Dynamical and rheological properties of soft colloid suspensions

Soft colloids comprise a wide class of materials, ranging from linear polymers over polymeric assemblies, such as star polymers and dendrimers, to vesicles, capsules, and even cells. Suspensions of such colloids exhibit remarkable responses to imposed flow fields. This is related to their ability to undergo conformational changes and elastic deformations, and the adaptation of their dynamical behavior. The rational design of soft particles for targeted applications or the unraveling of their biological function requires an understanding of the relation between their microscopic properties and their macroscopic response. Here, mesoscale computer simulations provide an invaluable tool to tackle the broad range of length and time scales. In this article, we discuss recent theoretical and simulation results on the rheological behavior of ultrasoft polymeric colloids, vesicles, capsules, and cells. The properties of both, individual particles and semi-dilute suspensions, are addressed.     

Synthesis and rheological properties of cation-exchanged Laponite suspensions

In this paper we report our new approach to synthesize cation-exchanged Laponite suspensions. General observations of the prepared samples indicated that an aqueous suspension of 1 wt.% Laponite retained its free flowing liquid phase characteristics even after aging for several weeks. When bivalent cationic metals (Cu, Co, Ni) were ablated into the suspension, the strong charge of the crystal face was reduced and, on standing, the suspension gelled becoming highly viscous. This sol–gel transition was induced by the formation of a space-filled structure due to both van der Waals and electrostatic bonds between the positively charged rims and negatively charged faces. Rheological properties of such prepared suspensions were measured using a Brookfield DV-II Pro Viscometer with a small sample adapter (SSA18/13RPY). The yield strengths of 2.2 N/m², 3.2 N/m², and 1.7 N/m² were measured for Ni-, Co-, and Cu-modified Laponite suspensions, respectively. These yield strengths are sufficiently high for suspending weighting materials such as barite which requires the gel strength of about 0.5 N/m².     

Quasi-static electrorheological properties of hematite/silicone oil suspensions under DC electric fields

In this work, a modified rheometer has been used to gain information on the "start-up" of the shear flow of an electrorheological (ER) fluid consisting of hematite particles dispersed in silicone oil. The results show that unelectrified suspensions behave essentially as fluids, continuously deforming upon application of shear. However, this behavior changes in the presence of an electric field. For low fields and low volume fractions of solids, a solidlike (drastic increase in shear stress after the strain is applied) behavior is observed for small deformations. If the strain is increased, the yield starts and a transition to a viscoelastic-plastic nature is observed. Finally, a plastic behavior is characteristic of the post-yield regime. If the field strength and solids content are high, a discontinuous flow profile develops. These results, together with direct structural observations, suggest that the observed behavior is compatible with the formation of layers of particles electrophoretically deposited on the electrodes; the layers turn into rings when the shear field is applied. It is the slip of the fluid between these rings that can be considered responsible for the ER effect in these suspensions.     

Measurement of rheological properties of corn stover suspensions

Corn stover is currently being evaluated as a feedstock for ethanol production. The corn stover suspensions fed to reactors typically range between 10 and 40% solids. To simulate and design bioreactors for processing highly loaded corn stover suspensions, the rheologic properties of the suspension must be measured. In systems with suspended solids, rheologic measurements are difficult to perform owing to settling in the measurement devices. In this study, viscosities of corn stover suspensions were measured using a helical ribbon impeller viscometer. A calibration procedure is required for the impeller method in order to obtain the shear rate constant, k, which is dependent on the geometry of the measurement system. The corn stover suspensions are described using a power law flow model.     

Dispersion stabilities and rheological properties of fumed silica suspensions

Herein, we have reviewed fumed silica suspensions in dispersing fluids, polymer melts, and polymer solutions, focusing on their dispersion stability and rheological properties as a function of the surface character of fumed silica powders and the silica volume fraction, ?. Hydrophilic fumed silica powders are well dispersed at ? < 0.01 in polar dispersing fluids or polar polymer melts, and their phase states change from sol to gel with increasing ?. Such changes should also be strongly related to the rheological responses of the hydrophilic fumed silica suspensions, which change from Newtonian flow behavior to gel-like elasticity with increasing ?. On the other hand, hydrophobic fumed silica powders are stabilized in both polar and nonpolar dispersing fluids, depending on the interactions between the surface hydrophobic moieties and the dispersing fluids, in addition to those between the residual surface silanol groups and dispersing fluid, except for the particle–particle interactions. Moreover, the effects of the adsorption and desorption of polymers, as well as of non-adsorbing polymers on the dispersion stability and rheological behavior of fumed silica suspensions are discussed, by taking account of their optical microscopic observation and SANS curves.     

