Thermodynamic Assessment of the System

Transcription

1 Mitglied der Helmholtz-Gemeinschaft GTT-Technologies, 13th Annual Workshop, September 14-16, 2011 Thermodynamic Assessment of the System Al 2 -K 2 O-Na 2 O- -CaO-MgO Elena Yazhenskikh (1), Klaus Hack (2), Michael Müller (1) (1) Forschungszentrum Jülich, IEK-2 (Microstructure and properties of materials), Germany (2) GTT-Technologies, Germany

2 Contents Motivation and aim of the work Models and optimisation procedure Results of re-assessment for binary systems Assessment for Na 2 O-K 2 O-Al 2 - system Assessment for K 2 O-Al 2 - +MgO, CaO system Conclusions and outlook GTT-Technologies, 13th Annual Workshop, September 2011 Folie 2

3 Motivation and aims Thermodynamic calculation/prediction for slag relevant oxide systems, which are difficult from the point of view of experimental measurements Na 2 O CaO K 2 O MgO Calculation requires: Reliable database, based on the experimental data Software Al 2 HOTVEGAS Available databases are not sufficient to model the complete coal ash (slag) system Purpose of out work - development of a new data base, which is: applicable for the slag relevant system containing alumina, silica, alkali, alkali-earth oxides suitable for the calculations and/or predictions of the phase equilibria and other thermodynamic properties by variation of temperature and composition GTT-Technologies, 13th Annual Workshop, September 2011 Folie 3

4 Modelling of liquid and solid solutions Applied and chosen model for the phases under consideration Phase name Associate species model Multi-sublattice model Liquid Liquid pure oxides, binary and ternary liquid species - Mullite Al 6 Si 2 O 13 : Al 6 Si 2 O 13 1/4, Al 2, 2 (Al 3+ ) 1 (Al 3+ ) 1 (Al 3+, Si 4+ ) 1 (O 2-, Va) 5 (Mao et al., 2005) Na disilicate (Na 1-x K x ) 2 Si 2 O 5 : Na 2 Si 2 O 5, K 2 Si 2 O 5 (Na 1+, K 1+ )2(Si 4+ )2(0 2- )5 K or Na aluminate Nepheline, carnegieite Natrium aluminate AlkAlO 2 - low T, high T (Al 3+, Si 4+ ) 1 (K 1+, Na 1+ Va 0 ) 1 (O 2- ) 2 Nepheline (low T), carnegieite (high T) (Al 3+, Si 4+ ) 2 Va 0 1 (Na1+, Va 0 ) 1 (O 2- ) 4 NaAlO 2 - low T, high T (Al 3+, Si 4+ ) 1 (Na 1+, Va 0 ) 1 (O 2- ) 2 (Fe is by GTT considered) K 2 MgSiO 4 - Reciprocal: (Mg 2+,Si 4+ ) 1 (Si 4+ ) 1 (K 1+,Va 0 ) 2 (O 2- ) 4 Beta alumina (Na 1+,K 1+ ) 1 (Al 3+ ) 9 (O 2- ) 14 Beta`` alumina (Na 1+,K 1+ ) 1 (Al 3+ ) 12 (O 2- ) 19 (Mg is by GTT considered) Feldspar (Na 1+,K 1+ ) 1 (Al 3+ ) 1 (Si 4+ ) 3 (O 2- ) 8 GTT-Technologies, 13th Annual Workshop, September 2011 Folie 4

5 Database development Experimental data: phase diagram data, activity data (if they are available) Choice of the suitable model Initial data for pure solid and liquid substances, liquid and solid solution components disagreement OptiSage in Adjustable parameters: ΔH 298 f and S 298 for the liquid and solid solution species ΔH 298 f and S 298 for the pure solid compounds (part.) interaction parameters between species optimisation Comparison of the results with exp. data Re-assessment: Gibbs energy for pure oxides were changed from FACT to SGTE Pure Substance database New dataset agreement GTT-Technologies, 13th Annual Workshop, September 2011 Folie 5

6 Results of re-assessment for binary systems-1 Alk 2 O-, Alk=Na, K Alk 2 O-Al 2, Alk=Na, K Temperature, C Morey Kracek Loeffler Haller Na 4 SiO 4 Na 6 Si 2 O 7 Na 2 Si Na 2 Si 2 O 5 Na 6 Si 8 O 19 Temperature, C Rolin, Thanh 2100 De Vries, Roth Weber, Venero liquid Al 2 ) - Al 2 ) Na 2 O NaAlO 2 Na 2 Al 12 O 19 NaAl 9 O Al 2O3 - Al 2O3) mole / +Na 2 O mole Al 2 /Al 2 +Na 2 O Temperature, C Kracek Liquid K 2SiO3 K 2Si2O5 K 2 Si 4 O Temperature, C K 2 O Roth Moya KAlO 2 K 2 Al 12 O 19 Al 2 ) Al 2 ) KAl 9 O 14 Al 2O3 Al2O3) mole / +K 2 O mole Al 2 /Al 2 +K 2 O GTT-Technologies, 13th Annual Workshop, September 2011 Folie 6

