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1.
Hindered rotation was considered in calculations of the conformational parameters of a series of polyheteroarylenes with bulky side substituents by the Monte-Carlo method. Within the range of experimental errors, the results of calculations for several polyarylates coincide with the values of conformational rigidity, determined from hydrodynamic experimental data. The proposed procedure was used to estimate the rigidities of a number of polymers with bulky side substuents for which experimental determination is difficult. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1287–1296, July, 1998.  相似文献   
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The dependence of the glass transition and initial decomposition temperatures of polyperyleneimide and polynaphthylimide on the conformational rigidity was studied by the Monte Carlo, Kuhn segment, and quantum chemical AM1 methods. The corresponding linear plots can be used for estimation of the glass transition and initial decomposition temperatures when experimental determination is difficult.  相似文献   
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Solution characterization of the thermotropic liquid–crystalline copolyester synthesized from terephthalic acid, phenyl hydroquinone, and (1-phenylethyl) hydroquinone (2 : 1 : 1) has been performed. Viscometry, size exclusion chromatography, and light scattering have been carried out under the optimal conditions found for measurement: 85°C in a 50/50 mixture by weight of phenol/1,2,4-trichlorobenzene. The absolute weight-average molecular weight from light-scattering measurements served for calibration of indirect methods of charac-terization (e.g., the limiting viscosity number [η] is related to the molecular weight by [η] = 5.10 × 10?4 Mw0.72), and the molecular weight per unit chain length, $ \bar M_L * $, from light scattering and size exclusion chromatography (SEC) is found to be 28 Å?1, consistent with theoretical expectations. The calculated persistence length q is 28 Å. Moreover, the meth-odology of SEC characterization enables the kinetics of solid-state postpolymerization of this liquid-crystalline copolyester to be studied. © 1993 John Wiley & Sons, Inc.  相似文献   
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郑喜印 《数学学报》1998,41(1):19-28
本文研究了Banach空间上凸函数项级数,给出了Moreau Rockafelar定理的推广,做为它的应用,获得了Kuhn Tucker定理的一个部分推广.  相似文献   
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Silicon has a tremendous importance as an electronic, structural and optical material. Modeling the interaction of a silicon surface with a pointed asperity at room temperature is a major step towards the understanding of various phenomena related to brittle as well as ductile regime machining of this semiconductor. If subjected to pressure or contact loading, silicon undergoes a series of stress-driven phase transitions accompanied by large volume changes. In order to understand the material's response for complex non-hydrostatic loading situations, dedicated constitutive models are required. While a significant body of literature exists for the dislocation dominated high-temperature deformation regime, the constitutive laws used for the technologically relevant rapid low-temperature loading have severe limitations, as they do not account for the relevant phase transitions. We developed a novel finite deformation constitutive model set within the framework of thermodynamics with internal variables that captures the stress induced semiconductor-to-metal (cd-Siβ-Si), metal-to-amorphous (β-Sia-Si) as well as amorphous-to-amorphous (a-Sihda-Si, hda-Sia-Si) transitions. The model parameters were identified in part directly from diamond anvil cell data and in part from instrumented indentation by the solution of an inverse problem. The constitutive model was verified by successfully predicting the transformation stress under uniaxial compression and load–displacement curves for different indenters for single loading–unloading cycles as well as repeated indentation. To the authors' knowledge this is the first constitutive model that is able to adequately describe cyclic indentation in silicon.  相似文献   
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Three polysaccharides, Rhizobium leguminosarum 8002 EPS(I), Rhizobium trifolii TA1-EPS (II), Rhizobium leguminosarum 127K87 EPS (III), produced by bacteria of Rhizobium genus have been investigated by static and dynamic light scattering combined with chirooptical measurements. All three polymers have the same backbone but differ in the length of the side chains and in the content of minor substituents. An isothermal conformational transition coil → helix was observed with I and II by adding salt (NaCl). The molecular parameters of the polysaccharides in the ordered state were determined by light-scattering data. Increasing the ionic strength a shrinking of the helix was observed accompanied by a corresponding decrease in the radius of gyration. An extraordinary chain stiffness in terms of Kuhn segment lengths was found in both cases, similar to that already observed for other microbial polysaccharides. In the case of III no disorder → order transition was induced by the salt, and the scattering behavior corresponds to that of a rather flexible polymer with a characteristic ratio C = 24. The incapability of III to form a helical structure is attributed to the effect of the very long side chain. The analysis of the time correlation functions revealed typical flexible chain behavior for all three polysaccharides. This behavior for the two ordered polymers is in agreement with a recent theory by Maggs and is due to bending modes of the rods. ©1995 John Wiley & Sons, Inc.  相似文献   
9.
The effect of substituents on the conformational rigidity of the six-membered dihydrocycle constituting the repeating unit of heterocyclic polymers was studied by the semiempirical AM1 method and by conformational analysis. The polymer rigidity can be controlled over a wide range by choosing appropriate substituents in the dihydrocycle. An original procedure was proposed for calculating the Kuhn segment of the copolymer taking into account the Boltzmann factor. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 797–801, May, 2000  相似文献   
10.
The present two-part study aims at investigating the specific effects of Mohr–Coulomb matrix on the strength of ductile porous materials by using a kinematic limit analysis approach. While in the Part II, static and kinematic bounds are numerically derived and used for validation purpose, the present Part I focuses on the theoretical formulation of a macroscopic strength criterion for porous Mohr–Coulomb materials. To this end, we consider a hollow sphere model with a rigid perfectly plastic Mohr–Coulomb matrix, subjected to axisymmetric uniform strain rate boundary conditions. Taking advantage of an appropriate family of three-parameter trial velocity fields accounting for the specific plastic deformation mechanisms of the Mohr–Coulomb matrix, we then provide a solution of the constrained minimization problem required for the determination of the macroscopic dissipation function. The macroscopic strength criterion is then obtained by means of the Lagrangian method combined with Karush–Kuhn–Tucker conditions. After a careful analysis and discussion of the plastic admissibility condition associated to the Mohr–Coulomb criterion, the above procedure leads to a parametric closed-form expression of the macroscopic strength criterion. The latter explicitly shows a dependence on the three stress invariants. In the special case of a friction angle equal to zero, the established criterion reduced to recently available results for porous Tresca materials. Finally, both effects of matrix friction angle and porosity are briefly illustrated and, for completeness, the macroscopic plastic flow rule and the voids evolution law are fully furnished.  相似文献   
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