CN117568694A - Three-dimensional graphite sphere reinforced copper-based heat conduction composite material and preparation method thereof - Google Patents
Three-dimensional graphite sphere reinforced copper-based heat conduction composite material and preparation method thereof Download PDFInfo
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- CN117568694A CN117568694A CN202311533878.7A CN202311533878A CN117568694A CN 117568694 A CN117568694 A CN 117568694A CN 202311533878 A CN202311533878 A CN 202311533878A CN 117568694 A CN117568694 A CN 117568694A
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- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 110
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 109
- 239000010949 copper Substances 0.000 title claims abstract description 109
- 239000010439 graphite Substances 0.000 title claims abstract description 108
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 107
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000002131 composite material Substances 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000007747 plating Methods 0.000 claims abstract description 46
- 239000006260 foam Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000004070 electrodeposition Methods 0.000 claims abstract description 11
- 238000003825 pressing Methods 0.000 claims abstract description 9
- 238000011049 filling Methods 0.000 claims abstract description 6
- 238000007731 hot pressing Methods 0.000 claims abstract description 5
- 238000002490 spark plasma sintering Methods 0.000 claims abstract description 5
- 238000000465 moulding Methods 0.000 claims abstract description 4
- 238000003828 vacuum filtration Methods 0.000 claims abstract description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 16
- 238000009713 electroplating Methods 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 12
- 238000000151 deposition Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 235000010333 potassium nitrate Nutrition 0.000 claims description 6
- 239000004323 potassium nitrate Substances 0.000 claims description 6
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 6
- 239000001509 sodium citrate Substances 0.000 claims description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 6
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- 239000001476 sodium potassium tartrate Substances 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 12
- 230000017525 heat dissipation Effects 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 13
- 238000000967 suction filtration Methods 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 239000007770 graphite material Substances 0.000 description 5
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229940074439 potassium sodium tartrate Drugs 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 239000011156 metal matrix composite Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Abstract
The invention discloses a three-dimensional graphite sphere reinforced copper-based heat conduction composite material and a preparation method thereof, comprising the following steps: A. plating graphite spheres on the surface of the foam copper by using an electrodeposition method to prepare a composite framework; B. placing the composite skeleton in a die, and filling copper powder into holes in the skeleton by vacuum filtration to obtain a composite; C. applying pressure to the die, and pre-pressing the composite body into a blank by cold press molding; D. and carrying out vacuum hot pressing or spark plasma sintering on the blank, and taking out to obtain the product. The foam copper-graphite ball-copper composite heat dissipation material prepared by the invention not only has good heat dissipation performance, but also has good mechanical property, and overcomes the defects of the existing composite material in the aspects of heat conductivity, thermal expansion coefficient, mechanical property and the like.
Description
Technical Field
The invention relates to the field of metal matrix composite materials, in particular to a three-dimensional graphite sphere reinforced copper matrix heat conduction composite material and a preparation method thereof.
Background
Among the materials, metals and composite materials thereof have high thermal conductivity, good electrical conductivity, mechanical properties, corrosion resistance and the like, and are often used for preparing electronic packaging materials. The pure copper has higher heat conduction performance, the heat conductivity is about 376W/(m.K), and the pure copper is an ideal heat dissipation material for a high-power device shell and a heat sink. However, copper has a relatively large thermal expansion coefficient (about 16.9X10) -6 K) are difficult to achieve effective matching with semiconductor chip materials and the like. The copper-based composite material has significantly reduced thermal expansion coefficient and is easy to obtain higher thermal conductivity by adding the inorganic nonmetallic material reinforcement. The chemical components of the graphite material are mainly single carbon elements, the carbon material has higher intrinsic heat conductivity, and can provide more excellent heat conduction performance under the condition of reducing the weight of the device, so that the graphite material is an ideal reinforcement of the heat conduction composite material. In order to meet various requirements of technical development, graphite materials are designed and researched into various forms, such as graphite spheres, graphite foam, graphite flakes, graphene and the like.
In recent years, high-performance metal matrix composite materials, typified by "graphite/metal composite materials", are rapidly developing toward high heat dissipation, low thermal expansion, high toughness, and the like. The graphite/metal composite material is a development direction which is pursued in the aspects of improving the product performance, simplifying the preparation process, reducing the production cost and the like. Graphite exhibits high efficiency thermal conductivity along the basal plane direction, with a theoretical thermal conductivity as high as 2000W/(m·k), whereas the thermal conductivity in the direction perpendicular to the graphite sheet is lower, with a theoretical value of only 6W/(m·k). In order to solve the anisotropy of the thermal conductivity of graphite, researchers uniformly disperse spherical particles made of graphite into a copper matrix, however, the thermal conductivity of the prepared composite material is far lower than a theoretical value. The main reason is that the interface wettability of copper and graphite balls is poor, so that the defect exists in the composite material, the interface binding property is poor, and the heat transmission in the heat dissipation process is hindered.
