WO2017143625A1 - High thermal conductive composite material, thermal conductive sheet prepared from material, and preparation method therefor - Google Patents

High thermal conductive composite material, thermal conductive sheet prepared from material, and preparation method therefor Download PDF

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WO2017143625A1
WO2017143625A1 PCT/CN2016/075381 CN2016075381W WO2017143625A1 WO 2017143625 A1 WO2017143625 A1 WO 2017143625A1 CN 2016075381 W CN2016075381 W CN 2016075381W WO 2017143625 A1 WO2017143625 A1 WO 2017143625A1
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silicone rubber
alumina
component
composite material
sheet
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PCT/CN2016/075381
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French (fr)
Chinese (zh)
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柯瑞林
柯冰
王玲
彭保
曾敏
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深圳市欧姆阳科技有限公司
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Publication of WO2017143625A1 publication Critical patent/WO2017143625A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

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  • the invention relates to a heat conductive composite material, in particular to a high thermal conductivity silicone rubber composite material with high thermal conductivity, good safety performance, good stability, high resilience and good flexibility, and heat conduction made of the heat conductive material.
  • the sheet and the preparation method thereof belong to the technical field of heat conduction of thermal interface materials.
  • the heat dissipation problem of electronic devices is mostly solved by various forms of heat sinks.
  • electronic devices there are many contact faces between various electronic components and the heat sink, and there are gaps between them, resulting in poor heat flow.
  • a thermal conductive silicone rubber sheet is usually filled between the contact faces, and the use is made.
  • the thermal conductivity of the silicone rubber sheet is soft and the elastic variable under the action of low pressure, which is in close contact with the rough surface structure, so as to remove the heat generated by the microprocessor, the graphics processor and other important chips, reduce or even eliminate the air. Thermal resistance.
  • thermal silicone rubber At present, the heat dissipation mode of thermal silicone rubber is mostly selected in two ways:
  • the inorganic non-metal oxides or nitrides such as alumina, aluminum nitride, etc.
  • the thermal conductivity is poor, and the thermal conductivity is generally around 1.5-3 W/m.k, which is not suitable for the heat dissipation requirements of high-power components.
  • the thermal conductivity of the prepared thermal conductive silicone rubber is greatly improved, and its thermal conductivity can be 5.0-8 W/mk or higher, but its conductivity is also high, and the safety is very high. Large constraints, and thus have great limitations in practical applications.
  • the object of the present invention is to provide a novel high thermal conductive composite material and a preparation method thereof, which can achieve a thermal conductivity of 10 W/mk or more, and have good safety performance. Good stability, high resilience and good flexibility. It is suitable for interface heat transfer between heat-generating components and heat-dissipating components or similar applications.
  • a first object of the present application is to provide a highly thermally conductive composite material comprising the following components in mass percent:
  • the nano-alumina (Al 2 O 3 ) has a particle diameter of 60-150 nm and a purity of ⁇ 99.0%, and the thermal conductivity and insulation of the material can be improved due to good interfacial compatibility, smooth surface and excellent dispersibility. performance.
  • the basic characteristics are as follows: high sphericity, dense particles, specific surface area ⁇ 23m 2 /g, high surface activity, bulk density: ⁇ 0.37g/cm 3 , thermal conductivity: 30W/mK, which can be added to the substrate. Improve its thermal conductivity.
  • the micron alumina (Al 2 O 3 ) has a particle diameter of 1-100 ⁇ m and a purity of ⁇ 99.6%, and the thermal conductivity and the insulating property of the material can be improved due to excellent dispersibility.
  • Its basic characteristics are: appearance: white powder, purity ⁇ 99.6%, particle size: 1-100 ⁇ m, specific surface area ⁇ 1.06m 2 /g, density: 3.97g/cm 3 , thermal conductivity: 30W/mK, its original crystal particles Larger, narrow particle size distribution, ultra-low oil absorption, added to the substrate, can improve its thermal conductivity.
  • the silicon carbide whiskers ( ⁇ -SiC Whisker) have a length of 10-40 ⁇ m and a diameter of 0.05-0.2 ⁇ m, and the added amount is 0.5-5% of the total amount. Since the nano-SiC has a large aspect ratio, the particles are easier.
  • the heat conductive mesh chain is formed inside the substrate system to reduce the internal void ratio of the material and improve the thermal conductivity.
  • the basic characteristics are: ⁇ -SiC whisker has large aspect ratio, high surface smoothness, high diameter ratio, regular crystal structure and excellent heat conduction.
  • the performance, the thermal conductivity is 155 W/mK, the density is 3.21 g/cm 3 , and the thermal expansion coefficient is 4.3 ⁇ 10 -6 /K.
  • the hexagonal boron nitride has a particle diameter of 15 ⁇ m, a purity of >98%, and an addition amount of 3-10% of the total amount. In addition to maintaining excellent thermal conductivity, it also has good insulation and lubricity and chemical stability.
  • the basic characteristics are as follows: the crystal structure of hexagonal boron nitride has a structure similar to graphite layer, and presents a white powder with loose, lubricious, easy moisture absorption, light weight and other properties, density 2.27g/cm 3 , thermal conductivity 250w/mk
  • the coefficient of thermal expansion is: 2 ⁇ 10 -6 /K. It has excellent insulation performance, 10 14 ⁇ -cm at 25 ° C, 2.5 ⁇ 10 -4 at low dielectric loss of 108 Hz, dielectric constant of 4, microwave and infrared ray, and low friction coefficient: U is 0.16.
  • the graphene sheet has a length of 3-20 ⁇ m and a thickness of 20 nm, and the amount of addition is 0.1-1.2% of the total amount, and in the case where the amount of addition is extremely small, the heat can be made Conducted faster in the horizontal direction.
  • Its basic characteristics are: high surface area: 2675m 2 /g, low density: 1.89g/cm 3 , thermal conductivity 5300W/mk.
  • the carbon nanotubes have an OD particle diameter of >50 nm, an ID particle diameter of 5-15 nm, a length of 10-20 um, and a purity of >92%, which can be added in an amount due to an excessive aspect ratio.
  • the thermal conductivity and mechanical strength of the material can be greatly improved. Its basic characteristics are: specific surface area > 60 m 2 /g. Bulk density: 0.18 g/cm 3 , density: 2.1 g/cm 3 , thermal conductivity 3000 W/mk.
  • the content of the methyl vinyl silicone rubber (VMQ) is 0.5-2%
  • the methyl vinyl silicone rubber has a molecular weight of 500-700,000
  • the vinyl content is 0.07-0.15 mol%, and the processing property thereof is obtained.
  • anti-compression permanent deformation performance is good.
  • the content of the dimethyl silicone oil (molecular formula: (CH 3 ) 3 SiO[(CH 3 ) 2 SiO]n-Si(CH 3 ) 3 )) is 5-12%, and the dimethicone used is The viscosity is 50-500 cps.
  • the content of the hydroxy silicone oil (molecular formula: HO[(CH 3 ) 2 SiO] n H) is 0.5-2%, the hydroxy silicone oil used is a small molecule hydroxy silicone oil, viscosity (25 ° C): 25-30 cps The hydroxyl content is 8%.
  • the content of the vulcanizing agent is 0.1-0.5%, and 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane (molecular formula: C 16 H 34 O 4 ) is used.
  • the scent of the vulcanizing agent used after vulcanization is relatively small in the alkyl peroxide.
  • the iron powder has an average diameter of 5-10 ⁇ m, a sheet thickness of 50-100 nm, a specific surface area of >15 m 2 /g, and a purity of 99.9%.
  • Color black
  • topography ultra-fine flake powder, ultra-fine flake iron powder prepared by physical and mechanical method, is a highly active zero-valent iron powder, with high coercivity, high specific saturation magnetization, high signal noise Advantages such as better than oxidation resistance.
  • the nickel powder has a purity of ⁇ 99.7%, a particle size of 0.5-1.5 ⁇ m, a bulk density of 0.5-0.9 g/cm 3 , a specific surface area of 2.0-6.0 m 2 /g, and a carbon and oxygen content ⁇ 0.3. %.
  • Color gray black
  • topography bead chain powder, with high saturation magnetization and high magnetic permeability, with a special three-dimensional chain superfine particle network, its unique bead structure can produce a good conductive and thermal network.
  • the content of the cobalt powder (Co) is 5-15%, the purity is ⁇ 99.9%, the average particle diameter is 1.0 ⁇ m, the bulk density is 0.83 g/cm 3 , the density is 8.9 g/cm 3 , and the specific surface area : 8.0 m 2 /g, the sum of carbon and oxygen content is ⁇ 0.42%, and the sum of metal impurities is ⁇ 0.03%.
  • a second object of the present invention is to provide a thermally conductive sheet made of the above composite material, which is an insulating thermally conductive layer and an electrically and thermally conductive layer in the order of distance from the heat source, and the thermally conductive layer comprises a component one.
  • the thermally conductive layer comprises component two and component three, each component comprising the following components in percentages:
  • the insulating and heat conducting layer is used for receiving the heat source. Due to the electrical insulation, the heat generating chip and the heat generating component can be protected, and the heat energy can be absorbed quickly and safely; the conductive heat conductive layer contacts the heat sink to better conduct heat energy and improve the material. Comprehensive thermal conductivity.
  • a third object of the present application is to provide a method for preparing the above thermally conductive sheet:
  • thermally conductive silicone rubber sheet composite material provided by the invention is made of the above mass percentage components, and the specific preparation process comprises the following steps:
  • filler nano alumina, micro alumina, silicon carbide whisker, hexagonal boron nitride, graphene sheet, carbon nanotube, iron powder, nickel powder and cobalt powder are separately placed in the dryer. Dry at 3-4 hours at 100-120 °C;
  • silicone rubber pretreatment methyl vinyl silicone rubber and dimethyl silicone oil are added to the mill for mixing and grinding to obtain a silicone rubber matrix;
  • step 3 Vacuum mixing: The silicone rubber matrix obtained in step 2 is placed in a vacuum kneader, and the first is added with hydroxy silicone oil, and then the main heat-conductive filler of component one is added in order from the least to the order of the filler quality.
