Computational Thermodynamics

of Alloys using CVM

S. Lele and B. Nageswara Sarma

Centre of Advanced Study
Dept. of Metallurgical Engg., IT-BHU, Varanasi

BHU SL/BNS ’07

 Coworkers

G Srinivasa Gupta
Shreyansh Shah
Manoj Kumar
V Arvind
Nikhil Singh
G Vamsi Madhav
A Pandey

BHU SL/BNS ’07

 Introduction

¾ CALPHAD: Enthalpy: Redlich-Kister expansion

Entropy: Ideal with additional temperature
dependent terms similar to enthalpy expression
¾ Only phase diagram & thermodynamic inputs
No structural input or output
¾ No physical basis for energy/entropy
parameters
¾ No proper vibrational mixing effects
¾ Extrapolation to multicomponent systems
problematic owing to non-physical parameters
in enthalpy and non-physical entropy

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 Cluster Expansion-Cluster Variation Methods

• CVM (Kikuchi, 1951)

Configurational entropy of mixing
• Ordering using CVM (van Baal, 1973, Sanchez &
de Fontaine, 1978)
Calculation of fcc ordering phase diagrams
Correct topology
• CE (Sanchez et al, 1984)
Configurational enthalpy of mixing including
multicomponent case
• CE-CVM (Schlijper, 1983-85)
Exact in thermodynamic limit (infinite clusters)

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 Cluster Expansion-Cluster Variation Methods

• CE-CVM: Hierarchy of increasingly accurate

approximations suitable for computational
thermodynamics.

• Applied to many phase diagram calculations-

ternary systems, interstitial solutions, oxides,
magnetic phases (Saunders & Miodownik, 1998,
Chang et al., 2004).

• No systematic effort to standardize methods

and create data base.

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 Plan of presentation

• Choice of standard orthogonal basis

(Sarma & Lele, 2005)
Energy parameter database
• Vibrational mixing contributions (Sarma & Lele, 2007)
Model independent approximate formulation
• Solvent basis formulation for efficient & robust
computation (Sarma et al. 2007)
Exact results at infinite dilution
• Special points of phase diagrams (Gupta et al. 2005)
Initial values of energies for optimization
• Simultaneous optimization of PD & TC data

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 Maximal Clusters

• Cluster : Set of sites (a closed graph)

• BCC : Irregular Tetrahedron (T)
• FCC/CPH : Tetrahedron+Octahedron
(TO)

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 Cluster Configurations

• Cluster configurations: Populate atomic

species on cluster sites, e.g. AA, AB & BB on
pairs of sites.
• Cluster variables: Probabilities (fractions) of
occurrence of cluster configurations.
- Not all independent
• Correlation functions: Independent set of
configurational variables (Sanchez et al., 1984).

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 Occupation & Site Operators
• Occupation operator :
PiA (PiB, PiC) = 1 if an A (B, C) atom at site i
= 0 otherwise.
PiA + PiB + PiC = 1 => 1 dependent variable

• Site operator : σi(k) = tA(k) PiA + tB(k) PiB + tC(k) PiC

⎡ 1 ⎤ ⎡1 1 1 ⎤ Pi ⎤ ⎡ A

⎢σ (1) ⎥ = ⎢ t (1) t (1) (1) ⎥ ⎢ B ⎥

⎢ i ⎥ ⎢A B tC ⎥ ⎢ Pi ⎥
⎢⎣σ i( 2) ⎥⎦ ⎢⎣t A( 2) t B( 2) tC( 2) ⎥⎦ ⎢⎣ Pi C ⎥⎦
tA(k), tB(k) & tC(k) : Nos. representing types of atoms
No. of site operators 1 less than components.
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 Choice of Basis
• Orthogonal basis (for data base) : Row wise
orthogonal T-matrices lead to orthogonal σi(k)
vectors (Cenedese & Gratias, 1991, Sarma & Lele, 2005).
• Solvent basis : The occupation operators for all
solute atoms are independent while that for solvent
is treated as dependent.

Orthogonal A-Solvent
⎡ 1 1 1⎤ ⎡1 1 1⎤
⎢ −1 1 0 ⎥ ⎢0 1 0⎥
⎢ ⎥ ⎢ ⎥
⎢⎣−1/ 2 −1/ 2 1⎥⎦ ⎢⎣0 0 1⎥⎦
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 Correlation Functions & Cluster Variables

• Each correlation function is an average of an

appropriate product of site operators over all
sites (by definition)

〈σ i 〉 = u1 〈σ iσ j 〉 = u2

• Each cluster variable is an average of an

appropriate product of occupation operators

〈 Pi 〉 = x B
B
〈 Pi P 〉 = y BB
B
j
B

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• Inverting the orthogonal T-matrix for a binary
⎡ Pi A ⎤ 1 ⎡1 − 1⎤ ⎡ 1 ⎤
⎢ B⎥ = ⎢ ⎥ ⎢σ ⎥
⎣ Pi ⎦ 2 ⎣1 1 ⎦⎣ i ⎦
• Each cluster variable can be expressed in terms of
correlation functions, e.g.,

