High-temperature anti-oxidation ablation material and preparation method and application thereof

Abstract

The invention relates to a high-temperature anti-oxidation ablation material as well as a preparation method and application thereof. The chemical composition of the high-temperature oxidation-resistant ablation material powder is (Hfx, Zry, Taz, Tip, Wq, Mom) B < 2-nvol% SiC, (Hfx, Zry, Taz, Tip, Wq, Mom) C-nvol% SiC or (xHfB < 2-y > ZrB < 2-z > TaB < 2-p > TiB < 2-q > WB < 2-m > MoB < 2 >)-n vol% SiC, (xHfC-y > ZrC-z > TaC-p TiC-q > WC-mMoC)-nvol% SiC, wherein the value of x and the value of y are both 0.05-0.9, preferably 0.5-0.9, the value of z and the value of p are both 0.01-0.2, the value of q and the value of m are both 0-0.05, x + y + z + p + q + m = 1, and the value of n is 0-20.

Description

Technical Field

[0001] This invention belongs to the field of ultra-high temperature ceramic materials technology, specifically relating to a high-temperature oxidation-resistant ablation boride / carbide-based powder material, its preparation method, and its application in ceramics and coating materials. Background Technology

[0002] Borides and carbides, as typical representatives of ultra-high temperature ceramics, possess properties such as high melting point, high thermal conductivity, low coefficient of thermal expansion, high chemical stability, low catalytic coefficient, and high emissivity, making them a class of high-temperature structural materials with broad application prospects in the aerospace field. However, single-phase borides and carbides suffer from poor oxidation resistance, limiting their application at high temperatures. Taking ZrB2 as an example, ZrB2 undergoes significant oxidation above 800℃ (ZrB2 + 5 / 2O2 = ZrO2 + B2O3). The oxidation product B2O3 can hinder oxygen permeation at temperatures below 1000℃, but when the temperature exceeds 1200℃, B2O3 rapidly volatilizes, forming a porous oxide layer that fails to provide protection, thus continuously oxidizing ZrB2.

[0003] Adding silicides to borides and carbides can improve the density and oxidation resistance of borides / carbides. Silicides oxidize at high temperatures to form a stable glassy phase, SiO2, which better isolates oxygen penetration. However, with increasing service temperatures, the vigorous volatilization of SiO2 can damage the oxide layer structure, forming a porous morphology, especially when the temperature exceeds its boiling point (2200℃). Summary of the Invention

[0004] To address the aforementioned technical problems, the present invention aims to provide a high-temperature resistant oxidative ablation boride / carbide-based powder material, its preparation method, and its application in ceramics and coating materials.

[0005] In a first aspect, the present invention provides a high-temperature antioxidant ablation material powder, wherein the chemical composition of the high-temperature antioxidant ablation material powder is: (Hf x ,Zr y ,Ta z Ti p W q Mo m B2-nvol%SiC, (Hf) x ,Zr y ,Ta z Ti p W q Mo m)C-nvol%SiC or (xHfB2-yZrB2-zTaB2-pTiB2-qWB2-mMoB2)-n vol%SiC, (xHfC-yZrC-zTaC-pTiC-qWC-mMoC)-nvol%SiC; Wherein: the values ​​of x and y are both 0.05 to 0.9, preferably 0.5 to 0.9, the values ​​of z and p are both 0.01 to 0.2, the values ​​of q and m are both 0 to 0.05, x+y+z+p+q+m=1, and the value of n is 0 to 20.

[0006] Preferably, the preparation process of the high-temperature antioxidant ablation material powder includes a direct mixing method or a thermal reduction method.

[0007] Preferably, the direct mixing method includes the following steps: weighing metal boride or metal carbide and silicon carbide powder according to the chemical composition stoichiometry of the above-mentioned high-temperature anti-oxidation and ablation material powder, and mixing them evenly to obtain the final product.

[0008] Preferably, the thermal reduction method includes the following steps: according to the chemical composition stoichiometry of the above-mentioned high-temperature anti-oxidation ablation material powder, the oxide powder corresponding to the metal element in the metal boride or metal carbide is weighed and subjected to thermal reduction reaction with B4C or C powder to synthesize metal boride or metal carbide solid solution powder, and then silicon carbide powder is mixed evenly with the metal boride or metal carbide solid solution powder to obtain the final product.

[0009] Secondly, the present invention provides a high-temperature oxidation-resistant ablation ceramic material, wherein the preparation method of the high-temperature oxidation-resistant ablation ceramic material includes the following steps: sintering the above-mentioned high-temperature oxidation-resistant ablation material powder by discharge plasma sintering or hot pressing sintering to obtain the high-temperature oxidation-resistant ablation ceramic material.

[0010] Preferably, the process parameters for the discharge plasma sintering include: vacuum degree 50-200 Pa, heating rate 100-200 °C / min, sintering temperature 1500-2200 °C, sintering pressure 10-60 MPa, and sintering time 5-30 min.

[0011] Preferably, the process parameters for hot pressing sintering include: vacuum degree 50-200 Pa, heating rate 5-30 °C / min, sintering temperature 1500-2200 °C, sintering pressure 10-60 MPa, and sintering time 30-300 min.

