FOLLOWUS
a.Key Laboratory of Rubber-Plastics, Qingdao University of Science & Technology, Qingdao 266042, China
b.School of Chemical Engineering, Key Laboratory of Rubber-Plastics, Qingdao University of Science & Technology, Qingdao 266042, China
c.State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China
zhanghao@qust.edu.cn (H.Z.)
skyan@qust.edu.cn or skyan@mail.buct.edu.cn (S.K.Y.)
Received:07 December 2024,
Revised:24 December 2024,
Accepted:2025-01-07,
Published Online:13 March 2025,
Published:2025-02
Scan QR Code
Li, H. P.; Lian,g J. M.; Song, H. Y.; Zhu, H. Q.; Zhao, W. P.; Wang, S. J.; Zhang, H.; Yan, S. K. Poly(vinylidene fluoride) of different β-phase/γ-phase ratio prepared by heat controlled spin coating and potassium bromide as nucleating agent. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-025-3302-1
Hai-Peng Li, Jia-Meng Liang, Hao-Ying Song, et al. Poly(vinylidene fluoride) of Different
Li, H. P.; Lian,g J. M.; Song, H. Y.; Zhu, H. Q.; Zhao, W. P.; Wang, S. J.; Zhang, H.; Yan, S. K. Poly(vinylidene fluoride) of different β-phase/γ-phase ratio prepared by heat controlled spin coating and potassium bromide as nucleating agent. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-025-3302-1 DOI:
Hai-Peng Li, Jia-Meng Liang, Hao-Ying Song, et al. Poly(vinylidene fluoride) of Different
Herein
a simple method for preparing poly(vinylidene fluoride) (PVDF) films with controlled
β
/
γ
ratios by spin-coating assisted by potassium bromide (KBr) is proposed. The results show that the relative fraction of the
β
phase (denoted as
F
β
) for the films prepared on the KBr surface first decreased until a critical temperature (denoted as
T
c
) was reached
and then increased with increasing spin-coating temperature. This was related to the dissolved K and Br ions in the films. Further experiments showed that below
T
c
high humidity can enhance
F
β
but exhibit an adverse effect at and above
T
c
. The high content of K and Br ions in the PVDF/KBr blend film and larger shear stress can facilitate the formation of the
β
phase
leading exclusively to the formation of
β
- and
γ
-phases. The mechanism responsible for the change in
F
β
with temperature was proposed: below
T
c
the decrease in water intake with increasing temperature results in the decline of
F
β
whereas above
T
c
the increase in
F
β
with temperature is attributed to the synergistic effect of ions and shear stress. Ultimately
this paves the way for fabricating PVDF films with tailored
β
/
γ
ratios for electroactive and energy-harvesting applications.
Qian, X.; Chen, X.; Zhu, L.; Zhang, Q. M. Fluoropolymer ferroelectrics: multifunctional platform for polar-structured energy conversion. Science 2023 , 380 , eadg0902..
Costa, C. M.; Cardoso, V. F.; Martins, P.; Correia, D. M.; Gonçalves, R.; Costa, P.; Correia, V.; Ribeiro, C.; Fernandes, M. M.; Martins, P. M.; Lanceros-Méndez, S. Smart and multifunctional materials based on electroactive poly(vinylidene fluoride): recent advances and opportunities in sensors, actuators, energy, environmental, and biomedical applications. Chem. Rev. 2023 , 123 , 11392−11487..
Zhang, L.; Li, S.; Zhu, Z.; Rui, G.; Du, B.; Chen, D.; Huang, Y.-F.; Zhu, L. Recent progress on structure manipulation of poly(vinylidene fluoride)-based ferroelectric polymers for enhanced piezoelectricity and applications. Adv. Funct. Mater. 2023 , 33 , 2301302..
Furukawa, T. Ferroelectric properties of vinylidene fluoride copolymers. Phase Transit. 1989 , 18 , 143−211..
