裂解气相色谱质谱法研究增塑剂邻苯二甲酸二甲酯的热降解机理

用裂解气相色谱-质谱联用方法研究了橡胶产品中使用的增塑剂邻苯二甲酸二甲酯(DMP)在不同温度条件下的热裂解行为.对不同温度条件下裂解产物的分析表明,在初始阶段DMP的裂解产物主要为二氧化碳、苯、甲苯和苯甲酸甲酯.随着温度的升高苯甲酸甲酯进一步裂解成为分子质量更小的自由基,并发生稠环化反应形成更稳定的菲、蒽、间-联三苯、三亚苯等芳香族多环化合物.根据分析实验提供的裂解产物信息和有机物热裂解化学反应的原理对DMP的热裂解反应机理作了探讨,表明在废旧合成橡胶热裂解回收过程中,增塑剂DMP的高温裂解会产生多环芳烃污染物.应选择合适裂解工艺和裂解温度,以减少对环境的污染.     

Comparative analysis of heterogeneous solid and soft materials by adsorption, NMR and thermally stimulated depolarisation current methods

Structural characterisation of such bio-objects as fibrinogen solution, yeast cells, wheat seeds and bone tissues has been done using two versions of cryoporometry based on the integral Gibbs-Thomson (IGT) equation for freezing point depression of pore liquids and the measurements by ¹H NMR spectroscopy (180-200 < T < 273 K) and the thermally stimulated depolarisation current (TSDC) method (90 < T < 273 K) of structured water. The IGT equation was solved using a self-consisting regularization procedure including the maximum entropy principle applied to the distribution function of pore size (PSD). Both methods give clear pictures of changes in the structural characteristics caused, e.g., by hydration and swelling of wheat seeds and yeast cells, coagulation and interaction of fibrinogen with solid nanoparticles in the aqueous media, and the human bone tissue disease.     

Influence of organic modifiers on morphology and crystallization of poly(ϵ‐caprolactone)/synthetic clay intercalated nanocomposites

ε‐caprolactone was polymerized in the presence of neat montmorillonite or organomontmorillonites to obtain a variety of poly(ε‐caprolactone) (PCL)‐based systems loaded with 10 wt % of the silicates. The materials were thoroughly investigated by different X‐ray scattering techniques to determine factors affecting structure of the systems. For one of the nanocomposites it was found that varying the temperature in the range corresponding to crystallization of PCL causes reversible changes in the interlayer distance of the organoclay. Extensive experimental and literature studies on this phenomenon provided clues indicating that this effect might be a result of two‐dimensional ordering of PCL chains inside the galleries of the silicate. Small angle X‐ray scattering and wide angle X‐ray scattering investigation of filaments oriented above melting point of PCL revealed that polymer lamellae were oriented perpendicularly to particles of unmodified silicate, while in PCL/organoclay systems they were found parallel to clay tactoids. Calorimetric and microscopic studies shown that clay particles are effective nucleating agents. In the nanocomposites, PCL crystallized 20‐fold faster than in the neat polymer. The crystallization rate in nanocomposites was also significantly higher than in microcomposite. Further research provided an insight how the presence of the filler affects crystalline fraction and spherulitic structure of the polymer matrix in the investigated systems. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2350–2367, 2007     

Andreev-Fano Effect in a Hybrid Normal-Metal/Superconductor Interferometer

We report on a new type of Fano effect, named as Andreev-Fano effect, in a hybrid normal-metal/supeeconductor (N/S) interferometer embedded with a quantum dot. Compared with the conventional Fano effect, AndreevFano effect has some new features related to the characteristics of Andreev reflection. In the Iinear response regime, the line shape is the square of the conventional Fano shape, while in the nonlinear transport, a sharp resonant structure is superposed on an expanded interference pattern, which is qualitatively different from the conventional Fano effect. The phase dependence of the hybrid N/S interferometer is also distinguished from those of all-N or all-S interferometers.     

A Tin(IV) Porphyrin with Two Axial Organometallic NCN‐Pincer Platinum Units

A tin(IV) porphyrin was combined with two axial NCN‐pincer platinum(II) fragments by utilizing the oxophilicity of the apical positions on the tin atom and the acidic nature of the NCN‐pincer platinum derived benzoic acid. The solid‐state structure determined by X‐ray crystallography revealed some close contacts between the pincer complexes and the meso‐p‐tolyl subsitutents of the porphyrin. It was shown by ¹H NMR spectroscopy that these close contacts were not present in solution and that this compound can potentially act as a novel building block for supramolecular architectures.     

Structure of norbornene-fused 3,1-oxazine double cycloadducts

Pentacyclic isoxazolines were obtained by the cycloaddition of benzonitrile oxide to norbornene-azetidinone-fused 3,1-oxazines. The constitutions of two of the isomers obtained, and the configurations and conformations of all products, were determined by means of ¹H and ¹³C NMR spectroscopy and DNOE experiments.     

Surface and interfacial properties of PVDF/acrylic copolymer blends before and after UV exposure

Morphological and chemical properties of both the surface and interface of poly(vinylidene fluoride)/poly(methyl methacrylate)-co-poly(ethyl acrylate) (PVDF/PMMA-co-PEA) blend films have been investigated before and after the samples were exposed to ultraviolet (UV) irradiation using a xenon arc lamp at 50 °C and 9% relative humidity (RH) for 7 months. Surface and interfacial morphologies were studied by atomic force microscopy (AFM). Chemical composition information was obtained by confocal Raman microscopy, attenuated total reflection-FTIR spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), and contact angle measurements. Results show an enrichment of the PVDF material at the air surface, while the acrylic copolymer enriches the interface. Blends having greater than 50% mass fraction of PVDF show little change in the surface morphology after UV exposure for 7 months. However, for a lower PVDF content, blends exhibit significant degradation of PMMA-co-PEA copolymer and a much rougher surface after UV exposure. Microstructural changes in the PVDF spherulites are also observed after UV degradation. It is found that the surface and interfacial morphologies are correlated with the chemical properties.     

一种基于能带工程设计的CaAsSb/InP异质结双极晶体三极管

异质结晶体三极管（HBT）的性能与其材料体系密不可分，利用能带工程可以大大优化器件的结构，提高器件性能，文章从分析HBT的能带结构及设计要求入手，介绍了一种利用能带工程设计的基于GaAsSb/InP材料体系的新型HBT器件的结构及其性能，分析了该器件与其它材料体系器件相比所具有的优异特性，说明了对HBT的各区材料，其带边的相对位置所起的重要作用，最后，文章还报道了近期的实验情况，说明了GaAsSb/InP体系HBT的实际性能与理论预言一致。