In-Depth TEM Investigation on Structural Inhomogeneity within a Primary LixNi0.835Co0.15Al0.015O2 Particle: Origin of Capacity Decay during High-Rate Discharge

The structural stability of cathode materials during electrochemical reactions, in particular, under high-rate discharge, is pertinent to the design and development of new electrode materials. This study investigates the structural inhomogeneity that develops within a single LiNi_0.835Co_0.15Al_0.015O₂ (NCA83) particle during a fast discharging process under different cutoff voltages. Some of the NCA83 particles discharged from a high cutoff voltage (4.8 V) developed surface areas in which the layered structure was recovered, although the interiors retained the degraded spinel structure. These micro- and nano-scale structural inversions from high cutoff voltage seem highly correlated with structural evolutions in the initial charged state, and may ultimately degrade the cycling stability. This study advances understanding of the structural inhomogeneity within primary particles during various electrochemical processes and may facilitate the development of new Ni-rich cathode materials.     

Analysis of Voice and Quantitative Measurement of Glottal Gap After Thyroplasty Type I in the Treatment of Unilateral Vocal Paralysis

Thyroplasty type I is one of several surgical treatments in which improving the voice of unilateral vocal fold paralysis is the ultimate objective. The goal of the surgery is the medialization of the paralyzed vocal fold. The purpose of this study is to evaluate the effectiveness of thyroplasty type I through acoustical analysis, aerodynamic measures, and quantitative videostroboscopic measurements. We report on 20 patients with unilateral vocal cord paralysis who underwent thyroplasty type I. We performed preoperative and postoperative video image analysis (normalized glottal gap area) and computer-assisted voice analysis (fundamental frequency, jitter, shimmer, noise-to-harmonic ratio, mean phonation time, mean flow rate, mean subglottic pressure) in all patients. The glottal gap was significantly reduced after thyroplasty type I. Postoperative voice quality was characterized by an improved pitch and amplitude pertubation (jitter and shimmer), phonation time (mean phonation time), and subglottic pressure (mean subglottic pressure). Thyroplasty type I is an effective method for regaining glottal closure and vocal function.     

Efficiency comparison of subcritical OTEC power cycle using various working fluids

This paper presents an investigation into the thermal efficiency and main component size of the subcritical ocean thermal energy conversion (OTEC) power cycle using various working fluids under different operation conditions. The analysis procedure was performed with a simulation program written in Engineering Equation Solver. With the given analysis conditions, efficiencies of three types of working fluids were evaluated and compared. It was found that the thermal efficiencies of the subcritical OTEC power cycle depend strongly on the evaporating and condensing temperature, and turbine efficiency, while not roughly depending on superheating degrees and pump efficiencies. With a thorough grasp of these results, an efficient OTEC power cycle can be designed. R717 and R404A yielded the highest and lowest thermal efficiencies among the wet fluids, and R22 showed the largest efficiency among the dry fluids. For the iso-entropic fluids, R245fa provided the highest thermal efficiency. In comparison of main component sizes, R404A and R744 had the largest and smallest condenser size, respectively. Also, R744 exhibited the smallest evaporator size, and R404A and R227ea show the largest size. And R744 and R245fa gave the largest and smallest pump size, respectively. From the results of thermal efficiency and main components for various working fluids in the OTEC power cycle, R717 in the subcritical OTEC power cycle is the preferred working fluid, except for its toxicity and flammability.     

Theoretical studies on mechanical and electronic properties of s-triazine sheet

Abstract

Mechanical and electronic properties of s-triazine sheet are studied using first-principles calculations based on density functional theory. The in-plane stiffness and bulk modulus for s-triazine sheet are found to be less than that of heptazine. The reduction can be related to the nature of the covalent bonds connecting the adjacent sheets and the number of atoms per unit cell. The Poisson’s ratio of s-triazine sheet is half the value to that of graphene. Additionally, the calculated values of the two critical strains (elastic and yielding points) of s-triazine sheet are in the same order of magnitude to that for heptazine which was calculated using MD simulations in the literature. It is also demonstrated that s-triazine sheet can withstand larger tension in the plastic region. These results established a stable mechanical property for s-triazine sheet. We found a linear relationship of bandgap as a function of bi-axial tensile strain within the harmonic elastic region. The reduced steric repulsion of the lone pairs (p_x-, p_y-) causes the p_z-like orbital to shift to high energy, and consequently an increase in the bandgap. We find no electronic properties modulation of the s-triazine sheet under electric field up to a peak value of 10 V/nm. Such noble properties may be useful in future nanomaterial applications.     

Efficiency enhancement of flexible dye-sensitized solar cell with sol–gel formed Nb2O5 blocking layer

We investigated the effect of a Nb₂O₅ blocking layer formed through the sol–gel method introduced to a titanium metal foil electrode in a flexible dye sensitized solar cell. The blocking layer formed directly on the working electrode physically separates the working electrode from the electrolyte, and prevents back transfer of electrons from the electrode to the electrolyte. The gel processing conditions (sol reaction time) and heat treatment temperature used in formation of the Nb₂O₅ blocking layer have been shown to affect the performance of the dye sensitized solar cell and optimal values of these parameters have been determined. A sol reaction time of 45 min and heat treatment temperature of 550 °C has been observed to result in optimal cell performance (η = 6.185%, J_sc = 13.233 mA/cm², V_oc = 0.672 V, ff = 0.694). Introduction of an Nb₂O₅ blocking layer enhances solar cell efficiency by 39.7%, which is much greater than the increase of 24.6% observed in a similar cell containing a TiO₂ blocking layer under standard illumination conditions. The results obtained via Nb₂O₅ have been observed to be superior to those obtained via a TiO₂ blocking layer.     

