CN112877560B - Diamond/copper composite material and preparation method thereof - Google Patents

Diamond/copper composite material and preparation method thereof Download PDF

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Publication number
CN112877560B
CN112877560B CN202110034857.5A CN202110034857A CN112877560B CN 112877560 B CN112877560 B CN 112877560B CN 202110034857 A CN202110034857 A CN 202110034857A CN 112877560 B CN112877560 B CN 112877560B
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diamond
copper
composite material
surfactant
pure copper
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CN112877560A (en
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吴劲频
周强
黄紫彬
罗莉
潘锡翔
温禄
魏世超
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Jiangxi Ionic Rare Earth Engineering Research Co ltd
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Jiangxi Ionic Rare Earth Engineering Research Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/17—Metallic particles coated with metal
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1005—Pretreatment of the non-metallic additives
    • C22C1/101—Pretreatment of the non-metallic additives by coating
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper

Abstract

The invention belongs to the technical field of composite materials, and provides a diamond/copper composite material and a preparation method thereof, wherein the preparation method provided by the invention comprises the steps of uniformly dispersing diamond particles on a pure copper substrate in a sedimentation mode, and then depositing copper in gaps formed by the diamond particles by adopting an electrodeposition method, so that the dispersion uniformity of copper and diamond on the surface of the pure copper substrate is improved, and the binding force between the copper and diamond deposition layer and the surface of the pure copper substrate is also ensured; the preparation method provided by the invention has mild operation conditions. The data of the examples show that: the diamond/copper composite material provided by the invention has the mass percentage of diamond of 12.7-42.5%; the thermal conductivity of the diamond/copper composite material is 415-617W/mK.

Description

Diamond/copper composite material and preparation method thereof
Technical Field
The invention relates to the technical field of composite materials, in particular to a diamond/copper composite material and a preparation method thereof.
Background
In recent years, with the increasing demands for light weight, high efficiency and miniaturization of electronic products, packaging materials with high thermal conductivity have become hot research spots at home and abroad. Diamond/copper composites have received much attention because of their high thermal conductivity.
At present, the main preparation methods of the diamond/copper composite material comprise a powder metallurgy method, a high-temperature high-pressure method, a discharge plasma sintering method and a liquid infiltration method. Of these preparation methods, powder metallurgy is generally required to be carried out at high temperatures above 1000 ℃, which leads to graphitization of diamond; the high-temperature high-pressure method not only needs to apply high temperature but also needs to apply certain pressure in the process of preparing the diamond/copper composite material, and the preparation conditions are severe; in addition, the discharge plasma sintering method is difficult to obtain the diamond/copper composite material with higher diamond content; the liquid infiltration method has higher requirements on preparation equipment. Various problems occurring in these preparation methods severely restrict the development of the diamond/copper composite material and limit the application of the diamond/copper composite material in packaging.
Disclosure of Invention
In view of the above, the present invention is directed to a diamond/copper composite material and a method for preparing the same. The preparation method provided by the invention has mild reaction conditions, and diamond particles are well compounded with copper and combined on the surface of a pure copper matrix.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a diamond/copper composite material, which comprises the following steps:
soaking a pure copper matrix in an electrolyte solution, and after diamond particles in the electrolyte solution are completely settled in the pure copper matrix, carrying out electrodeposition by taking the pure copper matrix with the settled diamond particles as a cathode and a phosphorus-containing copper sheet as an anode to obtain a diamond/copper composite material;
the electrolyte solution includes copper ions, a surfactant, and diamond particles.
Preferably, the electrolyte solution is an aqueous solution comprising the following concentration components: 40-60 g/L of copper ions, 0.01-10 g/L of surfactant and 1.5-3.5 g/L of diamond particles.
Preferably, the pH value of the electrolyte solution is 2-5 or 8-9.
Preferably, the diamond particles have a particle size of 15 to 55 μm.
Preferably, the surface of the diamond particles is further coated with a metal layer, and the material of the metal layer is WC, Cr, Ni or Mn; the wrapping amount of the metal layer is 20-200% of the weight of the diamond particles.
