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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]

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]

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]

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]

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]

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]

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 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]

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]

Scientific questions surrounding the shear-dependent microstructure of carbon black suspensions are motivated by a desire to predict and control complex rheological and electrical properties encountered under shear. In this work, direct structural measurements over a hierarchy of length scales spanning from nanometers to tens of micrometers are used to determine the microstructural origin of the suspension viscosity measured at high shear rates. These experiments were performed on a series of dense suspensions consisting of high-structured carbon blacks from two commercial sources suspended in two Newtonian fluids, propylene carbonate and light mineral oil. The shear-induced microstructure was measured at a range of applied shear rates using Rheo-VSANS (very small angle neutron scattering) and Rheo-USANS (ultra-small angle neutron scattering) techniques. A shear-thinning viscosity is found to arise due to the self-similar break up of micrometer-sized agglomerates with increasing shear intensity. This self-similarity yields a master curve for the shear-dependent agglomerate size when plotted against the Mason number, which compares the shear force acting to break particle-particle bonds to the cohesive force holding bonds together. It is found that the agglomerate size scales as R g , agg ∼ M n − 1 . Inclusion of the particle stress contribution extends the relevance of the Mason number to concentrated suspensions such as those relevant to the processing of carbon black suspensions for various applications. [ABSTRACT FROM AUTHOR]

Recently, Mwasame et al. [“On the macroscopic modeling of dilute emulsions under flow,” J. Fluid Mech. 831, 433 (2017)] developed a macroscopic model for the dynamics and rheology of a dilute emulsion with droplet morphology in the limit of negligible particle inertia using the bracket formulation of non-equilibrium thermodynamics of Beris and Edwards [Thermodynamics of Flowing Systems: With Internal Microstructure (Oxford University Press on Demand, 1994)]. Here, we improve upon that work to also account for particle inertia effects. This advance is facilitated by using the bracket formalism in its inertial form that allows for the natural incorporation of particle inertia effects into macroscopic level constitutive equations, while preserving consistency to the previous inertialess approximation in the limit of zero inertia. The parameters in the resultant Particle Inertia Thermodynamically Consistent Ellipsoidal Emulsion (PITCEE) model are selected by utilizing literature-available mesoscopic theory for the rheology at small capillary and particle Reynolds numbers. At steady state, the lowest level particle inertia effects can be described by including an additional non-affine inertial term into the evolution equation for the conformation tensor, thereby generalizing the Gordon-Schowalter time derivative. This additional term couples the conformation and vorticity tensors and is a function of the Ohnesorge number. The rheological and microstructural predictions arising from the PITCEE model are compared against steady-shear simulation results from the literature. They show a change in the signs of the normal stress differences that is accompanied by a change in the orientation of the major axis of the emulsion droplet toward the velocity gradient direction with increasing Reynolds number, capturing the two main signatures of particle inertia reported in simulations. [ABSTRACT FROM AUTHOR]

• The method to study the microstructure of asphalt binders by SANS was established. • The microstructure of asphalt binders was found and the micelle size was calculated. • The relationship between rheological properties and microstructure of asphalt was analyzed. • The SBS modified mechanism was proved by SANS. The microstructure of asphalt binders is believed to have a significant impact on the performance of binders used in roadway constructions. However, there are only limited studies of their nanoscale to microscale structures. Here, small angle neutron scattering (SANS) is used to study the nanoscale structure of neat asphalt binder, styrene-butadienestyrene (SBS) block copolymers and SBS modified asphalt binder. The SANS pattern for asphalt binder demonstrates that it exhibits a colloidal structure comprised of asphaltenes surrounded by resins dispersed in saturates and aromatics. Fractal-core-shell model fits to these patterns indicate that the asphaltene core size decreases with increasing temperature. Both SANS and rheology confirm that SBS modified asphalt has a thermo-reversible phase transition around 110 °C, where the SBS micelles swell and lose scattering contrast above this temperature. The thermo-reversibility of this phenomenon indicates that the mechanism of SBS modification is mostly a physical modification of the nanoscale structure as proposed in the colloidal model of asphalt. Modeling of the SANS patterns shows that neat SBS and SBS dispersed in asphalt binder have a lamellar structure surrounded by a shell. These results are useful for understanding the relationship between the nanoscale structure of asphalt binder and pavement performance, as well as potentially developing new types of modified asphalt binders. [ABSTRACT FROM AUTHOR]

