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At least 37 records · Page 2

Low resistance silver contacts to indium phosphide - Electrical and metallurgical considerations

The electrical and metallurgical behavior of the Ag-InP contact system has been investigated. Specific contact resistivity (Rc) values in the low 10 exp -6 Ohm sq cm range are readily achieved on n-InP (Si: 1.7 x 10 exp 18/cu cm) after sintering at 400 C for several minutes. The low Rc values, however, are shown to be accompanied by dissolution of InP into the metallization, resulting in device degradation. An analysis of the sinter-induced metallurgical interactions shows this system to be similar to the well-characterized Au-InP system, albeit with fundamental differences. The similarities include the dissociative diffusion of In, the reaction-suppressing effect of SiO2 capping, and especially, the formation of a phosphide layer at the metal-InP interface. The low post-sinter Rc values in the Ag-InP system may be due to the presence of a AgP2 layer at the metal-InP interface; low values of Rc can be achieved without incurring device degrading metallurgical interactions by introducing a thin AgP2 layer between the InP and the current carrying metallization.

Weizer, Victor G.↗

The Cool Flames Experiment

A space-based experiment is currently under development to study diffusion-controlled, gas-phase, low temperature oxidation reactions, cool flames and auto-ignition in an unstirred, static reactor. At Earth's gravity (1g), natural convection due to self-heating during the course of slow reaction dominates diffusive transport and produces spatio-temporal variations in the thermal and thus species concentration profiles via the Arrhenius temperature dependence of the reaction rates. Natural convection is important in all terrestrial cool flame and auto-ignition studies, except for select low pressure, highly dilute (small temperature excess) studies in small vessels (i.e., small Rayleigh number). On Earth, natural convection occurs when the Rayleigh number (Ra) exceeds a critical value of approximately 600. Typical values of the Ra, associated with cool flames and auto-ignitions, range from 104-105 (or larger), a regime where both natural convection and conduction heat transport are important. When natural convection occurs, it alters the temperature, hydrodynamic, and species concentration fields, thus generating a multi-dimensional field that is extremely difficult, if not impossible, to be modeled analytically. This point has been emphasized recently by Kagan and co-workers who have shown that explosion limits can shift depending on the characteristic length scale associated with the natural convection. Moreover, natural convection in unstirred reactors is never "sufficiently strong to generate a spatially uniform temperature distribution throughout the reacting gas." Thus, an unstirred, nonisothermal reaction on Earth does not reduce to that generated in a mechanically, well-stirred system. Interestingly, however, thermal ignition theories and thermokinetic models neglect natural convection and assume a heat transfer correlation of the form: q=h(S/V)(T(bar) - Tw) where q is the heat loss per unit volume, h is the heat transfer coefficient, S/V is the surface to volume ratio, and (T(bar) - Tw ) is the spatially averaged temperature excess. This Newtonian form has been validated in spatially-uniform, well-stirred reactors, provided the effective heat transfer coefficient associated with the unsteady process is properly evaluated. Unfortunately, it is not a valid assumption for spatially-nonuniform temperature distributions induced by natural convection in unstirred reactors. "This is why the analysis of such a system is so difficult." Historically, the complexities associated with natural convection were perhaps recognized as early as 1938 when thermal ignition theory was first developed. In the 1955 text "Diffusion and Heat Exchange in Chemical Kinetics", Frank-Kamenetskii recognized that "the purely conductive theory can be applied at sufficiently low pressure and small dimensions of the vessel when the influence of natural convection can be disregarded." This was reiterated by Tyler in 1966 and further emphasized by Barnard and Harwood in 1974. Specifically, they state: "It is generally assumed that heat losses are purely conductive. While this may be valid for certain low pressure slow combustion regimes, it is unlikely to be true for the cool flame and ignition regimes." While this statement is true for terrestrial experiments, the purely conductive heat transport assumption is valid at microgravity (mu-g). Specifically, buoyant complexities are suppressed at mu-g and the reaction-diffusion structure associated with low temperature oxidation reactions, cool flames and auto-ignitions can be studied. Without natural convection, the system is simpler, does not require determination of the effective heat transfer coefficient, and is a testbed for analytic and numerical models that assume pure diffusive transport. In addition, mu-g experiments will provide baseline data that will improve our understanding of the effects of natural convection on Earth.

