Protective coating and method for its production and use, high-frequency electrotome

Abstract

The present application relates to the technical field of protective coating, and particularly relates to a protective coating, a preparation method and application thereof, and a high-frequency electrotome. The present application provides a protective coating, which comprises a Ti transition layer and a functional layer arranged in sequence on the surface of a substrate; the material of the functional layer is TiZrHfTaCuN, and the TiZrHfTaCuN is a multi-element solid solution structure. The protective coating has the characteristics of high hardness, high conductivity and low surface energy (hydrophobic property), thereby ensuring the stable anti-adhesion performance of the high-frequency electrode in a complex surgical environment.

Description

Technical Field

[0001] This invention relates to the field of protective coating technology, and in particular to a protective coating, its preparation method and application, and a high-frequency electrosurgical unit. Background Technology

[0002] High-frequency electrosurgical units (HFEMs) are key instruments widely used in modern surgery. Their working principle involves the electrode tip contacting the tissue, inducing Joule heating by using radiofrequency alternating current to cause oscillation of charged particles within the tissue. This leads to tissue dehydration and protein coagulation, achieving a synergistic effect of cutting and hemostasis. Compared to traditional surgical instruments, HFEMs offer advantages such as precise incisions, less bleeding, less damage to surrounding tissues, and lower surgical risk, and are widely used in most clinical surgical scenarios, including laparoscopic surgery and plastic surgery. However, in actual use, the local temperature of the electrode can rapidly rise to approximately 100°C or even higher, causing dehydration, crusting, and even carbonization of blood and soft tissue. These deformed or carbonized products easily adhere to and deposit on the electrode surface, forming a stable adhesion layer. On the one hand, this adhesion layer hinders uniform current conduction, causing local power concentration and further temperature increases, resulting in thermal adhesion, reducing cutting efficiency and affecting hemostasis. On the other hand, continuous thermo-electric coupling can also cause the decomposition of the attached tissue and generate harmful fumes, threatening the safety of medical personnel and potentially leading to tissue burns and wound enlargement, increasing the risk of secondary injury to the patient. Furthermore, surface adhesion can affect the stable discharge of electrodes and accelerate the degradation of device performance, significantly shortening its service life. Therefore, inhibiting the adhesion of blood and tissue to the electrode surface and improving its anti-thermal adhesion properties has become a key scientific problem and an important development direction that urgently needs to be solved in the field of medical high-frequency electrosurgical units.

[0003] Currently, various strategies have been proposed to improve the anti-adhesion performance of high-frequency electrodes to address the issue of tissue adhesion on the electrode surface. These strategies mainly include introducing auxiliary devices, constructing surface coatings, and implementing surface patterning designs. Adding auxiliary devices typically reduces the temperature of the electrode working end by introducing a cooling circulation system or saline perfusion, thereby slowing down tissue thermal adhesion. However, these methods often require additional integration of the electrode structure, increasing instrument size, affecting the surgical field of view, and significantly increasing processing complexity and manufacturing costs, limiting their flexibility in clinical application. Surface patterning, on the other hand, constructs micro / nanostructures on the electrode surface to reduce the actual contact area between the tissue and the electrode and promotes heat dissipation to some extent, thus achieving an anti-adhesion effect. However, such structures are easily filled with tissue debris or carbonized products during actual service, leading to a decrease in the anti-adhesion effect. Furthermore, their processing is complex and their stability is limited, making it difficult to maintain performance advantages in the long term. In contrast, surface coating technology has attracted widespread attention due to its high controllability. For example, introducing a polytetrafluoroethylene (PTFE) coating on the electrode surface can effectively reduce surface energy, thereby reducing tissue adhesion. However, PTFE is an insulating material, which weakens the conductivity of the electrode and may decompose under high temperatures, releasing potentially harmful substances and posing a risk to patient safety. Furthermore, depositing hexamethyldisiloxane (HMDSO) coatings can form a low-adhesion interface with some hydrophobicity, significantly reducing soft tissue adhesion. However, these coatings lack stability under high temperatures and electrothermal coupling, easily experiencing performance degradation or even peeling, making long-term reliable service difficult. In summary, existing methods still have significant shortcomings in terms of structural complexity, service stability, and safety. Therefore, there is an urgent need to develop functional coatings that combine high hardness, high conductivity, and low surface energy (hydrophobic properties) to achieve stable anti-adhesion performance of high-frequency electrodes in complex surgical environments. Summary of the Invention