On the other hand, graphite spheres are dispersed in a copper matrix to form heat conduction islands, the two-phase interface thermal resistance of the graphite spheres/copper matrix is far greater than that among graphite particles, and the high interface thermal resistance severely restricts the heat conduction performance of the graphite spheres/copper matrix composite material. The connectivity between the graphite nodules can be improved, so that the interface thermal resistance can be greatly reduced, and the thermal conductivity of the composite material can be effectively improved, so that the control of the spatial distribution of the graphite nodules in the composite material is a key for improving the thermal conductivity of the composite material.
Disclosure of Invention
The invention aims at: aiming at the problems, the three-dimensional graphite sphere reinforced copper-based heat conduction composite material and the preparation method thereof are provided to overcome the problems in the prior art.
The technical scheme adopted by the invention is as follows: a preparation method of a three-dimensional graphite sphere reinforced copper-based heat conduction composite material comprises the following steps:
A. plating graphite spheres on the surface of the foam copper by using an electrodeposition method to prepare a composite framework;
B. placing the composite skeleton in a die, and filling copper powder into holes in the skeleton by vacuum filtration to obtain a composite;
C. applying pressure to the die, and pre-pressing the composite body into a blank by cold press molding;
D. and carrying out vacuum hot pressing or spark plasma sintering on the blank, and taking out to obtain the product.
Further, the pore diameter of the foam copper is 20-40PPI, and the thickness of the foam copper is 2-8mm; the particle size of the graphite nodules is 20-40 mu m; the particle size of the copper powder is 5-50 mu m.
Further, in the step A, the copper foam and the graphite nodules are pretreated, and the pretreatment process of the copper foam comprises the following steps: ultrasonic cleaning is carried out on the foamy copper sequentially through acetone and hydrochloric acid solution, then deionized water is used for washing, and then drying is carried out;
the pretreatment process of the graphite nodules comprises the following steps: dispersing graphite nodules in acetone, soaking, washing with deionized water after soaking, and drying.
In the step A, preparing electroplating solution, pouring the electroplating solution into an electroplating bath, dispersing graphite spheres in the electroplating solution, taking foam copper as a cathode, taking a copper sheet as an anode, switching on a power supply, starting deposition, and washing and drying after the deposition is finished.
Further, the foam copper cathode is fixed in the middle of the electroplating bath, a piece of phosphor copper anode is respectively placed at two sides, the power supply is turned on, the stirring is carried out while the deposition is carried out, and the stirring speed is 150-350rpm.
Further, in the electrodeposition, the plating voltage is 1 to 3V (for example, 1V, 1.5V, 2V, 3V, etc.), the plating time is 6 to 16 hours, and the plating time is determined according to the voltage and the specific conditions of the copper foam and the graphite nodule size, but is not suitable to be too long or too short.
Further, the electroplating solution is prepared by mixing and dissolving copper sulfate, sodium potassium tartrate, sodium citrate and potassium nitrate in deionized water according to a mass ratio of 18-22:3-5:30-40:4-5 (for example, 18:3:30:4, 20:4:36:4.8, 22:5:40:5, etc.).
In the step C, the mold in the cold pressing process is a stainless steel mold, the cold pressing pressure is 10-20MPa (for example, 10MPa, 15MPa, 20MPa and the like), and the pressure is maintained for 1-3min.
Further, the mold in the sintering process is a graphite mold, the sintering pressure is 30-50MPa (for example, 30MPa, 40MPa, 50MPa, etc.), the sintering temperature is 800-950 ℃ (for example, 800 ℃, 850 ℃, 950 ℃ etc.), and the heat preservation time is 10-80min, for example, 10min, 50min, 60min, 80min, etc.
The invention further provides a three-dimensional graphite sphere reinforced copper-based heat conduction composite material, which is prepared by the preparation method.
