CN112280312B - Heat-conducting and wave-absorbing integrated graphene thermal interface material and preparation method thereof - Google Patents
Heat-conducting and wave-absorbing integrated graphene thermal interface material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a heat-conducting wave-absorbing integrated graphene thermal interface material and a preparation method thereof, which are used for preparing a graphene thermal interface material with excellent heat-conducting property and high insulating property by respectively taking graphene oxide as a carrier and selecting a heat-conducting insulating material and a magnetic insulating material to be compounded and reduced, wherein the electromagnetic shielding property of the graphene thermal interface material is less than-20 dB at the absorption of 3-5 GHz.
Description
Technical Field
The invention relates to a heat-conducting wave-absorbing integrated graphene thermal interface material and a preparation method thereof, in particular to a high-heat-conducting, electromagnetic-shielding and insulation-integrated graphene thermal interface material and a preparation method thereof, and belongs to the technical field of graphene heat-conducting and shielding materials.
Background
The introduction of high frequency in the 5G era, the upgrading of hardware parts and the multiplication of the quantity of internet equipment and antennas, the electromagnetic interference between the equipment and inside the equipment is ubiquitous, and the harm of the electromagnetic interference and the electromagnetic radiation to the electronic equipment is increasingly serious. Meanwhile, along with the updating and upgrading of electronic products, the power consumption of equipment is continuously increased, and the heat productivity is also rapidly increased. The bottleneck of future high-frequency and high-power electronic products is the electromagnetic radiation and heat generated by the electronic products, and in order to solve the problem, more and more electromagnetic shielding and heat conducting devices are added into the electronic products during design. Therefore, the role of electromagnetic shielding and heat dissipation materials and devices will become more important, and the demand will continue to increase greatly in the future. Therefore, it is very urgent and important to develop a thermal interface material with high thermal conductivity and battery shielding.
Graphene has attracted much attention as a novel carbon material since its discovery in 2004. The material is a quasi-two-dimensional crystal material which is composed of sp2 hybridized carbon atoms and has the thickness of only a single atomic layer or a plurality of single atomic layers, and has excellent performances of high light transmittance, electric conductivity, thermal conductivity, high specific surface area, high strength, flexibility and the like. Since graphene has excellent heat conductivity, the thermal conductivity of the graphene is as high as 5000W/(m.K), which is 10 times that of copper, and the graphene also has a thermal conductivity of as high as 2600 m2The specific surface area is ultrahigh and the specific surface area is 100 times of that of steel, and the steel has good flexibility and extensibility. Therefore, graphene is an ideal light-weight and efficient heat management material in theory. However, the material has ultrahigh conductivity, so that the thermal interface material has conductivity, and the nano structure of the graphene-based material is beneficial to multiple internal reflection and scattering of electromagnetic waves. Secondly, the large number of defects caused by the functional groups is the main factor responsible for the high dielectric losses, since the functional groups and defects cause an asymmetric distribution of charges forming dipoles which will rotate in the direction of the electromagnetic field, converting the electromagnetic energy into thermal energy due to the presence of relaxation losses. Therefore, how to utilize the excellent thermal conductivity and electromagnetic shielding performance of graphene and overcome the electrical conductivity of graphene is a major concern at present.
In the prior art, CN111334260A discloses that a heat-conducting, electromagnetic shielding and insulating interface material is prepared by adding shaped carbon and graphitized carbon-coated magnetic particles and conventional heat-conducting filler into room-temperature vulcanized rubber, wherein the heat conductivity is 2.49W/(mK); under 500V test voltage, the volume resistivity is 2.03 multiplied by 1016 omega cm; at the frequency of 8.2GHz, the electromagnetic shielding rate reaches 72.7%. The heat conduction of the method still depends on the heat conduction of the traditional heat conduction filler, so that the heat conduction performance is low, the maximum wave-absorbing frequency band is 8.2GHz, and the heat conduction performance and the shielding performance are not suitable for the 5G field.
CN109486191A utilizes high-performance heat-conducting electromagnetic shielding materials (metal, alloy or carbon/metal) as heat-conducting electricity to prepare heat-conducting shielding glue, the heat conductivity coefficient of the glue is more than 3W/mK, the hardness Shore A is less than 40, the method directly adopts noble metals as the conductive shielding filler, the cost is very high, the electricity is conducted, and no mention is made about the shielding frequency band.
