CN102199304B - Modification method for polyvinylidene fluoride (PVDF) film - Google Patents
Modification method for polyvinylidene fluoride (PVDF) film Download PDFInfo
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Abstract
The invention discloses a modification method for a PVDF film, which enables the technical problem that the UV irradiation modified PVDF film prepared by the prior art has poor crystallinity to be solved. The technical scheme in the invention is as follows: a UVb lamp with a wavelength of 173 nm is employed, voltage is adjusted to 3 to 9 KV, UV light source irradiance is controlled to be in a range from 20 to 80 mv/cm<2>, irradiation lasts for 5 to 15 min, and therefore a PVDF film modified by ultraviolet light can be obtained. According to the invention, since the UVb lamp with a wavelength of 173 nm is employed, the irradiation intensity is 40 mv/cm<2>, and the irradiation lasts for 10 or 15 min, the PVDF film with a larger grain size and better crystallinity is obtained.
Description
Technical field
The present invention relates to a kind of method of modifying of film, particularly a kind of method of modifying of PVDF film.
Background technology
Document " Katan; M.Narjis; A.Siegmann.The Effect of Some Fluoropolymers ' Structures on Their Response to UV Irradiation.Journal of Applied Polymer Science.1998,70 (8): 1471～1481 " discloses a kind of ultraviolet radiation to PVDF film method of modifying, its primary process: under 50 ℃ of conditions; With the UVb light irradiation 2400h of 313-550nm, every at a distance from sample index of 200h survey.But this method of modifying exists obvious deficiency, and the uv lamp yield of radiation is too low, has only 1～5mw/cm
2, and wavelength is the shortest has only 313mm.So PVDF film (hereinafter to be referred as the PVDF film) percent crystallinity is undesirable, when irradiation time reached 200h～2400h, percent crystallinity had only 28.12%～40.10%, is difficult to be applied in the engineering field.
Summary of the invention
In order to overcome the deficiency of the resulting PVDF thin film crystallization of existing ultraviolet radiation modified polyvinilidene difluoroethylene film process degree difference; The present invention provides a kind of method of modifying of PVDF film; This method adopts the UVb lamp of 173nm; Regulating voltage to 3～9KV is controlled at 20～80mw/cm with the ultraviolet source irradiance
2Scope, irradiation 5～15min can improve the percent crystallinity of PVDF film.
The technical solution adopted for the present invention to solve the technical problems: a kind of method of modifying of PVDF film is characterized in comprising the steps:
(a) the polyvinylidene fluoride resin powder is dissolved in N by the proportioning of mass ratio 10～30%, in the dinethylformamide,, processes PVDF solution at 30～60 ℃ of following supersound process 10～60min.
(b) after the preparation of PVDF solution is accomplished, in the vacuum of 0.2～0.5Pa, degas.
(c) with the PVDF drips of solution of being prepared on clean silicon substrate, be statically placed on the horizontal stand, make the edge of PVDF solution casting film-forming to silicon chip under the tensile effect, process the PVDF film.
(d) with the PVDF film through 200～300 ℃ of fusion 10～30min after, put into quenching in 0 ℃ of mixture of ice and water rapidly, afterwards through 120～300 ℃ of annealing.
The PVDF pellicular front that (e) will pass through step (d) processing is to source of radiation exiting surface horizontal positioned, and regulating voltage to 3～9KV is controlled at 20～80mv/cm with the ultraviolet source irradiance
2Scope, irradiation 5～15min.
The invention has the beneficial effects as follows: owing to adopt the UVb lamp of 173nm, at 40mv/cm
2Irradiation 10min or 15min under the irradiation intensity have obtained the PVDF film of percent crystallinity 53.05% or 54.8%.At yield of radiation 20～80mv/cm
2The time, irradiation time drops to 5～15min by 200～2400h of background technology; Percent crystallinity brings up to 45.90～54.80% by 28.12～40.10% of background technology.
Below in conjunction with accompanying drawing and embodiment the present invention is elaborated.
