Ultra-high temperature ablation resistant (HfZr) C1-x coating as well as preparation method and application thereof

Abstract

The invention discloses an ultrahigh temperature ablation resistant (HfZr) C1-x coating as well as a preparation method and application thereof. The preparation method comprises the following steps: by adopting a magnetron sputtering technology, taking an Hf target and a Zr target as target materials and taking carbon source gas as working gas, depositing on the surface of a substrate to form an ultrahigh-temperature ablation-resistant (HfZr) C1-x coating, wherein the (HfZr) C1-x coating has a face-centered cubic structure which is preferentially oriented by a (111) crystal face. According to the method, the magnetron sputtering technology is adopted, acetylene flux is adjusted, the carbon content in the coating is changed, the (HfZr) C1-x coating with variable components is prepared, direct contact between a high-temperature environment and a base material is blocked due to the high-melting-point characteristic of (HfZr) C1-x and oxide of the (HfZr) C1-x, and damage to a base caused by an ablation environment is remarkably reduced.

Description

Technical Field

[0001] The present invention belongs to the field of ablative protection coatings, and particularly relates to a coating of (HfZr)C for ultra-high temperature ablation resistance 1-x and its preparation method and application. Background Art

[0002] In the field of aerospace, key components such as the head, wings, and engine tail nozzles of aircraft are the key core components that determine the safety and long-term performance of the aircraft. The local temperature on the surface of high-speed aircraft can reach over 1000 °C, and at the same time, it faces strong coupling damage of multiple factors such as high-temperature oxidation, mechanical property attenuation, and airflow erosion, which are extremely likely to cause the rapid failure of service components. Under such working conditions, relying solely on the ultra-high temperature ablation resistance of the components is difficult to ensure the efficient and long-life service of the components. Therefore, preparing an ultra-high temperature protection coating on the workpiece surface is an effective protection method. Ultra-high temperature ceramics (UHTCs) refer to transition metal carbides, borides, nitrides, etc. with melting points exceeding 3000 °C. HfC, ZrC, and their oxides have relatively high melting points and exhibit good stability in high-temperature environments, and are preferred phases for preparing ultra-high temperature ablation-resistant coatings. At present, plasma spraying, CVD, etc. are mostly used at home and abroad to prepare ablation-resistant coatings. The above preparation methods have complex processes, high requirements for the physical and chemical properties of the substrate material, and it is difficult to accurately control the phase composition of the coating, with certain application limitations. Summary of the Invention

[0003] The main purpose of the present invention is to provide a coating of (HfZr)C for ultra-high temperature ablation resistance 1-x and its preparation method and application to overcome the deficiencies of the prior art.

[0004] To achieve the foregoing invention purpose, the technical solutions adopted by the present invention include:

[0005] An embodiment of the present invention provides a preparation method for a coating of (HfZr)C for ultra-high temperature ablation resistance 1-x which includes:

[0006] Providing a substrate;

[0007] And, using magnetron sputtering technology, using an Hf target and a Zr target as target materials, and using a carbon source gas as the working gas, thereby depositing a coating of (HfZr)C for ultra-high temperature ablation resistance on the surface of the substrate 1-x wherein the (HfZr)C 1-x coating has a face-centered cubic structure with (111) crystal plane preferred orientation.

[0008] An embodiment of the present invention also provides the coating of (HfZr)C for ultra-high temperature ablation resistance prepared by the foregoing preparation method1-x Coating; the (HfZr)C 1-x The coating has a face-centered cubic structure with a preferred orientation of the (111) crystal plane.

[0009] The embodiment of the present invention also provides the application of the aforementioned ultra-high temperature ablation-resistant (HfZr)C 1-x coating in the field of aerospace ablation-resistant protective coatings.

