Rheological behavior of concentrated suspensions as affected by the dynamics of the mixing process

The rheological characterizations of concentrated suspensions are generally carried out assuming “well-mixed” suspensions. However, the variation of the concentration distributions of the ingredients of the formulation, i.e., the “goodness of mixing”, the size and shape distributions of the particle clusters and the rheological behavior of the suspension all depend on the thermo-mechanical history that the suspension is exposed to during the mixing process. Here, various experimental tools are used for the characterization of the degree of mixedness (concentration distributions) of various ingredients along with the characterization of rheological material functions, wall slip behavior and the maximum packing fraction of a graphite/elastomer suspension. The degree of mixedness values of the ingredients of the suspensions processed using batch and continuous processes and under differing operating conditions were characterized quantitatively using wide-angle X-ray diffraction and thermo gravimetric analysis and were elucidated under the light of the electrical properties of the suspension as affected by the mixing process. Upon achieving better homogeneity of the graphite particles and the binder and decreases in the size and breadth of the size distributions of particle clusters (as inferred from electrical measurements and maximum packing fraction values), the elasticity (storage modulus) and the shear viscosity (magnitude of the complex viscosity from small-amplitude oscillatory shear and shear viscosity from steady torsional and capillary rheometry) of the suspension decreased significantly and the wall slip velocity values increased. These findings demonstrate the intimate relationships that exist between the rheological behavior of concentrated suspensions and the thermo-mechanical history that they are exposed to during the processing stage and suggest that the preparation conditions for suspensions should be carefully selected and well documented to achieve reproducible characterization of rheological material functions.     

Direct measurements of shear-induced particle migration in suspensions of bimodal spheres

A variety of studies reported in the literature have established that initially well mixed suspensions subjected to non-homogeneous shear flows attain an anisotropic particulate structure. It has also been shown that non-homogeneous shearing causes suspensions of unimodal spheres to demix, i.e., gradients in solids concentration are formed. The objective of this study was to determine the effect of non-homogeneous shear flows on suspensions of bimodal particles, and specifically, to determine if the solids concentration gradients which develop are accompanied by size segregation of the coarse with respect to the fine fraction. We used the simplest and most direct methods to determine the relative solids concentrations: visual observation of tracer particles in transparent suspensions and physical separation of the coarse and fine solid fractions. Three different types of non-homogeneous shear flows were examined, and in each case the data support two main conclusions: 1) suspended particles migrate from regions of high shear rate to regions of low shear rate, and 2) the coarse fraction of particles migrates much faster than the fine fraction, leading to size segregation of initially well-mixed suspensions. While the former conclusion is consistent with other studies reported in the literature, to our knowledge this paper provides the first data supporting and, to a limited extent, quantifying the latter conclusion.     

Dynamics and rheology of a dilute suspension of dipolar nonspherical particles in an external field: Part 1. Steady shear flows

Suspensions of small nonspherical particles having dipolar moments exhibit non-Newtonian behavior under the influence of shear and external fields. Numerical methods are presented for calculating the rheological and rheo-optical properties of dilute suspensions of Brownian particles having permanent dipoles subject to time-dependent shear and external fields. The numerical methods employ the Galerkin method of weighted residuals to solve the differential equation for the particle orientation distribution function. The steady-state shear flow intrinsic viscosity of suspensions of particles with sufficiently extreme aspect ratio is predicted to exhibit a maximum value attained for intermediate shear rates at selected field orientations. These numerical results provide valuable insight into the coupling which occurs between the effects of rotary Brownian motion, the hydrodynamic resistance of nonspherical particles, and the external torque exerted on dipolar particles. The results are applicable to both suspensions of magnetic particles and electrically dipolar particles.     

Flow instabilities in capillary flow of concentrated suspensions

The development of flow instabilities during the capillary flow of two concentrated suspensions filled with 76.5 and 65.6% by volume solids was investigated. The flow instabilities manifested themselves by the development of concentration gradients as a result of the filtering of the binder, superimposed on the bulk motion of the suspension. The effects of apparent shear rate, capillary diameter and the surface roughness of the particles were investigated. The use of the comparison of the filtration rate with the bulk velocity of the suspension during flow is shown to be promising for the prediction of the apparent shear rate at which filtration-based flow instabilities occur.     

