An empirical model predicting the viscosity of highly concentrated, bimodal dispersions with colloidal interactions

The relationship between particle size distribution and viscosity of concentrated dispersions is of great industrial importance, since it is the key to get high solids dispersions or suspensions. The problem is treated here experimentally as well as theoretically for the special case of strongly interacting colloidal particles. An empirical model based on a generalized Quemada equation is used to describe η as a function of volume fraction for mono- as well as multimodal dispersions. The pre-factor η˜ accounts for the shear rate dependence of η and does not affect the shape of the η vs φ curves. It is shown here for the first time that colloidal interactions do not show up in the maximum packing parameter and φ_max can be calculated from the particle size distribution without further knowledge of the interactions among the suspended particles. On the other hand, the exponent ɛ is controlled by the interactions among the particles. Starting from a limiting value of 2 for non-interacting either colloidal or non-colloidal particles, ɛ generally increases strongly with decreasing particle size. For a given particle system it then can be expressed as a function of the number average particle diameter. As a consequence, the viscosity of bimodal dispersions varies not only with the size ratio of large to small particles, but also depends on the absolute particle size going through a minimum as the size ratio increases. Furthermore, the well-known viscosity minimum for bimodal dispersions with volumetric mixing ratios of around 30/70 of small to large particles is shown to vanish if colloidal interactions contribute significantly. Received: 7 June 2000/Accepted: 12 February 2001     

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     

Rheological behaviour of spray-dried egg yolk/xanthan gum aqueous dispersions

This paper provides information on the microstructure of, and reports particle size distributions and rheological results for, aqueous dispersions of spray-dried egg yolk and xanthan gum prepared on a laboratory scale using two types of homogenisers. Laser light scattering results demonstrated that higher energy input during homogenisation yielded a dispersion with a lower average particle size and a wider polydispersity, slightly influencing the linear dynamic viscoelastic functions due to the low concentration of egg yolk particles. These dispersions exhibited weak gel properties at the composition studied. The mechanical spectrum and the corresponding relaxation spectrum were dominated by the xanthan/gum-water matrix which controls the structure of the continuous phase. This fact explained the lack of any wall depletion effects. Several controlled-rate and controlled-stress rotational rheometers and a capillary rheometer were used to obtain information on flow properties. The shear rate dependence of steady state viscosity was determined through twelve decades, and was fitted using the Carreau equation. The kinetics of structural recovery after steady-state shear was studied by start-up at the inception of shear and flow interrupted experiments under controlled shear history. The results were analysed in terms of the ratio of a time-dependent amount of overshoot to the amount of overshoot of the original sample, using the addition of two first order equations. Additionally, combined steady state flow properties at fixed shear stress/oscillatory shear experiments were also used. The increase of the storage modulus with time, checking a linear viscoelastic response, tracked the structural recovery after steady shear. Laser light scattering of sheared samples helped gain a better understanding of the role of egg yolk particles on the rheology of these dispersions. Received: 6 February 2000 Accepted: 5 September 2000     

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.     

Rheological behavior of concentrated suspensions as affected by the dynamics of the mixing process

The rheological characterizations of concentrated suspensions are generally carried out assuming “well-mixed” suspensions. However, the variation of the concentration distributions of the ingredients of the formulation, i.e., the “goodness of mixing”, the size and shape distributions of the particle clusters and the rheological behavior of the suspension all depend on the thermo-mechanical history that the suspension is exposed to during the mixing process. Here, various experimental tools are used for the characterization of the degree of mixedness (concentration distributions) of various ingredients along with the characterization of rheological material functions, wall slip behavior and the maximum packing fraction of a graphite/elastomer suspension. The degree of mixedness values of the ingredients of the suspensions processed using batch and continuous processes and under differing operating conditions were characterized quantitatively using wide-angle X-ray diffraction and thermo gravimetric analysis and were elucidated under the light of the electrical properties of the suspension as affected by the mixing process. Upon achieving better homogeneity of the graphite particles and the binder and decreases in the size and breadth of the size distributions of particle clusters (as inferred from electrical measurements and maximum packing fraction values), the elasticity (storage modulus) and the shear viscosity (magnitude of the complex viscosity from small-amplitude oscillatory shear and shear viscosity from steady torsional and capillary rheometry) of the suspension decreased significantly and the wall slip velocity values increased. These findings demonstrate the intimate relationships that exist between the rheological behavior of concentrated suspensions and the thermo-mechanical history that they are exposed to during the processing stage and suggest that the preparation conditions for suspensions should be carefully selected and well documented to achieve reproducible characterization of rheological material functions.     

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.     

A theoretical research to effective viscosity of colloidal dispersions

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Rheological properties of lightly crosslinked carboxy copolymers in aqueous solutions

The rheological properties of a series of lightly crosslinked carboxy copolymers in aqueous solutions have been evaluated in steady shear and dynamic oscillatory modes. Viscosity profiles and the behavior of storage modulus are related to the chemical composition of the copolymers and their crosslinking density. A maximum in viscosity and in storage modulus which depends on the type of crosslinking agent used is explained by a combination of a chain entanglement mechanism and a closely-packed spheres model. The recovery of viscosity and storage modulus after shearing is very fast and is related to the very fast rearrangement of the microgel structure as a function of time.     

