CN116240491A - A kind of scalpel coating and its preparation method and application - Google Patents

Abstract

The invention discloses a scalpel coating, a preparation method and application thereof, and relates to the field of anti-adhesion coatings. The scalpel coating provided by the present invention comprises metal zirconium transition layer, equistoichiometric ratio ZrN intermediate layer and surface overstoichiometric ZrN _x layer in turn; N/Zr=0.9～1.1 in equal stoichiometric ratio ZrN layer; overstoichiometric ratio In the ZrN _x layer, N/Zr=1.15-1.3; wherein the metal zirconium transition layer, the equistoichiometric ZrN intermediate layer and the surface overstoichiometric ZrN _x layer have thicknesses of 200-230nm, 620-650nm, and 220-250nm respectively. Based on the hydrophobicity and low reflectivity of the _ZrNx layer, the excellent physical and mechanical properties of the ZrN layer, and the strong binding force between the ZrN layer to the Zr transition layer and the _ZrNx layer, the coating provided by the present invention has both anti- Adhesive properties, low reflectivity and excellent physical properties have broad application prospects in high-frequency surgical electrosurgical units.

Description

A kind of scalpel coating and its preparation method and application

technical field

The invention relates to the field of anti-adhesion coatings, in particular to a scalpel coating and its preparation method and application.

Background technique

High-frequency surgical electric knife is a new type of minimally invasive surgical instrument. It generates high-frequency and high-voltage current through the discharge of the knife tip electrode, contacts with high-impedance biological tissue, and forms a high-temperature environment near the tissue. The thermal effect can denature and dehydrate tissue cell proteins. Therefore, the high-frequency electrosurgical knife has the functions of cutting and hemostasis at the same time. Its hemostatic effect is good and the operation is simple, which not only reduces the operation time, but also reduces the probability of complications, so it is widely used in clinical practice. However, just because the cells and tissues will be dehydrated and denatured by high temperature, the denatured tissues will form scabs during the operation, which will adhere to the surface of the blade, and then be further carbonized by the high temperature of the electric knife, and the adhesion will be stronger. The existence of scabs will increase the resistance of the scalpel blade, which in turn will lead to an increase in the temperature of the electric knife, which will affect the cutting accuracy and easily cause thermal damage to non-target tissues and induce complications. The scabs adhering to the surface of the blade are not easy to fall off and need to be manually cleaned by the surgeon, which will increase the operation time. In addition, the high-frequency electrosurgical knife head is usually bright metallic color, which will reflect glare light under the illumination of the surgical lamp, interfere with the doctor's line of sight and reduce the accuracy of the operation.

At present, there are mainly three ways to try to solve the above problems of high-frequency electric knife: blade surface structure modification, blade surface coating modification, and surface structure-coating modification. The prior art discloses a PTFE (polytetrafluoroethylene) coating coated on the electrode surface of the knife head, which increases the hydrophobicity of the surface of the scalpel so as to reduce the tissue adhering to the blade during surgery. However, PTFE will produce harmful exhaust gas when subjected to high temperature, and PTFE is a soft coating, which has poor bonding force with the surface of the scalpel and is easy to fall off. It will remain in the patient's body during the operation, affecting the recovery of the patient and even causing poisoning. Another prior art discloses a hydrophobic anti-reflective coating composed of _SiO2 particles and organic hydrophobic groups on their surface. However, since the main component of the coating is silicon dioxide, the mechanical strength is insufficient, so it is not suitable for coating Cover the surface of the scalpel.

Contents of the invention

Aiming at the problems in the prior art that the surface of the scalpel is easy to reflect glare light and the coating that modifies the surface of the scalpel is easy to fall off, the present invention provides a coating of a scalpel, which is a ZrN/ZrN _x composite Coating, based on the physical and mechanical properties of ZrN, the low reflectivity of the ZrN _x layer on the surface, and the hydrophobicity of ZrN and ZrN _x , the scalpel coating has good physical properties, mechanical strength, anti-biological tissue adhesion and anti-reflection performance ; At the same time, because ZrN has a higher binding force to the ZrN _x layer and the zirconium transition layer, the scalpel coating is not easy to come off from the scalpel surface.

