CN114318263B - Oxidation-resistant, wear-resistant and antifriction gradient nano metal coating and preparation method thereof - Google Patents
Oxidation-resistant, wear-resistant and antifriction gradient nano metal coating and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of medium-high temperature oxidation and self-lubrication, and particularly provides an antioxidant, wear-resistant and antifriction gradient nano metal coating and a preparation method thereof. By utilizing the sputtering characteristic and adjusting the temperature and the vacuum degree in real time in the magnetron sputtering film plating process, the nano metal coating with the grain size in gradient distribution from the surface to the inside can be obtained in one step by a single target material without other processes. The coating has simple preparation process, is suitable for but not limited to common carbon steel, alloy steel, bearing steel, copper-based, titanium-based, cobalt-based or nickel-based high-temperature alloy, and can be used for high-temperature bearings, bushings and other transmission components which can bear high temperature of more than 400 ℃ and are in service in high-temperature environments. Based on the characteristics of promoting the selective oxidation of Al and Cr, improving the surface hardness and promoting the stratification of enamel of oxides, the coating has excellent comprehensive properties of medium-high temperature oxidation resistance, wear resistance, self-lubrication and the like.
Description
Technical Field
The invention belongs to the technical field of medium-high temperature oxidation and self-lubrication, and relates to an antioxidant, wear-resistant and antifriction gradient nano metal coating and a preparation method thereof.
Background
With the rapid development of aerospace and aerospace technologies in China, multi-factor coupling damage caused by increasingly harsh service environments becomes a main failure mode of materials, and the design difficulty of key parts is greatly increased. Transmission components such as high-temperature bearings and bushings in power systems of aero-engines, gas turbines and aerospace craft serving in high-temperature environments bear friction force (surface shear stress) and are subjected to oxidation reaction with environmental media (such as oxygen), and the failure of the components is accelerated by the cooperative coupling of friction wear and high-temperature oxidation, so that the key factors influencing the reliability and the service life of the whole system are achieved.
In order to solve the problems of high-temperature corrosion and frictional wear of key parts, researchers propose adding a self-lubricating phase into a high-temperature resistant metal or ceramic material to improve the wear resistance of the high-temperature resistant metal or ceramic material. Such as the National Aeronautics and Space Administration (NASA) by chemical vapor deposition on NiCr, cr 2 O 3 Adding high-temperature resistant self-lubricating CaF into the metal ceramic matrix 2 /BaF 2 Eutectic, thereby realizing the high-temperature self-lubricating function of the material. However, the common high-temperature self-lubricating phase with more ceramics can greatly reduce the fracture toughness of the material, and has poor interface compatibility with alloy and ceramics, thereby greatly limiting the application of the high-temperature-resistant self-lubricating composite material. Meanwhile, the influence of high-temperature corrosion performance on the effective operation of parts is mostly ignored in the existing research. Due to the high-temperature oxidation of the alloy material, the growth of the oxide film can quickly fill the clearance (the clearance width is about 10-20 mu m) of the inner ring and the outer ring of the originally narrow joint bearing, so that the bearing is locked and fails at high temperature. This is particularly true for precision bearings with high requirements for play accuracy and narrow play.
On the basis of not changing the mechanical property of the alloy, the application of the coating is one of effective measures for realizing the wear resistance and oxidation resistance of the material. Among them, DLC (diamond-like carbon) and WC-Co (Ni) composite coatings are considered to be ideal wear-resistant coatings due to the extremely low friction coefficient, but are oxidized and volatilized at high temperature, so that the application of the DLC and WC-Co (Ni) composite coatings at high temperature is greatly limited. The CrTiN coating can accelerate the damage of a shaft, a sheath and the like matched with a metal component to a grinding piece due to the extremely high hardness of the CrTiN coating. The organic coating is susceptible to structural change at high temperature and is not suitable for use in high temperature environments. Therefore, in order to solve the problem of corrosive wear of the motion and transmission parts serving in a high-temperature environment, a novel anti-oxidation, wear-resistant and anti-wear protective coating needs to be developed.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide an antioxidant, wear-resistant and antifriction gradient nano metal coating and a preparation method thereof, so as to solve the problem of corrosion and abrasion of a transmission part in service in a high-temperature environment.
