High-entropy max phase ceramic coating and method of making and ceramic material and applications thereof

Abstract

The application discloses a preparation method of a ceramic coating, and relates to the technical field of ceramic coating preparation, and discloses a high-entropy MAX phase ceramic coating, a preparation method of the high-entropy MAX phase ceramic coating, and a ceramic material and application thereof. The disclosed preparation method comprises the following steps: depositing a coating on the surface of a substrate by using a high-power pulse magnetron sputtering method; and the target material used in the high-power pulse magnetron sputtering process is a composite component target material prepared by hot pressing, and the molar ratio of the element components is M:Al:N=1.9-2.1:1:0.8-1.1, and the M element is selected from at least five kinds of Ti, V, Zr, Nb, Ta and Hf, and the percentage of each kind of metal element in the M element is between 5-35%. The high-entropy MAX phase ceramic coating is prepared by using the preparation method. The ceramic material is obtained by depositing the high-entropy MAX phase ceramic coating on the surface of a substrate by using the preparation method. The preparation method of the coating can prepare the high-entropy MAX coating with good performance, and the preparation process of the method does not introduce active nitrogen gas, and the method has good repeatability.

Description

Technical Field

[0001] This invention relates to the field of ceramic coating preparation technology, and more specifically, to high-entropy MAX phase ceramic coatings, their preparation methods, ceramic materials, and their applications. Background Technology

[0002] MAX phase is a new type of ceramic material with a layered structure, and its chemical formula is M. n+1 AX n In the formula, n is an integer, M is a transition metal element, A is a group IIIA to VA element, and X is carbon or nitrogen. Depending on the value of n, MAX phases can be divided into 211, 312, and 413 series, possessing the excellent properties of both metals and ceramics due to their unique crystal structure. In recent years, with the vigorous development of high-entropy materials research, these novel multi-principal element materials, composed of multiple elements in equal or near-equal amounts, exhibit many structural, mechanical, electrical, and magnetic properties different from traditional materials. This material design concept has been further extended to the field of high-entropy MAX phases. When four or more elements simultaneously occupy the M or A sites in a MAX phase, a high-entropy MAX phase is formed, different from traditional MAX phase solid solutions (where no more than two elements are dissolved in one location). Moreover, due to the complex composition of high-entropy MAX phases, adjusting the composition of the M or A sites allows for more precise control of the target composition, thereby enabling more targeted regulation of its properties. High-entropy MAX phase coatings can couple the size effect generated by the low-dimensional morphology of the coating with the unique multi-principal element characteristic effect of high-entropy materials, thus exhibiting comprehensive performance superior to bulk MAX phase and traditional MAX phase coatings, such as better hardness, corrosion resistance, wear resistance, radiation resistance and high-temperature oxidation resistance, showing great application potential in extreme service environments such as aerospace and nuclear reactors.

[0003] Currently, sputtering deposition is the most commonly used technique for preparing high-entropy ceramic coatings. In preparing nitride high-entropy ceramic coatings, reactive sputtering is mainly employed, where reactive N2 gas is introduced during sputtering to react with the sputtered particles and generate the desired coating. However, due to the introduction of the reactive gas, the target material reacts with the gas on the target surface to form compounds. The media synthesis rate exceeds the sputtering rate, resulting in a grayish-white coating on the target surface, causing "target poisoning" and hindering the coating process. Furthermore, the reactive gas flow rate fraction significantly affects the structure of the deposited coating, making it difficult to control and obtain high-entropy MAX phase coatings with a narrow composition range where the X-site is N, and experimental repeatability is poor. Therefore, there are few reports on the preparation of high-entropy MAX phase ceramic coatings with the X-site being N, severely restricting its development. Therefore, developing an easy-to-operate method for preparing high-entropy MAX phase ceramic coatings is of great significance for studying their performance and promoting their application.

[0004] In view of this, the present invention is proposed. Summary of the Invention

[0005] The purpose of this invention is to provide high-entropy MAX phase ceramic coatings, their preparation methods, ceramic materials, and their applications.

