考虑Stefan影响的单颗粒硼着火过程研究

针对含硼推进剂固体火箭冲压发动机内单颗粒硼的着火过程展开了系统研究. 考虑硼颗粒周围气相流动以及硼颗粒与周围环境间的传热传质过程, 建立了考虑Stefan流作用的一维硼颗粒着火模型, 研究了硼颗粒实现着火和未能实现着火两种典型情形下硼颗粒及周围气相的参数变化规律, 对两种情形下Stefan流的变化规律及其成因展开了详细分析. 研究表明, 在硼颗粒实现着火的过程中, 液态B₂O₃的蒸发及硼的 氧化均能在硼颗粒的反应自加热作用下急剧加速, 硼颗粒表面附近的氧气和气相B₂O₃分布变化剧烈; 在未能实现着火的过程中, 液态B₂O₃的蒸发和氧气消耗的质量流率相对较小, 并逐渐趋于稳定, 硼颗粒表面附近的氧气和气相B₂O₃分布相对变化很小.在两种典型情形下, 硼颗粒外表面的Stefan流都会经历先由周围空间流向颗粒表面, 而后变为由颗粒表面流向周围空间的过程. 关键词： 固体火箭冲压发动机 硼颗粒 着火过程 Stefan流     

Measurement of the double layer capacitance of aluminium samples by holographic interferometry

In the present investigation, holographic interferometry was utilized for the first time to measure the double layer capacitance of aluminium samples during the initial stage of anodization processes in an aqueous solution without any physical contact. The anodization process (oxidation) of the aluminium samples was carried out chemically in different sulphuric acid concentrations (0.5–3.125% H₂S0₄) at room temperature. In the meantime, a method of holographic interferometry was used to measure the thickness of anodization (oxide film) of the aluminium samples in aqueous solutions. Along with the holographic measurement, a mathematical model was derived in order to correlate the double layer capacitance of the aluminium samples in solutions to the thickness of the oxide film of the aluminium samples which forms due to the chemical oxidation. The thickness of the oxide film of the aluminium samples was measured by real-time holographic interferometry. Consequently, holographic interferometry is found to be very useful for surface finish industries, especially for monitoring the early stage of anodization processes of metals, in which the thickness of the anodized film as well as the double layer capacitance of the aluminium samples can be determined in situ. In addition, a comparison was made between the obtained data of the double layer capacitance from the holographic measurements and the double layer capacitance data obtained from measurements of electrochemical impedance spectroscopy. The comparison indicates that there is good agreement between the data from both techniques.     

Effect of polymorphic phase transformations in alumina layer on ignition of aluminium particles

The mechanism of aluminium oxidation is quantified and a simplified ignition model is developed. The model describes ignition of an aluminium particle inserted in a hot oxygenated gas environment: a scenario similar to the particle ignition in a reflected shock in a shock tube experiment. The model treats heterogeneous oxidation as an exothermic process leading to ignition. The ignition is assumed to occur when the particle's temperature exceeds the alumina melting point. The model analyses processes of simultaneous growth and phase transformations in the oxide scale. Kinetic parameters for both direct oxidative growth and phase transformations are determined from thermal analysis. Additional assumptions about oxidation rates are made to account for discontinuities produced in the oxide scale as a result of increase in its density caused by the polymorphic phase changes. The model predicts that particles of different sizes ignite at different environment temperatures. Generally, finer particles ignite at lower temperatures. The model consistently interprets a wide range of the previously published experimental data describing aluminium ignition.     

