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.     

Decorating surface charge of graphite nanoplate using an electrostatic coupling agent for 3-dimensional polymer nanocomposite

Here, we report a facile approach to electrostatically couple the surface charges of graphite nanoplate (GNP) fillers and poly(methyl methacrylate) (PMMA) polymer particles using ethylene maleic anhydride (EMA) copolymer as an electrostatic coupling agent. Our strategy involved switching the intrinsic repulsive electrostatic interactions between the directly exfoliated GNPs fillers and the PMMA particles to attractive electrostatic surface interactions for preparing core(PMMA)-shell (GNP) precursor in order to optimizing 3-dimensionally dispersed polymer nanocomposite. As a result, the electrical conductivity of the composites dramatically increased by a factor of 16.7 in the EMA-coupled GNP/PMMA composites compared with that of the EMA-free GNP/PMMA composites. In addition, the percolation threshold was also notably reduced from 0.32 to 0.159 vol% after electrostatic coupling of the GNPs fillers and PMMA particles. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48390.     

Facile modifications of polyimide via chloromethylation: II. Synthesis and characterization of thermocurable transparent polyimide having methylene acrylate side groups

From chloromethylated polyimide, a useful starting material for modification of aromatic polyimides, a thermocurable transparent polyimide having acrylate side groups was prepared. In the presence of 1,8‐diazabicyclo[5,4,0]undec‐7‐ene, chloromethylated polyimide was esterified with acrylic acid to synthesize poly(imide methylene acrylate). The polymer was soluble in organic solvent, which makes it possible to prepare a planar film by spin coating. The polymer film became insoluble after thermal treatment at 230 °C for 30 min. Optical transparency of the film at 400 nm (for 1 µm thickness) was higher than 98 % and not affected by further heating at 230 °C for 250 min. Adhesion properties measured by the ASTM D3359‐B method ranged from 4B to 5B. Preliminary results of planarization testing showed a high degree of planarization (DOP) value (>0.53). These properties demonstrate that poly(imide methylene acrylate) could be utilized as a thermocurable transparent material in fabricating display devices such as TFT‐LCD. Copyright © 2004 Society of Chemical Industry     

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.     

Study on the c-axis preferred orientation of ZnO film on various metal electrodes

ZnO thin film was deposited on various metal electrodes by reactive sputtering, and c-axis preferred orientation of the film has been studied. ZnO, which has high piezoelectricity, is promising for oscillators or filter devices such as surface acoustic wave (SAW) device, gas sensor, and film bulk acoustic resonator (FBAR). But, for the application of ZnO film for these devices, the film should be grown with c-axis normal to the electrode. In this study, Pt, Al, and Au were deposited on Si wafer, and the surface roughness and crystal structure of the ZnO film on the electrode were investigated using AFM, scanning electron microscopy (SEM), and X-ray diffraction (XRD). Columnar structures of ZnO films were grown with c-axis normal to all electrodes, and among them Pt electrode showed the highest preferred orientation of ZnO film.     

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.     

A finite element analysis of damage propagation during metal forming process

In this paper damage propagation during metal forming process is investigated with the concept of continuum damage mechanics. An isotropic damage model based on the theory of materials of type N is adopted to describe the damage process of a ductile material with large elasto-viscoplastic deformation. To solve the finite elasto-viscoplasticity problem, a reasonable kinematic strain measure for largely deformed solids is used and the damage constitutive equations based on thermodynamical framework are developed. The stiffness degradation of the loaded material is chosen as a damage measure. An extended interior penalty method is used to impose the contact condition on the boundary. The highly nonlinear equilibrium equations are reduced to the incremental weak form and approximated by the total Lagrangian finite element method. The displacement control method along with the modified Riks' continuation technique based on displacement parameter is used to solve the incremental iterative equations. As numerical examples, upsetting, backward extrusion and punch problems are simulated and the results of damage propagation and J₂ stress contours with and without damage are presented. For punch problems, spring back and residual stresses are also presented.