CN116356254A - Multilayer hard coating structure for improving fatigue life of hard coating and preparation method thereof - Google Patents

Multilayer hard coating structure for improving fatigue life of hard coating and preparation method thereof Download PDF

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CN116356254A
CN116356254A CN202310234795.1A CN202310234795A CN116356254A CN 116356254 A CN116356254 A CN 116356254A CN 202310234795 A CN202310234795 A CN 202310234795A CN 116356254 A CN116356254 A CN 116356254A
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hard coating
layer
nano
multilayer
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李刘合
李花
张然
徐晔
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Beihang 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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641—Nitrides
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    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • 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
    • C23C14/0635—Carbides
    • 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
    • C23C14/0664—Carbonitrides
    • 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
    • C23C14/067—Borides
    • 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
    • C23C14/08—Oxides
    • 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
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • C23C14/325—Electric arc evaporation

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Abstract

The invention provides a multilayer hard coating structure for prolonging the fatigue life of a metal member and a preparation method thereof. The coating structure comprises a nano multi-layer hard coating and at least one single-layer hard coating, wherein the nano multi-layer hard coating and the at least one single-layer hard coating are overlapped on the surface of the metal component. The multilayer hard coating structure introduces more hard coating interfaces, can effectively deflect fatigue microcracks expanded by the metal component under a low stress level and effectively inhibit the initiation and expansion of microcracks in the hard coating under a high stress level, thereby remarkably improving the fatigue life of the metal component and promoting the application of the hard coating in an alternating load service environment.

Description

Multilayer hard coating structure for improving fatigue life of hard coating and preparation method thereof
Technical Field
The invention relates to a hard coating technology, in particular to a multilayer coating structure for improving the fatigue life of a hard coating and a preparation method thereof.
Background
With the continuous appearance of new materials for key parts of machinery and the improvement of tolerance requirements of the new materials in a severe service environment, the hard coating is considered to be the most convenient and most efficient surface strengthening measure for improving the performances of friction resistance, corrosion resistance, high-temperature oxidation resistance and the like of main parts of machinery due to higher hardness and stable physicochemical properties. However, there is a phenomenon that there is a mismatch between physical properties such as a hard coating lattice, a microstructure, an elastic modulus, and the like, and a soft component base, thereby causing deterioration of fatigue strength and reduction of service reliability of the component.
Aiming at the problem, the traditional method is to carry out corresponding improvement research on the preparation process and the device of the hard coating, such as changing the matrix bias voltage from direct current to pulse, the generated compact columnar crystals can effectively delay the crack propagation speed and improve the fatigue life of the hard coating; for another example, a magnetic filter device is introduced in the cathodic arc ion plating, so that the number of large particles of the hard coating is reduced, the stress concentration points on the surface of the hard coating are reduced, and the purpose of improving the fatigue life of the hard coating is achieved. However, in view of the limitations of intrinsic defects of coating preparation technology, it is difficult to achieve significant improvements in fatigue life of hard coatings by conventional methods.
In recent years, some research and improvement work is done on the structural design of hard coatings. If a soft coating with proper thickness is introduced into the hard coating or the thickness ratio of the hard coating to the soft coating is regulated, the toughness of the hard coating is improved, the concentrated stress at the crack tip of the hard coating is relaxed, the propagation and the expansion of quick cracks are inhibited, and the purpose of further improving the fatigue life of the hard coating is achieved.
Although the soft-hard alternating multilayer coating system improves the toughness and the fatigue life of the soft coating system through the introduction of the soft coating, the strength of the coating system is easily reduced, and the capability of the hard coating for resisting external deformation is reduced.
Disclosure of Invention
The invention aims to provide a multilayer hard coating structure for prolonging the fatigue life of a hard coating and a preparation method thereof, so as to prolong the fatigue life of the hard coating and serve the practical working condition application of mechanical parts.
In order to achieve the above object, the present invention provides a multi-layered hard coating structure for improving fatigue life of a metal member, the coating structure comprising a nano multi-layered hard coating and at least one single-layered hard coating, the nano multi-layered hard coating and the at least one single-layered hard coating being stacked on a surface of the metal member.
Preferably, adjacent hard coatings in the nano multilayer hard coating are composed of different elements or elements with the same kind and different content.
Preferably, the nano-multilayer hard coating comprises one or more of carbide, boride, nitride, oxide and carbonitride; the single-layer hard coating comprises one or two of carbide, boride, nitride, oxide and carbonitride; the thickness of each layer in the nano multilayer hard coating is 0-1000 nm, especially not less than 2nm.