7 Results of re-assessment for binary systems-2 Mullite Temperature, C Welch Aramaki, Roy Horibe, Kuwabara Klug et al. Aksay, Pask eut K Associate species model (introduced by Spear at al. in 2002): Al 6 Si 2 O 13 1/4, Al 2, 2 4 sublattice model (introduced by Mao et al. in 2005): (Al 3+ ) 1 (Al 3+ ) 1 (Al 3+, Si 4+ ) 1 (O 2-, Va) 5 Prochazka, Klug Okada 1987 Hamano 1986 SMIM + (s4) slag + SMIM SMIM mole Al 2 /Al 2 + Galachov et al. MacDowell, Beall Risbud, Pask (1977) slag + Al 2 (s) Incong K Exp(Klug) K SMIM+ Al 2 (s) Model parameters are optimised for both melting behaviour of mullite GTT-Technologies, 13th Annual Workshop, September 2011 Folie 7 Temperature, C Temperature, C Congruent SMCM Incongruent SMIM

8 Assessment for ternary system Na 2 O-K 2 O- Predicted phase fields and ternary points K 2 O - Na 2 O - Na 2 O Four-Phase Intersection Points with Slag F.C. Kracek, The ternary system K 2 Si - Na 2 Si -, J. Phys. Chem., 36 [10], (1932), Interacting components: Na 2 Si *2/3 - K 2 Si *2/3 Na 2 Si 2 O 5 *1/2 - K 2 Si 2 O 5 *1/2 Na 2 Si *2/3 - K 2 Si 2 O 5 *1/2 Na 2 Si 2 O 5 *1/2 - K 2 Si *2/3 1: 2: 3: 4: 5: 6: 7: 8: 9: 10: 11: 12: 1: 2: 3: 4: 5: 6: 7: 8: 9: 10: 11: 12: Si2Na6O7_solid(s) / SiNa2O3_solid(s) / SiNa4O4_solid(s) Na2O_s1(gamma)(s) / Na2O_s2(beta)(s2) / SiNa4O4_solid(s) (Na,K)2Si2O5 / Si2Na2O5_solid-(s3) / SiNa2O3_solid(s) (Na,K)2Si2O5 / Si2Na2O5_solid-(s3) / Si8Na6O19_solid(s) K2SiO3_solid(s) / SiNa2O3_solid(s) / SiNa4O4_solid(s) (Na,K)2Si2O5 / K2Si2O5_solid-c(s3) / SiNa2O3_solid(s) (Na,K)2Si2O5 / Si8Na6O19_solid(s) / SiO2_quartz_beta(s3) K2Si2O5_solid-c(s3) / K2SiO3_solid(s) / SiNa2O3_solid(s) K2O_s3(solid)(s3) / Na2O_s1(gamma)(s) / SiNa4O4_solid(s) (Na,K)2Si2O5 / K2Si4O9_solid-b(s2) / SiO2_quartz_beta(s3) (Na,K)2Si2O5 / K2Si2O5_solid-c(s3) / K2Si4O9_solid-b(s2) K2O_s3(solid)(s3) / K2SiO3_solid(s) / SiNa4O4_solid(s) A = Na2O, B = K2O, C = SiO2 W(A) W(B) W(C) o C K 2 O(s3) 12 2 K 2 Si (s) Na 2 O SiNa 4 O 4 (s) mass fraction SiNa 2 (s) K 2 Si 2 O 5 (s3) Si 2 Na 6 O 7 (s) 6 11 Na 4 SiO Na 6 Si 2 O 7 Si 2Na 2O 5(s3) Na 2 Si 4 Na 2 Si 2 O 5 (s5) Na 6 Si 8 O 19 K 2 Si 4 O 9 (s) K 2 O SiO K 2 Si K 2 Si 2 O 5 K 2 Si 4 O 2 9 GTT-Technologies, 13th Annual Workshop, September 2011 Folie 8

9 Quasi binary section in the Na 2 O-K 2 O- system K 2 Si - Na 2 Si Temperature, C Kracek Liquid + K 2 Si (s) Liquid Liquid + Na 2 Si (s) Na 2 (s) + K 2 Si (s) Free energy of mixing, J/ mole fraction of Na metasilicate Metasilicate, exp [Belton et al] calculated, our database calculated, FACT database mass percent Na 2 Si /Na 2 Si +K 2 Si K 2 Si 2 O 5 - Na 2 Si 2 O 5 Temperature, C Kracek Liquid + K 2 Si 2 O 5 (s3) Liquid Free energy of mixing, J/ mole fraction of Na disilicate Disilicate, exp [Belton et al] calculated, our database calculated, FACT database mass percent Na 2 Si 2 O 5 /Na 2 Si 2 O 5 +K 2 Si 2 O 5 [Belton et al.] G.R. Belton, U.V. Choudary, D.R. Gaskell, Thermodynamics of mixing in molten sodium-potassium silicates, Phys. Chem.Process. Metall., Richardson Conf., (1974), GTT-Technologies, 13th Annual Workshop, September 2011 Folie 9

