Oriented crystallization of PEG induced by confinement in cylindrical nanopores: structural and thermal properties.

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.

Chain Tilt and Crystallization of Ethylene Oxide Oligomers with Midchain Defects.

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 36° ≤ ϕ ≤ 60°.

Changes in the bending modulus of AOT based microemulsions induced by the incorporation of polymers in the water core.

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.