CN-121976158-A - Composite coating, arched composite coating, and preparation methods and applications thereof

CN121976158ACN 121976158 ACN121976158 ACN 121976158ACN-121976158-A

Abstract

The invention provides a composite coating, an arched composite coating, and a preparation method and application thereof. The composite coating comprises metal layers and ceramic layers which are alternately arranged along the thickness direction, and at least part of the metal layers and the ceramic layers are corrugated structures which undulate along the thickness direction of the composite coating. The composite coating is heat treated to enable it to be transformed from a corrugated structure to an arched composite coating having arched structural units. The composite coating and the arched composite coating provided by the invention have excellent mechanical properties, can keep high hardness and high elastic modulus at high temperature, and simultaneously have extremely high surface quality.

Inventors

WANG LIPING
REN SIMING
ZHANG XICAI
WANG HAIXIN

Assignees

中国科学院宁波材料技术与工程研究所

Dates

Publication Date: 20260505
Application Date: 20260202

Claims (10)

1. A composite coating layer comprising metal layers and ceramic layers alternately arranged in a thickness direction, wherein at least part of the metal layers and ceramic layers have a corrugated structure undulating in the thickness direction of the composite coating layer.
2. The composite coating according to claim 1, wherein the metal layer and the ceramic layer have a single-layer thickness of nanometer scale, so that the composite coating has a corrugated nanometer multi-layer structure; and/or the ratio of the single-layer thicknesses of the metal layer and the ceramic layer is 1:2-1:4; And/or the single-layer thickness of the metal layer is 1 nm-20 nm, and the single-layer thickness of the ceramic layer is 5 nm-20 nm; and/or the metal contained in the metal layer comprises one or more combinations of Ta, ti, cr, zr; And/or the material of the ceramic layer comprises B 4 C; and/or the total thickness of the composite coating is 1-3 mu m; and/or the hardness of the composite coating at 500 ℃ is more than 80% of the hardness at room temperature, and the elastic modulus at 500 ℃ is more than 80% of the hardness at room temperature; And/or the composite coating is prepared by adopting an unbalanced magnetron sputtering technology in a multi-target co-sputtering mode.
3. An arched composite coating, comprising metal layers and ceramic layers alternately arranged in a thickness direction, wherein at least part of the metal layers and ceramic layers have protrusions facing a surface of the arched composite coating, thereby providing an arched structural unit to a cross section of the arched composite coating.
4. The arched composite coating of claim 3, wherein the protrusions have a height of 5nm to 20 nm; and/or the section of the arched composite coating is provided with arched structure units which are arranged in an array; and/or, the monolayer thickness of the metal layer and the ceramic layer is nano-scale, so that the arched composite coating has an arched nano multi-layer structure; And/or the single-layer thickness of the metal layer is 1 nm-20 nm, and the single-layer thickness of the ceramic layer is 5 nm-20 nm; and/or the metal contained in the metal layer comprises one or more combinations of Ta, ti, cr, zr; And/or the material of the ceramic layer comprises B 4 C; and/or the total thickness of the arched composite coating is 1-3 mu m.
5. A preparation method of a composite coating is characterized by comprising the steps of adopting an unbalanced magnetron sputtering technology and adopting a multi-target co-sputtering mode to prepare a first metal target, a first ceramic target, a second metal target and a second ceramic target which are sequentially and annularly arranged, placing a substrate to be sputtered in the middle of the annularly arranged target, and rotating the substrate in a biaxial rotation mode during sputtering.
6. The method of manufacturing a ceramic device according to claim 5, wherein the first metal of the first metal target comprises Ti, the second metal of the second metal target comprises Ta, ti, cr, zr or a combination of one or more of them, and the materials of the first and second ceramic targets comprise B 4 C; And/or the first metal target is a titanium target, the second metal target is a tantalum target, the first ceramic target is a first boron carbide target, and the second ceramic target is a second boron carbide target; and/or the technological conditions of the unbalanced magnetron sputtering technology comprise that the target current of the first ceramic target and the second ceramic target is 3.0-5.0A, the target current of the second metal target is 0.3-2.0A, and the target current of the first metal target is 3-7A, preferably, the target current of the second metal target is 0.6A-1.0A; And/or the bias voltage of the substrate is-20V to-100V, and/or the rotating speed of the substrate is 0.5rpm to 2rpm; And/or the working gas comprises argon, the flow rate of the working gas is 10-20 sccm, the air pressure of the reaction chamber is 0.1-0.3 Pa, and the working distance is 10-30 cm; And/or the cavity background vacuum is 1×10 -5 mbar ~ 5×10 -5 mbar; and/or the total deposition time is 2-6 h.
7. A method of preparing an arcuate composite coating, comprising: a composite coating prepared by the preparation method of claim 5 or 6; and carrying out heat treatment on the composite coating to obtain the arched composite coating.
8. The arched composite coating according to claim 7, wherein the temperature of the heat treatment is 300-500 ℃, and/or the heat treatment is kept for 10-30 hours, and/or the temperature is raised to the temperature required by the heat treatment at a temperature raising rate of 1-10 ℃ per minute; and/or controlling the ratio of the single-layer thicknesses of the metal layer and the ceramic layer in the composite coating to be 1:2-1:4, and then carrying out the heat treatment.
9. A high strength and toughness coating structure comprising: the metal transition layer is used for being combined with the base material and comprises a first metal; The gradient transition layer is formed on the metal transition layer, and the gradient transition layer comprises a first metal, a second metal and a ceramic material, wherein the content of the first metal gradually decreases along the direction away from the metal transition layer, and the content of the second metal and the ceramic material gradually increases along the direction away from the metal transition layer; The composite coating of claim 1 or 2 or the arched composite coating of claim 3 or 4 formed on the gradient transition layer.
10. Use of the composite coating of claim 1 or 2, the arched composite coating of claim 3 or 4, or the high strength and toughness coating structure of claim 9 in the manufacture of aerospace equipment, nuclear power plant, marine engineering equipment, or microelectronic devices.

