CN109370155B - Method for preparing field nonlinear conductive composite material, prepared composite material and application - Google Patents
Method for preparing field nonlinear conductive composite material, prepared composite material and application Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention discloses a preparation method of a field-induced nonlinear conductive composite material, a prepared composite material and application, and relates to the field of nonlinear conductive composite materials. The method comprises the following steps: taking KH560, ethanol and deionized water to obtain a solution A; adding GO into the solution A, and reacting for 3-5h at 75-85 ℃ to obtain a suspension B; adding alkali into the suspension B to enable the pH to be =10, adding hydrazine hydrate, dispersing, heating to 85-95 ℃ to react for 5-7h to obtain suspension C, washing, performing suction filtration, and drying a filter cake to obtain RKGO powder; mixing RKGO powder, epoxy resin E-51 and acetone to obtain a suspension D, reacting at 75-85 ℃ until the acetone is volatilized and is completely cooled to 45-50 ℃, adding 2-ethyl-4-methylimidazole liquid, reacting, pumping bubbles and curing to obtain a composite material; the RKGO in the composite material is filled with 0.75-1.50% by mass. The preparation method is simple, low in cost, short in reaction time and easy for mass preparation; the prepared composite material has light weight, good uniformity and high conductive nonlinear coefficient, and can be used in the fields of overvoltage protection, lightning surge protection, static prevention and self-adaptive electromagnetic pulse protection.
Description
Technical Field
The invention relates to the field of nonlinear conductive composite materials, in particular to a preparation method of a reduced modified graphene/epoxy resin field nonlinear conductive composite material, a prepared composite material and application.
Background
In recent years, large-scale integrated circuits are widely used on military electronic information equipment, and informatization and intellectualization of electronic systems and equipment are greatly improved. Meanwhile, with the continuous development and application of electromagnetic pulse weapons (EMP) such as high-power microwaves, the electromagnetic environment of the space is more and more severe, and the electromagnetic environment effect of electronic systems and equipment is more and more obvious. Therefore, the key to ensure the normal performance of electronic systems and equipment is to make electromagnetic protection work.
The electromagnetic protection material is one of effective means for solving the electromagnetic protection as an effective barrier for electromagnetic threats. The traditional electromagnetic protection material utilizes the absorption attenuation or reflection of the traditional electromagnetic protection material on incident electromagnetic waves to further isolate the electromagnetic waves from protected electronic equipment, thereby achieving the purpose of electromagnetic protection. However, such materials shield both useful and malicious electromagnetic signals, preventing the electronic device from being properly connected to the outside world. Therefore, how to deal with the contradiction between the normal signal receiving and transmitting of the electronic equipment and the overvoltage, lightning surge, electrostatic discharge and strong electromagnetic pulse protection attack becomes the key for solving the problem.
An energy selection surface structure (ESS) is provided by the national defense science and technology university Liu Pai nationality and the like, an energy selection surface is constructed by utilizing a PIN diode, the effectiveness of the electromagnetic energy selection surface is preliminarily verified, and due to the defects of slow response time, conduction delay and the like of a diode material, the diode material is difficult to effectively protect against instant electromagnetic pulse. The nature of the energy selection surface is to realize metal/insulation phase change induced by electromagnetic field from the material layer surface, so that the impedance of the energy selection surface is changed. Theoretically, a material with low impedance is needed for efficiently shielding electromagnetic waves, a material with high impedance is needed for efficiently transmitting the electromagnetic waves, the two completely different requirements are 2, one material can simultaneously meet the 2 requirements, the material has the characteristic of impedance variation, namely, the material is in a high impedance state under the irradiation of low-power weak-field safe electromagnetic waves, and is mutated into a low impedance state under the irradiation of high-power strong-field harmful electromagnetic waves, the material belongs to the category of intelligent materials, and the material system has the functions of automatically sensing external environment information and generating the best response, and is generally called as an environment adaptive intelligent electromagnetic protection material. For a fast rising edge, narrow band electromagnetic pulse, the phase change response time of the material must not be slower than the pulse duration to ensure effective implementation of the shielding performance.
