CN113860903B - Preparation method of high-thermal-conductivity graphite-copper composite board - Google Patents
Preparation method of high-thermal-conductivity graphite-copper composite board Download PDFInfo
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- CN113860903B CN113860903B CN202111113921.5A CN202111113921A CN113860903B CN 113860903 B CN113860903 B CN 113860903B CN 202111113921 A CN202111113921 A CN 202111113921A CN 113860903 B CN113860903 B CN 113860903B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
- C04B37/02—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles
- C04B37/021—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles in a direct manner, e.g. direct copper bonding [DCB]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/04—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the partial melting of at least one layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/302—Conductive
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2311/00—Metals, their alloys or their compounds
- B32B2311/12—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2313/00—Elements other than metals
- B32B2313/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
- C04B2237/32—Ceramic
- C04B2237/36—Non-oxidic
- C04B2237/363—Carbon
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
- C04B2237/40—Metallic
- C04B2237/407—Copper
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
- C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
- C04B2237/52—Pre-treatment of the joining surfaces, e.g. cleaning, machining
Abstract
The invention discloses a preparation method of a high-thermal-conductivity graphite-copper composite board, and belongs to the technical field of heat sink composite boards. The method comprises the following specific steps: step 1, polishing high-thermal-conductivity graphite, and then ultrasonically cleaning the graphite by using acetone; step 2, wrapping the high-heat-conductivity graphite by using a mixture of chromium salt and NaCl/KCl salt, and placing the high-heat-conductivity graphite into an alumina crucible; heating the crucible to enable the mixture of the chromium salt and the NaCl/KCl salt to be in a molten state, stirring and carrying out heat treatment; step 3, taking the high-thermal-conductivity graphite out of the molten salt solution, and carrying out ultrasonic cleaning on the high-thermal-conductivity graphite by using deionized water; step 4, placing high-heat-conductivity graphite on an alumina carrier in a stainless steel chamber, simultaneously placing high-purity copper on a high-heat-conductivity graphite plate, and then heating to melt the copper; and 5, cooling to room temperature to obtain the high-thermal-conductivity graphite-copper composite plate. The invention has simple production process and high bonding strength of graphite and copper.
Description
Technical Field
The invention relates to the technical field of heat sink composite boards, in particular to a preparation method of a high-thermal-conductivity graphite-copper composite board.
Background
With the development of electronic products toward higher power and higher integration. The power density greatly rises, the heat productivity per unit volume is larger and larger, and the performance, reliability and service life of the device are seriously affected by the temperature rise and the increase of the thermal stress between the packaging material and the chip. Heat dissipation has become a bottleneck limiting the development and application of high power devices. The heat dissipation capability of electronic products depends on peripheral heat dissipation materials to a great extent, while the heat conduction materials (such as aluminum and copper) used in traditional products are limited by the self heat conductivity and weight of the materials, so that the development requirements of the new generation of technology in China cannot be met, and the development and application of the new generation of heat sink materials with low density and higher heat dissipation capability is urgent.
The graphite with high thermal conductivity is a material with the highest specific heat conductivity known at present and is a preferred material for solving the heat dissipation problem of a new generation of high-power electronics in China. Although graphite with high thermal conductivity has the conditions for replacing the existing thermal management materials in terms of specific gravity and heat dissipation, the graphite with high thermal conductivity is rarely practically applied to electronic products at present. The method is mainly influenced by the following two factors:
(1) The high-thermal-conductivity graphite belongs to a two-dimensional material, has low strength and bending strength less than 20MPa, and particularly has extremely low peel strength in a two-dimensional plane direction, which makes the application of the graphite in practical components difficult.
(2) The high heat conduction graphite is difficult to weld and can not be assembled with an electronic device. The traditional solder can not form good wetting to the high-heat-conductivity graphite, but a few high-heat-conductivity graphite and other components are connected in a bonding mode, but the bonding interface has huge thermal resistance, so that the heat transfer effect of the high-heat-conductivity graphite as a heat sink is obviously reduced. The surface modification method can well solve the problems of poor wettability and mismatched thermal expansion coefficient of copper on the graphite surface, such as electroplating, chemical plating, solid-phase evaporation and the like, however, the traditional surface modification method cannot realize metallurgical bonding of graphite and a coating, and the bonding strength of the surface modified graphite and metal is difficult to guarantee.