CN110294939A utilizes heat-conducting fillers such as flake graphite powder, flake nickel-plated graphite powder, flake gold copper powder and flake silver powder as heat-conducting fillers, spherical nickel powder, carbonyl iron powder, carbonyl nickel powder, nickel-coated carbon powder, nickel-coated aluminum powder, silver-coated aluminum powder and silver-coated copper powder as wave-absorbing fillers, and prepares a thermal interface material with a heat conductivity coefficient of more than 10W/mK by orienting two-dimensional heat-conducting fillers.
Disclosure of Invention
The invention aims to provide a heat-conducting wave-absorbing integrated graphene thermal interface material and a preparation method thereof, wherein graphene oxide is respectively used as a carrier, and a heat-conducting insulating material and a magnetic insulating material are selected to be compounded and reduced with the graphene oxide, so that the graphene thermal interface material with excellent heat-conducting property and high insulating property can be prepared, and the electromagnetic shielding property of the graphene thermal interface material is less than-20 dB at the absorption of 5 GHz.
The invention is realized by the following technical scheme: a preparation method of a heat-conducting wave-absorbing integrated graphene thermal interface material comprises the steps of taking graphene oxide as a carrier, respectively compounding a heat-conducting insulating material and a magnetic insulating material on the graphene oxide to obtain corresponding graphene-heat-conducting insulating composite material and graphene-magnetic insulating composite material, mixing the reduced graphene-heat-conducting insulating composite material and graphene-magnetic insulating composite material with vinyl silicone oil, a catalyst, an inhibitor and hydrogen-containing silicone oil, and carrying out calendering and curing to obtain the graphene thermal interface material.
According to the weight parts, 100 parts of heat-conducting insulating material, 0.1-5 parts of cation modifier, 10-50 parts of absolute ethyl alcohol and 0.01-1 part of concentrated hydrochloric acid are mixed, 1-10 parts of graphene oxide is added under ultrasonic, and then the graphene-heat-conducting insulating composite material is prepared after stirring and drying.
Adding 100 parts by weight of graphene-heat-conducting insulating composite material into 10-100 parts by weight of reducing agent with mass concentration of 1-10%, and stirring, filtering and drying to obtain the graphene-heat-conducting insulating composite filler.
According to the weight parts, 100 parts of magnetic insulating material, 0.1-5 parts of cation modifier, 10-50 parts of absolute ethyl alcohol and 0.01-1 part of concentrated hydrochloric acid are mixed, 1-10 parts of graphene oxide is added under ultrasonic, and then the graphene-magnetic insulating composite material is prepared after stirring and drying.
Adding 100 parts by weight of graphene-magnetic insulation composite material into 10-100 parts by weight of reducing agent with mass concentration of 1-10%, stirring, filtering and drying to obtain the graphene-magnetic insulation composite filler.
According to parts by weight, stirring and mixing 1-200 parts of reduced graphene-heat conduction insulation composite material, 1-200 parts of reduced graphene-magnetic insulation composite material, 100 parts of vinyl silicone oil, 0.01-0.5 part of catalyst, 0.01-0.5 part of inhibitor and 1-25 parts of hydrogen-containing silicone oil in a double star stirrer, and then carrying out calendering and curing to obtain the graphene thermal interface material.
The graphene oxide is graphene with the number of layers smaller than 3 and the sheet diameter of 10-100 um.
The particle size of the heat-conducting insulating material is 100 nm-10 um, and the heat-conducting insulating material is selected from one or two of aluminum oxide, aluminum nitride, silicon nitride, boron nitride, silicon dioxide, magnesium oxide, zinc oxide and silicon carbide.
The particle size of the magnetic insulating material is 100 nm-10 um, and the magnetic insulating material is selected from at least one of ferrite, carbonyl iron powder and carbonyl nickel powder.
In the process of preparing the graphene-heat-conducting insulating composite material and the graphene-magnetic insulating composite material, the cation modifier is a substance with amino groups, such as 3-aminopropyltrimethoxysilane, but is not limited to the substance, and at least one of alkyl quaternary ammonium salt, quaternary ammonium salt containing heteroatoms, quaternary ammonium salt containing benzene rings and quaternary ammonium salt containing heterocycles can be selected. The reducing agent used for the reduction of the two is at least one selected from glucose, vitamins, hydrogen iodide, hydrazine hydrate, NaBH4 and sodium disulfite.