10 Assessment for ternary system K 2 O-Al Al 2 - K 2 O J.F. Schairer, N.L. Bowen, The system K 2 O-Al 2 -, Am. J. Sci. 253 (1955) Interacting components Al 2 KAlSi 2 O 6 *1/2 K 2 Si 2 O 5 *1/2 - KAlSi 2 O 6 *1/2 Si 2 O 4 *1/2 - KAlSi 2 O 6 *1/2 Al 6 Si 2 O 13 *1/4 - KAlSi 2 O 6 *1/2 K 2 Si *2/3 - KAlSi 2 O 6 *1/2 K 2 Si 4 O 9 *1/3 - KAlSi 2 O 6 *1/2 - KAlO : 2: 3: 4: 5: 6: 7: 8: 9: 10: 11: 12: 13: 14: 15: 16: 1: 2: 3: 4: 5: 6: 7: 8: 9: 10: 11: 12: 13: 14: 15: 16: Four-Phase Intersection Points w ith Slag (K,Na)(Fe,Al)O2_HT / Al2O3_alpha(s) / KAl9O14_k-beta-alumin(s) (K,Na)(Fe,Al)O2_HT / Al2O3_alpha(s) / K4Si3Al4O14_tetragon(s) Al2O3_alpha(s) / K4Si3Al4O14_tetragon(s) / KSiAlO4_kaliophyllit(s2) Al2O3_alpha(s) / KSi2AlO6_leucite(rhf(s2) / KSiAlO4_kaliophyllit(s2) Al2O3_alpha(s) / KSi2AlO6_leucite(rhf(s2) / Mullite KSi2AlO6_leucite(rhf(s2) / KSi3AlO8_k-feldspar(s2) / Mullite KSi3AlO8_k-feldspar(s2) / Mullite / SiO2_cristobalite_be(s5) (K,Na)(Fe,Al)O2_HT / K2SiO3_solid(s) / K4Si3Al4O14_tetragon(s) K2SiO3_solid(s) / K4Si3Al4O14_tetragon(s) / KSiAlO4_kaliophyllit(s2) KSi3AlO8_k-feldspar(s2) / SiO2_cristobalite_be(s5) / SiO2_quartz_beta(s3) K2Si2O5_solid-c(s3) / KSi2AlO6_leucite(rhf(s2) / KSiAlO4_kaliophyllit(s2) K2Si2O5_solid-c(s3) / KSi2AlO6_leucite(rhf(s2) / KSi3AlO8_k-feldspar(s2) K2Si2O5_solid-c(s3) / K2SiO3_solid(s) / KSiAlO4_kaliophyllit(s2) K2Si4O9_solid-b(s2) / KSi3AlO8_k-feldspar(s2) / SiO2_quartz_beta(s3) K2Si2O5_solid-c(s3) / K2Si4O9_solid-b(s2) / KSi3AlO8_k-feldspar(s2) (K,Na)(Fe,Al)O2_HT / K2O_s3(solid)(s3) / K2SiO3_solid(s) A = SiO2, B = K2O, C = Al2O3 W(A) W(B) W(C) o C (K,Na)(Fe,Al)O2_HT K 2 O KAl 9 O 14 K 2 Al 12 O 19 Al 2 mass fraction KAlSi3O8 K KAlSi 2 O 6 2 Si 2 O 5 K 2 Si K 2 Si K 2 Si 4 O 9 K 2 Si 4 O 9 K2Si2O5 KAlSiO 4 K4Si3Al4O14(s) KAlO 2 Mullite 4 KAlSi 3 O 8 (k-feldspar) KAlSi 2 O 6 - K 2 Si 2 O KAlSi 2 O 6 (leucite) KAlSiO 4 K 4 Si 3 Al 4 O 14 Al 2 (s) Al 3 Si 2 O 13 KAl 9 O 14 R.S. Roth, Phase equilibrium research in portions of the potassium oxidemagnesium oxide-iron (III) oxidealuminium oxide-silicon dioxide system, Adv. Chem. 186 (1980) T(C) (K,Na)(Fe,Al)O2_HT Slag (K,Na)(Fe,Al)O2_HT + K4Si3Al4O14(s) K 4 Si 3 Al 4 O 14 KSiAlO 4 KSi 2 AlO 6 Schairer, Bowen (1955) Extrapol.line, Roth (1980) Roth, exp. no melting Roth, exp. partially melting Roth, exp. completely melting KSi 3 AlO 8 Slag Slag + (s5) (s3) + KSi 3AlO 8(s2) KSi 3AlO 8(s2) + (s2) mass /( +KAlO 2 ) T(C) K 2 Si 2 O 5 Schairer, Bowen slag 905 K 2 Si 2 O 5 + KAlSi 2 O 6 (s) mass KAlSi 2 O 6 /(KAlSi 2 O 6 +K 2 Si 2 O 5 ) 1683 KAlSi 2 O 6 (s2) GTT-Technologies, 13th Annual Workshop, September 2011 Folie 10

