title: Formation and phase transitions of methane hydrates under dynamic loadings: compression rate dependent kinetics.
abstract: We describe high-pressure kinetic studies of the formation and phase transitions of methane hydrates (MH) under dynamic loading conditions, using a dynamic-diamond anvil cell (d-DAC) coupled with time-resolved confocal micro-Raman spectroscopy and high-speed microphotography. The time-resolved spectra and dynamic pressure responses exhibit profound compression-rate dependences associated with both the formation and the solid-solid phase transitions of MH-I to II and MH-II to III. Under dynamic loading conditions, MH forms only from super-compressed water and liquid methane in a narrow pressure range between 0.9 and 1.6 GPa at the one-dimensional (1D) growth rate of 42 μm/s. MH-I to II phase transition occurs at the onset of water solidification 0.9 GPa, following a diffusion controlled mechanism. We estimated the activation volume to be -109±29 Å(3), primarily associated with relatively slow methane diffusion which follows the rapid interfacial reconstruction, or martensitic displacements of atomic positions and hydrogen bonds, of 5(12)6(2) water cages in MH-I to 4(3)5(12)6(3) cages in MH-II. MH-II to III transition, on the other hand, occurs over a broad pressure range between 1.5 and 2.2 GPa, following a reconstructive mechanism from super-compressed MH-II clathrates to a broken ice-filled viscoelastic solid of MH-III. It is found that the profound dynamic effects observed in the MH formation and phase transitions are primarily governed by the stability of water and ice phases at the relevant pressures.
authors.affiliation: Institute for Shock Physics and Department of Chemistry, Washington State University, Pullman, Washington 99164, USA.
authors.forename: Jing-Yin
authors.initials: JY
authors.lastname: Chen
authors.forename: Choong-Shik
authors.initials: CS
authors.lastname: Yoo
mesh_terms: D004058:Diffusion; D007700:Kinetics; D008697:Methane / Q000737:chemistry*; D056004:Molecular Dynamics Simulation; D044367:Phase Transition; D011312:Pressure; D014867:Water / Q000737:chemistry*
chemical_list: D014867:Water; D008697:Methane