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NASA NTRS1990

Studies of mechano-chemical interactions in the tribological behavior of materials

Mechano-chemical interaction studies can contribute to the understanding of wear and friction of materials. Specific examples of experimental results relative to the subject are discussed. There are two parts: one describes the synergistic effect of corrosion and wear of iron sliding on sapphire in sulfuric acid, and the other describes the effect of surface films on the wear and friction of plasma-deposited diamondlike carbon (amorphous hydrogenated carbon) films in sliding contact with silicon nitride. The concentration of acid (pH) is an important factor in controlling the iron loss caused by wear-corrosion processes in sulfuric acid. The mechanical action can cause chemical reactions to proceed much faster than they would otherwise. The diamondlike carbon (DLC) films are shown to behave tribologically much like bulk diamond. In a dry nitrogen environment, a mechano-chemical reaction produces a substance which greatly decreases the coefficient of friction. In a moist air environment, mechano-chemical interactions drastically reduce the wear life of DLC films and water vapor greatly increases friction.

Miyoshi, Kazuhisa↗

NASA NTRS1990

Impact constraints on the environment for chemical evolution and the continuity of life

The moon and the earth were bombarded heavily by planetesimals and asteroids that were capable of interfering with chemical evolution and the origin of life. This paper explores the frequency of giant terrestrial impacts able to stop prebiotic chemistry in the probable regions of chemical evolution. The limited time available between impacts disruptive to prebiotic chemistry at the time of the oldest evidence of life suggests the need for a rapid process for chemical evolution of life. On the other hand, rapid chemical evolution in cloud systems and lakes or other shallow evaporating water bodies would have been possible because reactants could have been concentrated and polymerized rapidly in this environment. Thus life probably could have originated near the surface between frequent surface-sterilizing impacts. There may not have been continuity of life depending on sunlight because there is evidence that life, existing as early as 3.8 Gyr ago, may have been destroyed by giant impacts. The first such organisms on earth were probably not the ancestors of present life.

Oberbeck, Verne R.↗

NASA NTRS1991

Chemically Layered Porous Solids

Aerogels and other porous solids in which surfaces of pores have chemical properties varying with depth below macroscopic surfaces prepared by sequences of chemical treatments. Porous glass or silica bead treated to make two depth zones having different chemical properties. Beads dropped along tube filled with flowing gas containing atomic oxygen, generated in microwave discharge. General class of materials treatable include oxides of aluminum, silicon, zirconium, tin, titanium, and nickel, and mixtures of these oxides. Potential uses of treated materials include chromatographic separations, membrane separations, controlled releases of chemicals, and catalysis.

Koontz, Steve↗

NASA NTRS1989

Modeling of high speed chemically reacting flow-fields

The SPARK3D and SPARK3D-PNS computer programs were developed to model 3-D supersonic, chemically reacting flow-fields. The SPARK3D code is a full Navier-Stokes solver, and is suitable for use in scramjet combustors and other regions where recirculation may be present. The SPARK3D-PNS is a parabolized Navier-Stokes solver and provides an efficient means of calculating steady-state combustor far-fields and nozzles. Each code has a generalized chemistry package, making modeling of any chemically reacting flow possible. Research activities by the Langley group range from addressing fundamental theoretical issues to simulating problems of practical importance. Algorithmic development includes work on higher order and upwind spatial difference schemes. Direct numerical simulations employ these algorithms to address the fundamental issues of flow stability and transition, and the chemical reaction of supersonic mixing layers and jets. It is believed that this work will lend greater insight into phenomenological model development for simulating supersonic chemically reacting flows in practical combustors. Currently, the SPARK3D and SPARK3D-PNS codes are used to study problems of engineering interest, including various injector designs and 3-D combustor-nozzle configurations. Examples, which demonstrate the capabilities of each code are presented.

Drummond, J. P.↗

NASA NTRS1990

Chemical evolution of the early Martian hydrosphere

The chemical evolution of the early Martian hydrosphere is discussed. The early Martian ocean can be modeled as a body of relatively pure water in equilibrium with a dense carbon dioxide atmosphere. The chemical weathering of lavas, pyroclastic deposits, and impact melt sheets would have the effect of neutralizing the acidity of the juvenile water. As calcium and other cations are added to the water by chemical weathering, they are quickly removed by the precipitation of calcium carbonate and other minerals, forming a deposit of limestone beneath the surface of the ocean. As the atmospheric carbon dioxide pressure and the temperature decrease, the Martian ocean would be completely frozen. Given the scenario for the chemical evolution of the northern lowland plains of Mars, it should be possible to draw a few conclusions about the expected mineralogy and geomorphology of this regions.