We present new dynamic rheological tests of human blood that motivate an improved model for the thixotropic shear rheology of human blood. Unidirectional large amplitude oscillatory shear (UD-LAOS) is proposed as a dynamic test relevant for understanding in vivo arterial pulsatile blood flow, and data are presented for two healthy donors studied previously using more traditional steady and step-rate experiments. The model analyzes the overall extra stress of the system in two components. A thixotropic component is represented by a structure-kinetics model coupled with a stress expression containing both viscoelastic and thixotropic elements to account for the presence of linear aggregates of red blood cells, known as rouleaux, which form at low shear rates. Another component is viscoelastic, described through an extend White–Metzner approach. It corresponds to the stresses that arise due to the isolated red blood cells, which deform at high shear rates. The combined model is fit to experimental steady shear and UD-LAOS data for two healthy donors and is subsequently used to predict the stress response of the blood sample to UD-LAOS experiments over a broad range of strain amplitudes and frequencies. Comparison to the previous models for transient blood rheology shows a significantly improved fit over a range of physiologically relevant flow conditions. In addition, this analysis demonstrates the usefulness of UD-LAOS tests with regards to understanding the microstructural evolution in blood under transient flow. [ABSTRACT FROM AUTHOR]

The microstructure and rheological properties of colloidal suspensions depend on particle size and shape. This work aims to further control the size, shape, and polydispersity of anisotropic silica colloids, to reduce particle size, and to provide additional mechanistic insights on a prevalent, water-in-oil emulsion synthesis method. Key findings show that the dimensions of anisotropic silica particles can be systematically varied by approximately fivefold, with a limiting minimum particle size (D ≈ 60 nm, L ≈ 300 nm) obtained from emulsions with excess polyvinylpyrrolidone (PVP) and sodium citrate. The synthesis conditions are identified and discussed for which the emulsion composition, temperature, sonication, polymer entanglements, mixing, and other perturbations may induce or mitigate emulsion instabilities, citrate precipitation, a competing mechanism of templated growth, termination of anisotropic growth, irregular silica structures, and fiber formation. An improved mechanistic understanding will expand the roadmap for rational design and synthetic control of anisotropic colloids using sol-gel silica chemistry confined within water-in-oil emulsions. [ABSTRACT FROM AUTHOR]

A stable dispersion of silica nanoparticles in a common ionic liquid [C4mim][BF4] that exhibits significant shear thickening is formulated by controlling the strength of hydrogen bonding between the nanoparticle surface and the anion of [C4mim][BF4]. Colloidal stability is demonstrated to be due to the formation of solvation layers, the properties of which are determined by scattering measurements. Timetemperature superposition measurements and the onset of yielding behavior in steady shear indicate the increase of particle-particle attraction and loss of stability of colloidal dispersions above 30 °C. Small angle neutron scattering and dynamic light scattering measurements confirm the reduction in solvation layering at elevated temperatures, leading to a transition from stable dispersion to unstable, attractive gel with increasing temperature (i.e., an inverse melting transition). It is demonstrated how controlling specific surface-anion interactions through chemical functionality can be used to formulate nanoparticle dispersions in ionic liquids with specific rheological properties. [ABSTRACT FROM AUTHOR]

Colloidal gels exhibit time-dependent bulk properties. However, the processes and mechanisms by which aging occurs are poorly understood, which complicates the prediction of macroscopic behavior in these systems. Using a model, thermoreversible, adhesive hard sphere system consisting of octadecyl-coated silica nanoparticles dispersed in tetradecane, rheological aging is quantitatively related to structural aging. By simultaneously measuring the bulk properties and gel microstructure using rheometry and small angle neutron scattering, respectively, we show a one-to-one correspondence between the time-dependent storage modulus and the microstructure, and further, that this correspondence is independent of the gel's thermal and shear history. At the working volume fraction, the gel is homogeneous and, unlike phase-separated gels, aging behavior is not due to heterogeneous coarsening. Instead, the results presented here are consistent with homogeneous, local particle rearrangements as the mechanism of rheological aging. By establishing a quantitative and predictive relationship between the underlying microstructure and bulk mechanical properties, the results of this study may be (1) industrially relevant to products that age on commercially relevant timescales, (2) applicable to other dynamically arrested systems, such as metallic glasses, and (3) valuable in the design of new materials. [ABSTRACT FROM AUTHOR]

