Wear-resistant and corrosion-resistant nanometer multilayer ceramic-based film and preparation method and application thereof

Abstract

The application discloses a wear-resistant and corrosion-resistant nanometer multilayer ceramic-based film and a preparation method and application thereof. The wear-resistant and corrosion-resistant nanometer multilayer ceramic-based film comprises a chromium transition layer and a nanometer multilayer composite structure which are sequentially stacked in the thickness direction of the film. The nanometer multilayer composite structure comprises a plurality of period units which are stacked and arranged. Each period unit comprises a tungsten diboride / carbon nanometer layer and a carbon nanometer layer. The tungsten diboride / carbon nanometer layer in the period unit adjacent to the chromium transition layer is arranged adjacent to the chromium transition layer. The top end of the nanometer multilayer composite structure is the carbon nanometer layer. The wear-resistant and corrosion-resistant nanometer multilayer ceramic-based film has high bonding force, low atmospheric environment friction coefficient, good antifriction and wear resistance, good seawater corrosion resistance, can meet the lubrication stability and long service life requirements of a ship transmission system component, and makes up the shortcomings of poor salt mist resistance of a carbon-based film.

Description

Technical Field

[0001] The present invention belongs to the technical field of surface treatment, and in particular relates to a wear-resistant and corrosion-resistant nano multilayer ceramic-based film and a preparation method and application thereof. Background Art

[0002] Guided by the goal of strengthening the military, combat-oriented training and exercises are increasing in intensity year by year, and equipment is being used more frequently. Proper equipment maintenance is particularly important, especially for amphibious armored vehicles, which are frequently exposed to seawater and are susceptible to corrosion. The power components of amphibious armored vehicles (such as transmission gears and shafts, or other transmission mechanisms) generally do not come into direct contact with seawater. The high-temperature evaporation of seawater produces a severe salt spray, exposing transmission components in contact with air to an even harsher corrosive environment. For mechanical open motion systems / components exposed to tropical marine atmosphere, friction and wear are primarily addressed through self-lubricating coatings, while corrosion is primarily addressed through insulating and corrosion-resistant coatings. However, the actual operating environment of amphibious equipment is subject to a combination of damage, including salt spray and wear. Therefore, developing a novel, highly effective anti-friction, wear-resistant, and corrosion-resistant film is crucial for improving component performance and reducing operating costs.

[0003] Diamond-like carbon-based films have attracted considerable attention as solid lubricants due to their exceptional properties, including high hardness, high wear resistance, and low coefficient of friction. However, in marine salt spray environments, graphite readily absorbs moisture or is oxidized by corrosive media into complex oxides, causing corrosion and a sharp deterioration in tribological properties. Tungsten diboride (WB2) films are a new type of superhard film that exhibits high hardness, a high melting point, chemical inertness, and thermal conductivity. The formation of WOx during wear imparts excellent self-lubricity. However, research has shown that tungsten oxides have difficulty forming a transfer film that adheres to steel balls, resulting in WB2 films retaining a high coefficient of friction. Summary of the Invention

[0004] The main purpose of the present invention is to provide a wear-resistant and corrosion-resistant nano-multilayer ceramic-based film and its preparation method and application, so as to overcome the shortcomings of the prior art.

[0005] To achieve the aforementioned object of the invention, the technical solutions adopted by the present invention include:

[0006] One aspect of the present invention provides a wear-resistant and corrosion-resistant nano-multilayer ceramic-based film, comprising: a chromium transition layer and a nano-multilayer composite structure sequentially stacked in a thickness direction thereof, wherein the nano-multilayer composite structure comprises a plurality of stacked periodic units, each periodic unit comprising a tungsten diboride / carbon (WB2 / C) nanolayer and a carbon nanolayer;

[0007] The tungsten diboride / carbon nanolayer in the periodic unit adjacent to the chromium transition layer is arranged adjacent to the chromium transition layer, and the top of the nano multilayer composite structure is the carbon nanolayer.

[0008] Another aspect of the present invention provides a method for preparing a wear-resistant and corrosion-resistant nano-multilayer ceramic-based film, comprising:

[0009] A chromium transition layer is deposited on the substrate surface using multi-arc ion plating technology;

[0010] Using magnetron sputtering technology, tungsten diboride / carbon nanolayers and carbon nanolayers are sequentially deposited on the chromium transition layer to form a periodic unit. 100 periodic units are repeatedly prepared to obtain a wear-resistant and corrosion-resistant nano-multilayer ceramic-based film.

[0011] Another aspect of the present invention provides a wear-resistant and corrosion-resistant nano-multilayer ceramic-based film prepared by the preparation method.

[0012] Another aspect of the present invention provides the use of the wear-resistant and corrosion-resistant nano-multilayer ceramic-based film in substrate protection, wherein the substrate includes at least a partial surface of a marine equipment transmission system or component.

[0013] Compared with the prior art, the present invention has at least the following beneficial effects:

[0014] The present invention adopts advanced materials, preparation technology and appropriate modulation ratio, and the tungsten diboride / carbon nanolayer and carbon nanolayer film prepared by synergistic action can induce tungsten oxide lubrication, have high bonding force, low friction coefficient in atmospheric environment, good anti-friction and anti-wear performance, and seawater corrosion resistance, can meet the requirements of lubrication stability and long service life of ship transmission system components, and make up for the disadvantage of poor salt spray resistance of carbon-based films. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments recorded in the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0016] Figure 1 Schematic diagram of the structure of the wear-resistant and corrosion-resistant nano multilayer ceramic-based film obtained in Example 3 of the present invention;

[0017] Figure 2 This is a cross-sectional SEM image of the wear-resistant and corrosion-resistant nano-multilayer ceramic-based film prepared in Example 3 of the present invention;

[0018] Figure 3is a transmission diagram of the wear-resistant and corrosion-resistant nanometer multilayer ceramic-based film prepared in Example 3 of the present application;

