State of the thermodynamic database for the BOFdePhos project K. Hack, T. Jantzen, GTT-Technologies, Herzogenrath GTT Users Meeting, July 2015, Herzogenrath
Contents Old LD converter model database Necessary components for BOFdePhos Contributions covering sulphur Contributions covering phosphorous
The old thermodynamic data Source: THERDAS system and literature Elementary components: Ar, Al, C, Ca, Fe, H, O, S, Si, Mg, B, N, Mn, P Solution phases: GAS (ideal): 60 species in total SLAG (IRSID cell model): CaO, MgO, Al2O3, SiO2, FeO, Fe2O3, MnO,(PO)2O3
The old thermodynamic data Solution phases (continued): LIQ_Fe (Wagner dilute sol.) Fe and Al,C,Ca,O,S,Si,Mg,B,N,H,Mn,P BCC_Fe (Wagner dilute sol.) Fe and Al,B,C,N,O,S,Si,Mn,P,H FCC_Fe (Wagner dilute sol.) Fe and Al,B,C,N,O,S,Si,Mn,P,H
The old thermodynamic data Solution phases (continued): MeS (ideal) CaS,FeS,MnS Stoichiometric phases: 100 compounds, among these P2O5 and three calcium phosphates CaCO3, MgCO3, dolomite as input substances
Output from LD-Sage old database, Jalkanen reference data No info on P2O5 transfered to graph!!!
Output from LD-Sage old database, Jalkanen reference data Click here to obtain report!
3000 CaS - FeS 1 bar Thermodynamic database Sulphide subsystems [Heumann, 1942] 2500 2000 Slag T(C) 1500 Slag + Oldhamite Oldhamite Slkag + FeS(s4) 1000 500 FeS(s4) + Oldhamite FeS(s2) + Oldhamite FeS + Oldhamite 0 0 20 40 60 80 100 wt% CaS/(CaS+FeS)
2500 2600 2700 2800 GTT-Technologies Thermodynamic database Ternary systems with sulphide component Al 2 O 3 - CaS - CaO 1600 o C, 1 bar 0.16 0.14 0.12 [Ozturk and Turkdogan,1984] [Piao,Lee,Kang,2013] CaAl 4 O 7 + CaAl 12 O 19 + CaS Al 2 O 3 - CaS - CaO Projection (Slag), 1 bar CaS/(Al 2O3+CaS+CaO) (g/g) 0.1 0.08 0.06 0.04 0.02 0 MeO + Slag + CaS MeO + Slag Slag + CaS Slag wt% Al 2 O 3 /(Al 2 O 3 +CaS+CaO) Slag + CaAl 4 O 7 + CaS Slag + CaAl 4 O 7 0 10 20 30 40 50 60 70 80 MeO 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 4 Ca 3 Al 2 O 6 CaS CaS 2000 1900 1800 65 CaAl 2 O 4 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 Ca CaO 12 Al 14 O 33 Al 2 O 3 2100 mole fraction T(min) = 1352.33 o C, T(max) = 2898.8 o C CaAl 12 O 19 3CaAl 4 O 7 2 1 Al 2 O 3 2800 2650 2400 2150 1900 1650 1400 T o C
Thermodynamic database The Fe-O-S system O - S - Fe Projection (Slag), 1 atm S mole fraction S 0.1 0.2 0.3 0.4 0.5 1000 C 1100 C 1200 C 1300 C 1400 C 1500 C 0.1 0.2 0.3 0.4 0.5 Fe 0.9 0.8 0.7 mole fraction Fe 0.6 0.5 O V. Raghavan, Phase diagrams of Ternary Iron Alloys, Part 2, Ternary systems containing Iron and Sulphur, The Indian Institute of Metals, Calcutta,1988.
