Metal nitride / metal alternating nanocomposite coating and method for producing same

Abstract

The present application relates to a kind of metal nitride / metal alternative nanocomposite coating and its preparation method, composite coating includes: metal transition layer is arranged on substrate, and intermediate metal layer and soft metal doped metal nitride layer are sequentially and alternately stacked on metal transition layer;Wherein soft metal doped metal nitride layer as the surface layer of composite coating;Metal transition layer is used metal in Cr, Ti or Zr one kind;Metal element used in intermediate metal layer is in Au, Ag or Cu one kind;Metal element used in soft metal doped metal nitride layer and metal used in metal transition layer are identical.Preparation method includes: using multi-arc ion plating method is sequentially deposited each layer on substrate.Compared with prior art, the multilayer structure coating prepared by the present application has excellent anti-adhesion performance, can effectively reduce the generation of smoke, and has excellent biocompatibility.

Description

Technical Field

[0001] This invention belongs to the field of medical device and thin film material preparation technology, and relates to a method for preparing a metal nitride / metal alternating nanocomposite coating. In particular, it relates to a multi-layered nanocomposite coating with anti-adhesion metal nitride (M1M2N) and metal (M2) alternating nanocomposite structure on the surface of a high-frequency electrosurgical stainless steel electrode. Specifically, it relates to a method for preparing a multi-layered nanocomposite coating with metal nitride (M1M2N) and metal (M2) alternating nanocomposite structure on the surface of stainless steel material using a multi-arc ion plating method. Background Technology

[0002] With the development of modern medicine, medical devices, as an important component of modern medicine, directly affect the therapeutic effect of surgery. Minimally invasive surgery has been a hot topic in surgical development since the beginning of the new century. Doctors use minimally invasive instruments to complete surgeries, and these instruments directly or indirectly affect the therapeutic effect and patient recovery. High-frequency electrosurgical units (HFOS) are a commonly used minimally invasive medical device. Since their development by Drs. Bovie and Cushing in 1926, they have been widely used in surgery and interventional endoscopy, gradually becoming one of the important modern medical devices in the operating room. They use radiofrequency (300kHz-5MHz) alternating current to cut and coagulate tissue; they are electrosurgical energy devices and belong to the category of surgical instruments. HFOS have both dissection and cutting functions as well as hemostasis functions, and have gradually replaced traditional scalpels in surgery.

[0003] However, the following problems currently hinder the development of high-frequency electrosurgical units (HFOS). First, the large amount of surgical smoke or vapor produced and the subsequent poor visibility make it a difficult tool to use in laparoscopic surgery. Second, due to the high-temperature thermal field and high-frequency electric field on the electrode surface during HFOS operation, human tissue adheres to the electrode surface and is difficult to remove. Furthermore, the adhered tissue hinders energy transfer, exacerbates adhesion, and tears tissue. The high temperature of the electrode can also cause thermal damage or even necrosis to surrounding tissues or organs through heat diffusion, leading to symptoms such as inflammatory reactions, fibrinolysis, and coagulation system disorders. Therefore, during surgery, doctors often frequently clean the adhered material on the HFOS surface with medical gauze, significantly prolonging the operation time and causing instrument corrosion. The problem of tissue adhesion on the stainless steel electrode surface greatly limits the development of HFOS, and it is urgent to solve this problem.

[0004] Chinese patent CN108950548A discloses a chromium-chromium nitride composite coating, a nanocomposite cutting tool with the chromium-chromium nitride composite coating deposited thereon, and its preparation method. The chromium-chromium nitride composite coating is a multi-layered coating structure composed of alternating chromium and chromium nitride layers. This structure can be applied to metal parts, cutting tools, molds, and other products, not only improving the surface hardness and corrosion resistance but also giving the surface better impact resistance and wear resistance. However, this cutting tool still suffers from the problem of tissue adhesion during use. Summary of the Invention

[0005] The purpose of this invention is to provide a method for preparing a metal nitride / alternating metal nanocomposite coating to solve the problem of adhesion of high-frequency electrosurgical electrode tissue.

[0006] The objective of this invention can be achieved through the following technical solutions:

[0007] A metal nitride / alternating metal nanocomposite coating includes a metal transition layer disposed on a substrate, and an intermediate metal layer and a soft metal-doped metal nitride layer alternately stacked on the metal transition layer.

[0008] The soft metal-doped metal nitride layer is used as the surface layer of the composite coating.

