CN119776819A - A method for coating insulating ceramic coating on the surface of copper/diamond composite material - Google Patents
A method for coating insulating ceramic coating on the surface of copper/diamond composite material Download PDFInfo
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Abstract
The invention provides a method for plating an insulating ceramic coating on the surface of a copper/diamond composite material, and relates to the technical field of composite material surface insulating treatment. The method comprises the steps of surface pretreatment, surface sand blasting, surface insulation ceramic coating, wherein the surface pretreatment is carried out on the surface of a substrate made of a copper/diamond composite material with high heat conductivity to obtain a substrate with a clean surface, the surface sand blasting is carried out on the substrate with the clean surface to obtain a substrate with a rough surface, and the insulation ceramic coating is plated, wherein the ceramic powder after ball milling is deposited on the substrate with the rough surface through an aerosol nozzle by an aerosol deposition device to obtain the substrate with the insulation ceramic coating. The method prepares the copper/diamond composite material with the insulating coating, which has the advantages of uniform component distribution, uniform performance, and synergistic improvement of thermal conductivity and resistivity, through surface pretreatment, surface sand blasting treatment and insulating ceramic coating plating, is simple and easy to operate, has low cost, short flow and high efficiency, and is beneficial to industrial mass production and popularization.
Description
Technical Field
The invention relates to the technical field of insulating treatment of composite material surfaces, in particular to a method for plating an insulating ceramic coating on a copper/diamond composite material surface.
Background
The information technology industry is strategic, basic and pilot industry related to national economy and safety and development, and the electronic components are basic stones supporting the development of the information technology industry. With the continuous development of the 5G and new energy automobile fields, the power and voltage of circuit components are continuously increased, and the circuit component substrate is required to have the performances of high heat conduction, high voltage resistance, high temperature resistance, corrosion resistance and the like. And the metal copper and the diamond have high heat conductivity, and the heat conductivity of the copper/diamond composite material prepared by compounding the metal copper and the diamond is several times that of the traditional Cu-W alloy, al-Si and Al/SiC composite material. The thermal expansion coefficient of the copper/diamond composite material is more adaptive to that of the semiconductor material, so that the thermal stress generated in the service process can be reduced. However, the application of copper/diamond composite materials in the field of practical packaging also faces some of the problems to be solved.
For example, the addition of insulating diamond particles, while reducing the electrical conductivity of the copper/diamond composite to some extent, is conductive in nature, since the conductive copper matrix is a continuous phase. The conductive properties of copper/diamond composites limit their use in high voltage electronic components.
Although the composite material can be insulated by coating the surface of the copper/diamond composite material with a polymer material, the thermal conductivity of the polymer is generally lower than 1W/mK, the polymer has poor temperature resistance, and the polymer is easy to fail and flow at high temperature, so that the electronic components are damaged. Although the ceramic coating can be prepared by the traditional sintering or vapor deposition method to insulate the composite material, the preparation temperature is close to or higher than the melting point of copper, the interface microstructure of the copper/diamond composite material can be damaged, the thermophysical property of the composite material is reduced, and the rate of depositing the ceramic coating by the methods such as magnetron sputtering is only 1-3 mu m/h, which is not suitable for preparing the micron-sized coating. Therefore, there is a need to develop an efficient method of insulating copper/diamond composites at room temperature.
Chinese patent CN113073294a discloses a heat conductive insulating coating fully plated on the surface of a high heat conductive integrated circuit package substrate and a preparation method thereof, in which the insulating AlN coating or SiC coating is plated on the surface of a substrate in all directions without dead angles by utilizing multi-arc ion vapor deposition plating, the preparation process is obviously complex, the operation difficulty is high, the resistivity of the prepared coating is low, and the heat conductive performance and the resistance performance cannot be effectively and synergistically improved.
Chinese patent CN101202331a discloses a method for preparing an insulating film material for a battery, which comprises plating the insulating film material by a sputtering method, however, the target material selected for the film prepared by the method needs to be nitrided or oxidized in the sputtering process, so that the distance between the target and the substrate needs to be controlled greatly in the sputtering process, the sputtering time needs 100 minutes at maximum, and the composition distribution of the obtained film material is not uniform.
Chinese patent CN117637262a discloses a method for preparing an insulating layer and a metal substrate having an insulating layer, in which holes are formed on the surface of a metal substrate by etching the metal substrate, first insulating particles are laid, the first insulating particles are melted by heat treatment and filled in gaps between the holes and the first insulating particles, and the insulating layer is solidified, wherein the insulating layer is composed of fluoropolymer particles, and the insulating layer is poor in temperature resistance although the insulating property can be improved.
