CN115233171A - High-entropy superlattice nitride coating and preparation method thereof - Google Patents

High-entropy superlattice nitride coating and preparation method thereof Download PDF

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CN115233171A
CN115233171A CN202210725009.3A CN202210725009A CN115233171A CN 115233171 A CN115233171 A CN 115233171A CN 202210725009 A CN202210725009 A CN 202210725009A CN 115233171 A CN115233171 A CN 115233171A
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coating
entropy
superlattice
target
nitride coating
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CN115233171B (en
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杜昊
戴厚富
张泽
李潇阳
刘浩
康建军
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Guizhou University
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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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • 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
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • 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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  • Engineering & Computer Science (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The invention discloses a high-entropy superlattice nitride coating and a preparation method thereof, belonging to the technical field of coatings. The preparation method of the coating comprises the following steps: at Ar and N 2 Sputtering Al in atmosphere by high-power pulse magnetron sputtering 25 Cr 25 Ti 25 Nb 25 Alloy target and V elementary substance target, al 25 Cr 25 Ti 25 Nb 25 The alloy target and the V elementary substance target alternately work. The coating of the invention increases the fracture toughness of the coating and reduces the residual compressive stress of the coating by coherent strain between superlattice interfaces while further improving the hardness of the coating, and in addition, the metal atom proportion of the AlCrTiNbN layer meets the atom proportion requirement of high-entropy nitride to metal vacancy elements, thereby meeting the requirements of high-entropy nitride on the atomic proportion of the metal vacancy elementsThe strengthening standard of (2) also meets the standard of improving the fracture toughness of the coating by the superlattice coating. The preparation method of the coating has strong applicability to equipment, and can realize the regulation and control of the nano level of the film layers and the accurate control of the thickness proportion among the film layers by controlling the number of sputtering pulses.

Description

High-entropy superlattice nitride coating and preparation method thereof
Technical Field
The invention belongs to the technical field of coatings, and relates to a high-entropy superlattice nitride coating and a preparation method of the high-entropy superlattice nitride coating.
Background
Since the introduction of the concept of high-entropy alloy, it has been receiving much attention because of its excellent properties. The high-entropy alloy is superior to the traditional alloy in the aspects of hardness, corrosion resistance, friction and wear resistance and the like. The improvement of the performance of the high-entropy alloy is caused by the interaction of four basic effects, namely a high-entropy effect on thermodynamics, a lattice distortion effect on a structure, a slow diffusion effect on kinetics and a cocktail effect on performance.
The metal bond in the high-entropy alloy is replaced by a covalent bond or an ionic bond with high bond energy to form a high-entropy ceramic material, such as high-entropy nitride, and the hardness, wear resistance and oxidation resistance of the material can be further improved to meet engineering and application requirements. The high-entropy nitride can be used as a hard coating with special functions to be applied to the surface of a workpiece, so that the overall corrosion resistance, wear resistance, thermal stability and the like of the workpiece are improved, and the effect is higher than that of the traditional binary or ternary nitride. However, for the high-entropy nitride coating prepared by the physical vapor deposition method, due to the inherent high lattice distortion effect, the high-entropy nitride coating is often high in hardness, but low in fracture toughness and high in residual stress, so that the high-entropy nitride coating is large in bonding strength difference on different substrates, and if the substrate is heated in the coating deposition process, the coating is often dropped in the cooling process, and the application of the high-entropy nitride coating is severely limited.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a high-entropy superlattice nitride coating and a preparation method thereof, which aim to solve the technical problems in the prior art.
The technical scheme adopted by the invention is as follows: a high entropy superlattice nitride coating comprising periodically alternating layers of AlCrTiNbN and VN.
Wherein, the thickness proportion relation of the AlCrTiNbN layer and the VN layer of the coating is as follows: 1 to 7:1.
wherein, the thickness proportion relation of the AlCrTiNbN layer and the VN layer is as follows: 7:1.
wherein, the atomic ratio relation of the AlCrTiNbN layer is as follows: al, cr, ti, nb, N = 7 to 12, and 52 to 65.
