Evolution of Local Structural Ordering and Chemical Distribution upon Delithiation of a Rock Salt–Structured Li1.3Ta0.3Mn0.4O2 Cathode

Lithium‐rich disordered rock‐salt oxides have attracted great interest owing to their promising performance as Li‐ion battery cathodes. While experimental and theoretical efforts are critical in advancing this class of materials, a fundamental understanding of key property changes upon Li extraction is largely missing. In the present study, single‐crystal synthesis of a new disordered rock‐salt cathode material, Li_1.3Ta_0.3Mn_0.4O₂ (LTMO), and its use as a model compound to investigate Li concentration–driven evolution of local cationic ordering, charge compensation, and chemical distribution are reported. Through the combined use of 2D and 3D X‐ray nanotomography, it is shown that Li removal accompanied by oxygen oxidation is correlated with the development of morphological defects such as particle cracking. Chemical heterogeneity, quantified by subparticle level distribution of Mn valence state, is minimal during Mn redox, which drastically increases upon the formation of cracks during oxygen redox. Density functional theory and bond valence sum mismatch calculations reveal the presence of local short‐range ordering in the pristine oxide, which gradually disappears along with the extraction of Li. The study suggests that with cycling the transformation into true cation–disordered state can be expected, which likely impacts the voltage profile and obtainable energy density of the oxide cathodes.     

A simple mathematical analysis on the effect of sand in Cr(VI) reduction using zero valent iron

A simple mathematical model was proposed to analyze the enhancement of Cr(VI) reduction when sand materials are added to the zero valent iron (ZVI). Natural decay of Cr(VI) in a control experiment was analyzed by using a zero-order decay reaction. Adsorption kinetics of Cr(VI) to sand was modeled as a first-order reversible process, and the reduction rate by ZVI was treated as a first-order reaction. Natural decay of Cr(VI) was also included in other experiments, i.e., the adsorption to sand, the reduction by ZVI, and both adsorption and reduction when sand and ZVI are present together. The model parameters were estimated by fitting the solution of each model to the corresponding experimental data. To observe the effect of sand addition to ZVI, both adsorption and reduction rate models were considered simultaneously including the natural decay. The solution of the combined model was fitted to the experimental data to determine the first-order adsorption and reduction rate constants when sand as well as ZVI is present. The first-order reduction rate constant in the presence of sand was about 35 times higher than that with ZVI only.     

Training ratio and comparison of trained vector quantizers

The vector quantizer (VQ) codebook is usually designed by clustering a training sequence (TS) drawn from the underlying distribution function. In order to cluster a TS, we may use the K-means algorithm (generalized Lloyd (1982) algorithm) or the self-organizing map algorithm. In this paper, a survey of trained VQ performance is conducted to study the effect of the training ratio on training quantizers. The training ratio, which is defined by the ratio of the TS size to the codebook size, is dependent on the VQ structure. Hence, different VQs may show different training properties, even though the VQs are designed for the same TS. A numerical comparison of trained VQs is then conducted in conjunction with deriving their training ratios. Through the comparison, it is shown that structured VQs can achieve better performance than the full-search scheme if the codebooks are trained by a finite TS. Further, we can derive a design or comparison guideline that maintains equal training ratios in training different VQs.     

Effect of bulk flow pulsations on film cooling with compound angle holes

Experiments are conducted to investigate the effects of bulk flow pulsations on film cooling with compound angle holes. A row of five film cooling holes is considered with orientation angles of 0°, 30°, 60°, and 90° at a fixed inclination angle of 35°. Static pressure pulsations are produced by an array of six rotating shutter blades, which extend across the span of the exit of the wind tunnel test section. The pulsation frequency is fixed at 36 Hz, but changes in the time-averaged blowing ratios of 0.5, 1.0 and 2.0 produce three different coolant Strouhal numbers, 3.6, 1.8 and 0.9, respectively. Detailed film cooled boundary layer temperature distributions are measured by a cold wire and the adiabatic film cooling effectiveness by thermochromic liquid crystal (TLC). The boundary layer temperature surveys show that pulsations induce large disruptions to the boundary layer temperature distribution and the film coverage. As the orientation angle increases, the injectant concentration spreads further into the spanwise direction because of pulsations than the steady case. With pulsations the adiabatic film cooling effectiveness value decreases regardless of the orientation angle. The amount of reduction, however, depends on the orientation angle in such a way that the larger the orientation angle is, the smaller the reduction is.     

