Recent Developments in FactSage Thermochemical Software and Databases Christopher. W. Bale,* E. Bélisle*, P. Chartrand*, S.A. Decterov*, G. Eriksson**, A. Gheribi*, K. Hack**, I.-H. Jung*, J. Melançon*, A.D. Pelton*, S. Petersen** and C. Robelin* * CRCT - Center for Research in Computational Thermochemistry, École Polytechnique de Montréal (University of Montreal) ** GTT-Technologies Aachen - presented at the TMS Annual Meeting, San Diego, 2014 : Celebrating the Megascale: EPD Symposium in Honor of David G.C. Robertson To download this power point presentation visit > Conferences and Workshops FactSage 1
FactSage Thermochemical Software and Databases FactSage 2
FactSage Thermochemical Software and Databases Recent Developments in 1. Databases 2. Equilib 3. Viscosities 4. Fact-Optimal 5. Phase Diagrams 6. Fact-Web FactSage 3
1. Many Types of Databases FactPS, FToxid, FTOxCN, FTsalt, FSstel, SGTE have been updated in FactSage 6.4 FactSage 4
1. FToxid - the FACT Oxide Databases FToxid solution database - Major Oxide Solutions Slag: CaO-MgO-Al 2 O 3 -SiO 2 -FeO-Fe 2 O 3 -MnO-Mn 2 O 3 -Ti2O 3 -TiO 2 + gas solubility such as S (SO2), P, H (OH), N, C, F Spinel: (Al, Co 2+, Co 3+, Cr 2+, Cr 3+, Fe 2+, Fe 3+, Mg, Ni 2+, Zn) [Al, Co 2+, Co 3+, Cr 3+, Fe 2+, Fe 3+, Mg, Ni 2+, Zn, ] 2 O 4 Pyroxenes: (Ca, Fe 2+, Mg) M2 (Fe 2+, Fe 3+, Mg, Al ) M1 (Fe 3+, Al, Si) B Si A O 6 Olivine: (Ca, Fe 2+, Mg, Mn, Ni, Co, Zn) [Ca, Fe 2+, Mg, Mn, Ni, Co, Zn] SiO 4 Melilite: (Ca) 2 [Mg, Fe 2+, Fe 3+, Al, Zn] {Fe 3+, Al, Si} 2 O 7 Monoxide: CaO - MgO - MnO - CoO - NiO - FeO (+ Fe 2 O 3 - Al 2 O 3 - ZnO - Cr 2 O 3 ) a-ca 2 SiO 4 : a-ca 2 SiO 4 ( + Fe 2 SiO 4, Mg 2 SiO 4, Mn 2 SiO 4 ) a -Ca 2 SiO 4 : a -Ca 2 SiO 4 ( + Fe 2 SiO 4, Mg 2 SiO 4, Mn 2 SiO 4, Pb 2 SiO 4, Zn 2 SiO 4 ) Wollastonite: CaSiO 3 ( + FeSiO 3, MgSiO 3, MnSiO 3 ) Corundum: Al 2 O 3 - Cr 2 O 3 - Fe 2 O 3 Ilmenite: (Fe 2+, Mg, Mn, Ti 3+ ) (Ti 4+, Ti 3+ )O 3 Pseudobrookite: (Fe 2+, Mg, Mn, Ti 3+ ) (Ti 4+, Ti 3+ ) 2 O 5 26 other solid solutions + 251 oxide compounds with 355 phases in the FToxid pure substances database FactSage 5
1. Many Types of Databases Typical databases and phases used in iron and steel processing : FactPS - FACT pure substances - all gaseous species, stoichiometric solid and liquid species; FToxid - FACT oxides - many solution phases (slag, spinel, monoxide, olivine, etc.) and pure solid and liquid oxides (but no gas phase); FTmisc -FACT miscellaneous - FeLq liquid solution phase. For steelmaking calculations (slags / refractories / gases / molten iron), or FSstel - FactSage steel - solid and liquid steel phases and also includes a number of gases, oxides, sulfides, nitrides, etc. For steel solidification and alloy design. When more than one database is used in an equilibrium calculation, there may be duplicate and possibly conflicting data for the same compound species. In FactSage 6.4 an automatic exclusion strategy is applied to compound species such that duplicate or conflicting species are no longer selected. FactSage 6
