CN114409944A - Method for rapidly inducing polyvinylidene fluoride film to generate alpha-gamma phase change - Google Patents
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
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- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
A method for rapidly inducing a polyvinylidene fluoride film to generate alpha-gamma phase transition comprises the steps of taking N, N-dimethylformamide as a solvent, preparing a PVDF solution with the mass concentration of 3% -10%, uniformly blade-coating the prepared solution on a dry and clean glass sheet or silicon wafer substrate, drying at 60-100 ℃ for 6-24 hours to completely remove the solvent to obtain the PVDF film, eliminating heat history at 190-210 ℃, nucleating into alpha-phase crystal nuclei at 30-160 ℃, soaking in ionic liquid, rapidly phase-changing into gamma ' -phase crystals at 140-170 ℃ to obtain the PVDF film with high gamma ' -content, wherein the gamma ' -phase content is up to 92%; because the method of crystallization and rapid annealing is adopted, the generation speed of the gamma-PVDF is greatly improved, and the high-temperature-resistant polyvinylidene fluoride dielectric film can be rapidly prepared; the preparation process is simple, the operation is convenient, the continuous production can be realized, the performance is excellent, the high temperature resistance and the chemical corrosion resistance are realized, the ferroelectric and piezoelectric properties are stronger, and the preparation method can be applied to sensors, capacitors, high-temperature-resistant energy storage elements and thermosensitive materials.
Description
Technical Field
The invention belongs to the technical field of preparation of gamma-phase polyvinylidene fluoride (PVDF) films, and particularly relates to a method for rapidly inducing a PVDF film to generate alpha-gamma phase transition.
Background
Functional polymer film materials have been receiving wide attention from all parties, and especially polymer materials with special properties are the focus of research.
Polyvinylidene fluoride (PVDF) is a polymorphic, semi-crystalline polymer with three of the most common crystalline forms, alpha, beta, and gamma. The alpha-phase polyvinylidene fluoride has excellent mechanical properties and can be widely applied to the fields of chemical industry, solar devices, electronics and the like; the beta-phase polyvinylidene fluoride has good piezoelectric and ferroelectric effects, and is often applied to the fields of energy conversion devices, such as pressure sensitive devices, humidity sensitive devices and the like; the gamma phase has ferroelectricity and piezoelectricity, has thermal stability and Curie temperature higher than those of the beta phase, is an excellent flexible high-temperature-resistant piezoelectric material, and can be applied to the aspects of energy storage devices and the like. In the prior art, a polyvinylidene fluoride film containing a gamma phase is generally prepared through long-time high-temperature annealing or through adding a gamma-phase nucleating agent; chinese patent CN113248762A discloses a method for preparing a gamma-phase polyvinylidene fluoride film, which discloses that a polyvinylidene fluoride melt forms alpha crystal nucleus at a lower temperature and then is annealed at a high temperature to obtain the gamma-phase film; however, the annealing time is too long, which results in higher energy consumption, higher cost and lower productivity. Chinese patent CN113248762A discloses a method for rapidly preparing a gamma-phase polyvinylidene fluoride film, which is to obtain the gamma-phase film by high-temperature annealing after forming alpha crystal nucleus at a lower temperature by a polyvinylidene fluoride melt, but has the problems of larger energy consumption, higher cost, lower productivity and the like caused by overlong annealing time.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for rapidly inducing a polyvinylidene fluoride film to generate alpha-gamma phase transition, which is characterized in that a polyvinylidene fluoride (PVDF) film with high gamma phase content is prepared by low-temperature crystallization, coating with an ionic liquid or a quaternary ammonium salt solution and rapid annealing at high temperature, has short growth time and easy industrialization, and has the advantages of convenient preparation operation, simple process, continuous production and excellent performance.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for rapidly inducing a polyvinylidene fluoride film to generate alpha-gamma phase transition specifically comprises the following steps:
1) preparing a PVDF solution with the mass concentration of 3-10% by taking N, N-dimethylformamide as a solvent;
2) uniformly blade-coating the solution prepared in the step 1) on a dry and clean glass sheet or silicon wafer substrate, and drying at 60-100 ℃ for 6-24h to completely remove the solvent to obtain a PVDF film;
3) melting the PVDF film prepared in the step 2) at the temperature of 190-210 ℃ to eliminate the heat history, then transferring to the temperature of 30-160 ℃ within 10-30s, and preserving the heat for 5-600 min;
4) uniformly coating a layer of ionic liquid or quaternary ammonium salt solution on the PVDF film prepared in the step 3), and standing for 5-20min to prepare a PVDF cured film;
5) annealing the PVDF film coated with the ionic liquid or the quaternary ammonium salt solution prepared in the step 4) at the temperature of 140-160 ℃, and preserving the heat for 10-60min to prepare the PVDF cured film.
