Relaxations and relaxor-ferroelectric-like response of nanotubularly confined poly(vinylidene fluoride)
File(s)
Author(s)
Type
Journal Article
Abstract
Herein, we elucidate the impact of tubular confinement on the structure and relaxation behavior of poly(vinylidene difluoride) (PVDF) and how these affect the para-/ferroelectric behavior of this polymer. We use PVDF nanotubes that were solidified in anodic aluminum oxide (AAO) templates. Dielectric spectroscopy measurements evidence a bimodal relaxation process for PVDF nanotubes: besides the bulk-like α-relaxation, we detect a notably slower relaxation that is associated with the PVDF regions of restricted dynamics at the interface with the AAO pore. Strikingly, both the bulk-like and the interfacial relaxation tend to become temperature independent as the temperature increases, a behavior that has been observed before in inorganic relaxor ferroelectrics. In line with this, we observe that the real part of the dielectric permittivity of the PVDF nanotubes exhibits a broad maximum when plotted against the temperature, which is, again, a typical feature of relaxor ferroelectrics. As such, we propose that, in nanotubular PVDF, ferroelectric-like nanodomains are formed in the amorphous phase regions adjacent to the AAO interface. These ferroelectric nanodomains may result from an anisotropic chain conformation and a preferred orientation of local dipoles due to selective H-bond formation between the PVDF macromolecues and the AAO walls. Such relaxor-ferroelectric-like behavior has not been observed for nonirradiated PVDF homopolymer; our findings thus may enable in the future alternative applications for this bulk commodity plastic, e.g., for the production of electrocaloric devices for solid-state refrigeration which benefit from a relaxor-ferroelectric-like response.
Date Issued
2017-03-19
Date Acceptance
2017-03-13
Citation
Chemistry of Materials, 2017, 29 (8), pp.3515-3525
ISSN
1520-5002
Publisher
American Chemical Society
Start Page
3515
End Page
3525
Journal / Book Title
Chemistry of Materials
Volume
29
Issue
8
Copyright Statement
© 2017 American Chemical Society
Sponsor
Commission of the European Communities
Identifier
http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000400233100020&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=1ba7043ffcc86c417c072aa74d649202
Grant Number
654682
Subjects
Science & Technology
Physical Sciences
Technology
Chemistry, Physical
Materials Science, Multidisciplinary
Chemistry
Materials Science
GLASS-TRANSITION TEMPERATURE
X-RAY-SCATTERING
CYLINDRICAL NANOPORES
COLD CRYSTALLIZATION
SEGMENTAL DYNAMICS
ORGANIC MATERIALS
PHASE-TRANSITION
ULTRATHIN FILMS
POLYMER-FILMS
THIN-FILMS
Publication Status
Published