Preferably, a single-layer nitride hard coating, two nitride nano hard coatings of the same type and different content, two nitride nano hard coatings of the same composition and different thickness as the two nitride nano hard coatings, and a single-layer carbonitride hard coating are stacked in this order on the surface of the base body of the metal member from inside to outside.
Preferably, the multi-layer hard coating structure further comprises a transition coating connected with the metal component, wherein the transition coating can be a pure metal simple substance or one or more of carbide, boride, nitride, oxide and carbonitride.
On the other hand, the invention also provides a preparation method of the multilayer coating for improving the fatigue life of the metal component, which comprises the following steps: (1) Pretreating a substrate to obtain a clean substrate surface; (2) According to the composition of the multi-layer coating elements, selecting a target material and a gas source, adopting a cathodic arc method, adjusting the rotation axis number of a sample rotating frame, the target material current and the substrate bias voltage, and preparing a stacked multi-layer hard coating structure, namely a nano multi-layer hard coating and at least one single-layer hard coating, on the surface of the sample substrate.
Preferably, the multilayer coating layer comprises a nitride hard coating layer, four nano hard coating layers and a carbonitride hard coating layer from inside to outside in sequence relative to the surface of the metal component; in the step (2), after the substrate is placed in the rotating frame, starting the rotation axis number, wherein the rotation axis number is 1-3, closing the vacuum cavity, and after the required vacuum degree is reached, starting the heating pipe to ensure that the vacuum temperature is preferably increased to 430-450 ℃; removing an oxide film on the surface of the substrate by utilizing argon ion glow cleaning, wherein the technological parameters are as follows: the temperature is 430-450 ℃, the working pressure of argon is 1-1.5 Pa, the bias voltage is 1000V, and the cleaning time is 30-60 min; coarsening the surface of the substrate by utilizing metal ion etching, and carrying out technological parameters: the temperature is 430-450 ℃, the substrate bias voltage is-500V to-600V, and the etching time is 2-3 min; selecting a target material based on the element types in the nitride hard coating, taking nitrogen as working gas, and taking a direct current power supply as an arc source, wherein the process conditions comprise: the temperature is 430-450 ℃, the target arc flow is 160-170A, the working air pressure is 1 Pa-1.5 Pa, and the bias voltage is-80V to-120V; selecting a target material based on element types in a four-layer nano hard coating structure, taking nitrogen as working gas, taking a direct current power supply as an arc source, and preparing on the nitride hard coating, wherein the process conditions comprise: the temperature is 430-450 ℃, and the arc flow is 80-140A; the thicknesses of the first layer and the second layer of nanometer hard coating from inside to outside are 50 nm-70 nm, and the thicknesses of the third layer and the fourth layer of nanometer hard coating are 500 nm-550 nm and 250 nm-300 nm respectively in sequence; selecting a target material based on the element types in the carbonitride hard coating, taking nitrogen and acetylene as working gases and a direct current power supply as an arc source, depositing on the four-layer nano hard coating, wherein the process conditions comprise: the temperature is 430-450 ℃, the target arc flow is 150-160A, the working air pressure is 0.5-1 Pa, the partial pressure ratio of nitrogen to acetylene is 0.07-0.2, and the bias voltage is-100V to-140V.
Preferably, the metal member is a TC6 blade, and the substrate pretreatment in the step (1) includes: grinding and polishing: sequentially polishing TC6 blade matrixes by using 400-mesh, 800-mesh, 1200-mesh, 1500-mesh and 2500-mesh SiC sand paper, and polishing the surfaces of the TC6 blade matrixes by using diamond grinding paste with the particle size of 1.5 mu m; acid washing and alkali washing: then sequentially applying an acidic and alkaline cleaning agent to remove oil and oxide on the surface of the blade without changing the acidity and alkalinity of the surface of the matrix; ultrasonic cleaning with ethanol; vacuumizing; argon ion glow cleaning; etching metal Ti ions; and said step (2) comprises: depositing a TiN layer; depositing four layers (Ti, al) of N nanostructures: taking two targets of a metal Ti target and a Ti3Al1 target as targets and nitrogen as working gas, and depositing a (Ti, al) N first nano sub-layer on the TiN layer; then exchanging arc flows of the two targets, depositing a (Ti, al) N second nano-sublayer, thus forming a minimum period in the (Ti, al) N nano-structure multilayer, repeating, and finally forming the (Ti, al) N nano-structure multilayer; and depositing a TiCN layer, namely depositing on the (Ti, al) N nano-structure multilayer by taking metal Ti as a target material.
