Permeability of N2, Ar,He, O2, and CO2 through as‐extruded amorphous and biaxially oriented polyester films: Dependence on chain mobility

For as‐extruded amorphous and biaxially orientated polyester films based on poly(ethylene terephthalate), poly(ethylene naphthalate), and copolymers containing poly(ethylene terephthalate) and poly(ethylene naphthalate) moieties, permeability, diffusion, and solubility coefficients are interpreted in terms of chain mobility. The influence of polymer morphology is determined by comparison of the data for as‐extruded amorphous sheets and materials produced with different biaxial draw ratios. The crystallinities of the samples were assessed using differential scanning calorimetry and density measurements. Changes in mobility at a molecular level were investigated using dielectric spectroscopy and dynamic mechanical thermal analysis. The study, in conjunction with our earlier work, leads to the conclusion that the key to understanding differences in gas transport is the difference in local chain motions rather than in free volume. This was illustrated by the permeability results for He, Ar, N₂, and O₂ in the range of polyesters. However, the permeability of CO₂ was found to require alternative explanations because of polymer–penetrant interactions. For biaxially oriented samples, the differences in diffusivity are not only due to differences in local chain motions, but also additional constraints resulting from the increased crystallinity and chain rigidity—which also act to hinder segmental mobility. The effectiveness of the reduction in permeability in the biaxially oriented films is consequently determined by the ability of the polymer chains to effectively align and form crystalline structures. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2916–2929, 2004     

Viscosity,particle size distribution,and structural investigation of tetramethyloxysilane/2‐hydroxyethyl methacrylate sols during the sol–gel process with acid and base catalysts

The tetramethoxysilane (TMOS)/2‐hydroxylethyl methacrylate (HEMA) hybrid gels were synthesized with acid and base catalysts, via the in situ polymerization of HEMA, with and without the cosolvent methanol. With methanol in the TMOS/HEMA sol, the enhanced esterification and depolymerization reactions of the silanols resulted in a slower growth of silica particles. The silica particles that were synthesized with an acid catalyst were less than 40 nm. The thermal resistance of the poly(2‐hydroxyethyl methacrylate) (PHEMA) chains was enhanced by the addition of colloidal silica. The Fourier transform infrared characterizations and the exothermal peaks on the differential scanning calorimetry traces of these hybrid gels indicated chemical hybridization occurring as a result of condensation of the colloid silica and PHEMA at higher temperatures. Hence, the residual weight content of the hybrid gel after its synthesis with the base catalyst was even higher than the content of TMOS in the hybrid sol. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3476–3486, 2004     

Electrochemical determination of serotonin and the competitive adsorption with dopamine at 5,5-ditetradecyl-2-(2-trimethylammonioethyl)-1,3-dioxane bromide lipid film modified by glassy carbon electrode.

A novel and effective approach to sensitively determine serotonin, known as 5-hydroxytryptamine (5-HT), has been proposed based on a 5,5-ditetradecyl-2-(2-trimethylammonioethyl)-1,3-dioxane bromide (DTDB) self-assembled lipid bilayer membrane modified glassy carbon electrode (DTDB/GCE). A DTDB/GCE shows the strong electrocatalysis for the oxidation of 5-HT, with the peak potential shifted to less positive value of 0.376 V vs. SCE, and effectively eliminates the interference from ascorbic acid (AA), even in the presence of 100-fold concentration of AA. Differential pulse voltammetry (DPV) gave a linear current for 5-HT from 2.0 x 10(-7) to 1.0 x 10(-5) M. At the DTDB/GCE, the oxidation of 5-HT was controlled by the adsorption process; for 5-HT coexisting with DA, the competitive adsorption was observed.     

Novel fixed‐site–carrier polyvinylamine membrane for carbon dioxide capture

Fixed‐site–carrier membranes were prepared for the facilitated transport of CO₂ by casting polyvinylamine (PVAm) on various supports, such as poly(ether sulfone) (PES), polyacrylonitrile (PAN), cellulose acetate (CA), and polysulfone (PSO). The cast PVAm on the support was crosslinked by various methods with glutaraldehyde, hydrochloric acid, sulfuric acid, and ammonium fluoride. Among the membranes tested, the PVAm cast on polysulfone and crosslinked by ammonium fluoride showed the highest selectivity of CO₂ over CH₄ (>1000). The permeance of CO₂ was then measured to be 0.014 m³ (STP)/(m² bar h) for a 20 μm thick membrane. The effect of the molecular weight of PVAm and feed pressure on the permeance was also investigated. The selectivity increased remarkably with increasing molecular weight and decreased slightly with increased pressure in the range of 1 to 4 bar. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4326–4336, 2004     

Pressure and temperature dependence of the gas‐transport properties of dense poly[2,6‐toluene‐2,2‐bis(3,4‐dicarboxylphenyl)hexafluoropropane diimide] membranes