11 Assessment for ternary system Na 2 O-Al Al 2 - Na 2 O J.F. Schairer, N.L. Bowen, The system Na 2 O-Al 2 -, Am. J. Sci. 254(2) (1956) Interacting components Al 2 NaAlSi 3 O 8 *2/5 Na 2 Si 2 O 5 *1/2 NaAlSi 3 O 8 *2/5 Na 2 Si 2 O 5 *1/2 NaAlSiO 4 *2/3 Si 2 O 4 *1/2 NaAlSi 3 O 8 *2/5 Si 2 O 4 *1/2 NaAlSiO 4 *2/3 Na 2 Si *2/3 NaAlSi 3 O 8 *2/5 Na 2 Si *2/3 NaAlSiO 4 *2/3 Na 2 Si *2/3 NaAlO 2 NaAlSi 3 O 8 *2/5-NaAlSiO 4 *2/3 NaAlO 2 - NaAlSiO 4 *2/3 Si 2 O 4 *1/2 Na 2 Si 2 O 5 /1/2 - NaAlSi 3 O 8 *2/5 1: 2: 3: 4: 5: 6: 7: 8: 9: 10: 11: 12: 13: 14: 15: 16: 17: 18: 19: 20: 21: 22: 1: 2: 3: 4: 5: 6: 7: 8: 9: 10: 11: 12: 13: 14: 15: 16: 17: 18: 19: 20: 21: 22: Four-Phase Intersection Points with Slag (K,Na)(Fe,Al)O2_HT / Al12Na2O19_beta2-alum(s) / Al9NaO14_beta-alumina(s) (K,Na)(Fe,Al)O2_HT / Al9NaO14_beta-alumina(s) / Carnegieite Al2O3_alpha(s) / Al9NaO14_beta-alumina(s) / Carnegieite Al2O3_alpha(s) / Carnegieite / Nepheline (K,Na)(Fe,Al)O2_HT / Carnegieite / Nepheline (K,Na)(Fe,Al)O2_HT / (K,Na)(Fe,Al)O2_LT / Nepheline Al2O3_alpha(s) / Mullite / Si3AlNaO8_high-albit(s2) Al2O3_alpha(s) / Nepheline / Si3AlNaO8_high-albit(s2) Mullite / Si3AlNaO8_high-albit(s2) / SiO2_cristobalite_be(s5) (K,Na)(Fe,Al)O2_HT / Na2O_s2(beta)(s2) / Na2O_s3(alpha)(s3) (K,Na)(Fe,Al)O2_HT / Si2Na6O7_solid(s) / SiNa4O4_solid(s) (K,Na)(Fe,Al)O2_HT / Na2O_s2(beta)(s2) / SiNa4O4_solid(s) Si3AlNaO8_high-albit(s2) / SiO2_cristobalite_be(s5) / SiO2_quartz_beta(s3) (K,Na)(Fe,Al)O2_HT / (K,Na)(Fe,Al)O2_LT / Si2Na6O7_solid(s) (K,Na)(Fe,Al)O2_LT / Si2Na6O7_solid(s) / SiNa2O3_solid(s) (K,Na)(Fe,Al)O2_LT / Nepheline / SiNa2O3_solid(s) Si2Na2O5_solid-(s3) / Si3AlNaO8_high-albit(s2) / Si8Na6O19_solid(s) Si3AlNaO8_high-albit(s2) / Si8Na6O19_solid(s) / SiO2_quartz_beta(s3) Si2Na2O5_solid-(s2) / Si2Na2O5_solid-(s3) / SiNa2O3_solid(s) Si2Na2O5_solid-(s2) / Si2Na2O5_solid-(s3) / Si3AlNaO8_high-albit(s2) Nepheline / Si2Na2O5_solid-(s2) / Si3AlNaO8_high-albit(s2) Nepheline / Si2Na2O5_solid-(s2) / SiNa2O3_solid(s) NaAl O 14 Na 2 O NaAlO 2 Na 2 Al 12 O 19 Al 2 Predicted phase fields and ternary points A = SiO2, B = Na2O, C = Al2O3 W(A) W(B) W(C) o C Neph Na 2 Si SiNa2O3(s) NaAlSiO Na 6 Si 2 O 7 Carn Si2Na6O7(s) Na SiO Al 6 Si 3 O Na 6 Si 8 O 19 Na 2 Si 2 O 5 mass fraction Si2Na2O5(s3) SiO2(s5) 13 Si3AlNaO8 (K,Na)(Fe,Al)O2_HT Mullite Al9NaO14(s) 1 NaAlSi 3 O 8 Al2O3(s) T(K) exp. Scairer (1956) extrapolated Neph-NaAlSi2O6 + Al 6Si 2O 13(s) + NaAlSi 3O 8(s2) Al 2 - NaAlSi 3 O 8 slag slag + Al 2(s4) mass Al 2 /(Al 2 +NaAlSi 3 O 8 ) GTT-Technologies, 13th Annual Workshop, September 2011 Folie 11

