CN103113602A - Method for preparing high-oriented gamma phase polyvinylidene fluoride PVDF thin film - Google Patents
Method for preparing high-oriented gamma phase polyvinylidene fluoride PVDF thin film Download PDFInfo
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Abstract
The invention relates to a method for preparing a high-oriented gamma phase polyvinylidene fluoride PVDF thin film. The method comprises the following steps of: 1) first, casting a thin film for PVDF liquor to heat, insulate and eliminate thermal history, and quickly cooling the PVDF thin film at 50 DEG C/min to 160-170 DEG C; and 2) applying pressure to melt by a polymethylsiloxane plate to apply a shear stress, standing at 160-170 DEG C, wherein the crystallizing form at 160-163 DEG C is converted to alpha crystallizing form, and conversion from alpha crystallizing form to gamma crystallizing form occurs at 168-170 DEG C; the crystallizing crystal nucleus is alpha crystal nucleus at 164-167 DEG C, and the crystallizing form at 168-170 DEG C is gamma crystallizing form. A polarizing microscope, a scanning electron microscope and an infrared spectrometer represent crystallization of the melt in a shear stress field and a crystal structure after crystallization, so that the method is simple in process, and simple, convenient and accessible, and the problem that pure gamma phase PVDF thin film cannot be obtained by isothermal crystallization is solved. The gamma phase PVDF thin film which is high in purity, high in orientation and excellent in thermodynamic property can be prepared.
Description
Technical field
The invention belongs to polyvinylidene difluoride (PVDF) PVDF film preparing technology field, be specifically related to a kind of method for preparing high orientation γ phase polyvinylidene fluoride PVDF film.
Background technology
Polyvinylidene difluoride (PVDF) PVDF has both the characteristic of resins for universal use and fluoro-resin, except having good high thermal resistance, chemical resistance, scale resistance, anti-x radiation x, weather resistance, also having the properties such as piezoelectricity, dielectricity, pyroelectricity, is the product that in present fluoro-containing plastic film, output is at the second place.
The diversified use properties of PVDF has substantial connection with its crystalline structure complicated and changeable (α, β, γ, δ and ε equate), and phase co-conversion under certain condition between various crystal formation crystal.But, people's common concern be α, β, three kinds of crystal formations of γ.The alpha-crystal form that is obtained by fusion-crystallization belongs to oblique system, and molecular chain is the TGTG' conformation, because the opposite not salience(-cy) of molecular chain dipole polarity makes the PVDF of this crystal formation to use as common plastics.Beta crystal belongs to rhombic system, and molecular chain is alltrans TTT conformation, and the zigzag chain conformation of polarity makes the PVDF of this crystal formation show than the forceful electric power performance.The important crystal formation of another of PVDF is the γ crystal formation, and its molecular chain is the TTTGTTTG' conformation, and the crystal of this crystal formation is the same with the β crystal also has ferroelectric effect, has very large using value as pyroelectricity material at high-technology field.
But the γ crystalline phase needs less condensate depression just can obtain, by melting high temperature crystallization or high temperature annealing method, even under very little condensate depression due to lower nucleation and growth speed, also can not get a large amount of γ crystalline phases, and the α crystalline phase exists in a large number also; Successfully prepared the method for the PVDF nano-array whisker of γ type by anodic oxidation aluminium formwork solution impregnation method, expensive because technical requirements is high, use value is little; And adding a small amount of γ film such as the acquisition of the nucleators such as KBr, degree of crystallinity and fusing point are lower.Also have some also to have the shortcoming of aforesaid method as preparation γ film process such as micro-embossing technology.Based on this, the present invention is intended to inquire into simple and easy to do and high γ phase content PVDF thin film technology method.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the purpose of this invention is to provide a kind of method for preparing high orientation γ phase polyvinylidene fluoride PVDF film.
