CN111118460A - Rotary titanium target and preparation method thereof - Google Patents
Rotary titanium target and preparation method thereof Download PDFInfo
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- CN111118460A CN111118460A CN202010029277.2A CN202010029277A CN111118460A CN 111118460 A CN111118460 A CN 111118460A CN 202010029277 A CN202010029277 A CN 202010029277A CN 111118460 A CN111118460 A CN 111118460A
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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
- 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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- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
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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
- C23C24/045—Impact or kinetic deposition of particles by trembling using impacting inert media
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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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
- C23C4/08—Metallic material containing only metal elements
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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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/131—Wire arc spraying
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a rotary titanium target and a preparation method thereof. The preparation method of the rotary titanium target has the advantages of simple process, convenient operation, wide alloy component range and suitability for large-scale industrial production, the purity of the prepared target material is more than or equal to 99.95 percent, the relative density is more than or equal to 95 percent, the size is not limited, the thickness can reach 3-12 mm, the length can reach 4000mm, the oxygen content is less than or equal to 1200ppm, the crystal grain size is small, and the components are stable.
Description
Technical Field
The invention relates to the technical field of sputtering targets, in particular to a rotary titanium target and a preparation method thereof.
Background
Titanium has the characteristics of low density, good corrosion resistance, no toxicity or magnetism, weldability, good biocompatibility, strong surface decoration property and the like, and is widely applied to the fields of aviation, aerospace, chemical industry, petroleum, electric power, medical treatment, buildings, sports goods and the like. At present, the titanium target mainly comprises a plane target, a multi-arc cylindrical target, an integrated tube target and the like. Most titanium targets are produced by smelting and a spraying process is less.
Cold spraying is a spraying technology based on the aerodynamic principle, and is characterized in that high-pressure gas is utilized to generate ultrahigh-sound-speed airflow through a contraction and expansion pipe, powder is axially fed into the ultrahigh-sound-speed airflow, and the ultrahigh-sound-speed airflow is accelerated and then impacts a matrix to generate plastic deformation to be deposited on the surface of the matrix to form a coating. The spraying mode basically does not change the organization structure, so the coating has high density, small grain size and small stress (expressed as residual compressive stress), and can be used for preparing thick coatings; however, titanium has poor plastic deformation, and how to form a coating with a certain thickness by cold spraying needs to be solved urgently.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a rotary titanium target and a preparation method thereof, the method has simple process and convenient operation, and the prepared target has high purity, unlimited size, low oxygen content and small grain size.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a rotary titanium target comprises the following steps:
(1) preparing titanium powder with the average grain diameter D50 of 30-80 um: when the particle size of the titanium powder is small, the specific surface area is increased, the mutual friction of molecules is increased, the powder is easy to agglomerate, the continuous production is not facilitated, and the production efficiency is influenced; the density of the sprayed product is reduced and the appearance is poor; the powder is too fine to facilitate subsequent recovery, and therefore titanium powder with a D50 particle size of 30-80 μm, especially D50 ═ 30-60 μm, is selected;
(2) performing surface treatment on the target base tube;
(3) cold spraying: and (3) mounting the surface-treated target base tube on a transmission device, enabling the target base tube to rotate around a central shaft, enabling the spray gun to relatively move back and forth along the horizontal direction of the target base tube, starting the cooling device, then carrying out cold spraying on the titanium powder on the surface of the target base tube through the spray gun, and depositing to form a coating to obtain the target.
The method adopts the cold spraying process to prepare the rotary titanium target material, has simple process and convenient operation, and the coating of the prepared target material has high density, small grain size, low oxygen content, no change of tissue structure and stable components by optimizing the grain size of the titanium powder.
Preferably, in the step (1), the purity of the titanium powder is more than or equal to 99.95%, the plasticity of the titanium is mainly dependent on the purity of the titanium, the higher the purity of the titanium is, the greater the plasticity is, the more favorable the spraying is, and the utilization rate of the powder is higher.
Preferably, in the step (2), the target base tube is a stainless steel tube or a titanium tube, preferably a 304 nonmagnetic stainless steel tube, and the cost is low.
Preferably, in the step (2), the surface treatment includes sand blasting and priming.
Preferably, the abrasive used for the blasting is white corundum, wire cut pellets or cast steel grit, preferably cast steel grit.