The shear rate-dependent rheological properties of soft to rigid colloidal suspensions are studied using computational models. We show that a contact force defined based on an elastohydrodynamic deformation theory captures an important rheological behavior of colloidal suspensions: While near hard-sphere particles exhibit a strong and continuous shear thickening the evolves to a constant viscosity state, soft suspensions undergo a second shear-thinning regime at high Peclet numbers when the hydrodynamic stresses become larger than the modulus of the colloidal particles. We measure N1 and N2 to be large and negative in the shear-thickening regime; however, for soft spheres at the onset of second shear-thinning N2 reduces in magnitude and eventually becomes positive. We show that for near hard-sphere suspensions, colloidal pressure, shear stress, and normal stress difference coefficients tend to diverge near the maximum packing fraction while P > σ > N1 > N2. [ABSTRACT FROM AUTHOR]

The microstructure and rheologicalproperties of micellar solutionsof Pluronic block copolymers (PEOx–PPOy–PEOx)in deuterated ethylammonium nitrate (dEAN, a protic ionic liquid)are studied by small- and ultrasmall-angle neutron scattering (SANSand USANS), fluorescence microscopy, and shear rheology. A homologousseries of three Pluronics with similar PPO block length (F127 (PEO106–PPO70–PEO106), P123(PEO20–PPO70–PEO20),and L121 (PEO5–PPO70–PEO5)) are examined to explore the effect of the relative balance ofsolvophilic to solvophobic block size on the self-assembled microstructure.Both F127 and P123 form spherical micelles in dEAN that assemble intoface-centered and body-centered cubic supramolecular crystals, respectively,upon increasing concentration or temperature. The transition fromdisordered to crystalline (ordered) structures manifests as a sol–gelrheological transition. A richer phase diagram is observed in theL121/dEAN system: due to its low solvophilicity in dEAN, L121 self-assemblesinto structures with low curvatures, namely, vesicles in the diluteregime, elongated (wormlike) micelles at intermediate concentrationsand low temperatures, a nematic phase in concentrated solutions, andmultilamellar phases at high temperatures. Highly viscoelastic solutionsare created by the self-assembly of entangled L121 wormlike micelles.Structural length scales of the three Pluronic/dEAN systems in thevarious mesophases are determined from SANS and USANS. [ABSTRACT FROM AUTHOR]

Structure-property relationships of alkali-activated aluminosilicate gels are studied using rheology, neutron scattering, solid-state NMR, and TEM to develop a pseudo-ternary state diagram. Empirical gel states are classified by the rheological behavior (sol-gel transition and scaling of storage modulus with aluminum concentration). The state boundaries are compared to alkali-activated materials from the literature including denser binders. This work focuses on two compositions of dilute gels, formulated to specifically quantify the effects of pH and aluminum concentration on gel microstructure and rheology. Gels formulated at constant pH of 12.5 show a change in morphology and silicon coordination, but consistent mass fractal dimension as aluminum concentration is increased. This microstructural behavior contrasts the characterization of gels previously formulated with a variable pH (range 3–11) which is dependent on aluminum concentration. These results inform the complicated interactions in the polycondensation reaction of alkali-activated binders and lead to a state diagram which unifies many structure-property observations reported for these materials. Structure-property relationships for two formulations of N-A-S-H gels are compared and plotted in a pseudo-ternary state diagram which includes other compositions of N-A-S-H gels and alkali-activated binders from the literature, shaded according to the scaling of the storage modulus where applicable. [Display omitted] [ABSTRACT FROM AUTHOR]

Abstract: An algorithm has been developed to create structural models for amorphous carbons using Monte Carlo simulations in the canonical ensemble. The simulation method used follows the experimental preparation of nanoporous carbons (NPC) by pyrolysis from polyfurfuryl alcohol as a guideline. The resulting structure exhibits properties that compare favorably to those observed experimentally for real NPCs. These atomistic NPC models are approaching a realistic representation of NPCs used for gas separations and as such, are being used to study the diffusion of small gas molecules in these materials. Limitations of the method and possible improvements are discussed. [Copyright &y& Elsevier]