[0012] Thirdly, the present invention provides a high-temperature anti-oxidation ablation coating. The preparation method of the high-temperature anti-oxidation ablation coating includes the following steps: the above-mentioned high-temperature anti-oxidation ablation material powder is sequentially subjected to ball milling, spray granulation and high-temperature heat treatment to obtain spherical powder suitable for spraying, and then sprayed onto the substrate surface by plasma spraying technology to obtain the high-temperature anti-oxidation ablation coating.

[0013] Preferably, the process parameters of the plasma spraying technology include: plasma generating gas Ar: 30-50 slpm, plasma generating gas H2: 2-20 slpm, powder carrier gas Ar: 3-10 slpm; spraying distance: 100-350 mm; spraying power: 30-55 kW; powder feeding rate: 5-40 rpm; spraying pressure: 100-1000 mbar; spraying atmosphere: air or argon atmosphere, preferably argon atmosphere.

[0014] Preferably, the matrix includes C / C composite material, C / SiC composite material, SiC / SiC composite material, ceramic-modified composite material, or metal and its alloy material.

[0015] Beneficial effects The ceramic and coating materials prepared by the high-temperature anti-oxidation and ablation material powder with specific chemical composition designed by the present invention have the following characteristics: (1) They have a solid solution microstructure and good high-temperature structural stability; (2) In oxygen-containing or oxygen-rich high-temperature environments, they can generate an oxide layer with a dense structure. The oxide layer is thin, has good oxygen diffusion barrier properties, and has the characteristics of being resistant to airflow erosion and having a low volatilization rate, which makes the material have excellent anti-oxidation and anti-ablation properties in high-temperature or ultra-high-temperature environments; (3) The coating material has a low coefficient of thermal expansion and good bonding performance with composite materials. Attached Figure Description

[0016] Figure 1 The boride solid solution (Hf) prepared in Example 1 4 / 5 ,Zr 1 / 15 ,Ta 1 / 15 Ti 1 / 15 SEM image of B2 powder; Figure 2 The (Hf) prepared in Examples 1 and 2 and Comparative Examples 1 and 2 4 / 5 ,Zr 1 / 15 ,Ta 1 / 15 Ti 1 / 15 B2、(Zr) 13 / 30 ,Hf 13 / 30 ,Ta 1 / 15 Ti 1 / 15 )B2、ZrB2、(Zr 1 / 4 ,Hf 1 / 4 ,Ta 1 / 4 Ti1 / 4 XRD pattern of B2 ceramic material; Figure 3 The (Hf) prepared in Examples 1, 2 and Comparative Example 2 4 / 5 ,Zr 1 / 15 ,Ta 1 / 15 Ti 1 / 15 B2、(Zr) 13 / 30 ,Hf 13 / 30 ,Ta 1 / 15 Ti 1 / 15 B2、(Zr) 1 / 4 ,Hf 1 / 4 ,Ta 1 / 4 Ti 1 / 4 B2 Cross-sectional morphology and elemental distribution diagram of ceramic materials; Figure 4 The (Hf) prepared in Examples 1 and 2 and Comparative Examples 1 and 2 4 / 5 ,Zr 1 / 15 ,Ta 1 / 15 Ti 1 / 15 B2、(Zr) 13 / 30 ,Hf 13 / 30 ,Ta 1 / 15 Ti 1 / 15 )B2、ZrB2、(Zr 1 / 4 ,Hf 1 / 4 ,Ta 1 / 4 Ti 1 / 4 Macroscopic morphology of B2 ceramic block after laser ablation; Figure 5 The (Hf) prepared in Example 1 4 / 5 ,Zr 1 / 15 ,Ta 1 / 15 Ti 1 / 15 Cross-sectional morphology of B2 ceramic after laser ablation; Figure 6 The (Zr) prepared in Example 2 13 / 30 ,Hf 13 / 30 ,Ta 1 / 15 Ti 1 / 15 Cross-sectional morphology of B2 ceramic after laser ablation; Figure 7 The image shows the cross-sectional morphology of the ZrB2 ceramic prepared in Comparative Example 1 after laser ablation. Figure 8 The (Zr) prepared in Comparative Example 2 1 / 4 ,Hf 1 / 4 ,Ta 1 / 4 Ti 1 / 4 Cross-sectional morphology image after B2 laser ablation; Figure 9 The (Hf) prepared in Examples 3-5 and Comparative Examples 3 and 44 / 5 ,Zr 1 / 15 ,Ta 1 / 15 Ti 1 / 15 B2、(Hf) 4 / 5 ,Zr 1 / 15 ,Ta 1 / 15 Ti 1 / 15 B2-10 vol.% SiC, (Zr) 4 / 5 ,Hf 1 / 20 ,Ta 1 / 20 Ti 1 / 20 W 1 / 20 )B2-20vol.%SiC, ZrB2-30vol.%SiC, (Hf 1 / 4 ,Zr 1 / 4 ,Ta 1 / 4 Ti 1 / 4 XRD pattern of B2 coating; Figure 10 (Hf) prepared in Example 3 4 / 5 ,Zr 1 / 15 ,Ta 1 / 15 Ti 1 / 15 Cross-sectional morphology of coating B2; Figure 11 (Hf) prepared in Example 3 4 / 5 ,Zr 1 / 15 ,Ta 1 / 15 Ti 1 / 15 Macroscopic morphology of B2 coating after plasma flame ablation; Figure 12 (Hf) prepared in Example 4 4 / 5 ,Zr 1 / 15 ,Ta 1 / 15 Ti 1 / 15 Macroscopic morphology of B2-10 vol.% SiC coating after plasma flame ablation; Figure 13 The (Zr) prepared in Example 5 4 / 5 ,Hf 1 / 20 ,Ta 1 / 20 Ti 1 / 20 W 1 / 20 Macroscopic morphology of B2-20 vol.% SiC coating after plasma flame ablation; Figure 14 The image shows the macroscopic morphology of the ZrB2-30 vol% SiC coating prepared in Comparative Example 3 after plasma flame ablation. Figure 15 The (Hf) prepared in Comparative Example 4 1 / 4 ,Zr 1 / 4 ,Ta 1 / 4 Ti 1 / 4Macroscopic morphology of B2 coating after plasma flame ablation. Detailed Implementation

