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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]

Starting from a suspension of elastic dumbbells or chain-like particle aggregates as a simple model of a viscoelastic liquid, the rheological equation of state is inductively derived into which the concept of an "elastic strain component" (recoverable strain) is incorporated and can be understood as a nonlinear extension of the so-called "generalized Maxwell model." Here, the liquid is characterized by a sequence of nested continua, each associated with an elasticity law. The consideration of the directional dependence of the mobility of the structural elements requires that the behavior of the liquids represented in this way generally deviates from a Weissenberg liquid. [ABSTRACT FROM AUTHOR]

In this work, we outline the development of a thermodynamically consistent microscopic model for a suspension of aggregating particles under arbitrary, inertia-less deformation. As a proof-of-concept, we show how the combination of a simplified population-balance-based description of the aggregating particle microstructure along with the use of the single-generator bracket description of nonequilibrium thermodynamics, which leads naturally to the formulation of the model equations. Notable elements of the model are a lognormal distribution for the aggregate size population, a population balance-based model of the aggregation and breakup processes and a conformation tensor-based viscoelastic description of the elastic network of the particle aggregates. The resulting example model is evaluated in steady and transient shear forces and elongational flows and shown to offer predictions that are consistent with observed rheological behavior of typical systems of aggregating particles. Additionally, an expression for the total entropy production is also provided that allows one to judge the thermodynamic consistency and to evaluate the importance of the various dissipative phenomena involved in given flow processes. [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]

We derive a statistical mechanical model for colloidal interactions mediated by polymer-like micelles (PLMs) that adsorb at the colloid surface. The model considers the end-adsorption and reversible scission of ideal chains, and is based on experimentally measurable parameters relevant to PLMs. The model predicts interparticle attractions due to micellar bridging that are stronger and longer-range than those encountered in ordinary telechelic polymers. Mapping the analytical potential onto the more familiar Double Yukawa potential allows, for the first time, accurate, a priori prediction of suspension microstructure and phase behavior when compared to experimental data for model nanoparticles dispersed in wormlike micelles over a range of solution conditions. [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]

The mechanics of understanding a new application of the bracket theory of Non-Equilibrium Thermodynamics that allows for the incorporation of microstructural inertia effects within conformation tensor-based constitutive models of macroscopic material behavior is presented. Introducing inertia effects generally requires the replacement of a first order in time evolution equation for the conformation tensor by a second order one. Through the analysis of a simple damped oscillator we bring forward here the close connection to the structural dissipation brackets present in the two cases, with the weights being inverted as one transitions from the inertialess to the inertial description. Moreover, one may also describe inertial effects in material flow in certain situations through a simple modification of the first order evolution equation for the conformation tensor, which consists of adding a new non-affine term that couples the conformation and the vorticity tensors, as detailed in a recent publication (P. M. Mwasame, N. J. Wagner and A. N. Beris, Phys. Fluids, 30 (2018), 030704). As shown there, when applied to the low particle Reynolds flow of dilute emulsions, this reduced inertial flow model provides predictions consistent with literature-available microscopically based asymptotic results. [ABSTRACT FROM AUTHOR]

Stabilized-emulsions often undergo Ostwald ripening owing to the higher solubility of the smaller droplets. Their rheological properties are a direct result of the interplay between their microstructure and flow, which in turn affect their processing as well as their applications. In a recent study [Mwasame et al., "On the macroscopic modelling of dilute emulsions under flow," J. Fluid Mech. 831, 433–473 (2017)], the use of a unit determinant conformation tensor to represent morphological changes has been advanced within the context of a thermodynamically consistent theory for a dilute monodisperse emulsion. The resulting model was validated against previously developed asymptotic theory that was also used to obtain all model parameters. In the present work, the first key innovation is to show how this theory can be extended to allow for multiple conformation tensors, subject to a single joint constraint originating from the mass conservation of the dispersed phase, in order to allow for the representation of dilute polydisperse emulsions undergoing Ostwald ripening. The second enabling innovation of this work is to show how to introduce correct dissipative terms into the dissipation bracket to account for mass transfer processes. The approach is illustrated for the particular case of a bidisperse emulsion. The model illustrates how multiple transport phenomena and thermodynamic effects can be seamlessly combined within a thermodynamically consistent approach. This work allows for not only the coexistence of a bimodal population of droplets but also the evaluation of their deformability and effective rheology in the presence of Ostwald ripening as the largest size droplets increase in mass at the expense of the smaller ones. [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.

