Cluster Expansions for Realistic

Precipitation Kinetics:
Guinier-Preston Zone Formation in an
Al 2 a/o Cu Alloy

RAMOLS
February 8, 2018
Marcel H.F. Sluiter
M.H.F.Sluiter@TUDelft.NL
TU Delft, Dept. MSE, virtual materials & mechanics
Delft, the Netherlands
1
outline
Some comments on modeling & computational
materials science

Lattice gas & cluster expansions

illustration of recent work – Early stages of

precipitation in Al 2% Cu alloy

2
 Computational Materials Science
Conventional: 1900~
model (theory)  parameterization
parameters from experimental data
measurement  determination of “unknown” parameter
or  description/prediction of phenomenon

3
 Computational Materials Science
Conventional: 1900~
model (theory)  parameterization
parameters from experimental data
measurement  determination of “unknown” parameter
or  description/prediction of phenomenon

e.g. X-ray crystal structure determination:

theory of diffraction  crystal structure,
atomic scattering factors, X-ray wavelength
scattering factors, wavelength from experiment
diffraction pattern  crystal structure (becomes known)
when crystal structure is known  can predict diffraction pattern

4
 Computational Materials Science
Conventional: 1900~
model (theory)  parameters (from experiment)
measurement  determination of “unknown” parameter
or  description/prediction of phenomenon

Ab initio modeling: 1980~

(only) ab initio data to predict/guide/describe experiment

5
 Computational Materials Science
Conventional: 1900~
model (theory)  parameters (from experimental data)
measurement  determination of “unknown” parameter
or  description/prediction of phenomenon

Ab initio modeling: 1980~

(only) ab initio data to predict/guide/describe experiment

Integrated computational materials engineering: 2008~

Focus on process instead of property [Combine models in a chain]

6
 Computational Materials Science
Conventional: 1900~
model (theory)  parameters (from experimental data)
measurement  determination of “unknown” parameter
or  description/prediction of phenomenon

Ab initio modeling: 1980~

Integrated computational materials engineering: 2010~

Big Data & the Materials Genome: 2010~

• Ab initio database “harvesting”
• speed-up materials development
• automate “discovery”, serendipity by brute force

7
Computational
Ab initio modeling
Materials Science
Integrated computational materials engineering:
Big Data & the materials genome

What is next?
THIS?

“there is plenty of room at the bottom”

(Feynman)

8
Understanding & Insight

Especially when data is available without limit

9
 Atomistic potentials
• ab initio calculations remain too slow for large scales
• Constructing potentials (force fields) is labor intensive
 automated tool for generating potentials

10
 Lattice gas models
Solid solutions and precipitation: Lattice gas models
Lattice gas:
fixed lattice
at every lattice position
one and only one
atom
multiple atom species
(vacancy is also atom
species)

Thermodynamics of crystalline solids (phase diagrams, etc.)

11
CE: clusters
Clusters: groups of points (preferably compact)
points, pair1, pair2, triangles, squares
grouped by symmetry
CE: cluster probabilities
Point: A (white), B (black)
Pair: AA, AB, BA, BB; etc.
Cluster Expansion (CE)
Property of a lattice gas linearly expanded in terms of
correlation functions

H = enthalpy (expandable property)

J = effective correlation (cluster) interaction,
x = correlation function
(measure of AA and BB, AB pairs, <s s>),
s = structure, a = type of correlation (cluster)
CE: correlation functions
Correlation functions: form a “basis”, independent
variables that describe the cluster probabilities &
configuration

Cluster probabilities are NOT independent

Pi(A)+Pi(B)=1
Pij(AA)+Pij(AB)+Pij(BA)+Pij(BB)=1
Pi(A)=Pij(AB)+Pij(AA) sumrules
Pij(AB)=Pij(BA) (high symmetry lattices)
i,j site labels
CE: sumrules
Pi(A)+Pi(B)=1
Pij(AA)+Pij(AB)+Pij(BA)+Pij(BB)=1
Pi(A)=Pij(AB)+Pij(AA)
Pij(AB)=Pij(BA) (high symmetry lattices)

Knowledge of Pi(A) and Pij(AA) is adequate to

determine Pi(B), Pij(AB), Pij(BA), Pij(BB)

 Pi(A) and Pij(AA) are valid (but not unique)

choices as correlation functions (CF) xi and xij
CE: CF & “simple” structures

fcc L12 L10 L12 fcc

Al4Cu0 Al3Cu1 Al2Cu2 Al1Cu3 Al4Cu0

For simple periodic structure CFs can be determined easily

Al3Cu: P(A)=3/4; P(B)=1/4;
P(AA)=P(AB) =1/2; P(BB)=0
CE: Structure Inversion
(Connolly-Williams)

For a set of structures “s” both H(s) and xa(s) are known 
inversion gives Ja
CE: Structure Inversion
How to find the best set of clusters/correlations a?

