A nano-layer enhanced multi-element antibacterial and abrasion-resistant coating and a preparation method thereof

Abstract

The application discloses a nano-layer enhanced multi-element antibacterial and abrasion-resistant coating and a preparation method thereof. The coating takes a metal part as a substrate, and comprises, from the substrate outward, a monovalent elemental metal layer, a binary nitride layer, a ternary nitride layer, and an alternating layer of the ternary nitride layer and a quaternary nitride layer doped with an active antibacterial metal element, wherein the active antibacterial metal element is copper or silver, and the content of the active antibacterial metal element doped in the quaternary nitride is 0.5at% to 8.0at%. The application optimizes the adding mode of the antibacterial metal element in the subsurface layer, forms a layer column alternating period structure, that is, a microstructure matching the nitride columnar crystal layer and the antibacterial element-containing dense layer, adjusts the existing form and diffusion behavior of the active antibacterial metal element, promotes the ionization of the surface, and constructs a film substrate system with excellent mechanical properties, corrosion resistance, abrasion resistance and antibacterial properties, thereby having a wide application prospect in the field of metal part protection.

Description

Technical Field

[0001] This invention relates to the field of coating technology, specifically to a nano-layer reinforced multi-component antibacterial and wear-resistant coating and its preparation method. Background Technology

[0002] Nitride coatings possess advantages such as high hardness, oxidation resistance, wear resistance, and corrosion resistance, and are widely used in the surface protection of cutting tools and marine metal parts. To further improve their antibacterial properties, researchers have successively developed multi-component nitride coatings doped with active antibacterial metal elements such as copper and silver. These coatings not only provide significant bactericidal effects but also offer advantages such as improved wear resistance, dense microstructure, and stress relief. Non-equilibrium magnetron sputtering offers advantages such as high deposition rate, low-temperature deposition, and environmental friendliness, enabling the formation of dense coatings without significant defects and with high film-substrate bonding strength. In existing research, CN109778121 discloses a Zr-Cu-N nanocomposite wear-resistant antibacterial coating and its preparation method. Although it exhibits a nano-hardness of up to 25 GPa and an antibacterial rate of 99%, the cost of zirconium metal is too high. CN115772639 discloses a high-entropy alloy / ceramic composite anti-cavitation and anti-wear coating and its preparation method. Although it has excellent anti-cavitation and anti-wear properties, its high-entropy alloy powder raw material has the disadvantages of high cost and difficulty in preparation. At the same time, the atmospheric supersonic flame spraying preparation method has many coating defects and low thermal efficiency, resulting in high cost. Neither of these methods meets the requirements of low-cost and green environmental protection industrial production.

[0003] Furthermore, the doping concentration of antibacterial metal elements exhibits a certain "threshold concentration." Too low a concentration results in weak antibacterial activity, while too high a concentration leads to the precipitation of soft metals, inhibiting nitride crystal growth and easily forming galvanic corrosion, significantly reducing the mechanical and corrosion resistance of the coating. Current research primarily focuses on optimizing the content of these elements, while further work is needed to regulate their form and diffusion behavior through specific structural designs. Moreover, methods for preparing nanolayer-reinforced multi-element antibacterial and wear-resistant coatings—which combine excellent mechanical, corrosion-resistant, abrasion-resistant, and antibacterial properties—by optimizing the addition of antibacterial metal elements to the subsurface layer to form an alternating columnar periodic structure, promoting surface ionization, and constructing a film-based system possessing superior mechanical, corrosion-resistant, abrasion-resistant, and antibacterial properties, have not yet been publicly disclosed. Summary of the Invention

[0004] Purpose of the invention: In order to solve the technical problems existing in the prior art, the present invention aims to provide a nano-layer reinforced multi-element antibacterial and wear-resistant coating that is low in cost, environmentally friendly and has excellent mechanical properties, corrosion resistance, wear resistance and antibacterial properties. Furthermore, the present invention also provides a method for preparing the nano-layer reinforced multi-element antibacterial and wear-resistant coating.