Nonequilibrium Brownian dynamics simulations are used to study the effect of polydispersity on the thermodynamics, rheology, microstructure, and shear-induced disorder–order transition in suspensions of charged colloids. Approximately 43 000 particles with 2000 different components of a discretized Schulz distribution at polydispersities from 0% to 30% are simulated on a massively parallel computer. Recent advances in the integral equation theory for polydisperse suspensions are tested and verified with respect to both structure and equilibrium mechanical properties. The low shear rate rheology for both monodisperse and polydisperse suspensions is found to be well represented by the Ree–Eyring model. At higher shear rates an ordered ‘‘string’’ phase is shear induced for low polydispersities (<10%). Increasing the polydispersity further (>=20%) inhibits the ordering, suggesting the existence of a critical polydispersity beyond which a colloidal suspension cannot be induced into an ordered state by shearing. The validity of a generalized, nonequilibrium Stokes–Einstein relationship for polydisperse colloids is also investigated. © 1996 American Institute of Physics. [ABSTRACT FROM AUTHOR]

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]

The two-particle correlation function is related to the structure factor by an integral transform and serves as an important connection between suspension microstructure, scattering experiments, and macroscopic properties. The nonequilibrium structure factor for a shearing colloidal suspension of spherical particles is expanded in spherical harmonics. Through this expansion, we demonstrate formal relationships between the experimentally accessible static structure factor, bulk stresses, and optical dichroism and birefringence, demonstrating that a limited number of expansion terms are required to characterize the suspension rheology. Low shear limiting theories are expressed in terms of this expansion, demonstrating the utility of the expansion for comparison of experimental measurements of nonequilibrium structure factors to theoretical predictions. Although flow birefringence and the thermodynamic shear stress are calculated as weighted integrals over the nonequilibrium microstructure in the low shear limit, no simple stress-optical coefficient is found. The expansion is proposed as a consistent methodology for analysis of experimental data and presentation of theoretical predictions, providing a means of interpreting rheo-optical data. [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]

Optical measurements were used to detect structural anisotropy in concentrated dispersions over a range of Peclet numbers. Silica spheres of 49 and 130 nm radii with grafted octadecyl chains were dispersed in cyclohexane at volume fractions from 0.1 to 0.4. The apparatus consisted of a Couette cell with the dispersion in the annulus probed by a HeNe laser beam parallel to the axis of rotation. The dichroism and birefringence of the transmitted beam varied linearly with shear rate at low Peclet numbers with an orientation coincident with the principle direction of shear. Increasing the Peclet number, by increasing the particle size, produced a nonlinear response with the orientation tending to align in the direction of flow. A theory coupling the nonequilibrium microstructure under shear to the optical properties of the suspension enables direct interpretation of the dichroism. Comparison of sample dichroism calculations for two different forms of the theory demonstrates that the optical technique can be used to discriminate between theories which predict the microstructure. [ABSTRACT FROM AUTHOR]

