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.     

Computer simulation of the rheology of concentrated star polymer suspensions

We use particle-based computer simulations to study the rheology of suspensions of high-functionality star polymers with long entangled arms. Such particles have properties which are intermediate between those of soft colloidal particles and entangled polymer chains. In the simulations, each star polymer is coarse-grained to a single particle. In order to faithfully reproduce dynamical properties, it is very important to not only include time-averaged interactions (potentials of mean force) but to also account for transient interactions induced by entanglements between the arms of different star polymers. Using a model which has all these features, it is found that, for sufficiently high shear rates, the start-up shear stress displays an overshoot. With increasing concentration, the core interactions increasingly dominate the initial stress response, leading to a maximum in the stress overshoot at relatively low strain values (0.1 to 0.5). Transient forces start to dominate after this initial stage. In a simulated experiment in which the shear rate is suddenly stepped-down from a high to a lower value, the stress shows a clear undershoot, with the minimum stress again at a relatively low strain value (based on the new shear rate). Finally, it is shown that a stress plateau develops in the flow curve. This plateau is absent when the transient forces between the polymer stars are not taken into account.     

Prediction of multiple overshoots in shear stress during fast flows of bidisperse polymer melts

We present a differential constitutive model of stress relaxation in polydisperse linear polymer melts and solutions that contains contributions from reptation, contour-length fluctuations, and chain stretching. The predictions of the model during fast start-up and steady shear flows of polymer melts are in accord with experimental observations. Moreover, in accordance with reported experimental literature (Osaki et al. in J Polym Sci B Polym Phys 38:2043–2050, 2000), the model predicts, for a range of shear rates, two overshoots in shear stress during start-up of steady shear flows of bidisperse polymer melts having components with widely separated molar masses. Two overshoots result only when the stretch or Rouse relaxation time of the higher molar mass component is longer than the terminal relaxation time of the lower molar mass component. The “first overshoot” is the first to appear with increasing shear rate and occurs as a result of the stretching of longer chains. Transient stretching of the short chains is responsible for the early time second overshoot. The model predictions in steady and transitional extensional flows are also remarkable for both monodisperse and bidisperse polymer solutions. The computationally efficient differential model can be used to predict rheology of commercial polydisperse polymer melts and solutions.     

Microstructure constitutive equation for discotic nematic liquid crystalline materials –

The rheological material functions predicted by a previously selected constitutive equation (CE) for discotic mesophases are presented. The predicted relations among rheological properties, shear-induced microstructure, processing conditions and material parameters of discotic mesophases are characterized and discussed. The first and second normal stress differences corresponding to planar (i.e., 2-D orientation) microstructure mode of discotic nematics are found to be qualitatively similar to those for rod-like nematics despite the existing differences in flow-orientation characteristics. The first (second) normal stress difference for discotic mesophases corresponding to non-planar (i.e., 3-D orientation) microstructure mode is always positive (positive or negative depending on viscous effects) and is found to be due to flow-induced biaxiality. The effect of change in nematic potential (or temperature) on rheological properties of discotic mesophases is also presented. The apparent shear viscosities for various microstructure modes and material properties are also presented and shown to agree qualitatively with the available experimental data. Though only restricted validation of the predicted results with the actual experimental data of discotics is possible, the present study provides essential theoretical feedback to the on-going experimental work being pursued in understanding the processing behavior of mesophase pitches. Received: 24 February 1998 Accepted: 15 May 1998     

Impact of texture on stress growth in thermotropic liquid crystalline polymers subjected to step-shear

The Landau-de Gennes tensor order parameter equations of nemato-dynamics are formulated, solved and used to find the impact of textural transformation on stress growth in thermotropic liquid crystalline polymers subjected to shear start-up flow. The simulated textural transformations include nucleation and annihilation of twist inversion walls. Coarsening processes include wall-wall annihilation, wall pinching and wall-bounding surface reactions. In the absence of defect-related effects, the stress growth is characterized by an early stress plateau, intermediate power law growth, and a late stage stress plateau. As the Deborah number (De) increases, flow-induced textural transformations affect the late stage and then the intermediate stress growth stage. Defects are found to be stress sinks, and so removal of defects increases stress. At lower Deborah numbers, few defects arise and coarsening rates are low, so the main texture effect in this regime is in the late stage plateau region, causing localized step increases. At Deborah numbers close to one, nucleation and coarsening rates increase, and textural effects appear closer and closer to the intermediate stress growth regime. As De increases further, coarsening by pinching processes overcomes nucleation, and all defects disappear in the intermediate stress growth regime, causing the stress growth to exhibit a smooth staircase shape. Strain and amplitude scaling is not observed. Simulated textural transformations show that smooth staircase stress growth is the result of defect annihilation processes. The non-monotonic stress growth is consistent with experimental observations. Simulated textures provide specific knowledge important to the eventual understanding of the rheologies of textured liquid crystal polymers.     

