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We investigate the aging behavior in a well-studied model system comprised of a colloidal suspension of thermoreversible adhesive hard spheres (AHS) but thermally quenched below the gel transition to much larger depths than previously studied. The aging behavior in the model AHS system is monitored by small amplitude oscillatory shear rheology measurements conducted while rapidly quenching from the liquid state at 40 °C to a temperature below the gel temperature, and new, anomalous aging behaviors are observed. Shallow quenches lead to monotonic development of the elastic modulus with time, consistent with prior reports for the development of a homogeneous gel [Gordon et al., J. Rheol. 61, 23–34 (2017)]. However, for deeper quenches, a unique and new phenomenon is reported, namely, after an initial rise in the modulus, a reproducible drop in the modulus is observed, followed by a plateau in the modulus value. This drop can be gradual or sudden and the extent of the drop depends on the quench depth. After this drop in the modulus, AHS gel evolves toward a quench-path independent state over the experimental timescale. These effects of the extent of quenching on aging behavior are hypothesized to be a consequence of quenching into different underlying thermodynamic states of colloidal gels and the possible influence of the adhesive glass dynamical arrest for the deepest quenches. The research connects homogeneous gelation with heterogeneous gel formation due to phase separation and shows that the extent of quench can be used as an independent parameter to govern the rheological response of the arrested gel. [ABSTRACT FROM AUTHOR]

Model aluminosilicate (N‐A‐S‐H) gel systems give insight to the complex reaction occurring in alkali‐activated binders, allowing for more precise control over chemical composition and exhibiting simpler kinetics. Small angle neutron scattering, oscillatory rheology, and solid‐state NMR were used to characterize N‐A‐S‐H gel samples and relate structure, chemical composition, and rheology. Aluminum concentration was varied in the gel samples at fixed silica and sodium concentration. Past the percolation point, the gel develops in two regimes distinct in structure and rheological behavior. The first gel regime is characterized by increase in modulus and initial formation of fractal structures following a diffusion‐limited monomer‐cluster aggregation mechanism. The second gel regime at higher aluminum concentrations is characterized by a modulus plateau and structure development via reaction‐limited aggregation of existing clusters. NMR data indicate a saturation of aluminum in the network at the transition between gel regimes, which may be pH driven. Understanding the structure‐property relationships critical to formation of the N‐A‐S‐H gel can give valuable insight to the reaction mechanism in alkali‐activated binders and the influence of chemical composition on resultant structure and mechanical properties. [ABSTRACT FROM AUTHOR]

The shear induced microstructure for electrostatic and Brownian suspensions are compared using in situ small angle neutron scattering (SANS). The dispersions consist of 75 nm Stöber silica coated with 3-(trimethoxysilyl) propyl methacrylate (TPM) and have a zeta potential of -42.6 ± 4.7 mV. Neutralizing the surface charge with 0.066 M— nitric acid yields stable hard-sphere dispersions. SANS is conducted over a range of shear rates on the charge-stabilized and Brownian suspensions to test the order-disorder transition and hydrocluster mechanisms for shear thickening, and demonstrate the influence of stabilizing forces on the shear induced microstructure evolution. Through treatment of the colloidal micromechanics, shear induced changes in the microstructure are correlated to the hydrodynamic component of the shear stress and the thermodynamic component of the normal stress, i.e., the method of "Rheo-SANS" is developed. The results demonstrate that hydrocluster formation accompanies the shear thickening transition. [ABSTRACT FROM AUTHOR]

Studies the effects of colloidal interactions on the kinetics and extent of adsorption using a dynamic simulation of colloidal adsorption. Diffusion by Brownian dynamics accounted for by the simulation; Characterization of particle-particle and particle-surface interactions; Classes of charged colloidal particles considered.