In summary, due to the adoption of the technical scheme, the beneficial effects of the invention are as follows:
1. according to the invention, the foam copper framework is used as a template to prepare the foam copper-graphite nodule-copper composite heat dissipation material, wherein foam copper provides a template for forming a three-dimensional network in the composite material for graphite nodules, meanwhile, a complete copper heat conduction path is reserved, strength support is provided for filling of subsequent copper powder, and the formed three-dimensional network framework not only improves the heat conduction performance of the composite material, but also improves the mechanical property of the composite material;
2. the through hole structure of the foam copper-graphite nodule composite skeleton enables the copper matrix to form a continuous phase in the three-dimensional network, and a double-communication structure of graphite nodule and copper is formed in the composite material; compared with the uniform distribution of graphite nodules, the three-dimensional network formed by the foam copper templates can obviously improve the heat conduction performance of the composite material under the condition of less addition of the graphite nodules;
3. according to the foam copper-graphite nodule composite skeleton prepared by the electrodeposition method, graphite nodules are loaded on the foam copper skeleton, copper plating layers are plated on the surfaces of the graphite nodules, and the problem of poor wettability between the graphite nodules and a copper matrix is effectively solved by the formation of the copper plating layers;
4. the invention improves the compactness of the composite material by cold press molding and discharge plasma sintering, improves the interface combination between graphite spheres and copper in the composite material, and improves the heat conducting property of the composite material.
Drawings
FIG. 1 is a schematic diagram of a process flow for preparing a foam copper-graphite nodule-copper composite material according to the present invention;
FIG. 2 is a plane microstructure of the composite material prepared in example 1 of the present invention;
FIG. 3 is a cross-sectional microstructure of the composite material prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings.
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
As shown in fig. 1, the preparation method of the three-dimensional graphite sphere reinforced copper-based heat conduction composite material comprises the following steps:
s1, preparing the following materials: the pore diameter of the foam copper is 30PPI, the thickness is 5mm, the diameter of the cylindrical foam copper is 30mm, the particle diameter of the graphite nodules is 20 mu m, and the particle diameter of the pure copper powder is 6.5 mu m;
s2, sequentially passing the foamy copper through acetone and hydrochloric acid solution, ultrasonically cleaning for 10min, then washing with deionized water, putting into a vacuum drying oven, drying at 60 ℃ for 2h, and removing impurities, oxides and the like on the surface of the foamy copper; dispersing graphite spheres in acetone, soaking for 12 hours, cleaning with deionized water, and drying in a blast oven at 60 ℃ for 6 hours after suction filtration is completed;
s3, dissolving 20g of copper sulfate pentahydrate, 4g of potassium sodium tartrate, 36g of sodium citrate and 4.8g of potassium nitrate in 400mL of deionized water, stirring uniformly to obtain a plating solution, pouring the plating solution into a plating bath, and adding graphite spheres to disperse the plating solution in the plating solution;
s4, connecting the foamy copper with a cathode, fixing the foamy copper in the middle of the electroplating bath, respectively placing a copper sheet at two sides of the electroplating bath to be connected with an anode, connecting a circuit, adjusting a direct-current stabilized power supply to enable the power supply voltage to be 1.5V, stirring while depositing, and enabling the stirring rotation speed to be 300rpm, wherein the plating time is 14 hours;
s5, placing the graphite ball-foamy copper composite skeleton obtained after electrodeposition into a stainless steel die, placing the die into a vacuum suction filtration device, and sucking copper powder dispersed in deionized water into skeleton holes until the whole skeleton is filled;
s6, after the suction filtration is finished, placing the die into a vacuum drying oven, drying at 60 ℃ for 12 hours, and applying 10MPa pressure to the die after the drying is finished, and maintaining the pressure for 2 minutes to obtain a cold-pressed blank of the composite material;
and S7, placing the cold-pressed blank body into a graphite mold for vacuum hot-pressing sintering, wherein the sintering pressure is 50MPa, the temperature is raised to 900 ℃, the heat is preserved for 60 minutes, the blank body is cooled to room temperature along with a furnace, and the three-dimensional graphite ball-copper composite material is obtained, and the plane and section microstructure of the composite material are respectively shown in figures 2 and 3. As can be seen from fig. 2 and 3, the copper foam is used as a template, the graphite nodules are plated on the copper foam skeleton to form a three-dimensional continuous structure, and the graphite nodules maintain a three-dimensional interconnection structure after being prepared into a composite material.
The volume fraction of graphite spheres in the obtained three-dimensional graphite sphere-copper composite material is 10.5%, the compactness of the composite material reaches 98.1%, the thermal conductivity in the in-plane direction is 403.6W/(m.K), and the tensile strength reaches 304.5MPa.
