CN103570959B - A kind of preparation method of polyvinylidene fluoride/one-dimensicolumnar columnar structural lead titanate monocrystal nanofiber composite film - Google Patents
A kind of preparation method of polyvinylidene fluoride/one-dimensicolumnar columnar structural lead titanate monocrystal nanofiber composite film Download PDFInfo
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- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 60
- 239000002121 nanofiber Substances 0.000 title claims abstract description 55
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000011521 glass Substances 0.000 claims abstract description 7
- 238000004528 spin coating Methods 0.000 claims abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 48
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 20
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 claims description 20
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 20
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 20
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 12
- 229940069328 povidone Drugs 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 12
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 9
- 239000006185 dispersion Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 230000000873 masking effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000005616 pyroelectricity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of preparation method of polyvinylidene fluoride/one-dimensicolumnar columnar structural lead titanate monocrystal nanofiber composite film, first the method adopts polymer auxiliary water thermal response method to prepare one-dimensional columnar structure lead titanate monocrystal nano fiber, secondly nanofiber is dissolved in dimethyl formamide, be uniformly mixed with polyvinylidene difluoride (PVDF)/dimethyl formamide solution, this mixing solutions carries out spin coating masking on ito glass.The laminated film tentatively prepared is dried at 60-90 DEG C, obtains polyvinylidene fluoride/one-dimensicolumnar columnar structural lead titanate monocrystal nanofiber composite film.Present invention process process is simple, is easy to control, and pollution-free, cost is low, is easy to scale operation; Obtained one-dimensional columnar structure lead titanate monocrystal nano fiber dispersion is good, and length-to-diameter ratio is large, and is uniformly dispersed in laminated film; Obtained polyvinylidene fluoride/one-dimensicolumnar columnar structural lead titanate monocrystal nanofiber composite film uniformity coefficient is high, and dielectric properties are good.
Description
Technical field
The present invention relates to a kind of preparation method of polyvinylidene fluoride/one-dimensicolumnar columnar structural lead titanate monocrystal nanofiber composite film, belong to ceramic and field of nanocomposite materials.
Background technology
In recent years, due to the high speed development of electronic industry, propose increasing requirement to the functionalization of the miniaturization of components and parts, filming and material, the development research of the therefore research of piezoelectricity film material with function, particularly polymer composites becomes the focus of research.Lead titanate is owing to having abundant physicals, and such as excellent ferroelectric, piezoelectric & dielectric properties, have a wide range of applications in field of electronic devices such as high dielectric capacitor, piezoelectric transducer, pyroelectricity sensor and non-volatility ferroelectric storeies.Polyvinylidene difluoride (PVDF) is the flexible ferroelectric material of current widespread use, the advantage such as have that density is little, the high and specific acoustic resistance of stable chemical performance, easily processing, physical strength is low, also also exists that dielectric loss is high, not easily polarization and the shortcoming such as use temperature is low simultaneously.Therefore, research and development polyvinylidene difluoride (PVDF)/piezo-electric ceramic composite material can overcome respective deficiency as a kind of novel matrix material, there is the features such as high pressure is electrical, high dielectric property, strong snappiness, low density, easily processing, numerous areas can be waited to replace the application of piezoceramic material in economical and military affairs, tool is of great significance.
Summary of the invention
The object of the present invention is to provide a kind of technique simple, process is easy to the preparation method of the polyvinylidene fluoride/one-dimensicolumnar columnar structural lead titanate monocrystal nanofiber composite film controlled.
