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21.
Electro-organic synthesis without supporting electrolyte: Possibilities of solid polymer electrolyte technology 总被引:1,自引:0,他引:1
J. Jörissen 《Journal of Applied Electrochemistry》2003,33(10):969-977
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. 相似文献
22.
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 相似文献
23.
J. Gegner 《Materialwissenschaft und Werkstofftechnik》2003,34(3):290-297
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. 相似文献
24.
V S R Murthy 《Bulletin of Materials Science》1993,16(2):87-108
Research and development efforts on high-temperature, oxidation-resistant fibres have increased over the past decade due to
the demand for light-weight, stiff and strong composite materials in aerospace applications. Varieties of ‘high-performance’,
continuous, non-oxide fibres with low-density, high tensile strength and tensile modulus have been developed either from organic
precursors or via chemical vapour deposition for fabrication of ceramic matrix composites. Fibres derived from polymer precursors
(e.g. Nicalon, Tyranno, HPZ) are small in diameter (compared to CVD monofilaments) and are ideally suited for ceramic composites.
Processing, microstructural stability and mechanical properties of these newly developed SiC and Si3N4 base fibres are briefly reviewed in this paper. 相似文献
25.
从测得的竞聚率计算了单体链节在聚[苯乙烯-甲基丙烯酸β(甲基亚硫酰基)乙酯](PSM)中的序列分布。苯乙烯(S)或甲基丙烯酸β(甲基亚硫酰基)乙酯(M)的长序列的概率随着PSM中相应单体含量的增加而增加。对于S和M摩尔分数大致相等的PSM,单体链节的长序列分布函数值相接近。用与此结构相近的PSM合成的稀土金属络合物,其催化活性不佳。在M短序列分布和S长序列分布较高的情况下,络合物的催化活性最好。所得聚丁二烯的微观结构与PSM中单体单元的分布无关。 相似文献
26.
A quantum chemical study of the binding of Li+ cation to polyalkyloxides has been carried out. The lithium cation interaction with three polyalkyloxides (polyethylene oxide (PEO), polytrimethylene oxide (PTMO), and polypropylene oxide (PPO)) has been investigated using ab initio molecular orbital theory at the HF/6-31G* level with molecular models for the polymers. Coordination by one to six oxygens was considered. In addition, higher level calculations were carried out using G3(MP2) theory for coordination of Li+ by one oxygen. For coordination of lithium by one oxygen, the binding energy ordering is PTMO>PPO>PEO, with PTMO having the largest lithium cation affinity. The same ordering is found for larger coordination numbers with the exception of coordination by six oxygens, where the ordering changes due to the steric interactions. 相似文献
27.
Banded textures produced in a thermotropic liquid crystal polymer by shearing between glass slides are examined by using both transmission electron and polarized light microscopy. The periodic variation in director orientation about the shear axis, as measured by light microscopy, is shown to be distinctly different from that indicated by electron diffraction. Measurements of birefringence and observation of Zernicke phase contrast indicate periodic variations in optical properties of the polymer, in step with the bands. Such effects are accounted for in terms of a synchronous rotation of the planar aromatic groups about the molecular chain axes. Evidence for an out-of-plane component of molecular orientation is also presented. 相似文献
28.
29.
Paul J. Flory 《Polymer International》1985,17(2):96-102
The earliest investigations on rubber elasticity, commencing in the 19th century, were necessarily limited to phenomenological interpretations. The realisation that polymers consist of very long molecular chains. commencing c. 1930, gave impetus to the molecular theory of rubber elasticity (1932-). according to which the high deformability of an elastomer, and the elastic force generated by deformation, stem from the configurations accessible to long molecular chains. Theories of rubber elasticity put forward from 1934-1946 relied on the assumption that the junctions of the rubber network undergo displacements that are affine in macroscopic strain. The theory of James and Guth (1947) dispensed with this premise, and demonstrated instead that the mean positions of the junctions of a ‘phantom’ network consisting of Gaussian chains devoid of material properties are affine in the strain. The vital significance of the distinction between the actual distribution of chain vectors in a network and their distribution if the junctions would be fixed at their mean positions went unnoticed for nearly 30 years. Experimental investigations, commencing with the incisive work of Gee in 1946. revealed large departures from the relationship of stress to strain predicted by the theories cited. This discrepancy prompted extensive studies, theoretical and experimental, during succeeding years. Inquiry into the fundamentals of polymer networks, formed for example by interlinking very long polymer molecules, exposed the need to take account of network imperfections, typically consisting of chains attached at only one end to a network junction. Various means were advocated to make corrections for these imperfections. The cycle rank ζ of the network has been shown (1976) to be the fundamental measure of its connectivity, regardless of the junction functionality and pattern of imperfections. Often overlooked is the copious interpenetration of the chains comprising typical elastomeric networks. Theories that attempt to represent such networks on a lattice are incompatible with this universal feature. Moreover, the dense interpenetration of chains may limit the ability of junctions in real networks to accommodate the fluctuations envisaged in the theory of phantom networks. It was suggested in 1975 that departures from the form predicted for the elastic equation of state are due to constraints on the fluctuations of junctions whose effect diminishes with deformation and with dilation. Formulation of a self-consistent theory based on this suggestion required recognition of the non-affine connection between the chain vector distribution function and the macroscopic strain in a real network, which may partake of characteristics of a phantom network in some degree. Implementation of the idea was achieved through postulation of domains of constraint affecting the equilibrium distribution of fluctuations of network junctions from their mean positions. This led in due course to a theory that accounts for the relationship of stress to strain virtually throughout the ranges of strain accessible to measurement. The theory establishes connections between structure and elastic properties. This is achieved with utmost frugality in arbitrary parameters. 相似文献
30.
十二酰胺丙基二甲基羟乙基氯化铵与十二烷基硫酸钠水溶液的表面吸附和胶束形成 总被引:1,自引:0,他引:1
利用十二酰胺丙基二甲胺和氯乙醇反应 ,合成了十二酰胺丙基二甲基羟乙基氯化铵 (DDHA)阳离子表面活性剂 ,将其与十二烷基硫酸钠 (SDS)以不同摩尔比进行混合 ,测定了混合系统的表面张力 ,计算了单一系统和混合系统的饱和吸附量、分子最小截面积 ,表面层和胶束中 DDHA的摩尔分率及分子间相互作用参数 ,目视观察了混合系统的浑浊情况。结果表明 :在降低γcmc和 cmc方面 ,DDHA SDS混合系统有协同效应 ,表面层和胶束的组成与二组分配比有关 ,但是非对称的 ,等物质的量混合物中 ,DDHA在胶束和表面层中具有较大的摩尔分数。DDHA与 SDS在实验测定的各混合系统中都不出现混浊 相似文献