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The transformation of amorphous silica to crystalline silica under hydrothermal conditions

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Abstract

Hydrothermal syntheses were made mainly in the binary system SiO2-H2O in a temperature range between 300 ° C and 500 ° C and pressures from 0.2 kbar up to 4.0 kbar with various starting materials. In this way the transformation behavior of different amorphous silicas via cristobalite and keatite to quartz were observed. This behavior depends mainly on the parameters: pressure, temperature, run duration and state of the starting material. Four reaction paths have been observed: in most experiments the complete reaction sequence “amorphous silica→cristobalite→keatite→quartz” took place. Less often the reactions: “amorphous silica→cristobalite→quartz” and: “amorphous silica→keatite→quarts” were observed. Very few samples were found with a direct transition of amorphous silica into quartz at high pressures. A kinetic model is given in form of a pressure-temperature-time diagram of the system SiO2-H2O under hydrothermal conditions.

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References

  • Alexander, G.B., Heston, W.M., Iler, H.K.: The solubility of amorphous silica in water. J. Phys. Chem. 58, 453–455 (1954)

    Google Scholar 

  • Bettermann, P.: Petrographische und betontechnologische Untersuchungen zur Alkaliempfindlichkeit von Geschiebefeuerstein aus Schleswig-Holstein. Diplomarbeit Universität Kiel, p. 245, Kiel 1972

  • Bettermann, P., Ackermand, D.: Comparison flint-chert, based on chemical data. (abstract in: collected abstracts, 9th gen. meet., IMA, 1974) in press: J. Sed. Petrol. 1975

  • Bricker, O.P.: Stability constants and Gibbs free energies of formation of magadiite and kenyaite. Am. Mineralogist 54, 1026–1033 (1969)

    Google Scholar 

  • Brousse, R.: Minéralogie et Pétrographie des roches volcaniques du massif du Mont Dore (auvergne). Bull. Soc. Franc. Mineral. 84, 131–186 (1961)

    Google Scholar 

  • Campbell, A.S., Fyfe, W.S.: Hydroxyl-ion catalysis of the hydrothermal crystallization of amorphous silica, a possible high-temperature pH-indicator. Am. Mineralogist 45, 464–468 (1960)

    Google Scholar 

  • Carr, R.M., Fyfe, W.S.: Some observations on the crystallization of amorphous silica. Am. Mineralogist 43, 908–916 (1958)

    Google Scholar 

  • Correns, C.W.: Beiträge zur Petrographie und Genesis der Lydite, (Kieselschiefer). Mitt. preuss. geol. Landesanstalt, 18–36, Berlin 1924

    Google Scholar 

  • Correns, C.W.: Zur Geochemie der Diagenese, 1. Das Verhalten von CaCO3 und SiO2. Geochim. Cosmochim. Acta, 1, 49–54 (1950)

    Article  Google Scholar 

  • Endell, J.: Röntgenographischer Nachweis kristalliner Zwischenzustände bei der Bildung von Cristobalit aus Kieselgur beim Erhitzen. Kolloid Z. 111, 19–22 (1948)

    Google Scholar 

  • Ernst, W.G., Calvert, S.E.: An experimental study of the recrystallization of porcelanite and its bearing on the origin of some bedded chert. Am. J. Sci. 269A (Schairer-Volume), 114–133 (1969)

    Google Scholar 

  • Eugster, H.P.: Hydrous sodium silicates from Lake Magadi, Kenya: precursors of bedded chert. Science 157, 1177–1180 (1967)

    Google Scholar 

  • Eugster, H.P.: Inorganic bedded cherts from the Magadi area, Kenya. Contrib. Mineral. Petrol. 22, 1–31 (1969)

    Google Scholar 

  • Flörke, O.W.: Strukturanomalien bei Tridymit und Cristobalit. Ber. Dt. Keram. Ges. 369–381 (1955a)

  • Flörke, O.W.: Zur Frage des “Hoch”-cristobalit in Opalen, Bentoniten und Gläsern. Neues Jahrb. Mineral. Monatsh. 217–223 (1955b)

  • Flörke, O.W.: Die Kristallarten des SiO2 und ihr Umwandlungsverhalten. Ber. Dt. Keram. Ges. 38, 89–97 (1961)

    Google Scholar 

  • Flörke, O.W.: Untersuchungen an amorphem und mikrokristallinem SiO2. Chem. Erde 22, 91–110 (1962)

    Google Scholar 

  • Flörke, O.W.: Die Modifikationen des SiO2. Fortschr. Mineral. 44, 181–230 (1967)

