Flow of concentrated solutions of starlike micelles under large-amplitude oscillatory shear

The non-linear viscoelasticity of concentrated solutions and glasses of soft starlike micelles has been studied by large-amplitude oscillatory shear (LAOS). The non-linear response has been analysed using current schemes of Fourier transform (FT) rheology, and its character has been determined by the phase of the third harmonic contribution to the stress. The limitations of FT rheology and related analysis methods are discussed, and an alternative method is presented that takes into account all the higher harmonics. This method reveals a strain-hardening character of intracycle non-linearities at large strain amplitudes for all volume fractions. We also show that, although the relation of LAOS with steady shear measurements works qualitatively, due to inherent limitations of LAOS, steady shear data cannot be reproduced quantitatively.     

Influence of the particle size and volume fraction on micro-damage of the composites

The bulk and shear modulus of metal matrix composites with various volume fractions of particles are modified based on the Eshelby’s equivalent inclusion method combined with self-consistent scheme. By introducing the modified modulus, a new model, which can predict the particle size effects on the stress–strain relation under interfacial debonding damage between matrix and particles, is established. The results obtained from the present investigation show a better agreement with the experimental data.     

Steady shear rheology of dilute polystyrene particle gels

This paper describes an experimental study on dispersions of monodisperse polystyrene (PS) spheres with a typical radius of 1 μm, dispersed in an electrolyte at high ionic strength, screening the electrostatic repulsion. These suspensions gelate at rest even at low volume fractions of PS particles. The density of the particles is matched with the solvent by using deuterium oxide for volume fractions φ≤0.117. Steady-state flow curves, viscosity as a function of shear rate, are measured and reported for 0.014<φ<0.322. The measured flow curves are analyzed on the basis of two models: 1. In the giant floc model (van Diemen and Stein 1983, 1984; Schreuder et al. 1986, 1987; Laven et al. 1988), at low shear rates, the shear is not distributed homogeneously but is limited to certain shear planes; the energy dissipation during steady flow is due primarily to overcoming the viscous drag on the suspended particles during motion caused by encounters of particles in the shear planes. Though this model was developed for higher solid volume fractions (0.35–0.425), we found that it also describes the rheology of dilute particle gels for 0.15≤φ≤0.3, using the same values for the parameters in the model as in the high solid volume fraction region. For φ<0.15, the model also describes the data if the fraction of distance by which a moving particle entrains its neighbors, is assumed to increase in this φ region. 2. The model of de Rooij (de Rooij et al. 1993, 1994) considers aggregates in shear flow to be monodisperse impermeable spheres with a fractal structure. The permeability is taken into account by considering a hydrodynamic radius smaller than the gyration radius in the Krieger-Dougherty expression for the hydrodynamic contribution to the viscosity. Through the use of a yield criterion the aggregate radius is modeled as a function of shear rate. We found that the model describes our experimental results, with a combination of parameter values used already by de Rooij, but only for φ<0.15. Received: 7 May 1998 Accepted: 22 December 1998     

Dynamic simulation of non-spherical particulate suspensions

Particle-level simulation has been employed to investigate rheology and microstructure of non-spherical particulate suspensions in a simple shear flow. Non-spherical particles in Newtonian fluids are modeled as three-dimensional clusters of neutrally buoyant, non-Brownian spheres linked together by Hookean-type constraint force. Rotne–Prager correction to velocity disturbance has been employed to account for far-field hydrodynamic interactions. An isolated rod-like particle in simple shear flow exhibits a periodic orientation distribution, commonly referred to as Jeffery orbit. Lubrication-like repulsive potential between clusters have been included in simulation of rod-like suspensions at various aspect ratios over dilute to semi-dilute volume fractions. Shear viscosity evaluated by orientation distribution qualitatively agrees with one obtained by direct computation of shear stress.     