Preferably, the mode of priming treatment is electric arc spraying, flame spraying or plasma spraying, and the raw material used for priming treatment is selected from wire materials or powder, wherein the wire materials are selected from at least one of copper aluminum wires, copper nickel wires, nickel aluminum wires and Monel wires; the powder is at least one of nickel-coated aluminum composite powder and aluminum-coated nickel composite powder.
Preferably, the priming means is arc spraying, preferably cupronickel arc spraying. The cost is relatively low by using the copper-nickel wire for electric arc spraying; the surface activation performance is high after priming, and the bonding strength with a subsequent coating is high; the environmental pollution is small.
Preferably, the surface roughness Ra of the target base tube after the priming treatment is 220-. When roughness is large, the bonding strength of the powder particles and the base pipe after priming is better, but when roughness is too large, the whole priming layer is more uneven, and the bonding strength is reduced.
Preferably, in the step (3), the rotation speed of the target base tube is 120-. The rotating speed is high, and the internal stress of the target material is favorably reduced; but the rotating speed of the base tube of the target material is too high, so that the requirement on equipment is high, and the long-term stable production is not facilitated.
Preferably, in the step (3), the moving speed of the spray gun is 20-40mm/s, preferably 20-30 mm/s.
Preferably, in the step (3), the process parameters of the cold spraying are as follows: the main gas pressure is 4-8Mpa, the carrier gas pressure is 4.5-8.5Mpa, the main gas heating temperature is 500-. For cold spraying, particle kinetic energy is critical to forming the coating. The gas pressure is high and the velocity of the particles is relatively high. The main gas pressure is 4-8MPa according to the production equipment and the titanium powder plasticity condition. When the gas pressure is constant, the speed of the powder particles can be further increased by heating the preheated gas; at the same time, higher temperatures favor plastic deformation of the powder particles upon impact. The main gas heating temperature is 500-1000 ℃ in combination with the self characteristics of the powder. In cold spraying, the supersonic two-phase flow leaving the nozzle is affected by air, and its speed, direction and temperature will change. This requires a compromise, with the optimal spray distance being selected to be 10-80 mm.
Preferably, the main gas and the carrier gas are nitrogen or inert gas, and further preferably, the main gas and the carrier gas for cold spraying are respectively and independently selected from nitrogen or helium; still more preferably, the main gas and carrier gas used for cold spraying are nitrogen gas. The cost of the nitrogen is lower.
Preferably, in the step (3), the dust removal air port corresponds to the circumferential area of the spray gun and moves back and forth along with the spray gun during cold spraying, and the undeposited powder is collected and can be recycled and sold, so that the cost is reduced.
The preparation method of the rotary titanium target further comprises the step of machining the target prepared in the step (3) to obtain a finished rotary titanium target product.
The invention aims to reduce the thermal expansion of the base tube and the coating by arranging a cooling device in cold spraying. Preferably, the cooling device comprises a water cooling device or an air cooling device, wherein the water cooling device is used for introducing circulating water into the target base pipe, and the water temperature is 5-40 ℃; the air cooling device is characterized in that air knives are arranged around the target base tube, and the gas used for air cooling is low-temperature compressed air or nitrogen; further preferably, a water cooling device is arranged for cooling during cold spraying, and the used water is normal temperature water.
The invention also provides the rotary titanium target prepared by the method, wherein the oxygen content of the rotary titanium target is less than or equal to 1000ppm, and the grain size is less than or equal to 40 mu m.
For the rotary titanium target, the machine needs to be stopped to replace a new target material after the rotary titanium target is used to a certain size or the surface of the titanium target needs to be treated after problems occur. The invention also provides a repair method of the rotary titanium target, which adopts a cold spraying mode to repair and specifically comprises the following steps:
(1) preparing titanium powder with the average grain diameter D50 of 30-80 mu m;
(2) carrying out surface treatment on the residual target;
(3) cold spraying: installing the surface-treated residual target on a transmission device, enabling the residual target to rotate around a central shaft of the residual target, enabling a spray gun to relatively move back and forth along the horizontal direction of the residual target, starting a cooling device, then cold spraying titanium powder on the surface of the residual target through the spray gun, depositing to form a coating, and obtaining a repaired target,
wherein, the rotating speed of the residual target is 120-200r/min, preferably 150-180 r/min;
the moving speed of the spray gun is 20-40mm/s, preferably 20-30 mm/s;
the technological parameters of cold spraying are as follows: the main gas pressure is 4-8Mpa, the carrier gas pressure is 4.5-8.5Mpa, the heating temperature of the main gas is 500-; still further preferably, the main gas and the carrier gas used for cold spraying are nitrogen, and the nitrogen is low in cost.
