Hostname: page-component-77c89778f8-7drxs Total loading time: 0 Render date: 2024-07-21T13:30:20.721Z Has data issue: false hasContentIssue false

The Chemistry of Al-Tobermorite and its Coexisting Phases AT 175°C

Published online by Cambridge University Press:  21 February 2011

Mary W. Barnes
Affiliation:
Materials Research Laboratory, The Pennsylvania State University, University Park, PA 16802
Barry E. Scheetz
Affiliation:
Materials Research Laboratory, The Pennsylvania State University, University Park, PA 16802
Get access

Abstract

The substitution of Al into the structure of tobermorite was investigated, along with the resultant phase assemblages that compatibly coexist with the Al-tobermorite. All experiments were conducted under hydrothermal conditions at saturated steam pressure. The temperatures of the experiments varied from 90° to 190°C and times from 1 to 28 days. Ca/Si ratios varied from 0.7 to 1.7, Al/(Al+Si) from 0.12 to 0.30. NaOH varied from none to 5 moles/mole tobermorite constituents. X-ray diffraction was used not only to identify phases but to determine degree of substitution and the rate of approach to steady state.

Maximum Al substitution was found to be Al/(Al+Si) = 0.13, and the maximum interlayer spacing was 11.42 ± 0.015 Å. This is in agreement with previously published work which found a trace of hydrogarnet at Al(Al+Si) = 0.15 and a maximum interlayer spacing of 11.45 ± 0.02 A. When Al concentrations in the mix are greater than enough to make maximum Al-tobermorite, “low”-hydrogarnet (“low”-hydrogarnet has ∼0.1 SiO2 per mole). As Al concentration is raised, a variable composition hydrogamet is formed and then a “high”-garnet of constant composition (SiO2 = 0.7 moles/mole hydrogarnet) is formed.

NaOH was found to have a major effect on the kinetics and the phase assemblages at a given time. Al-tobermorite, although stable at 90°C, converts to xonotlite at 175°C in the absence of NaOH. In its presence, even at a level too low to make Na-containing phases, Al-tobermorite persists at 21 days at 175°C. In the absence of NaOH, at 175°C, Al-tobermorite forms at up to 7–10 days but is converted to xonotlite at 28 days. Coexisting phases are gyrolite and cowlesite at Ca/Si ≥ 1 and hillebrandite and “low”-garnet at Ca/Si > 1. When there is enough NaOH to form Na-containing phases, Al-tobermorite coexists with reyerite and analcime at Ca/Si > 1. At Ca/Si < 1 and Al less than the composition on the tie line between Al-tobermorite and “low”-garnet, Al-tobermorite coexists with “low”-garnet and portlandite. In the compatibility triangle between Al-tobermorite, “low”-garnet, and “high”-garnet, Al-tobermorite coexists with variable Si-gamet. When Al exceeds its limiting value on the tie line, Al-tobermorite-“high”-gamet, the assemblage is Al-tobermorite-“high”-gamet-cowlesite.

