Rare Events in Stochastic Partial Differential Equations on Large Spatial Domains

A methodology is proposed for studying rare events in stochastic partial differential equations in systems that are so large that standard large deviation theory does not apply. The idea is to deduce the behavior of the original model by breaking the system into appropriately scaled subsystems that are sufficiently small for large deviation theory to apply but sufficiently large to be asymptotically independent from one another. The methodology is illustrated in the context of a simple one-dimensional stochastic partial differential equation. The application reveals a connection between the dynamics of the partial differential equation and the classical Johnson–Mehl–Avrami–Kolmogorov nucleation and growth model. It also illustrates that rare events are much more likely and predictable in large systems than in small ones due to the extra entropy provided by space.     

Mechanochemical metathesis synthesis and characterization of nano-structured MnV2O6·xH2O (x=2, 4)

A solid-state metathesis approach for the synthesis of hydrated MnV₂O₆·xH₂O (x=2, 4) materials driven by mechanochemical activation energy has been demonstrated. The metathesis pathway of forming the desired product is confirmed by the presence of high lattice energy by-product such as NaCl. The structural, optical, and chemical properties of the synthesized materials are examined by powder X-ray diffraction, X-ray photoelectron spectroscopy, thermo gravimetric analysis, scanning electron microscopy, transmission electron microscopy, and diffused reflectance measurements in the UV–vis range. The valence state of Mn and V was determined to be +2 and +5, respectively, for the title compounds and the bandgap values determined showed these materials are likely to be semiconductors.     

Computer simulation, thermodynamic and microstructural studies of benzamide–benzoic acid eutectic system

Phase diagram of benzamide–benzoic acid system has been studied by the thaw–melt method. Linear velocities of crystallization of the components and the eutectic mixture were determined at different undercoolings. Values of the heat of fusion were obtained from DSC studies. Excess Gibbs free energy, excess enthalpy and excess entropy of mixing were calculated. In order to know the nature of interaction between the two components, FT-IR spectral analyses were done. In addition to these studies, computer simulation has been done to obtain an idea about the interaction energy and the optimized geometry of the eutectic mixture. Microstructural studies showed the formation of an irregular structure in the eutectic mixture, which changed with aging and on addition of impurities.     

Crystallisation of Ba1-xSrxZn2Si2O7 from BaO/SrO/ZnO/SiO2 glass with different ZrO2 and TiO2 concentrations

The effect of different nucleation agents such as ZrO₂ and TiO₂ was investigated for a first time with respect to their crystallisation behaviour in the glass system BaO-SrO-ZnO-SiO₂. In all studied glasses, a Ba_1-xSr_xZn₂Si₂O₇ (0.1 ≤ x ≤ 0.9) solid solution crystallized. This phase was first described in 2015 to possess a similar structure as the high temperature phase of BaZn₂Si₂O₇ and a thermal expansion close to zero or even negative. It may find applications e.g. as cook panels, telescope mirrors, and furnace windows. Kinetic parameters of the crystallisation process were determined by supplying different heating rates in a differential scanning calorimeter (DSC). The results were evaluated using the equations of Ozawa and Kissinger with respect to the activation energies. Furthermore, the Ozawa method was used for the determination of Avrami parameters, which provides further information on the nucleation and crystallisation processes. Scanning electron microscopy including electron backscatter diffraction (EBSD) was used to characterise the microstructure, to determine the crystallite size and the crystal orientation. For the characterisation of the occurring crystalline phases, X-ray diffraction was used.     

Mathematical modeling of grown-in defects formation in Czochralski silicon

On the basis of a mathematical model proposed previously [S. Kobayashi, J. Crystal Growth 174 (1997) 163], oxygen precipitation in growing Czochralski (CZ) crystals is analyzed, and the calculated results are compared with experimental data of grown-in defects observed with laser scattering tomography (LST). The behavior of oxygen precipitates is qualitatively very similar to that of grown-in defects, but there are quantitative discrepancies between the calculation and the observation. The formation process of grown-in defects is discussed.     

