CN105802123B - The method that graphene, CNT and phenolic resin prepare negative permittivity material - Google Patents
The method that graphene, CNT and phenolic resin prepare negative permittivity material Download PDFInfo
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- CN105802123B CN105802123B CN201610335082.4A CN201610335082A CN105802123B CN 105802123 B CN105802123 B CN 105802123B CN 201610335082 A CN201610335082 A CN 201610335082A CN 105802123 B CN105802123 B CN 105802123B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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Abstract
The invention discloses a kind of method that graphene, CNT and phenolic resin prepare negative permittivity material, by graphene powder, carbon nanotube powder and Phenolic resin powder, carries out ball milling mixing, then adds PVA solution, and grinding is uniform；Among powder is poured into mould, flakiness is suppressed.In composite prepared by the present invention there is a certain amount of functional group in the surface of graphene, these functional groups are not to interconnect, also it is non-conductive, between repulsion be present, and it is attached between the lamella of graphene, and it is distributed in graphenic surface and turns into boundary layer, can be used for limiting leakage electrical conduction current, so as to reduce dielectric loss.
Description
Technical field
The invention belongs to negative permittivity material prepare technical field, more particularly to a kind of graphene, CNT and
The method that phenolic resin prepares negative permittivity material.
Background technology
Negative dielectric material is that the dielectric constant values measured under the wave band of some frequencies the material of negative value occur, due to material
The change of structure and cause conductance to be changed into variable journey transition by tunnel conduction, this is to cause dielectric constant the original of negative value occur
Cause.Negative dielectric material has a wide range of applications in many fields, such as resonator, wave filter and oscillator etc..
Therefore artificial synthesized negative dielectric material is critically important.Negative dielectric material is typically by insulating body and highly conductive material
Material, which is combined into exceed, to be oozed material to design.In existing technology, mainly there are metal-base composites and polymer composites
Deng.But near percolation threshold, because the conductance of metal material is very high, and then cause high dielectric loss.People have thought
Some methods are gone out, have such as introduced the nanostructured of insulating barrier or mixing, made the reduction of leakage electrical conduction current, so that near percolation threshold
Dielectric loss is changed into low-dielectric loss.In the present invention, graphene is added, because containing on the surface of graphene a certain amount of
Functional group, these functional groups are simultaneously non-conductive, and are attached between the lamella of graphene, when graphene forms multi-disc Rotating fields,
Functional group between layers can influence the transfer of electronics, reduce leakage electrical conduction current, cause low dielectric to be damaged equivalent to insulating barrier
Consumption.
The content of the invention
The purpose of the present invention is exactly to solve the above problems, there is provided a kind of graphene, CNT and phenolic resin-made
The method of standby negative permittivity material.
To achieve these goals, the present invention adopts the following technical scheme that：
A kind of method that graphene, CNT and phenolic resin prepare negative permittivity material, step are as follows：
(1) by graphene (GR) powder, CNT (CNTS) powder and Phenolic resin powder, ball milling mixing is carried out, so
After add PVA solution, grinding is uniform；
(2) among powder being poured into mould, flakiness is suppressed.
It is preferred that：Graphene and the total mass fraction of CNT are 6%-14% in the step (1).
It is preferred that：The mass ratio of graphene and CNT is 1 in the step (1):1、2:1、1:2.
It is preferred that：PVA volume fraction is 2.2%-2.8% (preferably 2.5%) in the step (1).
It is preferred that：PVA addition is in the step (1)：3 to 5 drops are added with dropper.
It is preferred that：Ball-milling Time is 3-8 minutes (preferably 5 minutes) in the step (1).
It is preferred that：The condition of tabletting in the step (2)：Under 35MPa pressure, pressurize 3 minutes, diameter 20mm is pressed into,
Thickness is 1 to 3mm thin slice.
The negative permittivity material that the above method is prepared, the material is in resonator, wave filter and oscillator is prepared
Application.
Beneficial effects of the present invention：
Graphene and CNT, the lamellar structure and CNT of graphene in composite prepared by the present invention be present
Tubular structure it is compound mutually, connection interlaced with each other, the three-dimensional network shape to communicate with one another is uniformly distributed and formd between particle
Structure, the electrical conductive behavior of electronics is promoted, the electrical conductive behavior of composite is changed into variable journey transition from tunnel conduction, so as to go out
Negative dielectric is showed, the surface of graphene has a certain amount of functional group in addition, and these functional groups are not to interconnect, and are not led yet
Electricity, between repulsion be present, and be attached between the lamella of graphene, and be distributed in graphenic surface and turn into boundary layer,
It can be used for limiting leakage electrical conduction current, so as to reduce dielectric loss.