The thickness of the liquid film coated in the step 2) is 100-500 mu m.
The coating thickness in the step 4) is 0.1-1 μm.
In the step 4), the ionic liquid comprises: 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium tetrafluoroborate or N-butylpyridinium hexafluorophosphate; the quaternary ammonium salt comprises cetyl trimethyl ammonium bromide, dodecyl trimethyl ammonium bromide or choline chloride.
And (3) characterizing the PVDF cured film prepared in the step 5) by using a polarizing microscope, a Fourier infrared absorption spectrum, a differential scanning calorimeter and an X-ray diffractometer in sequence, and obtaining that the crystal form of the polyvinylidene fluoride base film is a gamma' crystal form.
The invention has the beneficial effects that:
the invention adopts a solution blade coating method to prepare a high-temperature resistant PVDF dielectric film (PVDF cured film), PVDF rapidly nucleates into alpha-phase crystal nuclei at the temperature of 30-160 ℃, and the PVDF rapidly changes into gamma-phase crystals at the temperature of 140-160 ℃ after being coated with ionic liquid or quaternary ammonium salt solution, so that the alpha-gamma phase change degree of the PVDF is improved, and the gamma-phase content can reach 92%; and because of adopting the low-temperature crystallization mode, thus has accelerated the growth rate; compared with the traditional melt crystallization method, the method greatly improves the phase change speed of the gamma phase and accelerates the phase change degree of the gamma phase, so that the high-temperature resistant PVDF dielectric film can be quickly prepared, and the method has the characteristics of low energy consumption, low cost and high productivity.
Drawings
FIG. 1 is an infrared absorption spectrum of example 1 of the present invention.
FIG. 2 is an infrared absorption spectrum of example 3 of the present invention.
FIG. 3 is an infrared absorption spectrum of example 4 of the present invention.
FIG. 4 is a comparison of an ionic liquid uncoated and annealed PVDF film with an ionic liquid coated and annealed PVDF film under a polarizing microscope.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
Example 1
A method for rapidly inducing a polyvinylidene fluoride film to generate alpha-gamma phase transition specifically comprises the following steps:
1) preparing a PVDF solution with the mass concentration of 3% by taking N, N-dimethylformamide as a solvent;
2) uniformly blade-coating the solution prepared in the step 1) on a dry and clean glass sheet, wherein the thickness of a blade-coated liquid film is 100 mu m, and drying the glass sheet at 60 ℃ for 24h to completely remove the solvent to obtain a PVDF film;
3) melting the PVDF film prepared in the step 2) at 190 ℃ to eliminate thermal history, then transferring to 30 ℃ within 30s, and preserving heat for 5 min;
4) uniformly coating a layer of 1-butyl-3-methylimidazole hexafluorophosphate with the thickness of 0.1-1 mu m on the PVDF film prepared in the step 3), and standing for 20 min;
5) annealing the PVDF film prepared in the step 4) at 140 ℃, and preserving heat for 60min to prepare the PVDF cured film.
Example 2
A method for rapidly inducing a polyvinylidene fluoride film to generate alpha-gamma phase transition specifically comprises the following steps:
1) preparing a PVDF solution with the mass concentration of 5% by taking N, N-dimethylformamide as a solvent;
2) uniformly blade-coating the solution prepared in the step 1) on a dry and clean glass sheet, wherein the thickness of a blade-coated liquid film is 200 mu m, and drying the glass sheet at 70 ℃ for 20h to completely remove the solvent to obtain a PVDF film;
3) melting the PVDF film prepared in the step 2) at 195 ℃ to eliminate thermal history, then transferring to 90 ℃ within 20s, and preserving heat for 30 min;
4) uniformly coating a layer of 1-butyl-3-methylimidazole tetrafluoroborate with the thickness of 0.3 mu m on the PVDF film prepared in the step 3), and standing for 15 min;
5) annealing the PVDF film prepared in the step 4) at 145 ℃, and preserving heat for 50min to prepare the PVDF cured film.