Preferably, the substrate pretreatment in the step (1) includes: grinding and polishing: sequentially polishing TC6 blade matrixes by using 400-mesh, 800-mesh, 1200-mesh, 1500-mesh and 2500-mesh SiC sand paper, and polishing the surfaces of the TC6 blade matrixes by using diamond grinding paste with the particle size of 1.5 mu m; acid washing and alkali washing: then sequentially applying an acidic and alkaline cleaning agent to remove oil and oxide on the surface of the blade without changing the acidity and alkalinity of the surface of the matrix; ultrasonic cleaning with ethanol; vacuumizing: placing TC6 blades on a rotating frame, starting the number of rotating shafts, adjusting the number of the rotating shafts to 1-3, closing the vacuum cavity, and opening a heating pipe to 450 ℃ when the vacuum degree reaches 1X 10-3 Pa; argon ion glow cleaning: the temperature is 450 ℃, the working pressure of argon is 1Pa, the bias voltage is 1000V, and the cleaning time is 40min; metal Ti ion etching: the temperature is 450 ℃, the nitrogen pressure is 1Pa, the substrate bias voltage is-500V, and the etching time is 2min.
Preferably, the step (2) includes: depositing a TiN layer: taking metal Ti as a target material, taking nitrogen as working gas, wherein the temperature is 450 ℃, the arc flow is 150A, the working air pressure is 1Pa, and the bias voltage is-100V; depositing four layers (Ti, al) of N nanostructures: taking two targets of a metal Ti target and a Ti3Al1 target as targets, taking nitrogen as working gas, and depositing a (Ti, al) N first nano-layer with the thickness of 55nm on a TiN layer at the temperature of 450 ℃ at the Ti target arc flow 80A and the Ti1Al3 target arc flow 160A; then exchanging arc flows of the two targets, depositing a (Ti, al) N second nano-sublayer with the thickness of 55nm, thus forming a minimum period in the (Ti, al) N nano-structure multilayer, and repeating 9 periods; the thickness of the first nanometer sub-layer in the last period is 500nm, the thickness of the other nanometer sub-layer is 250nm, and finally the (Ti, al) N nanometer structure multilayer is formed; and depositing a TiCN layer, wherein metal Ti is used as a target material, nitrogen and acetylene are used as working gases, a direct current power supply is used as an arc source, the TiCN layer is deposited on the (Ti, al) N nano-structure multilayer, and the process conditions comprise: the temperature is 450 ℃, the target arc flow 160A, the working pressure is 0.8Pa, and the partial pressure ratio of acetylene and nitrogen PC2H2:PN2 is gradually increased from 0.07 to 0.2; bias-100V.
Preferably, the step (2) includes: depositing a TiN layer: taking metal Ti as a target material, taking nitrogen as working gas, wherein the temperature is 450 ℃, the arc flow is 150A, the working air pressure is 1Pa, and the bias voltage is-100V; depositing four layers (Ti, al) of N nanostructures: taking two targets of a metal Ti target and a Ti3Al1 target as targets, taking nitrogen as working gas, and depositing a (Ti, al) N first nano-layer with the thickness of 65nm on a TiN layer at the temperature of 450 ℃ at the Ti target arc flow 80A and the Ti1Al3 target arc flow 160A; then exchanging arc flow of the two targets, depositing a (Ti, al) N second nano-sublayer with the thickness of 65nm, thus forming a minimum period in the (Ti, al) N nano-structure multilayer, repeating 9 periods, wherein the thickness of the first nano-sublayer in the last period is 500nm, and the thickness of the other nano-sublayer is 250nm, and finally forming the (Ti, al) N nano-structure multilayer; and depositing a TiCN layer, wherein metal Ti is used as a target material, nitrogen and acetylene are used as working gases, a direct current power supply is used as an arc source, the TiCN layer is deposited on the (Ti, al) N nano-structure multilayer, and the process conditions comprise: the temperature is 450 ℃, the target arc flow 160A, the working pressure is 0.8Pa, and the partial pressure ratio of acetylene and nitrogen PC2H2:PN2 is gradually increased from 0.07 to 0.2; bias-100V.
In the present invention, the coating layer may be formed by stacking any combination of nano multi-layered hard coating layers and single-layered hard coating layers.
Preferably, the nano-multilayer hard coating has a hardness of each layer of coating greater than the hardness of the metal component.