[0017] The present invention will be further illustrated by the following embodiments. It should be understood that the following embodiments are for illustrative purposes only and are not intended to limit the present invention.

[0018] First, this invention provides a boride-based or carbide-based high-temperature oxidation-resistant ablation material powder with excellent high-temperature oxidation-resistant ablation properties. The chemical composition of the high-temperature oxidation-resistant ablation material powder can be: (hafnium Hf...) x Zirconium (Zr) y ,Ta z Titanium (Ti) p , Tungsten W q ,Molybdenum Mo m B2-nvol%SiC, (Hf) x ,Zr y ,Ta z Ti p W q Mo m The formula is (xHfB2-yZrB2-zTaB2-pTiB2-qWB2-mMoB2)-n vol%SiC or (xHfC-yZrC-zTaC-pTiC-qWC-mMoC)-n vol%SiC; wherein: the values ​​of x and y are both 0.05 to 0.9, preferably 0.5 to 0.9, the values ​​of z and p are both 0.01 to 0.2, the values ​​of q and m are both 0 to 0.05, x+y+z+p+q+m=1, and the value of n is 0 to 20.

[0019] Among them, HfB2, ZrB2, TaB2, and TiB2 are all hexagonal crystal systems with similar atomic radii. Similarly, ZrC, HfC, TaC, and TiC are all face-centered cubic crystals. Therefore, the boride-based and carbide-based high-temperature oxidation-resistant ablation material powders provided by this invention readily form continuous solid solutions at high temperatures. The formation of solid solutions not only improves the high-temperature strength and hardness of the material, but also, because the solid solutions contain two or more transition gold elements, the high-temperature oxidation resistance of the material can be improved through the synergistic effect of multiple transition gold oxides.

[0020] It should be noted that the chemical composition of the high-temperature anti-oxidation ablation material powder provided by this invention involves non-equimolar proportions of various metals, and the proportions of Hf and Zr are controlled to be greater than or equal to the proportions of Ta and Ti. If the metal elements are proportioned in equimolar ratios to form a high-entropy boron / carbide, such as (Hf... 1 / 4 ,Zr 1 / 4 ,Ta 1 / 4 Ti 1 / 4B2, where the oxidation products of Ti and Ta elements have low melting points, will lead to (Hf) 1 / 4 ,Zr 1 / 4 ,Ta 1 / 4 Ti 1 / 4 The oxide layer formed by SiO2 under ultra-high temperature environments contains excessive liquid substances, making it unable to form a stable structure. Especially under airflow erosion conditions, the coating is prone to failure, resulting in a short service life. Therefore, appropriately reducing the proportion of Ta and Ti elements and increasing the proportion of Hf and Zr elements can adjust the composition of the oxidation products, particularly the ratio of high-melting-point solid-phase oxidation products to low-melting-point liquid-phase oxidation products, thereby improving the material's overall resistance to oxidation, ablation, and airflow erosion. Furthermore, the liquid products (oxides of Ti and Ta) have high boiling points, which can compensate for the low boiling point and rapid volatilization rate of SiO2. Therefore, the material composition provided by this invention exhibits superior oxidation and ablation resistance.

[0021] In some embodiments, the preparation process of the high-temperature antioxidant ablation material powder may include a direct mixing method or a thermal reduction method.

[0022] The direct mixing method may include the following steps: weighing metal boride or metal carbide and silicon carbide powder according to the chemical composition stoichiometry of the above-mentioned high-temperature anti-oxidation ablation material powder, and mixing them evenly to obtain the final product.

[0023] In some embodiments, in the direct mixing method, the purity of the metal boride, metal carbide, and silicon carbide powder is ≥99.0wt%, and the particle size range can be 0.1 to 10 μm.