Besides, the catalyst is mainly Pt catalyst, and the inhibitor is mainly one or more of maleate, fumarate, organic phosphine and alkyne inhibitor.
The graphene thermal interface material prepared by the method has the following properties:
hardness: 20-40 Shore C;
the sustainable working temperature is as follows: -45 to 200 ℃;
flame retardant rating: v-0;
coefficient of thermal conductivity: 1-8W/m.K;
breakdown voltage: 1-6 KV/mm;
shielding: the absorption is 1 to 18GHz, and the absorption is less than-20 dB at 3 to 5 GHz.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the method of the invention uses the conventional heat-conducting insulating filler (heat-conducting insulating material) and the magnetic insulating filler (magnetic insulating material) to load on the graphene sheet to prepare the graphene composite filler, and can use the property of positive charge on the surface of the graphene and negative charge of the graphene to carry out electrostatic self-assembly and the chemical reaction of the groups on the filler and the hydroxyl and carboxyl on the graphene to form covalent bonds, so that the filler can be stably loaded on the graphene sheet and has the following effects:
A. the heat-conducting insulating filler provides dielectric loss and heat-conducting property;
B. the magnetic insulating filler provides magnetic loss and magnetic absorption;
C. insulating filler is loaded on graphene, so that the obtained graphene composite filler has high insulating property;
D. the excellent thermal conductivity of the graphene enables the thermal conductivity of the thermal interface material to be excellent, the oil absorption value of the graphene is greatly reduced after loading, and the addition amount can be greatly increased.
(2) Compared with CN111334260A, the method of the invention can be known that CN111334260A uses heat-conducting and shielding fillers to load graphene, the nuclear layer is magnetic particles, the shell layer is a carbon material, the carbon material has heat-conducting capability and enhances the electromagnetic shielding capability of magnetic materials, and the structure and the effect of the method are different from the structure and the effect of the method of the invention using graphene sheets as carriers to load heat-conducting insulating materials and magnetic insulating materials, therefore, compared with CN111334260A, the method of the invention has higher frequency band absorption on the basis of exerting the high heat-conducting characteristic of graphene two-dimensional materials, and the shielding performance parameters of the invention are as follows: the absorption is 1 to 18GHz, and the absorption is less than-20 dB at 3 to 5 GHz.
(3) Compared with CN109486191A, the graphene thermal interface material prepared by the method does not adopt conductive metal as a filler, the breakdown voltage of the prepared graphene thermal interface material is 1-6 KV/mm, the thermal conductivity coefficient is 1-8W/m.K, and the insulating property and the thermal conductivity of the graphene thermal interface material are superior to those of CN 109486191A.
(4) Compared with CN110294939A, CN110294939A shows that the wave-absorbing gasket with high heat conductivity is prepared from heat-conducting filler by using flaky graphite powder, but the wave-absorbing gasket is limited by the length direction and the size, has complex working procedures and is not suitable for large-scale production.
In conclusion, the invention provides a preparation method of the graphene thermal interface material which can be realized by adopting a conventional production mode, the graphene oxide is used as a carrier, so that the conventional heat-conducting powder and the magnetic filler are loaded on the graphene oxide, thereby forming composite powder, obtaining heat-conducting property by reducing the graphene oxide loaded composite filler, wherein the graphene-heat conducting and insulating composite filler provides dielectric loss and heat conducting performance, while the graphene-magnetic and insulating composite filler provides magnetic dielectric loss and heat conducting performance, the graphene composite filler obtained by loading the insulating functional filler on the graphene has high insulating property, the graphene composite filler and the insulating functional filler are compounded properly to prepare the thermal interface material which has both heat-conducting property and electromagnetic shielding property and is insulating, the production size is not limited, the process is simple, and the method is more suitable for large-scale production.
Drawings
Fig. 1 is a shielding performance test chart of the graphene thermal interface material.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1:
the embodiment provides a heat-conducting wave-absorbing integrated graphene thermal interface material.
The preparation steps are as follows:
s1, counting by weight, 100 parts of Al with the particle size D50 of 2um2O3Adding the mixture into a high-speed stirrer, adding 1 part of KH-550 into 50 parts of absolute ethyl alcohol, mixing, adding into the high-speed stirrer, then adding 0.01 part of concentrated hydrochloric acid, stirring for 30min, finally adding 1 part of single-layer graphene oxide powder with the sheet diameter of 20-30 um under ultrasonic (100 MHz), stirring for 30min, and drying to obtain the graphene-heat-conducting insulating composite material.
