Ion Association in [bmim][PF6]/Naphthalene Mixtures: An Experimental and Computational Study

Mixtures of room temperature ionic liquids (IL) with neutral organic molecules provide a valuable testing ground to investigate the interplay of the ionic and molecular-dipolar state in dense Coulomb systems at near ambient conditions. In the present study, the viscosity eta and the ionic conductivity a of 1-n-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6])/naphthalene mixtures at T = 80 degrees C have been measured at 10 stoichiometries spanning the composition range from pure naphthalene to pure [bmim][PF6]. The viscosity grows nearly monotonically with increasing IL mole fraction (x), whereas the conductivity per ion displays a clear peak at x approximate to 15%. The origin of this maximum has been investigated using molecular dynamics simulations based on a classical force field. Snapshots of the simulated samples show that the conductivity maximum is due to the gradual transition in the IL component from an ionic state at high x to a dipolar fluid made of neutral ion pairs at low x. At concentrations x <0.20 the ion pairs condense into molecular-thin filaments bound by dipolar forces and extending in between nanometric droplets of IL. These results are confirmed and complemented by the computation of dynamic and transport properties in [bmim][PF6]/naphthalene mixtures at low IL concentration.

A computational study of the mechanism of CO oxidation by a ceria supported surface rhodium oxide layer

A mechanism of CO oxidation by a thin surface oxide of Rh supported on ceria is proposed: CO is oxidized by the Rh-oxide film, which is subsequently reoxidized by a ceria surface O atom. The proposed mechanism is supported by in situ Raman spectroscopic investigations.

A combined transient and computational study of the dissociation of N(2)O on platinum catalysts

The energetics of the low-temperature adsorption and decomposition of nitrous oxide, N(2)O, on flat and stepped platinum surfaces were calculated using density-functional theory (DFT). The results show that the preferred adsorption site for N(2)O is an atop site, bound upright via the terminal nitrogen. The molecule is only weakly chemisorbed to the platinum surface. The decomposition barriers on flat (I 11) surfaces and stepped (211) surfaces are similar. While the barrier for N(2)O dissociation is relatively small, the surface rapidly becomes poisoned by adsorbed oxygen. These findings are supported by experimental results of pulsed N(2)O decomposition with 5% Pt/SiO(2) and bismuth-modified Pt/C catalysts. At low temperature, decomposition occurs but self-poisoning by O((ads)) prevents further decomposition. At higher temperatures some desorption Of O(2) is observed, allowing continued catalytic activity. The study with bismuth-modified Pt/C catalysts showed that, although the activation barriers calculated for both terraces and steps were similar, the actual rate was different for the two surfaces. Steps were found experimentally to be more active than terraces and this is attributed to differences in the preexponential term. (C) 2004 Elsevier Inc. All rights reserved.

Integration Of Strength and Process Modelling of Friction-Stir-Welded Fuselage Panels

In order to reduce potential uncertainties and conservatism in welded panel analysis procedures, understanding of the relationships between welding process parameters and static strength is required. The aim of this study is to determine and characterize the key process induced properties of advanced welding assembly methods on stiffened panel local buckling and collapse performance. To this end, an in-depth experimental and computational study of the static strength of a friction stir welded fuselage skin-stiffener panel subjected to compression loading has been undertaken. Four welding process effects, viz. the weld joint width, the width of the weld Heat Affected Zone, the strength of material within the weld Heat Affected Zone and the magnitude of welding induced residual stress, are investigated. A fractional factorial experiment design method (Taguchi) has been applied to identify the relative importance of each welding process effect and investigate effect interactions on both local skin buckling and crippling collapse performance. For the identified dominant welding process effects, parametric studies have been undertaken to identify critical welding process effect magnitudes and boundaries. The studies have shown that local skin buckling is principally influenced by the magnitude of welding induced residual stress and that the strength of material in the Heat Affected Zone and the magnitude of the welding induced residual stress have the greatest influence on crippling collapse behavior.