Type
Research Article
Copyright
Copyright © Materials Research Society 1991

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

1. Roy, D. M. and Johnson, A. M., “Investigations of stabilities of calcium silicate hydrates at elevated temperatures and pressures,” Proceedings of International Symposium of Autoclaved Calcium Silicate Building Products, 1965, Soc. Chem. Ind. London, 114120 (1967).Google Scholar
2. Scheetz, B. E. and Roy, D. M., “Preliminary survey of the stability of silica-rich cementitious mortar, 8L-22 and 84-12 tuff,” LA 11222-MS, 00-70, Los Alamos National Laboratory, Los Alamos, NM (1989).Google Scholar
3. Diamond, S., White, J. L., and Dolch, W. L., “Effects of isomorphous substitution in hydrothermally synthesized tobermorite,” American Mineralogist, 51, 388401 (1966).Google Scholar
4. Taylor, H. F. W., ”Crystal chemistry of portland cement hydration products,” Sixth International Symposium in Chemistry of Cement, Moscow, 346 (1974).Google Scholar
5. Kalousek, G. L., “Crystal chemistry of hydrous calcium silicates: I. Substitution of aluminum in the lattice of tobermorite,” Journal of the American Ceramic Society, 40, 7480 (1957).Google Scholar
6. Chan, C. F. and Mitsuda, T., “Formation of III A tobermorite from mixtures of lime and colloidal silica with quartz,” Cement and Concrete Research, 8, 135138 (1978).Google Scholar
7. Kurbus, B., Bakula, F., and Gabrovcek, R., “Reactivity of SiO2 fume from ferrosilicon production with Ca(OH)2 under hydrothermal conditions,” Cement and Concrete Research, 15, 134–140.Google Scholar
8. Gard, J. A. and Taylor, H. F. W., “A further investigation of tobermorite from Loch Eynort, Scotland,” Mineralogical Magazine, 31, 361370 (1957).Google Scholar
9. Taylor, H. F. W. and Roy, D. M., “Structure and composition of hydrates,” Seventh International Congress on the Chemistry of Cement, Paris, 2.2-2.13 (1980).Google Scholar
10. Wieker, W., Grimmer, A. R., Winkler, A., Maegi, M., Tarmak, M., and Lippman, E., “Solid state high-resolution 29Si NMR spectroscopy of synthetic 14 Å, 11 Å, and 9 Å tobermorites, Cement and Concrete Research, 12, 333339 (1982).Google Scholar
11. Chan, C. F., Sakiyama, M., and Mitsuda, T., “Kinetics of the CaO-quartz-H2O reaction at 120° and 180°C in suspensions,” Cement and Concrete Research, 8, 16 (1978).Google Scholar
12. Speakman, K., “The stability of tobermorite in the system CaO-SiO2-H2O at elevated temperatures and pressures,” Mineralogical Magazine, 36, 10901102 (1968).Google Scholar
13. Aitken, A. and Taylor, H. F. W., “Hydrothermal reactions in lime-quartz pastes,” J. Applied Chemistry, 10, 715 (1960).Google Scholar
14. Hara, N. and Midgley, H. G., “The determination of crystallinity of tobermorite in autoclaved products,” Cement and Concrete Research, 10, 213221 (1980).Google Scholar
15. Alexanderson, J., “Relations between structure and mechanical properties of autoclaved concrete,” Cement and Concrete Research, 9, 507514 (1979).Google Scholar
16. Kurczyk, H. G. and Schwiete, H. E., “Concerning the hydration products of C3S and β-C2S,” Fourth International Symposium on the Chemistry of Cement, Washington, DC, 349358 (1960).Google Scholar
17. Barnes, M. W. and Scheetz, B. E., “The relation of microstructure to composition and formation temperature of Al-substituted tobermorite,” Abstracts, Materials Research Society Annual Meeting, Boston, p. 536 (1986).Google Scholar
18. Mitsuda, T., “Synthesis of tobermorite from zeolite,” Mineral J., 6, 143158 (1970).Google Scholar
19. Mitsuda, T. and Taylor, H. F. W., “Influence of aluminum on the conversion of calcium silicate hydrate gels into 11 Å tobermorite at 90°C and 120”C,” Cement and Concrete Research, 5, 203210 (1975).Google Scholar
20. Sakiyama, M. and Mitsuda, T., “Hydrothermal reaction between C-S-H and kaolinite for the formation of tobermorite at 180°C,” Cement and Concrete Research, 7, 681686 (1977).Google Scholar