The method of the present invention may further comprise the steps of:
(3) After the nano multilayer coating is prepared, when the temperature of the vacuum chamber is reduced to 80 ℃, the molecular pump and the mechanical pump are gradually closed, the air inlet valve is opened, and the sample is taken out.
The invention has the following effects and benefits:
compared with the existing multilayer technology for improving the fatigue life of the hard coating, the invention introduces the hard coating with nanometer thickness into the multilayer hard coating through the design thinking of combining the nanometer structure and the multilayer structure, increases the internal interface and crystal face of the coating, improves the toughness of the hard coating, increases the radial expansion resistance of cracks in the hard coating, deflects the radial crack expansion direction of the cracks, and obviously improves the fatigue life of the hard coating. Meanwhile, the invention increases the internal interface and crystal face of the coating, thereby effectively enhancing the strength of the coating. Namely, the multilayer hard coating structure designed by the invention can not only improve the fatigue life of the hard coating, but also enhance the hardness of the coating. The preparation method of the multilayer hard coating has simple process and strong industrial operability, and can easily realize uniform coating preparation on different components.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly described below, and it is apparent that the drawings in the description below are only used to explain the concept of the present invention.
FIG. 1 is a schematic cross-sectional microstructure of one example of a multilayer hard coating structure of the present invention;
fig. 2 is a process flow diagram corresponding to the method of the present invention.
Detailed Description
For a clearer understanding of the above objects, features and advantages of the present invention, the present invention will be described in further detail with reference to the accompanying drawings and examples.
The embodiments described herein are specific embodiments of the present invention, which are intended to be illustrative and exemplary of the inventive concept, and should not be construed as limiting the scope of the invention and embodiments of the invention. In addition to the embodiments described herein, those skilled in the art can adopt other obvious solutions based on the disclosure of the claims and specification of the present application, including those adopting any obvious substitutions and modifications to the embodiments described herein.
The drawings in the present specification are schematic views, which assist in explaining the concept of the present invention, and schematically show the shapes of the respective parts and their interrelationships.
A schematic cross-sectional microstructure of the multilayer hard coating of the invention is shown in FIG. 1, and comprises a matrix material 1, a single-layer hard coating 2, a nano multilayer hard coating 7 and a single-layer hard coating 8. The nano multilayer hard coating 7 is formed by circularly arranging nitride hard coatings with the same nano thickness and different contents, and specifically comprises the following components: firstly, nitride hard coatings 3 and 4 with the same types and different contents are sequentially arranged, and finally nitride hard coatings 5 and 6 with the same components as the nitride hard coatings 3 and 4 and different thicknesses are respectively prepared. The single-layer hard coat layer 2 and the single-layer hard coat layer 8 are nitride and carbonitride, respectively.
The nitrogen-containing single-layer hard coat layer 2 is located on the metal member, the nano-multilayer hard coat layer 7 is located between the nitride 2 and the carbonitride 8, and the carbonitride 8 is a surface layer structure of the multilayer hard coat layer structure.
In a preferred embodiment, the thickness of the hard coating layers 3 and 4 in the nano multi-layered hard coating layer is preferably 50nm to 70nm, more preferably 55nm to 65nm.
In a preferred embodiment, the hard coating layers 5, 6 in the nano multi-layered hard coating layer are preferably 500nm to 600nm and 200nm to 300nm in this order.
Referring again to fig. 2, in another aspect, the present invention further provides a method for preparing the above-mentioned preferred embodiment multilayer coating structure, including:
(1) Pretreating a substrate to obtain a clean substrate surface;
(2) Selecting target materials and gas sources required by preparing the multilayer coating, adjusting the rotation axis number of a substrate, the power source and bias voltage of the target materials by adopting a cathodic arc method, and sequentially preparing on the surface of the substrate: nitride 2, nano-multilayer hard coating 7 and carbonitride 8.
In the present invention, the base material is not particularly limited, and the base includes any one of stainless steel, high-speed steel, cemented carbide, and titanium alloy, and is not limited to the above base types.
According to the polishing process for the pretreatment of the matrix material, siC sand paper with the mesh number increasing gradually from 400 meshes to 2500 meshes can be used for polishing, and then diamond grinding paste with the particle size of 1.5 mu m can be used for polishing the surface of the matrix;
in the present invention, the industrial cleaning agent is not specifically limited, and conventional industrial degreasing and descaling agents are also acceptable. In the embodiment of the invention, the cleaning agents adopt acidic cleaning agents and alkaline cleaning agents in sequence, so that the acid and the alkali of the surface of the matrix are not changed while the pollutants such as surface oxides, nitrides and the like are removed.
