New Preparation Method of Nanocrystalline Materials by Impulse Plasma in Liquid

A new method to fabricate nanomaterials by using Impulse Plasma in Liquid is presented. Impulse plasma appears from inter-electrode space break-down in high potential difference between two electrodes submerged into a dielectric liquid, while the power supply is relatively small that is insufficient to excite an arc discharge. By changing the dielectric liquid, we can obtain metallic particles, oxides, carbides. This method does not require vacuum chamber and high energy, thus, can provide economical preparation of various types of nanomaterials. Nanocrystalline powder of titanium oxide was prepared using purified water as a dielectric liquid. Metallic nanoparticles of ytterbium, silver and copper were also prepared by the impulse plasma between a pair of the same material electrodes submerged in styrene. In addition, fullerene C₆₀ was synthesized by the impulse plasma in toluene. Nanoparticles of TiC, WC, TaC were also synthesized by the impulse plasma in styrene.     

Ion hydration near air/water interfaces and the structure of liquid surfaces

Negative adsorption of ions, commonly observed at air-water interfaces, is examined in terms of models of restricted polarization of the solvent by ions at the interface and the structure of the liquid interface. The Born and other models of ionic hydration are applied to evaluate the self-energy of the ion arising in the region of solvent near its interface and in the vacuum or vapour beyond. The adsorption energy of an ion varies substantially with distance from the liquid interface so that a distribution of ions arises as a function of distance from the interface. Integration of this distribution gives an expression, and results, for the ionic surface excess. The diffuse-layer potential, which an unequal distribution of cations and anions give rise to, gives a contribution to the surface potential of the electrolyte solution at finite concentrations.Structural aspects of the liquid interface at which ions are negatively adsorbed are discussed in terms of Stefan's ratio and the superficial excess entropies of various liquid surfaces. These entropies are related to the cohesive energy densities of the bulk liquids. Ion solvent-structure co-sphere interactions with structured interfaces will lead to specificity of negative adsorption of ions.     

润湿特性对超级电容器储能动力学的影响机理

润湿特性对超级电容器储能性能有着至关重要的影响。借助分子动力学模拟,本文研究了润湿特性对超级电容器储能动力学行为的影响。以石墨烯和晶体铜作为疏电解液和亲电解液电极材料。结果表明,在充电过程中,亲电解液铜电极呈现出非对称的U型微分电容曲线,负极电容是正极的～5.77倍,不同于经典双电层理论Gouy-Chapman-Stern(对称U型)和疏电解液型。该现象与离子自由能阻力分布密切相关,负极自由能阻力远小于正极(～2倍)和疏电解液电极,进而有利于强化双电层结构对电极电压的响应能力,导致更高微分电容。通过微分离子电荷密度,本文再现了微分电容演变规律,并发现改善润湿性会显著降低双电层厚度。最后,我们指出润湿性直接影响储能微观机理,将电荷储存机制从离子吸附和交换共同主导(疏电解液)转变到离子吸附主导(亲电解液)。本文所得结论揭示了润湿特性对储能动力学行为影响的原子层级机理,对超级电容器材料设计、构筑与润湿特性调控具有重要指导意义。     

Free energy calculations,enhanced by a gaussian ansatz,for the “chemical work” distribution

