CN116583086A - Preparation method of high-heat-conductivity insulating copper/diamond composite material - Google Patents
Preparation method of high-heat-conductivity insulating copper/diamond composite material Download PDFInfo
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- CN116583086A CN116583086A CN202310725724.1A CN202310725724A CN116583086A CN 116583086 A CN116583086 A CN 116583086A CN 202310725724 A CN202310725724 A CN 202310725724A CN 116583086 A CN116583086 A CN 116583086A
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- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 222
- 239000010432 diamond Substances 0.000 title claims abstract description 222
- 239000010949 copper Substances 0.000 title claims abstract description 81
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 74
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000007639 printing Methods 0.000 claims abstract description 21
- 238000005245 sintering Methods 0.000 claims abstract description 19
- 239000010936 titanium Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 15
- 238000001704 evaporation Methods 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 14
- 238000007731 hot pressing Methods 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 239000002002 slurry Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000009826 distribution Methods 0.000 claims abstract description 7
- 238000007788 roughening Methods 0.000 claims abstract description 6
- 238000007747 plating Methods 0.000 claims abstract description 5
- 238000007650 screen-printing Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 238000009413 insulation Methods 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000000889 atomisation Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 5
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 229920001225 polyester resin Polymers 0.000 claims description 5
- 239000004645 polyester resin Substances 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims 1
- 239000010410 layer Substances 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000002791 soaking Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000002344 surface layer Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005275 alloying Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B17/00—Insulators or insulating bodies characterised by their form
- H01B17/56—Insulating bodies
- H01B17/60—Composite insulating bodies
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- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
Abstract
The invention discloses a preparation method of a high-heat-conductivity insulating copper/diamond composite material, which is characterized in that an artificial diamond sheet and diamond powder are subjected to acid washing roughening treatment respectively; preparing metal titanium with the thickness of 100-500 nm on the surfaces of the diamond sheet and the diamond powder by adopting a vacuum micro-evaporation titanium plating process to obtain a titanium-plated diamond sheet and a titanium-plated diamond powder; mixing copper alloy powder and titanized diamond powder with different volume ratios to obtain a copper/diamond mixture, wherein the diamond content is distributed in a gradient manner, and the maximum diamond content is 60vt percent and the minimum diamond content is 0; respectively adding the mixture into the resin mixed solution, and stirring and uniformly mixing to obtain printing slurry with the diamond content in gradient distribution; sequentially printing slurry on the surface of a titanized diamond sheet through screen printing, wherein the diamond content is from high to low, the content of the outermost layer is 0, and putting the titanium-plated diamond sheet into a vacuum oven for baking and solidifying, and cooling to obtain a copper/diamond prefabricated member; and (3) placing the obtained prefabricated member into a vacuum hot pressing furnace for hot pressing sintering, and finally obtaining the high-heat-conductivity insulating copper/diamond composite material.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a preparation method of a heat-conducting and insulating composite material.
Background
The continuous innovation of electronic information technology promotes the development of power devices to two extreme directions, namely, the larger the output power is, the smaller the size of the device is, and the larger the heat flux density is. How to achieve efficient dissipation of high heat flux density has become a key technology for system design.
The diamond is a three-dimensional ultrahigh heat conducting material, the heat conductivity is approximately isotropic in all directions, the heat conductivity is in the range of 1200-2000W/mK, and the thermal expansion coefficient is 0.8-1.1 x 10 -6 Volume resistivity (25 ℃ C.) > 10 15 Omega cm. Although diamond/copper, diamond/aluminum and other composite materials have higher thermal conductivity and a suitable thermal expansion coefficient as a new generation of thermal management materials, they cannot be used in applications requiring specific insulation or dielectric properties due to the presence of a metal matrix.
At present, the high heat conduction insulating material mainly comprises surface metallization of ceramics such as aluminum nitride, aluminum oxide and the like, and has the insulating property of ceramics and the heat conduction of metals, but the heat conduction of the material is less than 400W/Mk. The high heat conduction insulating composite material prepared by the patent CN 103187131B and the preparation method thereof are composed of the high heat conduction composite material and an insulating layer plated on the high heat conduction composite material. According to the scheme, the insulating layer is prepared by adopting a chemical vapor deposition mode, the thermal conductivity of the insulating layer is more than 400W/Mk, but the insulating layer is low in deposition efficiency, and the production efficiency is severely limited by the defects of complicated preparation process and the like.
