CN114015981B - Rare earth doped erosion-resistant protective coating and preparation method thereof - Google Patents
Rare earth doped erosion-resistant protective coating and preparation method thereof Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 146
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 127
- 230000003628 erosive effect Effects 0.000 title claims abstract description 66
- 239000011253 protective coating Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002346 layers by function Substances 0.000 claims abstract description 124
- 239000010410 layer Substances 0.000 claims abstract description 80
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000001681 protective effect Effects 0.000 claims abstract description 18
- 238000000992 sputter etching Methods 0.000 claims abstract description 15
- 230000003014 reinforcing effect Effects 0.000 claims abstract 3
- 239000000758 substrate Substances 0.000 claims description 129
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 72
- 238000000151 deposition Methods 0.000 claims description 70
- 239000007789 gas Substances 0.000 claims description 57
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 57
- 230000008021 deposition Effects 0.000 claims description 50
- 239000010936 titanium Substances 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 45
- 229910008484 TiSi Inorganic materials 0.000 claims description 44
- 238000000576 coating method Methods 0.000 claims description 31
- 229910052757 nitrogen Inorganic materials 0.000 claims description 31
- 239000011248 coating agent Substances 0.000 claims description 27
- 238000005516 engineering process Methods 0.000 claims description 23
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- 238000006243 chemical reaction Methods 0.000 claims description 17
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- 238000010884 ion-beam technique Methods 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
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- 229910001069 Ti alloy Inorganic materials 0.000 claims description 12
- 238000005728 strengthening Methods 0.000 claims description 12
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 36
- 150000002500 ions Chemical class 0.000 description 20
- 229910052786 argon Inorganic materials 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
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- 229910001873 dinitrogen Inorganic materials 0.000 description 10
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- 238000011161 development Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- 229910010038 TiAl Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
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- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
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- 230000015556 catabolic process Effects 0.000 description 1
- -1 cemented carbide Inorganic materials 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
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- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3435—Applying energy to the substrate during sputtering
- C23C14/345—Applying energy to the substrate during sputtering using substrate bias
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3485—Sputtering using pulsed power to the target
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention discloses a rare earth doped anti-erosion 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 reinforcing 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 laminated, wherein 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. The rare earth doped erosion resistant protective coating has excellent mechanical properties such as high hardness, toughness and the like, and good erosion resistance, and meanwhile, the preparation process of the protective coating is simple, so that the erosion resistant protective performance under certain severe working conditions can be realized.
Description
Technical Field
The invention relates to a protective coating, in particular to a rare earth doped anti-erosion protective coating for the surface of a substrate and a preparation method thereof, belonging to the technical field of surface treatment.
Background
With the development of the use requirements of the aircraft in severe environments, the requirements on blade materials are gradually increased. However, when an aircraft runs in a solid particle sandy environment, various metal materials used by the current blades are easy to erode and damage, so that the fuel consumption of the aircraft engine is increased, and the service life of the aircraft engine is reduced. For an aeroengine, erosion easily occurs on the surface of a compressor blade, and a Physical Vapor Deposition (PVD) protective coating can effectively protect a blade metal base material, reduce sand erosion damage, inhibit surface degradation, and improve the durability and service life of parts under the action of sand impact.
Conventional PVD erosion resistant coatings are based on hard ceramic coatings, the high hardness of which is believed to be a major factor in improving erosion resistance. Various binary nitrides and carbides have become candidates for hard coatings, such as TiN, crN, zrN, WC and the like. However, the coating has high hardness, but has strong brittleness and poor fracture toughness, and is difficult to form good protection on a metal substrate under the severe erosion action of solid particles. How to design and prepare a coating with excellent erosion resistance is of great significance to 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 aim of the invention, the invention adopts the following technical scheme:
the embodiment of the invention provides a rare earth doped erosion-resistant protective coating, which comprises 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, wherein the ion etching layer, the Ti layer, the TiN layer, 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 laminated in the thickness direction of the rare earth doped erosion-resistant protective coating, 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 package 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.
Further, the doping content of rare earth elements in the first rare earth doped TiAlSiN functional layer is 0.02-0.8at%, and the grain size is 100-200 nm.
Further, the doping content of rare earth elements in the second rare earth doped TiAlSiN functional layer is 0.8-1.2at%, and the grain size is 40-80 nm.
Further, the doping content of rare earth elements in the third rare earth doped TiAlSiN functional layer is 1.2-2.4at% 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 anti-erosion protective coating.
In some preferred embodiments, the method of preparation 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 of 40-50 sccm and nitrogen with the flow of 10-20 sccm into a reaction cavity, and sequentially 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; the high-power pulse magnetron sputtering target has the power of 2.5-3.5 KW, the pulse width of 50-200 mu s, the frequency of 500-1000HZ, the substrate negative bias voltage of 100-200V and the deposition time of 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, 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 a twin crystal structure, the third functional layer has an amorphous wrapped nanocrystalline structure, and compared with a single-structure coating, the coating material has excellent mechanical properties such as high hardness, toughness and the like through the comprehensive action of different functional layers, so that the erosion-resistant protective performance under certain harsh working conditions can be realized.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings may be obtained according to the drawings without inventive effort to those skilled in the art.