[0019] Figure 4 is a bonding force test diagram of the wear-resistant and corrosion-resistant nanometer multilayer ceramic-based film prepared in Example 3 of the present application;

[0020] Figure 5 is a friction curve diagram of the wear-resistant and corrosion-resistant nanometer multilayer ceramic-based film prepared in Example 3 of the present application under atmospheric friction;

[0021] Figure 6 is a sample diagram of the film samples obtained in Examples 1-3 and Comparative Examples 1-3 of the present application after salt spray for 7 days;

[0022] Figure 7 is a diagram of the average friction coefficient and wear rate of the wear-resistant and corrosion-resistant nanometer multilayer ceramic-based film prepared in Example 3 of the present application after salt spray for 7 days. DETAILED DESCRIPTION

[0023] In view of the problems existing in the prior art, the inventors of the present application have conducted extensive and in-depth research, and provide a wear-resistant and corrosion-resistant nanometer multilayer ceramic-based film, a preparation method and application thereof, which mainly comprises the following steps: designing a nanometer multilayer structure film through structural design, setting the alternating cycle period of tungsten diboride / carbon target and carbon target by adjusting the sputtering time of the carbon target, and depositing tungsten diboride / carbon nanolayers and carbon nanolayers on the surface of the substrate to prepare the nanometer multilayer film. The WB2 / C nanometer multilayer film of the present application can exhibit excellent tribological properties under the atmosphere, reduce the friction coefficient of the A1B2 type WB2 film, and still maintain good friction performance under the salt spray environment, thereby making up for the poor salt spray resistance of the carbon-based film.

[0024] The technical scheme, its implementation process and principles will be further explained and described as follows.

[0025] As an aspect of the technical scheme of the present application, a wear-resistant and corrosion-resistant nanometer multilayer ceramic-based film comprises: a chromium transition layer and a nanometer multilayer composite structure which are sequentially stacked in the thickness direction of the film, wherein the nanometer multilayer composite structure comprises a plurality of period units which are stacked, and each period unit comprises a tungsten diboride / carbon nanolayer and a carbon nanolayer.

[0026] The tungsten diboride / carbon nanolayer in the period unit adjacent to the chromium transition layer is arranged adjacent to the chromium transition layer, and the top end of the nanometer multilayer composite structure is the carbon nanolayer.

[0027] In some embodiments, the nanometer multilayer composite structure comprises 100 period units.

[0028] In some embodiments, the nanomultilayer composite structure comprises tungsten diboride / carbon nanolayers and carbon nanolayers arranged in an alternating sequence.

[0029] In some embodiments, the content of C atoms in the wear-resistant and corrosion-resistant nanomultilayer ceramic-based film is 65-80%, the content of W atoms is 9-11%, and the content of B atoms is 14-26%.

[0030] In some embodiments, the thickness of the chromium transition layer is 80-100 nm.

[0031] In some embodiments, the thickness of the carbon nanolayer is 5-8 nm.

[0032] In some embodiments, the thickness of the tungsten diboride / carbon nanolayer is 8-12 nm.

[0033] In some embodiments, the thickness of the wear-resistant and corrosion-resistant nanomultilayer ceramic-based film is 1380-2100 nm.

[0034] In some embodiments, the bonding strength of the wear-resistant and corrosion-resistant nanomultilayer ceramic-based film is 28-30 N.

[0035] In some embodiments, the friction coefficient of the wear-resistant and corrosion-resistant nanomultilayer ceramic-based film in an atmospheric environment at room temperature is 0.2-0.28, and the wear rate is 2.91-4.21 x 10 -7 mm 3 / Nm.

[0036] In some embodiments, the friction coefficient of the wear-resistant and corrosion-resistant nanomultilayer ceramic-based film in a salt spray environment at room temperature for 7 days is 0.25-0.35, and the wear rate is 10-16 x 10 -7 mm 3 / Nm.

[0037] As another aspect of the technical solution of the present application, a preparation method of a wear-resistant and corrosion-resistant nanomultilayer ceramic-based film is provided, which comprises:

[0038] depositing a chromium transition layer on the surface of the substrate by using a multi-arc ion plating technology;

[0039] depositing tungsten diboride / carbon nanolayers and carbon nanolayers in an alternating sequence on the chromium transition layer by using a magnetron sputtering technology to form a periodic unit, repeating the preparation of 100 periodic units, and obtaining the wear-resistant and corrosion-resistant nanomultilayer ceramic-based film.

[0040] In some embodiments, the preparation method specifically includes: performing plasma etching treatment on the substrate; wherein the plasma etching treatment includes: applying a bias voltage of 180 to 220 V to the substrate, an etching time of 30 to 40 minutes, and an etching temperature of 200 to 300°C.

[0041] In some embodiments, the material of the substrate includes at least any one of 316 stainless steel or single crystal silicon wafer, but is not limited thereto.

[0042] In some embodiments, the preparation method specifically includes: using multi-arc ion plating technology, using a chromium target as a cathode target material, using an inert gas as a working gas, applying a target current to the chromium target, applying a negative bias voltage to the substrate, and depositing the chromium transition layer on the substrate surface;

[0043] Among them, the target current in the multi-arc ion plating technology is 20-30A, the bias voltage is 20-30V, the gas flow rate of the working gas is 350-400sccm, the deposition time is 480-500s, and the rotation speed is 1-3r / min; the inert gas includes argon.

[0044] In some embodiments, the preparation method further comprises: using magnetron sputtering technology, using a tungsten diboride / carbon target as a cathode target material, using an inert gas as a working gas, applying a target current to the tungsten diboride / carbon target, and applying a negative bias voltage to the substrate, thereby depositing a tungsten diboride / carbon nanolayer on the chromium transition layer;

[0045] Among them, the target current in the magnetron sputtering technology is 40-60A, the power is 3-4kW, the gas flow rate of the working gas is 200-300sccm, the deposition time is 60-80s, and the rotation speed is 3-5r / min; the inert gas includes argon.