The simple shearing of a suspension of charge-stabilized, colloidal particles close to the melting line is investigated by massively parallel, nonequilibrium Brownian dynamics (NEBD) simulation. The suspension undergoes a discontinuous transition from a distorted fluid structure to an ordered ‘‘string’’ phase. Comparisons between simulations of 43 000, 4725 particles, and previous NEBD work on ≤500 particles proves that shear-induced ordering is not an artifact of the small system sizes. We also show that the shear-rate dependence of the rheological properties obtained from NEBD is different than those obtained from nonequilibrium molecular dynamics (NEMD), a consequence of the solvent damping not being present in NEMD. The validity of the Ree–Eyring model for viscosity and the stress-optic law for colloids are tested. Further, a type of generalized Stokes–Einstein relationship is discovered for systems under shear. © 1996 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Structure measurements of a suspension of charged polystyrene spheres with significant polydispersity (16%) are reported for a wide range of particle and added salt concentrations and scattering wave vector. Small angle neutron scattering yielded the structure factors of concentrated samples that have had extensive rheological characterization. A Schulz distribution was used as a model of the particle size distribution to reduce the intensity data and as a basis for the theoretical fits of the structure factors. Static light scattering measurements yielded the structure factors of diluted, deionized samples. Dynamic light scattering was also performed to study the relaxation of these structures. These measured structures were fit with a recent theory that accounts for both size and charge polydispersity in the suspension. These results and the previous extensive, rheological investigations and physical characterization yield a complete data set on a well-characterized, model system that can be used to test theories of the statics and dynamics of polydisperse colloidal suspensions. [ABSTRACT FROM AUTHOR]

The shear flow of non-Brownian glass spheres suspended in a concentrated colloidal dispersion that exhibits non-Newtonian rheology is investigated. At low volume fractions, the addition of non-Brownian spherical particles to the colloidal dispersion leads to an increase in the steady shear viscosity as well as the dynamic moduli. The flow curves of these suspensions are qualitatively similar to the suspending colloidal dispersion medium, and as such, in this semidilute regime, the suspension data can be shifted on to that of the colloidal dispersion medium at constant shear stress with shift factors comparable to those predicted for spherical particles in a Newtonian fluid. At higher volume fractions of non-Brownian spheres, the shear thickening power law exponent increases with the addition of non-Brownian particles. This increase in the shear thickening power law exponent is shown to be consistent with the effects of confinement on the shear thickening colloidal dispersion by the larger non-Brownian particles. [ABSTRACT FROM AUTHOR]

Reversible shear thickening is common in concentrated dispersions of Brownian hard-spheres at high-shear rates. We confirm the existence of a well-defined colloidal shear-thickened state through experimental measurements of the shear stress and the first and second normal stress differences in the shear-thickened state as a function of the particle volume fraction for a model dispersion of near hard-spheres. The shear stress and normal stress differences are observed to grow linearly with the shear rate in the shear-thickened state and both normal stress differences are observed to be negative. Our experimental results show the shear-thickened state of colloidal dispersions can be described by three material properties--the shear viscosity and first and second normal stress difference coefficients--that are a function of the volume fraction. All three material properties are found to diverge with a power law scaling as ... close to maximum packing, &#934max, which is found to be 0.54 ± 0.01. We find ηr,sts>γ2,sts>γ1,sts. These results are consistent with theoretical predictions for shear thickening by hydrocluster formation and quantitatively comparable to Stokesian Dynamics simulations. We further postulate and show that these material properties are consistent with those measured for non-Brownian suspensions. [ABSTRACT FROM AUTHOR]

Abstract: The complex rheological behaviour of suspensions is very strongly affected by the details of the microstructure and the interparticle forces by which it is controlled. The difficulties involved in characterizing the microstructure, in particular during flow, caused the development of suspension rheology to lag behind that of polymer rheology. Progress in theory, experiments and simulation is rapidly changing the picture, providing opportunities for further significant developments. Possible evolutions in six areas of suspension rheology are discussed here. [Copyright &y& Elsevier]

Dispersions of multiarm star polymers in an athermal solvent are studied as a model system to explore the effects of soft colloidal interactions on the dynamics of colloidal glasses. Linear viscoelastic measurements in the glassy state are congruent with Mode Coupling Theory predictions for hard sphere glasses at moderate frequencies, indicating similarities in the relaxation processes of hard and soft colloidal glasses near equilibrium. On the other hand, distinct features of the star relaxation (related to arm disengagement) are observed to affect the nonlinear behavior associated with shear melting of the glass, which exhibits transitions previously unreported for hard sphere systems. Whereas a single maximum in G″(γ) is evident under large amplitude oscillatory shear at frequencies near the beta relaxation, secondary transitions between yielding and the onset of macroscopic flow are observed at higher and lower frequencies. The latter are annealed out upon complete fluidization of the star polymer suspension. The overall nonlinear behavior of the soft glassy suspension is interpreted in terms of two primary mechanisms: (i) deformation and yielding of the cage-like glassy microstructure, as in the hard sphere case, and (ii) local stretching and disengagement of interpenetrating arms of the colloidal star polymers. [ABSTRACT FROM AUTHOR]

