Investigation of shear thinning behavior and microstructures of MWCNT/epoxy and CNF/epoxy suspensions under steady shear conditions

This report investigates the steady-state viscosities of multiwall carbon nanotube (MWCNT)/epoxy and carbon nanofiber (CNF)/epoxy suspensions with varying filler concentrations under different shear rates at various temperatures. In situ observation of filler networks suggests the build-up of shear induced MWCNT and CNF agglomerates at low shear rates, which correlates with the measured shear thinning behavior. The agglomeration process in MWCNT/epoxy suspensions is enhanced at lower shear rates in the case of higher temperatures, whereas, at high shear rates, both nano-fillers show good dispersion. Shear thinning behavior is observed for both types of fillers, and shear thinning exponential parameters are evaluated as a function of filler content. The shear thinning exponent increases in conjunction with increase in filler content, but it is found to saturate at a specific value, independently of filler material. Finally, the micromechanical elasticity-based analogy model is applied to the prediction of steady state shear viscosity of suspensions at higher shear rates with the assumption of complete dispersion and alignment of individual nano-fillers in suspensions. The predicted viscosities and the experimental data at higher shear rates are compared. The results conclude that fairly good agreement can be seen for the cases of CNF/epoxy suspensions at lower temperatures, whereas MWCNT/epoxy suspensions and CNF/epoxy suspensions at higher temperatures show discrepancy between the prediction and the experimental data.     

Integral equation for calculation of distribution function of activation energy of shear viscosity

A new technique of calculation of a distribution function of activation energy (f(E)) of shear viscosity based on a regularization procedure applied to the Fredholm integral equation of the first kind has been developed using the Baxter-Drayton and Brady model for concentrated and flocculated suspensions. This technique has been applied to the rheological data obtained at different shear rates for aqueous suspensions with fumed silica A-300 and low-molecular (3,4,5-trihydroxybenzoic acid and 1,5-dioxynaphthalene) or high-molecular (poly(vinyl pyrrolidone) of 12.7 kDa and ossein of 20-29 kDa) compounds over a wide concentration range (up to 25 wt% of both components) and at different temperatures. Monomodal f(E) distributions are observed for the suspensions with individual A-300 or A-300 with a low amount of adsorbed organics. In the case of larger amounts of nanosilica and organics the f(E) distributions are multimodal because of stronger structurization and coagulation of the systems that require a high energy to break the coagulation structures resisting to the shear flow.     

Flow-Induced Anisotropy in Mixtures of Associative Polymers and Latex Particles

The effect of associative polymers on the structure and rheological behavior of colloidal suspensions is discussed. Adding associative polymer is known to increase the viscosity of the suspensions. At high shear rates the increase is close to what could be expected on the basis of the hydrodynamic effects of the added polymer. At low shear rates the viscosity increases much more. Small-angle light scattering (SALS) during flow is used here to investigate the underlying structural mechanisms. The SALS patterns indicate that the associative polymer changes the particulate structure: characteristic butterfly patterns appear even at relatively low particle volume fractions. They are not present in the suspensions without associative polymer. The patterns indicate that fluctuations in particle concentration are more pronounced in the flow direction than in the vorticity direction and that anisotropic particulate structures with an orientation along the vorticity direction develop. The evolution of their characteristic length scale during flow has been followed over time. Changing the hydrophilic part of the polymer from polyacrylamide to polyacrylic acid induces stronger associative interactions. In the suspensions this results in a reduction of the relative viscosity rather than an increase. The difference in degree of associativity between the polymers also has an effect on the SALS patterns in the suspensions both at rest and during flow. The rheology as well as the SALS suggest the presence of a strong polymer network in the second system. The competition between adsorption of the associative polymer on the particles with the intermolecular associations between the polymer chains seems to be responsible for the observed differences. Copyright 2000 Academic Press.     

Structural network theory for a filled polymer melt in large amplitude oscillatory shear

The large amplitude oscillatory shear (LAOS) behavior of a high density polyethylene (HDPE) pipe resin containing 2% carbon black has been measured with a sliding plate rheometer incorporating a shear stress transducer. We have evaluated a structural network theory recently proposed by De Kee and Chan Man Fong for suspensions, in LAOS. This model provides for the creation of junctions due to an imposed flow field, and has been proposed as a generalization of the Liu kinetic rate equation, to model the complex behavior of suspensions. A new model, also based on the transient network concept, is proposed for filled polymer melts, and has the desirable feature of separating the effects of the filler material from the entanglement kinetics of the pure polymer. Both models are able to fit the steady shear viscosity data measured for this material. We find that both models are capable of predicting the LAOS behavior of this material, except for severe conditions.     

