CN114086179A - Preparation method of diamond wear-resistant coating on surface of copper substrate - Google Patents
Preparation method of diamond wear-resistant coating on surface of copper substrate Download PDFInfo
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- CN114086179A CN114086179A CN202111369442.XA CN202111369442A CN114086179A CN 114086179 A CN114086179 A CN 114086179A CN 202111369442 A CN202111369442 A CN 202111369442A CN 114086179 A CN114086179 A CN 114086179A
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- 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
- C23C28/027—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 including at least one metal matrix material comprising a mixture of at least two metals or metal phases or metal matrix composites, e.g. metal matrix with embedded inorganic hard particles, CERMET, MMC.
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- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
- C23C16/27—Diamond only
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/02—Electrophoretic coating characterised by the process with inorganic material
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/22—Servicing or operating apparatus or multistep processes
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- 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
Abstract
The invention discloses a method for preparing a diamond wear-resistant coating on the surface of a copper matrix, which comprises the steps of firstly, carrying out electrophoretic deposition on diamond particles and strong carbide metal element particles on the surface of the matrix in a dispersion distribution manner to prepare an electrophoretic deposition layer, then, carrying out annealing treatment on the copper matrix after electrophoretic deposition in a protective atmosphere, so that the strong carbide metal element particles, the diamond particles and the copper matrix respectively form high-strength combination of metal carbide and metal compound at the interface, and then, carrying out chemical vapor deposition on a diamond coating on the annealed matrix. The wear-resistant coating prepared by the invention has the advantages of high bonding strength with a substrate, difficult shedding, high wear resistance, strong corrosion resistance, good heat conductivity, short preparation period and simple process.
Description
Technical Field
The invention belongs to the technical field of wear-resistant coatings, and particularly relates to a preparation method of a diamond wear-resistant coating on the surface of a copper substrate.
Background
Copper is a metal material with excellent machining performance, easy welding, high heat conductivity and low price. However, the defects of poor surface wear resistance, easy oxidation during use and the like of copper limit the application of the copper in practical production. If a compact diamond coating can be deposited on copper, the frictional wear performance of a copper matrix can be enhanced, the corrosion resistance of the matrix can be improved by utilizing the chemical stability of the diamond coating, and the diamond coating has wide application prospect in the preparation of high-performance wear-resistant tools and cutting tools.
However, copper is a non-strong carbide forming element, the affinity of diamond and copper is very poor, and the difference of the thermal expansion coefficients of diamond and copper is very large, so that diamond deposition on the surface of a copper substrate is very difficult, a high-strength bonding interface cannot be obtained, a diamond layer is very easy to fall off and crack in the deposition or use process, and the excellent performance of a diamond coating is difficult to exert. Therefore, enhancing the bonding force between the copper substrate and the diamond coating is the key to preparing high performance diamond coatings on copper.
At present, the method of Cu matrix alloying and transition layer deposition on the surface of Cu is mainly adopted to improve the bonding strength of the copper matrix and the diamond coating. Alloying of a Cu matrix refers to alloying copper with other metals with good bonding properties with diamond, thereby improving the bonding strength between the copper matrix and the diamond coating, and Wan team et al studied vapor deposition of diamond Coatings on Cu-W and Cu-WC substrates, and improved the bonding strength between the matrix and diamond by doping tungsten or tungsten carbide in copper, "Surface & Coatings Technology" 284 (2015) 133-. The method has the defects that the influence of Cu-W and Cu-WC on the bonding force of the chemical vapor deposition diamond coating is greatly influenced by the content of matrix elements, the preparation cost of the alloy is high, and the method still has great limitation in the using process. The transition layer deposited on the surface of the Cu is formed by depositing a transition layer with high bonding performance with copper and diamond at the interface of the copper and the diamond coating to improve the bonding strength of the copper substrate and the diamond coating, and the Chinese patent application No. CN2019109
64078.8A Cu-based CVD diamond heat sink sheet and its preparation method are provided, wherein a metal transition layer is formed between the diamond layer deposited by copper and chemical vapor deposition by magnetron sputtering to improve the bonding strength between copper and diamond layer, however, the diamond directly grown on the metal transition layer has large internal stress and is easy to fall off and crack when being subjected to external force.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a preparation method of a diamond wear-resistant coating on the surface of a copper substrate. The diamond wear-resistant coating with high bonding strength, good wear resistance, high preparation speed and high mechanical strength can be obtained on the copper substrate by the method.