Pearlman, Howard↗

Diffusion in mixed solvents. II - The heat of mixing parameter

Correlation of second-order rate constants for many reactions involving electron transfer between organic molecules, solvated electron reactions, iodine diffusion coefficients, and triplet state electron transfer reactions has been made with the heat of mixing parameter (HMP) for the aqueous binary solvent systems. The aqueous binary solvents studied are those containing methanol or ethanol (type I solvent); 1-propanol or tert-butyl alcohol (type II solvent); or sucrose or glycerol (type III solvent). A plot of the HMP vs. the diffusion parameter for each reaction yields superimposable curves for these reactions in a particular solvent mixture over the entire solvent mixture range, irrespective of the value of the reaction's rate constant or diffusion coefficient in water.

Carapellucci, P. A.↗

Scientific objectives of the primitive body sample return missions: An approach from the light-induced effect on water vapor

Water is undoubtedly one of the most crucial components of the solar nebula for determining planetary composition: planets were formed from the accretion of the dust particles in the nebula, and the redox state of Fe in the particles can be determined by the reaction of Fe with water vapor diffused into the interior of the particle in the early stage of solar system formation. It has been discussed from various observations that the cores of Mercury, Venus, and the Earth might be metallic Fe, although the core of the Earth may be somewhat oxidized by the high pressure and temperature reaction of liquid Fe with perovskite at the boundary of the mantle and the core, whereas the core of Mars may be highly oxidized, as suggested by its low density. Isotopic anomalies of various elements have frequently been observed in the solar system (in planetary atmospheres and in meteorites) and some of them can be attributed to the injection of exotic particles formed in other stars into the solar nebula. Hydrogen and D anomalies in planetary atmospheres were frequently believed to correlate with the differential escape of H and D from the exospheres of Venus and Mars, although no one knows the primordial D/H ratios before thermal escape. This paper explains the decrease of the observed D/H ratios with distance from the sun by considering the light-induced drift effect to displace H2(16)O alone to the outside in the solar nebula.

Shimizu, Mikio↗

In situ analysis of CO during chemisorption and oxidation on graphite: Supported Pt by FTIR-microspectrometry

For chemisorption and oxidation on Pt/HOPG (highly-orientated pyrolytic) graphite, reflectance Fourier Transform Infrared (FTIR)-microspectrometry reveals a variable state and reactivity for CO. Even for model surface science systems, where surface heterogeneity is minimal, surface diffusion may be too slow relative to the reaction rate to avoid segregation of reactants into surface islands under steady-state conditions. Thus in CO oxidation on Pt (where the relevant surface diffusion coefficients are such that D sub O less than D sub CO) then reactant CO islands exists at the perimeters of which the surface reaction is thought to occur. Furthermore CO can chemisorb on metals in linear and bridge forms to extents which vary with precise faces predominantly exposed coverage, etc. Infrared has long been used to probe the nature of adsorbed CO on model film and heterogeneous surfaces, but it may now be that FTIR-microspectrometry will allow the state of this adsorbate and reactant to be investigated with a spatial resolution of 4.4 microns on model (and real) catalytic surfaces.

Self, Valerie A.↗

The chemistry and diffusion of aircraft exhausts in the lower stratosphere during the first few hours after fly-by

An analysis of the hydrogen-nitrogen-oxygen reaction systems in the lower stratosphere as they are initially perturbed by individual aircraft engine exhaust plumes was conducted in order to determine whether any significant chemical reactions occur, either among exhaust chemical species, or between these species and the environmental ozone, while the exhaust products are confined to intact plume segments at relatively high concentrations. The joint effects of diffusive mixing and chemical kinetics on the reactions were also studied, using the techniques of second-order closure diffusion/chemistry models. The focus of the study was on the larger problem of the potential depletion of ozone by supersonic transport aircraft exhaust materials emitted into the lower stratosphere.

