CN111020479B - High-shielding-piece corrosion-resistant multi-element coating, preparation method thereof and device used by preparation method - Google Patents

High-shielding-piece corrosion-resistant multi-element coating, preparation method thereof and device used by preparation method Download PDF

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CN111020479B
CN111020479B CN201911355671.9A CN201911355671A CN111020479B CN 111020479 B CN111020479 B CN 111020479B CN 201911355671 A CN201911355671 A CN 201911355671A CN 111020479 B CN111020479 B CN 111020479B
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deposition
tisin
film layer
tisicn
high shielding
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CN111020479A (en
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廖斌
欧阳晓平
何光宇
何卫锋
罗军
陈琳
张旭
吴先映
庞盼
韩然
英敏菊
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Beijing Normal University
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    • C—CHEMISTRY; METALLURGY
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    • 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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
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    • 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
    • C23C14/04—Coating on selected surface areas, e.g. using masks
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    • 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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/081—Oxides of aluminium, magnesium or beryllium
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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
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • C23C14/325—Electric arc evaporation
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    • 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
    • C23C14/3485—Sputtering using pulsed power to the target
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    • 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
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/40—Coatings including alternating layers following a pattern, a periodic or defined repetition

Abstract

The invention provides a high shielding piece corrosion-resistant multi-element coating, a preparation method thereof and a device used by the preparation method, and belongs to the technical field of thin film deposition. The preparation method of the high shielding piece corrosion-resistant multi-element coating provided by the invention comprises the following steps: alternately and circularly depositing a TiSiN film layer and a TiSiCN film layer on a high shielding piece matrix by using a carbon-silicon target and a carbon-silicon-titanium target as cathodes and using a magnetic filtration deposition method, a multi-arc deposition method and a first high-power pulse magnetic control method to obtain a TiSiN/TiSiCN composite alternate layer; depositing Al on the surface of the TiSiN/TiSiCN composite alternating layer by a second high-power pulse magnetic control method2O3And (5) coating to obtain the high shielding piece corrosion-resistant multi-element coating. The high shielding piece prepared by the method is excellent in erosion resistance, salt mist resistance, acid and alkali corrosion resistance and the like of the corrosion-resistant multi-element coating by using three methods of magnetic filtration deposition, multi-arc deposition and high-power pulse magnetic control in a matching manner.

Description

High-shielding-piece corrosion-resistant multi-element coating, preparation method thereof and device used by preparation method
Technical Field
The invention relates to the technical field of thin film deposition, in particular to a high shielding piece corrosion-resistant multi-element coating, a preparation method thereof and a device used by the preparation method.
Background
When a helicopter or a conveyor takes off, lands and hovers at low altitude in a desert environment, an engine of the helicopter or the conveyor inevitably sucks a large amount of sand grains, and the sand grains repeatedly impact the blades of the air compressor to cause material abrasion and fatigue cracks; when a helicopter or a transporter takes off, lands and hovers at low altitude in a marine environment, an engine of the helicopter or the transporter can not avoid sucking a large amount of saline water, and blades can be seriously corroded due to the action of heat-salt-force in the high-speed rotation process; the flight safety and reliability of the aircraft engine are seriously affected, and the service life of the aircraft engine is greatly reduced.
In order to improve the performance of an engine against sand impact, corrosion and the like, a hard and high-density coating is generally required to be deposited on the surface of a compressor blade. However, the higher the compactness of the coating, the greater the internal stress of the film layer, the greater the brittleness of the coating, and the insufficient toughness of the coating; the lower the compactness of the coating, the smaller the internal stress of the film layer, the poorer the relative compactness of the film layer and the poorer the corrosion resistance in a high-salt-spray environment. Therefore, the existing corrosion-resistant coating cannot meet the requirements of increasing the toughness and corrosion resistance of the blade surface coating at the same time.
Disclosure of Invention
The invention aims to provide a high-shielding-piece corrosion-resistant multi-element coating, a preparation method thereof and a device used by the preparation method. The preparation method provided by the invention can simultaneously increase the hard erosion wear resistance and the corrosion resistance of the coating.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a high shielding piece corrosion-resistant multi-element coating, which comprises the following steps:
alternately and circularly depositing a TiSiN film layer and a TiSiCN film layer on a high shielding piece matrix by using a carbon-silicon target and a carbon-silicon-titanium target as cathodes and using a magnetic filtration deposition method, a multi-arc deposition method and a first high-power pulse magnetic control method to obtain a TiSiN/TiSiCN composite alternate layer;
depositing Al on the surface of the TiSiN/TiSiCN composite alternating layer by a second high-power pulse magnetic control method2O3And (5) coating to obtain the high shielding piece corrosion-resistant multi-element coating.
Preferably, the high shielding piece base body is in contact with a TiSiN film layer or a TiSiCN film layer in the TiSiN/TiSiCN composite alternating layer; the Al is2O3The film layer is contacted with the TiSiN film layer or the TiSiCN film layer in the TiSiN/TiSiCN composite alternating layer.
Preferably, the working conditions of the magnetic filtration deposition method comprise: the cathode target is a carbon-silicon target, the current is 1-50A, the angle between the direction of the pulse magnetic field and the plane of the cathode is 45-90 degrees, the cathode arcing current is 1-100A, and the magnetic filtering current intensity is 1.0-2.0A.
Preferably, the working conditions of the multi-arc deposition method include: the cathode target is a carbon-silicon target, the cathode arcing current is 1-120A, and the arc voltage is 10-40V.
Preferably, the working conditions of the first high-power pulse magnetron method include: the cathode target material is a carbon-silicon-titanium target, the arc starting power is 2-12 kW, the voltage is 0-400V, the current is 0-300A, the voltage of pulse bias is 20-50 kV, the pulse width is 0.1-1.2 ms, the pulse frequency is 1-100 Hz, the duty ratio is 0-1/10000, the peak power is 5-15 kW, and the deposition time is 1-10 h.
Preferably, the operating conditions of the second high power pulse method include: the cathode target is an aluminum target, the voltage of pulse bias is 20-50 kV, the pulse width is 0.1-1.2 ms, the pulse frequency is 1-100 Hz, the first duty ratio is less than 1/10000, and the peak power is 5-15 kW; the voltage of the DC bias is 1-600V, and the second duty ratio is 1-80%.
The invention provides a high shielding member corrosion-resistant multi-element coating prepared by the preparation method in the technical scheme, which comprises a TiSiN/TiSiCN composite alternating layer and Al which are sequentially stacked on the surface of a high shielding member substrate2O3A film layer; the TiSiN-The TiSiCN composite alternating layer comprises TiSiN film layers and TiSiCN film layers which are alternately stacked.
Preferably, the Al is2O3The thickness of the film layer is 0.1-15 μm.
Preferably, the total thickness of the TiSiN/TiSiCN composite alternating layer is 1-50 mu m.
