CN114015981A

CN114015981A - Rare earth doped erosion-resistant protective coating and preparation method thereof

Info

Publication number: CN114015981A
Application number: CN202111262258.5A
Authority: CN
Inventors: 王丽; 汪爱英; 张栋; 阮海涛; 王振玉
Original assignee: Ningbo Institute Of Industrial Technology; Ningbo Institute of Material Technology and Engineering of CAS
Current assignee: Ningbo Institute Of Industrial Technology; Ningbo Institute of Material Technology and Engineering of CAS
Priority date: 2021-10-28
Filing date: 2021-10-28
Publication date: 2022-02-08
Anticipated expiration: 2041-10-28
Also published as: CN114015981B

Abstract

The invention discloses a rare earth-doped erosion-resistant protective coating and a preparation method thereof. The rare earth-doped anti-erosion protective coating comprises an ion etching layer, a Ti layer serving as a bonding coordination layer, a TiN layer serving as a bonding strengthening layer, a first rare earth-doped TiAlSiN functional layer serving as a first functional layer, a second rare earth-doped TiAlSiN functional layer serving as a second functional layer and a third rare earth-doped TiAlSiN functional layer serving as a third functional layer, wherein the first rare earth-doped TiAlSiN functional layer, the second rare earth-doped TiAlSiN functional layer and the third rare earth-doped TiAlSiN functional layer are sequentially stacked, and rare earth elements doped with the first rare earth-doped TiAlSiN functional layer, the second rare earth-doped TiAlSiN functional layer and the third rare earth-doped TiAlSiN functional layer comprise Y and/or Ce. The rare earth doped erosion-resistant protective coating has excellent mechanical properties such as high hardness, high toughness and the like and good erosion resistance, and meanwhile, the preparation process of the protective coating is simple, and the erosion-resistant protective performance under certain severe working conditions can be realized.

Description

Rare earth doped erosion-resistant protective coating and preparation method thereof

Technical Field

The invention relates to a protective coating, in particular to a rare earth-doped erosion-resistant protective coating on the surface of a matrix and a preparation method thereof, belonging to the technical field of surface treatment.

Background

With the development of the use requirement of the airplane in a severe environment, the requirement on the blade material is gradually increased. However, when an airplane runs in a solid particle sandy environment, various metal materials used by the existing blades are easy to erode and damage, so that the fuel consumption of an aircraft engine is increased, and the service life of the aircraft engine is shortened. For an aircraft engine, erosion is easy to occur on the surface of a compressor blade, a Physical Vapor Deposition (PVD) protective coating can effectively protect a blade metal base material, reduce sand erosion damage, inhibit surface deterioration, improve the durability of parts under the action of sand impact and prolong the service life of the parts.

The conventional PVD erosion resistant coating is based on a hard ceramic coating, and the high hardness of the coating is considered to be a major factor in improving the erosion resistance. Various binary nitrides and carbides have become candidates for hard coatings, such as TiN, CrN, ZrN, WC, and the like. However, although the coating has high hardness, it has high brittleness and poor fracture toughness, and it is difficult to form good protection for the metal substrate by the violent erosion of the solid particles. How to design and prepare the coating with excellent erosion resistance has important significance for the development of high-performance aeroengines.

Disclosure of Invention

The invention mainly aims to provide a rare earth doped erosion-resistant protective coating and a preparation method thereof, thereby overcoming the defects in the prior art.

In order to achieve the purpose, the invention adopts the following technical scheme:

the embodiment of the invention provides a rare earth doped anti-erosion protective coating, which comprises an ion etching layer, a Ti layer serving as a bonding coordination layer, a TiN layer serving as a bonding strengthening layer, a first rare earth doped TiAlSiN functional layer serving as a first functional layer, a second rare earth doped TiAlSiN functional layer serving as a second functional layer and a third rare earth doped TiAlSiN functional layer serving as a third functional layer which are sequentially stacked in the thickness direction of the rare earth doped anti-erosion protective coating, wherein the first rare earth doped TiAlSiN functional layer has a solid solution strengthened crystal structure, the second rare earth doped TiAlSiN functional layer has a nano twin crystal structure, the third rare earth doped TiAlSiN functional layer has an amorphous wrapped nano crystal structure, the rare earth elements doped by the first rare earth doped TiAlSiN functional layer, the second rare earth doped TiAlSiN functional layer and the third rare earth doped TiAlSiN functional layer comprise Y and/or Ce.

Furthermore, the doping content of the rare earth element in the first rare earth doped TiAlSiN functional layer is 0.02-0.8 at%, and the grain size is 100-200 nm.

Furthermore, the doping content of the rare earth element in the second rare earth doped TiAlSiN functional layer is 0.8-1.2 at%, and the grain size is 40-80 nm.

Furthermore, the doping content of the rare earth element in the third rare earth doped TiAlSiN functional layer is 1.2-2.4 at%, and the grain size is 20-30 nm.

The embodiment of the invention also provides a preparation method of the rare earth doped erosion-resistant protective coating, which comprises the following steps: and sequentially depositing an ion etching layer, a Ti layer, a TiN layer, a first rare earth doped TiAlSiN functional layer, a second rare earth doped TiAlSiN functional layer and a third rare earth doped TiAlSiN functional layer on the surface of the substrate by adopting an ion beam technology and a high-power pulse magnetron sputtering technology to obtain the rare earth doped erosion-resistant protective coating.

In some preferred embodiments, the preparation method comprises: adopting a high-power pulse magnetron sputtering technology, taking TiAlY and/or TiAlCe and TiSi double targets as targets, introducing protective gas with the flow rate of 40-50 sccm and nitrogen with the flow rate of 10-20 sccm into the reaction cavity, and thus co-sputtering and depositing a first rare earth doped TiAlSiN functional layer, a second rare earth doped TiAlSiN functional layer and a third rare earth doped TiAlSiN functional layer on the surface of the substrate deposited with the TiN layer in sequence; wherein, the power of the high-power pulse magnetron sputtering target is 2.5-3.5 KW, the pulse width is 50-200 mus, the frequency is 500-1000HZ, the negative bias of the substrate is 100-200V, and the deposition time is 20-120 min.