Another object of the present invention is to provide a method for preparing a scalpel coating.

Another object of the present invention is to provide a scalpel.

In order to achieve the above object, the present invention provides the following technical solutions: a scalpel coating, which successively includes a metal zirconium transition layer, an equal stoichiometric ZrN layer, and a surface cross-stoichiometric ZrN _x layer; N/Zr=0.9～1.1; N/Zr=1.15～1.3 in the stoichiometric ratio ZrN _x layer; metal zirconium transition layer, equal stoichiometric ratio ZrN intermediate layer and surface stoichiometric ratio ZrN _x layer thickness are 200～ 230nm, 620~650nm, 220~250nm.

In the scalpel coating provided by the present invention, metal nitrides ZrN and _ZrNx belong to ceramic materials, and the physical properties such as thermal expansion coefficient are quite different from those of the metal scalpel substrate. Therefore, the present invention introduces a layer between the ZrN layer and the substrate The metal Zr layer makes the physical and mechanical properties between each layer change gradually, reducing the probability that the coating will fall off from the surface of the scalpel due to heat and other conditions.

The present invention adopts stoichiometric _ZrNx layer (N/Zr=1.15～1.3) as the outermost layer of the coating, because in metal nitrides exceeding the stoichiometric ratio, the electrons of d orbitals in the transition metal zirconium will transfer to Nitride is formed on excess N atoms, and the free electrons inside the nitride layer are reduced, so the probability of incident light interacting with free electrons to generate reflected light is reduced. At the same time, the appearance of ZrN _x is dark gray, so ZrN _{The x-} layer has low reflectivity. In addition, the introduction of nitrogen makes zirconium nitride have a certain degree of hydrophobicity, so adding a layer of ZrN _x layer on the surface of the scalpel can improve the performance of the scalpel against biological tissue adhesion at the same time, and prevent the scalpel from being damaged by tissue adhesion. Problems arise from increased electrical resistance and thermal damage to non-target tissue.

However, the presence of excessive N elements will affect the bonding between the ZrN _x layer and the Zr layer, so that the binding force between the two layers will drop. Therefore, the present invention introduces a new method between the surface ZrN _x layer and the Zr transition layer A layer of ZrN intermediate layer with equal stoichiometric ratio (N/Zr=0.9～1.1), the intermediate layer has strong binding force for ZrN _x layer and Zr layer, and has excellent physical and mechanical properties, which can improve the scalpel The physical properties such as mechanical strength and electrical conductivity of the coating, and the improvement of electrical conductivity further reduces the probability of increased electrical resistance and thermal damage to non-target tissues due to the adhesion of biological tissues on the surface of the scalpel.

In order to ensure that the coating does not affect the use of the high-frequency electrosurgical knife, the present invention limits the total thickness of the scalpel coating to about 1 μm. Among them, the thickness of the metal zirconium transition layer is 200-230nm, which is the conventional thickness of the metal transition layer introduced when the ceramic material coating is prepared on the metal substrate; the thickness of the equistoichiometric ZrN intermediate layer is 620-650nm, which is lower than At 620nm, the physical and mechanical properties of the intermediate layer are insufficient, and the electrical conductivity, hardness, and bonding force to the scalpel substrate of the scalpel coating are difficult to surpass the level of the prior art, and when the thickness of the intermediate layer is higher than 650nm, the scalpel The total thickness of the coating will thus increase, affecting the normal operation of the scalpel, and the preparation cost of the coating will also increase; the thickness of the surface stoichiometric ZrN _x layer is 220-250nm, and the surface layer below 220nm is difficult to improve The anti-reflection performance of the scalpel coating is because the appearance of the middle equistoichiometric ZrN layer is golden yellow, which is easy to reflect glare light, and the too thin dark gray surface layer cannot cover the middle layer well, and the too thin A thick surface layer will affect the electrical conductivity and mechanical properties of the scalpel coating.

The invention protects a preparation method of a scalpel coating, which specifically comprises the following steps: sequentially depositing a metal Zr transition layer, an equistoichiometric ZrN intermediate layer and a surface overstoichiometric ZrN _x layer on a substrate.