Enumerate all possibilities (impossibly many permutations)

Aufbau: add the one that improves fit the most, repeatedly
genetic algorithm, simulated annealing, compressive sensing,
LASSO etc.
 CE: quick evaluation
linear eqn. allows very quick evaluations
 Ground states searches &
searches for extreme properties

b 73, 174204 (2006) with C. Colinet & A. Pasturel

 Ground state search in fcc Al-Cu
Solid state part of Ag-Pt
phase diagram

Al Cu

Code available “iCVM” (M.H.F.Sluiter@tudelft.nl)

 Lattice gas models
Solid solutions and precipitation: Lattice gas models
Thermodynamics (phase diagrams, etc.)
Now… realistic kinetics

Vacancy formation energy depends strongly on neighborhood

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 Lattice gas models
Solid solutions and precipitation: Lattice gas models
Thermodynamics (phase diagrams, etc.)
Now realistic kinetics
Vacancy formation energy depends strongly on neighborhood
Barriers for diffusion also depend STRONGLY on neighborhood

23
GP zones in Al 2 a/o Cu at 450 K

453K HRTEM image

(courtesy Chunhui Liu &
Henny Zandbergen, TUD)
diffusion activation barriers in
concentrated alloys
Absorbing Markov chains
GP-I  GP-II zones
Al 2% Cu after a quench from 750 K
to 300 K
Al-Cu-Vac
Diffusion activation barrier neighborhood
n: how many Cu
dependent (0.2 eV ~ 1 eV) atoms around a Cu
Vacancy concentration 3e-5 atom
(T=750 K, DHvac=0.67eV)
Jump attempt frequency: 1 THz
T=300 K
kinetic Monte Carlo simulation
in Al 2 a/o Cu at 300 K
Code & simulation
with dr Xi Zhang
“Real” Alloys: Multi-Component Alloys
AA6061(at.%)
Al-0.9Mg-0.59Si-0.09Cu-0.28Fe-0.07Cr-0.05Mn-0.02Zn-0.05Ti

AA6061 at room T
with and without Sn
addition

minor alloying elements

cannot be ignored
0.004% Sn  30x slow down
Sn-vacancy binding, or
activation energies involved
too?
 Conclusions
Strong drive towards modeling materials properties &
processes integrally

(Interatomic) interactions at the heart of materials related

simulations

Lattice gas formalism moving from thermodynamics towards

kinetics

Kinetics is rich and complex field – even in the highly

idealized area of lattice gases

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 Software
Cluster expansion & cluster
variation method:
iCVM
m.h.f.sluiter@tudelft.nl

All electron code:

TOMBO
Newest version:
Ohno@ync.ac.jp

MEAM potential fitting:

MEAMfit
CPC repository
Newest version:
andrew.duff@stfc.ac.uk

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Cluster expansions of diffusion
activation barriers (& attempt freq)
(Non)Constant diffusion
activation barriers
Materials Properties
Most basic properties: thermodynamics!
Derivatives of the energy of a material:
dE
CV =
dT V , Ni ,... d 2E
B = Vo
dV 2 V =V d 2E
o Cij =
d�i d�j

Some properties more indirect:

a (T ) � V (T ) : min[G (T , P = Po )]
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 Computational Databases III
Extended by Ceder group at MIT: >154 experimentally known
x-tal structures for >82 binary alloys (ternary alloys are not
public)  datamining structure predictor. Fisher et al. Nat.
Mater. 5, 641 (2006)

A.R. Oganov et al. USPEX (Universal Structure Predictor:

Evolutionary Xtallography,
http://mysbfiles.stonybrook.edu/~aoganov/USPEX.html)
Oganov & Glass, J Chem Phys 124, 244704 (2006)
can generate entirely new structures and their
energetic/crystal structure details!