Nonlinear viscoelastic properties of MR fluids under large-amplitude-oscillatory-shear

Nonlinear viscoelastic properties of the MR fluid, MRF-132LD, under large-amplitude oscillatory shear were investigated. This was accomplished by carrying out the experiments under the amplitude sweep mode and the frequency sweep mode, using a rheometer with parallel-plate geometry. Investigations under the influence of various magnetic field strength and temperatures were also conducted. MR fluids behave as nonlinear viscoelastic or viscoplastic materials when they are subjected to large-amplitude shear, where the storage modulus decreases rapidly with increasing strain amplitude. Hence, MR fluid behaviour ranges from predominantly elastic at small strain amplitudes to viscous at high strain amplitudes. Large-amplitude oscillatory shear measurements with frequency sweep mode reveal that the storage modulus is independent of oscillation frequency and approaches plateau values at low frequencies. With increasing frequency, the storage modulus shows a decreasing trend before increasing again. This trend may be explained by micro-structural variation. In addition, the storage modulus increases gradually with increasing field strength but it shows a slightly decreasing trend with temperature.     

Effects of particle softness on the rheology and yielding of colloidal glasses

We studied the linear and nonlinear rheology of colloidal glasses consisting of hard spheres and soft core-shell particles at several volume fractions to explore the effects of particle softness on the mechanical properties and yielding. Creep and recovery and oscillatory shear measurements were used to determine the shear elastic modulus and the yield strain. Both hard and soft sphere glasses exhibited ‘entropic cage elasticity’ below random close packing, whereas for compressed soft spheres at higher effective volume fractions, the yield strain was determined by shell elasticity. The shear modulus followed a strong increase with volume fraction for hard spheres and a much weaker one for soft particles reflecting their interparticle potential. Nonlinear effects, revealed as strong distortions of the stress signal during yielding, were analyzed via Fourier transform rheology and Lissajous plots. The significant contribution of the nonlinearities was analyzed in terms of strain softening and hardening mechanisms within a cycle of oscillation and discussed in relation to particle softness.     

Numerical simulations of linear viscoelasticity of monodisperse emulsions of Newtonian drops in a Newtonian fluid from dilute to concentrated regime

The bulk viscoelastic properties of monodisperse emulsions of Newtonian drops in a Newtonian matrix subjected to small amplitude oscillatory shear (SAOS) flow are investigated by means of arbitrary Lagrangian Eulerian finite element method 3D numerical simulations. Volume fractions of the suspended phase from the dilute to the concentrated regime (up to 30 %), and a range of several orders of magnitude of the drops-to-matrix viscosity ratio and of the frequency of the oscillatory flow are examined; the eventual presence of slip between the two fluids is also considered. The computational results are compared with theory, yielding a quantitative agreement with Oldroyd (Proc R Soc Lond A 218:122–132, 1953) predictions in a wide range of values of the considered parameters, even well beyond the dilute regime, and also in the cases with slip.     

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.     

Rheology of concentrated suspensions containing mixtures of spheres and fibres

Optimising flow properties of concentrated suspensions is an important issue common for many industries. The rheology of concentrated suspensions has therefore been studied intensively both experimentally and theoretically. Most studies have focused on monodisperse and polydisperse suspensions of either spheres or fibres. In practice, most suspensions contain particles that are polydisperse both in size and shape. A mixing rule for such systems is expected to be a powerful tool for engineers and product designers. Therefore in this work, suspensions of spheres, fibres and mixtures thereof were characterised using rotational shear rheometry and in-line image analyses. Thereby, total solids volume concentration and fibre fraction was varied. Results from transient and steady-state shear rheometry are discussed with respect to concentration, fibre fraction, and shear induced microstructure. Experimentally obtained viscosity data were accurately fitted using the model proposed by Farris (T Soc Rheol 12:281, 1968) for mixtures of monodisperse non-interacting spheres of different sizes.Originally presented at the Annual European Rheology Conference 2003, AERC 2003     

Filling the gap between transient and steady shear rheology of aqueous graphene oxide dispersions

Even though the rheological behavior of aqueous graphene oxide (G-O) dispersions has been shown to be strongly time-dependent, only few transient measurements have been reported in the literature. In this work, we attempt to fill the gap between transient and steady shear rheological characterizations of aqueous G-O dispersions in the concentration range of 0.004 < ? <?3.5 wt%, by conducting comprehensive rheological measurements, including oscillatory shear flow, transient shear flow, and steady shear flow. Steady shear measurements have been performed after the evaluation of transient properties of the G-O dispersions, to assure steady-state conditions. We identify the critical concentration ? _c =?0.08 wt% (where G-O sheets start to interact) from oscillatory shear experiments. We find that the rheology of G-O dispersions strongly depends on the G-O concentration ?. Transient measurements of shear viscosity and first normal stress difference suggest that G-O dispersions behave like nematic polymeric liquid crystals at ?/? _c =?25, in agreement with other work reported in the literature. G-O dispersions also display a transition from negative to positive values of the first normal stress difference with increasing shear rates. Experimental findings of aqueous graphene oxide dispersions are compared and discussed with models and experiments reported for nematic polymeric liquid crystals, laponite, and organoclay dispersions.     