FIG. 1 is a schematic structural view of a rare earth doped erosion protection coating in accordance with an exemplary embodiment of the present invention;
FIG. 2 is a graph of hardness, H/E, H, of the rare earth doped erosion resistant protective coating of example 1 of the present invention 3 /E 2 A data map;
FIG. 3 is a graph of erosion rate for a rare earth doped erosion resistant protective coating according to example 1 of the present invention;
fig. 4 is a TEM image of the twin crystal structure of the rare earth doped erosion resistant protective coating of example 1 of the present invention.
Detailed Description
In view of the defects in the prior art, the inventor discovers that the atomic radius and the ionic radius of the rare earth element are far larger than those of common metal ions through a large number of experimental exploration, and the rare earth element has abnormal active chemical properties, can generate high-stability compounds and intermetallic compounds with hydrogen and nitrogen and a plurality of non-metals, so that rare earth doped TiAlSiN coatings with different structures are designed. The technical scheme, the implementation process, the principle and the like are further explained as follows.
As an aspect of the present invention, referring to fig. 1, the rare earth doped erosion resistant protective coating includes an ion etching layer, a Ti layer as a bonding coordination layer, a TiN layer as a bonding strengthening layer, a first rare earth doped tiaalsin functional layer as a first functional layer, a second rare earth doped tiaalsin functional layer as a second functional layer, and a third rare earth doped tiaalsin 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 tiaalsin functional layer has a solid solution strengthening crystal structure, the second rare earth doped tiaalsin functional layer has a nano twin crystal structure, the third rare earth doped tiaalsin functional layer has an amorphous encapsulation nanocrystalline structure, and rare earth elements doped by the first rare earth doped tiaalsin functional layer, the second rare earth doped tiaalsin functional layer, and the third rare earth doped tiaalsin functional layer include 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 0.02-0.8at%, and the grain size is 100-200 nm. The first functional layer has a solid solution strengthening crystal structure (the rare earth element replaces Al atoms in the cubic phase to be solid solution in a replacement way under the condition of low doping content), and is deformed in coordination with the strengthening layer, so that the binding force between the coating and the matrix 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 tiaalsin functional layer is 0.8-1.2at% and the grain size is 40-80 nm. The second functional layer has a nano twin crystal structure, and as the doping content of rare earth elements (Y, ce and the like) is increased, a nano twin crystal structure is formed, and the hardness of the coating is increased. The mechanism of twinning is: the preferred orientation of the coating is determined by the lowest plane energy, mainly by the 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. Above a certain thickness (on the order of 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 low mobility yttrium retards the growth of columnar grains, promotes crystalline nuclei, reduces grain size, and is primarily controlled by surface energy. Finer grains are stacked on the {200} plane, and the film growth direction is [111]. The mechanism of such twinning is similar to that of twinning 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 tiaalsin functional layer is 1.2-2.4at%, and the grain size is 20-30 nm. The third functional layer has an amorphous package nanocrystalline structure, the rare earth content continues to increase, segregation is formed at the grain boundary, grain boundary strengthening is formed, and multi-layer disturbance 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 synergistic mechanism between the above layers in the present application is: the first functional layer has a solid solution strengthening crystal structure, and is deformed in coordination with the strengthening layer, so that the binding force between the coating and the matrix is improved; the second functional layer has a nano twin crystal structure, the hardness of the coating is improved, and the third functional layer has a grain boundary reinforced amorphous wrapped nano crystal structure, so that cracks are expanded in the material to generate multilayer disturbance. On the whole, the composite functional layer combines the high hardness toughness and the structural advantage of the coating, inhibits dislocation proliferation sources and annihilates the dislocation proliferation sources at the edge of a grain boundary, so that the initiation and development of cracks on the surface of the coating in the erosion process are macroscopically inhibited, the cracking and the cracking of the coating under stress are avoided, the matching relationship between the coating and a titanium alloy matrix and between the coating and an interface is optimized, and the cooperative deformation capability of a base material/a coating system is improved.
Further, the thickness of the ion etching layer is 50-100 nm.
Further, the thickness of the bonding coordination layer is 75-150 nm. The thermal matching coefficient of the bonding coordination layer (Ti layer) is positioned between the matrix and the TiN layer, and can coordinate deformation.
Further, 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, so that the bonding force can be improved.
Further, the thickness of the rare earth doped erosion-resistant protective coating is 2.0-5 mu m.
Further, 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 anti-erosion protective coating with high hardness, high toughness and excellent anti-erosion performance can be obtained through the combination of the three functional layers.
As another aspect of the technical scheme of the present invention, the preparation method of the rare earth doped erosion resistant protective coating 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 anti-erosion protective coating.
In some embodiments, the method of preparation 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 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.
In some embodiments, the method of preparation specifically comprises: and (3) introducing protective gas with the flow 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 substrate negative bias voltage is 50-200V, and the deposition time is 5-10 min.
In some embodiments, the method of preparation specifically comprises: and (3) 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, continuously depositing a TiN layer on the surface of the substrate deposited with the Ti layer by using the high-power pulse magnetron sputtering, 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 10-15 min.
