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.     

Rheology of immiscible blends with particle-induced drop clusters

We consider the effects of 2.7-μm-diameter hydrophobic silica particles added to droplet–matrix blends of polyethylene oxide (PEO) and polyisobutylene (PIB). The particles adsorb on the surface of the PEO drops but protrude considerably into the PIB phase. Hence, it is possible for a single particle to adsorb onto two PEO drops simultaneously. Such particles are called “bridging” particles, and they the glue drops into noncoalescing clusters. Flow visualization studies show that shearing the sample promotes bridging-induced clustering of drops and that the structure of the clusters depends on the shear rate. Rheologically, the most significant consequence of bridging-induced drop clustering appears to be a plateau in G′ at low frequencies characteristic of gel-like behavior. The gel-like behavior develops fully after shearing the sample, and the kinetics of gel formation are faster with increasing shear stress or increasing drop volume fraction. The gel-like behavior suggests that the bridging-induced drop clusters form a weak network. Apart from particle bridging, optical microscopy also reveals that particles can organize into a hexagonal lattice on the drops’ surfaces, a phenomenon that has only been noted in aqueous systems previously. Finally, rheology and flow visualization both suggest that particles promote coalescence of drops. This is surprising in light of much past research that shows that particles that are preferentially wetted by the continuous phase generally hinder coalescence in droplet–matrix systems.     

Evidence for re-entrant behavior in laponite–PEO systems

We observe evidence of re-entrant behavior in dispersions of a discotic clay, laponite, with added polymer. Under basic conditions, neat laponite forms a disordered colloidal glass. Rheologically, this phase behaves as a viscoelastic solid, and dynamic light scattering shows evidence of non-ergodic behavior. Addition of low molecular weight poly(ethylene oxide) (PEO) melts the glass, resulting in a low-viscosity liquid with fast dynamics. We believe this is due to a depletion force caused by excess PEO chains in solution. A viscoelastic solid is re-formed with the addition of high molecular weight PEO, which we believe to be caused by polymer chains bridging between laponite particles. The physics in our system is quite different from the hard sphere/nonadsorbing polymer systems for which re-entrant glass transitions have been reported in the literature; however, we believe there may be similarities between these phenomena. To our knowledge, this is the first evidence of a type of re-entrant behavior in anisotropic colloids.     

A thermodynamic approach to the rheology of highly interactive filler-polymer mixtures. Part II. Comparison with polystyrene/nanosilica mixtures

The dynamic properties as a function of frequency and strain amplitude, steady-state viscosity as a function of shear rate, and transient shear stresses at startup and cessation of shear flow of polystyrene (PS)/fumed silica mixtures of various concentrations were investigated. An abrupt change in the viscoelastic properties was noticed at a concentration above 1% by volume. Observations by means of scanning electron microscopy (SEM) indicate the presence of a three-dimensional network through the bridging of filler particles by the adsorbed polymer. The viscoelastic behavior is simulated utilizing a theory proposed in Part I (Havet and Isayev 2001) based on a double network created by the entangled polymer matrix and the adsorbed polymer with filler concentration taken into account through the bridging density of polymer-filler interactions and a hydrodynamic reinforcement. The steps taken for determining the model parameters required to carry out the simulation are described. The major features of the rheological behavior of highly interactive polymer-filler mixtures are captured qualitatively and in some cases, quantitatively predicted.     

Extensional flow behavior of polymer solutions and particle suspensions in a spinning motion

Mechanical spinning of fluid filaments was used to generate an extensional flow, in which rheological measurements were obtained for a Newtonian fluid, two aqueous polymer solutions, and two fluid suspensions of rod-shaped particles. The tensile stress was determined by measuring the tensile force of the fluid filament while the kinematics were determined from photographic measurement of the filament profile and the assumption of a flat velocity profile. The measured tensile stresses for the Newtonian fluid matched predicted stresses, thereby confirming the validity of the experimental technique.The spinning behavior of each polymer solution could be correlated as stress versus extension rate. The apparent “spinning viscosity” increased with increasing rate of extension, in contrast to shear-thinning behavior in viscometric flow. For the fluid suspensions, the presence of rod-shaped particles increased the apparent viscosity far more in extensional flow than in shear. Tensile stresses calculated from a theoretical formula for suspensions proposed by Batchelor agreed rather well with experiment. Some general criteria for the interpretation of the spinning experiment are proposed, and some microrheological implications of the present findings are discussed.     

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.     

