?

Binary Phase Diagrams

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BINARY PHASE DIAGRAMS

Dr. Guna Selvaduray

How many phases in each?

For solids: Chemically and structurally distinct

Source: Barret, Nix & Tetelman, The Principles of Engineering

The Gibbs Phase Rule

Thermodynamic Parameter: Melting Point (T)

How does mixing of A-A and B-B bonds affect T?

(A-B) = x(A-A) + (1-x) (B-B)

Where x is the mole fraction of A in B

G. Selvaduray - SJSU Source: ??

Source: Barret, Nix & Tetelman, The Principles of Engineering

Source: Barret, Nix & Tetelman, The Principles of Engineering

Hansen & Anderko, Constitution of Binary

Hansen & Anderko, Constitution of Binary

Hansen & Anderko, Constitution of Binary

Source: Callister, Materials Science and Engineering:

When foreign atoms are incorporated into a crystal structure,

Substitutional Solid Solution: Foreign (solute) atoms occupy

Interstitial Solid Solutions: Foreign (solute) atoms occupy

Limited or Partial Solid Solubility: There is a limit to how much

The (Inverse) Lever Rule

Source: Smith, Principles of Materials Science

Source: Callister, Materials Science and Engineering:

Source: Callister, Materials Science and Engineering:

Eutectic: L = α (s) + β (s); e.g., Pb-Sn

Hansen & Anderko, Constitution of Binary

Hansen & Anderko, Constitution of Binary

The microstructure developed depends on

Source: Askeland, The Science & Engineering

Source: Askeland, The Science & Engineering

Source: Askeland, The Science & Engineering

Source: Askeland, The Science & Engineering

Draw an activity-composition diagram for

G. Selvaduray - SJSU  SJSU-Selvaduray

G. Selvaduray - SJSU  SJSU-Selvaduray

Hansen & Anderko, Constitution of Binary

Hansen & Anderko, Constitution of Binary

Source: Barret, Nix & Tetelman, The Principles of Engineering

Source: Flinn & Trojan, Engineering Materials

Source: Askeland, The Science & Engineering

Source: Hansen & Anderko, Constitution

If densityppt < densitymatrix

Source: Electronic Materials Handbook Volume 1:

Source: Hansen & Anderko,

Source: Hansen & Anderko,

Source: Hansen & Anderko,

e.g., the Al-Au system

Interdiffusion does not necessarily occur at

Source: Hansen & Anderko,

Source: Askeland, The Science & Engineering

Source: Smith, Principles of Materials Science

Source: Hansen & Anderko,

Source: Hansen & Anderko,

Source: Hansen & Anderko,

Source: Hansen & Anderko,

Source: Hansen & Anderko,

Source: Hansen & Anderko,

Source: Hansen & Anderko,

Source: Hansen & Anderko,

 Chemical composition of each phase

 Amount of each phase

G. Selvaduray - SJSU  SJSU-Selvaduray

G. Selvaduray - SJSU SJSU-Selvaduray

G. Selvaduray - SJSU SJSU-Selvaduray

Chemical composition of each phase

Amount of each phase

G. Selvaduray - SJSU SJSU-Selvaduray

G. Selvaduray - SJSU SJSU-Selvaduray