CN108796493B - Hole sealing modification method for cold spraying coating on surface of light metal - Google Patents
Hole sealing modification method for cold spraying coating on surface of light metal Download PDFInfo
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- CN108796493B CN108796493B CN201810563205.9A CN201810563205A CN108796493B CN 108796493 B CN108796493 B CN 108796493B CN 201810563205 A CN201810563205 A CN 201810563205A CN 108796493 B CN108796493 B CN 108796493B
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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
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- C23C24/02—Coating starting from inorganic powder by application of pressure only
- C23C24/04—Impact or kinetic deposition of 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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/06—Solid state diffusion of only metal elements or silicon into metallic material surfaces using gases
- C23C10/08—Solid state diffusion of only metal elements or silicon into metallic material surfaces using gases only one element being diffused
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Abstract
The invention relates to the technical field of light metal surface protection, in particular to a technical method for hole sealing and modification of a light metal surface protection coating. The invention discloses a plasma deposition heat treatment process method for sealing and diffusing a cold spraying coating on the surface of a light metal based on a double-layer glow plasma diffusion technology; the light metal workpiece treated by cold spraying coating is put into a double-glow furnace, the target material with the same material as the workpiece and the coating is heated by using double hollow cathode glow discharge effect, the target material is placed on a source electrode frame, is heated to form evaporation and sputtering under the bombardment of plasma generated by glow discharge, is deposited on the surface of the workpiece, and is diffused when the workpiece is heated, and the cold spraying of the workpiece is subjected to hole sealing and diffusion treatment, so that holes on the surface and inside of the coating are eliminated, and a diffusion layer is formed between the coating and a base workpiece, so that the defect of low bonding strength between the cold spraying coating and the base workpiece is overcome.
Description
Technical Field
The invention relates to the technical field of surface protection of shells and parts of airplanes, ships, automobiles and the like, in particular to a technical method for hole sealing and modification of a light metal surface protective coating.
Background
Cold spraying is a coating preparation technology in which metal particles are accelerated to a critical speed (supersonic speed) by compressed air, and the metal particles are physically deformed and accumulated after directly hitting the surface of a substrate to form a coating. The metal particles are flattened on the surface of the substrate and firmly attached, and the metal particles are not melted in the whole process. The cold spraying basically has no working condition requirement, and the noise is less than 60 decibels. The cold spraying has no high temperature, no flame, no dangerous gas, no radiation and chemical waste, free-hand operation, high safety, good directionality and strong operability, and has wide application in the preparation and maintenance of coating of airplanes, ships and automobiles.
In order to improve the corrosion resistance of the aircraft skin and parts, cold spraying technology is generally adopted to carry out coating protection and maintenance on the aircraft skin and parts. However, protective coatings prepared by cold spraying often have the defects of multiple holes and insufficient bonding strength. These defects cause the coating to lose its protective properties rapidly under service conditions.
The double-glow plasma diffusion plating technology (hereinafter referred to as double glow) is to form an alloy layer with special physical and chemical properties on the surface of a conductive material by using plasma and a solid metal material as a supply source of elements to be diffused. In a vacuum chamber, two cathodes and one anode are provided. One of the cathodes is made of the element to be alloyed, called the source, and a controllable direct current power supply is connected between the anode and the cathode (workpiece) and the source, respectively. When the vacuum chamber reaches a certain vacuum degree and argon is filled to reach a certain working pressure, two direct current power supplies are connected, so that two groups of glow discharge, namely double-layer glow discharge, are respectively generated between the anode and the workpiece and between the anode and the source electrode. Under the action of argon ion bombardment generated by glow discharge, alloy elements on the source and the workpiece surface are sputtered, and because the source potential is set to be lower than the workpiece potential or the source power density is higher than the workpiece power density, the supply quantity of particles sputtered from the source is far more than the reverse sputtering quantity of the cathode, so that atoms of the sputtered elements to be diffused fly to the workpiece surface at high speed, are adsorbed by the workpiece surface and diffuse inwards, and the designed alloy layer is formed on the workpiece surface. The temperature can be accurately controlled by adjusting parameters such as working air pressure, source electrode potential, cathode electrode potential and the like, the control of the content of alloy elements and the thickness of a permeable layer in an alloy layer can be realized under certain heat preservation time, and a diffusion layer (creep weight. the current situation and the development of the plasma surface metallurgy technology. the Chinese engineering science 2002 is formed between a coating and a substrate workpiece;2:36-41.）。
based on the principle, the double glow technology can be used for eliminating the holes of the cold spraying coating and improving the bonding strength of the coating and the workpiece. The process method has important significance for further research and application of the cold spraying technology in the technical field of surface protection of shells and parts of airplanes, ships, automobiles and the like.