In the invention, after the substrate is placed on the rotating frame, the number of the rotating shafts is started, and the number of the rotating shafts of the substrate is preferably 1-3. And then closing the vacuum cavity, and after the required vacuum degree is reached, opening the heating pipe to ensure that the vacuum temperature is preferably increased to 400-500 ℃, more preferably 430-450 ℃.
In the invention, the argon ion glow cleaning can remove the oxide film on the surface of the substrate, and preferable technological parameters include: the temperature is 400-500 ℃, more preferably 430-450 ℃; the working pressure of argon is 1 Pa-1.5 Pa, the bias voltage is 1000V, and the cleaning time is 30 min-60 min;
in the invention, the metal ion etching can coarsen the surface of the substrate, improve the binding force between the coating and the substrate, and process parameters are as follows: the temperature is preferably 400-500 ℃, more preferably 430-450 ℃, the substrate bias is-500V-600V, and the etching time is 2-5 min, more preferably 2-3 min.
In the invention, the nitride hard coating 2 is deposited on the substrate 1 by taking the element types in the nitride hard coating 2 as the basis, selecting a target material, taking nitrogen as working gas and taking a direct current power supply as an arc source. Preferred process conditions include: the temperature is 400-500 ℃, more preferably 430-450 ℃; target arc flow 140A-180A, more preferably 160A-170A; the working air pressure is 1 Pa-1.5 Pa; bias voltage is-80V to-120V.
In the invention, the nano multilayer hard coating 7 is prepared in the nitride hard coating 2 by taking element types in a nano multilayer hard coating structure as a basis, selecting a target material, taking nitrogen as working gas and taking a direct current power supply as an arc source. Preferred process conditions include: the temperature is 400-500 ℃, more preferably 430-450 ℃; arc flow 80A-180A, more preferably 80A-140A; the thicknesses of the single-layer hard coatings 3 and 4 before the last two layers of the nano multilayer hard coatings are 50 nm-70 nm; the thicknesses of the last two layers of coatings are 500 nm-600 nm and 200 nm-300 nm in sequence, and the most preferable thicknesses are respectively: 500nm to 550nm and 250nm to 300nm.
In the invention, the carbonitride surface layer 8 is deposited on the nano multilayer coating structure 7 by selecting a target material based on the element types in the carbonitride surface layer 8, using nitrogen and acetylene as working gases and using a direct current power supply as an arc source. Preferred process conditions include: the temperature is 400-500 ℃, more preferably 430-450 ℃; the target arc flow 140A-180A, more preferably 150A-160A; the working air pressure is 0.5 Pa-1 Pa; the partial pressure ratio of the nitrogen to the acetylene is 0.07-0.2; bias voltage is-100V to-140V.
In the invention, after the preparation of the nano multilayer coating is completed, when the temperature of the vacuum chamber is reduced to 80 ℃, the molecular pump and the mechanical pump are gradually closed, the air inlet valve is opened, and the sample is taken out.
The present invention provides a nano multi-layer coating for improving fatigue life of a hard coating and a preparation method thereof, which are described in detail below with reference to examples, but the present invention is not limited to the scope of the present invention.
Example 1: the implementation is a TiAlCN multilayer hard coating structure for prolonging the fatigue life of TC6 blades and a preparation method under single-axis rotation, and the preparation method comprises the following steps:
pretreatment of a matrix:
grinding and polishing: sequentially polishing TC6 blade matrixes by using 400-mesh, 800-mesh, 1200-mesh, 1500-mesh and 2500-mesh SiC sand paper, and polishing the surfaces of the TC6 blade matrixes by using diamond grinding paste with the particle size of 1.5 mu m;
acid washing and alkali washing: then sequentially applying an acidic and alkaline cleaning agent to remove oil and oxide on the surface of the blade without changing the acidity and alkalinity of the surface of the matrix;
ultrasonic cleaning with ethanol: ultrasonic cleaning is carried out in ethanol solvent for 15min.
Vacuumizing: the TC6 blades are placed on the rotating frame, the rotating shaft number is started, and the rotating shaft number is adjusted to be 1. Closing the vacuum cavity, and opening the heating pipe to 450 ℃ when the vacuum degree reaches 1X 10-3 Pa.
Argon ion glow cleaning: the temperature is 450 ℃, the working pressure of argon is 1Pa, the bias voltage is 1000V, and the cleaning time is 40min;
metal Ti ion etching: the temperature is 450 ℃, the nitrogen pressure is 1Pa, the substrate bias voltage is-500V, and the etching time is 2min.