  • a graphene sheet, a carbon nanotube, a silicon carbide whisker, a nano-alumina, a hexagonal boron nitride and a micro-alumina are sequentially added; then an auxiliary thermally conductive filler of the third component is added to the silicone rubber matrix,
  • the order of addition is also based on the order of the mass of the filler from small to large, that is, the cobalt powder, the iron powder and the nickel powder are sequentially added and kneaded in a vacuum kneader, and vacuum kneaded for 30-40 minutes to obtain a thermally conductive silicone rubber compound;
  • the mixed heat-conducting silicone rubber compound rubber is sealed with a plastic bag, left to stand for 20-24 hours, and then placed on the open machine on the thin pass, using the standard thin pass mode, thin pass 5 -7 times, adding vulcanizing agent 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane during the thin pass process, thinning the film, and entering the forming mold;
  • a layer region (the outer ring directly has an excitation coil to form a strong magnetic field region), that is, a conductive heat conduction layer is formed, and a layer region of the lower partial layer region (with no surrounding excitation coil outside) forms an insulating heat conduction layer, and the applicant performs an experiment. 98% of the components are gathered in the upper zone, and 98% of the material in the lower zone is component-aggregate;
  • Mold vulcanization After thin filming, it is molded at 160-180 ° C for 15-20 minutes under high temperature molding to obtain a formed sheet-like silicone rubber composite.
  • Secondary vulcanization the formed sheet-like silicone rubber composite obtained in the previous step is at 200-210 ° C. The next secondary vulcanization is for 4-5 hours, further vulcanization reduces the peroxide content, and volatilizes the small molecular substance to obtain a high-quality sheet-shaped thermally conductive silicone rubber composite material.
  • the thermal conductivity of the thermal conductive silicone rubber material is generally about 1.5-3W/mk, and the material of the invention can achieve a thermal conductivity of more than 10 W/mk through special formulation and technical means, and greatly improve the thermal conductivity of the material. .
  • Filler innovation At present, only single or small fillers are selected for matching in the industry. We study a number of fillers and comprehensive influences, particle size, morphology selection, surface wettability treatment, doping fraction for each material. Adjustment, combined with its own thermal conductivity and electrical conductivity balance treatment, scientifically match the different types of fillers, try to maximize the thermal conductivity, while maintaining the safety, resilience and flexibility of the material itself.
  • FIG. 1 is a schematic structural view of a thermally conductive sheet made of a high thermal conductive composite material according to the present application
  • 1 is a heat source
  • 2 is an insulating and thermally conductive layer
  • 3 is an electrically and thermally conductive layer
  • 4 is a heat sink.
  • a highly thermally conductive composite comprising the following components in mass percent:
  • the heat conductive sheet made of the above composite material is in the order of a distance from the heat source 1 in the order of the heat source 1 and the conductive heat conductive layer 2 and the conductive heat conductive layer 3, and the insulating heat conductive layer 2 is in contact with the heat source 1.
  • the conductive and thermally conductive layer 3 is in contact with the heat sink 4.
  • the insulating and thermally conductive layer 2 comprises a component one and a component two.
  • the electrically and thermally conductive layer 3 comprises a component two and a component three, and the percentage of each component is as shown in the above table.
  • the manufacturing process of the above thermal conductive sheet is as follows:
  • filler nano alumina, micro alumina, silicon carbide whisker, hexagonal boron nitride, graphene sheet, carbon nanotube, iron powder, nickel powder and cobalt powder are separately placed in the dryer. Dry at 120 ° C for 3 hours;
  • Silicone rubber pretreatment adding methyl vinyl silicone rubber and dimethyl silicone oil to the grinding machine for mixing Grinding to obtain a silicone rubber matrix;
  • step 3 Vacuum mixing: The silicone rubber matrix obtained in step 2 is placed in a vacuum kneader, and the first is added with hydroxy silicone oil, and then the main heat-conductive filler of component one is added in order from the least to the order of the filler quality.
  • a graphene sheet, a carbon nanotube, a silicon carbide whisker, a nano-alumina, a hexagonal boron nitride and a micro-alumina are sequentially added; then an auxiliary thermally conductive filler of the third component is added to the silicone rubber matrix,
  • the order of addition is also based on the order of the mass fraction of the filler from small to large, that is, the cobalt powder, the iron powder and the nickel powder are sequentially added and kneaded in a vacuum kneader, and vacuum kneaded for 35 minutes to obtain a thermally conductive silicone rubber compound;
  • a magnetic field is applied during molding in the mold, the magnetic field strength is 150kA/m, the thickness of the mold is set to 2mm, the upper part of the mold is surrounded by the excitation coil, and the magnetic field in the magnetic circuit is controlled by adjusting the current in the excitation coil.
  • the strength the test found that when the excitation current is adjusted to 1.5A, the effect is best, so that the three magnetic particles in the mold are clustered in a layer under the action of the magnetic field (the outer ring directly has the excitation coil to become strong).
  • the magnetic field region that is, the conductive heat conduction layer is formed, and the lower partial layer region (ie, there is no surrounding excitation coil outside) forms an insulating and thermally conductive layer;
  • Mold vulcanization After thin filming, it is molded by high temperature molding at 170 ° C for 15 minutes to obtain a formed sheet-like silicone rubber composite material;
  • the thermally conductive sheet is prepared from the components described in the above table, and the specific preparation process comprises the following steps:
  • filler nano alumina, micro alumina, silicon carbide whisker, hexagonal boron nitride, graphene sheet, carbon nanotube, iron powder, nickel powder and cobalt powder are separately placed in the dryer. Dry at 120 ° C for 4 hours;
  • silicone rubber pretreatment methyl vinyl silicone rubber and dimethyl silicone oil are added to the mill for mixing and grinding to obtain a silicone rubber matrix;
  • Vacuum mixing Put the silicone rubber matrix obtained in step 2 into a vacuum kneader, first add hydroxy silicone oil, and then add the main thermal conductive filler of component one, according to the order of the filler quality from small to large. Adding to the silicone rubber matrix, ie adding graphene sheets, carbon nanotubes, silicon carbide whiskers, nano-alumina, hexagonal boron nitride and micro-alumina in turn; then adding the auxiliary thermal conductive filler of component three to the silicone rubber matrix The order of addition is also based on the order of the mass fraction of the filler from small to large, that is, the cobalt powder, the iron powder and the nickel powder are sequentially added and kneaded in a vacuum kneader, and vacuum kneaded for 40 minutes to obtain a thermally conductive silicone rubber compound;
  • the mixed heat-conducting silicone rubber compound rubber is sealed with a plastic bag, left to stand for 20 hours, and then placed on the open machine through a thin pass, using a standard thin pass mode, thin pass 5 times,
  • the vulcanizing agent 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane is added during the thin pass process, and the sheet is thinned and then enters the forming mold;
  • the outer ring directly has the excitation coil to form a strong magnetic field region), that is, the conductive heat conduction layer is formed, and the lower partial layer region (the outer layer does not surround the excitation coil) forms an insulating heat conduction layer, and 98% of the experiments performed by the applicant are performed.
  • the component three is gathered in the upper layer region, and 98% of the material in the lower layer region is the component-aggregate;
  • Molding vulcanization After thin filming, it is molded by high temperature molding at 160 ° C for 20 minutes to obtain a formed sheet-like silicone rubber composite material.
  • the formed sheet-like silicone rubber composite obtained in the previous step is secondarily vulcanized at 210 ° C for 5 hours, further vulcanized to reduce the peroxide content, and volatilize the small molecular substance to obtain a high-quality sheet.
  • Thermally conductive silicone rubber composite is secondarily vulcanized at 210 ° C for 5 hours, further vulcanized to reduce the peroxide content, and volatilize the small molecular substance to obtain a high-quality sheet.
  • the thermal conductivity can be 6.7W/m.k and the hardness reaches 60 (shore 00).
  • the specific preparation process includes the following steps:
  • filler nano alumina, micro alumina, silicon carbide whisker, hexagonal boron nitride, graphene sheet, carbon nanotube, iron powder, nickel powder and cobalt powder are separately placed in the dryer. Dry at 110 ° C for 4 hours;
  • silicone rubber pretreatment methyl vinyl silicone rubber and dimethyl silicone oil are added to the mill for mixing and grinding to obtain a silicone rubber matrix;
  • step 3 Vacuum mixing: The silicone rubber matrix obtained in step 2 is placed in a vacuum kneader, and the first is added with hydroxy silicone oil, and then the main heat-conductive filler of component one is added in order from the least to the order of the filler quality.
  • a graphene sheet, a carbon nanotube, a silicon carbide whisker, a nano-alumina, a hexagonal boron nitride and a micro-alumina are sequentially added; then an auxiliary thermally conductive filler of the third component is added to the silicone rubber matrix,
  • the order of addition is also based on the order of the mass of the filler from small to large, that is, the addition of cobalt powder, iron powder,
  • the nickel powder is kneaded in a vacuum kneader and vacuum kneaded for 40 minutes to obtain a thermally conductive silicone rubber compound;
  • the mixed heat-conducting silicone rubber compound rubber is sealed with a plastic bag, left to stand for 24 hours, and then placed on the open machine through a thin pass, using a standard thin pass mode, thin through 7 times,
  • the vulcanizing agent 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane is added during the thin pass process, and the sheet is thinned and then enters the forming mold;
  • the outer ring directly has the excitation coil to form a strong magnetic field region), that is, the conductive heat conduction layer is formed, and the lower partial layer region (the outer layer is not surrounded by the excitation coil) forms an insulating heat conduction layer.