In view of the above, a low-cost, high-strength and high-thermal conductivity (thermal conductivity > 600W/Mk) insulating copper/diamond composite material and a preparation method thereof are technical problems to be solved.
Disclosure of Invention
The invention aims to provide a preparation method of a high-heat-conductivity insulating copper/diamond composite material, wherein an intermediate sandwich layer is an artificial sheet-shaped diamond with a certain thickness and high heat conductivity and insulation, an upper layer and a lower layer are copper/diamond composite layers distributed in a gradient mode, and the high-heat-conductivity insulating copper/diamond composite material with low cost and high strength is obtained after hot-pressing sintering.
In order to achieve the above purpose, the following technical scheme is adopted:
the preparation method of the high-heat-conductivity insulating copper/diamond composite material comprises the following steps:
(1) Respectively carrying out acid washing and roughening treatment on the artificial diamond sheet and the diamond powder;
(2) Preparing metal titanium with the thickness of 100-500 nm on the surfaces of the diamond sheet and the diamond powder by adopting a vacuum micro-evaporation titanium plating process to obtain a titanium-plated diamond sheet and a titanium-plated diamond powder;
(3) Mixing copper alloy powder and titanized diamond powder with different volume ratios to obtain a copper/diamond mixture, wherein the diamond content is in gradient distribution, and the maximum diamond content is 60vt percent and the minimum diamond content is 0vt percent; respectively adding the mixture into the resin mixed solution, and stirring and uniformly mixing to obtain printing slurry with the diamond content in gradient distribution;
(4) Printing slurry with gradient diamond content on the surface of the titanized diamond sheet obtained in the step (2) sequentially through screen printing, wherein the diamond content is from high to low, the content of the outermost layer is 0, and putting the titanium plated diamond sheet into a vacuum oven for baking and solidifying, and cooling to obtain a copper/diamond prefabricated member;
(5) And (3) placing the obtained prefabricated member into a vacuum hot pressing furnace for hot pressing sintering, and finally obtaining the high-heat-conductivity insulating copper/diamond composite material.
According to the scheme, the heat conductivity of the diamond sheet in the step 1 is 1000-1500W/mk, the thickness is 0.2-0.5 mm, and the volume resistivity (25 ℃) is more than 10 15 Ω㎝。
According to the scheme, the diamond powder in the step 1 has the particle size of 50-100 um, preferably 50-75um.
According to the scheme, the vacuum micro-evaporation titanizing process in the step 2 comprises the following steps:
placing the diamond sheet and diamond micropowder into a special crucible of a vacuum micro-evaporation coating machine, wherein the vacuum degree is more than 5 x 10 -4 Heating up after Pa, preserving heat for 60-90 min after the temperature reaches 700-800 ℃, and keeping vacuum cooling to room temperature after coating is finished to obtain the titanized diamond sheet and the titanized diamond powder.
According to the scheme, the resin mixed solution in the step 3 is prepared by mixing saturated polyester resin, dibasic acid ester organic solvent and isocyanate curing agent according to the mass ratio of (4-6) (4-5) (0.5-1).
According to the scheme, the copper alloy powder in the step 3 is prepared by a water-gas combined atomization powder preparation process, and the granularity is 10-100 um, preferably 20-50 um; the weight fractions of the components are as follows: b: 0.06-0.8%, P: 0.002-0.2%, cr:0.02 to 0.5 percent of Al:0.01 to 0.2 percent and the balance of Cu.
According to the scheme, step 3 comprises the steps of putting the titanized diamond powder and the copper alloy powder into a mixer to respectively prepare four different volume fraction copper/diamond mixtures with the diamond volume fractions of 60%, 40%, 20% and 0%.
According to the scheme, in the step 3, the copper/diamond mixture and the resin mixed solution are mixed according to the mass ratio of 2 (1-1.5).