The evaluation of the free energy is essential in molecular simulation because it is intimately related with the existence of multiphase equilibrium. Recently, it was demonstrated that it is possible to evaluate the Helmholtz free energy using a single statistical ensemble along an entire isotherm by accounting for the “chemical work” of transforming each molecule, from an interacting one, to an ideal gas. In this work, we show that it is possible to perform such a free energy perturbation over a liquid vapor phase transition. Furthermore, we investigate the link between a general free energy perturbation scheme and the novel nonequilibrium theories of Crook's and Jarzinsky. We find that for finite systems away from the thermodynamic limit the second law of thermodynamics will always be an inequality for isothermal free energy perturbations, resulting always to a dissipated work that may tend to zero only in the thermodynamic limit. The work, the heat, and the entropy produced during a thermodynamic free energy perturbation can be viewed in the context of the Crooks and Jarzinsky formalism, revealing that for a given value of the ensemble average of the “irreversible” work, the minimum entropy production corresponded to a Gaussian distribution for the histogram of the work. We propose the evaluation of the free energy difference in any free energy perturbation based scheme on the average irreversible “chemical work” minus the dissipated work that can be calculated from the variance of the distribution of the logarithm of the work histogram, within the Gaussian approximation. As a consequence, using the Gaussian ansatz for the distribution of the “chemical work,” accurate estimates for the chemical potential and the free energy of the system can be performed using much shorter simulations and avoiding the necessity of sampling the computational costly tails of the “chemical work.” For a more general free energy perturbation scheme that the Gaussian ansatz may not be valid, the free energy calculation can be expressed in terms of the moment generating function of the “chemical work” distribution. © 2014 Wiley Periodicals, Inc.     

A surface-induced transition in polymeric nematics

New polymeric liquid crystals can be treated as standard nematic liquid crystals when only their bulk properties are at issue, but they exhibit peculiar surface properties. The most striking one is that biaxial distributions may be induced on a confining surface. On continuously varying the surface anchoring conditions, we find a first-order phase transition from planar to homeotropic alignment in the bulk. Moreover, the decay towards these uniaxial states is radically different in the two cases: it is asymptotically exponential in the former, whereas it happens abruptly at a finite depth in the latter. There is precisely one surface biaxial distribution that induces bistability between these decay modes: it depends on the elastic constants in the Landau-de Gennes free energy functional. The analysis of the model we propose can prove useful in detecting the sign of the difference between splay and bend constants.     

Balancing local order and long-ranged interactions in the molecular theory of liquid water

A molecular theory of liquid water is identified and studied on the basis of computer simulation of the TIP3P model of liquid water. This theory would be exact for models of liquid water in which the intermolecular interactions vanish outside a finite spatial range, and therefore provides a precise analysis tool for investigating the effects of longer-ranged intermolecular interactions. We show how local order can be introduced through quasichemical theory. Long-ranged interactions are characterized generally by a conditional distribution of binding energies, and this formulation is interpreted as a regularization of the primitive statistical thermodynamic problem. These binding-energy distributions for liquid water are observed to be unimodal. The Gaussian approximation proposed is remarkably successful in predicting the Gibbs free energy and the molar entropy of liquid water, as judged by comparison with numerically exact results. The remaining discrepancies are subtle quantitative problems that do have significant consequences for the thermodynamic properties that distinguish water from many other liquids. The basic subtlety of liquid water is found then in the competition of several effects which must be quantitatively balanced for realistic results.     

High transmittance blue-phase liquid crystal displays with slit-shaped electrode

A blue-phase liquid crystal displays (BP-LCDs) with slit-shaped pixel and common electrodes structure is proposed to increase the transmittance. It generates not only in plane field between the pixel electrodes, but also fringe field above the common electrodes. As a result, the high transmittance is obtained. The aperture ratio is also improved because of the capacitor between the pixel and common electrodes.     

Blue-phase liquid crystal display with insulating protrusion

In order to lower the saturation voltage and enhance the transmittance of in-plane switching blue-phase liquid crystal display (IPS-BPLCD), IPS-BPLCD with insulating protrusion is proposed. The single-protrusion (only set on the top of pixel electrode) and double-protrusion (set on the top of pixel and common electrodes) structures are investigated in this work. The potential distribution changes when the protrusion is used. There is a thicker transverse electric field in BPLC range, because the stronger electric field at the edges of the electrodes is decentralised into BPLC range. As a result, the saturation voltage is reduced from 36.3 V to 28.9 V when the double-protrusion structure is used, and transmittance is increased by ~20%. The contrast ratio is larger than 1000:1 in 60° viewing cone using a half-wave biaxial film. Both single-protrusion and double-protrusion structures have the uniform gamma curves at large oblique viewing angles. Moreover, the off-axis image distortion index is 0.1590 at 60º polar angle when zigzag electrodes are used.     

