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.     

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.     

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.     

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.     

Recombination of electrons in a plasma expanding into a vacuum

As noted in a paper by one of the authors [1], when a hot ionized gas expands into a vacuum, at a certain moment ionization equilibrium must necessarily break down. Shortly after this point, which may be found by the method indicated in [1], ionizing events become very rare and only recombination occurs in the gas. In [1] photorecombination and triple collisions with the capture of an electro to the ground level of the atom were considered. Here the recombination did not proceed to the end: on expanding to infinity and cooling to zero the gas remained partially ionized.Papers have recently appeared [2–7] in which the significant role of triple collisions with the capture of electrons to upper atomic levels is noted. The recombination process has a cascade character at low temperatures and densities which are not excessively small. At first, the electron is captured by one of the upper atomic levels in a triple collision with an ion and another electron. Subsequently, as a result of electron collisions of the second kind, and later also as a result of radiative transitions, the bound electron descends through the energy levels to the atomic ground state. The recombination coefficient for such a process depends much more strongly on the electron temperature T than for a triple collision with capture directly by the ground level (as T^–9/2 as opposed to T^–1), and at low temperatures cascade recombination proceeds much more quickly than capture to the ground level. Since this casts doubt upon the conclusions of [1] regarding the residual ionization when a plasma expands into a vacuum, we were led to re-examine the question, which, as will be clear from what follows, is not considerably more complicated.     

N-space collision model for rotation-translation energy exchange in DSMC collisions

A new discrete simulation Monte Carlo (DSMC) collision model for molecules possessing an integer number of classical degrees of freedom for molecular structure energy is proposed. The total molecular energy (translation plus molecular structure) is represented by a velocity in five-dimensional space. Each collision is an elastic N-sphere collision in N-space, where N= 3, 4, or 5. For N=5, there is a maximum chance of exchange of energy between the two components of velocity, which represent the rotation energy and the three components that represent the translational velocity. For N=3, there is no change in the rotation energy of each molecule, and for N=4, there is an intermediate chance that rotation and translation energy will be exchanged. The exchange probability ϕ can be set to give the desired rotational relaxation rate. To achieve any realistic viscosity μ(T), the N-space model must be coupled with a modified collision procedure known as ν-DSMC. The new model is shown to match the results of molecular dynamics calculations for the internal structure of a Mach 7 shock, with a saving of about 20% in CPU time compared to standard DSMC using the standard Borgnakke-Larsen exchange model.     

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.     

Dynamic Monte Carlo simulation of surface recombination

A dynamic model for the Monte Carlo method is developed to analyze the atom recombination on a catalytic surface. A numerical method for the study of this model is considered. The concentrations of physically and chemically adsorbed atoms obtained using this approach are in good agreement with experimental data and with the numerical results obtained on the basis of the phenomenological model and by other authors with the aid of the Monte Carlo method.     

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.     

A variational approach to coarse graining of equilibrium and non-equilibrium atomistic description at finite temperature

The aim of this paper is the development of equilibrium and non-equilibrium extensions of the quasicontinuum (QC) method. We first use variational mean-field theory and the maximum-entropy (max-ent) formalism for deriving approximate probability distribution and partition functions for the system. The resulting probability distribution depends locally on atomic temperatures defined for every atom and the corresponding thermodynamic potentials are explicit and local in nature. The method requires an interatomic potential as the sole empirical input. Numerical validation is performed by simulating thermal equilibrium properties of selected materials using the Lennard-Jones (LJ) pair potential and the embedded-atom method (EAM) potential and comparing with molecular dynamics results as well as experimental data. The max-ent variational approach is then taken as a basis for developing a three-dimensional non-equilibrium finite-temperature extension of the QC method. This extension is accomplished by coupling the local temperature-dependent free energy furnished by the max-ent approximation scheme to the heat equation in a joint thermo-mechanical variational setting. Results for finite-temperature nanoindentation tests demonstrate the ability of the method to capture non-equilibrium transport properties and differentiate between slow and fast indentation.     