A micromechanical model for the onset of shear thickening in polymer stabilized colloidal dispersions is derived. The model incorporates both the stabilizing forces of the polymer brush or “coat” and the associated modification of the hydrodynamic interactions. Comparison is made to simulations and experiments on well-characterized dispersions. The model is shown to provide a quantitative prediction for the onset of shear thickening in polymer coated colloidal dispersions as compared to simulations. For comparison with experiments, where independent characterization of some parameters is not available, the onset of shear thickening can be predicted with realistic assumptions for the model parameters. The model quantifies the sensitivity of the shear thickening transition to both the interaction potential and the hydrodynamic permeability of the polymer coat. [ABSTRACT FROM AUTHOR]

[Display omitted] Colloidal suspensions of anisotropic particles are ubiquitous in particle-based industries. Consequently, there is a need to quantify the effects of particle shape on equilibrium phases and kinetic state transitions, particularly at lower aspect ratios (L / D ≈ 1–10). We present a new, colloidal system comprised of hollow, octadecyl-coated silica rods with 40 nm diameter with controlled aspect ratio and thermoreversible short-range attractions. Rheology and dynamic light scattering measurements on suspensions of these hollow adhesive hard rods with nominal aspect ratio ≈3 suspended in tetradecane exhibit thermoreversible gelation without complicating effects of gravitational settling. Small angle neutron scattering measurements of the microstructure are analyzed to determine the effective strength of attraction in the form of Baxter sticky parameter. Quantitative agreement is found with simulation predictions of the thermoreversible gel transition as a function of volume fraction, further validating a universal state diagram and providing guidance for the effects of aspect ratio on gelation. [ABSTRACT FROM AUTHOR]

The device described measures a two-dimensional projection of the light scattered from a sheared, optically clear colloidal suspension and decomposes the pattern to identify quantitatively the effects of shear on the structure of the dispersion. The evolution of the nonequilibrium structure for a hard-sphere suspension is traced from low to high shear rates at moderate to dense concentrations and is related qualitatively to rheological properties. At high shear rates shear induces order in dense suspensions. Comparison of the measured nonequilibrium structure factor at low shear rates to theoretical predictions based on pairwise additive interactions confirms the importance of many-body hydrodynamics, as suggested by similar discrepancies between measurements of the steady shear viscosity and predictions from the same theory. Scalings that correlate the shear rate dependence of the viscosity appear to work for the microstructure as well. Measurements of a similar suspension with weak long-range repulsions demonstrates the sensitivity of the nonequilibrium microstructure to the form of the interparticle potential. [ABSTRACT FROM AUTHOR]

The particle size dependence of the reversible shear thickening transition in dense colloidal suspensions is explored. Five suspensions of monodisperse silica are synthesized via the Sto¨ber synthesis. The physicochemical properties of the dispersions are quantified using transmission electron microscopy, dynamic light scattering, small angle light scattering, electrophoresis, and viscometry. Rheology measurements indicate a critical stress marking the onset of reversible shear thickening that depends on the dispersion's particle size, concentration, polydispersity, and interparticle interactions. A simplified two particle force balance between the interparticle repulsive forces and the hydrodynamic compressive forces is used to derive a scaling relationship between this critical shear stress and the suspension properties. The scaling is tested against the fully characterized silica dispersions, which span nearly a decade in particle size. Furthermore, bimodal mixtures of the dispersions are employed to evaluate the accuracy of the scaling to predict the critical shear stress for dispersions with varying degrees of polydispersity. The success of the scaling supports the hydrocluster mechanism for shear thickening and suggests methods for controlling shear thickening by tailoring particle properties. © 2001 American Institute of Physics. [ABSTRACT FROM AUTHOR]