Strain stiffening of non-colloidal hard sphere suspensions dispersed in Newtonian fluid near liquid-and-crystal coexistence region

Concentrated hard sphere suspensions often show an interesting nonlinear behavior, called strain stiffening, in which the viscosity or modulus starts to increase at critical strain amplitude. Sudden increase of rheological properties is similar to shear thickening; however, the particle dynamics in the strain stiffening under oscillatory shear flow does not necessarily coincide with the mechanism of shear thickening under step shear flow. In this study, we have systematically investigated the nonlinear rheology of non-colloidal (>1???m) hard sphere suspensions dispersed in Newtonian fluid near liquid-and-crystal coexistence region in order to better understand the strain stiffening behavior. The suspensions near liquid-and-crystal coexistence region are known to locally form the closed packing structure. The critical strain amplitude which is the onset of strain stiffening was different for the storage and loss modulus. But they converged to each other as the suspension forms a more crystalline structure. The critical strain amplitude was independent of medium viscosity, imposed angular frequency, and particle size, but was strongly dependent upon particle volume fraction. The onset of strain stiffening was explained in terms of shear-induced collision due to particle motion in the closed packing structure. Nonlinear stress wave-forms, which reflect the micro-structural change, were observed with the onset of strain stiffening. During the strain stiffening, enhanced elastic stress before and after flow reversal was observed which originates from changes in the suspension microstructure. Nonlinearity of the shear stress in terms of Fourier intensity was extremely increased up to 0.55. Beyond the strain stiffening, the suspension responded liquid-like and the nonlinearity decreased but the elastic shear stress was still indicating the microstructure rearrangement within a cycle.     

Splitting of coherent precipitates caused by elastic non-equilibrium

During the process of nickel-based superalloys, gamma prime particles often split into doublets, quartets, or octets. It is an interesting instability phenomenon as it defies conventional surface thermodynamics. Particle splitting is examined through the discrete atom method, which is based on the combination of statistical mechanics and linear elasticity. Splitting phenomena may be classified into two: commensurate elastic instability and incommensurate elastic instability. In the former, the elastic anisotropy of a coherent particle is commensurate with that of the matrix phase, and a non-equilibrium elastic state may cause particle splitting provided that relaxation of the elastic strain energy can exceed the accompanying interfacial energy increase. Incommensurate elastic instability arises when the anisotropy ratios of the precipitate and matrix phase have opposite signs, for example, when the elastically soft direction of the matrix is parallel to the hard direction of the particle phase. The strain energy tends to relax along the elastically soft directions of both phases: thus the particle stretches along its own soft directions while yielding its hard directions to the matrix phase. Such a splitting can end up with a symmetry in the arrangement of particles, but requires a condition that the bulk moduli of both matrix and precipitate phase are comparable to each other.     

钛酸钙系电流变液在直流电场下损耗模量的研究

研究了直流电场下钛酸钙系电流变液在动态振荡剪切模式下损耗模量的变化。用流变仪测试了不同颗粒体积分数材料在不同的温度和电场下损耗模量随应变的关系曲线。讨论了颗粒体积分数、温度、电场强度以及频率对材料损耗模量的影响。以理论推导和试验数据拟合的方法给出了损耗模量与颗粒体积分数、振荡频率、温度以及电场强度等参数的半经验数学关系式。理论值对比试验结果表明,本文损耗模量表达式与试验结果符合较好,可以用于预测直流电场下钛酸钙系电流变液在动态振荡剪切模式下颗粒体积分数、温度、电场强度、频率和剪切应变对损耗模量的影响。     

Scaling and mesostructure of Carbopol dispersions

Rheological measurements were performed on aqueous dispersions of two commercial crosslinked polymer microgels, Carbopol Ultrez 10 and Carbopol ETD 2050, prepared over a wide range of concentration and pH. For all concentrations studied, both the yield stress and the elastic modulus initially increased dramatically with pH and displayed broad peaks at intermediate pH. This is consistent with the onset of jamming of the Carbopol particles due to a rapid increase in particle size caused by osmotic swelling in the presence of NaOH. Scaling of both yield stress and elasticity with concentration was observed only at higher concentrations, which we believe indicates a change from a percolated structure at low volume fractions to a space filling network of compressed particles at high volume fractions. This model is supported by confocal microscopy of fluorescently dyed Carbopol dispersions.     