Stress relaxation and creep of polymer gels in solvent under uniaxial and biaxial deformations

Stress relaxation and creep of polymer gels in solvent under various deformation modes such as uniaxial, strip-biaxial, and equibiaxial were theoretically investigated. The magnitudes of relaxed stress and the creep at equilibrium under each deformation mode were derived by a thermodynamic consideration of gel system. Combining a constitutive equation of gel with the equation of motion of polymer network, the stress and strain under each deformation mode have been formulated. The theory proposed here was applied to the rectangular gels under various deformations to calculate the stress relaxation and creep behavior of polymer networks in solvent. Two methods different in treatment of swelling under the constant strain or stress were employed for the calculation: one is based on the assumption that the swelling proceeds isotropically, and the other considers the anisotropic swelling process. The results obtained by the two methods mainly differ in the diffusion mode determining the swelling behavior. The possibility of undershoot of relative strain in load-free direction in the creep is also expected.     

一种考虑非比例附加损伤的多轴低周疲劳模型

在实际工作环境中,机械结构往往承受着多轴非比例循环载荷.相比多轴比例循环加载,多轴非比例循环加载由于产生了附加强化现象,造成机械结构疲劳寿命下降.通过分析薄壁圆筒管件在非比例加载工况下应力应变变化规律和发生破坏位置,本文基于临界面法提出一种考虑多轴非比例附加损伤的疲劳模型.该模型将最大剪切应变幅平面作为临界面,提出一个新的附加强化因子,结合临界面上切应变幅和正应变幅组成新的多轴疲劳损伤参量.此参量不仅考虑了非比例加载下临界面上正应变幅和切应变幅对材料造成的疲劳损伤,还考虑到应变路径的变化和材料非比例加载敏感特性对材料疲劳寿命的影响.考虑到实际情况下模型所需材料附加强化系数有时难以获得的情况,给出了材料附加强化系数的有关近似计算公式.只需要材料基本力学参数便可得到材料附加强化系数,方便工程实际应用.采用8种材料的多轴疲劳寿命数据对提出的新模型进行检验,结果表明所提出的新模型与传统多轴疲劳模型相比预测寿命精度更高.      

Influence of void nucleation on ductile shear fracture at a free surface

An approximate continuum model of a ductile, porous material is used to study the influence of the nucleation and growth of micro-voids on the formation of shear bands and the occurrence of surface shear fracture in a solid subject to plane strain tension. Bifurcation into diffuse modes is analysed for a plane strain tensile specimen described by these constitutive relations, which account for a considerable plastic dilatancy due to void growth and for the possibility of non-normality of the plastic flow law. In particular, bifurcation into surface wave modes and the possible influence of such modes triggering shear bands is investigated. For solids with initial imperfactions such as a surface undulation, a local material inhomogeneity on an inclusion colony, the inception and growth of plastic flow localization is analysed numerically. Both the formation of void-sheets and the final growth of cracks in the shear bands is described numerically. Some special features of shear band development in the solid obeying non-normality are studied by a simple model problem.     

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.     

