Method for remarkably improving bonding strength of high-temperature interface of ceramic coating

Abstract

The invention provides a method for remarkably improving the high-temperature interface bonding strength of a ceramic coating, and relates to the technical field of ceramic coatings. The method for remarkably improving the high-temperature interface bonding strength of the ceramic coating comprises the steps of substrate surface cleaning, magnetron sputtering preparation of a transition layer and magnetron sputtering preparation of the ceramic coating. The Ti transition layer is firstly deposited on the substrate, the thickness of the Ti transition layer is increased, smooth transition of the ceramic coating and the metal matrix is ensured, meanwhile, the deposition temperature, the sputtering rate and the thickness of the Ti transition layer in the magnetron sputtering process are regulated and controlled, internal stress is reduced, and formation of an interface amorphous thin layer is avoided; the high-temperature and high-bonding-strength ceramic coating is prepared, and it is avoided that an interface is partially crystallized in a high-temperature environment to form a disordered amorphous-nanocrystalline structure, and the interface is embrittled.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ceramic coating, in particular to a method for significantly improving the high-temperature interface bonding strength of ceramic coating. BACKGROUND

[0002] In the modern industrial manufacturing system, metal materials have become the basic materials in many key fields due to their excellent mechanical properties and processability. However, metal materials are prone to wear, corrosion and other problems in complex and variable service environments, such as high temperature, high humidity, strong corrosive medium and high friction, which not only greatly shortens the service life of metal parts, but also may cause safety hazards.

[0003] As a new type of surface protective coating, ceramic material coating has many advantages such as high hardness, good chemical stability, excellent wear resistance and low friction coefficient. Coating on the metal surface can significantly improve the comprehensive performance of the metal, and has broad application prospects in mechanical processing, mold manufacturing, aerospace and electronic information industries. Although ceramic coating has obvious advantages, the coating prepared by the current mainstream method of plating ceramic material on the metal surface has many problems to be solved in the bonding force with the metal matrix.

[0004] The defects of the existing method of plating ceramic coating on the metal surface in the bonding force lead to the problems of peeling and cracking of the coating in actual application, which seriously limits the performance of ceramic material coating and the expansion of application range.

[0005] Therefore, it is of great practical significance and broad market prospect to develop a method for significantly improving the bonding force of ceramic material coating and metal matrix. SUMMARY

[0006] In order to solve the technical problems of poor bonding force between metal matrix and ceramic coating, peeling, cracking and other problems in actual application in the prior art, the present application provides a method for significantly improving the high-temperature interface bonding strength of ceramic coating. The technical solution is as follows:

[0007] A method for significantly improving the high-temperature interface bonding strength of ceramic coating, the method for significantly improving the high-temperature interface bonding strength of ceramic coating comprises substrate surface cleaning, transition layer magnetron sputtering preparation and ceramic coating magnetron sputtering preparation, and the specific process is as follows:

[0008] S1, substrate surface cleaning: heat the metal matrix and place it in a vacuum sputtering coating machine, adjust the vacuum degree, then fill argon, start the substrate bias to clean the ion source surface, and get the cleaned metal matrix;

[0009] S2, magnetron sputtering preparation of the transition layer: the metal substrate of S1 is selected with transition layer material metal Ti, argon is introduced, the power of the Ti target is adjusted, the transition layer Ti is deposited on the surface of the metal substrate of S1 by using the magnetron sputtering technology, and the metal substrate covered with the transition layer Ti is obtained;

[0010] S3, magnetron sputtering preparation of the ceramic coating: argon and nitrogen are introduced, the substrate bias is set, the target corresponding to the ceramic coating is turned on, the ceramic coating is deposited on the surface of the metal substrate covered with the transition layer, and the ceramic coating-transition layer-metal substrate is obtained after cooling.

[0011] Optionally, the heating temperature of the metal substrate in S1 is 500 DEG C; the substrate bias in S1 is turned on to -1000 V to -600 V; and the cleaning time in S1 is 5-15 min.