Disclosure of Invention
The invention provides a method for plating an insulating ceramic coating on the surface of a copper/diamond composite material, which aims to solve the technical problems that in the prior art, the surface insulativity and the heat conductivity of the copper/diamond composite material cannot be cooperatively improved, the component selection of a prepared insulating layer can only consider the insulativity and the heat conductivity, or the preparation process is complex, the operation difficulty is high, the process is long, the thermophysical property of the composite material can be damaged in the preparation process, the industrial production is not facilitated, and the like. The technical scheme is as follows:
a method for plating an insulating ceramic coating on the surface of a copper/diamond composite material, which comprises the following steps:
S1, surface pretreatment, namely pretreating the surface of a substrate of a high-heat-conductivity copper/diamond composite material to obtain a substrate with a clean surface;
S2, performing surface sand blasting treatment, namely performing ceramic particle sand blasting treatment on the substrate with the clean S1 surface to obtain a substrate with a rough surface;
and S3, plating an insulating ceramic coating, namely depositing ceramic powder subjected to ball milling treatment on the substrate with the rough surface S2 through an aerosol nozzle by an aerosol deposition device to obtain the substrate with the insulating ceramic coating.
Optionally, the diamond volume fraction of the copper/diamond composite material with high thermal conductivity in S1 is 30-70%, the thermal conductivity is 600-900W/mK, and the pretreatment comprises surface sand paper polishing, surface cleaning and vacuum drying.
Optionally, the surface abrasive paper in S1 is polished to the surface of the copper/diamond composite substrate by 200-mesh abrasive paper, 400-mesh abrasive paper, 600-mesh abrasive paper and 1000-mesh abrasive paper respectively, the surface cleaning is ultrasonic cleaning in acetone solution for 5-30min, and the vacuum drying is carried out in a vacuum drying oven.
Optionally, the ceramic particles used in the sand blasting treatment in S2 are alumina particles of 100-200 μm, the spraying distance is 150-250mm, the spraying angle is 70-90 degrees, and the spraying time is 1-5min.
Alternatively, the surface roughness Ra of the surface roughened substrate in S2 is 5-10 μm.
Optionally, the aerosol deposition device in S3 includes an aerosol powder bin, an aerosol deposition bin, a sample rack for placing a substrate, and an aerosol nozzle, wherein the aerosol powder bin is filled with ceramic powder after ball milling treatment, the sample rack moves along x and y directions, the aerosol nozzle uses high-purity nitrogen or argon as a powder feeding gas, and the flow rate of the argon or nitrogen is 1-10L/min.
Optionally, the ceramic powder in S3 is any one of alumina, aluminum nitride and silicon nitride, the grain diameter is 0.1-4 mu m, the ceramic powder is filled into a ball mill for ball milling, the ball milling time is 1-6h, and the ball milling speed is 50-200rmp, so as to obtain the ceramic powder with uniform ball milling.
Optionally, the copper/diamond composite substrate in S3 is 5-15mm from the aerosol nozzle.
Alternatively, the deposition in S3 is to deposit a ceramic coating on the surface of a substrate with rough surface at 20-50 ℃, the moving speed of the nozzle is 0.5-5 mm/S, and the deposition time is 0.5-10min.
Optionally, the substrate thermal conductivity of the insulating ceramic coating in S3 is 600-900W/mK, which is reduced by 0.5-3% compared with that of the unplated composite material, the average thickness of the insulating ceramic coating is 0.5-20 mu m, the compactness is 95-99%, the resistivity is higher than 10 13 Ω & cm, the dielectric constant under the current frequency of 2MHz is 8-9, and the surface roughness is lower than that of the unplated copper/diamond composite material and is 2-4 mu m.
Compared with the prior art, the technical scheme has at least the following beneficial effects:
According to the scheme, the method for plating the insulating ceramic coating on the surface of the copper/diamond composite material can solve the technical problems that in the prior art, the surface insulativity and the heat conductivity of the copper/diamond composite material cannot be cooperatively improved, the component selection of the prepared insulating layer only can consider one aspect of the insulativity and the heat conductivity, or the preparation process is complex, the operation difficulty is high, the flow is long, the thermal physical property of the composite material can be damaged in the preparation process, the industrial production is not facilitated, and the like.
According to the invention, the surface of the copper/diamond composite material substrate is polished by using 200-mesh, 400-mesh, 600-mesh and 1000-mesh sand paper respectively, oxide and pollutants on the surface of the composite material are removed, and then the surface is cleaned by using an ultrasonic organic solvent, so that the doping impurities of the coating in the subsequent preparation and the influence on the component uniformity of the coating are avoided.
The ball milling treatment of submicron ceramic powder ensures that the ball milled powder has uniform granularity and good fluidity, and the invention has the functions of uniformly distributing coating components and improving the adhesive force, resistivity and thermal conductivity of the coating and a substrate in the preparation of the ceramic coating.
The invention adjusts the distance between the copper/diamond composite material substrate and the aerosol nozzle by controlling the movement of the sample frame along the x and y directions, controls the flow rate of the carrier gas for powder feeding, combines the movement range, the movement speed and the deposition time of the nozzle, and finally precisely controls the deposition range and the thickness of the ceramic coating.
The invention tests the thermal conductivity of the copper/diamond composite material by using a laser flash method, and discovers that the thermal conductivity of the copper/diamond composite material is only reduced by 3 percent after a layer of aluminum oxide coating with the thickness of 9 mu m is deposited. Because the particle size of the alumina powder used for aerosol deposition is small and the powder speed is high, the compactness (95-99%) of the alumina coating and the interfacial binding force of the alumina coating and the copper/diamond composite material are effectively increased. And when the scanning electron microscope is used for observation, defects such as pores and the like are not observed at the interface between the coating and the composite material.
