Physical and chemical aspects of the study of clusters, nanostructures and nanomaterials
Founded at 2009

Investigation of the physical properties of PVDF thin films obtained by 4D printing

N.V. Vostrov1, A.V. Solnyshkin1, I.M. Morsakov2, A.N. Belov3, P.N. Krylov1

1 Tver State University
2 JSC "SPC "Tvergeofizika"
3 National Research University of Electronic Technology

DOI: 10.26456/pcascnn/2022.14.561

Original article

Abstract: In this work, we searched for the optimal way to create ferroelectric nanostructured composite materials based on 4D-printed polyvinylidene fluoride polymer films. Method fused deposition modeling allow using polyvinylidene fluoride and its copolymers not only in microelectronics as pyroelectric and piezoelectric sensors, as well as creating dynamic memory elements, organic solar cells and used in robotics. At the first stage of the work, the authors were selected optimal extrusion parameters for the manufacture of a thread from powder and granules. The next stage of the work included the analysis and determination of printing parameters by the method of layer-by-layer filament deposition to obtain the best quality of polymer films. Using scanning electron microscopy, the existence of two phases, a polar β-phase and a nonpolar α-phase, is shown, where the crystalline phase is observed in the form of lamellar crystals chaotically oriented in the α-phase matrix. Pyroelectric measurements performed by the dynamic method showed the presence of a noticeable pyroelectric response in polyvinylidene fluoride films obtained using additive technologies, bypassing the orientation extraction stage. The calculation of the pyroelectric coefficient gives values corresponding to the values of the pyroelectric coefficient for polyvinylidene fluoride samples obtained by traditional methods.

Keywords: composite, polymer ferroelectric, additive technologies, 4D printing, 3D printing, spontaneous polarization, piezoelectric effect, pyroelectric effect, scanning electron microscope

  • Nikita V. Vostrov – Junior Researcher, Management of Scientific Research, Tver State University
  • Alexander V. Solnyshkin – Dr. Sc., Professor, Condensed Matter Physics Department, Tver State University
  • Ivan M. Morsakov – Researcher, JSC "SPC "Tvergeofizika"
  • Alexey N. Belov – Dr. Sc., Professor, Integrated Electronics and Microsystems Department, National Research University of Electronic Technology
  • Pavel N. Krylov – Senior Laboratory Assistant, Physical Chemistry Department, Tver State University


Vostrov, N.V. Investigation of the physical properties of PVDF thin films obtained by 4D printing / N.V. Vostrov, A.V. Solnyshkin, I.M. Morsakov, A.N. Belov, P.N. Krylov // Physical and chemical aspects of the study of clusters, nanostructures and nanomaterials. — 2022. — I. 14. — P. 561-571. DOI: 10.26456/pcascnn/2022.14.561. (In Russian).