A self-similar behavior for the relative viscosity of concentrated suspensions of rigid spheroids

A viscosity model for suspensions of rigid particles with predictive capability over a wide range of particle volume fraction and shear conditions is of interest to quantify the transport of suspensions in fluid flow models. We study the shear viscosity of suspensions and focus on the effect of particle aspect ratio and shear conditions on the rheological behavior of suspensions of rigid bi-axially symmetric ellipsoids (spheroids). We propose a framework that forms the basis to microscopically parameterize the evolution of the suspension microstructures and its effect on the shear viscosity of suspensions. We find that two state variables, the intrinsic viscosity in concentrated limit and the self-crowding factor, control the state of dispersion of the suspension. A combination of these two variables is shown to be invariant with the imposed shear stress (or shear rate) and depends only on the particle aspect ratio. This self-similar behavior, tested against available experimental and numerical data, allows us to derive a predictive model for the relative viscosity of concentrated suspensions of spheroids subjected to low (near zero) strain rates. At higher imposed strain rates, one needs to constrain one of the state variables independently to constrain the state of dispersion of the suspension and its shear dynamic viscosity. Alternatively, the obtained self-similar behavior provides the means to estimate the state variables from the viscosity measurements made in the laboratory, and to relate them to microstructure rearrangements and evolution occurring during deformation.     

Flowing colloidal suspensions in non-Newtonian suspending fluids: Decoupling the composite birefringence

The rheology of dilute, colloidal suspensions in polymeric suspending fluids can be studied with simultaneous dichroism and birefringence measurements. The dichroism provides a direct measure of the particle dynamics, but the birefringence is a composite property with independent contributions from the suspended particles and the polymer molecules. For suspensions where the contribution from the particles is significant, the composite birefringence must be decoupled in order to analyze the dynamics of the polymeric suspending fluid. A method to perform the decoupling is derived and then demonstrated through transient shear flow experiments with dilute suspensions ofFeOOH particles in semi-dilute, xanthan gum suspending fluids. The birefringence of the xanthan gum suspending fluid is calculated from experimental measurements of the composite birefringence and the dichroism of the suspension. To gather information on particle/polymer interactions, the calculated birefringence is compared to the birefringence of xanthan gum solutions containing no suspended particles and the dirchoism is compared to that of a suspension in a Newtonian fluid.     

Numerical study of concentrated fluid–particle suspension flow in a wavy channel

The particle migration effects and fluid–particle interactions occurring in the flow of highly concentrated fluid–particle suspension in a spatially modulated channel have been investigated numerically using a finite volume method. The mathematical model is based on the momentum and continuity equations for the suspension flow and a constitutive equation accounting for the effects of shear‐induced particle migration in concentrated suspensions. The model couples a Newtonian stress/shear rate relationship with a shear‐induced migration model of the suspended particles in which the local effective viscosity is dependent on the local volume fraction of solids. The numerical procedure employs finite volume method and the formulation is based on diffuse‐flux model. Semi‐implicit method for pressure linked equations has been used to solve the resulting governing equations along with appropriate boundary conditions. The numerical results are validated with the analytical expressions for concentrated suspension flow in a plane channel. The results demonstrate strong particle migration towards the centre of the channel and an increasing blunting of velocity profiles with increase in initial particle concentration. In the case of a stenosed channel, the particle concentration is lowest at the site of maximum constriction, whereas a strong accumulation of particles is observed in the recirculation zone downstream of the stenosis. The numerical procedure applied to investigate the effects of concentrated suspension flow in a wavy passage shows that the solid particles migrate from regions of high shear rate to low shear rate with low velocities and this phenomenon is strongly influenced by Reynolds numbers and initial particle concentration. Copyright © 2008 John Wiley & Sons, Ltd.     

