FactSage Workshop for beginners

FactSage
Basics and Advanced

Junghwan Kim and In-Ho Jung

Dept. of Mining and Materials Eng., McGill Univ.

[email protected]
[email protected]

Montreal
1 2014
REVIEW OF
ENGINEERING
THERMODYNAMICS

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2 2014
 Gibbs energy

G = H – TS; G: Gibbs Energy, H: Enthalpy, S: Entropy

1. For pure element or pure compound (Al, O2, Al2O3, etc.)

G  H  TS
o
T
o
T
o
T
T T
Cp
H  H   C p dT S S  
o o o o : Cp = a + bT + cT-2
T 298 K T 298 K dT
298 K 298 K
T + dTlnT + · · ·
is known (measurable)
is enthalpy for compound at 298 K with
reference of pure stable elemental species is standard entropy at 298 K
At 298 K 1 atm ( H 0oK  0 , unknown) ( S 0oK  0 )

Standard state for H : ΔH 298K

o
0
for all stable elements at 1atm and 298K. * In FactSage compound database,
o
Fe(bcc), Fe(fcc), Fe(l), H2O(l), H2O(g), H2(g), ΔH 298K , S 298 K ,C p , are stored
o

O2(g), O(g), CaO, FeO, C(s), CO2, CO,. Absolute Gibbs Energy of compound
relative to elemental species.

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3 2014
 Gibbs energy

2. Chemical reaction between pure compounds (No solution)

nA + mB = AnBm

Grxn  G Aon Bm  (nG Ao  mG Bo )

 H rxn
o
 TS rxn
o

In many thermo books, these H rxn o o

, S rxn are given.
These values are not absolute values, but dependent on each chemical
reaction.
 In the FactSage, therefore, absolute Gibbs energy of each species
(relative to elemental species) is stored. Then, the reaction Gibbs
energy for each reaction is automatically calculated from the Gibbs
energy of each species.

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4 2014
 Gibbs energy

3. Chemical reaction involving gas

nA + O2(g) = AnO2

Grxn  GAonO2  (nG Ao  mGOo2 )

Gi  Gio  RT ln Pi
for gas species i

 G o  mRT ln PO2
At Equilibrium state Grxn  0

 G o   RT ln( P 1 m )
O2

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 Gibbs energy

3. Chemical reaction involving gas (continue)

In general, for aA + bB(g) = cC + dD(g)

At Equilibrium
PDd
G   RT ln( Pb )
o
B

G o   RT ln K K: Equilibrium constant

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6 2014
 Gibbs energy

4. Chemical reaction involving solid or liquid solution

Gi ( in so ln)  G o
i ( pure )  RT ln(ai ) a: activity

change of Gibbs energy of i in solution

by interacting with surrounding species
Definition of activity

Pure Gas A Gas Mixture

p Ao pA PA
aA  o   A xA
PA
∴ activity is movement of species in solution
Pure Liquid A A in solution

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 Gibbs energy
4. Chemical reaction involving solid or liquid solution (continue)
Definition of activity (continue)
1
ai  ( pi / pio )   i xi
(+) deviation: repulsion between i and other species
(+) deviation  ai  xi : more active chemical reaction of i
ai ideal
(-) deviation: attraction between i and other species
 ai  xi : less active chemical reaction of i
(-) deviation

0 xi 1

In general, for aA + bB(g) = cC + dD(g)

Grxn   Gproducts   Greactants
At Equilibrium
* FactSage solution database contain the
aCc PDd
G   RT ln( a a Pb )
o model and model parameters to calculate
Gi  ai
A B

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8 2014
 Gibbs energy minimization

In most of thermodynamic book, we always calculate equilibrium condition

Grxn  0 G o   RT ln K eq
But in reality, we want to first know the direction of reaction

mA + nB Inputs (initial condition)

many possible outputs Tfinal, Pfinal

A2B (m-2)A
(n-1)B
A2B (m-3)A
AB2 (m-1)A
(n-2)B
AB2 (n-3)B
(m-x)A
(n-y)B
(xA-yB)soln
Final equilibrium state?

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9 2014
 Gibbs energy minimization

(continue)
 We have to find out which phase assemblage is most stable at given Tf
and Pf with respect to the mass balance with inputs.
 Gibbs energy minimization routine. (ChemSage, Solgas-mix, etc.)
The most stable phase assemblage has the lowest Gibbs energy.

In FactSage
i) Put inputs amount
ii) Select all possible phases (solid compounds, solid solutions,
liquid solutions, gases)
iii) Set Tfinal and Pfinal
iv) Calculation (Gibbs energy minimization routine)
v) Equilibrium phases

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 Ellingham diagram
(A)
- Collection of ΔGo for oxidation reaction
mA + O2 = AmO2 (reference: 1 mol of O2)
ΔGo (kJ / mole of O2)

- Only consider for pure species.

(No solutions are considered.)
A + O2 = AO2
(a AO2 )
G  G o  RT ln , (G  0 : Equilibrium)
(B) (a A ) ( pO2 )
G o  RT ln pO2
G o  ( R ln pO2 )  T

2Fe + O2 = 2FeO …... (A)

2Mg + O2 = 2MgO …. (B)

T (K) (B)-(A) =>

Mg + FeO = Fe + MgO: ΔGo < 0

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11 2014
 Solution thermodynamics

A-B solution, (Solid or Liquid solution)

Gsolution   xi Gi
Gi  Gio  RT ln ai Gi: partial Gibbs energy of i in solution

g solution g Bo

g Ao Δ g mix
g A  g Ao  RT ln aA g B  B
RT ln a A
g A  A
XB
i : Chemical potential of i

 ( xAGAo  xBGBo )  RT ( xA ln aA  xB ln aB )
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 Solution thermodynamics

A-B solution, (Solid or Liquid solution)

Gsoln  ( xAGAo  xBGBo )  RT ( xA ln a A  xB ln aB )

1. Ideal solution:  A  1,  B  1
Gsoln  ( xAGAo  xBGBo )  RT ( xA ln xA  xB ln xB )

2. Regular solution: RT ln  A   AB xB2 Ω: Regular solution parameter

Gsoln  ( xAGAo  xBGBo )  RT ( xA ln xA  xB ln xB )   AB xA xB

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 Solution thermodynamics

A-B solution, (Solid or Liquid solution)

Gsoln  ( xAGAo  xBGBo )  RT ( xA ln a A  xB ln aB )

3. General solution:  A  f ( x, T )
Gsoln  ( xAGAo  xBGBo )  RT ( xA ln xA  xB ln xB )  G ex
G ex    AB
ij
x iA xBj
i , j 1

* FactSage has many complex solution models and model parameters and
solution database contains optimized model parameters reflecting Gibbs energy
more accurately.

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 Gibbs Energy vs. Phase Diagram

 Phase diagram is the collection of minimum Gibbs energy

assemblage of given system with temperature.

T1

Porter, D.A., and Easterling, K.E., Phase Transformation in Metals and Alloys, 2 nd Ed. CHAMAN & HALL (1992)

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 Gibbs Energy vs. Phase Diagram

 Phase diagram is the collection of minimum Gibbs energy

assemblage of given system with temperature.

T2

Porter, D.A., and Easterling, K.E., Phase Transformation in Metals and Alloys, 2 nd Ed. CHAMAN & HALL (1992)

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 Gibbs Energy vs. Phase Diagram

 Phase diagram is the collection of minimum Gibbs energy

assemblage of given system with temperature.

T3

Porter, D.A., and Easterling, K.E., Phase Transformation in Metals and Alloys, 2 nd Ed. CHAMAN & HALL (1992)

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17 2014
 Gibbs Energy vs. Phase Diagram

 Phase diagram is the collection of minimum Gibbs energy

assemblage of given system with temperature.

T4

Porter, D.A., and Easterling, K.E., Phase Transformation in Metals and Alloys, 2 nd Ed. CHAMAN & HALL (1992)

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Thermodynamic Database Development: FactSage

Pure compound

GTo  HTo  TSTo

T
 Calorimetry

C
emf
H To  H 298
o
K  dT
p
 Knudsen cell
298 K
T 298 K  Vapor pressure
Cp Cp
S S    
o o o
T 298 K dT S 298 K dT
298 K
T 0K
T

Solution
 emf (activity)
G ex    AB
ij
x iA xBj  Knudsen cell (activity)
i , j 1
 Vapor pressure (activity)
 Solution calorimetry (enthalpy)
 Phase diagram

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19 2014
 Dilute Solution

(+) deviation

aA ideal
(-) deviation  o
A
aA   xo
A A: Henry’s law
slope
 A   Ao
0 xA 1

Constant slope

Henrian activity coefficient

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20 2014
 Dilute Solution
Most of refining process involves impurity elements (dilute solutes)
 Henrian activity is important

For example, Al-deoxidation process in steelmaking,

2 Al  3O  Al2O3 (s)
(a Al2O3 ) (a Al 2O3 )
G   RT ln
o
  RT ln
(a Al2 ) (aO3 ) ( Alo X Al2 ) ( Oo X O3 )
 Alo is the Henrian activity coefficient of Al in pure liquid Fe

Now, if we have other elements in Fe such as O, Mn, C, etc.

there is interaction between Al and these elements.
 Change of  Al from  Al : interaction coefficients
o

ln  Al  ln  Al
o
  AlAl x Al   Al
O
xO   Al
C
xC  ...
* FactSage FTmisc-FeLQ database contains these Henrian activity
coefficients and interaction parameters for liquid steel.

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 Change of Standard State
Gibbs Energy

g io( wt .%)

gio( H )

g io( R ) RT ln ai ( H ) RT ln ai ( wt %) Gi  Gio( R )  RT ln ai ( R )  Gio( H )  RT ln ai ( H )

RT ln ai ( R )
 Gio( wt .%)  RT ln ai ( wt .%)
gi ( gi )

 Raoultian standard state  Henrian standard state

Gio( RH )  RT ln  io ai ( H )  f i xi
ln f i   ii xi   i j x j   ik xk  ...
 Raoultian standard state  1 wt.% standard state

G o   io M Bulk
 RT ln


ai ( wt .%)  f i xi
i ( R  wt %)
 100 M i  log fi  eii [wt%i ]  eij [wt% j ]  eik [wt%k ]  ...

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 Heat evolution calculation

H = H final - H initial =
𝑻𝒎𝒆𝒍𝒕𝒊𝒏𝒈 𝑻𝒇𝒊𝒏𝒂𝒍 A(L)
𝑪𝒑(𝒔) + 𝑯𝒎𝒆𝒍𝒕𝒊𝒏𝒈 + 𝑪𝒑(𝒍)
𝑻𝒊𝒏𝒊𝒕𝒊𝒂𝒍 𝑻𝒎𝒆𝒍𝒕𝒊𝒏𝒈 H final

CP(l)
Heat (enthalpy)

Hm (melting)

A(s)
CP(s)

H initial
process

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 Heat evolution calculation

Hf = heat of formation (or reaction)

from A(s) + B(s) to AB(s)
A(s) (typically negative value)
Heat (enthalpy)

B(s)

Hf AB(s)

process

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24 2014
 Heat evolution calculation
A(L)

B(L)
Heat (enthalpy)

A-B solution
(liquid)
A(s)

B(s)

AB(s)
process
In FactSage, the H initial and H final are directly calculated because the H of each phase
is calculated from the thermodynamic equations of each solid or liquid phases.
It is important to select proper initial and final materials’ states and temperatures.

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25 2014
 Gibbs energy of reaction

Greaction  (  ni g i ) products  (  ni g i ) reactants

gi  o
gi  RT ln ai
Activity of i
Standard state should be checked carefully

In FactSage, G o
reaction(between pure compounds) can be calculated
from the “Reaction” module, and the activity of each reactant/product
component can be calculated using “Equilib” module.

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FACTSAGE Intro.
- FactSage Introduction
- Databases in FactSage

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 FactSage Introduction

All materials processes involve

“Thermodynamics” and “Kinetics”.

Thermodynamics (Equilibrium) tells where we go.

Kinetics tells how fast we can go.

FactSage can provide Thermodynamic calculations for:

- Multicomponent (< 48 elements) Chemical reaction equilibria
- Phase diagrams up to 8 component systems
- Thermodynamic properties such as heat balance, G, H, S, etc.

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 FactSage Introduction
Gas, Oxide, Salt and Alloy databases

Scheil Cooling Calculation

as cast microstructure Phase diagram
Data mining program Multicomponent
Equilibrium Calculation (FactOptimal) phase diagram section
Equilibrium reactions
as annealed microstructure
Alloy design

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 Material Processing and FactSage

Process What we can do with FactSage

Extraction / Refining /
Gas/Slag/Matte/Salt/Metal/Refractory reactions
Recycling
Scheil cooling calculation (as-cast microstructure)
Casting
Solidification software
Multicomponent equilibrium calculations
Annealing /
Secondary phase precipitation
Homogenization
Solidification software
TMP / Forming
Final treatment:
Oxidation phase diagram, E-pH diagram, Gas corrosion
Oxidation / Corrosion
reactions
/ Surface treatment
All kinds of thermodynamic properties:
Thermodynamic
properties Heat balance, G, H, S, activity, partial pressure of gases,
etc..
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 Database in FactSage
Brief History of FACTSAGE Database Development

1976~2001: F*A*C*T  2001~present: FactSage (a fusion of F*A*C*T + ChemSage)

< 1998 : FACT database (before 1998)

1999~2003 : FACT53 database

2000~2004 : FACT Consortium project (2000~2004): 16 companies

pyrometallurgy (ferrous, non-ferrous), hydrometallurgy-corrosion, glassmaking
- FACT53 database  FToxid, FTmisc, FThall, FTsalt, FThelg,..
- New alloy databases: FSStel, FSlite, FScopp, SGTE, ….

