MM-231: Phase Equilibria & Microstructure

Course Outline
Spring 2013

Course Aim
To understand the basics of phase equilibria, Phase
diagram and evolution of microstructure in different
processing conditions. These are the bases for the
developmentofadvancedengineeringmaterials.

Course Contents
PhaseruleandPhasediagrams
Microstructures
Diffusion
Nucleation&growth
Solidification
Annealing
Transformations
Note:Contentsofthecoursemaychangeaccordingto
thecircumstances.
Text Book
PhysicalMetallurgyPrinciplesbyRezaAbbaschian,
RobertE.Reed-Hill,4thedition,(2009).
Phase

MM-231: Phase Equilibria & Microstructure

Course Outline
Spring 2013

Course Aim
To understand the basics of phase equilibria, Phase
diagram and evolution of microstructure in different
processing conditions. These are the bases for the
developmentofadvancedengineeringmaterials.

Course Contents
PhaseruleandPhasediagrams
Microstructures
Diffusion
Nucleation&growth
Solidification
Annealing
Transformations
Note:Contentsofthecoursemaychangeaccordingto
thecircumstances.
Text Book
PhysicalMetallurgyPrinciplesbyRezaAbbaschian,
RobertE.Reed-Hill,4thedition,(2009).
PhaseDiagramsandHeterogeneousEquilibriua:A
PracticalIntroductionbyB.Predel,M.Hoch,(2004).

Reference Books
AnintroductiontoMaterialsEngineeringand
SciencebyBrianS.Mitchell,AJohnWiley&
Sons,Inc.,(2004).
EssentialsofMaterialsScienceand
Engineering,2ndEdition,DonaldR.Askeland,
CL-Engineering,(2010).
PhaseDiagramsinMetallurgy,Their
DevelopmentandApplicationbyFrederickN.
Rhines,(1956).

Grading Policy
Quizzes(Un-announced):20%,Assignments:
5%,MidTerm:30%,FinalExam:45%
Attendance:Minimum80%forappearingin
thefinalexam.

PHASES
A phase is a homogeneous portion of a system
with
uniform
physical
and
chemical
characteristics, in principle separable from the
restofthesystem
A difference in either physical or chemical
properties constitutes a phase
gaseous state
seeminglyonlyonephaseoccurs(gasesalways
mix)
liquid state
oftenonlyonephaseoccurs(homogeneous
solutions),e.g.,saltwater,moltenNa2O-SiO2
twoimmiscibleliquids(orliquidmixtures)count
astwophases
solid state
crystallinephases:e.g.,ZnOandSiO2=two
phases
polymorphs:e.g.,wurtziteandsphaleriteZnS
aredifferentphases
solidsolutions=onephase(e.g.,Al2O3-Cr2O3
mixtures)

Note:metastablephasesdonotappearon
equilibriumphasediagrams.

First Assignment
Definitionsandunderstandingofbasicterms
ofthermodynamics
InternalEnergy
Entropy
Enthalpy
Lawsofthermodynamics
Freeenergy
GibbsFreeenergy
HelmholtzFreeEnergy
Note:Notonly,youshouldmakeawritten
assignmentbutyoumusthaveaclearideaof
thesetermsandallthiswillbeaskedand
discussedintheclass.
Referencebook:Introductiontothe
thermodynamicsofmaterials,4thEditionby
DavidR.Gaskell,Taylor&Francisgroup
(2003)

DEFINITION
A Phase Diagram describes the state of a
materials system in thermodynamic
equilibrium as a function of temperature,
pressure and composition.

Phase Diagrams are maps of the

equilibrium phases associated with
various combinations of temperature,
pressure, and composition.

One-component (unary)
phase diagram

Two-component (binary)
phase diagram

Three-component (ternary)
phase diagram
(partial isothermal section)

Why Do We Need Phase Diagrams?

For example:
to understand solidification processes
( microstructure properties)
metallurgy, geology,

to characterize compounds and phases

CrTe (actually Cr1-xTe)
YbInCu4 (valence transition; transition temp.
different due to nonstoichiometry)

to understand reactions
welding
soldering
contacting of semiconductors
surface layers (hardening, e.g.)

First Fe-C
Phase Diagram
(1897)
Sir William Chandler
Roberts-Austen

Number of Metallic Phase Diagrams

(Assumption: 80 metallic elements)
No. of
components
n

No. of
possible
systems

Approximate No. of
investigated
systems

80

80

3 160

2 500

82 160

3 000

1 581 580

200

24 141 016

20

300 500 200

3 176 716 400

approximately
1023 40-component
systems!

