Pressure–volume–temperature data and surface tension of blends of poly(ethylene oxide) and poly(methyl acrylate) in the melt

The pressure–volume–temperature behavior of miscible blends of poly(ethylene oxide) (PEO) and poly(methyl acrylate) (PMA) was studied over extended ranges of temperature and pressure. From pressure–volume–temperature data, the reduction parameters for the Flory‐Orwoll‐Vrij equation‐of‐state were determined. It was found that reduction parameters as well as density, thermal expansion coefficient, and isothermal compressibility vary with composition in a nonlinear manner. The surface tension of the blends in the molten state was measured over the whole composition range using the sessile drop method. The surface tension was found to display negative deviation from additivity pointing toward a remarkable surface excess of PMA. Moreover, surface tension displays a minimum in the range of low PEO content at weight fraction of ～0.19. In addition, the temperature coefficient of surface tension shows negative deviation from linearity. It stays constant when PMA is in excess. Results are discussed in terms of equation‐of‐state thermodynamics. The minimum of surface tension can be well explained by weak self‐association of PEO in the bulk. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1893–1900, 2010     

MDYB-3有机玻璃在不同应变率下的一维屈服行为

对MDYB-3有机玻璃进行了多组不同应变率(10-3~3 000 s-1)下的压缩实验, 得到准静态下的屈服应力与动态下的峰值应力。沿其增强与面内2个方向进行准静态压缩实验, 以分析定向拉伸对屈服应力的影响, 修正了Ree-Eyring模型与Cooperative模型以描述定向有机玻璃的屈服行为。采用Johnson-Cook模型描述屈服后的黏塑性行为。结果表明Cooperative屈服模型比Ree-Eyring屈服模型更接近实验结果, 且能准确描述准静态屈服应力。动态压缩下的峰值应力为失效应力, 说明试样在1 500 s-1以上应变率下未达到屈服应力时已经发生破坏。Johnson-Cook模型对于单条曲线拟合良好, 但无法准确描述材料的应变率相关性。     

Fe2O3-PMMA复合纳米材料的制备及磁性和溶解性

溶胶-凝胶法;磁化率;Fe2O3纳米粒子;Fe2O3-PMMA复合纳米材料的制备及磁性和溶解性     

国产航空有机玻璃(PMMA)的非线性应力松弛行为研究

实验测定了国产航空有机玻璃PMMA在室温(20℃)、3—20.45％应变量范围内的应力松驰曲线。将用于表述中低应变率下加卸载循环的应力—应变行为的非线性本构理论,也即以考虑弹性和粘弹性变形的标准线性体和考虑塑性变形的活化粘壶作串联耦合的本构模型扩展应用到应力松弛状态,给出了相应的本构理论方程。对实验测得的应力松弛曲线进行数值拟合计算,吻合结果良好。表明所提出的本构模型也适用于描述PMMA的非线性应力松弛行为。得到了平衡态的应力一应变曲线,曲线的单调变化,表明不存在屈服极大值及以后的应变软化效应。     

Dynamic aspects of phase decomposition in reactive blends of polycarbonate and syndiotactic polymethyl methacrylate

Dynamics of phase separation in bisphenol-A polycarbonate (PC)/syndiotactic polymethyl methacrylate (sPMMA) blends has been investigated by means of time-resolved light scattering. Solvent-cast films of the PC/sPMMA blends were transparent, suggestive of miscible character. Several temperature jumps were carried out at a 50/50 PC/sPMMA composition from a homogeneous state (room temperature) into a two-phase regime. The process of phase separation first occurred for some considerable period, then it was followed by phase dissolution driven by chemical reaction. The thermodegradative reaction of sPMMA triggered the dissolution process by probably forming PC/sPMMA graft or random copolymers at the interface, which eventually resulted in a single phase. However, annealing at elevated temperatures for an extended period could lead to cross-linking, and thus a two-phase structure could be fixed permanently. The early stage of spinodal decomposition was interpreted in terms of the linearized Cahn-Hilliard theory. In the late stages of spinodal decomposition, the relationship between scattering peak wavenumber and time was found to obey a power law, but the exponents showed a strong dependence on temperature jumps. The temporal universal scaling failed due to the influence of the chemical reaction. © 1995 John Wiley & Sons, Inc.     

Structure-property relationships in a reactively coupled ductile matrix/brittle dispersed phase blend