 Create a database automatically! 36

 Computational Databases IV
Correlations in data (87 A-B alloys with A3B of Fe3C type 52
have AB2 of MgCu2 type)

More structures in energy database

 More accurate prediction of
not yet computed crystal structures

Fisher et al. Nat. Mater. 5, 641 (2006) 37

 Computational Databases V
Other properties being compiled: superhard materials,
bandgap engineering, Diffusion…
D = a2 f v exp[ -(Gvac + Gmig)/kT ]
= a2 f v exp[(Svac+Smig)/k] exp[-(Hvac+Hmig)/kT]
= Do exp[ - Q/kT ]

Beginning efforts (all impurities in Al)

Simonovic & Sluiter Phys. Rev. B 79 054304 (2009).

Experimental data compiled in “Dictra” “JMatPro”

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Database: filling in missing data
Ab initio computations to fill in gaps in experimental data

squares: current predictions

circles: expt
triangles: other calcs

Blue: magnetic

39

D. Simonovic & M. Sluiter, Phys. Rev. B 79 054304 (2009)

 With missing data tendencies appear
Ab initio computations to fill in gaps in experimental data

Linear Q(VX)

INSIGHT! 40

Partial molar volume well-known: practical!

 How databases with experimental
data benefit the computational
(materials science) field

my own journey of discovery in the wonderful world of the

Pauling File of Pierre Villars and many co-workers

1) Finding superstructures (ordered structures based on

some simple lattices such as fcc, bcc, or hcp)

2) Finding ground states in alloys that were believed to be

non-compound forming
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Superstructures
Ordered structures in alloys

fcc superstructures: CuAu-I L10 Cu3Au L12

Found experimentally, not systematical at all!

Let’s try to find superstructures methodically…

42

M. Sluiter, Phase Transitions 80, 299 (2007).

 Databases: finding superstructures
In superstructures all atomic positions have the same
nearest neighbor polyhedron
(atomic environment type [P. Villars et al.])

fcc

 In the structure database find those structures in which

each of the positions has the nearest neighbor
polyhedron of the underlying lattice

43

M. Sluiter, Phase Transitions 80, 299 (2007).

Databases: finding fcc superstructures
Many known structures for the first time identified as fcc
superstructures

More than a dozen “new” fcc prototype structures:

e.g. Mo3Al8

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M. Sluiter, Phase Transitions 80, 299 (2007).

 Databases: finding bcc superstructures
Many known structures for the first time identified as bcc
superstructures – some quite complex Zr9Pt11 (6
inequivalent positions, tI40, space group #87)

About 70 bcc
superstructures found!
45

M. Sluiter, Phase Transitions 80, 299 (2007).

 Databases: finding hcp superstructures
Cu10Sb3 (5 inequivalent positions, hP26, space group #176)

46

M. Sluiter, Phase Transitions 80, 299 (2007).

Computational Materials Science…

Historically:
• 1) composition + (crystal) structure  a property
• 2) increasing sophistication to get that one property
• 3) each composition+structure = individual case
• 4) reverse: properties  composition + structure
generally NOT possible

Most practical (industrial applications)?

properties  composition + structure
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 First step towards from
properties  structure/composition

Simply predict the structure of all the compounds

in a mixture of elements

We cannot do it yet!

In recent years much progress (datamining structure

predictor, USPEX) …but… extremely computer
intensive – is there something more simple and
intuitive?

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 Finding Compounds were we know of
none! E.g. Au-Si and Au-Ge

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E Tasci, M Sluiter, A Pasturel, P Villars, Acta Materialia 58, 449 (2010)
 Mimic Nature …

Start with computer simulation of the liquid alloy and

determine local structure in the liquid
If we simulate the liquid at low temperature, the liquid
should start resembling the solid state
At the eutectic, we can go
down in T the most 
most obvious point to try

50

E Tasci, M Sluiter, A Pasturel, P Villars, Acta Materialia 58, 449 (2010)

 Computed local structure in the Au-Si
liquid
Coordination
numbers in
the liquid,
around Si
and around
Au atoms

Which crystal
structures
match?
51

E Tasci, M Sluiter, A Pasturel, P Villars, Acta Materialia 58, 449 (2010)

 Crystal structure with the same local
structure (coordination numbers) as
the Au-Si liquid
27 prototype structures only!

