Clustering and mechanics in dense depletion and thermal gels

We report on the microstructure and mechanical properties (elastic modulus) of concentrated depletion and thermal gels of octadecyl-coated silica particles for different values of the strength of interaction--polymer concentration for depletion gels and temperature for thermal gels. The depletion gels are composed of dense clusters and voids, while the thermal gels are devoid of clusters. Shear breaks up clusters in depletion gels while it induces clustering in the thermal gels. In both of these gels, the microstructure recovers to the presheared state upon cessation of shear. The recovery of the elastic modulus mimics the microstructure in the sense that the elastic modulus recovers to the presheared sheared state after shearing is stopped. Calculations of the gel boundary by modeling the interactions with an effective one-component square-well model reveals that suspensions with similar ranges of attraction gel at the same volume fraction at a fixed strength of attraction. Calculations of the elastic modulus using the na?ve mode coupling theory for depletion gels are in good agreement with experimental measurements provided clustering is taken into account and have the same magnitude as the elastic moduli of thermal gels with similar strengths of attraction. These calculations, in addition to the experimental observations reinforce the point that the microscopic parameter determining the elastic modulus of dense gels and its recovery is the localization length which is only a fraction of the particle diameter and not the structure on the length scale of the particle diameter and larger.     

Rheological aspects of colloidal gels in thermoresponsive microgel suspensions: formation,structure, and linear and nonlinear viscoelasticity

This review focuses on the rheological aspects of colloidal gels that are a three-dimensional sparse network made of aggregated attractive particles formed in the aqueous suspensions of microgels composed of thermoresponsive polymers. Heating changes the dominant interparticle interactions from repulsive to attractive because of the hydrophilic-to-hydrophobic transition. Under appropriate conditions, the hydrophobic microgel suspensions form colloidal gels behave as a yield fluid. The elastic and yielding features of the colloidal gels are considerably different from those of the repulsive glass which is formed by the dense packing of the hydrophilic microgels at low temperatures. The thermoresponsive microgel suspensions undergoing colloidal gelation have attracted much attention from not only the academic interests but also the potentials as a functional suspension because they show interesting and marked changes in viscoelasticity when subjected to temperature variation. We discuss the criteria and dynamics of colloidal gelation, the structure, and linear and nonlinear viscoelasticity of the colloid gels with an emphasis on the results of the experimental studies.     

Diffusing-Wave Spectroscopy of Concentrated Alumina Suspensions during Gelation

Using diffusing-wave spectroscopy, we followed the aggregation and gelation of concentrated (30 vol%) alumina suspensions. The suspensions were destabilized by either shifting the pH to the isoelectric point or by increasing the ionic strength. Both effects can be achieved continuously and homogeneously by using an enzyme-catalyzed internal chemical reaction. Based on the light-scattering data, we could derive quantitative information about the sol-gel transition and the viscoelastic properties of the gels, as well as a characterization of changes in the microstructure. The elastic moduli determined from light scattering are found to be in good agreement with rheological measurements. Copyright 2001 Academic Press.     

Effect of pH and Salt on Rheological Properties of Aerosil Suspensions

Ionic strength and pH will influence the zeta potential of suspended particles, and consequently particle interactions and rheological properties as well. In this study the rheological properties and aggregation behaviour of Aerosil particles dispersed in aqueous solutions with various pH and salt concentration were studied. The potential energy was estimated by the DLVO theory and short range hydration forces and compared to the experimentally determined zeta potential. The strongest attraction between particles occurs at the isoelectric point (pH 4) and resulted in large aggregates, which gave relatively higher values of viscosity, yield stress, moduli, and shear thinning effects. The relative viscosity as a function of volume fraction was fitted to the Krieger and Dougherty model for all the suspensions. Oscillation measurements showed that the suspensions display elastic behaviour at low pH and viscous behavior at high pH. Furthermore, suspensions with high salt content had higher storage moduli. A power law dependency of storage moduli with volume fraction could be used to indicate the interaction strength between particles.     

