Mesoscale Simulation of the Effect of pH on the Hydration Rate, Morphology, and Mechanical Performance of a Calcium-Silicate-Hydrate Gel
Publication: Journal of Materials in Civil Engineering
Volume 35, Issue 9
Abstract
The pH plays a key role in the hydration process of cement clinker and thus determines the morphology and mechanical performance of cement-based materials. Herein the effect of pH on the nucleation rate, morphology, and mechanical performance of calcium-silicate-hydrate (C-S-H) gel was explored by performing grand canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulation. The results show that the packing fraction of C-S-H gel increases correspondingly as the pH increases. Concerning the morphology of C-S-H gel, the results of specific surface area, coordination structure, cluster size distribution, and pore size distribution indicate that with the increase of pH, the spatial distribution is more heterogeneous and the shape of cluster changes from fibril-like to spherical. In addition, as the decrease of pH, the particles are distributed uniformly thus leading to the increase of mechanical properties. These results acquired from this mesoscale simulation provide insights into the role of pH during cement hydration which is a vital step connecting the nanoscale characterization to its engineering application and designing high-performance cement-based materials.
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Data Availability Statement
Some or all data, models, or code that support the findings of this study are available from the corresponding author upon reasonable request.
Acknowledgments
Financial support from National Natural science foundation of China under Grant Nos. U2006224, 51978352, 52178221, and 51908308, Natural science foundation of Shandong Province under Grant No. ZR2020JQ25, ZR2022YQ55, and Qingdao Science and Technology Leading Talent 19-3-2-13-zhc are gratefully acknowledged.
References
Abdolhosseini Qomi, M. J., et al. 2014. “Combinatorial molecular optimization of cement hydrates.” Nat. Commun. 5 (1): 1–10. https://doi.org/10.1038/ncomms5960.
Baroghel-Bouny, V., M. Mainguy, T. Lassabatere, and O. Coussy. 1999. “Characterization and identification of equilibrium and transfer moisture properties for ordinary and high-performance cementitious materials.” Cem. Concr. Res. 29 (8): 1225–1238. https://doi.org/10.1016/S0008-8846(99)00102-7.
Bhattacharya, S., and K. E. Gubbins. 2006. “Fast method for computing pore size distributions of model materials.” Langmuir 22 (18): 7726–7731. https://doi.org/10.1021/la052651k.
Bonnaud, P. A., C. Labbez, R. Miura, A. Suzuki, N. Miyamoto, N. Hatakeyama, A. Miyamoto, and K. J. Van Vliet. 2016. “Interaction grand potential between calcium–silicate–hydrate nanoparticles at the molecular level.” Nanoscale 8 (7): 4160–4172. https://doi.org/10.1039/C5NR08142D.
Bullard, J. W., H. M. Jennings, R. A. Livingston, A. Nonat, G. W. Scherer, J. S. Schweitzer, K. L. Scrivener, and J. J. Thomas. 2011. “Mechanisms of cement hydration.” Cem. Concr. Res. 41 (12): 1208–1223. https://doi.org/10.1016/j.cemconres.2010.09.011.
Campbell, A. I., V. J. Anderson, J. S. van Duijneveldt, and P. Bartlett. 2005. “Dynamical arrest in attractive colloids: The effect of long-range repulsion.” Phys. Rev. Lett. 94 (20): 208301. https://doi.org/10.1103/PhysRevLett.94.208301.
Coasne, B., K. E. Gubbins, and R. J. M. Pellenq. 2004. “A grand canonical Monte Carlo study of adsorption and capillary phenomena in nanopores of various morphologies and topologies: Testing the BET and BJH characterization methods.” Part. Part. Syst. Char. 21 (2): 149–160. https://doi.org/10.1002/ppsc.200400928.
Constantinides, G., and F.-J. Ulm. 2007. “The nanogranular nature of C–S–H.” J. Mech. Phys. Solids 55 (1): 64–90. https://doi.org/10.1016/j.jmps.2006.06.003.
Edelsbrunner, H., and E. P. Mücke. 1994. “Three-dimensional alpha shapes.” ACM Trans. Graphic 13 (1): 43–72. https://doi.org/10.1145/174462.156635.
Garrault, S., T. Behr, and A. Nonat. 2006. “Formation of the C−S−H layer during early hydration of tricalcium silicate grains with different sizes.” J. Phys. Chem. B 110 (1): 270–275. https://doi.org/10.1021/jp0547212.
Garrault, S., E. Finot, E. Lesniewska, and A. Nonat. 2005. “Study of CSH growth on surface during its early hydration.” Mater. Struct. 38 (4): 435–442. https://doi.org/10.1007/BF02482139.
