Segmented polymer networks containing amino‐dendrimers

Polymer networks in which poly(propylene imine) dendrimers (Astramol?) are connected to each other by linear polytetrahydrofuran (polyTHF) segments, were prepared by two methods. The first method was a one‐step procedure in which bifunctionally living polyTHF, obtained by initiation of the THF polymerization with trifluoromethane sulfonic anhydride (triflic anhydride), was reacted with an amino‐dendrimer. This reaction was very fast but did not allow formation of the end products. The second method was a two‐step procedure. In a first step, living polyTHF, prepared with acryloyloxybutyl triflate as initiator, was grafted on an amino‐dendrimer, to form a star‐like, acrylate‐terminated polyTHF multi‐macromonomer with the dendrimer as core. In a second step, networks were obtained by Michael addition between the acrylate end‐groups and unreacted amino‐groups of the dendrimer. This cross‐linking reaction occurred spontaneously upon heating of the solution of the multi‐macromonomer with gelation times varying from a few minutes to a few hours, depending on the temperature and the composition of the prepolymers. With this method it was possible to prepare networks in the form of coatings or films. © 2003 Society of Chemical Industry     

Electro-organic synthesis without supporting electrolyte: Possibilities of solid polymer electrolyte technology

The application of ion exchange membranes as solid polymer electrolytes (SPE) in fuel cells is state-of-the-art. This technology needs no supporting electrolyte; consequently it can be applied for electro-organic syntheses in order to save process steps. In this case the process is not predetermined to a maximized energy efficiency so that the selection of the cell design, of the electrode materials and of the operating conditions can be focused on a high selectivity of the electrode reactions. The electro-osmotic stream, which is caused by the solvation shells of the ions during their migration through the membrane, and hence is a typical property of SPE technology, has a significant effect on the electrode reactions. It generates enhanced mass transfer at the electrodes, which is beneficial for reaction selectivity. It can be influenced by the choice of, and possibly by the preparation of, the membrane. An additional remarkable advantage of SPE technology is the exceptional long durability of oxide coated electrodes. By combination of several process engineering methods stable operation of SPE cells has been realized, even for examples of non-aqueous reaction systems. Experiments up to 6000 h duration and in cells of up to 250 cm² membrane area show the potential for industrial application.     

Phosphorus‐containing polyaryloxydiphenylsilanes with high flame retardance arising from a phosphorus–silicon synergistic effect

Polyaryloxydiphenylsilanes were prepared from phosphorus‐containing diols and diphenydichlorolsilane through solution polymerization. With a stoichiometric imbalance in feed monomers, the resulting polymers exhibited moderate melting points and good processing properties. The polymers prepared showed initial decomposition temperatures above 340 °C, excellent thermal stability, high char yields at 850 °C and very high limited oxygen index values of 56–59. The polymers' char yields and their (P + Si) contents showed linear relationships. © 2003 Society of Chemical Industry     

Effects of diacrylate monomers on the bond strength of polymer concrete to wet substrates

The bond strengths of polymer concretes containing up to 15% (based on polymer resin) of diacrylate (DA) monomers were examined and compared with those without DA. A change occurring with the addition of DA monomers was an increase in the bond strength of polymer concrete to wet substrates. Zinc diacrylate (ZDA) and calcium diacrylate (CDA) were each used as an additive to monomers and resins [methyl methacrylate (MMA), polyester, and two kinds of epoxies]. The variables were amount of the DA monomers and surface conditions (wet or dry and smooth or rough). Bond strengths were measured by tension bond. ZDA was found to improve the bond strength of MMA and polyester, whereas CDA improved the bond strength of epoxies. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 991–1000, 2003     

Thermodynamic and Transport Properties of Liquid HFC-227ea

The thermal conductivity and heat capacity of liquid 1,1,1,2,3,3,3-hepta-fluoropropane (HFC-227ea) have been studied by a high-frequency thermal-wave method over the temperature range of 294 to 345 K at pressures up to 2.8 MPa. The purity of the samples used throughout the measurements is 99.99 mol%. The experimental uncertainties of the thermal conductivity and heat capacity measurements were estimated to be within ±1.5 and ±2%, respectively. The thermal conductivity of HFC-227ea in the liquid phase decreases as temperature increases, while the pressure has an opposite effect.     

