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At least 1,135 records · Page 63

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

The goal of this program 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 degradation. 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. The interaction of hydrogen with the surfaces of alpha-2(Ti3Al) titanium aluminide, gamma(TiAl) titanium aluminide, and beryllium were studied.

Shanabarger, Mickey R.↗

Kinetics of phase transformation in glass forming systems

The objectives of this research were to (1) develop computer models for realistic simulations of nucleation and crystal growth in glasses, which would also have the flexibility to accomodate the different variables related to sample characteristics and experimental conditions, and (2) design and perform nucleation and crystallization experiments using calorimetric measurements, such as differential scanning calorimetry (DSC) and differential thermal analysis (DTA) to verify these models. The variables related to sample characteristics mentioned in (1) above include size of the glass particles, nucleating agents, and the relative concentration of the surface and internal nuclei. A change in any of these variables changes the mode of the transformation (crystallization) kinetics. A variation in experimental conditions includes isothermal and nonisothermal DSC/DTA measurements. This research would lead to develop improved, more realistic methods for analysis of the DSC/DTA peak profiles to determine the kinetic parameters for nucleation and crystal growth as well as to assess the relative merits and demerits of the thermoanalytical models presently used to study the phase transformation in glasses.

Ray, Chandra S.↗

The Effect of Polymer Char on Nitridation Kinetics of Silicon

Effects of polymer char on nitridation kinetics of attrition milled silicon powder have been investigated from 1200 to 1350 C. Results indicate that at and above 1250 C, the silicon compacts containing 3.5 wt percent polymer char were fully converted to Si3N4 after 24 hr exposure in nitrogen. In contrast, the silicon compacts without polymer char could not be fully converted to Si3N4 at 1350 C under similar exposure conditions. At 1250 and 1350 C, the silicon compacts with polymer char showed faster nitridation kinetics than those without the polymer char. As the polymer char content is increased, the amount of SiC in the nitrided material is also increased. By adding small amounts (approx. 2.5 wt percent) of NiO, the silicon compacts containing polymer char can be completely nitrided at 1200 C. The probable mechanism for the accelerated nitridation of silicon containing polymer char is discussed.

Chan, Rickmond C.↗

LSENS: A General Chemical Kinetics and Sensitivity Analysis Code for homogeneous gas-phase reactions. Part 1: Theory and numerical solution procedures

LSENS, the Lewis General Chemical Kinetics and Sensitivity Analysis Code, has been developed for solving complex, homogeneous, gas-phase chemical kinetics problems and contains sensitivity analysis for a variety of problems, including nonisothermal situations. This report is part 1 of a series of three reference publications that describe LENS, provide a detailed guide to its usage, and present many example problems. Part 1 derives the governing equations and describes the numerical solution procedures for the types of problems that can be solved. The accuracy and efficiency of LSENS are examined by means of various test problems, and comparisons with other methods and codes are presented. LSENS is a flexible, convenient, accurate, and efficient solver for chemical reaction problems such as static system; steady, one-dimensional, inviscid flow; reaction behind incident shock wave, including boundary layer correction; and perfectly stirred (highly backmixed) reactor. In addition, the chemical equilibrium state can be computed for the following assigned states: temperature and pressure, enthalpy and pressure, temperature and volume, and internal energy and volume. For static problems the code computes the sensitivity coefficients of the dependent variables and their temporal derivatives with respect to the initial values of the dependent variables and/or the three rate coefficient parameters of the chemical reactions.