The invention is realized by the following technical scheme:
a preparation method of a diamond wear-resistant coating on the surface of a copper substrate comprises the following steps:
1) electrophoretic deposition: polishing, smoothing and cleaning a copper matrix, placing the copper matrix in an electrophoretic solution of strong carbide metal element particles and diamond particles, and depositing a layer of electrophoretic deposition layer in which the metal particles and the diamond particles are distributed in a dispersed manner on the copper matrix;
2) annealing: annealing the copper substrate subjected to electrophoretic deposition in the step 1), and cooling to room temperature to form a metal carbide interface layer between the metal particles and the diamond particles and a metal diffusion layer between the metal particles and the copper substrate;
3) chemical vapor deposition of diamond coating: and 2) carrying out chemical vapor deposition on a diamond coating on the copper substrate annealed in the step 2).
Further, in the electrophoretic deposition in the step 1), the granularity of the diamond particles is 5 nm-100 nm, and the granularity of the strong carbide metal element particles is 30 nm-150 nm.
Further, in the electrophoretic deposition of the step 1), the electrophoretic solution consists of solute and solvent; the solute comprises the following raw materials in parts by weight: 52-80 parts of strong carbide metal element particles, 25-65 parts of diamond particles, 1-15 parts of iodine, 1-10 parts of acetone and 1-10 parts of deionized water; the solvent is an alcohol organic matter; the solute concentration of the electrophoresis solution is 10 g/L-80 g/L.
Further, the alcohol organic matter is ethanol and isobutanol.
Further, after the electrophoresis solution is prepared in proportion, firstly stirring the mixture for 5 to 30min by using a glass rod, then ultrasonically dispersing the mixture for 10 to 60 min to obtain a suspension, then starting electrophoretic deposition, repeating the electrophoretic deposition process for 2 to 8 times, wherein the time is 1 to 5 min each time, after the completion of each process, stirring the electrophoresis solution for 5 to 30min and ultrasonically dispersing the electrophoresis solution for 10 to 60 min, and then carrying out next electrophoresis, wherein the distance between an electrophoresis polar plate is 10 to 100 mm, and the electrophoretic deposition voltage is 30 to 90V; and after the electrophoretic deposition process is finished, putting the copper matrix into a vacuum drying oven for drying, wherein the drying temperature is 100-120 ℃, and the drying time is 1-2 h.
Furthermore, in the electrophoretic deposition process, a mechanical stirrer or a magnetic stirrer is adopted to stir the electrophoretic solution, and the rotating speed of the mechanical stirrer or the magnetic stirrer is 100 r/min-300 r/min.
Further, in the annealing of the step 2), the copper matrix is annealed at the temperature of 800-1000 ℃ for 30-90 min and then cooled to the room temperature.
Further, in the chemical vapor deposition diamond coating of the step 3), the deposition method comprises a hot wire CVD method, a direct current jet CVD method and a microwave plasma CVD method.
Furthermore, in the chemical vapor deposition diamond coating of the third step, the diamond grain size in the diamond coating is 10 nm-100 μm, and the coating thickness is 10 μm-300 μm.
Further, in the electrophoretic deposition in the step 1), the strong carbide metal element particles are one or a mixture of Ti particles, Cr particles, Zr particles, V particles and Hf particles.
