High-binding-force wear-resistant and corrosion-resistant coating as well as preparation method and application thereof

Abstract

The invention discloses a high-binding-force wear-resistant and corrosion-resistant coating as well as a preparation method and application thereof. The preparation method of the high-binding-force wear-resistant corrosion-resistant coating comprises the following steps: preparing a gradient nano texture on the surface of a base material by utilizing electric pulse-assisted ultrasonic rolling to form a texture layer; sequentially depositing a bottoming layer, a conversion layer and a functional layer on the surface of the texture layer by using a non-equilibrium closed field magnetron sputtering technology; after a sample is subjected to vacuum annealing, a strengthening layer is formed on the surface of the sample through an ultrasonic rolling extrusion technology. According to the method, the electric pulse auxiliary ultrasonic rolling technology, the magnetron sputtering PVD technology and the ultrasonic rolling extrusion technology are creatively combined, the abrasion resistance and corrosion resistance of the metal surface are effectively improved, the bonding strength between a base material and a coating is remarkably enhanced, and therefore the technical problem that a film layer is prone to falling off is solved. In addition, the preparation method has the advantages of high efficiency, low consumption, environmental protection and the like.

Description

Technical Field

[0001] The present invention belongs to the technical field of surface coating and precision processing, and in particular relates to a high-bonding wear-resistant and corrosion-resistant coating and a preparation method and application thereof. Background Art

[0002] Metal materials such as 316L stainless steel, TC4 titanium alloy, and YG8 cemented carbide are widely used in the manufacture of high-load mechanical components such as molds, gears, and bearings due to their excellent strength and formability. However, under complex operating conditions (such as corrosive media, cyclic stress, and high-temperature friction), critical load-bearing areas of these components are prone to stress corrosion cracking (SCC), abrasive wear, and fatigue fracture, resulting in a 30%–60% reduction in service life. To improve the service performance of these materials, researchers have widely adopted surface modification technologies, including thermal spraying, vacuum heat treatment, electroplating, electroless plating, solid infiltration, hydrothermal methods, physical vapor deposition (PVD), and chemical vapor deposition (CVD).

[0003] PVD technology has attracted significant attention due to its ease of operation, controllable process, and suitability for continuous production, making it a widely used advanced surface treatment technology internationally. PVD coatings, with their excellent wear and corrosion resistance, are widely used in aerospace, automotive, and medical industries. The technology is also widely used on a variety of workpieces, including tools, molds, spare parts, and fasteners, significantly extending their service life and improving production efficiency. Furthermore, the PVD coating process is environmentally friendly and pollution-free.

[0004] However, the interfacial bonding strength between PVD coatings and substrates is often insufficient to withstand the high external loads encountered in practical applications, leading to coating peeling or delamination, which in turn affects their service life. Currently, most solutions involve depositing a metal primer layer (such as Ti, Cr, Zr, etc.) on the metal substrate to enhance the film-base bonding, but this approach is still relatively limited and cannot meet the requirements of applications with higher performance requirements. Summary of the Invention

[0005] In view of the shortcomings of the existing technology, the purpose of the present invention is to provide a high-bonding wear-resistant and corrosion-resistant coating and its preparation method and application, which are used to solve the technical problem that the PVD coating in the existing technology is easy to fall off during use.

[0006] The purpose of the present invention is achieved through the following technical solutions: A high-bonding wear-resistant and corrosion-resistant coating is provided with a texture layer, a primer layer, a conversion layer, a functional layer and a strengthening layer in sequence from the inside to the outside; wherein, The texture layer is a gradient nanolayer with a honeycomb structure; the base layer is a Me metal layer, and Me is at least one of Ti, Cr, Nb, Al, Si and Mo; The conversion layer is composed of n alternately deposited units, each unit comprising a layer of metal carbonitride Me-N:C deposited at a high bias voltage and a layer of metal carbonitride Me-N:C deposited at a low bias voltage, n ≥ 3, and the Me is consistent with the base layer; The functional layer is composed of multiple layers of gradient Me-Nb:C deposited at different powers, and the Me is consistent with the base layer; the strengthening layer is formed by ultrasonic rolling extrusion treatment on the surface of the functional layer.

[0007] In the present invention, the provision of the texture layer can achieve three-dimensional mechanical interlocking between the substrate and the coating. Through the three-dimensional mechanical interlocking structure, the coating can be more firmly attached to the substrate material. This structure increases the contact area and physical locking effect, thereby significantly improving the bonding strength between the coating and the substrate.