[0046] In some embodiments, the preparation method specifically includes: using magnetron sputtering technology, using a carbon target as a cathode target material, using an inert gas as a working gas, applying a target current to the carbon target, and applying a negative bias voltage to the substrate, thereby depositing a carbon nanolayer on the tungsten diboride / carbon nanolayer;

[0047] Among them, the target current in the magnetron sputtering technology is 40-60A, the power is 5-6kW, the gas flow rate of the working gas is 200-300sccm, the deposition time is 180-300s, and the rotation speed is 3-5r / min; the inert gas includes argon.

[0048] In some more specific embodiments, the preparation method may include the following steps:

[0049] (1) performing plasma etching on the substrate;

[0050] The plasma etching process includes applying a bias voltage of 180 to 200 V to the substrate, etching for 30 to 40 minutes, and etching at a temperature of 200 to 300° C.

[0051] (2) using a multi-arc ion plating technique, using a chromium target as a cathode target material, using argon as a working gas, applying a target current to the chromium target, applying a negative bias voltage to the substrate, and depositing the chromium transition layer on the substrate surface;

[0052] The target current in the multi-arc ion plating technology is 20-30A, the bias voltage is 20-30V, the flow rate of the working gas is 350-400sccm, the deposition time is 480-500s, and the rotation speed is 1-3r / min.

[0053] (3) using magnetron sputtering technology, with a tungsten diboride / carbon target as a cathode target material, argon as a working gas, applying a target current to the tungsten diboride / carbon target, and applying a negative bias voltage to the substrate, thereby depositing a tungsten diboride / carbon nanolayer on the chromium transition layer;

[0054] The target current in the magnetron sputtering technology is 40-60A, the power is 3-4kW, the flow rate of the working gas is 200-300sccm, the deposition time is 60-80s, and the rotation speed is 3-5r / min.

[0055] (4) using magnetron sputtering technology, with a carbon target as the cathode target material, argon as the working gas, applying a target current to the carbon target, and applying a negative bias voltage to the substrate, thereby depositing a carbon nanolayer on the tungsten diboride / carbon nanolayer;

[0056] The target current in the magnetron sputtering technology is 40-60A, the power is 5-6kW, the flow rate of the working gas is 200-300sccm, the deposition time is 180-300s, and the rotation speed is 3-5r / min.

[0057] (5) Repeat steps 3 and 4 for 100 cycles to deposit a nano-multilayer composite film on the surface of the chromium transition layer.

[0058] As another aspect of the technical solution of the present invention, it also provides a wear-resistant and corrosion-resistant nano-multilayer ceramic-based film prepared by the preparation method.

[0059] As another aspect of the technical solution of the present invention, it also provides the use of the wear-resistant and corrosion-resistant nano-multilayer ceramic-based film in substrate protection, where the substrate includes at least a partial surface of a marine equipment transmission system or component.

[0060] Furthermore, the marine equipment includes ships.

[0061] In summary, the present invention deposits a wear-resistant and corrosion-resistant nano-multilayer ceramic-based film on the substrate surface by regulating the sputtering time of the carbon target and establishing alternating cycles of tungsten diboride / carbon targets and carbon targets. The wear-resistant and corrosion-resistant nano-multilayer ceramic-based film of the present invention can significantly reduce the friction coefficient of the surface of transmission components while also exhibiting excellent wear and corrosion resistance. It can operate stably for long periods in harsh marine environments, significantly extending the service life and maintenance cycle of transmission components.

[0062] In order to make the purpose, technical solutions and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with embodiment. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention. Those skilled in the art will make modifications or equivalent substitutions based on understanding the technical solution of the present invention, without departing from the spirit and scope of the technical solution of the present invention, and all should be encompassed within the protection scope of the present invention.

[0063] Where specific experimental procedures or conditions are not specified in the examples, the experiments were carried out according to conventional experimental procedures or conditions described in literature in the field. Reagents or instruments used without manufacturer specified are commercially available. Commercially available options for other raw materials and instruments not mentioned are conventional and do not relate to the core technical means of the present invention.

[0064] Example 1

[0065] In this embodiment, the substrate material is 316 steel or single crystal silicon wafer. Magnetron sputtering technology is used to prepare a wear-resistant and corrosion-resistant nano-multilayer ceramic-based film on the substrate surface, which mainly includes the following steps:

[0066] The substrate surface was mechanically polished, and the substrate material was placed in an acetone solution for ultrasonic cleaning for 15 minutes, dried with nitrogen, and then placed in an anhydrous ethanol solution for ultrasonic cleaning for 15 minutes, and dried with nitrogen.

[0067] The cleaned substrate was placed in a vacuum chamber and evacuated to a vacuum degree of less than 6×10 -4 mbar, then heated to 180°C and pressure to 4×10 -4 mbar, pressure to 3×10 -5 mbar. Sputtering targets were cleaned using WB2 / C targets (purity 99.9 at.%, weight ratio 50:50) and C targets. Wear-resistant and corrosion-resistant nano-multilayer ceramic thin films were deposited. High-purity argon was filled into the chamber. A Cr target (purity 99.99 at.%), a WB2 / C target (purity 99.9 at.%, weight ratio 50:50), and a C target (purity 99.99 at.%) were used for control and setup. The specific steps are as follows:

[0068] (1) Plasma etching: a bias voltage of 200 V was applied to the substrate, the program run time was 40 min, and the chamber temperature was 300 °C;

[0069] (2) Multi-arc ion plating chromium target, current of 30.0A, bias voltage of 20V, working gas of Ar, gas flow rate of 350sccm, deposition time of 480s, rotation speed of 2r / min to deposit a chromium transition layer on the substrate surface;

[0070] (3) Magnetron sputtering of WB2 / C target, sputtering current of 50.0A, power of 4kW, working gas of Ar, gas flow of 200sccm, deposition time of 60s, and rotation speed of 3r / min;

[0071] (4) Magnetron sputtering C target, sputtering current 50.0A, power 5kW, working gas Ar, gas flow rate 200sccm, deposition time 180s, rotation speed 3r / min;

[0072] (5) Repeat steps 3 and 4 for 100 cycles to deposit a nano-multilayer composite film on the surface of the chromium transition layer.