[0009] The metal used in the metal transition layer is one of Cr, Ti or Zr;

[0010] The metal element used in the intermediate metal layer is one of Au, Ag or Cu;

[0011] In the aforementioned soft metal-doped metal nitride layer, the metal element in the metal nitride is the same as the metal used in the metal transition layer, and the soft metal element is the same as the metal used in the intermediate metal layer. Further, the metal used in the metal transition layer is Cr; and the metal element used in the intermediate metal layer is Cu.

[0012] Furthermore, the thickness of the metal transition layer is 80–120 nm; the thickness of the intermediate metal layer is 100–500 nm; and the thickness of the soft metal-doped metal nitride layer is 100–1000 nm.

[0013] Furthermore, the composite coating comprises 1 to 4 sets of alternately stacked intermediate metal layers and soft metal-doped metal nitride layers.

[0014] A method for preparing a metal nitride / alternating metal nanocomposite coating includes: depositing a metal transition layer on a substrate using a multi-arc ion plating method, and then sequentially depositing an intermediate metal layer and a soft metal-doped metal nitride layer on the metal transition layer to obtain a metal nitride / alternating metal nanocomposite coating.

[0015] Furthermore, the deposition process of the metal transition layer is carried out in an argon atmosphere with an argon pressure of 0.5 to 2.5 Pa, a pulse bias voltage of -100 to -500 V, a target current of 70 to 90 A, and a deposition time of 5 to 15 min.

[0016] Furthermore, when the metal used in the metal transition layer is Cr, the argon pressure is 0.6 Pa, the pulse bias voltage is -100 to -500 V, the target current is 80 A, and the deposition time is 10 min.

[0017] When the metal used in the metal transition layer is Ti, the argon pressure is 0.6 Pa, the pulse bias voltage is -100 to -500 V, the target current is 85 A, and the deposition time is 10 min.

[0018] When the metal used in the metal transition layer is Zr, the argon pressure is 0.6 Pa, the pulse bias voltage is -100 to -500 V, the target current is 85 A, and the deposition time is 10 min.

[0019] Furthermore, the deposition process of the intermediate metal layer is carried out in an argon atmosphere with an argon pressure of 0.5 to 2.5 Pa, a pulse bias voltage of -80 to -120 V, a target current of 40 to 70 A, and a deposition time of 10 to 60 min.

[0020] Furthermore, when the metal used in the intermediate metal layer is Ag, the argon pressure is 0.6 Pa, the pulse bias voltage is -100 V, the duty cycle is 80%, the target current is 55 A, and the deposition time is 30 min.

[0021] When the metal used in the intermediate metal layer is Cu, the argon pressure is 0.6 Pa, the pulse bias voltage is -100 V, the duty cycle is 80%, the target current is 65 A, and the deposition time is 15 to 30 min.

[0022] When the metal used in the intermediate metal layer is Au, the argon pressure is 0.6 Pa, the pulse bias voltage is -100 V, the duty cycle is 80%, the target current is 45 A, and the deposition time is 15 to 30 min.

[0023] Furthermore, the deposition process of the soft metal-doped metal nitride layer is carried out in a nitrogen atmosphere with a nitrogen pressure of 1-3 Pa, a pulse bias voltage of -80 to -120 V, two metal target currents of 70-90 A, and a co-deposition time of 25-60 min.

[0024] Furthermore, during the deposition of the soft metal-doped metal nitride layer, the nitrogen pressure is 1–3 Pa and the deposition time is 15–30 min.

[0025] When one of the metal elements used in the soft metal doped metal nitride layer is Cr, the pulse bias voltage is -100V and the Cr target current is 80A.

[0026] When one of the metal elements used in the soft metal doped metal nitride layer is Zr or Ti, the pulse bias voltage is -100V and the Zr target or Ti target current is 85A.

[0027] When one of the metal elements used in the soft metal doped metal nitride layer is Ag, the pulse bias voltage is -100V and the Ag target current is 55A.

[0028] When one of the metal elements used in the soft metal doped metal nitride layer is Cu, the pulse bias voltage is -100V and the Cu target current is 65A.

[0029] When one of the metal elements used in the soft metal doped metal nitride layer is Au, the pulse bias voltage is -100V and the Au target current is 45A.

