Abstract
Recent advances in the characterization of the glassy aluminosilicate phases in coal fly ashes are reviewed and discussed in terms of the development of new models describing their mechanism of formation, composition, structural relationships and chemical reactivity. Characterization techniques such as electron microscopy, x-ray diffraction, infrared and Raman spectroscopy, nuclear magnetic resonance and Mössbauer spectroscopies, thermal analysis, acid dissolution, silanation, and density fractionation have been used as experimental probes, and reveal a range of information relating to the glass phases from the macro, through the micro, to the nano-structural levels. Complex inter- and intra-particle heterogeneity in ash is observable not only in bulk chemical and mineralogical analyses but also at the molecular level in the constituent glasses. Remarkable relationships between ash particle size, density and glass composition have been observed and lead to a new proposed mechanism for ash morphogenesis based on temperature-viscosity effects in the mineral precursor melts in the boiler flame. A glass-ceramic model for fly ash particle structure is proposed and discussed in terms of phase relations in the CaO–SiO2–Al2O3 and FeO–Fe2O3–A12O3–SiO2 systems, modification of the aluminosilicate glasses by alkali and alkaline earth metal cations, and microheterogeneity involving glass devitrification and phase separation.
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References
P.J. Jackson, J. Appl. Chem. 1, 605, (1957).
H.S. Simons and J.W. Jeffery, J. Appl. Chem. 10, 328 (1960).
. J.D. Watt and D.J. Thorne, J. Appl. Chem. 15, 585 (1965).
E. Raask, J. Inst. Energy 52, 70 (1980); Trans. A.S.M.E., paper no. 81-JPGC-Fu-1, Oct. 1981.
L.D. Hulett and A.J. Weinberger, Env. Sci. Technol. 14, 965 (1980); L.D. Hulett, A.J. Weinberger, K.J. Northcutt and N.M. Ferguson, Science 210., 1356 (1980); L.D. Hulett, A.J. Weinberger, N.M. Ferguson, K.J. Northcutt and W.S. Lyon, in Trace Elements and Phase Relations in Fly Ash. EPRI Report EA-1822, May 1981.
S. Diamond, Cem. Conc. Research 13, 459 (1983).
. B. Mather, Cem. Conc. Research 14, 887 (1984).
M. van Roode and R.T. Hemmings, CANMET Contract Report No. ISQ83-00162, July 1985; E. Douglas, P. Mainwaring, M. van Roode and R.T. Hemmings, CANMET Report No. 85-6E, Oct. 1985; M. van Roode, E. Douglas and R.T. Hemmings, Cem. Conc. Research 17, 183(1987).
P.K. Mehta, Cem. Conc. Research 15, 669 (1985).
R.T. Hemmings and E.E. Berry, in Fly Ash and Coal Conversion Bv-Products: Characterization. Utilization and Disposal II. edited by G.J. McCarthy, F.P. Glasser, D.M. Roy and S. Diamond, Mat. Res. Soc. Symp. Proc. Vol. 65. (Materials Research Society, Pittsburgh, 1986) pp. 91–104.
H. Uchikawa, S. Uchida and S. Hanehara, Proc. 8th Int. Congress on the Chemistry of Cement. Vol. IV, Rio de Janeiro, Brazil, Sept. 22–27, 1986, pp. 245–250.
R.T. Hemmings, E.E. Berry, B.J. Cornelius and B.E. Scheetz, in Fly Ash and Coal Conversion By-Products: Characterization. Utilization and Disposal III, edited by G.J. McCarthy, F.P. Glasser and D.M. Roy, Mat. Res. Soc. Symp. Proc. Vol. 86 (Materials Research Society, Pittsburgh, 1987) pp. 81–98.
R.T. Hemmings and E.E. Berry, Evaluation of Plastic Filler Applications for Leached Fly Ash. EPRI Report CS-4765/RP2422-11, Sept. 1986.
E.E. Berry, R.T. Hemmings and D.M. Golden, in Fly Ash and Coal Conversion By-Products: Characterization. Utilization and Disposal HI. edited by G.J. McCarthy, F.P. Glasser and D.M. Roy, Mat. Res. Soc. Symp. Proc. Vol. 86 (Materials Research Society, Pittsburgh, 1987) pp. 365–380.
R.T. Hemmings, E.E. Berry and D.M. Golden, Proc. 8th Int. Ash Util. Symp.. Washington, Oct. 28–31, 1987, paper 38-A (EPRI CS-5362/P2422).