Thermodynamic database Data for pure P2O5 P 2 1.5 L H T H 0.5 L O' T O' T O log 10 P(bar) -0.5 H-P 2-1.5 Gas O-P 2 O'-P 2-2.5 0.8 1 1.2 1.4 1.6 1.8 2 2.2 2.4 2.6 1000/TK
Thermodynamic database Binary systems, including Fe-X Fe -OO 3500 2900 Liquid (Me) + Gas [85Kub] [43Tay] [70Dis] [78Fis] 2300 Liquid (Me) Slag Slag + Gas MgO Al 2 O 3 - MgO Al 2 O 3 Slag + Liquid (Me) T(K) 2900 Spinel Slag + bcc-a2 1700 MeO MeO + fcc-a1 1100 Fe 2 O Meo + bcc-a2 3 500 0 0.2 0.4 0.6 0.8 1 mole O/(Fe+O) T(C) 2700 Slag 2500 2300 Slag + MeO 2100 MeO 1900 [Lejus 1964] 1700 1500 [Alper 1962] [Rankin 1916] [Viechniki 1974] [Roy et al 1953] [Chiang and Kingery 1989] SPINEL 1300 1100 [Mori 1982] [Stubican and Roy 1965] [Shirasuka and Yamaguchi 1974] [Navrotsky et al 1986] SPINEL + Al 2 O 3 900 [Saalfeld and Jagodzinski 1957] [Viertel and Seifert 1980] 700 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 mole Al 2 O 3 /(Al 2 O 3 +MgO)
Thermodynamic database CaO - P 2 2600 GTT [Hill, 1944] [Trömmel, 1961, DTA] [Trömmel, 1961, hot stage microscope] 2100 MeO + Slag Slag 1600 Ca 3 (PO 4 ) 2 (s3) T(C) Ca 3 (PO 4 ) 2 (s2) Ca 2 O 7 P 2 (s3) 1100 MeO + Ca 4 (PO 4 ) 2 O Ca 2 O 7 P 2 (s2) 600 Ca 3 (PO 4 ) 2 Ca 2 P 6 O 17 Ca 4 (PO 4 ) 2 O Ca 2 P 2 O 7 Ca(PO 3 ) 2 CaP 4 O 11 P 2 (s2) + CaP 4 O 11 100 0 20 40 60 80 100 wt%p 2
Thermodynamic database Isopleth section Ca 2 SiO 4 -Ca 3 P 2 O 8 Ca 2 SiO 4 - Ca 3 P 2 O 8 2500 2300 2100 1900 1700 Slag C2S_C3P [W. Fix, G. Trömel, R. Heinke, 1969] T(C) 1500 1300 1100 900 700 C2S_PRIME CC2S_C3P + Ca 3 (PO 4 ) 2 (s2) C2S_C3P + Ca 3 (PO 4 ) 2 Ca 5 P 2 SiO 12 + Ca 3 (PO 4 ) 2 W. Fix, H. Heymann, and R. Heinke, J. Am. Ceram. Soc., 52 [6] 346-347 (1969). Ca 5 P 2 SiO 12 500 Ca 7 P 2 Si 2 O 16 C2S_PRIME + Ca 2 SiO 300 4 0 20 40 60 80 100 wt% Ca 3 P 2 O 8 /(Ca 2 SiO 4 +Ca 3 P 2 O 8 ) R. W. Nurse, J. H. Welch, W. H. Gutt, J. Chem. Soc.,1077-1083 (1959).