Hilst, G. R.↗

Atom movements occurring at solid metal-semiconductor interfaces

Solid metal-semiconductor interfaces often undergo chemical reaction at rather low temperatures, in some cases not much above room temperature. After some general discussion of these reactions, more detailed consideration is given to simple noncompound-forming systems, and, in particular, to the Si-Al, Ge-Al, and Si-Au systems. Diffusive transport of Si or Ge in these solid metallizations is very rapid, though the converse process, diffusion of metal in solid Si or Ge, is usually so slow as to be negligible. The interface reaction itself is less well understood but is becoming controllable in intrinsically favorable cases like Ge-Al and in other cases by more sophisticated means.

Mccaldin, J. O.↗

Electromagnetic containerless reaction of samarium with cobalt for the formation of samarium-cobalt alloys

The electromagnetic levitation technique has been used to obtain nearly stoichiometric SmCo5, with the reaction temperature controlled by a gas jet. The results of several experiments carried out at a 450 kHz, 25 kw RF power levitation facility using different reaction times and cooling rates are presented. It is shown that reaction rates achieved with the levitation technique are larger than the expected diffusion rate in the system liquid samarium-solid cobalt. It is also shown that substantial mixing occurs in the RF-levitated melt.

Chang, C. W.↗

A Role of the Reaction Kernel in Propagation and Stabilization of Edge Diffusion Flames of C1-C3 Hydrocarbons

Diffusion flame stabilization is of essential importance in both Earth-bound combustion systems and spacecraft fire safety. Local extinction, re-ignition, and propagation processes may occur as a result of interactions between the flame zone and vortices or fire-extinguishing agents. By using a computational fluid dynamics code with a detailed chemistry model for methane combustion, the authors have revealed the chemical kinetic structure of the stabilizing region of both jet and flat-plate diffusion flames, predicted the flame stability limit, and proposed diffusion flame attachment and detachment mechanisms in normal and microgravity. Because of the unique geometry of the edge of diffusion flames, radical back-diffusion against the oxygen-rich entrainment dramatically enhanced chain reactions, thus forming a peak reactivity spot, i.e., reaction kernel, responsible for flame holding. The new results have been obtained for the edge diffusion flame propagation and attached flame structure using various C1-C3 hydrocarbons.

Takahashi, Fumiaki↗

Nanoscale and Microscale Iron Emulsions for Treating DNAPL

This study demonstrated the feasibility of using emulsified nanoscale and microscale iron particles to enhance dehalogenation of (Dense Non-Aqueous Phase Liquid) DNAPL free-phase. The emulsified system consisted of a surfactant-stabilized, biodegradable oil-in-water emulsion with nanoscale or microscale iron particles contained within the emulsion droplets. It was demonstrated that DNAPLs, such as trichloroethene (TCE), diffuse through the oil membrane of the emulsion particle whereupon they reach an aqueous interior and the surface of an iron particle where dehalogenation takes place. The hydrocarbon reaction by-products of the dehalogenation reaction, primarily ethene (no chlorinated products detected), diffuse out of the emulsion droplet. This study also demonstrated that an iron-emulsion system could be delivered in-situ to the DNAPL pool in a soil matrix by using a simulated push well technique. Iron emulsions degraded pure TCE at a rate comparable to the degradation of dissolved phase TCE by iron particles, while pure iron had a very low degradation rate for free-phase TCE. The iron-emulsion systems can be injected into a sand matrix where they become immobilized and are not moved by flowing water. It has been documented that surfactant micelles possess the ability to pull pooled TCE into emulsion droplets where degradation of TCE takes place.

