CN109370155A - Field causes non-linear conducing composite material preparation method, obtained composite material and application - Google Patents
Field causes non-linear conducing composite material preparation method, obtained composite material and application Download PDFInfo
- Publication number
- CN109370155A CN109370155A CN201811207637.2A CN201811207637A CN109370155A CN 109370155 A CN109370155 A CN 109370155A CN 201811207637 A CN201811207637 A CN 201811207637A CN 109370155 A CN109370155 A CN 109370155A
- Authority
- CN
- China
- Prior art keywords
- composite material
- linear
- conducing composite
- suspension
- field
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/40—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes epoxy resins
-
- 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
- C08K2201/001—Conductive additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
-
- 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
Abstract
The invention discloses a kind of to cause non-linear conducing composite material preparation method, obtained composite material and application, is related to non-linear conducing composite material field.Steps are as follows: taking KH560, ethyl alcohol and deionized water, obtains solution A；GO is added in solution A, 75-85 DEG C of reaction 3-5h obtains suspension B；Alkali, which is added, to suspension B makes pH=10, and hydrazine hydrate is added, and after dispersion, is heated to 85-95 DEG C of reaction 5-7h and obtains suspension C, washing filters, and filtration cakes torrefaction obtains RKGO powder；RKGO powder, epoxy resin E-51 and acetone are mixed, suspension D is obtained, 75-85 DEG C of reaction to acetone volatilization is completely cooled down to 45-50 DEG C, 2-ethyl-4-methylimidazole liquid is added, reacts, and solidifies to obtain composite material after pumping bubble；RKGO filling quality score is 0.75%-1.50% in composite material.The preparation method is simple, at low cost, and the reaction time is short, is easy to largely prepare；Composite material light weight obtained, uniformity are good, conductive nonlinear factor is high, can be used for overvoltage protection, lightning surge protection, antistatic and self-adaptive electromagnetic pulse protection field.
Description
Technical field
Modified graphene/asphalt mixtures modified by epoxy resin the present invention relates to non-linear conducing composite material field, after especially a kind of reduction
Rouge field causes non-linear conducing composite material preparation method, obtained composite material and application.
Background technique
In recent years, large scale integrated circuit is widely used on Military Electronics information equipment, significant increase electricity
The informationization and intelligence of subsystem and equipment.At the same time, continuous with the electromagnetic pulse weapons such as High-Power Microwave (EMP)
Development and utilization, cause the electromagnetic environment in space more and more severe, the electromagnetic environmental effects of electronic system and equipment are increasingly significant.
Therefore, carrying out electromagnetic protection work is the key that guarantee that electronic system and equipment are brought into normal play performance.
The effective barrier that microwave defense material is threatened as electromagnetism is one of the effective means for solving electromagnetic protection.Tradition
Microwave defense material be using it to the attenuation by absorption of incident electromagnetic wave or reflection and then by electromagnetic wave and protected electronics
Equipment blocking is opened, to achieve the purpose that electromagnetic protection.But this kind of material all carries out useful and malice electromagnetic signal
Shielding, so that electronic equipment and extraneous normally associate receive obstruction.Therefore, the normal receiving and transmitting signal of electronic equipment how is handled
Contradiction between the protection attack of overvoltage, lightning surge, static discharge and strong electromagnetic pulse becomes the pass solved the problems, such as
Key.
Liu Pei state of the National University of Defense technology etc. proposes a kind of energy selection surface texture (ESS), is constructed using PIN diode
Energy selection surface and the preliminary identification validity of electromagnetic energy selection surface, but rung since diode material itself exists
The drawbacks such as slow, on-delay, make it be difficult to realize effective protection for moment electromagnetic pulse between seasonable.The sheet on energy selection surface
Matter is the insulator/metal phase transformation realized under electromagnetic field induction from material level, its impedance is made to change.It theoretically sees,
High-efficiency shielding electromagnetic wave needs low-impedance material, and high efficiency transmission electromagnetic wave then to need the material of high impedance, this is 2 kinds complete
Different demands will make a kind of material while meet 2 kinds of demands, and this material must have the characteristic of impedance, i.e., in low function
Under the irradiation of rate feeble field safety electromagnetic wave, it is in high-impedance state, sports low resistance state under the irradiation of high power high field unwanted electromagnetic wave, this
Class material belongs to intellectual material scope, has automatic sensing external environmental information and generates the material system of best response function,
We are normally referred to as environment self-adaption intelligent electromagnetic protective materials.For fast rising edge, narrowband electromagnetic pulse, material
The phase transformation response time must not be slower than the pulse duration just and can ensure that effective implementation of protective performance.
