Synthesis of new thermosetting poly(2,6‐dimethyl‐1,4‐phenylene oxide)s containing epoxide pendant groups

A new class of thermosetting poly(2,6‐dimethyl‐1,4‐phenylene oxide)s containing pendant epoxide groups were synthesized and characterized. These new epoxy polymers were prepared through the bromination of poly(2,6‐dimethyl‐1,4‐phenylene oxide) in halogenated aromatic hydrocarbons followed by a Wittig reaction to yield vinyl‐substituted polymer derivatives. The treatment of the vinyl‐substituted polymers with m‐chloroperbenzoic acid led to the formation of epoxidized poly(2,6‐dimethyl‐1,4‐phenylene oxide) with variable pendant ratios, and the structures and properties were studied with nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and gel permeation chromatography. The ratios of pendant functional groups were tailored for the polymer properties, and the results showed that the glass‐transition temperatures increased as the benzylic protons were replaced by bromo‐, vinyl‐, or epoxide‐functional groups, whereas the thermal stability decreased in comparison with the original polymer. Within a molar fraction of 20–50%, the degree of functionalization had little effect on the glass‐transition temperature; however, it correlated inversely with the thermal stability of each functionalized polymer. The thermal curing behavior of the epoxide‐functionalized polymer was enhanced by the increment of the pendant functionality, which resulted in a significant increase in the glass‐transition temperature as well as the thermal stability after the curing reaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5875–5886, 2006     

Synthesis of poly(ethylene oxide) with pending 2,2,6,6‐tetramethylpiperidine‐1‐oxyl groups and its further initiation of the grafting polymerization of styrene

A new stratagem for the synthesis of amphiphilic graft copolymers of hydrophilic poly(ethylene oxide) as the main chain and hydrophobic polystyrene as the side chains is suggested. A poly(ethylene oxide) with pending 2,2,6,6‐tetramethylpiperidine‐1‐oxyls [poly(4‐glycidyloxy‐2,2,6,6‐tetramethylpiperidine‐1‐oxyl‐co‐ethylene oxide)] was first prepared by the anionic ring‐opening copolymerization of ethylene oxide and 4‐glycidyloxy‐2,2,6,6‐tetramethylpiperidine‐1‐oxyl, and then the graft copolymerization of styrene was completed with benzoyl peroxide as the initiator in the presence of poly(4‐glycidyloxy‐2,2,6,6‐tetramethylpiperidine‐1‐oxyl‐co‐ethylene oxide). The polymerization of styrene was under control, and comblike, amphiphilic poly(ethylene oxide)‐g‐polystyrene was obtained. The copolymer and its intermediates were characterized with size exclusion chromatography, ¹H NMR, and electron spin resonance in detail. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3836–3842, 2006     

Effects of the architecture and environment on polymeric molecular assemblies of novel amphiphilic diblock copolynorbornenes with narrow polydispersity via living ring‐opening metathesis polymerization

Diblock copolymers of 5‐(methylphthalimide)bicyclo[2.2.1]hept‐2‐ene (NBMPI) and 1,5‐cyclooctadiene were synthesized by living ring‐opening metathesis polymerization with a well‐defined catalyst {RuCl₂(CHPh)[P(C₆H₁₁)₃]₂}. Unhydrogenated diblock copolymers showed two glass transitions due to poly(NBMPI) and polybutadiene segments, such as two glass‐transition temperatures at ?86.5 and 115.3 °C for poly 1a and ?87.2 and 115.3 °C for poly 1b . However, only one melting temperature could be observed for hydrogenated copolymers, such as 119.8 °C for poly 2a and 121.7 °C for poly 2b . The unhydrogenated diblock copolymer with the longer poly(NBMPI) chain (poly 1a ; temperature at 10% mass loss = 400 °C) exhibited better thermal stability than the one with the shorter poly(NBMPI) chain (poly 1b ; temperature at 10% mass loss = 385 °C). Two kinds of hydrogenated diblock copolymers, poly 2a and poly 2b , exhibited relatively poor solubility but better thermal stability than unhydrogenated diblock copolymers because of the polyethylene segments. Poly[(hydrochloride quaternized 2‐norbornene‐5‐methyleneamine)‐b‐butadiene]‐1 (poly 3a ) was obtained after the hydrolysis and quaternization of poly 1a . Dynamic light scattering measurements indicated that the hydrodynamic diameters of the cationic copolymer (poly 3a ) in water (hydrodynamic diameter = 1580 nm without salt), methanol/water (4/96 v/v; hydrodynamic diameter = 1500 nm without salt), and tetrahydrofuran/water (4/96 v/v; hydrodynamic diameter = 1200 nm without salt) decreased with increasing salt (NaCl) concentration. The effect of temperature on the hydrodynamic diameter of hydrophobically modified poly 3a was also studied. The inflection point of the hydrodynamic diameter of poly 3a was observed at various polymer concentrations around 30 °C. The critical micelle concentration of hydrophobically modified poly 3a was observed at 0.018 g dL^?1. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2901–2911, 2006     

Mechanical endurance of polymer electrolyte membrane and PEM fuel cell durability