2004~2010 : Mini-consortiums
- Al consortium (Alcoa, Alcan, and Norsk-Hydro)
- Glass consortium (Corning, Schott, and Saint-Gobain)
- Light alloy (Al, Mg) consortium (Al consor., GM and MagNET): FTlite
- Steelmaking consortium (Posco, RIST, and Tata Steel Europe)

2011~2014 : Mini-consortiums
- Al consortium (3 companies), Glass consortium (3 companies)
- Steelmaking consortium: 11 companies  Consortium database (‘CON1’)

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 Database in FactSage
Brief History of FACTSAGE Database Development

1976~2001: F*A*C*T  2001~present: FactSage (a fusion of F*A*C*T + ChemSage)

< 1998 : FACT database (before 1998)

1999~2003 : FACT53 database

2000~2004 : FACT Consortium project (2000~2004): 16 companies

pyrometallurgy (ferrous, non-ferrous), hydrometallurgy-corrosion, glassmaking
- FACT53 database  FToxid, FTmisc, FThall, FTsalt, FThelg,..
- New alloy databases: FSStel, FSlite, FScopp, SGTE, ….

2004~2010 : Mini-consortiums
- Al consortium (Alcoa, Alcan, and Norsk-Hydro)
- Glass consortium (Corning, Schott, and Saint-Gobain)
- Light alloy (Al, Mg) consortium (Al consor., GM and MagNET): FTlite
- Steelmaking consortium (Posco, RIST, and Tata Steel Europe)

2011~2014 : Mini-consortiums
- Al consortium (3 companies), Glass consortium (3 companies)
- Steelmaking consortium: 11 companies  Consortium database (‘CON1’)

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32 2014
Database in FactSage for Ferrous/Non-Ferrous Applications

FACTPS: All gaseous species, stoichiometric solid and liquid species

(organic, inorganic). It used to be called as FACT53
 Similar to thermodynamic table like JANAF, Barin-Kubaschewski

FToxid: Most updated Oxide database with

- many solution phases (slag, spinel, monoxide, olivine, etc.)
- pure solid and liquid oxides, No gas phase

FTmisc: FeLq solution

- most reliable liquid steel database for steelmaking calculations
(slags/refractories/gases/molten iron)
Cu-Lq, Pb-Lq, Zn-Lq solution, etc.
Matte and other Sulfides

FSStel: solid and liquid steel phases

(also includes small number of gases, oxides, sulfides, nitrides, etc.)
- for steel solidifications and alloy design.
- liquid steel: reasonable calculations for steelmaking applications

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 FTmisc (FeLq) and FSStel

FeLq
Liquid Fe containing Ag,Al,B,Ba,C,Ca,Ce,Co,Cr,Cu,H,Hf,La,Mg,Mn,Mo,N,Nb,Nd,Ni,O,P,Pb,Pd,S,Si,
Sn,Ta,Th,Ti,U,V,W,Zr. This phase is better suited for calculations involving iron and steelmaking processes
(optimized for iron-rich solutions only).
 Based on the Unified Interaction Parameter Formalism (advanced than Classical Wagner’s Interaction
parameter formalism) with associate model for deoxidation. Many interaction parameters between metallic
elements are taken from JSPS (Japanese compilation)

FSStel database
The elements included in the FactSage FSstel steel database are:
Al, B, Bi, C, Ca, Ce, Co, Cr, Cu, Fe, Hf, La, Mg, Mn, Mo, N, O, Nb, Ni, P, Pb, S, Sb, Si, Sn, Ta, Te,
Ti, V, W, Zn, Zr
 FCC/BCC: Fe / Carbide / Nitride are all treated as FCC phases
 Fe with N and C : use J option (3-miscibility gaps).
 Fe with N or C : use I option (2-miscibility gaps).
 Also recommend to use I option for BCC phase
For example, see Fe-Ti-Nb-C-N example.

 Liquid: O and S are treated as associate model

 FCC ordered phase (FCC_L12), BCC ordered phase (BCC_B2) normally slow down the calculations
significantly. If you are not really interested in order/disorder transitions, do not to select these phases.

Carbon: when C content is lower than ~ 1%, Fe3C (metastable) phase is normally formed instead of C (stable).
So, in the selection of solid phases, “unselect” C solid phases.

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 FToxid database
Main solution phases when T > 1550oC (steelmaking)

 Slag (I option): CaO-MgO-Al2O3-SiO2-FeO-Fe2O3-MnO-Mn2O3-Ti2O3-TiO2…

+ Gas solubility such as S (SO2), P, H (OH), N, C, F, …

 Spinel (I option) (SPIN): (Mg,Fe,Mn,Co,Ni,Zn)(Al,Fe,Cr,Co,Mn,Va)2O4, extensive solid solution

containing MgAl2O4, MgCr2O4, MgFe2O4, FeCr2O4, Fe3O4, FeAl2O4, Cr3O4, MnAl2O4,
MnCr2O4, MnFe2O4, etc.
(AlSp): (Fe,Mg,Mn)Al2O4-Al2O3 solution

 a-, a’-Ca2SiO4 (aC2S, bC2S): Ca2SiO4 (C2S) rich solution with limited solubility of Mg2SiO4,
Fe2SiO4, Mn2SiO4,etc.

 Olivine (Oliv): Mg2SiO4, Fe2SiO4, etc. (Mg,Fe,Ca,Mn,Ni,Zn,Co,Cr,etc.)2SiO4, covering

forsterite (Mg2SiO4), fayalite (Fe2SiO4), -Ca2SiO4, monticellite CaMgSiO4, tephroite Mn2SiO4.
I option specially when Ca2SiO4 exists.

 Corundum (CORU): (Al,Cr,Fe,Mn)2O3 solution, the solution of Al2O3, Cr2O3 and Fe2O3. Solid
miscibility gaps exist between the constituents. I option required.

 Monoxide (halite) (MeO_): of CaO-MgO-FeO-MnO-NiO-Fe2O3-Al2O3-Cr2O3 etc. well-known

lime (CaO), periclase (MgO) and wustite (FeO). I option especially when CaO and MgO exist
together.

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 FToxid database
 Mn/Ti oxides:
i) ilmenite (ILME): (FeTiO3(ilmenite)–Ti2O3–MgTiO3–MnTiO3 + Al2O3),
ii) pseudo-brookite (PSEU): (Ti3O5–FeTi2O5-MgTi2O5–MnTi2O5 ),
iii) Ti-spinel (TiSp): (Mg,Fe,Mn)[Mg,Fe,Mn,Ti,Al]2O4
iv) Rutile (TiO2):TiO2 + Ti2O3-ZrO2 solid solution

 Mullite (Mull): non-stoichiometric Al6Si2O13 with possible solubility of B.

(MulF): stoichiometric Al6Si2O13 with dilute Fe6Si2O13.

Melilite (Mel_): Ca2[Mg,Fe2+,Fe3+,Al](Fe3+,Al,Si)2O7. Akermanite Ca2MgSi2O7 and gehlenite

Ca2Al2SiO7 form the melilite solid solution stable below 1590 °C.

Main solution phases when T < 1550oC (solidification of slag)

 Wollastonite (Woll): (Ca,Mg,Mn)SiO3, which is a CaSiO3 rich phase stable below 1300 °C.
Pseudo-wollastonite is stoichiometric CaSiO3 stable below 1550 °C.
pyroxene (pPyr, oPyr, cPyr): (Mg,Ca,Fe)[Mg,Fe]Si2O6, which is a MgSiO3-rich phase stable
below 1560 °C. proto-, ortho-, low-clino-pyroxene exist. Clino-pyroxene is a CaMg2SiO6-rich
phase, which is stable below 1390 °C.
 Rhodonite (Rhod): (Mn,Ca)SiO3, a MnSiO3-rich solid stable below 1300 °C.

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 FToxid database

Main solution phases in CaO-Al2O3-SiO2-FetO system when high PO2 (air)

CAFS Ca2(Al,Fe)8SiO16, CAF6 Ca(Al, Fe)12O19, CAF3 Ca(Al,Fe)6O10, CAF2 Ca(Al,Fe)4O7

CAF1 Ca(Al,Fe)2O4, C2AF Ca2(Al,Fe)2O5, C3AF Ca3(Al,Fe)2O6

Main solution phases when T < 1550oC (mould flux, Na2O containing system)

 Nepheline (Neph): NaAlSiO4 with excess SiO2.

 Carnegeite (Carn): NaAlSiO4 with excess SiO2.
 NaAlO2 (NASl): low temperature - NaAlO2 with excess NaAlSiO4
 NaAlO2 (NASh): high temperature - NaAlO2 with excess NaAlSiO4
 Combeite (NCSO): Na4CaSi3O9 (bombeite) – Na2Ca2Si3O9 solid solution

 Feldspar (Feld): complete solution between Anorthite(CaAl2Si2O8)-Albite(NaAlSi3O8)

 NCA2: (Na2,Ca)O·Na2O·2Al2O3 solid solution

 C3A1: Ca3Al2O6 dissolving Na2O, (Ca,Na2)1Ca8Al6O18 solution

Most updated version of Na2O containing system in available in “CON1” database

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 Alloy database: Others

• FSCopp: Copper alloy development (all binary Cu-X systems

• FSlite: Old database for FTlite

• FSupsi: High purity Si database for solar cell grade Si production

• FSnobl: Noble alloy database for Ag, Au, Ir, Os, Pd, Pt, Rh, Ru refining

• SGnobl: Similar to FSnobl

• SGsold: Solder alloy database

• SGTE 2011: developed by SGTE (www.sgte.org): Applicable to all

general alloy system. But less accurate than other dedicated databases for
specific region.

• FTlite: Light metal database (formerly FSlite)

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 FTlite database
Thermodynamic data & parameters for:
* 139 solution phases
HCP(HCP_A3) Ag, Al, Be, Ca, Ce, Cr, Cu, Fe, In, Li, Mg, Mn, Mo, Na, Ni, Sb, Sc, Si, Sn, Sr, Ta, Ti, Y, Zn, Zr, RE
Liquid As HCP + hydrogen, carbon, boron
BCC & FCC Similar list as HCP
Gamma (-Al12Mg17) Mg, Al, Zn, Li
Al8Mn5 Al, Cu, Fe, Mn, Si
AlxMny with Fe (x=4 & y=1; x=11 & y =4)
Tau- & Phi- ternary Mg-Al-Zn phases
Laves C14, C15, C36 Al, Ba, Ca, Mg, Sr, Zn, (RE) (being updated)
LC14: Laves_C14: Mg2Zn, Mg2Y, CaLi2, Mg2Ca, Mg2Sr, Mg2Ba
LC15: Laves_C15: MgCu2, Mg2Ce, Mn2Y, Al2Y, Al2Ce, Al2Ca, Al2Sc, Al2Sr
LC36: Laves_C36: MgNi2
Mg2X (X = Si,Sn,Ge,Pb) Mg2Si, Mg2Sn, Mg2Ge, Mg2Pb
– …
* 681 pure compounds
* Thousands of gaseous species (from the FACT53 Database)

– Volumetric data & parameters

For the Mg-Al-Zn-Mn-(Fe) system

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FactSage Basic
- Documentation
- View Data
- Compound
- Reaction
- Equilib
- Phase Diagram

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Documentation

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Documentation

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Documentation

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View Data

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 View Data

Enter the species you wish to view in the database.

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 View Data
Available elements and compounds list in the selected database.

Double click

Thermodynamic properties

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View Data

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 View Data

List of solutions

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View Data

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Compound

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 Compound

Enter the species you wish to view in the database.

Read only
database

Read and Write

database

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Compound

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Compound

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 Compound

Creating own database

Entering species by ‘copy and paste’ or ‘drag and drop’

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Compound
The «Mixer»feature permits the generation
of new compound data using simple
algebra on the data of already stored
compounds.

