Kinetic study of the crosslinking reaction of 1,2‐polybutadiene with dicumyl peroxide in the absence and presence of vinyl acetate

The crosslinking reaction of 1,2-polybutadiene (1,2-PB) with dicumyl peroxide (DCPO) in dioxane was kinetically studied by means of Fourier transform near-infrared spectroscopy (FTNIR). The crosslinking reaction was followed in situ by the monitoring of the disappearance of the pendant vinyl group of 1,2-PB with FTNIR. The initial disappearance rate (R₀) of the vinyl group was expressed by R₀ = k[DCPO]^0.8[vinyl group]^−0.2 (120 °C). The overall activation energy of the reaction was estimated to be 38.3 kcal/mol. The unusual rate equation was explained in terms of the polymerization of the pendant vinyl group as an allyl monomer involving degradative chain transfer to the monomer. The reaction mixture involved electron spin resonance (ESR)-observable polymer radicals, of which the concentration rapidly increased with time owing to a progress of crosslinking after an induction period of 200 min. The crosslinking reaction of 1,2-PB with DCPO was also examined in the presence of vinyl acetate (VAc), which was regarded as a copolymerization of the vinyl group with VAc. The vinyl group of 1,2-PB was found to show a reactivity much higher than 1-octene and 3-methyl-1-hexene as model compounds in the copolymerization with VAc. This unexpectedly high reactivity of the vinyl group suggested that an intramolecular polymerization process proceeds between the pendant vinyl groups located on the same polymer chain, possibly leading to the formation of block-like polymer. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4437–4447, 2004     

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     

Segmental and secondary dynamics in hydrogen‐bonded poly(4‐vinylphenol)/poly(methyl methacrylate) blends

Broadband dielectric spectroscopy was used to study the segmental (α) and secondary (β) relaxations in hydrogen‐bonded poly(4‐vinylphenol)/poly(methyl methacrylate) (PVPh/PMMA) blends with PVPh concentrations of 20–80% and at temperatures from ?30 to approximately glass‐transition temperature (T_g) + 80 °C. Miscible blends were obtained by solution casting from methyl ethyl ketone solution, as confirmed by single differential scanning calorimetry T_g and single segmental relaxation process for each blend. The β relaxation of PMMA maintains similar characteristics in blends with PVPh, compared with neat PMMA. Its relaxation time and activation energy are nearly the same in all blends. Furthermore, the dielectric relaxation strength of PMMA β process in the blends is proportional to the concentration of PMMA, suggesting that blending and intermolecular hydrogen bonding do not modify the local intramolecular motion. The α process, however, represents the segmental motions of both components and becomes slower with increasing PVPh concentration because of the higher T_g. This leads to well‐defined α and β relaxations in the blends above the corresponding T_g, which cannot be reliably resolved in neat PMMA without ambiguous curve deconvolution. The PMMA β process still follows an Arrhenius temperature dependence above T_g, but with an activation energy larger than that observed below T_g because of increased relaxation amplitude. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3405–3415, 2004     

二氟甲烷分子3a1和2b2轨道的电子动量谱

借助电子动量谱学结合量子化学理论和其他方法可以给出轨道电子在整个空间的分布信息,由此给出电子运动的完备描述[1,2 ] .清华大学电子动量谱学实验室近几年已成功地对甲烷[3] 、异丁烷[4 ] 、环戊烷[5] 、二乙酰等[6 ] 分子的轨道电子动量分布进行了测量.我们利用第二代电子动量谱仪首次对CH2 F2 分子3a1和2b2 轨道的电子动量谱进行测量,并与理论计算结果作了比较.同时还计算了坐标空间和动量空间中电子在x - y平面的密度分布.电子动量谱学最基本的过程是(e ,2e)反应,即电子与靶粒子碰撞而发生的电离过程.而对于(e ,2e)反应,含有大量信…     

二茂铁在高温热解乙二胺制备CN_x纳米管过程中的催化性能研究

采用高温热解法 ,以二茂铁 乙二胺有机溶剂为前驱液制备CNx 纳米管过程中 ,改变前驱液配比 ,对 86 0℃ ,不同二茂铁含量条件下制备出的CNx 纳米管进行了产量统计、形貌结构观察和拉曼光谱研究。结果显示 :随着前躯液中二茂铁含量的相对增大 ,不但CNx 纳米管产量随之增加 ,而且产物中“竹节状”结构纳米管相对“中空”结构纳米管的比重也增大 ;拉曼光谱结果进一步证实了由于“竹节状”结构CNx 纳米管的含量或比重增加所带来的纳米管样品整体或平均含氮量的升高而导致的样品结晶有序程度的降低。对单独钴粉和二茂铁催化条件下生成CNx 纳米管的形貌观察进一步证实 :二茂铁在热解法制备“竹节状”结构CNx 纳米管过程中的浮动催化作用显著 ,有利于实现含氮量较高、结构均匀的CNx 纳米管的可控制生长。     