To achieve these goals, the technical solution used in the present invention is: a kind of method for preparing high orientation γ phase polyvinylidene fluoride PVDF film includes following steps:
1) at first the solution-cast film heating to 195 of polyvinylidene difluoride (PVDF) PVDF～205 ℃ insulation 10min are eliminated thermal histories, subsequently polyvinylidene difluoride (PVDF) PVDF film is cooled to rapidly 160～170 ℃ with the speed of 50 ℃/min;
2) utilize the polymethyl siloxane plate to apply 10
4～10
5Pa pressure applies shear-stress with the shearing rate of 0.4～2.0m/s to melt, standing 48～168h under 160～170 ℃, crystalline structure after the crystallisation process of melt and crystallization are completed in polarized light microscopy Microscopic observation shear stress field, discovery is alpha-crystal form at 160～163 ℃ of lower Crystal types, through annealing under this temperature field, the alpha-crystal form transformation of γ crystal formation phase in opposite directions can occur; Be the α nucleus at 164～167 ℃ of lower crystallization nucleus, transformation mutually to the γ crystal formation when impelling alpha-crystal form growing, energy unnecessary under this temperature field is occuring, and phase velocity is greater than the alpha-crystal form speed of growth, when the transition front catch up with growth front, alpha-crystal form stops growing, and γ crystal formation then begins to grow; 168～170 ℃ of Crystal types are the γ crystal formation;
3) cylindrulite after crystallization is adopted the characterization methods such as infrared spectra FTIR, scanning electronic microscope SEM, transmission electron microscope TEM, differential scanning calorimeter DSC analyze crystalline structure and the pattern of PVDF cylindrulite, with the crystal formation of checking cylindrulite.
The invention has the beneficial effects as follows:
PVDF can generate the cylindrulite of high-orientation, high nucleation density in shear stress field.Studies show that, in stress field, the nucleation rate of melt significantly improves.Therefore, near the PVDF melting temperature time, due to the effect of shear stress field, nucleation rate, the nucleation density of PVDF significantly improve when temperature, and its growth velocity also slightly increases.Density is enough high when shearing, even in the very little situation of condensate depression, also can just can obtain in the very short time cylindrulite film of PVDF.Then, with form, structure and the performance of the film after under different condensate depression, crystallization is completed by infrared spectra FTIR, scanning electronic microscope SEM, transmission electron microscope TEM, differential scanning calorimeter DSC characterization method research plane of crystal, with the crystal formation of checking cylindrulite.The advantage of this patent maximum is simple for process, and crystalline melting point is high in film, the γ cylindrulite content of the PVDF film of preparation reaches 100% substantially, has solved the problem that isothermal crystal can't obtain pure γ phase PVDF film.
Embodiment:
Below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment one
A kind of method for preparing high orientation γ phase polyvinylidene fluoride PVDF film includes following steps:
1) at first the solution-cast film heating to 200 of a polyvinylidene difluoride (PVDF) PVDF ℃ insulation 10min is eliminated thermal history, subsequently polyvinylidene difluoride (PVDF) PVDF film is cooled to rapidly 170 ℃ with the speed of 50 ℃/min;
2) utilize the polymethyl siloxane plate to apply 10
5Pa pressure applies shear-stress with the shearing rate of 1.5m/s to melt, and standing 96h under 170 ℃ can obtain γ phase PVDF film, the crystalline structure after the crystallisation process of melt and crystallization are completed in polarized light microscopy Microscopic observation shear stress field;
3) cylindrulite after crystallization is adopted the characterization methods such as infrared spectra FTIR, scanning electronic microscope SEM, transmission electron microscope TEM, differential scanning calorimeter DSC analyze crystalline structure and the pattern of PVDF cylindrulite, with the crystal formation of checking cylindrulite.
Result shows, is the γ crystal formation at the cylindrulite of 170 ℃ of crystallization 96h, obtains the PVDF film of γ crystal formation.
