CN111534049A - High-thermal-conductivity and high-electrical-conductivity carbon fiber polymer-based composite material and preparation method thereof - Google Patents
High-thermal-conductivity and high-electrical-conductivity carbon fiber polymer-based composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a high-thermal-conductivity and electric-conductivity carbon fiber polymer-based composite material and a preparation method thereof; the composite material is prepared by taking carbon fibers with uniform diameters as raw materials, preparing a carbon fiber soft felt oriented in a plane by utilizing an air flow network forming technology and a needle punching method, then depositing silver nanoparticles on the surface of the carbon fibers by adopting a solvent reduction method to prepare a novel carbon fiber-silver nanoparticle hybrid fiber felt, uniformly doping high-thermal-conductivity filler into the carbon fiber-silver nanoparticle hybrid fiber felt by utilizing a vacuum filtration method, and finally preparing the carbon fiber-silver nanoparticle hybrid fiber felt through a vacuum assisted transfer molding compound forming process (RTM) and an annealing process. The composite material introduces nano silver particles and other high-heat-conductivity fillers on the basis of carbon fibers to realize synergistic action and increase a heat-conducting path, realizes ordered arrangement of hybrid carbon fibers in a polymer by utilizing a compression limited range, and connects the carbon fibers with one another and other heat-conducting fillers through a low-melting-point nano silver melting technology, so that the heat-conducting path of the composite material is increased, the thermal resistance among the fillers is reduced, and the heat conduction, mechanics, electrical performance and electromagnetic shielding effectiveness of the composite material are effectively increased.
Description
Technical Field
The invention belongs to the technical field of preparation of heat-conducting and electric-conducting composite materials, and particularly relates to a high-heat-conducting and electric-conducting carbon fiber polymer-based composite material and a preparation method thereof.
Background
With the rapid development of the electronic information industry, the application of electronic components gradually develops towards the directions of high power, high integration and high density, and the problem of heat dissipation becomes a bottleneck restricting the development of the industries of integrated circuits, high-power electronic components, high-power lighting devices, high-power electric locomotives and hybrid locomotives. The heat dissipation problem of electronic components causes the fault to reach 55% of the total fault, so that the service life of product equipment is reduced, people put forward more recent and higher requirements on heat conduction materials, besides high heat conductivity, the heat dissipation material also needs to have a lower expansion coefficient to ensure the packaging of electronic components, and in addition, the heat dissipation material also needs to have excellent comprehensive properties such as light weight, excellent mechanical property, easy process, chemical corrosion resistance and the like. Especially, the light weight has important significance in the field of aerospace aircrafts. The development of the electronic information industry has promoted the development of heat conductive materials.
The polymer material has the excellent characteristics of light weight, chemical corrosion resistance, easy processing and forming, excellent electrical insulation performance, excellent mechanical and fatigue resistance performance and the like, and gradually replaces the traditional metal and ceramic heat conduction materials. Especially, in the recently developed Light Emitting Diode (LED) industry, the government and the enterprise have been vigorously developed due to the characteristics of energy saving, environmental protection, high brightness, etc., but the high power and the small volume make the heat dissipation problem become the bottleneck restricting the development. Wherein 75-80% of the electrical energy is dissipated in a thermal manner, which seriously affects the service life of the LED, and the heat is mainly solved by the heat conductive material and the structural design.
How to improve the heat conduction and the heat conduction performance of the epoxy composite material of the insulating layer simultaneously, improve the service life of the LED chip, solve the heat dissipation problem of the honeycomb structure board in the aerospace field and the electromagnetic shielding effectiveness become important issues once.
