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An improved population balance‐based rheological constitutive framework for polydisperse aggregating suspensions is derived by incorporating detailed models for orthokinetic and perikinetic aggregation and shear breakage processes. The framework accounts for critical properties such as dynamic arrest, viscoelasticity, kinematic hardening, thixotropy, and yield stress to generate a full range of thixotropic elasto‐viscoplastic (TEVP) response. Additionally, the model is thermodynamically consistent because the dynamics and timescales are completely determined by internal structural and kinetic variables. The model connects the rheological response to the structural descriptors such as the size distribution of agglomerates, mean sizes, fractal dimension, and agglomerate volume fraction. Predictions are compared against a wide range of shear rheology measurements data for model thixotropic suspensions of fumed silica and carbon black, including large amplitude oscillatory shear (LAOS), as well as ultra‐small angle neutron scattering under steady shear (Rheo‐uSANS). [ABSTRACT FROM AUTHOR]

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]

Carbon black suspensions exhibit complex, shear-dependent macroscopic properties that are a consequence of the state of the suspension microstructure. In this work, the shear-induced microstructure of a model, reversible suspension of conductive carbon black in propylene carbonate is measured using simultaneous steady shear rheology and small angle neutron scattering. These experiments provide microstructural evidence for a bifurcation in the rheological properties. We show that the demarcation line for this bifurcation is the inverse Bingham number, Bi−1, which relates the magnitude of the stress response to an applied shear rate to the yield stress of the presheared suspension. At high shear rates where Bi−1 > 1, the suspension flows homogeneously and exhibits a thixotropic response that arises due to the self-similar breakdown of agglomerates with increasing shear rate. Conversely, at low shear rates where Bi−1 < 1, the applied shear drives the densification and growth of these agglomerates. This densification process leads to a gravitationally driven instability resulting in an inhomogeneous volume fraction distribution along the height of the geometry that is a function of both time under shear and shear rate. Under these shear conditions, the suspension exhibits apparent rheopexy, or antithixotropy, where a significant decline in the viscosity is observed with a step down in shear rate. The unique microstructural measurements presented here reconcile many observations in the literature regarding carbon black suspensions, including an apparent shear-thickening behavior, tunability of both the yield stress and elasticity through shear history, and transient macroscopic properties. [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]

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]

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]

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]

The rheology and particle alignment of suspensions of anisotropic-precipitated calcium carbonate particles of various aspect ratios is investigated using small-angle neutron scattering simultaneous with rheological measurement (Rheo-SANS). Rheo-SANS experiments were performed at concentrations from dilute to those exhibiting continuous and discontinuous shear thickening behavior. Long axis flow alignment is evident in all systems over the range of shear rates investigated. The flow alignment is shown to increase with particle aspect ratio, the applied shear stress (up to the point of shear thickening), and particle loading. For samples exhibiting shear thickening behavior, the highest degree of flow alignment occurs at the critical stress associated with the onset of shear thickening. Irrespective of particle aspect ratio, a gradual reduction in flow alignment with increasing applied stress is observed beyond the critical stress in continuously shear thickening samples, whereas discontinuously shear thickening samples maintain nearly the same degree of flow alignment within the shear thickening regime. The results are shown to be consistent with hydrocluster formation as the mechanism of shear thickening. The critical volume fraction for discontinuous shear thickening is shown to coincide with the equilibrium isotropic-nematic phase transition at higher aspect ratios. [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]

Recently, reversible cluster formation was identified as an underlying cause of anomalously large solution viscosities observed in some concentrated monoclonal antibody (mAb) formulations, which poses a major challenge to the use of subcutaneous injection for some mAbs. A fundamental understanding of the structural and dynamic origins of high viscosities in concentrated mAb solutions is thus of significant relevance to mAb applications in human health care, as well as being of scientific interest. Herein, we present a detailed investigation of an IgG1-based mAb to relate the short-time dynamics and microstructure to significant viscosity changes over a range of pharmaceutically relevant physiochemical conditions. The combination of light scattering, small-angle neutron scattering, and neutron spin echo measurement techniques conclusively demonstrates that, upon addition of Na2SO4, these antibodies form strongly bound reversible dimers at dilute concentrations that interact with each other to form large, loosely bound, transient clusters when concentrated. This hierarchical structure formation in solution causes a significant increase in the solution viscosity. [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]

Shear-induced structural transitions of a micellar cubic phase during large amplitude oscillatory shear flow is studied with time-resolved oscillatory rheological small angle neutron scattering. This technique allows us to resolve the structural changes within a cycle of oscillation. By applying a strain rate near the critical melting shear rate, melting and recrystallization occurs in a cyclic mode. The maximum degree of order is observed when the shear stress reaches a plateau value during the large amplitude oscillatory shear cycle, whereas melting is maximized at the strain rate wave peaks. This structural evolution confirms the cyclic mechanism of sticking and sliding of 2D hexagonal close-packed layers [I. W. Hamley et al, Phys. Rev. E 58, 7620 (1998)]. [ABSTRACT FROM AUTHOR]