Polymer Enhancement Mechanisms in Cementitious Materials: Insights from Atomistic Simulation
Publication: Journal of Materials in Civil Engineering
Volume 36, Issue 3
Abstract
The mechanical properties of organic/inorganic composites at a macroscopic level are largely determined by the interaction mechanisms at the interface. However, there have been limited microscopic studies on these interactions. To address this knowledge gap, this study used molecular dynamics (MD) simulation to examine the interfacial structures, kinetics, and energetics between calcium silicate hydrate (CSH) and polymers. The purpose of this investigation is to shed light on the factors contributing to the variations in mechanical properties of the materials and to provide atomic-level guidance for nanocomposite toughening studies. Three polymers, polyacrylamide (PAM), sodium polyacrylate (PAAS), and polymethacrylic acid sodium sulfonate (PAMAS), were incorporated into the nanochannels of CSH sheets to create polymer/calcium silicate hydrated composites. Our simulations revealed that calcium atoms at the CSH surface act as intermediaries bridging polymers and the CSH through and metal atoms in polymer functional groups through . Furthermore, hydrogen bonds between the interface water molecules and the polymer and CSH matrix were observed through and bonds. Uniaxial tensile simulations were carried out to assess the mechanical behavior of composites, with results indicating that all three materials failed at their interfaces. Analysis of chemical bonding at the point of failure revealed that PAM/CSH exhibits the highest number and stability of chemical bonds and thus the best mechanical properties, followed by PAAS/CSH, with the worst being PAMAS/CSH. Our study provides fundamental atomic-level insights into the differences in interaction mechanisms and macroscopic mechanical properties of composites through molecular dynamics simulation, offering a theoretical basis for polymer modification of CSH and the genetic improvement of cementitious materials.
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Data Availability Statement
All data, models, and code generated or used during the study appear in the published article.
Acknowledgments
Financial support came from from the National Key Research and Development Project (2022YFE0133800); National Natural Science Foundation of China under Grant Nos. U2006224, 52178221, and 51978352; Natural Science Foundation of Shandong Province under Grant Nos. ZR2020JQ25, ZR2022YQ55, and 2019KJG010; and Taishan Scholars tsqn.201812090 supported by Shandong Province.
References
Akinyemi, B. A., and T. E. Omoniyi. 2020. “Repair and strengthening of bamboo reinforced acrylic polymer modified square concrete columns using ferrocement jackets.” Sci. Afr. 8 (Jul): e00378. https://doi.org/10.1016/j.sciaf.2020.e00378.
Allen, A. J., J. J. Thomas, and H. M. Jennings. 2007. “Composition and density of nanoscale calcium–silicate–hydrate in cement.” Nat. Mater. 6 (4): 311–316. https://doi.org/10.1038/nmat1871.
Allouzi, R., H. Almasaeid, A. Alkloub, O. Ayadi, R. Allouzi, and R. Alajarmeh. 2023. “Lightweight foamed concrete for houses in Jordan.” Case Stud. Constr. Mater. 18 (Jul): e01924. https://doi.org/10.1016/j.cscm.2023.e01924.
Bahranifard, Z., F. F. Tabrizi, and A. R. Vosoughi. 2019. “An investigation on the effect of styrene-butyl acrylate copolymer latex to improve the properties of polymer modified concrete.” Constr. Build. Mater. 205 (Apr): 175–185. https://doi.org/10.1016/j.conbuildmat.2019.01.175.
Chen, B. M., G. Qiao, D. S. Hou, M. H. Wang, and Z. J. Li. 2020. “Cement-based material modified by in-situ polymerization: From experiments to molecular dynamics investigation.” Composites, Part B 194 (Aug): 108036. https://doi.org/10.1016/j.compositesb.2020.108036.
Chen, J., M. Qiao, N. X. Gao, J. Z. Wu, G. C. Shan, B. S. Zhu, and Q. P. Ran. 2021. “Acrylate based post-acting polymers as novel viscosity modifying admixtures for concrete.” Constr. Build. Mater. 312 (Dec): 125414. https://doi.org/10.1016/j.conbuildmat.2021.125414.
Cohen, C.-E., F. Malmaison, D. Didier, M. Quintard, and B. Bazin. 2008. “Modeling at different length scales of the wormholing phenomenon.” Chem. Eng. Sci. 63 (May): 3088–3099. https://doi.org/10.1016/j.ces.2008.03.021.
