Recent Developments of FactSage Software and Databases

Prof. Patrice Chartrand

Prof. In-Ho Jung

Montreal, Canada

CALPHAD XLIII – Changsha, 2014

Colleagues and collaborators

• Prof. Christopher W. Bale • Prof. Arthur D. Pelton • Prof. Patrice Chartrand • Dr. Sergei Decterov • Dr. Jacques Melançon • Dr. Christian Robelin • Dr. Aïmen Gheribi

2 CALPHAD XLIII - Changsha, 2014

• Dr. Gunnar Eriksson • Prof. Klaus Hack • Dr. Stefan Petersen • Dr. Juergen Korb

• Prof. In-Ho Jung • Dr. Marie-Aline Van Ende • Dr. Pierre Hudon • Dr. Manas Paliwal • Dr. Minkyu Paik • Dr. Sazol Kumar Das • Ms. Elmira Moosavi-Khoonsari

• Ms. Ève Bélisle • Mr. Philippe Ouzilleau • Dr. Lilin Jin • Dr. Jian Wang • Dr. James Sangster • Ms. Evgenia Sokolenko • Mr. Zhizun Zhu

• Dr. Philip Spencer

• Mr. Junghwan Kim • Mr. Dong-Geun Kim • Mr. Bikram Konar • Mr. Eric Thibodeau • Mr. Saikat Chatterjee • Mr. Sourav Panda • Mr. Senlin Cui • Mr. Sunyong Kwon

Colleagues and collaborators

• Prof. Christopher W. Bale • Prof. Arthur D. Pelton • Prof. Patrice Chartrand • Dr. Sergei Decterov • Dr. Jacques Melançon • Dr. Christian Robelin • Dr. Aïmen Gheribi

• Dr. Gunnar Eriksson • Prof. Klaus Hack • Dr. Stefan Petersen • Dr. Juergen Korb

• Prof. In-Ho Jung • Dr. Marie-Aline Van Ende • Dr. Pierre Hudon • Dr. Manas Paliwal • Dr. Minkyu Paik • Dr. Sazol Kumar Das • Ms. Elmira Moosavi-Khoonsari

• Ms. Ève Bélisle • Mr. Philippe Ouzilleau • Dr. Lilin Jin • Dr. Jian Wang • Dr. James Sangster • Ms. Evgenia Sokolenko • Mr. Zhizun Zhu

• Dr. Philip Spencer

• Mr. Junghwan Kim • Mr. Dong-Geun Kim • Mr. Bikram Konar • Mr. Eric Thibodeau • Mr. Saikat Chatterjee • Mr. Sourav Panda • Mr. Senlin Cui • Mr. Sunyong Kwon

COLLABORATORS • Prof. Youn-Bae Kang (Postech) • Prof. Eugene Jak (U. Queensland) • Dr. Dennis Shishin (U. Queensland) • Dr. Viktoria Prostakova (U. Queensland) • Dr. Jean-Philippe Harvey (CalTech) • Dr. Guillaume Lambotte (MIT) • Dr. Wan-Yi Kim (POSCO) • Dr. Adarsh Shukla (GE, India) • Dr. Peter Waldner (U. Leoben) • Prof. Zhanmin Cao (USTB) • Dr. Daniel K. Lindberg (Abo Akademi)

Outline

• A brief history of FactSage

• Current version: FactSage 6.4

• Upcoming version: FactSage 7.0

A brief history…

• The F*A*C*T / FactWin Era (EPM, 1976-2001)

• F*A*C*T on the MUSIC operating system with international connectivity (1976+);

• F*A*C*T on DOS (1994-1999) and FactWin on Windows (1999-2001);

• Modules (EQUILIB, REACTION, PREDOM, EpH, COMPOUND) coded in Fortran;

• Gibbs energy minimisation based on the SOLGASMIX algorithm of Dr. Gunnar Eriksson (U. Umea, Ecole Polytechnique de Montreal, RWTH, GTT-Technologies).

• A single integrated database.

Prof. Arthur D. Pelton and Prof. Christopher W. Bale (May, 1974)

A brief history…

• The ChemSage Era (RWTH / GTT, 1982-2001)

• ChemSage on DOS (1982-2001+) coded in Fortran;

• Gibbs energy minimisation based on the SOLGASMIX algorithm of Dr. Gunnar Eriksson (U. Umea, Ecole Polytechnique de Montreal, RWTH, GTT-Technologies).

• Application oriented mini-databases;

• ChemApp, a dynamically-linked library for user programs.

