Numerical Simulation of Gaseous Detonation of H_2-O_2 Mixture with Detailed Chemical Reaction Model

采用高精度的ENO格式和基于基元化学反应的真实化学反应模型求解氢氧混合气体一维爆轰波的精细结构。采用直接起爆方法得到稳定传播的爆轰波,计算的爆轰波阵面参数和实验相当符合。对爆轰波反应区化学反应的研究表明,参与反应的不同组分具有不同类型的变化特征。网格尺寸影响的研究表明,计算结果的精度随着网格尺寸的增加而增加,并能保持较好的收敛性。移动网格研究结果表明,网格运动速度和爆轰速度接近时,两者的相互作用对计算结果产生一定影响。

Displacive To Order-Disorder Two-Step Phase Transition Model For Para-Ferroelectric Transition

Two-step phase transition model, displacive to order-disorder, is proposed. The driving forces for these two transitions are fundamentally different. The displacive phase transition is one type of the structural phase transitions. We clearly define the structural phase transition as the symmetry broking of the unit cell and the electric dipole starts to form in the unit cell. Then the dipole-dipole interaction takes place as soon as the dipoles in unit cells are formed. We believe that the dipole-dipole interaction may cause an order-disorder phase transition following the displacive phase transition. Both structural and order-disorder phase transition can be first-order or second-order or in between. We found that the structural transition temperatures can be lower or equal or higher than the order-disorder transition temperature. The para-ferroelectric phase transition is the combination of the displacive and order-disorder phase transitions. It generates a variety of transition configurations along with confusions. In this paper, we discuss all these configurations using our displacive to order-disorder two-step phase transition model and clarified all the confusions.

气相爆轰波马赫反射的实验和数值研究

爆燃和爆轰是自然界中普遍存在的两种自然现象。在一定条件下爆燃完成向爆轰的转变，爆轰形成以后会出现典型的胞格结构，在爆轰波传播过程中遇到障碍物时会发生马赫反射。对这些现象的理论和实验研究在工程和科学上都有着重大的意义。在本文的实验研究中，采用爆轰激波管和烟熏膜技术对可燃气体DDT过程及爆轰波马赫反射问题进行了研究。在不同初压和楔角的情况下进行了系统的实验，得到了清晰的胞格结构图象和三波点轨迹图象。在本文的数值模拟中采用了简化的二阶段化学反应模型，整个化学反应过程被分为两个阶段：诱导反应阶段和放热反应阶段。该模型采用两个无量纲参数α和β来表示化学反应的进程。初始时刻两个参数值都为1，诱导反应开始时α的值由1逐渐减小到0，进入放热反应阶段β的值逐渐减小直到化学反应达到平衡。本文采用了全新的数值方法CE／SE对可燃气体的DDT过程和爆轰波马赫反射问题进行了数值模拟。CE／SE方法是一种在概念和方法上都和以往不同的数值方法。该方法具有构造简单、分辨率高等优点，同时格式保证了在局部和全局均满足时空意义上的守恒律。本文的研究结果表明：爆轰波遇到楔面会发生类似冲击波的正规反射和马赫反射现象。在不同楔角和初压条件下，反射前后爆轰波的胞格尺寸、形状等性质都会有明显的差别。同时三波点迹线与楔面的夹角也会有相应的变化。这些结果对于深入理解可燃气体的DDT过程和爆轰波的马赫反应射机理有重要价值。最后需要提出的是我们把全新的CE／SE方法推广到带有化学反应的流动计算中，计算结果表明这种推广是成功的。

Numerical Study on Critical Wedge Angle of Cellular Detonation Reflections

The critical wedge angle (CWA) for the transition from regular reflection (RR) to Mach reflection (MR) of a cellular detonation wave is studied numerically by an improved space-time conservation element and solution element method together with a two-step chemical reaction model. The accuracy of that numerical way is verified by simulating cellular detonation reflections at a 19.3∘ wedge. The planar and cellular detonation reflections over 45∘–55∘ wedges are also simulated. When the cellular detonation wave is over a 50∘ wedge, numerical results show a new phenomenon that RR and MR occur alternately. The transition process between RR and MR is investigated with the local pressure contours. Numerical analysis shows that the cellular structure is the essential reason for the new phenomenon and the CWA of detonation reflection is not a certain angle but an angle range.