The invention also provides a device used in the preparation method in the technical scheme, which comprises a vacuum chamber, a multi-arc deposition device, a magnetic filtration deposition device, a first high-power pulse magnetron deposition device and a second high-power pulse magnetron deposition device;
the vacuum chamber is cylindrical; the multi-arc deposition device, the magnetic filtering deposition device, the first high-power pulse magnetron deposition device and the second high-power pulse magnetron deposition device are sequentially distributed along the circumferential direction of the vacuum chamber.
The invention provides a preparation method of a high shielding piece corrosion-resistant multi-element coating, which comprises the following steps: alternately and circularly depositing a TiSiN film layer and a TiSiCN film layer on a high shielding piece matrix by using a carbon-silicon target and a carbon-silicon-titanium target as cathodes and using a magnetic filtration deposition method, a multi-arc deposition method and a first high-power pulse magnetic control method to obtain a TiSiN/TiSiCN composite alternate layer; depositing Al on the surface of the TiSiN/TiSiCN composite alternating layer by a second high-power pulse magnetic control method2O3And (5) coating to obtain the high shielding piece corrosion-resistant multi-element coating.
Compared with the single anti-corrosion technology, the invention integrates the multi-arc deposition technology, the magnetic filtration deposition technology and the high-power pulse magnetic control technology, and can simultaneously increase the hardness, the erosion and wear resistance and the corrosion resistance of the blade of the coating, thereby forming the high-efficiency anti-corrosion coating. Compared with the traditional single bias technology, the high-power pulse bias and direct-current bias coupling technology is adopted as the bias, the ultrahigh-power pulse bias and direct-current bias coupling technology has an ultrahigh pulse peak value, the release of film stress can be realized under the transient heat peak effect, meanwhile, due to the high electric field intensity, the plasma can obtain sufficient energy, the diffraction of the plasma can be well realized, and the surface of a high-shielding part can be provided with a corrosion-resistant multi-element coating with high compactness and good uniformity.
Compared with a single film system, the high shielding piece corrosion-resistant multi-element coating prepared by the invention is a multi-layer composite system, is formed by compositing MAX phase and ternary ceramic phase, the ceramic phase for depositing TiSiN by magnetic filtration has high toughness, the MAX phase for depositing TiSiCN by high-power pulse has high hardness, and the film layer combined with high hardness and high toughness has good high/low-angle erosion resistance; the alumina ceramic phase prepared by utilizing the high-power pulse has good oxygen resistance, so that the integral coating of the high shielding piece corrosion-resistant multi-element coating has good corrosion resistance, and particularly has excellent corrosion resistance under the condition of high air pressure.
The device for preparing the corrosion-resistant multi-element coating of the high shielding piece is continuous rotary coating deposition, has good reliability and repeatability of equipment, has the advantages of high deposition rate and low time cost, and can realize batch production.
Drawings
FIG. 1 is a schematic diagram of a shielding component, wherein 101 is an un-shielded area, 102 is a high-shielded area, and 103 is an ultra-high-shielded area;
FIG. 2 is a schematic view of the high barrier corrosion-resistant multi-component coating, wherein 201 is the high barrier substrate, 202 is the TiSiN film, 203 is the TiSiCN film, and 204 is Al2O3A film layer;
FIG. 3 is a schematic view of a coating apparatus, wherein 31 is a magnetic filter deposition device, 32 is a first high power pulse deposition device, 33 is a second high power pulse deposition device, 34 is a multi-arc deposition device, 301 is a vacuum chamber door of the deposition device, 302 is a magnetic filter deposition port, 303 is a vacuum chamber wall, 304 is a first high power pulse deposition port, 305 is a second high power pulse deposition port, 306 is a multi-arc deposition port, and 307 is a fixture tool;
FIG. 4 is an erosion pattern for the high barrier erosion resistant multi-component coating prepared in example 1;
FIG. 5 is a sectional SEM image of a high barrier corrosion resistant multi-component coating prepared in example 5;
FIG. 6 is a hardness and toughness test chart of the corrosion-resistant multi-component coating of the high barrier material prepared in examples 1-5, wherein (a) - (b) are hardness test charts, and (c) - (e) are toughness test charts.
Detailed Description
The invention provides a preparation method of a high shielding piece corrosion-resistant multi-element coating, which comprises the following steps:
alternately and circularly depositing a TiSiN film layer and a TiSiCN film layer on a high shielding piece matrix by using a carbon-silicon target and a carbon-silicon-titanium target as cathodes and using a magnetic filtration deposition method, a multi-arc deposition method and a first high-power pulse magnetic control method to obtain a TiSiN/TiSiCN composite alternate layer;
depositing Al on the surface of the TiSiN/TiSiCN composite alternating layer by a second high-power pulse magnetic control method2O3And (5) coating to obtain the high shielding piece corrosion-resistant multi-element coating.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
According to the invention, a carbon-silicon target and a carbon-silicon-titanium target are used as cathodes, and a TiSiN film layer and a TiSiCN film layer are alternately and circularly deposited on a high shielding piece matrix by using a magnetic filtration deposition method, a multi-arc deposition method and a first high-power pulse magnetic control method, so that the TiSiN/TiSiCN composite alternate layer is obtained.
In the invention, the high shielding member substrate may be in contact with the TiSiN film layer or the TiSiCN film layer.
In the invention, the high shielding piece can be an engine blade, a water turbine impeller or a cutter, and in the embodiment of the invention, the corrosion-resistant multi-element coating is prepared by taking the engine blade as a substrate. In the present invention, a schematic diagram of the high shielding member is shown in fig. 1, where 101 is an unobstructed area, 102 is a high shielding area, and 103 is an ultra-high shielding area.
According to the invention, the high shielding piece matrix is preferably cleaned, and then the TiSiN film layer and the TiSiCN film layer are alternately and circularly deposited on the high shielding piece matrix. In the present invention, the cleaning is preferably performed by cleaning the surface of the substrate with an anode layer ion source. In the present invention, the anode layer ion source is preferably a gas ion source, more preferably a hydrogen ion source, an oxygen ion source, a nitrogen ion source, or an argon ion source; the energy of the anode layer ion source is preferably 1-1000 eV, more preferably 200-800 eV, and most preferably 400-600 eV; the beam intensity of the anode layer ion source is preferably 1-5A, more preferably 2-4A, and most preferably 3A. In the present invention, the surface roughness of the high shield base obtained after cleaning is preferably 0.1 to 0.3. mu.m, and more preferably 0.2. mu.m. In the invention, by cleaning the high shielding piece matrix with low energy, the oxide on the surface of the high shielding piece matrix can be completely etched by selecting different gases, the exposed matrix is a 'fresh' matrix and can be well contacted with a subsequently deposited film layer, and the bonding strength between the film layer and the matrix is further obviously improved.
