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At least 55 records · Page 3

Investigation of reaction kinetics and interfacial phase formation in Ti3Al + Nb composites

Titanium aluminide metal matrix composites are prominent materials systems being considered for high temperature aerospace applications. One of the major problems with this material is the reactivity between existing reinforcements and the matrix after prolonged thermal exposure. This paper presents results from an investigation of reaction kinetics between Ti-14Al-21Nb (wt pct) and SCS-6 fibers and SiC fibers with surface coatings of TiB2, TiC, TiN, W, and Si. Microstructural evaluation of the reaction layers as well as matrix regions around the fibers is presented.

Wawner, F. E.↗

The kinetics of lunar glass formation, revisited

The nucleation frequency of Lunar Composition 70019, a lithified soil breccia from the center of a small crater in the Taurus-Littrow Valley, is determined using a relation that describes nucleation throughout the volume of a liquid together with measurements of the time required at temperatures of 780 to 930 C to obtain sensibly crystalline bodies. Curves indicating the time required at a given temperature to reach a particular fraction crystallized are shown to have the general form predicted by kinetic analysis. Nucleation frequencies are evaluated by applying such analysis to a curve representing the transition between glassy material and material with a sensible degree of crystallinity. The results obtained are found to be in excellent agreement with the values expected from the classical theory of homogeneous nucleation, indicating that such nucleation represents the dominant contribution to crystal formation, at least over the range of undercoolings covered (250 to 400 C).

Klein, L. C.↗

Solidification kinetics and metastable phase formation in binary Ti-Al

Electromagnetic levitation was used to solidify near-equiatomic alloys of Ti-Al at various bulk undercoolings. Detailed thermal histories were acquired during experiments using optical pyrometry with sampling rates as fast as 500 KHz. Solidification and other high-temperature transformation pathways were deduced from the thermal data and microstructural analysis. Recalescence rise times were employed to determine semiquantitative primary solidification kinetics for the different phases. Primary beta solidification was observed at compositions well into the equilibrium alpha regime; this is presented as part of a near-equiatomic nucleation domain diagram that shows the primary solidification phase that results for each combination of nucleation temperature and composition. Solidification kinetics are faster for primary beta than they are for primary alpha. For undercoolings less than about 150 K, the primary solidification kinetics are about an order of magnitude slower for gamma than for alpha.

Anderson, C. D.↗

Nonequilibrium shock wave structure, 1. Kinetics of nitric oxide formation and decomposition, 2

Theoretical and numerical aspects of molecular flow simulation focussed on the development of collision models for diatomic and triatomic gases undergoing rotational excitation and energy exchange. A laser absorption technique is proposed and analyzed as sufficiently sensitive for measuring rotational populations in a nonequilibrium shock wave. Also reported is a survey of available literature on NO chemical rate data in preparation for experiments on NO decompensation kinetics in atmospheric pollution.

Kruger, C. H.↗

Thermodynamics and kinetics of pack aluminide coating formation on IN-100

An investigation of the effects of pack variables on the formation of aluminide coatings on nickel-base superalloy IN-100 was conducted. Also, the thermodynamics and kinetics of coating formation were analyzed. Observed coating weights were in good agreement with predictions made from the analysis. Pack temperature rather than pack aluminum activity controls the principal coating phase formed. In 1 weight percent aluminum packs, aluminum weight gains were related to the halide pack activator. Solid-state nickel diffusion controlled coating formation from sodium fluoride and chloride and ammonium fluoride activated packs. In other ammonium and sodium halide activated 1 weight percent aluminum packs, gaseous diffusion controlled coating formation.

Levine, S. R.↗

Thermodynamics and kinetics of pack aluminide coating formation on IN-100

An investigation of the effects of pack variables on the formation of aluminide coatings on nickel-base superalloy IN-100 was conducted. Also, the thermodynamics and kinetics of coating formation were analyzed. Observed coating weights were in good agreement with predictions made from the analysis. Pack temperature rather than pack aluminum activity controls the principal coating phase formed. Solid-state nickel diffusion controlled coating formation from sodium fluoride and chloride and ammonium fluoride activated packs. In other ammonium and sodium halide activated 1 weight percent aluminum packs, gaseous diffusion controlled coating formation.