[0006] This invention is implemented as follows:

[0007] In a first aspect, the present invention provides a method for preparing a high-entropy MAX phase ceramic coating, comprising:

[0008] A coating was deposited on the substrate surface using high-power pulsed magnetron sputtering.

[0009] The target material used in high-power pulsed magnetron sputtering is a composite material with an elemental molar ratio of M:Al:N = 1.9~2.1:1:0.8~1.1. The M element is selected from at least five of Ti, V, Zr, Nb, Ta and Hf, and the percentage of each metal element in the M element is between 5% and 35%.

[0010] The deposition parameters for high-power pulsed magnetron sputtering include: heating the substrate to a temperature of 300–800°C, using argon as the working gas, using a target power of 2–20 kW, using a peak current of 300–600 A, using a pulse duration of 50–1000 μs, and using a pulse frequency of 50–500 Hz.

[0011] In an optional implementation, the deposition parameters for high-power pulsed magnetron sputtering also include: operating pressure of 0.5 to 3.0 Pa and substrate bias of -50 to -100 V.

[0012] In an optional embodiment, the preparation of a target material is further included before high-power pulsed magnetron sputtering, and the preparation method includes:

[0013] The raw material powder is cold-pressed to obtain a green body;

[0014] The green blank is then placed in an environment of 700-1200℃ and 30-50MPa under an argon atmosphere for hot pressing and sintering for 50-70 minutes.

[0015] Optionally, the pressure applied during cold pressing is 5 to 300 MPa.

[0016] In an optional embodiment, the raw material powder is any combination of element M, nitride of element M, M-Al intermetallic compound, and aluminum powder, as long as the molar ratio of elemental composition is M:Al:N = 1.9~2.1:1:0.8~1.1.

[0017] In an optional embodiment, the particle size of the mixed powder is 200-400 mesh;

[0018] Optionally, the purity of the mixed powder is greater than 95%.

[0019] In an optional implementation, element M is composed of five elements: Ti, V, Zr, Ta, and Hf, with a molar ratio of 1:1:1:1:1 or 1:1:1:1:0.5.

[0020] In an optional embodiment, the substrate surface is further subjected to self-glow cleaning prior to coating deposition;

[0021] Optionally, the vacuum level is controlled to be less than 3.0 × 10⁻⁶ before cleaning the substrate surface. -3 Pa.

[0022] In optional embodiments, the matrix is ​​a nickel-based alloy or a high-entropy alloy material.

[0023] Secondly, the present invention provides a high-entropy MAX phase ceramic coating, which is prepared by the preparation method described in the foregoing embodiments.

[0024] Thirdly, the present invention provides a ceramic material obtained by depositing a high-entropy MAX phase ceramic coating on the surface of a substrate using the preparation method described in the foregoing embodiments.

[0025] Fourthly, the present invention provides the application of the aforementioned high-entropy MAX phase ceramic coating or the aforementioned ceramic material in aerospace equipment and nuclear reactor equipment.

[0026] The present invention has the following beneficial effects:

[0027] The method for preparing high-entropy MAX phase ceramic coatings provided by this invention utilizes high-power pulsed laser deposition technology. The resulting coating exhibits a dense structure and good stability. Furthermore, due to the high power output and high target ionization rate, the deposited particles possess higher energy, facilitating diffusion and promoting the formation of a complex high-entropy MAX phase, M2AlN (where M represents at least five of Ti, V, Zr, Nb, Ta, and Hf, with each element accounting for 5% to 35% of the total). In addition, since the target material contains nitrogen, the nitrogen in the coating originates directly from the target, eliminating the need to introduce nitrogen gas during deposition and preventing target poisoning. Moreover, the method provided in this invention, by eliminating the need for an active gas during preparation, readily yields high-entropy MAX phase coatings with a narrow composition range where the X-position is N, exhibiting good repeatability. Attached Figure Description

[0028] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0029] Figure 1 The image shown is the XRD pattern of the coating obtained in Example 1 of this invention.