Preferably, the method for depositing the coating is a DC magnetron sputtering method, which specifically includes the following steps:

Introduce a mixed gas of argon and nitrogen into the vacuum chamber, control the proportion of nitrogen in the mixed gas and the vacuum degree of the vacuum chamber, and open the Zr target for deposition;

The proportion of nitrogen in the mixed gas atmosphere is 12 to 15% when depositing an equistoichiometric ZrN intermediate layer;

The proportion of nitrogen gas in the mixed gas atmosphere is 44-52% when depositing the stoichiometric _ZrNx layer on the surface.

The scalpel coating prepared by magnetron sputtering can improve the physical and mechanical properties, hydrophobicity and anti-reflective properties while making the surface of the coating have fewer defects, which cannot be achieved by other deposition methods: For example, when the coating is deposited by the cathodic arc deposition method, although the coating has excellent adhesion to the substrate, the surface of the coating has a lot of defects and unevenness, and the properties of the coating are not uniform, which is difficult to meet the requirements of preparation. Scalpel requirements.

The specific value of N/Zr in the middle layer and the surface layer in the scalpel coating is determined by the ratio of nitrogen in the magnetron sputtering vacuum chamber to the mixed gas atmosphere during deposition. When DC magnetron sputtering is used to deposit different composition layers in the scalpel coating, the proportion of nitrogen in the mixed gas atmosphere should be controlled in the ranges of 12-15% and 44-52%, respectively, so that the middle layer and N/Zr of the surface layer is controlled in the ranges of 0.9-1.1 and 1.15-1.3, respectively.

More preferably, before the DC magnetron sputtering, the scalpel substrate is washed with water and cleaned with argon ions.

Washing the substrate with water and argon ions can make the substrate cleaner and more conducive to the deposition of the scalpel coating.

In a specific embodiment of the present invention, the specific operation steps of water washing and argon ion cleaning on the scalpel substrate are as follows:

Add metal cleaning powder in deionized water, turn on ultrasonic cleaning scalpel substrate, after cleaning, clean residual metal cleaning powder with deionized water, rinse with absolute ethanol, and dry the substrate with dry compressed air. Place the substrate on the workpiece support in the vacuum chamber, evacuate the vacuum chamber until the vacuum degree is below 4.0× ^10-3 Pa, control the temperature at 300-350°C, feed argon gas into the deposition chamber, and keep the pressure of the vacuum chamber at 0.8-3 Pa. 1pa, set the bias voltage of the workpiece support to -550～-600V, and work for 20 minutes, then turn on the ion source, pass argon gas into the ion source, keep the pressure of the vacuum chamber at 0.8～1Pa, set the current of the ion source to 20A, set the bias of the workpiece support Voltage -150 ~ -200V, working time is 15min.

More preferably, in the DC magnetron sputtering method, the overall pressure of the vacuum chamber is 0.2-0.8 Pa.

The overall air pressure in the vacuum chamber must first be higher than 0.2Pa, so that the magnetron sputtering power supply can ionize the inert gas molecules and bombard the target; however, the overall air pressure in the vacuum chamber should not be higher than 0.8Pa, otherwise too many gas molecules will hinder the The movement path of the bombarded metal ions in the target makes it difficult to deposit on the substrate smoothly, and it is difficult to form a uniform coating.

More preferably, the power of the magnetron sputtering power supply in the DC magnetron sputtering method is 3.5-4kW.

If the sputtering power is too small, the useful work done by the sputtering power supply cannot meet the requirements of glow discharge; if the sputtering power is too large, the deposition rate of the coating will be too high, resulting in an increase in the temperature of the substrate, and further The uniformity and compactness of the coating are reduced, which affects the anti-reflection and other properties of the coating.

More preferably, the bias voltage of the substrate in the DC magnetron sputtering method is -50~-200V.

Under the same other conditions, the higher the substrate bias, the stronger the effect of substrate anti-sputtering, the lower the deposition rate, the higher the required deposition time, and the defects inside the coating; Affect the effect of the coating. When the bias voltage of the substrate is lower than -50V, the electrons emitted by the sputtering power supply have less energy when they reach the substrate, so the coating grown on the surface of the substrate has finer grains, and the coating is more Porosity, strength and other properties have declined.

