Challenge and Solution of Characterizing Glass Transition Temperature for Conjugated Polymers by Differential Scanning Calorimetry
Abstract
Thermomechanical properties of polymers greatly depend on their glass transition temperature (Tg). Differential scanning calorimetry (DSC) is commonly used to measure Tg of polymers. Yet, many conjugated polymers (CPs), especially donor–acceptor CPs (D–A CPs), do not show a clear glass transition when measured by conventional DSC using simple heat and cool scan. In this work, we discuss the origin of the difficulty for measuring T g in such type of polymers. The changes in specific heat capacity (Δcp) at Tg were accurately probed for a series of CPs by DSC. The results showed a significant decrease in Δcp from flexible polymer (0.28 Jg-1 K-1 for polystyrene) to rigid CPs (10-3 Jg-1 K-1 for a naphthalene diimide-based D–A CP). When a conjugation breaker unit (flexible unit) is added to the D–A CPs, we observed restoration of the Δc p at Tg by a factor of 10, confirming that backbone rigidity reduces the Δcp. Additionally, an increase in the crystalline fraction of the CPs further reduces Δcp. We conclude that the difficulties of determining Tg for CPs using DSC are mainly due to rigid backbone and semicrystalline nature. We also demonstrate that physical aging can be used on DSC to help locatemore »
- Authors:
-
[1];
[1];
[1];
[1];
[5];
[6];
[3];
[1]
- Univ. of Southern Mississippi, Hattiesburg, MI (United States)
- Purdue Univ., West Lafayette, IN (United States)
- Univ. of Windsor, ON (Canada)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
- Publication Date:
- Research Org.:
- Univ. of Southern Mississippi, Hattiesburg, MS (United States); Argonne National Laboratory (ANL), Argonne, IL (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); University of Southern Mississippi, Hattiesburg, MS (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; Natural Sciences and Engineering Research Council of Canada (NSERC); National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1599384
- Alternate Identifier(s):
- OSTI ID: 1574507; OSTI ID: 1735960; OSTI ID: 1774742; OSTI ID: 1783058; OSTI ID: 1985407
- Grant/Contract Number:
- SC0019361; NETGP‐508526‐17; RGPIN‐2017‐06611; OIA‐1757220; AC02‐76SF00515; AC02‐06CH11357; AC02-06CH11357; AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Polymer Science. Part B, Polymer Physics
- Additional Journal Information:
- Journal Volume: 57; Journal Issue: 23; Journal ID: ISSN 0887-6266
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; conjugated polymers; glass transition; heat capacity; organic electronics; specific heat capacity
Citation Formats
Qian, Zhiyuan, Galuska, Luke, McNutt, William W., Ocheje, Michael U., He, Youjun, Cao, Zhiqiang, Zhang, Song, Xu, Jie, Hong, Kunlun, Goodman, Renée B., Rondeau‐Gagné, Simon, Mei, Jianguo, and Gu, Xiaodan. Challenge and Solution of Characterizing Glass Transition Temperature for Conjugated Polymers by Differential Scanning Calorimetry. United States: N. p., 2019.
Web. doi:10.1002/polb.24889.
Qian, Zhiyuan, Galuska, Luke, McNutt, William W., Ocheje, Michael U., He, Youjun, Cao, Zhiqiang, Zhang, Song, Xu, Jie, Hong, Kunlun, Goodman, Renée B., Rondeau‐Gagné, Simon, Mei, Jianguo, & Gu, Xiaodan. Challenge and Solution of Characterizing Glass Transition Temperature for Conjugated Polymers by Differential Scanning Calorimetry. United States. https://doi.org/10.1002/polb.24889
Qian, Zhiyuan, Galuska, Luke, McNutt, William W., Ocheje, Michael U., He, Youjun, Cao, Zhiqiang, Zhang, Song, Xu, Jie, Hong, Kunlun, Goodman, Renée B., Rondeau‐Gagné, Simon, Mei, Jianguo, and Gu, Xiaodan. Sun .
"Challenge and Solution of Characterizing Glass Transition Temperature for Conjugated Polymers by Differential Scanning Calorimetry". United States. https://doi.org/10.1002/polb.24889. https://www.osti.gov/servlets/purl/1599384.
@article{osti_1599384,
title = {Challenge and Solution of Characterizing Glass Transition Temperature for Conjugated Polymers by Differential Scanning Calorimetry},
author = {Qian, Zhiyuan and Galuska, Luke and McNutt, William W. and Ocheje, Michael U. and He, Youjun and Cao, Zhiqiang and Zhang, Song and Xu, Jie and Hong, Kunlun and Goodman, Renée B. and Rondeau‐Gagné, Simon and Mei, Jianguo and Gu, Xiaodan},
abstractNote = {Thermomechanical properties of polymers greatly depend on their glass transition temperature (Tg). Differential scanning calorimetry (DSC) is commonly used to measure Tg of polymers. Yet, many conjugated polymers (CPs), especially donor–acceptor CPs (D–A CPs), do not show a clear glass transition when measured by conventional DSC using simple heat and cool scan. In this work, we discuss the origin of the difficulty for measuring T g in such type of polymers. The changes in specific heat capacity (Δcp) at Tg were accurately probed for a series of CPs by DSC. The results showed a significant decrease in Δcp from flexible polymer (0.28 Jg-1 K-1 for polystyrene) to rigid CPs (10-3 Jg-1 K-1 for a naphthalene diimide-based D–A CP). When a conjugation breaker unit (flexible unit) is added to the D–A CPs, we observed restoration of the Δc p at Tg by a factor of 10, confirming that backbone rigidity reduces the Δcp. Additionally, an increase in the crystalline fraction of the CPs further reduces Δcp. We conclude that the difficulties of determining Tg for CPs using DSC are mainly due to rigid backbone and semicrystalline nature. We also demonstrate that physical aging can be used on DSC to help locate and confirm the glass transition for D-A CPs with weak transition signals.},
doi = {10.1002/polb.24889},
journal = {Journal of Polymer Science. Part B, Polymer Physics},
number = 23,
volume = 57,
place = {United States},
year = {Sun Nov 17 00:00:00 EST 2019},
month = {Sun Nov 17 00:00:00 EST 2019}
}
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