高体积百分比颗粒增强聚合物材料的有效粘弹性性质

聚合物材料通常表现为粘弹性性质．为了改进聚合物材料的力学性能,通常将某种无机材料以颗粒或纤维的形式填充到聚合物中,从而得到增强、增韧的聚合物基复合材料．提出了一个新的细观力学模型,用于预测颗粒增强聚合物复合材料的有效粘弹性性质,尤其针对高体积百分比的颗粒夹杂复合材料,该方法基于Laplace变换和双夹杂相互作用的弹性模型．计算了玻璃微珠/ED-6复合材料的有效松弛模量以及恒应变率下的应力应变关系．计算结果表明在高体积百分比下该文方法比基于Mori Tanaka方法预测的粘弹性效应明显减弱．     

扩张流变法研究表面活性剂在界面上的聚集行为

近年发展起来的界面流变测定技术在研究界面性质方面具有许多独特之处.本文结合我们的工作,总结了近年来有关该技术在表面活性剂界面聚集行为研究中的应用,讨论了扩张频率、表面活性剂浓度及疏水链长、无机盐和温度对表面扩张流变行为的影响,同时探讨了小分子表面活性剂与高分子表面活性剂表面扩张流变行为的区别以及小分子表面活性剂在气/液界面与液/液表面的扩张流变性的差异.大量研究表明,借助于界面流变性的测定不仅可以研究发生在界面上和界面附近的微观弛豫过程,而且可以探讨界面上超分子聚集体的形成,进而为乳状液和泡沫等分散体系的稳定性提供依据.     

Birefringence measurements in extensional flow of polyisobutylene around an expanding bubble

Birefringence in liquid polymers offers the possibility of obtaining information about stress in complex flows. In this work, this is done for extensional flows of polyisobutylene in a “breathing bubble” rheometer. In this type of rheometer, a bubble consisting of an incompressible, low-viscosity fluid (usually water) is injected into the sample with a nozzle. Expanding or collapsing the bubble by adding or removing water induces biaxial or uniaxial extension in the surrounding sample. The pressure difference between the bubble and the surroundings can be measured and compared to the predictions of constitutive equations. This measurement only gives one integral value for a complex flow history. In this paper, the birefringence around the bubble is measured in order to learn more about the flow. This is done by comparing pressure and birefringence results to those of standard constitutive equations for a polyisobutylene sample. A good agreement between the pressure and optical measurements and the theory is found with a single value of the stress-optical constant. Received: 25 June 1997 Accepted: 12 November 1997     

De la microstructure du polymère à ses propriétés rhéologiquesFrom the microstructure of polymers towards their rheological properties

We extend the previous work by Benallal et al. on the relationship between structure and rheological properties of linear polymer melts. The aim of this paper is to quantify the effect of the chemical structure on the viscoelastic properties. We show that these properties are governed by the monomer dimensions and the interaction energy. To cite this article: A. Allal et al., C. R. Physique 3 (2002) 1451–1458.     

Simple method for determining the critical molecular weight from the loss modulus

The normal concept is that the critical molecular weight (M_C) is about twice as large as the entanglement molecular weight (M_e). However, experimental data have shown considerable deviations from M_C ≈ 2M_e. Furthermore, a determination of M_C requires samples with a wide range of molecular weights, including weights lower than M_C and higher than M_C. In this article, we suggest a simple method for determining M_C from the loss moduli of nearly monodisperse linear polymers with M ? M_C. We consider two characteristic relaxation times, which correspond to the local maximum and minimum of the loss modulus. M_C is determined from the intersection of two phenomenological relaxation times as a function of the molecular weight. The method precisely agrees with M_C ≈ 2M_e, which is not shown by conventional methods. Moreover, our method provides a determination of relaxation time τ_e, at which chain segments first feel the constraints imposed by the conceptual tube, without the measurement of the tube diameter and the monomeric friction coefficient, which may be determined by complicated procedures with a lot of data. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2724–2729, 2004     

Some remarks on the propagation and non-propagation of discontinuities in linearly viscoelastic liquids

The equations of linear viscoelasticity with a bounded memory kernel have been shown to propagate singularities in a similar way as hyperbolic equations. In this paper, we investigate a model problem for a certain class of unbounded memory kernels. It is shown thatC -solutions are obtained, although there is a discontinuity in the boundary conditions.     

On Implicit Constitutive Theories

In classical constitutive models such as the Navier-Stokes fluid model, and the Hookean or neo-Hookean solid models, the stress is given explicitly in terms of kinematical quantities. Models for viscoelastic and inelastic responses on the other hand are usually implicit relationships between the stress and the kinematical quantities. Another class of problems wherein it would be natural to develop implicit constitutive theories, though seldom resorted to, are models for bodies that are constrained. In general, for such materials the material moduli that characterize the extra stress could depend on the constraint reaction. (E.g., in an incompressible fluid, the viscosity could depend on the constraint reaction associated with the constraint of incompressibility. In the linear case, this would be the pressure.) Here we discuss such implicit constitutive theories. We also discuss a class of bodies described by an implicit constitutive relation for the specific Helmholtz potential that depends on both the stress and strain, and which does not dissipate in any admissible process. The stress in such a material is not derivable from a potential, i.e., the body is not hyperelastic (Green elastic).     

Volume changes in glassy polymers

Summary Constitutive equations are derived for compressible glassy polymers at non-isothermal loading with finite strains. The model is based on the theory of temporary networks in its version of adaptive links concept. The stress–strain relations are applied to the analysis of uniaxial extension of a viscoelastic bar. Explicit formulas are developed for time-dependent Young's modulus and Poisson's ratio of the bar at small strains. Results of numerical simulation are compared with experimental data for polycarbonate, polyethylene, and poly(methyl methacrylate). It is demonstrated that (i) longitudinal stresses do not affect the specific free volume in the region of linear viscoelasticity at strains up to about 0.2%, and cause substantial changes in the free volume in the region of nonlinear viscoelasticity at strains about 1.0%; (ii) in the latter case, the increment of the free-volume fraction is proportional to the increase in the specific volume. Received 3 April 1998; accepted for publication 22 June 1998     

Strain-coupling effects in branched polymers

The applicability of a strain-coupling integral constitutive equation to the analysis of the nonlinear viscoelasticity of branched polymers is evaluated. A simpler and more efficient method is proposed for evaluating the material functions of the strain-coupling constitutive equation.