[0004] In view of this, the purpose of the present invention is to provide a protective coating, its preparation method and application, and a high-frequency electrosurgical unit. The protective coating has the characteristics of high hardness, high conductivity and low surface energy (hydrophobic properties), thereby ensuring the stable anti-adhesion performance of the high-frequency electrode in complex surgical environments.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a protective coating comprising a Ti transition layer and a functional layer sequentially stacked on the surface of a substrate; The functional layer is made of TiZrHfTaCuN, and TiZrHfTaCuN has a multi-component solid solution structure.

[0006] Preferably, the atomic percentages of Ti, Zr, Hf, and Ta in the TiZrHfTaCuN are independently 10.0~14.0 at.%; The atomic percentage of Cu in the TiZrHfTaCuN is 2.0~6.0 at.% The atomic percentage of N in the TiZrHfTaCuN is 45.0~55.0 at.%.

[0007] The present invention also provides a method for preparing the protective coating described in the above technical solution, comprising the following steps: The protective coating is obtained by sequentially depositing a Ti transition layer and a functional layer on the substrate surface using magnetron sputtering.

[0008] Preferably, before the deposition is performed, the substrate is further subjected to ultrasonic cleaning and ion cleaning in sequence.

[0009] Preferably, the ultrasonic cleaning includes ultrasonic cleaning in acetone, ethanol and water in sequence; The power of ultrasonic cleaning at each stage is 220~260 W and the time is 15~20 min.

[0010] Preferably, the working gas for ion cleaning is argon, the argon gas introduction rate is 50~100 sccm, and the working gas pressure is 1.0~2.5 Pa; the substrate is connected to an RF power supply, the voltage of which is 800~1000 V, the duty cycle is 40~60%, and the time is 30 min; the substrate temperature is 100~500 ℃, and the substrate rotation speed is 5~20 rpm.

[0011] Preferably, the deposition conditions of the Ti transition layer are as follows: the working gas is argon, the argon gas flow rate is 20~40 sccm, the working gas pressure is 0.3~1.0 Pa, the target material is a Ti target, the Ti target is connected to a DC power supply with a current of 8~12 A; the substrate is connected to an RF power supply with a voltage of 50~150 V, a duty cycle of 50~90%, and a time of 30 min; the substrate temperature is 100~500 ℃, and the substrate rotation speed is 5~20 rpm.

[0012] Preferably, the deposition conditions of the functional layer are as follows: the working gas is argon, the argon gas flow rate is 20~40 sccm, the reactant gas is nitrogen, the nitrogen gas flow rate is 50~100 sccm, the working gas pressure is 0.3~1.0 Pa, the target material is a TiZrHfTa target and a Cu target, the TiZrHfTa target and the Cu target are respectively connected to a DC power supply, the current of the TiZrHfTa target is 8~12 A, and the current of the Cu target is 0.5~3.0 A; the substrate is connected to an RF power supply, the voltage of the RF power supply is 50~150 V, the duty cycle is 50~90%, and the time is 60~120 min; the substrate temperature is 100~500 ℃, and the substrate rotation speed is 5~20 rpm.

[0013] The present invention also provides the application of the protective coating described in the above technical solution or the protective coating prepared by the preparation method described in the above technical solution in the field of high-frequency electrosurgical protection.

[0014] The present invention also provides a high-frequency electrosurgical unit, comprising a high-frequency electrosurgical unit substrate and a protective coating on the surface of the high-frequency electrosurgical unit substrate; The protective coating is the protective coating described in the above technical solution or the protective coating prepared by the preparation method described in the above technical solution.

[0015] The present invention provides a protective coating comprising a Ti transition layer and a functional layer sequentially stacked on the surface of a substrate; the functional layer is made of TiZrHfTaCuN, and the TiZrHfTaCuN is a multi-component solid solution structure.