[0008] The setting of the base layer is mainly used to buffer thermal stress and enhance the interface bonding strength between the coating and the substrate. In addition, the selection of Me is determined according to the type and function of the substrate material. Furthermore, metal elements with a thermal expansion coefficient close to that of the substrate material are preferably selected.

[0009] The present invention adopts a gradient structure design of "base layer-conversion layer-functional layer". Through the step-by-step transition between each layer, the thermal stress caused by the difference in thermal expansion coefficient between the substrate and the coating is effectively alleviated, thereby suppressing the interface stress concentration and preventing the expansion of cracks.

[0010] The strengthening layer is designed to repair the hole defects in the coating, reduce the generation of crack sources, and reduce the surface roughness of the material.

[0011] Preferably, the thickness of the primer layer is 20-100 nm, the thickness of the conversion layer is 100-800 nm, the thickness of the functional layer is 80-1100 nm, and the total thickness of the high-adhesion wear-resistant and corrosion-resistant coating is 200-2000 nm. More preferably, the total thickness of the high-adhesion wear-resistant and corrosion-resistant coating is 500-1500 nm.

[0012] The method for preparing the above-mentioned high-adhesion wear-resistant and corrosion-resistant coating comprises the following steps: The surface of the substrate is subjected to gradient nanotexturing by electric pulse-assisted ultrasonic rolling to form a textured layer. Using unbalanced closed-field magnetron sputtering technology, a primer layer, a conversion layer, and a functional layer are sequentially deposited on the surface of the texture layer; After vacuum annealing, the sample was subjected to ultrasonic rolling extrusion technology to form a strengthening layer on its surface.

[0013] In some embodiments of the present invention, to ensure the cleanliness and appropriate roughness of the substrate surface, thereby improving the bonding strength between the coating and the substrate and the quality of the coating, the substrate surface needs to be polished, ultrasonically cleaned, and then dried before use. Specifically, the selected substrate surface is ground and polished using sandpaper of 80#, 180#, 220#, 280#, 320#, 400#, 600#, 800#, 1200#, 1500#, and 2000#, in sequence; the polished substrate is then ultrasonically cleaned with acetone, ethanol, and deionized water for 15 to 30 minutes to remove surface dust and oil stains, and then vacuum dried for use.

[0014] In some embodiments of the present invention, in order to remove the oxide film and impurities on the textured surface and activate its surface state, the sample after the texture layer processing is placed in a cleaned vacuum chamber and plasma cleaning is performed. Specifically, the chamber needs to be vacuumed to 1×10 -3 Pa, then introduce argon and adjust the pressure to maintain at 0.15~0.20Pa, turn the turntable to 3~6r / min, and apply -800~-1000V bias, and plasma cleaning for 15~30min.

[0015] Preferably, the step of preparing gradient nanotexture on the surface of the substrate by using electric pulse assisted ultrasonic rolling to form a texture layer comprises: The substrate was fixed, and the static pressure of the electric pulse-assisted ultrasonic rolling process was set to 500~2000N, the amplitude to 5~20μm, the vibration frequency to 15~40kHz, the feed speed to 0.05~0.5mm / r, the pulse current frequency to 100~1500Hz, and the peak current to 200~1000A.

[0016] Preferably, the step of depositing the base layer includes: waiting for the background vacuum of the chamber to be less than 8×10 -4 Pa, adjust the working vacuum to 0.15~0.25Pa, connect a high-power pulsed DC power supply, set the Me metal target power to 3~8kW, the power frequency to 100~1000Hz, the pulse width to 50~200µs, the bias voltage to -300~-1000V, and the deposition temperature to 50~200℃.

[0017] Preferably, the step of depositing the conversion layer includes: introducing nitrogen and adjusting the flow rate of nitrogen and argon to 4:6 respectively, maintaining the vacuum degree at 0.20~0.25Pa; keeping the sputtering parameters of the Me metal target consistent with the base deposition step, then turning on the graphite target and connecting to a DC pulse power supply, setting its power to 0.5~3kW, the deposition temperature to 50~200℃, and the bias voltage alternately set between -300V and -600V, and performing alternating deposition of Me-N:C layers until the required number of layers is reached.

[0018] Preferably, the step of depositing the functional layer includes: turning off the nitrogen, adjusting the argon flow rate to 120 sccm, and maintaining the vacuum degree at 0.22~0.25 Pa; keeping the sputtering parameters of the Me metal target and the graphite target consistent with the conversion layer deposition step; turning on the Nb target and connecting to a high-power pulsed DC power supply, setting its power supply power from 2 kW to 5 kW at a rate of 0.1 kW / min, the frequency is 10~1000 Hz, the pulse width is 50~200µs, the bias voltage is -300~-1000 V, and the deposition temperature is controlled at 50~200°C. Under these conditions, the Me-Nb:C functional gradient layer is deposited.