The preparation method of polyvinylidene fluoride/one-dimensicolumnar columnar structural lead titanate monocrystal nanofiber composite film of the present invention, comprises following processing step:
1) tetrabutyl titanate is dissolved in ethylene glycol monomethyl ether, is made into the tetrabutyl titanate solution that concentration is 0.51mol/L;
2) under whipped state, instill the ammonia soln that mass concentration is 30%, tetrabutyl titanate hydrolysis is precipitated in the tetrabutyl titanate solution that step 1) obtains, after filtration, washing, obtains titanium precipitation;
3) lead nitrate is dissolved in deionized water, forms the lead nitrate aqueous solution, regulate Pb
2+ionic concn is 0.55mol/L;
4) potassium hydroxide, polyvinylpyrrolidone and polyvinyl alcohol are dissolved in deionized water respectively, the aqueous povidone solution that configuration concentration is the potassium hydroxide aqueous solution of 0.5mol/L, concentration is 2g/L and concentration are the polyvinyl alcohol water solution of 2g/L;
5) by obtained above the lead nitrate aqueous solution, potassium hydroxide aqueous solution, polyvinyl alcohol water solution and aqueous povidone solution by volume 1:1:1:0.05-0.8 and Ti precipitation join in the reactor inner bag of tetrafluoroethylene, its volume is regulated to reach 80% of reactor inner bag volume with deionized water, stir at least 10-30min, obtain suspension liquid;
6) reactor inner bag step 5) being configured with reaction mass is placed in reactor, and sealing, at 180-200
oafter carrying out hydro-thermal reaction 8-12h at C temperature, be placed in air Temperature fall to room temperature, take out reactant, filter, by deionized water and washes of absolute alcohol reaction product, dry, obtain one-dimensional columnar structure lead titanate monocrystal nano fiber;
7) by polyvinylidene difluoride (PVDF) powder stirring and dissolving in dimethyl formamide;
8) be dissolved in dimethyl formamide by the one-dimensional columnar structure lead titanate monocrystal nano fiber ultrasonic oscillation that step 6) is obtained, the mass ratio of one-dimensional columnar structure lead titanate monocrystal nano fiber and step 7) polyvinylidene difluoride (PVDF) powder is 5%-30%;
9) the molten liquid-phase mixing that solution step 7) obtained and step 8) obtain, stirs 30-60min;
10) mixing solutions of step 9) gained is spin-coated on ito glass is filmed;
11) laminated film that step 10) is obtained is dried at 60-90 DEG C, obtain polyvinylidene fluoride/one-dimensicolumnar columnar structural lead titanate monocrystal nanofiber composite film.
The purity of tetrabutyl titanate of the present invention, ethylene glycol monomethyl ether, lead nitrate, potassium hydroxide, polyvinylpyrrolidone, polyvinyl alcohol and dimethyl formamide is all not less than chemical pure.
Above-mentioned steps 10) described in spin coating rotating speed can be 1500-3000 rev/min.
Polyvinylidene fluoride/one-dimensicolumnar columnar structural lead titanate monocrystal nanofiber composite film of the present invention, its one-dimensional columnar structure lead titanate monocrystal nano fiber is evenly distributed in polyvinylidene difluoride (PVDF) substrate, and the thickness of this laminated film is 4.3-5 μm.
Present invention process process is simple, is easy to control, and pollution-free, cost is low, is easy to scale operation; Obtained one-dimensional columnar structure lead titanate monocrystal nano fiber dispersion is good, and length-to-diameter ratio is large, and is uniformly dispersed in laminated film; Obtained polyvinylidene fluoride/one-dimensicolumnar columnar structural lead titanate monocrystal nanofiber composite film uniformity coefficient is high, and dielectric properties are good.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of polyvinylidene fluoride/one-dimensicolumnar columnar structural lead titanate monocrystal nanofiber composite film;
Fig. 2 is the SEM picture of polyvinylidene fluoride/one-dimensicolumnar columnar structural lead titanate monocrystal nanofiber composite film;
Fig. 3 be polyvinylidene fluoride/one-dimensicolumnar columnar structural lead titanate monocrystal nanofiber composite film at room temperature, the graph of a relation of specific inductivity and frequency.
Embodiment
Below in conjunction with embodiment, the inventive method is described in further detail.
