Elastic recovery of immiscible blends 1. Analysis after steady state shear flow

Due to the interfacial tension, immiscible blends can show an elastic recovery that is substantially larger than that of their pure components. Here it is attempted to relate the elastic recovery after steady shear flow to the underlying morphology. On the one hand, the predictions of the Palierne and the Doi-Ohta models are calculated for the flow conditions during recoil. On the other hand, systematic recoil experiments after steady state shearing have been performed on a model blend. As the component polymers hardly show any recoil under the stresses applied in these tests, the measured recovery can be attributed completely to the action of the interface. Comparison of the model predictions with the experimental results shows that the recoverable strain can be derived quantitatively from the linear Palierne theory. Although the droplet deformation remained limited during the preshear, the retardation time predicted by this model has to be multiplied by the aspect ratio of the droplet phase to the power 2/3 to describe the experiments. For conditions in which the material does not show an intrinsic length scale, particular scaling relations as derived from the Doi-Ohta theory are found to apply also to recoil. Received: 5 August 1998 Accepted: 17 November 1998     

Stress relaxation as a microstructural probe for immiscible polymer blends

Relaxation has been investigated in immiscible blends that consist of slightly viscoelastic components. Both the shear and normal stresses have been measured after cessation of steady shear flow as well as after transient shear histories. The latter can generate a fibrillar structure which can relax by either retraction or break-up via end-pinching or Rayleigh instabilities. Each of these three relaxation mechanisms is reflected in the shape of the stress curves, from which also the corresponding structural time scales can be deduced. The experimental results have been used to evaluate the Doi-Ohta and Lee-Park models for immiscible blends. The scaling relations by Doi-Ohta are confirmed by the experimental results, but none of the existing models can correctly predict the complex relaxation behaviour observed for a highly deformed droplet phase. In the present study an alternative approach has been proposed. The stress relaxation due to fibril break-up via Rayleigh instabilities has been predicted successfully by combining physical models for the structural changes with the basic approach of the Doi-Ohta model.     

Stress relaxation behavior of co-continuous PS/PMMA blends after step shear strain

Stress relaxation probing on the immiscible blends is an attractive route to reveal the time-dependent morphology–viscoelasticity correlations under/after flow. However, a comprehensive understanding on the stress relaxation of co-continuous blends, especially after subjected to a shear strain, is still lacking. In this work, the stress relaxation behavior of co-continuous polystyrene/poly(methyl methacrylate) (50/50) blends with different annealing times, strain levels, and temperatures was examined under step shear strain and was correlated with the development of their morphologies. It was found that co-continuous blends display a fast relaxation process which corresponded to the relaxation of bulk polymer and a second slower relaxation process due to the recovery of co-continuous morphology. The stress relaxation rates of co-continuous blends tend to decrease due to the coarsening of instable co-continuous structure during annealing. Furthermore, the stress relaxation of the co-continuous blends is strongly affected by the change of viscosity and interfacial tension caused by the temperature. The contribution of morphological coarsening, viscosity, and interfacial tension variation on the stress relaxation behavior of co-continuous blends was discussed based on the Lee–Park model and time–temperature superposition principle, respectively.     

Rheological properties of PDMS/clay nanocomposites and their sensitivity to microstructure

The effect of microstructure on the rheology of clay/polymer nanocomposites is investigated using dispersions of organically treated clay in nearly Newtonian poly(dimethylsiloxane). Degree of dispersion and floc size are altered by using two different dispersion procedures and by changing the shear history. The scaling for dynamic moduli of attractive colloids applies, except for a possible relaxation mechanism at very low frequencies. The time to reach the crossover at a given frequency is found to be extremely sensitive to the dispersion procedure used. Hydrodynamic and elastic components of the steady state stress, on the other hand, evolve in a very similar fashion for the different systems. Although the relaxation times of the elastic stress components change drastically with flow-induced changes in structure, the dispersion process hardly has an effect at all. Intermittent start-up flows in the forward and reverse directions show that anisotropy persists long after the flow has been arrested, even at shear rates where no large reversible flocs are present. The degree of dispersion only had a limited effect on the anisotropy. Finally, the effect of shear on structure recovery has been studied. Very low shear rates are found to increase the rate of recovery, even for small strains.     