Cygan, R. T., J.-J. Liang, and A. G. Kalinichev. 2004. “Molecular models of hydroxide, oxyhydroxide, and clay phases and the development of a general force field.” J. Phys. Chem. B 108 (4): 1255–1266. https://doi.org/10.1021/jp0363287.
Dauber-Osguthorpe, P., V. A. Roberts, D. J. Osguthorpe, J. Wolff, M. Genest, and A. T. Hagler. 1988. “Structure and energetics of ligand binding to proteins: Escherichia coli dihydrofolate reductase-trimethoprim, a drug-receptor system.” Proteins Struct. Funct. Bioinf. 4 (1): 31–47. https://doi.org/10.1002/prot.340040106.
Donati, I., F. Asaro, and S. Paoletti. 2009. “Experimental evidence of counterion affinity in alginates: The case of non-gelling ion Mg2+.” J. Phys. Chem. B 113 (39): 12877–12886. https://doi.org/10.1021/jp902912m.
Donati, I., A. Ceasaro, and S. Paoletti. 2006. “Specific versus counterion condensation. Nongelling ions polyuronate systems.” Biomacro 7 (May): 281–287. https://doi.org/10.1021/bm050646p.
Gagandeep. 2021. “Experimental study on strength characteristics of polymer concrete with epoxy resin.” Mater. Today Proc. 37 (Jan): 2886–2889. https://doi.org/10.1016/j.matpr.2020.08.665.
Gu, L. A., T. J. Liu, K. Wu, Z. H. Yang, Z. Y. Wen, Z. L. Zhang, G. De Schutter, and H. X. Li. 2022. “Comparative study on the role of PAM and PANA on the property of fresh cement paste.” Cem. Concr. Compos. 133 (Oct): 104701. https://doi.org/10.1016/j.cemconcomp.2022.104701.
Hamid, S. A. 1981. “The crystal structure of the 11Å natural tobermorite .” Zeitschrift für Kristallographie–Crystall. Mater. 154 (3–4): 189–198.
Hammodat, W. W. 2021. “Investigate road performance using polymer modified concrete.” Mater. Today Proc. 42 (Jan): 2089–2094. https://doi.org/10.1016/j.matpr.2020.12.290.
Hassan, R. M. 2020. “Prospective and comparative Novel technique for evaluation the affinity of alginate for binding the alkaline-earth metal ions during formation the coordination biopolymer hydrogel complexes.” Int. J. Biol. Macromol. 165 (Dec): 1022–1028. https://doi.org/10.1016/j.ijbiomac.2020.09.155.
Hirai, T., K. Yagi, K. Nakai, K. Okamoto, D. Murai, and H. Okamoto. 2022. “High-entropy polymer blends utilizing in situ exchange reaction.” Polymer 240 (Feb): 124483. https://doi.org/10.1016/j.polymer.2021.124483.
Hou, D. S., Q. R. Yang, P. Wang, Z. Q. Jin, M. H. Wang, Y. Zhang, and X. P. Wang. 2021. “Unraveling disadhesion mechanism of epoxy/CSH interface under aggressive conditions.” Cem. Concr. Res. 146 (Aug): 106489. https://doi.org/10.1016/j.cemconres.2021.106489.
Hou, D. S., J. Yu, and P. Wang. 2019. “Molecular dynamics modeling of the structure, dynamics, energetics and mechanical properties of cement-polymer nanocomposite.” Composites, Part B 162 (Apr): 433–444. https://doi.org/10.1016/j.compositesb.2018.12.142.
Hou, D. S., J. R. Zhang, Z. J. Li, and Y. Zhu. 2015. “Uniaxial tension study of calcium silicate hydrate (C-S-H): Structure, dynamics and mechanical properties.” Mater. Struct. 48 (11): 3811–3824. https://doi.org/10.1617/s11527-014-0441-1.
Hou, D. S., H. P. Zheng, P. Wang, X. M. Wan, B. Yin, M. H. Wang, and J. R. Zhang. 2022. “Molecular dynamics study on sodium chloride solution transport through the calcium-silicate-hydrate nanocone channel.” Constr. Build. Mater. 342 (Aug): 128068. https://doi.org/10.1016/j.conbuildmat.2022.128068.
