CN109161845B - Marine environment wear-resistant self-lubricating nano composite coating and preparation method and application thereof - Google Patents

Abstract

The invention relates to a marine environment wear-resistant self-lubricating nano composite coating and a preparation method and application thereof. The nano composite coating comprises a TiN transition layer and a nano composite layer which are sequentially arranged on the surface of the substrate, and the nano composite layer comprises a TiBON layer and a TiBO layer which are sequentially and alternately arranged on the surface of the TiN transition layer. The nano composite coating provided by the invention takes TiN as a transition layer, so that the connection between the nano composite layer and the substrate is enhanced, and the bonding force of the whole coating is increased; the nano composite layer formed by the TiBON layer and the TiBO layer has high hardness and low friction coefficient, and has self-lubricating property in marine environment, and the TiBON layer and the TiBO layer are sequentially alternated to reduce the stress of the coating, so that the wear resistance and the corrosion resistance are further improved. Experimental results show that the hardness of the wear-resistant self-lubricating nano composite coating provided by the invention can reach 32GPa, and the service life of marine equipment components applying the coating can be prolonged by more than 5 times.

Description

A marine environment wear-resistant self-lubricating nanocomposite coating and its preparation method and application

technical field

The invention belongs to the technical field of hard coatings, and in particular relates to a marine environment wear-resistant self-lubricating nano-composite coating and a preparation method and application thereof.

Background technique

Hard coating is an effective way to strengthen the surface of materials, exert the potential of materials, and improve production efficiency. It is a kind of surface coating, which means that the microhardness deposited on the surface of the base by physical or chemical methods is greater than a certain value of surface coating. Hard coatings have been widely used in the cutting industry, mold industry, geological drilling, textile industry, machinery manufacturing and aerospace fields, and play an increasingly important role. Among them, the application of hard coating in the cutting industry can not only process materials that are difficult to process with ordinary cutting tools such as cutters and drills, but also improve the accuracy of cutting and exert superhardness, toughness, wear resistance, self-lubricating, etc. The advantage is considered to be a revolution in the history of cutting. However, due to the high concentration of acid ions such as Cl-, SO42-, HCO3- in seawater, it has a strong corrosion and damage effect on the marine machinery of metal materials, which can easily lead to the failure of mechanical parts and even the main body of the machinery. This requires Oil extraction machinery, marine transportation hulls, etc. have good corrosion resistance. After years of research, it is found that surface treatment of materials, especially forming a protective layer with strong corrosion resistance on the surface is the most effective and lowest cost method. Therefore, the study of corrosion-resistant films in seawater environment has become a At present, the development of marine resources is the top priority.

After a lot of research, it is found that polymer materials and ceramic materials have their own shortcomings under the condition of water lubrication. Therefore, in order to meet the requirements of low friction coefficient and low wear rate of water-lubricated friction parts, a layer with a thickness of only Nanocomposite films of several micrometers or even hundreds of nanometers, short running-in periods and good water-lubricated friction properties have become a better solution. However, there are many types of nanocomposite films, not all hard films have good water-lubricated tribological properties, and there are many films whose tribological properties (coefficient of friction and wear rate) under water-lubricated conditions are relatively dry. Worse, and prone to spalling and failure quickly due to bond issues.

Therefore, it is of great research significance and application value to study the water-lubricated tribological properties of different hard films and obtain a coating with high hardness, corrosion resistance and wear resistance.

SUMMARY OF THE INVENTION

The purpose of the present invention is to overcome the defects and deficiencies of the water-lubricated tribological properties of the hard film in the prior art, and to provide a marine environment wear-resistant self-lubricating nanocomposite coating. In the nanocomposite coating provided by the invention, the multi-layer nanocomposite structure TiBON/TiBO coating has both hardness tester corrosion resistance, and at the same time generates borate in the seawater friction environment, has a self-lubricating function, further reduces the friction coefficient, and improves the Wear resistance; multi-layer nano-composite structure boron oxide can reduce the internal stress of the coating, improve the bonding force and service life, and has important application value in the field of marine equipment surface protection.

