State of the thermodynamic database for the BOFdePhos project
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1 State of the thermodynamic database for the BOFdePhos project K. Hack, T. Jantzen, GTT-Technologies, Herzogenrath GTT Users Meeting, July 2015, Herzogenrath
2 Contents Old LD converter model database Necessary components for BOFdePhos Contributions covering sulphur Contributions covering phosphorous
3 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
4 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
5 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
6 Output from LD-Sage old database, Jalkanen reference data No info on P2O5 transfered to graph!!!
7 Output from LD-Sage old database, Jalkanen reference data Click here to obtain report!
8 3000 CaS - FeS 1 bar Thermodynamic database Sulphide subsystems [Heumann, 1942] Slag T(C) 1500 Slag + Oldhamite Oldhamite Slkag + FeS(s4) FeS(s4) + Oldhamite FeS(s2) + Oldhamite FeS + Oldhamite wt% CaS/(CaS+FeS)
9 GTT-Technologies Thermodynamic database Ternary systems with sulphide component Al 2 O 3 - CaS - CaO 1600 o C, 1 bar [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) 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 MeO Ca 3 Al 2 O 6 CaS CaS CaAl 2 O Ca CaO 12 Al 14 O 33 Al 2 O mole fraction T(min) = o C, T(max) = o C CaAl 12 O 19 3CaAl 4 O Al 2 O T o C
10 Thermodynamic database The Fe-O-S system O - S - Fe Projection (Slag), 1 atm S mole fraction S C 1100 C 1200 C 1300 C 1400 C 1500 C Fe mole fraction Fe O V. Raghavan, Phase diagrams of Ternary Iron Alloys, Part 2, Ternary systems containing Iron and Sulphur, The Indian Institute of Metals, Calcutta,1988.
11 Thermodynamic database Data for pure P2O5 P L H T H 0.5 L O' T O' T O log 10 P(bar) -0.5 H-P Gas O-P 2 O'-P /TK
12 Thermodynamic database Binary systems, including Fe-X Fe -OO 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-a MeO MeO + fcc-a Fe 2 O Meo + bcc-a mole O/(Fe+O) T(C) 2700 Slag Slag + MeO 2100 MeO 1900 [Lejus 1964] [Alper 1962] [Rankin 1916] [Viechniki 1974] [Roy et al 1953] [Chiang and Kingery 1989] SPINEL [Mori 1982] [Stubican and Roy 1965] [Shirasuka and Yamaguchi 1974] [Navrotsky et al 1986] SPINEL + Al 2 O [Saalfeld and Jagodzinski 1957] [Viertel and Seifert 1980] mole Al 2 O 3 /(Al 2 O 3 +MgO)
13 Thermodynamic database CaO - P 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 wt%p 2
14 Thermodynamic database Isopleth section Ca 2 SiO 4 -Ca 3 P 2 O 8 Ca 2 SiO 4 - Ca 3 P 2 O Slag C2S_C3P [W. Fix, G. Trömel, R. Heinke, 1969] T(C) 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] (1969). Ca 5 P 2 SiO Ca 7 P 2 Si 2 O 16 C2S_PRIME + Ca 2 SiO 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., (1959).
15 Thermodynamic database FeO - P 2 - Fe Fe/(FeO+P 2 ) (g/g) = 0.001, 1 bar [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 Fe18 P 2 O 24 Fe 3 P 2 O 8 BCC_A MeO + Fe 18 P 2 O 24 BCC_A2 + SPINEL + Fe 18 P 2 O 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
16 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
17 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)
18 Phosphorous Distribution CaO - FeO - P 2 - Fe Fe/(CaO+FeO+P 2 ) (g/g) = , 1600 o C, 1 bar P 2 [Trömel, 1959] Red line Phosphorous Capacity [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 FeO percent by weight CaO
19 Phosphorous Distribution 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] Ca3(PO4)2 Ca-rich MeO 1600 C 1700 C Ca-rich MeO wt% FeO in slag In-Ho Jung et al.
20 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.
21 Thank you for your attention!
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