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.     

Role of Electrostatic Repulsion on the Viscosity of Bidisperse Silica Suspensions

The flow behavior of bidisperse aqueous silica suspensions has been studied at different electrolyte concentrations as a function of shear rate, total volume fraction of the particles, and volume ratio of small to large particles. It is shown that the range of the electrostatic repulsion plays an important role in determining the viscosity of the suspension. Binary mixtures of particles of longer range repulsive forces showed higher viscosities than the suspensions of shorter range electrostatic interactions. Bimodal suspensions of long-range interactions showed non-Newtonian behavior over wider ranges of shear due to the deformation of the ionic cloud around the particles, which is larger in these systems. The viscosity of bimodal suspensions used in this study was scaled with respect to the viscosity of the related monosized systems and the viscosity of one bimodal suspension at a fixed total volume fraction of the particles, employing our earlier scaling method. The model normalizes the effect of colloidal forces by introducing a scaling factor that collapses the data into a single curve for bimodal suspensions of a particular size ratio, and it is shown that the model is valid for systems with both short-range and long-range repulsive forces. Copyright 1999 Academic Press.     

Time dependent viscosity of concentrated alumina suspensions

Viscometric investigations of concentrated aqueous alumina suspensions with particles smaller than 5 μm have been performed. Experimental flow curves indicate thixotropy in the shear rate interval between =20 and 640 s⁻¹. In the range smaller than =200 s⁻¹ we found pseudoplastic flow behavior, in the higher range the material shows dilatancy. The non-Newtonian behavior results from a small content of sodium aluminum oxide in the alumina suspension. This gives rise to interparticle forces that can drive the suspension into a gel-like state. The time scale of this process is some days. On the short-time scale of some hours the material ages slowly increasing moderately the apparent viscosity. Studying the relaxation process after a shear rate jump, the shear stress time dependency at constant shear rate follows an exponential law. There is a single particular relaxation time for each shear rate. The relaxation towards a steady state occurs asymptotically over some 10³ s. Flow curves calculated from steady state data after relaxation processes are below the experimental flow curves which were measured during some 100 s. The flow curves follow the Herschel–Bulkley formula. The shape of the viscosity curves indicates changes of suspension structure at ca. =200 and 400 s⁻¹. At constant shear rates in the interval between =400 and 450 s⁻¹ the apparent viscosity of the alumina suspension fluctuates periodically in time in the same manner found for other suspensions. This effect is interpreted as periodic organization of agglomeration and deglomeration processes. Supposing, that the stabilisation energy of agglomerates is of the order of the energy introduced by the mechanical shear field, the observation of oscillations at =400 s⁻¹ is in agreement with the drastic slope change in the viscosity curves.     

On the theory of oscillating flows in complex liquids

Experiments with highly concentrated suspensions and other complex liquids frequently demonstrate nonmonotonic N- or S-shaped dependences of viscous stress σ on shear rate $ \dot \gamma $ \dot \gamma and strong oscillations of the shear rate at a constant flow-inducing external stress, as well as oscillations of the viscous stress at a constant average shear rate. A phenomenological mathematical model is proposed for oscillating flows according to which oscillations arise when an applied stress (or the average shear rate, depending on the design of an experiment) is in the descending region of the σ-$ \dot \gamma $ \dot \gamma dependence and a complex liquid exhibits pronounced viscoelastic properties.     

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).     

Rheological peculiarities of concentrated suspensions

The rheological properties of concentrated suspensions of metal oxides dispersed in transformer oil, which are used as electrorheological fluids, are systematically studied. Colloidal particles have intermediate sizes between nano- and microsized scales. Low-amplitude dynamic measurements show that the storage moduli of the examined suspensions are independent of frequency and these materials should be considered as solidlike elastic media. The storage modulus is proportional to the five-powdered particle volume concentration. At the same time, a transition through an apparent yield stress with a reduction in the viscosity by approximately six orders of magnitude is distinctly seen upon shear deformation. The character of the rheological behavior depends on the regime of suspension deformation. At very low shear rates, a steady flow is possible; however, upon an increase in the rate, an unsteady regime is realized with development of self-oscillations. When constant shear stresses are preset, in some range of stresses, thickening of the medium takes place, which can also be accompanied by self-oscillations. In order to gain insight into the nature of this effect, measurements are performed for samples with different volume/surface ratios, which show that, in some deformation regimes, suspension is separated into layers and slipping occurs along a low-viscosity layer with a thickness of several dozen microns. Direct observations show a distinct structural inhomogeneity of the flow. The separation and motion of layers with different compositions explain the transition to the flow with the lowest apparent Newtonian viscosity. Thus, the deformation of concentrated suspensions is associated with self-oscillations of stresses and slipping along a low-viscosity interlayer.     