2. Equilib Module - Many Types of Calculations Equilib calculates the conditions for multiphase, multicomponent equilibria, with a wide variety of tabular and graphical output modes, under a large range of constraints through Gibbs energy minimization. There are many different types of calculations, for example : Equilibrium using data from single or multiple databases Scheil-Gulliver and Equilibrum Cooling Casting software Open calculations Viscosities of slags and glasses Simulation of processes macro processing Streams and recycling Fact-XML customized output tables, spreadsheets, graphs Fact-Function-Builder customized functions FactOptimal identify the optimal conditions for alloy and process design using thermodynamic and property databases FactSage 7
2. Equilib desulfurizing a steel by CaSi. Mixing databases Reactants Compounds from FactPS, FTmisc & FToxid conflicting & duplicate species automatically excluded Solutions from FTmisc and FToxid Final conditions: <A> = 0.015 T = 1627 C P = 1 atm and Calculate >> FactSage 8
2. Equilib - desulfurizing a steel by CaSi addition Mixing 3 databases FactPS, FTmisc, FToxid Gas phase, mainly Ar - FactPS database Liquid steel FTmisc database Slag containing sulfur FToxid database No solids (activity<1) - mixed databases FactSage 9
2. Equilib Macro Processing simulation of BOF Equilib Macro Processing simulation of the Basic Oxygen Steelmaking process, where the hot metal is refined into raw liquid steel Schematic representation of the reaction zones in the BOF process: (a) soft blowing period; (b) medium and hard blowing periods Simulation results: Top - change in metal composition Bottom - change in slag composition FactSage 10
2. Equilib Macro Processing simulation of ISASMELT FactSage 11
3. Viscosities of slags and glasses There are two viscosity databases for oxide solutions. The melts database for liquid and super-cooled slags where viscosities are not too high: Al 2 O 3 -B 2 O 3 -CaO-FeO-Fe 2 O 3 -K 2 O-MgO-MnO-Na 2 O-NiO-PbO -SiO 2 -TiO 2 -Ti 2 O 3 -ZnO-F - melts The glasses database at and below the glass transition temperatures: Al 2 O 3 -B 2 O 3 -CaO-K 2 O-MgO-Na 2 O-PbO-SiO 2 - glasses In principle, the glasses database is valid over the whole temperature range from liquid melts to glasses, but sometimes it is slightly less accurate for liquid slags than the melts database. FactSage 12
ln(visc) [PaS] 3. Viscosities in Na 2 O-Al 2 O 3 -SiO 2 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9-3 0.9 Fig. 16 Fig. 17 0.8 0.7 SiO 2 0.6 0.5 0.4 mole fraction T = 1400 C 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 Riebling, 1966 Fig. 20 Toplis et al., 1997 Fig. 19 Fig. 18 7 6 5 4 3 2 1 0-1 0-2 0.3 0.2 0.1 25 20 Na 2 O Al 2 O 3 1 Viscosities calculated using the melts database 1200 1400 1600 C mole fraction SiO 2 = 0.67 Toplis et al. 1997 Stein and Spera, 1993 Riebling, 1966 Kim and Lee, 1997 15 below liquidus 10 1200 C 5 1400 C 1600 C 0 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 molar ratio Al 2 O 3 / (Al 2 O 3 +Na 2 O) FactSage 13