Depositing a TiAlCN nano multilayer coating structure on a substrate:
and (3) depositing the TiN layer: the metal Ti is used as a target material, nitrogen is used as working gas, the temperature is 450 ℃, the arc flow is 150A, the working air pressure is 1Pa, and the bias voltage is-100V.
Deposition of the (Ti, al) N nanostructure multilayer process: taking two targets of a metal Ti target and a Ti3Al1 target as targets, taking nitrogen as working gas, and depositing a (Ti, al) N first nano-layer with the thickness of 55nm on a TiN layer at the temperature of 450 ℃ at the Ti target arc flow 80A and the Ti1Al3 target arc flow 160A; then exchanging the arc flow of the two targets, depositing a second (Ti, al) N nano-sublayer with the thickness of 55nm, thus forming the minimum period in the (Ti, al) N nano-structure multilayer, and repeating 9 periods. The thickness of the first nanometer sub-layer in the last period is 500nm, the thickness of the other nanometer sub-layer is 250nm, and finally the (Ti, al) N nanometer structure multilayer is formed.
And depositing the TiCN layer, namely depositing on the (Ti, al) N nano-structure multilayer by taking metal Ti as a target material and taking nitrogen and acetylene as working gases and taking a direct current power supply as an arc source. The process conditions include: the temperature is 450 ℃, the target arc flow 160A, the working pressure is 0.8Pa, and the partial pressure ratio of acetylene and nitrogen PC2H2:PN2 is gradually increased from 0.07 to 0.2; bias-100V.
(3) After the TiAlCN nano multilayer coating is prepared, when the temperature of the vacuum chamber is reduced to 80 ℃, the molecular pump and the mechanical pump are gradually closed, the air inlet valve is opened, and the TC6 blade is taken out.
And on the vibration fatigue test platform, the fatigue life of the TC6 blade plated with the TiAlCN nano multilayer coating is improved by 61.9% relative to the substrate when the maximum stress value sigma max=500 MPa is applied.
Example 2: the implementation is a TiAlCN multilayer hard coating structure for prolonging the fatigue life of TC6 blades and a preparation method under triaxial rotation, and the preparation method comprises the following steps:
the present example differs from the embodiment of example 1 in the point that step (1) d, specifically:
pretreatment of a matrix:
vacuumizing: the TC6 blades are placed on the rotating frame, the rotating shaft number is started, and the rotating shaft number is adjusted to 3. Closing the vacuum cavity, and opening the heating pipe to 450 ℃ when the vacuum degree reaches 1X 10-3 Pa.
And on the vibration fatigue test platform, the fatigue life of the TC6 blade plated with the TiAlCN nano multilayer coating is improved by 39 times relative to the substrate by applying the maximum stress value sigma max=500 MPa.
Example 3: the example is a TiAlCN multilayer hard coating structure for prolonging the fatigue life of a stainless steel blade and a preparation method under triaxial rotation, and the preparation method comprises the following steps:
the embodiment differs from the embodiment of example 2 in step (2) b, specifically:
depositing a TiAlCN nano multilayer coating structure on a substrate:
deposition of the (Ti, al) N nanostructure multilayer process: taking two targets of a metal Ti target and a Ti3Al1 target as targets, taking nitrogen as working gas, and depositing a (Ti, al) N first nano-layer with the thickness of 65nm on a TiN layer at the temperature of 450 ℃ at the Ti target arc flow 80A and the Ti1Al3 target arc flow 160A; then exchanging the arc flow of the two targets, depositing a (Ti, al) N second nano-sublayer with the thickness of 65nm, thus forming the minimum period in the (Ti, al) N nano-structure multilayer, and repeating 9 periods. The thickness of the first nanometer sub-layer in the last period is 500nm, the thickness of the other nanometer sub-layer is 250nm, and finally the (Ti, al) N nanometer structure multilayer is formed.
The multilayer hard coating structure introduces more hard coating interfaces, can effectively deflect fatigue microcracks expanded by the metal component under a low stress level and effectively inhibit the initiation and expansion of microcracks in the hard coating under a high stress level, thereby remarkably improving the fatigue life of the metal component and promoting the application of the hard coating in an alternating load service environment.
The embodiments of a multilayer hard coating structure for improving fatigue life of a hard coating and a method of manufacturing the same according to the present invention are described above for the purpose of explaining the spirit of the present invention. Specific features of the inventive concept may be devised in accordance with the effects of the features disclosed above, all of which are within the reach of a person skilled in the art. Moreover, the above disclosed features are not limited to the disclosed combinations with other features, and other combinations between features may be made by those skilled in the art in accordance with the purpose of the present invention to achieve the purpose of the present invention.

