Hostname: page-component-78c5997874-ndw9j Total loading time: 0 Render date: 2024-11-10T07:22:09.878Z Has data issue: false hasContentIssue false
  • English
  • Français

Alteration of nanocrystalline calcium silicate hydrate (C-S-H) at pH 9.2 and room temperature: a combined mineralogical and chemical study

Published online by Cambridge University Press:  02 January 2018

Nicolas C. M. Marty ,
Sylvain Grangeon ,
Fabienne Warmont  and
Catherine Lerouge
Nicolas C. M. Marty*
Affiliation:
BRGM, D3E/SVP, 3 Avenue C. Guillemin, F-45060 Orléans Cedex 2, France
Sylvain Grangeon
Affiliation:
BRGM, D3E/SVP, 3 Avenue C. Guillemin, F-45060 Orléans Cedex 2, France
Fabienne Warmont
Affiliation:
ICMN (Interface, Confinement, Matériaux et Nanostructures) - UMR 7374 – CNRS - Université d’Orléans, 1b rue de la Férollerie, 45071 Orléans Cedex 2, France
Catherine Lerouge
Affiliation:
BRGM, D3E/SVP, 3 Avenue C. Guillemin, F-45060 Orléans Cedex 2, France
*
*E-mail: n.marty@brgm.fr
Rights & Permissions [Opens in a new window]

Abstract

Core share and HTML view are not available for this content. However, as you have access to this content, a full PDF is available via the ‘Save PDF’ action button.

Calcium silicate hydrate (C-S-H) alteration was studied with flow-through experiments at 25°C and pH 9.2. Three materials with apparent Ca/Si ratios (C/S ratios) of 1.47, 1.38 and 0.86 were investigated. Physical (thermogravimetric analyses/differential thermal analysis), mineralogical (X-ray diffraction) and chemical (electron probe microanalysis, transmission electron microscopy/energy dispersive X-ray spectrometry) analyses were performed to characterize the reacting minerals. Initial stoichiometric C/S ratios were 1.22, 1.22 and 0.85, respectively. The excess of Ca is attributed mainly to the presence of calcium hydroxide intimately mixed in with C-S-H particles.

The C-S-H chemical compositions were monitored during flow-through experiments in order to determine the mineral stoichiometry needed for reaction kinetics. Under our experimental conditions the stoichiometric C/S ratios decreased continuously with time. A close to stoichiometric dissolution was observed after 2 days of experiments. Using an integrated approach, the kinetics was found to be a function of the C/S.

A decrease in layer-to-layer distance in the early stage of the alteration process is interpreted as interlayer Ca/Na exchange (Na being part of the pH buffering solution). A second dissolution step, marked by a close to stoichiometric release of Ca and Si, undoubtedly results from layer dissolution. The structural similarity of C-S-H and tobermorite was confirmed.

Keywords

calcium silicate hydrateC-S-Hdissolutionkineticsalteration product
Type
Research Article
Information
Mineralogical Magazine , Volume 79 , Issue 2 , April 2015 , pp. 437 - 458
Creative Commons
Creative Common License - CCCreative Common License - BY
© [2015] The Mineralogical Society of Great Britain and Ireland. This is an open access article distributed under the terms of the Creative Commons Attribution (CC BY) licence (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2015