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

the rare earth-doped erosion-resistant protective coating provided by the invention has excellent mechanical properties and good erosion resistance, and meanwhile, the preparation process of the rare earth-doped erosion-resistant protective coating is simple, a high-power pulse magnetron sputtering technology is used, a composite functional layer is prepared by accurately regulating and controlling the content of rare earth elements, the first functional layer has a solid solution strengthening structure, the second functional layer has an isometric crystal structure, and the third functional layer has an amorphous coated nanocrystalline structure.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.

FIG. 1 is a schematic structural view of a rare earth doped erosion resistant protective coating in an exemplary embodiment of the present invention;

FIG. 2 is a graph of the hardness, H/E, H, of the rare earth doped erosion resistant protective coating in example 1 of the present invention³/E²A data graph;

FIG. 3 is a graph of the erosion rate of the rare earth doped erosion resistant protective coating in example 1 of the present invention;

FIG. 4 is a TEM image of a twin crystal structure of the rare earth-doped erosion-resistant protective coating in example 1 of the present invention.

Detailed Description

In view of the defects in the prior art, the inventor discovers through a large number of experiments that the atomic radius and the ionic radius of the rare earth element are far larger than those of common metal ions, the rare earth element has extremely active chemical properties, and can generate high-stability compounds and intermetallic compounds with nitrogen hydroxide and a plurality of non-metals, so that rare earth doped TiAlSiN coatings with different structures are designed. The technical solution, its implementation and principles, etc. will be further explained as follows.

As one aspect of the technical solution of the present invention, a rare earth doped erosion resistant protective coating is provided, as shown in fig. 1, which includes an ion etching layer, a Ti layer as a bonding coordination layer, a TiN layer as a bonding reinforcement layer, a first rare earth doped TiAlSiN functional layer as a first functional layer, a second rare earth doped TiAlSiN functional layer as a second functional layer, and a third rare earth doped TiAlSiN functional layer as a third functional layer, which are sequentially stacked in a thickness direction of the rare earth doped erosion resistant protective coating, wherein the first rare earth doped TiAlSiN functional layer has a solid solution reinforced crystal structure, the second rare earth doped TiAlSiN functional layer has a nano-twin crystal structure, the third rare earth doped TiAlSiN functional layer has an amorphous wrapped nano-crystal structure, and rare earth elements doped by the first rare earth doped TiAlSiN functional layer, the second rare earth doped TiAlSiN functional layer, and the third rare earth doped TiAlSiN functional layer include Y, and Y, Ce, and the like.

In some preferred embodiments, the doping content of the rare earth element in the first rare earth doped TiAlSiN functional layer is 0.02-0.8 at%, and the grain size is 100-200 nm. The first functional layer has a solid solution strengthened crystal structure (under low doping content, rare earth elements replace Al atoms in a cubic phase for solid solution), and is coordinated with the strengthening layer to deform, so that the binding force between the coating and the substrate is improved.

Further, the thickness of the first rare earth doped TiAlSiN functional layer is 600-1500 nm.

In some preferred embodiments, the doping content of the rare earth element in the second rare earth doped TiAlSiN functional layer is 0.8-1.2 at%, and the grain size is 40-80 nm. The second functional layer has a nanometer twin crystal structure, and the nanometer twin crystal structure is formed along with the increase of the doping content of rare earth elements (Y, Ce and the like), so that the hardness of the coating is increased. The twin formation mechanism is: the preferred orientation of the coating is determined by the lowest plane energy, mainly by the combination of surface energy and strain energy, and the cubic nitriding phase tends to be {200} at the beginning of film formation because of its highest bulk density, i.e., lowest surface energy. Beyond a certain thickness (about a few microns depending on the deposition conditions), grains tend to grow on 111 because strain energy dominates in thicker coatings. The columnar grains of the coating in the present invention exhibit a pronounced <111> orientation, while the low mobility yttrium hinders the growth of columnar grains, promotes nucleation, reduces grain size, primarily controlled by surface energy. The finer grains are stacked on the {200} plane with the film growth direction [111 ]. The twin mechanism is similar to that in the transformation from austenite to martensite in steel.

Further, the thickness of the second rare earth doped TiAlSiN functional layer is 500-1000 nm.

In some preferred embodiments, the doping content of the rare earth element in the third rare earth doped TiAlSiN functional layer is 1.2-2.4 at%, and the grain size is 20-30 nm. The third functional layer has an amorphous coated nanocrystalline structure, the rare earth content continues to increase, the rare earth content is segregated at a grain boundary to form grain boundary strengthening, and multilayer deflection is generated when cracks are expanded, so that the damage tolerance of the coating is improved.

Further, the thickness of the third rare earth doped TiAlSiN functional layer is 800-2000 nm.

The mechanism of synergy between the above layers in this application is: the first functional layer has a solid solution strengthening crystal structure and is coordinated with the strengthening layer to deform, so that the binding force between the coating and the substrate is improved; the second functional layer has a nanometer twin crystal structure to improve the hardness of the coating, and the third functional layer has a crystal boundary reinforced amorphous coated nanometer crystal structure to enable cracks to propagate in the material to generate multilayer deflection. In conclusion, the composite functional layer combines the high hardness toughness and the structural advantage of the coating, inhibits a dislocation multiplication source and annihilates the dislocation multiplication source at the edge of a grain boundary, thereby macroscopically inhibiting the initiation and development of cracks on the surface of the coating in the erosion process, avoiding the fracture and cracking of the coating under stress, optimizing the matching relationship between the coating and a titanium alloy matrix and between the coating and the interface, and improving the cooperative deformation capability of a base material/coating system.

Furthermore, the thickness of the ion etching layer is 50-100 nm.

Furthermore, the thickness of the combination coordination layer is 75-150 nm. The thermal matching coefficient of the combination coordination layer (Ti layer) is between the substrate and the TiN layer, and the deformation can be coordinated.

Furthermore, the thickness of the bonding strengthening layer is 200-300 nm. The thermal matching coefficient of the bonding strengthening layer (TiN layer) is between the Ti layer and the functional layer, and the bonding force can be improved.

Further, the thickness of the rare earth doped erosion-resistant protective coating is 2.0-5 mu m.

Furthermore, the erosion rate of the rare earth-doped erosion-resistant protective coating is 0.02-0.04 mg/g.

In conclusion, the rare earth doped erosion-resistant protective coating with high hardness, high toughness and excellent erosion resistance can be obtained by combining the three functional layers.