In some embodiments, the method of preparation specifically comprises: and (3) 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 of 40-50 sccm and nitrogen with the flow of 10-20 sccm into the reaction cavity, and sequentially 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.
Specifically, the process conditions for depositing the first rare earth doped tiaalsin functional layer include: and (3) introducing protective gas (Ar gas) with the flow of 40-50 sccm, nitrogen with the flow of 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 mu s, 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 tiaalsin functional layer include: and (3) introducing protective gas (Ar gas) with the flow of 40-50 sccm, nitrogen with the flow of 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 mu s, the frequency is 500-1000Hz, the negative bias 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 tiaalsin functional layer include: and (3) introducing protective gas (Ar gas) with the flow of 40-50 sccm, nitrogen with the flow of 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 mu s, the frequency is 500-1000Hz, the negative bias voltage 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 protection coating specifically includes the following steps:
s1: placing a substrate sample in a reaction cavity, vacuumizing, heating the reaction cavity to 300-450 ℃, and etching the substrate by using an ion beam for 10-20 min to form an ion etching layer, wherein the argon flow is 30-40 sccm, the ion source current is 0.1-0.3A, and the ion source power 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 mu s, the frequency is 500-1000Hz, the substrate negative bias voltage is 50-200V, and the deposition time is 5-10 min;
s3: introducing Ar gas of 40-50 sccm and nitrogen gas of 10-20 sccm into the reaction cavity, and depositing a TiN layer serving as a bonding reinforcement 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 [ mu ] s, the frequency is 500-1000Hz, the substrate negative bias is 50-200V, and the deposition time is 10-15 min;
s4: ar gas is introduced into the reaction cavity for 40-50 sccm, nitrogen gas is introduced for 10-20 sccm, tiAlY (or Ce) and TiSi dual targets are adopted to co-sputter and deposit a first functional layer TiAlSiYN, a second functional layer TiAlSiYN and a third functional layer TiAlSiYN on the surface of a substrate, the power of a high-power pulse magnetron sputtering target is 2.5-3.5 KW, the pulse width is 50-200 mu s, the frequency is 500-1000HZ, the substrate negative bias voltage 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 high-power pulse magnetron sputtering process parameters of the double targets in the step S4, so that the functional layers with different coating structures are obtained.
Further, the protective coating is suitable for a variety of substrates including stainless steel, high speed steel, cemented carbide, titanium alloys, and the like.
As another aspect of the technical scheme of the invention, the rare earth doped anti-erosion protective coating prepared by the method is related.
In summary, by the technical scheme, the rare earth doped erosion resistant protective coating has excellent mechanical properties and good erosion resistance, and has the following technical advantages: the process is simple, the high-power pulse magnetron sputtering technology is used for preparing the composite functional layer by accurately regulating and controlling the content of rare earth elements, the first functional layer is provided with a solid solution strengthening structure, the second functional layer is provided with a twin crystal structure, the third functional layer is provided with an amorphous package nanocrystalline structure, and compared with a single-structure coating, the coating material has excellent mechanical characteristics such as high hardness, high toughness and the like through the comprehensive effect of different functional layers, so that the erosion protection performance under certain severe working conditions can be realized.
The technical solution of the present invention will be described in further detail below with reference to a number of preferred embodiments and accompanying drawings, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. It should be noted that the examples described below are intended to facilitate the understanding of the present invention and are not intended to limit the present invention in any way. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The test methods in the following examples, in which specific conditions are not noted, generally follow conventional conditions.
Example 1
In this embodiment, a method for preparing a rare earth doped erosion resistant protective coating includes the following steps:
(1) Respectively ultrasonically cleaning stainless steel, high-speed steel, silicon chip, hard alloy, titanium alloy matrix with acetone and ethanol for 15min, oven drying, placing into vacuum cavity, and pre-vacuumizing to 3.0X10 -5 Torr; argon is introduced into the film coating cavity, the flow rate of the argon is 40sccm, the air pressure is maintained at 2.0 mTorr, a direct current pulse bias voltage of-100V is applied to the substrate, and the surface of the substrate is etched by utilizing an ion beam, wherein the process is maintained for 20 minutes; the temperature of the cavity is 300 ℃, the current of the ion source is 0.2A, the power of the ion source is 200W, and the thickness is 80nm.
(2): and 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 mu s, the frequency is 1000HZ, the negative bias voltage of the substrate is 200V, the deposition time is 5min, and the thickness is 75nm.
(3): the high-purity Ti target deposits a TiN layer on the surface of the substrate, ar gas is introduced into the cavity at 50sccm, the nitrogen flow is 20sccm, the voltage of the high-power pulse magnetron sputtering target is 800V, the target power is 2.5KW, the pulse width is 100 mu s, the frequency is 1000HZ, the negative bias of the substrate is 200V, the deposition time is 10min, and the thickness is 200nm.
(4): the method comprises the steps that a first functional layer TiAlSiYN is deposited on the surface of a substrate by a high-purity TiAlY target and a TiSi target, wherein Ar gas is introduced into a cavity, the flow rate of nitrogen is 20sccm, the voltage of the TiAlY target is 800V, the target power is 2.5KW, the pulse width is 100 [ mu ] s, the frequency is 1000HZ, the voltage of the TiSi target is 800V, the target power is 2.5KW, the pulse width is 100 [ mu ] s, the frequency is 1000HZ, the negative bias voltage of the substrate is 200V, the deposition time is 60min, and the substrate is positioned in the middle of the TiAlY target and the TiSi target.