Disclosure of Invention
The invention aims to solve the problems of low heat-conducting property increasing efficiency, high heat resistance among fillers, poor electric conductivity of the composite material, low electromagnetic shielding efficiency and the like of the existing filling type heat-conducting and electric-conducting composite material along with the increase of the content of the fillers. The invention takes carbon fiber as raw material, utilizes airflow network forming technology and needle punching method to prepare carbon fiber soft felt oriented in plane, and then deposits silver nano particles on the surface of the carbon fiber to prepare novel carbon fiber silver nano particle hybrid fiber felt. And (3) doping the high-thermal-conductivity filler into the carbon fiber silver nanoparticle hybrid fiber felt by adopting a vacuum filtration method, and finally preparing the high-thermal-conductivity high-performance fiber composite material by adopting a vacuum-assisted transfer molding compound forming process. The research introduces nano silver and high-thermal-conductivity filler on the basis of carbon fiber to realize synergistic action and increase a thermal conduction path, realizes ordered arrangement of the thermal-conductivity filler in the hybrid carbon fiber by utilizing a compression limited domain, connects the carbon fiber and the thermal-conductivity filler with each other by a low-melting-point nano silver melting technology, realizes reduction of thermal resistance, synergistic increase of thermal conductivity and electrical conductivity of a fully-connected carbon fiber-nano silver-thermal-conductivity filler hybrid fiber felt, regulates and controls a filler network, designs and optimizes a high-density low-thermal-resistance high-conductivity network, and achieves the aims of improving the thermal conductivity and electromagnetic shielding efficiency of a polymer composite material.
The purpose of the invention is realized by the following technical scheme:
the high-thermal-conductivity and electric-conductivity carbon fiber polymer matrix composite material comprises 0.1-50% of thermal-conductivity filler, 0.01-10% of nano-silver and 0.1-50% of carbon fiber; the nano-silver hybrid carbon fibers in the composite material are arranged in a vertical direction in an oriented manner.
The size diameter of the carbon fiber is 100nm-50 μm; the nano silver has a particle size of 1-90 nm.
The heat conducting filler comprises one or more of boron nitride nanosheets, graphene oxide nanosheets, graphene, metal nanosheets, transition metal carbon, nitride (MXene), boron nitride nanotubes, carbon nanotubes, silicon carbide nanowires, metal nanowires or metal particles.
The polymer is selected from one or more of epoxy resin, polyimide, silicon rubber, polyacrylic acid, phenolic resin, urea resin or polyurethane.
The preparation method of the high-thermal-conductivity and electric-conductivity carbon fiber polymer-based composite material comprises the following steps:
A. the method comprises the following steps of taking one-dimensional carbon fibers with uniform size distribution as raw materials, preparing a carbon fiber composite soft felt formed by stacking x-axis and y-axis planes through an airflow network forming technology, and penetrating partial fibers along the up-down direction of a z-axis through a needle punching method to form the carbon fiber soft felt;
B. b, reducing silver nitrate in polyvinylpyrrolidone (PVP) aqueous solution through N, N Dimethylformamide (DMF) to deposit silver particles on the surface of the carbon fiber soft felt obtained in the step A, and wrapping the carbon fiber felt by using a metal copper mesh in the process to prevent the whole orientation arrangement structure of the carbon fiber felt from being damaged in the reaction process, so as to obtain the carbon fiber hybrid composite fiber with deposited nano silver particles;
C. b, paving the nano silver particle deposited carbon fiber hybrid composite fiber obtained in the step B in a Buchner funnel by adopting a vacuum filtration method, uniformly pouring high-thermal-conductivity filler solutions with different contents into the Buchner funnel in the vacuumizing process, and drying to prepare the high-thermal-conductivity filler doped carbon fiber/silver nano particle composite fiber soft felt;
D. and D, taking the high-thermal-conductivity filler-doped carbon fiber/silver nanoparticle composite fiber soft felt obtained in the step C as a thermal-conductivity filler network, completely soaking the composite fiber soft felt in a polymer prepolymer at room temperature by adopting a vacuum Resin Transfer Molding (RTM), curing at high temperature under pressure, and then annealing at high temperature to prepare the carbon fiber nano-silver polymer composite material.
In the step A, the proportion of the x-y plane of the carbon fiber soft felt to the fibers in the z direction can be regulated to (50-250): 1.
in the step B, the concentration of the silver nitrate in the aqueous solution is 5-20 mg/mL.