Disclosure of Invention
In view of this, the invention provides a preparation method of a high thermal conductivity graphite-copper composite plate. The method has simple production process and high bonding strength of graphite and copper.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a high-thermal-conductivity graphite-copper composite plate comprises the following steps:
step 1, polishing a high-thermal-conductivity graphite plate, and ultrasonically cleaning the graphite plate by using acetone;
step 2, wrapping the high-heat-conductivity graphite plate by using a mixture of chromium salt, naCl and KCl, and placing the wrapped graphite plate into an alumina crucible; heating the crucible to enable the mixture of the chromium salt, the NaCl and the KCl to be in a molten state, stirring and carrying out heat treatment;
step 3, taking out the high-thermal-conductivity graphite plate from the molten salt solution, and ultrasonically cleaning the high-thermal-conductivity graphite plate by using deionized water;
step 4, placing high-heat-conductivity graphite on an alumina carrier in a high-temperature furnace, simultaneously placing high-purity copper on a high-heat-conductivity graphite plate, and then heating to melt the copper;
and 5, cooling to room temperature to obtain the high-thermal-conductivity graphite-copper composite plate.
Further, in step 1, the surface of the graphite plate with high thermal conductivity is first ground flat with P180, P600 and P1200 grade silicon carbide paper, and then polished with 2.5 μm diamond gypsum.
Further, in step 2, the chromium salt is chromic anhydride.
Further, in step 2, the mass ratio of the chromium salt in the mixture is 10%, and the molar ratio of NaCl to KCl in the mixture is 1.
Further, in the step 2, the temperature of the heat treatment is 1100 to 1400 ℃, and the time of the heat treatment is 1 to 3 hours.
Further, in step 4, the heating was performed in an argon stream at 1100 ℃ for 1 hour.
The invention adopts the technical scheme to produce the beneficial effects that:
1. the surface modification provided by the invention has the advantages that the molten chloride has good wettability to graphite, and the chromic anhydride solution is easy to permeate into the high-heat-conductivity graphite and reacts with the graphite to generate a layer of Cr x C y The metallurgical layer has high bonding strength.
2. In the prior art, the brazing alloy causes metal to diffuse into copper, so that the thermal property and the mechanical property of the copper are reduced. The good wettability of the copper on the surface of the modified graphite in the invention allows pure copper to be directly connected with the modified graphite, avoiding the use of brazing alloy.
3. The strong interfacial bonding between copper and highly thermally conductive graphite of the present invention is achieved by utilizing mechanical interlocking within the spatial constraints of the graphite network; and the production process is simple and easy to realize.
Drawings
FIG. 1 is a schematic flow chart of an embodiment of the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and the detailed description.
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
A preparation method of a high-thermal-conductivity graphite-copper composite plate comprises the following steps:
1) Polishing and cleaning, namely polishing the high-thermal-conductivity graphite, and then ultrasonically cleaning the graphite by using acetone to remove impurities on the surface;
2) Surface modification, namely fixing the high-heat-conductivity graphite obtained in the step 1) in an alumina crucible and covering the high-heat-conductivity graphite with a mixture of chromium salt and NaCl/KCl salt. Uniformly stirring the molten salt solution, and then carrying out heat treatment;
3) Cleaning, taking out the high-heat-conductivity graphite plate after heat treatment, and then cleaning the graphite plate in an ultrasonic cleaning machine by using deionized water;
4) Copper-graphite connection, namely placing the high-heat-conductivity graphite plate obtained in the step 3) on an alumina carrier in a stainless steel chamber, placing high-purity copper (99.999 wt.%) in a solid form on the high-heat-conductivity graphite plate, and heating to melt the high-heat-conductivity copper;
5) And cooling to room temperature, and taking out the high-thermal-conductivity graphite-copper composite plate.
Preferably, in the step 1), the surface is firstly ground flat by using P180, P600 and P1200-grade silicon carbide papers, and then polished by using 2.5 mu m diamond gypsum.
Preferably, in the step 2), the chromium salt is chromic anhydride.
Optimally, in the step 2), the mass ratio of the chromium salt in the mixture is about 10%, and the molar ratio of NaCl/KCl in the mixture is =1.
Preferably, in the step 2), the heat treatment temperature is 1100-1400 ℃, and the heat treatment time is 1-3 hours.
Preferably, in the step 4), the heating is performed in an argon gas flow at 1100 ℃ for 1 hour.
Referring to fig. 1, 1) polishing the high thermal conductivity graphite, and then ultrasonically cleaning the graphite with acetone to remove impurities on the surface;
the surface was first ground flat with P180, P600 and P1200 grade silicon carbide paper and then polished with 2.5 μm diamond plaster.
2) Fixing the graphite with high thermal conductivity obtained in the step 1) in an alumina crucible, and covering the graphite with a mixture of chromium salt and NaCl/KCl salt. Uniformly stirring the molten salt solution, and then carrying out heat treatment;
the chromium salt is preferably chromic anhydride.
The mass ratio of the chromium salt in the mixture is about 10%, and the molar ratio of NaCl/KCl in the mixture is =1.
The heat treatment temperature is 1100-1400 ℃, and the heat treatment time is 1-3 hours.