Thermodynamic database FeO - P 2 - Fe Fe/(FeO+P 2 ) (g/g) = 0.001, 1 bar 1800 1600 [L.Chang, 2010] [G. Trömmel, K. Schwerdtfeger, 1963, DTA] 1400 BCC_A2 + Slag Slag + Liquid [G. Trömmel, K. Schwerdtfeger, 1963, melting] 1200 BCC_A2 + MeO BCC_A2 + MeO + Slag T(C) 1000 BCC_A2 + Slag + Fe 3 P 2 O 8 800 Fe18 P 2 O 24 Fe 3 P 2 O 8 BCC_A2 600 + MeO + Fe 18 P 2 O 24 BCC_A2 + SPINEL + Fe 18 P 2 O 24 400 BCC_A2 + SPINEL + Fe 3 P 2 O 8 Fe 2 P 2 O 7 Slag + Liquid + FeP 2 O 6 Slag + Liquid + P 2 (s3) 200 FeP 2 O 6 Liquid + P 2 (s3) + FeP 2 O 6 0 wt%p 2 /(FeO+P 2 ) Liquid + P 2 (s2) + FeP 2 O 6 0 20 40 60 80 100
Liquidus surface in Ca 3 P 2 O 8 -Al 2 O 3 -SiO 2 before optimisation P.D.S. St. Pierre, J. Am. Ceram. Soc., 39[4], (1956), pp. 147-150.
Thermodynamic database Phosphorous containing phases in present database: Gas: Liquid oxide: Solid solutions: P, P2O5 as well as N2,O2,CO,CO2,SiO and many others P2O5 as well as 23 P2O5-containing associate species 7 phosphates 1 silicate-phosphate (C2S-C3P) 4 phosphates with limited SiO2 solubility 4 silicates with limited P2O5 (PO4) solubility Stoichiometric compounds: P and P2O5 as well as 56 phosphides, phosphates or silico-phosphates Liquid-Fe: Mg, Mn, Ca, O, S, P Wish-lists????? Fe-liq: Fe-P-C-Si-Mn-O (Mg,S,Al,Cr) Slag: CaO-MgO-MnO-SiO2-Al2O3-FeO-Fe2O3-P2O5 (CaS,FeS,MgS,MnS)
Phosphorous Distribution CaO - FeO - P 2 - Fe Fe/(CaO+FeO+P 2 ) (g/g) = 0.0001, 1600 o C, 1 bar P 2 [Trömel, 1959] Red line Phosphorous Capacity 10 20 30 40 50 60 70 80 90 10 20 30 40 50 60 70 80 90 [Turkodogan, 1967] CaO, [Trömel, 1962] CaO+Ca 4 P 2 O 9, [Trömel, 1962] [Knuppel, 1959] [Nagabayashi, 1988] Slag + Liquid Slag + Liquid + Ca 3 (PO 4 ) 2 (s3) Slag + Liquid + Ca 4 (PO 4 ) 2 O Slag + Liquid + Ca 4 (PO 4 ) 2 O Slag + Slag#2 + Liquid MeO + Slag + Liquid + Ca 4 (PO 4 ) 2 O Slag + Slag#2 + Liquid Slag + Liquid + Ca 3 (PO 4 ) 2 (s3) MeO + Slag + Liquid MeO + Slag + Liquid Slag + Liquid 10 20 30 40 50 60 70 80 90 10 20 30 40 50 60 70 80 90 FeO 90 80 70 60 50 40 percent by weight 30 20 10 CaO
Phosphorous Distribution 4 3.5 P-distribution between molten iron and the slag Preliminary results [Nagabayashi,1988, 1600 C] [Shirota,1985, 1700 C] GTT Log[% P in slag/% P in Fe] 3 2.5 2 Ca3(PO4)2 Ca-rich MeO 1600 C 1700 C Ca-rich MeO 1.5 1 0 10 20 30 40 50 60 wt% FeO in slag In-Ho Jung et al.
Summary and Outlook A self-consistent thermodynamic database for the system CaO-MgO-Al 2 O 3 -FeO-Fe 2 O 3 -MnO-Mn 2 O 3 -P 2 -SiO 2 with inclusion of S in form of CaS-MgS-FeS-MnS as well as Al 2 S 3, Na 2 S, K 2 S is underway. The GTT Oxide database is a useful source for standard systems. BOFdePhos-specific data are being assessed. The new database will be used to generate an application oriented datafile that is compatible with the ChemApp Programmers Library which is used in SimuSage and subsequently in the converter model LD-Sage.
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