The rheology of suspensions of porous zeolite particles in polymer solutions

We present data and predictive models for the shear rheology of suspended zeolite particles in polymer solutions. It was found experimentally that suspensions of zeolite particles in polymer solutions have relative viscosities that dramatically exceed the Krieger–Dougherty predictions for hard sphere suspensions. Our investigations show that the major origin of this discrepancy is due to the selective absorption of solvent molecules from the suspending polymer solution into zeolite pores. The effect raises both the polymer concentration in the suspending medium and the particle volume fraction in the suspension. Consequently, both the viscosity of the polymer solution and the particle contribution to the suspension viscosity are increased. We propose a predictive model for the viscosity of porous zeolite suspensions by incorporating a solvent absorption parameter, α, into the Krieger–Dougherty model. We experimentally determined the solvent absorption parameter by comparing viscosity data for suspensions of porous and nonporous MFI zeolite particles. Our results are in good agreement with the theoretical pore volume of MFI particles.     

Suspensions of monodisperse spheres in polymer melts: particle size effects in extensional flow

Suspensions in polymeric, viscoelastic liquids have been studied in uniaxial extensional flow. The fibre wind-up technique has been used for this purpose. The effects of particle size and particle volume fraction have been investigated, using monodisperse, spherical particles. The results have been compared with shear flow data on the same materials. The values of the relative extensional viscosities at low stretching rates are in agreement with the relative shear viscosities and relative moduli. This indicates that hydrodynamic forces are stronger than the particle interaction forces. At larger strain rates strain hardening occurs; it is suppressed when particles are added. Small aggregating particles reduce the strain hardening more strongly than larger particles; strain hardening can even be totally eliminated. When further increasing the stretching rate, hydrodynamic effects dominate again and the effect of particle size effect on strain hardening disappears.     

Bimodal model of slurry viscosity with application to coal-slurries. Part 2. High shear limit behavior

It is shown that in a truly bimodal coal-water slurry the hydrodynamic interactions between the coarse particles impose on the fine fraction a shear rate higher than that applied externally by the viscometer walls. A semi-empirical function of the coarse volume fraction is obtained for this correction factor to the applied shear rate. The derivation of this shear correction factor is based on lubrication concepts and introduces the maximum packing fraction,ø _m, at which flow can take place.ø _m is obtainable from a simple dry packing experiment. It is shown that the contribution of the coarse particles to the viscosity rise can be successfully described by a viscosity model employing the same concepts used to derive the shear correction factor. The bimodal model is applied in the high shear limit to polymodal coal slurries with a continuous particle size distribution. In the model, the contribution of the coarse particles to the viscosity rise is taken from separate viscosity measurements for the coarse coal particles, while the contribution to the viscosity of the fine coal particles is taken to be that given by the measured viscosity of colloidal suspensions of monomodal rigid spheres. It is shown that there is a ratio of coarse to fine fraction volumes in the continuous size distribution, corresponding to a specific separating particle size, for which the measured viscosities of the polymodal slurries match almost perfectly over the whole solids volume fraction range with the viscosity values obtained using the bimodal approach. The match is found to be relatively insensitive to the precise value of the separating particle size.     

Rheological characterization of bimodal colloidal dispersions

In order to investigate the effect of the particle size distribution on the rheological properties of concentrated colloidal dispersions both steady-state shear and oscillatory measurements have been performed on well-characterized bimodal dispersions of sterically stabilized PMMA particles. Replacing a minor amount of large particles by small ones in a concentrated dispersion, keeping the total effective volume fraction constant, decreases the viscosity quite drastically. On the other hand, replacing a small amount of small particles by big ones hardly effects the viscosity at all. This behavior can be attributed to the deformability of the stabilizing polymer layer. A procedure is proposed to calculate the limiting viscosities in a bimodal colloidal dispersion starting from the characteristics of the monodisperse systems. A good agreement has been obtained between the calculated values and the experimental results. The linear viscoelastic properties of the concentrated dispersions have been investigated by means of oscillatory measurements. The plateau values of the storage modulus for the bimodal dispersions decrease with an increasing fraction of the coarse particles. By substituting the bimodal dispersion by an equivalent monodisperse system the storage modulus can be superimposed on the values for the monodisperse suspensions when plotted as a function of the mean interparticle distance.     

