CN105037761A - Preparation method for polyvinylidene fluoride nanometer film with beta crystal phase - Google Patents
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Abstract
The invention provides a preparation method for a polyvinylidene fluoride (PVDF) nanometer film with a beta crystal phase, which belongs to the fields of pyroelectric thin film materials and terahertz detection. The preparation method comprises the following steps: dissolving graphene oxide and polyvinylidene fluoride in an organic solvent and carrying out ultrasonic treatment and magnetic stirring so as to obtain a uniformly dispersed film-making solution; standing the film-making solution for defoaming; preparing a wet film by using a spin coating method; and subjecting the film to heat treatment in an atmospheric environment to realize drying and crystallization of the film so as to obtain the polyvinylidene fluoride nanometer film with the beta crystal phase. According to the invention, the content of the beta crystal phase in PVDF is increased by doping of GO and the PVDF nanometer film is prepared by using the spin coating method; the preparation method is simple, is easy to control, has low requirements on equipment and low cost and can realize preparation under common atmospheric conditions; and the prepared PVDF film is uniform and smooth, has good compactness and stable pyroelectric performance and provides powerful support for development of a thin-film pyroelectric terahertz detector.
Description
Technical field
The invention belongs to pyroelectric film material field and terahertz detection field, relate to function nano method for manufacturing thin film, be specially a kind of preparation method with polyvinylidene difluoride (PVDF) (PVDF) nano thin-film of β crystalline phase.
Background technology
Polyvinylidene difluoride (PVDF) (PVDF) has good piezoelectricity, pyroelectric and ferroelectricity.Make it as film functional materials at sensor, transverter, be widely used in the fields such as biomedicine.
PVDF has multiple crystalline structure, and 5 kinds of known at present structures are α respectively, beta, gamma, δ and ε type.Wherein α crystalline phase is TGTG
-1structure, dipole positive and negative charge center superposition spontaneous polarization strength is zero, does not have piezoelectric property.β crystalline phase is alltrans type, has higher spontaneous polarization strength, is the important crystal phase structure in PVDF.But α crystalline phase is the most stable structure of minimum energy in PVDF5 kind crystalline phase, generally, PVDF from solution or under molten state crystallization all can only obtain α crystalline phase, therefore preparation has the Important Problems that the PVDF thin film of high β crystalline phase is research at present.
At present, the PVDF thin film with β crystalline phase can be obtained by mechanical stretching, document: A.SalimietcFTIRstudiesof β-phasecrystalformationinstretchedPVDFfilms, 2003, disclose in 22:699 – 704A.Salimi and prepared pvdf membrane by mechanical stretching, the pvdf membrane β crystal content prepared is not high, and the film of preparation is thicker, and can not exactly by film preparation on required substrate.Electrostatic spinning process is also one of common methods of preparation PVDF thin film, document: YongjinAhnetcEnhancedPiezoelectricPropertiesofElectrospu nPoly (vinylidenefluoride)/MultiwalledCarbonNanotubeCompositesDuetoHigh β-PhaseFormationinPoly (vinylidenefluoride), the method of electrostatic spinning is openly adopted to prepare PVDF thin film in 2013,117:11791-11799; But its equipment requirements is high, and preparation process is loaded down with trivial details, be not suitable for large-scale production.Doped nanoparticle (such as titanium dioxide, Graphene, carbon nanotube etc.) caused the extensive concern of people in recent years; Document: WCGanetcEffectofTiO
2onenhancedpyroelectricactivityofPVDFcomposite, 2014, disclose by titania-doped preparation PVDF thin film in 23WCGan, but β crystal content is little in its PVDF thin film prepared, mainly generate δ crystalline phase, and the polarizability of δ crystalline phase only has the half of β crystalline phase; And document: YuJetcGraphenenanocompositesbasedonpoly (vinylidenefluoride) structureandproperties, 2011, in 32:1483 – 1491, open employing adds a small amount of Graphene and prepares PVDF thin film in PVDF, but in this preparation method, because Graphene dispersiveness is in a solvent very poor, could well must be dispersed in PVDF by adding dispersion agent or carrying out surface modification to it; Further, document: M.ElAchabyetcPiezoelectric β-polymorphformationandpropertiesenhancementingrapheneoxid e – PVDFnanocompositefilms, 2012, doped with oxygen functionalized graphene and casting method is openly utilized to prepare PVDF thin film in 258:7668-7677, the method can overcome other nano materials can not be dispersed in difficulty in PVDF very well, but adopts its thickness of film prepared by casting method generally in micron dimension.
Summary of the invention
The object of the invention is to provide a kind of preparation method with the polyvinylidene fluoride nanometer film of β crystalline phase for the problems referred to above; This preparation method's technique is simple, adopt graphene oxide (GO) as hotchpotch, be there is by spin coating proceeding preparation the PVDF nano thin-film of high β crystal content, and GO can improve the crystallization rate of PVDF as nucleator, reduce the spherulite size of PVDF.
