Polyvinylidene fluoride-trifluoroethylene film having nanorod array on surface and preparation thereof

Abstract

The application discloses a polyvinylidene fluoride trifluoroethylene film with nanorod array on the surface and a preparation method thereof, and belongs to the field of biomedical materials. The preparation method comprises the following steps: preparing a polyvinylidene fluoride trifluoroethylene film by a solution casting method, and performing annealing crystallization treatment; stacking the polyvinylidene fluoride trifluoroethylene film on an anodic aluminum oxide template, heating and heat preservation on a hot plate, and naturally cooling along with the hot plate; then, dissolving the anodic aluminum oxide template by using a sodium hydroxide solution, cleaning multiple times by using deionized water and ethanol to remove residual sodium hydroxide, and drying; and performing polarization treatment. The preparation method is simple, and the cost is relatively low; the polyvinylidene fluoride trifluoroethylene film with nanorod array on the surface can be obtained, the polyvinylidene fluoride trifluoroethylene film has good piezoelectric performance, can provide electrical signal stimulation to cells or tissues, and has good biocompatibility, so that the polyvinylidene fluoride trifluoroethylene film can be used as a biomedical implant, and cell growth and tissue repair and regeneration can be promoted.

Description

Technical Field

[0001] This invention relates to the field of biomedical materials, specifically to polyvinylidene fluoride trifluoroethylene thin films with nanorod arrays on their surfaces and their preparation. Background Technology

[0002] Piezoelectricity is an intrinsic property of biological tissues, playing an important role in a variety of physiological phenomena. Piezoelectricity can be found in different parts of the human body, such as bones, tendons, and skin, and many functions of human cells and organs are controlled by electrical signals.

[0003] Piezoelectric materials are a class of materials that generate electrical signals upon deformation. Due to their advantage of generating stable localized electrical stimulation without the need for externally implanted electrodes, piezoelectric materials have attracted considerable attention in the field of bioelectrically active materials. Currently, different piezoelectric materials are applied to various tissue repair processes, particularly in bone and nerve tissue repair.

[0004] When bioelectroactive materials are implanted in the body, receptors on the cell membrane actively seek external signals provided by the implant surface in contact with them, and an interaction inevitably occurs between the biological environment and the material surface. Cells in contact with the material can sense its surface features and integrate extracellular matrix (ECM) protein cues through signal transduction pathways, ultimately guiding cell fate. Therefore, the interface between biomaterials and the physiological environment, i.e., the material surface, has a significant impact on cell-material interactions. Changes in cell behavior on materials are related to specific surface properties of the material. Topological structure (roughness, porous structure, patterning), chemical characteristics (surface composition, chemical groups), and physical properties (hydrophilicity / hydrophobicity, surface energy, surface potential) are all considered to contribute to the individual or synergistic regulation of cell behavior. These cues have been used to regulate almost all aspects of cell behavior, from cell adhesion and diffusion to proliferation and differentiation. Describing the regulation of cell behavior by material surface properties is crucial for the rational design of novel biomaterials, implants, and medical devices.

[0005] Polyvinylidene fluoride (PVDF) possesses excellent piezoelectricity, thermal stability, and biocompatibility, making it a high-performance electroactive biomaterial. In recent years, various PVDF nanomaterials have been used to regulate cell behavior or promote tissue repair. Among various PVDF-based polymers, the copolymer of PVDF and trifluoroethylene (P(VDF-TrFE)) exhibits the best piezoelectric properties. Although the piezoelectric properties of the copolymer can be improved by optimizing the VDF / TrFE ratio, its piezoelectric properties as a polymer are still lower than many inorganic piezoelectric ceramics and single crystals. In recent years, researchers have enhanced the piezoelectric effect of piezoelectric polymers by designing specialized micro / nanostructures. Many novel fabrication techniques for micro / nanostructures have emerged, such as electron beam lithography, ultraviolet lithography, focused ion beam lithography, and self-assembly. For example, Chinese patent application CN111694219A discloses a method for fabricating self-assembled three-dimensional micro / nano structures, including: surface pretreatment; spin-coating SU8 photoresist; pre-baking; alignment and exposure; post-baking; development; secondary spin coating; pre-baking; secondary exposure; post-baking; secondary development; transfer and self-assembly to obtain a self-assembled three-dimensional micro / nano structure. However, the application of the above-mentioned technologies is significantly limited by either high costs or uncontrollable processes. Therefore, developing a novel micro / nano structure, especially one fabricated with simple processes and low cost, is of great value and significance. Summary of the Invention