[0005] Technical solution: The nano-layer-enhanced multi-element antibacterial and wear-resistant coating of the present invention uses a metal part as a substrate, and from the substrate outwards includes an alternating layer of a single elemental metal layer, a binary nitride layer, a ternary nitride layer, a ternary nitride layer / quaternary nitride layer doped with active antibacterial metal elements, and a ternary nitride layer.

[0006] Furthermore, the metal parts are selected from stainless steel, titanium alloy, cobalt-chromium alloy, nickel alloy, magnesium alloy, tantalum alloy or zirconium alloy.

[0007] Furthermore, the mono-elemental metal is titanium or chromium, and the mono-elemental metal layer serves as the underlayer to improve the adhesion between the film and the substrate, with a thickness of 200 nm to 500 nm; the binary nitride is titanium nitride or chromium nitride, and the binary nitride layer is a nitride layer based on the mono-elemental metal, serving as a transition layer to alleviate abrupt changes in stress and performance, with a thickness of 250 nm to 1000 nm; the ternary nitride is titanium aluminum nitride or chromium aluminum nitride, and the ternary nitride layer is a nitride layer based on the binary nitride with added metal elements that can improve mechanical properties and corrosion resistance, serving as the main component of the coating, with a thickness of 1000 nm to 3000 nm.

[0008] Furthermore, the active antibacterial metal element in the quaternary nitride layer doped with the active antibacterial metal element exists in ionic form, achieving efficient utilization of the antibacterial performance of the active antibacterial metal element throughout the coating; the active antibacterial metal element is copper or silver, and its doping content in the quaternary nitride is 0.5 at% to 8.0 at%, preferably 2.07 at% to 7.20 at%; the quaternary nitride is titanium aluminum copper nitride, titanium aluminum silver nitride, chromium aluminum copper nitride, or chromium aluminum silver nitride; the microstructure of the alternating layer of ternary nitride / quaternary nitride doped with the active antibacterial metal element is a periodic structure of alternating columnar layers, that is, an alternating structure of columnar nitride crystal layers and dense layers containing antibacterial metal elements, and the active antibacterial metal element exists in ionic form in the quaternary nitride layer.

[0009] Furthermore, the thickness of the alternating layer of ternary nitride / quaternary nitride doped with active antibacterial metal element is 400nm to 500nm, and the alternation period is 1 to 3; the thickness of the ternary nitride layer is 100nm to 200nm.

[0010] The method for preparing the nano-layer-reinforced multi-element antibacterial and wear-resistant coating of the present invention includes the following steps:

[0011] (1) The surface of the metal substrate is pretreated by high-energy bombardment using magnetron sputtering to remove the oxide layer;

[0012] (2) A uni-elemental metal layer, a binary nitride layer and a ternary nitride layer are sequentially deposited on the surface of the substrate after the oxide layer is removed;

[0013] (3) An alternating layer of ternary nitride layer / quaternary nitride layer doped with active antibacterial metal element is deposited on the ternary nitride layer, presenting a periodic structure of alternating columnar layers, that is, a microstructure of alternating columnar nitride crystal layers and dense layers containing antibacterial metal element, and the active antibacterial metal element exists in the form of ionic state.

[0014] (4) Finally, a ternary nitride layer is deposited to obtain a nano-layer-enhanced multi-component antibacterial and wear-resistant coating.

[0015] Further, in step (1), the process parameters of the high-energy bombardment pretreatment are: high-energy bombardment is performed using argon ions, the substrate bias voltage is -200V to -800V, and the target current is 0.1A to 1A. The pretreatment can effectively remove the oxide layer on the substrate surface and roughen the substrate surface to produce microscopic unevenness, thereby improving the film-substrate adhesion.

[0016] Further, in step (2), the target material for depositing the unary elemental metal layer and the binary nitride layer is a titanium elemental metal target or a chromium elemental metal target; the target material for depositing the ternary nitride layer is a titanium elemental metal target or a chromium elemental metal target and an aluminum elemental metal target; the deposition parameters are: substrate bias voltage of -30V to -150V, target power of 500W to 2500W.

[0017] Further, in step (3), the target material for depositing the quaternary nitride layer doped with active antibacterial metal elements is a titanium elemental metal target or a chromium elemental metal target, an aluminum elemental metal target, a copper elemental metal target or an aluminum elemental metal target; the deposition parameters are: substrate bias voltage of -30V to -150V, and target power of copper elemental metal target or aluminum elemental metal target of 100W to 500W.

