Skip to main content
SpringerLink
Log in

Formation of hard hematite-cemented solids in steam generators: An analog of lithification of Fe-containing sedimentary rocks

  • Published:
Clays and Clay Minerals

Abstract

The formation of hard hematite in steam generators with relatively high levels (5–10 µg/L) of dissolved oxygen at temperatures around 280–290°C and pressures around 6–8 MPa can serve as an analog for the formation of hard hematite in sedimentary processes. Furthermore, in steam generators, as well as in nature, hematite is an effective cementing agent, capable of incorporating as much as twice its own weight of other solids to form a hard composite material. Laboratory simulations showed ferrihydrite to be the likely starting material for the formation of hard, dense hematite at temperatures much lower than those required for sintering of anhydrous hematite. These laboratory simulations, performed at temperatures around 260°C and pressures of ∼500 MPa, resulted in the formation of hard hematite or hematite-based composite solids over periods of 3–5 h, compared with several months in steam generators and many years in nature. The amount of water present during the synthesis (10–15% of the weight of dry ferrihydrite) and the gradual removal of water proved to be key parameters in the formation of hard, dense hematite. The mechanism, studied by means of X-ray diffractometry, Mössbauer spectroscopy and infrared spectroscopy, appeared to involve build-up, then gradual condensation of OH bridges, leading to the conversion of ferrihydrite to hydrohematite with approximately 4–5% of residual water. The presence of other solids, such as copper and its oxides, alumina and silica, in large quantities, resulted in smaller grain size of the hydrohematite product but did not affect its mechanical properties. On the other hand, the use of hydrazine to provide a reducing environment produced goethite during the precursor synthesis stage and soft magnetite during the pressing stage. However, whenever hematite was produced, it could not be subsequently reduced to magnetite by hydrazine under the reaction conditions specified above. The mechanical properties as well as the spectroscopic characteristics of the product of pressing agreed with observations on sedimentary hematite-cemented rocks.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  • Bagchi, T.P. and Sen, P.K. (1982) Kinetics of densification of powder compacts during the initial stage of sintering with constant rates of heating. A thermal analysis approach. Thermochimica Acta, 56, 269–283.

    Article  Google Scholar 

  • Barron, V., Rendon, J.L., Torrent, J. and Serna, C.J. (1984) Relation of infrared, crystallochemical, and morphological properties of Al-substituted hematites. Clays and Clay Minerals, 32, 475–479.

    Article  Google Scholar 

  • Burns, R., Cherepakhov, G., Mark, J.T. and Skulte, P. (1996) Indian Point 2 Station. Pp. A-43–A-47 in: PWR Secondary Water Chemistry Guidelines — Revision 4, EPRI TR-102134-R4, (A. McIlree, P. Millett and C.J. Wood, editors). Electric Power Research Institute, Palo Alto, California, USA.

    Google Scholar 

  • Campbell, A.S., Schwertmann, U. and Campbell, P.A. (1997) Formation of cubic phases on heating ferrihydrite. Clay Minerals, 32, 615–622.

    Article  Google Scholar 

  • Carlson, L. and Schwertman, U. (1981) Natural ferrihydrites in surface deposits from Finland and their association with silica. Geochimica et Cosmochimica Acta, 45, 421–429.

    Article  Google Scholar 

  • Childs, C.W. (1992) Ferrihydrite: A review of structure, properties and occurrence in relation to soils. Zeitschrift fuer Pflanzenernaehrung und Bodenkunde, 155, 441–448.

    Article  Google Scholar 

  • Cornejo, J. (1986) The effect of heat treatment on textural evolution of ferrihydrite. Materials Chemistry and Physics, 15, 369–377.

    Article  Google Scholar 

  • Cornell, R.M. and Giovanoli, R. (1988) The influence of copper on the transformation of ferrihydrite (5Fe2O3·9H2O) into crystalline products in alkaline media. Polyhedron, 7, 385–391.

    Article  Google Scholar 

  • Cornell, R.M. and Schwertmann, U. (2003) The Iron Oxides, 2nd edition. Wiley-VCH, Weinheim, Germany.

    Book  Google Scholar 

  • Cornell, R.M., Giovanoli, R. and Schindler, P.W. (1987) Effect of silicate species on the transformation of ferrihydrite into goethite and hematite in alkaline media. Clays and Clay Minerals, 35, 21–28.

    Article  Google Scholar 

  • Cornell, R.M., Giovanoli, R. and Schneider, W. (1989) Review of the hydrolysis of iron(III) and the crystallization of amorphous iron(III) hydroxide hydrate. Journal of Chemical Technology and Biotechnology, 46, 115–134.

    Article  Google Scholar 

  • Crosby, W.O. (1891) On the contrast in color of the soils of high and low latitudes. American Geologist, 8, 77.