对数值模拟气相爆轰中二阶段化学反应模型再研究

采用改进的高精度时-空守恒元解元算法(the space-time conservation element and solution element method,CE/SE method)和考虑组分的二阶段化学反应模型(Sichel的二步模型)对气相爆轰问题的数值模拟进行了分析.分析发现采用Sichel的二步模型得到的数值结果虽然比早期二阶段化学反应模型(旧二步模型)更接近实验值,但是仍然不能得到爆轰过程准确气体动力学参数.为此通过修改组分的质量分数分布形式对Sichel的二步模型进行了改造,然后采用新的二步模型对平面爆轰波进行了数值模拟.数值结果表明采用新的二步模型计算得到气体动力学参数更接近于实验值和基元反应模型的计算值,在计算精度上有较大提高.

Cellular Cell Bifurcation Of Cylindrical Detonations

Cellular cell pattern evolution of cylindrically-diverging detonations is numerically simulated successfully by solving two-dimensional Euler equations implemented with an improved two-step chemical kinetic model. From the simulation, three cell bifurcation modes are observed during the evolution and referred to as concave front focusing, kinked and wrinkled wave front instability, and self-merging of cellular cells. Numerical research demonstrates that the wave front expansion resulted from detonation front diverging plays a major role in the cellular cell bifurcation, which can disturb the nonlinearly self-sustained mechanism of detonations and finally lead to cell bifurcations.

Self-organized generation of transverse waves in diverging cylindrical detonations

Self-organized generation of transverse waves associated with the transverse wave instabilities at a diverging cylindrical detonation front was numerically studied by solving two-dimensional Euler equations implemented with an improved two-step chemical kinetic model. After solution validation, four mechanisms of the transverse wave generation were identified from numerical simulations, and referred to as the concave front focusing, the kinked front evolution, the wrinkled front evolution and the transverse wave merging, respectively. The propagation of the cylindrical detonation is maintained by the growth of the transverse waves that match the rate of increase in surface area of the detonation front to asymptotically approach a constant average number of transverse waves per unit length along the circumference of the detonation front. This cell bifurcation phenomenon of cellular detonations is discussed in detail to gain better understanding on detonation physics.

Reduced models of chemical reaction in chaotic flows

We describe and evaluate two reduced models for nonlinear chemical reactions in a chaotic laminar flow. Each model involves two separate steps to compute the chemical composition at a given location and time. The “manifold tracking model” first tracks backwards in time a segment of the stable manifold of the requisite point. This then provides a sample of the initial conditions appropriate for the second step, which requires solving one-dimensional problems for the reaction in Lagrangian coordinates. By contrast, the first step of the “branching trajectories model” simulates both the advection and diffusion of fluid particles that terminate at the appropriate point; the chemical reaction equations are then solved along each of the branched trajectories in a second step. Results from each model are compared with full numerical simulations of the reaction processes in a chaotic laminar flow.

A model for doped-oxide-source diffusion with a chemical reaction at the silicon-silicon dioxide interface

A mathematical model for doped-oxide-source diffusion is proposed. In this model the concept of segregation of impurity at the silicon-silicon dioxide is used and also a constant of “rate limitation” is introduced through a chemical reaction at the interface.

Two-step self-assembly of hierarchically-ordered nanostructures

Due to their unique size- and shape-dependent physical and chemical properties, highly hierarchically-ordered nanostructures have attracted great attention with a view to application in emerging technologies, such as novel energy generation, harvesting, and storage devices. The question of how to get controllable ensembles of nanostructures, however, still remains a challenge. This concept paper first summarizes and clarifies the concept of the two-step self-assembly approach for the synthesis of hierarchically-ordered nanostructures with complex morphology. Based on the preparation processes, two-step self-assembly can be classified into two typical types, namely, two-step self-assembly with two discontinuous processes and two-step self-assembly completed in one-pot solutions with two continuous processes. Compared to the conventional one-step self-assembly, the two-step self-assembly approach allows the combination of multiple synthetic techniques and the realization of complex nanostructures with hierarchically-ordered multiscale structures. Moreover, this approach also allows the self-assembly of heterostructures or hybrid nanomaterials in a cost-effective way. It is expected that widespread application of two-step self-assembly will give us a new way to fabricate multifunctional nanostructures with deliberately designed architectures. The concept of two-step self-assembly can also be extended to syntheses including more than two chemical/physical reaction steps (multiple-step self-assembly).