In fact, field cause (or electroluminescent) resistance material has the impedance characteristic of above-mentioned self-adaptive electromagnetic protective materials, i.e.,
The resistance of material generates violent variation and non-linear conductive characteristic is presented with electric field (voltage) or electric current.Gather under electric field action
Closing object based composites has non-linear conductive characteristic, the non-linear conductive features of composite material especially under forceful electric power field action
It is more obvious.For filled polymer conducing composite material, the intrinsic attribute of filler (or referred to as component) is to influence
The key factor of material macroscopic view effective performance.In recent years with the development of functional composite material, it has been found that in some polymerizations
Suitable metal oxide, nano metal or alloy powder are mixed in object material, can make such polymer-based nano composite wood
Material has non-linear conductive characteristic under electric field induction, before having preferable application as self-adapting intelligent microwave defense material
Scape.Domestic Zou consoles that the degree more early has studied the polypropylene-base for mixing Al or Ag micro mist and the conduction of polyvinyl dichloride based composites is opened
Characteristic is closed, is found near a certain electric field threshold value, the resistance value of composite material occurs significantly to become with the variation of external electric field
Change, it is special to the conductive switch of composite material when mixing type, the average particle size, volume ratio difference of metal or alloy particle
Property have large effect.Chen Guohua team of Huaqiao University has studied epoxy resin/graphite nano micro-flake conducing composite material and exists
Nonlinear conduction behavior under electric field action finds that the conductivity of compound system has by force non-linear and right to extra electric field
The nonlinear conduction behavior of this system gives theoretical explanation.
The two-dimentional carbon nanomaterial of graphene (Graphene) conduct (have be in nanoscale in one-dimensional square in space,
And remaining bidimensional is macro-size), the excellent electric conductivity that is both possessed with blocky graphite, thermal conductivity and it is stable chemically
Matter, and have novel characteristics and superhigh specific surface area possessed by two-dimension nano materials, high light transmittance and high electron mobility,
Physicochemical property is unique, Functionally structure, optical material, catalyst and in terms of have extremely
It is widely applied, is current most popular one of the material for most having application prospect.There is self-adaptation nonlinear using graphene exploitation
Conducing composite material has potential application prospect.The superhigh specific surface area and Ultralight feature of graphene make it as filling out
There is lower percolation threshold, since graphene is easy to reunite in organic solvent, difficult compatibility, it is therefore necessary to solve graphene when material
Self-adaptation nonlinear conductive material can be just prepared in the problem balanced between intrinsic property and raising matrix compatibility.
Summary of the invention
Non-linear conducing composite material preparation method is caused the technical problem to be solved in the present invention is to provide a kind of, obtained is answered
Condensation material and application, the preparation process is simple, easy to operate, low in cost, and the reaction time is shorter, is easy to largely prepare；It is made
Composite material light weight, uniformity is good, conductive nonlinear factor is high, can be used for overvoltage protection, lightning surge protection, anti-
Field is protected in electrostatic and self-adaptive electromagnetic pulse.
In order to solve the above technical problems, the technical solution used in the present invention is: a kind of causes non-linear conductive composite wood
Expect preparation method, includes the following steps:
(1) epoxy silane coupling KH560, ethyl alcohol and deionized water are taken, obtains solution A after dispersion；
(2) it adds graphene oxide into solution A, after dispersion, it is outstanding that modified graphene oxide is obtained after 75-85 DEG C of reaction 3-5h
Supernatant liquid B；
(3) aqueous slkali is added into suspension B makes suspension B keep pH value alkalinity, and hydrazine hydrate is taken to be added in suspension B,
After dispersing under room temperature, it is heated to 85-95 DEG C and is stirred to react after 5-7h to obtain suspension C, washing filters, and filter cake is freeze-dried
Modified graphene powder after being restored afterwards；
(4) modified graphene powder, epoxy resin E-51 and the acetone after reduction are mixed and is dispersed, obtain suspension D, in
75-85 DEG C of reaction, until 45-50 DEG C is cooled to after acetone volatilization completely, addition 2-ethyl-4-methylimidazole liquid, reaction, very
Solidify the modified graphene after being restored-epoxy resin field after empty pump bubble and causes non-linear conducing composite material；
It is 0.75%-1.50% that field, which causes the powder filled mass fraction of modified graphene after restoring in non-linear conducing composite material,.
