CN108912683B - Thermal interface material based on low-melting-point metal/heat-conducting particle composite heat-conducting network and preparation method thereof - Google Patents
Thermal interface material based on low-melting-point metal/heat-conducting particle composite heat-conducting network and preparation method thereof Download PDFInfo
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- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
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Abstract
The invention discloses a thermal interface material based on a low-melting-point metal/heat-conducting particle composite heat-conducting network and a preparation method thereof, belonging to the technical field of thermal interface materials. The material is prepared by taking low-melting-point metal, heat-conducting particles, a foaming agent and high-molecular polymer as raw materials and adopting the processes of metallurgical interconnection of the low-melting-point metal and the heat-conducting particles, pyrolysis of the foaming agent for pore formation, vacuum infiltration of the high-molecular polymer and the like. The efficient three-dimensional heat conduction channel constructed by the low-melting-point metal and the heat conduction particles enables the material to have extremely high heat conductivity; the use of the high molecular polymer and the low-melting-point metal ensures the high elasticity and flexibility of the material; in the using process, metallurgical interconnection is formed between the low-melting-point metal and the interface of the metal substrate, the high-molecular polymer and the substrate generate an adhesion effect, and the two connection modes not only provide extremely low interface thermal resistance, but also limit the overflow problem of the low-melting-point metal.
Description
Technical Field
The invention relates to the technical field of thermal interface materials, in particular to a thermal interface material based on a low-melting-point metal/heat-conducting particle composite heat-conducting network and a preparation method thereof.
Background
With the high power, high assembly density and microminiaturization of electronic components, the power density of electronic equipment is increased sharply and even reaches 100W/cm2The level of (c). Temperature rise has an important influence on the working state and physical structure of the circuit, and usually changes the electrical parameters of active devices, even causes complete failure of electronic components. Therefore, how to effectively ensure the heat dissipation of the electronic component becomes a key factor that restricts the performance and reliability of the electronic component from further improving. In the service process of the electronic equipment, most of heat needs to be dissipated through the heat sink, and a large number of gaps inevitably exist between the heat source and the heat sink, so that the heat dissipation efficiency of the electronic equipment is seriously affected.Therefore, a high thermal conductivity and soft thermal interface material is needed to ensure good contact between the heat source and the heat sink, and finally the purposes of reducing contact thermal resistance and improving heat transfer efficiency are achieved.
The traditional thermal interface material comprises heat-conducting silicone grease, a phase-change material, a heat-conducting silicone sheet and the like, and generally consists of a polymer material and heat-conducting particles, and the great heat resistance among the heat-conducting particles determines that the traditional thermal interface material has poor heat-conducting performance, so that the increasingly harsh heat dissipation requirements of high-performance electronic components are difficult to meet.
Disclosure of Invention
Aiming at the defects of the existing thermal interface material, the invention aims to provide the thermal interface material based on the low-melting-point metal \ heat-conducting particle composite heat-conducting network and the preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a thermal interface material based on low-melting-point metal \ heat-conducting particle composite heat-conducting network is composed of low-melting-point metal, heat-conducting particles and high molecular polymer; wherein: the heat conduction particles are connected by low-melting-point metal serving as a connecting agent to form a three-dimensional heat conduction network channel; and the pores among the three-dimensional heat-conducting network channels are filled with high molecular polymers. In the thermal interface material, the volume ratio of the low-melting-point metal, the heat conducting particles and the high molecular polymer is (20-40): (20-40): (20-60).
And the pores among the three-dimensional heat conduction network channels are in a three-dimensional communication network structure.
The low-melting-point metal is pure metal or alloy, the melting point of the low-melting-point metal is lower than 80 ℃, and the chemical components of the low-melting-point metal contain one or more of gallium, bismuth, cadmium, tin, lead, dysprosium and indium.
The heat conducting particles are metal heat conducting fillers and/or inorganic nonmetal heat conducting fillers, and the surfaces of the inorganic nonmetal heat conducting fillers can be subjected to metallization treatment; the metal heat-conducting filler is one or more of copper, copper alloy, aluminum alloy, silver alloy, iron alloy, zinc alloy, tin and tin alloy, and the inorganic nonmetal heat-conducting filler is one or more of diamond, boron nitride, aluminum oxide, aluminum nitride, silicon nitride, graphite, a carbon nanotube and graphene.