[0010] Compared with the prior art, the beneficial effects of the present invention are as follows: starting from the flux of the carbon source gas (acetylene) during the deposition process, by adjusting the carbon content in the carbon source gas, the phase and composition of the carbide in the coating are accurately regulated. This method does not rely on complex equipment and preparation methods, only requires a simple magnetron sputtering method and gas flux adjustment. The prepared (HfZr)C 1-x coating has the characteristics of high density and good continuity, can effectively alleviate the oxidation and gas flow erosion damage caused by high-temperature ablation conditions, and has potential application value in the field of aerospace ablation-resistant protective coatings; in addition, the wide range of composition changes can make the coating exhibit wear resistance, friction reduction, and corrosion resistance and other properties. Brief Description of the Drawings

[0011] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the description of the embodiments or the prior art. Obviously, the drawings in the following description are only some embodiments recorded in the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0012] Figures 1a - 1b It is a graph of the ablation morphology and surface temperature of the ultra-high temperature ablation-resistant (HfZr)C 1-x coating prepared on the graphite substrate in Example 1 of the present invention;

[0013] Figures 2a - 2d It is an element distribution map of the (HfZr)C 1-x coating prepared on the graphite substrate in Example 1 of the present invention after ablation;

[0014] Figures 3a - 3b It is a graph of the ablation morphology and surface temperature of the ultra-high temperature ablation-resistant (HfZr)C 1-x coating prepared on the silicon carbide substrate in Example 2 of the present invention;

[0015] Figures 4a - 4b It is a graph of the ablation morphology and surface temperature of the ultra-high temperature ablation-resistant (HfZr)C 1-x coating prepared on the silicon carbide substrate in Example 3 of the present invention;

[0016] Figure 5It is the morphology diagram of the coating prepared on the graphite matrix after ablation in Comparative Example 1 of the present invention;

[0017] Figure 6 It is the morphology diagram of the coating prepared on the silicon carbide matrix after ablation in Comparative Example 2 of the present invention;

[0018] Figure 7 It is the (HfZr)C 1-x microscopic morphology diagram of the coating in a typical embodiment of the present invention. Detailed implementation manners

[0019] In view of the defects of the prior art, the inventors of this case have proposed the technical solution of the present invention through long-term research and a large number of practices. The technical solution of the present invention will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts fall within the protection scope of the present invention.

[0020] Specifically, as an aspect of the technical solution of the present invention, a method for preparing a coating resistant to ultra-high temperature ablation (HfZr)C 1-x coating includes:

[0021] Providing a substrate;

[0022] And, using the magnetron sputtering technique, using Hf target and Zr target as target materials, and using a carbon source gas as the working gas, thereby depositing a coating resistant to ultra-high temperature ablation (HfZr)C 1-x coating on the surface of the substrate; wherein, the (HfZr)C 1-x coating has a face-centered cubic structure with a preferred orientation of the (111) crystal plane.

[0023] The present invention uses the magnetron sputtering technique for coating deposition. This method is relatively simple and time-saving, and can directly regulate the phase composition and volume ratio in the coating by adjusting the acetylene gas flux, realizing the precise regulation of the microstructure and phase composition of the coating.

[0024] The present invention can precisely regulate the phase composition and relative volume fraction in the coating within a wide range by adjusting the flux of the reaction gas during the coating deposition process, enabling the coating to exhibit different physical and chemical properties, thereby showing different ablation-resistant properties.

[0025] In some preferred embodiments, the coating resistant to ultra-high temperature ablation (HfZr)C 1-x coating is composed of nanoscale carbide (HfZr)C 1-x particles.

[0026] In some preferred embodiments, the coating resistant to ultra-high temperature ablation (HfZr)C1-x The coating consists of Hf metal, Zr metal and carbon-poor (HfZr)C 1-x Carbides, where 0<x<1.

[0027] In some preferred embodiments, the ultra-high temperature ablation resistant (HfZr)C 1-x The coating composition includes carbides and amorphous carbon in a stoichiometric ratio of (HfZr)C.

[0028] In some preferred embodiments, the preparation method specifically includes: using magnetron sputtering technology, using Hf target and Zr target as target materials, using carbon source gas and inert gas as working gas, applying negative bias voltage to the substrate, applying target power to the target material, thereby depositing ultrahigh temperature ablation resistant (HfZr)C on the surface of the substrate 1-x Coating; wherein, the gas pressure in the reaction chamber is 0.4-0.6Pa, the target power is 12-15kW, the substrate negative bias voltage is 50-150V, the temperature of the reaction chamber is 200-450℃, the deposition time is 10-20h, the flux of the carbon source gas is 20-60sccm, and the flux of the inert gas is 150-350sccm.

[0029] In some embodiments, the deposition of (HfZr)C 1-x The target power used for the coating is 12-14kW, the reaction chamber temperature is 300-450°C, and argon and acetylene are the working gases in the chamber.

