Molecular level knowledge of nucleation and growth of clathrate hydrates is of importance for advancing fundamental understanding on the nature of water and hydrophobic hydrate formers, and their interactions that result in the formation of ice-like solids at temperatures higher than the ice-point. The stochastic nature and the inability to probe the small length and time scales associated with the nucleation process make it very difficult to experimentally determine the molecular level changes that lead to the nucleation event. Conversely, for this reason, there have been increasing efforts to obtain this information using molecular simulations. Accurate knowledge of how and when hydrate structures nucleate will be tremendously beneficial for the development of sustainable hydrate management strategies in oil and gas flowlines, as well as for their application in energy storage and recovery, gas separation, carbon sequestration, seawater desalination, and refrigeration. This article reviews various aspects of hydrate nucleation. First, properties of supercooled water and ice nucleation are reviewed briefly due to their apparent similarity to hydrates. Hydrate nucleation is then reviewed starting from macroscopic observations as obtained from experiments in laboratories and operations in industries, followed by various hydrate nucleation hypotheses and hydrate nucleation driving force calculations based on the classical nucleation theory. Finally, molecular simulations on hydrate nucleation are discussed in detail followed by potential future research directions.
A one-parameter model is presented for the thermal conductivity of nanofluids containing dispersed metallic nanoparticles. The model takes into account the decrease in thermal conductivity of metal nanoparticles with decreasing size. Although literature data could be correlated well using the model, the effect of the size of the particles on the effective thermal conductivity of the nanofluid could not be elucidated from these data. Therefore, new thermal conductivity measurements are reported for six nanofluids containing silver nanoparticles of different sizes and volume fractions. The results provide strong evidence that the decrease in the thermal conductivity of the solid with particle size must be considered when developing models for the thermal conductivity of nanofluids.
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