Dynamic mechanical properties of suspensions of micellar casein particles

Small micellar casein particles, so-called submicelles, were obtained by removing colloidal calcium phosphate from native casein by adding sodium polyphosphate. Aqueous submicelle suspensions were characterized using light scattering and rheology as a function of concentration and temperature. The casein submicelles behave like soft spheres that jam at a critical concentration (C(c)) of about 100 g L(-1). The viscosity does not diverge at C(c), but increases sharply, similarly to that of multiarm star polymers. C(c) increases weakly with increasing temperature, which leads to a strong decrease of the viscosity close to and above C(c). Concentrated submicelle suspensions show strong shear-thinning above a critical shear rate and the shear stress becomes independent of the shear rate. The critical shear rates at different temperatures and concentrations are inversely proportional to the zero-shear viscosity. At much higher shear rates, the shear stress fluctuates strongly in time indicating inhomogeneous flow. The frequency dependence of casein submicelle suspensions is characterized by elastic behavior at high frequencies (concentrations) and viscous behavior at low frequencies (concentrations).     

Shear-Induced Changes in Rheological Reponses and Neutron Scattering Properties of Hydrophobic Silica Suspensions at Low Silica Concentrations

Rheological responses of hydrophobic fumed silica powders, whose surface silanol groups were modified by hexadecane, suspended in 1,4-dioxane at lower silica concentrations than 6.8 vol% have been investigated as a function of the silica concentration. Transient shear stress behavior before attaining the steady-state shear stress could be classified into three regimes as follows, irrespective of the silica concentration: at the lower shear rates than ca. 0.3 s^?1 a stress overshoot was observed, at the shear rate ranges from 0.3 to 30 s^?1 sustained oscillations in shear stresses were exhibited and these oscillations were first observed for the suspensions at the low particle concentrations, and beyond the shear rate of 30 s^?1 a sigmoid decrease of the shear stress with increasing time, that is, structural breakdown, was observed. At the steady state the silica suspensions showed shear thickening. Small angle neutron scattering (SANS) measurements of the silica suspension under shear flow provided that changes in the SANS intensities were well correlated with the shear thickening behavior. However, shear thinning behavior at higher shear rates did not cause any changes in the SANS intensities.     

Time-Dependent and Shear-Dependent Transient Viscosity of an Alumina Suspension

The transient viscosity of a well-dispersed Alumina–polyvinyl butyral tape-casting slurry have been investigated at the shear domain of 1–8 s^?1 with the help of a conventional Couette device. The slurry under these shear rates shows a combination of shear dependence and time dependence based upon the applied shear. Attempts have been made to explain the diverse rheological behavior of the slurry. Many studies involving powder loading, milling time, extended shear up ramp, extended shear down ramp, time- and shear-dependent viscosities of the supernatant, and continual shearing have been conducted to explore the probable reasons behind such diverse behavior of the slurry. The findings of these studies strongly suggest that at the shear rates, shear-induced hydrodynamic diffusion plays a major role in dictating the time-dependent viscosity profile of the suspension. Further analysis of the results points out that the observed viscosity profiles are the resultant of the two major competitive processes of shear-induced hydrodynamic disffusion and shear rejuvenation. The results obtained in the present investigation also strongly indicate that the time-dependent behavior of the suspensions under shear opens up an alternative route of characterization of well-dispersed ceramics suspensions.     

The vane method and kinetic modeling: shear rheology of nanofibrillated cellulose suspensions

We conduct rheological characterization of nanofibrillated cellulose (NFC) suspensions, a highly non-Newtonian complex fluid, at several concentrations. Special care is taken to cope with the prevalent problems of time scale issues, wall depletion and confinement effects. We do this by combining the wide-gap vane geometry, extremely long measurement times, and modeling. We take into account the wide-gap related stress heterogeneity by extending upon mainstream methods and apply a gap correction. Furthermore, we rationalize the experimental data through a simple viscous structural model. With these tools we find that, owing to the small size of the particles subjected to Brownian motion, the NFC suspensions exhibit a critical shear rate, where the flow curve experiences a turning point. This makes the steady state of these suspensions at low shear rates non-unique. To optimize various mixing and pumping applications, such history dependent tendency of NFC suspensions to shear band needs to be taken into account.     

