07 Data Modeling For Thermodynamics

Thermo-Calc Software
www.thermocalc.com
MAI Data Management Workshop:
Data Modeling for Thermodynamics
and Other Properties
June 8-10, 2011 - Dayton, OH
P K Mason
(1)
, A. Engstrm
(2)
, J. Bratberg
(2)
, Q. Chen
(2)
1. Thermo-Calc Software Inc
2. Thermo-Calc Software AB
Software: Thermo-Calc
Software for thermodynamic calculations that can be applied to a range of applications including:
Calculating stable and meta-stable phase equilibrium
Transformation temperatures
Amount and composition of phases
Thermochemical data such as;
enthalpies
heat capacity,
activities, etc.
Predicting driving forces and transformation temperatures
And much more.
Thermodynamic
Database
R- and -phase
Alloy 1
( )

i m
x P T G , ,
( )
0
, ,
=
i
i m
x
G
x P T G N G
Software: DICTRA
2.60 m
Ball screw for the Airbus
A380 aircraft: a martensitic
as carburized stainless steel
0,0
0,4
0,8
1,2
1,6
2,0
2,4
2,8
3,2
3,6
4,0
4,4
4,8
0 100 200 300 400 500 600 700 800 900 m
%C
profil carbone calcul en fin d'enrichissement
profil carbone calcul aprs 3h de diffusion
Fe-12Cr-2Ni-2Mo-0.12C at 955C:
Calculated carbon profile at the end of the enrichment step
Calculated carbon profile after 3h of diffusion
Example: Simulation of carbon evolution in
high alloyed steels by Aubert & Duval, France.
Turpin et al., Met. Trans. A
36(2005), pp. 2751-60
Distance from surface (m)
C
a
r
b
o
n

c
o
n
t
e
n
t

(
%
)
Carburizing and decarburization
Microsegregation during solidification
Precipitate growth and dissolution
Precipitate coarsening
Interdiffusion in coating/substrate
TLP bonding of alloys and much more
Where does CALPHAD fit?
Thermodynamics: Gibbs energy
Diffusion: Mobility
Phase Field Method
Langer-Schwartz
First Principles Calculation
From atoms to microstructure: The aim is to predict
microstructure evolution and materials properties.
CALPHAD
f()
Interfacial energy & Volume & Elastic constants

The development of consistent databases where each phase is described
separately using models based on physical principles and parameters
assessed from experimental data is a key feature of this technique.
Thermodynamic data
Computational thermodynamics and CALPHAD (1)
Thermochemical measurements:
Enthalpy
Entropy
Heat capacity
Activity
Phase equilibria:
Liquidus
Solidus
Phase boundary
Gibbs Energy of
Individual Phases
Applications
) , , ( P T x f G
m
=
Computational thermodynamics and CALPHAD (2)
N. Saunders and A.P. Miodownik, CALPHAD
(Calculation of Phase Diagrams): A Comprehensive
Guide, Pergamon Materials Series, 1998
A thermodynamic database in our understanding means a collection of
polynomials describing the Gibbs energy for the individual phases of a
system, as a function of temperature, (pressure) and composition.
Thermodynamic database (1)
( )