Technical scheme of the present invention is: a kind of preparation method with the polyvinylidene fluoride nanometer film of β crystalline phase, comprises the following steps:
Graphene oxide and polyvinylidene difluoride (PVDF) are dissolved in organic solvent by step 1., and ultrasonic and magnetic agitation obtains finely dispersed film making solution, and wherein the mass percent of graphene oxide, polyvinylidene difluoride (PVDF) and organic solvent consists of:
Graphene oxide: 0.1-1wt%,
Polyvinylidene difluoride (PVDF): 5-10wt%,
Organic solvent: 89-94wt%;
Step 2. is by film making solution standing and defoaming;
Step 3. adopts spin-coating method to prepare wet film;
Step 4. thermal treatment under atmospheric environment makes film drying and crystallization, is namely prepared into the polyvinylidene fluoride nanometer film with β crystalline phase.
Preferably, selected organic solvent is DMF.
When described step 1 prepares film making solution, ultrasonic is 27-60 DEG C with temperature in the process of magnetic agitation, and ultrasonic time is 1 ~ 3 hour, and churning time is 1 ~ 4 hour.
The condition of described step 2 deaeration is: leave standstill placement 1 ~ 2 hour under room temperature condition.
Described step 3 adopts spin-coating method to prepare in wet film process, and low speed is 500 revs/min, the time is 10 seconds, at a high speed for 1500-5000 rev/min, the time is 20 ~ 60 seconds.
Described step 4 heat-treat condition is: temperature is 50 ~ 75 DEG C, and the time is 12 ~ 24 hours.
In the present invention, the thickness of the polyvinylidene fluoride nanometer film (PVDF/GO film) with β crystalline phase prepared is 100 ~ 500nm.The crystal grain diameter of the PVDF/GO film prepared is 3 ~ 5 μm.
The present invention proposes a kind of preparation method with the polyvinylidene fluoride nanometer film of β crystalline phase, is improved the content of β crystalline phase in PVDF on the one hand by doping GO, adopts spin coating proceeding to prepare PVDF nano thin-film on the other hand; GO can reduce the spherulite size of PVDF thin film effectively as nucleator, and GO is easily dispersed in PVDF, does not need add dispersion agent or carry out surface modification to GO; Simultaneously, method preparation technology provided by the invention is simply easy to control, equipment requirements is low, with low cost, can prepare under common atmospheric conditions, the PVDF thin film of preparation is even, smooth, compactness is good, pyroelectric property is stablized, and the development for thin-film material pyroelectricity terahertz detector provides and provides powerful support for.
Accompanying drawing explanation
Fig. 1 is the polyvinylidene fluoride nanometer thin film preparation process schema that the present invention has β crystalline phase.
Fig. 2 is the FTIR figure that GO doping content is respectively the PVDF thin film of 0wt% and 1wt%.
Fig. 3 is the SEM exterior view of pure PVDF thin film.
The SEM exterior view of Fig. 4 to be GO doping content be PVDF thin film of 1wt%.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further details:
In the present embodiment, preparing the PVDF thin film that GO doping content is respectively 0wt% and 1wt% respectively, i.e. pure PVDF thin film and the invention provides the polyvinylidene fluoride nanometer film with β crystalline phase, further illustrating invention effect of the present invention by comparing; Concrete preparation process comprises the following steps:
Step 1. adopts DMF (N, N-Dimethylformamide are called for short DMF) to be organic solvent amount, gets 10mLDMF and loads in beaker 1, take 1gPVDF and add in beaker 1; Then measure 10mlDMF to load in beaker 2, take 1gPVDF and 100mgGO and add in beaker 2;
Beaker 1 and beaker 2 are put into ultrasonic cleaner, and ultrasonic frequency is 80W, and ultrasonic time is 2h, and ultrasonic temperature is no more than 60 DEG C; Finally respectively beaker 1 and beaker 2 are put into magnetic stirring apparatus, whipping temp is room temperature, and churning time is 1 hour;
Step 2. at ambient temperature, by solution left standstill deaeration in 1 hour;
Step 3. adopts spin-coating method to prepare wet film, and on a si substrate, first low speed applies, then high speed film forming in solution sol evenning machine coating step 2 obtained; When preparing pure PVDF thin film, low speed is 500 revs/min, and the time is 10 seconds, and be 1500 revs/min at a high speed, the time is 30 seconds; During preparation PVDF/GO film, low speed is 500 revs/min, and the time is 10 seconds, and be 1500 revs/min at a high speed, the time is 60 seconds;
Step 4. thermal treatment under atmospheric environment makes film drying and crystallization, and heat-treat condition is: temperature is 75 DEG C, 24 hours time.
