FactSage 3

FactSage Practical
MSE302
Practical 3. Phase Diagram Calculation

Acknowledgements
The teaching team of MSE302 is grateful to:
Professor Mansoor Barati (UofT)
Professor Elmira Moosavi (ETS)
Professor Arthur Pelton (CRCT)
Professors In-Ho Jung and M. –A. Van Ende (Seoul National University)
Dr. Sina Mostaghel (SNC-Lavalin)
Professor Kinnor Chattopadhyay (UofT)
Drs. Daigen Fukayama, Takahiro Sasaki (RCCM)
Drs. Moritz to Baden and Guixuan Wu (GTT Technologies)
Sustainable Materials Processing Lab FactSage Team MSE Department, University of Toronto
Phase Diagram Calculations in FactSage
We have already shown in the FactSage Overview that there are three modules
which are available in FactSage 7.3 for the calculation of phase diagrams:
✓ Predom Module.
✓ EpH Module.
✓ Phase Diagram Module.
In MSE302, since our focus is mainly on the non-aqueous system, the EpH
module will not be discussed. However, you should be aware that in fields of
electrochemistry and hydrometallurgy, the EpH module has found wide
applications.
Phase Diagram Calculations in FactSage
Predom Module and Phase Diagram Module
Phase Diagram Calculation.
FactSage Practical
MSE302
Predom Module
Predominance Diagram
The predominance diagrams are a particularly simple type of phase diagram
that have many applications in the fields of hot corrosion, chemical vapor
deposition, etc.
Let us discuss the construction of a predominance diagram using the Cu-SO2 -O2
system.
Pelton, Phase Diagrams and Thermodynamic Modeling of Solutions, 2019 (Chapter 2.4.3) 6
Predominance Diagram: Theoretical Basis
Predominance Diagram of the Cu-SO2 -O2 System at 700 °C
Areas: domains of stability of

various solid compounds of
Cu, S and O.
Lines (univariant): coexistence of

two solid phases (in equilibrium)
Triple (Invariant) Points: coexistence

Logarithms of the partial pressures. of three solid phases (in equilibrium).
A predominance diagram can be constructed by calculating the lines which
indicate the coexistence of two solid compounds. The detailed procedure has
been discussed by Bale et al.
We formulate a reaction for the formation of each solid phase, always from 1.0
mol of Cu and involving the gaseous species whose pressures are used as the
axes; here, we use SO2 and O2 .
−0.5
Cu + 0.5O2 = CuO; ∆𝑟 𝑔 = ∆𝑟 𝑔° + 𝑅𝑇ln 𝑃O2
−0.25
Cu + 0.25O2 = 0.5CuO; ∆𝑟 𝑔 = ∆𝑟 𝑔° + 𝑅𝑇ln 𝑃O2
1 −1
Cu + SO2 = CuS + O2 ; ∆𝑟 𝑔 = ∆𝑟 𝑔° + 𝑅𝑇ln 𝑃O2 𝑃𝑆O2
−1 −1
Cu + SO2 + O2 = CuSO4 ; ∆𝑟 𝑔 = ∆𝑟 𝑔° + 𝑅𝑇ln 𝑃O2 𝑃SO2
At equilibrium, ∆𝑟 𝑔 = 0, and log 𝑃SO2 ~log 𝑃O2 can be calculated.

Bale et al. Can. Metall. Q. 25, 107-112
You can repeat the above procedure for the formation of Cu2 S, Cu2 SO4 , and
Cu2 SO5 .
You may note that in some equilibrium equations, there is no 𝑃O2 or 𝑃SO2 . This
means that the equilibrium between two solid compounds are independent of
𝑃O2 or 𝑃SO2 , and the lines would be horizontal or vertical.
Also, by reformulating the reaction for the formation of each solid phase, in
terms of, for example, S2 and O2 rather than SO2 and O2 , a predominance
diagram with logarithms of 𝑃S2 and 𝑃O2 as axes can be constructed.
Application I of Predominance Diagram
Say we introduce a large amount of SO2 and O2 into a system, the gas mixture
reacts with a small amount of Cu. Because the amount of Cu is small, the change
in the gas composition is negligible. If we adjust 𝑃SO2 and 𝑃O2 , different
products would result. A predominance diagram of Cu-SO2 -O2 can be used to
study this problem.
Gas in
(Constant 𝑃SO2 , 𝑃O2 )
Gas out
Cu
Application II of Predominance Diagram
You may notice from the predominance diagram of the Cu-SO2 -O2 system, there
is a curve shown by the crosses. Along this curve, the total (hydrostatic)
pressure is 1.0 bar.
We can fix a constant hydrostatic pressure of 1 bar by placing
Weights the system in a cylinder fitted with a piston (left graph). Under
this condition, if the gas phase is present, then the gas phase
Piston consists not only of SO2 and O2 , but also of other species such
Gas
as S2 , S3 , O3 , etc. whose equilibrium partial pressures can be
Condensed
calculated.
It is noted that when the total (hydrostatic) pressure is
controlled, 𝑃SO2 and 𝑃O2 can not be independently varied.
Application II of Predominance Diagram
The cross line is used to study the system’s equilibria when we have a closed
system and the total (hydrostatic) pressure is controlled. Above the total
pressure line, the total pressure is greater than 1.0 bar even though the sum of
the partial pressures of SO2 and O2 might be less than 1.0 bar. Caution must
therefore be exercised using such diagrams. If the total pressure is no greater
than 1.0 bar, states above the 𝑃total = 1.0 bar are inaccessible. In other words,
the calculated diagram for a total (hydrostatic) pressure of 1.0 bar terminates at
this line.
Predom Module: Cu-S-O System
The Predom Module allows you to calculate predominance diagrams. These
diagrams are calculated under quite restrictive conditions.
✓ Only compound databases are accessed.
✓ Temperature is fixed (isothermal calculation).
The partial pressures are permitted to vary for non-metallic species, and the
total pressure which is the sum of the partial pressures of all species can also
vary.
Again, before you work on your project, check the Directory!!!
13
Database Selection
Choose FactPS.
This might be the default database

