High-antibacterial-property doped carbon-based film layer of medical nickel-titanium alloy and preparation method thereof

Abstract

The invention relates to the technical field of material preparation, and provides a high-antibacterial-property doped carbon-based film layer of a medical nickel-titanium alloy and a preparation method of the high-antibacterial-property doped carbon-based film layer of the medical nickel-titanium alloy, and the preparation method comprises the steps that a nickel-titanium alloy base material is pretreated, and pretreatment comprises polishing and ultrasonic cleaning; putting the pretreated nickel-titanium alloy base material into a vacuum chamber; argon is introduced into the vacuum chamber, and plasma cleaning is conducted on the nickel-titanium alloy base material in the vacuum chamber; the nickel-titanium alloy base material subjected to plasma cleaning is subjected to film coating treatment through target materials, so that a high-antibacterial-property doped carbon-based film layer is formed on the surface of the nickel-titanium alloy base material, and the target materials comprise a titanium dioxide target and a silver-carbon composite target; in terms of atomic percent, the content of silver in the high-antibacterial-property doped carbon-based film layer is 5%-20%, the content of titanium dioxide is 3%-15%, and the content of carbon is 30%-85%, so that the high-antibacterial-property doped carbon-based film layer of the medical nickel-titanium alloy has antibacterial property and structural stability; and the service life of the high-antibacterial-property doped carbon-based film layer of the medical nickel-titanium alloy is prolonged.

Description

Technical Field

[0001] The present application relates to the technical field of material preparation, and in particular to a highly antibacterial doped carbon-based film layer of medical nickel-titanium alloy and a preparation method thereof. Background Art

[0002] The membranes used in related technologies are prone to performance defects. Antimicrobial membrane materials commonly used in related technologies suffer from technical bottlenecks such as insufficient corrosion resistance, weak physical and chemical stability, and a short service life. Traditional wear-resistant membranes also suffer from inherent flaws such as limited functionality, lack of antimicrobial efficacy, high internal stress, and insufficient membrane-substrate bonding strength. Consequently, improvements to these membranes are urgently needed. Summary of the Invention

[0003] The main purpose of this application is to provide a highly antibacterial doped carbon-based film layer of medical nickel-titanium alloy and a preparation method thereof, aiming to solve the technical problem that the film layer of the nickel-titanium alloy substrate is prone to performance defects.

[0004] In a first aspect, an embodiment of the present application provides a method for preparing a highly antibacterial doped carbon-based film layer of a medical nickel-titanium alloy, comprising:

[0005] Pre-treating the nickel-titanium alloy substrate, wherein the pre-treatment includes polishing and ultrasonic cleaning;

[0006] placing the pretreated nickel-titanium alloy substrate into a vacuum chamber;

[0007] introducing argon gas into the vacuum chamber to perform plasma cleaning on the nickel-titanium alloy substrate in the vacuum chamber;

[0008] The plasma-cleaned nickel-titanium alloy substrate is plated using a target material to form a highly antibacterial doped carbon-based film layer on the surface of the nickel-titanium alloy substrate. The target material includes a titanium dioxide target and a silver-carbon composite target. In terms of atomic percentage, the silver content in the highly antibacterial doped carbon-based film layer is 5% to 20%, the titanium dioxide content is 3% to 15%, and the carbon content is 30% to 85%.

[0009] In a second aspect, an embodiment of the present application further provides a highly antibacterial doped carbon-based film layer of a medical nickel-titanium alloy, wherein the highly antibacterial doped carbon-based film layer is prepared according to the above-mentioned method for preparing the highly antibacterial doped carbon-based film layer of a medical nickel-titanium alloy.

[0010] In a third aspect, an embodiment of the present application further provides a coated part, comprising:

[0011] Nitinol substrate; and

[0012] The highly antibacterial doped carbon-based film layer is formed on the surface of the nickel-titanium alloy substrate; the highly antibacterial doped carbon-based film layer is prepared according to the preparation method of the highly antibacterial doped carbon-based film layer of the medical nickel-titanium alloy.

[0013] An embodiment of the present application provides a highly antibacterial doped carbon-based film layer of a medical nickel-titanium alloy and a preparation method thereof. The preparation method comprises: pretreating a nickel-titanium alloy substrate, the pretreatment comprising polishing and ultrasonic cleaning; placing the pretreated nickel-titanium alloy substrate in a vacuum chamber; introducing argon gas into the vacuum chamber to plasma-clean the nickel-titanium alloy substrate in the vacuum chamber; using a target material to perform a coating treatment on the plasma-cleaned nickel-titanium alloy substrate to form a highly antibacterial doped carbon-based film layer on the surface of the nickel-titanium alloy substrate; in terms of atomic percentage, the silver content in the highly antibacterial doped carbon-based film layer is 5% to 20%, the titanium dioxide content is 3% to 15%, and the carbon content is 30% to 85%.

[0014] The silver included in the highly antibacterial doped carbon-based film layer of medical nickel-titanium alloy can provide long-lasting antibacterial activity for the highly antibacterial doped carbon-based film layer. The titanium dioxide included in the highly antibacterial doped carbon-based film layer can be used to enhance the photocatalytic antibacterial effect. The carbon included in the highly antibacterial doped carbon-based film layer can be used to construct a diamond-like carbon (DLC) structure. Based on this, the highly antibacterial doped carbon-based film layer can maintain the inherent biocompatibility and mechanical properties advantages of the DLC structure, and through the synergistic effect of the silver-titanium-carbon three-phase, make the highly antibacterial doped carbon-based film layer have both antibacterial properties and structural stability. When the highly antibacterial doped carbon-based film layer has antibacterial properties and structural stability, it is beneficial to improve the service life of the highly antibacterial doped carbon-based film layer. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following is a brief introduction to the drawings required for use in the description of the embodiments. Obviously, the drawings described below are some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without any creative work.

[0016] Figure 1 This is a flow chart of a method for preparing a highly antibacterial doped carbon-based film layer of a medical nickel-titanium alloy provided in an embodiment of the present application.

[0017] Figure 2 This is a schematic block diagram of the structure of a highly antibacterial doped carbon-based film layer of a medical nickel-titanium alloy according to one embodiment of the present application;

[0018] Figure 3 1 is a schematic block diagram of the structure of a highly antibacterial doped carbon-based film layer of medical nickel-titanium alloy according to another embodiment of the present application;

[0019] Figure 4 is a schematic diagram of a silver-carbon composite target according to an embodiment of the present application;

[0020] Figure 5 is a schematic block diagram of the structure of a highly antibacterial doped carbon-based film layer of medical nickel-titanium alloy according to another embodiment of the present application;

[0021] Figure 6 1 is a schematic block diagram of the structure of a highly antibacterial doped carbon-based film layer of medical nickel-titanium alloy according to another embodiment of the present application;

[0022] Figure 7 1 is a schematic block diagram of the structure of a highly antibacterial doped carbon-based film layer of medical nickel-titanium alloy according to another embodiment of the present application;

[0023] Figure 8 It is a microscopic image of the film layer in the related art;

[0024] Figure 9 This is a microscopic image of the highly antibacterial doped carbon-based film layer of the medical nickel-titanium alloy involved in Example 4 of the present application;

[0025] Figure 10 yes Figure 9 Raman spectroscopy of highly antibacterial doped carbon-based films on medical nickel-titanium alloys;

[0026] Figure 11 yes Figure 9 Antibacterial test chart corresponding to the high antibacterial doped carbon-based film layer of the medical nickel-titanium alloy involved;

[0027] Figure 12 This is a microscopic image of the highly antibacterial doped carbon-based film layer of the medical nickel-titanium alloy involved in Example 5 of the present application;

[0028] Figure 13 yes Figure 12 Raman spectroscopy of highly antibacterial doped carbon-based films on medical nickel-titanium alloys;

[0029] Figure 14 yes Figure 12 Antibacterial test diagram of the highly antibacterial doped carbon-based film layer of the medical nickel-titanium alloy involved. DETAILED DESCRIPTION

[0030] The following will be combined with the drawings in the embodiments of this application to clearly and completely describe the technical solutions in the embodiments of this application. Obviously, the embodiments described are part of the embodiments of this application, not all of them. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

[0031] The flowcharts shown in the accompanying drawings are for illustrative purposes only and do not necessarily include all contents and operations / steps, nor must they be executed in the order described. For example, some operations / steps may be decomposed, combined, or partially merged, so the actual execution order may vary depending on the actual situation.

[0032] The following describes some embodiments of the present application in detail with reference to the accompanying drawings. In the absence of conflict, the following embodiments and features in the embodiments may be combined with each other.

[0033] See also Figure 1 , Figure 1 This is a flow chart of a method for preparing a highly antibacterial doped carbon-based film layer of a medical nickel-titanium alloy provided in an embodiment of the present application.

[0034] like Figure 1 As shown, the method for preparing the highly antibacterial doped carbon-based film layer of the medical nickel-titanium alloy includes steps S101 to S104.

[0035] S101. Pre-treating the nickel-titanium alloy substrate, including polishing and ultrasonic cleaning.

[0036] For example, the nickel-titanium alloy substrate can be used for medical purposes. Accordingly, the nickel-titanium alloy substrate can also be called medical nickel-titanium alloy.

[0037] In some embodiments, the nickel-titanium alloy substrate is polished.

[0038] For example, the surface of the nickel-titanium alloy substrate can be polished to reduce the surface roughness of the nickel-titanium alloy substrate. For example, the surface roughness of the nickel-titanium alloy substrate after polishing can be less than or equal to a preset roughness threshold. The preset roughness threshold can be determined based on the surface roughness of a mirror surface so that the surface smoothness of the nickel-titanium alloy substrate after polishing can match the smoothness of the mirror surface.

[0039] When the nickel-titanium alloy substrate is polished, the surface defects of the nickel-titanium alloy substrate, such as scratches, oxide impurities, etc., can be reduced, and the surface roughness of the nickel-titanium alloy substrate can be optimized. Based on the optimization of the surface roughness of the nickel-titanium alloy substrate, when the medical nickel-titanium alloy is subsequently subjected to high antibacterial doped carbon-based coating, it is beneficial to improve the film-base bonding force between the nickel-titanium alloy substrate and the high antibacterial doped carbon-based film layer. Accordingly, when the surface of the nickel-titanium alloy substrate is polished, the unevenness of the nickel-titanium alloy substrate can be reduced, so as to improve the uniformity of the high antibacterial doped carbon-based film layer when the medical nickel-titanium alloy is subsequently prepared.

[0040] In some embodiments, the nickel-titanium alloy substrate is ultrasonically cleaned.

[0041] For example, the ultrasonic cleaning process of a nickel-titanium alloy substrate includes: ultrasonically cleaning the nickel-titanium alloy substrate using acetone, alcohol, and deionized water in sequence. After the nickel-titanium alloy substrate is ultrasonically cleaned, the nickel-titanium alloy substrate can be dried using nitrogen gas.