Stress-dependent molecular pathways of silica-water reaction

Stress-corrosion of silica by water is studied by exploring the stress-dependent potential energy surface computed quantum mechanically at the level of molecular orbital theory. An ordered silica nanorod with clearly defined nominal tensile stress is constructed to model a structural unit of the stressed crack tip. Three competing hydrolysis reaction pathways are determined, each involving a distinct initiation step. Water dissociation, molecular chemisorption, and direct siloxane bond rupture dominate at low, intermediate, and high stress levels, respectively. A linear stress dependence in the thermodynamic driving force, not commonly considered in the criterion of brittle fracture initiation, is shown to originate from surface relaxation associated with bond rupture. This effect is particularly important in determining the Griffith condition of crack extension for nano-sized systems when spatial accommodation of foreign molecules is involved in the process of bond breaking. The physical origin of the stress dependence of kinetic barrier is revealed by a perturbation analysis of the minimum energy path parametrized by the continuous mechanical stress.     

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.     

有机二硫化物极压添加剂结构与润滑性能的理论研究

运用Gaussian98量子化学程序包,采用密度泛函理论(DFT)及从头算(ab initio)方法,在B3LYP/6-31G和HF/6-31G水平上对12种有机二硫化物的分子几何构型、电子结构、分子轨道指数及与铁原子簇的相互作用等进行了理论计算;由前线分子轨道理论分析了反应的活性原子和活性键,运用轨道能量近似原则讨论了有机二硫化物与铁原子的作用方式;以前线电子密度、超离域性指数和原子净电荷等参数作为表征有机二硫化物与金属作用强弱的判据,分析了有机二硫化物与铁原子间键合的强弱及反应性大小.结果表明:当有机二硫化物与铁接触时,趋向于发生S-S键和C-S键断裂;随碳链的增长,有机二硫化物的抗磨性能增强,极压性能减弱,与相应的摩擦磨损试验结果一致.所用的量子化学方法在润滑添加剂结构-性能研究领域具有良好的应用前景,可用以指导润滑添加剂的分子设计.     

Nonequilibrium excitation of internal molecular degrees of freedom in the shock layer during hypersonic flight

A kinetic scheme of processes including the formation and quenching of electronically and vibrationally excited particles is proposed for the shock layer adjacent to the surface of a body flying at hypersonic speed. We present results of a numerical calculations for the stagnation point obtained under the thin viscous shock layer approximation for space shuttle flight conditions.We show that the release of atom recombination energy into the internal molecular degrees of freedom and the finite rate of relaxation reduce the calculated heat flux by 20 %.This article was processed using Springer-Verlag T_EX Shock Waves macro package 1.0 and the AMS fonts, developed by the American Mathematical Society.     

Effect of nonuniform accommodation coefficient distribution on the couette flow

The Couette flow is considered for surfaces with nonuniformly distributed energy accommodation coefficients α. It is shown that at Knudsen numbers greater or of the order of unity heat fluxes and viscous stresses can be considerably optimized by varying the surface distribution of α at a fixed integral value. At the same time, for Kn ≪ 1 the flows with nonuniformly distributed α are similar with the flow with a constant accommodation coefficient equal to its mean value.     

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.     

Accommodation coefficients for molecular hydrogen on a graphite surface

On the basis of the molecular dynamics simulation method the trajectories of hydrogen molecules reflected from a graphite surface are calculated with account for its structure and the thermal motion of carbon atoms. The velocity distribution after the reflection is obtained as a function of the velocity magnitude and direction of the incident molecules and the surface temperature. In the case of heat transfer between symmetric surfaces in the free-molecular regime, the energy accommodation coefficients are calculated for hydrogen on graphite as functions of the gas and wall temperatures. The results obtained are in agreement with experimental data.     