The thermal conductivity of the substrate of the insulating ceramic coating prepared by the invention is 600-900W/mK, which is reduced by 0.5-3% compared with that of the unplated composite material, the average thickness of the insulating ceramic coating is 0.5-20 mu m, the density is 95-99%, the resistivity is higher than 10 13 Ω & cm, the dielectric constant under the current frequency of 2MHz is 8-9, and the surface roughness is lower than that of the unplated copper/diamond composite material and is 2-4 mu m.
In a word, compared with other traditional methods, the method for preparing the copper/diamond composite material with the insulating coating by surface pretreatment, surface sand blasting and insulating ceramic coating plating has the advantages of uniform component distribution, uniform performance, synergistic improvement of thermal conductivity and resistivity, simplicity, easiness in operation, environment friendliness, low cost, short flow and high efficiency, and is beneficial to industrial mass production and popularization.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a cross-sectional scanning electron microscope image of a substrate with an insulating ceramic coating layer prepared by a method for plating an insulating ceramic coating layer on a copper/diamond composite material surface according to example 1 of the present invention;
FIG. 2 is a surface scanning electron microscope image of a substrate with an insulating ceramic coating prepared by the method of plating an insulating ceramic coating on the surface of a copper/diamond composite material according to example 1 of the present invention;
fig. 3 is a surface scanning electron microscope image of a copper/diamond composite material before plating in example 1 of the present invention.
Detailed Description
The technical scheme of the invention is described below with reference to the accompanying drawings.
In embodiments of the invention, words such as "exemplary," "such as" and the like are used to mean serving as an example, instance, or illustration. Any embodiment or design described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments or designs. Rather, the term use of an example is intended to present concepts in a concrete fashion. Furthermore, in embodiments of the present invention, the meaning of "and/or" may be that of both, or may be that of either, optionally one of both.
In the embodiments of the present invention, "image" and "picture" may be sometimes used in combination, and it should be noted that the meaning of the expression is consistent when the distinction is not emphasized.
In embodiments of the present invention, sometimes a subscript such as W 1 may be written in a non-subscript form such as W1, and the meaning of the expression is consistent when de-emphasizing the distinction.
In order to make the technical problems, technical solutions and advantages to be solved more apparent, the following detailed description will be given with reference to the accompanying drawings and specific embodiments.
A method for plating an insulating ceramic coating on the surface of a copper/diamond composite material, which comprises the following steps:
S1, surface pretreatment, namely pretreating the surface of a substrate of a high-heat-conductivity copper/diamond composite material to obtain a substrate with a clean surface;
S2, performing surface sand blasting treatment, namely performing ceramic particle sand blasting treatment on the substrate with the clean S1 surface to obtain a substrate with a rough surface;
and S3, plating an insulating ceramic coating, namely depositing ceramic powder subjected to ball milling treatment on the substrate with the rough surface S2 through an aerosol nozzle by an aerosol deposition device to obtain the substrate with the insulating ceramic coating.
In particular, the diamond volume fraction of the copper/diamond composite material with high thermal conductivity in S1 is 30-70%, the thermal conductivity is 600-900W/mK, and the pretreatment comprises surface sand paper polishing, surface cleaning and vacuum drying.
Specifically, the surface abrasive paper in S1 is polished to the surface of the copper/diamond composite substrate by 200 mesh abrasive paper, 400 mesh abrasive paper, 600 mesh abrasive paper and 1000 mesh abrasive paper respectively, the surface cleaning is ultrasonic cleaning in acetone solution for 5-30min, and the vacuum drying is carried out in a vacuum drying oven.
In particular, the ceramic particles used in the sand blasting treatment in S2 are alumina particles of 100-200 mu m, the spraying distance is 150-250mm, the spraying angle is 70-90 degrees, and the spraying time is 1-5min.
In particular, the surface roughness Ra of the surface roughened substrate in S2 is 5-10 μm.
Particularly, the aerosol deposition device in the S3 comprises an aerosol powder bin, a sample rack and an aerosol nozzle, wherein the sample rack is used for placing a substrate, ceramic powder after ball milling treatment is filled in the aerosol powder bin, the sample rack moves along the x and y directions, high-purity nitrogen or argon is selected as powder feeding gas for the aerosol nozzle, and the flow rate of the argon or the nitrogen is 1-10L/min.
Specifically, the ceramic powder in S3 is any one of alumina, aluminum nitride and silicon nitride, the grain diameter is 0.1-4 mu m, the ceramic powder is filled into a ball mill for ball milling, the ball milling time is 1-6h, and the ball milling speed is 50-200rmp, so as to obtain the ceramic powder with uniform ball milling.
In particular, the copper/diamond composite substrate in S3 is 5-15mm from the aerosol nozzle.
In particular, the deposition in S3 is to deposit a ceramic coating on the surface of a substrate with rough surface at 20-50 ℃, the moving speed of the nozzle is 0.5-5 mm/S, and the deposition time is 0.5-10min.