Example 2
The preparation method of the three-dimensional graphite sphere reinforced copper-based heat conduction composite material comprises the following steps:
s1, preparing the following materials: the pore diameter of the foam copper is 30PPI, the thickness is 3mm, the diameter of the cylindrical foam copper is 30mm, the particle diameter of the graphite spheres is 40 mu m, and the particle diameter of the pure copper powder is 20 mu m for standby;
s2, sequentially passing the foamy copper through acetone and hydrochloric acid solution, ultrasonically cleaning for 10min, then washing with deionized water, putting into a vacuum drying oven, drying at 60 ℃ for 2h, and removing impurities, oxides and the like on the surface of the foamy copper; dispersing graphite spheres in acetone, soaking for 12 hours, cleaning with deionized water, and drying in a blast oven at 60 ℃ for 6 hours after suction filtration is completed;
s3, dissolving 20g of copper sulfate pentahydrate, 4g of potassium sodium tartrate, 36g of sodium citrate and 4.8g of potassium nitrate in 400mL of deionized water, stirring uniformly to obtain a plating solution, pouring the plating solution into a plating bath, and adding graphite spheres to disperse the plating solution in the plating solution;
s4, connecting the foamy copper with a cathode, fixing the foamy copper in the middle of the electroplating bath, respectively placing a copper sheet at two sides of the electroplating bath to be connected with an anode, connecting a circuit, adjusting a direct-current stabilized power supply to enable the power supply voltage to be 1.5V, stirring while depositing, and enabling the stirring rotation speed to be 300rpm, wherein the plating time is 12 hours;
s5, placing the graphite ball-foamy copper composite skeleton obtained after electrodeposition into a stainless steel die, placing the die into a vacuum suction filtration device, and sucking copper powder dispersed in deionized water into skeleton holes until the whole skeleton is filled;
s6, after the suction filtration is finished, placing the die into a vacuum drying oven, drying at 60 ℃ for 12 hours, and applying 10MPa pressure to the die after the drying is finished, and maintaining the pressure for 2 minutes to obtain a cold-pressed blank of the composite material;
and S7, placing the cold-pressed blank body into a graphite die for spark plasma sintering, wherein the sintering pressure is 40MPa, heating to 850 ℃, preserving heat for 10min, and cooling to room temperature along with a furnace to obtain the three-dimensional graphite ball-copper composite material.
The volume fraction of graphite spheres in the obtained three-dimensional graphite sphere-copper composite material is 7.9%, the compactness of the composite material reaches 98.1%, the thermal conductivity in the in-plane direction is 394.6W/(m.K), and the tensile strength reaches 295.1MPa.
Example 3
The preparation method of the three-dimensional graphite sphere reinforced copper-based heat conduction composite material comprises the following steps:
s1, preparing the following materials: the pore diameter of the foam copper is 20PPI, the thickness is 5mm, the diameter of the cylindrical foam copper is 30mm, the particle diameter of the graphite nodules is 20 mu m, and the particle diameter of the pure copper powder is 10 mu m;
s2, sequentially passing the foamy copper through acetone and hydrochloric acid solution, ultrasonically cleaning for 10min, then washing with deionized water, putting into a vacuum drying oven, drying at 60 ℃ for 2h, and removing impurities, oxides and the like on the surface of the foamy copper; dispersing graphite spheres in acetone, soaking for 12 hours, cleaning with deionized water, filtering, and drying in a blast oven at 60 ℃ for 6 hours;
s3, dissolving 20g of copper sulfate pentahydrate, 4g of potassium sodium tartrate, 36g of sodium citrate and 4.8g of potassium nitrate in 400mL of deionized water, stirring uniformly to obtain a plating solution, pouring the plating solution into a plating bath, and adding graphite spheres to disperse the plating solution in the plating solution;
s4, connecting the foamy copper with a cathode, fixing the foamy copper in the middle of an electroplating bath, respectively placing a copper sheet at two sides of the electroplating bath to be connected with an anode, connecting a circuit, adjusting a direct-current stabilized power supply to enable the power supply voltage to be 2.5V, stirring while depositing, and enabling the stirring rotation speed to be 300rpm, wherein the plating time is 14 hours;
s5, placing the graphite ball-foamy copper composite skeleton obtained after electrodeposition into a stainless steel die, placing the die into a vacuum suction filtration device, and sucking copper powder dispersed in deionized water into skeleton holes until the whole skeleton is filled;
s6, after the suction filtration is finished, placing the die into a vacuum drying oven, drying at 60 ℃ for 12 hours, and applying 10MPa pressure to the die after the drying is finished, and maintaining the pressure for 2 minutes to obtain a cold-pressed blank of the composite material;
and S7, placing the cold-pressed blank body into a graphite die for spark plasma sintering, wherein the sintering pressure is 45MPa, heating to 900 ℃, preserving heat for 10min, and cooling to room temperature along with a furnace to obtain the three-dimensional graphite ball-copper composite material.