Interaction of molecules with the surface of a solid

The interaction of molecules and atoms with the surface of a solid is considered on the basis of classical mechanics. A two-dimensional square lattice with atoms arranged at the lattice points was taken as the model for describing a solid. It is assumed that only neighboring atoms interact in the solid, while the gas molecules interact with the atoms located in its surface layer.As a result of collisions with the surface, a gas molecule loses a part of its kinetic energy, and this process is characterized by the energy accommodation coefficient. In addition, another coefficient is introduced which takes account of that part of the energy of translational motion converted into energy of internal motion of the molecule (vibration and rotation). The possibility of the occurrence of inelastic losses and some special features of this phenomenon are illustrated by the interaction of a diatomic molecule with an isolated atom.The available experimental data on the interaction of particles of gas with the surface of a solid are essentially associated with the low-energy region (the temperature of the gas is less than or on the order of several hundreds of degrees). One of the objectives of this research was to find the distribution function of particles reflected from the surface; in particular, the hypothesis of diffuse-specular reflection is tested [1–3]. However, the few experimental results provide evidence of the effect of a large number of factors on the nature of the interaction, rather than make it possible to establish strict laws for the process.The theoretical investigations were conducted along the line of improving simple models-instead of modelling a solid by a one-dimensional chain of atoms [4,5], two and three-dimensional lattices are introduced [6–8]. It is noted in [6] that the interaction of gas particles with a one -dimensional chain differs from the interaction with a three-dimensional lattice, and this fact can lead to a considerable divergence in the values of the accommodation coefficient when the mass of the incident molecule is comparable with the mass of an atom of the solid. It also follows from [6] that if we describe the interaction between gas atoms and those of the solid by the Morse potential, then we can select the parameters of the potential so that the calculated data will agree with the experimental data. Moreover, good results are obtained if we make use of parameters of the potential determined on the basis of the combination rule [7].The interaction of atoms of gas with a three-dimensional lattice of finite size is considered in [8]. Forces with the Lennard-Jones potential act between gas atoms and atoms of the solid. The classical equations of motion of all particles were solved numerically on electronic computers.In these references, a gas particle (molecule or atom) is regarded as a whole; however, the problem of the influence of internal degrees of freedom on the coefficients of energy and momentum exchange between the gas particles and the solid is interesting. An attempt is made in this work to take this influence into account on the basis of classical mechanics.     

颤振环境MoS2/Ag薄膜碰撞滑动接触摩擦性能研究

基于空间机构的运动特性,考虑空间颤振环境的影响,采用粗粒化分子动力学研究MoS₂/Ag薄膜的碰撞滑动接触摩擦性能,建立颤振环境碰撞滑动接触摩擦的粗粒化分子动力学模型,对比了纯Ag和MoS₂/Ag薄膜的摩擦性能,研究了初始碰撞速度、滑动速度以及空间温度对碰撞滑动接触摩擦过程的影响.结果表明：与纯Ag相比,MoS₂/Ag薄膜表现出更优异的摩擦性能;压头碰撞速度对动能有一定的贡献,初始碰撞速度的增加会增大压头压入基体的深度,使得平均摩擦力增大;滑动速度的增加会加剧原子间的相互剪切摩擦,使平均摩擦力增加;MoS₂/Ag薄膜在100～500 K温度范围内表现出良好的摩擦性能,当空间温度为600 K时,其摩擦性能降低,并伴随着MoS₂膜的破裂.     

The analytical modeling of propane-oxygen mixture at catalytic micro-channel

In the present work the effect of catalytic surface reaction on non-reactive bulk flow in micro-channel is investigated. The reaction surface is analyzed with assumption of constant wall temperature. To solve this problem, the energy, mole fraction and catalytic reaction equations are solved by trial and error process. The analysis show that most sensitive parameter is fuel conversion and the sensitivity of hydraulic diameter is more than longitude coordinates.