In particular, the thermal conductivity of the substrate of the insulating ceramic coating in S3 is 600-900W/mK, which is reduced by 0.5-3% compared with that of the unplated composite material, the average thickness of the insulating ceramic coating is 0.5-20 mu m, the compactness is 95-99%, the resistivity is higher than 10 13 Ω & cm, the dielectric constant under the current frequency of 2MHz is 8-9, and the surface roughness is lower than that of the unplated copper/diamond composite material and is 2-4 mu m.
Example 1
A method for plating an insulating ceramic coating on the surface of a copper/diamond composite material, which comprises the following steps:
S1, surface pretreatment, namely pretreating the surface of a copper/diamond composite substrate with the diamond volume fraction of 67% and the thermal conductivity of 812W/mK, wherein the pretreatment comprises surface sand paper polishing, surface cleaning and vacuum drying, wherein the surface sand paper polishing comprises the steps of polishing the surface of the copper/diamond composite substrate through 200-mesh sand paper, 400-mesh sand paper, 600-mesh sand paper and 1000-mesh sand paper, the surface cleaning comprises the steps of ultrasonic cleaning in an acetone solution at 20 ℃ for 10min, and the vacuum drying is carried out in a vacuum drying oven to obtain a surface-cleaned substrate;
s2, performing surface sand blasting treatment, namely performing ceramic particle sand blasting treatment on the substrate with the clean S1 surface, wherein the ceramic particles used in the sand blasting treatment are aluminum oxide particles with the particle diameter of 150 mu m, the spraying distance is 160mm, the spraying angle is 75 degrees, and the spraying time is 5 minutes, so as to obtain the substrate with the rough surface, wherein the surface roughness Ra of the substrate with the rough surface is 8.5 mu m;
And S3, plating an insulating ceramic coating, wherein the aerosol deposition device comprises an aerosol powder bin, an aerosol deposition bin, a sample rack and an aerosol nozzle, wherein the sample rack is used for placing a substrate, ceramic powder subjected to ball milling treatment is filled in the aerosol powder bin, the sample rack moves along the x and y directions, the aerosol nozzle adopts high-purity nitrogen as powder feeding gas, the flow rate of the nitrogen is 5L/min, the aerosol deposition bin is vacuumized to below 500Pa by using a vacuum pump, the alumina powder with the particle size of 0.7 mu m is subjected to ball milling treatment for 4 hours at the ball milling speed of 100rmp, the distance between the copper/diamond composite substrate and the aerosol nozzle is 10mm, the ceramic powder subjected to ball milling treatment is deposited on the substrate with the rough surface at the surface of S2 through the aerosol nozzle by the aerosol deposition device, the ceramic coating is deposited on the surface of the substrate with the rough surface at the temperature of 20 ℃, the moving speed of the nozzle is 5mm/S, and the deposition time is 5min, so that the substrate with the insulating ceramic coating is obtained.
The thermal conductivity of the substrate of the insulating ceramic coating prepared in the embodiment is 804W/mK, which is reduced by 1% compared with that of an unplated composite material, the average thickness of the insulating ceramic coating is 8 mu m, the compactness is 99%, the resistivity is higher than 1.2 multiplied by 10 13 omega cm, the dielectric constant at the current frequency of 2MHz is 8.6, and the surface roughness is lower than that of the unplated copper/diamond composite material and is 3.5 mu m. Fig. 1 and 2 are a cross-section and a surface scanning electron microscope image, respectively, of the alumina-coated copper/diamond composite material prepared in example 1, in which the copper matrix of the composite material after plating was completely covered with an alumina coating and a part of the diamond particle region was covered with the coating, compared to the copper/diamond composite material before plating (fig. 3).
Example 2
A method for plating an insulating ceramic coating on the surface of a copper/diamond composite material, which comprises the following steps:
S1, surface pretreatment, namely pretreating the surface of a substrate of a copper/diamond composite material with the diamond volume fraction of 65% and the thermal conductivity of 812W/mK, wherein the pretreatment comprises surface sand paper polishing, surface cleaning and vacuum drying, wherein the surface sand paper polishing comprises the steps of polishing the surface of the substrate of the copper/diamond composite material through 200-mesh sand paper, 400-mesh sand paper, 600-mesh sand paper and 1000-mesh sand paper, the surface cleaning comprises the steps of ultrasonic cleaning in an acetone solution at 20 ℃ for 10min, and the vacuum drying is carried out in a vacuum drying oven to obtain a substrate with a clean surface;
s2, performing surface sand blasting treatment, namely performing ceramic particle sand blasting treatment on the substrate with the clean S1 surface, wherein the ceramic particles used in the sand blasting treatment are aluminum oxide particles with the particle diameter of 150 mu m, the spraying distance is 160mm, the spraying angle is 75 degrees, and the spraying time is 5 minutes, so as to obtain the substrate with the rough surface, wherein the surface roughness Ra of the substrate with the rough surface is 8.5 mu m;
And S3, plating an insulating ceramic coating, wherein the aerosol deposition device comprises an aerosol powder bin, an aerosol deposition bin, a sample rack and an aerosol nozzle, wherein the sample rack is used for placing a substrate, ceramic powder subjected to ball milling treatment is filled in the aerosol powder bin, the sample rack moves along the x and y directions, the aerosol nozzle adopts high-purity nitrogen as powder feeding gas, the flow rate of the nitrogen is 10L/min, the aerosol deposition bin is vacuumized to below 500Pa by using a vacuum pump, the alumina powder with the particle size of 0.7 mu m is subjected to ball milling treatment for 4 hours at the ball milling speed of 100rmp, so that uniform ceramic powder is obtained, the distance between a copper/diamond composite substrate and the aerosol nozzle is 6mm, the ceramic powder subjected to ball milling treatment is deposited on the substrate with rough surface at the surface of S2 through the aerosol nozzle, the ceramic coating is deposited on the surface of the substrate with rough surface at the temperature of 20 ℃, the moving speed of the nozzle is 5mm/S, and the deposition time is 3min, so that the substrate with the insulating ceramic coating is obtained.