Free-surface flow of concentrated suspensions

Free-surface flows of concentrated suspensions exhibit many interesting phenomena such as particle segregation and surface corrugation. In this work the flow structures associated with free-surface has been studied experimentally. The free-surface velocity for neutrally buoyant suspension of uniform spheres in a gravity driven inclined channel flow was determined by particle imaging velocimetry (PIV) technique. Experiments were carried out for concentrated suspensions with particle fractions ? ranging from 0.40 to 0.50. The measured velocities show blunted profile in the channel. The blunting of the velocity profile increases with the particle concentration. The rms velocity fluctuations measured at the free-surface progressively increase with particle fraction ? and are linear in shear rate γ. The surface roughness were characterized by analyzing the power spectral density of the refracted light from the free-surface. The characteristics observed are in support of earlier findings.     

Shear and squeeze rheometry of suspensions of magnetic polymerized chains

We present the first experimental results on the magnetorheology of suspensions of non-Brownian magnetic ellipsoidal particles. These particles are made of spherical iron particles linked by polymers and are called polymerized chains. Steady shear, oscillatory shear, and oscillatory squeeze rheological tests have been performed. The rheological properties of the suspension of polymerized chains have been compared with those of the suspension of spherical iron particles. In shear flow, both suspensions develop nearly the same yield stress, while in squeeze flow, the yield stress is several times higher for the suspension of polymerized chains. We show that the squeezing force of a suspension of spherical particles is an increasing function of the magnetic field intensity at low magnetic fields but decreases dramatically at higher fields. Surprisingly, this phenomenon, attributed to cavitation or air entrainment, does not occur in the suspension of polymerized chains.     

Probability model of solid to liquid-like transition of a fluid suspension after a shear flow onset

The complexity of interactions of different origin between particles in dense fluid suspensions limits application of the concepts of classical mechanics for finding a relation between individual particles dynamics, and the macroscopic dynamic response. For this reason, the probability model of suspension flow after a shear flow onset is proposed that incorporates our certain lack of understanding of environments effects. These effects are identified in the model with the random rate of particles arrival to flow. The multiplication rule is used to sweep from the individual particles to the entire system. The resulting probability of the system shift to flow represents well the measured boundary position, separating the flowing suspension from its solid-like state, and proves thus the appropriate choice of representation of the particle interaction effects.     

Shear-thickening flow of suspensions of carbon nanofibers in aqueous PVA solutions

The suspensions of carbon nanofibers in aqueous poly(vinyl alcohol) solutions were prepared in the presence of spherical carbon black particles, and the steady-shear viscosity and dynamic viscoelasticity were measured for complex suspensions. Although the single suspensions of carbon black are highly stable, the flocculation of carbon nanofibers is promoted by the addition of carbon black particles. The complex suspensions show remarkable shear thickening in the steady-flow and strain hardening in oscillatory shear with large amplitude. The nonlinear responses strongly depend on the carbon black concentration, whereas the dynamic viscoelasticity at low strains in the linear ranges is not significantly influenced. As the highly elastic effects arise from the long-range motion of particles, the possible mechanism may be the orientation of nanofibers in strong shear fields. The suspensions show the time-dependent behavior of viscosity when the time-scale of measurements is shorter than that of structural recovery to the isotropic states.     

The Dilute Rheology of Swimming Suspensions: A Simple Kinetic Model

A simple kinetic model is presented for the shear rheology of a dilute suspension of particles swimming at low Reynolds number. If interparticle hydrodynamic interactions are neglected, the configuration of the suspension is characterized by the particle orientation distribution, which satisfies a Fokker-Planck equation including the effects of the external shear flow, rotary diffusion, and particle tumbling. The orientation distribution then determines the leading-order term in the particle extra stress in the suspension, which can be evaluated based on the classic theory of Hinch and Leal (J Fluid Mech 52(4):683–712, 1972), and involves an additional contribution arising from the permanent force dipole exerted by the particles as they propel themselves through the fluid. Numerical solutions of the steady-state Fokker-Planck equation were obtained using a spectral method, and results are reported for the shear viscosity and normal stress difference coefficients in terms of flow strength, rotary diffusivity, and correlation time for tumbling. It is found that the rheology is characterized by much stronger normal stress differences than for passive suspensions, and that tail-actuated swimmers result in a strong decrease in the effective shear viscosity of the fluid.     