Rheological properties of suspensions of TiO2 particles in polymer solutions. 1. Shear viscosity

This paper presents results on the rheological behaviour of suspensions of two kinds of TiO₂ particles in two different polymer solutions. The particles differ in their hydrophilic or hydrophobic properties. The dispersing media are a solution of high molecular weight polyisobutylene in decalin and a solution of a low molecular weight polybutene in decalin. The concentrations of polymer are adjusted in order to get the same zero shear viscosity. The shear viscosity measurements display an apparent yield stress in some cases. The existence and the values of the yield stress depend on the volume fraction of solid particles and on the type of particles. The evolution of the intrinsic viscosity and of the maximum packing fraction vs the shear rate is interpreted in terms of evolution of the size and of the shape of aggregates of particles under shear. The effect of temperature on the development of the yield stress is also discussed. The results are completed by microscopic observations.     

Composite viscoelasticity in glassy,transitional and molten states

As part of a study of viscous and elastic behaviors, over a range of temperatures from below the glass transition up to the hot melt, we here report steady-shear viscosities at 0.007 to 13 s^?1 and at 160 to 220 °C of polystyrene containing 0 to 60% by mass of 0.18-micron diameter titanium dioxide particles. The materials were shearthinning without a yield stress, with a constant activation energy at constant stress, but having a shear-dependent activation energy at constant shear rate — proportional to the volume fraction of the polymer matrix. Superposition of the flow curves at different temperatures for the unfilled and filled systems was possible. All the data were represented by one equation with four parameters: 1) a shear stress coefficient (units Pa · s²); 2) a characteristic stress level for non-Newtonian behavior, independent of temperature and composition; 3) an activation energy at constant stress; and 4) an Einstein coefficient (or intrinsic viscosity of the filler). Other equations also fitted the data, but the others diverged widely when extrapolated.     

Bimodal model of slurry viscosity with application to coal-slurries. Part 1. Theory and experiment

The rheological behavior of stable slurries is shown to be characterized by a bimodal model that represents a slurry as made up of a coarse fraction and a colloidal size fine fraction. According to the model, the two fractions behave independently of each other, and the non-Newtonian behavior of the viscosity is solely caused by the colloidal fraction, while the coarse fraction increases the viscosity level through hydrodynamic interactions. Data from experiments run with colloidal coal particles of about 2–3 µm average size dispersed in water show the viscosity of these colloidal suspensions to exhibit a highly shearrate-dependent behavior and, in the high shear limit, to match very closely the viscosity of suspensions of uniform size rigid spheres although the coal volume fraction must be determined semi-empirically. Different amounts of coarse coal particles are added to the colloidal suspension and the viscosity of the truly bimodal slurries measured as a function of shear rate. In agreement with the bimodal model, the measured shear viscosities show the coarse fraction to behave independently of the colloidal fraction and its contribution to the viscosity rise to be independent of the shear rate. It is shown that the shear rate exerted on the colloidal fraction is higher than that applied by the viscometer as a result of hydrodynamic interactions between the coarse particles, and that it is this effective higher shear rate which is necessary to apply in the correlations. For determining the coal volume fraction a relatively simple and quite accurate measurement technique is developed for determining the density and void fraction of coarse porous particles; the technique directly relates volume fraction to mass fraction.     

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.     

Überlegungen zur Scherviskosität von Suspensionen aufgrund einer Dimensionsanalyse

Dimensional analysis of the motion of solid particles suspended in a fluid phase shows that the macroscopic relative shear viscosity of suspensions generally depends not only on the volume concentration and particle shape but also on two Reynolds numbers and a dimensionless sedimentation number. These dimensionless numbers are formed using parameters characterizing the structure and motion of the suspension at the microscopic level. The analysis was based on the assumptions that the dispersed particles are rigid and sufficiently large that Brownian motion may be neglected, that the continuous fluid phase is Newtonian and that the interactions between particles and between particles and fluid phase are only hydrodynamic. The Reynolds numbers describe the influence of the inertial forces at the microscopic level, and the sedimentation number the influence of gravity. The dimensionless numbers can be neglected if their values are much smaller than one. For each of the dimensionless numbers both the shear rate and the particle size influence the shear viscosity. Thus sedimentation number is large for low shear rates, whereas the Reynolds numbers are large for high shear rates. The viscosity function for one suspension can be transformed into the viscosity function for another suspension with geometrically similar particles but of a different size. The scale-up rules are derived from the requirement that the relevant dimensionless numbers must be constant. The influence of non-hydrodynamic effects at the microscopic level on the shear viscosity can be detected by deviations from the derived scale-up rules.     