The high molecular polymer is organic silicon resin, or epoxy resin, polyperfluorinated ethylene propylene or polystyrene and the like.
The preparation method of the thermal interface material based on the low-melting-point metal/heat-conducting particle composite heat-conducting network takes low-melting-point alloy, heat-conducting particles, a foaming agent and a high molecular polymer as raw materials, and the thermal interface material is prepared and obtained by adopting liquid metal and heat-conducting particle metallurgical interconnection, foaming agent pyrolysis pore-forming and high molecular polymer vacuum infiltration processes in sequence. The method specifically comprises the following steps:
(1) metallurgical interconnection of liquid metal and heat conducting particles: putting low-melting-point metal and heat conducting particles into a container according to a proportion, and repeatedly stirring to obtain a completely wetted and fully mixed material; placing the obtained mixed material in a constant temperature furnace, and placing the mixed material at a certain temperature for a period of time to form firm metallurgical bonding between the low-melting-point metal and the heat conducting particles;
(2) and (3) pyrolysis and pore-forming of a foaming agent: adding a foaming agent into the mixed material placed for a period of time in the step (1) in proportion, fully mixing, placing into a mold, and performing compression molding; placing the sample after the pressing forming in a constant temperature furnace, and placing for a period of time at a certain temperature to completely decompose the foaming agent, thereby obtaining a three-dimensional network structure material with continuous pores distributed;
(3) the high molecular polymer vacuum infiltration process comprises the following steps: taking the three-dimensional network structure material with the distributed continuous pores obtained in the step (2) out of the constant temperature furnace, and placing the material in a low temperature environment such as a refrigerator or liquid nitrogen to solidify low-melting-point metal in the material; and then immersing the material in a liquid high molecular polymer, placing the material in a vacuum furnace, filling the liquid high molecular polymer into pores of the material through a vacuum infiltration process, and after the liquid high molecular polymer is solidified at high temperature, polishing and cutting to obtain the thermal interface material.
In the step (1), the proportion of the heat-conducting particles in the mixed material is 10-90 wt.%, and the particle size of the heat-conducting particles is 0.001-500 μm; in the step (2), the weight of the added foaming agent accounts for 0.5-30% of the weight of the mixed material; the foaming agent is ammonium bicarbonate particles, and the particle size of the foaming agent is 0.1-500 mu m.
In the step (1), the heat preservation temperature of the obtained mixed material in a constant temperature furnace is 100-1400 ℃, and the heat preservation time is 0.1-48 h; in the step (2), the heat preservation temperature of the sample after the press forming in the constant temperature furnace is 50-500 ℃, and the heat preservation time is 0.1-48 h.
The design mechanism and the beneficial effects of the invention are as follows:
1. the thermal interface material of the invention is a three-dimensional heat conduction network channel constructed by low-melting-point metal and heat conduction particles; the pores among the three-dimensional heat conduction network channels are filled with high molecular polymers. The efficient three-dimensional heat conduction channel constructed by the low-melting-point metal and the heat conduction particles enables the material to have extremely high heat conductivity, and meanwhile, the stress problem caused by the mismatch of thermal expansion coefficients of the silicon chip and the heat sink can be effectively solved.
2. According to the invention, the foaming agent is decomposed at high temperature to construct a three-dimensional continuous pore network, the high molecular polymer is impregnated and filled in a vacuum manner, and the use of the high molecular polymer and the low-melting-point metal ensures that the material has good elasticity and flexibility. If the low-melting-point metal is used alone and no high-molecular polymer is used, the low-melting-point metal has the risk of leakage and is not suitable for occasions with requirements on shock absorption.
3. In the use process of the thermal interface material, the interface of the low-melting-point metal and the metal substrate forms metallurgical interconnection, the high molecular polymer and the substrate generate bonding effect, and the two connection modes not only provide extremely low interface thermal resistance, but also limit the overflow problem of the low-melting-point alloy.
Drawings
FIG. 1 is a schematic diagram illustrating the preparation principle of the thermal interface material of the present invention.
Fig. 2 is a microstructure photograph of the high thermal conductivity elastomer thermal interface material in example 1.
FIG. 3 is a physical display of the high thermal conductivity elastomer thermal interface material in example 1.