Levine, S. R.↗

Kinetics of oxygen atom formation during the oxidation of methane behind shock waves

An experimental and analytical study of the formation of oxygen atoms during the oxidation of methane and methane-hydrogen mixtures behind incident shock waves was carried out over the temperature range 1790-2584 K at reaction pressures between 1.2 and 1.7 atm. Oxygen atom levels were determined indirectly by measurement of emission from reaction of O with CO. On the basis of these data and ignition-delay data reported in the literature, a kinetic scheme for methane oxidation was assembled. The proposed kinetic mechanism, in general, predicts higher peak oxygen atom levels than the current oxidation mechanisms proposed by Bowman and Seery and by Skinner and his co-workers.

Jachimowski, C. J.↗

Highly efficient peptide formation from N-acetylaminoacyl-AMP anhydride and free amino acid

The kinetics of formation of the N-blocked dipeptide, N-acetylglycylglycine, from N-acetylglycyl adenylate anhydride and glycine in aqueous solution at 25 C, and at various PH's are reported. The reaction is of interest in that over a physiologically relevant pH range (6-8), peptide synthesis proceeds more rapidly than hydrolysis, even at those pH's at which this compound becomes increasingly susceptible to base-catalyzed hydrolysis. Under similar conditions, the corresponding unblocked aminoacyl adenylate anhydrides are considerably more unstable, and undergo appreciable hydrlysis in the presence of free amino acid. Because N-blocked aminoacyl adenylate anhydrides serve as model compounds of peptidyl adenylate anhydrides, these results suggest that primitive amino acid polymerization systems may have operated by cyclic reactivation of the peptidyl carboxyl group, rather than that of the incoming amino acid.

Mullins, D. W., Jr.↗

The formation of lunar breccias - Sintering and crystallization kinetics

The process of clastic breccia formation by viscous sintering in a stress-free environment is analyzed by treating crystallization and sintering as concurrent, competing processes. The kinetic analysis of crystallization is based on the construction of continuous cooling curves corresponding to the degree of crystallinity observed in the matrix of the breccia. These curves are obtained from corresponding time-temperature-transformation curves, which in turn are constructed from measured values of the crystal growth rate together with calculated values of the nucleation frequency. The kinetic analysis of sintering is based on a modification of the Frenkel (1945) treatment of viscous sintering appropriate for conditions of continuous cooling. The analysis is applied to Lunar Composition 70019 to illustrate the approach. It is shown that it is possible from the kinetic analysis to estimate both the rate at which a given breccia cooled and the minimum temperature at which the matrix particles came in contact. The results obtained for Lunar Composition 70019 seem physically reasonable and suggest that this sample cooled on the surface of the moon in its present form rather than buried in an ejecta blanket from which it was later excavated.

Uhlmann, D. R.↗

Effects of Buoyancy on Laminar, Transitional, and Turbulent Gas Jet Diffusion Flames

Gas jet diffusion flames have been a subject of research for many years. However, a better understanding of the physical and chemical phenomena occurring in these flames is still needed, and, while the effects of gravity on the burning process have been observed, the basic mechanisms responsible for these changes have yet to be determined. The fundamental mechanisms that control the combustion process are in general coupled and quite complicated. These include mixing, radiation, kinetics, soot formation and disposition, inertia, diffusion, and viscous effects. In order to understand the mechanisms controlling a fire, laboratory-scale laminar and turbulent gas-jet diffusion flames have been extensively studied, which have provided important information in relation to the physico-chemical processes occurring in flames. However, turbulent flames are not fully understood and their understanding requires more fundamental studies of laminar diffusion flames in which the interplay of transport phenomena and chemical kinetics is more tractable. But even this basic, relatively simple flame is not completely characterized in relation to soot formation, radiation, diffusion, and kinetics. Therefore, gaining an understanding of laminar flames is essential to the understanding of turbulent flames, and particularly fires, in which the same basic phenomena occur. In order to improve and verify the theoretical models essential to the interpretation of data, the complexity and degree of coupling of the controlling mechanisms must be reduced. If gravity is isolated, the complication of buoyancy-induced convection would be removed from the problem. In addition, buoyant convection in normal gravity masks the effects of other controlling parameters on the flame. Therefore, the combination of normal-gravity and microgravity data would provide the information, both theoretical and experimental, to improve our understanding of diffusion flames in general, and the effects of gravity on the burning process in particular.

Bahadori, M. Yousef↗

Research on rechargeable oxygen electrodes.