Embodiment two
A kind of method for preparing high orientation γ phase polyvinylidene fluoride PVDF film includes following steps:
1) at first the solution-cast film heating to 205 of a polyvinylidene difluoride (PVDF) PVDF ℃ insulation 10min is eliminated thermal history, subsequently polyvinylidene difluoride (PVDF) PVDF film is cooled to rapidly 165 ℃ with the speed of 50 ℃/min;
2) utilize the polymethyl siloxane plate to apply 10
5Pa pressure applies shear-stress with the shearing rate of 2.0m/s to melt, and standing 72h under 165 ℃ can obtain γ phase PVDF film, the crystalline structure after the crystallisation process of melt and crystallization are completed in polarized light microscopy Microscopic observation shear stress field;
3) adopt infrared spectra FTIR, scanning electronic microscope SEM, transmission electron microscope TEM, differential scanning calorimeter DSC characterization method to analyze crystalline structure and the pattern of PVDF cylindrulite to the cylindrulite after crystallization, with the crystal formation of checking cylindrulite.
Result shows, is the α nucleus at 165 ℃ of crystallization nucleations, α occurs simultaneously to the phase transformation of γ crystal formation when alpha-crystal is grown.Over growth velocity, alpha-crystal form stops growing when transformation rate, and the γ crystal formation begins growth.Crystallization 72h obtains the PVDF film of full γ phase.
Embodiment three
A kind of method for preparing high orientation γ phase polyvinylidene fluoride PVDF film includes following steps:
1) at first the solution-cast film heating to 195 of a polyvinylidene difluoride (PVDF) PVDF ℃ insulation 10min is eliminated thermal history, subsequently polyvinylidene difluoride (PVDF) PVDF film is cooled to rapidly 160 ℃ with the speed of 50 ℃/min;
2) utilize the polymethyl siloxane plate to apply 10
5Pa pressure applies shear-stress with the shearing rate of 0.6m/s to melt, standing 48h under 160 ℃, can obtain α phase PVDF film, crystallization continues after 2 days after annealing 120h at 160 ℃ of temperature, obtain the γ phase film after the phase transformation of α phase, the crystalline structure after the crystallisation process of melt and crystallization are completed in polarized light microscopy Microscopic observation shear stress field;
3) cylindrulite after crystallization is adopted the characterization methods such as infrared spectra FTIR, scanning electronic microscope SEM, transmission electron microscope TEM, differential scanning calorimeter DSC analyze crystalline structure and the pattern of PVDF cylindrulite, with the crystal formation of checking cylindrulite.
Result shows, be the α nucleus at 160 ℃ of crystallization nucleations, after crystallization 48h, annealing 120h days at this temperature, obtain the γ phase PVDF film after the α phase transformation, and the melt temperature of the present embodiment gained γ phase PVDF film is than embodiment 1 and 2 gained γ high 8～12 ℃ of left and right of melt temperature of PVDF film mutually.
Claims (4)
1. a method for preparing high orientation γ phase polyvinylidene fluoride PVDF film, is characterized in that, includes following steps:
1) at first the solution-cast film heating to 195 of polyvinylidene difluoride (PVDF) PVDF～205 ℃ insulation 10min are eliminated thermal histories, subsequently polyvinylidene difluoride (PVDF) PVDF film is cooled to rapidly 160～170 ℃ with the speed of 50 ℃/min;
2) utilize the polymethyl siloxane plate to apply 10
4～10
5Pa pressure applies shear-stress with the shearing rate of 0.4～2.0m/s to melt, standing 48～168h under 160～170 ℃, crystalline structure after the crystallisation process of melt and crystallization are completed in polarized light microscopy Microscopic observation shear stress field, discovery is alpha-crystal form at 160～163 ℃ of lower Crystal types, through annealing under this temperature field, the alpha-crystal form transformation of γ crystal formation phase in opposite directions can occur; Be the α nucleus at 164～167 ℃ of lower crystallization nucleus, transformation mutually to the γ crystal formation when impelling alpha-crystal form growing, energy unnecessary under this temperature field is occuring, and phase velocity is greater than the alpha-crystal form speed of growth, when the transition front catch up with growth front, alpha-crystal form stops growing, and γ crystal formation then begins to grow; 168～170 ℃ of Crystal types are the γ crystal formation;
3) cylindrulite after crystallization is adopted the characterization methods such as infrared spectra FTIR, scanning electronic microscope SEM, transmission electron microscope TEM, differential scanning calorimeter DSC analyze crystalline structure and the pattern of PVDF cylindrulite, with the crystal formation of checking cylindrulite.
