CN116021011A - Preparation method of graphene-coated copper powder particle reinforced cold spray copper-based composite coating - Google Patents
Preparation method of graphene-coated copper powder particle reinforced cold spray copper-based composite coating Download PDFInfo
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Abstract
A preparation method of a graphene coated copper powder particle reinforced cold spray copper-based composite coating relates to a preparation method of a copper-based composite coating. The invention discloses a preparation method of a graphene-coated copper powder particle reinforced cold spray copper-based composite coating, which comprises the steps of growing graphene on the surface of copper powder particles in situ by PECVD technology to obtain graphene-coated copper powder particles, using an optimized low-energy ball milling process to obtain copper composite powder with uniformly distributed graphene-coated copper powder particles, avoiding tissue defects caused by graphene agglomeration, improving the bonding strength of the coating and a substrate and the tissue uniformity inside the coating based on the low-temperature process and the extremely fast deposition rate of the cold spray technology, and being beneficial to obtaining the graphene-coated copper powder particle reinforced copper-based composite coating with excellent thermal, electric, mechanical and wear resistance.
Description
Technical Field
The invention relates to a preparation method of a copper-based composite coating.
Background
The conductive coating is widely applied to the fields of construction, transportation, manufacturing, mining, education, military, aerospace and the like, and the pure copper coating has excellent electrical conductivity and thermal conductivity, but has poor hardness and wear resistance, and the pure copper coating is easy to generate serious abrasion and even fragmentation under some extreme service conditions, so that serious potential safety hazards and economic and personnel losses are caused.
Graphene is a two-dimensional allotrope of carbon, produced by 1-s and 2-p orbital hybridization, forming a hexagonal carbocyclic ring. In graphene, each carbon atom is sp 2 After hybridization, there is one free electron, which is present in the pi orbitals. Pi orbitals help to dislocate the electron network and couple high carrier (electron) concentrations with large carrier mobilities at room temperature. These unique characteristics of graphene enable localized conduction of carriers to near-micron dimensions, making it an ideal additive for improving thermoelectric performance of metals. The mechanical property, the thermoelectric property and the wear resistance of the copper coating are obviously improved after the copper coating is reinforced by graphene, but because the graphene has large specific surface area and high surface energy, agglomeration is easy to occur, and the copper coating is unfavorable for being uniformly dispersed in a copper matrix. The traditional method for coating the graphene on the copper surface comprises a mechanical ball milling method, a chemical growth method and the like, wherein the mechanical ball milling method has poor coating uniformity, long time consumption and low bonding strength between the graphene and copper particles, the graphene is easy to separate from the copper particles after ball milling, and the chemical growth method needs to use various chemical reagents, is complex in operation and is easy to cause environmental pollution.
The conventional preparation methods of the graphene reinforced copper-based composite coating comprise thermal spraying, laser cladding, chemical vapor deposition and the like, wherein in the methods, the process temperature of the thermal spraying and the laser cladding is extremely high, severe thermal damage is easily caused to a substrate to be processed, the formed coating also has higher thermal stress, and the coating has defects such as cracks, gaps and the like; the thickness of the coating prepared by chemical vapor deposition is limited, and is usually below tens of micrometers, the deposition rate of the coating is relatively slow, and the process for simultaneously depositing the composite film layer of graphene and copper is complex.
Disclosure of Invention
In order to solve the defects in the prior art, the invention discloses a preparation method of a graphene-coated copper powder particle reinforced cold spray copper-based composite coating, which creatively introduces a PECVD technology, grows graphene on the surfaces of copper powder particles in situ to obtain graphene-coated copper powder particles, uses an optimized low-energy ball milling process to obtain copper composite powder with uniformly distributed graphene-coated copper powder particles, avoids tissue defects caused by graphene agglomeration, and can improve the bonding strength of the coating and a substrate and the tissue uniformity inside the coating based on the low-temperature process and the extremely fast deposition rate of the cold spray technology, thereby being beneficial to obtaining the graphene-coated copper powder particle reinforced copper-based composite coating with excellent thermal, electric and mechanical properties and wear resistance.