Buckling analysis for delaminated composites using plate bending elements based on higher‐order zig‐zag theory

A finite element based on the efficient higher‐order zig‐zag theory with multiple delaminations is developed. The bending part of the formulation is constructed from the concept of DKQ element. Unlike conventional elements, a developed element has its reference in the bottom surface which simplifies zig‐zag terms on formulation. Exact patch solutions are developed on elements which have the bottom reference system. The present element passes proper bending patch tests in the arbitrary mesh configurations in isotropic materials. Zig‐zag formulation is adopted to model laminated plates with multiple delaminations. To assess the accuracy and efficiency of the present element based on higher‐order zig‐zag theory with multiple delaminations, the linear buckling problem of laminated plates with multiple delaminations has been analysed. The results have been compared with three‐dimensional elasticity solutions. The present element works as an efficient tool for analysing the behaviour of the laminated composites with multiple delaminations. Copyright © 2002 John Wiley & Sons, Ltd.     

Three-temperature modeling of carrier-phonon interactions in thin GaAs film structures irradiated by picosecond pulse lasers

This article investigates numerically the carrier-phonon interactions in thin gallium arsenide (GaAs) film structures irradiated by subpicosecond laser pulses to figure out the role of several recombination processes on the energy transport during laser pulses and to examine the effects of laser fluences and pulses on non-equilibrium energy transfer characteristics in thin film structures. The self-consistent hydrodynamic equations derived from the Boltzmann transport equations are established for carriers and two different types of phonons, i.e., acoustic phonons and longitudinal optical (LO) phonons. From the results, it is found that the two-peak structure of carrier temperatures depends mainly on the pulse durations, laser fluences, and nonradiative recombination processes, two different phonons are in nonequilibrium state within such lagging times, and this lagging effect can be neglected for longer pulses. Finally, at the initial stage of laser irradiation, SRH recombination rates increases sufficiently because the abrupt increase in carrier number density no longer permits Auger recombination to be activated. For thin GaAs film structures, it is thus seen that Auger recombination is negligible even at high temperature during laser irradiation.     

Application of artificial neural networks to the analysis of two‐dimensional fluorescence spectra in recombinant E coli fermentation processes

A two‐dimensional (2D) spectrofluorometer was used to monitor various fermentation processes with recombinant E coli for the production of 5‐aminolevulinic acid (ALA). The whole fluorescence spectral data obtained during a process were analyzed using artificial neural networks, ie self‐organizing map (SOM) and feedforward backpropagation neural network (BPNN). The SOM‐based classification of the whole spectral data has made it possible to qualitatively associate some process parameters with the normalized weights and variances, and to select some useful combinations of excitation and emission wavelengths. Based on the classified fluorescence spectra a supervised BPNN algorithm was used to predict some of the process parameters. It was also shown that the BPNN models could elucidate some sections of the process's performance, eg forecasting the process's performance. Copyright © 2005 Society of Chemical Industry     

Epitaxial growth of GaN on (0001) Al<Subscript>2</Subscript>O<Subscript>3</Subscript> via solution-cast seed layer formation process using Ga(mDTC)<Subscript>3</Subscript>

This paper reports an alternative method for the growth of GaN epitaxial layer on (0001) Al₂O₃ substrate by hot-wall vapor phase epitaxy technique. Tris (N,N-dimethyldithiocarbamato)-gallium (III), Ga(mDTC)₃ was introduced as a precursor material for the seed layer formation in the growth of GaN. Optimal growth conditions with seed layers formed by the Ga(mDTC)₃ concentration of 0.047 mol/L were identified: Growth temperature was found to be 850 °C, and optimal distance between the reactant outlet and substrate was determined to be 12.5 cm. Characterization results showed that this growth method produce high-crystallinity GaN epitaxial layers at a relatively lower growth temperature compared to the existing growth techniques and simplify the growth process.