聚醚型聚氨酯增强增韧环氧树脂的研究

用聚丙二醇(PPG400,PPG1000)与异佛尔酮二异氰酸酯(IPDI)反应制备了聚氨酯(PU)预聚体,然后通过与环氧树脂(EP)的加成反应和环氧树脂的固化反应将聚氨酯引入环氧固化物网络,并研究了两种聚醚型聚氨酯对环氧树脂的改性效果。结果发现,聚氨酯的引入不但起到了增韧的作用,而且使体系的强度有了很大的提高。随聚氨酯用量增大,PU/EP材料拉伸强度、弯曲强度、冲击强度均先增大后减小,过多的聚氨酯用量导致其不能接人环氧固化物网络;分子链较短的PPG400型聚氨酯的改性效果优于PPG1000,PU与EP的质量之比的最佳值为15%～20%;1,4-丁二醇/三羟甲基丙烷的引入能够使体系中聚氨酯分子链增长并交联成网状,但并不能进一步提高PU/EP材料的强度和韧性。     

New approach for the preparation of nanoporous polyorganosilicate low‐k films

The distribution of pores and the mechanical properties of materials are the key factors in preparing satisfactory low‐k films. In the present study, a kind of silsesquioxane‐polyethylene glycol (SSQ‐PEG) was synthesized and used as a template to make the distribution of pores more even in the low‐k films. The crosslinking density of films could be adjusted by the sol‐gel of tetramethoxysilane/dimethoxydimethylsilane with various proportions. The porosity of films could also be adjusted with different proportions of pendant PEG chains introduced. A dielectric constant as low as 2.1 had been achieved for nanoporous polyorganosilicate films with good tenacity. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1238–1243, 2007     

Investigation on process parameters of electrospinning system through orthogonal experimental design

Electrospinning is a very simple and versatile method of creating polymer‐based high‐functional and high‐performance nanofibers. But most of the investigations are not systematic and describe the electrospinning process without quantitative accuracy. Inconsistent and even opposite results have been reported, which has hindered the consistent interpretation of the experiments. Orthogonal experimental method was used to investigate qualitative and quantitative correlations between fiber characteristics (diameters and morphologies) and the processing and materials parameters. Uniform fibers can be obtained without any beads by proper selection of the processing parameters, and a lower glass transition temperature was observed for electrospun fibers than that of native polymer. Results of statistical analysis showed that significant influences were observed for polymer molecular weight and solution concentration on fiber diameters, and there were significant effects of polymer molecular weight, solution concentration, and solvent system on fiber morphologies. Meanwhile, solution concentration and polymer molecular weight, and polymer molecular weight and solvent system had obvious interaction effects. Regression analysis revealed quantitative relations of fiber diameters and beads percent, that is, Y₁ = 72.8X₁ ? 8.1X₂ + 138.8, Y₂ = ?3.2X₁ + 0.4X₂ + 60.5, where Y₁ is fiber diameter (nm), Y₂ beads percent (%), X₁ solution concentration (%, w/w), and X₂ polymer molecular weight (kDa). Validation test showed that the experimental values of fiber size and beads percent were in good agreement with the calculated ones. Based on these results, optimal conditions could be obtained for predetermined diameters and morphologies for electrospun fibers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3105–3112, 2007     

Mechanism of the particle formation during the oxidative polymerization of 2,6‐dimethylphenol in an aqueous medium

The changes of the molecular weight and particle size with time during the oxidative polymerization of 2,6‐dimethylphenol in an aqueous medium were studied. At the beginning of the oxidative polymerization, the oligomers with the hydrophilic phenoxy anion at the end of oligomer chains are formed rapidly in the aqueous medium. When the molecular weight of the oligomer reaches up to a critical value, the oligomer precipitates out from the water, resulting in the formation of the original particle (or domain). With the increase of the molecular weight, the concentration of the phenoxy anion and the surface charge density of the original particles decrease; therefore, the repulsion force between original particles weaken and the stability of particles in water decreases, resulting in the coagulation of the original particle and the formation of the primary particle. With the further progression of the polymerization, the primary particles coagulate and final particles are formed. A three‐stage mechanism of the particle formation is proposed, that is, the particle nucleation, first coagulation, and second coagulation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3649–3653, 2007     

Ti5Si3电极层表面沉积BST薄膜及其介电性能研究

使用溶胶-凝胶法在涂覆有Ti5Si3电极层的玻璃基板上成功制备了Ba/Sr为64的BST薄膜,并对该薄膜在600℃进行了热处理.使用XRD,阻抗分析仪对薄膜进行了测试,研究了不同热处理条件对薄膜介电性能的影响.结果表明,由于非氧化物Ti5Si3电极层中氧空位等缺陷含量少,因此可成功制备缺陷少,质量良好的BST薄膜.快速升温可得到的薄膜晶相含量较多,多次重复热处理使薄膜中晶相的缺陷相对较少;控制薄膜的热处理条件,可以控制薄膜的电容和损耗.     