References

Allen, A.J., Thomas, J.J. and Jennings, H.M. (2007) Composition and density of nanoscale calciumsilicate-hydrate in cement. Nature Materials, 6, 311–316.CrossRefGoogle ScholarPubMed
Bach, T.T.H., Coumes, C.C.D., Pochard, I., Mercier, C., Revel, B. and Nonat, A. (2012) Influence of temperature on the hydration products of low pH cements. Cement and Concrete Research, 42, 805–817.CrossRefGoogle Scholar
Bach, T.T.H., Chabas, E., Pochard, I., Cau Dit Coumes, C., Haas, J., Frizon, F. and Nonat, A. (2013) Retention of alkali ions by hydrated low-pH cements: Mechanism and Na+/K+ selectivity. Cement and Concrete Research, 51, 14–21.CrossRefGoogle Scholar
Baston, G.M.N., Clacher, A.P., Heath, T.G., Hunter, F.M.I., Smith, V. and Swanton, S.W. (2012) Calcium silicate hydrate (C-S-H) gel dissolution and pH buffering in a cementitious near field. Mineralogical Magazine, 76, 3045–3053.CrossRefGoogle Scholar
Blanc, P., Bourbon, X., Lassin, A. and Gaucher, E.C. (2010) Chemical model for cement-based materials: Temperature dependence of thermodynamic functions for nanocrystalline and crystalline C-S-H phases. Cement and Concrete Research, 40, 851–866.CrossRefGoogle Scholar
Blanc, P., Lassin, A., Piantone, P., Azaroual, M., Jacquemet, N., Fabbri, A. and Gaucher, E.C. (2012) Thermoddem: A geochemical database focused on low temperature water/rock interactions and waste materials. Applied Geochemistry, 27, 2107–2116.CrossRefGoogle Scholar
Bonaccorsi, E., Merlino, S. and Taylor, H.F.W. (2004) The crystal structure of jennite, Ca9Si6O18 (OH)6·8H2O. Cement and Concrete Research, 34, 1481–1488.CrossRefGoogle Scholar
Brunauer, S. (1962) Tobermorite Gel-The heart of concrete. American Scientist, 50, 210–229.Google Scholar
Butcher, E.J., Borwick, J., Collier, N. and Williams, S.J. (2012) Long term leachate evolution during flowthrough leaching of a vault backfill (NRVB). Mineralogical Magazine, 76, 3023–3031.CrossRefGoogle Scholar
Chen, J.J., Sorelli, L., Vandamme, M., Ulm, F.-J. and Chanvillard, G. (2010) A coupled nanoindentation/ SEM-EDS study on low water/cement ratio portland cement paste: evidence for C-S-H/Ca(OH)2 nanocomposites. Journal of the American Ceramic Society, 93, 1484–1493.Google Scholar
Claret, F., Sakharov, B.A., Drits, V.A., Velde, B., Meunier, A., Griffault, L. and Lanson, B. (2004) Clay minerals in the Meuse-Haute Marne Underground Laboratory (France): possible influence of organic matter on clay mineral evolution. Clays and Clay Minerals, 52, 515–532.CrossRefGoogle Scholar
Cong, X. and Kirkpatrick, R.J. (1996) 29Si and 17O NMR investigation of the structure of some crystal-line calcium silicate hydrates. Advanced Cement Based Materials, 3, 133–143.CrossRefGoogle Scholar
Drits, V.A., Lindgreen, H., Sakharov, B.A. and Salyn, A.S. (1997) Sequence structure transformation of illite-smectite-vermiculite during diagenesis of Upper Jurassic shales, North Sea. Clay Minerals, 35, 351–371.CrossRefGoogle Scholar
Galı, S., Ayora, C., Alfonso, P., Tauler, E. and Labrador, M. (2001) Kinetics of dolomite-portlandite reaction: Application to portland cement concrete. Cement and Concrete Research, 31, 933–939.CrossRefGoogle Scholar
Garbev, K., Bornefeld, M., Beuchle, G. and Stemmermann, P. (2008) Cell dimensions and composition of nanocrystalline calcium silicate hydrate solid solutions. Part 2: X-Ray and thermogravimetry study. Journal of the American Ceramic Society, 91, 3015–3023.CrossRefGoogle Scholar
Garcia Calvo, J.L., Hidalgo, A., Alonso, C. and Fernandez Luco, L. (2010) Development of low-pH cementitious materials for HLRW repositories: Resistance against ground waters aggression. Cement and Concrete Research, 40, 1290–1297.CrossRefGoogle Scholar
Gherardi, F., Audigane, P. and Gaucher, E.C. (2012) Predicting long-term geochemical alteration of wellbore cement in a generic geological CO2 confinement site: Tackling a difficult reactive transport modeling challenge. Journal of Hydrology, 420–421.Google Scholar
Glasser, F.P. (2001) Mineralogical aspects of cement in radioactive waste disposal. Mineralogical Magazine, 65, 621–633.CrossRefGoogle Scholar
Grangeon, S., Claret, F., Lerouge, C., Warmont, F., Sato, T., Anraku, S., Numako, C., Linard, Y. and Lanson, B. (2013a) On the nature of structural disorder in calcium silicate hydrates with a calcium/silicon ratio similar to tobermorite. Cement and Concrete Research, 52, 31–37.CrossRefGoogle Scholar