〈 Pi P j 〉 =
B B 1
( 1 + 2 〈σ i 〉 + 〈σ iσ j 〉 )
4
1
⇒ y BB = (1 + 2 u 1 + u 2 )
4
• Cluster variables : independent of basis =>
transformation relations among correlation functions
defined on different bases (Sarma & Lele, 2005)

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 Cluster Expansion Method
• The internal energy U (as well as any
configuration-dependent property) of the system
can be expressed as (Sanchez et al., 1984)

U = ∑ ei mi ui
• Sum truncated by choice of maximal cluster.
mi : multiplicity, ei : effective cluster interaction /
cluster expansion coefficient (ECI / CEC)
• Configurational enthalpy / energy of mixing
ΔH = ΔU = ∑ ei mi Δui
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 Maximal Clusters

• No. of Correlation Functions

(microscopic variables, binary)
BCC : 4 FCC : 9 CPH : 13
• BCC : I- & II-Neighbour Pairs, Triangle,
Tetrahedron

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 CEC Transformations

• Enthalpy : Independent of basis => Known

transformations among ui give
transformations among ei defined on different
bases (Sarma & Lele, 2005).

• Required to define multicomponent system

CECs consistently with known sub-system
CECs.

• For bcc ternary, there are 18 CECs, 4 each

from 3 binary subsystems and 6 purely
ternary CECs (3 triangle+3 tetrahedral
interactions)(Sarma & Lele, 2005).
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 CECs

• Similarly, for quaternary systems, the purely

quaternary interactions are solely due to
tetrahedral and higher cluster interactions.

• For T and TO approximations respectively,

interactions only up to quaternary and 6-atom
ones are relevant.

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 Cluster Variation Method

• Configurational entropy of mixing is expressed

in terms of Boltzmann summations of the type

– R mi[ yi ln yi ]

for each of the (sub)clusters such that each

cluster is counted just as many times as it’s
multiplicity mi.
• Each term multiplied by Kikuchi-Barker
coefficient to ensure this and summed

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 Vibrational & Electronic Effects : Unary Systems
c p = c har + c anh + c el
⎡ (θ D (2) )2 ⎛ γe ⎞ ⎤
c p = 3R ⎢1 − 2
+⎜A+ ⎟T + BT ⎥
2

⎣ 20T ⎝ 3R ⎠ ⎦
⎡ 3(θ D ( 2) )
2
Gve = a + R ⎢ − (1 − 3 ln θ D (0) )T − 3T ln T +
⎣ 40T
⎛ γe ⎞ 2 1 3⎤
− ⎜A+
3
2 ⎟T − 2 BT ⎥
⎝ 3R ⎠ ⎦

• θD(n) correspond to cut-off frequencies ωD(n) in a Debye model

which reproduces correctly the nth moment of the vibrational
frequency ω for a given phonon density of states. (Grimvall, 1986)

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 CALPHAD Database for Unary Systems
⎡ 3(θ D (2) )
2
( )
Gve = a + R ⎢− 1 − 3 ln θ D (0) T − 3T ln T +
⎣ 40T

3⎛ γe ⎞ 2 1 3⎤
− 2 ⎜ A+ ⎟T − 2 BT ⎥
⎝ 3R ⎠ ⎦
• Database (Dinsdale 1991)

Gve = a + bT + cT ln T + ∑ d nT n
• Usually n = -1, 2 and 3
• Both expressions have terms with same
functional dependence on T.

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 Debye Temperatures

• Moruzzi et al. (1988) (empirical)

1/ 2 1/ 2
⎡ r0 BT ⎤ ⎡ kE b ⎤
θ D = G fcc ⎢ ⎥ = G fcc ⎢ ⎥
⎣ M ⎦ ⎣ M ⎦
BT : compressibility, Eb : binding energy, k : potential
dependent constant, M : atomic mass
• Assume this result for each of the θD(n)
1
⎡ kEb ⎤ 2
θ D (n) = Gα (n) ⎢ ⎥
⎣ M ⎦
k is same but Gα(n) different for each θD(n) for each
phase α.
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 Vibrational & Electronic Mixing Contributions

First Approach
• Vibrational : Included through Debye model, by
expanding say ΔlnθD similar to enthalpy of mixing,
with different CECs.

• Twice the no. of parameters, but configurational

dependence of these contributions is well
represented.

• Electronic : Included in cp through a linear T term.