Knowledge of the nanoscale distribution of proteins in chromatographic resins is critical to our mechanistic understanding of separations performance. However, the nano- to mesoscale architecture of these materials is challenging to characterize using conventional techniques. Small-angle neutron scattering was used to probe (1) the nano- to mesoscale structure of chromatographic media and (2) protein sorption in these media in situ with protein-scale resolution. In particular, we characterize the effect of the architecture of cellulose-based and traditional and dextran-modified agarose-based ion-exchange resins on the nanoscale distribution of a relatively small protein (lysozyme) and two larger proteins (lactoferrin and a monoclonal antibody) at different protein loadings. Traditional agarose-based resins (SP Sepharose FF) can be envisioned as comprising long, thin strands of helical resin material around which the proteins adsorb, while higher static capacities are achieved in dextran-modified resins (SP Sepharose XL and Capto S) due to protein partitioning into the increased effective binding volume provided by the dextran. While protein size is shown not to affect the underlying sorption behavior in agarose-based resins such as SP Sepharose FF and XL, it plays an important role in the cellulose-based S HyperCel and the more highly cross-linked agarose-based Capto S, where size-exclusion effects prevent larger proteins from binding to the base matrix resin strands. Based on the data, we propose that entropic partitioning effects such as depletion forces may drive the observed protein crowding. In general, these observations elucidate the structure and point to the mechanism of protein partitioning in different classes of chromatographic materials, providing guidance for optimizing their performance. [ABSTRACT FROM AUTHOR]

In situ measurements are an increasingly important tool to inform the complex relationship between nanoscale properties and macroscopic material measurements. Knowledge of these phenomena can be used to develop new materials to meet the performance demands of next generation technologies. Conductive complex fluids have emerged as an area of research where the electrical and mechanical properties are key design parameters. To study the relationship between microstructure, conductivity, and rheology, we have developed a small angle neutron scattering (SANS) compatible Couette rheological geometry capable of making impedance spectroscopy measurements under continuous shear. We have also mounted this geometry on a commercial strain controlled rheometer with a modified forced convection oven. In this manuscript, we introduce the simultaneous measurement of impedance spectroscopy, rheological properties and SANS data. We describe the validation of this dielectric RheoSANS instrument and demonstrate its operation using two systems—an ion gel comprising Pluronic® surfactant and ionic liquid, ethyl-ammonium nitrate, and poly(3-hexylthiophene) organogel prepared in a mixture of hexadecane and dichlorobenzene. In both systems, we use this new measurement capability to study the microstructural state of these materials under two different protocols. By monitoring their dielectric rheology at the same time as the SANS measurement, we demonstrate the capacity to directly probe structure-property relationships inherent to the macroscopic material response. [ABSTRACT FROM AUTHOR]

Densities and viscosities of binary mixtures containing 1-butyl-3-methylimidazolium tetrafluoroborate with water over the salt-rich region concentrations are reported for a temperature range of (283.15 to 373.15) K and compared with literature. The temperature dependence of the mixture densities and dynamic viscosities are accurately described by an empirical, linear relationship and by the Vogel-Fulcher-Tammann (VFT) equation, respectively. We identify a correlation between the excess mixture viscosity and the excess molar volume in the ionic liquid rich regime that is motivated by free volume theory. The broader validity of this correlation is tested against literature data for aqueous mixtures of similar ionic liquids. [ABSTRACT FROM AUTHOR]

Novel measurements of the spatiotemporal microstructure of a continuous shear thickening colloidal suspension under shear cessation and reversal using small angle neutron scattering in a 1–2 shear cell are presented for moderate to high Péclet numbers. In the shear cessation experiments from high Péclet shear flow, two-step relaxation mechanism is found. Particles first readily diffuse on a characteristic timescale of single particle Brownian motion, followed by slower relaxation dynamics on a timescale of short-time self-diffusion when caging effects start dominating. In the shear reversal experiment, the unchanged scattering intensity and the quick flip in anisotropic structure around the shear thickened state suggest the persistence of hydroclusters without transitioning through the equilibrium structure, at least in a time resolution of 0.01 s. Access to the time evolution of microstructure provides valuable insights into the spatiotemporal details of interparticle interactions governing colloidal suspension rheology, such as Brownian, hydrodynamic, and nanotribological forces. [ABSTRACT FROM AUTHOR]