Fluids in nanospaces: molecular simulation studies to find out key mechanisms for engineering

We have analyzed various phenomena that occur in nanopores, focusing on elucidating their key mechanisms, to advance the effective engineering use of nanoporous materials. As ideal experimental systems, molecular simulations can effectively provide information at the molecular level that leads to mechanistic insight. In this short review, several of our recent results are presented. The first topic is the critical point depression of Lennard-Jones fluid in silica slit pores due to finite size effects, studied by our original Monte Carlo (MC) technique. We demonstrate that the first layers of adsorbed molecules in contact with the pore walls act as a “fluid wall” and impose extra finite size effects on the fluid confined in the central portion of the pore. We next present a new kernel for pore size distribution (PSD) analysis, based entirely on molecular simulation, which consists of local isotherms for nitrogen adsorption in carbon slit pores at 77 K. The kernel is obtained by combining grand canonical Monte Carlo (GCMC) method and open pore cell MC method that was developed in the previous study. We show that overall trends of the PSDs of activated carbons calculated with our new kernel and with conventional kernel from non-local density functional theory are nearly the same; however, apparent difference can be seen between them. As the third topic, we apply a free energy analysis method with the aid of GCMC simulations to investigate the gating behavior observed in a porous coordination polymer, and propose a mechanism for the adsorption-induced structural transition based on both the theory of equilibrium and kinetics. Finally, we construct an atomistic silica pore model that mimics MCM-41, which has atomic-level surface roughness, and perform molecular simulations to understand the mechanism of capillary condensation with hysteresis. We calculate the work required for the gas–liquid transition from the simulation data, and show that the adsorption branch with hysteresis for MCM-41 arise from spontaneous capillary condensation from a metastable state.     

X-ray microcalorimeter based on superconducting transition edge sensors.

We have tried to realize an X-ray imaging spectrometer based on the superconducting transition edge sensor (TES) with high energy resolution, a large pixel array, a relatively high absorption efficiency and a high count rate. Our single pixel of Ir/Au TES achieved an excellent energy resolution of 9.4 eV for 5.9 keV X-rays. We have also proposed a pixellated array of Ir-TES where we slightly modify the bias point of each pixel and identify the pixel from the response function of each pixel. Our 10-pixel device, where all pixels are parallel biased, obtained 13 eV (FWHM) at 3 keV energy resolution and 80 microm position resolution. So far, we could successfully operate a 20-pixels device. Further, we are now trying to improve the count rate and the absorption efficiency of TESes, by developing our original new TES geometry which having a radiation absorber that self-adjusts the operating temperature.     

Graphene and carbon nanotube composite electrodes for supercapacitors with ultra-high energy density

We describe a graphene and single-walled carbon nanotube (SWCNT) composite film prepared by a blending process for use as electrodes in high energy density supercapacitors. Specific capacitances of 290.6 F g(-1) and 201.0 F g(-1) have been obtained for a single electrode in aqueous and organic electrolytes, respectively, using a more practical two-electrode testing system. In the organic electrolyte the energy density reached 62.8 Wh kg(-1) and the power density reached 58.5 kW kg(-1). The addition of single-walled carbon nanotubes raised the energy density by 23% and power density by 31% more than the graphene electrodes. The graphene/CNT electrodes exhibited an ultra-high energy density of 155.6 Wh kg(-1) in ionic liquid at room temperature. In addition, the specific capacitance increased by 29% after 1000 cycles in ionic liquid, indicating their excellent cyclicity. The SWCNTs acted as a conductive additive, spacer, and binder in the graphene/CNT supercapacitors. This work suggests that our graphene/CNT supercapacitors can be comparable to NiMH batteries in performance and are promising for applications in hybrid vehicles and electric vehicles.     