[0018] Further, in steps (2) to (4), during the deposition process of the magnetron sputtering method, the sputtering atmosphere is a mixture of argon and nitrogen, the argon flow rate is 20 sccm to 40 sccm, the nitrogen flow rate is 10 sccm to 30 sccm, the deposition pressure is 0.1 Pa to 0.4 Pa, the deposition temperature is 150℃ to 200℃, the target-substrate distance is 12.5 cm to 14.5 cm, the total deposition time is 250 min to 300 min, and the total coating thickness is 1 μm to 5 μm.

[0019] Invention Principle: This invention utilizes magnetron sputtering to sequentially deposit a mono-elemental metal layer, a binary nitride layer, and a ternary nitride layer on the surface of a metal part substrate. Subsequently, an alternating layer of ternary nitride layers / quaternary nitride layers doped with active antibacterial metal elements is deposited within the top layer, followed by another ternary nitride layer, resulting in a nanolayer-reinforced multi-element antibacterial and wear-resistant coating. This invention optimizes the addition method (content and location) of the antibacterial metal elements in the subsurface layer, forming an alternating columnar structure—a microstructure alternating between columnar nitride crystal layers and dense layers containing antibacterial elements. Simultaneously, a discrete alloying method creates alternating copper-poor and copper-rich layers. Even with no or low-content additions, the columnar crystal microstructure is maintained in the nanocomposite layer. Antibacterial metal element atoms diffuse and dissolve into the nitride lattice, existing in an ionic state and difficult to precipitate. However, the wide grain boundaries of the columnar crystals facilitate diffusion, promoting surface ionization and thus enhancing the antibacterial properties of the coating. At high concentrations, the columnar crystals of the nanocomposite layer become denser, and the precipitation of fine grains increases the resistance to dislocation movement, thereby improving mechanical properties. Furthermore, the soft metal can release stress at crack tips, enhancing the coating's toughness. By controlling the addition of antibacterial metal elements, nanocomposite multilayer nitride coatings with different microstructures were constructed, forming a microstructure with periodically matched nitride columnar crystal layers and dense layers containing antibacterial metal elements. This promotes surface ionization, creating a film-based system that combines excellent mechanical properties, corrosion resistance, abrasion resistance, and antibacterial properties.

[0020] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages:

[0021] (1) The present invention prepares a metal substrate containing a uni-element metal layer, a binary nitride layer and a ternary nitride layer, forming a good bond and optimizing the performance. The gradient transition layer can alleviate the degree of stress discontinuity and increase the load-bearing capacity and plastic resistance.

[0022] (2) In this invention, alternating layers of ternary nitrides / quaternary nitrides containing active antibacterial metal elements with different contents and positions are first incorporated into the top layer deposition. Through discrete alloy design, a periodic structure of alternating columnar layers is presented, namely, the microstructure of alternating columnar nitride crystal layers and dense layers containing antibacterial elements. The active antibacterial elements exist in the ionic state, which can achieve excellent mechanical and antibacterial properties. In addition, the soft antibacterial metal elements in the quaternary nitride layer can release the stress at the crack tip and improve the toughness of the coating. At the same time, it can relieve the internal stress of the coating and improve the wear resistance.

[0023] (3) In the end, a ternary nitride layer is deposited on the surface of the alternating layer, which can provide selective diffusion channels to form a high surface ion content and construct a membrane-based system with excellent mechanical properties, corrosion resistance, abrasion resistance and antibacterial properties.

[0024] (4) The preparation method of the nano-layer reinforced multi-element antibacterial and wear-resistant coating of the present invention is simple and easy to implement, with strong film-substrate adhesion and good comprehensive performance. Attached Figure Description

[0025] Figure 1 This is a schematic diagram of the structure of the nanolayer-reinforced multi-element antibacterial and wear-resistant coating of the present invention;

[0026] Figure 2 These are schematic diagrams of the coatings obtained in Examples 1-2 and Comparative Examples 1-3 of the present invention.

[0027] Figure 3 The photoelectron spectra of the coatings obtained in Examples 1-2 and Comparative Examples 1-4 of this invention are shown.