12 Results of the assessment for the system NaAlO 2 - NaAlSi 3 O 8 (Albite) - Schairer and Bowen (1956) NaAlSiO 4 NaAlSi 3 O 8 Greig, Barth(1938) 1526 C 1526 C NaAlSiO 4 -NaAlO 2 Schairer and Bowen (1956) 1118 C - NaAlO 2 Sublattice solutions are added: (Al 3+, Si 4+, Fe 3+ ) 1 (Na 1+, K 1+,Va 0 ) 1 (O 2- ) 2 for NaAlO 2 (low T, high T) (Al 3+, Si 4+ ) 2 (Va 0 ) 1 (Na 1+, Va 0 ) 1 (O 2- ) 4 for NaAlSiO 4 (Neph, Carn) Problems: T(K) (K,Na)(Fe,Al)O2_HT exp.data, Greig and Barth (1938) exp.data, Schairer and Brown (1956) Slag (K,Na)(Fe,Al)O2_HT + Carn Slag + Neph Slag + (s5) Nepheline Si 3AlNaO 8(s2) + (s5) Si 3 AlNaO 8 (s2) + (s3) (K,Na)(Fe,Al)O2_LT + Neph Nepheline + Si3AlNaO8(s2) Unknown solubility boundaries for NaAlO 2 (low T, high T) solutions Nepheline + Si 3AlNaO 8(s) mole /( +NaAlO 2 ) GTT-Technologies, 13th Annual Workshop, September 2011 Folie

13 Feldspar section in the quaternary system Na 2 O-K 2 O-Al 2 - KAlSiO 4 - NaAlSiO 4 Interacting components in liquid NaAlSi 3 O 8 *2/5 - KAlSi 2 O 6 *1/2 NaAlSi 3 O 8 - KAlSi 3 O Schairer (1950) Waldbaum(1969) strain-free solvus Slag + KSi 2 AlO 6 (s2) Slag T(C) 1000 Slag + FSPA 800 FSPA 600 FSPA + FSPA#2 Schairer, J.F., The alkali-feldspar join in the system NaAlSiO 4 -KAlSiO 4 -, J. Geol. 58 (5) (1950 ) mass NaAlSi 3 O 8 /(NaAlSi 3 O 8 +KAlSi 3 O 8 ) Sublattice solution (Al 3+ ) 1 (Na 1+, K 1+ ) 1 (Si 4+ ) 3 (O 2- ) 8 for feldspar is added. GTT-Technologies, 13th Annual Workshop, September 2011 Folie 13

14 Ternary system K 2 O-MgO- Liquid binary associate species K 2 O-, MgO-K 2 O, MgO- are kept new ternary species are introduced: (K 2 MgSiO 4 )/2, (K 2 MgSi 5 O 12 )/4 new interaction parameters between binary and ternary species are added Solids binary compounds from K 2 O-, MgO-K 2 O, MgO- are kept new ternary compounds (K 2 MgSiO 4, K 2 MgSi 3 O 8, K 2 MgSi 5 O 12, E.W. Roedder, The system K 2 O-MgO-, Am. J. Sci. 249(2) (1951) K 2 Mg 5 Si 12 0, K 4 Mg 2 Si 5 O 14, K 10 Mg 5 Si 11 2 ) are introduced reciprocal solid solution (Mg 2+,Si 4+ ) 1 (Si 4+ ) 1 (K 1+,Va 0 ) 2 (O 2- ) 4 is added Interacting components in liquid Si 2 O 4 *1/2 K 2 MgSi 5 O 12 *1/4 MgSi -K 2 MgSiO 4 *1/2 MgSi -K 2 MgSi 5 O 12 *1/4 K 2 MgSiO 4 *1/2 - K 2 MgSi 5 O 12 *1/4 Si 2 O 4 *1/2 MgSi -K 2 MgSi 5 O 12 *1/4 System K 2 O-MgO- ; various binary sub-systems System MgO SiO2-K 2 O 5MgO 12 ; partially binary; K 2 O 7 not a compound GTT-Technologies, 13th Annual Workshop, September 2011 Folie 14