The present study develops a fully consistent extension of the approach pioneered by Farris ["Prediction of the viscosity of multimodal suspensions from unimodal viscosity data," Trans. Soc. Rheol. 12, 281-301 (1968)] to describe the viscosity of polydisperse suspensions significantly improving upon our previous model [P. M. Mwasame, N. J. Wagner, and A. N. Beris, "Modeling the effects of polydispersity on the viscosity of noncolloidal hard sphere suspensions," J. Rheol. 60, 225-240 (2016)]. The new model captures the Farris limit of large size differences between consecutive particle size classes in a suspension. Moreover, the new model includes a further generalization that enables its application to real, complex suspensions that deviate from ideal non-colloidal suspension behavior. The capability of the new model to predict the viscosity of complex suspensions is illustrated by comparison against experimental data. [ABSTRACT FROM AUTHOR]

The microstructure of mixtures of deuterated water in the ionic liquid [C4mim][BF4] is investigated by small-angle neutron scattering (SANS) measurement. In the salt-rich region, water dissolves in the ionic liquid up to 0.7 mole fraction, whereupon distinct, nanometer-sized water clusters are observed. These water nanoclusters increase in size with increasing water addition while the mole ratio of water dissolved into the ionic liquid nanostructure increases from 2 to 4. These results provide direct confirmation for recent simulations as well insight into the source of nonidealities in some thermophysical and transport properties (e.g., density and viscosity) of salt-rich aqueous mixtures reported in the literature. [ABSTRACT FROM AUTHOR]

The microstructure of mixtures of deuterated water in the ionic liquid [C4mim][BF4] is investigated by small-angle neutron scattering (SANS) measurement. In the salt-rich region, water dissolves in the ionic liquid up to 0.7 mole fraction, whereupon distinct, nanometer-sized water clusters are observed. These water nanoclusters increase in size with increasing water addition while the mole ratio of water dissolved into the ionic liquid nanostructure increases from 2 to 4. These results provide direct confirmation for recent simulations as well insight into the source of nonidealities in some thermophysical and transport properties (e.g., density and viscosity) of salt-rich aqueous mixtures reported in the literature. [ABSTRACT FROM AUTHOR]

he present study develops an extension of the approach pioneered by Farris [Trans. Soc. Rheol. 12, 281-301 (1968)] to model the viscosity in polydisperse suspensions. Each smaller particle size class is assumed to contribute to the suspension viscosity through a weighting function in two ways: first, indirectly, by altering the background viscosity, and second, directly, by increasing the contribution of the larger particles to the suspension viscosity. The weighting functions are developed in a consistent fashion as a power law with the exponent, h, a function of the relative volume fraction ratio and the base, g, a function of the solid particle size ratio. The model is fit to available theoretical and experimental results for the viscosity of several binary suspensions and shows good to excellent agreement depending on the functions g and h chosen. Once parameterized using binary suspension viscosity data, the predictive capability to model the viscosity of arbitrary continuous size distributions is realized by representing such distributions with equivalent ternary approximations selected to match the first six moments of the actual size distribution. Model predictions of the viscosity of polydisperse suspensions are presented and compared against experimental data. [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]

SANS directly measures the structure of protein-surfactant complexes in bulk solution and thus can reliably evaluate the surfactant binding to a protein. However, there are concerns of protein stability that can be caused either by protein-protein interactions or by the surface of prefilled syringes that are usually siliconized and cause proteins to denature at these hydrophobic oil-water interfaces. [Extracted from the article]

Measurements of the nanoscale structure of chromatographic adsorbents and the associated distribution of sorbed protein within the media can facilitate improvements in such media. We demonstrate a new technique for this purpose using small-angle neutron scattering (SANS) to characterize the nano- to microscale structure of the chromatographic media and sorbed protein under conditions relevant for preparative chromatographic separations. The adsorption of lysozyme on cellulosic S HyperCel™ (Pall Corporation), a strong cation exchanger, was investigated by SANS. The scattering spectrum is reduced to three contributions arising from (1) the chromatographic medium, (2) discrete protein molecules, and (3) the distribution of sorbed protein within the medium. These contributions are quantified for a range of protein loadings. The total concentration of protein in the chromatographic media can be quantified from the SANS spectrum and the protein is observed to retain its tertiary structure upon adsorption, within the resolution of the method. Further analysis of the SANS spectra shows that protein adsorption is uniform in the media. These measurement techniques provide new and valuable nanoscale information about protein sorption in chromatographic media. [ABSTRACT FROM AUTHOR]

