Chemische Zusammensetzung und Mikrostruktur polymerabgeleiteter Gläser und Keramiken im System Si–C–O. Teil 2: Charakterisierung der Gefügeausbildung mittels hochauflösender Durchstrahlungselektronenmikroskopie und Feinbereichsbeugung

Chemical Composition and Microstructure of Polymer‐Derived Glasses and Ceramics in the Si–C–O System. Part 2: Characterization of microstructure formation by means of high‐resolution transmission electron microscopy and selected area diffraction Liquid or solid silicone resins represent the economically most interesting class of organic precursors for the pyrolytic production of glass and ceramics materials on silicon basis. As dense, dimensionally stable components can be cost‐effectively achieved by admixing reactive filler powders, chemical composition and microstructure development of the polymer‐derived residues must be exactly known during thermal decomposition. Thus, in the present work, glasses and ceramics produced by pyrolysis of the model precursor polymethylsiloxane at temperatures from 525 to 1550 °C are investigated. In part 1, by means of analytical electron microscopy, the bonding state of silicon was determined on a nanometre scale and the phase separation of the metastable Si–C–O matrix into SiO₂, C and SiC was proved. The in‐situ crystallization could be considerably accelerated by adding fine‐grained powder of inert fillers, such as Al₂O₃ or SiC, which permits effective process control. In part 2, the microstructure is characterized by high‐resolution transmission electron microscopy and selected area diffraction. Turbostratic carbon and cubic β‐SiC precipitate as crystallization products. Theses phases are embedded in an amorphous matrix. Inert fillers reduce the crystallization temperature by several hundred °C. In this case, the polymer‐derived Si–C–O material acts as a binding agent between the powder particles. Reaction layer formation does not occur. On the investigated pyrolysis conditions, no crystallization of SiO₂ was observed.     

Stabilization of bioethanol recovery with silicone rubber‐coated ethanol‐permselective silicalite membranes by controlling the pH of acidic feed solution

In order to produce highly concentrated bioethanol by pervaporation using an ethanol‐permselective silicalite membrane, techniques to suppress adsorption of succinic acid, which is a chief by‐product of ethanol fermentation and causes the deterioration in pervaporation performance, onto the silicalite crystals was investigated. The amount adsorbed increased as the pH of the aqueous succinic acid solution decreased. The pervaporation performance also decreased with decreasing pH when the ternary mixtures of ethanol/water/succinic acid were separated. Using silicalite membranes individually coated with two types of silicone rubber, pervaporation performance was significantly improved in the pH range of 5 to 7, when compared with that of non‐coated silicalite membranes in ternary mixtures of ethanol/water/succinic acid. Moreover, when using a silicalite membrane double‐coated with the two types of silicone rubber, pervaporation performance was stabilized at lower pH values. In the separation of bioethanol by pervaporation using the double‐coated silicalite membrane, removal of accumulated substances having an ultraviolet absorption maximum at approximately 260 nm from the fermentation broth proved to be vital for efficient pervaporation. Copyright © 2005 Society of Chemical Industry     

The flame retardant mechanism of polyolefins modified with chalk and silicone elastomer

This paper presents the current understanding of the flame retardant mechanism of Casico?. The study includes the flame retardant effect of each individual component: ethylene–acrylate copolymer, chalk and silicone elastomer, as well as the formation of an intumescent structure during heating. The flame retardant properties were investigated by cone calorimetry and oxygen index tests. To obtain insight into the flame retardant mechanism, heat treatment under different conditions has also been performed. The results indicate that the flame retardant mechanism of Casico is complex and is related to a number of reactions, e.g. ester pyrolysis of acrylate groups, formation of carbon dioxide by reaction between carboxylic acid and chalk, ionomer formation and formation of an intumescent structure stabilized by a protecting char. Special emphasis is given to the formation of the intumescent structure and its molecular structure as evaluated from ¹³C MAS‐NMR and ²⁹Si MAS‐NMR, ESCA and XRD analysis. After treatment at 500°C the intumescent structure consists mainly of silicon oxides and calcium carbonate and after treatment at 1000°C the intumescent structure consists of calcium silicate, calcium oxide and calcium hydroxide. Copyright © 2003 John Wiley & Sons, Ltd.     

Continuous formation of slurry ice by cooling water–oil emulsion in a tube

Water-silicone oil emulsion with an additive, (C₂H₅O)₃SiC₃H₆NH₂, was examined as a heat storage material. A spiral tube used as a heat exchanger was immersed in a low temperature bath and the emulsion was circulated in the tube to make ice continuously. Ice was separated from the ice–liquid suspension in an outlet tank. The amount of formed ice, the temperatures of the inlet and the outlet of the heat exchanger, and the temperatures in the tube wall were measured and the overall heat transfer coefficient and the heat flux through the tube were calculated. Experiments were carried out, varying the flow rate, the temperature of cooling brine, and the thickness of tube wall. The condition under which slurry ice was formed continuously without adhesion of ice to the cooling wall was clarified. Though decrease in the thermal resistance of the tube increased the rate of ice formation or raised the brine temperature, it narrowed the range of the flow rate and of the brine temperature in which slurry ice was formed continuously.     