[0042] When the nickel-titanium alloy substrate is ultrasonically cleaned, pollutants and oxide impurities on the surface of the nickel-titanium alloy substrate can be removed, which can subsequently reduce the adverse effects of pollutants and oxide impurities on the high antibacterial doped carbon-based coating process of the medical nickel-titanium alloy, thereby facilitating the subsequent enhancement of the film-base bonding force between the nickel-titanium alloy substrate and the high antibacterial doped carbon-based film layer.

[0043] S102, placing the pretreated nickel-titanium alloy substrate into a vacuum chamber.

[0044] For example, the term "vacuum chamber" can be used to refer to a chamber of a vacuum chamber. A vacuum chamber can be used to refer to a sealed container capable of maintaining a vacuum environment within the vacuum chamber. For example, a vacuum chamber can be constructed by exhausting the gas within the vacuum chamber through an exhaust system, creating an environment below atmospheric pressure, i.e., a vacuum state.

[0045] In some embodiments, the nickel-titanium alloy substrate can be fixed on a substrate stage within a vacuum chamber.

[0046] When the pretreated nickel-titanium alloy substrate is placed in a vacuum chamber, the air can be isolated to reduce the adverse effects of air on the high antibacterial doped carbon-based coating process of the medical nickel-titanium alloy.

[0047] S103, introducing argon gas into the vacuum chamber to perform plasma cleaning on the nickel-titanium alloy substrate in the vacuum chamber.

[0048] For example, when argon gas is introduced into a vacuum chamber, it can ionize to form a plasma within the vacuum chamber. The vacuum chamber can utilize the plasma to perform plasma cleaning on a nickel-titanium alloy substrate within the vacuum chamber. For example, when the plasma includes argon ions, the argon ions bombard the nickel-titanium alloy substrate within the vacuum chamber, removing contaminants and oxide impurities from the surface of the nickel-titanium alloy substrate, thereby achieving plasma cleaning of the nickel-titanium alloy substrate within the vacuum chamber.

[0049] In some embodiments, the plasma cleaning process of the nickel-titanium alloy substrate includes: evacuating a vacuum chamber; starting the lighting system of the vacuum chamber; introducing argon gas into the vacuum chamber; setting the rotation speed of the substrate stage that fixes the nickel-titanium alloy substrate in the vacuum chamber; and applying a bias voltage to the nickel-titanium alloy substrate fixed on the substrate stage to plasma clean the nickel-titanium alloy substrate in the vacuum chamber.

[0050] For example, during the plasma cleaning process of nickel-titanium alloy substrates, the vacuum degree of the vacuum chamber is 10 -7 Pa~10 -3 Pa; the lighting power of the lighting system of the vacuum chamber ranges from 20W to 40W; the gas flow rate of argon gas ranges from 160sccm to 200sccm; the rotation speed of the substrate stage ranges from 3rpm to 7rpm; the bias voltage applied to the nickel-titanium alloy substrate ranges from 450V to 550V; and the time for plasma cleaning of the nickel-titanium alloy substrate is from 10min to 20min.

[0051] When argon gas is introduced into the vacuum chamber and the nickel-titanium alloy substrate in the vacuum chamber is plasma cleaned, the pollutants and oxide impurities on the surface of the nickel-titanium alloy substrate can be removed, and the adverse effects of the pollutants and oxide impurities on the high antibacterial doped carbon-based coating process of the medical nickel-titanium alloy can be reduced. For example, the possibility of forming a high antibacterial doped carbon-based film layer on the pollutants or oxide impurities on the surface of the nickel-titanium alloy substrate is reduced, which is beneficial to the subsequent enhancement of the film-base bonding force between the nickel-titanium alloy substrate and the high antibacterial doped carbon-based film layer.

[0052] S104. Using a target material, the nickel-titanium alloy substrate after plasma cleaning is plated to form a highly antibacterial doped carbon-based film layer on the surface of the nickel-titanium alloy substrate. The target material includes a titanium dioxide target and a silver-carbon composite target. In terms of atomic percentage, the silver content in the highly antibacterial doped carbon-based film layer is 5% to 20%, the titanium dioxide content is 3% to 15%, and the carbon content is 30% to 85%.

[0053] like Figure 2 or Figure 3 As shown, a highly antimicrobial doped carbon-based film is formed on the surface of a nickel-titanium alloy substrate. The highly antimicrobial doped carbon-based film includes silver, titanium dioxide, and carbon, so the silver-titanium-carbon three-phase in the highly antimicrobial doped carbon-based film can act synergistically. The highly antimicrobial doped carbon-based film can also include silver, titanium dioxide, carbon, and nitrogen, so the silver-titanium-carbon-nitrogen four-phase in the highly antimicrobial doped carbon-based film can act synergistically.

[0054] By using a target material to coat a plasma-cleaned nickel-titanium alloy substrate, a highly antibacterial doped carbon-based film can be formed on the surface of the nickel-titanium alloy substrate. When the target material comprises a titanium dioxide target or a silver-carbon composite target, the highly antibacterial doped carbon-based film of the medical nickel-titanium alloy comprises silver, titanium dioxide, and carbon. In atomic percentages, the silver content of the highly antibacterial doped carbon-based film is 5% to 20%, the titanium dioxide content is 3% to 15%, and the carbon content is 30% to 85%.

[0055] For example, the target material of the titanium dioxide target can be prepared according to a target material raw material of the titanium dioxide target. The target material raw material of the titanium dioxide target can include titanium dioxide powder.

[0056] In some embodiments, a target material for a titanium dioxide target is obtained. For example, the target material for the titanium dioxide target comprises titanium dioxide powder. The titanium dioxide powder can be treated to obtain micron-sized particles. The treated titanium dioxide powder can then be bonded together using a binder. The bonded titanium dioxide powder is then formed under high pressure to obtain the target material for the titanium dioxide target.

[0057] For example, the target material of the silver-carbon composite target can be prepared according to a target material raw material of the silver-carbon composite target. The target material raw material of the silver-carbon composite target can include silver and carbon.

[0058] In some embodiments, a target material for a silver-carbon composite target is obtained. For example, the target material for a silver-carbon composite target includes silver and carbon. The silver and carbon can be treated to obtain micron-sized particles. The treated silver and carbon can then be bonded together using an adhesive. The bonded silver and carbon are then formed under high pressure to obtain the target material for the silver-carbon composite target.

[0059] For example, the mass ratio of silver to carbon in the silver-carbon composite target is in the range of 1:(2-3).

[0060] In an exemplary embodiment, the mass ratio of silver to carbon in the silver-carbon composite target is 1:2.37.

[0061] By controlling the mass ratio of silver and carbon in the silver-carbon composite target, the silver content and carbon content in the highly antibacterial doped carbon-based film layer formed on the surface of the nickel-titanium alloy substrate can be controlled, which is beneficial to improving the convenience of coating medical nickel-titanium alloy with highly antibacterial doped carbon-based coating.

[0062] For example, a silver-carbon composite target is a disc-shaped target composed of fan-shaped silver units and fan-shaped carbon units with the same radius, wherein the central angle of the fan-shaped silver unit is θ1, the central angle of the fan-shaped carbon unit is θ2, θ1+θ2=360°; wherein the ratio of θ1 to θ2 is in the range of 1:(10~12).

[0063] like Figure 4 As shown, the silver-carbon composite target may include sector-shaped silver units and sector-shaped carbon units. The sector-shaped silver units may include silver. The sector-shaped carbon units may include carbon.

[0064] In an exemplary embodiment, the ratio of the central angle θ1 of the sector-shaped silver unit to the central angle θ2 of the sector-shaped carbon unit in the silver-carbon composite target is 1:11.

[0065] By controlling the ratio between the central angles of the fan-shaped silver units and the fan-shaped carbon units in the silver-carbon composite target, the silver content and carbon content in the highly antibacterial doped carbon-based film layer formed on the surface of the nickel-titanium alloy substrate can be controlled, which is beneficial to improving the convenience of coating medical nickel-titanium alloy with highly antibacterial doped carbon-based coating.

[0066] When a titanium dioxide target and a silver-carbon composite target are prepared, the titanium dioxide target and the silver-carbon composite target can be used to coat a treated nickel-titanium alloy substrate to form a highly antibacterial doped carbon-based film layer on the surface of the nickel-titanium alloy substrate. In terms of atomic percentage, the highly antibacterial doped carbon-based film layer comprises 5% to 20% silver, 3% to 15% titanium dioxide, and 30% to 85% carbon.

[0067] The silver in the highly antimicrobial doped carbon-based film layer of medical nickel-titanium alloy can exist in the form of silver nanoparticles. Since the silver in the highly antimicrobial doped carbon-based film layer has antimicrobial properties, the silver in the highly antimicrobial doped carbon-based film layer can provide long-lasting antimicrobial activity to the highly antimicrobial doped carbon-based film layer. Accordingly, the highly antimicrobial doped carbon-based film layer can utilize the antimicrobial properties of silver to provide antimicrobial protection for the nickel-titanium alloy substrate.

[0068] Titanium dioxide in the highly antibacterial carbon-based film layer of medical nickel-titanium alloys exhibits antibacterial properties. For example, titanium dioxide can generate active oxidative species through photocatalysis, effectively killing bacteria through a physical and chemical combination, thereby enhancing the photocatalytic antibacterial effect. Accordingly, the highly antibacterial carbon-based film layer can utilize the antibacterial properties of titanium dioxide to provide antibacterial protection for the nickel-titanium alloy substrate.

[0069] The carbon in the highly antibacterial carbon-based film layer of medical nickel-titanium alloy can be used to construct a DLC structure. For example, the hybridization of carbon atoms can be controlled by physical or chemical methods, such as controlling the hybridization of carbon atoms to sp 3 Hybridization can allow it to approach diamond properties, forming a DLC structure. For example, the hybridization of carbon atoms can be controlled by methods such as ion beam deposition and plasma-enhanced chemical vapor deposition, which are not limited here. The DLC structure can have biocompatibility and mechanical performance advantages, and the carbon in the highly antibacterial doped carbon-based film layer can be used to improve the structural stability of the highly antibacterial doped carbon-based film layer.

[0070] Under the synergistic effect of the silver-titanium-carbon three-phase in the high antibacterial doped carbon-based film layer of medical nickel-titanium alloy, the high antibacterial doped carbon-based film layer can have both antibacterial properties and structural stability.

[0071] For traditional film layer systems, there are the following technical contradictions: when the thickness of the film layer in the traditional film layer system is too high, it is easy to cause internal stress accumulation, insufficient interface bonding strength and the risk of film layer falling off, and at the same time lead to a significant increase in process costs; when the thickness of the film layer in the traditional film layer system is too low, it is difficult to maintain physical and chemical stability, and it is easy to induce problems such as the dissolution of related ions in the nickel-titanium alloy substrate, such as nickel ions.

