Density functional theory and molecular dynamics studies of the energetics and kinetics of electroactive polymers : PVDF and P(VDF-TrFE)
We used first principles methods to study static and dynamical mechanical properties of the ferroelectric polymer poly(vinylidene fluoride) (PVDF) and its copolymer with trifluoro ethylene (TrFE). We use density functional theory [within the generalized gradient approxi...
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| Format: | Journal Article |
| Language: | English |
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2011
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| Online Access: | https://hdl.handle.net/10356/92218 http://hdl.handle.net/10220/6863 |
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| author | Su, Haibin Strachan, Alejandro Goddard III, William A. |
| author2 | School of Materials Science & Engineering |
| author_facet | School of Materials Science & Engineering Su, Haibin Strachan, Alejandro Goddard III, William A. |
| author_sort | Su, Haibin |
| collection | NTU |
| description | We used first principles methods to study static and dynamical mechanical properties of the ferroelectric
polymer poly(vinylidene fluoride) (PVDF) and its copolymer with trifluoro ethylene (TrFE). We use density
functional theory [within the generalized gradient approximation (DFT-GGA)] to calculate structure and energetics
for various crystalline phases for PVDF and P(VDF-TrFE). We find that the lowest energy phase for
PVDF is a nonpolar crystal with a combination of trans (T) and gauche (G) bonds; in the case of the copolymer
the role of the extra (bulkier) F atoms is to stabilize T bonds. This leads to the higher crystallinity and
piezoelectricity observed experimentally. Using the MSXX first principles-based force field (FF) with molecular
dynamics (MD), we find that the energy barrier necessary to nucleate a kink (gauche pairs separated by
trans bonds) in an all-T crystal is much lower (14.9 kcal/mol) in P(VDF-TrFE) copolymer than in PVDF
(24.8 kcal/mol). This correlates with the observation that the polar phase of the copolymer exhibits a solidsolid
transition to a nonpolar phase under heating while PVDF directly melts. We also studied the mobility of
an interface between polar and nonpolar phases under uniaxial stress; we find a lower threshold stress and a
higher mobility in the copolymer as compared with PVDF. Finally, considering plastic deformation under
applied shear, we find that the chains for P(VDF-TrFE) have a very low resistance to sliding, particularly along
the chain direction. The atomistic characterization of these “unit mechanisms” provides essential input to
mesoscopic or macroscopic models of electro-active polymers. |
| first_indexed | 2024-10-01T04:49:00Z |
| format | Journal Article |
| id | ntu-10356/92218 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T04:49:00Z |
| publishDate | 2011 |
| record_format | dspace |
| spelling | ntu-10356/922182023-07-14T15:51:22Z Density functional theory and molecular dynamics studies of the energetics and kinetics of electroactive polymers : PVDF and P(VDF-TrFE) Su, Haibin Strachan, Alejandro Goddard III, William A. School of Materials Science & Engineering DRNTU::Engineering::Materials::Magnetic materials We used first principles methods to study static and dynamical mechanical properties of the ferroelectric polymer poly(vinylidene fluoride) (PVDF) and its copolymer with trifluoro ethylene (TrFE). We use density functional theory [within the generalized gradient approximation (DFT-GGA)] to calculate structure and energetics for various crystalline phases for PVDF and P(VDF-TrFE). We find that the lowest energy phase for PVDF is a nonpolar crystal with a combination of trans (T) and gauche (G) bonds; in the case of the copolymer the role of the extra (bulkier) F atoms is to stabilize T bonds. This leads to the higher crystallinity and piezoelectricity observed experimentally. Using the MSXX first principles-based force field (FF) with molecular dynamics (MD), we find that the energy barrier necessary to nucleate a kink (gauche pairs separated by trans bonds) in an all-T crystal is much lower (14.9 kcal/mol) in P(VDF-TrFE) copolymer than in PVDF (24.8 kcal/mol). This correlates with the observation that the polar phase of the copolymer exhibits a solidsolid transition to a nonpolar phase under heating while PVDF directly melts. We also studied the mobility of an interface between polar and nonpolar phases under uniaxial stress; we find a lower threshold stress and a higher mobility in the copolymer as compared with PVDF. Finally, considering plastic deformation under applied shear, we find that the chains for P(VDF-TrFE) have a very low resistance to sliding, particularly along the chain direction. The atomistic characterization of these “unit mechanisms” provides essential input to mesoscopic or macroscopic models of electro-active polymers. Published version 2011-07-06T00:51:16Z 2019-12-06T18:19:28Z 2011-07-06T00:51:16Z 2019-12-06T18:19:28Z 2004 2004 Journal Article Su, H., Strachan, A. & Goddard III, W. A. (2004). Density functional theory and molecular dynamics studies of the energetics and kinetics of electroactive polymers: PVDF and P(VDF-TrFE). Physical Review B, B70. https://hdl.handle.net/10356/92218 http://hdl.handle.net/10220/6863 10.1103/PhysRevB.70.064101 en Physical review B © 2004 American Physical Society. This paper was published in Physical Review B and is made available as an electronic reprint (preprint) with permission of American Physical Society. The paper can be found at: [DOI: http://dx.doi.org/10.1103/PhysRevB.70.064101]. One print or electronic copy may be made for personal use only. Systematic or multiple reproduction, distribution to multiple locations via electronic or other means, duplication of any material in this paper for a fee or for commercial purposes, or modification of the content of the paper is prohibited and is subject to penalties under law. 8 p. application/pdf |
| spellingShingle | DRNTU::Engineering::Materials::Magnetic materials Su, Haibin Strachan, Alejandro Goddard III, William A. Density functional theory and molecular dynamics studies of the energetics and kinetics of electroactive polymers : PVDF and P(VDF-TrFE) |
| title | Density functional theory and molecular dynamics studies of the energetics and kinetics of electroactive polymers : PVDF and P(VDF-TrFE) |
| title_full | Density functional theory and molecular dynamics studies of the energetics and kinetics of electroactive polymers : PVDF and P(VDF-TrFE) |
| title_fullStr | Density functional theory and molecular dynamics studies of the energetics and kinetics of electroactive polymers : PVDF and P(VDF-TrFE) |
| title_full_unstemmed | Density functional theory and molecular dynamics studies of the energetics and kinetics of electroactive polymers : PVDF and P(VDF-TrFE) |
| title_short | Density functional theory and molecular dynamics studies of the energetics and kinetics of electroactive polymers : PVDF and P(VDF-TrFE) |
| title_sort | density functional theory and molecular dynamics studies of the energetics and kinetics of electroactive polymers pvdf and p vdf trfe |
| topic | DRNTU::Engineering::Materials::Magnetic materials |
| url | https://hdl.handle.net/10356/92218 http://hdl.handle.net/10220/6863 |
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