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At least 559 records · Page 31

Tafel Slope Analyses for Homogeneous Catalytic Reactions

Tafel analysis of electrocatalysts is essential in their characterization. This paper analyzes the application of Tafel-like analysis to the four-electron nonelectrochemical oxidation of water by the stoichiometric homogeneous 1-electron oxidant [Ru(bpy)3]3+ to dioxygen catalyzed by homogeneous catalysts, [Ru4O4(OH)2(H2O)4(γ-SiW10O36)2]10− (Ru4POM) and [Co4(H2O)2(PW9O34)2]10– (Co4POM). These complexes have slow electron exchange rates with electrodes due to the Frumkin effect, which precludes the use of known electrochemical methods to obtain Tafel plots at ionic strengths lower than 0.5 M. The application of an electron transfer catalyst, [Ru(bpy)3]3+/2+, increases the rates between the Ru4POM and electrode, but a traditional Tafel analysis of such a complex system is precluded due to a lack of appropriate theoretical models for 4-electron processes. Here, we develop a theoretical framework and experimental procedures for a Tafel-like analysis of Ru4POM and Co4POM, using a stoichiometric molecular oxidant [Ru(bpy)3]3+. The dependence of turnover frequency (TOF) as a function of electrochemical solution potential created by the [Ru(bpy)3]3+/[Ru(bpy)3]2+ redox couple (an analog of the Tafel plot) was obtained from kinetics data and interpreted based on the suggested reaction mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Practical quantitative fringe interpretation in a composite mobile holographic nondestructive test system

A simplified theoretical model for the interpretation of the double-exposure holographic interference fringe loci due to the general three-dimensional displacements has been derived for the specific composite mobile holographic nondestructive test system. The model, representing a good approximation to a more tedious theoretical result, predicts that a combination of in-plane and out-of-plane displacements of the surface will produce concentric circular-shaped fringe patterns.

Liu, H.-K.↗

Use of the Jacchia /1977/ empirical model in a dynamical model of upper-atmospheric helium

This brief report describes an investigation of the effects of using the Jacchia (1977) model in place of the Jacchia (1971) model for specifying the background gas pressure in the theoretical model of thermospheric helium described by Straus, et al. (1977). Changes in the global transport of helium caused by a small increase in the latitudes at which the background gas pressure extrema occur lead to much better agreement of the model predictions with data taken by the mass spectrometers on board the Esro 4 and OGO 6 satellites.

Straus, J. M.↗

Fission-induced plasmas

The possibility of creating a plasma from fission fragments, and to utilize the energy of the particles to create population inversion that would lead to laser action is investigated. An investigation was made of various laser materials which could be used for nuclear-pumped lasing. The most likely candidate for a fissioning material in the gaseous form is uranium hexafluoride - UF6, and experiments were performed to investigate materials that would be compatible with it. One of the central problems in understanding a fission-induced plasma is to obtain a model of the electron behavior, and some preliminary calculations are presented. In particular, the rates of various processes are discussed. A simple intuitive model of the electron energy distribution function is also shown. The results were useful for considering a mathematical model of a nuclear-pumped laser. Next a theoretical model of a (3)He-Ar nuclear-pumped laser is presented. The theory showed good qualitative agreement with the experimental results.

Harries, W. L.↗

Gamma-ray spectroscopy - Status and prospects

Contemporary gamma-ray spectroscopy instruments and their results are reviewed. Sensitivities of 10 to the -4th to 10 to the -3rd ph/sq cm-sec have been achieved for steady sources and 10 to the -2nd to 1 ph/sq cm-sec for transient sources. This has led to the detection of gamma-ray lines from more than 40 objects representing 6 classes of astrophysical phenomena. The lines carry model-independent information and are of fundamental importance to theoretical modeling and our understanding of the objects. The objectives and anticipated results of future instruments are discussed. Several instruments in development will have a factor of 10 sensitivity improvement to certain phenomena over contemporary instruments. A factor of 100 improvement in sensitivity will allow the full potential of gamma-ray spectroscopy to be realized. Instrument concepts which would achieve this with both present and advanced techniques are discussed.

Matteson, J. L.↗

Selecting a model of the neutral atmosphere

The characteristics and applicability of some of the more frequently used atmospheric models covering the thermosphere are discussed from the point of view of selecting the most appropriate model for an engineering or scientific problem. Models based on satellite atmospheric drag are the earliest examples of global models and are still widely used for engineering studies. Later models based on satellite instrumentation and ground based measurements were originally aimed at scientific studies of the atmosphere, but their absolute accuracies for total densities are now similar to those of drag based models while providing better thermospheric temperature, composition, and winds. Theoretical models are now approaching the accuracy of climatological empirical models and may surpass them in the near future. Each new model generation, however, is more complicated and costly to run on a computer.

Hedin, A. E.↗

Review of the workshop

During the workshop, the importance of an interplay between observations, laboratory simulations, theoretical modeling, and instrument characterization was highlighted. The laboratory and theoretical fits to astronomical spectra are underlined. The importance of calibrations and of the observations performed by the Infrared Space Observatory (ISO) for the understanding of stars are stressed.

Harwit, Martin↗

Numerical Modeling of Physical Vapor Transport in Contactless Crystal Growth Geometry

Growth from the vapor under conditions of limited contact with the walls of the growth ampoule is beneficial for the quality of the growing crystal due to reduced stress and contamination which may be caused by interactions with the growth container. The technique may be of a particular interest for studies on crystal growth under microgravity conditions: elimination of some factors affecting the crystal quality may make interpretation of space-conducted processes more conclusive and meaningful. For that reason, and as a part of our continuing studies on 'contactless' growth technique, we have developed a computational model of crystal growth process in such system. The theoretical model was built, and simulations were performed using the commercial computational fluid dynamics code, (CFD) ACE. The code uses an implicit finite volume formulation with a gray discrete ordinate method radiation model which accounts for the diffuse absorption and reflection of radiation throughout the furnace. The three-dimensional model computes the heat transfer through the crystal, quartz, and gas both inside and outside the ampoule, and mass transport from the source to the crystal and the sink. The heat transport mechanisms by conduction, natural convection, and radiation, and mass transport by diffusion and convection are modeled simultaneously and include the heat of the phase transition at the solid-vapor interfaces. As the thermal boundary condition, temperature profile along the walls of the furnace is used. For different thermal profiles and furnace and ampoule dimensions, the crystal growth rate and development of the crystal-vapor and source-vapor interfaces (change of the interface shape and location with time) are obtained. Super/under-saturation in the ampoule is determined and critical factors determining the 'contactless' growth conditions are identified and discussed. The relative importance of the ampoule dimensions and geometry, the furnace dimensions and its temperature, and the properties of the grown material are analyzed. The results of the simulations are compared with related experimental results on growth of CdTe, CdZnTe, ZnTe, PbTe, and PbSnTe crystals by this technique.

Palosz, W.↗

NASA Hybrid Reflectometer Project

Time-domain and frequency-domain reflectometry have been used for about forty years to locate opens and shorts in cables. Interpretation of reflectometry data is as much art as science. Is there information in the data that is being missed? Can the reflectometers be improved to allow us to detect and locate defects in cables that are not outright shorts or opens? The Hybrid Reflectometer Project was begun this year at NASA Ames Research Center, initially to model wire physics, simulating time-domain reflectometry (TDR) signals in those models and validating the models against actual TDR data taken on testbed cables. Theoretical models of reflectometry in wires will give us an understanding of the merits and limits of these techniques and will guide the application of a proposed hybrid reflectometer with the aim of enhancing reflectometer sensitivity to the point that wire defects can be detected. We will point out efforts by some other researchers to apply wire physics models to the problem of defect detection in wires and we will describe our own initial efforts to create wire physics models and report on testbed validation of the TDR simulations.

Lynch, Dana↗

Introductory Comments on Stellar Atmospheric Structure and Its Modeling

A general historical perspective on stellar atmospheric models is presented. Some comments on the priori speculative-theoretical modeling of the star, its atmosphere, and its environment are made. In contrast to this more speculative type of investigation, an empirical-theoretical program is defined. The objectives of the program are to delineate atmospheric structural patterns, properties of the local stellar environment, and some necessary characteristics of subatmospheric structure as inferred from the observations of nonthermal fluxes and phenomena, and thermodynamic self consistency.

Source record↗

Modelling the effects of turbulence on acoustic wave propagation

A review of recent theoretical modeling of the effects of turbulence on acoustic wave propagation is presented. The Born approximation limit of the smoothing method of Keller and of the kinetic theory method of Howe are compared with the classical perturbation results of Chernov. Secular growth is observed in the higher order terms of the kinetic theory method of Howe when multiple scaling is ignored. The forward propagation - beam broadening model of Brown and Clifford is discussed as well as the single scatter model of DeLoach and of Rudd. Each model is examined with respect to its prediction of conservation of energy.

Harris, W. L.↗

Modeling features in the redshift-space halo power spectrum with perturbation theory

In this work, we study the ability of perturbative models with effective field theory contributions and infra-red resummation to model the redshift space clustering of biased tracers in models where the linear power spectrum has "features"- either imprinted during inflation or induced by non-standard expansion histories. We show that both Eulerian and Lagrangian perturbation theory are capable of reproducing the Fourier space two-point functions of halos up to the non-linear scale from a suite of 40963 particle N-body simulations. This is the first demonstration that perturbative models can accurately fit the redshift-space clustering of biased tracers in N-body simulations of such theories. By comparing different theoretical models and IR resummation schemes we assess the current theoretical uncertainty in predicting power spectra for models with features. Our results suggest that future surveys will be able to detect or tightly constrain features in the primordial spectrum below the one percent level across a wide range of scales.

redshift surveys↗

Establishment of computerized numerical databases on thermophysical and other properties of molten as well as solid materials and data evaluation and validation for generating recommended reliable reference data

The Center for Information and Numerical Data Analysis and Synthesis, (CINDAS), measures and maintains databases on thermophysical, thermoradiative, mechanical, optical, electronic, ablation, and physical properties of materials. Emphasis is on aerospace structural materials especially composites and on infrared detector/sensor materials. Within CINDAS, the Department of Defense sponsors at Purdue several centers: the High Temperature Material Information Analysis Center (HTMIAC), the Ceramics Information Analysis Center (CIAC) and the Metals Information Analysis Center (MIAC). The responsibilities of CINDAS are extremely broad encompassing basic and applied research, measurement of the properties of thin wires and thin foils as well as bulk materials, acquisition and search of world-wide literature, critical evaluation of data, generation of estimated values to fill data voids, investigation of constitutive, structural, processing, environmental, and rapid heating and loading effects, and dissemination of data. Liquids, gases, molten materials and solids are all considered. The responsibility of maintaining widely used databases includes data evaluation, analysis, correlation, and synthesis. Material property data recorded on the literature are often conflicting, diverging, and subject to large uncertainties. It is admittedly difficult to accurately measure materials properties. Systematic and random errors both enter. Some errors result from lack of characterization of the material itself (impurity effects). In some cases assumed boundary conditions corresponding to a theoretical model are not obtained in the experiments. Stray heat flows and losses must be accounted for. Some experimental methods are inappropriate and in other cases appropriate methods are carried out with poor technique. Conflicts in data may be resolved by curve fitting of the data to theoretical or empirical models or correlation in terms of various affecting parameters. Reasons (e.g. phase transitions) must be found for unusual dependence or any anomaly. Such critical evaluation involves knowledge of theory, experience in measurement, familiarity with metallurgy (microstructural behavior) and not inconsiderable judgment. An examination of typical data compiled and analyzed by CINDAS shows that the thermal conductivity of a material reported in the literature may vary by a factor of two of more; the range of reported values increases as temperature increases reflecting the difficulty of high temperature measurements. Often only estimates of melt behavior are available, despite the importance of melt properties in modeling, welding, or other solidification processes. There may be only a few measurements available for properties such as kinematic viscosity, even for widely used materials such as stainless steel. In the face of such a paucity of existing data and in a national environment where too few new data are being generated it is nonetheless the responsibility of CINDAS to select and disseminate recommended values of a wide variety of thermophysical properties.

Ho, C. Y.↗

Thundercloud electrification models in atmospheric electricity and meteorology

A survey is presented of presently-available theoretical models. The models are classified into three main groups: (1) convection models, (2) precipitation models, and (3) general models. The strengths and weaknesses of the models, their dimensionalities and degrees of sophistication, the nature of their inputs and outputs, and the various specific charging mechanisms treated by them, are considered. In results obtained to date, the convection models predict no significant electrification enhancement based on conductivity gradients and convection alone, with the assumed air circulation patterns. Results of the precipitation models show that the initial electrification can occur rapidly and stably through noninductive collision mechanisms involving ice, and breakdown-strength electric fields can relatively easily be achieved subsequently through the collisional-inductive mechanism. A critical difficulty of the collision mechanisms is imprecise knowledge of relaxation times versus contact times, which can easily lead to overestimates of electrification. The general model results tend to support those of the precipitation models in emphasizing the high potential effectiveness of the collisional-inductive mechanism.

Parker, L. W.↗

Modeling and optimum time performance for concurrent processing

The development of a new graph theoretic model for describing the relation between a decomposed algorithm and its execution in a data flow environment is presented. Called ATAMM, the model consists of a set of Petri net marked graphs useful for representing decision-free algorithms having large-grained, computationally complex primitive operations. Performance time measures which determine computing speed and throughput capacity are defined, and the ATAMM model is used to develop lower bounds for these times. A concurrent processing operating strategy for achieving optimum time performance is presented and illustrated by example.

Mielke, Roland R.↗

The impact of UVCS/SOHO observations on models of ion-cyclotron resonance heating of the solar corona

The compatibility between theoretical models and observations of the temperatures and anisotropic distributions of hydrogen and minor ions in the solar corona is examined. The ultraviolet coronagraph spectrometer (UVCS) instrument onboard SOHO measured hydrogen kinetic temperatures along lines of sight in coronal holes in excess of 3 x 10(exp 6) K and O(+5) ion kinetic temperatures of at least 2 x 10(exp 8) K. Various features of plasma heating by the dissipation of high-frequency ion-cyclotron resonance Alfven waves, which may be the most natural physical mechanism to produce certain plasma conditions, are examined. Preliminary quantitative models of the ion motion in polar coronal holes are presented, and it is shown that such models can be used to predict the spectrum of waves required to reproduce the observations. Indeed, the more ionic species that are observed spectroscopically, the greater the extent in frequency space the wave spectrum can be inferred.

Cranmer, S. R.↗

Small Signal Modelling and Control of the Hydrogen Mixer for Facility E1

We have undertaken the theoretical modelling of an existing liquid hydrogen (LH2) and gas hydrogen (GH2) mixer subsystem of the E1 Ground Test Facility at NASA John C. Stennis Space Center. The E1 test facility carries out comprehensive ground-based testing and certification of various liquid rocket engines and their components. The mixer described in this work is responsible for combining high pressure LH2 and GH2 to produce a hydrogen flow that meets certain thermodynamic properties before it is fed into a test article. The desired properties are maintained by precise control of the mixture of LH2 and GH2 flows. The mixer is modelled as a general multi-flow lumped volume for single constituent fluids using density and internal energy as states. The set of nonlinear differential equations is linearized about an equilibrium point and the resulting two-state, 3-input linear model is analyzed as a possible candidate for control design.

Barbieri, Enrique↗