21. Mitsuda, T. and Chan, C. F., “Anomalous tobermorite in autoclaved aerated concrete,” Cement and Concrete Research, 7, 191194 (1977).Google Scholar
22. Hamely, S. A. S. El, Mitsuda, T., and Taylor, H. F. W., “Synthesis of normal and anomalous tobermorites,” Cement and Concrete Research, 7, 429438 (1977).Google Scholar
23. Heilman, R. B., “Interaction of cements and radioactive waste forms in multicomponent systems at 200°C: Part II. Mineralogical changes of cement,” Cement and Concrete Research, 18(4), 554560 (1988).Google Scholar
24. Hara, N. and Inouye, N., “Formation of jennite and its thermal behavior,” Proceedings of the First International Symposium on Hydrothermal Reactions, Ed. Somiya, S., 849–858 (1982).Google Scholar
25. Gabrovcek, R., Kurbus, B., and Lengar, Z., “Comparison of unsubstituted and aluminum-containing synthetic tobermorites characterized by different methods,” Cement and Concrete Research, 16, 325332 (1986).Google Scholar
26. Komarneni, S., Roy, R., and Roy, D. M., “Al-substituted tobermorite: The coordination of aluminum as revealed by solid state 27Al magic angle spinning (MAS) NMR,” Cement and Concrete Research, 15, 723728.Google Scholar
27. Mitsuda, T. and Taylor, H. F. W., “Normal and anomalous tobermorites,” Mineralogical Magazine, 42, 229235 (1978).Google Scholar
28. Komarneni, S., Roy, D. M., and Roy, R., “Al-substituted tobermorite: Shows cation exchange,” Cement and Concrete Research, 12, 773780 (1982).Google Scholar
29. Komarneni, S., Roy, R., and Roy, D. M., “Pseudomorphism in xonotlite and tobermorite with Co2+ and Ni2+ exchange for Ca+2 at 25°C,” Cement and Concrete Research, 16, 4758 (1986).Google Scholar
30. Komarneni, S. and Tsuji, M., “Selective cation exchange in substituted tobermorites,” Journal of the American Ceramic Society, 22(9), 16681674 (1989).Google Scholar
31. Tsuji, M. and Komameni, S., “Alkali metal ion exchange and selectivity of Alsubstituted tobermorite,” J. Mat. Res., in press (1990).Google Scholar
32. Mitsuda, T., “Paragenesis of 11 Å tobermorite and poorly crystalline hydrated magnesium silicate,” Cement and Concrete Research, 3, 7180 (1973).Google Scholar
33. Mitsuda, T., Saito, J., and Hattori, E., “Influence of starting materials on the hydrothermal formation of xonotlite at 180°C,” International Symposium on Hydrothermal Reactions, Yokohama, 823838 (1982).Google Scholar
34. Alujevic, V., Bezjak, A., and Glasnovic, A., “Kinetic study of the hydrothermal reaction in CaO-quartz system,” Cement and Concrete Research, 16, 695699 (1986).Google Scholar
35. Peppler, R. B., “The system of lime, silica and water at 180°C,” J. Res. Nat. Bur. Standards, 54, 205211 (1955).Google Scholar
36. Moorehead, D. R. and McCartney, E. R., “The mechanism of the quartz-lime solution reaction at temperatures up to 500°C,” Symposium on Autoclaved Calcium Silicate Building Products, London, 1965, 8691 (1967).Google Scholar
37. Kalousek, G. L., Mitsuda, T., and Taylor, H. F. W., “Xonotlite: Cell thermogravimetry and analytical electron microscopy,” Cement and Concrete Research, 7, 305312 (1977).Google Scholar
38. Roy, D. M., White, E. L., Langton, C. A., and Grutzeck, M. W., “Potential new high temperature cements for geothermal wells,” Proc. International Symp. Oilfield and Geothermal Chem., Houston, SPE Pub. 7877, 153161 (1979).Google Scholar
39. Luke, K., Taylor, H. F. W., and Kalousek, G. L., “Some factors affecting formation of truscottite and xonotlite at 300°–350°C,” Cement and Concrete Research, 11, 197203 (1981).Google Scholar
40. Roy, D. M., Langton, C. A., Grutzeck, M. W., and White, E. L., ”Hydrothermal high temperature cements for potential geothermal applications,” Society of Petroleum Engineers of AIME, publication SPE 8994, presented at the Fifth International Symposium on Oilfield and Geothermal Chemistry, Stanford, CA (1980).Google Scholar
