CN111876735B - Preparation method of wear-resistant and antibacterial Cr-Mo-Ag-Si-C-N multi-element composite film - Google Patents

Abstract

The invention discloses a preparation method of a Cr-Mo-Ag-Si-C-N multi-element composite film with wear resistance and antibiosis, belonging to the field of surface engineering and tribology. The method comprises the following steps: 1) installing the base material on a sample stage in a coating instrument, and bombarding and cleaning and activating the surface of the substrate by using Ar ion beams; 2) introducing Ar gas, rotating the sample table, and depositing a Cr transition layer with the thickness of about 0.2 mu m by using a coating instrument; 3) ar gas and N are introduced₂Gas, depositing a CrN gradient layer on the Cr transition layer; starting a Mo target direct current power supply, gradually increasing the Mo target sputtering current, and depositing a CrMoN gradient layer on the CrN gradient layer; 4) introducing Ar gas and N₂And gas and trimethyl silane gas, starting an Ag target power supply, fixing sputtering current of each target, and preparing the CrMoAgSiCN multi-element composite film on the CrMoN gradient layer. According to the invention, the Cr-Mo-Ag-Si-C-N multi-element composite film with different microstructures, excellent mechanical property and self-lubricating property, good corrosion resistance, wear resistance and antibacterial property is obtained by changing the sputtering current of the Ag target.

Description

Preparation method of wear-resistant and antibacterial Cr-Mo-Ag-Si-C-N multi-element composite film

The technical field is as follows:

the invention relates to a preparation method of a Cr-Mo-Ag-Si-C-N multi-element composite film with wear resistance and antibiosis, belonging to the field of surface engineering and tribology.

Background art:

the Cr-N film has good oxidation resistance and wear resistance, and has wide development potential in the aspect of tool protection. However, with the development of the industrial and manufacturing fields, Cr — N thin films have gradually failed to satisfy the increasing demands in terms of high hardness, low friction coefficient, and excellent corrosion resistance. Researchers have introduced trimethylsilylThe alkyl (TMS) is used for preparing a quaternary Cr-Si-C-N film, the solid solution strengthening effect of the film at low Si content is enhanced in hardness, and due to the good lubricating and anti-wear effect of amorphous carbon and Si (OH) formed by the hydration reaction of Si element in water environment₄The lubricating layer provides the film with a lower coefficient of friction. However, the quaternary Cr-Si-C-N film has poor tribological performance under insufficient lubrication conditions and does not have antifouling and antibacterial properties. Research shows that Mo has solid solution strengthening effect after being doped into film and is favorable to strengthening mechanical performance. And in the seawater environment, the Mo-containing film forms MoO with a layered structure in friction₃As a self-lubricating layer, it effectively reduces the coefficient of friction. MoO₃Further formation of H molybdate in water₂MoO₄With water and hydrogen ions H₃O⁺The effects of destroying the pH balance, enzymes and transmission systems in the bacteria are realized, and the adhesion of the bacteria and the formation of a biological film are effectively prevented. This indicates that the introduction of Mo element contributes to the realization of bactericidal characteristics of the film surface. On the other hand, by doping Ag element, the Ag soft lubricating film distributed and covered on the surface of the film shows excellent high wear resistance. Meanwhile, the film releases metal ions Ag in the environment of bacteria liquid⁺Plays a certain role in sterilization, and has a certain effect of reacting with molybdate radical ion MoO₄ ^2-Generate silver molybdate Ag under the coordination of₂MoO₄Has low friction and shows excellent inhibitory and killing effects on Escherichia coli and Staphylococcus aureus. Therefore, the Cr-Mo-Ag-Si-C-N multi-element composite film has more excellent self-lubricating tribology and sterilization characteristics than the quaternary Cr-Si-C-N film. However, no research has been made on the multi-element Cr-Mo-Ag-Si-C-N thin film.

The invention content is as follows:

the invention provides a preparation method of a Cr-Mo-Ag-Si-C-N multi-element composite film with wear resistance and antibacterial property, which is characterized in that the Cr-Mo-Ag-Si-C-N multi-element composite film with different microstructures, excellent mechanical property and self-lubricating property, good corrosion resistance, wear resistance and antibacterial property is obtained by changing Ag target sputtering current.

The invention adopts the following technical scheme for solving the technical problems:

a preparation method of a Cr-Mo-Ag-Si-C-N multi-element composite film with wear resistance and antibiosis comprises the following steps:

(1) opening a cavity door of the closed unbalanced magnetron sputtering coating instrument, cleaning and drying a substrate, and installing a sample table in a cavity of the coating instrument;

(2) vacuumizing the cavity of the coating instrument to 2.0 x 10^-6Torr, simultaneously heating the vacuum cavity to 150 ℃, and accelerating the evaporation of residual water in the cavity;

(3) when the cavity is cooled to room temperature, introducing high-purity Ar gas, and cleaning and activating the surface of the substrate by utilizing Ar ion beams; after cleaning, continuously introducing Ar gas, starting a magnetron sputtering power supply, allowing the target material to run for 5min, and removing oxides attached to the surface of the target material;

(4) keeping introducing high-purity Ar gas, wherein the flow rate of the Ar gas is fixed to be 50 sccm; rotating the sample table, and setting the rotating speed to be 10 rpm; regulating the sputtering current of a Cr target to be 4.0A, negatively biasing the substrate to 80V, depositing for 10min, and preparing a Cr transition layer with the thickness of about 0.2 mu m on the substrate;

(5) ar gas and N are introduced₂Setting the sputtering current of a Cr target to be 4.0A and the deposition time to be 15min, and depositing a Cr-N gradient layer on the Cr transition layer; starting a magnetron sputtering direct-current power supply of the Mo target, gradually increasing the sputtering current of the Mo target to 2.0A, depositing for 15min, and further depositing a Cr-Mo-N gradient layer on the Cr-N gradient layer;

(6) introducing Ar gas and N₂The flow rate of TMS gas is fixed at 15sccm, and the pressure of the cavity is stabilized to 2.3 × 10^-3And Torr, starting a magnetron sputtering direct-current power supply of the Ag target, fixing the sputtering current of the Cr target and the Mo target, and preparing the Cr-Mo-Ag-Si-C-N multi-element composite film on the Cr-Mo-N gradient layer.

The substrate in the step (1) is any one of a monocrystalline silicon wafer, glass, stainless steel, high-speed steel and titanium alloy.

And (2) after the substrate is cleaned and dried in the step (1), specifically, ultrasonically cleaning the polished monocrystalline silicon wafer or titanium alloy in acetone, alcohol and deionized water in sequence, and drying by using a hair dryer.

And (3) introducing high-purity Ar gas, setting the flow rate of the Ar gas to be 50sccm, negatively biasing the substrate to 450V, and cleaning for 30 min.

In the step (5), the sputtering current of the Cr target is set to be 4.0A, the negative bias voltage of the substrate is-80V, the duty ratio is 50%, the OEM is 50%, and the deposition time is 15 min.

And (3) starting the magnetron sputtering direct-current power supply of the Ag target in the step (6), setting the sputtering current of the Ag target to be 0.2A-1.0A, the sputtering current of the fixed Cr target to be 4.0A, the sputtering current of the fixed Mo target to be 2.0A, negative bias of a substrate to 80V, duty ratio to be 50%, OEM to be 50%, and deposition time to be 50min-70 min.

The invention has the following beneficial effects:

(1) the preparation process is simple and easy to operate, and the film can be prepared at room temperature.

(2) There is no limitation on the choice of substrate material.

(3) The Cr, Mo and Ag content of the Cr-Mo-Ag-Si-C-N multi-component composite film can be adjusted by magnetron sputtering target current, the Si and C content can be adjusted by TMS gas flow rate, and the N content can be adjusted by OEM (rapid feedback optical emission monitor).

(4) The antibacterial performance of the Cr-Mo-Ag-Si-C-N multi-component composite film can be enhanced by increasing Ag target current.

Description of the drawings:

FIG. 1 shows the nanoindentation hardness and the elastic modulus of a Cr-Mo-Ag-Si-C-N multi-component composite film prepared by example 1 of the method of the present invention.

FIG. 2 shows the X-ray diffraction pattern of the Cr-Mo-Ag-Si-C-N multi-component composite film prepared in example 1 by the method of the present invention.

FIG. 3(a) is a scanning electron microscope image of the surface of the Cr-Mo-Ag-Si-C-N-0.2 multi-component composite film prepared by the method of example 1, the surface roughness of which is 34 nm; FIG. 3(b) is a scanning electron microscope image of the surface of the Cr-Mo-Ag-Si-C-N-0.4 multi-component composite film, the surface roughness is 35 nm; FIG. 3(C) is a scanning electron microscope image of the surface of the Cr-Mo-Ag-Si-C-N-0.6 multi-component composite film, the surface roughness is 37 nm; FIG. 3(d) is a scanning electron microscope image of the surface of the Cr-Mo-Ag-Si-C-N-0.8 multi-component composite film, the surface roughness is 40 nm; FIG. 3(e) is a scanning electron microscope image of the surface of the Cr-Mo-Ag-Si-C-N-1.0 multi-component composite film, the surface roughness of which is 45 nm.

