CN114086142A - High-entropy alloy rotary target and preparation method of cold spraying thereof - Google Patents
High-entropy alloy rotary target and preparation method of cold spraying thereof Download PDFInfo
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- CN114086142A CN114086142A CN202111433186.6A CN202111433186A CN114086142A CN 114086142 A CN114086142 A CN 114086142A CN 202111433186 A CN202111433186 A CN 202111433186A CN 114086142 A CN114086142 A CN 114086142A
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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- B22F9/00—Making metallic powder or suspensions thereof
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- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
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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
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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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
- C23C24/00—Coating starting from inorganic powder
- C23C24/02—Coating starting from inorganic powder by application of pressure only
- C23C24/04—Impact or kinetic deposition of particles
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
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Abstract
The invention relates to a preparation technology of a high-entropy alloy target material, in particular to a high-entropy alloy rotary target material and a cold spraying preparation method thereof. The method for preparing the high-entropy alloy rotary target material by adopting cold spraying comprises the following steps: step 1, carrying out ball milling prealloying on metal powder to obtain prealloyed powder; step 2, annealing the pre-alloyed powder in vacuum, grinding and sieving to obtain pre-treated powder; step 3, pretreating the base material to obtain a pretreated base material; and 4, cold spraying the pretreatment powder onto the surface of the pretreatment substrate. The invention relates to a cold spraying process, and the prepared target material has high purity and low oxygen content. During cold spraying, the speed of the particles is high, the solid particles reach the surface of the substrate at a high speed to generate plastic deformation, and the subsequent particles continuously impact the particles in the early stage to enable the target material to be continuously densified, so that the density of the target material is high.
Description
Technical Field
The invention relates to a preparation technology of a high-entropy alloy target material, in particular to a high-entropy alloy rotary target material and a cold spraying preparation method thereof.
Background
At present, the research on high-entropy alloys is increasing day by day, and the high-entropy alloys require that each component is close to an equimolar ratio, and the proportion of elements is between 5 and 35 percent. The research on the high-entropy alloy film gradually becomes a hotspot with the birth of the high-entropy alloy, and magnetron sputtering is the most important method for preparing the high-entropy alloy film. At present, the high-entropy alloy film is prepared on the surface of a tool and a die by virtue of the characteristics of superior mechanical property, strong corrosion resistance and the like, so that the service life of the tool and the die can be prolonged, and the production efficiency can be improved. The target material is used as a basic material for magnetron sputtering, and the quality of the target material plays an important role in the property of the film. The target material frequently used in the laboratory is a plane target material, more circular or rectangular target materials exist, the utilization rate of the target material is low, and only research and use can be provided. The target designed by the invention is a rotary target, can be widely applied to actual production, and has wide application range and high repeated utilization rate compared with a plane target. This requires the rotary target material to have advantages of high purity, high density, large-size integration, and the like.
In order to meet higher research and development and production requirements, a new technology for preparing a high-quality high-entropy alloy rotary target material is urgently needed.
Disclosure of Invention
The purpose of the invention is as follows: provides a high-entropy alloy rotary target material and a cold spraying preparation method thereof.
The technical scheme is as follows: the invention provides a method for preparing a high-entropy alloy rotary target material by adopting cold spraying, which comprises the following steps: step 1, carrying out ball milling prealloying on metal powder to obtain prealloyed powder; step 2, annealing the pre-alloyed powder in vacuum, grinding and sieving to obtain pre-treated powder; step 3, pretreating the base material to obtain a pretreated base material; and 4, cold spraying the pretreatment powder onto the surface of the pretreatment substrate.
In another aspect, the invention further provides the high-entropy alloy rotary target material prepared by the method, the relative density of the high-entropy alloy rotary target material is not less than 99%, the length of the high-entropy alloy rotary target material can reach 5000mm, and the unilateral thickness of the high-entropy alloy rotary target material can reach 4 mm.
