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All sourcesNASA NTRSDOE OSTI
NASA NTRS1993

Thermal coatings for titanium-aluminum alloys

Titanium aluminides and titanium alloys are candidate materials for use in hot structure and heat-shield components of hypersonic vehicles because of their good strength-to-weight characteristics at elevated temperature. However, in order to utilize their maximum temperature capability, they must be coated to resist oxidation and to have a high total remittance. Also, surface catalysis for recombination of dissociated species in the aerodynamic boundary layer must be minimized. Very thin chemical vapor deposition (CVD) coatings are attractive candidates for this application because of durability and very light weight. To demonstrate this concept, coatings of boron-silicon and aluminum-boron-silicon compositions were applied to the titanium-aluminides alpha2 (Ti-14Al-21Nb), super-alpha2 (Ti-14Al-23-Nb-2V), and gamma (Ti-33Al-6Nb-1Ta) and to the titanium alloy beta-21S (Ti-15Mo-3Al-3Nb-0.2Si). Coated specimens of each alloy were subjected to a set of simulated hypersonic vehicle environmental tests to determine their properties of oxidation resistance, surface catalysis, radiative emittance, and thermal shock resistance. Surface catalysis results should be viewed as relative performance only of the several coating-alloy combinations tested under the specific environmental conditions of the LaRC Hypersonic Materials Environmental Test System (HYMETS) arc-plasma-heated hypersonic wind tunnel. Tests were also conducted to evaluate the hydrogen transport properties of the coatings and any effects of the coating processing itself on fatigue life of the base alloys. Results are presented for three types of coatings, which are as follows: (1) a single layer boron silicon coating, (2) a single layer aluminum-boron-silicon coating, and (3) a multilayer coating consisting of an aluminum-boron-silicon sublayer with a boron-silicon outer layer.

Cunnington, George R.↗
NASA NTRS2017

Development of a Detailed Surface Chemistry Framework in DSMC

Many of the current direct simulation Monte Carlo (DSMC) codes still employ only simple surface catalysis models. These include only basic mechanisms such as dissociation, recombination, and exchange reactions, without any provision for adsorption and finite rate kinetics. Incorporating finite rate chemistry at the surface is increasingly becoming a necessity for various applications such as high speed re-entry flows over thermal protection systems (TPS), micro-electro-mechanical systems (MEMS), surface catalysis, etc. In the recent years, relatively few works have examined finite-rate surface reaction modeling using the DSMC method.In this work, a generalized finite-rate surface chemistry framework incorporating a comprehensive list of reaction mechanisms is developed and implemented into the DSMC solver SPARTA. The various mechanisms include adsorption, desorption, Langmuir-Hinshelwood (LH), Eley-Rideal (ER), Collision Induced (CI), condensation, sublimation, etc. The approach is to stochastically model the various competing reactions occurring on a set of active sites. Both gas-surface (e.g., ER, CI) and pure-surface (e.g., LH, desorption) reaction mechanisms are incorporated. The reaction mechanisms could also be catalytic or surface altering based on the participation of the bulk-phase species (e.g., bulk carbon atoms). Marschall and MacLean developed a general formulation in which multiple phases and surface sites are used and we adopt a similar convention in the current work. Microscopic parameters of reaction probabilities (for gas-surface reactions) and frequencies (for pure-surface reactions) that are require for DSMC are computed from the surface properties and macroscopic parameters such as rate constants, sticking coefficients, etc. The energy and angular distributions of the products are decided based on the reaction type and input parameters. Thus, the user has the capability to model various surface reactions via user-specified reaction rate constants, surface properties and parameters.

Gas↗
NASA NTRS1974

Interstellar molecules - Origin by catalytic reactions on grain surfaces

To determine the compound distribution formed by surface catalysis, mixtures of CO, D2, and ND2 were heated with nickel-iron or montmorillonite clay catalysts for 49-214 hours at 250 to 300 C. Compounds identified include most of the known polyatomic interstellar molecules, as well as homologous series of acetylenes, dienes, alcohols, aldehydes, ketones, ethers, esters, nitriles, amines, etc., and cyclic compounds such as furans and pyrroles. These homologous series are uniquely characteristic of surface catalysis. A search for the heavier members of these series, predicted to occur at 1/10th to 1/1,000th the abundance of the lightest members, thus comprises a crucial test of this mechanism.

