Lecture OpenCalphad OC-2014

A free software for thermodynamic calculations
Bo Sundman1 , Ursula R Kattner2 , Mauro Palumbo3 and

Suzana G Fries3
1
INSTN CEA Saclay, France

NIST, Gaithersburq, MD, USA
ICAMS, Ruhr University Bochum, Germany
2
March 7, 2014
Abstract
The use of thermodynamics in many applications suffers from the
lack of a high quality open source software for multicomponent
systems. The aim of the OC software is to fill this gap.
TMS 7 March 2013, Bo Sundman et al.
Abstract
The use of thermodynamics in many applications suffers from the
lack of a high quality open source software for multicomponent
systems. The aim of the OC software is to fill this gap.
It is also very important for the development of thermodynamic
databases to improve the thermodynamic models implemented in
the software. An open source software with a GNU license will
make it easier for those interested to develop and test new models.
Content
Data structures
Software for storage, retrieval and calculation of the Gibbs

energy for a single phase, the model package.
Software for calculation of equilibria for various conditions.
User interface.
Assessment of experimental and theoretical data for

thermodynamic databases.
Software library for application programmes like phase field

simulations.
The elements
A thermodynamic system is buit from

elements. Vacancies and electrons are
included.
The elements and species

included.
The species are stoichiometric
combinations of elements.
The elements, species and phases

included.
The phases have species as
constituents. The phases can have
different models, constituents,
sublattices, magnetic contribution.
The elements, species and phases

included.
The phases have species as
constituents. The phases can have
different models, constituents,
sublattices, magnetic contribution.
Model parameters describe the Gibbs
energy but also other composition
dependent properties like Curie
temperature, elastic constants,
mobilities, etc.
Parameter tree for a phase (A,D)(B,C)
The parameters for a phase are stored in a tree structure.

The endmember records specify one constituent in each sublattice
and has a property record list which contain an expression of the
Gibbs energy and maybe other things like the Curie temperature,
mobilities etc. for this endmember.

The endmember records specify one constituent in each sublattice
and has a property record list which contain an expression of the
Gibbs energy and maybe other things like the Curie temperature,
mobilities etc. for this endmember.Each interaction record contains
one more constituent in a sublattice and has also a property list.

In fact the data structure gives the model equation:
Gm = yA yB ( GA:B + yC (LA:B,C + yD LA,D:B,C ) + yD LA,D:B ) +
Static and dynamic data
The data for elements, species

and model parameters are
independent on the external
conditions on the system
Static and dynamic data

Dynamic data
The data for elements, species

and model parameters are
independent on the external
conditions on the system
The amount and constitution of

the phase varies with the external
conditions like temperatue and
composition and are stored in the
equilibrium record.
Parallell execution
Dynamic data
In addition to the dynamic phase

data the current conditions are
also stored in the equilibrium
record. In simple cases there is
just one equilibrium record but
each is independent and can be
executed in parallel.
Parallell execution
Dynamic data
In addition to the dynamic phase

data the current conditions are
also stored in the equilibrium
record. In simple cases there is
just one equilibrium record but
each is independent and can be
executed in parallel.
This is useful for application
software like mapping phase
diagrams, assessment of model
parameters using experimental
and theoretical data and for
phase field simulations when
each gridpoint can have its own
set of conditions.
Models of phases
The simplest model is an ideal substitutional solution of the

elements. The elements have just a Gibbs energy of formation
for the phase: GA , relative to a reference state.
Models of phases

The next step is to have an ideal mixing of species as

constituents, like in an ideal gas. Each species I has a Gibbs
energy of formation: Gi .
Models of phases


The next step is to introduce interactions between the

constituents, i.e. a regular solution. The interaction can
depend on the temperature, T , and the constitution, Y .
Models of phases


