Preparation method and application of supersonic arc sprayed laminated structure wear-resistant ceramic coating

Abstract

The present invention belongs to the technical field of wear-resistant coatings, and discloses a method and application of preparing a Cu-TiN / TiO2 laminated structure composite ceramic coating using supersonic arc spraying technology. The present invention can control the proportion of each phase in the coating by spraying different diameter ratios between heterogeneous wires, and can achieve uniform distribution of Ti nitrogen oxides and Cu elemental substance inside the coating. Its unique Cu-TiN / TiO2-Cu laminated structure can enable the coating to achieve different hardness and toughness matching, thereby improving the wear resistance of the coating under different service environments. The preparation method of the coating is simple, there are no harsh requirements for the construction and processing environment, and the preparation efficiency is high. The coating can be used for the surface protection of various workpieces and engineering structures in fields such as engineering equipment serving in marine environments and those near the sea where wear conditions are relatively severe.

Description

Technical Field

[0001] The present invention belongs to the technical field of thermal spraying wear-resistant coating preparation, and particularly relates to a preparation method and application of a Cu-TiN / TiO2 laminated structure wear-resistant composite ceramic coating prepared by supersonic arc spraying technology. Background Art

[0002] Engineering equipment serving in coastal or marine environments is subject to the combined effects of multiple material failure mechanisms. These include corrosion from aggressive ions in seawater, erosive wear from seawater and its inclusions, and contact wear between engineering equipment. The strong coupling of these factors often leads to deterioration of the material's mechanical properties, accelerating the aging and failure of engineering equipment, and reducing its operational stability and service life. Surface coatings can improve material performance and durability, effectively mitigating environmental damage such as corrosion and abrasion to the substrate, and are widely used in industry, aviation, and marine applications. Ti nitride and oxide coatings are popular choices for surface protective coatings due to their excellent wear, erosion, and corrosion resistance, as well as their excellent adhesion to the substrate. Cu and Cu alloys offer excellent mechanical properties, resistance to seawater corrosion, erosion corrosion, and excellent resistance to marine biofouling. The Cu phase, with its low hardness and elastic modulus, creates an appropriate hardness-toughness match with the hard ceramic phase, thereby enhancing the coating's wear resistance. Therefore, the preparation of a composite coating with a laminated structure and wear resistance has significant application value in protecting engineering equipment serving in marine environments.

[0003] Supersonic arc spraying (HSA) has been recognized as a practical and effective on-site repair solution. It is also a relatively inexpensive thermal spray process, capable of producing a dense, ultrafine-grained coating within the sprayed coating. Arc spraying also offers flexible raw material design, allowing for the use of metal wires of varying sizes and powder-cored wires containing ceramic hybrids. This allows the spraying process to be applied regardless of site or workpiece size. During the spraying process, the insulated wires melt instantly in the high-temperature arc zone, where high-pressure gas atomizes them into high-velocity molten droplets. These droplets impact the substrate, forming a stacked coating. Arc spraying metal-ceramic composite coatings typically utilize alloy metal wires or powder-cored wires containing core materials in varying proportions. However, the complex preparation process for alloy wires, limited compositional design, and high production costs limit the production of large-scale composite ceramic coatings. Furthermore, the melting point, particle size, dispersion, and oxidation characteristics of the metal or ceramic particles encapsulating the powder-cored wires significantly impact the coating's performance. Poor melting and atomization of powder particles during spraying and incomplete dispersion of molten droplets on the substrate will lead to excessive defects in the coating, thus affecting the overall performance of the coating. Summary of the Invention

[0004] To overcome the shortcomings and deficiencies of the aforementioned prior art, the primary objective of the present invention is to provide a laminated, wear-resistant composite ceramic coating. This coating utilizes commercially available pure Ti and Cu wires of varying diameters as raw materials. Using supersonic arc spraying technology, by manipulating the diameter of the heterogeneous metal wires in a coaxial wire feed wheel and the parameters during the spraying process, Cu-TiN / TiO2 laminated, wear-resistant composite ceramic coatings with varying Cu contents are prepared on the surfaces of commonly used engineering equipment and materials, such as structural steel and aluminum alloys.

[0005] Another object of the present invention is to provide a method for preparing the above-mentioned laminated wear-resistant composite ceramic coating.

[0006] Another object of the present invention is to provide an application of the above-mentioned laminated wear-resistant composite ceramic coating.