The preparation method of the graphene coated copper powder particle reinforced cold spray copper-based composite coating comprises the following steps:
firstly, in a methane atmosphere, adopting a plasma enhanced chemical vapor deposition method to grow a graphene layer on the surface of copper powder in situ to obtain graphene coated copper powder particles;
secondly, carrying out low-energy ball milling on the graphene coated copper powder particles and the copper powder by utilizing a ball mill, so that the graphene coated copper powder particles are uniformly distributed in the copper powder, and obtaining mixed powder; the mass ratio of the copper powder to the graphene coated copper powder particles is 1-3:1;
and thirdly, spraying the mixed powder obtained in the second step on a substrate by adopting cold spraying to obtain the graphene coated copper powder particle reinforced copper-based composite coating.
The invention has the principle and beneficial effects that:
1. according to the invention, a PECVD method and a low-energy ball milling are combined to obtain the copper powder particles coated with graphene, so that the bonding strength of graphene and copper powder can be effectively improved, the graphene can be uniformly distributed in the copper powder, the bonding effect of the graphene and the copper particles is good, agglomeration is not easy, and the preparation of the graphene-coated copper powder particle reinforced copper-based composite coating with excellent thermal, electrical, mechanical and wear resistance properties is facilitated.
2. In the process of growing graphene on the surface of copper powder particles in situ by adopting a Plasma Enhanced Chemical Vapor Deposition (PECVD) technology, the surface contacted with gas can realize film deposition, and the method has a good film deposition effect on the complex geometric surface. The invention adopts PECVD technology to grow graphene on the surface of copper powder particles in situ, has high deposition rate, uniform graphene coating, larger coating area, high bonding strength with copper particles, and is not easy to separate graphene from copper powder in composite powder, thereby avoiding the agglomeration of graphene to a great extent, and further effectively avoiding the defects of cracks and the like caused by the agglomeration of graphene in the subsequent coating; in addition, the temperature is firstly increased to 500 ℃ and kept at the temperature in the preheating stage of PECVD, so that the grain refinement of copper powder can be promoted, and the compact and uniform structure in the subsequent coating can be obtained.
3. The invention adopts cold spraying technology, can carry out coating deposition at lower temperature (usually hundreds of degrees centigrade) and higher deposition speed (usually the coating deposition can reach millimeter-level thickness per minute), the temperature of the spraying process is far lower than the melting point of copper, the mixed powder is less affected by heat, no phase change occurs in the spraying process, the generation of thermal stress and thermal defects in the coating is greatly inhibited, the invention has excellent tissue morphology and mechanical property, the thickness is between tens of micrometers and tens of millimeters, and the bonding strength of the prepared coating and a base material is high, so that the graphene coated copper powder particle reinforced copper-based composite coating with excellent thermal, electric, mechanical and wear resistance properties is prepared.
Drawings
FIG. 1 shows the Raman test result of the mixed powder prepared in the second step of example 1;
fig. 2 is a physical view of the PEEK substrate with the graphene coated copper powder particle-reinforced copper-based composite coating prepared in example 1.
Detailed Description
The technical scheme of the invention is not limited to the specific embodiments listed below, and also comprises any reasonable combination of the specific embodiments.
The first embodiment is as follows: the preparation method of the graphene-coated copper powder particle reinforced cold spray copper-based composite coating comprises the following steps:
firstly, in a methane atmosphere, adopting a plasma enhanced chemical vapor deposition method to grow a graphene layer on the surface of copper powder in situ to obtain graphene coated copper powder particles;
the plasma enhanced chemical vapor deposition comprises the following steps: firstly, copper powder is spread on a quartz plate, and is placed in a vacuum chamber, vacuumized until the air pressure is below 40Pa, heated and dried for 10-30min, and then methane is introduced until the air pressure is recovered to 1.01X10 5 Pa, vacuumizing again until the air pressure is lower than 40Pa, and introducing methane to maintain the air pressure at 40-66.7Pa; then heating the vacuum chamber at a heating rate of 10 ℃/min, keeping the temperature for 10-30min after heating to 500 ℃, and stopping heating; naturally lowering the temperature of the vacuum chamber, and preserving the temperature for 10-3000min when the temperature is lowered to 300 ℃; the plasma exciter is started while the temperature is maintained, and the exciting power is set to be 150-500W; the set heat preservation time is related to the thickness of the graphene; wherein the flow rate of methane is 1-50sccm.