[0073] The wear-resistant and corrosion-resistant nano-multilayer ceramic-based film was prepared as sample 1, and its specific composition parameters are shown in Table 1.

[0074] The sample 1 film obtained after the above deposition process was subjected to the following tests:

[0075] (1) The film thickness was measured using a scanning electron microscope.

[0076] (2) The bonding performance of the film was tested using the Revetest scratch test system (CSM, Revetest). Three scratch tests were performed at different positions. The experimental conditions were loading speed: 3 mm / min, scratch length: 5 mm, and loading force: 100 N. The test results are shown in Table 2.

[0077] (3) Dry friction tests were conducted using a tribometer (TRB3) at 25°C in an atmospheric environment, with two to three repetitions. A GCr15 steel ball was used as the counterpart, and a reciprocating motion was employed with a frequency of 5 Hz, a track length of 5 mm, a travel distance of 180 m, and a normal load of 5 N. A surface profiler (ASTQ) was used to obtain the wear cross-section, which was multiplied by the travel step length to obtain the wear volume. The wear volume was then divided by the load and travel to obtain the wear rate. The results of the friction coefficient and wear rate tests are shown in Table 3.

[0078] (4) Dry friction tests were conducted on samples exposed to salt spray for 7 days at 25°C using a friction tester (TRB3). The test was repeated 2 to 3 times. A GCr15 steel ball was used as the counterpart. A reciprocating method was used with a frequency of 5 Hz, a track length of 5 mm, a running distance of 180 m, and a normal load of 5 N. A surface profiler (ASTQ) was used to obtain the wear cross section. The wear volume was obtained by multiplying it by the running step length. The wear volume was then divided by the load and travel to obtain the wear rate. The results of the test friction coefficient and wear rate are shown in Table 4.

[0079] Example 2

[0080] In this embodiment, the substrate material is 316 steel or single crystal silicon wafer. Magnetron sputtering technology is used to prepare a wear-resistant and corrosion-resistant nano-multilayer ceramic-based film on the substrate surface, which mainly includes the following steps:

[0081] The substrate surface was mechanically polished, and the substrate material was placed in an acetone solution for ultrasonic cleaning for 15 minutes, dried with nitrogen, and then placed in an anhydrous ethanol solution for ultrasonic cleaning for 15 minutes, and dried with nitrogen.

[0082] The cleaned substrate was placed in a vacuum chamber and evacuated to a vacuum degree of less than 6×10 -4 mbar, then heated to 180°C and pressure to 4×10 -4 mbar, then keep the temperature at 160℃ and the pressure at 3×10 -5 mbar. Sputtering targets were cleaned using WB2 / C targets (purity 99.9 at.%, weight ratio 50:50) and C targets. Wear-resistant and corrosion-resistant nano-multilayer ceramic thin films were deposited. High-purity argon was filled into the chamber. A Cr target (purity 99.99 at.%), a WB2 / C target (purity 99.9 at.%, weight ratio 50:50), and a C target (purity 99.99 at.%) were used for control and setup. The specific steps are as follows:

[0083] (1) Plasma etching: a bias voltage of 200 V was applied to the substrate, the program run time was 40 min, and the chamber temperature was 300 °C;

[0084] (2) Multi-arc ion plating chromium target, current of 30.0A, bias voltage of 20V, working gas of Ar, gas flow rate of 350sccm, deposition time of 480s, rotation speed of 2r / min to deposit a chromium transition layer on the substrate surface;

[0085] (3) Magnetron sputtering of WB2 / C target, sputtering current of 50.0A, power of 4kW, working gas of Ar, gas flow of 200sccm, deposition time of 60s, and rotation speed of 3r / min;

[0086] (4) Magnetron sputtering C target, sputtering current 50.0A, power 5kW, working gas Ar, gas flow rate 200sccm, deposition time 240s, rotation speed 3r / min;

[0087] (5) Repeat steps 3 and 4 for 100 cycles to deposit a nano-multilayer composite film on the surface of the chromium transition layer.

[0088] The wear-resistant and corrosion-resistant nano-multilayer ceramic-based film was prepared as sample 2, and its specific composition parameters are shown in Table 1.

[0089] The sample 2 film obtained after the above deposition process was subjected to the following tests:

[0090] (1) The film thickness was measured using a scanning electron microscope.

[0091] (2) The bonding performance of the film was tested using the Revetest scratch test system (CSM, Revetest). Three scratch tests were performed at different positions. The experimental conditions were loading speed: 3 mm / min, scratch length: 5 mm, and loading force: 100 N. The test results are shown in Table 2.

[0092] (3) A dry friction test was conducted at 25 degrees using a friction tester (TRB3) with 2N3 repetitions. A GCr15 steel ball was used as the counterpart, and a reciprocating method was adopted with a frequency of 5 Hz, a track length of 5 mm, a running distance of 180 m, and a normal load of 5 N. A surface profiler (ASTQ) was used to obtain the wear cross section, which was multiplied by the running step length to obtain the wear volume. The wear volume was then divided by the load and travel to obtain the wear rate. The test friction coefficient and wear rate results are shown in Table 3.

