Journal of Polymer Science Part B: Polymer Physics, Vol.45, No.6, 666-676, 2007
Spontaneous formation of hierarchical proton-conductive structures in sulfonated poly(p-phenylene terephthalamide) copolymer films
Two partially sulfonated. copolymers of poly(p-phenylene terephthalamide) were studied; the sulfonated diamine to nonsulfonated diamine ratios were x = 1 and x = 2. Polymer solutions in water demonstrated lyotropic liquid-crystalline behavior, with the critical concentration for nematic phase formation being around 0.7 wt%. Films of these copolymers could be considered for fuel-cell applications. The in-plane proton conductivities were of the order of 10(-3) to 10(-2) S cm(-1) between 20 and 90 degrees C. Increasing the sulfonation level resulted in a more conductive material. Spontaneous alignment of the polymer occurred during film formation, as revealed by X-ray diffraction. Scattering along the polymer backbone was observed perpendicular to the film, implying that the polymer chains were homeotropically aligned with respect to the film. The average degree of alignment was determined to be 0.66 and 0.77 for x = 1 and x = 2, respectively. Evidence of secondary layering within the plane of the film was seen in SEM images. These layers could provide a pathway for proton conduction to occur within the plane of the film. (c) 2007 Wiley Periodicals, Inc.
Keywords:liquid-crystalline polymers (LCP);membranes;polyelectrolytes;self-assembly;structure-property relations;supramolecular structures;X-ray