Stress relaxation after steady shear flow in immiscible model polymer blends

Stress relaxation in immiscible blends is studied for a well defined shear history, i.e. after prolonged steady state shearing. Model systems are used that consist of quasi-Newtonian liquid polymers. Hence the relaxation is dominated by changes in the morphology of the interface. Both shear stress and the first normal stress are considered. The measurements cover the entire concentration range. For dilute blends the interfacial contribution to the stress relaxation compares well with model predictions. Deviations occur when the matrix phase is slightly elastic. In that case the similarity between the relaxation of shear and normal stresses is also lost. The latter is attributed to a wider drop size distribution.Increasing the concentration of the disperse phase results in a complex evolution of the characteristic relaxation times. The normal stresses relax systematically slower than the shear stresses and the concentration curve includes two maxima. Even for equiviscous components the concentration curves are not symmetrical. It is concluded that even a slight degree of elasticity in the matrix phase drastically affects the morphology and the interfacial relaxation of such blends.     

Transient rheological behaviour of poly-para-henylenetherephthalamide (PpPTA) in sulphuric acid

Nearly all the available information on the transient flow behaviour of liquid crystalline polymers has been obtained on model systems, especially on solutions of polybenzylglutamate (PBG) and hydroxypropylcellulose (HPC). The assessment of rheological models has been based almost entirely on these model systems. It is not clear how much of the available theoretical and experimental knowledge can be applied to systems of industrial relevance, which have quite different molecular structures. Here, an industrial lyotropic system, poly(p-phenylenetherephthalamide) (PpPTA) in sulphuric acid (TWARON from AKZO), is investigated. Various techniques to study transient behaviour are used, these include measurements of transient shear and normal stresses after sudden changes in shear rate, dynamic moduli and stress relaxation after cessation of flow and elastic recoil. At all shear rates studied the PpPTA solution is shear thinning, and the first normal stress difference remains positive. For the stress transients a strain scaling applies reasonably well as it did in model systems. The moduli increase with time upon cessation of flow, indicating that the molecules become less oriented in the previous flow direction. This particular behaviour is similar to that of HPC. Transients also resemble more closely those of HPC rather than those of PBG. This latter difference might be attributed to the higher flexibility of HPC and PpPTA chains as compared with PBG molecules.     

Rheological properties of disperse systems at low shear stresses

Three-dimensional network structures can be built up in disperse systems due to long-range colloidal interactions between the dispersed particles. The rheological behaviour of such coagulation structures has been studied by means of creep and recovery experiments at low shear stresses, i.e. by measuring the shear strain as a function of time under constant stress and after removal of stress. Measurements of this type give insight into the elastic and viscous deformations and the retardation times necessary to reach equilibrium or steady-state conditions.Results obtained with dispersions of pigments in polymer solutions and with monodisperse polymer latexes indicate the existence of an equilibrium state at low shear stresses with a predominant elastic deformation and a high viscosity suggesting that the disperse systems investigated do not behave exactly as rigid gels but apparently exhibit a dynamic equilibrium of structural break-down and formation under applied stress. This behaviour is approximately described by a 4-parameter-model with an instantaneous and a steady-state compliance, one retardation time, and a viscosity.At higher shear stresses thixotropic structural break-down occurs resulting in a transition from the rheological behaviour described here to a liquid-like state with a comparatively low viscosity. In this stress range the viscoelastic properties become strongly time-dependent.These measurements give evidence of the presence of two types of deformation: an instantaneous, purely elastic deformation attributable to the unperturbed coagulation structure and the creep-recovery behaviour of an elastic liquid apparently related to the breaking and re-forming of bonds.     

