Dynamical probes of chemical interactions at interfaces

We report on the application of two experimental techniques developed in the field of atomic and molecular physics to investigate the dynamics of catalytic processes on a molecular scale in (model) cata!ysts. With these techniques, time-resolved pump-probe laser spectroscopy and molecular beam scattering, better insights into the fundamental processes relevant to catalysis can be obtained. With the first technique, time-resolved (picosecond) non-linear infared spectroscopy, zeolite catalysts and zeolite-adsorbate interactions are investigated. Microscopic structural information on the bare catalyst, as well as insights into the dynamics of interaction processes between catalyst and reactant (viz. zeolite and adsorbate) on a molecular scale are obtained. With the second technique, a molecular beam experiment, we obtain dynamical information on the interaction between catalytic metal surfaces and molecules; transient surface species and steric effects are observed

On understanding the microstructure of SiC/SiC Ceramic Matrix Composites (CMCs) after a material removal process

The unique material nature (e.g. hard, brittle, heterogeneous and orthotropic) of SiC-based Ceramic Matrix Composites (CMCs) highly affects the outcomes of machining process by inducing high thermo-mechanical loads during material removal. This can result in severe material damage which in turn causes a reduction of the in-service life of critical structural ceramic components (such as in aero-engines or nuclear reactors). In this study, the phenomenon by which the material removal mechanism during drilling influences the CMC surface integrity are discussed by characterising the fracture and deformation phenomena on the CMC's constituents - i.e. SiC and Si materials. Moreover, the strain induced to the surface, together with the changes in chemical composition are characterised via micro Raman spectroscopy and related to the principles of residual stresses upon cutting. This results in a novel understanding of the material removal process that governs cutting of SiC-based CMCs while emphasising how the different microstructure, morphology and nature of ceramics behave under the same cutting conditions. This study has therefore led to a comprehension of how the microstructure of complex hierarchical ceramic materials such as SiC/SiC CMCs is affected by a mechanical cutting process and opens avenues to understand the structure damage under other machining operations (e.g. milling, grinding)

Demographic impacts of utility rate designs

Historically, utility customers have been differentiated into various customer classes, based on their utility service demand characteristics. In this paper we argue that greater differentiation, if based on value and cost of service, can be justified on grounds of economic efficiency, and if done properly can also promote economic equity. This would require a break with traditional customer classifications. With this break, more detailed information on how and why certain utility services arc consumed would be required. In line with the issue of heterogeneity, within the residential customer class, is the differential impact that different utility rates might have on different population groups. The purpose of this paper is to show how differences in the pattern of energy use may give rise to disparate economic impacts depending on the rate structure and how more equitable and efficient outcomes might be achieved if these differences are taken into account. For this purpose, an analytical model has been developed under the auspices of the US Department of Energy, Office of Economic Impact and Diversity. The Energy Policy Socioeconomic Impact Model (EPSIM), an econometric simulation model, has been developed to assess the economic impact of utility rate designs and demand-side management programs on various population groups. The following discussion provides a conceptual description of the theoretical underpinnings associated with the EPSIM

Spectral theory for the failure of linear control in a nonlinear stochastic system

We consider the failure of localized control in a nonlinear spatially extended system caused by extremely small amounts of noise. It is shown that this failure occurs as a result of a nonlinear instability. Nonlinear instabilities can occur in systems described by linearly stable but strongly nonnormal evolution operators. In spatially extended systems the nonnormality manifests itself in two different but complementary ways: transient amplification and spectral focusing of disturbances. We show that temporal and spatial aspects of the nonnormality and the type of nonlinearity are all crucially important to understanding and describing the mechanism of nonlinear instability. Presented results are expected to apply equally to other physical systems where strong nonnormality is due to the presence of mean flow rather than the action of control.Comment: Submitted to Physical Review

Electronic structure and superconductivity of Europium

We have calculated the electronic structure of Eu for the bcc, hcp, and fcc crystal structures for volumes near equilibrium up to a calculated 90 GPa pressure using the augmented-plane wave method in the local-density approximation. The frozen-core approximation was used with a semi-empirical shift of the f-states energies in the radial Schr$\ddot{o}$dinger equation to move the occupied 4f valence states below the $\Gamma_1$ energy and into the core. This shift of the highly localized f-states yields the correct europium phase ordering with lattice parameters and bulk moduli in good agreement with experimental data. The calculated superconductivity properties under pressure for the $\it bcc$ and $\it hcp$ structures are also found to agree with and follow a $T_c$ trend similar to recent measurement by Debessai et al.$^1$Comment: 8 page

An assessment of the wear characteristics of microcutting arrays produced from polycrystalline diamond and cubic boron nitride composites