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Compound

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 Compound

GTo  HTo  TSTo

T T
Cp
H  H  C S S  
o o o o
T 298 K p dT T 298 K dT
298 K 298 K
T
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Compound

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 Compound

Creating another phase

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 Compound
1. ΔH298, S298, Cp
Two ways to add Gibbs energy
for second phase

2. ΔHtransforamtion, Ttransformation

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Compound

Same as window in Viewdata

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 Reaction

• Reaction module calculates thermo-chemical properties of species, a mixtures of

species, or a chemical reaction.
• Only accesses compound databases (no solutions) and assumes ideal gases
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 Reaction
Add a product
Add a reactant
Open
New Reaction

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 Reaction
• Calculation can be quickly performed
• In this example, temperature is being varied
• Transitions are also calculate

Calculation Syntax
[Start] [End] [Step]

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 Reaction
• Phase with the lowest Gibbs energy is the most stable

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 Reaction
• The same can be done for a reaction
• The reaction will be balanced by the software
• Equilibrium constants are also calculated

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 Reaction

• Problems can also be completed with non standard states

• Standard states
– PO2(g) = 1.0 atm
– aCu(s) = 1.0

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 Reaction

• To compete this kind of equation 3 variables must be set. In the figure

below partial pressure, activity, and dG have been set to calculate
temperature.
• Only ideal systems can be considered (activity coefficient = 1)

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Reaction
• Non equilibrium calculation (no K)
• DH=enthalpy of fusion
• Can plot results

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Reaction

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 Reaction
• Composition can be varied by using the <A> operator (alpha)
• Following example considers the combustion of CH4 with variable
oxygen (typical heat problem)
• Each phase must be specified

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 Reaction
• Can fix and two components and solve for the third
• A=2 is the stoichiometric reaction, excess oxygen reduces the heat
available to the system
• The flame temperature can be calculated assume an adiabatic reaction
dH=0

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 Equilibrium

• Equilib is the workhorse of FactSage

• Calculates equilibrium based on reactants
• Best shown through examples

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 Equilibrium
Comparison with Reaction

• What products can be formed from the following reaction

at 25°C?
• Mg + 3 Cu2O + 2 Fe3C + Ar ?
– MgO + 6 Cu + 4.5 Fe + 2 C + 0.5 Fe3O4 + Ar
– MgO + 6 Cu + 4.667 Fe + 2 C+ 0.667 Fe2O3 + Ar
– MgCO3 + 6 Cu + 6 Fe + 1 C + Ar
– Etc
• These are all possible reactions
• Equilib identifies all the possible products and compares the
dG of each reaction, identifying the most thermodynamically
favour reaction.

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Equilibrium

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 Equilibrium

• Mg + 3 Cu2O + 2 Fe3C + Ar
• Similar prompt as reaction module (no product)

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 Equilibrium

• This is where you can examine the reactants and consider the final
conditions to consider
• In this example pure liquids are not selected to reduce the number of
calculation

Summary of Reactants

Products to consider

You may also set other final conditions

Final Conditions
25°C and 1 atm

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 Equilibrium

• Results Menu
– Mass is balanced
– Shows stable and non-stable
compounds
– Close attention to mols and
activity

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 Equilibrium

• Scrolling down
– Reactants
– Products
– Final conditions Final Conditions

Reactants

Gases

Products
Stable

You can change the format of the

results but typically you will want
both Fact + ChemSage

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 Equilibrium

• The list menu contains all the computed information and allows for
modification of the output options
• Same results
– Changed format

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 Equilibrium
Adiabatic Combustion
FactPS database
This example will demonstrate a few
features
1. The use of alpha for two variables
2. Specifying target dH
(adiabatic dH=0)

This will produce a series of temperature

results
The expected max is at 2/3
2 O2 for every CH4
Calculations are done every 0.01 step

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 Equilibrium

Multiple solutions at once

Easiest way to examine

results is graphically

The Results
Processor prompt
appears

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 Equilibrium

Press the “Axes” button and pick the conditions

Alpha is the <A> variable

This plot shows the expected result, a

maximum at 0.67

Smaller steps in <A> will provide a smoother

curve

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 Equilibrium
Working with Activity

FactPS database
• Consider FeS with a given partial pressure of oxygen

Right click gas to examine the gas

species

A selection window will appear

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 Equilibrium
Right click the “+” for O2(g) and select activity and enter the desired value

Once activity is fixed a custom solution

notification is shown
Clicking details allows you
to make changes

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 Equilibrium

Additional oxygen added to fix partial pressure

PO2=0.01 atm

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 Equilibrium
Ideal and Non-Ideal Gas

FactPS database

First we’ll examine an ideal gas

Choose normal + transition

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 Equilibrium
Transitions are calculated
Note the difference in volume and complete change in phase

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 Equilibrium

Same problem but now real

boiling point is now 100°C

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 Equilibrium
Target calculations
(a)Transitions:
do calculation between initial and final temperature and find all phase transition
between them
Mg - Al

700
FactSage

(b) Precipitation target: find temperature at which any other phase

begins to precipitate out from the targeted phase
Liquid

560

Liquid + HCP_A3 Liquid + FCC_A1

FCC_A1
420
HCP_A3

Gamma
T(C)

Gamma + Al 30Mg23(s)

280 (c) Formation target: find the temperature at which

HCP_A3 + Gamma
the targeted phase begin to form FCC_A1 + Beta_AlMg

140
Gamma + Beta_AlMg

0
0 0.2 0.4 0.6 0.8 1

mole Al/(Mg+Al)

To learn more, go to ??
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 Equilibrium
Transition calculation
FTlite database
(1) Select the compositions
(2) Select “transitions” instead of “normal”

Range of temperature: “initial final interval”

Calculate Initial (0 oC) to final (700oC) temperature with interval of 10 oC
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 Equilibrium

Calculation results at every 100 oC intervals

input composition

What is this complex thing ?

-> model structure in database
-> output for modeling people

elemental composition of gamma phase

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 Equilibrium
Phase transition happens at this temperature

Although the amount of Gamma phase is zero,

the activity (a = 1) tells Gamma phase begins to
form at this temperature

activity (a) of this phase = 0.45598

a = 1: stable phase, a < 1: unstable

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 Equilibrium
Precipitation target calculation

automatic default estimated value

For target calculation, this

temperature should remain blank

Liquid is selected as precipitation target phase (P). Then, FactSage will calculate liquidus
temperature of a given composition
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 Equilibrium

Mg - Al

700
FactSage

Liquid

560

Liquid + HCP_A3 Liquid + FCC_A1

FCC_A1
420
HCP_A3

Gamma
T(C)

Gamma + Al 30Mg23(s)

280

HCP_A3 + Gamma

FCC_A1 + Beta_AlMg

140
Gamma + Beta_AlMg

0
0 0.2 0.4 0.6 0.8 1

mole Al/(Mg+Al)

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Equilibrium

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 Equilibrium

Mg - Al

700
FactSage

Liquid

560

Liquid + HCP_A3 Liquid + FCC_A1

FCC_A1
420
HCP_A3

Gamma
T(C)

Gamma + Al 30Mg23(s)

280

HCP_A3 + Gamma

FCC_A1 + Beta_AlMg

140
Gamma + Beta_AlMg

0
0 0.2 0.4 0.6 0.8 1

mole Al/(Mg+Al)

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 Equilibrium

Mg - Al

700
FactSage

Liquid

560

Liquid + HCP_A3 Liquid + FCC_A1

FCC_A1
420
HCP_A3

Gamma
T(C)

Gamma + Al 30Mg23(s)

280

HCP_A3 + Gamma

FCC_A1 + Beta_AlMg

140
Gamma + Beta_AlMg

0
0 0.2 0.4 0.6 0.8 1

mole Al/(Mg+Al)

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 Equilibrium
Formation target calculation

automatic default estimated value

For target calculation, this

temperature should remain blank
Liquid is selected as formation target phase (F). Then, FactSage will calculate solidus
temperature of a given composition
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 Equilibrium

Mg - Al

700
FactSage

Liquid

560

Liquid + HCP_A3 Liquid + FCC_A1

FCC_A1
420
HCP_A3

Gamma
T(C)

Gamma + Al 30Mg23(s)

280

HCP_A3 + Gamma

FCC_A1 + Beta_AlMg

140
Gamma + Beta_AlMg

0
0 0.2 0.4 0.6 0.8 1

mole Al/(Mg+Al)

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 Equilibrium
Variation of phase fraction with temperature

Transition calculation from 700oC to 200oC with 10oC interval

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 Equilibrium
(3) Click to select X, Y axes
(1)
Click to plot the results

(5) Selection of phases

Select the phase to plot

(4)

(2)
Click to setup axes
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 Equilibrium
Special care is required for the phase selection

Pure compounds such as Mg, Al, intermetallic compounds

Tip for
“phase fraction vs. temperature diagram”

All phases which have amount > 0 in “Pure Solids”

and “SOLUTIONS” should be selected.

Solutions such as liquid, hcp, fcc, gamma phases

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 Equilibrium
0.91 Mg + 0.09 Al
c:\FactSage61\Equi0.res 5M ay10

1.00 HCP#1 Liqu#1

HCP#1
HCP#1

0.80

0.60
gram

0.40

0.20 Solidus Liquidus

Gama
Liqu#1
0
200 300 400 500 600 700
T(C)

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 Equilibrium

If we want to plot the compositional variation inside of solution

phases, we have to select the elements in this “ELEMENTS”
section.

For example, if we want to plot the variation of Al and Mg

concentrations in liquid phase with temperature, we have to
select Al_Liq#1 and Mg_Liq#1.

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 Equilibrium
Converting reactant mass units (mol, g or lb)

Point the arrow in the mass input box to view the mass conversion.

Point the arrow in the species input box to view the molecular weight.

For example you may wish to specify the matte component in grams.
1. Right-click on the matte mass input box to open the mass menu.
2. Select: Convert this reactant amount to > g

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 Equilibrium
You can mix the mass units by including a 'mol', 'g' or 'lb' in the reactant amount.

If the default mass units is g, the

following is equivalent to the above
system:

Or if you like, you can always explicitly specify

the mass units for each reactant amount to
make your reactants data entry independent of
the default mass units.

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 Equilibrium
Creating new stream : Fe-0.1C-1Mn-1Si at 1600oC
FTmisc database (FeLQ): liquid steel

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Equilibrium

Save the liquid FeLQ phase as

a stream

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 Equilibrium
Import stream : Fe-0.1C-1Mn-1Si at 1600oC

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 Equilibrium
Heat balance: Fe-0.1C-1Mn-1Si(1600oC) + Al (25oC)
Adiabatic calculation :
Delta(H) = 0

Calculated adiabatic
temperature = 1605.5 oC

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 Equilibrium
Open Calculation - off-gas removal

RH – Vacuum degassing process

Stream Fe-0.1C-1Mn-1Si + O2
at 1600oC and 0.01 atm

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 Equilibrium
Open Calculation - results

Carbon content decreases due

to the reactions:
C + O2 = CO2
C + 0.5O2 = CO

New slag formed due to Si and

Mn oxidation:
Mn + 0.5O2 = MnO
Si + O2 = SiO2

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 Equilibrium
Open Calculation - plot of log(wt% liquid steel)

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 Equilibrium
Open Calculation - log(wt%) vs page
100% [FTmisc-FeLQ_Fe-liq] + <A> O2
c:\FactSage\casestudy\Equi0.res 21M ay09
2.00 Fe_FeLQ Fe_FeLQ Fe_FeLQ Fe_FeLQ

1.00

0 Mn_FeLQ
Si_FeLQ Mn_FeLQ Mn_FeLQ Mn_FeLQ
Si_FeLQ
log10(weight %)

Si_FeLQ
Si_FeLQ

-1.00

-2.00
O_FeLQ O_FeLQ
O_FeLQ O_FeLQ
C_FeLQ C_FeLQ C_FeLQ C_FeLQ
-3.00

-4.00
1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00
- page -
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 Phase Diagram

Phase Diagram is a generalized module that permits one to calculate, plot and edit unary,
binary, ternary and multicomponent phase diagram sections where the axes can be various
combinations of T, P, V, composition, activity, chemical potential, etc.