Secondly, carrying out low-energy ball milling on the graphene coated copper powder particles and the copper powder by utilizing a ball mill, so that the graphene coated copper powder particles are uniformly distributed in the copper powder, and obtaining mixed powder; the mass ratio of the copper powder to the graphene coated copper powder particles is 1-3:1;
and thirdly, spraying the mixed powder obtained in the second step on a substrate by adopting cold spraying to obtain the graphene coated copper powder particle reinforced copper-based composite coating.
The present embodiment has the following advantageous effects:
1. according to the embodiment, the mode of combining the PECVD method and the low-energy ball milling is adopted to obtain the copper powder particles coated with the graphene, so that the bonding strength of the graphene and the copper powder can be effectively improved, the graphene can be uniformly distributed in the copper powder, the bonding effect of the graphene and the copper particles is good, agglomeration is not easy, and the graphene-coated copper powder particle reinforced copper-based composite coating with excellent thermal, electric, mechanical and wear resistance properties can be prepared.
2. In the process of growing graphene on the surfaces of copper powder particles in situ by adopting a Plasma Enhanced Chemical Vapor Deposition (PECVD) technology, the embodiment can realize film deposition on the surfaces contacted with gas, and has good film deposition effect on the surfaces with complex geometry. The method adopts PECVD technology to grow graphene on the surface of copper powder particles in situ, has high deposition rate, uniform graphene coating and larger coating area, has high bonding strength with copper particles, is not easy to separate graphene from copper powder in composite powder, avoids the agglomeration of graphene to a great extent, and further effectively avoids the defects of cracks and the like caused by the agglomeration of graphene in the subsequent coating; in addition, the temperature is firstly increased to 500 ℃ and kept at the temperature in the preheating stage of PECVD, so that the grain refinement of copper powder can be promoted, and the compact and uniform structure in the subsequent coating can be obtained.
3. The embodiment adopts a cold spraying technology, can carry out coating deposition at a lower temperature (generally hundreds of ℃) and a higher deposition speed (generally the coating deposition can reach millimeter-level thickness per minute), the temperature of the spraying process is far lower than the melting point of copper, the mixed powder is less affected by heat, no phase change occurs in the spraying process, the generation of thermal stress and thermal defects in the coating is greatly inhibited, the coating has excellent tissue morphology and mechanical property, the thickness is between tens of micrometers and tens of millimeters, and the prepared coating has high bonding strength with a base material, so that the graphene coated copper powder particle reinforced copper-based composite coating with excellent thermal, electric, mechanical and wear resistance properties is prepared.
The second embodiment is as follows: the first difference between this embodiment and the specific embodiment is that: in the first step, the purity of the copper powder is 99.9%, the particles are spherical, the particle size is 40-60 mu m, and the purity of methane gas is 99.99%.
And a third specific embodiment: this embodiment differs from the first or second embodiment in that: in the second step, the purity of the copper powder is 99.9%, the particles are spherical, and the particle size is 40-60 mu m.
The specific embodiment IV is as follows: this embodiment differs from one of the first to third embodiments in that: in the second step, the ball mill is a planetary ball mill.
Fifth embodiment: this embodiment differs from one to four embodiments in that: the plasma enhanced chemical vapor deposition in the first step comprises the following steps: firstly, copper powder is spread on a quartz plate, and is placed in a vacuum chamber, vacuumized to the air pressure below 40Pa, heated and dried for 10min, and then methane is introduced until the air pressure is recovered to 1.01X10 5 Pa, vacuumizing again until the air pressure is below 40Pa, and slowly introducing methane to maintain the air pressure at 40-66.7Pa; then heating the vacuum chamber at a heating rate of 10 ℃/min, keeping the temperature for 10-30min after heating to 500 ℃, and stopping heating; naturally lowering the temperature of the vacuum chamber, and preserving the temperature for 10-3000min when the temperature is lowered to 300 ℃; the plasma exciter is started while the temperature is maintained, and the exciting power is set to be 150-500W; the set heat preservation time is related to the thickness of the graphene; wherein the flow rate of methane is 1-50sccm.