i m
x P T f G , , =
Advantages of the tdb format
- open framework ASCII text file
- essentially a mark up language
- extendable with a variety of key words
- not limited to one software code or application
- can have more than one description (tdb) for the same system
Limitations of the tdb format
- Not a linked, SQL type relational database, or HTML, XML
- therefore changes made in one tdb do not translate to other tdbs
automatically. need for an improved system of management?
Thermodynamic database (2)
PARAMETER G(HCP_A3,CO:VA;0) 298.15 +GHSERCO;,,N !
PARAMETER G(HCP_A3,NI:VA;0) 298.15 +GHCPNI;,,N !
FUNCTION GHSERCO 298.15 +310.241+133.36601*T
-25.0861*T*LN(T)-.002654739*T**2-1.7348E-07*T**3
+72527*T**(-1) 1768.0 Y -17197.666+253.28374*T
-40.5*T*LN(T)+9.3488E+30*T**(-9);,, N !
FUNCTION GHSERNI 298.15 -5179.159+117.854*T
-22.096*T*LN(T)-.0048407*T**2;
1728.0 Y -27840.655+279.135*T-43.1*T*LN(T)
+1.12754E+31*T**(-9);,, N !
PARAMETER L(HCP_A3,CO,NI:VA;0) 298.15 -1620-.385*T;,,N !
PARAMETER TC(HCP_A3,CO:VA;0) 298.15 +1396;,,N !
PARAMETER BMAGN(HCP_A3,CO:VA;0) 298.15 1.35;,,N !
PARAMETER TC(HCP_A3,NI:VA;0) 298.15 633;,,N !
PARAMETER BMAGN(HCP_A3,NI:VA;0) 298.15 .52;,,N !
PARAMETER TC(HCP_A3,CO,NI:VA;0) 298.15 411;,,N !
PARAMETER TC(HCP_A3,CO,NI:VA;1) 298.15 -99;,,N!
PARAMETER BMAGN(HCP_A3,CO,NI:VA;0) 298.15 1.046;,,N !
PARAMETER BMAGN(HCP_A3,CO,NI:VA;1) 298.15 .165;,,N !
CALPHAD Methodology
Start
Literature Survey
Reassessment of
related systems treated
with the previous models.
Choice of models for
Gibbs energy of the
various phases.
Selection of
experimental
information.
Estimation of
lacking data.
Parameter
evaluation:
Optimization
and
Estimations.
Comparisons between
experimental data and
model calculations.
Analysis of the
extrapolations to
higher order systems
Assessed description.
Reconsideration of the
models accepted.
New experimental
study.
Reconsideration of selected
data. Identification of
inconsistent information..
Reconsideration of weights
or parameters to be
optimized.
Consideration of
higher-order
information.
Reevaluation
of lower-order
parameters.
Thermodynamic Modeling
Gibbs energy per mole for a solution phase is normally divided in:
ph
m
xs
m
ideal
m m m
G G G G G + + + =
0
Ideal solution model
Regular solution model
Real solution
reference surface
configurational contribution
physical contribution
excess term
Thermo-Calc Software Binary - Real solutions
o
B B
o
A A m
G x G x G + =
0
( )
B B A A
ideal
m
x x x x RT G ln ln + =
xs
m
ideal
m m m
G G G G + + =
0
=
=
0
,
) (
k
k
B A B A
k
B A
xs
m
x x L x x G
( ) .... ) ( ) (
2
,
2
,
1
,
0
B A B A B A B A B A B A
x x L x x L L x x + + =
Redlich-Kister Expansion
Ternary solutions
o
C C
o
B B
o
A A m
G x G x G x G + + =
0
( )
C C B B A A
ideal
m
x x x x x x RT G ln ln ln + + =
.... + + =