Blends of t-butylaminoethyl methacrylate grafted polyethylene (PE-g-tBAEMA) with methyl methacrylate-methacrylic acid copolymer (PMMA-MAA) and polymethyl methacrylate (PMMA) were prepared in a Banbury type batch mixer. The effects of component proportions and processing conditions on the melt flow index, morphology, impact, and tensile properties of the resulting polymer blends were investigated. The interfacial chemical reaction was studied using Fourier transform infrared (FTIR) technique. It was observed that the melt index of the blends was reduced with increasing melt processing temperature and mixing time, indicating the formation of PE-g-PMMA block copolymer. New IR bands at 1554, 1628, 1800, and 1019 cm^?1 were observed only for PE-g-tBAEMA/PMMA-MAA, the reactive blends, but not for PE-g-tBAEMA/PMMA, the nonreactive blend. These IR bands were attributed to the amide, carboxylate anion and methacrylimide formation resulting from the chemical reaction between the secondary amine on the PE-g-tBAEMA/PMMA moiety and the carboxylic acid on PMMA-MAA segment. The morphology of the blends in various compositions was examined using scanning electron microscopy (SEM) and related to their mechanical properties. All of the blends have a domain structure whose morphology is strongly dependent on the concentration of the dispersed phase. Furthermore, the PE-g-tBAEMA/PMMA-MAA reactive blends were shown to have much finer morphology than the corresponding nonreactive blends. For the reactive polymer blends consisting of brittle particles dispersed in the ductile matrices, the PE-g-tBAEMA/PMMA-MAA, impact and tensile result higher than predicted by the additivity rule were observed. The toughening of polyethylene by PMMA was explained by a “cold-drawing” mechanism. The Young's modulus of the blends and the extent of interfacial adhesion were analyzed with Takayanagi and Sato-Furukawa's theories. © 1993 John Wiley & Sons, Inc.     

三维大孔TiO2光催化剂的制备及其催化性能

 以聚甲基丙烯酸甲酯微球为模板,以钛酸正丁酯为原料,采用溶胶-凝胶法制备了具有三维结构的大孔TiO2. 采用差示扫描量热、热重-微分热重、X射线衍射、红外光谱、扫描电子显微镜和氮气吸附等手段对样品进行了表征. 结果表明,高温热处理后得到的三维大孔TiO2光催化剂的孔径为200 nm左右,孔径分布均匀, TiO2纳米晶粒中锐钛矿相和金红石相的含量分别为82%和18%. 光催化氧化实验表明,此种三维结构的TiO2对甲基橙溶液具有较好的光催化氧化性能.     

A sensitive solid-phase fluoroimmunoassay for detection of opiates in urine

An automated flow fluorometer designed for kinetic binding analysis was adapted to develop a solid-phase competitive fluoroimmunoassay for urinalysis of opiates. The solid phase consisted of polymer beads coated with commercial monoclonal antibodies (MAbs) raised against morphine. Fluorescein-conjugated morphine (FL-MOR) was used as the fluorescein-labeled hapten. The dissociation equilibrium constant (K _D ) for the binding of FL-MOR to the anti-MOR MAb was 0.23 nM. The binding of FL-MOR to the anti-MOR MAb reached steady state within minutes and was displaced effectively by morphine and other opiates. Morphine-3-glucuronide (M3G), the major urinary metabolite of heroin and morphine, competed effectively with FL-MOR in a concentration-dependent manner for binding to the antimorphine MAb and was therefore used to construct the calibration curve. The sensitivity of the assay was 0.2 ng/mL for M3G. The assay was effective at concentrations of M3G from 0.2 to 50 ng/mL, with an IC₅₀ of 2 ng/mL. Other opiates and heroin metabolites that showed >50% crossreactivity when present at 1 μg/mL included codeine, morphine-6-glucuronide, and oxycodone. Methadone showed very low crossreactivity (<5%), which is a benefit for testing in patients being treated for opiate addictions. The high sensitivity of the assay and the relatively high cutoff value for positive opiate tests allows very small sample volumes (e.g., in saliva or sweat) to be analyzed. A double-blind comparison using 205 clinical urine samples showed good agreement between this single-step competitive assay and a commercially performed enzyme multiplied immunoassay technique for the detection of opiates and benzoylecgonine (a metabolite of cocaine).     

Dispersion polymerization of methyl methacrylate: Mechanism of particle formation

The mechanism for the formation of micron-size polymer particles in the dispersion polymerization of methyl methacrylate was investigated by applying dynamic light scattering to monitor the evolution of the average particle size in the early stages of the polymerization. In addition, the contributions of physically adsorbed stabilizer and graft copolymer were evaluated by measuring the bound, unbound (adsorbed), and free stabilizer, and by determining the amount of added stabilizer required in seeded dispersion polymerizations. Twenty nanometer particles (termed nuclei) were the smallest particles detected and are considered to be formed by aggregation of growing polymer chains precipitating from solution as they exceed their critical chain length. Aggregation of these nuclei with themselves and their aggregates continues until mature and stable particles are formed. This occurs when sufficient stabilizer occupies the particle surface which includes both the polymeric stabilizer [poly(vinylpyrrolidone)] and its graft copolymer which is created in situ. The effects of process variables are discussed based on this mechanistic picture of the dispersion polymerization process. © 1994 John Wiley & Sons, Inc.     

富勒烯在溶液和有机玻璃薄膜中的吸收光谱研究

利用在甲苯中溶解富勒烯与有机玻璃（ＰＭＭＡ）的方法，我们分别制得了掺Ｃ６０以及掺Ｃ７０有机玻璃薄膜．分别研究了Ｃ６０和Ｃ７０在溶液、有机玻璃薄膜两种不同状态下的吸收光谱，实验结果表明：有机玻璃这种固态环境对富勒烯的吸收特性影响很小，富勒烯在有机玻璃薄膜中的吸收曲线同在溶液状态时基本相同．Ｃ６０在有机玻璃薄膜中的吸收峰相对于溶液中峰位略有红移，但Ｃ７０的情况则刚好相反，它在前者的吸收峰相对于后者峰位蓝移，分析了产生这种现象的原因