[0072] In the case where the highly antibacterial doped carbon-based film layer of the medical nickel-titanium alloy prepared in the embodiment of the present application includes silver, titanium dioxide and carbon, the synergistic effect of the three phases of silver-titanium-carbon in the highly antibacterial doped carbon-based film layer can effectively regulate the stress distribution within the highly antibacterial doped carbon-based film layer and optimize the membrane-base bonding performance of the highly antibacterial doped carbon-based film layer. Accordingly, the proportion of active ingredients in the highly antibacterial doped carbon-based film layer can also be precisely controlled to reduce the risk of precipitation of high-concentration metal ions while ensuring the long-term chemical stability of the highly antibacterial doped carbon-based film layer. When the long-term chemical stability of the highly antibacterial doped carbon-based film layer is improved, it is beneficial to improve the service life of the highly antibacterial doped carbon-based film layer.

[0073] In some embodiments, a target material is used to perform a sputtering coating process on the plasma-cleaned nickel-titanium alloy substrate to form a highly antibacterial doped carbon-based film layer on the surface of the nickel-titanium alloy substrate.

[0074] For example, the target materials include titanium dioxide targets and silver-carbon composite targets. Titanium dioxide targets and silver-carbon composite targets can be used to sputter a plasma-cleaned nickel-titanium alloy substrate to form a highly antibacterial doped carbon-based film on the surface of the nickel-titanium alloy substrate.

[0075] For example, target materials include titanium dioxide targets, silver-carbon composite targets, and carbon targets. These targets can be used to sputter a plasma-cleaned nickel-titanium alloy substrate to form a highly antibacterial doped carbon-based film on the surface of the nickel-titanium alloy substrate.

[0076] The target material of the carbon target can be prepared according to a target material raw material of the carbon target. The target material raw material of the carbon target can include graphite.

[0077] For example, a target material for a carbon target is obtained. For example, the target material for a carbon target includes graphite. The graphite can be treated to produce micron-sized particles. The treated graphite can then be bonded together using an adhesive. The bonded graphite is then formed under high pressure to produce the target material for the carbon target.

[0078] For example, in the process of using a target material and a sputtering method to coat the nickel-titanium alloy substrate after plasma cleaning, the gas environment of the vacuum chamber in which the nickel-titanium alloy substrate is located can also be changed, such as introducing methane into the vacuum chamber or introducing nitrogen into the vacuum chamber. In the case where the gas environment of the vacuum chamber in which the nickel-titanium alloy substrate is located changes, the nickel-titanium alloy substrate after plasma cleaning can be sputtered using at least titanium dioxide and a silver-carbon composite target to form a highly antibacterial doped carbon-based film layer on the surface of the nickel-titanium alloy substrate. Correspondingly, the nickel-titanium alloy substrate after plasma cleaning can also be sputtered using titanium dioxide targets, silver-carbon composite targets, and carbon targets to form a highly antibacterial doped carbon-based film layer on the surface of the nickel-titanium alloy substrate.

[0079] In some embodiments, a plasma-cleaned nickel-titanium alloy substrate is plated using a titanium dioxide target, a silver-carbon composite target, and a carbon target to form a highly antibacterial doped carbon-based film layer on the surface of the nickel-titanium alloy substrate; in terms of atomic percentage, the silver content in the highly antibacterial doped carbon-based film layer is 6% to 20%, the titanium dioxide content is 3% to 10%, and the carbon content is 70% to 85%.

[0080] like Figure 2 As shown, when the high antibacterial doped carbon-based film layer includes silver, titanium dioxide, and carbon, it is equivalent to plating a DLC structure doped with silver and titanium dioxide on the surface of a nickel-titanium alloy substrate. The high antibacterial doped carbon-based film layer can achieve the synergistic effect of the three phases of silver-titanium-carbon, so that the high antibacterial doped carbon-based film layer has both structural stability and antibacterial properties.

[0081] In some embodiments, the nickel-titanium alloy substrate after plasma cleaning is plated using a titanium dioxide target, a silver-carbon composite target, a carbon target, and nitrogen to form a highly antibacterial doped carbon-based film layer on the surface of the nickel-titanium alloy substrate. In terms of atomic percentage, the silver content in the highly antibacterial doped carbon-based film layer is 5% to 20%, the titanium dioxide content is 6% to 15%, the carbon content is 30% to 60%, and the nitrogen content is 5% to 35%.

[0082] like Figure 3 As shown, when the high antibacterial doped carbon-based film layer of medical nickel-titanium alloy includes silver, titanium dioxide, carbon and nitrogen, it is equivalent to plating a DLC structure doped with silver, titanium dioxide and nitrogen on the surface of the nickel-titanium alloy substrate. The high antibacterial doped carbon-based film layer can have both structural stability and antibacterial properties through the synergistic effect of the four phases of silver-titanium-carbon-nitrogen.

[0083] Doping nitrogen into the highly antibacterial doped carbon-based film layer of medical nickel-titanium alloy can form strong covalent bonds between nitrogen and carbon and titanium in the highly antibacterial doped carbon-based film layer, thereby improving the hardness and wear resistance of the highly antibacterial doped carbon-based film layer. For example, doping nitrogen into the DLC structure of the highly antibacterial doped carbon-based film layer can form an N-DLC structure, thereby controlling the hybridization mode of carbon atoms in the highly antibacterial doped carbon-based film layer to be sp 3 Hybridization, thereby balancing the hardness and toughness of the high antibacterial doped carbon-based film layer. At the same time, the high antibacterial doped carbon-based film layer can use the N-DLC structure to adjust the crystallinity and defect density of the high antibacterial doped carbon-based film layer, thereby effectively alleviating the internal stress generated during the high-energy deposition process and enhancing the film-base bonding force between the nickel-titanium alloy substrate and the high antibacterial doped carbon-based film layer. Furthermore, nitrogen doping in the high antibacterial doped carbon-based film layer can reduce the optical band gap of titanium dioxide by regulating the electronic structure of titanium dioxide, so that it has visible light response ability and thus has photocatalytic activity under visible light. Moreover, the nitrogen and silver in the high antibacterial doped carbon-based film layer can act synergistically to enhance the spectral antibacterial effect of the high antibacterial doped carbon-based film layer. Based on this, the high antibacterial doped carbon-based film layer formed on the surface of the nickel-titanium alloy substrate can have both antibacterial properties and structural stability, which is beneficial to improving the service life of the high antibacterial doped carbon-based film layer.

[0084] Exemplarily, the process of coating a NiTi alloy substrate after plasma cleaning using a target material includes: changing the gas flow rate of argon gas introduced into a vacuum chamber; turning on the RF power supply of the vacuum chamber; setting the sputtering power of the target material; and sputtering the NiTi alloy substrate after plasma cleaning using the target material.

[0085] For example, the sputtering power of the titanium dioxide target ranges from 110W to 150W; the sputtering power of the silver-carbon composite target ranges from 20W to 40W; or, the coating time of the plasma-cleaned nickel-titanium alloy substrate ranges from 30 minutes to 120 minutes.

[0086] For example, the range of the gas flow rate of the argon gas after the gas flow rate is changed is 30 sccm to 70 sccm.

[0087] In some embodiments, before using the target to perform a coating process on the plasma-cleaned nickel-titanium alloy substrate, the surface oxide of the target may be removed.

[0088] For example, before using a target to sputter a plasma-cleaned nickel-titanium alloy substrate, the sample shutter in the vacuum chamber can be closed and the target can be allowed to idle for a preset time to remove surface oxides. The sample shutter in the vacuum chamber can then be opened to allow the target to sputter the nickel-titanium alloy substrate. The preset time can be pre-set or user-configured and is not limited here.

[0089] During the process of coating a plasma-cleaned nickel-titanium alloy substrate using a target, a transition layer and a surface doping layer can be formed on the surface of the nickel-titanium alloy substrate, thereby forming a highly antibacterial doped carbon-based film layer. For example, the surface doping layer can serve as a highly antibacterial doped carbon-based film layer.

[0090] In some embodiments, a nickel-titanium alloy substrate after plasma cleaning is plated using a first target material to form a transition layer; the first target material includes a titanium target; a second target material is plated to form a surface doping layer on the side of the transition layer away from the nickel-titanium alloy substrate, thereby forming a highly antibacterial doped carbon-based film layer; the second target material includes a titanium dioxide target and a silver-carbon composite target; in terms of atomic percentage, the silver content in the highly antibacterial doped carbon-based film layer is 5% to 20%, the titanium dioxide content is 6% to 15%, the carbon content is 30% to 60%, and the nitrogen content is 5% to 35%.

[0091] For example, in order to further enhance the film-substrate bonding strength between the nickel-titanium alloy substrate and the highly antibacterial doped carbon-based film layer and reduce the internal stress of the highly antibacterial doped carbon-based film layer, a transition layer can be formed on the surface of the nickel-titanium alloy substrate and a surface doping layer can be formed on the side of the transition layer away from the nickel-titanium alloy substrate during the process of forming the highly antibacterial doped carbon-based film layer on the surface of the nickel-titanium alloy substrate, thereby forming the highly antibacterial doped carbon-based film layer. The transition layer and the surface doping layer can enhance the film-substrate bonding strength between the nickel-titanium alloy substrate and the highly antibacterial doped carbon-based film layer and reduce the internal stress of the highly antibacterial doped carbon-based film layer.

[0092] like Figure 5 As shown, the transition layer is formed on the surface of the nickel-titanium alloy substrate, and the surface doping layer is formed on the side of the transition layer away from the surface of the nickel-titanium alloy substrate. The transition layer may include at least one of a Ti transition sublayer, a TiC transition sublayer, and a TiCN transition sublayer. For example, when the transition layer only includes a Ti transition sublayer, the Ti transition sublayer may also be referred to as a Ti transition layer. The surface doping layer may be doped with silver, titanium dioxide, carbon, and nitrogen. Based on this, the highly antibacterial doped carbon-based film layer of the medical nickel-titanium alloy can enhance the structural stability and antibacterial performance of the highly antibacterial doped carbon-based film layer through the synergistic effect of the silver-titanium-carbon-nitrogen four-phase.

[0093] In some embodiments, the process of coating a nickel-titanium alloy substrate after plasma cleaning with a first target to form a transition layer includes: changing the gas flow rate of argon gas introduced into a vacuum chamber; turning on the radio frequency power supply of the vacuum chamber; setting the sputtering power of the first target; and sputtering the nickel-titanium alloy substrate after plasma cleaning with the first target.

[0094] For example, before sputtering the plasma-cleaned nickel-titanium alloy substrate using the first target, the surface oxide of the first target can be removed. The steps for removing the surface oxide of the first target can be referred to the aforementioned description of removing the surface oxide of the target, and will not be repeated here.

[0095] In some embodiments, the process of using a second target material for coating to form a surface doping layer on the side of the transition layer away from the nickel-titanium alloy substrate includes: turning off the first target material; setting the sputtering power of the second target material; and using the second target material to sputter the nickel-titanium alloy substrate after the transition layer is formed.

[0096] For example, before using the second target to sputter the nickel-titanium alloy substrate after forming the transition layer, the surface oxide of the second target can be removed. The steps for removing the surface oxide of the second target can refer to the above description of removing the surface oxide of the target, and will not be repeated here.