for examples.
The maximum number of Metals is 3.
14
Define Elements: Metals and Non-metals
The maximum number of Metals is 3.
Click on “Next” to activate the calculation.
The maximum number of Non-

metals is also 3.
15
Define List of Species Click on “List” to see all the species that are going to be
considered. You could eliminate species from consideration,
but there is no need to do so – the program effectively does
that for us since it displays only the stable species.
16
Define Parameters: Pressures and Temperature
Total hydrostatic pressure.
Temperature is 700 °C.
Axes: partial pressures

of species.
Choose “diagram”. The triple

points can be calculated by
choosing “invariant point”.
17
Define Parameters: Pressures and Temperature
For a given total hydrostatic pressure of 1

atm, when 𝑃O2 is low, 𝑃SO2 is also low. This is
because that 𝑃S2 is high. As 𝑃O2 increases, S2
is gradually converted to SO2 and the
condensed phases go from a sulfide to oxide,
and to sulfate.
You are suggested to perform the calculations

at other temperatures and use the Figure
Module to impose these diagrams (See the
Supplementary material).
18
Predom Module: Cr-C-O System
The second example we will look at is the Cr-C-O system at 1800 K.
Here, the maximum carbon activity is set as 10. In

reality, the carbon activity cannot exceed unity. The
program permits one to calculate the diagram under
the conditions that cannot be achieved in practice.
However, we should never use ridiculously high
values for activities and partial pressures. 19
Along the curve of the total hydrostatic pressure of 1 atm, as

𝑃O2 increases, the carbon activity is dropping because of an
increasing amount of CO2 in the gas phase (consider: C +
CO2 = CO).
At low 𝑃O2 , the main gas species is CO. It is therefore

interesting to choose 𝑃CO as the Y-axis.
20
Choose 𝑃CO as the Y-axis.
21
At low 𝑃O2 , 𝑃CO is close to unity.
It is also noted, along the curve of the total pressure of 1 atm, as 𝑃O2 is
reduced, Cr2 O3 is reduced to carbide, but not metallic Cr. This reveals
that we cannot hope to make pure Cr metal by carbothermic reduction.
22
FactSage Practical
MSE302
Phase Diagram Module: Unary and Binary

System
Phase Diagram Module
Phase diagrams are a graphical representation of phase equilibria, showing
the phases at equilibrium with respect to temperature, pressure, etc. We have
already shown various types of phase diagrams for systems containing
stoichiometric compounds as well as solution phases in lectures. For binary
systems, the most common type is 𝑇~𝑋B diagram.
The Phase Diagram Module is a very powerful module and is superior to the
Predom Module in many ways. However, it takes a lot of care to use it correctly.
The general rules of constructing single-valued phase diagrams is thoroughly
discussed by Pelton.
Like the Equilib Module, selection of databases, especially, solution database, and
selection of the phases that may exist at equilibrium are quite challenging for
high-order systems. Always consult the Documentation Module!!!
Pelton, Phase Diagrams and Thermodynamic Modeling of Solutions, 2019 (Chapter 7.5) 24
Phase Diagram Module: H2 O
Let us start with a simple example: unary phase diagram of H2 O. We would like
to know how the equilibrium between water vapor, liquid water and ice is
shifted when the system’s pressure and temperature are varied.
We would like to plot a diagram that is the similar to the graph below.
25
Components Window: Define Components
Don’t forget to check your Directory.
We are plotting single-component phase diagram: H2 O
26
Components Window: Choose Units
Left click
27
Components Window: Choose Database(s)
We are considering the equilibrium between water vapor, liquid water and ice.
Therefore, only FactPS is required.
28
Menu Window: Choose Products/Phases (Compounds and Solution Phases)
We need to tell FactSage which phases should be considered before

performing equilibrium calculations. Then FactSage will only retrieve the
models of the selected phases from the chosen database, and then
perform the minimization of Gibbs energy under the conditions that will
be specified later.
Choose H2 O 𝑔 , H2 O 𝑙 and H2 O 𝑠 .
29
Menu Window: Choose Variables
We are calculating log 𝑃 ~𝑇 phase diagram.
Temperature range.
Pressure range. We are using