In fact, the field-induced (or electro-) resistive material has the impedance-varying characteristics of the adaptive electromagnetic shielding material, that is, the resistance of the material changes dramatically with the electric field (voltage) or current, and thus exhibits nonlinear conductive characteristics. The polymer-based composite material has nonlinear conductive characteristics under the action of an electric field, and the nonlinear conductive characteristics of the composite material are more obvious particularly under the action of a strong electric field. For filled polymer conductive composites, the intrinsic properties of the filler (otherwise known as the component) are key factors affecting the macroscopic performance of the material. In recent years, with the development of functional composite materials, people find that a proper amount of metal oxide, nano metal or alloy powder is doped into some polymer materials, so that the polymer-based nano composite material has nonlinear conductive characteristics under the induction of an electric field, and has better application prospects as a self-adaptive intelligent electromagnetic protection material. In China, Zhouyou, et Al earlier studied the conductive switching characteristics of Al or Ag micro powder doped polypropylene-based and poly-dichloroethylene-based composite materials, and found that the resistance value of the composite material is greatly changed along with the change of an external electric field near a certain electric field threshold, and when the types, average granularity and volume ratio of doped metal or alloy particles are different, the conductive switching characteristics of the composite material are greatly influenced. The university of Huaqiao Chen China Hua team researches the nonlinear conductive behavior of the epoxy resin/graphite nano-microchip conductive composite material under the action of an electric field, finds that the conductivity of the composite system has strong nonlinearity to an applied electric field, and gives theoretical explanation on the nonlinear conductive behavior of the system.
Graphene (Graphene) as a two-dimensional carbon nanomaterial (with one dimension in the space being at a nanoscale, and the other two dimensions being macroscopic) has excellent electrical conductivity, thermal conductivity and stable chemical properties of bulk graphite, novel characteristics of two-dimensional nanomaterials, ultrahigh specific surface area, high light transmittance and high electron mobility, unique physical and chemical properties, and extremely wide application in polymer functional materials, optical materials, catalysts, high-performance solar cells and the like, and is one of the most popular materials with application prospects at present. The graphene is utilized to develop the self-adaptive nonlinear conductive composite material, and the potential application prospect is achieved. Due to the characteristics of ultrahigh specific surface area and ultra-light weight of graphene, the graphene has a lower percolation threshold when used as a filler, and the graphene is easy to agglomerate in an organic solvent and is difficult to be compatible, so that the self-adaptive nonlinear conductive material can be prepared only by solving the problem of balance between the intrinsic characteristics of the graphene and the compatibility of a matrix.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a field-induced nonlinear conductive composite material, the prepared composite material and application, wherein the preparation method has the advantages of simple process, simple and convenient operation, low cost, short reaction time and easy mass preparation; the prepared composite material has light weight, good uniformity and high conductive nonlinear coefficient, and can be used in the fields of overvoltage protection, lightning surge protection, static prevention and self-adaptive electromagnetic pulse protection.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a method for preparing a field nonlinear conductive composite material comprises the following steps:
(1) taking epoxy silane coupling agent KH560, ethanol and deionized water, and dispersing to obtain solution A;
(2) adding graphene oxide into the solution A, dispersing, and reacting at 75-85 ℃ for 3-5h to obtain a modified graphene oxide suspension B;
(3) adding an alkali solution into the suspension B to keep the pH value of the suspension B alkaline, adding hydrazine hydrate into the suspension B, dispersing at normal temperature, heating to 85-95 ℃, stirring and reacting for 5-7h to obtain a suspension C, washing, performing suction filtration, and freeze-drying a filter cake to obtain reduced modified graphene powder;
(4) mixing and dispersing the reduced modified graphene powder, epoxy resin E-51 and acetone to obtain a suspension D, reacting at 75-85 ℃, cooling to 45-50 ℃ after the acetone is completely volatilized, adding 2-ethyl-4-methylimidazole liquid, reacting, vacuumizing and curing to obtain the reduced modified graphene-epoxy resin field nonlinear conductive composite material;
the filling mass fraction of the reduced modified graphene powder in the field nonlinear conductive composite material is 0.75-1.50%.