The life of proton exchange membrane fuel cells (PEMFC) is currently limited by the mechanical endurance of polymer electrolyte membranes and membrane electrode assemblies (MEAs). In this paper, the authors report recent experimental and modeling work toward understanding the mechanisms of delayed mechanical failures of polymer electrolyte membranes and MEAs under relevant PEMFC operating conditions. Mechanical breach of membranes/MEAs in the form of pinholes and tears has been frequently observed after long‐term or accelerated testing of PEMFC cells/stacks. Catastrophic failure of cell/stack due to rapid gas crossover shortly follows the mechanical breach. Ex situ mechanical characterizations were performed on MEAs after being subjected to the accelerated chemical aging and relative humidity (RH) cycling tests. The results showed significant reduction of MEA ductility manifested as drastically reduced strain‐to‐failure of the chemically aged and RH‐cycled MEAs. Postmortem analysis revealed the formation and growth of mechanical defects such as cracks and crazing in the membranes and MEAs. A finite element model was used to estimate stress/strain states of an edge‐constrained MEA under rapid RH variations. Damage metrics for accelerated testing and life prediction of PEMFCs are discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2346–2357, 2006     

Preparation and Characterization of a Cobalt‐Containing Mono‐Phosphine Ligand and its Coordinated Molybdenum Complex

A cobalt‐containing monodentate phosphine [(μ₂‐PPh₂CH₂PPh₂‐κ²P)Co₂(CO)₄][μ₂‐η²‐PhC≡CP(i‐Pr)₂] 2f , was prepared from the reaction of (μ₂‐PPh₂CH₂PPh₂‐κ²P)Co₂(CO)₆ 1 with PhC≡CP(i‐Pr)₂. It was accompanied by an oxidized compound, [(μ₂‐PPh₂CH₂PPh₂‐κ²P)Co₂(CO)₄][μ₂‐η²‐PhC≡CP(=O)(i‐Pr₂)] 2fo during the chromatographic process. Further reaction of 2f with Mo(CO)₆ resulted in the formation of a 2f ‐ligated molybdenum complex 4 , [(μ₂‐PPh₂CH₂PPh₂‐κ²P)Co₂(CO)₄][μ₂‐η²‐PhC≡CP(i‐Pr₂)‐κP]‐Mo(CO)₅.     

聚甲基丙烯酸甲酯掺杂Ce3+的飞秒激光三维信息存储

用飞秒激光(200 fs,1 kHz,800 nm)脉冲在掺杂稀土离子Ce3 的聚甲基丙烯酸甲酯(PMMA)膜中进行了光存储实验研究,包括对样品的吸收光谱、激光照射前后的电子旋转共振(Electron spin resonance,ESR)光谱的测量和讨论。结果表明掺杂稀土离子Ce3 的聚甲基丙烯酸甲酯膜具有较低的写入阈值,有利于高速、并行的三维光存储。实验结果采用传统光学显微镜并行读出。给出了四层存储结果(点间距和层间距分别是4μm和16μm),并讨论了脉冲能量的大小对空腔尺寸的影响,进行高密度存储时,在保证读出信号灰度值足够大的情况下,应选择尽量小的激光脉冲写入能量。实验结果表明这种材料可以应用于三维光信息存储。     

短路过渡电弧焊电流信号的近似熵分析

依据近似熵的理论和算法，从非线性角度对纯CO₂保护气体条件下短路过渡电弧焊的电流信号进行了近似熵分析.通过对不同的送丝速度、给定电压及气体流量下电流信号的近似熵计算和比较，表明近似熵可以作为短路过渡稳定性的评判标准.近似熵越大，波动越小，焊接过程就越稳定. 关键词： 非线性 近似熵 短路过渡 稳定性     

Synthesis of double silylene-bridged binuclear titanium complexes and their use as catalysts for ethylene polymerization

Five new double silylene-bridged binuclear titanium complexes were synthesized by the reaction of RCpTiCl₃ and Li₂[μ,μ-(SiMe₂)₂ (C₅H₃)₂] in toluene. They were all well characterized. These complexes activated with methylaluminoxane (MAO) are highly active catalysts (2.33 × 10⁵ g PE/mol Cat h) for the polymerization of ethylene even at low Al/Ti (Al/Ti = 300). The molecular weight distribution of the polymer indicates broad or bimodal (MWD = 26.76) distribution.     

Investigation on the barrier height and inhomogeneity of nickel silicide Schottky

The apparent Schottky barrier height (SBH) of the nickel silicide Schottky contacts annealed at different temperatures was investigated based on temperature dependence of I-V characteristic. Thermionic emission-diffusion (TED) theory, single Gaussian and double Gaussian models were employed to fit I-V experimental data. It is found the single Gaussian and double Gaussian SB distribution model can give a very good fit to the I-V characteristic of apparent SBH for different annealing temperatures. Also, the apparent SBH and the leakage current increase with annealing temperatures under reverse voltage. In addition, the homogeneity of interfaces for the samples annealed at temperatures of 500 and 600 °C is much better than that of the samples annealed at temperatures of 400, 700, and 800 °C. This may result from the phase transformation of nickel silicide due to the different annealing temperatures and from the low Schottky barrier (SB) patches.     

微量元素制剂辅助治疗复发性口疮疗效观察

报道了１０３例ＲＡＵ患者使用微量元素制剂辅助治疗的临床疗效观察。将两个实验组分别与对照组比较。结果显示：应用锌、铁制剂辅助雷公藤、复方丹参等治疗的实验组Ｉ效果优于雷公藤、复方丹参对照组（Ｐ〈０．０１），而仅用锌、铁制剂治疗的实验组Ⅱ临床效果比对照组差（Ｐ〈０．０１），但锌、铁制剂有改善ＲＡＵ临床症状作用，而不能较好地控制其复发。