The rheology and three-dimensional microstructure of a concentrated viscoelastic solution of the triblock copolymer poly(ethylene oxide)106-poly(propylene oxide)6 8-poly(ethylene oxide)106 (Pluronic F127) in the protic ionic liquid ethylammonium nitrate are measured by small angle neutron scattering (SANS) under flow in three orthogonal planes. This solution's shear-thinning viscosity is due to the formation of two-dimensional hexagonal close-packed (HCP) sliding layer structure. Shear-melting of the crystalline structure is observed without disruption of the selfassembled micelles, resulting in a change in flow properties. Spatially resolved measurements in the 1-2 plane reveal that both shear-melting and sliding are not uniform across the Couette gap. Melting and recrystallization of the HCP layers occur cyclically during a single large amplitude oscillatory shear (LAOS) cycle, in agreement with the "stick-slip" flow mechanism proposed by Hamley et al. [Phys. Rev. E 58, 7620-7628 (1998)]. Analysis of 3D "structural" Lissajous curves show that the cyclic melting and sliding are direct functions of the strain rate amplitude and show perfect correlation with the cyclic stress response during LAOS. Both viscosity and structural order obey the Delaware-Rutgers rule. Combining rheology with in situ spatiotemporally resolved SANS is demonstrated to elucidate the structural origins of the nonlinear rheology of complex fluids. [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]

The short-time diffusivity of dicolloid particles as a function of particle volume fraction ɸ from 0.01 ≤ ɸ ≤ 0.6 is measured using diffusing wave spectroscopy. The diffusivities of symmetric and asymmetric dicolloids are compared with similarly sized spheres. The short-time diffusivity is independent of salt concentration and decreases with increasing volume fraction for both spheres and asymmetric dicolloids. Symmetric dicolloids have a higher diffusivity than spheres at similar volume fractions. This difference is accounted for by rescaling the dicolloid volume fraction based on the ratio of the random close-packing volume fractions of spheres and dicolloids. Finally, a useful method is provided for calculating the diffusivity of symmetric dicolloid particles of arbitrary aspect ratio based on the calculated hydrodynamic resistance of Zabarankin [Proc. R. Soc. A 463, 2329 (2007)]. [ABSTRACT FROM AUTHOR]

Oppositely charged polyelectrolyte-surfactant mixtures are ubiquitous in biology and the basis of numerous consumer healthcare products. Despite their broad use, however, a rational approach to their formulation remains challenging because of the complicated association mechanisms. Through compilation and analysis of literature reports and our own research, we have developed a semiempirical correlation of the binding strength of surfactants to polyelectrolytes in salt-free mixtures as a function of the polyion linear charge density and the surfactant hydrophobicity. We have found that the cooperative binding strength increases as the square of the polyelectrolyte's linear charge density and in proportion to the surfactant's hydrophobicity, such that a quantitative relationship holds across a broad range of polyelectrolytes. Deviations from the correlation reveal the role of system-specific interactions not considered in the analysis. This engineering relationship aids in the rational design of oppositely charged polyelectrolyte-surfactant formulations for consumer products and biomedicines by enabling the prediction of binding strengths in polyelectrolyte-surfactant mixtures based on mesoscale parameters determined from the chemical composition. [ABSTRACT FROM AUTHOR]

