Abstract
In this work, solvent composition effects on the average particle size and polydispersity of the commercial perfluorinated sulfonic acid (PFSA) membrane, i.e., Flemion®, in different solution mixtures were studied. Dynamic light scattering experiments were employed to determine the aggregate sizes of dispersed PFSA polymers in different water/alcohol solutions. The particle size distribution of the solute was analyzed and discussed for different solvent–solute systems. As the solvent gets more compatible with the Flemion®, the particle size reduced. Increasing the water content in propanol/water mixture increased the average particle size of the solute. Comparing three solution mixtures shows that the mean particle size increased as the solvent was changed in the order of ethanol, methanol and propanol. Differential scanning calorimetry (DSC) tests were conducted on the films obtained by recasting from different solution compositions. The results of DSC tests were used to investigate the water absorption and other thermal behavior. Structural properties such as equivalent weight of the polymer, free volume and the degree of aggregation of ionic groups or size of the clusters can influence the water uptake. DSC test results showed four different endothermic peaks which can be attributed to removal of surface and intergrain structural absorbed water, melting of crystalline segments and thermal degradation of the polymer, respectively.
Similar content being viewed by others
References
Kim DK, Choi EJ, Song HH, Kim MS (2016) Experimental and numerical study on the water transport behavior through Nafion® 117 for polymer electrolyte membrane fuel cell. J Membr Sci 497:194–208
Park JW, Wycisk R, Pintauro PN (2015) Nafion/PVDF nanofiber composite membranes for regenerative hydrogen/bromine fuel cells. J Membr Sci 490:103–112
Yoon SK, Lee JY, Kim TH, Yu DM, Hong SK, Hong YT (2015) Multiblock copolymers based on poly(p-phenylene)-co-poly(arylene ether sulfone ketone) with sulfonated multiphenyl pendant groups for polymer electrolyte fuel cell (PEMFC) application. Eur Polym J 66:1–11
Yao Y, Li J, Lu H, Gou J, Hui D (2015) Investigation into hybrid configuration in electrospun nafion/silica nanofiber. Compos Part B Eng 69:478–483
Doyle M, Lewittes ME, Roelofs MG, Perusich SA, Lowrey RE (2001) Relationship between ionic conductivity of perfluorinated ionomeric membranes and nonaqueous solvent properties. J Membr Sci 184:257–273
Tsai CE, Hwang BJ (2007) Intermolecular interactions between methanol/water molecules and Nafion® membrane: an infrared spectroscopy study. Fuel Cell 5:408–416
Affoune AM, Yamada A, Umeda M (2005) Conductivity and surface morphology of Nafion® membrane in water and alcohol environments. J Power Sources 148:9–17
Kumai S, Fukatsu Y, Mihara H, Tokura R (2003) Process for recovering fluoropolymers. US Patent 6515102
Miyake H, Sugaya Y, Asawa T (1983) Organic solution of fluorinated copolymer having carboxylic acid groups. US Patent 4385150
Kumai S, Fukatsu Y, Mihara H, Tokura R (2006) Process for recovering fluoropolymers. US Patent 7015263
Ma CH, Yu TL, Lin HL, Huang YT, Chen YL, Jeng US, Huang Lai Y, Sun YS (2009) Morphology and properties of Nafion® membranes prepared by solution casting. Polymer 50:1764–1777
Garcia-Villaluenga JP, Seoane B, Barragan VM, Ruiz-Bauza C (2003) Osmotic behaviour of a Nafion® membrane in methanol–water electrolyte solutions. J Colloid Interface Sci 263:217–222
Miyake H, Sugaya Y, Yamabe M (1998) Synthesis and properties of perfluorocarboxylated polymers. J Fluorine Chem 92:137–140
Kirsh YE, Smirnov SA, Pokov YM, Timashev SF (1990) Perfluorinated carbon-chain copolymers with functional groups and cation exchange membranes based on them: synthesis, structure and properties. Russ Chem Rev 59:970–994