Influence of the ignition delay time on the explosion parameters of hydrocarbon–air–oxygen mixtures at elevated pressure and temperature

Combustion phenomena change as the conditions in which they are occurring change. Proper understanding and reliable prediction of these phenomena, including important explosion indexes (e.g., flammability limits, explosion pressures), are required for achieving safe and optimal performance of industrial processes and creating new applications. To this end, we investigated the influence of the residence time on aforementioned parameters of n-butane–oxygen mixture and a typical mixture for ethylene oxide production: methane–ethylene–oxygen, focusing on how elevated conditions affect the upper explosion limit and the explosion pressure. Elevated initial conditions (T = 230 °C, P = 4–16 bar) cause pre-ignition reactions to occur in the regime of the low temperature oxidation mechanism (LTOM). These reactions change the mixture composition prior to ignition. For both mixtures investigated, these changes in the initial mixture composition, due to pre-ignition reactions, result in a different explosion pressure. This is significant, because pressure rise is used as the ignition criterion. Consequently, a different classification of the investigated mixtures, as flammable or non-flammable, is possible, depending on the residence time prior to ignition. The experimental results are compared with theoretical calculations performed using detailed reaction kinetic models.     

An experimental investigation on pre-ignition phenomena: Emphasis on the role of turbulence

Pre-ignition is an undesirable ignition event that affects chemical kinetic measurements in chemical reactors. Meanwhile, it appears randomly in engineering systems and is highly relevant to the soft knock or much stronger and detrimental super-knock in modern downsized engines. Currently its origins are still not fully understood. In this study, the role of turbulence in pre-ignition phenomena was experimentally investigated using a novel rapid compression machine. Different turbulent flow fields were achieved through calibrated orifice plates. Stoichiometric isooctane/air mixtures were tested under engine-relevant conditions in a target pressure range of 15–50 bar and a temperature range of 720–860 K. Useful insights into pre-ignition mechanism were obtained by combining instantaneous pressure acquisition with simultaneously recorded high-speed imaging. The experimental results demonstrate that owning to turbulent mixing with colder boundary layers, ignition timing is delayed when compared to ideal homogeneous compression ignition scenarios. However, pre-ignition phenomena can still be observed and become pronounced at lower target pressures with longer ignition delays. Moreover, pre-ignition formation can be characterized by single or multiple spherical flame kernels, distributed discretely inside core mixture or at near-wall regions. Different from the auto-ignition scenarios dominated by the chemical reactivity of test mixture, these pre-ignition flame kernels feature standard deflagration propagation. Finally, a dimensionless scaling analysis shows that pre-ignition formation is closely associated with turbulent length scale and laminar flame thickness.     

A new ignition time model applied to super knock

An ignition time model is developed to model super knock in a compression engine. The model assumes that thermoacoustic interaction is the primary mechanism for the onset of super knock. By ignoring diffusive effects, a simple transport equation for the time to ignition of a fluid particle is derived. The significantly reduced cost of the chemistry model allows for complex hydrocarbon fuels to be simulated. Additionally, a zonal model for the secondary ignition of a charge due to the action of an expanding flame is developed. The flame compresses the unburned gas, causing the temperature and pressure to rise, which yields a pre-ignition in the unburned gas before the charge is engulfed by the flame. It is shown that the ignition time model compares well to the detailed chemical model with less than 1% difference in the prediction of ignition delay. Using this ignition time model, a multi-dimensional simulation of super knock in a rapid compression machine corresponding to the configuration of Wang et al. [1] is performed. It is found that interaction of the shock with the flame and the side wall of the cylinder significantly enhances the strength of the shock, and the in-cylinder pressure exceeds 300 bar. From the pressure rise predicted by the simulation, it is concluded that simulated ignition is a super knock event. Since the ignition time model excludes diffusive effects on the chemistry, it is proposed that acoustic resonance of the cylinder is the primary driver in the development of super knock for the configuration under examination and that inhomogeneous ignition due to transient flame compression could be a key mechanism for super knock.     