[0007] The purpose of the present invention is achieved through the following solutions:

[0008] A laminated wear-resistant composite ceramic coating is prepared by supersonic arc spraying of pure Ti wires and pure Cu wires of different diameters. The coating is a Cu-TiN / TiO2 laminated wear-resistant composite ceramic coating.

[0009] Preferably, the copper element in the laminated wear-resistant composite ceramic coating exists primarily in the form of elemental copper, with a minimal amount of cuprous oxide present. Cu does not form impurity phases that could affect its corrosion resistance. Titanium primarily exists in the form of titanium nitrides and titanium oxides, and Ti does not form intermediate phases that could affect its hardness and wear resistance. The proportions of the various phases in the composite coating vary depending on the diameter difference between the pure Cu and pure Ti wires during the spraying process.

[0010] Preferably, the main components of the laminated wear-resistant composite ceramic coating are Cu, TiN, TiO2, TiN 0.3 and Cu2O.

[0011] Preferably, the content of Cu in the laminated wear-resistant composite ceramic coating is 8.3%-66.6%, more preferably 8.3%-35.8%.

[0012] The thickness of the laminated wear-resistant composite ceramic coating is 200-1000 μm.

[0013] The purity of the Ti wire and Cu wire is preferably ≥99.9%.

[0014] The diameter of the Ti wire is 0.5-2.0 mm, preferably 1.5 mm.

[0015] The diameter of the Cu wire is 0.2-2.0 mm.

[0016] The lengths of the Ti wire and the Cu wire are ≥2000 mm.

[0017] A method for preparing the above-mentioned laminated wear-resistant composite ceramic coating includes the following steps: fixing pure Ti wire and pure Cu wire of different diameter ratios through a coaxial roller wire feeding device, spraying after setting the spraying parameters on the control panel, and obtaining a composite ceramic coating.

[0018] The present invention controls the diameter ratio of two heterogeneous metal wires during supersonic synchronous wire feeding arc spraying, and relies on the mutual reaction of heterogeneous metal wires of different diameters during melting, atomization, and flight at the arc tip to obtain a high-performance composite ceramic coating of corresponding components. During the spraying process, the stability of the wire, the speed and oxidation reaction of the molten droplet flight, the pseudo-alloy reaction between the molten droplets, and the interaction between the molten droplets and the substrate all need to be precisely controlled by regulating the spraying parameters. This preparation method can achieve precise control of the coating thickness and the nitrogen oxide content of Cu and Ti in the coating, so that the composite coating meets the protection requirements of the surface of engineering equipment under multiple working conditions. The spraying process is simple and has strong construction adaptability. It is a relatively efficient and low-cost coating preparation method.

[0019] A large amount of equipment currently in service in marine environments or coastal environments, such as ships, offshore drilling platforms, cross-sea bridges, oil and gas pipelines, etc., are generally constructed using cast iron, structural steel, aluminum alloys, etc. Particularly on equipment that will withstand heavy loads and dynamic loads, a large amount of structural steels with higher strength, such as Q345, Q390, Q420, Q460, Q500, etc., are used. Therefore, the base material selected for use during spraying of the present invention is at least one of structural steel and aluminum alloy, preferably one of Q345, Q390, Q420, Q460, Q500, and more preferably Q345B structural steel.

[0020] The size of the substrate is preferably a small round block of Ø25*9 mm; the surface of the substrate is roughened before use, preferably by sandblasting.

[0021] The parameters of the supersonic arc spraying process are as follows: the arc working voltage is 38-44V, the arc working current is 40-120A, the wire feeding speed is 3m / min-10m / min, the compressed air pressure is 0.8Mpa, and the spraying distance is 120mm. The speed of the servo motor that controls the movement of the spray gun is 5-20mm / s in the horizontal direction. According to different wire feeding voltages and wire feeding speeds, the optimal single spraying time is 15-50S, preferably 18-40s. The coating can be sprayed repeatedly until the coating thickness is 200-1000μm, but the continuous spraying time should not be too long to prevent the coating from having large thermal stress cracking. The above-mentioned metal wire melts in the high-temperature arc area, and after being accelerated by high-pressure gas, supersonic atomized small droplets are formed, which then collide, diffuse, flatten, and quickly solidify on the substrate to form a functional coating with dense structure, few defects, strong bonding force, high hardness, and certain laminated structure wear resistance.