[0030] Furthermore, the target power is 12-14 kW, the substrate negative bias voltage is 100 V, the reaction chamber temperature is 400-450° C., the carbon source gas is acetylene, and the inert gas is argon.

[0031] Furthermore, the target power is 12 kW, the substrate negative bias voltage is 100 V, and the reaction chamber temperature is 400° C.

[0032] In the present invention, (HfZr)C 1-x The coating preparation principle is at least that when the acetylene flux is less than 40 sccm, the coating contains a small amount of Hf, Zr metal elements and carbon-poor (HfZr)C 1-x carbides; when the acetylene flux increases, the carbon deficiency in the coating is gradually alleviated, and the volume fraction of the metal element decreases significantly; when the acetylene flux is greater than 40sccm, the coating is basically composed of carbides with a stoichiometric ratio of (HfZr)C, and also contains a small amount of amorphous carbon.

[0033] Further, the carbon source gas includes acetylene, but is not limited thereto.

[0034] Further, the inert gas includes argon, but is not limited thereto.

[0035] Furthermore, the volume fraction of the carbon source gas in the working gas is 7%-20%.

[0036] Furthermore, the substrate includes a graphite substrate or a silicon carbide substrate, and is not limited thereto.

[0037] Furthermore, the purity of the Hf target and the Zr target is greater than 99.99 wt.%.

[0038] In some preferred embodiments, the preparation method further includes: first performing surface pretreatment on the substrate, and then depositing a (HfZr)C 1-x coating resistant to ultra-high temperature ablation on the surface of the substrate by magnetron sputtering technology; wherein, the surface pretreatment includes surface treatment and ion bombardment cleaning treatment.

[0039] Furthermore, the surface pretreatment includes: grinding and polishing the substrate, and then performing ultrasonic cleaning.

[0040] Furthermore, the grinding and polishing treatment makes the surface roughness of the substrate at least 2-3 μm.

[0041] Furthermore, first perform preliminary grinding treatment on the surface with sandpaper, the surface roughness after treatment is 2-3 μm, and place the substrate in acetone and alcohol respectively for ultrasonic treatment.

[0042] Furthermore, the ion bombardment cleaning treatment includes: placing the substrate obtained by surface treatment in a reaction chamber at a temperature of 200-450 °C and a vacuum degree of 4-6×10 -3 Pa, introducing argon gas, applying a negative bias voltage of 500-600 V to the substrate, and then performing ion bombardment cleaning treatment on the surface of the substrate.

[0043] In some preferred embodiments, the preparation method further includes: after the deposition of the (HfZr)C 1-x coating is completed, wait until the reaction temperature in the chamber drops below 100 °C, and take out the substrate with the (HfZr)C 1-x coating deposited on its surface.

[0044] In some embodiments, the microscopic morphology of the (HfZr)C 1-x coating is as shown in Figure 7 the figure.

[0045] In some more specific embodiments, the preparation method of the (HfZr)C 1-x coating resistant to ultra-high temperature ablation includes:

[0046] Providing a graphite or silicon carbide substrate.

[0047] Using magnetron sputtering technology, with pure Hf and Zr targets as sputtering targets, argon and acetylene as working gases, applying a negative bias voltage to the substrate and a target power to the Hf and Zr metal targets, deposit (HfZr)C on the surface of graphite or silicon carbide 1-x a protective coating, and the coating has a face-centered cubic structure with a (111) crystal plane preferred orientation;

[0048] Among them, the specific process parameters adopted by the magnetron sputtering technology include: the gas pressure in the reaction chamber is 0.4 - 0.6 Pa, the substrate negative bias voltage is 100 V, the metal target power is 12 - 15 kW, the chamber temperature during the deposition process is 200 - 450 °C, the total deposition time is 10 - 20 h, and the volume fraction of acetylene gas in the working gas is 7% - 20%.

[0049] Another aspect of the embodiment of the present invention also provides a (HfZr)C anti-ultra-high temperature ablation coating prepared by the aforementioned preparation method 1-x coating, and the (HfZr)C 1-x coating has a face-centered cubic structure with a (111) crystal plane preferred orientation.

