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Updated: Nov 14, 2025

Methane Hydrate Crystallization on Sessile Water Droplets
Published on: May 26, 2021
Structural evolution of methane hydrate under pressures up to 134 GPa
Hirokazu Kadobayashi1, Hisako Hirai2, Hiroaki Ohfuji3
1National Institute for Materials Science (NIMS), Tsukuba, Ibaraki 305-0044, Japan.
Abstract:
High-pressure experiments were performed to understand the structural evolution of methane hydrate (MH) up to 134 GPa using x-ray powder diffraction (XRD) and Raman spectroscopy with diamond anvil cells. XRD revealed the distinct changes in the diffraction lines of MH owing to phase transition from a guest-ordered state phase [MH-III(GOS)] to a new high-pressure phase (MH-IV) at 33.8-57.7 GPa. MH-IV was found to be stable up to at least 134 GPa without decomposition into solid methane and high-pressure ices. Raman spectroscopy showed the splits in the C-H vibration modes ν3 and ν1 of guest methane molecules in filled-ice Ih (MH-III) at 12.7 GPa and 28.6 GPa, respectively. These splits are caused by orientational ordering of guest methane molecules contained in the hydrate structure, as observed in a previous study. These results suggest that the structural evolution of the filled-ice structure of MH is caused by successive orientational ordering of guest methane molecules, thereby inducing changes in the host framework formed by water molecules.
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