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Comparative Study of Hydration Kinetics of Cement and Tricalcium Silicate Using Terahertz Spectroscopy and Density Functional Theory Simulations

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Abstract

Cement hydration is a process involving simultaneous reactions of cement constituents, primarily tricalcium silicate (C3S) and dicalcium silicate (C2S), with the formation of key hydration products, calcium silicate hydrate (C–S–H) and calcium hydroxide (Ca(OH)2). Compared to the conventionally explored mid-infrared spectroscopy which is bond specific, terahertz (THz) spectroscopy is highly sensitive to crystalline arrangements and resonances in THz frequency range are primarily due to bulk vibrational modes. Hence, THz spectroscopy can be an effective complimentary tool to study the hydration process as C3S gets converted to different polymorphs of C–S–H. To understand the origin and variation of THz resonances of C3S, C–S–H polymorphs and Ca(OH)2, vibrational modes of C3S, tobemorite 9, tobermorite 14, jennite, and portlandite have been calculated using density functional theory simulations. The origin of the main resonances has been studied using vibrational density of states. Simulations show, for C3S, the resonance around 520 cm−1 appears due to combined effect of symmetric and asymmetric vibrations in SiO4 tetrahedra, the resonance around 450 cm−1 appears due to the combined effect of symmetric and asymmetric SiO4 tetrahedra, and CaO vibrations and the resonance around 318 cm−1 is primarily due to CaO vibrations. THz spectroscopy has been performed to track and understand the contribution of C3S in cement hydration. By combining the simulation and experiments, this work clearly explains the reduction of 520 cm−1 resonance, the constant intensity of 450 cm−1 resonance and frequency shift of the main resonances as C3S is transformed into various polymorphs of C–S–H during hydration.

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Acknowledgements

The authors would like to thank Director, CSIR-CEERI, Director, CSIR-SERC, Scientist-in-charge, CEERI, Chennai, for their support throughout the research work and acknowledge the financial support through CSIR network project CSC-0128 (FUTURE). The research work has been carried out with the equipment of CSIR Innovation Complex for which authors would like to thank Director, CSIR-SERC. Shaumik Ray would like to thank CSIR-Senior Research Fellowship for the financial support. The authors would like to thank Rikard Ylmen for his kind suggestions in sample preparation.

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Authors and Affiliations

  1. Council of Scientific and Industrial Research (CSIR), Central Electronics Engineering Research Institute (CEERI), Chennai, Tamil Nadu, 600113, India

    Shaumik Ray, Jyotirmayee Dash, Nirmala Devi & Bala Pesala

  2. Academy of Scientific and Innovative Research, Chennai, Tamil Nadu, 600113, India

    Shaumik Ray, Jyotirmayee Dash, Nirmala Devi, Saptarshi Sasmal & Bala Pesala

  3. Council of Scientific and Industrial Research (CSIR), Structural Engineering Research Centre (SERC), Chennai, Tamil Nadu, 600113, India

    Saptarshi Sasmal

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  1. Shaumik Ray
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Correspondence to Bala Pesala.

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Ray, S., Dash, J., Devi, N. et al. Comparative Study of Hydration Kinetics of Cement and Tricalcium Silicate Using Terahertz Spectroscopy and Density Functional Theory Simulations. J Infrared Milli Terahz Waves 39, 651–666 (2018). https://doi.org/10.1007/s10762-018-0501-7

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