The cold spraying process parameters are as follows: main gas pressure: 5-6.5Mpa, carrier gas pressure: 5-7 Mpa; the main air heating temperature is 850 ℃ and 920 ℃; the distance between the spray guns is 30-45mm, which is more beneficial to preparing the target material with high density, high purity, low oxygen content and small grain size.
The surface treatment in the repairing method can be cleaning by absolute ethyl alcohol or polishing after the cleaning by absolute ethyl alcohol.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method of the rotary titanium target has the advantages of simple process, convenient operation, wide alloy component range and suitability for large-scale industrial production, the purity of the prepared target material is more than or equal to 99.95 percent, the relative density is more than or equal to 95 percent, the size is not limited, the thickness can reach 3-12 mm, the length can reach 4000mm, the oxygen content is less than or equal to 1200ppm, the grain size is small, the change of the structure is avoided, and the components are stable.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples. It will be understood by those skilled in the art that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the examples, the experimental methods used were all conventional methods unless otherwise specified, and the materials, reagents and the like used were commercially available without otherwise specified.
Example 1:
a preparation method of a rotary titanium target comprises the following steps:
1) preparing titanium powder with D50 being 30 mu m and the purity being 3N 5;
2) selecting a titanium tube with the inner diameter of 80mm, the outer diameter of 88mm and the tube length of 500mm as a target base tube; carrying out sand blasting treatment on the target base tube by using cast steel sand, and then using a copper-nickel wire for electric arc priming, wherein the surface roughness Ra of the target base tube after the priming treatment is 260-350 mu m;
3) mounting the primed target base tube on transmission equipment, and adjusting a motor to enable the base tube to rotate around a central shaft; starting cold spraying equipment, enabling a cold spraying spray gun to move back and forth relatively in the horizontal direction, introducing normal-temperature water as circulating cooling water, enabling a dust removal air port to face the circumferential area of the spray gun and move back and forth along with the spray gun, facilitating collection of undeposited powder, enabling titanium powder to be sputtered onto the surface of a base tube at a high speed through the cold spraying spray gun to form a coating through deposition, and obtaining a target material, wherein main gas and carrier gas used for cold spraying adopt nitrogen, the carrier gas pressure is 5Mpa, and the technological parameters of cold spraying are specifically shown in Table 1:
TABLE 1
4) And machining the target after cold spraying to obtain a finished product.
The detection shows that the thickness of the coating of the titanium target prepared by the embodiment is 3mm, the density is 95%, the oxygen content is 1000ppm, the powder utilization rate is 65%, and the coating bonding strength is 86 Mpa.
Example 2:
a preparation method of a rotary titanium target comprises the following steps:
1) preparing titanium powder with D50 being 35.8 μm and 4N purity;
2) selecting a stainless steel tube with the inner diameter of 100mm, the outer diameter of 108mm and the tube length of 850mm as a target base tube; carrying out sand blasting treatment on the target base tube by using cast steel sand, and then using a copper-nickel wire for electric arc priming, wherein the surface roughness Ra of the target base tube after the priming treatment is 260-350 mu m;
3) mounting the primed target base tube on transmission equipment, and adjusting a motor to enable the base tube to rotate around a central shaft; starting cold spraying equipment, enabling a cold spraying spray gun to move back and forth relatively in the horizontal direction, introducing normal-temperature water as circulating cooling water, enabling a dust removal air port to face the circumferential area of the spray gun and move back and forth along with the spray gun, facilitating collection of undeposited powder, enabling titanium powder to be sputtered onto the surface of a base tube at a high speed through the cold spraying spray gun to form a coating through deposition, and obtaining a target material, wherein main gas and carrier gas used for cold spraying adopt nitrogen, the carrier gas pressure is 5Mpa, and the technological parameters of cold spraying are specifically shown in a table 2:
TABLE 2
| Main air pressure Mpa | Main air flow Slpm | Heating temperature of main gas |
| 5.5 | 2200 | 750 |
| Base pipe rotating speed r/min | Moving speed mm/s of spray gun | Distance mm of spray gun |
| 130 | 30 | 35 |
4) And machining the target after cold spraying to obtain a finished product.