Another set of CECs, if required. Usually ignored.
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 Mixing Contributions to Debye Temp. of Alloys
Second Approach
• Recall 1
⎡ kEb ⎤ 2
θ D (n) = Gα (n) ⎢ ⎥
⎣M ⎦
• Assume this relation is valid for alloys. Further,
assume M & k to be geometric averages.
• Mixing effects arise through the Eb and are
automatically included
1
⎛ x A E A + x B E B + ΔE b ⎞
2

θ D ( n ) = (θ A ( n ) ) xA
(θ B ( n ) ) xB
⎜⎜ xA xB
⎟⎟
⎝ E A E B ⎠
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 Mixing Contributions to Debye Temp. of Alloys

⎡ 1/ 2 ⎤
Δ ln θ D (0) ≈ ⎢ ⎥ ΔH c
⎣ x A E A + xB EB ⎦
• where ΔEb => ΔHc .
Similarly for other terms in cp.
• The scaling factor has a magnitude of ~ 10-4.
• This is similar to the factors obtained from
optimization of phase diagrams of Sc-Ti, Sc-Zr,
Ti-Zr and Hf-Ti systems using first approach.

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 Mixing Contributions to Debye Temp. of Alloys
• Richardson (1974) observed empirically that the
contributions to entropy of mixing due to thermal
effects are proportional to those due to
configurational effects, with a proportionality
constant of ≈1/3000 similar to present scaling
factor.
• Compatible with unary system database and
directly applicable to multi-component systems.
• No additional mixing parameters.
• Thus the approximations made seem to be
justified for the small vibrational mixing effects.
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 Free Energy

• Thus, the free energy of mixing (ΔG) is given by

ΔG = ΔGc + ΔGve ,
and is a function of
(i) model energy parameters - CECs (ei),
(ii) temperature (T) & composition (xB) and
(iii) correlation functions (ui)

ΔG = f (ei ; T, xB ; ui)

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 Simultaneous Optimization

• Energy parameters (CECs) :

Determine by minimization of χ2 wrt ei.
2
N
⎛ εi ⎞
χ = ∑ ⎜⎜ ⎟⎟
2

i =1 ⎝ σ i ⎠
ε = error = xobs – xcalc or Tobs – Tcalc, etc.
σi = standard deviation for each data point.

Outer loop. Levenberg-Marquardt method. Each

iteration yields a correction dei to the initial ei.

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• Macroscopic Variables (Tcalc & xBcalc) :
Solve equilibrium equations for any two of the set of
two compositions and temperature knowing third
ΔμA = ΔμB = 0.
Middle loop. Newton-Raphson method.
Each iteration yields a correction dxBcalc to the initial
xBcalc for either phase or dTcalc to the initial Tcalc.

• Microscopic Variables (ui) :

Determine by minimizing free energy for each phase
wrt ui.
Inner loop. Newton-Raphson method.
Each iteration yields a correction dui to the initial ui.

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 Initial Values of CECs for Optimization

• Successful optimization requires initial values

of CECs sufficiently close to the true values to
reproduce the topology of the phase diagram
and definition of the errors.
• These can be estimated from special points
of the phase diagrams.
(i) Initial slopes of phase boundaries
– dilute solutions
(ii) Consolute point
(iii) Congruent point

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 Sc-Zr System

Beaudry and Daane, 1963 Optimized data:

Phase equilibria data

β (Sc, Zr)

α (Sc, Zr)

CVM Optimized phase diagram

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 β

Sc Ti

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 SRO Parameters

• Cowley-Warren short range order parameters

<P AB
> < Pi P >
A B

σ ij = 1 − ij
= 1−
j

x A xB x A xB
• Can be computed only in physically based
models such as CVM. Conversely, can be
used as input data.

• First neighbour SRO parameter for Sc-Ti in

bcc phase at different temperatures. (Vertical
lines at spinodal compositions)
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BHU SL/BNS ’07
 Summary

• Systems with disordered phases can be

optimized by using CVM

• Method for defining CECs for higher order

systems, such as ternary system A-B-C, based
on the CECs for component systems A-B, B-C &
C-A in a consistent manner.

• Experimental effort for multicomponent systems

can be minimised.

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 Summary
• Approximate method for including vibrational
contributions developed. Requires no additional
mixing parameters.

• Analytical CVM results for solutions at infinite

dilution. Provide accurate initial values for
correlation functions.

• Estimation of CECs from phase diagram special

points.

• Computational burden reduced by 100 times.

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 Thank you all !

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 Comparison of Calc & Obs Data

• Sc-Zr Congruent point

Calc.:26 at.% Zr, 1407°C
Obs. :30 at.%Zr, 1415°C

• Sc-Ti Monotectoid temperature

Calc.:13.2, 47.5, 74.4 at.%Ti, 1050°C
Obs. :12.8, 47.4, 74.2 at.%Ti, 1050°C

Eutectoid temperature
Calc.:8.6, 92.6, 93.1 at.%Ti, 875°C
Obs. :8.5, 92.1, 93.1 at.%Ti, 875°C

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