journal article·2007Open access

A Raman Study of the Sulfated Cement Hydrates: Ettringite and Monosulfoaluminate

Guillaume Renaudin, Rachid Segni, Dorota Mentel, Jean-Marie Nedelec, Fabrice Leroux, Christine Taviot-Gueho

Abstract

Ettringite (the AFt Ca6Al2(OH)12·(SO4)3·26H2O compound) and monosulfoaluminate (the AFm Ca4Al2(OH)12·SO4·6H2O compound) phases were synthesised by the coprecipitation method and studied by micro-Raman spectroscopy. Hydrogen bond network, involving sulfate anions, ensures the cohesion of the structure of these two compounds; the columnar struture of ettringite as well as the lamellar structure of monosulfoaluminate. Raman spectroscopy has been used as a probe to investigate mainly the inter-columnar and the inter-lamellar regions of the structures. Raman spectra allowed the characterization of the local environment of sulfate anions and the hydrogen bond networks. A significant asset brought by Raman spectroscopy is the ability to work on hydrated cement products without specific sample preparation; i.e. without a risk to dammage these hydrated compounds. Several examples of the possibilities brought by Raman spectroscopy in cement chemistry are given in this paper. A space group redetermination of the ettringite structure was performed on the basis of the point symmetry of sulfate tetrahedra. The inter-columnar region of ettringite was compared to the inter-lamellar region of monosulfoaluminate as these two structural parts contain the same species. The thermal behaviors at the beginning of the dehydration (up to 390 K) and the iron substitution in ettringite were also investigated.
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Research context

OpenAlex topics: Concrete and Cement Materials Research · Clay minerals and soil interactions · Building materials and conservation

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Affiliations

Laboratoire des Matériaux Inorganiques, UMR CNRS 6002, Université Blaise Pascal, and Ecole Nationale Supérieure de Chimie de Clermont-Ferrand, France.

References (44)