[0050] Furthermore, the thickness of the (HfZr)C anti-ultra-high temperature ablation 1-x coating is 37 - 45 μm.

[0051] Furthermore, at room temperature, the nano-hardness of the (HfZr)C anti-ultra-high temperature ablation 1-x coating is 12 - 24 GPa, and the elastic modulus is 200 - 300 GPa.

[0052] Another aspect of the embodiment of the present invention also provides the application of the aforementioned (HfZr)C anti-ultra-high temperature ablation 1-x coating in the field of aerospace anti-ablative protective coatings.

[0053] For example, the application in the anti-ablative protective coatings of key components such as the head, wing or engine tail nozzle of an aircraft.

[0054] In summary, the (HfZr)C prepared by the method in the present invention 1-xThe coating has a continuous and dense microstructure. The coating is mainly composed of columnar crystals, with no obvious gaps between grains. The coating and the substrate are well-bonded, with no obvious voids. In the high-temperature ablation evaluation test, the coating can exist on the substrate in the temperature range of 1000 - 1700 °C, avoiding direct contact between the ablation environment and the substrate material, and alleviating the damage to the substrate caused by high-temperature ablation. The implementation of the technical solution does not require complex equipment and preparation methods. Only a simple magnetron sputtering method is needed. The temperature range during the preparation process is wide, and the coating can be deposited on the surfaces of various materials. By regulating the acetylene flux during the deposition process, the types and relative volume ratios of the phases in the coating can be precisely regulated, realizing the differentiation of the ablation-resistant protection function. The obtained coating has potential application prospects in the field of ultra-high temperature ablation-resistant protection.

[0055] The present invention discloses a (HfZr)C coating resistant to ultra-high temperature ablation 1-x and its preparation method and application. The preparation method of the (HfZr)C 1-x coating includes: using magnetron sputtering technology, with elemental metal Hf and Zr targets as the targets, acetylene and argon as the working gases, applying target power to the Hf and Zr targets, applying negative bias voltage to the substrate, and depositing the (HfZr)C 1- x coating on the surface of the substrate. This coating has a face-centered cubic structure with a preferred orientation of (111). The present invention prepares an ablation-resistant protection coating on graphite and silicon carbide substrates, uses magnetron sputtering technology and adjusts the acetylene flux to change the carbon content in the coating, and prepares a (HfZr)C 1-x solid solution coating system with variable composition. The change in the types and contents of the coating phases will lead to different ablation-resistant performances, and the high melting point characteristics of (HfZr)C 1-x and its oxides help to block direct contact between the high-temperature environment and the substrate material, significantly reducing the damage caused by the ablation environment to the substrate.

[0056] The following further details the technical solution of the present invention in conjunction with several preferred embodiments and the accompanying drawings. These embodiments are implemented on the premise of the technical solution of the present invention, and the detailed implementation methods and specific operation processes are given. However, the protection scope of the present invention is not limited to the following embodiments.

[0057] In the following embodiments, the experimental materials used, unless otherwise specified, can be purchased from conventional biochemical reagent companies.

[0058] Example 1

[0059] In this example, the preparation method of the (HfZr)C 1-x coating uses magnetron sputtering technology to deposit a protective coating with a thickness of about 35 - 40 μm on the surface of the graphite substrate. The main steps are as follows:

[0060] (1) Mechanically polish the surface of the graphite matrix sample, and then ultrasonically clean it with acetone and alcohol respectively for 30 minutes each.

[0061] (2) Install the cleaned sample on the bracket inside the cavity, and evacuate the cavity until the vacuum degree inside the cavity reaches 0.4 Pa, then heat it to a temperature of 400 °C.

[0062] (3) Etch the pre-installed target and the matrix to remove the adsorbed contaminants on the surface for 10 minutes each. Apply a negative bias voltage of 600 V during the etching of the matrix.

[0063] (4) Deposit the (HfZr)C 1-x coating. Use pure metal targets of Hf and Zr, with a target power of 12 kW, an acetylene flux of 40 seem, argon as the protective gas, a matrix negative bias voltage of 100 V, a deposition time of 15 h, and a turntable rotation speed of 2 rpm.

[0064] (5) In this embodiment, the hardness of the coating is 24 GPa and the elastic modulus is 310 GPa.