[0024] The thermal reduction method may include the following steps: according to the chemical composition stoichiometry of the above-mentioned high-temperature anti-oxidation and ablation material powder, the oxide powder corresponding to the metal element in the metal boride or metal carbide is weighed and subjected to thermal reduction reaction with B4C or C powder to synthesize metal boride solid solution powder or metal carbide solid solution powder, and then silicon carbide powder is mixed evenly with the metal boride solid solution or metal carbide solid solution powder to obtain the final product.

[0025] In some embodiments, in the thermal reduction method, the purity of the oxide powder corresponding to the metal element in the metal boride or metal carbide is ≥99.0wt%, and the particle size range can be 0.1 to 10 μm.

[0026] In some embodiments, in the thermal reduction method, the mass of B4C and C powders can be 10-40 wt% of the total mass of the metal oxide powders; the purity of B4C and C powders can be ≥99.0 wt%, and the particle size range can be 0.1-10 μm.

[0027] In some embodiments, the thermal reduction reaction can be carried out under vacuum conditions, with a vacuum degree of 50-200 Pa, a heating rate of 5-15 °C / min, a reaction temperature of 1500-2000 °C, and a holding time of 2-6 h.

[0028] In some embodiments, the purity of the metal boride solid solution powder, the metal carbide solid solution powder, and the silicon carbide powder can all be ≥99.0wt%, and the particle size range can all be 0.1~10μm.

[0029] This invention also provides a high-temperature oxidation-resistant ablation ceramic material prepared using the aforementioned high-temperature oxidation-resistant ablation material powder. Furthermore, the powder can be used as an additive phase in ceramics or composite materials to improve their resistance to high-temperature oxidation and ablation. As a high-temperature structural material, this material can be applied in high-temperature, oxygen-containing environments.

[0030] The preparation method of the high-temperature anti-oxidation and ablation ceramic material may include the following steps: sintering the above-mentioned high-temperature anti-oxidation and ablation material powder by discharge plasma sintering or hot pressing sintering to obtain the high-temperature anti-oxidation and ablation ceramic material.

[0031] In some embodiments, the process parameters of the spark plasma sintering may include: vacuum degree 50-200 Pa, heating rate 100-200 °C / min, sintering temperature 1500-2200 °C, sintering pressure 10-60 MPa, and sintering time 5-30 min.

[0032] In some embodiments, the process parameters of the hot pressing sintering may include: vacuum degree 50-200 Pa, heating rate 5-30 °C / min, sintering temperature 1500-2200 °C, sintering pressure 10-60 MPa, and sintering time 30-300 min.

[0033] The ablation resistance of the ceramic material is characterized by measuring the depth (or height) of ablation pits (or protrusions) on the surface of the high-temperature oxidation-resistant ablation ceramic after ablation using a super depth-of-field microscope, where the depth of the pits is negative and the height of the protrusions is positive. The microstructural changes of the high-temperature oxidation-resistant ablation ceramic before and after ablation are observed using a scanning electron microscope, and the thickness of the oxide layer after ablation is measured to characterize the ablation resistance of the bulk material.

[0034] The present invention also provides a high-temperature antioxidant ablation coating prepared using the above-mentioned high-temperature antioxidant ablation material powder. This coating material can significantly improve the high-temperature antioxidant ablation performance of the substrate material.

[0035] The preparation method of the high-temperature anti-oxidation ablation coating may include the following steps: ball milling, spray granulation and high-temperature heat treatment of the above-mentioned high-temperature anti-oxidation ablation material powder to obtain spherical powder suitable for spraying, and then spraying it on the substrate surface by plasma spraying technology to obtain the high-temperature anti-oxidation ablation coating.

[0036] In some embodiments, the high-temperature heat treatment can be performed at a temperature of 1300-2000°C for 1-6 hours.

[0037] In some embodiments, the process parameters of the plasma spraying technology may include: plasma generating gas Ar: 30-50 slpm, plasma generating gas H2: 2-20 slpm, powder carrier gas Ar: 3-10 slpm; spraying distance: 100-350 mm; spraying power: 30-55 kW; powder feeding rate: 5-40 rpm; spraying pressure: 100-1000 mbar; spraying atmosphere: air or argon atmosphere, preferably argon atmosphere.

[0038] In some embodiments, the matrix may include C / C composite materials, C / SiC composite materials, SiC / SiC composite materials, ceramic-modified composite materials, or metals and their alloys.

[0039] In some embodiments, the thickness l0 of the plasma-sprayed coating can be 100-1000 μm.

[0040] The ablation resistance of the bulk material is characterized by measuring the thickness change of the coating before and after ablation using a micrometer. The calculation formula is: R d =(l0-l t ) / t, where: R d l is the linear ablation rate, l0 is the original thickness of the coating sample, and l t t represents the thickness of the coating sample after ablation, and t represents the ablation time.

[0041] The following examples further illustrate the present invention in detail. It should also be understood that the following examples are only for further explanation of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention are within the scope of protection of the present invention. The specific process parameters, etc., in the following examples are merely examples within a suitable range; that is, those skilled in the art can make appropriate selections within the range based on the description herein, and are not intended to be limited to the specific values ​​in the examples below. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.