3) Taking out the high-heat-conductivity graphite plate after heat treatment, and then cleaning the graphite plate in an ultrasonic cleaning machine by using deionized water;
4) Placing the high-thermal-conductivity graphite plate obtained in the step 3) on an alumina carrier in a stainless steel chamber, placing high-purity copper (99.999 wt.%) on the high-thermal-conductivity graphite plate in a solid form, and heating to melt the high-thermal-conductivity copper;
the heating was carried out at 1100 ℃ for 1 hour in an argon stream.
5) Cooling to room temperature, taking out the high heat conduction graphite-copper composite plate
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the invention, so that any modifications, equivalents, improvements, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (5)
1. The preparation method of the high-thermal-conductivity graphite-copper composite plate is characterized by comprising the following steps of:
step 1, polishing a high-thermal-conductivity graphite plate, and ultrasonically cleaning the graphite plate by using acetone;
step 2, wrapping the high-heat-conductivity graphite plate by using a mixture of chromium salt, naCl and KCl, and placing the wrapped graphite plate into an alumina crucible; heating the crucible to enable the mixture of the chromium salt, the NaCl and the KCl to be in a molten state, stirring and carrying out heat treatment;
step 3, taking out the high-heat-conductivity graphite plate from the molten salt solution, and carrying out ultrasonic cleaning on the high-heat-conductivity graphite plate by using deionized water;
step 4, placing a high-heat-conductivity graphite plate on an alumina carrier in a high-temperature furnace, simultaneously placing high-purity copper on the high-heat-conductivity graphite plate, and then heating to melt the copper;
step 5, cooling to room temperature to obtain the high-thermal-conductivity graphite-copper composite plate;
in step 2, the chromium salt is chromic anhydride.
2. The method for preparing a high thermal conductivity graphite-copper composite plate according to claim 1, wherein in step 1, the surface of the high thermal conductivity graphite plate is polished by silicon carbide paper of P180, P600 and P1200 grades in sequence, and finally polished by 2.5 μm diamond gypsum.
3. The method for preparing a high thermal conductive graphite-copper composite plate according to claim 1, wherein in step 2, the mass ratio of the chromium salt in the mixture is 10%, and the molar ratio of NaCl to KCl in the mixture is 1.
4. The method for preparing the high-thermal-conductivity graphite-copper composite board according to claim 1, wherein in the step 2, the heat treatment temperature is 1100-1400 ℃, and the heat treatment time is 1-3 hours.
5. The method for preparing a high thermal conductivity graphite-copper composite plate according to claim 1, wherein in step 4, the heating is performed in an argon gas flow at 1100 ℃ for 1 hour.
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| CN113860903B true CN113860903B (en) | 2023-01-24 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005037734A1 (en) * | 2003-10-09 | 2005-04-28 | Politecnico Di Torino | Process to join carbon based materials to metals and its applications |
| CN102146552A (en) * | 2010-02-09 | 2011-08-10 | 航天材料及工艺研究所 | Copper/graphite compound material and preparation method thereof |
| CN103924119A (en) * | 2014-04-23 | 2014-07-16 | 北京科技大学 | Ultrahigh heat conduction graphite flake/copper composite material and preparation method thereof |
| CN107900327A (en) * | 2017-11-16 | 2018-04-13 | 北京科技大学 | A kind of method that combination 3D printing technique prepares diamond/copper composite material |
| CN109320298A (en) * | 2018-10-17 | 2019-02-12 | 中国科学院山西煤炭化学研究所 | A method of improving foamy graphite surface wettability |
| CN111114041A (en) * | 2020-01-07 | 2020-05-08 | 中国电子科技集团公司第十六研究所 | Composite material with high-thermal-conductivity graphite-copper interpenetrating structure and preparation method thereof |
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- 2021-09-23 CN CN202111113921.5A patent/CN113860903B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005037734A1 (en) * | 2003-10-09 | 2005-04-28 | Politecnico Di Torino | Process to join carbon based materials to metals and its applications |
| CN102146552A (en) * | 2010-02-09 | 2011-08-10 | 航天材料及工艺研究所 | Copper/graphite compound material and preparation method thereof |
| CN103924119A (en) * | 2014-04-23 | 2014-07-16 | 北京科技大学 | Ultrahigh heat conduction graphite flake/copper composite material and preparation method thereof |
| CN107900327A (en) * | 2017-11-16 | 2018-04-13 | 北京科技大学 | A kind of method that combination 3D printing technique prepares diamond/copper composite material |
| CN109320298A (en) * | 2018-10-17 | 2019-02-12 | 中国科学院山西煤炭化学研究所 | A method of improving foamy graphite surface wettability |
| CN111114041A (en) * | 2020-01-07 | 2020-05-08 | 中国电子科技集团公司第十六研究所 | Composite material with high-thermal-conductivity graphite-copper interpenetrating structure and preparation method thereof |
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