Effect of the degree of crosslinking on penetrant transport in polystyrene

The effect of the degree of crosslinking of glassy polymers on the transport mechanism of penetrants was investigated using a series of divinyl benzene (DVB)-crosslinked polystyrenes of nominal crosslinking ratio X from 0.001 38 to 0.060 mol DVB/mol styrene. The number average molecular weight between crosslinks, $\text{M}\text{?}{}_{\mathrm{<mtext>c</mtext>}}$, was determined from equilibrium swelling experiments in cyclohexane. Dynamic swelling experiments with cyclohexane at 30°C showed that the mechanism of penetrant transport was anomalous. An overshoot in the penetrant uptake was observed, characteristic of macromolecular relaxations and of changing solubility of the cyclohexane in the continuously swelling polystyrene. Photographs of various samples during the swelling process showed that solvent crazing occurred predominantly in loosely crosslinked samples.     

Heat capacities of polyethylene and linear fluoropolymers

Heat capacities at constant pressure, C_p, and at constant volume C_v, were calculated with the help of normal mode frequency spectra and compared to experimental data for crystalline or semicrystalline polyethylene, poly(vinyl fluoride), poly(vinylidene fluoride), polytrifluooroethylene and poly(tetrafluoroethylene). A calculation scheme using a Tarasov function for 2N skeletal vibrational modes and an approximation of the residual 7N normal modes from known data on polyethylene and polytetrafluoroethylene is developed for all homologous, linear fluoropolymers. N is the number of carbon backbone atoms of the repeating unit. Calculations can be carried out over the whole temperature range 0 K to melting. For the two theta temperatures and the constant A₀ used for C_v to C_p conversion, fluorine-concentration dependent curves are given. The relations are expected to hold also for copolymers and blends of intermediate fluorine contents. Recommended experimental (data bank) heat capacities agree to ±2.5% with the calculations.     

Ionic liquids as electrolytes

Salts having a low melting point are liquid at room temperature, or even below, and form a new class of liquids usually called room temperature ionic liquids (RTIL). Information about RTILs can be found in the literature with such key words as: room temperature molten salt, low-temperature molten salt, ambient-temperature molten salt, liquid organic salt or simply ionic liquid. Their physicochemical properties are the same as high temperature ionic liquids, but the practical aspects of their maintenance or handling are different enough to merit a distinction. The class of ionic liquids, based on tetraalkylammonium cation and chloroaluminate anion, has been extensively studied since late 1970s of the XX century, following the works of Osteryoung. Systematic research on the application of chloroaluminate ionic liquids as solvents was performed in 1980s. However, ionic liquids based on aluminium halides are moisture sensitive. During the last decade an increasing number of new ionic liquids have been prepared and used as solvents. The general aim of this paper was to review the physical and chemical properties of RTILs from the point of view of their possible application as electrolytes in electrochemical processes and devices. The following points are discussed: melting and freezing, conductivity, viscosity, temperature dependence of conductivity, transport and transference numbers, electrochemical stability, possible application in aluminium electroplating, lithium batteries and in electrochemical capacitors.     

A Thermo-Mechanical Study of Some Epoxy Adhesives Subjected to Combined Dynamic and Static Stresses

The object of the present study was to investigate the effect of superimposed dynamic and static stresses on mechanical and thermal properties of some epoxy adhesives. It was found that combinations of shear creep and torsional oscillations, applied simultaneously to adhesive joints at temperatures within the glassy range of the adhesive, led to strengthening of the joints in shear and to an increase in the glass transition temperature of the adhesive. Similar loading stresses applied at temperatures close to the T_g of the adhesive, led to opposite effects on the above mentioned properties of the joints. The width of the glassy-rubbery transition of the adhesives increased, in the whole range of temperatures used in this study and for all epoxy compositions, as a result of subjecting the joints to superimposed dynamic and static stresses. The broadening of the glass transition was interpreted as a result of the stiffening of polymer network during the combined stressing experiments. A linear relationship was found between the area of endothermal peaks in the first DSC scan of specimens subjected prior to test to superimposed dynamic and static stresses at temperatures below T_g, and the shear strength of the joints. In agreement with this observation and with literature data, a linear relationship was revealed also between the glass transition temperature of the resins (measured in the first DSC scan) and the shear strength of the joints. Based on experimental observations and on some literature information, it was suggested that the strengthening of the joint, as well as the changes in thermal properties of the adhesives, are mainly due to physical processes, such as short-range orientation of network chains and an increase in intermolecular interaction between highly polar sites of the network. The possibility that superimposed stressing led to changes in chemical crosslinking was discussed but it seems that no such reactions occurred.     

Ultrahigh performance of Ti-based glassy alloy tube sensor for Coriolis mass flowmeter

Bulk metallic glasses （BMGs） have potential applications for both structural and functional components owing to their good mechanical properties. With the aim of demonstrating great engineering value of BMGs, a direct melt-forming technique based on suction casting for the production of glassy alloy tubes was developed. The fabrication, structure, geometry, properties and sensor performance of the tubes were examined. The results show that the Coriolis mass flowmeters using the Ti-based glassy alloy sensor tube exhibit excellent measurement sensitivity, viz. 28.5 times higher than that of the conventional flowmeter manufactured using stainless steel （SUS316） tube.     

