The application of Raman spectroscopy to the tribology of polymers

This paper reviews the use of Raman spectroscopy for investigations in polymer tribology. In particular, a number of studies dealing with the problem of surface plasticisation in engineering polymers have been reported and are reviewed in this paper. Solvent and thermally-induced plasticisation have been examined using Raman spectroscopy. The polymers poly(ether ether ketone), nylon and polycarbonate have been investigated and are discussed here.     

Transient and steady‐state conduction in ethyl cellulose (EC)–poly(methyl methacrylate) (PMMA) blends

Transient discharging currents and steady‐state conduction in solution‐grown ethyl cellulose (EC)–poly(methyl methacrylate) (PMMA) blends measured as a function of temperature (30–80 °C) and field strength (10–100 kV cm⁻¹) are reported. Transient currents are found to follow the Curie–VonSchweidler law, characterized by different slopes in short‐ and long‐time regions, having different decay constant values lying between 0.75–0.99, and 1.68–1.95. The corresponding activation energies are found to increase with time of measurement of discharge current. Isochronal characteristics (ie current versus temperature plots at constant times) constructed from the data seem to reveal a broad peak observed at 60 °C. The dependence of dark current at different temperatures (30–80 °C) in a metal (1)–EC–PMMA blend–metal (1)/(2) system on the applied voltage in the range 10–100 kV cm⁻¹ has also been studied; the current is found to be strongly temperature dependent. Dipole polarization and space charge resulting from trapping of injected charge carriers in energetically distributed traps and induced dipoles created because of the piling up of charge carriers at the phase boundary of the heterogeneous components of the blend are considered to account for the observed transient currents. The results of current–voltage measurement on blends are interpreted to show that the low‐field steady‐state conduction is ohmic in nature, and in high fields the charge carriers are generated by field‐assisted lowering of coulombic barriers at the traps and are conducted through the bulk of the material by a hopping process between the localized states by a Jonscher–Ansari Poole–Frenkel mechanism. The modified P–F barrier is calculated to be 1.89 × 10⁻¹⁹ J (1.18 eV), 1.92 × 10⁻¹⁹ J (1.20 eV) and 1.95 × 10⁻¹⁹ J (1.22 eV) for P₁, P₂ and P₃ blends, respectively. © 2000 Society of Chemical Industry     

Electron‐beam processing of destructurized allylurea–starch blends: Immobilization of plasticizer by grafting

Allylurea (AU) was used as a reactive additive with poor aptitude to homopolymerization for obtaining grafted plasticized starch films with stabilized physical properties. Potato starch was mixed with AU (30–50 parts per hundred/pph) in a mixer operating at 125°C. Upon storage in well‐defined hygrothermal conditions, the resulting thermoplastic material shows strong plasticizer migration revealed by AU crystals blooming at the samples surface and exhibits strong opacity assigned to phase separation of the organic additive inside the material. Freshly prepared thermoplastic films of appropriate thickness were exposed to a 175‐kV electron beam (EB) radiation for inducing covalent grafting of AU by a free radical process. FTIR monitoring of the resulting chemical changes in thin films of AU–starch blends indicates unambiguously the transformation of AU allylic bond. High irradiation doses are required for achieving complete conversion of AU in the blend. However, no detectable AU migration was observed for intermediate AU conversion, probably as a consequence of higher plasticizer solubility in the grafted polysaccharide. Examination of the viscoelastic properties by dynamic mechanical thermal analysis shows that artificial aging by placing the films alternatively in high and low relative humidity (RH) atmosphere does not significantly alter the thermomechanical spectrum of the material reconditioned in a cell at 58% RH. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 409–417, 1999     

增塑剂对纤维素膜表面结构和性能的影响

天然纤维素膜不经任何处理直接干燥,膜发脆、卷曲,作用不大.采用甘油做增塑剂来改变纤维素膜的柔顺性,研究了不同的增塑条件对纤维素膜表面结构和性能的影响及甘油的塑化机理.通过力学性能测试、表面形态的观察及红外光谱分析,研究表明,甘油在一定程度上改变了纤维素膜的柔顺性,但同时却使纤维素膜的力学性能变差,并且增塑的膜经水洗后,甘油易流失,增塑效果减弱.     

Thermal and NMR Studies of Polystyrene Blends

Abstract

The effect of addition of poly (propylene oxide) (PPO) and polystyrene with low molecular weight (LPS) to polystyrene (PS) was investigated blending these polymers in a Haake internal mixer. The PPO and LPS range was established up to 10% by weight. The blends were analysed by differential scanning calorimetry (DSC) and carbon-13 nuclear magnetic resonance spectroscopy at solid state (NMR), using conventional NMR techniques as cross-polarisation/magic angle spinning (CP/MAS) and proton spin-lattice relaxation time in the rotating frame (T ₁ ^H _p ). The addition of 1 and 5% of PPO and 5% of LPS to PS made the blends of PS/PPO and PS/LPS more rigid.     

Thermoplastic Starch Processing and Characteristics—A Review

Canola Council of Canada, Winnipeg, Manitoba, Canada The rising costs of nonrenewable feedstocks and environmental concerns with their industrial usage have encouraged the study and development of renewable products, including thermoplastic starch (TPS). Starch is an abundant, plant-based biodegradable material with interesting physicochemical characteristics that can be exploited, and this has received attention for development of TPS products. Starch exhibits usable thermoplastic properties when plasticizers, elevated temperatures, and shear are present. The choice of plasticizer has an effect on TPS, even when these have similar plasticization principles. Most TPS have glass transition temperature, T_g, in the range of approximately ?75 to 10°C. Glassy transition of TPS is detected by differential scanning calorimeter (DSC) and thermodynamic analyzer (DMA), although DMA has been found to be more sensitive and effective. TPS has low tensile properties, typically below 6 MPa in tensile strength (TS). The addition of synthetic polymers, nanoclay, and fiber can improve TS and water-resistance ability. The moisture sorption behavior of TPS is described in GAB and BET models, from which monolayer moisture content and specific area are derived. Current studies on surface tension, gas permeability, crystallinity, and so on of the TPS are also reviewed.     

拉曼光谱在高分子中的应用新进展

综述了拉曼技术在高分子科学研究中近年来的最新进展 ,包括聚合物共混物的相容性、表面增塑机理、应力松弛和应变过程的监测以及拉曼成像、聚合反应监控、固化过程监测、聚合物结晶过程监控、聚合物水溶液和凝胶体系中水的结构及分子间、分子内相互作用力的研究。     

UPVC加工中的"诱导塑化”作用

揭示出在ＵＰＶＣ加工过程中存在“诱导塑化”作用,对产生“诱导塑化”的原因进行了精辟的分析,并指出在生产中如何把握好“诱导塑化”作用是至关重要的。     

超临界CO_2增强聚合物加工的研究与应用进展

对超临界CO2环境中聚合物加工方法的研究、应用现状与进展进行了综述。基于SC-CO2对聚合物的增塑作用,可开发出许多相关用途,如聚合物改性、聚合物共混、聚合物复合材料、多孔微泡沫材料、微粒化以及聚合物浸渍/灌注/插嵌等。在对研究现状和结果进行梳理总结后,认为SC-CO2对聚合物加工过程的增强作用机理可归结为:SC-CO2对聚合物的溶胀,导致增塑,进而降低了聚合物的玻璃化温度、黏度、表面张力,增强了小分子化合物在聚合基质中的扩散系数。此外,CO2作为绿色溶剂,是有机溶剂的良好替代品,因此具有广阔的应用前景。