Pd5As UTe5 Ti9Se2 Zr9S2 Co2Al9 Pd4S PtPb4 RhBi4

PtSn4 NbTe4 AuPb3 V3S Sc3Co Cu3As …

Out of a database (Pauling File) with 30.000

structures with 2700 prototypes

For 27 structures we can perform ab initio

calculations in not too much time….
52

E Tasci, M Sluiter, A Pasturel, P Villars, Acta Materialia 58, 449 (2010)

 Eureka! A compound is found for Au-Si
Au4Si with Pd4S prototype structure has exothermic
formation enthalpy (only one among the 27 structures)

Si (blue) completely
surrounded by 8 Au (red)

Strong attraction Si-Au

(already deducted by
Turnbull and Chen 1964!)

53

E Tasci, M Sluiter, A Pasturel, P Villars, Acta Materialia 58, 449 (2010)

 Au-Ge phase diagram just like Au-Si …
Ge is a little larger than Si  local structure in
the Au-Ge liquid ≠ Au-Si liquid !

54

E Tasci, et al PRB (2010)

 Au-Ge phase diagram just like Au-Si …
Now only 11 prototype crystal structures
Again just one of them exothermic: Pt5P2 type

Quite unlike
Au-Si structure
but
Ge atom again
Au neighbors
only (6)

55

E Tasci, et al PRB (2010)

 Summary (1)
New approaches to database generation emerging:
computational databases

a) stable structures, energetics (thermodynamics)

b) physical properties (diffusivity, other transport properties)

Opportunity to fill gaps in the experimental data

Possibility to discover tendencies previously not apparent

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Summary (2)
Databases: amazing unforeseen applications
finding superstructures
finding compounds in non-compound forming alloys (Au-
Si, Au-Ge)

many other applications exist! (scarcity [In,Sc],

environmental/health substitutions [Pb,Ni,Cr 6+], energy
materials)

design databases with flexible use in mind

justification for database construction – much more than
compilation of scattered data  research tool construction
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Complex models!
Interatomic interactions  interatomic
(de)bonding  molecules

Modeling of epoxy on Al2O3, influence of H2O

(courtesy Barend Thijsse & S. Echeverri-Restrepo)
58
Tools & Algorithms
Elastic Tensor
• ab initio calculation much easier and faster
than measurement
• typical disagreement with expt: 5%
automated tool for online database (free)
http://www.materialsproject.org/

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 CE: Why a linear form?

Formation enthalpy of an organic molecule:

e.g. CH4 from diamond and H2 gas
CH4  C + 2H2
4 C-H bonds formed
2 C-C bonds sacrificed (in diamond C has 4 C nearest neighbors
=> 2 C-C bonds per C)
2 H-H bonds lost (2H2 molecules atomized)
DHform(CH4)=4DH(C-H)-2DH(C-C)-2DH(H-H)
CF: multinaries
Cluster probabilities are redundant
Pi(A)+Pi(B) +Pi(C) = 1
Pij(AA)+Pij(AB)+Pij(AC)+Pij(BA)+Pij(BB)+Pij(BC)
+Pij(CA)+Pij(CB) +Pij(CC) = 1
Pi(A)=Pij(AA)+Pij(AB)+ Pij(AC); etc.
Pij(AB)=Pij(BA) ; Pij(AC)=Pij(CA); etc.

Knowledge of Pi(A), Pi(B) and Pij(AA), Pij(AB),

Pij(BB) is adequate to determine all Pi, Pij

 Pi(A), Pi(B) and Pij(AA), Pij(AB), Pij(BB) are

valid (but not unique) as CF x1 – x5
CF: sumrules & multinaries

Can always “ignore” one species for determining

the correlation functions:
AB binary ignore B Pi(A), Pij(AA)
ABC ternary ignore C Pi(A), Pi(B), Pij(AA),
Pij(AB), Pij(BB)

RULE: correlation functions for N-component

system = probabilities of the N-1 system

For binary only pure A clusters needed  “cluster

expansion” instead of “correlation fn expansion”
 Struct. Inversion: completeness
How to find the best set of clusters/correlations a ?

Completeness: all subclusters (sub correlations) are included

also
If pair included, then also its constituent points,
If triangle included, then also its constituent pairs

Why “completeness”?
invariance when change of choice of CF