Specific embodiment six: this embodiment differs from one of the first to fifth embodiments in that: the plasma enhanced chemical vapor deposition in the first step comprises the following steps: firstly, copper powder is spread on a quartz plate, and is placed in a vacuum chamber, vacuumized to the air pressure below 40Pa, heated and dried for 10min, and then methane is introduced until the air pressure is recovered to 1.01X10 5 Pa, vacuumizing again until the air pressure is below 40Pa, and slowly introducing methane to maintain the air pressure at 40-66.7Pa; then heating the vacuum chamber at a heating rate of 10 ℃/min, keeping the temperature for 10min after heating to 500 ℃, and stopping heating; naturally lowering the temperature of the vacuum chamber, and preserving the temperature for 10-3000min when the temperature is lowered to 300 ℃; the plasma exciter is started while the temperature is maintained, and the exciting power is set to be 150-500W; the set heat preservation time is related to the thickness of the graphene; wherein the flow rate of methane is 1-50sccm.
Seventh embodiment: this embodiment differs from one of the first to sixth embodiments in that: the low-energy ball milling in the second step comprises the following steps: mixing copper powder and graphene coated copper powder particles, and then filling the mixture into a ball milling tank; vacuumizing, introducing argon, dry milling at ball-milling speed of 50-200r/min and ball-milling at ball-material ratio of 8-12:1 for 4-10 hr,
and (3) carrying out unidirectional rotation, and stopping rotating for 10min every 1h of ball milling to obtain mixed powder, wherein the mixed powder is copper composite powder with uniformly distributed graphene coated copper powder particles.
Eighth embodiment: this embodiment differs from one of the first to seventh embodiments in that: the cold spraying in the third step comprises the following steps:
ultrasonically cleaning a substrate to be sprayed with absolute ethyl alcohol for 5-60min, taking out, drying, performing sand blasting on the surface to be sprayed, and cleaning the surface to be sprayed with an air gun after the treatment; loading the mixed powder obtained in the second step into a powder feeder, fixing a substrate, then carrying out cold spraying by using a spray gun, adopting argon as powder feeding gas, wherein a cold spraying track is S-shaped, the row spacing of the spraying track is 1.5-3mm, the spraying beam current and the surface to be sprayed are 90 degrees, the gun speed is 50-200mm/S, the vertical distance between a gun muzzle and the surface to be sprayed is 10-50mm, the chamber air pressure is 3-6MPa, and the chamber temperature is 700 ℃. The spraying times can be adjusted at will according to the required coating thickness.
Detailed description nine: this embodiment differs from one to eight of the embodiments in that: the cold spraying in the third step comprises the following steps: ultrasonically cleaning a substrate to be sprayed with absolute ethyl alcohol for 5-60min, taking out, drying, performing sand blasting on the surface to be sprayed, and cleaning the surface to be sprayed with an air gun after the treatment; and (3) loading the mixed powder obtained in the step two into a powder feeder, fixing a substrate, then carrying out cold spraying by using a spray gun, adopting argon gas as powder feeding gas, wherein a cold spraying track is S-shaped, the row spacing of the spraying track is 1.5mm, the spraying beam current and the surface to be sprayed are 90 degrees, the gun speed is 100mm/S, the vertical distance between a gun opening and the surface to be sprayed is 20mm, the chamber air pressure is 3.5MPa, and the chamber temperature is 700 ℃.
Detailed description ten: this embodiment differs from one of the embodiments one to nine in that: in the graphene coated copper powder particle reinforced copper-based composite coating obtained in the step three, the graphene accounts for 0.005-0.1wt% of the total metal.
Example 1
The preparation method of the graphene-coated copper powder particle reinforced cold spray copper-based composite coating comprises the following steps:
in a methane atmosphere, a graphene layer grows on the surface of copper powder in situ by a plasma enhanced chemical vapor deposition method to obtain graphene coated copper powder particles; wherein, the purity of the copper powder is 99.9%, the particles are spherical, the particle size is 40 μm, and the purity of the methane gas is 99.99%.