the logarithm scale.
Left click
30
Results
Triple point (please read the coordinates).
31
Phase Diagram Module: Fe-Cr System
The second example guides you through the calculation of the 𝑇~𝑋B diagrams
for binary alloy system.
Say we would like to calculate the Fe-Cr phase diagram. We are aware that in this
system, both stoichiometric compounds and solution phases could exist.
Therefore, we need to determine which database(s) should be used. To do this,
we could either use the search function in the Documentation Module, or use
the View Data Module.
32
Search the Fe-Cr system in the Documentation Module.
These pre-made phase diagrams using the

databases listed here are provided by FactSage
developers. You can choose one of them (ONLY
one) to calculate the Fe-Cr phase diagram.
However, we don’t have the access to all these
databases.
33
View the model quality for the Fe-Cr system in the View Data Module.
The above information from the Documentation Module and View Data Module indicates
that FTlite could be used to calculate the Fe-Cr system.
34
1. Don’t forget to check your Directory.
2. Add a new Component.
35
Components Window: Choose Units
Left click
36
Choose FTlite only.
37
Left click on the column of “Base-Phase” or

“Full Name” to display the solution description.
We need to tell FactSage which phases should be

considered before performing equilibrium calculations.
Then FactSage will only retrieve the models of the
selected phases from the chosen database, and then
perform the minimization of Gibbs energy under the
conditions that will be specified later.
38
1. There is no need to choose pure liquids because we will

choose liquid alloy.
2. Select all the pure solids.

Right click to open the “Selection Window”. All the pure
solids that are considered are indicated by a sign “+”. You
can remove some of solids manually. However, there is no
need to do so in this simple binary system. Screening of
the pure solids is normally required when multiple
databases are used or when we want to include some
meta-stable phases in the calculation (for example, Fe3 C
in the Fe-C phase diagram)
39
Note: the [I]-option only means we are considering

the possibility of immiscibility, and it might not
appear in the calculation results.
40
A Note: for the calculation of phase diagrams of a binary system which has been
optimized in the FactSage databases, we normally use the default settings when
choose phases, that is, all pure solids and all solutions (some default setting is
[I]-option). However, when calculating higher-order systems which requires the
selection of multiple databases, caution must be exercised and screening of
certain phases is necessary.
41
We are calculating 𝑇~𝑋B phase diagram.
Temperature range.
Pressure, if not exceedingly

high, has a negligible effect on
phase equilibria of the Fe-Cr
Left click system. Put 1 atm.
𝑛Fe
= 𝑋Fe
𝑛Fe + 𝑛Cr
42
Results: Click on “Calculate” to generate the phase diagram.
Use this to manually add labels for

different regions. This will label all single-phase regions.
This will list all the invariant reactions

in “Stable Phases” window (next slide)
and the reaction numbers are shown
on the diagram.
43
Results: Click on “Calculate” to generate the phase diagram.
All the stable phases (compounds and solutions) are listed. Also
included are the structural information of these phases.
All the invariant reactions (the number of degree of freedom is zero)

are listed.
Please note the number of components for these
two equilibria is 1.
44
Results: 2-phases tie-lines mode
This 2-phases tie-lines mode allows us to draw tie lines in a 2-phase region.
Please you mouse in a 2-phase region and left click.
45
Results: phase equilibrium mode
Phase equilibrium mode can be used to quickly calculate the

phase equilibrium under a given temperature and composition.
The results are shown on next slide.
46
Results: phase equilibrium mode
Specified Temperature and Composition
The phases at equilibrium.
Phase compositions.
47
Save Results
You can use the Figure Module to open .fig file and save it as other graph format.
Also, if you change the .fig to .txt, you can open the file using NotePad and extract all
the phase diagram data (ZPF lines).
48
Phase Diagram Module: Fe-O2 System
The third example guides you through the calculation of the 𝑇~𝑋B diagrams as
well as two-potential phase diagrams. We will use the Fe-O2 system as the
example.
First, let us calculate the 𝑇~𝑋B diagram for the Fe-O2 system.
49
Search the Fe-O (not Fe-O2 ) system in the Documentation Module.
FToxid should contain the optimized model

parameters for all the possible oxide phases in the
Fe-O system (FToxid database only contains the
models for oxide phases).
Note we do not have the access to TDnucl database.
50
Choose units
51
Before we choose the database(s), let us check the pre-made phase diagram.
Note: the Fe-Liq phase is a

solution phase. Limited
amounts of oxygen are dissolved
in liquid Fe. However, FToxid
does not contain a phase model
for Fe-Liq which is liquid metal.
These Fe structures have no

solubility for oxygen. However,
FToxid does not contain phase
models for pure metals.
52
We use the View Data Module to determine which other databases are needed.
First, check the Liquid Solution.
This might be a suitable phase for the liquid
We want to find the Liquid metal. However, no solubility limit of oxygen
Solution containing Fe and O. is noted. This would make the liquid metal
indistinguishable from the Slag phase.
Number refers to the type of phase

model. See the supplementary of
Solution Module.
Note: there is no need to check the FTdemo database.
53
First, check the Liquid Metal.
This phase sets the solubility limit of oxygen in
liquid Fe. This is exactly what we need for a
liquid metal phase.
Similar to FSstel-Liqu, no solubility limit of oxygen

was set.
Note: there is no need to check the FTdemo database.