In Paper I [J. W. Swan et al., J. Rheol. 58, 307-338 (2014)], we derived an exact theoretical description of medium amplitude oscillatory shear for a semidilute colloidal dispersion. Through solution of the Smoluchowski equation governing the spatial distribution of suspended particles in the semidilute limit, we calculated the stresses that arise from an oscillatory linear flow as an expansion in powers of the rate of deformation. Here, this is extended to calculation of the first departures from linearity in the first and third harmonics of the suspension stress driven by oscillatory deformation. The role of hydrodynamic interactions is investigated via the excluded-annulus model in which particles are given an impenetrable core with a radius larger than their hydrodynamic radius. The ratio of these length scales controls the strength of hydrodynamic interactions. The third harmonic of the suspension stress is predicted to be dominated by hydrodynamic stresses at high frequency, a result that is shown to be valid experimentally for the oscillatory shear response of concentrated near hard-sphere dispersions. The calculations anticipate recent experimental observations on model near hard-sphere colloidal dispersions, and quantitative agreement is demonstrated when the predictions are scaled appropriately to account for volume fraction effects. The first departures from linearity in harmonics of the suspension stress are separated into several material functions that are independent of the flow geometry. These functions are generated from detailed numerical solutions, while asymptotic analysis is shown to predict the values of these functions at high frequency. These exact calculations provide a basis for understanding the onset of nonlinear rheological behavior of colloidal suspensions under dynamic oscillatory flow. [ABSTRACT FROM AUTHOR]

The assembly of ordered dicolloid monolayers is directedby anelectric field. The dicolloid particles are polystyrene latex witha maximum equatorial diameter 3.45 μm and length 4.63 μm.The monolayer structure is characterized using small-angle light scatteringand bright-field microscopy. With increasing field strength from 26.7to 200 VRMS/cm, a transition from a disordered monolayer,to first orientationally ordered, and then translationally orderedtwo-dimensional (2D) arrays occurs. A c2mmplane group symmetry dominates the ordered structure but is presentalongside structures with p2 symmetry, leading toa spread in the angular distribution of the light scattering peaks.The order–disorder transition dependence on field strengthand frequency is similar to that observed for colloidal spheres; athigher frequencies, stronger fields are required to assemble particles.Optimal ordered structures reflect a balance between inducing sufficientlystrong interparticle interactions while limiting the rate of formationto ensure the growth of large crystalline domains. [ABSTRACT FROM AUTHOR]

Abstract: The split Hopkinson pressure bar experimental technique is used to evaluate the squeezing flow response of a concentrated, discontinuously thickening colloidal suspension of spherical silica particles loaded at high stresses/strain rates. These results provide insight into the transitional behavior of these materials, as well as the post-transitional response under compressive loading. A method of analyzing the strain and strain rate dependent behavior is presented to identify modes of material response (viscous, elastic, etc.). Experimental results are presented as stress–strain–strain rate plots and a surface fitting approach is used to develop a phenomenological model describing the overall response. From this model, it is possible to identify regions of elastic and viscous behavior using a gradient analysis approach. It was found that, after an initial period of viscous deformation, the suspension behaves like a viscoelastic material – this regime corresponds well with transition in which large clusters of particles percolate. This is followed by a third, viscous regime in which the material undergoes viscous deformation. At the highest stresses, a plateau region of plastic deformation has been identified. This approach and the conditions under which it may be applied are described in detail in the paper. [Copyright &y& Elsevier]

Abstract: The behavior of a concentrated, hard-sphere colloidal suspension is evaluated using the split Hopkinson pressure bar (SHPB) experimental technique. The composition of the suspension is measured using thermograviometric analysis before and after loading. This, combined with recorded pressure distributions, result in the conclusion that the suspension undergoes high rate squeezing flow. Experimental results demonstrate that the suspension exhibits shear thickening consistent with that observed in standard rotational rheometry. At sufficiently high stresses the suspension exhibits a second regime of shear thinning behavior that is consistent with elastohydrodynamic theory that incorporates the shear modulus of the particles themselves. Further increases in stress result in irreversible behavior, i.e., rather than fracturing or crushing, the particles form non-reversible agglomerates during testing. This fact is demonstrated through the use of dynamic light scattering and electron microscopy. This behavior occurs within a regime of viscous material response which is seen to occur at normal strain rates and stresses over 104 s−1 and 40MPa, respectively. [Copyright &y& Elsevier]