The titanium target prepared in the embodiment has a coating thickness of 5mm, a density of 95%, an oxygen content of 950ppm, and a powder utilization rate of 74%.
Example 3:
a preparation method of a rotary titanium target comprises the following steps:
1) preparing titanium powder with D50 being 40 mu m and the purity being 4N 5;
2) selecting a stainless steel tube with the inner diameter of 125mm, the outer diameter of 133mm and the tube length of 1220mm as a target base tube; carrying out sand blasting treatment on the target base tube by using cast steel sand, and then using a copper-nickel wire for electric arc priming, wherein the surface roughness Ra of the target base tube after the priming treatment is 260-350 mu m;
3) mounting the primed target base tube on transmission equipment, and adjusting a motor to enable the base tube to rotate around a central shaft; starting cold spraying equipment, enabling a cold spraying spray gun to move back and forth relatively in the horizontal direction, introducing normal-temperature water as circulating cooling water, enabling a dust removal air port to face the circumferential area of the spray gun and move back and forth along with the spray gun, facilitating collection of undeposited powder, enabling titanium powder to be sputtered onto the surface of a base tube at a high speed through the cold spraying spray gun to form a coating through deposition, and obtaining a target material, wherein main gas and carrier gas used for cold spraying adopt nitrogen, the carrier gas pressure is 5Mpa, and the technological parameters of cold spraying are specifically shown in a table 3:
TABLE 3
| Main air pressure Mpa | Main air flow Slpm | Heating temperature of main gas |
| 5.5 | 2220 | 830 |
| Base pipe rotating speed r/min | Moving speed mm/s of spray gun | Distance mm of spray gun |
| 150 | 25 | 45 |
4) And machining the target after cold spraying to obtain a finished product.
The titanium target prepared by the embodiment has the coating thickness of 7.5mm, the density of 96%, the oxygen content of 850ppm and the powder utilization rate of 81% through detection.
Example 4:
a preparation method of a rotary titanium target comprises the following steps:
1) preparing titanium powder with D50 being 45 mu m and the purity being 4N 5;
2) selecting a stainless steel tube with the inner diameter of 125mm, the outer diameter of 133mm and the tube length of 2600mm as a target base tube; carrying out sand blasting treatment on the target base tube by using cast steel sand, and then using a copper-nickel wire for electric arc priming, wherein the surface roughness Ra of the target base tube after the priming treatment is 260-350 mu m;
3) mounting the primed target base tube on transmission equipment, and adjusting a motor to enable the base tube to rotate around a central shaft; starting cold spraying equipment, enabling a cold spraying spray gun to move back and forth relatively in the horizontal direction, introducing normal-temperature water as circulating cooling water, enabling a dust removal air port to face the circumferential area of the spray gun and move back and forth along with the spray gun, facilitating collection of undeposited powder, enabling titanium powder to be sputtered onto the surface of a base tube at a high speed through the cold spraying spray gun to form a coating through deposition, and obtaining a target material, wherein main gas and carrier gas used for cold spraying adopt nitrogen, the carrier gas pressure is 5Mpa, and the technological parameters of cold spraying are specifically shown in a table 4:
TABLE 4
4) And machining the target after cold spraying to obtain a finished product.
The titanium target prepared by the embodiment has the coating thickness of 9mm, the density of 96%, the oxygen content of 800ppm and the powder utilization rate of 89% through detection.
Example 5:
a preparation method of a rotary titanium target comprises the following steps:
1) preparing titanium powder with the purity of 5N and the D50 being 55 mu m;
2) selecting a stainless steel tube with the inner diameter of 125mm, the outer diameter of 133mm and the tube length of 3191mm as a target base tube; carrying out sand blasting treatment on the target base tube by using cast steel sand, and then using a copper-nickel wire for electric arc priming, wherein the surface roughness Ra of the target base tube after the priming treatment is 260-350 mu m;
3) mounting the primed target base tube on transmission equipment, and adjusting a motor to enable the base tube to rotate around a central shaft; starting cold spraying equipment, enabling a cold spraying spray gun to move back and forth relatively in the horizontal direction, introducing normal-temperature water as circulating cooling water, enabling a dust removal air port to face the circumferential area of the spray gun and move back and forth along with the spray gun, facilitating collection of undeposited powder, enabling titanium powder to be sputtered onto the surface of a base tube at a high speed through the cold spraying spray gun to form a coating through deposition, and obtaining a target material, wherein main gas and carrier gas used for cold spraying adopt nitrogen, the carrier gas pressure is 6Mpa, and the technological parameters of cold spraying are specifically shown in a table 5:
4) and machining the target after cold spraying to obtain a finished product.