Contribution of redox-active properties of compost-derived humic substances in hematite bioreduction

The compost-derived humic substances(HS) can function as electron mediators for promoting hematite bioreduction because of its redox capacity. Humification process can affect redox capacities of compostderived HS by changing its intrinsic structure. However, the redox properties of compost-derived HS linking with hematite bioreduction during composting still remain unclear. Herein, we investigated the redox capacities of compost-derived HS, and assessed the responses of the redox capacities to t...     

Study of the rheological properties of dispersed lignite suspensions

The aim of this study was to determine the basic rheological parameters of dispersed highly concentrated lignite aqueous suspensions. Typical dilatant behavior was observed, where critical parameters of dilatancy were determined for different size fractions and concentrations. To modify the non-Newtonian behavior of the lignite highly concentrated suspensions, the effect of surfactant addition on the flow parameters of the suspensions was determined. Received: 5 March 1999/Accepted in revised form: 1 September 1999     

Adsorption and rheological characteristics of humic acid salts at liquid-gas interfaces

Du Noöy ring and oscillating droplet methods are used to study the adsorption and dilatation rheological characteristics (viscoelastic modulus and phase angle) of aqueous solutions of humic acid salts at liquid-gas interfaces. It is established that the equilibrium surface tension and limiting surface elasticity of humic acid salt solutions are in good agreement with the model of a real two-dimensional solution that was previously proposed for biopolymers. Based on the results of analyzing dynamic surface tension and adsorption kinetics, it is shown that humic acid salts are characterized by a nondiffusion (barrier) adsorption mechanism.     

Influence of cross-link density on rheological properties of temperature-sensitive microgel suspensions

The influence of the cross-link density on rheological properties of thermosensitive microgels was investigated. The temperature-sensitive hydrogel particles consisted of poly (N-isopropylacrylamide) (PNiPAM) chemically cross-linked with several different molar ratios of N,N′-methylenebisacrylamide. The variation of cross-link density leads to soft spheres that possess a different particle interaction potential and a different swelling ratio. With increasing temperature the microgel particles decrease in size and with it the effective volume fraction, which leads to strong changes in rheological properties. The relative zero-shear viscosity and the plateau modulus at different temperatures superpose to mastercurves when plotted versus the effective volume fraction. Up to an effective volume fraction of 0.5 the microgels behaved like hard spheres and the maximum volume fraction, as determined from the divergence of the zero-shear viscosity, was mainly dominated by the polydispersity of the spheres and not by the cross-link density. The plateau modulus, on the other hand, revealed soft-sphere behavior and the interaction potential became softer with decreasing cross-linker content. Received: 15 December 1999 Accepted: 15 February 2000     

Interfacial rheological properties of adsorbed protein layers and surfactants: a review

Proteins and low molecular weight (LMW) surfactants are widely used for the physical stabilisation of many emulsions and foam based food products. The formation and stabilisation of these emulsions and foams depend strongly on the interfacial properties of the proteins and the LMW surfactants. Therefore these properties have been studied extensively. In this review an overview is given of interfacial properties of proteins at a mesoscopic scale and the effect of LMW surfactants (emulsifiers) on them. Properties addressed are the adsorbed amount, surface tension (reduction), network formation at interfaces and possible conformational changes during and after adsorption. Special attention is given to interfacial rheological behaviour of proteins at expanding and compressing interfaces, which simulate the behaviour in real emulsions and foams. It will be illustrated that information on interfacial rheological properties, protein conformation and interactions between adsorbed molecules can be obtained by changing experimental conditions. The relation between interfacial rheology and emulsion and foam stabilisation is subsequently addressed. It is concluded that there is a need for new measuring devices that monitor several interfacial properties on a mesoscopic and microscopic scale at the same time, and for physical models describing the various processes of importance for proteins. Real progress will only be possible if both are combined in an innovative way.     

PAA/PEO comb polymer effects on rheological properties and inter-particle forces in aqueous silica suspensions

The effects of a poly(acrylic acid) (PAA)-poly(ethylene) (PEO) comb polymer dispersant on the rheological properties and inter-particle forces in aqueous silica suspensions have been studied under varying pH conditions. The comb polymer was found to adsorb more strongly under acidic than basic conditions, indicating that the PAA backbone of the copolymer preferentially adsorbs onto silica surfaces with the PEO "teeth" extending out from the surface into the solution. In the presence of low concentrations of copolymer, the silica suspensions were stable due to electrostatic repulsions between the silica surfaces. At higher copolymer concentrations and under neutral and basic conditions, where the copolymer interacted only weakly with silica, the suspensions showed a transition from a dispersed to weakly flocculated state and attractive forces were measured between silica surfaces. Under acidic conditions, the silica dispersion also destabilized at intermediate copolymer adsorbed density and then was re-stabilized at higher adsorbed coverage. The silica suspensions were stable at high copolymer coverage due to steric repulsions between the particles. The destabilization at intermediate coverage is thought to be due to polymer bridging between particles or possibly depletion forces.     