Flow curves of dense colloidal dispersions: schematic model analysis of the shear-dependent viscosity near the colloidal glass transition

A recently proposed schematic model for the nonlinear rheology of dense colloidal dispersions is compared to flow curves measured in suspensions that consist of thermosensitive particles. The volume fraction of this purely repulsive model system can be adjusted by changing temperature. Hence, high volume fractions (phi相似文献   

Rheological behavior of silica suspensions in aqueous solutions of associating polymer

Associating polymers are hydrophilic long-chain molecules containing a small amount of hydrophobic groups. The aqueous solutions show viscoelastic responses above some critical concentrations because a three-dimensional structure is formed by association of hydrophobic groups. When the associating polymers are added to silica suspensions at low concentrations, the flocculation is induced by bridging mechanisms, and the flow of suspensions become shear-thinning. For suspensions prepared with polymer solutions in which the associating network is developed, the viscosity decreases, shows a minimum, and then increases with increasing particle concentration. The viscosity decrease may arise from the breakdown of associating network due to adsorption of polymer chains onto the silica surfaces. As the particle concentration is increased, the polymer concentration in solution is decreased, and finally, all polymer chains are adsorbed on the surfaces. Beyond this point, the partial coverage of particle surfaces takes place and strong interactions are generated between particles by polymer bridging. Since the stable suspensions are converted to highly flocculated systems, the viscosity is increased and the flow becomes shear-thinning. The concentration effect of silica particles on the viscosity behavior of suspensions can be explained by a combination of viscosity decrease in solution due to polymer adsorption and viscosity increase due to flocculation.     

Size effect on the rheological behavior of nanoparticle suspensions in associating polymer solutions

Associating polymers are hydrophilic long-chain molecules containing a small amount of hydrophobic groups and tend to create bonds between chains by reversible associating interactions. The effects of associating polymer on the steady-shear viscosity and dynamic viscoelasticity are studied for suspensions of silica nanoparticles with diameters of 8, 18, and 25 nm. The silica particles of 8 nm are entrapped in the transient network of associating polymer by reversible adsorption. The enhancement of network results in the high viscosity with a Newtonian flow profile in the limit of zero shear rate. In suspensions of 25 nm silica, the hydrophobes extending from the chains adsorbed onto different particles can form a micelle by association interactions. The multichain bridging gave rise to the shear-thinning flow and high storage modulus at low frequencies. The suspensions of 25 nm silica are characterized as flocculated systems. Because of intermediate curvature, the flexible bridges are formed between silica particles of 18 nm. When the flexible bridges are highly extended within the lifetime in shear fields, the suspensions show shear-thickening flow. The shear-thickening flow can be attributed to the elastic effect of flexible bridges.     

Influence of poly(ethylene oxide) brushes on the rheological properties of MgO colloidal suspensions in water

A combined experimental and multiscale simulation study of the influence of polymer brush modification on interactions of colloidal particles and rheological properties of dense colloidal suspensions has been conducted. Our colloidal suspension is comprised of polydisperse MgO colloidal particles modified with poly(ethylene oxide) (PEO) brushes in water. The shear stress as a function of shear rate was determined experimentally and from multiscale simulations for a suspension of 0.48 volume fraction colloids at room temperature for both bare and PEO-modified MgO colloids. Bare MgO particles exhibited strong shear thinning behavior and a yield stress on the order of several Pascals in both experiments and simulations. In contrast, simulations of PEO-modified colloids revealed no significant yielding or shear thinning and viscosity only a few times larger than solvent viscosity. This behavior is inconsistent with results obtained from experiments where modification of colloids with PEO brushes formed by adsorption of PEO-based comb-branched chains resulted in relatively little change in suspension rheology compared to bare colloids over the range of concentration of comb-branch additives investigated. We attribute this discrepancy in rheological properties between simulation and experiment for PEO-modified colloidal suspensions to heterogeneous adsorption of the comb-branch polymers.     

Phase behavior of a simple dipolar fluid under shear flow in an electric field

Nonequilibrium molecular dynamics simulations are performed on a dense simple dipolar fluid under a planar Couette shear flow. Shear generates heat, which is removed by thermostatting terms added to the equations of motion of the fluid particles. The spatial structure of simple fluids at high shear rates is known to depend strongly on the thermostatting mechanism chosen. Kinetic thermostats are either biased or unbiased: biased thermostats neglect the existence of secondary flows that appear at high shear rates superimposed upon the linear velocity profile of the fluid. Simulations that employ a biased thermostat produce a string phase where particles align in strings with hexagonal symmetry along the direction of the flow. This phase is known to be a simulation artifact of biased thermostatting, and has not been observed by experiments on colloidal suspensions under shear flow. In this paper, we investigate the possibility of using a suitably directed electric field, which is coupled to the dipole moments of the fluid particles, to stabilize the string phase. We explore several thermostatting mechanisms where either the kinetic or configurational fluid degrees of freedom are thermostated. Some of these mechanisms do not yield a string phase, but rather a shear-thickening phase; in this case, we find the influence of the dipolar interactions and external field on the packing structure, and in turn their influence on the shear viscosity at the onset of this shear-thickening regime.     