[0006] In view of this, the present invention provides a polyvinylidene fluoride (PVDF) trifluoroethylene film with a nanorod array on its surface and its preparation method. The preparation method of the present invention is simple and low in cost, and the obtained PVDF trifluoroethylene film has a uniformly distributed and highly ordered nanorod array on its surface.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0008] The present invention provides a polyvinylidene fluoride trifluoroethylene film, the surface of which presents a uniformly distributed and highly ordered array of PVTF nanorods.

[0009] In some specific embodiments of the present invention, the length of the PVTF nanorod is 3 to 8 μm and the diameter of the PVTF nanorod is 20 to 500 nm.

[0010] Meanwhile, the present invention also provides a method for preparing the above-mentioned polyvinylidene fluoride trifluoroethylene film, comprising the following steps:

[0011] S1. A solution obtained by mixing and stirring polyvinylidene fluoride trifluoroethylene powder with N,N-dimethylformamide is dropped onto a substrate, and the solution is uniformly dispersed using a coating device to form a film. After annealing, a PVTF film is obtained.

[0012] S2. The PVTF film is stacked on an anodized aluminum template, placed on a hot plate for heating and kept at that temperature for a period of time, and then cooled naturally with the hot plate. Then, it is immersed in a sodium hydroxide solution to dissolve and remove the anodized aluminum template. After washing with deionized water and ethanol several times, it is dried to obtain an arrayed PVTF film.

[0013] S3. The arrayed PVTF film is subjected to polarization treatment.

[0014] In some specific examples of the present invention, in step S1, the feeding ratio of polyvinylidene fluoride trifluoroethylene powder to N,N-dimethylformamide is 1g:(6-12)ml, preferably 1g:6ml.

[0015] In some specific embodiments of the present invention, in step S1, the substrate is a glass plate, preferably a tempered glass plate.

[0016] In some specific embodiments of the present invention, in step S1, the height of the coating applicator is set to 60-90 μm, preferably 70 μm.

[0017] In some specific embodiments of the present invention, in step S1, the annealing temperature is 180-220°C, preferably 210°C.

[0018] In some specific embodiments of the present invention, in step S1, the annealing time is 0.5 to 2 hours, preferably 1 hour.

[0019] In some specific embodiments of the present invention, in step S1, the thickness of the PVTF film is 50-90 μm, preferably 55 μm.

[0020] In some specific embodiments of the present invention, in step S2, the temperature of the heating plate is 160-220°C, preferably 160°C.

[0021] In some specific embodiments of the present invention, in step S2, the heat preservation time on the hot plate is 5 to 20 minutes, preferably 5 minutes.

[0022] In some specific embodiments of the present invention, in step S2, the concentration of the NaOH solution is 0.05 to 5 mol / L, preferably 2 mol / L.

[0023] In some specific embodiments of the present invention, in step S2, the soaking time of the NaOH solution is 10 min to 24 hours, preferably 30 min.

[0024] In some specific embodiments of the present invention, in step S2, the drying temperature is 30-50°C, preferably 37°C.

[0025] In some specific embodiments of the present invention, in step S2, the pore size of the anodic aluminum oxide template is 20-500 nm.

[0026] In some specific embodiments of the present invention, in step S3, the polarization treatment adopts the corona polarization method.