The invention provides an antioxidant, wear-resistant and antifriction gradient nano metal coating, which has the same components as an alloy matrix, and has a nano columnar crystal structure, the grain size is increased from the surface to the inside of the coating from small to 5-500 nm, and the thickness of the coating is 20-100 mu m.
In the antioxidant, wear-resistant and antifriction gradient nano metal coating, the gradient nano metal coating is obtained by a single target material in one step without other processes by adjusting the temperature and the vacuum degree in real time in the magnetron sputtering coating process.
In the antioxidant, wear-resistant and antifriction gradient nano metal coating, the temperature range in the magnetron sputtering process is 100-250 ℃, and the vacuum degree range is 1 multiplied by 10 -1 ~6×10 -3 Pa。
In the antioxidant, wear-resistant and antifriction gradient nano metal coating, the gradient nano metal coating is suitable for common carbon steel, alloy steel, bearing steel, copper-based, titanium-based, cobalt-based or nickel-based high-temperature alloy.
In the antioxidant, wear-resistant and antifriction gradient nano metal coating, after the coating is coated on the common carbon steel, alloy steel, bearing steel, copper-based, cobalt-based or nickel-based bearing and bushing processing materials, the coefficient of reciprocating friction is 0.2-0.4, and the wear rate is 5.0 multiplied by 10 -5 ~5.0×10 -6 mm 3 The oxidation resistance is more than or equal to 1000 hours at 400-900 ℃.
The invention also provides a preparation method of the antioxidant, wear-resistant and antifriction gradient nano metal coating, which comprises the following steps:
step 1: preparing a target material, namely preparing the target material consistent with the components of the substrate by a vacuum melting technology according to the selected components of the substrate, and then polishing the surface of the target material for later use;
step 2: pretreating a sample, namely grinding the surface of the sample by using SiC abrasive paper, then polishing by using polishing paste, and finally ultrasonically cleaning by using a mixed solution of acetone and alcohol for later use;
and step 3: the nano metal coating is prepared by adopting a magnetron sputtering technology, and the size of nano crystal grains in the coating is controlled to gradually increase from the surface to the inside of the coating by adjusting the temperature and the vacuum degree in real time in the magnetron sputtering coating process.
In the preparation method of the antioxidant, wear-resistant and antifriction gradient nano metal coating, the step 3 is specifically as follows:
step 3.1: suspending a substrate sample on a rotating stand 10-20 cm away from a target before preparation, and rotating the sample in the preparation process to ensure that the thickness of the coating on the surface of the substrate is uniform; the target material is arranged on a cathode water-cooling target sleeve, a chamber is closed, a mechanical pump and a molecular pump are used for pumping vacuum, and when the vacuum degree reaches 2 multiplied by 10 -5 Heating is started when the pressure is Pa;
step 3.2: when the vacuum degree of the chamber reaches 6 multiplied by 10 -3 When the temperature reaches 250 ℃ above Pa, introducing argon to ignite a cathode arc, controlling the flow of the argon by a flowmeter, controlling the flow range to be 3-6 Sccm, and controlling the argon pressure to be 0.1-0.2 Pa;
step 3.3: during sputtering, the temperature of the chamber is reduced and the vacuum degree of the chamber is improved in real time by switching on and off the heating equipment and the molecular pump so as to adjust the grain size;
step 3.4: at the end of the deposition, when the chamber temperature decreased below 50 ℃, the molecular pump and mechanical pump were turned off and the sample was removed.
In the preparation method of the antioxidant, wear-resistant and antifriction gradient nano metal coating, step 3 is as follows:
when the vacuum degree is more than or equal to 6 multiplied by 10 -3 Pa, the grain size range is 70-500 nm at the temperature of 250-200 ℃;
when the vacuum degree is 6 multiplied by 10 -3 ~3×10 -2 Pa, the grain size range is 10-70 nm at the temperature of 200-150 ℃;
when the vacuum degree is 3 multiplied by 10 -2 ~1×10 -1 Pa, and the grain size is 5-10 nm at the temperature of 150-100 ℃.
In the preparation method of the antioxidant, wear-resistant and antifriction gradient nano metal coating, the sputtering in the step 3 adopts a constant power mode, and the power is as follows: 2000-4000W; the sputtering rate is 3-6 mu m/h, and the deposition time is as follows: 6 to 15 hours.
