Transient rheology of discotic mesophases

This paper presents an analysis of the role of orientation on the rheology of discotic mesophases subjected to slow shear start-up flows, using a projection of the Landau-de Gennes equations of nematodynamics. Analysis of the shear stress surface as a function of tilt and twist orientation with respect to the shear plane shows that the stress surface is dense in well-oriented and periodically located sets of maxima and minima. Thus overshoots and undershoot stress responses to shear-start up are predicted to be the rule rather than the exception. In-plane (within the shear plane) shear start-up stress responses can exhibit multiple, single, or no overshoots, depending on the number of maxima traversed on the way to steady state. Responses originating from orientations close to the vorticity axis lead to stress undershoots. Complex stress responses, such as a weak overshoot-strong undershoot sequence, are found for intermediate tilt-twist initial states. In-plane modes lead to amplitude and strain scaling. Out-of-plane modes do not display amplitude or strain scaling. These results provide will be useful to interpret and use transient shear rheological data of carbonaceous mesophases and highly filled suspensions of disc-like particles.     

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.     

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.     

Rheological properties of concentrated latex suspensions of poly(styrene-butadiene)

Concentrated suspensions of charged latex particles of poly(styrene-butadiene) have been used as model systems to investigate the influence of surface charges on the rheology of colloidal suspensions. The suspensions were found to behave as elastic solids at small strains and to require a finite stress to flow. This was related to an ordered structure of the suspensions at rest, resulting from electrostatic and van der Waals forces. Important shear-thinning effects were observed as a consequence of structure rearrangements under shear. At a fixed shear rate, the steady-shear viscosity as a function of the ionic strength exhibits a minimum. Under oscillatory shear flow, the behavior of the concentrated suspensions was found to be non-linear above a very small strain amplitude. The non-linear output signal from dynamic experiments was analyzed using a fast Fourier transform algorithm. A maximum in the third harmonic intensity as a function of the strain amplitude was observed and the intensity of higher harmonics decreased with increasing ionic strength. The behavior of the suspensions could be adequately described using the structural model of Yziquel et al. (Yziquel F, Carreau PJ, Moan M, Tanguy PA (1999) Rheological modeling of concentrated colloidal suspensions. J Non-Newtonian Fluid Mech 86:133–155).     

Brownian dynamics simulation of multiphase suspension of disc-like particles and polymers

A computational model is proposed for simulating the flow of polymer nanocomposites. This model is based on a multiphase suspension of disc-like particles and polymers. The particles are represented by oblate spheroid particles that interact with each other via the Gay-Berne (GB) potential, and the polymers are modeled by finitely extensible nonlinear elastic (FENE) chains that interact with each other via the repulsive Lennard-Jones potential. The interaction between an oblate spheroid particle and a FENE chain is also considered using a modified GB potential. A Brownian dynamics simulation of the shear flows of this system was conducted to investigate the orientation behavior of disc-like particles and the rheological properties of this system. The orientation of disc-like particles was affected by polymers, and the particles in a suspension were well aligned in flows because of the flow orientation property of polymers. The predicted shear viscosity exhibited shear thinning, and the normal stress differences agree qualitatively with experimental measurements of polymer/clay nanocomposites. The simulation results suggest that the present model has the potential to be used as a computational model for polymer nanocomposites.     

Shearing and mixing effects on synthesis and properties of organoclay/polyester nanocomposites

Mixing of solid nanoparticles in viscous fluids is a key stage in synthesis of nanocomposites and can affect their final properties. A multi-step preparatory mixing is developed to synthesize the nanocomposites of layered silicate in thermosetting polymers. This study aims to investigate the influences of mixing conditions and steps taken to process the thermosetting nanocomposites on the viscoelastic properties of suspensions. We also examine subsequent influences of mixing on the microstructure and dispersion state of cured hybrids of organically modified clays in a polyester resin. The nanocomposites were prepared in a sequential mixing process developed for the model nanocomposites of organoclays and thermoset resin. Depending on the mixing conditions, the final nanocomposites showed mixed intercalated and moderately to highly delaminated structure. TEM images show that the nanoclay galleries are dispersed in the polymer phase after curing reactions. The startup viscosities and linear viscoelastic properties of the nanocomposites are significantly influenced by the extent and the time duration of mixing. These observations indicate that extensive mechanical mixing combined with a stationary step followed by moderate shear mixing can improve the polymer and nanoparticle interactions at the interface. In the last part of this work, we develop a simple but efficient mathematical formulation on the flow of oblate spheroids in viscous media and compare selected model predictions with the measured startup shear viscosities of suspensions.     