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

Another object of the present invention is to provide the application of the above-mentioned nanocomposite coating in the surface protection of marine equipment.

For realizing the above-mentioned purpose of the invention, the present invention adopts following technical scheme:

A wear-resistant self-lubricating nanocomposite coating in marine environment, comprising a TiN transition layer and a nanocomposite layer sequentially arranged on the surface of a substrate, the nanocomposite layer comprising a TiBON layer and a TiBO layer alternately arranged on the surface of the TiN transition layer; the The TiBON layer is a nanocomposite structure including TiN, TiB ₂ nanocrystals, amorphous BN and amorphous oxide TiO ₂ . The atomic percentage of titanium in the TiBON layer is 29-40%, and the atomic percentage of boron is 16-16%. 22%, the atomic percentage of oxygen is 7-16%, and the atomic percentage of nitrogen is 35-46%; the TiBO layer is a nanocomposite structure including TiB2 nanocrystalline and amorphous oxide _{TiO2 ;} the TiBO In the layer, the atomic percentage of titanium element is 30-40%, the atomic percentage of boron element is 9-25%, and the atomic percentage of oxygen element is 40-52%.

The amorphous oxide referred to in the present invention refers to TiO ₂ .

The hard film represented by nitrogen-boron-based film has many excellent physical and chemical properties, especially its high hardness, anti-wear, anti-oxidation and corrosion resistance. The vigorous development of shipping, offshore operations, water conservancy devices and other related industries has broadened new horizons. However, the increase in hardness is not the only indicator for evaluating hard nanocomposite coatings. For applications in marine environments, it is more important to improve the corrosion resistance and wear resistance of coatings.

The TiN transition layer can improve the bonding force between the nanocomposite layer and the substrate, enhance the use effect of the coating, and improve the service life of the coating.

The function of the TiBON layer is: the layer has excellent wear resistance and low coefficient of friction, as well as high hardness and self-lubricating properties.

The function of the TiBO layer is: the layer has excellent wear resistance, low stress and low friction coefficient, and has both high hardness and self-lubricating properties.

The alternating and periodic arrangement of the TiBON layer and the TiBO layer can reduce the stress of the coating, increase the crystal plane structure and grain boundary of the coating, and further improve the wear resistance and corrosion resistance.

The nano-composite coating provided by the invention uses TiN as the transition layer, which enhances the connection between the nano-composite layer and the substrate and increases the bonding force of the overall coating; the nano-composite layer composed of the TiBON layer and the TiBO layer has both high hardness and low friction. coefficient, self-lubricating properties in marine environment, and the sequential alternation of TiBON layers and TiBO layers can reduce the stress of the coating and further improve the wear resistance and corrosion resistance properties. The experimental results show that the hardness of the wear-resistant and self-lubricating nano-composite coating provided by the present invention can reach 32GPa, and the service life of marine equipment components using the coating can be increased by more than 5 times.

Preferably, the thickness of each TiBON layer and TiBO layer is independently selected from 2˜50 nm.

More preferably, the thicknesses of each TiBON layer and TiBO layer are independently selected from 10-30 nm.

More preferably, the thicknesses of each TiBON layer and TiBO layer are independently selected from 15-25 nm.

Preferably, the number of the TiBON layers is 10-100 layers.

More preferably, the number of the TiBON layers is 20-80 layers,

More preferably, the number of the TiBON layers is 40-50 layers.

Preferably, in the TiBON layer, the atomic percentage of titanium is 32%, the atomic percentage of boron is 19%, the atomic percentage of oxygen is 13%, and the atomic percentage of nitrogen is 36%.

Preferably, the grain size of the TiBON layer is 2-15 nm.

More preferably, the grain size of the TiBON layer is 3-8 nm.

Preferably, in the TiBO layer, the atomic percentage of titanium element is 33%, the atomic percentage of boron element is 19%, and the atomic percentage of oxygen element is 48%.

Preferably, the grain size of the TiBO layer is 3-12 nm.

More preferably, the grain size of the TiBO layer is 4-6 nm.