[0027] In some specific embodiments of the present invention, in step S3, the piezoelectric coefficient d of the target product obtained by the polarization treatment is... 33 Satisfies: -20pC / N≤d 33 <0pC / N or 0pC / N <d 33 ≤20pC / N.

[0028] In some specific embodiments of the present invention, in step S3, the voltage of the high-voltage electric field for polarization treatment is 8 to 15 kV, and the polarization treatment time is 40 to 60 minutes.

[0029] In some specific embodiments of the present invention, in step S3, the voltage of the high-voltage electric field for polarization treatment is 8.20 kV, and the polarization treatment time is 40 min.

[0030] Compared with the prior art, the present invention has the following beneficial technical effects:

[0031] (1) The polyvinylidene fluoride trifluoroethylene film with a nanorod array on the surface of the present invention has a uniformly distributed and highly ordered PVTF nanorod array on the surface, with high orientation and crystallinity. Its piezoelectric properties are significantly improved compared with unmodified PVTF film, which can provide electrical signal stimulation to cells or tissues and has good biocompatibility. It can be used as a biomedical implant to promote cell growth and tissue repair and regeneration.

[0032] (2) The preparation method of the present invention is simple to operate, relatively low in cost, and easy to control. By adjusting parameters such as heating temperature and holding time, the morphology of the surface nanorod array structure can be changed, thereby obtaining nanorod array structures with different distributions and lengths. Furthermore, by adjusting the polarization parameters, polyvinylidene fluoride trifluoroethylene films with nanorod arrays on the surface with different dipole orientations and different surface potentials can be obtained. Attached Figure Description

[0033] Figure 1A The XRD patterns are obtained by X-ray diffraction characterization of the PVTF film obtained in step (1) of this embodiment, the arrayed PVTF film obtained in step (2), and the target product obtained in this embodiment.

[0034] Figure 1BThe Fourier transform infrared (FTIR) spectra are obtained by performing Fourier transform infrared spectroscopy analysis on the PVTF film obtained in step (1) of this embodiment, the arrayed PVTF film obtained in step (2), and the target product obtained in this embodiment.

[0035] Figure 2A The contact angle test results of the PVTF film obtained in step (1) of Example 1 are as follows.

[0036] Figure 2B The contact angle test results are those of the target product obtained in Example 1.

[0037] Figure 3A This is a SEM image of the surface morphology of the PVTF film obtained in step (1) of Example 1.

[0038] Figure 3B This is a SEM image of the surface morphology of the arrayed PVTF film obtained in step (2) of Example 1.

[0039] Figure 3C This is a SEM image of the cross-sectional morphology (partial) of the arrayed PVTF film obtained in step (2) of Example 1.

[0040] Figure 3D This is an SEM image of the surface morphology of the target product obtained in Example 1.

[0041] Figure 4 This is a surface potential map of the PVTF thin film obtained in step (1) of Example 1 using a Kelvin probe microscope.

[0042] Figure 5 This is a surface potential map of the arrayed PVTF thin film obtained in step (2) of Example 1 using a Kelvin probe microscope.

[0043] Figure 6 This is a surface potential map of the target product obtained in Example 1 using a Kelvin probe microscope.

[0044] Figure 7 This is a comparison of the cell viability of mouse bone marrow mesenchymal stem cells cultured for three days after being seeded onto the target product obtained in Example 1 and the PVTF planar film obtained in step (1), as determined by the CCK-8 assay.

[0045] Figure 8 This is an SEM image of the surface morphology of the target product obtained in Example 2. Detailed Implementation

[0046] To better illustrate the present invention and facilitate understanding of its technical solutions, the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments. It should be understood that the following embodiments are for illustrative purposes only and do not represent or limit the scope of protection of the present invention; the scope of protection of the present invention is defined by the claims.

