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.     

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.     

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.     

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.     

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.     

The effect of nonequilibrium dissociation on boundary layer flow

The effect of nonequilibrium non-Arrhenius dissociation kinetics, which cannot be reduced to two-temperature kinetics, on the microparameter distribution in a boundary layer and, in particular, on the heat transfer to the surface of the body is considered with reference to the flow of a binary mixture of nitrogen molecules and nitrogen atoms in the neighborhood of the stagnation point on a blunt body.Moscow. Translated from Izvestiya Rossiiskoi Akademii Nauk, Mekhanika Zhidkosti i Gaza, No. 4, pp. 168–178, July–August, 1995.     

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.     

Model of the physico-chemical kinetics behind the front of a very intense shock wave in air

A model of the physico-chemical kinetics of the reactions taking place behind the front of an intense shock wave propagating in air with a speed of 9–14 km/s is proposed. The problem of describing the chemical reactions, namely, molecular dissociation and exchange reactions involving vibrationally excited molecules in the absence of vibrational equilibrium, is solved. The vital role of the vibrational excitation delay in the dissociation of oxygen and nitrogen is established. The rate of the exchange reaction between nitrogen molecules and oxygen atoms in the shock wave depends only slightly on the vibrational excitation level. It is demonstrated that the rate constants for thermally nonequilibrium dissociation reactions can be represented within the framework of the one-temperature approximation at constant vibrational temperatures of the dissociating species satisfying quasi-stationary conditions.Moscow. Translated from Izvestiya Rossiiskoi Akademii Nauk, Mekhanika Zhidkosti i Gaza, No. 2, pp. 169–182, March–April, 1995.     

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.     

Catalytic properties of a copper transducer for determining flow parameters in a high-frequency induction plasmatron

The rate coefficients of the elementary stages of the complete system of heterogeneous catalytic recombination of dissociated oxygen on a copper oxide surface are determined on the basis of quantum-mechanics calculations within the framework of cluster models. The coefficients are used to calculate the dependence of the effective coefficient of heterogeneous catalytic recombination of oxygen atoms on the temperature and the partial pressure on a wide range of surface conditions. It is established that it can considerably vary depending on these conditions.     

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.     

Modeling of the catalytic properties of high-temperature surface insulation in a dissociated carbon dioxide — Nitrogen mixture

A model of the heterogeneous catalysis of a dissociated carbon dioxide — nitrogen mixture on high-temperature heat-shield coatings is developed; the model takes into account nonequilibrium adsorption-desorption reactions of nitrogen and oxygen atoms and carbon dioxide molecules and their recombination in the Eley-Rideal reactions. On the basis of a comparison of the calculated heat fluxes in dissociated carbon dioxide with those measured on the VGU-4 plasma generator of the Institute for Problems in Mechanics of the RAS, the parameters of the catalysis model in question are chosen for three modern oxidant-resistant coating materials. The performances of these coatings are compared for the conditions of Mars Miniprobe entry into the Martian atmosphere. Their usability for the entry path considered is shown. Moscow. Translated from Izvestiya Rossiiskoi Akademii Nauk, Mekhanika Zhidkosti i Gaza, No. 1, pp. 106–116, January–February, 2000. The study was carried out with the support of the Russian Foundation for Basic Research (project No. 99-01-00259) and the “Integratisya“ Federal Program (project No. 2.1–414).     

Determination of the constants of electrochemical reactions and the ion mobility coefficients in weakly conducting liquids from an analysis of the current—voltage characteristics

The problem is considered of the passage of a direct current through a solution of a weak electrolyte in a two-dimensional cell. Allowance is made for the electrochemical reactions of dissociation and reconbination which take place in the electrolyte when the rate of dissociation of the molecules is regarded as dependent on the electric field intensity [1–3]. For electrolytes whose recombination coefficient is of the order of magnitude of the Langevin coefficient, theoretical current—voltage characteristics are given for the limiting cases of large and small values of the characteristic times for the ion concentrations to be changed by electrochemical reactions and the transport of ions by the electric field. A method of determining the dissociation rate, the recombination coefficient, and the ion mobility coefficients is proposed on the basis of comparison of the theoretical and experimental current—voltage characteristics.Translated from Izvestiya Akademii Nauk SSSR, Mekhanika Zhidkosti i Gaza, No. 6. pp. 113–120, November–December, 1984.     