Stability and Flow-Induced Flocculation of Fumed Silica Suspensions in Mixture of Water-Glycerol

A systematic investigation has been performed to relate the effect of glycerol composition to the rheological properties of aqueous suspensions of hydrophilic fumed silica at pH far from the isoelectric point. Steady state/dynamic rheology and electrophoresis measurements are compared to correlate the stability of the suspension with particle-particle and particle-solvent interactions. Although the extent of electrostatic stability is reduced by addition of glycerol, the rheological properties show a transition from a highly flocculated gel to stable dispersions containing no microstructures. This is attributed to a high degree of hydrogen-bonding between glycerol and the Aerosil surface silanol groups. Small dissociation of NaCl and particles reduce the effect of ion exchange and particle bridging mechanisms when the suspensions destabilise in the presence of glycerol. The high viscosity of glycerol is important with respect to the formation of a thick solvation layer around the particles. These parameters give rise to short-range, non-DLVO repulsive solvation forces, which stabilise the dispersion. At intermediate concentrations of glycerol (30–60 wt%) the apparent viscosity increase abruptly and irreversibly as both the extent and time of shearing are increased. The shear rate for the onset of the shear thickening is found to be retarded by decreasing the particle and salt concentration as well as by increasing the glycerol concentration. It is postulated that at intermediate glycerol concentration, where the height of the energy barrier is small, mechanical forces can activate the particles to overcome the energy barrier to enter the region where attractive forces dominate. Here, domination of the hydrodynamic forces to the colloidal forces under the shear results in formation of irreversible gels which does not relax to its initial condition.     

Rheological Properties of Silica Particle Suspensions in Mineral Oil

The rheological properties of particles suspended in a non‐polar mineral oil have been investigated as a function of volume fraction of particles, particle size, surface properties and shear rate. Three different types of particles were investigated; glass microspheres, monodisperse silica particles and fumed silica. The suspensions showed shear thinning behavior at higher volume fractions, and the viscosity increased with decreasing particle size. The hydrophobic particles display lass shear thinning effects. The relative viscosity of all the suspensions was well fitted to the Krieger and Dougherty model.     

Rheology of binary colloidal structures assembled via specific biological cross-linking

The selectivity and range of energies offered by specific biological interactions serve as valuable tools for engineering the assembly of colloidal particles into novel materials. In this investigation, high affinity biological interactions between biotin-coated "A" particles (RA = 0.475 microm) and streptavidin-coated "B" particles (RB = 2.75 microm) drive the self-assembly of a series of binary colloidal structures, from colloidal micelles (a large B particle coated by smaller A particles) to elongated chain microstructures (alternating A and B particles), as the relative number of small (A) to large (B) particles (2 < or = NA/NB < or = 200) is decreased at a low total volume fraction (10(-4) < or = phiT < or = 10(-3)). At a significantly higher total volume fraction (phiT > or = 10(-1)) and a low number ratio (NA/NB = 2), the rheological behavior of volume-filling particle networks connected by streptavidin-biotin bonds is characterized. The apparent viscosity (eta) as a function of the shear rate gamma, measured for networks at phiT = 0.1 and 0.2, exhibits shear-rate-dependent flow behavior, and both the apparent viscosity and the extent of shear thinning increase upon an increase of a factor of 2 in the total volume fraction. Micrographs taken before and after shearing show a structural breakdown of the flocculated binary particle network into smaller flocs, and ultimately a fluidlike suspension, with increasing shear rate. Rheological measurements provide further proof that suspension microstructure is governed by specific biomolecular interactions, as control experiments in which the streptavidin molecules on particles were blocked displayed Newtonian flow behavior. This investigation represents the first attempt at measuring the rheology of colloidal suspensions where assembly is driven by biomolecular cross-linking.     