As another aspect of the technical solution of the present invention, a method for preparing a rare earth-doped erosion-resistant protective coating is provided, which comprises: and sequentially depositing an ion etching layer, a Ti layer, a TiN layer, a first rare earth doped TiAlSiN functional layer, a second rare earth doped TiAlSiN functional layer and a third rare earth doped TiAlSiN functional layer on the surface of the substrate by adopting an ion beam technology and a high-power pulse magnetron sputtering technology to obtain the rare earth doped erosion-resistant protective coating.

In some embodiments, the method of making specifically comprises: and placing the substrate in a reaction cavity, vacuumizing, heating the reaction cavity to 300-450 ℃, and etching the substrate for 10-20 min by using an ion beam to form an ion etching layer, wherein the flow of the protective gas is 30-40 sccm, the current of the ion source is 0.1-0.3A, and the power of the ion source is 100-300W.

In some embodiments, the method of making specifically comprises: and introducing protective gas with the flow rate of 40-50 sccm into the reaction cavity by adopting a high-power pulse magnetron sputtering technology, depositing a metal Ti layer on the surface of the substrate deposited with the ion etching layer by using a high-power pulse magnetron sputtering Ti target, wherein the target power is 2.5-3.5 KW, the pulse width is 50-200 mu s, the frequency is 500-1000Hz, the negative bias voltage of the substrate is 50-200V, and the deposition time is 5-10 min.

In some embodiments, the method of making specifically comprises: and introducing protective gas with the flow rate of 40-50 sccm and nitrogen with the flow rate of 10-20 sccm into the reaction cavity by adopting a high-power pulse magnetron sputtering technology, and continuously depositing a TiN layer on the surface of the substrate deposited with the Ti layer by using high-power pulse reaction magnetron sputtering, wherein the target power is 2.5-3.5 KW, the pulse width is 50-200 mus, the frequency is 500-1000Hz, the negative bias voltage of the substrate is 50-200V, and the deposition time is 10-15 min.

In some embodiments, the method of making specifically comprises: the method comprises the steps of adopting a high-power pulse magnetron sputtering technology, taking TiAlY and/or TiAlCe and TiSi double targets as targets, introducing protective gas with the flow rate of 40-50 sccm and nitrogen with the flow rate of 10-20 sccm into a reaction cavity, and thus co-sputtering and depositing a first rare earth doped TiAlSiN functional layer, a second rare earth doped TiAlSiN functional layer and a third rare earth doped TiAlSiN functional layer on the surface of a substrate deposited with a TiN layer in sequence.

Specifically, the process conditions for depositing the first rare earth doped TiAlSiN functional layer include: the flow rate of the protective gas (Ar gas) into the reaction chamber is 40-50 sccm, the flow rate of the nitrogen gas is 10-20 sccm, the voltage of the high-power pulse magnetron sputtering target is 700-800V, the power of the high-power pulse magnetron sputtering target is 2.5-3.5 KW, the pulse width is 50-200 mus, the frequency is 500-1000Hz, the negative bias voltage of the substrate is 100-200V, and the deposition time is 20-120 min.

Specifically, the process conditions for depositing the second rare earth doped TiAlSiN functional layer include: the flow rate of the protective gas (Ar gas) into the reaction chamber is 40-50 sccm, the flow rate of the nitrogen gas is 10-20 sccm, the voltage of the high-power pulse magnetron sputtering target is 800-1000V, the power of the high-power pulse magnetron sputtering target is 2.5-3.5 KW, the pulse width is 50-200 mus, the frequency is 500-1000Hz, the negative bias voltage of the substrate is 100-200V, and the deposition time is 20-120 min.

Specifically, the process conditions for depositing the third rare earth doped TiAlSiN functional layer include: the flow rate of the protective gas (Ar gas) into the reaction chamber is 40-50 sccm, the flow rate of the nitrogen gas is 10-20 sccm, the voltage of the high-power pulse magnetron sputtering target is 1000-1200V, the power of the high-power pulse magnetron sputtering target is 2.5-3.5 KW, the pulse width is 50-200 mus, the frequency is 500-1000Hz, the negative bias of the substrate is 100-200V, and the deposition time is 20-120 min.

Further, the protective atmosphere includes an inert gas such as argon (Ar), but is not limited thereto.

In some more specific embodiments, the preparation method of the rare earth-doped erosion-resistant protective coating specifically includes the following steps:

s1: placing a substrate sample in a reaction cavity, vacuumizing, heating the reaction cavity to 300-450 ℃, etching the substrate for 10-20 min by using an ion beam to form an ion etching layer, wherein the flow of argon is 30-40 sccm, the current of an ion source is 0.1-0.3A, and the power of the ion source is 100-300W;

s2: introducing Ar gas of 40-50 sccm into the reaction cavity, depositing a metal Ti layer serving as a bonding coordination layer on the surface of a substrate by using a high-power pulse magnetron sputtering high-purity Ti target, wherein the target power is 2.5-3.5 KW, the pulse width is 50-200 mus, the frequency is 500-1000Hz, the negative bias voltage of the substrate is 50-200V, and the deposition time is 5-10 min;

s3: introducing Ar gas of 40-50 sccm and nitrogen of 10-20 sccm into the reaction cavity, depositing a TiN layer serving as a bonding strengthening layer on the surface of the substrate by using high-power pulse reaction magnetron sputtering, wherein the target power is 2.5-3.5 KW, the pulse width is 50-200 mus, the frequency is 500-1000Hz, the negative bias voltage of the substrate is 50-200V, and the deposition time is 10-15 min;

s4: introducing Ar gas of 40-50 sccm and nitrogen of 10-20 sccm into the reaction cavity, adopting TiAlY (or Ce) and TiSi double-target co-sputtering to deposit a first functional layer, a second functional layer and a third functional layer TiAlSiYN on the surface of the substrate, wherein the power of the high-power pulse magnetron sputtering target is 2.5-3.5 KW, the pulse width is 50-200 mus, the frequency is 500-1000HZ, the negative bias voltage of the substrate is 100-200V, and the deposition time is 20-120 min.

According to the invention, the doping content of rare earth is regulated and controlled by regulating and controlling the technological parameters of the double-target high-power pulse magnetron sputtering in the step S4, so that functional layers with different coating structures are obtained.

Further, the protective coating is suitable for various substrates, including stainless steel, high-speed steel, hard alloy, titanium alloy and the like.

