CN108264710A - A kind of preparation method of PVDF-TrFE/ graphenes high-performance composite materials - Google Patents
A kind of preparation method of PVDF-TrFE/ graphenes high-performance composite materials Download PDFInfo
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- CN108264710A CN108264710A CN201710350063.3A CN201710350063A CN108264710A CN 108264710 A CN108264710 A CN 108264710A CN 201710350063 A CN201710350063 A CN 201710350063A CN 108264710 A CN108264710 A CN 108264710A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/02—Elements
- C08K3/04—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention discloses a kind of preparation methods of PVDF TrFE high performance piezoelectric films, are divided into following steps：1st, PVDF TrFE powder and graphene nano particle are stirred evenly in DMF solution using ultrasonic stirrer and mechanical agitator；2nd, by obtained mixed solution in drying box primary crystal；3rd, the film after primary crystal is axially stretched on stretching-machine；4th, the film after stretching is heat-treated；5th, it polarizes to the film of heat treatment.Its advantage is：It is of low cost, piezoelectric property is high, easy to operate, technological requirement is low.
Description
Technical field
The present invention relates to a kind of preparation methods of composite material, and in particular to adds graphene to PVDF-TrFE to enhance
The preparation method of its piezoelectric property.
Background technology
Self energizing technology is that one kind of energy conversion into the electric energy and driving element work around devices use itself is advanced
Technology is widely used in the fields such as wireless sensor, building health monitoring, machine on-line monitoring, micro-nano device.Realizing energy
In the piezoelectric material for measuring transformation, PVDF and its copolymer with its pollution-free, acid-alkali-corrosive-resisting, moulding is convenient, flexible good the features such as,
Widely paid close attention to.However, in the primary crystal film of PVDF and its copolymer, non-depressed electrical α crystalline phases be it is main into
Point, thus in order to improve its piezoelectric effect, need to change intramolecular crystal structure so that piezoelectric membrane is changed into piezoelectricity
Based on property β crystalline phases.
Increasing the method for the β crystalline phases of material at present has axial tension, high temperature and pressure, highfield polarization, addition nano particle
The methods of.
Chinese patent CN205352811U devises a kind of graphene PVDF composite membranes, and PVDF is sandwiched using two layer graphenes
Film forms sandwich structure, which can improve the efficiency on protein to pvdf membrane, while also improve composite membrane
Mechanical strength.Chinese patent CN106370290A devises a kind of PVDF nanofibers/graphene/elastomer piezoelectric sensing
Device prepares the piezoelectric fabric of graphene/elastomer package PVDF, the type sensor mechanical property using electrostatic spinning technique
Stablize, the power supply for not needing to be additional is supported.
There has been no the Patent Publications about PVDF-TrFE addition nano-particle reinforcement piezoelectric properties at present.
Invention content
The core of the present invention is the preparation flow by improving composite material, and the excellent piezoelectric polymer of processability is thin
Film has many advantages, such as that generating capacity is strong, flexible, at low cost.
The method of the present invention, includes the following steps：
1st, suitable trace graphite alkene is weighed using electronic balance, adds in the DMF solution of corresponding mass；
2nd, it is stirred 15 minutes, is continuously stirred twice using ultrasonic stirrer；
3rd, suitable PVDF-TrFE powder, mass ratio DMF are added in into mixed solution:PVDF-TrFE=3.5:1；
4th, said mixture is stirred evenly using planetary stirrer, 2000 revs/min of rotating speed, 15 minutes time；
5th, it is stirred 5 minutes using ultrasonic stirrer；
6th, it is stirred 10 minutes using planetary stirrer, ultrasonic stirrer stirs 5 minutes；
7th, it reuses planetary stirrer to stir 3 minutes, 2000 revs/min of rotating speed, deaeration later 1 minute；
8th, the mixed solution by above-mentioned acquisition is coated on ceramic vessel, is placed in minienvironment testing machine dry, temperature
60 DEG C, humidity 0%, 4 hours drying times；
9th, the mixture for obtaining step 8 is 12 hours dry in vacuum drier, 40 DEG C of temperature, and it is thin to obtain primary crystal
Film；
10th, the primary crystal film that step 9 obtains under 65 DEG C or so is stretched, 10 mm/min of rate of extension, drawn
Stretch multiplying power 4.5~5.5；
11st, the stretched film for obtaining step 10, is heat-treated in vacuum drying chamber, 127 DEG C of temperature, the time 1
Hour：(1) vacuum drying chamber temperature is risen to 50 DEG C, then film is put into drying box；(2) by temperature with 2 DEG C/min's
Speed rises to 113 DEG C and keeps preheating for 30 minutes；(3) temperature is raised to 127 DEG C and is kept for 1 hour；
12nd, the film that step 11 is obtained is sticked into aluminium foil as electrode；
13rd, film is polarised using substep polarization method, polarized electric field maximum intensity is 60MV/m.