Nonlinear viscoelasticity of PP/PS/SEBS blends

The nonlinear viscoelastic behavior of polypropylene/polystyrene (PP/PS) blends compatibilized or not with the linear triblock copolymer (styrene-ethylene-/butylene-styrene, SEBS) was investigated. Start-up of steady-shear at rates from 0.1 to 10 s^–1 was carried out using a controlled strain rotational rheometer and a sliding plate rheometer for strain histories involving one or several shear rates. The shear stress and first normal shear stress difference were measured as functions of time, and the morphologies of the samples before and after shearing were determined. For each strain history except that involving a single shear rate of 0.1 s^–1 the blends showed typical non-linear viscoelastic behavior: a shear stress overshoot/undershoot, depending on the history, followed by a steady state for each step. The first normal stress difference increased monotonically to a steady-state value. The values of the stresses increased with the addition of SEBS. The shear stress overshoot and undershoot and the times at which they occurred depended strongly on the strain history, decreasing for a subsequent shear rate step performed in the same direction as the former, and the time at which stress undershoot occurred increased for a subsequent shear rate step performed in the opposite direction, irrespective of the magnitude of the shear rate. This behavior was observed for all the blends studied. The time of overshoot in a single-step shear rate experiment is inversely proportional to the shear rate, and the steady-state value of N₁ scaled linearly with shear rate, whereas the steady-state shear stress did not. The average diameter of the dispersed phase decreased for all strain histories when the blend was not compatibilized. When the blend was compatibilized, the average diameter of the dispersed phase changed only during the stronger flows. Experimental data were compared with the predictions of a model formulated using ideas of Doi and Ohta (1991), Lacroix et al. (1998) and Bousmina et al. (2001). The model correctly predicted the behavior of the uncompatibilized blends for single-step shear rates but not that of the compatibilized blends, nor did it predict morphologies after shearing.     

In-plane modal testing of a free isotropic rectangular plate

In-plane vibration modes of an aluminum panel were experimentally identified from frequency response tests. Responses were measured on the panel edges and at selected locations on the panel surface. The measurements on the surface were made by attaching accelerometers oriented parallel to the panel plane. Resonance frequencies, relative damping ratios and mode shapes were established for the lowest 12 in-plane modes found in the frequency range between 1600 and 7000 Hz. A damping ratio of less than 0.05 percent of critical damping is proved to be valid for the aluminum panel. A finite element software was used to calculate 12 corresponding theoretical in-plane eigenfrequencies and mode shapes. An outline for a nondestructive procedure is suggested to estimate the input data for the elastic constants of an isotropic plate model. Two of the modes were used in analogy with the flexural vibration of beams and plates. The modes illustrate the deformation pattern including shear deformations, through the thickness, for the bending modes of thick beams or plates. The Rayleigh-Timoshenko theory also was used for the calculation of these two eigenfrequencies.     

The origin of stress-oscillation damping during startup and reversal of torsional shearing of nematics

Using a controlled-temperature shear cell mounted on a polarizing microscope, we observe the behavior of nematic 4,4-n-octyl-cyanobiphenyl (8CB) during start-up and reversal of shearing in a torsional parallel-plate geometry and correlate this behavior with rheological measurements. During the start-up, a sequence of birefringent rings, or twist walls, are observed that originate at the sample edge and propagate radially inward. Each twist wall is a thin region in which the director is twisted out of the plane of the velocity and velocity-gradient directions. The radial variation of in-plane orientation can be explained by the variation of strain in the parallel-plate device. A high Ericksen-number solution of the Leslie-Ericksen equations predicts a damped oscillatory shear stress response which agrees quantitatively with the measured stress oscillations out to an edge strain of around 50. The damping of the stress oscillations is due to the nonuniformity of strain in the parallel-plate geometry. On reversal of the flow, if the strain, , is smaller than about 500 units, the damping of stress oscillations is reversed; this correlates with an outward radial migration of twist walls. When > 500, disclinations nucleate and spoil the reversibility of stress damping.Deceased     

Rheo-optical investigations of lyotropic mesophases of polymeric surfactants

The shear orientation of hexagonal and lamellar liquid crystalline phases of polymeric surfactants was investigated by rheo-optical techniques (flow birefringence (Δn), small-angle light scattering) as well as by nuclear magnetic resonance and optical microscopy. The evolution of birefringence in the hexagonal phase is discussed for simple and oscillatory shear, and an alignment of rodlike micelles along the flow direction was found. A shear induced formation of vesicles (“onions”) is observed with the lamellar phase. They displayed a characteristic four-lobe pattern in depolarized light scattering. Above a critical shear stress vesicles were degraded and perpendicularly aligned lamellae (i.e. with their normal along the vorticity direction) were obtained. A comparison of experiments performed at constant stress and constant rate revealed that the vesicle to planar lamellae transition occurred above a critical shear stress. The behavior of the polysoap lyotropic mesophases under shear, i.e. the strain dependent alignment in the hexagonal phase, the shear induced formation of vesicles, and a transition to planar lamellae in the lamellar phase, is very similar to the behavior of lyotropic mesophases formed by low molar mass surfactants or amphiphilic block copolymers. The geometrical constraints that are introduced when amphiphilic side groups are fixed to a polymer backbone do not significantly alter the response of the mesophase to a shear deformation. Received: 4 May 1999 /Accepted: 19 July 1999     

A crack on the grain boundary — An analysis based on crystal plasticity theory

The influence of the mismatch of the lattice orientation on the deformation and stress fields of a crack located on the grain boundary is studied by means of the finite-element analysis taking account of finite deformatio and finite lattice rotation. The plane strain calculations for an fcc crystal subjected to mode I loading are performed on the basis of the crystalline plasticity described by a planar three-slip model. For the crack-tip shapes and the dominant deformation modes on slip systems, results of all the cases analysed here are in qualitative agreement with the earlier analytical and numerical solutions. Our results indicate that the lattice orientation difference may greatly influence the shear stress along the grain boundary which is related to grain-boundary sliding, while the normal stress along the grain boundary, which may induce cleavage fracture, is virtually insensitive to it. The influence of the lattice orientations on the crack-tip fields is also investigated under small-scale-yielding conditions and the comparison with the results of finite deformation is made.     

压缩-剪切复合应力下PMMA材料的静态力学特性研究

通过压缩具有一定倾斜角(0°,10°,15°,20°和25°)试件和双剪切模型试件,实现了单轴压缩、压缩-剪切复合应力以及纯剪切三种应力状态,得到PMMA(聚甲基丙烯酸甲酯)在相应应力状态下的应力-应变曲线,同时对不同应力状态下试件的破坏模式进行了分析。结果表明:在不同受力环境中材料的强度和破坏的机理不同;同单轴压缩状态下相比,材料在压缩-剪切复合应力状态下屈服极限、强度极限以及破坏应变均不同程度的增大,呈现明显的"剪切增强"现象。单轴压缩与压缩-剪切应力状态下试件的破坏模式均为在试件短对角面上出现明显的剪切屈服带,由应力分析得出试件剪应力在短对角面上达到最大,引起在此平面上分子链间滑动从而产生应变软化形成剪切屈服带;双剪切试件的破坏模式为与剪切面呈45°的斜面。     

Probing shear-banding transitions of the VCM model for entangled wormlike micellar solutions using large amplitude oscillatory shear (LAOS) deformations

We explore the use of large amplitude oscillatory shear (LAOS) deformation to probe the dynamics of shear-banding in soft entangled materials, primarily wormlike micellar solutions which are prone to breakage and disentanglement under strong deformations. The state of stress in these complex fluids is described by a class of viscoelastic constitutive models which capture the key linear and nonlinear rheological features of wormlike micellar solutions, including the breakage and reforming of an entangled network. At a frequency-dependent critical strain, the imposed deformation field localizes to form a shear band, with a phase response that depends on the frequency and amplitude of the forcing. The different material responses are compactly represented in the form of Lissajous (phase plane) orbits and a corresponding strain-rate and frequency-dependent Pipkin diagram. Comparisons between the full network model predictions and those of a simpler, limiting case are presented.     

A unified multiaxial fatigue damage parameter

According to the critical plane principle, a unified multiaxial fatigue damage parameter is presented based on the varying behaviour of the strains of the critical plane. Both the parameters of the maximum shear strain amplitude and normal strain excursion between adjacent turning points of the maximum shear strain on the critical plane are considered in the multiaxial fatigue damage parameter presented. An equivalent strain amplitude is made with both parameters of the maximum shear strain amplitude and normal strain excursion by means of von Mises criterion. Thus a new multiaxial fatigue damage parameter proposed in this paper may be used under either proportional or nonproportional loading, and may also be reduced to a uniaxial form. It is used to predict multiaxial fatigue life and good agreement is demonstrated by experimental data. The project is supported by the National Doctoral Foundation of China and National Natural Science Foundation of China.     

一种统一的多轴疲劳损伤参量

城分析多轴损伤临界面上的应变化特性的基础上,根据多轴疲劳临界损伤平面原理,提出利用多轴介面上的最大剪切应变幅与相临两个最大剪切应变值之间的法向应变幅所合成的ｖｏｎ Ｍｉｓｅｓ等效应变幅作为多轴疲劳损伤参量,该参量不含有任何材料常数,不仅能够适用于多轴比例与非比例加载下,而且可退化成单轴的形式,经四种材料的试验验证,结果是令人满意的。     

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.