As another aspect of the technical scheme of the invention, the invention relates to the rare earth doped anti-erosion protective coating prepared by the method.

In summary, by the above technical scheme, the rare earth-doped erosion-resistant protective coating of the present invention has excellent mechanical properties and good erosion resistance, and has the following technical advantages: the method has the advantages that the process is simple, the high-power pulse magnetron sputtering technology is used, the composite functional layer is prepared by accurately regulating and controlling the content of the rare earth elements, the first functional layer has a solid solution strengthening structure, the second functional layer has an isometric crystal structure, the third functional layer has an amorphous coated nanocrystalline structure, compared with a single-structure coating, through the comprehensive action of different functional layers, the coating material has excellent mechanical properties such as high hardness and toughness, and the erosion protection performance under certain harsh working conditions can be realized.

The technical solutions of the present invention will be described in further detail below with reference to several preferred embodiments and accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. It is to be noted that the following examples are intended to facilitate the understanding of the present invention, and do not set forth any limitation thereto. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The test methods in the following examples, which are not specified under specific conditions, are generally carried out under conventional conditions.

Example 1

In this embodiment, a preparation method of a rare earth-doped erosion-resistant protective coating includes the following steps:

(1) ultrasonic cleaning of stainless steel, high-speed steel, silicon chip, hard alloy and titanium alloy substrate with acetone and ethanol respectivelyWashing for 15min, oven drying, placing in vacuum chamber, pre-vacuumizing to 3.0 × 10^-5Torr; introducing argon into the coating cavity, wherein the flow of the argon is 40sccm, keeping the air pressure at 2.0mTorr, applying a DC pulse bias of-100V on the substrate, etching the surface of the substrate by using an ion beam, and keeping the process for 20 minutes; the temperature of the cavity was 300 ℃, the ion source current was 0.2A, the ion source power was 200W, and the thickness was 80 nm.

(2): a high-power pulse magnetron sputtering technology is used, a metal Ti layer is deposited on the surface of a substrate by a high-purity Ti target, Ar gas is introduced into a cavity for 40sccm, the voltage of the high-power pulse magnetron sputtering Ti target is 800V, the target power is 2.5KW, the pulse width is 100 mus, the frequency is 1000HZ, the negative bias voltage of the substrate is 200V, the deposition time is 5min, and the thickness is 75 nm.

(3): depositing a TiN layer on the surface of a substrate by using a high-purity Ti target, introducing Ar gas of 50sccm into a cavity, introducing the nitrogen flow of 20sccm, controlling the voltage of the high-power pulse magnetron sputtering target to be 800V, controlling the target power to be 2.5KW, controlling the pulse width to be 100 mus, controlling the frequency to be 1000HZ, controlling the negative bias voltage of the substrate to be 200V, controlling the deposition time to be 10min and controlling the thickness to be 200 nm.

(4): the method comprises the steps that a first functional layer TiAlY and TiSi target is deposited on the surface of a substrate through a high-purity TiAlY and TiSi target, Ar gas is introduced into a cavity of 50sccm, the nitrogen flow is 20sccm, the TiAlY target voltage is 800V, the target power is 2.5KW, the pulse width is 100 KW, the pulse width is 1000HZ, the negative bias voltage of the substrate is 200V, the deposition time is 60min, and the substrate is located in the middle of the TiAlY target and the TiSi target.

(5): depositing a second functional layer TiAlSiYN on the surface of a substrate by using high-purity TiAlY and TiSi targets, introducing 50sccm of Ar gas into a cavity, wherein the nitrogen flow is 20sccm, the TiAlY target voltage is 1000V, the target power is 3KW, the pulse width is 100 microseconds, the frequency is 1000HZ, the TiSi target voltage is 800V, the target power is 3KW, the pulse width is 100 microseconds, the frequency is 1000HZ, the negative bias voltage of the substrate is 200V, and the deposition time is 60 min.

(6): depositing a third functional layer TiAlSiYN on the surface of a substrate by using high-purity TiAlY and TiSi targets, introducing 50sccm of Ar gas into a cavity, controlling the nitrogen flow to be 20sccm, the TiAlY target voltage to be 1200V, the target power to be 3.5KW, the pulse width to be 100 mus, the frequency to be 1000HZ, the TiSi target voltage to be 1000V, the target power to be 3.5KW, the pulse width to be 100 mus, the frequency to be 1000HZ, the negative bias voltage to be 200V of the substrate and the deposition time to be 60 min.

FIG. 2 shows the hardness H/E, H of the rare earth doped erosion-resistant protective coating prepared in this example³/E²The data figure, figure 3 is the erosion rate graph of the rare earth doping erosion resistant protective coating, figure 4 is the TEM image of the twin crystal structure of the rare earth doping erosion resistant protective coating. As can be seen from the above figures, the hardness of the rare earth doped erosion-resistant protective coating is 31.69GPa +/-2.2 GPa, the elastic modulus is 346.04GPa +/-22.85 GPa, the erosion rate is 0.039mg/g +/-0.015 mg/g, the erosion rate of the matrix titanium alloy is 0.432mg/g +/-0.039 mg/g, the protective effect is effectively achieved, and the efficiency is improved by 10 times.

The erosion rate test results of the rare earth doped erosion resistant protective coating prepared in this example are shown in table 1.

Example 2

(1) ultrasonic cleaning stainless steel, high-speed steel, silicon chip, hard alloy and titanium alloy matrix with acetone and ethanol for 15min, oven drying, placing in vacuum chamber, and pre-vacuumizing to 3.0 × 10^-5Torr; introducing argon into the coating cavity, wherein the flow of the argon is 40sccm, keeping the air pressure at 2.0mTorr, applying a DC pulse bias of-100V on the substrate, etching the surface of the substrate by using an ion beam, and keeping the process for 20 minutes; the temperature of the cavity was 300 ℃, the ion source current was 0.1A, the ion source power was 100W, and the thickness was 50 nm.

(2): a high-power pulse magnetron sputtering technology is used, a metal Ti layer is deposited on the surface of a substrate by a high-purity Ti target, 45sccm of Ar gas is introduced into a cavity, the bias voltage of the high-power pulse magnetron sputtering Ti target is 800V, the target power is 3KW, the pulse width is 50 mus, the frequency is 500HZ, the negative bias voltage of the substrate is 150V, the deposition time is 8min, and the thickness is 120 nm.