S2, adding 100 parts by weight of conventional magnetic insulating material carbonyl iron powder with the particle size of D50 being 3 microns into a high-speed stirrer, adding 0.1 part of KH-550 into 50 parts of absolute ethyl alcohol, mixing, adding into the high-speed stirrer, then adding 0.01 part of concentrated hydrochloric acid, stirring for 10-30 min, finally adding 1 part of single-layer graphene oxide with the particle size of 20-30 microns under ultrasonic waves (100 MHz), stirring for 30min, and drying to obtain the graphene-magnetic insulating composite material.
S3, adding 100 parts by weight of the graphene-heat-conducting insulating composite material into 100 parts by weight of aqueous dispersion of hydrogen iodide with the mass concentration of 5%, stirring for 60min at 80 ℃, filtering, and drying to obtain the graphene-heat-conducting insulating composite filler.
Adding 100 parts by weight of the graphene-magnetic insulating composite material into 100 parts by weight of aqueous dispersion of 5% hydrogen iodide, stirring at 80 ℃ for 60min, filtering, and drying to obtain the graphene-magnetic insulating composite filler.
S4, stirring and mixing 100 parts of the graphene-heat conduction insulation composite filler, 100 parts of the graphene-magnetic insulation composite filler, 100 parts of vinyl silicone oil, 0.3 part of platinum catalyst, 0.2 part of maleic anhydride inhibitor and 20 parts of hydrogen-containing silicone oil in a double star stirrer, and then carrying out calendering and curing at 150 ℃ for 20min to obtain the graphene thermal interface material.
Example 2:
the embodiment provides a heat-conducting wave-absorbing integrated graphene thermal interface material.
The preparation steps are as follows:
s1, adding 100 parts by weight of silicon nitride with the particle size D50 of 100nm into a high-speed stirrer, adding 0.1 part of KH-550 into 10 parts of absolute ethyl alcohol, mixing, adding into the high-speed stirrer, then adding 0.01 part of concentrated hydrochloric acid, stirring for 10min, finally adding 1 part of single-layer graphene oxide with the particle size of 10-20 microns under ultrasonic (200 MHz), stirring for 10min, and drying to obtain the graphene-heat-conducting insulating composite material.
S2, adding 100 parts by weight of conventional magnetic insulating material carbonyl nickel powder with the particle size of D50 being 100nm into a high-speed stirrer, adding 0.1 part of KH-550 into 10 parts of absolute ethyl alcohol, mixing, adding into the high-speed stirrer, then adding 0.01 part of concentrated hydrochloric acid, stirring for 10min, finally adding 1 part of single-layer graphene oxide with the particle size of 10-20 microns under ultrasonic (200 MHz), stirring for 10, and drying to obtain the graphene-magnetic insulating composite material.
S3, adding 100 parts by weight of the graphene-heat-conducting insulating composite material into 100 parts by weight of 1% glucose aqueous dispersion, stirring for 10min at 80 ℃, filtering, and drying to obtain the graphene-heat-conducting insulating composite filler.
Adding 100 parts by weight of the graphene-magnetic insulating composite material into 100 parts by weight of 1% glucose aqueous dispersion, stirring at 80 ℃ for 10min, filtering, and drying to obtain the graphene-magnetic insulating composite filler.
S4, stirring and mixing 50 parts of the graphene-heat conduction insulation composite filler, 50 parts of the graphene-magnetic insulation composite filler, 100 parts of vinyl silicone oil, 0.01 part of platinum catalyst, 0.01 part of fumarate inhibitor and 25 parts of hydrogen-containing silicone oil in a double star stirrer, and then carrying out calendering and curing at 150 ℃ for 20min to obtain the graphene thermal interface material.
Example 3:
the embodiment provides a heat-conducting wave-absorbing integrated graphene thermal interface material.
The preparation steps are as follows:
s1, adding 100 parts by weight of silicon dioxide with the particle size D50 of 10um into a high-speed stirrer, adding 5 parts by weight of KH-550 into 50 parts by weight of absolute ethyl alcohol, mixing, adding into the high-speed stirrer, then adding 1 part by weight of concentrated hydrochloric acid, stirring for 30min, finally adding 10 parts by weight of double-layer graphene oxide with the particle size of 90-100 um under ultrasound (500 MHz), stirring for 30min, and drying to obtain the graphene-heat-conducting insulating composite material.
