Thermodynamic potentials and thermodynamic relations in nonextensive thermodynamics

The generalized Gibbs free energy and enthalpy are derived in the framework of nonextensive thermodynamics by using the concept of the physical temperature and the physical pressure. Some relations of the thermodynamical potentials are changed due to the difference between the physical temperature and the inverse of Lagrange multiplier. We derive the thermodynamical relation between the heat capacities at a constant volume and at a constant pressure using the generalized thermodynamical potential. We find that it has a different form from the traditional one in Gibbs thermodynamics. But, the expressions of the heat capacities in this framework using the generalized thermodynamical potentials are still the same as the traditional one.     

Optical fiber humidity sensor based on evanescent-wave scattering

The phenomenon of evanescent-wave scattering (EWS) is used to design an optical-fiber humidity sensor. Porous solgel silica (PSGS) coated on the surface of a silica optical-fiber core scatters evanescent waves that penetrate the coating layer. Water molecules in the gas phase surrounding the optical fiber can be absorbed into the inner surface of the pores of the porous silica. The absorbed water molecules form a thin layer of liquid water on the inner surface of the porous silica and enhance the EWS. The amount of water absorbed into the PSGS coating is in dynamic equilibrium with the water-vapor pressure in the gas phase. Therefore the humidity in the air can be quantitatively determined with fiber-optic EWS caused by the PSGS coating. The humidity sensor reported here is fast in response, reversible, and has a wide dynamic range. The possible interference caused by EWS to an optical-fiber gas sensor with a reagent-doped PSGS coating as a transducer is also discussed.     

虫蛀玉米种子的空气耦合超声波检测

提出了一种基于空气耦合超声波技术的玉米种子虫蛀孔洞颗粒和完好颗粒分类识别方法·首先根据玉米颗粒的弹性模量、泊松比和密度等物理量计算出了玉米颗粒的声速,并根据检测精度需求设定了激励信号频率。然后采用MATLAB对采集的两类种子超声波信号数据进行分析处理,并分析了种子厚度和摆放方位对超声波响应特征的影响。最后建立了K近邻(KNN)、簇类独立软模式法(SIMCA)、Fisher线性判别(LDA)和决策树(DT)识别模型,并对模型性能进行了测试.结果表明;种子孔洞深度、胚部厚度和正反面方位不同,即超声波在种子表面的反射程度不同、在种子中传播声程不同,则起声波信号衰减程度不同,导致接收到信号的幅值不同,且样本点在主成分分析(PCA)特征空间的分布也不同。4种识别模型均可以实现对两类玉米的分类识别,其中KNN模型性能最佳,其对虫蛀孔洞颗粒和完好颗粒的正确识别率分别为98%100%,误差带为2%,0。此结果说明采用空气耦合超声波技术可以实现对玉米种子虫蛀孔洞颗粒的检测。     

Tuning Pt–Cu nanostructures by bromide ions and their superior electrocatalytic activities for methanol oxidation reaction

Dendritic Pt–Cu nanoparticles were synthesized by a facile one-step method with the help of surfactant Brij58 at room temperature, and we also studied the effects of different Pt–Cu ratios on the morphology and size of nanoparticles. In addition, we further tuned the morphology of the Pt–Cu nanostructures by introducing bromide ions, eventually leading to the appearance of some tripod-like structures. Compared with dendritic Pt–Cu and commercial Pt black, these tripod-like Pt–Cu nanostructures exhibited higher electrocatalytic activity and CO tolerance for catalyzing methanol oxidation.

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Improving the rate performance and stability of LiNi<Subscript>0.6</Subscript>Co<Subscript>0.2</Subscript>Mn<Subscript>0.2</Subscript>O<Subscript>2</Subscript> in high voltage lithium-ion battery by using fluoroethylene carbonate as electrolyte additive

Fluoroethylene carbonate (FEC) is investigated as the electrolyte additive to improve the electrochemical performance of high voltage LiNi_0.6Co_0.2Mn_0.2O₂ cathode material. Compared to LiNi_0.6Co_0.2Mn_0.2O₂/Li cells in blank electrolyte, the capacity retention of the cells with 5 wt% FEC in electrolytes after 80 times charge-discharge cycle between 3.0 and 4.5 V significantly improve from 82.0 to 89.7%. Besides, the capacity of LiNi_0.6Co_0.2Mn_0.2O₂/Li only obtains 12.6 mAh g^?1 at 5 C in base electrolyte, while the 5 wt% FEC in electrolyte can reach a high capacity of 71.3 mAh g^?1 at the same rate. The oxidative stability of the electrolyte with 5 wt% FEC is evaluated by linear sweep voltammetry and potentiostatic data. The LSV results show that the oxidation potential of the electrolytes with FEC is higher than 4.5 V vs. Li/Li⁺, while the oxidation peaks begin to appear near 4.3 V in the electrolyte without FEC. In addition, the effect of FEC on surface of LiNi_0.6Co_0.2Mn_0.2O₂ is elucidated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The analysis result indicates that FEC facilitates the formation of a more stable surface film on the LiNi_0.6Co_0.2Mn_0.2O₂ cathode. The electrochemical impedance spectroscopy (EIS) result evidences that the stable surface film could improve cathode electrolyte interfacial resistance. These results demonstrate that the FEC can apply as an additive for 4.5 V high voltage electrolyte system in LiNi_0.6Co_0.2Mn_0.2O₂/Li cells.     