Radhakrishnan, Krishnan↗

Troilite formation kinetics and growth mechanism in the solar nebula

Troilite formation via the reaction Fe(s) + H2S(g) + H2(g) is the major mechanism for S retention in grains in the solar nebula. Thermodynamic calculations predict that troilite condenses from a solar composition gas. We present experimental results on the kinetics and growth of troilite crystals on Fe metal at temperature (450-650 C) and composition (50-1000 ppm H2S in H2) conditions similar to those in the solar nebula. The fraction of Fe reacted (based on gravimetric data) is plotted at 450, 505, 575, and 650 C. The thickness change of unreacted iron (measured by optical microscopy) is plotted at 575 and 650 C vs. time. the weight change per unit area varies as the square root of time at the lower temperatures and varies linearly with time at the highest temperature. The growth behavior along the lower isotherms is due to diffusion. This behavior suggests sulfide diffusion to the metal-sulfide interface and suggests Fe(2+) diffusion to the sulfide-gas interface. The reaction along the highest isotherm appears to be interface controlled. The formation of troilite crystals is a rapid process forming measurable layers in a few hours. The crystalgrowth is complicated. Initially there are intergrowths of troilite into the pure Fe metal. As the reaction progresses two distinct layers of troilite crystals form. One is in contact with the Fe metal and consists of small randomly oriented crystals with pore space between them. The outermost layer contains large crystals that are all oriented in the same direction. The intergrowth layer is much smaller at 650 C than at 575 C. This suggest that FeS nucleation is inhibited at the higher temperature, accounting for the initially slower reaction rate. Once nucleated, the reaction kinetics are apparently controlled by the growth of the crystals at the interface.

Lauretta, D. S.↗

Development and analysis of prognostic equations for mesoscale kinetic energy and mesoscale (subgrid scale) fluxes for large-scale atmospheric models

Generated by landscape discontinuities (e.g., sea breezes) mesoscale circulation processes are not represented in large-scale atmospheric models (e.g., general circulation models), which have an inappropiate grid-scale resolution. With the assumption that atmospheric variables can be separated into large scale, mesoscale, and turbulent scale, a set of prognostic equations applicable in large-scale atmospheric models for momentum, temperature, moisture, and any other gaseous or aerosol material, which includes both mesoscale and turbulent fluxes is developed. Prognostic equations are also developed for these mesoscale fluxes, which indicate a closure problem and, therefore, require a parameterization. For this purpose, the mean mesoscale kinetic energy (MKE) per unit of mass is used, defined as E-tilde = 0.5 (the mean value of u'(sub i exp 2), where u'(sub i) represents the three Cartesian components of a mesoscale circulation (the angle bracket symbol is the grid-scale, horizontal averaging operator in the large-scale model, and a tilde indicates a corresponding large-scale mean value). A prognostic equation is developed for E-tilde, and an analysis of the different terms of this equation indicates that the mesoscale vertical heat flux, the mesoscale pressure correlation, and the interaction between turbulence and mesoscale perturbations are the major terms that affect the time tendency of E-tilde. A-state-of-the-art mesoscale atmospheric model is used to investigate the relationship between MKE, landscape discontinuities (as characterized by the spatial distribution of heat fluxes at the earth's surface), and mesoscale sensible and latent heat fluxes in the atmosphere. MKE is compared with turbulence kinetic energy to illustrate the importance of mesoscale processes as compared to turbulent processes. This analysis emphasizes the potential use of MKE to bridge between landscape discontinuities and mesoscale fluxes and, therefore, to parameterize mesoscale fluxes generated by such subgrid-scale landscape discontinuities in large-scale atmospheric models.

Avissar, Roni↗

Kinetic and thermodynamic properties of a convecting plasma in a two-dimensional dipole field

Charged particle guiding center motion is considered in the magnetic field of a two-dimensional ('line') dipole on which is superimposed a small, static, perpendicular electric field. The parallel equation of motion is that of a simple harmonic oscillator for cos theta, the cosine of magnetic colatitude theta. Equations for the perpendicular electric and magnetic drifts are derived as well as their bounce-averaged forms. The latter are solved to yield a bounce-averaged guiding center trajectory, which is the same as that obtained from conversation of magnetic moment mu, longitudinal invariant J, and total (kinetic plus electrostatic) energy K. The algebraic simplicity of the trajectory equations is also manifest in the forms of the invariants. An interesting result is that guiding centers drift in such a way that they preserve the values of their equatorial pitch angles and (equivalently) mirror latitudes. The most general Maxwellian form of the equilibrium one-particle distribution function f is constructed from the invariants, and spatially varying density and pressure moments, parallel and perpendicular to the magnetic field, are identified. Much of the paper deals with the more restricted problem in which f is specified as a bi-Maxwellian over a straight line of finite length in the equatorial plane of the dipole and perpendicular to field lines. This might be thought of as specifying a cross-tail ion injection source; our formalism then describes the subsequent spatial development. The distribution away from the source is a scaled bi-Maxwellian but one that is cut off at large and small kinetic energies, which depend on position. Density and pressure components are reduced from the values they would have if the total content of individual flux tubes convected intact. The equatorial and meridional variations of density and pressure components are examined and compared systematically for the isotropic and highly anisotropic situations. There appears to be little qualitative difference due to anisotropy. An anisotropy measure is defined, and its spatial variation determined as a signature of possible MHD instability. Extreme values are found, larger than at the source, but the plasma beta in such regions is probably so low as to render the effect inconsequential energetically. Finally, the possible consequence of 'nonadia- batic' pressure profiles on electrostatic interchanges is considered, and a boundary delineating stabilizing and destabilizing regions determined.