> > > i i j j k
ijk k j i
i i j
ij j i
xs
m
I x x x I x x G
From
Binary
From
Ternary
xs
m
ideal
m m m
G G G G + + =
0
The POP file
Experiments are described like an equilibrium calculation.
CHANGE-STATUS PHASE FCC LIQ=FIX 1
SET-COND T=1000 P=1E5
LABEL AFL
EXPERIMENT X(LIQ,CR)=0.22 : 0.02
COMMENT give the journal or other source
CHANGE-STATUS LIQ=FIX 1
SET-REFERENCE-STATE CR LIQ * 1E5
SET-REFERENCE-STATE FE LIQ * 1E5
SET-COND T=2000 P=1E5 X(CR)=.15
EXPERIMENT HMR=-4500:500
Normally collected from the literature
Reliable data is selected and critically assessed
Both phase diagram data or thermodynamic data (H,C
p
...)
can be used
H
m
(
L
i
q
u
i
d
)
Binary and ternary systems
TCNI5: A database for Ni superalloys
Al B C Co Cr Fe Hf Mo N Nb Ni Pd Pt Re Si Ta Ti V W
B x
C x x
Co x x x
Cr x x x x
Fe x x x x x
Hf x x x x x x
Mo x x x x x x x
N x x x x x x
Nb x x x x x x x x x
Ni x x x x x x x x x x
Pd x x x x x x x x x x
Pt x x x x x x x x x x
Re x x x x x x x x x x x x
Si x x x x x x x x x x x x x x
Ta x x x x x x x x x x x x x x x
Ti x x x x x x x x x x x x x x x x
V x x x x x x x x x x x x x x x x x
W x x x x x x x x x x x x x x x x x x
Zr x x x x x x x x x x x x x x x x x x x
20 + 3 elements.
Nearly all binary subsystems assessed for full range composition
All Ni containing ternaries plus other ternary systems also
assessed to full range of composition
292 intermetallic and solution phases
From: Saunders & Miedownik: Calphad -a comprehensive review
iation Averagedev
d % 4 <
Higher order systems: Real alloys for
validation
CALPHAD is about transforming data
CALPHAD has been historically built on good quality experimental
thermodynamic (equilibrium) data (and where necessary
supplemented using theoretical techniques). As such, data is an input
for the CALPHAD community.
CALPHAD also generates and outputs data. Value is added by taking
experimental and theoretical data, developing modular databases
based on the well established CALPHAD methodology which allows
calculations to be made for higher order, multicomponent multiphase
systems of industrial relevance (e.g. alloy design / process
optimization and operational performance).
This approach makes data re-usable and applicable across a broad
range of systems and also provides an important building block for
multi-scale modeling approaches.
Data in, Data stored and Data out
3 Categories of data
Raw Data (data in)
Experimental data
Theoretical data
Refined/Assessed/Transformed Data (data stored, databases)
Do not store raw data
Gibbs energies stored as polynomial functions
Critically assessed interaction parameters enable calculated reproduction
of experimental data
Calculated Data (Data out)
Reproduce most of the raw data.
Make predictions in industry-relevant high-order multicomponent systems
with just data from the constituent low-order systems
Sources of thermodynamic data
Two types of data
Basic thermodynamic and phase equilibrium data the building
blocks of thermodynamic databases
Experimental
Phase equilibrium (phase diagrams) for binary and ternary system
(liquidus/solidus/phase boundary)
Thermodynamic data for compounds/stoichiometric phases
Activity measurements etc
Theoretical
Estimation and Ab initio calculations
Higher order (multi-component data) validation for alloys etc
Experimental
Cp, liquidus/solidus/phase boundary data etc for real alloys
Volume fraction of carbides etc
Calculation of tendency to form sigma
phase: SAF 2507
Fe Base
Cr 23 27%
Ni 6 8%
Mo 3 5%
N 0.25 0.29%
C 0 0.03%
Nominal composition:
Fe 25% Cr 7% Ni 4% Mo 0.27% N 0.02% C
Predict the temperature when sigma-phase becomes stable within
some composition variation:
Volume data
Molar Volume data
V0(phase, constituent array) is the volume at 298.15 K and 1 bar
VA(phase, constituent array) is the integrated thermal expansivity at
1 bar.
Both of these can be composition dependent
G = p V
Adding molar volumes allows volume fractions of phases, density
and coefficient of thermal expansion to be calculated.
Molar volume data are required for e.g. phase field and
precipitation modeling codes.
dT
dV
V
dT V V
T
T
m m
1
,
0
0 0
= =

Molar Volume data
The molar volumes for a system is calculated in a similar way as the
Gibbs energy. For a binary A-B system we have.
o
B B
o
A A m
V x V x V + =
0
xs
m m m
V V V + =
0
=
=
0
,
) (
k
k
B A B A
k
B A
xs
m
x x L x x V
( ) .... ) ( ) (
2
,
2
,
1
,
0
B A B A B A B A B A B A
x x L x x L L x x + + =
Redlich-Kister Expansion
-2
0
2
4
6
8
10
12
14
16
18
10
-3
[
L
(
T
)
-
L
(
2
9
3
)
]
/
L
(
2
9
3
)
200 400 600 800 1000 1200 1400
TEMPERATURE_KELVIN

Example:
Calculated Relative Length Change of Inconel X750
Application of volume data
Example:
Calculated density for some Ni-base alloys
7900
8000
8100
8200
8300
8400
8500

C
a
l
c
u
l
a
t
e
d

d
e
n
s
i
t
y

(
k
g
/
m
3
)
7900 8000 8100 8200 8300 8400 8500
Experimental density (kg/m3)
Inconel 600
Inconel 625
Inconel 718
Inconel X750
Ni-base alloy
Nimocast 75
Udimet 500
Udimet 710
-1%
+1%
6600
6800
7000
7200
7400
7600
7800
8000
D
e
n
s
i
t
y
,

k
g
/
m
3
0 500 1000 1500 2000
TEMPERATURE_KELVIN
NPL recommended
Steel 316: Fe-12Ni-17Cr-1.0Si-2.0Mn-2.5Mo-0.3Cu-0.08C (wt%)
Solidification process
Combining with Scheil or DICTRA simulation, density variation
during solidification can be calculated more properly.
Mobility data
Diffusion controlled simulations (2)
All simulations depend on assessed kinetic and thermodynamic
data. The data are supplied in databases.
| )
| ) J
z t
c
DATABASES
Kinetic Thermodynamics
Mobilities
Gibbs Energy
Diffusivities
Solve Diffusion
where
2
2
c
G
Boundary conditions
(External or Internal)
A numerical finite difference scheme is used for solving a
system of coupled parabolic partial differential equations
| ) | |
| )
z
c
D J
=
2
2
~
c
G
M D
n
kj
CALPHAD for mobility databases
Diffusion without a chemical
gradient:
-Tracer diffusion coefficients
Diffusion under a chemical gradient:
- Chemical interdiffusion coefficients
- Intrinsic diffusion coefficients
Logarithm of the Atomic Mobility for
Individual Elements
Applications
( ) ) , , ( ln P T x f RTM
B
=
Mobility data for Al-Ni
Tracer self-diffusion coefficients of Al and Ni:
),
142000
exp( 10 71 . 1
4 *
RT
D
Al