  • 98% The component three is gathered in the upper layer region, and 98% of the material in the lower layer region is the component-aggregate;
  • Mold vulcanization After thin filming, it is molded at 180 ° C for 18 minutes under high temperature molding to obtain a formed sheet-like silicone rubber composite material;
  • the formed sheet-like silicone rubber composite obtained in the previous step is secondarily vulcanized at 206 ° C for 4.5 hours, further vulcanized to reduce the peroxide content, and volatilize the small molecular substance to obtain a high-quality sheet.
  • Thermally conductive silicone rubber composite is secondarily vulcanized at 206 ° C for 4.5 hours, further vulcanized to reduce the peroxide content, and volatilize the small molecular substance to obtain a high-quality sheet.
  • the thermal conductivity can be 10W/m.k and the hardness reaches 55 (shore 00).

Abstract

A high thermal conductive composite material. The high thermal conductive composite material comprises the following components in percentage content by mass: 5% to 10% of nano-alumina, 20% to 45% of micron-alumina, 0.5% to 5% of silicon carbide whisker, 3% to 10% of hexagonal boron nitride, 0.1% to 1.2% of graphene sheets, 0.1% to 6% of carbon nanotubes, 0.5% to 2% of methyl vinyl silicone rubber, 5% to 12% of simethicone, 0.5% to 2% of hydroxyl silicone oil, 0.1% to 0.5% of a vulcanizing agent, 5% to 15% of iron powder, 10% to 25% of nickel powder and 5% to 15% of cobalt powder.

Description

一种高导热复合材料和由该材料制成的导热片及其制备方法High thermal conductive composite material and thermal conductive sheet made of the same and preparation method thereof 技术领域Technical field
本发明申请涉及一种导热复合材料，特别是一种导热系数高、安全性能好、稳定性好、回弹性高、柔顺性好的高导热硅橡胶复合材料及由所述导热材料制成的导热片及其制备方法，属于热界面材料导热技术领域。The invention relates to a heat conductive composite material, in particular to a high thermal conductivity silicone rubber composite material with high thermal conductivity, good safety performance, good stability, high resilience and good flexibility, and heat conduction made of the heat conductive material. The sheet and the preparation method thereof belong to the technical field of heat conduction of thermal interface materials.
背景技术Background technique
随着工业生产和科学技术的发展，在电器领域，电子产品朝着网络化、智能化、微型化的方向发展，使得电子元件和逻辑电路向全、轻、薄、小的方向发展，电子产品的发热量也随之增加，其工作环境急剧向高温方向变化。电子元器件温度每升高2℃，其可靠性就下降10％，因此散热问题也就成了设备能否正常运行的关键问题。因此需要高导热的材料，有效的散去电子设备产生的热量，这关系到产品的使用寿命和质量的可靠性。With the development of industrial production and science and technology, in the field of electrical appliances, electronic products are developing in the direction of network, intelligence and miniaturization, making electronic components and logic circuits develop in a full, light, thin and small direction, electronic products. The amount of heat generated also increases, and the working environment changes sharply toward high temperatures. For every 2 °C increase in temperature of electronic components, the reliability is reduced by 10%, so the heat dissipation problem becomes a key issue for the normal operation of the equipment. Therefore, a material with high thermal conductivity is needed to effectively dissipate the heat generated by the electronic device, which is related to the service life and quality reliability of the product.
目前，电子设备的散热问题，大多通过各种形式的散热器来解决。但在电子设备中，各种电子元件与散热器之间有许多接触面，它们之间存在空隙，导致热流不畅，为了解决这一问题，通常在接触面之间填充导热硅橡胶片，利用导热硅橡胶片其材质的柔软及在低压迫力作用下的弹性变量，为其粗糙表面构造密合接触，以便将微处理器、绘图处理器和其它重要芯片产生的热量带走，降低乃至消除空气热阻。At present, the heat dissipation problem of electronic devices is mostly solved by various forms of heat sinks. However, in electronic devices, there are many contact faces between various electronic components and the heat sink, and there are gaps between them, resulting in poor heat flow. In order to solve this problem, a thermal conductive silicone rubber sheet is usually filled between the contact faces, and the use is made. The thermal conductivity of the silicone rubber sheet is soft and the elastic variable under the action of low pressure, which is in close contact with the rough surface structure, so as to remove the heat generated by the microprocessor, the graphics processor and other important chips, reduce or even eliminate the air. Thermal resistance.
目前，业内对导热硅橡胶的散热模式大多选用两种方式：At present, the heat dissipation mode of thermal silicone rubber is mostly selected in two ways:
1、90％以上选用无机非金属氧化物或氮化物，譬如氧化铝、氮化铝等，作为填料对聚合物进行填充，制备出绝缘型导热硅橡胶材料。但导热性能差，导热系数一般在1.5-3W/m.k左右，不适合大功率元器件的散热需求。1. More than 90% of the inorganic non-metal oxides or nitrides, such as alumina, aluminum nitride, etc., are used as fillers to fill the polymer to prepare an insulating thermally conductive silicone rubber material. However, the thermal conductivity is poor, and the thermal conductivity is generally around 1.5-3 W/m.k, which is not suitable for the heat dissipation requirements of high-power components.
2、其它的部分，选用金属粉体或者碳纤维、石墨烯、碳纳米管等碳基材料， 作为填料对聚合物进行填充，制备出的导热硅橡胶导热性能有大幅度提升，其导热系数可以做到5.0-8W/m.k或更高，但它同时其导电性能也很高，安全性受到很大的制约，从而在实际的应用中有很大的局限性。2, other parts, the choice of metal powder or carbon fiber, graphene, carbon nanotubes and other carbon-based materials, Filling the polymer as a filler, the thermal conductivity of the prepared thermal conductive silicone rubber is greatly improved, and its thermal conductivity can be 5.0-8 W/mk or higher, but its conductivity is also high, and the safety is very high. Large constraints, and thus have great limitations in practical applications.
发明内容Summary of the invention
针对目前导热硅橡胶片存在的上述问题，本发明申请的目的在于，提供一种新型高导热复合材料及其制备方法，所述材料可以达到10W/m.k以上的导热系数，同时具备安全性能好、稳定性好、回弹性高、柔顺性好的优点，适用于发热元件和散热元件间的界面传热或类似用途。In view of the above problems of the current thermal conductive silicone rubber sheet, the object of the present invention is to provide a novel high thermal conductive composite material and a preparation method thereof, which can achieve a thermal conductivity of 10 W/mk or more, and have good safety performance. Good stability, high resilience and good flexibility. It is suitable for interface heat transfer between heat-generating components and heat-dissipating components or similar applications.
本发明申请的第一个目的是提供一种高导热复合材料，所述的高导热复合材料包括以下质量百分含量的各种组分：A first object of the present application is to provide a highly thermally conductive composite material comprising the following components in mass percent:
组分Component 质量百分比％% by mass
纳米氧化铝Nano alumina 5-10％5-10%
微米氧化铝Micron alumina 20-45％20-45%
碳化硅晶须Silicon carbide whiskers 0.5-5％0.5-5%
六方氮化硼Hexagonal boron nitride 3-10％3-10%
石墨烯片Graphene sheet 0.1-1.2％0.1-1.2%
碳纳米管Carbon nanotube 0.1-6％0.1-6%
甲基乙烯基硅橡胶Methyl vinyl silicone rubber 0.5-2％0.5-2%
二甲基硅油Dimethicone 5-12％5-12%
羟基硅油Hydroxy silicone oil 0.5-2％0.5-2%
硫化剂Vulcanizing agent 0.1-0.50.1-0.5
铁粉Iron powder 5-15％5-15%
镍粉Nickel powder 10-25％10-25%
钴粉Cobalt powder 5-15％5-15%
进一步的，所述纳米氧化铝(Al2O3)的粒径为60-150nm，纯度≥99.0％，由于其界面相容性好、表面光滑、分散性优良，可以提高材料的导热性和绝缘性能。其基本特征如下：具有球形度高、颗粒致密，比表面积≤23m2/g，高表面活性，松 装密度：≤0.37g/cm3，导热率：30W/m.K，加入基材中，能够明显提高其导热性能。Further, the nano-alumina (Al 2 O 3 ) has a particle diameter of 60-150 nm and a purity of ≥99.0%, and the thermal conductivity and insulation of the material can be improved due to good interfacial compatibility, smooth surface and excellent dispersibility. performance. The basic characteristics are as follows: high sphericity, dense particles, specific surface area ≤23m 2 /g, high surface activity, bulk density: ≤0.37g/cm 3 , thermal conductivity: 30W/mK, which can be added to the substrate. Improve its thermal conductivity.
进一步的，所述微米氧化铝(Al2O3)的粒径为1-100μm，纯度≥99.6％，由于分散性优良，可以提高材料的导热性和绝缘性能。其基本特征为：外观：白色粉末，纯度≥99.6％，粒径：1-100μm，比表面积≤1.06m2/g，密度：3.97g/cm3，导热率：30W/m.K，其原晶颗粒较大，粒径分布窄，吸油量超低，加入基材中，能够提高其导热性能。Further, the micron alumina (Al 2 O 3 ) has a particle diameter of 1-100 μm and a purity of ≥99.6%, and the thermal conductivity and the insulating property of the material can be improved due to excellent dispersibility. Its basic characteristics are: appearance: white powder, purity ≥99.6%, particle size: 1-100μm, specific surface area ≤1.06m 2 /g, density: 3.97g/cm 3 , thermal conductivity: 30W/mK, its original crystal particles Larger, narrow particle size distribution, ultra-low oil absorption, added to the substrate, can improve its thermal conductivity.