Embodiment 1
1) 1.736g tetrabutyl titanate is dissolved in 10ml ethylene glycol monomethyl ether, obtains tetrabutyl titanate solution;
2) under whipped state, instill the ammonia soln that mass concentration is 30%, tetrabutyl titanate hydrolysis is precipitated in the tetrabutyl titanate solution that step 1) obtains, after filtration, washing, obtains titanium precipitation;
3) lead nitrate is dissolved in deionized water, forms the lead nitrate aqueous solution, regulate Pb
2+ionic concn is 0.55mol/L;
4) potassium hydroxide, polyvinylpyrrolidone and polyvinyl alcohol are dissolved in deionized water respectively, the aqueous povidone solution that configuration concentration is the potassium hydroxide aqueous solution of 0.5mol/L, concentration is 2g/L and concentration are the polyvinyl alcohol water solution of 2g/L;
5) by the lead nitrate aqueous solution obtained above, potassium hydroxide aqueous solution, polyvinyl alcohol water solution, aqueous povidone solution by volume 1:1:1:0.5 and Ti precipitation join in the reactor inner bag of tetrafluoroethylene, its volume is regulated to reach 80% of reactor inner bag volume with deionized water, stir 20min, obtain suspension liquid;
6) reactor inner bag step 5) being configured with reaction mass is placed in reactor, and sealing, 190
oafter carrying out hydro-thermal reaction 10h at C temperature, be placed in air Temperature fall to room temperature, take out reactant, filter, by deionized water and washes of absolute alcohol reaction product, dry, obtain one-dimensional columnar structure lead titanate monocrystal nano fiber.The good dispersity of this nanofiber, length-to-diameter ratio is 150-300;
7) by polyvinylidene difluoride (PVDF) powder stirring and dissolving in dimethyl formamide;
8) be dissolved in dimethyl formamide by the one-dimensional columnar structure lead titanate monocrystal nano fiber ultrasonic oscillation that step 6) is obtained, the mass ratio of one-dimensional columnar structure lead titanate monocrystal nano fiber and step 7) polyvinylidene difluoride (PVDF) powder is 20%;
9) the molten liquid-phase mixing that solution step 7) obtained and step 8) obtain, stirs 45min;
10) be spin-coated on ito glass by the mixing solutions of step 9) gained and be filmed, rotating speed is 3000 revs/min;
11) laminated film that step 10) is obtained is dried in 80 DEG C of baking ovens, obtain the polyvinylidene fluoride/one-dimensicolumnar columnar structural lead titanate monocrystal nanofiber composite film of thickness 4.5 μm.
As shown in Figure 1, as seen from the figure, the corresponding strong peak of diffraction is one-dimensional columnar structure lead titanate to the XRD figure spectrum of this laminated film.Fig. 2 is the SEM picture of polyvinylidene fluoride/one-dimensicolumnar columnar structural lead titanate monocrystal nanofiber composite film, as seen from the figure, the length of one-dimensional columnar structure lead titanate monocrystal nano fiber is about 30-50 μm, diameter is about 100-300nm, and one-dimensional columnar structure lead titanate monocrystal nano fiber is evenly dispersed in polyvinylidene difluoride (PVDF) substrate.Fig. 3 be polyvinylidene fluoride/one-dimensicolumnar columnar structural lead titanate monocrystal nanofiber composite film at room temperature, the graph of a relation of its specific inductivity and frequency.As we know from the figure, under 1kHz frequency, the specific inductivity of laminated film is 10.5.Along with the rising of frequency, specific inductivity reduces gradually, and especially in 200kHz-5MHz range of frequency, specific inductivity declines quickly, has occurred relaxation phenomena, has belonged to dipole-orientation polarization.