Hasegawa, R.; Kobayashi, M.; Tadokoro, H. Molecular conformation and packing of poly(vinylidene fluoride). Stability of three crystalline forms and the effect of high pressure. Polym. J. 1972 , 3 , 591−599..
Davis, G. T.; McKinney, J. E.; Broadhurst, M. G.; Roth, S. C. Electric-field-induced phase changes in poly(vinylidene fluoride). J. Appl. Phys. 1978 , 49 , 4998−5002..
Hattori, T.; Kanaoka, M.; Ohigashi, H. Improved piezoelectricity in thick lamellar β -form crystals of poly(vinylidene fluoride) crystallized under high pressure. J. Appl. Phys. 1996 , 79 , 2016−2022..
Sencadas, V.; Gregorio Jr, R.; Lanceros-Méndez, S. α to β phase transformation and microestructural changes of PVDF films induced by uniaxial stretch. J. Macromol. Sci . 2009 , 48 , 514−525..
Gradys, A.; Sajkiewicz, P.; Adamovsky, S.; Minakov, A.; Schick, C. Crystallization of poly(vinylidene fluoride) during ultra-fast cooling. Thermochim. Acta 2007 , 461 , 153−157..
Feng, M.; Wan, R.; Hu, J.; Li, H.; Wang, S.; Yan, S.; Sun, X. The γ → β phase-transitionbehavior of polyvinylidene fluoride under uniaxial drawing. CrystEngComm 2023 , 25 , 5184−5192..
Martins, P.; Lopes, A. C.; Lanceros-Mendez, S. Electroactive phases of poly(vinylidene fluoride): determination, processing and applications. Prog. Polym. Sci. 2014 , 39 , 683−706..
Yin, Z.; Tian, B.; Zhu, Q.; Duan, C. Characterization and application of PVDF and its copolymer films prepared by spin-coating and Langmuir–Blodgett method. Polymers 2019 , 11 , 2033..
Benz, M.; Euler, W. B.; Gregory, O. J. The role of solution phase water on the deposition of thin films of poly(vinylidene fluoride). Macromolecules 2002 , 35 , 2682−2688..
Cardoso, V. F.; Minas, G.; Costa, C. M.; Tavares, C. J.; Lanceros-Mendez, S. Micro and nanofilms of poly(vinylidene fluoride) with controlled thickness, morphology and electroactive crystalline phase for sensor and actuator applications. Smart Mater. Struct. 2011 , 20 , 087002..
Yoon, S.; Prabu, A. A.; Kim, K. J.; Park, C. Metal Salt-induced ferroelectric crystalline phase in poly(vinylidene fluoride) films. Macromol. Rapid Commun. 2008 , 29 , 1316−1321..
Ramasundaram, S.; Yoon, S.; Kim, K. J.; Lee, J. S.; Park, C. Crystalline structure and ferroelectric response of poly(vinylidene fluoride)/organically modifi ed silicate thin films prepared by heat controlled spin coating. Macromol. Chem. Phys. 2009 , 210 , 951−960..
Mandal, D.; Kim, K. J.; Lee, J. S. Simple synthesis of palladium nanoparticles, β -phase formation, and the control of chain and dipole orientations in palladium-doped poly(vinylidene fluoride) thin films. Langmuir 2012 , 28 , 10310−10317..
Ramasundaram, S.; Yoon, S.; Kim, K. J.; Lee, J. S. Direct preparation of nanoscale thin films of poly(vinylidene fluoride) containing β-crystalline phase by heat-controlled spin coating. Macromol. Chem. Phys. 2008 , 209 , 2516−2526..
Dhevi, D. M.; Prabu, A. A.; Kim, K. J. FTIR studies on polymorphic control of PVDF ultrathin films by heat-controlled spin coater. J. Mater. Sci. 2016 , 51 , 3619−3627..