S2, adding 100 parts by weight of conventional magnetic insulating material ferrite with the particle size D50 of 8 microns into a high-speed stirrer, adding 5 parts by weight of KH-550 into 50 parts by weight of absolute ethyl alcohol, mixing, adding into the high-speed stirrer, adding 1 part by weight of concentrated hydrochloric acid, stirring for 30min, adding 10 parts by weight of double-layer graphene oxide with the particle size of 90-100 microns under ultrasound (500 MHz), stirring for 30min, and drying to obtain the graphene-magnetic insulating composite material.
S3, adding 100 parts by weight of the graphene-heat-conducting insulating composite material into 50 parts by weight of aqueous dispersion of hydrazine hydrate with the mass concentration of 10%, stirring for 50min at 80 ℃, filtering, and drying to obtain the graphene-heat-conducting insulating composite filler.
Adding 100 parts by weight of the graphene-magnetic insulation composite material into 50 parts by weight of aqueous dispersion of hydrazine hydrate with the mass concentration of 10%, stirring for 50min at 80 ℃, filtering and drying to obtain the graphene-magnetic insulation composite filler.
S4, stirring and mixing 200 parts of the graphene-heat conduction insulation composite filler, 200 parts of the graphene-magnetic insulation composite filler, 100 parts of vinyl silicone oil, 0.5 part of platinum catalyst, 0.5 part of organic phosphine inhibitor and 25 parts of hydrogen-containing silicone oil in a double star stirrer, and then carrying out calendering and curing at 150 ℃ for 10min to obtain the graphene thermal interface material.
Example 4:
the embodiment provides a heat-conducting wave-absorbing integrated graphene thermal interface material.
The preparation steps are as follows:
s1, adding 50 parts by weight of aluminum nitride with the particle size D50 of 1um and 50 parts by weight of silicon nitride with the particle size D50 of 1um into a high-speed stirrer, adding 0.2 part of KH-550 into 30 parts of absolute ethyl alcohol, mixing, adding into the high-speed stirrer, then adding 0.15 part of concentrated hydrochloric acid, stirring for 30min, finally adding 5 parts of single-layer graphene oxide with the particle size of 30-40 um under ultrasound (800 MHz), stirring for 10-30 min, and drying to obtain the graphene-heat-conducting insulating composite material.
S2, adding 50 parts by weight of ferrite with the particle size D50 of 2um and 50 parts by weight of carbonyl iron powder with the particle size D50 of 2um into a high-speed stirrer, adding 0.2 part of KH-550 into 40 parts of absolute ethyl alcohol, mixing, adding into the high-speed stirrer, then adding 0.05 part of concentrated hydrochloric acid, stirring for 30min, finally adding 5 parts of single layer with the particle size of 30-40 um under ultrasonic (800 MHz), stirring for 30min, and drying to obtain the graphene-magnetic insulation composite material.
S3, adding 100 parts by weight of the graphene-heat-conducting insulating composite material into 60 parts by weight of aqueous dispersion of NaBH4 with the mass concentration of 4%, stirring for 60min at 80 ℃, filtering, and drying to obtain the graphene-heat-conducting insulating composite filler.
Adding 100 parts by weight of the graphene-magnetic insulation composite material into 60 parts by weight of aqueous dispersion of NaBH4 with the mass concentration of 4%, stirring for 60min at 80 ℃, filtering, and drying to obtain the graphene-magnetic insulation composite filler.
S4, stirring and mixing 1 part of the graphene-heat conduction insulation composite filler, 1 part of the graphene-magnetic insulation composite filler, 100 parts of vinyl silicone oil, 0.01 part of platinum catalyst, 0.01 part of alkyne inhibitor and 1 part of hydrogen-containing silicone oil in a double star stirrer, and then carrying out calendering and curing at 150 ℃ for 30min to obtain the graphene thermal interface material.
Example 5:
the embodiment provides a heat-conducting wave-absorbing integrated graphene thermal interface material.