FIG. 4 is a photograph of the microstructure of the thermal interface material in example 2.
FIG. 5 is a photograph of the microstructure of the thermal interface material in example 3.
FIG. 6 is a photograph of the microstructure of the thermal interface material in example 4.
Detailed Description
The invention is further illustrated by the following figures and examples, which are given solely for the purpose of illustration and are not intended to be limiting.
Example 1:
the preparation principle of the thermal interface material of the embodiment is shown in fig. 1, and the specific process is as follows:
(1) preparing a low-melting-point alloy: mixing gallium (purity 99.99%) and titanium powder (1600 mesh, purity 99.99%) according to a mass ratio of 99:1, fully stirring, and placing in a 200 ℃ constant temperature furnace for heat preservation for 2h to obtain the low-melting-point alloy-gallium titanium alloy.
(2) Mixing titanium-plated diamond particles (325 meshes, vacuum-evaporated titanium) and gallium-titanium alloy according to the mass ratio of 1:1.6, placing the mixture in a mortar, repeatedly grinding and stirring for 15min to ensure that gallium and the titanium-plated diamond particles are completely wetted and fully mixed, and placing the mixture in a constant temperature furnace at 200 ℃ for heat preservation for 2h to ensure that gallium and titanium form firmer metallurgical bonding.
(3) Preparing a foaming agent: grinding the ammonium bicarbonate into fine particles, sieving the fine particles through stainless steel standard sieves with different mesh numbers to obtain the ammonium bicarbonate particles with the particle size of 34-50 mu m.
(4) Adding the prepared foaming agent into the mixture prepared in the second step according to the mass ratio of 5%, fully mixing, and then placing the mixture into a mold at the ratio of 1.16 multiplied by 106And compacting and molding the material under the pressure Pa.
(5) And (3) placing the molded sample prepared in the fourth step into a heat preservation furnace, preserving heat for 8 hours at 80 ℃, and preserving heat for 2 hours at 120 ℃ to ensure that ammonium bicarbonate is completely decomposed, thereby obtaining the three-dimensional network structure material with continuous pores.
(6) Taking out the sample from the heat preservation furnace, placing the sample in a low-temperature environment such as a refrigerator or liquid nitrogen to solidify gallium-titanium alloy in the material, then immersing the material in organic silicon resin, placing the material in a vacuum furnace, and filling the organic silicon resin into pores of the material through a vacuum infiltration process. Epoxy resin, fluorinated ethylene propylene or polystyrene and the like can be adopted to replace organic silicon resin in the step, and the similar effect is achieved.
(7) The organic silicon resin is solidified at 120 ℃, and is ground, polished and cut to obtain the high-heat missile body thermal interface material, and the microscopic structure photo of the high-heat missile body thermal interface material is shown in figure 2. As can be seen from fig. 2, the thermal interface material is formed by constructing three-dimensional heat-conducting network channels from low-melting-point alloy and heat-conducting particles, and filling pores between the three-dimensional heat-conducting network channels with high molecular polymer.
(8) The novel thermal interface material is shown in figure 3, and the thermal diffusivity is 13.527mm after being tested2(Netzsch LFA447), specific heat capacity of 0.608J/g.K (Mettler-Toledo DSC3), density of 3.56g/cm3(Archimedes drainage method), the thermal conductivity is 29.28W/m.K (, RT), and the Shore A hardness is 19.9-25.2.
Example 2:
(1) mixing low-melting-point metal gallium (purity 99.99%) and heat-conducting particle copper particles (150 meshes, purity 99.99%) according to a mass ratio of 1:2, fully stirring, and keeping the temperature at 50 ℃ for 10 min. Preparing a foaming agent: grinding the ammonium bicarbonate into fine particles, sieving the fine particles through stainless steel standard sieves with different mesh numbers to obtain the ammonium bicarbonate particles with the particle size of 34-50 mu m.
(2) Adding the prepared foaming agent into the mixture prepared in the first step according to the mass ratio of 5%, fully mixing, then placing the mixture into a mold, and placing the mixture at the mass ratio of 1.16 multiplied by 106And compacting and molding the material under the pressure Pa.