In the present invention, the magnetic filtration deposition method preferably comprises the steps of: and enabling the ions generated by the titanium-silicon target to sequentially pass through the first shaking pulse oscillation coil and the drainage coil. In the present invention, the first shaking pulse coil is preferably disposed in the vicinity of the cathode. In the invention, the working conditions of the magnetic filtration deposition method comprise: the cathode target is preferably a titanium silicon target, and the current is preferably 1-50A, more preferably 10-40A, and most preferably 20-30A; the angle between the direction of the pulse magnetic field and the plane of the cathode is preferably 45-90 degrees, more preferably 50-80 degrees, and most preferably 60-70 degrees; the cathode arcing current is preferably 1-100A, more preferably 10-80A, and most preferably 40-60A; the magnetic filtering current intensity is preferably 1.0-2.0A, more preferably 1.2-1.8A, and most preferably 1.4-1.6A. The invention adopts a magnetic filtration deposition method to fill the holes formed by the multi-arc deposition technology in the deposition process and improve the compactness of the film layer.
In the invention, the current of the first oscillating pulse coil is strong pulse current and mainly controls the movement of titanium silicon arc spots, the direction of the strong pulse magnetic field and the plane of the cathode target are provided with an angle, the arc spots are unstable when the angle is larger than the angle range, the first oscillating pulse coil can greatly reduce the local ablation of long-time arc starting points, and the liquid drops are greatly reduced; the titanium-silicon dual-target arc spot motion control device is different from the existing metal arc source control coil, the titanium-silicon arc state is different from the metal, the titanium-silicon dual-target arc spot motion control difficulty is very high due to the fact that the bulk density, the melting point and the like of the titanium-silicon dual-target arc spot motion control device are different, the titanium-silicon dual-target arc spot motion is hardly influenced by a general weak magnetic field, and the titanium-silicon arc spot motion can be controlled by a proper strong magnetic field. In the present invention, the drainage wire wrap is preferably a wire wrap of the magnetic filtration elbow, wrapped around the magnetic filtration elbow.
In the present invention, the working conditions of the multi-arc deposition method include: the cathode target is preferably a titanium silicon target, the cathode arc starting current is preferably 1-120A, more preferably 10-100A, and most preferably 30-80A; the arc pressure is preferably 10-40V, more preferably 15-30V, and most preferably 20-30V. The invention adopts a multi-arc deposition method to overcome the defects of slow deposition speed, low efficiency and high internal stress of the magnetic filtration deposition and high-power pulse magnetic control technology, and improves the hard erosion wear resistance and the corrosion resistance of the corrosion-resistant multi-element coating.
In the invention, the working conditions of the first high-power pulse magnetron method comprise: the cathode target is preferably a titanium silicon carbon target; the arcing power is preferably 2-12 kW, more preferably 4-10 kW, and most preferably 6-8 kW; the voltage is preferably 0-400V, more preferably 50-300V, and most preferably 100-300V; the current is preferably 0 to 300A, more preferably 50 to 300A, and most preferably 100 to 300A; the voltage of the pulse bias is preferably 20-50 kV, more preferably 30-40 kV, and most preferably 35 kV; the pulse width is preferably 0.1-1.2 ms, more preferably 0.2-1.0 ms, and most preferably 0.5-0.8 ms; the pulse frequency is preferably 1-100 Hz, more preferably 10-80 Hz, and most preferably 30-60 Hz; the duty ratio is preferably 0-1/10000, more preferably 1/100000-1/10000; the peak power is preferably 5-15 kW, more preferably 7-12 kW, and most preferably 8-10 kW; the deposition time is preferably 1-10 h, more preferably 2-8 h, and most preferably 4-6 h.
In the invention, in the alternate circulation deposition process, the revolution speeds of the deposition port of the equipment adopted by the magnetic filtration deposition method, the deposition port of the equipment adopted by the multi-arc deposition method and the deposition port of the equipment adopted by the high-power pulse magnetic control method are independently and preferably 0.1-10 r/min, more preferably 1-8 r/min, and most preferably 2-5 r/min; the deposition time of the magnetic filtration deposition method, the multi-arc deposition method and the high-power pulse magnetic control method is not specially limited, and the thickness composite requirement of each film layer can be ensured, specifically, the deposition time is 0-10 s independently, more preferably 2-8 s, and most preferably 3-5 s.
In the invention, the negative pressure in the alternate cycle deposition process is preferably set to be high-power pulse and direct-current negative pressure coupling, so that the plating of a high-shielding workpiece can be realized, and the uniformity of the whole workpiece film layer within the diameter of 250mm is preferably 10-20, more preferably 12-18%, and most preferably 15%.
The invention adopts a magnetic filtration deposition method and a high-power pulse magnetic control method to be matched with a multi-arc deposition method, simultaneously comprehensively considers the interaction between each coil and a positive bias parameter by controlling the process parameters of the three methods, and the parameters are mutually influenced, so that the cathode arc source can normally and stably work, and the strength of the led-out plasma beam is high. Because the magnetic filtration deposition is a high-density deposition device, excessive use of the magnetic filtration deposition device without a multi-arc device can greatly increase the internal stress of the film, resulting in cracking or falling off of the film; too much multi-arc deposition device also can make rete compactness worsen, and the multi-arc deposition granule is many, forms the hole easily to make the corrosion resistance of whole rete deviate from.
After the TiSiN/TiSiCN composite alternating layer is obtained, Al is deposited on the surface of the TiSiN/TiSiCN composite alternating layer by a second high-power pulse magnetic control method2O3And (5) coating to obtain the high shielding piece corrosion-resistant multi-element coating.
In the present invention, the Al2O3The film layer may be in contact with the TiSiN film layer or may be in contact with the TiSiCN film layer.
In the present invention, the operating conditions of the second high power pulse magnetron method preferably include: the cathode target is preferably an aluminum target; the bias voltage is preferably 20-50 kV, more preferably 30-40 kV, and most preferably 50 kV; the pulse width is preferably 0.1-1.2 ms, more preferably 0.2-1.0 ms, and most preferably 0.5-0.8 ms; the pulse frequency is preferably 1-100 Hz, more preferably 10-80 Hz, and most preferably 30-60 Hz; the first duty cycle is preferably <1/10000, more preferably 1/100000-1/10000; the peak power is 5-15 kW, more preferably 7-12 kW, and most preferably 8-10 kW; the voltage of the DC bias is preferably 1-600V, more preferably 50-500V, and most preferably 200-400V; the second duty ratio is preferably 1 to 80%, more preferably 10 to 60%, and most preferably 30 to 50%.
In the present invention, the Al2O3In the deposition process of the film layer, the revolution speed of a deposition port of equipment adopted by the second high-power pulse magnetic control method is preferably 0.1-10 r/min, more preferably 1-8 r/min, and most preferably 2-5 r/min; the deposition time of the second high-power pulse magnetron method is not specially limited, and Al can be ensured2O3The thickness of the film layer is required to be composite, specifically 0-10 s, more preferably 2-8 s, and most preferably 3-5 s.