Claims (10)

1. A multilayer hard coating structure for improving the fatigue life of a metal member, characterized in that the coating structure comprises a nano multilayer hard coating and at least one single-layer hard coating, and the nano multilayer hard coating and the at least one single-layer hard coating are superposed on the surface of the metal member.
2. The multilayer hard coating structure according to claim 1, wherein adjacent hard coatings in the nano multilayer hard coating are composed of different elements or are composed of elements of the same kind and different contents.
3. The multilayer hard coating structure according to claim 1, wherein the nano-multilayer hard coating comprises one or more of carbide, boride, nitride, oxide, and carbonitride;
the single-layer hard coating comprises one or two of carbide, boride, nitride, oxide and carbonitride;
the thickness of each layer in the nano multilayer hard coating is 0-1000 nm, especially not less than 2nm.
4. The multilayer hard coating structure according to claim 1, wherein a single layer nitride hard coating, two nitride nanohard coatings of the same kind and different content, two nitride nanohard coatings of the same composition and different thickness as the aforementioned two nitride nanohard coatings, and a single layer carbonitride hard coating are stacked in this order from inside to outside on the substrate surface of the metal member.
5. The multilayer hard coating structure according to any one of claims 1 to 4, further comprising a transition coating layer connected to the metal member, the transition coating layer being a pure metal simple substance or one or more of carbide, boride, nitride, oxide, carbonitride.
6. A preparation method of a multilayer coating for improving the fatigue life of a metal member comprises the following steps:
(1) Pretreating a substrate to obtain a clean substrate surface;
(2) According to the composition of the multi-layer coating elements, selecting a target material and a gas source, adopting a cathodic arc method, adjusting the rotation axis number of a sample rotating frame, the target material current and the substrate bias voltage, and preparing a stacked multi-layer hard coating structure, namely a nano multi-layer hard coating and at least one single-layer hard coating, on the surface of the sample substrate.
7. The method according to claim 6, wherein the multilayer coating layer comprises one layer of nitride hard coating layer, four layers of nano hard coating layer, and one layer of carbonitride hard coating layer in this order from the inside to the outside with respect to the surface of the metal member;
in the step (2), after the substrate is placed in the rotating frame, starting the rotation axis number, wherein the rotation axis number is 1-3, closing the vacuum cavity, and after the required vacuum degree is reached, starting the heating pipe to ensure that the vacuum temperature is preferably increased to 430-450 ℃;
removing an oxide film on the surface of the substrate by utilizing argon ion glow cleaning, wherein the technological parameters are as follows: the temperature is 430-450 ℃, the working pressure of argon is 1-1.5 Pa, the bias voltage is 1000V, and the cleaning time is 30-60 min;
coarsening the surface of the substrate by utilizing metal ion etching, and carrying out technological parameters: the temperature is 430-450 ℃, the substrate bias voltage is-500V to-600V, and the etching time is 2-3 min;
selecting a target material based on the element types in the nitride hard coating, taking nitrogen as working gas, and taking a direct current power supply as an arc source, wherein the process conditions comprise: the temperature is 430-450 ℃, the target arc flow is 160-170A, the working air pressure is 1 Pa-1.5 Pa, and the bias voltage is-80V to-120V;
selecting a target material based on element types in a four-layer nano hard coating structure, taking nitrogen as working gas, taking a direct current power supply as an arc source, and preparing on the nitride hard coating, wherein the process conditions comprise: the temperature is 430-450 ℃, and the arc flow is 80-140A; the thicknesses of the first layer and the second layer of nanometer hard coating from inside to outside are 50 nm-70 nm, and the thicknesses of the third layer and the fourth layer of nanometer hard coating are 500 nm-550 nm and 250 nm-300 nm respectively in sequence;
selecting a target material based on the element types in the carbonitride hard coating, taking nitrogen and acetylene as working gases and a direct current power supply as an arc source, depositing on the four-layer nano hard coating, wherein the process conditions comprise: the temperature is 430-450 ℃, the target arc flow is 150-160A, the working air pressure is 0.5-1 Pa, the partial pressure ratio of nitrogen to acetylene is 0.07-0.2, and the bias voltage is-100V to-140V.