含氮类金刚石薄膜的紫外辐照研究

 用射频等离子体方法在玻璃基底上制备的类金刚石（DLC）薄膜，采用离子注入法掺氮，并对掺氮DLC薄膜紫外（UV）辐照前后的性能变化进行了研究。研究结果表明：随氮离子注入剂量及UV辐照时间的增加，位于2 930cm^-1附近的SP ³C-H吸收峰明显变小，而位于1 580cm^-1附近的SP2C-H吸收峰则明显增强，薄膜的电阻率明显呈下降趋势；随UV辐照时间的增加，位于1 078cm^-1附近的Si-O-Si键数量及位于786cm^-1附近的Si-C键数量明显增加。即氮离子注入和UV辐照明显改变了DLC薄膜的结构与特性。     

Hydroxylation-induced modifications of the Al2O3/NiAl(0 0 1) surface at low water vapour pressure

STM, STS, LEED and XPS data for crystalline θ-Al₂O₃ and non-crystalline Al₂O₃ ultra-thin films grown on NiAl(0 0 1) at 1025 K and exposed to water vapour at low pressure (1 × 10⁻⁷-1 × 10⁻⁵ mbar) and room temperature are reported. Water dissociation is observed at low pressure. This reactivity is assigned to the presence of a high density of coordinatively unsaturated cationic sites at the surface of the oxide film. The hydroxyl/hydroxide groups cannot be directly identify by their XPS binding energy, which is interpreted as resulting from the high BE positions of the oxide anions (O_1s signal at 532.5-532.8 eV). However the XPS intensities give evidence of an uptake of oxygen accompanied by an increase of the surface coverage by Al³⁺ cations, and a decrease of the concentration in metallic Al at the alloy interface. A value of ∼2 for the oxygen to aluminium ions surface concentration ratio indicates the formation of an oxy-hydroxide (AlO_xOH_y with x + y ∼ 2) hydroxylation product. STM and LEED show the amorphisation and roughening of the oxide film. At P(H₂O) = 1 × 10⁻⁷ mbar, only the surface of the oxide film is modified, with formation of nodules of ∼2 nm lateral size covering homogeneously the surface. STS shows that essentially the valence band is modified with an increase of the density of states at the band edge. With increasing pressure, hydroxylation is amplified, leading to an increased coverage of the alloy by oxy-hydroxide products and to the formation of larger nodules (∼7 nm) of amorphous oxy-hydroxide. Roughening and loss of the nanostructure indicate a propagation of the reaction that modifies the bulk structure of the oxide film. Amorphisation can be reverted to crystallization by annealing under UHV at 1025 K when the surface of the oxide film has been modified, but not when the bulk structure has been modified.     

Heat-treatment studies of molybdenum oxide-monohydrate

The dehydration of molybdic acid, MoO₃---H₂O, was studied by thermal analysis, X-ray diffractometry and FTIR spectroscopy. The results show that an intermediate phase, MoO₃-2/3H₂O is formed at 216 °C and the monoclinic form of MoO₃ is grown above 350 °C. The mechanism of dehydration and structural rearrangement were confirmed by the features of the infrared spectra showing formation of corner-shared MoO₆ octahedra.     

Complementary spectroscopic techniques to model the association of contaminant uranium with structural surfaces

Contaminant uranium poses unique problems for decontamination of former weapons processing and nuclear power facilities, as well as chemical plants, waste storage sites and former mining facilities. In addition, dealing with the possibility of intentional (i.e., a terrorist act) or accidental release of radioactive material in a populated area requires an accurate understanding of the nature of the association of such material with structural surfaces. These surfaces must also be considered in the context of repeated contamination, and the importance of atmospheric exposure, interaction with other possible contaminants, and corrosion or surface degradation due to such exposure must be taken into account. Complementary spectroscopic techniques, especially surface spectroscopies, are essential in developing models for the interaction of contaminants with surfaces and interfaces. In this review (which also presents new data on uranium association with corroding steel surfaces), we collect models of this association as determined by spectroscopic techniques, assess the important considerations in the development of more accurate models, and address some of the questions which remain.