Publications

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A one-dimensional isobaric reactor model is used to simulate hydrogen isotope exchange processes taking place during flow through a powdered palladium bed. This simple model is designed to serve primarily as a platform for the initial development of detailed chemical mechanisms that can then be refined with the aid of more complex reactor descriptions. The one-dimensional model is based on the Sandia in-house code TPLUG, which solves a transient set of governing equations including an overall mass balance for the gas phase, material balances for all of the gas-phase and surface species, and an ideal gas equation of state. An energy equation can also be solved if thermodynamic properties for all of the species involved are known. The code is coupled with the Chemkin package to facilitate the incorporation of arbitrary multistep reaction mechanisms into the simulations. This capability is used here to test and optimize a basic mechanism describing the surface chemistry at or near the interface between the gas phase and a palladium particle. The mechanism includes reversible dissociative adsorptions of the three gas-phase species on the particle surface as well as atomic migrations between the surface and the bulk. The migration steps are more general than those used previously in that they do not require simultaneous movement of two atoms in opposite directions; this makes possible the creation and destruction of bulk vacancies and thus allows the model to account for variations in the bulk stoichiometry with isotopic composition. The optimization code APPSPACK is used to adjust the mass-action rate constants so as to achieve the best possible fit to a given set of experimental data, subject to a set of rigorous thermodynamic constraints. When data for nearly isothermal and isobaric deuterium-to-hydrogen (D {yields} H) and hydrogen-to-deuterium (H {yields} D) exchanges are fitted simultaneously, results for the former are excellent, while those for the latter show pronounced deviations at long times. These discrepancies can be overcome by postulating the presence of a surface poison such as carbon monoxide, but this explanation is highly speculative. When the method is applied to D {yields} H exchanges intentionally poisoned by known amounts of CO, the fitting results are noticeably degraded from those for the nominally CO-free system but are still tolerable. When TPLUG is used to simulate a blowdown-type experiment, which is characterized by large and rapid changes in both pressure and temperature, discrepancies are even more apparent. Thus, it can be concluded that the best use of TPLUG is not in simulating realistic exchange scenarios, but in extracting preliminary estimates for the kinetic parameters from experiments in which variations in temperature and pressure are intentionally minimized.

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Porous materials having multiple scales of porosity afford the opportunity to combine the high surface area and functionality of nanopores with the superior charge/discharge characteristics of wider transport channels. However, the relative volume fractions assigned to nanopores and transport channels must be thoughtfully balanced because the introduction of transport channels reduces the volume available for nanopore functionality. In the present paper, the optimal balance between nanopore capacity and system response time is achieved by adjusting the aperture and spacing of a family of transport channels that provide access to adjacent nanopores during recharge/discharge cycles of materials intended for storage of gas or electric charge. A diffusive transport model is used to describe alternative processes of viscous gas flow, Knudsen gas flow, and ion diffusion or electromigration. The coupled transport equations for the nanopores and transport channels are linearized and solved analytically for a periodic variation in external gas pressure, ion concentration, or electric potential using a separation-of-variables approach in the complex domain. Optimization of these solutions yields closed-form expressions for channel apertures and spacing that provide maximum discharge of gas or electric charge for a fixed system volume and a desired discharge time. © 2009 The American Physical Society.

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Hierarchical nanoporous materials afford the opportunity to combine the high surface area and functionality of nanopores with the superior charge/discharge characteristics of wider transport channels. In the present paper we optimize the apertures and spacing of a family of transport channels providing access to a surrounding nanoporous matrix during recharge/discharge cycles of materials intended for storage of gas or electric charge. A diffusive transport model is used to describe alternative processes of viscous gas flow, Knudsen gas flow, and ion diffusion. The coupled transport equations for the nanoporous matrix and transport channels are linearized and solved analytically for a periodic variation in external gas pressure or ion density using a separation-of-variables approach in the complex domain. Channel apertures and spacing are optimized to achieve maximum inflow/outflow from the functional matrix material for a fixed system volume.

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Numerical methods are employed to examine the transport of charged species in pressure-driven and electroosmotic flow along nanoscale channels having an electric double-layer thickness comparable to the channel size. In such channels, the electric field inherent to the double layer produces transverse species distributions that depend on species charge. Flow along the channel thus yields mean axial species speeds that also depend on the species charge, enabling species separation and identification. Here we characterize field-flow separations of this type via the retention and plate height. For pressure-driven flows, we demonstrate that mean species speeds along the channel are uniquely associated with a single species charge, allowing species separation based on charge alone. In contrast, electroosmotic flows generally yield identical speeds for several values of the charge, and these speeds generally depend on both the species charge and electrophoretic mobility. Coefficients of dispersion for charged species in both planar and cylindrical geometries are presented as part of this analysis. © 2006 American Chemical Society.

Analytical and numerical solutions are presented for steady evaporating flow in open microchannels having a rectangular cross section and a uniform depth. The flow, driven by the axial gradient of capillary pressure, generally consists of an entry region where the meniscus is attached to the top corners of the channel followed by a jump-like transition to a corner-flow region in which the meniscus progressively recedes into the bottom corners of the channel. Illustrative numerical solutions are used to guide the derivation of an easily applied analytical approximation for the maximum sustainable heat flux or capillary limit. © 2005 Elsevier Ltd. All rights reserved.

The oxidation of zirconium alloys is one of the most studied processes in the nuclear industry. The purpose of this report is to provide in a concise form a review of the oxidation process of zirconium alloys in the moderate temperature regime. In the initial ''pre-transition'' phase, the surface oxide is dense and protective. After the oxide layer has grown to a thickness of 2 to 3 {micro}m's, the oxidation process enters the ''post-transition'' phase where the density of the layer decreases and becomes less protective. A compilation of relevant data suggests a single expression can be used to describe the post-transition oxidation rate of most zirconium alloys during exposure to oxygen, air, or water vapor. That expression is: Oxidation Rate = 13.9 g/(cm{sup 2}-s-atm{sup -1/6}) exp(-1.47 eV/kT) x P{sup 1/6} (atm{sup 1/6}).

Numerical methods are employed to examine the work, electric power input, and efficiency of electrokinetic pumps at a condition corresponding to maximum pump work. These analyses employ the full Poisson-Boltzmann equations and account for both convective and conductive electric currents, including surface conductance. We find that efficiencies at this condition of maximum work depend on three dimensionless parameters, the normalized zeta potential, normalized Debye layer thickness, and a fluid property termed the Levine number indicating the nominal ratio of convective to conductive electric currents. Efficiencies at maximum work exhibit a maximum for an optimum Debye layer thickness when the zeta potential and Levine number are fixed. This maximum efficiency increases with the square of the zeta potential when the zeta potential is small, but reaches a plateau as the zeta potential becomes large. The maximum efficiency in this latter regime is thus independent of the zeta potential and depends only on the Levine number. Simple analytical expressions describing this maximum efficiency in terms of the Levine number are provided. Geometries of a circular tube and planar channel are examined. © 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.