Disclosure of Invention
The invention aims to overcome the defects that the cold spraying protective coating on the surface of the light metal in the prior art often has many holes and insufficient bonding strength, and provides a surface protection technology for sealing and modifying the cold spraying coating on the surface of the light metal. According to the invention, a double-layer glow plasma diffusion plating technology is adopted to carry out hole sealing modification treatment on the workpiece prepared by the cold spraying coating on the surface of the light metal, so that the porosity of the coating is greatly reduced, a diffusion layer is formed between the coating and the substrate workpiece, the bonding strength of the cold spraying coating and the substrate workpiece is obviously improved, and the protection performance of the coating is improved.
The technical principle of the double-layer glow plasma diffusion plating of the invention is as follows: in a vacuum chamber, two cathodes and an anode are arranged; one of the cathodes is a target material with the same material as a light metal surface cold spray coating, and is placed in a crucible made of a conductive material (such as graphite, refractory metal or high-temperature alloy), and is also called as a source electrode; the other cathode is a base workpiece; the anode is a grounding electrode, namely a furnace body; a controllable direct current power supply is respectively connected between the anode and the cathode workpiece and between the anode and the source target material; when the vacuum chamber reaches a certain vacuum degree and argon is filled to reach a certain working pressure, two direct current power supplies are connected to enable two groups of glow discharges to be generated between the anode and the cathode workpiece and between the anode and the source target respectively; under the bombardment action of argon ions generated by glow discharge, the source electrode is heated and melted and generates evaporation, and meanwhile, the bombardment of the argon ions also sputters a large amount of coating atoms and atom groups which are the same as the material. The sputtered and evaporated atoms and radicals fly to the surface of the workpiece at high speed and are adsorbed by the surface of the workpiece for deposition. The electric field applied to the workpiece also generates glow discharge to heat the workpiece, and after reaching a proper temperature, the coating deposited on the surface of the workpiece is diffused inwards with the same material atoms, so that the coating on the surface of the workpiece is more compact, the porosity is greatly reduced, and a diffusion layer with a certain thickness is formed between the substrate workpiece and the coating. The temperature can be accurately controlled by adjusting parameters such as working air pressure, source electrode potential, cathode potential, source electrode-workpiece distance and the like, and the control of the compactness of the coating and the thickness of the diffusion layer can be realized under certain heat preservation time.
The invention realizes the purpose through the following technical scheme: a hole sealing modification method for a light metal surface cold spraying coating is characterized in that a double-layer glow plasma diffusion plating furnace is adopted to carry out diffusion plating on a workpiece prepared by the light metal cold spraying coating, and a diffusion layer is formed between a light metal matrix and the cold spraying coating.
Preferably, the hole sealing modification method of the light metal surface cold spray coating comprises the following specific steps: placing the light metal surface cold spraying coating and the same material target material into a vacuum chamber and placing the vacuum chamber on a source electrode, and placing a light metal surface cold spraying coating workpiece below the source electrode to adjust a certain electrode spacing; adjusting a vacuum chamber to reach a certain vacuum degree, filling argon to working pressure, applying direct-current negative voltage to a source electrode to enable the target material in the source electrode to be slightly melted and keep a discharge sputtering state, then applying negative voltage to a light metal surface cold spray coating workpiece to enable the workpiece to be heated to a process temperature, adjusting the negative voltage of the light metal surface cold spray coating workpiece to 200-750V, and keeping the temperature for a certain time; and then cooling and discharging from the furnace to obtain the hole sealing modified light metal surface cold spraying coating workpiece.