体积分数对基于沸石和硅油的悬浮液的电流变性能的影响

用 HAAKE RV2 0型流变仪 ,在不同外加电场强度和不同颗粒体积分数下测试了基于沸石和硅油的电流变液的剪切应力变化 .结果表明 :随着外加电场强度升高 ,电流变液的零电场粘度急剧增加 ,电流变液的剪切屈服应力增加 ;随着电流变液中沸石颗粒体积分数升高 ,电流变液的剪切屈服强度急剧上升 .这种变化可以用颗粒间作用力与颗粒间距的关系、单位面积的颗粒链数目变化以及多体作用对电流变液性能的影响来解释     

磁流变弹性体若干物理量的数值分析

应用有限元方法,考虑了颗粒的磁化饱和过程与非线性磁化过程,计算得到了磁流变弹性体中的磁场分布,进而研究了在不同磁场大小、不同颗粒体积比浓度下磁流变弹性体在成链方向的相对磁导率,计算结果和实验结果取得了一致。利用Maxwell应力张量,计算了磁场引起的磁流变弹性体的附加剪切模量。分析了颗粒体积比浓度、外加磁场对磁流变弹性体的磁致剪切模量的影响。研究了颗粒为旋转椭球形状时,颗粒的放置方式与其长短轴之比对磁流变弹性体的磁致剪切模量的影响。计算结果表明,磁流变弹性体的相对磁导率随颗粒体积比浓度的增大而增大,随磁场强度的增大而减小,颗粒的形状和放置方式对磁流变效应有很大的影响。     

A review on wall slip in high solid dispersions

High solid dispersions are soft materials made of colloidal or non-colloidal particles dispersed at high volume fractions in a liquid matrix. They include hard sphere glasses, colloidal pastes, concentrated emulsions, foams, and vesicles. These materials are prone to exhibit different kinds of flow heterogeneities: shear banding, wall slip, and fracture. While wall slip is often considered as a nuisance by experimentalists, it appears to be a fundamental component to the way that high solid dispersions respond to mechanical deformation. Moreover, the ability of soft materials to slip onto surfaces allows them to move readily and efficiently in many natural phenomena and industrial processes. This review surveys recent developments and current research in the field. Topics like wall slip detection and control, microscopic modeling for rigid and soft particles materials, and the relation between wall slip and other flow heterogeneities are discussed. We also identify important open issues for future research.     

Visualization of the breakdown of dilute particles gels during steady-shear

A feature of models concerning the rheology of coagulated suspensions is the development of shear planes. An experimental set-up was developed in which we investigated, by visual analysis, whether shear planes really develop in such systems during steady-shear. A transparent coagulated PTFE dispersion was used, in which the refractive indices of the continuous and dispersed phases were matched, for the formation of a gel. Coagulation was effected by adding NaCl to a concentration of 0.5 M. Polystyrene particles were built into the gel structure as tracer particles. During steady-shear the velocities and trajectories of the tracer particles were analyzed by Particle Tracking Velocimetry (PTV). Indeed layers with approximately the same velocity were observed for a coagulated PTFE-gel, during steady-shear. Deviations from rectilinear motion of the tracer particles were observed. These observations correspond with the assumptions of the giant floc model in which the shear is not distributed homogeneously, but limited to certain shear planes. Deviations from rectilinear motion of the tracer particles in a dilute gel correspond with the results found by Folkersma et al. (1998) in which the distance by which a moving particle entrains its neighbours was assumed to be larger at low volume fractions (≈0.1) than at high volume fractions (≈0.4). Received: 7 May 1998 Accepted: 31 August 1998     

Dependence of nonlinear elasticity on filler size in composite polymer systems

Nanosized filler particles enhance the mechanical properties of polymer composites in a size-dependent fashion. This is puzzling, because classical elasticity is inherently scale-free, and models for the elasticity of composite systems never predict a filler-size dependence. Here, we study the industrially important system of silica-filled rubbers, together with a well-characterized model-filled crosslinked gel and show that at high filler content both the linear and nonlinear elastic properties of these systems exhibit a unique scaling proportional to the cube of the volume fraction divided by the particle size. This remarkable behavior makes it possible to predict the full mechanical response of particle-filled rubbers for small but finite deformations based solely on the rheology of the matrix and the size and modulus of the filler particles.     