Interparticle interactions in concentrated suspensions and their bulk (rheological) properties

The interparticle interactions in concentrated suspensions are described. Four main types of interactions can be distinguished: (i) "Hard-sphere" interactions whereby repulsive and attractive forces are screened. (ii) "Soft" or electrostatic interactions determined by double layer repulsion. (iii) Steric repulsion produced by interaction between adsorbed or grafted surfactant and polymer layers. (iv)and van der Waals attraction mainly due to London dispersion forces. Combination of these interaction energies results in three main energy-distance curves: (i) A DLVO type energy-distance curves produced by combination of double layer repulsion and van der Waals attraction. For a stable suspension the energy-distance curve shows a "barrier" (energy maximum) whose height must exceed 25kT (where k is the Boltzmann constant and T is the absolute temperature). (ii) An energy-distance curve characterized by a shallow attractive minimum at twice the adsorbed layer thickness 2δ and when the interparticle-distance h becomes smaller than 2δ the energy shows a sharp increase with further decrease of h and this is the origin of steric stabilization. (iii) an energy-distance curve characterized by a shallow attractive minimum, an energy maximum of the DLVO type and a sharp increase in energy with further decrease of h due to steric repulsion. This is referred to as electrosteric repulsion. The flocculation of electrostatically and sterically stabilized suspensions is briefly described. A section is devoted to charge neutralization by polyelectrolytes and bridging flocculation by polymers. A distinction could be made between "dilute", "concentrated" and "solid suspensions" in terms of the balance between the Brownian motion and interparticle interaction. The states of suspension on standing are described in terms of interaction forces and the effect of gravity. The bulk properties (rheology) of concentrated suspensions are described starting with the case of very dilute suspensions (the Einstein limit with volume fraction Φ≤0.01), moderately concentrated suspensions (0.2>Φ≥0.1) taking into account the hydrodynamic interaction and concentrated suspensions (Φ>0.2) where semi-empirical theories are available. The rheological behavior of the above four main types of interactions is described starting with "hard-sphere" systems where the relative viscosity-volume fraction relationship could be described. The rheology of electrostatically stabilized suspensions was described with particular reference to the effect of electrolyte that controls the double layer extension. The rheology of sterically stabilized systems is described using model polystyrene suspensions with grafter poly(ethylene oxide) layers. Finally the rheology of flocculated suspensions was described and a distinction could be made between weakly and strongly flocculated systems.     

Influence of the exchangeable cations on stability and rheological properties of montmorillonite suspensions

The effects of NaCl and CaCl₂ on the colloid stability and rheological properties of Na- and Ca-montmorillonite dispersions were studied. The distribution of cations between the surface and the bulk phase was determined. For both of monocationic montmorillonite, the critical coagulation concentration were 250 mmol NaCl/dm³ and 2 mmol CaCl₂/dm³. The changes in the Bingham yield stresses of Na- and Ca-montmorillonite dispersions as functions of the NaCl and CaCl₂ concentration could be explained in terms of the surface excess amount and equilibrium concentration of the cations, the second electroviscous effect and the formation of a gel structure.     

Effects of steric and hydrophobic forces on the rheological properties of ZrO2 suspensions

 The effect of pH on the flow behavior of ZrO₂ suspensions containing polyacrylic and octanoic acids was evaluated. In the flocculated pH regime, the flow behavior is highly shearthinning and can be described by a power-law model. The shear-thinning behavior increases with increasing degree of flocculation. Maximum shearthinning was observed at the zero zeta potential condition. Hydrophobic interaction arising from adsorbed octanoic acid was found to enhance the shear-thinning behavior. No such enhancement was observed for adsorbed polyacrylic acid. It was also illustrated that the viscosity–pH behavior is a mirror image of the yield stress–pH behavior. A quantitative particle-pair interactions model incorporating steric and hydrophobic interactions was proposed to explain the effects of polyacrylic and octanoic acids on the maximum yield stress. Received: 23 May 1997 Accepted: 4 June 1997     

The effect of a magnetic field on the rheological properties of iron-aerosil-glycerol suspensions

The viscosity of a suspension consisting of iron nanoparticles, aerosil, and glycerol has been studied under the conditions of a rotational flow in the presence and absence of a magnetic field. At low shear rates, the viscosity is governed by the magnetic field and increases 40 times with a rise in the field strength; at high shear rates, the effect of the mechanical stress field prevails. In this case, the relative viscosity increases by 1.4 times, and its concentration dependence in the magnetic field is described by a curve passing through a maximum.     