Figure of description
Fig. 1 PVDF-TrFE piezoelectric patches paste position schematic diagrames
Specific embodiment
With reference to embodiment, the invention will be further described：
Embodiment 1：
The target of the embodiment is manufacture PVDF-TrFE/ graphene composite material films, and the content of graphene is
0.05wt%, a length of 3cm of film, width 1cm, thickness is about 300 μm before stretching, and thickness is about 100 μm after stretching.
Used material has PVDF-TrFE powder, commercial graphite alkene, and solvent is DMF solution (purity>99%).Material
Parameter see the table below：
The property of table 1PVDF-TrFE
| Molecular weight | 350000 | Fusion temperature | 153℃ |
| Curie temperature | 118℃ | Constituent：VDF/TrFE | 75/25 (mol%) |
| Form | It is powdered |
The property of 2 graphene of table
| Density | >1g/cm3 | Elasticity modulus | 1TPa |
| Tensile strength | 130GPa | Conductivity | 106S/cm |
| Thermal conductivity | About 5000W/mK | Specific surface area | 2630m2/g |
Specific making step is as follows：
1st, 4mg graphenes are weighed using electronic balance, adds in 28g DMF solutions；
2nd, it is stirred 15 minutes, is continuously stirred twice using ultrasonic stirrer；
3rd, the PVDF-TrFE powder of 8g is added in into mixed solution；
4th, said mixture is stirred evenly using planetary stirrer, 2000 revs/min of rotating speed, 15 minutes time；
5th, it is stirred 5 minutes using ultrasonic stirrer；
6th, it is stirred 10 minutes using planetary stirrer, ultrasonic stirrer stirs 5 minutes；
7th, it reuses planetary stirrer to stir 3 minutes, 2000 revs/min of rotating speed, deaeration later 1 minute；
8th, the mixed solution by above-mentioned acquisition is poured on ceramic vessel, and sample path length is about 2.5mm, length and width for 15cm ×
6.5cm is placed in minienvironment testing machine dry, temperature 60 C, humidity 0%, 4 hours drying times；
9th, the mixture for obtaining step 8 is 12 hours dry in vacuum drier, 40 DEG C of temperature, and it is thin to obtain primary crystal
Film；
10th, the primary crystal film that step 9 obtains under 65 DEG C or so is stretched, 10 mm/min of rate of extension, drawn
Stretch multiplying power 4.5~5.5；It first carries out preheating for 5 minutes before stretching, keeps temperature after stretching again about 5 minutes；
11st, the stretched film for obtaining step 10, is heat-treated in vacuum drying chamber, 127 DEG C of temperature, the time 1
Hour：(1) vacuum drying chamber temperature is risen to 50 DEG C, then film is put into drying box；(2) by temperature with 2 DEG C/min's
Speed rises to 113 DEG C and keeps preheating for 30 minutes；(3) temperature is raised to 127 DEG C and is kept for 1 hour；
12nd, the heat treatment rear film that step 11 is obtained is cut into 1cm wide, the thin slice of 3cm long, length edge stretching side
To；
13rd, the film that step 12 is obtained is sticked into aluminium foil as electrode；
14th, film is polarised using substep polarization method, polarized electric field initial intensity be 20MV/m, the duration
8 minutes, suspend 4 minutes；Each step electric field strength increases 10MV/m, and maximum field intensity is 60MV/m；
15th, PVDF-TrFE films are adhered to using size as shown in Figure 1 on aluminium sheet, the thickness of aluminium sheet is 1mm；
16th, the generating capacity of piezoelectric patches is tested.
Claims (7)
1. a kind of preparation method of PVDF-TrFE/ graphene composite materials, it is characterized in that including the following steps：
(1) using ultrasonic stirrer and mechanical agitator by PVDF-TrFE powder and graphene nano particle in DMF solution
It stirs evenly；
(2) obtained mixed solution in drying box is cured, obtains primary crystal film；
(3) film after primary crystal is axially stretched on stretching-machine；
(4) film after stretching is heat-treated；
(5) it polarizes to the film after heat treatment.
