Low-frequency conductivity of low wear high-entropy alloys.

High-entropy alloys (HEAs) provide new research avenues for alloy combinations in the periodic table, opening numerous possibilities in novel-alloy applications. However, their electrical characteristics have been relatively underexplored. The challenge in establishing an HEA electrical conductivity model lies in the changes in electronic characteristics caused by lattice distortion and complexity of nanostructures. Here we show a low-frequency electrical conductivity model for the Nb-Mo-Ta-W HEA system. The cocktail effect is found to explain trends in electrical-conductivity changes in HEAs, while the magnitude of the reduction is understood by the calculated plasma frequency, free electron density, and measured relaxation time by terahertz spectroscopy. As a result, the refractory HEA Nb15Mo35Ta15W35 thin film exhibits both high hardness and excellent conductivity. This combination of Nb15Mo35Ta15W35 makes it suitable for applications in atomic force microscopy probe coating, significantly improving their wear resistance and atomic-scale image resolution.

Unveiling transient current response in bilayer oxide-based physical reservoirs for time-series data analysis.

Physical reservoirs employed to map time-series data and analyze extracted features have attracted interest owing to their low training cost and mitigated interconnection complexity. This study reports a physical reservoir based on a bilayer oxide-based dynamic memristor. The proposed device exhibits a nonlinear current response and short-term memory (STM), satisfying the requirements of reservoir computing (RC). These characteristics are validated using a compact model to account for resistive switching (RS) via the dynamic evolution of the internal state variable and the relocation of oxygen vacancies. Mathematically, the transient current response can be quantitatively described according to a simple set of equations to correlate the theoretical framework with experimental results. Furthermore, the device shows significant reliability and ability to distinguish 4-bit inputs and four diverse neural firing patterns. Therefore, this work shows the feasibility of implementing physical reservoirs in hardware and advances the understanding of the dynamic response.

Preferential lattice expansion of polypropylene in a trilayer polypropylene/polyethylene/polypropylene microporous separator in Li-ion batteries.

The abnormal lattice expansion of commercial polypropylene (PP)/polyethylene (PE)/polypropylene (PP) separator in lithium-ion battery under different charging current densities was observed by in-situ X-ray diffraction. Significant lattice changes of both PP and PE were found during the low current density charging. The capacity fading and the resistance value of the cell measured at 0.025 C (5th retention, 92%) is unexpectedly larger than that at 1.0 C (5th retention, 97.3%) from the electrochemical impedance spectroscopic data. High-resolution scanning electron microscopy is employed to witness the pore changes of the trilayered membrane. Density functional theory calculations were used to investigate the mechanism responsible for the irregular results. The calculations revealed that the insertion of Li-ion and EC molecule into PP or PE are thermodynamically favourable process which might explain the anomalous significant lattice expansion during the low current density charging. Therefore, designing a new separator material with a more compact crystalline structure or surface modification to reduce the Li insertion during the battery operation is desirable.

Effect of 1,3-Propane Sultone on the Formation of Solid Electrolyte Interphase at Li-Ion Battery Anode Surface: A First-Principles Study.

Density functional theory is applied to investigate the reductive reactions of reductive-type additive, 1,3-propane sultone (PS), on the formation of solid electrolyte interphase (SEI) near the lithium-ion battery anode surface. Different from the studies that mostly focus on the reduction dissociation of a specific molecule, we adopt an iterative method that systematically considered most possible reactants from the environment in every round of the reaction. The thermodynamically favorable reaction in each round was chosen. Its products then proceed to the following step. At least four iterations of reactions were calculated. The favorable products in each round were then analyzed to understand the trend of the series reactions. With the iterative method, the compounds in every reaction round can be inspected in detail. The method not only predicted the compounds that are consistent with those observed in the experiments but also provide insights into how PS forms an effective SEI. In the solvent state, the most stable reduction states of PS and electrolyte ethylene carbonate (EC) are confirmed as the initial reactants further interact with the environment supplies. First, with the addition of PS, the reduction of PS is prior to EC, which would suppress the reduction of EC and decrease the generation of ethene gas. Second, the compounds from the initial reaction round of PS are lithiated ones and show higher reduction ability than that of EC, while the latter show lower reduction ability than that of the EC, which terminated the reactions. This would be the critical properties for reductive-type additive to form an effective SEI film.

Using the high-temperature phase transition of iron sulfide minerals as an indicator of fault slip temperature.

The transformation of pyrite into pyrrhotite above 500 °C was observed in the Chelungpu fault zone, which formed as a result of the 1999 Chi-Chi earthquake in Taiwan. Similarly, pyrite transformation to pyrrhotite at approximately 640 °C was observed during the Tohoku earthquake in Japan. In this study, we investigated the high-temperature phase-transition of iron sulfide minerals (greigite) under anaerobic conditions. We simulated mineral phase transformations during fault movement with the aim of determining the temperature of fault slip. The techniques used in this study included thermogravimetry and differential thermal analysis (TG/DTA) and in situ X-ray diffraction (XRD). We found diversification between 520 °C and 630 °C in the TG/DTA curves that signifies the transformation of pyrite into pyrrhotite. Furthermore, the in situ XRD results confirmed the sequence in which greigite underwent phase transitions to gradually transform into pyrite and pyrrhotite at approximately 320 °C. Greigite completely changed into pyrite and pyrrhotite at 450 °C. Finally, pyrite was completely transformed into pyrrhotite at 580 °C. Our results reveal the temperature and sequence in which the phase transitions of greigite occur, and indicate that this may be used to constrain the temperature of fault-slip. This conclusion is supported by field observations made following the Tohoku and Chi-Chi earthquakes.

