Highly corrosion-resistant composite coating, and preparation method and application thereof

Abstract

The application discloses a high corrosion-resistant composite coating, which comprises Me layers and Me(O) layers arranged periodically and alternately, and the bottom layer and the top layer of the high corrosion-resistant composite coating are Me layers; oxygen is dissolved in the Me(O) layers, and the solid solution amount of the oxygen is 1-25 at.%; and Me is selected from one of Cr, Zr and Ti in the Me layers and the Me(O) layers. Compared with the prior art, the application introduces oxygen ions periodically, etches the interface, forms a Me / Me(O) multilayer structure, breaks the continuous growth of columnar crystals, blocks the fast diffusion channel of corrosion ions, increases the compactness of the coating, and makes the coating have high corrosion resistance.

Description

Technical Field

[0001] This invention belongs to the field of surface treatment technology, specifically relating to a highly corrosion-resistant composite coating, its preparation method, and its application. Background Technology

[0002] Electroplating metals (chromium, titanium, zirconium, etc.) is a traditional surface plating technology that holds a crucial position in the electroplating industry. However, chromium electroplating, especially hexavalent chromium electroplating, is a severe environmental pollutant, prompting active research both domestically and internationally on alternative technologies. Unlike electroplating, physical vapor deposition (PVD) is a green coating preparation technology that uses plasma generated by gas glow discharge under vacuum to deposit a film. It boasts numerous advantages, including low deposition temperature, wide substrate applicability, smooth and dense coating surface, and easy fine-tuning of composition, making it a promising candidate for developing and industrializing alternative metal coatings.

[0003] Existing PVD alternatives to electroplating technologies mainly include conventional magnetron sputtering and arc ion plating. However, coatings deposited using traditional DC-mode PVD, such as Cr coatings, suffer from penetrating columnar crystal defects. Breaking these columnar crystals often involves multilayer composites, but existing multilayer technologies suffer from heterogeneous interfaces, easily leading to galvanic corrosion. HiPIMS technology, a high-ionization physical vapor deposition technique based on traditional DC magnetron sputtering, has garnered significant attention in materials research and applications in recent years and is considered a major milestone in PVD development. This technology increases plasma density and the ionization rate of sputtered atoms through high-power pulsed discharge. The high ionization rate of the target allows for better control of film growth, and the energy and direction of ion deposition can be controlled by applying a bias voltage. Therefore, compared to DC or RF methods, coatings deposited using HiPIMS exhibit denser grain sizes, stronger film-substrate adhesion, higher coating quality, and wider applications.

[0004] The present invention provides an alternative electroplated chromium coating prepared using HiPIMS synchronous pulse bias technology. It does not use other phases, has a simple preparation process, and exhibits excellent corrosion resistance, making it a significant advantage among alternatives to electroplated chromium. Summary of the Invention

[0005] The purpose of this invention is to provide a highly corrosion-resistant composite coating that is not only simple to prepare, but also has excellent corrosion resistance and high coating density.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is: a high corrosion-resistant composite coating, comprising a Me layer and a Me(O) layer arranged in a periodic alternation, wherein the bottom layer and the top layer of the high corrosion-resistant composite coating are both Me layers, the Me(O) layer contains dissolved oxygen, and the dissolved oxygen content is 1 to 25 at.%, wherein the Me layer and the Me(O) layer are selected from one of Cr, Zr, and Ti.

[0007] Preferably, the thickness of the highly corrosion-resistant composite coating is 500-1500 nm, and the thickness of the Me(O) layer is 3-10 nm.

[0008] Preferably, the number of Me(O) layers is 3-10.

[0009] The second objective of this invention is to provide a method for preparing a highly corrosion-resistant composite coating, the method specifically comprising the following steps:

[0010] S1. After cleaning and drying the substrate, fix it on the sample stage of the magnetron sputtering equipment, and evacuate the cavity to a vacuum level of less than 3.0 × 10⁻⁶ at room temperature. -3 Pa;

[0011] S2. Perform Ar plasma etching on the substrate;

[0012] S3. A Me layer is deposited on the substrate that has been etched in step S2 using a high-power pulsed magnetron sputtering synchronous pulse bias technology.

[0013] S4. Oxygen etching is performed on the Me layer obtained in step S3 to obtain the Me(O) layer;

[0014] S5. Repeat steps S3 and S4 according to the set number of Me(O) layers;

[0015] S6. Using high-power pulsed magnetron sputtering synchronous pulse bias technology, a top Me layer is sputtered onto the coating obtained in step S5 to obtain a highly corrosion-resistant composite coating.

[0016] Preferably, in step S2, the Ar plasma etching conditions are as follows: argon flow rate of 30-50 sccm, sputtering pressure of 0.1-0.3 Pa, bias voltage of -90--110 V, ion source current of 0.1-0.3 A, etching temperature of room temperature, and etching time of 5-30 min.