Geiger, Cherie L.↗

Thermodynamics and kinetics of reactions in protective coating systems

Investigations of fluoride activated packs with Al:Ni ratios greater than 50 a/o prove that the specimen surface is not in equilibrium with the pack at high Al:Ni ratios but that an activity gradient exists between pack and specimen. Therefore, gaseous diffusion and possibly surface reactions play a role in determining the overall rate of Al deposition in such packs. Noticeable differences in coating behavior have been obtained in packs activated with chloride and iodide, and it appears that poorest results are obtained with iodides, better with chlorides, and best with fluorides. A numerical method has been perfected for calculating rates of solid-state diffusion controlled coating formation, allowing for the variation of diffusivity with composition in the NiAl phase. Layer growth rates can now be accurately predicted from a knowledge of the surface and substrate compositions. Furthermore, the correct diffusion profiles are obtained by this method. These differ substantially from the profile obtained when the diffusivity is assumed constant.

Gupta, B.↗

Numerical Determination of Critical Conditions for Thermal Ignition

The determination of ignition or thermal explosion in an oxidizing porous body of material, as described by a dimensionless reaction-diffusion equation of the form .tu = .2u + .e-1/u over the bounded region O, is critically reexamined from a modern perspective using numerical methodologies. First, the classic stationary model is revisited to establish the proper reference frame for the steady-state solution space, and it is demonstrated how the resulting nonlinear two-point boundary value problem can be reexpressed as an initial value problem for a system of first-order differential equations, which may be readily solved using standard algorithms. Then, the numerical procedure is implemented and thoroughly validated against previous computational results based on sophisticated path-following techniques. Next, the transient nonstationary model is attacked, and the full nonlinear form of the reaction-diffusion equation, including a generalized convective boundary condition, is discretized and expressed as a system of linear algebraic equations. The numerical methodology is implemented as a computer algorithm, and validation computations are carried out as a prelude to a broad-ranging evaluation of the assembly problem and identification of the watershed critical initial temperature conditions for thermal ignition. This numerical methodology is then used as the basis for studying the relationship between the shape of the critical initial temperature distribution and the corresponding spatial moments of its energy content integral and an attempt to forge a fundamental conjecture governing this relation. Finally, the effects of dynamic boundary conditions on the classic storage problem are investigated and the groundwork is laid for the development of an approximate solution methodology based on adaptation of the standard stationary model.

Luo, W.↗

Summer Work Experience: Determining Methane Combustion Mechanisms and Sub-Scale Diffuser Properties for Space Transporation System Engine Testing

To assess engine performance during the testing of Space Shuttle Main Engines (SSMEs), the design of an optimal altitude diffuser is studied for future Space Transportation Systems (STS). For other Space Transportation Systems, rocket propellant using kerosene is also studied. Methane and dodecane have similar reaction schemes as kerosene, and are used to simulate kerosene combustion processes at various temperatures. The equations for the methane combustion mechanism at high temperature are given, and engine combustion is simulated on the General Aerodynamic Simulation Program (GASP). The successful design of an altitude diffuser depends on the study of a sub-scaled diffuser model tested through two-dimensional (2-D) flow-techniques. Subroutines given calculate the static temperature and pressure at each Mach number within the diffuser flow. Implementing these subroutines into program code for the properties of 2-D compressible fluid flow determines all fluid characteristics, and will be used in the development of an optimal diffuser design.

Williams, Powtawche N.↗

Measuring Hydrogen Concentrations in Metals

Commercial corrosion-measurement system adapted to electrochemical determination of hydrogen concentrations in metals. New technique based on diffusion of hydrogen through foil specimen of metal. In sample holder, hydrogen produced on one side of foil, either by corrosion reaction or by cathodic current. Hydrogen diffused through foil removed on other side by constant anode potential, which leads to oxidation of hydrogen to water. Anode current is measure of concentration of hydrogen diffusing through foil. System used to study hydrogen uptake, hydrogen elimination by baking, effect of heat treatment, and effect of electroplating on high-strength steels.