Show source-provided references
1. Allman, R. (1977). “Refinement of the hydrid layer structure Ca2Al(OH)6·½SO4·3H2O.” Neues Jahrbuch für Mineralogie Monatshefte, 217, 136-144.
2. Bannister, F. A., Hey, M. H. and Bernal, J. D. (1936). “Ettringite from Scawt Hill.” Mineralogical Magazine, 24, 324-328.
3. Bensted, J. (1976a). “Uses of Raman spectroscopy in cement chemistry.” Journal of the American Ceramic Society, 59 (3-4), 140-143.10.1111/j.1151-2916.1976.tb09451.x ↗
4. Bensted, J. (1976b). “Appraisal of the calcium sulfate - water system by Raman spectroscopy.” Zement Kalk Gips, 29 (9), 416-418.
5. Bensted, J. (1977). “Raman spectral studies of carbonation phenomena.” Cement and Concrete Research, 7 (2), 161-164.10.1016/0008-8846(77)90026-6 ↗
6. Bensted, J. (1999). Colloquium on Techniques for Characterization of Cement Hydration-New and Old Techniques, Society of Chemical Industry Constructions Materials Group, London (1999).
7. Black, L., Breen, C., Yarwood, J., Deng, C.-S., Phipps, J. and Maitland, G. (2006a). “In situ Raman analysis of hydrating C3A and C4AF pastes in presence and absence of sulfate.” Advances in Applied Ceramics, 1005 (4), 209-216.10.1179/174367606X120179 ↗
8. Black, L., Breen, C., Yarwood, J., Deng, C.-S., Phipps, J. and Maitland, G. (2006b). “Hydration of tricalcium aluminate (C3A) in the presence and absence of gypsum - studied by Raman spectroscopy and X-ray diffraction.” Journal of Materials Chemistry, 16, 1263-1272.10.1039/b509904h ↗
9. Black, L., Breen, C., Yarwood, J., Garbev, K., Stemmermann, P. and Gasharova, B. (2007). “Structural features of C-S-H (I) and its carbonation in air - A Raman spectroscopic study. Part II: Carbonated phases.” Journal of the American Ceramic Society, 90 (3), 908-917.
10. Boeyens, J. C. A. and Icharam, V. V. H. (2002). “Redetermination of the crystal structure of calcium sulfate dihydrate, CaSO4·2H2O.” Zeitschrift fuer Kristallographie, 217, 9-10.
11. Brough, A. R. and Atkinson, A. (2001). “Micro-Raman spectroscopy of thaumasite.” Cement and Concrete Research, 31 (3), 421-424.10.1016/S0008-8846(00)00459-2 ↗
12. Conjeaud, M. and Boyer, H. (1980). “Some possibilities of Raman microprobe in cement chemistry.” Cement and Concrete Research, 10 (1), 61-70.10.1016/0008-8846(80)90052-6 ↗
13. Buhlert, R. and Kuzel, H.-J. (1971). “The replacement of Al3+ by Cr3+ and Fe3+ in ettringite.” Zement Kalk Gips, 2, 83-85.
14. Courtois, A., Dusausoy, Y., Lafaille, A. and Protas, J. (1968). “Preliminary study of the crystal structure of ettringite.” Comptes rendus de l'Académie des Sciences de Paris - Série D, 266 (19), 1911-1913. (in French)
15. Deb, S. K., Manghnani, M. H., Ross, K., Livingston, R. A. and Monteiro, P. J. M. (2003). “Raman scattering and X-ray diffraction study of the thermal decomposition of an ettringite-group crystal.” Physics and Chemistry of Minerals, 30, 31-38.
16. El-Turki, A., Ball, R. J. and Allen, G. C. (2007). “The influence of relative humidity on structural and chemical changes during carbonation of hydraulic lime.” Cement and Concrete Research, 37 (8), 1233-1240.10.1016/j.cemconres.2007.05.002 ↗
17. Falk, M. (1975). In: W. A. Adams Ed. Chemistry and physics of aqueous gas solution. Princeton: Electrochem. Soc. Inc., 19.
18. Garbev, K., Stemmermann, P., Black, L., Breen, C., Yarwood, J. and Gasharova, B. (2007). “Structural features of C-S-H (I) and its carbonation in air - A Raman spectroscopic study. Part I: Fresh phases.” Journal of the American Ceramic Society, 90 (3), 900-907.
19. Gastaldi, D., Boccaleri, E., Canonico, F. and Bianchi, M. (2007). “The use of Raman spectroscopy as a versatile characterization tool for calcium sulfoaluminate cements: a compositional and hydration study.” Journal of Materials Science, 42 (20), 8426-8432.10.1007/s10853-007-1790-8 ↗
20. Ghosh, S. N. and Handoo, S. K. (1980). “Infrared and Raman spectral studies in cement and concrete (review).” Cement and Concrete Research, 10 (6), 771-782.10.1016/0008-8846(80)90005-8 ↗
21. Hartman, M. R. and Berliner, R. (2006). “Investigation of the structure of ettringite by time-of-flight neutron powder diffraction techniques.” Cement and Concrete Research, 36, 364-370.10.1016/j.cemconres.2005.08.004 ↗
22. Ibanez, J., Artus, L., Cusco, R., Lopez, A., Menendez, E. and Andrade, M. C. (2007). “Hydration and carbonation of monoclinic C2S and C3S studied by Raman spectroscopy.” Journal of Raman Spectroscopy, 38 (1), 61-67.10.1002/jrs.1599 ↗