Anders, E.↗
NASA NTRS1975

On the origin of molecular 'handedness' in living systems

Elementary particle effects (beta-decay) provide only a weakly handed radiation in the biologically effective energy ranges. Global magnetic effects coupled to sunlight are randomized by paleomagnetic reversals. A persistent terrestrial handed bias at possible local biopoetic sites offers a more promising explanation for the origin of the 'handedness' of the molecules found among living systems on earth. Magnetite in lava flows maintains a handed bias for surface catalysis through many magnetic reversals. Indirect evidence for the hypothesis that magnetite contaminated with sulfur is a possible biopoetic site (Granick, 1957) has been provided by the molecular structure of ferredoxin - a single strand of the 14 primordial amino acids wrapped around an FeS core. Lava flows have been suggested as biopoetic sites by Fox (1964), since their temperature and chemical composition might allow for the rapid synthesis of prebiotic compounds at the surface of the primitive earth. The additional fact that magetite in lava flows also provides a persistent handed site for surface catalysis offers a further argument for the experimental investigation of this specific biopoetic environment.

Noyes, H. P.↗
NASA NTRS1992

Effect of non-equilibrium flow chemistry on the heating distribution over the MESUR forebody during a Martian entry

Effect of flow field properties on the heating distribution over a 140 deg blunt cone was determined for a Martian atmosphere using Euler, Navier-Stokes (NS), viscous shock layer (VSL), and reacting boundary layer (BLIMPK) equations. The effect of gas kinetics on the flow field and the surface heating distribution were investigated. Gas models with nine species and nine reactions were implemented into the codes. Effects of surface catalysis on the heating distribution were studied using a surface kinetics model having five reactions.

Chen, Yih-Kang↗
NASA NTRS1993

Analysis of hypersonic arcjet flow fields and surface heating of blunt bodies

A Gauss-Seidel implicit aerothermodynamic Navier-Stokes computational CFD code with thermochemical surface conditions (GIANTS) and with appropriate boundary conditions was developed for the analysis of hypersonic arcjet flows over large angle blunt bodies. Two-dimensional axisymmetric multicomponent full Navier-Stokes equations were solved, together with boundary conditions, to account for the surface slip, surface catalysis, and energy and mass conservation at the body surface. It is shown that the predictions for isothermal, noncatalytic, and no-slip surface conditions which are made using the GIANTS code with simple boundary conditions agree with those of the LAURA code, and the predicted normalized heating distributions over the forebody surface with boundary conditions for various cone angles are consistent with the trends of data from arcjet experiments.

Chen, Y.-K.↗
NASA NTRS1975

Computational procedure for three-dimensional boundary layers on aircraft and aerospace vehicles

An implicit numerical procedure is developed to solve the full three-dimensional laminar, boundary layer equations over realistic aircraft and spacecraft configurations. This procedure utilizes splined functions in the direction normal to the surface and finite differences in the cross flow direction. Calculation of off-pitch plane attachment and detachment lines can be calculated. The solution procedure permits the incorporation of a wide variety of turbulent models and boundary conditions including; entropy layer procedures, specified surface temperatures or heat flux distributions, surface catalysis, mass addition, and the coupling to both three-dimensional inviscid codes and surface ablation codes. In addition, reasonable computing times are obtained.

Kendall, R. M.↗
NASA NTRS1992

Theoretical study of the design of a catalyst for para to ortho hydrogen conversion

The theory of Petzinger and Scalapino (1973) was thoroughly reviewed, and all of the basic equations for paramagnetic para to ortho hydrogen catalysis re-derived. There are only a few minor phase errors and errors of omission in the description of the theory. Three models (described by Petzinger and Scalapino) for the rate of para to ortho H2 catalysis were worked out, and uniform agreement obtained to within a constant factor of 2 pi. The analytical methods developed in the course of this study were then extended to two new models, which more adequately describe the process of surface catalysis including transfer of hydrogen molecules onto and off of the surface. All five equations for the para to ortho catalytic rate of conversion are described. The two new equations describe the catalytic rate for these models: H2 on the surface is a 2-D gas with lifetime tau; and H2 on the surface is a 2-D liquid undergoing Brownian motion (diffusion) with surface lifetime tau.

Coffman, Robert E.↗
NASA NTRS2003

Catalyzed Combustion of Bipropellants for Micro-Spacecraft Propulsion

This paper addresses the need to understand the physics and chemistry involved in propellant combustion processes in micro-scale combustors for propulsion systems on micro-spacecraft. These spacecraft are planned to have a mass less than 50 kilograms with attitude control estimated to be in the 10 milli-Newton thrust class. These combustors are anticipated to be manufactured using Micro Electrical Mechanical Systems (MEMS) technology and are expected to have diameters approaching the quenching diameter of the propellants. Combustors of this size are expected to benefit significantly from surface catalysis processes. Miniature flame tube apparatus is chosen for this study because microtubes can be easily fabricated from known catalyst materials and their simplicity in geometry can be used in fundamental simulations for validation purposes. Experimentally, we investigated the role of catalytically active surfaces within 0.4 and 0.8 mm internal diameter microtubes, with special emphases on ignition processes in fuel rich gaseous hydrogen and gaseous oxygen. Flame thickness and reaction zone thickness calculations predict that the diameters of our test apparatus are below the quenching diameter of the propellants in sub-atmospheric tests. Temperature and pressure rise in resistively heated platinum and palladium microtubes was used as an indication of exothermic reactions. Specific data on mass flow versus preheat temperature required to achieve ignition are presented. With a plug flow model, the experimental conditions were simulated with detailed gas-phase chemistry, thermodynamic properties, and surface kinetics. Computational results generally support the experimental findings, but suggest an experimental mapping of the exit temperature and composition is needed.