[0016] Compared with the prior art, the protective coating of the present invention has the following beneficial effects: 1) The protective coating of the present invention has high hardness and high film-substrate adhesion, which can limit and improve the wear resistance and service stability of the substrate surface, and avoid wear or peeling during use; the Ti transition layer can effectively improve the bonding strength between the coating and the substrate; the high-entropy engineering design concept of the functional layer can enhance the solid solution effect, and the lattice distortion enhances the resistance to dislocation movement, thereby effectively suppressing dislocation slip and improving the material hardness. 2) The protective coating of this invention has high hydrophobicity, which promotes anti-adhesion performance: The protective coating of this invention has a high surface contact angle and exhibits significant hydrophobic properties, which can effectively reduce the interfacial free energy between tissue and electrode, thereby reducing the adhesion of blood and soft tissue. The introduction of Cu element has a synergistic regulatory effect on the surface chemical state and microstructure: After Cu enters the crystal lattice in solid solution form, its electronic structure tends to be saturated, allowing it to interact electronically with surrounding transition metal atoms, regulating the electron distribution of surface atoms, making the surface electron occupancy state more stable and tending towards a full shell characteristic. This optimized electronic structure weakens the surface's adsorption capacity for polar water molecules, reduces surface energy, thereby weakening the wetting behavior of tissue on the surface and the interfacial bonding strength, ultimately achieving excellent anti-adhesion performance. 3) Antibacterial properties to prevent surgical infection: The protective coating of the present invention has good antibacterial properties, which helps to reduce the risk of intraoperative infection: The introduced Cu element can kill bacteria by destroying the bacterial cell membrane structure, effectively inhibiting surgical infection caused by bacterial adhesion and improving the biosafety of the coating. Attached Figure Description

[0017] Figure 1 Bar charts showing the antibacterial rates of the protective coatings described in the control group, Examples 1 and 3, and Comparative Examples 1 and 2; Figure 2 The results are the cytotoxicity test results of the protective coatings described in Examples 1-3; Figure 3 The results are the hardness test results of the protective coatings described in Examples 1-2 and Comparative Examples 1-2. Detailed Implementation

[0018] This invention provides a protective coating comprising a Ti transition layer and a functional layer sequentially stacked on the surface of a substrate; The functional layer is made of TiZrHfTaCuN, and TiZrHfTaCuN has a multi-component solid solution structure.

[0019] In this invention, the thickness of the Ti transition layer is preferably 0.2~1.0 μm, more preferably 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm or 1.0 μm. In embodiments of this invention, the thickness of the Ti transition layer can be 0.5 μm or 1.0 μm.

[0020] In this invention, the thickness of the functional layer is preferably 0.5~2.0 μm, more preferably 0.5 μm, 1 μm, 1.5 μm or 2.0 μm. In an embodiment of this invention, the thickness of the functional layer can be 1.0 μm.

[0021] In this invention, the atomic percentages of Ti, Zr, Hf and Ta in the TiZrHfTaCuN are preferably 10.0~14.0 at.%, more preferably 10.0 at.%, 11.0 at.%, 12.0 at.%, 13.0 at.% or 14.0 at.%.

[0022] In this invention, the atomic percentage of Cu in the TiZrHfTaCuN is preferably 2.0~6.0 at.%, more preferably 2.0 at.%, 3.0 at.%, 4.0 at.%, 5.0 at.% or 6.0 at.%.

[0023] In this invention, the atomic percentage of N in the TiZrHfTaCuN is preferably 45.0~55.0 at.%, more preferably 45.0 at.%, 46.0 at.%, 47.0 at.%, 48.0 at.%, 49.0 at.%, 50.0 at.%, 51.0 at.%, 52.0 at.%, 53.0 at.%, 54.0 at.%, or 55.0 at.%.

[0024] The present invention also provides a method for preparing the protective coating described in the above technical solution, comprising the following steps: The protective coating is obtained by sequentially depositing a Ti transition layer and a functional layer on the substrate surface using magnetron sputtering.

[0025] In this invention, the substrate is preferably 304 stainless steel.

[0026] In this invention, prior to the deposition, the substrate is preferably subjected to ultrasonic cleaning and ion cleaning sequentially. The ultrasonic cleaning preferably includes sequential ultrasonic cleaning in acetone, ethanol, and water, wherein the water is preferably deionized water. The power of each stage of ultrasonic cleaning is preferably 220-260 W, more preferably 220 W, 230 W, 240 W, 250 W, or 260 W; the time is preferably 15-20 min, more preferably 15 min, 16 min, 17 min, 18 min, 19 min, or 20 min. After each stage of ultrasonic cleaning, the invention preferably includes drying, which is preferably performed using nitrogen gas.