A research program is described which consisted of studying the effects of electrode cycling in very pure KOH solutions, with and without controlled additions of impurities, on oxide formation, oxygen evolution kinetics, oxygen reduction kinetics (including hydrogen peroxide formation), and changes in electrode structure. Bright platinum, platinized platinum, and Teflon-bonded platinum black electrodes were studied. Three main problem areas are identified: the buildup of a refractory anodic layer on prolonged cycling, which leads to a degradation of performance; the dissolution and subsequent deposition of dendritic platinum in the separator, leading to short-circuit ing and loss of electrocatalyst; and the disruptive effect of bubbling during gas evolution on charge. Each of these problem areas is analyzed, and remedial solutions are proposed.

Giner, J.↗

Contribution to "AIAA Aerospace Year in Review" article

The NASA Marshall Space Flight Center Microgravity Science Program is dedicated to promoting our understanding of materials processing by conducting relevant experiments in the microgravity environment and supporting related modeling efforts with the intent of improving ground-based practices. Currently funded investigations include research on dopant distribution and defect formation in semiconductors, microstructural development and transitions in dendritic casting alloys, coarsening phenomena, competition between thermal and kinetic phase formation, and the formation of glassy vs. crystalline material. NASA Microgravity Materials Science Principle Investigators are selected for funding either through a proposal in response to a NASA Research Announcement or by collaborating on a team that has successfully proposed to a foreign space agency research announcement. In the latter case, a US investigator can then apply to NASA for funding through an unsolicited proposal. The International Space Station (ISS) facilities used for the experimental investigations are provided primarily by partnering with foreign agencies and often US investigators are working as a part of a larger team studying a specific area of materials science. Facilities for conducting experiments aboard the ISS include the European Space Agency (ESA) Low Gradient Facility (LGF) and the Solidification and Quench (SQF) modular inserts to the Materials Research Rack/Materials Science Laboratory and are primarily used for controlled solidification studies. The French Space Agency (CNES) provided DECLIC facility allows direct observation of morphological development in transparent materials that solidify analogously to metals. The ESA provided Electro ]Magnetic Levitator (EML) is designed to levitate, melt and then cool samples in order to determine material properties, study nucleation behavior, and document phase transitions. Finally, the Microgravity Science Glovebox (MSG) serves as a onboard facility for supporting the hardware required to conduct a number of smaller, short-term investigations.

Grugel, Richard N.↗

Kinetic Simulations of Current-Sheet Formation and Reconnection at a Magnetic X Line

The integration of kinetic effects into macroscopic numerical models is currently of great interest to the plasma physics community, particularly in the context of magnetic reconnection. We are examining the formation and reconnection of current sheets in a simple, two-dimensional X-line configuration using high resolution particle-in-cell (PIC) simulations. The initial potential magnetic field is perturbed by thermal pressure introduced into the particle distribution far from the X line. The relaxation of this added stress leads to the development of a current sheet, which reconnects for imposed stress of sufficient strength. We compare the evolution and final state of our PIC simulations with magnetohydrodynamic simulations assuming both uniform and localized resistivities, and with force-free magnetic-field equilibria in which the amount of reconnect ion across the X line can be constrained to be zero (ideal evolution) or optimal (minimum final magnetic energy). We will discuss implications of our results for reconnection onset and cessation at kinetic scales in dynamically formed current sheets, such as those occurring in the terrestrial magnetotail and solar corona.

Black, C.↗

Kinetics and mechanism of the formation of water cluster ions from O2(plus) and H2O in He, Ar, N2, and O2 at 296 K

The reaction sequence leading from O2(+) to H3O(+)-H2O was examined in He, Ar, N2 and O2 carrier gases in a flowing afterglow system. The rate constants for the reactions were measured and the kinetic analysis for their determination is presented. For M = N2, two new steps involving the formation and reaction of O2(+)-N2 were proposed and examined. The rate constants are discussed and compared with other experimental values.

Howard, C. J.↗

Kinetics and Thermochemistry of ClCO Formation from the Cl + CO Association Reaction