The titanium target prepared by the embodiment has the coating thickness of 10.5mm, the density of 96.5%, the oxygen content of 750ppm and the powder utilization rate of 94% through detection.
TABLE 5
| Main air pressure Mpa | Main air flow Slpm | Heating temperature of main gas |
| 6 | 2170 | 890 |
| Base pipe rotating speed r/min | Moving speed mm/s of spray gun | Distance mm of spray gun |
| 180 | 20 | 30 |
Example 6:
a preparation method of a rotary titanium target comprises the following steps:
1) preparing titanium powder with D50 being 60 mu m and the purity being 5N;
2) selecting a stainless steel tube with the inner diameter of 125mm, the outer diameter of 133mm and the tube length of 38970mm as a target base tube; carrying out sand blasting treatment on the target base tube by using cast steel sand, and then using a copper-nickel wire for electric arc priming, wherein the surface roughness Ra of the target base tube after the priming treatment is 260-350 mu m;
3) mounting the primed target base tube on transmission equipment, and adjusting a motor to enable the base tube to rotate around a central shaft; starting cold spraying equipment, enabling a cold spraying spray gun to move back and forth relatively in the horizontal direction, introducing normal-temperature water as circulating cooling water, enabling a dust removal air port to face the circumferential area of the spray gun and move back and forth along with the spray gun, facilitating collection of undeposited powder, enabling titanium powder to be sputtered onto the surface of a base tube at a high speed through the cold spraying spray gun to form a coating through deposition, and obtaining a target material, wherein main gas and carrier gas used for cold spraying adopt nitrogen, the carrier gas pressure is 7Mpa, and the technological parameters of cold spraying are specifically shown in a table 6:
TABLE 6
| Main air pressure Mpa | Main air flow Slpm | Heating temperature of main gas |
| 6.5 | 2170 | 920 |
| Base pipe rotating speed r/min | Moving speed mm/s of spray gun | Distance mm of spray gun |
| 180 | 20 | 30 |
4) And machining the target after cold spraying to obtain a finished product.
Through detection, the coating surface of the titanium target prepared in the embodiment has small pits, the thickness is 12mm, the density is 95%, the oxygen content is 926ppm, and the powder utilization rate is 80%.
Comparative example 1:
a preparation method of a rotary titanium target comprises the following steps:
1) preparing titanium powder with D50 being 30 mu m and the purity being 3N 5;
2) selecting a titanium tube with the inner diameter of 125mm, the outer diameter of 133mm and the tube length of 500mm as a target base tube, and removing impurities such as surface dirt and the like by absolute ethyl alcohol;
3) mounting the target base tube on transmission equipment, and adjusting a motor to enable the target base tube to rotate around a central shaft; starting cold spraying equipment, enabling a cold spraying spray gun to relatively reciprocate in the horizontal direction, and introducing normal-temperature water as circulating cooling water; meanwhile, the dust removal air port is opposite to the circumferential area of the spray gun and moves back and forth along with the spray gun, so that undeposited powder can be collected conveniently, titanium powder is sputtered onto the surface of the base tube at a high speed through the cold spraying spray gun to form a coating through deposition, a target material is obtained, wherein main gas and carrier gas used for cold spraying are nitrogen, the pressure of the carrier gas is 5Mpa, and the technological parameters of cold spraying are as shown in Table 7:
TABLE 7
4) And machining the target after cold spraying to obtain a finished product.
Through detection, the titanium target coating prepared by the comparative example has no cracks and pits, and the target has the following indexes: the thickness is 3mm, the density is 95%, the oxygen content is 980ppm, the powder utilization rate is 57%, and the bonding strength is 78 MPa.