Schaefer, M. W.↗

NASA NTRS1991

A numerical study of shock wave/boundary layer interaction in nonequilibrium chemically reacting air - The effects of catalytic walls

This paper presents a numerical study that investigate the effects of nonequilibrium chemistry, and in particular, wall catalycity on the separated flow region generated by an oblique shock wave impinging upon a flat plate boundary layer. To obtain a solution to this problem, the full two dimensional Navier-Stokes equations were solved using MacCormack's predictor-corrector time dependent technique on a rectangular grid. Nonequilibrium chemistry was included by utilizing the 5 species, 17 reaction modified Dunn-Kang chemical kinetics model. Separate results were obtained for: calorically perfect, chemically reacting - noncatalytic wall, and chemically reacting - fully catalytic wall cases, for a given set of flow conditions. A direct comparison of all three cases revealed a slight decrease in the peak heat transfer for the noncatalytic wall case, as compared to the calorically perfect case. On the other hand, the fully catalytic wall case had a tremendous increase in the peak surface heat transfer. It is concluded that, for the particular conditons treated here (nearly frozen flow in the free stream), the effects of the nonequilibrium chemically reacting flow on the shock-wave/boundary-layer interaction depend critically on the catalycity of the wall, having virtually no effect for the case of a noncatalytic wall, and exerting a tremendous effect for a fully catalytic wall.

Grumet, Adam A.↗

NASA NTRS1991

Shock strength effects on separated flows in non-equilibrium chemically reacting air - Shock wave/boundary layer interaction

This work is part of a general study to examine the effects of nonequilibrium chemical reactions on hypersonic separated flows. In particular, the work presented is the first attempt to quantitatively predict the effects of impinging shock strength on the separation region in non-equilibrium chemically reacting air over a flat plate. Of special interest is the local heat transfer rate to the plate at the reattachment point. The effects of chemically non-equilibrium on the flow field are assessed by making direct comparisons to the results calculated assuming a calorically perfect flow. Chemical reactions are found to increase heat transfer rates, and this increase becomes significantly larger as Reynolds number increases.

Ballaro, Charles A.↗

NASA NTRS1991

Spatial and temporal variability of the extent of chemically processed stratospheric air

Simulations of the spatial and temporal variability of the extent of chemically processed air in the Arctic stratosphere have been carried out using a three-dimensional chemistry-transport model for the winters of 1979 and 1989. Chemically processed air is identified in the model as that in which the amounts of hydrogen chloride (HCl) calculated with parameterized loss for conditions appropriate to polar stratospheric cloud (PSC) formation are substantially smaller than those calculated in a model with gas phase chemistry only. It is seen that chemically processed air may be identified over much of the Arctic lower stratosphere from early January to late February, with HCl depletions being larger in 1989 than in 1979. Near the latitude of the Arctic circle, there is important spatial and temporal variability in the extent of chemically processed air. There is some evidence for transport to midlatitudes of processed air during these winters, but the HCl reductions are much smaller and more sporadic than those near the pole. At 62 and 42N, processed air is calculated to occur preferentially over the longitude regions from 60-120E and 270-330E.

Kaye, Jack A.↗

NASA NTRS1990

Chemical reacting flows

Future aerospace propulsion concepts involve the combustion of liquid or gaseous fuels in a highly turbulent internal airstream. Accurate predictive computer codes which can simulate the fluid mechanics, chemistry, and turbulence-combustion interaction of these chemical reacting flows will be a new tool that is needed in the design of these future propulsion concepts. Experimental and code development research is being performed at LeRC to better understand chemical reacting flows with the long-term goal of establishing these reliable computer codes. Our approach to understand chemical reacting flows is to look at separate, more simple parts of this complex phenomenon as well as to study the full turbulent reacting flow process. As a result, we are engaged in research on the fluid mechanics associated with chemical reacting flows. We are also studying the chemistry of fuel-air combustion. Finally, we are investigating the phenomenon of turbulence-combustion interaction. Research, both experimental and analytical, is highlighted in each of these three major areas.