[0093] (4) Dry friction tests were conducted on samples exposed to salt spray for 7 days at 25°C using a friction tester (TRB3). The test was repeated 2 to 3 times. A GCr15 steel ball was used as the counterpart. A reciprocating method was used with a frequency of 5 Hz, a track length of 5 mm, a running distance of 180 m, and a normal load of 5 N. A surface profiler (ASTQ) was used to obtain the wear cross section. The wear volume was obtained by multiplying it by the running step length. The wear volume was then divided by the load and travel to obtain the wear rate. The results of the test friction coefficient and wear rate are shown in Table 4.

[0094] Example 3

[0095] In this embodiment, the substrate material is 316 steel or single crystal silicon wafer. Magnetron sputtering technology is used to prepare W wear-resistant and corrosion-resistant nano-multilayer ceramic-based thin films on the substrate surface, which mainly includes the following steps:

[0096] The substrate surface was mechanically polished, and the substrate material was placed in an acetone solution for ultrasonic cleaning for 15 minutes, dried with nitrogen, and then placed in an anhydrous ethanol solution for ultrasonic cleaning for 15 minutes, and dried with nitrogen.

[0097] The cleaned substrate was placed in a vacuum chamber and evacuated to a vacuum degree of less than 6×10 -4 mbar, then heated to 180°C and pressure to 4×10 -4 mbar, then keep the temperature at 160℃ and the pressure at 3×10 -5 mbar. Sputtering cleans a WB2 / C target (99.9 at.%, 50:50 weight ratio) and a C target. Deposition of wear-resistant and corrosion-resistant nano-multilayer ceramic-based thin films is performed. The chamber is filled with high-purity argon gas. A Cr target (99.99 at.%), a WB2 / C target (99.9 at.%, 50:50 weight ratio), and a C target (99.99 at.%) are used for control setup. The specific steps are as follows:

[0098] (1) Plasma etching: a bias voltage of 200 V was applied to the substrate, the program run time was 40 min, and the chamber temperature was 300 °C;

[0099] (2) Multi-arc ion plating chromium target, current of 30.0A, bias voltage of 20V, working gas of Ar, gas flow rate of 350sccm, deposition time of 480s, rotation speed of 2r / min to deposit a chromium transition layer on the substrate surface;

[0100] (3) Magnetron sputtering of WB2 / C target, sputtering current of 50.0A, power of 4kW, working gas of Ar, gas flow of 200sccm, deposition time of 60s, and rotation speed of 3r / min;

[0101] (4) Magnetron sputtering C target, sputtering current 50.0A, power 5kW, working gas Ar, gas flow rate 200sccm, deposition time 300s, rotation speed 3r / min;

[0102] (5) Repeat steps 3 and 4 for 100 cycles to deposit a nano-multilayered film on the surface of the chromium transition layer.

[0103] The wear-resistant and corrosion-resistant nano-multilayer ceramic-based film was prepared as sample 3, and its specific composition parameters are shown in Table 1.

[0104] The sample 3 film obtained after the above deposition process was subjected to the following tests:

[0105] (1) The film thickness was measured using a scanning electron microscope.

[0106] (2) The bonding performance of the film was tested using the Revetest scratch test system (CSM, Revetest). Three scratch tests were performed at different positions. The experimental conditions were loading speed: 3 mm / min, scratch length: 5 mm, and loading force: 100 N. The test results are shown in Table 2.

[0107] (3) Dry friction tests were conducted at 25 degrees using a friction tester (TRB3) and repeated 2 to 3 times. A GCr15 steel ball was used as the counterpart, and a reciprocating method was adopted with a frequency of 5 Hz, a track length of 5 mm, a running distance of 180 m, and a normal load of 5 N. A surface profiler (ASTQ) was used to obtain the wear cross section. The wear volume was multiplied by the running step length, and the wear rate was obtained by dividing the wear volume by the load and travel. The test friction coefficient and wear rate results are shown in Table 3.

[0108] (4) Dry friction tests were conducted on samples exposed to salt spray for 7 days at 25°C using a friction tester (TRB3). The test was repeated 2 to 3 times. A GCr15 steel ball was used as the counterpart. A reciprocating method was used with a frequency of 5 Hz, a track length of 5 mm, a running distance of 180 m, and a normal load of 5 N. A surface profiler (ASTQ) was used to obtain the wear cross section. The wear volume was obtained by multiplying it by the running step length. The wear volume was then divided by the load and travel to obtain the wear rate. The results of the test friction coefficient and wear rate are shown in Table 4.

[0109] The cross-sectional SEM image of the wear-resistant and corrosion-resistant nano multilayer ceramic-based film obtained in Example 3 is as follows: Figure 2 As shown, the transmission diagram is Figure 3 As shown in the figure, the bonding force morphology is as follows Figure 4 The friction curve of atmospheric friction is shown as follows. Figure 5 As shown in Figure 2, the average friction coefficient and wear rate of the wear-resistant and corrosion-resistant nano-multilayer ceramic-based film in a salt spray environment for 7 days are as follows: Figure 7 shown.

[0110] Comparative Example 1

[0111] In this embodiment, the substrate material is 316 steel or single crystal silicon wafer. Magnetron sputtering technology is used to prepare a wear-resistant and corrosion-resistant nano-multilayer ceramic-based film on the substrate surface, which mainly includes the following steps:

[0112] The substrate surface was mechanically polished, and the substrate material was placed in an acetone solution for ultrasonic cleaning for 15 minutes, dried with nitrogen, and then placed in an anhydrous ethanol solution for ultrasonic cleaning for 15 minutes, and dried with nitrogen.