Effect of Debye screening on ionization energy of components of air plasma

The effect of Coulomb interaction on the shift of energy levels of the components of air plasma is estimated. For illustrating the procedure of computation, the shift of the energy levels of hydrogen are computed. A simple method of computation of the shift of energy levels is given, which offers the possibility of cutting the computer time by a factor of 10–30. The dependence of the shift of the ground level of atoms of hydrogen, argon, nitrogen, and oxygen on Debye radius D is obtained for 20 D 2000 atomic units.Translated from Zhurnal Prikladnoi Mekhaniki i Tekhnicheskoi Fiziki, No. 1, pp. 35–39, January–February, 1973.In conclusion, the author thanks V. G. Sevast'yanenko for guidance, advice, and comments, and N. M. Kuznetsov for valuable discussions.     

Localized viscoelastoplastic strain in mesovolume of heterogeneous medium under different loading types

The localized viscoelastoplastic strain in the mesovolume of heterogeneous media under quasi-static and dynamic loading is investigated. The generalized Bingham–Shwedov model is used; it consists of a combination of Dragon–Mroz's for elastoplasticity and Maxwell's model of viscoelasticity. Any variational finite-difference scheme for solving the quasi-static problem of elastoplastic yielding of a heterogeneous solid can be taken into account. A modified Lagrange's variance equation for analyzing the stress–strain state can be described by the non-symmetric stress tensor. Approximation of spatial derivatives is made by using the twofold partition of spatial domain in tetrahedronal or three-angular (in two-dimensional space) unit cell of mesh-work. Finite difference for deformation is made use of in two or three space dimensions and time. Results for heterogeneous medium with complex form and large number of interior surfaces are obtained for quasi-static and dynamics problems.     

Flow of a dual-temperature plasma in the channel of a disk-magnetohydrodynamic generator,taking account of nonequilibrium ionization and recombination reactions

The establishment of a supersonic one-dimensional flow of a dual-temperature, partially ionized plasma is investigated in the channel of a disk-MHD generator, taking account of nonequilibrium ionization and recombination reactions. A detailed formulation of the problem is given in [1]; flows are considered in the absence of ionization and recombination reactions and in the case of equilibrium reactions.Moscow. Translated from Izvestiya Akademii Nauk SSSR. Mekhanika Zhidkosti i Gaza, No. 6, pp. 135–142, November–December, 1972.     

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.     

Gas dynamic ozone generator

The formation of ozone when partially dissociated oxygen flows out of a supersonic nozzle has been investigated experimentally and theoretically. The supersonic flow of a chemically reacting gas mixture containing excess O atoms is calculated in the one-dimensional approximation for a class of plane wedge-shaped nozzles. It is shown that for initial gas pressures ahead of the nozzle inlet of about 10 atm and a temperatureT ₀=1000 K in nozzles with a total vertex angle of 30°C and a throat dimensionh.=1 mm it is possible to obtain an ozone concentration of about 1%, which is comparable with ordinary ozonizers, while the output of the device is two to three orders greater. Experiments on a shock tube fitted with a nozzle to measure the absorption of UV radiation by oxygen recombining in the nozzle under highly nonoptimal conditions revealed the presence in the flow of ozone molecules formed as a result of O+O₂ recombination.Moscow. Translated from Izvestiya Rossiiskoi Akademii Nauk, Mekhanika Zhidkosti i Gaza, No. 6, pp. 139–148, November–December, 1994.     

Bounds for the effective properties of heterogeneous plates

This paper presents new bounds for heterogeneous plates which are similar to the well-known Hashin–Shtrikman bounds, but take into account plate boundary conditions. The Hashin–Shtrikman variational principle is used with a self-adjoint Green-operator with traction-free boundary conditions proposed by the authors. This variational formulation enables to derive lower and upper bounds for the effective in-plane and out-of-plane elastic properties of the plate. Two applications of the general theory are considered: first, in-plane invariant polarization fields are used to recover the “first-order” bounds proposed by Kolpakov [Kolpakov, A.G., 1999. Variational principles for stiffnesses of a non-homogeneous plate. J. Meth. Phys. Solids 47, 2075–2092] for general heterogeneous plates; next, “second-order bounds” for n-phase plates whose constituents are statistically homogeneous in the in-plane directions are obtained. The results related to a two-phase material made of elastic isotropic materials are shown. The “second-order” bounds for the plate elastic properties are compared with the plate properties of homogeneous plates made of materials having an elasticity tensor computed from “second-order” Hashin–Shtrikman bounds in an infinite domain.