Extensional rheology of concentrated poly(ethylene oxide) solutions

The shear and extensional rheology of three concentrated poly(ethylene oxide) solutions is examined. Shear theology including steady shear viscosity, normal stress difference and linear viscoelastic material functions all collapse onto master curves independent of concentration and temperature. Extensional flow experiments are performed in fiber spinning and opposed nozzles geometries. The concentration dependence of extensional behavior measured using both techniques is presented. The zero-shear viscosity and apparent extensional viscosities measured with both extensional rheometers exhibit a power law dependence with polymer concentration. Strain hardening in the fiber spinning device is found to be of similar magnitude for all test fluids, irrespective of strain rate. The opposed nozzle device measures an apparent extensional viscosity which is one order of magnitude smaller than the value determined with the fiber spinline device. This could be attributed to errors caused by shear, dynamic pressure, and the relatively small strains developed in the opposed nozzle device. This instrument cannot measure local kinematics or stresses, but averages these values over the non-homogenous flow field. These results show that it is not possible to measure the extensional viscosity of non-Newtonian and shear thinning fluids with this device. Fiber spin-line experiments are coupled with a momentum balance and constitutive model to predict stress growth and diameter profiles. A one-mode Giesekus model accurately captures the plateau values of steady and dynamic shear properties, but fails to capture the gradual shear thinning of viscosity. Giesekus model parameters determined from shear rheology are not capable of quantitatively predicting fiber spinline kinematics. However, model parameters fit to a single spinline experiment accurately predict stress growth behavior for different applied spinline tensions.     

Effect of poly(ethylene oxide) on the rheological behavior of silica suspensions

The steady-shear viscosity, dynamic viscoelasticity, and sedimentation behavior were measured for silica suspensions dispersed in aqueous solutions of poly(ethylene oxide) (PEO). For suspensions prepared with polymer solutions in which the transient network is developed by entanglements, the viscosity at a given shear rate decreases, shows a minimum, and then increases with increasing particle concentration. Because the suspensions are sterically stabilized under the conditions where the particle surfaces are fully covered with by a thick layer of adsorbed polymer, the viscosity decrease can be attributed to the reduction of network density in solution. But under the low coverage conditions, the particles are flocculated by bridging and this leads to a viscosity increase with shear-thinning profiles. The polymer chains with high molecular weights form flexible bridges between particles. The stress-dependent curve of storage modulus measured by a stress amplitude sweep shows an increase prior to a drastic drop due to structural breakdown. The increase in elastic responses may arise from the restoring forces of extended bridges with high deformability. The effect of PEO on the rheological behavior of silica suspensions can be explained by a combination of concentration reduction of polymer in solution and flocculation by bridging.     

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.     

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.     

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.     

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     

Rheology of concentrated microgel solutions

Viscosity, modulus, and yield stress for 0–6 wt% aqueous solutions of Carbopol 941 were investigated using constant shear rate, constant shear stress, and dynamic oscillatory experiments. The microgel character of the polymer was evident from the solid-like behavior of the solutions above 1 wt%. Yield stress increased with concentration, but yield occurred at a critical shear strain of 40%, independent of concentration. The static stress-strain relationship became non-linear at ~ 25% strain, in fair agreement with the onset of non-linear response in the storage modulus at ~ 10% strain. Small strain moduli from static and low frequency measurements agreed rather well; modulus values obtained from the recoverable strain after yielding were 30–40% smaller. Solutions flowed at near-constant stress in the low shear rate regime; at higher rates the stress increases with shear rate more rapidly. The viscosity did not obey the Cox-Merz rule. Steady-state viscosity scaled with polymer concentration to the 3/4 power. Results were interpreted using a cellular, deformable sphere model for the polymer, in analogy to emulsions and foams.     

