Abstract
The nanoscale structures of graft-type polymer electrolyte membranes (PEMs), prepared by radiation-induced graft polymerization (grafting) of styrene onto poly(ethylene-co-tetrafluoroethylene) (ETFE) films followed by sulfonation, were investigated using a small-angle neutron scattering (SANS) technique. For comparison, SANS measurements were also performed on two precursor materials, the original ETFE film and polystyrene (PS)-grafted films. The SANS profiles of the grafted films showed shoulder peaks at a d-spacing of ∼30 nm, which were attributed to the PS grafts introduced into the amorphous phases between the ETFE lamellar crystals. This grafting would result in the construction of a stack structure with alternating ETFE crystalline and PS-grafted layers as a repeating unit. In the ETFE PEMs, the spacing of the PS sulfonic acid (PSSA) grafts and ETFE crystals increased because the graft regions were enlarged by the volume of the attached sulfonic acid groups. Interestingly, the graft/crystal stack spacing in the PEMs did not increase from the dry- to fully-hydrated states. This finding implies restricted water absorption in the PSSA grafts between the ETFE lamellar crystals. In other words, most of the PSSA grafts introduced outside of the lamellae were considered to be hydrated and to act as proton conduction pathways.
Similar content being viewed by others
Log in or create a free account to read this content
Gain free access to this article, as well as selected content from this journal and more on nature.com
or
References
Smitha, B., Sridhar, S. & Khan, A. A. Solid polymer electrolyte membranes for fuel cell applications—a review. J. Membr. Sci. 259, 10–26 (2005).
Wang, Y., Chen, K. S., Mishler, J., Cho, S. C. & Adroher, X. C. A review of polymer electrolyte membrane fuel cells: technology, applications, and needs on fundamental research. Appl. Energy 88, 981–1007 (2011).
Nasef, M. M. & Hegazy, E. S. A. Preparation and applications of ion exchange membranes by radiation-induced graft copolymerization of polar monomers onto non-polar films. Prog. Polym. Sci. 29, 499–561 (2004).
Gubler, L., Gürsel, S. A. & Scherer, G. G. Radiation grafted membranes for polymer electrolyte fuel cells. Fuel Cells 5, 317–335 (2005).
Mauritz, K. A. & Moore, R. B. State of understanding of nafion. Chem. Rev. 104, 4535–4585 (2004).
Gierke, T. D., Munn, G. E. & Wilson, F. C. The morphology in nafion perfluorinated membrane products as determined by wide- and small-angle X-ray studies. J. Polym. Sci. Polym. Phys. Ed. 19, 1687–1704 (1981).
Balog, S., Gasser, U., Mortensen, K., Gubler, L., Scherer, G. G. & Youcef, H. B. Correlation between morphology, water uptake, and proton conductivity in radiation-grafted proton-exchange membranes. Macromol. Chem. Phys. 211, 635–643 (2010).
Funaki, A., Arai, K., Aida, S., Phongtamrug, S. & Tashiro, K. Influence of third monomer on the crystal phase transition behavior of ethylene-tetrafluoroethylene copolymer. Polymer (Guildf) 49, 5497–5503 (2008).
Mortensen, K., Gasser, U., Gürsel, S. A. & Scherer, G. G. Structural characterization of radiation-grafted block copolymer films, using SANS technique. J. Polym. Sci. Part B Polym. Phys. 46, 1660–1668 (2008).
Seguchi, T. & Tamura, N. Mechanism of decay of alkyl radicals in irradiated polyethylene on exposure to air as studied by electron spin resonance. J. Phys. Chem. 77, 40–44 (1973).
Seguchi, T. & Tamura, N. Electron spin resonance studies on radiation graft copolymerization in polyethylene. II. Grafting initiated by allyl radicals trapped in irradiated polyethylene. J. Polym. Sci. Polym. Chem. Ed. 12, 1953–1964 (1974).
Smit, I. & Bezjak, A. Structural changes in the grafted copolymer polyethylene-styrene. Polymer (Guildf) 22, 590–596 (1981).
Iwase, H., Sawada, S., Yamaki, T., Maekawa, Y. & Koizumi, S. Preirradiation graft polymerization of styrene in a poly(tetrafluoroethylene) film investigated by time-resolved small-angle neutron scattering. Int. J. Polym. Sci., 2011 doi:10.1155/2011/301807.
Roe, R. J. Methods of X-ray and Neutron Scattering in Polymer Science ch. 5 176–184 (Oxford University Press, New York, 2000).
Sawada, S., Yamaki, T., Ozawa, T., Suzuki, A., Terai, T. & Maekawa, Y. Structural analysis of radiation-grafted polymer electrolyte membranes by dissipative particle dynamics simulation. Kobunshi Ronbunshu (in Japanese) 67, 224–227 (2010).
Acknowledgements
This work was supported by Grant-in-Aid for Young Scientists (B) from Japan Society for the Promotion of Science (JSPS) (Grant number: 22750208).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Sawada, Si., Yamaguchi, D., Putra, A. et al. Nanoscale structures of radiation-grafted polymer electrolyte membranes investigated via a small-angle neutron scattering technique. Polym J 45, 797–801 (2013). https://doi.org/10.1038/pj.2012.218
Received:
Revised:
Accepted:
Published:
Issue date:
DOI: https://doi.org/10.1038/pj.2012.218