[0017] Preferably, after Ar plasma etching, a Me target pre-sputtering treatment is performed before depositing the Me layer. The steps of the Me target pre-sputtering treatment are as follows: connect a HiPIMS power supply to the Me target, introduce argon gas into the magnetron sputtering equipment cavity, with an argon gas flow rate of 40-60 sccm, a sputtering pressure of 0.1-0.3 Pa, a sputtering power of 2000-4000 W, a discharge voltage of 800-1200 V, a peak current of 4-6 A, a pulse frequency of 400-600 Hz, a pulse width of 80-120 μs, a sputtering time of 5-10 min, and a deposition temperature of room temperature.

[0018] Preferably, the specific operation of step S3 is as follows: Connect the HiPIMS synchronous pulse bias power supply, adjust the distance between the sample stage and the Me target in the magnetron sputtering equipment cavity, introduce argon gas and turn on the high-power sputtering power supply, with an argon gas flow rate of 40-60 sccm, a sputtering pressure of 0.1-0.3 Pa, a pulse frequency of 300-700 Hz, a pulse width of 80-120 μs, a sputtering power of 400-600 W, a discharge voltage of 60-100 V, and a peak current of 4-6 A; or, with a synchronous pulse bias discharge frequency of 300-700 Hz, a sputtering power of 2000-4000 W, a discharge voltage of 800-1200 V, a peak current of 4-6 A, a deposition temperature of room temperature, and a deposition time of 5 min.

[0019] Preferably, the specific operation of step S4 is as follows: adjust the distance between the sample stage and the ion source in the magnetron sputtering equipment cavity, introduce oxygen and turn on the DC power supply, the oxygen flow rate is 100-120 sccm, the sputtering pressure is 0.1-0.3 Pa, the bias voltage is -90--110 V, the ion source current is 0.1-0.3 A, the etching temperature is room temperature, and the etching time is 15 min.

[0020] Preferably, the specific operation of step S5 is as follows: Connect the HiPIMS synchronous pulse bias power supply, adjust the distance between the sample stage and the Me target in the magnetron sputtering equipment cavity, introduce argon gas and turn on the high-power sputtering power supply, with an argon gas flow rate of 40-60 sccm, a sputtering pressure of 0.1-0.3 Pa, a pulse frequency of 300-700 Hz, a pulse width of 80-120 μs, a sputtering power of 400-600 W, a discharge voltage of 60-100 V, and a peak current of 4-6 A; or, with a synchronous pulse bias discharge frequency of 300-700 Hz, a sputtering power of 2000-4000 W, a discharge voltage of 800-1200 V, a peak current of 4-6 A, a deposition temperature of room temperature, and a deposition time of 10 min.

[0021] The third objective of this invention is to provide an application of a highly corrosion-resistant composite coating in automobiles and smart homes.

[0022] Compared with the prior art, the present invention has the following advantages:

[0023] 1. By periodically introducing oxygen ions for etching, the interface is passivated and a Me / Me(O) multilayer structure is formed. Without introducing heterogeneous elements and heterogeneous interfaces, the continuous growth of columnar crystals is interrupted, the rapid diffusion channel of corrosion ions is blocked, the coating density is increased, and the coating exhibits high corrosion resistance.

[0024] 2. This invention uses high-power pulsed magnetron sputtering with synchronous pulsed bias technology to deposit the Me layer. Compared with traditional DC magnetron sputtering, the plasma density and energy obtained are higher, and the surface of the prepared coating is smoother and denser.

[0025] 3. The coating deposition process used in this invention has a low deposition temperature and a wide range of applicable substrates, including but not limited to copper substrates, stainless steel substrates, and plastic (ABS) substrates. It also has good adhesion to the substrate, and the coating is not easy to peel off during service. Attached Figure Description

[0026] Figure 1 This is a schematic diagram of the highly corrosion-resistant composite coating obtained in Example 1 of the present invention;

[0027] Figure 2 This is an XRD structure diagram of the highly corrosion-resistant composite coating obtained in Example 1 of the present invention;

[0028] Figure 3 This is a scanning electron microscope image of the surface of the highly corrosion-resistant composite coating obtained in Example 1 of the present invention;

[0029] Figure 4 The figures show the 48-hour acid salt spray corrosion test results of the high corrosion resistant composite coating prepared in Example 1 of the present invention and the coating prepared in Comparative Example 1; wherein (a) is the morphology of the high corrosion resistant composite coating prepared in Example 1 of the present invention after 48 hours of acid salt spray corrosion test; and (b) is the morphology of the composite coating prepared in Comparative Example 1 of the present invention after 48 hours of acid corrosion test.

[0030] Figure 5 The images show the macroscopic morphology and optical microscope images of the highly corrosion-resistant composite coating prepared in Example 1 after abrasion testing.

[0031] Figure 6 The images show the macroscopic morphology of the coating prepared in Comparative Example 3 after abrasion testing and its morphology under an optical microscope.