The next step is to introduce interactions between the

constituents, i.e. a regular solution. The interaction can
depend on the temperature, T , and the constitution, Y .
For crystalline phases one must take long range ordering into
account using sublattices for example in interstitial solutions,
Laves, etc. For such models we can introduce the Gibbs
energy of formation of an end-members with one
constituent in each sublattice, like GFe:Cr:Cr:Fe:Cr

for a 5
sublattice model of the phase.
The Compound Energy Formalism, CEF

The Compound Energy Formalism (CEF) contains all these models
(and many more) as special cases. In addition the constituents can
be charged like in a spinel phase and one can model the magnetic
contribution to the Gibbs energy as a separate function depending
on the Curie temperature and the Bohr magneton number. The
generic formula of CEF for a phase is
Gm =
srf
Gm T
cfg
Sm +
Gm +
phys
Gm
(1)
The term phys Gm can describe special contributions to the Gibbs

energy for example ferromagnetic transitions.
The CEF model has been implemented in the OC software.
Software, modules
The OC software is modulized in the following way. Each module
depends on the more basic ones.
Application programs using the OC application software

interface. The assessment module is a special application
integrated in the OC software.
Software, modules

Module for calculation and plotting of diagrams.
Software, modules

Module for single equilibrium calculation for the flexible

external conditions on T , P, overall composition, chemical
potentials, specification of fix phases etc. This module must
iterate by varing the amount of the phases and their
constitutions to find the minimum for the given set of
conditions.
Software, modules

Module for single equilibrium calculation for the flexible

external conditions on T , P, overall composition, chemical
potentials, specification of fix phases etc. This module must
iterate by varing the amount of the phases and their
constitutions to find the minimum for the given set of
conditions.
Module with different thermodynamic models to calculate the

molar Gibbs energy and partial derivatives with respect to
T , P, Y for each phase in the system.
Running an OC macro to calculate an equilibrium in the C-Cr-Fe

system:
OC:macro ocex02b
OC:read tdb ccrfe
reading a TDB file
Created records for elements, species, phases:
end members, interactions, properties:
TP-funs, composition sets, equilibria:
state variable functions, references, additions:
3
23
80
3
11
16
10
7
9
57
1
2
OC:set c t=1000 p=1e5

OC:set c n(fe)=.75 n(c)=.1 n(cr)=.15
OC:c e
Entering calceq2
Composition set(s) created:
1
Grid minimization:
167 gridpoints
0.0000E+00 s and
16 clockcycles
Done grid minimization,
3 stable phase(s):
Too soon to remove phase
8
3
0
Not added comp.set with same composition as stable phase:
8
1
2
Solution found after
19 iterations.
Equilibrium calculation
1.5600E-02 s and
32 clockcycles
OC:list res 1
Conditions .................................................:
1: T=1000, 2: P=100000, 3: N(FE)=0.75, 4: N(C)=0.1, 5: N(CR)=0.15
Degrees of freedom are
0
Some global data ...........................................:
T=
1000.00 K (
726.85 C), P= 1.0000E+05 Pa, V= 0.0000E+00 m3
N=
1.0000E+00 moles, B=
5.0886E-02 kg, RT=
8.3145E+03 J/mol
G= -4.3287E+04 J, G/N= -4.3287E+04 J/mol, H= 2.1653E+04 J, S= 6.4940E+01 J/K
Some component data ........................................:
Component name
Moles
Mole-fr Chem.pot/RT Activities
C
1.0000E-01 0.10000 -2.6108E+00 7.3478E-02
CR
1.5000E-01 0.15000 -7.4883E+00 5.5957E-04
FE
7.5000E-01 0.75000 -5.0959E+00 6.1218E-03
Ref.state
SER (default)
SER (default)
SER (default)
Some Phase data ............................................:

Phase: BCC_A2
Status: Entered
Driving force:
0.0000E+00
Formula units:
6.6716E-01, Moles of atoms/formula unit:
1.0003E+00
Moles 6.6737E-01, Mass 3.7232E-02 kg, Volume 0.0000E+00 m3, Mole fractions:
FE
9.88074E-01 CR
1.16085E-02 C
3.17582E-04
Phase: M7C3_AUTO#2
Status: Entered
Driving force:
0.0000E+00
Formula units:
1.0000E+01
CR
4.27665E-01 C
3.00000E-01 FE
2.72335E-01
OC:set status phase liquid=fix 0