Preferably, graphene oxide with a thickness of 0.6-1.0nm, lamella diameter is 0.5-5 μm, number of plies 1-2, specific surface
Product is 1000-1217m2/g。
Preferably, in solution A, the volume ratio of ethyl alcohol and deionized water is 2.5-3.5: 1.
Preferably, the mass ratio of graphene oxide and epoxy silane coupling KH560 are 9-11: 1.
Preferably, the mass ratio of modified graphene oxide and hydrazine hydrate is 7-9: 10.
Preferably, in step (3), into suspension B be added aqueous slkali make suspension B keep pH value 9.5-10.5 it
Between.
It is further preferred that aqueous slkali, which is added, into suspension B makes suspension B keep pH value 10 in step (3).
Preferably, in step (3), aqueous slkali is KOH solution；Washing is to be washed with ethyl alcohol and deionized water；Freeze-drying
To be dried in vacuo for 24 hours in vacuum freeze drier in -50 DEG C.
Preferably, the mass ratio of epoxy resin E-51 and 2-ethyl-4-methylimidazole is 100: 3-5.
Preferably, in suspension B, the grams of epoxy resin E-51 and the ratio between ml of acetone are 0.9-1.1: 10.
Above-mentioned field causes the application of solid polymer based composites obtained by non-linear conducing composite material preparation method: compound
Material protects field for overvoltage protection, lightning surge protection, antistatic and self-adaptive electromagnetic pulse.
Graphene oxide abbreviation GO in the present invention, modified graphene oxide abbreviation KGO, the modified graphene after reduction is referred to as
RKGO。
The beneficial effects of adopting the technical scheme are that
(1) modified graphene/epoxy resin field after present invention reduction causes the preparation process of non-linear conducing composite material simple,
Easy to operate, low in cost, the reaction time is shorter, is easy to largely prepare；Obtained composite material light weight, uniformity be good,
Conductive nonlinear factor is high, can be applied to overvoltage protection, lightning surge protection, antistatic and self-adaptive electromagnetic pulse protection
Field.
(2) the modified graphene RKGO preparation method simple process after the reduction that the present invention uses, it is easy to operate, and to reality
It is lower to test environmental requirement, low in cost, the reaction time is shorter, is easy to largely prepare, and RKGO product obtained is single layer or few layer
Laminated structure has compared with high length-diameter ratio, purity is high, and uniformity and dispersibility are preferable.
(3) epoxy resin selection thermal stability of the present invention and the higher E-51 model of dielectric constant, high strength after curing,
Solvent resistance is good, stability is strong, mechanical performance is excellent.Field causes the preparation of non-linear conducing composite material to use solution blended process work
Skill has many advantages, such as that simple process, easily operated, final product quality is stable and is convenient for addition auxiliary agent.
(4) present invention carries out that KH560 and hydrazine hydrate be modified and reduction to graphene oxide, then in a polymer matrix into
Row is filled lower than the low concentration of percolation threshold, so that composite material material under normality weak-field condition is externally rendered as insulation material
Material, the electron energy in modified graphene after outfield increases and restores surmount the potential barrier of insulating body formation between conductive filler
When, it will a large amount of tunneling electrons and conductive are generated, to generate significant conductive switch effect, the free tunnel in material at this time
Electron amount increases sharply, and increases substantially the conductivity and current-carrying capability of composite material, to can realize that material critical field is adjustable
And the double effects that conductivity is significantly promoted after phase transformation, it solves material normality high resistant and field causes the difficulty of low-resistance characteristic
Topic provides technology branch effectively to carry out overvoltage protection, lightning surge protection, antistatic and self-adaptive electromagnetic pulse protection
Support.