Self-Etching-Induced Morphological Evolution of ZnO Microrods Grown on FTO Glass by Hydrothermal Method.

In this research, the zinc oxide (ZnO) microrods were grown by hydrothermal method on fluorine-doped tin oxide (FTO) glass functionalized by self-assembled monolayer of octadecyltrimethoxysilane (ODS; CH3(CH2)17Si(OCH3)3). The sharp-tip or polygonal shape with specific facets at the top end of ZnO microrods can be obtained by post retention at low temperature. The morphologies were characterized by the field-emission scanning electron microscope (FESEM) and transmission electron microscopy (TEM). The results confirm that the morphology change at the top end is due to self-etching. The mechanism responsible for the formation of various top-end morphologies was proposed. The specific facets that left after 6-h retention were identified. The room-temperature micro-photoluminescence spectra showed a strong ultraviolet emission at 387 nm, and a broad emission at a range of from 500 to 700 nm. The morphology change also influences the photoluminescence (PL) spectra. A satellite peak in the UV emission spectra was observed. The peak may be attributed to the morphology effect of the microrods.

Optimization of the dye-sensitized solar cell performance by mechanical compression.

In this study, the P25 titanium dioxide (TiO2) nanoparticle (NP) thin film was coated on the fluorine-doped tin oxide (FTO) glass substrate by a doctor blade method. The film then compressed mechanically to be the photoanode of dye-sensitized solar cells (DSSCs). Various compression pressures on TiO2 NP film were tested to optimize the performance of DSSCs. The mechanical compression reduces TiO2 inter-particle distance improving the electron transport efficiency. The UV-vis spectrophotometer and electrochemical impedance spectroscopy (EIS) were employed to quantify the light-harvesting efficiency and the charge transport impedance at various interfaces in DSSC, respectively. The incident photon-to-current conversion efficiency was also monitored. The results show that when the DSSC fabricated by the TiO2 NP thin film compressed at pressure of 279 kg/cm(2), the minimum resistance of 9.38 Ω at dye/TiO2 NP/electrolyte interfaces, the maximum short-circuit photocurrent density of 15.11 mA/cm(2), and the photoelectric conversion efficiency of 5.94% were observed. Compared to the DSSC fabricated by the non-compression of TiO2 NP thin film, the overall conversion efficiency is improved over 19.5%. The study proves that under suitable compression pressure the performance of DSSC can be optimized.

Effect of compressed TiO2 nanoparticle thin film thickness on the performance of dye-sensitized solar cells.

In this study, dye-sensitized solar cells (DSSCs) were fabricated using nanocrystalline titanium dioxide (TiO2) nanoparticles as photoanode. Photoanode thin films were prepared by doctor blading method with 420 kg/cm2 of mechanical compression process and heat treatment in the air at 500°C for 30 min. The optimal thickness of the TiO2 NP photoanode is 26.6 µm with an efficiency of 9.01% under AM 1.5G illumination at 100 mW/cm2. The efficiency is around two times higher than that of conventional DSSCs with an uncompressed photoanode. The open-circuit voltage of DSSCs decreases as the thickness increases. One DSSC (sample D) has the highest conversion efficiency while it has the maximum short-circuit current density. The results indicate that the short-circuit current density is a compromise between two conflict factors: enlargement of the surface area by increasing photoanode thickness and extension of the electron diffusion length to the electrode as the thickness increases.

Order-disorder phase transformation of triacylglycerols: effect of the structure of the aliphatic chains.

Plant oils have been used as environmentally benign lubricants since they present high viscosity index and flash points and low evaporation loss. Triacylglycerols (TAG) are the major components of naturally occurring oils and fats and are able to produce high strength lubricant films. One of the main concerns that hinders the usage of triacylglycerols as lubricants, however, is the thermal stability of these molecules. In this paper, we report on the effect of chain structure on density, viscosity, and thermal stability of triacylglycerols using molecular dynamics simulations. The selected triacylglycerols are trilauroylglycerol (LLL-TAG), tristearoylglycerol (SSS-TAG), trans-trioleoylglycerol (trans-OOO-TAG), and trans-trilinolenoylglycerol (trans-LeLeLe-TAG). The first two TAGs are saturated molecules with a different number of carbons in the chain, and the second two TAGs are monounsaturated and polyunsaturated molecules, respectively. The computed results demonstrate that the length of the aliphatic chain influences the physical properties of triacylglycerols. TAGs with short chain (LLL-TAG) show higher density than TAGs with longer chains. Viscosity is determined by the degree of recoil of the aliphatic chains and by the number and location of unsaturated bonds. Thermal stability, as represented by the ability of triacylglycerols to stay in a disordered phase during the cooling process, is related to the order-disorder phase transition temperature. Since the phase transition temperature can be correlated to the thermal stability during the cooling process, LeLeLe-TAG shows the highest thermal stability among the systems considered. These results can aid in the design of molecules with specific lubrication properties.

Ab initio molecular dynamics study of methanol adsorption on copper clusters.

The preferential structures of small copper clusters Cun (n=2-9) and the adsorption of methanol molecules on these clusters are examined with first principles, molecular dynamics simulations. The results show that the copper clusters undergo systematic changes in bond length and bond order associated with altering their preferential structures from one-dimensional structures, to two-dimensional and three-dimensional structures. The results also indicate that low coordination number sites on the copper clusters are both the most favorable for methanol adsorption and have the greatest localization of electronic charge. The simulations predict that charge transfer between the neutral copper clusters and the incident methanol molecules is a key process by which adsorption is stabilized. Importantly, the changes in the dimensionality of the copper clusters do not significantly influence methanol adsorption.