Raman Spectroscopy Study on the Hydration Behaviors of Portland Cement Pastes during Setting
Publication: Journal of Materials in Civil Engineering
Volume 27, Issue 8
Abstract
In the research reported in this paper, an in-situ observation on the hydration of cement pastes with various water-to-cement () ratios was implemented by Raman spectroscopy (RS). The RS was applied to study the paste continuously after cement mixing with water until the final setting was complete. Hydration products, including calcium hydroxide (CH), calcium-silicate-hydrate (C-S-H) gel, and ettringite were detected. The CH and C-S-H gel were present consistently with slight intensity changes in the RS patterns after their first detections. In all the pastes studied, the intensity of ettringite remained constant first, followed by a rapid increasing period; thereafter it began to decrease. Within the measuring duration a new peak assigned to monosulfate was detected in the pastes with ratios of 0.35 and 0.40. These Raman detections were also analyzed together with the setting time and heat evolution to elucidate the early hydration mechanism.
Get full access to this article
View all available purchase options and get full access to this article.
Acknowledgments
The financial supports from the National Science Foundation (CMMI-1265983), the Department of Civil and Environmental Engineering, and the Graduate School Diversity Research Grant for Graduate Students (CODRE) at the University of Louisville are highly appreciated. The writers also thank the Conn’s Center for Renewable Energy Research in the University of Louisville (Kentucky, United States) for providing Raman spectroscopy. The writers also appreciate CEMEX Technical Center for cement chemical composition analysis.
References
ASTM. (2008). “Standard test method for time of setting of hydraulic cement by Vicat needle.”, West Conshohocken, PA.
ASTM. (2009). “Standard test method for measurement of heat of hydration of hydraulic cementitious materials using isothermal conduction calorimetry.”, West Conshohocken, PA.
Bartels, R. H., Beatty, J. C., and Barsky, B. A. (1987). An introduction to splines for use in computer graphic and geometric modeling, M. Kaufmann Publishers, Los Altos, CA.
Bensted, H. (1976). “Use of Raman spectroscopy in cement chemistry.” J. Am. Ceram. Soc., 59(3–4), 140–143.
Black, L., Breen, C., Yarwood, J., Deng, C.-S., Phipps, J., and Maitland, G. (2006). “Hydration of tricalcium aluminate () in the presence and absence of gypsum—Studied by Raman spectroscopy and X-ray diffraction.” J. Mater. Chem., 16(13), 1263–1272.
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.” J. Am. Ceram. Soc., 90(3), 908–917.
Bonen, D., Johnson, T. J., and Sarkar, S. L. (1994). “Characterization of principal clinker materials by FT-Raman microspectroscopy.” Cement Concrete Res., 24(5), 959–965.
Bullard, J. W., et al. (2011). “Mechanisms of cement hydration.” Cement Concrete Res., 41(12), 1208–1223.
Conjeaud, M., and Boyer, H. (1980). “Some possibilities of Raman microprobe in cement chemistry.” Cement Concrete Res., 10(1), 61–70.
Frías, M., and Martínez-Ramírez, S. (2009). “Use of micro-Raman spectroscopy to study reaction kinetics in blended white cement pastes containing metakaolin.” J. Raman Spectrosc., 40(12), 2063–2068.
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.” J. Am. Ceram. Soc., 90(3), 900–907.
Garg, N. (2012). “Raman spectroscopy for characterizing and determining the pozzolanic reactivity of fly ashes.” M.S. thesis, Iowa State Univ., Ames, IA.
Garg, N., Wang, K., and Martin, S. W. (2013). “A Raman spectroscopic study of evolution of sulfates and hydroxides in cement-fly ash pastes.” Cement Concrete Res., 53, 91–103.
Gastaldi, D., Boccaleri, E., Canonico, F., and Bianchi, M. (2007). “The use of Raman spectroscopy as a versatile characterization tool for calciumsulphoaluminate cements: A compositional and hydration study.” J. Mater. Sci., 42(20), 8426–8432.
Hadley, D. W., Dolch, W. L., and Diamond, S. (2000). “On the occurrence of hollow-shell hydration grains in hydrated cement paste.” Cement Concrete Res., 30(1), 1–6.
Kirkpatrick, R. J., Yarger, J. L., McMillan, P. F., Yu, P., and Cong, X. D. (1997). “Raman spectroscopy of C-S-H, tobermorite, and jennite.” Adv. Cement Based Mater., 5(3–4), 93–99.
