Björn Kuttich

Form fluctuations of polymer loaded spherical microemulsions studied by neutron scattering and dielectric spectroscopy

We investigate the structure and shell dynamics of the droplet phase in water/AOT/octane microemulsions with polyethyleneglycol (MW = 1500) molecules loaded in the droplets. Size and polydispersity of the droplets is determined with small angle X-ray scattering and small angle neutron scattering experiments. Shell fluctuations are measured with neutron spin echo spectroscopy and related to the dynamic percolation seen in dielectric spectroscopy. Shell fluctuations are found to be well described by the bending modulus of the shell and the viscosities inside and outside the droplets. Addition of the polymer decreases the modulus for small droplets. For large droplets the opposite is found as percolation temperature shifts to higher values.

Polymer loaded microemulsions: Changeover from finite size effects to interfacial interactions

Form fluctuations of microemulsion droplets are observed in experiments using dielectric spectroscopy (DS) and neutron spin echo spectroscopy (NSE). Previous work on dioctyl sodium sulfosuccinate based water in oil microemulsions in the droplet phase has shown that adding a water soluble polymer (Polyethylene glycol M = 1500 g mol-1) modifies these fluctuations. While for small droplet sizes (water core radius rc < 37 Å) compared to the size of the polymer both methods consistently showed a reduction in the bending modulus of the surfactant shell as a result of polymer addition, dielectric spectroscopy suggests the opposite behaviour for large droplets. This observation is now confirmed by NSE experiments on large droplets. Structural changes due to polymer addition are qualitatively independent of droplet size. Dynamical properties, however, display a clear variation with the number of polymer chains per droplet, leading to the observed changes in the bending modulus. Furthermore, the contribution of structural and dynamical properties on the changes in bending modulus shifts in weight. With increasing droplet size, we initially find dominating finite size effects and a changeover to a system, where interactions between the confined polymer and the surfactant shell dominate the bending modulus.

Water/PEG Mixtures: Phase Behavior, Dynamics and Soft Confinement

Abstract Polyethylene glycol is water soluble and forms an eutectic system with water. The eutectic temperature is −19 °C for M=1500 g mol−1 and increases with molecular weight. The dielectric relaxation spectrum of the mixtures exhibits a strong loss maximum in ϵ″ (ω) similar to pure water. Relaxation time increases with the addition of PEG. Activation energies exhibit a maximum of 0.35 eV at molar fraction χp≈0.2. This compares well with results on ethanol water mixtures. Adding PEG molecules to nanoscopic water droplets of inverse microemulsions has only small impact on the bending modulus κ of a non-ionic microemulsion. In AOT based microemulsions an increase or decrease of κ is found in dependence on the size of the droplets. This is in accordance with the variation of the dynamic percolation transition in the same systems.

Metallopolymer-Based Block Copolymers for the Preparation of Porous and Redox-Responsive Materials

Metallopolymers are a unique class of functional materials because of their redox-mediated optoelectronic and catalytic switching capabilities and, as recently shown, their outstanding structure formation and separation capabilities. Within the present study, (tri)block copolymers of poly(isoprene) (PI) and poly(ferrocenylmethyl methacrylate) having different block compositions and overall molar masses up to 328 kg mol-1 are synthesized by anionic polymerization. The composition and thermal properties of the metallopolymers are investigated by state-of-the-art polymer analytical methods comprising size exclusion chromatography, 1H NMR spectroscopy, differential scanning calorimetry, and thermogravimetric analysis. As a focus of this work, excellent microphase separation of the synthesized (tri)block copolymers is proven by transmission electron microscopy, scanning electron microcopy, energy-dispersive X-ray spectroscopy, small-angle X-ray scattering measurements showing spherical, cylindrical, and lamellae morphologies. As a highlight, the PI domains are subjected to ozonolysis for selective domain removal while maintaining the block copolymer morphology. In addition, the novel metalloblock copolymers can undergo microphase separation on cellulose-based substrates, again preserving the domain order after ozonolysis. The resulting nanoporous structures reveal an intriguing switching capability after oxidation, which is of interest for controlling the size and polarity of the nanoporous architecture.

Molecular mobility in cellulose and paper

We study the dielectric relaxation in paper of different density and in microcrystalline cellulose in a temperature range between 150 K and 350 K. Qualitatively the spectra display the same relaxations α, β, γ. An additional relaxation, βwet, is found in humidified samples. The adsorption of water is determined and related to the humidity of the surrounding. Two adsorption processes are identified as primary and secondary adsorption at the hydroxyl groups in the amorphous domains of the cellulose. The γ process in the dielectric spectrum is found to be directly related to the amount of water adsorbed in the sample. While qualitatively the differences to unprocessed, microcrystalline cellulose are negligible, quantitatively the less localised β-relaxation shows an increased relaxation strength induced by the geometrical confinement and orientation effects due to the processing into cellulose fibres. While the manufacturing process leads to paper with different density and porosity there is no significant change in water uptake, structure or dynamics.

Aggregate Structure and Dynamic Percolation in Microemulsions

This contribution deals with a special class of soft matter systems called microemulsions. They are mixtures of oil and water stabilized with a surfactant. The stabilisation is achieved through the reduction of interfacial tension by the amphiphilic surfactant. They thus consist of oil and water phases separated by a surfactant layer. The nanoscopic structure of these phases, in particular that of spherical nano droplets, is analysed in this chapter. The impact of temperature and mixing ratio of the constituents is shown. The fascinating phenomenon of dynamic droplet percolation and aggregation near a temperature induced phase separation are discussed. Microemulsions provide an excellent model system for the investigation of confinement effects on molecules. Conversely these guest molecules modify structural and dynamical properties of the microemulsion. This may even lead to the formation of transient networks with short time gel-like and long time self-diffusion dynamics of droplets.