In the present invention, Al is deposited2O3The film layer mainly has the effect of improving the corrosion resistance of the high shielding piece, and the overall corrosion characteristic of the high shielding piece is improved by more than 10 times compared with that of a high shielding base body without a coating; meanwhile, the supporting layer is a TiSiN/TiSiCN composite alternating layer with high hardness and high toughness, so that the outermost layer of alumina also has high erosion resistance, and the erosion resistance of the outermost layer of alumina is 2-15 times that of the substrate.
Compared with the single anti-corrosion technology, the multi-arc technology adopted by the invention can make up for the defects of low deposition speed, low efficiency and high internal stress of magnetic filtration deposition and high-power pulse magnetic control technology; the magnetic filtration deposition and high-power pulse magnetron deposition technology can fill multiple arcs in the deposition process to form holes and improve the compactness of the film layer, namely the invention combines the high ionization rate and high compactness of the magnetic filtration deposition, the low internal stress and high compactness of the high-power pulse and the high deposition efficiency and high reliability of the multiple arc deposition, therefore, the fusion of the three technologies can simultaneously increase the hard erosion and abrasion resistance of the coating and the corrosion resistance of the blade, thereby forming the high-efficiency anticorrosive coating. Compared with the traditional single bias technology, the bias voltage is a high-power pulse bias and direct-current bias coupling technology, the ultrahigh pulse peak value is achieved, the release of film stress can be achieved under the transient heat peak effect, meanwhile, due to the fact that the electric field intensity is high, the plasma can obtain sufficient energy, good diffraction of the plasma can be achieved, and surface coating of a high-shielding part is achieved. The deposition process integrates ultra-high power ultra-short duty ratio and low-pressure high duty ratio, can reduce internal stress and improve binding force by using instant strong heat peak effect of ultra-high power bias voltage, can also improve continuity of a film layer by using low-pressure high duty ratio and reduce film layer sputtering caused by long-time high negative pressure, and under the combined action of the three methods, simultaneously controls all working conditions within the range, can enable all working conditions to be mutually influenced, and mutually restricts the matching of arcing current, matrix composite bias voltage and the like, and the film layer deposited under the parameters has high compactness, strong abrasion resistance and high deposition rate.
The invention provides a high shielding member corrosion-resistant multi-element coating prepared by the preparation method in the technical scheme, which comprises a TiSiN/TiSiCN composite alternating layer and Al which are sequentially stacked on the surface of a high shielding member substrate2O3A film layer; the TiSiN/TiSiCN composite alternating layer comprises TiSiN film layers and TiSiCN film layers which are alternately stacked.
In the present invention, the schematic view of the corrosion-resistant multi-component coating of the high barrier is shown in FIG. 2-1 or 2-2, wherein 201 is the high barrier substrate, 202 is the TiSiN film, 203 is the TiSiCN film, and 204 is Al2O3The combination of layers 202 and 203 is an alternating TiSiN/TiSiCN layer.
In the invention, the thickness of the TiSiN/TiSiCN alternating film layer is preferably 1-50 μm, more preferably 10-40 μm, and most preferably 20-30 μm.
In the present invention, the Al2O3The thickness of the film layer is preferably 0.1 to 15 μm, more preferably 1 to 12 μm, and most preferably 5 to 10 μm.
The high shielding piece corrosion-resistant multi-element coating provided by the invention has the following advantages: 1. the film base binding force is excellent; 2. the internal stress of the film layer is ultralow; 3. the film has high elastic modulus, good toughness and strong abrasion resistance; 4. the film deposition rate is high; 5. the plasma diffraction performance is good during film coating, and the method is suitable for surface treatment of high-shielding workpieces; 6. the surface roughness of the film layer is low, and the film layer is smooth.
The invention also provides a device used in the preparation method in the technical scheme, which comprises a vacuum chamber, a multi-arc deposition device, a magnetic filtration deposition device, a first high-power pulse magnetron deposition device and a second high-power pulse magnetron deposition device;
the vacuum chamber is cylindrical; the multi-arc deposition device, the magnetic filtration deposition device, the first high-power pulse magnetron deposition device and the second high-power pulse magnetron deposition device are sequentially distributed along the circumferential direction of the vacuum chamber; the multi-arc deposition device, the magnetic filtration deposition device, the first high-power pulse magnetron deposition device and the second high-power pulse magnetron deposition device are respectively connected with the vacuum chamber through O rings.
The device for preparing the high-shielding-piece corrosion-resistant multi-component coating comprises a vacuum chamber, wherein the vacuum chamber comprises a vacuum chamber 303, and the vacuum chamber is used for providing a vacuum environment required by preparing the high-shielding-piece corrosion-resistant multi-component coating.
In the present invention, the multi-arc deposition device 34, the magnetic filter deposition device 31, the first high power pulsed magnetron deposition device 32 and the second high power pulsed magnetron deposition device 33 are connected to the vacuum chamber preferably through O-rings, respectively.
The device for preparing the high shielding piece corrosion-resistant multi-element coating comprises a multi-arc deposition device 34, wherein the multi-arc deposition device is provided with a deposition device vacuum chamber door 301 and a multi-arc deposition port 306, and the multi-arc deposition device 34 is connected with the multi-arc deposition port 306 through an O ring to ensure sealing. In the invention, the multi-arc deposition device is used for improving the overall deposition rate of the film and reducing the internal stress of the film.
The device for preparing the high-shielding-piece corrosion-resistant multi-element coating comprises a magnetic filtration deposition device, wherein the magnetic filtration deposition device 31 comprises a magnetic filtration deposition port 302, and the magnetic filtration deposition device 31 is connected with the magnetic filtration deposition port 302 through an O-ring to ensure sealing. In the invention, the magnetic filtration and deposition device has the function of improving the overall compactness of the membrane layer.
The device for preparing the high-shielding-piece corrosion-resistant multi-element coating comprises a first high-power pulse magnetron deposition device 32, wherein the first high-power pulse magnetron deposition device 32 is provided with a first high-power pulse deposition port 304, and the first high-power pulse magnetron deposition device 32 is connected with the first high-power pulse deposition port 304 and is connected through an O ring to ensure sealing. In the invention, the first high-power pulse magnetron deposition is used for preparing the TiSiC film layer.
The device for preparing the corrosion-resistant multi-element coating of the high shielding piece comprises a second high-power pulse magnetron deposition device 33, wherein the second high-power pulse magnetron deposition device 33 is provided with a second high-power pulse deposition port 305, the second high-power pulse magnetron deposition device 33 is connected with the second high-power pulse deposition port 305, and sealing is guaranteed through O-ring connection. In the invention, the second high-power pulse magnetron deposition is used for preparing the TiSiCN film layer.