OC:set c t=none
OC:c e
OC:list,,,,,
Conditions .................................................:
1: P=100000, 2: N(FE)=0.75, 3: N(C)=0.1, 4: N(CR)=0.15, 5: <LIQUID>=0
Degrees of freedom are
0
Some global data ...........................................:
T=
1536.30 K ( 1263.15 C), P= 1.0000E+05 Pa, V= 0.0000E+00 m3
N=
1.0000E+00 moles, B=
5.0886E-02 kg, RT=
1.2774E+04 J/mol
G= -8.4166E+04 J, G/N= -8.4166E+04 J/mol, H= 4.5920E+04 J, S= 8.4675E+01 J/K
Some component data ........................................:
Component name
Moles
Mole-fr Chem.pot/RT Activities Ref.state
C
1.0000E-01 0.10000 -3.9252E+00 1.9739E-02 SER (default)
CR
1.5000E-01 0.15000 -7.7362E+00 4.3671E-04 SER (default)
FE
7.5000E-01 0.75000 -6.7148E+00 1.2128E-03 SER (default)
Some Phase data ............................................:
Phase: LIQUID
Status: Fixed
Driving force:
0.0000E+00
Formula units:
0.0000E+00, Moles of atoms/formula unit:
1.0000E+00
Moles 0.0000E+00, Mass 0.0000E+00 kg, Volume 0.0000E+00 m3, Mole fractions:
FE
6.84186E-01 CR
1.69723E-01 C
1.46091E-01
Phase: FCC_A1
Status: Entered
Driving force:
0.0000E+00
Formula units:
1.0650E+00
FE
8.36622E-01 CR
1.02347E-01 C
6.10314E-02
Phase: M7C3
Status: Entered
Driving force:
0.0000E+00
Formula units:
1.0000E+01
CR
3.94573E-01 FE
3.05427E-01 C
3.00000E-01
Thermodynamic databases
For any application of computational thermodynamics (CT) one
must have a database with the model parameters. In the simplest
case one can just use results from DFT calculations of the
enthalpies of formation of the different phases.
Calculations of equilibria require that the energy parameters have
an accuracy of a few joule (less than 0.1 meV) and thus
calculations based only on DFT results can be very far from the
experimental information. But the assessment procedure in CT
makes it possible to combine DFT reults with experimental data to
obtain model parameters with a good fit to reality.
Calculations of equilibria require that the energy parameters have
an accuracy of a few joule (less than 0.1 meV) and thus
calculations based only on DFT results can be very far from the
experimental information. But the assessment procedure in CT
makes it possible to combine DFT reults with experimental data to
obtain model parameters with a good fit to reality.
Most high quality databases are commercial but there are a few
smaller databases available free. However, you must be careful
using databases that may not be maintained and updated by an
experienced and skillfull assessment team.
Single equilibrium calculation

To find the equilibrium at fixed temperature, pressure and
composition one must minimize the total Gibbs energy of the
system. The models describe the molar Gibbs energy, Gm and the
total energy is:
G=
Gm
where is the amount of the phases.
(2)
Single equilibrium calculation

To find the equilibrium at fixed temperature, pressure and
composition one must minimize the total Gibbs energy of the
system. The models describe the molar Gibbs energy, Gm and the
total energy is:
G=
Gm
(2)
where is the amount of the phases.

If one has other conditions like fixed volume, chemical potentials or
fixed phases one can modify the Gibbs energy by the use of
Lagrangian multipliers.
Single equilibrium calculation, Lagrangian method

The algorithm for minimization that is implemented in OC was
proposed by Hillert (1981). It uses Lagrangian multipliers to take
care of both external and interal constraints. For constant
composition and fixed T and P an example is:
L=G+
(NA
MA
)A +
XX
X ,(s)
1) (3)
,(s) (
yi
i
is the amount
where NA is the total amount of component A, MA
of A in , yi is the constituent fraction of i . A and are
Single equilibrium calculation, Lagrangian method

The algorithm for minimization that is implemented in OC was
proposed by Hillert (1981). It uses Lagrangian multipliers to take
care of both external and interal constraints. For constant
composition and fixed T and P an example is:
L=G+
(NA
MA
)A +
XX
X ,(s)
1) (3)
,(s) (
yi
i
is the amount
where NA is the total amount of component A, MA
of A in , yi is the constituent fraction of i . A and are
The first constraint is the massbalance and the second that the
sum of constituent fractions in each sublattice of is unity.
By differentiating the Lagrangian function with respect to the
different variables we obtain many relations.
Single equilibrium calculation module, step 1

