CN108328605B - High-temperature-resistant graphene heat dissipation film and preparation method thereof - Google Patents
High-temperature-resistant graphene heat dissipation film and preparation method thereof Download PDFInfo
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- CN108328605B CN108328605B CN201810061943.3A CN201810061943A CN108328605B CN 108328605 B CN108328605 B CN 108328605B CN 201810061943 A CN201810061943 A CN 201810061943A CN 108328605 B CN108328605 B CN 108328605B
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K7/00—Constructional details common to different types of electric apparatus
- H05K7/20—Modifications to facilitate cooling, ventilating, or heating
- H05K7/2039—Modifications to facilitate cooling, ventilating, or heating characterised by the heat transfer by conduction from the heat generating element to a dissipating body
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5846—Reactive treatment
Abstract
The invention discloses a high-temperature-resistant graphene heat dissipation film and a preparation method thereof. Firstly, preparing a pure graphene heat dissipation film, then depositing inorganic nanoparticles on the surface of the graphene film, and further forming a high-temperature-resistant metal carbide protective layer on the surface of the graphene film through an in-situ electrothermal reaction. The method overcomes the defect that the heat dissipation effect is gradually deteriorated due to oxidation reaction in the long-term service process of the graphene heat dissipation film, and the high-temperature-resistant graphene heat dissipation film can be prepared quickly and efficiently by adopting the in-situ electrothermal reaction.
Description
Technical Field
The invention relates to a graphene heat dissipation film, in particular to a high-temperature-resistant graphene heat dissipation film and a preparation method thereof.
Background
The graphene has the highest thermal conductivity of known materials, and the graphene heat dissipation film prepared by a specific assembly technology is expected to play an important role in the fields of microelectronic devices and high-temperature heat management. However, the graphene heat dissipation film has poor high temperature resistance, and particularly in a high-temperature heat source environment, the heat dissipation performance of the graphene heat dissipation film is remarkably reduced due to oxidation reaction. Therefore, how to improve the stability of the graphene heat-conducting film under high-temperature conditions and construct a high-temperature-resistant graphene heat-dissipation film has important significance for the practical application of the graphene heat-dissipation film.
Disclosure of Invention
The invention aims to solve the problem that the existing graphene heat dissipation film is poor in high-temperature resistance, and provides a high-temperature-resistant graphene heat dissipation film and a preparation method thereof.
The invention aims to realize a high-temperature-resistant graphene heat dissipation film by the following technical scheme, which comprises a graphene heat dissipation layer and high-temperature-resistant nano protection layers positioned on two sides of the graphene heat dissipation layer, wherein the high-temperature-resistant nano protection layers are made of metal carbide. The heat dissipation film can provide heat dissipation temperature within the range of 30-2000 ℃ for a long time, and oxidation failure does not occur under the high-temperature condition.
Further, the metal carbide is one or more of titanium carbide, tantalum carbide, tungsten carbide, zirconium carbide and hafnium carbide which are mixed according to any proportion.
A preparation method of a high-temperature-resistant graphene heat dissipation film comprises the following steps:
(1) and casting the graphene oxide solution on a flat substrate, and drying to obtain the graphene oxide film.
(2) And (2) placing the graphene oxide film obtained in the step (1) in a high-temperature furnace, and carrying out heat treatment for 0.5-1.5 h under the protection of inert gas argon, wherein the heat treatment temperature range is 2000-3000 ℃, so as to obtain the graphene film.
(3) And (3) rolling the graphene film obtained in the step (2) to obtain the graphene heat dissipation film.
(4) And (4) depositing a metal layer or an inorganic metal oxide layer on the surface of the graphene heat dissipation film obtained in the step (3) by adopting a chemical method or a physical method.
(5) In an inert gas, reacting metal or inorganic oxide deposited on the surface of the graphene heat dissipation film with surface carbon of the graphene film through in-situ electric heating reaction to form metal carbide, thereby obtaining the high-temperature resistant graphene heat dissipation film.
Further, the deposited metal or inorganic metal oxide in the step (4) comprises one or more of titanium, tantalum, tungsten, zirconium, hafnium, titanium oxide and the like which are mixed according to any proportion.
Further, in the step (5), the temperature of the electric heating reaction is 1000-2000 ℃, and the reaction time is 0.5-2 h.
