技术领域Technical Field
本发明涉及表面涂层技术领域，具体涉及一种利用聚合物转化陶瓷制备的C/C复合材料抗氧化烧蚀涂层及其制备方法和应用。The invention relates to the technical field of surface coatings, and in particular to a C/C composite material anti-oxidation ablation coating prepared by polymer-converted ceramics, and a preparation method and application thereof.
背景技术Background technique
近年来，随着航空航天技术的高速发展，对热防护系统所需的超高温结构材料提出了更加苛刻的要求。飞行器构件不仅要承受高速粒子和燃气流的冲刷和高温极端环境，还要克服横向和剪切应力。这种严苛的服役环境要求超高温结构材料具有耐高温性能、抗氧化/烧蚀性能、优异的力学性能，以及低密度等特点。In recent years, with the rapid development of aerospace technology, more stringent requirements have been put forward for ultra-high temperature structural materials required for thermal protection systems. Aircraft components must not only withstand the erosion of high-speed particles and gas flows and high-temperature extreme environments, but also overcome lateral and shear stresses. This harsh service environment requires ultra-high temperature structural materials to have high temperature resistance, oxidation resistance/ablation resistance, excellent mechanical properties, and low density.
碳/碳(C/C)复合材料由于具有低密度、高比强度、低热膨胀系数，及在超过2000℃的高温环境下表现出优异的热稳定性(抗热震及耐烧蚀性能)和力学强度，是迄今唯一可用于3000℃以上的复合材料。然而，C/C复合材料与其他碳质材料一样存在一个致命的缺点，即在高温有氧环境中具有很高的氧化敏感性。研究表明，C/C复合材料在空气中的初始氧化温度仅为370℃，且在超过500℃以上发生急剧氧化，严重的氧化将导致C/C复合材料的力学性能显著降低，从而限制其在高温氧化环境中的应用。目前，以防止含氧气体接触和扩散为前提，在材料表面制备耐高温氧化的涂层技术被视作为C/C复合材料在2000℃以上提供长时防护的有效手段。Carbon/carbon (C/C) composites are the only composite materials that can be used above 3000℃ due to their low density, high specific strength, low thermal expansion coefficient, and excellent thermal stability (thermal shock resistance and ablation resistance) and mechanical strength in high temperature environments above 2000℃. However, C/C composites, like other carbonaceous materials, have a fatal disadvantage, that is, they have high oxidation sensitivity in high temperature aerobic environments. Studies have shown that the initial oxidation temperature of C/C composites in air is only 370℃, and rapid oxidation occurs above 500℃. Severe oxidation will lead to a significant decrease in the mechanical properties of C/C composites, thereby limiting their application in high temperature oxidative environments. At present, the technology of preparing high temperature oxidation-resistant coatings on the surface of materials is regarded as an effective means to provide long-term protection for C/C composites above 2000℃, based on the premise of preventing contact and diffusion of oxygen-containing gases.
料浆涂覆结合高温气相渗硅法在C/C复合材料表面能够制备出致密的、与基体结合强度高的富硅涂层。通常，研究人员选用无机陶瓷粉体作为原料溶解于无水乙醇中制得用于涂覆的浆料。然而，无论是纳米级粉体还是微米级粉体均无法完全溶解获得溶质均匀、悬浮稳定的料浆，由于浆料的不均匀性和不稳定性，实际制备中很难得到理想厚度和低孔隙率的预涂层。Slurry coating combined with high-temperature vapor phase siliconization can produce a dense, highly bonded silicon-rich coating on the surface of C/C composites. Usually, researchers use inorganic ceramic powders as raw materials and dissolve them in anhydrous ethanol to prepare slurry for coating. However, neither nano-scale powders nor micro-scale powders can be completely dissolved to obtain a slurry with uniform solute and stable suspension. Due to the inhomogeneity and instability of the slurry, it is difficult to obtain a pre-coating with ideal thickness and low porosity in actual preparation.
发明内容Summary of the invention
针对上述背景技术中存在的不足，本发明主要针对陶瓷料浆的均匀性和稳定性问题，以及抗氧化烧蚀涂层与C/C复合材料间的界面难相容的问题。本发明提供一种利用聚合物转化陶瓷制备的C/C复合材料抗氧化烧蚀涂层及其制备方法和应用。该方法通过料浆涂覆结合高温气相渗硅法将聚合物转化超高温陶瓷引入C/C复合材料表面制备得到富硅陶瓷涂层。其制备工艺成本低、工艺简单、质量可靠性高、可设计性强。In view of the deficiencies in the above-mentioned background technology, the present invention mainly addresses the uniformity and stability of ceramic slurries, as well as the problem of poor compatibility of the interface between the anti-oxidation ablative coating and the C/C composite material. The present invention provides an anti-oxidation ablative coating for C/C composite materials prepared by using polymer-converted ceramics, and a preparation method and application thereof. The method introduces polymer-converted ultra-high temperature ceramics into the surface of C/C composite materials by slurry coating combined with high-temperature gas phase siliconization to prepare a silicon-rich ceramic coating. The preparation process has low cost, simple process, high quality reliability and strong designability.
