Molecular Dynamics Study of Water and Ions Transported during the Nanopore Calcium Silicate Phase: Case Study of Jennite
Publication: Journal of Materials in Civil Engineering
Volume 26, Issue 5
Abstract
Durability is an important property that determines the long-term behavior of cement-based materials. Water and ions are transported in nanopores of calcium-silicate-hydrate (C-S-H) gels, the main element in cement-based material, which significantly influences the durability of cement. Because of its structural similarity, jennite, an important mineral analog of C-S-H gel, is first taken to investigate the transport behavior at a molecular level. In this paper, structural and dynamical properties of the water/ions and the jennite interface are studied by the molecular dynamics (MD) simulation method. On the (001) surface of jennite, water molecules diffusing in the channel between silicate chains demonstrate the following structural water features: large density, good orientation preference, ordered interfacial organization, and low diffusion rate. The channel water molecules have more H-bonds connected with the neighboring water molecules and solid surface. As the distance from the channel increases, the structural and dynamical behavior of water molecules varies and gradually translates into bulk water properties at 10–15 Å from the liquid-solid interface. With respect to the interaction between jennite and the ions, the surface demonstrates repulsion and adsorption. With increased ion concentration, the jennite adsorption capability for is enhanced because and aggregate to form a cluster in the interfacial region. The simulation results, matching well with the Nuclear Magnetic Resonance (NMR) studies and isotherm adsorption tests, give a molecular-scale interpretation of experimental studies.
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Acknowledgments
Financial support from the China Ministry of Science and Technology under 2009CB623200 is gratefully acknowledged.
References
Allen, A. J., Thomas, J. J., and Jennings, H. M. (2007). “Composition and density of nanoscale calcium silicate hydrate in cement.” Nature Mat., 6, 311–316.
Andersson, K., Allard, B., Bengtsson, M., and Magnusson, B. (1989). “Chemical composition of cement pore solutions.” Cement Concr. Res., 19(3), 327–332.
Arya, C., and Xu, Y. (1995). “Effect of cement type on chloride binding and corrosion of steel in concrete.” Cement Concr. Res., 25(4), 893–902.
Bakker, H. J. (2008). “Structural dynamics of aqueous salt solutions.” Chem. Rev., 108(4), 1456–1473.
Bergstrom, P. A., and Lindgren, J. (1991). “An IR study of the hydration of perchlorate, nitrate, iodide, bromide, chloride, and sulfate anions in aqueous solution.” J. Phys. Chem., 95(22), 8575–8580.
Bonaccorsi, E., Merlino, S., and Taylor, H. (2004). “The crystal structure of jennite .” Cement Concr. Res., 34(9), 1481–1488.
Bonnaud, P. A., Ji, Q., Coasne, B., Pellenq, R. J.-M., and Van Vliet, K. J. (2012). “Thermodynamics of water confined in porous calcium-silicate-hydrates.” Langmuir, 28(31), 11422–11432.
Bordallo, H. N., Aldridge, L. P., and Desmedt, A. (2006). “Water dynamics in hardened ordinary portland cement paste or concrete: From quasi-elastic neutron scattering.” J. Phys. Chem. B, 110(36), 17966–17976.
Cong, X., and Kirkpatrick, R. (1996). “ MAS NMR study of the structure of calcium silicate hydrate.” Adv. Cement Base. Mater., 3(3–4), 144–156.
Cygan, R. T., Greathouse, J. A., Heinz, H., and Kalinichev, A. G. (2009). “Molecular models and simulations of layered materials.” J. Mat. Chem., 19(17), 2470–2481.
Cygan, R. T., Liang, J. J., and Kalinichev, A. G. (2004). “Molecular models of hydroxide, oxyhydroxide, and clay phases and the development of a general force field.” J. Phys. Chem., 108(4), 1255–1266.
Dolado, J. S., Griebel, M., and Hamaekers, J. (2007). “A molecular dynamic study of cementitious calcium silicate hydrate (C-S-H) gels.” J. Amer. Ceram. Soc., 90(12), 3938–3942.
Dolado, J. S., Griebel, M., Hamaekers, J., and Heberc, F. (2011). “The nano-branched structure of cementitious calcium-silicate-hydrate gel.” J. Mater. Chem., 21(12), 4445–4449.
Janika, J. A., Kurdowsk, W., Podsiadey, R., and Samset, J. (2001). “Fraxtal structure of CSH and tobermorite phases.” Acta Phys. Pol., 100(4), 529–537.
Jennings, H. M. (2008). “Refinements to colloid model of C-S-H in cement: CM II.” Cement Concr. Res., 38(3), 275–289.
Ji, Q., Pellenq, R. J., and Van Vliet, K. J. (2012). “Comparison of computational water models for simulation of calcium silicate hydrate.” Comp. Mat. Sci., 53(1), 234–240.
Kalinichev, A. G., and Kirkpatrick, R. J. (2002). “Molecular dynamics modeling of chloride binding to the surfaces of calcium hydroxide, hydrated calcium aluminate, and calcium silicate phases.” Chem. Mater., 14(8), 3539–3549.
