Morphology of a highly asymmetric double crystallizable poly(epsilon-caprolactone-b-ethylene oxide) block copolymer

The morphology of a highly asymmetric double crystallizable poly(epsilon-caprolactone-b-ethylene oxide) (PCL-b-PEO) block copolymer has been studied with in situ simultaneously small and wide-angle x-ray scattering as well as atomic force microscopy. The molecular masses Mn of the PCL and PEO blocks are 24,000 and 5800, respectively. X-ray scattering and rheological measurements indicate that no microphase separation occurs in the melt. Decreasing the temperature simultaneously triggers off a crystallization of PCL and microphase separation between the PCL and PEO blocks. Coupling and competition between microphase separation and crystallization results in a morphology of PEO spheres surrounded by PCL partially crystallized in lamella. Further decreasing temperature induces the crystallization of PEO spheres, which have a preferred orientation due to the confinements from hard PCL crystalline lamella and from soft amorphous PCL segments in different sides. The final morphology of this highly asymmetric block copolymer is similar to the granular morphology reported for syndiotactic polypropylene and other (co-) polymers. This implies a similar underlying mechanism of coupling and competition of various phase transitions, which is worth further exploration.     

Autosoliton model of the spinning fronts of reaction

Experiments with reaction fronts (detonation waves and solidflames) reveal that, near the combustion limit, the fronts movein a spinning regime when localized zones of intensive reactiontravel along spiral trajectories. In the paper, the spinningwave is interpreted as an autosoliton and described phenomenologicallyby a nonlinear partial differential equation. The equation isstudied numerically, and the presence of the stable spinningand autosoliton solutions is shown.     

Dynamic properties of microemulsions modified with homopolymers and diblock copolymers: the determination of bending moduli and renormalization effects

The properties of bicontinuous microemulsions, consisting of water, oil, and a surfactant, can be modified by the addition of diblock copolymers (boosting effect) and homopolymers (inverse boosting effect) or a combination of both. Here, the influence of the addition of homopolymers (PEP(X) and PEO(X), X=5k or 10k molecular weight) on the dynamics of the surfactant layer is studied with neutron spin echo spectroscopy (NSE). Combining the results with the previous findings for diblock copolymers allows for a better separation of viscosity and bending modulus effects. With the addition of homopolymers, a significant increase of the relaxation rate compared to the pure microemulsion has been observed. The influence on the bending rigidity kappa is measured with NSE experiments. Homopolymer addition reduces kappa by up to Deltakappa approximately -0.5k(B)T, whereas the diblock copolymer yields an increase of kappa by approximately 0.3k(B)T. Comparison of the bending moduli that are obtained by analysis of the dynamics to those obtained from small angle neutron scattering (SANS) sheds light on the different renormalization length scales for NSE and SANS. Variation of the surfactant concentration at otherwise constant conditions of homopolymer or diblock-copolymer concentration shows that NSE results are leading to the pure bending rigidity, while the renormalized one is measured with SANS.