Detailed description of the invention
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments；
Fig. 1 is the TEM figure of KGO suspension B obtained in the embodiment of the present invention 1；
Fig. 2 is the SEM figure of RKGO powder obtained in the embodiment of the present invention 1；
Fig. 3 is the TEM figure of RKGO suspension C obtained in the embodiment of the present invention 1；
Fig. 4 is that the field that RKGO filling quality score obtained is 0.75% in the embodiment of the present invention 1 causes non-linear conducing composite material
Microcell SEM figure；
Fig. 5 is that the field that RKGO filling quality score obtained is 1.00% in the embodiment of the present invention 2 causes non-linear conducing composite material
Microcell SEM figure；
Fig. 6 is that the field that RKGO filling quality score obtained is 1.50% in the embodiment of the present invention 3 causes non-linear conducing composite material
Microcell SEM figure；
Fig. 7 is the volt-ampere song that field obtained causes non-linear conducing composite material under difference RKGO compound particle filling concentration of the invention
Line chart.
Specific embodiment
Primary Chemical used is as shown in table 1 in embodiment, and GO, KH560, KOH and hydrazine hydrate are for synthesizing RKGO；Second
Alcohol and deionized water for solvent needed for being equipped with reaction and wash suspension, to obtain pure RKGO；Acetone and
2E4MZ for realizing composite material solidification.
1 Primary Chemical of table
| Experiment reagent | Referred to as | Specification | Manufacturer/supplier |
| Single-layer graphene oxide | GO | AR | The rich science and technology of Suzhou carbon |
| Epoxy silane coupling | KH560 | AR | Sinopharm Chemical Reagent Co., Ltd. |
| Hydrazine hydrate | N2H4 | AR | Sinopharm Chemical Reagent Co., Ltd. |
| Potassium hydroxide | KOH | AR | Tianjin Kermel Chemical Reagent Co., Ltd. |
| 2-ethyl-4-methylimidazole | 2E4MZ | AR | Shandong West Asia chemistry limited liability company |
| Ethyl alcohol | AR | Tianjin Yong great chemical reagent Co., Ltd | |
| Acetone | AR | Tianjin Yong great chemical reagent Co., Ltd | |
| Epoxy resin E-51 | ER | AR | Chuzhou Hui Sheng Electron Material Co., Ltd |
For all reagents in embodiment without being further purified, embodiment is deionized water with water.
Embodiment 1
Modified graphene/epoxy resin field after reduction causes non-linear conducing composite material preparation method, includes the following steps:
(1) firstly, 50ml deionized water, 150ml ethyl alcohol and 10mg KH560 is taken to pour into beaker, ultrasonic disperse 1h to KH560 is complete
All-hydrolytic obtains mixed solution A.
(2) it then takes 100mg GO to be added in solution A, after ultrasonic disperse, is heated to 80 DEG C and is stirred to react 4h to obtain KGO outstanding
Supernatant liquid B.
(3) a small amount of KOH solution is added into suspension B and makes system pH=10, and take 147.06mg hydrazine hydrate to be added and suspend
In liquid B, after dispersing under room temperature, it is heated to 90 DEG C of magnetic agitation reaction 6h and obtains RKGO suspension C.
(4) after suspension C ethyl alcohol, deionized water being washed, filtered three times, vacuum freeze drier is put into -50 DEG C
Vacuum drying for 24 hours, obtains the RKGO powder of black.
(5) it takes RKGO 50mg, acetone 100 ml and epoxy resin E-51 9.57g to pour into beaker and sealed with preservative film to burn
Rim of a cup, ultrasonic disperse about 30min, obtains suspension D, is heated to 80 DEG C later and is stirred to react 4h, then removes preservative film, continues
Heating stirring becomes black even thick liquid, to guarantee that acetone evaporated is complete, obtains until suspension D no longer generates bubble
Liquid composite material system.
