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A tooth rheometer designed to investigate the influence of large amplitude oscillatory shear on the macroscopic orientation of complex fluids is described. The rheometer allows in-situ two-directional small-angle scattering measurements, making it possible to observe in particular the orientation process of hierarchically structured block copolymers in dynamics. Experiments performed with a linear poly(vinyl methyl ether) show that, despite a considerable gap/width ratio, the rheometer can be used for adequate rheological measurements. In addition we found an unexpected dependence of the dynamic parameters on the rheometer gap. The small amount of sample required favors the use of this rheometer for measuring the rheological characteristics of new compounds.

Summary: Using the bond fluctuation model (BFM), simulations have been performed on molecular bottle brushes with two chemically different types of side chains. In the first part of this work, rigidity of the backbone is imposed. The influence of solvent quality and side chain length on the intramolecular phase separation of side chain material, leading to Janus cylinders, has been investigated and compared to theoretical predictions. In the second part of this work, the restriction of rigidity for the backbone is relaxed. In a poor solvent, the side chain material collapses into a globular state. Several globules containing each one type of side chain material are connected together by backbone material. When imposing different solvent conditions for both types of side chains, a bending of the backbone is found as predicted by theory and observed in very recent experiments. Comparison between typical snapshots in θ solvent. The side chain length is 25 beads. Dark and light coloured side chains repel each other.

Combination of self-assembly at different length scales leads to structural hierarchies. It offers rich possibilities to construct nanostructured matter, nanoscale parts, and switching (responsive) properties based on the phase transitions of the self-assembled structures. Complexation of oligomeric amphiphiles to polymers using ionic interactions, coordination, or hydrogen bonding leads to polymeric comb-shaped supramolecules (complexes), which self-assemble at a length scale of a few nm. Self-assembly at an order of magnitude larger length scale is provided by block copolymers, and combination of the latter two concepts leads to structural hierarchies. They provide e.g. templates for mesoporous materials and nano-objects, and allow switching conductivity and switching optical properties. Structural hierarchies are also observed by complexing moderately monodisperse polymeric rods with amphiphiles. Finally, self-assembly at even a larger length scale upon using colloidal particles may be combined to the above structures, as encouraged by recent observations.

Several alkyl side chains are bonded to each polymeric repeat unit using both coordinated ligands and electrostatically bound counterions to directly control the interface curvature of the self-organized structures. 2,6-Bis(octylaminomethyl)pyridine is Zn-coordinated to poly(4-vinylpyridine) (P4VP) with dodecylbenzenesulfonate (DBS) counterions, leading to multicomb polymeric supramolecules, poly[(4VP)Zn(2,6-bis(octylaminomethyl)pyridine)(DBS)2]. Coordination is evidenced by infrared spectroscopy and visualized by quantum chemical calculations. The amorphous hexagonal self-organized structures are characterized using X-ray measurements.

A Monte Carlo study is presented to discuss the influence of the side-chain topology on the enhancement of the persistence length of a molecular bottle-brush in a dilute athermal solution due to the excluded volume interactions between the side chains. The structures investigated consisted of freely jointed backbones of 100 hard spheres (beads) of diameter 1 to which 50 equally flexible side chains were grafted. The diameter of the side-chain beads was varied from 1 to 3 in the same units. For every given size of the side-chain bead, the length of the side chains was varied from 4 to 20 beads. The ratio between the persistence length and the bottle-brush diameter, which is the determining factor for lyotropic behavior of conventional semi-flexible chains, was found to be almost independent of the side-chain length. At the same time, it was found to increase considerably with increasing size of the side-chain beads, suggesting that by a proper choice of the chemistry lyotropic behavior of molecular bottle-brushes due to excluded-volume interactions between the side chains might be achieved. Moreover, relatively short side chains can be used since the side-chain length has only a minor influence on the ratio between the persistence length and the diameter. These findings are in a good agreement with recent experimental observations.

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