[0028] Figure 4 The mechanical properties of the coatings obtained in Examples 1-2 and Comparative Examples 1-4 of this invention are shown in the diagram.

[0029] Figure 5 The corrosion resistance diagrams are for the coatings obtained in Examples 1-2 and Comparative Examples 1-4 of this invention.

[0030] Figure 6 The graphs show the wear and corrosion resistance of the coatings obtained in Examples 1-2 and Comparative Examples 1-4 of this invention.

[0031] Figure 7 The diagram shows the antibacterial properties of the coatings obtained in Examples 1-2 and Comparative Examples 1-4 of this invention. Detailed Implementation

[0032] The present invention will now be further described in conjunction with specific embodiments and accompanying drawings.

[0033] like Figure 1 As shown, the nanolayer-enhanced multi-element antibacterial and wear-resistant coating (G) of the present invention uses a metal part as a substrate (A). From the substrate (A) outwards, it includes a mono-elemental metal layer (B) with a thickness of 200nm to 500nm, a binary nitride layer (C) with a thickness of 250nm to 1000nm, a ternary nitride layer (D) with a thickness of 1000nm to 3000nm, an alternating layer of ternary nitride / quaternary nitride doped with active antibacterial metal elements with a thickness of 400nm to 500nm (E), and a ternary nitride layer (F) with a thickness of 100nm to 200nm, wherein the alternation period of the alternating layers is 1 to 3.

[0034] Example 1: The preparation method of the nano-layer-reinforced multi-element antibacterial and wear-resistant coating of the present invention includes the following steps:

[0035] (1) First, place two high-purity titanium targets, one high-purity aluminum target, and one high-purity copper target on the four magnetotubes inside the cavity, respectively. Then, ultrasonically clean the 316 stainless steel substrate (A) in alcohol for 10 minutes and dry it for later use. Next, assemble the metal substrate part (A) onto the cavity fixture, introduce high-purity argon gas at 40 sccm, and wait for the cavity vacuum to reach 4 × 10⁻⁶. -5 At mbar, the surface of the substrate (A) is bombarded with high-energy argon ions by high bias sputtering to remove the oxide layer. The substrate bias is set to 400V, the main alloying element target is a titanium target and the current is 0.5A.

[0036] (2) Subsequently, a mono-titanium metal layer (B) with a thickness of 400nm-500nm, a binary titanium nitride layer (C) with a thickness of 900nm-1000nm, and a ternary titanium aluminum nitride layer (D) with a thickness of 2900nm-3000nm were sequentially deposited on the surface of a 316 stainless steel substrate (A) by magnetron sputtering. The deposition gas pressure was adjusted to 0.23Pa, the target-substrate distance was 12.5cm-14.5cm, a mixture of argon and nitrogen was used during sputtering, the substrate bias voltage was -90V, the deposition temperature was 150℃-200℃, the Ti target power was 1500W-2000W, the Al target power was 2000W-2500W, the nitrogen flow rate gradient was increased to 24-28sccm, the gradient increased the Ti target current to 6A and the Al target current to 8A, and the transition layer alleviated the discontinuity of mechanical properties and reduced internal stress.

[0037] (3) During the last 30 minutes of the top layer deposition, a quaternary titanium-aluminum-copper-nitrogen layer containing active antibacterial metal elements is incorporated into the middle and lower 20 minutes to form a three-cycle alternating layer (E) of titanium-aluminum-nitrogen / titanium-aluminum-copper-nitrogen. The copper target power is 360W to 500W, the total thickness is 400nm to 500nm (the layer thickness here is the total thickness of the three cycles), and the copper content is 7.20at%.

[0038] (4) The ternary nitride layer (F) was redeposited on the surface for 10 minutes with a thickness of 100 nm to 200 nm, resulting in a multi-element antibacterial and wear-resistant coating (G) with a total thickness of 1 μm to 5 μm. The total deposition time was 250 min to 300 min. After deposition, the power was turned off, and the material was allowed to cool naturally to room temperature, maintaining the pressure in the pressure chamber consistent with the air pressure. The sample was designated as S5.