According to the scheme, the printing slurry with the diamond content from high to low is sequentially stacked and printed on the surface of the titanized diamond sheet in the step 4, and the printing thickness of each layer is 0.1-0.2 mm.
According to the scheme, the hot press sintering process conditions in the step 5 comprise:
vacuum degree is 10 -1 ～10 -2 Pa, inert atmosphere or hydrogen-argon mixed reducing atmosphere with hydrogen volume fraction of 5%, heatingIn the process, heating to 900-1050 ℃ at a speed of 5-20 ℃/min, preserving heat for 30-120 min, starting to pressurize after the heat preservation is finished, wherein the pressurizing pressure is 1-5 MPa, and the pressurizing time is 30-120 min.
Compared with the prior art, the invention has the following beneficial effects:
synthetic diamond has high thermal conductivity and insulation, but its surface energy is high, thermal expansion coefficient is very different from other materials, and it is difficult to realize high-strength compounding. According to the invention, the surface area of the diamond is increased by roughening the surfaces of the artificial diamond and the diamond powder. Meanwhile, a metal titanium protective layer is prepared by a vacuum evaporation coating technology, and the metal titanium is a metal with very active chemical property and is easy to form Ti with copper and the like 2 Cu, tiCu, and the like. Researches show that the thicker metal film can prevent the overall heat conductivity of diamond-metal, and the vacuum micro-evaporation plating process can well control the growth speed of the metal film, so that the metal titanium is uniformly coated on the surfaces of the artificial diamond sheet and the diamond powder. The invention can solve the problem of diamond surface energy and regulate and control the overall heat resistance of the metal titanium film to copper/diamond.
The invention adopts the structure that the middle core layer is the upper layer and the lower layer of the artificial diamond sheet are of gradient distribution copper/diamond. The artificial diamond sheet can separate copper/diamond on the upper surface layer from copper/diamond on the lower surface layer to achieve good heat conduction and insulation properties; the invention prepares the copper/diamond gradient on the surface of the artificial diamond sheet, and solves the problems that the interface joint is cracked and the heat conduction is poor due to the large difference of the thermal expansion coefficients of the artificial diamond sheet and the copper/diamond.
According to the copper alloy powder designed by the invention, B, P trace alloying elements are added, and on one hand, copper powder is oxidized into CuO by trace oxygen elements in the sintering process 2 While B, P element plays a role in deoxidizing CuO 2 The oxide of B and the oxide of P are generated by reducing Cu and are discharged out of the hearth, so that the performance of the copper diamond is improved. Cr and Al elements are dissolved into a Cu matrix to increase the strength of the Cu matrix, and meanwhile, the Cr and Al elements are spread on the surface of the diamond to form a multi-element solid solution with Ti and Cu, so that the copper alloy skeleton and the diamond are improvedAnd the bonding strength of the metal film is improved.
The invention adopts high-temperature pressure sintering, and oxidation films are easy to form on the surfaces of copper alloy powder in the high-temperature sintering to prevent sintering, and an external force is applied in the sintering process to break the oxidation films, so that the copper/diamond density is improved.
The hardness of the diamond particles is higher and can reach 10 Mohs hardness, and the processing difficulty is higher. The diamond content of the outermost layer of the high-heat-conductivity insulating copper/diamond composite material is 0, so that the surface processability is ensured, and the surface roughness Ra is less than or equal to 0.2.
The invention has the beneficial effects that:
according to the high-heat-conductivity insulating copper/diamond composite material and the preparation method thereof, the artificial diamond sheet is used as a sandwich layer, copper/diamond materials are distributed in an up-down gradient mode, and copper with a certain thickness is coated on the surface of the artificial diamond sheet. Has the advantages of high strength, high heat conduction (heat conductivity is more than 600W/mk), low thermal expansion and high insulation; the upper and lower surfaces can be machined to prepare high-precision high-heat-conductivity insulating parts with higher requirements on finish.
The preparation process provided by the invention is simple and convenient, and is suitable for mass industrialized production.