[0030] Figure 2 This is a SEM image of the coating obtained in Example 2 of the present invention;

[0031] Figure 3 Here is a SEM image of the coating obtained in Example 3 of this invention;

[0032] Figure 4 This is a SEM image of the coating obtained in Example 4 of the present invention;

[0033] Figure 5 The image shows the XRD pattern of the coating prepared according to the specifications. Detailed Implementation

[0034] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0035] The high-entropy MAX phase ceramic coating, its preparation method, and the ceramic material provided in the embodiments of the present invention will be described in detail below.

[0036] The method for preparing a high-entropy MAX phase ceramic coating provided in this embodiment of the invention includes:

[0037] A coating was deposited on the substrate surface using high-power pulsed magnetron sputtering.

[0038] The target material used in high-power pulsed magnetron sputtering is a composite material with an elemental molar ratio of M:Al:N = 1.9~2.1:1:0.8~1.1. The M element is selected from at least five of Ti, V, Zr, Nb, Ta and Hf, and the percentage of each metal element in the M element is between 5% and 35%.

[0039] The deposition parameters for high-power pulsed magnetron sputtering include: heating the substrate to a temperature of 300–800°C, target power of 2–20 kW, peak current of 300–600 A, pulse duration of 50–1000 μs, and pulse frequency of 50–500 Hz.

[0040] The preparation method provided in this invention uses high-power pulsed laser deposition technology to prepare the coating. The prepared coating has a dense structure and good stability. Moreover, due to the high power supply and high target ionization rate, the deposited particles have higher energy and are easier to diffuse, which can promote the formation of a complex high-entropy MAX phase M2AlN (M is at least five of Ti, V, Zr, Nb, Ta, and Hf, and the percentage of each element is between 5% and 35%). In addition, since the target contains nitrogen, the nitrogen in the coating comes directly from the target. There is no need to introduce active nitrogen gas during the deposition process, and the "target poisoning" phenomenon caused by nitrogen introduction will not occur. At the same time, since the method provided in this invention does not require the introduction of active gas during the preparation process, it is easy to obtain a high-entropy MAX phase coating with a narrow composition range of N at the X position, and the repeatability is good.

[0041] In the preparation method provided in the embodiments of the present invention, the deposition parameters of the high-power pulsed magnetron sputtering method have a significant impact on the performance of the obtained coating. For example, if the substrate temperature is too low, below 300°C, the atomic energy is low, making it difficult to form an ordered structure phase and more inclined to form an amorphous coating. If it is too high, above 800°C, it will be more inclined to form a variety of binary nitride coatings. The power level will affect the ionization rate of sputtered atoms and the energy of ions, thereby affecting the phase composition in the coating.

[0042] Specifically, the preparation method is as follows:

[0043] S1, Target Material Preparation

[0044] The target material is a composite component. As long as the element ratio of M, Al and N is 1.9-2.1:1:0.8-1.1, it is acceptable. It is not required that it is a composite of single compounds, multiple compounds, or a composite of elements.

[0045] For example, the preparation methods of the target material are as follows:

[0046] The raw material powder, which has been ball-milled, dried and mixed evenly, is cold-pressed under a pressure of 5 to 300 MPa (e.g., 5 MPa, 10 MPa, 50 MPa, 100 MPa, 200 MPa or 300 MPa) to obtain a green blank.

[0047] After obtaining the green blank, it is placed in a hot pressing sintering furnace, argon gas is introduced into it, the temperature is raised to 700-1200℃ (e.g., 700℃, 800℃, 1000℃ or 1200℃), and the pressure is controlled at 30-50MPa (e.g., 30MPa, 40MPa or 50MPa) for hot pressing sintering for 50-70min (e.g., 50min, 60min or 70min). After that, the pressure is unloaded and the furnace is cooled to room temperature to prepare a composite bulk target material containing multiple components.