进一步的，所述碳化硅晶须(β-SiC Whisker)的长度为10-40μm，直径为0.05-0.2μm，添加量为总量的0.5-5％，由于纳米SiC长径比大，粒子更易在基材体系内部形成导热网链，减少材料内部空隙率，提高导热性能，其基本特征：β-SiC晶须长径比大、表面光洁度高、直径率高、晶体结构规整，具有优良的导热性能，导热系数为155W/m.K，密度3.21g/cm3，热膨胀系数4.3×10-6/K。Further, the silicon carbide whiskers (β-SiC Whisker) have a length of 10-40 μm and a diameter of 0.05-0.2 μm, and the added amount is 0.5-5% of the total amount. Since the nano-SiC has a large aspect ratio, the particles are easier. The heat conductive mesh chain is formed inside the substrate system to reduce the internal void ratio of the material and improve the thermal conductivity. The basic characteristics are: β-SiC whisker has large aspect ratio, high surface smoothness, high diameter ratio, regular crystal structure and excellent heat conduction. The performance, the thermal conductivity is 155 W/mK, the density is 3.21 g/cm 3 , and the thermal expansion coefficient is 4.3×10 -6 /K.
进一步的，所述六方氮化硼(HBN)的粒径为15μm，纯度＞98％，添加量为总量的3-10％。其除了保持优异的导热性外，还具有良好的绝缘性和润滑性和化学稳定性。基本特征如下：六方氮化硼的晶体结构具有类似石墨层状的结构，呈现松散、润滑、易吸潮、质轻等性状的白色粉末，密度2.27g/cm3，热导率为250w/m.k，热膨胀系数为：2×10-6/K。具有优良的绝缘性能，25℃为1014Ω-cm，低介电损耗108HZ时为2.5×10-4，介电常数为4，可透微波和红外线，低的摩擦系数：U为0.16。Further, the hexagonal boron nitride (HBN) has a particle diameter of 15 μm, a purity of >98%, and an addition amount of 3-10% of the total amount. In addition to maintaining excellent thermal conductivity, it also has good insulation and lubricity and chemical stability. The basic characteristics are as follows: the crystal structure of hexagonal boron nitride has a structure similar to graphite layer, and presents a white powder with loose, lubricious, easy moisture absorption, light weight and other properties, density 2.27g/cm 3 , thermal conductivity 250w/mk The coefficient of thermal expansion is: 2 × 10 -6 /K. It has excellent insulation performance, 10 14 Ω-cm at 25 ° C, 2.5 × 10 -4 at low dielectric loss of 108 Hz, dielectric constant of 4, microwave and infrared ray, and low friction coefficient: U is 0.16.
进一步的，所述石墨烯片的长度为3-20μm，厚度为20nm的层片状结构，添加量为总量的0.1-1.2％，其在添加量极少的情况下，就可以使热量在水平方向更快速地传导。其基本特征：高表面面积：2675m2/g，密度低：1.89g/cm3，热传导率5300W/m.k。Further, the graphene sheet has a length of 3-20 μm and a thickness of 20 nm, and the amount of addition is 0.1-1.2% of the total amount, and in the case where the amount of addition is extremely small, the heat can be made Conducted faster in the horizontal direction. Its basic characteristics are: high surface area: 2675m 2 /g, low density: 1.89g/cm 3 , thermal conductivity 5300W/mk.
进一步的，所述碳纳米管(CNTs)的OD粒径>50nm，ID粒径：5-15nm，长度10-20um，纯度>92％，由于具有超大的长径比，可以使其在添加量极少的情况 下，就可以大幅度提高材料的导热性及力学强度。其基本特征：比表面积>60m2/g。松装密度：0.18g/cm3，密度：2.1g/cm3，热传导率3000W/m.k。Further, the carbon nanotubes (CNTs) have an OD particle diameter of >50 nm, an ID particle diameter of 5-15 nm, a length of 10-20 um, and a purity of >92%, which can be added in an amount due to an excessive aspect ratio. In very rare cases, the thermal conductivity and mechanical strength of the material can be greatly improved. Its basic characteristics are: specific surface area > 60 m 2 /g. Bulk density: 0.18 g/cm 3 , density: 2.1 g/cm 3 , thermal conductivity 3000 W/mk.
进一步的，所述甲基乙烯基硅橡胶(VMQ)的含量为0.5-2％，采用的甲基乙烯基硅橡胶分子量为50-70万，乙烯基含量为0.07-0.15mo1％，其加工性能及抗压缩永久变形性能不错。Further, the content of the methyl vinyl silicone rubber (VMQ) is 0.5-2%, the methyl vinyl silicone rubber has a molecular weight of 500-700,000, and the vinyl content is 0.07-0.15 mol%, and the processing property thereof is obtained. And anti-compression permanent deformation performance is good.
进一步的，所述二甲基硅油(分子式：(CH3)3SiO[(CH3)2SiO]n-Si(CH3)3)的含量为5-12％，所采用的二甲基硅油粘度为50-500cps。Further, the content of the dimethyl silicone oil (molecular formula: (CH 3 ) 3 SiO[(CH 3 ) 2 SiO]n-Si(CH 3 ) 3 )) is 5-12%, and the dimethicone used is The viscosity is 50-500 cps.
进一步的，所述羟基硅油(分子式：HO[(CH3)2SiO]nH)的含量为0.5-2％，所采用的羟基硅油为小分子羟基硅油，粘度(25℃)：25-30cps，羟基含量8％。Further, the content of the hydroxy silicone oil (molecular formula: HO[(CH 3 ) 2 SiO] n H) is 0.5-2%, the hydroxy silicone oil used is a small molecule hydroxy silicone oil, viscosity (25 ° C): 25-30 cps The hydroxyl content is 8%.
进一步的，所述硫化剂的含量为0.1-0.5％，采用2，5-二甲基-2，5-二(叔丁基过氧基)己烷(分子式：C16H34O4)，所采用的该硫化剂在硫化后的气味在烷基过氧化物中较微小。Further, the content of the vulcanizing agent is 0.1-0.5%, and 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane (molecular formula: C 16 H 34 O 4 ) is used. The scent of the vulcanizing agent used after vulcanization is relatively small in the alkyl peroxide.
进一步的，所述铁粉的平均片径为5-10μm，片厚为50-100nm，比表面积>15m2/g，纯度≥99.9％。颜色：黑色，形貌：超细片状粉末，超细片状铁粉采用物理机械法制备，为具有高度活性的零价铁粉，具有高矫顽力，高比饱和磁化强度，高信噪比和抗氧化性好等优点。Further, the iron powder has an average diameter of 5-10 μm, a sheet thickness of 50-100 nm, a specific surface area of >15 m 2 /g, and a purity of 99.9%. Color: black, topography: ultra-fine flake powder, ultra-fine flake iron powder prepared by physical and mechanical method, is a highly active zero-valent iron powder, with high coercivity, high specific saturation magnetization, high signal noise Advantages such as better than oxidation resistance.
进一步的，所述镍粉的纯度≥99.7％，粒度为0.5-1.5μm，松装密度为0.5-0.9g/cm3，比表面积：2.0-6.0m2/g，碳和氧的含量≤0.3％。颜色:灰黑色，形貌：珠链状粉末，具有高饱和磁化强度和高磁导率，具有特殊的三维链状超精细颗粒网络，其独特的链珠状结构可产生良好的导电导热网络。Further, the nickel powder has a purity of ≥99.7%, a particle size of 0.5-1.5 μm, a bulk density of 0.5-0.9 g/cm 3 , a specific surface area of 2.0-6.0 m 2 /g, and a carbon and oxygen content ≤0.3. %. Color: gray black, topography: bead chain powder, with high saturation magnetization and high magnetic permeability, with a special three-dimensional chain superfine particle network, its unique bead structure can produce a good conductive and thermal network.
进一步的，所述钴粉(Co)的含量为5-15％，纯度≥99.9％，平均粒径为1.0μm，松装密度：0.83g/cm3，密度：8.9g/cm3，比表面积：8.0m2/g，碳和氧的含量总和 ≤0.42％，金属杂质含量总和≤0.03％。Further, the content of the cobalt powder (Co) is 5-15%, the purity is ≥99.9%, the average particle diameter is 1.0 μm, the bulk density is 0.83 g/cm 3 , the density is 8.9 g/cm 3 , and the specific surface area : 8.0 m 2 /g, the sum of carbon and oxygen content is ≤ 0.42%, and the sum of metal impurities is ≤ 0.03%.
本发明申请的第二个目的是提供由上述复合材料制成的导热片，所述导热片按照距离热源由近及远的顺序依次为绝缘导热层和导电导热层，绝缘导热层包括组分一和组分二，导电导热层包括组分二和组分三，各组分包括下述百分含量的各种成分：A second object of the present invention is to provide a thermally conductive sheet made of the above composite material, which is an insulating thermally conductive layer and an electrically and thermally conductive layer in the order of distance from the heat source, and the thermally conductive layer comprises a component one. And component two, the electrically conductive layer comprises component two and component three, each component comprising the following components in percentages:
Figure PCTCN2016075381-appb-000001
Figure PCTCN2016075381-appb-000001
其中，绝缘导热层用于接收热源，由于电绝缘，可以起到保护发热芯片、发热元器件的作用，可以安全地快速吸收热能；导电导热层接触散热器，可以更好的传导热能，提高材料的综合导热性能。The insulating and heat conducting layer is used for receiving the heat source. Due to the electrical insulation, the heat generating chip and the heat generating component can be protected, and the heat energy can be absorbed quickly and safely; the conductive heat conductive layer contacts the heat sink to better conduct heat energy and improve the material. Comprehensive thermal conductivity.