[0113] The cleaned substrate was placed in a vacuum chamber and evacuated to a vacuum degree of less than 6×10 -4 mbar, then heated to 180°C and pressure to 4×10 -4mbar, then keep the temperature at 160℃ and the pressure at 3×10 -5 mbar. Sputtering targets were cleaned using WB2 / C targets (purity 99.9 at.%, 50:50 weight ratio) and C targets. Wear-resistant and corrosion-resistant nano-multilayer ceramic-based thin films were deposited. High-purity argon was filled into the chamber. A Cr target (purity 99.99 at.%), a WB2 target (purity 99.9 at.%), and a C target (purity 99.99 at.%) were used for control and setup. The specific steps are as follows:

[0114] (1) Plasma etching: a bias voltage of 200 V was applied to the substrate, the program run time was 40 min, and the chamber temperature was 300 °C;

[0115] (2) Multi-arc ion plating chromium target, current of 30.0A, bias voltage of 20V, working gas of Ar, gas flow rate of 350sccm, deposition time of 480s, rotation speed of 2r / min to deposit a chromium transition layer on the substrate surface;

[0116] (3) Magnetron sputtering of WB2 / C target, sputtering current 50.0A, power 4kW, working gas Ar, gas flow rate 200sccm, deposition time 60s, rotation speed 3r / min;

[0117] (4) Magnetron sputtering C target, sputtering current 50.0A, power 5kW, working gas Ar, gas flow rate 200sccm, deposition time 120s, rotation speed 3r / min;

[0118] (5) Repeat steps 3 and 4 for 100 cycles to deposit a nano-multilayer composite film on the surface of the chromium transition layer.

[0119] The wear-resistant and corrosion-resistant nano-multilayer ceramic-based film was prepared as sample 4, and its specific composition parameters are shown in Table 1.

[0120] The sample 4 film obtained after the above deposition process was subjected to the following tests:

[0121] (1) The film thickness was measured using a scanning electron microscope.

[0122] (2) The bonding performance of the film was tested using the Revetest scratch test system (CSM, Revetest). Three scratch tests were performed at different positions. The experimental conditions were loading speed: 3 mm / min, scratch length: 5 mm, and loading force: 100 N. The test results are shown in Table 2.

[0123] (3) Dry friction tests were conducted at 25 degrees using a friction tester (TRB3) and repeated 2 to 3 times. A GCr15 steel ball was used as the counterpart, and a reciprocating method was adopted with a frequency of 5 Hz, a track length of 5 mm, a running distance of 180 m, and a normal load of 5 N. A surface profiler (ASTQ) was used to obtain the wear cross section. The wear volume was multiplied by the running step length, and the wear rate was obtained by dividing the wear volume by the load and travel. The test friction coefficient and wear rate results are shown in Table 3.

[0124] (4) Dry friction tests were conducted on samples exposed to salt spray for 7 days at 25°C using a friction tester (TRB3). The test was repeated 2 to 3 times. A GCr15 steel ball was used as the counterpart. A reciprocating method was used with a frequency of 5 Hz, a track length of 5 mm, a running distance of 180 m, and a normal load of 5 N. A surface profiler (ASTQ) was used to obtain the wear cross section. The wear volume was obtained by multiplying it by the running step length. The wear volume was then divided by the load and travel to obtain the wear rate. The results of the test friction coefficient and wear rate are shown in Table 4.

[0125] Comparative Example 2

[0126] In this embodiment, the substrate material is 316 steel or single crystal silicon wafer. The WB2 / C thin film is prepared on the substrate surface using magnetron sputtering technology, which mainly includes the following steps:

[0127] The substrate surface was mechanically polished, and the substrate material was placed in an acetone solution for ultrasonic cleaning for 15 minutes, dried with nitrogen, and then placed in an anhydrous ethanol solution for ultrasonic cleaning for 15 minutes, and dried with nitrogen.

[0128] The cleaned substrate was placed in the magnetron sputtering chamber and evacuated to a vacuum degree of less than 6×10 -4 mbar, then heated to 180°C and pressure to 4×10 -4 mbar, then keep the temperature at 160℃ and the pressure at 3×10 -5 mbar. The target distance was adjusted for 5 minutes, and then the target was sputtered and cleaned for 25 minutes. The WB2 / C thin film was deposited by filling the chamber with high-purity argon gas. A Cr target (99.99 at.%) and a WB2 / C target (99.9 at.%, 50:50 weight ratio) were used in the setup and magnetron sputtering. The specific steps are as follows:

[0129] (1) Plasma etching: a bias voltage of 200 V is applied to the substrate, the program running time is 40 min, and the chamber temperature is 300 °C.

[0130] (2) Multi-arc ion plating chromium target, current 50.0A, power 5kW, working gas Ar, gas flow rate 150sccm, deposition time 900s, rotation speed 3r / min to deposit a chromium transition layer on the substrate surface;

[0131] (3) The chromium target and the WB2 / C target were sputtered simultaneously, with a sputtering current of 50.0 A, a power of 5 kW and 4 kW respectively, an Ar working gas, a gas flow rate of 150 sccm, a deposition time of 900 s, and a rotation speed of 3 r / min;

[0132] (4) WB2 / C target sputtering current is 50.0A, power is 4kW, working gas is Ar and C2H2, gas flow rate is 200sccm and 0sccm respectively, deposition time is 9000s, rotation speed is 3r / min, WB2 / C film is deposited on the surface of chromium transition layer;

[0133] The prepared tungsten diboride-based composite film is sample 5, and its specific composition parameters are shown in Table 1.

[0134] The film of Sample 5 prepared after the above deposition treatment was subjected to the following tests:

[0135] (1) The film thickness was measured using a scanning electron microscope.

[0136] (2) The bonding performance of the film was tested using the Revetest scratch test system (CSM, Revetest). Three scratch tests were performed at different positions. The experimental conditions were loading speed: 3 mm / min, scratch length: 5 mm, and loading force: 100 N. The test results are shown in Table 2.

[0137] (3) Dry friction tests were conducted at 25 degrees using a friction tester (TRB3) and repeated 2 to 3 times. A GCr15 steel ball was used as the counterpart, and a reciprocating method was adopted with a frequency of 5 Hz, a track length of 5 mm, a running distance of 180 m, and a normal load of 5 N. A surface profiler (ASTQ) was used to obtain the wear cross section. The wear volume was multiplied by the running step length, and the wear rate was obtained by dividing the wear volume by the load and travel. The test friction coefficient and wear rate results are shown in Table 3.