Li, G., Y. Ding, T. Y. Gao, Y. M. Qin, Y. J. Lv, and K. J. Wang. 2021. “Chloride resistance of concrete containing nanoparticle-modified polymer cementitious coatings.” Constr. Build. Mater. 299 (Sep): 123736. https://doi.org/10.1016/j.conbuildmat.2021.123736.
Liang, R., Q. Liu, D. S. Hou, Z. J. Li, and G. X. Sun. 2022. “Flexural strength enhancement of cement paste through monomer incorporation and in situ bond formation.” Cem. Concr. Res. 152 (Mar): 106675. https://doi.org/10.1016/j.cemconres.2021.106675.
Liang, Y. Z., and J. K. Zhou. 2023. “Influence of initial tensile stress on mechanical properties of calcium silicate hydrate under various strain rates by molecular dynamics simulation.” Chem. Phys. Lett. 810 (Jan): 140184. https://doi.org/10.1016/j.cplett.2022.140184.
Liu, B. Q., C. Z. Huang, M. Gu, H. T. Zhu, and H. L. Liu. 2007. “Preparation and mechanical properties of in situ growth TiC whiskers toughening ceramic matrix composite.” Mater. Sci. Eng., A 460–461 (Jul): 146–148. https://doi.org/10.1016/j.msea.2007.01.009.
Liu, G., Z. D. Qian, D. Y. Yang, Y. Liu, and Y. X. Yin. 2022a. “Investigation of asphalt concrete used as the ballastless track substructure in long-span railway bridges.” Case Stud. Constr. Mater. 17 (Dec): e01396. https://doi.org/10.1016/j.cscm.2022.e01396.
Liu, Q., Z. Y. Lu, X. X. Liang, R. Liang, Z. J. Li, and G. X. Sun. 2021. “High flexural strength and durability of concrete reinforced by in situ polymerization of acrylic acid and 1-acrylanmido-2-methylpropanesulfonic acid.” Constr. Build. Mater. 292 (Jul): 123428. https://doi.org/10.1016/j.conbuildmat.2021.123428.
Liu, Y. T., D. J. Zheng, E. H. Cao, X. Wu, and Z. Y. Chen. 2022b. “Cracking risk analysis of face slabs in concrete face rockfill dams during the operation period.” Structures 40 (Jun): 621–632. https://doi.org/10.1016/j.istruc.2022.04.054.
Lv, Y. Q., H. J. Wu, H. Dong, H. Y. Zhao, M. Li, and F. L. Huang. 2023. “Experimental and numerical simulation study of fiber-reinforced high strength concrete at high strain rates.” J. Build. Eng. 65 (Apr): 105812. https://doi.org/10.1016/j.jobe.2022.105812.
Manzano, H., S. Moeini, F. Marinelli, A. C. T. van Duin, F.-J. Ulm, and R. J. M. Pellenq. 2012. “Confined water dissociation in microporous defective silicates: Mechanism, dipole distribution, and impact on substrate properties.” J. Am. Chem. Soc. 134 (4): 2208–2215. https://doi.org/10.1021/ja209152n.
Nonat, A. 2004. “The structure and stoichiometry of CSH.” Cem. Concr. Res. 34 (9): 1521–1528. https://doi.org/10.1016/j.cemconres.2004.04.035.
Parsi, S. S., G. Mertz, and A. S. Whittaker. 2022. “Evaluation of design equations for out-of-plane shear strength of deep concrete sections in nuclear power plant buildings.” Nucl. Eng. Des. 386 (Jan): 111545. https://doi.org/10.1016/j.nucengdes.2021.111545.
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.
Qiao, G., D. S. Hou, P. Wang, and Z. Y. Lu. 2021. “Insights on failure modes of calcium-silicate-hydrate interface strengthened by polyacrylamides: Structure, dynamic and mechanical properties.” Constr. Build. Mater. 278 (Apr): 122406. https://doi.org/10.1016/j.conbuildmat.2021.122406.
Rai, U. S., and R. K. Singh. 2005. “Effect of polyacrylamide on the different properties of cement and mortar.” Mater. Sci. Eng., A 392 (1–2): 42–50. https://doi.org/10.1016/j.msea.2004.08.050.