FIG. 4(a) is a cross-sectional scanning electron microscope of the Cr-Mo-Ag-Si-C-N-0.2 multi-component composite film prepared by example 1 according to the method of the present invention; FIG. 4(b) is a cross-sectional scanning electron microscope image of the Cr-Mo-Ag-Si-C-N-0.4 multi-component composite film; FIG. 4(C) is a cross-sectional scanning electron micrograph of a Cr-Mo-Ag-Si-C-N-0.6 multi-component composite film; FIG. 4(d) is a cross-sectional scanning electron microscope of the Cr-Mo-Ag-Si-C-N-0.8 multi-component composite film; FIG. 4(e) is a sectional scanning electron microscope of the Cr-Mo-Ag-Si-C-N-1.0 multi-component composite film.

FIG. 5(a) friction coefficients of a Cr-Mo-Ag-Si-C-N multi-component composite film and a SiC ball prepared under different Ag target currents against grinding in artificial seawater; FIG. 5(b) average steady-state friction coefficient of the SiC ball and Cr-Mo-Ag-Si-C-N multi-component composite film prepared under different Ag target currents against grinding in artificial seawater.

FIG. 6 is a graph showing the anti-E.coli characteristics of Cr-Mo-Ag-Si-C-N multi-component composite films prepared at different Ag target currents.

FIG. 7 is a schematic diagram of the installation layout of the fixed substrate position and the metallic Cr, Mo and Ag targets in the closed unbalanced magnetron sputtering coating apparatus.

The specific implementation mode is as follows:

the invention is described in further detail below with reference to the accompanying drawings.

The Cr-Mo-Ag-Si-C-N multi-element composite film with both wear resistance and antibiosis is prepared by adopting a closed unbalanced magnetron sputtering coating instrument, and the method can deposit the Cr-Mo-Ag-Si-C-N multi-element composite film on almost all substrates under a simple manual operation instrument. The method comprises the following specific steps:

(1) opening a cavity door of the closed unbalanced magnetron sputtering coating instrument, cleaning and drying a substrate, and installing a sample table in a cavity of the coating instrument; the substrate can be any one of monocrystalline silicon piece, glass, stainless steel, high-speed steel and titanium alloy;

(2) vacuumizing the cavity of the coating instrument to 2.0 x 10^-6Torr, heating the vacuum cavity and keeping the temperature of the cavity at 150 ℃ simultaneously, and accelerating the evaporation of residual water in the cavity;

(3) and when the cavity is cooled to room temperature, introducing high-purity Ar gas, and cleaning and activating the surface of the substrate by utilizing Ar ion beams. The Ar gas flow rate is set to 50sccm, the substrate is negatively biased to-450V, and the cleaning time is 30 min. After cleaning, continuously introducing Ar gas, starting a magnetron sputtering power supply,

the target material is run for 5min, and oxides attached to the surface of the target material are removed;

(4) high-purity Ar gas is kept introduced, and the flow rate of the Ar gas is fixed at 50 sccm. The sample stage was rotated at a speed of 10 rpm. Regulating the sputtering current of a Cr target to be 4.0A, negatively biasing the substrate to 80V, depositing for 10min, and preparing a Cr transition layer with the thickness of about 0.2 mu m on the substrate;

(5) ar gas and N are introduced₂The rotating speed of the rotating sample table is set to 10rpm, the sputtering current of the Cr target is set to 4.0A, the negative bias voltage of a substrate is-80V, the duty ratio is 50 percent, and the OEM is 50 percent (N is controlled by a fast feedback optical emission detector)₂Flow rate while introducing Ar gas and N₂After the mixed gas of the gas is mixed, the OEM for generating nitride is set to be 50%), the deposition time is 15min, and a Cr-N gradient layer is deposited on the Cr transition layer; and starting a magnetron sputtering direct-current power supply of the Mo target, gradually increasing the sputtering current of the Mo target to 2.0A, and further depositing the Cr-Mo-N gradient layer on the Cr-N gradient layer for 15 min.

(6) Introducing Ar gas and N₂The flow rate of TMS gas is fixed at 15sccm, and the pressure of the cavity is stabilized to 2.3 × 10^-3Torr, the rotating speed of a rotating sample stage is set to 10rpm, a magnetron sputtering direct current power supply of an Ag target is started, the sputtering current of the Ag target is set to be 0.2A-1.0A, the sputtering current of a fixed Cr target is set to be 4.0A, the sputtering current of a fixed Mo target is set to be 2.0A, the negative bias voltage of a substrate is-80V, the duty ratio is 50%, and OEM is 50% (N is controlled by a fast feedback optical emission detector)₂Flow rate while introducing Ar gas and N₂And after the gas mixture, the OEM for generating nitride is set to be 50%), the deposition time is 50-70 min, and the Cr-Mo-Ag-Si-C-N multi-element composite film is prepared on the Cr-Mo-N gradient layer.

The preparation method of the Cr-Mo-Ag-Si-C-N multi-component composite film with both wear resistance and antibacterial property according to the present invention is illustrated by the following specific examples.

The embodiment of the invention is implemented according to the following steps:

(1) substrate and target preparation

The single crystal Si (100) plate was cut into a size of 6X 6cm using a natural diamond glass cutter²Small blocks; machining the Ti6Al4V titanium alloy into a titanium alloy through lathe cutting

The wafer (2) has a surface roughness of 100nm or less (Ra. ltoreq.100 nm) by polishing and buffing. And (3) ultrasonically cleaning a single crystal Si (100) sheet and a polished Ti6Al4V titanium alloy wafer in acetone, alcohol and deionized water in sequence, drying by using a hair drier, and clamping on a sample table in a cavity of a coating instrument. Four targets of 2 Cr targets, 1 Mo target and 1 Ag target were used and mounted in a coating apparatus as shown in FIG. 7.

(2) Target and substrate ion cleaning

The background vacuum degree reaches 1.5 multiplied by 10^-6And when the Torr is used, introducing Ar gas (60sccm), setting the negative bias of the substrate to be 600V and the duty ratio to be 50 percent, and bombarding the surface of the substrate by utilizing Ar ions to remove pollutants on the surface and activate the deposition surface. After the cleaning, the metal Cr target, the Mo target and the Ag target were run for 10min while keeping the flow rate of Ar gas at 60sccm, so as to remove the oxides attached to the surface of the target material.

(3) Film preparation

High-purity Ar gas is kept introduced, and the flow rate of the Ar gas is fixed at 60 sccm. The sample stage was rotated at a speed of 10 rpm. The sputtering current of the Cr target is adjusted to be 4.0A, the negative bias voltage of the substrate is minus 100V, the deposition time is 10min, and a Cr transition layer with the thickness of about 0.2 mu m is prepared on the substrate. Ar gas and N are introduced₂Setting the sputtering current of a Cr target to be 4.0A, negative bias voltage-80V of a substrate, duty ratio of 50 percent, OEM (original equipment manufacture) to be 50 percent, and deposition time to be 20min for mixed gas of gas, and depositing a Cr-N gradient layer on the Cr transition layer; and starting a magnetron sputtering direct-current power supply of the Mo target, gradually increasing the sputtering current of the Mo target to 4.0A, and further depositing the Cr-Mo-N gradient layer on the Cr-N gradient layer for 20 min. Introducing Ar gas and N₂The flow rate of TMS gas is fixed at 15sccm, and the pressure of the cavity is stabilized to 2.3 × 10^-3Torr, starting the magnetron sputtering DC power supply of the Ag target and setting the sputtering of the Ag targetThe jet current is 0.4A-2.0A, the fixed Cr target sputtering current is 4.0A, the fixed Mo target sputtering current is 4.0A, the substrate negative bias voltage is-100V, the duty ratio is 50%, the OEM (original equipment manufacture) is 50%, the deposition time is 60min-80min, and the Cr-Mo-Ag-Si-C-N multi-element composite film is prepared on the Cr-Mo-N gradient layer.

Example 1

(1) Substrate and target preparation

The single crystal Si (100) sheet was cut into a size of 10X 10cm using a natural diamond glass cutter²Small blocks; machining the Ti6Al4V titanium alloy into a titanium alloy through lathe cutting

The wafer (2) has a surface roughness of 30nm or less (Ra. ltoreq.30 nm) by polishing and buffing. And (3) ultrasonically cleaning a single crystal Si (100) sheet and a polished Ti6Al4V titanium alloy wafer in acetone, alcohol and deionized water in sequence, drying by using a hair drier, and clamping on a sample table in a cavity of a coating instrument. Four targets, 2 Cr targets, 1 Mo target and 1 Ag target, are used and installed in a coating instrument.