[0097] Exemplarily, the first target material includes a titanium target, and the second target material includes a titanium dioxide target and a silver-carbon composite target.

[0098] The target material of the titanium target can be prepared according to the target material raw material of the titanium target. The target material raw material of the titanium target can include titanium powder.

[0099] In some embodiments, a target material for a titanium target is obtained. For example, the target material for the titanium target includes titanium powder. The titanium powder can be treated to obtain micron-sized particles. The treated titanium powder can then be bonded together using a binder. The bonded titanium powder is then formed under high pressure to obtain the target material for the titanium target.

[0100] During the formation of the surface doping layer, nitrogen can be used to modify the atmosphere of the vacuum chamber housing the nickel-titanium alloy substrate. For example, a second target and nitrogen can be used to form the surface doping layer on the side of the transition layer away from the nickel-titanium alloy substrate. In atomic percentages, the highly antibacterial doped carbon-based film layer contains 5% to 20% silver, 6% to 15% titanium dioxide, 30% to 60% carbon, and 5% to 35% nitrogen.

[0101] like Figures 5 to 7As shown, the highly antimicrobial doped carbon-based film layer of medical nickel-titanium alloy can include silver, titanium dioxide, carbon, and nitrogen. The synergistic effect of the silver-titanium-carbon-nitrogen four-phase in the highly antimicrobial doped carbon-based film layer helps improve the adhesion of the highly antimicrobial doped carbon-based film layer, relieve the stress of the highly antimicrobial doped carbon-based film layer, improve the bonding strength between the nickel-titanium alloy substrate and the highly antimicrobial doped carbon-based film layer, and enhance the antimicrobial performance of the highly antimicrobial doped carbon-based film layer.

[0102] For example, the transition layer includes a Ti transition layer. A titanium target is used to sputter the plasma-cleaned nickel-titanium alloy substrate to form the transition layer. A second target is used to coat the transition layer to form a surface doping layer on a side of the transition layer away from the nickel-titanium alloy substrate.

[0103] like Figure 5 As shown, the transition layer of the nickel-titanium alloy substrate may include a Ti transition layer and a surface doping layer formed on a side of the Ti transition layer away from the nickel-titanium alloy substrate. The surface doping layer can serve as a highly antibacterial doped carbon-based film layer.

[0104] For example, the transition layer includes a Ti transition sublayer and a TiC transition sublayer. A titanium target is used to sputter a plasma-cleaned nickel-titanium alloy substrate to form the Ti transition sublayer. A titanium target and methane are used to form a TiC transition sublayer on the side of the Ti transition sublayer away from the nickel-titanium alloy substrate. A second target is then used to perform a coating process to form a surface doping layer on the side of the TiC transition sublayer away from the nickel-titanium alloy substrate.

[0105] like Figure 6 As shown, the transition layer of the nickel-titanium alloy substrate may include a Ti transition sublayer, a TiC transition sublayer, and a surface doping layer formed on the side of the TiC transition sublayer away from the nickel-titanium alloy substrate. The surface doping layer can serve as a highly antibacterial doped carbon-based film layer.

[0106] For example, the transition layer includes a Ti transition sublayer, a TiC transition sublayer, and a TiCN transition sublayer. A titanium target is used to sputter a plasma-cleaned nickel-titanium alloy substrate to form a Ti transition sublayer. A titanium target and methane are used to form a TiC transition sublayer on the side of the Ti transition sublayer away from the nickel-titanium alloy substrate. A titanium target, methane, and nitrogen are used to form a TiCN transition sublayer on the side of the TiC transition sublayer away from the nickel-titanium alloy substrate. A second target is then used to perform a coating process to form a surface doping layer on the side of the TiCN transition sublayer away from the nickel-titanium alloy substrate.

[0107] like Figure 7As shown, the transition layer of the nickel-titanium alloy substrate can include a Ti transition sublayer, a TiC transition sublayer, a TiCN transition sublayer, and a surface doping layer formed on the side of the TiCN transition sublayer away from the nickel-titanium alloy substrate. The surface doping layer can serve as a highly antibacterial doped carbon-based film layer.

[0108] When the surface of the nickel-titanium alloy substrate is coated with a transition layer and a surface doping layer, the nickel-titanium alloy substrate, the transition layer and the highly antibacterial doped carbon-based film layer can be used as a gradient composite structure to effectively regulate the stress distribution in the highly antibacterial doped carbon-based film layer, optimize the film-base bonding performance, and at the same time, by precisely controlling the proportion of active ingredients, it not only avoids the risk of high-concentration metal ion precipitation, but also ensures the long-term chemical stability of the highly antibacterial doped carbon-based film layer, which is beneficial to improving the structural stability of the highly antibacterial doped carbon-based film layer. Correspondingly, since the highly antibacterial doped carbon-based film layer can be doped with silver, titanium dioxide and nitrogen, it is beneficial to improve the antibacterial properties of the highly antibacterial doped carbon-based film layer. Based on this, the synergistic effect of the silver-titanium-carbon-nitrogen four phases in the highly antibacterial doped carbon-based film layer enables the highly antibacterial doped carbon-based film layer to have both antibacterial properties and structural stability. For example, nitrogen doping modulates the electronic structure of titanium dioxide, significantly reducing its optical band gap and enabling it to respond to visible light. This, in turn, allows titanium dioxide to exhibit photocatalytic antibacterial properties under visible light, which in turn helps improve the antibacterial properties of highly antibacterial doped carbon-based films. The structural stability and improved antibacterial properties of highly antibacterial doped carbon-based films contribute to a longer service life.

[0109] The method for preparing a highly antibacterial doped carbon-based film layer of a medical nickel-titanium alloy provided in an embodiment of the present application includes: pretreating a nickel-titanium alloy substrate, the pretreatment including polishing and ultrasonic cleaning; placing the pretreated nickel-titanium alloy substrate in a vacuum chamber; introducing argon gas into the vacuum chamber to plasma-clean the nickel-titanium alloy substrate in the vacuum chamber; using a target material to perform a coating treatment on the plasma-cleaned nickel-titanium alloy substrate to form a highly antibacterial doped carbon-based film layer on the surface of the nickel-titanium alloy substrate; in terms of atomic percentage, the silver content in the highly antibacterial doped carbon-based film layer is 5% to 20%, the titanium dioxide content is 3% to 15%, and the carbon content is 30% to 85%.

[0110] The silver included in the highly antibacterial doped carbon-based film layer of medical nickel-titanium alloy can provide long-lasting antibacterial activity for the highly antibacterial doped carbon-based film layer. The titanium dioxide included in the highly antibacterial doped carbon-based film layer can be used to enhance the photocatalytic antibacterial effect. The carbon included in the highly antibacterial doped carbon-based film layer can be used to construct a DLC structure. Based on this, the highly antibacterial doped carbon-based film layer can maintain the inherent biocompatibility and mechanical properties advantages of the DLC structure, and through the synergistic effect of the silver-titanium-carbon three-phase, make the highly antibacterial doped carbon-based film layer have both antibacterial properties and structural stability. When the highly antibacterial doped carbon-based film layer has antibacterial properties and structural stability, it is beneficial to improve the service life of the highly antibacterial doped carbon-based film layer.

[0111] The following specific examples illustrate the preparation method and performance of the highly antibacterial doped carbon-based film layer of the medical nickel-titanium alloy in the embodiments of the present application.

[0112] Example 1:

[0113] Using target materials, magnetron sputtering is used to plate DLC doped with silver and titanium dioxide on the surface of nickel-titanium alloy substrate to form a highly antibacterial doped carbon-based film layer. Target materials include titanium dioxide target, silver-carbon composite target and carbon target. Highly antibacterial doped carbon-based film layer of medical nickel-titanium alloy such as Figure 2 shown.

[0114] The preparation process of the highly antibacterial doped carbon-based film layer of medical nickel-titanium alloy includes:

[0115] (1) Providing a nickel-titanium alloy substrate and pre-treating the nickel-titanium alloy substrate: polishing the nickel-titanium alloy substrate until the surface smoothness of the nickel-titanium alloy substrate matches the smoothness of a mirror surface; ultrasonically cleaning the nickel-titanium alloy substrate with acetone, alcohol, and deionized water in sequence to remove surface oil and other contaminants on the nickel-titanium alloy substrate, and drying the nickel-titanium alloy substrate after ultrasonic cleaning with nitrogen.

[0116] (2) Placing the pretreated nickel-titanium alloy substrate into a vacuum chamber: Fixing the pretreated nickel-titanium alloy substrate onto a substrate stage in the vacuum chamber.

[0117] (3) Plasma cleaning of the nickel-titanium alloy substrate in the vacuum chamber: evacuate the vacuum chamber to a vacuum degree of 8×10 -4Pa; start the lighting system of the vacuum chamber and set the lighting power of the lighting system to 30W; introduce argon gas into the vacuum chamber, control the gas flow rate of argon gas to 180sccm, and maintain the working gas pressure of the vacuum chamber to 9.5Pa by adjusting the opening of the gate valve in the vacuum chamber to 8%; set the rotation speed of the substrate stage of the vacuum chamber to 5rpm, and apply a 500V bias voltage to the nickel-titanium alloy substrate fixed on the substrate stage; continuously clean the nickel-titanium alloy substrate under the above conditions for 10 minutes to bias clean the nickel-titanium alloy substrate, use oxygen plasma and argon plasma to bombard the surface of the nickel-titanium substrate to remove surface contaminants, and use argon plasma to bombard the surface of the nickel-titanium alloy substrate to remove surface oxide impurities.

[0118] (4) Coating: Keep argon gas flowing into the vacuum chamber and change the gas flow rate of argon gas to 70 sccm; maintain the working gas pressure of the vacuum chamber at 1.3 Pa by adjusting the opening of the plug valve in the vacuum chamber to 25%; start the RF power of the vacuum chamber; control the power of the titanium dioxide target to 130 W, the power of the silver-carbon composite target to 40 W, and the power of the carbon target to 200 W; control the titanium dioxide target, the silver-carbon composite target and the carbon target to run empty for 10 minutes to remove the surface oxides of the titanium dioxide target, the silver-carbon composite target and the carbon target; open the sample baffle in the vacuum chamber to allow the titanium dioxide target, the silver-carbon composite target and the carbon target to sputter the nickel-titanium alloy substrate after plasma cleaning; sputter the nickel-titanium alloy substrate after plasma cleaning under the above conditions for 2 hours to form a highly antibacterial doped carbon-based film layer on the surface of the nickel-titanium alloy substrate.

[0119] In this embodiment, the thickness of the highly antibacterial doped carbon-based film layer can reach 310nm. In terms of atomic percentage, the silver content of the highly antibacterial doped carbon-based film layer is 6% to 20%, the titanium dioxide content is 3% to 10%, and the carbon content is 70% to 85%. The highly antibacterial doped carbon-based film layer can achieve both structural stability and antibacterial properties through the synergistic effect of the silver-titanium-carbon three-phase, thereby improving the service life of the highly antibacterial doped carbon-based film layer.