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Buckling/post-buckling strength of friction stir welded aircraft stiffened panels

Assembling aircraft stiffened panels using friction stir welding offers potential to reduce fabrication time in comparison to current mechanical fastener assembly, making it economically feasible to select structurally desirable stiffener pitching and novel panel configurations. With such a departure from the traditional fabrication process, much research has been conducted on producing strong reliable welds, with less examination of the impact of welding process residual effects on panel structural behaviour and the development of appropriate design methods. This article significantly expands the available panel level compressive strength knowledge, demonstrating the strength potential of a welded aircraft panel with multiple lateral and longitudinal stiffener bays. An accompanying computational study has determined the most significant process residual effects that influence panel strength and the potential extent of panel degradation. The experimental results have also been used to validate a previously published design method, suggesting accurate predictions can be made if the conventional aerospace design methods are modified to acknowledge the welding altered panel properties.

Binding of Calcium and Carbonate to Polyacrylates

Polyacrylate molecules can be used to slow the growth of calcium carbonate. However, little is known about the mechanism by which the molecules impede the growth rate. A recent computational study (Bulo et al. Macromolecules 2007, 40, 3437) used metadynamics to investigate the binding of calcium to polyacrylate chains and has thrown some light on the coiling and precipitation of these polymers. We extend these simulations to examine the binding of calcium and carbonate to polyacrylate chains. We show that calcium complexed with both carbonate and polyacrylate is a very stable species. The free energies of calcium-carbonate-polyacrylate complexes, with different polymer configurations, are calculated, and differences in the free energy of the binding of carbonate are shown to be due to differences in the amount of steric hindrance about the calcium, which prevents the approach of the carbonate ion.

High pressure CO2 absorption studies on imidazolium-based ionic liquids:Experimental and simulation approaches

A combined experimental-computational study on the CO absorption on 1-butyl-3-methylimidazolium hexafluophosphate, 1-ethyl-3-methylimidazolium bis[trifluoromethylsulfonyl]imide, and 1-butyl-3-methylimidazolium bis[trifluoromethylsulfonyl]imide ionic liquids is reported. The reported results allowed to infer a detailed nanoscopic vision of the absorption phenomena as a function of pressure and temperature. Absorption isotherms were measured at 318 and 338K for pressures up to 20MPa for ultrapure samples using a state-of-the-art magnetic suspension densimeter, for which measurement procedures are developed. A remarkable swelling effect upon CO absorption was observed for pressures higher than 10MPa, which was corrected using a method based on experimental volumetric data. The experimental data reported in this work are in good agreement with available literature isotherms. Soave-Redlich-Kwong and Peng-Robinson equations of state coupled with bi-parametric van der Waals mixing rule were used for successful correlations of experimental high pressure absorption data. Molecular dynamics results allowed to infer structural, energetic and dynamic properties of the studied CO+ionic liquids mixed fluids, showing the relevant role of the strength of anion-cation interactions on fluid volumetric properties and CO absorption. © 2012 Elsevier B.V.

High-pressure deformation mechanism in scolecite: A combined computational-experimental study

Pressure-induced structural modifications in scolecite were studied by means of in situ synchrotron X-ray powder diffraction and density functional computations. The experimental cell parameters were refined up to 8.5 GPa. Discontinuities in the slope of the unit-cell parameters vs. pressure dependence were observed; as a consequence, an increase in the slope of the linear pressure-volume dependence is observed at about 6 GPa, suggesting an enhanced compressibility at higher pressures. Weakening and broadening of the diffraction peaks reveals increasing structural disorder with pressure, preventing refinement of the lattice parameters above 8.5 GPa. Diffraction patterns collected during decompression show that the disorder is irreversible. Atomic coordinates within unit cells of different dimensions were determined by means of Car-Parrinello simulations. The discontinuous rise in compressibility at about 6 GPa is reproduced by the computation, allowing us to attribute it to re-organization of the hydrogen bonding network, with the formation of water dimers. Moreover we found that, with increasing pressure, the tetrahedral chains parallel to c rotate along their elongation axis and display an increasing twisting along a direction perpendicular to c. At the same time, we observed the compression of the channels. We discuss the modification of the Ca polyhedra under pressure, and the increase in coordination number (from 4 to 5) of one of the two Al atoms, resulting from the approach of a water molecule. We speculate that this last transformation triggers the irreversible disordering of the system.

Accurate computational methods for two-electron atom-laser interactions

We discuss the application of quantitatively accurate computational methods to the study of laser-driven two-electron atoms in short intense laser pulses. The fundamental importance of such calculations to the subject area is emphasized. Calculations of single- and double-electron ionization rates at 390 nm are presented. (C) 2001 Optical Society of America.