[0042] Example 1

[0043] The preparation method of high-temperature antioxidant ablation material powder and ceramic material provided in this embodiment includes the following steps: (1) According to (Hf) 4 / 5 ,Zr 1 / 15 ,Ta 1 / 15 Ti 1 / 15 The chemical composition of B2 was determined by weighing HfO2, ZrO2, Ta2O5, and TiO2 powders, each with a purity of 99.0 wt.% and a particle size of 0.1–10 μm, and adding them to a ball mill jar. Then, 20 wt% of B4C, with a purity of 99.0 wt% and a particle size range of 0.1–10 μm, was added and mixed. The mixed powder was then subjected to a boronothermic reduction reaction under ultra-high temperature heat treatment to obtain a boride solid solution (HfO2). 4 / 5 ,Zr 1 / 15 ,Ta 1 / 15 Ti 1 / 15 B2 powder. (2) Using spark plasma sintering technology (heating rate 150℃ / min, sintering temperature 2000℃, sintering pressure 30MPa, sintering time 10min), a 5mm thick and 10mm diameter (Hf) shell was prepared in a vacuum environment. 4 / 5 ,Zr 1 / 15 ,Ta 1 / 15 Ti 1 / 15 B2 High-temperature oxidation-resistant ablation ceramic materials.

[0044] Example 2

[0045] The preparation methods of the high-temperature antioxidant ablation material powder and ceramic material provided in this embodiment are the same as those in Example 1. The main difference is that the chemical composition of the high-temperature antioxidant ablation boride-based powder is (Zr 13 / 30 ,Hf 13 / 30 ,Ta 1 / 15 Ti 1 / 15 )B2.

[0046] Comparative Example 1

[0047] The preparation methods of the material powder and ceramic material provided in this comparative example are the same as those in Example 1. The main difference is that the boride-based powder is prepared by direct mixing and its chemical composition is pure phase ZrB2.

[0048] Comparative Example 2

[0049] The preparation methods of the powder and ceramic materials provided in this comparative example are the same as those in Example 1. The main difference is that the chemical composition of the boride-based powder is (Zr 1 / 4 ,Hf 1 / 4 ,Ta 1 / 4 Ti 1 / 4 )B2.

[0050] Figure 1 The boride solid solution (Hf) prepared in Example 1 4 / 5 ,Zr 1 / 15 ,Ta 1 / 15 Ti 1 / 15 SEM image of B2 powder. As can be seen from the image, the powder prepared in Example 1 is in the form of aggregated particles with a size of approximately nanometers.

[0051] Figure 2 The (Hf) prepared in Examples 1 and 2 and Comparative Examples 1 and 2 4 / 5 ,Zr 1 / 15 ,Ta 1 / 15 Ti 1 / 15 B2、(Zr) 13 / 30 ,Hf 13 / 30 ,Ta 1 / 15 Ti 1 / 15 )B2、ZrB2、(Zr 1 / 4 ,Hf 1 / 4 ,Ta 1 / 4 Ti 1 / 4 XRD pattern of B2 ceramic material. As can be seen from the figure, the prepared ceramic bulk contains almost no impurity phases, and the diffraction peaks of the solid solution bulk are single, indicating good solid solution.

[0052] Figure 3 The (Hf) prepared in Examples 1, 2 and Comparative Example 2 4 / 5 ,Zr 1 / 15 ,Ta 1 / 15 Ti 1 / 15 B2、(Zr) 13 / 30 ,Hf 13 / 30 ,Ta 1 / 15 Ti 1 / 15 B2、(Zr) 1 / 4 ,Hf 1 / 4 ,Ta 1 / 4 Ti 1 / 4 Cross-sectional morphology and elemental distribution of the B2 ceramic material. As can be seen from the figure, the elemental distribution in the cross-section of the ceramic material prepared in the examples is uniform, indicating good solid solution properties.

[0053] A CO2 laser ablation testing system (Changzhou Lantai Optoelectronic Technology Co., Ltd., China) was used to test (Hf) 4 / 5 ,Zr 1 / 15 ,Ta 1 / 15 Ti 1 / 15The B2 ceramic block underwent ablation testing to examine its resistance to oxidation and ablation in a high-temperature, oxygen-rich environment. During the ablation process, a dual-color infrared pyrometer (Marathon MR1SC, Raytek, USA) was used to measure the surface temperature at the ablation center. The measured ablation temperature exceeded 1800℃, and the heat flux density was 71.6 MW / m³. 2 .