Drawings
Fig. 1: the invention relates to a preparation process flow chart of a high-heat-conductivity insulating copper/diamond composite material.
Fig. 2: titanium coated diamond powder morphology and energy spectrum in example 1.
Fig. 3: the invention discloses a structural schematic diagram of a high-heat-conductivity insulating copper/diamond composite material.
Detailed Description
The following examples further illustrate the technical aspects of the present invention, but are not intended to limit the scope of the present invention.
The specific embodiment provides a preparation method of a high-heat-conductivity insulating copper/diamond composite material, which comprises the following process flows with reference to the accompanying figure 1:
(1) Respectively carrying out acid washing and roughening treatment on the artificial diamond sheet and the diamond powder; comprises soaking artificial diamond sheet and diamond powder with 150g/L NaOH solution for 30min to remove fat, and washing with waterTo neutrality; then 80% (volume ratio of concentrated nitric acid to water is 4:1) HNO is used 3 Soaking in the solution for 40min for roughening treatment, washing with water to neutrality and drying;
(2) Preparing metal titanium with the thickness of 100-500 nm on the surfaces of the diamond sheet and the diamond powder by adopting a vacuum micro-evaporation titanium plating process to obtain a titanium-plated diamond sheet and a titanium-plated diamond powder;
(3) Mixing copper alloy powder and titanized diamond powder with different volume ratios to obtain a copper/diamond mixture, wherein the diamond content is in gradient distribution, and the maximum diamond content is 60vt percent and the minimum diamond content is 0vt percent; respectively adding the mixture into the resin mixed solution, and stirring and uniformly mixing to obtain printing slurry with the diamond content in gradient distribution;
(4) Printing slurry with gradient diamond content on the surface of the titanized diamond sheet obtained in the step (2) sequentially through screen printing, wherein the diamond content is from high to low, the content of the outermost layer is 0, and putting the titanium plated diamond sheet into a vacuum oven for baking and solidifying, and cooling to obtain a copper/diamond prefabricated member;
(5) And (3) placing the obtained prefabricated member into a vacuum hot pressing furnace for hot pressing sintering, and finally obtaining the high-heat-conductivity insulating copper/diamond composite material.
Specifically, the thermal conductivity of the diamond sheet is 1000-1500W/mk, the thickness is 0.2-0.5 mm, and the volume resistivity (25 ℃) is more than 10 15 Omega cm. The diamond powder has a particle size of 50-100 um, preferably 50-75um.
Specifically, the vacuum micro-evaporation titanizing process in the step 2 comprises the following steps:
placing the diamond sheet and diamond micropowder into a special crucible of a vacuum micro-evaporation coating machine, wherein the vacuum degree is more than 5 x 10 -4 Heating up after Pa, preserving heat for 60-90 min after the temperature reaches 700-800 ℃, and keeping vacuum cooling to room temperature after coating is finished to obtain the titanized diamond sheet and the titanized diamond powder.
Specifically, the resin mixed solution in the step 3 is prepared by mixing (4-6) saturated polyester resin, (4-5) dibasic acid ester organic solvent and isocyanate curing agent according to the mass ratio of (0.5-1).
Specifically, the copper alloy powder is prepared by adopting a water-gas combined atomization powder preparation process, and the granularity is 10-100 um, preferably 20-50 um; the weight fractions of the components are as follows: b: 0.06-0.8%, P: 0.002-0.2%, cr:0.02 to 0.5 percent of Al:0.01 to 0.2 percent and the balance of Cu.
Specifically, step 3 comprises the steps of putting the titanized diamond powder and the copper alloy powder into a mixer to respectively prepare four different volume fraction copper/diamond mixtures with the diamond volume fractions of 60%, 40%, 20% and 0%. The copper/diamond mixture and the resin mixed solution are mixed according to the mass ratio of 2 (1-1.5).
Specifically, in the step 4, printing slurry with the diamond content from high to low is sequentially stacked and printed on the surface of the titanized diamond sheet, and the printing thickness of each layer is 0.1-0.2 mm.