(6) liquid composite material system obtained is cooled to 45 DEG C in step (5), 0.38g 2E4MZ liquid is poured into, in 45
Pour into the mold for applying wipe release agent in advance after DEG C being stirred to react 1min, be first stored at room temperature under vulcanizer pressurization for 24 hours, then at
It is demoulded after standing 4h at 100 DEG C, obtains the field that RKGO mass fraction is 0.75% and cause non-linear conducing composite material.
Embodiment 2
Modified graphene/epoxy resin field after reduction causes non-linear conducing composite material preparation method, includes the following steps:
Before (1)-(4) step with embodiment 1.
(5) it takes RKGO 100mg, acetone 100ml and epoxy resin E-51 9.52g to pour into beaker and sealed with preservative film to burn
Rim of a cup, ultrasonic disperse about 30min, obtains suspension D, is heated to 80 DEG C later and is stirred to react 4h, then removes preservative film, continues
Heating stirring is complete up to acetone evaporated, obtains liquid composite material system.
(6) liquid composite material system obtained is cooled to 45 DEG C in step (5), 0.38g 2E4MZ liquid is poured into, in 45
Pour into the mold for applying wipe release agent in advance after DEG C being stirred to react 1min, be first stored at room temperature under vulcanizer pressurization for 24 hours, then at
It is demoulded after standing 4h at 100 DEG C, obtains the field that RKGO mass fraction is 1.00% and cause non-linear conducing composite material.
Embodiment 3
Modified graphene/epoxy resin field after reduction causes non-linear conducing composite material preparation method, includes the following steps:
Before (1)-(4) step with embodiment 1.
(5) it takes RKGO 150mg, acetone 100ml and epoxy resin E-51 9.47g to pour into beaker and sealed with preservative film to burn
Rim of a cup, ultrasonic disperse about 30min, obtains suspension D, is heated to 80 DEG C later and is stirred to react 4h, then removes preservative film, continues
Heating stirring is complete up to acetone evaporated, obtains liquid composite material system.
(6) liquid composite material system obtained is cooled to 45 DEG C in step (5), 0.38g 2E4MZ liquid is poured into, in 45
Pour into the mold for applying wipe release agent in advance after DEG C being stirred to react 1min, be first stored at room temperature under vulcanizer pressurization for 24 hours, then at
It is demoulded after standing 4h at 100 DEG C, obtains the field that RKGO mass fraction is 1.50% and cause non-linear conducing composite material.
KGO, RKGO and field cause structural characterization and the performance test of non-linear conducing composite material
1, KGO structural characterization obtained:
Fig. 1 schemes for the TEM of KGO suspension B obtained in the embodiment of the present invention 1；The present invention is limited using Japan's JEOL microscope
The JEM-2100 type transmission electron microscope (Transmission Electron Microscopy, TEM) of company's production is right
Micro-structure of the KGO product in suspension carries out observation analysis.From figure 1 it appears that the KGO generated is with single layer structure
Main, lamella diameter is about 1-2 μm, reunite less, fold it is small, uniformity and dispersibility are preferable, maintain original material GO's substantially
Good microstructure.
2, RKGO structural characterization obtained:
Fig. 2 schemes for the SEM of RKGO powder obtained in the embodiment of the present invention 1；The present invention is using German karr Zeiss microscope
Co., Ltd production 300 type scanning electron microscope of GeminiSEM (Scanning Electron Microscopy,
SEM observation analysis) is carried out to the micro-structure of RKGO product powder.From figure 2 it can be seen that the RKGO powder generated is due to hydration
The reduction of hydrazine causes piece diameter to have compared with GO and is obviously reduced, but substantially still exists with single layer structure, reunites few, fold
Mild degree shows that the modification of coupling agent KH560 plays good protective effect to the microstructure of KGO, greatly reduces also
Damage of the original work to its structure.
Fig. 3 schemes for the TEM of RKGO suspension C obtained in the embodiment of the present invention 1.The present invention still uses Japanese JEOL micro-
Mirror Co., Ltd production JEM-2100 type transmission electron microscope (Transmission Electron Microscopy,
TEM).From figure 3, it can be seen that the single layer structure of major part RKGO keeps good, scheme in conjunction with the SEM of RKGO, it has been confirmed that table
The modification of bright coupling agent KH560 plays the role of the protection of KGO microstructure very important.