The thermal conductivity of the substrate of the insulating ceramic coating prepared in the embodiment is 808W/mK, which is reduced by 0.5% compared with that of the unplated composite material, the average thickness of the insulating ceramic coating is 6 mu m, the compactness is 99%, the resistivity is higher than 1.0X10 11 Ω & cm, the dielectric constant at the current frequency of 2MHz is 8.2, and the surface roughness is lower than that of the unplated copper/diamond composite material and is 2.5 mu m.
Example 3
A method for plating an insulating ceramic coating on the surface of a copper/diamond composite material, which comprises the following steps:
S1, surface pretreatment, namely pretreating the surface of a copper/diamond composite substrate with the diamond volume fraction of 62% and the thermal conductivity of 780W/mK, wherein the pretreatment comprises surface sand paper polishing, surface cleaning and vacuum drying, wherein the surface sand paper polishing comprises the steps of polishing the surface of the copper/diamond composite substrate through 200-mesh sand paper, 400-mesh sand paper, 600-mesh sand paper and 1000-mesh sand paper, the surface cleaning comprises the steps of ultrasonic cleaning for 20min in an acetone solution at 20 ℃, and the vacuum drying is carried out in a vacuum drying box to obtain a surface-cleaned substrate;
s2, performing surface sand blasting treatment, namely performing ceramic particle sand blasting treatment on the substrate with the clean S1 surface, wherein the ceramic particles used in the sand blasting treatment are aluminum oxide particles with the particle diameter of 150 mu m, the spraying distance is 160mm, the spraying angle is 75 degrees, and the spraying time is 5 minutes, so as to obtain the substrate with the rough surface, wherein the surface roughness Ra of the substrate with the rough surface is 8.5 mu m;
And S3, plating an insulating ceramic coating, wherein the aerosol deposition device comprises an aerosol powder bin, an aerosol deposition bin, a sample rack and an aerosol nozzle, wherein the sample rack is used for placing a substrate, ceramic powder subjected to ball milling treatment is filled in the aerosol powder bin, the sample rack moves along the x and y directions, the aerosol nozzle adopts high-purity nitrogen as powder feeding gas, the flow rate of the nitrogen is 9L/min, the aerosol deposition bin is vacuumized to below 500Pa by using a vacuum pump, the alumina powder with the particle size of 0.5 mu m is subjected to ball milling treatment for 5 hours, the ball milling speed is 50rmp, so that uniform ceramic powder is obtained, the distance between a copper/diamond composite substrate and the aerosol nozzle is 14mm, the ceramic powder subjected to ball milling treatment is deposited on the substrate with rough surface at the temperature of 20 ℃ through the aerosol nozzle, the movement speed of the nozzle is 4mm/S, and the deposition time is 9min, so that the substrate with the insulating ceramic coating is obtained.
The insulating ceramic coating prepared in the embodiment has the substrate heat conductivity of 773W/mK, which is reduced by 0.9% compared with that of the unplated composite material, the insulating ceramic coating has the average thickness of 9 mu m, the compactness of 99%, the resistivity of higher than 1.0X10 13 Ω & cm, the dielectric constant of 8.8 under the current frequency of 2MHz, and the surface roughness of lower than that of the unplated copper/diamond composite material of 3 mu m.
