Micro-computed tomography of growth and decomposition of clathrate hydrates : time-lapse non-destructive imaging of gas hydrates on the mesoscopic scale

• Main Author: Arzbacher, Stefan
• Format: Thesis
• Language: English
• Published: Universität Innsbruck 2020
• Subjects: 500 Naturwissenschaften und Mathematik; Ice; permafrost
• Online Access: https://dx.doi.org/10.25924/opus-3805; https://opus.fhv.at/3805

Clathrate hydrates, or hydrates for short, are inclusion compounds in which water molecules form a hydrogen-bonded host lattice that accommodates the guest molecules. While vast amounts of hydrates are known to exist in seafloor sediments and in the permafrost on Earth, these occurrences might be dwarfed by the amounts of hydrates occurring in space and on celestial bodies. Since methane is the primary guest molecule in most of the natural occurrences on Earth, hydrates are considered a promising source of energy. Moreover, the ability of one volume of hydrate to store about 170 volumes of gas, make hydrates a promising functional material for various industrial applications. While the static properties of hydrates are reasonably well known, the dynamics of hydrate formation and decomposition are insufficiently understood. For instance, the stochastic period of hydrate nucleation, the memory effect, and the self-preservation phenomenon complicate the development of predictive models of hydrate dynamics. Additionally, the influence of meso- and macroscopic defects as well as the roles of mass and heat transport on different length scales remain to be clarified. Due to its non-invasive and non-destructive nature and the high spatial resolution of approx. 1µm or even less, micro-computed X-ray attenuation tomography ( µCT ) seems to be the perfect method for the study of the evolving structures of forming or decomposing hydrates on the meso- and macroscopic length scale. However, for the naturally occurring hydrates of low atomic number guests the contrast between hydrate, ice, and liquid water is typically very weak because of similar X-ray attenuation coefficients. So far, good contrast was only restricted to synchrotron beamline experiments which utilize the phase information of monochromatic X-rays. In this thesis it is shown that with the help of a newly developed sample cell, a contrast between the hydrate and the ice phase sufficiently good for the reliable segmentation of the materials can also be achieved in conventional tube-based µCT . An accurate pressure and temperature management, i.e., the added functionality of the cell, further allows for cross-correlation of structural and thermodynamic data. The capability of this µCT setup is demonstrated in a series of studies on the formation and decomposition of hydrates which yield new insights for the development of a novel route to hydrate synthesis. At last, this thesis points towards possibilities how better models of hydrate formation and decomposition can be developed with the aid of µCT and computer simulations.