From example 1 and comparative example 1, we can see that: when the same powder is cold-sprayed on a titanium pipe, the difference between the direct spraying (comparative example 1) and the spraying after the sand blasting priming (example 1) is mainly the difference of the bonding strength of the coating, and the difference of the powder utilization rate is not large. This is related to the repair of the remaining target of the titanium target.
Comparative example 2:
a preparation method of a rotary titanium target comprises the following steps:
1) preparing titanium powder with D50 being 40 mu m and the purity being 3N;
2) selecting a stainless steel tube with the inner diameter of 125mm, the outer diameter of 133mm and the tube length of 1220mm as a target base tube; carrying out sand blasting treatment on the target base tube by using cast steel sand, and then using a copper-nickel wire for electric arc priming, wherein the surface roughness Ra of the target base tube after the priming treatment is 260-350 mu m;
3) mounting the primed target base tube on transmission equipment, and adjusting a motor to enable the base tube to rotate around a central shaft; starting cold spraying equipment, enabling a cold spraying spray gun to move back and forth relatively in the horizontal direction, introducing normal-temperature water as circulating cooling water, enabling a dust removal air port to face the circumferential area of the spray gun and move back and forth along with the spray gun, facilitating collection of undeposited powder, enabling titanium powder to be sputtered onto the surface of a base tube at a high speed through the cold spraying spray gun to form a coating through deposition, and obtaining a target material, wherein main gas and carrier gas used for cold spraying adopt nitrogen, the carrier gas pressure is 5Mpa, and the technological parameters of cold spraying are specifically shown in a table 8:
TABLE 8
| Main air pressure Mpa | Main air flow Slpm | Heating temperature of main gas |
| 5.5 | 2220 | 830 |
| Base pipe rotating speed r/min | Moving speed mm/s of spray gun | Distance mm of spray gun |
| 150 | 25 | 45 |
4) And machining the target after cold spraying to obtain a finished product.
The titanium target prepared by the comparative example is detected to have the coating thickness of 7.5mm, the density of 96 percent, the oxygen content of 900ppm and the powder utilization rate of 68 percent.
For example 3 and comparative example 2, the same particle size powder, the same spray process parameters, and the higher the purity of the powder, the better the plastic deformation, and the relatively high powder utilization.
Comparative example 3
A preparation method of a rotary titanium target comprises the following steps:
1) preparing titanium powder with D50 being 90 mu m and the purity being 4N 5;
2) selecting a stainless steel tube with the inner diameter of 125mm, the outer diameter of 133mm and the tube length of 2600mm as a target base tube; carrying out sand blasting treatment on the target base tube by using cast steel sand, and then using a copper-nickel wire for electric arc priming, wherein the surface roughness Ra of the target base tube after the priming treatment is 260-350 mu m;
3) mounting the primed target base tube on transmission equipment, and adjusting a motor to enable the base tube to rotate around a central shaft; starting cold spraying equipment, enabling a cold spraying spray gun to move back and forth relatively in the horizontal direction, introducing normal-temperature water as circulating cooling water, enabling a dust removal air port to face the circumferential area of the spray gun and move back and forth along with the spray gun, facilitating collection of undeposited powder, enabling titanium powder to be sputtered onto the surface of a base tube at a high speed through the cold spraying spray gun to form a coating through deposition, and obtaining a target material, wherein main gas and carrier gas used for cold spraying adopt nitrogen, the carrier gas pressure is 5Mpa, and the technological parameters of cold spraying are specifically shown in a table 9:
TABLE 9
| Main air pressure Mpa | Main air flow Slpm | Heating temperature of main gas |
| 6.5 | 2170 | 920 |
| Base pipe rotating speed r/min | Moving speed mm/s of spray gun | Distance mm of spray gun |
| 150 | 30 | 40 |
4) And machining the target after cold spraying to obtain a finished product.
The titanium target coating prepared by the comparative example has no crack but has larger pits through detection. The coating thickness was 9mm, the density was 92%, the oxygen content was 900ppm, and the powder utilization rate was 77%.
For example 4 and comparative example 3, the powders were of different particle size and of the same purity. When the particle size of the powder becomes large, even if the main gas pressure and the main gas temperature are increased to expect that the particles can be plastically deformed after running at a high speed, the particles with larger particle size are not deformed to form pits; and as the thickness of the coating layer increases, pits become gradually larger from small to large, and finally the coating layer possibly takes on a honeycomb shape.