Two colloidal suspensions of paucidisperse, spherical silica particles with different surface chemistries leading to extreme limits of surface contact friction are studied to identify experimental differences in shear rheology and microstructure and quantitatively test theory and simulation models. The nonequilibrium microstructure in the plane of shear is measured by flow-small angle neutron scattering for steady shear states spanning the shear thinning and shear thickening regimes. The shear rheology and microstructure are compared against predictions from theory for Brownian hard sphere suspensions and state-of-the-art simulation methods that incorporate either contact friction or enhanced lubrication hydrodynamics. The first normal stress differences are confirmed to distinguish between these micromechanical mechanisms for stress enhancement in the shear thickened regime. The nonequilibrium microstructure in the plane of shear shows more anisotropy for the suspension with higher interparticle friction. A significant fourfold symmetry is confirmed and found to be amplified with increasing surface contact friction in the shear thickened state. The differences in shear-induced microstructures between suspensions with varying contact friction demonstrate that the nonequilibrium microstructure can distinguish between nanotribological interactions in the shear thickened state. Statistical comparison of experiments with simulations indicates that better resolution of microstructures in simulation models is required to be validated by the experimental data presented. Implications for the development of theories for colloidal suspension rheology are discussed. [ABSTRACT FROM AUTHOR]

High-structured carbon fillers are ubiquitous as the conductive additive comprising suspension-based electrochemical energy storage technologies. Carbon black networks provide the necessary electrical conductivity as well as mechanical percolation in the form of a yield stress. Despite their critical role in determining system performance, a full mechanistic understanding of the relationship between the electrical transport characteristics of the percolated, conductive networks of carbon black, and the rheological properties is lacking, which hinders the rational design and optimization of flowable electrodes and the processing of electrolytes for batteries. Here, we report on the microstructural origin of the rheological and electrical properties of two commonly used conductive additives in neat propylene carbonate. From quiescent mechanical and structural studies, we find that the gelation of these carbon black suspensions is best described by the dynamic arrest of a clustered fluid phase. In contrast, the temperature and frequency dependence of the ac conductivity near this transition shows that mesoscale charge transport is determined by hopping between localized states that does not require a stress-bearing network. This unique combination of microstructural characterization with rheological and electrical measurements enables testing prevailing theories of the connection between electrical and mechanical percolation as well as improving conductive additives to enhance electrochemical performance. [ABSTRACT FROM AUTHOR]

The rheological characterization of a model, nearly ideal thixotropic carbon black suspension first proposed by Dullaert and Mewis (JNNFM 139: 21-30, 2006) is extended to include large amplitude oscillatory shear (LAOS) flow, shear flow reversal, and unidirectional LAOS flow (UD-LAOS). We show how this broader data set is useful for validating and improving constitutive models of thixotropy. We apply this new data to further test a recently developed structure-kinetics model, the Modified Delaware Thixotropy Model (Armstrong et al., J Rheol. 60: 433-450, 2016a), as well as to better understand the microstructural basis and validity of strain-rate superposition methods proposed for soft solids. This comparison identifies the limitations of models based on a scalar description of microstructure, which cannot fully capture the reversal of flow directionality inherent in LAOS flow. Further, we use the model to identify a possible microstructural justification for the hypothesized technique of strain-rate frequency superposition in soft solids. [ABSTRACT FROM AUTHOR]

In this work, we assess the capability of two thermodynamically consistent, microstructure-based models to predict the rheology and microstructure of a model wormlike micellar surfactant solution known to exhibit shear banding undergoing transient simple shear and large amplitude oscillatory shear deformations in a cylindrical Couette rheometer. The microstructure of the surfactant solution was simultaneously measured during the rheometric tests using small angle neutron scattering and this data is used along with the bulk rheometry to critically evaluate the models. The first model is a new, two-species model specifically developed for wormlike micelles, whereas the second model is the well-known Giesekus model with solvent and diffusion. The new model accounts for the microstructural dynamics including flow-induced micellar breakage and recombination, which is shown to be necessary to predict some of the measured rheology and microstructure. More species should be included to improve the quantitative comparison with experiments, as well as nonlinear relaxation, as judged by the success of the Giesekus model to represent certain features of the time-dependent data. More experimental research is needed to validate the role of flow-induced breakage in the nonlinear rheology of wormlike micellar surfactant solutions. [ABSTRACT FROM AUTHOR]