In the step C, the solvent of the high thermal conductive filler solution is one or more selected from N, N-dimethylformamide, tetrahydrofuran, ethanol, acetone, deionized water, dimethyl sulfoxide and ethyl acetate.
In the step D, the pressure is 5-30 MPa; the high-temperature curing temperature is 90-250 ℃, and the time is 0.5-12 h; the high-temperature annealing temperature is 100-250 ℃, and the time is 0.5-12 h.
The invention takes carbon fiber as raw material, utilizes airflow network forming technology and needle punching method to prepare carbon fiber soft felt oriented in plane, and then deposits silver nano particles on the surface of the carbon fiber to prepare novel carbon fiber silver nano particle hybrid fiber felt. And (3) doping the high-thermal-conductivity filler into the carbon fiber silver nanoparticle hybrid fiber felt by adopting a vacuum filtration method, and finally preparing the high-thermal-conductivity high-performance fiber composite material by adopting a vacuum-assisted transfer molding compound forming process. The invention introduces nano silver and high heat conduction filler on the basis of carbon fiber to realize synergistic action and increase heat conduction path, realizes ordered arrangement of the heat conduction filler in the hybrid carbon fiber by utilizing compression limited domain, and connects the carbon fiber and the heat conduction filler with each other by a low-melting-point nano silver melting technology to form a filler network structure containing mutually contacted and oriented arrangement. The special structure can enable the filler to form a high-efficiency heat conduction path in the filled composite material, the purpose that the heat conduction performance of the polymer-based composite material can be obviously improved by adding a small amount of high-heat-conduction filler is achieved, and the composite material is anisotropic, has high heat conduction and electric conductivity in the vertical direction and has more advantages in heat management application. The preparation method of the similar heat-conducting composite filler is not reported.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention designs and prepares a novel and efficient heat-conducting and electric-conducting filler frame, which is based on a self-made anisotropic carbon fiber soft felt, utilizes the melting characteristic of nano-silver particles, dopes high-heat-conducting filler to construct a heat-conducting and electric-conducting bridge between carbon fibers, prepares a polymer composite material which has vertical orientation and is rich in heat-conducting and electric-conducting circuit lines, effectively reduces the interface thermal resistance between the fillers and achieves the purpose of greatly improving the heat-conducting performance and the electromagnetic shielding effectiveness of the composite filler;
2. in the composite material constructed by the invention, high vertical direction thermal conductivity and high electrical conductivity can be achieved under the condition of smaller filler content, so that the addition amount of expensive high thermal conductivity filler is effectively reduced, and the production cost of the composite material is reduced;
3. the filler network structure constructed by doping the high-thermal-conductivity filler among the carbon fibers by utilizing the melting characteristic of the nano-silver particles can obviously improve the thermal conductivity of the material, is expected to be applied to electronic devices as an interface thermal management material, and has wide application prospect;
4. the heat-conducting and electric-conducting polymer composite material disclosed by the invention is simple in preparation process, economic in cost and suitable for large-scale industrial production.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a schematic view showing a process for producing a carbon fiber soft felt obtained in example 1 of the present invention;
FIG. 2 is a flow chart illustrating a process for preparing the epoxy resin/carbon fiber/nano silver/thermal conductive filler composite prepared in example 1;
fig. 3 is a graph of the morphology of the carbon fiber soft felt before and after silver deposition prepared in example 1.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit of the invention. All falling within the scope of the present invention.
The test specimen of the present invention was molded by hot pressing in a flat vulcanizing machine (model QLB-D, shanghai rubber machinery factory).
The morphology of the polymer prepared by the invention and the composite fiber thereof is observed by a field emission Scanning Electron Microscope (SEM) (Nova NanoSEM 450 model, FEI company in USA).
The heat conductivity of the sample prepared by the invention is measured by adopting a laser heat conduction instrument (LFA 457 HT HyperFlash @, NanoFlash, Netzsch).