Non-linear viscoelastic response of magnetic fiber suspensions in oscillatory shear

This paper reports the first study on the large amplitude oscillatory shear flow for magnetic fiber suspensions subject to a magnetic field perpendicular to the flow. The suspensions used in our experiments consisted of cobalt microfibers of the average length of 37 μm and diameter of 4.9 μm, dispersed in a silicon oil. Rheological measurements have been carried out at imposed stress using a controlled stress magnetorheometer. The stress dependence of the shear moduli presented a staircase-like decrease with, at least, two viscoelastic quasi-plateaus corresponding to the onset of microscopic and macroscopic scale rearrangement of the suspension structure, respectively. The frequency behavior of the shear moduli followed a power-law trend at low frequencies and the storage modulus showed a high-frequency plateau, typical for Maxwell behavior. Our simple single relaxation time model fitted reasonably well the rheological data. To explain a relatively high viscous response of the fiber suspension, we supposed a coexistence of percolating and pivoting aggregates. Our simulations revealed that the former became unstable beyond some critical stress and broke in their middle part. At high stresses, the free aggregates were progressively destroyed by shear forces that contributed to a drastic decrease of the moduli. We have also measured and predicted the output strain waveforms and stress–strain hysteresis loops. With the growing stress, the shape of the stress–strain loops changed progressively from near-ellipsoidal one to the rounded-end rectangular one due to a progressive transition from a linear viscoelastic to a viscoplastic Bingham-like behavior.     

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.     

Transient phenomena in thixotropic systems

A nonlinear rheological model which accounts for the time-dependent elastic, viscous and yielding phenomena is developed in order to describe the flow behavior of thixotropic materials which exhibit yield stress. A key feature of the formulation is a smooth transition from an ‘elastically’ dominated response to a ‘viscous’ response without a discontinuity in the stress–strain curve. The model is phenomenological and is based on the kinetic processes responsible for structural changes within the thixotropic material. As such, it can predict thixotropic effects, such as stress overshoot during start-up of a steady shear flow and stress relaxation after cessation of flow. Thus this model extends a previously proposed viscoplastic model [J. Rheol. 34 (1991) 647] to include thixotropy.An analysis and comparison to experimental data involving oscillatory shear flow are provided to evaluate the accuracy of the model and to estimate the model parameters in a prototype concentrated suspension. The experiments were conducted using a series of concentrated suspensions of silicon particles and silicon carbide whiskers in polyethylene. The data obtained with this experimental system indicated much better agreement between the theory and experiments that obtained in earlier work.     

A microstructural investigation of the nonlinear response of electrorheological suspensions

In the preceding paper, Part 1, the transition from linear to nonlinear behavior for electrorheological (ER) suspensions under start-up of steady shear flow was found to first arise from the slight rearrangement of unstable structures. In this paper, we investigate the transition to nonlinear behavior for ER suspensions under oscillatory shear flow, focusing on the role of the rearrangement of unstable structures, and employing experimental and simulation results. Again, we find that nonlinear deformation first arises from these rearrangements, as opposed to the gross rearrangement or rupture of particulate chains. The Fourier transform of the simulated time-dependent shear stress is employed to quantify the dependence of the critical strain on the deformation frequency and electric field strength. The predicted behavior is consistent with experimental trends. Methods for verifying the predictions are discussed, as well as possible avenues for exploiting this information in improved operating strategies and improved ER fluids.     