鸟嘌呤和8-羟基脱氧鸟嘌呤核苷在聚甘氨酸修饰电极上的电化学行为及其同时测定

在优化的实验条件下,利用电化学方法制备了甘氨酸修饰电极,对修饰膜的电活性进行了表征.用循环伏安法研究了鸟嘌呤(G)和8一羟基脱氧鸟嘌呤核苷(8-OH-dG)在聚甘氨酸修饰电极上的电化学行为,并建立了对两者进行分别检测和同时检测的分析方法.实验结果表明,聚甘氨酸修饰电极可以增强鸟嘌呤和8-羟基脱氧鸟嘌呤核苷在电极表面的吸附,并且可以加快鸟嘌呤和8-羟基脱氧鸟嘌呤核苷在电极表面的电子传输,使两种电活性物质在聚甘氨酸修饰电极上的电化学信号明显增大,检测灵敏度大大提高,并且该修饰电极具有良好的稳定性和重现性.可用于鸟嘌呤和8-羟基脱氧鸟嘌呤核昔的分别和同时检测.     

Electrochemical determination of imidacloprid using nanosilver Nafion/nanoTiO2 Nafion composite modified glassy carbon electrode

A novel biocompatible environment friendly nanosilver Nafion^®/nanoTiO₂ Nafion^® modified glassy carbon electrode was prepared by a simple procedure and characterized. This modified electrode was used as a sensing electrode for the detection of imidacloprid. Cyclic voltammetry, differential pulse voltammetry and amperometry were used in this work. The reduction potential of imidacloprid on this electrode is lower compared to other electrodes reported in the literature. The LOD and LOQ values obtained for the sensing of imidacloprid on this modified electrode are comparable to the values reported in the literature.     

A label-free amperometric immunosensor based on horseradish peroxidase functionalized carbon nanotubes and bilayer gold nanoparticles

In this work, a novel label-free amperometric immunosensor has been constructed for detecting α-1-fetoprotein (AFP) based on nanocomposite of horseradish peroxidase (HRP) labeled carbon nanotubes (CNTs). First, the gold nanoparticles (AuNPs) were electrodeposited on the surface of the glass carbon electrode by electrochemical reduction of gold chloride tetrahydrate (HAuCl₄) to immobilize horseradish peroxidase labeled carbon nanotubes (HRP-CNTs). Then HRP-CNTs bioconjugate was immobilized on the surface of the electrodeposited AuNPs layer by the combination of forces (coordination and electrostatic force). Subsequently, it was immersed into gold colloidal nanoparticles (GNPs) solution, which was used to immobilize antibody biomolecules (anti-AFP). Enhanced sensitivity was obtained by using bioconjugates featuring HRP labeled (HRP-CNTs), which had lager specific surface area and good electronic catalysis (current response signal) compared to carbon nanotubes. Under optimized conditions, the linear ranges were from 0.2 to 200 ng mL⁻¹ with a detection limit of 0.067 ng mL⁻¹ (at an S/N of 3). The proposed immunosenor showed good precision, acceptable stability and reproducibility and could be used for the detection AFP in normal human serum, which provided a potential alternative tool for the detection of protein in clinical diagnosis.     

基于NaOH刻蚀玻碳电极的电化学传感器在检测膀胱癌DNA中的应用

制备了一种基于活化的玻碳电极的新型电化学DNA生物传感器,可用于膀胱癌DNA的检测.通过循环伏安法(CV)实现玻碳电极在NaOH溶液中的刻蚀,使电极表面负载大量官能团,为DNA提供连接位点,由Laviron方程计算得到玻碳电极表面的羧基浓度为 1.022×10-6 mol/cm2.亚甲基蓝(MB)作为电化学检测的杂交指示剂.采用原子力显微镜(AFM)对刻蚀后的电极进行了形貌表征.在最优杂交条件下,通过差分脉冲法(DPV)计算出最佳检测限为5.677×10-13 mol/L(n=5),适用目标 DNA浓度范围1×10-8 mol/L~1×10-12 mol/L.该传感器有望用于实际样品中膀胱癌DNA的快速检测.     

2,4,6-三氨基嘧啶在玻碳电极上的电化学行为

用线性扫描伏安法 (LSV)、循环伏安法 (CV)和微分脉冲伏安法 (DPV)等电化学手段研究了 2 ,4,6 三氨基嘧啶 (TAP)的电化学行为。结果表明 :该化合物在玻碳电极表面存在吸附特性 ,在 0 .1 0mol·L- 1 的 pH 5 .0Britton Robinson (B R)缓冲溶液中于1 .2 0V(vs.Ag/AgCl)处有一灵敏的氧化峰。在选定的最佳条件下 ,其浓度在 8.0× 1 0 - 6～ 3.2×1 0 - 4 mol·L- 1 范围内与氧化峰电流有良好的线性关系 ,检测限为 6.5× 1 0 - 6mol·L- 1 。