20230102-MT-205-PD-BNS-L-1 To L-3 (2022-2023) Notes-1

MT-205 Phase Computational
Diagrams Thermodynamics
(2022-2023) of Materials
ICME :
Prof. B. Nageswara Sarma
Dept. of Metallurgical Engg.
Integrated
IIT (BHU), Varanasi Computational
Materials Engg.
Computational Design of Materials

IIT (BHU), Varanasi MT 205 PD BNS L-1 to L-3 Jan, 2023
Syllabus
Unary Systems: Thermodynamic conditions of

equilibrium in closed and open systems.
Gibbs energy-temperature-pressure diagrams and
properties of substances. Scientific Group
Thermodata Europe (SGTE) database. Condensed
phase rule. Allotropy. Degree of
transformations. (3 L)

Syllabus
Binary Systems with Two Phase Equilibria: Gibbs energy-
composition diagrams. Solution models. Isomorphous
systems. Calculation of liquidus and solidus in ideal
systems. Lever rule. Iso-Gibbs energy curves. Equilibrium
diagrams for systems exhibiting moderate departures
from ideal behaviour. Congruent minimum and congruent
maximum.

Syllabus
Equilibrium and quasi-equilibrium solidification in
isomorphous systems and corresponding microstructures.
Stability of a phase. Stability function. Miscibility gap and
chemical spinodal boundaries. Thermodynamic
conditions and determination of miscibility gap, spinodal
boundaries and consolute point. Decomposition inside
and outside spinodal boundary and the microstructural
features. Illustrative examples. (9 L)

Syllabus
Binary Systems exhibiting Invariant Reactions: Possible
invariant reactions and the thermodynamic conditions.
Eutectic systems. Primary and eutectic solidification and
resulting microstructures. Ag-Cu, Al-Si and Pb-Sn
systems. Eutectoid, monotectic and monotectoid systems.
Peritectic systems. Solidification in peritectic systems and
resulting microstructures. Cu-Zn system. Peritectoid,
syntectic and metatectic systems.

Syllabus
Ordered phases. Al-Cu and Ti-Al systems.

Metastability. Iron-graphite and iron-cementite
phase diagrams. Rules for construction of phase
diagrams for complex systems. Typical errors and
necessary corrections in the construction of phase
diagrams. (12 L)

Syllabus
Ternary Systems: Graphical representation of ternary

phase diagrams. Isothermal and vertical sections.
Ternary isomorphous systems.
Computation of liquidus and solidus boundaries.
Congruent minimum and congruent maximum.
Ternary eutectic systems. (6 L)

Syllabus
Computation of Phase Diagrams: CALPHAD methods and

computation of multicomponent multi-phase equilibria and
phase diagrams. (3 L)
Experimental Determination of Phase Diagrams:
Isothermal methods. Microscopy, x-ray diffraction
electrical resistivity and magnetic methods. Diffusion
multiples. Non-isothermal
methods. Thermal analysis and dilatometry. (6 L)

Textbooks
1. P. Gordon: Principles of Phase Diagrams in Materials
Systems, McGraw-Hill, 1968.
2. S.P. Gupta, Phase Equilibria in Materials, Allied, 2003.
3. D.R.F. West and N. Saunders: Ternary Phase
Diagrams in Materials Science, 3rded., Woodhead, 2002.
4. J.-C. Zhao (Ed.): Methods for Phase Diagram
Determination, Elsevier, 2007.

Reference books
1. D.A. Young: Phase Diagrams of Elements, Univ. of

California, 1991.
2. H.A.J. Oonk and M.T. Calvet: Equilibrium
between Phases of Matter, Springer, 2008.
3. M.H.G. Jacobs and H.A.J. Oonk: Equilibrium
between Phases of Matter-Supplement,
Springer, 2011.

Reference books
5. A. Prince: Alloy Phase Equilibria, Elsevier, 1966.

6. C.H.P. Lupis: Chemical Thermodynamics of Materials,
North Holland, 1983.
7. M. Hillert: Phase Equilibria, Phase Diagrams and Phase
Transformations, 2nd ed., Cambridge, 2007.
8. ASM Handbook Vol.3: Alloy Phase Diagrams, ASM
International, 1992.
9.T.B. Massalsky (ed.): Binary Alloy Phase Diagrams, 2nd
ed. (in 3 volumes), ASM International, 1990.