15 Assessment for ternary system K 2 O-MgO- - KMg 0.5 Si 0.5 O KMS 3 - Roedder (1951); KMS-KMS 3 Roth (1980) 1400 K 4 Mg 2 Si 5 O 14 (s) T(C) Tet Ort eut A`, 1030 C Mon 1: 2: 3: 4: 5: 6: 7: 8: 9: 10: 11: 12: 13: 14: 15: 16: 17: 18: 19: 20: 1: 2: 3: 4: 5: 6: 7: 8: 9: 10: 11: 12: 13: 14: 15: 16: 17: 18: 19: 20: Four-Phase Intersection Points w ith Slag SiMgO3_clinoenstatite(s) / SiO2_cristobalite_be(s5) / SiO2_liq(s) KMS-SiO2 / MgO_solid(s2) / SiMg2O4_forsterite(s) K10Si11Mg5O32_tetrago(s) / KMS-SiO2 / SiMg2O4_forsterite(s) K10Si11Mg5O32_tetrago(s) / K4Si5Mg2O14_ortho(s) / SiMg2O4_forsterite(s) K2Si12Mg5O30_roedderi(s) / SiMg2O4_forsterite(s) / SiMgO3_protoenstatit(s4) K2Si12Mg5O30_roedderi(s) / SiMgO3_protoenstatit(s4) / SiO2_cristobalite_be(s5) K2Si12Mg5O30_roedderi(s) / K2Si5MgO12_solid(s) / SiMg2O4_forsterite(s) K2Si5MgO12_solid(s) / K4Si5Mg2O14_ortho(s) / SiMg2O4_forsterite(s) K2Si3MgO8_solid(s) / K2Si5MgO12_solid(s) / K4Si5Mg2O14_ortho(s) K2Si12Mg5O30_roedderi(s) / K2Si5MgO12_solid(s) / SiO2_cristobalite_be(s5) K10Si11Mg5O32_tetrago(s) / K2Si2O5_solid-c(s3) / KMS-SiO2 K10Si11Mg5O32_tetrago(s) / K2Si3MgO8_solid(s) / K4Si5Mg2O14_ortho(s) K2Si5MgO12_solid(s) / SiO2_cristobalite_be(s5) / SiO2_quartz_beta(s3) K10Si11Mg5O32_tetrago(s) / K2Si2O5_solid-c(s3) / K2Si3MgO8_solid(s) K2Si2O5_solid-c(s3) / K2Si3MgO8_solid(s) / K2Si5MgO12_solid(s) K2Si2O5_solid-c(s3) / K2SiO3_solid(s) / KMS-SiO2 K2O_s3(solid)(s3) / KMS-SiO2 / MgO_solid(s2) K2Si4O9_solid-b(s2) / K2Si5MgO12_solid(s) / SiO2_quartz_beta(s3) K2Si2O5_solid-c(s3) / K2Si4O9_solid-b(s2) / K2Si5MgO12_solid(s) K2O_s3(solid)(s3) / K2SiO3_solid(s) / KMS-SiO2 A = SiO2, B = MgO, C = K2O W(A) W(B) W(C) o C K 2 O - MgO MgSi KMS 3 Mg 2 SiO KMS KM 5 S 12 K 2 Si 4 O K 2 Si 2 O 5 16 KMS 5 K 2 M 2 S 5 K 2 Si 20 K 5 M 5 S Hex K 2 MgSiO 4 (s) K 10 Mg 5 Si 11 2 (s) K 2 MgSi 3 O 8 (s) K 2 MgSi 5 O 12 (s) mole /( +KMg 0.5 Si 0.5 O 2 ) MgSi - K 2 Si 7 O T(C) exp. data-roedder (1951) Slag Slag + SiMg 2O4(s) Slag + SiMgO3(s4) + SiMg2O4(s) Slag + SiMgO3(s4) SiMg(s4) + K 2Si 12Mg 50(s) K 2Si 12Mg 50(s) + SiMg(s3) K 2Si12Mg5O30(s) + SiMgO3(s2) K 2 Si 12 Mg 5 0 Slag + K 2Si 12Mg 50(s) Slag + (s5) K2Si12Mg5O30(s) + SiO2(s3) + K2Si5MgO12(s) MgO mass fraction K 2 O K2Si12Mg5O30(s) + K2Si5MgO12(s) + SiO2(s2) mass K 2 Si 7 O 15 /(MgSi +K 2 Si 7 O 15 ) GTT-Technologies, 13th Annual Workshop, September 2011 Folie 15