The rheology and shear-induced structures of a series of self-assembled surfactant wormlike micelles (WLMs) with varying levels of branching are measured using rheo- and flow-small angle neutron scattering (SANS). The degree of branching in the mixed cationic/anionic surfactant (cetyltrimethylammonium tosylate/sodium dodecyl benzene sulfonate) WLMs is controlled via the addition of the hydrotropic salt sodium tosylate and verified by cryo-transmission electron microscopy. The linear viscoelasticity of the low salt (linear) micellar solutions is well described as an extended Maxwell (Oldroyd-B) fluid, and samples exhibit shear banding under steady-shear flow. The linear viscoelasticity of more highly branched solutions deviates from Maxwellian behavior, where the plateau in G' gradually increases in slope with increasing salt content. The higher salt solutions exhibit a shear thinning regime, followed by a shear thickening regime at high shear rates. Micelle segmental alignment in the flow-gradient plane is a nonmonotonic function of salt level and radial position. Spatially resolved measurements of the segmental alignment corroborate shear banding in the linear WLMs, and the absence of shear banding with branching. Rheo-SANS measurements show that the onset of shear thickening at high rates corresponds to a structural transition. The results of this study link micellar microstructure and topology to the measured shear rheology of WLM solutions. [ABSTRACT FROM AUTHOR]

Recently, atypical static features of microstructural ordering in low-salinity lysozyme protein solutions have been extensively explored experimentally and explained theoretically based on a short-range attractive plus long-range repulsive (SALR) interaction potential. However, the protein dynamics and the relationship to the atypical SALR structure remain to be demonstrated. Here, the applicability of semi-analytic theoretical methods predicting diffusion properties and viscosity in isotropic particle suspensions to low-salinity lysozyme protein solutions is tested. Using the interaction potential parameters previously obtained from static structure factor measurements, our results of Monte Carlo simulations representing seven experimental lysoyzme samples indicate that they exist either in dispersed fluid or random percolated states. The self-consistent Zerah-Hansen scheme is used to describe the static structure factor, S(q), which is the input to our calculation schemes for the short-time hydrodynamic function, H(q), and the zero-frequency viscosity η. The schemes account for hydrodynamic interactions included on an approximate level. Theoretical predictions for H(q) as a function of the wavenumber q quantitatively agree with experimental results at small protein concentrations obtained using neutron spin echo measurements. At higher concentrations, qualitative agreement is preserved although the calculated hydrodynamic functions are overestimated. We attribute the differences for higher concentrations and lower temperatures to translational-rotational diffusion coupling induced by the shape and interaction anisotropy of particles and clusters, patchiness of the lysozyme particle surfaces, and the intra-cluster dynamics, features not included in our simple globular particle model. The theoretical results for the solution viscosity, η, are in qualitative agreement with our experimental data even at higher concentrations. We demonstrate that semi-quantitative predictions of diffusion properties and viscosity of solutions of globular proteins are possible given only the equilibrium structure factor of proteins. Furthermore, we explore the effects of changing the attraction strength on H(q) and η. [ABSTRACT FROM AUTHOR]

The microstructure-rheology relationship for a model, thermoreversible nanoparticle gel is investigated using a new technique of time-resolved neutron scattering under steady and timeresolved large amplitude oscillatory shear (LAOS) flows. A 21 vol. % gel is tested with varying strength of interparticle attraction. Shear-induced structural anisotropy is observed as butterfly scattering patterns and quantified through an alignment factor. Measurements in the plane of flow show significant, local anisotropy develops with alignment along the compressional axis of flow, providing new insights into how gels flow. The microstructure-rheology relationship is analyzed through a new type of structure-Lissajous plot that shows how the anisotropic microstructure is responsible for the observed LAOS response, which is beyond a response expected for a purely viscous gel with constant structure. The LAOS shear viscosities are observed to follow the "Delaware-Rutgers" rule. Rheological and microstructural data are successfully compared across a broad range of conditions by scaling the shear rate by the strength of attraction, providing a method to compare behavior between steady shear and LAOS experiments. However, important differences remain between the microstructures measured at comparatively high frequency in LAOS experiments and comparable steady shear experiments that illustrate the importance of measuring the microstructure to properly interpret the nonlinear, dynamic rheological response. [ABSTRACT FROM AUTHOR]

