Andreas Korwitz

In situ Synthesis of Poly(ethylene terephthalate)/layered Silicate Nanocomposites by Polycondensation

The goal of the work presented here was to develop nanocomposites consisting of layered silicates and poly(ethylene terephthalate) (PET). Two nanocomposite preparation methods were compared: first, the usual melt compounding technique, and second, in-situ synthesis of PET in presence of different types of layered silicates. Montmorillonite (MMT) without and with organophilic modification was employed as layered silicate. In most cases, PETs with acceptable properties (molecular weight and discoloration) were synthesized in presence of different MMTs although the molecular weights of the in-situ PETs were lower than the control sample. These materials were used as masterbatch for PET nanocom-posites with 5 wt.% inorganic content. The exfoliation in both types of nanocomposites was not complete, but they showed a good distribution of clay within the polymer matrix.

The miscibility of poly(butylene terephthalate) (PBT) with phosphorus polyester flame retardants

Phosphorus polyesters provide sustainable flame retardancy to conventional polyesters like PET (poly(ethylene terephthalate)) and PBT (poly(butylene terephthalate)). Their use as a flame retardant additive results in the formation of a classical polymer blend. The morphology of such blends should determine the resulting fire behavior and has therefore to be examined in detail. This study investigates the state of miscibility in blends of standard polyesters (mainly PBT) with phosphorus (co)polyesters mainly using the behavior of the glass transition (T g). The T g values were determined by modulated DSC measurements and compared to the ones calculated assuming complete miscibility according to the Fox–Flory concept. The homopolyesters are completely immiscible with each other. Miscibility can be improved by transesterification reactions in the melt as well as by copolyester consisting of segments of PBT or PET and the phosphorus polymer.

Temperature dependant structural changes in thin films of random semifluorinated PMMA copolymers

Semifluorinated (SF) side chain polymers show phase separation between polymer backbone and SF side chains. Due to strong interaction between SF segments the side chains determine the structure behaviour strongly, often resulting in layered structures in which backbones and layers of SF side chains alternate. The interest in this work was directed to find out the dependence of these structures on concentration of SF side chains. Thin films of random copolymers consisting of methylmethacrylate (MMA) and semifluorinated side chain methacrylate (SFMA) segments and with different fluorine content in the perfluoroalkyl side chains (abbreviated as H10F10 and H2F8) were prepared by spin-coating. Phase separation and structure changes were initiated by external subsequent annealing. Corresponding bulk material served as basic information. Generation of ordered structures and variation of film parameters were observed using different X-ray scattering methods (XRR, GIWAXS, and GISAXS). The phase behaviour in bulk is governed by the SF side chain amount and their specific fluorine content which control the self-organization tendency of SF side chains. Additionally, the confinement in thin films generates an orientation of side chains normally to film surface. Key words: T-dependant X-ray scattering, GISAXS, phase separation, thin films, random copolymers, semifluorinated polymers a) Author to whom correspondence should be addressed. Electronic mail: djeh@ipfdd.de

Effects of nanoparticles on phase morphology in thin films of phase-separated diblock copolymers

This study investigates the morphology changes in thin diblock copolymer (DiBCP) films occurring in the interaction with modified nanoparticles (NPs). Magnetite (Fe 3 O 4 ) and silica (SiO x ) were prepared and used. Poly(pentyl methacrylate-b-methyl methacrylate) (PPMA-b-PMMA) (70/30 mol mol −1 , hcp cylinders of the PMMA phase) DiBCP were employed to prepare thin films having thicknesses to realize standing cylinders in pure DiBCP films. The investigations aimed at two topics: (1) morphology after controlled incorporation of organo-modified NP (gold, silver, Fe 3 O 4 , SiO x ) and (2) additional solvent vapour annealing (SVA) with tetrahydrofuran (and chloroform for comparison). The laterally ordered morphology in thin films was examined by GISAXS and atomic force microscopy. Keeping the same type of morphology in nanocomposites, the dimensions of the periodic nanostructure altered depending on type and amount of incorporated NP. It was found that SiO x clusters enlarge the lateral distance of the PMMA cylinders, whereas metallic NPs reduce this parameter. Applying SVA improves the phase separation slightly, whereas lateral distances were kept constant or were reduced a little. Switching of domain orientation upon SVA could not be detected in the presence of NPs located at the polymer/substrate interface.