Stress overshoots of organoclay nanocomposites in transient shear flow

Forward and reverse stress growth experiments have been conducted on polypropylene/organoclay nanocomposites containing the same clay loading but characterized by different microstructures. Stress overshoots have been observed for the initial start-up experiments and for the following reverse start-up experiments after a certain rest time. The amplitude of these overshoots increased with the applied shear rate and rest time, but the overshoots occurred at the same strain of about 1.7. The overshoots are related to the structure of the nanocomposites, in particular the magnitude of the overshoots increased with the degree of the clay exfoliation in the matrix. Two models, initially developed for colloidal suspensions and fiber suspensions, have been used to describe the observed phenomena. The overshoots are fairly well predicted by the first (structure network) model and explained by the competing effects of the structure breakdown under flow and reorganization during rest time. However, the model predicts that the shear stress following the overshoot decreases and reaches steady-state too rapidly. The second model developed for ellipsoid suspensions describes quite well the stress overshoots for the initial forward flow, but no effect of rest time is predicted. A modified version has been proposed by adding a molecular diffusivity contribution in the Folgar–Tucker equation. The effect of the particle disorientation is qualitatively predicted, but the kinetics is too slow compared to that deduced from experiments.     

60Si2Mn螺旋弹簧的压缩应力松弛行为与贮存寿命预测

为评价60Si2Mn螺旋压缩弹簧的室温松弛特性,利用InstronE3000K8953型小吨位电子动静态疲劳试验机,对其在不同温度和初始应力水平条件下进行了高温压缩加速应力松弛试验,研究了环境温度、初始应力水平对松弛行为的影响.基于粘弹性体模型,揭示了应力松弛过程中弹性应变向塑性应变的转化特性与塑性应变随松弛时间的变化规律.在对应力松弛前后弹簧丝材金相和TEM微结构进行对比分析的基础上,探讨了应力松弛的微观机制.结果表明,环境温度与初始应力水平对松弛速率具有显著影响.基于应力松弛过程的热激活特性,建立了60Si2Mn螺旋压缩弹簧的贮存寿命预测方程,并对不同应力水平下弹簧的室温和高温贮存寿命进行了合理预测.     

Effects of compatibilization on rheological properties of PS/PB blends and investigation of Doi–Ohta scaling relationship in double start-up of shear experiments

The rheological properties for the blends of polystyrene and polybutadiene were investigated and the effect of compatibilizer styrene butadiene rubber (SBR), on the blends were studied and the results compared with the non-compatibilized blends. The frequency sweep, step shear strain and shear stress growth experiments were carried out for the blends. The results showed that with addition of compatibilizer the changes in behavior of the rheological properties of blends are observed. These rheological variations could be related to the reduction of interfacial tension and size of dispersed phase. Furthermore, the validity of Doi–Ohta scaling relationship in double start-up experiments was studied. It is shown that this scaling relationship becomes more reliable with increasing the amount of PB and compatibilizer.     

超高分子量聚乙烯材料的应力松弛研究

采用实验方法研究超高分子量聚乙烯(UHMWPE)材料,在不同温度、应变率和初始应变的条件下进行单轴压缩应力松弛实验,得出松弛应力与时间成非线性关系,且温度越高、应变率越大、初始应变越小,则最终稳定的应力值越小的结论．采用时间分数阶粘弹性模型,结合Boltzmann叠加原理推导出UHMWPE材料在整个加载段及松弛段的应力响应函数,并与实验数据最小二乘拟合．结果表明,时间分数阶Scott-Blair模型能很好地描述UHMWPE材料的粘弹性行为．     

Comparison of viscous and elastic properties of polyolefin melts in shear and elongation

Viscous and elastic properties of a linear polypropylene (PP) and a long-chain branched low-density polyethylene (LDPE) have been investigated by creep and creep–recovery experiments in shear and elongation. The data obtained verify the ratios between the linear values of the viscosities and the steady-state elastic compliances in shear and elongation predicted by the theory of linear viscoelasticity. In the nonlinear range, no simple correlation between the viscous behaviour in shear and elongation exists. The elongational viscosity of the PP decreases with increasing stress analogously to the shear thinning observed; the linear range extends to higher stresses in elongation than in shear, however. The LDPE shows thinning in shear and strain hardening in elongational flow. For the LDPE, a linear steady-state elastic tensile compliance corresponding to one third of the linear steady-state elastic compliance in shear was determined. For the PP, this theoretically predicted value is approximately reached. Analogous to the viscous behaviour, the linear range extends to higher stresses in elongation than in shear. For both materials, the steady-state elastic compliances in the nonlinear range decrease with increasing stress in shear as well as in elongation. However, the decrease in elongation is more pronounced.     