Preferably, in the TiN transition layer, the atomic percentage of titanium is 50-58%, and the atomic percentage of nitrogen is 42-50%; the thickness of the TiN transition layer is 100-800 nm.

More preferably, the thickness of the TiN transition layer is 200-500 nm.

More preferably, the thickness of the TiN transition layer is 300-400 nm.

Preferably, the base body is aluminum-titanium alloy or stainless steel.

More preferably, the matrix is Ti-6Al-4V alloy.

It should be understood that the composition of the Ti-6Al-4V is not particularly limited in the present invention, and the Ti-6Al-4V alloy known to those skilled in the art for high-temperature corrosion-resistant parts of engines and marine equipment can be used.

The preparation method of above-mentioned nanocomposite coating, comprises the steps:

S1: deposit a TiN transition layer on the surface of the substrate;

S2: TiBON layers and TiBO layers are alternately deposited on the surface of the TiN transition layer obtained in S1, so as to obtain a marine environment wear-resistant self-lubricating nanocomposite coating.

Preferably, the TiBON layer is prepared through the following process: using TiB ₂ as a deposition target, feeding N ₂ and O ₂ into the TiBON layer, and depositing the TiBON layer; the volume ratio of N ₂ and O ₂ is 1:2 ~4:1.

Preferably, the TiBO layer is prepared by the following process: using TiB ₂ as a deposition target, feeding Ar and O ₂ to obtain the TiBO layer, and the volume ratio of Ar and O ₂ is 1:2-3 :1.

Preferably, in S1, a TiN transition layer is deposited on the surface of the substrate by using cathodic arc ion plating technology.

The present invention has no special limitation on the operation of the cathodic arc ion plating technology of the TiN transition layer, and the technical solution of the cathodic arc ion plating technology well known to those skilled in the art can be used.

Preferably, the parameters of the cathodic arc ion plating technology are: substrate speed of 2 to 8 rpm, sputtering temperature of 300 to 500° C., reactive gas nitrogen, deposition gas pressure of 1.0 to 1.8 Pa, bias voltage of 100 to 180 V, and target current of 40 to 40 100A, deposition time 10-30min.

Preferably, the parameters of the cathodic arc ion plating technology are: substrate speed of 3-6 rpm, sputtering temperature of 400-450°C, reactive gas nitrogen, deposition gas pressure of 1.3-1.5Pa, bias voltage of 130-160V, target current of 60- 75A, deposition time 15-25min.

Preferably, in S2, a high-power pulsed magnetron sputtering technique is used to deposit the TiBON layer and the TiBO layer alternately in sequence.

In the present invention, the high-power pulsed magnetron sputtering deposition can further enable the coating to have excellent film-base adhesion, reduce the internal stress of the coating, and improve the wear resistance and the hardness of the coating.

More preferably, the process of the high-power pulsed magnetron sputtering technology is: open the TiB ₂ target, deposit the TiBO layer; then open the N ₂ flow valve, deposit the TiBON layer; repeat the deposition of the TiBO layer and the TiBON layer to the described The nanocomposite layer deposition is complete.

Preferably, the parameters for depositing the TiBO layer are: sputtering gas argon, reactive gas oxygen, the total pressure of argon and oxygen is 0.4-1.2Pa, the pressure ratio of argon and oxygen is 1-3:3-1, the speed of the substrate is 2～10rpm, sputtering temperature 300～500℃, target average current 3～8A, target peak current 300～800A, target peak voltage 300～800V, duty ratio 1～8%.

More preferably, the parameters for depositing the TiBON layer are: sputtering gas argon, reactive gases oxygen and nitrogen, the total pressure of argon and oxygen is 0.6-1.0Pa, and the pressure ratio of nitrogen and oxygen is 1-2:2-1, The substrate speed is 3-6rpm, the sputtering temperature is 300-500℃, the average target current is 2-6A, the target peak current is 400-700A, the target peak voltage is 500-800V, and the duty cycle is 3-6%.

Preferably, after the alternate deposition, S2 further includes the step of cooling the deposited product.

