Vibrational Sum Frequency Generation (SFG) Analysis of Ferroelectric Response of PVDF-Based Copolymer and Terpolymer

Inseok Chae; Saad Ahmed; Hassene Ben Atitallah; Jiawei Luo; Qing Wang; Zoubeida Ounaies; Seong H. Kim

doi:10.1021/acs.macromol.7b00188

Vibrational Sum Frequency Generation (SFG) Analysis of Ferroelectric Response of PVDF-Based Copolymer and Terpolymer

Inseok Chae, Saad Ahmed, Hassene Ben Atitallah, Jiawei Luo, Qing Wang, Zoubeida Ounaies, Seong H. Kim

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

21 Scopus citations

Abstract

In poly(vinylidene difluoride) (PVDF)-based polymers, the alignment of dipoles of the crystalline β phase with all-trans conformations is responsible for ferroelectricity; however, there is a lack of direct spectroscopic evidence for this phenomenon. We report in situ monitoring of the molecular orientations associated with ferroelectric responses of PVDF-based polymers using vibrational sum frequency generation (SFG) spectroscopy. The orientation of CH₂ groups with respect to the −(CH₂CF₂)_n- chain axis of the poled β domains in a PVDF copolymer was determined from the SFG dependence of an uniaxially aligned sample on the laser polarization and azimuthal angle. The relative intensities of CH₂ symmetric and asymmetric stretch modes as well as their total intensities revealed the transformation of the all-trans conformation domains during the electrical poling of PVDF based co- and terpolymer films.

Original language	English (US)
Pages (from-to)	2838-2844
Number of pages	7
Journal	Macromolecules
Volume	50
Issue number	7
DOIs	https://doi.org/10.1021/acs.macromol.7b00188
State	Published - Apr 11 2017

All Science Journal Classification (ASJC) codes

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

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10.1021/acs.macromol.7b00188

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title = "Vibrational Sum Frequency Generation (SFG) Analysis of Ferroelectric Response of PVDF-Based Copolymer and Terpolymer",

abstract = "In poly(vinylidene difluoride) (PVDF)-based polymers, the alignment of dipoles of the crystalline β phase with all-trans conformations is responsible for ferroelectricity; however, there is a lack of direct spectroscopic evidence for this phenomenon. We report in situ monitoring of the molecular orientations associated with ferroelectric responses of PVDF-based polymers using vibrational sum frequency generation (SFG) spectroscopy. The orientation of CH2 groups with respect to the −(CH2CF2)n- chain axis of the poled β domains in a PVDF copolymer was determined from the SFG dependence of an uniaxially aligned sample on the laser polarization and azimuthal angle. The relative intensities of CH2 symmetric and asymmetric stretch modes as well as their total intensities revealed the transformation of the all-trans conformation domains during the electrical poling of PVDF based co- and terpolymer films.",

author = "Inseok Chae and Saad Ahmed and Atitallah, {Hassene Ben} and Jiawei Luo and Qing Wang and Zoubeida Ounaies and Kim, {Seong H.}",

note = "Funding Information: This work was supported by the Air Force Office of Scientific Research (AFOSR) (grant FA9550-16-1-0062). The fs broadband SFG system used in this study was constructed with the support from the Center for Lignocellulose Structure and Formation (CLSF), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, and Office of Basic Energy Sciences under Award DESC0001090. The authors acknowledge Dr. Jiezhu Jin for preparation of PVDF-HFP samples for this study and Dr. Laura Bradley for some of preliminary tests in the past. Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

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AU - Chae, Inseok

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AU - Atitallah, Hassene Ben

AU - Luo, Jiawei

AU - Wang, Qing

AU - Ounaies, Zoubeida

AU - Kim, Seong H.

N1 - Funding Information: This work was supported by the Air Force Office of Scientific Research (AFOSR) (grant FA9550-16-1-0062). The fs broadband SFG system used in this study was constructed with the support from the Center for Lignocellulose Structure and Formation (CLSF), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, and Office of Basic Energy Sciences under Award DESC0001090. The authors acknowledge Dr. Jiezhu Jin for preparation of PVDF-HFP samples for this study and Dr. Laura Bradley for some of preliminary tests in the past. Publisher Copyright: © 2017 American Chemical Society.

PY - 2017/4/11

Y1 - 2017/4/11

N2 - In poly(vinylidene difluoride) (PVDF)-based polymers, the alignment of dipoles of the crystalline β phase with all-trans conformations is responsible for ferroelectricity; however, there is a lack of direct spectroscopic evidence for this phenomenon. We report in situ monitoring of the molecular orientations associated with ferroelectric responses of PVDF-based polymers using vibrational sum frequency generation (SFG) spectroscopy. The orientation of CH2 groups with respect to the −(CH2CF2)n- chain axis of the poled β domains in a PVDF copolymer was determined from the SFG dependence of an uniaxially aligned sample on the laser polarization and azimuthal angle. The relative intensities of CH2 symmetric and asymmetric stretch modes as well as their total intensities revealed the transformation of the all-trans conformation domains during the electrical poling of PVDF based co- and terpolymer films.

AB - In poly(vinylidene difluoride) (PVDF)-based polymers, the alignment of dipoles of the crystalline β phase with all-trans conformations is responsible for ferroelectricity; however, there is a lack of direct spectroscopic evidence for this phenomenon. We report in situ monitoring of the molecular orientations associated with ferroelectric responses of PVDF-based polymers using vibrational sum frequency generation (SFG) spectroscopy. The orientation of CH2 groups with respect to the −(CH2CF2)n- chain axis of the poled β domains in a PVDF copolymer was determined from the SFG dependence of an uniaxially aligned sample on the laser polarization and azimuthal angle. The relative intensities of CH2 symmetric and asymmetric stretch modes as well as their total intensities revealed the transformation of the all-trans conformation domains during the electrical poling of PVDF based co- and terpolymer films.

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Vibrational Sum Frequency Generation (SFG) Analysis of Ferroelectric Response of PVDF-Based Copolymer and Terpolymer

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