Huang, T. S.↗

Kinetic Alfven waves as a source of plasma transport at the dayside magnetopause

As the shocked solar wind with variable plasma density and magnetic field impinges on the dayside magnetopause, it is likely to generate large-scale Alfven waves at the solar wind magnetosphere interface. However, large gradients in the density and magnetic field at the magnetopause boundary effectively couple large-scale Alfven waves with kinetic Alfven waves may play an important role in plasma transport at the dayside magnetopause and in electron acceleration along field lines. The transport can occur because, unlike the magnetohydrodynamic (MHD) shear Alfven wave, the kinetic Alfven wave has an associated parallel electric field which breaks down the 'frozen-in' condition and decouples the plasma from field lines. We calculate the average deviation of the plasma from the field line from which we estimate the diffusion coefficient associated with these 'bundles' of lead to acceleration of electrons along field lines in the magnetopause boundary and may possibly provide an explanation for observed counterstreaming electron beams characterized by energies of 50-200 eV.

Lee, L. C.↗

A time-dependent gyro-kinetic model of thermal ion upflows in the high-latitude F region

Ample evidence supports the significance of the high-latitude ionospheric contribution to magnetospheric plasma. Assuming flux conservation along a flux tube, the upward field-aligned ion flows observed in the magnetosphere require high-latitude ionospheric field-aligned ion upflows of the order of 10(exp 8) to 10(exp 9)/sq cm/s. Since radar and satellite observations of high-latitude F region flows at times exceed this flux requirement by an order of magnitude, the thermal ionospheric upflows are not simply the ionospheric response to a magnetospheric flux requirement. Several ionospheric ion upflow mechanisms have been proposed, but simulations based on fluid theory do not reproduce all the observed features of ionospheric ion upflows. Certain asymmetries in the statistical morphology of high-latitude F region ion upflows suggest that the ion upflows may be generated by ion-neutral frictional heating. We developed a single-component (O(+)), time-dependent gyro-kinetic model of the high-latitude F region response to frictional heating in which the neutral exobase is a discontinuous boundary between fully collisional and collisionless plasmas. The concept of a discontinuous neutreal exobase and the assumption of a constant and uniform polarization electric field reduce the ion velocity distribution function, from which we can compute the ion density, parallel velocity, parallel and perpendicular temperature, and parallel flux. Using our model, we simulated the response of a convecting flux tube between 500 km and 2500 km to various frictional heating inputs; the results were both qualitatively and quantitatively different from fluid model results, which may indicate an inadequacy of the fluid theory approach. The gyro-kinetic frictional heating model responses to the various simulations were qualitatively similar: (1) initial perturbations of all the modeled parameters propagated rapidly up the flux tube, (2) transient values of the ion parallel velocity, temperature, and flux exceeded 3 km/s, 2 x 10(exp 4) K, and 10(exp 9)/sq cm/s, respectively, (3) a second transient regime developed wherein the parallel temperature drops to very low values (a few hundred Kelvins), and (4) well after heating ceased, large parallel temperatures and large downward parallel velocities and fluxes developed as the flux tube slowly returned to diffusive equilibrium. The ion velocity distributions during the simulation are often non-Maxwellian and are sometimes composed of two distinct ion populations.