[0047] In the following examples, reagents or instruments whose manufacturers are not specified are all commercially available products. For example, the glass plate is tempered glass, and the vinylidene fluoride-trifluoroethylene copolymer (i.e., polyvinylidene fluoride-trifluoroethylene, P(VDF-TrFE), abbreviated as PVTF) is manufactured by Piezotech, France, and its model number is: FC30, in which the molar ratio of vinylidene fluoride monomer to trifluoroethylene monomer is 7:3. The anodic aluminum oxide template uses a 0.1µm pore size AAO membrane, brand GE Whatman, model 6809-7013-Whatman aluminum oxide membrane.

[0048] The corona polarization device includes a high-voltage DC power supply and a round-tipped electrode needle. The round-tipped electrode needle is placed 1 cm above the sample and connected to the positive and negative terminals of the power supply, respectively, with the negative electrode plate below the sample. The voltage is gradually increased until a critical voltage is reached to initiate corona discharge, which is maintained for a certain period of time.

[0049] Cell viability was determined using the CCK-8 (Cell Counting Kit-8) method: Frozen rat bone marrow mesenchymal stem cells (MSCs) were thawed and cultured in DMEM low-glucose medium for 3 days, then digested with trypsin, resuspended, and prepared into a concentration of 1.0 × 10⁻⁶ cells / day. 5 A cell suspension of 1 cell / mL was used to seed 0.5 mL of the suspension onto 1 cm × 1 cm sample surfaces in each well of a 24-well plate. The plates were then incubated in a constant temperature and humidity incubator at 37°C and 5% CO2, replacing the medium with fresh DMEM low-glucose medium every other day. After 3 days of incubation, the samples were transferred to new 24-well plates. Under light-protected conditions, 500 μL of DMEM low-glucose medium and 50 μL of CCK-8 were added to each well, and the plates were incubated at 37°C for 2 hours. Finally, the absorbance (OD value) at 450 nm was measured using a microplate reader.

[0050] Example 1

[0051] (1) Mix 1g of PVTF powder with 6ml of N,N-dimethylformamide (DMF) and stir magnetically for 6h to obtain a PVTF solution; drop the PVTF solution onto a glass plate and use a coating device to uniformly disperse the solution to form a film. The coating device height is set to 70μm. Anneal and crystallize in a muffle furnace at 210℃ for 1h to obtain a PVTF film with a thickness of 55μm.

[0052] (2) The PVTF film was washed with deionized water and ethanol in sequence and then dried. The anodic aluminum oxide template was washed with deionized water and ethanol in sequence and then dried. Then, the PVTF film was stacked on the anodic aluminum oxide template (i.e., the PVTF film was placed on the anodic aluminum oxide template), placed on a hot plate and heated to 160°C. After holding at this temperature for 5 minutes, the sample was allowed to cool naturally with the hot plate. Subsequently, the sample was immersed in a 2 mol / L NaOH solution for 30 minutes to dissolve and remove the anodic aluminum oxide template. Finally, the sample was washed with deionized water and ethanol multiple times to remove any NaOH solution residue and then dried at 37°C to obtain the arrayed PVTF film.

[0053] (3) The arrayed PVTF film obtained in step (2) was polarized by corona polarization. The voltage of the high voltage field for polarization was 8.20 kV and the polarization time was 40 min to obtain the target product.

[0054] Performance and Testing:

[0055] The PVTF film obtained in step (1) of this embodiment, the arrayed PVTF film obtained in step (2), and the target product obtained in this embodiment were characterized by X-ray diffraction, and their XRD patterns are shown below. Figure 1A As shown. Figure 1A In the image, the diffraction peaks near 20.7° and 38.0° correspond to the (200) and (001) reflections of the PVTF β phase. From... Figure 1A As can be seen, the PVTF film, the arrayed PVTF film, and the target product are all β-phase PVTF crystals.