Dispersion state and rheology of hectorite particles in water over a broad range of salt and particle concentrations

The relationship between the rheological properties of deionized aqueous suspensions of hectorite particles and the dispersion states of the particles has been studied with a broad range of salt and particle concentrations. The shear viscosity of the hectorite suspensions decreases drastically after exhaustively deionizing the suspensions with ion-exchange resins. By means of DLS measurements, it is clarified that the average size of the flocs of hectorite particles decreases and reaches the Stokes diameter of the individual particle as the degree of deionization advances. This fact strongly supports the idea that the electrical double layer around the hectorite particles expands significantly in the exhaustively deionized state and the particles are well-dispersed individually and do not form a three-dimensional network structure composed of particles, whereas such a network structure forms in the presence of a large amount of salt. In the case of exhaustively deionized state, the suspension forms a glassy state, at high particle fractions. The results show the importance of the electrical double layer that causes a strong repulsive force among the particles on the particle dispersion state, especially in the exhaustive deionization area below 10^− 4 M, and on the rheological properties; the hectorite suspension can be considered a Newtonian liquid in the deionized state, but it becomes elastic-solid in the presence of salt above a certain concentration confirmed by normal stress measurements.     

Influence of medium viscosity and adsorbed polymer on the reversible shear thickening transition in concentrated colloidal dispersions

The influence of medium viscosity on the onset of shear thickening of silica dispersions is investigated with two different methods. In the first method, the sample temperature is varied over a narrow range for two different suspensions. For the first suspension, the stress at the onset of shear thickening, or the critical stress, was found to be independent of sample viscosity, and the shear viscosity scaled with Peclet number, as expected. The critical stress for the second suspension was not independent of sample viscosity, and the Peclet number scaling was only moderately successful. The differences were attributed to changes in particle interactions with temperature. In the second method, the molecular weight of an oligomeric silicone oil medium is varied. In principle, this method should maintain constant chemical interactions as medium viscosity varies; however the polymer is found to adsorb onto the silica surface and delay shear thickening to higher stresses with increasing molecular weight. The critical stress for the highest molecular weight systems, which is highly dependent on particle loading, overlays with an effective volume fraction based on the hydrodynamic diameter of the polymer-stabilized colloids. The results of both methods suggest that if all other properties of the dispersion are held constant, critical stress is independent of medium viscosity.     

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.     

Shear behaviour of biopolymer suspensions with spheroidal and cylindrical particles

The rheological behaviour of suspensions is influenced by many parameters, one of which is the particle shape. For rigid particle suspensions a number of studies demonstrate the effects of the particle aspect ratio. Indeed, fibres are widely used as rheology modifiers in different materials such as synthetic polymers. This work is concerned with testing the hypothesis that regularly shaped particles with aspect ratios larger than one that are made of gelled biopolymers could be used as rheology modifiers for biopolymer solutions. Biopolymers, and mixtures thereof are a widely used ingredient in foods and other products with structure functionality. Tailoring rheology modifiers by morphology offers an alternative to using different biopolymers. It is demonstrated how biopolymer suspensions with regular spheroidal, or cylindrical particle shapes can be produced by gelling the droplet phase of a liquid two phase biopolymer mixture in a shear field. Biopolymers were chosen such that gelation is initiated by cooling. Shear-cooling at constant stresses leads to the formation of ellipsoidal particles. Cylindrical particles can be generated by stepping up the shear stress prior to gelation, i.e., stretching the droplet phase into fibrils, and trapping the shape prior to break-up through gelation. Morphologies and steady shear rheological data for suspensions of the two biopolymers gellan and κ-carrageenan with an internal phase volume of 0.2 are reported. The influence of particle shape on relative viscosity is pronounced. At high shear stresses particle orientation leads to decreased viscosity with increasing particle aspect ratio. In the low shear region, higher aspect ratio suspensions show higher viscosities. Additionally, the material properties, including the interfacial tension, which influence the suspension morphology are reported. Received: 3 March 2000 Accepted: 22 August 2000     