54
First, check the Liquid Metal.
The above information shows that FTmisc-FeLQ is probably the best candidate
for the liquid metal phase. Therefore, FTmisc database should be chosen.
For the solid metallic Fe phases, since the solubility is very low, you can choose
either FactPS database which ignores the solubility of oxygen, or FSstel database
which considers the dissolution of oxygen (FSstel-BCC and FSstel-FCC). Here, we
choose FactPS .
Now let us reproduce the Fe-O phase diagram before we calculate the Fe-𝐎𝟐
phase diagram.
55
FactPS is chosen so that different solid pure Fe structures

can be considered when calculating the phase diagram.
A must-have database based on the pre-made phase diagram

shown in Documentation. This database includes the models
for Slag which is an ionic solution and other solid solutions
of oxide.
This database is chosen because it contains the model which

describes the liquid metal, that is, Fe-rich solution.
56
Select all the solutions and use the default settings

of immiscibility gaps.
Choose all the pure solids. FactSage 7.3 version is quite “smart”.
When multiple databases contain the data for same species,
FactSage will suppress the duplicates. You can edit the priority.
57
𝑛O
= 𝑋O
𝑛Fe + 𝑛O
58
Results: Fe-O Phase Diagram (𝑇~𝑋O Phase Diagram)
59
A Note on the Fe-O Phase Equilibrium: “Gas Suppression” Condition
It is worth noting that the Fe-O phase diagram shown on Slide does not include
the gas phase. That is, the gas phase is suppressed.
Say we fix a constant hydrostatic pressure of 1 atm by placing
the condensed phases in a cylinder fitted with a piston (left
Weights graph). If the total gas pressure at equilibrium (i.e., sum of the
partial pressures exerted by the gaseous species in the vapor
Piston phase generated by incomplete vaporization of the
Condensed components) is less than 1 atm, there will be no gas phase
Phases
present. This condition is referred to as “gas suppression”
condition. Clearly, if we heat or cool the system, the overall
composition of the condensed phases remain constant.
Pelton, Phase Diagrams and Thermodynamic Modeling of Solutions, 2019 (Chapter 7.8) 60
A Note on the Fe-O Phase Equilibrium: Fixed Oxygen Potential
Different from the previous condition under which the composition of the
condensed phases remains unchanged, another condition is to control the
oxygen content in the gas phase, i.e., constant partial pressure 𝑃O2 .
Note: the mass ratio of gas to condensed
Gas in
phases is large enough so that the
(Constant 𝑃O2 )
Gas out composition of gas-in and that gas-out is
Condensed Phases same.
When the above system reaches equilibrium, the condensed phases (solid
and/or liquid) are equilibrated with a gas phase with fixed 𝑃O2 . Say we wish to
fix 𝑃O2 in the range of 10−24 to 1 atm. Now let us plot the oxygen isobars on the
Fe-O phase diagram.
61
Back to the Menu Window (Slide)
Right click to open the

Selection Window.
Click on OK and you will

see “Z” appears.
Right click
62
Back to the Menu Window (Slide) You may noticed this region is different from
the case when gas is suppressed.
You are allowed to add other 𝑃O2 values even

after the calculation of phase diagram.
63
A Note on the Fe-O Phase Equilibrium: Fixed Oxygen Potential
The calculated Fe-O phase diagram with the 𝑃O2 isobars can be used to study a
heating or cooling process.
Say we are controlling the oxygen partial pressure 𝑃O2 = 10−8 atm. From the
calculated Fe-O phase diagram, it is seen that along the line of 𝑃O2 = 10−8 atm,
the highest temperature is > 1800 ℃, and the condensed phase should be pure
iron. Now, if we cool this system while keeping the oxygen partial pressure
constant (10−8 atm), the composition of the condensed phase will be changed
along the line of 𝑃O2 = 10−8 atm because of the oxidation.
The above simple analysis shows that the variables, i.e., temperature,
composition of the condensed phases and 𝑃O2 are correlated. As West and
Saunders commented that the partial pressure of oxygen is a function of both
temperature and composition.
West and Saunders, Ternary Phase Diagrams in Materials Science, 3 rd Edition, 2002 64
Now, we have successfully reproduce the Fe-O phase diagram shown in the
Documentation. To calculate the Fe-O2 phase diagram, we need to change the
component “O” to “O2 ”, but do not change the phase selection.
You can calculate either the condition under which the gas phase is suppressed,
or the condition of fixed 𝑃O2 . Here, we only show the calculation when the gas
phase is suppressed.
65
Results: Fe-O2 Phase Diagram (𝑇~𝑋O2 Phase Diagram)
66
Next, let us look at two-potential phase diagrams. We will again use the Fe-O2
system as the example to calculate 𝑇~𝜇O2 (thermal potential~chemical
potential) for the Fe-O2 system.
You might ask why we want to use 𝜇O2 as a variable? From the master equation,
we know,
𝜇O2 = 𝜇°O2 + 𝑅𝑇ln 𝑃O2
This means that, the topology of the 𝑇~𝜇O2 diagram is same to that of the
𝑇~𝑅𝑇ln 𝑃O2 diagram. Clearly, we are very interested in the effect of 𝑃O2 on the
phase equilibria. However, you should note that the topology of the 𝑇~𝜇O2
diagram is different from that of the 𝑇~ln 𝑃O2 diagram.
Pelton, Phase Diagrams and Thermodynamic Modeling of Solutions, 2019 (Chapter 7) 67
Back to the Menu Window, and activate the Variables Window
You don’t have to choose the gas species.
Choose RTln(a) as a variable.
68
Results: Fe-O2 Phase Diagram (Two-potential Phase Diagram)
You may need to add labels manually.
This is a very useful