Kang, S. J.; Park, Y. J.; Sung, J.; Jo, P. S.; Park, C.; Kim, K. J.; Cho, B. O. Spin cast ferroelectric beta poly(vinylidene fluoride) thin films via rapid thermal annealing. Appl. Phys. Lett. 2008 , 92 , 012921..
He, X.; Yao, K. Crystallization mechanism and piezoelectric properties of solution-derived ferroelectric poly(vinylidene fluoride) thin films. Appl. Phys. Lett. 2006 , 89 , 112909..
Lovinger, A. J. Crystallization of the β phase of poly(vinylidene fluoride) from the melt. Polymer 1981 , 22 , 412−413..
Miyazaki, T.; Takeda, Y.; Akasaka, M.; Sakai, M.; Hoshiko, A. Preparation of isothermally crystallized γ -form poly(vinylidene fluoride) films by adding a KBr powder as a nucleating agent. Macromolecules 2008 , 41 , 2749−2753..
Miyazaki, T.; Takeda, Y. Role of the KBr surfaces in crystallization of poly(vinylidene fluoride) films with a KBr powder as a nucleating agent. Eur. Polym. J. 2014 , 61 , 1−12..
Grubb, D. T.; Cebe, P.; Choi, K. W. Solution grown crystals of poly(vinylidene fluoride): the effect of ionic species on growth. Ferroelectrics 1984 , 57 , 121−138..
Nie, Y.; Zhao, W.; Chen, X.; Zhang, H.; Hu, J.; Wang, S.; Yan, S. Different cryst allization behaviors of poly(vinylidene fluoride) blended with or coated with cetyltrimethylammonium bromide. Macromolecules 2023 , 56 , 8214−8221..
Benz, M.; Euler, W. B.; Gregory, O. J. The influence of preparation conditions on the surface morphology of poly(vinylidene fluoride) films. Langmuir 2001 , 17 , 239−243..
Li, W. J.; Meng, Q. J.; Zheng, Y. S.; Zhang, Z. C.; Xia, W. M.; Xu, Z. Electric energy storage properties of poly(vinylidene fluoride). Appl. Phys. Lett. 2010 , 96 , 192905..
Ghosh, S. K.; Rahman, W.; Middya, T. R.; Sen, S.; Mandal, D. Improved breakdown strength and electrical energy storage performance of γ -poly(vinylidene fluoride)/unmodified montmorillonite clay nano-dielectrics. Nanotechnology 2016 , 27 , 215401..
Valentin, V. K. The structure and properties of block poly(vinylidene fluoride) and systems based on it. Russ. Chem. Rev. 1996 , 65 , 865..
Jurczuk, K.; Galeski, A.; Mackey, M.; Hiltner, A.; Baer, E. Orientation of PVDF α and γ crystals in nanolayered films. Colloid Polym. Sci. 2015 , 293 , 1289−1297..
Tashiro, K.; Kobayashi, M.; Tadokoro, H. Vibrational spectra and disorder-order transition of poly(vinylidene fluoride) form III. Macromolecules 1981 , 14 , 1757−1764..
Huang, Z. X.; Li, L. W.; Huang, Y. Z.; Rao, W. X.; Jiang, H. W.; Wang, J.; Zhang, H. H.; He, H. Z.; Qu, J. P. Self-poled piezoelectric polymer composites via melt-state energy implantation. Nat. Commun. 2024 , 15 , 819..
Meng, N.; Ren, X.; Santagiuliana, G.; Ventura, L.; Zhang, H.; Wu, J.; Yan, H.; Reece, M. J.; Bilotti, E. Ultrahigh β-phase content poly(vinylidene fluoride) with relaxor-like ferroelectricity for high energy density capacitors. Nat. commun. 2019 , 10 , 4535..
Li, M.; Wondergem, H. J.; Spijkman, M. J.; Asadi, K.; Katsouras, I.; Blom, P. W. M.; de Leeuw, D. M. Revisiting the δ -phase of poly(vinylidene fluoride) for solution-processed ferroelectric thin films. Nat. Mater. 2013 , 12 , 433−438..