Schneider, Steven J.↗
NASA NTRS2003

Catalyzed Ignition of Bipropellants in Microtubes

This paper addresses the need to understand the physics and chemistry involved in propellant combustion processes in micro-scale combustors for propulsion systems on micro-spacecraft. These spacecraft are planned to have a mass less than 50 kilograms with attitude control estimated to be in the 10 milli-Newton thrust class. These combustors are anticipated to be manufactured using Micro Electrical Mechanical Systems (MEMS) technology and are expected to have diameters approaching the quenching diameter of the propellants. Combustors of this size are expected to benefit significantly from surface catalysis processes. Miniature flame tube apparatus is chosen for this study because microtubes can be easily fabricated from known catalyst materials and their simplicity in geometry can be used in fundamental simulations to more carefully characterize the measured heat transfer and pressure losses for validation purposes. Experimentally, we investigate the role of catalytically active surfaces within 0.4 and 0.8 mm internal diameter micro-tubes, with special emphases on ignition and extinction processes in fuel rich gaseous hydrogen and gaseous oxygen. Flame thickness and reaction zone thickness calculations predict that the diameters of our test apparatus are below the quenching diameter of the propellants in sub-atmospheric tests. Temperature and pressure rises in resistively heated platinum and palladium micro-tubes are used as an indication of exothermic reactions. Specific data on mass flow versus preheat temperature required to achieve ignition are presented.

Schneider, Steven J.↗
NASA NTRS2016

Orion EFT-1 Catalytic Tile Experiment Overview and Flight Measurements

This paper describes the design and results of a surface catalysis flight experiment flown on the Orion Multipurpose Crew Vehicle during Exploration Flight Test 1 (EFT1). Similar to previous Space Shuttle catalytic tile experiments, the present test consisted of a highly catalytic coating applied to an instrumented TPS tile. However, the present catalytic tile experiment contained significantly more instrumentation in order to better resolve the heating overshoot caused by the change in surface catalytic efficiency at the interface between two distinct materials. In addition to collecting data with unprecedented spatial resolution of the "overshoot" phenomenon, the experiment was also designed to prove if such a catalytic overshoot would be seen in turbulent flow in high enthalpy regimes. A detailed discussion of the results obtained during EFT1 is presented, as well as the challenges associated with data interpretation of this experiment. Results of material testing carried out in support of this flight experiment are also shown. Finally, an inverse heat conduction technique is employed to reconstruct the flight environments at locations upstream and along the catalytic coating. The data and analysis presented in this work will greatly contribute to our understanding of the catalytic "overshoot" phenomenon, and have a significant impact on the design of future spacecraft.

Salazar, Giovanni↗
NASA NTRS1992

Numerical procedures for three-dimensional computational surface thermochemistry

Models and equations for surface thermochemistry and near-surface thermophysics of aerodynamically-heated thermal protection materials are reviewed, with particular emphasis on computational boundary conditions for surface mass and energy transfer. The surface energy and mass balances, coupled with an appropriate ablation or surface catalysis model, provide complete thermochemical boundary conditions for a true multidisciplinary solution of the fully coupled fluid-dynamics/solid mechanics problem. Practical approximate solutions can be obtained by using a detailed model with full thermophysics for either the solid or fluid phase amd a semianalytic method for the other half of the problem. A significant increase in the state-of-the-art in aerothermal computational fluid dynamics is possible by uniting CFD methodology with surface thermochemistry boundary conditions and the heat-balance-integral method.

Milos, Frank S.↗
NASA NTRS1994

Review of numerical procedures for computational surface thermochemistry

Models and equations for surface thermochemistry and near-surface thermophysics of aerodynamically heated thermal protection materials are reviewed, with particular emphasis on computational boundary conditions for surface mass and energy transfer. The surface energy and mass balances, coupled with an appropriate ablation or surface catalysis model, provide complete thermochemical boundary conditions for a true multidisciplinary solution of the fully coupled fluid-dynamics/solid mechanics problem. Practical approximate solutions can be obtained by using a detailed model with full thermophysics for either the solid or fluid phase and a semianalytic method for the other half of the problem. A significant increase in the state-of-the-art in aerothermal computational fluid dynamics is possible by uniting computational fluid dynamic (CFD) methodology with surface thermochemistry boundary conditions and the heat-balance-integral method.

