M. C. Newstein

Microstructural changes in a colloidal liquid in the shear thinning and shear thickening regimes

The structure of a colloidal suspension under shear flow was studied by in situ small angle neutron scattering (SANS). This suspension exhibited shear thinning at low shear rates and shear thickening at high shear rates. Under quiescent conditions, the SANS profiles were azimuthally symmetric and contained a well-defined scattering maximum. This is due to local, liquidlike correlations between neighboring particles. Increasing shear rate lead to changes in the interparticle correlations. These changes are quantified by obtaining the anisotropic structure factor of the suspension under shear flow. We found an increased probability for the formation of inter-particle clusters in the gradient-vorticity plane. This results in an increase in the low angle scattering intensity in the flow direction, and the scattering peak, observed under quiescent conditions, is reduced to a shoulder. We found no evidence for a shear-induced phase transition in our experimental window. At low shear rates (γ), the microstructu...

Effect of quench depth on grain structure in quiescently ordered block copolymers

Grain growth in a polystyrene–polyisoprene block copolymer melt is studied by time-resolved depolarized light scattering after a quiescent quench from the disordered to the ordered state. At shallow quench depths, classical nucleation and growth kinetics are observed. Grains comprising the equilibrated ordered phase nucleate and grow by consuming the surrounding disordered phase. In contrast, deep quenches result in the formation of disorganized grains with an average order parameter that is well below the equilibrium value. Small angle neutron scattering and rheological experiments were conducted to facilitate the interpretation of the light scattering data. We show that the nonequilibrium grain structure formed during deep quenches is due to extremely high nucleation density. Under these circumstances, the space required for the formation of equilibrated grains is unavailable.

Kinetics of microemulsion formation in polymer mixtures

The kinetics of microemulsion formation in a multicomponent blend of two homopolymers and a block copolymer was studied by neutron scattering. The scattering profiles indicate the presence of large length-scale defects that coexist with the periodic microemulsion. With time, the large-scale structures undergo coarsening, while the periodic structures undergo refinement, i.e., they become more organized. The defect density at a given temperature can be controlled to some extent by thermal history.

Characterization of a Block Copolymer with a Wide Distribution of Grain Sizes

Block copolymer/lithium salt mixtures are an emerging class of lithium battery electrolytes. Previous studies have shown that the ionic conductivity of these materials is a sensitive function of grain size. Both depolarized light scattering (DPLS) and small-angle X-ray scattering (SAXS) have proven to be effective techniques for elucidating the grain structure of block copolymer (BCP) materials. DPLS is particularly useful for the characterization of samples with grain sizes larger than 1 μm, whereas SAXS is particularly well suited for samples with grain sizes smaller than 0.1 μm. We present the results of both DPLS and SAXS measurements of grain structure in a BCP/lithium salt mixture that was annealed after being initially prepared by freeze-drying from solution. The combination of the two techniques demonstrates that our sample is characterized by an extremely wide distribution of grain sizes. In particular, the sample has a large population of small sub-micrometer-sized grains that cannot be detected...