    Google Scholar 

  • Dang, M.-Z., Rancourt, D.G., Dutrizac, J.E., Lamarche, G. and Provencher, R. (1997) Protohematite-hydrohematite-hematite: structuro-chemical phase relationships in hematite-like materials. Clays Our Future, Proceedings of the 11th International Clay Conference, 265–270.

  • Drits, V.A., Sakharov, B.A., Salyn, A.L. and Manceau, A. (1993) Structural model for ferrihydrite. Clay Minerals, 28, 185–207.

    Article  Google Scholar 

  • Drits, V.A., Gorshkov, A.I., Sakharov, B.A., Salyn, A.L., Manceau, A. and Sivtsov, A.B. (1995) Ferrihydrite and its phase transformations during heating in the oxidizing and reducing environments. Lithology and Mineral Resources, 1, 76–84.

    Google Scholar 

  • Eggleton, R.A. and Fitzpatrick, R.W. (1988) New data and a revised structural model for ferrihydrite. Clays and Clay Minerals, 36, 111–124.

    Article  Google Scholar 

  • Fischer, W.R. (1988) Microbiological reactions of iron in soils. Pp. 715–748 in: Iron in Soils and Clay Minerals (J.W. Stucki, B.A. Goodman and U. Schwertmann, editors). NATO ASI Series, 217. D. Reidel Publishing Company, Dordrecht, The Netherlands.

    Chapter  Google Scholar 

  • Friedman, G.M. and Sanders, J.E. (1978) Principles of Sedimentology. Wiley, New York, NY, p. 235.

    Google Scholar 

  • Glasauer, S.M., Hug, P., Weidler, P.G. and Gehring, A.U. (2000) Inhibition of sintering by Si during the conversion of Si-rich ferrihydrite to hematite. Clays and Clay Minerals, 48, 51–56.

    Article  Google Scholar 

  • Inouye, K., Ishii, S., Kaneko, K. and Ishikawa, T. (1972) Effect of copper(II) on the crystallization of α-iron oxide hydrate [α-FeOOH]. Zeitschrift für Anorgische und Allgemeine Chemie, 391, 86–96.

    Article  Google Scholar 

  • Jambor, J.L. and Dutrizac, J.E. (1998) Occurrence and constitution of natural and synthetic ferrihydrite, a widespread iron oxyhydroxide. Chemical Reviews, 98, 2549–2585.

    Article  Google Scholar 

  • Kündig, W. and Bömmel, H. (1966) Some properties of supported small a-Fe2O3 particles determined with the Mössbauer effect. Physical Review, 142, 327–333.

    Article  Google Scholar 

  • Labuda, E. (1996) Reactions of iron oxides at elevated pressures and temperatures. PhD dissertation, The Catholic University of America, Washington, D.C., 262 pp.

    Google Scholar 

  • Lewis, D.G. and Schwertmann, U. (1979) The influence of aluminum on the formation of iron oxides. IV. The influence of aluminum concentration, hydroxide concentration, and temperature. Clays and Clay Minerals, 27, 195–200.

    Article  Google Scholar 

  • Lunden, D.G. and Dean, W. (1979) Biochemistry of iron. Pp. 211–251 in: Biogeochemical Cycling of Mineral-forming Elements (P.A. Trudinger and D.J. Swaine, editors). Elsevier, Amsterdam.

    Chapter  Google Scholar 

  • Pfaff, G. and Feltz, A. (1990) Solid-state reactivity and mechanisms in oxide systems. VI. Sintering behaviour of hematite prepared by the hydrothermal method. Solid State Ionics, 38, 25–29.

    Article  Google Scholar 

  • Ruan, H.D., Frost, R.L., Kloprogge, J.T. and Duong, L. (2002) Infrared spectroscopy of goethite dehydroxylation: III. FT-IR microscopy of in situ study of the thermal transformation of goethite to hematite. Spectrochimica Acta, Part A: Molecular and Biomolecular Spectroscopy, 58A, 967–981.

    Article  Google Scholar 

  • Russell, J.D. (1979) Infrared spectroscopy of ferrihydrite: Evidence for the presence of structural hydroxyl groups. Clay Minerals, 14, 109–114.

    Article  Google Scholar 

  • Schultz, M.F., Benjamin, M.M. and Ferguson, J.F. (1987) Adsorption and desorption of metals on ferrihydrite: Reversibility of the reaction and sorption properties of the regenerated solid. Environmental Science and Technology, 21, 863–869.

    Article  Google Scholar 

  • Schwertmann, U. and Cornell, R.M. (2000) Iron Oxides in the Laboratory, 2nd edition. Wiley-VCH, Weinheim, Germany.

    Book  Google Scholar 

  • Schwertmann, U. and Murad, E. (1990) The influence of aluminum on iron oxides: XIV. Aluminum-substituted magnetite synthesized at ambient temperatures. Clays and Clay Minerals, 38, 196–202.