Example 1
The embodiment relates to a high-thermal-conductivity and high-electrical-conductivity carbon fiber polymer-based composite material and a preparation method thereof, wherein the composite material is prepared by doping silver nanowires with nano silver particles to hybridize a carbon fiber composite felt and then performing a vacuum assisted transfer molding compound forming process and an annealing process; the nano-silver hybrid composite fibrofelt is a composite carbon fiber soft felt formed by depositing nano-silver particles on the surface of a carbon fiber felt through DMF (dimethyl formamide) reduction of silver nitrate; the nano silver is melted in the composite material at 150 ℃ to connect the carbon fiber and the silver nanowire with each other, so that a fully-connected hybrid heat-conducting network is realized, the thermal resistance is reduced, and the heat conduction and the electrical property are increased. The composite material is prepared by the following steps:
A. preparing anisotropic carbon fiber soft felt: a carbon fiber composite soft felt formed by stacking x-axis planes and y-axis planes is prepared by taking one-dimensional carbon fibers (the diameter is about 10 mu m) with uniform size distribution as raw materials through an airflow network forming technology, and is shown in figure 1. In the soft felt structure, the fibers are randomly and disorderly arranged in a plane, and the fibers have no binding force and are very easy to disperse. On the basis, part of the fibers penetrate through the fibers randomly dispersed in the plane along the vertical direction of the z axis by a needle punching method to form the carbon fiber soft felt. The existence of the z-axis fibers increases the bonding force between the upper fiber layer and the lower fiber layer, so that the fiber felt is an integral soft carbon fiber felt with an x-y-z structure. In the anisotropic structure of the long carbon fiber, the ratio of the x-y plane to the z-direction fiber can be regulated to be 100: 1;
B. preparing the hybrid composite fiber of the carbon fiber with deposited nano silver particles: by 500mL of N, N Dimethylformamide (DMF) and 20g of AgNO3Mixing of aqueous solutions (10mg/mL)Adding a certain amount of PVP and fully stirring. And (3) wrapping the carbon fiber felt by using a metal copper mesh to prevent the overall orientation arrangement structure of the carbon fiber felt from being damaged in the reaction process, and adding the carbon fiber felt into the mixed solution to react for 1h at 45 ℃. Putting the hybrid composite fiber into an oven at 80 ℃ for drying for 6 hours;
C. preparing the silver nanowire doped carbon fiber/silver nanoparticle composite fiber: b, paving the nano silver particle deposited carbon fiber hybrid composite fiber obtained in the step B in a Buchner funnel by adopting a vacuum filtration method, uniformly pouring ethanol solution (200mL) containing 0.1g of silver nanowires subjected to ultrasonic dispersion for 30 minutes in advance into the Buchner funnel in the vacuumizing process, filtering, and then putting into an oven at 80 ℃ for drying treatment to prepare the silver nanowire doped carbon fiber/silver nano particle composite fiber soft felt;
D. preparing a carbon fiber/nano silver polymer composite material: epoxy resin and a curing agent are firstly uniformly mixed, a nano-wire-doped carbon fiber/silver nano-particle composite fiber soft felt is used as a heat-conducting filler network, 5g of the composite fiber soft felt is completely immersed in the epoxy resin by adopting a vacuum resin transfer molding method (RTM) at room temperature, and the RTM method has the advantages that no air holes exist in the system, and simultaneously the RTM method can perform space compression on the carbon fiber soft felt to limit the area and increase the contact of silver nano-wires with carbon fibers and silver nano-particles, so that the ordered arrangement of carbon fiber/nano-silver frames is maintained. The carbon fiber nano silver polymer composite material is prepared by mould pressing at 100 ℃ for 60 minutes under the pressure of 10MPa, high-temperature curing and then high-temperature annealing at 150 ℃ for 6 hours, and the preparation process of the composite material is shown in figure 2.