Phase Diagrams
Structure of the Lecture
Basics

(Phase rule, lever rule, )

Unary (one-component) systems

Binary systems
types of phase diagrams
-x diagrams
invariant reactions
complex systems
possible errors

Ternary systems

types of phase diagrams

types of representations
(isotherms, isopleths,
liquidus projections, Scheil diagrams)
invariant reactions
complex systems

Quaternary systems
p-T diagrams for higher-order systems

Books on Phase Equilibria

B. Predel: Heterogene Gleichgewichte: Grundlagen und

Anwendungen; Steinkopf (Darmstadt), 1982
B. Predel, M. Hoch, M. Pool: Phase Diagrams and
Heterogeneous Equilibria; Springer (Berlin), 2004
F.N. Rhines: Phase Diagrams in Metallurgy: Their Development
and Application; McGraw-Hill (New York), 1956
P. Gordon: Principles of Phase Diagrams in Materials
Systems; McGraw-Hill (New York), 1968
A. Prince: Alloy Phase Equilibria; Elsevier (Amsterdam), 1966
J. Zernike: Chemical Phase Theory; N.V. UitgeversMaatschappij Ae.E. Kluwer (Deventer), 1955

Collections of Phase Diagrams

T.B. Massalski et al. (Ed.): Binary Alloy Phase Diagrams

(3 Volumes); ASM International (Materials Park, OH), 1995.
P. Villars, A. Prince, H. Okamoto (Ed.): Handbook of Ternary
Alloy Phase Diagrams (10 Volumes) , ASM International
(Materials Park, OH), 1995.

Journals on Phase Diagrams

Journal of Phase Equilibria and Diffusion; Springer

CALPHAD - Computer Coupling of Phase Diagrams and
Thermochemistry; Elsevier

GIBBS PHASE RULE

P+F=C+2
or
F=C+2P
P = number of phases
C = number of components
F = degrees of freedom
(number of variables that can be
varied independently)

If the pressure is kept constant:

P + F = C + 1
or
F = C + 1 P

PHASE EQUILIBRIA IN UNARY SYSTEMS

Example: H2O
221bar

A
1.01325bar

6.1mbar

F=C-P+2

A, B:

C = 1, P = 1
F=11+2=2
C:
C = 1, P = 2
F=12+2=1
Triple Pt.:
C = 1, P = 3
F=13+2=0

Example: H2O

1 MPa = 106 Pa = 10 bar

Example: CO2

ALLOTROPY

Elements can exist in more than one (crystalline) forms

POLYMORPHISM

A substance can exist in more than one crystalline

forms

TRANSFORMATIONS

Enantiotropic transformation
Example: S S

Bothstableforms

H2O(s) H2O(l)
Monotropic transformation
x
Example: Pw Pr

Onlyonestableform

(Principle)

met

1.01 bar

met/G
Tm(met)

Tm

Tb

TRANSFORMATIONS
Gibbs Energy vs. Temperature
(p = const.)

Stableintostable
phase,reversible
Phase stable
(enantiotropic transformation)

Phase metastable
(monotropic transformation
possible )

Metastableinto
stablephase,
irreversible

[Pa]

UNARY PHASE DIAGRAMS:

EXAMPLES

SiO2 (schematic)
(series of monotropic
transformations)

Fe
(enantiotropic
transformations)

TRIPLE POINTS OF METALS

Metall

T (C)

p (atm)

p (Pa)

Ag

960

0.000 1

1.01101

As

814

36 *)

3.65106

Ba

704

0.001

1.01102

Ca

850

0.000 1

1.01101

Cu

1083

0.000 000 78

7.910-2

Fe()

1535

0.000 05

5.1

Hg

-39

0.000 000 001 3

1.3210-4

Mn

1240

0.001

1.01102

Ni

1455

0.000 1

1.01101

Pb

327

0.000 000 1

1.0110-2

Pt

1773

0.000 001

1.0110-1

Sr

770

0.000 1

1.01101

Zn

419

0.05

5.07103

*) As: 1 atm (sublimation) at 610C

Isomorphous Systems
p-T-x Diagram
p-T diagram of pure A

T-x diagram

p-T diagram of pure B

p-x diagram

p = constant !
tie line
(Konnode)

Gibbs Energy of Mixing

Basis of the
CALPHAD-Method
to calculate
phase diagrams

LEVER RULE
T

(1-y)

xBL

xB

xB

N = total number of atoms

y = fraction of atoms in phase
(1-y) = fraction of atoms in phase L

y : (1-y) = a : b
a

N(1-y)

Ny

Solidification

for case
of coring

Coring
Assumption:
homogeneous equilibrium
in the liquid phase is
always retained

Frozen first
Frozen last

Dendritic
solidification

Minima and Maxima

xB

P b-T l p hase diagr am .

xB

Error
xTl

Pb

Special Cases:

A ssessed A u - C u ph ase diagr am .

A ssessed A u - N i p h ase diagr am .