Full article (in Russian): download PDF file


1. Bar-Cohen Y., Anderson I.A. Electroactive polymer (EAP) actuators – background review, Mechanics of Soft Materials, 2019, vol. 1, issue 1, art. no. 5, 14 p. DOI: 10.1007/s42558-019-0005-1.
2. Lang S.B., Muensit S. Review of some lesser-known applications of piezoelectric and pyroelectric polymers, Applied Physics A, 2006, vol. 85, issue 2, pp. 125-134. DOI: 10.1007/s00339-006-3688-8.
3. Naber R.C.G., Asadi K., Blom P.W.M. et al. Organic nonvolatile memory devices based on ferroelectricity, Advanced Materials, 2010,vol. 22, issue 9, pp. 933-945. DOI: 10.1002/adma.200900759.
4. Ramadan K.S., Sameoto D., Evoy S. A review of piezoelectric polymers as functional materials for electromechanical transducers, Smart Materials and Structures, 2014, vol. 23, issue 3, art. no. 033001, 27 p. DOI: 10.1088/0964-1726/23/3/033001.
5. Solnyshkin A.V., Morsakov I.M., Bogomolov A.A. et al. Dynamic pyroelectric response of composite based on ferroelectric copolymer of poly(vinylidene fluoride-trifluoroethylene) and ferroelectric ceramics of barium lead zirconate titanate, Applied Physics A, 2015, vol. 121, issue. 1, pp. 311-316. DOI: 10.1007/s00339-015-9446-z.
6. Ducrot P.-H., Dufour I., Ayela C. Optimization of PVDF-TrFE processing conditions for the fabrication of organic mems resonators, Scientific Reports, 2016, vol. 6, issue. 1, 7 p. DOI: 10.1038/srep19426.
7. Soulestin T., Ladmiral V., Domingues F.D.S. et al. Vinylidene fluoride- and trifluoroethylene-containing fluorinated electroactive copolymers. How does chemistry impact properties? Progress in Polymer Science, 2017, vol. 72, pp. 16-60. DOI: 10.1016/j.progpolymsci.2017.04.004.
8. Ruan L., Yao X., Chang Y. et al. Properties and applications of the β phase poly(vinylidene fluoride), Polymers, 2018, vol. 10, issue 3, art. no. 228, 27 p. DOI: 10.3390/polym10030228.
9. Belovickis J., Ivanov M., Samulionis V. et al. Dielectric, ferroelectric, and piezoelectric investigation of polymer-based P(VDF-TrFE) composites, Physica Status Solidi B, 2017, vol. 255, issue 3, art. no. 1700196, 6 p. DOI: 10.1002/pssb.201700196.
10. Yin Z., Tian B., Zhu Q. et al. Characterization and Application of PVDF and Its Copolymer Films Prepared by Spin-Coating and Langmuir–Blodgett Method, Polymers, 2019, vol. 11, art. no. 2033, 32 p. DOI: 10.3390/polym11122033.
11. Li H., Wang R., Han S.-T. et al. Ferroelectric polymers for non-volatile memory devices: a review, Polymer International, 2020, vol. 69, issue 6, pp. 533-544. DOI: 10.1002/pi.5980.
12. Li Q., Zhao J., He B. et al. Solution processable poly(vinylidene fluoride)-based ferroelectric polymers for flexible electronics, APL Materials, 2021,vol. 9, issue 1, art. no. 010902, 11 p. DOI: 10.1063/5.0035539.
13. Zhu H., Fu C., Mitsuishi M. Organic ferroelectric field-effect transistor memories with poly(vinylidene fluoride) gate insulators and conjugated semiconductor channels: a review, Polymer International, 2021, vol. 70, issue 4, pp. 404-413. DOI: 10.1002/pi.6029.
14. Solnyshkin A.V., Wegener M., Künstler W. et al. Anomalies of dielectric properties of vinylidene fluoride-trifluoroethylene copolymer films, Physics of the Solid State, 2008, vol. 50, issue 3, pp. 562-567. DOI: 10.1134/S1063783408030281.
15. Ngoa T.D., Kashania A., Imbalzanoa G. et al. Additive manufacturing (3D printing): A review of materials, methods, applications and challenges, Composites Part B: Engineering, 2018, vol. 143, pp. 172-196. DOI: 10.1016/j.compositesb.2018.02.012.
16. Ryder M.A., Lados D.A., Iannacchione G.S. Peterson A.M. Fabrication and properties of novel polymer-metal composites using fused deposition modeling, Composites Science and Technology, 2018, vol. 158, pp. 43-50. DOI: 10.1016/j.compscitech.2018.01.049.
17. Zheng X., Deotte J., Alonso M.P. et al. Design and optimization of a light-emitting diode projection micro- stereolithography three-dimensional manufacturing, Review of Scientific Instruments, 2012, vol. 83, issue 12, art. no. 125001, 7 p. DOI:10.1063/1.4769050.
18. Ahn D., Kweon J.-H., Choi J., Lee S. Quantification of surface roughness of parts processed by laminated object manufacturing, Journal of Materials Processing Technology, 2012, vol. 212, issue 2, pp. 339-346. DOI: 10.1016/j.jmatprotec.2011.08.013.
19. Truby R.L., Lewis J.A. Printing soft matter in three dimensions, Nature, 2016, vol. 540, pp. 371-378. DOI: 10.1038/nature21003.
20. Yap C. Y., Chua C. K., Dong Z.L. et al. Review of selective laser melting: materials and applications, Applied Physics Reviews, 2015, vol. 2, issue 4, art. no. 041101, 22 p. DOI:10.1063/1.4935926.
21. Chen A.-N., Wu J.-M., Liu K. et al. High-performance ceramic parts with complex shape prepared by selective laser sintering: a review, Advances in Applied Ceramics, 2017, vol. 117, issue 2, pp. 100-117. DOI: 10.1080/17436753.2017.1379586.
22. Chen C., Wang X., Wang Y. et al. Additive manufacturing of piezoelectric materials, Advanced Functional Materials, 2020, vol. 30, issue 52, art. no. 2005141, 29 p. DOI: 10.1002/adfm.202005141.
23. Baklanova K.D., Solnyshkin A.V., Kislova I.L. et al. Pyroelectric properties and local piezoelectric response of lithium niobate thin films, Physica Status Solidi A, 2017, vol. 215, issue 5, art. no. 1700690, 6 p. DOI: 10.1002/pssa.201700690.

Content |