支化聚合物的熔体流变特性

从支化聚合物的流变特性表征以及分子结构和温度对其流变行为的影响三个方面综述了支化聚合物的流变特性，长链支化结构明显延缓了整个高分子的松驰过程，这集中表现在剪切条件下的应变软化和拉伸条件下的应变硬化，而且，长链支化使得时－温等效原理不再有效，对温度的依赖性也表现出一定的复杂性，改进蛇行理论和耦合模型可以解释部分实验结果，但又都存在不足，因此，对于支化聚合物独特的流变行为，还需进一步的深入研究。     

A numerical approach to spherical indentation techniques for material property evaluation

In this work, some inaccuracies and limitations of prior indentation theories, which are based on experimental observations and the deformation theory of plasticity, are investigated. Effects of major material properties on the indentation load-deflection curve are examined via finite element (FE) analyses based on incremental plasticity theory. It is confirmed that subindenter deformation and stress-strain distribution from deformation plasticity theory are quite dissimilar to those obtained from incremental plasticity theory. We suggest an optimal data acquisition location, where the strain gradient is the least and the effect of friction is negligible. A new numerical approach to indentation techniques is then proposed by examining the FE solutions at the optimal point. Numerical regressions of obtained data exhibit that the strain-hardening exponent and yield strain are the two key parameters which govern the subindenter deformation characteristics. The new indentation theory successfully provides a stress-strain curve and material properties with an average error of less than 3%.     

Uniaxial elongational viscosity of PS/a small amount of UHMW-PS blends

A series of polystyrene (PS) and a small amount of ultra high molecular weight (UHMW) PS blends have been prepared by using tetrahydrofuran (THF). Matrix PS has an M_w of 423,000 (M_w/M_n= 2.36) and UHMW-PS has either an M_w of 3,220,000 (M_w/M_n= 1.05) or 15,400,000 (M_w/M_n=1.30) in the range of concentration from 0 wt% to 1.5 wt%. The influence of a small amount of UHMW on dynamic viscoelasticity was investigated. At the frequency lower than 0.001 rad/s, the enhancement of G′ was observed by the incorporation of a small amount of UHMW. And the degree of enhancement was in the order of M_w of UHMW and its concentration. The measurement of uniaxial elongational viscosity for the blends was performed and the effects of UHMW on strain-hardening properties were analyzed at equal strain-rate conditions. The concentration of UHMW where the strain-hardening becomes substantially stronger was determined. To get more insight into the cause of enhancement of strain-hardening at a certain concentration, the damping function from step-shear stress relaxation was measured. The influence of a small amount of UHMW on the damping function was found to be small. It was interpreted, from time- and strain-dependency points, that the enhancement of strain-hardening by a small amount of UHMW was governed by the long relaxation time. Received: 6 September 2000 Accepted: 11 January 2001     

The strain-hardening behaviour of linear and long-chain-branched polyolefin melts in extensional flows

By generalizing the Doi-Edwards model to the Molecular Stress Function theory of Wagner and Schaeffer, the extensional viscosities of polyolefin melts in uniaxial, equibiaxial and planar constant strain-rate experiments starting from the isotropic state can be described quantitatively. While the strain hardening of four linear polymer melts (two high-density polyethylenes, a polystyrene and a polypropylene) can be accounted for by a tube diameter that decreases affinely with the average stretch, the two long-chain-branched polymer melts considered (a low-density polyethylene and a long-chain branched polypropylene) show enhanced strain hardening in extensional flows due to the presence of long-chain branches. This can be quantified by a molecular stress function, the square of which is quadratic in the average stretch and which follows from the junction fluctuation theory of Flory. The ultimate magnitude of the strain-hardening effect is governed by a maximum value of the molecular stress, which is specific to the polymer melt considered and which is the only free non-linear parameter of the theory. Received: 1 June 1999/Accepted: 24 November 1999     

Multiscale modeling of strain-hardening cementitious composites

This research involves the multiscale characterization of strain-hardening cementitious composites under tensile loading. The sensitivity of cracking behavior to fiber dispersion is studied using a special form of lattice model, in which each fiber is explicitly represented. It is shown that the nonlocal modeling of fiber bridging forces is essential for obtaining realistic patterns of crack development and strain-hardening behavior. Crack count and crack size are simulated for progressively larger levels of tensile strain. The influence of fiber dispersion is clearly evident: regions with significantly fewer fibers act as defects, reducing strength and strain capacity of the material.     

Quasi-static cylindrical cavity expansion in an elastoplastic compressible Mises solid

The self-similar elastoplastic field induced by quasi-static expansion of a pressurized cylindrical cavity is investigated for Mises solids under the assumption of plane-strain. Material behavior is modeled by the elastoplastic J₂ flow theory with the standard hypoelastic version. The theory accounts for elastic-compressibility and allows for arbitrary strain-hardening (or softening) in the plastic range. A formulation of the exact governing equations is presented and analyzed in detail for the remote elastic field and for asymptotic plastic behavior near the cavity wall, along with numerical investigations for the entire deformation zone. An analytical solution was obtained under the axially-hydrostatic assumption (axial stress coincides with hydrostatic stress) within an error of about 2% or less as compared to the exact, numerically evaluated, value of cavitation pressure. Two ad-hoc compressibility approximations for cavitation pressure are suggested. These relations, which give very accurate results, appear to provide tight lower and upper bounds on the exact value of cavitation pressure within an error of less than 0.5%.     

Suspensions of monodisperse spheres in polymer melts: particle size effects in extensional flow

Suspensions in polymeric, viscoelastic liquids have been studied in uniaxial extensional flow. The fibre wind-up technique has been used for this purpose. The effects of particle size and particle volume fraction have been investigated, using monodisperse, spherical particles. The results have been compared with shear flow data on the same materials. The values of the relative extensional viscosities at low stretching rates are in agreement with the relative shear viscosities and relative moduli. This indicates that hydrodynamic forces are stronger than the particle interaction forces. At larger strain rates strain hardening occurs; it is suppressed when particles are added. Small aggregating particles reduce the strain hardening more strongly than larger particles; strain hardening can even be totally eliminated. When further increasing the stretching rate, hydrodynamic effects dominate again and the effect of particle size effect on strain hardening disappears.     

Viscoelastic flow simulation of polytetrafluoroethylene (PTFE) paste extrusion

Polytetrafluoroethylene (PTFE) is known to be a polymer that shows inherent microstructure formation during cold processing such as paste extrusion. To model such a complex flow, a viscoelastic constitutive equation is proposed that takes into account the continuous change of the paste microstructure during flow, through fibril formation. The mechanism of fibrillation is captured through a microscopic model for a structural parameter ξ that represents the percentage of fibrillated domains of the paste. The proposed viscoelastic constitutive equation consists of a viscous shear-thinning term (Carreau model) and an elastic term (modified Mooney–Rivlin model), the relative contribution of the two depending on ξ. The viscous and elastic parameters of the model are determined by using shear and extensional rheometry on the paste. Finite element simulations based on the proposed constitutive relation with the measured model parameters predict reasonably well the variations of the extrusion pressure with the apparent shear rate and the die geometrical characteristics.