Preferably, the thickness of the graphene oxide is 0.6-1.0nm, the diameter of a lamella is 0.5-5 μm, the number of layers is 1-2, and the specific surface area is 1000-2/g。
Preferably, the volume ratio of ethanol to deionized water in the solution A is 2.5-3.5: 1.
Preferably, the mass ratio of the graphene oxide to the epoxy silane coupling agent KH560 is 9-11: 1.
Preferably, the mass ratio of the modified graphene oxide to the hydrazine hydrate is 7-9: 10.
Preferably, in step (3), an alkali solution is added to suspension B to maintain suspension B at a pH of between 9.5 and 10.5.
Further preferably, in step (3), an alkali solution is added to the suspension B to maintain the suspension B at a pH of 10.
Preferably, in the step (3), the alkali solution is a KOH solution; washing is washing by using ethanol and deionized water; the freeze drying is vacuum drying at-50 deg.C for 24 hr in vacuum freeze dryer.
Preferably, the mass ratio of the epoxy resin E-51 to the 2-ethyl-4-methylimidazole is 100: 3-5.
Preferably, in the suspension B, the ratio of the grams of the epoxy resin E-51 to the milliliters of the acetone is 0.9-1.1: 10.
The application of the solid polymer matrix composite prepared by the field nonlinear conductive composite preparation method comprises the following steps: the composite material is used in the fields of overvoltage protection, lightning surge protection, static prevention and self-adaptive electromagnetic pulse protection.
In the invention, the graphene oxide is called GO for short, the modified graphene oxide is called KGO for short, and the reduced modified graphene is called RKGO for short.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
(1) the preparation method of the reduced modified graphene/epoxy resin field nonlinear conductive composite material is simple in process, simple and convenient to operate, low in cost, short in reaction time and easy to prepare in large quantities; the prepared composite material has light weight, good uniformity and high conductive nonlinear coefficient, and can be applied to the fields of overvoltage protection, lightning surge protection, static prevention and self-adaptive electromagnetic pulse protection.
(2) The preparation method of the reduced modified graphene RKGO adopted by the invention has the advantages of simple process, simple and convenient operation, lower requirement on experimental environment, low cost, shorter reaction time and easy mass preparation, and the prepared RKGO product has a single-layer or few-layer lamellar structure, higher length-diameter ratio, high purity, better uniformity and dispersibility.
(3) The epoxy resin of the invention adopts E-51 type with higher thermal stability and dielectric constant, and has high strength, good solvent resistance, strong stability and excellent mechanical property after being cured. The preparation of the field nonlinear conductive composite material adopts a solution blending method process, and has the advantages of simple process, easy operation, stable finished product quality, convenient addition of auxiliary agents and the like.
(4) The invention modifies and reduces graphene oxide by KH560 and hydrazine hydrate, then low-concentration filling below a percolation threshold is carried out in the polymer matrix, so that the composite material is externally presented as an insulating material under normal weak field conditions, when the external field is increased and the energy of electrons in the reduced modified graphene exceeds the potential barrier formed by the insulating matrix among the conductive fillers, a large amount of tunnel electrons are generated and the modified graphene is conductive, thereby generating obvious conductive switching effect, the quantity of free tunnel electrons in the material is increased sharply, the conductivity and the current carrying capacity of the composite material are greatly improved, therefore, the dual effects of adjusting the critical field of the material and greatly improving the conductivity after phase change can be realized, the problems of high resistance in the normal state and low resistance in the field of the material are solved, and the technical support is provided for effectively performing overvoltage protection, lightning surge protection, static prevention and self-adaptive electromagnetic pulse protection.