In the method, the strong carbide metal element and the carbon have strong affinity and can be combined with the carbon to form a stable compound (carbonization) under certain conditions; high-temperature annealing and CVD diamond deposition treatment can form a carbide layer between the elements and the diamond, and the bonding strength of the diamond coating is improved; meanwhile, under high-temperature treatment, the selected strong carbide metal element can generate solid solution reaction with copper and form a stable metallurgical structure. Also, carbides dispersed in the electrodeposited layer and at the diamond coating/electrodeposited layer interface may also serve to enhance the toughness and crack resistance of the coating. Therefore, the method comprises the steps of firstly carrying out electrophoretic deposition on the surface of a copper substrate to obtain a strong carbide metal element particle/diamond particle electrophoretic layer which is uniformly distributed; then annealing the copper matrix subjected to electrophoretic deposition at a certain temperature to form metal carbide between the metal element particles of the strong carbide and the diamond particles, and forming a diffusion layer between the metal particles and the copper matrix; finally, a layer of uniform and compact diamond coating is deposited on the annealed copper matrix by chemical vapor deposition.
Compared with the prior art, the invention has the following beneficial effects:
1) according to the wear-resistant coating prepared by the method, copper is used as a matrix, diamond particles and strong carbide metal element particles are dispersed and distributed on the surface of the matrix through electrophoretic deposition, and then the copper matrix subjected to electrophoretic deposition is subjected to annealing treatment in a protective atmosphere, so that metal carbides are formed between the metal particles and the diamond particles, and a diffusion layer is formed between the metal particles and the copper matrix, so that the bonding strength of the copper matrix and diamond is improved.
2) The wear-resistant coating prepared by the method further improves the bonding strength of the diamond coating and the electrophoretic deposition layer by carbide formed at the interface of the diamond coating and the electrophoretic deposition layer when the diamond is deposited by chemical vapor deposition, and in addition, the layer can also serve as a buffer zone when the coating is stressed, so that the stress in the coating is dispersed, and the bonding performance, the toughness and the crack resistance of the coating are enhanced.
3) The diamond particles in the electrophoretic deposition layer of the wear-resistant coating prepared by the method can be used as nucleation centers in the chemical deposition process, so that the time required by the deposition of the diamond coating is shortened, and the bonding strength of the obtained wear-resistant coating and a substrate is improved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate exemplary embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention.
FIG. 1 is a schematic cross-sectional view of a sample after electrophoretic deposition according to example 1 of the present invention.
Fig. 2 is a schematic cross-sectional structure diagram of a sample after annealing in example 1 of the present invention.
FIG. 3 is a schematic cross-sectional view of a sample after chemical vapor deposition according to example 1 of the present invention.
FIG. 4 is a schematic view of the electrophoretic deposition process in the method of the present invention.
In the figure: 1-metal copper sheet, 2-strong carbide metal element particles, 3-diamond particles, 4-electrophoretic deposition layer, 5-metal diffusion layer, 6-diamond coating, 7-electrophoretic anode, 8-mechanical stirrer or magnetic stirrer.
Detailed Description
In order that those skilled in the art will better understand the present invention, a more complete and complete description of the present invention is provided below in conjunction with the accompanying drawings and examples. It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
Example 1
A preparation method of a diamond wear-resistant coating on the surface of a copper substrate comprises the following steps:
1) preparing an electrophoresis solution: adding 60g of Ti metal particles, 350 g of diamond particles, 11 g of iodine, 10g of acetone and 10g of deionized water into a beaker filled with isobutanol, stirring for 5 min by using a glass rod, then placing the beaker into ultrasonic dispersion equipment, and ultrasonically dispersing for 60 min to obtain a suspension, and finally obtaining an electrophoretic solution with the solute concentration of 60 g/L; wherein, the Ti metal particles are used as strong carbide metal element particles 2, the particle size is 30 nm, and the particle size of the diamond particles 3 is 80 nm.