Models, theories, and simulations for the low shear viscosity of Brownian, hard-sphere dispersions are examined and evaluated against literature data. Hydrodynamic and thermodynamic contributions are explicitly treated and the volume fraction dependence of the experimental data is validated against the high frequency or high shear viscosity. A good description of the data is realized by a new, semiempirical model based on mode coupling theory, where [lowercase_phi_synonym]m=[lowercase_phi_synonym]g=0.57, supporting dynamical arrest at the ideal glass transition. [ABSTRACT FROM AUTHOR]

Micellar solutions of hexadecyltrimethylammonium bromide(CTAB)in a protic ionic liquid, ethylammonium nitrate (EAN), are studiedby shear rheology, polarizing optical microscopy (POM), conductivitymeasurements, and small angle neutron scattering (SANS). Three concentrationregimes are examined: A dilute regime (with concentrations [CTAB]< 5 wt %) consisting of noninteracting spherical micelles, a semidiluteregime (5 wt % ≤ [CTAB] ≤ 45 wt %) where micelles interactvia electrostatic repulsions, and a concentrated regime (45 wt % <[CTAB] ≤ 62 wt %) where a reversible, temperature-dependentisotropic (L1) to hexatic (Hex) phase transition is observed.The L1–Hex transition, which has been predictedbut not previously observed, is characterized by (1) a sharp increasein the shear viscosity, (2) the formation of focal conical birefringencetextures (observed by POM), and (3) enhancement of the crystallineorder, evidenced by the appearance of Bragg reflections in the SANSprofiles. Ionic conductivity is not sensitive to the L1–Hex transition, which corroborates the absence of topologicaltransitions. [ABSTRACT FROM AUTHOR]

In this Article, we report the dielectrophoretic assemblyof colloidalparticles and show how the kinetics of assembly and degree of orderingdepend on the particle size, charge, solution ionic strength, andfield strength and frequency. A special dielectrophoresis (DEP) samplecell is constructed and validated to quantitatively measure directedself-assembly via sequential light scattering and optical microscopymeasurements. Our results confirm the recently established scalingfor the order–disorder transition and extend it to higher scaledfrequencies. The limiting scaling of the order–disorder transitionand particle electrophoretic mobility are correctly predicted by thestandard electrokinetic model (SEKM). In particular, the order–disordertransition line is predicted from the particle properties using arecently proposed empirical scaling law and the SEKM over an orderof magnitude in particle size. [ABSTRACT FROM AUTHOR]

Large amplitude oscillatory shear (LAOS) is an increasingly popular nonlinear rheological test method, and the interpretation of the measurements is still an active area of research. Here, we demonstrate a new method whereby the nonlinear parameters of a popular constitutive equation used to model polymeric and other viscoelastic systems, the Giesekus model, may be determined directly from LAOS measurements without complicated, nonlinear model fitting. We define the stress response of the sample as an expansion in deformation strain and oscillation frequency. To leading order in strain, we derive the explicit analytic expressions for the first three harmonics of the stress response during LAOS for the Giesekus constitutive model. This allows for rapid determination of the Giesekus model parameters, including the nonlinear coupling parameter, directly from plots of the response obtained from modern rheological instruments. We demonstrate the validity, utility, and limits of this new method on a well-studied wormlike micelle (WLM) surfactant solution, cetyltrimethylammonium bromide (CTAB), and water. This robust and simple approach is especially advantageous for systems where steady shearing in the nonlinear regime is problematic and can provide rapid determination of parameters in rheological constitutive equations. [ABSTRACT FROM AUTHOR]

The article discusses the role of shear thickening in colloidal dispersions. It states that a change in viscosity will likely to happen when colloidal fluids experience shear stress resulting to the stiffening of the products such as paints, cements and shampoos. It adds that scientists and physics community have studied the highly nonlinear materials to deal the problems occurring in the shear-thickening colloidal dispersions.