In the present invention, a schematic diagram of the apparatus for preparing the corrosion-resistant multi-component coating of the high shielding member is shown in fig. 3, wherein 31 is a magnetic filtration deposition apparatus, 32 is a first high power pulse deposition apparatus, 33 is a second high power pulse deposition apparatus, 34 is a multi-arc deposition apparatus, 301 is a vacuum chamber door of the deposition apparatus, 302 is a magnetic filtration deposition port, 303 is a vacuum chamber wall, 304 is a first high power pulse deposition port, 305 is a second high power pulse deposition port, 306 is a multi-arc deposition port, 307 is a fixture tool, and the multi-arc deposition apparatus 34 and the multi-arc deposition port 306 are connected by an O-ring to ensure sealing; the magnetic filtering and depositing device 31 is connected with the magnetic filtering and depositing port 302 through an O ring to ensure sealing; the first high-power pulse magnetron deposition device 32 is connected with the first high-power pulse deposition port 304 and is sealed by being connected with an O ring; the second and high power pulsed magnetron deposition devices 33 are connected to the first high power pulsed deposition port 305 and are connected by O-rings to ensure sealing. In the invention, the high shielding piece is fixed on the fixture tool through a bolt to rotate, the rotating device is preferably a servo motor, and the servo motor realizes transmission with the fixture tool through magnetic fluid sealing.
In the invention, the method for preparing the corrosion-resistant multi-element coating of the shielding piece on the surface of the high shielding piece substrate by using the device for preparing the corrosion-resistant multi-element coating of the high shielding piece preferably comprises the following steps: the high shielding part is fixed on a clamp tool 307 through a bolt to perform revolutionWhen the high shielding component revolves to the multi-arc deposition port 306, the multi-arc deposition device deposits a TiSiN film layer on the surface of the high shielding component substrate, when the high shielding component revolves to the magnetic filtering deposition port 302, the magnetic filtering device deposits a compact TiSiN film layer on the surface of the TiSiN film layer, and when the high shielding component revolves to the first high-power pulse magnetic control deposition port 304, the first high-power pulse magnetic control deposition device deposits a TiSiCN film layer on the surface of the TiSiN film layer; repeating the deposition steps to obtain a TiSiN/TiSiCN composite alternating layer; closing the multi-arc deposition device, the magnetic filtration deposition device and the first high-power pulse magnetic control deposition device, opening the second high-power pulse magnetic control deposition device, and depositing Al on the surface of the TiSiN/TiSiCN composite alternate layer by the second high-power pulse magnetic control deposition device when revolving to the first high-power pulse magnetic control deposition port 3052O3And (5) film layer.
In the invention, the method for preparing the corrosion-resistant multi-element coating of the shielding piece on the surface of the high shielding piece substrate by using the device for preparing the corrosion-resistant multi-element coating of the high shielding piece preferably comprises the following steps: fixing the high shielding part on a clamp tool 307 through a bolt for revolution, and depositing a TiSiCN film on the surface of the TiSiN film by using a first high-power pulse magnetic control deposition device when the high shielding part revolves to a first high-power pulse magnetic control deposition port 304; when the device revolves to the multi-arc deposition port 306, the multi-arc deposition device deposits a TiSiN film layer on the surface of the high shielding component substrate, when the device revolves to the magnetic filtering deposition port 302, the magnetic filtering device deposits a compact TiSiN film layer on the surface of the TiSiN film layer, and the deposition steps are repeated to obtain a TiSiN/TiSiCN composite alternate layer; closing the multi-arc deposition device, the magnetic filtration deposition device and the first high-power pulse magnetic control deposition device, opening the second high-power pulse magnetic control deposition device, and depositing Al on the surface of the TiSiN/TiSiCN composite alternate layer by the second high-power pulse magnetic control deposition device when revolving to the first high-power pulse magnetic control deposition port 3052O3And (5) film layer.
The device for preparing the corrosion-resistant multi-element coating of the high shielding piece is continuous rotary coating deposition, has good reliability and repeatability of equipment, has high deposition rate and low time cost, and can realize batch production.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
S1: and cleaning the surface of the substrate by using an Ar ion source, wherein the energy of the anode layer ion source is 250eV, and the beam intensity is 4A, so that the high shielding piece substrate is obtained.
S2: fixing the high shielding component on a clamp tool 307 through bolts, and performing revolution at the speed of 2r/min, wherein when the high shielding component revolves to a multi-arc deposition port 306, a TiSiN film layer is deposited on the surface of a high shielding component substrate by the multi-arc deposition device, when the high shielding component revolves to a magnetic filtering deposition port 302, a compact TiSiN film layer is deposited on the surface of the TiSiN film layer by the magnetic filtering device, and when the high shielding component revolves to a first high-power pulse magnetic control deposition port 304, a TiSiCN film layer is deposited on the surface of the TiSiN film layer by the first high; repeating the deposition steps to obtain a TiSiN/TiSiCN composite alternating layer;
wherein the thickness of the TiSiN/TiSiCN composite alternating layer is 3 mu m;
the working conditions of the magnetic filtration and deposition are as follows: the pulse coil current is 25A, the cathode titanium silicon target arcing current is 50A, and the magnetic filtering current intensity is 2.0A;
the working conditions of the multi-arc deposition method are as follows: the titanium silicon target arcing current is 60A, and the arc voltage is 25V;
the working conditions of the high-power pulse magnetic control method are as follows: the cathode target material is a titanium silicon carbon target, the arc starting power is 4kW, the voltage is 200V, and the current is 25A;
the high shield itself is biased with high power pulses of 35kV, 0.6ms pulse width, 50Hz pulse frequency, less than 1/10000 duty cycle, and 10kW peak power.
S3: closing the multi-arc deposition device, the magnetic filtration deposition device and the first high-power pulse magnetron deposition device, and opening the second high-power pulse magnetron deposition device at the speed of 2r/minWhen the device revolves to the first high-power pulse magnetron deposition port 305, the second high-power pulse magnetron deposition device deposits Al on the surface of the TiSiN/TiSiCN composite alternate layer2O3A film layer is formed to obtain the high shielding piece anti-corrosion multi-element coating;
wherein, Al2O3The thickness of the film layer is 1 μm;
the working conditions of the high-power pulse magnetic control technology are as follows: the cathode target material is an aluminum target material, the arc starting power is 4kW, the voltage is 200V, and the current is 25A;
the high shield itself is biased with high power pulses of 35kV, 0.6ms pulse width, 50Hz pulse frequency, less than 1/10000 duty cycle, and 10kW peak power.
The corrosion resistance of the high shielding corrosion-resistant multi-component coating prepared in the embodiment is tested, the test solution is 3.5 wt% sodium chloride solution, and the abrasion equipment is an MFT-EC4000 electrochemical corrosion friction and wear tester. The erosion graph of the high shielding member erosion-resistant multi-component coating prepared in the embodiment is shown in fig. 4, and as can be seen from fig. 4, the erosion potential of the high shielding member erosion-resistant multi-component coating is higher, which indicates that the high shielding member erosion-resistant multi-component coating prepared in the invention has good erosion resistance, and the film friction coefficient is about 0.5 after being lower and stable; the width of the grinding mark is about 282 mu m (the scale is 100 mu m), and the grinding mark is mainly adhesive wear and pitting corrosion, so that the high shielding part anti-corrosion multi-element coating prepared by the invention has excellent anti-corrosion and anti-wear properties.