2) Electrophoretic deposition: as shown in fig. 4, polishing, smoothing and cleaning a metal copper sheet 1, placing the metal copper sheet in an electrophoresis tank, adding a prepared electrophoresis solution into the electrophoresis tank, taking the metal copper sheet 1 as an electrophoresis cathode, controlling the distance between the metal copper sheet 1 and an electrophoresis anode to be 50 mm, carrying out electrophoresis deposition for 3 times under an electrophoresis voltage of 60V, wherein each time is 5 min, stopping electrophoresis after each electrophoresis deposition is finished, stirring the electrophoresis solution for 5 min and carrying out ultrasonic dispersion for 60 min again, then carrying out electrophoresis for the next time according to the steps, stirring the electrophoresis solution by using a mechanical stirrer or a magnetic stirrer, and setting the rotating speed of the mechanical stirrer or the magnetic stirrer 8 to be 100 r/min; after the electrophoretic deposition is finished, the sample is placed into a vacuum drying oven for drying, the temperature of the vacuum drying oven is 100 ℃, the drying time is 2 hours, and finally, a layer of electrophoretic deposition layer 4 with metal particles and diamond particles 3 distributed in a dispersion mode is formed on the metal copper sheet 1 in a deposition mode, as shown in figure 1.
3) And (3) annealing: cleaning and drying the metal copper sheet 1 subjected to electrophoretic deposition, putting the metal copper sheet into an annealing furnace, annealing, cooling to room temperature, annealing at 1000 ℃ for 90 min in the protective atmosphere of argon, cooling to room temperature, forming a metal carbide interface layer between the metal particles and the diamond particles 3, and forming a metal diffusion layer 5 between the metal particles and the copper matrix, as shown in fig. 2.
4) Chemical vapor deposition of diamond coating: depositing a diamond coating 6 by adopting an MPCVD method, putting a metal copper sheet 1 into an MPCVD system, vacuumizing to below 5 Pa, introducing methane and hydrogen, controlling the flow rate of the methane to be 40 sccm and the flow rate of the hydrogen to be 1000 sccm, controlling the temperature of the metal copper sheet 1 to be 800 ℃, and carrying out chemical vapor deposition for 6 h under the air pressure of 3.5 KPa, and finally depositing on the metal copper sheet 1 to form a diamond coating 6, wherein the thickness of the diamond coating 6 is 10 mu m, and the size of diamond grains is 10 nm, as shown in figure 3.
Example 2
A preparation method of a diamond wear-resistant coating on the surface of a copper substrate comprises the following steps:
1) preparing an electrophoresis solution: adding 56g of Ti metal particles, 24 g of Hf metal particles, 365 g of diamond particles, 15 g of iodine, 4g of acetone and 8g of deionized water into a beaker filled with isobutanol, stirring for 20 min by using a glass rod, then placing the beaker into ultrasonic dispersion equipment for ultrasonic dispersion for 10min to obtain a suspension, and finally obtaining an electrophoretic solution with the solute concentration of 80 g/L; wherein, the mixed particle of Ti metal particle and Hf metal particle is used as the strong carbide metal element particle 2, the particle size is 90 nm, and the particle size of the diamond particle 3 is 100 nm.
2) Electrophoretic deposition: polishing, smoothing and cleaning a metal copper sheet 1, placing the metal copper sheet in an electrophoresis tank, adding a prepared electrophoresis solution into the electrophoresis tank, taking the metal copper sheet 1 as an electrophoresis cathode, controlling the distance between the metal copper sheet 1 and an electrophoresis anode to be 10 mm, carrying out electrophoresis deposition for 2 times under 30V electrophoresis voltage, wherein the time of each time is 3 min, stopping electrophoresis after each electrophoresis deposition is finished, stirring the electrophoresis solution for 20 min and carrying out ultrasonic dispersion for 40 min again, then carrying out next electrophoresis according to the steps, stirring the electrophoresis solution by adopting a mechanical stirrer or a magnetic stirrer, and regulating the rotating speed of the mechanical stirrer or the magnetic stirrer 8 to be 200 r/min; and after the electrophoretic deposition is finished, drying the sample in a vacuum drying oven at the temperature of 120 ℃ for 2 h, and finally depositing a layer of electrophoretic deposition layer 4 with metal particles and diamond particles 3 distributed in a dispersed manner on the metal copper sheet 1.