Loranc, M.↗

Kinetic structure of intermediate shocks: Implications for the magnetopause

A general study of the structure and stability of intermediate shocks (IS) in an isotropic plasma is presented using a hybrid as well as a resistive Hall MHD code. Special emphasis is put on the question of whether the rotational layers observed at the magnetopause can be intermediate shocks. The shocks are formed dynamically by the interaction between a flowing plasma and a stationary piston. Coplanar ISs (both strong and weak) are found to be stable in a collisionless plasma. The existence of slow shocks in a high beta plasma is also established for the first time. Noncoplanar ISs are found to be time-dependent, evolving toward a rotational discontinuity (RD) after some characteristic time tau which can be quite long (1000 Omega(exp -1), where Omega is the ion gyrofrequency). The value tau is larger the closer the rotation angle is to 180 deg. Rotations larger than 180 deg are found to be unstable, decaying into a state of minimum shear (i.e., rotation angle less than 180 deg). There are various length scales associated with an IS in the kinetic regime. The shortest scale is found to be the length scale over which rotation of the transverse component of the magnetic field takes place. This scale can have a half width as small as one ion inertial length (c/omega(sub p)) for electron sense rotations and 3c/omega(sub p) for ion sense rotations, for an upstream ion beta of unity. Both of these scales are consistent with the observed thickness at the magnetopause and identical to the corresponding RD scales. A detailed study of the mode conversion of the Alfven ion cyclotron waves (A/IC) waves across both slow and intermediate shocks and the resulting downstream wave spectrum are presented. The possibility that the large number of relfected ions observed at the magnetopause may be due to the presence of strong ISs is considered. The identification of strong ISs and their distinction from RDs should be possible in observations due to significant differences that exist between jump conditions and overall structure of the two discontinuities. The jumps in the plasma parameters across a weak IS are typically small. This together with the fact that the weak ISs and RDs have very similar thickness and other overall properties makes the distinction between weak ISs and RDs in the observations largely inconsequential. However, at large noncoplanarity angles the weak IS approaches the RD limit in a relatively short time (approximately less than 100 Omega (exp -1)). Thus, magnetopause rotations with large noncoplanarity angles are most likely either RDs or strong ISs. Finally, direct comparisons between fluid (resistive Hall MHD) and kinetic simulations show that fluid theory is not applicable to study of ISs in a collisionless plasma.

Karimabadi, H.↗

Kinetic aspects of reconnection at the magnetopause

Observations presented here support the kinetic (or single particle) description of reconnection where ions interacting with the magnetopause conserve their pitch angles or change them by equal amounts as in adiabatic motion. These observations include ion reflection and transmission at the magnetopause and time of flight effects associated with the magnetopause layers, with an emphasis here on ion reflection. Velocities of the reflected distributions predicted from this kinetic description are in good agreement with observed velocities. However, predicted velocities for the transmitted distributions are often higher than observed ones. Reflected distributions are also heated at the magnetopause; however, this heating is less important than the large scale ion motion. Reflection coefficients at the magnetopause are high (averaging 30%), appear to be the same on either side of the magnetopause, and have little or no dependence on ion mass. Time of flight effects result from the finite extent of the reconnection layers and are best observed at the edges of the layers.

Fuselier, Stephen A.↗

Turbulence in the solar wind: Kinetic effects

Although a casual look at the fluctuating magnetic and velocity fields in the solar wind may be reminiscent of a chaotic and disordered flow, there is, nonetheless. considerable organization and structure in the temporal and spatial evolution of those fluctuations. Much of that evolution is controlled by processes operating on rather large scales for example, in the inner heliosphere, the fluctuations in magnetic and velocity are highly correlated in the sense of outward propagating Alfven waves. This correlation can be destroyed both in time and distance by the velocity gradients present between fast and slow streams and by other nonlinear processes which stir the medium, producing a turbulent cascade of energy from large to small scales. Many aspects of this turbulent evolution can be described using fluid models; however, at some scale the fluid approximation breaks down and a more detailed paradigm is necessary. The breakdown is evident in the power spectrum of magnetic fluctuations at scales approaching the wavelength of ion cyclotron waves. At those scales, as evident in Mariner 10 and other magnetometer data, the spectrum bends over and the fluctuations damp, possibly heating the ambient plasma. Some evidence for heating of the solar wind is present in the Voyager data. Fluid models can be modified to some extent to incorporate aspects of a kinetic treatment. This is done by modifying the dissipation terms in the fluid equations and by including extra terms, such as the Hall term. As the scale lengths of phenomena shrink further and approach the spatial and temporal scales characteristic of electron phenomena, the fluid description must be abandoned altogether and a fully kinetic treatment is required. One example is the generation of Langmuir solitons produced by the electron beams that generate type 3 solar radio bursts.