2. a kind of preparation method of PVDF-TrFE/ graphene composite materials according to claim 1, it is characterized in that：Alternately
Using ultrasonic wave stirring and mechanical agitation, specially (1) stirred when preparing graphene DMF mixed liquors using ultrasonic stirrer
It mixes 15 minutes, continuously stirs twice；(2) it after PVDF-TrFE powder is put into the mixed liquor of (1), is stirred using planetary stirrer
It mixes 15 minutes, is stirred 5 minutes using ultrasonic wave later, then planetary stirrer stirring 10 minutes, then ultrasonic wave stirs 5 points
Clock, then stirred 3 minutes with planetary stirrer, deaeration 1 minute.
3. a kind of preparation method of PVDF-TrFE/ graphene composite materials according to claim 1, DMF and PVDF-
The mass ratio of TrFE is 3.5:1.
4. a kind of preparation method of PVDF-TrFE/ graphene composite materials according to claim 1, it is characterized in that：It will power
Profit requires 2 mixed solutions obtained to be coated on ceramic vessel, and it is wet to be placed on drying, temperature 60 C in minienvironment testing machine
Degree 0%, 4 hours drying times.
5. a kind of preparation method of PVDF-TrFE/ graphene composite materials according to claim 1, it is characterized in that：Right
It is required that the mixture obtained in 4 is 12 hours dry in vacuum drier, 40 DEG C of temperature obtains primary crystal film.
6. a kind of preparation method of PVDF-TrFE/ graphene composite materials according to claim 1, it is characterized in that：It obtains
Primary crystal film be axially stretched under 65 DEG C or so, 10 mm/min of rate of extension, stretching ratio 4.5~5.5.
7. a kind of preparation method of PVDF-TrFE/ graphene composite materials according to claim 1, it is characterized in that：It will obtain
The stretched film obtained, is heat-treated, 127 DEG C of temperature, 1 hour time, specially in vacuum drying chamber：(1) by vacuum
Drying box temperature rises to 50 DEG C, and then film is put into drying box；(2) temperature is risen to 113 DEG C simultaneously with the speed of 2 DEG C/min
It keeps preheating for 30 minutes；(3) temperature is raised to 127 DEG C and is kept for 1 hour.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109972136A (en) * | 2019-03-26 | 2019-07-05 | 浙江大学 | A kind of preparation method of oriented growth P (VDF-TrFE) film |
| CN112870391A (en) * | 2020-12-24 | 2021-06-01 | 深圳先进技术研究院 | Ferroelectric antibacterial material and preparation method and application thereof |
| CN115252872A (en) * | 2022-09-30 | 2022-11-01 | 北京大学口腔医学院 | Antibacterial dressing based on ferroelectric material and preparation method and application thereof |
Citations (1)
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| CN103788550B (en) * | 2014-01-08 | 2016-04-20 | 重庆大学 | The preparation method of a kind of PVDF-HFP/CB piezo-electricity composite material film and this film |
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2017
- 2017-05-18 CN CN201710350063.3A patent/CN108264710A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103788550B (en) * | 2014-01-08 | 2016-04-20 | 重庆大学 | The preparation method of a kind of PVDF-HFP/CB piezo-electricity composite material film and this film |
Non-Patent Citations (3)
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| Z Y JIANG 等: "Formation of piezoelectric β-phase crystallites in poly(vinylidene fluoride)-graphene oxide nanocomposites under uniaxial tensions", 《J. PHYS. D: APPL. PHYS.》 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109972136A (en) * | 2019-03-26 | 2019-07-05 | 浙江大学 | A kind of preparation method of oriented growth P (VDF-TrFE) film |
| CN109972136B (en) * | 2019-03-26 | 2020-09-04 | 浙江大学 | Preparation method of oriented growth P (VDF-TrFE) film |
| CN112870391A (en) * | 2020-12-24 | 2021-06-01 | 深圳先进技术研究院 | Ferroelectric antibacterial material and preparation method and application thereof |
| CN115252872A (en) * | 2022-09-30 | 2022-11-01 | 北京大学口腔医学院 | Antibacterial dressing based on ferroelectric material and preparation method and application thereof |
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Application publication date: 20180710 |