[0054] Figure 4 The (Hf) prepared in Examples 1 and 2 and Comparative Examples 1 and 2 4 / 5 ,Zr 1 / 15 ,Ta 1 / 15 Ti 1 / 15 B2、(Zr) 13 / 30 ,Hf 13 / 30 ,Ta 1 / 15 Ti 1 / 15 )B2、ZrB2、(Zr 1 / 4 ,Hf 1 / 4 ,Ta 1 / 4 Ti 1 / 4 Macroscopic morphology image of B2 ceramic bulk after laser ablation. As can be seen from the image, (Hf) 4 / 5 ,Zr 1 / 15 ,Ta 1 / 15 Ti 1 / 15 The surface of B2 ceramic is relatively smooth, without obvious pits or protrusions, indicating excellent resistance to oxidation and ablation. The height of the ablated area, measured using a super-depth-of-field microscope, is approximately 10 μm. (Zr) 13 / 30 ,Hf 13 / 30 ,Ta 1 / 15 Ti 1 / 15 The surface of the ZrB2 ceramic remained intact after ablation, with small ablation scars appearing at the ablation center, the height of which was approximately 162 μm. The ZrB2 ceramic block developed pits after CO2 ablation, with a depth of approximately -80 μm measured by hyper-depth-of-field. 1 / 4 ,Hf 1 / 4 ,Ta 1 / 4 Ti 1 / 4 After CO2 ablation, a large meteorite crater appeared on the B2 ceramic block. The depth of the crater was measured to be approximately -328 μm using a super depth-of-field microscope.

[0055] Figure 5 The (Hf) prepared in Example 1 4 / 5 ,Zr 1 / 15 ,Ta 1 / 15 Ti 1 / 15 Cross-sectional morphology of B2 ceramic after laser ablation. As can be seen from the figure, the internal structure of the oxide layer is relatively dense and the oxide layer is relatively thin, with a thickness of approximately 130 μm.

[0056] Figure 6 The (Zr) prepared in Example 2 13 / 30 ,Hf 13 / 30 ,Ta 1 / 15 Ti 1 / 15 Cross-sectional morphology of B2 ceramic after laser ablation. As can be seen from the figure, the internal structure of the oxide layer is relatively dense and the oxide layer is relatively thin, with a thickness of approximately 350 μm.

[0057] Figure 7 The image shows the cross-sectional morphology of the ZrB2 ceramic prepared in Comparative Example 1 after laser ablation. As can be seen from the image, the oxide layer contains pores and cracks, exhibiting a loose structure and easy detachment, indicating poor ablation resistance and limited protective effect.

[0058] Figure 8 The (Zr) prepared in Comparative Example 2 1 / 4 ,Hf 1 / 4 ,Ta 1 / 4 Ti 1 / 4 The image shows the cross-sectional morphology after B2 laser ablation. As can be seen from the image, the oxidation products volatilized violently under ultra-high temperature conditions, forming pits.

[0059] Table 1 below shows the observation of oxide layer thickness and morphology after ablation of four types of ceramic blocks prepared in Examples 1 and 2 and Comparative Examples 1 and 2 of this invention:

[0060] As can be seen from Table 1 above, in Comparative Example 2 (Zr 1 / 4 ,Hf 1 / 4 ,Ta 1 / 4 Ti 1 / 4 The thickness of the B2 ceramic oxide layer is 370 μm, while in Example 1, the (Hf) layer... 4 / 5 ,Zr 1 / 15 ,Ta 1 / 15 Ti 1 / 15 The oxide layer thickness of ZrB2 ceramic is approximately 130 μm, a reduction of about one-third, exhibiting excellent oxidation resistance compared to ZrB2 and (Zr) in the comparative example. 1 / 4 ,Hf 1 / 4 ,Ta 1 / 4 Ti 1 / 4 Compared to B2 ceramics, (Hf) 4 / 5 ,Zr 1 / 15 ,Ta 1 / 15 Ti 1 / 15 B2 ceramics exhibit advanced resistance to oxidation and ablation.

[0061] Example 3

[0062] The method for preparing high-temperature antioxidant ablation material powder and coating provided in this embodiment includes the following steps: (1) According to (Hf) 4 / 5 ,Zr 1 / 15 ,Ta 1 / 15 Ti 1 / 15 To determine the chemical composition of B2, weigh out HfB2, ZrB2, TaB2, and TiB2 powders with a purity of 99.0 wt.% and a particle size of 0.1–10 μm and add them to a ball mill jar. Then, pour in ethanol until all the powders are submerged. Mix the powders using a ball mill, pass the mixed powder through a spray granulation tower, and then treat the powders at high temperature to obtain spherical powders suitable for spraying. (2) Using vacuum plasma spraying technology (process parameters: plasma generating gas Ar 40 slpm, plasma generating gas H2 10 slpm, powder carrier gas Ar 8 slpm, spraying distance 280 mm, spraying power 40 kW, powder feeding rate 20 rpm, spraying pressure 100 mbar, argon spraying atmosphere), a 310 μm thick (Hf) layer was prepared on a C / C composite matrix with a SiC transition layer. 4 / 5 ,Zr 1 / 15 ,Ta 1 / 15 Ti 1 / 15 B2 High-temperature anti-oxidation and ablation coating.

[0063] Example 4

[0064] The preparation method of the high-temperature antioxidant ablation material powder and coating provided in this embodiment is the same as in Example 3, the main difference being that the chemical composition of the high-temperature antioxidant ablation material powder is (Hf 4 / 5 ,Zr 1 / 15 ,Ta 1 / 15 Ti 1 / 15 )B2-10vol%SiC.