Assignments, Exams & Evaluation
4 Practice Assignments : 10
1 Final Assignment : 10
Mid Sem Exam : 30
End Sem Exam : 50
Total : 100 Marks
Relative Grading, ensuring minimum learning levels.

Introduction (2)
➢ One common area of MSE and ME is
the selection/design of materials & processing
schedules and design/manufacture of components
for engineering applications.
➢ Materials Behaviour at microscopic scale:

design and characterization of microstructures.
➢ Design and fabrication of engineering components:

at different length and time scales,
temperature & pressure conditions.
➢ Ensuring better service life and performance.

Introduction (3)
➢ The tetrahedron emphasizes the four interdependent,
distinct aspects of materials science:
processing, structure, properties and performance.
➢ From an educational point of view, it is critical to identify
what students learn about each corner of the tetrahedron.

Introduction (4)
https://gems.matse.illinois.edu/educators/
Introduction (5): MSE Overview
➢ Thermodynamics of Materials:
Equilibrium state of materials
Thermodynamic and thermophysical properties
➢ Phase Diagrams: Graphical depiction of equlm state
➢ Phase Transformations: Kinetics, effect of T and time…
➢ Heat (Thermomechanical) Treatments
➢ Processing of Materials: Desired/Tailored Microstructure
➢ Non-equlm Processing of Materials: Stability of Microstructure
➢ Mechanics/Mechanical Behaviour of Materials
➢ Dislocation Dynamics/Defect Interactions
➢ Strengthening Mechanisms in Materials…
➢ Alloy Design and Development/Manufacture of components.
➢ Fracture Mechanics, Failure Analysis and Component Integrity
Thermodynamics of Materials
➢ Classical Thermodynamics:
Treat matter as continuum ==> (T, P, x)
➢ Statistical Thermodynamics:
Atomistic nature of matter ==> (T, P, x, ui )
– Classical Statistical Thermodynamics
Newtonian Mechanics Classical Statistics
– Quantum Statistical Thermodynamics
Quantum Mechanics Quantum Statistics
➢ G of each phase in the system as a function of

(T, P, x, ui ) and adjustable model parameters
called interaction parameters, say, ei.
➢ These ei characterize the system ==> Database.

TD Models
➢ Model consists of a set of assumptions which map the
physical reality of the system into a mathematical
framework.

Computational Thermodynamics (CT)
➢ TD Models: Multicomponent, multiphase systems.
➢ Materials-systems consist of a phase, or multiple phases.
➢ Each of these phases can have one or more components.
➢ Unary, binary, ternary, quaternary, quinary, etc.
➢ In the classical thermodynamics sense, a phase is
characterized by its temperature, pressure and
(composition ?) chemical potentials of the components.
➢ CT involves finding the characteristic ei for the materials

systems, corresponding to a meaningful and standardized
model, using which, many properties of the system can
be readily computed, without having to depend on
experiments.
Why CT?

“On the equilibrium of heterogeneous substances” (1876)

Phases and Components
The criterion for equilibrium expressed in the equation
(dG)T,P = 0 for a reversible process
is applicable for a closed system, that is, the composition
of the system is fixed and for which the only energy
exchanges with the surroundings are due to heat transfer
and work done against pressure.
In the study of materials, we are frequently interested in
systems that may also undergo compositional changes by
mass transfer.
To facilitate the treatment of such systems, a discussion of
the terms phase and component is necessary.

Phases and Components (contd)
➢ Any system under equilibrium may be either
homogeneous or heterogeneous.
➢ A homogeneous system exhibits uniform properties (on a
microscopic and macroscopic scales, but not on atomic
scale) throughout the system and contains only one
physical boundary, that between the system and its
surroundings. Such a system is called a single-phase
system.
➢ Practically, in systems made up of metals and alloys in the
solid state, internal boundaries called grain (or more
precisely homophase) boundaries are present.
➢ If the grain size is not too small (> 1μm), the effects of
these boundaries on structure insensitive properties are
negligible.