[0019] Preferably, the parameters of the vacuum annealing are: annealing temperature is 400-800°C, annealing time is 1-3h, vacuum degree is 10 -4 ~10 -5 Pa.

[0020] In the present invention, the residual stress inside the material can be effectively eliminated through vacuum annealing treatment, while promoting the improvement of the coating density.

[0021] Preferably, the step of forming the strengthening layer using ultrasonic rolling extrusion technology includes: applying a static pressure of 20~80N, selecting an amplitude of 0.5~5μm, and maintaining a feed speed of 100~300mm / min during ultrasonic rolling extrusion.

[0022] In the present invention, the PVD coating is strengthened by adopting ultrasonic rolling extrusion technology, and high-frequency vibration energy is simultaneously applied during the mechanical rolling process to form a synergistic strengthening effect. This composite treatment promotes the elastic-plastic deformation of the coating material at the nanoscale, thereby effectively repairing hole defects, reducing crack sources, and reducing surface roughness, ultimately significantly improving the overall performance of the coating.

[0023] Application of the above-mentioned high-bonding wear-resistant and corrosion-resistant coating in surface treatment of metal materials.

[0024] Preferably, the metal material is any one of stainless steel, titanium, titanium alloy, nickel-based alloy, aluminum, aluminum alloy and cemented carbide.

[0025] Preferably, the stainless steel is one of 304 stainless steel, 310 stainless steel, 316 stainless steel, 316L stainless steel and 904L stainless steel.

[0026] Preferably, the titanium alloy is one of α titanium alloy and α+β titanium alloy. Preferably, the aluminum alloy is one of an Al-Cu alloy, an Al-Mn alloy, an Al-Si alloy and an Al-Mg alloy.

[0027] Preferably, the nickel-based alloy is one of a Ni-Cr alloy, a Ni-Cr-Mo alloy, a Ni-Co-Cr alloy and a Ni-Fe-Cr alloy.

[0028] Preferably, the nickel alloy is one of a nickel-based high-temperature alloy, a nickel-based corrosion-resistant alloy and a nickel-based wear-resistant alloy. Preferably, the cemented carbide is one of a WC-TiC-Co alloy, a WC-Co alloy and a WC-TiC-TaC / NbC-Co alloy.

[0029] In summary, the present invention improves the coating bonding performance through five synergistic strengthening strategies: 1. Three-dimensional nano-texture interface design: Electric pulse-assisted ultrasonic rolling technology is used to process grooved nano-texture on the surface of the metal substrate, expanding the interface bonding from a two-dimensional plane to a three-dimensional structure, and improving the coating-substrate interface bonding strength by increasing the spatial adhesion area; 2. Plasma activation pretreatment: Plasma cleaning is used to simultaneously achieve physical etching (enhanced mechanical anchoring), chemical activation (promote chemical bond formation) and interface impurity removal on the ultrasonic rolling pretreatment surface, significantly optimizing the interface bonding conditions; 3. Gradient coating structure regulation: A "base layer-conversion layer-functional layer" gradient system is designed to alleviate the difference in thermal expansion coefficient between the substrate and the coating through layer-by-layer gradient transition, thereby inhibiting interface stress concentration and crack propagation; 4. Deposition dynamics optimization: By precisely controlling parameters such as substrate bias, deposition temperature and deposition rate, the mobility and diffusion ability of the coating atoms are enhanced, and dense atomic-level bonding at the interface is achieved; 5. Residual stress elimination: Vacuum annealing treatment is used to release the internal stress of the PVD coating and further strengthen the membrane-substrate bonding strength.

[0030] Compared with the prior art, the present invention has the following beneficial effects: (1) The high-bonding wear-resistant and corrosion-resistant coating provided by the present invention can not only effectively improve the wear resistance and corrosion resistance of the metal surface, but also significantly enhance the bonding force between the film and the substrate, solve the problem of PVD coating easily falling off and causing failure, and improve the durability and stability of the coating material.

