Phillip Servio

Gas hydrate phase equilibrium in the system methane–carbon dioxide–neohexane and water

Abstract Incipient equilibrium hydrate formation conditions for the methane–carbon dioxide–neohexane–water system were obtained by employing the isothermal pressure search method. Two gas mixtures containing 80 and 50% methane respectively on a water-free basis were used. At a given temperature, the incipient hydrate formation pressure from the 80–20 gas mixture with neohexane was found to be lower by about 1 MPa from the hydrate formation pressure for the system without neohexane. This is considered to be an indication that structure H hydrate forms. The results for the 50–50 gas mixture, however, indicate that only below a temperature of approximately 277.5 K it is possible to form structure H hydrate.

Reducing Ice Adhesion on Nonsmooth Metallic Surfaces: Wettability and Topography Effects

The effects of ice formation and accretion on external surfaces range from being mildly annoying to potentially life-threatening. Ice-shedding materials, which lower the adhesion strength of ice to its surface, have recently received renewed research attention as a means to circumvent the problem of icing. In this work, we investigate how surface wettability and surface topography influence the ice adhesion strength on three different surfaces: (i) superhydrophobic laser-inscribed square pillars on copper, (ii) stainless steel 316 Dutch-weave meshes, and (iii) multiwalled carbon nanotube-covered steel meshes. The finest stainless steel mesh displayed the best performance with a 93% decrease in ice adhesion relative to polished stainless steel, while the superhydrophobic square pillars exhibited an increase in ice adhesion by up to 67% relative to polished copper. Comparisons of dynamic contact angles revealed little correlation between surface wettability and ice adhesion. On the other hand, by considering the ice formation process and the fracture mechanics at the ice-substrate interface, we found that two competing mechanisms governing ice adhesion strength arise on nonplanar surfaces: (i) mechanical interlocking of the ice within the surface features that enhances adhesion, and (ii) formation of microcracks that act as interfacial stress concentrators, which reduce adhesion. Our analysis provides insight toward new approaches for the design of ice-releasing materials through the use of surface topographies that promote interfacial crack propagation.

Ab initio DFT study of structural and mechanical properties of methane and carbon dioxide hydrates

The structural and mechanical properties of methane and carbon dioxide hydrates were investigated using density functional theory simulations. Well-established equations of state of solids and exchange-correlation functionals were used for fitting the unit lattice total energy as a function of volume, and the full second-order elastic constants of these two gas hydrates were determined by energy–strain analyses. The polycrystalline elastic properties were also calculated from the unit lattice results. The final results for methane hydrate agree well with available experimental data and with other theoretical results. The two gas hydrates were found to be highly elastically isotropic, but they differed significantly in shear properties. The presented results for carbon dioxide hydrates are the first complete set reported so far. The results are a significant contribution to the ab initio material characterisation of gas hydrates required for ongoing fundamental studies and technological applications.

Kinetics of Ethane Hydrate Growth on Latex Spheres Measured by a Light Scattering Technique

Abstract: A high pressure, temperature‐controlled sapphire equilibrium cell is used to observe the nucleation and growth behavior of gas hydrates in bulk water or on spheres suspended in water. Gas hydrate crystals are grown on positively and negatively charged latex spheres. The experiments have been conducted on an ethane‐water system that is known to form structure I hydrate. Experiments were carried out at temperatures between 278.0 K and 278.6 K and pressures ranging from 1,300 kPa to 1,500 kPa. A light scattering apparatus was used to monitor the hydrate formation process. In particular, the photomultiplier voltage was recorded over time in order to observe the effects of latex spheres on the nucleation and growth of gas hydrates. More experiments need to be performed to better ascertain the hydrate nucleation and growth behavior in the presence of latex spheres.

Fractal and Lacunarity Analyses: Quantitative Characterization of Hierarchical Surface Topographies

Biomimetic hierarchical surface structures that exhibit features having multiple length scales have been used in many technological and engineering applications. Their surface topographies are most commonly analyzed using scanning electron microscopy (SEM), which only allows for qualitative visual assessments. Here we introduce fractal and lacunarity analyses as a method of characterizing the SEM images of hierarchical surface structures in a quantitative manner. Taking femtosecond laser-irradiated metals as an example, our results illustrate that, while the fractal dimension is a poor descriptor of surface complexity, lacunarity analysis can successfully quantify the spatial texture of an SEM image; this, in turn, provides a convenient means of reporting changes in surface topography with respect to changes in processing parameters. Furthermore, lacunarity plots are shown to be sensitive to the different length scales present within a hierarchical structure due to the reversal of lacunarity trends at specific magnifications where new features become resolvable. Finally, we have established a consistent method of detecting pattern sizes in an image from the oscillation of lacunarity plots. Therefore, we promote the adoption of lacunarity analysis as a powerful tool for quantitative characterization of, but not limited to, multi-scale hierarchical surface topographies.