Garrault, S., and A. Nonat. 2001. “Hydrated layer formation on tricalcium and dicalcium silicate surfaces: Experimental study and numerical simulations.” Langmuir 17 (26): 8131–8138. https://doi.org/10.1021/la011201z.
Goyal, A., K. Ioannidou, C. Tiede, P. Levitz, R. J.-M. Pellenq, and E. Del Gado. 2020. “Heterogeneous surface growth and gelation of cement hydrates.” J. Phys. Chem. C 124 (28): 15500–15510. https://doi.org/10.1021/acs.jpcc.0c02944.
Ioannidou, K., E. Del Gado, F.-J. Ulm, and R. J.-M. Pellenq. 2017. “Inhomogeneity in cement hydrates: Linking local packing to local pressure.” J. Nanomech. Micromech. 7 (2): 04017003. https://doi.org/10.1061/(ASCE)NM.2153-5477.0000120.
Ioannidou, K., M. Kanduč, L. Li, D. Frenkel, J. Dobnikar, and E. Del Gado. 2016a. “The crucial effect of early-stage gelation on the mechanical properties of cement hydrates.” Nat. Commun. 7 (1): 1–9. https://doi.org/10.1038/ncomms12106.
Ioannidou, K., K. J. Krakowiak, M. Bauchy, C. G. Hoover, E. Masoero, S. Yip, F. J. Ulm, P. Levitz, R. J. Pellenq, and E. Del Gado. 2016b. “Mesoscale texture of cement hydrates.” Proc. Natl. Acad. Sci. U.S.A. 113 (8): 2029–2034. https://doi.org/10.1073/pnas.1520487113.
Ioannidou, K., R. J. M. Pellenq, and E. Del Gado. 2014. “Controlling local packing and growth in calcium-silicate-hydrate gels.” Soft Matter 10 (8): 1121–1133. https://doi.org/10.1039/C3SM52232F.
Kanchanason, V., and J. Plank. 2017. “Role of pH on the structure, composition and morphology of CSH–PCE nanocomposites and their effect on early strength development of portland cement.” Cem. Concr. Res. 102 (Dec): 90–98. https://doi.org/10.1016/j.cemconres.2017.09.002.
Li, Z., X. Zhou, H. Ma, and D. Hou. 2022. Advanced concrete technology. Hoboken, NJ: Wiley.
Liu, H., S. Dong, L. Tang, N. M. A. Krishnan, G. Sant, and M. Bauchy. 2019. “Effects of polydispersity and disorder on the mechanical properties of hydrated silicate gels.” J. Mech. Phys. Solids 122 (Jan): 555–565. https://doi.org/10.1016/j.jmps.2018.10.003.
Livingston, R., J. Schweitzer, C. Rolfs, H. Becker, and S. Kubsky. 2001. “Characterization of the induction period in tricalcium silicate hydration by nuclear resonance reaction analysis.” J. Mater. Res. 16 (3): 687–693. https://doi.org/10.1557/JMR.2001.0108.
Ma, H., D. Hou, and Z. Li. 2015. “Two-scale modeling of transport properties of cement paste: Formation factor, electrical conductivity and chloride diffusivity.” Comput. Mater. Sci. 110 (Dec): 270–280. https://doi.org/10.1016/j.commatsci.2015.08.048.
Masoero, E., E. Del Gado, R. J. Pellenq, F. J. Ulm, and S. Yip. 2012. “Nanostructure and nanomechanics of cement: Polydisperse colloidal packing.” Phys. Rev. Lett. 109 (15): 155503. https://doi.org/10.1103/PhysRevLett.109.155503.
Masoero, E., E. Del Gado, R. J. M. Pellenq, S. Yip, and F.-J. Ulm. 2014. “Nano-scale mechanics of colloidal C–S–H gels.” Soft Matter 10 (3): 491–499. https://doi.org/10.1039/C3SM51815A.
Matsuyama, H., and J. Young. 2000. “Effects of pH on precipitation of quasi-crystalline calcium silicate hydrate in aqueous solution.” Adv. Cem. Res. 12 (1): 29–33. https://doi.org/10.1680/adcr.2000.12.1.29.
Mikhail, R. S., L. E. Copeland, and S. Brunauer. 1964. “Pore structures and surface areas of hardened portland cement pastes by nitrogen adsorption.” Can. J. Chem. 42 (2): 426–438. https://doi.org/10.1139/v64-060.
Nicoleau, L., A. Nonat, and D. Perrey. 2013. “The di-and tricalcium silicate dissolutions.” Cem. Concr. Res. 47 (May): 14–30. https://doi.org/10.1016/j.cemconres.2013.01.017.