Example 3
A method for rapidly inducing a polyvinylidene fluoride film to generate alpha-gamma phase transition specifically comprises the following steps:
1) preparing a PVDF solution with the mass concentration of 7% by taking N, N-dimethylformamide as a solvent;
2) uniformly blade-coating the solution prepared in the step 1) on a dry and clean glass sheet, wherein the thickness of a blade-coated liquid film is 300 mu m, and drying the glass sheet at 80 ℃ for 16h to completely remove the solvent to obtain a PVDF film;
3) melting the PVDF film prepared in the step 2) on a heating table at 200 ℃ to eliminate heat history, then transferring to 120 ℃ within 15s, and preserving heat for 60 min;
4) uniformly coating a layer of 10 wt% hexadecyl trimethyl ammonium bromide aqueous solution with the thickness of 0.5 mu m on the PVDF film prepared in the step 3), and standing for 12 min;
5) annealing the PVDF film prepared in the step 4) at 150 ℃, and preserving heat for 40min to prepare the PVDF cured film.
Example 4
A method for rapidly inducing a polyvinylidene fluoride film to generate alpha-gamma phase transition specifically comprises the following steps:
1) preparing a PVDF solution with the mass concentration of 9% by taking N, N-dimethylformamide as a solvent;
2) uniformly blade-coating the solution prepared in the step 1) on a dry and clean silicon wafer substrate, wherein the thickness of a blade-coated liquid film is 400 mu m, and drying the liquid film at 90 ℃ for 12h to completely remove the solvent to obtain a PVDF film;
3) melting the PVDF film prepared in the step 2) at 205 ℃ to eliminate heat history, then transferring to 150 ℃ within 12s, and preserving heat for 120 min;
4) uniformly coating a layer of 10 wt% choline chloride aqueous solution with the thickness of 0.8 mu m on the PVDF film prepared in the step 3), and standing for 10 min;
5) annealing the PVDF film prepared in the step 4) at 155 ℃, and preserving heat for 20min to prepare the PVDF cured film.
Example 5
A method for rapidly inducing a polyvinylidene fluoride film to generate alpha-gamma phase transition specifically comprises the following steps:
1) preparing a PVDF solution with the mass concentration of 10% by taking N, N-dimethylformamide as a solvent;
2) uniformly blade-coating the solution prepared in the step 1) on a dry and clean silicon wafer substrate, wherein the thickness of a blade-coated liquid film is 500 mu m, and drying the liquid film at 100 ℃ for 6h to completely remove the solvent to obtain a PVDF film;
3) melting the PVDF film prepared in the step 2) at 210 ℃ to eliminate heat history, then transferring to 160 ℃ within 10s, and preserving heat for 600 min;
4) uniformly coating a layer of 10 wt% N-butylpyridinium hexafluorophosphate with the thickness of 1 mu m on the PVDF film prepared in the step 3), and standing for 5 min;
5) annealing the PVDF film prepared in the step 4) at 160 ℃, and preserving heat for 10min to prepare the PVDF cured film.
And (3) characterizing the PVDF cured film prepared in the step 5) in the above embodiment by using a polarization microscope, a Fourier infrared absorption spectrum, a differential scanning calorimeter and an X-ray diffractometer in sequence, and obtaining that the crystal form of the polyvinylidene fluoride base film is a gamma' crystal form.
The characterization methods of the polarizing microscope, the Fourier infrared absorption spectrum, the differential scanning calorimeter and the X-ray diffractometer are well known in the field.
Comparative example:
1) preparing a PVDF solution with the mass concentration of 10% by taking N, N-Dimethylformamide (DMF) as a solvent;
2) uniformly coating the solution prepared in the step 1) on a dry and clean glass sheet by a hanging rod, and drying in an oven at 100 ℃ for 6 hours to completely remove the solvent to obtain a PVDF film;
3) melting the PVDF film prepared in the step 2) on a heating table at 210 ℃ to eliminate heat history, then transferring the PVDF film to a heating table at 160 ℃ within 10s, and preserving heat for 600 min;
4) uniformly coating a layer of water on the PVDF film prepared in the step 3) by using absorbent cotton, and standing for 20 min;
5) annealing the PVDF film prepared in the step 4) on a heating table at 160 ℃, and preserving heat for 60 min.
The crystallized film is characterized by means such as a polarizing microscope, an infrared absorption spectrum and the like, so that the PVDF only generates few gamma phases, and the characteristic absorption peak of gamma cannot be observed by the infrared absorption spectrum.
All the tests are performed in triplicate, and the test accuracy is guaranteed.
Referring to fig. 1, PVDF has low nucleation capability and slow growth rate at high temperature.
Referring to fig. 2 and fig. 3, after the PVDF grows at a high temperature through low-temperature nucleation, the nucleation rate of the PVDF is greatly increased, the growth rate of the spherulites is obviously increased, the size of the spherulites is reduced, and the amount of the melt which is not completely grown in the PVDF is obviously reduced.
Referring to a polarizing microscope image taken at 183 ℃ in fig. 4, it can be seen that the phase transition degree of α - γ of PVDF is greatly improved and the γ phase content can reach 92% by the PVDF film coated with the ionic liquid and annealed.
