Modeling of catalytic activity of an Al2O3 surface on the basis of the first principles

The adsorption, desorption, impact, and associative heterogeneous recombination rate coefficients are determined for atomic oxygen in the temperature range between 500 and 2000 K on the basis of quantum chemical data on the energy of interaction of atomic and molecular oxygen with the clusters that model an α-Al₂0₃ surface. These coefficients are used to calculate the heterogeneous recombination probabilities and the heat fluxes to the surface under the conditions similar to those of the MESOX facility.     

Simulation of oxygen atom adsorption on an Al<Subscript>2</Subscript>O<Subscript>3</Subscript> surface by the density functional method

Several cluster models of oxygen atom adsorption on an Al₂O₃ surface are constructed on the basis of the density functional method. The performed quantum mechanical computations allow one to reveal a number of important features of the potential energy surface to describe the heterogeneous catalytic processes with the use of molecular dynamics methods. The heterogeneous recombination of oxygen atoms is simulated according to the Eley-Rideal mechanism. It is shown that the potential energy surface should be used with consideration of the internal relaxation of surface monolayers to correctly describe the process under study.     

Diffusion separation of chemical elements on a catalytic surface

An asymptotic expansion of the solution, for large Schmidt numbers, of the system of equations of a chemically nonequilibrium multicomponent boundary layer on the catalytic surface of a blunt body [1] is used to obtain expressions for the diffusion fluxes of the reaction products and chemical elements and the heat flux as functions of the gradients of the reaction product concentrations, chemical element concentrations and enthalpy across the boundary layer. It is shown that when the body is exposed to a supersonic air flow, the diffusion separation of the chemical element oxygen depends importantly on the atom concentration at the outer edge of the boundary layer and the nature of the homogeneous and heterogeneous catalytic reactions. If the surface promotes the rapid recombination of oxygen atoms and is chemically neutral with respect to nitrogen atoms, then an excess of the chemical element oxygen is formed on the body. Otherwise we get an enhanced concentration of the element nitrogen. As distinct from the case of an ideally catalytic wall [2–4], on a surface possessing the property of catalytic selectivity the diffusion separation of chemical elements takes place even when only atoms are present at the outer edge of the boundary layer. On a chemically neutral surface diffusion separation may be caused by homogeneous recombination reactions between oxygen and nitrogen atoms if their rate constants are essentially different.Translated from Izvestiya Akademii Nauk SSSR, Mekhanika Zhidkosti i Gaza, No. 4, pp. 115–121, July–August, 1988.     

Analysis of catalytic properties of siliconized heat-shielding coatings

The catalytic properties of heat-shielding coatings (β-cristobalite and SiC) used on space vehicles are analyzed on the basis of the microscopic approach with consideration of the molecular structure of the near-surface layer. The heterogeneous recombination coefficient of oxygen atoms and the recombination energy accommodation coefficient are determined. The energy distribution by internal degrees of freedom is calculated. In particular, it is found that, when the energy of collision of atoms with the surface is small, the oxygen atom heterogeneous recombination is more efficient for SiC coatings, whereas this recombination is more efficient in the case of β-cristobalite if the collision energy is large. Nevertheless, the heat-transfer coefficient is greater for SiC coatings in the studied range of collision energy variations, since the recombination energy accommodation is larger.     

Experimental and Theoretical Simulation of Heterogeneous Catalysis in Aerothermochemistry (a Review)

The design of aerospace vehicles has required the solution of radically new scientific and technological problems. One of the important problems has been to create reusable heat shield materials. In [1, 2] information concerning the methods and results of solving these problems, including the development of composites from ultrathin quartz fibers and carbon-carbon materials for the “Buran” orbital vehicle heat shield, was presented. The basic thermophysical characteristics of these materials include both the rate or probability coefficients of heterogeneous nitrogen and oxygen atom recombination and the accommodation coefficients of energy recombination at high surface temperatures. In the present paper the experimental and computational aspects of determining these parameters, which are also of interest for new heat shield materials for future space transport systems, are discussed.     

