Rigid Rod Polymers Having Flexible Side Chains. 3. Structural Investigations on a Novel Layered Mesophase Formed by Thermotropic Poly(1,4-phenylene-2,5-dialkoxy terephthalate)s

A series of thermotropic poly(1,4-phenylene-2,5-di-n-alkoxy terephthalate)s with the length of the n-alkoxy side chains being varied between n = 2 and n = 18 carbon atoms has been examined by optic...

Residual Stresses in Glasses

The history dependence of the glasses formed from flow-melted steady states by a sudden cessation of the shear rate $\dot\gamma$ is studied in colloidal suspensions, by molecular dynamics simulations, and mode-coupling theory. In an ideal glass, stresses relax only partially, leaving behind a finite persistent residual stress. For intermediate times, relaxation curves scale as a function of $\dot\gamma t$, even though no flow is present. The macroscopic stress evolution is connected to a length scale of residual liquefaction displayed by microscopic mean-squared displacements. The theory describes this history dependence of glasses sharing the same thermodynamic state variables, but differi…

Crystallization-induced switching of the morphology of poly(ethylene oxide)-block-polybutadiene micelles

We studied the morphology of micelles formed by a well-defined poly(1,2-butadiene)-block-poly(ethylene oxide) diblock copolymer (PB-b-PEO). Dissolved in n-heptane at 70 °C, that is, above the melting point of PEO, spherical micelles are formed due to the selectivity of the solvent for the PB-block. If the solutions are cooled down to low temperatures, the liquid PEO-block crystallizes within the cores of the spherical micelles that remain stable. If, however, the solutions are quenched to 30 °C, the spherical micelles aggregate to a novel meander-like structure within several minutes. In its final state, the meander-like super-structure is crystalline, as revealed by time-resolved wide-angl…

Polymides 3a and 3b with stiff-chains bearing trioxaoctyl or tetraoxaundecyl side chains were synthesized and characterized. The polycondensation was done with pyromellitic anhydride and N,N′-bis(1-imidazolylcarbonyl)-2,5-(1,4,7-trioxaoctyl)- or 2,5-(1,4,7,10-tetraoxaundecyl)-1,4-phenylenediamine (2a or 2b). 3b, being sufficiently soluble, was characterized by 13C NMR spectroscopy. The results of IR and 13C NMR spectroscopy prove the presence of the correct imide structure. In solid state 3a and 3b form layered structures with the side chains being in a disordered state.

Residual order in amorphous dry films of polymer latices: indications of an influence of particle interaction

Abstract We report small angle X-ray scattering and atomic force microscopy measurements on macroscopically thick, dry films of polymer latex particles. While the surface of dried droplets has long range order due to layering effects, the overall bulk structure is amorphous. This holds for both low charge polymethylmetacrylate particles and for highly charged polystyrene particles with additional stabilisation with sodiumdodecylsurfate. In the latter case, however, considerable amounts of residual crystal-like order is observed.

Vitrification in restricted geometry: dry films of colloidal particles

We prepared dry films of colloidal particles from surfactant co-stabilized polystyrene and poly(methyl methacrylate) latex spheres of moderate polydispersity. The film thickness was varied from monolayer to some 20 μm. The average structure and the influence of polydispersity was analyzed by small-angle X-ray scattering. An analysis of local microscopic structures was performed by force microscopy on the least polydisperse sample. Irrespective of the thickness, we observe the formation of only short-ranged order which is rather pronounced but changes its qualitative character in the vicinity of the substrate. The observations suggest a bulk structure of small, defect-rich and stacking fault…

Tribute to Axel Müller on the occasion of his 65th birthday