The PECVD method comprises the following steps: spreading copper powder on quartz plate, vacuum-pumping to air pressure of 35Pa, heating and oven drying for 10min, and introducing methane to air pressure of 1.01X10 5 Pa, vacuumizing again to the air pressure of 35Pa, and slowly introducing methane to maintain the air pressure at 40Pa; then heating the vacuum chamber at a heating rate of 10 ℃/min, keeping the temperature for 10min after heating to 500 ℃, and stopping heating; naturally reducing the temperature of the vacuum chamber, and starting a heater to keep the temperature when the temperature is reduced to 300 ℃; meanwhile, starting a plasma exciter, wherein the exciting power is 200W, and setting the heat preservation time (namely the graphene growth time) to be 20min; wherein, the flow rate of methane is 30sccm.
Secondly, carrying out low-energy ball milling on the graphene coated copper powder particles and the copper powder by adopting a planetary ball mill, so that the graphene coated copper powder particles are uniformly distributed in the copper powder, and obtaining mixed powder; wherein, the purity of the copper powder is 99.9%, the particles are spherical, and the particle diameter is 40 μm.
The low-energy ball milling comprises the following steps: mixing copper powder and graphene coated copper powder particles according to a mass ratio of 1:1, and then filling the mixture into a ball milling tank; vacuum pumping, argon gas feeding, dry grinding in ball grinding process, ball grinding speed of 100r/min, low energy ball grinding for 8h, unidirectional rotation, stopping rotation for 10min every 1h ball grinding to obtain copper composite powder with uniformly distributed graphene coated copper powder particles, and Raman test shown in FIG. 2 shows that three characteristic peaks of graphene appear in the obtained mixed powder.
And thirdly, processing the obtained mixed powder by adopting a cold spraying technology to obtain the graphene coated copper powder particle reinforced copper-based composite coating.
The cold spraying technology processing process comprises the following steps: ultrasonically cleaning a PEEK substrate with absolute ethyl alcohol for 10min, taking out and drying, performing sand blasting on the surface to be sprayed, and cleaning the surface to be sprayed with an air gun after the treatment; loading the obtained mixed powder into a powder feeder, fixing a PEEK base material, then carrying out cold spraying by using a spray gun, adopting argon gas as powder feeding gas, enabling a cold spraying track to be S-shaped, enabling the row spacing of the spraying track to be 1.5mm, enabling a spraying beam to be 90 degrees with the surface to be sprayed, enabling the gun speed to be 100mm/S, enabling the vertical distance between a gun muzzle and the surface to be sprayed to be 20mm, enabling the air pressure of a chamber to be 3.5MPa, enabling the temperature of the chamber to be 700 ℃, and repeating spraying for 10 times.
In the graphene-coated copper powder particle-reinforced cold spray copper-based composite coating obtained in the embodiment, the graphene accounts for 0.04% by weight of the total metal.
Example 2
The preparation method of the graphene-coated copper powder particle reinforced cold spray copper-based composite coating comprises the following steps:
firstly, in a methane atmosphere, a graphene layer grows on the surface of copper powder in situ by a plasma chemical vapor deposition (PECVD) method to obtain graphene coated copper powder particles; wherein, the purity of the copper powder is 99.9%, the particles are spherical, the particle size is 50 μm, and the purity of the methane gas is 99.99%.
The PECVD method comprises the following steps: spreading copper powder on quartz plate, vacuum-pumping to air pressure of 40Pa, heating and oven drying for 20min, and introducing methane to air pressure of 1.01X10 5 Pa, vacuumizing again to the air pressure of 40Pa, and slowly introducing methane to maintain the air pressure at 66.7Pa; then heating the vacuum chamber at a heating rate of 10 ℃/min, keeping the temperature for 15min after heating to 500 ℃, and stopping heating; naturally reducing the temperature of the vacuum chamber, and starting a heater to keep the temperature when the temperature is reduced to 300 ℃; at the same time, the plasma exciter is started, the exciting power is 250W, and the heat preservation time is set (namely, when the graphene growsInterval) is 30min; wherein, the flow rate of methane is 50sccm.
