Incipient microphase separation in short chain perfluoropolyether-block-poly(ethylene oxide) copolymers
Abstract
Here, incipient microphase separation is observed by wide angle X-ray scattering (WAXS) in short chain multiblock copolymers consisting of perfluoropolyether (PFPE) and poly(ethylene oxide) (PEO) segments. Two PFPE–PEO block copolymers were studied; one with dihydroxyl end groups and one with dimethyl carbonate end groups. Despite having a low degree of polymerization (N ~ 10), these materials exhibited significant scattering intensity, due to disordered concentration fluctuations between their PFPE-rich and PEO-rich domains. The disordered scattering intensity was fit to a model based on a multicomponent random phase approximation to determine the value of the interaction parameter, χ, and the radius of gyration, Rg. Over the temperature range 30–90 °C, the values of χ were determined to be very large (~2–2.5), indicating a high degree of immiscibility between the PFPE and PEO blocks. In PFPE–PEO, due to the large electron density contrast between the fluorinated and non-fluorinated block and the high value of χ, disordered scattering was detected at intermediate scattering angles, (q ~ 2 nm-1) for relatively small polymer chains. Finally, our ability to detect concentration fluctuations was enabled by both a relatively large value of χ and significant scattering contrast.
- Authors:
-
[1];
[4];
[2];
- Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division; Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering
- Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry
- Adam Mickiewicz Univ. in Poznań (Poland). Faculty of Physics. NanoBioMedical Centre
- Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry; North Carolina State Univ., Raleigh, NC (United States). Dept. of Chemical and Biomolecular Engineering
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division. Environmental Energy Technologies Division; Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering
- Publication Date:
- Research Org.:
- State Univ. of New York (SUNY), Syracuse, NY (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1597269
- Alternate Identifier(s):
- OSTI ID: 1474994
- Grant/Contract Number:
- SC0012673; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Soft Matter
- Additional Journal Information:
- Journal Volume: 13; Journal Issue: 22; Journal ID: ISSN 1744-683X
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; Wide angle X-ray scattering; Thermodynamics; Perfluoropolyether
Citation Formats
Chintapalli, Mahati, Timachova, Ksenia, Olson, Kevin R., Banaszak, Michał, Thelen, Jacob L., Mecham, Sue J., DeSimone, Joseph M., and Balsara, Nitash P. Incipient microphase separation in short chain perfluoropolyether-block-poly(ethylene oxide) copolymers. United States: N. p., 2017.
Web. doi:10.1039/C7SM00738H.
Chintapalli, Mahati, Timachova, Ksenia, Olson, Kevin R., Banaszak, Michał, Thelen, Jacob L., Mecham, Sue J., DeSimone, Joseph M., & Balsara, Nitash P. Incipient microphase separation in short chain perfluoropolyether-block-poly(ethylene oxide) copolymers. United States. https://doi.org/10.1039/C7SM00738H
Chintapalli, Mahati, Timachova, Ksenia, Olson, Kevin R., Banaszak, Michał, Thelen, Jacob L., Mecham, Sue J., DeSimone, Joseph M., and Balsara, Nitash P. Thu .
"Incipient microphase separation in short chain perfluoropolyether-block-poly(ethylene oxide) copolymers". United States. https://doi.org/10.1039/C7SM00738H. https://www.osti.gov/servlets/purl/1597269.
@article{osti_1597269,
title = {Incipient microphase separation in short chain perfluoropolyether-block-poly(ethylene oxide) copolymers},
author = {Chintapalli, Mahati and Timachova, Ksenia and Olson, Kevin R. and Banaszak, Michał and Thelen, Jacob L. and Mecham, Sue J. and DeSimone, Joseph M. and Balsara, Nitash P.},
abstractNote = {Here, incipient microphase separation is observed by wide angle X-ray scattering (WAXS) in short chain multiblock copolymers consisting of perfluoropolyether (PFPE) and poly(ethylene oxide) (PEO) segments. Two PFPE–PEO block copolymers were studied; one with dihydroxyl end groups and one with dimethyl carbonate end groups. Despite having a low degree of polymerization (N ~ 10), these materials exhibited significant scattering intensity, due to disordered concentration fluctuations between their PFPE-rich and PEO-rich domains. The disordered scattering intensity was fit to a model based on a multicomponent random phase approximation to determine the value of the interaction parameter, χ, and the radius of gyration, Rg. Over the temperature range 30–90 °C, the values of χ were determined to be very large (~2–2.5), indicating a high degree of immiscibility between the PFPE and PEO blocks. In PFPE–PEO, due to the large electron density contrast between the fluorinated and non-fluorinated block and the high value of χ, disordered scattering was detected at intermediate scattering angles, (q ~ 2 nm-1) for relatively small polymer chains. Finally, our ability to detect concentration fluctuations was enabled by both a relatively large value of χ and significant scattering contrast.},
doi = {10.1039/C7SM00738H},
journal = {Soft Matter},
number = 22,
volume = 13,
place = {United States},
year = {Thu May 18 00:00:00 EDT 2017},
month = {Thu May 18 00:00:00 EDT 2017}
}
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