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 Phase Diagram
Binary phase diagram: CaO-SiO2
There is a stable miscibility gap in slag; automatic selection by FactSage

FToxid database

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 Phase Diagram

CaO - SiO2

2000

Ca2SiO4(s3) + CaO(s)

ASlag-liq
1800
ASlag-liq + ASlag-liq#2
ASlag-liq + Ca2SiO4(s3)

1600

ASlag-liq + SiO2(s6)
T(C)

Ca3SiO5(s) + CaO(s) ASlag-liq + CaSiO3(s2)

1400

SiO2(s4) + CaSiO3(s2)
1200

CaO(s) + Ca2SiO4(s2)

1000
0 20 40 60 80 100

mass 100SiO2/(CaO+SiO2)

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 Phase Diagram
Ternary phase diagram: CaO-SiO2-Al2O3 isothermal section

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 Phase Diagram
CaO - SiO2 - Al2O3
o
1550 C
FactSage
SiO2

0. 9

0. 1
ASlag-liq + SiO2(s6)

0. 8

0. 2
0. 7

0. 3
0. 6

0. 4
ASlag-liq + Mullite
0. 5

0. 5
ASlag-liq
0. 4

0. 6
ASlag-liq + Ca2SiO4(s3)
0. 3

0. 7
ASlag-liq + Al2O3(s4)
0. 2

0. 8
0. 1

0. 9
ASlag-liq + CaO(s)
0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1
CaO Al2O3
mass fraction

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 Phase Diagram
Ternary system: section in ternary (isopleth)
SiO2

1:1

CaO Al2O3

CaO – SiO2
=0
CaO + SiO2 + Al2O3
CaO = SiO2
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 Phase Diagram
CaO-SiO2-Al2O3 Vertical section
at (wt%CaO/wt%SiO2 ) = 1
CaO - SiO2 - Al2O3
mass (CaO-SiO2)/(CaO+SiO2+Al 2O3) = 0
1800

ASlag-liq + Al2O3(s4)

1640
ASlag-liq

1480 ASlag-liq + CaAl12O19(s)

ASlag-liq + CaSiO3(s2)
T(C)

ASlag-liq + Ca2Al2SiO7(s)

1320

1160

1000
0 20 40 60 80 100

mass 100Al2O3/(CaO+SiO2+Al2O3)

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 Phase Diagram

SiO2

1:1

CaO Al2O3

(CaO)0.017832(SiO2)0.016643
Molar ratio
= 1 = 1
56.0774 (g/mol) 60.0843 (g/mol)
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 Phase Diagram
CaO - SiO2 - Al2O3
mass (CaO-SiO2)/(CaO+SiO2+Al 2O3) = 0
1800

ASlag-liq + Al2O3(s4)

1640
ASlag-liq

1480 ASlag-liq + CaAl12O19(s)

ASlag-liq + CaSiO3(s2)
T(C)
ASlag-liq + Ca2Al2SiO7(s)

1320

1160

1000
0 20 40 60 80 100

mass 100Al2O3/(CaO+SiO2+Al2O3)

Exercise SiO2 Exercise SiO2

1. 2.
1:2
2:1

CaO Al2O3 CaO Al2O3

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 Phase Diagram
Quaternary diagram: iso-composition section

This is NOT 10% Al2O3 section !!

1) Equilib calculation mode

2) Click here

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 Phase Diagram
How to calculate 10% section exactly ?
CaO+MgO+SiO2 = 1.0 (100%), Al2O3 should be 10%
CaO+MgO+SiO2 = 1.0, Al2O3 = x
x/(1+x) = 0.1 (=10%)
x = 0.11111
So, if we give Al2O3 = 0.11111  Al2O3 = 10%

1) Equilib calculation mode

2) Click here
= 10% Al2O3
This is 10% Al2O3 section !!

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 Phase Diagram
Quaternary system: CaO-Ca2SiO4-MgAl2O4

CaO

Al2O3
SiO2

MgO
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 Phase Diagram
AZ31 – Sr phase diagram
FTlite database

In FactSage, all the input is in molar formula.

Thus, in order to add AZ31 (97wt%Mg-3wt%Al-1wt%Zn), we have to do conversion
of the composition into molar fraction first. Then, add this molar formula as input
97wt%Mg-3wt%Al-1wt%Zn -> 0.96897Mg-0.027277Al-0.0037517Zn

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 Phase Diagram
Mg0.96897Al0.027277Zn0.0037517 - Sr

700
Liquid

560 Liquid + HCP_A3

Liquid + HCP_A3 + Laves_C15

420 HCP_A3 + Laves_C15 + Mg 17Sr2(s)

T(C)

HCP_A3 + Al 4Sr(s)
HCP_A3 + Laves_C15
280

HCP_A3 + Laves_C15 + Al 4Sr(s)

140

MgZn + HCP_A3 + Gamma + Al 4Sr(s) HCP_A3 + Al 4Sr(s) + Laves_C15 + SrZn 5(s)

0
0 0.01 0.02 0.03 0.04 0.05
mass Sr/(Mg0.96897Al0.027277Zn0.0037517+Sr)
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 Phase Diagram
AZ31 – Sr – Ca isothermal section

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 Phase Diagram
Mg0.96897Al0.027277Zn0.0037517 - Sr - Ca
o
300 C
0.03
mass Ca/(Mg 0.96897Al0.027277Zn0.0037517+Sr+Ca)

Laves_C15 + Laves_C14 + HCP_A3

0.024
Laves_C15 + HCP_A3 + Laves_C14 + Mg 17Sr2(s)

0.018
Laves_C15 + HCP_A3 + Mg 17Sr2(s)

Laves_C15 + HCP_A3

0.012

0.006

Laves_C15 + HCP_A3 + D13(ca,sr,ba)

0
0 0.006 0.012 0.018 0.024 0.03
mass Sr/(Mg0.96897Al0.027277Zn0.0037517+Sr+Ca)

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 Phase Diagram
Mg-Al-Zn + 1% Sr triangle /rectangular isothermal section

For the triangle phase diagram of more than 4 component system, special care is
needed to set correct composition.

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 Phase Diagram
Mg - Al - Zn - Sr
o
500 C, mass Sr/(M g+Al+Zn) = 0.010101

Mg

0. 9

0. 1
Liquid + HCP_A3

0. 8

0. 2
0. 7

0. 3
0. 6

0. 4
0. 5 Liquid

0. 5
0. 4

0. 6
Liquid + Al 4Sr(s)
0. 3

0. 7
0. 2

0. 8
Liquid + FCC_A1 + Al 4Sr(s)
0. 1

0. 9
FCC_A1 + Al 4Sr(s)
0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1
Zn Al
mass fractions /(Mg+Al+Zn)

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 Phase Diagram
Mg-Al-Zn + 1% Sr triangle /rectangular isothermal section

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 Phase Diagram
Mg - Al - Zn - Sr
o
500 C, mass Sr/(M g+Al+Zn+Sr) = 0.01
0.05

0.04
mass Zn/(Mg+Al+Zn+Sr)

Liquid + HCP_A3

0.03

Liquid + HCP_A3 + Al 4Sr(s)

0.02

0.01

HCP_A3 + Al 4Sr(s)
HCP_A3 + Mg 17Sr2(s)
0
0 0.02 0.04 0.06 0.08 0.1
mass Al/(Mg+Al+Zn+Sr)
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 Phase Diagram
Projection calculation (Liquidus projection): Mg-Al-Zn

Step: interval of isothermal

temperature liquidus lines

“O” option for the target projection phase

(Liquid in most of cases)

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 Phase Diagram
Al - Mg - Zn
Data from FTlite - FACT light alloy databases

Zn
o o
Four-Phase Intersection Points with Liquid T(min) = 340.89 C, T(max) = 660.31 C
HCP_Zn

0. 9
1: AlMgZn_Tau / FCC_A1#1 / Laves_C14#1

0. 1
2: AlMgZn_Tau / Beta_AlMg / Gamma
3: AlMgZn_Tau / Beta_AlMg / FCC_A1#1
4:
5:
AlMgZn_Tau / Laves_C14#1 / Mg2Zn3
AlMgZn_Tau / Gamma / Phi
9 Mg2Zn11

0. 8

0. 2
6: Gamma / HCP_A3#1 / Phi
7
7: FCC_A1#1 / Laves_C14#1 / Mg2Zn11
8: AlMgZn_Tau / Mg2Zn3 / MgZn
9: FCC_A1#1 / HCP_Zn / Mg2Zn11
Univariant line

0. 7

0. 3
10: HCP_A3#1 / Mg51Zn20_<mg7zn3>_oi1 / MgZn
11: AlMgZn_Tau / HCP_A3#1 / Phi
12: AlMgZn_Tau / HCP_A3#1 / MgZn
(phase boundary)
0. 6

0. 4
A = Zn, B = Mg, C = Al
o
X(A) X(B) X(C) C
1: 0.35365 0.18471 0.46164 467.78
2:
3:
0.04094 0.37786 0.58120 447.57
0.04248 0.36009 0.59743 446.26
Laves_C14
0. 5

0. 5
4: 0.33110 0.60810 0.06080 428.12
5: 0.16296 0.66052 0.17652 385.07
6:
7:
0.16267 0.69979 0.13755 364.35
0.80148 0.07683 0.12168 360.17
Mg2Zn3 Isotherms
0. 4

0. 6
8: 0.25899 0.69007 0.05094 353.59
9:
10:
0.85034 0.05789 0.09177 347.54
0.28328 0.71522 0.00150 345.23
1
(liquidus)
11: 0.23357 0.70211 0.06432 342.67
4
0. 3

0. 7
12: 0.24168 0.70263 0.05570 340.89

10
8
12
MgZn 11
AlMgZn_Tau
0. 2

0. 8
Phi FCC_A1
6 5
0. 1

0. 9
HCP_A3
Gamma 2 3
Beta_AlMg
0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1
Mg Al
mole fraction

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FactSage Advanced in Equilib

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138 2014
 J option (3 possible miscibility gaps): Fe-Nb-Ti-C-N system
FSstel database:
solid and liquid steel phases

“J” option is needed for a phase which has more than 2 possible miscibility gaps.
Most well known example is Fe FCC phase in steel with (Ti,Nb)(C,N) phase formation.
Since Ti(C,N) and Nb(C,N) have FCC cyrstal structure, we describe both FCC metallic
phase and carbonitride phase using the same FCC phase model. Thus, in order to do
proper calculations, J option should be applied to FCC phase in this case.

Montreal
139 2014
Austenite phase

Ti(C,N) ppt.

Nb(C,N) ppt.

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140 2014
 99.875 Fe + 0.018 Ti + 0.068 Nb + 0.039 C +
c:\Workshop\Equi0.res 30Apr10
0.10

0.08
FCC#2 FCC#2 FCC#2

FCC#2

0.06
gram

0.04 99.875 Fe + 0.018 Ti + 0.068 Nb + 0.039 C +

FCC#3 FCC#3
FCC#3 c:\Workshop\Equi0.res 30Apr10
FCC#3
100 BCC#1 FCC#1
BCC#1
0.02
90
BCC#1
80
0
600 650 700 750 800 850 900 950 1000
T(C) 70

60
gram

50

40

30

20
FCC#1
10

FCC#1
0 CEME
FCC#2
FCC#3 FCC#2
FCC#3 FCC#2
FCC#3 FCC#2
FCC#3
600 650 700 750 800 850 900 950 1000
T(C)

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141 2014
 Cooling Calculations

The Equilib module enables you to perform cooling calculations

and display the phase transitions and compositions during

• Equilibrium cooling
• Scheil-Gulliver cooling
• Full annealing of cast alloys

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142 2014
 Al-Mg-Zn : Equilibium cooling – L-Option

FTlite database

Equilibrium Cooling
of Liquid Al-Mg-Zn
• cooling step ‘10’
• T-auto √
• final mass ‘0’

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143 2014
Al-Mg-Zn : Equilibium cooling – Summary of Results

Montreal
144 2014
Al-Mg-Zn : Equilibium cooling – Plot Results

Montreal
145 2014
Al-Mg-Zn : Equilibium cooling – Plot Results

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146 2014
Graphical output of Scheil target calculation

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147 2014
Al-Mg-Zn : Equilibrium cooling XMg=0.8,XAl=0.15,XZn=0.05
Al-Mg-Zn polythermal liquidus projection
calculated by Phase DiagramAl - Mg - Znwith data taken
from FTlite –Data
FACT light
from FTlite alloy
- FACT databases
light alloy databases

Zn
o o
Four-Phase Intersection Points with Liquid T(min) = 340.89 C, T(max) = 660.31 C
HCP_Zn

0. 9
1: AlMgZn_Tau / FCC_A1#1 / Laves_C14#1

0. 1
2: AlMgZn_Tau / Beta_AlMg / Gamma
3: AlMgZn_Tau / Beta_AlMg / FCC_A1#1
4:
5:
AlMgZn_Tau / Laves_C14#1 / Mg2Zn3
AlMgZn_Tau / Gamma / Phi
9 Mg2Zn11

0. 8

0. 2
6: Gamma / HCP_A3#1 / Phi 7
7: FCC_A1#1 / Laves_C14#1 / Mg2Zn11
8: AlMgZn_Tau / Mg2Zn3 / MgZn
9: FCC_A1#1 / HCP_Zn / Mg2Zn11 Crystallization path for

0. 7

0. 3
10: HCP_A3#1 / Mg51Zn20_<mg7zn3>_oi1 / MgZn
11: AlMgZn_Tau / HCP_A3#1 / Phi Equilibrium cooling
12: AlMgZn_Tau / HCP_A3#1 / MgZn

0. 6
A = Zn, B = Mg, C = Al Alloy composition:

0. 4
o
X(A) X(B) X(C) C 80 mol % Mg
1: 0.35365 0.18471 0.46164 467.78
2:
3:
0.04094 0.37786 0.58120 447.57
0.04248 0.36009 0.59743 446.26
Laves_C14 15 mol % Al
5 mol % Zn
0. 5

0. 5
4: 0.33110 0.60810 0.06080 428.12
5: 0.16296 0.66052 0.17652 385.07
6:
7:
0.16267 0.69979 0.13755 364.35
0.80148 0.07683 0.12168 360.17 Mg2Zn3
0. 4

0. 6
8: 0.25899 0.69007 0.05094 353.59
9: 0.85034 0.05789 0.09177 347.54
10: 0.28328 0.71522 0.00150 345.23
11: 0.23357 0.70211 0.06432 342.67 1
4
0. 3

12: 0.24168 0.70263 0.05570 340.89

0. 7
10
8
12
MgZn 11
AlMgZn_Tau
0. 2

0. 8
Phi FCC_A1
6 5
0. 1

0. 9
HCP_A3
Gamma 2 3
Beta_AlMg
0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1
Mg Al
mole fraction

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148 2014
 Scheil target phase

The program performs a Gulliver-Scheil cooling calculation. That is, as phases precipitate
from the Scheil target phase they are dropped from the total mass balance.
A value of T (the initial temperature) must be specified in the Final Conditions frame.
Normally, the Scheil calculation is repeated until the Scheil Target phase disappears. However
it is possible to stop the calculation by either specifying a second temperature in the Final
Conditions frame, or by specifying a target mass.
When a Scheil phase is selected the «Scheil Target frame» in the Menu Window becomes
activated and a cooling step (0.1 to 250) must be specified in this Scheil Target frame.
The Scheil target phase must be the gas phase or a real solution. If it is a liquid phase (such
as FToxid-SlagA and FACT-SALT) then the precipitates are generally solids - it would be
unusual in this case to select and include other liquids or the gas phase in the calculation.
If the Scheil target phase is the gas phase then the precipitates could be any or all of the
other compound and solution phases. To activate a Scheil target gas phase, first select the
gas species in the usual way. Then with the mouse-right-button click on the gas '+' check box
in the compound species frame of the Menu Window - this will open the Species Selection
window. Point to the '+' column of any selected gas species and then click with the mouse-
right-button and then select «Scheil cooling gas phase».

