Nonmonotonic Glass Transition Temperature of Polymer Films Supported on Polymer Brushes

Hoyeon Lee; Vaidyanathan Sethuraman; Yeongsik Kim; Wooseop Lee; Du Yeol Ryu; Venkat Ganesan

doi:10.1021/acs.macromol.8b00290

Nonmonotonic Glass Transition Temperature of Polymer Films Supported on Polymer Brushes

Hoyeon Lee, Vaidyanathan Sethuraman, Yeongsik Kim, Wooseop Lee, Du Yeol Ryu, Venkat Ganesan

Department of Chemical and Biomolecular Engineering

Research output: Contribution to journal › Article › peer-review

15 Citations (Scopus)

Abstract

We modulated the grafting density (σ) and chain length of polystyrene (PS) brushes on substrates to probe their effect on the glass transition temperature (T_g) in overlaying PS thin films. The T_g of PS films was analyzed as a function of brush thickness (or σR_g ²), where R_g is the radius of gyration of PS brushes. Our results indicate that PS films below 90 nm exhibit a nonmonotonic dependence of T_g on grafting density with the maximum T_g occurring near the regime of wetting-dewetting transition of the overlaying melt. The maximum T_g was found to be higher than the value of bulk PS system. Computer simulation results suggest that such trends arise as a consequence of the environment of enhanced friction presented by the brush layer and the overlap between the polymer film and the grafted layer.

Original language	English
Pages (from-to)	4451-4461
Number of pages	11
Journal	Macromolecules
Volume	51
Issue number	12
DOIs	https://doi.org/10.1021/acs.macromol.8b00290
Publication status	Published - 2018 Jun 26

Bibliographical note

Funding Information:
V.G. acknowledges funding in part by grants from the Robert A. Welch Foundation (Grant F1599), the National Science Foundation (DMR-1306844), to King Abdullah University of Science and Technology (OSR-2016-CRG5-2993-1). Acknowledgment is also made to the Donors of the American Chemical Society Petroleum Research Fund for partial support of this research (56715-ND9). D.Y.R. acknowledges funding by the NRF grants (2017R1A2A2A05001048, 2017R1A4A1014569) funded by the Ministry of Science, ICT & Future Planning (MSIP), Korea. H.L. acknowledges funding by the Yonsei University Research Fund (2016-12-0011).

Publisher Copyright:
© 2018 American Chemical Society.

All Science Journal Classification (ASJC) codes

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

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10.1021/acs.macromol.8b00290

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title = "Nonmonotonic Glass Transition Temperature of Polymer Films Supported on Polymer Brushes",

abstract = "We modulated the grafting density (σ) and chain length of polystyrene (PS) brushes on substrates to probe their effect on the glass transition temperature (Tg) in overlaying PS thin films. The Tg of PS films was analyzed as a function of brush thickness (or σRg 2), where Rg is the radius of gyration of PS brushes. Our results indicate that PS films below 90 nm exhibit a nonmonotonic dependence of Tg on grafting density with the maximum Tg occurring near the regime of wetting-dewetting transition of the overlaying melt. The maximum Tg was found to be higher than the value of bulk PS system. Computer simulation results suggest that such trends arise as a consequence of the environment of enhanced friction presented by the brush layer and the overlap between the polymer film and the grafted layer.",

author = "Hoyeon Lee and Vaidyanathan Sethuraman and Yeongsik Kim and Wooseop Lee and Ryu, {Du Yeol} and Venkat Ganesan",

note = "Funding Information: V.G. acknowledges funding in part by grants from the Robert A. Welch Foundation (Grant F1599), the National Science Foundation (DMR-1306844), to King Abdullah University of Science and Technology (OSR-2016-CRG5-2993-1). Acknowledgment is also made to the Donors of the American Chemical Society Petroleum Research Fund for partial support of this research (56715-ND9). D.Y.R. acknowledges funding by the NRF grants (2017R1A2A2A05001048, 2017R1A4A1014569) funded by the Ministry of Science, ICT & Future Planning (MSIP), Korea. H.L. acknowledges funding by the Yonsei University Research Fund (2016-12-0011). Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",

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AU - Lee, Hoyeon

AU - Sethuraman, Vaidyanathan

AU - Kim, Yeongsik

AU - Lee, Wooseop

AU - Ryu, Du Yeol

AU - Ganesan, Venkat

N1 - Funding Information: V.G. acknowledges funding in part by grants from the Robert A. Welch Foundation (Grant F1599), the National Science Foundation (DMR-1306844), to King Abdullah University of Science and Technology (OSR-2016-CRG5-2993-1). Acknowledgment is also made to the Donors of the American Chemical Society Petroleum Research Fund for partial support of this research (56715-ND9). D.Y.R. acknowledges funding by the NRF grants (2017R1A2A2A05001048, 2017R1A4A1014569) funded by the Ministry of Science, ICT & Future Planning (MSIP), Korea. H.L. acknowledges funding by the Yonsei University Research Fund (2016-12-0011). Publisher Copyright: © 2018 American Chemical Society.

PY - 2018/6/26

Y1 - 2018/6/26

N2 - We modulated the grafting density (σ) and chain length of polystyrene (PS) brushes on substrates to probe their effect on the glass transition temperature (Tg) in overlaying PS thin films. The Tg of PS films was analyzed as a function of brush thickness (or σRg 2), where Rg is the radius of gyration of PS brushes. Our results indicate that PS films below 90 nm exhibit a nonmonotonic dependence of Tg on grafting density with the maximum Tg occurring near the regime of wetting-dewetting transition of the overlaying melt. The maximum Tg was found to be higher than the value of bulk PS system. Computer simulation results suggest that such trends arise as a consequence of the environment of enhanced friction presented by the brush layer and the overlap between the polymer film and the grafted layer.

AB - We modulated the grafting density (σ) and chain length of polystyrene (PS) brushes on substrates to probe their effect on the glass transition temperature (Tg) in overlaying PS thin films. The Tg of PS films was analyzed as a function of brush thickness (or σRg 2), where Rg is the radius of gyration of PS brushes. Our results indicate that PS films below 90 nm exhibit a nonmonotonic dependence of Tg on grafting density with the maximum Tg occurring near the regime of wetting-dewetting transition of the overlaying melt. The maximum Tg was found to be higher than the value of bulk PS system. Computer simulation results suggest that such trends arise as a consequence of the environment of enhanced friction presented by the brush layer and the overlap between the polymer film and the grafted layer.

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Nonmonotonic Glass Transition Temperature of Polymer Films Supported on Polymer Brushes

Abstract

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