Ignition model of boron particle based on the change of oxide layer structure

The oxide layer of boron particle is generally regarded as a two-layer structure the inner layer is B₂O₃ and the outer is (BO)_n. However, under lower temperature, a tiny layer of B₂O₃ can be generated at the surface of the (BO)_n and form a three-layer structure during the ignition process, which has been proven by experimental phenomenon. Accordingly, a parameter xo is adopted to represent the thickness of the outer B₂O₃(l) layer (outermost layer), and a simplified kinetic and diffusion model for the ignition process of boron particles in dry and wet atmosphere is developed with considering the generation and consumption process of the outermost layer. The ignition process is divided into two parts (ignition delay and first-stage combustion) by the parameter xo. The ignition temperature is defined as the particle temperature at the moment that xo reaches 0. When xo?>?0, the particle is under the ignition delay process, and the evaporation product is B₂O₃(g). When xo?=?0, the particle turns to the first-stage combustion process. (BO)_n is exposed to the environment, the evaporation products are B₂O₂(g) and B₂O₃(g), and the particle is under the two-layer structure. The oxygen diffusion inward is available during these two processes. The ignition time which is predicted by this model is in good agreement with published experimental data. Under a real ramjet condition, higher ambient temperature and concentration of water vapor can reduce both the maximum value of xo and the ignition time. The ignition temperature decreases with higher water vapor concentration, but increases with the higher ambient temperature.     

Electrochemical impedence spectroscopy versus optical interferometry techniques during anodization of aluminium

In the present investigation, holographic interferometry was utilized for the first time to measure in situ the thickness of the oxide film, alternating current (AC) impedance, and double layer capacitance of aluminium samples during anodization processes in aqueous solution without any physical contact. The anodization process (oxidation) of the aluminium samples was carried out by the electrochemical impedance spectroscopy (EIS), in different concentrations of sulphuric acid (1.0–2.5% H₂SO₄) at room temperature. In the mean time, the real-time holographic interferometric was used to measure the thickness of anodized (oxide) film of the aluminium samples in aqueous solutions. Also, mathematical models were applied to measure the AC impedance, and double layer capacitance of aluminium samples by holographic interferometry, during anodization processes in aqueous solution. Consequently, holographic interferometric is found very useful for surface finish industries especially for monitoring the early stage of anodization processes of metals, in which the thickness of the anodized film, the AC impedance, and the double layer capacitance of the aluminium samples can be determined in situ. In addition, a comparison was made between the electrochemical values obtained from the holographic interferometry measurements and from measurements of EIS. The comparison indicates that there is good agreement between the data from both techniques.     

Investigation of lubricant induced pre-ignition and knocking combustion in an optical spark ignition engine

An experimental study was performed to investigate lubricant oil induced pre-ignition and knocking combustion process in a single cylinder spark ignition (SI) engine with full bore overhead optical access. Lubricant oil was deliberately injected to the exhaust area through a specially modified direct injector to trigger the stochastic pre-ignition in a premixed air and fuel mixture. Simultaneous heat release analysis and high speed combustion imaging were used to study the pre-ignition and combustion processes. Outlier detection based on robust statistical methods was validated as an effective and efficient approach to identify sporadic pre-ignition. When pre-ignition occurred, the pre-ignited flame-front exhibited much faster propagating speed than that of the normal spark-ignited flame-front in the first stage of flame development. In several cycles, pre-ignition was followed by the pre-ignited propagating flame-front and then a separate spark-ignited flame-front before they subsequently merged together. In a few other cycles, pre-ignition led to heavy knocking combustion caused either by the auto-ignition close to the flame-front or near the cylinder wall, or both. The ultimate knock intensity of such cycles was determined by the timing, size, and location of end-gas auto-ignition of the unburned gas. Furthermore, optical detection of the oil droplet entrained combustion in the cycle subsequent to the knocking combustion cycle implied that high frequency oscillation pressure waves ejected lubricant from the piston-ring crevice.     

Magnetic propulsion of intense lithium streams in a tokamak magnetic field

This paper describes the effect and gives the theory of magnetic propulsion which allows driving free surface plasma facing liquid lithium streams in tokamaks. In the approximation of a thin flowing layer the MHD equations are reduced to one integrodifferential equation which takes into account the propulsion effect, viscosity, and the drag force due to magnetic pumping and other interactions with the magnetic field. A stability criterion is obtained for stabilization of the "sausage" instability of the streams by centrifugal force.     