Wherein, the atomic ratio relationship of the VN layer is: v, N = 48 to 52, 48 to 52.
A preparation method of a high-entropy superlattice nitride coating comprises the following steps: at Ar and N 2 Sputtering Al in atmosphere by high-power pulse magnetron sputtering 25 Cr 25 Ti 25 Nb 25 An alloy target and a V elemental target.
Wherein Al is sputtered by using a high-power pulse magnetron sputtering method 25 Cr 25 Ti 25 Nb 25 The method for alloying the target comprises the following steps: the negative pulse width is 10 to 50 mu s, the negative pulse frequency is 1000 to 2000 Hz, and the peak current is 1 to 2A/cm 2 。
The method for sputtering the V elemental target by using the high-power pulse magnetron sputtering method comprises the following steps: the negative pulse width is 10 to 50 mu s, the negative pulse frequency is 1000 to 2000 Hz, and the peak current is 0.5 to 1.5A/cm 2 。
Wherein the method of high power pulse magnetron sputtering is used for sputtering Al 25 Cr 25 Ti 25 Nb 25 The method for preparing the alloy target and the V elementary substance target comprises the following steps: al (aluminum) 25 Cr 25 Ti 25 Nb 25 And the alloy target and the V elementary substance target alternately work.
Wherein Al is sputtered by using a high-power pulse magnetron sputtering method 25 Cr 25 Ti 25 Nb 25 The method for preparing the alloy target and the V elementary substance target comprises the following steps: al (Al) 25 Cr 25 Ti 25 Nb 25 Al when the alloy target and the V elementary substance target work alternately 25 Cr 25 Ti 25 Nb 25 Of alloy targets and V-elementary targetsThe number of pulses is 1.5X 10 4 ~9×10 4 。
The invention has the beneficial effects that: compared with the prior art, the invention has the following effects:
(1) The high-entropy superlattice nitride coating introduces the superlattice structure of the AlCrTiNbN layer and the VN layer, increases the fracture toughness of the coating and reduces the residual compressive stress of the coating through coherent strain between superlattice interfaces while further improving the hardness of the coating, wherein the residual stress of the coating can be reduced from-4.1 +/-0.21 GPa (comparative example I) to-1.7 +/-0.23 GPa (example I), H 3 /E *2 From 0.166 (comparative example one) to 0.196 (example two), in addition, the metal atom ratio of the AlCrTiNbN layer meets the atom ratio requirement of the high-entropy nitride to the metal vacancy element, so that the AlCrTiNbN layer also meets the strengthening standard of the high-entropy nitride; it is particularly important that the greater the residual stress, the more easily the coating peels off, and the smaller the H/E, the less abrasion resistant the coating.
(2) The preparation method of the high-entropy superlattice nitride coating provided by the invention adopts Al 25 Cr 25 Ti 25 Nb 25 The alloy target and the V elementary substance target are alternately sputtered to realize the construction of a superlattice structure, and the nano-level regulation of the film layers and the accurate control of the thickness proportion among the film layers can also be realized by controlling the number of sputtering pulses. Compared with the traditional mode of closing the target baffle alternatively or rotating the workpiece, the preparation method has strong applicability to coating equipment, high utilization rate of the target and more accurate control on the thickness of the film.
Drawings
Fig. 1 is a pulse schematic diagram and a coating structure schematic diagram of target discharge in a high-entropy superlattice nitride coating preparation method.
FIG. 2 is a graph showing the residual stress of the coating in the first comparative example, the first embodiment, the second embodiment and the third embodiment;
FIG. 3 shows H/E and H of the coatings of comparative example one, example two and example three 3 /E *2 。
Detailed Description
The invention is further described below with reference to specific examples.