Example 4
A method for plating an insulating ceramic coating on the surface of a copper/diamond composite material, which comprises the following steps:
S1, surface pretreatment, namely pretreating the surface of a copper/diamond composite substrate with the diamond volume fraction of 67% and the thermal conductivity of 886W/mK, wherein the pretreatment comprises surface sand paper polishing, surface cleaning and vacuum drying, wherein the surface sand paper polishing comprises the steps of polishing the surface of the copper/diamond composite substrate through 200-mesh sand paper, 400-mesh sand paper, 600-mesh sand paper and 1000-mesh sand paper, the surface cleaning comprises the steps of ultrasonic cleaning in an acetone solution at 20 ℃ for 10min, and the vacuum drying is carried out in a vacuum drying oven to obtain a surface-cleaned substrate;
S2, performing surface sand blasting treatment, namely performing ceramic particle sand blasting treatment on the substrate with the clean S1 surface, wherein the ceramic particles used in the sand blasting treatment are alumina particles with the particle diameter of 100 mu m, the spraying distance is 160mm, the spraying angle is 85 degrees, and the spraying time is 1min, so as to obtain the substrate with the rough surface, and the surface roughness Ra of the substrate with the rough surface is 6.4 mu m;
And S3, plating an insulating ceramic coating, wherein the aerosol deposition device comprises an aerosol powder bin, an aerosol deposition bin, a sample rack and an aerosol nozzle, wherein the sample rack is used for placing a substrate, ceramic powder subjected to ball milling treatment is filled in the aerosol powder bin, the sample rack moves along the x and y directions, high-purity nitrogen is selected as powder feeding gas by the aerosol nozzle, the flow rate of the nitrogen is 2L/min, the aerosol deposition bin is vacuumized to be less than 1000Pa by using a vacuum pump, the alumina powder with the particle size of 3 mu m is subjected to ball milling treatment for 6 hours, the ball milling speed is 50rmp, so that ceramic powder subjected to ball milling uniformity is obtained, the distance between a copper/diamond composite substrate and the aerosol nozzle is 14mm, the ceramic powder subjected to ball milling treatment is deposited on the substrate with rough surface at the S2 through the aerosol nozzle, the ceramic coating is deposited on the surface of the substrate with rough surface at the temperature of 20 ℃, the moving speed of the nozzle is 4mm/S, and the deposition time is 7min, so that the substrate with the insulating ceramic coating is obtained.
The insulating ceramic coating prepared in the embodiment has the substrate heat conductivity of 859W/mK, which is 3% lower than that of the unplated composite material, the insulating ceramic coating has the average thickness of 9 mu m, the compactness of 95%, the resistivity of higher than 1.0X10 13 Ω & cm, the dielectric constant of 8.7 under the current frequency of 2MHz, and the surface roughness of lower than that of the unplated copper/diamond composite material of 3 mu m.
Example 5
A method for plating an insulating ceramic coating on the surface of a copper/diamond composite material, which comprises the following steps:
S1, surface pretreatment, namely pretreating the surface of a copper/diamond composite substrate with the diamond volume fraction of 67% and the thermal conductivity of 760W/mK, wherein the pretreatment comprises surface sand paper polishing, surface cleaning and vacuum drying, wherein the surface sand paper polishing comprises the steps of polishing the surface of the copper/diamond composite substrate through 200-mesh sand paper, 400-mesh sand paper, 600-mesh sand paper and 1000-mesh sand paper, the surface cleaning comprises the steps of ultrasonic cleaning in an acetone solution at 20 ℃ for 5min, and the vacuum drying is carried out in a vacuum drying box to obtain a surface-cleaned substrate;
S2, performing surface sand blasting treatment, namely performing ceramic particle sand blasting treatment on the substrate with the clean S1 surface, wherein the ceramic particles used in the sand blasting treatment are alumina particles with the particle diameter of 100 mu m, the spraying distance is 160mm, the spraying angle is 85 degrees, and the spraying time is 1min, so as to obtain the substrate with the rough surface, and the surface roughness Ra of the substrate with the rough surface is 6.4 mu m;
And S3, plating an insulating ceramic coating, wherein the aerosol deposition device comprises an aerosol powder bin, an aerosol deposition bin, a sample rack and an aerosol nozzle, wherein the sample rack is used for placing a substrate, ceramic powder subjected to ball milling treatment is filled in the aerosol powder bin, the sample rack moves along the x and y directions, high-purity nitrogen is selected as powder feeding gas by the aerosol nozzle, the flow rate of the nitrogen is 10L/min, the aerosol deposition bin is vacuumized to be less than 1000Pa by using a vacuum pump, the alumina powder with the particle size of 3 mu m is subjected to ball milling treatment for 5 hours, the ball milling speed is 50rmp, so that ceramic powder subjected to ball milling uniformity is obtained, the distance between a copper/diamond composite substrate and the aerosol nozzle is 5mm, the ceramic powder subjected to ball milling treatment is deposited on the substrate with rough surface at the S2 through the aerosol nozzle, the ceramic coating is deposited on the surface of the substrate with rough surface at the temperature of 20 ℃, the moving speed of the nozzle is 4mm/S, and the deposition time is 9min, so that the substrate with the insulating ceramic coating is obtained.
The thermal conductivity of the substrate of the insulating ceramic coating prepared in the embodiment is 754W/mK, which is reduced by 0.8% compared with that of an unplated composite material, the average thickness of the insulating ceramic coating is 18 mu m, the compactness is 96%, the resistivity is higher than 2.1 multiplied by 10 13 omega cm, the dielectric constant at the current frequency of 2MHz is 8.7, and the surface roughness is lower than that of the unplated copper/diamond composite material and is 4 mu m.