Senthil, K., L. Pelecanos, S. Rupali, R. Sharma, K. Saini, M. A. Iqbal, and N. K. Gupta. 2023. “Experimental and numerical investigation of transient dynamic response on reinforced concrete tunnels against repeated impact loads.” Int. J. Impact Eng. 178 (Aug): 104604. https://doi.org/10.1016/j.ijimpeng.2023.104604.
Sidhu B. S., M. Singh, and J. Singh. 2022. “Experimental analysis of ethylene–ter–polymer (ETA) and poly phosphoric acid (PPA) for modified bituminous concrete.” Mater. Today Proc. 48 (Jan): 1211–1216. https://doi.org/10.1016/j.matpr.2021.08.251.
Starr, J., E. M. Soliman, E. N. Matteo, T. Dewers, J. C. Stormont, and M. M. R. Taha. 2021. “Mechanical characterization of low modulus polymer-modified calcium-silicate-hydrate (C-S-H) binder.” Cem. Concr. Compos. 124 (Nov): 104219. https://doi.org/10.1016/j.cemconcomp.2021.104219.
Varun, B. K., and C. P. Anila Kumar. 2021a. “Flexural and shear characteristics of polymer modified high volume fly ash concrete.” Mater. Today Proc. 46 (Jan): 289–293. https://doi.org/10.1016/j.matpr.2020.08.040.
Varun, B. K., and C. P. Anila Kumar. 2021b. “Strength characteristics of polymer modified high volume fly ash concrete.” Mater. Today Proc. 46 (Jan): 285–288. https://doi.org/10.1016/j.matpr.2020.08.038.
Wang, J. R., H. B. Zhang, Y. Zhu, Z. X. Yan, and H. C. Chai. 2022. “Acrylamide in-situ polymerization of toughened sulphoaluminate cement-based grouting materials.” Constr. Build. Mater. 319 (Apr): 126105. https://doi.org/10.1016/j.conbuildmat.2021.126105.
Wang, P., G. Qiao, Y. P. Guo, Y. Zhang, D. S. Hou, Z. Q. Jin, J. R. Zhang, M. H. Wang, and X. X. Hu. 2020. “Molecular dynamics simulation of the interfacial bonding properties between graphene oxide and calcium silicate hydrate.” Constr. Build. Mater. 260 (Nov): 119927. https://doi.org/10.1016/j.conbuildmat.2020.119927.
Yin, B., X. L. Hua, D. M. Qi, P. Wang, G. Qiao, F. Y. Fan, X. J. Hua, X. P. Wang, and D. S. Hou. 2022. “Performance cement-based composite obtained by in-situ growth of organic-inorganic frameworks during the cement hydration.” Constr. Build. Mater. 336 (Jun): 127533. https://doi.org/10.1016/j.conbuildmat.2022.127533.
Zang, Y., Q. R. Yang, P. Wang, X. P. Wang, D. S. Hou, T. J. Zhao, and J. Q. Chen. 2022. “Molecular dynamics simulation of calcium silicate hydrate/tannic acid interfacial interactions at different temperatures: Configuration, structure and dynamic.” Constr. Build. Mater. 326 (Apr): 126820. https://doi.org/10.1016/j.conbuildmat.2022.126820.
Zhang, H. B., S. W. Yao, J. R. Wang, R. Zhou, Y. Zhu, and D. H. Zou. 2023. “Tensile properties of sulfoaluminate cement-based grouting materials toughened by in-situ polymerization of acrylamide.” Constr. Build. Mater. 375 (Apr): 130885. https://doi.org/10.1016/j.conbuildmat.2023.130885.
Zhou, Y., D. Hou, H. Manzano, C. A. Orozco, G. Geng, P. J. M. Monteiro, and J. Liu. 2017. “Interfacial connection mechanisms in calcium-silicate-hydrates/polymer nanocomposites: A molecular dynamics study.” ACS Appl. Mater. Interfaces 9 (46): 41014–41025. https://doi.org/10.1021/acsami.7b12795.
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Published In
Journal of Materials in Civil Engineering
Volume 36 • Issue 3 • March 2024
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© 2024 American Society of Civil Engineers.
History
Received: Mar 13, 2023
Accepted: Sep 8, 2023
Published online: Jan 3, 2024
Published in print: Mar 1, 2024
Discussion open until: Jun 3, 2024
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