Goldstein, M. L.↗

Comparison of CME masses and kinetic energies near the Sun and in the inner heliosphere

Masses have now been determined for many of the CMEs observed in the inner heliosphere by the HELIOS 1 and 2 zodiacal light photometers. The speed of the brightest material of each CME has also been measured so that, for events having both mass and speed determinations, the kinetic energies of the CMEs are estimated. We compare the masses and kinetic energies of the individual CMEs measured in the inner heliosphere by HELIOS and near the Sun from observations by the SOLWIND (1979-1983) and SMM coronagraphs (1980). Where feasible we also compare the speeds of the same CMEs. We find that the HELIOS masses and energies tend to be somewhat larger by factors of 2-5 than those derived from the coronagraph data. We also compare the distribution of the masses and energies of the HELIOS and coronagraph CMEs over the solar cycle. These results provide an important baseline for observations of CMEs from coronagraphs, from the ISEE-3/ICE, WIND and Ulysses spacecraft and in the future from SOHO.

Webb, D. F.↗

Kinetics of Cyclic Oxidation and Cracking and Finite Element Analysis of MA956 and Sapphire/MA956 Composite System

Sapphire fiber-reinforced MA956 composites hold promise for significant weight savings and increased high-temperature structural capability, as compared to unreinforced MA956. As part of an overall assessment of the high-temperature characteristics of this material system, cyclic oxidation behavior was studied at 1093 C and 1204 C. Initially, both sets of coupons exhibited parabolic oxidation kinetics. Later, monolithic MA956 exhibited spallation and a linear weight loss, whereas the composite showed a linear weight gain without spallation. Weight loss of the monolithic MA956 resulted from the linking of a multiplicity of randomly oriented and closely spaced surface cracks that facilitated ready spallation. By contrast, cracking of the composite's oxide layer was nonintersecting and aligned nominally parallel with the orientation of the subsurface reinforcing fibers. Oxidative lifetime of monolithic MA956 was projected from the observed oxidation kinetics. Linear elastic, finite element continuum, and micromechanics analyses were performed on coupons of the monolithic and composite materials. Results of the analyses qualitatively agreed well with the observed oxide cracking and spallation behavior of both the MA956 and the Sapphire/MA956 composite coupons.

Lee, Kang N.↗

Kinetics of Static Strain Aging in Polycrystalline NiAl-based Alloys

The kinetics of yield point return have been studied in two NiAl-based alloys as a function of aging time at temperatures between 300 and 700 K. The results indicate that the upper yield stress increment, Delta sigma(sub u) (i.e., stress difference between the upper yield point and the final flow stress achieved during prestraining), in conventional purity (CP-NiAl) and in high purity carbon-doped (NiAl-C) material first increased with a t(exp 2/3) relationship before reaching a plateau. This behavior suggests that a Cottrell locking mechanism is the cause for yield points in NiAl. In addition, positive y-axis intercepts were observed in plots of Delta sigma(sub u) versus t(exp 2/3) suggesting the operation of a Snoek mechanism. Analysis according to the Cottrell Bilby model of atmosphere formation around dislocations yields an activation energy for yield point return in the range 70 to 76 kJ/mol which is comparable to the activation energy for diffusion of interstitial impurities in bcc metals. It is, thus, concluded that the kinetics of static strain aging in NiAl are controlled by the locking of dislocations by Cottrell atmospheres of carbon atoms around dislocations.