The design idea of the invention is as follows:
Hall-Petch shows that the room temperature strength of the polycrystal is increased along with the reduction of the grain size, and the nano coating applied to the surface is beneficial to improving the hardness of the material so as to improve the wear resistance. And the nanocrystallization is favorable for promoting the selective oxidation of Al and Cr so as to improve the oxidation resistance of the alloy. Finally, the oxide preferentially nucleates at the defects such as grain boundaries and the like, and the grain boundaries are increased, so that the grain size of the oxide is reduced, the sintering, namely the enamel stratification, of the oxide is promoted, and the aim of reducing the friction coefficient is finally achieved.
The invention has the advantages and the technical effects that:
1. the coating prepared by the invention has simple process, is not limited by the structure of an alloy matrix, can be used for coating the surface of a workpiece with a complex structure, and is suitable for but not limited to various base materials such as common carbon steel, alloy steel, bearing steel, copper base, titanium base, cobalt base or nickel base superalloy and the like.
2. The coating prepared by the invention can be removed and then coated after long-term use, and has small influence on the mechanical property of the base material.
3. The coating prepared by the invention has a compact structure and excellent oxidation resistance in a high-temperature environment.
4. The coating prepared by the invention has excellent wear resistance and low friction coefficient, and can achieve the effect of long-term wear resistance.
Drawings
FIG. 1 is a transmission photograph of a cross section of the coating prepared in example 1 at 1 μm from the surface;
FIG. 2 is a transmission photograph of a cross section of the coating prepared in example 1 at 10 μm from the surface;
FIG. 3 is a plot of the room temperature coefficient of friction of the K38G alloy and the gradient nanolayered coating of example 2;
FIG. 4 is the surface topography of the 12Cr1MoV alloy steel of example 5 after 30-minute friction;
FIG. 5 is the surface topography of the gradient nanolayered coating of example 5 rubbed for 30 minutes.
Detailed Description
The invention provides an antioxidant, wear-resistant and antifriction gradient nano metal coating, which has the same components with an alloy matrix, and has a nano columnar crystal structure, the size of crystal grains is increased from the surface to the inside of the coating from small to small, the size range of the crystal grains is 5-500 nm, and the thickness of the coating is 20-100 mu m.
The gradient nano metal coating is obtained by a single target material through real-time adjustment of temperature and vacuum degree in the magnetron sputtering coating process without other processes. The temperature range in the magnetron sputtering process is 100-250 ℃, and the vacuum degree range is 1 multiplied by 10 -1 ~6×10 -3 Pa. The gradient nano metal coating is suitable for common carbon steel, alloy steel, bearing steel, copper base, titanium base, cobalt base or nickel base high temperature alloy. Aiming at the bearing and bushing processing materials of common carbon steel, alloy steel, bearing steel, copper base, cobalt base or nickel base, the reciprocating friction coefficient is 0.2-0.4 and the wear rate is 5.0 multiplied by 10 after the coating is coated -5 ~5.0×10 -6 mm 3 The oxidation resistance is more than or equal to 1000 hours at 400-900 ℃.
The invention also provides a preparation method of the antioxidant, wear-resistant and antifriction gradient nano metal coating, which comprises the following steps:
step 1: preparing a target material, namely preparing the target material consistent with the components of the substrate by a vacuum melting technology according to the selected components of the substrate, and then polishing the surface of the target material for later use;
step 2: pretreating a sample, namely grinding the surface of the sample by using SiC abrasive paper, then polishing by using polishing paste, and finally ultrasonically cleaning by using a mixed solution of acetone and alcohol for later use;
and step 3: the nano metal coating is prepared by adopting a magnetron sputtering technology, and the size of nano crystal grains in the coating is controlled to gradually increase from the surface to the inside of the coating by adjusting the temperature and the vacuum degree in real time in the magnetron sputtering coating process. Wherein the step 3 specifically comprises the following steps:
step 3.1: suspending a substrate sample on a rotating stand 10-20 cm away from a target before preparation, and rotating the sample in the preparation process to ensure that the thickness of the coating on the surface of the substrate is uniform; the target material is arranged on a cathode water-cooling target sleeve, a chamber is closed, a mechanical pump and a molecular pump are used for pumping vacuum, and when the vacuum degree reaches 2 multiplied by 10 -5 Heating is started when the pressure is Pa;
step 3.2: when the vacuum degree of the chamber reaches 6 multiplied by 10 -3 When the temperature reaches 250 ℃ above Pa, introducing argon to ignite a cathode arc, controlling the flow of the argon by a flowmeter, controlling the flow range to be 3-6 Sccm, and controlling the argon pressure to be 0.1-0.2 Pa;
step 3.3: during sputtering, the temperature of the chamber is reduced and the vacuum degree of the chamber is improved in real time by switching on and off the heating equipment and the molecular pump so as to adjust the grain size;
when the vacuum degree is more than or equal to 6 multiplied by 10 -3 Pa, at 250-200 deg.C, the grain size is 70-500 nm.