[0065] (6) Refer to the ablation test standard of GJB 323A - 1996 for ablation materials. Use the oxy-acetylene ablation method to evaluate the ablation resistance performance of the (HfZr)C 1-x coating on the surface of the graphite matrix at 1200 °C. The flame gun is about 20 mm away from the coating, and the ablation time is 60 s.

[0066] (7) Figures 1a - 1b This is the surface morphology of the (HfZr)C 1-x coating after the ablation test in this embodiment and the curve of the surface temperature change of the coating during the ablation process. During the ablation process at 1200 °C, the coating basically remains intact and there is no obvious peeling phenomenon.

[0067] (8) Figures 2a - 2d This is the element distribution of the surface coating after ablation. There is a significant oxidation phenomenon on the ablation coating surface, and the surface is basically covered by oxides of Hf and Zr. The high melting point and high stability characteristics of the oxides can reduce the surface damage of the matrix.

[0068] Example 2

[0069] The method for preparing the (HfZr)C 1-x coating described in this embodiment uses magnetron sputtering technology to deposit a protective coating with a thickness of about 35 - 40 μm on the surface of the silicon carbide matrix. The main steps are as follows:

[0070] (1) Mechanically polish the surface of the matrix sample, and then ultrasonically clean it with acetone and alcohol respectively for 30 minutes each.

[0071] (2) Install the cleaned specimen on the bracket inside the cavity, and evacuate the cavity until the vacuum degree inside the cavity reaches 0.5 Pa, then heat the vacuum cavity to a temperature of 400 °C.

[0072] (3) Etch the pre-installed target and substrate to remove the adsorbed surface contaminants, with the time for both being 10 min, and apply a negative bias voltage of 600 V during the etching of the substrate.

[0073] (4) When preparing the deposited HfZrC coating, use pure metal targets of Hf and Zr, with the target power being 12 kW, the acetylene flux being 45 sccm, the protective gas being argon, the substrate negative bias voltage being 100 V, the deposition time being 20 h, and the turntable rotation speed being 2 rpm.

[0074] (5) In this embodiment, the hardness of the coating is 22 GPa and the elastic modulus is 300 GPa.

[0075] (6) Referring to the ablation test standard of GJB 323A-1996 for ablation materials, use the oxy-acetylene ablation method to evaluate the ablation resistance performance of the (HfZr)C coating on the surface of the silicon carbide substrate at 1500 °C. The flame gun is about 15 mm away from the coating, and the ablation time is 60 s. 1-x The ablation time is 60 s.

[0076] (7) Figures 3a - 3b For the (HfZr)C coating after the ablation test in this embodiment 1-x The surface morphology of the coating and the curve of the surface temperature change of the coating during the ablation process are shown. During the ablation process, the coating basically remains intact without obvious peeling phenomenon. The complete protective coating helps to relieve the high-temperature damage caused by the ablation environment to the substrate and reduce the ablation failure rate.

[0077] Example 3

[0078] The method for preparing the (HfZr)C coating described in this embodiment 1-x uses the magnetron sputtering technique to deposit a protective coating with a thickness of about 35 - 40 μm on the surface of the silicon carbide substrate. The main steps are as follows:

[0079] (1) Mechanically polish the surface of the substrate specimen, and then ultrasonically clean it with acetone and alcohol respectively for 30 min each.

[0080] (2) Install the cleaned specimen on the bracket inside the cavity, and evacuate the cavity until the vacuum degree inside the cavity reaches 0.5 Pa, then heat the vacuum cavity to a temperature of 450 °C.

[0081] (3) Etch the pre-installed target and substrate to remove the adsorbed surface contaminants, with the time for both being 10 min, and apply a negative bias voltage of 600 V during the etching of the substrate.

[0082] (4) When preparing the deposited HfZrC coating, pure metal targets of Hf and Zr are used, the target power is 12 kW, the acetylene flux is 50 sccm, the protective gas is argon, the substrate negative bias voltage is 150 V, the deposition time is 20 h, and the turntable rotation speed is 2 rpm.

[0083] (5) In this embodiment, the hardness of the coating is 13 GPa and the elastic modulus is 210 GPa.