Effects of pH and phosphate on the adsorptive fractionation of purified Aldrich humic acid on kaolinite and hematite

The molecular weight (MW) fractionation of purified Aldrich humic acid (PAHA) resulting from adsorption on kaolinite and hematite was investigated for different solution pH and phosphate conditions. Adsorption was highly pH-dependent, with higher uptake at lower pH values. For all pH conditions, the weight-average MW (MWw) of residual PAHA remaining in solution after adsorption deviated from the original MWw, indicating that preferential adsorption of certain MW components occurred. The extent of preferential adsorption depended on the percent carbon adsorption at a given pH condition. For similar percent carbon adsorption ranges, a greater extent of preferential adsorption of the higher MW PAHA components was observed with higher pH values as demonstrated by the lowest residual MWw value occurring at pH 9. Detailed analyses of selected residual PAHA samples clearly showed that adsorption selectivity for particular MW components was strongly influenced by solution pH. The extent of preferential adsorption of lower MW PAHA components decreased in the presence of a small amount of phosphate. This effect was more evident for hematite than kaolinite, and became greater with lower solution pH irrespective of the mineral type. The different fractionation patterns observed for PAHA were reasonably well explained by the physicochemical trends occurring in its MWw fractions and the underlying sorption processes.     

The effect of particle shape on the structure and rheological properties of carbon-based particle suspensions

The structure and rheological properties of carbon-based particle suspensions, i.e., carbon black(CB), multi-wall carbon nanotube(MWNT), graphene and hollow carbon sphere(HCS) suspended in polydimethylsiloxane(PDMS), are investigated. In order to study the effect of particle shape on the structure and rheological properties of suspensions, the content of surface oxygen-containing functional groups of carbon-based particles is controlled to be similar. Original spherical-like CB(fractal filler), rod-like MWNT and sheet-like graphene form large agglomerates in PDMS, while spherical HCS particles disperse relatively well in PDMS. The dispersion state of carbon-based particles affects the critical concentration of forming a rheological percolation network. Under weak shear, negative normal stress differences(ΔN) are observed in CB, MWNT and graphene suspensions, while ΔN is nearly zero for HCS suspensions. It is concluded that the vorticity alignment of CB, MWNT and graphene agglomerates under shear results in the negative ΔN. However, no obvious structural change is observed in HCS suspension under weak shear, and accordingly, the ΔN is almost zero.     

Synchrotron SAXS/WAXD and rheological studies of clay suspensions in silicone fluid

Suspensions of two commercial smectite clays, montmorillonite KSF and montmorillonite K10, in a low-viscosity silicone oil (Dow Corning 245 Fluid) were studied by simultaneous synchrotron small-angle X-ray scattering (SAXS)/wide-angle X-ray diffraction (WAXD) techniques and rheological measurements. In the 0.5% (w/v) KSF clay suspension and two K10 clay suspensions (0.5% and 1.0%), WAXD profiles below 2theta=10.0 degrees did not display any characteristic reflection peaks associated with the chosen montmorillonite clays, while corresponding SAXS profiles exhibited distinct scattering maxima, indicating that both clays were delaminated by the silicone oil. In spite of the large increase in viscosity, the clay suspensions exhibited no gel characteristics. Dynamic rheological experiments indicated that the clay/silicone oil suspensions exhibited the behavior of viscoelasticity, which could be influenced by the type and the concentration of the clay. For the K10 clay suspensions, the frequency-dependent loss modulus (G") was greater in magnitude than the storage modulus (G') in the concentration range from 0.5 to 12.0%. The increase in the clay concentration shifted the crossover point between G' and G" into the accessible frequency range, indicating that the system became more elastic. In contrast, the KSF clay suspension exhibited lower G' and G" values, indicating a weaker viscoelastic response. The larger viscoelasticity response in the K10 clay suspension may be due to the acid treatment generating a higher concentration of silanol groups on the clay surface.     

Combined electrical and rheological properties of shear induced multiwall carbon nanotube agglomerates in epoxy suspensions

In this work the rheological and electrical properties of semi-dilute carbon nanotube (CNT)–epoxy suspensions have been discussed. The suspensions are produced using two types of industrially available CNTs (Nanocyl 3150 and 7000) and using two different dispersion techniques, namely 3-roll milling and sonication. In-situ optical microscopic analysis and electrical conductivity measurements have been conducted. It is shown that despite using CNTs with similar aspect ratios, the dispersability of the raw material and the time stability of the suspensions are quite different. Additionally, viscosity measurements are used to evaluate the initial dispersion quality and time stability.