A new material for use as a proton exchange membrane in fuel cells has been developed: a blend of a perfluorocyclobutane-based block ionomer (S-PFCB) and Poly (vinylidene-co-hexafluoropropylene) (Kynar Flex, KF). This thesis details the work done thus far to characterize the morphology of this material, using small angle x-ray scattering, differential scanning calorimetry, atomic force micrscopy, and some other techniques to a lesser extent. Small angle x-ray scattering (SAXS) of pure S-PFCB showed a strong block copolymer- associated phase separation, on the order of 25 nm. Differential scanning Calorimetry (DSC) confirmed this finding. SAXS also revealed the presence of a peak representing individual ionic aggregates on the order of 3 nm. Finally, it was shown with DSC that no crystallinity develops in the S-PFCB block copolymer, while one of the blocks, known as 6F, crystallizes extensively. SAXS of incremental blend compositions of KF and S-PFCB revealed a steady increase in size of the block copolymer phase separation peak in SAXS, demonstrative of the miscibility of KF and the non-sulfonated 6F block of S-PFCB. Furthermore, this incremental study determined the scattering vector range relevant for comparing amounts of KF crystallinity. DSC of incremental blend compositions revealed two phases of KF crystallinity develops upon cooling a membrane, independent of cooling rate. Atomic force microscopy (AFM), small angle x-ray scattering (SAXS), and differential scanning calorimetry (DSC) corroborate to suggest a nonuniform morphology through the thickness of solution cast membranes. Also, the effect of different casting temperatures and after-casting anneals on morphology was assessed. Future work on this project involves morphological studies at various relative humidities and temperatures, as well as following up on discoveries already made. Finally, transmission electron micrscopy (TEM) should be performed to provide a visual analog, which will greatly help in developing an accurate morphological model. / Master of Science

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Small angle X-ray scattering (SAXS) has been widely used in polymer science to study the nano-scale morphology of various polymers. The data obtained from SAXS give information about sizes and shapes of macromolecules, characteristic distances of partially ordered materials, pore sizes, and so on. The understanding of these structural parameters is crucial in polymer science in that it will help to explain the origin of various properties of polymers, and guide design of future polymers with desired properties. We have been able to further develop the contrast variation method in SAXS to study the morphology of Nafion 117CS containing different alkali metal ions in solid state. Contrast variation allows one to manipulate scattering data to obtain desired morphological information. At room temperature, only the crystalline peak was found for Na⁺-form Nafion, while for Cs⁺-form Nafion only the ionic peak was observed. The utilization of one dimensional correlation function on different counterion forms of Nafion further demonstrates the necessity of contrast variation method in obtaining more detailed morphological information of Nafion. This separation of the ionic peak and the crystalline peak in Nafion provides a means to independently study the crystalline and ionic components without each other's effect, which could be further applied to other ionomer systems. We also designed time resolved SAXS experiments to study the morphological development during solution processing Nafion. As solvent was removed from Nafion dispersion through evaporation, solid-state morphological development occurred through a variety of processes including phase-inversion, aggregation of interacting species (e.g., ionic functionalities), and crystallization of backbone segments. To probe the real-time morphological development during membrane processing that accurately simulates industrial protocols, a unique sample cell has been constructed that allows for through-film synchrotron SAXS data acquisition during solvent evaporation and film formation. For the first time, this novel experiment allows for a complete analysis of structural evolution from solution/dispersion to solid-state film formation, and we were able to show that the crystallites within Nafion develop later than the formation of ionic domains, and they do not reside in the cylindrical particles, but are dispersed in solution/dispersion. Besides bulk morphology of Nafion, we have also performed Grazing Incident SAXS to study the surface morphology of Nafion. We were able to manipulate the surface morphology of Nafion via neutralizing H⁺-form Nafion with different large organic counterions, as well as annealing Nafion thin films under different temperatures. This not only allows to obtain more detailed information of the nano-structures in Nafion thin films, but also provides a means to achieve desired morphology for better fuel cell applications. We have also been able to study the polymer chain conformation in solution via measuring persistence length by utilizing solution SAXS. Different methods have been applied to study the SAXS profiles, and the measured persistence lengths for stilbene and styrenic alternating copolymers range from 2 to 6 nm, which characterizes these copolymers into a class of semi-rigid polymers. This study allows to elucidate the steric crowding effect on the chain stiffness of these polymers, which provides fundamental understanding of polymer chain behaviors in solution. Self-assembling in block copolymers has also been studied using SAXS. We established a morphological model for a multiblock copolymer used as a fuel cell material from General Motors®, and this morphological model could be used to explain the origins of the mechanical and transport properties of this material. Furthermore, several other block copolymers have been studied using SAXS, which showed interesting phase separated morphologies. These morphological data have been successfully applied to explain the origins of various properties of these block copolymers, which provide fundamental knowledge of structure-property relationship in block copolymers. / Ph. D.