Structure of electrical double layer at gold electrode in cyanide solution

The potential distribution in electrical double layer is calculated, basing on the data on the electrode charge and cyanide-ion adsorption at the gold electrode. It is shown that the integral capacitances of regions in the dense layer are not unambiguous functions of the electrode potential or charge per se, but depend also on the amount of specifically adsorbed ions Γ. A function is proposed for the describing of the Γ dependence of the dense layer integral capacitances.     

Self-assembled cotton-like copper–molybdenum sulfide and phosphide as a bifunctional electrode for green energy storage and production

As the world's energy needs grow and environmental concerns intensify, there is an increasing need for research into developing new materials that may be used in energy production and storage. Herein, we developed copper-molybdenum (Cu–Mo) sulfide and phosphide-based cotton-like nanoarchitectures via hydrothermal strategy and they were characterized using various analytical techniques. The prepared sulfide and phosphide-based materials showed HER overpotentials of 207 mV and 147 mV, respectively, as well as Tafel slope values of 118 mV/dec and 109 mV/dec at 10 mA/cm². While OER at the same current density showed 270 mV and 213 mV overpotentials with 82 mV/dec and 48 mV/dec Tafel slope, respectively. In addition, the prepared sulfide and phosphide-based materials showed significant performance towards supercapacitors, displaying specific capacitances of 3.5 and 5.2 F/cm² at 3 mA/cm², and retaining their specific capacitances by 86.9 and 69.4%, respectively, after 4,000 cycles with 100% Coulombic efficiency. These materials have the potential to be employed for energy production and storage because of their excellent electrochemical characteristics and bifunctional performance.     

Removal of Pararosaniline Hydrochloride Dye (Basic Red 9) from Aqueous Solution by Electrocoagulation: Experimental,Kinetics, and Modeling

In this work, the removal of pararosaniline hydrochloride (Basic red 9) dye from aqueous solutions by electrocoagulation was investigated. The effect of parameters such as current density, initial pH, electrolysis time, inter-electrode distance, initial dye concentration and salt concentration on dye removal efficiency were investigated. The experimental results showed that 99% dye removal was observed after 30 minutes of electrolysis for an initial dye concentration of 100 mg/L, current density of 111.1 A/m² and initial pH of 7.0. It was observed that an increase in current density, time of operation and decrease in inter-electrode distance improved the dye removal efficiency. The optimum pH range for highest dye removal was 5.0–10.25. It was also observed that increase in salt concentration in the solution reduces the specific electrical energy consumption. The kinetic study inferred that the dye removal primarily follows a first order reaction. Finally, phenomenological models were proposed to illustrate the dependence of dye removal rate constant and specific electrical energy consumption on current density, inter-electrode distance, initial dye concentration and salt concentration.     

计算液态混合物内能和内压的统计热力学理论

假定二元液态混合物分子间的相互作用势能可以表示成多体相互作用势能的和,分子间的力为短程力,相互作用势能只与分子间的相对距离有关.利用分布函数理论导出了二元液态混合物的过剩内能和内压的公式.二元液态混合物的过剩内能和内压可以表示成体积的幂级数形式,其中的系数可以用多体相互作用势和多体径向分布函数表出.讨论了单元液体的内压和过剩内能的表达式,在两种特殊情形下,过剩内能和内压的表达式分别与Egelstaff的微扰论结果及Frank的实验结果具有相同的形式.讨论了二元混合物内压和内能的两个特例,其一,在特殊情形下,给出了混合液体过剩内能的混合规则的一个证明.其二,给出的二元混合物的过剩内能和内压的表达式与Frank的实验结果具有相同的形式.     