(5): the high-purity TiAlY and TiSi targets deposit a second functional layer TiAlSiYN on the surface of a substrate, ar gas is introduced into a cavity, the flow rate of nitrogen is 20sccm, the voltage of the TiAlY target is 1000V, the target power is 3KW, the pulse width is 100 [ mu ] s, the frequency is 1000HZ, the voltage of the TiSi target is 800V, the target power is 3KW, the pulse width is 100 [ mu ] s, the frequency is 1000HZ, the negative bias voltage of the substrate is 200V, and the deposition time is 60min.
(6): the high-purity TiAlY and TiSi targets deposit a third functional layer TiAlSiYN on the surface of a substrate, ar gas is introduced into a cavity, the flow rate of nitrogen is 20sccm, the voltage of the TiAlY target is 1200V, the target power is 3.5KW, the pulse width is 100 [ mu ] s, the frequency is 1000HZ, the voltage of the TiSi target is 1000V, the target power is 3.5KW, the pulse width is 100 [ mu ] s, the frequency is 1000HZ, the negative bias voltage of the substrate is 200V, and the deposition time is 60min.
Referring to FIG. 2, the hardness, H/E, H, of the rare earth doped erosion protection coating prepared in this example 3 /E 2 Fig. 3 is an erosion rate diagram of the rare earth doped erosion resistant protective coating, and fig. 4 is a twin crystal structure TEM diagram of the rare earth doped erosion resistant protective coating. From the above figures, the rare earth doped erosion-resistant protective coating has the hardness of 31.69 GPa+/-2.2 GPa, the elastic modulus of 346.04 GPa+/-22.85 GPa, the erosion rate of 0.039 mg/g+/-0.015 mg/g and the matrix titanium alloy erosion rate of 0.432 mg/g+/-0.039 mg/g, thus effectively playing a role in protection and improving the efficiency 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
In this embodiment, a method for preparing a rare earth doped erosion resistant protective coating includes the following steps:
(1) Respectively ultrasonically cleaning stainless steel, high-speed steel, silicon chip, hard alloy, titanium alloy matrix with acetone and ethanol for 15min, oven drying, placing into vacuum cavity, and pre-vacuumizing to 3.0X10 -5 Torr; argon is introduced into the film coating cavity, the flow rate of the argon is 40sccm, the air pressure is maintained at 2.0 mTorr, a direct current pulse bias voltage of-100V is applied to the substrate, and the surface of the substrate is etched by utilizing an ion beam, wherein the process is maintained 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 50nm.
(2): and 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 45sccm, the bias voltage of the high-power pulse magnetron sputtering Ti target is 800V, the target power is 3KW, the pulse width is 50 mu s, the frequency is 500HZ, the negative bias voltage of the substrate is 150V, the deposition time is 8min, and the thickness is 120nm.
(3): the high-purity Ti target deposits a TiN layer on the surface of the substrate, 50sccm of Ar gas and 20sccm of nitrogen gas are introduced into the cavity, the voltage of the high-power pulse magnetron sputtering target is 800V, the target power is 3.0KW, the pulse width is 100 mu s, the frequency is 500HZ, the negative bias voltage of the substrate is 150V, the deposition time is 12min, and the thickness is 240nm.
(4): the method comprises the steps that a first functional layer TiAlSiYN is deposited on the surface of a substrate by a high-purity TiAlY target and a TiSi target, wherein Ar gas is introduced into a cavity, the flow rate of nitrogen is 20sccm, the voltage of the TiAlY target is 700V, the target power is 2.8KW, the pulse width is 100 [ mu ] s, the frequency is 500HZ, the voltage of the TiSi target is 700V, the target power is 2.8KW, the pulse width is 100 [ mu ] s, the frequency is 500HZ, the negative bias voltage of the substrate is 200V, the deposition time is 60min, and the substrate is positioned in front of the TiAlY target.
(5): the high-purity TiAlY and TiSi targets deposit a second functional layer TiAlSiYN on the surface of a substrate, ar gas is introduced into a cavity, the flow rate of nitrogen is 20sccm, the voltage of the TiAlY targets is 800V, the target power is 3.1KW, the pulse width is 100 [ mu ] s, the frequency is 500HZ, the voltage of the TiSi targets is 800V, the target power is 3.1KW, the pulse width is 100 [ mu ] s, the frequency is 500HZ, the negative bias voltage of the substrate is 200V, and the deposition time is 60min.
(6): the high-purity TiAlY and TiSi targets deposit a third functional layer TiAlSiYN on the surface of a substrate, ar gas is introduced into a cavity, the flow rate of nitrogen is 20sccm, the voltage of the TiAlY target is 1200V, the target power is 3.4KW, the pulse width is 100 [ mu ] s, the frequency is 500HZ, the voltage of the TiSi target is 1000V, the target power is 3.4KW, the pulse width is 100 [ mu ] s, the frequency is 500HZ, the negative bias voltage of the substrate is 200V, and the deposition time is 60min.