Preferably, the cooling is carried out in the deposition atmosphere.

Preferably, the end temperature of the cooling is below 120°C.

Preferably, the end temperature of the cooling is below 80°C.

Preferably, before S1, the substrate further includes the steps of sequentially performing pretreatment, sputter cleaning and activation.

The present invention does not have a special limitation on the operation of the pretreatment, and the technical solution of the pretreatment well-known to those skilled in the art can be adopted.

Preferably, the process of the pretreatment is washing and drying.

Preferably, the washing is ultrasonication in acetone and absolute ethanol in sequence; the time of ultrasonication in acetone and absolute ethanol is independently 15-30 min.

More preferably, the ultrasonic time in acetone and absolute ethanol is both 20min.

Preferably, the drying is using clean compressed air.

Preferably, the parameters of the sputtering cleaning are as follows: the rotational speed of the substrate is 2-8rpm, the sputtering temperature is 300-500°C, the sputtering gas is argon, the sputtering gas pressure is 0.3-1.2Pa, the bias voltage is 800-1200V, and the sputtering cleaning is performed. Time 10 ~ 30min.

In the present invention, the sputter cleaning can improve the bonding ability between the substrate and the TiN transition layer.

More preferably, the parameters of the sputtering cleaning are: the speed of the substrate is 4～6rpm, the sputtering temperature is 350～400℃, the sputtering gas is argon, the sputtering gas pressure is 0.5～0.8Pa, the bias voltage is 900～1100V, and the sputtering gas is argon. The spray cleaning time is 20 to 35 minutes.

Preferably, the activation is carried out by using a Ti cathode arc target; the parameters of the activation are: the speed of the substrate is 2-9 rpm, the sputtering temperature is 300-500°C, the sputtering gas is argon, the sputtering gas pressure is 0.8-1.5Pa, and the bias voltage is 400 ～800V, target current 40～100A, deposition time 5～25min.

In the present invention, the activation is to bombard the surface of the substrate with Ti ions, increase the energy state of the particles on the surface of the substrate, generate a metal layer, and enhance the bonding force between the coating and the substrate.

Preferably, the parameters of the activation are: the speed of the substrate is 3～6rpm, the sputtering temperature is 400～450℃, the sputtering gas is argon, the sputtering gas pressure is 1.0～1.2Pa, the bias voltage is 500～700V, and the target current is 60～80A , the deposition time is 10-15min.

The application of the above-mentioned nanocomposite coating in marine equipment surface protection is also within the protection scope of the present invention.

Compared with the prior art, the present invention has the following beneficial effects:

The nano-composite coating provided by the invention uses TiN as the transition layer, which enhances the connection between the nano-composite layer and the substrate and increases the bonding force of the overall coating; the nano-composite layer composed of the TiBON layer and the TiBO layer has both high hardness and low friction. coefficient, self-lubricating properties in marine environment, and the sequential alternation of TiBON layers and TiBO layers can reduce the stress of the coating and further improve the wear resistance and corrosion resistance properties. The experimental results show that the hardness of the wear-resistant and self-lubricating nano-composite coating provided by the present invention can reach 32GPa, and the service life of marine equipment parts using the coating can be increased by more than 5 times.

Description of drawings

FIG. 1 is an XRD diffraction image of the wear-resistant self-lubricating nanocomposite coating provided in Example 1 of the present invention.

2 is a TEM image of the wear-resistant self-lubricating nanocomposite coating provided in Example 1 of the present invention;

FIG. 3 is a friction and wear image of the wear-resistant self-lubricating nanocomposite coating (b) provided in Example 2 of the present invention and Comparative Example 3 (a).

Detailed ways

The present invention is further described below in conjunction with the examples. These examples are only intended to illustrate the present invention and not to limit the scope of the present invention. The experimental methods that do not specify specific conditions in the following examples are usually in accordance with the conventional conditions in the field or the conditions suggested by the manufacturer; the raw materials, reagents, etc. used, unless otherwise specified, are available from commercial channels such as conventional markets. The obtained raw materials and reagents. Any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention fall within the scope of protection claimed by the present invention.