It is compound using graphene, CNT and phenolic resin in the inventive method, graphene have excellent optics,
Mechanics, electrically and thermally property, excellent thermal conductivity, can make up that polymer composites cause because of lower thermal conductivity can not
The shortcomings that being used in high power environment.
The numerical value of composite negative permittivity prepared by the present invention is controllable, when the mass fraction of regulation carbon material
When, the composites of different negative permittivity values can be obtained.
In the inventive method, selecting 3 to 5 drop volume fractions, PVA solution makes as adhesive for 2.5% PVA solution
Powdered raw material can more easily be pressed it is blocking, select add amount for 3 to 5 drip because PVA can cause to press when excessive
The sample of system is excessively sticky, but PVA solution content causes bonding effect bad again very little, and the drop of PVA solution 3 to 5 left and right can make original
Material has good bonding effect and occurred without sticky phenomenon.
Step (1) selects ball milling in the present invention, compared with other mechanical means, can make graphene, CNT and phenol
Urea formaldehyde is mixed more uniformly, and during running at high speed, three is uniformly distributed each other, 3-8 minutes
The structure that Ball-milling Time avoids raw material is destroyed.
Phenolic resin is used in the present invention, compared with other thermosetting resins, density is small after having solidification, mechanical strength,
Calorific intensity is high, becomes the advantages of sexual orientation is small, has preferable mechanical property and heat resistance, be good insulating materials, at this
Can be used as insulating body in experiment, and with graphene and CNT it is compound after, the mechanical property of product is good, mechanical strength
Height, it is easy to test.
Brief description of the drawings
Fig. 1 is the dielectric constant of composite and the relation curve of frequency prepared in embodiment 4
Fig. 2 is the electrical conductivity of composite and the relation curve of frequency prepared in embodiment 4.
Embodiment
The present invention is further described with reference to the accompanying drawings and examples.
Embodiment 1
Pan paper is put on electronic balance, takes graphene to be put on electronic balance with clean key, weighs 0.025g
Graphene, the graphene weighed up is poured into container；A pan paper is taken to be put on electronic balance again, with other clean key
Spoon takes CNT to weigh 0.025g CNTs to electronic balance, the CNT weighed up is poured into same with graphene
In individual container；Take a pan paper to be put on electronic balance again, take phenolic resin to be weighed to electronic balance with clean key
0.70g phenolic resin, the phenolic resin weighed up is poured into identical container.Mixed-powder in container is poured into ball grinder
In, the ball milling of progress 5 minutes, then stop ball milling, ball grinder is removed, well mixed powder is poured into mortar, with drop
Pipe instills the PVA solution that 4 drop volume fractions are 2.5%, grinds 5 minutes.Powder is poured among the mould of tabletting, mould diameter
20mm, it is put under forcing press, pressure is tuned into 35Mpa, and pressurize 3 minutes, then it is stripped, disc-shaped tabletting made of taking-up,
It is 6.67%, GR to obtain graphene and CNT total concentration：CNTS=1：1 composite.
Embodiment 2
Pan paper is put on electronic balance, takes graphene to be put on electronic balance with clean key, weighs 0.0335g
Graphene, the graphene weighed up is poured into container；A pan paper is taken to be put on electronic balance again, with other clean key
Spoon takes CNT to weigh 0.0165g CNTs to electronic balance, the CNT weighed up is poured into same with graphene
In individual container；Take a pan paper to be put on electronic balance again, take phenolic resin to be weighed to electronic balance with clean key
0.70g phenolic resin, the phenolic resin weighed up is poured into identical container.Mixed-powder in container is poured into ball grinder
In, the ball milling of progress 5 minutes, then stop ball milling, ball grinder is removed, well mixed powder is poured into mortar, with drop
Pipe instills the PVA solution that 4 drop volume fractions are 2.5%, grinds 5 minutes.Powder is poured among the mould of tabletting, mould diameter
20mm, it is put under forcing press, pressure is tuned into 35Mpa, and pressurize 3 minutes, then it is stripped, disc-shaped tabletting made of taking-up,
It is 6.67%, GR to obtain graphene and CNT total concentration:CNTS=2：1 composite.