[0022] The above-mentioned laminated wear-resistant composite ceramic coating is preferably used for surface protection of various workpieces and engineering structures in areas such as engineering equipment serving in marine environments and those near the sea where wear is severe, such as ship surfaces, offshore platforms, and bridge platforms located in tidal areas.

[0023] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0024] (1) The present invention utilizes supersonic arc spraying technology to control the pure Ti wire and pure Cu wire of different diameters on the coaxial wire feed wheel, thereby realizing the preparation of Cu-TiN / TiO2 laminated structure wear-resistant composite ceramic coatings with different Cu contents. Compared with other thermal spraying methods, the raw materials of the metal-ceramic composite coatings with different Cu contents prepared by the present invention are pure metal wires, and the spraying is carried out in an atmospheric environment. Compared with other preparation methods that use mixed powder as spraying raw materials and the spraying atmosphere is protective gas. The present invention has lower preparation costs, simpler preparation processes and adaptability to large-scale equipment construction sites.

[0025] (2) Finely control the parameters of each phase of spraying. After the pure Cu and Ti wires are rapidly melted in the high-temperature arc tip area, violent reactions occur between the atomized droplets of Cu and Ti, and between the droplets and the surrounding air. After the mixed droplets fly at high speed for a distance, they are quickly deposited and diffused on the substrate to form a stable and firm Cu-TiN / TiO2 laminated structure wear-resistant composite ceramic coating. Compared with other methods for preparing Cu-Ti composite ceramic coatings, the coating prepared by the present invention can achieve controllable composition, thickness and microstructure, and the Cu phase and TiN / TiO2 ceramic phase are uniformly distributed in the coating. The uniform distribution of Cu elements can form a reasonable hardness and toughness match with the hard phase TiN / TiO2, thereby improving wear resistance. The nitrogen oxides of Cu element and Ti have relatively stable chemical properties and high corrosion resistance, so the Cu-TiN / TiO2 composite coating has good corrosion resistance.

[0026] (3) Compared with the single-component Cu-Ti composite coating, the coating prepared by the present invention has flexible and variable design of each phase composition, which can meet the different usage requirements of the composite coating's wear resistance and corrosion resistance under marine environment conditions. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 Schematic diagram of coating preparation.

[0028] Figure 2 is the X-ray diffraction pattern of the coating.

[0029] Figure 3 Photoelectron diffraction pattern of the coating.

[0030] Figure 4 The cross-sectional morphology and surface morphology of the coating.

[0031] Figure 5 Schematic diagram of coating wear volume under different friction and wear environments. DETAILED DESCRIPTION

[0032] The present invention will be described in further detail below with reference to the Examples and accompanying drawings, but the embodiments of the present invention are not limited thereto. Where specific conditions are not specified in the Examples, conventional conditions or conditions recommended by the manufacturer were followed. Reagents or instruments used, where the manufacturer is not specified, are commercially available conventional products.

[0033] Example 1

[0034] The surface of the Q345B workpiece was roughened by sandblasting with brown corundum sand with an average particle size of 2.0 mm to enhance the bonding strength between the coating and the substrate. The sandblasting pressure was 0.7 MPa, the sandblasting angle was 90°, the sandblasting distance was 50 mm, and the sandblasting time per substrate was 15 seconds. A pure Cu wire with a purity of 99.9%, a diameter of 0.4 mm, and a length of 2000 mm was used as the consumable anode for the spray power supply. A pure Ti wire with a purity of 99.9%, a diameter of 1.5 mm, and a length of 2000 mm was used as the consumable cathode for the spray power supply. Before spraying, the wire surface was cleaned of any surface deposits and oxide layers using sandpaper and then ultrasonically cleaned. After the wire and the Q345B substrate (Ø25 x 9 mm) were fixed in corresponding molds, an SX-1000 supersonic arc spraying machine was used to deposit a wear-resistant laminated composite ceramic coating. The main parameters of the spraying process are: arc working voltage 39±1V, arc working current 50±10A, compressed air 0.8Mpa, spraying distance 120mm, horizontal movement speed of the spray gun 6mm / s, wire feeding speed of the wire at both ends of the spray gun 3m / min, no interval during the spraying process, spraying lasts 40s, and the spray gun sprays back and forth on the substrate surface four times.

