Rheology of silica-filled polystyrene: From microcomposites to nanocomposites

Rheology and viscoelastic behavior of polystyrene (PS)/silica microcomposites and nanocomposites were studied. The apparent viscosity, transient shear stress growth after startup shear flow and stress relaxation after cessation of flow at various shear rates, the complex dynamic viscosity, the storage and loss moduli at small and large strain amplitudes and various frequencies were performed. The effect of size, shape and volume concentration of silica was discussed. The maximum volume concentration, corresponding to the concentration at which the relative viscosity of mixtures goes to infinity, with respect to the hydrodynamic contribution of the particles and to polymer-filler interactions was obtained. The difference between the yield stress and residual stress is shown. The domain of equivalence between the apparent viscosity as a function of the shear rate in steady state flow and the complex dynamic viscosity as a function of the strain rate amplitude in highly nonlinear region of oscillatory flow was established. The viscoelastic behavior was interpreted based on the morphology of microcomposites and nanocomposites observed by SEM.     

Rheological properties of immiscible polymer blends under parallel superposition shear flow

The small amplitude oscillations can be superimposed parallelly on steady shear flows. The resulting moduli provide information about time‐ and shear‐dependent microstructure. For this purpose, model blends composed of polydimethylsiloxane and polyisobutylene with the viscosity ratio of 7.9 and 0.25 are investigated. The resulting moduli are compared with the results derived from numerical calculation as well as analytical solutions, developed here by introducing the conditions under parallel superposition flow field into MM model. Good agreement is found in the interfacial contribution of the storage moduli for blend with low volume fraction. Moreover, detailed analysis on hydrodynamic interaction between droplets is given to explain the discrepancies. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 431–440, 2008     

Mechanical behavior and wrinkling patterns of phase-separated binary polymer blend film

The wrinkling of phase-separated binary polymer blend film was studied through combining the Monte Carlo (MC) simulation for morphologies with the lattice spring model (LSM) for mechanical properties. The information of morphology and structure obtained by use of MC simulation is input to the LSM composed of a three-dimensional network of springs, which allows us to determine the wrinkling and the mechanical properties of polymer blend film, such as strain, stress, and Young’s modulus. The simulated results show that the wrinkling of phase-separated binary polymer blend film is related not only to the structure of morphology, but also to the disparity in elastic moduli between polymers of blend. Our simulation results provide fundamental insight into the relationship between morphology, wrinkling, and mechanical properties for phase-separated polymer blend films and can yield guidelines for formulating blends with the desired mechanical behavior. The wrinkling results also reveal that the stretching of the phase-separated film can form the micro-template, which has a wide application prospect.     

Dynamics of Dendrimeric Molecules Undergoing Simple Shear Flow: A Nonequilibrium Brownian Dynamics Study

Nonequilibrium Brownian dynamics (NEBD) simulations are used to model the dynamics of six generations of dendrimers undergoing shear flow. A coarse‐grained bead‐spring model is proposed, which incorporates springs with stretching and bending potentials. The bending constant is used as one of the primary independent variables to control the deformability of the molecules. Rheological and conformational properties, such as viscosity, normal stress differences, visco‐elastic moduli, flow birefringence, mean square radius of gyration, and degree of prolateness, are observed under both transient (startup and cessation of flow) and steady‐state conditions. Comparisons are made with the corresponding linear chain analogs of the same molecular weight. The model qualitatively describes many of the experimentally observed effects in these systems, most notably a Newtonian viscosity profile (no shear thinning) and a maximum in the dependence of the intrinsic viscosity on the molecular weight. The dendrimers are also characterized by negligible start‐up overshoots in the transient viscosity and birefringence.     