Effect of the incomplete accommodation of the heterogeneous recombination energy on heat fluxes to a quartz surface

Taking both the heterogeneous catalytic processes, including the surface formation of particles with excited internal degrees of freedom, and the processes of multicomponent diffusion and heat transfer in the MESOX apparatus fully into account makes it possible to obtain a recombination coefficient and an accommodation coefficient of the oxygen-atoms-on-quartz recombination energy which are in good agreement with the experimental data. The heterogeneous catalysis model constructed can be used effectively for predicting the heat fluxes to the surface of reentry vehicles on their entry into the Earth’s atmosphere.     

On the recombination mechanism of atomic nitrogen near a catalytic surface in a stream of dissociated air

It is shown that the heterogeneous recombination of nitrogen atoms on a catalytically active surface in a stream of dissociated air is accompanied by intense gas-phase recombination of the nitrogen in exchange reactions whose rate is determined by the rate of heterogeneous recombination of atomic oxygen.Translated from Izvestiya Akademii Nauk SSSR, Mekhanika Zhidkosti i Gaza, No. 3, pp. 156–158, May–June, 1980.     

Formulas for the heat and diffusion fluxes to a catalytic surface in a chemically nonequilibrium multicomponent boundary layer

On the basis of an asymptotic expansion of the solution of the equations of a multicomponent chemically nonequilibrium boundary layer for large Schmidt numbers, formulas are obtained for the heat flux and the diffusion fluxes of the reaction products and chemical elements on a surface with arbitrary catalytic activity. The results are compared with well-known analytic and numerical solutions. The comparison reveals the high accuracy of the formulas proposed. The results of calculating the diffusional separation of the mixture due to the selectivity of the catalytic properties of the surface with respect to recombination of oxygen and nitrogen atoms are presented. Values of the reduction of the convective heat fluxes due to the catalytic properties of the surface are obtained over a wide range of conditions in the free stream.Moscow. Translated from Izvestiya Rossiiskoi Akademii Nauk, Mekhanika Zhidkosti i Gaza, No. 2, pp. 171–176, March–April, 1996.     

Methods and Results of an Experimental Determination of the Catalytic Activity of Materials at High Temperatures

Methods of experimental determination of the rate constants of heterogeneous catalytic recombination of nitrogen and oxygen atoms in dissociated subsonic nitrogen and air flows generated by a high-frequency inductive plasmatron are discussed. Together with the values of the probability of heterogeneous recombination used in the literature, the rate constant of the elementary process of nitrogen atomic recombination is determined in accordance with the Langmuir-Hinshelwood mechanism.     

Increased heat transfer to a titanium surface with oxygen injection into the nonequilibrium boundary layer

The results of an experimental and numerical investigation of the heat transfer between a subsonic jet of dissociated nitrogen and a titanium surface, through which molecular oxygen is blown into the jet, are presented. It is established that in the nonequilibrium boundary layer regime the dependence of the heat flux on the injected oxygen flow rate is nonmonotonic. At a certain flow rate the heat transfer to the titanium surface reaches a maximum that considerably exceeds (by 20%) the heat transfer to an impermeable wall. The observed increase in heat transfer in the presence of injection is attributed to the interaction of the gas-phase exchange reactions and the recombination of atoms on the titanium surface, which has sharply different catalytic properties with respect to the recombination of nitrogen and oxygen atoms.Translated from Izvestiya Akademii Nauk SSSR, Mekhanika Zhidkosti i Gaza, No. 4, pp. 148–155, July–August, 1991.     

Numerical estimation of heterogeneous reaction constants in the flow of rarefied gas through a cylindrical channel

The Direct Simulation Monte Carlo method is used to study the influence of the coefficients of heterogeneous dissociation and recombination reactions on the rarefied gas flow through a cylindrical channel. It is established that the degree of dissociation of the flow coming out of the channel is significantly dependent on the relationship between the dissociation and recombination coefficients. The technique for determining the dissociation and recombination coefficients on the basis of the experimental data is proposed.     

Simulation of heterogeneous atom recombination on spacecraft heat shield coatings using the methods of molecular dynamics

An efficient method of investigating the processes of interaction between gas mixtures and catalytic surfaces is developed within the framework of classical molecular dynamics. The recombination and chemical-energy accommodation coefficients on the catalytic surface can be determined with fewer computational resources than in the quantum-mechanical and semiclassical approaches. Oxygen atom recombination on a β-cristobalite surface of the type frequently used in spacecraft heat shield systems is investigated. The probability of atom recombination and the recombination energy accommodation coefficient obtained are in satisfactory agreement with the available experimental data and calculations made by means of the semiclassical method. The hypothesis that the probability of the Eley-Rideal reaction decreases and the probability of atom adsorption increases with increase in the atom collision energy is confirmed. It is attributable to the tendency of atoms to be trapped in the potential well and be desorbed in the atomic state when the surface collision energy is high instead of entering into a recombination reaction and then being desorbed in the molecular state.     