[0048] Specifically, the raw material powder contains M, Al, and N elements in a molar ratio of 1.9–2.1:1:0.8–1.1 (e.g., 1.9:1:0.8, 2:1:1, or 2.1:1:1.1). For example, the raw material powder can be a mixture of M element, M nitride, M-Al intermetallic compound, and aluminum powder. The M element is selected from at least five of Ti, V, Zr, Nb, Ta, and Hf.

[0049] The raw materials can be any combination of metal powder and corresponding nitride powder or intermetallic compound powder. The powder cost is relatively low, and the composition of the target material can be controlled by adjusting the content of different components in the starting powder, thereby regulating the composition of the coating. In this case, there are no specific restrictions on the specific powders used in the raw material formulation, as long as the above-mentioned elemental molar ratio requirements are met.

[0050] Furthermore, element M can be composed of Ti, V, Zr, Ta, and Hf. For ease of formulation, a molar ratio of these five elements of 1:1:1:1:1 or 1:1:1:1:0.5 can be considered.

[0051] Preferably, to ensure a coating with better performance, the particle size of the raw material powder is 200-400 mesh, and its purity is greater than 95%.

[0052] S2, Coating preparation by high-power pulsed magnetron sputtering

[0053] The substrate is placed inside the cavity of a high-power pulsed magnetron sputtering device, and the back-bottom vacuum is first evacuated to less than 3.0 × 10⁻⁶. -3 Pa, introduce flowing argon gas, adjust the gas pressure to 6 Pa, apply a bias voltage of -500V, and a duty cycle of 80% to perform self-glow cleaning on the substrate;

[0054] After the substrate cleaning is completed, adjust the heating substrate temperature to 300–800℃ (e.g., 300℃, 400℃, 500℃, 600℃, or 800℃), use argon as the working gas, set the working pressure to 0.5–3.0 Pa (e.g., 0.5 Pa, 1 Pa, 2 Pa, or 3 Pa), set the substrate bias voltage to -50–-100V (e.g., -50V, -80V, or -100V), and set the target power to 2–20KW (e.g., 2KW, 5KW, 10KW). Coating deposition is performed using a pulse duration of 50–1000 μs (e.g., 50 μs, 100 μs, 200 μs, 500 μs, 800 μs, or 1000 μs) and a pulse frequency of 50–500 Hz (e.g., 50 Hz, 100 Hz, 200 Hz, 300 Hz, 400 Hz, or 500 Hz).

[0055] Furthermore, the matrix can be selected from nickel-based alloys or high-entropy alloys. It should be noted that nickel-based alloys or high-entropy alloys are only one option in this embodiment; other materials, such as alumina, carbon steel, or zirconium-based alloys, can also be used in other embodiments of this invention.

[0056] The high-entropy MAX phase ceramic coating provided in this application embodiment is prepared using the preparation method provided in this application embodiment. This coating exhibits excellent hardness, corrosion resistance, wear resistance, radiation resistance, and high-temperature oxidation resistance.

[0057] The ceramic material provided in this application embodiment is obtained by depositing a high-entropy MAX phase ceramic coating on the substrate surface using the preparation method provided in this application embodiment. Due to the high-entropy MAX phase ceramic coating on its surface, this material also exhibits excellent hardness, corrosion resistance, wear resistance, radiation resistance, and high-temperature oxidation resistance, making it suitable for applications in extreme service environments such as aerospace and nuclear reactors.

[0058] The embodiments of the present invention also provide the application of the above-mentioned high-entropy MAX phase ceramic coating or the above-mentioned ceramic material in aerospace equipment and nuclear reactor equipment.