Description of drawings
Fig. 1 is the PVDF film grain size of processing under the different irradiation intensities and the change curve of texture coefficient.
Fig. 2 is melt quenching β under the different irradiation intensities-phase PVDF film X ray diffracting spectrum.
Embodiment
Embodiment 1, and 0.5g is dissolved in polar solvent N with the polyvinylidene fluoride resin powder, among the dinethylformamide 5ml, handles at 30 ℃ of down ultrasonic 60min.After the solution preparation is accomplished, in the vacuum of 0.5Pa, degas, to improve the density of PVDF film.The PVDF drips of solution of being prepared on clean silicon chip, is statically placed on the horizontal stand, makes the edge of solution casting film-forming to silicon chip under the tensile effect.With the PVDF film through 200 ℃ of fusion 30min after, put into quenching in 0 ℃ of mixture of ice and water rapidly, obtaining the PVDF film through 120 ℃ of annealing afterwards.To source of radiation exiting surface horizontal positioned, regulating voltage is controlled ultraviolet source irradiance 20mv/cm to 3KV with the PVDF pellicular front
2Irradiation time 15min obtains the film of the PVDF of ultraviolet radiation modification at last.
Embodiment 2, and 0.5g is dissolved in polar solvent N with the polyvinylidene fluoride resin powder, among the dinethylformamide 5ml, handle at 35 ℃ of down ultrasonic 50min.After the solution preparation is accomplished, in the vacuum of 0.3Pa, degas, to improve the density of PVDF film.The PVDF drips of solution of being prepared on clean silicon chip, is statically placed on the horizontal stand, makes the edge of solution casting film-forming to silicon chip under the tensile effect.With the PVDF film through 230 ℃ of fusion 25min after, put into quenching in 0 ℃ of mixture of ice and water rapidly, obtaining the PVDF film through 150 ℃ of annealing afterwards.To source of radiation exiting surface horizontal positioned, regulating voltage is controlled ultraviolet source irradiance 30mv/cm to 5KV with the PVDF pellicular front
2Irradiation time 13min obtains the film of the PVDF of ultraviolet radiation modification at last.
Embodiment 3, and 1.0g is dissolved in polar solvent N with the polyvinylidene fluoride resin powder, among the dinethylformamide 5ml, handle at 40 ℃ of down ultrasonic 30min.After the solution preparation is accomplished, in the vacuum of 0.3Pa, degas, to improve the density of PVDF film.The PVDF drips of solution of being prepared on clean silicon chip, is statically placed on the horizontal stand, makes the edge of solution casting film-forming to silicon chip under the tensile effect.With the PVDF film through 250 ℃ of fusion 20min after, put into quenching in 0 ℃ of mixture of ice and water rapidly, obtaining the PVDF film through 200 ℃ of annealing afterwards.To source of radiation exiting surface horizontal positioned, regulating voltage is to 6KV with the PVDF pellicular front, and control ultraviolet source irradiance is at 40mv/cm
2, radiated time is 10min, obtains the film of the PVDF of ultraviolet radiation modification at last.
Embodiment 4, and 1.0g is dissolved in polar solvent N with the polyvinylidene fluoride resin powder, among the dinethylformamide 5ml, handle at 45 ℃ of down ultrasonic 40min.After the solution preparation is accomplished, in the vacuum of 0.2Pa, degas, to improve the density of PVDF film.The PVDF drips of solution of being prepared on clean silicon chip, is statically placed on the horizontal stand, makes the edge of solution casting film-forming to silicon chip under the tensile effect.With the PVDF film through 270 ℃ of fusion 18min after, put into quenching in 0 ℃ of mixture of ice and water rapidly, obtaining the PVDF film through 250 ℃ of annealing afterwards.To source of radiation exiting surface horizontal positioned, regulating voltage is to 7KV with the PVDF pellicular front, and control ultraviolet source irradiance is at 50mv/cm
2, radiated time is 10min, obtains the film of the PVDF of ultraviolet radiation modification at last.
