Cu-MgF2复合纳米金属陶瓷薄膜的电导特性研究

用射频磁控共溅射法制备了Cu体积分数分别为 10 % ,15 % ,2 0 %和 3 0 %的Cu MgF2 复合金属陶瓷薄膜 .用x射线衍射、x射线光电子能谱和变温四引线技术对薄膜的微结构、组分及电导特性进行了测试分析 .微结构分析表明 :制备的Cu MgF2 复合薄膜由fcc Cu晶态纳米微粒镶嵌于主要为非晶态的MgF2 陶瓷基体中构成 ,Cu晶粒的平均晶粒尺寸随组分增加从 11 9nm增至 17 8nm .5 0— 3 0 0K温度范围内的电导测试结果表明 :当Cu体积分数qM 由 15 %增加到 2 0 %时 ,Cu MgF2 复合薄膜的电阻减小了 8个量级 ,得出制备的复合薄膜渗透阈qCM 应处于 15 %和 2 0 %之间 .qM 在 10 %和 15 %之间的薄膜呈介质导电状态 ,而在 2 0 %和 3 0 %之间的薄膜则呈金属导电状态 .从理论上讨论了复合薄膜中杂质电导和本征电导的激活能及其对电导的贡献 ,并讨论了Cu MgF2 复合纳米金属陶瓷薄膜的渗透阈 ,得到了和实验一致的结果     

The fabrication and characterization of poly(lactic acid) scaffolds for tissue engineering by improved solid–liquid phase separation

In this article a new technique was developed to fabricate scaffolds with a unique microstructure by solid–liquid separation in combination with particulate-leaching. Firstly, the effects of polymer concentration, quenching temperature on the porous morphology and the mechanical property of obtained scaffolds during solid–liquid separation have been investigated. Then, salt granules as porogen were introduced into the solid–liquid phase separation to produce the unique pore structure of the scaffold. The pore diameter of the scaffold could be controlled with the particulate size and the wall of pores possessed special microstructure, which enhanced the pore interconnectivity. The cell culture results confirmed that a good interconnectivity of the scaffold prepared by the improved solid–liquid separation was useful for nutrition transportation and cell proliferation. Copyright © 2003 John Wiley & Sons, Ltd.     

Local chain‐configuration dependence of the mechanisms of the chemical reaction of poly(vinyl chloride). IX. Novel results on stereoselectivity of chlorination reaction

A poly(vinyl chloride) (PVC) sample was chlorinated in solution in the presence of 2,2′‐azobisisobutyronitrile and by the fluid‐bed method. The aim was to evaluate the scope of the stereoselectivity of the chlorination reaction. The quantitative microstructural analysis of the residual PVC with a degree of chlorination was followed by ¹³C NMR spectroscopy. From the evolution of the content of isotactic (mm), heterotactic (mr), and syndiotactic (rr) triads and of mmmm, mmmr, and rmmr isotactic pentads in the unchlorinated parts of the polymer, it was unambiguously inferred that the chlorination reaction proceeds by a stereoselective mechanism in that the mr heterotactic triads are the most reactive structures followed by the isotactic triad at mmmr and rmmr pentads. This conclusion was confirmed on the basis of the Fourier transform infrared results. The results provide valuable information regarding the effect of tacticity and related local conformations in the chemical reactions of PVC. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 508–519, 2003     

矿化剂和烧成温度对合成锆莫来石材料的显微结构与性能的影响

运用精细化工艺方法,选择适当的矿化剂,采用矾土生料和锆英石砂烧结合成锆莫来石材料,试验表明:引入矿化剂或提高烧成温度均可以促进锆英石的分解,加速固相反应和烧结的进行。1550℃保温2小时烧后的试样具有良好的显微结构和常温性能。     

Synthesis and characterization of functional gradient copolymers of allyl methacrylate and butyl acrylate

Functional spontaneous gradient copolymers of allyl methacrylate (A) and butyl acrylate (B) were synthesized via atom transfer radical polymerization. The copolymerization reactions were carried out in toluene solutions at 100 °C with methyl 2‐bromopropionate as the initiator and copper bromide with N,N,N′,N″,N″‐pentamethyldiethylenetriamine as the catalyst system. Different aspects of the statistical reaction copolymerizations, such as the kinetic behavior, crosslinking density, and gel fraction, were studied. The gel data were compared with Flory's gelation theory, and the sol fractions of the synthesized copolymers were characterized by size exclusion chromatography and nuclear magnetic resonance spectroscopy. The copolymer composition, demonstrating the gradient character of the copolymers, and the microstructure were analyzed. The experimental data agreed well with data calculated with the Mayo–Lewis terminal model and Bernoullian statistics, with monomer reactivity ratios of 2.58 ± 0.37 and 0.51 ± 0.05 for A and B, respectively, an isotacticity parameter for A of 0.24, and a coisotacticity parameter of 0.33. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5304–5315, 2006     

纤维双相钢的组织形成及对性能的影响

研究了纤维双相15Mn2Nb钢组织的形成及对性能的影响.结果表明,纤维双相钢具有优异的强塑性匹配,是一种天然的复合材料.其纤维组织的获取主要取决于合金化和热处理工艺规程,而合金元素Nb阻碍铁素体再结晶是形成纤维组织的关键.     