3, modified graphene/epoxy resin field after restoring causes the Characterization for Microstructure of non-linear conducing composite material
In order to preferably observe the RKGO distribution on the scene caused in non-linear conducing composite material, it is to filling quality score
0.75%, 1.00%, 1.50% sample has carried out SEM phenetic analysis, as Figure 4-Figure 6.
It is analyzed by Fig. 4-6, RKGO is on the scene to be caused substantially to be evenly distributed in non-linear conducing composite material, and dispersibility is preferable, nothing
It is obvious to reunite, and as filling concentration improves, RKGO is formd more and more potential conductive logical from minority overlap joint multilayer overlap joint
Road.Since RKGO filling quality score is smaller, and the insulator interface that epoxy resin-base generates between RKGO, therefore in outside
Field strength will not be conductive when lower, and when strong electromagnetic pulse field action occurs in outside, composite material can occur field and cause Insulator-Metal phase
Become, so that the composite material abrupt transients of script high-impedance state are low resistance state, generates apparent nonlinear conduction behavior.
4, modified graphene/epoxy resin field after restoring causes the nonlinear wind vibration of non-linear conducing composite material to survey
Test result and analysis
Fig. 7 is that the particle-filled mass fraction of RKGO is respectively that 0.75%, 1.00% and 1.50% lower field obtained causes non-linear conduction multiple
The non-linear volt-ampere curve figure of condensation material, the results showed that, since 0.75wt%, the different particle-filled mass fractions of RKGO are answered
Condensation material all has more apparent nonlinear conduction behavior, and with the raising of filling concentration, the conductive switch of composite material
Voltage decreases, and different degrees of variation also has occurred in corresponding nonlinear factor.Therefore, field prepared by the present invention causes non-thread
Property conducing composite material, good field can be showed under low filling quality score causes conductive switch property, and fills
More critical fields are lower, this, which shows the particle-filled type composite material of modified graphene really, can effectively adjust the switch of material
Critical field strength, moreover, because non-linear conduction can be caused compound with the filler feature of lower filling quality score and Ultralight, field
Material not only may be implemented critical field regulation and increase substantially conductivity and current-carrying capability, but also reduce cost and convenient for answering
With there is better prospect.
Claims (10)
1. a kind of causes non-linear conducing composite material preparation method, characterized by the following steps:
(1) epoxy silane coupling KH560, ethyl alcohol and deionized water are taken, obtains solution A after dispersion；
(2) it adds graphene oxide into solution A, after dispersion, it is outstanding that modified graphene oxide is obtained after 75-85 DEG C of reaction 3-5h
Supernatant liquid B；
(3) aqueous slkali is added into suspension B makes suspension B keep pH value alkalinity, and hydrazine hydrate is taken to be added in suspension B,
After dispersing under room temperature, it is heated to 85-95 DEG C and is stirred to react after 5-7h to obtain suspension C, washing filters, and filter cake is freeze-dried
Modified graphene powder after being restored afterwards；
(4) modified graphene powder, epoxy resin E-51 and the acetone after reduction are mixed and is dispersed, obtain suspension D, in
75-85 DEG C of reaction, until 45-50 DEG C is cooled to after acetone volatilization completely, addition 2-ethyl-4-methylimidazole liquid, reaction, very
Solidify the modified graphene after being restored-epoxy resin field after empty pump bubble and causes non-linear conducing composite material；
It is 0.75%-1.50% that field, which causes the powder filled mass fraction of modified graphene after restoring in non-linear conducing composite material,.
2. field according to claim 1 causes non-linear conducing composite material preparation method, it is characterised in that the graphene oxide
With a thickness of 0.6-1.0nm, lamella diameter is 0.5-5 μm, number of plies 1-2, specific surface area 1000-1217m2/g。
3. field according to claim 1 causes non-linear conducing composite material preparation method, it is characterised in that: in solution A, ethyl alcohol and
The volume ratio of deionized water is 2.5-3.5: 1.
4. field according to claim 1 causes non-linear conducing composite material preparation method, it is characterised in that: graphene oxide and ring
The mass ratio of oxysilane coupling agent KH560 is 9-11: 1.