Embodiment 5, and 1.8g is dissolved in polar solvent N with the polyvinylidene fluoride resin powder, among the dinethylformamide 6ml, handle at 60 ℃ of down ultrasonic 20min.After the solution preparation is accomplished, in the vacuum of 0.2Pa, degas, to improve the density of PVDF film.The PVDF drips of solution of being prepared on clean silicon chip, is statically placed on the horizontal stand, makes the edge of solution casting film-forming to silicon chip under the tensile effect.With the PVDF film through 300 ℃ of fusion 15min after, put into quenching in 0 ℃ of mixture of ice and water rapidly, obtaining the PVDF film through 300 ℃ of annealing afterwards.To source of radiation exiting surface horizontal positioned, regulating voltage is to 9KV with the PVDF pellicular front, and control ultraviolet source irradiance is at 80mv/cm
2, irradiation time 8min.Obtain the film of the PVDF of ultraviolet radiation modification at last.
Embodiment 6, and 1.8g is dissolved in polar solvent N with the polyvinylidene fluoride resin powder, among the dinethylformamide 6ml, handle at 50 ℃ of down ultrasonic 10min.After the solution preparation is accomplished, in the vacuum of 0.4Pa, degas, to improve the density of PVDF film.The PVDF drips of solution of being prepared on clean silicon chip, is statically placed on the horizontal stand, makes the edge of solution casting film-forming to silicon chip under the tensile effect.With the PVDF film through 300 ℃ of fusion 10min after, put into quenching in 0 ℃ of mixture of ice and water rapidly, obtaining the PVDF film through 280 ℃ of annealing afterwards.To source of radiation exiting surface horizontal positioned, regulating voltage is to 8KV with the PVDF pellicular front, and control ultraviolet source irradiance is at 60mv/cm
2, irradiation time 5min.Obtain the film of the PVDF of ultraviolet radiation modification at last.
As can beappreciated from fig. 1, along with the increase of ultraviolet radiation illumination, the mean sizes of β-phase crystal grain takes place obviously to change.(＜40mW/cm when radiant illumination is low
2), compared to the PVDF film of irradiation not, PVDF film grain-size increases along with the increase of radiant illumination behind the irradiation, and is increased to 60mW/cm when irradiation illumination
2The time, its grain-size begins again to reduce.Equally, the texture coefficient of β-phase (110) crystal face also changes along with the increase of radiant illumination, and demonstrates with grain-size and change identical variation tendency.This is illustrated in the uv-radiation process, under the low relatively radiant illumination condition, can cause the irradiation-induced degradation reaction of polymkeric substance, makes some macromolecular chains rupture, and the sub-chain motion increased activity also possibly arranged the entering crystalline region again.And the direction of its rearrangement can just make that so also the polymkeric substance preferred orientation is more obvious along the differently-oriented directivity of crystalline region.Be increased to 60mW/cm and work as radiant illumination
2The time, then can cause the radiation injury of crystalline region, radiation injury has made average grain size reduce, and causes the decline of thin film alignment degree thereby lead PVDF.
As can be seen from Figure 2,, the diffraction peak of two obvious α-phases of representative in its diffracting spectrum, also occurred, be respectively 2 θ=17.8 (100) and 2 θ=18.4 (020) except going out to represent outside the diffraction main peak of β-phase in 2 θ=20.5 ° (110,200).Obviously, the PVDF film that behind the high-temperature fusion quenching, obtains not is simple β-phase crystallization, but contains the mixed crystal of α-phase.(irradiation illumination 40mW/cm when receiving ultraviolet light irradiation
2, time 10min), diffraction peak does not take place obviously to change, and does not have new structure to occur yet, and still, can find to represent the diffraction intensity of the diffraction main peak of β-phase to descend rapidly, in addition, α-phase diffraction peak strong also with the notable difference that has without uv irradiation.And along with ultraviolet radiation illumination is increased to 80mW/cm
2, in the strong decline of β-phase diffraction main peak, α-phase diffraction peak also has decline to a certain degree.This means that ultraviolet light irradiation has tangible destruction to the β-phase crystal of melt quenching preparation.