The erosion rate test results of the rare earth doped erosion resistant protective coating prepared in this example are shown in table 1.
Example 3
In this embodiment, a method for preparing a rare earth doped erosion resistant protective coating includes the following steps:
(1) Respectively ultrasonically cleaning stainless steel, high-speed steel, silicon chip, hard alloy, titanium alloy matrix with acetone and ethanol for 15min, oven drying, placing into vacuum cavity, and pre-vacuumizing to 3.0X10 -5 Torr; argon is introduced into the film coating cavity, the flow rate of the argon is 40sccm, the air pressure is maintained at 2.0 mTorr, a direct current pulse bias voltage of-100V is applied to the substrate, and the surface of the substrate is etched by utilizing an ion beam, wherein the process is maintained for 20 minutes; the temperature of the cavity is 300 ℃, the current of the ion source is 0.3A, the power of the ion source is 300W, and the thickness is 100nm.
(2): and 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 mu s, the frequency is 800HZ, the negative bias voltage of the substrate is 50V, the deposition time is 10min, and the thickness is 150nm.
(3): the high-purity Ti target deposits a TiN layer on the surface of the substrate, 50sccm of Ar gas and 20sccm of nitrogen gas are introduced into the cavity, the voltage of the high-power pulse magnetron sputtering target is 800V, the target power is 3.5KW, the pulse width is 100 mu s, the frequency is 800HZ, the negative bias voltage of the substrate is 50V, the deposition time is 15min, and the thickness is 300nm.
(4): the method comprises the steps that a high-purity TiAlCE target and a TiSi target deposit a first functional layer TiAlSiCeN on the surface of a substrate, ar gas is introduced into a cavity at 50sccm, the flow rate of nitrogen gas is 20sccm, the target voltage of the TiAlCE target is 750V, the target power is 3.5KW, the pulse width is 200 [ mu ] s, the frequency is 800HZ, the target voltage of the TiSi target is 800V, the target power is 3.5KW, the pulse width is 100 [ mu ] s, 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): the high-purity TiAlCE and TiSi targets deposit a second functional layer TiAlSiCeN on the surface of a substrate, 50sccm of Ar gas is introduced into a cavity, the flow rate of nitrogen is 20sccm, the voltage of the TiAlCE target is 900V, the target power is 3.5KW, the pulse width is 200 [ mu ] s, the frequency is 800HZ, the voltage of the TiSi target is 800V, the target power is 3.0KW, the pulse width is 100 [ mu ] s, the frequency is 800HZ, the negative bias voltage of the substrate is 100V, and the deposition time is 60min.
(6): the high-purity TiAlCE and TiSi targets deposit a third functional layer TiAlSiCeN on the surface of a substrate, 50sccm of Ar gas is introduced into a cavity, the flow rate of nitrogen is 20sccm, the voltage of the TiAlCE target is 1100V, the target power is 3.0KW, the pulse width is 200 [ mu ] s, the frequency is 800HZ, the voltage of the TiSi target is 1000V, the target power is 2.5KW, the pulse width is 100 [ mu ] s, the frequency is 800HZ, the negative bias voltage of the substrate is 100V, and the deposition time is 60min.
The erosion rate test results of the rare earth doped erosion resistant protective coating prepared in this example are shown in table 1.
Example 4
In this embodiment, a method for preparing a rare earth doped erosion resistant protective coating includes the following steps:
(1) Respectively ultrasonically cleaning stainless steel, high-speed steel, silicon chip, hard alloy, titanium alloy matrix with acetone and ethanol for 15min, oven drying, placing into vacuum cavity, and pre-vacuumizing to 3.0X10 -5 Torr; argon is introduced into the film coating cavity, the flow rate of the argon is 30 sccm, the air pressure is maintained at 2.0 mTorr, a direct current pulse bias voltage of-100V is applied to the substrate, and the surface of the substrate is etched by utilizing an ion beam, wherein the process is maintained for 10 minutes; the temperature of the cavity is 450 ℃, the current of the ion source is 0.1A, the power of the ion source is 100W, and the thickness is 50nm.
(2): and 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 mu s, the frequency is 800HZ, the negative bias voltage of the substrate is 200V, the deposition time is 5min, and the thickness is 50nm.
(3): the high-purity Ti target deposits a TiN layer on the surface of the substrate, ar gas is introduced into a cavity at 40sccm, nitrogen gas is introduced into the cavity at 15sccm, the voltage of the high-power pulse magnetron sputtering target is 800V, the target power is 3.5KW, the pulse width is 50 mu s, the frequency is 800HZ, the negative bias of the substrate is 100V, the deposition time is 15min, and the thickness is 250nm.
(4): the method comprises the steps that a first functional layer TiAlSiYN is deposited on the surface of a substrate by a high-purity TiAlY target and a TiSi target, wherein Ar gas is introduced into a cavity, the flow rate of nitrogen is 10sccm, the voltage of the TiAlY target is 800V, the target power is 2.5KW, the pulse width is 50 [ mu ] s, the frequency is 1000HZ, the voltage of the TiSi target is 800V, the target power is 2.5KW, the pulse width is 80 [ mu ] s, the frequency is 500HZ, the negative bias voltage of the substrate is 150V, the deposition time is 20min, and the substrate is positioned in front of the TiAlY target.