[0120] Example 2:

[0121] Using target materials, plasma enhanced chemical vapor deposition is used to plate DLC doped with silver and titanium dioxide on the surface of nickel-titanium alloy substrate to form a highly antibacterial doped carbon-based film. Target materials include titanium dioxide targets and silver-carbon composite targets. Highly antibacterial doped carbon-based film layers for medical nickel-titanium alloys such as Figure 2 shown.

[0122] The preparation process of the highly antibacterial doped carbon-based film layer of medical nickel-titanium alloy includes:

[0123] (1) Providing a nickel-titanium alloy substrate and pre-treating the nickel-titanium alloy substrate.

[0124] (2) Place the pretreated nickel-titanium alloy substrate into a vacuum chamber.

[0125] (3) Plasma cleaning of the nickel-titanium alloy substrate in the vacuum chamber.

[0126] (4) Coating: Keep argon flowing into the vacuum chamber and change the gas flow rate of argon to 30 sccm; introduce methane into the vacuum chamber and control the gas flow rate of methane to 30 sccm, and the ratio between the gas flow rates of methane and argon is 1:1; control the opening of the plug valve in the vacuum chamber to 15%, and maintain the working gas pressure in the vacuum chamber to 3.2 Pa; start the RF power supply of the vacuum chamber, such as controlling the working power of the RF power supply to 100 W; control the sputtering power of the titanium dioxide target to 130 W and the sputtering power of the silver-carbon composite target to 40 W; control the titanium dioxide target and the silver-carbon composite target to run empty for 10 minutes to remove the surface oxides of the titanium dioxide target and the silver-carbon composite target; open the sample baffle in the vacuum chamber to allow the titanium dioxide target and the silver-carbon composite target to sputter the nickel-titanium alloy substrate after plasma cleaning; sputter the nickel-titanium alloy substrate after plasma cleaning under the above conditions for 30 minutes to form a highly antibacterial doped carbon-based film layer on the surface of the nickel-titanium alloy substrate.

[0127] In this embodiment, the thickness of the highly antibacterial doped carbon-based film layer can reach 345nm. In terms of atomic percentage, the silver content of the highly antibacterial doped carbon-based film layer is 6% to 20%, the titanium dioxide content is 3% to 10%, and the carbon content is 70% to 85%. The highly antibacterial doped carbon-based film layer can achieve both structural stability and antibacterial properties through the synergistic effect of the silver-titanium-carbon three-phase, thereby improving the service life of the highly antibacterial doped carbon-based film layer.

[0128] For processes (1) to (3) in this embodiment, reference may be made to processes (1) to (3) in Example 1, and no further details will be given here.

[0129] Example 3:

[0130] Using target materials, magnetron sputtering and plasma enhanced chemical vapor deposition are used to plate DLC doped silver doped titanium dioxide on the surface of nickel titanium alloy substrate to form a highly antibacterial doped carbon-based film layer. Target materials include titanium dioxide target, silver carbon composite target and carbon target. Highly antibacterial doped carbon-based film layer for medical nickel titanium alloy such as Figure 2 shown.

[0131] The preparation process of the highly antibacterial doped carbon-based film layer of medical nickel-titanium alloy includes:

[0132] (1) Providing a nickel-titanium alloy substrate and pre-treating the nickel-titanium alloy substrate.

[0133] (2) Place the pretreated nickel-titanium alloy substrate into a vacuum chamber.

[0134] (3) Plasma cleaning of the nickel-titanium alloy substrate in the vacuum chamber.

[0135] (4) Coating: Keep argon flowing into the vacuum chamber and change the gas flow rate of argon to 30sccm; introduce methane into the vacuum chamber and control the gas flow rate of methane to 30sccm, and the ratio between the gas flow rates of methane and argon is 1:1; control the opening of the plug valve in the vacuum chamber to 25%, and maintain the working pressure in the vacuum chamber to 3.2Pa; start the RF power supply of the vacuum chamber, such as controlling the working power of the RF power supply to 100W; control the sputtering power of the titanium dioxide target to 130W, and the silver-carbon composite The sputtering power of the target is 40W, and the sputtering power of the carbon target is 200W; the titanium dioxide target, the silver-carbon composite target, and the carbon target are controlled to run empty for 10 minutes to remove the surface oxides of the titanium dioxide target, the silver-carbon composite target, and the carbon target; the sample baffle in the vacuum chamber is opened to allow the titanium dioxide target, the silver-carbon composite target, and the carbon target to sputter the plasma-cleaned nickel-titanium alloy substrate; under the above conditions, the plasma-cleaned nickel-titanium alloy substrate is sputtered for 1 hour to form a highly antibacterial doped carbon-based film layer on the surface of the nickel-titanium alloy substrate.

[0136] In this embodiment, the thickness of the highly antimicrobial doped carbon-based film layer can reach 530 nm. In atomic percentage, the silver content of the highly antimicrobial doped carbon-based film layer is 6%-20%, the titanium dioxide content is 3%-10%, and the carbon content is 70%-85%. Through the synergistic effect of the silver-titanium-carbon three-phase, the highly antimicrobial doped carbon-based film layer can simultaneously possess structural stability and antimicrobial properties, thereby extending the service life of the highly antimicrobial doped carbon-based film layer.

[0137] For processes (1) to (3) in this embodiment, reference may be made to processes (1) to (3) in Example 1, and no further details will be given here.

[0138] Example 4:

[0139] Using target materials, DLC doped with silver, titanium dioxide and nitrogen is plated on the surface of nickel-titanium alloy substrate. Target materials include titanium dioxide target, silver-carbon composite target and carbon target. Highly antibacterial doped carbon-based film layer of medical nickel-titanium alloy, such as Figure 3 shown.

[0140] The preparation process of the highly antibacterial doped carbon-based film layer of medical nickel-titanium alloy includes:

[0141] (1) Providing a nickel-titanium alloy substrate and pre-treating the nickel-titanium alloy substrate.

[0142] (2) Place the pretreated nickel-titanium alloy substrate into a vacuum chamber.

[0143] (3) Plasma cleaning of the nickel-titanium alloy substrate in the vacuum chamber.

[0144] (4) Coating: Keep argon gas flowing into the vacuum chamber and change the gas flow rate of argon gas to 70 sccm; introduce nitrogen gas into the vacuum chamber and control the gas flow rate of nitrogen gas to 2 sccm; control the opening of the plug valve in the vacuum chamber to 25%, and maintain the working gas pressure in the vacuum chamber to 1.3 Pa; start the RF power supply in the vacuum chamber; control the power of the titanium dioxide target to 130 W, the power of the silver-carbon composite target to 40 W, and the power of the carbon target to 200 W; control the titanium dioxide target, the silver-carbon composite target and the carbon target to run empty for 10 minutes to remove the surface oxides of the titanium dioxide target, the silver-carbon composite target and the carbon target; open the sample baffle in the vacuum chamber to allow the titanium dioxide target, the silver-carbon composite target and the carbon target to sputter the nickel-titanium alloy substrate after plasma cleaning; sputter the nickel-titanium alloy substrate after plasma cleaning under the above conditions for 2 hours to form a highly antibacterial doped carbon-based film layer on the surface of the nickel-titanium alloy substrate.

[0145] In this embodiment, the thickness of the highly antimicrobial doped carbon-based film layer can reach 320 nm. In terms of atomic percentage, the highly antimicrobial doped carbon-based film layer comprises 5% to 15% silver, 6% to 15% titanium dioxide, 30% to 60% carbon, and 5% to 15% nitrogen.

[0146] For processes (1) to (3) in this embodiment, reference may be made to processes (1) to (3) in Example 1, and no further details will be given here.

[0147] See also Figure 8 , Figure 8 This is a microscopic image of the film layer in the related art.

[0148] See also Figure 9 , Figure 9 This is a microscopic image of the highly antibacterial doped carbon-based film layer of the medical nickel-titanium alloy involved in Example 4 of the present application.

[0149] The film layer in the related art includes an intrinsic DLC structure, which refers to a pure DLC material that is not doped with any other elements on the basis of carbon and has a diamond-like structure.

[0150] Since the highly antimicrobial doped carbon-based film layer of this embodiment can be doped with silver, titanium dioxide, and nitrogen, the highly antimicrobial doped carbon-based film layer of this embodiment can have a doped DLC structure. The doped DLC structure is used to indicate a DLC material doped with other elements on the basis of carbon, having a diamond-like structure.

[0151] Figure 8 as well as Figure 9 The obtained structures can be obtained by scanning the film layer with intrinsic DLC structure in the related art and the high antibacterial doped carbon-based film layer involved in this embodiment respectively using a scanning electron microscope (SEM).

[0152] For the highly antibacterial doped carbon-based film layer involved in this embodiment, the elemental composition of the material can be analyzed using an energy dispersive X-ray spectroscopy (EDS). The elemental composition of the material of the highly antibacterial doped carbon-based film layer is shown in the following table:

[0153] element number of atoms Normalized mass (%) atom(%) C 6 14.45 35.38 N 7 6.18 12.98 O 8 13.98 25.69 Ti 22 23.76 14.60 Ag 47 41.64 11.35 total 100 100

[0154] See also Figure 10 , Figure 10 yes Figure 9 Raman spectroscopy of the highly antibacterial doped carbon-based film layers involved.

[0155] like Figure 10 As shown, for the highly antibacterial doped carbon-based film layer, at 1363 cm -1 The characteristic peak of amorphous carbon, D peak, was observed at 221.4 cm -1 ; at 1566cm -1 The characteristic peak of amorphous carbon, namely the G peak, was observed at 150.9 cm -1 The intensity ratio of D peak to G peak ID / IG is 0.99. The smaller the ID / IG ratio is, the higher the sp 3 Based on this, it can be determined that the highly antibacterial doped carbon-based film layer still has a DLC structure. Accordingly, it can be determined that the highly antibacterial doped carbon-based film layer still has a certain structural stability.

[0156] See also Figure 11 , Figure 11 yes Figure 9 Antibacterial test diagram corresponding to the highly antibacterial doped carbon-based film layer of the medical nickel-titanium alloy involved.

[0157] like Figure 11As shown, compared to the blank control group, the highly antimicrobial doped carbon-based film showed significantly less Staphylococcus aureus after 12 and 24 hours of stasis. According to ISO 22196 testing, the highly antimicrobial doped carbon-based film in this example achieved a 24-hour inhibition rate of 99.5% against Staphylococcus aureus. This demonstrates that the highly antimicrobial doped carbon-based film exhibits superior antimicrobial properties.

[0158] In the case of DLC structure doped with silver, titanium dioxide and nitrogen on the surface of nickel-titanium alloy substrate, by controlling the content of silver, titanium dioxide, carbon and nitrogen in the high antibacterial doped carbon-based film layer, the silver-titanium-carbon-nitrogen four-phase in the high antibacterial doped carbon-based film layer can be made to work synergistically, so that the high antibacterial doped carbon-based film layer can have both antibacterial properties and structural stability, thereby improving the service life of the high antibacterial doped carbon-based film layer.