[0032] Figure 7 The image shows the surface profilometer test results of the highly corrosion-resistant composite coating prepared in Example 1.

[0033] Figure 8 The image shows the surface profilometer test results of the coating prepared in Comparative Example 3. Detailed Implementation

[0034] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

[0035] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0036] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be readily apparent to those skilled in the art. This application specification and embodiments are merely exemplary.

[0037] The present invention provides a highly corrosion-resistant composite coating comprising a Me layer and a Me(O) layer arranged in a periodic alternation, wherein the bottom and top layers of the highly corrosion-resistant composite coating are both Me layers, and oxygen is dissolved in the Me(O) layer, wherein the amount of oxygen dissolved is 1 to 25 at.%, and Me in the Me layer and the Me(O) layer is selected from one of Cr, Zr and Ti.

[0038] In a specific embodiment, the thickness of the highly corrosion-resistant composite coating is 500-1500 nm, and the thickness of the Me(O) layer is 3-10 nm.

[0039] In a specific embodiment, the number of Me(O) layers is 3-10.

[0040] The second objective of this invention is to provide a method for preparing a highly corrosion-resistant composite coating, which specifically includes the following steps:

[0041] S1. After cleaning and drying the substrate, fix it on the sample stage of the magnetron sputtering equipment, and evacuate the cavity to a vacuum level of less than 3.0 × 10⁻⁶ at room temperature. -3 Pa;

[0042] S2. The substrate is subjected to Ar plasma etching. The conditions for Ar plasma etching are as follows: argon flow rate of 30-50 sccm, sputtering pressure of 0.1-0.3 Pa, bias voltage of -90--110 V, ion source current of 0.1-0.3 A, etching temperature of room temperature, and etching time of 5-30 min.

[0043] The pre-sputtering treatment of S3 and Me targets is as follows: Connect the HiPIMS power supply to the Me target, introduce argon gas into the magnetron sputtering equipment cavity, with an argon gas flow rate of 40-60 sccm, a sputtering pressure of 0.1-0.3 Pa, a sputtering power of 2000-4000 W, a discharge voltage of 800-1200 V, a peak current of 4-6 A, a pulse frequency of 400-600 Hz, a pulse width of 80-120 μs, a sputtering time of 5-10 min, and a deposition temperature of room temperature;

[0044] S4. Using high-power pulsed magnetron sputtering with synchronous pulsed bias technology, deposit a Me layer on the substrate etched in step S2. The specific operation is as follows: Connect the HiPIMS synchronous pulsed bias power supply, adjust the distance between the sample stage and the Me target in the magnetron sputtering equipment cavity, introduce argon gas and turn on the high-power sputtering power supply. The argon gas flow rate is 40-60 sccm, the sputtering pressure is 0.1-0.3 Pa, the pulse frequency is 300-700 Hz, the pulse width is 80-120 μs, the sputtering power is 400-600 W, the discharge voltage is 60-100 V, and the peak current is 4-6 A. The synchronous pulsed bias discharge frequency is 300-700 Hz, the sputtering power is 2000-4000 W, the discharge voltage is 800-1200 V, the peak current is 4-6 A, the deposition temperature is room temperature, and the deposition time is 5 min.

[0045] S4. Oxygen etching is performed on the Me layer obtained in step S3 to obtain the Me(O) layer. The specific operation is as follows: Adjust the distance between the sample stage and the ion source in the magnetron sputtering equipment cavity, introduce oxygen and turn on the DC power supply. The oxygen flow rate is 100-120 sccm, the sputtering pressure is 0.1-0.3 Pa, the bias voltage is -90--110 V, the ion source current is 0.1-0.3 A, the etching temperature is room temperature, and the etching time is 15 min. S5. Repeat steps S3 and S4 according to the set number of Me(O) layers.

[0046] S6. Using high-power pulsed magnetron sputtering with synchronous pulse bias technology, a top Me layer is sputtered onto the coating obtained in step S5 to obtain a highly corrosion-resistant composite coating. The specific operation is as follows: Connect the HiPIMS synchronous pulse bias power supply, adjust the distance between the sample stage and the Me target in the magnetron sputtering equipment cavity, introduce argon gas and turn on the high-power sputtering power supply. The argon gas flow rate is 40-60 sccm, the sputtering gas pressure is 0.1-0.3 Pa, the pulse frequency is 300-700 Hz, the pulse width is 80-120 μs, the sputtering power is 400-600 W, the discharge voltage is 60-100 V, and the peak current is 4-6 A. The synchronous pulse bias discharge frequency is 300-700 Hz, the sputtering power is 2000-4000 W, the discharge voltage is 800-1200 V, the peak current is 4-6 A, the deposition temperature is room temperature, and the deposition time is 10 min.

[0047] The third objective of this invention is to provide an application of a highly corrosion-resistant composite coating in automobiles and smart homes.

[0048] The technical effects of the present invention will be described below with reference to specific embodiments.

