Effect of interlamellar interactions on shear induced multilamellar vesicle formation.

Shear-induced multilamellar vesicle (MLV) formation has been studied by coupling the small-angle neutron scattering (SANS) technique with neutron spin echo (NSE) spectroscopy. A 10% mass fraction of the nonionic surfactant pentaethylene glycol dodecyl ether (C12E5) in water was selected as a model system for studying weak inter-lamellar interactions. These interactions are controlled either by adding an anionic surfactant, sodium dodecyl sulfate, or an antagonistic salt, rubidium tetraphenylborate. Increasing the charge density in the bilayer induces an enhanced ordering of the lamellar structure. The charge density dependence of the membrane bending modulus was determined by NSE and showed an increasing trend with charge. This behavior is well explained by a classical theoretical model. By considering the Caillé parameters calculated from the SANS data, the layer compressibility modulus B¯ is estimated and the nature of the dominant inter-lamellar interaction is determined. Shear flow induces MLV formation around a shear rate of 10 s-1, when a small amount of charge is included in the membrane. The flow-induced layer undulations are in-phase between neighboring layers when the inter-lamellar interaction is sufficiently strong. Under these conditions, MLV formation can occur without significantly changing the inter-lamellar spacing. On the other hand, in the case of weak inter-lamellar interactions, the flow-induced undulations are not in-phase, and greater steric repulsion leads to an increase in the inter-lamellar spacing with shear rate. In this case, MLV formation occurs as the amplitude of the undulations gets larger and the steric interaction leads to in-phase undulations between neighboring membranes.

Colloidal Nanoparticle Interaction Transition during Solvent Evaporation Investigated by in-Situ Small-Angle X-ray Scattering.

In-situ scanning small-angle X-ray scattering (SAXS) experiments have been performed to probe the drying of a single suspended droplet of silica colloids. It has been demonstrated that the formation of a nanoparticle shell during drying can be confirmed just by measuring the temporal evolution of the spatial transmission profile across the drying droplet. The shrinkage of the droplet stops once the shell is formed. The temporal dependence of the shell thickness and droplet radius has been estimated by quantitative analysis of the functionality of the transmission profiles. It is revealed that the position of the correlation peak originating from interactions between silica nanoparticles evolves linearly during the initial stage of drying and exhibits sigmoidal growth behavior in later stages. The interaction between colloidal particles in different drying stages has been investigated. We provide experimental confirmation of the transition from repulsive interaction to a capillary-driven short-range attraction during shell formation. The present work demonstrates that in-situ scanning SAXS on a suspended droplet is an invaluable technique for monitoring the dynamic self-organization of colloids as it probes the drying of complex fluids without the interference of a substrate.

Chain conformation in polymer nanocomposites with uniformly dispersed nanoparticles.

The effect of nanoparticles (NP) on chain dimensions in polymer melts has been the source of considerable theoretical and experimental controversy. We exploit our ability to ensure a spatially uniform dispersion of 13 nm silica NPs miscible in polystyrene melts, together with neutron scattering, x-ray scattering, and transmission electron microscopy, to show that there is no measurable change in the polymer size in miscible mixtures, regardless of the relative sizes of the chains and the nanoparticles, and for NP loadings as high as 32.7 vol%. Our results provide a firm basis from which to understand the properties of polymer nanocomposites.

Small-angle neutron scattering for in†situ probing of ion adsorption inside micropores.

Confined ions: The high penetrating power and sensitivity of neutron scattering to isotope substitution are harnessed to observe changes in the ion concentration in a porous carbon material as a function of the applied potential and the pore size. Depending on the solvent properties and the solvent-pore-wall interactions, either enhanced or reduced ion electroadsorption may take place.

Polymer dimensions in good solvents: crossover from semidilute to concentrated solutions.

Using small-angle neutron scattering, we studied the variation of the polymer radius of gyration (R_{g}) as a function of polymer concentration (varphi) for solutions of a flexible-chain poly(methyl methacrylate) in chloroform. We observed for the first time a distinct crossover between swollen coils in the semidilute regime, where R_{g};{2} proportional, variantvarphi;{-0.26+/-0.03}, and unperturbed coils in the concentrated regime, where R_{g} is independent on concentration. The crossover occurs at varphi;{double dagger} approximately 0.15, a value that agrees reasonably well with varphi;{double dagger} approximately 0.21 +/- 0.035, estimated with a scaling relationship between varphi;{double dagger} and the coil overlap concentration varphi;{*}.

Adsorption of supercritical CO2 in aerogels as studied by small-angle neutron scattering and neutron transmission techniques.

Small-angle neutron scattering (SANS) has been used to study the adsorption behavior of supercritical carbon dioxide (CO2) in porous Vycor glass and silica aerogels. Measurements were performed along two isotherms (T=35 and 80 degrees C) as a function of pressure (P) ranging from atmospheric up to 25 MPa, which corresponds to the bulk fluid densities ranging from rho(CO2) approximately 0 to 0.9 gcm3. The intensity of scattering from CO2-saturated Vycor porous glass can be described by a two-phase model which suggests that CO2 does not adsorb on the pore walls and fills the pore space uniformly. In CO2-saturated aerogels an adsorbed phase is formed with a density substantially higher that of the bulk fluid, and neutron transmission data were used to monitor the excess adsorption at different pressures. The results indicate that adsorption of CO2 is significantly stronger in aerogels than in activated carbons, zeolites, and xerogels due to the extremely high porosity and optimum pore size of these materials. SANS data revealed the existence of a compressed adsorbed phase with the average density approximately 1.07 gcm3, close to the density corresponding to closely packed van der Waals volume of CO2. A three-phase model [W. L. Wu, Polymer 23, 1907 (1982)] was used to estimate the volume fraction phi3 of the adsorbed phase as a function of the fluid density, and gave phi3 approximately 0.78 in the maximum adsorption regime around rho(CO2) approximately 0.374 gcm3. The results presented in this work demonstrate the utility of SANS combined with the transmission measurements to study the adsorption of supercritical fluids in porous materials.

Density fluctuations near the liquid-gas critical point of a confined fluid.

We report the results of an experimental study of the effect of a dilute silica network on liquid-gas critical phenomena in carbon dioxide (CO2). Using small-angle neutron scattering, we measured the correlation length of the density fluctuations in bulk (xi(bulk)) and confined CO2 (xi(conf)) as a function of temperature and average fluid density. We find that quenched disorder induced by an aerogel suppresses density fluctuations: xi(conf) loses the Ising model divergence characteristic of xi(bulk) and does not exceed the size of pores in the homogeneous region.

Universal aspects of macromolecules in polymer blends, solutions, and supercritical mixtures.

We demonstrate that macromolecules in miscible polymer blends may behave as good, Theta, and poor polymeric solvents for each other. We construct a conceptual phase diagram, delineating the range of validity of the random-phase approximation, outside of which polymers contract or expand beyond their unperturbed dimensions, contrary to common assumptions. Remarkably, the correlation length for polymer blends, solutions, and supercritical mixtures collapses onto a master curve, reflecting universal behavior for macromolecules in polymeric and small-molecule Theta solvents.