Nielsen, O., and R. M. Martin. 1983. “First-principles calculation of stress.” Phys. Rev. Lett. 50 (9): 697. https://doi.org/10.1103/PhysRevLett.50.697.
Pellenq, R. J.-M., A. Kushima, R. Shahsavari, K. J. Van Vliet, M. J. Buehler, S. Yip, and F.-J. Ulm. 2009. “A realistic molecular model of cement hydrates.” Proc. Natl. Acad. Sci. U.S.A. 106 (38): 16102–16107. https://doi.org/10.1073/pnas.0902180106.
Pellenq, R.-M., and P. Levitz. 2002. “Capillary condensation in a disordered mesoporous medium: A grand canonical Monte Carlo study.” Mol. Phys. 100 (13): 2059–2077. https://doi.org/10.1080/00268970210129265.
Plassard, C., E. Lesniewska, I. Pochard, and A. Nonat. 2005. “Nanoscale experimental investigation of particle interactions at the origin of the cohesion of cement.” Langmuir 21 (16): 7263–7270. https://doi.org/10.1021/la050440+.
Promentilla, M. A. B., T. Sugiyama, T. Hitomi, and N. Takeda. 2009. “Quantification of tortuosity in hardened cement pastes using synchrotron-based X-ray computed microtomography.” Cem. Concr. Res. 39 (6): 548–557. https://doi.org/10.1016/j.cemconres.2009.03.005.
Rehan, M., W. L. Mattice, and U. W. Suter. 2006. Rotational isomeric state models in macromolecular systems. Berlin: Springer.
Sciortino, F., P. Tartaglia, and E. Zaccarelli. 2005. “One-dimensional cluster growth and branching gels in colloidal systems with short-range depletion attraction and screened electrostatic repulsion.” J. Phys. Chem. B 109 (46): 21942–21953. https://doi.org/10.1021/jp052683g.
Shishehbor, M., D. Sakaniwa, D. Stefaniuk, K. Krakowiak, and M. A. Qomi. 2022. “On the significance of interfacial chemistry on the strength of fly ash-cement composites.” Cem. Concr. Res. 151 (Jan): 106619. https://doi.org/10.1016/j.cemconres.2021.106619.
Stukowski, A. 2009. “Visualization and analysis of atomistic simulation data with OVITO–the open visualization tool.” Modell. Simul. Mater. Sci. Eng. 18 (1): 015012. https://doi.org/10.1088/0965-0393/18/1/015012.
Stukowski, A. 2014. “Computational analysis methods in atomistic modeling of crystals.” JOM 66 (3): 399–407. https://doi.org/10.1007/s11837-013-0827-5.
Suda, Y., T. Saeki, and T. Saito. 2015. “Relation between chemical composition and physical properties of CSH generated from cementitious materials.” J. Adv. Concr. Technol. 13 (5): 275–290. https://doi.org/10.3151/jact.13.275.
Tajuelo Rodriguez, E., I. Richardson, L. Black, E. Boehm-Courjault, A. Nonat, and J. Skibsted. 2015. “Composition, silicate anion structure and morphology of calcium silicate hydrates (CSH) synthesised by silica-lime reaction and by controlled hydration of tricalcium silicate ().” Adv. Appl. Ceram. 114 (7): 362–371. https://doi.org/10.1179/1743676115Y.0000000038.
Taylor, H. F. 1997. Cement chemistry. London: Thomas Telford.
Thomas, J. J., H. M. Jennings, and A. J. Allen. 1998. “The surface area of cement paste as measured by neutron scattering: Evidence for two CSH morphologies.” Cem. Concr. Res. 28 (6): 897–905. https://doi.org/10.1016/S0008-8846(98)00049-0.
Yao, H., L. Ouyang, and W. Y. Ching. 2007. “Ab initio calculation of elastic constants of ceramic crystals.” J. Am. Ceram. Soc. 90 (10): 3194–3204. https://doi.org/10.1111/j.1551-2916.2007.01931.x.
Yaphary, Y. L., F. Sanchez, D. Lau, and C. S. Poon. 2021. “Mechanical properties of colloidal calcium-silicate-hydrate gel with different gel-pore ionic solutions: A mesoscale study.” Micropor. Mesopor. Mat. 316 (Mar): 110944. https://doi.org/10.1016/j.micromeso.2021.110944.
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Journal of Materials in Civil Engineering
Volume 35 • Issue 9 • September 2023
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© 2023 American Society of Civil Engineers.
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Received: Jun 13, 2022
Accepted: Feb 9, 2023
Published online: Jun 23, 2023
Published in print: Sep 1, 2023
Discussion open until: Nov 23, 2023
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