[0138] (4) Dry friction tests were conducted on samples exposed to salt spray for 7 days at 25°C using a friction tester (TRB3). The test was repeated 2 to 3 times. A GCr15 steel ball was used as the counterpart. A reciprocating method was used with a frequency of 5 Hz, a track length of 5 mm, a running distance of 180 m, and a normal load of 5 N. A surface profiler (ASTQ) was used to obtain the wear cross section. The wear volume was obtained by multiplying it by the running step length. The wear volume was then divided by the load and travel to obtain the wear rate. The results of the test friction coefficient and wear rate are shown in Table 4.

[0139] Comparative Example 3

[0140] In this embodiment, the substrate material is 316 steel or single crystal silicon wafer. The carbon film is prepared on the substrate surface using magnetron sputtering technology, which mainly includes the following steps:

[0141] The substrate surface was mechanically polished, and the substrate material was placed in an acetone solution for ultrasonic cleaning for 15 minutes, dried with nitrogen, and then placed in an anhydrous ethanol solution for ultrasonic cleaning for 15 minutes, and dried with nitrogen.

[0142] The cleaned substrate was placed in the magnetron sputtering chamber and evacuated to a vacuum degree of less than 6×10 -4 mbar, then heated to 180°C and pressure to 4×10 -4 mbar, then keep the temperature at 160℃ and the pressure at 3×10 -5 mbar. The target distance was adjusted for 5 minutes, and then the target was sputtered and cleaned for 25 minutes. To deposit a carbon composite film, the chamber was filled with high-purity argon gas. A Cr target (99.99 at.%) and a C target (99.9 at.%) were used in a 50:50 weight ratio. Magnetron sputtering technology was used. The specific steps were as follows:

[0143] (1) Plasma etching: a bias voltage of 200 V is applied to the substrate, the program running time is 40 min, and the chamber temperature is 300 °C.

[0144] (2) Multi-arc ion plating chromium target, current 50.0A, power 5kW, working gas Ar, gas flow rate 150sccm, deposition time 900s, rotation speed 3r / min to deposit a chromium transition layer on the substrate surface;

[0145] (3) Magnetron sputtering of a C target with Ar and C2H2 as working gases at flow rates of 200 sccm and 75 sccm, respectively, a deposition time of 9000 s, and a rotation speed of 3 r / min to deposit a C composite film on the surface of the chromium transition layer;

[0146] The prepared C composite film is sample 6, and its specific composition parameters are shown in Table 1.

[0147] The sample 6 film obtained after the above deposition process was subjected to the following tests:

[0148] (1) The film thickness was measured using a scanning electron microscope.

[0149] (2) The bonding performance of the film was tested using the Revetest scratch test system (CSM, Revetest). Three scratch tests were performed at different positions. The experimental conditions were loading speed: 3 mm / min, scratch length: 5 mm, and loading force: 100 N. The test results are shown in Table 2.

[0150] (3) Dry friction tests were conducted using a tribometer (TRB3) at 25°C in an atmospheric environment, with 2-3 repeats. A GCr15 steel ball was used as the counterpart, and a reciprocating method was employed with a frequency of 5 Hz, a track length of 5 mm, a running distance of 180 m, and a normal load of 5 N. A surface profiler (ASTQ) was used to obtain the wear cross-section, which was multiplied by the running step length to obtain the wear volume. The wear volume was then divided by the load and travel to obtain the wear rate. The results of the test friction coefficient and wear rate are shown in Table 3.

[0151] (4) Dry friction tests were conducted on samples exposed to salt spray for 7 days at 25°C using a friction tester (TRB3). The test was repeated 2 to 3 times. A GCr15 steel ball was used as the counterpart. A reciprocating method was used with a frequency of 5 Hz, a track length of 5 mm, a running distance of 180 m, and a normal load of 5 N. A surface profiler (ASTQ) was used to obtain the wear cross section. The wear volume was multiplied by the running step length, and the wear rate was obtained by dividing the wear volume by the load and travel. The results of the test friction coefficient and wear rate are shown in Table 4.

[0152] Table 1 Composition parameters of the film samples obtained in Examples 1-3 and Comparative Examples 1-3

[0153]

[0154] It can be seen from Table 2 that the wear-resistant and corrosion-resistant nano-multilayer ceramic-based film sample 3 obtained in Laboratory 3 has the best bonding strength.

[0155] Table 2 Binding strength data of film samples obtained in Examples 1-3 and Comparative Examples 1-3

[0156]

[0157] The friction coefficients and wear rates of the film samples obtained in Examples 1-3 and Comparative Examples 1-3 under atmospheric conditions are shown in Table 3. The wear-resistant and corrosion-resistant nano-multilayer ceramic-based film sample 3 in Example 3 has the best friction coefficient and the best wear rate.

[0158] Table 3 Friction and wear of film samples obtained in Examples 1-3 and Comparative Examples 1-3 under atmospheric conditions

[0159]

[0160] The corrosion of the film samples obtained in Examples 1-3 and Comparative Examples 1-3 under salt spray environment for 7 days is as follows: Figure 6 As shown, sample 4 in comparative example 1, sample 5 in comparative example 2, and samples 1-3 in embodiments 1-3 were not corroded, while the film C in comparative example 3 showed film peeling.

[0161] The friction coefficients and wear rates of the film samples obtained in Examples 1-3 and Comparative Examples 1-3 under a salt spray environment for 7 days are shown in Table 4. On the basis that film samples 1-5 were not corroded, the wear-resistant and corrosion-resistant nano-multilayer ceramic-based film sample 3 in Example 3 had the best friction coefficient and the best wear rate.