Example 6
A method for plating an insulating ceramic coating on the surface of a copper/diamond composite material, which comprises the following steps:
S1, surface pretreatment, namely pretreating the surface of a substrate of a copper/diamond composite material with the volume fraction of diamond of 64 percent and the thermal conductivity of 637W/mK, wherein the pretreatment comprises surface sand paper polishing, surface cleaning and vacuum drying, wherein the surface sand paper polishing comprises the steps of polishing the surface of the substrate of the copper/diamond composite material through 200-mesh sand paper, 400-mesh sand paper, 600-mesh sand paper and 1000-mesh sand paper, the surface cleaning comprises the steps of ultrasonic cleaning in an acetone solution at 20 ℃ for 6min, and the vacuum drying is carried out in a vacuum drying oven to obtain a substrate with a clean surface;
S2, performing surface sand blasting treatment, namely performing ceramic particle sand blasting treatment on the substrate with the clean S1 surface, wherein the ceramic particles used in the sand blasting treatment are alumina particles with the particle diameter of 100 mu m, the spraying distance is 160mm, the spraying angle is 85 degrees, and the spraying time is 1min, so as to obtain the substrate with the rough surface, and the surface roughness Ra of the substrate with the rough surface is 6.4 mu m;
And S3, plating an insulating ceramic coating, wherein the aerosol deposition device comprises an aerosol powder bin, an aerosol deposition bin, a sample rack and an aerosol nozzle, wherein the sample rack is used for placing a substrate, ceramic powder subjected to ball milling treatment is filled in the aerosol powder bin, the sample rack moves along the x and y directions, high-purity nitrogen is selected as powder feeding gas by the aerosol nozzle, the flow rate of the nitrogen is 10L/min, the aerosol deposition bin is vacuumized to be less than 1000Pa by using a vacuum pump, the alumina powder with the particle size of 3 mu m is subjected to ball milling treatment for 5 hours, the ball milling speed is 50rmp, so that ceramic powder subjected to ball milling uniformity is obtained, the distance between a copper/diamond composite substrate and the aerosol nozzle is 5mm, the ceramic powder subjected to ball milling treatment is deposited on the substrate with rough surface at the S2 through the aerosol nozzle, the ceramic coating is deposited on the surface of the substrate with rough surface at the temperature of 20 ℃, the moving speed of the nozzle is 4mm/S, and the deposition time is 9min, so that the substrate with the insulating ceramic coating is obtained.
The insulating ceramic coating prepared in the embodiment has the substrate heat conductivity of 631W/mK, which is reduced by 2.5% compared with that of the unplated composite material, the insulating ceramic coating has the average thickness of 18 mu m, the compactness of 96%, the resistivity of higher than 2.1 multiplied by 10 13 omega cm, the dielectric constant of 8.7 under the current frequency of 2MHz, and the surface roughness of lower than that of the unplated copper/diamond composite material of 4 mu m.
According to the scheme, the method for plating the insulating ceramic coating on the surface of the copper/diamond composite material can solve the technical problems that in the prior art, the surface insulativity and the heat conductivity of the copper/diamond composite material cannot be cooperatively improved, the component selection of the prepared insulating layer only can consider one aspect of the insulativity and the heat conductivity, or the preparation process is complex, the operation difficulty is high, the flow is long, the thermal physical property of the composite material can be damaged in the preparation process, the industrial production is not facilitated, and the like.
According to the invention, the surface of the copper/diamond composite material substrate is polished by using 200-mesh, 400-mesh, 600-mesh and 1000-mesh sand paper respectively, oxide and pollutants on the surface of the composite material are removed, and then the surface is cleaned by using an ultrasonic organic solvent, so that the doping impurities of the coating in the subsequent preparation and the influence on the component uniformity of the coating are avoided.
The ball milling treatment of submicron ceramic powder ensures that the ball milled powder has uniform granularity and good fluidity, and the invention has the functions of uniformly distributing coating components and improving the adhesive force, resistivity and thermal conductivity of the coating and a substrate in the preparation of the ceramic coating.
The invention adjusts the distance between the copper/diamond composite material substrate and the aerosol nozzle by controlling the movement of the sample frame along the x and y directions, controls the flow rate of the carrier gas for powder feeding, combines the movement range, the movement speed and the deposition time of the nozzle, and finally precisely controls the deposition range and the thickness of the ceramic coating.
The invention tests the thermal conductivity of the copper/diamond composite material by using a laser flash method, and discovers that the thermal conductivity of the copper/diamond composite material is only reduced by 3 percent after a layer of aluminum oxide coating with the thickness of 9 mu m is deposited. Because the particle size of the alumina powder used for aerosol deposition is small and the powder speed is high, the compactness (95-99%) of the alumina coating and the interfacial binding force of the alumina coating and the copper/diamond composite material are effectively increased. And when the scanning electron microscope is used for observation, defects such as pores and the like are not observed at the interface between the coating and the composite material.
The thermal conductivity of the substrate of the insulating ceramic coating prepared by the invention is 600-900W/mK, which is reduced by 0.5-3% compared with that of the unplated composite material, the average thickness of the insulating ceramic coating is 0.5-20 mu m, the density is 95-99%, the resistivity is higher than 10 13 Ω & cm, the dielectric constant under the current frequency of 2MHz is 8-9, and the surface roughness is lower than that of the unplated copper/diamond composite material and is 2-4 mu m.