5. field according to claim 1 causes non-linear conducing composite material preparation method, it is characterised in that: modified graphene oxide
Mass ratio with hydrazine hydrate is 7-9: 10.
6. field according to claim 1 causes non-linear conducing composite material preparation method, which is characterized in that in step (3), alkali soluble
Liquid is KOH solution；Washing is to be washed with ethyl alcohol and deionized water；Freeze-drying is true in -50 DEG C in vacuum freeze drier
Sky is dry for 24 hours.
7. field according to claim 1 causes non-linear conducing composite material preparation method, it is characterised in that: epoxy resin E-51 and
The mass ratio of 2-ethyl-4-methylimidazole is 100: 3-5.
8. field according to claim 1 causes non-linear conducing composite material preparation method, which is characterized in that in suspension D, epoxy
The grams of resin E-51 and the ratio between ml of acetone are 0.9-1.1: 10.
9. a kind of as claim 1-8 described in any item cause solid polymerization obtained by non-linear conducing composite material preparation method
Object based composites.
10. a kind of field as claimed in claim 9 causes solid polymer base obtained by non-linear conducing composite material preparation method multiple
The application of condensation material, it is characterised in that the composite material is for overvoltage protection, lightning surge protection, antistatic and adaptive
Answer Spark gap field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811207637.2A CN109370155B (en) | 2018-10-17 | 2018-10-17 | Method for preparing field nonlinear conductive composite material, prepared composite material and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811207637.2A CN109370155B (en) | 2018-10-17 | 2018-10-17 | Method for preparing field nonlinear conductive composite material, prepared composite material and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109370155A true CN109370155A (en) | 2019-02-22 |
| CN109370155B CN109370155B (en) | 2020-09-15 |
Family
ID=65399966
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811207637.2A Active CN109370155B (en) | 2018-10-17 | 2018-10-17 | Method for preparing field nonlinear conductive composite material, prepared composite material and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109370155B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110348054A (en) * | 2019-06-11 | 2019-10-18 | 河海大学 | A kind of particle reinforced material conductivity calculation method of the body containing hard core-soft core structure |
| CN110615972A (en) * | 2019-10-18 | 2019-12-27 | 北京航空航天大学 | Preparation method of high-toughness epoxy-graphene nanocomposite material with anti-abalone shell structure |
| CN111484705A (en) * | 2020-04-17 | 2020-08-04 | 中国人民解放军陆军工程大学 | Zinc oxide coated graphene/epoxy resin nonlinear conductive composite material and preparation method thereof |
| CN112080106A (en) * | 2020-09-16 | 2020-12-15 | 中国人民解放军陆军工程大学 | Graphene-carbon nanotube/epoxy resin nonlinear conductive composite material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104093786A (en) * | 2011-09-01 | 2014-10-08 | 伦斯勒理工学院 | Graphene oxide polymer with nonlinear resistivity |
| CN105647468A (en) * | 2016-04-07 | 2016-06-08 | 兰州天烁新能源有限公司 | Wave-absorbing material based on grapheme and preparation method thereof |
-
2018
- 2018-10-17 CN CN201811207637.2A patent/CN109370155B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104093786A (en) * | 2011-09-01 | 2014-10-08 | 伦斯勒理工学院 | Graphene oxide polymer with nonlinear resistivity |
| CN105647468A (en) * | 2016-04-07 | 2016-06-08 | 兰州天烁新能源有限公司 | Wave-absorbing material based on grapheme and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| YANG YUAN, ET AL.: "Nonlinear DC Conduction Behavior in Graphene Nanoplatelets/Epoxy Resin Composites", 《IOP CONF. SER.: MATER. SCI. ENG.》 * |
| 李禾等: "低填料比石墨烯/环氧树脂复合材料非线性电导机理的实验研究", 《高电压技术》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110348054A (en) * | 2019-06-11 | 2019-10-18 | 河海大学 | A kind of particle reinforced material conductivity calculation method of the body containing hard core-soft core structure |
| CN110348054B (en) * | 2019-06-11 | 2020-11-06 | 河海大学 | Method for calculating electric conductivity of particle reinforced material containing hard core-soft shell structure |