Secondly, carrying out low-energy ball milling on the graphene coated copper powder particles and the copper powder by adopting a planetary ball mill, so that the graphene coated copper powder particles are uniformly distributed in the copper powder, and obtaining mixed powder; wherein, the purity of the copper powder is 99.9%, the particles are spherical, and the particle diameter is 50 μm.
The low-energy ball milling comprises the following steps: mixing copper powder and graphene coated copper powder particles according to a mass ratio of 3:1, and then filling the mixture into a ball milling tank; and vacuumizing, then introducing argon, performing dry grinding in the ball-milling process, wherein the ball-milling speed is 200r/min, performing low-energy ball milling for 4 hours, and performing unidirectional rotation, wherein the ball-milling is stopped for 10 minutes every 1 hour, so as to obtain the copper composite powder with uniformly distributed graphene coated copper powder particles.
And thirdly, processing the obtained mixed powder by adopting a cold spraying technology to obtain the graphene coated copper powder particle reinforced copper-based composite coating.
The cold spraying technology processing process comprises the following steps: ultrasonically cleaning a PEEK substrate with absolute ethyl alcohol for 20min, taking out and drying, performing sand blasting on the surface to be sprayed, and cleaning the surface to be sprayed with an air gun after the treatment; loading the obtained mixed powder into a powder feeder, fixing a PEEK base material, performing cold spraying by using a spray gun, adopting argon gas as powder feeding gas, enabling a cold spraying track to be S-shaped, enabling the row spacing of the spraying track to be 2mm, enabling a spraying beam to form 90 degrees with the surface to be sprayed, enabling the gun speed to be 200mm/S, enabling the vertical distance between a gun opening and the surface to be sprayed to be 30mm, enabling the pressure of a chamber to be 4MPa, enabling the temperature of the chamber to be 700 ℃, and repeating spraying for 20 times.
In the graphene-coated copper powder particle-reinforced cold spray copper-based composite coating obtained in the embodiment, the graphene accounts for 0.025% by weight of the total metal.
Example 3
The preparation method of the graphene-coated copper powder particle reinforced cold spray copper-based composite coating comprises the following steps:
firstly, in a methane atmosphere, enabling a graphene layer to grow on the surface of copper powder in situ by a plasma chemical vapor deposition method, and obtaining graphene coated copper powder particles; wherein, the purity of the copper powder is 99.9%, the particles are spherical, the particle diameter is 60 mu m, and the purity of the methane gas is 99.99%.
The PECVD method comprises the following steps: spreading copper powder on quartz plate, vacuum-pumping to air pressure of 35Pa, heating and oven drying for 15min, and introducing methane to air pressure of 1.01X10 5 Pa, vacuumizing again to the air pressure of 35Pa, and slowly introducing methane to maintain the air pressure at 60Pa; then heating the vacuum chamber at a heating rate of 10 ℃/min, keeping the temperature for 15min after heating to 500 ℃, and stopping heating; naturally reducing the temperature of the vacuum chamber, and starting a heater to keep the temperature when the temperature is reduced to 300 ℃; meanwhile, starting a plasma exciter, wherein the exciting power is 225W, and setting the heat preservation time (namely the graphene growth time) to be 50 minutes; wherein, the flow rate of methane is 40sccm.
Secondly, carrying out low-energy ball milling on the graphene coated copper powder particles and the copper powder by adopting a planetary ball mill, so that the graphene coated copper powder particles are uniformly distributed in the copper powder, and obtaining mixed powder; wherein, the purity of the copper powder is 99.9%, the particles are spherical, and the particle diameter is 60 μm.
The low-energy ball milling comprises the following steps: mixing copper powder and graphene coated copper powder particles according to a mass ratio of 2:1, and then filling the mixture into a ball milling tank; and vacuumizing, then introducing argon, performing dry grinding in the ball-milling process, wherein the ball-milling speed is 150r/min, performing low-energy ball milling for 6 hours, and performing unidirectional rotation, wherein the ball milling is stopped for 10 minutes every 1 hour, so as to obtain the copper composite powder with uniformly distributed graphene coated copper powder particles.
And thirdly, processing the obtained mixed powder by adopting a cold spraying technology to obtain the graphene coated copper powder particle reinforced copper-based composite coating.