Mularz, Edward J.↗

NASA NTRS1992

Influences of chemical sympathectomy, demedullation, and hindlimb suspension on the V(O2)max of rats

The contributions of catecholamines from the adrenal medulla to the reduction in maximal oxygen consumption is investigated in chemically sympathectomized rats. The rats are injected with saline and chemically sympathectomized, and approximately half of the rats are surgically demedullated. The subjects undergo head-down suspension for two weeks and are examined in terms of submaximal mechanical efficiency, treadmill run time, and maximal oxygen consumption. Rats with adrenal medullas and injected with saline demonstrate reduced levels of maximal O consumption, whereas chemically sympathectomized rats with adrenal medullas showed no significant reduction. Reduced levels of maximal O consumption is also noted in the sympathectomized demedullated rats. The paper concludes that circulating epinephrine enhances the attenuation of the decrease in the maximal O consumption caused by chemical sympathectomy.

Woodman, Christopher R.↗

NASA NTRS1992

Reflectance spectroscopy of fresh whole leaves for the estimation of chemical concentration

Remotely sensed plant-canopy data in the visible and near-IR ranges are used to establish relations between the canopy reflectance and the chemical content of the leaves. The mathematical relation is generated by means of stepwise regression based on the derivative reflectance at certain wavelengths. Fourier filtering and sample control are used to minimize instrument noise and spectral overlap respectively, and absorption features are noted that correspond to sugar and protein. The coefficients of determination between estimated and measured concentrations are at least 0.82 for such substances as starch and chlorophyll. It is recommended in the analysis of remotly sensed canopy data that the chemicals with strong spectral overlaps with the chemical of interest be accounted for in order to estimate foliar chemical concentrations accurately.

Curran, Paul J.↗

NASA NTRS1993

Improved inhalation technology for setting safe exposure levels for workplace chemicals

Threshold Limit Values recommended as allowable air concentrations of a chemical in the workplace are often based upon a no-observable-effect-level (NOEL) determined by experimental inhalation studies using rodents. A 'safe level' for human exposure must then be estimated by the use of generalized safety factors in attempts to extrapolate from experimental rodents to man. The recent development of chemical-specific physiologically-based toxicokinetics makes use of measured physiological, biochemical, and metabolic parameters to construct a validated model that is able to 'scale-up' rodent response data to predict the behavior of the chemical in man. This procedure is made possible by recent advances in personal computer software and the emergence of appropriate biological data, and provides an analytical tool for much more reliable risk evaluation and airborne chemical exposure level setting for humans.

Stuart, Bruce O.↗

NASA NTRS1993

A kinetic and equilibrium analysis of silicon carbide chemical vapor deposition on monofilaments

Chemical kinetics of atmospheric pressure silicon carbide (SiC) chemical vapor deposition (CVD) from dilute silane and propane source gases in hydrogen is numerically analyzed in a cylindrical upflow reactor designed for CVD on monofilaments. The chemical composition of the SiC deposit is assessed both from the calculated total fluxes of carbon and silicon and from chemical equilibrium considerations for the prevailing temperatures and species concentrations at and along the filament surface. The effects of gas and surface chemistry on the evolution of major gas phase species are considered in the analysis.

Gokoglu, S. A.↗

NASA NTRS1992

Prediction of Chemical Vapor Deposition Rates on Monofilaments and Its Implications for Fiber Properties

Deposition rates are predicted in a cylindrical upflow reactor designed for chemical vapor deposition (CVD) on monofilaments. Deposition of silicon from silane in a hydrogen carrier gas is chosen as a relevant example. The effects of gas and surface chemistry are studied in a two-dimensional axisymmetric flow field for this chemically well-studied system. Model predictions are compared to experimental CVD rate measurements. The differences in some physical and chemical phenomena between such small diameter (about 150 microns) fiber substrates and other typical CVD substrates are highlighted. The influence of the Soret mass transport mechanism is determined to be extraordinarily significant. The difficulties associated with the accurate measurement and control of the fiber temperature are discussed. Model prediction sensitivities are investigated with respect to fiber temperatures, fiber radii, Soret transport, and chemical kinetic parameters. The implications of the predicted instantaneous rates are discussed relative to the desired fiber properties for both the batch and the continuous processes.