Has the advantages that: the method for preparing the powder by using the MA (mechanical alloying), the high-temperature annealing and the grinding can avoid composition segregation and nonuniformity, and can avoid oxidation and impurity influence of grinding balls due to the fact that the ball milling process is short in time and is carried out under the protection of inert gas. The invention uses a cold spraying process, and the prepared target material has high purity and low oxygen content. During cold spraying, the speed of the particles is high, the solid particles reach the surface of the substrate at a high speed to generate plastic deformation, and the subsequent particles continuously impact the particles in the early stage to enable the target material to be continuously densified, so that the density of the target material is high. In addition, the method has the advantages of simple process, convenient operation and low requirement on operators, and the sprayed target is large-size integrated and does not need to be bound, so that the subsequent procedures are reduced, and the production cost is reduced.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and drawings.
In order to make the aforementioned and other objects, features and advantages of the present invention comprehensible, preferred embodiments accompanied with figures are described in detail below.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic process flow diagram of the method for preparing the high-entropy alloy rotary target material by cold spraying.
In the figure:
1-a feeding machine; 2-a heater; 3-a nozzle; 4-a substrate.
Detailed Description
The invention provides a method for preparing a high-entropy alloy rotary target material by adopting cold spraying, which comprises the following steps: step 1, carrying out ball milling prealloying on metal powder to obtain prealloyed powder; step 2, annealing the pre-alloyed powder in vacuum, grinding and sieving to obtain pre-treated powder; step 3, pretreating the base material to obtain a pretreated base material; and 4, cold spraying the pretreatment powder onto the surface of the pretreatment substrate.
Specifically, the cold spray gun is adopted to move back and forth in the spraying area at a certain speed, and metal powder is deposited on the surface of the base material at a high speed through the cold spray gun to be molded; constant-temperature circulating cooling water is always introduced into the substrate to cool the target material so as to control the temperature of the surface of the target material and prevent the target material from cracking; when the cold spray gun moves, the dust removal system moves synchronously with the cold spray gun to collect the undeposited powder, so that the undeposited powder is prevented from being mixed into the target material, and the density and the purity of the target material are ensured.
The method for preparing the powder by using the MA (mechanical alloying), the high-temperature annealing and the grinding can avoid composition segregation and nonuniformity, and can avoid oxidation and impurity influence of grinding balls due to the fact that the ball milling process is short in time and is carried out under the protection of inert gas. The invention uses a cold spraying process, and the prepared target material has high purity and low oxygen content. The method has the advantages of simple process, convenient operation and low requirement on operators, and the sprayed target is large-size integrated without binding, thereby reducing subsequent procedures and lowering production cost.
Wherein, optionally, the ball milling prealloying step is as follows: process control agents are added to the metal powder and ball milled under vacuum.
Alternatively, the process control agent may be, but is not limited to, gasoline.
Optionally, the temperature for annealing the pre-alloyed powder is 1100-1300 ℃, and the heat preservation time is 0.5-2 h.
Optionally, the pre-treatment powder has a particle size of no more than 50 μm.
Optionally, the step of pretreating the substrate comprises: the substrate surface was grit blasted, rinsed and degreased using organic solvents.
Optionally, the sand used for sand blasting is SiC, and the granularity is 16-36 meshes.
As shown in fig. 1, optionally, the specific steps of cold spraying the pretreatment powder onto the surface of the pretreated substrate are: and spraying the pretreatment powder to the surface of the pretreatment substrate after the pretreatment powder is sprayed out from a nozzle by using high-temperature compressed gas as boosting gas.
Specifically, the pretreatment powder is fed into the cold spray equipment along the feeder 1, and the compressed gas is heated by the heater 2 and then conveyed to the nozzle 3 to be sprayed out to the surface of the base material 4.
Optionally, the high-temperature compressed gas is air, nitrogen or helium; the temperature of the high-temperature compressed gas is 400-600 ℃, and the pressure is 1-10 MPa.
Optionally, the distance from the nozzle to the base material is 15-30 mm; the moving speed of the nozzle is 50-100 mm/s.
Specifically, during cold spraying, the solid particles reach the surface of the substrate at a high speed to generate plastic deformation, and the subsequent particles continuously impact the particles in the early stage to continuously densify the target, so that the density of the target is high.