diagram. It shows the
stability regions of various
condensed phases.
69
FactSage Practical
MSE302
Phase Diagram Module: Ternary System

Phase Diagram Module
The phase diagram for a ternary system requires a space model. Because of this,
we normally calculate isothermal sections and liquidus projections which are
easier to view in a 2D space.
The Phase Diagram Module can be used to calculate above phase diagrams for
ternary systems. Two examples will be presented, one is metallic system and the
other is oxide system.
A Note: most binaries have been critically assessed using existing experimental
data and therefore the binary phase diagrams reported by different accessors
(or model developers) generally agree with each other. However, this is not true
for ternary and higher-order systems. Since the amount of work in measuring
even one isothermal section of a relatively simple ternary phase diagram is
enormous, most of ternary phase diagrams and higher-order phase diagrams are
estimates extrapolated from critically evaluated binaries, and validated using
limited amounts of experimental data.
71
Phase Diagram Module: Al-Mg-Zn System
Let us review the FTlite database. Go to the Documentation Module, navigate to
“[FTlite] – FACT Al-Alloy and Mg-alloy databases”, and open the PDF document of
“general description and list of optimized systems”.
72
The above description shows that the FTlite database could be used to calculate
the Al-Mg-Zn system.
Note: for the FTlite database, no pre-made phase diagram for ternary systems by
CRCT (only binary systems) is available. That is, you won’t be able to find the Al-
Mg-Zn phase diagrams calculated using the FTlite database from the
Documentation Module. You might be able to find a few Al-Mg-Zn phase
diagrams calculated using the SGTE (alloy) database. Unfortunately, we do not
have the access to the SGTE database.
73
Choose Units.
74
Choose FTlite only.
75
Select all the solutions and use the default settings

of immiscibility gaps.
Choose all the pure solids. You should know that selection of some of the pure solids is not
necessary, e.g., Mg(hcp_A3), Mg2Zn(C36) etc., because there are corresponding solution
phases which include these pure solids as endmembers. For example, FTlite-A3 (HCP-A3)
in the Solution phases, if XMg = 1, FTlite-A3 becomes Mg(hcp_A3). However, in most
cases, it does no harm if these phases are selected. 76
A Note on the Selection of Products/Phases
To make FactSage more user-friendly, the developers of commercial databases
have added some key features to the databases, for example:
✓ [+], [I], and [J] indicate the possibility of miscibility, two-phase immiscibility,
and three-phase immiscibility.
✓ All the endmembers of solution phases are included in the pure solids.
These features permit the FactSage users who do not have a good knowledge of
thermodynamics to perform relatively reliable calculations for simple systems.
However, for complex real-world problems, an advanced FactSage user always
performs screening of products to avoid the appearance of unreasonable phases
in the equilibrium calculations.
77
Menu Window: Set up the Variables (Liquidus Projections)
For ternary systems, we use Gibbs triangle to

describe the composition (only 2 are needed).
This will permit the calculation of projection

diagrams. Also, the isotherms are specified
by max, min and increments.
A-Corner would be Zn.
𝑛Zn
= 𝑋Zn
𝑛Al + 𝑛Mg + 𝑛Zn
78
Right click to change FTlite-Liqu to the option of “P – precipitate target phase”.
We are calculating the liquidus projection, which

means other solids phases (primary crystallization
solids) are precipitating from the liquid.
The options of “univariants” and

“isotherms” must be selected.
They are important elements of
liquidus projection diagrams. 79
Results: Liquidus Projection of the Al-Mg-Zn System (FTlite Database)
All the invariant reactions.
You can add new isotherms here. On

the diagram, the isotherms are shown
as non-black lines.
80
Comparison with the diagrams from SGTE2017 and ASM Handbook.
Don’t be surprised if you find that the discrepancy exists for the liquidus Al-Mg-
Zn projections from different sources. After all, they are all just estimates!!!
81
Back to Variable Window (Slide): Isothermal Sections
Now we want to calculate the isothermal

section of the Al-Mg-Zn system at 20 °C.
82
Change FTlite-Liqu to the option of “standard stable phase”.
83
Results: Isothermal Section of the Al-Mg-Zn System (FTlite Database)
Tie Triangle
You need to manually label the regions.
This allows us to plot the tie lines for two-phase regions.