[0031] (2) The preparation method of the high-bonding wear-resistant and corrosion-resistant coating provided by the present invention adopts electric pulse assisted ultrasonic rolling technology, introduces instantaneous high-energy pulse current, significantly affects the plasticity, recrystallization, phase transformation and organizational evolution of metal materials, enhances the dislocation migration of the surface layer of the material, promotes the healing of microcracks, reduces the number of defects, and improves the surface quality of the substrate. It not only overcomes the technical defects of single ultrasonic rolling technology that is prone to wrinkling, cracking and crushing, but also solves the problem that traditional ultrasonic rolling is difficult to process superhard materials such as cemented carbide, and expands the processing range of ultrasonic rolling technology.

[0032] (3) The present invention provides a method for preparing a high-bonding wear-resistant and corrosion-resistant coating, which strengthens the PVD coating through the innovative application of ultrasonic rolling extrusion. It is based on a traditional rolling and extrusion device, and by improving the rolling extrusion wheel structure and integrating an ultrasonic vibration module, high-frequency vibration energy is superimposed during the mechanical rolling process. The combined effect of mechanical rolling and high-frequency vibration promotes nanoscale elastic-plastic deformation of the coating material, repairs coating pore defects and reduces crack sources, while reducing surface roughness, thereby significantly improving the overall service performance of the coating. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 This is a schematic structural diagram of the high-adhesion, wear-resistant, and corrosion-resistant coating of the present invention.

[0034] Figure 2 The figure is a bar chart comparing the bonding strength of the coatings prepared in Example 1 and Comparative Examples 1-3.

[0035] Figure 3 The figure is a comparative bar chart of the self-corrosion current density of the coatings prepared in Example 1 and Comparative Examples 1-3.

[0036] Figure 4 The figure is a bar chart comparing the wear rates of the coatings prepared in Example 1 and Comparative Examples 1 to 3. DETAILED DESCRIPTION

[0037] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0038] Example 1 A method for preparing a high-adhesion wear-resistant and corrosion-resistant coating, the specific steps are as follows: (1) First, a TC4 titanium alloy with a size of 50 mm × 50 mm × 5 mm was selected as the substrate and polished to a roughness of Ra = 0.2 ± 0.1 μm. The substrate was then ultrasonically cleaned in acetone, ethanol, and deionized water for 20 min to remove surface dust and oil stains, and then vacuum dried for later use. (2) The substrate was fixed on the machine tool workbench and its surface was nanotextured using an ultrasonic rolling device. The static pressure, amplitude, vibration frequency, feed rate, pulse current frequency, and peak current were set to 1000 N, 8 μm, 28 kHz, and 0.15 mm / r, respectively, in the numerical control system. After processing, the substrate was ultrasonically cleaned in acetone, ethanol, and deionized water for 30 min to remove dust and oil stains on the surface, and then vacuum dried for use. (3) Wait for the background vacuum of the chamber to be pumped down to 5.0×10 -3 Pa, then introduce argon Ar (Ar flow rate 100 sccm) to maintain the pressure at 0.20~0.24 Pa, then start the turntable at 4r / min, and apply -800V bias to the turntable, sputter clean for 10 minutes to remove the residue on the turntable surface; then turn off the bias power supply, open the target baffle, and sputter clean for 15 minutes to remove impurities on the target surface, and then load the substrate into the furnace; (4) Wait for the background vacuum of the chamber to be pumped down to 1×10 -3 Pa, then introduce argon Ar (Ar flow rate 100sccm) to maintain the vacuum degree at 0.15~0.20Pa, turn the turntable to 5r / min, and apply -1000V bias. Plasma cleaning for 15min removes the oxide film and impurities on the surface of the substrate, forming uniform nano-scale pits, increasing the effective contact area, providing mechanical interlocking anchor points, and thus enhancing the film-substrate bonding strength; (5) Wait until the background vacuum of the chamber is less than 8×10 -4 When the working vacuum is adjusted to 0.2 Pa, a high-power pulsed DC power supply is connected, and the Ti target power is set to 3.0 kW, the frequency is 600 Hz, the pulse width is 50 μs, the bias voltage is set to -800 V, the deposition temperature is 150 ° C, and the coating time is 15 min to deposit the bottom layer Ti; (6) Immediately introduce N2 and adjust the flow rates of N2 and argon Ar to 40 sccm:60 sccm respectively (the vacuum degree is maintained at 0.20~0.25 Pa); keep the Ti target sputtering parameters unchanged, turn on the graphite target (connect to the DC pulse power supply), set the graphite target power supply power to 2 kW; the deposition temperature is 150 ° C, the bias voltage is set to -300 V and -600 V (alternate deposition under -300 V and -600 V conditions, each layer deposition time is 5 min, and 6 layers are deposited in a cycle), the coating time is 30 min, and a Ti-N:C transition alternating layer, i.e., a conversion layer, is obtained; (7) Immediately turn off N2 and adjust the Ar flow rate to 120 sccm (vacuum maintained at 0.22~0.25 Pa); keep the sputtering parameters of the Ti target and graphite target unchanged, turn on the Nb target (connect to a high-power pulsed DC power supply), set its power supply power from 2 kW to 5 kW (gradient of 0.1 kW / min), frequency to 1000 Hz, pulse width to 70 μs; set the bias voltage to -1000 V; temperature to 150 ° C, coating time to 30 min, and deposit a Ti-Nb:C functional gradient layer, i.e., a functional layer; (8) Place the sample in step (7) into a vacuum muffle furnace and adjust the vacuum to 5.0×10 -4 Pa, set the annealing temperature to 500 ° C, maintain for 2 h, and complete the vacuum annealing treatment; (9) The surface of the sample in step (8) was strengthened by ultrasonic rolling extrusion technology with a processing static pressure of 50 N, an amplitude of 1.1 μm, and a feed speed of 150 mm / min to form a strengthening layer.