The gas‐transport properties of poly[2,6‐toluene‐2,2‐bis(3,4‐dicarboxylphenyl)hexafluoropropane diimide] (6FDA‐2,6‐DAT) have been investigated. The sorption behavior of dense 6FDA‐2,6‐DAT membranes is well described by the dual‐mode sorption model and has certain relationships with the critical temperatures of the penetrants. The solubility coefficient decreases with an increase in either the pressure or temperature. The temperature dependence of the diffusivity coefficient increases with an increase in the penetrant size, as the order of the activation energy for the diffusion jump is CH₄ > N₂ > O₂ > CO₂. Also, the average diffusion coefficient increases with increasing pressure for all the gases tested. As a combined contribution from sorption and diffusion, permeability decreases with increases in the pressure and the kinetic diameter of the penetrant molecules. Even up to 32.7 atm, no plasticization phenomenon can be observed on flat dense 6FDA‐2,6‐DAT membranes from their permeability–pressure curves. However, just as for other gases, the absolute value of the heat of sorption of CO₂ decreases with increasing pressure at a low‐pressure range, but the trend changes when the feed pressure is greater than 10 atm. This implies that CO₂‐induced plasticization may occur and reduce the positive enthalpy required to create a site into which a penetrant can be sorbed. Therefore, a better diagnosis of the inherent threshold pressure for the plasticization of a glassy polymer membrane may involve examining the absolute value of the heat of sorption as a function of pressure and identifying the turning point at which the gradient of the absolute value of the heat of sorption against pressure turns from a negative value to a positive one. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 354–364, 2004     

Relationship between the dynamic softening transition and wet sliding friction of elastomer compounds

For properly chosen elastomer compounds, thermorheological characterization is combined with an examination of the variation of the wet sliding friction with temperature. A conceptual argument leads to the assumption that the wet sliding friction should maximize at the energy dissipation peak associated with the dynamic softening transition at a characteristic frequency determined by the sliding speed and the effective smallest surface asperity scale. The dynamic softening transition is characterized with the peak in tan δ/G′ⁿ, where tan δ is the loss tangent, G′ is the elastic modulus, and n is a constant between 0 and 1. The William–Landel–Ferry transform is uncritically applied for extrapolating the position of the peak in tan δ/G′ⁿ at high frequencies. Even based on the criterion of tan δ, the results obtained on a concrete surface indicate that the effective smallest asperity scale is of order of 100 μm. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2467–2478, 2004     

Differential scanning calorimetry and thermogravimetric analysis investigation of the thermal properties and degradation of some radiation‐grafted films and membranes

The influence of irradiation and grafting on the crystallinity of three base polymers has been investigated with differential scanning calorimetry. Grafting has the largest effect on the base polymer crystallinity and results in a reduction of the crystallinity. The thermal degradation of the base polymers and grafted films has been investigated with thermogravimetric analysis. The extent of the fluorination of the base polymer, the irradiation method, and the graft level all influence the thermal degradation and its activation energy. It is proposed that the variation of the chain lengths of the grafted polystyrene chains is actually a primary underlying factor responsible for the influence of these various parameters on the degradation process. The first results of a comparative thermal analysis of some fuel‐cell membranes are also presented, and the promise and shortcomings of this method are discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2612–2624, 2004     

Structure,morphology, and crystallization process of isotactic polypropylene/hydrogenated hydrocarbon resin blends

The structure, morphology, and isothermal and nonisothermal crystallization of isotactic polypropylene/low‐molecular‐mass hydrocarbon resin blends (iPP/HR) (up to 20% in weight of HR) have been studied, using optical and electron microscopy, wide‐ and small‐angle X‐ray and differential scanning calorimetry. New structures and morphologies can be activated, using appropriate preparation and crystallization conditions and blend composition. For every composition and crystallization condition, iPP crystallizes in α‐form, with a spherulitic morphology. The size of iPP spherulites increases with resin content, whereas the long period decreases. In the range of crystallization temperatures investigated, HR modifies the birefringence of iPP spherulites, favoring the formation of radial lamellae and changing the ratio between tangential and radial lamellae. Spherulitic radial growth rates, overall crystallization rates, and melting temperatures are strongly affected by resin, monotonically decreasing with resin content. This confirms miscibility in the melt between the two components of the blends. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3368–3379, 2004     

高功率LDA紧密侧面抽运Nd:YLF两级双程离轴放大系统实验研究

 介绍了一台10mm口径两级双程离轴放大系统，实现了对5mm×5mm口径光束的激光放大，耦合系统采用高功率LDA紧密侧面直接抽运棒状Nd:YLF方式。分析并实验研究了在不同抽运电流、放大脉冲与放大器LDA抽运时刻的不同延时及不同注入能量条件下，放大系统及光束每次放大时放大特性的规律。实验得到：在放大系统5mm×5mm软光阑处注入1.58mJ能量时，放大系统可输出129.2mJ能量，能量提取效率达到19.5%，满足该系统的设计指标。     

光学非球面二次曲面常数及顶点曲率的研究

受光学非球面制造过程中诸工艺参数的影响,能否保证非球面顶点曲率及二次曲面常数的精度是一个重要问题。基于二次曲面方程,推导出确定光学非球面二次曲面常数k以及顶点曲率半径r的一组算法,并在对一块口径为760mm×200mm标准非球面反射镜的实际测算中进行拟合,经过优化,拟合精度达到Δk=0.015,Δr=0.341mm,从而有效的控制了光学非球面制造过程中的顶点曲率及二次曲面常数的偏差。