41. Cann, J. R., “Gyrolite and Reyerite from ‘S Airde Beinn, northern Mull,” Mineralogical Magazine, 35, 14 (1965).Google Scholar
42. Harker, R. I., “Dehydration series in the system CaSiO3-SiO2-H2O,” Journal of the American Ceramic Society, 47, 521529 (1964).Google Scholar
43. Assarsson, G. O., “Hydrothermal reactions between calcium hydroxide and amorphous silica in atmospheres of unsaturated steam,” J. Phys. Chem., 60, 15591564 (1956); “Hydrothermal reactions between calcium hydroxide and muscovite and feldspar at 120°–220°C,” J. Phys. Chem., 64, 626–632 (1960).Google Scholar
44. Meyer, J. W. and Jaunarajs, K. L., “Synthesis and crystal chemistry of gyrolite and reyerite,” American Mineralogist, 46, 913933 (1961).Google Scholar
45. Livingstone, A., “Reyerite, tobermorite, calcium analcime and bytownite from amygdales in Skye basalt,” Mineralogical Magazine, 52, 711713 (1988).Google Scholar
46. Cornu, F., Min. Petr. Mitt. (Tschermak) 1906–1907, 25, 211, 519 (1906).Google Scholar
47. Chalmers, R. A., Farmer, V. C., Harker, R. I., Kelly, S., and Taylor, H. F. W., “Reyerite,” Mineralogical Magazine, 33, 821840 (1964).Google Scholar
48. Clement, S. C. and Ribbe, P. H., “New locality, formula, and proposed structure for reyerite,” American Mineralogist, 58, 517522 (1973).Google Scholar
49. Fleischer, M., Glossary of Mineral Species, The Mineralogical Record Inc., Tucson (1983).Google Scholar
50. Merlino, S., “Gyrolyte: Its crystal structure and crystal chemistry,” Mineralogical Magazine, 52, 377387 (1988).Google Scholar
51. Taylor, H. F. W., “Hydrothermal reactions in the system CaO-SiO2-H2O and in the steam curing of cement and cement-silica products,” Fourth International Symposium on the Chemistry of Cement, Washington, DC, 167203 (1960).Google Scholar
52. Mitsuda, T. and Banno, S., “Hydrothermal formation of pseudowollastonite from lime-quartz mixes at 165°C and 200°C,” Cement and Concrete Research, 7, 457460 (1977).Google Scholar
53. Hara, N., Chan, C. F., and Mitsuda, T., “Formation of 14 Å-tobermorite,” Cement and Concrete Research, 8, 113116 (1978).Google Scholar
54. Gottardi, G. and Galli, E., Natural Zeolites, Springer Verlag, Berlin (1985).Google Scholar
55. Langton, C. A., White, E. L., Grutzeck, M. W., and Roy, D. M., “High temperature cements with geothermal applications,” Seventh International Congress on the Chemistry of Cement, Paris, V, 145151 (1980).Google Scholar
56. Sacerdoti, M. and Passaglia, E., “The crystal structure of katoite and implications for the hydrogrossular group,” Bull. Mineral., 108, 18 (1985).Google Scholar
57. Flint, E. P., McMurdie, H. F., and Wells, L. S., “Hydrothermal and x-ray studies of the garnet-hydrogarnet series and the relationship of the series to hydration products of portland cement,” J. Res. Nat. Bur. Standards, 26, 1333 (1941).Google Scholar
58. Lea, F. M., The Chemistry of Cement and Concrete, Edward Arnold Ltd. (1970).Google Scholar
59. Passaglia, E. and Rinaldi, R., “Katoite, a new member of the Ca3(AlSiO4)3-Ca3Al(OH)12 series and a new nomenclature for the hydrogrossular group of minerals,” Bull. Mineral., 107, 605618 (1984).Google Scholar
60. Hoyle, S. Q. and Grutzeck, M. W., “Effects of phase composition on the strontium leachability of cement-based waste forms,” Advances in Ceramics, 20, 149153 (1987).Google Scholar
61. MacDowell, J. F., “Hydrogarnet-gehlenite hydrate cements from CaO-Al2O3-SiO2 glasses,” Eighth International Congress on the Chemistry of Cement, 4, 423428 (1986).Google Scholar
62. Roy, D. M. and Roy, R., “Crystalline solubility and zeolite behavior in garnet phases in the system CaO-Al2O3-SiO2-H2O,” Fourth International Symposium on the Chemistry of Cement, Washington, DC, 307314 (1960).Google Scholar
63. Kobayashi, S. and Shoji, T., “Infrared analysis of the grossular-hydrogrossular series,” Mineralogical Journal, 11, 331343 (1983).Google Scholar
64. Joint Committee for Powder Diffraction Standards, File 19–1364 (1989).Google Scholar