Laser flash photolysis of Cl2/CO/M mixtures (M = N2, CO, Ar, CO2) has been employed in conjunction with Cl((sup 2)P(sub J)) detection by time-resolved resonance fluorescence spectroscopy to investigate equilibration kinetics in the reactions Cl((sup 2)P(sub J)) + CO ClCO as a function of temperature (185-260 K) and pressure (14-200 Torr). The association and dissociation reactions are found to be in the low-pressure limit over the range of experimental conditions investigated. In N2 and/or CO buffer gases, the temperature dependences of the ClCO formation and dissociation reaction rate constants are described by the Arrhenius expressions k(sub 1) = (1.05 +/- 0.36) x 10(exp -34) exp[(810 +/- 70)/T] cm(exp 6)/molecules(exp 2).s and k(sub -1) = (4.1 +/- 3.1) x 10(exp -10) exp[(-2960 +/- 60)/T]cu cm/(molecule.s) (errors are 2 sigma). Second- and third-law analyses of the temperature dependence of the equilbrium constant (k/k-1) lead to the following thermodynamic parameters for the association reaction: Delta-H(sub 298) = -7.7 +/- 0.6 kcal/mol, Delta-H(sub 0) = -6.9 +/- 0.7 kcal/mol, Delta-S(sub 298) = -23.8 +/- 2.0 cal/mole.K, Delta-H(sub f,298)(ClCO) = 5.2 +/- 0.6 kcal/mol (errors are 2 sigma). The results repported in this study significantly reduce the uncertainties in all reported kinetic and thermodynamic parameters.

Nicovich, J. M.↗

Experimental and Computational Study fo CH, CH*, and OH* in an Axisymmetric Laminar Diffusion Flame

In this study, we extend the results of previous combined numerical and experimental investigations of an axisymmetric laminar diffusion flame in which difference Raman spectroscopy, laser-induced fluorescence (LIF), and a multidimensional flame model were used to generate profiles of the temperature and major and minor species. A procedure is outlined by which the number densities of ground-state CH (X(sup 2)II) excited-state CH (A(sup 2)Delta, denoted CH*), and excited-state OH (A(sup 2)Sigma, denoted OH*) are measured and modeled. CH* and OH* number densities are deconvoluted from line-of-sight flame-emission measurements. Ground-state CH is measured using linear LIF. The computations are done with GRI Mech 2.11 as well as an alternate hydrocarbon mechanism. In both cases, additional reactions for the production and consumption of CH* and OH* are added from recent kinetic studies. Collisional quenching and spontaneous emission are responsible for the de-excitation of the excited-state radicals. As with our previous investigations, GRI Mech 2.11 continues to produce very good agreement with the overall flame length observed in the experiments, while significantly under predicting the flame lift-off height. The alternate kinetic scheme is much more accurate in predicting lift-off height but overpredicts the over-all flame length. Ground-state CH profiles predicted with GRI Mech 2.11 are in excellent agreement with the corresponding measurements, regarding both spatial distribution and absolute concentration (measured at 4 ppm) of the CH radical. Calculations of the excited-state species show reasonable agreement with the measurements as far as spatial distribution and overall characteristics are concerned. For OH*, the measured peak mole fraction, 1.3 x 10(exp -8), compared well with computed peaks, while the measured peak level for CH*, 2 x 10(exp -9), was severely underpredicted by both kinetic schemes, indicating that the formation and destruction kinetics associated with excited-state species in flames require further research.

Walsh, K. T.↗

Analytical study of mechanisms for nitric oxide formation during combustion of methane in a jet-stirred combustor

The role of chemical kinetics in the formation of nitric oxide during the combustion of methane was examined analytically by means of a detailed chemical mechanism for the oxidation of methane, for the reaction between hydrocarbon fragments, and for the formation of nitric oxide. By comparing predicted nitric oxide levels with values reported in the literature from jet-stirred combuster experiments, it was determined that the nitric oxide levels observed in fuel-rich flames cannot be described by a mechanism in which the rate of nitric oxide formation is controlled solely by the kinetics of oxygen atom formation. A proposed mechanism for the formation of nitric oxide in methane-rich flames reproduces the observed levels. The oxidation of hydrogen cyanide appears to be an important factor in nitric oxide formation.

Jachimowski, C. J.↗

Development of a model and computer code to describe solar grade silicon production processes

Two computer codes were developed for describing flow reactors in which high purity, solar grade silicon is produced via reduction of gaseous silicon halides. The first is the CHEMPART code, an axisymmetric, marching code which treats two phase flows with models describing detailed gas-phase chemical kinetics, particle formation, and particle growth. It can be used to described flow reactors in which reactants, mix, react, and form a particulate phase. Detailed radial gas-phase composition, temperature, velocity, and particle size distribution profiles are computed. Also, deposition of heat, momentum, and mass (either particulate or vapor) on reactor walls is described. The second code is a modified version of the GENMIX boundary layer code which is used to compute rates of heat, momentum, and mass transfer to the reactor walls. This code lacks the detailed chemical kinetics and particle handling features of the CHEMPART code but has the virtue of running much more rapidly than CHEMPART, while treating the phenomena occurring in the boundary layer in more detail.

Gould, R. K.↗