[0049] Example 1

[0050] like Figure 1 As shown, this embodiment provides a highly corrosion-resistant composite coating. The substrate is a plastic base, and the power supply used is a high-power pulsed magnetron sputtering power supply and a synchronous pulse bias voltage. A Cr target is used as the magnetron source. The preparation method of the highly corrosion-resistant composite coating on the substrate surface is as follows:

[0051] A. Substrate pretreatment: The substrate is ultrasonically cleaned with alcohol and then dried.

[0052] B. Sample mounting: Fix the treated substrate onto the sample stage of the magnetron sputtering equipment;

[0053] C. Vacuum preparation of the cavity: Evacuate the cavity to 3.0 × 10⁻⁶. -3 Below Pa, the temperature is room temperature;

[0054] D. Etching the substrate: Plasma glow lithography was performed on the substrate under the conditions of bias voltage of -100V, argon flow rate of 40sccm, ion source current of 0.2A, and sputtering pressure of 0.2Pa. The etching time was 15 minutes, with a 5-minute rest period after every 5 minutes of etching.

[0055] E. Pre-sputtering: Connect the HiPIMS power supply to the Cr target, introduce argon gas into the magnetron sputtering equipment cavity, with an argon gas flow rate of 50 sccm, a sputtering pressure of 0.15 Pa, a sputtering power of 3000 W, a discharge voltage of 1000 V, a peak current of 5 A, a pulse frequency of 500 Hz, a pulse width of 100 μs, a sputtering time of 5 min, and a temperature of room temperature;

[0056] F. Sputtering Cr Coating: Connect the HiPIMS synchronous pulse bias power supply, adjust the distance between the sample stage and the Cr target in the magnetron sputtering equipment cavity, introduce argon gas and turn on the high-power sputtering power supply. The argon gas flow rate is 50 sccm, the sputtering pressure is 0.15 Pa, the pulse frequency is 500 Hz, the pulse width is 100 μs, the sputtering power is 500 W, the discharge voltage is 80 V, and the peak current is 5 A. The synchronous pulse bias discharge frequency is 500 Hz, the sputtering power is 3000 W, the discharge voltage is 1000 V, and the peak current is 5 A. The deposition temperature is room temperature, and the deposition time is 5 minutes. A sample with a Cr coating is obtained. Stop sputtering and let it rest for 5 minutes.

[0057] G. Oxygen etching: Adjust the distance between the sample stage and the ion source in the magnetron sputtering equipment chamber, introduce oxygen and turn on the DC power supply. The oxygen flow rate is 110 sccm, the sputtering pressure is 0.25 Pa, the bias voltage is -100 V, the ion source current is 0.2 A, the etching temperature is room temperature, the etching time is 15 minutes, and after every 5 minutes of etching, rest for 5 minutes.

[0058] H. Each step, F and G, constitutes one cycle, for a total of 3 cycles;

[0059] I. Sputtering Cr coating: The sputtering process is the same as F, except that the sputtering time is 10 minutes, and there is a 5-minute rest after every 5 minutes of sputtering, resulting in a Cr coating with a multi-layer structure. The sample is then removed.

[0060] The microstructure of the highly corrosion-resistant composite coating prepared in Example 1 was analyzed using scanning electron microscopy and energy dispersive spectroscopy (EDS). The surface morphology is as follows: Figure 3 As shown in the table below, the surface elemental atomic percentages analyzed by EDS energy dispersive spectroscopy are as follows:

[0061] element At% Cr 83.9 C 10.8 O 5.3

[0062] As can be seen from the table above, the surface of the high corrosion-resistant composite coating contains trace amounts of oxygen after oxygen etching. XRD pattern analysis of the high corrosion-resistant composite coating yields the following results: Figure 2 As shown, the analysis revealed that O dissolved in the crystal lattice rather than forming chromium oxide.

[0063] Example 2

[0064] In this embodiment, the substrate is a Cu substrate, the power supply used is a high-power pulsed magnetron sputtering power supply and a synchronous pulse bias voltage, and a Ti target is used as the magnetron source. The preparation method of the PVD Ti multilayer coating on the substrate surface is as follows:

[0065] A. Matrix pretreatment: The matrix is ​​ultrasonically cleaned with acetone and then dried.

[0066] B. Sample mounting: Fix the treated substrate onto the sample stage of the magnetron sputtering equipment;

[0067] C. Vacuum preparation of the cavity: Evacuate the cavity to 3.0 × 10⁻⁶. -3 Below Pa, the temperature is room temperature;

[0068] D. Etching the substrate: Plasma glow lithography was performed on the substrate under the conditions of a bias voltage of -100V, an argon flow rate of 40sccm, and an ion source current of 0.2A for 15 minutes.