Rheo‐optical studies of the effect of shear flow on the structure of elastomer blends

The effect of shear flow on the structure of a phase‐separated, near‐critical blend of 50/50 (w/w) poly(styrene‐ran‐butadiene) and polybutadiene was studied with two different custom‐built rheo‐optical instruments that combined polymer melt flow and small‐angle light scattering (SALS). The deformation of the phase domains during shear flow was nonaffine, and the SALS patterns evolved from a spinodal ring (SR) pattern to a squashed SR with two high‐intensity lobes, to an H‐pattern, to a butterfly pattern with a dark streak along the equator, and finally to a steady‐state, elliptical pattern. The SALS patterns were explained in terms of a network model, in which the strands of the network first orient in the flow direction, then extend in this direction, and finally break up into droplets aligned in the flow direction. According to this picture, the strands in the vorticity direction do not deform until relatively high strains, after which the periodicity of the network begins to disappear. Supporting this model was the observation that the transitions between the different SALS patterns corresponded to inflections and/or maxima in the shear stress or first normal stress difference. Increasing the shear rate changed the kinetics of the structure evolution and reduced the size of the phase‐separated droplets in the steady state. No evidence was obtained for flow‐induced miscibility. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1725–1738, 2004     

Structure and mechanical properties for binary blends of polypropylene and ethylene‐1‐hexene copolymer

The structure and mechanical properties of the injection‐molded products for the binary blends composed of an isotactic polypropylene (PP) and a rubbery ethylene‐1‐hexene copolymer (EHR) were studied. The following two types of blends were employed: one is the incompatible blend of PP and ethylene‐rich EHR; the other is the compatible blend of PP and 1‐hexene‐rich EHR. The incompatible blend shows a phase‐separated morphology, in which EHR domains in the skin layer highly orient to the flow direction. On the other hand, the compatible blend shows fairly homogeneous morphology in the skin and core regions, in which EHR molecules are dissolved into the amorphous PP region. The measurements of birefringence and infrared dichroism revealed that the magnitude of molecular orientation along the flow direction for the compatible blend is larger than that for the incompatible blend. Nevertheless, it was also found that anisotropy of the mechanical properties for the compatible blend is less prominent, which is attributed to lack of the mechanical connection between neighbor crystalline fragments aligned perpendicular to the flow direction. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 701–713, 1999     

Effect of shear on subsequent rheological transients in polymeric liquid crystals

The transient rheological behaviour of a lyotropic polymeric liquid crystal is investigated. The system consists of a 12% by weight solution of poly(γ-benzyl-L-glutamate) in m-cresol. The structural changes caused by steady state shearing and by large amplitude oscillatory flow are measured. This is done by following the linear moduli upon cessation of flow. The stress transients during a stepwise increase in shear rate are used for the same purpose. Flow always increases the subsequent moduli in the system used, but the mode and the intensity of the flow have a complex effect. The variable domain structure seems to be responsible for most of the measured behaviour. The data put specific constraints on the detailed mechanisms that can contribute to the global transient stress.     

Stratified morphology of a polypropylene/elastomer blend following channel flow

A thermoplastic olefin blend consisting of isotactic polypropylene (PP) and an ethylene‐butene copolymer (EBR) impact modifier (25 wt % EBR) was subjected to a short, high‐shear pulse within the flow channel of a pressure‐driven microextruder following low‐shear channel filling from a reservoir of the melt. The resulting morphology was examined by laser scanning confocal fluorescence microscopy (LSCFM), with contrast provided by a fluorescent tracer in the EBR minor phase. Shear experiments were performed under isothermal conditions with a known wall shear stress for a specified duration, providing a well‐defined thermal and flow history. Low‐shear channel filling produces small droplets across the central region of the channel and large droplets, consistent with steady‐state shear, in the regions near the channel walls. After cooling the molten blend to a crystallization temperature of 153 °C, a brief interval (5 s ～ 1/2000 of the quiescent crystallization time) of high shear (wall shear stress: 0.1 MPa) induces rapid, highly oriented crystallization and a stratified morphology. Ex situ LSCFM reveals a “skin” at the channel walls (～70 μm) in which greatly elongated fiberlike droplets, oriented along the flow direction, are embedded in highly oriented crystalline PP. Further from the walls but directly beside the skin layers are surprising zones in which EBR domains show no deformation or orientation. Several zones of intermediate deformation and orientation at an angle to the flow direction are located closer to the center of the channel. At the center of the channel, EBR droplets are spherical, as expected for channel flow. The various strata are explained by the interplay of droplet deformation, breakup, and coalescence with the shear‐induced crystallization kinetics of the matrix. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2842–2859, 2002     

