ALBERT

Description: We describe a new and efficient technique to grow aggregates of pure methane hydrate in quantities suitable for physical and material properties testing. Test specimens were grown under static conditions by combining cold, pressurized CH4 gas with granulated H2O ice, and then warming the reactants to promote the reaction CH4(g) + 6H2O(s→l) → CH4·6H2O (methane hydrate). Hydrate formation evidently occurs at the nascent ice/liquid water interface on ice grain surfaces, and complete reaction was achieved by warming the system above the ice melting point and up to 290 K, at 25−30 MPa, for approximately 8 h. The resulting material is pure, cohesive, polycrystalline methane hydrate with controlled grain size and random orientation. Synthesis conditions placed the H2O ice well above its melting temperature while reaction progressed, yet samples and run records showed no evidence for bulk melting of the unreacted portions of ice grains. Control experiments using Ne, a non-hydrate-forming gas, showed that under otherwise identical conditions, the pressure reduction and latent heat associated with ice melting are easily detectable in our fabrication apparatus. These results suggest that under hydrate-forming conditions, H2O ice can persist metastably to temperatures well above its ordinary melting point while reacting to form hydrate. Direct observations of the hydrate growth process in a small, high-pressure optical cell verified these conclusions and revealed additional details of the hydrate growth process. Methane hydrate samples were then tested in constant-strain-rate deformation experiments at T = 140−200 K, Pc = 50−100 MPa, and ε = 10-4−10-6 s-1. Measurements in both the brittle and ductile fields showed that methane hydrate has measurably different strength than H2O ice, and work hardens to an unusually high degree compared to other ices as well as to most metals and ceramics at high homologous temperatures. This work hardening may be related to a changing stoichiometry under pressure during plastic deformation; X-ray analyses showed that methane hydrate undergoes a process of solid-state disproportionation or exsolution during deformation at conditions well within its conventional stability field.

Description: An overview is provided of time-independent physical/chemical properties as related to crystal structures. The following two points are illustrated in this review:  (1) Physical and chemical properties of structure I (sI) and structure II (sII) hydrates are well-defined; measurements have begun on sH. Properties of sI and sII are determined by the molecular structures, described by three heuristics:  (i) Mechanical properties approximate those of ice, perhaps because hydrates are 85 mol % water. Yet each volume of hydrate may contain as much as 180 volumes (STP) of the hydrate-forming species. (ii) Phase equilibrium is set by the size ratio of guest molecules within host cages, and three-phase (Lw−H−V) equilibrium pressure depends exponentially upon temperature. (iii) Heats of formation are set by the hydrogen-bonded crystals and are reasonably constant within a range of guest sizes. (2) Fundamental research challenges are (a) to routinely measure the hydrate phase (via diffraction, NMR, Raman, etc.), and (b) to formulate an acceptable model for hydrate formation kinetics. The reader may wish to investigate details of this review further, via references contained in several recent monographs.