Observations on the rheological response of alkali activated fly ash suspensions: the role of activator type and concentration

This paper reports the influence of activator type and concentration on the rheological properties of alkali-activated fly ash suspensions. A thorough investigation of the rheological influences (yield stress and plastic viscosity) of several activator parameters, including: (i) the cation type and concentration of alkali hydroxide and (ii) the alkali-to-binder ratio (n) and silica modulus (M_s), and (iii) the volume of the activation solution, on the suspension rheology is presented. The results indicate a strong dependence on the cation and its concentration in the activation solution. The viscosity of the activation solution and the volumetric solution-to-powder ratio are shown to most strongly influence the plastic viscosity of the suspension. The suspension yield stress is predominantly influenced by the changes in fly ash particle surface charge and the ionic species in the activator. A shift from non-Newtonian to Newtonian flow behavior is noted in the case of silicate-based suspensions for M_s?≤?1.5. This behavior, which is not observed at higher M_S values, or when the fly ash is dispersed in hydroxide solutions or pure water, is hypothesized to be caused by colloidal siliceous species present in this system, or surface charge effects on the fly ash particles. Comparisons of the rheological response of alkali-activated suspensions to that of portland cement-water suspensions are also reported.     

Effect of polymer bridging on rheological properties of dispersions of charged silica particles in the presence of low-molecular-weight physically adsorbed poly(ethylene oxide)

 The effect of a low-molecular-weight physically adsorbed poly(ethylene oxide) on the rheological behavior of aqueous dispersions of silica particles (as a model system) has been investigated. Particular attention is given to the evolution of the rheological behavior with increasing polymer concentration in the system at different volume fractions of the particles. Experiments were performed in the absence of salt and just the pH of the dispersion was adjusted to 9.5, a condition at which the system is electrostatically stable and electrostatic repulsive forces are long range in nature. It was observed that the shear viscosity and the linear viscoelastic functions of the dispersion at 55 vol% increase initially through the addition of polymer, reach a maximum, and then decrease to a minimum with further addition of polymer to the system. At higher polymer concentrations, there may be an increase in the viscosity of the dispersion owing to an increase in the concentration of free polymer chains in the medium causing depletion flocculation in the system. The increase in the rheological behavior of the dispersion at low polymer coverage is attributed to polymer bridging flocculation caused by a low-molecular-weight poly(ethylene oxide) in the system. Comparison of the data given here with the results of earlier studies on the viscosity behavior of the system in the presence of salt (0.01 M) indicates that the range of the electrostatic repulsion has a significant role in the rheological behavior of the system. Received: 7 February 2001 Accepted: 18 October 2001     

Effect of fumed silica nanoparticles on the morphology and rheology of immiscible polymer blends

We examined the effect of interfacially active particles on the morphology and rheology of droplet/matrix blends of two immiscible homopolymers. Experiments were conducted on polybutadiene/polydimethylsiloxane (10/90) blend and the inverse system. The effects of fumed silica nanoparticles, at low particle loadings (0.1–2.0 wt%), were examined by direct flow visualization and by rheology. Fumed silica nanoparticles were found to significantly affect the morphology of polymer blends, inducing droplet cluster structure and decreasing the droplet size, regardless of which phase wets the particles preferentially. This is surprising in light of much past research that shows that particles are capable of bridging and thus induce droplet cluster structure in droplet/matrix systems only when they are preferentially wetted by the continuous phase. Therefore, there should exist other possible mechanisms responsible for these droplet cluster structures except for the bridging mechanism. We proposed a particle-flocculating mechanism based on the fact that fumed silica particles readily flocculate due to their high aspect ratio, fractal-like shape, or interparticle attractions. Optical microscopy also reveals that the clustering structure becomes more extensive, and the droplet sizes in the clusters become smaller when the particle loading is increased. Rheologically, the chief effect of particles is to change the flow behavior from a liquid-like rheology to gel-like behavior. This gel-like behavior can be attributed to droplet clustering. Moreover, it should be emphasized that such gel-like behavior can be seen in the blends regardless of which phase wets the particles preferentially, suggesting that, once again, bridging is not the only cause of droplet clustering.     