Self-organized domain microstructures in a plate-like particle suspension subjected to rapid simple shear

The evolution of the microstructure and rheological properties of plate-like particle suspensions subjected to rapid simple shear is studied numerically. In response to the shear-induced strain, particles in the suspensions rearrange to form a steady-state microstructure, and the suspension viscosity reaches a steady value. Under this condition, the microstructure is composed of two domains having different particle fractions and particle orientations. In the matrix (particle-poor) and cluster (particle-rich) domains, the particles’ long axes are oriented subparallel to the shear plane and normal to the maximum compressive principal direction, respectively. A higher particle concentration and friction coefficient enhance the development of cluster domains relative to matrix domains leading the intensity of the preferred particle orientation to decrease and the number of contacting particles, the aspect ratio of clusters, the inter-particle force, and the suspension viscosity to increase. The domain microstructure is governed by two factors: (1) geometric relations between the particle orientation and the maximum compressive axes and (2) the magnitude of particle–fluid and particle–particle interactions. The first factor results in the coupling of the particle orientation and the local fraction of particles, which is an important character of the domain microstructure. The second factor controls the relative development of the cluster and matrix domains through the change in the particles’ rotational behavior. Our results suggest that the microstructure of plate-like suspensions subjected to rapid shear is predictable in terms of the cluster stability, which has important implications for the kinematics of flow-related microstructures in nature and manufacturing.     

Three-dimensional numerical simulation of drops suspended in simple shear flow at finite Reynolds numbers

A three-dimensional study of suspension of drops in simple shear flow has been performed at finite Reynolds numbers. Results are obtained using a finite difference/front tracking method in a periodic domain. The effects of the Reynolds number and the Capillary number are addressed at two volume fractions: 0.195 and 0.34. It is observed that suspensions of deformable drops exhibit a shear-thinning behavior. Similar to the motion of a single drop, drops migrate away from the walls. The effective viscosity, the first and the second normal stress differences oscillate around a mean value in all cases. The first normal stress difference increases with the Capillary number, the Reynolds number and the volume fraction. Results show that drops deform more and orient more in the flow direction as the Capillary number or the volume fraction is increased. Also, the average size of clusters is smaller than for suspension of rigid particles. The radial dependence of the pair distribution function across the channel has been studied. This dependency shows that the tendency to form clusters is reduced as the Capillary number increases or the volume fraction decreases.     

The bulk electroviscous effect

Electroviscous stresses arise as hydrodynamic flows disturb the ionic (Debye) clouds that screen charged surfaces in electrolyte solutions. The contribution thereof to the effective bulk viscosity (also known as the second or volume viscosity) of two-phase suspensions is quantified here. Specifically, the bulk viscosity of two model suspensions is calculated: (1) a dilute dispersion of rigid charged spherical particles immersed in a compressible electrolyte that undergoes uniform dilatation and (2) a dilute suspension of charged gas bubbles expanding uniformly in an incompressible electrolyte. In both cases, it is assumed that the fluid flow only slightly drives the Debye cloud out of equilibrium, which formally requires that the ratio of the ion diffusion to flow time scales—a Péclet number—is small. For a suspension of rigid particles, the electroviscous contribution to the effective bulk viscosity is proportional to the particle volume fraction and decreases monotonically as the ratio of the particle radius to the Debye length increases. Similar behavior is well known for the electroviscous contribution to the effective shear viscosity of a dilute hard-sphere suspension; a quantitative comparison between the bulk and shear viscosities is made. In contrast, the electroviscous contribution to the bulk viscosity of a dilute suspension of bubbles is independent of the bubble volume fraction and attains a finite value in the limit of vanishing Debye length.     

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.