[0030] Medical high-frequency electrosurgical units are generally made of stainless steel and other metallic materials. In humid environments, their surfaces adsorb a large number of hydroxyl groups, resulting in high surface energy and hydrophilicity. During surgery, the high-frequency electrosurgical unit inevitably comes into contact with the patient's blood and tissues. Due to adhesion, blood mixed with soft tissue forms a blood film on the surface of the electrosurgical unit, which gradually dehydrates under high temperatures, forming a scab or even carbonizing, resulting in stronger adhesion. Applying modified coatings is one of the effective methods to solve the problem of tissue adhesion with high-frequency electrosurgical units, which places higher demands on the coating materials in terms of hydrophobicity, thermal conductivity, electrical conductivity, and mechanical strength. As is well known, coatings of common soft metals (such as Cu, Ag, and Au) doped with metal nitrides (such as TiN, CrN, and ZrN) are stable, possessing high mechanical strength and hydrophobicity, but limited thermal and electrical conductivity. While soft metal coatings alone possess excellent thermal and electrical conductivity, they are easily oxidized and lose their thermal and electrical conductivity under the high-temperature arc of a high-frequency electrosurgical unit. By combining two coatings, a metal nitride coating serves as a surface protective layer, providing hydrophobic properties and mechanical strength, while a soft metal layer acts as an intermediate layer, providing thermal and electrical conductivity. This results in a high-strength coating with both high hydrophobicity and high thermal and electrical conductivity, which can solve the problem of tissue adhesion in high-frequency electrosurgical units and facilitate the widespread application of high-frequency electrosurgical units.

[0031] Based on this, the present invention provides a multilayer nanocomposite coating of alternating metal nitride (M1M2N) and metal (M2), which is prepared by multi-arc ion plating technology. The targets used are pure metal M1 targets (99.9%) and pure metal M2 targets (99.9%), and stainless steel electrodes are selected as the substrate material. The M2 layer is deposited by multi-arc ion deposition, and the M1M2N layer is deposited by reaction deposition. This structure coating not only has excellent anti-adhesion effect, but also improves the mechanical properties, electrical properties, and corrosion resistance of stainless steel electrodes. The preparation method of the M1M2N / M2 multilayer structure coating is simple, efficient, and versatile, and has good prospects for industrial application.

[0032] Compared with the prior art, the present invention has the following characteristics:

[0033] 1) This invention enables the preparation of a multilayer coating of metal nitride (M1M2N) and metal (M2) on the surface of a stainless steel electrode of a high-frequency electrosurgical unit. The preparation method is simple and easy to mass-produce.

[0034] 2) The multilayer coating prepared by this invention has excellent anti-blocking properties, can effectively reduce smoke generation, and has excellent biocompatibility;

[0035] 3) The multi-layer structure coating prepared by this invention is smooth and dense. Moreover, the multi-arc ion plating technology has a higher ionization rate and a higher adhesion between the coating and the substrate compared with other vacuum coating technologies.

[0036] 4) The metal nitride (M1M2N) and metal (M2) multilayer structure coatings prepared by this invention not only have excellent mechanical properties, but also have excellent corrosion resistance and electrical properties.

[0037] 5) The method of this invention has low equipment cost, simple process flow, and the prepared coating has a wide range of applications. It can be applied on a large scale to the surface modification of electrosurgical instruments. Attached Figure Description

[0038] Figure 1 A schematic diagram showing the structural dimensions and surface coating structure of a stainless steel electrode.

[0039] Figure 2 The image shown is a cross-sectional scanning electron microscope (SEM) image of Example 3.

[0040] Figure 3 This is the element scan distribution (EDS) diagram of the cross-section in Example 3;

[0041] Figure 4 The results of microhardness tests for Examples 1 and 3 are shown.

[0042] Figure 5 Image showing the water contact angle of Example 3;

[0043] Figure 6 The resistivity test results are for Example 3;

[0044] Figure 7 The polarization curve test results are for Example 3;

[0045] Figure 8 Comparison of the electrode of Example 3 with other electrodes after electrocution: (a) Comparative Example 1; (b) Comparative Example 2; (c) Example 3;

[0046] Figure 9 Scanning electron microscope (SEM) images of the cross-section of the electrode after cutting (left): (a) Uncoated electrode of Comparative Example 1, (c) Electrode with CrN coating of Example 1; Histogram of adhesion tissue thickness (right): (b) Uncoated electrode of Comparative Example 1, (d) Electrode with CrN coating of Example 1.

[0047] Figure 10 (a) SEM image and (b) histogram of the thickness of the adhered tissue after electrode cutting in Example 3;

[0048] Explanation of markings in the diagram:

[0049] S - Substrate; M1 - Metal transition layer; M2 - Intermediate metal layer; M1M2N - Soft metal doped metal nitride layer. Detailed Implementation

[0050] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments.

[0051] like Figure 1 The illustrated metal nitride / alternating metal nanocomposite coating includes a metal transition layer M1 disposed on a substrate S, and an intermediate metal layer M2 and a soft metal-doped metal nitride layer M1M2N alternately stacked on the metal transition layer M1; wherein the soft metal-doped metal nitride layer M1M2N serves as the surface layer of the composite coating; the metal used in the metal transition layer M1 is one of Cr, Ti, or Zr; the metal element used in the intermediate metal layer M2 is one of Au, Ag, or Cu; in the soft metal-doped metal nitride layer M1M2N, the metal element in the metal nitride is the same as the metal used in the metal transition layer M1, and the soft metal element is the same as the metal used in the intermediate metal layer M2.

