CN107686635B - Preparation method of graphene/solid epoxy resin high-thermal-conductivity composite material - Google Patents
Preparation method of graphene/solid epoxy resin high-thermal-conductivity composite material Download PDFInfo
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- CN107686635B CN107686635B CN201710997458.2A CN201710997458A CN107686635B CN 107686635 B CN107686635 B CN 107686635B CN 201710997458 A CN201710997458 A CN 201710997458A CN 107686635 B CN107686635 B CN 107686635B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
- B02C17/10—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls with one or a few disintegrating members arranged in the container
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
- B29C44/04—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles consisting of at least two parts of chemically or physically different materials, e.g. having different densities
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/34—Auxiliary operations
- B29C44/60—Measuring, controlling or regulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
Abstract
The invention relates to a preparation method of a graphene/solid epoxy resin high-thermal-conductivity composite material. The method comprises the steps of carrying out cold mould pressing operation on graphene in a mould after the surface of solid epoxy resin is coated, enabling the graphene materials to be in contact with each other under the action of pressure to form a heat conduction channel, then carrying out heating treatment on the mixture, enabling the solid epoxy resin to partially break through isolated graphene sheets under the action of heat and pressure, realizing sintering and curing among epoxy resin particles, realizing the structural and functional integration of the materials, and obtaining the high-heat-conductivity composite material.
Description
Technical Field
The invention relates to the field of high-heat-conductivity materials, in particular to a preparation method of a graphene/solid epoxy resin high-heat-conductivity composite material.
Background
In recent years, the size of each chip is further reduced, the power is increased, heat is concentrated in the small-sized chip, the heat density of the chip is higher, and when the junction temperature changes, microscopic parameters such as internal electron and hole concentration, forbidden bandwidth, carrier mobility and the like are changed, so that a series of problems such as accelerated aging of the chip, shortened service life and the like are caused, and even the chip fails. Therefore, new high thermal conductivity composite materials are imperative.
Graphene is a two-dimensional single-layer carbon atom crystal, and compared with a three-dimensional material, the low-dimensional structure of graphene can significantly reduce boundary scattering of phonons at grain boundaries and endow the graphene with a special phonon diffusion mode. Thermal conductivity is a fundamental physical property of graphene materials, even up to 5300W/m-k. Due to the rapid heat conduction and heat dissipation characteristics of the graphene, the graphene becomes an excellent heat dissipation material, and can be used for heat dissipation of devices such as smart phones, tablet computers, high-power energy-saving LEDs, satellite circuits and laser weapons. Although graphene has great potential in the field of thermal management, these properties are based on its microscopic nanoscale and are difficult to directly utilize. Therefore, the preparation of the nano-scale graphene material into a macroscopic material and the maintenance of the nano effect of the macroscopic material, and the reduction of the interface contact thermal resistance between the macroscopic material and the substrate are important ways for the large-scale application of graphene in thermal management.
There are mentioned in an article "graphene/epoxy resin composite research progress" published by wane of the institute of materials science and engineering, university of wuhan and chinese science and dawn and once dawn: mixing graphene nanoplatelets into an epoxy matrix by using a double-center mixing disperser, or uniformly dispersing the graphene nanoplatelets into the epoxy matrix by using a ball milling mode, or grafting graphene oxide with thermotropic liquid crystal epoxy molecules; the graphene/epoxy resin composite material prepared by the method has good thermal conductivity. In the prior art, various solvents are added for catalysis in the preparation of the graphene/epoxy resin composite material. A pure graphene/epoxy composite material cannot be obtained.
Graphene has high theoretical thermal conductivity, and the thermal conductivity coefficient is as high as 5300W/m.k, and the traditional preparation method of the high-thermal-conductivity graphene resin composite material is to mix graphene into a resin material system, so that the graphene material is wrapped in a resin matrix, and the graphene is isolated, and the high-thermal-conductivity graphene resin matrix composite material cannot be obtained. Therefore, the structure of graphene as a high thermal conductivity reinforcing material needs to be designed and optimized.
