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Electroactive poly(vinylidene fluoride)-based structures for advanced applications

Nature Protocols volume 13, pages 681–704 (2018)Cite this article

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Abstract

Poly(vinylidene fluoride) (PVDF) and its copolymers are the polymers with the highest dielectric constants and electroactive responses, including piezoelectric, pyroelectric and ferroelectric effects. This semicrystalline polymer can crystallize in five different forms, each related to a different chain conformation. Of these different phases, the β phase is the one with the highest dipolar moment and the highest piezoelectric response; therefore, it is the most interesting for a diverse range of applications. Thus, a variety of processing methods have been developed to induce the formation of the polymer β phase. In addition, PVDF has the advantage of being easily processable, flexible and low-cost. In this protocol, we present a number of reproducible and effective methods to produce β-PVDF-based morphologies/structures in the form of dense films, porous films, 3D scaffolds, patterned structures, fibers and spheres. These structures can be fabricated by different processing techniques, including doctor blade, spin coating, printing technologies, non-solvent-induced phase separation (NIPS), temperature-induced phase separation (TIPS), solvent-casting particulate leaching, solvent-casting using a 3D nylon template, freeze extraction with a 3D poly(vinyl alcohol) (PVA) template, replica molding, and electrospinning or electrospray, with the fabrication method depending on the desired characteristics of the structure. The developed electroactive structures have shown potential to be used in a wide range of applications, including the formation of sensors and actuators, in biomedicine, for energy generation and storage, and as filtration membranes.

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Figure 1
Figure 2: Schematic representation of the preparation of the PVDF-based solution.
Figure 3: Schematic representation of the preparation of β-PVDF films by doctor blade (option A).
Figure 4: Schematic representation of the preparation of β-PVDF by spin coating (option B).
Figure 5: Schematic representation of the preparation of patterned P(VDF-TrFE) films by ink-jet printing (option C).
Figure 6: Schematic representation of the preparation of patterned P(VDF-TrFE) films by screen printing (option D).
Figure 7: Schematic representation of the preparation of patterned P(VDF-TrFE) by spray printing/coating (option E).
Figure 8: Schematic representation of the preparation of porous β-PVDF films by NIPS (option F).
Figure 9: Schematic representation of the preparation of porous β-PVDF films by TIPS (option G).
Figure 10: Schematic representation of the preparation of 3D β-PVDF scaffolds by solvent-casting particulate leaching (option H).
Figure 11: Schematic representation of the preparation of 3D β-PVDF scaffolds by solvent-casting and 3D nylon templates (option I).
Figure 12: Schematic representation of the preparation of 3D β-PVDF scaffolds by freeze extraction with a 3D PVA template (option J).
Figure 13: Schematic representation for the preparation of patterned β-PVDF structures by replica molding (option K).
Figure 14: Schematic representation of the preparation of β-PVDF fibers and spheres by electrospinning and electrospraying (options L and M, respectively).
Figure 15: PVDF film thickness as a function of rotational velocity.
Figure 16: Representative SEM images of the distinct structures/morphologies that can be obtained from the different protocols using PVDF or its copolymers.

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Acknowledgements

The authors thank the FCT (Fundação para a Ciência e Tecnologia) for financial support under the framework of Strategic Funding grants UID/FIS/04650/2013, UID/EEA/04436/2013 and UID/QUI/0686/2016; and projects PTDC/EEI-SII/5582/2014 and PTDC/CTM-ENE/5387/2014; as well as through FEDER funds from COMPETE 2020—Programa Operacional Competitividade e Internacionalização (POCI). Funding in the framework of the EuroNanoMed 2016 call, Project LungChek ENMed/0049/2016, is also acknowledged. The authors also thank the FCT for financial support under grants SFRH/BPD/90870/2012 (C.R.), SFRH/BPD/112547/2015 (C.M.C.), SFRH/BPD/121526/2016 (D.M.C.), SFRH/BD/98219/2013 (J.O.), SFRH/BPD/96227/2013 (P.M.) and SFRH/BPD/98109/2013 (V.F.C.). Financial support from the Spanish Ministry of Economy and Competitiveness (MINECO) through project MAT2016-76039-C4-3-R (AEI/FEDER, UE) (including FEDER financial support) and from the Basque Government Industry Department under the ELKARTEK Program is also acknowledged.

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Authors and Affiliations

  1. Centro de Física, Universidade do Minho, Campus de Gualtar, Braga, Portugal

    Clarisse Ribeiro, Carlos M Costa, Juliana Oliveira, Pedro Martins, Renato Gonçalves, Vanessa F Cardoso & Senentxu Lanceros-Méndez

  2. Centro de Engenharia Biológica (CEB), Universidade do Minho, Campus de Gualtar, Braga, Portugal

    Clarisse Ribeiro

  3. Centro de Química, Universidade do Minho, Campus de Gualtar, Braga, Portugal

    Carlos M Costa

  4. Departamento de Química e CQ-VR, Universidade de Trás-os-Montes e Alto Douro, Vila Real, Portugal

    Daniela M Correia

  5. Basque Center for Materials, Applications and Nanostructures (BCMaterials), UPV/EHU Science Park, Leioa, Spain

    Daniela M Correia & Senentxu Lanceros-Méndez

  6. Centre for Mechanical and Aerospace Science and Technologies (C-MAST), Universidade da Beira Interior, Covilhã, Portugal

    João Nunes-Pereira

  7. Departamento de Eletrónica Industrial (DEI), CMEMS-UMinho, Universidade do Minho, Campus de Azurém, Guimarães, Portugal

    Vanessa F Cardoso

  8. IKERBASQUE,,

    Senentxu Lanceros-Méndez

  9. Basque Foundation for Science, Bilbao, Spain

    Senentxu Lanceros-Méndez

Authors
  1. Clarisse Ribeiro
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  2. Carlos M Costa
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  3. Daniela M Correia
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  4. João Nunes-Pereira
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  5. Juliana Oliveira
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  6. Pedro Martins
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  7. Renato Gonçalves
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  8. Vanessa F Cardoso
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  9. Senentxu Lanceros-Méndez
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Contributions

All authors contributed equally to this work, being responsible for the different protocols: P.M. and J.O.: doctor blade and printing; V.F.C.: spin-coating and patterned porous structures; C.M.C. and J.N.-P.: porous films by NIPS and TIPS; C.R. and D.M.C.: 3D scaffolds; D.M.C. and R.G.: fibers and spheres; and S.L.-M.: conceived, designed and supervised the project. All authors contributed to the writing and editing of the manuscript.

Corresponding author

Correspondence to Senentxu Lanceros-Méndez.

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Competing interests

The authors declare no competing financial interests.

Integrated supplementary information

Supplementary Figure 1 Optical microscope images of nylon templates used to fabricate PVDF scaffolds.

Optical microscope images of nylon templates for obtaining PVDF scaffolds with pore diameters of a) 60 and b) 150 μm. The scale bar (100 μm) is valid for both images.

Supplementary Figure 2 Optical microscope images of pre-molds used to fabricate patterned porous PVDF structures.

Optical microscope images of: a) SU-8 pre-mold fabricated by photolithography; b) PDMS mold fabricated by replica molding using the SU-8 pre-mold. The scale bar (150 μm) is valid for both images.

Supplementary information

Supplementary Text and Figures

Supplementary Figures 1 and 2, and Supplementary Methods. (PDF 689 kb)

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Ribeiro, C., Costa, C., Correia, D. et al. Electroactive poly(vinylidene fluoride)-based structures for advanced applications. Nat Protoc 13, 681–704 (2018). https://doi.org/10.1038/nprot.2017.157

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