Diffusive dynamics during the high-to-low density transition in amorphous ice.

Water exists in high- and low-density amorphous ice forms (HDA and LDA), which could correspond to the glassy states of high- (HDL) and low-density liquid (LDL) in the metastable part of the phase diagram. However, the nature of both the glass transition and the high-to-low-density transition are debated and new experimental evidence is needed. Here we combine wide-angle X-ray scattering (WAXS) with X-ray photon-correlation spectroscopy (XPCS) in the small-angle X-ray scattering (SAXS) geometry to probe both the structural and dynamical properties during the high-to-low-density transition in amorphous ice at 1 bar. By analyzing the structure factor and the radial distribution function, the coexistence of two structurally distinct domains is observed at T = 125 K. XPCS probes the dynamics in momentum space, which in the SAXS geometry reflects structural relaxation on the nanometer length scale. The dynamics of HDA are characterized by a slow component with a large time constant, arising from viscoelastic relaxation and stress release from nanometer-sized heterogeneities. Above 110 K a faster, strongly temperature-dependent component appears, with momentum transfer dependence pointing toward nanoscale diffusion. This dynamical component slows down after transition into the low-density form at 130 K, but remains diffusive. The diffusive character of both the high- and low-density forms is discussed among different interpretations and the results are most consistent with the hypothesis of a liquid-liquid transition in the ultraviscous regime.

Macroscopic defects upon decomposition of CO2 clathrate hydrate crystals.

Micrometer- and submicrometer-sized pores and macroscopic defects like cracks and tubular channels can be found in a variety of clathrate hydrates (hydrates for short) during formation and decomposition. Their origin, their evolution in time, and their effect on hydrate decomposition kinetics are unclear. We used time-lapse micro computed tomography (µCT) in combination with temperature control and pressure monitoring to study the formation and evolution of pores and macroscopic defects in decomposing CO2 hydrates at subzero (Celsius) temperature. Our results suggest that the decomposition of hydrates is always accompanied by the formation of pores and an increase of the apparent hydrate volume by more than 3%. Hydrate decomposition often starts with the formation of cracks inside the hydrate and not necessarily at the free surface of the hydrate, which frequently remains intact for a long period and seems to be self-preserved in some regions. Decomposition spreads out from these cracks in a uniform fashion yielding a variety of macroscopic features. In some cases, the propagating decomposition front seems to get blocked by planar barriers inside the hydrate yielding regions with high resistance against decomposition. This, together with a generally heterogeneous distribution of decomposition resistant regions, challenges the shrinking core model of hydrate decomposition as well as the popular ice-rind theory used to explain the effect of self-preservation.