[0012] Optionally, the argon flow introduced in S2 is 15-20 sccm; the power of the Ti target in S2 is 100-300 W; the temperature when the transition layer Ti is deposited in S2 is 450-550 DEG C; and the thickness of the transition layer Ti after deposition in S2 is 100-150 nm.

[0013] Optionally, the nitrogen flow in S3 is 2-4 sccm; and the substrate bias set in S3 is -140 V to -80 V.

[0014] Optionally, the ceramic coating deposited in S3 is a TiBN ceramic coating.

[0015] Optionally, the ceramic coating deposited in S3 is a TiSiNAlCrY ceramic coating.

[0016] Optionally, the target corresponding to the TiBN ceramic coating is a TiB2 target and a Ti target, wherein the power of the TiB2 target is 20-40 W, the power of the Ti target is 150-250 W; the TiBN deposition time is 3-5 h; and the temperature when the TiBN is deposited is 450-550 DEG C.

[0017] Optionally, the target corresponding to the TiSiNAlCrY ceramic coating is an AlCrY target, a Ti target and a TiSi target, wherein the power of the AlCrY target is 100-200 W, the power of the Ti target is 150-250 W, and the power of the TiSi target is 20-40 W; the TiSiNAlCrY deposition time is 3-5 h; and the temperature when the TiSiNAlCrY is deposited is 450-550 DEG C.

[0018] The technical principle of the application is as follows:

[0019] The metal substrate surface is preheated by ion beam bombardment in a vacuum environment, nanoscale concave-convex structures, oxide layer and contaminants are formed by physical sputtering of high-energy ions, the metal surface atoms are activated to be in a high active state to increase the surface roughness and chemical activity, the first principle calculation is used to screen Ti as a transition layer, the Ti transition layer is deposited on the metal substrate surface by magnetron sputtering technology, the interface thermal stress is buffered by the characteristic that the thermal expansion coefficient of the Ti transition layer is between the metal substrate and the ceramic coating, and the atomic level intermingling metallurgical bonding is formed by high temperature diffusion and the substrate; when the ceramic coating is deposited, the atomic diffusion is enhanced, the lattice distortion is reduced, the sputtering rate is slowed down, and the dynamic stress accumulation is reduced by increasing the deposition temperature, so that the amorphous layer is avoided to be formed at the interface due to the 'quenching' effect in the early stage of coating deposition, the heat stress transmission path is prolonged by adjusting the thickness of the transition layer, the internal stress of the coating is reduced in multiple dimensions, the strong chemical bonding is formed by using the metal bond of the activated surface and the transition layer, the covalent bond of the transition layer and the coating, the high-temperature interface bonding strength of the ceramic coating and the metal substrate is significantly improved by combining the mechanical interlocking effect of the rough surface and the coating.

[0020] Compared with the prior art, the technical scheme has at least the following beneficial effects:

[0021] The vacuum ion source surface cleaning treatment of the present application can increase the surface roughness of the metal, activate the metal surface atoms, and make them in a high-energy active state, thereby enhancing the bonding strength between the coating and the substrate; on this basis, by depositing a Ti transition layer on the metal substrate and increasing the thickness of the Ti transition layer, the heat stress transmission path can be prolonged, the interface thermal stress can be reduced, and the bonding energy of the ceramic coating can be improved at high temperature; in addition, the deposition temperature and sputtering rate of the magnetron sputtering process are regulated, the deposition atoms are given sufficient surface migration energy by increasing the deposition temperature, the deposition atoms are fully diffused and arranged in order on the surface, a good crystalline coating-substrate interface is formed, the sputtering rate is slowed down and the high-energy particle bombardment energy is reduced by reducing the target power, the dynamic stress accumulation in the coating is avoided, thereby avoiding the formation of an amorphous layer at the interface due to the 'quenching' effect in the early stage of coating deposition, avoiding the formation of an unordered amorphous-nanocrystalline structure and a brittle interface due to the crystallization of the interface at high temperature; at the same time, the deposition time is prolonged to increase the atomic rearrangement opportunity, the coating density is improved, and finally the ceramic coating and the metal substrate form a strong interface bonding. BRIEF DESCRIPTION OF DRAWINGS