Drawings
The invention is described in further detail below with reference to the drawings and the detailed description;
FIG. 1 is a TEM image of KGO suspension B prepared in example 1 of the present invention;
FIG. 2 is an SEM image of RKGO powder made in example 1 of the invention;
FIG. 3 is a TEM image of RKGO suspension C prepared in example 1 of the present invention;
FIG. 4 is a micro-domain SEM image of a field non-linear conductive composite with a 0.75% RKGO loading mass fraction made in example 1 of the invention;
FIG. 5 is a micro-domain SEM image of a field non-linear conductive composite with a RKGO filler mass fraction of 1.00% made in example 2 of the invention;
FIG. 6 is a micro-domain SEM image of a field non-linear conductive composite with a RKGO filler mass fraction of 1.50% made in example 3 of the invention;
FIG. 7 is a plot of voltammetry for field-induced nonlinear conductive composites made with different loading concentrations of RKGO composite particles in accordance with the present invention.
Detailed Description
The main chemical reagents used in the examples are shown in table 1, GO, KH560, KOH and hydrazine hydrate for the synthesis of RKGO; ethanol and deionized water are used for preparing a solvent required by the reaction and washing the suspension to obtain pure RKGO; acetone and 2E4MZ were used to effect curing of the composite.
TABLE 1 Main chemical reagents
| Experimental reagent | For short | Specification of | Manufacturer/supplier |
| Single-layer graphene oxide | GO | AR | Suzhou carbon feng technology |
| Epoxy siliconAlkane coupling agents | 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-Xia chemical Co., Ltd |
| Ethanol | AR | TIANJIN YONGDA CHEMICAL REAGENT Co.,Ltd. | |
| Acetone (II) | AR | TIANJIN YONGDA CHEMICAL REAGENT Co.,Ltd. | |
| Epoxy resin E-51 | ER | AR | Chuzhou Huisheng electronic materials Co Ltd |
All reagents in the examples were not further purified and the water used in the examples was deionized water.
Example 1
The preparation method of the reduced modified graphene/epoxy resin field nonlinear conductive composite material comprises the following steps:
(1) firstly, 50ml of deionized water, 150ml of ethanol and 10mg of KH560 are poured into a beaker and ultrasonically dispersed for 1 hour until the KH560 is completely hydrolyzed to obtain a mixed solution A.
(2) And then 100mg of GO is added into the solution A, and after ultrasonic dispersion, the mixture is heated to 80 ℃ and stirred to react for 4 hours to obtain KGO suspension B.
(3) Adding a small amount of KOH solution into the suspension B to ensure that the pH of the system is =10, adding 147.06mg of hydrazine hydrate into the suspension B, dispersing at normal temperature, heating to 90 ℃, and carrying out magnetic stirring reaction for 6 hours to obtain RKGO suspension C.
(4) And washing the suspension C with ethanol and deionized water, performing suction filtration for three times, and putting the suspension C into a vacuum freeze dryer to perform vacuum drying for 24 hours at the temperature of 50 ℃ below zero to obtain black RKGO powder.
(5) And (2) pouring 50mg of RKGO, 100ml of acetone and E-519.57 g of epoxy resin into a beaker, sealing the opening of the beaker by using a preservative film, ultrasonically dispersing for about 30min to obtain a suspension D, heating to 80 ℃, stirring for reacting for 4h, removing the preservative film, and continuously heating and stirring until the suspension D does not generate bubbles any more to form black uniform viscous liquid so as to ensure that the acetone is completely evaporated to obtain a liquid composite material system.
(6) And (3) cooling the liquid composite material system prepared in the step (5) to 45 ℃, pouring 0.38g of 2E4MZ liquid, stirring at 45 ℃ for reaction for 1min, pouring into a mold coated with a release agent in advance, standing at room temperature for 24h under the pressure of a vulcanizing machine, standing at 100 ℃ for 4h, and then demolding to obtain the field nonlinear conductive composite material with the RKGO mass fraction of 0.75%.
Example 2
The preparation method of the reduced modified graphene/epoxy resin field nonlinear conductive composite material comprises the following steps:
the foregoing (1) to (4) are the same as in example 1.
(5) And pouring 100mg of RKGO, 100ml of acetone and E-519.52 g of epoxy resin into a beaker, sealing the opening of the beaker with a preservative film, ultrasonically dispersing for about 30min to obtain a suspension D, heating to 80 ℃, stirring for reacting for 4h, removing the preservative film, and continuously heating and stirring until the acetone is completely evaporated to obtain a liquid composite material system.