84
Comparison with the diagrams from SGTE2017 and ASM Handbook.
Again, there is a discrepancy between different phases diagrams reported from

different sources.
85
Phase Diagram Module: SiO2 -CaO-Al2 O3 System
Now let us calculate an oxide system which consists of SiO2 , CaO, and Al2 O3 . It is
worth mentioning that the ternary SiO2 -CaO-Al2 O3 phase diagram is actually an
isopleth of the quaternary Si-Ca-Al-O system along the line:
𝑛O = 2𝑛Si + 𝑛Ca + 1.5𝑛Al
This relationship is met in every condensed phases. Therefore, strictly speaking,
the ternary SiO2 -CaO-Al2 O3 phase diagram is a “quasi-” ternary phase diagram.
You also should note that the pressure, more specifically, 𝑃O2 , has a negligible
effect on the phase equilibria of the SiO2 -CaO-Al2 O3 system because all the
metals have only one oxidation state.
Pelton, Phase Diagrams and Thermodynamic Modeling of Solutions, 2019 (Chapter 6) 86
First, let us search this system in the Documentation Module.
Three isothermal sections calculated using the FToxid database are

found. Let us first reproduce these diagrams. (In doing so, we will
find out if some phases should not be selected.)
87
Choose Units.
88
Choose FToxid only because we are only dealing

with oxides (solid and/or liquid).
89
Let us choose all pure solids and all solution phases. For solution phases,
choose the default setting of immiscibility. If the three isothermal sections
found from the Documentation Module can be reproduced, then probably
no phase is required to be removed.
90
Menu Window: Set up the Variables (Isothermal Sections)
Isothermal section at 1200 °C.
Gibbs triangle.
A corner: pure SiO2 .
C corner: pure Al2 O3 .
B corner: pure CaO.
91
Menu Window: Set up the Variables
92
Results: Isothermal Section of the SiO2 -CaO-Al2 O3 System (FToxid Database)
93
94
95
Comparison with the three pre-made isothermal sections indicates that choosing
all the pure solids and solution phases from the FToxid database permits one to
generate reliable phase diagrams for the SiO2 -CaO-Al2 O3 system.
Now, we can calculate the isothermal sections at other temperatures using the
same selection of the phases. Please try to calculate the isothermal sections at
1800 °C, 1500 °C, and 1100 °C.
96
Before we calculate the liquidus projection of the SiO2 -CaO-Al2 O3 system, let us
think about the following question:
Who critically assessed the SiO2 -CaO-Al2 O3 system?
The development of CALPHAD databases (e.g., FactSage databases) is based on
numerous thermodynamic assessment work for binaries, ternaries, etc. These
work was either published in journals or communicated internally.
For FactSage, the references of thermodynamic assessments are complied as
“List of references” in the Documentation Module. Then the next question is
how can we find the references which were used to build the FactSage
databases?
97
What are the references used for the SiO2 -CaO-Al2 O3 system?
Right click
One way to find the references of assessments

for a given system is to look at the “Information”
of solution phases. It is recommended to choose
the solid solutions which are unique to the
system of interest. Here, we use Mullite.
The references numbers are shown at the
bottom.
98
A complete thermodynamic assessment for the

SiO2 -CaO-Al2 O3 system was detailed in this paper.
Also included are the calculated phase diagrams.
Link
99
This liquidus projection calculated by the

accessors used wt.% as compositional
scale. Now let us use FactSage – FToxid to
reproduce this phase diagram.
Eriksson and Pelton, Metallurgical Transactions B, Vol.24, No. 5, pp807-816 (1993) 100
Back to the Menu Window (Slide): Change the mass unit to gram.
Mass unit: gram
101
Back to the Variables Window (Slide)
Choose the projection option and set the isotherms.
A corner: pure SiO2 .

𝑚SiO2
= mass fraction SiO2
𝑚SiO2 + 𝑚Al2 O3 + 𝑚CaO
Note: mass fraction is not wt.%.
102
Menu Window (Slide): Choose Liquid (Slag) as the precipitate target phase.
We are calculating the liquidus projection, which

means other solids phases (primary crystallization
solids) are precipitating from the liquid.
103
Results: the Liquidus Projection of the SiO2 -CaO-Al2 O3 System
You may notice there are lines which cross with

each other. As the equilibrium state shown on a
phase diagram must be uniquely defined, the
crossing of lines is not permitted.
If you manually label the phase regions, you will
find that there is a region which is labeled both as
Melilite and Ca2 Al2 SiO7 .
104
The issue of having crossing or redundant lines when calculating the liquidus
projection is usually because we choose both the solution phase and its
endmembers from pure solids.
It is worth mentioning that the topology of the space model for a ternary system
like the SiO2 -CaO-Al2 O3 system is quite complex. When FactSage is performing
the “Gibbs energy minimization” calculation, if there are two Gibbs energy
functions of which the values are close (e.g., the Gibbs energy of a solution phase
and its endmembers), the calculation which gives single-value solutions might be
challenging. Furthermore, the algorithm of the “Gibbs energy minimization” is
based on numerical methods (not analytical!!!). Because of this, if we rearrange
the A, B, and C corner, the complexity of the “Gibbs energy minimization” might
be different, and the diagrams might look slightly different. Actually, one strategy
of resolving the issue when the calculated phase diagram contains crossing and
redundant lines is to switch the components at the A, B, and C corner.
Hack, FactSage Tech (FactSage\Information\FactSage-Tech) 105
After we swapped Al2 O3 and CaO, crossing and

intersecting lines still are present.
106
After we swapped SiO2 and Al2 O3 , crossing and