The graphene is organically combined with the epoxy resin, and the high polymer material is modified by utilizing the rapid heat conduction characteristic and the rapid heat dissipation characteristic of the graphene, so that the good balance of the heat conduction characteristic and the processability can be achieved. The high-thermal-conductivity graphene/epoxy resin composite material can achieve the heat dissipation performance comparable to that of metal.
Disclosure of Invention
The invention is to provide a preparation method of a graphene/solid epoxy resin high-thermal-conductivity composite material, which has the advantages of low cost, no organic solvent, no toxicity, environmental protection, convenience in operation, easiness in industrial production and the like.
In order to solve the technical problems, the technical scheme of the invention is as follows: a preparation method of a graphene/solid epoxy resin high-thermal-conductivity composite material comprises the following steps:
(1) selecting solid epoxy resin with the mass fraction of 90-99.9 wt% and graphene with the mass fraction of 0.1-10 wt%; the solid epoxy resin also comprises 5-45% of a curing agent;
(2) uniformly mixing solid epoxy resin and graphene, and then sending the mixture into a mould for cold mould pressing and forming; the uniform mixing is completed in a ball mill, and the solid epoxy resin and the graphene are subjected to ball milling modification to be tightly combined and ensure that graphene sheet layers are in good contact;
(3) and heating and curing the formed material to obtain the high-heat-conductivity composite material.
Further, the step (3): or directly heating and curing in the mould after cold mould pressing and forming on the mould to obtain the high-heat-conductivity composite material.
Further, the curing agent is one or more of a dicyandiamide curing agent, an imidazole curing agent or an anhydride curing agent.
Further, the graphene is single-layer graphene or few-layer graphene nanoplatelets.
Further, the solid epoxy resin matrix is NPES-602 or NPES-605. Or other similar solid epoxy designation.
Further, the ball milling time is 12-120 hours.
Further, the pressure of the cold die pressing is 10-200 MPa.
Further, the temperature for heating and curing is 100-180 ℃.
Compared with the prior art, the invention has the following beneficial effects:
1. carrying out ball milling modification after the solid epoxy resin is wrapped with graphene, and carrying out cold die pressing and then heating curing to obtain the high-thermal-conductivity graphene/solid epoxy resin composite material;
2. the product of the invention has extremely high heat conductivity, the highest heat conductivity coefficient is more than 32.0W/mK, and the temperature resistance is good, so the product can be normally used at 150 ℃;
3. the product has the advantages of low cost, no solvent, environmental protection, convenient operation and easy industrial production, is an excellent high-heat-conducting material, and can be widely applied to the fields of heat dissipation devices, electronic equipment, chemical energy sources, automobile industry, aerospace and the like.
Detailed Description
Example 1: ball-milling graphene, solid epoxy resin powder and a curing agent for 12 hours, wherein the content of the graphene is 0.1 wt%, the content of the solid epoxy resin matrix and the curing agent is 99.9 wt% (wherein the curing agent accounts for 5%), uniformly mixing, performing cold mould pressing treatment, the pressure is 10MPa, releasing the pressure, taking out a sample, heating to 120 ℃ and curing to obtain the graphene/solid epoxy resin high-thermal-conductivity composite material. The thermal conductivity of the composite material is 0.8W/mK.
Example 2: ball-milling graphene, solid epoxy resin powder and a curing agent for 48 hours, wherein the content of the graphene is 1 wt%, the content of the solid epoxy resin matrix and the curing agent is 99 wt% (wherein the curing agent accounts for 15%), uniformly mixing, then carrying out cold mould pressing treatment, the pressure is 100MPa, releasing pressure, taking out a sample, heating to 120 ℃ and curing to obtain the graphene/solid epoxy resin high-thermal-conductivity composite material. The thermal conductivity of the composite material was 6.1W/mK.
Example 3: ball-milling graphene, solid epoxy resin powder and a curing agent for 72 hours, wherein the content of the graphene is 5 wt%, the content of the solid epoxy resin matrix and the curing agent is 95 wt% (wherein the curing agent accounts for 20%), uniformly mixing, then carrying out cold mould pressing treatment, the pressure is 100MPa, releasing pressure, taking out a sample, heating to 150 ℃ and curing to obtain the graphene/solid epoxy resin high-thermal-conductivity composite material. The thermal conductivity of the composite material is 30.2W/mK.