3) Annealing: cleaning and drying the metal copper sheet 1 subjected to electrophoretic deposition, putting the metal copper sheet into an annealing furnace, annealing, cooling to room temperature, annealing at 800 ℃ for 30min in an argon protective atmosphere, cooling to room temperature, forming a metal carbide interface layer between metal particles and diamond particles 3, and forming a metal diffusion layer 5 between the metal particles and a copper matrix.
4) Chemical vapor deposition of diamond coating: depositing a diamond coating 6 by adopting an MPCVD method, putting a metal copper sheet 1 into an MPCVD system, vacuumizing to below 5 Pa, introducing methane and hydrogen, controlling the flow rate of the methane to be 30 sccm and the flow rate of the hydrogen to be 1000 sccm, controlling the temperature of the metal copper sheet 1 to be 900 ℃, and carrying out chemical vapor deposition for 10 hours under the air pressure of 18 KPa, and finally depositing on the metal copper sheet 1 to form a diamond coating 6, wherein the thickness of the diamond coating 6 is 100 mu m, and the size of diamond grains is 100 nm.
Example 3
A preparation method of a diamond wear-resistant coating on the surface of a copper substrate comprises the following steps:
1) preparing an electrophoresis solution: adding 33.8g of Ti metal particles, 18.2g of Zr metal particles, 325 g of diamond particles, 1g of iodine, 7 g of acetone and 1g of deionized water into a beaker filled with ethanol, stirring for 10min by using a glass rod, then placing the beaker into ultrasonic dispersion equipment for ultrasonic dispersion for 25 min to obtain a suspension, and finally obtaining an electrophoretic solution with the solute concentration of 10 g/L; wherein, the mixed particle of Ti metal particle and Zr metal particle is used as the strong carbide metal element particle 2, the particle size is 150 nm, and the particle size of the diamond particle 3 is 5 nm.
2) Electrophoretic deposition: polishing, smoothing and cleaning a metal copper sheet 1, placing the metal copper sheet in an electrophoresis tank, adding a prepared electrophoresis solution into the electrophoresis tank, taking the metal copper sheet 1 as an electrophoresis cathode, controlling the distance between the metal copper sheet 1 and an electrophoresis anode to be 100 mm, carrying out electrophoresis deposition for 8 times under an electrophoresis voltage of 75V, wherein the time of each time is 1min, stopping electrophoresis after each electrophoresis deposition is finished, stirring the electrophoresis solution for 10min and carrying out ultrasonic dispersion for 25 min again, then carrying out electrophoresis for the next time according to the steps, stirring the electrophoresis solution by using a mechanical stirrer or a magnetic stirrer, and setting the rotating speed of the mechanical stirrer or the magnetic stirrer 8 to be 180 r/min; and after the electrophoretic deposition is finished, drying the sample in a vacuum drying oven at the temperature of 110 ℃ for 1 h, and finally depositing a layer of electrophoretic deposition layer 4 with metal particles and diamond particles 3 distributed in a dispersed manner on the metal copper sheet 1.
3) Annealing: cleaning and blow-drying the metal copper sheet 1 subjected to electrophoretic deposition, putting the metal copper sheet into an annealing furnace, annealing, cooling to room temperature, annealing at 920 ℃ for 75 min in the protective atmosphere of argon, cooling to room temperature, forming a metal carbide interface layer between the metal particles and the diamond particles 3, and forming a metal diffusion layer 5 between the metal particles and the copper matrix.
4) Chemical vapor deposition of diamond coating: depositing a diamond coating 6 by adopting an MPCVD method, putting a metal copper sheet 1 into an MPCVD system, vacuumizing to below 5 Pa, introducing methane and hydrogen, controlling the flow rate of the methane to be 50 sccm and the flow rate of the hydrogen to be 1000 sccm, controlling the temperature of the metal copper sheet 1 to be 950 ℃, and carrying out chemical vapor deposition for 7 h under the air pressure of 14 KPa, and finally depositing on the metal copper sheet 1 to form a diamond coating 6, wherein the thickness of the diamond coating 6 is 300 mu m, and the size of diamond grains is 100 mu m.