The cold spraying technology processing process comprises the following steps: ultrasonically cleaning a PEEK substrate with absolute ethyl alcohol for 15min, taking out and drying, performing sand blasting on the surface to be sprayed, and cleaning the surface to be sprayed with an air gun after the treatment; loading the obtained mixed powder into a powder feeder, fixing a PEEK base material, then carrying out cold spraying by using a spray gun, adopting argon gas as powder feeding gas, enabling a cold spraying track to be S-shaped, enabling the row spacing of the spraying track to be 2mm, enabling a spraying beam to be 90 degrees with the surface to be sprayed, enabling the gun speed to be 150mm/S, enabling the vertical distance between a gun opening and the surface to be sprayed to be 25mm, enabling the pressure of a chamber to be 3.8MPa, enabling the temperature of the chamber to be 700 ℃, and repeating spraying for 15 times.
In the graphene-coated copper powder particle-reinforced cold spray copper-based composite coating obtained in the embodiment, the graphene accounts for 0.045% by weight of the total metal.
Claims (10)
1. A preparation method of a graphene coated copper powder particle reinforced cold spray copper-based composite coating is characterized by comprising the following steps: the preparation method of the graphene coated copper powder particle reinforced cold spray copper-based composite coating comprises the following steps:
firstly, in a methane atmosphere, adopting a plasma enhanced chemical vapor deposition method to grow a graphene layer on the surface of copper powder in situ to obtain graphene coated copper powder particles;
the plasma enhanced chemical vapor deposition comprises the following steps: firstly, copper powder is spread on a quartz plate, and is placed in a vacuum chamber, vacuumized until the air pressure is below 40Pa, heated and dried for 10-30min, and then methane is introduced until the air pressure is recovered to 1.01X10 5 Pa, vacuumizing again until the air pressure is lower than 40Pa, and introducing methane to maintain the air pressure at 40-66.7Pa; then heating the vacuum chamber at a heating rate of 10 ℃/min, keeping the temperature for 10-30min after heating to 500 ℃, and stopping heating; naturally lowering the temperature of the vacuum chamber, and preserving the temperature for 10-3000min when the temperature is lowered to 300 ℃; the plasma exciter is started while the temperature is maintained, and the exciting power is set to be 150-500W; the set heat preservation time is related to the thickness of the graphene; wherein the flow rate of methane is 1-50sccm.
Secondly, carrying out low-energy ball milling on the graphene coated copper powder particles and the copper powder by utilizing a ball mill, so that the graphene coated copper powder particles are uniformly distributed in the copper powder, and obtaining mixed powder; the mass ratio of the copper powder to the graphene coated copper powder particles is 1-3:1;
and thirdly, spraying the mixed powder obtained in the second step on a substrate by adopting cold spraying to obtain the graphene coated copper powder particle reinforced copper-based composite coating.
2. The method for preparing the graphene-coated copper powder particle-reinforced cold spray copper-based composite coating, according to claim 1, is characterized in that: in the first step, the purity of the copper powder is 99.9%, the particles are spherical, the particle size is 40-60 mu m, and the purity of methane gas is 99.99%.
3. The method for preparing the graphene-coated copper powder particle-reinforced cold spray copper-based composite coating, according to claim 1, is characterized in that: in the second step, the purity of the copper powder is 99.9%, the particles are spherical, and the particle size is 40-60 mu m.
4. The method for preparing the graphene-coated copper powder particle-reinforced cold spray copper-based composite coating, according to claim 1, is characterized in that: in the second step, the ball mill is a planetary ball mill.
5. The method for preparing the graphene-coated copper powder particle-reinforced cold spray copper-based composite coating, according to claim 1, is characterized in that: the plasma enhanced chemical vapor deposition in the first step comprises the following steps:
firstly, copper powder is spread on a quartz plate, and is placed in a vacuum chamber, vacuumized to the air pressure below 40Pa, heated and dried for 10min, and then methane is introduced until the air pressure is recovered to 1.01X10 5 Pa, vacuumizing again until the air pressure is below 40Pa, and slowly introducing methane to maintain the air pressure at 40-66.7Pa; then heating the vacuum chamber at a heating rate of 10 ℃/min, keeping the temperature for 10-30min after heating to 500 ℃, and stopping heating; naturally lowering the temperature of the vacuum chamber, and preserving the temperature for 10-3000min when the temperature is lowered to 300 ℃; the plasma exciter is started while the temperature is maintained, and the exciting power is set to be 150-500W; the flow rate of methane is 1-50sccm.