Example 4: ball-milling graphene, solid epoxy resin powder and a curing agent for 120 hours, wherein the content of the graphene is 10 wt%, the content of the solid epoxy resin matrix and the curing agent is 90 wt% (wherein the curing agent accounts for 25%), uniformly mixing, then carrying out cold mould pressing treatment, the pressure is 200MPa, releasing pressure, taking out a sample, heating to 180 ℃ and curing to obtain the graphene/solid epoxy resin high-thermal-conductivity composite material. The thermal conductivity of the composite material was 21.6W/mK.
Example 5: ball-milling graphene, solid epoxy resin powder and a curing agent for 48 hours, wherein the content of the graphene is 6 wt%, the content of the solid epoxy resin matrix and the curing agent is 94 wt% (wherein the curing agent accounts for 30%), uniformly mixing, performing cold mould pressing treatment under the pressure of 120MPa, relieving pressure, taking out a sample, heating to 150 ℃ and curing to obtain the graphene/solid epoxy resin high-thermal-conductivity composite material. The thermal conductivity of the composite material is 32.5W/mK.
Example 6: ball-milling graphene, solid epoxy resin powder and a curing agent for 96 hours, wherein the content of the graphene is 4 wt%, the content of the solid epoxy resin matrix and the curing agent is 96 wt% (wherein the curing agent accounts for 35%), uniformly mixing, then carrying out cold mould pressing treatment, the pressure is 80MPa, releasing pressure, taking out a sample, heating to 100 ℃ and curing to obtain the graphene/solid epoxy resin high-thermal-conductivity composite material. The thermal conductivity of the composite material is 24.8W/mK.
Example 7: ball-milling graphene, solid epoxy resin powder and a curing agent for 24 hours, wherein the content of the graphene is 2 wt%, the content of the solid epoxy resin matrix and the curing agent is 98 wt% (45% of the curing agent), uniformly mixing, performing cold mould pressing treatment under the pressure of 15MPa, relieving pressure, taking out a sample, heating to 160 ℃, and curing to obtain the graphene/solid epoxy resin high-thermal-conductivity composite material. The thermal conductivity of the composite material is 18.8W/mK.
By comparing example 1 with example 7, it can be shown that the graphene is coated with the solid epoxy resin and then is subjected to cold die pressing, and graphene materials are contacted with each other under the action of pressure to form a heat conduction channel, but the graphene cannot obtain a high heat conduction composite material with practical use strength only by physical engagement. Therefore, the mixture of the solid epoxy resin and the graphene is heated, so that the solid epoxy resin partially breaks through the isolated graphene sheet layer under the action of heat and pressure, sintering and curing are realized among the epoxy resin particles, the heat-conducting composite material with certain strength is obtained, and the structural and functional integration of the material is realized.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (8)
1. A preparation method of a graphene/solid epoxy resin high-thermal-conductivity composite material is characterized by comprising the following steps:
(1) selecting solid epoxy resin with the mass fraction of 90-99.9 wt% and graphene with the mass fraction of 0.1-10 wt%; the solid epoxy resin also comprises 5-45% of a curing agent;
(2) uniformly mixing solid epoxy resin and graphene, and then sending the mixture into a mould for cold mould pressing and forming; the uniform mixing is completed in a ball mill, and the solid epoxy resin and the graphene are subjected to ball milling modification to be tightly combined and ensure that graphene sheet layers are in good contact;
(3) and heating and curing the formed material to obtain the high-heat-conductivity composite material.
2. The preparation method of the graphene/solid epoxy resin high-thermal-conductivity composite material according to claim 1, characterized in that: the step (3): or directly heating and curing in the mould after cold mould pressing and forming on the mould to obtain the high-heat-conductivity composite material.
3. The preparation method of the graphene/solid epoxy resin high-thermal-conductivity composite material according to claim 1, characterized in that: the curing agent is one or more of dicyandiamide curing agent, imidazole curing agent or anhydride curing agent.