(3) And (3) placing the sample prepared in the third step into a heat preservation furnace, preserving heat for 8h at 80 ℃, and preserving heat for 2h at 120 ℃ to ensure that ammonium bicarbonate is completely decomposed, thereby obtaining the three-dimensional network structure material with continuous pores.
(4) And taking the sample out of the heat preservation furnace, placing the sample in a low-temperature environment such as a refrigerator or liquid nitrogen to solidify gallium in the material, then immersing the material in the organic silicon resin, placing the material in a vacuum furnace, and filling the organic silicon resin into the pores of the material through a vacuum infiltration process. Epoxy resin, fluorinated ethylene propylene or polystyrene and the like can be adopted to replace organic silicon resin in the step, and the similar effect is achieved.
(6) The organic silicon resin is cured at a high temperature of 120 ℃, and is polished and cut to obtain the high-heat-conductivity interface material, and a microscopic structure photo of the high-heat-conductivity interface material is shown in figure 4. As can be seen from fig. 4, the thermal interface material is formed by constructing three-dimensional heat-conducting network channels by using low-melting-point metal and heat-conducting particles, and filling pores between the three-dimensional heat-conducting network channels with high molecular polymer.
(7) The thermal diffusivity of the novel thermal interface material is 13.09mm2(s), specific heat capacity of 0.433J/g.K, density of 5.61g/cm3The thermal conductivity was 31.82W/mK.
Example 3:
the preparation process of the thermal interface material of this example is as follows:
(1) chemically plating copper on the surface of boron nitride (the particle diameter is approximately equal to 5 mu m, and the purity is 99.9%), mixing low-melting-point metal gallium (the purity is 99.99%) with boron nitride particles subjected to metallization treatment (the surface copper-plated boron nitride) according to the mass ratio of 1:1, fully stirring, and preserving heat at 50 ℃ for 10 min.
(2) Preparing a foaming agent: grinding the ammonium bicarbonate into fine particles, sieving the fine particles through stainless steel standard sieves with different mesh numbers to obtain the ammonium bicarbonate particles with the particle size of 34-50 mu m.
(3) Adding the prepared foaming agent into the mixture prepared in the first step according to the mass ratio of 5%, fully mixing, then placing the mixture into a mold, and placing the mixture at the mass ratio of 1.16 multiplied by 106And compacting and molding the material under the pressure Pa.
(4) And (3) placing the sample prepared in the third step into a heat preservation furnace, preserving heat for 8h at 80 ℃, and preserving heat for 2h at 120 ℃ to ensure that ammonium bicarbonate is completely decomposed, thereby obtaining the three-dimensional network structure material with continuous pores.
(5) And taking the sample out of the heat preservation furnace, placing the sample in a low-temperature environment such as a refrigerator or liquid nitrogen to solidify gallium in the material, then immersing the material in the organic silicon resin, placing the material in a vacuum furnace, and filling the organic silicon resin into the pores of the material through a vacuum infiltration process. Epoxy resin, fluorinated ethylene propylene or polystyrene and the like can be adopted to replace organic silicon resin in the step, and the similar effect is achieved.
(6) And (3) curing the organic silicon resin at a high temperature of 120 ℃, and grinding, polishing and cutting to obtain the high-heat-conductivity interface material. The microstructure photograph is shown in FIG. 5. As can be seen from fig. 5, the thermal interface material is formed by constructing three-dimensional heat-conducting network channels from low-melting-point alloy and heat-conducting particles, and filling pores between the three-dimensional heat-conducting network channels with high molecular polymer.
(7) The thermal conductivity of the novel thermal interface material is 6.6W/m.K measured by a steady-state heat flow method.
Example 4:
the preparation process of the thermal interface material of this example is as follows:
(1) mixing titanium-plated diamond particles (325 meshes, vacuum-evaporated titanium) and gallium according to the mass ratio of 1:1.6, placing the mixture in a mortar, repeatedly grinding and stirring for 15min to ensure that the gallium and the titanium-plated diamond particles are completely wetted and fully mixed, and placing the mixture in a constant temperature furnace at 200 ℃ for heat preservation for 2h to ensure that the gallium and the titanium form firmer metallurgical bonding.
(2) Preparing a foaming agent: grinding the ammonium bicarbonate into fine particles, sieving the fine particles through stainless steel standard sieves with different mesh numbers to obtain the ammonium bicarbonate particles with the particle size of 34-50 mu m.