More preferably, the temperature of the substrate in the DC magnetron sputtering method is 300-350°C.

The temperature of the substrate affects the diffusion ability of sputtered atoms on it, the lower the temperature, the slower the diffusion of coating atoms sputtered on the substrate, and the more defects of the coating. If the temperature of the substrate is limited to the above range, the scalpel coating with fewer defects can be prepared, and the physical and mechanical properties of the coating will be better.

More preferably, in the DC magnetron sputtering method, the deposition time is 15-25 minutes when depositing the metal Zr transition layer.

When the magnetron sputtering deposition time is 15-25 minutes, combined with the adjustment of the substrate bias voltage, magnetron sputtering power supply and other parameters, the thickness of the metal zirconium transition layer can be controlled within the range of 200-230nm. The deposition time is longer, but the substrate bias is relatively lowered, and the thickness of the metal zirconium transition layer can also be controlled within the above range, but the grain size and compactness of the coating will be affected, which will eventually affect the coating. Comprehensive performance.

More preferably, in the DC magnetron sputtering method, the deposition time is 85-95 minutes when depositing the equistoichiometric ZrN intermediate layer.

When the magnetron sputtering deposition time is 85-95min, combined with the adjustment of the substrate bias voltage, magnetron sputtering power and other parameters, the thickness of the equistoichiometric ZrN intermediate layer can be controlled within the range of 620-650nm.

More preferably, in the direct current magnetron sputtering method, the deposition time is 45-65 minutes when depositing a surface-overstoichiometric ZrN _x layer.

When the magnetron sputtering deposition time is 45-65min, combined with the adjustment of the substrate bias voltage, magnetron sputtering power supply and other parameters, the thickness of the surface stoichiometric _ZrNx layer can be controlled within the range of 220-250nm .

The present invention also protects a scalpel, the surface of which has the above-mentioned scalpel coating.

Compared with prior art, the beneficial effect of the present invention is:

The present invention introduces a stoichiometric _ZrNx layer on the surface of the high-frequency surgical electric knife to form a very thin layer of dark gray layer, which reduces the reflectivity of the scalpel surface and improves the hydrophobicity of the scalpel surface, thereby improving the operation efficiency. Anti-biological tissue adhesion properties of the knife surface. In order to reduce the probability of shedding between the metal substrate and the metal nitride ceramic material due to reasons such as differences in thermal expansion coefficients, the present invention introduces a metal Zr transition layer on the surface of the metal substrate. However, the bonding force between the metallic Zr transition layer and the _ZrNx layer is insufficient. The physical properties such as hardness, thermal conductivity, and electrical resistivity of the equal stoichiometric ratio ZrN intermediate layer are all relatively excellent, and have strong binding force to Zr and _ZrNx , so the present invention is also between the Zr transition layer and the _ZrNx layer. A ZrN interlayer is introduced in between. The scalpel coating provided by the present invention has both high physical and mechanical properties, high anti-bioadhesion and low reflectivity, can significantly improve the cutting performance of medical high-frequency electrosurgical surgery and reduce the exposure of doctors to surgical lights during surgery. interference.

Description of drawings

Fig. 1 is a schematic structural view of the scalpel coating provided by the present invention.

Fig. 2 is the preparation method route of scalpel coating provided by the present invention.

Fig. 3 is the contact angle test result of the scalpel coating provided in Example 1 of the present invention.

Fig. 4 is the test result of the contact angle of the equistoichiometric ZrN coating provided in Comparative Example 3 of the present invention.

Fig. 5 is the contact angle test result of the stoichiometric ZrN _x coating provided in Comparative Example 4 of the present invention.

FIG. 6 shows the thickness and color of the equistoichiometric ZrN coating provided in Comparative Example 3 of the present invention.

Fig. 7 shows the thickness and color of the stoichiometric ZrN _x coating provided in Comparative Example 4 of the present invention.