Electrodeposition of Pd–Ag alloy nanowires on highly oriented pyrolytic graphite

This paper reports findings of an investigation of Pd–Ag alloy nanowires on the step edges of highly oriented pyrolytic graphite (HOPG) by electrochemical deposition at room temperature. Scanning electron microscopy (SEM) images reveal that these alloy nanowires (109–430 nm) are uniform in diameter, and have lengths up to 100–500 μm. The electrodeposition process involves the initial formation of nanowires induced at the step edges of the oxidized HOPG substrate at a very negative potential and subsequent growth at a constant low current density to coalesce the discontinuous nanowires. Alloy nanowires with a 20–25% silver content can be obtained when the ratio of Pd and Ag in the solution is carefully controlled. The SEM images demonstrate that the alloy nanowire arrays are continuous, parallel, ordered, well-aligned and have a narrow distribution of diameters. The Pd–Ag alloy nanowire arrays are promising materials for fabricating hydrogen nanosensors.     

Synthesis and characterization of poly(butyl acrylate)/silica and poly(butyl acrylate)/silica/poly(methyl methacrylate) composite particles

Poly(butyl acrylate)/poly(methyl methacrylate) (PBA/PMMA) core–shell particles embedded with nanometer‐sized silica particles were prepared by emulsion polymerization of butyl acrylate (BA) in the presence of silica particles preabsorbed with 2,2′‐azobis(2‐amidinopropane)dihydrochloride (AIBA) initiator and subsequent MMA emulsion polymerization in the presence of PBA/silica composite particles. The morphologies of the resulting PBA/silica and PBA/silica/PMMA composite particles were characterized, which showed that AIBA could be absorbed effectively onto silica particles when the pH of the dispersion medium was greater than the isoelectric potential point of silica. The critical amount of AIBA added to have stable dispersion of silica particles increased as the pH of the dispersion medium increased. PBA/silica composite particles prepared by in situ emulsion polymerization using silica preabsorbed with AIBA showed higher silica absorption efficiency than did the PBA/silica composite particles prepared by direct mixing of PBA latex and silica dispersion or by emulsion polymerization in which AIBA was added after the mixing of BA and silica. The PBA/silica composite particles exhibited a raspberrylike morphology, with silica particles “adhered” to the surfaces of the PBA particles, whereas the PBA/silica/PMMA composite latex particles exhibited a sandwich morphology, with silica particles mainly at the interface between the PBA core and the PMMA shell. Subsequently, the PBA/silica/PMMA composite latex obtained had a narrow particle size distribution and good dispersion stability. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3425–3432, 2006     

Cytotoxic Triosmium Carbonyl Clusters: A Structure–Activity Relationship Study

A structure–activity relationship (SAR) study of the triosmium carbonyl cluster Os₃(CO)₁₀(NCCH₃)₂ was carried out with a series of clusters of the general formula Os₃(CO)_12?nL_n, cationic osmium clusters and a hemi‐labile maltolato‐Os cluster. The SAR results showed that good solubility in DMSO and at least one vacant site are required for cytotoxicity. In vitro evaluation of these new compounds showed that some are selectively active against estrogen receptor (ER)‐independent MDA‐MB‐231 breast cancer cell lines relative to ER‐dependent MCF‐7 breast cancer cells, suggesting that the compounds have a different biological target specific to MDA‐MB‐231 cells. In particular, the maltolato cluster exhibits strong antiproliferative activity, with an IC₅₀ value of 3 μM after only 24 h incubation. Additionally, biochemical assays conducted with the cationic cluster show that it induces apoptosis, although a biological target has not yet been identified. Further research to establish the molecular targets of these compounds and to develop improved organometallic clusters as potential breast cancer therapeutics is underway.     

基于孔补偿的三坐标测量臂误差研究及应用

研究FARO三坐标测量臂测量方程的建立方法和系统误差组成,并根据该误差模型采用简单快捷的孔补偿原理对三坐标测量臂进行多组数据的标定校准。利用校准好的三坐标测量臂对变速箱端盖进行孔直径和定位中心距的高精度测量,为实现变速箱端盖逆向设计制造和保证定位孔定位的可靠性提供科学数据。     

Synthesis of fluoroalkyl‐modified polyester and its application in improving the hydrophobicity and oleophobicity of cured polyester coatings

The fluoroalkyl‐modified polyester (PE‐F_n) was synthesized by the reaction of polyester resin (PE) and fluorinated isocyanate, and the structure of the synthesized product was characterized by proton nuclear magnetic resonance (¹H‐NMR) and fluorine nuclear magnetic resonance (¹⁹F‐NMR). The water and oil wettability of the cured PE coatings with PE‐F_n as additives was investigated by contact angle meter. The results showed that the introduction of an extremely low concentration of PE‐F_n into PE led to the increase in contact angle of water and diiodomethane on cured PE coatings, and the decrease in the surface free energy. The X‐ray photoelectron spectroscopic (XPS) analysis showed that the F/C molar ratio in the outer few nanometers was significantly higher than that in the bulk, indicating that the fluoroalkyl groups in PE‐F_n had enriched on the coating surface. It was also found that longer fluoroalkyl groups and fluoroalkyl groups with ? CF₃ at its end had the higher tendency to aggregate on the coating surface. The topological structures of the cured coatings were recorded by an atomic force microscope under tapping mode and the results revealed that there was a strong surface segregation of fluorinated species. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39812.