[0052] A metal nitride / alternating metal nanocomposite coating, which can be represented as S / M1 / (M2 / M1M2N). nThe coating consists of an M1 metal layer as a transition layer to improve the adhesion between the coating and the substrate; a highly thermally and electrically conductive metal M2 as an intermediate layer to enhance both thermal and electrical conductivity; and an M1M2N coating formed by doping metal M2 with metal M1 nitride as a protective layer to provide hydrophobic properties and mechanical strength. (M2 / M1M2N) n The nanocomposite multilayer coating is a high-strength coating with high hydrophobicity and high thermal and electrical conductivity, which can effectively solve the problem of tissue adhesion in high-frequency electrosurgical treatment.

[0053] In some preferred embodiments, the thickness of the metal transition layer M1 is 80–120 nm; the thickness of the intermediate metal layer M2 is 100–500 nm; and the thickness of the soft metal-doped metal nitride layer M1M2N is 100–1000 nm.

[0054] In some preferred embodiments, the composite coating includes 1 to 4 sets of alternately stacked intermediate metal layers M2 and soft metal-doped metal nitride layers M1M2N.

[0055] A method for preparing a metal nitride / alternating metal nanocomposite coating includes the following steps:

[0056] S1: Cleaning the substrate: First, polish the substrate S, then use acetone and anhydrous ethanol to ultrasonically clean it for at least 30 minutes (40 kHz) in sequence, and finally dry it with a nitrogen gun and clamp it into the vacuum chamber.

[0057] The substrate S is made of stainless steel, including austenitic stainless steel (such as 304, 321, 316, 310, etc.), ferritic stainless steel and martensitic stainless steel (such as 430, 420, 410, etc.), with a chromium content of at least 10.5% and a carbon content of no more than 1.2%.

[0058] Polishing process: Using sandpaper of grits 280, 600, 1000, 2000, and 5000 in order from smallest to largest, followed by fine polishing with diamond polishing paste;

[0059] The substrate temperature required for coating preparation is 350–550℃, and the substrate bias voltage is -100V to -300V.

[0060] S2: Vacuuming: With the cooling water operating normally, turn on the mechanical pump, Roots pump, and molecular pump until the vacuum level reaches 5×10⁻⁶. -3 When the pressure reaches Pa, the cavity heating resistor is activated. After the temperature reaches the set value, evacuation continues until the cavity vacuum level is at least 5 × 10⁻⁶. - 3 Pa, and maintain heating time for at least 3 hours;

[0061] S3: Glow Glow Cleaning Substrate: After evacuation and sufficient heating, argon gas is introduced into the vacuum chamber, and the pulse bias voltage and duty cycle are set. The pulse bias voltage power supply is then turned on for cleaning.

[0062] Glow photopolymerization is used to clean the substrate to remove residual gases, particles, and other contaminants from the substrate surface, thereby enhancing the adhesion of the coating.

[0063] S4: Preparation of metal transition layer M1: Adjust the argon flow rate, set the M1 metal target arc power supply current and turn on the power supply, and deposit the pulse bias voltage from -500V to -100V.

[0064] In some preferred embodiments, the deposition process of the metal transition layer M1 is carried out in an argon atmosphere with an argon pressure of 0.5–2.5 Pa, a pulse bias voltage of -100–-500 V, a target current of 70–90 A, and a deposition time of 5–15 min. More preferably, when the metal used in the metal transition layer M1 is Cr, the argon pressure is 0.6 Pa, the pulse bias voltage is -100–-500 V, the target current is 80 A, and the deposition time is 10 min; when the metal used in the metal transition layer M1 is Ti, the argon pressure is 0.6 Pa, the pulse bias voltage is -100–-500 V, the target current is 85 A, and the deposition time is 10 min; when the metal used in the metal transition layer M1 is Zr, the argon pressure is 0.6 Pa, the pulse bias voltage is -100–-500 V, the target current is 85 A, and the deposition time is 10 min.