Furthermore, the invention also provides the high-entropy alloy rotary target material prepared by the method, the relative density of the high-entropy alloy rotary target material is not lower than 99%, the length of the high-entropy alloy rotary target material can reach 5000mm, the unilateral thickness of the target material can reach 4mm, and the requirements of large-area high-quality coating and scientific research and production by recycling the target material are met.
Example 1
The embodiment is a preparation method of an AlCoCrFeNi high-entropy alloy planar target material, which comprises the following steps:
(1) weighing and proportioning powder: selecting Fe, Co, Cr, Ni and Al powder with the purity of more than or equal to 99.9 percent, and weighing according to equal atomic percentage.
(2) Pre-alloying powder: using a WC ball milling tank and milling balls, wherein the ball-material ratio is 8: putting the weighed mixed powder into a ball milling tank, adding gasoline as a process control agent, starting a mechanical pump and a molecular pump to vacuumize to 10-3 Pa, filling argon to start ball milling for 5 hours, and preventing too small particle size caused by overlong ball milling time.
(3) And (3) vacuum annealing: and (3) annealing by using a vacuum annealing furnace, wherein the powder subjected to ball milling needs to be spread during charging, the powder is heated to 1200 ℃ without preheating, the temperature is kept for 1h, furnace cooling (optimization) is carried out, the furnace cooling can be carried out to 600 ℃ for air cooling, and a furnace door is opened below 100 ℃.
(4) Grinding and sieving the powder agglomerates: ball-milling the powder agglomerate obtained after vacuum annealing, wherein the ball-to-material ratio is 10: 1, both the ball milling tank and the grinding balls are made of WC materials, the ball milling tank is vacuumized to below 10-3 Pa after the aggregates are placed in the ball milling tank, argon is filled for ball milling for 1 hour, the ball milled powder is screened, and powder with the particle size of 1-50 mu m is used for cold spraying.
(5) Pretreatment of a base material: mechanically polishing to remove an oxide layer of a stainless steel substrate, ultrasonically cleaning for 30min, drying, and finally performing sand blasting treatment on the stainless steel substrate, wherein SiC is used for the sand blasting treatment, and the granularity is 16-36 meshes;
(6) cold spraying high-entropy alloy powder: compressed helium is used as boosting gas, the pressure of carrier gas is 10MPa, and the temperature of carrier gas is 400 ℃. A stainless steel Laval nozzle is used, the distance between the nozzle and the substrate is 15mm, the spraying angle is 80-90 degrees, and the moving speed of the nozzle is 100 mm/s. Spraying to 5mm on the pretreated stainless steel plate.
The performance of the target is analyzed by using a scanning electron microscope, a metallographic microscope for analysis, a high-precision electronic scale, a mutual inductance coupling plasma mass spectrometer (ICP) and an X-ray diffractometer (XRD), the thickness of the high-entropy alloy plane target is 5mm, the relative density is 99.3%, the purity is more than or equal to 99.99%, the porosity is less than or equal to 0.7%, and the average grain size is less than 60 microns.
Example 2
The embodiment is a preparation method of an AlCoCrFeNi high-entropy alloy rotating target, and the difference between the embodiment and the embodiment 1 is only that:
(1) weighing and proportioning powder: selecting Fe, Co, Cr, Ni and Al powder with the purity of more than or equal to 99.9 percent, and weighing according to equal atomic percentage.
(2) Pre-alloying powder: using a WC ball milling tank and milling balls, wherein the ball-material ratio is 8: putting the weighed mixed powder into a ball milling tank, adding gasoline as a process control agent, starting a mechanical pump and a molecular pump to vacuumize to 10-3 Pa, filling argon to start ball milling for 5 hours, and preventing too small particle size caused by overlong ball milling time.
(3) And (3) vacuum annealing: and (3) annealing by using a vacuum annealing furnace, wherein the ball-milled powder is spread during charging, is not required to be preheated, is heated to 1100 ℃ for heat preservation for 2h, is cooled along with the furnace (preferably), and can also be cooled to 600 ℃ along with the furnace for air cooling, and a furnace door is opened below 100 ℃.