[0027] In this invention, prior to the ion cleaning, it is preferable to place the substrate in a sample tray and mount it on a sample rack, then install two TiZrHfTa targets, one Cu target, and one Ti target at four different target locations, and subsequently evacuate and purge the coating chamber with argon gas. The distances between the four targets and the substrate are preferably 6-10 cm, more preferably 6 cm, 7 cm, 8 cm, 9 cm, or 10 cm.

[0028] In this invention, the purity of the TiZrHfTa target, Cu target and Ti target is preferably 99.9~99.99%; the TiZrHfTa target, Cu target and Ti target are all rectangular, with a preferred size of 110 mm * 90 mm and a preferred thickness of 5 mm.

[0029] In this invention, controlling the positional relationship between the substrate and the target material can ensure that the target material glows and the released plasma is uniformly deposited onto the substrate surface.

[0030] The present invention does not impose any special limitations on the vacuuming process, and adopts a process well known to those skilled in the art to achieve a vacuum degree of 6×10. -5 Pa.

[0031] In this invention, the working gas for ion cleaning is preferably argon, and the flow rate of the argon is preferably 50-100 sccm, more preferably 50 sccm, 60 sccm, 70 sccm, 80 sccm, 90 sccm, or 100 sccm; the working gas pressure is preferably 1.0-2.5 Pa, more preferably 1.0 Pa, 1.5 Pa, 2 Pa, or 2.5 Pa; the substrate is connected to an RF power supply, and the voltage of the RF power supply is preferably 800-1000 V, more preferably 800 V, 850 V, 900 V, 950 V, or 1000 V; the duty cycle is preferably 40-60%, more preferably 40%, 45%, 50%, 55%, or 60%; the time is preferably 30 min; the substrate temperature is preferably 100-500 °C, more preferably 100 °C, 200 °C, 300 °C, 400 °C, or 500 °C. The temperature is ℃; the rotational speed of the substrate is preferably 5~20 rpm, more preferably 5 rpm, 10 rpm, 15 rpm or 20 rpm. In this invention, the temperature of the substrate is preferably obtained by heating under vacuum.

[0032] In this invention, the deposition conditions of the Ti transition layer are preferably as follows: the working gas is preferably argon, and the argon gas inlet rate is preferably 20~40 sccm, more preferably 20 sccm, 25 sccm, 30 sccm, 35 sccm or 40 sccm; the working gas pressure is preferably 0.3~1.0 Pa, more preferably 0.3 Pa, 0.4 Pa, 0.5 Pa, 0.6 Pa, 0.7 Pa, 0.8 Pa, 0.9 Pa or 1.0 Pa; the target material is preferably a Ti target, and the Ti target is connected to a DC power supply with a current preferably 8~12 A, more preferably 8 A, 9 A, 10 A, 11 A or 12 A; the substrate is connected to an RF power supply with a voltage preferably 50~150 V, more preferably 50 V, 60 V, 70 V, 80 V, 90 V, 100 V, 110 V, 120 V, 130 V, 140 V or 150 V. V; the duty cycle is preferably 50-90%, more preferably 50%, 60%, 70%, 80% or 90%; the time is preferably 30 min; the substrate temperature is preferably 100-500℃, more preferably 100℃, 200℃, 300℃, 400℃ or 500℃; the substrate rotation speed is preferably 5-20 rpm, more preferably 5 rpm, 10 rpm, 15 rpm or 20 rpm.