The invention has the following technical effects:
1. the primary raw material of the graphene oxide is graphite, and the raw material is wide in source, easy to obtain and low in cost;
2. the in-situ electric heating reaction is adopted, the high temperature can be realized under the condition of lower voltage, and the reaction of the graphene and the metal or inorganic oxide can be realized in a very short time;
3. by constructing the high-temperature-resistant nano protective layer, the reaction of oxygen in the air and graphene can be effectively prevented, and the thermal stability of the heat dissipation film in the air, especially the thermal stability under a high-temperature condition (more than 800 ℃), is improved.
Detailed Description
The invention provides a high-temperature-resistant graphene heat dissipation film which is composed of a graphene heat dissipation layer and a high-temperature-resistant nano protection layer, can effectively dissipate heat of a high-temperature (800-3000 ℃) heat source, and is strong in structural stability under a high-temperature condition. The invention also provides a preparation method of the high-temperature-resistant graphene heat dissipation film, which comprises the steps of firstly preparing a pure graphene film, then depositing metal or inorganic oxide on the surface of the graphene film, and forming a metal carbide protective layer on the surface of the graphene film through in-situ electrothermal reaction to finally obtain the high-temperature-resistant graphene heat dissipation film protected by the metal carbide nano layer.
The present invention will be further described with reference to the following examples. The present invention is further illustrated by the following examples, which are not to be construed as limiting the scope of the invention, and the non-essential changes and modifications thereof by those skilled in the art can be made without departing from the spirit and scope of the invention.
Example 1:
(1) and (3) casting the graphene oxide solution of 1mg/ml on a flat substrate, and drying to obtain the graphene oxide film.
(2) And (2) placing the graphene oxide film obtained in the step (1) in a high-temperature furnace, and carrying out heat treatment for 1.5h at 2000 ℃ under the protection of inert gas argon to obtain the graphene film.
(3) And (3) carrying out rolling treatment on the graphene film obtained in the step (2) to obtain a dense graphene heat dissipation film.
(4) And (4) depositing metal tungsten on the surface of the graphene heat dissipation film obtained in the step (3) by adopting a physical vapor deposition method.
(5) And applying voltage to the graphene film to perform in-situ electrothermal reaction, and reacting the deposited tungsten metal with surface carbon of the graphene film to obtain the high-temperature-resistant tungsten carbide nano layer. Wherein the temperature of the electric heating reaction is 1600 ℃, and the reaction time is 2 h.
Through the steps, the high-temperature-resistant graphene heat dissipation film with uniform and compact thickness is obtained. The thickness of the film is 10-20 mu m, and the graphene is oriented and arranged along the plane direction. The thermal conductivity of the film is more than 1000W/mK, the high temperature resistance is good, and the film can effectively dissipate heat of a heat source at the temperature of more than 800 ℃.
Example 2:
(1) and (3) casting the graphene oxide solution of 1mg/ml on a flat substrate, and drying to obtain the graphene oxide film.
(2) And (2) placing the graphene oxide film obtained in the step (1) in a high-temperature furnace, and carrying out heat treatment for 1.0h at 2500 ℃ under the protection of inert gas argon to obtain the graphene film.
(3) And (3) carrying out rolling treatment on the graphene film obtained in the step (2) to obtain a dense graphene heat dissipation film.
(4) And (4) depositing metal tantalum on the surface of the graphene heat dissipation film obtained in the step (3) by adopting a physical vapor deposition method.
(5) And applying voltage to the graphene film to perform in-situ electrothermal reaction, and reacting the deposited tantalum with surface carbon of the graphene film to form the high-temperature-resistant tantalum carbide nano layer. Wherein the temperature of the electric heating reaction is 1800 ℃, and the reaction time is 1 h.
Through the steps, the high-temperature-resistant graphene heat dissipation film with the surface covered with the tantalum carbide and uniform and dense in thickness is obtained. The thickness of the film is 10-20 mu m, and the graphene is oriented and arranged along the plane direction. The thermal conductivity of the film is more than 1000W/mK, the high temperature resistance is good, and the film can effectively dissipate heat of a heat source at the temperature of more than 800 ℃.
Example 3
(1) And (3) casting the graphene oxide solution of 1mg/ml on a flat substrate, and drying to obtain the graphene oxide film.
