Methane Hydrate Structure I Dissociation Process and Free Surface Analysis.

Methane hydrates are crystalline solids of water that contain methane molecules trapped inside their molecular cavities. Gas hydrates with methane as a guest molecule form structure I hydrates with two small dodecahedral cages and six tetra decahedral large cages. This study assesses the influence of occupation and the behavior of methane release from the molecular perspective during the dissociation process, particularly for the purpose of testing a series of molecular dynamics simulations. The dissociation cases conducted include an ideal 4 × 4 × 4 and 2 × 2 × 2 supercell methane hydrate system while inducing dissociation with two different types of temperature-rising functions for understanding the limitation and capability. These temperature-rising functions are temperature ramping and a single temperature step simulating in 5-7 various conditions. Temperature step results showed the earliest dissociation starting 50 ps into the simulation at an ΔT of 100 K, while at an ΔT of 80 K, dissociation was not observed. There was not a distinct dissociation preference observed between large and small cages, so it appears that the dissociation affects the entire structure uniformly when temperature increases are applied throughout the system rather than transport from a boundary. Temperature ramping simulations showed that the dissociation temperature increased with a higher heating rate. The mean-squared displacement results for the oxygen atoms in the water molecules at a high heating rate of 400 TK/s showed behavior similar to that for methane gas. As in the temperature step simulation, there were no clear differences in dissociation between large and small cages, which suggested homogeneous dissociation in all cases. Finally, a coordination analysis was performed on a 3 × 4 × 4 structure I methane hydrate with two free surfaces to demonstrate clear free surface boundaries and its location.

Dataset for SO2, SO3, H2SO4 and H2O infrared absorption spectra at 300° C and 350° C temperatures.

The data presented here consists of library spectra obtained for use with a laser absorption spectroscopy gas sensor. The spectra include absorbance data for SO2, SO3, H2O and H2SO4 at 300° C and 350° C temperatures in two wavelength bands, 7-8 µm and 8-9 µm. Datasets were collected in a heated multi-pass absorption Herriott cell using two tunable external cavity quantum cascade laser sources, with the resulting transmission signal measured using a thermoelectrically cooled MCT detector. The absorbance was calculated from measurements taken with and without gas samples and scaled for the length of the multi-pass cell. The data will be useful for scientists and engineers building SO3 and H2SO4 gas sensing equipment for emission monitoring, process control, and other applications.

Experimental studies on combined production of CH4 and safe long-term storage of CO2 in the form of solid hydrate in sediment.

The production of the confirmed enormous resources of CH4 trapped in permafrost and deep ocean sediments in the form of hydrates has been hampered by the lack of an extraction procedure that is both effective and environmentally sensitive. This research explores experimentally the dynamic rate limiting steps in the dissociation of methane hydrates and the formation of CO2 hydrates in a sediment matrix. The use of CO2 injection and substitution for hydrate extraction takes advantage of novel thermodynamics and also provides a safe storage option for greenhouse gas. This experimental work incorporates a high-pressure facility dedicated for CH4 hydrates exchange with CO2 that replicates creation of natural gas hydrate from incoming gas below water in the pore space. The hydrate formation/exchange chamber follows the state-of-art hydrate science and is equipped with sensors distributed in several sections: the top section for gas release, a CH4 hydrate section, and a subsequent injection of CO2 from the bottom section, which also mimics hydrate dissociation towards incoming seawater through fracture systems connected from the seafloor. Four experimental conditions were examined. They comprise pure CO2 injection, and 10, 20, and 30 mole% N2 added to the CO2. We observed an increase in CH4 release from pure CO2 injection to 10 mole% N2 addition. A significant extra release of CH4 occurred by stepping up to 20 mole% N2 addition but no significant change was observed from 20 to 30 mole% N2 addition. Maximum conversion in this study is 34 mole% of CO2, and 2 mole% N2 taking the place of methane hydrate in large and small cavities. The results also show that effective substitution for hydrate production cannot rely on pure carbon dioxide injection.