➢ Phase is all those portions of a system, each of
which is separated from its surroundings by a
definite interface, possessing the same intensive
and molar properties when the system is in
thermodynamic equlm, or exhibiting a continuous
variation in intensive and molar properties when
the system is in a non-equilibrium condition.
➢ A heterogeneous system contains two or more
homogeneous systems, or phases, each
separated from the others by distinct physical
boundaries called heterophase boundaries.

➢ Components are defined as the minimum number of
chemical species that may be independently varied in
amount and by means of which the compositions of every
phase in the system may be completely specified under
given experimental conditions.
➢ In general, the number of components is simply equal to
the number of elements in the system.
➢ In complex systems, however, the number of components
may not be immediately apparent and in practice will
depend on experimental conditions as well as the
definition of equilibrium.
➢ Two illustrative examples :

Consider a system composed of H2, O2, and H2O.
At standard T and P, there are two phases,
one a liquid consisting of an aqueous solution of H2 and O2,
the other a vapour containing the two gases and water vapour.
Any chemical reaction between H2, O2, and H2O is extremely
slow and can be neglected. However, the following equilibria do
occur H2 (liquid) = H2 (vapour) ;
O2 (liquid) = O2 (vapour) ;
H2O (liquid) = H2O (vapour).
All three species, H2, O2, and H2O are independently variable
and all must be specified. The number of components is three.
At high temperatures, the reaction 2 H2 + O2 = 2 H2O proceeds to
equilibrium rapidly. Only two of the three species need to be
specified. The number of components is two.
Consider : Cementite (Fe3C), in equilibrium with a solid
solution of C in solid iron (ferrite), in steel.
Fe3C is not strictly a stable phase. At RT, Fe3C decomposes
to ferrite and graphite very slowly, so that Fe3C may be
considered to be a stable species. Thus, the number of
components is three.
The decomposition of Fe3C does proceed essentially to
equilibrium at heat treatment temperatures.
Thus, the amounts of only two of the three species may be
independently varied, and the number of components
becomes two.
The choice of species as components is arbitrary, but for
convenience the elemental species Fe and C are chosen.
Great Materials Moments

Notes on Thermodynamics of Materials by P. Rama Rao et al. (2016)

Notes on Thermodynamics of Materials by P. Rama Rao et al. (2016)
Phase diagrams are the
beginning of wisdom,
not the end of it.
- Sir William Hume-Rothery
Phase diagrams depict the regions of stability of

phases present in the system under equilibrium
conditions as a function of temperature, pressure and
composition.
They are also known as equilibrium diagrams/
constitution diagrams.

Phase Diagrams
Initially, the determination and the use of phase diagrams
were largely empirical.
However, there is a firm basis for such diagrams in the
science of thermodynamics.
A large number of binary and some multicomponent phase
diagrams have been calculated from thermodynamics
during the last thirty years.
The calculations are complex, but increasing computing
power at relatively low cost has made this possible.
Solution models of varying rigour and accuracy are being
employed for this purpose.
CALPHAD, CVM, First Principles calculations, etc.

Experimental Techniques for PDs
Dynamic / Non-isothermal Techniques (Fix x, vary T)
Differential Thermal Analysis
Differential Scanning Calorimetry
Chemical Potential (EMF) Techniques
Magnetic Susceptibility Measurements
Resistivity Measurements
Dilatometric Methods
Static / Isothermal Techniques (Fix T, vary x)
Metallography (Optical & TEM)
X-ray (Phase Disappearance & Parametric) Methods
Sampling/ Equilibriation Methods
Diffusion Couples
Several expts, still uncertain!!

Computational Thermodynamics (CT)

Solution Models: Binary Systems
➢ Consider a binary disordered substitutional solid solution
➢ Total N atomic sites, occupied by
NA A atoms & NB B atoms, such that NA + NB = N.
Ideal solution model

(Drastic assumption)
A and B atoms are
identical in all respects,
except for the names/
labels attached to them.
Random/ideal mixing.

Ideal Solution Model (Binary Systems):
Simple Isomorphous System
➢ Gibbs energy of mixing
𝑖𝑑 = R𝑇 𝑋 ln 𝑋 + 𝑋 ln 𝑋
𝐺𝑚 𝐴 𝐴 𝐵 𝐵
➢ Simple isomorphous phase diagram
➢ Applications (e.g.1):
➢ Transient Liquid Phase Bonding
or Diffusion Brazing
A thin Cu foil, clamped between

thick Ni plates & heated above TCu.
Schmid-Fetzer, JPED (2014)
Solid bond is stable almost up to solidus !!