Detailed ways

The specific implementation examples of the present invention are given below to further describe the present invention in detail. However, the examples do not limit the present invention in any form. Unless otherwise specified, the raw material reagents used in the examples of the present invention are conventionally purchased raw material reagents.

Example 1

A scalpel coating, comprising a scalpel substrate, a metal zirconium transition layer, an equal stoichiometric ZrN layer, and a surface over-stoichiometric ZrN _x layer; N/Zr=1.0 in the equal-stoichiometric ZrN layer; over-stoichiometric N/Zr=1.2 in the ratio ZrN _x layer; the metal zirconium transition layer, the equistoichiometric ZrN intermediate layer and the surface overstoichiometric ZrN _x layer have thicknesses of 220nm, 645nm, and 240nm, respectively.

The preparation method of above-mentioned embodiment 1 scalpel coating specifically comprises the steps:

S1. Add metal cleaning powder in deionized water, clean the scalpel substrate with ultrasonic waves, clean the residual metal cleaning powder with deionized water, then rinse with absolute ethanol, dry with dry compressed air, and then place the substrate in a vacuum chamber On the workpiece support, the vacuum chamber is evacuated until the vacuum degree is below 4.0×10 ^–3 Pa, the temperature is controlled at 330°C, 250 sccm of argon gas is introduced into the deposition chamber, and the pressure is kept at 0.8 Pa, and the bias voltage of the workpiece support is set to -600V. Time 20 minutes, then turn on the ion source, pass argon 600sccm into the ion source, keep the strong pressure at 1Pa, set the ion source current to 20A, set the workpiece support bias to -200V, and work for 15 minutes to perform argon ion cleaning;

S2. Control the temperature of the substrate at 330°C, feed argon gas into the vacuum chamber, and control the overall pressure of the vacuum chamber to 0.6Pa; at the same time, set the bias voltage of the substrate to -100V, set the sputtering power supply to 4kW, turn on the Zr target, and deposit for 20min ;

S3. Control the temperature of the substrate to 330°C, feed a mixed gas of nitrogen and argon into the vacuum chamber, control nitrogen to account for 14% of the mixed gas, and control the overall pressure of the vacuum chamber to 0.6Pa; at the same time, set the bias voltage of the substrate to -100V , set the sputtering power supply at 4kW, turn on the Zr target, and deposit for 90min;

S4. Control the temperature of the substrate to be 330°C, feed a mixed gas of nitrogen and argon into the vacuum chamber, control nitrogen to account for 50% of the total gas, and control the overall pressure of the vacuum chamber to 0.6Pa; meanwhile, set the bias voltage of the substrate to -100V, The sputtering power supply was set at 4kW, a mixed gas of argon and nitrogen was introduced into the vacuum chamber, the Zr target was turned on, and the deposition was carried out for 60 minutes. After the deposition was completed, a substrate with a scalpel coating on the surface could be obtained.

Example 2

A scalpel coating, which differs from the scalpel coating provided in Example 1 in that: N/Zr=1.1 in the equistoichiometric ZrN layer.

The preparation method of above-mentioned embodiment 2 scalpel coating, the difference with embodiment 1 is:

S3. The proportion of nitrogen in the mixed gas is 15%.

Example 3

A scalpel coating, which differs from the scalpel coating provided in Example 1 in that: N/Zr=0.9 in the equistoichiometric ZrN layer.

The preparation method of above-mentioned embodiment 3 scalpel coating, the difference with embodiment 1 is:

S3. The proportion of nitrogen in the mixed gas is 12%.

Example 4

A scalpel coating, which differs from the scalpel coating provided in Example 1 in that: N/Zr=1.15 in the overstoichiometric ZrN _x layer.

The preparation method of above-mentioned embodiment 4 scalpel coating, the difference with embodiment 1 is:

S4. The proportion of nitrogen in the mixed gas is 40%.

Example 5

A scalpel coating, which differs from the scalpel coating provided in Example 1 in that: N/Zr=1.3 in the overstoichiometric ZrN _x layer.

The preparation method of above-mentioned embodiment 5 scalpel coating, the difference with embodiment 1 is:

S4. The proportion of nitrogen in the mixed gas is 52%.