Tl

Superstructures
Miscibility Gap
Au

xNi

Ni

Au

xCu

Cu

Eutectic Systems
Eutectic
Line

e: Eutectic Point

T
Metastable extension
into two-phase field!

xB

xB

The Boundary Rule: Any p-phase region

can be bounded only by regions containing
p +/- 1 phases, where p denotes the number
of phases.
The Boundary Curvature Rule: Boundaries
of one-phase regions must meet with
curvatures such that the boundaries
extrapolate into the adjacent two-phase
regions.
The Solubility Rule: All components are
soluble to some degree in all phases

Eutectic Reaction
Invariant Reaction:

Often: lamellar microstructure

of eutectic alloys

 G-x

binary eutectic

Eutectic Systems: Examples

Al-Si

Ag-Cu

Pb-Bi

Al-Sn

Eutectic Systems:
Primary Crystallization and Microstructure

Hypereutectic Al-Si 14% alloy:

primary crystallization

Hypereutectic Al-Si 14% alloy:

final microstructure

Eutectic Systems:
Solidification and Non-equilibrium

xB

No eutectic mixture
should be detected in
this case, however ...

xB

Eutectic Systems:
Isothermal Diffusion / Diffusion Couples

900C

700C

Eutectic Systems:
Limiting Cases
degenerate
eutectic
T

xB

xB

Eutectic Systems:
Errors
(from a customer journal of the company METTLER)

Eutectoid Systems
heat

cool
+

Eutectoid Reaction:

TL
TS
T

Te

Eutectoid
Fe Fe3C
(Pearlite)

+ Fe3C

hypoeutectoid: 0.3 % C

eutectoid: 0.8 % C

: bcc (Ferrite)
: fcc (Austenite)
: bcc
Fe3C: cementite

hypereutectoid: 1.2 % C

Eutectoid Reactions
A ssessed F e- T e p h ase diagr am .

Examples

Fe-Te

A ssessed N i- Z n ph ase diagram .

Ni-Zn

Monotectic Systems
Monotectic Reaction:

L1 L2 +
L2

L2

L2

L2

... the phase field L1+L2 can be

regarded as being made up of an
infinite number of tie-lines ...

Monotectic Systems
Solidification

Monotectic Systems
Examples

A ssessed C u- P b p h ase diagr am .

Cu-Pb

A ssessed B i- F e p h ase diagr am .

Cu

Pb

Bi

Fe

Bi-Fe
(limiting case with
virtually no
solubility in the
solid and very
limited solubility
in the liquid state)

Monotectic Systems
A ssessed N i- A g p h ase diagr am .

Ni

Examples

Ag

uppercriticalsolution
temperature(UCST

PeritecticReaction

A very rare example. Peritectic

reactionsarefrequentcomponentsof
complex phase diagrams with many
phases, but they rarely occur as the
onlyfeatureofaphasediagram.

Threestagesofperitecticreactionina
directionallysolidifiedhigh-speedsteel.(a)Firststagestructure.Darkgrayisaustenite;whiteis
ferrite.Themottledstructureisquenchedliquid.
(b)Subsequentperitectictransformationof(a).
(c)Furtherperitectictransformationof(b).Dark
grayinthemiddleofthewhiteferriteisnewly
formedliquid.Source:ASM Handbook, Vol. 9,
Metallography and Microstructures,2004,p100

Peritectoid Systems
+

A ssessed A g- A l p h ase diagr am .

Ag

Al

Complex Binary Systems

A ssessed A g- O s p h ase diagr am .

Examples
Reaction e:
L2 G +
(Os)
Reaction r:
G + (Os)
L1

A ssessed C u- Sn p h ase di agr am . F rom [44R ay ].

Ag

Os

Reaction l
(Metatectic or
Catatectic Reaction):

+L

Cu

Sn

Complex Binary Systems

Possible Errors

Complex Binary Systems

Technically Important Systems

A ssessed C u- Z n ph ase diagr am .

Cu-Zn = Brass

A ssessed F e- C p h ase diagr am .

Cu

Zn

Fe-C = Steel

Martensite

Fe

Complex Binary Systems

Diffusion Couple

Tie line

SolidSolutions
Asolid-statesolution:acrystallinematerialwith
variablecomposition
Twotypes:
Substitutional(soluteatom/ionreplacessolvent
atom/ion)
Interstitial(soluteatom/ionoccupiesinterstitialsite)
Formationofsolidsolutionsfavoredby:
similaratomic/ionicradii(15%)
Samecrystalstructure
Similarelectronegativities
Samevalency

Example:
Al2O3-Cr2O3
(substitutional,
complete)
Si-Ge
(substitutional,
complete)
Fe-C(interstitial,
partial)
Substitutional(a)andinterstitial(b)