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.     

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.     

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.     

Steady shear rheology of dilute polystyrene particle gels

This paper describes an experimental study on dispersions of monodisperse polystyrene (PS) spheres with a typical radius of 1 μm, dispersed in an electrolyte at high ionic strength, screening the electrostatic repulsion. These suspensions gelate at rest even at low volume fractions of PS particles. The density of the particles is matched with the solvent by using deuterium oxide for volume fractions φ≤0.117. Steady-state flow curves, viscosity as a function of shear rate, are measured and reported for 0.014<φ<0.322. The measured flow curves are analyzed on the basis of two models: 1. In the giant floc model (van Diemen and Stein 1983, 1984; Schreuder et al. 1986, 1987; Laven et al. 1988), at low shear rates, the shear is not distributed homogeneously but is limited to certain shear planes; the energy dissipation during steady flow is due primarily to overcoming the viscous drag on the suspended particles during motion caused by encounters of particles in the shear planes. Though this model was developed for higher solid volume fractions (0.35–0.425), we found that it also describes the rheology of dilute particle gels for 0.15≤φ≤0.3, using the same values for the parameters in the model as in the high solid volume fraction region. For φ<0.15, the model also describes the data if the fraction of distance by which a moving particle entrains its neighbors, is assumed to increase in this φ region. 2. The model of de Rooij (de Rooij et al. 1993, 1994) considers aggregates in shear flow to be monodisperse impermeable spheres with a fractal structure. The permeability is taken into account by considering a hydrodynamic radius smaller than the gyration radius in the Krieger-Dougherty expression for the hydrodynamic contribution to the viscosity. Through the use of a yield criterion the aggregate radius is modeled as a function of shear rate. We found that the model describes our experimental results, with a combination of parameter values used already by de Rooij, but only for φ<0.15. Received: 7 May 1998 Accepted: 22 December 1998     

Characterization of polymer dispersions by Fourier transform rheology

Fourier transform rheology is a very sensitive technique to characterize non-linear rheological fluid properties. It has been applied here for the first time to polymer dispersions in water and the results are compared to those from conventional rheology, namely steady and small amplitude oscillatory shear experiments. The investigated systems are mainly based on styrene and n-butylacrylate. A first attempt was made to evaluate how far colloidal parameters like particle volume fraction and ionic strength as well as chemical composition and surface characteristics of the dispersed particles are reflected in FT-rheology spectra. Significantly different non-linearities are observed for highly concentrated dispersions of particles with different T_g. These differences are not detected in linear oscillatory shear and show up in steady shear only at significantly higher shear rates. Particle surface characteristics influence the non-linear response in oscillatory shear significantly and the intensity of the overtones is found to be higher for a dispersion of particles with a “hairy” swollen surface layer as compared to a system of smooth particles, although the solids content was adjusted to match the steady shear viscosity. The intensity of the overtones in FT-rheology strongly decrease upon dilution. At a solid content below 35% no differences are observed in the FT-experiments for the systems investigated here, whereas the differences in steady shear are very pronounced in this concentration range. A significant influence of added salt onto the non-linear response is detected for some systems, which might be correlated to the stability of these systems. The observed phenomena certainly cannot be explained in terms of constitutive equations or microstructural statistical mechanical models at present. Thus, FT-rheology yields information complementary to classical steady or linear oscillatory shear experiments. Received: 11 December 2000 Accepted: 8 April 2001     

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.     

Rheology of poly(methyl methacrylate-<Emphasis Type="Italic">co</Emphasis>-styrene) particles suspended in water: effects of electrostatic surface layer

 Linear and nonlinear viscoelastic properties were examined for aqueous suspensions of monodisperse poly(methyl methacrylate-co-styrene) (MS) particles having the radius a ₀ =45 nm and the volume fractions φ=0.428−0.448. These particles had surface charges and the resulting electrostatic surface layer (electric double layer) had a thickness of t_s=5.7 nm. At low frequencies in the linear viscoelastic regime, the MS particles behaved approximately as the Brownian hard particles having an effective radius a _eff=a ₀ + t_s, and the dependence of their zero-shear viscosity η₀ on an effective volume fraction φ_eff (={a _eff/a ₀}³φ) agreed with the φ dependence of η₀ of ideal hard-core silica suspensions. In a range of φ_eff < 0.63, this φ_eff dependence was well described by the Brady theory. However, the φ_eff dependence of the high-frequency plateau modulus was weaker and the terminal relaxation mode distribution was narrower for the MS suspensions than for the hard-core suspensions. This result suggested that the electrostatic surface layer of the MS particles was soft and penetrable (at high frequencies). In fact, this “softness” was more clearly observed in the nonlinear regime: the nonlinear damping against step strain was weaker and the thinning under steady shear was less significant for the MS suspension than for the hard-core silica suspensions having the same φ_eff. These weaker nonlinearities of the concentrated MS particles with φ_eff∼ 0.63 (maximum volume fraction for random packing) suggested that the surface layers of those particles were mutually penetrating to provide the particles with a rather large mobility. Received: 10 July 2001 Accepted: 2 November 2001     

