Department of Applied Physics, Chalmers University of Technology, SE-41296 Goteborg, SwedenDepartment of Chemistry, Faculty of Science, Okayama University of Science, 1-1 Ridaicho, Okayama 700-0005, Japan.
[Show abstract][Hide abstract] ABSTRACT: Many of water's peculiar physical properties are still not well understood, and one of the most important unresolved questions is its glass transition related dynamics. The consensus has been to accept a glass transition temperature (T(g)) around 136 K, but this value has been questioned and reassigned to about 165 K. We find evidence that the dielectric relaxation process of confined water that has been associated with the long accepted T(g) of water (130-140 K) must be a local process which is not related to the actual glass transition. Rather, our data indicate a glass transition at 160-165 K for bulk water and about 175 K for confined water (depending on the confining system).
[Show abstract][Hide abstract] ABSTRACT: The dynamics of water confined in silica matrices MCM-41 C10 and C18, with pore diameter of 21 and 36 A, respectively, is examined by broadband dielectric spectroscopy (10(-2)-10(9) Hz) and differential scanning calorimetry for a wide temperature interval (110-340 K). The dynamics from capillary condensed hydration water and surface monolayer of water are separated in the analysis. Contrary to previous reports, the rotational dynamics are shown to be virtually independent on the hydration level and pore size. Moreover, a third process, also reported for other systems, and exhibiting a saddlelike temperature dependence is investigated. We argue that this process is due to a Maxwell-Wagner process and not to strongly bound surface water as previously suggested in the literature. The dynamics of this process is strongly dependent on the amount of hydration water in the pores. The anomalous temperature dependence can then easily be explained by a loss of hydration water at high temperatures in contradiction to previous explanations.
The Journal of Chemical Physics 05/2008; 128(15):154503. · 3.12 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: The effect of confinement on the solid-liquid phase transitions of water was studied by using DSC and FT-IR measurements. Enthalpy changes upon melting of frozen water in MCM-41 and SBA-15 were determined as a function of pore size and found to decrease with decreasing pore size. The melting point also decreased almost monotonically with a decrease in pore size. Analysis of the Gibbs-Thomson relation on the basis of the thermodynamic data showed that there were two stages of interfacial free energy change after the constant region, i.e., below a pore size of 6.0 nm: a gradual decrease down to 3.4 nm and another decrease after a small jump upward. This fact demonstrates that the simple Gibbs-Thomson relation, i.e., a linear relation between the melting point change and the inverse pore size, is limited to the range not far from the melting point of bulk water. FT-IR measurements suggest that the decrease in enthalpy change and interfacial free energy change with decreasing pore size reflect the similarity of the structures of both liquid and solid phases of water in smaller pores at lower temperatures.
Physical Chemistry Chemical Physics 08/2006; 8(27):3223-31. · 4.20 Impact Factor
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