Example 6

A kind of scalpel coating, and the difference of the scalpel coating provided in embodiment 1 is: metal zirconium transition layer, equistoichiometric ratio ZrN middle layer and surface superstoichiometric ratio ZrN _x layer thickness are respectively 200nm, 650nm , 220nm.

The preparation method of above-mentioned embodiment 6 scalpel coating, the difference with embodiment 1 is:

S2. The deposition time is 17min;

S3. The deposition time is 92min;

S4. The deposition time is 55 minutes.

Example 7

A kind of scalpel coating, and the difference of the scalpel coating provided in embodiment 1 is: metal zirconium transition layer, equistoichiometric ratio ZrN intermediate layer and surface superstoichiometric ratio ZrN _x layer thickness are respectively 230nm, 620nm , 250nm.

The preparation method of above-mentioned embodiment 7 scalpel coatings, the difference with embodiment 1 is:

S2. Deposition time is 23min;

S3. The deposition time is 86min;

S4. The deposition time is 63 minutes.

Comparative example 1

A kind of scalpel coating, and the difference of the scalpel coating provided in embodiment 1 is: the thickness of metal zirconium transition layer, equistoichiometric ratio ZrN middle layer and surface stoichiometric ZrN _x layer is respectively 215nm, 641nm and 124.5nm.

Comparative example 2

A kind of scalpel coating, and the difference of the scalpel coating provided in embodiment 1 is: the thickness of metal zirconium transition layer, equistoichiometric ratio ZrN middle layer and surface stoichiometric ZrN _x layer is respectively 219nm, 217nm and 243nm.

Comparative example 3

A ZrN coating, the difference from the scalpel coating provided in Example 1 is that the coating only includes a metal zirconium transition layer and an equistoichiometric ZrN layer.

Comparative example 4

A _ZrNx coating, the difference from the scalpel coating provided in Example 1 is that the coating only includes a metal zirconium transition layer and an equistoichiometric ZrN layer.

Performance Testing

Bonding force test: Anton Parr RST ³ large-load scratch tester was used for the experiment. A Rockwell C-type diamond indenter with a radius of 200.0 μm was used. The load range was 1.0-100.0 N, the linear loading rate was 100 N/min, and the scratch length was 3.0mm, repeat the test 3 times for a single sample.

Hardness and elastic modulus test: test with Anton Parr NHT ² (TTX) nano-indentation instrument, the maximum indentation depth should be less than 10% of the coating thickness, the maximum load is 5.0mN, the loading is maintained for 5.0s, and a single sample is repeatedly tested for 15 Second-rate.

Elastic modulus test: Anton Parr NHT ² (TTX) nano-indenter was used for testing.

Coating thickness test: Measured with a SU8820 cross-sectional scanning electron microscope.

Normal temperature average friction coefficient test: measured by Aton Paar THT-1000.

Wear rate test: Anton Paar THT-1000 ball-disk high-temperature friction and wear tester is used for testing, the temperature is 25°C, the relative humidity is 55%, the friction pair is Al ₂ O ₃ ball with a diameter of 6mm, and the linear speed is 0.1m/ s, the wear scar diameter is 4mm, and the friction sliding distance is 7.53m. Obtain the three-dimensional shape data of the friction marks with a laser confocal microscope, and calculate the wear rate by combining the Archard equation: Wr=V/(F*L), where Wr is the wear rate (mm ³ /Nm), and V is the wear volume (mm ³ ) , F is the vertical load (N), L is the wear distance; the load in this experiment is 3N, and the distance is 7.53m.

Resistivity test: Measured by LSP20171 four-probe instrument.

Contact angle test: drop 0.02mL/drop on the surface of the coating, and use JCJTest software to measure the contact angle between the coating and the water drop.

Anti-adhesion test: cut pig small intestine with a scalpel coated with the scalpel coating provided in Example 1 for ten times, and record the cutting time of each scalpel and the state of the cutting head after cutting.

