Aqueous Solid Formation Kinetics in High-Pressure Methane at Trace Water Concentrations.

Natural gas containing trace amounts of water is frequently liquefied at conditions where aqueous solids are thermodynamically stable. However, no data are available to describe the kinetics of aqueous solid formation at these conditions. Here, we present experimental measurements of both solid formation kinetics and solid-fluid equilibrium for trace concentrations of (12 ± 0.7) ppm water in methane using a stirred, high-pressure apparatus and visual microscopy. Along isochoric pathways with cooling rates around 1 K·min-1, micron-scale aqueous solids were observed to form at subcoolings of (0.3-8.6) K, relative to an average equilibrium melting temperature of (253 ± 1.9) K at (8.9 ± 0.08) MPa; these data are consistent with predicted methane hydrate dissociation conditions within the uncertainty of both the experiment and model. The 36 measured formation events were used to construct a cumulative formation probability distribution, which was then fitted with a model from Classical Nucleation Theory, enabling the extraction of kinetic and thermodynamic nucleation parameters. While the resulting nucleation parameter values were comparable to those published for methane hydrate formation in bulk-water systems, the observed growth kinetics were distinctly different with only a small percentage of the water in the system converting into micron-scale solids over the experimental time scale. These results may help explain how cryogenic heat exchangers in liquefied natural gas facilities can operate for long periods without blockages forming despite being at very high subcoolings for aqueous solids.

Hydrate nucleation and growth on water droplets acoustically-levitated in high-pressure natural gas.

Hydrate formation was studied using water droplets acoustically levitated in high-pressure natural gas. Despite the absence of solid interfaces, the droplets' area-normalised nucleation rate was about four times faster than in steel autoclave measurements with interfacial areas roughly 200 times larger. Multiple stages of stochastic, template-free hydrate growth were observed.

Gas Hydrate Formation Probability Distributions: The Effect of Shear and Comparisons with Nucleation Theory.

Gas hydrate formation is a stochastic phenomenon of considerable significance for any risk-based approach to flow assurance in the oil and gas industry. In principle, well-established results from nucleation theory offer the prospect of predictive models for hydrate formation probability in industrial production systems. In practice, however, heuristics are relied on when estimating formation risk for a given flowline subcooling or when quantifying kinetic hydrate inhibitor (KHI) performance. Here, we present statistically significant measurements of formation probability distributions for natural gas hydrate systems under shear, which are quantitatively compared with theoretical predictions. Distributions with over 100 points were generated using low-mass, Peltier-cooled pressure cells, cycled in temperature between 40 and -5 °C at up to 2 K·min-1 and analyzed with robust algorithms that automatically identify hydrate formation and initial growth rates from dynamic pressure data. The application of shear had a significant influence on the measured distributions: at 700 rpm mass-transfer limitations were minimal, as demonstrated by the kinetic growth rates observed. The formation probability distributions measured at this shear rate had mean subcoolings consistent with theoretical predictions and steel-hydrate-water contact angles of 14-26°. However, the experimental distributions were substantially wider than predicted, suggesting that phenomena acting on macroscopic length scales are responsible for much of the observed stochastic formation. Performance tests of a KHI provided new insights into how such chemicals can reduce the risk of hydrate blockage in flowlines. Our data demonstrate that the KHI not only reduces the probability of formation (by both shifting and sharpening the distribution) but also reduces hydrate growth rates by a factor of 2.

Frequency-based nanoparticle sensing over large field ranges using the ferromagnetic resonances of a magnetic nanodisc.

Using finite element micromagnetic simulations, we study how resonant magnetisation dynamics in thin magnetic discs with perpendicular anisotropy are influenced by magnetostatic coupling to a magnetic nanoparticle. We identify resonant modes within the disc using direct magnetic eigenmode calculations and study how their frequencies and spatial profiles are changed by the nanoparticle's stray magnetic field. We demonstrate that particles can generate shifts in the resonant frequency of the disc's fundamental mode which exceed resonance linewidths in recently studied spin torque oscillator devices. Importantly, it is shown that the simulated shifts can be maintained over large field ranges (here up to 1 T). This is because the resonant dynamics (the basis of nanoparticle detection here) respond directly to the nanoparticle stray field, i.e. detection does not rely on nanoparticle-induced changes to the magnetic ground state of the disc. A consequence of this is that in the case of small disc-particle separations, sensitivities to the particle are highly mode- and particle-position-dependent, with frequency shifts being maximised when the intense stray field localised directly beneath the particle can act on a large proportion of the disc's spins that are undergoing high amplitude precession.

High domain wall velocities via spin transfer torque using vertical current injection.

Domain walls, nanoscale transition regions separating oppositely oriented ferromagnetic domains, have significant promise for use in spintronic devices for data storage and memristive applications. The state of these devices is related to the wall position and thus rapid operation will require a controllable onset of domain wall motion and high speed wall displacement. These processes are traditionally driven by spin transfer torque due to lateral injection of spin polarized current through a ferromagnetic nanostrip. However, this geometry is often hampered by low maximum wall velocities and/or a need for prohibitively high current densities. Here, using time-resolved magnetotransport measurements, we show that vertical injection of spin currents through a magnetic tunnel junction can drive domain walls over hundreds of nanometers at ~500 m/s using current densities on the order of 6 MA/cm(2). Moreover, these measurements provide information about the stochastic and deterministic aspects of current driven domain wall mediated switching.