[0033] In this invention, the deposition conditions of the functional layer are preferably as follows: the working gas is preferably argon, and the argon gas inlet rate is preferably 20-40 sccm, more preferably 20 sccm, 25 sccm, 30 sccm, 35 sccm or 40 sccm; the reaction gas is preferably nitrogen, and the nitrogen gas inlet rate is preferably 50-100 sccm, more preferably 50 sccm, 60 sccm, 70 sccm, 80 sccm, 90 sccm or 100 sccm; the working gas pressure is preferably 0.3-1.0 Pa, more preferably 0.3 Pa, 0.4 Pa, 0.5 Pa, 0.6 Pa, 0.7 Pa, 0.8 Pa, 0.9 Pa or 1.0 Pa; the target material is a TiZrHfTa target and a Cu target; the TiZrHfTa target and the Cu target are respectively connected to a DC power supply, and the current of the TiZrHfTa target is preferably 8-12 A, more preferably 8 A, 9 A, 10 A, 11 A. The current of the Cu target is preferably 0.5~3.0 A, more preferably 0.5 A, 1.0 A, 1.5 A, 2.0 A, 2.5 A or 3.0 A; the substrate is connected to an RF power supply, the voltage of which is preferably 50~150V, more preferably 50V, 100V or 150V; the duty cycle is preferably 50~90%, more preferably 50%, 60%, 70%, 80% or 90%; the time is preferably 60~120 min, more preferably 60 min, 80 min, 100 min or 120 min; the temperature of the substrate is preferably 100~500 ℃, more preferably 100 ℃, 200 ℃, 300 ℃, 400 ℃ or 500 ℃; the rotation speed of the substrate is preferably 5~20 rpm, more preferably 5 rpm, 10 rpm, 15 rpm or 20 rpm.

[0034] In this invention, by designing the Ti transition layer structure and optimizing the deposition conditions, the bonding strength between the coating and the substrate can be effectively improved by promoting interface transition and structural densification.

[0035] After the deposition is completed, the present invention preferably includes cooling, which is preferably natural cooling in an inert atmosphere.

[0036] The present invention also provides the application of the protective coating described in the above technical solution or the protective coating prepared by the preparation method described in the above technical solution in the field of high-frequency electrosurgical protection.

[0037] The present invention also provides a high-frequency electrosurgical unit, comprising a high-frequency electrosurgical unit substrate and a protective coating on the surface of the high-frequency electrosurgical unit substrate; The protective coating is the protective coating described in the above technical solution or the protective coating prepared by the preparation method described in the above technical solution.

[0038] The following detailed description, in conjunction with embodiments, illustrates the protective coating, its preparation method, its application, and the high-frequency electrosurgical unit provided by this invention. However, these descriptions should not be construed as limiting the scope of protection of this invention.

[0039] Example 1 The 304 stainless steel substrate was sequentially placed in acetone, ethanol and deionized water and ultrasonicated for 15 min at 250 W ultrasonic power and then dried with nitrogen gas to obtain a clean substrate. Place the cleaned substrate into the sample tray and mount it on the sample holder. Install two TiZrHfTa targets, one Cu target, and one Ti target at four designated target locations (the distance between the target and the cleaned substrate is 9 cm; each target has a purity of 99.99%, is rectangular, and measures 110 mm x 90 mm with a thickness of 5 mm). Then, close the coating chamber and evacuate to a vacuum level of 6 × 10⁻⁶. -5 After Pa, the sample holder was heated to 300 ℃ under vacuum. The rotation speed of the sample holder was adjusted to 10 rpm. Argon gas was introduced into the coating chamber (flow rate of 60 sccm). The working gas pressure was adjusted to 2 Pa by controlling the regulating valve. The sample holder was then connected to the radio frequency power supply for ion cleaning (voltage of 950 V, duty cycle of 50%, time of 30 min). The working gas pressure was then adjusted to 0.35 Pa (argon gas flow rate of 30 sccm) by controlling the regulating valve. The Ti target was connected to a DC power supply, and the sample rotation rack was connected to an RF power supply to deposit a Ti transition layer (DC power supply current of 10 A, RF power supply voltage of 80 V, duty cycle of 65%, time of 30 min). Argon and nitrogen gases were introduced and the working pressure in the coating chamber was maintained at 0.35 Pa through regulating valves (argon flow rate of 30 sccm and nitrogen flow rate of 65 sccm). Two TiZrHfTa targets were connected to DC power supply 1 and DC power supply 2 respectively, and the Cu target was connected to DC power supply 3. After the sample rotation rack was connected to the radio frequency power supply, the functional layer was deposited (the current of DC power supply 1 and DC power supply 2 was 10 A, the current of DC power supply 3 was 2 A, the voltage of the radio frequency power supply was 80 V, the duty cycle was 65%, and the time was 120 min). The power supply was turned off, sputtering was stopped, and the sample was naturally cooled to room temperature in an argon atmosphere before being placed in the atmospheric environment to obtain a protective coating (the thickness of the Ti transition layer was 0.5 ± 0.05 μm, the thickness of the functional layer was 1 ± 0.05 μm, and the composition was: Ti 13.2 at.%, Zr 13.7 at.%, Hf 10.1 at.%, Ta 10.3 at.%, Cu 3.9 at.%, and N 48.8 at.%). The mechanical properties and hardness of the protective coating were tested using a nanoindenter equipped with a Berkovich-type diamond pyramid indenter in continuous stiffness measurement (CSM) mode. The adhesion between the coating and the substrate was tested using a multifunctional material surface tester, and the critical load for adhesion was obtained. The water contact angle of the coating surface was measured using an optical contact angle meter. The antiplatelet adhesion performance of the coating was evaluated using a platelet adhesion assay. Colony counting was performed using the colony forming unit (CFU) method, and the antibacterial rate of the coating was calculated. Cells were stained using a live / dead cell staining kit, and the cytotoxicity of the coating was evaluated by detecting the ratio of live to dead cells. The hardness of the protective coating is 35.2 ± 0.3 GPa (e.g., ...). Figure 3 As shown), the critical load for adhesion was 33 N, and the water contact angle was 130°. Compared with a 304 stainless steel substrate, the platelet adhesion rate decreased by 70.37% to 17.27%; at the same time, the antibacterial rate increased by 66.61% to 99.17% (as shown). Figure 1 (As shown).