[0069] E. Pre-sputtering: Connect the HiPIMS power supply to the Ti target, introduce argon gas into the magnetron sputtering equipment cavity, with an argon gas flow rate of 50 sccm, a sputtering gas pressure of 0.15 Pa, a sputtering power of 3000 W, a discharge voltage of 1000 V, a peak current of 5 A, a pulse frequency of 500 Hz, a pulse width of 100 μs, a sputtering time of 5 min, and a temperature of room temperature;

[0070] F. Sputtering Ti Coating: Connect the HiPIMS synchronous pulse bias power supply, adjust the distance between the sample stage and the Ti target in the magnetron sputtering equipment cavity, introduce argon gas and turn on the high-power sputtering power supply. The argon gas flow rate is 50 sccm, the sputtering pressure is 0.15 Pa, the pulse frequency is 500 Hz, the pulse width is 100 μs, the sputtering power is 500 W, the discharge voltage is 80 V, and the peak current is 5 A. The synchronous pulse bias discharge frequency is 500 Hz, the sputtering power is 3000 W, the discharge voltage is 1000 V, and the peak current is 5 A. The deposition temperature is room temperature, and the deposition time is 5 minutes. A sample with a Ti coating is obtained. Stop sputtering.

[0071] G. Oxygen etching: Adjust the distance between the sample stage and the ion source in the magnetron sputtering equipment chamber, introduce oxygen and turn on the DC power supply. The oxygen flow rate is 110 sccm, the sputtering pressure is 0.25 Pa, the bias voltage is -100 V, the ion source current is 0.2 A, the etching temperature is room temperature, and the etching time is 15 minutes.

[0072] H. Each step, F and G, constitutes one cycle, for a total of 3 cycles;

[0073] I. Sputtering Ti coating: The sputtering process is the same as F, except that the sputtering time is 10 minutes, resulting in a Ti coating with a multi-layer structure. The sample is then removed.

[0074] Example 3

[0075] In this embodiment, the substrate is a stainless steel substrate, the power supply is a high-power pulsed magnetron sputtering power supply and a synchronous pulse bias voltage, and a Zr target is used as the magnetron source. The preparation method of the PVD-Zr ​​multilayer coating on the substrate surface is as follows:

[0076] A. Matrix pretreatment: The matrix is ​​ultrasonically cleaned with acetone and then dried.

[0077] B. Sample mounting: Fix the treated substrate onto the sample stage of the magnetron sputtering equipment;

[0078] C. Vacuum preparation of the cavity: Evacuate the cavity to 3.0 × 10⁻⁶. -3 Below Pa, the temperature is room temperature.

[0079] D. Etching the substrate: Plasma glow lithography was performed on the substrate under the conditions of a bias voltage of -100V, an argon flow rate of 40sccm, and an ion source current of 0.2A for 15 minutes.

[0080] E. Pre-sputtering: Connect the HiPIMS power supply to the Zr target, introduce argon gas into the magnetron sputtering equipment cavity, with an argon gas flow rate of 50 sccm, a sputtering gas pressure of 0.15 Pa, a sputtering power of 3000 W, a discharge voltage of 1000 V, a peak current of 5 A, a pulse frequency of 500 Hz, a pulse width of 100 μs, a sputtering time of 5 min, and a temperature of room temperature;

[0081] F. Sputtering Zr Coating: Connect the HiPIMS synchronous pulse bias power supply, adjust the distance between the sample stage and the Zr target in the magnetron sputtering equipment cavity, introduce argon gas and turn on the high-power sputtering power supply. The argon gas flow rate is 50 sccm, the sputtering pressure is 0.15 Pa, the pulse frequency is 500 Hz, the pulse width is 100 μs, the sputtering power is 500 W, the discharge voltage is 80 V, and the peak current is 5 A. The synchronous pulse bias discharge frequency is 500 Hz, the sputtering power is 3000 W, the discharge voltage is 1000 V, and the peak current is 5 A. The deposition temperature is room temperature, and the deposition time is 5 minutes. A sample with a Zr coating is obtained. Stop sputtering.

[0082] G. Oxygen etching: Adjust the distance between the sample stage and the ion source in the magnetron sputtering equipment chamber, introduce oxygen and turn on the DC power supply. The oxygen flow rate is 110 sccm, the sputtering pressure is 0.25 Pa, the bias voltage is -100 V, the ion source current is 0.2 A, the etching temperature is room temperature, and the etching time is 15 minutes.

[0083] H. Each step, F and G, constitutes one cycle, for a total of 3 cycles;

[0084] I. Sputtering Zr coating: The sputtering process is the same as F, except that the sputtering time is 10 minutes, resulting in a Zr coating with a multi-layer structure. The sample is then removed.

[0085] Comparative Example 1:

[0086] The only difference from Example 1 is that in steps E, F, H, and I, this comparative example uses a DC power supply; all other conditions are the same as in Example 1. The specific process is as follows:

[0087] A. Substrate pretreatment: The substrate is ultrasonically cleaned with alcohol and then dried.