16 Ternary system K 2 O-CaO CaO - - K 2 O mass fraction CaO Ca 3 SiO 5 Ca 2 SiO 4 Ca 3 Si 2 O 7 CaSi K 2 CaSiO 4 K 2 Ca 2 Si 6 O 15 K 4 CaSi 3 O 9 (K2Ca23Si12O48) (K 2Ca 6Si 4O 15) K 2 Ca 2 Si 9 O K 2 O K 2 Si K 2 Si 2 O K 2 Si 4 O 9 5 K 4 CaSi 6 O 15 K 8 CaSi 10 O 25 Morey, Kracek (1930) Kahlenberg (2006) Taylor (1941) E. Arroyabe (2009) K 2 Ca 3 Si 6 O 16 G.W. Morey, F.C. Kracek, N.L. Bowen, The ternary system K 2 O-CaO-,J. Soc. Glass Technol. 14 (1930) Liquid binary associate species K 2 O-, CaO-K 2 O, CaO- are kept new ternary species are introduced: (K 2 CaSiO 4 )/2 new interaction parameters between binary and ternary species are added Solids binary compounds from K 2 O-, CaO-K 2 O, CaO- are kept new ternary compounds (K 2 CaSiO 4, K 4 CaSi 3 O 9,K 2 Ca 2 Si 9 O 21, K 8 CaSi 10 O 25, K 4 CaSi 6 O 15, K 2 Ca 2 Si 6 O 15, K 2 Ca 3 Si 6 O 16 ) are introduced Interacting components in liquid K 2 Si *2/3 CaSi K 2 Si *2/3 CaO K 2 O Ca 2 O 2 K 2 Si 2 O 5 *1/2 CaSi K 2 Si *2/3 Ca 2 SiO 4 *2/3 K 2 Si 2 O 5 *1/2 Si 2 O 4 *1/2 - CaSi GTT-Technologies, 13th Annual Workshop, September 2011 Folie 16