When the vacuum degree is 6 multiplied by 10 -3 ~3×10 -2 Pa, and the grain size range is 10-70 nm at the temperature of 200-150 ℃.
When the vacuum degree is 3 multiplied by 10 -2 ~1×10 -1 Pa, at 150-100 deg.C, the grain size is 5-10 nm.
Step 3.4: at the end of the deposition, when the chamber temperature decreased below 50 ℃, the molecular pump and the mechanical pump were turned off and the sample was taken out.
In specific implementation, the sputtering in the step 3 adopts a constant power mode, and the power is as follows: 2000-4000W; the sputtering rate is 3-6 mu m/h, and the deposition time is as follows: 6 to 15 hours.
The present invention is described in detail below with reference to the drawings and examples, but the scope of the present invention is not limited by the drawings and examples.
Example 1
The preparation method comprises the following steps of preparing a gradient nano metal coating on the surface of bearing steel GCr15 serving as a matrix, wherein the preparation process comprises the following steps:
(1) Preparing a target material: the GCr15 alloy target material is prepared by adopting a vacuum melting technology, and comprises the following chemical components: 0.95wt.%, cr:1.65wt.%, si:0.15wt.%, mn:0.25wt.%, ni:0.3wt.%, cu:0.25wt.%, mo:0.1wt.% and Fe balance. The target was then cut to dimensions 382 × 128 × 8mm and surface polished for use.
(2) Sample pretreatment: GCr15 steel was cut into 15X 10X 2mm samples by wire-cut electrical discharge machining. Then, the surface of the sample is ground by 240-2000 # SiC abrasive paper, then is polished by 2.5 mu m polishing paste, and finally is polished by a polishing machine 1: and ultrasonically cleaning for 15 minutes by using a mixed solution of acetone and alcohol with the proportion of 3.
(3) Preparing a coating: the coating is prepared by adopting a magnetron sputtering technology. Before preparation, the sample is hung on a rotating frame which is 10-20 cm away from the target material, and the sample is rotated in the preparation process to ensure that the thickness of the coating on the surface of the substrate is uniform. The target material is arranged on a cathode water-cooling target sleeve, the chamber is closed, and the chamber is vacuumized by a mechanical pump and a vacuum pump. When the vacuum degree reaches 2 x 10 -5 Heating is started at Pa. When the vacuum degree of the chamber reaches 6 multiplied by 10 -3 Pa, the temperature reaches 250 ℃, nitrogen is introduced at the flow rate of 4Sccm to start sputtering, the sputtering power is 2000W, and the argon pressure is 0.1Pa. During the period, the temperature of the chamber is reduced and the vacuum degree of the chamber is increased in real time by switching on and off the heating equipment and the molecular pump. The coating time depends on the thickness of the required coating, the sputtering deposition time is 8h, and the thickness of the film layer is 20 mu m.
FIG. 1 is a transmission photograph of a cross section of the coating prepared in example 1 at 1 μm from the surface. FIG. 2 is a transmission photograph of a cross-section of the coating prepared in example 1 at 10 μm from the surface. The coating is shown as an ultra-fine nano columnar crystal structure, and the grain size is smaller and is about 5nm closer to the surface.
Example 2
The difference from the embodiment 1 is that the base alloy is K38G nickel base alloy, the alloy base is used as a comparison experiment, and oxidation products of the alloy are NiO and NiCr after the alloy is oxidized for 500 hours at 800 DEG C 2 O 4 And Cr 2 O 3 . The oxidation weight gain is 0.5mg/cm 2 . Oxidizing the gradient nano metal coating for 500h to generate Cr on the surface 2 O 3 The oxidation weight gain is 0.17mg/cm 2 . In the room temperature friction wear test, when the load is 10N, the friction coefficient curve of the alloy and the coating is shown in figure 3, the friction coefficient of the alloy is as high as 1.1, and the friction coefficient of the nanocrystalline coating is rapidly reduced to a stable value of 0.3 after 5 minutes of friction.