[0039] Comparative Example 1 A method for preparing a wear-resistant and corrosion-resistant PVD coating on a metal surface, comprising the following steps: (1) First, a TC4 titanium alloy with a size of 50 mm × 50 mm × 5 mm was selected as the substrate and polished to a roughness of Ra = 0.2 ± 0.1 μm. The substrate was then ultrasonically cleaned in acetone, ethanol, and deionized water for 20 min to remove surface dust and oil stains, and then vacuum dried for later use. (2) Wait for the background vacuum of the chamber to be pumped down to 5.0×10 -3 Pa, then introduce argon Ar (Ar flow rate 100 sccm) to maintain the pressure at 0.20~0.24 Pa, then start the turntable at 4r / min, and apply -800V bias to the turntable, sputter clean for 10 minutes to remove the residue on the turntable surface; then turn off the bias power supply, open the target baffle, and sputter clean for 15 minutes to remove impurities on the target surface, and then load the substrate into the furnace; (3) Wait for the background vacuum of the chamber to be pumped down to 1×10 -3 Pa, then introduce argon Ar (Ar flow rate 100sccm) to maintain the vacuum degree at 0.15~0.20Pa, turn the turntable at 5r / min, and apply -1000V bias. Plasma cleaning for 15min removes the oxide film and impurities on the surface of the substrate, forming uniform nano-scale pits, increasing the effective contact area, providing mechanical interlocking anchor points, and thus enhancing the film-substrate bonding strength; (4) Wait until the background vacuum of the chamber is less than 8×10 -4When the working vacuum is adjusted to 0.2 Pa, a high-power pulsed DC power supply is connected, and the Ti target power is set to 3.0 kW, the frequency is 600 Hz, the pulse width is 50 μs, the bias voltage is set to -800 V, the deposition temperature is 150 ° C, and the coating time is 15 min to deposit the bottom layer Ti; (5) Immediately introduce N2 and adjust the flow rates of N2 and argon Ar to 40 sccm:60 sccm respectively (the vacuum degree is maintained at 0.20~0.25 Pa); keep the Ti target sputtering parameters unchanged, turn on the graphite target (connect to the DC pulse power supply), and set the graphite target power supply power to 2 kW; the deposition temperature is 150 ° C, the bias voltage is set to -300 V and -600 V (alternate deposition under -300 V and -600 V conditions, each layer deposition time is 5 min, and 6 layers are deposited in a cycle), the coating time is 30 min, and the Ti-N:C transition alternating layer is deposited; (6) Immediately turn off N2 and adjust the Ar flow rate to 120 sccm (the vacuum is maintained at 0.22~0.25 Pa); keep the sputtering parameters of the Ti target and graphite target unchanged, turn on the Nb target (connect to a high-power pulsed DC power supply), set its power supply power from 2 kW to 5 kW (gradient of 0.1 kW / min), frequency to 1000 Hz, pulse width to 70 µs; set the bias voltage to -1000 V; temperature to 150 °C, coating time to 30 min, and deposit the Ti-Nb:C functional gradient layer.