Lee, S. G.; Ha, J. W.; Sohn, E. H.; Park, I. J.; Lee, S. B. Enhancement of polar crystalline phase formation in transparent PVDF-CaF 2 composite films. Appl. Surf. Sci. 2016 , 390 , 339−345..
Cai, X.; Lei, T.; Sun, D.; Lin, L. A critical analysis of the α, β and γ phases in poly(vinylidene fluoride) using FTIR. RSC Adv. 2017 , 7 , 15382−15389..
Gregorio, R.; Borges, D. S. Effect of crystallization rate on the formation of the polymorphs of solution cast poly(vinylidene fluoride). Polymer 2008 , 49 , 4009−4016..
Maji, S.; Sarkar, P. K.; Aggarwal, L.; Ghosh, S. K.; Mandal, D.; Sheet, G.; Acharya, S. Self-oriented β -crystalline phase in the polyvinylidene fluoride ferroelectric and piezo-sensitive ultrathin Langmuir–Schaefer film. Phys. Chem. Chem. Phys. 2015 , 17 , 8159−8165..
Soin, N.; Boyer, D.; Prashanthi, K.; Sharma, S.; Narasimulu, A. A.; Luo, J.; Shah, T. H.; Siores, E.; Thundat, T. Exclusive self-aligned β-phase PVDF films with abnormal piezoelectric coefficient prepared via phase inversion. Chem. Commun. 2015 , 51 , 8257−8260..
Chan, K. Y.; Li, C. L.; Wang, D. M.; Lai, J. Y. Formation of porous structures and crystalline phases in poly(vinylidene fluoride) membranes prepared with nonsolvent-induced phase separation—roles of solvent polarity. Polymers 2023 , 15 , 1314..
Jung, J. T.; Kim, J. F.; Wang, H. H.; di Nicolo, E.; Drioli, E.; Lee, Y. M. Understanding the non-solvent induced phase separation (NIPS) effect during the fabrication of microporous PVDF membranes via thermally induced phase separation (TIPS). J. Membr. Sci. 2016 , 514 , 250−263..
Qiu, Z.; Lei, T.; Li, S.; Cai, X.; Yang, K. Insights into polymorphic transition of PVDF during nonsolvent-induced phase separation. Macromolecules 2024 , 57 , 1159−1168..
Liang, C. L.; Mai, Z. H.; Xie, Q.; Bao, R. Y.; Yang, W.; Xie, B. H.; Yang, M.-B. Induced formation of dominating polar phases of poly(vinylidene fluoride): positive ion–CF 2 dipole or negative ion–CH 2 dipole interaction. J. Phys. Chem. B 2014 , 118 , 9104−9111..
Chu, Z.; Zhao, R.; Wang, B.; Liu, L.; Ma, Z.; Li, Y. Ef fect of ions on the flow-induced crystallization of poly(vinylidene fluoride). Macromolecules 2021 , 54 , 3800−3809..
Benz, M.; Euler, W. B. Determination of the crystalline phases of poly(vinylidene fluoride) under different preparation conditions using differential scanning calorimetry and infrared spectroscopy. J. Appl. Polym. Sci. 2003 , 89 , 1093−1100..
Li, X.; Han, Y.; An, L. Surface morphology evolution of thin triblock copolymer films during spin coating. Langmuir 2002 , 18 , 5293−5298..
Salimi, A.; Yousefi, A. A. Conformational changes and phase transformation mechanisms in PVDF solution-cast films. J. Polym. Sci. Part B: Polym. Phys. 2004 , 42 , 3487−3495..
Nangia, A.; Desiraju, G. R. Pseudopolymorphism: occurrences of hydrogen bonding organic solvents in molecular crystals. Chem. Commun . 1999 , 605−606..
0
Views
0
Downloads
0
CSCD
Publicity Resources
Related Articles
Related Author
Related Institution