Full‐chain dynamics of entangled linear and star polymers

The full‐chain dynamics and the linear viscoelastic properties of monodisperse, entangled linear and star polymers are simulated consistently via an equilibrium stochastic algorithm, based on a recently proposed full‐chain reptation theory 1 that is able to treat self‐consistently mechanisms of chain reptation, chain‐length fluctuations, and constraint release. In particular, it is the first time that the full‐chain simulation for star polymers is performed without subjecting to the great simplifications usually made. To facilitate the study on linear viscoelasticity, we employ a constraint release mechanism that resembles the idea of tube dilation, in contrast to the one used earlier in simulating flows, where constraint release was performed in a fashion similar to double reptation. Predictions of the simulation are compared qualitatively and quantitatively with experiments, and excellent agreement is found for all investigated properties, which include the scaling laws for the zero‐shear‐rate viscosity and the steady‐state compliance as well as the stress relaxation and dynamic moduli, for both polymer systems. The simulation for linear polymers indicates that the full‐chain reptation theory considered is able to predict very well the rheology of monodisperse linear polymers under both linear viscoelastic and flow conditions. The simulation for star polymers, on the other hand, strongly implies that double reptation alone is insufficient, and other unexplored mechanisms that may further enhance stress relaxation of the tube segments near the star center seem crucial, in explaining the linear viscoelasticity of star polymers. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 248–261, 2000     

稳态双曲流场中液/液混合的粘性液滴哑铃分散模型

通过对稳态双曲流场中液／液混合体系分散相液滴所受分散作用力的分析，建立了粘性液滴的哑铃分散模型．趋于将两粘性液滴分开的分散作用力与粘度比、流场类型和强度、液滴半径、哑铃取向和尺寸有关．该模型解释了流场类型与分散作用的关系．流场类型对液滴的分散具有很大影响，在纯应变拉伸流场中分散作用力是简单剪切流场中的两倍，因而对于液滴的分散，拉伸流场较简单剪切流场更有效，这与以前的实验结论符合．当体系粘度比趋于无穷大时本模型转化为刚性哑铃分散模型     

The effect of phase‐separated morphology on the rheological properties of polystyrene/poly(vinyl methyl ether) blend

The effect of phase‐separated morphology on the rheological properties of polystyrene/poly(vinyl methyl ether) (PS/PVME) blend was investigated by optical microscopy (OM), light scattering (LS) method, and rheology. The blend had a lower critical solution temperature (LCST) of 112°C obtained by turbidity experiment using LS at a heating rate of 1°C/h. Three different blend compositions (critical 30/70 PS/PVME by weight) and two off‐critical (50/50 and 10/90)) were prepared. The rheological properties of each composition were monitored with phase‐separation time after a temperature jump from a homogeneous state to the preset phase‐separation temperature. For the 30/70 and 50/50 blends, it was found that with phase‐separation time, the storage and loss moduli (G′ and G″) increased at shorter times due to the formation of co‐continuous structures resulting from spinodal decomposition. Under small oscillatory shearing, shear moduli gradually decreased with time at longer phase‐separation times due to the alignment of co‐continuous structures toward the flow direction, as verified by scanning electron microscopy. However, for the 10/90 PS/PVME blend, the rheological properties did not change with phase‐separation times. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 889–906, 1999     

Fiber motion and rheology of suspensions with uniform fiber orientation

One of the main goals in the studies of fiber suspensions is the prediction of fiber orientation in a short fiber composite part, using the processing variables, mold geometry, and material characteristics. The rheological properties of the fiber suspensions are strongly associated with the fiber orientation distribution. The understanding of the relations between the fiber structure in the suspension and its rheological properties is a key step in the design and implementation of processing operations. The fiber motion in shear flow is analyzed in this article. The study is focused on the relation between fiber orientation and rheological properties for a suspension with uniform (delta function) fiber orientation distribution in a Newtonian fluid. The study shows that the rheological properties of the suspension, measured during the start up of steady shear flow, can be used to determine the fiber orientation in the sample. The first normal stress coefficient is the property to measure in order to determine whether or not the suspension has a random fiber orientation. Any of the shear flow transient rheological properties can be used to determine the fiber initial orientation. It was found that the normal stress coefficients can show negative or positive values depending on the fiber orientation. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1788–1799, 2000     