Antifungal effects of 3D scaffold type gelatin/Ag nanoparticles biocomposite prepared by solution plasma processing

The 3D scaffold type biocomposites of gelatin/silver nanoparticles were prepared through the silver nanoparticles (Ag NPs) formation in gelatin solution using solution plasma process (SPP) and their antifungal activity was evaluated. The mixture of 3% gelatin solution and silver precursor (AgNO₃; 1–10 mM) was subject to discharge at high voltage (1600 V) under the controlled conditions to form the suspension of Ag NPs in the gelatin matrix. The freeze-drying process of lyophilization was employed to fabricate the 3D scaffold type biocomposite of gelatin/Ag NPs from the suspension. The water-insoluble property was improved by cross-linking using UV-irradiation (λ = 254 nm for 15 min). The physical and chemical characteristics of the biocomposite were investigated using UV–vis spectroscopy, EDS, FE-SEM, and TEM. The results indicated that the 3D scaffold biocomposite of gelatin/Ag NPs had spherical shape with approximately 11–12 nm of diameter. The antifungal activity analysis suggested that the biocomposite with Ag NPs could inhibit the growth of Candida albicans as well as that of hyphae and spores of Aspergillus parasiticus significantly. MIC of the biocomposite for C. albicans and A. parasiticus was determined as 80 μg/ml and 240 μg/ml of Ag NPs, respectively. The growth inhibition of 92.8% was observed in the biocomposite with 10 mM Ag against C. albicans.     

Nucleophilic substitution reactions promoted by oligoethylene glycols: a mechanistic study of ion‐pair SN2 processes facilitated by Lewis base

We present a mechanistic study for nucleophilic substitution (S_N2) reactions facilitated by multifunctional n‐oligoethylene glycols (n‐oligoEGs) using alkali metal salts MX (M⁺ = Cs⁺, K⁺, X^– = F^–, Br^–, I^–, CN^–) as nucleophilic agents. Density functional theory method is employed to elucidate the underlying mechanism of the S_N2 reaction. We found that the nucleophiles react as ion pairs, whose metal cation is ‘coordinated’ by the oxygen atoms in oligoEGs acting as Lewis base to reduce the unfavorable electrostatic effects of M⁺ on X^–. The two terminal hydroxyl (?OH) function as ‘anchors’ to collect the nucleophile and the substrate in an ideal configuration for the reaction. Calculated barriers of the reactions are in excellent agreement with all experimentally observed trends of S_N2 yields obtained by using various metal cations, nucleophiles and oligoEGs. The reaction barriers are calculated to decrease from triEG to pentaEG, in agreement with the experimentally observed order of efficiency (triEG < tetraEG < pentaEG). The observed relative efficiency of the metal cations Cs⁺ versus K⁺ is also nicely demonstrated (larger [better] barrier [efficiency] for Cs⁺ than for K⁺). We also examine the effects of the nucleophiles (F^–, Br^–, I^–, CN^–), finding that the magnitudes of reaction barriers are F^– > CN^– > Br^– > I^–, elucidating the observation that the yield was lowest for F^–. It is suggested that the role of oxygen atoms in the promoters is equivalent to that of –OH group in bulky alcohols (tert‐butyl or amyl‐alcohol) for S_N2 fluorination reactions previously studied in our lab. Copyright © 2012 John Wiley & Sons, Ltd.     

A new analytical theory for earing generated from anisotropic plasticity

Commercial canmaking processes include drawing, redrawing and several ironing operations. It is experimentally observed that during the drawing and redrawing processes earing develops, but during the ironing processes earing is reduced. It is essential to understand the earing mechanism during drawing and ironing for an advanced material modeling. A new analytical approach that relates the earing profile to r-value and yield stress directionalities is presented in this work. The analytical formula is based on the exact integration of the logarithmic strain. The derivation is for a cylindrical cup under the plane stress condition based on rigid perfect plasticity while force equilibrium is not considered. The earing profile is obtained solely from anisotropic plastic properties in simple tension. The earing mechanism is explained from the present theory with explicit formulae. It has been proved that earing is the combination of the contributions from r-value and yield stress directionalities. From a directionality (y-axis) vs. angle from the rolling (x-axis) plot, the earing profile is generated to be a scaled mirror image of the r-value directionality with respect to 90° (x = 90) and also a scaled mirror image of the yield stress directionality with respect to the reference yield stress (y = 1). Three different materials (Al-5% Mg alloy, AA 2090-T3 and AA 3104 RPDT control coil) are considered for verification purposes. This approach provides a fundamental basis for understanding the earing mechanism. In practice, the present theory is also very useful for the prediction of the earing profile of a drawn and iron cup and its related convolute cut-edge design for an earless cup.     

Construction of biorthogonal wavelet vectors

The construction of all possible biorthogonal wavelet vectors corresponding to a given biorthogonal scaling vector may not be easy as that of biorthogonal uniwavelets. In this paper, we give some theorems about the construction of biorthogonal wavelet vectors, which is followed by simple computations for constructing all parametrized biorthogonal wavelet vectors supported in [-1,1]. This approach is also suitable for the case of compactly supported orthogonal uniwavelet. Moreover, we give examples parametrizing all biorthogonal wavelet vectors corresponding to well known biorthogonal scaling vectors.