Distribution of practical work

and brief introduction to

Thermo-Calc and assessment
Hannu Sippola, Niko Hellstén

Course CHEM-E6115: Thermodynamics of modeling and simulation

Contents of the lecture
• Aims of the practical work

• Distribution of practical work

• Computational thermodynamics

• Introduction to Thermo-Calc software

• Preparation of files for assessment using Thermo-Calc

Aims of the practical work
• Become aware of computational thermodynamics and software

• Understand the basic philosophy of doing a thermodynamic

assessment

• Experience the basic work flow in thermodynamic assessment by

doing an assessment of a simple binary eutectic system and writing a
report about it
Project work
• Practice assessment in groups of 2-3
• Every group does an assessment of a binary eutectic metal system using
Thermo Calc software ->stable phases considered only
• Written report of the work is required

• Systems to choose from

• Al-Ge
• Pb-Sn
• Cu-Zn

• You can learn from the published articles for the well assessed systems of
your assignment.
Additional information
• Deadline of the report is the middle of May
• The report should be around 20 pages containing:
• (i) detailed literature survey, evaluation and selection,
• (ii) model description and model selection and
• (iii) final results of the plots you can make.
• Also, the SETUP file, POP file, MACRO file for calculating phase diagram and
thermodynamic properties should be attached as appendices.

• A lecture going into details of the assessment held next Tuedsay (21.3.) at
10:15 am at V3

• Office time is Tuesdays 10 – 12 am, B358, Niko Hellstén,

[email protected], Tel: 040 719 6323
Suggested course of action
• 1) Download and install Thermo-Calc

• 2) Get to know the basics of the software following the user guide
and examples

• 3) Get to know the system you are trying to assess and search the
literature for more knowledge and experimental data

• 4) Try to write the SETUP, POP, EXP and MACRO files

Computational Thermodynamics
• The use of computer software to perform
thermodynamic calculations (CALPHAD method)
Thermodynamic
• Software: Thermo-Calc, MTDATA, FactSage, Pandat relations

• Results of calculations depend on the assessed

descriptions stored in thermodynamic databases

• The software can print all thermodynamic

information from the calculation graphically or in
tabular form
• Plotting of phase diagrams, Gibbs energy curves, Cp
functions etc
• Numerical values of the calculations Properties
Phase diagram
ΔH,Cp,µ
Reference material
These books describe thermodynamic modeling using the CALPHAD
method (CALculation of PHAse Diagrams or The Computer Coupling of
Phase Diagrams and Thermochemistry) and experimental methods.
All books are available also in electronic form.

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Thermo-Calc
• Software for thermodynamic calculations:
• Stable and meta-stable heterogeneous phase equilibria
• Amounts of phases and their compositions
• Thermochemical data such as enthalpies, heat capacity
and activities
• Transformation temperatures, such as liquidus and solidus
• Driving force for phase transformations
• Phase diagrams (binary, ternary and multi-component)
• Solidification applying the Scheil-Gulliver model
• Thermodynamic properties of chemical reactions
Introduction of Thermo-Calc
• Graphical user interface

• Character based console mode

• Calculations performed by giving commands
• Commands can be abbreviated, for example LIST_SYSTEM -> l s
• Complete explanation of each command found in Console Mode Command Reference Manual
• Assessment can only be done in the console mode

• Modular structure
• A specific module for different tasks, for example data retrieval, equilibrium calculations,
processing of plots etc

• The theory mentioned in the previous lecture happens in the background -> only results
are shown
 Calculations with Thermo-Calc
System • DATA
definition

Perform • POLY,
calculations BIN etc

Print results • POST

Introduction to Assessment with Thermo-Calc
• Computational thermodynamics software is useless without
databases of high quality.

• Assessing, optimising and validating individual thermodynamic

systems, followed by the construction of an internally consistent
CALPHAD database is essential.
CALPHAD Technique - assessment methodology
Critical Evaluation
Literature survey
• Phase diagram data
• Thermodynamic quantities Extrapolation of higher order system
• Crystallographic information
• First principle calculation Establishment of thermodynamic database

Selection and evaluation of data available

Model description of each phase Application

Data optimization
Optimization of parameters in the model
• Basic procedure of doing
assessment Weight of data

Comparison with the exp. and calc. data

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Data optimization
• The Gibbs energy of the whole system is the sum of the products of Gibbs
energy of each phase multiplied by the amount of that phase

• Each phase in a system is described using a mathematical model of its Gibbs

energy, mostly G-T, X and P.

• The mathematical model is made up of parameters, by optimizing the

parameters, the thermodynamic properties of a system can be calculated.

It is about adjusting the model parameters so that calculated equilibria

and thermodynamic properties fit well with the experimental ones.