[0065] S5: Preparation of intermediate metal layer M2: Adjust argon flow rate, adjust pulse bias and duty cycle, set M2 target power supply current and turn on power, deposit for 5-60 min;

[0066] In some preferred embodiments, the deposition process of the intermediate metal layer M2 is carried out in an argon atmosphere with an argon pressure of 0.5–2.5 Pa, a pulse bias voltage of -80–-120 V, a target current of 40–70 A, and a deposition time of 10–35 min. More preferably, when the metal used in the intermediate metal layer M2 is Ag, the argon pressure is 0.6 Pa, the pulse bias voltage is -100 V, the duty cycle is 80%, the target current is 55 A, and the deposition time is 30 min; when the metal used in the intermediate metal layer M2 is Cu, the argon pressure is 0.6 Pa, the pulse bias voltage is -100 V, the duty cycle is 80%, the target current is 65 A, and the deposition time is 15–30 min; when the metal used in the intermediate metal layer M2 is Au, the argon pressure is 0.6 Pa, the pulse bias voltage is -100 V, the duty cycle is 80%, the target current is 45 A, and the deposition time is 15–30 min.

[0067] S6: Preparation of soft metal-doped metal nitride layers M1M2N: Adjust the flow rates of argon (Ar) and nitrogen (N2) to achieve the set working pressure. Set the currents for targets M1 and M2 and turn on the power supply, allowing deposition to proceed for 5–60 minutes.

[0068] In some preferred embodiments, the deposition process of the soft metal doped metal nitride layer M1M2N is carried out in a nitrogen atmosphere with a nitrogen pressure of 1 to 3 Pa, a pulse bias voltage of -80 to -120 V, two metal target currents of 50 to 90 A, and a co-deposition time of 25 to 60 min. More preferably, during the deposition of the soft metal-doped metal nitride layer, the nitrogen pressure is 1–3 Pa, and the deposition time is 15–30 min; when one of the metal elements used in the soft metal-doped metal nitride layer is Cr, the pulse bias voltage is -100 V, and the Cr target current is 80 A; when one of the metal elements used in the soft metal-doped metal nitride layer is Zr or Ti, the pulse bias voltage is -100 V, and the Zr or Ti target current is 85 A; when one of the metal elements used in the soft metal-doped metal nitride layer is Ag, the pulse bias voltage is -100 V, and the Ag target current is 55 A; when one of the metal elements used in the soft metal-doped metal nitride layer is Cu, the pulse bias voltage is -100 V, and the Cu target current is 65 A; when one of the metal elements used in the soft metal-doped metal nitride layer is Au, the pulse bias voltage is -100 V, and the Au target current is 45 A.

[0069] S7: Repeat steps S5 and S6;

[0070] S8: Deposition complete: First, turn off the arc target power supply and pulse bias power supply, then stop the gas supply, and then turn off the heating. After the temperature inside the chamber drops below 100℃, turn off the pumping system sequentially. After the temperature inside the chamber drops to room temperature, open the vent, and finally open the vacuum chamber and remove the experimental sample.

[0071] The following embodiments are implemented based on the above-described technical solution of the present invention, and provide detailed implementation methods and specific operation processes. However, the scope of protection of the present invention is not limited to the following embodiments.

[0072] In the following examples, electrochemical tests were performed on an electrochemical testing workstation (CHI660E) using a three-electrode testing system. The three electrodes included a saturated calomel electrode, a platinum electrode, and a working electrode for preparing the experimental sample. During the test, the exposed area was 20 mm × 10 mm, and the working electrode area was 2 cm². 2 All other test surfaces were insulated and sealed with epoxy resin.

[0073] Electrochemical polarization curves—Tafel curves—are used to characterize the corrosion resistance of materials, thereby analyzing the corrosion mechanism of coatings. The electrolyte used in this work was a 3.5 wt.% sodium chloride (NaCl) solution, and the test temperature was room temperature (20℃). The main test procedure was as follows: the working electrode sample was immersed for at least 30 minutes, and after the open circuit potential-time curve (OCPT) stabilized, the scan rate was set to 10 mV / s to test the corrosion resistance.

[0074] In vitro simulated electrosurgical cutting experiments were conducted using a WillyForce FX-8C high-frequency electrosurgical unit from the USA. The cutting electrode used was a pre-prepared CrN-coated electrode. Additionally, as a control, an untreated electrode from Zhejiang Shuyou Instrument Equipment Co., Ltd. and a commercially available PTFE-coated electrode were used for electrosurgical cutting experiments. Test equipment included: one electrosurgical pen; one electrosurgical unit; one disposable electrode plate; one piece of lean pork; and test electrodes. Test method: Lean pork was simulated to cut 3-4 cm sections at 20W power, and after five cuts, the tissue adhesion of the electrodes was observed.