The first embodiment is as follows: a high entropy superlattice nitride coating, the coating is composed of periodically alternating AlCrTiNbN layers and VN layers, the thickness ratio of the AlCrTiNbN layers and the VN layers is 1:1, the atomic ratio relationship of the AlCrTiNbN layer is as follows: the atomic ratio of Al to Cr to Ti to Nb to N = 12: 8: 7: 8: 65, VN layer is: n = 48: 52, and the preparation method of the high-entropy superlattice nitride coating comprises the following steps: at Ar and N 2 Sputtering Al in atmosphere by high-power pulse magnetron sputtering 25 Cr 25 Ti 25 Nb 25 Alloy target and V elementary substance target, al 25 Cr 25 Ti 25 Nb 25 The sputtering negative pulse width of the alloy target is 10 mus, the negative pulse frequency is 1000 Hz, and the peak current is 2A/cm 2 V the sputtering negative pulse width of the elemental target is 50 mus, the negative pulse frequency is 2000 Hz, and the peak current is 0.5A/cm 2 ，Al 25 Cr 25 Ti 25 Nb 25 Alloy target and V simple substance target, when they are alternatively worked, al 25 Cr 25 Ti 25 Nb 25 The number of pulses of the alloy target and the V elemental target was 1.5X 10 4 。
In this example, the thickness ratio of the AlCrTiNbN layer to the VN layer in the coating was determined to be about 1:1, modulation period of 1.6 nm, residual stress of-1.7 +/-0.23 GPa, H/E and H 3 /E *2 0.096 and 0.194, respectively.
The second embodiment: a high entropy superlattice nitride coating consisting of periodically alternating AlCrTiNbN layers and VN layers, the thickness ratio relationship of AlCrTiNbN layers and VN layers being 4:1, the atomic ratio relationship of the AlCrTiNbN layer is as follows: the Al, cr, ti, nb and N are = 10: 10: 10: 10: 60, and the atomic ratio of the VN layer is as follows: n = 50: 50, and the preparation method of the high-entropy superlattice nitride coating comprises the following steps: at Ar and N 2 Sputtering Al in atmosphere by high-power pulse magnetron sputtering 25 Cr 25 Ti 25 Nb 25 Alloy target and V elementary substance target, al 25 Cr 25 Ti 25 Nb 25 The sputtering negative pulse width of the alloy target is 20 mus, the negative pulse frequency is 1500 Hz, and the peak currentIs 1.5A/cm 2 The sputtering negative pulse width of the V elementary substance target is 20 mus, the negative pulse frequency is 1500 Hz, and the peak current is 1A/cm 2 ，Al 25 Cr 25 Ti 25 Nb 25 Alloy target and V simple substance target, when they are alternatively worked, al 25 Cr 25 Ti 25 Nb 25 The pulse number of the alloy target and the V elementary substance target is 4.5 multiplied by 10 4 。
In this example, the thickness ratio of the alcrtiinnbn layer to the VN layer in the coating was found to be about 4:1, modulation period of 4.8 nm, residual stress of-2.6 +/-0.21 GPa, H/E and H 3 /E *2 0.096 and 0.196, respectively.
Example three: a high entropy superlattice nitride coating, the coating is composed of periodically alternating AlCrTiNbN layers and VN layers, the thickness ratio relationship of the AlCrTiNbN layers and the VN layers is 7:1, the atomic ratio relationship of the AlCrTiNbN layer is as follows: the atomic ratio relation of Al, cr, ti, nb and N = 12: 12: 12: 12: 52 and the VN layer is as follows: n = 52: 48, and the preparation method of the high-entropy superlattice nitride coating comprises the following steps: at Ar and N 2 Sputtering Al in atmosphere by high-power pulse magnetron sputtering 25 Cr 25 Ti 25 Nb 25 Alloy target and V elementary substance target, al 25 Cr 25 Ti 25 Nb 25 The sputtering negative pulse width of the alloy target is 50 mus, the negative pulse frequency is 2000 Hz, and the peak current is 1A/cm 2 The sputtering negative pulse width of the V elementary substance target is 10 mu s, the negative pulse frequency is 1000 Hz, and the peak current is 1.5A/cm 2 ，Al 25 Cr 25 Ti 25 Nb 25 Alloy target and V simple substance target, when they are alternatively worked, al 25 Cr 25 Ti 25 Nb 25 The pulse number of the alloy target and the V elementary substance target is 9 multiplied by 10 4 。
It was found that in this example, the thickness ratio of the AlCrTiNbN layer to the VN layer in the coating was about 7:1, modulation period of 9.6 nm, residual stress of-2.6 +/-0.21 GPa, H/E and H 3 /E *2 0.096 and 0.194, respectively.