Example 2
S1: and cleaning the surface of the substrate by using an Ar ion source, wherein the energy of the anode layer ion source is 250eV, and the beam intensity is 4A, so that the high shielding piece substrate is obtained.
S2: fixing the high shielding component on a clamp tool 307 through bolts, and performing revolution at the speed of 3r/min, wherein when the high shielding component revolves to a multi-arc deposition port 306, a TiSiN film layer is deposited on the surface of a high shielding component substrate by the multi-arc deposition device, when the high shielding component revolves to a magnetic filtering deposition port 302, a compact TiSiN film layer is deposited on the surface of the TiSiN film layer by the magnetic filtering device, and when the high shielding component revolves to a first high-power pulse magnetic control deposition port 304, a TiSiCN film layer is deposited on the surface of the TiSiN film layer by the first high; repeating the deposition steps to obtain a TiSiN/TiSiCN composite alternating layer;
wherein the thickness of the TiSiN/TiSiCN composite alternating layer is 3 mu m;
the working conditions of the magnetic filtration and deposition are as follows: the pulse coil current is 25A, the cathode titanium silicon target arcing current is 50A, and the magnetic filtering current intensity is 2.0A;
the working conditions of the multi-arc deposition method are as follows: the titanium silicon target arcing current is 60A, and the arc voltage is 25V;
the working conditions of the high-power pulse magnetic control method are as follows: the cathode target material is a titanium silicon carbon target, the arc starting power is 5kW, the voltage is 200V, and the current is 25A;
the high shield itself is biased with high power pulses of 25kV, 0.6ms pulse width, 50Hz pulse frequency, less than 1/10000 duty cycle, and 10kW peak power.
S3: closing the multi-arc deposition device, the magnetic filtration deposition device and the first high-power pulse magnetron deposition device, opening the second high-power pulse magnetron deposition device, and revolving to the first high-power pulse magnetron deposition port 305 at the speed of 3r/min, wherein the second high-power pulse magnetron deposition device deposits Al on the surface of the TiSiN/TiSiCN composite alternating layer2O3A film layer is formed to obtain the high shielding piece anti-corrosion multi-element coating;
wherein, Al2O3The thickness of the film layer is 1.5 mu m;
the working conditions of the high-power pulse magnetic control technology are as follows: the cathode target material is an aluminum target material, the arc starting power is 5kW, the voltage is 200V, and the current is 25A;
the high shield itself is biased with high power pulses of 25kV, 0.6ms pulse width, 50Hz pulse frequency, less than 1/10000 duty cycle, and 10kW peak power.
Example 3
S1: and cleaning the surface of the substrate by using an Ar ion source, wherein the energy of the anode layer ion source is 250eV, and the beam intensity is 4A, so that the high shielding piece substrate is obtained.
S2: fixing the high shielding component on a clamp tool 307 through bolts, and performing revolution at the speed of 4r/min, wherein when the high shielding component revolves to a multi-arc deposition port 306, a TiSiN film layer is deposited on the surface of a high shielding component substrate by the multi-arc deposition device, when the high shielding component revolves to a magnetic filtering deposition port 302, a compact TiSiN film layer is deposited on the surface of the TiSiN film layer by the magnetic filtering device, and when the high shielding component revolves to a first high-power pulse magnetic control deposition port 304, a TiSiCN film layer is deposited on the surface of the TiSiN film layer by the first high; repeating the deposition steps to obtain a TiSiN/TiSiCN composite alternating layer;
wherein the thickness of the TiSiN/TiSiCN composite alternating layer is 3 mu m;
the working conditions of the magnetic filtration and deposition are as follows: the pulse coil current is 25A, the cathode titanium silicon target arcing current is 50A, and the magnetic filtering current intensity is 2.0A;
the working conditions of the multi-arc deposition method are as follows: the titanium silicon target arcing current is 60A, and the arc voltage is 25V;
the working conditions of the high-power pulse magnetic control method are as follows: the cathode target material is a titanium silicon carbon target, the arc starting power is 6kW, the voltage is 200V, and the current is 25A;
the high shield itself is biased with high power pulses of 25kV, 0.6ms pulse width, 50Hz pulse frequency, less than 1/10000 duty cycle, and 10kW peak power.
S3: closing the multi-arc deposition device, the magnetic filtration deposition device and the first high-power pulse magnetron deposition device, opening the second high-power pulse magnetron deposition device, and revolving to the first high-power pulse magnetron deposition port 305 at the speed of 4r/min, wherein the second high-power pulse magnetron deposition device deposits Al on the surface of the TiSiN/TiSiCN composite alternating layer2O3A film layer is formed to obtain the high shielding piece anti-corrosion multi-element coating;
wherein, Al2O3The thickness of the film layer is 2 μm;
the working conditions of the high-power pulse magnetic control technology are as follows: the cathode target material is a titanium silicon carbon target, the arc starting power is 6kW, the voltage is 200V, and the current is 25A;
the high shield itself is biased with high power pulses of 25kV, 0.6ms pulse width, 50Hz pulse frequency, less than 1/10000 duty cycle, and 10kW peak power.
Example 4
S1: and cleaning the surface of the substrate by using an Ar ion source, wherein the energy of the anode layer ion source is 250eV, and the beam intensity is 4A, so that the high shielding piece substrate is obtained.
S2: fixing the high shielding component on a clamp tool 307 through bolts, and performing revolution at the speed of 5r/min, wherein when the high shielding component revolves to a multi-arc deposition port 306, a TiSiN film layer is deposited on the surface of a high shielding component substrate by the multi-arc deposition device, when the high shielding component revolves to a magnetic filtering deposition port 302, a compact TiSiN film layer is deposited on the surface of the TiSiN film layer by the magnetic filtering device, and when the high shielding component revolves to a first high-power pulse magnetic control deposition port 304, a TiSiCN film layer is deposited on the surface of the TiSiN film layer by the first high; repeating the deposition steps to obtain a TiSiN/TiSiCN composite alternating layer;
wherein the thickness of the TiSiN/TiSiCN composite alternating layer is 3 mu m;
the working conditions of the magnetic filtration and deposition are as follows: the pulse coil current is 25A, the cathode titanium silicon target arcing current is 50A, and the magnetic filtering current intensity is 2.0A;
the working conditions of the multi-arc deposition method are as follows: the titanium silicon target arcing current is 60A, and the arc voltage is 25V;
the working conditions of the high-power pulse magnetic control method are as follows: the cathode target material is a titanium silicon carbon target, the arc starting power is 7kW, the voltage is 200V, and the current is 25A;
the high shield itself is biased with high power pulses of 25kV, 0.6ms pulse width, 50Hz pulse frequency, less than 1/10000 duty cycle, and 10kW peak power.