Shear-thickening flow of nanoparticle suspensions flocculated by polymer bridging

The steady-shear viscosity, dynamic viscoelasticity, and stress relaxation behavior were measured for suspensions of silica nanoparticles dispersed in aqueous solutions of poly(ethylene oxide) (PEO). The suspensions of silica with diameters of 8-25 nm show striking shear-thickening profiles in steady shear and highly elastic responses under large strains in oscillatory shear. Since the silica particles are much smaller than the polymer coils, one molecule can extend through several particles by intrachain bridging. Each polymer coil may remain isolated as a floc unit and the silica particles hardly connect two flocs. Therefore, the flow of suspensions is Newtonian with low viscosity at low shear rates. When the polymer coils containing several nanoparticles are subjected to high shear fields, three-dimensional network is developed over the system. The shear-thickening flow may arise from the elastic forces of extended bridges. But, the polymer chain is easily detached from particle surface by thermal energy because of large curvature of particles. As a result, the network structures are reversibly broken down in a quiescent state and the suspensions behaves as viscoelastic fluids with the zero-shear viscosity.     

Rheology of polystyrene latexes with adsorbed and free gelatin

The rheology of monodisperse polystyrene latex particles of two different particle radii (26 and 67 nm) has been studied with a range of concentrations of the polyampholyte gelatin. Gelatin contributes to the rheology by adsorption to the particles and by thickening the continuous phase. High viscosities and strong shear thinning are measured for low volume fractions of latex. A procedure is presented to deconvolute the effects of free and bound gelatin by applying simple hard-sphere models. This procedure allows us to estimate the effective size of the gelatin-covered particles as well as the continuous-phase gelatin concentration and viscosity. The layer thicknesses from rheology agree well with those from PCS. The effect of varying particle volume fraction, ionic strength, pH and gelatin and surfactant concentration on the rheology of these suspensions is presented. For the smaller latex, the adsorbed layer occupies a greater fraction of the effective volume. Increasing free polymer concentration reduces the adsorbed-layer thickness. The reduced critical shear stress increases with the suspension viscosity for suspensions of the 26 nm latex but is constant for the 67 nm latex. At very high shear (>2000 s⁻¹), the suspensions show excess shear thinning over that expected from a hard-sphere model. This excess thinning is attributed to deformation of the adsorbed gelatin layer under high shear stress and interpreted in terms of an empirical interparticle potential.     

Viscosity contribution of an arbitrary shape rigid aggregate to a dilute suspension

The study of rheological response of solid suspensions is essential in understanding the relationships governing their kinematics and dynamics. However the study is complicated mainly by the complex interplay between suspension rheology and hydrodynamic behavior of the suspended solids, which for most of the practically occurring situations have complex and arbitrary shapes, and exact equations accounting for their hydrodynamic contribution are not available. For this reason, using a recently developed methodology capable of computing the average rigid body resistance matrix of arbitrary shaped clusters made of uniform sized spheres, Brownian dynamic simulations under shear conditions are performed for clusters with different geometries with the objective of estimating their intrinsic viscosity. The population of clusters chosen encompassed a broad range of morphologies, such as fractals with a wide range of masses and fractal dimension values, dense clusters with spherical and spheroidal aspect ratios, similar to those produced during coagulation experiments of colloidal suspensions. It was found that fractal clusters with low fractal dimensions and spheroidal clusters have sufficient structural anisotropies to show deviations from Einstein's relationship, and display a moderate shear thinning behavior, as well as a non-negligible linear viscoelasticity. On the other hand, clusters with high fractal dimensions tend to behave progressively more like spheres as their fractal dimension increases. We also found that the intrinsic viscosity of all clusters, independent of their morphology, can be quantitatively predicted by means of an equivalent ellipsoid model, in which clusters are modeled as ellipsoids with the same principal moments of inertia.     

Rheology of water-in-water suspensions formed with lightly sulfonated ionomers

The formation and rheological properties of water-in-water suspensions formed by mixing a dilute nonaqueous solution containing a lightly sulfonated ionomer with an aqueous solution are described. The spheres formed via this process are composed of a very thin (approximately 2000 Å), ionically crosslinked gel membrane which separates the continuous aqueous phase from the encapsulated aqueous phase. The membrane itself is composed of the lightly sulfonated ionomer (i. e., sulfonated polystyrene) swollen with the nonaqueous solvent. Interestingly, surface tension measurements indicate that the sulfonated ionomer in this nonaqueous solvent has no significant interfacial activity. Viscometric measurements confirm that aqueous solvents containing these spheres have considerably enhanced viscosity even in the presence of high concentrations of a salt or acid. Thixotropic behavior is observed at low shear rates, whereas Newtonian behavior is observed at higher rates of shear (> 40 sec^–1). Cessation of stress reverts the viscosity to its initial value. Dilution studies show that the streamlines in the flowing exterior aqueous phase cause circulation of the aqueous fluid within the sphere. These results point to the fluid-like characteristics of the gel membrane, since transmission of the stress across the membrane is not dramatically inhibited. Comparison of the low shear rate data with the Mooney equation support these conclusion.     