Electrical double layer and rheological properties of yttria-stabilized zirconia suspensions in solutions of high molecular weight polyacrylic acid polymers

This work deals with the effect of the adsorption of two high molecular weight polyacrylic acid polymers (Carbopol) on the interfacial properties, and the rheology of aqueous zirconia suspensions. Since the Carbopol-covered particles can be thought of as soft colloids, Ohshimas theory was used to gain information on the surface potential and the charge density of the polymer layer (Ohshima H (1995) Electrophoretic mobility of soft particles. Colloids Surf A Physicochem Eng Aspects 103:249–255). The effect of the pH of the solution on the double layer characteristics is related to the different conformations of the adsorbed molecules provoked by the dissociation of the acrylic groups present in polymer molecules. The electrokinetic properties of the suspensions are studied for different pH and Carbopol concentrations in solution in order to investigate the possible stabilization of the suspensions by electrostatic repulsion between the particles. The rheological behavior of the suspensions was investigated in steady-state and dynamic conditions, and the corresponding yield stress and storage modulus were obtained in absence and presence of polymer in solution. The competition between bridging flocculation provoked by polymer adsorption and electrosteric stabilization determines the rheological properties of the suspensions. In the pH range investigated, bridging flocculation predominates at the neutral pH because of the graft of the uncoiled polymer to more than one particle, while at the extreme pH values (pH 3, pH 9) steric or electrosteric stabilization seems to be the predominant mechanism that explains the rheological results. These facts were confirmed by estimating the zirconia particle (or aggregate) diameter in the liquid medium by means of light scattering measurements.     

Particle-induced bridging in immiscible polymer blends

Pickering emulsions are emulsions whose drops are stabilized against coalescence by particles adsorbed at their interface. Recent research on oil/water/particle systems shows that particles can sometimes adsorb at two oil/water interfaces. Such “bridging particles” can glue together drops of oil in water or vice versa. We hypothesize that the same effect should apply in immiscible polymer blends with droplet-matrix morphologies, viz., added particles should glue together drops and give rise to particle-bridged drop clusters. We test this hypothesis in PIB-in-PDMS blends [PIB, poly(isobutylene); PDMS, poly(dimethylsiloxane)] with fumed silica particles. Direct visualization shows that the particles can indeed induce clustering of the drops, and the blends appear to show gel-like behavior. Such gel-like behavior is confirmed by dynamic oscillatory experiments. However, we are unable to conclusively attribute the gel-like behavior to droplet clustering: Association of the fumed silica particles in the bulk, which itself causes gel-like behavior, confounds the results and prevents clear analysis of the gluing effect of the particles. We conclude that PIB/PDMS/fumed silica is not a good model system, for studying particle-containing polymer blends. We instead propose that spherical monodisperse silica particles can offer a far more convenient model system, and provide direct visual evidence of gluing of PIB drops in a PDMS matrix.     

Non-linear viscoelastic behavior of fumed silica suspensions

Suspensions of fumed silica exhibit a wide range of rheological properties depending on the nature and magnitude of the interparticle forces. In a non-polar fluid, the particles interact through hydrogen bonding and can form a three-dimensional network. The microstructure formation is responsible for the non-linear viscoelastic behavior of fumed silica suspensions, even at very small strain. These non-linear rheological properties have been studied in small amplitude oscillatory experiments as a function of particle size, surface treatment of particles, suspending medium polarity and solids concentration. The non-linear viscoelastic behavior is characterized by a non-sinusoidal waveform of the signal response. For suspensions in a non-polar fluid, both the elastic and the loss moduli are shown to be sensitive to the strain amplitude: the elastic modulus is decreasing with increasing strain whereas the loss moduli is initially increasing with strain. We have chosen to examine the dissipated energy which is clearly related to the breakup of the suspension structure. A comparison of model predictions and the experimental data shows the limitations of these models, recently proposed in the literature to describe the behavior of colloidal suspensions. Received: 9 March 1998 Accepted: 17 November 1998     

Viscosity of suspensions in polymeric solutions

Viscosities of suspended particles in polymeric solutions depend upon dissolved polymer concentration, volume fraction of particles and shear rate. In this analysis of viscosity data, relative viscosity was defined as the ratio of suspension viscosity to solution viscosity at the same shear stress rather than shear rate. These relative viscosities reached asymptotic values at high shear stress for all concentrations of dissolved polymer and for all particle loadings. At a given particle loading, the asymptotic values of relative viscosity were nearly independent of the concentration of dissolved polymer. Realtive viscosities were correlated with volume fraction by the one-constant equation of Maron and Pierce.     

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.     

Linear viscoelasticity of ZrO 2 nanoparticle dispersions with associative polymers

ZrO₂ nanoparticle dispersions containing associative polymers exhibit two relaxation modes: Maxwellian behavior at high frequency imparted by the associating polymers and a power law spectrum at low frequency generated by the particle dynamics. The timescales and volume fraction dependence of the dispersions reflect weak attractions between particles with adsorbed polymer layers dispersed in a percolated network of associative polymer. The Baxter stickiness parameter extracted from the high frequency viscosity data indicates strong attractions, whereas the high frequency modulus reveals three sources of elasticity: micelle–micelle associations in the solution, rigidity of the particles and adsorbed layer, and adsorbed layer–adsorbed layer interactions. The sol-gel transition of the dispersions occurs around 12–14% particle loading. Comparison with latex dispersions suggests a slower relaxation mode and greater rigidity with the ZrO₂ particles.     