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.     

Rheological properties of concentrated latex suspensions of poly(styrene-butadiene)

Concentrated suspensions of charged latex particles of poly(styrene-butadiene) have been used as model systems to investigate the influence of surface charges on the rheology of colloidal suspensions. The suspensions were found to behave as elastic solids at small strains and to require a finite stress to flow. This was related to an ordered structure of the suspensions at rest, resulting from electrostatic and van der Waals forces. Important shear-thinning effects were observed as a consequence of structure rearrangements under shear. At a fixed shear rate, the steady-shear viscosity as a function of the ionic strength exhibits a minimum. Under oscillatory shear flow, the behavior of the concentrated suspensions was found to be non-linear above a very small strain amplitude. The non-linear output signal from dynamic experiments was analyzed using a fast Fourier transform algorithm. A maximum in the third harmonic intensity as a function of the strain amplitude was observed and the intensity of higher harmonics decreased with increasing ionic strength. The behavior of the suspensions could be adequately described using the structural model of Yziquel et al. (Yziquel F, Carreau PJ, Moan M, Tanguy PA (1999) Rheological modeling of concentrated colloidal suspensions. J Non-Newtonian Fluid Mech 86:133–155).     

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.     

A phenomenological modification of rheological models for concentrated two-phase systems: application to a thermoplastic/thermoset blend

This paper considers an improvement of the emulsion models to take into account concentrated emulsions with no coalescence but with significant interaction between particles. For this purpose, a term proportional to the volume fraction of material in excess to the percolation threshold is added to the dynamic modulus. Its usefulness was tested to model the viscoelastic behavior in oscillatory shear flow of concentrated and diluted blends of a thermoplastic polystyrene with an epoxy-amine thermoset. These blends experience phase separation upon polymerization and the volume fraction of separated phase varies continuously with time. At low volume fraction of dispersed phase, the behavior could be described with a simple emulsion model that takes into account the plastisizing, dilution, and phase separation mechanisms. However, for concentration in excess to the percolation threshold, the modification can cope with a larger increase in the modulus related to the mechanical percolation of the dispersed particles.     

Correlation between the high-frequency elastic modulus and the interparticle interaction potential in zirconium oxide colloidal suspensions

In this work, we study the high-frequency elastic modulus of aqueous suspensions made with two kinds of zirconium oxide particles, one commercially available and the other synthesized as monodisperse spheres. The effect of volume fraction of solid, ionic strength (sodium chloride as indifferent electrolyte) and particle geometry is taken into account in the study on this viscoelastic property of the suspensions. Frequency sweeps were performed at a fixed value of the applied shear-stress in order to obtain the frequency-limiting value of the elastic modulus by rheometrical methods. On the other hand, the high-frequency modulus is theoretically calculated independently by means of the models proposed by Buscall and co-workers, Wagner and Bergenholtz and co-workers, which correlate the interaction potential between particles with this rheological parameter. The approach to the interparticle potential is the extended DLVO theory, which considers the electrical repulsion between charged colloidal particles, the van der Waals attraction and the acid–base interaction that can be attractive or repulsive depending on the thermodynamic nature of the solid–liquid interface.     

New insights on fumed colloidal rheology—shear thickening and vorticity-aligned structures in flocculating dispersions

We investigate the rheology of dilute dispersions of fumed colloidal particles with attractive interactions in hydrocarbon liquids. Surprisingly, these systems display shear thickening due to the breakdown of densified flocs and a concomitant increase in the effective volume fraction of the fractal particles in the fluid. We show that this shear thickening is controlled by a critical stress and accompanied by a positive increase in the first normal stress difference, N ₁, at the shear thickening transition. This is in contrast to the well-known hydrocluster mechanism of shear thickening in concentrated hard-sphere and repulsive systems. Gel elasticity depends strongly on the stress applied to suspensions in preshear, scaling roughly as \(G'\sim\sigma_{\text{preshear}}^{2}\). We propose a simple model to account for these results in terms of the cluster number density determined by the preshear stress. At low shear rates, vorticity-aligned aggregates are present at \(\dot\gamma\approx 10^0 {\rm{s}}^{-1}\) . In this regime, the system displays a small but noticeable increase in viscosity on increasing shear rate. We investigate the effect of tool roughness and find that wall slip is not responsible for the observed phenomena. Instead, the increase in the apparent viscosity results from increased flow resistance due to the presence of gap-spanning log-like flocs in rolling flow.