Transmission electron microscopy study of an AlN nucleation layer for the growth of GaN on a 7-degree off-oriented (0 0 1) Si substrate by metalorganic vapor phase epitaxy

We have investigated the morphology of the high-temperature-grown AlN nucleation layer and its role in the early stage of GaN growth, by means of transmission electron microscopy. The nitride was selectively grown on a 7-degree off-oriented (0 0 1) patterned Si substrate by metalorganic vapor phase epitaxy. AlN was deposited on the inclined unmasked (1 1 1) facet in the form of islands. The size of the islands varied along the slope, which is attributable to the diffusion of the growth species in the vapor phase. The GaN nucleation occurred at the region where rounded AlN islands formed densely. The threading dislocations were observed to generate in the GaN nucleated region.     

The effect of magnetic fields on the electrodeposition of iron

The effect of a uniform magnetic field with flux density up to 1 T on the electrodeposition of Fe from sulphate electrolyte has been investigated under different field configurations relative to the electrode surface. Voltammetric and chronoamperometric experiments have been carried out coupled with an electrochemical quartz crystal microbalance for in situ mass change measurements. The structure and morphology of the deposited films were determined by scanning electron microscopy, atomic force microscopy and X-ray diffraction measurements. Results show that, when the magnetic field is applied parallel to the electrode surface, the limiting current density and the deposition rate are increased due to the magnetohydrodynamic effect. The nucleation process is also affected in parallel configuration; the current density of the maximum on the chronoamperograms is decreased, and an additional nucleation step might be observed. This effect is attributed to the hydrodynamic response of the electrochemical system. No significant influence on the electrochemical reaction was observed when a magnetic field was applied perpendicular to the electrode. But in this configuration, the morphology of deposited layers is changed by the magnetic field. The morphology changes are discussed. No effect of the magnetic field on the crystallographic structure was observed.     

Synchronous Dual Electrolyte Additive Sustains Zn Metal Anode with 5600 h Lifespan

Despite conspicuous merits of Zn metal anodes, the commercialization is still handicapped by rampant dendrite formation and notorious side reaction. Manipulating the nucleation mode and deposition orientation of Zn is a key to rendering stabilized Zn anodes. Here, a dual electrolyte additive strategy is put forward via the direct cooperation of xylitol (XY) and graphene oxide (GO) species into typical zinc sulfate electrolyte. As verified by molecular dynamics simulations, the incorporated XY molecules could regulate the solvation structure of Zn²⁺, thus inhibiting hydrogen evolution and side reactions. The self-assembled GO layer is in favor of facilitating the desolvation process to accelerate reaction kinetics. Progressive nucleation and orientational deposition can be realized under the synergistic modulation, enabling a dense and uniform Zn deposition. Consequently, symmetric cell based on dual additives harvests a highly reversible cycling of 5600 h at 1.0 mA cm⁻²/1.0 mAh cm⁻².     

Growing ZIF-8 Seeds on Charged COF Substrates toward Efficient Propylene-Propane Separation Membranes

We report a covalent organic framework (COF) induced seeding strategy to fabricate metal–organic framework (MOF) membranes. Contrary to graphene oxide nuclei-depositing substrate, COF substrate has uniform pore size, high microporosity and abundant functional groups. We designed a series of charged COF nanosheets to induce the formation of ZIF-8@COF nanosheet seeds with high aspect ratio over 150, which were readily processed into a compact and uniform seed layer. The resulting ZIF-8 membranes with thickness down to 100 nm exhibit an ultrahigh C₃H₆/C₃H₈ separation performance and superior long-term stability. Our strategy is also validated by fabricating ultrathin ZIF-67 and UiO-66 membranes.     

碳纤维微晶结构的形成与生长

碳纤维的微晶结构是影响其性能的决定性因素,本论文采用广角X-射线衍射法研究了聚丙烯腈预氧纤维在碳化阶段中微晶结构的形成、生长与转变过程。研究结果表明:在1000℃以下,经预氧化反应形成的不连续多环芳香平面结构沿平行于纤维轴的方向堆积并逐渐靠近,形成类似于晶核的微晶结构生长中心,表现为类石墨片层间距的减小而晶粒增长缓慢;当温度高于1000℃时,晶粒的生长速度明显加快,形成三维有序的微晶结构;在温度高于1500℃的石墨化阶段,类石墨微晶结构进行重排,晶粒尺寸迅速增加。根据这一规律,可以通过控制晶核生成和晶粒生长速度的匹配,进行碳纤维的结构设计和调控。