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Minerals in cement chemistry: A single-crystal neutron diffraction and Raman spectroscopic study of thaumasite, Ca3Si(OH)6(CO3)(SO4)·12H2O

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Published/Copyright: April 2, 2015
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American Mineralogist
From the journal American Mineralogist Volume 97 Issue 7

Abstract

Thaumasite, Ca3Si(OH)6(CO3)(SO4)⋅12H2O, is recognized as a secondary-alteration mineral and indicator of sulfate attack in Portland cement in contact with sulfate-rich groundwater, especially in cold regions. The hydrogen positions in thaumasite have been determined from single-crystal neutron diffraction structure refinements at 300 and 22 K. No phase transitions occur within the temperature range investigated. The structure of thaumasite is largely held together by hydrogen bonding. The major structural units [CO3 groups, SO4 tetrahedra, Si(OH)6 octahedra, and Ca(OH)4(H2O)4 polyhedra] are interconnected via 10 distinct hydrogen bonds. Analysis of the difference-Fourier maps of the nuclear density reveals the positions of all 10 hydrogen atoms in the structure, and the hydrogen bonding becomes shorter (stronger) upon decreasing temperature to 22 K. The SO4 tetrahedron expands upon decreasing temperature (i.e., negative thermal expansion at the molecular level), driven by shortening of the hydrogen bonding between [Ca3Si(OH)6(H2O)12]4+ columns. Polarized Raman spectra of thaumasite show that the ν1 symmetric stretching modes of Si(OH)6, SO4, and CO3 occur at 658, 983, and 1066 cm-1, respectively. In addition, the out-of-plane bending mode (ν2) and asymmetric stretching mode (ν3) of the carbonate group are tentatively assigned to bands at 887 and 1400 cm-1, respectively. Bands at 418 and 455 cm-1 (and possibly at 477 cm-1) are attributed to the symmetric bending modes (ν2) of the sulfate group, and we observe a possible asymmetric stretching mode (ν3) of SO4 at 1090-1100 cm-1. Splitting of some sulfate and carbonate vibrational modes may occur due to hydrogen bonding on all the oxygen sites. At 1685-1710 cm-1 we observe the H2O bending modes (H-O-H), and from 2900-3600 cm-1 there are 13 distinct bands associated with bending overtones and the O-H stretching vibrations corresponding to H-positions determined in the neutron diffraction study. The effect of the low-temperature stability of thaumasite on the pronounced “thaumasite sulfate attack” of Portland cements observed in cold regions is discussed.

Keywords : Thaumasite; Portland cements; crystal chemistry; single-crystal neutron diffraction; Raman spectroscopy; hydrogen bonding
Received: 2011-11-23
Accepted: 2012-4-3
Published Online: 2015-4-2
Published in Print: 2012-7-1

© 2015 by Walter de Gruyter Berlin/Boston

Articles in the same Issue

  1. Mercury (Hg) mineral evolution: A mineralogical record of supercontinent assembly, changing ocean geochemistry, and the emerging terrestrial biosphere
  2. The 3.65 Å phase, MgSi(OH)6: Structural insights from DFT-calculations and T-dependent IR spectroscopy
  3. Vertical zonation of the Barcroft granodiorite, White Mountains, California: Implications for magmatic processes
  4. Minerals in cement chemistry: A single-crystal neutron diffraction and Raman spectroscopic study of thaumasite, Ca3Si(OH)6(CO3)(SO4)·12H2O
  5. A new high-pressure phase transition in natural Fe-bearing orthoenstatite
  6. Aluminum solubility in TiO2 rutile at high pressure and experimental evidence for a CaCl2-structured polymorph
  7. First record and timing of UHP metamorphism from zircon in the Xitieshan terrane: Implications for the evolution of the entire North Qaidam metamorphic belt
  8. Lead in zircon at the atomic scale
  9. Characterization of fluor-chlorapatites by electron probe microanalysis with a focus on time-dependent intensity variation of halogens
  10. An inversion-based self-calibration for SIMS measurements: Application to H, F, and Cl in apatite
  11. Second boiling effects on the Al-content of hornblende rims from an exhumed Cretaceous arc pluton, Stewart Island, New Zealand
  12. Heat transfer in plagioclase feldspars
  13. Transport properties and equation of state of 1-bar eutectic melt in the system CaAl2Si2O8-CaMgSi2O6 by molecular dynamics simulation
  14. High-pressure behavior of zoisite
  15. A first-principle investigation of antigorite up to 30 GPa: Structural behavior under compression
  16. Reynoldsite, Pb2Mn4+2 O5(CrO4), a new phyllomanganate-chromate from the Blue Bell claims, California and the Red Lead mine, Tasmania
  17. A new cubic perovskite in PbGeO3 at high pressures
  18. Manganoquadratite, AgMnAsS3, a new manganese-bearing sulfosalt from the Uchucchacua polymetallic deposit, Lima Department, Peru: Description and crystal structure
  19. Leucostaurite, Pb2[B5O9]Cl·0.5H2O, from the Atacama Desert: The first Pb-dominant member of the hilgardite group, and micro-determination of boron in minerals by PIGE
  20. Synthetic LiAlGe2O6: The first pyroxene with P21/n symmetry
  21. Panguite, (Ti4+,Sc,Al,Mg,Zr,Ca)1.8O3, a new ultra-refractory titania mineral from the Allende meteorite: Synchrotron micro-diffraction and EBSD
  22. Buseckite, (Fe,Zn,Mn)S, a new mineral from the Zakłodzie meteorite
  23. Experimental calibration of the effect of H2O on plagioclase crystallization in basaltic melt at 200 MPa
  24. High-pressure and high-temperature titanium solution mechanisms in silicate-saturated aqueous fluids and hydrous silicate melts
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  26. Graphite in the martian meteorite Allan Hills 84001
https://doi.org/10.2138/am.2012.4058
Keywords for this article
Thaumasite; Portland cements; crystal chemistry; single-crystal neutron diffraction; Raman spectroscopy; hydrogen bonding