Elongational-flow predictions of the Leonov constitutive equation

The basic thermodynamic ideas from rubber-elasticity theory which Leonov employed to derive his constitutive model are herein summarized. Predictions of the single-mode version are presented for homogeneous elongational flows including stress growth following start-up of steady flow, stress decay following sudden stretching and following cessation of steady flow, elastic recovery following cessation of steady flow, energy storage in steady-state flow, and the velocity profile in constantforce spinning. Using parameters of the multiple-mode version which fit the linearviscoelastic data, the Leonov-model predictions of elongational stress growth during, and elastic recovery following, steady elongation are calculated numerically and compared to the experimental results for Melt I and to the Wagner model. It is found that the Leonov model, as originally formulated, agrees qualitatively with the data, but not quantitatively; the Wagner model gives quantitative agreement, but requires much nonlinear data with which to fit model parameters. Quantitative agreement can be obtained with the Leonov model, if the nonequilibrium potential which relates recoverable strain to strain rate is adjusted empirically. This can most simply be done by making each relaxation time dependent upon the recoverable strain. The Leonov model, unlike the Wagner model, is derived from an entropic constitutive equation, which is advantageous for calculating stored elastic energy or viscous dissipation. The Leonov model also has an appealingly simple differential form, similar to the upper-convected Maxwell model, which, in numerical calculations, may be an important advantage over the integral Wagner model.     

Rheology and flow-birefringence from viscoelastic polymer-clay solutions

 The shear orientation of viscoelastic clay-polymer solutions was investigated by means of rheology and flow birefringence (Δn). The polymer chains are in dynamic adsorption/desorption equilibrium with the clay particles to form a “network”. The elastic behavior of the network was characterized by constant stress, oscillatory shear, and stress relaxation experiments. Constant stress experiments indicated a yield stress upon which shear flow started and no strain recovery could be observed. Oscillatory shear experiments showed a broad elastic region followed by flow when a critical strain was reached. Stress relaxation experiments showed several relaxation times when the same critical strain was reached. Experiments under steady flow characterized the transient behavior of the network. With increasing steady shear rate a pronounced minimum in birefringence was observed at a critical shear rate. The shear rate dependent viscosity showed near power law behavior and no corresponding critical feature. While birefringence detects orientational effects on a microscopic length scale, rheology averages over macroscopic changes in the sample. The same degree of orientation could be achieved under constant shear rate or constant stress conditions. Received: 25 January 2001 Accepted: 22 May 2001     

Kinematic hardening model suitable for ratchetting with steady-state

A new kinematic hardening model useful for simulating the steady-state in ratchetting is developed within the framework of the strain hardening and dynamic recovery format. The model is formulated to have two kinds of dynamic recovery terms, which operate at all times and only in a critical state, respectively. The model is examined on the basis of nonproportional experiments of Modified 9Cr–1Mo steel at 550°C and IN738LC at 850°C. The experiments include multiaxial, as well as uniaxial, ratchetting, multiaxial cyclic stress relaxation, and nonproportional cyclic straining along a butterfly-type strain path. It is shown that the model is successful in simulating the experiments, and that the model is featured by the capability of representing appropriately the steady-state in ratchetting under multiaxial and uniaxial cyclic loading.     

Bread dough rheology: an improved damage function model

We describe an improved damage function model for bread dough rheology. The model has relatively few parameters, all of which can easily be found from simple experiments as discussed in this paper. Small deformations in the linear region are described by a gel-like power-law memory function. Then, we consider a set of large non-reversing deformations—stress relaxation after a step of shear, steady shearing and elongation beginning from rest and biaxial stretching. With the introduction of a revised strain measure which includes a Mooney–Rivlin term, all of these motions can be well described by the damage function described previously. For reversing step strains, larger amplitude oscillatory shearing and recoil we present a discussion which shows how the damage function model can be applied in these cases.     