(5): the high-purity TiAlY and TiSi targets deposit a second functional layer TiAlSiYN on the surface of a substrate, ar gas is introduced into a cavity, the flow rate of nitrogen is 15sccm, the voltage of the TiAlY target is 800V, the target power is 3.1KW, the pulse width is 50 [ mu ] s, the frequency is 500HZ, the voltage of the TiSi target is 800V, the target power is 3.1KW, the pulse width is 100 [ mu ] s, the frequency is 500HZ, the negative bias voltage of the substrate is 150V, and the deposition time is 20min.
(6): the high-purity TiAlY and TiSi targets deposit a third functional layer TiAlSiYN on the surface of a substrate, ar gas is introduced into a cavity at 40sccm, the nitrogen flow is 10sccm, the TiAlY target voltage is 1000V, the target power is 2.5KW, the pulse width is 50 [ mu ] s, the frequency is 500HZ, the TiSi target voltage is 1000V, the target power is 3.4KW, the pulse width is 100 [ mu ] s, the frequency is 500HZ, the substrate negative bias voltage is 150V, and the deposition time is 120min.
Example 5
In this embodiment, a method for preparing a rare earth doped erosion resistant protective coating includes the following steps:
(1) Respectively ultrasonically cleaning stainless steel, high-speed steel, silicon chip, hard alloy, titanium alloy matrix with acetone and ethanol for 15min, oven drying, placing into vacuum cavity, and pre-vacuumizing to 3.0X10 -5 Torr; argon is introduced into the film coating cavity, the flow rate of the argon is 35sccm, the air pressure is maintained at 2.0 mTorr, a direct current pulse bias voltage of-100V is applied to the substrate, and the surface of the substrate is etched by utilizing an ion beam, wherein the process is maintained for 15 minutes; the temperature of the cavity is 400 ℃, the current of the ion source is 0.1A, the power of the ion source is 100W, and the thickness is 50nm.
(2): by using a high-power pulse magnetron sputtering technology, 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 high-power pulse magnetron sputtering Ti target is biased for 800V, the target power is 3.2KW, the pulse width is 500 mu s, the frequency is 800HZ, the substrate negative bias is 200V, the deposition time is 5min, and the thickness is 50nm.
(3): the high-purity Ti target deposits a TiN layer on the surface of the substrate, ar gas is introduced into a cavity at 40sccm, nitrogen gas is introduced into the cavity at 10sccm, the voltage of the high-power pulse magnetron sputtering target is 800V, the target power is 3.5KW, the pulse width is 200 mu s, the frequency is 800HZ, the negative bias of the substrate is 100V, the deposition time is 10min, and the thickness is 200nm.
(4): the method comprises the steps that a first functional layer TiAlSiYN is deposited on the surface of a substrate by a high-purity TiAlY target and a TiSi target, wherein Ar gas is introduced into a cavity at 45sccm, the flow rate of nitrogen is 15sccm, the voltage of the TiAlY target is 750V, the target power is 2.5KW, the pulse width is 150 [ mu ] s, the frequency is 500HZ, the voltage of the TiSi target is 800V, the target power is 2.5KW, the pulse width is 80 [ mu ] s, the frequency is 300HZ, the negative bias voltage of the substrate is 200V, the deposition time is 120min, and the substrate is positioned in front of the TiAlY target.
(5): the high-purity TiAlY and TiSi targets deposit a second functional layer TiAlSiYN on the surface of a substrate, ar gas is introduced into a cavity at 45sccm, the nitrogen flow is 10sccm, the TiAlY target voltage is 800V, the target power is 2.5KW, the pulse width is 100 [ mu ] s, the frequency is 500HZ, the TiSi target voltage is 800V, the target power is 3.1KW, the pulse width is 100 [ mu ] s, the frequency is 500HZ, the substrate negative bias voltage is 200V, and the deposition time is 120min.
(6): the high-purity TiAlY and TiSi targets deposit a third functional layer TiAlSiYN on the surface of a substrate, ar gas is introduced into a cavity at 45sccm, the nitrogen flow is 15sccm, the TiAlY target voltage is 1200V, the target power is 3.4KW, the pulse width is 100 [ mu ] s, the frequency is 500HZ, the TiSi target voltage is 1000V, the target power is 3.4KW, the pulse width is 100 [ mu ] s, the frequency is 500HZ, the substrate negative bias voltage is 200V, and the deposition time is 20min.
Comparative example 1
In this comparative example, a method for preparing a protective coating comprises the steps of:
(1) Ultrasonic cleaning stainless steel, high-speed steel, silicon chip, hard alloy, titanium alloy matrix with acetone and ethanol for 15min, oven drying, and standingPre-evacuating to 3.0X10 in vacuum chamber -5 Torr; argon is introduced into the film coating cavity, the flow rate of the argon is 40sccm, the air pressure is maintained at 2.0 mTorr, a direct current pulse bias voltage of-100V is applied to the substrate, and the surface of the substrate is etched by utilizing an ion beam, wherein the process is maintained 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 50nm.