[0056] Fourier transform infrared (FTIR) spectroscopy analysis was performed on the PVTF film obtained in step (1) of this embodiment, the arrayed PVTF film obtained in step (2), and the target product obtained in this embodiment. The FTIR images are shown below. Figure 1B As shown. Figure 1B In the middle, at 870cm -1 and 1279cm -1 The characteristic β-phase band of PVTF is displayed here. From... Figure 1B As can be seen, the PVTF film, the arrayed PVTF film, and the target product are all β-phase PVTF.

[0057] The contact angle of the PVTF film obtained in step (1) and the target product obtained in step (3) of Example 1 were tested respectively, and the results are as follows: Figure 2A and Figure 2B As shown, the contact angles were 74.8° and 126.3°, respectively, indicating that the hydrophilicity and hydrophobicity of the target product were significantly different from those of the unmodified pure PVTF film.

[0058] The surface morphology of the PVTF film obtained in step (1), the surface morphology of the arrayed PVTF film obtained in step (2), the cross-sectional morphology (the cross-sectional segment near the surface) of the arrayed PVTF film obtained in step (2), and the surface morphology of the target product obtained in Example 1 were observed using scanning electron microscopy. The SEM images are shown below. Figures 3A to 3D As shown.

[0059] Figure 3A In the study, the surface morphology of the PVTF film exhibits a typical wrinkled morphology after PVTF crystallization. Figure 3B In the study, the surface morphology of the arrayed PVTF film is characterized by a highly ordered array of PVTF nanorods with a diameter of approximately 200 nm. Figure 3C As can be seen, the nanorods in the cross-sectional section near the surface are all upright, and the morphology also shows a highly ordered array of PVTF nanorods. The length of the nanorods is about 3 μm and the diameter of the nanorods is about 200 nm. Figure 3D In the study, the surface morphology of the target product was almost identical to that of the arrayed PVTF film, still exhibiting a highly ordered array of PVTF nanorods with a diameter of approximately 200 nm. Simultaneously, it was observed that the cross-sectional morphology of the target product was almost identical to that of the arrayed PVTF film, also exhibiting a highly ordered array of PVTF nanorods with a length of approximately 3 μm and a diameter of approximately 200 nm. It is evident that the surface morphology of the film underwent a significant change before and after arraying: transforming from a planar film to a highly ordered arrayed film; while the surface morphology remained almost unchanged before and after polarization treatment.

[0060] The product obtained by corona polarization of the PVTF film in step (1) was measured using a static piezoelectric coefficient D33 measuring instrument, which showed its surface piezoelectric coefficient d. 33 The piezoelectric coefficient is -11 pC / N; the target product was measured using a static piezoelectric coefficient D33 measuring instrument, and the surface piezoelectric coefficient d of the target product was displayed. 33 The value is -15 pC / N. This indicates that the piezoelectric properties of the target product are improved compared to the unmodified pure PVTF film.

[0061] The potential signal on the surface of the PVTF film obtained in step (1) was detected using a Kelvin probe microscope, and the potential diagram is shown below. Figure 4 As shown in the figure, the surface potential of the PVTF film is 0.09V. Using a Kelvin probe microscope, the potential signal on the surface of the arrayed PVTF film obtained in step (2) was detected, and its potential diagram is shown in the figure. Figure 5 As shown, the surface potential of the arrayed PVTF film is -2.45V. The potential signal on the surface of the target product obtained in Example 1 was detected using a Kelvin probe microscope, and its potential diagram is shown below. Figure 6 As shown, the surface potential of the target product is greater than 12V. This result indicates that the absolute value of the surface potential of the film increases after array construction; and the absolute value of the surface potential of the film increases significantly after polarization treatment.

[0062] Mouse bone marrow mesenchymal stem cells (MSCs) were seeded onto the target product obtained in Example 1 and the PVTF planar film obtained in step (1), respectively, and cell viability was measured using the CCK-8 assay. The results are as follows: Figure 7 As shown. From Figure 7 It can be seen that the OD value of the cells inoculated with the target product obtained in this embodiment 1 is higher than that of the cells inoculated on the PVTF planar film obtained in step (1), indicating that the target product obtained in this embodiment 1 has better cell compatibility and is more conducive to cell adhesion and proliferation.