Claims (10)
1. A method for rapidly inducing a polyvinylidene fluoride film to generate alpha-gamma phase transition is characterized by comprising the following steps: the method specifically comprises the following steps:
1) preparing a PVDF solution with the mass concentration of 3-10% by taking N, N-dimethylformamide as a solvent;
2) uniformly blade-coating the solution prepared in the step 1) on a dry and clean glass sheet or silicon wafer substrate, and drying at 60-100 ℃ for 6-24h to completely remove the solvent to obtain a PVDF film;
3) melting the PVDF film prepared in the step 2) at the temperature of 190-210 ℃ to eliminate the heat history, then transferring to the temperature of 30-160 ℃ within 10-30s, and preserving the heat for 5-600 min;
4) uniformly coating a layer of ionic liquid or quaternary ammonium salt solution on the PVDF film prepared in the step 3), and standing for 5-20min to prepare a PVDF cured film;
5) annealing the PVDF film coated with the ionic liquid or the quaternary ammonium salt solution prepared in the step 4) at the temperature of 140-160 ℃, and preserving the heat for 10-60min to prepare the PVDF cured film.
2. The method for rapidly inducing the alpha-gamma phase transition of the polyvinylidene fluoride film according to claim 1, wherein the method comprises the following steps: in the step 4), the ionic liquid comprises: 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium tetrafluoroborate or N-butylpyridinium hexafluorophosphate; the quaternary ammonium salt comprises cetyl trimethyl ammonium bromide, dodecyl trimethyl ammonium bromide or choline chloride.
3. The method for rapidly inducing the alpha-gamma phase transition of the polyvinylidene fluoride film according to claim 1, wherein the method comprises the following steps: the thickness of the liquid film in the step 2) is 100-500 mu m.
4. The method for rapidly inducing the alpha-gamma phase transition of the polyvinylidene fluoride film according to claim 1, wherein the method comprises the following steps: the coating thickness in the step 4) is 0.1-1 μm.
5. The method for rapidly inducing the alpha-gamma phase transition of the polyvinylidene fluoride film according to claim 1, wherein the method comprises the following steps: and (3) characterizing the PVDF cured film prepared in the step 5) by using a polarizing microscope, a Fourier infrared absorption spectrum, a differential scanning calorimeter and an X-ray diffractometer in sequence, and obtaining that the crystal form of the polyvinylidene fluoride base film is a gamma' crystal form.
6. The method for rapidly inducing the alpha-gamma phase transition of the polyvinylidene fluoride film according to claim 1, wherein the method comprises the following steps: the method specifically comprises the following steps:
1) preparing a PVDF solution with the mass concentration of 3% by taking N, N-dimethylformamide as a solvent;
2) uniformly blade-coating the solution prepared in the step 1) on a dry and clean glass sheet, wherein the thickness of a blade-coated liquid film is 100 mu m, and drying the glass sheet at 60 ℃ for 24h to completely remove the solvent to obtain a PVDF film;
3) melting the PVDF film prepared in the step 2) at 190 ℃ to eliminate thermal history, then transferring to 30 ℃ within 30s, and preserving heat for 5 min;
4) uniformly coating a layer of 1-butyl-3-methylimidazole hexafluorophosphate with the thickness of 0.1-1 mu m on the PVDF film prepared in the step 3), and standing for 20 min;
5) annealing the PVDF film prepared in the step 4) at 140 ℃, and preserving heat for 60min to prepare the PVDF cured film.
7. The method for rapidly inducing the alpha-gamma phase transition of the polyvinylidene fluoride film according to claim 1, wherein the method comprises the following steps: the method specifically comprises the following steps:
1) preparing a PVDF solution with the mass concentration of 5% by taking N, N-dimethylformamide as a solvent;
2) uniformly blade-coating the solution prepared in the step 1) on a dry and clean glass sheet, wherein the thickness of a blade-coated liquid film is 200 mu m, and drying the glass sheet at 70 ℃ for 20h to completely remove the solvent to obtain a PVDF film;
3) melting the PVDF film prepared in the step 2) at 195 ℃ to eliminate thermal history, then transferring to 90 ℃ within 20s, and preserving heat for 30 min;
4) uniformly coating a layer of 1-butyl-3-methylimidazole tetrafluoroborate with the thickness of 0.3 mu m on the PVDF film prepared in the step 3), and standing for 15 min;
5) annealing the PVDF film prepared in the step 4) at 145 ℃, and preserving heat for 50min to prepare the PVDF cured film.