Dr. Gunnar Eriksson (May, 2011)

A brief history…

• The FactSage Era (2001-…)

6.4 version

• Released in May 2013

6.4 version

• FT, FS, SG, TD Databases

FT Databases • Databases that are developed exclusively in Montreal,

Canada, at the CRCT, Ecole Polytechnique (Profs Pelton and Chartrand) and by McGill University (Prof. Jung);

FS Databases • Databases that are developed exclusively in Montreal,

Canada, at the CRCT Ecole Polytechnique, by McGill University, by GTT-Technologies (Dr. K. Hack) and by the Spencer Group (Dr. P. Spencer);

SG Databases • Databases that are developed by SGTE;

TD Databases • Databases that are developed by ThermoData

(Grenoble, France).

6.4 version

• FT Databases

FactPS Database

• General Pure Substance Database;

• 4776 pure compounds from compilations and from critically assessed, optimized data.

• Can be combined, to complement data, with other databases • Same reference states (HSER, 3rd Law entropy).

6.4 version

• FT Databases

FToxid Database

• Contains data for all pure oxides and oxide solutions (solid and liquid) formed among Al2O3, CaO, FeO, Fe2O3, MgO, SiO2.

• Includes various combinations of the above oxides with oxides of As2O3, B2O3, CoO, CrO, Cr2O3, Cu2O, GeO2, K2O, Na2O, MnO, Mn2O3, NiO, PbO, SnO, TiO2, Ti2O3, ZnO, ZrO2.

• Includes data for Al2O3-Re2O3 systems, where Re = La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu.

• The liquid/glass solution phase is called FToxid-Slag. FToxid-Slag includes dilute solutions of S, SO4, PO4, H2O/OH, CO3, F, Cl, I.

6.4 version

• FT Databases

FTsalt Database

• Contains data for pure salts and salt solutions formed among various combinations of the 25 cations: • Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, NH4, Mn, Al, Fe(II),

Fe(III), Co, Ni, Pb, La, Ce, Nd, U, Pu, Th, Cr, Mo and 8 anions:

• F, Cl, Br, I, NO3, OH, CO3, SO4.

6.4 version

• FT Databases

FTmisc Database

• Contains data for various system;

• the system S-Cu-Fe-Mn-Ni-Co-Cr.

• the matte smelting (Pb-Zn) system S-Cu-Fe-Ni-Co-Pb-Zn-As.

• liquid Fe with dilute solutes Al, B, Bi, C, Ca, Ce, Co, Cr, Mg, Mn, Mo, N, Nb, Ni, O, P, Pb, S, Sb, Si, Te, Ti, V, W, Zn, Zr.

• liquid Sn with dilute solutes Al, Ca, Ce, Co, Cr, Cu, Fe, H, Mg, Mo, Na, Ni, O, P, S, Se, Si, Ti

• liquid Pb with dilute solues Ag, As, Au, Bi, Cu, Fe, Na, O, S, Sb, Sn, Zn

• the Hg-Cd-Zn-Te system

6.4 version

• FT Databases

FThall Database

• Specialty database for the Hall-Heroult Process:

• Pure solids and solution phases in the LiF-NaF-MgF2-CaF2-AlF3-Li2O-Na2O-MgO-CaO-Al2O3-Al4C3-CO2 system

• liquid metal Al-Mg-Na-Li-Ca-F-O-C.

6.4 version

• FT Databases

FTOxCN Database

• Specialty database for the oxycarbonitrides in reducing conditions

• Developed for the carbothermal reduction of alumina

• contains data for performing equilibrium calculations in the Al-(Si-Ca-Mg-Fe)-C-O-N-S system at very high temperatures.

6.4 version

• FT Databases

FTfrtz Database

• Specialty database for ammonium-based fertilizers.

• Contains data for 26 pure salts and 14 salt solutions based on the family of ammonium nitrate (NH4NO3), ammonium di-hydrogen phosphate (NH4H2PO4), ammonium chloride (NH4Cl) and ammonium sulfate ((NH4)2SO4) fertilizers with additions of their corresponding potassium salts (and in some cases sodium salts). The model covers the addition of roughly up to 50 wt.% water (H2O).

6.4 version

• FT Databases

FThelg Database

• Contains infinite dilution properties for over 1400 aqueous solute species taken from the GEOPIG-SUPCRT Helgeson public database and include the Helgeson equation of state for temperatures up to 350ºC and pressures up to 165 bar. Solute concentrations up to 0.5 molal.

6.4 version

• FT Databases

FTpulp Database

• Specialty Database for pulp and paper recovery boilers (combustion of black liquor, and corrosion applications);

• Contains data for the system Na, K // Cl, SO4, S2O7, CO3, O, OH, S, S2, S3, S4, S5, S6, S7, S8.