[0084] (6) Referring to the ablation test standard of GJB 323A - 1996 for ablation materials, the oxy - acetylene ablation method is adopted to evaluate the ablation resistance performance of the (HfZr)C coating on the surface of the silicon carbide substrate at 1300 °C. The flame gun is about 20 mm away from the coating, and the ablation time is 60 s. 1-x The ablation resistance performance of the coating is evaluated. The flame gun is about 20 mm away from the coating, and the ablation time is 60 s.

[0085] (7) Figures 4a - 4b For the (HfZr)C coating after the ablation test in this embodiment 1-x The surface morphology of the coating and the curve of the surface temperature change of the coating during the ablation process are shown. During the ablation process, the coating basically remains intact without obvious peeling phenomenon. The complete protective coating helps to relieve the high - temperature damage caused by the ablation environment to the substrate and reduce the ablation failure rate.

[0086] Example 4

[0087] The method for preparing the (HfZr)C coating described in this embodiment 1-x adopts the magnetron sputtering technology to deposit a protective coating with a thickness of about 35 - 40 μm on the surface of the graphite substrate. The main steps are as follows:

[0088] (1) The surface of the graphite substrate sample is mechanically polished, and then ultrasonically cleaned with acetone and alcohol respectively for 30 min each.

[0089] (2) The cleaned sample is installed on the bracket in the cavity, and the cavity is evacuated until the vacuum degree in the cavity reaches 0.4 Pa and then heated to a temperature of 200 °C.

[0090] (3) The pre - installed target and the substrate are etched to remove the adsorbed surface contaminants for 10 min each. A negative bias voltage of 500 V is applied during the etching of the substrate.

[0091] (4) When depositing the (HfZrC) 1-x coating, pure metal targets of Hf and Zr are used, the target power is 15 kW, the acetylene flux is 20 sccm, the protective gas is argon, the substrate negative bias voltage is 50 V, the deposition time is 15 h, and the turntable rotation speed is 2 rpm.

[0092] (5) The (HfZrC) prepared in this embodiment1-x The coating has good ablation resistance, slightly worse than that of Example 1.

[0093] Example 5

[0094] In the preparation method of the (HfZr)C1-x coating described in this example, a protective coating with a thickness of about 35 - 40 μm was deposited on the surface of the graphite substrate by magnetron sputtering technology. The main steps are as follows:

[0095] (1) The surface of the graphite substrate sample was mechanically polished, and then ultrasonically cleaned with acetone and alcohol respectively for 30 minutes each.

[0096] (2) The cleaned sample was installed on the bracket in the cavity, and the cavity was evacuated until the vacuum degree in the cavity reached 0.4 Pa and then heated to a temperature of 300 °C.

[0097] (3) The pre-installed target and the substrate were etched to remove the adsorbed contaminants on the surface for 10 minutes each. A negative bias voltage of 550 V was applied during the etching of the substrate.

[0098] (4) Deposit the (HfZr)C 1-x coating. Hf and Zr pure metal targets were used. The target power was 13 kW, the acetylene flux was 60 sccm, the protective gas was argon, the substrate negative bias voltage was 150 V, the deposition time was 15 h, and the turntable rotation speed was 2 rpm.

[0099] (5) The (HfZr)C 1-x coating prepared in this example has good ablation resistance, slightly worse than that of Example 1.

[0100] Comparative Example 1

[0101] The method is the same as that of Example 1, except that the Hf pure metal target is missing. The coating consists of a single ZrC, and the ablation resistance of the coating was evaluated under the same test conditions. Figure 5 Figure shows the macroscopic morphology of the graphite sample after the ablation test. During the test, rapid spalling of the coating occurred. After the test, the coating on the surface of the graphite sample completely peeled off, exposing the graphite substrate to the ablation damage environment.

[0102] Comparative Example 2

[0103] The method is the same as that of Example 1, except that the Zr pure metal target is missing. The coating consists of a single HfC, and the ablation resistance of the coating was evaluated under the same test conditions. Figure 6 Figure shows the macroscopic morphology of the SiC sample after the ablation test. During the test, rapid spalling of the coating occurred. After the test, the coating on the surface of the SiC sample completely peeled off, failing to avoid the ablation damage of the SiC substrate.

[0104] In addition, with reference to the foregoing embodiments, the inventors of this case also conducted tests using other raw materials, process operations, and process conditions described in this specification, and all obtained relatively ideal results.