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149 2014
 Scheil target phase

T1
Equilib. T2
Cooling L1 L2
Scheil
Cooling

L1
T1
T3

T2 L2
L3

T3
L3
Te

T<Te

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150 2014
 Al-Mg-Zn : Scheil-Gulliver cooling – L-Option

Scheil Cooling
of Liquid Al-Mg-Zn
• cooling step ‘10’
• check T-auto √
• enter final mass
‘0’
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151 2014
Graphical output of Scheil target calculation

- Calculation ends at temperature of final disappearance of liquid

- Graph shows phase distribution

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152 2014
Al-Mg-Zn : Scheil cooling XMg=0.8,XAl=0.15,XZn=0.05
Al-Mg-Zn polythermal liquidus projection
calculated by Phase DiagramAl - Mg - Znwith data taken
from FTlite –Data
FACT light
from FTlite alloy
- FACT databases
light alloy databases

Zn
o o
Four-Phase Intersection Points with Liquid T(min) = 340.89 C, T(max) = 660.31 C
HCP_Zn

0. 9
1: AlMgZn_Tau / FCC_A1#1 / Laves_C14#1

0. 1
2: AlMgZn_Tau / Beta_AlMg / Gamma
3: AlMgZn_Tau / Beta_AlMg / FCC_A1#1
4:
5:
AlMgZn_Tau / Laves_C14#1 / Mg2Zn3
AlMgZn_Tau / Gamma / Phi
9 Mg2Zn11

0. 8

0. 2
6: Gamma / HCP_A3#1 / Phi 7
7: FCC_A1#1 / Laves_C14#1 / Mg2Zn11
8: AlMgZn_Tau / Mg2Zn3 / MgZn
9: FCC_A1#1 / HCP_Zn / Mg2Zn11 Crystallization path for

0. 7

0. 3
10: HCP_A3#1 / Mg51Zn20_<mg7zn3>_oi1 / MgZn
11: AlMgZn_Tau / HCP_A3#1 / Phi Scheil cooling
12: AlMgZn_Tau / HCP_A3#1 / MgZn

0. 6
A = Zn, B = Mg, C = Al Alloy composition:

0. 4
o
X(A) X(B) X(C) C 80 mol % Mg
1: 0.35365 0.18471 0.46164 467.78
2:
3:
0.04094 0.37786 0.58120 447.57
0.04248 0.36009 0.59743 446.26
Laves_C14 15 mol % Al
5 mol % Zn
0. 5

0. 5
4: 0.33110 0.60810 0.06080 428.12
5: 0.16296 0.66052 0.17652 385.07
6:
7:
0.16267 0.69979 0.13755 364.35
0.80148 0.07683 0.12168 360.17 Mg2Zn3
0. 4

0. 6
8: 0.25899 0.69007 0.05094 353.59
9: 0.85034 0.05789 0.09177 347.54
10: 0.28328 0.71522 0.00150 345.23
11: 0.23357 0.70211 0.06432 342.67 1
4
0. 3

12: 0.24168 0.70263 0.05570 340.89

0. 7
10
8
>

12
MgZn 11
AlMgZn_Tau
0. 2

0. 8
Phi FCC_A1
6 5
0. 1

0. 9
HCP_A3
Gamma 2 3
Beta_AlMg
0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1
Mg Al
mole fraction

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153 2014
Al-Mg-Zn-Mn : Scheil cooling AZ91 + 0.25 wt.% Mn alloy

Scheil Cooling
of Liquid Al-Mg-Zn-Mn
• cooling step ‘10’
• check T-auto √
• enter final mass ‘0’

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154 2014
Al-Mg-Zn-Mn : Scheil cooling – Summary and Transitions
AZ91 + 0.25 wt.% Mn alloy:

89.75Al-9Mg-Zn-0.25Mg
(wt%)
Summary

Transitions

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155 2014
Al-Mg-Zn-Mn : Scheil cooling - Microstructure Constituents
Summary & Transitions
x100
Microstructure
constituents of AZ91 +
0.25 wt.% Mn alloy
after Scheil cooling.

Final disappearance
of liquid at 340.89°C

Montreal
156 2014
 Al-Mg-Zn-Mn : Scheil cooling - Microstructure Constituents
• Solidification software
(extended Scheil cooling)
• Scheil cooling + post equilibration (annealing) of Scheil microstructure
• AZ91 alloy + 0.25 wt.% Mn
CONS. PHASE TOTAL AMT/gram
1 1 ‘Al8Mn5’ 5.2241E-04

2 1 HCP 6.4599E+01
Tracking 2 2 ‘Al8Mn5’ 2.8231E-01
microstructure Amount & Average Composition of the HCP phase
3 1 HCP 1.5644E+01
constituents 3 2 Al11Mn4 1.4638E-01
wt. % Mg Al Zn Mn
4 1 HCP 1.7084E+00 2 64.599 96.19 3.67 0.125 195 ppm
Output : 4 2 ‘Al4Mn’ 1.7892E-02
Solidification 3 15.644 92.25 7.45 0.298 14.7 ppm
5 1 HCP 4.9213E+00
temperature of 5 2 ‘Al12Mg17’ 1.1878E+01 4 1.708 89.22 10.34 0.440 1.2 ppm
340.89°C 5 3 ‘Al4Mn’ 2.6558E-02
5 4.921 88.95 10.03 1.021 0.7 ppm
6 1 HCP 1.9669E-01
6 2 Phi 4.0423E-01
6 0.197 89.77 5.14 5.086 0.1 ppm
6 3 ‘Al4Mn’ 1.7904E-05 7 0.024 90.55 2.93 6.519 0.2 ppm
6 4 Al11Mn4 3.8196E-05
8 0.042 90.57 2.90 6.538 0.2 ppm
7 1 HCP 2.4177E-02
7 2 Tau 3.5706E-02
7 3 Al11Mn4 1.4894E-06

8 1 HCP 4.2084E-02
8 2 MgZn 5.1501E-02
8 3 Tau 2.1364E-02
8 4 Al11Mn4 2.3786E-06

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157 2014
Al-Mg-Zn-Mn : Selecting constituent 2 HCP phase for annealing

1° Point mouse to constituent 2

HCP_A3 and double-click

2° Click OK to recycle HCP_A3

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158 2014
Al-Mg-Zn-Mn : HCP phase imported into Reactant Window

Change mass from 100% => 100 g

List of components in HCP phase

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159 2014
Al-Mg-Zn-Mn : Equilibrium calculation – annealing HCP phase

Anneal at 150 to 500 oC

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160 2014
Al-Mg-Zn-Mn : Plotting annealed HCP phase

Montreal
161 2014
Al-Mg-Zn-Mn : Graph of annealed HCP phase
Equilibrium phase distribution in HCP phase of
constituent 2 after annealing (HCP + precipitates)

Montreal
162 2014
Al-Mg-Zn-Mn : Equilibrium calculation – annealing HCP phase
• Solidification software
(extended Scheil cooling)
• Scheil cooling + post equilibration 2

of Scheil microstructure
HCP

1
Annealing of HCP in ‘2’
• AZ91 alloy + 0.25 wt.% Mn 'Al 12Mg17'
0

log10(wt.%)
Tracking microstructure constituents -1
'Al99Mn23'
Annealing Al4Mn Al11Mn4

Phases vs T for HCP in the different -2 'Al8Mn5'

microstructural constituents -3

Amount & Average Composition of the HCP phase -4

150 200 250 300 350
o
400 450 500

at 340.89oC Temperature ( C)

wt. % Mg Al Zn Mn 1.5 HCP

2 64.599 96.19 3.67 0.125 195 ppm 1

Annealing of HCP in ‘3’
.5

3 15.644 92.25 7.45 0.298 14.7 ppm 0

'Al12Mg17'

log10(wt.%)
-.5
4 1.708 89.22 10.34 0.440 1.2 ppm
-1

5 4.921 88.95 10.03 1.021 0.7 ppm -1.5

-2
6 0.197 89.77 5.14 5.086 0.1 ppm -2.5

Al4Mn
7 0.024 90.55 2.93 6.519 0.2 ppm -3 'Al 99Mn23'
Al11Mn4

-3.5
8 0.042 90.57 2.90 6.538 0.2 ppm -4
150 200 250 300 350 400 450 500
o
Temperature ( C)

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163 2014
 Scheil cooling calculation of AZ31 alloy
Solidification path calculation: AZ31

100

90 Alpha-Mg

80

amount of each phase (wt%)

70

60

Eutectic Mg Dendrite
50

40

30

20

Liquid
10
Mg17Al12
0 PHI
300 350 400 450 500 550 600 650 700
o
Temperature, C
Microstructure of as-cast AZ31
Scheil Cooling calculation

Scheil cooling calculations tell us the solidification path

• Primary phase, precipitation, and eutectic reaction.
• Dendrite boundary (eutectics, segregation)
-> Estimation of as-cast microstructure

Montreal
164 2014
 Scheil cooling calculation of AZ31 alloy

Corning effect of Mg dendrite: AZ31

50

40
(B)
boundary
(A)
weight percent

30
Mg dendrite
Liquid - Al
20
A
Liquid - Zn
B
10
alpha Mg - Al

alpha Mg - Zn
0
300 350 400 450 500 550 600 650 700
o
Temperature, C

change of composition
In dendrite & boundary

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165 2014
Scheil cooling calculation of AZ31 alloy

Montreal
166 2014
Scheil cooling calculation of AZ31 alloy

Montreal
167 2014
Scheil cooling calculation of AZ31 alloy

Montreal
168 2014
Scheil cooling calculation of AZ31 alloy

Montreal
169 2014
 Fixed activity of gas and solid species
Fixed pO2 in Fe-Cr-O2
2

FSStel, FToxid, FactPS database

Specify the activity of the selected

species or set a range of activities
1
(linear or log scale)

Montreal
170 2014
 Fixed partial pressure of a gas : O2

Results at log(pO2) = -20

Small amount of Cr2O3

can form on top of the
Fe-20%Cr alloy

Montreal
171 2014
Fixed partial pressure of a gas : O2
Fixed pO2 in MgO-FetO-SiO2 slag

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172 2014
 Fixed partial pressure of a gas : O2
Results at log(pO2) = -15

Results at log(pO2) = -10

Results at log(pO2) = -2

The amounts of FeO and Fe2O3 change with PO2

Montreal
173 2014
Composition target: target S content in liquid steel
Composition Target: slag / liquid steel equilibrium

“ How to calculate optimum amount of CaSi to reduce S

in liquid steel to a targeted composition”

Montreal
174 2014
Composition target: target S content in liquid steel
Add CaSi (<A>) to reduce [%S] in Fe-LIQUID to 0.002%.

Montreal
175 2014
Composition target: target S content in liquid steel
Amount of CaSi = 0.96 gram to obtain [%S] = 0.002%

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176 2014
‘Table’ menu: Many calculations under the same condition
Before using the table menu, setup calculation condition for one composition.

FToxid database

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177 2014
Check the format of the table

Now we have to create the table with many different

compositions: the content of column should be
prepared as shown in “Reaction Table”

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178 2014
(1) Create Excel file

(2) Save as “text” file

(3) Import in Equilib

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179 2014
(4) After import, ‘Close Table’ again.

(5) In the main menu, click “Table” to

activate the calculation for “table”
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180 2014
 Simple counter-cross inter-diffusion calc.