(2) Target and substrate ion beam cleaning

The background vacuum degree reaches 2.0 multiplied by 10^-6And when the Torr is used, introducing Ar gas (50sccm), setting the negative bias of-450V of the substrate and the duty ratio of 50%, bombarding the surface of the substrate by utilizing Ar ions, and removing pollutants on the surface of the substrate and activating the deposition surface. After the cleaning, the metal Cr target, the Mo target and the Ag target were run for 5min while keeping the flow rate of Ar at 50sccm, to remove the oxides attached to the surface of the target.

(3) Film preparation

High-purity Ar gas is kept introduced, and the flow rate of the Ar gas is fixed at 50 sccm. The sample stage was rotated at a speed of 10 rpm. The sputtering current of the Cr target is adjusted to be 4.0A, the negative bias voltage of the substrate is minus 80V, the deposition time is 10min, and a Cr transition layer with the thickness of about 0.2 mu m is prepared on the substrate. Ar gas and N are introduced₂Setting the sputtering current of a Cr target to be 4.0A, negative bias voltage-80V of a substrate, duty ratio of 50 percent, OEM (original equipment manufacture) to be 50 percent and deposition time of 15min for mixed gas of gas, and depositing a Cr-N gradient layer on the Cr transition layer; starting a magnetron sputtering direct-current power supply of the Mo target, gradually increasing the sputtering current of the Mo target to 2.0A, wherein the deposition time is 15min, and performing magnetron sputtering on a Cr-N ladderAnd a Cr-Mo-N gradient layer is further deposited on the gradient layer. Introducing Ar gas and N₂The flow rate of TMS gas is fixed at 15sccm, and the pressure of the cavity is stabilized to 2.3 × 10^-3And Torr, starting a magnetron sputtering direct-current power supply of the Ag target, setting the sputtering current of the Ag target to be 0.2A-1.0A, the sputtering current of the fixed Cr target to be 4.0A, the sputtering current of the fixed Mo target to be 2.0A, negative bias of a substrate to be 80V, duty ratio to be 50%, OEM to be 50%, deposition time to be 50min-70min, and preparing the Cr-Mo-Ag-Si-C-N multi-element composite film on the Cr-Mo-N gradient layer.

(4) Detection of thin films

1) Measurement of hardness: the hardness of the Cr-Mo-Ag-Si-C-N multi-component composite film was measured by a diamond nanoindenter, as shown in FIG. 1.

2) Determination of crystal phase structure: the crystal phase structure of the Cr-Mo-Ag-Si-C-N multi-component composite film was determined by X-ray diffraction spectroscopy, as shown in FIG. 2.

3) Analysis of SEM morphology: the surface morphology of the Cr-Mo-Ag-Si-C-N multi-component composite film is observed by a field emission scanning electron microscope, which is shown in figure 3.

4) Analysis of SEM morphology: the cross-sectional morphology of the Cr-Mo-Ag-Si-C-N multi-component composite film was observed by a field emission scanning electron microscope, see FIG. 4.

5) Testing of the coefficient of friction: the friction coefficient of the Cr-Mo-Ag-Si-C-N multi-element composite film and the SiC ball in the artificial seawater for grinding is recorded by a friction tester, and is shown in figure 5.

6) And (3) testing of antibacterial performance: after the film was completely immersed in the E.coli solution for a period of time, the anti-E.coli properties of the Cr-Mo-Ag-Si-C-N multi-component composite film were measured by a bacterial counting method, see FIG. 6.

(5) Evaluation of abrasion resistance and antibacterial property of film

The Cr-Mo-Ag-Si-C-N multi-element composite film and the SiC ball are oppositely ground in artificial seawater to obtain the following product: the friction coefficients of Cr-Mo-Ag-Si-C-N films prepared by different Ag target currents are all 0.145-0.175, and Si (OH) is formed by friction chemical reaction of friction pairs under the condition of water lubrication₄、MoO₃The lubricity of the antifriction lubricating layer and Ag at the friction interface is critical for low coefficient of friction. Cr (chromium) componentthe-Mo-Ag-Si-C-N film shows good wear resistance. Among them, the average steady state friction coefficient of Cr-Mo-Ag-Si-C-N films prepared at an Ag target current of 0.4A was the lowest, only 0.146. This is attributable to its highest hardness and highest hard-to-elastic ratio.

Completely immersing the Cr-Mo-Ag-Si-C-N multi-element composite film in the escherichia coli liquid for 6 hours and 12 hours, and then counting the escherichia coli liquid after the experiment again to obtain the following results: the Cr-Mo-Ag-Si-C-N multi-element composite film prepared under the low Ag target current (0.2A) shows a certain bactericidal property within the immersion time of 6 hours, and the film does not play a bactericidal role any more after 12 hours. The reason is that the original film has a low Ag content, and the surface of the film has Ag on the surface for a period of time⁺After releasing, Ag is not released and diffused on the surface of the film⁺And an antibacterial effect is not formed. For Cr-Mo-Ag-Si-C-N multi-element composite films prepared under high Ag target currents (0.6A and 1.0A), the films have good killing performance on escherichia coli within 6 hours or 12 hours of immersion time. With the increase of Ag target current and immersion time, the antibacterial effect of the film is better and better. The Cr-Mo-Ag-Si-C-N multi-component composite film prepared under the highest Ag target current (1.0A) is beneficial to more Ag due to the largest area of the Ag particles covered on the surface and the highest surface Ag content⁺Release and diffusion. In Ag⁺After reacting with and binding to thiol groups in E.coli, the action of enzymes in the bacteria is destroyed and the bacteria are killed. In addition, Ag⁺It can also diffuse through the fluid environment and into the cell membrane, thereby disrupting and destroying the cell membrane. The Cr-Mo-Ag-Si-C-N multi-element composite film prepared under the highest Ag target current (1.0A) shows the most excellent antibacterial performance.

In summary, it can be found that: the Cr-Mo-Ag-Si-C-N multi-element composite film prepared by the invention has good wear resistance and excellent antibacterial property, and is a multifunctional film with both wear resistance and antibacterial property.

Example 2

(1) Substrate and target preparation

Cutting the single crystal Si (100) plate into 6 × 6cm size with a natural diamond knife²Is cut into small blocks by spark wire

The high-speed steel (W6Mo5Cr4V2) wafer is prepared by grinding and polishing the high-speed steel until the roughness Ra is 100nm, ultrasonically cleaning a single crystal Si (100) wafer and the polished high-speed steel wafer in acetone, alcohol and deionized water in sequence, drying by using a hair drier, and clamping on a sample table in a cavity of a coating instrument. Four targets, namely 1 Cr target, 1 Mo target, 1 Ag target and 1 Si target, are used and are arranged in a coating instrument.

(2) Target and substrate ion cleaning

The background vacuum degree reaches 2.0 multiplied by 10^-6And when the Torr is used, introducing Ar gas (60sccm), setting the negative bias of the substrate to be 600V and the duty ratio to be 50 percent, and bombarding the surface of the substrate by utilizing Ar ions to remove pollutants on the surface and activate the deposition surface. After cleaning, the Ar gas flow rate is kept at 60sccm, and the metal Cr target, the Mo target, the Ag target and the non-metal Si target are run for 10min to remove the oxides attached to the surface of the target material.

(3) Film preparation

High-purity Ar gas is kept introduced, and the flow rate of the Ar gas is fixed at 60 sccm. The sample stage was rotated at a speed of 10 rpm. The sputtering current of the Cr target is adjusted to be 4.0A, the negative bias voltage of the substrate is minus 100V, the deposition time is 10min, and a Cr transition layer with the thickness of about 0.2 mu m is prepared on the substrate. Ar gas and N are introduced₂Setting the sputtering current of a Cr target to be 4.0A, negative bias voltage-80V of a substrate, duty ratio of 50 percent, OEM (original equipment manufacture) to be 50 percent and deposition time of 15min for mixed gas of gas, and depositing a Cr-N gradient layer on the Cr transition layer; and starting a magnetron sputtering direct-current power supply of the Mo target, gradually increasing the sputtering current of the Mo target to 2.0A, and further depositing the Cr-Mo-N gradient layer on the Cr-N gradient layer for 15 min. Introducing Ar gas and N₂Gas and C₂H₂Gas mixture of gases, C₂H₂The gas flow rate is fixed at 15sccm, and the gas pressure in the cavity is stabilized to 2.3 × 10^-3Torr, starting a magnetron sputtering direct current power supply of a metal Ag target and a non-metal Si target, setting the sputtering current of the Ag target to be 0.2A-1.0A, the sputtering current of a fixed Si target to be 2.0A, the sputtering current of a fixed Cr target to be 4.0A, the sputtering current of a fixed Mo target to be 2.0A, negative bias voltage of a substrate to 100V, duty ratio of 50 percent and OEM (original equipment manufacture) to be 50 percent, and sinkingThe deposition time is 50min-70min, and the Cr-Mo-Ag-Si-C-N multi-element composite film is prepared on the Cr-Mo-N gradient layer.