Energy Fluctuations in a Direct Current Plasma Torch with Inter-Electrode Inserts Operated at Reduced Pressure

Direct current (dc) plasma torch with inter-electrode inserts has the merits of fixed arc length, relative high enthalpy and may show advantages in future plasma processes where stability and controllability are must-have. Energy fluctuations in the plasma may result from power supply ripple, arc length variation, and/or acoustic oscillation. Using an improved power supply with a flat waveform, the characteristics of an argon plasma energy instabilities under reduced pressure were studied by means of simultaneously monitoring the arc voltage and arc current spectrum. Dependence of the arc fluctuation behavior on the plasma generating parameters, such as the current intensity, the plasma gas flow rates and the vacuum chamber pressure were investigated and discussed. Results show that the plasma torch has a typical U-shaped voltage-ampere characteristic (VAC). The correlation between the VAC and the probability of energy distributions was studied. Through pressure measurements at the cathode cavity and the vacuum chamber, the existence of sonic flow in the inter-electrode insert channel was confirmed.     

A single-cell-gap transflective liquid crystal display with a vertically aligned cell

A single-cell-gap transflective liquid crystal display with a vertically aligned cell using square ring electrode is demonstrated. The top substrate has a top planar common electrode, a square ring pixel electrode is coated on the bottom substrate, while a bumpy reflector is coated under the bottom substrate. In this device, the planar common electrode and square ring pixel electrode generate a strong longitudinal electric field in the transmissive region (T region) and a weak fringe field in the reflective region (R region). As result, the T and R regions accumulate the same optical phase retardation. The simulation results show that the display exhibits reasonably low operating voltage, high transmittance and well-matched voltage-dependent transmittance and reflectance curves. Besides, fabrication process of the transflective liquid crystal display is very simple.     

胶体离子超级电容器的比容量评价

胶体离子超级电容器作为一种新型的超级电容器,其同时具有能量密度和功率密度高的独特优势。 目前已经发展了包括多种过渡金属阳离子和稀土阳离子,例如Mn²⁺、Fe²⁺、Co²⁺、Ni²⁺、Cu²⁺、Sn²⁺、Sn⁴⁺、La³⁺、Ce³⁺、Er³⁺和Yb³⁺的胶体离子超级电容器体系。 在电化学反应中,识别出电活性物质的存在形式对研究电极反应机理和提高比容量具有重要价值。 本文主要通过对电活性物质比容量的探讨,理解这种新型胶体离子超级电容器的电化学储能机理。 评述了胶体离子超级电容器的比容量核算方式,提出了以阳离子为标准核算比容量的原因,并与传统超级电容器的核算方式进行了比较,表明胶体离子超级电容器在提高能量密度方面具有潜在优势,有望突破现有电化学储能设备的技术瓶颈,实现下一代高能量储能器件的开发。     

Physics of artificial nano-structures on surfaces

Quantum electron transport through nano-structures such as metal atomic wires or molecular bridges is investigated with various theoretical approaches. The difference of the quantization feature between Na and Al atom wires is explained based on the eigenchannel analyses combined with the recursion-transfer matrix calculation. The eigenchannels are calculated self-consistently for Au atom wires at finite bias voltage and the nonlinear conductance is explored in relation to the offset energies of d band channels. As for molecular bridges, we find that a remarkable metalization is caused, if the coupling of the molecule with the metal electrode is enhanced. Internal current distribution within the molecular networks is discussed and exotic properties of the quantum transport is found. In particular, a strong induced loop current is revealed circulating the ring part of the molecule. The direction of the loop current is switched sharply when the electron incident energy sweeps a degenerate molecular level.     

液体的内压和内能的统计热力学理论

利用分布函数理论导出了液体的内能和内压公式.液体的内压和过剩内能可以表示成体积的幂级数形式,其中的系数可以用多体相互作用势和多体径向分布函数表出,它们仅仅与温度有关.讨论了液体仅存在第n次多体相互作用势情形的内压和过剩内能的表达式,结果与Egelstaff的微扰理论结果具有相同的形式,不仅给出了相应参数的表达式而且适用于多体相互作用较强的情形.定义了物性参数α(T)和m,得到的液体过剩内能和内压的表达式与Frank实验结果具有相同的形式,其结果不仅给出了参数α(T)和m的表达式,而且指出了Frank的过剩内能和内压公式只适用于参数α(T)和m与体积无关的液体.