[0088] B. Sample mounting: Fix the treated substrate onto the sample stage of the magnetron sputtering equipment;

[0089] C. Vacuum preparation of the cavity: Evacuate the cavity to 3.0 × 10⁻⁶.-3 Below Pa, the temperature is room temperature;

[0090] D. Etching the substrate: Plasma glow lithography was performed on the substrate under the conditions of a bias voltage of -100V, an argon flow rate of 40sccm, and an ion source current of 0.2A. The etching time was 15 minutes, with a 5-minute rest period after every 5 minutes of etching.

[0091] E. Pre-sputtering: Argon gas is introduced into the cavity of the magnetron sputtering equipment to pre-sputter the Cr target to remove oxides or adsorbed impurities on the target surface; the pre-sputtering power is 3000W, the argon gas flow rate is 50sccm, the cavity vacuum is 2.5Pa, and the sputtering time is 5min.

[0092] F. Sputtering Cr Coating: Adjust the distance between the sample stage and the Cr target in the magnetron sputtering equipment cavity, set the argon flow rate to 50 sccm, the sputtering pressure to 0.25 Pa, the bias voltage to -80 V, the current to 5.0 A, the deposition temperature to room temperature, and the deposition time to 5 minutes to obtain a sample with a Cr coating. Stop sputtering and let it rest for 5 minutes.

[0093] G. Oxygen etching: Adjust the distance between the sample stage and the ion source in the magnetron sputtering equipment cavity, introduce oxygen and turn on the DC power supply. The oxygen flow rate is 110 sccm, the sputtering pressure is 0.25 Pa, the bias voltage is -100 V, the ion source current is 0.2 A, the etching temperature is room temperature, the etching time is 15 minutes, and there is a 5-minute rest after every 5 minutes of etching.

[0094] H. Each step, F and G, constitutes one cycle, for a total of 3 cycles;

[0095] I. Sputtering Cr coating: The sputtering process is the same as F, except that the sputtering time is 10 minutes, and there is a 5-minute rest after every 5 minutes of sputtering, resulting in a Cr coating with a multi-layer structure. The sample is then removed.

[0096] Comparative Example 2:

[0097] The only difference from Example 1 is that in steps F, H, and I, this comparative example uses only a HiPIMS power supply; all other conditions are the same as in Example 1. The specific process is as follows:

[0098] A. Substrate pretreatment: The substrate is ultrasonically cleaned with alcohol and then dried.

[0099] B. Sample mounting: Fix the treated substrate onto the sample stage of the magnetron sputtering equipment;

[0100] C. Vacuum preparation of the cavity: Evacuate the cavity to 3.0 × 10⁻⁶. -3 Below Pa, the temperature is room temperature;

[0101] D. Etching the substrate: Plasma glow lithography was performed on the substrate under the conditions of a bias voltage of -100V, an argon flow rate of 40sccm, and an ion source current of 0.2A. The etching time was 15 minutes, with a 5-minute rest period after every 5 minutes of etching.

[0102] E. Pre-sputtering: Connect the HiPIMS power supply to the Cr target, introduce argon gas into the magnetron sputtering equipment cavity, with an argon gas flow rate of 50 sccm, a sputtering pressure of 0.15 Pa, a sputtering power of 3000 W, a discharge voltage of 1000 V, a peak current of 5 A, a pulse frequency of 500 Hz, a pulse width of 100 μs, a sputtering time of 5 min, and a temperature of room temperature;

[0103] F. Sputtering Cr Coating: Adjust the distance between the sample stage and the Cr target in the magnetron sputtering equipment chamber, introduce argon gas and turn on the high-power sputtering power supply. The argon gas flow rate is 50 sccm, the sputtering pressure is 0.15 Pa, the pulse frequency is 500 Hz, the pulse width is 100 μs, the sputtering power is 500 W, the discharge voltage is 80 V, the peak current is 5 A, the deposition temperature is room temperature, and the deposition time is 5 minutes. A sample with a Cr coating is obtained. Stop sputtering and let it rest for 5 minutes.

[0104] G. Oxygen etching: Adjust the distance between the sample stage and the ion source in the magnetron sputtering equipment cavity, introduce oxygen and turn on the DC power supply. The oxygen flow rate is 110 sccm, the sputtering pressure is 0.25 Pa, the bias voltage is -100 V, the ion source current is 0.2 A, the etching temperature is room temperature, the etching time is 15 minutes, and there is a 5-minute rest after every 5 minutes of etching.

[0105] H. Each step, F and G, constitutes one cycle, for a total of 3 cycles;

[0106] I. Sputtering Cr coating: The sputtering process is the same as F, except that the sputtering time is 10 minutes, and there is a 5-minute rest after every 5 minutes of sputtering, resulting in a Cr coating with a multi-layer structure. The sample is then removed.