[0075] Comparative Example 1:

[0076] Size as Figure 1 The electrode is made of 304 stainless steel without coating. The total length of the electrode is c, which is 70 mm. The diameter of the handle is d, which is 2.35 mm. The length of the cutting head is a, which is 17 mm. The width is b, which is 2.25 mm. The thickness is e, which is 0.5 mm. The total length of the cutting head and connecting parts is f, which is 24 mm.

[0077] Comparative Example 2:

[0078] Size as Figure 1 Commercial PTFE-coated electrodes.

[0079] Example 1:

[0080] The preparation of a single-layer chromium nitride (CrN) coated electrode includes the following steps:

[0081] S1: Select size as shown Figure 1 The 304 stainless steel electrodes, after grinding, polishing, cleaning, and drying, were immediately placed into the sample stage of the machine cavity. The vacuum chamber was closed, and the vacuum system was used to evacuate the air to a pressure of 5 × 10⁻⁶. -3 Pa, then turn on the heating resistance wire and heat the sample substrate for 3 hours until the temperature reaches 350℃;

[0082] S2: Argon gas is introduced into the vacuum chamber and maintained at a pressure of 0.7 Pa. Glow emission cleaning is performed for 10 minutes.

[0083] S3: Adjust the argon flow rate to make the vacuum chamber pressure 0.6 Pa, turn on the Cr target power supply and set the current to 80 A. Set the pulse negative bias voltage to -500 V (2 min), -400 V (2 min), -300 V (2 min), -200 V (2 min), and -100 V (2 min), and deposit the metallic Cr transition layer for 10 min;

[0084] S4: Turn on the N2 flow meter and adjust the nitrogen flow rate to control the working gas pressure at 2Pa. Use a multi-arc power supply to ignite the cathode pure Cr target, and set the power supply current to 80A, the pulse bias voltage to -100V, the duty cycle to 80%, and deposit for 120min;

[0085] S5: Turn off the power supply and pulse bias power supply, then turn off the heating device. Wait for the temperature to drop to 100℃, then turn off the molecular pump, Roots pump, and mechanical pump in sequence. After standing for more than 6 hours, open the vacuum chamber and remove the sample.

[0086] Example 2:

[0087] The preparation of a (CrAgN / Ag)2 nanocomposite multilayer coated electrode includes the following steps:

[0088] S1: Select size as shown Figure 1 The 304 stainless steel electrodes, after grinding, polishing, cleaning, and drying, were immediately placed into the sample stage of the machine cavity. The vacuum chamber was closed, and the vacuum system was used to evacuate the air to a pressure of 5 × 10⁻⁶. -3 Pa, then turn on the heating resistance wire and heat the sample substrate for 3 hours until the temperature reaches 350℃;

[0089] S2: Argon gas is introduced into the vacuum chamber and maintained at a pressure of 0.7 Pa. Glow emission cleaning is performed for 10 minutes.

[0090] S3: Adjust the argon flow rate to make the vacuum chamber pressure 0.6Pa, and set the Cr target power supply current to 80A. Set the pulse negative bias voltage according to -500V (2min), -400V (2min), -300V (2min), -200V (2min), and -100V (2min). After deposition for 10min, turn off the Cr target power supply.

[0091] S4: In a flowing argon atmosphere of 0.6 Pa, turn on the Ag target power supply and set the current to 55 A, the pulse bias voltage to -100 V, the duty cycle to 80%, and deposit for 30 min;

[0092] S5: Turn on the nitrogen flow meter and adjust the nitrogen flow rate to control the working gas pressure to 2Pa. Turn on the Cr target power supply and set the current to 80A, pulse bias voltage to -100V, and duty cycle to 80%. At the same time, keep the Ag target power supply on and set the current to 55A, pulse bias voltage to -100V, and duty cycle to 80%. Co-deposit for 30 minutes.

[0093] S6: Repeat steps S4 and S5 in sequence;

[0094] S7: Turn off the power supply and pulse bias power supply, then turn off the heating device. Wait for the temperature to drop to 100℃, then turn off the molecular pump, Roots pump, and mechanical pump in sequence. After standing for more than 6 hours, open the vacuum chamber and remove the sample.

[0095] Example 3:

[0096] The preparation of a (CrCuN / Cu)2 nanocomposite multilayer coated electrode differs from Example 2 only in that:

[0097] In steps S4 and S5, the Cu target is replaced with the Ag target, and the current of the Cu target is set to 65A. The rest of the preparation process and parameters are the same as in Example 2.

[0098] The SEM image and EDS line scan image of the coating cross section are as follows: Figure 2 and Figure 3 As shown, it exhibits a distinct layered structure. Under the influence of the Cu metal layer, the microstructure of the CrCuN layer is a dense structure with almost no features.