[0059] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0060] Example 1

[0061] This embodiment provides a high-entropy MAX phase ceramic coating with (Ti,V,Zr,Ta,Hf)2AlN as the main phase deposited on an Al2O3 substrate using high-power pulsed magnetron sputtering technology, which is prepared by the following method:

[0062] (1) Target material preparation: First, weigh commercially available Ti powder (400 mesh, 99% purity), V powder (400 mesh, 99% purity), Zr powder (400 mesh, 99% purity), Ta powder (400 mesh, 99% purity), Hf powder (400 mesh, 99% purity), Al powder (400 mesh, 99% purity), TiN powder (200 mesh, 99% purity), VN powder (200 mesh, 99% purity), and ZrN powder (200 mesh, 99% purity) with a molar ratio of Ti:V:Zr:Ta:Hf:Al:TiN:VN:ZrN:TaN:HfN = 1:1:1:1:1:1:5:1:1:1:1:1, in a ratio of 200:1 ... 9%), TaN powder (200 mesh, 99% purity), and HfN powder (200 mesh, 99% purity) were used as initial powders, placed in a ball mill jar, and an appropriate amount of alcohol was added. The mixture was then ball-milled in a planetary ball mill for 24 hours. The homogeneous mixture was then allowed to stand and dry at room temperature for 24 hours, and sieved to obtain a dry homogeneous mixture. The powder was then placed into a graphite mold and cold-pressed under a pressure of 10 MPa. The mold and the powder were then placed in a hot press furnace, and Ar gas was introduced as a protective gas. The temperature was raised to 800°C at a rate of 10°C / min, and the pressure was increased to 30 MPa. The temperature and pressure were maintained for 1 hour, and the composite block target material with multiple components was obtained by sintering.

[0063] (2) Coating deposition: High-power pulsed magnetron sputtering technology was used. Before starting the coating deposition, the back vacuum was first evacuated to less than 1.0 × 10⁻⁶. -3 At 6 Pa, Ar gas was introduced and the pressure was adjusted to 6 Pa. A bias voltage of -500 V and a duty cycle of 80% were applied to perform self-glow cleaning on the Al2O3 substrate. Then, the furnace cavity was heated to 500 °C. The working gas was Ar gas, the working pressure was 0.5 Pa, the substrate bias voltage was -50 V, the target power was 5 kW, the peak current was 400 A, the pulse time was 50 μs, and the pulse frequency was 300 Hz. A high-entropy MAX phase ceramic coating with the main components of (Ti, V, Zr, Ta, Hf)2AlN was deposited.

[0064] The XRD pattern of the (Ti,V,Zr,Ta,Hf)2AlN high-entropy MAX phase ceramic coating is shown below. Figure 1 As shown in the figure, apart from the matrix peak, the main diffraction peak of the coating is the diffraction peak of the high-entropy MAX phase (Ti,V,Zr,Ta,Hf)2AlN, with fewer impurity phases. Therefore, a ceramic coating with the high-entropy MAX phase (Ti,V,Zr,Ta,Hf)2AlN as the main phase was successfully prepared.

[0065] Example 2

[0066] This embodiment provides a high-entropy MAX phase ceramic coating with (Ti,V,Zr,Ta,Hf)2AlN as the main phase deposited on a carbon steel substrate using high-power pulsed magnetron sputtering technology, which is prepared by the following method:

[0067] (1) Target material preparation: First, weigh commercially available Ti powder (400 mesh, 99% purity), V powder (400 mesh, 99% purity), Zr powder (400 mesh, 99% purity), Ta powder (400 mesh, 99% purity), Hf powder (400 mesh, 99% purity), Al powder (400 mesh, 99% purity), TiN powder (200 mesh, 99% purity), and VN powder (200 mesh, 99% purity) with a molar ratio of Ti:V:Zr:Ta:Hf:Al:TiN:VN:ZrN:TaN:HfN = 1:1:1:1:1:1:5:1:1:1:1:1, in a ratio of 200 mesh to 1:1:1:1:1:5:1:1:1:1:1. The initial powders were ZrN powder (200 mesh, 99% purity), TaN powder (200 mesh, 99% purity), and HfN powder (200 mesh, 99% purity), which were subjected to high-energy ball milling to obtain a dry and uniform mixture. Then, the powder was loaded into a graphite mold and cold-pressed under a pressure of 30 MPa. After that, the mold and the powder were placed in a hot press furnace, and Ar gas was introduced as a protective gas. The temperature was raised to 1200°C at a rate of 10°C / min, and the pressure was increased to 50 MPa. The temperature and pressure were held for 1 hour, and sintering was carried out to obtain a composite block target material with multiple components.