[0159] Doping nitrogen in the highly antibacterial doped carbon-based film layer can form strong covalent bonds between nitrogen and carbon and titanium in the highly antibacterial doped carbon-based film layer, thereby improving the hardness and wear resistance of the highly antibacterial doped carbon-based film layer. For example, doping nitrogen in the DLC structure of the highly antibacterial doped carbon-based film layer can form an N-DLC structure, thereby controlling the hybridization mode of carbon atoms in the highly antibacterial doped carbon-based film layer to be sp 3 Hybridization, thereby balancing the hardness and toughness of the high antibacterial doped carbon-based film layer. At the same time, the high antibacterial doped carbon-based film layer can use the N-DLC structure to adjust the crystallinity and defect density of the high antibacterial doped carbon-based film layer, thereby effectively alleviating the internal stress generated during the high-energy deposition process and enhancing the film-base bonding force between the nickel-titanium alloy substrate and the high antibacterial doped carbon-based film layer. Furthermore, nitrogen doping in the high antibacterial doped carbon-based film layer can reduce the optical band gap of titanium dioxide by regulating the electronic structure of titanium dioxide, so that it has visible light response ability and thus has photocatalytic activity under visible light. Moreover, the nitrogen and silver in the high antibacterial doped carbon-based film layer can act synergistically to enhance the spectral antibacterial effect of the high antibacterial doped carbon-based film layer. Based on this, the high antibacterial doped carbon-based film layer formed on the surface of the nickel-titanium alloy substrate can have both antibacterial properties and structural stability, which is beneficial to improving the service life of the high antibacterial doped carbon-based film layer.

[0160] Example 5:

[0161] A transition layer, such as a Ti transition layer, is plated on the surface of a nickel-titanium alloy substrate using a first target material, and a film coating process is performed using a second target material to plate DLC-doped silver, nitrogen, and titanium dioxide on the side of the Ti transition layer away from the nickel-titanium alloy substrate to form a surface doped layer, thereby forming a highly antibacterial doped carbon-based film layer. The first target material includes a titanium target, and the second target material includes a titanium dioxide target, a silver-carbon composite target, and a carbon target. Highly antibacterial doped carbon-based film layer for medical nickel-titanium alloys, such as Figure 5 shown.

[0162] The preparation process of the highly antibacterial doped carbon-based film layer of medical nickel-titanium alloy includes:

[0163] (1) Providing a nickel-titanium alloy substrate and pre-treating the nickel-titanium alloy substrate.

[0164] (2) Place the pretreated nickel-titanium alloy substrate into a vacuum chamber.

[0165] (3) Plasma cleaning of the nickel-titanium alloy substrate in the vacuum chamber.

[0166] (4) Coating: Keep argon gas flowing into the vacuum chamber and change the gas flow rate of argon gas to 70 sccm; introduce nitrogen gas into the vacuum chamber and control the gas flow rate of nitrogen gas to 6 sccm; control the opening of the plug valve in the vacuum chamber to 25%, and maintain the working pressure in the vacuum chamber to 1.3 Pa; start the RF power supply of the vacuum chamber; control the sputtering power of the titanium target to 200 W; control the titanium target to run empty for 10 minutes to remove the surface oxide of the titanium target; open the sample baffle in the vacuum chamber to allow the titanium target to sputter the nickel-titanium alloy substrate after plasma cleaning; sputter the nickel-titanium alloy substrate after plasma cleaning under the above conditions for 30 minutes to form a transition layer on the surface of the nickel-titanium alloy substrate, the transition layer including T i transition sublayer; turn off the titanium target; control the sputtering power of the titanium dioxide target to 130W, the sputtering power of the silver-carbon composite target to 40W, and the sputtering power of the carbon target to 200W; control the titanium dioxide target, the silver-carbon composite target and the carbon target to run empty for 10 minutes to remove the surface oxides of the titanium dioxide target, the silver-carbon composite target and the carbon target; open the sample baffle in the vacuum chamber to allow the titanium dioxide target, the silver-carbon composite target and the carbon target to sputter the nickel-titanium alloy substrate after the transition layer is formed; under the above conditions, the nickel-titanium alloy substrate after the transition layer is formed is sputtered for 2 hours to form a surface doping layer on the side of the transition layer, such as the Ti transition sublayer away from the nickel-titanium alloy substrate, and then form a highly antibacterial doped carbon-based film layer on the surface of the nickel-titanium alloy substrate.

[0167] In this embodiment, the thickness of the transition layer can reach 40 nm, and the thickness of the surface doped layer can reach 310 nm. Based on the thickness of the transition layer and the surface doped layer, the total thickness of the coating on the nickel-titanium alloy substrate can be determined to be 350 nm. In atomic percentage, the silver content of the highly antibacterial doped carbon-based film is 5% to 15%, the titanium dioxide content is 6% to 15%, the carbon content is 30% to 60%, and the nitrogen content is 20% to 35%.

[0168] For processes (1) to (3) in this embodiment, reference may be made to processes (1) to (3) in Example 1, and no further details will be given here.

[0169] See also Figure 12, Figure 12 This is a microscopic image of the highly antibacterial doped carbon-based film layer of the medical nickel-titanium alloy involved in Example 5 of the present application.

[0170] In this embodiment, a transition layer and a surface doping layer are plated on the surface of the nickel-titanium alloy substrate. Since the highly antibacterial doped carbon-based film layer of this embodiment can be doped with silver, titanium dioxide, and nitrogen, the highly antibacterial doped carbon-based film layer of this embodiment can have a doped DLC structure.

[0171] Figure 12 The high antibacterial doped carbon-based film layer involved in this embodiment can be obtained by scanning using SEM.

[0172] contrast Figure 8 as well as Figure 12 It can be seen that the wear resistance of the doped DLC structure involved in this embodiment is improved compared to the intrinsic DLC structure, which is equivalent to the structural stability of the highly antibacterial doped carbon-based film layer being improved compared to the film layer with intrinsic DLC.

[0173] For the highly antibacterial doped carbon-based film layer involved in this embodiment, the elemental composition of the material can be analyzed using an energy dispersive X-ray spectroscopy (EDS). The elemental composition of the material of the highly antibacterial doped carbon-based film layer is shown in the following table:

[0174] element number of atoms Normalized mass (%) atom(%) C 6 20.22 41.92 N 7 17.07 30.36 O 8 3.87 6.02 Ti 22 28.03 14.58 Ag 47 30.82 7.12 total 100 100

[0175] See also Figure 13 , Figure 13 yes Figure 12 Raman spectroscopy of the highly antibacterial doped carbon-based film layers involved.

[0176] like Figure 13 As shown, for the highly antibacterial doped carbon-based film layer, at 1356 cm -1 The characteristic peak of amorphous carbon, namely D peak, was observed at 226 cm -1 ; at 1562cm -1 The characteristic peak of amorphous carbon, namely the G peak, was observed at 153 cm -1 The intensity ratio of D peak to G peak ID / IG is 1.08. The smaller the ID / IG ratio is, the higher the sp 3 Based on this, it can be determined that the highly antibacterial doped carbon-based film layer still has a DLC structure. Accordingly, it can be determined that the highly antibacterial doped carbon-based film layer still has a certain structural stability.

[0177] See also Figure 14 , Figure 14 yes Figure 12Antibacterial test diagram of the highly antibacterial doped carbon-based film layer involved.

[0178] like Figure 14 As shown, compared to the blank control group, the highly antimicrobial doped carbon-based film showed significantly less Staphylococcus aureus after 12 and 24 hours of stasis. According to ISO 22196 testing, the highly antimicrobial doped carbon-based film in this example achieved a 24-hour inhibition rate of 99.5% against Staphylococcus aureus. This demonstrates that the highly antimicrobial doped carbon-based film exhibits superior antimicrobial properties.

[0179] When a transition layer and a surface doping layer are plated on the surface of the nickel-titanium alloy substrate, the nickel-titanium alloy substrate, the transition layer and the surface doping layer are equivalent to a gradient composite structure. The gradient composite structure can be used to improve the adhesion of the high antibacterial doped carbon-based film layer, relieve the stress of the high antibacterial doped carbon-based film layer, and improve the bonding force between the nickel-titanium alloy substrate and the high antibacterial doped carbon-based film layer. The surface doping layer in the gradient composite structure can be used to improve the antibacterial performance of the high antibacterial doped carbon-based film layer, thereby enabling the high antibacterial doped carbon-based film layer to have both antibacterial performance and structural stability. Accordingly, by controlling the content of silver, titanium dioxide, carbon and nitrogen in the high antibacterial doped carbon-based film layer, the silver-titanium-carbon-nitrogen four-phase synergistic effect in the high antibacterial doped carbon-based film layer can be achieved, which is beneficial to improving the antibacterial performance and structural stability of the nickel-titanium alloy substrate, thereby improving the service life of the high antibacterial doped carbon-based film layer.

[0180] Example 6:

[0181] The first target material is used to plate a transition layer, such as a Ti transition sublayer and a TiC transition sublayer, on the surface of the nickel-titanium alloy substrate. The second target material is used for coating to plate DLC, silver-doped, nitrogen-doped, and titanium dioxide on the side of the TiC transition sublayer away from the nickel-titanium alloy substrate to form a surface doped layer, thereby forming a highly antibacterial doped carbon-based film layer. The first target material includes a titanium target, and the second target material includes a titanium dioxide target, a silver-carbon composite target, and a carbon target. Highly antibacterial doped carbon-based film layer for medical nickel-titanium alloys such as Figure 6 shown.

[0182] The preparation process of the highly antibacterial doped carbon-based film layer of medical nickel-titanium alloy includes:

[0183] (1) Providing a nickel-titanium alloy substrate and pre-treating the nickel-titanium alloy substrate.

[0184] (2) Place the pretreated nickel-titanium alloy substrate into a vacuum chamber.

[0185] (3) Plasma cleaning of the nickel-titanium alloy substrate in the vacuum chamber.