Impact of input field characteristics on vibrational femtosecond coherent anti-Stokes Raman scattering thermometry.

In this paper, three ultrashort-pulse coherent anti-Stokes Raman scattering (CARS) thermometry approaches are summarized with a theoretical time-domain model. The difference between the approaches can be attributed to variations in the input field characteristics of the time-domain model. That is, all three approaches of ultrashort-pulse (CARS) thermometry can be simulated with the unified model by only changing the input fields features. As a specific example, the hybrid femtosecond/picosecond CARS is assessed for its use in combustion flow diagnostics; thus, the examination of the input field has an impact on thermometry focuses on vibrational hybrid femtosecond/picosecond CARS. Beginning with the general model of ultrashort-pulse CARS, the spectra with different input field parameters are simulated. To analyze the temperature measurement error brought by the input field impacts, the spectra are fitted and compared to fits, with the model neglecting the influence introduced by the input fields. The results demonstrate that, however the input pulses are depicted, temperature errors still would be introduced during an experiment. With proper field characterization, however, the significance of the error can be reduced.

Ultra-short pulsed off-axis digital holography for imaging dynamic targets in highly scattering conditions.

A single-shot digital holography system using an ultra-short pulsed laser is demonstrated to be very effective in suppressing the multiple-scattering noise associated with imaging dynamic targets in highly scattering environments, such as biological tissues and fuel injection systems. A planar off-axis reference wave configuration is used to generate a fixed carrier spatial frequency in the recorded holograms in order to separate coherent signal from incoherent noise in Fourier transformed holograms. The single-shot imaging system does not require averaging between multiple shots and can capture images of transient phenomena, such as the formation of diesel fuel injection sprays, and can overcome the problem of mechanical vibrations for recording holograms in industrial and laboratory environments.

Controlled continuous patterning of polymeric nanofibers on three-dimensional substrates using low-voltage near-field electrospinning.

We report on a continuous method for controlled electrospinning of polymeric nanofibers on two-dimensional (2D) and three dimensional (3D) substrates using low voltage near-field electrospinning (LV NFES). The method overcomes some of the drawbacks in more conventional near-field electrospinning by using a superelastic polymer ink formulation. The viscoelastic nature of our polymer ink enables continuous electrospinning at a very low voltage of 200 V, almost an order of magnitude lower than conventional NFES, thereby reducing bending instabilities and increasing control of the resulting polymer jet. In one application, polymeric nanofibers are freely suspended between microstructures of 3D carbon on Si substrates to illustrate wiring together 3D components in any desired pattern.

A transport model for nicotine in the tracheobronchial and pulmonary region of the lung.

Nicotine in mainstream cigarette smoke is predominantly present in the particulate phase. Interestingly, however, the deposition efficiency of smoke particles in the respiratory tract is less effective than is the nicotine retention. In the literature, four nicotine deposition mechanisms are identified: (a) direct gas deposition, (b) evaporative gas deposition, (c) particle deposition with evaporation, and (d) particle deposition with diffusion. In this article we present a physically motivated fundamental model to address nicotine deposition mechanisms (b) and (c) from the vapor phase. The model incorporates nicotine mass transport through estimates for the diffusion time across the epithelial layer and the time for nicotine vapor diffusion from the gas volume to the tissue surfaces in the tracheobronchial and pulmonary regions of the respiratory tract. The model comprises four mass transfer processes for nicotine at the surface of the respiratory tract epithelium: (1) conversion of free base nicotine from protonated nicotine; (2) free base nicotine transport across the epithelium; (3) free base nicotine evaporation; and (4) diffusion of free base nicotine vapor from the surface gas layer into the airway lumen. Results of the nicotine mass transport model suggest that the principal mechanism of nicotine delivery to the lung is by direct deposition of particles to the alveolar fluid lining, followed rapidly by evaporation into the lumen and then gas diffusion back to the surface as nicotine depletes in the surface layer through its transport across the epithelium.

Particle size distribution of nicotine in mainstream smoke from 2R4F, Marlboro Medium, and Quest1 cigarettes under different puffing regimens.