Preferably, the surfactant comprises one or more of a first surfactant, a second surfactant or a third surfactant; the first surfactant comprises one or more of gelatin, sodium dodecyl sulfate, thiourea, benzotriazole and ethylenediamine; the second surfactant comprises polyethylene glycol and/or polypropylene glycol; the third surfactant comprises copper chloride or copper cyanide.
Preferably, when the surfactant is a first surfactant, the concentration of the first surfactant is 0.01-1.5 g/L;
when the surfactants are a first surfactant and a second surfactant, the concentration of the first surfactant is 0.01-1 g/L; the concentration of the second surfactant is 0.01-1 g/L;
when the surfactants are a first surfactant and a third surfactant, the concentration of the first surfactant is 0.01-1.5 g/L; the concentration of the third surfactant is 0.05-2 g/L;
when the surfactants are a first surfactant, a second surfactant and a third surfactant, the concentration of the first surfactant is 0.01-1.5 g/L; the concentration of the second surfactant is 0.01-1 g/L, and the concentration of the third surfactant is 0.05-2 g/L;
when the surfactant is a second surfactant, the concentration of the second surfactant is 0.01-1 g/L;
when the surfactants are a second surfactant and a third surfactant, the concentration of the second surfactant is 0.01-1 g/L, and the concentration of the third surfactant is 0.05-2 g/L;
when the surfactant is a third surfactant, the concentration of the third surfactant is 0.05-2 g/L.
Preferably, the parameters of electrodeposition include: the current density is 0.5-14A/dm2The temperature is 20-50 ℃.
Preferably, the pure copper matrix is prepared by a method comprising the following steps:
polishing, cleaning and activating a pure copper matrix raw material to obtain a pure copper matrix;
the mass content of copper in the pure copper matrix raw material is more than or equal to 99.5 percent.
The invention also provides the diamond/copper composite material obtained by the preparation method in the technical scheme, which comprises a pure copper matrix and a diamond/copper composite material layer combined on the pure copper matrix; the mass content of diamond in the diamond/copper composite material layer is 10-60%.
The invention provides a preparation method of a diamond/copper composite material, which comprises the following steps: soaking a pure copper matrix in an electrolyte solution, and after diamond particles in the electrolyte solution are completely settled in the pure copper matrix, carrying out electrodeposition by taking the pure copper matrix with the settled diamond particles as a cathode and a phosphorus-containing copper sheet as an anode to obtain a diamond/copper composite material; the electrolyte solution includes copper ions, a surfactant, and diamond particles. According to the preparation method provided by the invention, diamond particles are uniformly dispersed on a pure copper substrate in a sedimentation mode, and then copper is deposited in gaps formed by the diamond particles by adopting an electrodeposition method, so that the dispersion uniformity of copper and diamond on the surface of the pure copper substrate is improved; meanwhile, copper is electrodeposited on a pure copper matrix, and the pure copper matrix and the deposit copper are made of one material, so that the strong binding force between the copper and diamond deposition layers and the surface of the pure copper matrix is ensured; the preparation method provided by the invention has mild operation conditions. The data of the examples show that: the diamond/copper composite material provided by the invention has the advantages that the mass percentage of diamond is 12.7-42.5%, and the content of diamond particles is high; the thermal conductivity of the diamond/copper composite material is 415-617W/mK.
Drawings
FIG. 1 is a scanning electron micrograph of a diamond/copper composite obtained in example 1;
FIG. 2 is an EDS diagram of the diamond/copper composite obtained in example 1;
FIG. 3 is a graph of the compositional analysis of point 1 in FIG. 2;
FIG. 4 is a graph of the compositional analysis of point 2 in FIG. 2;
FIG. 5 is a graph of the compositional analysis of point 3 in FIG. 2;
fig. 6 is a partially enlarged view of the diamond/copper composite obtained in example 2.
Detailed Description
The invention provides a preparation method of a diamond/copper composite material, which comprises the following steps:
and (2) soaking a pure copper matrix in an electrolyte solution, and after diamond particles in the electrolyte solution are completely settled in the pure copper matrix, carrying out electrodeposition by taking the pure copper matrix with the settled diamond particles as a cathode and a phosphorus-containing copper sheet as an anode to obtain the diamond/copper composite material.
In the present invention, the raw materials are preferably those commercially available, unless otherwise specified.
In the present invention, the pure copper matrix is preferably prepared by a method comprising the steps of: and polishing, cleaning and activating the raw material of the pure copper matrix to obtain the pure copper matrix. In the invention, the mass content of copper in the pure copper matrix raw material is preferably more than or equal to 99.5%; the material of the pure copper matrix is preferably red copper. The shape of the pure copper matrix raw material is not particularly limited, and a person skilled in the art can design the shape according to the actual requirement of the diamond/copper composite material. In the present invention, the grinding process preferably includes: the method comprises the following steps of sequentially polishing 200-mesh sand paper, 500-mesh sand paper, 1000-mesh sand paper and 2000-mesh sand paper, wherein the polishing time is not particularly limited as long as the surface of the pure copper substrate raw material can be smooth and flat. In the invention, the cleaning comprises ultrasonic cleaning and rinsing which are carried out in sequence; the washing comprises ethanol washing and water washing which are sequentially carried out; the time and parameters of the ultrasonic washing and rinsing are not particularly limited in the present invention, and the technical means well known to those skilled in the art can be adopted. In the present invention, the activating agent is preferably hydrochloric acid, and the activating manner is preferably immersion, that is, the activating process is particularly preferably: soaking the cleaned pure copper matrix raw material in the hydrochloric acid; the mass concentration of the hydrochloric acid is preferably 10%, and the activation time is preferably 0.1-5 h, and more preferably 1 h. After the activation, the invention preferably further comprises the step of washing and drying the activated pure copper matrix raw material with water to obtain the copper matrix. The parameters of the water washing and drying are not specifically limited in the present invention, and the technical means well known to those skilled in the art can be adopted. In the invention, the activation can remove oxide impurities on the surface of the pure copper matrix raw material, and the bonding force of the deposition layer and the matrix is ensured.
In the present invention, the electrolyte solution includes copper ions, a surfactant, and diamond particles, and the electrolyte solution is further preferably an aqueous solution including the following concentration components: 40-60 g/L of copper ions, 0.01-10 g/L of surfactant and 1.5-3.5 g/L of diamond particles.
In the invention, the concentration of copper ions in the electrolyte solution is preferably 40-60 g/L; the copper ions are preferably provided by a water-soluble copper salt; the water-soluble copper salt is preferably CuSO4·5H2O、CuCl2·2H2O and Cu (CN)2More preferably CuSO4·5H2O and CuCl2·2H2A mixture of O. In the present invention, the water-soluble copper salt functions to provide a source of copper ions for copper deposition.
In the invention, the concentration of the surfactant in the electrolyte solution is preferably 0.01-10 g/L, and the surfactant preferably comprises one or more of a first surfactant, a second surfactant or a third surfactant; the first surfactant preferably comprises one or more of gelatin, sodium dodecyl sulfate, thiourea, benzotriazole and ethylenediamine; the second surfactant comprises polyethylene glycol and/or polypropylene glycol; the third surfactant comprises copper chloride or copper cyanide.
In the invention, when the surfactant is preferably a first surfactant, the concentration of the first surfactant is preferably 0.01-1.5 g/L.
In the invention, when the surfactant is preferably a first surfactant and a second surfactant, the concentration of the first surfactant is preferably 0.01-1.5 g/L; the concentration of the second surfactant is preferably 0.01-1 g/L.
In the invention, when the surfactant is a first surfactant and a third surfactant, the concentration of the first surfactant is preferably 0.01-1.5 g/L; the concentration of the third surfactant is preferably 0.05-2 g/L.
In the invention, when the surfactant is preferably a first surfactant, a second surfactant and a third surfactant, the concentration of the first surfactant is preferably 0.01-1.5 g/L; the concentration of the second surfactant is 0.01-1 g/L, and the concentration of the third surfactant is 0.05-2 g/L.
When the surfactant is preferably a second surfactant, the concentration of the second surfactant is preferably 0.01-1 g/L;
when the surfactant is preferably a second surfactant and a third surfactant, the concentration of the second surfactant is preferably 0.01-1 g/L, and the concentration of the third surfactant is preferably 0.05-2 g/L;
when the surfactant is preferably a third surfactant, the concentration of the third surfactant is preferably 0.05-2 g/L.
In the invention, the surfactant can play a role in depositing layer grains, enabling the surface of the depositing layer to be bright and smooth or removing faults.
In the invention, the concentration of the diamond particles in the electrolyte solution is preferably 1.5-3.5 g/L; the particle size of the diamond particles is preferably 15-55 mu m. In the invention, the surface of the diamond particles is preferably further coated with a metal layer, and the material of the metal layer is preferably WC, Cr, Ni or Mn, and is further preferably WC; the thickness of the metal layer is preferably 70 mu m-1 mm; the wrapping weight of the metal layer is preferably 20-200% of the weight of the diamond particles; particularly preferred is that purchased from Henan yellow river cyclone, Inc. In the present invention, further, the diamond surface is plated with metal to increase the conductivity during the electrodeposition process and to make the bonding force between diamond and copper stronger.
In the invention, the pH value of the electrolyte solution is preferably 2-5 or 8-9; the reagent for adjusting the electrolyte solution is preferably hydrochloric acid and/or sulfuric acid, and the concentration and the addition amount of the hydrochloric acid or the sulfuric acid are not particularly limited as long as the pH value of the electrolyte solution is 2-5 or 8-9.
The preparation method of the electrolyte solution is not particularly limited, as long as the water-soluble copper salt, the surfactant, the ether organic substance and the diamond particles can be uniformly mixed.
In the present invention, when the pure copper matrix is immersed in the electrolyte solution, the pure copper matrix is preferably fixed to the template and immersed; the material of the template is preferably red copper; the shape of the template is not particularly limited, as long as the pure copper matrix can not move in the deposition process. The pure copper substrate is not particularly limited in the present invention as long as diamond particles can be deposited on the pure copper substrate, and in the present embodiment, the pure copper substrate is preferably horizontally disposed.
In the invention, the mass content of phosphorus in the phosphorus-containing copper sheet is preferably 1-8%, and more preferably 1%; the phosphorus-containing copper sheet is preferably a phosphorus bronze sheet.
In the present invention, the parameters of the electrodeposition preferably include: the current density is preferably 0.5 to 14A/dm2More preferably 0.5 to 7A/dm2(ii) a The time is preferably 0.5 to 10 hours, and more preferably 0.5 to 5 hours; the temperature is preferably 20-50 ℃; the temperature of the electrodeposition is preferably achieved by controlling the temperature of the electrolyte solution; the temperature of the electrolyte solution is preferably achieved by adding a heating rod to the electrolyte solution. In thatIn the present invention, the electrodeposition is preferably carried out under stirring, the stirring is preferably carried out by means of a stream of air introduced by a mechanical pump, the stream of air is preferably a stream of air, and the flow rate of the stream of air is preferably 2.5L/min.
The preparation method of the diamond/copper composite material provided by the invention has mild operation conditions, and can well combine diamond particles and copper on a copper matrix.
The invention also provides the diamond/copper composite material obtained by the preparation method in the technical scheme, wherein the diamond/copper composite material comprises a copper matrix and a diamond/copper composite material layer loaded on the copper matrix; the mass content of diamond in the diamond/copper composite material layer is 10-60%.
The diamond/copper composite material provided by the invention has good heat-conducting property and high diamond content.
The diamond/copper composite material and the method for manufacturing the same according to the present invention will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
In the embodiment, a circular diamond/copper composite material is prepared, namely, the shape of a pure copper matrix is circular, and the diameter of the pure copper matrix is 30 mm; the mass percentage of diamond in the round diamond/copper composite material is 12.7 percent, and the specific preparation method comprises the following steps:
(1) preparing CuSO4·5H2O content of 200g/L, CuCl2·2H21.6g/L of O, 0.02g/L of gelatin, 0.01g/L of thiourea, 0.01g/L of sodium dodecyl sulfate, 0.008g/L of polyethylene glycol and 1.5g/L of diamond particles (with the particle size of 48 mu m), and adjusting the pH value of the solution to 2 by using HCl;
(2) sequentially polishing the raw material of the round pure copper substrate by using 200-mesh abrasive paper, 500-mesh abrasive paper, 1000-mesh abrasive paper and 2000-mesh abrasive paper until the surface is smooth and flat, cleaning by using ultrasonic waves, washing by using ethanol and deionized water, soaking and activating for 1h by using hydrochloric acid (the mass concentration is 10%), washing by using the deionized water, fixing the round pure copper substrate on a template, and connecting a silver wire; putting the whole template (wherein, the round pure copper matrix is horizontally placed) into an electrolyte solution for soaking for 2 h;
(3) taking a pure copper matrix deposited with diamond particles as a cathode and taking a phosphorus bronze sheet with the phosphorus element mass content of 1% as an anode; the temperature of the electrolyte solution is controlled to be 25-30 ℃ by the heating rod, air flow with the flow rate of 2.5L/min is pumped by the mechanical pump, and the current density of the direct current power supply is adjusted to be 7A/dm2And maintaining the stable current for electrodeposition for 0.5h to obtain the diamond/copper composite material.
The thermal conductivity of the composite material is 415W/mK through testing.
The mass percent of diamond was measured to be 12.7% by dissolving away the copper in the diamond/copper composite.
Fig. 1 is an SEM image of the diamond/copper composite obtained in this example, and it can be seen from fig. 1 that diamond can be embedded in the deposited copper after a short electrodeposition.
FIG. 2 is an EDS chart of the diamond/copper composite material obtained in the present example, FIG. 3 is a composition analysis chart of point 1 in FIG. 2, FIG. 4 is a composition analysis chart of point 2 in FIG. 2, and FIG. 5 is a composition analysis chart of point 3 in FIG. 2; as can be seen from fig. 2 to 5: the deposited copper is in close contact with the diamond particles, and the deposited copper can fully wrap the diamond.
Example 2
In the embodiment, a circular diamond/copper composite material is prepared, namely a pure copper matrix is circular and has the diameter of 30 mm; the mass percentage of diamond in the circular diamond/copper composite material is 42.3%, and the specific preparation method comprises the following steps:
(1) preparing CuSO4·5H2O content of 200g/L, CuCl2·2H21.6g/L of O, 0.02g/L of gelatin, 0.01g/L of thiourea, 0.01g/L of sodium dodecyl sulfate, 0.008g/L of polyethylene glycol and 1.5g/L of diamond particles (with the particle size of 48 mu m), and adjusting the pH value of the solution to 2 by using HCl;
(2) sequentially polishing the raw material of the round pure copper substrate by using 200-mesh abrasive paper, 500-mesh abrasive paper, 1000-mesh abrasive paper and 2000-mesh abrasive paper until the surface is smooth and flat, cleaning by using ultrasonic waves, washing by using ethanol and deionized water, soaking and activating for 1h by using hydrochloric acid (the mass concentration is 10%), washing by using the deionized water, fixing the pure copper substrate above a template, and connecting a silver wire; putting the whole template (wherein, the round pure copper matrix is horizontally placed) into an electrolyte solution for soaking for 2 h;
(3) taking a pure copper matrix deposited with diamond particles as a cathode, taking a phosphorus bronze sheet with the phosphorus element mass content of 1% as an anode, controlling the temperature of an electrolyte solution to be 25-30 ℃ by a heating rod, pumping air flow with the flow speed of 2.5L/min by a mechanical pump, and enabling the current density of a direct current power supply to be 7A/dm2And maintaining the stable current for electrodeposition for 3 hours to obtain the diamond/copper composite material.
The thermal conductivity of the composite material is found to be 617W/mK through tests.
The mass percent of diamond in the diamond/copper composite was determined to be 42.3% by dissolving away the copper in the diamond/copper composite.
The resulting diamond/copper composite was observed by a metallographic apparatus, and FIG. 6 is a partially enlarged view of the diamond/copper composite obtained in this example, in which diamond particles were distributed in bright white dots and deposited copper was present in dark black portions. As can be seen from fig. 6: after the electrodeposition time reaches a certain time, the diamond particles are wrapped by copper.
Example 3
In the embodiment, a round diamond/copper composite material is prepared, namely, the shape of a pure copper matrix is round, and the diameter of the pure copper matrix is 30 mm; the diamond/copper composite material comprises 37.5% by mass of diamond, and the specific preparation method comprises the following steps:
(1) preparing CuSO4·5H2O content of 170g/L and CuCl2·2H21.6g/L of O, 0.02g/L of gelatin, 0.01g/L of thiourea, 0.01g/L of sodium dodecyl sulfate, 0.008g/L of polyethylene glycol and 1.5g/L of diamond particles (with the particle size of 48 mu m), and adjusting the pH value of the solution to 2 by using HCl;
(2) sequentially polishing the raw material of the round pure copper substrate by using 200-mesh abrasive paper, 500-mesh abrasive paper, 1000-mesh abrasive paper and 2000-mesh abrasive paper until the surface is smooth and flat, cleaning by using ultrasonic waves, then washing by using ethanol and deionized water, soaking and activating for 1h by using hydrochloric acid (the mass concentration is 10%), washing by using the deionized water, fixing the obtained round pure copper substrate above a template, and connecting a silver wire; putting the whole template (wherein, the round pure copper matrix is horizontally placed) into an electrolyte solution for soaking for 2 h;
(3) taking a pure copper matrix deposited with diamond particles as a cathode, taking a phosphorus bronze sheet with the phosphorus element mass content of 1% as an anode, controlling the temperature of an electrolyte solution to be 25-30 ℃ by a heating rod, pumping air flow with the flow speed of 2.5L/min by a mechanical pump, and enabling the current density of a direct current power supply to be 7A/dm2And maintaining the stable current for electrodeposition for 3 hours to obtain the diamond/copper composite material.
The thermal conductivity of the composite material is found to be 562W/mK through testing.
The mass percent of diamond in the diamond/copper composite was determined to be 37.5% by dissolving away the copper in the diamond/copper composite.
Example 4
In this example, a circular diamond/copper composite material is prepared, that is, a pure copper substrate is circular and has a diameter of 30mm, and the mass percentage of diamond in the circular diamond/copper composite material is 33.7%, and the specific preparation method is as follows:
(1) preparing CuSO4·5H2O content of 170g/L and CuCl2·2H21.6g/L of O, 0.02g/L of gelatin, 0.01g/L of sodium dodecyl sulfate, 0.02g/L of polyethylene glycol and 1.5g/L of diamond particles (with the particle size of 48 mu m), and adjusting the pH value of the solution to 2 by using HCl;
(2) sequentially polishing the raw material of the round pure copper substrate by using 200-mesh abrasive paper, 500-mesh abrasive paper, 1000-mesh abrasive paper and 2000-mesh abrasive paper until the surface is smooth and flat, cleaning by using ultrasonic waves, washing by using ethanol and deionized water, soaking and activating for 1h by using hydrochloric acid (the mass concentration is 10%), washing by using the deionized water, fixing the obtained pure copper substrate above a template, and connecting a silver wire; putting the whole template (wherein the round pure copper matrix is horizontally placed) into an electrolyte solution for soaking for 2 hours to obtain the pure copper matrix deposited with diamond particles;
(3) taking a pure copper matrix deposited with diamond particles as a cathode, taking a phosphorus bronze sheet with the phosphorus element mass content of 1% as an anode, controlling the temperature of an electrolyte solution to be 25-30 ℃ by a heating rod, pumping air flow with the flow rate of 2.5L/min by a mechanical pump, and adjusting the current density of a direct current power supply to be 7A/dm2And maintaining the stable current for electrodeposition for 3 hours to obtain the diamond/copper composite material.
The thermal conductivity of the composite material is found to be 521W/mK through testing.
The mass percent of diamond in the diamond/copper composite was determined to be 33.7% by dissolving away the copper in the diamond/copper composite.