(6) And (3) cooling the liquid composite material system prepared in the step (5) to 45 ℃, pouring 0.38g of 2E4MZ liquid, stirring and reacting at 45 ℃ for 1min, pouring into a mold coated with a release agent in advance, standing at room temperature for 24h under the pressure of a vulcanizing machine, standing at 100 ℃ for 4h, and then demolding to obtain the field nonlinear conductive composite material with the RKGO mass fraction of 1.00%.
Example 3
The preparation method of the reduced modified graphene/epoxy resin field nonlinear conductive composite material comprises the following steps:
the foregoing (1) to (4) are the same as in example 1.
(5) And (2) pouring 150mg of RKGO, 100ml of acetone and E-519.47 g of epoxy resin into a beaker, sealing the opening of the beaker with a preservative film, ultrasonically dispersing for about 30min to obtain a suspension D, heating to 80 ℃, stirring for reacting for 4h, removing the preservative film, and continuously heating and stirring until the acetone is completely evaporated to obtain a liquid composite material system.
(6) And (3) cooling the liquid composite material system prepared in the step (5) to 45 ℃, pouring 0.38g of 2E4MZ liquid, stirring at 45 ℃ for reaction for 1min, pouring into a mold coated with a release agent in advance, standing at room temperature for 24h under the pressure of a vulcanizing machine, standing at 100 ℃ for 4h, and then demolding to obtain the field nonlinear conductive composite material with the RKGO mass fraction of 1.50%.
Structural characterization and performance test of KGO, RKGO and field nonlinear conductive composite material
1. The prepared KGO has structural characteristics:
FIG. 1 is a TEM image of KGO suspension B obtained in example 1 of the present invention; the microstructure of the KGO product in suspension was observed and analyzed by a JEM-2100 type Transmission Electron Microscope (TEM) manufactured by JEOL microscope, Inc., Japan. As can be seen from FIG. 1, the formed KGO is mainly of single-layer structure, has a lamella diameter of about 1-2 μm, has less agglomeration, less wrinkles and better uniformity and dispersibility, and basically maintains the good microstructure of the original material GO.
2. Structural characterization of the prepared RKGO:
FIG. 2 is an SEM image of RKGO powder made in example 1 of the present invention; the microstructure of the RKGO product powder is observed and analyzed by a GeminiSEM 300 Scanning Electron Microscope (SEM) produced by Karl Zeiss microscope company Limited. As can be seen from FIG. 2, the sheet diameter of the produced RKGO powder is obviously reduced compared with GO due to the reduction effect of hydrazine hydrate, but the RKGO powder basically exists in a single-layer structure, has less aggregation and light wrinkle degree, and shows that the modification of the coupling agent KH560 plays a good role in protecting the microstructure of KGO, thereby greatly reducing the damage of the reduction effect on the structure.
FIG. 3 is a TEM image of RKGO suspension C made in example 1 of the invention. The present invention still employs a Transmission Electron Microscope (TEM) of JEM-2100 type manufactured by JEOL microscope, Inc., Japan. From fig. 3 it can be seen that most of the RKGO monolayer structure remained good, in combination with the SEM picture of RKGO it can be confirmed that the modification of the coupling agent KH560 plays a very important role in the protection of KGO microstructure.
3. Microstructure characterization of reduced modified graphene/epoxy resin field-induced nonlinear conductive composite material
To better observe the distribution of RKGO in the field nonlinear conductive composite, SEM characterization analysis was performed on samples with 0.75%, 1.00%, 1.50% packing mass fraction as shown in fig. 4-6.
From fig. 4-6, it is analyzed that RKGO is substantially uniformly distributed in the field-induced nonlinear conductive composite material, the dispersibility is better, no obvious agglomeration is generated, and with the increase of the filling concentration, RKGO is overlapped from a few overlapped layers to form more and more potential conductive paths. Because the RKGO is small in filling mass fraction, and an insulating interface is formed between the RKGO and the epoxy resin matrix, the RKGO cannot conduct electricity when the external field intensity is low, and when a strong electromagnetic pulse field effect appears outside, the composite material can undergo field insulation-metal phase change, so that the original composite material in a high-resistance state is instantly mutated into a low-resistance state, and an obvious nonlinear conducting behavior is generated.