Example 1

This embodiment provides a nanocomposite coating (coating 1), and the preparation method is as follows.

The pretreated Ti-6Al-4V substrate was evenly fixed on the support, loaded into the coating machine, adjusted the speed of the workpiece support to 3 rpm, pumped to a background vacuum of 1.0 × 10 ^-3 Pa, and turned on the heater at the same time. 300°C; open the argon gas flow valve, adjust the vacuum chamber to about 0.3Pa, apply a negative bias voltage of 1200V to the substrate, and perform glow sputtering cleaning for 10min;

Then reduce the negative bias voltage of the substrate to 400V, open the argon gas flow valve, control the gas pressure to 0.8Pa, open the Ti cathode arc target, adjust the target current to 40A, the deposition temperature to 500℃, bombard the substrate with high Ti ions for 5min to activate the substrate surface; Close the argon flow valve, open the nitrogen flow valve, the substrate bias voltage is reduced to 100V, the coating pressure is 1.0pa, the substrate temperature is 500°C, the target current is 40A, and the TiN transition layer is deposited for 10min; , the nitrogen/oxygen ratio is 1/2, the workpiece rack speed is 3rpm, the TiB ₂ target is turned on, the average current of high-power pulsed magnetron sputtering is adjusted to 3A, the peak current is 700A, the peak voltage is 500V, the duty cycle is 3%, and the TiBON layer is deposited 5 minutes; close the nitrogen flow valve, control the argon/oxygen ratio to 1/3, the average target current is 3A, the target peak current is 800A, the target peak voltage is 300V, the duty cycle is 1%, and TiBO is deposited for 5 minutes. In this way, the nitrogen flow valve is opened and closed alternately, the TiBON/TiBO layer is deposited for 60 minutes, the power is turned off, and the flow valve is closed.

The surface coating of the prepared sample is named as coating 1, and the XRD and TEM images of the coating are shown in Figures 1 and 2. The X-ray diffraction peaks of nanocrystalline TiN and TiB ₂ can be clearly seen in Figure 1, but the diffraction peaks of BN and oxide are not found, which can be speculated to be amorphous phase; Figure 2 shows that nanocrystalline grains and amorphous matrix Structure. Therefore, the monolithic coating is a nanocomposite structure of TiN, TiB2 nanocrystalline, amorphous BN and amorphous _oxide .

The atomic percentage and thickness of each layer of coating 1 are as follows:

TiN transition layer: titanium 52at.%, nitrogen 48at.%; thickness 120nm;

TiBON layer: titanium 30at.%, boron 20at.%, oxygen 14at.% and nitrogen 36at.%; thickness 10nm;

TiBO layer: titanium 35 at. %, boron 16 at. % and oxygen 49 at. %; thickness 12 nm.

Example 2

This embodiment provides a nanocomposite coating (coating 2), and the preparation method is as follows.

The pretreated Ti-6Al-4V substrate was evenly fixed on the support, loaded into the coating machine, adjusted the speed of the workpiece support to 3 rpm, pumped to a background vacuum of 1.0 × 10 ^-3 Pa, and turned on the heater at the same time. 300°C; open the argon flow valve, adjust the vacuum chamber to about 1.2Pa, apply a negative bias voltage of 1200V to the substrate, and perform glow sputtering cleaning for 35min;

Then reduce the negative bias voltage of the substrate to 800V, open the argon gas flow valve, control the gas pressure to 0.5Pa, open the Ti cathode arc target, adjust the target current to 40A, the deposition temperature to 500℃, bombard the substrate with high energy of Ti ions for 5min to activate the substrate surface; Close the argon flow valve, open the nitrogen flow valve, the substrate bias voltage is reduced to 100V, the coating pressure is 1.0pa, the substrate temperature is 500°C, the target current is 40A, and the TiN transition layer is deposited for 10min; , the nitrogen/oxygen ratio is 1/2, the workpiece rack speed is 3rpm, the TiB ₂ target is turned on, the average current of high-power pulsed magnetron sputtering is adjusted to 3A, the peak current is 700A, the peak voltage is 500V, the duty cycle is 8%, and the TiBON layer is deposited 5 minutes; close the nitrogen flow valve, control the argon/oxygen ratio to 1/3, the average target current is 3A, the target peak current is 800A, the target peak voltage is 300V, the duty cycle is 6%, and TiBO is deposited for 5 minutes. In this way, the nitrogen flow valve is opened and closed alternately, the TiBON/TiBO layer is deposited for 100 minutes, the power is turned off, and the flow valve is closed.