Preferably, the distance between the poles is 10-50 mm;
preferably, the pressure of the working air pressure is 10-80 Pa;
preferably, the voltage of the direct current negative voltage applied to the source electrode is 200-1000V;
preferably, the negative voltage of the negative voltage applied to the light metal surface cold spray coating workpiece is 200-1000V;
preferably, the process temperature is 200-900 ℃;
preferably, the heat preservation for a certain time is 0.5-10 hours.
Preferably, the cold spraying coating is a cold spraying pure titanium coating or a cold spraying pure copper coating;
the invention has the following beneficial effects:
1) the compactness of the coating of the light metal surface cold spray coating workpiece treated by adopting the double-layer glow plasma diffusion coating technology is greatly improved, and a diffusion layer is formed between the coating and the matrix workpiece, so that the bonding strength between the matrix workpiece and the cold spray coating is greatly improved;
2) due to the typicality of the research object, the research result can be popularized to other fields, and the engineering value is also very outstanding;
3) the previous research mostly focuses on the work of the dual-glow technology in the aspect of carrying out diffusion coating treatment on the surface of heavy metal with high melting point at higher working temperature (more than 700 ℃), and the invention fills the technical application blank of the dual-glow technology in carrying out surface treatment on light alloy at low temperature (less than 600 ℃).
Drawings
FIG. 1 is a schematic view of hole sealing modification treatment of a cold spray coating by a dual-glow technique.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention.
Example 1
Hole sealing modification treatment for cold spraying pure titanium coating on 2024 aluminum alloy surface
(1) And (4) sample pretreatment. And cleaning alcohol on the surface of the sample with the 2024 aluminum alloy surface cold spraying pure titanium coating and drying.
(2) Loading into a dual-glow diffusion coating furnace. Placing a pure titanium infiltration source and a 2024 aluminum alloy surface cold spraying pure titanium coating workpiece, and adjusting the electrode distance to be 40 mm.
(3) And (6) vacuumizing. Closing the air inlet, opening the vacuum pump, and pumping the air pressure in the furnace to 10-1Below Pa, argon is then introduced to a working pressure of 40 Pa.
(4) The sample was plasma cleaned. And (3) turning on cooling water, starting a power supply, turning on the power supply of the 2024 aluminum alloy surface cold spraying pure titanium coating workpiece, applying 500V voltage, and bombarding the 2024 aluminum alloy surface cold spraying pure titanium coating workpiece for about 30min by using plasma beams generated by glow discharge, wherein the sample is further cleaned on one hand, and the surface is activated on the other hand to facilitate the adsorption of active atoms.
(5) And (5) diffusion plating. After the pre-bombardment, applying a voltage of 600V to a source electrode of the dual-glow diffusion coating furnace until the pure titanium target material is micro-molten, and adjusting to 350-400V for keeping. And then, the voltage of a 2024 aluminum alloy surface cold spraying pure titanium coating workpiece is increased to 700V, the temperature of the sample reaches 350 ℃, and then the temperature is adjusted to 600-650V to keep the temperature.
(6) And (5) cooling. And after the temperature is kept for 3.5 hours, cutting off a source power supply of the pure titanium target, and regulating the voltage of the 2024 aluminum alloy surface cold spraying pure titanium coating workpiece to be about 200V, so that the 2024 aluminum alloy surface cold spraying pure titanium coating workpiece is in weak glow discharge and is gradually cooled.
(7) And (4) discharging. And cutting off the electrode power supply of the 2024 aluminum alloy surface cold spraying pure titanium coating workpiece after the temperature of the sample is reduced to be below 200 ℃, closing the Ar air valve, and cutting off the power supply of the vacuum pump and cooling water. And opening the air release valve to fill air, and opening the furnace cover and taking out the sample after the pressure of the working chamber is recovered to the air pressure.
After the hole sealing modification treatment by the double glow technology, the porosity of the cold spraying pure titanium coating on the surface of the 2024 aluminum alloy is reduced from 8.43% to 0.98%, a diffusion layer with the thickness of 2 mu m is formed between the pure titanium coating and the 2024 aluminum alloy, and the binding force between the pure titanium coating and the 2024 aluminum alloy substrate is improved from 43.5N to 77.9N.