(3): depositing a TiN layer on the surface of a substrate by using a high-purity Ti target, introducing 50sccm of Ar gas and 20sccm of nitrogen into a cavity, controlling the voltage of the high-power pulse magnetron sputtering target to be 800V, controlling the target power to be 3.0KW, controlling the pulse width to be 100 mus, controlling the frequency to be 500HZ, controlling the negative bias voltage of the substrate to be 150V, controlling the deposition time to be 12min and controlling the thickness to be 240 nm.

(4): the method comprises the steps that high-purity TiAlY and TiSi targets deposit a first functional layer TiAlSiYN on the surface of a substrate, Ar gas is introduced into a cavity of the substrate for 50sccm, the nitrogen flow is 20sccm, the TiAlY target voltage is 700V, the target power is 2.8KW, the pulse width is 100 microseconds, the frequency is 500 microseconds, the TiSi target voltage is 700V, the target power is 2.8KW, the pulse width is 100 microseconds, the frequency is 500 microseconds, the negative bias voltage of the substrate is 200 volts, the deposition time is 60 minutes, and the substrate is located in front of the TiAlY target.

(5): depositing a second functional layer TiAlSiYN on the surface of a substrate by using high-purity TiAlY and TiSi targets, introducing 50sccm of Ar gas into a cavity, wherein the nitrogen flow is 20sccm, the TiAlY target voltage is 800V, the target power is 3.1KW, the pulse width is 100 microseconds, the frequency is 500 microseconds, the TiSi target voltage is 800V, the target power is 3.1KW, the pulse width is 100 microseconds, the frequency is 500 microseconds, the negative bias voltage of the substrate is 200 volts, and the deposition time is 60 minutes.

(6): depositing a third functional layer TiAlSiYN on the surface of a substrate by using high-purity TiAlY and TiSi targets, introducing 50sccm of Ar gas into a cavity, controlling the nitrogen flow to be 20sccm, the TiAlY target voltage to be 1200V, the target power to be 3.4KW, the pulse width to be 100 microseconds, the frequency to be 500 microseconds, the TiSi target voltage to be 1000V, the target power to be 3.4KW, the pulse width to be 100 microseconds, the frequency to be 500 microseconds, the negative bias voltage to the substrate to be 200V, and the deposition time to be 60 minutes.

Example 3

(1) ultrasonic cleaning stainless steel, high-speed steel, silicon chip, hard alloy and titanium alloy matrix with acetone and ethanol for 15min, oven drying, placing in vacuum chamber, and pre-vacuumizing to 3.0 × 10^-5Torr; introducing argon into the coating cavity, wherein the flow of the argon is 40sccm, keeping the air pressure at 2.0mTorr, applying a DC pulse bias of-100V on the substrate, etching the surface of the substrate by using an ion beam, and keeping the process for 20 minutes; the temperature of the cavity was 300 ℃, the ion source current was 0.3A, the ion source power was 300W, and the thickness was 100 nm.

(2): a high-power pulse magnetron sputtering technology is used, a metal Ti layer is deposited on the surface of a substrate by a high-purity Ti target, Ar gas is introduced into a cavity for 50sccm, the voltage of the high-power pulse magnetron sputtering Ti target is 800V, the target power is 3.5KW, the pulse width is 200 mus, the frequency is 800HZ, the negative bias voltage of the substrate is 50V, the deposition time is 10min, and the thickness is 150 nm.

(3): depositing a TiN layer on the surface of a substrate by using a high-purity Ti target, introducing 50sccm of Ar gas and 20sccm of nitrogen into a cavity, controlling the voltage of the high-power pulse magnetron sputtering target to be 800V, controlling the target power to be 3.5KW, controlling the pulse width to be 100 mus, controlling the frequency to be 800HZ, controlling the negative bias voltage of the substrate to be 50V, controlling the deposition time to be 15min and controlling the thickness to be 300 nm.

(4): the method comprises the steps that a first functional layer TiAlCe and TiSi target is deposited on the surface of a substrate through a high-purity TiAlCe target, Ar gas is introduced into a cavity of the first functional layer TiAlSiCeN, the flow rate of nitrogen is 20sccm, the voltage of the TiAlCe target is 750V, the target power is 3.5KW, the pulse width is 200 microseconds, the frequency is 800HZ, the voltage of the TiSi target is 800V, the target power is 3.5KW, the pulse width is 100 microseconds, the frequency is 800HZ, the negative bias voltage of the substrate is 100V, the deposition time is 60min, and the substrate is positioned in front of the TiSi target.

(5): depositing a second functional layer TiAlSiCEN on the surface of the substrate by using high-purity TiAlCe and TiSi targets, introducing 50sccm of Ar gas into the cavity, wherein the nitrogen flow is 20sccm, the TiAlCe target voltage is 900V, the target power is 3.5KW, the pulse width is 200 mus, the frequency is 800HZ, the TiSi target voltage is 800V, the target power is 3.0KW, the pulse width is 100 mus, the frequency is 800HZ, the negative bias voltage of the substrate is 100V, and the deposition time is 60 min.

(6): depositing a third functional layer TiAlSiCEN on the surface of the substrate by using high-purity TiAlCe and TiSi targets, introducing 50sccm of Ar gas into the cavity, wherein the nitrogen flow is 20sccm, the TiAlCe target voltage is 1100V, the target power is 3.0KW, the pulse width is 200 mus, the frequency is 800HZ, the TiSi target voltage is 1000V, the target power is 2.5KW, the pulse width is 100 mus, the frequency is 800HZ, the negative bias voltage of the substrate is 100V, and the deposition time is 60 min.

Example 4

(1) ultrasonic cleaning stainless steel, high-speed steel, silicon chip, hard alloy and titanium alloy matrix with acetone and ethanol for 15min, oven drying, placing in vacuum chamber, and pre-vacuumizing to 3.0 × 10^-5Torr; introducing argon into the coating cavity, wherein the flow of the argon is 30sccm, keeping the air pressure at 2.0mTorr, applying a DC pulse bias of-100V on the substrate, etching the surface of the substrate by using an ion beam, and keeping the process for 10 minutes; the temperature of the cavity was 450 ℃, the ion source current was 0.1A, the ion source power was 100W, and the thickness was 50 nm.