Influence of the flow history on stress growth and structure changes in the thermotropic liquid crystalline polymer Vectra B950

The structure changes in the start-up flow of the thermotropic liquid crystalline polymer Vectra 8950 are probed by performing transient experiments after various flow histories. The shear and normal stress growth curves of a squeezed sample and of a randomly oriented sample show a pronounced overshoot at low strains, whereas the stress growth curve of a sample pre-sheared until steady state shows a gradual increase. This first peak is associated with the re-orientation of the director into the shearing plane. All stress transients show a second broad maximum at large strains that results from the generation of a steady defect network. The effect of varying the relaxation period after pre-shearing is reflected in the appearance of two peaks in the subsequent stress growth curves. One of these peaks shifts linearly with re laxation period and the other is more or less fixed in position. The orientation of the molecules during steady shear flow is on average in the flow direction. Intermediate orientation levels may exist in the transient depending on the amount of strain. The material is able to maintain the flow-induced orientation distribution for a long time after cessation of flow. This is reflected in a similar fashion in the initial magnitudes of the stresses and the dynamic moduli after various preshear strains. Moreover, the dynamic moduli decrease with time after cessation of steady shear flow, indicating that the orientation increases during relaxation.     

Relaxation behavior and modeling

Load relaxation tests deliver several orders of magnitude of inelastic strain rate data while elastic strains are converted into inelastic strains [see Lemaitre and Chaboche, 1994. (Mechanics of Solid Materials, Oxford University Press, Cambridge p. 264)]. Hart used this test for providing information on the inelastic deformation behavior for modeling purposes. Characteristic relaxation curves were obtained with ductile metals and alloys at room and high temperature showing a scaling relation derived from Hart's theory. Subsequent testing with servo-controlled testing machines and strain measurement on the gage length showed that an increase of prior strain rate also increased the average relaxation rate. For relaxation tests starting in the flow stress region, the relaxation curves can be independent of the stress and strain at the start of the relaxation tests. For the modeling of these newly found relaxation behaviors and other phenomena the viscoplasticity theory based on overstress (VBO) has been introduced. It is shown that VBO admits a long-term (asymptotic) solution that can be used with sufficient accuracy for the flow stress region of the stress–strain diagram. The long-term solution predicts the observed relaxation behaviors and that the relaxation curves coincide when shifted along the stress axis. This behavior is observed for the recently obtained data and is confirmed by two sets of the Hart-type data when they are plotted according to the new method.     

The effect of pre-shear on the extensional rheology of wormlike micelle solutions

The effect of initial microstructural deformation, alignment, and morphology on the response of wormlike micelle solutions in transient uniaxial extensional flows is investigated using a pre-shear device attached to a filament stretching rheometer. In filament stretching experiments, increasing the strength and the duration of the pre-shear just before stretch is found to delay the onset of strain hardening. In these experiments, the wormlike micelle solution filaments fail through a rupture near the axial midplane. The value of the elastic tensile stress at rupture is found to decrease with increasing pre-shear rate and duration. The most dramatic effects are observed at shear rates for which shear banding has been independently observed. The reduction in the strain hardening suggests that pre-shear before filament stretching might break down the wormlike micelles reducing their size before stretch. Strain hardening is also observed in capillary breakup rheometry experiments; however, the pre-sheared wormlike micelle solutions strain harden faster, achieve larger steady-state extensional viscosities and an increase in the extensional relaxation time with increasing shear rate and duration. The difference between the response of the wormlike micelles in filament stretching and capillary breakup experiments demonstrates the sensitivity of these self-assembling micelle networks to pre-conditioning.     

Modeling of steady and time-dependent responses in filled, uncured, and crosslinked rubbers

Filled polymer systems have been a subject of interest for rheologists for several decades. Their applications range from paints and pigments to high performance composite materials. Presently, there is a lack of complete understanding of the behavior of these materials under varying kinematic and dynamic conditions. Moreover, there is a lack of a comprehensive theory, which can simultaneously describe the rheology of filled rubbers, their chemorheology, and their behavior in the final fully cured state. The present work is aimed at capturing a wide range of rheological (viscoelastic and kinetic) properties of filled rubbers with one set of constitutive/kinetic equations and a flexible relaxation spectrum. The various experiments covered are yield-flow transition in creep, shear start up responses, dynamic behavior in the melt state, and the changes during the cure stage. In the post cure state, the manifestations in Mullins stress softening-hysteresis and recovery, large strain stress relaxations, and dynamic behavior are also demonstrated. Finally, the non-linearities during large strain dynamic deformations, accompanied by non-isothermal, viscoelastic, and structure effects are exemplified. Received: 24 July 2000 Accepted: 13 November 2000