Example 2
Hole sealing modification treatment for cold spraying pure copper coating on 2024 aluminum alloy surface
(1) And (4) sample pretreatment. The surface of the sample is cleaned with alcohol and dried, and polished and then cleaned if necessary.
(2) Loading into a dual-glow diffusion coating furnace. Placing a pure copper target material seepage source and a 2024 aluminum alloy surface cold spraying pure copper coating workpiece, and adjusting the electrode distance to 30 mm.
(3) And (6) vacuumizing. Closing the air inlet, opening the vacuum pump, and pumping the air pressure in the furnace to 10-1Below Pa, argon was then introduced to a working pressure of 30 Pa.
(4) The sample was plasma cleaned. And (3) turning on cooling water, starting a power supply, turning on the power supply of the 2024 aluminum alloy surface cold spraying pure copper coating workpiece, applying 400V voltage, and bombarding the 2024 aluminum alloy surface cold spraying pure copper coating workpiece for about 30min by using plasma beams generated by glow discharge, wherein the sample is further cleaned on one hand, and the surface is activated on the other hand to facilitate the adsorption of active atoms.
(5) And (5) diffusion plating. After the pre-bombardment, the source voltage of the pure copper target is 650V, and the target is adjusted to 400-450V for maintenance after the micro-melting. And then, the voltage of a 2024 aluminum alloy surface cold spraying pure copper coating workpiece is increased to 700V, the temperature of the sample reaches 400 ℃, and then the temperature is adjusted to 550-650V to keep the temperature.
(6) And (5) cooling. And after the heat preservation is carried out for 7 hours, cutting off a source power supply, and regulating the electrode voltage of the 2024 aluminum alloy surface cold spraying pure copper coating workpiece to be about 250V so that the workpiece electrode is in weak glow discharge and is gradually cooled.
(7) And (4) discharging. And cutting off the electrode power supply of the 2024 aluminum alloy surface cold spraying pure copper coating workpiece after the temperature of the sample is reduced to be below 200 ℃, closing the Ar air valve, and cutting off the power supply of the vacuum pump and cooling water. And opening the air release valve to fill air, and opening the furnace cover and taking out the sample after the pressure of the working chamber is recovered to the air pressure.
The porosity of the 2024 aluminum alloy surface after hole sealing modification treatment of the cold spraying pure copper coating is reduced to 0.53% from 6.71%, a diffusion layer with the thickness of 3 mu m is formed between the pure copper coating and the 2024 aluminum alloy, and the bonding force between the pure copper coating and the 2024 aluminum alloy substrate is improved to 65.1N from 31.3N.
Although the embodiments of the present invention have been described in detail, it should be understood that various changes, substitutions, and alterations can be made hereto without departing from the spirit and scope of the invention.
