Anisotropic Morphologies and Properties in Perfluorosulfonate Ionomer-Based Materials

The overall goal of this investigation was to elucidate specific structure-property relationships in perfluorosulfonate ionomers (PFSIs)-related materials. The project can be broken into two primary foci. First, we explored the current state of understanding related to morphology-property relationships in PFSIs with specific attention to the nano-scale organization of the ionic and crystalline domains. Specifically, the effect of uniaxial orientation on the structure and transport properties of Nafion® membranes was examined. Small angle X-ray scattering (SAXS) experiments on dry membranes that were uniaxially elongated showed a strong anisotropic morphology which was shown to persist over the swelling process without a significant relaxation. Herman's order parameters for the ionomer peak were strongly influenced by uniaxial deformation, which supports the presence of cylindrical rather than spherical morphology for ionic domains. Comparison of the water diffusion coefficients between unoriented and oriented samples revealed that uniaxial deformation of Nafion® membranes essentially enhances transport ability in one direction (i.e., the parallel to draw direction) and suppresses in the other two directions (i.e., two orthogonal directions relative to the stretching direction). Based on 1-dimensional analyses of oriented SAXS patterns at the azimuthal angle 90o, three recent models (lamellar model, semicrystalline rod-like model and fringed-micelle model) for the morphology of PFSIs were critically evaluated. The loss of meridional scattering, different orientation behavior of the crystalline and ionic domains, and inherent chain stiffness precludes the possibility of a chain-folded lamellar morphology. While the inter-aggregate dimensions remain constant at high draw ratios, the inter-crystalline spacings decrease significantly. Coupled with the distinctly different orientation behavior, these observations preclude the existence of crystallites solely within rod-like aggregates. While the worm-like ionic channel model was able to explain the behavior of SAXS and wide angle X-ray scattering (WAXS) relatively well, this model also had limitations such as (1) crystalline domains directly linked to the ionic domain (and thus a lack of amorphous domains) and (2) a presence of only a single ionic channel between two neighboring crystallites.

Second, electroactive materials, specifically ionic polymer-metal composites (IPMCs) that undergo bending motions with the stimulus of a relatively weak electric field were fabricated. To understand the role of the nanoscale morphology of the membrane matrix in affecting the actuation behavior of IPMC systems, we evaluated actuation performance of IPMCs subjected to uniaxial orientation. The PFSI nanostructure altered by uniaxial orientation mimicked the fibrillar structure of biological muscle tissue and yielded a new anisotropic actuation response. It was evident that IPMCs cut from films oriented perpendicular to the draw direction yielded displacement values that were significantly greater than that of unoriented IPMCs. In contrast, IPMCs cut from films oriented parallel to the draw direction appeared to resist bending and yield displacement values that were much less than that of the unoriented IPMC. This anisotropic actuation behavior was attributed to the contribution of the nanoscale morphology to the bulk bending modulus. Overall, this study clearly demonstrated, for the first time, the importance of the nanoscale morphology in affecting/controlling the actuation behavior in IPMC systems.