硅酸镓镧声表面波传感器的压力温度多参数解耦分析

针对硅酸镓镧声表面波压力传感器,提出了一种温度和压力的多参数解耦方法。理论上采用有限元方法与微扰理论结合,计算传感器在不同温度、压力下频率响应。根据计算结果,构造出传感器温度与压力的解耦公式。以一种基于LGS(0°,0°,100°)点压力式SAW传感器为例,理论计算得到其温度与压力解耦公式的具体参数,同时与在-55℃-125℃,0-1 MPa范围内的实验测试结果对比。理论分析和实验测试结果基本吻合,验证了温度压力多参量解耦方法的正确性。     

Optimization of Pretreatment Method for Alkylmercuries Speciation in Coal by High‐Performance Liquid Chromatography Coupled with UV‐Digestion Cold Vapor Atomic Fluorescence Spectrometry

Abstract

Exhaustive extraction of analytes in their original chemical forms from samples with complex matrices is a pivotal step for speciation analysis. Herein we propose a pretreatment method for extracting and preconcentrating methylmercury and ethylmercury from coal samples by using KBr–H₂SO₄/CuSO₄–C₆H₅CH₃–Na₂S₂O₃ system. The extraction conditions, including the volume of the organic phase and the extraction time, were optimized in detail. Speciation analysis of alkylmercuries was carried out by high‐performance liquid chromatography online coupled with UV‐digestion and cold vapor atomic fluorescence spectrometry. The detection limits were 0.6 ng mL^?1 for methylmercury and 1 ng mL^?1 for ethylmercury, respectively. The recoveries of methylmercury and ethylmercury spiked in a sample were 84% and 82%, respectively. The method was applied successfully to analysis of alkylmercuries in four coal samples collected from northeast China.     

Highly improved crystallization behavior of poly(L‐lactide) induced by a novel nucleating agent: substituted‐aryl phosphate salts

In this work, a novel nucleating agent (NA) based on substituted‐aryl phosphate salts was introduced into poly(L‐Lactide) (PLLA). The nonisothermal and isothermal crystallization behaviors of nucleated PLLA samples were investigated through differential scanning calorimetry (DSC), wide angle X‐ray diffraction, and polarized optical microscope (POM). Furthermore, the effect of annealing treatment on the cold crystallization behaviors of nucleated samples was also investigated. The results show that the crystallization of PLLA, whether for the melt crystallization (including nonisothermal and isothermal crystallization process) or for the cold crystallization (including the cold crystallization occurring during the DSC heating process and during the annealing process), is greatly dependent upon the content of NA. At relatively lower NA content (≤0.1 wt%), the nucleation effect of NA is inconspicuous, however, at higher NA content (≥0.2 wt%), it exhibits great nucleation effect for the crystallization of PLLA. Further results show that the double endothermic peak of PLLA depends on the temperature applied for the crystallization. Copyright © 2012 John Wiley & Sons, Ltd.     

Effect of temperature on the fluorescence emission of carbazole-substituted methylcellulose in dilute aqueous solutions

Fluorescent-labeled polymers, carbazole-substituted methylcelluloses (Cz-MCs) were synthesized through a two-step reaction by firstly introducing epoxy group to carbazole, and then reacting with MC. Structure of Cz-MC was characterized by using FTIR, NMR, elemental analysis and UV–vis spectroscopy. Aggregation behavior of Cz-MCs in dilute aqueous solution was investigated by a thermotropic study performed with dynamic laser light scattering. Cz-MCs displayed concentration self-quenching properties of fluorescence spectra both in H₂O and DMSO. The temperature effect on the fluorescent emission in dilute aqueous solution was explored. The results showed that the degree of substitution of carbazole and thermal aggregation of Cz-MC contributed to the formation of network structure between the molecules, consequently leading to the enhancement or quenching in fluorescence intensity.     

Study on the interaction between urea and cellulose by combining solid-state 13C CP/MAS NMR and extended Hückel charges

In this article, solid-state ¹³C CP/MAS NMR combined with extended Hückel charges was applied to investigate the interaction between urea and cellulose in the NaOH/urea aqueous solvent system. Direct experimental evidence was provided to support the interaction between urea and cellulose. The solid-state ¹³C CP/MAS NMR results revealed that complicated complexes are formed by urea, NaOH and cellulose in the solution. Excess urea exists in a free state, which explains why 7 wt% NaOH/12 wt% urea/81 wt% H₂O is the optimal ratio selection to dissolve cellulose. Based on the correlation in which the computed extended Hückel charge on carbon of urea is approximately inversely proportional to its ¹³C chemical shift, a possible interaction model of cellulose, NaOH and urea was proposed. Interactions exist between any two of urea, NaOH and cellulose, which results in the cellulose chain being surrounded by NaOH and urea molecules. NaOH and urea may be in the same surface layer of cellulose chains.