Grangeon, S., Claret, F., Linard, Y. and Chiaberge, C. (2013b) X-ray diffraction: a powerful tool to probe and understand the structure of nanocrystalline calcium silicate hydrates. Acta Crystallographica Section B, 69, 465–473.Google Scholar
Hadi, J., Grangeon, S., Warmont, F., Seron, A. and Greneche, J.-M. (2014) A novel and easy chemicalclock synthesis of nanocrystalline cobalt-iron bearing layered double hydroxides. Journal of Colloid and Interface Science, 434, 130–140.CrossRefGoogle ScholarPubMed
Halim, C.E., Short, S.A., Scott, J.A., Amal, R. and Low, G. (2005) Modelling the leaching of Pb, Cd, As, and Cr from cementitious waste using PHREEQC. Journal of Hazardous Materials, 125, 45–61.CrossRefGoogle ScholarPubMed
Harris, A.W., Manning, M.C., Tearle, W.M. and Tweed, C.J. (2002) Testing of models of the dissolution of cements-leaching of synthetic CSH gels. Cement and Concrete Research, 32, 731–746.CrossRefGoogle Scholar
Hoch, A.R., Baston, G.M.N., Glasser, F.P., Hunter, F.M.I. and Smith, V. (2012) Modelling evolution in the near field of a cementitious repository. Mineralogical Magazine, 76, 3055–3069.CrossRefGoogle Scholar
Houston, J.R., Maxwell, R.S. and Carroll, S.A. (2009) Transformation of meta-stable calcium silicate hydrates to tobermorite: reaction kinetics and molecular structure from XRD and NMR spectroscopy. Geochemical Transactions, 10:1. Kantro, D.L., Brunauer, S. and Weise, C.H. (1962) Development of surface in the hydration of calcium silicates. II. Extension of investigations to earlier and later stages of hydration. The Journal of Physical Chemistry, 66, 1804–1809.Google Scholar
Kim, J.J., Foley, E.M. and Reda Taha, M.M. (2013) Nano-mechanical characterization of synthetic calcium-silicate-hydrate (C-S-H) with varying CaO/SiO2 mixture ratios. Cement and Concrete Composites, 36, 65–70.CrossRefGoogle Scholar
Lanson, B., Marcus, M.A., Fakra, S., Panfili, F., Geoffroy, N. and Manceau, A. (2008) Formation of Zn-Ca phyllomanganate nanoparticles in grass roots. Geochimica et Cosmochimica Acta, 72, 2478–2490.CrossRefGoogle Scholar
Lanson, B., Sakharov, B.A, Claret, F. and Drits, V.A. (2009) Diagenetic smectite-to-illite transition in clay-rich sediments: a reappraisal of X-ray diffraction results using the multi-specimen method. American Journal of Science, 309, 476–516.CrossRefGoogle Scholar
Lasaga, A.C. (1998) Kinetic theory in the earth sciences. Princeton University Press, Princeton, New Jersey, USA. López-Arce, P., Gomez-Villalba, L.S., Pinho, L., Fernández-Valle, M.E., de Buergo, M.A´ . and Fort, R. (2010) Influence of porosity and relative humidity on consolidation of dolostone with calcium hydroxide nanoparticles: Effectiveness assessment with non-destructive techniques. Materials Characterization, 61, 168–184.Google Scholar
Manceau, A., Marcus, M.A., Grangeon, S., Lanson, M., Lanson, B., Gaillot, A.-C., Skanthakumar, S. and Soderholm, L. (2013) Short-range and long-range order of phyllomanganate nanoparticles determined using high-energy X-ray scattering. Journal of Applied Crystallography, 46, 193–209.CrossRefGoogle Scholar
Manzano, H., Dolado, J.S., Guerrero, A. and Ayuela, A. (2007) Mechanical properties of crystalline calciumsilicate-hydrates: comparison with cementitious C-SH gels. physica status solidi (a), 204, 1775–1780.CrossRefGoogle Scholar
Marty, N.C.M., Tournassat, C., Burnol, A., Giffaut, E. and Gaucher, E.C. (2009) Influence of reaction kinetics and mesh refinement on the numerical modelling of concrete/clay interactions. Journal of Hydrology, 364, 58–72.CrossRefGoogle Scholar
Marty, N.C.M., Cama, J., Sato, T., Chino, D., Villiéras, F., Razafitianamaharavo, A., Brendlé, J., Giffaut, E., Soler, J.M., Gaucher, E.C. and Tournassat, C. (2011) Dissolution kinetics of synthetic Na-smectite. An integrated experimental approach. Geochimica et Cosmochimica Acta, 75, 5849–5864.CrossRefGoogle Scholar
McCulloch, C.E., Angus, M.J., Crawford, R.W., Rahman, A.A. and Glasser, F.P. (1985) Cements in radioactive waste disposal: some mineralogical considerations. Mineralogical Magazine, 49, 211–221.CrossRefGoogle Scholar
Merlet, C. (1994) An accurate computer correction program for quantitative electron probe microanalysis. Mikrochimica Acta, 114–115.CrossRefGoogle Scholar
Merlino, S., Bonaccorsi, E. and Armbruster, T. (1999) Tobermorites; their real structure and order-disorder (OD) character. American Mineralogist, 84, 1613–1621.CrossRefGoogle Scholar
Merlino, S., Bonaccorsi, E. and Armbruster, T. (2001) The real structure of tobermorite 11Å: normal and anomalous forms, OD character and polytypic modifications. European Journal of Mineralogy, 13, 577–590.CrossRefGoogle Scholar