The test results are shown in Figures 1-7 and Tables 1-2 below:

The anti-biological tissue adhesion test result of the coating of table 1 embodiment 1

Cutting times Whether eschar 1 no 2 no 3 no 4 no 5 no 6 no 7 no 8 no 9 no 10 no

Table 2 embodiment and comparative example performance test result

Binding force/N Contact angle/° HSB Hue Anti-adhesion effect Example 1 31.5 98.6 31≤B≤34 excellent Example 2 30.7 97.8 31≤B≤34 excellent Example 3 33.1 100.3 31≤B≤34 excellent Example 4 32.5 97.4 31≤B≤34 excellent Example 5 29.2 98.3 32≤B≤35 excellent Example 6 30.9 99.7 31≤B≤34 good Example 7 31.7 98.1 31≤B≤34 excellent Comparative example 1 21.4 91 40≤B≤110 generally Comparative example 2 16.2 92 32≤B≤34 generally Comparative example 3 32.7 105 / (coated in gold) excellent Comparative example 4 15.3 96 32≤B≤33 generally

As can be seen from the results in Table 1, the scalpel coating provided by the present invention has excellent anti-biological tissue adhesion function, and the scalpel covered with the coating provided by the present invention, after fresh pig small intestine was cut ten times There was still no eschar, indicating that there was no adhesion of biological tissue.

As can be seen from the data in Table 2, in the scalpel coatings provided by Examples 1 to 7 of the present invention, since the coatings satisfy: N/Zr in the equistoichiometric ZrN layer is 0.9 to 1.1, the stoichiometric ratio The N/Zr in the ZrN _x layer is 1.15-1.3, the thickness of the metal zirconium transition layer, the equistoichiometric ZrN intermediate layer, and the surface over-stoichiometric ZrN _x layer are 200-230nm, 620-650nm, and 220-250nm, respectively. Conditions, so the bonding force between the coating and the scalpel substrate is basically above 30N, and it is not easy to fall off; at the same time, the contact angle of the coating is above 97°, which has good hydrophobicity, so it also has good The performance of anti-biological tissue adhesion; the HSB hue of the coating has also reached more than 31, the coating is dark, and the anti-reflection performance is excellent.

The scalpel coating provided in Comparative Example 1 is due to the insufficient thickness of the surface stoichiometric ratio ZrN _x layer, so the contact angle decreases and the anti-biological tissue adhesion performance decreases. , and the B value in the HSB hue increases. The B value in HSB controls the amount of black mixed into the pure color. The larger the B value, the less black in the coating color and the higher the lightness. Therefore, it can be seen from the data in Table 2 that the scalpel coating provided by Comparative Example 1 is resistant to Reflective performance will be reduced.

In the scalpel coating provided in Comparative Example 2, due to the insufficient thickness of the ZrN layer with an intermediate equistoichiometric ratio, the bonding force between the coating and the substrate as a whole is reduced.

For the ZrN coating provided in Comparative Example 3, although the binding force and hydrophobicity of the coating and the substrate all meet the requirements of the scalpel coating, but because there is no surface of the outermost layer through the stoichiometric ZrN _x layer, the coating presents Gold, not anti-reflective.

Although the _ZrNx coating provided in Comparative Example 4 has good hydrophobicity and anti-reflection properties, the binding force between the _ZrNx coating and the scalpel substrate is insufficient due to the absence of the intermediate equistoichiometric ZrN coating transition.

Fig. 1 is a schematic structural view of the scalpel coating provided by the present invention. It can be seen from FIG. 1 that the scalpel coating provided by the present invention sequentially includes a scalpel substrate, a metal zirconium transition layer, an equistoichiometric ZrN layer, and a surface overstoichiometric ZrN _x layer.

Fig. 2 is the preparation method route of scalpel coating provided by the present invention. As can be seen from Fig. 2, the preparation method of scalpel coating provided by the present invention mainly includes the steps of: depositing metal Zr transition layer, equal stoichiometric ratio ZrN intermediate layer and surface stoichiometric ZrNx layer on the substrate successively .

Fig. 3 is the contact angle test result of the scalpel coating provided in Example 1 of the present invention. It can be seen from FIG. 3 that the contact angle of the coating provided by Example 1 reaches 98.2°, which has good hydrophobicity.