[0040] Comparative Example 2 A method for preparing a wear-resistant and corrosion-resistant PVD coating on a metal surface, comprising the following steps: (1) First, a TC4 titanium alloy with a size of 50 mm × 50 mm × 5 mm was selected as the substrate and polished to a roughness of Ra = 0.2 ± 0.1 μm. The substrate was then ultrasonically cleaned in acetone, ethanol, and deionized water for 20 min to remove surface dust and oil stains, and then vacuum dried for later use. (2) Wait for the background vacuum of the chamber to be pumped down to 5.0×10 -3 Pa, then introduce argon Ar (Ar flow rate 100 sccm) to maintain the pressure at 0.20~0.24 Pa, then start the turntable at 4r / min, and apply -800V bias to the turntable, sputter clean for 10 minutes to remove the residue on the turntable surface; then turn off the bias power supply, open the target baffle, and sputter clean for 15 minutes to remove impurities on the target surface, and then load the substrate into the furnace; (3) Wait for the background vacuum of the chamber to be pumped down to 1×10 -3Pa, then introduce argon Ar (Ar flow rate 100sccm) to maintain the vacuum degree at 0.15~0.20Pa, turn the turntable at 5r / min, and apply -1000V bias. Plasma cleaning for 15min removes the oxide film and impurities on the surface of the substrate, forming uniform nano-scale pits, increasing the effective contact area, providing mechanical interlocking anchor points, and thus enhancing the film-substrate bonding strength; (4) Wait until the background vacuum of the chamber is less than 8×10 -4 When the working vacuum is adjusted to 0.2 Pa, a high-power pulsed DC power supply is connected, and the Ti target power is set to 3.0 kW, the frequency is 600 Hz, the pulse width is 50 μs, the bias voltage is set to -800 V, the deposition temperature is 150 ° C, and the coating time is 15 min to deposit the bottom layer Ti; (5) Immediately introduce N2 and adjust the flow rates of N2 and argon Ar to 40 sccm and 60 sccm respectively (the vacuum degree is maintained at 0.20~0.25 Pa); keep the Ti target sputtering parameters unchanged, turn on the graphite target (connect to the DC pulse power supply), and set the graphite target power supply power to 2 kW; the deposition temperature is 150 ° C, the bias voltage is set to -300 V and -600 V (alternate deposition under -300 V and -600 V conditions, each layer deposition time is 5 min, and 6 layers are deposited in a cycle), the coating time is 30 min, and the Ti-N:C transition alternating layer is deposited; (6) Immediately turn off N2 and adjust the Ar flow rate to 120 sccm (vacuum maintained at 0.22~0.25 Pa); keep the sputtering parameters of the Ti target and graphite target unchanged, turn on the Nb target (connect to a high-power pulsed DC power supply), set its power supply power from 2 kW to 5 kW (gradient of 0.1 kW / min), frequency to 1000 Hz, pulse width to 70 µs; set the bias voltage to -1000 V; temperature to 150 °C, coating time to 30 min, and deposit the Ti-Nb:C functional gradient layer; (7) Place the sample in step (6) into a vacuum muffle furnace and adjust the vacuum degree to 5.0×10 -4 Pa, set the annealing temperature to 500℃, maintain it for 2h, and complete the vacuum annealing treatment.