From the above examples and comparative examples, the purity of the titanium powder was not less than 4N; d50 is 30-60 mu m; the cold spraying process parameters are as follows: main gas pressure: 5-6.5Mpa, carrier gas pressure: 5-7 Mpa; the main air heating temperature is 850 ℃ and 920 ℃; the distance between the spray guns is 30-45mm, which is more beneficial to preparing the target material with high density, high purity, low oxygen content and small grain size.
The invention also provides two repair methods of the rotary titanium target.
One is direct cold spraying on the titanium target, mainly to the titanium target life cycle inner surface problem and repair, this repair method is specifically: wiping the surface of the residual target with absolute ethyl alcohol, and performing cold spraying on the residual target. Therefore, the stability of the grain size can be ensured, and the bonding layer is not adhered with cast steel grit and the like to influence the terminal coating product.
The other method is that the surface of the residual target is cleaned by absolute ethyl alcohol, and then the surface of the residual target is subjected to sand blasting treatment and then is subjected to cold spraying, and the method mainly aims at the residual target replaced by an equipment manufacturer. These targets are replaced after the end of their useful life. Therefore, to ensure a thicker coating is applied over the stub target, the stub target surface needs to be grit blasted to facilitate greater bond strength.
Example 7:
the embodiment is a method for repairing and spraying a 4mm coating on a backing integrated titanium target, and specifically comprises the following steps:
1) titanium powder with D50 ═ 45 μm and purity 5N (guest annealed titanium target purity 5N) was prepared;
2) this integrated titanium target was observed: the surface has a plurality of black spots, pits, chromatic aberration and the like; processing the surface, removing a coating with a certain thickness until no abnormity occurs, wiping the coating clean by absolute ethyl alcohol, and recording the outer diameter A of the current titanium target coating;
3) mounting the titanium target on a transmission device, and adjusting a motor to rotate around a central shaft; starting cold spraying equipment, enabling a cold spraying spray gun to move back and forth relatively in the horizontal direction, introducing normal-temperature water as circulating cooling water, enabling a dust removal air port to face the circumferential area of the spray gun and move back and forth along with the spray gun, facilitating collection of undeposited powder, enabling titanium powder to be sputtered onto the surface of a titanium target at a high speed through the cold spraying spray gun to deposit to form a coating, and obtaining a target material, wherein main gas and carrier gas used for cold spraying adopt nitrogen, the carrier gas pressure is 5Mpa, and the technological parameters of cold spraying are as shown in Table 10:
watch 10
| Main air pressure Mpa | Main air flow Slpm | Heating temperature of main gas |
| 5 | 2170 | 900 |
| Base pipe rotating speed r/min | Moving speed mm/s of spray gun | Distance mm of spray gun |
| 180 | 20 | 30 |
4) And machining the target after cold spraying to obtain a finished product, wherein the outer diameter size B of the target coating after spraying is obtained.
Through detection, the density of the repaired titanium target is 95%, the oxygen content is 750ppm, and the powder utilization rate is 94%. Performing destructive test on the target: the coating was run down from the outer diameter dimension B until the outer diameter dimension A was approached, and the contact surface condition was observed. As a result, no "peeling" or the like was observed.
Example 8:
the embodiment is a method for repairing and spraying a 9mm coating on a residual titanium target, which specifically comprises the following steps:
1) titanium powder having a purity of 4N (residual target purity of 4N) and D50 ═ 45 μm was prepared;
2) the surface of the residual target is wiped clean by absolute ethyl alcohol;
3) installing the residual target on a transmission device, and adjusting a motor to enable the residual target to rotate around a central shaft; starting cold spraying equipment, enabling a cold spraying spray gun to move back and forth relatively in the horizontal direction, introducing normal-temperature water as circulating cooling water, enabling a dust removal air port to face the circumferential area of the spray gun and move back and forth along with the spray gun, facilitating collection of undeposited powder, enabling titanium powder to be sputtered onto the surface of a titanium target at a high speed through the cold spraying spray gun to deposit to form a coating, and obtaining a target material, wherein main gas and carrier gas used for cold spraying adopt nitrogen, the carrier gas pressure is 5Mpa, and the technological parameters of cold spraying are specifically shown in a table 11:
TABLE 11
| Main air pressure Mpa | Main air flow Slpm | Heating temperature of main gas |
| 5.5 | 2170 | 900 |
| Base pipe rotating speed r/min | Moving speed mm/s of spray gun | Distance mm of spray gun |
| 180 | 20 | 30 |
4) And machining the target after cold spraying to obtain a finished product.