8. The method for rapidly inducing the alpha-gamma phase transition of the polyvinylidene fluoride film according to claim 1, wherein the method comprises the following steps: the method specifically comprises the following steps:
1) preparing a PVDF solution with the mass concentration of 7% by taking N, N-dimethylformamide as a solvent;
2) uniformly blade-coating the solution prepared in the step 1) on a dry and clean glass sheet, wherein the thickness of a blade-coated liquid film is 300 mu m, and drying the glass sheet at 80 ℃ for 16h to completely remove the solvent to obtain a PVDF film;
3) melting the PVDF film prepared in the step 2) on a heating table at 200 ℃ to eliminate heat history, then transferring to 120 ℃ within 15s, and preserving heat for 60 min;
4) uniformly coating a layer of 10 wt% hexadecyl trimethyl ammonium bromide aqueous solution with the thickness of 0.5 mu m on the PVDF film prepared in the step 3), and standing for 12 min;
5) annealing the PVDF film prepared in the step 4) at 150 ℃, and preserving heat for 40min to prepare the PVDF cured film.
9. The method for rapidly inducing the alpha-gamma phase transition of the polyvinylidene fluoride film according to claim 1, wherein the method comprises the following steps: the method specifically comprises the following steps:
1) preparing a PVDF solution with the mass concentration of 9% by taking N, N-dimethylformamide as a solvent;
2) uniformly blade-coating the solution prepared in the step 1) on a dry and clean silicon wafer substrate, wherein the thickness of a blade-coated liquid film is 400 mu m, and drying the liquid film at 90 ℃ for 12h to completely remove the solvent to obtain a PVDF film;
3) melting the PVDF film prepared in the step 2) at 205 ℃ to eliminate heat history, then transferring to 150 ℃ within 12s, and preserving heat for 120 min;
4) uniformly coating a layer of 10 wt% choline chloride aqueous solution with the thickness of 0.8 mu m on the PVDF film prepared in the step 3), and standing for 10 min;
5) annealing the PVDF film prepared in the step 4) at 155 ℃, and preserving heat for 20min to prepare the PVDF cured film.
10. The method for rapidly inducing the alpha-gamma phase transition of the polyvinylidene fluoride film according to claim 1, wherein the method comprises the following steps: the method specifically comprises the following steps:
1) preparing a PVDF solution with the mass concentration of 10% by taking N, N-dimethylformamide as a solvent;
2) uniformly blade-coating the solution prepared in the step 1) on a dry and clean silicon wafer substrate, wherein the thickness of a blade-coated liquid film is 500 mu m, and drying the liquid film at 100 ℃ for 6h to completely remove the solvent to obtain a PVDF film;
3) melting the PVDF film prepared in the step 2) at 210 ℃ to eliminate heat history, then transferring to 160 ℃ within 10s, and preserving heat for 600 min;
4) uniformly coating a layer of 10 wt% N-butylpyridinium hexafluorophosphate with the thickness of 1 mu m on the PVDF film prepared in the step 3), and standing for 5 min;
5) annealing the PVDF film prepared in the step 4) at 160 ℃, and preserving heat for 10min to prepare the PVDF cured film.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114716723A (en) * | 2022-05-01 | 2022-07-08 | 青岛科技大学 | Beta-phase polypropylene microporous membrane and preparation method thereof |
| CN115028871A (en) * | 2022-06-22 | 2022-09-09 | 陕西科技大学 | Method for preparing oriented gamma-phase polyvinylidene fluoride film |
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| CN113248762A (en) * | 2021-06-03 | 2021-08-13 | 陕西科技大学 | Method for rapidly preparing gamma-phase polyvinylidene fluoride film |
| CN113336986A (en) * | 2021-06-03 | 2021-09-03 | 陕西科技大学 | Preparation method of oriented gamma-phase PVDF/CTAB composite film |
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| CN113248762A (en) * | 2021-06-03 | 2021-08-13 | 陕西科技大学 | Method for rapidly preparing gamma-phase polyvinylidene fluoride film |
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| HUAN ZHOU ET.AL.: "Facilitated phase transformation of PVDF in its composite with an ionic liquid", 《POLYMER》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114716723A (en) * | 2022-05-01 | 2022-07-08 | 青岛科技大学 | Beta-phase polypropylene microporous membrane and preparation method thereof |
| CN114716723B (en) * | 2022-05-01 | 2023-08-08 | 青岛科技大学 | Beta-phase polypropylene microporous membrane and preparation method thereof |
| CN115028871A (en) * | 2022-06-22 | 2022-09-09 | 陕西科技大学 | Method for preparing oriented gamma-phase polyvinylidene fluoride film |
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