6. The method for preparing the graphene-coated copper powder particle-reinforced cold spray copper-based composite coating, according to claim 1, is characterized in that: the plasma enhanced chemical vapor deposition in the first step comprises the following steps:
firstly, copper powder is spread on a quartz plate, and is placed in a vacuum chamber, vacuumized to the air pressure below 40Pa, heated and dried for 10min, and then methane is introduced until the air pressure is recovered to 1.01X10 5 Pa, vacuumizing again until the air pressure is below 40Pa, and slowly introducing methane to maintain the air pressure at 40-66.7Pa; then heating the vacuum chamber at a heating rate of 10 ℃/min, keeping the temperature for 10min after heating to 500 ℃, and stopping heating; naturally lowering the temperature of the vacuum chamber, and preserving the temperature for 10-3000min when the temperature is lowered to 300 ℃; the plasma exciter is started while the temperature is maintained, and the exciting power is set to be 150-500W; the flow rate of methane is 1-50sccm.
7. The method for preparing the graphene-coated copper powder particle-reinforced cold spray copper-based composite coating, according to claim 1, is characterized in that: the low-energy ball milling in the second step comprises the following steps:
mixing copper powder and graphene coated copper powder particles, and then filling the mixture into a ball milling tank; vacuumizing, then introducing argon, performing dry grinding in the ball-milling process, wherein the ball-material ratio is 8-12:1, the ball-milling rotating speed is 50-200r/min, the low-energy ball milling is performed for 4-10h, the unidirectional rotation is performed, and the ball milling is stopped for 10min every 1h to obtain mixed powder, namely the copper composite powder with uniformly distributed graphene coated copper powder particles.
8. The method for preparing the graphene-coated copper powder particle-reinforced cold spray copper-based composite coating, according to claim 1, is characterized in that: the cold spraying in the third step comprises the following steps:
ultrasonically cleaning a substrate to be sprayed with absolute ethyl alcohol for 5-60min, taking out, drying, performing sand blasting on the surface to be sprayed, and cleaning the surface to be sprayed with an air gun after the treatment; loading the mixed powder obtained in the second step into a powder feeder, fixing a substrate, then carrying out cold spraying by using a spray gun, adopting argon as powder feeding gas, wherein a cold spraying track is S-shaped, the row spacing of the spraying track is 1.5-3mm, the spraying beam current and the surface to be sprayed are 90 degrees, the gun speed is 50-200mm/S, the vertical distance between a gun muzzle and the surface to be sprayed is 10-50mm, the chamber air pressure is 3-6MPa, and the chamber temperature is 700 ℃.
9. The method for preparing the graphene-coated copper powder particle-reinforced cold spray copper-based composite coating according to claim 8, which is characterized in that: the cold spraying in the third step comprises the following steps:
ultrasonically cleaning a substrate to be sprayed with absolute ethyl alcohol for 5-60min, taking out, drying, performing sand blasting on the surface to be sprayed, and cleaning the surface to be sprayed with an air gun after the treatment; and (3) loading the mixed powder obtained in the step two into a powder feeder, fixing a substrate, then carrying out cold spraying by using a spray gun, adopting argon gas as powder feeding gas, wherein a cold spraying track is S-shaped, the row spacing of the spraying track is 1.5mm, the spraying beam current and the surface to be sprayed are 90 degrees, the gun speed is 100mm/S, the vertical distance between a gun opening and the surface to be sprayed is 20mm, the chamber air pressure is 3.5MPa, and the chamber temperature is 700 ℃.
10. The method for preparing the graphene-coated copper powder particle-reinforced cold spray copper-based composite coating, according to claim 1, is characterized in that: in the graphene coated copper powder particle reinforced copper-based composite coating obtained in the step three, the graphene accounts for 0.005-0.1wt% of the total metal.
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