S3: closing the multi-arc deposition device, the magnetic filtration deposition device and the first high-power pulse magnetic control deposition device, opening the second high-power pulse magnetic control deposition device, and revolving to the first high-power pulse magnetic control deposition port 305 at the speed of 5r/min, wherein the second high-power pulse magnetic control deposition device deposits Al on the surface of the TiSiN/TiSiCN composite alternating layer2O3A film layer is formed to obtain the high shielding piece anti-corrosion multi-element coating;
wherein, Al2O3The thickness of the film layer is 2.5 mu m;
the working conditions of the high-power pulse magnetic control technology are as follows: the cathode target material is an aluminum target material, the arc starting power is 7kW, the voltage is 200V, and the current is 25A;
the high shield itself is biased with high power pulses of 25kV, 0.6ms pulse width, 50Hz pulse frequency, less than 1/10000 duty cycle, and 10kW peak power.
Example 5
S1: with Ar + H2And cleaning the surface of the substrate by an ion source, wherein the energy of the ion source of the anode layer is 250eV, and the beam intensity is 4A, so that the high shielding piece substrate is obtained.
S2: fixing the high shielding component on a clamp tool 307 through bolts, and performing revolution at the speed of 6r/min, wherein when the high shielding component revolves to a multi-arc deposition port 306, a TiSiN film layer is deposited on the surface of a high shielding component substrate by the multi-arc deposition device, when the high shielding component revolves to a magnetic filtering deposition port 302, a compact TiSiN film layer is deposited on the surface of the TiSiN film layer by the magnetic filtering device, and when the high shielding component revolves to a first high-power pulse magnetic control deposition port 304, a TiSiCN film layer is deposited on the surface of the TiSiN film layer by the first high; repeating the deposition steps to obtain a TiSiN/TiSiCN composite alternating layer;
wherein the thickness of the TiSiN/TiSiCN composite alternating layer is 3 mu m;
the working conditions of the magnetic filtration and deposition are as follows: the pulse coil current is 25A, the cathode titanium silicon target arcing current is 50A, and the magnetic filtering current intensity is 2.0A;
the working conditions of the multi-arc deposition method are as follows: the titanium silicon target arcing current is 60A, and the arc voltage is 25V;
the working conditions of the high-power pulse magnetic control method are as follows: the cathode target material is a titanium silicon carbon target, the arc starting power is 8kW, the voltage is 200V, and the current is 25A;
the high shield itself is biased with high power pulses of 25kV, 0.6ms pulse width, 50Hz pulse frequency, less than 1/10000 duty cycle, and 10kW peak power.
S3: closing the multi-arc deposition device, the magnetic filtration deposition device and the first high-power pulse magnetic control deposition device, opening the second high-power pulse magnetic control deposition device, and revolving to the first high-power pulse magnetic control deposition port 305 at the speed of 6r/min, wherein the second high-power pulse magnetic control deposition device alternately compounds TiSiN/TiSiCNAl deposited on the surface of the layer2O3A film layer is formed to obtain the high shielding piece anti-corrosion multi-element coating;
wherein, Al2O3The thickness of the film layer is 0.5 μm;
the working conditions of the high-power pulse magnetic control technology are as follows: the cathode target material is an aluminum target material, the arc starting power is 8kW, the voltage is 200V, and the current is 25A;
the high shield itself is biased with high power pulses of 25kV, 0.6ms pulse width, 50Hz pulse frequency, less than 1/10000 duty cycle, and 10kW peak power.
An SEM (scanning Electron microscope) of a cross section of the corrosion-resistant multi-component coating of the high shielding member prepared in the embodiment is shown in FIG. 5, and it can be seen from FIG. 5 that the inner circulation multi-layer composite structure of the film layer is a TiSiN/TiSiCN composite alternate layer, and the outermost layer is Al2O3The film layer, the multi-component corrosion-resistant film layer has strong integral compactness, no obvious holes and cracks and good quality.
FIG. 6 is a graph showing the hardness and toughness of the anti-corrosive multi-component coating of the high barrier material prepared in examples 1-5, wherein (a) is the TiSiCN coating deposited in examples 1-5 and the outermost Al layer2O3A change diagram of the hardness of the film layer brought by the change of the deposition power of the high-power pulse magnetic control during the film layer; as can be seen from (a), the higher the high power pulse power is, the higher Al is deposited2O3The higher the hardness of the film layer, H3/E2The ratio of (A) to (B) also has a related proportional relationship, the highest H3/E2May be 0.63. (b) As shown in the hardness diagrams of the high masks prepared in examples 1 to 5, it was found from (b) that the TiSiCN film layer and the outermost Al layer were deposited2O3The deposition power of the high-power pulse magnetic control is increased during film coating, the hardness of the integral film of the corrosion-resistant multi-element coating is increased firstly and then reduced, and the maximum value can be 44 Gpa. (c) And (d) and (e) are toughness maps of Rockwell indentation test of the high barrier corrosion resistant multi-component coatings prepared in examples 1, 3 and 5, respectively, wherein the toughness rating of the Rockwell indentation test is HF1, and the corrosion resistant multi-component coatings have high hardness and super toughness.
Example 6
S1: with Ar + H2And cleaning the surface of the substrate by an ion source, wherein the energy of the ion source of the anode layer is 500eV, and the beam intensity is 5A, so that the high shielding piece substrate is obtained.
S2: fixing the high shielding component on a clamp tool 307 through bolts, and performing revolution at the speed of 7r/min, wherein when the high shielding component revolves to a multi-arc deposition port 306, a TiSiN film layer is deposited on the surface of a high shielding component substrate by the multi-arc deposition device, when the high shielding component revolves to a magnetic filtering deposition port 302, a compact TiSiN film layer is deposited on the surface of the TiSiN film layer by the magnetic filtering device, and when the high shielding component revolves to a first high-power pulse magnetic control deposition port 304, a TiSiCN film layer is deposited on the surface of the TiSiN film layer by the first high; repeating the deposition steps to obtain a TiSiN/TiSiCN composite alternating layer;
wherein the thickness of the TiSiN/TiSiCN composite alternating layer is 3 mu m;
the working conditions of the magnetic filtration and deposition are as follows: the pulse coil current is 500A, the cathode titanium silicon target arcing current is 100A, and the magnetic filtering current intensity is 2.0A;
the working conditions of the multi-arc deposition method are as follows: the titanium silicon target arcing current is 120A, and the arc is 40A;
the working conditions of the high-power pulse magnetic control method are as follows: the cathode target material is a titanium silicon carbon target, the arc starting power is 4kW, the voltage is 400V, and the current is 50A;
the high shield itself is biased with high power pulses of 50kV, 1.2ms pulse width, 100Hz pulse frequency, less than 1/10000 duty cycle, and 15kW peak power.
