We present important new results from light-microscopy and rheometry on a moderately concentrated lyotropic smectic, with and without particulate additives. Shear-treatment aligns the phase rapidly, except for a striking network of oily-streak defects, which anneals out much more slowly. If spherical particles several microns in diameter are dispersed in the lamellar medium, part of the defect network persists under shear-treatment, its nodes anchored on the particles. The sample as prepared has substantial storage and loss moduli, both of which decrease steadily under shear-treatment. Adding particles enhances the moduli and retards their decay under shear. The data for the frequency-dependent storage modulus after various durations of sheartreatment can be scaled to collapse onto a single curve. The elasticity and dissipation in these samples thus arises mainly from the defect network, not directly from the smectic elasticity and hydrodynamics.

We study the melt rheology and molecular weight distribution of four short chain branched hyperbranched polyesters with different molecular weights and containing branched monomers of various alkyl chain lengths n (2 f 4; n is the number of CH2 groups in the alkyl chain). We find that the molecular weight distribution for all our samples obeys the static scaling form n(M) ∼ Mτ exp(-M/Mchar) where n(M) is the number density of hyperbranched polymers with mass M, Mchar is the largest characteristic molecular weight, and τ is the polydispersity exponent. The values of τ for all our samples (either 1.35 or 1.55) are close to but not the same as the mean field value of τ ) 1.5, a consequence of the fact that our polymers were synthesized under non-mean-field polycondensation conditions. For all our samples, we found that the rheology at low and intermediate frequencies could be modeled accurately using a dynamic scaling theory based on the Rouse model. This confirms that these hyperbranched polymers behave as polymeric fractals which are essentially unentangled. For these polymers, the fractal dimension in the melt was found to be consistent with the hyperscaling relation for hyperbranched polymers d f ) 3, although we found rheology to be rather insensitive to df for our system.

We present new non-linear data in extension and two different shear histories. These data are used to compare the effectiveness of using exponential shear data and uniaxial extension data to characterise the non-linear response of an industrial LDPE melt with the pom-pom molecular model. We conclude that extension and exponential shear both allow good predictions to be made in simple shear. However, the characterisation spectrum obtained from exponential shear data fails to predict the correct degree of strain hardening at low extension rates. From this study we are able to suggest circumstances under which exponential shear provides a useful characterisation of branched polymer melts.