4. FactOptimal - minimizes and/or maximizes a set of functions FactOptimal identifies the optimal conditions for alloy and process design uses Equilib and the Mesh Adaptive Direct Search (MADS) algorithm. FactOptimal minimizes and/or maximizes a set of functions: { f1(x1, x2... T, P); f2(x1, x2...t, P) } where the functions f (e.g. T, P, V, heat, mass, density, conductivity, ) are calculated by Equilib the functions may be non-smooth (e.g. liquidus ) the estimation of derivatives may be problematic the evaluations of f may be time consuming the function calculation may fail unexpectedly at some points the constraints may be non-linear, non-smooth or Boolean FactSage 14
4. FactOptimal - minimum liquidus temperature of Al-Cu-Zn-Mg FactOptimal locates the optimal composition of the alloy that minimizes the liquidus temperature and respects the constraints Constraints: X(Al) +X(Cu) < 0.2 r < 2.2 g/ml cost < $2,900/Ton Minimum T 436.75 o C Composition at the minimum T Plot of T o C vs # of Calcs. Values of the constraints: Al + Cu = 0.11534 r = 2.19997 g/ml cost = $2,900/Ton FactSage 15
Log [ (Poise)] 4. FactOptimal : minimum viscosity of steelmaking slags FactOptimal calculates optimum composition - minimizes the viscosity of the slag - minimizes the liquidus temperature - satisfies the constraints on composition Steelmaking slag : CaO-MgO-Al 2 O 3 -SiO 2 -FeO-CaF 2 Cpt. Constraints wt.% 37.41 - CaO 48.61% 9.37 - MgO 12.99% 16.53 - Al 2 O 3 22.95% 10.05 - SiO 2 12.50% 10.05 - FeO 18.20% Pareto Front: At 1752 K log(η) = -0.1 38.85% 11.55% 18.08% 10.38% 17.64% 0.8 0.6 0.4 0.2 0.0-0.2-0.4-0.1 No Equilib results CaF 2 0-5% 3.49% Composition varies along the Pareto Front Equilib 2000 calculations 1752 K Pareto Front 1660 1680 1700 1720 1740 1760 1780 1800 1820 1840 Temperature (K) FactSage 16
4. FactOptimal : optimize cryolitic electrolyte for Al production Alumina is dissolved in liquid electrolyte called cryolite: NaF - AlF 3 - CaF 2 - Al 2 O 3 Hall-Heroult : 2 Al 2 O 3(cryolite) + 3 C (anode) 4 Al (liquid) + 3 CO 2(gas) C anode Hall-Heroult Cell Al (liquid) cryolitic bath (liquid) Na 3 AlF 6 + AlF 3 +CaF 2 +Al 2 O 3 Objectives : minimize the density : better separation Al / bath maximize the ionic conductivity : better energy efficiency Constraints : T Operation = T Liquidus + 5 o C < 970 o C 1.2 CR = n(naf) / n(alf 3 ) 2.6 (typically, CR = 2.2 ± 0.4) 3 wt% CaF 2 10 2 wt% Al 2 O 3 5 FactSage 17
Electrical conductivity (S.cm -1 ) 4. FactOptimal : optimize cryolitic electrolyte for Al production 2.4 Optimal Pareto Pareto Front Objectives : - minimize the density - maximize the ionic conductivity 2.2 2.0 No Equilib results Typical industrial conditions 960 o C C D (max. ionic conductivity & max. density) The composition and temperature change along the Pareto Front. 1.8 1.6 1.4 A 1.80 1.85 1.90 1.95 2.00 2.05 2.10 2.15 B Density of the system (g.cm -3 ) Equilib results Point CR = n(naf) / n(alf 3 ) wt% CaF 2 wt% Al 2 O 3 T = T LIQUIDUS + 5 o C A 1.23 3.5 5.0 944 B 1.75 3.0 3.7 890 C 2.18 3.0 2.0 970 D 2.60 10.0 2.0 969 FactSage 18
4. FactOptimal : optimize cryolitic electrolyte for Al production Plots of compositions vs. conductivities and vs. densities along the Pareto Front Point CR = n(naf) / n(alf 3 ) wt% CaF 2 wt% Al 2 O 3 T = T LIQUIDUS + 5 o C A 1.23 3.5 5.0 944 B 1.75 3.0 3.7 890 C 2.18 3.0 2.0 970 D 2.60 10.0 2.0 969 FactSage 19