S3: closing the multi-arc deposition device, the magnetic filtration deposition device and the first high-power pulse magnetron deposition device, opening the second high-power pulse magnetron deposition device, and revolving to the first high-power pulse magnetron deposition port 305 at the speed of 7r/min, wherein the second high-power pulse magnetron deposition device deposits Al on the surface of the TiSiN/TiSiCN composite alternating layer2O3A film layer is formed to obtain the high shielding piece anti-corrosion multi-element coating;
wherein, Al2O3The thickness of the film layer is 3 μm;
the working conditions of the high-power pulse magnetic control technology are as follows: the cathode target material is an aluminum target material, the arc starting power is 4kW, the voltage is 400V, and the current is 50A;
the high shield itself is biased with high power pulses of 50kV, 1.2ms pulse width, 100Hz pulse frequency, less than 1/10000 duty cycle, and 15kW peak power.
Example 7
S1: with Ar + H2And cleaning the surface of the substrate by an ion source, wherein the energy of the ion source of the anode layer is 50eV, and the beam intensity is 3A, so that the high shielding piece substrate is obtained.
S2: fixing the high shielding component on a clamp tool 307 through bolts, and performing revolution at the speed of 8r/min, wherein when the high shielding component revolves to a multi-arc deposition port 306, a TiSiN film layer is deposited on the surface of a high shielding component substrate by the multi-arc deposition device, when the high shielding component revolves to a magnetic filtering deposition port 302, a compact TiSiN film layer is deposited on the surface of the TiSiN film layer by the magnetic filtering device, and when the high shielding component revolves to a first high-power pulse magnetic control deposition port 304, a TiSiCN film layer is deposited on the surface of the TiSiN film layer by the first high; repeating the deposition steps to obtain a TiSiN/TiSiCN composite alternating layer;
wherein the thickness of the TiSiN/TiSiCN composite alternating layer is 5 mu m;
the working conditions of the magnetic filtration and deposition are as follows: the pulse coil current is 10A, the cathode titanium silicon target arcing current is 1A, and the magnetic filtering current intensity is 2.0A;
the working conditions of the multi-arc deposition method are as follows: the titanium silicon target arcing current is 10A, and the arc is 10A;
the working conditions of the high-power pulse magnetic control method are as follows: the cathode target material is a titanium silicon carbon target, the arc starting power is 4kW, the voltage is 10V, and the current is 10A;
the high shield itself is biased with high power pulses at a voltage of 20kV, a pulse width of 0.1ms, a pulse frequency of 1Hz, a duty cycle of less than 1/10000, and a peak power of 5 kW.
S3: closing the multi-arc deposition device, the magnetic filtration deposition device and the first high-power pulse magnetic control deposition device, opening the second high-power pulse magnetic control deposition device, and when the second high-power pulse magnetic control deposition device revolves to the first high-power pulse magnetic control deposition port 305 at the speed of 8r/min, the second high-power pulse magnetic control deposition device deposits on the surface of the TiSiN/TiSiCN composite alternating layerAccumulated Al2O3A film layer is formed to obtain the high shielding piece anti-corrosion multi-element coating;
wherein, Al2O3The thickness of the film layer is 3.5 mu m;
the working conditions of the high-power pulse magnetic control technology are as follows: the cathode target material is an aluminum target material, the arc starting power is 4kW, the voltage is 5V, and the current is 5A;
the high shield itself is biased with high power pulses at a voltage of 20kV, a pulse width of 0.1ms, a pulse frequency of 1Hz, a duty cycle of less than 1/10000, and a peak power of 5 kW.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (5)

1. The preparation method of the corrosion-resistant multi-element coating of the high shielding component is characterized by comprising the following steps of:
fixing the high shielding component on a fixture tool for revolution, depositing a TiSiN film layer on the surface of a high shielding component substrate by a multi-arc deposition device when the high shielding component revolves to a multi-arc deposition port, depositing a compact TiSiN film layer on the surface of the TiSiN film layer by a magnetic filtration device when the high shielding component revolves to the magnetic filtration deposition port, and depositing a TiSiCN film layer on the surface of the TiSiN film layer by a first high-power pulse magnetic control deposition device when the high shielding component revolves to the first high-power pulse magnetic control deposition port; repeating the deposition steps to obtain a TiSiN/TiSiCN composite alternating layer;
or the high shielding part is fixed on a fixture tool for revolution, when the high shielding part revolves around the first high-power pulse magnetic control deposition port, the first high-power pulse magnetic control deposition device deposits a TiSiCN film layer on the surface of the high shielding part substrate, when the high shielding part revolves around the multi-arc deposition port, the multi-arc deposition device deposits a TiSiN film layer on the surface of the TiSiCN film layer, and when the high shielding part revolves around the magnetic filtering deposition port, the magnetic filtering device deposits a compact TiSiN film layer on the surface of the TiSiN film layer; repeating the deposition steps to obtain a TiSiN/TiSiCN composite alternating layer;
the high shielding component substrate is in contact with a TiSiN film layer or a TiSiCN film layer in the TiSiN/TiSiCN composite alternating layer;
the working conditions of the magnetic filtration deposition comprise: the current is 1-50A, the angle between the direction of the pulse magnetic field and the plane of the cathode is 45-90 degrees, the cathode arcing current is 1-100A, and the magnetic filtering current intensity is 1.0-2.0A;
the working conditions of the multi-arc deposition comprise: the cathode arcing current is 1-120A, and the arc voltage is 10-40V;
the working conditions of the first high-power pulse magnetron deposition comprise: the arc starting power is 2-12 kW, the voltage is 0-400V, the current is 0-300A, the voltage of pulse bias is 20-50 kV, the pulse width is 0.1-1.2 ms, the pulse frequency is 1-100 Hz, the duty ratio is 0-1/10000, the peak power is 5-15 kW, and the deposition time is 1-10 h;
depositing Al on the surface of the TiSiN/TiSiCN composite alternating layer by using second high-power pulse magnetron deposition2O3Coating to obtain anticorrosive multicomponent coating of the high shielding part;
the Al is2O3The film layer is contacted with the TiSiN film layer or the TiSiCN film layer in the TiSiN/TiSiCN composite alternating layer.
2. The method for preparing as claimed in claim 1, wherein the operating conditions of the second high power pulsed magnetron deposition include: the cathode target is an aluminum target, the voltage of pulse bias is 20-50 kV, the pulse width is 0.1-1.2 ms, the pulse frequency is 1-100 Hz, the first duty ratio is less than 1/10000, and the peak power is 5-15 kW; the voltage of the DC bias is 1-600V, and the second duty ratio is 1-80%.
3. The anticorrosive multi-component coating for the high shielding component prepared by the preparation method of any one of claims 1-2, which is characterized by comprising a TiSiN/TiSiCN composite alternating layer and Al which are sequentially stacked on the surface of a high shielding component substrate2O3A film layer; the TiSiN/TiSiCN composite alternating layer comprises TiSiN film layers and TiSiCN film layers which are alternately stacked.
4. The multi-component coating of claim 3, which isCharacterized in that Al is2O3The thickness of the film layer is 0.1-15 μm.
5. The multilayer coating of claim 3, wherein the total thickness of the TiSiN/TiSiCN composite alternating layers is 1-50 μm.
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