Small-angle static light scattering of concentrated silica suspensions during in situ destabilization

The aggregation of concentrated aqueous silica suspensions is characterized by means of static light scattering. We use an in situ destabilization mechanism based on the enzyme-catalyzed hydrolysis of urea. This method enables us to continuously and homogeneously change the interparticle potential from repulsive to attractive without disturbing the aggregation process. Moreover, our electrostatically stabilized suspensions can be destabilized by two different methods. In the first method, the pH is shifted toward the isoelectric point of the particles ( Delta pH method), thereby leading to a decrease of their surface charge. In the second method, the ionic strength is continuously increased at constant pH ( Delta I method), leading to a compression of the electrical double layer around the charged particles. A laboratory-built flat-cell light-scattering instrument is used, which allows fast data acquisition and an adjustment of the sample cell thickness. To circumvent multiple scattering effects, we use a very small sample thickness ( approximately 13 microm). In addition, the refractive index difference between the aqueous phase and the particles is reduced by adding sucrose to the liquid phase of our suspensions. We are able to characterize the structural changes at the very early stages of the destabilization process, where no significant effects are yet detected in macroscopic rheological measurements. While during the Delta pH destabilization, the scattering curve shows significant changes only after some characteristic delay time, it changes continuously during the Delta I destabilization. The latter is attributed to the formation of a weak pre-gel structure in the suspensions, as a shallow secondary minimum appears in the interparticle potential. Data are evaluated by using a HMSA square-well structure factor model. Results are in good agreement with those predicted from DLVO theory.     

Study of pH-triggered heteroaggregation and gel formation within mixed dispersions

This work involves an investigation of pH-triggered heteroaggregation and gelation within mixed dispersions of polystyrene (PS) and pigment particles. The PS particles were stabilised by a carboxylated alkyl ethoxylate surfactant which is pH-responsive. The pigment used was beta-copper phthalocyanine. The pigment particles contained a co-surfactant system consisting of the carboxylated alkyl ethoxylate and a non-ionic surfactant. The latter was a beta-naphthol ethoxylate. The PS and pigment particles were characterised using SEM, TEM, photon correlation spectroscopy and electrophoretic mobility measurements. The PS dispersions exhibited pH-triggered aggregation when the pH was decreased to below a critical value (pH(crit)), which was 1.9. Concentrated PS dispersions formed stable particle gels at pH values less than or equal to pH(crit). Dilute pigment dispersions were found to have a pH(crit) of 3.45. However, concentrated pigment dispersions did not form gels when the pH was decreased to below pH(crit). A phase diagram for the mixed dispersions was constructed which showed a gel phase existed at pH values between 2.0 and 3.0, which corresponds to a pH region higher than pH(crit) for the PS particles. This implicates PS-pigment inter-particle bonds in the gel structure. The heteroaggregate gels were investigated using dynamic rheological measurements and it was apparent that the highest elastic modulus values were obtained in the pH range of approximately 2 to 3. SEM images provided evidence of heteroaggregates with diameters of a few micrometers. These primary heteroaggregates are suggested to be the network forming unit for the gels formed in mixed dispersions. The data from the study are used to propose a conceptual model for the structure of the heteroaggregate gels.     

Hollow polymer particles that are pH-responsive and redox sensitive: two simple steps to triggered particle swelling, gelation and disassembly

A new, simple, two-step method is introduced for preparing hollow particles that are both pH-responsive and redox sensitive. Hollow poly(methyl methacrylate-co-methacrylic acid) particles swell at moderate pH values, form gels in concentrated dispersions and can be disassembled by adding reducing agents.     

Assessment of surfactant adsorption in oil-based magnetic colloids

We describe in this paper different and complementary experimental methods for assessing the adsorption of surfactants on metal particles in oil-based suspensions. Two different kinds of particles are dispersed in mineral oil: iron microparticles and CoNi nanoparticles. The adsorption of oleic acid in the Fe/oil interface in diluted suspensions can be determined by obtaining the adsorption isotherm. In addition, we present a method based on the time evolution of the optical absorbance of suspensions, from which the existence of adsorption can be inferred. For concentrated suspensions, the used of optical methods is not recommended, since they are affected by a significant inaccuracy. We present here a useful alternative based on electromagnetic induction phenomena. The results obtained allow a more comprehensive knowledge of the aggregation process in concentrated suspensions. With the same purpose, a third group of experiments, based on rheological techniques, is carried out in Fe/oil and CoNi/oil concentrated suspensions. In these series of experiments, the effect of three surfactants (oleic acid, aluminum stearate and lecithin) is tested by measuring either the viscosity, or the magnetic field-induced yield stress of the suspensions. The combination of these series of experiments gives us valuable information about the most appropriate surfactant/carrier combination capable of imparting a high stability and a strong magnetorheological response in magnetic colloids.     