本发明申请的第三个目的是提供上述导热片的制备方法：A third object of the present application is to provide a method for preparing the above thermally conductive sheet:
本发明所提供的导热硅橡胶片复合材料，由以上质量百分比组分制成，具体制备过程包括如下步骤：The thermally conductive silicone rubber sheet composite material provided by the invention is made of the above mass percentage components, and the specific preparation process comprises the following steps:
1、填料预处理：将纳米氧化铝、微米氧化铝、碳化硅晶须、六方氮化硼、石墨烯片、碳纳米管、铁粉、镍粉和钴粉单独分别在烘干机中，于100-120℃烘干3-4h备用； 1. Pretreatment of filler: nano alumina, micro alumina, silicon carbide whisker, hexagonal boron nitride, graphene sheet, carbon nanotube, iron powder, nickel powder and cobalt powder are separately placed in the dryer. Dry at 3-4 hours at 100-120 °C;
2、硅橡胶预处理：将甲基乙烯基硅橡胶与二甲基硅油加入到研磨机中进行混合研磨，得到硅橡胶基体；2, silicone rubber pretreatment: methyl vinyl silicone rubber and dimethyl silicone oil are added to the mill for mixing and grinding to obtain a silicone rubber matrix;
3、真空混炼：将步骤2所得到的硅橡胶基体放入真空捏合机中，最先加入羟基硅油，其次添加组分一的主要导热填料，依照填料质量从少到多的顺序依次添加到硅橡胶基体中，即依次添加石墨烯片、碳纳米管、碳化硅晶须、纳米氧化铝、六方氮化硼和微米氧化铝；然后添加组分三的辅助导热填料添加到硅橡胶基体中，加入顺序也是依据填料质量分量从少到多的顺序，也就是依次添加钴粉、铁粉、镍粉在真空捏合机中进行混炼，真空捏合30-40分钟，得到导热硅橡胶混炼胶；3. Vacuum mixing: The silicone rubber matrix obtained in step 2 is placed in a vacuum kneader, and the first is added with hydroxy silicone oil, and then the main heat-conductive filler of component one is added in order from the least to the order of the filler quality. In the silicone rubber matrix, a graphene sheet, a carbon nanotube, a silicon carbide whisker, a nano-alumina, a hexagonal boron nitride and a micro-alumina are sequentially added; then an auxiliary thermally conductive filler of the third component is added to the silicone rubber matrix, The order of addition is also based on the order of the mass of the filler from small to large, that is, the cobalt powder, the iron powder and the nickel powder are sequentially added and kneaded in a vacuum kneader, and vacuum kneaded for 30-40 minutes to obtain a thermally conductive silicone rubber compound;
4、静置返炼：将混好的导热硅橡胶混炼胶用胶袋密封包裹，静置20-24小时，然后把其放在开炼机上薄通，采用标准薄通模式，薄通5-7次，薄通过程中加入硫化剂2，5-二甲基-2，5-二(叔丁基过氧基)己烷，薄通后出片，进入成型模具；4. Resting and refining: The mixed heat-conducting silicone rubber compound rubber is sealed with a plastic bag, left to stand for 20-24 hours, and then placed on the open machine on the thin pass, using the standard thin pass mode, thin pass 5 -7 times, adding vulcanizing agent 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane during the thin pass process, thinning the film, and entering the forming mold;
5、强磁分层：在模具中成型处理时施加磁场，磁场强度控制在150-800kA/m，模具厚度设定为0.5-12mm，模具上部分环绕励磁线圈，通过调节励磁线圈中的电流大小来控制磁回路中磁场的强度，我们测试发现，当励磁电流调到1.5A时效果最佳，原先这些带磁性的金属粒子随机分散在硅橡胶基体中，在磁场作用下这些粒子成链状或网状排列，且随着磁场强度的增强，颗粒之间的间距变小，联系更紧密，这样更容易形成导热通路，这样模具内组分三带磁性的金属粒子在磁场的作用下链集在一个层区(外环直接有励磁线圈行成强磁场区)，即形成导电导热层，下部分层区(外部没有环绕励磁线圈)的层区，就形成绝缘导热层，申请人做的实验中，98％的组分三聚集在上层区域，下层区98％的材料是组分一聚集；5. Strong magnetic stratification: apply magnetic field during molding process in the mold, the magnetic field strength is controlled at 150-800kA/m, the thickness of the mold is set to 0.5-12mm, the part of the mold is surrounded by the excitation coil, and the current in the excitation coil is adjusted. To control the strength of the magnetic field in the magnetic circuit, we found that the best when the excitation current is adjusted to 1.5A, the original magnetic particles are randomly dispersed in the silicone rubber matrix, the particles are chained under the magnetic field or The mesh is arranged, and as the strength of the magnetic field increases, the spacing between the particles becomes smaller and the contact is tighter, so that it is easier to form a heat conduction path, so that the three magnetic particles in the mold are clustered under the action of the magnetic field. A layer region (the outer ring directly has an excitation coil to form a strong magnetic field region), that is, a conductive heat conduction layer is formed, and a layer region of the lower partial layer region (with no surrounding excitation coil outside) forms an insulating heat conduction layer, and the applicant performs an experiment. 98% of the components are gathered in the upper zone, and 98% of the material in the lower zone is component-aggregate;
6、模压硫化：薄通出片后，在160-180℃下高温模压硫化15-20分钟成型，得到成型好的片状硅橡胶复合材料。6. Mold vulcanization: After thin filming, it is molded at 160-180 ° C for 15-20 minutes under high temperature molding to obtain a formed sheet-like silicone rubber composite.
7、二次硫化：将上个步骤所得到的成型好的片状硅橡胶复合材料在200-210℃ 下二次硫化4-5小时，进一步硫化减少过氧化物含量，挥发小分子物质，得到优质片状的导热硅橡胶复合材料。7. Secondary vulcanization: the formed sheet-like silicone rubber composite obtained in the previous step is at 200-210 ° C. The next secondary vulcanization is for 4-5 hours, further vulcanization reduces the peroxide content, and volatilizes the small molecular substance to obtain a high-quality sheet-shaped thermally conductive silicone rubber composite material.
本发明申请所述的高导热复合材料具有以下的优点：The high thermal conductivity composite material described in the present application has the following advantages:
1、设计创新：目前业内对导热硅橡胶大部分考虑到绝缘性要求，基本上是利用无机非金属材料作为填料来增加其导热性能，其实仅利用了声子热传导，而有的选用包括金属、碳基填料形成的导热塑料，其导热系数可以做到5.0-8W/m.k或更高，但它同时其导电性能也很高，所以大部分弃用该方案，或者只用在非常特殊的要求不高的导热领域，如何保持高的导热性，而又把导电性控制在合理的范围，这是个技术难点，本发明同时充分利用了电子、声子导热机能，很好的解决了导热与不导电的平衡点；1. Design innovation: At present, most of the thermal conductivity silicone rubber in the industry considers the insulation requirements. Basically, inorganic non-metallic materials are used as fillers to increase its thermal conductivity. In fact, only phonon heat conduction is utilized, and some options include metal. The heat conductive plastic formed by the carbon-based filler can have a thermal conductivity of 5.0-8 W/mk or higher, but at the same time its electrical conductivity is also high, so most of the products are discarded, or only used in very special requirements. In the field of high heat conduction, how to maintain high thermal conductivity and control the conductivity in a reasonable range is a technical difficulty. The invention also fully utilizes the electronic and phonon heat conduction functions, and well solves the heat conduction and non-conduction. Balance point
2、效能创新：目前导热硅橡胶材料的导热系数一般在1.5-3W/m.k左右，而本发明材料自身通过特殊配方和技术手段可以达到10W/m.k以上的导热系数，大幅度地提高材料导热性能。2. Performance innovation: At present, the thermal conductivity of the thermal conductive silicone rubber material is generally about 1.5-3W/mk, and the material of the invention can achieve a thermal conductivity of more than 10 W/mk through special formulation and technical means, and greatly improve the thermal conductivity of the material. .
3、填料创新：目前业内只选用了单项或少项填料进行搭配，我们对多项填料及综合影响性进行研究，对每种材料的粒径、形态选取，表面润湿性处理，掺杂分数调节，结合其自身的导热性能和导电性能的平衡处理，对填料不同种类进行科学搭配，尽量使其导热性能达到极致，而又保持了材料本身的安全性、回弹性和柔顺性。3. Filler innovation: At present, only single or small fillers are selected for matching in the industry. We study a number of fillers and comprehensive influences, particle size, morphology selection, surface wettability treatment, doping fraction for each material. Adjustment, combined with its own thermal conductivity and electrical conductivity balance treatment, scientifically match the different types of fillers, try to maximize the thermal conductivity, while maintaining the safety, resilience and flexibility of the material itself.
附图说明DRAWINGS
图1为本发明申请所述高导热复合材料制成的导热片的结构示意图；1 is a schematic structural view of a thermally conductive sheet made of a high thermal conductive composite material according to the present application;
其中，1为热源、2为绝缘导热层、3为导电导热层、4为散热器。Wherein, 1 is a heat source, 2 is an insulating and thermally conductive layer, 3 is an electrically and thermally conductive layer, and 4 is a heat sink.
具体实施方式 detailed description
以下结合附图和具体实施方式对本发明申请所述的技术方案进行说明，目的是为了公众更好地理解所述技术方案，而不是对其进行任意限制。The technical solutions described in the application of the present invention are described below in conjunction with the accompanying drawings and specific embodiments for the purpose of better understanding of the technical solutions by the public, and not by way of limitation.
实施例一 Embodiment 1
一种高导热复合材料，包括以下质量百分含量的各种组分：A highly thermally conductive composite comprising the following components in mass percent:
Figure PCTCN2016075381-appb-000002
Figure PCTCN2016075381-appb-000002
如图1所示，由上述复合材料制成的导热片，所述导热片按照距离热源1由近及远的顺序依次为绝缘导热层2和导电导热层3，绝缘导热层2与热源1接触，导电导热层3与散热器4接触，绝缘导热层2包括组分一和组分二，导电导热层3包括组分二和组分三，各组分的百分含量如上表所示。As shown in FIG. 1 , the heat conductive sheet made of the above composite material is in the order of a distance from the heat source 1 in the order of the heat source 1 and the conductive heat conductive layer 2 and the conductive heat conductive layer 3, and the insulating heat conductive layer 2 is in contact with the heat source 1. The conductive and thermally conductive layer 3 is in contact with the heat sink 4. The insulating and thermally conductive layer 2 comprises a component one and a component two. The electrically and thermally conductive layer 3 comprises a component two and a component three, and the percentage of each component is as shown in the above table.