Gokoglu, S. A.↗

NASA NTRS1991

Modeling of InP metalorganic chemical vapor deposition

The growth of InP by metalorganic chemical vapor deposition (MOCVD) in a horizontal reactor is being modeled with a commercially available computational fluid dynamics modeling code. The mathematical treatment of the MOCVD process has four primary areas of concern: 1) transport phenomena, 2) chemistry, 3) boundary conditions, and 4) numerical solution methods. The transport processes involved in CVD are described by conservation of total mass, momentum, energy, and atomic species. Momentum conservation is described by a generalized form of the Navier-Stokes equation for a Newtonian fluid and laminar flow. The effect of Soret diffusion on the transport of particular chemical species and on the predicted deposition rate is examined. Both gas-phase and surface chemical reactions are employed in the model. Boundary conditions are specified at the inlet and walls of the reactor for temperature, fluid flow and chemical species. The coupled set of equations described above is solved by a finite difference method over a nonuniform rectilinear grid in both two and three dimensions. The results of the 2-D computational model is presented for gravity levels of zero- and one-g. The predicted growth rates at one-g are compared to measured growth rates on fused silica substrates.

Black, Linda R.↗

NASA NTRS1993

Numerical investigation of complex, transitional, and chemically reacting flows

This document is divided into two parts. Part A, on turbulent transport of chemical species in compressible reacting flows, includes the following topics: mixing of chemical species in reacting flows; chemically reacting turbulent flows; turbulent mixing of chemical species in reacting flows, which includes large eddy mixing, turbulent mixing, and molecular mixing; multiple time scale turbulence equations; species conservation equations for reacting flows; and a finite volume numerical method. Part B, on unsteady transitional flows over forced oscillatory surfaces, discusses unsteady transitional flow equations with moving boundaries and the application of the finite volume numerical solution method.

Kim, S.-W.↗

NASA NTRS1994

Calculation of Propulsive Nozzle Flowfields in Multidiffusing Chemically Reacting Environments

An advanced engineering model has been developed to aid in the analysis and design of hydrogen/oxygen chemical rocket engines. The complete multispecies, chemically reacting and multidiffusing Navier-Stokes equations are modelled, including the Soret thermal diffusion and the Dufour energy transfer terms. In addition to the spectrum of multispecies aspects developed, the model developed in this study is also conservative in axisymmetric flow for both inviscid and viscous flow environments and the boundary conditions employ a viscous, chemically reacting, reference plane characteristics method. Demonstration cases are presented for a 1030:1 area ratio nozzle, a 25 lbf film cooled nozzle, and a transpiration cooled plug and spool rocket engine. The results indicate that the thrust coefficient predictions of the 1030:1 and the 25 lbf film cooled nozzle are within 0.2 to 0.5 percent, respectively, of experimental measurements when all of the chemical reaction and diffusion terms are considered. Further, the model's predictions agree very well with the heat transfer measurements made in all of the nozzle test cases. The Soret thermal diffusion term is demonstrated to have a significant effect on the predicted mass fraction of hydrogen along the wall of the nozzle in both the laminar flow 1030:1 nozzle and the turbulent flow plug and spool nozzle analysis cases performed. Further, the Soret term was shown to represent an important fraction of the diffusion fluxes occurring in a transpiration cooled rocket engine.

Kacynski, Kenneth John↗

NASA NTRS1994

Computerized in vitro test for chemical toxicity based on tetrahymena swimming patterns

An apparatus and method for rapidly determining chemical toxicity was evaluated. The toxicity monitor includes an automated scoring of how motile biological cells (Tetrahymena pyriformis) slow down or otherwise change their swimming patterns in a hostile chemical environment. The device, called the Motility Assay Apparatus (MAA) is tested for 30 second determination of chemical toxicity in 20 aqueous samples containing trace organics and salts. With equal or better detection limits, results compare favorably to in vivo animal tests of eye irritancy, in addition to agreeing for all chemicals with previous manual evaluations of single cell motility.

Noever, David A.↗