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Title: Vibrational Spectroscopy for the Determination of Ionizable Group Content in Ionomer Materials

Abstract

An approach based on vibrational spectral measurements is described for determining the ionizable group content of ion conducting polymer membrane materials. Aimed at supporting the assessment of membrane stability and wear characteristics, performance is evaluated for attenuated total reflection Fourier transform infrared (ATR FT-IR) spectroscopy, confocal Raman microscopy, and ATR FT-IR microscopy using perfluorinated ionomer membrane standards. One set of ionomer standards contained a sulfonic acid ionizable group and the other a sulfonyl imide group. The average number of backbone tetrafluoroethylene (TFE) units separating the ionizable-group containing side chains was in the range of 7.2–2.1 (sulfonic acid set) and 10.5–4.6 (sulfonyl imide set). A poly(tetrafluoroethylene) (PTFE) sample was included as a blank, representing the limit of zero ionizable group (and maximum TFE) content. Calibration relationships were derived from area-normalized vibrational spectra. For all three methods, calibration models applied to independent spectral measurements of samples predicted the ratio of backbone TFE groups to ionizable groups in the repeat unit ( m) with a standard error of ≤ ±0.3. The confocal Raman and ATR FT-IR microscopy techniques achieved ideal blank responses and the lowest prediction errors, down to m ± 0.1 at the 90% confidence level. With its relative simplicity, low sample size requirements, and potentialmore » for quantitative micron-scale spatial mapping of the ionizable group content within a membrane, the approach has application to advancing materials development, including exploratory synthesis, durability and wear assessment, and in situ studies of membrane process.« less

Authors:
ORCiD logo [1];  [1];  [1];  [2];  [3];  [3];  [4];  [2];  [2]
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  1. Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, TX, USA
  2. Department of Chemistry, Clemson University, Hunter Laboratories, Clemson, SC, USA
  3. Department of Chemistry, University of Utah, Salt Lake City, UT, USA
  4. 3M Energy Components Group, 3M Center, St Paul, MN, USA (retired)
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1484422
Grant/Contract Number:  
FG03-93ER14333
Resource Type:
Published Article
Journal Name:
Applied Spectroscopy
Additional Journal Information:
Journal Name: Applied Spectroscopy Journal Volume: 72 Journal Issue: 1; Journal ID: ISSN 0003-7028
Publisher:
SAGE Publications
Country of Publication:
United States
Language:
English

Citation Formats

Korzeniewski, Carol, Liang, Ying, Zhang, Pei, Sharif, Iqbal, Kitt, Jay P., Harris, Joel M., Hamrock, Steven J., Creager, Stephen E., and DesMarteau, Darryl D. Vibrational Spectroscopy for the Determination of Ionizable Group Content in Ionomer Materials. United States: N. p., 2017. Web. doi:10.1177/0003702817728243.
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Korzeniewski, Carol, Liang, Ying, Zhang, Pei, Sharif, Iqbal, Kitt, Jay P., Harris, Joel M., Hamrock, Steven J., Creager, Stephen E., & DesMarteau, Darryl D. Vibrational Spectroscopy for the Determination of Ionizable Group Content in Ionomer Materials. United States. https://doi.org/10.1177/0003702817728243
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Korzeniewski, Carol, Liang, Ying, Zhang, Pei, Sharif, Iqbal, Kitt, Jay P., Harris, Joel M., Hamrock, Steven J., Creager, Stephen E., and DesMarteau, Darryl D. Fri . "Vibrational Spectroscopy for the Determination of Ionizable Group Content in Ionomer Materials". United States. https://doi.org/10.1177/0003702817728243.
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@article{osti_1484422,
title = {Vibrational Spectroscopy for the Determination of Ionizable Group Content in Ionomer Materials},
author = {Korzeniewski, Carol and Liang, Ying and Zhang, Pei and Sharif, Iqbal and Kitt, Jay P. and Harris, Joel M. and Hamrock, Steven J. and Creager, Stephen E. and DesMarteau, Darryl D.},
abstractNote = {An approach based on vibrational spectral measurements is described for determining the ionizable group content of ion conducting polymer membrane materials. Aimed at supporting the assessment of membrane stability and wear characteristics, performance is evaluated for attenuated total reflection Fourier transform infrared (ATR FT-IR) spectroscopy, confocal Raman microscopy, and ATR FT-IR microscopy using perfluorinated ionomer membrane standards. One set of ionomer standards contained a sulfonic acid ionizable group and the other a sulfonyl imide group. The average number of backbone tetrafluoroethylene (TFE) units separating the ionizable-group containing side chains was in the range of 7.2–2.1 (sulfonic acid set) and 10.5–4.6 (sulfonyl imide set). A poly(tetrafluoroethylene) (PTFE) sample was included as a blank, representing the limit of zero ionizable group (and maximum TFE) content. Calibration relationships were derived from area-normalized vibrational spectra. For all three methods, calibration models applied to independent spectral measurements of samples predicted the ratio of backbone TFE groups to ionizable groups in the repeat unit ( m) with a standard error of ≤ ±0.3. The confocal Raman and ATR FT-IR microscopy techniques achieved ideal blank responses and the lowest prediction errors, down to m ± 0.1 at the 90% confidence level. With its relative simplicity, low sample size requirements, and potential for quantitative micron-scale spatial mapping of the ionizable group content within a membrane, the approach has application to advancing materials development, including exploratory synthesis, durability and wear assessment, and in situ studies of membrane process.},
doi = {10.1177/0003702817728243},
journal = {Applied Spectroscopy},
number = 1,
volume = 72,
place = {United States},
year = {Fri Sep 15 00:00:00 EDT 2017},
month = {Fri Sep 15 00:00:00 EDT 2017}
}
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https://doi.org/10.1177/0003702817728243
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