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Hibbs M.R.,Sandia National Laboratories
Journal of Polymer Science, Part B: Polymer Physics | Year: 2013

Anion exchange membranes comprised of a poly(phenylene) backbone and one of five different cationic head-groups are prepared, briefly characterized, and tested for stability in 4 M KOH at 90 °C. The two membranes with resonance-stabilized cations (benzyl pentamethylguanidinium and benzyl N-methylimidazolium) show large (>25%) decreases in both conductivity and ion exchange capacity (IEC) after just one day of testing. The membrane with benzyl trimethylammonium cations shows a 33% loss of conductivity (14% decrease in IEC) after 14 days while the membrane with trimethylammonium cations attached by a hexamethylene spacer shows the least degradation: a 5% loss of conductivity over 14 days with no accompanying loss in IEC. A similar membrane which has a six-carbon spacer and a ketone adjacent to the phenyl ring shows much lower stability, suggesting that the ketone takes part in degradation reactions. © 2012 Wiley Periodicals, Inc. Source


Leung K.,Sandia National Laboratories
Journal of Physical Chemistry C | Year: 2012

Density functional theory and ab initio molecular dynamics simulations are applied to investigate the initial steps of ethylene carbonate (EC) decomposition on spinel Li 0.6Mn 2O 4(100) surfaces. EC is a key component of the electrolyte used in lithium ion batteries. We predict a slightly exothermic EC bond-breaking event on this oxide facet, which facilitates subsequent EC oxidation and proton transfer to the oxide surface. Both the proton and the partially decomposed EC fragment weaken the Mn-O ionic bonding network. Implications for an interfacial film made of decomposed electrolyte on cathode surfaces, and Li xMn 2O 4 dissolution during power cycling, are discussed. © 2012 American Chemical Society. Source


Nanogeochemistry-a newly emerging research field-attempts to understand geochemical reactions and mass transfers at nanometer scales, especially with regards to the formation of nanostructures in geochemical systems, emergent properties of these structures, and their controls on geochemical processes. The research also includes use of nanotechnology to design new materials and engineering approaches for effective natural resource extraction and environmental management. At the core of this new research field is the concept that, as the size of a material is reduced to nanometers, novel physical or chemical properties of the material may emerge that can be drastically different from those of the corresponding bulk phase and the material properties then become size-dependent. Nanostructures, which frequently occur in geologic materials, may directly control mineral phase stability, mineral-water interface chemistry, geochemical reaction kinetics, geo-fluid migration and transport, and even global biogeochemical cycles as a whole. This paper aims to provide a comprehensive review of recent progress in nanogeochemical research. The review is focused on two general types of nanostructures-nano solid phases and nanopores (nanofluids)-with an emphasis on the occurrence of each nanostructure in natural environments, the associated emergent properties, and the potential geochemical implications. Stemming from an increasing interest in shale gas research, a special discussion is provided on gas/oil disposition and migration in unconventional low-permeability reservoirs, wherein shale is treated as a nanocomposite material. Nanogeochemistry is a relatively young research field, and much remains to be explored. There is an urgent need for systematically characterizing specific nanostructures over the whole nanometer-size range and developing a general theoretical framework for data analysis and synthesis. There is also a need for developing experimental and modeling techniques to extrapolate the knowledge obtained from simple model systems to complex natural systems. © 2014 Elsevier B.V. Source


Bishop J.E.,Sandia National Laboratories
International Journal for Numerical Methods in Engineering | Year: 2014

A displacement-based continuous-Galerkin finite element formulation for general polyhedra is presented for applications in nonlinear solid mechanics. The polyhedra can have an arbitrary number of vertices or faces. The faces of the polyhedra can have an arbitrary number of edges and can be nonplanar. The polyhedra can be nonconvex with only the mild restriction of star convexity with respect to the vertex-averaged centroid. Conforming shape functions are constructed using harmonic functions defined on the undeformed configuration, thus requiring the use of a total-Lagrangian finite element formulation in large deformation applications. For nonlinear applications with computationally intensive constitutive models, it is important to minimize the number of element quadrature points. For this reason, an integration scheme is adopted in which the number of quadrature points is equal to the number of vertices. As a first step toward verifying the element behavior in the general nonlinear setting, several linear verification examples are presented using both random Voronoi meshes and distorted hexahedral meshes. For the hexahedral meshes, results for the polyhedral formulation are compared to those of the standard trilinear hexahedral formulation. The element behavior in the nearly incompressible regime is also examined. © 2013 John Wiley & Sons, Ltd. Source


Sheps L.,Sandia National Laboratories
Journal of Physical Chemistry Letters | Year: 2013

We present the time-resolved UV absorption spectrum of the B̃ ( 1A′) ← X̃ (1A′) electronic transition of formaldehyde oxide, CH2OO, produced by the reaction of CH2I radicals with O2. In contrast to its UV photodissociation action spectrum, the absorption spectrum of formaldehyde oxide extends to longer wavelengths and exhibits resolved vibrational structure on its low-energy side. Chemical kinetics measurements of its reactivity establish the identity of the absorbing species as CH2OO. Separate measurements of the initial CH2I radical concentration allow a determination of the absolute absorption cross section of CH2OO, with the value at the peak of the absorption band, 355 nm, of σabs = (3.6 ± 0.9) × 10-17 cm2. The difference between the absorption and action spectra likely arises from excitation to long-lived B̃ (1A′) vibrational states that relax to lower electronic states by fluorescence or nonradiative processes, rather than by photodissociation. © 2013 American Chemical Society. Source

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