The preparation steps are as follows:
s1, adding 100 parts by weight of silicon carbide with the particle size D50 of 500nm into a high-speed stirrer, adding 0.5 part of KH-550 into 50 parts of absolute ethyl alcohol, mixing, adding into the high-speed stirrer, then adding 0.05 part of concentrated hydrochloric acid, stirring for 20min, finally adding 6 parts of single-layer graphene oxide with the particle size of 20-30 um under ultrasonic (600 MHz), stirring for 20min, and drying to obtain the graphene-heat-conducting insulating composite material.
S2, adding 100 parts by weight of conventional magnetic insulating material carbonyl iron powder with the particle size D50 of 800nm into a high-speed stirrer, adding 0.5 part of KH-550 into 50 parts of absolute ethyl alcohol, mixing, adding into the high-speed stirrer, then adding 0.05 part of concentrated hydrochloric acid, stirring for 20min, finally adding 6 parts of single-layer graphene oxide with the particle size of 20-30 microns under ultrasonic waves (600 MHz), stirring for 20min, and drying to obtain the graphene-magnetic insulating composite material.
S3, adding 100 parts by weight of the graphene-heat-conducting insulating composite material into 20 parts by weight of aqueous dispersion of hydrogen iodide with the mass concentration of 6%, stirring for 50min at 80 ℃, filtering, and drying to obtain the graphene-heat-conducting insulating composite filler.
Adding 100 parts by weight of the graphene-magnetic insulating composite material into 20 parts by weight of aqueous dispersion of hydrogen iodide with the mass concentration of 6%, stirring for 50min at 80 ℃, filtering, and drying to obtain the graphene-magnetic insulating composite filler.
S4, stirring and mixing 100 parts of the graphene-heat conduction insulation composite filler, 100 parts of the graphene-magnetic insulation composite filler, 100 parts of vinyl silicone oil, 0.2 part of platinum catalyst, 0.1 part of maleic anhydride inhibitor and 18 parts of hydrogen-containing silicone oil in a double star stirrer, and then carrying out calendering and curing at 150 ℃ for 18min to obtain the graphene thermal interface material.
Example 6:
the embodiment provides a heat-conducting wave-absorbing integrated graphene thermal interface material.
The preparation steps are as follows:
s1, adding 100 parts by weight of silicon carbide with the particle size of 5 microns into a high-speed stirrer, adding 0.5 part of KH-550 into 50 parts of absolute ethyl alcohol, mixing, adding into the high-speed stirrer, then adding 0.01 part of concentrated hydrochloric acid, stirring for 30min, finally adding 1 part of single-layer graphene oxide with the particle size of 20-30 microns under ultrasound (500 MHz), stirring for 30min, and drying to obtain the graphene-heat-conducting insulating composite material.
S2, adding 100 parts by weight of conventional magnetic insulating material ferrite with the particle size of 8 microns into a high-speed stirrer, adding 0.1-5 parts by weight of KH-550 into 50 parts by weight of absolute ethyl alcohol, mixing, adding into the high-speed stirrer, then adding 0.01 part by weight of concentrated hydrochloric acid, stirring for 30min, finally adding 1 part by weight of single-layer graphene oxide with the particle size of 20-30 microns under ultrasonic wave (500 MHz), stirring for 30min, and drying to obtain the graphene-magnetic insulating composite material.
S3, adding 100 parts by weight of the graphene-heat-conducting insulating composite material into 30 parts by weight of aqueous dispersion of glucose and vitamins with the mass concentration of 5%, stirring for 40min at 80 ℃, filtering, and drying to obtain the graphene-heat-conducting insulating composite filler.
Adding 100 parts by weight of the graphene-magnetic insulating composite material into 30 parts by weight of aqueous dispersion of glucose and vitamins with the mass concentration of 5%, stirring for 40min at 80 ℃, filtering, and drying to obtain the graphene-magnetic insulating composite filler.
S4, stirring and mixing 180 parts of the graphene-heat conduction insulation composite filler, 180 parts of the graphene-magnetic insulation composite filler, 100 parts of vinyl silicone oil, 0.03 part of platinum catalyst, 0.25 part of alkyne inhibitor and 22 parts of hydrogen-containing silicone oil in a double star stirrer, and then carrying out calendering and curing at 150 ℃ for 25min to obtain the graphene thermal interface material.
Example 7:
the embodiment provides a heat-conducting wave-absorbing integrated graphene thermal interface material.