The implementation effect is as follows: the invention prepares the high-thermal-conductivity and electric-conductivity composite material with the carbon fiber-nano silver particle-nano silver wire structure which is oriented and connected with each other. As shown in the Scanning Electron Microscope (SEM) photograph of fig. 3, in the carbon fiber prepared in example 1, straight fibers were entangled with each other, the direction of the fibers was randomly distributed, and the diameter distribution range of the fibers was narrow at 80 to 12 μm. Furthermore, the surface of the fibers was smooth and no significant beading, fiber agglomeration or fiber entanglement was found. It can be seen in fig. 3b that the silver nanoparticles are well uniformly coated on the fiber in the form of individual particles, with a size of 20-50 nm. By applying the inventionThe prepared polymer composite material is tested for heat conductivity, and the conductivity of the pure polymer is 2.3 × 10-7S/cm, thermal conductivity of 0.18W/(m.K), electrical conductivity of the composite material in the fiber orientation direction and the direction perpendicular to the fiber direction of 0.72 and 0.0058S/cm, and thermal conductivity of the composite material in the fiber orientation direction and the direction perpendicular to the fiber direction of 0.92 and 0.31W/(m.K). It can be found that the composite material achieves a great increase in-plane thermal conductivity with less silver nanofibers and exhibits a higher thermal conductivity anisotropy. The above results show that compared with the prior art, the oriented and surface-contact network structure prepared by the invention has outstanding advantages in improving the thermal conductivity, and the polymer matrix composite material has high thermal conductivity increasing efficiency.
Comparative example 1
The comparative example relates to a preparation method of a heat-conducting epoxy resin composite material, wherein the composite material is formed by uniformly mixing 5g of carbon fibers, 0.1g of silver nanoparticles and 0.2g of silver nanowires. The nano composite material which is directly hot-pressed and randomly dispersed is prepared by grinding the mixed powder of the fillers, uniformly mixing the mixed powder with the epoxy resin and the curing agent, carrying out die pressing for 1 hour at 100 ℃ and under the pressure of 10MPa, taking out the mixture, and carrying out high-temperature annealing treatment for 6 hours in a vacuum oven.
The implementation effect that the conductivity of the pure polymer is 2.3 × 10 by testing the heat conductivity of the polymer composite material prepared by the comparative example 1-7S/cm, thermal conductivity of 0.18W/(m.K), electrical conductivity of 0.011S/cm, and thermal conductivity of 0.39W/(m.K) were observed, and the composite material achieved certain improvements in thermal and electrical conductivity with less silver nanowire addition, but it can be seen that the composite material in comparative example 1 had a relatively significantly lower thermal and electrical conductivity with the same silver addition.
Comparative example 2
The comparative example relates to a preparation method of a heat-conducting epoxy resin composite material, the composite material takes 5g of randomly oriented carbon fibers as a raw material, nano-silver particle deposited carbon fiber hybrid composite fibers are prepared by the same method as the step B in the example 1, 0.2g of silver nanowires, epoxy resin and a curing agent are uniformly mixed, the nano-silver particle deposited carbon fiber hybrid composite fibers are completely immersed in a composite epoxy resin prepolymer by a vacuum resin transfer molding method (RTM) at room temperature, the mixture is molded for 60 minutes at the pressure of 10MPa and the temperature of 100 ℃, and then the mixture is cured at high temperature and then annealed at the temperature of 150 ℃ for 6 hours to prepare the uniformly dispersed carbon fiber nano-silver polymer composite material.
The implementation effect is that the conductivity of the pure polymer is 2.3 × 10 by testing the heat conductivity of the polymer composite material prepared by the comparative example 2-7S/cm, thermal conductivity of 0.18W/(m · K), electrical conductivity of 0.034S/cm, and thermal conductivity of 0.46W/(m · K) of the composite material, it can be seen that the composite material achieves a certain improvement in thermal and electrical conductivity over comparative example 1 due to the contribution of nano-silver deposition, but it can be seen that the thermal and electrical conductivity of the composite material in comparative example 2 is significantly lower than that of the composite material in example 1 at the same amount of silver added.