Example 3
The difference from the embodiment 1 is that the base alloy is cobalt-based alloy (15 Cr-10Ni-56Co-14W-3Fe-0.4Si-1.5Mn-0.1C wt%), a gradient nano coating is prepared on the surface of the base alloy, the coating is consistent with the alloy components,there is no problem of interface stability of coating and alloy. By taking an alloy matrix as a comparison experiment, oxidation products of the alloy are CoO and CoCr after the alloy is oxidized for 100 hours at 900 DEG C 2 O 4 And Cr 2 O 3 . The oxidation weight gain is 1.28mg/cm 2 The thickness of the oxide layer has reached 10 μm. The surface of the gradient nanocrystalline coating is oxidized for 100 hours to generate Cr 2 O 3 The oxidation weight gain is 0.25mg/cm 2 80% lower than that of alloy. And simultaneously, a 400 ℃ frictional wear test is carried out on the nanocrystalline coating and the alloy. When the load is 10N, the friction coefficient of the alloy sample is as high as 0.6, and the curve fluctuation of the friction coefficient is large. Even though CoO with better sintering property is formed, the surface can not form a complete enamel layer after 30 minutes of friction, and the alloy is damaged to a certain extent. And the friction coefficient of the nanocrystalline coating rapidly decreases to a stable value of 0.27 after 5 minutes of friction.
Example 4
The difference from the embodiment 1 is that the matrix alloy is TiAl high-temperature alloy, and after the gradient nanocrystalline coating prepared on the alloy is oxidized for 100 hours at 900 ℃, the oxide film is Al 2 O 3 The oxidation weight gain is 0.23mg/cm 2 . While the oxidation weight gain of the TiAl alloy is 3.2mg/cm 2 The surface oxide film is TiO 2 . The coating greatly reduces the oxidation rate of the alloy.
Example 5
The difference from the embodiment 1 is that the base alloy is 12Cr1MoV alloy steel, and the surface of the alloy is coated with a gradient nano coating with the thickness of about 30 μm. Then, a room-temperature friction and wear experiment is carried out on the alloy and the coating, the load is 10N, the friction pair GCr15 bearing steel is rubbed for 30 minutes, and after the friction is carried out for 30 minutes, the surface appearance of the 12Cr1MoV alloy steel in the embodiment 5 is rubbed for 30 minutes; FIG. 5 is the surface topography of the gradient nanolayered coating of example 5 rubbed for 30 minutes. The alloy surface has a plurality of furrows and abrasive dust, the surface is worn by abrasive grains, the abrasion marks on the alloy surface are not obvious, the abrasive dust is not observed, an enamel layer is formed, and the abrasion mechanism is not adhered and worn. The abrasion loss of the alloy was 4.5X 10 -4 mm 3 /(Nm), the amount of abrasion of the coating was 5.2X 10 -6 mm 3 /(Nm), a reduction of two orders of magnitude over the alloy. From this the gradient can be knownThe nano coating obviously improves the abrasion resistance of the alloy.
Example 6
The difference from embodiment 2 is that the grain size distribution in the coating layer is different. The crystal grain size ranges of 5-10 nm, 10-70 nm and 70-500 nm in the embodiment 2 are 5 μm, 5 μm and 10 μm (1 #), respectively, and the corresponding thickness ranges in this embodiment are 8 μm, 7 μm and 5 μm (2 #); 10 μm, 5 μm (3 #), the frictional wear properties of the three coatings at room temperature were compared. The coefficient of friction curves for the three coatings at 10N are shown in FIG. 5, with coefficients of friction of 0.3,0.28, and 0.28 for the three coatings, indicating that all three coatings reduce the coefficient of friction of the alloy.
The above description is only a preferred embodiment of the present invention and should not be taken as limiting the scope of the invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.