[0040] Example 2 Referring to Example 1, the difference lies in that: the deposition time of the Ti transition layer is adjusted to 60 min, and the thickness of the Ti transition layer in the resulting protective coating is 1 μm; the hardness of the protective coating is 33.2 ± 0.5 GPa (e.g., ...). Figure 3 (As shown), other performance characteristics are the same.

[0041] Example 3 Referring to Example 1, the difference lies in that: the current of DC power supply 3 is 4A, and the time is 60 minutes; the composition of the resulting protective coating is: Ti 12.9 at.%, Zr 13.4 at.%, Hf 10.0 at.%, Ta 10.1 at.%, Cu 5.0 at.%, and N 48.6 at.%; The protective coating has a hardness of 24.2 ± 0.3 GPa, a critical adhesion load of 30 N, a water contact angle of 117.3°, an adhesion rate of 22.25%, and an antibacterial rate of 98.91% (e.g., ...). Figure 1 (As shown).

[0042] Comparative Example 1 Referring to Example 1, the difference is that during the preparation of the functional layer, the current of the Cu target connected to the DC power supply 3 is 0A, resulting in a protective coating (the thickness of the Ti transition layer is 0.5 μm, the thickness of the functional layer is 1 μm, and the composition is: Ti 14.1 at.%, Zr 14.8 at.%, Hf 10.8 at.%, Ta 11.0 at.%, Cu 0 at.% and N 49.3 at.%). The hardness of the protective coating is 31.7 ± 0.4 GPa (e.g., ...). Figure 3 As shown), the critical load for bonding force is 30 N, the water contact angle is 113.1°, the adhesion rate is 44.70%, and the antibacterial rate is 69.33% (as shown). Figure 1 As shown in the figure, it cannot meet the requirements for anti-adhesion and antibacterial properties.

[0043] Comparative Example 2 Referring to Example 1, the difference is that the duty cycle during the preparation of the Ti transition layer and the duty cycle during the preparation of the functional layer are both 30%, resulting in a protective coating; The critical load for adhesion of the protective coating is 11 N, and the hardness is 16.7 ± 0.5 GPa (e.g., Figure 3 As shown in the figure, it cannot meet the service requirements.

