A mathematical model for wet-chemical diffusion-controlled mask etching through a circular hole

Asymptotic solutions are presented for diffusion-controlled wet-chemical etching through a round hole in a mask. The three-dimensional diffusion field is assumed to be axisymmetric and fully developed. Two time regimes are considered. The first applies when the etched depth is small in comparison with the width of the mask opening. In the second, the depth of etching is much greater than the width of the mask opening. Explicit solutions are found for the shape of the etched surface as a function of the physical parameters. Among other things it is found that, as long as the etched pits are shallow, etching through small apertures is faster than through larger ones. The opposite is true for deep pits.     

Explosion energy in the synthesis of superhard phases

This article reviews works of the Institute for Problems of Materials Science evoted to the application of explosion energy for the synthesis of superhard phases (SHPs) based on phase transformations of layered structures of carbon and boron nitride at high pressures. Major attention is given to the development and application of the high-temperature shock compression method, which made it possible to synthesize a new structural form of carbon and to attain, for the first time, a 70% yield of cubic BN under shock compression. The diagram of BN phase transformations by different mechanisms is discussed, which demonstrates the dependence of the phase composition of shock compression products on the ordering degree of the starting graphite-like structure. __________ Translated from Poroshkovaya Metallurgiya, Vol. 46, No. 1–2(453), pp. 3–10, 2007.     

Electrochemically instantaneous reduction of conducting polyaniline-coated latex particles dispersed in acidic solution

A cathodic voltammetric wave was observed in an aqueous suspension of mono-dispersed, spherical polyaniline-coated polystyrene particles, whereas no anodic wave was detected. This irreversibility was common to particles with eight different diameters ranging from 0.2 to 7.5 μm. Such irreversibility cannot be found at polyaniline-coated electrodes, and thus is a property of the dispersion of polyaniline latex. The reduction current was controlled by diffusion of dispersed particles. The reduction, being the conversion from the electrical conducting state to the resistive one, should begin at a point of contact between the conducting particle and the electrode in order to be propagated to the whole particle rapidly. In contrast, the oxidation proceeds slowly with the propagation of conducting zone, during which Brownian motion lets the particle detach from the electrode. The number of loaded aniline units per particle, determined by weight analysis, ranged from 6 × 10⁶ (Ø 0.2 μm) to 3 × 10¹¹ (Ø 7.5 μm) and was proportional to 2.9 powers of the particle diameter. The diffusion-controlled current of the cathodic wave was proportional to 2.4 powers of the diameter. The difference in these powers, 0.5, agreed with a theoretical estimation of the diffusion-controlled current, the diffusion coefficient for which was given by the Stokes-Einstein equation.     

Spatial simulations in systems biology: from molecules to cells

Cells are highly organized objects containing millions of molecules. Each biomolecule has a specific shape in order to interact with others in the complex machinery. Spatial dynamics emerge in this system on length and time scales which can not yet be modeled with full atomic detail. This review gives an overview of methods which can be used to simulate the complete cell at least with molecular detail, especially Brownian dynamics simulations. Such simulations require correct implementation of the diffusion-controlled reaction scheme occurring on this level. Implementations and applications of spatial simulations are presented, and finally it is discussed how the atomic level can be included for instance in multi-scale simulation methods.     

煤粉再燃过程中主要气体体积分数的变化规律

在一维炉上对煤粉再燃过程中烟气内主要气体体积分数随再燃区初始氧体积分数的变化规律进行了研究.再燃温度为1 273 K时,脱硝效率及H2、CO体积分数曲线随再燃区氧体积分数升高均呈不规则"M"型.脱硝效率与H2体积分数出现峰值时的氧体积分数一致,CO体积分数峰值处的氧体积分数高一些.脱硝效率及H2、CO体积分数的第一次下降是由气相着火引起的.氧体积分数进一步上升时,煤焦被气相燃烧热引燃,颗粒温度的大幅跃升促使异相脱硝反应增强,脱硝效率及H2、CO、CH4体积分数再次上升.氧体积分数更高时煤焦燃烧开始受扩散控制,火焰自焦表面外移,颗粒升温趋缓,能够到达焦表面的氧气减少,必须有氧参与的异相还原反应减弱,脱硝效率再次下降.再燃温度更高时,脱硝效率及H2、CO体积分数的变化趋势与1 273 K时基本类似,但稍平缓.     

强磁场作用下材料扩散型固态相变的微观机理

为探讨强磁场对物质原子尺度行为(电子运动、离子扩散)的影响,采用光学显微镜研究强磁场作用下Fe-0.12%C合金的扩散型固态相变;采用数字多用表测量强磁场作用下的纯铝板电阻研究其电子分布.结果表明:随磁感应强度增强,Fe-0.12%C合金室温显微组织中,铁素体晶粒平行于磁场方向伸长并呈链状排列的趋势增强,珠光体团的长轴方向平行于磁场方向伸长的程度也增强;纯铝板的电阻在平行于磁场方向放置时减小,垂直于磁场方向放置时电阻有增加趋势.这是由于组成金属晶体的自由电子和排列成晶格状的金属离子在磁场作用下受到洛伦兹力的作用,随磁感应强度增强,沿磁场方向的电子浓度、金属离子扩散有增强趋势,导致磁场作用下材料扩散型相变的室温组织出现形状各向异性.     

