Morphological Characterization and Analysis of Ion-Containing Polymers Using Small Angle X-ray Scattering
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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.
- Doctoral Dissertations