Adopt the film of fourier transform infrared spectroscopy analyser (FTIR) test preparation, as shown in Figure 2: from FTIR spectrum figure, pure polyvinylidene difluoride film only has the transmission peaks of α crystalline phase, and the crystal phase structure of PVDF/GO film is based on β crystalline phase.
Adopt the thickness of step instrument test PVDF thin film, the thickness recording PVDF thin film is 309nm.
Adopt scanning electronic microscope (SEM) test to obtain the surface topography map of film, as shown in Figure 3 and Figure 4: schemed from SEM, the spherulite size of pure PVDF thin film is the spherulite size of 10-15 μm, PVDF/GO film is 3-5 μm; Illustrate that GO accelerates nucleation rate as nucleator in PVDF crystallisation process, reduce the spherulite size of PVDF.
The above, be only the specific embodiment of the present invention, arbitrary feature disclosed in this specification, unless specifically stated otherwise, all can be replaced by other equivalences or the alternative features with similar object; Step in disclosed all features or all methods or process, except mutually exclusive feature and/or step, all can be combined in any way.
Claims (7)
1. there is a preparation method for the polyvinylidene fluoride nanometer film of β crystalline phase, comprise the following steps:
Graphene oxide and polyvinylidene difluoride (PVDF) are dissolved in organic solvent by step 1., and ultrasonic and magnetic agitation obtains finely dispersed film making solution, and wherein the mass percent of graphene oxide, polyvinylidene difluoride (PVDF) and organic solvent consists of:
Graphene oxide: 0.1-1wt%,
Polyvinylidene difluoride (PVDF): 5-10wt%,
Organic solvent: 89-94wt%;
Step 2. is by film making solution standing and defoaming;
Step 3. adopts spin-coating method to prepare wet film;
Step 4. thermal treatment under atmospheric environment makes film drying and crystallization, is namely prepared into the polyvinylidene fluoride nanometer film with β crystalline phase.
2. by the preparation method of polyvinylidene fluoride nanometer film described in claim 1 with β crystalline phase, it is characterized in that, when described step 1 prepares film making solution, ultrasonic is 27-60 DEG C with temperature in the process of magnetic agitation, ultrasonic time is 1 ~ 3 hour, and churning time is 1 ~ 4 hour.
3. by the preparation method of polyvinylidene fluoride nanometer film described in claim 1 with β crystalline phase, it is characterized in that, the condition of described step 2 deaeration is: leave standstill placement 1 ~ 2 hour under room temperature condition.
4. by the preparation method of polyvinylidene fluoride nanometer film described in claim 1 with β crystalline phase, it is characterized in that, described step 3 adopts spin-coating method to prepare in wet film process, and low speed is 500 revs/min, the time is 10 seconds, at a high speed for 1500-5000 rev/min, the time is 20 ~ 60 seconds.
5., by the preparation method of polyvinylidene fluoride nanometer film described in claim 1 with β crystalline phase, it is characterized in that, described step 4 heat-treat condition is: temperature is 50 ~ 75 DEG C, and the time is 12 ~ 24 hours.
6., by the preparation method of polyvinylidene fluoride nanometer film described in claim 1 with β crystalline phase, it is characterized in that, selected organic solvent is DMF.
7. there is described in arbitrary by claim 1 to 6 preparation method of the polyvinylidene fluoride nanometer film of β crystalline phase, it is characterized in that, the thickness that described preparation method is prepared into the polyvinylidene fluoride nanometer film with β crystalline phase is 100 ~ 500nm, and the crystal grain diameter of film is 3 ~ 5 μm.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105295265A (en) * | 2015-12-07 | 2016-02-03 | 郑州轻工业学院 | Modified polyvinylidene fluoride super-hydrophobic material and preparation method thereof |
| CN106483104A (en) * | 2016-12-08 | 2017-03-08 | 中国计量大学 | Alcohol concentration measurement apparatus and method using PVDF Terahertz plasma resonance effect |
| CN106589431A (en) * | 2016-12-26 | 2017-04-26 | 清华大学深圳研究生院 | Pyroelectric flexible composite film and preparation method thereof |
| CN106596475A (en) * | 2016-12-08 | 2017-04-26 | 中国计量大学 | Apparatus and method for measuring alcohol content by using graphene and PVDF (polyvinylidene fluoride) terahertz plasmon resonance effect |