Comparative example 3
This comparative example relates to a method of preparing a thermally conductive epoxy resin composite material having an anisotropic carbon fiber soft felt prepared by the same method as in step B of example 1. 0.1g of silver nano particles and 0.2g of silver nano wires are uniformly mixed, the anisotropic carbon fiber soft felt is completely soaked in the composite epoxy resin prepolymer by adopting a vacuum resin transfer molding method (RTM) at room temperature, no air holes exist in the system, meanwhile, the anisotropic carbon fiber soft felt can be subjected to space compression and limited area to increase the mutual contact of the silver nano wires, the carbon fibers and the silver nano particles, and the ordered arrangement of the carbon fibers and the nano silver framework is kept. The carbon fiber nano silver polymer composite material is prepared by die pressing for 60 minutes at the pressure of 10MPa and the temperature of 100 ℃, curing at high temperature and then annealing at the temperature of 150 ℃ for 6 hours.
The implementation effect is as follows: by testing the thermal conductivity of the polymer composite material prepared in comparative example 2, the electrical conductivity of the composite material in the fiber orientation direction and the direction perpendicular to the fiber direction was 0.29 and 0.023S/cm, and the thermal conductivity of the composite material in the fiber orientation direction and the direction perpendicular to the fiber direction was 0.65 and 0.34W/(m.K). It can be found that the composite material achieves certain improvement of the thermal conductivity and the electrical conductivity compared with comparative example 1 and comparative example 2 due to certain anisotropy, but it can be seen that the thermal conductivity and the electrical conductivity are relatively obviously lower compared with the composite material in example 1 under the same addition amount.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (9)
1. The high-thermal-conductivity and electric-conductivity carbon fiber polymer matrix composite is characterized in that the filling volume of a thermal conductive filler in the composite is 0.1-50%, the filling volume of nano silver is 0.01-10%, and the filling volume of carbon fiber is 0.1-50%; the nano silver and the carbon fiber in the composite material are arranged in a vertical direction in an oriented manner;
the size diameter of the carbon fiber is 100nm-50 μm; the grain diameter of the nano silver is 1-90 nm.
2. The composite material of claim 1, wherein the thermally conductive filler is selected from one or more of boron nitride nanoplates, graphene oxide nanoplates, graphene, metal nanoplates, transition metal carbon, nitride (MXene), boron nitride nanotubes, carbon nanotubes, silicon carbide nanowires, metal nanowires, or metal particles.
3. The composite material of claim 1, wherein the polymer is selected from one or more of epoxy, polyimide, silicone rubber, polyacrylic acid, phenolic resin, urea formaldehyde resin, or polyurethane.
4. The preparation method of the composite material of any one of claims 1 to 3, wherein the composite material is prepared by doping the nano-silver hybrid carbon fiber composite felt with the high thermal conductive filler and then performing a vacuum assisted transfer molding compound molding process (RTM) and an annealing process; the nano-silver hybrid composite fibrofelt is a composite carbon fiber soft felt formed by depositing nano-silver particles on the surface of a carbon fiber felt through a solution reduction method; the nano silver is melted in the composite material at low temperature to connect the carbon fiber and the high-thermal-conductivity filler, so that a fully-connected hybrid thermal-conductive network is realized, the thermal resistance is reduced, and the thermal conductivity and the electrical property are improved.