107
After we swapped SiO2 and CaO, crossing and

108
After we swapped SiO2 and Al2 O3 , then SiO2 and

CaO, crossing and intersecting lines still are present.
109
After we swapped SiO2 and CaO, and then SiO2 and

Al2 O3 , crossing and intersecting lines still are present.
110
The above phase diagram calculations show that the process of “Gibbs energy
minimization” might be impeded when both the solution phases and some pure
solids which are the endmembers of these solution phases are selected.
How to resolve the issue of having crossing and intersecting lines? The solution
is very simple: remove all the pure solids which are the endmembers of the
solution phases.
111
Find the endmembers of solid phases
1. Show the Information of a solid phase.

2. Click on “Information”, and find the
section which describes the Endmembers in
pure compound database.
The endmember of FToxid-MeO_A for the
current SCA system is CaO.
112
The endmember of FToxid-Mel_A for the

current SCA system is Ca2 Al2 SiO7 .
113
The endmember of FToxid-Mel_A for the

current SCA system is Al6 Si2 O13 .
114
Remove the endmembers of solid phases from pure solids
Remove these two pure solids.

(Ignore Al6 Si2 O13 because it is not found.)
115
Then, perform the phase diagram calculation again.
The issue of having crossing and intersecting lines is

resolved. You can try other component arrangements
at the A, B, and C corner.
116
Results: the Liquidus Projection of the SiO2 -CaO-Al2 O3 System.
This allows you to remove all

the labels and isotherms.
117
A Note on the Phase Selection:
Although the selection of CaO and Ca2 Al2SiO7 from the list of pure solids did not
produce any redundant lines when the isothermal sections were calculated, it is
still recommended that all the endmembers of the solutions phases be removed.
Comparison with the phase diagram reported by Eriksson and Pelton:

You might notice that the liquidus projection of the SCA system calculated by the
current FToxid database is not exactly same to the one reported by Eriksson and
Pelton (CRCT Team). This is because FToxid is being constantly updated by CRCT
to improve the accuracy of models and to include other oxides.
Eriksson and Pelton, Metallurgical Transactions B, Vol.24, No. 5, pp807-816 (1993) 118
Phase Diagram Module: MgF2 -CaF2 System
From previous examples, it is seen that the FactSage databases (e.g,, FTlite,
FToxid) always contain a model for liquid solution. The model usually gives a
quite accurate description of the interactions between solution constituents. In
most cases, the model is non-ideal solution model. However, the Phase Diagram
Module permits one to choose instead of non-ideal liquid solution from the
FactSage databases, an ideal liquid solution.
Say we are looking at a simple eutectic system, MgF2 -CaF2 . Let us calculate the
phase diagram of the MgF2 -CaF2 system using both the ideal solution model and
the non-ideal solution model for the liquid MgF2 -CaF2 solution.
Note: for these two scenarios, only the liquid phase is different.
119
First, find the FactSage database that can be used to calculate the phase diagram
of the MgF2 -CaF2 system.
Two databases can be used, and both of them contain the

optimized model parameters for the MgF2 -CaF2 system.
Here, we choose the FTsalt database.
120
Choose the units.
121
Choose FTsalt only.
122
Choose all pure solids and all solution phases
(use default immiscibility settings).
Note: FTsalt-SALTA is the non-ideal solution
model for the MgF2 -CaF2 liquid.
123
Menu Window: Set up the Variables
We wish to calculate 𝑇~𝑋B type of phase diagram.
𝑛MgF2
= 𝑋MgF2
𝑛MgF2 + 𝑛CaF2
124
Menu Window: Calculate
125
Results: the MgF2 -CaF2 Phase Diagram
126
Results: Invariant Reactions
The invariant reaction labeled as “4” is the eutectic reaction.
127
Now, let us choose the MgF2 -CaF2 liquid which is modeled as an ideal solution.
Back to the Menu Window.
Remove FTsalt-SALTA.
To define an ideal liquid MgF2 -

CaF2 solution, we need both
pure liquid MgF2 and pure
liquid CaF2 . However, the FTsalt
database does not include the
model for pure liquid CaF2 .
Therefore, another database
(normally FactPS) must be
used.
128
Bac to Components Window: Add FactPS
Choose both FactPS and FTsalt.
129
Pure Solids: Remove all the pure solids from the FactPS database
Because we included the FactPS database, more

pure solids were added to the selection list. We
can manually remove all the pure solids from
the FactPS database. However, you don’t have to
do so.
130
Pure Liquids: Define Ideal Liquid 𝐌𝐠𝐅𝟐 -𝐂𝐚𝐅𝟐 Solution
Choose pure liquids of MgF2 and CaF2 .
Permit selection of “X” species.