上述导热片的制作过程如下：The manufacturing process of the above thermal conductive sheet is as follows:
1、填料预处理：将纳米氧化铝、微米氧化铝、碳化硅晶须、六方氮化硼、石墨烯片、碳纳米管、铁粉、镍粉和钴粉单独分别在烘干机中，于120℃烘干3h备用；1. Pretreatment of filler: nano alumina, micro alumina, silicon carbide whisker, hexagonal boron nitride, graphene sheet, carbon nanotube, iron powder, nickel powder and cobalt powder are separately placed in the dryer. Dry at 120 ° C for 3 hours;
2、硅橡胶预处理：将甲基乙烯基硅橡胶与二甲基硅油加入到研磨机中进行混 合研磨，得到硅橡胶基体；2. Silicone rubber pretreatment: adding methyl vinyl silicone rubber and dimethyl silicone oil to the grinding machine for mixing Grinding to obtain a silicone rubber matrix;
3、真空混炼：将步骤2所得到的硅橡胶基体放入真空捏合机中，最先加入羟基硅油，其次添加组分一的主要导热填料，依照填料质量从少到多的顺序依次添加到硅橡胶基体中，即依次添加石墨烯片、碳纳米管、碳化硅晶须、纳米氧化铝、六方氮化硼和微米氧化铝；然后添加组分三的辅助导热填料添加到硅橡胶基体中，加入顺序也是依据填料质量分量从少到多的顺序，也就是依次添加钴粉、铁粉、镍粉在真空捏合机中进行混炼，真空捏合35分钟，得到导热硅橡胶混炼胶；3. Vacuum mixing: The silicone rubber matrix obtained in step 2 is placed in a vacuum kneader, and the first is added with hydroxy silicone oil, and then the main heat-conductive filler of component one is added in order from the least to the order of the filler quality. In the silicone rubber matrix, a graphene sheet, a carbon nanotube, a silicon carbide whisker, a nano-alumina, a hexagonal boron nitride and a micro-alumina are sequentially added; then an auxiliary thermally conductive filler of the third component is added to the silicone rubber matrix, The order of addition is also based on the order of the mass fraction of the filler from small to large, that is, the cobalt powder, the iron powder and the nickel powder are sequentially added and kneaded in a vacuum kneader, and vacuum kneaded for 35 minutes to obtain a thermally conductive silicone rubber compound;
4、静置返炼：将混好的导热硅橡胶混炼胶用胶袋密封包裹，静置24小时，然后把其放在开炼机上薄通，薄通6次，薄通过程中加入硫化剂2，5-二甲基-2，5-二(叔丁基过氧基)己烷，薄通后出片，进入成型模具；4. Resting and refining: The mixed heat-conducting silicone rubber compound rubber is sealed with a plastic bag, left to stand for 24 hours, then placed on the open mill, thin-passed, thinned 6 times, and vulcanized during the thin pass process. 2,5-Dimethyl-2,5-di(tert-butylperoxy)hexane, which is thinned and then discharged into a molding die;
5、强磁分层：在模具中成型处理时施加磁场，磁场强度150kA/m，模具厚度设定为2mm，模具上部分环绕励磁线圈，通过调节励磁线圈中的电流大小来控制磁回路中磁场的强度，测试发现，当励磁电流调到1.5A时效果最佳，这样模具内组分三带磁性的金属粒子在磁场的作用下链集在一个层区(外环直接有励磁线圈行成强磁场区)，即形成导电导热层，下部分层区(即外部没有环绕励磁线圈)的层区，就形成绝缘导热层；5. Strong magnetic stratification: a magnetic field is applied during molding in the mold, the magnetic field strength is 150kA/m, the thickness of the mold is set to 2mm, the upper part of the mold is surrounded by the excitation coil, and the magnetic field in the magnetic circuit is controlled by adjusting the current in the excitation coil. The strength, the test found that when the excitation current is adjusted to 1.5A, the effect is best, so that the three magnetic particles in the mold are clustered in a layer under the action of the magnetic field (the outer ring directly has the excitation coil to become strong). The magnetic field region), that is, the conductive heat conduction layer is formed, and the lower partial layer region (ie, there is no surrounding excitation coil outside) forms an insulating and thermally conductive layer;
6、模压硫化：薄通出片后，在170℃下高温模压硫化15分钟成型，得到成型好的片状硅橡胶复合材料；6. Mold vulcanization: After thin filming, it is molded by high temperature molding at 170 ° C for 15 minutes to obtain a formed sheet-like silicone rubber composite material;
7、二次硫化：将上个步骤所得到的成型好的片状硅橡胶复合材料在200℃下二次硫化4小时，进一步硫化减少过氧化物含量，挥发小分子物质，得到优质片状的导热硅橡胶复合材料。7. Secondary vulcanization: The formed sheet-like silicone rubber composite obtained in the previous step is secondarily vulcanized at 200 ° C for 4 hours, further vulcanized to reduce the peroxide content, and volatilize small molecular substances to obtain high-quality flakes. Thermally conductive silicone rubber composite.
测试其相关性能如下:Test its related performance as follows:
性能指标Performance 单位unit 检测标准Testing standard 测试结果Test Results
硬度hardness Shore 00Shore 00 ASTM D2240ASTM D2240 5050
导热系数Thermal Conductivity W/mkW/mk ASTM D5470ASTM D5470 4.54.5
实施例二 Embodiment 2
配方二：Formula 2:
Figure PCTCN2016075381-appb-000003
Figure PCTCN2016075381-appb-000003
由上表所述各组分制备导热片，具体制备过程包括如下步骤：The thermally conductive sheet is prepared from the components described in the above table, and the specific preparation process comprises the following steps:
1、填料预处理：将纳米氧化铝、微米氧化铝、碳化硅晶须、六方氮化硼、石墨烯片、碳纳米管、铁粉、镍粉和钴粉单独分别在烘干机中，于120℃烘干4h备用；1. Pretreatment of filler: nano alumina, micro alumina, silicon carbide whisker, hexagonal boron nitride, graphene sheet, carbon nanotube, iron powder, nickel powder and cobalt powder are separately placed in the dryer. Dry at 120 ° C for 4 hours;
2、硅橡胶预处理：将甲基乙烯基硅橡胶与二甲基硅油加入到研磨机中进行混合研磨，得到硅橡胶基体；2, silicone rubber pretreatment: methyl vinyl silicone rubber and dimethyl silicone oil are added to the mill for mixing and grinding to obtain a silicone rubber matrix;
3、真空混炼：将步骤2所得到的硅橡胶基体放入真空捏合机中，最先加入羟基硅油，其次添加组分一的主要导热填料，依照填料质量从少到多的顺序依次添 加到硅橡胶基体中，即依次添加石墨烯片、碳纳米管、碳化硅晶须、纳米氧化铝、六方氮化硼和微米氧化铝；然后添加组分三的辅助导热填料添加到硅橡胶基体中，加入顺序也是依据填料质量分量从少到多的顺序，也就是依次添加钴粉、铁粉、镍粉在真空捏合机中进行混炼，真空捏合40分钟，得到导热硅橡胶混炼胶；3. Vacuum mixing: Put the silicone rubber matrix obtained in step 2 into a vacuum kneader, first add hydroxy silicone oil, and then add the main thermal conductive filler of component one, according to the order of the filler quality from small to large. Adding to the silicone rubber matrix, ie adding graphene sheets, carbon nanotubes, silicon carbide whiskers, nano-alumina, hexagonal boron nitride and micro-alumina in turn; then adding the auxiliary thermal conductive filler of component three to the silicone rubber matrix The order of addition is also based on the order of the mass fraction of the filler from small to large, that is, the cobalt powder, the iron powder and the nickel powder are sequentially added and kneaded in a vacuum kneader, and vacuum kneaded for 40 minutes to obtain a thermally conductive silicone rubber compound;
4、静置返炼：将混好的导热硅橡胶混炼胶用胶袋密封包裹，静置20小时，然后把其放在开炼机上薄通，采用标准薄通模式，薄通5次，薄通过程中加入硫化剂2，5-二甲基-2，5-二(叔丁基过氧基)己烷，薄通后出片，进入成型模具；4. Resting and refining: The mixed heat-conducting silicone rubber compound rubber is sealed with a plastic bag, left to stand for 20 hours, and then placed on the open machine through a thin pass, using a standard thin pass mode, thin pass 5 times, The vulcanizing agent 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane is added during the thin pass process, and the sheet is thinned and then enters the forming mold;
5、强磁分层：在模具中成型处理时施加磁场，磁场强度控制在400kA/m，模具厚度设定为0.5mm，模具上部分环绕励磁线圈，通过调节励磁线圈中的电流大小来控制磁回路中磁场的强度，我们测试发现，当励磁电流调到1.5A时效果最佳，原先这些带磁性的金属粒子随机分散在硅橡胶基体中，在磁场作用下这些粒子成链状或网状排列，且随着磁场强度的增强，颗粒之间的间距变小，联系更紧密，这样更容易形成导热通路，这样模具内组分三带磁性的金属粒子在磁场的作用下链集在一个层区(外环直接有励磁线圈行成强磁场区)，即形成导电导热层，下部分层区(外部没有环绕励磁线圈)的层区，就形成绝缘导热层，申请人做的实验中，98％的组分三聚集在上层区域，下层区98％的材料是组分一聚集；5. Strong magnetic stratification: Apply magnetic field during forming process in the mold, the magnetic field strength is controlled at 400kA/m, the mold thickness is set to 0.5mm, the upper part of the mold is surrounded by the excitation coil, and the magnetic force is controlled by adjusting the current in the excitation coil. The strength of the magnetic field in the loop, we found that the best when the excitation current is adjusted to 1.5A, the original magnetic particles are randomly dispersed in the silicone rubber matrix, the particles are chained or meshed under the action of a magnetic field. And as the strength of the magnetic field increases, the spacing between the particles becomes smaller and the contact is tighter, so that it is easier to form a heat conduction path, so that the three magnetic particles of the metal in the mold are clustered in a layer under the action of the magnetic field. (The outer ring directly has the excitation coil to form a strong magnetic field region), that is, the conductive heat conduction layer is formed, and the lower partial layer region (the outer layer does not surround the excitation coil) forms an insulating heat conduction layer, and 98% of the experiments performed by the applicant are performed. The component three is gathered in the upper layer region, and 98% of the material in the lower layer region is the component-aggregate;
6、模压硫化：薄通出片后，在160℃下高温模压硫化20分钟成型，得到成型好的片状硅橡胶复合材料。6. Molding vulcanization: After thin filming, it is molded by high temperature molding at 160 ° C for 20 minutes to obtain a formed sheet-like silicone rubber composite material.