Claims (4)
1. The gradient nano metal coating is characterized in that the components of the coating and an alloy matrix are consistent, the coating structure is a nano columnar crystal structure, the size of crystal grains is increased from the surface to the inside of the coating from small to small, the size range of the crystal grains is 5-500 nm, and the thickness of the coating is 20-100 mu m;
the gradient nano metal coating is obtained by a single target material in one step by adjusting the temperature and the vacuum degree in real time without other processes in the magnetron sputtering coating process;
the temperature range in the magnetron sputtering process is 100-250 ℃, and the vacuum degree range is 1 multiplied by 10 -1 ~6×10 -3 Pa;
When the vacuum degree is more than or equal to 6 multiplied by 10 -3 Pa, the grain size range is 70-500 nm at the temperature of 250-200 ℃;
when the vacuum degree is 6 multiplied by 10 -3 ~3×10 -2 Pa, the grain size range is 10-70 nm at the temperature of 200-150 ℃;
when the vacuum degree is 3 multiplied by 10 -2 ~1×10 -1 Pa, the grain size range is 5-10 nm at the temperature of 150-100 ℃;
the gradient nano metal coating is suitable for common carbon steel, alloy steel, bearing steel, copper base, titanium base, cobalt base or nickel base superalloy.
2. The oxidation-resistant, wear-resistant and friction-reducing gradient nanometal coating according to claim 1, wherein after the coating is applied to the processing materials of ordinary carbon steel, alloy steel, bearing steel, copper-based, cobalt-based or nickel-based bearing and bushing, the coefficient of reciprocating friction is 0.2-0.4, and the wear rate is 5.0 x 10 -5 ~5.0×10 -6 mm 3 The oxidation resistance is more than or equal to 1000 hours at 400-900 ℃.
3. A preparation method of an antioxidant, wear-resistant and antifriction gradient nano metal coating is characterized by comprising the following steps:
step 1: preparing a target material, namely preparing the target material consistent with the components of the substrate by a vacuum melting technology according to the selected components of the substrate, and then polishing the surface of the target material for later use;
step 2: pretreating a sample, namely grinding the surface of the sample by using SiC abrasive paper, then polishing by using polishing paste, and finally ultrasonically cleaning by using a mixed solution of acetone and alcohol for later use;
and step 3: preparing a nano metal coating by adopting a magnetron sputtering technology, and controlling the size of nano crystal grains in the coating by adjusting the temperature and the vacuum degree in real time in the magnetron sputtering coating process, wherein the size of the crystal grains is gradually increased from the surface to the inside of the coating and ranges from 5nm to 500nm;
the step 3 specifically comprises the following steps:
step 3.1: suspending a substrate sample on a rotating stand 10-20 cm away from a target before preparation, and rotating the sample in the preparation process to ensure that the thickness of the coating on the surface of the substrate is uniform; the target material is arranged on a cathode water-cooling target sleeve, a chamber is closed, a mechanical pump and a molecular pump are used for pumping vacuum, and when the vacuum degree reaches 2 multiplied by 10 -5 Heating is started when the pressure is Pa;
step 3.2: when the vacuum degree of the chamber reaches 6 multiplied by 10 -3 When the temperature reaches 250 ℃ above Pa, introducing argon to ignite a cathode arc, controlling the flow of the argon by a flowmeter, controlling the flow range to be 3-6 Sccm, and controlling the argon pressure to be 0.1 to E0.2Pa;
Step 3.3: during sputtering, the temperature of the chamber is reduced and the vacuum degree of the chamber is improved in real time by switching on and off the heating equipment and the molecular pump so as to adjust the grain size;
step 3.4: when the deposition is finished, when the temperature of the chamber is reduced to below 50 ℃, the molecular pump and the mechanical pump are closed, and a sample is taken out;
in the step 3:
when the vacuum degree is more than or equal to 6 multiplied by 10 -3 Pa, the grain size range is 70-500 nm at the temperature of 250-200 ℃;
when the vacuum degree is 6 multiplied by 10 -3 ~3×10 -2 Pa, the grain size range is 10-70 nm at the temperature of 200-150 ℃;
when the vacuum degree is 3 multiplied by 10 -2 ~1×10 -1 Pa, at 150-100 deg.C, the grain size is 5-10 nm.
4. The method for preparing the antioxidant, wear-resistant and antifriction gradient nano-metal coating according to claim 3, characterized in that the sputtering in the step 3 adopts a constant power mode, and the power is as follows: 2000-4000W; the sputtering rate is 3-6 mu m/h, and the deposition time is as follows: 6 to 15 hours.
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