[0035] The composite coating prepared in this example has a thickness of 250±30μm. The coating surface exhibits a uniform diffusion distribution of TiN / TiO2 (dark phase) and Cu (light phase), and the coating cross-section displays a typical laminated structure of TiN / TiO2 (dark phase) and Cu (light phase). EDS analysis shows that the coating is primarily composed of Ti oxynitrides, with a Cu content of 8.3%, making it a low-Cu composite ceramic coating. The coating surface and cross-sectional structure are smooth and dense, with a porosity of only 0.87%. Nanoindentation hardness testing shows that the coating has a hardness of 20.5±0.5GPa and an elastic modulus of 181±3Mpa, representing a nine-fold increase in hardness compared to the Q345B structural steel substrate. Under dry friction conditions with a normal load of 5N and 10N, the wear volume is only 16.6% and 11% of that of the Q345B substrate, respectively. Under a 10N normal load and a 3.5% NaCl corrosive solution, the wear volume is only 22% of that of the substrate. Among them, the wear resistance under 10N dry friction conditions is improved by more than 900% compared with the base material.

[0036] Example 2

[0037] The surface of the Q345B workpiece was roughened by sandblasting with brown corundum sand with an average particle size of 2.0 mm to enhance the bonding strength between the coating and the substrate. The sandblasting pressure was 0.7 MPa, the sandblasting angle was 85°, the sandblasting distance was 60 mm, and the sandblasting time per substrate was 15 seconds. A pure Cu wire with a purity of 99.9%, a diameter of 0.6 mm, and a length of 2000 mm was used as the consumable anode for the spray power supply. A pure Ti wire with a purity of 99.9%, a diameter of 1.5 mm, and a length of 2000 mm was used as the consumable cathode for the spray power supply. Before spraying, the wire surface was cleaned of any surface deposits and oxide layers using sandpaper and then ultrasonically cleaned. After the wire and the Q345B substrate (Ø25 x 9 mm) were fixed in corresponding molds, an SX-1000 supersonic arc spraying machine was used to deposit a wear-resistant laminated composite ceramic coating. The main parameters of the spraying process are: arc working voltage 40±1V, arc working current 60±10A, compressed air 0.8Mpa, spraying distance 120mm, horizontal movement speed of the spray gun 8mm / s, wire feeding speed of the wire at both ends of the spray gun 5m / min, no interval during the spraying process, spraying lasts 30s, and the spray gun sprays back and forth on the substrate surface 4 times.

[0038] The composite coating prepared in this example has a thickness of 300±30μm. The coating surface exhibits a uniform diffusion distribution of TiN / TiO2 (dark phase) and Cu (light phase). The cross-section of the coating exhibits a more pronounced typical laminated structure of TiN / TiO2 (dark phase) and Cu (light phase). EDS analysis shows that the coating is primarily composed of Ti oxynitrides, with a Cu content of 13.8%, making it a composite ceramic coating with a low Cu content. The coating surface and cross-sectional structure are smooth and dense, with a porosity of only 0.79%. Nanoindentation hardness testing shows that the coating has a hardness of 17.33±0.5GPa and an elastic modulus of 172±3Mpa, representing a sevenfold increase in hardness compared to the Q345B structural steel substrate. Under dry grinding conditions with a normal load of 5N and 10N, the wear volume is only 55% and 16% of that of the Q345B substrate, respectively. Under a 10N normal load and a 3.5% NaCl corrosive solution, the wear volume is only 52% of that of the substrate. Among them, the wear resistance under 10N dry grinding conditions is more than 600% higher than that of the base material.

[0039] Example 3

[0040] The surface of the Q345B workpiece was roughened by sandblasting using brown corundum sand with an average particle size of 2.0 mm to enhance the bonding strength between the coating and the substrate. The sandblasting pressure was 0.7 MPa, the blasting angle was 80°, the blasting distance was 65 mm, and the blasting duration per substrate was 20 seconds. A pure Cu wire with a purity of 99.9%, a diameter of 0.7 mm, and a length of 2000 mm was used as the consumable anode for the spray power supply. A pure Ti wire with a purity of 99.9%, a diameter of 1.5 mm, and a length of 2000 mm was used as the consumable cathode for the spray power supply. Before spraying, the wire surface was cleaned of any surface deposits and oxide layers using sandpaper and then ultrasonically cleaned. After the wire and the Q345B substrate (Ø25 x 9 mm) were fixed in corresponding molds, an SX-1000 supersonic arc spraying system was used to deposit a wear-resistant laminated composite ceramic coating. The main parameters of the spraying process are: arc working voltage 41±1V, arc working current 65±10A, compressed air 0.8Mpa, spraying distance 120mm, horizontal movement speed of the spray gun 10mm / s, wire feeding speed of the wire at both ends of the spray gun 6m / min, no interval during the spraying process, spraying lasts 25s, and the spray gun sprays back and forth on the substrate surface 4 times.