Embodiment 3
Pan paper is put on electronic balance, takes graphene to be put on electronic balance with clean key, weighs 0.0165g
Graphene, the graphene weighed up is poured into container；A pan paper is taken to be put on electronic balance again, with other clean key
Spoon takes CNT to weigh 0.0335g CNTs to electronic balance, the CNT weighed up is poured into same with graphene
In individual container；Take a pan paper to be put on electronic balance again, take phenolic resin to be weighed to electronic balance with clean key
0.70g phenolic resin, the phenolic resin weighed up is poured into identical container.Mixed-powder in container is poured into ball grinder
In, the ball milling of progress 5 minutes, then stop ball milling, ball grinder is removed, well mixed powder is poured into mortar, with drop
Pipe instills the PVA solution that 4 drop volume fractions are 2.5%, grinds 5 minutes.Powder is poured among the mould of tabletting, mould diameter
20mm, it is put under forcing press, pressure is tuned into 35Mpa, and pressurize 3 minutes, then it is stripped, disc-shaped tabletting made of taking-up,
It is 6.67%, GR to obtain graphene and CNT total concentration：CNTS=1：2 composite.
Embodiment 4
Pan paper is put on electronic balance, takes graphene to be put on electronic balance with clean key, weighs 0.0375g
Graphene, the graphene weighed up is poured into container；A pan paper is taken to be put on electronic balance again, with other clean key
Spoon takes CNT to weigh 0.0375g CNTs to electronic balance, the CNT weighed up is poured into same with graphene
In individual container；Take a pan paper to be put on electronic balance again, take phenolic resin to be weighed to electronic balance with clean key
0.675g phenolic resin, the phenolic resin weighed up is poured into identical container.Mixed-powder in container is poured into ball grinder
In, the ball milling of progress 5 minutes, then stop ball milling, ball grinder is removed, well mixed powder is poured into mortar, with drop
Pipe instills the PVA solution that 4 drop volume fractions are 2.5%, grinds 5 minutes.Powder is poured among the mould of tabletting, mould diameter
20mm, it is put under forcing press, pressure is tuned into 35Mpa, and pressurize 3 minutes, then it is stripped, disc-shaped tabletting made of taking-up,
It is 10%, GR to obtain graphene and CNT total concentration：CNTS=1：1 composite.As shown in Figure 1, composite
Dielectric constant is negative value, and is all negative value within 10MHz to 1GHz frequency range, it is seen that is had been obtained for needed for us
The negative permittivity material wanted.Because graphene and CNT in the composite be present, the lamellar structure of graphene
Compound mutually, the connection interlaced with each other with the tubular structure of CNT, and three-dimensional network-like structure communicating together is formd, make
The electrical conductive behavior of composite is changed into variable journey transition from tunnel conduction, so as to negative dielectric occur.As shown in Figure 2, we make
The conductivity values of standby composite are all very low in the range of 10MHz to 1GHz, and obtained composite dielectric properties are excellent
It is different.Because graphene in composite be present, a certain amount of functional group is contained on the surface of graphene, between these functional groups
Repulsion be present, among being distributed in composite with graphene, form boundary layer, so as to result in low conductivity, reduce
Electrical conduction current is leaked, reduces dielectric loss.
Embodiment 5
Pan paper is put on electronic balance, takes graphene to be put on electronic balance with clean key, weighs 0.050g
Graphene, the graphene weighed up is poured into container；A pan paper is taken to be put on electronic balance again, with other clean key
Spoon takes CNT to weigh 0.025g CNTs to electronic balance, the CNT weighed up is poured into same with graphene
In individual container；Take a pan paper to be put on electronic balance again, take phenolic resin to be weighed to electronic balance with clean key
0.675g phenolic resin, the phenolic resin weighed up is poured into identical container.Mixed-powder in container is poured into ball grinder
In, the ball milling of progress 5 minutes, then stop ball milling, ball grinder is removed, well mixed powder is poured into mortar, with drop
Pipe instills the PVA solution that 4 drop volume fractions are 2.5%, grinds 5 minutes.Powder is poured among the mould of tabletting, mould diameter
20mm, it is put under forcing press, pressure is tuned into 35Mpa, and pressurize 3 minutes, then it is stripped, disc-shaped tabletting made of taking-up,
It is 10%, GR to obtain graphene and CNT total concentration：CNTS=2：1 composite.