Ignition and extinction of low molecular weight esters in nonpremixed flows

An experimental and kinetic modeling study is carried out to characterize combustion of low molecular weight esters in nonpremixed, nonuniform flows. An improved understanding of the combustion characteristics of low molecular weight esters will provide insights on combustion of high molecular weight esters and biodiesel. The fuels tested are methyl butanoate, methyl crotonate, ethyl propionate, biodiesel, and diesel. Two types of configuration – the condensed fuel configuration and the prevaporized fuel configuration – are employed. The condensed fuel configuration is particularly useful for studies on those liquid fuels that have high boiling points, for example biodiesel and diesel, where prevaporization, without thermal breakdown of the fuel, is difficult to achieve. In the condensed fuel configuration, an oxidizer, made up of a mixture of oxygen and nitrogen, flows over the vaporizing surface of a pool of liquid fuel. A stagnation-point boundary layer flow is established over the surface of the liquid pool. The flame is stabilized in the boundary layer. In the prevaporized fuel configuration, the flame is established in the mixing layer formed between two streams. One stream is a mixture of oxygen and nitrogen and the other is a mixture of prevaporized fuel and nitrogen. Critical conditions of extinction and ignition are measured. The results show that the critical conditions of extinction of diesel and biodiesel are nearly the same. Experimental data show that in general flames burning the esters are more difficult to extinguish in comparison to those for biodiesel. At the same value of a characteristic flow time, the ignition temperature for biodiesel is lower than that for diesel. The ignition temperatures for biodiesel are lower than those for the methyl esters tested here. Critical conditions of extinction and ignition for methyl butanoate were calculated using a detailed chemical kinetic mechanism. The results agreed well with the experimental data. The asymptotic structure of a methyl butanoate flame is found to be similar to that for many hydrocarbon flames. This will facilitate analytical modeling, of structures of ester flames, using rate-ratio asymptotic techniques, developed previously for hydrocarbon flames.     

Burning structures and propagation mechanisms of nanothermites

Nanothermites demonstrate attractive combustion characteristics such as tunable reactivity and high energy density. There is however a lack of fundamental understanding on their burning structures and reaction mechanisms due to the multi-scale complexity associated with the material and reaction heterogeneities. This gap in turn hinders the optimization of nanothermite design with desirable microstructures and controllable burning properties. In this work, a high-speed microscopy imaging system was used to reveal the burning structure of Al/CuO nanothermites and to investigate the propagation mechanism of its flame front at micron and sub-millimeter scales which have not been studied. An Al/CuO nanothermite film was fabricated as a model structure. First, the previously proposed reactive sintering was confirmed as a micron-scale burning characteristic. Then, at the sub-millimeter scale, it was demonstrated that the non-uniform burning propagation of nanothermite films is featured with distinguishable roles of the active burning sites and the pre-ignition sites. The active burning sites are clusters of reactive sintering particles and the pre-ignition sites appear in the preheating regions where Al and CuO particles have not yet participated in the reaction due to insufficient ignition energy. These pre-ignition sites form randomly and are subsequently ignited by heat transferred from the adjacent active burning sites, resulting in an active burning propagation tangentially along the propagation front. At the same time, as the thermite reaction of nanoparticles in the unburnt region is initiated, the propagation front advances in the normal direction. This experimental work reveals that the burning propagation mechanism of nanothermite films is governed by active burning propagation in both tangential and normal directions of the propagation front. Although the rates of these two modes are on the same order of magnitude, the tangential propagation of active burning is slightly faster, implying that pre-ignition sites are readily ignited with lower ignition energy.     