7、二次硫化：将上个步骤所得到的成型好的片状硅橡胶复合材料在210℃下二次硫化5小时，进一步硫化减少过氧化物含量，挥发小分子物质，得到优质片状的导热硅橡胶复合材料。7. Secondary vulcanization: The formed sheet-like silicone rubber composite obtained in the previous step is secondarily vulcanized at 210 ° C for 5 hours, further vulcanized to reduce the peroxide content, and volatilize the small molecular substance to obtain a high-quality sheet. Thermally conductive silicone rubber composite.
通过检测后，导热系数可以做到6.7W/m.k，硬度达到60(shore 00)。 After the test, the thermal conductivity can be 6.7W/m.k and the hardness reaches 60 (shore 00).
实施例三 Embodiment 3
配方三：Formula 3:
Figure PCTCN2016075381-appb-000004
Figure PCTCN2016075381-appb-000004
具体制备过程包括如下步骤：The specific preparation process includes the following steps:
1、填料预处理：将纳米氧化铝、微米氧化铝、碳化硅晶须、六方氮化硼、石墨烯片、碳纳米管、铁粉、镍粉和钴粉单独分别在烘干机中，于110℃烘干4h备用；1. Pretreatment of filler: nano alumina, micro alumina, silicon carbide whisker, hexagonal boron nitride, graphene sheet, carbon nanotube, iron powder, nickel powder and cobalt powder are separately placed in the dryer. Dry at 110 ° C for 4 hours;
2、硅橡胶预处理：将甲基乙烯基硅橡胶与二甲基硅油加入到研磨机中进行混合研磨，得到硅橡胶基体；2, silicone rubber pretreatment: methyl vinyl silicone rubber and dimethyl silicone oil are added to the mill for mixing and grinding to obtain a silicone rubber matrix;
3、真空混炼：将步骤2所得到的硅橡胶基体放入真空捏合机中，最先加入羟基硅油，其次添加组分一的主要导热填料，依照填料质量从少到多的顺序依次添加到硅橡胶基体中，即依次添加石墨烯片、碳纳米管、碳化硅晶须、纳米氧化铝、六方氮化硼和微米氧化铝；然后添加组分三的辅助导热填料添加到硅橡胶基体中，加入顺序也是依据填料质量分量从少到多的顺序，也就是依次添加钴粉、铁粉、 镍粉在真空捏合机中进行混炼，真空捏合40分钟，得到导热硅橡胶混炼胶；3. Vacuum mixing: The silicone rubber matrix obtained in step 2 is placed in a vacuum kneader, and the first is added with hydroxy silicone oil, and then the main heat-conductive filler of component one is added in order from the least to the order of the filler quality. In the silicone rubber matrix, a graphene sheet, a carbon nanotube, a silicon carbide whisker, a nano-alumina, a hexagonal boron nitride and a micro-alumina are sequentially added; then an auxiliary thermally conductive filler of the third component is added to the silicone rubber matrix, The order of addition is also based on the order of the mass of the filler from small to large, that is, the addition of cobalt powder, iron powder, The nickel powder is kneaded in a vacuum kneader and vacuum kneaded for 40 minutes to obtain a thermally conductive silicone rubber compound;
4、静置返炼：将混好的导热硅橡胶混炼胶用胶袋密封包裹，静置24小时，然后把其放在开炼机上薄通，采用标准薄通模式，薄通7次，薄通过程中加入硫化剂2，5-二甲基-2，5-二(叔丁基过氧基)己烷，薄通后出片，进入成型模具；4. Resting and refining: The mixed heat-conducting silicone rubber compound rubber is sealed with a plastic bag, left to stand for 24 hours, and then placed on the open machine through a thin pass, using a standard thin pass mode, thin through 7 times, The vulcanizing agent 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane is added during the thin pass process, and the sheet is thinned and then enters the forming mold;
5、强磁分层：在模具中成型处理时施加磁场，磁场强度控制在800kA/m，模具厚度设定为12mm，模具上部分环绕励磁线圈，通过调节励磁线圈中的电流大小来控制磁回路中磁场的强度，我们测试发现，当励磁电流调到1.5A时效果最佳，原先这些带磁性的金属粒子随机分散在硅橡胶基体中，在磁场作用下这些粒子成链状或网状排列，且随着磁场强度的增强，颗粒之间的间距变小，联系更紧密，这样更容易形成导热通路，这样模具内组分三带磁性的金属粒子在磁场的作用下链集在一个层区(外环直接有励磁线圈行成强磁场区)，即形成导电导热层，下部分层区(外部没有环绕励磁线圈)的层区，就形成绝缘导热层，申请人做的实验中，98％的组分三聚集在上层区域，下层区98％的材料是组分一聚集；5. Strong magnetic stratification: Apply magnetic field during molding process in the mold, the magnetic field strength is controlled at 800kA/m, the mold thickness is set to 12mm, the upper part of the mold is surrounded by the excitation coil, and the magnetic circuit is controlled by adjusting the current in the excitation coil. The strength of the medium magnetic field, we found that the best when the excitation current is adjusted to 1.5A, the original magnetic particles are randomly dispersed in the silicone rubber matrix, the particles are arranged in a chain or mesh under the action of a magnetic field. And as the strength of the magnetic field increases, the spacing between the particles becomes smaller and the contact is closer, so that it is easier to form a heat conduction path, so that the three magnetic metal particles in the mold are clustered in one layer under the action of the magnetic field ( The outer ring directly has the excitation coil to form a strong magnetic field region), that is, the conductive heat conduction layer is formed, and the lower partial layer region (the outer layer is not surrounded by the excitation coil) forms an insulating heat conduction layer. In the experiment conducted by the applicant, 98% The component three is gathered in the upper layer region, and 98% of the material in the lower layer region is the component-aggregate;
6、模压硫化：薄通出片后，在180℃下高温模压硫化18分钟成型，得到成型好的片状硅橡胶复合材料；6. Mold vulcanization: After thin filming, it is molded at 180 ° C for 18 minutes under high temperature molding to obtain a formed sheet-like silicone rubber composite material;
7、二次硫化：将上个步骤所得到的成型好的片状硅橡胶复合材料在206℃下二次硫化4.5小时，进一步硫化减少过氧化物含量，挥发小分子物质，得到优质片状的导热硅橡胶复合材料。7. Secondary vulcanization: The formed sheet-like silicone rubber composite obtained in the previous step is secondarily vulcanized at 206 ° C for 4.5 hours, further vulcanized to reduce the peroxide content, and volatilize the small molecular substance to obtain a high-quality sheet. Thermally conductive silicone rubber composite.
通过实施后，导热系数可以做到10W/m.k，硬度达到55(shore 00)。After implementation, the thermal conductivity can be 10W/m.k and the hardness reaches 55 (shore 00).
应该理解的是，上述内容包括附图不是对所述技术方案的限制，事实上，在相同或近似的原理下，对所述技术方案进行的改进，包括对上述各组分百分含量的微小改动以及导热片制备方法中，对各步骤工艺条件的改变，只要满足导热复合材料及导热片的主要特性相近似，则都在本发明申请所要求的技术方案之内。 It should be understood that the above description including the accompanying drawings is not a limitation of the technical solutions. In fact, under the same or similar principles, the improvement of the technical solution includes a slight percentage of the above components. In the modification and the preparation method of the thermal conductive sheet, the change of the process conditions in each step is within the technical solution required by the present application as long as the main characteristics of the thermally conductive composite material and the thermal conductive sheet are approximated.

Claims (6)

  1. 一种高导热复合材料，其特征在于，所述的高导热复合材料包括以下质量百分含量的各种组分：A highly thermally conductive composite material characterized in that the high thermal conductivity composite material comprises various components in the following mass percentages:
    组分Component 质量百分比％% by mass 纳米氧化铝Nano alumina 5-10％5-10% 微米氧化铝Micron alumina 20-45％20-45% 碳化硅晶须Silicon carbide whiskers 0.5-5％0.5-5% 六方氮化硼Hexagonal boron nitride 3-10％3-10% 石墨烯片Graphene sheet 0.1-1.2％0.1-1.2% 碳纳米管Carbon nanotube 0.1-6％0.1-6% 甲基乙烯基硅橡胶Methyl vinyl silicone rubber 0.5-2％0.5-2% 二甲基硅油Dimethicone 5-12％5-12% 羟基硅油Hydroxy silicone oil 0.5-2％0.5-2% 硫化剂Vulcanizing agent 0.1-0.50.1-0.5 铁粉Iron powder 5-15％5-15% 镍粉Nickel powder 10-25％10-25% 钴粉Cobalt powder 5-15％5-15%
    。.