[0063] Example 2

[0064] (1) Mix 1g of PVTF powder with 6ml of N,N-dimethylformamide (DMF) and stir magnetically for 6h to obtain a PVTF solution; drop the PVTF solution onto a glass plate and use a coating device to uniformly disperse the solution to form a film. The coating device height is set to 70μm. Anneal and crystallize in a muffle furnace at 210℃ for 1h to obtain a PVTF film with a thickness of 55μm.

[0065] (2) The PVTF film was cleaned with deionized water and ethanol in sequence and then dried. The anodic aluminum oxide template was cleaned with deionized water and ethanol in sequence and then dried. Then, the PVTF film was stacked on the anodic aluminum oxide template, placed on a hot plate and heated to 190°C. After holding at this temperature for 20 minutes, the film was allowed to cool naturally with the hot plate. Subsequently, the sample was immersed in a 2 mol / L NaOH solution for 30 minutes to dissolve and remove the anodic aluminum oxide template. Finally, the film was cleaned with deionized water and ethanol multiple times to remove any NaOH solution residue and then dried at 37°C to obtain the arrayed PVTF film.

[0066] (3) The arrayed PVTF film obtained in step (2) was polarized by corona polarization. The voltage of the high voltage field for polarization was 8.20 kV and the polarization time was 40 min to obtain the target product.

[0067] XRD analysis showed that the target product obtained in Example 2 was a β-phase PVTF crystal. The surface morphology of the target product obtained in Example 2 was observed using scanning electron microscopy (SEM), and the SEM image is shown below. Figure 8 As shown. From Figure 8 It is evident that the surface morphology of the target product exhibits a highly ordered nanorod cluster structure.

[0068] The target product obtained in Example 2 was measured using a static piezoelectric coefficient D33 measuring instrument, and the surface piezoelectric coefficient d of the target product was displayed. 33 It is -16pC / N.

[0069] Example 3

[0070] (1) Mix 1g of PVTF powder with 6ml of N,N-dimethylformamide (DMF) and stir magnetically for 6h to obtain a PVTF solution; drop the PVTF solution onto a glass plate and use a coating tool to uniformly disperse the solution to form a film. The coating tool height is set to 70μm. Heat treat in a muffle furnace at 210℃ for 1h to anneal and crystallize to obtain a PVTF film with a film thickness of 55μm.

[0071] (2) The PVTF film was cleaned with deionized water and ethanol in sequence and then dried. The anodic aluminum oxide template was cleaned with deionized water and ethanol in sequence and then dried. Then, the PVTF film was stacked on the anodic aluminum oxide template, placed on a hot plate and heated to 160°C. After holding at this temperature for 10 minutes, the film was allowed to cool naturally with the hot plate. Subsequently, the sample was immersed in a 2 mol / L NaOH solution for 30 minutes to dissolve and remove the anodic aluminum oxide template. Finally, the film was cleaned multiple times with deionized water and ethanol to remove any NaOH solution residue and then dried at 37°C to obtain the arrayed PVTF film.

[0072] (3) The arrayed PVTF film obtained in step (2) was polarized by corona polarization. The voltage of the high voltage electric field for polarization was 12.0 kV and the polarization time was 40 min to obtain the target product.

[0073] The target product obtained in Example 3 was measured using a static piezoelectric coefficient D33 measuring instrument, and the surface piezoelectric coefficient d of the target product obtained in Example 3 was displayed. 33 It is -18pC / N.