SOLID MECHANICS↗
NASA NTRS1992

Stagnation-point heat-transfer rate predictions at aeroassist flight conditions

The results are presented for the stagnation-point heat-transfer rates used in the design process of the Aeroassist Flight Experiment (AFE) vehicle over its entire aeropass trajectory. The prediction methods used in this investigation demonstrate the application of computational fluid dynamics (CFD) techniques to a wide range of flight conditions and their usefulness in a design process. The heating rates were computed by a viscous-shock-layer (VSL) code at the lower altitudes and by a Navier-Stokes (N-S) code for the higher altitude cases. For both methods, finite-rate chemically reacting gas was considered, and a temperature-dependent wall-catalysis model was used. The wall temperature for each case was assumed to be radiative equilibrium temperature, based on total heating. The radiative heating was estimated by using a correlation equation. Wall slip was included in the N-S calculation method, and this method implicitly accounts for shock slip. The N-S/VSL combination of projection methods was established by comparison with the published benchmark flow-field code LAURA results at lower altitudes, and the direct simulation Monte Carlo results at higher altitude cases. To obtain the design heating rate over the entire forward face of the vehicle, a boundary-layer method (BLIMP code) that employs reacting chemistry and surface catalysis was used. The ratio of the VSL or N-S method prediction to that obtained from the boundary-layer method code at the stagnation point is used to define an adjustment factor, which accounts for the errors involved in using the boundary-layer method.

Gupta, Roop N.↗
NASA NTRS1972

Detection techniques for tenuous planetary atmospheres

The research for the development of new types of detectors for analysis of planetary atmospheres is summarized. Topics discussed include: corona discharge humidity detector, surface catalysis and exo-electron emission, and analysis of soil samples by means of exo-electron emission. A report on the exo-electron emission during heterogeneous catalysis is included.

Hoenig, S. A.↗
NASA NTRS1975

Detection techniques for tenuous planetary atmospheres

Electrostatic charging of dust and its effect on planetary atmospheres is discussed, along with its applications to Martian atmosphere. Laboratory and field experiments in dust storms indicate that the major atmospheric parameters on Mars include: (1) pressure, temperature, and relative humidity; (2) wind velocity and direction; (3) particulate size and composition; and (4) electrostatic charge and field gradient. Various instrumentation techniques adapted for a Mars Lander are briefly reviewed. The effect of exoelectron emission on surface catalysis is studied.

Hoenig, S. A.↗
NASA NTRS1977

Preliminary analysis of remote infrared imagery of shuttle during entry: An aerothermodynamic flight experiment

The preliminary feasibility of remote high-resolution infrared imagery of the space shuttle orbiter lower surface during entry to obtain accurate measurements of aerodynamic heat transfer to that vehicle was examined. In general, it was determined that such such images can be taken from an existing aircraft/telescope system (the C-141 AIRO) with a minimum modification or addition of systems using available technology. These images will have a spatial resolution of about 0.3 m and a temperature resolution much better than 2.5 percent. The data from these images will be at conditions and at a scale not reproducible in ground based facilities and should aid in the reduction of the prudent factors of safety required to account for phenomenological uncertainties on the thermal protection system design. Principal phenomena to be observed include laminar heating, boundary-layer transition, turbulent heating, surface catalysis, and flow separation and reattachment.

Swenson, B. L.↗
NASA NTRS1977

Origin of organic matter in the early solar system. VII - The organic polymer in carbonaceous chondrites

Degradation techniques, including pyrolysis, depolymerization, and oxidation, were used to study the insoluble polymer from the Murchison C2 chondrite. Oxidation with Cr2O7(2-) or O2/UV led to the identification of 15 aromatic ring systems. Of 11 aliphatic acids identified, three dicarboxylic acids presumably came from hydroaromatic portions of the polymer, whereas eight monocarboxylic acids probably derive from bridging groups or ring substituents. Depolymerization with CF3COO4 yielded some of the same ring systems, as well as alkanes (C1 through C8) and alkenes (C2 through C8), alkyl (C1 through C5) benzenes and naphthalenes, and methyl- or dimethyl -indene, -indane, -phenol, -pyrrole, and -pyridine. All these compounds were detected below 200 C, and are therefore probably indigenous constituents. The properties of the meteoritic polymer were compared with the properties of a synthetic polymer produced by the Fischer-Tropsch reaction. It is suggested that the meteoritic polymer was also produced by surface catalysis.

Hayatsu, R.↗