Lee SL, Yu TL, Lin LH, Liu WH, Lai CL (2004) Solution properties of Nafion® in methanol/water mixture solvent. Polymer 45:2853–2862
Ngo TT, Yu TL, Lin HL (2013) Nafion®-based membrane electrode assemblies prepared from catalyst inks containing alcohol/water solvent mixtures. J Power Sources 238:1–10
Ngo TT, Yu TL, Lin HL (2013) Influence of the composition of isopropyl alcohol/water mixture solvents in catalyst ink solutions on proton exchange membrane fuel cell performance. J Power Sources 225:293–303
Jong HY, Kim JY, Park JK (2011) Effect of Nafion® dispersion solvent on the interfacial properties between the membrane and the electrode of a polymer electrolyte membrane-based fuel cell. Solid State Ion 196:73–78
Hooshyari K, Javanbakht M, Naji L, Enhessari M (2014) Nanocomposite proton exchange membranes based on Nafion® containing Fe2TiO5 nanoparticles in water and alcohol environments for PEMFC. J Membr Sci 454:74–81
Zhao S, Zhang J, Wang Y (2013) Electro-casting of proton exchange membranes from a heterogeneous solution. J Power Sources 242:23–27
Tuminello WH (1994) Solvents for fluorinated polymers. US Patent 5290846 A
Pusey PN, Van Megen W (1989) Dynamic light scattering by non-ergodic media. Physica A 157:705–741
Mao Q, Sun G, Wang S, Sun H, TianY Tian J, Xin Q (2008) Application of hyperdispersion to cathode diffusion layer for direct methanol fuel cell. J Power Sources 175:826–832
Lin HL, Yu TL, Huang CH, Lin TL (2005) Morphology study of Nafion membranes prepared by solutions casting. J Polym Sci Polym Phys 43:3044–3057
Lin HL, Yu TL, Shen KS, Huang LN (2004) Effect of Triton-X on the preparation of Nafion/PTFE composite membranes. J Membr Sci 237:1–7
Takeshita Y, Becker E, Sakata S, Miwa T, Sawada T (2014) States of water absorbed in water-borne urethane/epoxy coatings. Polymer 55:2505–2513
Amjadi M, Rowshanzamir S, Peighmbardoust SJ, Sedghi S (2012) Preparation, characterization and cell performance of durable Nafion/SiO2 hybrid membrane for high-temperature polymeric fuel cell. J Power Sources 210:350–357
Iwai Y, Yamanishi T (2009) Thermal stability of ion-exchange Nafion N117CS membranes. Polym Degrad Stab 94:679–687
Lage LG, Delgado PG, Kawano Y (2004) Vibrational and thermal characterization of Nafion membranes substituted by alkaline earth cations. Eur Polym J 40:1309–1316
Mecheri B, D’Epifanio A, Traversa E, Licoccia S (2007) Effect of an ormosil-based filler on the physic-chemical and electrochemical properties of Nafion membranes. J Power Sources 169:247–252
Amjadi M, Rowshanzamir S, Peighambardoust SJ, Hosseini MG, Eikani MH (2010) Investigation of physical properties and cell performance of Nafion/TiO2 nanocomposite membranes for high temperature PEM fuel cells. Int J Hydrogen Energy 35:9252–9260
Kong Y, Hay JN (2002) The measurement of the crystallinity of polymers by DSC. Polymer 43:3873–3878
Minakov AA, Mordvintsev DA, Schick C (2004) Melting and reorganization of poly(ethylene terephthalate) on fast heating (1000 K/s). Polymer 45:3755–3763
Jung HY, Kim JW (2012) Role of the glass transition temperature of Nafion 117 membrane in the preparation of the membrane electrode assembly in a direct methanol fuel cell (DMFC). Int J Hydrogen Energy 37:12580–12585
Acknowledgments
The authors acknowledge the financial support of Iran Polymer and Petrochemical Institute to carry out this research.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Zeynali, M.E., Mohammadi, F. & Rabiee, A. Investigation of solvent–solute interactions and film properties of perfluorinated sulfonic acid (PFSA) ionomers. Iran Polym J 25, 589–596 (2016). https://doi.org/10.1007/s13726-016-0448-2
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s13726-016-0448-2