(4) Grinding and sieving the powder agglomerates: ball-milling the powder agglomerate obtained after vacuum annealing, wherein the ball-to-material ratio is 10: 1, both the ball milling tank and the grinding balls are made of WC materials, the ball milling tank is vacuumized to below 10-3 Pa after the aggregates are placed in the ball milling tank, argon is filled for ball milling for 1 hour, the ball milled powder is screened, and powder with the particle size of 1-50 mu m is used for cold spraying.
(5) Pretreatment of a base material: mechanically polishing to remove an oxide layer of the 304 stainless steel pipe, ultrasonically cleaning for 30min, drying, and finally performing sand blasting treatment on the 304 stainless steel pipe, wherein SiC is used for the sand blasting treatment, and the granularity is 16-36 meshes;
(6) cold spraying high-entropy alloy powder: compressed helium is used as boosting gas, the pressure of carrier gas is 10MPa, and the temperature of carrier gas is 400 ℃. A stainless steel Laval nozzle is used, the distance between the nozzle and the substrate is 15mm, the spraying angle is 80-90 degrees, the moving speed of the nozzle is 100mm/s, and the base tube is controlled to rotate around the central shaft at a certain rotating speed during powder spraying. Spraying to 5mm above the pretreated 304 stainless steel pipe.
The performance of the target material is analyzed by using a scanning electron microscope, a metallographic microscope for analysis, a high-precision electronic scale, a mutual inductance coupling plasma mass spectrometer (ICP) and an X-ray diffractometer (XRD), the thickness of the high-entropy alloy target material prepared by the embodiment is 6mm, the single side is 3mm, the relative density is 99.5%, the purity is more than or equal to 99.99%, the porosity is less than or equal to 0.5%, and the average grain size is less than 60 microns.
Example 3
The embodiment is a preparation method of an AlNiCoFeCrTi high-entropy alloy planar target material, which comprises the following steps:
(1) powder preparation: selecting Fe, Co, Cr, Ni, Al and Ti powders with the purity of more than or equal to 99.9 percent, and weighing according to equal atomic percentage.
(2) Pre-alloying powder: using a hard alloy ball milling tank and a steel ball milling, wherein the ball-material ratio is 8: putting the weighed mixed powder into a ball milling tank, adding gasoline as a process control agent, starting a mechanical pump and a molecular pump to vacuumize to 10-3 Pa, filling argon to start ball milling for 3 hours, and preventing too small particle size caused by overlong ball milling time.
(3) And (3) vacuum annealing: and (3) annealing by using a vacuum annealing furnace, spreading the ball-milled powder during charging, heating to 1300 without preheating, keeping the temperature for 0.5h, cooling with the furnace (preferably), or cooling with the furnace to 600 ℃ in an air-cooling manner, and opening a furnace door below 100 ℃.
(4) Grinding and sieving the powder agglomerates: ball-milling the powder agglomerate obtained after vacuum annealing, wherein the ball-to-material ratio is 10: 1, putting a hard alloy ball milling tank and steel milling balls into the ball milling tank, vacuumizing the ball milling tank to below 10-3 Pa, filling argon gas into the ball milling tank for ball milling for 1 hour, screening the ball milled powder, and using the powder with the particle size of 1-50 microns as cold spraying.
(5) Pretreatment of a base material: mechanically polishing to remove an oxide layer of a stainless steel substrate, ultrasonically cleaning for 30min, drying, and finally performing sand blasting treatment on the stainless steel substrate, wherein SiC is used for the sand blasting treatment, and the granularity is 16-36 meshes;
(6) cold spraying high-entropy alloy powder: compressed air is adopted as boosting gas, the pressure of carrier gas is 0.9MPa, and the temperature of carrier gas is 450 ℃. A stainless steel Laval nozzle is used, the distance between the nozzle and the substrate is 30mm, the spraying angle is 80-90 degrees, and the moving speed of the nozzle is 100 mm/s. Spraying to 5mm on the pretreated stainless steel plate.