Embodiment 2
1) 1.736g tetrabutyl titanate is dissolved in 10ml ethylene glycol monomethyl ether, obtains tetrabutyl titanate solution;
2) under whipped state, instill the ammonia soln that mass concentration is 30%, tetrabutyl titanate hydrolysis is precipitated in the tetrabutyl titanate solution that step 1) obtains, after filtration, washing, obtains titanium precipitation;
3) lead nitrate is dissolved in deionized water, forms the lead nitrate aqueous solution, regulate Pb
2+ionic concn is 0.55mol/L;
4) potassium hydroxide, polyvinylpyrrolidone and polyvinyl alcohol are dissolved in deionized water respectively, the aqueous povidone solution that configuration concentration is the potassium hydroxide aqueous solution of 0.5mol/L, concentration is 2g/L and concentration are the polyvinyl alcohol water solution of 2g/L;
5) by the lead nitrate aqueous solution obtained above, potassium hydroxide aqueous solution, polyvinyl alcohol water solution, aqueous povidone solution by volume 1:1:1:0.1 and Ti precipitation join in the reactor inner bag of tetrafluoroethylene, its volume is regulated to reach 80% of reactor inner bag volume with deionized water, stir 10min, obtain suspension liquid;
6) reactor inner bag step 5) being configured with reaction mass is placed in reactor, and sealing, 200
oafter carrying out hydro-thermal reaction 12h at C temperature, be placed in air Temperature fall to room temperature, take out reactant, filter, by deionized water and washes of absolute alcohol reaction product, dry, obtain one-dimensional columnar structure lead titanate monocrystal nano fiber.The good dispersity of this nanofiber, length-to-diameter ratio is 150-300;
7) by polyvinylidene difluoride (PVDF) powder stirring and dissolving in dimethyl formamide;
8) be dissolved in dimethyl formamide by the one-dimensional columnar structure lead titanate monocrystal nano fiber ultrasonic oscillation that step 6) is obtained, the mass ratio of one-dimensional columnar structure lead titanate monocrystal nano fiber and step 7) polyvinylidene difluoride (PVDF) powder is 10%;
9) solution step 7) obtained and the molten liquid-phase mixing obtained by step 8), stir 45min;
10) be spin-coated on ito glass by the mixing solutions of step 9) gained and be filmed, rotating speed is 2000 revs/min;
11) laminated film obtained in step 10) is dried in 60 DEG C of baking ovens, obtain the polyvinylidene fluoride/one-dimensicolumnar columnar structural lead titanate monocrystal nanofiber composite film of thickness 4.4 μm.
Embodiment 3
1) 1.736g tetrabutyl titanate is dissolved in 10ml ethylene glycol monomethyl ether, obtains tetrabutyl titanate solution;
2) under whipped state, instill the ammonia soln that mass concentration is 30%, tetrabutyl titanate hydrolysis is precipitated in the tetrabutyl titanate solution that step 1) obtains, after filtration, washing, obtains titanium precipitation;
3) lead nitrate is dissolved in deionized water, forms the lead nitrate aqueous solution, regulate Pb
2+ionic concn is 0.55mol/L;
4) potassium hydroxide, polyvinylpyrrolidone and polyvinyl alcohol are dissolved in deionized water respectively, the aqueous povidone solution that configuration concentration is the potassium hydroxide aqueous solution of 0.5mol/L, concentration is 2g/L and concentration are the polyvinyl alcohol water solution of 2g/L;
5) by the lead nitrate aqueous solution obtained above, potassium hydroxide aqueous solution, polyvinyl alcohol water solution, aqueous povidone solution by volume 1:1:1:0.05 and Ti precipitation join in the reactor inner bag of tetrafluoroethylene, its volume is regulated to reach 80% of reactor inner bag volume with deionized water, stir 10min, obtain suspension liquid;
6) reactor inner bag step 5) being configured with reaction mass is placed in reactor, and sealing, 200
oafter carrying out hydro-thermal reaction 12h at C temperature, be placed in air Temperature fall to room temperature, take out reactant, filter, by deionized water and washes of absolute alcohol reaction product, dry, obtain one-dimensional columnar structure lead titanate monocrystal nano fiber.The good dispersity of this nanofiber, length-to-diameter ratio is 150-300;
7) by polyvinylidene difluoride (PVDF) powder stirring and dissolving in dimethyl formamide;
8) be dissolved in dimethyl formamide by the one-dimensional columnar structure lead titanate monocrystal nano fiber ultrasonic oscillation that step 6) is obtained, the mass ratio of one-dimensional columnar structure lead titanate monocrystal nano fiber and step 7) polyvinylidene difluoride (PVDF) powder is 5%;
9) solution step 7) obtained and the molten liquid-phase mixing obtained by step 8), stir 30min;
10) be spin-coated on ito glass by the mixing solutions of step 9) gained and be filmed, rotating speed is 1500 revs/min;
11) laminated film obtained in step 10) is dried in 60 DEG C of baking ovens, obtain the polyvinylidene fluoride/one-dimensicolumnar columnar structural lead titanate monocrystal nanofiber composite film of thick 4.3 μm.