Note: “X” species are those with a lower priority.
131
132
Repeat for CaF2
133
Menu Window: Calculate when the liquid solution is ideal
134
Results: the MgF2 -CaF2 Phase Diagram (when the liquid solution is ideal)
135
Results: Invariant Reactions (when the liquid solution is ideal)
136
Comparison: Open the Figure Module
We will use the Figure Module to
superimpose the two phases
diagrams of the MgF2 -CaF2
system.
Run Figure
137
Comparison: Open the first phase diagram
138
Comparison: Open the first phase diagram
Before we superimpose the second
phase diagram, let us change the
color of lines on the first phase
diagram (FTsalt-SALTA) to red.
139
Comparison: Superimpose the second phase diagram
140
Comparison: Superimpose the second phase diagram
It is seen that the real liquid solution

model (FTsalt-SALTA, labeled as red)
gives lower liquidus lines and eutectic
temperature than if ideal liquid
solution model is used.
This means that liquid MgF2 and
liquid CaF2 exhibit negative deviation
from ideality. (Reason?)
141
In-Class Exercise
Question 1.
Calculate the predominance diagram of the Mo-C-O system at 1400 K. Use
log10 𝑃CO2 Τ1 atm as Y-axis, and log10 𝑃CO Τ1 atm as X-axis.
For a total hydrostatic pressure of 1 atm, what are the pressures of CO2 and CO
when metallic Mo is stable with its carbide phase at 1400 K?
142
In-Class Exercise
Question 2.
Calculate the Al-Mg phase diagram. Label all the liquid and all solid phases. Then
answer the following questions:
(a) What is the lowest melting point in the system?
(b) What is the maximum solubility of Mg in solid FCC Al?
(c) What is the maximum solubility of Al in solid HCP Mg?
(d) At 350 °C, what is the solubility limit of Mg in solid FCC Al? What is the
solubility limit Al in solid HCP Mg?
(e) Over what range of temperature is the Al30 Mg 23 phase stable?
(f) What is the non-stoichiometric range of the gamma phase (CBCC-A12)?
143
In-Class Exercise
Question 3.
Calculate the phase diagram for the Fe-Cr-O2 system at 1300 °C.
Use log10 𝑃O2 Τ1 atm as the Y-axis which varies from from −20 to 0, and use the
mole fraction of Cr 𝑋Cr as the X-axis which varies from 0 to 1. For an Fe-Cr alloy
with the composition of 𝑋Cr = 0.18, what is the maximum 𝑃O2 that will permit
this alloy to remain free of oxidation at 1300 °C?
144
In-Class Exercise
Question 4.
Calculate the “quasi-” binary phase diagram of the MgO-Al2 O3 system. Find the
temperature and specify the co-existing phases and reactions at all the invariant
points.
145
In-Class Exercise
Question 5.
Choose FTlite database to calculate the liquidus projection of the Al-Mg-Si and
isothermal sections at 500 and 1000 K (1 bar). Then compare them with the
diagrams calculated by SGTE2017 database (available from Documentation).
146

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FactSage Practical

Practical 3. Phase Diagram Calculation

Phase Diagram Calculation.

Practical 3. Phase Diagram Calculation

Areas: domains of stability of

Lines (univariant): coexistence of

Triple (Invariant) Points: coexistence

At equilibrium, ∆𝑟 𝑔 = 0, and log 𝑃SO2 ~log 𝑃O2 can be calculated.

Again, before you work on your project, check the Directory!!!

This might be the default database

The maximum number of Metals is 3.

The maximum number of Metals is 3.

Click on “Next” to activate the calculation.

The maximum number of Non-

Total hydrostatic pressure.

Temperature is 700 °C.

Axes: partial pressures

Choose “diagram”. The triple

For a given total hydrostatic pressure of 1

You are suggested to perform the calculations

Here, the maximum carbon activity is set as 10. In

Along the curve of the total hydrostatic pressure of 1 atm, as

At low 𝑃O2 , the main gas species is CO. It is therefore

Choose 𝑃CO as the Y-axis.

At low 𝑃O2 , 𝑃CO is close to unity.

Practical 3. Phase Diagram Calculation

Phase Diagram Module: Unary and Binary

Don’t forget to check your Directory.

We are plotting single-component phase diagram: H2 O

We need to tell FactSage which phases should be considered before

Pressure range. We are using

Triple point (please read the coordinates).

These pre-made phase diagrams using the

1. Don’t forget to check your Directory.

2. Add a new Component.

Choose FTlite only.

Left click on the column of “Base-Phase” or

We need to tell FactSage which phases should be

1. There is no need to choose pure liquids because we will

2. Select all the pure solids.

Note: the [I]-option only means we are considering

Pressure, if not exceedingly

Use this to manually add labels for

This will list all the invariant reactions

All the invariant reactions (the number of degree of freedom is zero)

Phase equilibrium mode can be used to quickly calculate the

Specified Temperature and Composition

The phases at equilibrium.

FToxid should contain the optimized model

Don’t forget to check your Directory.

Note: the Fe-Liq phase is a

These Fe structures have no

Number refers to the type of phase

Similar to FSstel-Liqu, no solubility limit of oxygen

Note: there is no need to check the FTdemo database.

FactPS is chosen so that different solid pure Fe structures

A must-have database based on the pre-made phase diagram

This database is chosen because it contains the model which

Select all the solutions and use the default settings