[0022] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed in the embodiment description will be briefly introduced. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0023] Figure 1 Figure 1 is a TEM image of the interface of the TiBN ceramic coating-transition layer-metal substrate prepared by the method for significantly improving the high-temperature interface bonding strength of ceramic coating according to Embodiment 1 of the present application;

[0024] Figure 2 Figure 2 is a TEM image of the interface of the TiBN ceramic coating-transition layer-metal substrate prepared by Comparative Example 1 of the present application;

[0025] Figure 3 Figure 3 is a diagram showing the variation of the internal stress of the TiBN ceramic coating in the TiBN ceramic coating-transition layer-metal substrate prepared by the method for significantly improving the high-temperature interface bonding strength of ceramic coating according to Embodiment 1 and Comparative Example 1 of the present application along the growth direction of the coating;

[0026] Figure 4 Figure 4 is a diagram showing the blister morphology of the TiBN ceramic coating in the TiBN ceramic coating-transition layer-metal substrate prepared by the method for significantly improving the high-temperature interface bonding strength of ceramic coating according to Embodiment 1 of the present application after high-temperature treatment at 450°C;

[0027] Figure 5 Figure 5 is a diagram showing the blister morphology of the TiBN ceramic coating in the TiBN ceramic coating-transition layer-metal substrate prepared by Comparative Example 1 of the present application after high-temperature treatment at 450°C. DETAILED DESCRIPTION

[0028] The technical solutions in the present application will be described below with reference to the accompanying drawings.

[0029] In the embodiments of the present application, the words such as "example", "for example" are used to represent as an example, illustration or description. Any embodiment or design scheme described as "example" in the present application should not be interpreted as more preferred or more advantageous than other embodiments or design schemes. In fact, the word "example" is intended to present the concept in a specific way. In addition, in the embodiments of the present application, the meaning expressed by "and / or" can be both, or can be one of the two.

[0030] In the embodiments of the present application, "image" and "picture" can be used interchangeably at times. It should be pointed out that when the distinction is not emphasized, the meanings expressed are consistent.

[0031] In the embodiments of the present application, sometimes the subscript such as W1 can be written in the form of non-subscript such as W1. When the distinction is not emphasized, the meanings expressed are consistent.

[0032] In order to make the technical problems, technical solutions and advantages of the present application more clear, the following will be described in detail with reference to the accompanying drawings and specific embodiments.

[0033] The application discloses a method for significantly improving high-temperature interface bonding strength of a ceramic coating, and belongs to the technical field of ceramic coating preparation.

[0034] S1, surface cleaning of a substrate: after heating, the metal substrate is placed in a vacuum sputtering film coating machine, the vacuum degree is adjusted, then argon is filled, and ion source surface cleaning is performed by opening a substrate bias, so that the cleaned metal substrate is obtained.

[0035] S2, preparation of a transition layer by magnetron sputtering: transition layer material metal Ti is selected for the metal substrate in S1, argon is introduced, the power of the Ti target is adjusted, and the transition layer Ti is deposited on the surface of the metal substrate in S1 by using a magnetron sputtering technology, so that the metal substrate covered with the transition layer Ti is obtained.

[0036] S3, preparation of a ceramic coating by magnetron sputtering: argon and nitrogen are introduced, a substrate bias is set, the corresponding target of the ceramic coating is opened, the ceramic coating is deposited on the surface of the metal substrate covered with the transition layer, and after cooling, the ceramic coating-transition layer-metal substrate is obtained.

[0037] In particular, the heating temperature of the metal substrate in S1 is 500 DEG C; the substrate bias is opened to -1000 V to -600 V in S1; and the cleaning time in S1 is 5-15 min.