Stress-Sensor Device Based on Flexoelectric Liquid Crystalline Membranes

Membrane flexoelectricity is an electromechanical coupling process that describes membrane bending and membrane electrical polarization caused by bending under electric fields. In this paper we propose, formulate, and characterize a stress-sensor device for mechanically loaded solids, consisting of a soft flexoelectric thin membrane attached to the loaded deformed solid. Because the curvature of the deformed solid is transferred to the attached flexoelectric membrane, the electromechanical transduction of the latter produces a charge that is proportional to the stress of the solid. The model of the stress-sensor device is based on the integration of the thermodynamics of polarizable membranes with isotropic solid elasticity, leading to a transfer function that identifies the elastic, electromechanical, and geometrical parameters involved in electrical-signal generation. The model is applied to representative normal bending and then to more complex off-axis bending of elastic bars. In all cases, a common transfer function shows the generic material and its geometric contributions. The sensor sensitivity increases linearly with flexoelectricity and the membrane-solid interface, and the sensitivity decreases with increasing membrane thickness and Youngs modulus of the solid. The theoretical results contribute to ongoing experimental efforts towards the development of anisotropic soft-matter-based stress-sensor devices through solid-membrane interactions and electromechanical transduction.

Atomistic modeling of structure II gas hydrate mechanics: Compressibility and equations of state

This work uses density functional theory (DFT) to investigate the poorly characterized structure II gas hydrates, for various guests (empty, propane, butane, ethane-methane, propane-methane), at the atomistic scale to determine key structure and mechanical properties such as equilibrium lattice volume and bulk modulus. Several equations of state (EOS) for solids (Murnaghan, Birch-Murnaghan, Vinet, Liu) were fitted to energy-volume curves resulting from structure optimization simulations. These EOS, which can be used to characterize the compressional behaviour of gas hydrates, were evaluated in terms of their robustness. The three-parameter Vinet EOS was found to perform just as well if not better than the four-parameter Liu EOS, over the pressure range in this study. As expected, the Murnaghan EOS proved to be the least robust. Furthermore, the equilibrium lattice volumes were found to increase with guest size, with double-guest hydrates showing a larger increase than single-guest hydrates, which has sign...

Quantitative stability analyses of multiwall carbon nanotube nanofluids following water/ice phase change cycling

Multiwall carbon nanotube nanofluids are regularly investigated for phase change enhancement between liquid and solid states owing to their improved heat transfer properties. The potential applications are numerous, the most notable being latent heat thermal energy storage, but the success of all nanofluid-assisted technologies hinges greatly on the ability of nanoparticles to remain stably dispersed after repeated phase change cycles. In this report, the stability of aqueous nanofluids made from oxygen-functionalized multiwall carbon nanotubes (f-MWCNTs) was profiled over the course of 20 freeze/thaw cycles. Sonication was used after each cycle to re-disperse clusters formed from the crystallization process. This study offers a quantitative evaluation of f-MWCNT-nanofluid stability as a result of phase change through optical characterization of concentration and particle size. It also provides insight into the integrity of the surface functionalities through zeta potential and XPS analyses. Concentration and particle size measurements showed moderate and consistent recoverability of f-MWCNT dispersion following ultrasonication. XPS measurements of solid-state MWCNTs exposed to freeze/thaw cycling in water, and zeta potential analyses of the nanofluids indicate that the surface oxygen content is preserved throughout phase change and over repeated cycles. These results suggest a resilience of oxygen-functionalized MWCNTs to the freezing and thawing of water, which is ideal for their utilization as phase change enhancers.

Molecular mobility in carbon dioxide hydrates

Gas hydrates are at the center of current materials research due to their critical importance to the environment and energy supply, and further progress requires knowledge of their mechanical properties. In this work we use molecular dynamics to study the molecular mobility in carbon dioxide hydrates. Specifically, the influences of induced vacancy defects and changes in composition on diffusion coefficients were studied. Introducing few water vacancy defects and a 3% change in cage occupancy changed the diffusion coefficient by almost two orders of magnitude and a factor of four, respectively. The diffusion coefficient of the water molecules was also influenced but to a much lesser extent.

METHANE HYDRATE STUDIES: DELINEATING PROPERTIES OF HOST SEDIMENTS TO ESTABLISH REPRODUCIBLE DECOMPOSITION KINETICS.

We have presented a summary of measurements on the physical properties of sediments relevant to methane hydrate recovery. The data includes not only geotechnical determinations, but also the CMT data that gives porosity values and pathways through the sediment material. The results show that CMT techniques can be used to study sediment properties on a micrometer-size scale. Since the technique is non-destructive, changes in the sediment microstructures as a function of pressure and temperature can be measured. It is also feasible to look at formation of methane hydrates in the sediment structure as has already been demonstrated [7–9]. A longer term challenge is to start from the microscale data and calculate the macroscopic quantities shown in Table 2. We also note that the CMT measurements help in identification of different minerals found in the sediments. This feature of CMT was not exploited in this survey.