E.E. Berry, R.T. Hemmings and B.J. Cornelius, this volume.
J.D. McClung and M.R. Geer, “Properties of Coal and Coal Impurities,” in Coal Preparation. edited by J.W. Leonard (Am. Inst. Mining, Metall. and Petrol. Engs., 1979); H.J. Gluskoter, “Mineral Matter and Trace Elements in Coal,” in Trace Elements in Fuel, edited by S.P. Babu (Am. Chem. Soc., Washington, D.C., 1975), pp. 1–22; R.B. Finkelman, in Flv Ash and Coal Conversion By-Products: Characterization. Utilization and Disposal II. edited by G.J. McCarthy, F.P. Glasser and D.M. Roy, Mat. Res. Soc. Symp. Proc. Vol. 65 (Materials Research Society, Pittsburgh, 1986) pp. 71–76.
E. Raask and C.J. Schilling, Ann. Ind. Hygeine 23, 147 (1980).
E. Raask, Fuel 48, 366 (1969).
E.T. Turkdogan, Physicochemical Properties of Molten Slags and Glasses. (The Metals Society, London, 1983), and references therein.
S.V. Mattigod and J.O. Ervin, Fuel 62, 927 (1983); T. Konuma, T. Kikuchi, and K. Furuya, J. Japan. Soc. Air Pollut. 12, 35 (1984); S.V. Mattigod, Scan. Elect. Microsc. 611 (1982).
G. Chaddha and M.S. Seehra, Appl. Phys. 16, 1767 (1983).
G.L. Fishe, B.A. Prentice, D. Silberman, J.M. Ondov, A.H. Biermann, R.C. Ragaini and A.R. McFarland, Env. Sci. Technol. 12, 447, (1978); D. Hansen, D. Silberman and G.L. Fisher, Env. Sci. Technol. 15, 1057 (1980); J.A. Campbell, J.C. Laul, K.K. Nielson and R.D. Smith, Anal. Chem. 50, 1032 (1978).
R.W. Linton, A. Loh, D.F. Natusch, C.A. Evans and P. Williams, Science 191, 852 (1976).
D.C. Cavin, W.A. Klemm and G. Burnet, Proc. Iowa Acad. Sci. 81, 130 (1974).
G.J. McCarthy, this volume.
G.J. McCarthy, K.D. Swanson, L.P. Keller and W.C. Blatter, Cem. Conc. Research 14, 471 (1984); G.J. McCarthy, D.M. Johansen, S.J. Steinwand and A. Thedchanamoorthy, Adv. X-Ray Anal. 21, in press.
H. Rawson, Properties and Applications of Glass. (Elsevier, Amsterdam, 1980), p. 1.
W. Vogel, Chemistry of Glass, edited by N. Kreidl (The American Ceramic Society, Inc., Columbus, Ohio, 1985).
A. Paul, Chemistry of Glasses. (Chapman and Hall, London, 1982).
J. Wong and C.A. Angell, Glass Structure by Spectroscopy. (Marcel Dekker, Inc., New York, 1976).
W.J. Zachariasen, J. Am. Ceram. Soc. 54, 3841 (1932).
B.E. Warren, Z. Kristallogr. Mineralog. Petrogr. 86 349 (1933).
A.F. Prebus and J.W. Michener, Ind. Eng. Chem. 46, 147 (1953); J. Zarzycki and R. Mezard, Phys. Chem. Glasses 3, 163 (1962); J.W. Cahn and R.J. Charles, Phys. Chem. Glasses 6, 181, (1965).
Scanning electronmicrographs courtesy of the Canadian Ceramic Society. Micrographs prepared by: (a) D.W. Jones, Dalhousie University, Halifax, Nova Scotia; and (b) P.J. Hayward and D.C. Doern Atomic Energy of Canada Limited, Pinawa, Manitoba.
P.F. James, J. Mat. Sci. 10, 1802 (1975).
J.F. MacDowell and G.H. Beall, J. Am. Ceram. Soc. 52, 17 (1969).
R.J. Stevenson and T.P. Huber, in Fly Ash and Coal Conversion By-Products: Characterization. Utilization and Disposal in. edited by G.J. McCarthy, F.P. Glasser, D.M. Roy and S. Diamond, Mat. Res. Soc. Symp. Proc. Vol. 86 (Materials Research Society, Pittsburgh, 1987) pp. 99–108, and references therein; R.J. Stevenson and J.C. Collier, this volume.