A materials B materials

concentration

A materials B materials

Any kind of counter-cross inter-diffusion reaction at interface can be simulated with

<A> option in Equilib. This assume the diffusivity of all components in both materials
are the same.

Montreal
181 2014
Joining of <A>Al-Mg // <1-A>AZ31
FTlite database

Montreal
182 2014
 <A> Al0.97Mg0.03 + <1-A> Mg0.965Al0.03Zn0.005
c:\Workshop\Equi0.res 30Apr10

1.00 Gama

0.80

Beta
Gama
Liqu#1
0.60
gram

0.40
HCP#1
Liqu#1
FCC#1

0.20

0
0 000.1 000.2 000.3 000.4 000.5 000.6 000.7 000.8 000.9 001
Alpha

Montreal
183 2014
 Counter-cross reaction: refractory / slag
Refractory Slag
95%Al2O3-5%MgO 60%CaO-40%SiO2

FToxid database

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184 2014
 Counter-cross reaction: refractory / slag

<0.6A> CaO + <0.4A> SiO2 + <0.95-0.95A> Al2O3 + <0.05-0.05A> MgO

c:\Workshop\AlloyDesign\Equi0.res 9M ay10

1.0 SLAGA#1 SLAGA#1

SLAGA#1
0.8

Ca2Mg2Al28O46(s)
0.6
gram

0.4

SLAGA#1

0.2

Ca2Mg2Al28O46(s)
Al2O3(s4) CaMg2Al16O27(s)
0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Alpha

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185 2014
 70

Counter-cross reaction: Refractories in VOD 60

composition of slag, wt%

[Refractory] 50
slag
refractories; 58MgO-6.5Al2O3-21 Cr2O3-13.5FeO

[Refractory]
40 CaO

[Slag]
slag; 50CaO-40SiO2-10Al2O3 (in wt%)
[Slag] 30
SiO2
20
MgO
10
Al2O3
FeO
Cr2O3
0
100
-0.1 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1
(1-x) refractory + x slag (by weight)

composition of periclase, wt%

90
Periclase
80
Spinel MgO
70

[Refractory]
60
periclase
relative amount of each phase, wt%

100

[Slag]
50

90 T=1650oC 40

80 30

20 FeO
70
Slag
[Refractory]

10
60 Cr2O3 Al2O3
1000
[Slag]

-0.1 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1
50
90 (1-x) refractory + x slag (by weight)

composition of spinel, wt%

40 80

30
Periclase
70 spinel

[Refractory]
20
60 Cr2O3

[Slag]
50
10 Spinel 40
0
-0.1 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 30
(1-x) refractory + x slag (by weight) 20
MgO
Al2O3
Jung et al., Taikabutsu, vol. 56, 2004, pp. 382-386. 10

0
FeO
1.0Montreal
186 -0.1 0.0 0.1 0.2 0.3 0.4 0.5 0.6
(1-x) refractory + x slag (by weight)
0.7 0.8 0.9 1.1
2014
 Heat balance: very important for industrial process

AmBn + etc. T2
1) How much heat is required to increase
temperature from T1 to T2 ?
+ or - Heat 2) If we add or remove a certain amount of
H from mixtures of materials, what would
be final temperature ?
A + B T1  Good for
a) Furnace capacity design
Heat of formation + T increase b) Heat balance calculation for alloying or
fluxing of materials to melt bath
c) Calculate exothermic or endothermic
Alloys T1 Flux heat generated during explosion
d) Process simulation for temperature
change

T2 ??

Heat of Dissolution
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187 2014
 Heat balance: Addition of Ferro-Mn into Liquid steel
Use two stream
2.
1.
65%Mn-35%Fe
25°C
Final
Temperature ?
1.
1600 °C, Liquid

Fe-1wt.%Al-0.8wt.%C 2.

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188 2014
Heat balance: Addition of Ferro-Mn into Liquid steel

Adiabatic condition
(dH = 0)

If we know the heat loss of the

ladle we can setup this here for the
final Temperature prediction

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189 2014
Heat balance: Addition of Ferro-Mn into Liquid steel

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190 2014
Heat balance: Cooling of AZ91 from 600 to 300oC

Stream : AZ31 alloy at 600 °C

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191 2014
Heat balance: Cooling of AZ91 from 600 to 300oC

Montreal
192 2014
Thermodynamic properties: Activity, ΔG, ΔH, ΔS etc.

Montreal
193 2014
Thermodynamic properties: Activity, ΔG, ΔH, ΔS etc.

Montreal
194 2014
Thermodynamic properties: Activity, ΔG, ΔH, ΔS etc.

Si(l)
Mg(l)

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195 2014
Thermodynamic properties: Activity, ΔG, ΔH, ΔS etc.

Montreal
196 2014
 Application: Activity calculations
Slag: binary, ternary and multi-component systems
FeLq : oxygen and alloying elements

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197 2014
Activity calculations – Binary system

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198 2014
Activity calculations – Binary system

Activity of solid or liquid standard state) ?

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199 2014
Activity calculations – Ternary system

Calculation of iso-activity line of SiO2

in the CaO-MgO-SiO2 system

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200 2014
Activity calculations – Ternary system

Save results in excel

or spread sheet form

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201 2014
 Activity calculations – Ternary system

Plot the results in triangle diagram

- Prepare the triangle frame
- Plot the A,B,C coordinate numbers in triangle diagram

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202 2014
Activity calculations – Quaternary or higher order system
Impossible to calculate iso-activity line of
A with fixed B composition in quaternary
A-B-C-D system yet.

Composition of Al2O3 is NOT 0.1

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203 2014
Activity calculations – Quaternary or higher order system

A. Draw phase diagram of A-B-C with fixed D, and Check the iso activity point
manually of A in phase diagram mode

B. Calculate activity of A in entire A-B-C with fixed D section and manually connect
iso-activity of A.

In future, iso-activity calculation mode will be added into Phase Diagram module.

Montreal
204 2014
 Activity of oxygen (wt% standard state) in liquid steel

RT ln γ oM  g oM ( Henrian S.S.)  g oM ( Pure Element S.S.)

 aM ( pure Element S .S .)  γ oM aM ( Henrian s.s.)

aO in FeLq

ln γOo  15280 / T  3.5 : value used in FeLq database; slightly different

depending on assessments

Reference pure element standard state of O in FeLq : Gas (0.5 O2)

100Mi
a i ( wt% std. state )  a i (Henrian std. state )
M Fe

Log aO(wt%) = Log(aO in FeLq) - Log((EXP(-15280/T+3.5)*55.847/100/16))

where T in Kelvin

Montreal
205 2014
Activity of oxygen (wt% standard state) in liquid steel

Dissolved Al, O, Al*O, Al2*O

aO in FeLq

Total dissolved Al and O

Montreal
206 2014
Activity of oxygen (wt% standard state) in liquid steel
aO in FeLQ Total dissolved Al and O

Dissolved
unassociated O

 Then, convert aO in FeLq to aO wt% s.s.

Montreal
207 2014
 New component in slag: Henrian activity coefficient

V2O3 containing slag // Liquid Fe-Al steel

 All V go to liquid Fe ??
(because no V oxide in slag yet)

Montreal
208 2014
New component in slag: Henrian activity coefficient

Setting activity coefficient

of V2O3 in slag

Montreal
209 2014
New component in slag: Henrian activity coefficient

Montreal
210 2014
 New component in slag: Henrian activity coefficient

V in FeLq = 0.577 wt%

V2O3 in slag = 0.134 wt%

The distribution of V between slag and metal can

be varied depending on the activity coefficient.
(evaluated from experimental data)

Montreal
211 2014
FactSage Advanced
in Phase Diagram

Montreal
212 2014
 Metastable phase: Fe-C binary system w/wo C (Fe3C)

Although C (carbon) is thermodynamically stable phase than Fe3C, C is not appearing in

most of low carbon steel. Thus, in order to do proper calculations, C should be removed
from above compound list in particular in steel.
In the same way, if a certain phase is not readily formed (sluggish to form), we can
unselect the phase to simulate the system more realistically.
Montreal
213 2014
 Fe - C

1600

Fe-LIQUID
1380
Fe-LIQUID + C(s)

Fe-LIQUID + FCC(c,n)

1160
FCC(c,n)

T(C)
940
Fe - C FCC(c,n) + C(s)

1600

720
Fe-LIQUID

1380
BCC_A2 + C(s)
500
Fe-LIQUID + FCC(c,n) 0 0.02 0.04 0.06 0.08 0.1
Fe-LIQUID + Fe3C(s) mass C/(Fe+C)
1160
FCC(c,n)
Stable phase diagram with C
T(C)

Fe-LIQUID + Fe3C(s)

940
Fe3C(s) + FCC(c,n)

720

BCC_A2 + Fe3C(s)

500
0 0.02 0.04 0.06 0.08 0.1
mass C/(Fe+C)

Metastable phase diagram without C

Montreal
214 2014
Fe oxide containing system: Fe saturation

Intentional addition of Fe to make Fe saturation

Montreal
215 2014
 Fe oxide containing system: Fe saturation

FeO - SiO2 - Fe
Fe/(FeO+SiO2) (g/g) = 0.001

1900

ASlag-liq + ASlag-liq#2 + Fe(liq)

1700 ASlag-liq + Fe(liq)

ASlag-liq + Fe(liq) + SiO2(s6)

1500 ASlag-liq + Fe(s) ASlag-liq + Fe(s) + SiO2(s6)
ASlag-liq + Fe(s) + SiO2(s4)
Intentional addition of Fe ASlag-liq + Fe(s2)
1300
to make Fe saturation
T(C)

ASlag-liq + Fe(s2) + SiO2(s4)

ASlag-liq + AMonoxide + Fe(s2)

1100 Fe(s2) + SiO2(s4) + Fe2SiO4(s)

AMonoxide + Fe(s2) + Fe 2SiO4(s)

900 Fe(s) + SiO2(s4) + Fe2SiO4(s)

Monoxide = FeO. But due to slightly AMonoxide + Fe(s) + Fe 2SiO4(s)

different Gibbs energies of FeO stored in 700

Fe(s) + SiO2(s2) + Fe2SiO4(s)
two databases, FeO from FACT53 Fe(s) + FeO(s) + Fe 2SiO4(s)
appears in the calculation.  for better 500
ASpinel + Fe(s) + Fe2SiO4(s) Fe(s) + SiO2(s) + Fe2SiO4(s)
calcs, remove FeO(s) from database 0 0.2 0.4 0.6 0.8 1
selection SiO2/(FeO+SiO2) (g/g)

Montreal
216 2014
Fe oxide containing system: fixed PO2

Fixing PO2 to control the

oxidation state of Fe

Montreal
217 2014
 Fe oxide containing system: fixed PO2

When PO2 is fixed with selection of Fe, slag and

Fe oxides can be reduced by Oxygen to Fe at FeO - SiO2 - O2
certain temperature and composition p(O2) = 10
-10
atm

1900

ASlag-liq + Fe(liq)
1700

Fe(liq) + SiO2(s6)

1500

ASlag-liq
1300
T(C)

ASlag-liq + AMonoxide ASlag-liq + SiO2(s4)

1100 Fe2SiO4(s) + SiO2(s4)

ASpinel + SiO2(s4)
900

ASpinel + SiO2(s2)

700
Fe2O3(s) + SiO2(s2)

500
0 0.2 0.4 0.6 0.8 1

SiO2/(FeO+SiO2) (g/g)

Montreal
218 2014
 Fe oxide containing system: fixed CO/CO2 gas

Fixing PO2 by CO/CO2 gas mixture

Select only CO, CO2 and O2 gas to simulate real experiment of oxide/gas equilibration.
 If we select all gases, some amount of oxides can be evaporated depending on the relative amount
of gas and oxide in the calculations

Montreal
219 2014
Fe oxide containing system: fixed CO/CO2 gas

FeO - SiO2 - CO - CO2

CO/(FeO+SiO2) (mol/mol) = 0.9,
CO2/(FeO+SiO2) (mol/mol) = 0.1

1900

gas_ideal + ASlag-liq + ASlag-liq#2

1700 gas_ideal + ASlag-liq + Fe(liq) gas_ideal + ASlag-liq

gas_ideal + ASlag-liq + SiO2(s6)

1500
gas_ideal + ASlag-liq + Fe(s)

gas_ideal + ASlag-liq + SiO 2(s4)

Fixing CO/CO2 ratio 1300 gas_ideal + ASlag-liq + Fe(s2)

T(C)

gas_ideal + ASlag-liq + AMonoxide + Fe(s2)

gas_ideal + ASlag-liq + Fe(s2) + SiO 2(s4)

1100

gas_ideal + AMonoxide + Fe(s2) + Fe 2SiO4(s) gas_ideal + Fe(s2) + SiO2(s4) + Fe2SiO4(s)

900

gas_ideal + AMonoxide + Fe(s) + Fe 2SiO4(s)

gas_ideal + Fe(s) + SiO2(s2)

700
gas_ideal + Fe(s) + Fe 2SiO4(s) gas_ideal + Fe(s) + SiO2(s2) + Fe2SiO4(s)