Phase diagrams: Zone Refining
➢ Applications (e.g.2):
➢ (Multiple) Zone Refining:
➢ Super pure Germanium
(Impurities < 1ppb)
Pfann, 1954, Bell Labs

In Praise of Phase Diagrams …
Phase diagrams are the

beginning of wisdom,
not the end of it.
- Sir William Hume-Rothery
Phase diagrams are as indispensable as

navigators’ maps in a voyage through
materials design and development.

Gibbs free energy, Chemical Potential (Thermodynamic

Potential), Gibbs Phase Rule, Gibbs-Duhem, Gibbs-Konovalov,
Conditions of Equilibrium, etc.
"Gibbs did for statistical mechanics and for thermodynamics,

what Laplace did for celestial mechanics and Maxwell did for
electrodynamics, namely, made his field a well-nigh finished
theoretical structure". - Robert A. Millikan


Outline
➢ Topology of phase diagrams
➢ Prototype phase diagrams
➢ Thermodynamic descriptions and solution models
➢ Calphad thermodynamics
➢ Applications
➢ Shortcomings and improvements

Topology of phase diagrams
Gibbs Phase Rule

F=C–P+2
Gibbs-Konovalov Equation
van der Waals Equation

Gibbs energy vs composition
G-x plots & corr. PD
Eutectic with Congr. min.
Congruent point
From “On the Equilibrium of Heterogeneous

Substances” by J.W. Gibbs, Transactions of
Connecticut Academy, 1876.

Isomorphous with congruent minimum
Incorrect
Correct

Phase boundary rule
Masing-Palatnik-Landau rule:
p+ + p- = r – d
No. of phases that appear / disappear = p+ / p-

Dimensionality of boundary = d
Dimensionality of phase diagram = r

Schreinemaker’s rule
Extension of boundaries of one phase region

Experimental determination
Static Methods:
Identification of phases present in equilibrated alloys at
(chosen) fixed temperatures.
Optical Microscopy, XRD, EPMA, Phase Disappearance
Method, etc.

Experimental determination
Dynamic Methods:
Identification of temperatures of transformation in alloys of
chosen compositions.
Differential thermal analysis, etc.
Ideal freezing curve of a solid- Ideal freezing curves of (1) a hypoeutectic alloy,
solution alloy (2) a eutectic alloy, and (3) a hypereutectic alloy
superimposed on a portion of a eutectic PD.
Certain uncertainties …
~150 expts.
Eutectoid ??
Beaudy and Daane (1962)

Simultaneous optimization & Computation of PDs
• Phase Equilibria data

Thermodynamic data
Structural data (SRO)
• All types of data need to be optimized based on a

physically meaningful, computationally efficient and
mathematically tractable thermodynamic model.
• CALPHAD (CALculation of PHAse Diagrams) methodology

• Unary Systems: SGTE database for standard
representation of Gibbs energy functions (Dinsdale,1991)
• Unary  Binary  Ternary  Quaternary etc.

Thermodynamic Models of Solutions
• Ideal solution model:

A and B atoms are identical except the labels.
Random distribution of atoms on atomic sites.

(Point approx.)
NO SHORT RANGE ORDER.
Hmix = 0 Smix = Sid = -R (xA Log xA + xB Log xB)
Gmix, id = RT (xA Log xA + xB Log xB)
G = xA GA0 + xB GB0 + RT (xA Log xA + xB Log xB)

• Regular solution model:

Only moderate departures from random distribution of
atoms on atomic sites.
NO SHORT RANGE ORDER.
Hmix = Ω xA xB ( to random approx. of unlike pairs)
Smix = Sid = -R (xA Log xA + xB Log xB)
G = xA GA0 + xB GB0 + RT (xA Log xA + xB Log xB) + Ω xA xB

• Quasi-chemical theory (pair-wise approx.):

Random distribution of pairs of atoms on pairs of
sites, namely, nAA, nAB, nBA, nBB pairs are randomly
distributed.
Smix = - (1/2) RZ (yAA Log yAA + yAB Log yAB + yBA Log yBA
+ yBB Log yBB) – (Z-1) R (xA Log xA + xB Log xB)
Hmix = Ω yAB
• SHORT RANGE ORDER is considered.