Thixotropy, yielding and ultrasonic Doppler velocimetry in pulp fibre suspensions

This paper reports thixotropy in concentrated pulp fibre suspensions and studies their transient flow behaviour using conventional rheometry coupled with a velocimetry technique. Specifically, an ultrasonic Doppler velocimeter is used in conjunction with a rate-controlled rheometer to deduce the local velocity profiles of pulp fibre suspensions. Pulp suspensions are found to exhibit a plateau in their flow curves where a slight increase in the shear stress generates a jump in the corresponding shear rate, implying the occurrence of shear banding. The velocity profiles were found to be discontinuous in the vicinity of the yielding radius where the Herschel–Bulkley model failed to predict the flow. Shear history and the time of rest prior to the measurement were found to play a significant role on the rheology and the local velocity profiles of pulp suspensions.     

Consistency tests for start-up and cessation deformations of viscoelastic fluids

The time-dependent shear stress and first normal stress difference were measured for a polystyrene solution for start-up and cessation-flow experiments over a relatively wide range of shear rate. Consistency tests for the K-BKZ model were applied to the data, and it was concluded that the K-BKZ equation generally does not satisfactorily describe the start-up and cessation data. Modified consistency tests were developed using a strain-coupling constitutive equation, and the evidence suggests that most of the differences between the predictions of the K-BKZ theory and experiment can be explained by including a strain-coupling effect in the rheological constitutive equation.     

On the elastic properties of model suspensions as investigated by creep recovery measurements in shear

 The elastic properties of model suspensions with spherical monodisperse hydrophilic glass spheres that were dispersed in a Newtonian liquid were determined in creep and creep recovery measurements in shear with a magnetic bearing torsional creep rheometer. The creep and creep recovery measurements were performed depending on the applied level of shear stresses ranging from 0.19 Pa to 200 Pa. Since the recoverable creep compliances of the chosen suspending medium (i.e. a low molecular weight polyisobutylene) were far below the lower limit of the resolution of the creep rheometer it can be considered to behave as purely viscous. By applying a large shear stress in the creep tests the investigated suspensions with a volume fraction of Φ _t =0.35 behave as Newtonian liquids, too. For these suspensions no significant recoverable creep compliances could be detected, as well. In contrast to the Newtonian state of suspensions at high shear stresses, where a shear induced ordering of the particles can be expected, a non-Newtonian behaviour arises by applying a very low shear stress in the creep test. In this state large recoverable creep compliances were detected for the suspensions. The magnitude of the recoverable creep compliances of the suspensions exceeded the largest creep compliances of polymer melts that are reported in the literature by more than two decades. From the results obtained by creep recovery measurements with a magnetic bearing torsional creep rheometer it can clearly be concluded that the particle structure present in the chosen model suspension gives rise to a pronounced elasticity. Received: 21 November 2000 Accepted: 12 July 2001     

Unsteady-state development of plane couette flow for viscoelastic fluids

Unsteady-state development of plane Couette flow for viscoelastic fluids is analyzed using a constitutive equation that can be obtained from molecular theory, in which the molecules are regarded as finitely extensible dumbbells. Typical features of the flow situation are as follows: (i) For a fluid with moderate elasticity, not only stress overshoot but also velocity overshoot are predicted. (ii) For suitable combinations of elasticity and gap width, and for some time intervals stress propagation and reflection phenomena are predicted. (iii) After a sufficient time has elapsed, the stress state behaves similarly to that corresponding to the start-up of a steady simple shear flow.     

基于邓肯-张的冻结粉质粘土本构模型试验研究

为研究冻结粉质粘土强度和变形特性,以沈阳地铁DK11+395联络通道处人工冻结粉质粘土为研究对象,通过冻土三轴剪切试验,研究了不同试验条件下冻结粉质粘土的强度和变形特性。试验结果表明：围压、温度和试件初始含水量是影响冻结粉质粘土强度和变形的主要因素。冻结粉质粘土偏应力-应变曲线呈应变硬化型,其破坏强度和切线弹性模量随围压和试件初始含水量的增加而增大,随温度的升高而减小,破坏偏应力比Rf取值在0.79~0.96之间。基于试验数据建立了以上述三因素为影响因子的冻结粉质粘土Duncan-Chang模型。通过回归分析,建立了模型参数a和b与围压、初始含水量和温度之间的线性回归公式。将依据模型计算的偏应力-应变曲线与对比试验曲线相比较,发现两者具有较好的吻合程度,说明建立的模型能够准确反映围压、初始含水量和温度等条件对冻结粉质粘土强度和变形的影响规律。上述研究成果为冻结粉质粘土强度和变形特性的研究提供了参考,为人工冻结法施工提供了指导,具有重要的理论意义和工程应用价值。     

Rheological behavior of fiber-filled polymers under large amplitude oscillatory shear flow

Small and large amplitude oscillatory shear measurements (SAOS and LAOS) were used to investigate the rheological behavior of short glass fibers suspended in polybutene and molten polypropylene. Raw torque and normal force signals obtained from a strain-controlled instrument (ARES rheometer) were digitized using an analog to digital converter (ADC) card to allow more precise data analysis. The fiber concentration did not affect the torque signal in the SAOS mode, except for its magnitude, whereas the normal force signal was too low to be measurable. With increasing strain amplitude, the magnitude of the torque became a function of time. Depending on the applied frequency and strain rate, the stress in the filled polybutene increased with time, whereas for reinforced polypropylene (viscoelastic matrix), the behavior was opposite, i.e. the stress decreased with time. These effects were more pronounced at high fiber content. In addition the primary normal stress differences were no longer negligible at large deformation amplitude and exhibited a non-sinusoidal periodic response. Fast Fourier transform (FFT) analysis was performed and the resulting spectra, along with Lissajous figures of the shear stress and the primary normal stress differences, are explained in terms of fiber orientation. The experimental results for the suspensions in polybutene are well predicted by the Folgar-Tucker-Lipscomb (FTL) model.     

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.     

Rheological determination of peptizing agents in bentonite clays

This paper presents the results of an evaluation of the rheological properties of commercial bentonite suspensions made from peptized and unpeptized clay samples collected over a six year time span. The rheological properties of these suspensions were measured between shear rates of 5.11 to 1022 s^–1 at concentrations of 15, 30, 45, 64.2 and 70 kg/m³. Bingham, power-law and Casson models were then fitted to the shear stress and shear rate values. Parameters derived from these models were then subjected to further analyses. Four rheological methods (termed peptization index tests) were developed to differentiate between peptized and unpeptized bentonite samples.     

Compressive properties of epoxidized soybean oil/clay nanocomposites

High- and low strain-rate compression experiments were conducted on epoxidized soybean oil (ESO)/clay nanocomposites with nanoclay weights of 0%, 5%, and 8%. A pulse-shaped split Hopkinson pressure bar (SHPB) was employed to conduct high strain-rate experiments. The pulse shaping technique ensures nearly constant-strain-rate deformation under dynamically equilibrated stresses in specimens such that accurate stress–strain curves at various high rates were obtained. A MTS 810 hydraulically driven materials testing system was used to obtain low strain-rate stress–strain curves. Strain-rate and nanoclay weight effects on the compressive properties of the nanocomposites were experimentally determined. A phenomenological strain-rate-dependent material model was presented to describe the stress–strain response. The model agrees well with the experimental data at both large and small strains as well as high and low strain rates.     

Rheological characterization of a solder paste for surface mount applications

Solder pastes used in surface mount soldering techniques (SMT) are very complex suspensions containing high volumes of metallic powder in a carrier fluid. The rheological complexity results largely from the carrier fluid itself, which is a suspension of colloidal particles. In this work, we have characterized the rheological properties of a typical carrier fluid and its solder paste containing 64 vol.% metallic powder. A six-blade vane geometry was used to avoid wall slip and sample fracture. All measurements were carried out following pre-shearing and rest time in order to obtain reproducible results. Steady shear experiments showed that the solder paste was highly shear-thinning and thixotropic. In oscillatory shear, the linear viscoelastic domain was found to be very narrow for both the suspending fluid and the paste. Frequency sweep tests in the linear domain revealed a gel-like structure with a nearly constant G′ for the suspending fluid and a slightly increasing G′ for the solder paste. From creep experiments, a yield stress of about 40 Pa was determined for the suspending fluid at temperatures between 25 and 40°C, and of 100 Pa at 4°C. A much larger yield stress, 480 Pa, was determined for the solder paste at 25°C.