The role of free volume, hydrogen bonding, and crosslinks on physical aging in polymers of intrinsic microporosity (PIMs)
Physical aging is a slow structural relaxation process characteristic of glassy polymers that results in reduced membrane permeabilities. In this study, PIM-1, the archetypal polymer of intrinsic microporosity (PIM), was post-synthetically modified to introduce components that are known to influence...
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Royal Society of Chemistry
2024
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| Online Access: | https://hdl.handle.net/1721.1/154134 |
| _version_ | 1824458239360630784 |
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| author | Joo, Taigyu Rodriguez, Katherine Mizrahi Lee, Hyunhee Acharya, Durga Doherty, Cara M. Smith, Zachary P. |
| author2 | Massachusetts Institute of Technology. Department of Chemical Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Chemical Engineering Joo, Taigyu Rodriguez, Katherine Mizrahi Lee, Hyunhee Acharya, Durga Doherty, Cara M. Smith, Zachary P. |
| author_sort | Joo, Taigyu |
| collection | MIT |
| description | Physical aging is a slow structural relaxation process characteristic of glassy polymers that results in reduced membrane permeabilities. In this study, PIM-1, the archetypal polymer of intrinsic microporosity (PIM), was post-synthetically modified to introduce components that are known to influence physical aging, such as hydrogen bonds and crosslinks. The effects of physical aging were monitored by permeation and sorption experiments, and structural changes were examined by positron annihilation lifetime spectroscopy (PALS) and other characterization techniques. The results suggest that higher initial fractional free volume is the primary factor contributing to higher rates of physical aging and that the introduction of hydrogen bonds and crosslinks reduces the initial free volume of PIM-1. In contrast, structural factors such as hydrogen bonds and crosslinks were the key factors in determining how permselectivity changed with physical aging. This study provides useful structure–property correlations and design principles related to free volume, hydrogen bonds, and crosslinks on physical aging behavior of microporous polymer membranes. |
| first_indexed | 2024-09-23T13:30:10Z |
| format | Article |
| id | mit-1721.1/154134 |
| institution | Massachusetts Institute of Technology |
| last_indexed | 2025-02-19T04:22:44Z |
| publishDate | 2024 |
| publisher | Royal Society of Chemistry |
| record_format | dspace |
| spelling | mit-1721.1/1541342025-01-08T04:43:16Z The role of free volume, hydrogen bonding, and crosslinks on physical aging in polymers of intrinsic microporosity (PIMs) Joo, Taigyu Rodriguez, Katherine Mizrahi Lee, Hyunhee Acharya, Durga Doherty, Cara M. Smith, Zachary P. Massachusetts Institute of Technology. Department of Chemical Engineering Massachusetts Institute of Technology. Department of Materials Science and Engineering Physical aging is a slow structural relaxation process characteristic of glassy polymers that results in reduced membrane permeabilities. In this study, PIM-1, the archetypal polymer of intrinsic microporosity (PIM), was post-synthetically modified to introduce components that are known to influence physical aging, such as hydrogen bonds and crosslinks. The effects of physical aging were monitored by permeation and sorption experiments, and structural changes were examined by positron annihilation lifetime spectroscopy (PALS) and other characterization techniques. The results suggest that higher initial fractional free volume is the primary factor contributing to higher rates of physical aging and that the introduction of hydrogen bonds and crosslinks reduces the initial free volume of PIM-1. In contrast, structural factors such as hydrogen bonds and crosslinks were the key factors in determining how permselectivity changed with physical aging. This study provides useful structure–property correlations and design principles related to free volume, hydrogen bonds, and crosslinks on physical aging behavior of microporous polymer membranes. Office of Naval Research; U.S. Department of Energy 2024-04-12T16:23:39Z 2024-04-12T16:23:39Z 2023-07 Article http://purl.org/eprint/type/JournalArticle 2050-7496 https://hdl.handle.net/1721.1/154134 Joo, Taigyu, Rodriguez, Katherine Mizrahi, Lee, Hyunhee, Acharya, Durga, Doherty, Cara M. et al. 2023. "The role of free volume, hydrogen bonding, and crosslinks on physical aging in polymers of intrinsic microporosity (PIMs)." Journal of Materials Chemistry A. PUBLISHER_CC https://doi.org/10.1039/D3TA01680C Journal of Materials Chemistry A Creative Commons Attribution https://creativecommons.org/licenses/by/3.0/ application/pdf Royal Society of Chemistry Royal Society of Chemistry |
| spellingShingle | Joo, Taigyu Rodriguez, Katherine Mizrahi Lee, Hyunhee Acharya, Durga Doherty, Cara M. Smith, Zachary P. The role of free volume, hydrogen bonding, and crosslinks on physical aging in polymers of intrinsic microporosity (PIMs) |
| title | The role of free volume, hydrogen bonding, and crosslinks on physical aging in polymers of intrinsic microporosity (PIMs) |
| title_full | The role of free volume, hydrogen bonding, and crosslinks on physical aging in polymers of intrinsic microporosity (PIMs) |
| title_fullStr | The role of free volume, hydrogen bonding, and crosslinks on physical aging in polymers of intrinsic microporosity (PIMs) |
| title_full_unstemmed | The role of free volume, hydrogen bonding, and crosslinks on physical aging in polymers of intrinsic microporosity (PIMs) |
| title_short | The role of free volume, hydrogen bonding, and crosslinks on physical aging in polymers of intrinsic microporosity (PIMs) |
| title_sort | role of free volume hydrogen bonding and crosslinks on physical aging in polymers of intrinsic microporosity pims |
| url | https://hdl.handle.net/1721.1/154134 |
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