| CN107955196A (en) * | 2017-11-28 | 2018-04-24 | 电子科技大学 | A kind of PVDF-HFP/GO preparation method of composite film for being used to improve β crystal contents |
| CN108963069A (en) * | 2018-06-28 | 2018-12-07 | 江苏大学 | A kind of preparation method of 3D printing poly meta fluoroethylene piezoelectric film |
| CN109686836A (en) * | 2018-11-27 | 2019-04-26 | 江苏大学 | A kind of preparation method of the 3D printing poly meta fluoroethylene piezoelectric film under uniform electric field |
| CN112480451A (en) * | 2020-10-26 | 2021-03-12 | 清华大学 | Polymer-based terahertz spatial light modulator and preparation method thereof |
| CN115322499A (en) * | 2022-08-19 | 2022-11-11 | 三三智能科技(日照)有限公司 | Piezoelectric film production process capable of reducing breakage rate |
| CN115869778A (en) * | 2023-03-02 | 2023-03-31 | 广东省科学院生态环境与土壤研究所 | PVDF nano-particle array porous membrane and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045795A (en) * | 2007-04-12 | 2007-10-03 | 中国科学院长春应用化学研究所 | Beta phase polyvinylidene fluoride composite film and preparation method thereof |
| CN102181067A (en) * | 2011-03-10 | 2011-09-14 | 西北工业大学 | Preparation method of gamma-phase polyvinylidene fluoride film |
| CN102416720A (en) * | 2011-08-17 | 2012-04-18 | 电子科技大学 | Vanadium oxide composite film and preparation method thereof |
-
2015
- 2015-07-06 CN CN201510392607.3A patent/CN105037761A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045795A (en) * | 2007-04-12 | 2007-10-03 | 中国科学院长春应用化学研究所 | Beta phase polyvinylidene fluoride composite film and preparation method thereof |
| CN102181067A (en) * | 2011-03-10 | 2011-09-14 | 西北工业大学 | Preparation method of gamma-phase polyvinylidene fluoride film |
| CN102416720A (en) * | 2011-08-17 | 2012-04-18 | 电子科技大学 | Vanadium oxide composite film and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| M. EL ACHABY ET.AL.: "Piezoelectric β-polymorph formation and properties enhancement in grapheneoxide-PVDF nanocomposite films", 《APPLIED SURFACE SCIENCE》 * |
| 于胜军: "《显示器件技术》", 31 August 2014 * |
| 温耀贤等: "《功能性塑料薄膜》", 30 September 2005 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105295265B (en) * | 2015-12-07 | 2018-01-12 | 郑州轻工业学院 | A kind of modified polyvinilidene fluoride super hydrophobic material and preparation method thereof |
| CN105295265A (en) * | 2015-12-07 | 2016-02-03 | 郑州轻工业学院 | Modified polyvinylidene fluoride super-hydrophobic material and preparation method thereof |
| CN106596475B (en) * | 2016-12-08 | 2024-05-17 | 中国计量大学 | Alcohol concentration measuring device and method using graphene and PVDF terahertz plasma resonance effect |
| CN106483104A (en) * | 2016-12-08 | 2017-03-08 | 中国计量大学 | Alcohol concentration measurement apparatus and method using PVDF Terahertz plasma resonance effect |
| CN106596475A (en) * | 2016-12-08 | 2017-04-26 | 中国计量大学 | Apparatus and method for measuring alcohol content by using graphene and PVDF (polyvinylidene fluoride) terahertz plasmon resonance effect |
| CN106589431A (en) * | 2016-12-26 | 2017-04-26 | 清华大学深圳研究生院 | Pyroelectric flexible composite film and preparation method thereof |
| CN107955196A (en) * | 2017-11-28 | 2018-04-24 | 电子科技大学 | A kind of PVDF-HFP/GO preparation method of composite film for being used to improve β crystal contents |
| CN108963069A (en) * | 2018-06-28 | 2018-12-07 | 江苏大学 | A kind of preparation method of 3D printing poly meta fluoroethylene piezoelectric film |
| CN108963069B (en) * | 2018-06-28 | 2022-01-11 | 上海凸申科技有限公司 | Preparation method of 3D printed polyvinylidene fluoride piezoelectric film |
| CN109686836B (en) * | 2018-11-27 | 2022-12-16 | 江苏大学 | Preparation method for 3D printing of polyvinylidene fluoride piezoelectric film under uniform electric field |
| CN109686836A (en) * | 2018-11-27 | 2019-04-26 | 江苏大学 | A kind of preparation method of the 3D printing poly meta fluoroethylene piezoelectric film under uniform electric field |
| CN112480451A (en) * | 2020-10-26 | 2021-03-12 | 清华大学 | Polymer-based terahertz spatial light modulator and preparation method thereof |
| CN112480451B (en) * | 2020-10-26 | 2022-03-18 | 清华大学 | Polymer-based terahertz spatial light modulator and preparation method thereof |
| CN115322499A (en) * | 2022-08-19 | 2022-11-11 | 三三智能科技(日照)有限公司 | Piezoelectric film production process capable of reducing breakage rate |
| CN115869778A (en) * | 2023-03-02 | 2023-03-31 | 广东省科学院生态环境与土壤研究所 | PVDF nano-particle array porous membrane and preparation method and application thereof |
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