[0041] The composite coating prepared in this example has a thickness of 350±30μm. The coating surface exhibits a uniform diffusion distribution of TiN / TiO2 (dark phase) and Cu (light phase). The cross-section of the coating displays a more pronounced typical laminated structure of TiN / TiO2 (dark phase) and Cu (light phase). EDS analysis shows that the coating is primarily composed of Ti oxynitrides, with a Cu content of 18.6%. The coating surface and cross-section structure are smooth and dense, with a porosity of only 0.67%. Nanoindentation hardness testing shows a hardness of 15.7±0.5GPa and an elastic modulus of 159±2MPa, representing a 6.5-fold increase in hardness compared to the Q345B structural steel substrate. Under dry grinding conditions with normal loads of 10N and 20N, the wear volume is only 23% and 56% of that of the Q345B substrate, respectively. Under a 10N normal load and 3.5% NaCl solution, the wear volume is only 28% of the substrate. The wear resistance under 10N dry grinding is over 400% higher than that of the substrate material.

[0042] Example 4

[0043] The surface of the Q345B workpiece was roughened by sandblasting with brown corundum sand with an average particle size of 2.0 mm to enhance the bonding strength between the coating and the substrate. The sandblasting pressure was 0.8 MPa, the sandblasting angle was 85°, the sandblasting distance was 60 mm, and the sandblasting time per substrate was 15 seconds. A pure Cu wire with a purity of 99.9%, a diameter of 1.0 mm, and a length of 2500 mm was used as the consumable anode for the spray power supply. A pure Ti wire with a purity of 99.9%, a diameter of 1.5 mm, and a length of 2500 mm was used as the consumable cathode for the spray power supply. Before spraying, the wire surface was cleaned of any surface deposits and oxide layers using sandpaper and then cleaned in an ultrasonic instrument. After the wire and the Q345B substrate (Ø25 x 9 mm) were fixed in corresponding molds, an SX-1000 supersonic arc spraying machine was used to deposit a wear-resistant laminated composite ceramic coating. The main parameters of the spraying process are: arc working voltage 42±1V, arc working current 100±10A, compressed air 0.8Mpa, spraying distance 120mm, horizontal movement speed of the spray gun 10mm / s, wire feeding speed of the wire at both ends of the spray gun 8m / min, no interval during the spraying process, spraying lasts 20s, and the spray gun sprays back and forth on the substrate surface 3 times.

[0044] The composite coating prepared in this example has a thickness of 400±50μm. The coating surface exhibits a uniform diffusion distribution of TiN / TiO2 (dark phase) and Cu (light phase). The cross-section of the coating displays a more pronounced, typical laminated structure of TiN / TiO2 (dark phase) and Cu (light phase). EDS analysis indicates a Cu content of 35.8% in the coating, with a ratio of Ti oxynitride to Cu of approximately 6:4, indicating a high Cu content in the composite ceramic coating. The coating's surface and cross-sectional structure are smooth and dense, with a porosity of only 0.54%. Nanoindentation hardness testing reveals a hardness of 10.16±0.8GPa and an elastic modulus of 155±5MPa, representing a 4.5-fold increase in hardness compared to the Q345B structural steel substrate. Under dry grinding conditions with normal loads of 10N and 20N, the wear volume is only 29% and 31% of that of the Q345B substrate, respectively. Under a 10N normal load and 3.5% NaCl solution, the wear volume is only 35% of that of the substrate. The wear resistance of the coating under 10N dry grinding conditions is improved by about 300% compared with the base material.

[0045] Example 5

[0046] The surface of the Q345B workpiece was roughened by sandblasting with brown corundum sand with an average particle size of 2.0 mm to enhance the bonding strength between the coating and the substrate. The sandblasting pressure was 0.8 MPa, the sandblasting angle was 90°, the sandblasting distance was 40 mm, and the sandblasting time per substrate was 20 seconds. A pure Cu wire with a purity of 99.9%, a diameter of 2.0 mm, and a length of 3000 mm was used as the consumable anode for the spray power supply. A pure Ti wire with a purity of 99.9%, a diameter of 1.5 mm, and a length of 3000 mm was used as the consumable cathode for the spray power supply. Before spraying, the wire surface was cleaned of any surface deposits and oxide layers using sandpaper and then ultrasonically cleaned. After the wire and the Q345B substrate (Ø25 x 9 mm) were fixed in corresponding molds, an SX-1000 supersonic arc spraying machine was used to deposit a wear-resistant laminated composite ceramic coating. The main parameters of the spraying process are: arc working voltage 45±1V, arc working current 120±10A, compressed air 0.8Mpa, spraying distance 120mm, horizontal movement speed of the spray gun 15mm / s, wire feeding speed of the wire at both ends of the spray gun 10m / min, no interval during the spraying process, spraying lasts 18s, and the spray gun sprays back and forth on the substrate surface 5 times.