Kjellsen, K. O., and Lagerblad, B. (2007). “Microstructure of tricalcium silicate and portland cement system at middle periods of hydration—Development of Hadley grains.” Cement Concrete Res., 37(1), 13–20.
Kjellsen, K. O., Lagerblad, B., and Jennings, H. M. (1997). “Hollow-shell formation–An important mode in the hydration of portland cement.” J. Mater. Sci., 32(11), 2921–2927.
Korpa, A., Kowald, T., and Trettin, R. (2009). “Phase development in normal and ultra high performance cementitious systems by quantitative X-ray analysis and thermoanalytical methods.” Cement Concrete Res., 39(2), 69–76.
Liu, F., and Sun, Z. (2013). “Feasibility study of using Raman spectroscopy to detect hydration in wet paste.” ACI Mater. J., 110(6), 611–618.
Odler, I. (2003). “Hydration, setting and hardening of portland cement.” Lea’s chemistry of cement and concrete, 4th Ed., P. C. Hewlett, ed., Elsevier, London, 241–297.
Potgieter-Vermaak, S. S., Potgieter, J. H., Belleil, M., DeWeerdt, F., and Van Grieken, R. (2006). “The application of Raman spectrometry to the investigation of cement. Part II: A micro-Raman study of OPC, slag and fly ash.” Cement Concrete Res., 36(4), 663–670.
Renaudin, G., Segni, R., Mentel, D., Nedelec, J., Leroux, F., and Taviot-Gueho, C. (2007). “A Raman study of the sulfated cement hydrates: Ettringite and monosulfate.” J. Adv. Concrete Technol., 5(3), 299–312.
Sahu, S., Exline, D. L., and Nelson, M. P. (2002). “Identification of thaumasite in concrete by Raman chemical imaging.” Cement Concrete Compos., 24(3–4), 347–350.
Scrivener, K. L. (2004). “Backscattered electron imaging of cementitious microstructures: Understanding and quantification.” Cement Concrete Compos., 26(8), 935–945.
Scrivener, K. L., Fullmann, T., Gallucci, E., Walenta, G., and Bermejo, E. (2004). “Quantitative study of portland cement hydration by X-ray diffraction/Rietveld analysis and independent methods.” Cement Concrete Res., 34(9), 1541–1547.
Tarrida, M., Madon, M., Rolland, B. L., and Colombet, P. (1995). “An in-situ Raman spectroscopy study of the hydration of tricalcium silicate.” Adv. Cement Based Mater., 2(1), 15–20.
Taylor, H. F. W. (1997). Cement chemistry, 2nd Ed., Thomas Telford Publishers, London.
Thomas, J. J., et al. (2011). “Modeling and simulation of cement hydration kinetics and microstructure development.” Cement Concrete Res., 41(12), 1257–1278.
Torréns-Martín, D., Fernández-Carrasco, L., and Martínez-Ramírez, S. (2013). “Hydration of calcium aluminates and calcium sulfoaluminate studied by Raman spectroscopy.” Cem. Concr. Res., 47, 43–50.
Venkiteela, G., and Sun, Z. (2010). “In-situ SEM study of cement particle growth during setting.” Cem. Concr. Compos., 32(3), 211–218.
Voigt, T., Ye, G., Sun, Z., Shah, S. P., and van Breugel, K. (2005). “Early age microstructure of portland cement mortar investigated by ultrasonic shear waves and numerical simulation.” Cement Concrete Res., 35(5), 858–866.
WiRE 3.3 [Computer software]. Renishaw, IL, Renishaw plc.
Ylmen, R., Jaglid, U., Steenari, B. M., and Panas, I. (2009). “Early hydration and setting of portland cement monitored by IR, SEM, and Vicat technique.” Cement Concrete Res., 39(5), 433–439.
Zingg, A., et al. (2008). “The microstructure of dispersed and non-dispersed fresh cement paste—New insight by cryo-microscopy.” Cement Concrete Res., 38(4), 522–529.
Information & Authors
Information
Published In
Journal of Materials in Civil Engineering
Volume 27 • Issue 8 • August 2015
Copyright
© 2014 American Society of Civil Engineers.
History
Received: Mar 19, 2014
Accepted: Sep 2, 2014
Published online: Oct 6, 2014
Discussion open until: Mar 6, 2015
Published in print: Aug 1, 2015
Authors
Metrics & Citations
Metrics
Citations
Download citation
If you have the appropriate software installed, you can download article citation data to the citation manager of your choice. Simply select your manager software from the list below and click Download.