Effect of polycarboxylate ether comb-type polymer on viscosity and interfacial properties of kaolinite clay suspensions

The interactions between kaolinite clay particles and a comb-type polymer (polycarboxylate ether or PCE), so-called PCE super-plasticizer, were investigated through viscosity and surface forces measurements by a rheometer and a Surface Forces Apparatus (SFA). The addition of PCE shows a strong impact on the viscosity of concentrated kaolinite suspensions in alkaline solutions (pH=8.3) but a weak effect under acidic conditions (pH=3.4). In acidic solutions, the high viscosity measured is attributed to the strong electrostatic interaction between negatively charged basal planes and positively charged edge surfaces of clay particles. Under the alkaline condition, the suspension viscosity was found to first increase significantly and then decrease with increasing PCE dosages. The results from surface forces measurement show that PCE molecules at low dosages can bridge the kaolinite particles in the concentrated suspensions via hydrogen bonding, leading to the formation of a kaolinite-PCE "network" and hence an increased suspension viscosity. At high PCE dosages, clay particles are fully covered by PCE molecules, leading to a more dispersed kaolinite suspensions and hence lower suspension viscosity due to steric repulsion between the adsorbed PCE molecules. The insights derived from measuring viscosity and interfacial properties of kaolinite suspensions containing varying amount of comb-type super-plasticizer PCE at different pH provide the foundation for many engineering applications and optimizing industrial processes.     

Negative electrorheological behavior in suspensions of inorganic particles

An investigation is described on the electric-field-induced structures in colloidal dispersions. Both rheological determinations and direct microscopic observations are used with that aim. The starting point of this study is the so-called electrorheological (ER) effect, consisting of the mechanical reinforcing of a fluid or suspension due to formation of chains of molecules or particles after being polarized by the action of the field. One macroscopic manifestation of this phenomenon is the transformation of the fluid from a typically Newtonian behavior to a viscoelastic material, with finite yield stress and high elastic modulus. The systems investigated were suspensions of elongated goethite (β-FeOOH) particles in silicone oils with varying amounts of silica nanoparticles. The results showed the rather unusual behavior known as "negative ER effect", which can be best described by saying that the application of an electric field reduces the yield stress and the elastic modulus, that is, produces destruction of structures rather than their build up. The negative behavior is also found for suspensions of other inorganic powders, including hematite and quartz. On the contrary, the usual positive ER response is found for suspensions of cellulose and montmorillonite clay. The same happens if goethite suspensions are prepared in high volume fractions, high-viscosity fluids, or both. All of the results found are compatible with the so-called interfacial model of electrorheology: the reduction of the yield stress of goethite suspensions when the applied field is high enough is the consequence of particle migration toward the electrodes because of charge injection and subsequent electrophoresis. The migration leaves the gap between the electrodes devoid of particles and explains the decrease in yield stress. The addition of silica nanoparticles contributes to reduce the strength of this effect by hindering the charging and making it necessary to increase the field strength to observe the negative effect. The model appears to also be applicable to cellulose, although the positive response found for such particles is explained by their large size: larger diameters bring about larger attraction forces between particles, leading to a tendency to produce strong aggregates. This is likely to occur in suspensions of colloids which, because of their relatively high electrical conductivity, tend to acquire charge even in such nonpolar liquids as silicone oils.     

Light Scattering Probes of Viscoelastic Fluids and Solids

In this article, we discuss recent advances in static and dynamic light scattering applied to soft materials. Special emphasis is given to light scattering methods that allow access to turbid and solid‐like systems, such as colloidal suspensions, emulsions, glasses, or gels. Based on a combination of single‐ and multispeckle detection schemes, it is now possible to cover an extended range of relaxation times from a few nanoseconds to minutes or hours and length scales below 1 nm up to several microns. The corresponding elastic properties of viscoelastic fluids or solid materials range roughly from below 1 Pa to several 100 kPa. Different applications are discussed such as light scattering from suspensions of highly charged colloidal particles, colloid and protein gels, as well as dense surfactant solutions.     