Investigation of the Influence of Different Heterogeneous Recombination Mechanisms on the Heat Fluxes to a Catalytic Surface in Dissociated Carbon Dioxide

A kinetic model of heterogeneous recombination in dissociated carbon dioxide on high-temperature heat-shield coatings is developed; the model takes into account the nonequilibrium adsorption-desorption reactions of oxygen atoms and their recombination in the Eley-Rideal and Langmuir-Hinshelwood reactions. On the basis of a comparison of the calculated heat fluxes in dissociated carbon dioxide with those measured in the VGU-3 plasma generator of the Institute for Problems in Mechanics of the Russian Academy of Sciences (IPM RAS) and the available literature data, the parameters of the catalysis model are chosen for the glassy coating of the Buran orbiter tile heat shield based on the SiO₂–B₂O₃–SiB₄ system. The effects of heterogeneous recombination proceeding in accordance with the Langmuir-Hinshelwood mechanism, as well as the processes involving carbon atoms and those involving physically adsorbed oxygen atoms, on the heat fluxes to the glassy coating are analyzed on the surface temperature range from 300 to 2000 K.     

Three-dimensional chemically nonequilibrium viscous shock layer on a catalytic surface with allowance for associated heat transfer

A three-dimensional flow of dissociating air past blunt bodies is investigated in the framework of the thin viscous shock layer theory. Multicomponent diffusion and homogeneous chemical reactions, including dissociation, recombination, and exchange reactions, are taken into account. The generalized Rankine-Kugoniot conditions are specified on the shock wave and the conditions which take into account the heterogeneous catalytic reactions, on the surface of the body. The viscous shock layer equations are solved together with the heat equations inside the coating, which is carbon with a deposited thin film of SiO₂, or quartz. The case of a thermally insulated surface is also considered. The problem for the case of the motion of a body along the re-entry trajectory into Earth's atmosphere is investigated numerically. The temperature of the surface and the heat flux toward it are given as a dependence on the height (tine) of the flight for different cases of the specification of the catalytic reactions. It is shown that the difference between the heat fluxes towards the thermally insulated surface and the fluxes toward the heat-conducting surface in the neighborhood of the stagnation point is of the order of 6–12% for all the cases considered. This makes it possible to decouple the solution of the problem of heat conduction in the body.Translated fron Izvestiya Akademii Nauk SSSR, Mekhanika Zhidkosti i Gaza, No. 6, pp. 140–146, November–December, 1985.deceased     

Analysis of the heterogeneous recombination of oxygen atoms on aluminum oxide by methods of quantum mechanics and classical dynamics

On the basis of the density-functional theory, cluster models of the adsorption of oxygen atoms on aluminum oxide are constructed and the corresponding potential-energy surface is calculated. Quantum-mechanical calculations showed that it is necessary to take into account the angular dependence of the potential-energy surface and the relaxation of the surface monolayers. Using this surface in molecular dynamics calculations made it possible to obtain the probabilities of the heterogeneous recombination of oxygen atoms on the α-Al₂O₃ surface, which are in good agreement with experimental data. The calculations performed substantially decrease the amount of experimental investigations necessary reliably to describe the heterogeneous catalysis on promising reusable heat shield coatings for analyzing heat transfer during spacecraft entry into the atmosphere.     

A hypersonic chemically nonequilibrium viscous shock layer oh wings with a catalytic surface

