Glassy Nature of Water in an Ultraconfining Disordered Material: The Case of Calcium鈭扴ilicate鈭扝ydrate
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- 作者：Mostafa Youssef ; Roland J.-M. Pellenq ; Bilge Yildiz
- 刊名：Journal of the American Chemical Society
- 出版年：2011
- 出版时间：March 2, 2011
- 年：2011
- 卷：133
- 期：8
- 页码：2499-2510
- 全文大小：1109K
- 年卷期：v.133,no.8(March 2, 2011)
- ISSN：1520-5126
文摘
We present the structural and dynamic nature of water ultraconfined in the quasi-two-dimensional nanopores of the highly disordered calcium鈭抯ilicate鈭抙ydrate (C-S-H), the major binding phase in cement. Our approach is based on classical molecular simulations. We demonstrate that the C-S-H nanopore space is hydrophilic, particularly because of the nonbridging oxygen atoms on the disordered silicate chains which serve as hydrogen-bond acceptor sites, directionally orienting the hydrogen atoms of the interfacial water molecules toward the calcium鈭抯ilicate layers. The water in this interlayer space adopts a unique multirange structure: a distorted tetrahedral coordination at short range up to 2.7 脜, a disordered structure similar to that of dense fluids and supercooled phases at intermediate range up to 4.2 脜, and persisting spatial correlations through dipole鈭抎ipole interactions up to 10 脜. A three-stage dynamics governs the mean square displacement (MSD) of water molecules, with a clear cage stage characteristic of the dynamics in supercooled liquids and glasses, consistent with its intermediate-range structure identified here. At the intermediate time scales corresponding to the 尾-relaxation of glassy materials, coincident with the cage stage in MSD, the non-Gaussian parameter indicates a significant heterogeneity in the translational dynamics. This dynamic heterogeneity is induced primarily because of the heterogeneity in the distribution of hydrogen bond strengths. The strongly attractive interactions of water molecules with the calcium silicate walls serve to constrain their motion. Our findings have important implications on describing the cohesion and mechanical behavior of cement from its setting to its aging.