In a first step we invert the matrix of second derivatives of the
Gibbs energy with respect to the constituent fractions:
eij
2 Gm
yi yj
1
(4)

eij
2 Gm
yi yj
1
(4)
This matrix is used to formulate an equation for correcting the

constituent fractions, yi :
yi =
X X MA
A
yj
eij A
X Gm
j
yj
eij
X 2 Gm
eij T
T yj
(5)
where A the chemical potential of component A. If T is constant

the T term cancels. All the partial derivatives are calculated
analytically in the model module.

eij
2 Gm
yi yj
1
(4)
This matrix is used to formulate an equation for correcting the

constituent fractions, yi :
yi =
X X MA
A
yj
eij A
X Gm
j
yj
eij
X 2 Gm
eij T
T yj
(5)
where A the chemical potential of component A. If T is constant

the T term cancels. All the partial derivatives are calculated
analytically in the model module. But to solve this we must first
find A and T which is done in a second step.

In the second step we formulate a system of linear equations to
obtain a new values of the chemical potentials, amounts of the
stable phases and temperature if it is variable. There is one
equation for each stable phase like
X
MA
A = Gm
(6)
if any chemical potential is fixed that term is moved to the right

hand side.

In the second step we formulate a system of linear equations to
obtain a new values of the chemical potentials, amounts of the
stable phases and temperature if it is variable. There is one
equation for each stable phase like
X
MA
A = Gm
(6)
if any chemical potential is fixed that term is moved to the right

hand side. For each condition on an extensive variable we obtain
an equation, which in a simple case, NA = fix, is:
P
MA
i yi
P P
B
MB
j yj eij B
where we find the matrix eij again.
MA =
P
P
MA
Gm
i
j yi yj eij

With the new values of the chemical potentials and amounts of
phases, we can obtain new constitutions of the phases using eq. 5.

If a phase amount becomes negative that phase should be removed
from the set of stable phases and if the driving force, G
X
G =
MA A Gm
(7)
A
for an unstable phase becomes positive that phase should be added

to the stable set of phases.

If a phase amount becomes negative that phase should be removed
from the set of stable phases and if the driving force, G
X
G =
MA A Gm
(7)
A
for an unstable phase becomes positive that phase should be added

to the stable set of phases.
If the change in chemical potentials and phase amounts are small
and all external conditions are fullfilled the calculation has
converged, otherwise we start again from step 1.
Grid minimizer, step 0

The algorithm described is an iterative method which depends
strongly on the initial configuration of the phases.
Grid minimizer, step 0

The algorithm described is an iterative method which depends
strongly on the initial configuration of the phases.
As an initial step 0 the OC software has a grid minimizer which
calculates the Gibbs energy of all phases over a grid of
compositions. These are treated as stoichiometric phases in a
preliminary minimization to find a set of gridpoints representing
the minimum. These gridpoints are used as initial guess and their
compositions are inserted as start constitutions for the interative
algorithm.
Grid minimizer 2
4
3
2
1
4
3
2
1
Gibbs energy (kJ/mol)
Two phases in a binary system can have Gibbs energy curves at a

fixed temperature and pressure like in (a). If the inital
compositions of these phase are as marked in (b) an iterative
minimizer, for a composition in the middle in the system, will find
the equilibrium marked with the common tangent in (c).
4
3
2
1
4
3
2
1
-1
-1
-1
-1
0.2
0.4
0.6
X(B)
0.8
1.0
0.2
0.4
0.6
X(B)
0.8
1.0
0.2
0.4
0.6
X(B)
0.8
1.0
0.2
0.4
0.6
X(B)
.
(a)
(b)
(c)
(d)
The real equilibrium is the common tangent marked in (d)
0.8
1.0
Grid minimizer 3
4
3
2
1
4
3
2
1
With a grid minimizer one calculates the Gibbs energy along the
curves at fixed compositions like in (e). These are treated as
individual phase with fix composition as in (f) in a first
minimization and one will find the two gridpoints representing the
lowest Gibbs energy in (g).
4
3
2
1
4
3
2
1
-1
-1
-1
-1
0.2
0.4
0.6
X(B)
0.8
1.0
0.2
0.4
0.6
X(B)
0.8
1.0
0.2
0.4
0.6
X(B)
0.8
1.0
0.2
.
(e)
(f)
(g)
Using these compositions as start points in an interative
minimization one will find the global minimim ib (h).
0.4
0.6
X(B)
(h)
0.8
1.0
On the list to do
The equilibrium calculation is currently not very stable, it
frequently fails and sometimes even converges to the wrong
equilibrium. This is mainly due to problems changing the set of
stable phases and to solve these problems we need a larger group
of testers who have patience enough to use the software and send
error reports.
On the list to do
error reports.
For the future the next thing is to develop the step and map
procedures for various types of diagrams.
and after that to develop an assessment module to fit model