Example 4
A preparation method of a diamond wear-resistant coating on the surface of a copper substrate comprises the following steps:
1) preparing an electrophoresis solution: adding 71 g of Cr metal particles, 338 g of diamond particles, 8g of iodine, 1g of acetone and 5g of deionized water into a beaker filled with isobutanol, stirring for 30min by using a glass rod, then placing the beaker into ultrasonic dispersion equipment, and ultrasonically dispersing for 10min to obtain a suspension, and finally obtaining an electrophoretic solution with the solute concentration of 35 g/L; wherein, the Hf metal particles are used as the strong carbide metal element particles 2, the particle size is 65 nm, and the particle size of the diamond particles 3 is 45 nm.
2) Electrophoretic deposition: polishing, smoothing and cleaning a metal copper sheet 1, placing the metal copper sheet in an electrophoresis tank, adding a prepared electrophoresis solution into the electrophoresis tank, taking the metal copper sheet 1 as an electrophoresis cathode, controlling the distance between the metal copper sheet 1 and an electrophoresis anode to be 75 mm, carrying out electrophoresis deposition for 5 times under an electrophoresis voltage of 90V, wherein each time is 4min, stopping electrophoresis after each electrophoresis deposition is finished, stirring the electrophoresis solution for 30min and carrying out ultrasonic dispersion for 10min again, then carrying out next electrophoresis according to the steps, stirring the electrophoresis solution by adopting a mechanical stirrer or a magnetic stirrer 8, and controlling the rotating speed of the mechanical stirrer or the magnetic stirrer to be 300 r/min; and after the electrophoretic deposition is finished, drying the sample in a vacuum drying oven, wherein the temperature of the vacuum drying oven is 105 ℃, and the drying time is 1 h, and finally depositing a layer of electrophoretic deposition layer 4 with metal particles and diamond particles 3 distributed in a dispersion manner on the metal copper sheet 1.
3) Annealing: cleaning and drying the metal copper sheet 1 subjected to electrophoretic deposition, putting the metal copper sheet into an annealing furnace, annealing, cooling to room temperature, annealing at 950 ℃ for 55 min under the protective atmosphere of argon, cooling to room temperature, forming a metal carbide interface layer between the metal particles and the diamond particles 3, and forming a metal diffusion layer 5 between the metal particles and the copper matrix.
4) Chemical vapor deposition of diamond coating: depositing a diamond coating 6 by adopting an MPCVD method, putting a metal copper sheet 1 into an MPCVD system, vacuumizing to below 5 Pa, introducing methane and hydrogen, controlling the flow rate of the methane to be 80sccm and the flow rate of the hydrogen to be 1000 sccm, controlling the temperature of the metal copper sheet 1 to be 900 ℃, and carrying out chemical vapor deposition for 8 h under the pressure of 10 KPa, and finally depositing on the metal copper sheet 1 to form a diamond coating 6, wherein the thickness of the diamond coating 6 is 200 microns, and the size of diamond grains is 30 microns.
The technical solutions in the embodiments of the present invention are clearly and completely described above, and the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (10)
1. A preparation method of a diamond wear-resistant coating on the surface of a copper matrix is characterized by comprising the following steps:
1) electrophoretic deposition: polishing, smoothing and cleaning a copper matrix, placing the copper matrix in an electrophoretic solution of strong carbide metal element particles and diamond particles, and depositing a layer of electrophoretic deposition layer in which the metal particles and the diamond particles are distributed in a dispersed manner on the copper matrix;
2) annealing: annealing the copper substrate subjected to electrophoretic deposition in the step 1), and cooling to room temperature to form a metal carbide interface layer between the metal particles and the diamond particles and form a metal diffusion layer between the metal particles and the copper substrate;
3) chemical vapor deposition of diamond coating: and 2) carrying out chemical vapor deposition on a diamond coating on the copper substrate annealed in the step 2).