[0047] The composite coating prepared in this example has a thickness of 600±50μm. The coating surface shows a uniform diffusion distribution of TiN / TiO2 (dark phase) and Cu (bright phase). The cross-section of the coating exhibits a more obvious typical laminated structure of TiN / TiO2 (dark phase) and Cu (bright phase). According to EDS analysis results, the Cu content in the coating is 66.6%, exceeding 50%, making it the most abundant phase. The coating surface and cross-sectional structure are smooth and dense, with a porosity of only 0.42%. According to nanoindentation hardness testing, the coating has a hardness of 8.77±0.2GPa and an elastic modulus of 130±1Mpa, which is 3.5 times harder than the Q345B structural steel substrate. Under dry grinding conditions with a normal load of 20N, the wear volume is 62% of that of the Q345B substrate. Under a normal load of 10N and a 3.5% NaCl corrosive solution, the wear volume is only 39% of the substrate. The coating exhibits good wear resistance under different friction and wear conditions.

[0048] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be considered as equivalent replacement methods and are included in the scope of protection of the present invention.

Claims

1. A laminated wear-resistant composite ceramic coating, characterized in that By coaxial wire feed wheel on different diameter ratios of pure Ti wire and pure Cu wire by supersonic arc spraying prepared, the wear-resistant composite ceramic coating is a Cu-TiN / TiO2 laminated structure composite ceramic coating; The method for preparing the laminated wear-resistant composite ceramic coating comprises the following steps: fixing pure Ti wire and pure Cu wire of different diameter ratios through a coaxial roller wire feeding device, spraying after setting the spraying parameters on the control panel, and obtaining the composite ceramic coating; The parameters of the supersonic arc spraying process are: arc working voltage of 38-44V, arc working current ≤150A, coaxial wire feeding speed of 3m / min-10m / min, compressed air pressure of 0.8Mpa, spraying distance of 120mm, and spraying atmosphere of atmospheric environment; The diameter of the Ti wire is 1.0-2.0 mm; the diameter of the Cu wire is 0.3-2.0 mm.

2. The laminated wear-resistant composite ceramic coating according to claim 1, characterized in that: The main components of the laminated wear-resistant composite ceramic coating are Cu, TiN, TiO2, TiN 0.3 , the Cu element does not generate an impurity phase that affects its corrosion resistance, and the Ti element does not generate an intermediate phase that affects its hardness and wear resistance.

3. The laminated wear-resistant composite ceramic coating according to claim 2, characterized in that: The content of Cu element in the laminated wear-resistant composite ceramic coating is 8.3%-66.6%.

4. The laminated wear-resistant composite ceramic coating according to claim 3, characterized in that: The content of Cu element in the laminated wear-resistant composite ceramic coating is 8.3%-35.8%.

5. The laminated wear-resistant composite ceramic coating according to claim 1, characterized in that: The thickness of the laminated wear-resistant composite ceramic coating is 200-1000 μm.

6. The laminated wear-resistant composite ceramic coating according to claim 1, characterized in that: The purity of the titanium wire is ≥99.9%, and the purity of the Cu wire is ≥99.9%.

7. The laminated wear-resistant composite ceramic coating according to claim 1, characterized in that: The speed of the servo motor that controls the movement of the spray gun is: 5-20 mm / s in the horizontal direction, the single spraying time is 15-50 s, and the spraying is repeated until the coating thickness is 200-1000 μm.

8. Use of the laminated wear-resistant composite ceramic coating according to any one of claims 1 to 6 in surface protection of engineering equipment serving in marine environments and various workpieces and engineering structures in coastal areas.

9. Use of the laminated wear-resistant composite ceramic coating according to any one of claims 1 to 6 on the surface of ships, offshore operating platforms, and bridge platforms located in tidal areas.

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