The volume fraction of graphite spheres in the obtained three-dimensional graphite sphere-copper composite material is 10.1%, the compactness of the composite material reaches 97.9%, the thermal conductivity in the in-plane direction is 396.4W/(m.K), and the tensile strength reaches 301.2MPa.
Example 4
The preparation method of the three-dimensional graphite sphere reinforced copper-based heat conduction composite material comprises the following steps:
s1, preparing the following materials: the pore diameter of the foam copper is 40PPI, the thickness is 3mm, the diameter of the cylindrical foam copper is 30mm, the particle diameter of the graphite nodules is 20 mu m, and the particle diameter of the pure copper powder is 6.5 mu m;
s2, sequentially passing the foamy copper through acetone and hydrochloric acid solution, ultrasonically cleaning for 10min, then washing with deionized water, putting into a vacuum drying oven, drying at 60 ℃ for 2h, and removing impurities, oxides and the like on the surface of the foamy copper; dispersing graphite spheres in acetone, soaking for 12 hours, cleaning with deionized water, filtering, and drying in a blast oven at 60 ℃ for 6 hours;
s3, dissolving 20g of copper sulfate pentahydrate, 4g of potassium sodium tartrate, 36g of sodium citrate and 4.8g of potassium nitrate in 400mL of deionized water, stirring uniformly to obtain a plating solution, pouring the plating solution into a plating bath, and adding graphite spheres to disperse the plating solution in the plating solution;
s4, connecting the foamy copper with a cathode, fixing the foamy copper in the middle of the electroplating bath, respectively placing a copper sheet at two sides of the electroplating bath to be connected with an anode, connecting a circuit, adjusting a direct-current stabilized power supply to enable the power supply voltage to be 1.5V, stirring while depositing, and enabling the stirring rotation speed to be 300rpm, wherein the plating time is 12 hours;
s5, placing the graphite ball-foamy copper composite skeleton obtained after electrodeposition into a stainless steel die, placing the die into a vacuum suction filtration device, and sucking copper powder dispersed in deionized water into skeleton holes until the whole skeleton is filled;
s6, after the suction filtration is finished, placing the die into a vacuum drying oven, drying at 60 ℃ for 12 hours, and applying 10MPa pressure to the die after the drying is finished, and maintaining the pressure for 2 minutes to obtain a cold-pressed blank of the composite material;
and S7, placing the cold-pressed blank body into a graphite die for vacuum hot-pressing sintering, wherein the sintering pressure is 50MPa, the temperature is raised to 900 ℃, the heat is preserved for 50min, and the three-dimensional graphite ball-copper composite material is obtained after cooling to room temperature along with a furnace.
The volume fraction of graphite spheres in the obtained three-dimensional graphite sphere-copper composite material is 8.8%, the compactness of the composite material reaches 97.5%, the thermal conductivity in the in-plane direction is 392.1W/(m.K), and the tensile strength reaches 295.6MPa.
Comparative example 1
Comparative example 1 is the same as example 1 except that in step S4, the plating time is 16h.
Test results: the volume fraction of graphite spheres in the obtained three-dimensional graphite sphere-copper composite material is 10.8%, the compactness of the composite material reaches 97.8%, the thermal conductivity in the in-plane direction is 401.5W/(m.K), and the tensile strength reaches 298.3MPa.
Comparative example 2
Comparative example 2 is the same as example 1 except that in step S4, the plating time is 12h.
Test results: the volume fraction of graphite spheres in the obtained three-dimensional graphite sphere-copper composite material is 8.3%, the compactness of the composite material reaches 97.8%, the thermal conductivity in the in-plane direction is 395.8W/(m.K), and the tensile strength reaches 292.4MPa.
Comparative example 3
Comparative example 3 is the same as example 1 except that in step S4, the plating time is 10 hours.
Test results: the volume fraction of graphite spheres in the obtained three-dimensional graphite sphere-copper composite material is 6.7%, the compactness of the composite material reaches 98.3%, the thermal conductivity in the in-plane direction is 387.5W/(m.K), and the tensile strength reaches 289.5MPa.