(4) Evaluation of abrasion resistance and antibacterial property of film

Si (OH) formed by the tribochemical reaction of friction pairs under water-lubricated conditions, as described in example 1₄、MoO₃The lubricity of the antifriction lubricating layer and Ag at the friction interface is critical for low coefficient of friction. The Cr-Mo-Ag-Si-C-N film shows good wear resistance. As described in example 1, the Cr-Mo-Ag-Si-C-N multi-component composite film prepared at a low Ag target current (0.2A) shows a certain bactericidal activity within a immersion time of 6h, and after 12h, the film does not play a bactericidal role any more. The reason is that the original film has a low Ag content, and the surface of the film has Ag on the surface for a period of time⁺After releasing, Ag is not released and diffused on the surface of the film⁺And an antibacterial effect is not formed. For Cr-Mo-Ag-Si-C-N multi-element composite films prepared under high Ag target currents (0.6A and 1.0A), the films have good killing performance on escherichia coli within 6 hours or 12 hours of immersion time. With the increase of Ag target current and immersion time, the antibacterial effect of the film is better and better. The Cr-Mo-Ag-Si-C-N multi-component composite film prepared under the highest Ag target current (1.0A) is beneficial to more Ag due to the largest area of the Ag particles covered on the surface and the highest surface Ag content⁺Release and diffusion. In Ag⁺After reacting with and binding to thiol groups in E.coli, the action of enzymes in the bacteria is destroyed and the bacteria are killed. In addition, Ag⁺It can also diffuse through the fluid environment and into the cell membrane, thereby disrupting and destroying the cell membrane. The Cr-Mo-Ag-Si-C-N multi-element composite film prepared under the highest Ag target current (1.0A) shows the most excellent antibacterial performance.

In summary, it can be found that: the Cr-Mo-Ag-Si-C-N multi-element composite film prepared by the invention has good wear resistance and excellent antibacterial property, and is a multifunctional film with both wear resistance and antibacterial property.

Example 3

(1) Substrate and target preparation

Using a natural diamond knife to make a single crystal Si (100) plateCutting into 6 × 6cm²Is cut into small blocks by spark wire

The high-speed steel (W6Mo5Cr4V2) wafer is prepared by grinding and polishing the high-speed steel until the roughness Ra is 100nm, ultrasonically cleaning a single crystal Si (100) wafer and the polished high-speed steel wafer in acetone, alcohol and deionized water in sequence, drying by using a hair drier, and clamping on a sample table in a cavity of a coating instrument. Four targets, namely 1 Cr target, 1 Mo target, 1 Ag target and 1C target, are used and are arranged in a coating instrument.

(2) Target and substrate ion cleaning

The background vacuum degree reaches 2.0 multiplied by 10^-6And when the Torr is used, introducing Ar gas (60sccm), setting the negative bias of the substrate to be 600V and the duty ratio to be 50 percent, and bombarding the surface of the substrate by utilizing Ar ions to remove pollutants on the surface and activate the deposition surface. After cleaning, the Ar gas flow rate is kept at 60sccm, and the metal Cr target, the Mo target, the Ag target and the nonmetal C target are idle run for 10min to remove the oxides attached to the surface of the target material.

(3) Film preparation

High-purity Ar gas is kept introduced, and the flow rate of the Ar gas is fixed at 60 sccm. The sample stage was rotated at a speed of 10 rpm. The sputtering current of the Cr target is adjusted to be 4.0A, the negative bias voltage of the substrate is minus 100V, the deposition time is 10min, and a Cr transition layer with the thickness of about 0.2 mu m is prepared on the substrate. Ar gas and N are introduced₂Setting the sputtering current of a Cr target to be 4.0A, negative bias voltage-80V of a substrate, duty ratio of 50 percent, OEM (original equipment manufacture) to be 50 percent and deposition time of 15min for mixed gas of gas, and depositing a Cr-N gradient layer on the Cr transition layer; and starting a magnetron sputtering direct-current power supply of the Mo target, gradually increasing the sputtering current of the Mo target to 2.0A, and further depositing the Cr-Mo-N gradient layer on the Cr-N gradient layer for 15 min. Introducing Ar gas and N₂The flow rate of TMS gas is fixed at 15sccm, and the pressure of the cavity is stabilized to 2.3 × 10^-3Torr, starting magnetron sputtering direct current power supply of metal Ag target and non-metal C target, setting the sputtering current of Ag target to be 0.2A-1.0A, the sputtering current of fixed C target to be 2.0A, the sputtering current of fixed Cr target to be 4.0A, the sputtering current of fixed Mo target to be 2.0A, and negative bias of substrate to be-100V, duty ratio of 50 percent, OEM 50 percent, deposition time of 50min-70min, and preparing the Cr-Mo-Ag-Si-C-N multi-element composite film on the Cr-Mo-N gradient layer.

(4) Evaluation of abrasion resistance and antibacterial property of film

Si (OH) formed by the tribochemical reaction of friction pairs under water-lubricated conditions, as described in example 1₄、MoO₃The lubricity of the antifriction lubricating layer and Ag at the friction interface is critical for low coefficient of friction. The Cr-Mo-Ag-Si-C-N film shows good wear resistance.

As described in example 1, the Cr-Mo-Ag-Si-C-N multi-component composite film prepared at a low Ag target current (0.2A) shows a certain bactericidal activity within a immersion time of 6h, and after 12h, the film does not play a bactericidal role any more. The reason is that the original film has a low Ag content, and the surface of the film has Ag on the surface for a period of time⁺After releasing, Ag is not released and diffused on the surface of the film⁺And an antibacterial effect is not formed. For Cr-Mo-Ag-Si-C-N multi-element composite films prepared under high Ag target currents (0.6A and 1.0A), the films have good killing performance on escherichia coli within 6 hours or 12 hours of immersion time. With the increase of Ag target current and immersion time, the antibacterial effect of the film is better and better. The Cr-Mo-Ag-Si-C-N multi-component composite film prepared under the highest Ag target current (1.0A) is beneficial to more Ag due to the largest area of the Ag particles covered on the surface and the highest surface Ag content⁺Release and diffusion. In Ag⁺After reacting with and binding to thiol groups in E.coli, the action of enzymes in the bacteria is destroyed and the bacteria are killed. In addition, Ag⁺It can also diffuse through the fluid environment and into the cell membrane, thereby disrupting and destroying the cell membrane. The Cr-Mo-Ag-Si-C-N multi-element composite film prepared under the highest Ag target current (1.0A) shows the most excellent antibacterial performance.

In summary, it can be found that: the Cr-Mo-Ag-Si-C-N multi-element composite film prepared by the invention has good wear resistance and excellent antibacterial property, and is a multifunctional film with both wear resistance and antibacterial property.

Example 4

(1) Substrate and target preparation

Cutting the single crystal Si (100) plate into 6 × 6cm size with a natural diamond knife²Is cut into small blocks by spark wire

The high-speed steel (W6Mo5Cr4V2) wafer is prepared by grinding and polishing the high-speed steel until the roughness Ra is 100nm, ultrasonically cleaning a single crystal Si (100) wafer and the polished high-speed steel wafer in acetone, alcohol and deionized water in sequence, drying by using a hair drier, and clamping on a sample table in a cavity of a coating instrument. Four targets, namely 1 Cr target, 1 Mo target, 1 Ag target and 1 Si target, are used and are arranged in a coating instrument.

(2) Target and substrate ion cleaning

The background vacuum degree reaches 2.0 multiplied by 10^-6And when the Torr is used, introducing Ar gas (60sccm), setting the negative bias of the substrate to be 600V and the duty ratio to be 50 percent, and bombarding the surface of the substrate by utilizing Ar ions to remove pollutants on the surface and activate the deposition surface. After cleaning, the Ar gas flow rate is kept at 60sccm, and the metal Cr target, the Mo target, the Ag target and the non-metal Si target are run for 10min to remove the oxides attached to the surface of the target material.

(3) Film preparation

High-purity Ar gas is kept introduced, and the flow rate of the Ar gas is fixed at 60 sccm. The sample stage was rotated at a speed of 10 rpm. The sputtering current of the Cr target is adjusted to be 4.0A, the negative bias voltage of the substrate is minus 100V, the deposition time is 10min, and a Cr transition layer with the thickness of about 0.2 mu m is prepared on the substrate. Ar gas and N are introduced₂Setting the sputtering current of a Cr target to be 4.0A, negative bias voltage-80V of a substrate, duty ratio of 50 percent, OEM (original equipment manufacture) to be 50 percent and deposition time of 15min for mixed gas of gas, and depositing a Cr-N gradient layer on the Cr transition layer; and starting a magnetron sputtering direct-current power supply of the Mo target, gradually increasing the sputtering current of the Mo target to 2.0A, and further depositing the Cr-Mo-N gradient layer on the Cr-N gradient layer for 15 min. Ar gas and N are introduced₂Gas mixture of gases until the pressure of the cavity is stabilized to 2.3 × 10^-3Torr, starting magnetron sputtering direct current power supply of a metal Ag target and a non-metal Si target, setting the sputtering current of the Ag target to be 0.2A-1.0A, the sputtering current of the fixed Si target to be 2.0A, the sputtering current of the fixed Cr target to be 4.0A, and the sputtering current of the fixed Mo target to be 2And 0A, preparing the Cr-Mo-Ag-Si-N multi-element composite film on the Cr-Mo-N gradient layer, wherein the substrate is negatively biased to 100V, the duty ratio is 50%, the OEM is 50%, and the deposition time is 50-70 min.