[0044] Test case 1. Antibacterial rate test: The antibacterial performance of samples was evaluated by culturing and counting the number of bacterial colonies eluted from the sample surface using the plate count method. A bacterial suspension treated under the same conditions but without samples was used as a control group. The inhibition rate was calculated based on the percentage reduction in colony count between the experimental group and the control group. The specific procedure was as follows: A bacterial suspension with a concentration of 10... 6 A CFU / mL suspension of Staphylococcus aureus was inoculated onto the sample surface and incubated at 37 °C for 24 h. After incubation, the sample was placed in 1 mL of phosphate-buffered saline (PBS) and gently shaken to allow for complete elution of bacteria adhering to the sample surface. Subsequently, the resulting bacterial suspension was diluted 10⁻⁶ times. 8 Take 100 μL of the diluted solution and spread it evenly on the surface of the agar medium, then incubate at 37 ℃ for 24 h. After incubation, observe the bacterial growth in each petri dish and count the colonies. in, Figure 1 The bar chart shows the antibacterial rate of the protective coatings described in the control group, Examples 1 and 3, and Comparative Examples 1 and 2. Figure 1 It can be seen that, compared with the uncoated control group, Examples 1 and 3 have significant antibacterial effects, with an antibacterial rate of over 98%, effectively inhibiting surgical infections caused by bacterial adhesion. The protective coatings described in Comparative Examples 1 and 2 have relatively poor ability to inhibit bacterial adhesion; 2. The cytotoxicity of the protective coatings described in Examples 1-3 was evaluated using a live / dead cell staining kit. Figure 2 The cytotoxicity test results of the protective coatings described in Examples 1-3 are provided by... Figure 2 It is evident that the protective coatings described in Examples 1-3 are all non-cytotoxic.

[0045] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A protective coating, characterized in that, It includes a Ti transition layer and a functional layer sequentially stacked on the substrate surface; The functional layer is made of TiZrHfTaCuN, and TiZrHfTaCuN has a multi-component solid solution structure.

2. The protective coating as described in claim 1, characterized in that, The atomic percentages of Ti, Zr, Hf, and Ta in the TiZrHfTaCuN composition are independently 10.0~14.0 at.% The atomic percentage of Cu in the TiZrHfTaCuN is 2.0~6.0 at.% The atomic percentage of N in the TiZrHfTaCuN is 45.0~55.0 at.%.

3. The method for preparing the protective coating according to claim 1 or 2, characterized in that, Includes the following steps: The protective coating is obtained by sequentially depositing a Ti transition layer and a functional layer on the substrate surface using magnetron sputtering.

4. The preparation method according to claim 3, characterized in that, Before the deposition is performed, the substrate is sequentially subjected to ultrasonic cleaning and ion cleaning.

5. The preparation method according to claim 4, characterized in that, The ultrasonic cleaning process includes sequential ultrasonic cleaning in acetone, ethanol, and water. The power of ultrasonic cleaning at each stage is 220~260 W and the time is 15~20 min.

6. The preparation method according to claim 4, characterized in that, The working gas for ion cleaning is argon, with an argon flow rate of 50-100 sccm and a working pressure of 1.0-2.5 Pa. The substrate is connected to an RF power supply with a voltage of 800-1000 V, a duty cycle of 40-60%, and a time of 30 min. The substrate temperature is 100-500 ℃, and the substrate rotation speed is 5-20 rpm.

7. The preparation method according to claim 3, characterized in that, The deposition conditions for the Ti transition layer are as follows: the working gas is argon, the argon gas flow rate is 20~40 sccm, the working gas pressure is 0.3~1.0 Pa, the target material is a Ti target, the Ti target is connected to a DC power supply with a current of 8~12 A; the substrate is connected to an RF power supply with a voltage of 50~150 V, a duty cycle of 50~90%, and a time of 30 min; the substrate temperature is 100~500 ℃, and the substrate rotation speed is 5~20 rpm.

8. The preparation method according to claim 3, characterized in that, The deposition conditions for the functional layer are as follows: the working gas is argon, with an argon flow rate of 20-40 sccm; the reactant gas is nitrogen, with a nitrogen flow rate of 50-100 sccm; and the working pressure is 0.3-1.0 Pa. The target materials are TiZrHfTa and Cu targets, respectively connected to a DC power supply. The current of the TiZrHfTa target is 8-12 A, and the current of the Cu target is 0.5-3.0 A. The substrate is connected to an RF power supply with a voltage of 50-150 V, a duty cycle of 50-90%, and a time of 60-120 min. The substrate temperature is 100-500 ℃, and the substrate rotation speed is 5-20 rpm.

9. The application of the protective coating according to claim 1 or 2 or the protective coating prepared by the preparation method according to any one of claims 3 to 8 in the field of high-frequency electrosurgical protection.

10. A high-frequency electrosurgical unit, characterized in that, Includes a high-frequency electrosurgical substrate and a protective coating on the surface of the high-frequency electrosurgical substrate; The protective coating is the protective coating of claim 1 or 2 or the protective coating prepared by the preparation method of any one of claims 3 to 8.

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