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31.
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
32.
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. 相似文献
33.
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
34.
改性双马来酰亚胺的研究 总被引:2,自引:0,他引:2
本文研究了双马来酰亚胺与烯丙基化合物形成的改性树脂体系的固化和热性能,讨论了单体配比、增韧剂、催化剂对性能的影响。 相似文献
35.
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
36.
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
37.
分子印迹技术及其应用 总被引:3,自引:0,他引:3
分子印迹技术是将高分子科学、材料科学、生物学、化学工程等有机集成。基于分子印迹技术所制备的分子印迹聚合物具有选择性高、稳定性好、应用范围广等特点 ,近年来得到了日益广泛和深入的研究。介绍了分子印迹技术的原理、分子印迹聚合物的制备方法、分子印迹技术的应用场合和实例 ,并简要预测了分子印迹技术领域未来的发展趋势。 相似文献
38.
聚合物降解产物伤害与糖甙键特异酶破胶技术 总被引:22,自引:1,他引:21
综述了钻井,完井,尤其是水力压裂作业中产生的多糖类聚合物伤害和应用糖甙键特异酶破胶,解除多糖类聚合物伤害的技术。第一节报道了聚合物降解产物造成的伤害,指出冻胶破胶液粘度低并不代表压裂液已从充填裂缝中充分返排,氧化破胶剂和普通酶破胶剂不能使多糖类聚合物充分降解,产生的大分子量,水不溶的降解产物可对地层造成伤害,消除伤害的办法是采用对糖甙键有特异性的各种水解酶作压裂液破胶剂或伤害地层处理剂。第二节报道了各种聚合物(纤维素,瓜尔胶,淀粉)糖甙键特异酶降解聚合物的机理。第三节报道了糖甙键特异酶(主要针对瓜尔胶)的应用性能测试及结果,包括岩心流动实验,含糖量和分子量测定,传导性测试。第四节介绍了糖甙键特异酶消除聚合物伤害和用作压裂液破胶剂的现场应用,包括选井原则,实施工艺要点及3个典型井例。 相似文献
39.
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
40.
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