=

) ln( ) ln(
*
i i
RTM RT D RT =
The tracer diffusion coefficient is
directly related to the mobility trough:
)
287000
exp( 10 26 . 2
4 *
RT
D
Ni

=

PARA MQ(FCC_A1&NI,NI:VA),, -287000+R*T*LN(2.26E-4)
In the database:
PARA MQ(FCC_A1&AL,NI:VA),, -284000+R*T*LN(7.50E-4)
PARA MQ(FCC_A1&NI,AL,NI:VA;0),, -113000+65.5*T
PARA MQ(FCC_A1&AL,AL:VA),, -142000+R*T*LN(1.71E-4)
PARA MQ(FCC_A1&AL,AL,NI:VA;0),, -41300-91.2*T
PARA MQ(FCC_A1&NI,AL:VA),, -145900+R*T*LN(4.40E-4)
Al
Ni
Impurity diffusion coefficient of Ni in pure Al and Al in pure Ni:

),
284000
exp( 10 5 . 7
4
RT
D
Ni
Al

=

)
145900
exp( 10 4 . 4
4
RT
D
Al
Ni

=

Interaction parameters:
Interaction parameters:
-15.0
-14.5
-14.0
-13.5
-13.0
-12.5
-12.0
-11.5
L
O
G
D
C
(
F
C
C
,
A
L
,
A
L
,
N
I
)
0 0.05 0.10 0.15 0.20
Mole-Fraction Al
1573
1523
1473
1423
1373
1323
1273
Ni-Al
Symbols are experimental
data taken from Yamamoto
et al, Trans. Jpn. Inst. Met.
21(1980), p. 601.
0
0.02
0.04
0.06
0.08
0.1
0.12
-1000 -500 0 500 1000
M
a
s
s

F
r
a
c
t
i
o
n
Distance (m)
Cr
Co
W
Ta
Al
Ti
Mo
Re
Hf
Nb
Experimental work performed by T. Hansen, P. Merewether,
B. Mueller, Howmet Corporation, Whitehall, MI.
From:
C. E. Campbell, Metallurgy Division, NIST
Ren-N4/Ren-N5 at 1293 C for 100 h
Ren-N4 Ren-N5

6.35 mm 6.35 mm
Double geometric grid: 200 points
is a 1010 matrix where all
coefficients depend on concentration
~
D
Databases used
Thermodynamics: ThermoTech
Kinetics: NIST Ni-mob
Example: Interdiffusion in Ni-base alloy/coating systems
Example: Interdiffusion in a Ni alloy
Interfacial energies
Modeling multicomponent nucleation
|
|
.
|
\
|