(3) Adding the prepared foaming agent into the mixture prepared in the second step according to the mass ratio of 5%, fully mixing, and then placing the mixture into a mold at the ratio of 1.16 multiplied by 106And compacting and molding the material under the pressure Pa.
(4) And (3) placing the molded sample prepared in the fourth step into a heat preservation furnace, preserving heat for 8 hours at 80 ℃, and preserving heat for 2 hours at 120 ℃ to ensure that ammonium bicarbonate is completely decomposed, thereby obtaining the three-dimensional network structure material with continuous pores.
(5) And taking the sample out of the heat preservation furnace, placing the sample in a low-temperature environment such as a refrigerator or liquid nitrogen to solidify the gallium-titanium alloy in the material, then immersing the material in epoxy resin, placing the material in a vacuum furnace, and filling the epoxy resin into the pores of the material through a vacuum infiltration process. In the step, organic silicon resin, fluorinated ethylene propylene or polystyrene and the like can be used to replace epoxy resin, and the like, so that the effect is similar.
(6) The epoxy resin is cured at the high temperature of 80 ℃, and is ground, polished and cut to obtain the high-heat missile body thermal interface material, and the microscopic structure photo of the high-heat missile body thermal interface material is shown in figure 6. As can be seen from fig. 6, the thermal interface material is formed by constructing three-dimensional heat-conducting network channels from low-melting-point alloy and heat-conducting particles, and filling pores between the three-dimensional heat-conducting network channels with high molecular polymer.
(7) The thermal diffusivity of the novel thermal interface material is 11.04mm2(s), specific heat capacity of 0.553J/g.K, density of 3.57g/cm3The thermal conductivity was 21.79W/mK.
Claims (8)
1. The preparation method of the thermal interface material based on the low-melting-point metal \ heat-conducting particle composite heat-conducting network is characterized by comprising the following steps of: the thermal interface material consists of low-melting-point metal, heat-conducting particles and high-molecular polymer; wherein: the heat conduction particles are connected by low-melting-point metal serving as a connecting agent to form a three-dimensional heat conduction network channel; the pores among the three-dimensional heat-conducting network channels are filled with high molecular polymers; the melting point of the low-melting-point metal is lower than 80 ℃, and the chemical components of the low-melting-point metal contain one or more of gallium, bismuth, cadmium, tin, lead, dysprosium and indium;
the preparation method of the thermal interface material based on the low-melting-point metal/heat-conducting particle composite heat-conducting network is characterized in that low-melting-point metal, heat-conducting particles, a foaming agent and a high-molecular polymer are used as raw materials, and the thermal interface material is prepared and obtained by adopting the processes of metallurgical interconnection of the low-melting-point metal and the heat-conducting particles, pyrolysis pore forming of the foaming agent and vacuum infiltration of the high-molecular polymer in sequence.
2. The preparation method of the thermal interface material based on the low-melting-point metal \ heat-conducting particle composite heat-conducting network as claimed in claim 1, is characterized in that: and the pores among the three-dimensional heat conduction network channels are in a three-dimensional communication network structure.
3. The preparation method of the thermal interface material based on the low-melting-point metal \ heat-conducting particle composite heat-conducting network as claimed in claim 1, is characterized in that: in the thermal interface material, the volume ratio of the low-melting-point metal, the heat conducting particles and the high molecular polymer is (20-40): (20-40): (20-60).
4. The preparation method of the thermal interface material based on the low-melting-point metal \ heat-conducting particle composite heat-conducting network as claimed in claim 1, is characterized in that: the heat conducting particles are metal heat conducting fillers and/or inorganic nonmetal heat conducting fillers, and the surfaces of the inorganic nonmetal heat conducting fillers can be subjected to metallization treatment; the metal heat-conducting filler is a pure metal or an alloy material, and the inorganic nonmetal heat-conducting filler is one or more of diamond, boron nitride, aluminum oxide, aluminum nitride, silicon nitride, graphite, a carbon nanotube and graphene.
5. The preparation method of the thermal interface material based on the low-melting-point metal \ heat-conducting particle composite heat-conducting network as claimed in claim 1, is characterized in that: the high molecular polymer is organic silicon resin, epoxy resin, fluorinated ethylene propylene or polystyrene.