Specifically, the hot press sintering process conditions in step 5 include:
vacuum degree is 10 -1 ～10 -2 Pa, inert atmosphere or hydrogen-argon mixed reducing atmosphere with hydrogen volume fraction of 5%, heating to 900-1050 ℃ at a speed of 5-20 ℃/min in the heating process, preserving heat for 30-120 min, starting to pressurize after preserving heat, wherein the pressurizing pressure is 1-5 MPa, and the pressurizing time is 30-120 min.
Example 1
1) Vacuum micro-evaporation titanizing treatment of artificial diamond sheet and diamond powder: firstly, soaking the artificial diamond sheet and diamond powder in 150g/L NaOH solution for 30min to remove fat, and then washing the artificial diamond sheet and diamond powder to be neutral; then 80% (volume ratio of concentrated nitric acid to water is 4:1) HNO is used 3 Soaking the solution for 40min to remove fat, washing with water to neutrality, and oven drying; placing the diamond sheet and diamond micropowder into a special crucible of a vacuum micro-evaporation coating machine, wherein the vacuum degree is more than 5 x 10 -4 Heating after Pa, keeping the temperature at 750 ℃ for 60min, keeping vacuum cooling to room temperature after coating, and taking out the product to obtain the titanized diamond sheet and the titanized diamond powder. The diamond particle size is 50um, the artificial diamond sheet has a heat conductivity of 1250W/mk, a thickness of 0.3mm and a volume resistivity (25 ℃) of 6.8x10 15 Omega cm. The morphology and the energy spectrum of the titanized diamond powder are shown in figure 2.
2) Polyester resin, dibasic acid ester organic solvent and isocyanate curing agent according to the mass ratio of 4:4: and 0.5, fully stirring and uniformly mixing to obtain a resin mixed solution. And respectively adding the four copper/diamond mixtures with the diamond volume fractions of 60%, 40%, 20% and 0% into the resin mixed solution, and stirring and uniformly mixing to obtain the copper/diamond printing paste. The copper alloy powder is prealloy powder prepared by a water-gas combined atomization powder process, and the granularity is 40-50 um. The weight fractions of the components are as follows: b:0.1%, P:0.005%, cr:0.05%, al:0.03%, cu: the balance. The method comprises the steps of carrying out a first treatment on the surface of the
3) The four copper/diamond printing pastes are sequentially stacked and printed on the surface of the titanized diamond sheet, the printing thickness of each layer is 0.1mm, the diamond content is distributed in a gradient way, and the surface layer content is 0. Placing the copper/diamond preform into a vacuum oven to bake for 30min at 120 ℃, and cooling to obtain an insulating copper/diamond preform;
4) The obtained prefabricated member is put into a vacuum hot pressing furnace for hot pressing sintering, and the process conditions are as follows: vacuum degree is 10 -1 Pa, a hydrogen-argon mixed reducing atmosphere with the hydrogen volume fraction of 5 percent, heating to 1000 ℃ at the speed of 6 ℃/min in the heating process, preserving heat for 60min, starting to pressurize after the heat preservation is finished, wherein the pressurizing pressure is 3MPa, and the pressurizing time is 30min.
The bonding strength of the copper diamond and the artificial diamond sheet of the high heat conduction insulating copper/diamond composite material obtained in the embodiment is 75Mpa, and the thermal expansion coefficient of the composite thermal conductivity 782W/Mk is: 7.6X10 -6 Per DEG C, volume resistivity (25 ℃) 5.3 x 10 15 Ω㎝。
The structural schematic diagram of the high heat conduction insulating copper/diamond composite material obtained in the embodiment is shown in fig. 3.