6.4 version

• FT Databases

FTlite Database

• Light Metal Alloys Database

• Includes the elements Ag, Al, As, Au, B, Ba, Be, Bi, C, Ce, Cr, Cu, Fe, Ga, Ge, H, Hf, Hg, In, K, La, Li, Mg, Mn, Mo, Na, Nb, Nd, Ni, O, P, Pb, S, Sb, Sc, Si, Sn, Sr, Ta, Ti, V, Y, W, Zn, Zr.

• Data are intended to provide a sound basis for calculations relating to the production and heat treatment of Al- and Mg-alloys.

6.4 version

• FS Databases

FScopp Database

• Directed primarily to the liquid state of Cu-rich alloys and includes the elements Ag, Al, As, Au, Ba, Be, Bi, C, Ca, Cd, Ce, Co, Cr, Cu, Fe, Ga, Ge, In, Li, Mg, Mn, Nb, Nd, Ni, O, P, Pb, Pd, Pt, Pr, S, Sb, Se, Si, Sm, Sn, Sr, Te, Ti, Tl, V, Y, Zn, Zr.

• Also includes data for Cu-rich solid phases.

• The database is generally valid for the temperature range of approximately 400 to 1600ºC.

6.4 version

• FS Databases

FSlead Database

• Directed primarily to the liquid state of Pb-rich alloys and includes the elements: Ag, Al, As, Au, Bi, C, Ca, Cd, Cu, Fe, Ga, Ge, Hg, In, Mn, Ni, O, Pb, Pd, S, Sb, Se, Si, Sn, Sr, Te, Tl, Zn, & Zr.

• Also includes data for Pb-rich solid phases.

• Is intended to provide a sound basis for calculations relating to lead production and refining.

6.4 version

• FS Databases

FSstel Database

• Database for steels and steelmaking processes.

• Contains data for 132 completely assessed binary alloy systems, 99 ternary and 17 quaternary systems that include the elements 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, Zr.

6.4 version

• FS Databases

FSupsi Database

• Directed primarily to the liquid state of Si-rich alloys, with the particular aim of enabling calculation of impurity concentration levels in ultra-pure silicon.

• Includes the following elements as impurities in liquid silicon: Al, Au, B, C, Ca, Co, Cr, Cu, Fe, Ge, In, Mg, Mn, N, Ni, O, P, Pb, Sb, Si, Sn, Te, Ti, V, Zn.

• The elements included in the Si-rich solid solution are B, C, Ge, N, Sn, Ti, Zn. All other elements are treated as insoluble in solid Si.

6.4 version

• Main modules: EQUILIB

1 kg of Cu concentrate (15oC)

6.4 version

0.1 kg of silica flux (15oC)

6.4 version

<A> kmol of humid air (15oC)

6.4 version

<AB> kmol of O2 (15oC)

6.4 version

How much air + enriched O2 are needed to reach 1260oC for heat losses of 50 kJ/kg of

concentrate

F6.4 version

<A> = 5.99 5.99 mol of air

+ 5.99 mol of O2

per kg of concentrate

F6.4 version

Gas SO2 = 47.6 mol.%

F6.4 version

31.4% SiO2

51.7% Fe(total)

0.37% Cu2O

F6.4 version

0.1 ppm wt. of H added Need the FactPS Database for H2(g) and other gaseous species

F6.4 version

Solidification target “L” on liquid – Scheil-Guliver cooling with 2oC step.

F6.4 version

5 microstructure constituents Final T = 556.10oC

F6.4 version

5 reactions upon cooling Final T = 556.10oC

F6.4 version

wt. % of phases vs T (log10 scale)

6.4 version

• Main modules: PHASE DIAGRAM

6.4 version

Automatic exclusion of undesired species from a lower priority database when using specialty database

6.4 version

X-axis x(AlF3)

6.4 version

Y-axis T

constant P = 1 atm

6.4 version

• T-X diagram • Isothermal sections (X-Y, Gibbs triangle,

reciprocal square) • Isoplethal sections • Chemical potential diagrams (log P vs T, log P

vs X, log P vs log a) • Volumetric diagrams • Enthalpy diagrams • Liquidus projections (X-Y, Gibbs triangle,

reciprocal square) • Solidus projections (X-Y, Gibbs triangle,

reciprocal square) • etc....

6.4 version

• Main modules: VISCOSITY

Structural viscosity model for slag sand glasses Modified Quasichemical Model Slag structure Viscosity

6.4 version

• What is new in the current version of FactSage ?