The performance of the target material is analyzed by using a scanning electron microscope, an energy spectrometer (EDS), a metallographic microscope for analysis, a high-precision electronic scale, a mutual inductance coupling plasma mass spectrometer (ICP) and an X-ray diffractometer (XRD), the thickness of the high-entropy alloy target material prepared by the embodiment is 5mm, the relative density is 99.1%, the purity is more than or equal to 99.99%, the porosity is less than or equal to 1%, and the average grain size is less than 45 microns.
Example 4
The embodiment is a preparation method of an AlNiCoFeCrTi high-entropy alloy rotating target, and the difference between the embodiment and the embodiment 3 is only that:
(1) powder preparation: selecting Fe, Co, Cr, Ni, Al and Ti powders with the purity of more than or equal to 99.9 percent, and weighing according to equal atomic percentage.
(2) Pre-alloying powder: using a hard alloy ball milling tank and a steel ball milling, wherein the ball-material ratio is 8: putting the weighed mixed powder into a ball milling tank, adding gasoline as a process control agent, starting a mechanical pump and a molecular pump to vacuumize to 10-3 Pa, filling argon to start ball milling for 3 hours, and preventing too small particle size caused by overlong ball milling time.
(3) And (3) vacuum annealing: and (3) annealing by using a vacuum annealing furnace, spreading the ball-milled powder during charging, heating to 1300 without preheating, keeping the temperature for 0.5h, cooling with the furnace (preferably), or cooling with the furnace to 600 ℃ in an air-cooling manner, and opening a furnace door below 100 ℃.
(4) Grinding and sieving the powder agglomerates: ball-milling the powder agglomerate obtained after vacuum annealing, wherein the ball-to-material ratio is 10: 1, putting a hard alloy ball milling tank and steel milling balls into the ball milling tank, vacuumizing the ball milling tank to below 10-3 Pa, filling argon gas into the ball milling tank for ball milling for 1 hour, screening the ball milled powder, and using the powder with the particle size of 1-50 microns as cold spraying.
(5) Pretreatment of a base material: mechanically polishing to remove an oxide layer of the 304 stainless steel pipe, ultrasonically cleaning for 30min, drying, and finally performing sand blasting treatment on the 304 stainless steel pipe, wherein SiC is used for the sand blasting treatment, and the granularity is 16-36 meshes;
(6) cold spraying high-entropy alloy powder: compressed air is adopted as boosting gas, the pressure of carrier gas is 0.9MPa, and the temperature of carrier gas is 450 ℃. A stainless steel Laval nozzle is used, the distance between the nozzle and the substrate is 30mm, the spraying angle is 80-90 degrees, the moving speed of the nozzle is 100mm/s, and the base tube is controlled to rotate around the central shaft at a certain rotating speed when powder is sprayed. Spraying to 5mm above the pretreated 304 stainless steel pipe.
The performance of the target material is analyzed by using a scanning electron microscope, a metallographic microscope for analysis, a high-precision electronic scale, a mutual inductance coupling plasma mass spectrometer (ICP) and an X-ray diffractometer (XRD), the thickness of the high-entropy alloy rotating target material prepared by the embodiment is 7mm, the thickness of a single side is more than 3mm, the relative density is 99.4%, the purity is more than or equal to 99.99%, the porosity is less than or equal to 1%, and the average grain size is less than 45 micrometers.
In a word, compared with the prior art, the target prepared by the cold spraying process has high purity and high density, particularly can obtain an expected structure, belongs to a high-end rotary target, and can be applied to a wider field. In addition, the spraying equipment is simple to operate, the number of operators is small, the target is large in size and integrated, and the cost of the target can be effectively reduced.
When the powder is subjected to cold spraying, the particle speed is high, the high-speed particles impact the surface of the matrix to generate violent deformation to form a coating, the coating is compact in structure, and the target material density is high. The target material prepared by the cold spraying process is a large-size integrated target material, splicing and binding are not needed, the cost is saved, the probability of arc discharge of the target material in the sputtering process is reduced, the quality of the target material is ensured, and the quality of a coating film is improved.