(4) Evaluation of abrasion resistance and antibacterial property of film

Si (OH) formed by the tribochemical reaction of friction pairs under water-lubricated conditions, as described in example 1₄、MoO₃The lubricity of the antifriction lubricating layer and Ag at the friction interface is critical for low coefficient of friction. The Cr-Mo-Ag-Si-N film shows good wear resistance.

As described in example 1, the Cr-Mo-Ag-Si-N multi-component composite film prepared at a low Ag target current (0.2A) shows a certain bactericidal activity within a immersion time of 6h, and after 12h, the film will not perform the bactericidal activity any more. The reason is that the original film has a low Ag content, and the surface of the film has Ag on the surface for a period of time⁺After releasing, Ag is not released and diffused on the surface of the film⁺And an antibacterial effect is not formed. For Cr-Mo-Ag-Si-N multi-element composite films prepared under high Ag target current (0.6A and 1.0A), the films have good killing performance on escherichia coli within 6 hours or 12 hours of immersion time. With the increase of Ag target current and immersion time, the antibacterial effect of the film is better and better. The Cr-Mo-Ag-Si-N multi-component composite film prepared under the highest Ag target current (1.0A) is beneficial to more Ag due to the largest area of the Ag particles covered on the surface and the highest surface Ag content⁺Release and diffusion. In Ag⁺After reacting with and binding to thiol groups in E.coli, the action of enzymes in the bacteria is destroyed and the bacteria are killed. In addition, Ag⁺It can also diffuse through the fluid environment and into the cell membrane, thereby disrupting and destroying the cell membrane. The Cr-Mo-Ag-Si-N multi-element composite film prepared under the highest Ag target current (1.0A) shows the most excellent antibacterial performance.

In summary, it can be found that: the Cr-Mo-Ag-Si-N multi-element composite film prepared by the invention has good wear resistance and excellent antibacterial property, and is a multifunctional film with both wear resistance and antibacterial property.

Example 5

(1) Substrate and target preparation

By cutting with a lathe

The 316L stainless steel and the high-speed steel (W6Mo5Cr4V2) are used as substrates, the surface roughness of the substrates is less than 70nm (Ra is less than or equal to 70nm) through grinding and polishing, the substrates are sequentially subjected to ultrasonic cleaning in acetone, alcohol and deionized water, dried by using a hair drier, and clamped on a sample table in a cavity of a coating instrument. Four targets, namely 1 Cr target, 1 Mo target, 1 Ag target and 1C target, are used and are arranged in a coating instrument.

(2) Target and substrate ion cleaning

The background vacuum degree reaches 3.0 multiplied by 10^-6And when the Torr is used, introducing Ar gas (50sccm), setting the negative bias of-450V of the substrate and the duty ratio of 50%, bombarding the surface of the substrate by utilizing Ar ions, and removing pollutants on the surface of the substrate and activating the deposition surface. After the cleaning, the metal Cr target, Mo target, Ag target and C target were run for 5min while keeping the Ar gas flow rate at 50sccm, to remove the oxides attached to the surface of the target material.

(3) Film preparation

High-purity Ar gas is kept introduced, and the flow rate of the Ar gas is fixed at 50 sccm. The sample stage was rotated at a speed of 10 rpm. The sputtering current of the Cr target is adjusted to be 4.0A, the negative bias voltage of the substrate is minus 80V, the deposition time is 10min, and a Cr transition layer with the thickness of about 0.2 mu m is prepared on the substrate. Ar gas and N are introduced₂Setting the sputtering current of a Cr target to be 4.0A, negative bias voltage-80V of a substrate, duty ratio of 50 percent, OEM (original equipment manufacture) to be 50 percent and deposition time of 15min for mixed gas of gas, and depositing a Cr-N gradient layer on the Cr transition layer; and starting a magnetron sputtering direct-current power supply of the Mo target, gradually increasing the sputtering current of the Mo target to 2.0A, and further depositing the Cr-Mo-N gradient layer on the Cr-N gradient layer for 15 min. Ar gas and N are introduced₂Gas mixture of gases until the pressure of the cavity is stabilized to 2.3 × 10^-3Torr, starting a magnetron sputtering direct-current power supply of an Ag target, setting the sputtering current of the Ag target to be 0.2A-1.0A, the sputtering current of a fixed Cr target to be 4.0A, the sputtering current of a fixed Mo target to be 2.0A, the sputtering current of a fixed C target to be 2.0A, negative bias voltage of a substrate to 80V, duty ratio of 50 percent, OEM (original equipment manufacturer) to 50 percent, deposition time of 50min-70min, and preparing Cr-Mo-Ag-C-N multi-component composite thin film on a Cr-Mo-N gradient layerAnd (3) a membrane.

(4) Evaluation of abrasion resistance and antibacterial property of film

Si (OH) formed by the tribochemical reaction of friction pairs under water-lubricated conditions, as described in example 1₄、MoO₃The lubricity of the antifriction lubricating layer and Ag at the friction interface is critical for low coefficient of friction. The Cr-Mo-Ag-C-N film shows good wear resistance.

As described in example 1, the Cr-Mo-Ag-C-N multi-component composite film prepared at low Ag target current (0.2A) shows a certain bactericidal activity within a immersion time of 6h, and after 12h, the film will not perform the bactericidal activity any more. The reason is that the original film has a low Ag content, and the surface of the film has Ag on the surface for a period of time⁺After releasing, Ag is not released and diffused on the surface of the film⁺And an antibacterial effect is not formed. For Cr-Mo-Ag-C-N multi-component composite films prepared under high Ag target current (0.6A and 1.0A), the films have good killing performance on escherichia coli within 6 hours or 12 hours of immersion time. With the increase of Ag target current and immersion time, the antibacterial effect of the film is better and better. The Cr-Mo-Ag-C-N multi-component composite film prepared under the highest Ag target current (1.0A) is beneficial to more Ag due to the largest area of the Ag particles covered on the surface and the highest surface Ag content⁺Release and diffusion. In Ag⁺After reacting with and binding to thiol groups in E.coli, the action of enzymes in the bacteria is destroyed and the bacteria are killed. In addition, Ag⁺It can also diffuse through the fluid environment and into the cell membrane, thereby disrupting and destroying the cell membrane. The Cr-Mo-Ag-C-N multi-element composite film prepared under the highest Ag target current (1.0A) shows the most excellent antibacterial performance.

In summary, it can be found that: the Cr-Mo-Ag-C-N multi-element composite film prepared by the invention has good wear resistance and excellent antibacterial property, and is a multifunctional film with both wear resistance and antibacterial property.

Example 6

(1) Substrate and target preparation

By cutting with a lathe

The 316L stainless steel and the high-speed steel (W6Mo5Cr4V2) are used as substrates, the surface roughness of the substrates is less than 70nm (Ra is less than or equal to 70nm) through grinding and polishing, the substrates are sequentially subjected to ultrasonic cleaning in acetone, alcohol and deionized water, dried by using a hair drier, and clamped on a sample table in a cavity of a coating instrument. Four targets, 2 Cr targets, 1 Mo target and 1 Ag target, were used and mounted in a coating apparatus.

(2) Target and substrate ion cleaning

The background vacuum degree reaches 3.0 multiplied by 10^-6And when the Torr is used, introducing Ar gas (50sccm), setting the negative bias of-450V of the substrate and the duty ratio of 50%, bombarding the surface of the substrate by utilizing Ar ions, and removing pollutants on the surface of the substrate and activating the deposition surface. After the cleaning, the metal Cr target, the Mo target and the Ag target were run for 5min while keeping the flow rate of Ar at 50sccm, to remove the oxides attached to the surface of the target.