The preparation steps are as follows:
s1, counting by weight, 40 parts of Al with the particle size D50 of 1um2O360 parts of silicon dioxide with the particle size D50 of 1um is added into a high-speed stirrer, 1.5 parts of KH-550 is added into 40 parts of absolute ethyl alcohol, the mixture is added into the high-speed stirrer after being mixed, then 1 part of concentrated hydrochloric acid is added, the stirring is carried out for 15min, finally, 5 parts of single-layer graphene oxide with the sheet diameter of 50-60 um is added under the ultrasonic wave (400 MHz), the stirring is carried out for 15min, and the graphene-heat conduction insulation composite material is prepared after the drying.
S2, adding 100 parts by weight of conventional magnetic insulating material carbonyl iron powder with the particle size of 4 microns into a high-speed stirrer, adding 0.5 part of KH-550 into 40 parts of absolute ethyl alcohol, mixing, adding into the high-speed stirrer, then adding 1 part of concentrated hydrochloric acid, stirring for 15min, finally adding 5 parts of single-layer graphene oxide with the particle size of 50-60 microns under ultrasound (400 MHz), stirring for 15min, and drying to obtain the graphene-magnetic insulating composite material.
S3, adding 100 parts by weight of the graphene-heat-conducting insulating composite material into 100 parts by weight of aqueous dispersion of hydrogen iodide with the mass concentration of 2%, stirring for 50min at 80 ℃, filtering, and drying to obtain the graphene-heat-conducting insulating composite filler.
Adding 100 parts by weight of the graphene-magnetic insulating composite material into 100 parts by weight of aqueous dispersion of 2% hydrogen iodide, stirring at 80 ℃ for 50min, filtering, and drying to obtain the graphene-magnetic insulating composite filler.
S4, stirring and mixing 100 parts of the graphene-heat conduction insulation composite filler, 100 parts of the graphene-magnetic insulation composite filler, 100 parts of vinyl silicone oil, 0.25 part of platinum catalyst, 0.25 part of organophosphine inhibitor and 10 parts of hydrogen-containing silicone oil in a double star stirrer, and then carrying out calendering and curing at 150 ℃ for 30min to obtain the graphene thermal interface material.
Example 8:
the embodiment provides a heat-conducting wave-absorbing integrated graphene thermal interface material.
The preparation steps are as follows:
s1, counting by weight, 100 parts of Al with the particle size D50 of 4um2O3Adding the mixture into a high-speed stirrer, adding 2 parts of KH-550 into 35 parts of absolute ethyl alcohol, mixing, adding into the high-speed stirrer, then adding 0.12 part of concentrated hydrochloric acid, stirring for 30min, finally adding 10 parts of single-layer graphene oxide with the sheet diameter of 10-20 um under ultrasonic (500 MHz), stirring for 30min, and drying to obtain the graphene-heat-conducting insulating composite material.
S2, adding 100 parts by weight of conventional magnetic insulating material carbonyl nickel powder with the particle size of 8 microns into a high-speed stirrer, adding 1 part of KH-550 into 40 parts of absolute ethyl alcohol, mixing, adding into the high-speed stirrer, then adding 0.08 part of concentrated hydrochloric acid, stirring for 30min, finally adding 10 parts of single-layer graphene oxide with the particle size of 10-20 microns under ultrasonic wave (500 MHz), stirring for 30min, and drying to obtain the graphene-magnetic insulating composite material.
S3, adding 100 parts by weight of the graphene-heat-conducting insulating composite material into 80 parts by weight of aqueous dispersion of sodium bisulfite with the mass concentration of 5%, stirring for 60min at 80 ℃, filtering, and drying to obtain the graphene-heat-conducting insulating composite filler.
Adding 100 parts by weight of the graphene-magnetic insulating composite material into 80 parts by weight of aqueous dispersion of sodium bisulfite with the mass concentration of 5%, stirring for 60min at 80 ℃, filtering, and drying to obtain the graphene-magnetic insulating composite filler.
S4, stirring and mixing 120 parts of the graphene-heat conduction insulation composite filler, 120 parts of the graphene-magnetic insulation composite filler, 100 parts of vinyl silicone oil, 0.1 part of platinum catalyst, 0.2 part of inhibitor fumarate and 15 parts of hydrogen-containing silicone oil in a double star stirrer, and curing at 150 ℃ for 40min to obtain the graphene thermal interface material.