[0074] Based on Examples 1-3, it can be observed that by adjusting parameters such as heating temperature and holding time, the morphology of the surface nanorod array structure can be altered, thereby obtaining nanorod array structures with different distributions and lengths. Furthermore, by adjusting polarization parameters, polyvinylidene fluoride (PVDF) and trifluoroethylene (PTFE) films with nanorod arrays on their surfaces can be obtained with different degrees of dipole orientation and different surface potentials. The PVDF and PTFE films with nanorod arrays on their surfaces of the present invention exhibit excellent piezoelectric properties, capable of providing electrical signal stimulation to cells or tissues, and possess good biocompatibility. Therefore, they can be used as biomedical implants to promote cell growth and tissue repair and regeneration. In addition, the preparation method of the present invention is simple to operate and has low cost.

[0075] Therefore, it is evident that the objective of this invention has been fully and effectively achieved. The function and structural principles of this invention have been demonstrated and explained in the embodiments. Any modifications can be made to the implementation methods without departing from these principles. Therefore, this invention includes all modified embodiments based on the spirit and scope of the claims.

Claims

1. A polyvinylidene fluoride-trifluoroethylene film, characterized by, The surface presents uniform distribution and highly ordered arrangement of PVTF nanorod array, and the polyvinylidene fluoride trifluoroethylene film is prepared by the following method: S1, polyvinylidene fluoride trifluoroethylene powder is mixed with N,N-dimethylformamide to obtain a solution, which is dropped on the substrate, and the solution is uniformly dispersed by a film applicator, and the height of the film applicator is set to 60-90 μm, and the film is formed after annealing treatment at 180-220 ℃ for 0.5-2 h to obtain a PVTF film; S2, the PVTF film is stacked on an anodic aluminum oxide template, heated on a hot plate and kept for a period of time, and the heating temperature is 160-220 ℃, and the hot plate is naturally cooled; Then, it is immersed in a sodium hydroxide solution to dissolve and remove the anodic aluminum oxide template; After washing with deionized water and ethanol for several times, drying, an arrayed PVTF film is obtained; S3, the arrayed PVTF film is polarized, and the voltage of the high voltage electric field of the polarization treatment is 8-15 kV, and the polarization treatment time is 40-60 min.

2. The polyvinylidene fluoride-trifluoroethylene film according to claim 1, wherein The length of the PVTF nanorod is 3-8 μm, and the diameter of the PVTF nanorod is 20-500 nm.

3. The method of producing a polyvinylidene fluoride-trifluoroethylene film according to claim 1 or 2, characterized by, The method comprises the following steps: S1, polyvinylidene fluoride trifluoroethylene powder is mixed with N,N-dimethylformamide to obtain a solution, which is dropped on the substrate, and the solution is uniformly dispersed by a film applicator, and the height of the film applicator is set to 60-90 μm, and the film is formed after annealing treatment at 180-220 ℃ for 0.5-2 h to obtain a PVTF film; S2, the PVTF film is stacked on an anodic aluminum oxide template, heated on a hot plate and kept for a period of time, and the hot plate is naturally cooled; Then, it is immersed in a sodium hydroxide solution to dissolve and remove the anodic aluminum oxide template; After washing with deionized water and ethanol for several times, drying, an arrayed PVTF film is obtained; S3, the arrayed PVTF film is polarized.

4. The production method according to claim 3, wherein In step S1, the feeding ratio of polyvinylidene fluoride trifluoroethylene powder to N,N-dimethylformamide is 1 g: (6-12) ml.

5. The production method according to claim 3, wherein In step S1, the film thickness of the PVTF film is 50-90 μm.

6. The production method according to claim 3, wherein In step S1, the annealing treatment temperature is 180-220 ℃.

7. The production method according to claim 3, wherein In step S2, the heating temperature on the hot plate is 160-220 ℃.

8. The production method according to claim 3, wherein In step S2, the pore size of the anodic aluminum oxide template is 20-500 nm.

9. The production method according to claim 3, wherein In step S3, the polarization treatment adopts corona polarization method.

10. The production method according to claim 9, wherein In step S3, the voltage of the high voltage electric field of the polarization treatment is 8-15 kV, and the polarization treatment time is 40-60 min.

Images