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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.

Many text books and publications do not focus on the necessity of chain tilting in crystalline lamellae of oligomers and polymers, a fundamental aspect of their crystallization already discussed by Flory. Herein we investigate the chain tilt of ethylene oxide oligomers (EOs) containing various midchain defects by WAXS, SAXS and solid state 13C MAS NMR spectroscopy. At low temperatures, one out of the two EO chains of EO9-meta-EO9 and EO11-TR-EO11 containing a 1,3-disubstituted benzene or a 1,4-disubstituted 1,2,3-triazole defect in central position of the oligomer chain forms crystals and the other EO chain as well as the defect remain in the amorphous phase. The aromatic midchain defect of these two oligomers can be incorporated into the crystalline lamella upon heating below Tm. Then, the adjoining amorphous EO chain crosses from the lamellae to the amorphous regions at an angle ξ, which is preordained by the substitution pattern of the aromatic defect, revealing that the chain tilt angle ranges between...

Nanoporous ion track-etched polycarbonate is ideally suited for the study of confined polymers via small angle X-ray scattering (SAXS) due to the strictly parallel orientation of the pores as well as their uncorrelated lateral distribution. Nanopores with radii ranging from 17 to 213 nm are prepared and coated with SiO2via atomic layer deposition in order to obtain a well-defined and homogeneous surface. A low molecular weight polyethylene glycol (PEG) homopolymer with a semicrystalline lamellar bulk structure is introduced into the nanopores via melt infiltration. At high temperatures SAXS measurements confirm a uniform filling of the pores with amorphous polymer. Upon cooling below the melting point of PEG, a concentrical structure of semicrystalline lamellae is revealed for large pore radii. We introduce models which successfully describe the combined scattering from nanopores and semicrystalline or amorphous PEG inside. DSC measurements of the confined polymer show a decrease of melting temperature and heat of fusion per gram polymer upon reduction of the pore radius and hint at a change in the lamellar configuration.

The bending modulus κ is known to be a crucial parameter for the stability of the droplet phase in microemulsion systems. For AOT based water in oil microemulsions the bending modulus of the surfactant has values close to kBT but can be influenced by the presence of polymers. In this work we focus on the water soluble polymer polyethylene glycol and how it influences the bending modulus. An increase by a factor of three is found. For the correct evaluation of the bending modulus via percolation temperatures and droplet radii, thus by dielectric spectroscopy and small angle X-ray scattering, the determination of the radii right at the percolation temperature is crucial as we will show, although it is often neglected. In order to precisely determine the droplet radii we will present a global fitting model which provides reliable results with a minimum number of free fitting parameters.

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.