[0039] Example 2: The basic steps are the same as in Example 1, except that in step (3), a quaternary titanium-aluminum-copper-nitrogen layer containing active antibacterial metal elements is deposited in the top layer for 10 minutes, with a copper content of 2.07 at%, forming a one-cycle titanium-aluminum-nitrogen / titanium-aluminum-copper-nitrogen alternating layer. The total deposition time is 20 minutes, and the total thickness is 400 nm to 500 nm. The ternary nitride layer is then deposited for 10 minutes with a thickness of 100 nm to 200 nm. The sample is designated as S4.

[0040] Comparative Example 1: The basic steps are the same as in Example 1, except that in step (3), a quaternary titanium-aluminum-copper-nitrogen layer containing active antibacterial metal elements is added to the top layer for the final deposition for 10 minutes, with a thickness of 200nm to 250nm and a copper content of 5.90 at.%. The sample number is recorded as S3.

[0041] Comparative Example 2: The basic steps are the same as in Example 1, except that in step (3), a quaternary titanium-aluminum-copper-nitrogen layer containing active antibacterial metal elements is added to the top layer for the final deposition for 30 minutes, with a thickness of 700nm to 800nm ​​and a copper content of 26.75 at%. The sample number is recorded as S2.

[0042] Comparative Example 3: The basic steps are the same as in Example 1, except that step (3) is omitted, and a single titanium aluminum nitrogen coating is used as the control group. The sample number is denoted as S1.

[0043] Comparative Example 4: No coating was applied, and performance tests were conducted using a 316 stainless steel (316LSS) substrate.

[0044] The structural schematic diagrams of the coatings obtained in Examples 1-2 and Comparative Examples 1-3 are shown below. Figure 2 As shown.

[0045] The coatings obtained in Examples 1-2 and Comparative Examples 1-4 were subjected to performance tests, and the results are shown in Table 1 and 2. Figures 3-7 .

[0046] As can be seen from the above examples and comparative results, Example 1, by incorporating a three-period titanium-aluminum-nitrogen / titanium-aluminum-copper-nitrogen alternating layer containing active antibacterial metal elements into the top layer deposition with a total thickness of approximately 400nm-500nm and a distance of 100nm-200nm from the surface, can obtain a nanolayer-reinforced multi-element antibacterial and wear-resistant coating with high comprehensive performance. It maintains high mechanical properties ( Figure 4 ) and high corrosion resistance ( Figure 5 Based on this, when placed in a simulated seawater solution containing 0.5 wt% quartz sand (particle size of 200 μm to 330 μm), its cumulative weight loss is only 1.30 mg. After 24 hours, the anti-Escherichia coli rate is as high as 99.68%, and the anti-Staphylococcus aureus rate is as high as 95.86%, both of which are superior to the coatings in other groups.

[0047] As the copper content increases, copper nanocrystals precipitate on the surface, which not only reduce mechanical properties and corrosion resistance but also hinder the diffusion of copper ions. Simultaneously, the dense quaternary titanium-aluminum-copper layer on the upper surface also impedes ion diffusion. However, in the top layer of the S5 coating, a three-periodic alternating layer of columnar ternary titanium-aluminum-nitrogen and dense quaternary titanium-aluminum-copper-nitrogen is deposited. The wide channels of the columnar crystals accelerate the diffusion of copper ions to the upper surface, while the dense quaternary titanium-aluminum-copper-nitrogen acts as a barrier to limit electrolyte and microporous penetration. Furthermore, the presence of copper ions eliminates the surface micropotential (i.e., galvanic corrosion) at the metal-electrolyte interface, thereby enhancing corrosion resistance. Low copper content and the presence of copper nanocrystals can suppress dislocation movement and grain boundary sliding in the nitride lattice, thus improving mechanical properties.

[0048] Table 1. Summary of the performance of the coatings obtained in Examples 1-2 and Comparative Examples 1-4

[0049]

[0050] Note: The steps for simulating cumulative weight loss in seawater over 24 hours are as follows: the sample is placed in a simulated seawater solution containing 0.5 wt% quartz sand (particle size of 200 μm to 330 μm), with an impact velocity of 10 m / s and an impact angle of 90°. The cumulative weight loss is then calculated after 24 hours.