Within the framework of the theory of a hypersonic viscous shock layer a study is made of flow round wings of infinite span with blunt leading edges at various angles of attack and slip. Account is taken of multicomponent diffusion, and homogeneous chemical reactions, including dissociation-recombination reactions and exchange reactions. On the shock wave the generalized Rankine-Hugoniot conditions are given, and on the surface of the body conditions which allow for heterogeneous catalytic reactions of the first order with reaction rate constants depending [1] or not depending [2] on the temperature. The cases of an ideally catalytic and a noncatalytic surface are also considered. The surface of the body is assumed to be heatinsulated. A numerical study was made of the problem in a broad range of variation in the angles of attack and slip for different cases of prescribed constants representing the rates of the heterogeneous reactions. The conditions of the flow corresponded to the motion of a body which possess a lifting force along the trajectory of entry into the Earth's atmosphere [3]. The dependences are given of the equilibrium temperature of the surface along the stagnation line of the wing on the height of the flight and the distribution of this temperature along the surface of wings with parabolic and hyperbolic contours. It is shown that for flow regimes with a relatively high degree of dissociation in cases when the proportion of atoms recombined on the surface of the body is small, the dependences of the heat flow and the temperature of the surface on the angle of slip are of a nonmonotonic nature.Translated from Izvestiya Akademii Nauk SSSR, Mekhanika Zhldkosti i Gaza., No. 6, pp. 127–135, November–December, 1984.     

Determination of the catalytic activity of materials by solving the equations of a nonequilibrium multicomponent boundary layer on a flat plate

A method is presented for determining the dependence of the probability of heterogeneous recombination γw from results of measurements of the heat flux Q_w to the surface of a catalytic sensor exposed to a pulsed supersonic flow of gas dissociated by an incident shock wave propagating in a shock tube. It is shown that the accuracy of the determination of γw depends not only on the accuracy of the measurements in the experiment, but also on the results of mathematical modeling of the flow of the dissociated gas over the surface of the body. Results from an analysis of an experiment are presented. Institute of Applied Mathematics and Mechanics at Tomsk University, Tomsk 634050. Translated from Prikladnaya Mekhanika i Tekhnicheskaya Fizika, Vol. 39, No. 4, pp. 110–117, July–August, 1998.     

Local modeling of the aerodynamic heating of the blunt body surface in subsonic high-enthalpy air flow. Theory and experiment on a high-frequency plasmatron

The concept of the local similarity of nonequilibrium boundary layers in high-enthalpy gas flows past blunt bodies is briefly described. The technical possibilities of the VGU-4 induction high-frequency plasmatron in modeling the aerodynamic heating of the hypothetical Pre-X (CNES) spacecraft in the vicinity of the stagnation point of a high-enthalpy air flow are presented. The engineering approach to quantitatively reproduce the thermochemical effect of a dissociated air flow on the vehicle surface in the high-heat region of the terrestrial entry trajectory is developed. In this approach the full-scale values of the total enthalpy, the stagnation pressure, and the velocity gradient at the stagnation point near the surface are reproduced in the experiment. The effective coefficients of O and N atom recombination on a silicone carbide (SiC) surface are determined under the conditions similar with those of the peak heating of the Pre-X vehicle surface in the vicinity of the flow stagnation point.     

Effect of surface catalytic activity on nonequilibrium heat transfer in a subsonic jet of dissociated nitrogen

The present paper investigates experimentally and numerically the effect of the heterogeneous recombination of atoms on the heat transfer of models in a subsonic jet of dissociated nitrogen for the conditions of an experiment in the VGU-2 plasma generator and determines the effective probabilities of the heterogeneous recombination of nitrogen atoms for a number of materials at high temperatures.Translated from Izvestiya Akademii Nauk SSSR, Mekhanika Zhidkosti i Gaza, No. 3, pp. 166–172, May–June, 1985.     

Ignition of hydrogen in a turbulent boundary layer on a plate

The ignition of hydrogen blown into a turbulent supersonic boundary layer on a flat plate is investigated numerically. It is assumed that the mixture consists of six chemically active components H, O, OH, H₂O, O₂, H₂ and inert nitrogen N₂. The boundary layer is divided into outer and inner regions, for which different expressions for the coefficients of turbulent transport are used. The influence of pulsations on the rates of the chemical reactions, and also the back reaction of the chemical processes on the mechanism of turbulent transfer are not taken into account. The surface of the plate is assumed to be absolutely catalytic with respect to the recombination reactions of the H and O atoms. The influence of the blowing intensity, the Mach number in the outer flow, and the pressure on the ignition delay is analyzed. The possibility of effective porous cooling of the surface when there is combustion in the boundary layer is demonstrated.Translated from Izvestiya Akademii Nauk SSSR, Mekhanika Zhidkosti i Gaza, No. 6, pp. 33–40, November–December, 1979.I thank V. G. Gromov and V. A. Levin for their interest in the work.