Example 9:
the graphene thermal interface materials of the embodiments 1 to 8 are respectively subjected to performance detection, and the detection method and data are shown in the following table 1. The shielding performance test of the graphene thermal interface material described in example 1 is shown in fig. 1.
Table 1 data sheet for performance test
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and all simple modifications and equivalent variations of the above embodiments according to the technical spirit of the present invention are included in the scope of the present invention.
Claims (5)
1. A preparation method of a heat conduction and wave absorption integrated graphene thermal interface material is characterized by comprising the following steps:
mixing 100 parts by weight of heat-conducting and insulating material with 0.1-5 parts by weight of cation modifier, 10-50 parts by weight of absolute ethyl alcohol and 0.01-1 part by weight of concentrated hydrochloric acid, adding 1-10 parts by weight of graphene oxide under ultrasonic, stirring and drying to obtain a graphene-heat-conducting and insulating composite material; adding 100 parts by weight of graphene-heat-conducting insulating composite material into 10-100 parts by weight of reducing agent with the mass concentration of 1-10%, stirring, filtering and drying to obtain reduced graphene-heat-conducting insulating composite filler,
mixing 100 parts by weight of magnetic insulating material, 0.1-5 parts by weight of cation modifier, 10-50 parts by weight of absolute ethyl alcohol and 0.01-1 part by weight of concentrated hydrochloric acid, adding 1-10 parts by weight of graphene oxide under ultrasonic, stirring and drying to obtain a graphene-magnetic insulating composite material; adding 100 parts by weight of graphene-magnetic insulation composite material into 10-100 parts by weight of reducing agent with the mass concentration of 1-10%, stirring, filtering and drying to obtain reduced graphene-magnetic insulation composite material,
according to parts by weight, stirring and mixing 1-200 parts of reduced graphene-heat conduction insulation composite material, 1-200 parts of reduced graphene-magnetic insulation composite material, 100 parts of vinyl silicone oil, 0.01-0.5 part of catalyst, 0.01-0.5 part of inhibitor and 1-25 parts of hydrogen-containing silicone oil in a double star stirrer, and then carrying out calendering and curing to prepare the graphene thermal interface material,
the performances of the graphene thermal interface material meet the following requirements:
hardness: 20-40 Shore C;
the sustainable working temperature is as follows: -45 to 200 ℃;
flame retardant rating: v-0;
coefficient of thermal conductivity: 1-8W/m.K;
breakdown voltage: 1-6 KV/mm;
shielding: the absorption is 1 to 18GHz, and the absorption is less than-20 dB at 3 to 5 GHz.
2. The preparation method of the heat-conducting wave-absorbing integrated graphene thermal interface material according to claim 1, which is characterized by comprising the following steps: the graphene oxide is graphene with the number of layers smaller than 3 and the sheet diameter of 10-100 um.
3. The preparation method of the heat-conducting wave-absorbing integrated graphene thermal interface material according to claim 1, which is characterized by comprising the following steps: the particle size of the heat-conducting insulating material is 100 nm-10 um, and the heat-conducting insulating material is selected from one or two of aluminum oxide, aluminum nitride, silicon nitride, boron nitride, silicon dioxide, magnesium oxide, zinc oxide and silicon carbide.
4. The preparation method of the heat-conducting wave-absorbing integrated graphene thermal interface material according to claim 1, which is characterized by comprising the following steps: the particle size of the magnetic insulating material is 100 nm-10 um, and the magnetic insulating material is selected from at least one of ferrite, carbonyl iron powder and carbonyl nickel powder.
5. The graphene thermal interface material prepared by the method of claim 1.
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| CN113999432B (en) * | 2021-11-18 | 2023-05-26 | 彗晶新材料科技(杭州)有限公司 | Fe 3 O 4 Preparation method of @ MWCNTs nanocomposite and electronic equipment |
| CN114133740B (en) * | 2021-11-23 | 2022-11-08 | 华南理工大学 | Heat-conducting wave-absorbing silicone rubber composite material and preparation method thereof |
| CN114133739B (en) * | 2021-11-23 | 2022-11-08 | 华南理工大学 | Silicone rubber wave-absorbing composite material and preparation method thereof |
| CN114525114A (en) * | 2022-02-28 | 2022-05-24 | 中国电子科技集团公司第三十三研究所 | Preparation method of graphene fiber-based heat-conducting wave-absorbing powder material |
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