[0051] For wear resistance (e.g.) Figure 6 As shown in the figure, the coating surface is mainly affected by the erosion of solid particles from quartz sand and the cavitation erosion of bubbles, resulting in cracks and peeling. Considering the correlation between mechanical properties, corrosion resistance, and abrasion resistance, compared with the S1 coating, the S2 coating has the lowest mechanical properties and the worst corrosion resistance, thus exhibiting the worst abrasion resistance. Furthermore, among the coatings with three different embedding depths of titanium aluminum copper nitride sublayers (S3, S4, and S5), the S5 coating has the smallest cumulative mass loss after 24 hours and exhibits the best abrasion resistance. The soft titanium aluminum copper nitride sublayer located on the upper surface can accelerate the damage to propagate into the coating interior, hence the poor abrasion resistance of the S3 coating, while the embedded soft titanium aluminum copper nitride sublayer acts as a buffer layer and disperses stress, forming a periodic structure of alternating "columnar (hard) nitride / dense (soft) nitride" layers. The interfaces between layers can act as barriers, restricting the substrate pathways. In this soft nitride / hard nitride multilayer system, soft nitride is used to provide ductility, while hard nitride is used to provide high hardness, which helps to release residual stress, change the direction of initial crack movement, and prevent dislocation movement and damage propagation. Therefore, the wear and corrosion resistance of the multi-interface S5 coating is better than that of the S4 coating.

[0052] For antibacterial properties (such as) Figure 7As shown in the figure, the antibacterial rate of all coatings was higher than 90%, with the S5 coating having the highest antibacterial rate of 99.68%. Since the radii of copper atoms (radius 117 pm), monovalent copper ions (radius 96 pm), and divalent copper ions (radius 72 pm) decrease sequentially, their diffusion ability is divalent copper ions greater than monovalent copper ions, which is greater than copper atoms. Based on XPS detection results (e.g....), Figure 3 As shown, divalent copper ions can be detected on the surface of the S5 coating and in the three titanium-aluminum-copper-nitrogen sublayers, and can diffuse along the channels between the columnar crystals. The S3 coating, however, contains copper metal on its surface, and both monovalent and divalent copper ions are present in the sublayer depth direction, resulting in inferior antibacterial properties compared to the S5 coating. In conclusion, controlling the sublayers that match different columnar structures to accelerate the generation and diffusion of copper ions on the coating surface is an innovative method that combines the wear resistance and antibacterial properties of titanium-aluminum-copper-nitrogen coatings.

[0053] This invention utilizes magnetron sputtering to sequentially deposit a single-element metal layer (B), a binary nitride layer (C), and a ternary nitride layer (D) on the surface of a metal part substrate (A). Finally, an alternating layer (E) of ternary nitride / quaternary nitride containing active antibacterial elements is first deposited within the top layer, followed by the deposition of a ternary nitride layer (F), resulting in a nanolayer-reinforced multi-element antibacterial and wear-resistant coating (G). By optimizing the addition method (content and location) of antibacterial elements in the subsurface layer, a periodic columnar structure is achieved, characterized by alternating columnar nitride crystal layers and dense layers containing antibacterial elements. Simultaneously, a discrete alloying method forms alternating copper-poor and copper-rich layers. Even with no or low-content antibacterial elements, the columnar crystal microstructure is maintained in the nanocomposite layer. Antibacterial element atoms diffuse and dissolve into the nitride lattice, existing in an ionic state and difficult to precipitate. However, the wide grain boundaries of the columnar crystals facilitate diffusion, promoting surface ionization and thus enhancing the antibacterial properties of the coating. At high concentrations, the columnar crystals of the nanocomposite layer become denser, and the precipitation of fine grains increases the resistance to dislocation movement, thereby improving mechanical properties. Furthermore, the soft metal can release stress at crack tips, enhancing the coating's toughness. By controlling the addition of antibacterial elements, nanocomposite multilayer nitride coatings with different microstructures were constructed, exhibiting an alternating columnar layer structure—a microstructure of alternating columnar nitride layers and dense layers containing antibacterial elements. This provides selective diffusion channels for copper atoms and ions, promoting surface ionization and constructing a film-based system that combines excellent mechanical properties, corrosion resistance, abrasion resistance, and antibacterial properties.