A theoretical research to effective viscosity of colloidal dispersions

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Nonlinear rheology of concentrated spherical silica suspensions: 3. Concentration dependence

Nonlinear rheology was examined for concentrated suspensions of spherical silica particles (with radius of 40 nm) in viscous media, 2.27/1 (wt/wt) ethylene glycol/glycerol mixture and pure ethylene glycol. The particles were randomly and isotropically dispersed in the media in the quiescent state, and their effective volume fraction φ_eff ranged from 0.36 to 0.59. For small strains, the particles exhibited linear relaxation of the Brownian stress σ_B due to their diffusion. For large step strains γ, the nonlinear relaxation modulus G(t,γ) exhibited strong damping and obeyed the time-strain separability. This damping was related to γ-insensitivity of strain-induced anisotropy in the particle distribution that resulted in decreases of σ_B/γ. The damping became stronger for larger φ_eff. This φ_eff dependence was related to a hard-core volume effect, i.e., strain-induced collision of the particles that is enhanced for larger φ_eff. Under steady/transient shear flow, the particles exhibited thinning and thickening at low and high γ˙, respectively. The thinning behavior was well described by a BKZ constitutive equation using the G(t,γ) data and attributable to decreases of a Brownian contribution, σ_B/γ˙. The thickening behavior, not described by this equation, was related to dynamic clustering of the particles and corresponding enhancement of the hydrodynamic stress at high γ˙. In this thickening regime, the viscosity growth η₊ after start-up of flow was scaled with a strain γ˙t. Specifically, critical strains γ_d and γ_s for the onset of thickening and achievement of the steadily thickened state were independent of γ˙ but decreased with increasing φ_eff. This φ_eff dependence was again related to the hard-core volume effect, flow-induced collision of the particles enhanced for larger φ_eff. Received: 26 June 1998 Accepted: 9 December 1998     

Energy Estimate of the Critical Reynolds Numbers in a Compressible Couette Flow. Effect of Bulk Viscosity

A variational problem of determining the critical Reynolds number of the laminar-turbulent transition is numerically solved within the framework of the nonlinear energy theory of stability of compressible flows. Stability of various modes in the Couette flow of a compressible gas is estimated by the method of collocations. It is demonstrated that the minimum critical Reynolds numbers in the range of the ratio of the bulk viscosity ηb to the shear viscosity η, which is realistic for diatomic gases, are reached for modes of streamwise disturbances. The critical Reynolds numbers increase as the bulk viscosity is increased in the interval η_b = 0-2η, with the maximum increase in the limit being approximately 30%.     

Quantitative rheological evaluation of phase inversion in two-phase polymer blends with cocontinuous morphology

 The present work is focused on the rheological properties of two-phase polymer blends in the phase inversion region. A large number of PS/PMMA- and PSAN/PMMA-blends has been investigated in order to establish a rheological criterion which allows the quantitative determination of the phase inversion concentration φ_PI by rheological means. Three rheological criteria based on the viscous and elastic blend properties such as maximum of dynamic viscosity η′, slope of G′, and maximum of G′ at a constant evaluation frequency have been tested. By correlating the rheological results to data from quantitative morphological analysis we could prove that the chosen rheological criteria are differently suitable for the determination of φ_PI. It has turned out that the G′ criterion is the most robust and most suitable one yielding an excellent correlation with morphological data. Based on these findings we propose a new simple equation for the prediction of φ_PI-values. Received: 14 March 2001 Accepted: 15 May 2001     

Simulation of the rheological properties of suspensions of oblate spheroidal particles in a Newtonian fluid