[0099] Its microhardness is as Figure 4 As shown, the (CrCuN / Cu)2 nanocomposite multilayer coating retains the excellent mechanical properties of Example 1 and has an extremely high hardness of 2710.7 HV.

[0100] Its water contact angle is as follows Figure 5 As shown, the water contact angle is as high as 108.21°, exhibiting good hydrophobicity.

[0101] The resistivity was obtained by combining the four-probe method with the coating thickness, as shown in the figure. Figure 6 As shown, the resistivity within the operating temperature range is only 2.02–2.33 × 10⁻⁶. -7 It has an Ω·m value and exhibits excellent electrical conductivity.

[0102] The polarization curves were tested using an electrochemical workstation in a 3.5 wt% sodium chloride solution, and the results are as follows: Figure 7 As shown, the corrosion current density is as low as 3.84 × 10⁻⁶. -7 A·cm -2 It has excellent corrosion resistance.

[0103] like Figure 8 As shown, in the in vitro simulated electrocautery experiment, it exhibited superior anti-adhesion properties compared to Comparative Example 1 and Comparative Example 2. Figure 9 As shown, the layered structure of the adhesive structure-CrN coating-SUS304 (Example 1) is clearly visible, with an average thickness of 3.6 μm, which is 38.89% less than that of the uncoated electrode (Comparative Example 1). Figure 10 As shown, under the same operating conditions, the CrN / Cu (i.e., CrCuN) composite coated electrode (Example 3) reduces weight by 60% compared to the ordinary electrode (Comparative Example 1) and by 20% compared to the CrN coated electrode (Example 1). Figure 9 and Figure 10 The thickness of the adhered tissue was reduced by 60% with both electrode cross sections, demonstrating a significant effect in reducing tissue adhesion.

[0104] Example 4:

[0105] The preparation of a (CrCuN / Cu)4 nanocomposite multilayer coated electrode differs from Example 2 only in that:

[0106] In steps S4 and S5, the Cu target is replaced with a Cu target, and the current of the Cu target is set to 65A.

[0107] In steps S4 and S5, the deposition time is 15 minutes.

[0108] In step S6, steps S4 and S5 are repeated three times in sequence;

[0109] The remaining preparation process and parameters are the same as in Example 2.

[0110] Example 5:

[0111] The preparation of a (ZrCuN / Cu)4 nanocomposite multilayer coated electrode differs from Example 4 only in that:

[0112] In steps S3 and S5, a Zr target is used to replace the Cr target, and the current is set to 85A.

[0113] The remaining preparation process and parameters are the same as in Example 4.

[0114] Example 6:

[0115] The preparation of a (TiCuN / Cu)4 nanocomposite multilayer coated electrode differs from Example 4 only in that:

[0116] In steps S3 and S5, a Ti target is used to replace the Cr target, and the current is set to 85A.

[0117] The remaining preparation process and parameters are the same as in Example 4.

[0118] Example 7:

[0119] The preparation of a (TiAgN / Ag)4 nanometer composite multilayer coated electrode differs from Example 6 only in that:

[0120] In steps S4 and S5, the Cu target is replaced with an Ag target, and the current of the Ag target is set to 55A.

[0121] The remaining preparation process and parameters are the same as in Example 6.

[0122] Example 8:

[0123] The preparation of a (ZrAuN / Au)4 nanometer composite multilayer coated electrode differs from Example 6 only in that:

[0124] In steps S4 and S5, the Cu target is replaced with an Au target, and the current of the Au target is set to 45A.

[0125] The remaining preparation process and parameters are the same as in Example 5.

[0126] As can be seen from the relevant performance tests and data analysis of the above embodiments, the M1M2N / M2 multilayer structure coated electrode can greatly reduce tissue adhesion and smoke generation, and the coating surface is smooth and the structure is dense. The M1M2N / M2 multilayer structure coating has excellent comprehensive performance: it has good hydrophobicity and extremely low resistivity, while also possessing excellent mechanical properties and corrosion resistance. The preparation process and equipment are mature, which is conducive to large-scale production and promotion.

[0127] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. A metal nitride / alternating metal nanocomposite coating, characterized in that, It includes a metal transition layer (M1) disposed on a substrate (S), and an intermediate metal layer (M2) and a soft metal doped metal nitride layer (M1M2N) alternately stacked on the metal transition layer (M1). The soft metal-doped metal nitride layer (M1M2N) is used as the surface layer of the composite coating; The metal used in the metal transition layer (M1) is one of Cr, Ti or Zr; The metal element used in the intermediate metal layer (M2) is one of Au, Ag or Cu; In the soft metal doped metal nitride layer (M1M2N), the metal element in the metal nitride is the same as the metal used in the metal transition layer (M1), and the soft metal element is the same as the metal used in the intermediate metal layer (M2).