Microstructure and Viscosity of Aggregating Colloids under Strong Shearing Force

Disaggregation under strong shearing force is simulated for an aggregating colloid based on a sticky particle model which can describe the disaggregating and aggregating kinetics, the deformation, and the rupture of clusters with a minimum number of parameters. For a 2-dimensional system, the viscosity and coordination number of the model colloid are calculated at each time step, and the changes of microstructure with shear flow are observed directly by displaying the configuration of particles onto a monitor. The viscosity depends on both area fraction and shear rate, but coordination number depends only on shear rate. Furthermore, the viscosity and coordination number at steady state are independent of the initial state of particles, which indicates that the disaggregation and aggregation are mutually reversible. Copyright 1999 Academic Press.     

Electrorheological properties and microstructure of silica suspensions

We present experimental and theoretical results on the electrorheological response and microstructure of colloidal suspensions composed of silica nanoparticles dispersed in a silicon oil, as a function of electric field strength and silica water content. Using small-angle neutrons scattering experiments, we determined the evolution of the static structure factor of the suspensions when an electric field is applied. Experimental data were fitted with model calculations using the Percus-Yevick solution for Baxter's hard-sphere adhesive potential. The obtained stickiness parameter is directly related to the polarization interactions that depend on the water content of silica particles. The influence of the polarization interparticle potential on the rheology of the silica dispersions was investigated in a second time. A microscopic theory for the shear viscosity of adhesive hard-sphere suspensions was successfully used which describes the steady shear viscosity of suspension in terms of the fractal concept.     

Stress jumps on weakly flocculated dispersions: steady state and transient results

Weakly flocculated, thixotropic suspensions have been investigated by means of fast stress jump experiments. With a suitable procedure, reliable stress relaxation data could be collected starting 20 ms after cessation of flow. This technique has been used to determine the elastic and hydrodynamic contributions to the shear stress. Steady state as well as transient flows have been studied for suspensions containing either fumed silica or carbon black particles in a Newtonian medium. In both systems, the elastic stress totally dominates the response at low shear rates and consequently also the apparent yield stress. This stress contribution becomes negligibly small at high shear rates. The hydrodynamic contribution to the viscosity has finite limits at both the low and high shear rate ends. The data are relevant for testing rheological models. As an illustration, it is shown that the data agree qualitatively with the model proposed by Potanin et al. (J. Chem. Phys. 102 (14) (1995) 5845-5853).     

Model filled rubber. II. Particle composition dependence of suspension rheology

Monodisperse size colloidal particles varying in chemical composition were synthesized by emulsifier‐free emulsion polymerization. Using a stress‐controlled rheometer, the rheological behavior of colloidal suspensions in a low molecular weight liquid polysulfide was investigated. All suspensions exhibited shear thinning behavior. The shear viscosity, dynamic moduli, and yield stress increased as interactions between particles and matrix increased. The rheological properties associated with network buildup in the suspensions were sensitively monitored by a kinetic recovery experiment. We propose that interfacial interactions by polar and hydrogen bonding between particles and matrix strongly promote affinity of matrix polymer to the filler particles, resulting in adsorption or entanglement of polymer chains on the filler surface. A network structure was formed consisting of particles with an immobilized polymer layer on the particle surface with each particle floc acting as a temporary physical crosslinking site. As the interfacial interaction increases, the adsorbed layer thickness on the filler particles, hence, the effective particle volume fraction, increases. As a result, the rheological properties were enhanced in the order PS < PMMA < PSVP. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 815–824, 1999     

Improving titanium dioxide dispersion in water through surface functionalization by a dicarboxylic acid

In this work, we show evidence of improving the dispersion of titanium dioxide particles in water. This is observed in the titanium dioxide-water colloid by the shear-thinning flow behavior in rheological measurements induced by the functionalization of a glutaric acid layer on the surface of titanium dioxide particles. The characterization of the layer was achieved by using infrared spectroscopy and ^13?C nuclear magnetic resonance. Rheological measurements corroborated that functionalization of TiO₂ particles decreases the rheological properties such as viscosity measurements at a constant shear rate in two orders of magnitude compared with the pure TiO₂ in suspensions. We present the results as a novel strategy to limit the formation of agglomerates in these colloidal suspensions, and this will be of great use in applications in the paints field and printing technologies.     

Effect of magnetic field on the rheological properties of poly(ethylene glycol) and poly(dimethylsiloxane) mixtures with aerosil and iron nanoparticles

The effect of a magnetic field on the viscosity of magnetorheological poly(ethylene glycol)-aerosil-iron nanoparticle and poly(dimethylsiloxane)-aerosil-iron nanoparticle suspensions is studied. The magnetic field leads to an increase in the viscosity of the suspensions by a factor of 20–300. The concentration dependence of the effect of magnetic field on the viscosity of the systems is described by a curve with a maximum. The dependences of viscosity on shear rate upon loading and unloading do not coincide, thus indicating the relaxation character of the flow process.