Kalinichev, A. G., Wang, J., and Kirkpatrick, R. J. (2007). “Molecular dynamics modeling of the structure, dynamics, and energetics of mineral water interfaces: Application to cement materials.” Cement Concr. Res., 37(3), 337–347.
Kerisit, S., and Liu, C. X. (2009). “Molecular simulation of water and ion diffusion in nanosized mineral fractures.” Environ. Sci. Tech., 43(3), 777–782.
Kirkpatrick, R., Kalinichev, A. G., and Wang, J. (2005). “Molecular dynamics modeling of mineral interlayers and surfaces: Structure and dynamics.” Mineralog. Mag., 69(3), 287–306.
Kirkpatrick, R. J., Yu, P., and Kalinichev, A. G. (2001). “Chloride binding to cement phases: Exchange isotherm, NMR, and molecular dynamics modeling studies.” Am. Ceram. Soc.: Mater. Sci. Concr., 2001, 77–92.
Lesko, S., Lesniewska, E., Nonat, A., Mutin, J., and Goudonnet, J. (2001). “Investigation by atomic force microscopy of forces at the origin of cement cohesion.” Ultramicroscopy, 82(1–2), 11–21.
Ma, H., and Li, Z. (2013). “Realistic pore structure of portland cement paste: Experimental study and numerical simulation.” Comp. Concr., 11(4), 317–336.
Mindess, S., Darwin, D., and Young, J. F. (2003). Concrete, 2nd Ed., Prentice Hall, Upper Saddle River, NJ.
Page, C., Short, N., and Holden, W. R. (1986). “The influence of different cements on chloride-induced corrosion of reinforcing steel.” Cement Concr. Res., 16(1), 79–86.
Pan, T. Y., and Liu, Y. J. (2009). “Computational molecular analysis of chloride transport in hydrated cement paste.” J. Trans. Res. Board, 2113(1), 31–40.
Pan, T. Y., Xia, K. M., and Wang, L. B. (2010). “Chloride binding to calcium silicate hydrates (C-S-H) in cement paste: A molecular dynamics analysis.” Intl. J. Pave. Eng., 11(5), 367–379.
Pellenq, R. J., et al. (2009). “A realistic molecular model of cement hydrates.” PNAS, 106(38), 16102–16107.
Pellenq, R. J., Lequeux, N., and Damme, H. V. (2008). “Engineering the bonding scheme in C-S-H: The iono-covalent framework.” Cement Concr. Res., 38(2), 159–174.
Plimpton, S., Thompson, A., and Crozier, P. (2010). “LAMMPS molecular dynamics simulator.” 〈http://lammps.sandia.gov/〉 (Aug. 1, 2010).
Richardson, I. G. (2004). “Tobermorite/jennite and tobermorite/calcium hydroxide-based models for the structure of C-S-H: Applicability to hardened pastes of tricalcium silicate, h-dicalcium silicate, Portland cement, and blends of Portland cement with blast-furnace slag, metakaol.” Cement Concr. Res., 34(9), 1733–1777.
Rotenberg, B., Marry, V., Malikova, N., and Turq, P. (2010). “Molecular simulation of aqueous solutions at clay surfaces.” J. Phys.: Cond. Mat., 22(28), 284114.
Tritthart, J. (1989). “Chloride binding in cement II. The influence of the hydroxide concentration in the pore solution of hardened cement paste on chloride binding.” Cement Concr. Res., 19(5), 683–691.
Vasconcelos, I. F., Bunker, B., and Cygan, R. T. (2007). “Molecular dynamics modelling of ion adsorption to the basal surfaces of kaolinite.” J. Phys. Chem. C, 111(18), 6753–6762.
Wang, J. W., Kalinichev, A. G., and Kirkpatrick, R. J. (2004). “Molecular modeling of water structure in nano-pores between brucite (001) surfaces.” Geochim. Cosmochim. Acta, 68(16), 3351–3365.
Wang, P. S., Ferguson, M. M., Eng, G., Bentz, D. P., Ferraris, C. F., and Clifton, J. R. (1998). “1H nuclear magnetic resonance characterization of Portland cement: Molecular diffusion of water studied by spin relaxation and relaxation time-weighted imaging.” J. Mat. Sci., 33(12), 3065–3071.
Youssef, M., Pellenq, R. J., and Yildiz, B. (2011). “Glassy nature of water in an ultraconfining disordered material: The case of calcium silicate hydrate.” J. Am. Chem. Soc., 133(8), 2499–2510.
Yu, P., and Kirkpatrick, R. J. (2001). “ NMR relaxation study of cement hydrate suspensions.” Cement Concr. Res., 31(10), 1479–1485.
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Published In
Journal of Materials in Civil Engineering
Volume 26 • Issue 5 • May 2014
Pages: 930 - 940
Copyright
© 2013 American Society of Civil Engineers.
History
Received: Jan 9, 2013
Accepted: Jun 25, 2013
Published online: Jun 27, 2013
Discussion open until: Nov 27, 2013
Published in print: May 1, 2014
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