| CN110615972A (en) * | 2019-10-18 | 2019-12-27 | 北京航空航天大学 | Preparation method of high-toughness epoxy-graphene nanocomposite material with anti-abalone shell structure |
| CN110615972B (en) * | 2019-10-18 | 2021-01-22 | 北京航空航天大学 | Preparation method of high-toughness epoxy-graphene nanocomposite material with anti-abalone shell structure |
| CN111484705A (en) * | 2020-04-17 | 2020-08-04 | 中国人民解放军陆军工程大学 | Zinc oxide coated graphene/epoxy resin nonlinear conductive composite material and preparation method thereof |
| CN111484705B (en) * | 2020-04-17 | 2023-01-10 | 中国人民解放军陆军工程大学 | Zinc oxide coated graphene/epoxy resin nonlinear conductive composite material and preparation method thereof |
| CN112080106A (en) * | 2020-09-16 | 2020-12-15 | 中国人民解放军陆军工程大学 | Graphene-carbon nanotube/epoxy resin nonlinear conductive composite material and preparation method thereof |
| CN112080106B (en) * | 2020-09-16 | 2023-03-28 | 中国人民解放军陆军工程大学 | Graphene-carbon nanotube/epoxy resin nonlinear conductive composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109370155B (en) | 2020-09-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109370155A (en) | Field causes non-linear conducing composite material preparation method, obtained composite material and application | |
| Zhou et al. | Ultrathin MXene/calcium alginate aerogel film for high‐performance electromagnetic interference shielding | |
| Bhadra et al. | A review of advances in the preparation and application of polyaniline based thermoset blends and composites | |
| Ganguly et al. | Polymer nanocomposites for electromagnetic interference shielding: a review | |
| CN107399735B (en) | Preparation method and application of graphene composite aerogel wave-absorbing material | |
| Farukh et al. | Enhanced electromagnetic shielding behavior of multi-walled carbon nanotube entrenched poly (3, 4-ethylenedioxythiophene) nanocomposites | |
| Oyharçabal et al. | Influence of the morphology of polyaniline on the microwave absorption properties of epoxy polyaniline composites | |
| EP2014718B1 (en) | Conductive composition, and their production method | |
| CN112876712A (en) | MXene-based flexible polyvinyl alcohol electromagnetic shielding composite film and preparation method thereof | |
| US20070096066A1 (en) | Conductive composition, conductive coating material, conductive resin, capacitor, photoelectric transducer, and their production method | |
| Bera et al. | Carbon nanohorn and graphene nanoplate based polystyrene nanocomposites for superior electromagnetic interference shielding applications | |
| CN109337102B (en) | Preparation method of self-adaptive electromagnetic pulse shielding film, prepared film and application | |
| Wu et al. | Electromagnetic interference shielding properties of solid-state polymerization conducting polymer | |
| Bai et al. | Controllable synthesis of leaflet-like poly (3, 4-ethylenedioxythiophene)/single-walled carbon nanotube composites with microwave absorbing property | |
| CN104448303A (en) | Ethylene-vinyl acetate copolymer/polyaniline composite conductive material and preparation method thereof | |
| CN113773688A (en) | Functionalized nano composite electromagnetic shielding coating and preparation method and application thereof | |
| CN107353551B (en) | Preparation method of light broadband electromagnetic shielding material | |
| CN112358630A (en) | Polystyrene-coated metal oxide nano particle and preparation method and application thereof | |
| CN111943150A (en) | Green stripping method for hexagonal boron nitride nanosheets | |
| Wang et al. | Tunable dielectric properties of carbon nanotube@ polypyrrole core-shell hybrids by the shell thickness for electromagnetic wave absorption | |
| Koo et al. | Polymer‐Based EMI Shielding Materials | |
| Sharma et al. | Recent Progress in Poly (3, 4‐Ethylene Dioxythiophene): Polystyrene Sulfonate Based Composite Materials for Electromagnetic Interference Shielding | |
| Liu et al. | Improved electromechanical properties of polydimethylsiloxane composites with sandwich structured Al (OH) 3@ GO nanosheets | |
| CN108211828B (en) | Method for preparing graphene carbon nanotube hybrid carbon slurry | |
| Varshney et al. | Designing of materials for EMI shielding applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |