CN111607716B - Method for preparing diamond/copper composite material with high surface finish by combining ultrasonic electrodeposition - Google Patents

Method for preparing diamond/copper composite material with high surface finish by combining ultrasonic electrodeposition Download PDF

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CN111607716B
CN111607716B CN202010701009.0A CN202010701009A CN111607716B CN 111607716 B CN111607716 B CN 111607716B CN 202010701009 A CN202010701009 A CN 202010701009A CN 111607716 B CN111607716 B CN 111607716B
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diamond
copper composite
composite material
copper
cooling
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CN111607716A (en
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武高辉
芶华松
林秀
陈国钦
王平平
修子扬
杨文澍
张强
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Harbin Jinwei Technology 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C3/00—Selection of compositions for coating the surfaces of moulds, cores, or patterns
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D23/00—Casting processes not provided for in groups B22D1/00 - B22D21/00
    • B22D23/04—Casting by dipping
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D23/00—Casting processes not provided for in groups B22D1/00 - B22D21/00
    • B22D23/06—Melting-down metal, e.g. metal particles, in the mould
    • 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
    • C22C1/1036—Alloys containing non-metals starting from a melt
    • 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
    • C22C1/1036—Alloys containing non-metals starting from a melt
    • C22C1/1073—Infiltration or casting under mechanical pressure, e.g. squeeze casting
    • 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/20—Electroplating using ultrasonics, vibrations

Abstract

A method for preparing a diamond/copper composite material with high surface finish by combining ultrasonic electrodeposition relates to a method for preparing a diamond/copper composite material. The purpose is to solve the problem that the surface finish degree of the existing high-heat-conductivity diamond copper composite material is low. The method comprises the following steps: preparing a mould, coating a release agent and drying; depositing a priming layer on the inner surface of the die cavity, and plating a copper film; the metal film-coated single-crystal diamond particles are filled in a cavity and impregnated. The diamond/copper composite material finally obtained by the method has the advantages of obviously improved surface smoothness, simple preparation process, good repeatability, stable product and good batch consistency. The obtained product can be directly applied to heat sinks, radiating fins or shells of high-power microwave power amplifiers and large-scale integrated circuits. The invention is suitable for preparing the diamond/copper composite material with high surface smoothness.

Description

Method for preparing diamond/copper composite material with high surface finish by combining ultrasonic electrodeposition
Technical Field
The invention relates to a preparation method of a diamond/copper composite material.
Background
With the increasing requirements of high thermal conductivity metal matrix composite material on dimensional accuracy and matching accuracy, the development of a preparation technology of diamond copper composite material with high surface finish and high thermal conductivity is urgent. At present, the method for improving the surface finish degree of metal matrix composite materials such as diamond/copper composite materials and the like is mainly realized by surface grinding in the later period, impurities and cutting stress are easily introduced into the surface grinding, and the required labor intensity is high. The diamond is arranged on the surface of the diamond copper composite material, so that the diamond copper composite material is very hard, and the grinding difficulty and the cost are very high.
The surface roughness of the existing high-thermal-conductivity diamond copper composite material without surface processing treatment (preparation state) is 2-3.6 microns, and the requirement of the technical fields of laser communication, electronic packaging and the like on high smoothness of a heat dissipation material cannot be met. The surface finish of the composite material is improved by a method of multiple grinding, for example, the patent number is CN201611226063.4, and the name is ' a surface processing method suitable for diamond/copper composite material ', and the patent method has higher requirements on grinding technology and consumes manpower cost '.
Disclosure of Invention
The invention provides a method for preparing a diamond/copper composite material with high surface finish by combining ultrasonic electrodeposition, aiming at solving the problem of low surface finish of the existing high-thermal-conductivity diamond/copper composite material.
The method for preparing the diamond/copper composite material with high surface finish by combining ultrasonic electrodeposition comprises the following steps:
firstly, preparing a mould; the requirements of the die are as follows: the roughness of the inner surface of the cavity is less than 6.3 microns, the heat conductivity is more than 90W/mK, and the average thermal expansion coefficient in the temperature range of 25-100 ℃ is less than 6 multiplied by 10-6/K；
Secondly, coating a release agent on the inner surface of the die cavity and drying;
depositing a copper film with the thickness of 0.8-1 mu m on the inner surface of the die cavity by adopting a magnetron sputtering method to serve as a priming layer, and plating a copper film with the thickness of 1-3 mm and the surface roughness of less than 1.5 mu m on the surface of the priming layer by adopting an ultrasonic electrodeposition method;
fourthly, filling the single crystal diamond particles coated with the metal film into the cavity of the die obtained in the third step to obtain a prefabricated body;
placing the prefabricated body in a crucible, placing the blocky base alloy on the upper part of the prefabricated body in the crucible, and placing the crucible in an air pressure infiltration furnace;
preheating a mould to 800-1000 ℃ under a protective atmosphere, then heating the blocky matrix alloy to 1100-1300 ℃ and preserving heat for 1-2 hours, and then melting the blocky matrix alloy; maintaining the temperature of the mold at 800-1000 ℃, increasing the air pressure in the air pressure infiltration furnace to 0.5-8 MPa, and maintaining the pressure for 5-30 min;
and sixthly, maintaining pressure and cooling in a stepped manner, cleaning the BN particles on the surface after demolding, and grinding or polishing to obtain the diamond copper composite material with high surface finish.
The principle and the beneficial effects of the invention are as follows:
1. the invention improves the air pressure infiltration preparation method of the high-heat-conductivity diamond/copper composite material, provides a preparation method of the high-heat-conductivity diamond/copper composite material with high surface smoothness, and is suitable for preparing the high-volume-fraction metal matrix composite material. Solves the problem of poor surface finish of the metal matrix composite in the prior art. The invention has the advantages of simple preparation process, good repeatability, stable product and good batch consistency. The obtained product can be directly applied to heat sinks, radiating fins or shells of high-power microwave power amplifiers and large-scale integrated circuits, and is particularly suitable for preparing high-thermal-conductivity diamond copper composite heat sink parts with bulges or steps.
2. The diamond/copper composite material prepared by the method has the volume fraction of the reinforcement body of 60-80%, the thermal conductivity of 750-870W/(mK) and the thermal diffusion coefficient of 320-367 mm2And/s, the surface roughness of the composite material sample piece with the surface of 130mm multiplied by 130mm reaches 0.05-0.1 mu m, and the smoothness is improved.
3. According to the invention, the fine-grained copper layer with high surface finish is obtained on the inner surface of the die cavity by controlling the electrodeposition process, the temperature of the die in the step five is controlled to be 800-1000 ℃, and the melting point of copper is 1085 ℃, so that a copper film plated on the die by the electrodeposition method cannot flow down in the infiltration process, and the defect caused by too fast solidification of the infiltrated copper due to too low temperature is avoided; the copper film is plated on the inner surface of the die cavity of the die, so that the surface finish of the prepared diamond/copper composite material can be improved, and the surface finish of the finally obtained diamond/copper composite material is also obviously improved. After demoulding, only simple polishing is needed, so that the method has the advantages of high efficiency, time saving, labor saving and labor cost saving, and belongs to an in-situ preparation method of the metal-based composite material with high surface smoothness.
Drawings
FIG. 1 is a schematic view of a mold structure, in which 1 is a powder filling port, 2 is a cavity, 3 is a mold, and 4 is a copper-clad layer;
FIG. 2 is an Atomic Force Microscope (AFM) topography photograph of the surface of the diamond/copper composite material prepared in example 1;
fig. 3 is a surface afm profile photograph of a sample of the diamond/copper composite prepared in comparative example 1 after grinding.
The specific implementation mode is as follows:
the technical scheme of the invention is not limited to the specific embodiments listed below, and any reasonable combination of the specific embodiments is included.
The first embodiment is as follows: the method for preparing the diamond/copper composite material with high surface finish by combining ultrasonic electrodeposition is carried out according to the following steps:
firstly, preparing a mould; the requirements of the die are as follows: the roughness of the inner surface of the cavity is less than 6.3 microns, the heat conductivity is more than 90W/mK, and the average thermal expansion coefficient in the temperature range of 25-100 ℃ is less than 6 multiplied by 10-6K; the mold with higher heat conductivity is selected to be beneficial to temperature equalization;
secondly, coating a release agent on the inner surface of the die cavity and drying;
depositing a copper film with the thickness of 0.8-1 mu m on the inner surface of the die cavity by adopting a magnetron sputtering method to serve as a priming layer, and plating a copper film with the thickness of 1-3 mm and the surface roughness of less than 1.5 mu m on the surface of the priming layer by adopting an ultrasonic electrodeposition method;
fourthly, filling the single crystal diamond particles coated with the metal film into the cavity of the die obtained in the third step to obtain a prefabricated body;
placing the prefabricated body in a crucible, placing the blocky base alloy on the upper part of the prefabricated body in the crucible, and placing the crucible in an air pressure infiltration furnace;
preheating a mould to 800-1000 ℃ under a protective atmosphere, then heating the blocky matrix alloy to 1100-1300 ℃ and preserving heat for 1-2 hours, and then melting the blocky matrix alloy; maintaining the temperature of the mold at 800-1000 ℃, increasing the air pressure in the air pressure infiltration furnace to 0.5-8 MPa, and maintaining the pressure for 5-30 min;
and sixthly, maintaining pressure and cooling in a stepped manner, cleaning the BN particles on the surface after demolding, and grinding or polishing to obtain the diamond copper composite material with high surface finish.
1. The embodiment improves the air pressure infiltration preparation method of the high-heat-conductivity diamond/copper composite material, provides a preparation method of the high-heat-conductivity diamond/copper composite material with high surface smoothness, and is suitable for preparing the high-volume-fraction metal matrix composite material. Solves the problem of poor surface finish of the metal matrix composite in the prior art. The preparation method has the advantages of simple preparation process, good repeatability, stable product and good batch consistency. The obtained product can be directly applied to heat sinks, radiating fins or shells of high-power microwave power amplifiers and large-scale integrated circuits, and is particularly suitable for preparing high-thermal-conductivity diamond copper composite heat sink parts with bulges or steps.
2. The volume fraction of the reinforcement in the diamond/copper composite material prepared by the method of the embodiment is 60-80%, the thermal conductivity is 750-870W/(mK), and the thermal diffusion coefficient is 320-367 mm2And/s, the surface roughness of the composite material sample piece with the surface of 130mm multiplied by 130mm reaches 0.05-0.1 mu m, and the smoothness is improved.
3. According to the embodiment, the fine-grained copper layer with high surface finish is obtained on the inner surface of the die cavity by controlling the electrodeposition process, the temperature of the die in the step five is controlled to be 800-1000 ℃, and the melting point of copper is 1085 ℃, so that a copper film plated on the die by the electrodeposition method cannot flow down in the infiltration process, and the defect caused by too fast solidification of the infiltrated copper due to too low temperature cannot be generated; the copper film is plated on the inner surface of the die cavity of the die, so that the surface finish of the prepared diamond/copper composite material can be improved, and the surface finish of the finally obtained diamond/copper composite material is also obviously improved. After demoulding, only simple polishing is needed, so that the method has the advantages of high efficiency, time saving, labor saving and labor cost saving, and belongs to an in-situ preparation method of the metal-based composite material with high surface smoothness.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: step one, the release agent is alcohol dispersion liquid of BN particles; the concentration of BN particles in the alcohol was 0.05 g/mL.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: and fourthly, the size of the single crystal diamond particles is 100-400 mu m, and the metal film plated on the single crystal diamond particles is a Ti film or a W film.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: and fourthly, the volume of the single crystal diamond particles coated with the metal film is 60-80% of the die cavity.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: and fourthly, the thickness of the metal film is 50-200 nm.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: and fifthly, the matrix alloy is pure copper or copper alloy.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: and fifthly, the volume of the blocky base alloy is 20-30 times of that of the prefabricated body.
The specific implementation mode is eight: the present embodiment differs from one of the first to seventh embodiments in that: step six the pressure-maintaining stepped cooling process comprises the following steps: when the temperature in the furnace is higher than 300 ℃, cooling at the cooling speed of 4 ℃/min under 2-5 MPa; when the temperature in the furnace is 300-100 ℃, cooling at the speed of 2 ℃/min under the pressure of 2-5 MPa; when the temperature in the furnace reaches below 100 ℃, releasing the pressure and naturally cooling to the room temperature.
The specific implementation method nine: the present embodiment differs from the first to eighth embodiments in that: step six the pressure-maintaining stepped cooling process comprises the following steps: when the temperature in the furnace is higher than 300 ℃, cooling at the cooling speed of 4 ℃/min under 3 MPa; when the temperature in the furnace is 600 ℃, cooling at the speed of 2 ℃/min under the pressure of 3 MPa; when the temperature in the furnace reaches below 100 ℃, releasing the pressure and naturally cooling to the room temperature.
The detailed implementation mode is ten: the present embodiment differs from one of the first to ninth embodiments in that: step six the pressure-maintaining stepped cooling process comprises the following steps: when the temperature in the furnace is higher than 300 ℃, cooling at the cooling speed of 4 ℃/min under 5 MPa; when the temperature in the furnace is 300 ℃, cooling at the speed of 2 ℃/min under the pressure of 5 MPa; when the temperature in the furnace reaches below 100 ℃, releasing the pressure and naturally cooling to the room temperature.
Example 1:
the method for preparing the diamond/copper composite material with high surface finish by combining ultrasonic electrodeposition comprises the following steps:
firstly, preparing a mould; the requirements of the die are as follows: the roughness of the inner surface of the cavity is 6.2 microns, the heat conductivity is 95W/mK, and the average thermal expansion coefficient in the temperature range of 25-100 ℃ is 5.66 multiplied by 10-6K; the material of the mould is ceramic;
secondly, coating a release agent on the inner surface of the die cavity and drying; the release agent is an alcohol dispersion of BN particles; the concentration of BN particles in the alcohol is 0.05 g/mL; alcohol concentration 99.7 wt.%; after drying, the alcohol is volatilized, and the release agent particles are attached to the inner surface of the cavity of the mold.
Depositing a copper film with the thickness of 0.8 mu m on the inner surface of the die cavity by adopting a magnetron sputtering method to serve as a bottom layer, and plating a copper film with the thickness of 1mm and the surface roughness of less than 1.5 mu m on the surface of the bottom layer by adopting an ultrasonic electrodeposition method;
fourthly, filling the single crystal diamond particles coated with the metal film into the cavity of the die obtained in the third step to obtain a prefabricated body;
the size of the single crystal diamond particles is 100 mu m, the metal film plated by the single crystal diamond particles is a Ti film, and the thickness of the metal film is 50 nm; the volume of the single crystal diamond particles coated with the metal film is 60 percent of the volume of the die cavity;
placing the prefabricated body in a crucible, placing the blocky base alloy on the upper part of the prefabricated body in the crucible, and placing the crucible in an air pressure infiltration furnace; preheating the die to 800 ℃ under the protective atmosphere, then heating the blocky matrix alloy to 1100 ℃ and preserving heat for 2 hours, and at the moment, melting the blocky matrix alloy; maintaining the temperature of the mold at 800 ℃, increasing the air pressure in the air pressure infiltration furnace to 1MPa, and maintaining the pressure for 10 min; at this time, the molten massive matrix alloy is infiltrated downwards into the diamond particles in the prefabricated body; the temperature of the die is maintained at 800 ℃, the melting point of the copper film is not reached, and the copper film can be ensured to be complete and not to melt;
the matrix alloy is pure copper; the volume of the massive matrix alloy is 20 times of that of the prefabricated body;
sixthly, pressure maintaining stepped cooling, removing surface BN particles after demolding, and polishing to obtain the diamond copper composite material with high surface finish;
the pressure-maintaining stepped cooling process comprises the following steps: when the temperature in the furnace is higher than 300 ℃, cooling at the cooling speed of 4 ℃/min under 5 MPa; when the temperature in the furnace is below 300 ℃ and above 100 ℃, cooling at the speed of 2 ℃/min under 4 MPa; when the temperature in the furnace reaches below 100 ℃, releasing the pressure and naturally cooling to the room temperature.
After the surface BN particles of the obtained component are cleaned, the component is directly exposed to a copper layer which is 1mm thick and does not contain diamond particles, and the component is easy to grind or polish. The diamond/copper composite material prepared by the prior art contains diamond on the surface, has high hardness and very high grinding or polishing difficulty.
FIG. 1 is a schematic view of a mold structure, in which 1 is a powder filling port, 2 is a cavity, 3 is a mold, and 4 is a copper-clad layer;
FIG. 2 is an Atomic Force Microscope (AFM) topography photograph of the surface of the diamond/copper composite material prepared in example 1; as can be seen in the figure, the highest part of the surface of the material within the range of 10 μm is 103.7nm, the lowest part is-81.2 nm, and the surface roughness is less than 200 nm;
the diamond/copper composite material prepared by the method has the volume fraction of the reinforcement body of 65 percent, the thermal conductivity of 750W/(mK) and the thermal diffusion coefficient of 320mm2The surface roughness Ra value of the composite material sample piece with the surface of 130mm multiplied by 130mm reaches 0.057 mu m (measured by a surface roughness meter), and the smoothness is improved.
Comparative example 1:
the method for preparing the diamond/copper composite material with high surface finish according to the comparative example comprises the following steps:
firstly, preparing a mould; the requirements of the die are as follows: the roughness of the inner surface of the cavity is 6.2 microns, the heat conductivity is 95W/mK, and the average thermal expansion coefficient in the temperature range of 25-100 ℃ is 5.66 multiplied by 10-6K; the material of the mould is ceramic;
secondly, coating a release agent on the inner surface of the die cavity and drying; the release agent is an alcohol dispersion of BN particles; the concentration of BN particles in the alcohol is 0.05 g/mL; alcohol concentration 99.7 wt.%; after drying, the alcohol is volatilized, and the release agent particles are attached to the inner surface of the cavity of the mold.
Filling the single crystal diamond particles coated with the metal film into the cavity of the die obtained in the step three to obtain a prefabricated body;
the size of the single crystal diamond particles is 100 mu m, the metal film plated by the single crystal diamond particles is a Ti film, and the thickness of the metal film is 50 nm; the volume of the single crystal diamond particles coated with the metal film is 60 percent of the volume of the die cavity;
fourthly, placing the prefabricated body in a crucible, placing the blocky base alloy on the upper part of the prefabricated body in the crucible, and placing the crucible in an air pressure infiltration furnace; preheating the die to 800 ℃ under the protective atmosphere, then heating the blocky matrix alloy to 1100 ℃ and preserving heat for 2 hours, and at the moment, melting the blocky matrix alloy;
the matrix alloy is pure copper; the volume of the massive matrix alloy is 20 times of that of the prefabricated body;
fifthly, pressure maintaining stepped cooling, and cleaning surface BN particles after demolding;
the pressure-maintaining stepped cooling process comprises the following steps: when the temperature in the furnace is higher than 300 ℃, cooling at the cooling speed of 4 ℃/min under 5 MPa; when the temperature in the furnace is below 300 ℃ and above 100 ℃, cooling at the speed of 2 ℃/min under 4 MPa; when the temperature in the furnace reaches below 100 ℃, releasing the pressure and naturally cooling to the room temperature.
The obtained member was polished to have a surface roughness Ra of 1.115 μm after cleaning the surface BN particles.
FIG. 3 is a surface AFM topography photograph of a diamond/copper composite sample prepared in comparative example 1 after grinding; it can be seen that the material surface in the 10 μm range is 536.3nm at the highest and-556.2 nm at the lowest, with a surface roughness greater than 1 μm.
Example 2:
the method for preparing the diamond/copper composite material with high surface finish by combining ultrasonic electrodeposition comprises the following steps:
firstly, preparing a mould; the requirements of the die are as follows: the roughness of the inner surface of the cavity is 6.0 microns, the heat conductivity is 100W/mK, and the average thermal expansion coefficient in the temperature range of 25-100 ℃ is 3.60 multiplied by 10-6K; the material of the mould is ceramic;
secondly, coating a release agent on the inner surface of the die cavity and drying; the release agent is an alcohol dispersion of BN particles; the concentration of BN particles in the alcohol is 0.05 g/mL; alcohol concentration 99.7 wt.%; after drying, the alcohol is volatilized, and the release agent particles are attached to the inner surface of the cavity of the mold.
Depositing a copper film with the thickness of 1 mu m on the inner surface of the die cavity by adopting a magnetron sputtering method to serve as a priming layer, and plating a copper film with the thickness of 3mm and the surface roughness of less than 1.5 mu m on the surface of the priming layer by adopting an ultrasonic electrodeposition method;
fourthly, filling the single crystal diamond particles coated with the metal film into the cavity of the die obtained in the third step to obtain a prefabricated body;
the size of the single crystal diamond particles is 400 mu m, the metal film plated by the single crystal diamond particles is a W film, and the thickness of the metal film is 200 nm; the volume of the single crystal diamond particles coated with the metal film is 65 percent of the die cavity;
placing the prefabricated body in a crucible, placing the blocky base alloy on the upper part of the prefabricated body in the crucible, and placing the crucible in an air pressure infiltration furnace; preheating the die to 1000 ℃ under the protective atmosphere, then heating the blocky matrix alloy to 1300 ℃ and preserving heat for 1h, and melting the blocky matrix alloy; maintaining the temperature of the mold at 1000 ℃, increasing the air pressure in the air pressure infiltration furnace to 8MPa, and maintaining the pressure for 30 min; at this time, the molten massive matrix alloy is infiltrated downwards into the diamond particles in the prefabricated body; the temperature of the die is maintained at 1000 ℃, the melting point of the copper film is not reached, and the copper film can be ensured to be complete and not to be melted;
the base alloy is a copper chromium alloy containing 2.0 wt.% chromium; the volume of the massive matrix alloy is 30 times of that of the prefabricated body;
sixthly, pressure maintaining stepped cooling, removing surface BN particles after demolding, and polishing to obtain the diamond copper composite material with high surface finish;
the pressure-maintaining stepped cooling process comprises the following steps: when the temperature in the furnace is higher than 300 ℃, cooling at the cooling speed of 4 ℃/min under 4 MPa; when the temperature in the furnace is 300-100 ℃, cooling at the speed of 2 ℃/min under 3 MPa; when the temperature in the furnace reaches below 100 ℃, releasing the pressure and naturally cooling to the room temperature.
After the surface BN particles of the obtained component are cleaned, the component is directly exposed to a copper layer which is 3mm thick and does not contain diamond particles, and the component is easy to grind or polish. The diamond/copper composite material prepared by the prior art contains diamond on the surface, has high hardness and very high grinding or polishing difficulty.
Example 3:
the method for preparing the diamond/copper composite material with high surface finish by combining ultrasonic electrodeposition comprises the following steps:
firstly, preparing a mould; the requirements of the die are as follows: the roughness of the inner surface of the cavity is 5.5 microns, the thermal conductivity is 105W/mK, and the average thermal expansion coefficient in the temperature range of 25-100 ℃ is 4.55 multiplied by 10-6K; the mould is made of graphite;
secondly, coating a release agent on the inner surface of the die cavity and drying; the release agent is an alcohol dispersion of BN particles; the concentration of BN particles in the alcohol is 0.05 g/mL; alcohol concentration 99.7 wt.%; after drying, the alcohol is volatilized, and the release agent particles are attached to the inner surface of the cavity of the mold.
Depositing a copper film with the thickness of 1 mu m on the inner surface of the die cavity by adopting a magnetron sputtering method to serve as a priming layer, and plating a copper film with the thickness of 1mm and the surface roughness of less than 1.5 mu m on the surface of the priming layer by adopting an ultrasonic electrodeposition method;
fourthly, filling the single crystal diamond particles coated with the metal film into the cavity of the die obtained in the third step to obtain a prefabricated body;
the size of the single crystal diamond particles is 100 mu m, the metal film plated by the single crystal diamond particles is a Ti film, and the thickness of the metal film is 50 nm; the volume of the single crystal diamond particles coated with the metal film is 70% of the die cavity;
placing the prefabricated body in a crucible, placing the blocky base alloy on the upper part of the prefabricated body in the crucible, and placing the crucible in an air pressure infiltration furnace; preheating the die to 800 ℃ under the protective atmosphere, then heating the blocky matrix alloy to 1100 ℃ and preserving heat for 2 hours, and at the moment, melting the blocky matrix alloy; maintaining the temperature of the mold at 800-1000 ℃, raising the air pressure in the air pressure infiltration furnace to 3MPa, and maintaining the pressure for 28 min; at this time, the molten massive matrix alloy is infiltrated downwards into the diamond particles in the prefabricated body; the temperature of the die is maintained at 800 ℃, the melting point of the copper film is not reached, and the copper film can be ensured to be complete and not to melt;
the matrix alloy is pure copper; the volume of the massive matrix alloy is 20 times of that of the prefabricated body;
sixthly, pressure maintaining stepped cooling, removing surface BN particles after demolding, and grinding or polishing to obtain the diamond copper composite material with high surface finish;
the pressure-maintaining stepped cooling process comprises the following steps: when the temperature in the furnace is higher than 300 ℃, cooling at the cooling speed of 4 ℃/min under 3 MPa; when the temperature in the furnace is more than 100 ℃ below 300, cooling at the speed of 2 ℃/min under 2 MPa; when the temperature in the furnace reaches below 100 ℃, releasing the pressure and naturally cooling to the room temperature.