Peptide-mediated selective adhesion of smooth muscle and endothelial cells in microfluidic shear flow

Microfluidic devices have recently emerged as effective tools for cell separation compared to traditional techniques. These devices offer the advantages of small sample volumes, low cost, and high purity. Adhesion-based separation of cells from heterogeneous suspensions can be achieved by taking advantage of specific ligand-receptor interactions. The peptide sequences Arg-Glu-Asp-Val (REDV) and Val-Ala-Pro-Gly (VAPG) are known to bind preferentially to endothelial cells (ECs) and smooth muscle cells (SMCs), respectively. This article examines the roles of REDV and VAPG and fluid shear stress in achieving selective capture of ECs and SMCs in microfluidic devices. The adhesion of ECs in REDV-coated devices and SMCs in VAPG-coated devices increases significantly compared to that of the nontargeted cells with decreasing shear stress. Furthermore, the adhesion of these cells is shown to be independent of whether these cells flow through the devices as suspensions of only one cell type or as a heterogeneous suspension containing ECs, SMCs, and fibroblasts. Whereas the overall adhesion of cells in the devices is determined mainly by shear stress, the selectivity of adhesion depends on the type of peptide and on the device surface as well as on the shear stress.     

Influence of interparticle interaction effects on the rheological properties of low density polyethylene filled with glass beads

The rheological properties of Low-density polyethylene (LDPE) compounds with different fractions of glass beads have been investigated by means of high pressure capillary rheometry. The purpose of this study is to find a functional approach for describing the flow behaviour of suspensions as a function of the volumetric filler content and the applied shear stress or shear rate, respectively. The flow behaviour of suspensions is influenced by interaction effects, which are dependent on the filler particle, its volume content and particle size. While small glass beads exhibit pronounced interparticle interaction effects even at low volumetric filler concentrations, large glass beads show a plateau of negligibly interactions up to approx. 20% volumetric filler content. With introducing a generalized interaction function the flow behaviour of the tested suspensions could be described with reasonable accuracy in consideration of the transition from negligible to pronounced interactions.     

ELECTRORHEOLOGICAL PROPERTIES OF POLYANILINE/PUMICE COMPOSITE SUSPENSIONS

Electrorheological （ER） properties of polyaniline （PAni）, pumice and polyaniline/pumice composites （PAPC） were investigated. Polyaniline and PAni/pumice composite were prepared by oxidative polymerization. PAni/pumice particlesbased ER suspensions were prepared in silicone oil （SO）, and their ER behavior was investigated as a function of shear rate, electric field strength, concentration and temperature. Sedimentation stabilities of suspensions were determined. It has been found that ER activity of all the suspensions increases with increasing electric field strength, concentration and decreasing shear rate. It has shown that the suspensions have a typical shear thinning non-Newtonian viscoelastic behavior. Yield stress of composite suspensions increased linearly with increasing applied electric field strength and with concentrations of the particles. The effect of high temperature on ER activity of purrfice/silicone oil systems was also investigated.     

Negative thixotropy of solutions of partially hydrolyzed polyacrylamide

We found that the character of negative thixotropy of partially hydrolyzed polyacrylamide in aqueous glycerol strongly depends on polymer concentration, glycerol content and shear rate applied. At low polymer and glycerol concentrations, shear stress and viscosity slowly increased during shearing to a limiting value. In addition to this behavior, a steep increase in shear stress as well as normal stress followed by their pronounced oscillations occurred at higher concentrations of both components and at higher shear rates. Similarly to the negative thixotropic effect in solutions of other polymers in organic solvents, the hydrodynamic conditions in which the effects set in seem to be controlled by the shear stress acting in the flowing solution; initial kinetics of the effect depends on solvent viscosity and shear stress applied. To explain the influence of the glycerol content and degree of ionization of the polymer on the minimum shear stress at which the effect sets in, a decisive role of intermolecular electrostatic repulsions in association of the polymer molecules in shear field is assumed.     

The influence of salt concentration on negative thixotropy in solutions of partially hydrolyzed polyacrylamide

The influence of NaCl concentration on negative thixotropy in aqueous glycerol solutions of partially hydrolyzed polyacrylamide have been investigated. It was found that negative thixotropy type I (a slow increase in viscosity with time of shearing) sets in at higher critical shear rates when the salt is present. On the other hand, critical shear rates for negative thixotropy type II (a rapid increase in viscosity followed by viscosity oscillation) did not depend on the salt addition. Using the critical shear stress as a hydrodynamic criterion for the occurrence of negative thixotropy, a possible explanation of the behavior is proposed.