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Title: Analysis of governing factors controlling gas transport through fresh and aged triptycene-based polyimide films

Abstract

In this report the fundamental gas transport properties and physical aging behavior of a series of triptycene-based polyimides with various substitution groups were investigated. Wide-angle x-ray diffraction revealed that the 6FDA-1,4-triptycene polyimides exhibit two chain packing domains with d-spacing values of ~6.7 Å and ~5.3 Å, corresponding to triptycene-induced chain packing disruption and chain segments lacking the triptycene moiety, respectively. Positron annihilation lifetime spectroscopy (PALS) showed a bimodal distribution of microcavity size made up of triptycene cleft cavities that are ~3 Å diameter and larger interchain cavities with an average diameter of ~7 Å. Additionally, PALS confirmed 6FDA-1,4-trip_CH3 has the lowest fractional free volume, primarily due to smaller contributions from the interchain cavities, and 6FDA-1,4-trip_CF3 has the largest fractional free volume. It was also found that the addition of substituent groups had a unique and positive effect on the aging properties over nine months, in which the addition of CH3 and CF3 groups led to permeability increases of ~20% and ~40%, respectively. This is caused by the combination of the lowered driving force for physical aging, the substituent groups sterically hindering tighter packing with time, and the interconnectivity and/or unblocking of free volume over time through small-scale, local chain motion.

Authors:
 [1];  [1];  [2];  [2];  [3];  [1]
+ Show Author Affiliations
  1. University of Notre Dame, IN (United States)
  2. Commonwealth Scientific and Industrial Research Organization (CSIRO), Victoria (Australia)
  3. Chinese Academy of Sciences (CAS), Beijing (China)
Publication Date:
Research Org.:
University of Notre Dame, IN (United States)
Sponsoring Org.:
USDOE Office of Science (SC); ACS Petroleum Research Fund; Australian Research Council
OSTI Identifier:
1534095
Alternate Identifier(s):
OSTI ID: 1397957
Grant/Contract Number:  
SC0010330; 56144-DNI10; DE40101359
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Membrane Science
Additional Journal Information:
Journal Volume: 522; Journal Issue: C; Journal ID: ISSN 0376-7388
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; triptycene; gas separation membrane; physical aging; fractional free volume; polyimide

Citation Formats

Weidman, Jennifer R., Luo, Shuangjiang, Doherty, Cara M., Hill, Anita J., Gao, Peiyuan, and Guo, Ruilan. Analysis of governing factors controlling gas transport through fresh and aged triptycene-based polyimide films. United States: N. p., 2016. Web. doi:10.1016/j.memsci.2016.09.013.
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Weidman, Jennifer R., Luo, Shuangjiang, Doherty, Cara M., Hill, Anita J., Gao, Peiyuan, & Guo, Ruilan. Analysis of governing factors controlling gas transport through fresh and aged triptycene-based polyimide films. United States. https://doi.org/10.1016/j.memsci.2016.09.013
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Weidman, Jennifer R., Luo, Shuangjiang, Doherty, Cara M., Hill, Anita J., Gao, Peiyuan, and Guo, Ruilan. Sat . "Analysis of governing factors controlling gas transport through fresh and aged triptycene-based polyimide films". United States. https://doi.org/10.1016/j.memsci.2016.09.013. https://www.osti.gov/servlets/purl/1534095.
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@article{osti_1534095,
title = {Analysis of governing factors controlling gas transport through fresh and aged triptycene-based polyimide films},
author = {Weidman, Jennifer R. and Luo, Shuangjiang and Doherty, Cara M. and Hill, Anita J. and Gao, Peiyuan and Guo, Ruilan},
abstractNote = {In this report the fundamental gas transport properties and physical aging behavior of a series of triptycene-based polyimides with various substitution groups were investigated. Wide-angle x-ray diffraction revealed that the 6FDA-1,4-triptycene polyimides exhibit two chain packing domains with d-spacing values of ~6.7 Å and ~5.3 Å, corresponding to triptycene-induced chain packing disruption and chain segments lacking the triptycene moiety, respectively. Positron annihilation lifetime spectroscopy (PALS) showed a bimodal distribution of microcavity size made up of triptycene cleft cavities that are ~3 Å diameter and larger interchain cavities with an average diameter of ~7 Å. Additionally, PALS confirmed 6FDA-1,4-trip_CH3 has the lowest fractional free volume, primarily due to smaller contributions from the interchain cavities, and 6FDA-1,4-trip_CF3 has the largest fractional free volume. It was also found that the addition of substituent groups had a unique and positive effect on the aging properties over nine months, in which the addition of CH3 and CF3 groups led to permeability increases of ~20% and ~40%, respectively. This is caused by the combination of the lowered driving force for physical aging, the substituent groups sterically hindering tighter packing with time, and the interconnectivity and/or unblocking of free volume over time through small-scale, local chain motion.},
doi = {10.1016/j.memsci.2016.09.013},
journal = {Journal of Membrane Science},
number = C,
volume = 522,
place = {United States},
year = {Sat Sep 10 00:00:00 EDT 2016},
month = {Sat Sep 10 00:00:00 EDT 2016}
}
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