2. The method for preparing the diamond wear-resistant coating on the surface of the copper substrate according to claim 1, wherein the diamond wear-resistant coating comprises the following steps: in the electrophoretic deposition of the step 1), the granularity of the diamond particles is 5 nm-100 nm, and the granularity of the strong carbide metal element particles is 30 nm-150 nm.
3. The method for preparing the diamond wear-resistant coating on the surface of the copper substrate according to claim 1 or 2, wherein the diamond wear-resistant coating comprises the following steps: in the electrophoretic deposition of the step 1), an electrophoretic solution consists of a solute and a solvent; the solute comprises the following raw materials in parts by weight: 52-80 parts of strong carbide metal element particles, 25-65 parts of diamond particles, 1-15 parts of iodine, 1-10 parts of acetone and 1-10 parts of deionized water; the solvent is an alcohol organic matter; the solute concentration of the electrophoresis solution is 10 g/L-80 g/L.
4. The method for preparing the diamond wear-resistant coating on the surface of the copper substrate according to claim 3, wherein the diamond wear-resistant coating comprises the following steps: the alcohol organic substance is ethanol and isobutanol.
5. The method for preparing the diamond wear-resistant coating on the surface of the copper substrate according to claim 4, wherein the diamond wear-resistant coating comprises the following steps: after the electrophoresis liquid is prepared in proportion, firstly stirring for 5-30 min by using a glass rod, then carrying out ultrasonic dispersion for 10-60 min to obtain a suspension, then starting electrophoretic deposition, repeating the electrophoretic deposition process for 2-8 times, wherein each time is 1-5 min, after each process is finished, carrying out 5-30 min stirring and 10-60 min ultrasonic dispersion on the electrophoresis liquid again, and then carrying out next electrophoresis, wherein the distance between electrophoresis polar plates is 10-100 mm, and the voltage of electrophoretic deposition is 30-90V; and after the electrophoretic deposition process is finished, putting the copper substrate into a vacuum drying oven for drying, wherein the drying temperature is 100-120 ℃, and the drying time is 1-2 h.
6. The method for preparing the diamond wear-resistant coating on the surface of the copper substrate according to claim 5, wherein the diamond wear-resistant coating comprises the following steps: in the electrophoretic deposition process, a mechanical stirrer or a magnetic stirrer is adopted to stir the electrophoretic solution, and the rotating speed of the mechanical stirrer or the magnetic stirrer is 100 r/min-300 r/min.
7. The method for preparing the diamond wear-resistant coating on the surface of the copper substrate according to claim 1, wherein the diamond wear-resistant coating comprises the following steps: in the annealing of the step 2), the copper matrix is annealed at the temperature of 800-1000 ℃ for 30-90 min and then cooled to room temperature.
8. The method for preparing the diamond wear-resistant coating on the surface of the copper substrate according to claim 1, wherein the diamond wear-resistant coating comprises the following steps: in the chemical vapor deposition diamond coating of the step 3), the deposition method comprises a hot wire CVD method, a direct current injection CVD method and a microwave plasma CVD method.
9. The method for preparing the diamond wear-resistant coating on the surface of the copper substrate according to claim 1 or 8, wherein the diamond wear-resistant coating comprises the following steps: in the chemical vapor deposition diamond coating in the step 3), the diamond grain size in the diamond coating is 10 nm-100 μm, and the coating thickness is 10 μm-300 μm.
10. The method for preparing the diamond wear-resistant coating on the surface of the copper substrate according to claim 1, wherein the diamond wear-resistant coating comprises the following steps: in the electrophoretic deposition of the step 1), the strong carbide metal element particles are one or a mixture of Ti particles, Cr particles, Zr particles, V particles and Hf particles.
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| CN114941167B (en) * | 2022-05-07 | 2023-06-20 | 安徽亚珠金刚石股份有限公司 | Uniform sand feeding device for diamond production wire saw |
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| CN114086179B (en) | 2023-08-04 |
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