Through detection, the density of the repaired titanium target is 96%, the oxygen content is 780ppm, and the powder utilization rate is 92%.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The preparation method of the rotary titanium target is characterized by comprising the following steps:
(1) preparing titanium powder with the average grain diameter D50 of 30-80 mu m, preferably 30-60 mu m;
(2) performing surface treatment on the target base tube;
(3) cold spraying: and (3) mounting the surface-treated target base tube on a transmission device, enabling the target base tube to rotate around a central shaft, enabling the spray gun to relatively move back and forth along the horizontal direction of the target base tube, starting the cooling device, then carrying out cold spraying on the titanium powder on the surface of the target base tube through the spray gun, and depositing to form a coating to obtain the target.
2. The method for preparing a rotary titanium target according to claim 1, wherein the purity of the titanium powder in the step (1) is not less than 99.95%.
3. The method for producing a rotating titanium target according to claim 1, wherein in the step (2), the surface treatment includes a blasting treatment and a primer treatment.
4. The method for preparing a rotary titanium target according to claim 3, wherein the abrasive used for the sand blasting is white corundum, steel wire cut shot or cast steel sand, preferably cast steel sand;
the priming treatment mode is electric arc spraying, flame spraying or plasma spraying, and raw materials used for the priming treatment are selected from wire materials or powder, wherein the wire materials are selected from at least one of copper aluminum wires, copper nickel wires, nickel aluminum wires and Monel wires; the powder is at least one selected from nickel-coated aluminum composite powder and aluminum-coated nickel composite powder, preferably, the priming treatment mode is electric arc spraying, and more preferably, copper-nickel wire electric arc spraying.
5. The method for preparing a rotary titanium target according to claim 4, wherein the surface roughness Ra of the target base tube after the priming treatment is 400 μm, preferably 350 μm and 220-.
6. The method for preparing a rotary titanium target according to claim 1, wherein in the step (3), the rotation speed of the target base tube is 120-200r/min, preferably 150-180 r/min.
7. The method for preparing a rotating titanium target according to claim 1, wherein in the step (3), the moving speed of the lance is 20 to 40mm/s, preferably 20 to 30 mm/s.
8. The method for preparing a rotary titanium target according to any one of claims 1 to 7, wherein in the step (3), the cold spraying process parameters are as follows: the main gas pressure is 4-8Mpa, the carrier gas pressure is 4.5-8.5Mpa, the main gas heating temperature is 500-.
9. The rotating titanium target prepared by the method of any one of claims 1-8, wherein the rotating titanium target has an oxygen content of 1000ppm or less and a grain size of 40 μm or less.
10. The method for repairing the rotating titanium target is characterized by comprising the following steps of:
(1) preparing titanium powder with the average grain diameter D50 of 30-80 mu m;
(2) carrying out surface treatment on the residual target;
(3) cold spraying: installing the surface-treated residual target on a transmission device, enabling the residual target to rotate around a central shaft of the residual target, enabling a spray gun to relatively move back and forth along the horizontal direction of the residual target, starting a cooling device, then cold spraying titanium powder on the surface of the residual target through the spray gun, depositing to form a coating, and obtaining a repaired target,
wherein, the rotating speed of the residual target is 120-200r/min, preferably 150-180 r/min;
the moving speed of the spray gun is 20-40mm/s, preferably 20-30 mm/s;
the technological parameters of cold spraying are as follows: the main gas pressure is 4-8Mpa, the carrier gas pressure is 4.5-8.5Mpa, the main gas heating temperature is 500-.
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| CN113355628A (en) * | 2021-05-24 | 2021-09-07 | 芜湖映日科技股份有限公司 | Method for enhancing bonding strength between base tube and target coating |
| CN114250461A (en) * | 2021-12-13 | 2022-03-29 | 广东省科学院新材料研究所 | Rotary rare earth target material and preparation method and application thereof |
| US20220241882A1 (en) * | 2019-06-25 | 2022-08-04 | Lisi Automotive | Method for attaching parts by spraying a powder of a ductile material; corresponding assembly |
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