Embodiment 6
Pan paper is put on electronic balance, takes graphene to be put on electronic balance with clean key, weighs 0.025g
Graphene, the graphene weighed up is poured into container；A pan paper is taken to be put on electronic balance again, with other clean
Key takes CNT to weigh 0.050g CNTs to electronic balance, the CNT weighed up is poured into same with graphene
In one container；Take a pan paper to be put on electronic balance again, phenolic resin is taken to electronic balance with clean key, claim
0.675g phenolic resin is taken, the phenolic resin weighed up is poured into identical container.Mixed-powder in container is poured into ball milling
In tank, the ball milling of 5 minutes is carried out, then stops ball milling, ball grinder is removed, well mixed powder is poured into mortar, used
Dropper instills the PVA solution that 4 drop volume fractions are 2.5%, grinds 5 minutes.Powder is poured among the mould of tabletting, mould is straight
Footpath 20mm, is put under forcing press, and pressure is tuned into 35Mpa, and pressurize 3 minutes, is then stripped, disc-shaped pressure made of taking-up
Piece, it is 10%, GR to obtain graphene and CNT total concentration：CNTS=1：2 composite.
Although above-mentioned the embodiment of the present invention is described with reference to accompanying drawing, model not is protected to the present invention
The limitation enclosed, one of ordinary skill in the art should be understood that on the basis of technical scheme those skilled in the art are not
Need to pay various modifications or deformation that creative work can make still within protection scope of the present invention.
Claims (6)
1. a kind of method that graphene, CNT and phenolic resin prepare negative permittivity material, it is characterized in that：Step is such as
Under：（1）By graphene powder, carbon nanotube powder and Phenolic resin powder, ball milling mixing is carried out, PVA solution is then added, grinds
Mill is uniform；（2）Among powder is poured into mould, flakiness is suppressed；
The step（1）The total mass fraction of middle graphene and CNT is 6%-14%；
The step（1）The mass ratio of middle graphene and CNT is 1:1、2:1、1:2；
The step（1）Middle PVA volume fraction is 2.2%-2.8%；
The step（1）Middle PVA addition is：3 to 5 drops are added with dropper.
2. the method as described in claim 1, it is characterized in that：The step（1）Middle PVA volume fraction is 2.5%.
3. the method as described in claim 1, it is characterized in that：The step（1）The middle ball milling mixing time is 3-8 minutes.
4. the method as described in claim 1, it is characterized in that：The step（2）The condition of middle compacting flakiness：35MPa pressure
Under power, pressurize 3 minutes is pressed into diameter 20mm, and thickness is 1 to 3mm thin slice.
5. the negative permittivity material that any described methods of claim 1-4 are prepared.
6. application of the negative permittivity material in resonator, wave filter and oscillator is prepared described in claim 5.
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| CN107868397B (en) * | 2016-09-23 | 2021-02-05 | 德州迈特新材料研究中心 | Composite material with weak negative dielectric constant and preparation method thereof |
| CN108570160B (en) * | 2017-03-13 | 2021-05-04 | 苏州市迈尔特材料科技有限公司 | Preparation method of super-structure capacitor material with MHz high dielectric constant |
| CN109516805B (en) * | 2017-09-20 | 2022-04-19 | 德州迈特新材料研究中心 | Preparation method of super-structure composite material with stable weak negative dielectric property |
| CN108794942B (en) * | 2018-07-09 | 2021-01-22 | 陕西科技大学 | Preparation method of polymer and three-dimensional porous graphene composite metamaterial |
| CN108929542B (en) * | 2018-08-09 | 2021-02-02 | 上海海事大学 | Polydimethylsiloxane/graphene flexible composite film with negative dielectric constant and preparation method thereof |
| CN110066484B (en) * | 2019-04-28 | 2020-12-15 | 上海海事大学 | Carbon nanotube-graphite-polyvinylidene fluoride ternary composite material with negative dielectric property and preparation method thereof |
| CN111944267B (en) * | 2020-07-30 | 2021-06-29 | 山东大学 | Preparation method of boron-doped graphene composite material and application of boron-doped graphene composite material as negative dielectric material |
| CN114163815B (en) * | 2021-12-24 | 2024-01-23 | 上海海事大学 | Composite material and preparation method thereof |
| CN115353708A (en) * | 2022-08-26 | 2022-11-18 | 云南协研科技有限公司 | Low-background conductive thermal insert special for scanning electron microscope and preparation method thereof |
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| CN102173157A (en) * | 2011-03-03 | 2011-09-07 | 海能达通信股份有限公司 | Antistatic composite material, electronic device shell and electronic device |
| CN102254584B (en) * | 2011-05-12 | 2014-09-03 | 中国科学院宁波材料技术与工程研究所 | General electronic paste based on graphene filler |
| CN103937295B (en) * | 2014-04-21 | 2015-08-19 | 苏州大学 | A kind of Graphene-titanium diboride oxide mixture and preparation method thereof |
| CN104614809B (en) * | 2015-01-12 | 2018-07-24 | 北京大学 | A kind of light polarization circulator and a kind of light polarization spinning solution |
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