(3) Film preparation

High-purity Ar gas is kept introduced, and the flow rate of the Ar gas is fixed at 50 sccm. The sample stage was rotated at a speed of 10 rpm. The sputtering current of the Cr target is adjusted to be 4.0A, the negative bias voltage of the substrate is minus 80V, the deposition time is 10min, and a Cr transition layer with the thickness of about 0.2 mu m is prepared on the substrate. Ar gas and N are introduced₂Setting the sputtering current of a Cr target to be 4.0A, negative bias voltage-80V of a substrate, duty ratio of 50 percent, OEM (original equipment manufacture) to be 50 percent and deposition time of 15min for mixed gas of gas, and depositing a Cr-N gradient layer on the Cr transition layer; and starting a magnetron sputtering direct-current power supply of the Mo target, gradually increasing the sputtering current of the Mo target to 2.0A, and further depositing the Cr-Mo-N gradient layer on the Cr-N gradient layer for 15 min. Introducing Ar gas and N₂Gas and C₂H₂Gas mixture of gases, C₂H₂The gas flow rate is fixed at 15sccm, and the gas pressure in the cavity is stabilized to 2.3 × 10^-3And Torr, starting a magnetron sputtering direct-current power supply of the Ag target, setting the sputtering current of the Ag target to be 0.2A-1.0A, the sputtering current of the fixed Cr target to be 4.0A, the sputtering current of the fixed Mo target to be 2.0A, negative bias of a substrate to be 80V, duty ratio to be 50%, OEM to be 50%, deposition time to be 50min-70min, and preparing the Cr-Mo-Ag-C-N multi-element composite film on the Cr-Mo-N gradient layer.

(4) Evaluation of abrasion resistance and antibacterial property of film

Si (OH) formed by the tribochemical reaction of friction pairs under water-lubricated conditions, as described in example 1₄、MoO₃The lubricity of the antifriction lubricating layer and Ag at the friction interface is critical for low coefficient of friction. The Cr-Mo-Ag-C-N film shows good wear resistance.

As described in example 1, the Cr-Mo-Ag-C-N multi-component composite film prepared at low Ag target current (0.2A) shows a certain bactericidal activity within a immersion time of 6h, and after 12h, the film will not perform the bactericidal activity any more. The reason is that the original film has a low Ag content, and the surface of the film has Ag on the surface for a period of time⁺After releasing, Ag is not released and diffused on the surface of the film⁺And an antibacterial effect is not formed. For Cr-Mo-Ag-C-N multi-component composite films prepared under high Ag target current (0.6A and 1.0A), the films have good killing performance on escherichia coli within 6 hours or 12 hours of immersion time. With the increase of Ag target current and immersion time, the antibacterial effect of the film is better and better. The Cr-Mo-Ag-C-N multi-component composite film prepared under the highest Ag target current (1.0A) is beneficial to more Ag due to the largest area of the Ag particles covered on the surface and the highest surface Ag content⁺Release and diffusion. In Ag⁺After reacting with and binding to thiol groups in E.coli, the action of enzymes in the bacteria is destroyed and the bacteria are killed. In addition, Ag⁺It can also diffuse through the fluid environment and into the cell membrane, thereby disrupting and destroying the cell membrane. The Cr-Mo-Ag-C-N multi-element composite film prepared under the highest Ag target current (1.0A) shows the most excellent antibacterial performance.

In summary, it can be found that: the Cr-Mo-Ag-C-N multi-element composite film prepared by the invention has good wear resistance and excellent antibacterial property, and is a multifunctional film with both wear resistance and antibacterial property.

Example 7

(1) Substrate and target preparation

By cutting with a lathe

316L stainless steel and high-speed steel (W6Mo5Cr4V2) as substratesAnd grinding and polishing to ensure that the surface roughness is below 70nm (Ra is less than or equal to 70nm), sequentially carrying out ultrasonic cleaning in acetone, alcohol and deionized water, drying by using a hair drier, and clamping on a sample table in a cavity of the coating instrument. Four targets, namely 1 Cr target, 1 Mo target, 1 Ag target and 1C target, are used and are arranged in a coating instrument.

(2) Target and substrate ion cleaning

The background vacuum degree reaches 3.0 multiplied by 10^-6And when the Torr is used, introducing Ar gas (50sccm), setting the negative bias of-450V of the substrate and the duty ratio of 50%, bombarding the surface of the substrate by utilizing Ar ions, and removing pollutants on the surface of the substrate and activating the deposition surface. After the cleaning, the metal Cr target, Mo target, Ag target and C target were run for 5min while keeping the Ar gas flow rate at 50sccm, to remove the oxides attached to the surface of the target material.

(3) Film preparation

High-purity Ar gas is kept introduced, and the flow rate of the Ar gas is fixed at 50 sccm. The sample stage was rotated at a speed of 10 rpm. The sputtering current of the Cr target is adjusted to be 4.0A, the negative bias voltage of the substrate is minus 80V, the deposition time is 10min, and a Cr transition layer with the thickness of about 0.2 mu m is prepared on the substrate. Ar gas and N are introduced₂Setting the sputtering current of a Cr target to be 4.0A, negative bias voltage-80V of a substrate, duty ratio of 50 percent, OEM (original equipment manufacture) to be 50 percent and deposition time of 15min for mixed gas of gas, and depositing a Cr-N gradient layer on the Cr transition layer; and starting a magnetron sputtering direct-current power supply of the Mo target, gradually increasing the sputtering current of the Mo target to 2.0A, and further depositing the Cr-Mo-N gradient layer on the Cr-N gradient layer for 15 min. Introducing Ar gas and N₂Gas and C₂H₂Gas mixture of gases, C₂H₂The gas flow rate is fixed at 15sccm, and the gas pressure in the cavity is stabilized to 2.3 × 10^-3And Torr, starting a magnetron sputtering direct-current power supply of the Ag target, setting the sputtering current of the Ag target to be 0.2A-1.0A, the sputtering current of the fixed Cr target to be 4.0A, the sputtering current of the fixed Mo target to be 2.0A, the sputtering current of the fixed C target to be 2.0A, negative bias voltage of a substrate to 80V, duty ratio of 50 percent, OEM (original equipment manufacturer) to 50 percent, deposition time of 50min-70min, and preparing the Cr-Mo-Ag-C-N multi-element composite film on the Cr-Mo-N gradient layer.

(4) Evaluation of abrasion resistance and antibacterial property of film

Under water-lubricated conditions, as described in example 1Si (OH) formed by tribochemical reaction of friction pair₄、MoO₃The lubricity of the antifriction lubricating layer and Ag at the friction interface is critical for low coefficient of friction. The Cr-Mo-Ag-C-N film shows good wear resistance.

As described in example 1, the Cr-Mo-Ag-C-N multi-component composite film prepared at low Ag target current (0.2A) shows a certain bactericidal activity within a immersion time of 6h, and after 12h, the film will not perform the bactericidal activity any more. The reason is that the original film has a low Ag content, and the surface of the film has Ag on the surface for a period of time⁺After releasing, Ag is not released and diffused on the surface of the film⁺And an antibacterial effect is not formed. For Cr-Mo-Ag-C-N multi-component composite films prepared under high Ag target current (0.6A and 1.0A), the films have good killing performance on escherichia coli within 6 hours or 12 hours of immersion time. With the increase of Ag target current and immersion time, the antibacterial effect of the film is better and better. The Cr-Mo-Ag-C-N multi-component composite film prepared under the highest Ag target current (1.0A) is beneficial to more Ag due to the largest area of the Ag particles covered on the surface and the highest surface Ag content⁺Release and diffusion. In Ag⁺After reacting with and binding to thiol groups in E.coli, the action of enzymes in the bacteria is destroyed and the bacteria are killed. In addition, Ag⁺It can also diffuse through the fluid environment and into the cell membrane, thereby disrupting and destroying the cell membrane. The Cr-Mo-Ag-C-N multi-element composite film prepared under the highest Ag target current (1.0A) shows the most excellent antibacterial performance.

In summary, it can be found that: the Cr-Mo-Ag-C-N multi-element composite film prepared by the invention has good wear resistance and excellent antibacterial property, and is a multifunctional film with both wear resistance and antibacterial property.

Example 8

(1) Substrate and target preparation

The single crystal Si (100) sheet was cut into a size of 10X 10cm using a natural diamond glass cutter²Small blocks; machining the Ti6Al4V titanium alloy into a titanium alloy through lathe cutting

The wafer (2) has a surface roughness of 30nm or less (Ra. ltoreq.30 nm) by polishing and buffing. And (3) ultrasonically cleaning a single crystal Si (100) sheet and a polished Ti6Al4V titanium alloy wafer in acetone, alcohol and deionized water in sequence, drying by using a hair drier, and clamping on a sample table in a cavity of a coating instrument. Four targets, namely 1 Cr target, 1 Mo target, 1 Ag target and 1 Si target, are used and are arranged in a coating instrument.

(2) Target and substrate ion beam cleaning

The background vacuum degree reaches 2.0 multiplied by 10^-6And when the Torr is used, introducing Ar gas (50sccm), setting the negative bias of-450V of the substrate and the duty ratio of 50%, bombarding the surface of the substrate by utilizing Ar ions, and removing pollutants on the surface of the substrate and activating the deposition surface. After the cleaning, the metal Cr target, Mo target, Ag target and Si target were run for 5min while keeping the flow rate of Ar gas at 50sccm, to remove the oxides attached to the surface of the target material.

