Entanglement network and relaxation temperature dependence of single‐site catalyzed ethylene/1‐hexene copolymers

In this work, we investigate the linear viscoelastic response of high molecular weight ethylene/1‐hexene copolymers, characterized by a narrow molecular weight distribution and comonomer content in the range from 0 to 10 mol %. A variation in the entanglement plateau modulus has been found in agreement with the recently developed packing length model. The packing model applied to viscoelastic data suggests decreased values of the characteristic ratio, accordingly with recent computer simulation results. The flow activation energy increases as the side chain content increases. This feature is thought to be related to the mobility of the molecules. The presence of side branches due to the comonomer hinders the mobility of the molecules, and increases the thermal barrier for the segmental motion. Then in the comonomer content range studied, the increase of the flow activation energy goes parallel with a decrease in the characteristic ratio. This result suggests that more parameters than only the stiffness of the chain modulate the thermal dependence of viscoelastic properties. A more refined study is necessary combining experiments with computer simulations in order to elucidate these aspects. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Viscoelastic properties of polyarylene ether nitriles/thermotropic liquid crystalline polymer blend

Polyarylene ether nitriles (PEN)/thermotropic liquid crystalline polymer (TLCP) blend was prepared via melt mixing. The immiscible phase morphologies, linear and nonlinear, as well as transient viscoelastic properties of the blend were studied using SEM, rheometer, and DMA. The linear dynamic viscoelastic behavior of the blend shows temperature dependence due to further evolution of the immiscible morphology and, as a result, the principle of time‐temperature superposition (TTS) is invalid. In the steady shear flow, the discrete TLCP phase is difficult to be broken up because of the high viscosity ratio of the blend systems, while is easy to be coarsened and followed by elongation, and finally, to form fibrous morphology at high TLCP content and high shear level. During this morphological evolution process, the transient stress response presents step increase and nonzero residual relaxation behavior, leading to increase of the dynamic viscoelastic responses after steady preshear. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Potential applications of poly(vinyl alcohol)‐congo red aqueous solutions and hydrogels as liquids for hydraulic fracturing

The authors report on the viscoelastic characterization of guar hydrogels obtained through complexation reactions with borax ions. These gels are compared with hydrogels obtained from poly(vinyl alcohol) of different degree of hydrolysis through complexation reactions with congo red. The effect of the degree of hydrolysis and both, the concentration of PVA and the concentration of congo red, on the viscoelastic properties of the hydrogels is analyzed. The potential use of the PVA‐based hydrogels as hydraulic fracturing liquids is discussed in relation to the commonly used fracturing liquid based on the guar–borax system. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The influence of fluid elasticity on wall effects for creeping sphere motion in cylindrical tubes

Experimental results are presented of wall effect for the slow motion of spheres in elastic, constant-viscosity liquids. The results are correlated in terms of diameter ratio for d/D < 0.3, and Weissenberg number We < 5. Weissenberg number is defined as We = 2θV_m/d, with θ the Maxwellian relaxation time (θ = N₁/2τγ). The wall effect is found to be adequately described by Newtonian expressions for small Weissenberg number, We < 0.01. For larger values of the Weissenberg number, We > 0.2, virtually no wall effect is discernible; the small effect observed is correlated by the wall factor expression The wall effect observed is ascribed to the influence of fluid elasticity alone, since all the fluids used were elastic to a greater or lesser extent, but showed no shear thinning.      

Modeling the large‐strain constitutive behavior of polycarbonate under isothermal and anisothermal conditions

The tensile behavior of polycarbonate was studied at large strains below the glass‐transition temperature. Experiments were carried out at a series of constant temperatures and also under conditions of falling temperatures. The specimens necked with a natural draw ratio of approximately 2, and the study was mainly focused on the necked material. Isothermal experiments revealed an elastic mechanism that initiated beyond the natural draw ratio. A model consisting of an Eyring process and two Gaussian elastic mechanisms was found to be applicable to both the isothermal and anisothermal stress‐relaxation and stress–strain results. The same model also produced reasonable estimates of the stresses generated during the necking process. In addition, a simple relationship between the isothermal and anisothermal stress relaxation was demonstrated. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2105–2116, 2005     

Influence of untreated and novel electron‐beam‐modified surface‐coated silica filler on the thermorheological properties of ethylene–octene copolymer

We developed surface‐modified silica fillers by coating these with an acrylate monomer, trimethylolpropane triacrylate, or a silane coupling agent, triethoxyvinyl silane, followed by electron‐beam irradiation at room temperature. These were incorporated in an ethylene–octene copolymer rubber. Thermorheological studies of the unvulcanized ethylene–octene copolymer and its untreated and modified silica‐filled composites were done with a shear dynamic oscillating rheometer. Modification of the silica filler, especially via the silanization process followed by electron beam treatment, significantly reduced filler–filler networking as revealed from the log–log plots of storage modulus and complex shear viscosity, and its real component. The rheological complexity of the compositions was analyzed from a double logarithmic plot of the storage modulus and loss modulus. The results obtained from the master curves constructed on the basis of the time–temperature superposition principle and the activation energy calculated from the Arrhenius equation for the flow of above these compounds further supported these findings. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2453–2459, 2003     

Molecular motions of non-crystalline poly(aryl ether-ether-ketone) PEEK and influence of elecron beam irradiation

The dynamic mechanical relaxation of non-crystalline poly(aryl ether-ether-ketone) PEEK and the one irradiated with electron beam were studied. The three distinct γ, β, α′ relaxation maxima were observed in unirradiated PEEK from low to high temperature. It was revealed from the study on the irradiation effects that three different molecular processes are overlapped in γ relaxation peak, i.e., molecular motion of water bound to main chain (peak temperature; at ?100°C), local motion of main chain (at ?80°C), and local mode of the aligned and/or oriented moiety (at ?40°C). The β relaxation connected with the glass transition occurred at 150°C and it shifted to higher temperature by irradiation. The α′ relaxation which can be attributed to rearrangement of molecular chain due to crystallization was observed in unirradiated PEEK ～ 180°C and its magnitude decreased with the increase in irradiation dose. This effect indicates the formation of structures inhibiting crystallization such as crosslinking and/or short branching during irradiation. A new relaxation, β′, appeared in the temperature range of 40° to 100°C by irradiation and its magnitude increased with dose. This relaxation was attributed to rearrangement of molecular chain from loosened packing around chain ends, which were introduced into the non-crystalline region by chain scission under irradiation, to more rigid molecular packing, From these observations, we proposed that deterioration in mechanical properties of non-crystalline PEEK by high energy electron beam was brought about not only by chain scission but structural changes such as crosslinking and/or branching in the main chain.     

Optimal error estimates of the penalty method for the linearized viscoelastic flows

In this article, optimal error estimates of the penalty method for the linearized viscoelastic flows equations arising in the Oldroyd model are derived. Furthermore, error estimates for the backward Euler time discretization scheme in L ² and H ¹-norms are obtained.     

Initial value methods for the primary two point boundary value problems in modeling viscoelastic flows

Initial value solvers through shooting methods will be used to compute solutions to the primary two-point boundary value problem arising in modeling viscoelastic flow. We will show that the classical Runge-Kutta methods will have at least h ²-order of convergence due to the presence of the singularity. Comparison with the work of others will also be presented through some numerical results and examples.