SAXS signature of the lamellar ordering of ionic domains of perfluorinated sulfonic-acid ionomers by electric and magnetic field-assisted casting.

At present, small angle X-ray scattering (SAXS) studies of perfluorinated sulfonic-acid ionomers (PFSAs) are unable to fully determine the true shape of their building blocks, as recent SAXS modelling predicts disk- and rod-like nanoionic domains as being equally possible. This scenario requires evidence-based findings to unravel the real shape of PFSA building blocks. Herein, a SAXS pattern signature for a lamellar nanophase separation of the ionic domains of Nafion is presented, backed by mid and far infrared spectroscopy (MIR and FIR) and wide angle X-ray scattering (WAXS) data of Nafion in different ionic forms, a broad range of ionic phase contents (EW ∼ 859-42 252 g eq-1) and temperatures. The study indicates that the lamellar arrangement of the ionic domains is the most representative morphology that accounts for the physical properties of this ionomer. The lamellar SAXS reflections of Nafion are enhanced in electric and magnetic field-aligned membranes, as confirmed by atomic force microscopy (AFM). Electric and magnetic field-assisted casting of Nafion allowed producing nanostructured and anisotropic films with the lamellas stacked perpendicularly to the field vector, which is the direction of interest for several applications. Such nanostructured Nafion membranes are bestowed with advanced optical and proton transport properties, making them promising materials for solar and fuel cells.

Interplay of α/ß-Relaxation Dynamics and the Shape of Ionomer Building Blocks.

The relation between the α/ß relaxations and the shape of the building blocks of ionomer materials is a key factor for programming an important temperature-dependent property: the memory of shape. However, the morphology of ionomers is indirectly obtained via modeling of small angle X-ray scattering (SAXS) data owing to the hardly accessible image characterization of the nanometric building blocks ‒ micelle-like cylindrical polymeric aggregates (radius ~2-6 nm and length >100 nm). Herein, broadband dielectric spectroscopy (BDS) measurements, free from electrode polarization effects, allowed identifying the time and temperature dependence of the polarization of different length scales of the ionomer matrix, and more importantly, by directly providing the aspect ratio of the radius and length of the polymeric aggregates for each desired temperature. This finding is essential for controlling the shape of ionomer based functional products under several stimuli conditions, thereby advancing remarkable applications, such as four dimensional (4D) printing.