Thermal,crystallization, mechanical,and rheological characteristics of poly(trimethylene terephthalate)/poly(ethylene terephthalate) blends

Blends of poly(trimethylene terephthalate) (PTT) and poly(ethylene terephthalate) in the amorphous state were miscible in all of the blend compositions studied, as evidenced by a single, composition‐dependent glass‐transition temperature observed for each blend composition. The variation in the glass‐transition temperature with the blend composition was well predicted by the Gordon–Taylor equation, with the fitting parameter being 0.91. The cold‐crystallization (peak) temperature decreased with an increasing PTT content, whereas the melt‐crystallization (peak) temperature decreased with an increasing amount of the minor component. The subsequent melting behavior after both cold and melt crystallizations exhibited melting point depression behavior in which the observed melting temperatures decreased with an increasing amount of the minor component of the blends. During crystallization, the pure components crystallized simultaneously just to form their own crystals. The blend having 50 wt % of PTT showed the lowest apparent degree of crystallinity and the lowest tensile‐strength values. The steady shear viscosity values for the pure components and the blends decreased slightly with an increasing shear rate (within the shear rate range of 0.25–25 s^?1); those of the blends were lower than those of the pure components. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 676–686, 2004     

Toughening of nylon 6 with a maleated core-shell impact modifier

Super-tough nylon 6 was prepared by using maleic anhydride grafted polyethylene-octene rubber/semicrystalline polyolefin blend (TPEg) as an impact modifier. The morphology, dynamic mechanical behavior, mechanical properties, and toughening mechanism were studied. Results indicate that TPEg with a semicrystalline polyolefin core and a polyethylene-octane rubber shell, possesses not only a better processability of extruding and pelletizing with a lower cost, but also an improved toughening effect in comparison with the maleated pure polyethylene-octene rubber. The shear yielding is the main mechanism of the impact energy dissipation. In addition, the influence of melt viscosity of nylon 6 on toughening effectiveness was also investigated. High melt viscosity of matrix is advantageous to the improvement of notched Izod impact strength. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1987–1994, 1998     

Parallel superposition of small- and large-amplitude oscillations upon steady shear flow of polymer fluids

The parallel superposition of small- and large-amplitude oscillations upon steady shear flow of elastic fluids has been considered. Theoretical results, obtained by numerical methods, are based upon the Leonov viscoelastic constitutive equation. Steady-state components, amplitude, and phase angle of oscillatory components of the shear stress, the first and second normal-stress differences as a function of shear rate, deformation amplitude, and frequency have been calculated. These oscillatory components include the first harmonic of the shear stresses and the first and second harmonic of the normal stresses. In the case of small-amplitude superposition, the effect of the steady shear flow upon frequency-dependent storage and loss moduli has been determined and compared with experimental data available in the literature for polymeric solutions and melts. In the case of large-amplitude superposition, the effect of oscillations upon the steady shear flow characteristics has been determined and compared with our experimental data for a polymeric melt. The experimental results for shear stress components have been found to be in good agreement with theoretical predictions, although there are some deviations for storage modulus at high shear rates. The deviations seem to be dependent on material. Moreover, the theory is unable to describe experimental data available for the first harmonic of normal stresses.     