The current methods for manufacturing super-abrasive elements result in a stochastic geometry of abrasives with random three-dimensional abrasive locations. This paper focuses on the evaluation of wear progression/failure characteristics of micro-abrasive arrays made of ultrahard composites (polycrystalline diamond—PCD; polycrystalline cubic boron nitride—PCBN) in cutting/wear tests against silicon dioxide workpiece. Pulsed laser ablation (Nd:YAG laser) has been used to manufacture repeatable patterns of micro-abrasive edges onto microstructurally different PCD/PCBN composites. Opposing to these highly engineered micro-abrasive arrays, conventional electroplated abrasive pads containing diamond and CBN abrasives, respectively, have been chosen as benchmarks and tested under the same conditions. Contact profiling, optical microscopy, and environmental scanning electron microscopy have been employed for the characterization of the abrasive arrays and electroplated tools before/during/after the wear/cutting tests. For the PCD abrasive micro-arrays, the type of grain and binder percentage proved to affect the wear performances due to the different extents of compressive stresses occurring at the grain boundaries. In this respect, the micro-arrays made of PCD with mixed diamond grain sizes have shown slower wear progression when compared to the electroplated diamond pads confirming the combination of the high wear resistance typical of the fine grain and the good shock resistance typical of the coarse grain structures. The micro-arrays made of fine grained diamond abrasives have produced lower contact pressures with the workpiece shaft, confirming a possible application in polishing or grinding. As for the PCBN abrasive micro-arrays, the increase of metallic binder and the presence of metalloids in the medium content-CBN specimens have shown to produce higher contact pressure with the workpiece when compared to the electroplated specimen, causing fracturing as the main wear mechanism; while the PCBN micro-array with purely a metallic binder phase has shown slower wear and lower contact pressure in comparison to the electroplated CBN specimen. Among all of the tested arrays, the mixed grained PCD and the purely metallic binder phase PCBN micro-arrays have shown slower wear when benchmarked to the electroplated pads, giving a possible application of their use in the cutting tool industry

Continuous trench, pulsed laser ablation for micro-machining applications

The generation of controlled 3D micro-features by pulsed laser ablation in various materials requires an understanding of the material's temporal and energetic response to the laser beam. The key enabler of pulsed laser ablation for micro-machining is the prediction of the removal rate of the target material, thus allowing real-life machining to be simulated mathematically. Usually, the modelling of micro-machining by pulsed laser ablation is done using a pulse-by-pulse evaluation of the surface modification, which could lead to inaccuracies when pulses overlap. To address these issues, a novel continuous evaluation of the surface modification that use trenches as a basic feature is presented in this paper. The work investigates the accuracy of this innovative continuous modelling framework for micro-machining tasks on several materials. The model is calibrated using a very limited number of trenches produced for a range of powers and feed speeds; it is then able to predict the change in topography with a size comparable to the laser beam spot that arises from essentially arbitrary toolpaths. The validity of the model has been proven by being able to predict the surface obtained from single trenches with constant feed speed, single trenches with variable feed speed and overlapped trenches with constant feed speed for three different materials (graphite, polycrystalline diamond and a metal-matrix diamond CMX850) with low error. For the three materials tested, it is found that the average error in the model prediction for a single trench at constant feed speed is lower than 5 % and for overlapped trenches the error is always lower than 10 %. This innovative modelling framework opens avenues to: (i) generate in a repeatable and predictable manner any desired workpiece microtopography; (ii) understand the pulsed laser ablation machining process, in respect of the geometry of the trench produced, therefore improving the geometry of the resulting parts; (iii) enable numerical optimisation for the beam path, thus supporting the development of accurate and flexible computer assisted machining software for pulsed laser ablation micro-machining applications

On the Normalization of the Neutrino-Deuteron Cross Section

As is well-known, comparison of the solar neutrino fluxes measured in SuperKamiokande (SK) by $\nu + e^- \to \nu + e^-$ and in the Sudbury Neutrino Observatory (SNO) by $\nu_e + d \to e^- + p + p$ can provide a ``smoking gun'' signature for neutrino oscillations as the solution to the solar neutrino puzzle. This occurs because SK has some sensitivity to all active neutrino flavors whereas SNO can isolate electron neutrinos. This comparison depends crucially on the normalization and uncertainty of the theoretical charged-current neutrino-deuteron cross section. We address a number of effects which are significant enough to change the interpretation of the SK--SNO comparison.Comment: 4 pages, 1 figure, submitted to PR

Ab initio Quantum and ab initio Molecular Dynamics of the Dissociative Adsorption of Hydrogen on Pd(100)

The dissociative adsorption of hydrogen on Pd(100) has been studied by ab initio quantum dynamics and ab initio molecular dynamics calculations. Treating all hydrogen degrees of freedom as dynamical coordinates implies a high dimensionality and requires statistical averages over thousands of trajectories. An efficient and accurate treatment of such extensive statistics is achieved in two steps: In a first step we evaluate the ab initio potential energy surface (PES) and determine an analytical representation. Then, in an independent second step dynamical calculations are performed on the analytical representation of the PES. Thus the dissociation dynamics is investigated without any crucial assumption except for the Born-Oppenheimer approximation which is anyhow employed when density-functional theory calculations are performed. The ab initio molecular dynamics is compared to detailed quantum dynamical calculations on exactly the same ab initio PES. The occurence of quantum oscillations in the sticking probability as a function of kinetic energy is addressed. They turn out to be very sensitive to the symmetry of the initial conditions. At low kinetic energies sticking is dominated by the steering effect which is illustrated using classical trajectories. The steering effects depends on the kinetic energy, but not on the mass of the molecules. Zero-point effects lead to strong differences between quantum and classical calculations of the sticking probability. The dependence of the sticking probability on the angle of incidence is analysed; it is found to be in good agreement with experimental data. The results show that the determination of the potential energy surface combined with high-dimensional dynamical calculations, in which all relevant degrees of freedon are taken into account, leads to a detailed understanding of the dissociation dynamics of hydrogen at a transition metal surface.Comment: 15 pages, 9 figures, subm. to Phys. Rev.