(2): and 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 at 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 mu s, the frequency is 1000HZ, the negative bias voltage of the substrate is 200V, the deposition time is 10min, and the thickness is 75nm.
(3): the high-purity Ti target deposits a TiN layer on the surface of the substrate, ar gas is introduced into the cavity at 50sccm, the nitrogen flow is 20sccm, the voltage of the high-power pulse magnetron sputtering target is 800V, the target power is 2.5KW, the pulse width is 100 mu s, the frequency is 1000HZ, the negative bias of the substrate is 200V, the deposition time is 10min, and the thickness is 100nm.
(4): the method comprises the steps of depositing a first functional layer TiAlSiYN on the surface of a substrate by a high-purity TiAlY and TiSi target, introducing Ar gas into a cavity, wherein the flow of the Ar gas is 50sccm, the flow of the nitrogen gas is 20sccm, the voltage of the TiAlY target is 800V, the current is 0.4A, the pulse width is 100 [ mu ] s, the frequency is 1000HZ, the voltage of the TiSi target is 800V, the target power is 3KW, the pulse width is 100 [ mu ] s, the frequency is 1000HZ, the negative bias of the substrate is 200V, and the deposition time is 60min.
The erosion rate test results of the coating prepared in this comparative example are shown in table 1.
Comparative example 2
In this comparative example, a method for preparing a protective coating comprises the steps of:
(1) Respectively ultrasonically cleaning stainless steel, high-speed steel, silicon chip, hard alloy, titanium alloy matrix with acetone and ethanol for 15min, oven drying, placing into vacuum cavity, and pre-vacuumizing to 3.0X10 -5 Torr; argon is introduced into the film coating cavity, the flow rate of the argon is 40sccm, the air pressure is maintained at 2.0 mTorr, a direct current pulse bias voltage of-100V is applied to the substrate, and the surface of the substrate is etched by utilizing an ion beam, wherein the process is maintained for 20 minutes; the temperature of the cavity is300. The ion source current was 0.1A, the ion source power was 100W, and the thickness was 50nm.
(2): and 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 20sccm 45sccm, the bias voltage of the high-power pulse magnetron sputtering Ti target is 800V, the target power is 3KW, the pulse width is 100 mu s, the frequency is 500HZ, the negative bias voltage of the substrate is 200V, the deposition time is 10min, and the thickness is 75nm.
(3): the high-purity Ti target deposits a TiN layer on the surface of the substrate, 50sccm of Ar gas and 20sccm of nitrogen gas are introduced into the cavity, the voltage of the high-power pulse magnetron sputtering target is 800V, the target power is 3.0KW, the pulse width is 100 mu s, the frequency is 500HZ, the negative bias voltage of the substrate is 200V, the deposition time is 10min, and the thickness is 150nm.
(4): the method comprises the steps that a first functional layer TiAlSiYN is deposited on the surface of a substrate by a high-purity TiAlY target and a TiSi target, wherein Ar gas is introduced into a cavity, the flow rate of nitrogen is 20sccm, the voltage of the TiAlY target is 700V, the target power is 2.8KW, the pulse width is 100 [ mu ] s, the frequency is 500HZ, the voltage of the TiSi target is 700V, the target power is 2.8KW, the pulse width is 100 [ mu ] s, the frequency is 500HZ, the negative bias voltage of the substrate is 200V, the deposition time is 60min, and the substrate is positioned in front of the TiAlY target.
(5): the high-purity TiAlY and TiSi targets deposit a second functional layer TiAlSiYN on the surface of a substrate, ar gas is introduced into a cavity, the flow rate of nitrogen is 20sccm, the voltage of the TiAlY target is 800V, the target power is 3,1KW, the pulse width is 100 mus, the frequency is 500HZ, the voltage of the TiSi target is 700V, the target power is 3.1KW, the pulse width is 100 mus, the frequency is 500HZ, the negative bias voltage of the substrate is 200V, and the deposition time is 60min.
The erosion rate test results of the coating prepared in this comparative example are shown in table 1.
Comparative example 3
In this comparative example, a method for preparing a protective coating comprises the steps of:
(1) Respectively ultrasonically cleaning stainless steel, high-speed steel, silicon chip, hard alloy and titanium alloy matrix with acetone and ethanol for 15min, oven drying, placing into a vacuum cavity, and pre-vacuumizing to 3.0X10-5 Torr; argon is introduced into the film coating cavity, the flow rate of the argon is 40sccm, the air pressure is maintained at 2.0 mTorr, a direct current pulse bias voltage of-100V is applied to the substrate, and the surface of the substrate is etched by utilizing an ion beam, wherein the process is maintained 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 50nm.
(2): and 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 at 20sccm and 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 mu s, the frequency is 1000HZ, the negative bias voltage of the substrate is 200V, the deposition time is 10min, and the thickness is 75nm.
(3): the high-purity Ti target deposits a TiN layer on the surface of the substrate, ar gas is introduced into the cavity at 50sccm, the nitrogen flow is 20sccm, the voltage of the high-power pulse magnetron sputtering target is 800V, the current is 3A, the target power is 2.5KW, the pulse width is 100 mu s, the frequency is 1000HZ, the negative bias of the substrate is 200V, the deposition time is 10min, and the thickness is 100nm.