A simulation algorithm was developed to predict the rheological properties of oblate spheroidal suspensions. The motion of each particle is described by Jeffery’s solution, which is then modified by the interactions between the particles. The interactions are considered to be short range and are described by results from lubrication theory and by approximating locally the spheroid surface by an equivalent spherical surface. The simulation is first tested on a sphere suspension, results are compared with known experimental and numerical data, and good agreement is found. Results are then presented for suspensions of oblate spheroids of two mean aspect ratios of 0.3 and 0.2. Results for the relative viscosity η _r, normal stress differences N ₁ and N ₂ are reported and compared with the few available results on oblate particle suspensions in a hydrodynamic regime. Evolution of the orientation of the particles is also observed, and a clear alignment with the flow is found to occur after a transient period. A change of sign of N ₁ from negative to positive as the particle concentration is increased is observed. This phenomenon is more significant as the particle aspect ratio increases. It is believed to arise from a change in the suspension microstructure as the particle alignment increases.     

Viscosity of concentrated noncolloidal bidisperse suspensions

At the same solid volume fraction (Φ) the relative viscosity (η _r ) of a concentrated noncolloidal bidisperse suspension of hard spherical particles is lower than that of a monodisperse suspension. In this paper a semi-analytical viscosity model of noncolloidal bidisperse suspensions is derived using an integration method. In this model the random loose packing density obtained by computer simulation is taken as the limit of solid volume fraction Φ _m which depends upon both the diameter ratio (λ) of large to small particles and the volume fraction of large particles (ξ=Φ _l /Φ). This model shows that at high solid volume fraction, Φ > 0.40, both λ and ξ significantly influence η _r . For example, at Φ=0.5, it predicts that for monodisperse suspensions η _r =70, while for bidisperse suspensions (λ=2 and ξ=0.7) η _r =40. Comparison shows that, at high solid volume fraction (0.4–0.5), the relative viscosity predicted by this model is in good agreement with that predicted by the work of Shapiro and Probstein (1992) and of Patlazhan (1993), but is higher than that predicted by the work of others. Received: 27 February 2001 Accepted: 25 April 2001     

Linear viscoelastic behavior of perfluorooctyl sulfonate micelles: effects of counter-ions

Linear viscoelastic behavior was investigated for aqueous solutions of perfluorooctyl sulfonate (C₈F₁₇SO⁻ ₃; abbreviated as FOS) micelles having a mixture of tetraethylammonium (N⁺(C₂H₅)₄; TEA) and lithium (Li⁺) ions as the counter-ions. The solutions had the same FOS concentration (0.1 mol l⁻¹) and various Li⁺ fractions in the counter-ions, φ_Li = 0−0.6, and the FOS micelles in these solutions formed threads which further organized into dendritic networks. At T ≤ 15 °C, the terminal relaxation time τ and the viscosity η, governed by thermal scission of the networks, increased with increasing φ_Li up to 0.55. A further increase of φ_Li resulted in decreases of τ and η and in broadening of the relaxation mode distribution. These rheological changes are discussed in relation to the role of TEA ions in thermal scission: Previous NMR studies revealed that only a fraction of TEA ions were tightly bound to the FOS micellar surfaces and these bound ions stabilized the thread/network structures. The concentration of non-bound TEA ions, C_TEA ^*, decreased and finally vanished on increasing φ_Li up to φ_Li ^* ≅ 0.6, and the concentration of the bound TEA ions significantly decreased on a further increase of φ_Li. The non-bound TEA ions appeared to catalyze the thermal scission of the FOS threads, and the observed increases of τ and η for φ_Li < 0.55 were attributed to the decrease of C_TEA ^*. On the other hand, the decreases of τ and η as well as the broadening of the mode distribution, found for φ_Li > 0.55 (where C_TEA ^* ≅ 0), were related to destabilization of the FOS threads/networks due to a shortage of the bound TEA ions and to the existence of concentrated Li⁺ ions. Viscoelastic data of pure FOSTEA and FOSTEA/FOSLi/TEACl solutions lent support to these arguments for the role of TEA ions in the relaxation of FOSTEA/FOSLi solutions. Received: 12 October 1999/Accepted: 1 November 1999     