SRO ??
Thank you all !

20230102-MT-205-PD-BNS-L-1 To L-3 (2022-2023) Notes-1

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MT-205 Phase Computational

Computational Design of Materials

Unary Systems: Thermodynamic conditions of

IIT (BHU), Varanasi MT 205 PD BNS L-1 to L-3 Jan, 2023

Binary Systems with Two Phase Equilibria: Gibbs energy-

composition diagrams. Solution models. Isomorphous

systems. Calculation of liquidus and solidus in ideal

systems. Lever rule. Iso-Gibbs energy curves. Equilibrium

diagrams for systems exhibiting moderate departures

from ideal behaviour. Congruent minimum and congruent

IIT (BHU), Varanasi MT 205 PD BNS L-1 to L-3 Jan, 2023

Equilibrium and quasi-equilibrium solidification in

isomorphous systems and corresponding microstructures.

Stability of a phase. Stability function. Miscibility gap and

chemical spinodal boundaries. Thermodynamic

conditions and determination of miscibility gap, spinodal

boundaries and consolute point. Decomposition inside

and outside spinodal boundary and the microstructural

features. Illustrative examples. (9 L)

IIT (BHU), Varanasi MT 205 PD BNS L-1 to L-3 Jan, 2023

Binary Systems exhibiting Invariant Reactions: Possible

invariant reactions and the thermodynamic conditions.

Eutectic systems. Primary and eutectic solidification and

resulting microstructures. Ag-Cu, Al-Si and Pb-Sn

systems. Eutectoid, monotectic and monotectoid systems.

Peritectic systems. Solidification in peritectic systems and

resulting microstructures. Cu-Zn system. Peritectoid,

syntectic and metatectic systems.

IIT (BHU), Varanasi MT 205 PD BNS L-1 to L-3 Jan, 2023

Ordered phases. Al-Cu and Ti-Al systems.

IIT (BHU), Varanasi MT 205 PD BNS L-1 to L-3 Jan, 2023

Ternary Systems: Graphical representation of ternary

IIT (BHU), Varanasi MT 205 PD BNS L-1 to L-3 Jan, 2023

Computation of Phase Diagrams: CALPHAD methods and

IIT (BHU), Varanasi MT 205 PD BNS L-1 to L-3 Jan, 2023

1. P. Gordon: Principles of Phase Diagrams in Materials

Systems, McGraw-Hill, 1968.

2. S.P. Gupta, Phase Equilibria in Materials, Allied, 2003.

3. D.R.F. West and N. Saunders: Ternary Phase

Diagrams in Materials Science, 3rded., Woodhead, 2002.

4. J.-C. Zhao (Ed.): Methods for Phase Diagram

Determination, Elsevier, 2007.

IIT (BHU), Varanasi MT 205 PD BNS L-1 to L-3 Jan, 2023

1. D.A. Young: Phase Diagrams of Elements, Univ. of

IIT (BHU), Varanasi MT 205 PD BNS L-1 to L-3 Jan, 2023

5. A. Prince: Alloy Phase Equilibria, Elsevier, 1966.

IIT (BHU), Varanasi MT 205 PD BNS L-1 to L-3 Jan, 2023

Mid Sem Exam : 30

End Sem Exam : 50

Total : 100 Marks

Relative Grading, ensuring minimum learning levels.

IIT (BHU), Varanasi MT 205 PD BNS L-1 to L-3 Jan, 2023

➢ Materials Behaviour at microscopic scale:

➢ Design and fabrication of engineering components:

➢ Ensuring better service life and performance.

IIT (BHU), Varanasi MT 205 PD BNS L-1 to L-3 Jan, 2023

IIT (BHU), Varanasi MT 205 PD BNS L-1 to L-3 Jan, 2023

➢ G of each phase in the system as a function of

➢ These ei characterize the system ==> Database.

IIT (BHU), Varanasi MT 205 PD BNS L-1 to L-3 Jan, 2023

➢ CT involves finding the characteristic ei for the materials

IIT (BHU), Varanasi MT 205 PD BNS L-1 to L-3 Jan, 2023