Leaching kinetics of antimony-bearing complex sulfides ore in hydrochloric acid solution with ozone

The leaching kinetics of Sb and Fe from antimony-bearing complex sulfides ore was investigated in HCl solution by oxidation–leaching with ozone. The effects of temperature, HCl concentration, stirring speed and particle size on the process were explored. It is found that the recoveries of Sb and Fe reach 86.1% and 28.8%, respectively, when the reaction conditions are 4.0 mol/L HCl, 900 r/min stirring speed at 85 °C with <0.074 mm particle size after 50 min leaching. XRD analysis indicates that no new solid product forms in the leaching residue and the leaching process can be described by shrinking core model. The leaching of Sb corresponds to diffusion-controlled model at low temperature (15–45 °C) and mixed-controlled model at high temperature (45–85 °C), and the apparent activation energies are 6.91 and 17.93 kJ/mol, respectively. The leaching of Fe corresponds to diffusion-controlled model, and the apparent activation energy is 1.99 kJ/mol. Three semi-empirical rate equations are obtained to describe the leaching process.     

An investigation of lithium transport through vanadium pentoxide xerogel film electrode by analyses of current transient and ac-impedance spectra

Lithium transport through vanadium pentoxide xerogel film electrode has been investigated in a 1 M solution of LiClO₄ in propylene carbonate by employing potentiostatic current transient technique and ac-impedance spectroscopy. From the comparison of the initial current experimentally measured with those initial currents theoretically calculated from the Ohm’s law and the Cottrell equation, it was confirmed that the cell-impedance-controlled constraint at the electrode surface is changed to the real potentiostatic boundary condition (diffusion-controlled constraint) when the potential step exceeds a critical value over the whole range of the lithium content. It was also found that the slope of the logarithmic current transient obtained at the lithium contents above 0.4 positively deviates in absolute value from 0.5 even under the real potentiostatic boundary condition, but the phase angle of the diffusion impedance under the semi-infinite diffusion condition negatively deviates in absolute value from 45° with increasing lithium content. With the aid of the X-ray diffractometry, the anomalous behaviours of the current transient and the diffusion impedance were discussed in terms of lithium transport through the interlayers with widely distributed spacings across the quasi-ordered xerogel film electrode. Furthermore, the current transient theoretically determined by employing the concept of interlayer spacing distribution coincided fairly well in form with that current transient experimentally measured.     

磨球直径对机械合金化合成TiC反应过程的影响

使用机械合金化方法在卧式行星式球磨机上制备了TiC。利用X射线衍射、扫描电子显微镜对粉末的微观结构和形貌的变化进行了分析。讨论了在机械合金化制备TiC过程中磨球直径对于球磨效率、球磨能量的传递以及Ti+C→TiC发生机理的影响,对于TiC的不同形成机理作出了解释。结果表明:在机械合金化制备TiC的过程中,磨球直径对于反应发生的速率和反应机理有着明显的影响,即当磨球直径较小时,Ti+C→TiC反应是以机械诱发扩散反应(MRD)的形式逐步进行的;当磨球直径较大时,反应是以自蔓燃反应(SHS)的形式快速进行的。     

Diffusion and phase transformation on interface between substrate and NiCrAlY in Y-PSZ thermal barrier coatings

NiCrAlY/Y₂O₃-Y-PSZ (yttria-partially stabilized zirconia) thermal barrier coatings were developed on a superalloy (Ni-10Co-9Cr-7W-5Al, wt.%) surface. The superalloys were first coated with a bond coat of Ni-19Cr-8Al-0.5Y (wt.%) alloy that was deposited by low-pressure plasma spraying and then covered with a top coat of ZrO₂-8wt.%Y₂O₃ by air plasma spraying. The microstructure near the interface was analyzed using an optical microscope, a scanning electron microscope, microhardness measurements, and x-ray diffraction, and the phases of composition were measured using an electron probe microanalyzer after exposure at 1100°C for different times in air or a vacuum. The reaction processes also were simulated using diffusion-controlled transformation (DICTRA) software in which diffusion was considered as being only the γ phase, and the γ′ phase was treated as spheroidal particles in γ. From the authors’ results, it can be concluded that a γ′-phase layer is observed at the interface between substrate and bond coat, and its thickness increases with increasing exposure times in air at 1100 °C. This layer showed good cohesion with the substrate and bond coat. It can also be concluded that the formation of the γ′-phase layer can be predicted from DICTRA simulation. The simulation also shows the same trend of the composition profiles as experimental data.