Compared with the high-temperature thermal spraying technology, the cold spraying technology is to spray powder by the propelling of compressed gas at a temperature far lower than the melting point of the material, and the powder particles finally impact on a substrate at a high speed of more than 200m/s to generate plastic deformation deposition to form a coating. Even in an open air environment, oxidation does not occur because the powder is not directly heated. The coating has the advantages of compact structure, low porosity, uniform components and the like. The cold spraying temperature is 500 ℃, the actually adopted heating rate is high, the powder cannot be melted, and the stable structure and structure of the powder can be kept without phase change.
In the case of spraying high-entropy alloy powder, the production of powder by the MA (mechanical alloying) method has been studied abroad. The high-entropy alloy target prepared by smelting often wastes more raw materials due to larger component melting point difference, and the unevenness and segregation of components cannot be avoided; mechanical alloying often results in powders that are supersaturated and suffer from defects such as stress, compositional segregation, and the like, which are difficult to control. The method adopts the MA + high-temperature annealing method, and the target material prepared after cold spraying has uniform components, no component segregation and high purity.
When powder is sprayed, the machine tool system controls the substrate tube to rotate around the central shaft at a certain rotating speed, the cold spray gun reciprocates in a spraying area at a certain speed, and the powder is sputtered onto the surface of the substrate at a high speed through the cold spray gun to form a coating; constant-temperature circulating cooling water is always introduced into the interior of the substrate tube to cool the target material, and the surface temperature of the target material is controlled to prevent the target material from cracking; when the cold spray gun moves, the dust removal system also moves synchronously with the cold spray gun to collect the undeposited powder and intermittently discharge the undeposited powder, so that the undeposited powder is prevented from being mixed into the target material, and the density and the purity of the target material are ensured. When the dust removal system discharges powder, argon is correspondingly filled to make up the loss of gas in the cavity, and the entrance of external air is reduced; the spray chamber is cooled by external compressed air or liquid gas. Or the spraying cavity is of a double-layer structure, and circulating water is introduced into the middle of the spraying cavity for cooling.
The relative density of the prepared target material is more than or equal to 99 percent, the length can reach 5000mm, the unilateral thickness of the target material can reach 4mm, and the requirements of large-area high-quality coating and scientific research and production by repeatedly utilizing the target material are met.
Although the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the details of the embodiments, and various equivalent modifications can be made within the technical spirit of the present invention, and the scope of the present invention is also within the scope of the present invention. It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition. In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A method for preparing a high-entropy alloy rotary target material by adopting cold spraying is characterized by comprising the following steps:
step 1, carrying out ball milling prealloying on metal powder to obtain prealloyed powder;
step 2, annealing the pre-alloyed powder in vacuum, grinding and sieving to obtain pre-treated powder;
step 3, pretreating the base material to obtain a pretreated base material;
and 4, cold spraying the pretreatment powder onto the surface of the pretreatment substrate.
2. The method of claim 1,
the ball milling pre-alloying step comprises: process control agents are added to the metal powder and ball milled under vacuum.
3. The method of claim 1,
and annealing the pre-alloyed powder at 1100-1300 ℃ for 0.5-2 h.
4. The method of claim 1,
the particle size of the pre-treatment powder does not exceed 50 μm.
5. The method of claim 1,
the steps of pretreating the base material are as follows: the substrate surface was grit blasted, rinsed and degreased using organic solvents.
6. The method of claim 5,
the sand used for sand blasting is SiC, and the granularity is 16-36 meshes.
7. The method of claim 1,
the specific steps of cold spraying the pretreatment powder onto the surface of the pretreated substrate are:
and spraying the pretreatment powder to the surface of the pretreatment substrate after the pretreatment powder is sprayed out from a nozzle by using high-temperature compressed gas as boosting gas.
8. The method of claim 7,
the high-temperature compressed gas is air, nitrogen or helium;
the temperature of the high-temperature compressed gas is 400-600 ℃, and the pressure is 1-10 MPa.
9. The method of claim 7,
the distance from the nozzle to the base material is 15-30 mm;
the moving speed of the nozzle is 50-100 mm/s.
10. A high-entropy alloy rotary target material prepared by the method of claim 1,
the relative density of the high-entropy alloy rotary target is not less than 99%, the length of the high-entropy alloy rotary target can reach 5000mm, and the thickness of a single side of the high-entropy alloy rotary target can reach 4 mm.
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