Claims (2)
1. A hole sealing modification treatment method for a cold spraying pure titanium coating on the surface of 2024 aluminum alloy comprises the following steps:
(1) sample pretreatment: cleaning alcohol on the surface of a sample with the 2024 aluminum alloy surface cold spraying pure titanium coating and drying;
(2) loading into a dual-glow diffusion coating furnace: placing a pure titanium infiltration source and a 2024 aluminum alloy surface cold spraying pure titanium coating workpiece, and adjusting the electrode spacing to be 40 mm;
(3) vacuumizing: closing the air inlet, opening the vacuum pump, and pumping the air pressure in the furnace to 10-1Pa below, then introducing argon to 40A working air pressure of Pa;
(4) plasma cleaning of the sample: turning on cooling water, starting a power supply, firstly turning on the power supply of the 2024 aluminum alloy surface cold spraying pure titanium coating workpiece, applying 500V voltage, and bombarding the 2024 aluminum alloy surface cold spraying pure titanium coating workpiece by using plasma beams generated by glow discharge for 30min, on one hand, further cleaning the sample, and on the other hand, activating the surface to facilitate the adsorption of active atoms;
(5) and (3) diffusion plating: after pre-bombardment, applying a voltage of 600V to a source electrode of the dual-glow diffusion coating furnace until the pure titanium target material is micro-molten, and adjusting to 350-400V for keeping; then, the voltage of a 2024 aluminum alloy surface cold spraying pure titanium coating workpiece is increased to 700V, the temperature of a sample reaches 350 ℃, and then the temperature is adjusted to 600-650V to keep the temperature;
(6) cooling: after the temperature is kept for 3.5 hours, cutting off a source power supply of the pure titanium target, and regulating the voltage of the 2024 aluminum alloy surface cold spraying pure titanium coating workpiece to 200V, so that the 2024 aluminum alloy surface cold spraying pure titanium coating workpiece is in weak glow discharge and gradually cooled;
(7) discharging: cutting off a power supply of a 2024 aluminum alloy surface cold spraying pure titanium coating workpiece electrode after the temperature of the sample is reduced to below 200 ℃, closing an Ar air valve, and cutting off a vacuum pump power supply and cooling water; opening an air release valve to fill air, opening a furnace cover after the pressure of the working chamber is recovered to the air pressure, and taking out a sample;
after the hole sealing modification treatment by the double glow technology, the porosity of the cold spraying pure titanium coating on the surface of the 2024 aluminum alloy is reduced from 8.43% to 0.98%, a diffusion layer with the thickness of 2 microns is formed between the pure titanium coating and the 2024 aluminum alloy, and the binding force between the pure titanium coating and the 2024 aluminum alloy matrix is improved from 43.5N to 77.9N.
2. A hole sealing modification treatment method for a cold spraying pure copper coating on the surface of 2024 aluminum alloy comprises the following steps:
(1) sample pretreatment: cleaning alcohol on the surface of a sample with the 2024 aluminum alloy surface cold spraying pure copper coating and drying;
(2) loading into a dual-glow diffusion coating furnace: placing a pure copper target material seepage source and a 2024 aluminum alloy surface cold spraying pure copper coating workpiece, and adjusting the electrode distance to 30 mm;
(3) vacuumizing: closing the air inlet, opening the vacuum pump, and pumping the air pressure in the furnace to 10-1Introducing argon to the working pressure of 30Pa below Pa;
(4) plasma cleaning of the sample: turning on cooling water, starting a power supply, firstly turning on the power supply of the 2024 aluminum alloy surface cold spraying pure copper coating workpiece, applying 400V voltage, and bombarding the 2024 aluminum alloy surface cold spraying pure copper coating workpiece for 30min by using plasma beams generated by glow discharge, on one hand, further cleaning the sample, and on the other hand, activating the surface to facilitate the adsorption of active atoms;
(5) and (3) diffusion plating: after pre-bombardment, applying 650V of the source voltage of the pure copper target material until the target material is micro-melted, and adjusting to 400-450V for keeping; then, the voltage of a 2024 aluminum alloy surface cold spraying pure copper coating workpiece is increased to 700V, the temperature of a sample reaches 400 ℃, and then the temperature is adjusted to 550-650V to keep the temperature;
(6) cooling: after heat preservation is carried out for 7 hours, a source power supply is cut off, the electrode voltage of a 2024 aluminum alloy surface cold spraying pure copper coating workpiece is reduced to 250V, the workpiece electrode is subjected to weak glow discharge, and the temperature is gradually reduced;
(7) discharging: cutting off a power supply of a 2024 aluminum alloy surface cold spraying pure copper coating workpiece electrode after the temperature of the sample is reduced to below 200 ℃, closing an Ar air valve, and cutting off a vacuum pump power supply and cooling water; opening an air release valve to fill air, opening a furnace cover after the pressure of the working chamber is recovered to the air pressure, and taking out a sample;
the porosity of the 2024 aluminum alloy surface after the hole sealing modification treatment of the cold spraying pure copper coating is reduced to 0.53% from 6.71%, a diffusion layer with the thickness of 3 mu m is formed between the pure copper coating and the 2024 aluminum alloy, and the bonding force between the pure copper coating and the 2024 aluminum alloy substrate is improved to 65.1N from 31.3N.
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