Following table is the changing value of PVDF thin film crystallization degree under different radiated times and the intensity.
From table, can find out that when radiated time was 5min, the percent crystallinity of PVDF piezoelectric membrane increased along with the increase of radiant illumination; When radiated time was 10min and 15min, the percent crystallinity of film always increased along with the increase of radiant illumination earlier, when radiant illumination reaches 60mW/cm
2The time, percent crystallinity begins again to descend.At radiant illumination 80mW/cm
2, during radiated time 15min, percent crystallinity is merely 45.90%, a little more than the percent crystallinity without the PVDF film of irradiation.It is thus clear that radiated time and radiant illumination all can exert an influence to PVDF polymer crystallization degree, and along with the increase of irradiation time and irradiation illumination, the uv irradiation effect is more obvious.
The contriver is in the disclosed process parameters range of technical scheme, and different parameter collocation are all tested, and have all obtained good effect.
Claims (3)
1. the method for modifying of a PVDF film is characterized in that comprising the steps:
(a) the polyvinylidene fluoride resin powder is dissolved in N by the proportioning of mass ratio 10～30%, in the dinethylformamide,, processes PVDF solution at 30～60 ℃ of following supersound process 10～60min;
(b) after the preparation of PVDF solution is accomplished, in the vacuum of 0.2～0.5Pa, degas;
(c) with the PVDF drips of solution of being prepared on clean silicon substrate, be statically placed on the horizontal stand, make the edge of PVDF solution casting film-forming to silicon chip under the tensile effect, process the PVDF film;
(d) with the PVDF film through 200～300 ℃ of fusion 10～30min after, put into quenching in 0 ℃ of mixture of ice and water rapidly, afterwards through 120～300 ℃ of annealing;
The PVDF pellicular front that (e) will pass through step (d) processing is to source of radiation exiting surface horizontal positioned, and regulating voltage to 3～9KV is controlled at 20～80mv/cm with the ultraviolet source irradiance
2Scope, irradiation 5～15min.
2. the method for modifying of PVDF film according to claim 1 is characterized in that: it is ultraviolet source irradiance 40mv/cm that said ultraviolet source irradiance cooperates with irradiation time
2, irradiation time 10min.
3. the method for modifying of PVDF film according to claim 1 is characterized in that: it is ultraviolet source irradiance 40mv/cm that said ultraviolet source irradiance cooperates with irradiation time
2, irradiation time 15min.
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| CN102504450B (en) * | 2011-11-04 | 2013-12-18 | 四川大学 | High-dielectric-constant polymer-potassium salt composite film material and preparation method thereof |
| CN102585411A (en) * | 2012-03-13 | 2012-07-18 | 苏州新区特氟龙塑料制品厂 | Formula of modified polyvinylidene fluoride with high chemical properties |
| CN106188604A (en) * | 2016-08-05 | 2016-12-07 | 宁波高新区斯汀环保科技有限公司 | A kind of preparation method of solar battery back film |
| CN112976531B (en) * | 2019-12-16 | 2022-11-18 | 浙江蓝天环保高科技股份有限公司 | Preparation method of modified polyvinyl fluoride resin |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4241128A (en) * | 1979-03-20 | 1980-12-23 | Bell Telephone Laboratories, Incorporated | Production of piezoelectric PVDF films |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4241128A (en) * | 1979-03-20 | 1980-12-23 | Bell Telephone Laboratories, Incorporated | Production of piezoelectric PVDF films |
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Effective date of registration: 20140815 Address after: 226600 fine chemical industry park, Haian Development Zone, Haian County, Nantong, Jiangsu Patentee after: Jiangsu Tiancheng Biochemical Products Co., Ltd. Patentee after: Northwestern Polytechnical University Address before: 710072 Xi'an friendship West Road, Shaanxi, No. 127 Patentee before: Northwestern Polytechnical University |