Linear and non-linear rheological behaviour of cement and silica suspensions. Effect of polymer addition

Oil well cement pastes and model silica suspensions demonstrate similar rheology: in oscillatory shear, beyond a critical stress, a sharp transition is ob- served between gel and liquid behaviour. In creep tests, an apparent yield stress and shear-thinning are followed by the appearance of shear thickening. The minimum viscosity measured in steady shear is close in value to the complex viscosity obtained from oscillatory measurements. The observations can be explained by the formation of liquid trapping aggregates whose compactness may be estimated by fitting the Tsenoglou model, and whose cohesion is reflected in the rigidity of the gel and in the critical strain (or stress) of gel dissolution. Substituting cement or silica particles by polymer redispersible powder causes a decrease of the storage modulus in the gel state and a lower viscosity, while leaving the general features of the flow curve unchanged. Decrease in material rigidity may be due to a weaker inter-particle attraction generated by the polymer presence. The decrease in viscosity is explained by a lessening of water entrapped within the aggregates, which now contain polymer particles which are less hydrophilic than either cement or silica.     

Rheology of particle suspensions in viscoelastic media. Wood flour-polypropylene melt

The dynamic mechanical behavior of suspensions of wood flour in polypropylene (PP) melts was investigated at varying filler concentrations. The main observed features were related to the viscoelastic nature of the polymer and to the filler aggregation, where the process of formation and destruction of particle clusters is governed by the polymer chain dynamics. The effect of the wood flour particles at low and large deformations was analyzed. The sample containing a wood flour concentration of 50% (by weight) showed a solid like behavior at low frequencies and was identified as the sample closer to a liquid-solid transition (LST). The values of the Newtonian viscosity obtained from sinusoidal oscillations at low frequencies were related to the concentration of filler in the suspensions. Moreover, a filler concentration scaling was found, that allows to obtain a master curve using the neat polymer as the reference and from which it is possible to calculate the dynamic mechanical behavior of all the suspensions. Apparently, for this system, the relaxation mechanisms of the neat polymer are not changed by the presence of the filler. However, the corresponding relaxation times are increased as a function of the filler concentration.     

Capillary-driven percolating networks in ternary blends of immiscible polymers and silica particles

We investigate the structure and rheology of a melt-blended ternary system composed of a continuous polymer phase, silica particles in the few-micron size range, and a small amount of a second immiscible polymer phase which preferentially wets the particles. The morphology of the ternary system is found to consist of a volume-spanning “pendular network” of particles bridged by menisci of the wetting polymer, as well as “capillary aggregates” which are large compact particle aggregates saturated by the wetting polymer. The ternary blends have strongly non-Newtonian melt rheology due to the pendular network. The relative extent of capillary aggregation depends on the melt-blending history, and the rheological properties can be used to track the changes in the blend structure. The pendular network is seen at a particle loading of only 10 vol.%, demonstrating that capillary bridging lowers the percolation threshold of a particle-filled polymer.      

Solutions of xanthan gum/guar gum mixtures: shear rheology,porous media flow,and solids transport in annular flow

Mixtures of xanthan and guar gum in aqueous solution were studied in two flow situations: simple shear and porous media. In addition, solids transport in vertical annular flow of sand suspensions was explored. The zero shear rate viscosity of the solutions displayed a pronounced synergy: the viscosity of the mixture is higher than that of the polymer solutions in a wide range of relative concentrations of the two polymers, in agreement with previous literature. However, at relatively high shear rates, the viscosity approaches the value of the more viscous xanthan gum solutions at mass fractions of xanthan gum between 0.1 and 0.15, and the degree of synergy substantially decreases. Stress relaxation experiments in simple shear indicate that the polymer mixtures exhibit a well-defined yield stress after relaxation that is absent in solutions of pure polymers. In porous media flow experiments, a synergistic behavior mimicking the shear flow results was obtained for the polymer mixtures at low shear rates. However, at a critical shear rate, the apparent viscosity in porous media flows exceeds the shear viscosity due to the elongational nature of flow in the pores. The solids transport capacity in annular flows is well-represented by trends in shear viscosity and stress relaxation behavior. However, the lack of viscosity synergy at high shear rates limits the applicability of the mixtures as a way to improve solids suspension capacity in annular flows.     

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.