Effect of Silicate Structure on Thermodynamic Properties of Calcium Silicate Melts: Quantitative Analysis of Raman Spectra

다국어 초록 (Multilingual Abstract)

The distribution of silicate anionic species (Qn units, n=0, 1, 2, 3) and the chemical speciation of oxygen in CaO-SiO2-MO (M=Mn and Mg) slags were investigated by micro-Raman spectroscopic analysis. Furthermore, the thermochemical properties were evaluated using a concentration of free oxygen and a degree of polymerization. A good linear relationship was obtained between sulfide capacity and concentration of free oxygen in the CaO–SiO2 (-MnO) melts at 1500 to 1600 °C. However, even though there was more abundant free oxygen in the CaO-SiO2-MgO system than in the CaO-SiO2 system, the sulfide capacity of the former was lower than the latter, indicating that the sulfur dissolution behavior in the silicate melts cannot be simply explained by the content of free oxygen, because the composition dependency of the stability ratio of oxygen and sulfide ions should be taken into account. The excess free energy of CaO, MgO and MnO linearly decreased as the ln (Q3/Q2) increased. The effect of the degree of polymerization on the excess free energy of mixing of MgO-containing slag was larger than that of MnO-containing slag, which was explained by the difference of the ionization potential between Mn2+ and Mg2+ ions.

참고문헌 (Reference)

1 J. F. Stebbins, 330 : 465-, 1987

2 J. Lee, 52 : 2145-, 2012

3 J. S. Park, 43 : 1550-, 2012

4 J. H. Heo, 43 : 1098-, 2012

5 D. J. Kim, 43 : 875-, 2012

6 K. Y. Ko, 43 : 440-, 2012

7 K. Y. Ko, 42 : 1224-, 2011

8 J. H. Park, 35 : 455-, 2011

9 C. J. B. Fincham, 178 : 4-, 1954

10 K. P. Abraham, 196 : 309-, 1960

11 R. G. Reddy, 18 : 591-, 1987

12 M. M. Nzotta, 24 : 300-, 1997

13 J. H. Park, 47 : 2038-, 2006

14 Y. B. Kang, 40 : 979-, 2009

15 M. K. Cho, 50 : 215-, 2010

16 G. H. Park, 51 : 1375-, 2011

17 Y. B. Kang, 42 : 1211-, 2011

18 J. H. Park, 52 : 764-, 2012

19 C. R. Masson, 48 : 1456-, 1970

20 A. K. Lahiri, 67 : 2952-, 1971

21 L. M. Barron, 57 : 809-, 1972

22 G. R. Belton, 4 : 2541-, 1973

23 D. R. Gaskell, 8 : 131-, 1977

24 P. C. Hess, 15 : 162-, 1977

25 M. S. Ghiorso, 84 : 107-, 1983

26 G. Ottonello, 282 : 72-, 2001

27 T. Furukawa, 75 : 3226-, 1981

28 S. A. Brawer, 63 : 2421-, 1975

29 S. A. Brawer, 23 : 261-, 1977

30 D. Virgo, 208 : 1371-, 1980

31 B. O. Mysen, 65 : 690-, 1980

32 P. McMillan, 69 : 622-, 1984

33 B. O. Mysen, 27 : 281-, 1990

34 C. M. Schramm, 106 : 4396-, 1984

35 R. D. Shannon, 32 : 751-, 1976

36 J. F. Stebbins, 390 : 60-, 1997

37 I. Georgieva, 31 : 3197-, 1996

38 I. Zebger, 351 : 3443-, 2005

39 K. A. Evans, 73 : 6847-, 2009

40 J. H. Park, 30 : 3181-, 2010

41 J. H. Park, 50 : 1078-, 2010

42 E. J. Jung, 45 : 2023-, 2010

43 A. Chrissanthopoulos, 48 : 118-, 2008

44 P. McMillan, 69 : 645-, 1984

45 Y. Q. Wu, 121 : 7883-, 2004

46 K. C. Mills, 33 : 148-, 1993

47 L. Zhang, 29 : 177-, 1998

48 J. H. Park, 282 : 7-, 2001

49 A. Bronson, 12 : 729-, 1981

50 C. W. Bale, 33 : 295-, 2009

51 M. O. Suk, 92 : 717-, 2009

52 Y. Waseda, "The Structure and Properties of Oxide Melts" World Scientific Publishing 1998

53 박주현, "The Effect of Boron Oxide on the Crystallization Behavior of MgAl2O4 Spinel Phase during the Cooling of the CaO-SiO2-10 mass.% MgO-30 mass.%Al2O3 Systems" 대한금속·재료학회 16 (16): 987-992, 2010

54 J. Etchepare, "Study by Raman Spectroscopy of Crystalline and Glassy Diopside, in Amorphous Materials" Wiley-Interscience 1972

55 K. C. Mills, "Slag Atlas, 2nd ed" Verlag Stahleisen GmbH 1995

56 B. O. Mysen, "Silicate Glasses and Melts: Properties and Structure" Elsevier 2005

57 박주현, "Phase Diagram Study for the CaO-SiO2-Cr2O3-5 mass.%MgO-10 mass.%MnO System" 대한금속·재료학회 15 (15): 677-681, 2009

58 C. H. P. Lupis, "Chemical Thermodynamics of Materials" Prentice Hall 1993

59 "CRCT-ThermFact and GTT-Technologies, FACTSAGE"