[0041] Comparative Example 3 A method for preparing a wear-resistant and corrosion-resistant PVD coating on a metal surface, comprising the following steps: (1) First, a TC4 titanium alloy with a size of 50 mm × 50 mm × 5 mm was selected as the substrate and polished to a roughness of Ra = 0.2 ± 0.1 μm. The substrate was then ultrasonically cleaned in acetone, ethanol, and deionized water for 20 min to remove surface dust and oil stains, and then vacuum dried for later use. (2) The substrate was fixed on the machine tool workbench and its surface was nanotextured using an ultrasonic rolling device. The static pressure, amplitude, vibration frequency, feed rate, pulse current frequency, and peak current of the CNC system were set to 1000 N, 8 μm, 28 kHz, 0.15 mm / r, 1200 Hz, and 500 A, respectively. After processing, the substrate was ultrasonically cleaned in acetone, ethanol, and deionized water for 30 min in sequence to remove dust and oil stains on the surface, and then vacuum dried for use. (3) Wait for the background vacuum of the chamber to be pumped down to 5.0×10 -3 Pa, then introduce argon Ar (Ar flow rate 100 sccm) to maintain the pressure at 0.20~0.24 Pa, then start the turntable at 4r / min, and apply -800V bias to the turntable, sputter clean for 10 minutes to remove the residue on the turntable surface; then turn off the bias power supply, open the target baffle, and sputter clean for 15 minutes to remove impurities on the target surface, and then load the substrate into the furnace; (4) Wait for the background vacuum of the chamber to be pumped down to 1×10 -3 Pa, then introduce argon Ar (Ar flow rate 100sccm) to maintain the vacuum degree at 0.15~0.20Pa, turn the turntable at 5r / min, and apply -1000V bias. Plasma cleaning for 15min removes the oxide film and impurities on the surface of the substrate, forming uniform nano-scale pits, increasing the effective contact area, providing mechanical interlocking anchor points, and thus enhancing the film-substrate bonding strength; (5) Wait until the background vacuum of the chamber is less than 8×10 -4 When the working vacuum is adjusted to 0.2 Pa, a high-power pulsed DC power supply is connected, and the Ti target power is set to 3.0 kW, the frequency is 600 Hz, the pulse width is 50 μs, the bias voltage is set to -800 V, the deposition temperature is 150 ° C, and the coating time is 15 min to deposit the bottom layer Ti; (6) Immediately introduce N2 and adjust the flow rates of N2 and argon Ar to 40 sccm and 60 sccm respectively (the vacuum degree is maintained at 0.20~0.25 Pa); keep the Ti target sputtering parameters unchanged, turn on the graphite target (connect to the DC pulse power supply), and set the graphite target power supply power to 2 kW; the deposition temperature is 150 ° C, the bias voltage is set to -300 V and -600 V (alternate deposition under -300 V and -600 V conditions, each layer deposition time is 5 minutes, and 6 layers are deposited in a cycle), the coating time is 30 minutes, and the Ti-N:C transition alternating layer is deposited; (7) Immediately turn off N2 and adjust the Ar flow rate to 120 sccm (vacuum maintained at 0.22~0.25 Pa); keep the sputtering parameters of the Ti target and graphite target unchanged, turn on the Nb target (connect to a high-power pulsed DC power supply), set its power supply power from 2 kW to 5 kW (gradient of 0.1 kW / min), frequency to 1000 Hz, pulse width to 70 µs; set the bias voltage to -1000 V; temperature to 150 °C, coating time to 30 min, and deposit the Ti-Nb:C functional gradient layer; (8) Place the sample in step (7) into a vacuum muffle furnace and adjust the vacuum to 5.0×10 -4 Pa, set the annealing temperature to 500℃, maintain it for 2h, and complete the vacuum annealing treatment.

[0042] The adhesion, corrosion resistance and wear resistance of the coatings prepared in Example 1 and Comparative Examples 1 to 3 were tested. Specifically; The coating surface was scratched using the multifunctional material surface tester MFT-4000 produced by Lanzhou Huahui Instrument Technology Co., Ltd. to quantitatively determine the coating's bonding strength. The wear resistance of the coating in artificial seawater environment was evaluated using a linear reciprocating friction and wear tester CETR–UMT–3MO; The corrosion resistance of the coating in 3.5wt% NaCl solution was evaluated using an electrochemical workstation PARSTAT 4000A produced by Princeton, USA. The above test results are shown in Table 1.

[0043] Table 1 Test results of bonding strength and wear and corrosion resistance

[0044] As shown in Table 1, compared with Comparative Examples 1 to 3, the coating prepared by the present invention exhibits significant advantages in terms of bonding strength, wear resistance, and corrosion resistance. Specifically, the bonding strength of the coating of the present invention is as high as 117N, which is 2.6 times that of Comparative Example 1; the self-corrosion current density is only 0.012μA / cm 2 , accounting for only 1.9% of that in comparative example 1; and the wear rate of the coating is only 1 / 16 of that in comparative example 1, indicating that its wear resistance is greatly improved.

[0045] like Figures 2-4 The following are bar graphs comparing the bonding strength, self-corrosion current density, and wear rate of the coatings prepared in Example 1 and Comparative Examples 1 to 3. These graphs more intuitively demonstrate that, compared to the comparative examples, the coatings prepared in the present invention exhibit superior bonding strength, corrosion resistance, and wear resistance, demonstrating their superior overall performance.

[0046] The specific embodiments of the present invention described above do not limit the scope of protection of the present invention. Any other corresponding changes and modifications made based on the technical concept of the present invention should be included in the scope of protection of the claims of the present invention.

Claims

1. A high-adhesion wear-resistant and corrosion-resistant coating, characterized in that: From the inside to the outside, there are a texture layer, a base layer, a conversion layer, a functional layer and a strengthening layer. The texture layer is a gradient nanolayer with a honeycomb structure; the base layer is a Me metal layer, and Me is at least one of Ti, Cr, Nb, Al, Si and Mo; The conversion layer is composed of n alternately deposited units, each unit comprising a layer of metal carbonitride Me-N:C deposited at a high bias voltage and a layer of metal carbonitride Me-N:C deposited at a low bias voltage, n ≥ 3, and the Me is consistent with the base layer; The functional layer is composed of multiple layers of gradient Me-Nb:C deposited at different powers, and the Me is consistent with the base layer; the strengthening layer is formed by ultrasonic rolling extrusion treatment on the surface of the functional layer.