Yes / Small-angle neutron scattering (SANS) and neutron spin-echo (NSE) have been used to investigate the temperature-dependent solution behaviour of highly-branched poly(N-isopropylacrylamide) (HB-PNIPAM). SANS experiments have shown that water is a good solvent for both HB-PNIPAM and a linear PNIPAM control at low temperatures where the small angle scattering is described by a single correlation length model. Increasing the temperature leads to a gradual collapse of HB-PNIPAM until above the lower critical solution temperature (LCST), at which point aggregation occurs, forming disperse spherical particles of up to 60 nm in diameter, independent of the degree of branching. However, SANS from linear PNIPAM above the LCST is described by a model that combines particulate structure and a contribution from solvated chains. NSE was used to study the internal and translational solution dynamics of HB-PNIPAM chains below the LCST. Internal HB-PNIPAM dynamics is described well by the Rouse model for non-entangled chains.

This thesis investigates the mechanisms behind natural silk spinning by integrating rheology, spectroscopy and small angle scattering to better understand this process and to guide our efforts towards mimicking Nature’s ways of producing high performance fibres. As a result of natural selection, arthropods such as spiders and moths have evolved the ability to excrete silk proteins in a highly controlled manner. Spun from liquid feedstocks, silk fibres are used ex vivo to build structures with mechanical properties currently unmatched by industrial filaments. As yet, relatively little attention has been directed to the investigation of spinning under biologically relevant conditions. To better understand how and why silk is spun, this thesis bridges the gap between liquid silk flow properties and structure development. To directly connect the two, I have developed and deployed novel experimental platforms that combine infrared spectroscopy and small angle scattering with rheology. This approach has clarified long-standing ambiguities on the structural root of silk’s apparently complex flow properties. Small angle scattering revealed the length scales involved in the flow induced solidification under a range of spinning conditions. Mo reover, infrared spectroscopy offered a unique perspective into silk’s formation process immediately after excretion. In a similar manner to the post-extrusion tuning of the properties of partly solidified spider silk filaments, this thesis has revealed that silkworm silk fibres are far from completely formed once excreted. One might describe the filaments of mulberry silkworm as seeded molten polymers that form its hydrogen bonding network and crystallises slowly on site. Consequently, it enlightens that post-spinning conditions are equally paramount for silkworm silk, giving an explanation for the relatively poorer mechanical properties. The comparison of silks from a range of species, allowed this hypothesis to be extended to wild silkworm silk. My insights into spinning had the fortuitous repercussion of facilitating silk fibre solubilisation leading to the development of better artificial silk feedstocks flowing like native silks. With these findings, I believe we are now in an improved position to conceive artificial fibres with properties rivalling those of Nature.

In the beginning of the twenty-first century, educational and commercial institutions have driven the demand for cheap and efficient data storage. The storage medium known as magnetic recording media has remained the mainstay for most computer systems due to its large storage capacity per dollar. With the recording media's ever-increasing storage density has come reductions in the magnetic grain size per bit. At the recording bit's density threshold, the magnetic grains become more susceptible to thermal activation, which can render the storage medium unusable. An accurate characterisation of the recording layer's sub-granular structure is essential for understanding the magnetic and thermal mechanisms of high-density recording media. Small-Angle Neutron Scattering (SANS) studies have been performed to investigate the magnetic and physical properties of longitudinal and perpendicular recording grains. The SANS studies of longitudinal magnetic recording media have probed the recording layer's magnetic grain size at a sub-nanometer resolution. In conjunction with these studies, SQUID magnetometry was used to characterise the recording grain's bulk magnetism. Measurements showed that the recording grain was composed of a ferromagnetic hard core (Co-enriched) and a weakly magnetic shell (Cr-enriched). These results provided important information on the grain's magnetic anisotropy, which determines the recording media's magnetic stability. The polarised SANS studies were used to characterise the recording layer's physical granular structure. It was shown that the physical grain size was comparable to its magnetic counterpart. These physical measurements provided insight into the recording grain's chemical composition. The magnetic properties of perpendicular magnetic recording media were studied using SANS and VSM measurements. The neutron scattering studies revealed that the recording grain was composed of a hard ferromagnetic centre enriched with cobalt. The VSM studies showed that the magnetic recording grains exhibited a large perpendicular magnetic anisotropy. These combined studies provided information on the recording grain's ferromagnetic composition and magnetic stability. The polarised SANS measurements showed the physical grain size to be slightly smaller than its magnetic counterpart. This size difference was attributed to the non-magnetic grain boundary composed of SiO2. The boundary thickness determined the degree of inter-granular exchange coupling. Further polarised studies investigated the recording layers switching behaviour, which revealed more information on the grain's magnetic stability.