Chronopotentiometry with power-law perturbation functions at an expanding plane electrode with and without a preceding blank period for systems with a coupled first-order homogeneous chemical reaction

The systems formalism is used to obtain the interfacial concentration transients for power-law current input at an expanding plane electrode. The explicit results for the concentration transients obtained here pertain to arbitrary homogeneous reaction schemes coupled to the oxidant and reductant of a single charge-transfer step and the power-law form without and with a preceding blank period (for two types of power-law current profile, say, (i) I(t) = I0(t−t0)q for t greater-or-equal, slanted t0, I(t) = 0 for t < t0; and (ii) I(t) = I0tq for t greater-or-equal, slanted t0, I(t) = 0 for t < t0). Finally the potential transients are obtained using Padé approximants. The results of Galvez et al. (for E, CE, EC, aC) (J. Electroanal. Chem., 132 (1982) 15; 146 (1983) 221, 233, 243), Molina et al. (for E) (J. Electroanal. Chem., 227 (1987) 1 and Kies (for E) (J. Electroanal. Chem., 45 (1973) 71) are obtained as special cases.

On the Two-Step Mechanism for Synthesis of Transition-Metal Nanoparticles

The two-step particle synthesis mechanism, also known as the Finke-Watzky (1997) mechanism, has emerged as a significant development in the field of nanoparticle synthesis. It explains a characteristic feature of the synthesis of transition metal nanoparticles, an induction period in precursor concentration followed by its rapid sigmoidal decrease. The classical LaMer theory (1950) of particle formation fails to capture this behavior. The two-step mechanism considers slow continuous nucleation and autocatalytic growth of particles directly from precursor as its two kinetic steps. In the present work, we test the two-step mechanism rigorously using population balance models. We find that it explains precursor consumption very well, but fails to explain particle synthesis. The effect of continued nucleation on particle synthesis is not suppressed sufficiently by the rapid autocatalytic growth of particles. The nucleation continues to increase breadth of size distributions to unexpectedly large values as compared to those observed experimentally. A number of variations of the original mechanism with additional reaction steps are investigated next. The simulations show that continued nucleation from the beginning of the synthesis leads to formation of highly polydisperse particles in all of the tested cases. A short nucleation window, realized with delayed onset of nucleation and its suppression soon after in one of the variations, appears as one way to explain all of the known experimental observations. The present investigations clearly establish the need to revisit the two-step particle synthesis mechanism.

The Development of a Two-Dimensional Transient Catalyst Model for Direct Injection Two-Stroke Applications.

This paper describes the development of a two-dimensional transient catalyst model. Although designed primarily for two-stroke direct injection engines, the model is also applicable to four-stroke lean burn and diesel applications. The first section describes the geometries, properties and chemical processes simulated by the model and discusses the limitations and assumptions applied. A review of the modeling techniques adopted by other researchers is also included. The mathematical relationships which are used to represent the system are then described, together with the finite volume method used in the computer program. The need for a two-dimensional approach is explained and the methods used to model effects such as flow and temperature distribution are presented. The problems associated with developing surface reaction rates are discussed in detail and compared with published research. Validation and calibration of the model is achieved by comparing predictions with measurements from a flow reactor. While an extensive validation process, involving detailed measurements of gas composition and thermal gradients, has been completed, the analysis is too detailed for publication here and is the subject of a separate technical paper.

The Validation of a Two-Dimensional Transient Catalyst Model for Direct Injection Two-Stroke Applications

This paper describes the detailed validation of a computer model designed to simulate the transient light-off in a two-stroke oxidation catalyst. A plug flow reactor is employed to provide measurements of temperature and gas concentration at various radial and axial locations inside the catalyst. These measurements are recorded at discrete intervals during a transient light-off in which the inlet temperature is increased from ambient to 300oC at rates of up to 6oC/sec. The catalyst formulation used in the flow reactor, and its associated test procedures, are then simulated by the computer and a comparison made between experimental readings and model predictions. The design of the computer model to which this validation exercise relates is described in detail in a separate technical paper. The first section of the paper investigates the warm-up characteristics of the substrate and examines the validity of the heat transfer predictions between the wall and the gas in the absence of chemical reactions. The predictions from a typical single-component CO transient light-off test are discussed in the second section and are compared with experimental data. In particular the effect of the temperature ramp on the light-off curve and reaction zone development is examined. An analysis of the C3H6 conversion is given in the third section while the final section examines the accuracy of the light-off curves which are produced when both CO and C3H6 are present in the feed gas. The analysis shows that the heat and mass transfer calculations provided reliable predictions of the warm-up behaviour and post light-off gas concentration profiles. The self-inhibition and cross-inhibition terms in the global rate expressions were also found to be reasonably reliable although the surface reaction rates required calibration with experimental data.