Example 5
In this embodiment, a circular diamond/copper composite material is prepared, that is, a pure copper substrate is circular and has a diameter of 30mm, and the mass percentage of diamond in the circular diamond/copper composite material is 30.3%, and the specific preparation method is as follows:
(1) preparing CuSO4·5H2O content of 170g/L and CuCl2·2H21.6g/L of O, 0.02g/L of gelatin, 0.01g/L of sodium dodecyl sulfate, 0.02g/L of polyethylene glycol, 1.5g/L of electrolytic solution of diamond particles (which are purchased from Henan Huanghe Hei whirlwind Co., Ltd., the particle size of 48 mu m, the thickness of the WC layer is 50nm, and the mass of the WC layer is 27 percent of that of the diamond particles) coated with a WC layer, and the pH value of the solution is adjusted to 8.8 by HCl;
(2) sequentially polishing the raw material of the round pure copper substrate by using 200-mesh abrasive paper, 500-mesh abrasive paper, 1000-mesh abrasive paper and 2000-mesh abrasive paper until the surface is smooth and flat, cleaning by using ultrasonic waves, washing by using ethanol and deionized water, soaking and activating for 1h by using hydrochloric acid (the mass concentration is 10%), washing by using the deionized water, fixing the obtained pure copper substrate above a template, and connecting a silver wire; putting the whole template (wherein the round copper matrix is horizontally placed) into an electrolyte solution for soaking for 2 hours;
(3) the pure copper matrix deposited with diamond particles is taken as a cathode, a phosphor bronze sheet with the phosphor element mass content of 1% is taken as an anode, and a heating rod is used for controllingThe temperature of the electrolyte solution is 25-30 ℃, air flow with the flow rate of 2.5L/min is pumped by a mechanical pump, and the current density of the direct current power supply is adjusted to 7A/dm2Maintaining stable current for electrodeposition for 2.5h to obtain the diamond/copper composite material;
the thermal conductivity of the composite material is found to be 508W/mK through testing.
The mass percent of diamond in the diamond/copper composite was determined to be 30.3% by dissolving away the copper in the diamond/copper composite.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (2)

1. A preparation method of a diamond/copper composite material is characterized by comprising the following steps:
(1) preparing CuSO4·5H2O content of 200g/L, CuCl2·2H2The pH value of the electrolytic solution with the O content of 1.6g/L, the gelatin content of 0.02g/L, the thiourea content of 0.01g/L, the sodium dodecyl sulfate content of 0.01g/L, the concentration of polyethylene glycol of 0.008g/L and the diamond particles of 1.5g/L is adjusted to be 2 by HCl, and the particle size of the diamond particles is 48 mu m;
(2) sequentially polishing the raw material of the round pure copper substrate by using 200-mesh abrasive paper, 500-mesh abrasive paper, 1000-mesh abrasive paper and 2000-mesh abrasive paper until the surface is smooth and flat, cleaning by using ultrasonic waves, washing by using ethanol and deionized water, soaking and activating for 1h by using hydrochloric acid, washing by using the deionized water, fixing the pure copper substrate above a template, and connecting a silver wire; putting the whole template into an electrolyte solution for soaking for 2 hours; wherein, the round pure copper matrix is horizontally arranged; the mass concentration of the hydrochloric acid is 10%;
(3) the method comprises the steps of taking a pure copper matrix deposited with diamond particles as a cathode, taking a phosphorus bronze sheet with the phosphorus element mass content of 1% as an anode, controlling the temperature of an electrolyte solution to be 25-30 ℃ by a heating rod, and pumping the electrolyte solution at the flow rate of 2.5L/min by a mechanical pumpAir flow, the current density of the DC power supply is 7A/dm2And maintaining the stable current for electrodeposition for 3 hours to obtain the diamond/copper composite material.
2. The diamond/copper composite material obtained by the preparation method according to claim 1, which comprises a pure copper substrate and a diamond/copper composite material layer bonded to the pure copper substrate; the mass content of diamond in the diamond/copper composite material layer is 42.3%.
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