Embodiment 4
1) 1.736g tetrabutyl titanate is dissolved in 10ml ethylene glycol monomethyl ether, obtains tetrabutyl titanate solution;
2) under whipped state, instill the ammonia soln that mass concentration is 30%, tetrabutyl titanate hydrolysis is precipitated in the tetrabutyl titanate solution that step 1) obtains, after filtration, washing, obtains titanium precipitation;
3) lead nitrate is dissolved in deionized water, forms the lead nitrate aqueous solution, regulate Pb
2+ionic concn is 0.55mol/L;
4) potassium hydroxide, polyvinylpyrrolidone and polyvinyl alcohol are dissolved in deionized water respectively, the aqueous povidone solution that configuration concentration is the potassium hydroxide aqueous solution of 0.5mol/L, concentration is 2g/L and concentration are the polyvinyl alcohol water solution of 2g/L;
5) by the lead nitrate aqueous solution obtained above, potassium hydroxide aqueous solution, polyvinyl alcohol water solution, aqueous povidone solution by volume 1:1:1:0.8 and Ti precipitation join in the reactor inner bag of tetrafluoroethylene, its volume is regulated to reach 80% of reactor inner bag volume with deionized water, stir 30min, obtain suspension liquid;
6) reactor inner bag step 5) being configured with reaction mass is placed in reactor, and sealing, 180
oafter carrying out hydro-thermal reaction 8h at C temperature, be placed in air Temperature fall to room temperature, take out reactant, filter, by deionized water and washes of absolute alcohol reaction product, dry, obtain one-dimensional columnar structure lead titanate monocrystal nano fiber.The good dispersity of this nanofiber, length-to-diameter ratio is 150-300;
7) by polyvinylidene difluoride (PVDF) powder stirring and dissolving in dimethyl formamide;
8) be dissolved in dimethyl formamide by the one-dimensional columnar structure lead titanate monocrystal nano fiber ultrasonic oscillation that step 6) is obtained, the mass ratio of one-dimensional columnar structure lead titanate monocrystal nano fiber and step 7) polyvinylidene difluoride (PVDF) powder is 30%;
9) solution step 7) obtained and the molten liquid-phase mixing obtained by step 8), stir 60min;
10) be spin-coated on ito glass by the mixing solutions of step 9) gained and be filmed, rotating speed is 3000 revs/min;
11) laminated film obtained in step 10) is dried in 90 DEG C of baking ovens, obtain the polyvinylidene fluoride/one-dimensicolumnar columnar structural lead titanate monocrystal nanofiber composite film that thickness is 4.9 μm.