4. The preparation method of the graphene/solid epoxy resin high-thermal-conductivity composite material according to claim 1, characterized in that: the graphene is single-layer graphene or few-layer graphene nanoplatelets.
5. The preparation method of the graphene/solid epoxy resin high-thermal-conductivity composite material according to claim 1, characterized in that: the solid epoxy resin matrix is NPES-602 or NPES-605.
6. The preparation method of the graphene/solid epoxy resin high-thermal-conductivity composite material according to claim 1, characterized in that: the ball milling time is 12-120 hours.
7. The preparation method of the graphene/solid epoxy resin high-thermal-conductivity composite material according to claim 1, characterized in that: the pressure of the cold die pressing is 10-200 MPa.
8. The preparation method of the graphene/solid epoxy resin high-thermal-conductivity composite material according to claim 1, characterized in that: the temperature for heating and curing is 100-180 ℃.
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| CN201710997458.2A CN107686635B (en) | 2017-10-24 | 2017-10-24 | Preparation method of graphene/solid epoxy resin high-thermal-conductivity composite material |
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| CN107686635A CN107686635A (en) | 2018-02-13 |
| CN107686635B true CN107686635B (en) | 2020-03-06 |
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| CN108395677B (en) * | 2018-04-24 | 2020-06-19 | 江苏道蓬科技有限公司 | Graphene modified powder epoxy resin and preparation method thereof |
| IL265374B2 (en) * | 2019-03-14 | 2023-11-01 | Israel Aerospace Ind Ltd | Composite material with increase thermal conductivity and method for manufacture thereof |
| BR102020015342A2 (en) * | 2020-07-28 | 2022-02-08 | Universidade Federal De Minas Gerais | PROCESS FOR INCORPORATION OF CARBON NANOMATERIALS INTO A SOLID PHASE FBE POLYMERIC MATRIX, PRODUCT AND USE |
Citations (4)
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| CN103627139A (en) * | 2013-09-25 | 2014-03-12 | 杭州师范大学 | Preparation method of functionalized graphene oxide/epoxy resin nanocomposite |
| CN105176086A (en) * | 2014-05-28 | 2015-12-23 | 中国科学院苏州纳米技术与纳米仿生研究所 | Oriented graphene/polymer composite system, and preparation method and application thereof |
| CN106398122A (en) * | 2016-10-13 | 2017-02-15 | 常州大学 | Graphene and epoxy resin composite foam material and preparation method thereof |
| CN106810818A (en) * | 2015-11-30 | 2017-06-09 | 航天特种材料及工艺技术研究所 | A kind of Graphene modified epoxy and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103627139A (en) * | 2013-09-25 | 2014-03-12 | 杭州师范大学 | Preparation method of functionalized graphene oxide/epoxy resin nanocomposite |
| CN105176086A (en) * | 2014-05-28 | 2015-12-23 | 中国科学院苏州纳米技术与纳米仿生研究所 | Oriented graphene/polymer composite system, and preparation method and application thereof |
| CN106810818A (en) * | 2015-11-30 | 2017-06-09 | 航天特种材料及工艺技术研究所 | A kind of Graphene modified epoxy and preparation method thereof |
| CN106398122A (en) * | 2016-10-13 | 2017-02-15 | 常州大学 | Graphene and epoxy resin composite foam material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Fabrication of Graphene/Epoxy Resin Composites with Much Enhanced Thermal Conductivity via Ball Milling Technique;Wenman Guo, et al.;《J. APPL. POLYM. SCI.》;20140306;第131卷(第15期);第40565（1-5）页 * |
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Effective date of registration: 20191107 Address after: Jinyuan Road, Jimei District of Xiamen City, Fujian Province, No. 398 361022 Applicant after: Xiamen Hailai Lighting Co.,Ltd. Applicant after: Huaqiao University Address before: Jinyuan Road, Jimei District of Xiamen City, Fujian Province, No. 398 361022 Applicant before: Xiamen Hailai Lighting Co.,Ltd. |
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