(2) And (2) placing the graphene oxide film obtained in the step (1) in a high-temperature furnace, and carrying out heat treatment for 0.5h at 3000 ℃ under the protection of inert gas argon to obtain the graphene film.
(3) And (3) carrying out rolling treatment on the graphene film obtained in the step (2) to obtain a dense graphene heat dissipation film.
(4) And (4) depositing a titanium dioxide nano layer on the surface of the graphene heat dissipation film obtained in the step (3) by adopting a chemical deposition method.
(5) And applying voltage to the graphene film to perform in-situ electrothermal reaction, and reacting the deposited nano titanium dioxide with surface carbon of the graphene film to form a high-temperature-resistant titanium carbide nano layer. Wherein the temperature of the electric heating reaction is 2000 ℃, and the reaction time is 0.5 h.
Through the steps, the high-temperature-resistant graphene heat dissipation film with uniform thickness and the surface covered with the titanium carbide is obtained. The thickness of the film is 10-20 mu m, and the graphene is oriented and arranged along the plane direction. The thermal conductivity of the film is more than 1000W/mK, the high temperature resistance is good, and the film can effectively dissipate heat of a heat source at the temperature of more than 800 ℃.
The above-described embodiments are intended to illustrate rather than to limit the invention, and any modifications and variations of the present invention are within the spirit of the invention and the scope of the appended claims.
Claims (4)
1. The high-temperature-resistant graphene heat dissipation film is characterized by comprising a graphene heat dissipation layer and high-temperature-resistant nano protective layers positioned on two sides of the graphene heat dissipation layer, wherein the high-temperature-resistant nano protective layers are made of metal carbide; the high-temperature-resistant graphene heat dissipation film is prepared by the following steps:
(1) casting the graphene oxide solution on a flat substrate, and drying to obtain a graphene oxide film;
(2) placing the graphene oxide film obtained in the step (1) in a high-temperature furnace, and carrying out heat treatment for 0.5-1.5 h under the protection of inert gas argon, wherein the heat treatment temperature range is 2000-3000 ℃, so as to obtain a graphene film;
(3) rolling the graphene film obtained in the step (2) to obtain a graphene heat dissipation film;
(4) depositing a metal layer or an inorganic metal oxide layer on the surface of the graphene heat dissipation film obtained in the step (3) by adopting a chemical method or a physical method;
(5) in an inert gas, reacting metal or inorganic metal oxide deposited on the surface of the graphene heat dissipation film with surface carbon of the graphene film through in-situ electric heating reaction to form metal carbide, thereby obtaining the high-temperature resistant graphene heat dissipation film.
2. The high-temperature-resistant graphene heat dissipation film according to claim 1, wherein the metal carbide is one or more selected from titanium carbide, tantalum carbide, tungsten carbide, zirconium carbide and hafnium carbide, and is mixed according to any proportion.
3. The high-temperature-resistant graphene heat dissipation film according to claim 1, wherein in the step (4), the metal layer comprises one or more of titanium, tantalum, tungsten, zirconium, and hafnium mixed according to any mixture ratio; the inorganic metal oxide is titanium oxide.
4. The high-temperature-resistant graphene heat dissipation film according to claim 1, wherein in the step (5), the temperature of the electrothermal reaction is 1000-2000 ℃, and the reaction time is 0.5-2 h.
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| CN111136586A (en) * | 2019-12-27 | 2020-05-12 | 重庆秦嵩科技有限公司 | Surface treatment method for radar signal acquisition, generation and processing module structure |
| CN111484002B (en) * | 2020-04-17 | 2023-06-09 | 南京动量材料科技有限公司 | Preparation method and application of porous graphene film |
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| CN101913598A (en) * | 2010-08-06 | 2010-12-15 | 浙江大学 | Method for preparing graphene membrane |
| CN104210168A (en) * | 2014-09-10 | 2014-12-17 | 浙江碳谷上希材料科技有限公司 | Preparation method for graphene and metal composite electromagnetic shielding film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101913598A (en) * | 2010-08-06 | 2010-12-15 | 浙江大学 | Method for preparing graphene membrane |
| CN104210168A (en) * | 2014-09-10 | 2014-12-17 | 浙江碳谷上希材料科技有限公司 | Preparation method for graphene and metal composite electromagnetic shielding film |
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