Yielding behavior of thermo-reversible colloidal gels

The breakdown of structure in gelled suspensions due to the application of an external stress results in flow. Here we explore the onset of flow by investigating the onset of nonlinear behavior in the elastic moduli of a widely studied class of thermo-reversible gels over a range of volume fractions. We employ the system composed of octadecyl-coated silica particles (radius = 24 nm) suspended in decalin that displays a transition from a liquid to a gel below a volume-fraction-dependent gel temperature, Tgel. The perturbative yield stress at which the gel modulus drops to 90% of its value in the linear viscoelastic limit is found to increase monotonically with volume fraction and decreasing temperature. The recently proposed activated barrier-hopping theory of Schweizer and co-workers1,2 presents a framework to capture the impact of external forces on the mechanical properties of structurally arrested systems. By characterizing particle interactions with a Yukawa potential and employing the resultant static structure factor as input into the activated barrier-hopping theory, we make predictions for how the elastic modulus evolves with the applied stress. Comparisons of these calculations with experiments reveal that the theory does an excellent job of quantitatively capturing the perturbative yield stresses over the entire range of volume fractions and temperatures explored in the study. The match of predictions with experimental results suggests that the theory not only captures particle localization but also how this localization is modulated in the presence of an external stress.     

Rheology of concentrated carbon nanotube suspensions

The rheological properties of non-Brownian carbon nanotube suspensions are measured over a range of nanotube volume fractions spanning the transition from semidilute to concentrated. The polymer-stabilized nanotubes are "sticky" and form a quiescent elastic network with a well-defined shear modulus and yield stress that both depend strongly on nanotube volume fraction with different but related critical exponents. We compare controlled-strain-rate and controlled-stress measurements of yielding in shear flow, and we study the effect of slow periodic stress reversal on yielding and the arrest of flow. Our measurements support a universal scaling of both the linear viscoelastic and steady-shear viscometric response. The former allows us to extract the elastic shear modulus of semidilute nanotube networks for values that are near or below the resolution limit of the rheometers used, while the latter provides a similar extrapolation of the yield stress. A simple scaling argument is used to model the dependence of yield stress and elastic modulus on concentration.     

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.     

Stability of dispersions of colloidal hematite/yttrium oxide core-shell particles

The colloidal stability of suspensions of hematite/yttria core/shell particles is investigated in this work and compared with that of the pure hematite cores. The different electrical surface characteristics of yttrium and iron oxides, as well as the diameters of both types of spherical particles, dominate the overall process of particle aggregation. The aggregation kinetics of the suspensions was followed by measuring their optical absorbance as a function of time. By previously calculating the extinction cross section of particle doublets, it was demonstrated that for both core and core/shell particles the turbidity of the suspensions should increase on aggregation. Such an increase was in fact found in the systems in spite of the ever-present tendency of the particles to settle under gravity. The authors used the initial slope of the turbidity increment time plots as a measure of the ease of aggregation between particles. Thus, they found that the essential role played by pH on the charge generation on the two oxides and the shift of one pH unit between the isoelectric points of hematite and yttria manifest in two features: (i) the stability decreases on approaching the isoelectric point from either the acid or basic side and (ii) the maximum instability is found for hematite at pH 7 and for hematite/yttria at pH 8, that is, close to the isoelectric points of alpha-Fe(2)O(3) and Y(2)O(3), respectively. The role of added electrolyte is simply to yield the suspensions of either type more unstable. Using the surface free energy of the particles, the authors could estimate their Hamaker constants in water. From these and their zeta potentials, the DLVO theory of stability was used to quantitatively explain their results.     