Anomalous rheology of polypyrrole nanoparticle/alginate suspensions: effect of solids volume fraction, particle size, and electronic state

The rheology of dispersions of polypyrrole (PPY) nanoparticles (nPPY) is compared to that of micron-sized PPY particles (CPPY), each suspended in aqueous sodium alginate. With increasing PPY volume fraction, the Newtonian viscosity of the CPPY/alginate suspensions exhibits a ??normal?? increase, whereas that of the nPPY/alginate suspensions decreases to a minimum and then increases again. Enhanced elasticity, indicative of agglomerate formation via bridging interactions with the alginate, is observed only in the CPPY rheology. By comparing doped versus dedoped nPPY particles, and investigating the effect of nPPY particle size, we conclude that the negative viscosity change of the nPPY dispersions is due to adsorption of a dense layer of alginate, resulting in a decrease in bulk alginate concentration. The viscosity upturn at higher nPPY volume fractions indicates the onset of particle agglomeration via bridging interactions with alginate. The results demonstrate improved dispersability of both doped and dedoped nPPY over CPPY particles.     

The rheology of strongly-flocculated suspensions

The rheology of strongly-flocculated dispersions of colloidal particles has been investigated at particle concentrations where a continuous network is formed rather than a collection of discrete flocs. Such networks are shown to possess a true yield stress in both shear and in uniaxial compression (as realised in a centrifuge). Properties measured as a function of particle concentration and particle size include the yield stresses in shear (σ_y) and compression (P_y); the limiting and strain-dependent, instantaneous shear moduli G_O and G(γ); the elastic recovery at finite strains, and the rate of centrifugally-driven compaction. The yield stresses and moduli appear to show a power-law dependence on particle concentration with G_O and P_y, having the same power-law index and σ_y a somewhat lower one. The data are in part consistent with predictions based on the idea that the networks have a heterogeneous structure comprising a collection of interconnected fractal aggregates. The behaviour as a function of particle size and concentration is however not completely scaleable as might be expected on this basis. Thus, whereas the shear yield stress could be scaled to remove its dependence on particle radius a and volume fraction φ (over the measured range 0.25 μm ⩽ a ⩽ 3.4 μm; 0.05 ⩽ φ ⩽ 0.25) as could the strain dependent modulus (0.25 ⩽ a ⩽ 1.3 μm; 0.08 ⩽ 0.25), the particle-size and concentration dependence of P_y and G_O could only be scaled for particles with radii between 0.16 and 0.5 μm, smaller and larger particles having different and much higher power-law index in respect of their concentration dependencies. In the case of the smaller particles the failure of the scaling is thought to be due to an anomaly since these particles distort significantly under the influence of the strong van der Waals forces and this causes the aggregates to be more compact then they otherwise would be. The reasons for the failure at larger sizes is not clear.     

Modulus-switching viscoelasticity of electrorheological networks

To form an electrorheological network (ERN), semiconducting nanoparticles were embedded in a polymer that was cross-linked to restrict particle motion. The microstructure ranged from random to aligned, depending on the degree of field-induced particle alignment during chemical network formation. We investigated in detail the softness effects of the matrix, having a relatively low storage modulus, on the dynamic rheological behavior of the ERN and analyzed its anisotropy. The anisotropy of the microstructure was probed rheologically with the modes of small-amplitude oscillatory shear (loading perpendicular to the field direction) and compression (loading in the field direction). The storage shear modulus was found to be a function of the applied electric field, particle volume fraction, and the pre-alignment electric field strength during the cross-linking reaction of the matrix, which governs the thickness of particle columns and intercolumn distance. Nonlinear behavior at small strain (below 0.1%) was conspicuous; this nonlinear viscoelasticity was accompanied by only a limited deformation of ordered connectivity. Throughout this study, we fabricated the ERN with the highly controllable modulus-switching effect acting in a shear-mode operation. Managing this anisotropy of an ERN by the electrical and chemical process is important in the design of smart materials that will provide improved stability and mechanical strength compared with fluid-type electrorheological materials and faster response time compared with that of conventional charged polymer gel.     