WuM1-1羽状分支水平井充气钻井液技术

WuM1-1井由1口多分支水平井和1口采气的直井组成。该井斜井段短,井斜率在30°/100 m以上,主井眼和10个分支井段总进尺6182 m,98%以上在煤层中钻进,煤层脆、压实性较好,更易发生掉块。为满足钻井对井壁稳定性、润滑性、井眼净化以及煤层保护等的要求,采用钾铵基聚合物防塌钻井液进行充气欠平衡钻井,在钻进中保持钻井液有合适的粘度、切力,选用合适的注气压力和注气量以及当量钻井液密度;每钻完一个立柱坚持循环几分钟,上下划眼一次,并泵入CMC高粘钻井液,配合有效使用固控设备,尽量使井眼干净;复配使用粉末状固体润滑剂和液体润滑剂。该钻井液性能稳定,易于维护,悬浮携岩能力强,润滑性好,井眼畅通,保证了WuM1-1井安全、快速、优质施工。该井在煤层钻进中无阻卡现象,井壁稳定,没有出现井壁掉块或井垮现象,水平连通一次成功,10口分支井悬空侧钻一次成功,只用57 d即顺利完井,比该地区常规钻井快49倍。     

Spin probe study of semi‐interpenetrating polymer networks based on polyurethane and polymethacrylate functional prepolymers

The motional transition and heterogeneity of semi‐interpenetrating networks (SIPNs) based on polyurethane (PU) with carboxylic groups and methacrylic copolymer (PM) with tertiary amine groups were studied by the electron spin resonance (ESR) spin probe method. The concentration of functional groups in both prepolymers varied from 0 to 0.45 mmol g^?1. Spin‐probed SIPNs show that the temperature‐dependent spectra are sensitive to polymer interactions imposed by functional groups. These interactions determine the free volume distribution in the matrix and temperature at which motional transition takes place. The fraction of free volume increases with functional group concentration and reaches its maximum at 0.25 mmol g^?1. Further increases in the functional group concentration reduce the free volume. The results of the networks with strong interactions are discussed in terms of the interference of the plasticizing effect of the PU component and the formation of possible cluster cross‐links, which restricts segmental motions. Copyright © 2003 Society of Chemical Industry     

The effect of annealing on the elastoplastic and viscoelastic responses of isotactic polypropylene

Observations are reported on isotactic polypropylene (i) in a series of tensile tests with a constant strain rate on specimens annealed for 24 h at various temperatures in the range from 110 to 150 °C, (ii) in two series of creep tests in the subyield region of deformations on samples not subjected to thermal treatment and on specimens annealed at 140 °C, and (iii) in a series of tensile relaxation tests on non-annealed specimens. Constitutive equations are derived for the elastoplastic and non-linear viscoelastic responses of semicrystalline polymers. A polymer is treated as an equivalent transient network of macro-molecules bridged by junctions (physical cross-links, entanglements and lamellar blocks). The network is assumed to be highly heterogeneous, and it is thought of as an ensemble of meso-regions with different activation energies for separation of strands from temporary nodes. The elastoplastic behavior is modelled as sliding of junctions in meso-domains with respect to their reference positions driven by macro-deformation. The viscoelastic response is attributed to detachment of active strands from temporary junctions and attachment of dangling chains to the network. Constitutive equations for isothermal deformations with small strains are derived by using the laws of thermodynamics. Adjustable parameters in the stress–strain relations are found by fitting the experimental data.     

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.     

CFH-Ⅱ型翻车机传动齿轮轴承座的座脚螺栓联接失效分析与改进

分析了CFH-Ⅱ型翻车机传动齿轮轴承座的座脚螺栓组联接失效(松动)的原因，得出控制和保证合适的螺栓组联接预紧力是防止螺栓联接失效(松动)的关键；依据现场条件，对座脚螺栓进行了设计改进；提出了一种适合现场使用的螺栓预热伸长的装配方法，经实践验证此法是简单可靠的装配方法。