  2. 根据权利要求1所述的高导热复合材料，其特征在于：所述纳米氧化铝的粒径为60-150nm，纯度≥99.0％；所述微米氧化铝的粒径为1-100μm，纯度≥99.6％；所述碳化硅晶须的长度为10-40μm，直径为0.05-0.2μm；所述六方氮化硼的粒径为15μm，纯度＞98％；所述石墨烯片的长度为3-20μm，厚度为20nm；所述碳纳米管的OD粒径>50nm，ID粒径：5-15nm，长度10-20um，纯度>92％。The high thermal conductive composite material according to claim 1, wherein the nano-alumina has a particle diameter of 60-150 nm and a purity of ≥99.0%; the micro-alumina has a particle diameter of 1-100 μm and a purity of ≥99.6. The silicon carbide whisker has a length of 10-40 μm and a diameter of 0.05-0.2 μm; the hexagonal boron nitride has a particle diameter of 15 μm and a purity of >98%; and the graphene sheet has a length of 3-20 μm. The thickness is 20 nm; the carbon nanotubes have an OD particle size of >50 nm, an ID particle size of 5-15 nm, a length of 10-20 um, and a purity of >92%.
  3. 根据权利要求1或2所述的高导热复合材料，其特征在于：所述甲基乙烯基硅橡胶分子量为50-70万，乙烯基含量为0.07-0.15mo1％；所述二甲基硅油的粘度为50-500cps；所述羟基硅油的粘度为25-30cps，羟基含量8％；所述硫化剂为2，5-二甲基-2，5-二(叔丁基过氧基)己烷。The high thermal conductive composite material according to claim 1 or 2, wherein the methyl vinyl silicone rubber has a molecular weight of from 500 to 700,000 and a vinyl content of from 0.07 to 0.15 mol%; the dimethyl silicone oil The viscosity is 50-500 cps; the viscosity of the hydroxy silicone oil is 25-30 cps, and the hydroxyl content is 8%; the vulcanizing agent is 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane .
  4. 根据权利要求1或2所述的高导热复合材料，其特征在于：所述铁粉的 平均片径为5-10μm，片厚为50-100nm，比表面积>15m2/g，纯度≥99.9％；所述镍粉的纯度≥99.7％，粒度为0.5-1.5μm，松装密度为0.5-0.9g/cm3，比表面积：2.0-6.0m2/g，碳和氧的含量≤0.3％；所述钴粉(Co)的含量为5-15％，纯度≥99.9％，平均粒径为1.0μm，松装密度：0.83g/cm3，密度：8.9g/cm3，比表面积：8.0m2/g，碳和氧的含量总和≤0.42％，金属杂质含量总和≤0.03％。The high thermal conductive composite material according to claim 1 or 2, wherein the iron powder has an average diameter of 5-10 μm, a sheet thickness of 50-100 nm, a specific surface area of >15 m 2 /g, and a purity of 99.9%. The nickel powder has a purity of ≥99.7%, a particle size of 0.5-1.5 μm, a bulk density of 0.5-0.9 g/cm 3 , a specific surface area of 2.0-6.0 m 2 /g, and a carbon and oxygen content ≤0.3%; The content of the cobalt powder (Co) is 5-15%, the purity is ≥99.9%, the average particle diameter is 1.0 μm, the bulk density is 0.83 g/cm 3 , the density is 8.9 g/cm 3 , and the specific surface area is 8.0 m. 2 / g, the total content of carbon and oxygen is ≤ 0.42%, and the sum of metal impurities is ≤ 0.03%.
  5. 一种采用权利要求1所述的高导热复合材料制成的导热片，其特征在于，所述的导热片按照距离热源由近及远的顺序依次为绝缘导热层和导电导热层，绝缘导热层包括组分一和组分二，导电导热层包括组分二和组分三，各组分包括下述百分含量的各种成分：A thermally conductive sheet made of the high thermal conductive composite material according to claim 1, wherein the thermal conductive sheet is insulative heat conductive layer and conductive heat conductive layer in the order of distance from the heat source, and the heat conductive layer is insulated. Including component one and component two, the electrically and thermally conductive layer comprises component two and component three, each component comprising the following components in percentages:
    Figure PCTCN2016075381-appb-100001
    Figure PCTCN2016075381-appb-100001
  6. 权利要求5所述导热片的制备方法，其特征在于，包括如下的步骤：A method of preparing a thermally conductive sheet according to claim 5, comprising the steps of:
    1)填料预处理：将纳米氧化铝、微米氧化铝、碳化硅晶须、六方氮化硼、石墨烯片、碳纳米管、铁粉、镍粉和钴粉单独分别在烘干机中，于100-120℃烘干3-4h备用； 1) Pretreatment of filler: Nano alumina, micro alumina, silicon carbide whisker, hexagonal boron nitride, graphene sheet, carbon nanotube, iron powder, nickel powder and cobalt powder are separately placed in the dryer. Dry at 3-4 hours at 100-120 °C;
    2)硅橡胶预处理：将甲基乙烯基硅橡胶与二甲基硅油加入到研磨机中进行混合研磨，得到硅橡胶基体；2) Silicone rubber pretreatment: methyl vinyl silicone rubber and dimethyl silicone oil are added to a grinder for mixing and grinding to obtain a silicone rubber matrix;
    3)真空混炼：将步骤2)所得到的硅橡胶基体放入真空捏合机中，最先加入羟基硅油，其次添加组分一的主要导热填料，依照填料质量从少到多的顺序依次添加到硅橡胶基体中，即依次添加石墨烯片、碳纳米管、碳化硅晶须、纳米氧化铝、六方氮化硼和微米氧化铝；然后添加组分三的辅助导热填料添加到硅橡胶基体中，加入顺序也是依据填料质量分量从少到多的顺序，也就是依次添加钴粉、铁粉、镍粉在真空捏合机中进行混炼，真空捏合30-40分钟，得到导热硅橡胶混炼胶；3) Vacuum mixing: the silicone rubber substrate obtained in the step 2) is placed in a vacuum kneader, and the first is added with the hydroxy silicone oil, and then the main heat-conductive filler of the first component is added in order of decreasing the mass of the filler. Into the silicone rubber matrix, namely, adding graphene sheets, carbon nanotubes, silicon carbide whiskers, nano-alumina, hexagonal boron nitride and micro-alumina; then adding the auxiliary thermal conductive filler of component three to the silicone rubber matrix The order of addition is also based on the order of the mass fraction of the filler from small to large, that is, the cobalt powder, the iron powder and the nickel powder are sequentially added and kneaded in a vacuum kneader, and vacuum kneaded for 30-40 minutes to obtain a thermally conductive silicone rubber compound. ;
    4)静置返炼：将混好的导热硅橡胶混炼胶用胶袋密封包裹，静置20-24小时，然后把其放在开炼机上薄通，采用标准薄通模式，薄通5-7次，薄通过程中加入硫化剂2，5-二甲基-2，5-二(叔丁基过氧基)己烷，薄通后出片，进入成型模具；4) Resting and refining: The mixed heat-conducting silicone rubber compound rubber is sealed with a plastic bag, left to stand for 20-24 hours, and then placed on the open machine through a thin pass, using the standard thin pass mode, thin pass 5 -7 times, adding vulcanizing agent 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane during the thin pass process, thinning the film, and entering the forming mold;
    5)强磁分层：在模具中成型处理时施加磁场，磁场强度控制在150-800kA/m，模具厚度设定为0.5-12mm，模具上部分环绕励磁线圈，通过调节励磁线圈中的电流大小来控制磁回路中磁场的强度，我们测试发现，当励磁电流调到1.5A时效果最佳，原先这些带磁性的金属粒子随机分散在硅橡胶基体中，在磁场作用下这些粒子成链状或网状排列，且随着磁场强度的增强，颗粒之间的间距变小，联系更紧密，这样更容易形成导热通路，这样模具内组分三带磁性的金属粒子在磁场的作用下链集在一个层区，该层区的外环有励磁线圈，即形成导电导热层，下部分层区,该下部分层区外部没有环绕励磁线圈，就形成绝缘导热层，申请人做的实验中，98％的组分三聚集在上层区域，下层区98％的材料是组分一聚集； 5) Strong magnetic stratification: apply magnetic field during molding process in the mold, the magnetic field strength is controlled at 150-800kA/m, the mold thickness is set to 0.5-12mm, and the upper part of the mold is surrounded by the excitation coil, and the current in the excitation coil is adjusted. To control the strength of the magnetic field in the magnetic circuit, we found that the best when the excitation current is adjusted to 1.5A, the original magnetic particles are randomly dispersed in the silicone rubber matrix, the particles are chained under the magnetic field or The mesh is arranged, and as the strength of the magnetic field increases, the spacing between the particles becomes smaller and the contact is tighter, so that it is easier to form a heat conduction path, so that the three magnetic particles in the mold are clustered under the action of the magnetic field. a layer region, the outer ring of the layer region has an excitation coil, that is, an electrically conductive and thermally conductive layer is formed, and a lower partial layer region is formed. The outer portion of the lower portion of the layer region is not surrounded by an excitation coil to form an insulating and thermally conductive layer. In an experiment conducted by the applicant, 98 % of the component three is concentrated in the upper zone, and 98% of the material in the lower zone is component-aggregate;
    6)模压硫化：薄通出片后，在160-180℃下高温模压硫化15-20分钟成型，得到成型好的片状硅橡胶复合材料；6) Molding vulcanization: After thin filming, it is molded at 160-180 ° C for 15-20 minutes under high temperature molding to obtain a formed sheet-like silicone rubber composite material;
    7)二次硫化：将上个步骤所得到的成型好的片状硅橡胶复合材料在200-210℃下二次硫化4-5小时，进一步硫化减少过氧化物含量，挥发小分子物质，得到优质片状的导热硅橡胶复合材料。 7) Secondary vulcanization: the formed sheet-like silicone rubber composite obtained in the previous step is secondarily vulcanized at 200-210 ° C for 4-5 hours, further vulcanized to reduce the peroxide content, and volatilize the small molecular substance to obtain High quality sheet-shaped thermal silicone rubber composite.
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