[0065] Example 5

[0066] The preparation method of the high-temperature antioxidant ablation material powder and coating provided in this embodiment is the same as in Example 3, the main difference being that the chemical composition of the high-temperature antioxidant ablation material powder is (Zr 4 / 5 ,Hf 1 / 20 ,Ta 1 / 20 Ti 1 / 20 W 1 / 20 )B2-20vol.%SiC.

[0067] Comparative Example 3

[0068] The preparation methods of the material powder and coating provided in this comparative example are the same as those in Example 3, the main difference being that the chemical composition of the material powder is ZrB2-30 vol.% SiC.

[0069] Comparative Example 4

[0070] The preparation methods of the material powder and coating provided in this comparative example are the same as those in Example 4, the main difference being that the chemical composition of the material powder is (Hf) 1 / 4 ,Zr 1 / 4 ,Ta 1 / 4 Ti 1 / 4 )B2.

[0071] Figure 9 The (Hf) prepared in Examples 3-5 and Comparative Examples 3 and 4 4 / 5 ,Zr 1 / 15 ,Ta 1 / 15 Ti 1 / 15 B2、(Hf) 4 / 5 ,Zr 1 / 15 ,Ta 1 / 15 Ti 1 / 15 B2-10 vol.% SiC, (Zr) 4 / 5 ,Hf 1 / 20 ,Ta 1 / 20 Ti 1 / 20 W 1 / 20 )B2-20vol.%SiC, ZrB2-30vol.%SiC, (Hf 1 / 4 ,Zr 1 / 4 ,Ta 1 / 4 Ti 1 / 4 XRD pattern of B2 coating. As can be seen from the figure, each diffraction peak is independent and single, indicating that the coating has a single-phase structure with almost no impurity phase.

[0072] Figure 10 (Hf) prepared in Example 3 4 / 5 ,Zr 1 / 15 ,Ta 1 / 15 Ti 1 / 15 The cross-sectional morphology of the B2 coating is shown in the figure. As can be seen from the figure, the coating thickness is approximately 310 μm, the coating porosity is low, the interface bonding with the substrate is tight, and the coating quality is good.

[0073] The coatings prepared in Examples 3-5 and Comparative Examples 3 and 4 were subjected to ablation testing using a plasma flame ablation system (TA800, Beijing Qinhe Technology Co., Ltd., China) to examine their resistance to oxidation and ablation under high temperature, oxygen-rich, and strong airflow erosion conditions. During the ablation process, a dual-color infrared pyrometer (Marathon MR1SC, Raytek, USA) was used to measure the surface temperature at the ablation center. Measurements showed that the surface temperature of the coatings reached approximately 2100℃ during the ablation process, and the ablation time was as long as 600 seconds.

[0074] Figure 11(Hf) prepared in Example 3 4 / 5 ,Zr 1 / 15 ,Ta 1 / 15 Ti 1 / 15 Macroscopic morphology of the B2 coating after plasma flame ablation. The figure shows that (Hf) 4 / 5 ,Zr 1 / 15 ,Ta 1 / 15 Ti 1 / 15 The B2 coating maintained its morphology intact after 600s of ablation, with a linear ablation rate of only -0.18μm / s, exhibiting excellent ablation resistance.

[0075] Figure 12 (Hf) prepared in Example 4 4 / 5 ,Zr 1 / 15 ,Ta 1 / 15 Ti 1 / 15 Macroscopic morphology of B2-10 vol.% SiC coating after plasma flame ablation. The figure shows that (Hf) 4 / 5 ,Zr 1 / 15 ,Ta 1 / 15 Ti 1 / 15 The B2-10 vol.% SiC coating remained intact after ablation, with only small ablation marks at the ablation center and a linear ablation rate of only -0.29 μm / s, demonstrating excellent ablation resistance.

[0076] Figure 13 The (Zr) prepared in Example 5 4 / 5 ,Hf 1 / 20 ,Ta 1 / 20 Ti 1 / 20 W 1 / 20 Macroscopic morphology of B2-20 vol.% SiC coating after plasma flame ablation. The figure shows that (Zr... 4 / 5 ,Hf 1 / 20 ,Ta 1 / 20 Ti 1 / 20 W 1 / 20 The B2-20 vol.% SiC coating remained intact after 300 s of ablation, with small ablation marks appearing at the ablation center. The linear ablation rate was only -0.24 μm / s, demonstrating excellent ablation resistance.

[0077] Using the same equipment and conditions as in Example 3, ZrB2-30 vol.% SiC, (Hf 1 / 4 ,Zr 1 / 4 ,Ta 1 / 4 Ti 1 / 4 The B2 coating was tested, with an ablation time of 300s.

[0078] Figure 14The image shows the macroscopic morphology of the ZrB2-30 vol% SiC coating prepared in Comparative Example 3 after plasma flame ablation. As can be seen from the image, after ablation, the ZrB2-30 vol% SiC coating exhibits large ablation pits on its surface, exposing the black substrate, indicating that the coating has completely failed. The linear ablation rate of this coating is 2.43 μm / s, showing poor ablation resistance.