Drop-on-demand drop formation of colloidal suspensions

The drop formation dynamics in the drop-on-demand (DOD) inkjet process is studied for model inks including a Newtonian liquid and colloidal dispersions. The ink shear viscosity is a parameter often adjusted in tuning the DOD drop formation process. Apparent shear viscosity measured at low shear rates is currently used to characterize inkjet inks throughout both the inkjet industry and academia. However, during the ejection process in inkjet printing, very high shear rates (above 1 × 10⁵ s⁻¹) are involved. In this paper, the drop formation characteristics at 10 kHz drop formation rate in a DOD mode of a simple Newtonian liquid are compared with those of a colloidal suspension system which has the same low-shear-rate viscosity as the simple Newtonian liquid, but significantly different high-shear-rate viscosity. Under conditions of good jetting, the drop formation dynamics of the colloidal suspension is similar to that of the simple Newtonian liquid of similar low-shear viscosity, with only slight systematic differences observed. Good jetting is, however, difficult to obtain in the colloidal particle inks, with non-straight trajectories and non-axisymmetric ligaments commonly observed. These observations suggest that evaporation, nonuniform wetting, and particle-related changes in properties play a role when poor jetting behavior is observed for colloidal inks.     

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.     

Microstructure of shear-thickening concentrated suspensions determined by flow-USANS

Reversible shear thickening in colloidal suspensions is a consequence of the formation of hydroclusters due to the dominance of short-ranged lubrication hydrodynamic interactions at relatively high shear rates. Here, we develop and demonstrate a new method of flow-ultra small angle neutron scattering to probe the colloidal microstructure under steady flow conditions on length scales suitable to characterize the formation of hydroclusters. Results are presented for a model near hard-sphere colloidal suspension of 260 nm radius (10% polydisperse) sterically stabilized silica particles in poly(ethylene glycol) at shear rates in the shear thinning and shear thickening regime for dilute, moderately concentrated, and concentrated (ordered) suspensions. Hydrocluster formation is observed as correlated, broadly distributed density fluctuations in the suspension with a characteristic length scale of a few particle diameters. An order–disorder transition is observed to be coincident with shear thickening for the most concentrated sample, but the shear-thickened state shows hydrocluster formation. These structural observations are correlated to the behavior of the shear viscosity and discussed within the framework of theory, simulation, and prior experiments.     

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

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

Rheological properties of disperse systems at low shear stresses

Three-dimensional network structures can be built up in disperse systems due to long-range colloidal interactions between the dispersed particles. The rheological behaviour of such coagulation structures has been studied by means of creep and recovery experiments at low shear stresses, i.e. by measuring the shear strain as a function of time under constant stress and after removal of stress. Measurements of this type give insight into the elastic and viscous deformations and the retardation times necessary to reach equilibrium or steady-state conditions.Results obtained with dispersions of pigments in polymer solutions and with monodisperse polymer latexes indicate the existence of an equilibrium state at low shear stresses with a predominant elastic deformation and a high viscosity suggesting that the disperse systems investigated do not behave exactly as rigid gels but apparently exhibit a dynamic equilibrium of structural break-down and formation under applied stress. This behaviour is approximately described by a 4-parameter-model with an instantaneous and a steady-state compliance, one retardation time, and a viscosity.At higher shear stresses thixotropic structural break-down occurs resulting in a transition from the rheological behaviour described here to a liquid-like state with a comparatively low viscosity. In this stress range the viscoelastic properties become strongly time-dependent.These measurements give evidence of the presence of two types of deformation: an instantaneous, purely elastic deformation attributable to the unperturbed coagulation structure and the creep-recovery behaviour of an elastic liquid apparently related to the breaking and re-forming of bonds.     

The role of the mathematical mean value theorem (MVT) in rheometry: an easy way to convert apparent flow curves into correct ones

The mean value theorem of integral calculus guarantees that the apparent viscosity η _a can easily be converted into the correct viscosity η. For ordinary liquids there is a direct identity between η _a and η but the apparent shear rate (or apparent shear stress) has to be shifted to the representative shear rate γ˙^ (or representative shear stress τ^). A model free approximation scheme is introduced which implies a constant shift factor. The corresponding approximation for η is acceptable for liquids most commonly encountered. For plastic fluids the relation between η and η _a is more complex since it involves a function depending upon α; the yield stress relative to the maximum stress within the viscometer. Using the same approximation scheme as before the shift factor will involve α as well. The corresponding approximation of η is shown to be acceptable for the whole range of α. Received: 7 February 2000/Accepted: 15 February 2000