Chemical Durability Studies of Perfluorinated Sulfonic Acid Polymers and Model Compounds under Mimic Fuel Cell Conditions
Abstract
Peroxide radical treatments of a perfluorinated ionomer used in polymer electrolyte membrane (PEM) fuel cells and its small molecule analogues were carried out, along with analysis of the resultant products. Molecules containing terminal carboxylic acids degraded at least 1 order of magnitude faster than noncarboxylate materials; all of the systems did show peroxide-initiated degradation nonetheless. Product analysis suggests that terminal carboxylic acids react according to a sequential chain shortening, consistent with previous studies. Cleavage of side chains from both polymer and model compounds was also observed to be important and in fact may be the dominate pathway in low carboxyl content commercial PEM membranes, based on the following comparison of reactivity and concentration. The relative reactivities of carboxylic chain ends and ether linkages is approximately 500, as calculated using model compounds fluoride generation rates. Commercial perfluorosulfonic acid (PFSA) products contain minimal carboxylic acid end groups, and the side chain concentrations are of 2−3 orders of magnitude higher than carboxylic acid end groups.
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These species have not been previously reported in environmental media, to the best of the authors' knowledge.
“While these species have not been previously reported in environmental media, to the best of our knowledge, the literature of fluorochemical manufacturers proposes a few possible structures in this group, primarily as side products in fluoropolymer production and degradation.(55–57)”
From Identification of Per- and Polyfluoroalkyl Substances in the Cape Fear River by High Resolution Mass Spectrometry and Nontargeted Screening (2019) · cites this paper as [57]
The literature of fluorochemical manufacturers proposes a few possible structures in this group, primarily as side products in fluoropolymer production and degradation.
“While these species have not been previously reported in environmental media, to the best of our knowledge, the literature of fluorochemical manufacturers proposes a few possible structures in this group, primarily as side products in fluoropolymer production and degradation.(55–57)”
From Identification of Per- and Polyfluoroalkyl Substances in the Cape Fear River by High Resolution Mass Spectrometry and Nontargeted Screening (2019) · cites this paper as [57]
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New Insights into Perfluorinated Sulfonic-Acid Ionomers
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- Authors
- Zhou, C., Guerra, M. A., Qiu, Z.-M., Zawodzinski, & Schiraldi, D. A.
- Affiliations
- 3M (United States) (US)
- Corresponding author
- Schiraldi, David A.
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 2007-11-01
- Volume
- 40
- Issue
- 24
- Pages
- 8695-8707
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W1986509723
- Cited by
- 149
- References
- 13
- Citations by year
- 2026: 9 · 2025: 7 · 2024: 7 · 2023: 3 · 2022: 6 · 2021: 6 · 2020: 7 · 2019: 5 · 2018: 8 · 2017: 7 · 2016: 4 · 2015: 5 · 2014: 8 · 2013: 7 · 2012: 12
- FWCI
- 10.40
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Macromolecules (publishedVersion)
- Topics
- Physical Sciences › Engineering › Electrical and Electronic Engineering › Fuel Cells and Related Materials
- Physical Sciences › Materials Science › Polymers and Plastics › Synthesis and properties of polymers
- Physical Sciences › Environmental Science › Environmental Chemistry › Per- and polyfluoroalkyl substances research
- Keywords
- perfluorinated ionomers, proton exchange membrane fuel cells, chemical durability, side-chain cleavage, chain shortening, perfluorosulfonic acid membranes
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