Metz, V. and Ganor, J. (2001) Stirring effect on kaolinite dissolution rate. Geochimica et Cosmochimica Acta, 65, 3475–3490.CrossRefGoogle Scholar
Morandeau, A., Thiéry, M. and Dangla, P. (2014) Investigation of the carbonation mechanism of CH and C-S-H in terms of kinetics, microstructure changes and moisture properties. Cement and Concrete Research, 56, 153–170.CrossRefGoogle Scholar
Nonat, A. (2004) The structure and stoichiometry of CS-H. Cement and Concrete Research, 34, 1521–1528.CrossRefGoogle Scholar
Parkhurst, D.L. and Appelo, C.A.J. (1999) User’s Guide to PHREEQC (version 2): A computer program for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations. U.S. Department of the Interior, U.S. Geological Survey, Water-Resources Investigations Report 99-4259. Renaudin, G., Russias, J., Leroux, F., Cau-dit-Coumes, C. and Frizon, F. (2009) Structural characterization of C-S-H and C-A-S-H samples-Part II: Local environment investigated by spectroscopic analyses. Journal of Solid State Chemistry, 182, 3320–3329.Google Scholar
Richardson, I.G. (2004) Tobermorite/jennite-and tobermorite/calcium hydroxide-based models for the structure of C-S-H: applicability to hardened pastes of tricalcium silicate, b-dicalcium silicate, Portland cement, and blends of Portland cement with blast-furnace slag, metakaolin, or silica fume. Cement and Concrete Research, 34, 1733–1777.CrossRefGoogle Scholar
Richardson, I.G. (2008) The calcium silicate hydrates. Cement and Concrete Research, 38, 137–158.CrossRefGoogle Scholar
Šauman, Z. (1971) Carbonization of porous concrete and its main binding components. Cement and Concrete Research, 1, 645–662.CrossRefGoogle Scholar
Savage, D. (2011) A review of analogues of alkaline alteration with regard to long-term barrier performance. Mineralogical Magazine, 75, 2401–2418.CrossRefGoogle Scholar
Schneider, J., Cincotto, M.A. and Panepucci, H. (2001) 29Si and 27Al high-resolution NMR characterization of calcium silicate hydrate phases in activated blastfurnace slag pastes. Cement and Concrete Research, 31, 993–1001.CrossRefGoogle Scholar
Schweizer, C.R. (1999) Calciumsilikathydrat-Mineralien: Lösungskinetik und ihr Einfluss auf das Auswaschverhalten von Substanzen aus einer A b l a g e r u n g m i t R üc k s t ä n d e n a u s Müllverbrennungsanlagen. PhD thesis, University of Basel, Switzerland, p. 113. Skinner, L.B., Chae, S.R., Benmore, C.J., Wenk, H.R. and Monteiro, P.J.M. (2010) Nanostructure of calcium silicate hydrates in cements. Physical Review Letters, 104, 195502. Sugiyama, D. (2008) Chemical alteration of calcium silicate hydrate (C-S-H) in sodium chloride solution. Cement and Concrete Research, 38, 1270–1275.Google Scholar
Suzuki, K. and Nishikawa, T. and Ito, S. (1985) Formation and carbonation of C-S-H in water. Cement and Concrete Research, 15, 213–224.CrossRefGoogle Scholar
Taylor, H.F.W. (1986) Proposed structure for calcium silicate hydrate gel. Journal of the American Ceramic Society, 69, 464–467.CrossRefGoogle Scholar
Trapote-Barreira, A., Cama, J. and Soler, J.M. (2014) Dissolution kinetics of C-S-H gel. Flow-through experiments. Physics and Chemistry of the Earth, Parts A/B/C, 70–71. 17–31.CrossRefGoogle Scholar
Vandamme, M. and Ulm, F.J. (2013) Nanoindentation investigation of creep properties of calcium silicate hydrates. Cement and Concrete Research, 52, 38–52.CrossRefGoogle Scholar
Vieillard, P. and Rassineux, F. (1992) Thermodynamic and geochemical modelling of the alteration of two cement matrices. Applied Geochemistry, 7, Supplement 1, 125–136.CrossRefGoogle Scholar
Villain, G., Thiery, M. and Platret, G. (2007) Measurement methods of carbonation profiles in concrete: Thermogravimetry, chemical analysis and gammadensimetry. Cement and Concrete Research, 37, 1182–1192.CrossRefGoogle Scholar
Watson, C.E., Savage, D., Wilson, J., Walker, C. and Benbow, S.J. (2012) The long-term cement studies project: the UK contribution to model development and testing. Mineralogical Magazine, 76, 3445–3455.CrossRefGoogle Scholar
Wilson, J.C., Benbow, S.J., Metcalfe, R., Savage, D., Walker, C.S. and Chittenden, N. (2011) Fully coupled modeling of long term cement well seal stability in the presence of CO2. Energy Procedia, 4, 5162–5169.CrossRefGoogle Scholar
Supplementary material: File

Marty et al. supplementary material

Appendix

Download Marty et al. supplementary material(File)
File 175.6 KB