Synthesis of biodegradable copolymers with low‐toxicity zirconium compounds. V. Multiblock and random copolymers of L‐lactide with trimethylene carbonate obtained in copolymerizations initiated with zirconium(IV) acetylacetonate

Using zirconium(IV) acetylacetonate as an initiator of lactide/trimethylene carbonate copolymerization allowed us to obtain high‐molecular‐weight copolymers with high efficiency. The reactivity ratios of the comonomers were 13.0 for lactide and 0.53 for trimethylene carbonate. Despite the large differences between the values of the reactivity ratios, copolymers with randomized chain structures were obtained. This phenomenon occurred as a result of an intensive intermolecular transesterification process proceeding along with the reaction of copolymer chain growth and modifying its final structure. Conducting the copolymerization at the relatively low temperature of about 110 °C, which minimized the influence of intermolecular transesterification, made it possible to obtain semicrystalline copolymers with multiblock structures. Increasing the temperature of copolymerization up to 180 °C was associated with strong intensification of the transesterification reactions. At this temperature, amorphous copolymers were obtained with identical compositions but highly randomized chain structures. An analysis of the chain microstructures of the obtained copolymers, determining the average length of the blocks, the intermolecular transesterification ratio, and the degree of chain randomization, was conducted by means of NMR spectroscopy. For this purpose, very specific signal assignment in the carbonyl and methylene carbon regions of the ¹³C NMR spectra to appropriate comonomer sequences of polymeric chains was performed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3184–3201, 2006     

Synthesis of biodegradable copolymers with low‐toxicity zirconium compounds. IV. Copolymerization of glycolide with trimethylene carbonate and 2,2‐dimethyltrimethylene carbonate: Microstructure analysis of copolymer chains by high‐resolution nuclear magnetic resonance spectroscopy

The results of the copolymerization of glycolide with cyclic trimethylene carbonate and 2,2‐dimethyltrimethylene carbonate are described. The copolymerization was conducted in the presence of low‐toxicity zirconium(IV) acetylacetonate as an initiator. With this kind of initiator, the composition of the comonomer units in the copolymer chains was assumed to be obtained with high efficiency. Despite significant differences in the comonomer reactivity, in copolymers containing comparable amounts of glycolidyl and carbonate sequences, highly randomized chain structures were observed. This effect resulted from strong intermolecular transesterification that proceeded during the studied copolymerization and caused glycolidyl microblock randomization. The assignment of the spectral NMR lines to appropriate comonomer sequences of polymeric chains was performed in the region of methylene protons of glycolidyl units in ¹H NMR spectra of the copolymers and in the carbonyl region of carbon spectra. The equations were formulated for a detailed characterization of the obtained copolymer chains, the average lengths of the blocks, and the transesterification and randomization coefficients. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 98–114, 2006     

Synthesis of TiO2–SiO2/polymer core–shell microspheres with a microphase‐inversion method

A novel microphase‐inversion method was proposed for the preparation of TiO₂–SiO₂/poly(methyl methacrylate) core–shell nanocomposite particles. The inorganic–polymer nanocomposites were first synthesized via a free‐radical copolymerization in a tetrahydrofuran solution, and the poor solvent was added slowly to induce the microphase separation of the nanocomposite and result in the formation of nanoparticles. The average particle sizes of the microspheres ranged from 70 to 1000 nm, depending on the reaction conditions. Transmission electron microscopy and scanning electron microscopy indicated a core–shell morphology for the obtained microspheres. Thermogravimetric analysis and X‐ray photoelectron spectroscopy measurements confirmed that the surface of the nanocomposite microspheres was polymer‐rich, and this was consistent with the core–shell morphology. The influence of the synthetic conditions, such as the inorganic composition and the content of the crosslinking monomer, on the particle properties was studied in detail. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3911–3920, 2006     

铜发光中心的分布和位错显微结构的关系

本文作者根据显著观测和发光光谱的测试结果表证实了在ＺｎＳ：Ｃｕ单晶中，蓝色铜发光中心及绿色铜发光中心的分布和位错线区域的横向与纵向的显著与纵向的显著结构有着固定的对应关系。