Claims (4)
1. the preparation method of polyvinylidene fluoride/one-dimensicolumnar columnar structural lead titanate monocrystal nanofiber composite film, the thickness of this laminated film is 4.3-5 μm, and its preparation comprises the following steps:
1) tetrabutyl titanate is dissolved in ethylene glycol monomethyl ether, is made into the tetrabutyl titanate solution that concentration is 0.51mol/L;
2) under whipped state, instill the ammonia soln that mass concentration is 30%, tetrabutyl titanate hydrolysis is precipitated in the tetrabutyl titanate solution that step 1) obtains, after filtration, washing, obtains titanium precipitation;
3) lead nitrate is dissolved in deionized water, forms the lead nitrate aqueous solution, regulate Pb
2+ionic concn is 0.55mol/L;
4) potassium hydroxide, polyvinylpyrrolidone and polyvinyl alcohol are dissolved in deionized water respectively, the aqueous povidone solution that configuration concentration is the potassium hydroxide aqueous solution of 0.5mol/L, concentration is 2g/L and concentration are the polyvinyl alcohol water solution of 2g/L;
5) by obtained above the lead nitrate aqueous solution, potassium hydroxide aqueous solution, polyvinyl alcohol water solution and aqueous povidone solution by volume 1:1:1:0.05-0.8 and Ti precipitation join in the reactor inner bag of tetrafluoroethylene, its volume is regulated to reach 80% of reactor inner bag volume with deionized water, stir at least 10-30min, obtain suspension liquid;
6) reactor inner bag step 5) being configured with reaction mass is placed in reactor, and sealing, at 180-200
oafter carrying out hydro-thermal reaction 8-12h at C temperature, be placed in air Temperature fall to room temperature, take out reactant, filter, by deionized water and washes of absolute alcohol reaction product, dry, obtain one-dimensional columnar structure lead titanate monocrystal nano fiber;
7) by polyvinylidene difluoride (PVDF) powder stirring and dissolving in dimethyl formamide;
8) be dissolved in dimethyl formamide by the one-dimensional columnar structure lead titanate monocrystal nano fiber ultrasonic oscillation that step 6) is obtained, the mass ratio of one-dimensional columnar structure lead titanate monocrystal nano fiber and step 7) polyvinylidene difluoride (PVDF) powder is 5%-30%;
9) the molten liquid-phase mixing that solution step 7) obtained and step 8) obtain, stirs 30-60min;
10) mixing solutions of step 9) gained is spin-coated on ito glass is filmed;
11) laminated film that step 10) is obtained is dried at 60-90 DEG C, obtain polyvinylidene fluoride/one-dimensicolumnar columnar structural lead titanate monocrystal nanofiber composite film.
2. the preparation method of polyvinylidene fluoride/one-dimensicolumnar columnar structural lead titanate monocrystal nanofiber composite film according to claim 1, is characterized in that the purity of described tetrabutyl titanate, ethylene glycol monomethyl ether, lead nitrate, potassium hydroxide, polyvinylpyrrolidone, polyvinyl alcohol and dimethyl formamide is all not less than chemical pure.
3. the preparation method of polyvinylidene fluoride/one-dimensicolumnar columnar structural lead titanate monocrystal nanofiber composite film according to claim 1, is characterized in that the thickness of the polyvinylidene fluoride/one-dimensicolumnar columnar structural lead titanate monocrystal nanofiber composite film obtained is 4.3-5 μm.
4. the preparation method of polyvinylidene fluoride/one-dimensicolumnar columnar structural lead titanate monocrystal nanofiber composite film according to claim 1, is characterized in that the spin coating rotating speed described in step 10) is 1500-3000 rev/min.
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| CN103880298A (en) * | 2014-02-19 | 2014-06-25 | 浙江大学 | Method for preparing one-dimensional tetragonal lead titanate single crystal nanofiber/polyvinylidene fluoride composite film |
| CN104261464A (en) * | 2014-09-29 | 2015-01-07 | 浙江大学 | Preparation method of one-dimensional lead titanate/cadmium sulfide composite nano structure |
| CN106589431B (en) * | 2016-12-26 | 2020-03-10 | 清华大学深圳研究生院 | Pyroelectric flexible composite film and preparation method thereof |
| CN106751250B (en) * | 2017-01-12 | 2019-03-08 | 上海交通大学医学院附属新华医院 | A kind of polymer piezoelectric composite material and preparation method and application |
| CN108328650B (en) * | 2018-03-20 | 2019-10-15 | 浙江理工大学 | One one-step hydro-thermal synthesis method of one-dimensional Perovskite Phase lead titanates nanofiber |
| CN110320519A (en) * | 2019-06-09 | 2019-10-11 | 重庆工商大学融智学院 | A kind of expression of spatial data and fast display method |
| CN112011174B (en) * | 2020-09-07 | 2022-06-28 | 陕西科技大学 | Preparation method of nano silicon dioxide/nitrogen-doped modified fibrous composite material |
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