(2): a high-power pulse magnetron sputtering technology is used, a metal Ti layer is deposited on the surface of a substrate by a high-purity Ti target, Ar gas is introduced into a cavity for 48sccm, the bias voltage of the high-power pulse magnetron sputtering Ti target is 800V, the target power is 3.2KW, the pulse width is 500 mus, the frequency is 800HZ, the negative bias voltage of the substrate is 200V, the deposition time is 5min, and the thickness is 50 nm.

(3): depositing a TiN layer on the surface of a substrate by using a high-purity Ti target, introducing Ar gas of 40sccm and nitrogen of 15sccm into a cavity, controlling the voltage of the high-power pulse magnetron sputtering target to be 800V, controlling the target power to be 3.5KW, controlling the pulse width to be 50 mus, controlling the frequency to be 800HZ, controlling the negative bias voltage of the substrate to be 100V, controlling the deposition time to be 15min and controlling the thickness to be 250 nm.

(4): the method comprises the steps that high-purity TiAlY and TiSi targets deposit a first functional layer TiAlSiYN on the surface of a substrate, Ar gas is introduced into a cavity for 40sccm, the nitrogen flow is 10sccm, the TiAlY target voltage is 800V, the target power is 2.5KW, the pulse width is 50 microseconds, the frequency is 1000HZ, the TiSi target voltage is 800V, the target power is 2.5KW, the pulse width is 80 microseconds, the frequency is 500HZ, the negative bias voltage of the substrate is 150V, the deposition time is 20min, and the substrate is located in front of the TiAlY target.

(5): depositing a second functional layer TiAlSiYN on the surface of a substrate by using high-purity TiAlY and TiSi targets, introducing Ar gas of 40sccm into a cavity, wherein the nitrogen flow is 15sccm, the TiAlY target voltage is 800V, the target power is 3.1KW, the pulse width is 50 microseconds, the frequency is 500 microseconds, the TiSi target voltage is 800V, the target power is 3.1KW, the pulse width is 100 microseconds, the frequency is 500 microseconds, the negative bias voltage of the substrate is 150 volts, and the deposition time is 20 minutes.

(6): depositing a third functional layer TiAlSiYN on the surface of a substrate by using high-purity TiAlY and TiSi targets, introducing Ar gas of 40sccm into a cavity, wherein the nitrogen flow is 10sccm, the TiAlY target voltage is 1000V, the target power is 2.5KW, the pulse width is 50 microseconds, the frequency is 500 microseconds, the TiSi target voltage is 1000V, the target power is 3.4KW, the pulse width is 100 microseconds, the frequency is 500 microseconds, the negative bias voltage of the substrate is 150 volts, and the deposition time is 120 minutes.

Example 5

(1) ultrasonic cleaning stainless steel, high-speed steel, silicon chip, hard alloy and titanium alloy matrix with acetone and ethanol for 15min, oven drying, placing in vacuum chamber, and pre-vacuumizing to 3.0 × 10^-5Torr; introducing argon into the coating cavity, wherein the flow of the argon is 35sccm, keeping the air pressure at 2.0mTorr, applying a DC pulse bias of-100V on the substrate, etching the surface of the substrate by using an ion beam, and keeping the process for 15 minutes; the temperature of the cavity was 400 ℃, the ion source current was 0.1A, the ion source power was 100W, and the thickness was 50 nm.

(3): depositing a TiN layer on the surface of a substrate by using a high-purity Ti target, introducing 40sccm of Ar gas and 10sccm of nitrogen gas into a cavity, controlling the voltage of the high-power pulse magnetron sputtering target to be 800V, controlling the target power to be 3.5KW, controlling the pulse width to be 200 mus, controlling the frequency to be 800HZ, controlling the negative bias voltage of the substrate to be 100V, controlling the deposition time to be 10min and controlling the thickness to be 200 nm.

(4): the method comprises the steps of depositing a first functional layer TiAlY and TiSi target on the surface of a substrate by using a high-purity TiAlY and TiSi target, introducing Ar gas of 45sccm into a cavity, controlling the nitrogen flow to be 15sccm, the TiAlY target voltage to be 750V, the target power to be 2.5KW, the pulse width to be 150 microseconds, the frequency to be 500 microseconds, the TiSi target voltage to be 800 Vs, the target power to be 2.5KW, the pulse width to be 80 microseconds, the frequency to be 300 microseconds, the negative bias voltage to the substrate to be 200 Vs, the deposition time to be 120 minutes, and the substrate to be positioned in front of the TiAlY target.

(5): depositing a second functional layer TiAlSiYN on the surface of a substrate by using high-purity TiAlY and TiSi targets, introducing Ar gas of 45sccm into a cavity, wherein the nitrogen flow is 10sccm, the TiAlY target voltage is 800V, the target power is 2.5KW, the pulse width is 100 microseconds, the frequency is 500HZ, the TiSi target voltage is 800V, the target power is 3.1KW, the pulse width is 100 microseconds, the frequency is 500HZ, the negative bias voltage of the substrate is 200V, and the deposition time is 120 min.

(6): depositing a third functional layer TiAlSiYN on the surface of a substrate by using high-purity TiAlY and TiSi targets, introducing Ar gas of 45sccm into a cavity, wherein the nitrogen flow is 15sccm, the TiAlY target voltage is 1200V, the target power is 3.4KW, the pulse width is 100 microseconds, the frequency is 500 microseconds, the TiSi target voltage is 1000V, the target power is 3.4KW, the pulse width is 100 microseconds, the frequency is 500 microseconds, the negative bias voltage of the substrate is 200V, and the deposition time is 20 minutes.

Comparative example 1

In this comparative example, a method of preparing a protective coating includes the steps of:

(1) ultrasonic cleaning stainless steel, high-speed steel, silicon chip, hard alloy and titanium alloy matrix with acetone and ethanol for 15min, oven drying, placing in vacuum chamber, and pre-vacuumizing to 3.0 × 10^-5Torr; introducing argon into the coating cavity, wherein the flow of the argon is 40sccm, keeping the air pressure at 2.0mTorr, applying a DC pulse bias of-100V on the substrate, etching the surface of the substrate by using an ion beam, and keeping the process for 20 minutes; the temperature of the cavity is 300 ℃, the current of the ion source is 0.1A, the power of the ion source is 100W, and the thickness is 50 nm.