The prepared surface coating of the sample is named as coating 2. Figure 3 shows the friction and wear images of the wear-resistant and self-lubricating nanocomposite coating (b) in Example 2 and Comparative Example 3 (a). It can be clearly seen from the figure that the wear resistance of coating 2 is better than that of comparative example 3 in marine environment.

The atomic percentages and thicknesses of Coating 2 are as follows:

TiN transition layer: titanium 51at.%, nitrogen 49at.%; thickness 400nm;

TiBON layer: titanium 32at.%, boron 19at.%, oxygen 13at.% and nitrogen 36at.%; thickness 25nm;

TiBO layer: titanium 33 at. %, boron 19 at. % and oxygen 48 at. %; thickness 30 nm.

Example 3

This embodiment provides a nanocomposite coating (coating 3), and the preparation method is as follows.

The pretreated Ti-6Al-4V substrate was evenly fixed on the support, loaded into the coating machine, adjusted the workpiece support speed to 5 rpm, pumped to a background vacuum of 1.0 × 10 ^-3 Pa, and turned on the heater at the same time. 400°C; open the argon flow valve, adjust the vacuum chamber to about 1.2Pa, apply a negative bias voltage of 1200V to the substrate, and perform glow sputtering cleaning for 20min;

Then reduce the negative bias voltage of the substrate to 800V, open the argon gas flow valve, control the gas pressure to 0.5Pa, open the Ti cathode arc target, adjust the target current to 80A, the deposition temperature to 500℃, bombard the substrate with high energy of Ti ions for 15min to activate the substrate surface; Close the argon flow valve, open the nitrogen flow valve, the substrate bias voltage is reduced to 120V, the coating pressure is 1.0Pa, the substrate temperature is 500℃, the target current is 60A, and the TiN transition layer is deposited for 10min; , the nitrogen/oxygen ratio is 2/1, the workpiece rack speed is 3rpm, the TiB ₂ target is turned on, the average current of high-power pulsed magnetron sputtering is adjusted to 3A, the peak current is 700A, the peak voltage is 500V, the duty cycle is 3%, and the TiBON layer is deposited 5 minutes; close the nitrogen flow valve, control the argon/oxygen ratio to be 3/1, the average target current is 3A, the target peak current is 800A, the target peak voltage is 300V, the duty cycle is 3%, and TiBO is deposited for 8 minutes. In this way, the nitrogen flow valve is opened and closed alternately, the TiBON/TiBO layer is deposited for 90 minutes, the power is turned off, and the flow valve is closed.

The prepared sample surface coating is named as coating 3, and its atomic percentage and thickness of the coating are as follows:

TiN transition layer: titanium 55at.%, nitrogen 45at.%; thickness 380nm;

TiBON layer: titanium 30at.%, boron 20at.%, oxygen 15at.% and nitrogen 35at.%; thickness 18nm;

TiBO layer: titanium 40at.%, boron 15at.% and oxygen 45at.%; thickness 9nm.

It should be understood that other atomic percentages and thicknesses of TiN transition layers, TiBON layers and TiBO layers can be obtained by controlling the deposition conditions, which will not be repeated here.

Comparative Example 1

A sample containing only a titanium-nitrogen buffer layer prepared on a Ti-6Al-4V alloy substrate by the method described in Example 1 was named coating 4.

Comparative Example 2

A sample containing only a titanium-nitrogen buffer layer and a TiBON layer prepared on a Ti-6Al-4V alloy substrate by the method described in Example 1 is named coating 5.