Comparative example one (AlCrTiNbN coating):
AlCrthe atomic ratio relation of the TiNbN layer is as follows: the atomic ratio relation of Al, cr, ti, nb and N = 12: 12: 12: 12: 52 and the VN layer is as follows: n = 52: 48, and the preparation method of the high-entropy superlattice nitride coating comprises the following steps: at Ar and N 2 Sputtering Al in atmosphere by high-power pulse magnetron sputtering 25 Cr 25 Ti 25 Nb 25 Alloy target of Al 25 Cr 25 Ti 25 Nb 25 The sputtering negative pulse width of the alloy target is 20 mus, the negative pulse frequency is 1000 Hz, and the peak current is 2A/cm 2 。
The detection proves that in the comparative example, the residual stress of the AlCrTiNbN coating is-4.1 +/-0.21 GPa 3 /E *2 0.090 and 0.166, respectively.
To illustrate the structure and properties of the tool surface coatings obtained in the above examples and comparative examples, the present invention examined them as follows:
(1) Residual stress
The residual stress of the coatings in (a) example one, (b) example two, (c) example three and (d) comparative example one were tested by matrix bending test using PANalytical Empyrean type XRD, and it can be seen that a high entropy superlattice nitride coating according to the present invention has a lower residual compressive stress at higher entropy nitride coatings.
(2) Dura mater ratios H/E and H 3 /E *2
Hard film ratios H/E and H of the coatings in (a) example one, (b) example two, (c) example three, (d) comparative example one were tested and calculated using a Triboidender model TI 950 nanoindenter 3 /E *2 It can be seen that the high-entropy superlattice nitride coating has higher hard film ratio H/E and H 3 /E *2 And thus has a stronger fracture toughness.
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily think of the changes or substitutions within the technical scope of the present invention, and therefore the scope of the present invention shall be subject to the protection scope of the claims.

Claims (9)

1. A high entropy superlattice nitride coating, characterized by: the coating comprises periodically alternating layers of AlCrTiNbN and VN.
2. A high entropy superlattice nitride coating in accordance with claim 1, wherein: the thickness proportion relation of the AlCrTiNbN layer and the VN layer of the coating is as follows: 1 to 7:1.
3. a high entropy superlattice nitride coating in accordance with claim 1, wherein: the thickness proportion relation of the AlCrTiNbN layer and the VN layer of the coating is as follows: 7:1.
4. a high entropy superlattice nitride coating in accordance with claim 1, wherein: the AlCrTiNbN layer atomic ratio relation is as follows: al, cr, ti, nb, N = 7 to 12, and 52 to 65.
5. A high entropy superlattice nitride coating in accordance with claim 1, wherein: the atomic ratio relationship of the VN layer is as follows: n = 48 to 52: 48 to 52.
6. A method of preparing a high entropy superlattice nitride coating as claimed in any one of claims 1-5, characterized in that: at Ar and N 2 Sputtering Al in atmosphere by high-power pulse magnetron sputtering 25 Cr 25 Ti 25 Nb 25 Alloy target and V elementary substance target, al 25 Cr 25 Ti 25 Nb 25 The alloy target and the V elementary substance target alternately work to prepare the high-entropy superlattice nitride coating.