Example 2
1) Vacuum micro-evaporation titanizing treatment of artificial diamond sheet and diamond powder: firstly, soaking the artificial diamond sheet and diamond powder in 150g/L NaOH solution for 30min to remove fat, and then washing the artificial diamond sheet and diamond powder to be neutral; then 80% (volume ratio of concentrated nitric acid to water is 4:1) HNO is used 3 Soaking the solution for 40min to remove fat, washing with water to neutrality, and oven drying; placing the diamond sheet and diamond micropowder into a special crucible of a vacuum micro-evaporation coating machine, wherein the vacuum degree is more than 5 x 10 -4 Heating after Pa, keeping the temperature at 750 ℃ for 60min, and keeping vacuum cooling to room temperature after coatingAnd taking out the product to obtain the titanized diamond sheet and titanized diamond powder. The diamond particle size is 100um, the artificial diamond sheet has a heat conductivity of 1250W/mk, a thickness of 0.3mm and a volume resistivity (25 ℃) of 6.8x10 15 Ω㎝。
2) Polyester resin, dibasic acid ester organic solvent and isocyanate curing agent according to the mass ratio of 4:5: and 0.8, fully stirring and uniformly mixing to obtain a resin mixed solution. And respectively adding the four copper/diamond mixtures with the diamond volume fractions of 60%, 40%, 20% and 0% into the resin mixed solution, and stirring and uniformly mixing to obtain the copper/diamond printing paste. The copper alloy powder is prealloy powder prepared by a water-gas combined atomization powder process, and the granularity is 40-50 um. The weight fractions of the components are as follows: b:0.5%, P:0.1%, cr:0.3%, al:0.2%, cu: the balance.
3) Four copper/diamond printing pastes are sequentially stacked and printed on the surface of the titanized diamond sheet, the printing thickness of each layer is 0.2mm, the diamond content is distributed in a gradient way, and the surface layer content is 0. Placing the copper/diamond preform into a vacuum oven to bake for 30min at 120 ℃, and cooling to obtain an insulating copper/diamond preform;
4) The obtained prefabricated member is put into a vacuum hot pressing furnace for hot pressing sintering, and the process conditions are as follows: vacuum degree is 10 -1 Pa, a hydrogen-argon mixed reducing atmosphere with the hydrogen volume fraction of 5 percent, heating to 950 ℃ at the speed of 6 ℃/min in the heating process, preserving heat for 60min, starting to pressurize after the heat preservation is finished, wherein the pressurizing pressure is 1MPa, and the pressurizing time is 30min.
Bonding strength of copper diamond and artificial diamond sheet of high heat conduction and insulation copper/diamond composite material obtained in this example: 58Mpa, integrated thermal conductivity: 695W/Mk, integrated thermal expansion coefficient: 7.2X10 -6 Volume resistivity at/deg.C: (25 ℃) 4.1 x 10 15 Ω㎝。
Comparative example 1
The volume fraction of diamond in the copper/diamond mixture of example 1 was varied and the experimental results are shown in table 1.
TABLE 1
Comparative example 2
The high temperature pressure sintering parameters in example 1 were varied and the experimental results are shown in table 2.
TABLE 2
| Comparative experiments | Temperature (temperature) | Pressure of | Results |
| 1 | 800℃ | 10Mpa | Cracking of artificial diamond sheet |
| 2 | 1000℃ | 3Mpa | The bonding strength of the copper diamond and the diamond sheet is 5MPa, and the thermal conductivity is 320W/mK |
| 3 | 1050℃ | 3Mpa | Copper diamond and diamond sheet bonding strength 75Mpa, comprehensive thermal conductivity 782W/M |
| 4 | 800℃ | 3Mpa | Copper diamond and diamond sheet bonding strength 2Mpa, comprehensive thermal conductivity 282W/M |
| 5 | 1050℃ | 1Mpa | The bonding strength of the copper diamond and the diamond sheet is 43Mpa, and the comprehensive heat conductivity is 565W/M |
The comparison shows that the volume fraction of diamond on different surface layers, the sintering temperature and the sintering pressure time which are too high or too low during sintering can influence the product performance.