(4): the method comprises the steps of depositing TiAlSiN on the surface of a substrate by a high-purity TiAl and TiSi target, introducing Ar gas into a cavity at a speed of 50sccm, introducing nitrogen gas at a flow of 20sccm, wherein the TiAl target voltage is 800V, the target power is 3KW, the pulse width is 100 mu s, the frequency is 1000HZ, the TiSi target voltage is 800V, the pulse width is 100 mu s, the frequency is 1000HZ, the substrate negative bias voltage is 200V, and the deposition time is 60min.
The erosion rate test results of the coating prepared in this comparative example are shown in table 1.
TABLE 1 erosion Rate results for examples 1-3 and comparative examples 1-3
In addition, the inventor refers to the previous examples and uses other raw materials, process operations and process strips in the specification
The pieces were tested and all gave the desired results.
While the invention has been described with reference to illustrative embodiments, those skilled in the art will appreciate that the invention may be practiced without departing from the invention
Various other changes, omissions, and/or additions may be made and substantial equivalents may be substituted for those in the practice without departing from the spirit and scope thereof
The elements of the examples. 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
The teachings of the present invention should be applied. Therefore, it is intended that the invention not be limited to the particular embodiments disclosed for carrying out this invention,
but that the invention will include all embodiments falling within the scope of the appended claims. In addition, unless specifically stated
The use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used
Etc. to distinguish one element from another element.
Claims (13)
1. A rare earth doped erosion resistant protective coating is characterized in that: 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 reinforcing 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 laminated 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 reinforcing crystal structure, the doping content of rare earth elements in the first rare earth doped TiAlSiN functional layer is 0.02-0.8at%, and the grain size is 100-200 nm; the second rare earth doped TiAlSiN functional layer has a nano twin crystal structure, the doping content of rare earth elements in the second rare earth doped TiAlSiN functional layer is 0.8-1.2at%, and the grain size is 40-80 nm; the third rare earth doped TiAlSiN functional layer has an amorphous wrapping nanocrystalline structure, the doping content of rare earth elements in the third rare earth doped TiAlSiN functional layer is 1.2-2.4at%, and the grain size is 20-30 nm; 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.
2. The rare earth doped erosion resistant protective coating of claim 1 wherein: 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 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 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 for preparing a rare earth doped erosion protection coating according to any one of claims 1 to 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 anti-erosion protective coating.
7. The preparation method according to claim 6, characterized by comprising the following steps: 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, characterized by comprising the following steps: and (3) introducing protective gas with the flow 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 substrate negative bias voltage is 50-200V, and the deposition time is 5-10 min.
9. The preparation method according to claim 6, characterized by comprising the following steps: and (3) 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, continuously depositing a TiN layer on the surface of the substrate deposited with the Ti layer by using the high-power pulse magnetron sputtering, 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 10-15 min.
10. The preparation method according to claim 6, characterized by comprising the following steps: and (3) 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 of 40-50 sccm and nitrogen with the flow of 10-20 sccm into the reaction cavity, and sequentially 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.
11. The method of claim 10, wherein the process conditions for depositing the first rare earth doped tiaalsin functional layer include: and (3) introducing protective gas with the flow of 40-50 sccm, nitrogen with the flow of 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 mu s, the frequency is 500-1000Hz, the negative bias of the substrate is 100-200V, and the deposition time is 20-120 min.
12. The method of claim 10, wherein the process conditions for depositing the second rare earth doped tiaalsin functional layer include: and (3) introducing protective gas with the flow of 40-50 sccm, nitrogen with the flow of 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 mu s, the frequency is 500-1000Hz, the negative bias of the substrate is 100-200V, and the deposition time is 20-120 min.
13. The method of claim 10, wherein the process conditions for depositing the third rare earth doped tiaalsin functional layer include: and (3) introducing protective gas with the flow of 40-50 sccm, nitrogen with the flow of 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 mu s, the frequency is 500-1000Hz, the negative bias voltage of the substrate is 100-200V, and the deposition time is 20-120 min.
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| CN109628896A (en) * | 2019-01-17 | 2019-04-16 | 四川大学 | A kind of gradient-structure TiAlSiYN polynary nanometer coating and preparation method thereof |
| CN109735803A (en) * | 2018-12-27 | 2019-05-10 | 广东工业大学 | A kind of TiSiYN multicomponent complex gradient cutter coat and preparation method thereof |
| CN110760797A (en) * | 2019-11-27 | 2020-02-07 | 宁波工业技术研究院 | Surface-tough erosion-resistant protective coating and preparation method and application thereof |
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| CN109735803A (en) * | 2018-12-27 | 2019-05-10 | 广东工业大学 | A kind of TiSiYN multicomponent complex gradient cutter coat and preparation method thereof |
| CN109628896A (en) * | 2019-01-17 | 2019-04-16 | 四川大学 | A kind of gradient-structure TiAlSiYN polynary nanometer coating and preparation method thereof |
| CN110760797A (en) * | 2019-11-27 | 2020-02-07 | 宁波工业技术研究院 | Surface-tough erosion-resistant protective coating and preparation method and application thereof |
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