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Workflow in assessment in Thermo-Calc

1) Preparation of files

2) Optimization

3) Checking results of optimization

Files needed for starting an assessment
• SETUP file with models and known and unknown parameters

• POP file with experimental data included

• EXP file with experimental data to be plotted and compared

• MACRO files for quick calculation of various diagrams

• Each file is a text-file consisting of Thermo-Calc commands

• The files can be written with any basic text editor, for example Notepad
• Formats and examples of the different files can be found for example in the reference
manuals
SETUP file, it contains
• Names of the elements and phases
• Models for the phases
• Gibbs energy functions for each phase

Tips:
For pure elements, the Gibbs energy values can be found in SGTE
(Scientific Group Thermodata Europe) collection (www.sgte.org)
Or extracted from the PURE database in the software, free

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SETUP file

These are the

parameters which are
optimized.
POP file
• The POP file contains the experimental and theoretical data collected
from literature and further experiments (invariant reactions, solubility
data, EMF data, Enthalpy)

• The experimental information is described with specific commands

(POLY commands), with some additional features

• The information in the POP file should be well organized and

documented

• The description of the experiment should be as close to the authentic

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experimental conditions as possible
 Liquid phase - Mixing enthalpy in the liquid phase

CREATE_NEW_EQUILIBRIUM 50 1 • Each experimental equilibrium should start with the command CREATE
CHANGE_STATUS PHASE LIQUID=FIX 1
• The first integer is an identifier of the equilibrium
SET_REFERENCE_STATE MG LIQUID * 1E5;
The second integer is an initialization code:
SET_REFERENCE_STATE CU LIQUID * 1E5;
0 = all components and phases initially suspended
SET_CONDITION P=P0 X(MG)=.87 T=1125
1 = all components entered but all phases suspended
EXPERIMENT HMR=-3200:600
2 = all components and phases entered initially
LABEL AL
• EXPERIMENT specifies the quantity to be fitted in the optimization
• LABEL helps to specify a batch of information that the user wants to
treat as one entity when setting weightings. It has maximum of 4
characters and starts with letter A

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 Liquid phase - Activity in the liquid phase
TABLE_HEAD 90 A table can be made if there is a lot of data
CREATE_NEW_EQUILIBRIUM @@,1
CHANGE_STATUS PHASE LIQ=FIX 1 TABLE-END !!!!!
SET_CONDITION X(LIQUID,MG)=@6
SET_CONDITION P=P0 T=@2
COMMENT is followed by the text that will be saved in the
EXPERIMENT ACR(MG)=@5:16%
SET_REFERENCE_STATE MG LIQ * 1E5 work file of the optimization
LABEL @1
GRAPHICS 1 @5 @2 MS1 ‘$’ also works but won’t be saved
SET_ALL_START_VALUES Y
COMMENT MG PRESSURE - JUNEJA GRAPHICS is used to automatically create an experimental
TABLE_VALUES data file (.EXP ) when the POP file is compiled:
$ T/K 10000/T Log10(aMg) aMg xMg
AL 1056 9.4698 -0.0466 0.8982 0.9005
AL 1032 9.6927 -0.0471 0.8972 0.9005
AL 1018 9.8254 -0.0474 0.8966 0.9005
AL 1010 9.9028 -0.0476 0.8962 0.9005
AL 990 10.1019 -0.0480 0.8953 0.9005
AL 979 10.2125 -0.0483 0.8948 0.9005
TABLE_END
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EXP file
• By compiling the .POP file with GRAPHIC command, EXP file can be
generated automatically.
TABLE_HEAD 60
CREATE_NEW_EQUILIBRIUM @@,1
CHANGE_STATUS PHASE LIQ=FIX 1
SET_CONDITION X(LIQ,MG)=@4
SET_CONDITION P=P0 T=@3
EXPERIMENT MUR(MG)=@2:20%
SET_REFERENCE_STATE MG LIQ * 1E5
LABEL @1
GRAPHICS 1 @4 @2 MS1
SET_ALL_START_VALUES Y
COMMENT MG PRESS - SCHMAHL AND SIEBEN
TABLE_VALUES

• One can also write the EXP file using DATAPLOT GRAPHICAL LANGUAGE
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MACRO files (.TCM)
• It is important to often check the fit between calculated values and
collected experimental data.
• It is efficient to create MACRO files to plot the graphs and make
comparisons rapidly.
• The MACRO files can help to plot not only the phase diagram, but
activities, chemical potentials, heat capacity and so on.

The MACRO files contain the commands that can be used in POLY and
in the POST modules.

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MACRO file – plot the phase diagram of Cu-Mg and the heat capacity of CuMg2
go p-3 go p-3
def-comp,,, def-comp,,
s-c p=1e5 t=1000 n=1 x(mg)=0.1 s-c t=1100 p=1e5 n=1 x(mg)=.6666667
c-e en fun cp=hm.t;
l-e,,, s-a-v 1 t 0 1500 10
s-a-v 1 x(mg) 0 1,, c-e
s-a-v 2 t 300 1500,, sa CuMg2 y
map,, step,,
sa cpd y
po pos
s-d-a x T
a-e-d y expfil.exp s-d-a y cp
0 ap y CuMg2 1:1
3 s-s y n 0 100
set-ax-tex x n T/K
pl,, set-ax-tex y n Heat capacity CuMg2 (J.Mol-1.K-1)
plot,,
du pdf m CuMg2
ba set-inter
ba
set-inter 25
Closing remarks
• After you have compiled the SETUP, POP, EXP and MACRO files, the
optimization is done in the parrot module.

• More about the optimization next week

• If you have any questions, feel free to contact me

 Thank you

[email protected]