[0105] It should be understood that the technical solutions of the present invention are not limited to the limitations of the above specific embodiments. Any technical deformation made according to the technical solutions of the present invention without departing from the gist of the present invention and the scope protected by the claims falls within the protection scope of the present invention.

Claims

1. A kind of ultra-high temperature ablation resistant (HfZr)C 1-x The method for preparing the coating is characterized in that: include: providing a substrate; And, using magnetron sputtering technology, using Hf target and Zr target as target materials, using carbon source gas as working gas, so as to deposit ultra-high temperature ablation resistant (HfZr)C on the surface of the substrate 1-x coating; wherein the (HfZr)C 1-x The coating has a face-centered cubic structure with a preferred orientation of the (111) crystal plane.

2. The preparation method according to claim 1, characterized in that: The ultra-high temperature ablation resistant (HfZr)C 1-x The coating is composed of nano-scale carbide (HfZr)C 1-x Particle composition; And / or, the ultra-high temperature ablation resistant (HfZr)C 1-x The coating consists of Hf metal, Zr metal and carbon-poor (HfZr)C 1-x Carbides, where 0<x<1; And / or, the ultra-high temperature ablation resistant (HfZr)C 1-x The coating composition includes carbides and amorphous carbon in a stoichiometric ratio of (HfZr)C.

3. The preparation method according to claim 1, characterized in that: Specifically include: The magnetron sputtering technology is adopted, Hf target and Zr target are used as target materials, carbon source gas and inert gas are used as working gas, negative bias voltage is applied to the substrate, target power is applied to the target material, so that ultra-high temperature ablation-resistant (HfZr)C is deposited on the surface of the substrate. 1-x Coating; wherein, the gas pressure in the reaction chamber is 0.4-0.6Pa, the target power is 12-15kW, the substrate negative bias voltage is 50-150V, the temperature of the reaction chamber is 200-450℃, the deposition time is 10-20h, the flux of the carbon source gas is 20-60sccm, and the flux of the inert gas is 150-350sccm.

4. The preparation method according to claim 3, characterized in that: The carbon source gas includes acetylene; and / or, the inert gas comprises argon; And / or, the volume fraction of the carbon source gas in the working gas is 7%-20%; And / or, the substrate includes a graphite substrate or a silicon carbide substrate.

5. The preparation method according to claim 1, characterized in that: Also includes: The substrate is first surface pretreated, and then magnetron sputtering technology is used to deposit ultra-high temperature ablation-resistant (HfZr)C on the substrate surface. 1-x Coating; wherein the surface pretreatment includes surface treatment and ion bombardment cleaning treatment.

6. The preparation method according to claim 5, characterized in that: The surface pretreatment includes: grinding and polishing the substrate, followed by ultrasonic cleaning; preferably, the grinding and polishing treatments at least make the surface roughness of the substrate 2-3 μm.

7. The preparation method according to claim 5, characterized in that: The ion bombardment cleaning process comprises: placing the substrate obtained by surface treatment at a temperature of 200-450°C and a vacuum degree of 4-6×10 -3 Argon gas is introduced into the Pa counter cavity, and a negative bias voltage of 500-600V is applied to the substrate, and then the surface of the substrate is cleaned by ion bombardment.

8. The preparation method according to claim 1, characterized in that: Also includes: In the ultra-high temperature ablation resistant (HfZr)C 1-x After the coating deposition is completed, wait until the reaction temperature of the chamber drops below 100°C and take out the (HfZr)C 1-x The substrate of the coating.

9. Ultra-high temperature ablation resistant (HfZr)C prepared by the preparation method according to any one of claims 1 to 8 1-x A coating, characterized in that: The (HfZr)C 1-x The coating has a face-centered cubic structure with a preferred orientation of the (111) crystal plane; Preferably, the ultra-high temperature ablation resistant (HfZr)C 1-x The thickness of the coating is 37-45 μm; preferably, at room temperature, the ultra-high temperature ablation resistant (HfZr)C 1-x The nanohardness of the coating is 12-24 GPa, and the elastic modulus is 200-300 GPa.

10. The ultra-high temperature ablation resistant (HfZr)C according to claim 9 1-x The coating is used in the field of ablation-resistant protective coatings for aerospace; preferably, it is used in ablation-resistant protective coatings for key components such as the head, wings or tail nozzle of an aircraft.

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