Comparative example 4
Comparative example 4 is the same as example 1 except that in step S4, the plating time is 8h.
Test results: the volume fraction of graphite spheres in the obtained three-dimensional graphite sphere-copper composite material is 5.2%, the compactness of the composite material reaches 98.5%, the thermal conductivity in the in-plane direction is 379.6W/(m.K), and the tensile strength reaches 281.7MPa.
As is clear from comparative examples 1 to 4, when the plating time is too long or too short, the density, thermal conductivity and tensile strength of the three-dimensional graphite nodule-copper composite material are reduced. It can be seen that too short or too long a plating time can negatively affect the performance of the three-dimensional graphite nodule-copper composite material, and the performance of the three-dimensional graphite nodule-copper composite material can be optimized only within a proper plating time range of the invention.
Comparative example 5
Comparative example 5 is the same as example 1 except that the electrodeposition treatment is not performed, but copper foam is immersed in the plating solution for 14 hours and then taken out.
The test results are: graphite nodules cannot be plated on the copper foam and cannot form a composite.
Comparative example 6
Comparative example 6 is the same as example 1 except that step S5 is not performed.
Test results: the volume fraction of graphite spheres in the obtained three-dimensional graphite sphere-copper composite material is 20.5%, the compactness of the composite material reaches 97.1%, the thermal conductivity in the in-plane direction is 389.6W/(m.K), and the tensile strength reaches 284.3MPa.
Therefore, when copper powder filling is absent, the graphite nodule-foam copper composite skeleton directly forms a composite material, the volume fraction of graphite nodule in the composite material is increased, and the density, the heat conductivity and the tensile strength of the three-dimensional graphite nodule-copper composite material are reduced. Thus, the lack of copper powder filling can negatively impact the three-dimensional graphite nodule-copper composite performance.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (10)
1. The preparation method of the three-dimensional graphite sphere reinforced copper-based heat conduction composite material is characterized by comprising the following steps of:
A. plating graphite spheres on the surface of the foam copper by using an electrodeposition method to prepare a composite framework;
B. placing the composite skeleton in a die, and filling copper powder into holes in the skeleton by vacuum filtration to obtain a composite;
C. applying pressure to the die, and pre-pressing the composite body into a blank by cold press molding;
D. and carrying out vacuum hot pressing or spark plasma sintering on the blank, and taking out to obtain the product.
2. The method of claim 1, wherein the copper foam has a pore size of 20-40PPI and a thickness of 2-8mm; the particle size of the graphite nodules is 20-40 mu m; the particle size of the copper powder is 5-50 mu m.
3. The method of claim 1, wherein in step a, copper foam and graphite nodules are pretreated, the copper foam pretreatment process comprising the steps of: ultrasonic cleaning is carried out on the foamy copper sequentially through acetone and hydrochloric acid solution, then deionized water is used for washing, and then drying is carried out;
the pretreatment process of the graphite nodules comprises the following steps: dispersing graphite nodules in acetone, soaking, washing with deionized water after soaking, and drying.
4. A method according to any one of claims 1 to 3, wherein in step a, the plating solution is prepared and poured into a plating tank, graphite spheres are dispersed in the plating solution, then copper foam is used as a cathode, a copper sheet is used as an anode, a power supply is turned on, deposition is started, and after the deposition is finished, the solution is rinsed and dried.
5. The method according to claim 4, wherein the copper foam cathode is fixed in the middle of the plating bath, a piece of phosphor copper anode is placed on each side, the power is turned on, the stirring is performed while the deposition is performed, and the stirring speed is 150-350rpm.
6. The method according to claim 5, wherein the electroplating voltage is 1 to 3V and the plating time is 6 to 16 hours when the electrodeposition is performed.
7. The method according to claim 4, wherein the plating solution is prepared by mixing and dissolving copper sulfate, sodium potassium tartrate, sodium citrate and potassium nitrate in deionized water according to a mass ratio of 18-22:3-5:30-40:4-5.
8. The method of claim 4, wherein in step C, the mold is a stainless steel mold, the cold pressing pressure is 10-20MPa, and the pressure is maintained for 1-3min.
9. The method of claim 4, wherein in step D, the mold is graphite mold, the sintering pressure is 30-50MPa, the sintering temperature is 800-950 ℃, and the heat preservation time is 10-80min.
10. The three-dimensional graphite sphere reinforced copper-based heat conduction composite material is characterized in that the composite material is prepared by the preparation method of any one of claims 1-9.
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