    Article  Google Scholar 

  • Schwertmann, U., Fitzpatrick, W.R., Taylor, R.M. and Lewis, D.G. (1979) The influence of aluminum on iron oxides. Part II. Preparation and properties of aluminum-substituted hematites. Clays and Clay Minerals, 27, 105–112.

    Article  Google Scholar 

  • Schwertmann, U., Friedl, J. and Stanjek, H. (1999) From Fe(III) ions to ferrihydrite and then to hematite. Journal of Colloid and Interface Science, 209, 215–223.

    Article  Google Scholar 

  • Stanjek, H. and Weidler, P.G. (1992) The effect of dry heating on the chemistry, surface area, and oxalate solubility of synthetic 2-line and 6-line ferrihydrites. Clay Minerals, 27, 397–412.

    Article  Google Scholar 

  • Torrent, J., Guzman, R. and Parra, M.A. (1982) Influence of relative humidity on the crystallization of Fe(III) oxides from ferrihydrite. Clays and Clay Minerals, 30, 337–340.

    Article  Google Scholar 

  • Turner, P. (1980) Continental Red Beds. Developments in Sedimentology, Vol. 29. Elsevier, Amsterdam.

    Google Scholar 

  • Towe, K.M. and Bradley, W.F (1967) Mineralogical constitution of colloidal hydrous ferric oxides. Journal of Colloid and Interface Science, 24, 384–392.

    Article  Google Scholar 

  • Van Houten, F.B. (1972) Iron and clay in tropical savanna alluvium, Northern Colombia. Contribution to the Origin of Red Beds. Geological Society of America Bulletin, 83, 2761–2772.

    Article  Google Scholar 

  • Van Houten, F.B. (1973) Origin of Red Beds. A review. 1961–1972. Annual Review of Earth and Planetary Science, 1, 39–61.

    Article  Google Scholar 

  • Varrin, R.D., Jr. (1996) Characterization of PWR Steam Generator Deposits, EPRI TR-106048. Electric Power Research Institute, Palo Alto, California, USA.

    Google Scholar 

  • Vempati, R.K. and Loeppert, R.H. (1989) Influence of structural and absorbed Si on the transformation of synthetic ferrihydrite. Clays and Clay Minerals, 37, 273–279.

    Article  Google Scholar 

  • Walker, T.R. (1967) Formation of Red Beds in modern and ancient deserts. Ganz-mavag Bulletin 78, 353–368.

    Google Scholar 

  • Walker, T.R. (1974) Formation of Red Beds in moist tropical climates. Hypothesis. Geological Society of America Bulletin, 85, 633–638.

    Article  Google Scholar 

  • Weidler, P.G. (1995) Surfaces of iron oxides. Dissertation, Technical University of Munich, Germany, 108 pp.

    Google Scholar 

  • Wightman, P.G. (2002) New insights into bacteria-related geochemical processes: co-adsorption, temperature dependence of protonation, and effects on iron-hydroxide precipitation. Dissertation, University of Notre Dame, Indiana, USA, 104 pp.

    Google Scholar 

  • Wolska, E. (1977) The significance of aluminum traces in the elimination of the goethite phase during the ageing of amorphous iron(III) hydroxide. Monatshefte für Chemie, 108, 819–828.

    Article  Google Scholar 

  • Wolska, E. (1981) The structure of hydrohematite. Zeitschrift für Kristallographie, 154, 69–75.

    Google Scholar 

  • Wolska, E. and Schwertmann, U. (1989) Nonstoichiometric structures during dehydroxylation of goethite. Zeitschrift für Kristallographie, 189, 223–237.

    Google Scholar 

  • Zhao, J., Huggins, F.E., Feng, Z. and Huffman, G.P. (1994) Ferrihydrite: surface structure and its effect on phase transformation. Clays and Clay Minerals, 42, 737–746.

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Sheppard T. Powell Associates, LLC, 1915 Aliceanna Street, Baltimore, Maryland, 21231, USA

    Ewa Labuda

  2. Consolidated Edison Co. of New York, Inc., New York, USA

    Galina Cherepakhov

  3. The Catholic University of America, 620 Michigan Avenue, N.E., Washington, DC, 20064, USA

    Aaron Barkatt

Authors
  1. Ewa Labuda
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Galina Cherepakhov
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Aaron Barkatt
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Aaron Barkatt.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Labuda, E., Cherepakhov, G. & Barkatt, A. Formation of hard hematite-cemented solids in steam generators: An analog of lithification of Fe-containing sedimentary rocks. Clays Clay Miner. 55, 59–70 (2007). https://doi.org/10.1346/CCMN.2007.0550105

Download citation

  • Received:

  • Revised:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1346/CCMN.2007.0550105

Key Words

Search

Navigation