– Para-equilibrium in EQUILIB and PHASE DIAGRAM Modules

– First-melting and solidus projections

– Enthalpy (H) – composition diagrams

– Automatic Reciprocal Diagram calculation settings

– « X » Species (avoid database inconsistencies)

6.4 version

• What is new in the current version of FactSage ? – Para-equilibrium in EQUILIB and PHASE DIAGRAM Modules

The user specifies, with an easy to use interface option, which species are diffusing

species (C, O, N, etc...)

6.4 version

• What is new in the current version of FactSage ? – Para-equilibrium in EQUILIB and PHASE DIAGRAM Modules

Carbon is the only diffusive species

CEMENTITE + BCC_A2

CEMENTITE + FCC_A1

FCC_A1

FCC_A1 + BCC_A2

Fe - C - MnMn/(Fe+C+Mn) (g/g) = 0.02, 1 atm

C/(Fe+C+Mn) (g/g)

0.000 0.005 0.010 0.015 0.020

FCC_A1

CEMENTITE + FCC_A1

CEMENTITE + BCC_A2

FCC_A1 + BCC_A2

Fe - C - Mn - paraequilibrium diffusing elements: CMn/(Fe+C+Mn) (g/g) = 0.02, 1 atm

C/(Fe+C+Mn) (g/g)

0.000 0.005 0.010 0.015 0.020

Full equilibrium Paraequilibrium

6.4 version

• Paraequilibrium

Blank no diffusion of any element: this is what happens during rapid solidification

r 14(s

Liquid + BCC_A2

Liquid

Cu - Zr1 atm

Zr/(Cu+Zr) (mol/mol)

0.0 0.2 0.4 0.6 0.8 1.0

Paraequilibrium diagram

BCC_A2

Liquid

HCP_A3FCC_A1

Cu - Zr - phase with minimum G1 atm

Zr/(Cu+Zr) (mol/mol)

0.0 0.2 0.4 0.6 0.8 1.0

Possible range for Amorphous formation

Full equilibrium

Paraequilibrium: Rapid solidification

0.10.20.30.40.50.60.70.80.9

Cu Zrmole fraction

Liquid

Laves_C36

BCC_A2

HCP_A3

FCC_A1

FCC_A1 BCC_A2HCP_A3

Cu - Zr - Mg - phase with minimum G

300oC, 1 atm

6.4 version

• What is new in the current version of FactSage ? – First-melting and solidus projections

6.4 version

• What is new in the current version of FactSage ? – Enthalpy (H) – composition diagrams

100 oC

200 oC

300 oC

400 oC

500 oC

600 oC

700 oC

800 oC

Liquid

Liq + Si

Liq + Si + SrSi2Al2

Liq + FCC_A1 + Si + SrSi2Al2

Liq + SrSi2Al2

Liq + FCC_A1

Liq + FCC_A1 + SrSi2Al2

FCC_A1 + Si + SrSi2Al2

FCC_A1 + Si + Mg2Si + SrSi2Al2

FCC_A1 + SrSi2Al2

FCC_A1 + Mg2Si + SrSi2Al2

Al - Si - Mg - Sr

0.3 wt.% Mg, 0.1 wt.% Sr

wt. % Si

0 5 10 15 20 25 30

6.4 version

30%SiO2

Tinitial

Iso-Temperature

Enthalpy diagram option

MgO FeO

CALPHAD XLIII - Changsha, 2014 55

125 oC

225 oC

325 oC

425 oC

525 oC

625 oC

725 oC

825 oC

925 oC

1025 oC

1125 oC

1225 oC

1325 oC

1425 oC

1525 oC

1625 oC

1725 oC

1825 oC

2025 oC2125

oC2225

oC2325

oC2425

AMonoxide + AMonoxide#2 + AOlivine

AMonoxide + AOlivine

ASlag-liq + AMonoxide + AOlivine

ASlag-liq + AOlivine

ASlag-liq

ASlag-liq + AMonoxide

AOlivine + SiO2(s)

AOlivine + SiO2(s2)

AOlivine + SiO2(s4)

MgO - FeO - SiO2

SiO2/(MgO+FeO+SiO

2) (g/g) = 0.3, 1 atm

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

0 0.1 0.2 0.3 0.4 0.5 0.6

6.4 version

• Macro processing for process simulation - Simple flow sheet type process calculations

- Complex process simulation model

- Input from & output to Excel file

6.4 version

• What is new in the current version of FactSage ? – Automatic Reciprocal Diagram calculation setting

Old type input

New type input

6.4 version

• What is new in the current version of FactSage ? – Automatic Reciprocal Diagram calculation setting