8. The method of manufacturing according to claim 6, wherein the metal member is a TC6 blade, and
the substrate pretreatment in the step (1) comprises the following steps:
a. grinding and polishing: sequentially polishing TC6 blade matrixes by using 400-mesh, 800-mesh, 1200-mesh, 1500-mesh and 2500-mesh SiC sand paper, and polishing the surfaces of the TC6 blade matrixes by using diamond grinding paste with the particle size of 1.5 mu m;
b. acid washing and alkali washing: then sequentially applying an acidic and alkaline cleaning agent to remove oil and oxide on the surface of the blade without changing the acidity and alkalinity of the surface of the matrix;
c. ultrasonic cleaning with ethanol;
d. vacuumizing;
e. argon ion glow cleaning;
f. etching metal Ti ions; and is also provided with
The step (2) comprises:
a. depositing a TiN layer;
b. depositing four layers (Ti, al) of N nanostructures: with metallic Ti target material and Ti 3 Al 1 Target material two targets are target material, nitrogen gas is working gas, and in TiN layerDepositing a (Ti, al) N first nano-layer; then exchanging arc flows of the two targets, depositing a (Ti, al) N second nano-sublayer, thus forming a minimum period in the (Ti, al) N nano-structure multilayer, repeating, and finally forming the (Ti, al) N nano-structure multilayer;
c. and depositing a TiCN layer, namely depositing on the (Ti, al) N nano-structure multilayer by taking metal Ti as a target material.
9. The method according to claim 8, wherein,
the step (2) comprises:
a. depositing a TiN layer: taking metal Ti as a target material, taking nitrogen as working gas, wherein the temperature is 450 ℃, the arc flow is 150A, the working air pressure is 1Pa, and the bias voltage is-100V;
b. depositing four layers (Ti, al) of N nanostructures: with metallic Ti target material and Ti 3 Al 1 Target material two targets are target material, nitrogen gas is working gas, temperature is 450 ℃, first in Ti target arc flow 80A, ti 1 Al 3 A target arc flow 160A, depositing a (Ti, al) N first nanosublayer with a thickness of 55nm on the TiN layer; then exchanging arc flows of the two targets, depositing a (Ti, al) N second nano-sublayer with the thickness of 55nm, thus forming a minimum period in the (Ti, al) N nano-structure multilayer, and repeating 9 periods; the thickness of the first nanometer sub-layer in the last period is 500nm, the thickness of the other nanometer sub-layer is 250nm, and finally the (Ti, al) N nanometer structure multilayer is formed;
c. and depositing a TiCN layer, wherein metal Ti is used as a target material, nitrogen and acetylene are used as working gases, a direct current power supply is used as an arc source, the TiCN layer is deposited on the (Ti, al) N nano-structure multilayer, and the process conditions comprise: the temperature is 450 ℃, the target arc flow is 160A, the working pressure is 0.8Pa, and the partial pressure ratio P of acetylene and nitrogen is C2H2 :P N2 Gradually increasing from 0.07 to 0.2; bias-100V.
10. The method according to claim 8, wherein,
the step (2) comprises:
a. depositing a TiN layer: taking metal Ti as a target material, taking nitrogen as working gas, wherein the temperature is 450 ℃, the arc flow is 150A, the working air pressure is 1Pa, and the bias voltage is-100V;
b. depositing four layers (Ti, al) of N nanostructures: taking two targets of a metal Ti target and a Ti3Al1 target as targets, taking nitrogen as working gas, and depositing a (Ti, al) N first nano-layer with the thickness of 65nm on a TiN layer at the temperature of 450 ℃ at the Ti target arc flow 80A and the Ti1Al3 target arc flow 160A; then exchanging arc flow of the two targets, depositing a (Ti, al) N second nano-sublayer with the thickness of 65nm, thus forming a minimum period in the (Ti, al) N nano-structure multilayer, repeating 9 periods, wherein the thickness of the first nano-sublayer in the last period is 500nm, and the thickness of the other nano-sublayer is 250nm, and finally forming the (Ti, al) N nano-structure multilayer;
c. and depositing a TiCN layer, wherein metal Ti is used as a target material, nitrogen and acetylene are used as working gases, a direct current power supply is used as an arc source, the TiCN layer is deposited on the (Ti, al) N nano-structure multilayer, and the process conditions comprise: the temperature is 450 ℃, the target arc flow is 160A, the working pressure is 0.8Pa, and the partial pressure ratio P of acetylene and nitrogen is C2H2 :P N2 Gradually increasing from 0.07 to 0.2; bias-100V.
CN202310234795.1A 2023-03-13 2023-03-13 Multilayer hard coating structure for improving fatigue life of hard coating and preparation method thereof Pending CN116356254A (en)

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