[0162] Table 4 Friction and wear of the film samples obtained in Examples 1-3 and Comparative Examples 1-3 under salt spray environment for 7 days

[0163]

[0164] The various aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and are not intended to limit the present invention, the scope of which is defined solely by the claims. Other embodiments, modifications and uses will be apparent to those skilled in the art without departing from the spirit and scope of the invention as claimed.

[0165] In addition, the inventors of this case also referred to the aforementioned embodiments and conducted experiments using other raw materials, process operations, and process conditions described in this specification, and obtained relatively ideal results.

[0166] Although the present invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions, and / or additions may be made and that substantial equivalents may be substituted for the elements of the embodiments without departing from the spirit and scope of the present invention. Additionally, many modifications may be made to adapt specific circumstances or materials to the teachings of the present invention without departing from the scope of the present invention. Therefore, it is not intended herein to limit the present invention to the disclosed specific embodiments for carrying out the present invention, but rather to include all embodiments within the scope of the appended claims. Furthermore, unless specifically stated, any use of the terms first, second, etc. does not indicate any order or importance, but rather uses the terms first, second, etc. to distinguish one element from another.

Claims

1. A wear-resistant and corrosion-resistant nano-multilayer ceramic-based film, characterized in that: The invention relates to a nanostructured composite material comprising a chromium transition layer and a nanostructured composite material sequentially stacked in a thickness direction, wherein the nanostructured composite material comprises a plurality of stacked periodic units, each periodic unit comprising a tungsten diboride / carbon nanolayer and a carbon nanolayer, and wherein the tungsten diboride / carbon nanolayer and the carbon nanolayer are alternately stacked in the nanostructured composite material; the nanostructured composite material comprises 100 periodic units; The tungsten diboride / carbon nanolayer in the periodic unit adjacent to the chromium transition layer is arranged adjacent to the chromium transition layer, and the top of the nano multilayer composite structure is the carbon nanolayer; In addition, the C atomic percentage in the wear-resistant and corrosion-resistant nano-multilayer ceramic-based film is 65-80%, the W atomic percentage is 9-11%, and the B atomic percentage is 14-26%; the mass ratio of tungsten diboride and carbon contained in the tungsten diboride / carbon target used to form the tungsten diboride / carbon nanolayer is 1:

1.

2. The wear-resistant and corrosion-resistant nano-multilayer ceramic-based film according to claim 1, characterized in that: The wear-resistant and corrosion-resistant nano multilayer ceramic-based film has a bonding force of 28-30N.

3. The wear-resistant and corrosion-resistant nano-multilayer ceramic-based film according to claim 1, characterized in that: The wear-resistant and corrosion-resistant nano multilayer ceramic-based film has a friction coefficient of 0.2-0.28 and a wear rate of 2.91-4.21x10 -7 mm 3 / Nm.

4. The wear-resistant and corrosion-resistant nano-multilayer ceramic-based film according to claim 1, characterized in that: The wear-resistant and corrosion-resistant nano multilayer ceramic-based film has a friction coefficient of 0.25-0.35 and a wear rate of 10-16x10 -7 mm 3 / Nm.

5. The method for preparing the wear-resistant and corrosion-resistant nano-multilayer ceramic-based film according to any one of claims 1 to 4, characterized in that: include: A chromium transition layer is deposited on the substrate surface using multi-arc ion plating technology; Using magnetron sputtering technology, tungsten diboride / carbon nanolayers and carbon nanolayers are alternately deposited on the chromium transition layer to form a periodic unit. 100 periodic units are repeatedly prepared to produce a wear-resistant and corrosion-resistant nano-multilayer ceramic-based film. The conditions for depositing the tungsten diboride / carbon nanolayer include: using a tungsten diboride / carbon target as a cathode target, using an inert gas as a working gas, applying a target current to the tungsten diboride / carbon target, applying a negative bias voltage to the substrate, applying a target current of 40-60A, a power of 3-4kW, a working gas flow rate of 200-300sccm, a deposition time of 60-80s, a rotation speed of 3-5r / min, and a mass ratio of tungsten diboride to carbon contained in the tungsten diboride / carbon target of 1:1; The conditions for depositing the carbon nanolayer include: using a carbon target as a cathode target material, using an inert gas as a working gas, applying a target current to the carbon target, applying a negative bias voltage to the substrate, the applied target current is 40~60A, the power is 5~6kW, the gas flow rate of the working gas is 200~300sccm, the deposition time is 180s~300s, and the rotation speed is 3~5r / min.

6. The preparation method according to claim 5, characterized in that include: Firstly, the substrate is subjected to plasma etching treatment, and then the chromium transition layer is deposited on the surface of the substrate; The plasma etching process includes applying a bias voltage of 180-220 V to the substrate, etching for 30-40 minutes, and etching at a temperature of 200-300° C.

7. The preparation method according to claim 6, characterized in that: The material of the substrate includes at least any one of 316 stainless steel or single crystal silicon wafer.

8. The preparation method according to claim 6, characterized in that include: The multi-arc ion plating technology is adopted, a chromium target is used as a cathode target material, an inert gas is used as a working gas, a target current is applied to the chromium target, a negative bias voltage is applied to the substrate, and the chromium transition layer is deposited on the surface of the substrate; The target current in the multi-arc ion plating technology is 20-30A, the bias voltage is 20-30V, the flow rate of the working gas is 350-400sccm, the deposition time is 480-500s, and the rotation speed is 1-3r / min.

9. The preparation method according to any one of claims 5 to 8, characterized in that: The inert gas includes argon.

10. Use of the wear-resistant and corrosion-resistant nano-multilayer ceramic-based film according to any one of claims 1 to 4 in substrate protection, wherein the substrate comprises at least a partial surface of a transmission system or component of marine equipment, and the marine equipment comprises a ship.

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