[0186] (4) Coating: Keep argon gas flowing into the vacuum chamber and change the argon gas flow rate to 70 sccm; control the opening of the plug valve in the vacuum chamber to 25%, and keep the working gas pressure in the vacuum chamber to 1.3 Pa; start the RF power supply of the vacuum chamber; control the sputtering power of the titanium target to 200 W; control the titanium target to run empty for 10 minutes to remove the surface oxide of the titanium target; open the sample baffle in the vacuum chamber to allow the titanium target to sputter the nickel-titanium alloy substrate after plasma cleaning; sputter the nickel-titanium alloy substrate after plasma cleaning for 30 minutes under the above conditions to form a Ti transition sublayer on the surface of the nickel-titanium alloy substrate; keep the titanium target open and introduce methane into the vacuum chamber with a methane gas flow rate of 10 sccm; control the titanium target to sputter the nickel-titanium alloy substrate after the Ti transition sublayer is formed for 30 minutes under the above conditions to make the Ti transition sublayer away from the nickel-titanium alloy substrate. The invention discloses a method for forming a TiC transition sublayer on one side of the nickel-titanium alloy substrate; closing the titanium target and stopping the introduction of methane into the vacuum chamber; introducing nitrogen into the vacuum chamber with a nitrogen gas flow rate of 2 sccm; controlling the sputtering power of the titanium dioxide target to 130 W, the sputtering power of the silver-carbon composite target to 40 W, and the sputtering power of the carbon target to 200 W; controlling the titanium dioxide target, the silver-carbon composite target and the carbon target to run empty for 10 minutes to remove the surface oxides of the titanium dioxide target, the silver-carbon composite target and the carbon target; opening the sample baffle in the vacuum chamber to allow the titanium dioxide target, the silver-carbon composite target and the carbon target to sputter the nickel-titanium alloy substrate after the transition layer is formed; under the above conditions, sputtering the nickel-titanium alloy substrate after the Ti transition sublayer and the TiC transition sublayer are formed for 2 hours to form a surface doping layer on the side of the TiC transition sublayer away from the nickel-titanium alloy substrate, thereby forming a highly antibacterial doped carbon-based film layer on the surface of the nickel-titanium alloy substrate.

[0187] In this embodiment, the thickness of the Ti transition sublayer can reach 40nm, the thickness of the TiC transition sublayer can reach 30nm, and the thickness of the transition layer can reach 70nm. The thickness of the surface doping layer can reach 310nm. According to the thickness of the Ti transition sublayer, the thickness of the TiC transition sublayer and the thickness of the surface doping layer, it can be determined that the total coating thickness of the nickel-titanium alloy substrate is 380nm. In terms of atomic percentage, the silver content in the high antibacterial doped carbon-based film layer is 5% to 20%, the titanium dioxide content is 6% to 15%, the carbon content is 30% to 60%, and the nitrogen content is 5% to 15%. The high antibacterial doped carbon-based film layer can achieve structural stability and antibacterial properties through the synergistic effect of the silver-titanium-carbon-nitrogen four phases, thereby improving the service life of the high antibacterial doped carbon-based film layer.

[0188] For processes (1) to (3) in this embodiment, reference may be made to processes (1) to (3) in Example 1, and no further details will be given here.

[0189] Example 7:

[0190] The first target material is used to plate a transition layer, such as a Ti transition sublayer, a TiC transition sublayer, and a TiCN transition sublayer, on the surface of the nickel-titanium alloy substrate. The second target material is used for coating to plate DLC, silver-doped, nitrogen-doped, and titanium dioxide on the side of the TiCN transition sublayer away from the nickel-titanium alloy substrate to form a surface doped layer, thereby forming a highly antibacterial doped carbon-based film layer. The first target material includes a titanium target, and the second target material includes a titanium dioxide target, a silver-carbon composite target, and a carbon target. Highly antibacterial doped carbon-based film layer for medical nickel-titanium alloys such as Figure 7 shown.

[0191] The preparation process of the highly antibacterial doped carbon-based film layer of medical nickel-titanium alloy includes:

[0192] (1) Providing a nickel-titanium alloy substrate and pre-treating the nickel-titanium alloy substrate.

[0193] (2) Place the pretreated nickel-titanium alloy substrate into a vacuum chamber.

[0194] (3) Plasma cleaning of the nickel-titanium alloy substrate in the vacuum chamber.

[0195] (4) Coating: Keep argon gas flowing into the vacuum chamber and change the gas flow rate of argon gas to 70 sccm; control the opening of the plug valve in the vacuum chamber to 25%, and maintain the working pressure in the vacuum chamber to 1.3 Pa; start the RF power supply of the vacuum chamber; control the sputtering power of the titanium target to 200 W; control the titanium target to run empty for 10 minutes to remove the surface oxide of the titanium target; open the sample baffle in the vacuum chamber to allow the titanium target to sputter the nickel-titanium alloy substrate after plasma cleaning; plasma clean the sample under the above conditions. The nickel-titanium alloy substrate after the Ti transition sublayer is sputtered for 30 minutes to form a Ti transition sublayer on the surface of the nickel-titanium alloy substrate; the titanium target is kept on, and methane is introduced into the vacuum chamber, and the gas flow rate of methane is 10 sccm; under the above conditions, the titanium target is controlled to sputter the nickel-titanium alloy substrate after the Ti transition sublayer is formed for 30 minutes to form a TiC transition sublayer on the side of the Ti transition sublayer away from the nickel-titanium alloy substrate; the titanium target is kept on, and methane is kept introduced into the vacuum chamber, and nitrogen is introduced into the vacuum chamber, and the gas flow rate of nitrogen is The titanium target was controlled to sputter the nickel-titanium alloy substrate after the Ti transition sublayer and the TiC transition sublayer were formed under the above conditions for 20 minutes, so as to form a TiCN transition sublayer on the side of the TiC transition sublayer away from the nickel-titanium alloy substrate; the titanium target was turned off and the introduction of methane was stopped; the sputtering power of the titanium dioxide target was controlled to be 130W, the sputtering power of the silver-carbon composite target was controlled to be 40W, and the sputtering power of the carbon target was controlled to be 200W; the titanium dioxide target, the silver-carbon composite target and the carbon target were controlled to run empty for 10 minutes to remove the titanium dioxide. surface oxides of the titanium target, the silver-carbon composite target and the carbon target; opening the sample baffle in the vacuum chamber to allow the titanium dioxide target, the silver-carbon composite target and the carbon target to sputter the nickel-titanium alloy substrate after the transition layer is formed; under the above conditions, the nickel-titanium alloy substrate after the Ti transition sublayer, the TiC transition sublayer and the TiCN transition sublayer are formed is sputtered for 2 hours to form a surface doped layer on the side of the TiCN transition sublayer away from the nickel-titanium alloy substrate, and then a highly antibacterial doped carbon-based film layer is formed on the surface of the nickel-titanium alloy substrate.

[0196] In this embodiment, the thickness of the Ti transition sublayer can reach 40nm, the thickness of the TiC transition sublayer can reach 30nm, the thickness of the TiCN transition sublayer can reach 20nm, and the thickness of the transition layer can reach 90nm. The thickness of the surface doping layer can reach 310nm. According to the thickness of the Ti transition sublayer, the thickness of the TiC transition sublayer, the thickness of the TiCN transition sublayer and the thickness of the surface doping layer, the total coating thickness of the nickel-titanium alloy substrate can be determined to be 400nm. In terms of atomic percentage, the silver content in the high antibacterial doped carbon-based film layer is 5% to 20%, the titanium dioxide content is 6% to 15%, the carbon content is 30% to 60%, and the nitrogen content is 5% to 15%. The high antibacterial doped carbon-based film layer can achieve both structural stability and antibacterial properties through the synergistic effect of the silver-titanium-carbon-nitrogen four-phase, thereby improving the service life of the high antibacterial doped carbon-based film layer.

[0197] For processes (1) to (3) in this embodiment, reference may be made to processes (1) to (3) in Example 1, and no further details will be given here.

[0198] The present application also provides a highly antibacterial doped carbon-based film layer of medical nickel-titanium alloy, which is prepared according to the aforementioned method for preparing the highly antibacterial doped carbon-based film layer of medical nickel-titanium alloy.

[0199] In some embodiments, the highly antimicrobial doped carbon-based film layer may include silver, titanium dioxide, and carbon. In atomic percentage, the silver content of the highly antimicrobial doped carbon-based film layer is 5% to 20%, the titanium dioxide content is 3% to 15%, and the carbon content is 30% to 85%. The highly antimicrobial doped carbon-based film layer can achieve both structural stability and antimicrobial properties through the synergistic effect of the silver, titanium, and carbon phases, thereby extending the service life of the highly antimicrobial doped carbon-based film layer.

[0200] For example, the highly antibacterial doped carbon-based film layer may also include silver, titanium dioxide, carbon, and nitrogen. In terms of atomic percentage, the silver content of the highly antibacterial doped carbon-based film layer is 5% to 20%, the titanium dioxide content is 6% to 15%, the carbon content is 30% to 60%, and the nitrogen content is 5% to 35%. The highly antibacterial doped carbon-based film layer can achieve both structural stability and antibacterial properties through the synergistic effect of the silver-titanium-carbon-nitrogen four-phase, thereby extending the service life of the highly antibacterial doped carbon-based film layer.

[0201] In some embodiments, the highly antibacterial doped carbon-based film may include a transition layer and a surface doped layer. The transition layer is formed on the surface of the nickel-titanium alloy substrate. The surface doped layer is formed on the side of the transition layer away from the nickel-titanium alloy substrate.

[0202] The highly antibacterial doped carbon-based film layer involved in this embodiment can refer to the relevant description of the highly antibacterial doped carbon-based film layer in the aforementioned embodiment, and will not be repeated here.

[0203] In the case where a highly antibacterial doped carbon-based film layer of medical nickel-titanium alloy is prepared according to the aforementioned method for preparing a highly antibacterial doped carbon-based film layer of medical nickel-titanium alloy, the silver included in the highly antibacterial doped carbon-based film layer can provide long-lasting antibacterial activity for the highly antibacterial doped carbon-based film layer. The titanium dioxide included in the highly antibacterial doped carbon-based film layer can be used to enhance the photocatalytic antibacterial effect. The carbon included in the highly antibacterial doped carbon-based film layer can be used to construct a DLC structure. The nitrogen included in the highly antibacterial doped carbon-based film layer can be used to construct an N-DLC structure. Based on this, the highly antibacterial doped carbon-based film layer can, on the basis of maintaining the inherent biocompatibility and mechanical properties advantages of the DLC structure, through the synergistic effect of the silver-titanium-carbon three-phase or the synergistic cooperation of the silver-titanium-carbon-nitrogen four-phase, make the highly antibacterial doped carbon-based film layer have both antibacterial properties and structural stability. When the highly antibacterial doped carbon-based film layer has antibacterial properties and structural stability, it is beneficial to improve the service life of the highly antibacterial doped carbon-based film layer.

[0204] The present application also provides a coated component. The coated component comprises: a nickel-titanium alloy substrate; and a highly antibacterial doped carbon-based film layer formed on the surface of the nickel-titanium alloy substrate; the highly antibacterial doped carbon-based film layer is prepared according to the aforementioned method for preparing a highly antibacterial doped carbon-based film layer of medical nickel-titanium alloy.

[0205] In some embodiments, the highly antimicrobial doped carbon-based film layer included in the coated component may include silver, titanium dioxide, and carbon. In atomic percentage, the silver content of the highly antimicrobial doped carbon-based film layer is 5% to 20%, the titanium dioxide content is 3% to 15%, and the carbon content is 30% to 85%. The highly antimicrobial doped carbon-based film layer can achieve both structural stability and antimicrobial properties through the synergistic effect of the silver, titanium, and carbon phases, thereby improving the service life of the highly antimicrobial doped carbon-based film layer and, in turn, the service life of the coated component.