[0079] Figure 15 The (Hf) prepared in Comparative Example 4 1 / 4 ,Zr 1 / 4 ,Ta 1 / 4 Ti 1 / 4 Macroscopic morphology of the B2 coating after plasma flame ablation. The figure shows that (Hf) 1 / 4 ,Zr 1 / 4 ,Ta 1 / 4 Ti 1 / 4 The B2 coating showed huge holes on the ablation surface, exposing the substrate, indicating that the coating had failed. The linear ablation rate of the coating was 8.10 μm / s, showing poor ablation resistance.

[0080] Table 2 below shows the ablation conditions, linear ablation rates, and morphological observations of the coatings prepared in Examples 3-5 and Comparative Examples 3 and 4 of this invention:

[0081] Although the present invention has been described in detail through the preferred embodiments above, it should be understood that the above description should not be considered as a limitation of the present invention. Various modifications and substitutions to the present invention will be apparent to those skilled in the art after reading the above description. Therefore, the scope of protection of the present invention should be defined by the appended claims.

Claims

1. A high-temperature antioxidant ablation material powder, characterized in that, The chemical composition of the high-temperature antioxidant ablation material powder is: (Hf x ,Zr y ,Ta z Ti p W q Mo m B2-nvol%SiC, (Hf) x ,Zr y ,Ta z Ti p W q Mo m )C-nvol%SiC or (xHfB2-yZrB2-zTaB2-pTiB2-qWB2-mMoB2)-n vol%SiC, (xHfC-yZrC-zTaC-pTiC-qWC-mMoC)-nvol%SiC; Wherein: the values ​​of x and y are both 0.05 to 0.9, preferably 0.5 to 0.9, the values ​​of z and p are both 0.01 to 0.2, the values ​​of q and m are both 0 to 0.05, x+y+z+p+q+m=1, and the value of n is 0 to 20.

2. The high-temperature anti-oxidation and ablation material powder according to claim 1, characterized in that, The preparation process of the high-temperature antioxidant ablation material powder includes direct mixing or thermal reduction.

3. The high-temperature antioxidant ablation material powder according to claim 3, characterized in that, The direct mixing method includes the following steps: weighing metal boride or metal carbide and silicon carbide powder according to the chemical composition stoichiometry of the high-temperature anti-oxidation ablation material powder according to any one of claims 1-2, and mixing them evenly to obtain the final product.

4. The high-temperature antioxidant ablation material powder according to claim 3, characterized in that, The thermal reduction method includes the following steps: according to the chemical composition stoichiometry of the high-temperature anti-oxidation ablation material powder as described in any one of claims 1-3, the oxide powder corresponding to the metal element in the metal boride or metal carbide is weighed and subjected to thermal reduction reaction with B4C or C powder to synthesize metal boride or metal carbide solid solution powder. Then, silicon carbide powder is mixed evenly with the metal boride or metal carbide solid solution powder to obtain the final product.

5. A high-temperature oxidation-resistant ablation-resistant ceramic material, characterized in that, The preparation method of the high-temperature anti-oxidation and ablation ceramic material includes the following steps: the high-temperature anti-oxidation and ablation material powder of any one of claims 1-4 is sintered by discharge plasma or hot pressing to obtain the high-temperature anti-oxidation and ablation ceramic material.

6. The high-temperature oxidation-resistant ablation-resistant ceramic material according to claim 5, characterized in that, The process parameters for the discharge plasma sintering include: vacuum degree 50-200 Pa, heating rate 100-200 °C / min, sintering temperature 1500-2200 °C, sintering pressure 10-60 MPa, and sintering time 5-30 min.

7. The high-temperature oxidation-resistant ablation-resistant ceramic material according to claim 5 or 6, characterized in that, The process parameters for hot pressing sintering include: vacuum degree 50-200 Pa, heating rate 5-30 °C / min, sintering temperature 1500-2200 °C, sintering pressure 10-60 MPa, and sintering time 30-300 min.

8. A high-temperature anti-oxidation and ablation coating, characterized in that, The preparation method of the high-temperature anti-oxidation ablation coating includes the following steps: the high-temperature anti-oxidation ablation material powder of any one of claims 1-4 is sequentially subjected to ball milling, spray granulation and high-temperature heat treatment to obtain spherical powder suitable for spraying, and then sprayed onto the substrate surface by plasma spraying technology to obtain the high-temperature anti-oxidation ablation coating.

9. The high-temperature anti-oxidation and ablation coating according to claim 8, characterized in that, The process parameters of the plasma spraying technology include: plasma generating gas Ar: 30-50 slpm, plasma generating gas H2: 2-20 slpm, powder carrier gas Ar: 3-10 slpm; spraying distance: 100-350 mm; spraying power: 30-55 kW; powder feeding rate: 5-40 rpm; spraying pressure: 100-1000 mbar; spraying atmosphere: air or argon atmosphere, preferably argon atmosphere.

10. The high-temperature anti-oxidation and ablation coating according to claim 8 or 9, characterized in that, The matrix includes C / C composite materials, C / SiC composite materials, SiC / SiC composite materials, ceramic-modified composite materials, or metals and their alloys.

Images