Automatic setup of electro-neutrality condition: Na + 2 Ca = F + Cl

7.0 version

FactSage 7.0

(to be released in Autumn 2014)

7.0 version

• What will be in the upcoming version of FactSage ? – New SOLUTION Module

7.0 version

• What will be in the upcoming version of FactSage ? – New SOLUTION Module

Toop interpolation Kohler interpolation

7.0 version

• What will be in the upcoming version of FactSage ? – Big update of our FToxid Database

1) Expansion of P2O5 in oxide database: CaO-MgO-FetO-MnO-SiO2-Al2O3-Na2O-BaO-Li2O- K2O-P2O5 for P distribution between steel/slag/gas/other in various pyrometallurgical applications.

2) Expansion of oxides toward oxy-fluoride systems: CaO-SiO2-Al2O3-MgO-Na2O-K2O-F (Ca,Al,Si,Mg,Na,K//O,F) for special refining slag, mold flux and other applications.

3) Improved K2O and Na2O in oxide system: CaO-SiO2-Al2O3-MgO-Na2O-K2O-etc. for coal combustion, ceramic processing, and other applications.

– New update for viscosity database Accuracy of FeO-Fe2O3 containing systems is largely improved.

7.0 version

• What will be in the upcoming version of FactSage ?

– New Refractory Metal Alloys Database • Carbide, Nitride, Boride and Silicide Systems

• B, C, N, Si with Al, Ca, Co, Cr, Fe, Hf, Mg, Mn, Mo, Nb, Ni, Re, Sc, Ta, Tc, Ti, V, W, Y, Zr

7.0 version

• What will be in the upcoming version of FactSage ?

– New FTnucl Database • Th-U-Np-Am-Pu + O-C-N + Fe-Ba-Zr-Ru + Li-Na-K-Rb-Cs + He-Ne-Ar-Xe-Kr

FTnucl

liquid

gas + liquid

liquid + C

FCC(dicarbide) + C

ThC2(monoclinic) + C

ThC2(CaC2) + C

FCC + FCC

FCC + ThC2FCC(metal) + FCC(carbide)

FCC(carbide)

liquid + FCC

BCC + FCC

FCC(dicarbide)

FCC(metal)

Th - C

mole fraction C

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

0.10.20.30.4

U Bamole fraction U

e fract

mole fra

ction B

Liquid

FCC_C1 + Liquid + Liquid#2

gas_ideal + A2BCX6 + Liquid

gas_ideal + A2BCX6 + BaUO4(s)

gas_ideal + Liquid + BaO(s)

FCC_C1 + Liquid

A2BCX6 + Liquid

FCC_C1 + A2BCX6 + Liquid

gas + Liq. + FCC_C1

P(O2) = 8.56x10-17

P(O2) = 3.38x10-16

P(O2) = 0.93 bar

Liq. + FCC_C1 + BaU2O6

P(O2) = 0.238 bar

Perovskite

FCC_C1 + BaU2U6 + Ba2U2O7

Liquid

Liq. + BaU2O6 + Ba2U2O7

BaU2O6

Ba2U2O7

Ba2U3O11

Ba3UO6

P(O2) = 1.93x10-2

P(O2) = 7.79x10-4

FCC_C1 + Ba2U2O7 + Perovskite

Ba - U - O

2273.15 K, 1 bar

Beyond 7.0 version

Beyond FactSage 7.0

(Autumn 2015 ?)

Solidification model (1D): 2015

Calculation takes less than 1 mins !! - Numerical calculation: Implicit method - Compositional independent Diffusivity - Multicomponent system

Solidification model (1D): 2015

Cooling rate (K/sec)

Mg-3%Al-1%Zn

Mg-3%Al

Future direction of FactSage

• FactSage was always developed from a university environment;

• Historically a strong emphasis has been given to thermodynamic and physical property model developments:

– Modified Quasichemical Model (1 subl. Pair, 2 subl. Pair, 2 subl. Quads)

– Unified Interaction Parameter Formalism;

– Viscosity (slags, salts, metals);

– Electrical conductivity and ionic mobilities;

– etc…

The FactSage development team remains fully dedicated to keep a strong fundamental background to CALPHAD type of modeling.

Future direction of FactSage

Thermodynamic models & databases

Physical properties database - Mobility (atoms, ions, …) - Viscosity - Molar volume/density - Thermal/electrical properties - Surface tension

Solidification simulation

Development of special process simulation tools for industrial applications

Precipitation/annealing simulation

Recent Developments of FactSage Software and Databases · A brief history… •The ChemSage Era...

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