=
kT
G
N Z J
s
*
*
exp ( )
|
.
|
\
|
=
t
J t J
S

exp
2 / 1
2
2
*
2
1
|
|
.
|
\
|

=
n
n
n
G
kT
Z
* 2
2
1
Z
=
=
*
*
4 r ( )
1
1
/
2
/ /

=
(
(
n
i
i i
i i
D X
X X

2
2 3
*
3
16
m
m
G
V
G
=

Format for interfacial energies in a tdb
Interfacial energies in the bulk
PHASE CEMENTITE%BCC_A2 % 2 3 1!
CONST CEMENTITE%BCC_A2 : CO,CR,FE%,MN,MO,NB,NI,V,W : C,N :!
PARAM V0(CEMENTITE%BCC_A2,CO:C;0) 298.15 +0.4; 6000 N REF07!
PARAM V0(CEMENTITE%BCC_A2,FE:C;0) 298.15 +0.4; 6000 N REF07!
Effective interfacial energy at a dislocation
PHASE CEMENTITE%BCC_A2%DIS % 2 3 1!
CONST CEMENTITE%BCC_A2%DIS : CO,CR,FE%,MN,MO,NB,NI,V,W : C,N :!
PARAM V0(CEMENTITE%BCC_A2%DIS,CO:C;0) 298.15 +0.4; 6000 N REF07!
Effective interfacial energy at a grain boundary
PHASE CEMENTITE%BCC_A2%GB % 2 3 1!
CONST CEMENTITE%BCC_A2%GB : CO,CR,FE%,MN,MO,NB,NI,V,W : C,N :!
PARAM V0(CEMENTITE%BCC_A2%GB,CO:C;0) 298.15 +0.174; 6000 N REF07!
Challenges and Future Needs
The CALPHAD community is a good example of where different
groups have collaborated and agreed on standardized models and
data that enabled the community to develop interconsistent datasets.
Examples include SGTE unary data (thermodynamic data for the elements on
which nearly all CALPHAD type assessments are based)
Openly published models and agreed reference states (G-H(SER))
Databases are more than just a collection of binary and ternary and
higher order assessments and systems. Multicomponent specialized
databases benefit from a database architect:
Oversees which models are used (and why)
Consistency of models
Consistency of data (e.g. if a ternary is switched out, you may need to recheck
the binary systems too)
Data Consistency and Collaboration
The key building blocks to constructing good quality thermodynamic
databases (which are in turn the building block of a lot of multi-scale
modeling) is thermodynamic data and phase equilibrium for binary
and ternary systems. From these, the CALPHAD methodology allows
extrapolation to higher order systems.
The key to these data are that they are not material specific (e.g. Al-Ni is applicable to
both Al alloys rich in Al and Ni alloys rich in Ni) and hence can be re-used.
But it is often these kinds of assessments which are not funded (or are often hidden) as
part of a broader program.
Skills to both measure these data, facilities to do so, and the expertise to critically
evaluate such data are decreasing
Need composition dependent and temperature dependent data for
both thermodynamics and mobility data, but also e.g. volume data,
interfacial energies, and other properties that can be overlayed onto
a CALPHAD type description.
Need low temperature data (where eqm may not be attained), data
for metastable phases
Data Needs and Challenges (1)
A common misconception of those not familiar with the CALPHAD
type databases is that a user can just collate some data for an
additional element and add it as though it were some simple
Microsoft Access database.
The reality is that as a minimum, the CALPHAD approach usually requires all
the binary systems to be assessed = [N * (N-1)] / 2 where N is the number of
elements or end-members. For example N=10 elements requires 45 binary
systems to be assessed. Expanding the database to 12 elements requires 60
binary systems to be assessed. Each binary system can take from a few days
to a few months to assess, assuming there is good quality experimental data
available.
As databases are expanded, it is not trivial to go back and reassess key binary
systems as new data become available.
Critical assessment is an art as well as a science requires experience.
Validation is an important part of the database development process.
This is best done in collaboration with industry. This presents the
challenge of being more closed, with less opportunity to bring the
data to a broader market and with often more restrictions.
There is a lot of potential in the capability to port data more easily
from one application / software package to another, but this would
require common standards and the willingness and cooperation of
commercial software developers to see the benefit (or have their
users demand it).
How do we link peripheral data e.g. Thermo-Calc calculates phase
equilibria (relates to crystal structures). How do we link to crystalline
databases? How do we link to other codes that calculate physical
properties related to the microstructure?
Future needs
While models and data have been derived for:
molar volumes
surface tension and viscosity
interfacial energies
these have been mostly for select databases, or even small subsets of
data. ICME places a larger demand, not just on developing models, but
populating the larger databases multiphase multicomponent databases
with these data.
Additionally, other data, such as these listed below, maybe desirable for
the future:
Elastic constants
Electrical resistivity
Thermal conductivity
Surface tension and viscosity
Butlers monolayer model for surface tensions:
Use of Thermodynamic Data to Calculate Surface Tension and
Viscosity of Sn-based Soldering Alloy Systems. Lee and Lee.
Journal of Electronic Materials, Vol. 30, No. 9, 2001
Hirais model for viscosity
Seetharamans model for viscosity
Thermo-Calc Software Lattice misfit & thermal stress
Thermal stress:
Lattice change of matrix A due to precipitate B
T
E

1
( )
B
A
y C
a
a
3
1
4
+
=
|
.
|
\
|

Thermal expansivity misfit
Lattice strain
Volume
database
Elastic moduli, C and E
Poissons ratio,
Elastic
database
Questions?

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Interfacial energy & Volume & Elastic constants

Impurity diffusion coefficient of Ni in pure Al and Al in pure Ni:

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