Prior work has demonstrated that colloidal suspensions can be ordered with large amplitude oscillatory shear (LAOS), showing that the final type and degree of ordering depends on the frequency and amplitude of the applied oscillation. Here, we present LAOS results for the kinetics of ordering for colloidal particles (d=1 μm) at [lowercase_phi_synonym]=0.54 from a shear disordered state over a range of frequencies and shear amplitudes. A custom rheolight scattering (rheo-LS) device is used to quantify the type and degree of crystalline order observed either as a six spot Bragg pattern or a three streak twinning pattern. The dynamic shear stress and the alignment factor derived from the rheo-LS show the same time-dependent behavior indicative of a primary relaxation that is exponential in time. The rate of ordering to the r-hcp state is found to scale with the amplitude of oscillation and inversely with the frequency over strains from 100% to 300% and frequencies from 0.5 to 5 Hz. These results show that the rate of LAOS ordering does not simply reflect the rate of deformation, but rather a more complex mechanism pointing toward competition between shear ordering and shear-induced defect generation. [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]

Abstract: Flow can induce reversible and irreversible structural changes in dispersions. The analysis of flow effects on microstructure and rheology remains one of the challenging problems in colloid science. The rheological manifestation of flow-induced structural changes is a variable viscosity. If the changes are reversible and time dependent, the effect is called thixotropy. The basic elements of this concept are reviewed here, including its definition and the relation with nonlinear viscoelasticity. The omnipresence of thixotropy is illustrated with a wide range of examples from natural and manmade colloidal systems. Its various rheological manifestations are reviewed as well as possible measurement procedures. The microstructural changes due to flow are quite complex and not fully understood. Existing models for thixotropic suspension rheology are categorized and evaluated. [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]

The phase behavior of novel hybrid diblock copolymers composed of poly(benzyl ether) dendrons of various generations grafted to deuterated polystyrene tails of varying molecular weights are examined by small angle neutron scattering. Blends of these hybrid copolymers with linear polystyrene of two molecular weights are shown to exhibit dissolution, microphase separation and microphase & mesophase separation depending on the relative molecular weights of the dendrons, tails, and matrix homopolymer. The results suggests that there is a strong entropic penalty against mixing polymers of dendritic architecture with linear chains, and that this driving force can be harnessed to create unique, nanostructured polymer materials. To cite this article: C. R. Chimie 6 (2003). [Copyright &y& Elsevier]

Electron transport in complex fluids, biology, and soft matter is a valuable characteristic in processes ranging from redox reactions to electrochemical energy storage. These processes often employ conductor-insulator composites in which electron transport properties are fundamentally linked to the microstructure and dynamics of the conductive phase. While microstructure and dynamics are well recognized as key determinants of the electrical properties, a unified description of their effect has yet to be determined, especially under flowing conditions. In this work, the conductivity and shear viscosity are measured for conductive colloidal suspensions to build a unified description by exploiting both recent quantification of the effect of flow-induced dynamics on electron transport and well-established relationships between electrical properties, microstructure, and flow. These model suspensions consist of conductive carbon black (CB) particles dispersed in fluids of varying viscosities and dielectric constants. In a stable, well-characterized shear rate regime where all suspensions undergo self-similar agglomerate breakup, competing relationships between conductivity and shear rate were observed. To account for the role of variable agglomerate size, equivalent microstructural states were identified using a dimensionless fluid Mason number, Mnf, which allowed for isolation of the role of dynamics on the flow-induced electron transport rate. At equivalent microstructural states, shear-enhanced particle-particle collisions are found to dominate the electron transport rate. This work rationalizes seemingly contradictory experimental observations in literature concerning the shear-dependent electrical properties of CB suspensions and can be extended to other flowing composite systems. [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]

An expression for the form birefringence of a shearing colloidal suspension is derived from the renormalization of Adriani and Gast [J. Chem. Phys. 91, 6282 (1990)]. Calculations based on recent predictions for the nonequilibrium microstructure of a shearing hard-sphere suspension are compared with previous measurements. The error in the predictions is in agreement with earlier comparisons of this structure against light scattering and rheological measurements. [ABSTRACT FROM AUTHOR]

The article presents technical comments on a paper by Rabb and Fahrenthold titled, "Evaluation of Shear-Thickening-Fluid Kevlar for Large-Fragment-Containment Applications." The goal of the study was to determine whether Kevlar fabrics treated with shear thickening fluids (STF) could enhance turbine fan-blade confinement barriers. The limitations of the experimental data are discussed in this technical comment, while the conclusions regarding protective applications are questioned.