(2): a high-power pulse magnetron sputtering technology is used, a metal Ti layer is deposited on the surface of a substrate by a high-purity Ti target, Ar gas is introduced into a cavity for 40sccm, the bias voltage of the high-power pulse magnetron sputtering Ti target is 800V, the target power is 2.5KW, the pulse width is 50-200 mus, the frequency is 1000HZ, the negative bias voltage of the substrate is 200V, the deposition time is 10min, and the thickness is 75 nm.

(3): depositing a TiN layer on the surface of a substrate by using a high-purity Ti target, introducing Ar gas of 50sccm into a cavity, introducing the nitrogen flow of 20sccm, controlling the voltage of the high-power pulse magnetron sputtering target to be 800V, controlling the target power to be 2.5KW, controlling the pulse width to be 100 mus, controlling the frequency to be 1000HZ, controlling the negative bias voltage of the substrate to be 200V, controlling the deposition time to be 10min and controlling the thickness to be 100 nm.

(4): the method comprises the steps of depositing a first functional layer TiAlY and TiSi target on the surface of a substrate by using a high-purity TiAlY and TiSi target, introducing 50sccm of Ar gas into a cavity, controlling the nitrogen flow to be 20sccm, the TiAlY target voltage to be 800V, the current to be 0.4A, the pulse width to be 100 microseconds, the frequency to be 1000 microseconds, the TiSi target voltage to be 800V, the target power to be 3KW, the pulse width to be 100 microseconds, the frequency to be 1000 microseconds, the negative bias voltage to the substrate to be 200V, and the deposition time to be 60 minutes.

The results of the erosion rate test of the coating prepared in this comparative example are shown in table 1.

Comparative example 2

(2): a high-power pulse magnetron sputtering technology is used, a metal Ti layer is deposited on the surface of a substrate by a high-purity Ti target, 20sccm and 45sccm of Ar gas are introduced into a cavity, the bias voltage of the high-power pulse magnetron sputtering Ti target is 800V, the target power is 3KW, the pulse width is 100 mus, the frequency is 500HZ, the negative bias voltage of the substrate is 200V, the deposition time is 10min, and the thickness is 75 nm.

(3): depositing a TiN layer on the surface of a substrate by using a high-purity Ti target, introducing 50sccm of Ar gas and 20sccm of nitrogen into a cavity, controlling the voltage of the high-power pulse magnetron sputtering target to be 800V, controlling the target power to be 3.0KW, controlling the pulse width to be 100 mus, controlling the frequency to be 500HZ, controlling the negative bias voltage of the substrate to be 200V, controlling the deposition time to be 10min and controlling the thickness to be 150 nm.

(4): the method comprises the steps that a first functional layer TiAlY and TiSi target is deposited on the surface of a substrate through a high-purity TiAlY and TiSi target, Ar gas is introduced into a cavity of the first functional layer TiAlSiYN, the nitrogen flow is 20sccm, the TiAlY target voltage is 700V, the target power is 2.8KW, the pulse width is 100 HZ, the negative bias voltage of the substrate is 200V, the deposition time is 60min, and the substrate is located in front of the TiAlY target.

(5): depositing a second functional layer TiAlSiYN on the surface of a substrate by using high-purity TiAlY and TiSi targets, introducing 50sccm of Ar gas into a cavity, wherein the nitrogen flow is 20sccm, the TiAlY target voltage is 800V, the target power is 3 and 1KW, the pulse width is 100 microseconds, the frequency is 500 microseconds, the TiSi target voltage is 700V, the target power is 3.1KW, the pulse width is 100 microseconds, the frequency is 500 microseconds, the negative bias voltage of the substrate is 200V, and the deposition time is 60 minutes.

Comparative example 3

(1) respectively ultrasonically cleaning stainless steel, high-speed steel, silicon chips, hard alloy and titanium alloy substrates for 15min by acetone and ethanol, drying, placing in a vacuum cavity, and pre-vacuumizing to 3.0 multiplied by 10 < -5 > Torr; introducing argon into the coating cavity, wherein the flow of the argon is 40sccm, keeping the air pressure at 2.0mTorr, applying a DC pulse bias of-100V on the substrate, etching the surface of the substrate by using an ion beam, and keeping the process for 20 minutes; the temperature of the cavity was 300 ℃, the ion source current was 0.1A, the ion source power was 100W, and the thickness was 50 nm.

(2): a high-power pulse magnetron sputtering technology is used, a metal Ti layer is deposited on the surface of a substrate by a high-purity Ti target, 20sccm and 40sccm of Ar gas are introduced into a cavity, the bias voltage of the high-power pulse magnetron sputtering Ti target is 800V, the target power is 2.5KW, the pulse width is 50-200 mus, the frequency is 1000HZ, the negative bias voltage of the substrate is 200V, the deposition time is 10min, and the thickness is 75 nm.

(3): depositing a TiN layer on the surface of a substrate by using a high-purity Ti target, introducing Ar gas of 50sccm into a cavity, introducing the nitrogen flow of 20sccm, controlling the voltage of the high-power pulse magnetron sputtering target to be 800V, controlling the current to be 3A, controlling the target power to be 2.5KW, controlling the pulse width to be 100 mus, controlling the frequency to be 1000HZ, controlling the negative bias voltage of the substrate to be 200V, controlling the deposition time to be 10min and controlling the thickness to be 100 nm.

(4): the TiAlSiN is deposited on the surface of a substrate by high-purity TiAls and TiSi targets, Ar gas is introduced into a cavity at a flow rate of 50sccm, the nitrogen flow rate is 20sccm, the TiAltarget voltage is 800V, the target power is 3KW, the pulse width is 100 mus, the frequency is 1000HZ, the TiSi target voltage is 800V, the pulse width is 100 mus, the frequency is 1000HZ, the negative bias voltage of the substrate is 200V, and the deposition time is 60 min.

TABLE 1 washout Rate results for examples 1-3 and comparative examples 1-3

Name (R)	Erosion Rate (mg/g)
		TC4	0.432±0.039
Example 1	0.039±0.015
		Example 2	0.042±0.012
Example 3	0.022±0.018
		Comparative example 1	0.253±0.017
Comparative example 2	0.174±0.047
		Comparative example 3	0.301±0.026

In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.

While the 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 substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.