Danford, M. D.↗

Preparation for microgravity - The role of the Microgravity Material Science Laboratory

Experiments at the NASA Lewis Research Center's Microgravity Material Science Laboratory using physical and mathematical models to delineate the effects of gravity on processes of scientific and commercial interest are discussed. Where possible, transparent model systems are used to visually track convection, settling, crystal growth, phase separation, agglomeration, vapor transport, diffusive flow, and polymer reactions. Materials studied include metals, alloys, salts, glasses, ceramics, and polymers. Specific technologies discussed include the General Purpose furnace used in the study of metals and crystal growth, the isothermal dendrite growth apparatus, the electromagnetic levitator/instrumented drop tube, the high temperature directional solidification furnace, the ceramics and polymer laboratories and the center's computing facilities.

Johnston, J. Christopher↗

Amorphous metallic films in silicon metallization systems

Diffusion barrier research was focussed on lowering the chemical reactivity of amorphous thin films on silicon. An additional area of concern is the reaction with metal overlays such as aluminum, silver, and gold. Gold was included to allow for technology transfer to gallium arsenide PV cells. Amorphous tungsten nitride films have shown much promise. Stability to annealing temperatures of 700, 800, and 550 C were achieved for overlays of silver, gold, and aluminum, respectively. The lower results for aluminum were not surprising because there is an eutectic that can form at a lower temperature. It seems that titanium and zirconium will remove the nitrogen from a tungsten nitride amorphous film and render it unstable. Other variables of research interest were substrate bias and base pressure during sputtering.

So, F.↗

International Symposium on Combustion, 15th, Tokyo, Japan, August 25-31, 1974, Proceedings

Recent theoretical and experimental studies concerned with detonation and pressure wave combustion interaction, fire and explosion research and safety, heterogeneous combustion, flame-flow interactions, kinetics of elementary reactions, pollution control in and by combustion systems, and ignition are presented. Some of the topics covered include critical power density for direct initiation of unconfined gaseous detonations, extinction of laminar diffusion flames for liquid fuels, combustion of bulk titanium in oxygen, flame propagation in small spheres of unconfined and slightly confined flammable mixtures, kinetics of the reaction of nitric oxide with hydrogen, production of chemi-ions and formation of CH and CH2 radicals in methane-oxygen and ethylene-oxygen flames, NOx emission characteristics in two-stage combustion, and spherical ignition of oxyhydrogen behind a reflected shock wave. Individual items are announced in this issue.

Source record↗

Calcium-Magnesium-Aluminosilicate (CMAS) Reactions and Degradation Mechanisms of Advanced Environmental Barrier Coatings

The thermochemical reactions between calcium-magnesium-aluminosilicate- (CMAS-) based road sand and several advanced turbine engine environmental barrier coating (EBC) materials were studied. The phase stability, reaction kinetics and degradation mechanisms of rare earth (RE)-silicates Yb2SiO5, Y2Si2O7, and RE-oxide doped HfO2 and ZrO2 under the CMAS infiltration condition at 1500 C were investigated, and the microstructure and phase characteristics of CMAS-EBC specimens were examined using Scanning Electron Microscopy (SEM) and X-ray Diffraction (XRD). Experimental results showed that the CMAS dissolved RE-silicates to form crystalline, highly non-stoichiometric apatite phases, and in particular attacking the silicate grain boundaries. Cross-section images show that the CMAS reacted with specimens and deeply penetrated into the EBC grain boundaries and formed extensive low-melting eutectic phases, causing grain boundary recession with increasing testing time in the silicate materials. The preliminary results also showed that CMAS reactions also formed low melting grain boundary phases in the higher concentration RE-oxide doped HfO2 systems. The effect of the test temperature on CMAS reactions of the EBC materials will also be discussed. The faster diffusion exhibited by apatite and RE-doped oxide phases and the formation of extensive grain boundary low-melting phases may limit the CMAS resistance of some of the environmental barrier coatings at high temperatures.

Ahlborg, Nadia L.↗