4. Nonlinear volt-ampere characteristic test result and analysis of reduced modified graphene/epoxy resin field nonlinear conductive composite material
FIG. 7 is a plot of nonlinear voltammetry for field-induced nonlinear conductive composites made with RKGO particles at 0.75%, 1.00% and 1.50% filled mass fractions, respectively, showing that from 0.75wt%, the composites with different filled mass fractions of RKGO particles all have a more pronounced nonlinear conductive behavior, and as the filling concentration increases, the conductive switching voltage of the composite decreases and the corresponding nonlinear coefficient also changes to different extents. Therefore, the field nonlinear conductive composite material prepared by the invention can show good field conductive switching property under the condition of low filling mass fraction, and the more filled field is, the lower the critical field is, which shows that the switch critical field intensity of the material can be effectively adjusted by the modified graphene particle filled composite material.
Claims (10)
1. A method for preparing a field nonlinear conductive composite material is characterized by comprising the following steps: the method comprises the following steps:
(1) taking epoxy silane coupling agent KH560, ethanol and deionized water, and dispersing to obtain solution A;
(2) adding graphene oxide into the solution A, dispersing, and reacting at 75-85 ℃ for 3-5h to obtain a modified graphene oxide suspension B;
(3) adding an alkali solution into the suspension B to keep the pH value of the suspension B alkaline, adding hydrazine hydrate into the suspension B, dispersing at normal temperature, heating to 85-95 ℃, stirring and reacting for 5-7h to obtain a suspension C, washing, performing suction filtration, and freeze-drying a filter cake to obtain reduced modified graphene powder;
(4) mixing and dispersing the reduced modified graphene powder, epoxy resin E-51 and acetone to obtain a suspension D, reacting at 75-85 ℃, cooling to 45-50 ℃ after the acetone is completely volatilized, adding 2-ethyl-4-methylimidazole liquid, reacting, vacuumizing and curing to obtain the reduced modified graphene-epoxy resin field nonlinear conductive composite material;
the filling mass fraction of the reduced modified graphene powder in the field nonlinear conductive composite material is 0.75-1.50%.
2. The method for preparing field nonlinear conductive composite material as claimed in claim 1, wherein the graphene oxide has a thickness of 0.6-1.0nm, a lamella diameter of 0.5-5 μm, a number of layers of 1-2, a specific surface area of 1000-2/g。
3. The method of making a field nonlinear conductive composite material as recited in claim 1, wherein: in the solution A, the volume ratio of ethanol to deionized water is 2.5-3.5: 1.
4. The method of making a field nonlinear conductive composite material as recited in claim 1, wherein: the mass ratio of the graphene oxide to the epoxy silane coupling agent KH560 is 9-11: 1.
5. The method of making a field nonlinear conductive composite material as recited in claim 1, wherein: the mass ratio of the modified graphene oxide to the hydrazine hydrate is 7-9: 10.
6. The method for producing a field nonlinear conductive composite material as claimed in claim 1, wherein in the step (3), the alkali solution is KOH solution; washing is washing by using ethanol and deionized water; the freeze drying is vacuum drying at-50 deg.C for 24 hr in vacuum freeze dryer.
7. The method of making a field nonlinear conductive composite material as recited in claim 1, wherein: the mass ratio of the epoxy resin E-51 to the 2-ethyl-4-methylimidazole is 100: 3-5.
8. The method for producing a field nonlinear conductive composite material as claimed in claim 1, wherein a ratio of grams of the epoxy resin E-51 to milliliters of acetone in the suspension D is 0.9 to 1.1: 10.
9. A solid polymer matrix composite prepared by the method of any one of claims 1 to 8.
10. Use of a solid polymer matrix composite material prepared by the method of making a field-induced nonlinear conductive composite material as claimed in claim 9, wherein the composite material is used in the fields of overvoltage protection, lightning surge protection, static electricity prevention and adaptive electromagnetic pulse protection.
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| 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 |
| 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 |
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