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At least 1,117 records · Page 62

Simulation studies of plasma waves in the electron foreshock - The transition from reactive to kinetic instability

Particle simulation experiments were used to analyze the electron beam-plasma instability. It is shown that there is a transition from the reactive state of the electron beam-plasma instability to the kinetic instability of Langmuir waves. Quantitative tests, which include an evaluation of the dispersion relation for the evolving non-Maxwellian beam distribution, show that a quasi-linear theory describes the onset of this transition and applies again fully to the kinetic stage. This stage is practically identical to the late stage seen in simulations of plasma waves in the electron foreshock described by Dum (1990).

Dum, C. T.↗

Morphological stability and kinetics in crystal growth from vapors

The following topics are discussed: (1) microscopy image storage and processing system; (2) growth kinetics and morphology study with carbon tetrabromide; (3) photothermal deflection vapor growth setup; (4) bridgman growth of iodine single crystals; (5) vapor concentration distribution measurement during growth; and (6) Monte Carlo modeling of anisotropic growth kinetics and morphology. A collection of presentations and publications of these results are presented.

Rosenberger, Franz↗

Thermodynamic properties and crystallization kinetics at high liquid undercooling

The heat capacities of liquid and crystalline Au-Pb-Sb alloys in the glass-forming composition range were measured with droplet emulsion and bulk samples. Based on the measured C(sub p) data, the entropy, enthalpy, and Gibbs free energy functions of the eutectic, solid mixture, and undercooled liquid were determined as a function of undercooling and compared with theoretical predictions. The results indicate an isentropic temperature at 313 + or - 5 K, which agrees well with experimental data for the glass transition. A kinetics analysis of the nucleation undercooling response suggests that the proper choice for the Gibbs free energy change during crystallization is most important in analyzing the nucleation kinetics. By classical nucleation theory, the prefactors obtained, based on a variety of theoretical predictions for the driving force, can differ by six orders of magnitude. If the nucleation rates are extrapolated to high undercooling, the extrapolations based on measured heat capacity data show agreement, whereas the predicted nucleation rates are inconsistent with results from drop tower experiments. The implications for microg experiments are discussed.

Fecht, Hans J.↗

Effect of ohmic, mass-transfer, and kinetic resistances on linear-sweep voltammetry in a cylindrical-pore electrode

A means is presented to account for the effect of ohmic, mass-transfer, and kinetic resistances on linear-sweep voltammograms by modeling a pore in a porous matrix as a cylindrical-pore electrode, and solving the mass and charge conservation equations in the context of this geometry for the simply redox reaction O + ne(-) yield R where both O and R are soluble species. Both analytical and numerical techniques are used to solve the governing equations. The calculated peak currents and potentials are correlated by empirical formulas to the measurable parameters: sweep rate, concentration of the redox species, diffusion coefficient, conductivity of the electrolyte, and pore dimensions. Using the correlations, a methodology is established for determining if the redox reaction kinetics are irreversible or reversible (Nernstian). If the reaction is irreversible, it is shown how the standard rate constant and the transfer coefficient may be extracted from linear-sweep voltammetry data, or, if the reaction is reversible, how the number of electrons transferred may be deduced.

Weidner, John W.↗

An investigation of the effect of surface impurities on the adsorption kinetics of hydrogen chemisorbed onto iron

The goal was to develop an understanding of heterogeneous kinetic processes for those molecular species which produce gaseous hydrogen degradation of the mechanical properties of metallic structural materials. Although hydrogen degradation of metallic materials is believed to result from dissolved protonic hydrogen, the heterogeneous hydrogen interface transport processes often dominate the kinetics of the degradation process. The initial step in the interface transport process is the dissociative chemisorption of the molecular species at the metal surface followed by hydrogen absorption into and transport through the bulk. Modern advanced aerospace applications often require the use of structural materials in high pressure hydrogen environments at temperatures which range from low cryogenic temperatures to very high temperatures (1300 K and greater). Materials proposed for these applications, such as the titanium aluminides, beta-titanium alloys, nickel- and cobalt-based superalloys, molybdenum-rhenium alloys, beryllium, and various beryllides, need to possess a high degree of immunity from hydrogen induced degradation of mechanical properties. In the present program, the interaction of hydrogen with the surfaces of alpha-2 (Ti3Al) titanium aluminide, gamma (TiAl) titanium aluminide, and beryllium were studied. The interaction of low pressure hydrogen with gamma titanium aluminide and beryllium was found to be relatively weak, in the sense that adsorption leads to a low surface concentration of dissociated hydrogen, i.e., the chemisorption process is reversible at room temperature (300 K) for gamma titanium aluminide and the sticking coefficient for chemisorption is extremely small for beryllium. Hydrogen was found to interact readily with alpha-2 titanium aluminide to form a stable surface hydride at 300 K. These results correlate well with other recent studies which show that the mechanical properties for alpha-2 titanium aluminide are readily degraded in hydrogen while gamma titanium aluminide exhibits less degradation and beryllium essentially no degradation. The interaction of oxygen with the surface of these materials has been studied, also, in the present program.

Shanabarger, Mickey R.↗

Kinetic friction attributed to enhanced radiation by cyclotron maser instability

Along the auroral field lines, a fraction of the energetic electrons injected from the magnetotail is reflected by the earth's convergent geomagnetic field. The reflected loss-cone electrons are unstable with respect to the cyclotron maser instability, resulting in the auroral kilometric radiation. This paper investigates the kinetic friction force exerted on the energetic electrons by the enhanced radiation field. It is found that the enhanced radiation results in a deceleration of reflected electrons, thereby providing an effective resistivity. In addition, the rate of decrease (increase) of effective perpendicular (parallel) kinetic temperatures is also evaluated. The analysis is carried out over various physical parameters such as the degree of loss cone, average particle energy, and the ratio of plasma frequency to cyclotron frequency.

Yoon, Peter H.↗

Combustion kinetics and sensitivity analysis computations

The stiff ordinary differential equation solution methods more commonly used for chemical kinetics problems are examined, and the efficiency and accuracy of several of the methods are compared by applying them to two combustion kinetics problems. The local sensitivity analysis methods developed to date are outlined, and their advantages and difficulties are briefly discussed. Examples are used to make comparisons among the different techniques.

Radhakrishnan, K.↗

Kinetic treatment of nonlinear magnetized plasma motions - General geometry and parallel waves

The expansion of kinetic equations in the limit of a strong magnetic field is presented. This gives a natural description of the motions of magnetized plasmas, which are slow compared to the particle gyroperiods and gyroradii. Although the approach is 3D, this very general result is used only to focus on the parallel propagation of nonlinear Alfven waves. The derivative nonlinear Schroedinger-like equation is obtained. Two new terms occur compared to earlier treatments, a nonlinear term proportional to the heat flux along the magnetic field line and a higher-order dispersive term. It is shown that kinetic description avoids the singularities occurring in magnetohydrodynamic or multifluid approaches, which correspond to the degenerate case of sound speeds equal to the Alfven speed, and that parallel heat fluxes cannot be neglected, not even in the case of low parallel plasma beta. A truly stationary soliton solution is derived.

Khabibrakhmanov, I. KH.↗

Kinetic Tetrazolium Microtiter Assay

Kinetic tetrazolium microtiter assay (KTMA) involves use of tetrazolium salts and Triton X-100 (or equivalent), nontoxic, in vitro color developer solubilizing colored metabolite formazan without injuring or killing metabolizing cells. Provides for continuous measurement of metabolism and makes possible to determine rate of action of antimicrobial agent in real time as well as determines effective inhibitory concentrations. Used to monitor growth after addition of stimulatory compounds. Provides for kinetic determination of efficacy of biocide, greatly increasing reliability and precision of results. Also used to determine relative effectiveness of antimicrobial agent as function of time. Capability of generating results on day of test extremely important in treatment of water and waste, disinfection of hospital rooms, and in pharmaceutical, agricultural, and food-processing industries. Assay also used in many aspects of cell biology.

Pierson, Duane L.↗

LSENS, a general chemical kinetics and sensitivity analysis code for gas-phase reactions: User's guide

A general chemical kinetics and sensitivity analysis code for complex, homogeneous, gas-phase reactions is described. The main features of the code, LSENS, are its flexibility, efficiency and convenience in treating many different chemical reaction models. The models include static system, steady, one-dimensional, inviscid flow, shock initiated reaction, and a perfectly stirred reactor. In addition, equilibrium computations can be performed for several assigned states. An implicit numerical integration method, which works efficiently for the extremes of very fast and very slow reaction, is used for solving the 'stiff' differential equation systems that arise in chemical kinetics. For static reactions, sensitivity coefficients of all dependent variables and their temporal derivatives with respect to the initial values of dependent variables and/or the rate coefficient parameters can be computed. This paper presents descriptions of the code and its usage, and includes several illustrative example problems.

Radhakrishnan, Krishnan↗

Pressure dependence of the oxygen reduction reaction at the platinum microelectrode/nafion interface - Electrode kinetics and mass transport

The investigation of oxygen reduction kinetics at the platinum/Nafion interface is of great importance in the advancement of proton-exchange-membrane (PEM) fuel-cell technology. This study focuses on the dependence of the oxygen reduction kinetics on oxygen pressure. Conventional Tafel analysis of the data shows that the reaction order with respect to oxygen is unity at both high and low current densities. Chronoamperometric measurements of the transport parameters for oxygen in Nafion show that oxygen dissolution follows Henry's isotherm. The diffusion coefficient of oxygen is invariant with pressure; however, the diffusion coefficient for oxygen is lower when air is used as the equilibrating gas as compared to when oxygen is used for equilibration. These results are of value in understanding the influence of O2 partial pressure on the performance of PEM fuel cells and also in elucidating the mechanism of oxygen reduction at the platinum/Nafion interface.

Parthasarathy, Arvind↗

Dynamical polar wind and its response to kinetic ion heating

The effect of the kinetic ion heating of the polar wind on the dynamic expansion of the polar wind outflow is investigated by incorporating the kinetic ion heating effect into a time-dependent hydrodynamic polar wind model in which the polar wind O(+) and H(+) continuity and momentum equations are solved in a flux tube from ionospheric to magnetospheric altitudes. Two limiting cases were considered: (1) preferential O(+) escape and (2) preferential H(+) heating. It was found that ion heating does not have much effect on the escape of H(+) ions because of the limiting nature of the H(+) escape fluxes. However, O(+) heating can substantially increase the upward O(+) pressure gradient in the heating region, indicating that O(+) heating is a viable explanation for the unexpectedly large O(+) fluxes frequently observed in the polar magnetosphere.

Chen, Margaret W.↗

Tungsten solution kinetics and amorphization of nickel in mechanically alloyed Ni-W alloys

The kinetics of solution of W, and the subsequent amorphization of Ni, in mechanically alloyed Ni-W alloys has been investigated. As W is a highly abrasive material in the energy intensive devices used for mechanical alloying, we studied the above reactions in different mills. One used hardened steel balls as the grinding media, and the other Al2O3. Abrasion is common to both mills, but Fe wear debris from the hardened steel enters into solution in the Ni rich phases whereas Al2O3 debris is present as small dispersoids. The kinetics of W solution and those of subsequent amorphization do not appear strongly affected by the Fe in solution or the Al2O3 dispersoid. Tungsten dissolves in crystalline Ni in amounts in excess of the equilibrium solubility during alloying. Amorphization of the Ni phase occurs if the W content in this phase exceeds ca. 28 at. pct.

Aning, A. O.↗

Comparison of kinetic models for atom recombination on high-temperature reusable surface insulation

Five kinetic models are compared for their ability to predict recombination coefficients for oxygen and nitrogen atoms over high-temperature reusable surface insulation (HRSI). Four of the models are derived using Rideal-Eley or Langmuir-Hinshelwood catalytic mechanisms to describe the reaction sequence. The fifth model is an empirical expression that offers certain features unattainable through mechanistic description. The results showed that a four-parameter model, with temperature as the only variable, works best with data currently available. The model describes recombination coefficients for oxygen and nitrogen atoms for temperatures from 300 to 1800 K. Kinetic models, with atom concentrations, demonstrate the influence of atom concentration on recombination coefficients. These models can be used for the prediction of heating rates due to catalytic recombination during re-entry or aerobraking maneuvers. The work further demonstrates a requirement for more recombination experiments in the temperature ranges of 300-1000 K, and 1500-1850 K, with deliberate concentration variation to verify model requirements.

Willey, Ronald J.↗

The kinetics of composite particle formation during mechanical alloying

The kinetics of composite particle formation during attritor milling of insoluble binary elemental powders have been examined. The effects of processing conditions (i.e., mill power, temperature, and charge ratio) on these kinetics were studied. Particle size distributions and fractions of elemental and composite particles were determined as functions of milling time and processing conditions. This allowed the deduction of phenomenological rate constants describing the propensity for fracture and welding during processing. For the mill-operating conditions investigated, the number of particles in the mill generally decreased with milling time, indicating a greater tendency for particle welding than fracture. Moreover, a bimodal size distribution is often obtained as a result of preferential welding. Copper and chromium 'alloy' primarily by encapsulation of Cr particles within Cu. This form of alloying also occurs in Cu-Nb alloys processed at low mill power and/or for short milling times. For other conditions, however, Cu-Nb alloys develop a lamellar morphology characteristic of mechanically alloyed two-phase ductile metals. Increasing mill power or charge (ball-to-powder weight) ratio (CR) increases the rate of composite particle formation.

Aikin, B. J. M.↗

Nova dust nucleation - Kinetics and photodissociation

Dust is observed to form in nova ejecta. The grain temperature is determined by the diluted nova radiation field rather than the gas kinetic temperature, making classical nucleation theory inapplicable. We used kinetic equations to calculate the growth of carbon nuclei in these ejecta. For expected values of the parameters too many clusters grew, despite the small sticking probability of atoms to small clusters, and the clusters only reached radii of about 100 A when the carbon vapor was depleted. We then included the effects of cluster photodissociation by ultraviolet radiation from the nova. This suppresses nucleation, but too well, and no grains form at all. Finally we suggest that a few growing carbon nuclei may be protected from photodissociation by a sacrificial surface layer of hydrogen.

Johnson, D. J.↗

Chemical kinetic studies of atmospheric reactions using tunable diode laser spectroscopy

IR absorption using tunable diode laser spectroscopy provides a sensitive and quantitative detection method for laboratory kinetic studies of atmospheric trace gases. Improvements in multipass cell design, real time signal processing, and computer controlled data acquisition and analysis have extended the applicability of the technique. We have developed several optical systems using off-axis resonator mirror designs which maximize path length while minimizing both the sample volume and the interference fringes inherent in conventional 'White' cells. Computerized signal processing using rapid scan (300 kHz), sweep integration with 100 percent duty cycle allows substantial noise reduction while retaining the advantages of using direct absorption for absolute absorbance measurements and simultaneous detection of multiple species. Peak heights and areas are determined by curve fitting using nonlinear least square methods. We have applied these techniques to measurements of: (1) heterogeneous uptake chemistry of atmospheric trace gases (HCl, H2O2, and N2O5) on aqueous and sulfuric acid droplets; (2) vapor pressure measurements of nitric acid and water over prototypical stratospheric aerosol (nitric acid trihydrate) surfaces; and (3) discharge flow tube kinetic studies of the HO2 radical using isotopic labeling for product channel and mechanistic analysis. Results from each of these areas demonstrate the versatility of TDL absorption spectroscopy for atmospheric chemistry applications.

Worsnop, Douglas R.↗

The Gaseous Explosive Reaction : A Study of the Kinetics of Composite Fuels

This report deals with the results of a series of studies of the kinetics of gaseous explosive reactions where the fuel under observation, instead of being a simple gas, is a known mixture of simple gases. In the practical application of the gaseous explosive reaction as a source of power in the gas engine, the fuels employed are composite, with characteristics that are apt to be due to the characteristics of their components and hence may be somewhat complex. The simplest problem that could be proposed in an investigation either of the thermodynamics or kinetics of the gaseous explosive reaction of a composite fuel would seem to be a separate study of the reaction characteristics of each component of the fuel and then a study of the reaction characteristics of the various known mixtures of those components forming composite fuels more and more complex. (author)

Stevens, F W↗