[0068] (2) Coating deposition: High-power pulsed magnetron sputtering technology was used. Before starting the coating deposition, the back vacuum was first evacuated to 3.0 × 10⁻⁶. -4 At 5 Pa, Ar gas was introduced and the pressure was adjusted to 5 Pa. A bias voltage of -600 V and a duty cycle of 60% were applied to perform self-glow cleaning on the substrate material. Then, the furnace cavity was heated to 500 °C. The working gas was Ar gas, the working pressure was 0.5 Pa, the substrate bias voltage was -100 V, the target power was 10 kW, the peak current was 500 A, the pulse time was 800 μs, and the pulse frequency was 100 Hz. A high-entropy MAX phase ceramic coating with the main components of (Ti, V, Zr, Ta, Hf)2AlN was deposited.

[0069] SEM images of the (Ti,V,Zr,Ta,Hf)2AlN high-entropy MAX phase ceramic coating are shown below. Figure 2 As shown in the figure, the prepared coating has a smooth and uniform surface, a dense structure, and no obvious cracks.

[0070] Example 3

[0071] This embodiment provides a method for depositing a high-entropy MAX phase ceramic coating with (Ti,V,Zr,Nb,Hf)2AlN as the main phase on a nickel-based alloy substrate using high-power pulsed magnetron sputtering technology. The coating is prepared by the following method:

[0072] (1) Target material preparation: First, weigh commercially available Ti powder (400 mesh, 99% purity), V powder (400 mesh, 99% purity), Zr powder (400 mesh, 99% purity), Nb powder (400 mesh, 99% purity), Hf powder (400 mesh, 99% purity), Al powder (400 mesh, 99% purity), TiN powder (200 mesh, 99% purity), and VN powder (200 mesh, 99% purity) in a molar ratio of Ti:V:Zr:Nb:Hf:Al:TiN:VN:ZrN:NbN:HfN = 1:1:1:1:1:5:1.1:1.1:1.1:1.1:1.1, with a molar ratio of Ti:V:Zr:Nb:HfN = 1:1:1:1:1:5:1.1:1.1:1.1:1.1:1.1. The initial powders (200 mesh, 99% purity), ZrN powder (200 mesh, 99% purity), NbN powder (200 mesh, 99% purity), and HfN powder (200 mesh, 99% purity) were ball-milled at high energy to obtain a dry and uniform mixture. Then, the powder was loaded into a graphite mold and cold-pressed under a pressure of 5 MPa. After that, the mold and the powder were placed in a hot press furnace, and flowing Ar gas was introduced as a protective gas. The temperature was raised to 700°C at a rate of 10°C / min, and the pressure was increased to 50 MPa. The temperature and pressure were held for 70 min, and sintering was carried out to obtain a composite block target material with multiple components.

[0073] (2) Coating deposition: High-power pulsed magnetron sputtering technology was used. Before starting the coating deposition, the back vacuum was first evacuated to 3.0 × 10⁻⁶. -4 At 5 Pa, Ar gas was introduced and the pressure was adjusted to 5 Pa. A bias voltage of -600 V and a duty cycle of 60% were applied to perform self-glow cleaning on the substrate material. Then, the substrate temperature was heated to 300 °C. The working gas was Ar gas, the working pressure was 3 Pa, the substrate bias voltage was -80 V, the target power was 2 kW, the peak current was 300 A, the pulse time was 1000 μs, and the pulse frequency was 500 Hz. A high-entropy MAX phase ceramic coating with the main components of (Ti, V, Zr, Nb, Hf)2AlN was deposited.

[0074] SEM images of the (Ti,V,Zr,Nb,Hf)2AlN high-entropy MAX phase ceramic coating are shown below. Figure 3 As shown.