    Google Scholar 

  • Flörke, O.W.: Transportation and deposition of SiO2 with H2O under supercritical conditions. Kristall und Technik 7, 159–166 (1972)

    Google Scholar 

  • Flörke, O.W., Jones, J.B., Schmincke, H.U.: Z. Krist. Laves-Festschrift, in press. (1975)

  • Flörke, O.W., Jones, J.B., Segnit, E.R.: Opal-CT crystals. Neues Jahrb. Mineral. Mh. '75.8, 369–377 (1975)

  • Fyfe, W.S., McKay, D.S.: Hydroxyl ion catalysis of the crystallization of amorphous silica at 330 ° C and some observations on the hydrolysis of albite solutions. Am. Mineral. 47, 83–89 (1962)

    Google Scholar 

  • Greenwood, R.: Thermal behavior of SiO2-X and its relation to the natural silica minerals. Am. Mineral. 52, 1662–1668 (1967)

    Google Scholar 

  • Hamilton, D.L., Henderson, C.M.B.: The preparation of silicate compositions by a gelling method. Mineral. Mag. 36, 832–838 (1968)

    Google Scholar 

  • Harder, H.: Experimente zur “Ausfällung” der Kieselsäure. Geochim. Cosmochim. Acta 29, 429–444 (1965)

    Article  Google Scholar 

  • Harder, H., Flehming, W.: Bildung von Quarz aus verdünnten Lösungen bei niedrigen Temperaturen. Naturwissenschaften 54, 140 (1967)

    Google Scholar 

  • Harder, H., Flehming, W.: Quarzsynthese bei tiefen Temperaturen. Naturwissenschaften 295–305 (1969)

  • Harder, H., Menschel, G.: Quarzbildungen am Meeresboden. Naturwissenschaften 54, 561 (1967)

    Google Scholar 

  • Heydemann, A.: Untersuchungen über die Bildungsbedingungen von Quarz im Temperaturbereich zwischen 100 ° C und 250 ° C. Beitr. Mineral Petrog. 10, 242–259 (1964)

    Google Scholar 

  • Hofmann, U., Rothe, A.: Über die Veränderung des Quarzes beim trockenen Mahlen. Z. Anorg. Allgem. Chem. 357, 196–201 (1968)

    Google Scholar 

  • Jones, J.B., Segnit, E.R.: The nature of opal. I. Nomenclature and constituent phases. J. Geol. Soc. Australia 18, 57–68 (1971)

    Google Scholar 

  • Kameyama, T., Naka, S.: Effect of water on transformation of amorphous silica to coesite. J. Am. Ceram. Soc. 57, 499 (1974)

    Google Scholar 

  • Keat, P.P.: A new crystalline silica. Science 120, 328–330 (1954)

    Google Scholar 

  • Keat, P.P.: The transformation of silicic acid to quartz and the synthesis of a new crystalline silica. Ph. D., Thesis, Rutgers University, New Jersey 1956

    Google Scholar 

  • Konnert, J.H., Karle, J., Ferguson, G.A.: Crystalline ordering in silica and germania glasses. Science 179, 177–178 (1973)

    Google Scholar 

  • Li, C.T.: Transformation mechanism between high-quartz and keatite phases of LiAlSi2O6 composition. Acta Cryst. B 27, 1132–1140 (1971)

    Article  Google Scholar 

  • Li, C.T.: The role of lithium in stabilizing some high-temperature silica phases, Z. Krist. 138, 216–236 (1973)

    Google Scholar 

  • Luth, W.C., Tuttle, O.F.: Externally heated cold-seal pressure vessels for use to 10000 bars and 750 ° C. Am. Mineral. 48, 1401–1403 (1963)

    Google Scholar 

  • Mackenzie, F.T., Gees, R.: Quartz: Synthesis at earth-surface conditions. Science 173, 533–535 (1971)

    Google Scholar 

  • Maglione, G., Servant, M.: Signification des silicates de sodium et des cherts néoformés dans les variations hydrologiques et climatiques holocènes du bassin tschadien. Compt. Rend. 277, 1721–1724 (1973)

    Google Scholar 

  • Mizutani, S.: Transformation of silica under hydrothermal conditions. J. Earth Sci. [Nagova Univ.] 14, 56–88 (1966)

    Google Scholar 

  • Mosebach, R.: Die Löslichkeit der gefällten Kieselsäure und des Kieselglases in Wasser bei höheren Temperaturen und Drucken. Neues Jahrb. Mineral., Abhandl. 89, 1–26 (1956)