Rheological characterization of high concentrated MFC gel from kenaf unbleached pulp

Microfibrillated Cellulose (MFC) was isolated from unbleached kraft pulp derived from kenaf bast fiber. MFC gels with different concentrations were manufactured from pulp with varying initial consistencies. The MFC was diluted to a consistency of around one percent using distilled water and was further homogenized by passing through a microfluidizer. In order to gain an understanding of the relative changes in behavior of the resulting MFC gels, their rheological properties were characterized. Results show that all of the gels exhibit a shear-thinning behavior. It was also determined that the rheological characteristics improved with increasing gel concentration, which was achieved by using higher pulp suspension consistencies. Diluted MFC that was derived from highly concentrated MFC had more variable modulus under the same strain and frequency compared to poorly concentrated MFC. But such a strong effect was not observed for viscosity. Additionally, the value of G′, ranging from 76 to 5325 Pa under the studied concentrations, was found to be fourfold the value of G″. In the low frequency range, G′ was almost independent of frequency, but was dependent on gel consistency with a coefficient of 3, indicating that MFC gels are elastic. These results show that it is possible to produce MFC gels with good rheological properties from high consistency kenaf pulp suspensions.     

Improved electrorheological effect in polyaniline nanocomposite suspensions

We prepared polyaniline (PANI)/clay composites that are composed of both PANI-clay nanocomposite particles and pure PANI particles. The PANI-clay nanocomposite particles were made during the polymerization process, wherein PANI particles are attached on the surface of exfoliated clay particles modified by an aminosilane group. The PANI/clay composites were used as electrorheological fluids (ERFs) by dispersing them in silicon oil. The PANI-clay nanocomposite particles, which can form columnar structure under an electric field, strongly enhance the mechanical rigidity of the suspensions. The maximum yield stress of the PANI/clay composite suspensions (15 wt% in silicon oil) was 1.6 kPa at 3 kV/mm, while that of pure PANI was 300 Pa at the same electric field. A mechanism to explain the yield behaviors of the PANI-based nanocomposite suspensions is proposed.     

Preparation of Micron Polymer-Fe Capsulized Composites by Mechanic Milling and MR Effect of Concentrated Suspensions

Polymer-Fe capsulized composite particles with micron-size are successfully prepared by directly milling the mixture of polymer and metallic iron powder. The effects of preparation conditions is discussed in detail. In addition, the magnetorheological fluid effect of concentrated suspensions consisting of these particles, and the stability of the particles anti-sedimentation in the concentrated suspensions are simply studied.     

Untypical rheological behaviour of the lignite–carboxymethylcellulose–water dispersion system

Suspensions of lignite in a solution of a high molecular weight carboxymethylcellulose show peculiar rheological behaviour. Unless the lignite concentration is sufficiently high, apparent viscosity and viscoelastic moduli of the suspension are lower than those of the pure solution. This effect is not suppressed by changing pH and seems to be common for low-concentrated suspensions in solutions of high molecular weight (bio)polymer. It is explained by specific structuring of the suspensions. Lignite particles at lower concentration separate long cellulose chains and facilitate their movement under shear flow. The particles loosen inter-chain contacts, disturb and release elastic gel-like structure formed by the long cellulose chains, which results in the low strain oscillatory deformation, the decrease in the moduli and the increase in the loss angle. If the amount of lignite particles is sufficiently high, suspension stiffening occurs as usual. No such effect was observed for suspensions prepared from the low molecular weight derivative. Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users.     

Nonlinear elasticity and yielding of nanoparticle glasses

We employ experiment and theory to explore the nonlinear elasticity and yielding of concentrated suspensions of nanoparticles which interact via purely repulsive forces. These glassy suspensions are found to exhibit high exponent power law or simple exponential dependences of the shear elastic modulus and perturbative yield stress on nanoparticle volume fraction, as well as a monotonic decrease of the perturbative yield strain with increasing concentration. Our experimental observations are in good agreement with the predictions of a recently developed microscopic statistical mechanical theory, which describes glassy dynamics based on a nonequilibrium free energy that incorporates local cage correlations and activated barrier hopping processes [(1) Schweizer, K. S.; Saltzman, E. J. J. Chem. Phys. 2003, 119, 1181. (2) Saltzman, E. J.; Schweizer, K. S. J. Chem. Phys. 2003, 119, 1197. (3) Kobelev, V.; Schweizer, K. S. Phy. Rev. E 2005, 71, 021401].