[0075] Example 4

[0076] This embodiment provides a high-entropy MAX phase ceramic coating with (Ti,V,Zr,Nb,Hf)2AlN as the main phase deposited on a zirconium-based alloy substrate using high-power pulsed magnetron sputtering technology. The coating is prepared by the following method:

[0077] (1) Target material preparation: First, weigh commercially available Ti powder (400 mesh, 99% purity), V powder (400 mesh, 99% purity), Zr powder (400 mesh, 99% purity), Nb powder (400 mesh, 99% purity), Hf powder (400 mesh, 99% purity), Al powder (400 mesh, 99% purity), and TiN powder (200 mesh, 99% purity) in a molar ratio of Ti:V:Zr:Nb:Hf:Al:TiN:VN:ZrN:NbN:HfN = 1.1:1.1:1.1:1.1:1.1:5:0.8:0.8:0.8:0.8:0.8. VN powder (200 mesh, 99% purity), ZrN powder (200 mesh, 99% purity), NbN powder (200 mesh, 99% purity), and HfN powder (200 mesh, 99% purity) were used as initial powders and subjected to high-energy ball milling to obtain a dry and uniform mixture. Then, the powder was loaded into a graphite mold and cold-pressed under a pressure of 300 MPa. After that, the mold and the powder were placed in a hot press furnace, and flowing Ar gas was introduced as a protective gas. The temperature was raised to 1000°C at a rate of 10°C / min, and the pressure was increased to 30 MPa. The temperature and pressure were held for 50 min, and sintering was carried out to obtain a composite block target material with multiple components.

[0078] (2) Coating deposition: High-power pulsed magnetron sputtering technology was used. Before starting the coating deposition, the back vacuum was first evacuated to 3.0 × 10⁻⁶. -4 At 5 Pa, Ar gas was introduced and the pressure was adjusted to 5 Pa. A bias voltage of -600 V and a duty cycle of 60% were applied to perform self-glow cleaning on the substrate material. Then, the furnace cavity was heated to 800 °C. The working gas was Ar gas, the working pressure was 0.5 Pa, the substrate bias voltage was -50 V, the target power was 20 kW, the peak current was 600 A, the pulse time was 50 μs, and the pulse frequency was 50 Hz. A high-entropy MAX phase ceramic coating with the main components of (Ti, V, Zr, Nb, Hf)2AlN was deposited.

[0079] SEM images of the (Ti,V,Zr,Nb,Hf)2AlN high-entropy MAX phase ceramic coating are shown below. Figure 4 As shown.

[0080] Comparative Example

[0081] This comparative example is basically the same as Example 1, except that the target power is 1KW.

[0082] The XRD pattern of the deposited ceramic coating is shown in the figure. Figure 5 As shown, it can be seen that, apart from the matrix diffraction peak, only obvious bulging diffraction peaks were observed, indicating that the coating prepared in this comparative example is an amorphous coating and did not obtain a high-entropy MAX phase with an ordered structure.

[0083] Experimental Example

[0084] The hardness, wear resistance, and corrosion resistance of the coatings prepared in each embodiment and comparative example were tested. The hardness of the coatings in the embodiments of the present invention was tested using a Bruker TI 980 nanoindenter; the tribological properties of the coatings in the embodiments of the present invention were evaluated by friction testing in air at room temperature using Si3N4 ceramic as the grinding ball; the corrosion resistance of the coatings was tested using an electrochemical workstation with a saturated NaCl solution as the etching solution. The test results are recorded in Table 1.

[0085] Table 1. Performance test results of samples prepared in each embodiment and comparative example.

[0086]

[0087]

[0088] As can be seen from the table above, the coatings of the samples prepared in the embodiments of this application have better hardness, wear resistance, and corrosion resistance. Comparing the comparative example with the corresponding Example 3, its hardness, wear resistance, and corrosion resistance are significantly worse. This indicates that the target power is low, and due to the low atomic ionization rate and limited energy, it is difficult to obtain an ordered crystal structure, and the coating density is low, making it impossible to obtain a high-entropy MAX phase coating with excellent performance.