[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]

In the present work, the macroscopic governing equations governing the heat and mass transfer for a general multicomponent system are derived via a systematic nonequilibrium thermodynamics framework. In contrast to previous approaches, the relative (with respect to the mass average velocity) component mass fluxes (relative species momenta) and the heat flux are treated explicitly, in complete analogy with the momentum flux. The framework followed here, in addition to allowing for the description of relaxation phenomena in heat and mass transfer, establishes to the fullest the analogy between all transport processes, momentum, heat, and mass transfer, toward which R. B. Bird contributed so much with his work. The inclusion of heat flux-based momentum as an additional variable allows for the description of relaxation phenomena in heat transfer as well as of mixed (Soret and Dufour) effects, coupling heat and mass transfer. The resulting models are Galilean invariant, thereby resolving a conundrum in the field, and always respect the second law of thermodynamics, for appropriate selection of transport parameters. The general flux-based dynamic equations reduce to the traditional transport equations in the limit when mass species and heat relaxation effects are negligible and are fully consistent with the equations established from the application of kinetic theory in the limit of dilute gases. As an added benefit, for the particular example case of hyperbolic diffusion we illustrate the application of the proposed models as a method to allow the use of powerful numerical solvers normally not available for solving mass transfer models more generally. [ABSTRACT FROM AUTHOR]

Future human space exploration and habitation on the lunar and Martian surfaces necessitates in-situ resource utilization (ISRU) for the development of construction materials tailored for infrastructure and environmental protection. Here we explore the use of lunar and Martian regoliths to create construction materials with properties suitable for such structures as landing pads. Alkali activation of a spectrum of lunar and Martian regolith simulants generates geopolymer binders under ambient and vacuum curing conditions as well as exposure to extreme high and low temperatures (600 and −80 °C). Compressive strength is reduced for binders prepared from each simulant after curing under vacuum and exposure to sub-zero temperatures. In lunar simulant binders, the compressive strength is increased after heating to 600 °C, but the opposite effect is observed in the Martian simulant binder. Amorphous aluminosilicate content and percentage of small particles in the simulants are hypothesized to have a positive impact on compressive strength under ambient curing. Iron and magnesium content may be responsible for decreased compressive strength of the Martian binder after heating. This study offers a robust framework for comparing performance of different simulants under the same curing protocols and environmental exposures, as well as offering insight as to the effects of vacuum curing, and exposure to high and low temperature environments on cured binder samples. Developing a landing pad by transporting activator to the lunar surface is shown to be conceptually feasible within current payload constraints. [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]

Acylated peptides composed of glucagon-like peptide-1 receptor agonists modified with a fatty acid side chain are an important class of therapeutics for type 2 diabetes and obesity but are susceptible to an unusual physical instability in the presence of hydrophobic surfaces, i.e., spontaneous emulsification, also known as ouzo formation in practice. In this work, light scattering, small-angle X-ray scattering, and circular dichroism measurements are used to characterize the physical properties of the semaglutide colloidal phase, including size distribution, shape, secondary structure, internal structure, and internal composition, as a function of solution physico-chemical conditions. The existence and size of the colloids formed are successfully predicted by a classical Rayleigh model, which identifies the parameters controlling their size and formation. Colloid formation is found to be catalyzed by hydrophobic surfaces, and formation rates are modeled as an autocatalytic reaction, enabling the formation of a master curve for various surfaces that elucidates the mechanism. Surfaces differ due to differences in surface wettability, which can be correlated with Hansen solubility parameters. This work provides insights into this unusual colloidal phenomenon and guides the peptide synthesis process and drug product formulation in the pharmaceutical industry. [ABSTRACT FROM AUTHOR]