[0054] In summary, the method of this invention can utilize magnetron sputtering technology. By optimizing the addition of antibacterial elements to the subsurface layer, this invention forms a layer-column alternating periodic structure, namely a microstructure that matches the nitride columnar crystal layer with a dense layer containing antibacterial elements. It regulates the existence form and diffusion behavior of active antibacterial elements, promotes surface ionization, and constructs a film-based system that combines excellent mechanical properties, corrosion resistance, abrasion resistance, and antibacterial properties, showing broad application prospects in the field of metal parts protection.

Claims

1. A nano-layer-reinforced multi-element antibacterial and wear-resistant coating, using a metal part as the substrate (A), characterized in that, The coating, from the substrate (A) outwards, comprises a single elemental metal layer (B), a binary nitride layer (C), a ternary nitride layer (D), an alternating layer of ternary nitride layers / quaternary nitride layers doped with active antibacterial metal elements (E), and a ternary nitride layer (F); the active antibacterial metal element is copper or silver, and its doping content in the quaternary nitride layer is 0.5 at.%~8.0 at.%; the thickness of the alternating layer (E) of ternary nitride layers / quaternary nitride layers doped with active antibacterial metal elements is 400 nm~500 nm, and the alternation period is 1~3; the thickness of the ternary nitride layer (F) is 100 nm~200 nm. nm; the microstructure of the alternating layers (E) of the ternary nitride layer / quaternary nitride layer doped with active antibacterial metal element is a periodic structure of alternating columnar layers, that is, alternating columnar nitride crystal layers and dense layers containing antibacterial metal element; the doped active antibacterial metal element exists in the quaternary nitride layer in the form of ionic state.

2. The nano-layer-reinforced multi-element antibacterial and wear-resistant coating according to claim 1, characterized in that, The metal parts are selected from stainless steel, titanium alloy, cobalt-chromium alloy, nickel alloy, magnesium alloy, tantalum alloy, or zirconium alloy.

3. A method for preparing a nanolayer-reinforced multi-element antibacterial and wear-resistant coating as described in claim 1, characterized in that, Includes the following steps: (1) The surface of the metal substrate (A) was pretreated by high-energy bombardment using magnetron sputtering to remove the oxide layer; (2) A single elemental metal layer (B), a binary nitride layer (C), and a ternary nitride layer (D) are sequentially deposited on the surface of the metal substrate (A) after the oxide layer is removed. (3) An alternating layer (E) of ternary nitride layer / quaternary nitride layer doped with active antibacterial metal element is deposited on the ternary nitride layer (D). (4) Finally, a ternary nitride layer (F) is deposited to obtain a nano-layer-enhanced multi-component antibacterial and wear-resistant coating.

4. The preparation method according to claim 3, characterized in that, In step (1), the process parameters for the high-energy bombardment pretreatment are: high-energy bombardment is performed using argon ions, the substrate bias voltage is -200 V to -800 V, and the target current is 0.1 A to 1 A.

5. The preparation method according to claim 3, characterized in that, In steps (2) to (4), the target material for depositing the unary elemental metal layer (B) and the binary nitride layer (C) is a titanium elemental metal target or a chromium elemental metal target; the target material for depositing the ternary nitride layer (D) is a titanium elemental metal target or a chromium elemental metal target and an aluminum elemental metal target. The target material for depositing quaternary nitride layers doped with active antibacterial metal elements is a titanium elemental metal target, a chromium elemental metal target, an aluminum elemental metal target, a copper elemental metal target, or a silver elemental metal target.

6. The preparation method according to claim 3, characterized in that, In steps (2) to (4), during the deposition process of the magnetron sputtering method, the sputtering atmosphere is a mixture of argon and nitrogen, the argon flow rate is 20 sccm~40 sccm, the nitrogen flow rate is 10 sccm~30 sccm, the deposition pressure is 0.1 Pa~0.4 Pa, the deposition temperature is 150℃~200 ℃, the target-substrate distance is 12.5cm~14.5 cm, the total deposition time is 250 min~300 min, and the total coating thickness is 1 μm~5 μm.

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