[0038] In particular, the argon flow introduced in S2 is 15-20 sccm; the power of the Ti target in S2 is 100-300 W; the temperature when the transition layer Ti is deposited in S2 is 450-550 DEG C; and the thickness of the deposited transition layer Ti in S2 is 100-150 nm.

[0039] In particular, the nitrogen flow in S3 is 2-4 sccm; and the substrate bias set in S3 is -140 V to -80 V.

[0040] In particular, the deposited ceramic coating in S3 is a TiBN ceramic coating.

[0041] In particular, the deposited ceramic coating in S3 is a TiSiNAlCrY ceramic coating.

[0042] In particular, the corresponding target of the TiBN ceramic coating is a TiB2 target and a Ti target, wherein the power of the TiB2 target is 20-40 W, the power of the Ti target is 150-250 W; the TiBN deposition time is 3-5 h; and the TiBN deposition temperature is 450-550 DEG C.

[0043] Specifically, the target materials corresponding to the TiSiNAlCrY ceramic coating are AlCrY target, Ti target, and TiSi target, wherein the power of AlCrY target is 100-200W, the power of Ti target is 150-250W, and the power of TiSi target is 20-40W; the deposition time of TiSiNAlCrY is 3-5h; and the deposition temperature of TiSiNAlCrY is 450-550℃.

[0044] Example 1

[0045] This embodiment provides a method for significantly improving the high-temperature interfacial bonding strength of ceramic coatings. The method includes substrate surface cleaning, magnetron sputtering preparation of a transition layer, and magnetron sputtering preparation of a TiBN ceramic coating. The specific process is as follows:

[0046] S1. Substrate surface cleaning: After heating the metal substrate, place it in a vacuum sputtering coating machine at a temperature of 500℃; adjust the vacuum level; then fill with argon gas, turn on the substrate bias voltage to -970V, and clean for 10 minutes to perform ion source surface cleaning to obtain the cleaned metal substrate.

[0047] S2. Magnetron sputtering preparation of the transition layer: Argon gas is introduced at a flow rate of 15 sccm; the target power of the Ti target is adjusted to 200W; magnetron sputtering is used to deposit a transition layer Ti on the surface of the S1 metal substrate at a temperature of 500℃ to obtain a metal substrate covered with the transition layer; the thickness of the transition layer after deposition is 130 nm.

[0048] S3. Magnetron sputtering preparation of ceramic coating: Argon and nitrogen are introduced, with a nitrogen flow rate of 2.6 sccm. The TiB2 target and Ti target are turned on, with a TiB2 target power of 30W and a Ti target power of 200W. The substrate bias voltage is set to -110V. TiBN is deposited on the surface of the metal substrate covered with the transition layer. The TiBN deposition temperature is 500℃ and the deposition time is 3h. After cooling, TiBN ceramic coating-transition layer-metal substrate is obtained.

[0049] like Figure 1 The image shown is a TEM image of the interface between the TiBN ceramic coating and the substrate obtained in Example 1. It can be seen from the image that the coating has good crystallization and good bonding with the substrate.

[0050] The TiBN ceramic coating-transition layer-metal substrate prepared in this embodiment has a bonding energy of 5.5 J / m at 450℃. 2 .

[0051] Comparative Example 1

[0052] This comparative example presents a method for significantly improving the high-temperature interfacial bonding strength of ceramic coatings. The method includes substrate surface cleaning, selection and suitability assessment of the transition layer material, magnetron sputtering preparation of the transition layer, and magnetron sputtering preparation of the TiBN ceramic coating. The specific process is as follows:

[0053] S1. Substrate surface cleaning: After heating the metal substrate, place it in a vacuum sputtering coating machine at a temperature of 400℃; adjust the vacuum level; then fill with argon gas, turn on the substrate bias voltage to -970V, and clean for 10 minutes to perform ion source surface cleaning to obtain the cleaned metal substrate.

[0054] S2. Magnetron sputtering preparation of the transition layer: Argon gas is introduced at a flow rate of 15 sccm; the target power of the Ti target is adjusted to 450W; magnetron sputtering is used to deposit a transition layer Ti on the surface of the S1 metal substrate at a temperature of 400℃, resulting in a metal substrate covered with the transition layer; the thickness of the transition layer after deposition is 60 nm.