17 Current results for ternary system K 2 O-CaO CaSi 2 O 5 - K 2 Si 2 O CaSi 2 O 5 T(C) K 2 Si 2 O 5 K 8 CaSi 10 O 25 K 4 CaSi 6 O mass CaSi 2 O 5 /(CaSi 2 O 5 +K 2 Si 2 O 5 ) CaSi - K 2 Si 4 O 9 CaO - - K 2 O Four-Phase Intersection Points with Slag#1'2 1: Ca2SiO4_alpha(s2) / Ca2SiO4_alpha_prime(s3) / CaK2SiO4_solid(s) 2: Ca2SiO4_alpha(s2) / Ca2SiO4_alpha_prime(s3) / Ca3SiO5_hatrurite(s) 3: Ca2SiO4_alpha(s2) / Ca2SiO4_alpha_prime(s3) / CaK2SiO4_solid(s) 4: 5: 6: 7: 8: 9: 10: 11: 12: 13: 14: 15: 16: 17: 18: 19: 20: 21: 22: 23: 24: 25: 26: 27: 28: 29: 30: 31: 32: 1: 2: 3: 4: 5: 6: 7: 8: 9: 10: 11: 12: 13: 14: 15: 16: 17: 18: 19: 20: 21: 22: 23: 24: 25: 26: 27: 28: 29: 30: 31: 32: Ca2SiO4_alpha(s2) / Ca2SiO4_alpha_prime(s3) / Ca3Si2O7_rankinite(s) Ca2SiO4_alpha_prime(s3) / Ca3SiO5_hatrurite(s) / CaO_solid(s2)(s) Ca2SiO4_alpha_prime(s3) / Ca3Si2O7_rankinite(s) / CaK2SiO4_solid(s) Ca3Si2O7_rankinite(s) / CaSiO3_pseudowollast(s2) / CaSiO3_wollastonite(s) CaSiO3_pseudowollast(s2) / CaSiO3_wollastonite(s) / SiO2_tridymite_gamma(s3) Ca2K2Si9O21_solid(s) / CaSiO3_wollastonite(s) / SiO2_tridymite_gamma(s3) Ca2K2Si6O15_solid(s) / Ca2K2Si9O21_solid(s) / CaSiO3_wollastonite(s) Ca3Si2O7_rankinite(s) / CaK2SiO4_solid(s) / CaSiO3_wollastonite(s) Ca2K2Si6O15_solid(s) / Ca3K2Si6O16_solid(s) / CaSiO3_wollastonite(s) CaK2SiO4_solid(s) / CaK4Si3O9_solid(s) / CaSiO3_wollastonite(s) Ca2K2Si6O15_solid(s) / Ca3K2Si6O16_solid(s) / CaK4Si6O15_solid(s) Ca3K2Si6O16_solid(s) / CaK4Si3O9_solid(s) / CaSiO3_wollastonite(s) CaK4Si3O9_solid(s) / CaK8Si10O25_solid(s) / K2Si2O5_solid-c(s3) CaK4Si3O9_solid(s) / CaK4Si6O15_solid(s) / CaK8Si10O25_solid(s) Ca3K2Si6O16_solid(s) / CaK4Si3O9_solid(s) / CaK4Si6O15_solid(s) CaK2SiO4_solid(s) / CaK4Si3O9_solid(s) / K2SiO3_solid(s) Ca2K2Si9O21_solid(s) / SiO2_quartz_beta(s3)(s2) / SiO2_tridymite_gamma(s3) Ca2K2Si6O15_solid(s) / Ca2K2Si9O21_solid(s) / CaK4Si6O15_solid(s) Ca2SiO4_alpha_prime(s3) / Ca2SiO4_olivine_gamma(s) / CaK2SiO4_solid(s) Ca2SiO4_alpha_prime(s3) / Ca2SiO4_olivine_gamma(s) / CaO_solid(s2)(s) Ca2SiO4_olivine_gamma(s) / CaK2SiO4_solid(s) / CaO_solid(s2)(s) CaK4Si3O9_solid(s) / K2Si2O5_solid-c(s3) / K2SiO3_solid(s) Ca2K2Si9O21_solid(s) / CaK4Si6O15_solid(s) / CaK8Si10O25_solid(s) Ca2K2Si9O21_solid(s) / K2Si4O9_solid-b(s2) / SiO2_quartz_beta(s3)(s2) CaK8Si10O25_solid(s) / K2Si2O5_solid-c(s3) / K2Si4O9_solid-b(s2) Ca2K2Si9O21_solid(s) / CaK8Si10O25_solid(s) / K2Si4O9_solid-b(s2) CaK2SiO4_solid(s) / K2O_s3(solid)(s3) / K2SiO3_solid(s) CaK2SiO4_solid(s) / K2O_s2(solid)(s2) / K2O_s3(solid)(s3) CaK2SiO4_solid(s) / CaO_solid(s2)(s) / K2O_s2(solid)(s2) A = CaO, B = K2O, C = SiO2 W(A) W(B) W(C) o C mass fraction CaO K 2 Ca 2 Si 6 O 15 K 2 CaSiO K 4 CaSi 3 O K 2 O K 2 Si K 2 Si 2 O K 2 Si 4 O Ca 3 SiO 5 21 Ca 2 SiO 4 4 Morey, Kracek (1930) Ca 3 Si 2 O K8 CaSi 10 O CaSi K 2 Ca 3 Si 6 O 16 K 4 CaSi 6 O 15 K 2 Ca 2 Si 9 O 21 T(C) K 2 CaSiO 4 T(C) K 2 CaSi 3 O 9 K 2 Si 4 O 9 K2Ca2Si 9O mass CaSi /(CaSi +K 2 Si 4 O 9 ) K 2 Si 2 O 5 - K 2 CaSiO 4 K 2 Ca 2 Si 6 O 15 CaSi mass K GTT-Technologies, 13th Annual Workshop, September Si 2 O 5 /(K 2 Si 2 O 5 +K 2 CaSiO 4 ) Folie 17

18 Conclusions The solution data for the binary systems Alk 2 O-, Alk 2 O-Al 2 (Alk=Na, K) and Al 2 - were re-optimised to accurate description of the phase diagrams taking into account the changes concerning the data on the pure liquid oxides Solid and liquid solutions in the ternary systems Na 2 O-K 2 O-, Alk 2 O-Al 2 - (Alk=Na, K) and quaternary Na 2 O-K 2 O-Al 2 - as well were described using the new database Sublattice model was successfully applied for the solid solutions in the many-component systems The ternary systems concerning earth alkali oxides are considered. The corresponding thermodynamic data on the new ternary compounds and the liquid and solid solutions are added in order to calculate the ternary phase diagrams GTT-Technologies, 13th Annual Workshop, September 2011 Folie 18

19 Outlook Assessment of the system NaAlSiO 4 -KAlSiO 4 - system Creation of the database for quaternary solutions with the compositions (Na, K)(Al, Si)O 4 and different structures Alk 2 O-MgO- (Alk=Na, K) systems should be finished Further fusion of the thermodynamic data on earth alkali- and alkali-containing parts of the slag relevant system NaAlSiO 4 KAlSiO 4 Mg 2 SiO 4 (Fo) Temperature, C CaAl 2 Si 2 O 8 (An) mass percent KAlSiO 4 /NaAlSiO 4 +KAlSiO 4 KAlSi 2 O 6 KAlSi 2 O 6 (Leu) GTT-Technologies, 13th Annual Workshop, September 2011 Folie 19

20 g{tç~ çéâ yéü çéâü tààxçà ÉÇ GTT-Technologies, 13th Annual Workshop, September 2011 Folie 20