[0107] Comparative Example 3:

[0108] The only difference from Example 1 is that this comparative example was not treated with oxygen plasma; all other conditions were the same as in Example 1. The specific process is as follows:

[0109] A. Substrate pretreatment: The substrate is ultrasonically cleaned with alcohol and then dried.

[0110] B. Sample mounting: Fix the treated substrate onto the sample stage of the magnetron sputtering equipment;

[0111] C. Vacuum preparation of the cavity: Evacuate the cavity to 3.0 × 10⁻⁶. -3 Below Pa, the temperature is room temperature;

[0112] D. Etching the substrate: Plasma glow lithography was performed on the substrate under the conditions of bias voltage of -100V, argon flow rate of 40sccm, ion source current of 0.2A, and sputtering pressure of 0.2Pa. The etching time was 15 minutes, with a 5-minute rest period after every 5 minutes of etching.

[0113] E. Pre-sputtering: Connect the HiPIMS power supply to the Cr target, introduce argon gas into the magnetron sputtering equipment cavity, with an argon gas flow rate of 50 sccm, a sputtering pressure of 0.15 Pa, a sputtering power of 3000 W, a discharge voltage of 1000 V, a peak current of 5 A, a pulse frequency of 500 Hz, a pulse width of 100 μs, a sputtering time of 5 min, and a temperature of room temperature;

[0114] F. Sputtering Cr Coating: Connect the HiPIMS synchronous pulse bias power supply, adjust the distance between the sample stage and the Cr target in the magnetron sputtering equipment chamber, introduce argon gas and turn on the high-power sputtering power supply. The argon gas flow rate is 50 sccm, the sputtering pressure is 0.15 Pa, the pulse frequency is 500 Hz, the pulse width is 100 μs, the sputtering power is 500 W, the discharge voltage is 80 V, and the peak current is 5 A. The synchronous pulse bias discharge frequency is 500 Hz, the sputtering power is 3000 W, the discharge voltage is 1000 V, the peak current is 5 A, the deposition temperature is room temperature, the deposition time is 30 minutes, and after every 5 minutes of deposition, rest for 5 minutes to obtain a sample with a Cr coating. Stop sputtering and remove the sample.

[0115] Performance testing:

[0116] 1. The coatings prepared in Example 1 and Comparative Example 1 were subjected to an acidic salt spray test for 48 hours, and the results are as follows: Figure 4 As shown, where Figure 4 (a) is a graph showing the 48-hour acid salt spray test results of the high corrosion resistant composite coating prepared in Example 1. It can be seen that the surface properties of the high corrosion resistant composite coating prepared in Example 1 are intact. Figure 4 (b) is a diagram of the 48h acid salt spray test results of the coating prepared in Comparative Example 1. It can be seen that the coating prepared in Comparative Example 1 has a large area of ​​peeling off. It can be seen that the use of high-power pulsed magnetron sputtering power supply and synchronous pulse bias voltage has achieved stable discharge of high ionized plasma, which makes the deposited high corrosion resistant composite coating better bonded to the substrate and has good corrosion resistance.

[0117] 2. The coatings prepared in Example 1 and Comparative Example 2 were subjected to abrasion tests. The results showed that the high corrosion resistant composite coating prepared in Example 1 exhibited better performance than the coating prepared in Comparative Example 2, indicating that the high corrosion resistant composite coating deposited by synchronous pulse bias technology has better adhesion to the substrate and good abrasion resistance.

[0118] 3. Abrasion tests were performed on the coatings obtained in Example 1 and Comparative Example 3, and the results are as follows: Figure 5 and Figure 6 As shown, from Figure 5 It can be seen that the highly corrosion-resistant composite coating prepared in Example 1 has significantly better abrasion resistance; from Figure 6 As can be seen, the abrasion portion of the coating prepared in Comparative Example 3 was completely peeled off, indicating that the high corrosion-resistant composite coating deposited using oxygen plasma treatment has better adhesion to the substrate and better abrasion resistance.

[0119] 4. The coatings obtained in Example 1 and Comparative Example 3 were subjected to surface profilometry tests, and the test results are as follows: Figure 7 and Figure 8 As shown, from Figure 7 It can be seen that the coating treated with oxygen plasma exhibits significantly better wear and corrosion resistance, with only slight peeling observed. Figure 8 It can be seen that the coating that was not treated with oxygen plasma completely peeled off, and the substrate was scratched. And from... Figure 7 and Figure 8 The comparison further shows that the wear mark depth of the coating prepared in Comparative Example 1 is about 20 times that of the high corrosion resistant composite coating prepared in Example 1. It can be seen that the high corrosion resistant composite coating deposited by oxygen plasma treatment can break the penetrating corrosion channels of columnar crystals and enhance the wear resistance of the coating.

[0120] While the disclosure is as stated above, its scope of protection is not limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of this disclosure, and all such changes and modifications will fall within the protection scope of this invention.