Comparative Example 3

A sample containing only a titanium-nitrogen buffer layer and a TiBO layer prepared on a Ti-6Al-4V alloy substrate by the method described in Example 1 is named coating 6.

The properties of the coatings obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were tested, and the results are shown in Table 1.

Table 1 Coating performance test results of Examples 1-3 and Comparative Examples 1-3

Numbering Hardness (<u>GPa</u>) Binding force (N) Seawater friction coefficient Coating 1 twenty four 63 0.08 Coating 2 32 65 0.12 Coating 3 18 60 0.12 Coating 4 20 45 0.56 Coating 5 twenty two 46 0.42 Coating 6 twenty four 37 0.48

It can be seen from the above comparative examples and examples that the wear-resistant self-lubricating nanocomposite coating provided by the present invention has high hardness, low friction coefficient in seawater environment, and strong bonding force between the coating and the substrate.

The above descriptions are only preferred embodiments of the present invention, and do not limit the present invention in any form. It should be pointed out that for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can also be made, and these improvements and modifications should also be regarded as the protection scope of the present invention.

Claims (10)

1. a marine environment wear-resistant self-lubricating nanocomposite coating, is characterized in that, comprises the TiN transition layer and the nanocomposite layer that are arranged successively on the substrate surface, and the nanocomposite layer comprises the TiBON that is alternately arranged successively on the surface of the TiN transition layer layer and TiBO layer; the TiBON layer is a nanocomposite structure including TiN, TiB2 nanocrystalline, amorphous BN and amorphous _{oxide TiO2} , the atomic percentage of titanium in the TiBON layer is 29-40%, boron The atomic percentage of elements is 16-22%, the atomic percentage of oxygen is 7-16%, and the atomic percentage of nitrogen is 35-46%; the TiBO layer is composed of TiB ₂ nanocrystalline and amorphous oxide TiO ₂ . Nano-composite structure; in the TiBO layer, the atomic percentage of titanium element is 30-40%, the atomic percentage of boron element is 9-25%, and the atomic percentage of oxygen element is 40-52%. 2 . The nanocomposite coating according to claim 1 , wherein the thicknesses of each TiBON layer and TiBO layer are independently selected from 2 to 50 nm. 3 . 3 . The nanocomposite coating according to claim 1 , wherein the number of the TiBON layers is 10-100 layers. 4 . 4. The nanocomposite coating according to claim 1, wherein in the TiBON layer, the atomic percentage of titanium is 32%, the atomic percentage of boron is 19%, and the atomic percentage of oxygen is 13%, The atomic percentage of nitrogen is 36%. 5 . The nanocomposite coating according to claim 1 , wherein in the TiBO layer, the atomic percentage of titanium is 33%, the atomic percentage of boron is 19%, and the atomic percentage of oxygen is 48%. 6 . 6. The nanocomposite coating according to claim 1, wherein in the TiN transition layer, the atomic percentage of titanium is 50-58%, and the atomic percentage of nitrogen is 42-50%; The thickness of the layer is 100 to 800 nm. 7. The preparation method of any one of the nanocomposite coatings of claims 1 to 6, characterized in that, comprising the steps of: S1: deposit a TiN transition layer on the surface of the substrate; S2: TiBON layers and TiBO layers are alternately deposited on the surface of the TiN transition layer obtained in S1, so as to obtain a marine environment wear-resistant self-lubricating nanocomposite coating. 8. The preparation method according to claim 7, wherein the TiBON layer is prepared by the following process: using TiB ₂ as a deposition target, feeding N ₂ and O ₂ , and depositing the TiBON layer; The volume ratio of N ₂ and O ₂ is 1:2 to 4:1. 9 . The preparation method according to claim 7 , wherein the TiBO layer is prepared by the following process: using TiB ₂ as a deposition target, feeding Ar and O ₂ into it, and depositing the TiBO layer, the Ar And the volume ratio of O ₂ is 1:2～3:1. 10. The application of any one of the nanocomposite coatings of claims 1 to 6 in the protection of marine equipment surfaces.

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