500
0 0.2 0.4 0.6 0.8 1

SiO2/(FeO+SiO2) (mol/mol)

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220 2014
Fe oxide containing system: fixed CO/CO2 gas

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221 2014
 Fe oxide containing system: fixed CO/CO2 gas
Fe2O3 - CO - CO2
Fe2O3/(CO+CO2) (mol/mol) = 1
2000

10mole
1800 <Closed system>
gas_ideal + ASlag-liq
CO-CO2 gas
1600
gas_ideal + ASlag-liq + ASpinel 1mole
1400
Fe2O3
gas_ideal + AMonoxide
1200

gas_ideal + ASpinel + AMonoxide

T(C)

1000
10mole CO-CO2 gas
800 gas_ideal + ASpinel + Fe 2O3(s)
gas_ideal + ASpinel
1mole <Open system>
600

gas_ideal + ASpinel + C(s) Fe2O3

400 C:\Workshop\Fe2O3-CO-CO2-large-Gas.wmf
5/3/2011

Fe2O3 - CO - CO2
200 Fe2O3/(CO+CO2) (mol/mol) = 0.1
ASpinel + FeCO3(s) + C(s) 2000
0
gas_ideal + FeCO3(s) + Fe2O3(s)
0 0.2 0.4 0.6 0.8 1
1800
CO/(CO+CO2) (mol/mol)

gas_ideal + LIQUID + ASlag-liq

1600 gas_ideal + ASlag-liq

gas_ideal + BCC_A2 + ASlag-liq

1400

1200
gas_ideal + AMonoxide
gas_ideal + ASpinel + AMonoxide gas_ideal + FCC_A1 + AMonoxide
T(C)

1mole 1000

CO-CO2 gas 800

gas_ideal + ASpinel gas_ideal + BCC_A2 + AMonoxide
gas_ideal + ASpinel + Fe 2O3(s)

1mole 600

Fe2O3 400 gas_ideal + ASpinel + C(s)

200

<Closed system> gas_ideal + FeCO3(s) + Fe2O3(s) gas_ideal + FeCO3(s) + C(s)

0
0 0.2 0.4 0.6 0.8 1

CO/(CO+CO2) (mol/mol)

Montreal
222 2014
CaO-FetO-SiO2 system with Fe saturation

Montreal
223 2014
CaO-FetO-SiO2 system with Fe saturation

CaO - FeO - SiO2 - Fe

o
1650 C, Fe/(CaO+FeO+SiO2) (g/g) = 0.001

SiO2

0. 9

0. 1
0. 8

0. 2
0. 7

0. 3
ASlag-liq + Fe(liq) + SiO2(s6)

0. 6

0. 4
0. 5

0. 5
0. 4

0. 6
0. 3

0. 7
ASlag-liq + Fe(liq)
ASlag-liq + a-Ca2SiO4 + Fe(liq)
0. 2

0. 8
ASlag-liq + AMonoxide + a-Ca2SiO4 + Fe(liq)
0. 1

0. 9
ASlag-liq + AMonoxide + Fe(liq)

0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1

CaO FeO
mass fractions /(CaO+FeO+SiO 2)

Montreal
224 2014
 CaO-FetO-SiO2-5wt%MgO system with Fe saturation

In FactSage phase diagram module, special

attention is required for the axis setting of
quaternary or higher order system.

The first three components are Always used as

A,B,C axis with 100% (1mole) base.
Therefore, for 5% MgO section, we have to set the MgO content as 0.05263 instead of 0.05

For x MgO section: y/(1+y) = x  ‘y’ = x(1-x) : ‘y’ is the value for FactSage

Montreal
225 2014
Oxidation diagram: Fe-Cr-O2
Combination of many databases:
FactPS: gases (if necessary)
FToxid: oxide phases
FSStel: fcc, bcc and other metallic phases

Right click

Montreal
226 2014
 Oxidation diagram: Fe-Cr-O2

Fe - Cr - O2
o
1600 C
-5

M2O3(corundum) + ASpinel
ASlag-liq + ASpinel ASpinel

-8

Fe-LIQUID + ASpinel

Fe-LIQUID + M2O3(corundum)
log10(p(O2)) (atm)

-11

Log pO2 for y-axis variable

-14

Fe-LIQUID
BCC_A2
-17

-20
0 0.2 0.4 0.6 0.8 1

mole Cr/(Fe+Cr)

Montreal
227 2014
 Predominance diagram: Fe-Mn-O2-S2

Combination of many databases:

FactPS: gases (if necessary)
FToxid: oxide phases
FSStel: fcc, bcc and other metallic phases

Remove duplicate compounds

Give a priority in database
Typically “FToxid > any metallic database > FactPS”

Montreal
228 2014
 Predominance diagram: Fe-Mn-O2-S2

O2 - S2 - Fe - Mn
o
1300 C, mass M n/(Fe+M n) = 0.3
0
MnSO4(s) + FeSO4(s)
BSpinel + MnSO4(s)

-4 BSpinel

BMonoxide + BSpinel
log10(p(O2)) (atm)

-8
BMonoxide

-12
ASlag-liq + FCC(c,n)
BMonoxide + FCC(c,n)
ASlag-liq

-16
FCC(c,n) + MnS(s)
FCC(c,n)
ASlag-liq + Fe-LIQUID
-20
-20 -16 -12 -8 -4 0
log10(p(S2)) (atm)

Montreal
229 2014
Enthalpy diagram: phase change with H

Montreal
230 2014
 Enthalpy diagram: phase change with H

Enthalpy diagram option

Tinitial
Iso-Temperature

30%SiO2

• Only X-Y type diagram allowed.

• Y axis should be Enthalpy (H-HTmin).
• Hinitial (HTmin) is the enthalpy of products stable at Tmin. For example, Fe2SiO4
(fayalite_olivine) and SiO2 are stable at 0% MgO and 30% SiO2 instead of FeO and
SiO2.
Montreal
231 2014
 Enthalpy diagram: phase change with H
MgO - FeO - SiO2
SiO2/(M gO+FeO+SiO2) (g/g) = 0.3, 1 atm

If we heat the mixture of (Monoxide + olivine) at 30 wt %

3000 o o o o o
2425 C 2325 C 2225 C 2125 C 2025 C

MgO and 30 wt % SiO2 from 25 oC by 1500 J/g, the

mixture becomes mixture of (liquid slag + olivine) at
ASlag-liq + AMonoxide

2500
ASlag-liq

o
1825 C
o
ASlag-liq + AMonoxide + AOlivine 1725 C
o
2000 1625 C
o
1525 C
o
1425 C
H - H25 C (J/g)

ASlag-liq + AOlivine
o
1325 C
1500 o
1225 C
o
1125 C
o
1025 C
o
925 C
1000 o
825 C
AOlivine + SiO2(s4)

about 1425 oC.

o
725 C
AMonoxide + AOlivine o
625 C
AOlivine + SiO2(s2) o
525 C
500 o
425 C
o
AOlivine + SiO2(s) 325 C
o
225 C
o
125 C

0 AMonoxide + AMonoxide#2 + AOlivine

0 0.1 0.2 0.3 0.4 0.5 0.6

MgO/(MgO+FeO+SiO2) (g/g)

If we increase the temperature of the mixture of (Monoxide + olivine) at 20 wt % MgO and 30 wt % SiO2
from 25 oC to 1625 oC, liquid slag is forming and the amount of heat required for this is about 2250 J/g.
Montreal
232 2014
 Enthalpy diagram: phase change with H
MgO - FeO - SiO2
SiO2/(M gO+FeO+SiO2) (g/g) = 0.4, 1 atm
3000 o o o o o
2325 C 2225 C 2125 C 2025 C 1925 C

ASlag-liq
2500

ASlag-liq + AMonoxide + AOlivine

o
1825 C
o
1725 C
o
2000 ASlag-liq + AOlivine
1625 C
o
1525 C
o
1425 C
H - H25 C (J/g)

o
1325 C
ASlag-liq + AClinopyroxene + AOlivine
1500 o
1225 C
ASlag-liq + AOlivine + SiO2(s4)
o
1125 C
o
1025 C
o
925 C
1000 AOlivine + SiO2(s4) o
AMonoxide + AOlivine 825 C
o
725 C
o
625 C
Orthopyroxene + AOlivine o
525 C
500 o
425 C
o
325 C
o
225 C
o
125 C

0
0 0.1 0.2 0.3 0.4 0.5

MgO/(MgO+FeO+SiO2) (g/g)

Montreal
233 2014
Solidus Projection (Formation target in ternary system)

Calculating a polythermal projection – the first melting surface

Montreal
234 2014
Solidus Projection (Formation target in ternary system)

Formation Projection

Liqiud Projection

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235 2014
 Paraequilibrium
Paraequilibrium (Partial equilibrium) vs Orthoequilibrium (Fully equilibrium)

Diffusion of C is much faster than Mn or Si

fcc bcc

Fe Fe
C
Mn Si

Fe Fe
Paraequilibrium
Time

C C
(partial equilibrium only for C)
Mn Si

Fe Fe
C C (Ortho)Equilibrium
Mn Mn
Si Si
Montreal
236 2014
Paraequilibrium: Steel A3 temperature

Montreal
237 2014
 Paraequilibrium: Steel A3 temperature
Fe - C - Mn
Mn/(Fe+C+Mn) (g/g) = 0.02, 1 atm
1000

FCC_A1
Full equilibrium
900

800
CEMENTITE + FCC_A1
T(C)

FCC_A1 + BCC_A2

700
Fe - C - Mn - paraequilibrium diffusing elements: C
Mn/(Fe+C+Mn) (g/g) = 0.02, 1 atm
1000
600
CEMENTITE + BCC_A2
Paraequilibrium
500
0.000 0.005 0.010 0.015 0.020
C/(Fe+C+Mn) (g/g) 900

FCC_A1

800
CEMENTITE + FCC_A1
T(C)

FCC_A1 + BCC_A2
700

600
CEMENTITE + BCC_A2

500
0.000 0.005 0.010 0.015 0.020
C/(Fe+C+Mn) (g/g)
Montreal
238 2014
 Paraequilibrium: Rapid solidification for amorphous metal

Blank  no diffusion of any element: this is what happens during rapid solidification
Montreal
239 2014
 Paraequilibrium: Rapid solidification for amorphous metal
Cu - Zr
1 atm

1400

Liquid Full equilibrium

1200

Liquid + BCC_A2

1000
T(C)

800
Cu5Zr(s) + Cu 51Zr14(s)
FCC_A1 + Cu5Zr(s)

Cu8Zr3(s) + Cu 51Zr14(s)

Cu8Zr3(s) + Cu 10Zr7(s)

600 CuZr 2(s) + Cu 10Zr7(s)

HCP_A3 + CuZr2(s)
Cu - Zr - phase with minimum G
400 1 atm
2000
200

1800
Paraequilibrium:
0
0.0 0.2 0.4 0.6 0.8 1.0
Rapid solidification
Zr/(Cu+Zr) (mol/mol) 1600

1400

1200
T(C)

1000 Liquid

800
BCC_A2

600

400
Possible range for
FCC_A1 HCP_A3
200
Amorphous formation
0
0.0 0.2 0.4 0.6 0.8 1.0
Zr/(Cu+Zr) (mol/mol)

Montreal
240 2014
Paraequilibrium: Rapid solidification for amorphous metal

Cu - Zr - Mg - phase with minimum G

o
300 C, 1 atm

Mg

HCP_A3

0. 9

0. 1
FCC_A1

0. 8

0. 2
BCC_A2

0. 7

0. 3
0. 6

0. 4
0. 5

0. 5
0. 4

0. 6
Laves_C36
0. 3

0. 7
0. 2

0. 8
Liquid
0. 1

0. 9
FCC_A1 BCC_A2
HCP_A3
0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1
Cu Zr
mole fraction

Montreal
241 2014
Viscosity

Montreal
242 2014
 Viscosity Calculation: S+L mixtures (Einstein-Roscoe Eq.)
Viscosity of liquid slag can be
calculated from “Viscosity”
module from slag composition
calculated from “Equilib” (Step-2)

Einstein-Roscoe Equation (one of the most well-accepted

equation of viscosity for solid+liquid mixture)

Viscosity (solid+liquid mixture)  Viscosity(liquid)  (1  solid fraction)-2.5

Original Einstein-Roscoe equation use ‘volume fraction of solid’

instead of ‘solid fraction’ and correction term for morphology,
but all these values are not very well-known for general solids,
we can simply use the solid fraction (wt fraction) for this
equation as approximation.
This value can be calculated using “Equilib” module at
given system composition and temperature (Step-1).
Montreal
243 2014
Viscosity Calculations “Step-1”: Composition of liquid slag

Montreal
244 2014
Viscosity Calculations “Step-2”: Viscosity of liquid slag
“Melts” database is for liquid slag

Take these results

Composition of liquid for next step
slag from Equilib

Montreal
245 2014
Viscosity Calculations “Step-3”: Liquid + Solid mixture

Einstein-Roscoe
Eq.
Amount
of slag Step-2

Amount of solids
(100-amount of liquid)