2. a kind of method for preparing high orientation γ phase polyvinylidene fluoride PVDF film according to claim 1, is characterized in that, includes following steps:
1) at first the solution-cast film heating to 200 of a polyvinylidene difluoride (PVDF) PVDF ℃ insulation 10min is eliminated thermal history, subsequently polyvinylidene difluoride (PVDF) PVDF film is cooled to rapidly 170 ℃ with the speed of 50 ℃/min;
2) utilize the polymethyl siloxane plate to apply 10
5Pa pressure applies shear-stress with the shearing rate of 1.5m/s to melt, and standing 96h under 170 ℃ can obtain γ phase PVDF film, the crystalline structure after the crystallisation process of melt and crystallization are completed in polarized light microscopy Microscopic observation shear stress field;
3) adopt infrared spectra FTIR, scanning electronic microscope SEM, transmission electron microscope TEM, differential scanning calorimeter DSC characterization method to analyze crystalline structure and the pattern of PVDF cylindrulite to the cylindrulite after crystallization, with the crystal formation of checking cylindrulite.
3. a kind of method for preparing high orientation γ phase polyvinylidene fluoride PVDF film according to claim 1, is characterized in that, includes following steps:
1) at first the solution-cast film heating to 205 of a polyvinylidene difluoride (PVDF) PVDF ℃ insulation 10min is eliminated thermal history, subsequently polyvinylidene difluoride (PVDF) PVDF film is cooled to rapidly 165 ℃ with the speed of 50 ℃/min;
2) utilize the polymethyl siloxane plate to apply 10
4Pa pressure applies shear-stress with the shearing rate of 2.0m/s to melt, and standing 72h under 165 ℃ can obtain γ phase PVDF film, the crystalline structure after the crystallisation process of melt and crystallization are completed in polarized light microscopy Microscopic observation shear stress field;
3) adopt infrared spectra FTIR, scanning electronic microscope SEM, transmission electron microscope TEM, differential scanning calorimeter DSC characterization method to analyze crystalline structure and the pattern of PVDF cylindrulite to the cylindrulite after crystallization, with the crystal formation of checking cylindrulite.
4. a kind of method for preparing high orientation γ phase polyvinylidene fluoride PVDF film according to claim 1, is characterized in that, includes following steps:
1) at first the solution-cast film heating to 195 of a polyvinylidene difluoride (PVDF) PVDF ℃ insulation 10min is eliminated thermal history, subsequently polyvinylidene difluoride (PVDF) PVDF film is cooled to rapidly 160 ℃ with the speed of 50 ℃/min;
2) utilize the polymethyl siloxane plate to apply 10
5Pa pressure applies shear-stress with the shearing rate of 0.6m/s to melt, standing 48h under 160 ℃, can obtain α phase PVDF film, crystallization continues after 2 days after annealing 120h at 160 ℃ of temperature, obtain the γ phase film after the phase transformation of α phase, the crystalline structure after the crystallisation process of melt and crystallization are completed in polarized light microscopy Microscopic observation shear stress field;
3) adopt infrared spectra FTIR, scanning electronic microscope SEM, transmission electron microscope TEM, differential scanning calorimeter DSC characterization method to analyze crystalline structure and the pattern of PVDF cylindrulite to the cylindrulite after crystallization, with the crystal formation of checking cylindrulite.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103497459A (en) * | 2013-08-23 | 2014-01-08 | 陕西科技大学 | Preparation method of polyvinylidene fluoride micrometer bulb tube |