(3) Film preparation

High-purity Ar gas is kept introduced, and the flow rate of the Ar gas is fixed at 50 sccm. The sample stage was rotated at a speed of 10 rpm. The sputtering current of the Cr target is adjusted to be 4.0A, the negative bias voltage of the substrate is minus 80V, the deposition time is 10min, and a Cr transition layer with the thickness of about 0.2 mu m is prepared on the substrate. Ar gas and N are introduced₂Setting the sputtering current of a Cr target to be 4.0A, negative bias voltage-80V of a substrate, duty ratio of 50 percent, OEM (original equipment manufacture) to be 50 percent and deposition time of 15min for mixed gas of gas, and depositing a Cr-N gradient layer on the Cr transition layer; and starting a magnetron sputtering direct-current power supply of the Mo target, gradually increasing the sputtering current of the Mo target to 2.0A, and further depositing the Cr-Mo-N gradient layer on the Cr-N gradient layer for 15 min. Turning off N₂Gas, namely continuously introducing mixed gas of Ar gas and TMS gas (trimethylsilane) to ensure that N is contained₂The gas is completely discharged, the flow rate of TMS gas is fixed at 15sccm, and the pressure of the cavity is stabilized to 2.3 × 10^-3And Torr, starting a magnetron sputtering direct-current power supply of an Ag target and a Si target, setting the sputtering current of the Ag target to be 0.2A-1.0A, the sputtering current of a fixed Cr target to be 4.0A, the sputtering current of a fixed Mo target to be 2.0A, the sputtering current of a fixed Si target to be 2.0A, negative bias of a substrate to 80V, duty ratio of 50 percent, OEM to 50 percent, deposition time to be 50min-70min, and preparing the Cr-Mo-Ag-Si-C multi-element composite film on the Cr-Mo-N gradient layer.

(4) Evaluation of abrasion resistance and antibacterial property of film

Si (OH) formed by the tribochemical reaction of friction pairs under water-lubricated conditions, as described in example 1₄、MoO₃The lubricity of the antifriction lubricating layer and Ag at the friction interface is critical for low coefficient of friction. The Cr-Mo-Ag-Si-C film shows good wear resistance.

As described in example 1, the Cr-Mo-Ag-Si-C multi-component composite film prepared at low Ag target current (0.2A) shows a certain bactericidal activity within 6h of immersion time, and the film will not play a bactericidal role after 12 h. The reason is that the original film has a low Ag content, and the surface of the film has Ag on the surface for a period of time⁺After releasing, Ag is not released and diffused on the surface of the film⁺And an antibacterial effect is not formed. For Cr-Mo-Ag-Si-C multi-component composite films prepared under high Ag target current (0.6A and 1.0A), the films have good killing performance on escherichia coli within 6 hours or 12 hours of immersion time. With the increase of Ag target current and immersion time, the antibacterial effect of the film is better and better. The Cr-Mo-Ag-Si-C multi-element composite film prepared under the highest Ag target current (1.0A) has the largest area of the Ag particles covered on the surface and the highest surface Ag content, so that the Cr-Mo-Ag-Si-C multi-element composite film is beneficial to more Ag⁺Release and diffusion. In Ag⁺After reacting with and binding to thiol groups in E.coli, the action of enzymes in the bacteria is destroyed and the bacteria are killed. In addition, Ag⁺It can also diffuse through the fluid environment and into the cell membrane, thereby disrupting and destroying the cell membrane. The Cr-Mo-Ag-Si-C multi-element composite film prepared under the highest Ag target current (1.0A) shows the most excellent antibacterial performance.

In summary, it can be found that: the Cr-Mo-Ag-Si-C multi-element composite film prepared by the invention has good wear resistance and excellent antibacterial property, and is a multifunctional film with both wear resistance and antibacterial property.

Example 9

(1) Substrate and target preparation

The single crystal Si (100) sheet was cut into a size of 10X 10cm using a natural diamond glass cutter²Small blocks; machining the Ti6Al4V titanium alloy into a titanium alloy through lathe cutting

The wafer (2) has a surface roughness of 30nm or less (Ra. ltoreq.30 nm) by polishing and buffing. And (3) ultrasonically cleaning a single crystal Si (100) sheet and a polished Ti6Al4V titanium alloy wafer in acetone, alcohol and deionized water in sequence, drying by using a hair drier, and clamping on a sample table in a cavity of a coating instrument. Four targets, namely 1 Cr target, 1 Mo target, 1 Ag target and 1C target, are used and are arranged in a coating instrument.

(2) Target and substrate ion beam cleaning

The background vacuum degree reaches 2.0 multiplied by 10^-6And when the Torr is used, introducing Ar gas (50sccm), setting the negative bias of-450V of the substrate and the duty ratio of 50%, bombarding the surface of the substrate by utilizing Ar ions, and removing pollutants on the surface of the substrate and activating the deposition surface. After the cleaning, the metal Cr target, Mo target, Ag target and C target were run for 5min while keeping the Ar gas flow rate at 50sccm, to remove the oxides attached to the surface of the target material.

(3) Film preparation

High-purity Ar gas is kept introduced, and the flow rate of the Ar gas is fixed at 50 sccm. The sample stage was rotated at a speed of 10 rpm. The sputtering current of the Cr target is adjusted to be 4.0A, the negative bias voltage of the substrate is minus 80V, the deposition time is 10min, and a Cr transition layer with the thickness of about 0.2 mu m is prepared on the substrate. Ar gas and N are introduced₂Setting the sputtering current of a Cr target to be 4.0A, negative bias voltage-80V of a substrate, duty ratio of 50 percent, OEM (original equipment manufacture) to be 50 percent and deposition time of 15min for mixed gas of gas, and depositing a Cr-N gradient layer on the Cr transition layer; and starting a magnetron sputtering direct-current power supply of the Mo target, gradually increasing the sputtering current of the Mo target to 2.0A, and further depositing the Cr-Mo-N gradient layer on the Cr-N gradient layer for 15 min. Turning off N₂Gas, namely continuously introducing mixed gas of Ar gas and TMS gas (trimethylsilane) to ensure that N is contained₂The gas is completely discharged, the flow rate of TMS gas is fixed at 15sccm, and the pressure of the cavity is stabilized to 2.3 × 10^-3Torr, starting a magnetron sputtering direct current power supply of an Ag target and a C target, setting the sputtering current of the Ag target to be 0.2A-1.0A, the sputtering current of a fixed Cr target to be 4.0A, the sputtering current of a fixed Mo target to be 2.0A, the sputtering current of a fixed C target to be 2.0A, negative bias voltage of a substrate to 80V, duty ratio of 50 percent, OEM to 50 percent, deposition time of 50min-70min, and performing sputtering on the Ag target and the C target for a period of time of 50min-70minPreparing the Cr-Mo-Ag-Si-C multi-element composite film on the Cr-Mo-N gradient layer.

(4) Evaluation of abrasion resistance and antibacterial property of film

Si (OH) formed by the tribochemical reaction of friction pairs under water-lubricated conditions, as described in example 1₄、MoO₃The lubricity of the antifriction lubricating layer and Ag at the friction interface is critical for low coefficient of friction. The Cr-Mo-Ag-Si-C film shows good wear resistance.

As described in example 1, the Cr-Mo-Ag-Si-C multi-component composite film prepared at low Ag target current (0.2A) shows a certain bactericidal activity within 6h of immersion time, and the film will not play a bactericidal role after 12 h. The reason is that the original film has a low Ag content, and the surface of the film has Ag on the surface for a period of time⁺After releasing, Ag is not released and diffused on the surface of the film⁺And an antibacterial effect is not formed. For Cr-Mo-Ag-Si-C multi-component composite films prepared under high Ag target current (0.6A and 1.0A), the films have good killing performance on escherichia coli within 6 hours or 12 hours of immersion time. With the increase of Ag target current and immersion time, the antibacterial effect of the film is better and better. The Cr-Mo-Ag-Si-C multi-element composite film prepared under the highest Ag target current (1.0A) has the largest area of the Ag particles covered on the surface and the highest surface Ag content, so that the Cr-Mo-Ag-Si-C multi-element composite film is beneficial to more Ag⁺Release and diffusion. In Ag⁺After reacting with and binding to thiol groups in E.coli, the action of enzymes in the bacteria is destroyed and the bacteria are killed. In addition, Ag⁺It can also diffuse through the fluid environment and into the cell membrane, thereby disrupting and destroying the cell membrane. The Cr-Mo-Ag-Si-C multi-element composite film prepared under the highest Ag target current (1.0A) shows the most excellent antibacterial performance.

In summary, it can be found that: the Cr-Mo-Ag-Si-C multi-element composite film prepared by the invention has good wear resistance and excellent antibacterial property, and is a multifunctional film with both wear resistance and antibacterial property.

