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      P(VDF-TrFE) nanofibers: structure of the ferroelectric and paraelectric phases through IR and Raman spectroscopies†

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      RSC Advances
      The Royal Society of Chemistry

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          Abstract

          This study elucidates the complex morphology and the related spectroscopic response of poly(vinylidene fluoride- co-trifluoroethylene) copolymer, with 80% molar VDF content, namely P(VDF-TrFE) (80/20). We investigate the molecular structure, the morphology and the thermal behaviour of P(VDF-TrFE) samples obtained as electrospun nanofibers; we discuss their thermal evolution crossing the Curie temperature and the structure resulting after annealing, giving a comparison with P(VDF-TrFE) films. The new experimental data here obtained, combined with previous spectroscopic studies carried out on piezoelectric fluorinated polymers and copolymers, allow identifying spectroscopic markers sensitive to the molecular structure, the molecular orientation, the conformational defects and the kind of crystalline phase. We assign the vibrational modes localized on TrFE units by combining experimental observation and density functional calculations carried out on suitable molecular models. This work provides a sound set of diagnostic tools, which can be exploited for the assessment of structure/property relationships aimed at clarifying the molecular mechanisms leading to the piezoelectric performance of fluorinated copolymers.

          Abstract

          This study elucidates the complex morphology and the related spectroscopic response of poly(vinylidene fluoride- co-trifluoroethylene) copolymer, with 80% molar VDF content, namely P(VDF-TrFE) (80/20).

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          Ferroelectric polymers.

          A Lovinger (1983)
          Piezoelectricity and pyroelectricity, traditionally encountered in certain single crystals and ceramics, have now also been documented in a number of polymers. Recently, one such polymer-poly(vinylidene fluoride)-and some of its copolymers have been shown to be ferroelectric as well. The extraordinary molecular and supermolecular structural requirements for ferroelectric behavior in polymers are discussed in detail, with particular emphasis on poly(vinylidene fluoride). Piezoelectric, pyroelectric, and ferroelectric properties are also briefly reviewed, as are some promising applications of such polymers.
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            The Piezoelectricity of Poly (vinylidene Fluoride)

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              High performance piezoelectric devices based on aligned arrays of nanofibers of poly(vinylidenefluoride-co-trifluoroethylene).

              Multifunctional capability, flexible design, rugged lightweight construction and self-powered operation are desired attributes for electronics that directly interface with the human body or with advanced robotic systems. For these applications, piezoelectric materials, in forms that offer the ability to bend and stretch, are attractive for pressure/force sensors and mechanical energy harvesters. Here, we introduce a large area, flexible piezoelectric material that consists of sheets of electrospun fibres of the polymer poly[(vinylidenefluoride-co-trifluoroethylene]. The flow and mechanical conditions associated with the spinning process yield free-standing, three-dimensional architectures of aligned arrangements of such fibres, in which the polymer chains adopt strongly preferential orientations. The resulting material offers exceptional piezoelectric characteristics, to enable ultra-high sensitivity for measuring pressure, even at exceptionally small values (0.1 Pa). Quantitative analysis provides detailed insights into the pressure sensing mechanisms, and establishes engineering design rules. Potential applications range from self-powered micro-mechanical elements, to self-balancing robots and sensitive impact detectors.
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                Author and article information

                Journal
                RSC Adv
                RSC Adv
                RA
                RSCACL
                RSC Advances
                The Royal Society of Chemistry
                2046-2069
                13 October 2020
                12 October 2020
                13 October 2020
                : 10
                : 62
                : 37779-37796
                Affiliations
                [a] Dipartimento di Chimica, Materiali e Ingegneria Chimica “Giulio Natta”, Politecnico di Milano, Piazza Leonardo da Vinci 32 20133 Milano Italy chiara.castiglioni@ 123456polimi.it
                [b] Center for Nano Science and Technology@PoliMi, Istituto Italiano di Tecnologia Via Pascoli 70/3 20133 Milano Italy
                Author information
                https://orcid.org/0000-0001-9682-0043
                https://orcid.org/0000-0003-2264-1792
                https://orcid.org/0000-0002-4577-0741
                https://orcid.org/0000-0003-2095-9852
                https://orcid.org/0000-0002-7917-426X
                https://orcid.org/0000-0002-6945-9157
                Article
                d0ra05478j
                10.1039/d0ra05478j
                9057215
                35515179
                2fb30b9b-104c-4a96-8be7-008638d1191c
                This journal is © The Royal Society of Chemistry
                History
                : 22 June 2020
                : 30 September 2020
                Page count
                Pages: 18
                Categories
                Chemistry
                Custom metadata
                Paginated Article

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