Montreal
246 2014
Case Study (Example)

Montreal
247 2014
Carburization and Decarburization of Steel

CO / CO2 is variable

Montreal
248 2014
Carburization and Decarburization of Steel

Montreal
249 2014
 Carburization and Decarburization of Steel

An amount of carbon in FCC phase (Fe)

weight %

<Alpha>

Montreal
250 2014
Carburization and Decarburization: Composition target

Composition Target:
“ How to calculate optimum amount of
CO2 to reduce C in steel to a targeted
composition”

Montreal
251 2014
 Carburization and Decarburization: Composition target

weight %

<Alpha>

Montreal
252 2014
P reduction in high purity Si using vacuum

FactSage ultrapure silicon database

This is special database for high purity Si
production

Montreal
253 2014
 P reduction in high purity Si using vacuum

Vacuum level

Montreal
254 2014
P reduction in high purity Si using vacuum

P content in liquid Si

weight %

Montreal
255 2014
B reduction in high purity Si using H2-H2O mixture

JOM, JOURNAL OF THE MINERALS, METALS AND

MATERIALS SOCIETY
Volume 64, Number 8 (2012), 952-956

Montreal
256 2014
 B reduction in high purity Si using H2-H2O mixture

Open calculations:
Simple reactor module
with off-gas removal

“Open” menu
Addition of <A> amount of gas and make chemical reaction
 Remove the gas as off gas
 Add another <A> gas for chemical reaction
 Remove the gas as off gas
 Do this iteration until reaching “10” step

Montreal
257 2014
B reduction in high purity Si using H2-H2O mixture

B product in gas phase

B reduction in liquid Si

Montreal
258 2014
 B reduction in high purity Si using H2-H2O mixture

B content in liquid Si
weight %

weight %

B content can be reduced with decreasing T

“page” in x-axis is amount of gas injected
(or considered as the degassing time)

Montreal
259 2014
Non-metallic Inclusion formation during metal solidification

T=1527°C

AWS 80th Annual Meeting, April 12–15, 1999, St. Louis,

Mo. Page 98-s to 105-s

Montreal
260 2014
Non-metallic Inclusion formation during metal solidification

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261 2014
Non-metallic Inclusion formation during metal solidification

To zoom-up the small part of the calculated

results, the axis of the figure should be changed

Zoom-up

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262 2014
 Non-metallic Inclusion formation during metal solidification
C Si Mn Al Ni S Ti O N
0.06 0.20 1.31 0.006 1.82 0.006 0.023 351ppm 115ppm

Montreal
263 2014
Non-metallic Inclusion formation during metal solidification

Zoom-up

Montreal
264 2014
 Carbide and Nitride precipitation in microalloyed steels

Microalloyed steels are used for special high-strength applications such as

pipelines. In order for the steel to acquire good mechanical properties, it needs to
be thermo-mechanically treated. FactSage can help in finding the correct
temperatures for treating these steels.
The steel is annealed in the
austenite region an then
cooled through the
temperatures Ar3 and Ar1
temperatures (continuous
cooling austenite to ferrite
transformation start and
finish.
Ar3
The goal of this study is to
find the ideal annealing
temperatures to avoid
precipitation of Nb
carbonitrides and promote
precipitation of NbC
Ar1

Montreal
265 2014
 Carbide and Nitride precipitation in microalloyed steels
1. A typical microalloyed steel composition is entered (For more information, refer to
J. Calvo et al. / Materials Science and Engineering A 520 (2009) 90–96)

2. Select only the FSstel database.

Montreal
266 2014
 Carbide and Nitride precipitation in microalloyed steels
1. We are interested in carbide, nitride and carbonitride
precipitation, so we will select all the solids…

2. … all the carbide

phases (select I-
3. … and select J-option option, possible two-
(possible 3-phase immiscibility) phase immiscibility)
for the FCC, BCC and HCP
phases. This is because
carbonitrides have similar
structure to austenite.

4. We will select a range of temperature encompassing the whole austenite phase.

Montreal
267 2014
 Carbide and Nitride precipitation in microalloyed steels
1. Plot g vs T(C) for all solids and solutions having a
maximum weight greater than 0

Montreal
268 2014
 Carbide and Nitride precipitation in microalloyed steels
1. From the graph,
we can deduce
equilibrium
transformation
temperatures from
austenite to ferrite.

2. We should also
look at the very low
compositions, since
all the microalloyed
elements will be
present in very small
quantities. Ae3

Ae1

Montreal
269 2014
 Carbide and Nitride precipitation in microalloyed steels
1. Using a log scale
is very convenient
for looking at the
microalloyed
Ae1
elements. Ae3

2. It is clearly seen
that the FCC#1, #2
and #3 phases are
forming. In this case,
they are probably
carbides and
nitrides.
We can chack this
by plotting their
composition with
temperature

Montreal
270 2014
 Carbide and Nitride precipitation in microalloyed steels
1. We will first select
all the species in
FCC#1 and se how
they are distributed.

Montreal
271 2014
 Carbide and Nitride precipitation in microalloyed steels
1. In the austenite
region, the FCC#1
phase is composed
mostly of iron (FeVa)

2. But below Ae3,

the dominant
species are MoC,
VC and NbC

Montreal
272 2014
 Carbide and Nitride precipitation in microalloyed steels
1. The FCC#2 phase
is composed mainly
of TiN and NbN at
austenite
temperatures…

2. … and of NbC
below Ae3

Montreal
273 2014
 Carbide and Nitride precipitation in microalloyed steels
1. Finally, the FCC#3
phase is composed
of Nb(C,N) at the
austenite
temperatures and of
TiN below Ae3

Montreal
274 2014
 Carbide and Nitride precipitation in microalloyed steels
1. We also note that
there is an HCP#1
phase present,
which appears only
below Ae3 and is
composed primarily
of Mo2C and Mn2C

Montreal
275 2014
 Carbide and Nitride precipitation in microalloyed steels
1. Now that we know temperature This
temperature temperature
what each phase is region for NbC
region is most region for NbN
composed of, it precipitation
favorable for precipitation
would be convenient
to plot the species Nb(C,N)
that interest us the precipitation
most, namely
(Nb,Ti,V)(C,N)

2. Copying the
amounts of NbC,
TiC, … species
contained in FCC#1,
FCC#2 and FCC#3
as well as the
carbide and
cementite phases to
Excel, the following
graph is obtained.
3. In summary, we can now figure out what the equilibrium precipitates will be at
each temperature for designing the thermal treatment needed.
Montreal
276 2014
Fact Optimal

Montreal
277 2014
 Improve the mechanical properties of AZ91 by addition of Ca and RE (FactOptimal)

We consider an AZ91 base alloy (Mg-Al-Zn). We want to improve the mechanical

properties by addition of Rare Earth elements (Ce,La) and calcium by simultaneously:

•maximizing the amount of C15-Al2Ca+aAl11Re3

– Al2Ca can improve the tensile and elongation properties of AZ91 due to grain
refinement. The formation of thermally stable Al11RE3 fine needle-shaped particles
along the grain boundaries significantly improves the creep properties

and

•maximizing the amount of Al12Mg17 in order to conserve AZ91 microstructure

properties

Other constraints employed in this example:

•Wt. %(Ce)+Wt. % (La) < 1 (to keep the price reasonable)

•density > 1.75 g/cm3
•Wt. %(HCP phase)>90
•the HCP phase must be a single phase (i.e. no miscibility gap)
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 Improve the mechanical properties of AZ91 by addition of Ca and RE (FactOptimal)

System: AZ91+RE+Ca

Step 1: Using Equilib we define the system and select the appropriate database: FTlite and
perform a single Equilb calculation.

Select only FTlite database

The temperature will be chosen

as a variable, therefore it is Include molar
irrelevant in the first Equilib volumes in order to
calculation. calculate the density

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 Improve the mechanical properties of AZ91 by addition of Ca and RE (FactOptimal)

Step 2: after a single Equilibrium calculation, open

FactOptimal and set up the objectives.

The two objectives are the maximum of the mass of two

different phases

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 Improve the mechanical properties of AZ91 by addition of Ca and RE (FactOptimal)

Step 2: after a single Equilibrium calculation, open

FactOptimal and set up the objectives.

The second objective is a sum of the mass of two precipitates

Note: this is a
selected species
within a solution

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 Improve the mechanical properties of AZ91 by addition of Ca and RE (FactOptimal)

Step 3: Set up the range of compositions and temperature.

In the variables section,

define range of compositions
and temperature.

The range of composition

corresponds to approximately the
composition of AZ91 alloys.

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 Improve the mechanical properties of AZ91 by addition of Ca and RE (FactOptimal)

Step 4: Set up the composition constraints.

In the constraints section we

click on Composition
constraints and select a sum
of 100 for all composition
variables, and we specify
that wt.% La + wt.% Ce ≤1

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 Improve the mechanical properties of AZ91 by addition of Ca and RE (FactOptimal)

Step 5: Set up the properties constraints.

We select only HCP A3#1 so that

HCP is a single phase (no miscibility
gap possible)

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 Improve the mechanical properties of AZ91 by addition of Ca and RE (FactOptimal)

Step 6: Set up the parameters and calculate.

The region between the two dashed line, is the region

with an acceptable amount of Al12Mg17 to conserve
the typical microstructure of AZ91. Beyond this range
the microstructure can be very different. The user has
to choose a compositions within this range.

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 Improve the mechanical properties of AZ91 by addition of Ca and RE (FactOptimal)

Step 7: Open a chosen point in Equilib and get the detailed results.

Summary of the Equilib file of the selected point

on the Optimal Pareto
6.628 Al + 2.058 Zn + 0.22 Ce + 0.343 La + 1.691 Ca + 89.06 Mg =

90.608 gram HCP_A3#1

(90.608 gram, 3.6754 mol, 5.1554E-02 litre, 1.7575 gram/cm3)

+ 4.3164 gram Gamma_Al12Mg17

(4.3164 gram, 2.7838E-03 mol, 2.0370E-03 litre, 2.1190 gram/cm3)

+ 4.0502 gram Laves_C15#1

(4.0502 gram, 4.3327E-02 mol, 1.9712E-03 litre, 2.0547 gram/cm3)

+ 0.95463 gram alpha-Al11RE3

(0.95463 gram, 1.3353E-03 mol, 2.3446E-04 litre, 4.0715 gram/cm3)+

+ 7.0761E-02 gram Phi

(7.0761E-02 gram, 1.9126E-04 mol, 2.5986E-05 litre, 2.7231 gram/cm3)

*****************************************************************
H G V S Cp
(J) (J) (litre) (J/K) (J/K)
*****************************************************************
1.36182E+04 -7.25584E+04 5.58228E-02 1.82134E+02 1.21185E+02

Total mass/gram = 100.00

System density/gram/cm3 = 1.7913

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Macro Process Simulation

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 Slag/Steel/Inclusion Reactions

• In FactSage, if we put slag, steel and non-metallic inclusion

Slag together and do calculations, it is impossible to distinguish
the slag and non-metallic inclusion phase.
Steel • Theoretically, the slag and inclusion composition should be
identical if the entire system is in equilibrium. However, the
inclusion typically formed by the deoxidation of molten steel
Inclusion take a time to be completely in equilibration with molten
slag.
• The only option to see the interaction between slag and
inclusion is to do two separate calculations, ‘Slag/Steel’ and
‘Steel/Inclusion’, and Steel can be shared between the
calculations. Therefore, the influence of Slag to Inclusion
chemistry can be calculated indirectly through the change of
Steel chemistry.
• In this calculations, the molten steel after the reaction with
molten slag should be stored as a mixture (stream) for the
input for next calculations with inclusion.
• Or, the calculations can be performed using the FactSage
macro processing simulation.

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 Modification of inclusion in LF by interaction with top slag

SiO2( + 15%Al2O3)
Top-Slag Composition Al6Si4O13
1531
80
1573
o

55CaO-15Al2O3–30SiO2 (wt%) 10
1550 C

16
[C] = 0.7wt%

00
70
SiO2
1291
14 ([Mn]+[Si])
20 = 1wt%
00
60
CaAl2Si2O8 Mn/Si = 2.0
Slag 1290
30

00
Ca3Si2O7 50

12
1151
Wollastonite 40

50
11
Ca2Al2SiO71274 Mn3Al2Si3O12
Steel 40

1464 Liquid
11
Slag 50 50
30
Ca2SiO4 s.s. 60
Inclusion 1667
20
1150
1200
1400
70
Monoxide 1600
10 180
200 0
220 0
0 80
230
0
80 70 60 50 40 30 20 10
CaO( + 15%Al2O3) Weight percent MnO( + 15%Al2O3)

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Slag/Steel/Inclusion Reaction: Macro processing Input Excel file

T = 1600C
System temperature
10 times iterations for (1) and (2) rxns.
Slag
(2)
Steel
(1)
Relative amount is important for the change of
inclusion chemistry
Inclusion

Macro process files will

be provided separately

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Slag/Steel/Inclusion Reaction: Macro processing Input Excel file

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