23. Jallad, K. N., Santhanam, M., Cohen, M. D. and Ben-Amotz, D. (2001). “Chemical mapping of thaumasite in sulfate-attacked cement mortar using near-infrared Raman imaging microscopy.” Cement and Concrete Research, 31 (6), 953-958.10.1016/S0008-8846(01)00514-2 ↗
24. Kirkpatrick, R. J., Yarger, J. L., McMillan, P. F., Yu, P. and Cong, X. (1997). “Raman spectroscopy of C-S-H, Tobermorite, and Jennite.” Advanced Cement Based Materials, 5 (3-4), 93-99.10.1016/S1065-7355(97)00001-1 ↗
25. Lovy, D. (1996). Program SPECTRAW, Version 1.40, Département de Chimie Physique, University of Geneva, Switzerland.
26. Ma, B., Gao, X., Byars, E. A. and Zhou, Q. (2006). “Thaumasite formation in a tunnel of Bapanxia Dam in Western China.” Cement and Concrete Research, 36 (4), 716-722.10.1016/j.cemconres.2005.10.011 ↗
27. Martinez-Ramirez, S., Sanchez-Cortes, S., Garcia-Ramos, J. V., Domingo, C., Fortes, C. And Blanco-Varela, M. T. (2003). “Micro-Raman spectroscopy applied to depth profiles of carbonates formed in lime mortar.” Cement and Concrete Research, 33 (12), 2063-2068.10.1016/S0008-8846(03)00227-8 ↗
28. Martinez-Ramirez, S., Frias, M. and Domingo, C. (2006). “Micro-Raman spectroscopy in white portland cement hydration: long-term study at room temperature.” Journal of Raman Spectroscopy, 37 (5), 555-561.10.1002/jrs.1428 ↗
29. Moore, A. E. and Taylor, H. F. W. (1968). “Crystal structure of ettringite.” Nature, 218, 1048-1049.10.1038/2181048a0 ↗
30. Moore, A. E. and Taylor, H. F. W. (1970). “Crystal structure of ettringite.” Acta Crystallographica, B26, 386-393.10.1107/S0567740870002443 ↗
31. Myneny, S. C., Traina, S. J., Waychunas, G. A. and Logan, T. J. (1998). “Vibrational spectroscopy of functional group chemistry and arsenate coordination in ettringite.” Geochimica and Cosmchimica Acta, 62 (21-22), 3499-3514.10.1016/S0016-7037(98)00221-X ↗
32. Newman, S. P., Clifford, S. J., Coveney, P. V., Gupta, V., Blanchard, J. D., Serafin, F., Ben-Amotz, D. and Diamond, S. (2005). “Anomalous fluorescence in near-infrared Raman spectroscopy of cementitious materials.” Cement and Concrete Research, 35 (8), 1620-1628.10.1016/j.cemconres.2004.10.001 ↗
33. Pöllmann, H., Kuzel, H.-J. and Wenad, R. (1989). “Compounds with ettringite structure.” Neues Jahrbuch für Mineralogie Monatshefte, 160 (2), 133-158.
34. Potgieter-Vermaak, S. S., Potgieter, J. H. and Van Grieken R. (2006). “The application of Raman spectrometry to investigate and characterize cement, Part I: A review.” Cement and Concrete Research, 36(4), 656-662.10.1016/j.cemconres.2005.09.008 ↗
35. Poupard, O., L'Hostis, V., Catinaud, S. and Petre-Lazar, I. (2006). “Corrosion damage diagnosis of a reinforced concrete beam after 40 years natural exposure in marine environment.” Cement and Concrete Research, 36(3), 504-520.10.1016/j.cemconres.2005.11.004 ↗
36. Prasad, P. S. R., Pradhan, A. and Gowd, T. N. (2001). “In situ micro-Raman investigation of dehydration mechanism in natural gypsum.” Current Science, 80 (9), 1203-1207.
37. Rasmussen, S. E., Jorgensen, J.-E. and Lundtoft, B. (1996). “Structure and phase transition of Na2SO4.” Journal of Applied Crystallography, 29, 42-47.10.1107/S0021889895008818 ↗
38. Renaudin, G., Rapin, J.-P., Humbert, B. and François, M. (2000). “Thermal behavior of the nitrated AFm phase Ca4Al2(OH)12·(NO3)2·4H2O and structure determination of the intermediate hydrate Ca4Al2(OH)12·(NO3)2·2H2O.” Cement and Concrete Research, 30 (2), 307-314.10.1016/S0008-8846(99)00251-3 ↗
39. Rodriguez-Carvajal, J. (2005). PROGRAM FullProf.2k, version 3.20, Laboratoire Léon Brillouin (CEA-CNRS), France, (FullProf.2k manual available on http://www-llb.cea.fr/fullweb/fp2k/fp2k_divers.htm).
40. Sahu, S., Exline, D. L. and Nelson, M. P. (2002). “Identification of thaumasite in concrete by Raman chemical imaging.” Cement and Concrete Composites, 24 (3-4), 347-350.10.1016/S0958-9465(01)00086-5 ↗
41. Shimada, Y. and Young, J. F. (2001). “Structural changes during thermal dehydration of ettringite.” Advances in Cement Research, 13 (2), 77-81.10.1680/adcr.2001.13.2.77 ↗
42. Skibsted, J. and Hall, C. (2007). “Characterization of cement minerals, cements and their reaction products at the atomic and nanoscale level.&rdquo
43. In: J. J. Beaudoin, J. M. Makar and L. Raki, Eds. 12th International Congress on the Chemistry of Cement, Montreal 8-13 July 2007.
44. Tarrida, M., Madon, M., Le Rolland, B. and Colombet, P. (1995). “An in-situ Raman spectroscopy study of the hydration of tricalcium silicate.” Advanced Cement Based Materials, 2 (1), 15-20.10.1016/1065-7355(95)90035-7 ↗