    Google Scholar 

  • Mosebach, R.: Theromodynamic behavior of quartz and other forms of silica in pure water at elevated temperatures and pressures with conclusion on their mechanism of solution. J. Geol. 65, 347–363 (1957)

    Google Scholar 

  • Nagasima, N.: Structure analysis of silicon dioxide films formed by oxidation of silane. J. Appl. Phys. 43, 3378–3386 (1972)

    Article  Google Scholar 

  • Nagelschmidt, G., Gordon, R.L., Griffin, O.G.: Surface of finely-ground silica. Nature 169, 539 (1952)

    Google Scholar 

  • Okamoto, G., Okura, T., Goto, T.: Properties of silica in water. Geochim. Acta 12, 123–132 (1957)

    Article  Google Scholar 

  • Olesch, M.: Synthese und Stabilität trioktaedrischer Calciumglimmer (Clintonit, Xanthophyllit, Brandisit). Dissertation Ruhr Universität, p. 197, Bochum 1973

  • Robarick, E.: Synthese und kristallographische Charakterisierung von SiO2-X. Diplomarbeit, Ruhr-universität, p. 67, Bochum 1974

    Google Scholar 

  • Schrader, R. Wissing, R., Kubsch, H.: Zur Oberflächenchemie von mechanisch aktiviertem Quarz. Z. Anorg. Allgem. Chem. 365, 191–198 (1969)

    Google Scholar 

  • Shropshire, J., Keat, P.P., Vaughan, P.A.: The crystal structure of keatite, a new form of silica. Z. Krist. 112, 400–413 (1959)

    Google Scholar 

  • Sievers, R.: Silica solubility, 0–200 ° C, and the diagenesis of siliceous sediments. J. Geol. 70, 127–150 (1962)

    Google Scholar 

  • Siffert, B., Wey, R.: Etude quantitative de la transformation de la silice en quartz entre 230 ° et 350 ° C en présence de bases alcalines. Silicates Ind. 32, 415–421 (1967)

    Google Scholar 

  • Simon, I.: Infra-red studies of glass. In: Modern aspects of the vitreous state, (J.D. Mackenzie, ed.), p. 120–151. London: Butterworth 1960

    Google Scholar 

  • Simon, I., McMahon, H.O.: Study of the structure of quartz, cristobalite and vitreous silica by reflection in infrared. J. Chem. Phys. 21, 23–30 (1953)

    Google Scholar 

  • Skinner, B.J., Appleman, D.E.: Melanophlogite, a cubic polymorph of silica. Am. Mineral. 48, 854–867 (1963)

    Google Scholar 

  • Tarr, W.A.: The origin of chert and flint. Univ. Missouri Studies, 1, (2), 1926

  • Tröger, W.E.: Optische Bestimmung der gesteinsbildenden Minerale. Teil 2 Textband, 2. Auflage, p. 822, Stuttgart: Nägele und Obermiller 1969

    Google Scholar 

  • Tuttle, O.F.: Two pressure vessels for silicate-water studies. Geol. Soc. Am. Bull. 60, 1727–1729 (1949)

    Google Scholar 

  • Wetzel, W.: Sedimentpetrographische Studien I. Feuerstein. Neues Jahrb. Mineral. 47, 39–78 (1923)

    Google Scholar 

  • Wetzel, W.: Die Entstehungsgeschichte verschiedener Arten von Kreidefeuersteinen, Z. D. DGG, Bd. 89 (1973)

  • Wetzel, W., Wetzel, O., Deflandre, G.: Die Feuersteine der Kreidezeit (Kieselsäure als Versteinerungsmittel). Umschau 45, 275–279 (1941)

    Google Scholar 

  • Wetzel, W.: Selektive Verkieselung. N. Jb. Paläont., Abh. 105, 1–10 (1957)

    Google Scholar 

  • Wey, R., Siffert, B.: Quelques observations quantitatives sur la transformation de la silice amorphe en quartz et cristobalite. Silicates Industriels 9, 419–424 (1961)

    Google Scholar 

  • Wilson, M.J., Russell, J.D., Tait, J.M.: A new interpretation of the structure of disordered α-cristobalite. Contrib. Mineral. Petrol. 47, 1–6 (1974)

    Google Scholar 

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Bettermann, P., Liebau, F. The transformation of amorphous silica to crystalline silica under hydrothermal conditions. Contr. Mineral. and Petrol. 53, 25–36 (1975). https://doi.org/10.1007/BF00402452

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