Fig. 4 is the test result of the contact angle of the equistoichiometric ZrN coating provided in Comparative Example 3 of the present invention. It can be seen from Fig. 4 that the contact angle of the coating provided by Comparative Example 3 reaches 105°, and also has good hydrophobicity.

Fig. 5 is the contact angle test result of the stoichiometric ZrN _x coating provided in Comparative Example 4 of the present invention. It can be seen from FIG. 5 that the contact angle of the stoichiometric _ZrNx coating provided by Comparative Example 4 reaches 96°, which also has good hydrophobicity.

FIG. 6 shows the thickness and color of the equistoichiometric ZrN coating provided in Comparative Example 3 of the present invention. It can be seen from FIG. 6 that the color of the coating provided by Comparative Example 3 is bright golden yellow, and the coating is very reflective.

Fig. 7 shows the thickness and color of the stoichiometric ZrN _x coating provided in Comparative Example 4 of the present invention. It can be seen from Figure 7 that the color of the coating provided by Comparative Example 4 is brownish gray, and the B in the HSB hue ranges from a maximum of 33 to a minimum of 32, all of which are lower than 40, and the coating is not easy to reflect light.

Apparently, the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, rather than limiting the implementation of the present invention. For those of ordinary skill in the art, other changes or changes in different forms can be made on the basis of the above description. It is not necessary and impossible to exhaustively list all the implementation manners here. All modifications, equivalent replacements and improvements made within the spirit and principles of the present invention shall be included within the protection scope of the claims of the present invention.

Claims (10)

1. A scalpel coating is characterized by sequentially comprising a metallic zirconium transition layer, a ZrN layer with equal stoichiometric ratio and a ZrN layer with surface over stoichiometric ratio _x A layer;

n/zr=0.9 to 1.1 in the equal stoichiometric ZrN layer;

the superstoichiometric ratio ZrN _x N/zr=1.15 to 1.3 in the layer;

the zirconium metal transition layer, the ZrN intermediate layer with equal stoichiometric ratio and the ZrN with surface over stoichiometric ratio _x The layer thicknesses are 200-230 nm, 620-650 nm and 220-250 nm respectively.

2. A method for preparing the scalpel coating according to claim 1, comprising the steps of: sequentially depositing a metallic Zr transition layer, a ZrN intermediate layer with equal stoichiometric ratio and surface over-stoichiometric ZrN on a substrate _x A layer.

3. The method for preparing the scalpel coating according to claim 2, wherein the deposition method is a direct current magnetron sputtering method, and specifically comprises the following steps:

introducing mixed gas of argon and nitrogen into the vacuum chamber, controlling the ratio of the nitrogen in the mixed gas and the vacuum degree in the vacuum chamber, and opening a Zr target for deposition;

the ratio of nitrogen in the mixed gas atmosphere is 12-15% when a ZrN intermediate layer with equal stoichiometric ratio is deposited;

the ratio of nitrogen in the mixed gas atmosphere is over stoichiometric ZrN on the deposition surface _x 44-52% of the layer.

4. The method for preparing a scalpel coating according to claim 3, wherein the overall air pressure of the vacuum chamber in the direct current magnetron sputtering method is 0.2-0.8 Pa.

5. A method of preparing a surgical knife coating as claimed in claim 3, wherein the power of the magnetron sputtering power supply in the dc magnetron sputtering method is 3.5 to 4kW.

6. The method for preparing a coating for a surgical knife according to claim 3, wherein the bias voltage of the substrate in the direct current magnetron sputtering method is-50 to-200V.

7. A method of preparing a surgical knife coating according to claim 3, wherein the temperature of the substrate in the dc magnetron sputtering process is 300 to 350 ℃.

8. The method for preparing a scalpel coating according to claim 3, wherein the deposition time is 15-25 min when the metallic Zr transition layer is deposited in the direct current magnetron sputtering method.

9. The method for preparing a scalpel coating as claimed in claim 3, wherein in the direct current magnetron sputtering method, the deposition time is 85-95 min when the intermediate layer with equal stoichiometric ratio ZrN is deposited.

10. A scalpel, characterized in that the scalpel surface has a scalpel coating as claimed in any one of claims 1 to 9.

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