parameters to experimental and theoretical data.
On the list to do
error reports.
For the future the next thing is to develop the step and map
procedures for various types of diagrams.
and after that to develop an assessment module to fit model

parameters to experimental and theoretical data.
In parallell more models will also be added, like the ionic liquid
model and the corrected quasichemical model for liquids.
Other features
The user interface is a rudimentary command interface with a

VAX/VMS flavour, a famous computer/operating system 30
years ago.
Other features

years ago.
The code is written in the new Fortran standard.
Other features

years ago.
The data structures and the code are quite extensively

documented.
Other features

years ago.

documented.
A number of sample macro files is supplied.
Other features

years ago.

documented.
An initial rudimentary software library is provided for the use

in application programmes.
Other features

years ago.

documented.

Free for non-commercial use.
Other features

years ago.

documented.

Free for non-commercial use.
All of this is available at:
http://www.opencalphad.org
Welcome to develop and use:
Thanks for listening

Lecture OpenCalphad OC-2014

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A free software for thermodynamic calculations

Bo Sundman1 , Ursula R Kattner2 , Mauro Palumbo3 and

INSTN CEA Saclay, France

TMS 7 March 2013, Bo Sundman et al.

TMS 7 March 2013, Bo Sundman et al.

Software for storage, retrieval and calculation of the Gibbs

Software for calculation of equilibria for various conditions.

Assessment of experimental and theoretical data for

Software library for application programmes like phase field

TMS 7 March 2013, Bo Sundman et al.

TMS 7 March 2013, Bo Sundman et al.

A thermodynamic system is buit from

The elements and species

TMS 7 March 2013, Bo Sundman et al.

A thermodynamic system is buit from

The elements, species and phases

TMS 7 March 2013, Bo Sundman et al.

A thermodynamic system is buit from

The elements, species and phases

TMS 7 March 2013, Bo Sundman et al.

A thermodynamic system is buit from

Parameter tree for a phase (A,D)(B,C)

The parameters for a phase are stored in a tree structure.

TMS 7 March 2013, Bo Sundman et al.

Parameter tree for a phase (A,D)(B,C)

The parameters for a phase are stored in a tree structure.

Parameter tree for a phase (A,D)(B,C)

The parameters for a phase are stored in a tree structure.

TMS 7 March 2013, Bo Sundman et al.

Parameter tree for a phase (A,D)(B,C)

The parameters for a phase are stored in a tree structure.

TMS 7 March 2013, Bo Sundman et al.

Static and dynamic data

The data for elements, species

Static and dynamic data

The data for elements, species

The amount and constitution of

TMS 7 March 2013, Bo Sundman et al.

In addition to the dynamic phase

TMS 7 March 2013, Bo Sundman et al.

In addition to the dynamic phase

The simplest model is an ideal substitutional solution of the

TMS 7 March 2013, Bo Sundman et al.

The simplest model is an ideal substitutional solution of the

The next step is to have an ideal mixing of species as

TMS 7 March 2013, Bo Sundman et al.

The simplest model is an ideal substitutional solution of the

The next step is to have an ideal mixing of species as

The next step is to introduce interactions between the

TMS 7 March 2013, Bo Sundman et al.

The simplest model is an ideal substitutional solution of the

The next step is to have an ideal mixing of species as

The next step is to introduce interactions between the

constituent in each sublattice, like GFe:Cr:Cr:Fe:Cr

TMS 7 March 2013, Bo Sundman et al.

The Compound Energy Formalism, CEF

The term phys Gm can describe special contributions to the Gibbs

TMS 7 March 2013, Bo Sundman et al.

Application programs using the OC application software

TMS 7 March 2013, Bo Sundman et al.

Application programs using the OC application software

Module for calculation and plotting of diagrams.

TMS 7 March 2013, Bo Sundman et al.

Application programs using the OC application software