Development and characterization of magnetorheological polymer gels

Magnetorheological materials have been used in many applications in recent years. To develop new materials, polyurethane and silicone polymer gels were investigated. Rheology is qualitatively controlled for each system by controlling the concentration of reactants and diluents. The resulting polymers have solid, gel, or liquid states, depending on the crosslinking and dilution. The gels were characterized through kinetic analysis. Differential scanning calorimetry (DSC) was used with analysis methods to find the kinetic properties for diluted and undiluted polyurethane systems. Heat of reaction, order of reaction, preexponential constant, and activation energy were obtained from the experimental DSC data. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2733–2742, 2002     

Resilient metal spring network silicone-matrix composite for separable interconnections

Resilient metal spring silicone-matrix conducting composites for separable interconnections in electronics were fabricated by the impregnation of silicone into a preform comprising randomly oriented C-shaped Cu-Be springs and a small proportion of Sn-Pb solder, which served to connect the springs at some of their intersections. Composites containing 6.1-9.8 vol.% total filler exhibited volume electrical resistivity 0.5-1.0 mΩ.cm and contact resistivity (with copper) 11-17 mΩ.cm². A compressive stress of about 30 kPa was needed for the low contact resistivity to be reached. The volume 17-26% and the contact resistivity increased by 5% after heating in air at 130-150°C for seven days. Composites containing <9 vol.% total filler showed no stress relaxation for seven days at 6.0% strain.     

Preparation and properties of silicone‐containing poly(methyl methacrylate) gels

Poly(methyl methacrylate) (PMMA) gels with varying amounts of silicone and solvent and constant amounts of crosslinker were prepared by solution free radical crosslinking copolymerization of methyl methacrylate (MMA), ethylene glycol dimethacrylate (EGDM), tetraethoxysilane (TEOS) and vinyltriethoxysilane (VTES) comonomer systems. They were then studied in benzene at a total monomer concentration of 3.5 mol L^?1 and 70 °C. The conversion of monomer, volume swelling ratio, weight fraction and gel point were measured as a function of the reaction time, silicone concentration and benzene content up to the onset of macrogelation. Structural characteristics of the gels were examined by using equilibrium swelling in benzene, gel fraction and Fourier‐transform infrared (FTIR) analysis. The morphology of the copolymers was also investigated by SEM. Based on the obtained results, it was concluded that the FTIR data did not have the capacity to show the presence of the VTES or TEOS moiety in these kinds of copolymers. On the other hand, the variation of weight fraction of gel, W_g, and its equilibrium volume swelling ratio in benzene, q_v, exhibited the same behaviour as that of MMA/EGDM copolymers. Also, the dilution of the monomer mixture resulted in an increase in the gel point and swelling degree and a decrease in the percent of conversion and gel fraction. Finally, TEOS is not an ideal silicone compound for reaction in the MMA/EGDM copolymerization system, whereas VTES is a suitable silicone comonomer for this system and it has been proved useful. Copyright © 2005 Society of Chemical Industry     

有机硅丙烯酸酯增深剂的制备及应用

由乙烯基三乙氧基硅烷与KH-550、丙烯酸酯类单体在阴/非离子表面活性剂存在下，通过乳液聚合制得带蓝光的半透明有机硅丙烯酸酯乳液．该乳液粘度小，有机硅质量分数15％，总固体质量分数30％，该增深剂既可单独使用，也可与氨基硅油乳液复配，经蓝色16电力纺、黑色03双绉等真丝产品增深，其增深度可达15％，但亲水性有所下降．     

UV-固化光纤色标油墨

报导了一类新型的化学功能材料———ＵＶ固化光纤色标油墨。该材料由可ＵＶ固化的有机硅环氧安息香酸丙烯酸酯（ＳＥＢＡ）和脂环族环氧丙烯酸酯（ＡＣＥＡ）两种光敏预聚物为基料，以自行合成的光敏染料———分散红氨基甲酸酯丙烯酸酯（ＲＵＡ）、分散蓝氨基甲酸酯丙烯酸酯（ＢＵＡ）和吖啶黄氨基甲酸酯丙烯酸酯（ＹＵＡ）为着色剂，加入必要的添加剂配制而成的ＵＶ固化光纤色标油墨。该色标油墨已在光纤生产中得到应用。     

FR-1型粘合剂的性能及其应用

介绍了FR-1型粘合剂用于氟橡胶、硅橡胶、三元乙丙橡胶与金属热硫化粘着，制作橡胶金属复合制品的情况。金属骨架经喷砂或表面化学处理并用溶剂清洗之后，涂FR—1型粘合剂，经预烘干后与橡胶进行热硫化粘着，效果良好。