Highlights: [•] We study the formation of nanovesicles of cationic surfactant DEEDMAC. [•] A method to determine nanovesicle volume fraction is demonstrated. [•] The method is verified by neutron scattering measurements. [ABSTRACT FROM AUTHOR]

We present experiments and simulations that show a fundamental scaling for both the rheology and microstructure of flowing gels. Unique flow-SANS measurements demonstrate that the structure orients along both the neutral and compression axis. We quantify the anisotropy using a single parameter, α, that scales by a dimensionless number, M', that arises from a force balance on a particle. Simulations support the scalings and confirm the results are independent of the shape and range of the potential suggesting a universal for colloidal gels with short-ranged attractions. [ABSTRACT FROM AUTHOR]

We present direct measurements of the evolution of the segmental-level microstructure of a stable shear-banding polymerlike micelle solution during flow startup and cessation in the plane of flow. These measurements provide a definitive, quantitative microstructural understanding of the stages observed during flow startup: an initial elastic response with limited alignment that yields with a large stress overshoot to a homogeneous flow with associated micellar alignment that persists for approximately three relaxation times. This transient is followed by a shear (kink) band formation with a flow-aligned low-viscosity band that exhibits shear-induced concentration fluctuations and coexists with a nearly isotropic band of homogenous, highly viscoelastic micellar solution. Stable, steady banding flow is achieved only after approximately two reptation times. Flow cessation from this shear-banded state is also found to be nontrivial, exhibiting an initial fast relaxation with only minor structural relaxation, followed by a slower relaxation of the aligned micellar fluid with the equilibrium fluid's characteristic relaxation time. These measurements resolve a controversy in the literature surrounding the mechanism of shear banding in entangled wormlike micelles and, by means of comparison to existing literature, provide further insights into the mechanisms driving shear-banding instabilities in related systems. The methods and instrumentation described should find broad use in exploring complex fluid rheology and testing microstructure-based constitutive equations. [ABSTRACT FROM AUTHOR]

The rheological behavior and microstructure of branched, cationic wormlike micellar (WLM) solutions of 40 mM erucyl bis(hydroxyethyl)methylammonium chloride (EHAC) are studied as a function of added salt (sodium salicylate) concentration, temperature, and shear rate via Rheosmall-angle light scattering (Rheo-SALS). These WLM solutions exhibit shear-enhanced concentration fluctuations leading to shear-induced phase separation (SIPS), manifested as visual turbidity under shear and the appearance of a characteristic 'butterfly' scattering pattern in Rheo-SALS experiments. Flow kinematics measurements in a Couette geometry are used to determine the relationship between SIPS and shear banding, i.e., the splitting of the flow into shear bands with different local shear rates. Modeling using the Giesekus constitutive equation aids in discrimination between banding and nonbanding solutions. The combination of Rheo-SALS, dynamic rheology, velocimetry, and constitutive equation modeling allows detailed exploration of the relationship between SIPS, shear banding, fluid microstructure, and the equilibrium phase behavior. [ABSTRACT FROM AUTHOR]

The shear rheology of a model wormlike micellar solution exhibits moderate shear thinning and curved flow velocity profiles without discontinuity (nonbanding case). The shear rheology and the flow kinematics are analyzed within the framework of the Giesekus constitutive equation. Macroscopically, the steady state flow curve of the solution exhibits shear thinning with a shear exponent <1 without hysteresis, indicative of a sample that does not shear band. The microstructure of the micellar network is probed by the combination of dynamic rheology, rheo-optics, and SANS. Flow kinematics in a Couette geometry are measured by particle tracking velocimetry and found to be consistent with predictions of the Giesekus constitutive equation fit to the bulk shear rheology. 1-2 plane SANS measurements of the segmental alignment under shear are also found to be in agreement with predictions of the constitutive equation, providing a coherent picture of the mechanisms by which wormlike micelles flow and shear thin. The degree of segmental alignment is found to lag behind predictions of the model, which is postulated to be a consequence of the long, branched topology of the wormlike micelles. [ABSTRACT FROM AUTHOR]