Example 10

(1) Substrate and target preparation

Single crystal Si (10) using a natural diamond glass cutter0) The sheet was cut into a size of 10X 10cm²Small blocks; machining the Ti6Al4V titanium alloy into a titanium alloy through lathe cutting

The wafer (2) has a surface roughness of 30nm or less (Ra. ltoreq.30 nm) by polishing and buffing. And (3) ultrasonically cleaning a single crystal Si (100) sheet and a polished Ti6Al4V titanium alloy wafer in acetone, alcohol and deionized water in sequence, drying by using a hair drier, and clamping on a sample table in a cavity of a coating instrument. Four targets, 2 Cr targets, 1 Mo target and 1 Ag target, are used and installed in a coating instrument.

(2) Target and substrate ion beam cleaning

The background vacuum degree reaches 2.0 multiplied by 10^-6And when the Torr is used, introducing Ar gas (50sccm), setting the negative bias of-450V of the substrate and the duty ratio of 50%, bombarding the surface of the substrate by utilizing Ar ions, and removing pollutants on the surface of the substrate and activating the deposition surface. After the cleaning, the metal Cr target, the Mo target and the Ag target were run for 5min while keeping the flow rate of Ar at 50sccm, to remove the oxides attached to the surface of the target.

(3) Film preparation

High-purity Ar gas is kept introduced, and the flow rate of the Ar gas is fixed at 50 sccm. The sample stage was rotated at a speed of 10 rpm. The sputtering current of the Cr target is adjusted to be 4.0A, the negative bias voltage of the substrate is minus 80V, the deposition time is 10min, and a Cr transition layer with the thickness of about 0.2 mu m is prepared on the substrate. Ar gas and N are introduced₂Setting the sputtering current of a Cr target to be 4.0A, negative bias voltage-80V of a substrate, duty ratio of 50 percent, OEM (original equipment manufacture) to be 50 percent and deposition time of 15min for mixed gas of gas, and depositing a Cr-N gradient layer on the Cr transition layer; and starting a magnetron sputtering direct-current power supply of the Mo target, gradually increasing the sputtering current of the Mo target to 2.0A, and further depositing the Cr-Mo-N gradient layer on the Cr-N gradient layer for 15 min. Turning off N₂Gas, namely continuously introducing mixed gas of Ar gas and TMS gas (trimethylsilane) to ensure that N is contained₂The gas is completely discharged, the flow rate of TMS gas is fixed at 15sccm, and the pressure of the cavity is stabilized to 2.3 × 10^-3Torr, starting a magnetron sputtering direct current power supply of the Ag target, setting the sputtering current of the Ag target to be 0.2A-1.0A, the sputtering current of the fixed Cr target to be 4.0A, the sputtering current of the fixed Mo target to be 2.0A, negative bias of a substrate to be 80V, duty ratio50 percent of OEM, and 50-70 min of deposition time, and preparing the Cr-Mo-Ag-Si-C multi-component composite film on the Cr-Mo-N gradient layer.

(4) Evaluation of abrasion resistance and antibacterial property of film

Si (OH) formed by the tribochemical reaction of friction pairs under water-lubricated conditions, as described in example 1₄、MoO₃The lubricity of the antifriction lubricating layer and Ag at the friction interface is critical for low coefficient of friction. The Cr-Mo-Ag-Si-C film shows good wear resistance.

As described in example 1, the Cr-Mo-Ag-Si-C multi-component composite film prepared at low Ag target current (0.2A) shows a certain bactericidal activity within 6h of immersion time, and the film will not play a bactericidal role after 12 h. The reason is that the original film has a low Ag content, and the surface of the film has Ag on the surface for a period of time⁺After releasing, Ag is not released and diffused on the surface of the film⁺And an antibacterial effect is not formed. For Cr-Mo-Ag-Si-C multi-component composite films prepared under high Ag target current (0.6A and 1.0A), the films have good killing performance on escherichia coli within 6 hours or 12 hours of immersion time. With the increase of Ag target current and immersion time, the antibacterial effect of the film is better and better. The Cr-Mo-Ag-Si-C multi-element composite film prepared under the highest Ag target current (1.0A) has the largest area of the Ag particles covered on the surface and the highest surface Ag content, so that the Cr-Mo-Ag-Si-C multi-element composite film is beneficial to more Ag⁺Release and diffusion. In Ag⁺After reacting with and binding to thiol groups in E.coli, the action of enzymes in the bacteria is destroyed and the bacteria are killed. In addition, Ag⁺It can also diffuse through the fluid environment and into the cell membrane, thereby disrupting and destroying the cell membrane. The Cr-Mo-Ag-Si-C multi-element composite film prepared under the highest Ag target current (1.0A) shows the most excellent antibacterial performance.

In summary, it can be found that: the Cr-Mo-Ag-Si-C multi-element composite film prepared by the invention has good wear resistance and excellent antibacterial property, and is a multifunctional film with both wear resistance and antibacterial property.

The foregoing is only a preferred embodiment of this invention and it should be noted that modifications can be made by those skilled in the art without departing from the principle of the invention and these modifications should also be considered as the scope of the invention.

Claims (6)

1. A preparation method of a Cr-Mo-Ag-Si-C-N multi-element composite film with wear resistance and antibiosis is characterized by comprising the following steps:

(1) opening a cavity door of the closed unbalanced magnetron sputtering coating instrument, cleaning and drying a substrate, and installing a sample table in a cavity of the coating instrument;

(2) vacuumizing the cavity of the coating instrument to 2.0 x 10^-6Torr, simultaneously heating the vacuum cavity to 150 ℃, and accelerating the evaporation of residual water in the cavity;

(3) when the cavity is cooled to room temperature, introducing high-purity Ar gas, and cleaning and activating the surface of the substrate by utilizing Ar ion beams; after cleaning, continuously introducing Ar gas, starting a magnetron sputtering power supply, allowing the target material to run for 5min, and removing oxides attached to the surface of the target material;

(4) keeping introducing high-purity Ar gas, wherein the flow rate of the Ar gas is fixed to be 50 sccm; rotating the sample table, and setting the rotating speed to be 10 rpm; regulating the sputtering current of a Cr target to be 4.0A, negatively biasing the substrate to 80V, depositing for 10min, and preparing a Cr transition layer with the thickness of 0.2 mu m on the substrate;

(5) ar gas and N are introduced₂Setting the sputtering current of a Cr target to be 4.0A and the deposition time to be 15min, and depositing a Cr-N gradient layer on the Cr transition layer; starting a magnetron sputtering direct-current power supply of the Mo target, gradually increasing the sputtering current of the Mo target to 2.0A, depositing for 15min, and further depositing a Cr-Mo-N gradient layer on the Cr-N gradient layer;

(6) introducing Ar gas and N₂The flow rate of trimethyl silane is fixed to be 15sccm, and the pressure of the cavity is stabilized to be 2.3 multiplied by 10^-3And Torr, starting a magnetron sputtering direct-current power supply of the Ag target, fixing the sputtering current of the Cr target and the Mo target, and preparing the Cr-Mo-Ag-Si-C-N multi-element composite film on the Cr-Mo-N gradient layer.

2. The preparation method of the Cr-Mo-Ag-Si-C-N multi-element composite film with wear resistance and antibacterial property according to claim 1, which is characterized in that: the substrate in the step (1) is any one of a monocrystalline silicon wafer, glass, stainless steel, high-speed steel and titanium alloy.

3. The preparation method of the Cr-Mo-Ag-Si-C-N multi-element composite film with wear resistance and antibacterial property according to claim 2, characterized in that: and (2) after the substrate is cleaned and dried in the step (1), specifically, ultrasonically cleaning the polished monocrystalline silicon wafer or titanium alloy in acetone, alcohol and deionized water in sequence, and drying by using a hair dryer.

4. The preparation method of the Cr-Mo-Ag-Si-C-N multi-element composite film with wear resistance and antibacterial property according to claim 1, which is characterized in that: and (3) introducing high-purity Ar gas, setting the flow rate of the Ar gas to be 50sccm, negatively biasing the substrate to 450V, and cleaning for 30 min.

5. The preparation method of the Cr-Mo-Ag-Si-C-N multi-element composite film with wear resistance and antibacterial property according to claim 1, which is characterized in that: in the step (5), the sputtering current of the Cr target is set to be 4.0A, the negative bias voltage of the substrate is-80V, the duty ratio is 50%, the OEM is 50%, and the deposition time is 15 min.

6. The preparation method of the Cr-Mo-Ag-Si-C-N multi-element composite film with wear resistance and antibacterial property according to claim 1, which is characterized in that: and (3) starting the magnetron sputtering direct-current power supply of the Ag target in the step (6), setting the sputtering current of the Ag target to be 0.2A-1.0A, the sputtering current of the fixed Cr target to be 4.0A, the sputtering current of the fixed Mo target to be 2.0A, negative bias of a substrate to 80V, duty ratio to be 50%, OEM to be 50%, and deposition time to be 50min-70 min.

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