The split Hopkinson pressure bar (SHPB) technique is implemented to evaluate the transient response of a colloidal suspension exhibiting shear thickening at strain rates and timescales never before explored in a laboratory instrument. These suspensions are shown to exhibit a discontinuous transition from fluid-like (shear thinning) to solid-like (shear thickening) behavior when evaluated using rotational rheometry. The effect of loading rate on this transition time is studied for a particle volume fraction of 0.54 using the SHPB technique. It is shown that the time required for transition to occur decreases logarithmically with loading rate. From these results, we conclude that transition is not triggered by a characteristic shear rate, but rather a critical shear strain is required. Results from SHPB experiments performed up to Peclet numbers of order 107 are presented and discussed for 0.50, 0.52, and 0.54 particle volume fraction suspensions. [ABSTRACT FROM AUTHOR]

Colloidal dispersions with a short-range attraction and long-range repulsion can exhibit an intriguing intermediate range order, manifested in scattering experiments as a low-q peak in the structure factor. Monte Carlo simulations are performed on fluids that exhibit intermediate range order to explicitly determine its connection to a possible state of microphase separation, equilibrium clustering. This is accomplished by decomposing the structure factor into cluster-cluster, monomer-monomer, and cross-correlations that cannot be extracted from experimental scattering patterns. Our simulation results indicate that the intermediate range order arises from either monomeric or cluster species, depending on solution conditions, and reflects the presence of a preferred length scale that is not trivially related to the interparticle potential. Further, criteria are established to define monomer, cluster, and percolated states in these systems that facilitate further studies. Combining scattering techniques with simulations provides an effective method for identifying clustered states in complex fluids. [ABSTRACT FROM AUTHOR]

Dense colloidal suspensions are processed in a wide variety of industries. Challenges for pumping suspensions and slurries at high concentrations include shear thickening and dilation, which can have deleterious consequences. These systems are shear sensitive close to the jamming point, meaning that a significant increase in high shear viscosity can be observed with just a few percent change in volume fractions. Therefore, accurate and rapid determination of the jamming point can greatly aid formulation. Typically, conventional rheometry identifies the jamming point by a time-consuming process, whereby multiple flow curves of suspensions of different volume fraction are measured and extrapolated to the volume fraction where the viscosity diverges. We present an alternative approach for rapid, one-step, experimental determination of the jamming point for aqueous suspensions. The procedure monitors the shear stress under constant shear stress or shear rate as the sample is dewatered using immobilization cell rheometry, until the viscosity diverges. The method is validated by comparing the results of this work with conventional rheometry for a model suspension. Then it is applied to examine the effect of grafting a short-chain polymer to particles, comprising an industrial suspension of silica-coated titania. Polymeric coating of the particles increases the jamming concentration and mitigates shear thickening, qualitatively consistent with predictions from simulations. [ABSTRACT FROM AUTHOR]

Understanding the mechanisms of clustering in colloids, nanoparticles, and proteins is of significant interest in material science and both chemical and pharmaceutical industries. Recently, using an integral equation theory formalism, Bomont et al. [J. Chem. Phys. 132, 184508 (2010)] studied theoretically the temperature dependence, at a fixed density, of the cluster formation in systems where particles interact with a hard-core double Yukawa potential composed of a short-range attraction and a long-range repulsion. In this paper, we provide evidence that the low-q peak in the static structure factor, frequently associated with the formation of clusters, is a common behavior in systems with competing interactions. In particular, we demonstrate that, based on a thermodynamic self-consistency criterion, accurate structural functions are obtained for different choices of closure relations. Moreover, we explore the dependence of the low-q peak on the particle number density, temperature, and potential parameters. Our findings indicate that enforcing thermodynamic self-consistency is the key factor to calculate both thermodynamic properties and static structure factors, including the low-q behavior, for colloidal dispersions with both attractive and repulsive interactions. Additionally, a simple analysis of the mean number of neighboring particles provides a qualitative description of some of the cluster features. [ABSTRACT FROM AUTHOR]

The role of gravity in gelation of adhesive hard spheres is studied and a critical criterion developed for homogeneous gelation within the gas-liquid binodal. We hypothesize that gelation by Brownian diffusion competes with phase separation enhanced by gravitational settling. This competition is characterized by the gravitational Péclet number Peg, which is a function of particle size, volume fraction, and gravitational acceleration. Through a systematic variation of the parameters, we observe the critical Peg of ~0.01 can predict the stability of gels composed of adhesive hard spheres. [ABSTRACT FROM AUTHOR]