Description

Composite coating, arched composite coating, and preparation methods and applications thereof Technical Field The invention belongs to the technical field of magnetron sputtering coating, and particularly relates to a composite coating, an arched composite coating, and a preparation method and application thereof. Background In the fields of aerospace, nuclear power and the like, key parts are in long-term service under the working conditions of high temperature and complex stress, and extremely high performance requirements are provided for protective coatings on the surfaces of the parts. The high toughness can improve the fracture resistance of the coating, avoid the coating from peeling off due to stress concentration, and further ensure the stable operation and high-reliability service of core equipment. Currently, a variety of surface coating techniques have been developed by researchers. However, although the metal coating has better toughness and ductility, the hardness is generally lower, and the metal coating is extremely easy to wear and fail when facing particle scouring or friction, so that the long-term protection requirement of key parts is difficult to meet. The ceramic coating has higher hardness and excellent high temperature resistance, but has higher brittleness, and when the ceramic coating bears vibration or thermal cycle load, microcracks are easily generated in the coating, so that the coating is invalid. Therefore, how to realize the tough integrated design of the coating so as to meet the requirements of the fields of aerospace, nuclear power and the like on the high-performance protective coating is one of the problems to be solved urgently. Disclosure of Invention In order to solve all or part of the technical problems, the invention provides the following technical scheme: A first aspect of the present invention provides a composite coating layer comprising metal layers and ceramic layers alternately arranged in a thickness direction, and at least part of the metal layers and ceramic layers have a corrugated structure undulating in the thickness direction of the composite coating layer. On one hand, the composite coating provided by the invention is provided with the laminated metal layer and ceramic layer, the metal layer can provide large deformation, the occurrence of brittle cracks is prevented, the ceramic layer can provide excellent bearing capacity and improve the coating strength, and on the other hand, the metal layer and the ceramic layer are in a corrugated structure which undulates along the thickness direction of the composite coating, and the structure can convert vertical load into compressive stress along the convex edge, so that the structural stability is enhanced from the stress angle. The two aspects of synergistic effect can lead the composite coating to show excellent toughness and excellent high-temperature mechanical property. In some embodiments, the monolayer thickness of the metal layer, ceramic layer is nano-scale, such that the composite coating has a corrugated nano-multilayer structure. In some embodiments, the ratio of the single-layer thicknesses of the metal layer and the ceramic layer is 1:2-1:4. In some embodiments, the monolayer thickness of the metal layer is 1nm to 20nm, preferably 2nm to 6 nm. In some embodiments, the thickness of the monolayer of the ceramic layer is 5nm to 20 nm, preferably 8 nm to 12 nm. In some embodiments, the composite coating has a total thickness of 1 μm to 3 μm. In some embodiments, the metal included in the metal layer comprises one or a combination of more of Ta, ti, cr, zr. In some embodiments, the material of the ceramic layer includes B 4 C. In some embodiments, the metal layer is a Ta layer and the ceramic layer is a B 4 C layer. In some embodiments, the surface roughness of the composite coating is 0.4 nm to 3 nm. In some examples, the hardness of the composite coating at 500 ℃ is 80% or more, and in some embodiments 85% or more, of the hardness at room temperature. In some examples, the composite coating has an elastic modulus at 500 ℃ of 80% or more at room temperature, and in some embodiments may reach 85% or more. In some embodiments, the hardness of the composite coating is above 25GPa under the room temperature condition, and can reach 25 GPa-35 GPa, the elastic modulus is above 200GPa, and can reach 200 GPa-400 GPa. In some embodiments, the composite coating is an amorphous coating. The outermost layer of the composite coating can be a metal layer or a ceramic layer. In some embodiments, the outermost layer of the composite coating is a metal layer, for example, including metallic tantalum or a metallic tantalum layer, and an oxide formed by oxidation of tantalum has a certain protection effect on the coating. In some embodiments, the composite coating is produced by multi-target co-sputtering using unbalanced magnetron sputtering techniques. A second aspect of the present invention provides an arche