Claims

1. The rare earth doped anti-erosion protective coating is characterized by comprising an ion etching layer, a Ti layer serving as a bonding coordination layer, a TiN layer serving as a bonding strengthening layer, a first rare earth doped TiAlSiN functional layer serving as a first functional layer, a second rare earth doped TiAlSiN functional layer serving as a second functional layer and a third rare earth doped TiAlSiN functional layer serving as a third functional layer, which are sequentially stacked in the thickness direction of the rare earth doped anti-erosion protective coating, wherein the first rare earth doped TiAlSiN functional layer has a solid solution strengthening crystal structure, the second rare earth doped TiAlSiN functional layer has a nano twin crystal structure, the third rare earth doped TiAlSiN functional layer has an amorphous wrapped nano crystal structure, and rare earth elements doped by the first rare earth doped TiAlSiN functional layer, the second rare earth doped TiAlSiN functional layer and the third rare earth doped TiAlSiN functional layer comprise Y and/or Ce.

2. The rare earth doped erosion resistant protective coating of claim 1, wherein: the doping content of rare earth elements in the first rare earth doped TiAlSiN functional layer is 0.02-0.8 at%, and the grain size is 100-200 nm; and/or the thickness of the first rare earth doped TiAlSiN functional layer is 600-1500 nm.

3. The rare earth doped erosion resistant protective coating of claim 1, wherein: the doping content of rare earth elements in the second rare earth doped TiAlSiN functional layer is 0.8-1.2 at%, and the grain size is 40-80 nm; and/or the thickness of the second rare earth doped TiAlSiN functional layer is 500-1000 nm.

4. The rare earth doped erosion resistant protective coating of claim 1, wherein: the doping content of rare earth elements in the third rare earth doped TiAlSiN functional layer is 1.2-2.4 at%, and the grain size is 20-30 nm; and/or the thickness of the third rare earth doped TiAlSiN functional layer is 800-2000 nm.

5. The rare earth doped erosion resistant protective coating of claim 1, wherein: the thickness of the ion etching layer is 50-100 nm; and/or the thickness of the combination coordination layer is 75-150 nm; and/or the thickness of the bonding strengthening layer is 200-300 nm; and/or the thickness of the rare earth doped erosion-resistant protective coating is 2.0-5 mu m; and/or the erosion rate of the rare earth-doped erosion-resistant protective coating is 0.02-0.04 mg/g.

6. The method of preparing the rare earth doped erosion resistant protective coating of any one of claims 1-5, comprising: and sequentially depositing an ion etching layer, a Ti layer, a TiN layer, a first rare earth doped TiAlSiN functional layer, a second rare earth doped TiAlSiN functional layer and a third rare earth doped TiAlSiN functional layer on the surface of the substrate by adopting an ion beam technology and a high-power pulse magnetron sputtering technology to obtain the rare earth doped erosion-resistant protective coating.

7. The preparation method according to claim 6, which specifically comprises: placing a substrate in a reaction cavity, vacuumizing, heating the reaction cavity to 300-450 ℃, and etching the substrate for 10-20 min by using an ion beam to form an ion etching layer, wherein the flow of protective gas is 30-40 sccm, the current of an ion source is 0.1-0.3A, and the power of the ion source is 100-300W;

and/or the substrate comprises stainless steel, high speed steel, cemented carbide or titanium alloy.

8. The preparation method according to claim 6, which specifically comprises: and introducing protective gas with the flow rate of 40-50 sccm into the reaction cavity by adopting a high-power pulse magnetron sputtering technology, depositing a metal Ti layer on the surface of the substrate deposited with the ion etching layer by using a high-power pulse magnetron sputtering Ti target, wherein the target power is 2.5-3.5 KW, the pulse width is 50-200 mu s, the frequency is 500-1000Hz, the negative bias voltage of the substrate is 50-200V, and the deposition time is 5-10 min.

9. The preparation method according to claim 6, which specifically comprises: and introducing protective gas with the flow rate of 40-50 sccm and nitrogen with the flow rate of 10-20 sccm into the reaction cavity by adopting a high-power pulse magnetron sputtering technology, and continuously depositing a TiN layer on the surface of the substrate deposited with the Ti layer by using high-power pulse reaction magnetron sputtering, wherein the target power is 2.5-3.5 KW, the pulse width is 50-200 mus, the frequency is 500-1000Hz, the negative bias voltage of the substrate is 50-200V, and the deposition time is 10-15 min.

10. The preparation method according to claim 6, which specifically comprises: adopting a high-power pulse magnetron sputtering technology, taking TiAlY and/or TiAlCe and TiSi double targets as targets, introducing protective gas with the flow rate of 40-50 sccm and nitrogen with the flow rate of 10-20 sccm into the reaction cavity, and thus co-sputtering and depositing a first rare earth doped TiAlSiN functional layer, a second rare earth doped TiAlSiN functional layer and a third rare earth doped TiAlSiN functional layer on the surface of the substrate deposited with the TiN layer in sequence;

preferably, the process conditions for depositing the first rare earth doped TiAlSiN functional layer include: protective gas with the flow rate of 40-50 sccm and nitrogen with the flow rate of 10-20 sccm are fed into the reaction cavity, the voltage of the high-power pulse magnetron sputtering target is 700-800V, the power of the high-power pulse magnetron sputtering target is 2.5-3.5 KW, the pulse width is 50-200 mus, the frequency is 500-1000Hz, the negative bias of the substrate is 100-200V, and the deposition time is 20-120 min;

preferably, the process conditions for depositing the second rare earth doped TiAlSiN functional layer include: protective gas with the flow rate of 40-50 sccm and nitrogen with the flow rate of 10-20 sccm are fed into the reaction cavity, the voltage of the high-power pulse magnetron sputtering target is 800-1000V, the power of the high-power pulse magnetron sputtering target is 2.5-3.5 KW, the pulse width is 50-200 mus, the frequency is 500-1000Hz, the negative bias of the substrate is 100-200V, and the deposition time is 20-120 min;

preferably, the process conditions for depositing the third rare earth doped TiAlSiN functional layer include: the protective gas with the flow rate of 40-50 sccm and the nitrogen with the flow rate of 10-20 sccm are fed into the reaction cavity, the voltage of the high-power pulse magnetron sputtering target is 1000-1200V, the power of the high-power pulse magnetron sputtering target is 2.5-3.5 KW, the pulse width is 50-200 mus, the frequency is 500-1000Hz, the negative bias of the substrate is 100-200V, and the deposition time is 20-120 min.