Articles in the same Issue

  1. Mercury (Hg) mineral evolution: A mineralogical record of supercontinent assembly, changing ocean geochemistry, and the emerging terrestrial biosphere
  2. The 3.65 Å phase, MgSi(OH)6: Structural insights from DFT-calculations and T-dependent IR spectroscopy
  3. Vertical zonation of the Barcroft granodiorite, White Mountains, California: Implications for magmatic processes
  4. Minerals in cement chemistry: A single-crystal neutron diffraction and Raman spectroscopic study of thaumasite, Ca3Si(OH)6(CO3)(SO4)·12H2O
  5. A new high-pressure phase transition in natural Fe-bearing orthoenstatite
  6. Aluminum solubility in TiO2 rutile at high pressure and experimental evidence for a CaCl2-structured polymorph
  7. First record and timing of UHP metamorphism from zircon in the Xitieshan terrane: Implications for the evolution of the entire North Qaidam metamorphic belt
  8. Lead in zircon at the atomic scale
  9. Characterization of fluor-chlorapatites by electron probe microanalysis with a focus on time-dependent intensity variation of halogens
  10. An inversion-based self-calibration for SIMS measurements: Application to H, F, and Cl in apatite
  11. Second boiling effects on the Al-content of hornblende rims from an exhumed Cretaceous arc pluton, Stewart Island, New Zealand
  12. Heat transfer in plagioclase feldspars
  13. Transport properties and equation of state of 1-bar eutectic melt in the system CaAl2Si2O8-CaMgSi2O6 by molecular dynamics simulation
  14. High-pressure behavior of zoisite
  15. A first-principle investigation of antigorite up to 30 GPa: Structural behavior under compression
  16. Reynoldsite, Pb2Mn4+2 O5(CrO4), a new phyllomanganate-chromate from the Blue Bell claims, California and the Red Lead mine, Tasmania
  17. A new cubic perovskite in PbGeO3 at high pressures
  18. Manganoquadratite, AgMnAsS3, a new manganese-bearing sulfosalt from the Uchucchacua polymetallic deposit, Lima Department, Peru: Description and crystal structure
  19. Leucostaurite, Pb2[B5O9]Cl·0.5H2O, from the Atacama Desert: The first Pb-dominant member of the hilgardite group, and micro-determination of boron in minerals by PIGE
  20. Synthetic LiAlGe2O6: The first pyroxene with P21/n symmetry
  21. Panguite, (Ti4+,Sc,Al,Mg,Zr,Ca)1.8O3, a new ultra-refractory titania mineral from the Allende meteorite: Synchrotron micro-diffraction and EBSD
  22. Buseckite, (Fe,Zn,Mn)S, a new mineral from the Zakłodzie meteorite
  23. Experimental calibration of the effect of H2O on plagioclase crystallization in basaltic melt at 200 MPa
  24. High-pressure and high-temperature titanium solution mechanisms in silicate-saturated aqueous fluids and hydrous silicate melts
  25. Thermodynamic behavior and properties of katoite (hydrogrossular): A calorimetric study
  26. Graphite in the martian meteorite Allan Hills 84001
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