Weaver, M. L.↗

Thermal Stability of Jet Fuels: Kinetics of Forming Deposit Precursors

The focus of this study was on the autoxidation kinetics of deposit precursor formation in jet fuels. The objectives were: (1) to demonstrate that laser-induced fluorescence is a viable kinetic tool for measuring rates of deposit precursor formation in jet fuels; (2) to determine global rate expressions for the formation of thermal deposit precursors in jet fuels; and (3) to better understand the chemical mechanism of thermal stability. The fuels were isothermally stressed in small glass ampules in the 120 to 180 C range. Concentrations of deposit precursor, hydroperoxide and oxygen consumption were measured over time in the thermally stressed fuels. Deposit precursors were measured using laser-induced fluorescence (LIF), hydroperoxides using a spectrophotometric technique, and oxygen consumption by the pressure loss in the ampule. The expressions, I.P. = 1.278 x 10(exp -11)exp(28,517.9/RT) and R(sub dp) = 2.382 x 10(exp 17)exp(-34,369.2/RT) for the induction period, I.P. and rate of deposit precursor formation R(sub dp), were determined for Jet A fuel. The results of the study support a new theory of deposit formation in jet fuels, which suggest that acid catalyzed ionic reactions compete with free radical reactions to form deposit precursors. The results indicate that deposit precursors form only when aromatics are present in the fuel. Traces of sulfur reduce the rate of autoxidation but increase the yield of deposit precursor. Free radical chemistry is responsible for hydroperoxide formation and the oxidation of sulfur compounds to sulfonic acids. Phenols are then formed by the acid catalyzed decomposition of benzylic hydroperoxides, and deposit precursors are produced by the reaction of phenols with aldehydes, which forms a polymer similar to Bakelite. Deposit precursors appear to have a phenolic resin-like structure because the LIF spectra of the deposit precursors were similar to that of phenolic resin dissolved in TAM.

Naegeli, David W.↗

Laboratory Kinetic Studies of OH and CO2 Relevant to Upper Atmospheric Radiation Balance

The purpose of this project was to quantify the rates of two processes which are crucial to our understanding of radiative energy balance in the upper atmosphere. The first process is radiative emission from vibrationally hot OH radicals following the H + O3 reaction in the upper mesosphere. The importance of this process depends strongly on the OH radiative emission coefficients. Our goal was to measure the OH permanent dipole moment in excited vibrational states and to use these measurements to construct an improved OH dipole moment function and improved radiative emission coefficients. Significant progress was made on these experiments including the construction of a supersonic jet source for vibrationally excited OH radicals. Unfortunately, our efforts to transport the OH radicals into a second lower pressure vacuum chamber were not successful, and we were unable to make improved dipole moment measurements for OH. The second key kinetic process which we attempted to quantify during this project is the rate of relaxation of bend-excited CO2 by oxygen atoms. Since excitation of the bending vibrational mode of CO2 is the major cooling mechanism in the upper mesosphere/lower thermosphere, the cooling rate of this region depends crucially on the rate of energy transfer out of this state. It is believed that the most efficient transfer mechanism is via atomic oxygen but the rate for this process has not been directly measured in the laboratory at appropriate temperatures and even the room temperature rate remains controversial. We attempted to directly measure the relaxation rate Of CO2 (010) by oxygen atoms using the discharge flow technique. This experiment was set up at Aerodyne Research. Again, significant progress was achieved in this experiment. A hot CO2 source was set up, bend excited CO2 was detected and the rate of relaxation of bend excited CO2 by He atoms was measured. Unfortunately, the project ran out of time before the oxygen atom kinetic studies could be implemented.

Nelson, David D.↗

Kinetics of the Reaction of O((sup 3)P) with CF3NO

A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of the reaction of O((sup 3)P) with CF3NO (k(2)) as a function of temperature. Our results are described by the Arrhenius expression k(2)(T) = (4.54 +/- 0.70) x 10(exp -l2)exp[(-560 +/- 46)/T] cu cm/molecule.s (243 K is less than or equal to T is less than or equal to 424 K); errors are 2 sigma and represent precision only. The O((sup 3)P) + CF3NO reaction is sufficiently rapid that CF3NO cannot be employed as a selective quencher for O2(alpha(1) Delta-g) in laboratory systems where O((sup 3)P) and O2(alpha 1 Delta g) coexist, and where O((sup 3)P) kinetics are being investigated.

Thorn, R. P.↗