含氰基离子液体的合成、表征及流变性质研究

摘要合成、 表征了一系列新的含氰基咪唑类离子液体. 测定了该离子液体的密度、 熔点及溶解性等物理性质, 研究了其在稳态、 瞬态和动态条件下的流变行为. 结果表明, 当剪切速率在0.1～50 s^-1范围内时, 其粘度不随剪切速率的变化而变化, 但随温度升高而降低, 粘流活化能随取代基长度变化呈现规律性变化. 对于1-丁基-3-氰乙基咪唑六氟磷酸盐离子液体, 维持剪切速率不变时, 其剪切应力和粘度均不随时间变化, 且随着温度的升高而降低; 在动态条件下, 在线性粘弹区, 复合粘度和损耗模量G″ 随温度升高而降低. 关键词     

Flow‐induced particle orientation and rheological properties of suspensions of organoclays in thermoplastic resins

The influence of nano‐scale particles on the viscoelastic properties of polymer suspensions is investigated. We have developed a simulation technique for the particle orientation and polymer conformation tensors to study various features of the suspensions. The nano‐particles are modeled as thin rigid oblate spheroid particles and the polymers as FENE‐P type viscoelastic and Newtonian fluid. Both interparticle and polymer‐particle interactions have been taken into account in our numerical computations. The nonlinear viscoelastic properties of nanocomposites of layered silicate particles in non‐Newtonian fluids are examined at the start‐up of shear flow and are interpreted using the model to examine the effects of model parameters as well as flow conditions on particle orientation, viscosity, and first normal stress difference of the suspensions. We have studied the microstructure of polymer‐clay nanocomposites using X‐ray diffraction (XRD) scattering and transmission electron microscopy (TEM). The rheology of these nanocomposites in step‐shear is shown to be fairly well predicted by the model. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 2003–2011, 2010     

Predictions of Some Internal Microstructural Models for Polymer Melts and Solutions in Shear and Elongational Flows

Summary: In this work, the behavior of some internal microstructural models with different mobility tensors has been studied for polymer melts and solutions under steady and transient simple shear and elongational flows. The time evolution equations for conformation and stress tensors in the models reviewed have their root in the Generalized Poisson bracket formalism. Two different families of conformational models have been selected for this study. The first family is based on the Modified Finitely Extensible Nonlinear Elastic (FENE‐P) energy while the second uses a Volume Preserving Conformational Rheological (VPCR) model based on the Hookean Helmholtz free energy function. Several expressions for the mobility tensor based on the previously mentioned energy functions are used to obtain the models. The sensitivity of both families of models to the choice of the mobility tensors on the prediction of material functions in the transient and steady flows is discussed. Also, effects of shear rate on the material functions in start‐up and relaxation shear flows for both models are studied. The predictions of both models are compared with experimental data taken from the literature for some polymer melts. These results show that the family of VPCR models is able to predict the steady shear and elongational flow material functions in an extended range of deformation rates whereas the family of FENE‐P models can predict the behavior of only some specified polymer melts.

Experimental data and VPCR model predictions for steady and elongational viscosity for PS [data of H. Munstedt, 1980].     

Thermoplastic blend demixing by a high‐pressure,high‐temperature process

The analysis of a thermoplastic polymer blend requires a precise separation of the blend components, which is usually performed by selective solvent extraction. However, when the components are high‐molecular‐weight polymers, a complete separation is very difficult. The use of fluids in near critical and supercritical conditions becomes a promising alternative to reach a much more precise separation. In this work, a method to separate reactive and physical blends from high‐molecular‐weight commercial polymers is proposed. Polyethylene (PE)/polystyrene (PS) blends were separated into their components with n‐propane, n‐pentane, and n‐heptane at near critical and supercritical conditions. The selectivity of each solvent was experimentally studied over a wide range of temperatures for assessing the processing windows for the separation of pure components. The entire PE phase was solubilized by n‐pentane and n‐heptane at similar temperatures, whereas propane at supercritical conditions could not dissolve the fraction of high‐molecular‐weight PE. The influence of the blend morphology and composition on the efficiency of the polymer separation was studied. In reactive blends, the in situ copolymer formed was solubilized with the PE phase by chemical affinity. The method proposed for blend separation is easy, rapid, and selective and seems to be a promising tool for blend separation, particularly for reactive blends, for which the isolation of the copolymer is essential for characterization © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2361–2369, 2005