7. A method for preparing a high entropy superlattice nitride coating as claimed in claim 6, characterized in that: method for sputtering Al by using high-power pulse magnetron sputtering 25 Cr 25 Ti 25 Nb 25 The alloy target has a negative pulse width of10 to 50 mu s, negative pulse frequency of 1000 to 2000 Hz, and peak current of 1 to 2A/cm 2 。
8. A method of preparing a high entropy superlattice nitride coating in accordance with claim 6, wherein: the parameters of sputtering the V elementary substance target by using a high-power pulse magnetron sputtering method are that the negative pulse width is 10 to 50 mu s, the negative pulse frequency is 1000 to 2000 Hz, and the peak current is 0.5 to 1.5A/cm 2 。
9. A method of preparing a high entropy superlattice nitride coating in accordance with claim 6, wherein: al (Al) 25 Cr 25 Ti 25 Nb 25 Al when the alloy target and the V elementary substance target work alternately 25 Cr 25 Ti 25 Nb 25 The pulse number of the alloy target and the V elementary substance target is 1.5 multiplied by 10 4 ~9×10 4 。
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Citations (8)

* Cited by examiner, † Cited by third party
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WO2000048725A1 (en) * 1999-02-17 2000-08-24 Oxxel Oxide Electronics Technology, Inc. Method for preparation of libraries using a combinatorial molecular beam epitaxy (combe) apparatus
CN1888125A (en) * 2006-07-20 2007-01-03 上海交通大学 Nanometer layered VN/SiO2 coating and its prepn
JP2010506083A (en) * 2006-10-04 2010-02-25 フェデラル−モグル・ブルシャイト・ゲーエムベーハー Piston rings for internal combustion engines
CN103212729A (en) * 2013-04-17 2013-07-24 重庆市硅酸盐研究所 Numerical control cutting tool with CrAlTiN superlattice coating and manufacturing method thereof
CN103774090A (en) * 2014-02-07 2014-05-07 上海理工大学 High-hardness TiSiN coating containing vanadium nitride nano insertion layer and preparation method of coating
CN108220880A (en) * 2018-01-30 2018-06-29 上海新弧源涂层技术有限公司 A kind of high rigidity high corrosion-resistant high-entropy alloy nitride coatings and preparation method thereof
CN112760610A (en) * 2021-01-25 2021-05-07 中国科学院兰州化学物理研究所 High-entropy nitride coating for surface protection of aviation bearing and preparation method thereof
CN114059029A (en) * 2021-11-18 2022-02-18 西华大学 Cr/CrN/NbN/NbXN rare earth superlattice coating for high-temperature alloy processing and preparation method thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000048725A1 (en) * 1999-02-17 2000-08-24 Oxxel Oxide Electronics Technology, Inc. Method for preparation of libraries using a combinatorial molecular beam epitaxy (combe) apparatus
CN1888125A (en) * 2006-07-20 2007-01-03 上海交通大学 Nanometer layered VN/SiO2 coating and its prepn
JP2010506083A (en) * 2006-10-04 2010-02-25 フェデラル−モグル・ブルシャイト・ゲーエムベーハー Piston rings for internal combustion engines
CN103212729A (en) * 2013-04-17 2013-07-24 重庆市硅酸盐研究所 Numerical control cutting tool with CrAlTiN superlattice coating and manufacturing method thereof
CN103774090A (en) * 2014-02-07 2014-05-07 上海理工大学 High-hardness TiSiN coating containing vanadium nitride nano insertion layer and preparation method of coating
CN108220880A (en) * 2018-01-30 2018-06-29 上海新弧源涂层技术有限公司 A kind of high rigidity high corrosion-resistant high-entropy alloy nitride coatings and preparation method thereof
CN112760610A (en) * 2021-01-25 2021-05-07 中国科学院兰州化学物理研究所 High-entropy nitride coating for surface protection of aviation bearing and preparation method thereof
CN114059029A (en) * 2021-11-18 2022-02-18 西华大学 Cr/CrN/NbN/NbXN rare earth superlattice coating for high-temperature alloy processing and preparation method thereof

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