Claims

1. A highly corrosion-resistant composite coating, characterized in that, The coating includes a periodically alternating Me layer and a Me(O) layer, wherein the bottom and top layers of the high corrosion-resistant composite coating are both Me layers. In the Me(O) layer, oxygen is dissolved in the crystal lattice, and the content of the dissolved oxygen is 1~25 at.%. In the Me layer and the Me(O) layer, Me is selected from one of Cr, Zr, and Ti.

2. The high corrosion-resistant composite coating as described in claim 1, characterized in that, The thickness of the highly corrosion-resistant composite coating is 500-1500 nm, and the thickness of the Me(O) layer is 3-10 nm.

3. The high corrosion-resistant composite coating as described in claim 1, characterized in that, The number of Me(O) layers is 3-10.

4. A method for preparing a highly corrosion-resistant composite coating as described in any one of claims 1-3, characterized in that, The preparation method specifically includes the following steps: S1. After cleaning and drying the substrate, fix it on the sample stage of the magnetron sputtering equipment, and evacuate the cavity to a vacuum level of less than 3.0 × 10⁻⁶ at room temperature. -3 Pa; S2. Perform Ar plasma etching on the substrate; S3. A Me layer is deposited on the substrate that has been etched in step S2 using a high-power pulsed magnetron sputtering synchronous pulse bias technology. S4. Oxygen etching is performed on the Me layer obtained in step S3 to obtain the Me(O) layer. The specific operation is as follows: Adjust the distance between the sample stage and the ion source in the magnetron sputtering equipment cavity, introduce oxygen and turn on the DC power supply. The oxygen flow rate is 100~120 sccm, the sputtering pressure is 0.1~0.3 Pa, the bias voltage is -90~-110 V, the ion source current is 0.1~0.3 A, the etching temperature is room temperature, and the etching time is 15 min. S5. Repeat steps S3 and S4 according to the set number of Me(O) layers; S6. Using high-power pulsed magnetron sputtering synchronous pulse bias technology, a top Me layer is sputtered onto the coating obtained in step S5 to obtain a highly corrosion-resistant composite coating.

5. The method for preparing the highly corrosion-resistant composite coating as described in claim 4, characterized in that, In step S2, the conditions for Ar plasma etching are as follows: argon flow rate of 30~50 sccm, sputtering pressure of 0.1~0.3 Pa, bias voltage of -90~-110 V, ion source current of 0.1~0.3 A, etching temperature of room temperature, and etching time of 5~30 min.

6. The method for preparing the highly corrosion-resistant composite coating as described in claim 4, characterized in that, After Ar plasma etching, a Me target pre-sputtering treatment is performed before depositing the Me layer. The steps of the Me target pre-sputtering treatment are as follows: connect a HiPIMS power supply to the Me target, introduce argon gas into the magnetron sputtering equipment cavity, with an argon gas flow rate of 40~60 sccm, a sputtering gas pressure of 0.1~0.3 Pa, a sputtering power of 2000~4000 W, a discharge voltage of 800~1200 V, a peak current of 4~6 A, a pulse frequency of 400~600 Hz, a pulse width of 80~120 μs, a sputtering time of 5~10 min, and a deposition temperature of room temperature.

7. The method for preparing the highly corrosion-resistant composite coating as described in claim 4, characterized in that, The specific operation of step S3 is as follows: Connect the HiPIMS synchronous pulse bias power supply, adjust the distance between the sample stage and the Me target in the magnetron sputtering equipment cavity, introduce argon gas and turn on the high-power sputtering power supply. The argon gas flow rate is 40~60 sccm, the sputtering pressure is 0.1~0.3 Pa, the pulse frequency is 300~700 Hz, the pulse width is 80~120 μs, the sputtering power is 400~600 W, the discharge voltage is 60~100 V, and the peak current is 4~6 A. The synchronous pulse bias discharge frequency is 300~700 Hz, the sputtering power is 2000~4000 W, the discharge voltage is 800~1200 V, the peak current is 4~6 A, the deposition temperature is room temperature, and the deposition time is 5 min.

8. The method for preparing the highly corrosion-resistant composite coating as described in claim 4, characterized in that, The specific operation of step S5 is as follows: Connect the HiPIMS synchronous pulse bias power supply, adjust the distance between the sample stage and the Me target in the magnetron sputtering equipment cavity, introduce argon gas and turn on the high-power sputtering power supply. The argon gas flow rate is 40~60 sccm, the sputtering pressure is 0.1~0.3 Pa, the pulse frequency is 300~700 Hz, the pulse width is 80~120 μs, the sputtering power is 400~600 W, the discharge voltage is 60~100 V, and the peak current is 4~6 A. The synchronous pulse bias discharge frequency is 300~700 Hz, the sputtering power is 2000~4000 W, the discharge voltage is 800~1200 V, the peak current is 4~6 A, the deposition temperature is room temperature, and the deposition time is 10 min.

9. The application of a highly corrosion-resistant composite coating as described in any one of claims 1-3 in automobiles and smart homes.

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