After the surface BN particles of the obtained component are cleaned, the component is directly exposed to a copper layer which is 1mm thick and does not contain diamond particles, and the component is easy to grind or polish. The diamond/copper composite material prepared by the prior art contains diamond on the surface, has high hardness and very high grinding or polishing difficulty.

Claims (8)

1. A method for preparing a diamond/copper composite material with high surface finish by combining ultrasonic electrodeposition is characterized by comprising the following steps: the method comprises the following steps:
firstly, preparing a mould; the requirements of the die are as follows: the roughness of the cavity inner surface is less than 6.3 microns, the thermal conductivity is greater than 90W/mK, and the mean thermal expansion coefficient in the temperature range 25-100℃ is less than 6 x 10-6/K；
Secondly, coating a release agent on the inner surface of the die cavity and drying;
depositing a copper film with the thickness of 0.8-1 mu m on the inner surface of the die cavity by adopting a magnetron sputtering method to serve as a priming layer, and plating a copper film with the thickness of 1-3 mm and the surface roughness of less than 1.5 mu m on the surface of the priming layer by adopting an ultrasonic electrodeposition method;
fourthly, filling the single crystal diamond particles coated with the metal film into the cavity of the die obtained in the third step to obtain a prefabricated body;
placing the prefabricated body in a crucible, placing the blocky base alloy on the upper part of the prefabricated body in the crucible, and placing the crucible in an air pressure infiltration furnace;
preheating a mould to 800-1000 ℃ under a protective atmosphere, then heating the blocky matrix alloy to 1100-1300 ℃ and preserving heat for 1-2 hours, and then melting the blocky matrix alloy; maintaining the temperature of the mold at 800-1000 ℃, increasing the air pressure in the air pressure infiltration furnace to 0.5-8 MPa, and maintaining the pressure for 5-30 min;
sixthly, pressure maintaining stepped cooling, removing surface BN particles after demolding, and grinding or polishing to obtain the diamond copper composite material with high surface finish;
step six the pressure-maintaining stepped cooling process comprises the following steps: when the temperature in the furnace is higher than 300 ℃, cooling at the cooling speed of 4 ℃/min under 2-5 MPa; when the temperature in the furnace is 300-100 ℃, cooling at the speed of 2 ℃/min under the pressure of 2-5 MPa; when the temperature in the furnace reaches below 100 ℃, releasing the pressure and naturally cooling to the room temperature.
2. The method of producing a high surface finish diamond/copper composite in combination with ultrasonic electrodeposition as claimed in claim 1 wherein: step one, the release agent is alcohol dispersion liquid of BN particles; the concentration of BN particles in the alcohol was 0.05 g/mL.
3. The method of producing a high surface finish diamond/copper composite in combination with ultrasonic electrodeposition as claimed in claim 1 wherein: and fourthly, the size of the single crystal diamond particles is 100-400 mu m, and the metal film plated on the single crystal diamond particles is a Ti film or a W film.
4. The method of producing a high surface finish diamond/copper composite in combination with ultrasonic electrodeposition as claimed in claim 1 wherein: and fourthly, the volume of the single crystal diamond particles coated with the metal film is 60-80% of the die cavity.
5. The method of producing a high surface finish diamond/copper composite in combination with ultrasonic electrodeposition as claimed in claim 1 wherein: and fourthly, the thickness of the metal film is 50-200 nm.
6. The method of producing a high surface finish diamond/copper composite in combination with ultrasonic electrodeposition as claimed in claim 1 wherein: and fifthly, the matrix alloy is pure copper or copper alloy.
7. The method of producing a high surface finish diamond/copper composite material in combination with ultrasonic electrodeposition as claimed in claim 1 wherein: and fifthly, the volume of the blocky base alloy is 20-30 times of that of the prefabricated body.
8. The method of producing a high surface finish diamond/copper composite in combination with ultrasonic electrodeposition as claimed in claim 1 wherein: step six the pressure-maintaining stepped cooling process comprises the following steps: when the temperature in the furnace is higher than 300 ℃, cooling at the cooling speed of 4 ℃/min under 5 MPa; when the temperature in the furnace is 300 ℃, cooling at the speed of 2 ℃/min under the pressure of 5 MPa; when the temperature in the furnace reaches below 100 ℃, releasing the pressure and naturally cooling to the room temperature.
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