Nicotine's dose and rate of delivery to the brain play an important role in its addiction and cardiovascular effects. Nicotine is mainly present in the particulate phase of cigarette smoke, and since particle size distribution controls the deposition behavior of particles in the respiratory tract, changes in the particle size distribution can produce variations in its regional and total dose to the lung. These variations can change its absorption rate and delivery to the brain. The particle size distribution of mainstream smoke (MS) varies with changes in puffing regimen and cigarette design and composition. This study examined nicotine in different particle size fractions of MS generated from 2R4F, Marlboro Medium, and Quest1 cigarettes using 3 puffing regimens: (1) FTC-like puff, 35 ml over 2 s; (2) short puff, 50 ml over 2 s; and (3) long puff, 100 ml over 10 s. MS was generated in a chamber at 37 degrees C and >95% relative humidity (RH), and size-segregated particles were collected using RJR cascade impactors. Particle size distribution was determined by spectrophotometry. Nicotine was analyzed using gas chromatography and mass spectrometry. Results showed that nicotine speciates in larger particles (1.1-1.9 microm diameter) under the long puffing regimen and in smaller particles (0.4-1.1 microm diameter) under the short puffing regimen, while mass median aerodynamic diameter of mainstream smoke particles was found to be approximately constant (0.9-1.0 microm) for the three puffing regimens. Overall, changes in puffing regimen have a significant effect on particle size distribution of nicotine and its deposited dose.

Using large electric fields to control transport in microgravity.

Transport control by large electric fields in microgravity may be subdivided according to whether the charge carriers are flame ions, ions produced by corona discharges, or electrically charged particles. Using electric fields to induce and direct convection through the drag exercised on neutral gas by ions and to manipulate dispersions and trajectories of electrically charged droplets and particles is especially effective in the absence of Earth's gravity. We have explored applications associated with each of these, and this review collects and summarizes briefly the principal findings of our research, which is scattered widely over the literature of combustion, electrostatics, and experimental science.

Crossed two-beam coherent anti-stokes Raman spectroscopy in dispersive media.

Coherent anti-Stokes Raman spectroscopy (CARS) is a nonlinear optical wave mixing process that is used in gas-phase systems to determine the energy distribution of the probed species (usually N2) and, through a fitting procedure, the temperature giving rise to it. CARS signal strengths are maximized when the phase matching condition is met. Because gases are generally non-dispersive, this phase matching condition can be found geometrically as a function of the crossing angles between the CARS beams and their wavelengths. In addition, perfect phase matching in non-dispersive media occurs automatically for collinear beams. To improve spatial resolution, however, intersecting the laser beams is desirable. Being a third-order process, phase matching for CARS in gases typically requires three input laser beams. This paper discusses and demonstrates the issues of phase matching for CARS when the medium is dispersive, and the ability for CARS phase matching to occur with only two crossed laser beams (one pump and one probe). This two-beam X-CARS in dispersive media can be used as an alignment tool for gas-phase CARS and may be relevant as a simpler diagnostic in high-pressure environments. The paper also discusses the effects of non-ideal phase matching in dispersive and non-dispersive media.

Temperature field measurements of small, nonpremixed flames with use of an Abel inversion of holographic interferograms.

Interferometry has been used for many years as a semi-quantitative image-based diagnostic for combustion research. In this paper, we use image-plane, double-pulse holographic interferograms of axisymmetric flames to infer their radial temperature distribution. An Abel inversion is performed on the fringe data to account for line-of-sight integration through the flame. The sensitivity of nonresonant refractive diagnostics decreases inversely with temperature, and the accuracy of the technique is discussed in this context. A small, nonpremixed capillary flame is investigated, and the temperatures inferred from interferometry are compared with those obtained with N2 coherent anti-Stokes Raman spectroscopy thermometry. Additionally, the thermal field of a burning monodisperse methanol droplet stream is investigated interferometrically. Because of their small size, both of these flames challenge the performance limit of temperature interferometery.