In a word, compared with other traditional methods, the method for preparing the copper/diamond composite material with the insulating coating by surface pretreatment, surface sand blasting and insulating ceramic coating plating has the advantages of uniform component distribution, uniform performance, synergistic improvement of thermal conductivity and resistivity, simplicity, easiness in operation, environment friendliness, low cost, short flow and high efficiency, and is beneficial to industrial mass production and popularization.
It should be understood that the term "and/or" is merely an association relationship describing the associated object, and means that three relationships may exist, for example, a and/or B, and may mean that a exists alone, while a and B exist alone, and B exists alone, wherein a and B may be singular or plural. In addition, the character "/" herein generally indicates that the associated object is an "or" relationship, but may also indicate an "and/or" relationship, and may be understood by referring to the context.
In the present invention, "at least one" means one or more, and "a plurality" means two or more. "at least one of" or the like means any combination of these items, including any combination of single item(s) or plural items(s). For example, at least one (a, b, or c) of a, b, c, a-b, a-c, b-c, or a-b-c may be represented, wherein a, b, c may be single or plural.
It should be understood that, in various embodiments of the present invention, the sequence numbers of the foregoing processes do not mean the order of execution, and the order of execution of the processes should be determined by the functions and internal logic thereof, and should not constitute any limitation on the implementation process of the embodiments of the present invention.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. The method for plating the insulating ceramic coating on the surface of the copper/diamond composite material is characterized by comprising the following steps of:
S1, surface pretreatment, namely pretreating the surface of a substrate of a high-heat-conductivity copper/diamond composite material to obtain a substrate with a clean surface;
S2, performing surface sand blasting treatment, namely performing ceramic particle sand blasting treatment on the substrate with the clean S1 surface to obtain a substrate with a rough surface;
and S3, plating an insulating ceramic coating, namely depositing ceramic powder subjected to ball milling treatment on the substrate with the rough surface S2 through an aerosol nozzle by an aerosol deposition device to obtain the substrate with the insulating ceramic coating.
2. The method for plating an insulating ceramic coating on a copper/diamond composite material according to claim 1, wherein the diamond volume fraction of the copper/diamond composite material with high thermal conductivity in S1 is 30-70%, the thermal conductivity is 600-900W/mK, and the pretreatment is surface sanding, surface cleaning and vacuum drying.
3. The method of plating an insulating ceramic coating on a copper/diamond composite surface according to claim 2, wherein the surface sanding in S1 is performed by sanding the surface of the copper/diamond composite substrate with 200 mesh, 400 mesh, 600 mesh and 1000 mesh sandpaper, respectively, the surface cleaning is ultrasonic cleaning in acetone solution for 5-30min, and the vacuum drying is performed in a vacuum drying oven.
4. The method for plating an insulating ceramic coating on a copper/diamond composite material surface according to claim 1, wherein the ceramic particles used in the sand blasting treatment in S2 are alumina particles of 100-200 μm, the blasting distance is 150-250mm, the blasting angle is 70-90 °, and the blasting time is 1-5min.
5. The method of plating an insulating ceramic coating on a copper/diamond composite surface according to claim 1, wherein the surface roughness Ra of the surface roughened substrate in S2 is 5 to 10 μm.
6. The method for plating an insulating ceramic coating on a copper/diamond composite material surface according to claim 1, wherein the aerosol deposition device in S3 comprises an aerosol powder bin, a sample holder for placing a substrate and an aerosol nozzle, wherein the aerosol powder bin is filled with ceramic powder after ball milling treatment, the sample holder moves along x and y directions, the aerosol nozzle adopts high-purity nitrogen or argon as powder feeding gas, and the flow rate of the argon or nitrogen is 1-10L/min.
7. The method for plating an insulating ceramic coating on a copper/diamond composite material surface according to claim 6, wherein the ceramic powder in S3 is any one of alumina, aluminum nitride and silicon nitride, the particle size is 0.1-4 μm, the ceramic powder is filled into a ball mill for ball milling for 1-6 hours, and the ball milling speed is 50-200rmp.
8. The method of claim 6, wherein the copper/diamond composite substrate in S3 is 5-15mm from the aerosol nozzle.
9. The method of plating an insulating ceramic coating on a copper/diamond composite surface according to claim 1, wherein the depositing in S3 is depositing the ceramic coating on the surface of the substrate having a surface roughness at 20 to 50 ℃, and the moving speed of the nozzle is 0.5 to 5 mm/S, and the depositing time is 0.5 to 10min.
10. The method of plating an insulating ceramic coating on a copper/diamond composite material according to claim 1, wherein the insulating ceramic coating in S3 has a substrate thermal conductivity of 600-900W/mK, a thermal conductivity reduced by 0.5-3% compared to the unplated composite material, an average thickness of 0.5-20 μm, a densification of 95-99%, a resistivity of higher than 10 13 Ω -cm, a dielectric constant of 8-9 at a current frequency of 2MHz, and a surface roughness of 2-4 μm lower than the unplated copper/diamond composite material.
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