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

The 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]

Abstract: A micromechanical model for the zero shear viscosity of polyampholyte-stabilized colloidal dispersions based on the osmotic overlap potential is proposed and tested against model system measurements. This model relates the shear viscosity of polyampholyte-stabilized colloidal dispersions to the oncotic pressure of polyampholyte solutions through an interparticle potential and an effective hard-sphere scaling. The results of viscosity calculations based on independently measured parameters compare favorably to experimental measurements on model, silica dispersions stabilized with adsorbed photographic grade gelatin. The results support a direct link between the capacity of polyampholytes and polyelectrolytes to stabilize dispersions and control dispersion viscosity and their solution oncotic pressure. The model is also demonstrated to provide a master curve for literature data for the zero shear viscosity of polyampholyte stabilized colloidal dispersions. [Copyright &y& Elsevier]

The adsorption of monoclonal antibodies (mAbs) on hydrophobic surfaces is known to cause protein aggregation and degradation. Therefore, surfactants, such as Poloxamer 188, are widely used in therapeutic formulations to stabilize mAbs and protect mAbs from interacting with liquid-solid interfaces. Here, the adsorption of Poloxamer 188, one mAb and their competitive adsorption on a model hydrophobic siliconized surface is investigated with neutron scattering coupled with contrast variation to determine the molecular structure of adsorbed layers for each case. Small angle neutron scattering measurements of the affinity of Poloxamer 188 to this mAb indicate that there is negligible binding at these solution conditions. Neutron reflectometry measurements of the mAb show irreversible adsorption on the siliconized surface, which cannot be washed off with neat buffer. Poloxamer 188 can be adsorbed on the surface already occupied by mAb, which enables partial removal of some adsorbed mAb by washing with buffer. The adsorption of the surfactant introduces significant conformational changes for mAb molecules that remain on the surface. In contrast, if the siliconized surface is first saturated with the surfactant, no adsorption of mAb is observed. Competitive adsorption of mAb and Poloxamer 188 from solution leads to a surface dominantly occupied with surfactant molecules, whereas only a minor amount of mAb absorbs. These findings clearly indicate that Poloxamer 188 can protect against mAb adsorption as well as modify the adsorbed conformation of previously adsorbed mAb. [ABSTRACT FROM AUTHOR]

Molecular engineering facilitates the development of a complex fluid with contradictory requirements of yield stress and sprayability, while minimizing the amount of structuring material (<0.05 wt%). This unique system can be achieved by a biopolymer hydrogel with tunable inter- and intra-molecular interactions for microstructural robustness and molecular extensibility by the variation of chemical conformations that microstructure breaks up under shear followed by a low molecularly extensible response. Blends of xanthan and konjac glucomannan containing 99.95 wt% water are demonstrated to satisfy these contradictory requirements and formulated as a function of KCl concentrations. A systematic study was performed using shear and extensional rheology and compared to a reference solution of polyethylene oxide (PEO), a well-known, Boger fluid, highlights the role of molecular elasticity in controlling critical rheological properties. Static light scattering (SLS) and simultaneous rheology and small-angle neutron scattering (RheoSANS) are also used to elucidate the equilibrium structure and flow dynamics. The blends exhibit a lower yield stress and extensional resistance with added KCl, which leads to good spray characteristics in contrast to strain-hardening PEO. The results suggest that the inter-molecular attractions between the two gums leading to network formation with appropriate stiffness, that break up readily under shear, and low molecular elasticity are critical molecular design parameters necessary to achieve sprayable, yields stress fluids. [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]

Abstract: We present a systematic study of the self-assembly of wormlike micelles (WLMs) comprised of cetyltrimethylammonium bromide (CTAB) and sodium nitrate (NaNO3) in aqueous solution as a function of CTAB concentration, NaNO3 concentration, and temperature throughout the dilute and semi-dilute regions of the phase diagram where linear micelles are observed. Combining measurements using isothermal titration calorimetry, rheometry, flow-birefringence, cryo-transmission electron microscopy (cryo-TEM), and small angle neutron scattering (SANS) enables complete characterization of the structure, thermodynamics, and rheology of CTAB/NaNO3 micelles. The addition of NaNO3 is found to increase the micellization enthalpy as well as the micellar scission energy, resulting in the elongation and growth of WLMs. We find quantitative agreement between the scission energy determined from rheology and the enthalpy of micellization determined from ITC, as well as for contour lengths extracted from rheology and SANS. At fixed molar ratio of NaNO3 and CTAB, the solution rheology exhibits scaling consistent with dilute, semi-dilute overlapping, and semi-dilute entangled regimes typically found in polymer solutions, as confirmed by cryo-TEM and SANS. The transition between these scaling regimes coincides with the structural transitions identified by SANS. The results validate the relationship between structural parameters and rheological behavior underlying theories for ionic WLMs. [Copyright &y& Elsevier]

The stability of dilute bimodal (diameter:100 and 200 nm) model latex dispersions is studied as a function of electrolyte concentration and particle number fraction by measuring perikinetic aggregation with dynamic light scattering. A formally correct expression for the effective, doublet stability ratio of a bimodal system is derived that accounts for the difference in the particle size and hence, extends the derivation by Hogg and co-workers [Trans. Faraday Soc. 62 (1966) 1638]. Including the particle size ratio predicts slightly lower stability ratios for polydisperse but chemically similar systems. Stability ratios for binary mixtures of model colloidal latices are extracted from aggregation measurements in the fractal aggregation regime and are compared to predictions based on DLVO calculations of the potential. The results suggest that the composition of the aggregates is dependent on the relative stability of the two components (and consequently, on electrolyte concentration) and is richer in the least stable component. [Copyright &y& Elsevier]