[0206] For example, the highly antibacterial doped carbon-based film layer included in the coated part may also include silver, titanium dioxide, carbon, and nitrogen. In terms of atomic percentage, the silver content of the highly antibacterial doped carbon-based film layer is 5% to 20%, the titanium dioxide content is 6% to 15%, the carbon content is 30% to 60%, and the nitrogen content is 5% to 35%. The highly antibacterial doped carbon-based film layer can achieve both structural stability and antibacterial properties through the synergistic effect of the silver-titanium-carbon-nitrogen four-phase, which helps to extend the service life of the highly antibacterial doped carbon-based film layer and, in turn, the service life of the coated part.

[0207] In some embodiments, a transition layer may be provided between the nickel-titanium alloy substrate and the highly antimicrobial doped carbon-based film layer of the coated article. The transition layer is formed on the surface of the nickel-titanium alloy substrate. The highly antimicrobial doped carbon-based film layer is formed as a surface doping layer on the side of the transition layer away from the nickel-titanium alloy substrate.

[0208] The highly antibacterial doped carbon-based film layer of the transition layer involved in this embodiment can refer to the relevant description of the highly antibacterial doped carbon-based film layer in the aforementioned embodiment, and will not be repeated here.

[0209] The coated part provided in the above embodiment includes: a nickel-titanium alloy substrate; and a highly antibacterial doped carbon-based film layer formed on the surface of the nickel-titanium alloy substrate. The highly antibacterial doped carbon-based film layer is prepared according to the preparation method of the highly antibacterial doped carbon-based film layer of the aforementioned medical nickel-titanium alloy.

[0210] The silver in the highly antibacterial doped carbon-based film layer can provide the highly antibacterial doped carbon-based film layer with long-lasting antibacterial activity. The titanium dioxide in the highly antibacterial doped carbon-based film layer can be used to enhance the photocatalytic antibacterial effect. The carbon in the highly antibacterial doped carbon-based film layer can be used to construct a DLC structure. The nitrogen included in the highly antibacterial doped carbon-based film layer can be used to construct an N-DLC structure. Based on this, the highly antibacterial doped carbon-based film layer can maintain the inherent biocompatibility and mechanical properties advantages of the DLC structure, and through the silver-titanium-carbon three-phase synergistic effect or the silver-titanium-carbon-nitrogen four-phase synergistic effect, the highly antibacterial doped carbon-based film layer can have both antibacterial properties and structural stability. When the highly antibacterial doped carbon-based film layer has both antibacterial properties and structural stability, it is beneficial to improve the service life of the highly antibacterial doped carbon-based film layer. Accordingly, when the service life of the high antibacterial doped carbon-based film layer is improved, the high antibacterial doped carbon-based film layer can provide long-term protection for the nickel-titanium alloy substrate, which is beneficial to improving the service life of the coated parts.

[0211] It should be understood that the terms used in this specification of the application are only for the purpose of describing specific embodiments and are not intended to limit the application. As used in this specification of the application and the appended claims, unless the context clearly indicates otherwise, the singular forms of "one", "an" and "the" are intended to include plural forms. It should also be understood that the term "and / or" used in this specification of the application and the appended claims refers to any combination of one or more of the associated listed items and all possible combinations, and includes these combinations. It should be noted that, in this article, the term "comprises", "comprising" or any other variant thereof is intended to cover non-exclusive inclusion, so that the process, method, article or system including a series of elements includes not only those elements, but also includes other elements not explicitly listed, or also includes elements inherent to such process, method, article or system. In the absence of more restrictions, the elements defined by the sentence "comprising one..." do not exclude the presence of other identical elements in the process, method, article or system including the element.

[0212] The serial numbers of the embodiments of the present application are for description only and do not represent the advantages or disadvantages of the embodiments. The above description is only a specific embodiment of the present application, but the scope of protection of the present application is not limited thereto. Any technician familiar with the technical field can easily think of various equivalent modifications or replacements within the technical scope disclosed in this application, and these modifications or replacements should be included in the scope of protection of this application. Therefore, the scope of protection of this application should be based on the scope of protection of the claims.

Claims

1. A method for preparing a highly antibacterial doped carbon-based film layer of medical nickel-titanium alloy, characterized in that: include: Pre-treating the nickel-titanium alloy substrate, wherein the pre-treatment includes polishing and ultrasonic cleaning; placing the pretreated nickel-titanium alloy substrate into a vacuum chamber; introducing argon gas into the vacuum chamber to perform plasma cleaning on the nickel-titanium alloy substrate in the vacuum chamber; The plasma-cleaned nickel-titanium alloy substrate is plated using a target material to form a highly antibacterial doped carbon-based film layer on the surface of the nickel-titanium alloy substrate. The target material includes a titanium dioxide target and a silver-carbon composite target. In terms of atomic percentage, the silver content in the highly antibacterial doped carbon-based film layer is 5% to 20%, the titanium dioxide content is 3% to 15%, and the carbon content is 30% to 85%.

2. The preparation method according to claim 1, characterized in that The target material is used to perform a coating process on the plasma-cleaned nickel-titanium alloy substrate to form a highly antibacterial doped carbon-based film layer on the surface of the nickel-titanium alloy substrate, comprising: The target material is used to perform a sputtering process on the nickel-titanium alloy substrate after plasma cleaning to form a highly antibacterial doped carbon-based film layer on the surface of the nickel-titanium alloy substrate.

3. The preparation method according to claim 1, characterized in that The target material is used to perform a coating process on the plasma-cleaned nickel-titanium alloy substrate to form a highly antibacterial doped carbon-based film layer on the surface of the nickel-titanium alloy substrate, comprising: The plasma-cleaned nickel-titanium alloy substrate is plated using a titanium dioxide target, a silver-carbon composite target, and a carbon target to form a highly antibacterial doped carbon-based film layer on the surface of the nickel-titanium alloy substrate; in terms of atomic percentage, the silver content in the highly antibacterial doped carbon-based film layer is 6% to 20%, the titanium dioxide content is 3% to 10%, and the carbon content is 70% to 85%.

4. The preparation method according to claim 1, characterized in that The target material is used to perform a coating process on the plasma-cleaned nickel-titanium alloy substrate to form a highly antibacterial doped carbon-based film layer on the surface of the nickel-titanium alloy substrate, comprising: The nickel-titanium alloy substrate after plasma cleaning is plated using a titanium dioxide target, a silver-carbon composite target, a carbon target, and nitrogen to form a highly antibacterial doped carbon-based film layer on the surface of the nickel-titanium alloy substrate; in terms of atomic percentage, the silver content in the highly antibacterial doped carbon-based film layer is 5% to 20%, the titanium dioxide content is 6% to 15%, the carbon content is 30% to 60%, and the nitrogen content is 5% to 35%.

5. The preparation method according to any one of claims 1 to 4, characterized in that The mass ratio of silver to carbon in the silver-carbon composite target is in the range of 1:(2-3); or, The silver-carbon composite target is a disc-shaped target composed of a fan-shaped single silver unit and a fan-shaped single carbon unit with the same radius, wherein the central angle of the fan-shaped silver unit is θ1, the central angle of the fan-shaped carbon unit is θ2, θ1+θ2=360°; wherein the ratio of θ1 to θ2 is in the range of 1:(10~12).

6. The preparation method according to any one of claims 1 to 4, characterized in that The sputtering power of the titanium dioxide target is in the range of 110W to 150W, and the sputtering power of the silver-carbon composite target is in the range of 20W to 40W; or The duration of the coating treatment on the nickel-titanium alloy substrate after plasma cleaning is 30 minutes to 120 minutes.

7. The preparation method according to any one of claims 1 to 4, characterized in that The target material is used to perform a coating process on the plasma-cleaned nickel-titanium alloy substrate to form a highly antibacterial doped carbon-based film layer on the surface of the nickel-titanium alloy substrate, comprising: The nickel-titanium alloy substrate after plasma cleaning is subjected to a coating treatment using a first target material to form a transition layer; the first target material comprises a titanium target; A second target material is used for coating treatment to form a surface doping layer on the side of the transition layer away from the nickel-titanium alloy substrate, thereby forming the highly antibacterial doped carbon-based film layer; the second target material includes a titanium dioxide target and a silver-carbon composite target; in terms of atomic percentage, the silver content in the highly antibacterial doped carbon-based film layer is 5% to 20%, the titanium dioxide content is 6% to 15%, the carbon content is 30% to 60%, and the nitrogen content is 5% to 35%.

8. The preparation method according to claim 7, characterized in that The method of using the first target material to perform a coating process on the plasma-cleaned nickel-titanium alloy substrate to form a transition layer includes: using a titanium target to perform a sputtering process on the plasma-cleaned nickel-titanium alloy substrate to form a transition layer; or, The transition layer includes a Ti transition sublayer and a TiC transition sublayer. The process of using a first target material to perform a coating process on the plasma-cleaned nickel-titanium alloy substrate to form the transition layer includes: using a titanium target to perform a sputtering process on the plasma-cleaned nickel-titanium alloy substrate to form a Ti transition sublayer; using a titanium target and methane to form a TiC transition sublayer on a side of the Ti transition sublayer away from the nickel-titanium alloy substrate; The coating process using the second target material to form a surface doped layer on the side of the transition layer away from the nickel-titanium alloy substrate includes: coating the TiC transition sublayer using the second target material to form a surface doped layer on the side away from the nickel-titanium alloy substrate; or, The transition layer includes a Ti transition sublayer, a TiC transition sublayer and a TiCN transition sublayer. The process of using a first target material to perform a coating process on the plasma-cleaned nickel-titanium alloy substrate to form the transition layer includes: using a titanium target to perform a sputtering process on the plasma-cleaned nickel-titanium alloy substrate to form a Ti transition sublayer; using a titanium target and methane to form a TiC transition sublayer on a side of the Ti transition sublayer away from the nickel-titanium alloy substrate; and using a titanium target, methane and nitrogen to form a TiCN transition sublayer on a side of the TiC transition sublayer away from the nickel-titanium alloy substrate. The method of using the second target material for coating to form a surface doping layer on the side of the transition layer away from the nickel-titanium alloy substrate includes: using the second target material for coating to form a surface doping layer on the side of the TiCN transition sublayer away from the nickel-titanium alloy substrate.

9. A highly antibacterial doped carbon-based film layer of medical nickel-titanium alloy, characterized in that: The highly antibacterial doped carbon-based film layer is prepared according to the method for preparing a highly antibacterial doped carbon-based film layer of medical nickel-titanium alloy according to any one of claims 1-8.

10. A coated part, characterized in that: include: Nitinol substrate; as well as A highly antibacterial doped carbon-based film layer is formed on the surface of the nickel-titanium alloy substrate; The highly antibacterial doped carbon-based film layer is prepared according to the method for preparing a highly antibacterial doped carbon-based film layer of medical nickel-titanium alloy according to any one of claims 1-8.

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