Phase Diagram

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-TemperatureTransformation) 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. 2. 3. 4. 5. M. Hansen & K. Anderko, Constitution of Binary Alloys, McGrawHill, 1958 R.P. Elliot, Constitution of Binary Alloys, First Supplement, McGraw-Hill, 1965 F.A. Shunk, Constitution of Binary Alloys, Second Supplement, McGraw-Hill,1969 ASM International, ASM Handbook Volume 3: Alloy Phase Diagrams, 1992 R. Hultgren, P.D. Desai, et al, Selected Values of the Thermodynamic Properties of Binary Alloys, ASM International, 1973
Useful References (contd)

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? (contd)

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 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
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 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: 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 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 300C. Calculate the following:
a) b) c) d) Weight % of liquid and at 250C Chemical composition of the liquid and at 250C Weight % of the liquid and just above the eutectic temperature Chemical composition of the liquid and at just above the eutectic temperature
Pb-Sn Phase Diagram
Invariant Reactions
Eutectic: Peritectic: L = (s) + (s); e.g., Pb-Sn (s) + L = (s); e.g., Pb-In
Monotectic: L1 = (s) + L2; e.g., Cu-Pb Syntectic: L1 + L2 = (s); e.g., Na-Zn Metatectic: (s) + (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 G. Selvaduray - SJSU
Source: Askeland, The Science & Engineering Of Materials, 1984, p 249
Example Problem 2
For the 70% Pb and 30% Sn alloy, calculate: (a) The weight percent of alpha and beta phases at 100C (b) The chemical composition of the and phases at 100C (c) Amount of primary and secondary (d) Amount of 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 Of Materials, 1973
Example Problem 3
Draw an activity-composition diagram for the Cu-Ni system at 1200C Draw an activity-composition diagram for the Ga-As system at 400C
SJSU-Selvaduray
Intermetallic Compounds
Line compounds Stoichiometric Ratio Stoichiometric Range
SJSU-Selvaduray
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 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 of Binary Alloys, 1958. p. 85
Heat Treatment vs Strength
Source: ??
Heat Treatment vs Ductility
Source: ?? G. Selvaduray - SJSU
Coherent & Incoherent Precipitates
Source: ?? G. Selvaduray - SJSU
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: Packaging, ASM International, 1989, p. 490
Fe-Ni Phase Diagram
Source: Hansen & Anderko, Constitution of Binary Alloys, 1958. p. 85 G. Selvaduray - SJSU
Fe-Cu Phase Diagram
Cu-Sn Phase Diagram
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

Ficks 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: (Pb rich) and (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
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 And Engineering, 1996, p.441
Experimental measurement of Hm from DSC
Mg-Si Phase Diagram
Al-Si Phase Diagram
Al-Mg Phase Diagram
Cr-Mo Phase Diagram
Cr-Ni Phase Diagram
Mo-Ni Phase Diagram
Au-Si Phase Diagram
Au-Sn Phase Diagram
Ternary Phase Diagrams

Three components Overall composition Number of phases Chemical composition of each phase Amount of each phase Solidification sequence
SJSU-Selvaduray
Example Problem 5
What is the maximum number of phases that can exist in a ternary system?
SJSU-Selvaduray

Phase Diagram

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Phase Diagram

Uploaded by

Copyright:

Available Formats

BINARY PHASE DIAGRAMS

Utility of Phase Diagrams

Limitations to use of Phase Diagrams

Useful References (contd)

What is a Phase? (contd)

One Component Phase Diagram

P-T Diagram for Water

One Component Phase Diagram

The Gibbs Phase Rule P+F=C+2

The Quasi-Chemical Approach

The Ideal Case

Nickel-Copper Phase Diagram

Germanium-Silicon Phase Diagram

Hume Rothery Rules

Tin-Lead Phase Diagram

Gold-Silicon Phase Diagram

Hansen & Anderko, Constitution of Binary Alloys, 1958. p. 232

Gold-Germanium Phase Diagram

Hansen & Anderko, Constitution of Binary Alloys, 1958. p. 206

Intermetallic Compound Formation

Arsenic-Gallium Phase Diagram

Hansen & Anderko, Constitution of Binary Alloys, 1958. p. 165

Working with Phase Diagrams

Copper-Silver Phase Diagram

Source: Callister, Materials Science and Engineering: An Introduction, 2000. p. 256

Solidus and Liquidus

Chemical Composition of Phases

Types of Solid Solubility

Amount of each phase

Source: Smith, Principles of Materials Science And Engineering, 1996, p.440

Cu-Ni Phase Diagram

Source: Callister, Materials Science and Engineering: An Introduction, 2000. p. 247

Pb-Sn Phase Diagram

Source: Callister, Materials Science and Engineering: An Introduction, 2000. p. 258

Pb-In Phase Diagram

Hansen & Anderko, Constitution of Binary Alloys, 1958. p. 855

Cu-Pb Phase Diagram

Hansen & Anderko, Constitution of Binary Alloys, 1958. p. 610

Composition dependence of microstructure

Composition dependence of microstructure

Source: Askeland, The Science & Engineering Of Materials, 1984, p 249

Composition dependence of microstructure

Source: Askeland, The Science & Engineering Of Materials, 1984, p 248

Composition dependence of microstructure

Source: Askeland, The Science & Engineering Of Materials, 1984, p 248

Source: Gaskell, Introduction to Thermodynamics Of Materials, 1973

Au-Sn Phase Diagram

Hansen & Anderko, Constitution of Binary Alloys, 1958. p. 233

Ag-Sn Phase Diagram

Hansen & Anderko, Constitution of Binary Alloys, 1958. p. 52

Using Phase Diagrams to determine Heat Treatability

Heat Treatment of Steels

Fe-C Phase Diagram

Age Hardening/Precipitation Strengthening

Age Hardening Al Alloys

Source: Askeland, The Science & Engineering Of Materials, 1984, p 281

Al-Cu Phase Diagram

Source: Hansen & Anderko, Constitution of Binary Alloys, 1958. p. 85

Heat Treatment vs Strength

Heat Treatment vs Ductility

Source: ?? G. Selvaduray - SJSU

Coherent & Incoherent Precipitates

Source: ?? G. Selvaduray - SJSU

Effect of aging on Electromigration