5. The method for preparing according to claim 4, characterized in that it comprises the steps of:
A. the method comprises the following steps of taking one-dimensional carbon fibers with uniform size distribution as raw materials, preparing a carbon fiber composite soft felt formed by stacking x-axis and y-axis planes through an airflow network forming technology, and penetrating partial fibers along the up-down direction of a z-axis through a needle punching method to form the carbon fiber soft felt;
B. b, reducing silver nitrate in polyvinylpyrrolidone (PVP) aqueous solution through N, N Dimethylformamide (DMF) to deposit silver particles on the surface of the carbon fiber soft felt obtained in the step A, and wrapping the carbon fiber felt by using a metal copper mesh in the process to prevent the whole orientation arrangement structure of the carbon fiber felt from being damaged in the reaction process, so as to obtain the carbon fiber hybrid composite fiber with deposited nano silver particles;
C. b, paving the nano silver particle deposited carbon fiber hybrid composite fiber obtained in the step B in a Buchner funnel by adopting a vacuum filtration method, uniformly pouring high-thermal-conductivity filler solutions with different contents into the Buchner funnel in the vacuumizing process, and drying to prepare the high-thermal-conductivity filler doped carbon fiber/silver nano particle composite fiber soft felt;
D. and D, taking the high-thermal-conductivity filler-doped carbon fiber/silver nanoparticle composite fiber soft felt obtained in the step C as a thermal-conductivity filler network, completely soaking the composite fiber soft felt in a polymer prepolymer at room temperature by adopting a vacuum Resin Transfer Molding (RTM), curing at high temperature under pressure, and then annealing at high temperature to prepare the carbon fiber nano-silver polymer composite material.
6. The preparation method of the carbon fiber polymer matrix composite material with high thermal and electrical conductivity as claimed in claim 5, wherein in the step A, the ratio of the x-y plane and z direction fibers of the carbon fiber soft felt can be regulated and controlled to be (50-250): 1.
7. the method for preparing a carbon fiber polymer matrix composite with high thermal and electrical conductivity as claimed in claim 5, wherein in the step B, the concentration of the silver nitrate in the aqueous solution is 5-20 mg/mL.
8. The method according to claim 5, wherein in step C, the solvent of the high thermal conductive filler solution is one or more selected from N, N-dimethylformamide, tetrahydrofuran, ethanol, acetone, deionized water, dimethyl sulfoxide, and ethyl acetate.
9. The method for preparing a high thermal conductive anisotropic polymer matrix composite according to claim 5, wherein in the step D, the pressure is 5 to 30 MPa; the high-temperature curing temperature is 90-250 ℃, and the time is 0.5-12 h; the high-temperature annealing temperature is 100-250 ℃, and the time is 0.5-12 h.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112563858A (en) * | 2020-12-03 | 2021-03-26 | 安徽爱意爱机电科技有限公司 | Four-way conductive slip ring suitable for high-temperature environment |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109161167A (en) * | 2018-08-29 | 2019-01-08 | 中国科学院深圳先进技术研究院 | A kind of boron nitride-silver/epoxy resin composite material and its preparation method and application |
| JP2019023268A (en) * | 2016-07-29 | 2019-02-14 | 名古屋ファインケミカル株式会社 | Epoxy composition, method for curing the same, and method for storing the same |
| CN110228248A (en) * | 2019-05-10 | 2019-09-13 | 上海交通大学 | A kind of high thermal conductivity anisotropic polymer based composites and preparation method thereof |
-
2020
- 2020-05-08 CN CN202010380312.5A patent/CN111534049B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019023268A (en) * | 2016-07-29 | 2019-02-14 | 名古屋ファインケミカル株式会社 | Epoxy composition, method for curing the same, and method for storing the same |
| CN109161167A (en) * | 2018-08-29 | 2019-01-08 | 中国科学院深圳先进技术研究院 | A kind of boron nitride-silver/epoxy resin composite material and its preparation method and application |
| CN110228248A (en) * | 2019-05-10 | 2019-09-13 | 上海交通大学 | A kind of high thermal conductivity anisotropic polymer based composites and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| HAO WANG等: "Efficient Thermal Transport Highway Construction Within Epoxy Matrix via Hybrid Carbon Fibers and Alumina Particles", 《ACS OMEGA》 * |
| KAI SUN等: "Flexible silver nanowire/carbon fiber felt metacomposites with weakly negative permittivity behavior", 《PHYSICAL CHEMISTRY CHEMICAL PHYSICS》 * |
Cited By (15)
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