Revisiting the generalized self-consistent scheme in composites: Clarification of some aspects and a new formulation

The determination of an effective property in composite materials necessitates the knowledge of some averaged field quantities in the constituents (like the average heat intensity or average strain) of a composite sample, which is subjected to homogeneous boundary conditions. In the generalized self-consistent scheme (GSCS) which is today a classical micromechanics model suited for the determination of the effective properties of matrix-based composites, those average quantities are estimated by using an auxiliary configuration in which a particulate phase is first surrounded by some matrix material and then embedded in the effective medium. In the present study, we revisit the GSCS both for two- and multi-phase matrix-based composites containing spherical particles, and clarify aspects related to the volume fractions of the particle core and matrix shell within the composite element which is embedded in the effective medium. The contribution of this study is believed to be mainly on the conceptual side and resides in a new formulation of the method in which the embedding volume fractions are determined in the course of the analysis by means of some fundamental relations on the averaged fields. The study is carried out in thermal conduction and elasticity and contains new results on the effective shear modulus of multi-phase composites.     

High frequency rheology of hard sphere colloidal dispersions measured with a torsional resonator

The high frequency rheology of model, hard sphere dispersions of charge-neutralized, coated silica particles in tetrahydrofurfuryl alcohol (THFA) was measured using two torsional resonators at five frequencies. The resulting elastic modulus shows ω^1/2 limiting behavior at high frequencies and is in quantitative agreement with the theoretical predictions of Lionberger and Russel [J. Rheol. 38 (1994) 1885]. The lack of a high frequency plateau is a signature of weaker hydrodynamic interactions acting at very small separations. Calculations verify that despite the lack of a high frequency plateau, these dispersions can exhibit reversible shear thickening at high shear rates, in agreement with experiment. Thus, the experiments verify the unique sensitivity of high frequency rheology to hydrodynamic properties at the particle surface.     

The flow of closely fitting particles in tapered tubes

The flow of rigid spheres, truncated cones and elastic incompressible spheres in tapered tubes is investigated assuming that the Reynolds equation is valid in the fluid and the linear theory of elasticity is applicable in the solid. It is shown that leading terms in the asymptotic expansion of pressure drop in terms of minimum fluid film thickness for neutrally buoyant rigid spheres and truncated cones are of higher order of magnitude compared to the corresponding terms for the flow of these particles in circular cylindrical tubes. The effect of taper angle on pressure drop is reduced in the case of soft elastic particles because of particle deformations and significant velocities at the particle surface.     

Onset of nonlinearity and yield strain of a model soft solid

For soft solids with their low modulus, small stress already results in large strain, which may cause nonlinearity and yielding. These potentially competing effects were studied on a clay/polybutadiene (clay/sPB) composite, which is a soft physical gel. Structural changes were introduced by oscillatory shear using large amplitude (LAOS). LAOS beyond a critical limit reduced the internal connectivity. This softened the already soft solid even further, thereby moving it closer to its physical gel point. For clay/sPB, the shear-induced changes were irreversible so that they could get probed using small amplitude shear (SAOS) frequency sweeps. Sequences of SAOS-LAOS-SAOS (SLS) where repeated with increasing LAOS amplitude and increasing duration. The flow-induced structural changes in the soft solid were attributed to yielding, which began to occur at about the same stress/strain values as found for the onset of nonlinearity in traditional SAOS to LAOS (StL) stress amplitude sweeps. The onset of nonlinearity and the yielding seem to be a strain activated process since the characteristic strain amplitude is independent of frequency and temperature, but not so for the characteristic stress amplitude. The duration of LAOS in a SLS experiment beyond yielding is an important parameter since flow-induced structural changes require time to grow.