Claims (10)
1. The preparation method of the high-heat-conductivity insulating copper/diamond composite material is characterized by comprising the following steps of:
(1) Respectively carrying out acid washing and roughening treatment on the artificial diamond sheet and the diamond powder;
(2) Preparing metal titanium with the thickness of 100-500 nm on the surfaces of the diamond sheet and the diamond powder by adopting a vacuum micro-evaporation titanium plating process to obtain a titanium-plated diamond sheet and a titanium-plated diamond powder;
(3) Mixing copper alloy powder and titanized diamond powder with different volume ratios to obtain a copper/diamond mixture, wherein the diamond content is distributed in a gradient manner, and the maximum diamond content is 60vt percent and the minimum diamond content is 0; respectively adding the mixture into the resin mixed solution, and stirring and uniformly mixing to obtain printing slurry with the diamond content in gradient distribution;
(4) Sequentially printing the printing slurry obtained in the step (3) on the surface of the titanized diamond sheet obtained in the step (2) through screen printing, wherein the diamond content is from high to low, the content of the outermost layer is 0, and putting the titanium plated diamond sheet into a vacuum oven for baking and solidifying, and cooling to obtain a copper/diamond prefabricated member;
(5) And (3) placing the obtained prefabricated member into a vacuum hot pressing furnace for hot pressing sintering, and finally obtaining the high-heat-conductivity insulating copper/diamond composite material.
2. The method for preparing a high thermal conductivity insulating copper/diamond composite material according to claim 1, wherein the diamond sheet in step 1 has a thermal conductivity of 1000-1500W/mk, a thickness of 0.2-0.5 mm, and a volume resistivity (25 ℃) of > 10 15 Ω㎝。
3. The method for preparing a high thermal conductivity insulating copper/diamond composite material according to claim 1, wherein the diamond powder in step 1 has a particle size of 50-100 um.
4. The method for preparing the high heat conduction and insulation copper/diamond composite material as claimed in claim 1, wherein the step 2 vacuum micro evaporation titanizing process comprises the following steps:
placing the diamond sheet and diamond micropowder into a special crucible of a vacuum micro-evaporation coating machine, wherein the vacuum degree is more than 5 x 10 -4 Heating up after Pa, preserving heat for 60-90 min after the temperature reaches 700-800 ℃, and keeping vacuum cooling to room temperature after coating is finished to obtain the titanized diamond sheet and the titanized diamond powder.
5. The preparation method of the high heat conduction and insulation copper/diamond composite material as claimed in claim 1, wherein the resin mixed solution in the step 3 is prepared by mixing saturated polyester resin, dibasic acid ester organic solvent and isocyanate curing agent according to the mass ratio of (4-6): (4-5): (0.5-1).
6. The method for preparing the high-heat-conductivity insulating copper/diamond composite material according to claim 1, wherein the copper alloy powder in the step 3 is prepared by a water-gas combined atomization powder preparation process, and the granularity is 10-100 um; the weight fractions of the components are as follows: b: 0.06-0.8%, P: 0.002-0.2%, cr:0.02 to 0.5 percent of Al:0.01 to 0.2 percent and the balance of Cu.
7. The method of producing a high thermal conductivity and insulating copper/diamond composite material according to claim 1, wherein step 3 comprises placing titanized diamond powder and copper alloy powder into a mixer to prepare four different volume fraction copper/diamond mixtures with diamond volume fractions of 60%, 40%, 20% and 0%, respectively.
8. The method for preparing the high-heat-conductivity insulating copper/diamond composite material according to claim 1, wherein the copper/diamond mixture and the resin mixed solution in the step 3 are mixed according to a mass ratio of 2 (1-1.5).
9. The method for preparing the high heat conduction and insulation copper/diamond composite material as claimed in claim 1, wherein in the step 4, printing slurry with the diamond content from high to low is sequentially stacked and printed on the surface of the titanized diamond sheet, and the printing thickness of each layer is 0.1-0.2 mm.
10. The method for preparing the high thermal conductivity and insulation copper/diamond composite material according to claim 1, wherein the hot press sintering process conditions in the step 5 comprise:
vacuum degree is 10 -1 ～10 -2 Pa, inert atmosphere or hydrogen-argon mixed reducing atmosphere with hydrogen volume fraction of 5%, heating to 900-1050 ℃ at a speed of 5-20 ℃/min in the heating process, preserving heat for 30-120 min, starting to pressurize after preserving heat, wherein the pressurizing pressure is 1-5 MPa, and the pressurizing time is 30-120 min.
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