E.E. DeGuire and S.H. Risbud, J. Mat. Sci. 19, 1760 (1984).
F.H. Hubbard, RJ. McGill, R.K. Dhir and M.S. Ellis, Min. Mag. 48, 251 (1984).
R.J. Lauf, in Application of Materials Techniques to Coal and Coal Wastes. Oak Ridge National Laboratory Report ORNL/TM-7663, Aug. 1981; Am. Ceram. Soc. Bull. 61, 487 (1982).
J.C. Qian, E.E. Lachowski and F.P. Glasser, this volume.
R.T. Hemmings, E.E. Berry and B.J. Cornelius, unpublished work.
C.M. Wang and H. Chen, Phys. Chem. Glasses 28, 39 (1987).
D. Virgo, B.O. Mysen and I. Kushiro, Science 208, 1371 (1980); B.O. Mysen, D. Virgo and C.M. Scarfe, Am. Mineralogist 65, 690 (1980).
D.W. Matson, S.K. Sharma and J.A. Philpotts, J. Non-Crystalline Solids 58, 323 (1983).
Raman data courtesy of B.E. Scheetz, Pennsylvania State University, and reported in part at the 2nd Int. Conf. on the Use of Fly Ash, Silica Fume, Slag and Natural Pozzolans in Concrete, Madrid, Spain, April 1986.
A.R.N. Eberendu and K.E. Daugherty, Cem. Conc. Research 14, 873 (1984).
G.P. Huffman, F.E. Huggins and G.R. Dunmyre, Fuel 60, 585 (1981).
K.E. Fox, T. Furukawa and W.B. White, Phys. Chem. Glasses 23, 169 (1982).
CC Hinckley, G.V. Smith, H. Twardowska, M. Saporoschenko, R.H. Shiley and R.A. Griffen, Fuel 59, 161 (1980).
T.L.H. Aikin, J. Cashion and A.L. Ottrey, Fuel 63, 1269 (1984).
G.Engelhardt, M. Nofz, K. Forkel, F.G. Wihsmann, M. Magi, A. Samoson and E. Lippmaa, Phys. Chem. Glasses 26, 157 (1985).
V.S. Ramachandran, Applications of Differential Thermal Analysis in Cement Chemistry. (Chem. Publ. Co. Inc., New York, 1969), pp. 196–201.
S.K. Chopra and C.A. Taneja, Proc. 5th Int. Symp. on the Chemistry of Cement. Tokyo, Japan, 1968, Part IV, pp. 228–236.
B.E. Scheetz, D.W. Strickler, M.W. Grutzeck and D.M. Roy, in Effects of Flyash Incorporation in Cement and Concrete, edited by S. Diamond, (Materials Research Society, University Park, PA, 1982), pp. 24–33.
S. Diamond, Cem. Conc. Research 16, 569 (1986).
C.W. Lentz, Inorg. Chem. 3, 574 (1964).
J. Gotz and C.R. Masson, J. Chem. Soc. (A), 2683 (1970), 686 (1971).
See for example, F.D. Tamas, A.K. Sarkar and D.M. Roy, in Hydraulic Cement Pastes: their Structure and Properties. (Cement & Concrete Assoc., Slough, U.K., 1976), p. 55; L.S. Dent Glasser, E.E. Lachowski, M.Y. Qureshi, H.P. Calhoun, D.J. Embree, W.D. Jamieson and C.R. Masson, Cem. Conc. Research 11, 775 (1981).
G.A. Norton, R. Markuszewski and H.R. Shanks. Env. Sci. Technol. 20, 409 (1986).
D.L. Biggs and J.J. Bruns, in Fly Ash and Coal Conversion By-Products: Characterization-Utilization and Disposal I. edited by G.J. McCarthy and R.J. Lauf, Mat. Res. Soc. Symp. Proc. Vol. 43 (Materials Research Society, Pittsburgh, 1985) pp. 21–29.
C.J. Warren and M.J. Dudas, Mobilization and Attenuation of Trace Elements in an Artificially Weathered Flv Ash. EPRI Report EA-4747, Electric Power Research Inst., Palo Alto (1986); M.J. Dudas, this volume.
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Hemmings, R.T., Berry, E.E. On the Glass in Coal Fly Ashes: Recent Advances. MRS Online Proceedings Library 113, 3–38 (1987). https://doi.org/10.1557/PROC-113-3
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DOI: https://doi.org/10.1557/PROC-113-3