Effects of electric fields and volume fraction on the rheology of hematite/silicone oil suspensions

Electrorheological (ER) fluids composed of iron(III) oxide (hematite) particles suspended in silicone oil are studied in this work. The rheological response has been characterized as a function of field strength, shear rate and volume fraction. The dielectric properties of the suspensions were first studied in order to get information about the conductivity of the solid. Rheological tests under a.c. electric fields elucidated the influence of the electric field strength and volume fraction on the field-dependent yield stress. It was found that this quantity scales as a square power law in both cases. The viscosities of electrified suspensions were found to increase by several orders of magnitude as compared to the unelectrified suspension at low shear rates, although at high shear rates hydrodynamic effects become dominant and no effects of the electric field on the viscosity are observed. The ER behaviour of the suspensions was analysed by considering the fundamental forces (of hydrodynamic and electrostatic origin) acting on the particles and it is found that, at a given volume fraction, all the dependencies of relative viscosity on shear rate and field strength can be described by a single function of the Mason number, Mn. Finally, two different chain models were used to explain the shear-thinning behaviour observed: rheological measurements showed a power-law dependence of relative viscosity decrease on the Mason number, _F~Mn, with –0.95.     

The modified constrained volume model predictions in shearing flow at nonunity viscosity ratio values

In this paper, the modified constrained volume model, which describes the evolution of anisotropy of immiscible polymer blends, composed of Newtonian components, was examined during shearing motion (steady and oscillatory) at various viscosity ratio values. We found that the linear correction to the rate of deformation tensor causes the droplet to change its volume at viscosity ratio values lower than unity, and to cause premature tumbling at viscosity ratio values larger than unity, in a case where retraction, breakup, and coalescence modules of the model were turned off. The use of Eshelby tensor, together with a closure to relate anisotropy to the Eshelby concentration tensor, mostly solved the problem. The model’s predictions are then shown at various capillary number values and at various viscosity ratio values. Comparison of model predictions to single droplet data at nonunity viscosity ratio value showed good agreement. Finally, model predictions of first normal stress difference during startup of steady shear are compared to experimental rheological results for immiscible polymer blends that are available in literature. Good predictions can be achieved by the introduction of a new switch function that controls the retraction and breakup modules. The model’s predictions at large amplitude oscillatory shear were examined. It was found that linear corrections to the velocity gradient tensor can be used for strains up to 100 %. For larger strain values, the Eshelby concentration tensor must be used.     

Viscosity of particle filled polymer melts

Summary Viscosities of particle filled polymer melts were measured at fairly low shear rate. Particles were glass beads, glass balloons, and silas balloons. Polymers were polyethylene and polystyrene. Flow curves were superimposed with respect to concentration of filler. The relative viscosity defined as the ratio of viscosity of filled polymer to that of unfilled polymer at the same shear stress is obtained as an asymptotic value even for highly filled material. The relation between relative viscosity and volume fraction of filler was represented by the equations derived byMaron andPierce orMooney. Only the distribution of particle size had influence on relative viscosity at a defined filler concentration. Yield stresses were estimated, and found to increase exponentially in the range of volume fraction from 0.1 to 0.5.

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Zusammenfassung Viskositäten von Polymerschmelzen, die mit Teilchen gefüllt worden waren, wurden bei mittleren Schergeschwindigkeiten bestimmt. Als Teilchen wurden Voll- und Hohlkugeln aus Glas, sowie sog. silas balloons, als Polymere Polyäthylen und Polystyrol verwendet. Die Fließkurven für verschiedene Füllstoffkonzentrationen wurden überlagert. Die relative Viskosität, definiert als das Verhältnis der Viskositäten von gefülltem und ungefülltem Polymer bei gleicher Schubspannung, besitzt einen asymptotischen Wert selbst für hoch gefülltes Material. Die Beziehung zwischen relativer Viskosität und Füllstoff-Volumenkonzentration läßt sich durch eine vonMaron undPierce oder eine vonMooney abgeleitete Gleichung beschreiben. Nur die Teilchengrößenverteilung hat bei einer definierten Füllstoffkonzentration einen Einfluß auf die relative Viskosität. Fließspannungen werden abgeschätzt und dafür in einem Konzentrationsbereich zwischen 0,1 und 0,5 ein exponentieller Anstieg gefunden.

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With 13 figures and 2 tables     

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.