[0089] In summary, the method for preparing high-entropy MAX phase ceramic coatings provided by this invention utilizes high-power pulsed laser deposition technology to prepare the coating, resulting in a dense structure and good stability. Furthermore, due to the high power supply and high target ionization rate, the deposited particles possess higher energy, facilitating diffusion and promoting the formation of a complex high-entropy MAX phase M2AlN (where M represents at least five of Ti, V, Zr, Nb, Ta, and Hf, with each element accounting for 5% to 35%). In addition, since the target material contains nitrogen, the nitrogen in the coating directly originates from the target material, eliminating the need to introduce nitrogen gas during deposition and preventing "target poisoning" caused by nitrogen introduction. Moreover, the method provided by this invention, by eliminating the need for introducing active gas during preparation, easily obtains high-entropy MAX phase coatings with a narrow composition range where N is at the X-position, exhibiting good repeatability.

[0090] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing a high-entropy MAX phase ceramic coating, characterized in that, include: A coating was deposited on the substrate surface using high-power pulsed magnetron sputtering. The target material used in high-power pulsed magnetron sputtering is a composite target material with an elemental molar ratio of M:Al:N = 1.9~2.1:1:0.8~1.

1. The M element is selected from at least five of Ti, V, Zr, Nb, Ta and Hf, and the percentage of each metal element in the M element is between 5% and 35%. The deposition parameters for high-power pulsed magnetron sputtering include: heating the substrate to a temperature of 300~800℃, using argon as the working gas, using a target power of 2~20kW, using a peak current of 300~600A, using a pulse duration of 50~1000μs, and using a pulse frequency of 50~500Hz.

2. The preparation method according to claim 1, characterized in that, The deposition parameters for high-power pulsed magnetron sputtering also include: working pressure of 0.5~3.0 Pa and substrate bias of -50~-100 V.

3. The preparation method according to claim 1, characterized in that, The preparation of the target material is also included before high-power pulsed magnetron sputtering, and the preparation methods include: The raw material powder is cold-pressed to obtain a green body; The green blank is then placed in an environment of 700~1200℃, 30~50MPa, and argon atmosphere for hot pressing and sintering for 50~70 minutes.

4. The preparation method according to claim 3, characterized in that, The pressure applied during cold pressing is 5~300MPa.

5. The preparation method according to claim 3, characterized in that, The elemental molar ratio of the raw material powder is M:Al:N = 1.9~2.1:1:0.8~1.1, which is an arbitrary mixture of element M, nitride of element M, intermetallic compound of M-Al, and aluminum powder.

6. The preparation method according to claim 5, characterized in that, The particle size of the mixed powder is 200-400 mesh.

7. The preparation method according to claim 5, characterized in that, The purity of the mixed powder is greater than 95%.

8. The preparation method according to claim 1, characterized in that, The M element is composed of five elements: Ti, V, Zr, Ta, and Hf, with a molar ratio of 1:1:1:1:1 or 1:1:1:1:0.

5.

9. The preparation method according to claim 1, characterized in that, The process also includes a self-glow cleaning of the substrate surface prior to coating deposition.

10. The preparation method according to claim 9, characterized in that, Before cleaning the substrate surface, the vacuum level is controlled to be less than 3.0 × 10⁻⁶. -3 Pa.

11. The preparation method according to claim 1, characterized in that, The substrate is a nickel-based alloy or a high-entropy alloy material.

12. A high-entropy MAX phase ceramic coating, characterized in that, It is prepared by the preparation method described in any one of claims 1 to 11.

13. A ceramic material, characterized in that, The high-entropy MAX phase ceramic coating is obtained by depositing the coating on the substrate surface using the preparation method described in any one of claims 1 to 11.

14. The application of the high-entropy MAX phase ceramic coating as described in claim 12 or the ceramic material as described in claim 13 in aerospace equipment and nuclear reactor equipment.

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