2. The high-adhesion wear-resistant and corrosion-resistant coating according to claim 1, characterized in that: The thickness of the primer layer is 20-100 nm, the thickness of the conversion layer is 100-800 nm, the thickness of the functional layer is 80-1100 nm, and the total thickness of the high-bonding wear-resistant and corrosion-resistant coating is 200-2000 nm.

3. The method for preparing the high-adhesion wear-resistant and corrosion-resistant coating according to any one of claims 1 to 2, characterized in that: The steps include: The surface of the substrate is subjected to gradient nanotexturing by electric pulse-assisted ultrasonic rolling to form a textured layer. Using unbalanced closed-field magnetron sputtering technology, a primer layer, a conversion layer, and a functional layer are sequentially deposited on the surface of the texture layer; After vacuum annealing, the sample was subjected to ultrasonic rolling extrusion technology to form a strengthening layer on its surface.

4. The method for preparing a high-adhesion wear-resistant and corrosion-resistant coating according to claim 3, characterized in that: The step of preparing gradient nanotexture on the surface of the substrate by using electric pulse assisted ultrasonic rolling to form a texture layer includes: The substrate was fixed, and the static pressure of the electric pulse-assisted ultrasonic rolling process was set to 500~2000N, the amplitude was 5~20μm, the vibration frequency was 15~40kHz, the feed speed was 0.05~0.5mm / r, the pulse current frequency was 100~1500Hz, and the peak current was 200~1000A.

5. The method for preparing a high-adhesion wear-resistant and corrosion-resistant coating according to claim 3, characterized in that: The step of depositing the bottom layer includes: waiting for the background vacuum of the chamber to be less than 8×10 -4 Pa, adjust the working vacuum to 0.15~0.25Pa, connect a high-power pulsed DC power supply, set the Me metal target power to 3~8kW, the power frequency to 100~1000Hz, the pulse width to 50~200µs, the bias voltage to -300~-1000V, and the deposition temperature to 50~200℃.

6. The method for preparing a high-adhesion wear-resistant and corrosion-resistant coating according to claim 5, characterized in that: The step of depositing the conversion layer includes: introducing nitrogen and adjusting the flow rate of nitrogen and argon to 4:6 respectively, maintaining the vacuum degree at 0.20~0.25Pa; keeping the sputtering parameters of the Me metal target consistent with the bottom layer deposition step, then opening the graphite target and connecting to a DC pulse power supply, setting its power to 0.5~3kW, the deposition temperature to 50~200℃, and the bias voltage alternately set between -300V and -600V, to perform alternating deposition of Me-N:C layers until the required number of layers is reached.

7. The method for preparing a high-adhesion wear-resistant and corrosion-resistant coating according to claim 6, characterized in that: The steps of depositing the functional layer include: turning off nitrogen, adjusting the argon flow rate to 120 sccm, and maintaining a vacuum degree of 0.22-0.25 Pa; keeping the sputtering parameters of the Me metal target and the graphite target consistent with the conversion layer deposition step; turning on the Nb target and connecting a high-power pulsed DC power supply, setting its power to increase from 2 kW to 5 kW at a rate of 0.1 kW / min, with a frequency of 10-1000 Hz, a pulse width of 50-200 μs, a bias voltage of -300--1000 V, and a deposition temperature of 50-200°C, to deposit the Me-Nb:C functional gradient layer under these conditions.

8. The method for preparing a high-adhesion wear-resistant and corrosion-resistant coating according to claim 3, characterized in that: The parameters of the vacuum annealing are: annealing temperature of 400-800°C, annealing time of 1-3 hours, vacuum degree of 10 -4 ~10 -5 Pa.

9. The method for preparing a high-adhesion wear-resistant and corrosion-resistant coating according to claim 3, characterized in that: The steps of forming the strengthening layer using ultrasonic rolling extrusion technology include: applying a static pressure of 20~80N, selecting an amplitude of 0.5~5μm, and maintaining a feed speed of 100~300mm / min during ultrasonic rolling extrusion.

10. Use of the high-adhesion wear-resistant and corrosion-resistant coating according to any one of claims 1 to 2 in surface treatment of metal materials.

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