[0055] S3. Magnetron sputtering preparation of ceramic coating: Argon and nitrogen are introduced, with a nitrogen flow rate of 2.6 sccm. The TiB2 target and Ti target are turned on, with a TiB2 target power of 80W and a Ti target power of 450W. The substrate bias voltage is set to -110V. TiBN is deposited on the surface of the metal substrate covered with the transition layer. The TiBN deposition temperature is 400℃ and the deposition time is 3h. After cooling, TiBN ceramic coating-transition layer-metal substrate is obtained.

[0056] Figure 2 The image shows a TEM image of the interface between the TiBN ceramic coating and the substrate obtained in Comparative Example 1. The image clearly shows the interface between the crystalline and amorphous materials, indicating poor bonding between the coating and the substrate.

[0057] The TiBN ceramic coating-transition layer-metal substrate prepared in this comparative example has a bonding energy of 1.7 J / m at 450 °C. 2 .

[0058] Figure 3 The graph shows the variation of internal stress along the growth direction of the TiBN ceramic coating in Example 1 and Comparative Example 1. It can be seen that the internal stress of Example 1 is significantly reduced compared to Comparative Example 1, so it can be inferred that the coating has a better bonding strength with the substrate.

[0059] Figure 4 , Figure 5The images show the blistering morphology of the TiBN ceramic coatings in Example 1 and Comparative Example 1 after high-temperature treatment at 450℃. The bonding energy was calculated based on this. The comparison shows that the bonding energy of the TiBN ceramic coating in Example 1 after high-temperature treatment at 450℃ is significantly higher than that in Comparative Example 1, indicating that its bonding strength is significantly improved at high temperatures.

[0060] Example 2

[0061] This embodiment provides a method for significantly improving the high-temperature interfacial bonding strength of ceramic coatings. The method includes substrate surface cleaning, magnetron sputtering preparation of a transition layer, and magnetron sputtering preparation of a TiSiNAlCrY ceramic coating. The specific process is as follows:

[0062] S1. Substrate surface cleaning: After heating the metal substrate, place it in a vacuum sputtering coating machine at a temperature of 500℃; adjust the vacuum level; then fill with argon gas, turn on the substrate bias voltage to -970V, and clean for 10 minutes to perform ion source surface cleaning to obtain the cleaned metal substrate.

[0063] S2. Magnetron sputtering preparation of the transition layer: Argon gas is introduced at a flow rate of 19 sccm; the target power of the Ti target is adjusted to 200W; a transition layer is deposited on the surface of the S1 metal substrate using magnetron sputtering technology at a deposition temperature of 500℃, resulting in a metal substrate coated with a Ti transition layer; the thickness of the transition layer after deposition is 150 nm.

[0064] S3. Magnetron sputtering preparation of ceramic coating: Argon and nitrogen are introduced, with a nitrogen flow rate of 2.2 sccm. AlCrY, Ti, and TiSi targets are turned on, with AlCrY target power of 150W, Ti target power of 200W, and TiSi target power of 30W. The substrate bias voltage is set to -80V. A TiSiNAlCrY ceramic coating is deposited on the surface of the metal substrate covered with the transition layer. The deposition temperature of TiSiNAlCrY is 500℃, and the deposition time is 3.5h. After cooling, a TiSiNAlCrY ceramic coating-transition layer-metal substrate is obtained.

[0065] Tests showed that the ceramic coating obtained in this embodiment bonded well with the metal substrate.

[0066] The formation of good crystals at the coating-substrate interface is mainly achieved by increasing the deposition temperature and reducing the deposition power, which is the key to improving the bonding strength. Furthermore, the cleaning of the substrate surface and the preparation of the transition layer by magnetron sputtering can further improve the bonding strength, thereby significantly improving the coating bonding strength.