2. The metal nitride / alternating metal nanocomposite coating according to claim 1, characterized in that, The metal used in the metal transition layer (M1) is Cr; the metal used in the intermediate metal layer (M2) is Cu.

3. The metal nitride / alternating metal nanocomposite coating according to claim 1, characterized in that, It includes 1 to 4 sets of alternately stacked intermediate metal layers (M2) and soft metal doped metal nitride layers (M1M2N).

4. A method for preparing a metal nitride / alternating metal nanocomposite coating, used to prepare the metal nitride / alternating metal nanocomposite coating as described in any one of claims 1-3, characterized in that, The method includes: depositing a metal transition layer (M1) on a substrate (S) using a multi-arc ion plating method, and then sequentially depositing an intermediate metal layer (M2) and a soft metal-doped metal nitride layer (M1M2N) on the metal transition layer (M1) to obtain a metal nitride / metal alternating nanocomposite coating.

5. The method for preparing a metal nitride / alternating metal nanocomposite coating according to claim 4, characterized in that, The deposition process of the metal transition layer (M1) is carried out in an argon atmosphere with an argon pressure of 0.5~2.5 Pa, a pulse bias voltage of -100~-500 V, a target current of 70~90 A, and a deposition time of 5~15 min.

6. The method for preparing a metal nitride / alternating metal nanocomposite coating according to claim 5, characterized in that, When the metal used in the metal transition layer (M1) is Cr, the argon pressure is 0.6 Pa, the pulse bias voltage is -100 ~ -500 V, the target current is 80 A, and the deposition time is 10 min; When the metal used in the metal transition layer (M1) is Ti, the argon pressure is 0.6 Pa, the pulse bias voltage is -100 ~ -500 V, the target current is 85 A, and the deposition time is 10 min; When the metal used in the metal transition layer (M1) is Zr, the argon pressure is 0.6 Pa, the pulse bias voltage is -100 ~ -500 V, the target current is 85 A, and the deposition time is 10 min.

7. The method for preparing a metal nitride / alternating metal nanocomposite coating according to claim 4, characterized in that, The deposition process of the intermediate metal layer (M2) is carried out in an argon atmosphere with an argon pressure of 0.5~2.5 Pa, a pulse bias voltage of -80~-120 V, a target current of 40~70 A, and a deposition time of 10~60 min.

8. The method for preparing a metal nitride / alternating metal nanocomposite coating according to claim 7, characterized in that, When the metal used in the intermediate metal layer (M2) is Ag, the argon pressure is 0.6 Pa, the pulse bias voltage is -100V, the duty cycle is 80%, the target current is 55 A, and the deposition time is 30 min. When the metal used in the intermediate metal layer (M2) is Cu, the argon pressure is 0.6 Pa, the pulse bias voltage is -100 V, the duty cycle is 80%, the target current is 65 A, and the deposition time is 15~30 min. When the metal used in the intermediate metal layer (M2) is Au, the argon pressure is 0.6 Pa, the pulse bias voltage is -100 V, the duty cycle is 80%, the target current is 45 A, and the deposition time is 15~30 min.

9. The method for preparing a metal nitride / alternating metal nanocomposite coating according to claim 4, characterized in that, The deposition process of the soft metal doped metal nitride layer (M1M2N) is carried out in a nitrogen atmosphere with a nitrogen pressure of 1~3 Pa, a pulse bias voltage of -80~-120 V, two metal target currents of 50~90 A, and a co-deposition time of 25~60 min.

10. The method for preparing a metal nitride / alternating metal nanocomposite coating according to claim 9, characterized in that, During the deposition of the soft metal-doped metal nitride layer (M1M2N), the nitrogen pressure is 1~3 Pa and the deposition time is 15~30 min; When one of the metal elements used in the soft metal doped metal nitride layer (M1M2N) is Cr, the pulse bias voltage is -100 V and the Cr target current is 80 A. When one of the metal elements used in the soft metal doped metal nitride layer (M1M2N) is Zr or Ti, the pulse bias voltage is -100 V and the Zr target or Ti target current is 85 A. When one of the metal elements used in the soft metal doped metal nitride layer (M1M2N) is Ag, the pulse bias voltage is -100 V and the Ag target current is 55 A. When one of the metal elements used in the soft metal doped metal nitride layer (M1M2N) is Cu, the pulse bias voltage is -100 V and the Cu target current is 65 A. When one of the metal elements used in the soft metal-doped metal nitride layer (M1M2N) is Au, the pulse bias voltage is -100 V and the Au target current is 45 A.

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