Measurement of the a.c. impedance of aluminium samples by holographic interferometry

In the present investigation, holographic interferometry was utilized for the first time to measure the alternating current (a.c.) impedance of aluminium samples during the initial stage of anodization processes in aqueous solution without any physical contact. The anodization process (oxidation) of the aluminium samples was carried out chemically in different sulphuric acid concentrations (0.5–3.125% H₂SO₄) at room temperature. In the mean time, a method of holographic interferometric was used to measure the thickness of anodization (oxide film) of the aluminium samples in aqueous solutions. Along with the holographic measurement, a mathematical model was derived in order to correlate the a.c. impedance of the aluminium samples in solutions to the thickness of the oxide film of the aluminium samples which forms due to the chemical oxidation. The thickness of the oxide film of the aluminium samples was measured by the real-time holographic interferometry. Consequently, holographic interferometry is found very useful for surface finish industries especially for monitoring the early stage of anodization processes of metals, in which the thickness of the anodized film as well as the a.c. impedance of the aluminium samples can be determined in situ. In addition, a comparison was made between the a.c. impedance values obtained from the holographic interferometry measurements and from measurements of electrochemical impedance spectroscopy. The comparison indicates that there is good agreement between the data from both techniques.     

Catalytic ignition and extinction of hydrogen: comparison of simulations and experiments

Surface ignition and extinction of hydrogen/air mixtures on platinum surfaces are modeled using a detailed surface kinetic mechanism and transport phenomena. It is shown that the platinum surface can be poisoned by different adsorbates, and the dynamic process of catalytic ignition and extinction is associated with a phase transition from one poisoning species to another. For certain temperatures, multiple poisoned states of the surface coexist. Comparison of simulations with experiments is conducted, and it is shown that the self-inhibition of hydrogen catalytic ignition is caused by poisoning of platinum by atomic hydrogen.     

XPS and LEED study of Pd and Au growth on alumina/Cu-Al surface

Metal-insulator-metal system was prepared using the single-crystalline Cu-9at.% Al(1 1 1) support. Oxidation of the substrate under well-controlled conditions at elevated temperature leads to the formation of well-ordered aluminium oxide layer. The Pd-Au topmost layer was prepared by a step-by-step deposition of both metals afterwards on the oxide layer at room temperature. Low energy electron diffraction (LEED) measurement did not confirm epitaxial growth of the metal overlayer and gave only a rise of diffuse background after each deposition step. The growth of Pd-Au overlayer exhibited Stranski-Krastanov mode influenced by intermetallic interaction between those metals. No binding energy shifts were visible for the core-level photoelectron peaks of the substrate and the oxide using X-ray photoelectron spectroscopy (XPS). In contrast, the binding energy shifts of Pd 3d and Au 4f photoelectron levels in both directions were observed during all depositions. Bimetallic interactions between the metals as well as size effects are further discussed.     

等离子体对含硼两相流扩散燃烧特性的影响

为排除来流空气对含硼燃气的掺混效应, 研究等离子体对含硼富燃料推进剂在补燃室二次燃烧过程的影响, 建立了含硼两相流平行进气扩散燃烧物理模型. 利用高速摄影仪拍摄了含硼燃气在补燃室二次燃烧的火焰图像, 分析了该物理模型的扩散燃烧特性和硼颗粒的二次点火距离. 采用硼颗粒的King点火模型、有限速度/涡耗散模型、颗粒轨道模型和RNG k-ε模型以及等离子体模型, 模拟了一定条件下等离子体对含硼两相流扩散燃烧过程的影响. 结果表明, 依据含硼燃气二次燃烧图像得到的硼颗粒二次点火距离, 与数值模拟结果基本一致, 保证了该物理模型和计算方法的可靠性. 含硼两相流经过等离子体区域后, 硼颗粒在运动轨迹上颗粒温度明显增加, 颗粒直径明显减小, B₂O₃的质量分数分布区域明显扩增, 70%的硼颗粒在到达补燃室2/3尺寸前燃烧效率已达到100%, 硼颗粒充分燃烧释放出更多热量导致中心流线区域温度增加近1/2, 可见等离子体可以明显强化含硼两相流的燃烧过程, 提高硼颗粒的燃烧效率.     