| CN104877152A (en) * | 2015-05-08 | 2015-09-02 | 陕西科技大学 | Method for preparing copper-based nanometer zinc oxide-polyvinylidene fluoride composite material |
| CN105540535A (en) * | 2015-12-29 | 2016-05-04 | 陕西科技大学 | Method for preparing multi-scale high-gamma-phase polyvinylidene fluoride hollow nanowires |
| CN106009426A (en) * | 2016-05-26 | 2016-10-12 | 陕西科技大学 | Preparation method of MgCl2-doped annular gamma-phase polyvinylidene-fluoride-base composite film |
| US9543322B2 (en) | 2014-09-09 | 2017-01-10 | Sabic Global Technologies B.V. | Methods for producing a thin film ferroelectric device using a two-step temperature process on an organic polymeric ferroelectric precursor material stacked between two conductive materials |
| CN109694486A (en) * | 2018-11-20 | 2019-04-30 | 北京化工大学 | The preparation method of 100% γ phase PVDF thin film |
| CN111205496A (en) * | 2020-02-28 | 2020-05-29 | 北京化工大学 | Preparation method of polyvinylidene fluoride gamma-type crystal |
| CN112708154A (en) * | 2021-01-08 | 2021-04-27 | 陕西科技大学 | Nucleation method for improving polyvinylidene fluoride gamma phase |
| CN113248762A (en) * | 2021-06-03 | 2021-08-13 | 陕西科技大学 | Method for rapidly preparing gamma-phase polyvinylidene fluoride film |
| CN115028871A (en) * | 2022-06-22 | 2022-09-09 | 陕西科技大学 | Method for preparing oriented gamma-phase polyvinylidene fluoride film |
-
2013
- 2013-01-21 CN CN2013100201701A patent/CN103113602A/en active Pending
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| LOVINGER, A.J.: ""Crystallization and morphology of melt-solidified poly(vinylidene fluoride)"", 《JOURNAL OF POLYMER SCIENCE, POLYMER PHYSICS EDITION》 * |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103497459A (en) * | 2013-08-23 | 2014-01-08 | 陕西科技大学 | Preparation method of polyvinylidene fluoride micrometer bulb tube |
| US9543322B2 (en) | 2014-09-09 | 2017-01-10 | Sabic Global Technologies B.V. | Methods for producing a thin film ferroelectric device using a two-step temperature process on an organic polymeric ferroelectric precursor material stacked between two conductive materials |
| CN104877152B (en) * | 2015-05-08 | 2017-07-07 | 陕西科技大学 | A kind of method for preparing copper-based nano zinc oxide polyvinylidene fluoride composite material |
| CN104877152A (en) * | 2015-05-08 | 2015-09-02 | 陕西科技大学 | Method for preparing copper-based nanometer zinc oxide-polyvinylidene fluoride composite material |
| CN105540535A (en) * | 2015-12-29 | 2016-05-04 | 陕西科技大学 | Method for preparing multi-scale high-gamma-phase polyvinylidene fluoride hollow nanowires |
| CN105540535B (en) * | 2015-12-29 | 2017-01-25 | 陕西科技大学 | Method for preparing multi-scale high-gamma-phase polyvinylidene fluoride hollow nanowires |
| CN106009426A (en) * | 2016-05-26 | 2016-10-12 | 陕西科技大学 | Preparation method of MgCl2-doped annular gamma-phase polyvinylidene-fluoride-base composite film |
| CN109694486A (en) * | 2018-11-20 | 2019-04-30 | 北京化工大学 | The preparation method of 100% γ phase PVDF thin film |
| CN109694486B (en) * | 2018-11-20 | 2022-10-14 | 北京化工大学 | Preparation method of 100% gamma-phase PVDF film |
| CN111205496A (en) * | 2020-02-28 | 2020-05-29 | 北京化工大学 | Preparation method of polyvinylidene fluoride gamma-type crystal |
| CN112708154A (en) * | 2021-01-08 | 2021-04-27 | 陕西科技大学 | Nucleation method for improving polyvinylidene fluoride gamma phase |
| CN112708154B (en) * | 2021-01-08 | 2022-06-07 | 陕西科技大学 | Nucleation method for improving polyvinylidene fluoride gamma phase |
| CN113248762A (en) * | 2021-06-03 | 2021-08-13 | 陕西科技大学 | Method for rapidly preparing gamma-phase polyvinylidene fluoride film |
| 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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Application publication date: 20130522 |