5. Phase Diagram - many types of phase diagrams For phase diagram calculations the axes and constants are various combinations of the variables T, 1/TK, P, log(p), RTln(P), V, log(v), log(a), Eh, ph, H and X. Type Y-axis X-axis 1 T P, log P, V, log V 2 P, log P, V, log V T 3 RTln(a), log(a) P, log(p) 4 P, log(p) RTln(a), log(a) 5 RTln(a), log(a) T 6 T RTln(a), log(a) 7 RTln(a), log(a) T 8 Eh ph (Pourbaix diagram) 9 V, log(v) X 10 H X 11 P, log(p) X 12 T X (classical temperature vs. composition) 13 RTln(a) X 14 X X (isothermal X vs Y section) 15 X X (isothermal Gibbs ternary) 16 X X (polythermal X vs Y projection) 17 X X (polythermal Gibbs ternary) T = temperature (or 1/TK), P = total pressure, V = total volume, H = enthalpy, a = activity (or fugacity), X = composition (mole fraction, weight fraction) FactSage 20
5. Phases and Phase diagrams: Na 2 O-Al 2 O 3 -CaO System Data taken from FToxid - FACT oxide databases (a:b:c) = ana 2 O.bCaO.cAl 2 O 3 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 Na 2 O 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 (1:8:3) (1:0:9) (0:3:1) Na 2 O - Al 2 O 3 - CaO CaO(s) Projection (Slag) CaAl 2 O 4 (s) CaAl 4 O 7 (s) Al 2 O 3 (s4) (0:1:1) (0:1:2) (0:1:6) 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 CaO Al 2 O 3 mole fraction NaAlO 2 (s2) (1:0:1) 1:1:2 NaAl 9 O 14 (s) N(a)C(b)A(c) = ana 2 O.bCaO.cAl 2 O 3 Slag (1:0:6) FactSage NC8A3 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 C3A Na 2 O - Al 2 O 3 - CaO 1200 o C Na 2 O 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 CA CA2 CA6 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 CaO Al 2 O 3 mole fraction NCA2 s.s Verweij and Saris (1986), maximum solubility NA NC3A8 NA6 NA9 FactSage NCA2: (Na 2,Ca)O Na 2 O 2Al 2 O 3 solid solution FactSage 21
5. Phase Diagram - first melting projection of Al-Mg-Zn Data taken from FTlite - FACT light metal alloy databases Magnification at low Mg concentrations. FactSage 22
5. Phase Diagram - polythermal projection reciprocal system Data taken from FTOxCN - FACT high-temperature oxycarbonitride databases (CaO) 3 -Al 2 O 3 -Ca 3 N 2 -(AlN) 2 Reciprocal diagram option FactSage 23
6. Fact-Web free limited access to FactSage via the Intenet Fact-Web consists of an educational package of interactive programs that provide access to all the compounds in the FactPS pure substances database and limited access to some of the FactSage modules - www.crct.polymtl.ca/factweb.php. Suite of Fact-Web modules FactSage 24
6. Fact-Web Reaction-Web module Sample input to Reaction-Web - taken from the Reaction-Web manual. FactSage 25
6. Fact-Web Reaction-Web module Sample output from Reaction-Web - taken from the Reaction-Web manual. FactSage 26
Recent Developments in FactSage Thermochemical Software and Databases FactSage software and database development is ongoing, for example a completely new Solution module is under development and should be ready for the next version of FactSage. new databases are being prepared: FTnucl the FACT nuclear database SPrefr the Spencer Group refractory database for hard metals. For the latest Information on the status of FactSage, documentation on all the modules and sample phase diagrams of hundreds of alloy, salt, oxide, etc. systems visit. FactSage 27