6. The preparation method of the thermal interface material based on the low-melting-point metal \ heat-conducting particle composite heat-conducting network as claimed in claim 1, is characterized in that: the method comprises the following steps:
(1) metallurgical interconnection of liquid metal and heat conducting particles: putting low-melting-point metal and heat conducting particles into a container according to a proportion, and repeatedly stirring to obtain a completely wetted and fully mixed material; placing the obtained mixed material in a constant temperature furnace, and placing the mixed material at a certain temperature for a period of time to form firm metallurgical bonding between the low-melting-point metal and the heat conducting particles;
(2) and (3) pyrolysis and pore-forming of a foaming agent: adding a foaming agent into the mixed material placed for a period of time in the step (1) in proportion, fully mixing, placing into a mold, and performing compression molding; placing the sample after the pressing forming in a constant temperature furnace, and placing for a period of time at a certain temperature to completely decompose the foaming agent, thereby obtaining a three-dimensional network structure material with continuous pores distributed;
(3) the high molecular polymer vacuum infiltration process comprises the following steps: taking the three-dimensional network structure material with the distributed continuous pores obtained in the step (2) out of the constant temperature furnace, and placing the material in a refrigerator or a liquid nitrogen low-temperature environment to solidify low-melting-point metal in the material; and then immersing the material in a liquid high molecular polymer, placing the material in a vacuum furnace, filling the liquid high molecular polymer into pores of the material through a vacuum infiltration process, and after the liquid high molecular polymer is solidified at high temperature, polishing and cutting to obtain the thermal interface material.
7. The preparation method of the thermal interface material based on the low-melting-point metal \ heat-conducting particle composite heat-conducting network as claimed in claim 6, characterized in that: in the step (1), the proportion of the heat-conducting particles in the mixed material is 10-90 wt.%, and the particle size of the heat-conducting particles is 0.001-500 μm; in the step (2), the weight of the added foaming agent accounts for 0.5-30% of the weight of the mixed material; the foaming agent is ammonium bicarbonate particles, and the particle size of the foaming agent is 0.1-500 mu m.
8. The preparation method of the thermal interface material based on the low-melting-point metal \ heat-conducting particle composite heat-conducting network as claimed in claim 6, characterized in that: in the step (1), the heat preservation temperature of the obtained mixed material in a constant temperature furnace is 50-1400 ℃, and the heat preservation time is 0.1-48 h; in the step (2), the heat preservation temperature of the sample after the press forming in a constant temperature furnace is 50-500 ℃, and the heat preservation time is 0.1-48 h.
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| CN110105758A (en) * | 2019-05-15 | 2019-08-09 | 东南大学 | A kind of preparation of the electronic package material based on liquid metal and its application method |
| CN110625877B (en) * | 2019-09-05 | 2021-06-08 | 上海阿莱德实业股份有限公司 | Preparation method of heat-conducting interface material |
| CN112625657B (en) * | 2019-09-24 | 2022-01-14 | 华为技术有限公司 | Packaging structure of heat conductor, heat conduction material and semiconductor device |
| CN110862572B (en) * | 2019-10-10 | 2022-08-09 | 仲恺农业工程学院 | Application of heat-conducting ceramic powder low-melting-point alloy composite powder |
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| CN115322556A (en) * | 2021-05-10 | 2022-11-11 | 上海交通大学 | High thermal/electrical conductivity polymer-based composite material with three-dimensional low-melting-point metal-based filler network and preparation thereof |
| CN113337231B (en) * | 2021-06-01 | 2022-10-04 | 中国科学院合肥物质科学研究院 | Epoxy composite material with heterostructure and preparation method thereof |
| CN115725273A (en) * | 2021-08-26 | 2023-03-03 | 华为技术有限公司 | Diamond-based heat-conducting filler, preparation method thereof, composite heat-conducting material and electronic equipment |
| CN113755141A (en) * | 2021-09-02 | 2021-12-07 | 宁波施捷电子有限公司 | Interface heat-conducting metal material and application thereof |
| CN113881354B (en) * | 2021-09-29 | 2022-07-22 | 湖北瑞宇空天高新技术有限公司 | Bonding repair method for carbon fiber reinforced carbon-based composite material, used bonding agent and preparation method thereof |
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