Brownian diode: Molecular motor based on a semi-permeable Brownian particle with internal potential drop

A model of an autonomous isothermal Brownian motor with an internal propulsion mechanism is considered. The motor is a Brownian particle which is semi-transparent for molecules of surrounding ideal gas. Molecular passage through the particle is controlled by a potential similar to that in the transition rate theory, i.e. characterized by two stationary states with a finite energy difference separated by a potential barrier. The internal potential drop maintains the diode-like asymmetry of molecular fluxes through the particle, which results in the particle?s stationary drift.     

Effect of plasma on combustion characteristics of boron

As it is very difficult to release boron energy completely, kinetic mechanism of boron is not clear, which leads to the lack of theoretical guidance for studying how to accelerate boron combustion. A new semi-empirical boron combustion model is built on the King combustion model, which contains a chemical reaction path; two new methods of plasma-assisted boron combustion based on kinetic and thermal effects respectively are built on the ZDPLASKIN zero-dimensional plasma model. A plasma-supporting system is constructed based on the planar flame, discharge characteristics and the spectral characteristics of plasma and boron combustion are analyzed. The results show that discharge power does not change the sorts of excited-particles, but which can change the concentration of excited-particles. Under this experimental condition,plasma kinetic effect will become the strongest at the discharge power of 40 W; when the discharge power is less than 40 W,plasma mainly has kinetic effect, otherwise plasma has thermal effect. Numerical simulation result based on plasma kinetic effect is consistent with the experimental result at the discharge power of 40 W, and boron ignition delay time is shortened by 53.8% at the discharge power of 40 W, which indicates that plasma accelerates boron combustion has reaction kinetic paths, while the ability to accelerate boron combustion based on thermal effect is limited.     

Novel post‐process for the passivation of a CMOS biosensor

Sensors, which are designed and fabricated in complementary metal oxide semiconductor (CMOS) technology, have become increasingly important in the field of bioelectronics. The standardized industry processes enable a fast, cheap, and reliable fabrication of biosensor devices with integrated addressing and processing units. However, the interfacing of such chips with a liquid environment has been a challenge in recent years. Especially for interfacing living cells with CMOS biosensors different elaborate post‐processes have been proposed. In this article we describe a novel and single step passivation of a CMOS biosensor using a bio‐compatible high‐permittivity thin film, which can be directly applied to the top aluminium layer of a CMOS process. The aluminium oxide and hafnium oxide multi‐layer thin films were prepared using atomic layer deposition at low process temperatures. Electrical I –V and capacitance measurements as well as electrochemical leakage current measurements were performed on films grown on aluminium bottom electrodes. The films showed a very low leakage current and were stable up to 6 V at a thickness of just 50 nm. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Experimental study and modeling of shock tube ignition delay times for hydrogen-oxygen-argon mixtures at low temperatures

Recent literature has indicated that experimental shock tube ignition delay times for hydrogen combustion at low-temperature conditions may deviate significantly from those predicted by current detailed kinetic models. The source of this difference is uncertain. In the current study, the effects of shock tube facility-dependent gasdynamics and localized pre-ignition energy release are explored by measuring and simulating hydrogen-oxygen ignition delay times. Shock tube hydrogen-oxygen ignition delay time data were taken behind reflected shock waves at temperatures between 908 to 1118 K and pressures between 3.0 and 3.7 atm for two test mixtures: 4% H₂, 2% O₂, balance Ar, and 15% H₂, 18% O₂, balance Ar. The experimental ignition delay times at temperatures below 980 K are found to be shorter than those predicted by current mechanisms when the normal idealized constant volume (V) and internal energy (E) assumptions are employed. However, if non-ideal effects associated with facility performance and energy release are included in the modeling (using CHEMSHOCK, a new model which couples the experimental pressure trace with the constant V, E assumptions), the predicted ignition times more closely follow the experimental data. Applying the new CHEMSHOCK model to current experimental data allows refinement of the reaction rate for H + O₂ + Ar ↔ HO₂ + Ar, a key reaction in determining the hydrogen-oxygen ignition delay time in the low-temperature region.