Low-frequency electrical properties of ice-silicate mixtures.

The low-frequency electrical properties of mixtures of silicates and saline H(2)O were measured over broad ranges of temperature and frequency to assess the subfreezing interactions between these materials synoptically, particularly the effects of adsorbed, unfrozen water. Adsorbed water content was determined using nuclear magnetic resonance. Materials were chosen to control effects of grain size and mineralogical complexity, and the initial salt content was also specified.

Raman studies of methane-ethane hydrate metastability.

The interconversion of methane-ethane hydrate from metastable to stable structures was studied using Raman spectroscopy. sI and sII hydrates were synthesized from methane-ethane gas mixtures of 65% or 93% methane in ethane and water, both with and without the kinetic hydrate inhibitor, poly(N-vinylcaprolactam). The observed faster structural conversion rate in the higher methane concentration atmosphere can be explained in terms of the differences in driving force (difference in chemical potential of water in sI and sII hydrates) and kinetics (mass transfer of gas and water rearrangement).

Copolymerization of divinylsilyl-11-silicotungstic acid with butyl acrylate and hexanediol diacrylate: synthesis of a highly proton-conductive membrane for fuel-cell applications.

Highly conducive to high conductivity: Polyoxometalates were incorporated in the backbone of a hydrocarbon polymer to produce proton-conducting films. These first-generation materials contain large, dispersed clusters of polyoxometalates. Although the morphology of these films is not yet optimal, they already demonstrate practical proton conductivities and proton diffusion within the clusters appears to be very high.

Low-frequency electrical properties of polycrystalline saline ice and salt hydrates.

We measured the 1 mHz-1 MHz electrical properties of ice-hydrate binary systems formed from solutions of NaCl, CaCl(2), and MgSO(4), with supplementary measurements of HCl. Below the eutectic temperature, electrical parameters are well described by mixing models in which hydrate is always the connected phase. Above the eutectic temperature, a salt concentration threshold of approximately 3 mM in the initial solution is required for the unfrozen brine fraction to form interconnected, electrically conductive networks.

NMR study of methane + ethane structure I hydrate decomposition.

The thermally activated decomposition of methane + ethane structure I hydrate was studied with use of 13C magic-angle spinning (MAS) NMR as a function of composition and temperature. The observed higher decomposition rate of large sI cages initially filled with ethane gas can be described in terms of a model where a distribution of sI unit cells exists such that a particular unit cell contains zero, one, or two methane molecules in the unit cell; this distribution of unit cells is combined to form the observed equilibrium composition. In this model, unit cells with zero methane molecules are the least stable and decompose more rapidly than those populated with one or two methane molecules leading to the observed overall faster decomposition rate of the large cages containing ethane molecules.

Molecular hydrogen storage in binary THF-H2 clathrate hydrates.

The hydrogen storage capacity of binary THF-H(2) clathrate hydrate has been determined as a function of formation pressure, THF composition, and time. The amount of hydrogen stored in the stoichiometric hydrate increases with pressure and exhibits asymptotic (Langmuir) behavior to approximately 1.0 wt % H(2).

Direct measure of the hydration number of aqueous methane.

A hydration number of 20 has been measured for aqueous CH4 in the temperature range 273-298 K on the basis of the simultaneous observation of the 13C isotropic resonance lines of CH4 in both aqueous solution and the dodecahedral cage of CH4 structure I hydrate. Additional experimental evidence and analysis reported in this paper suggest that the dominant aqueous hydration number of methane is 20.

Stable low-pressure hydrogen clusters stored in a binary clathrate hydrate.

Thermodynamic, x-ray diffraction, and Raman and nuclear magnetic resonance spectroscopy measurements show that clusters of H2 can be stabilized and stored at low pressures in a sII binary clathrate hydrate. Clusters of H2 molecules occupy small water cages, whereas large water cages are singly occupied by tetrahydrofuran. The presence of this second guest component stabilizes the clathrate at pressures of 5 megapascals at 279.