[0067] It should be understood that the term "and / or" in this article is merely a description of the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone. A and B can be singular or plural. Additionally, the character " / " in this article generally indicates an "or" relationship between the preceding and following related objects, but it can also represent an "and / or" relationship. Please refer to the context for a more accurate understanding.

[0068] In this invention, "at least one" means one or more, and "more than one" means two or more. "At least one of the following" or similar expressions refer to any combination of these items, including any combination of a single item or a plurality of items. For example, at least one of a, b, or c can represent: a, b, c, ab, ac, bc, or abc, where a, b, and c can be a single item or multiple items.

[0069] It should be understood that, in various embodiments of the present invention, the order of the above-mentioned process numbers does not imply the order of execution. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present invention.

[0070] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A method for significantly improving the high-temperature interfacial bonding strength of ceramic coatings, characterized in that, The method for significantly improving the high-temperature interfacial bonding strength of ceramic coatings includes substrate surface cleaning, magnetron sputtering preparation of the transition layer, and magnetron sputtering preparation of the ceramic coating. The specific process is as follows: S1. Substrate surface cleaning: After heating the metal substrate, place it in a vacuum sputtering coating machine, adjust the vacuum level, then fill it with argon gas, turn on the substrate bias voltage to perform ion source surface cleaning, and obtain the cleaned metal substrate. S2. Magnetron sputtering preparation of the transition layer: Select Ti as the transition layer material for the metal substrate of S1, introduce argon gas, adjust the target power of the Ti target, and use magnetron sputtering technology to deposit the transition layer Ti on the surface of the metal substrate of S1 to obtain a metal substrate covered with the transition layer Ti. S3. Magnetron sputtering preparation of ceramic coating: Argon and nitrogen are introduced, substrate bias is set, target material corresponding to ceramic coating is turned on, ceramic coating is deposited on the surface of metal substrate covered with transition layer, and ceramic coating-transition layer-metal substrate is obtained after cooling.

2. The method for significantly improving the high-temperature interfacial bonding strength of ceramic coatings according to claim 1, characterized in that, The heating temperature of the metal substrate in S1 is 500℃; the substrate bias voltage in S1 is turned on to -1000V~-600V; and the cleaning time in S1 is 5-15min.

3. The method for significantly improving the high-temperature interfacial bonding strength of ceramic coatings according to claim 1, characterized in that, The argon gas flow rate described in S2 is 15-20 sccm; the Ti target power described in S2 is 100-300 W; the temperature during the deposition of the Ti transition layer described in S2 is 450-550 °C; and the thickness of the Ti transition layer after deposition described in S2 is 100-150 nm.

4. The method for significantly improving the high-temperature interfacial bonding strength of ceramic coatings according to claim 1, characterized in that, The nitrogen flow rate in S3 is 2-4 sccm; and the base bias voltage in S3 is set to -140V to -80V.

5. The method for significantly improving the high-temperature interfacial bonding strength of ceramic coatings according to claim 1, characterized in that, The ceramic coating deposited in S3 is a TiBN ceramic coating.

6. The method for significantly improving the high-temperature interfacial bonding strength of ceramic coatings according to claim 1, characterized in that, The ceramic coating deposited in S3 is a TiSiNAlCrY ceramic coating.

7. The TiBN ceramic coating according to claim 5, characterized in that, The target materials corresponding to the TiBN ceramic coating are TiB2 target and Ti target, wherein the power of TiB2 target is 20-40W and the power of Ti target is 150-250W; the deposition time of TiBN is 3-5h; and the deposition temperature of TiBN is 450-550℃.

8. The TiSiNAlCrY ceramic coating according to claim 6, characterized in that, The target materials corresponding to the TiSiNAlCrY ceramic coating are AlCrY target, Ti target and TiSi target, wherein the power of AlCrY target is 100-200W, the power of Ti target is 150-250W and the power of TiSi target is 20-40W; the deposition time of TiSiNAlCrY is 3-5h; and the deposition temperature of TiSiNAlCrY is 450-550℃.

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