本发明第一个目的是提供一种利用聚合物转化陶瓷制备的C/C复合材料抗氧化烧蚀涂层的制备方法，包括以下步骤：The first object of the present invention is to provide a method for preparing a C/C composite material anti-oxidation ablation coating prepared by polymer-converted ceramics, comprising the following steps:
制备聚合物转化陶瓷粉体；Preparation of polymer-converted ceramic powders;
将SiC粉体均匀混合于酚醛树脂乙醇溶液中，获得浆料A；The SiC powder is uniformly mixed in the phenolic resin ethanol solution to obtain slurry A;
将SiC粉体以及聚合物转化陶瓷粉体均匀混合于酚醛树脂乙醇溶液中，获得浆料B；The SiC powder and the polymer-converted ceramic powder are uniformly mixed in the phenolic resin ethanol solution to obtain slurry B;
将浆料A、浆料B依次涂覆于C/C复合材料表面后，依次进行固化、碳化，在C/C复合材料表面获得预涂层；其中，将浆料A涂覆于C/C复合材料表面经干燥后，再涂覆浆料B；After slurry A and slurry B are sequentially applied to the surface of the C/C composite material, they are sequentially cured and carbonized to obtain a pre-coating layer on the surface of the C/C composite material; wherein, after slurry A is applied to the surface of the C/C composite material and dried, slurry B is then applied;
将带有预涂层的C/C复合材料，在惰性气氛中，于1800～2150℃，处理15～30min，即在C/C复合材料表面获得抗氧化烧蚀涂层。The C/C composite material with the pre-coating is treated in an inert atmosphere at 1800-2150° C. for 15-30 minutes to obtain an anti-oxidation and ablation coating on the surface of the C/C composite material.
优选的，所述聚合物转化陶瓷粉体是按照以下步骤制得：Preferably, the polymer-converted ceramic powder is prepared according to the following steps:
将硅烷类聚合物和过渡金属聚合物以一定比例混合，并溶于二甲苯溶液中，于70～90℃下混合均匀后，在惰性气氛中，于250～400℃，处理2～4h，即得聚合物转化陶瓷粉体。Silane polymer and transition metal polymer are mixed in a certain proportion and dissolved in a xylene solution. After being mixed evenly at 70-90° C., they are treated in an inert atmosphere at 250-400° C. for 2-4 hours to obtain polymer-converted ceramic powder.
优选的，所述过渡金属聚合物中的过渡金属元素为Hf、Zr、Ti或Ta。Preferably, the transition metal element in the transition metal polymer is Hf, Zr, Ti or Ta.
所述过渡金属聚合物和硅烷类聚合物质量比1：1.5～2。The mass ratio of the transition metal polymer to the silane polymer is 1:1.5-2.
优选的，固化的温度为200～300℃，固化时长为2～4h；碳化的温度为900～1100℃，碳化时长为2～4h。Preferably, the curing temperature is 200-300° C., and the curing time is 2-4 hours; the carbonization temperature is 900-1100° C., and the carbonization time is 2-4 hours.
优选的，所述C/C复合材料的密度为1.60-1.85g/cm3。Preferably, the density of the C/C composite material is 1.60-1.85 g/cm3 .
优选的，所述酚醛树脂乙醇溶液是按照酚醛树脂与无水乙醇按照质量比为1：5～7混合制得的。Preferably, the phenolic resin ethanol solution is prepared by mixing phenolic resin and anhydrous ethanol in a mass ratio of 1:5 to 7.
优选的，所述浆料A中，所述SiC粉体的质量分数为30～50wt％。Preferably, in the slurry A, the mass fraction of the SiC powder is 30-50wt%.
优选的，所述浆料B中，所述SiC的质量分数为10～20wt％，所述聚合物转化陶瓷粉体的质量分数为20～40wt％。Preferably, in the slurry B, the mass fraction of the SiC is 10-20wt%, and the mass fraction of the polymer-converted ceramic powder is 20-40wt%.
本发明第二个目的是提供一种C/C复合材料抗氧化烧蚀涂层。The second object of the present invention is to provide a C/C composite material anti-oxidation and ablation coating.
本发明第三个目的是提供一种涂层在C/C复合材料抗氧化烧蚀中的应用。The third object of the present invention is to provide a coating for use in anti-oxidation and ablation of C/C composite materials.
与现有技术相比，本发明的有益效果是：Compared with the prior art, the present invention has the following beneficial effects:
本发明提供的一种利用聚合物转化陶瓷制备的C/C复合材料抗氧化烧蚀涂层及其制备方法和应用，该方法首先采用Schlenk技术制备含过渡金属元素的硅基单源聚合物，接着依次通过低温交联、裂解以及高温热处理得到具有独特“类胶囊”式纳米结构的陶瓷粉体；其次通过料浆涂覆结合高温气相渗硅法在C/C复合材料表面制备抗氧化烧蚀涂层。料浆涂覆工艺通过调控料浆组分、料浆组分含量和涂覆次数对抗氧化烧蚀涂层的结构和厚度进行调控，借助高温气相渗硅工艺过程中硅蒸汽的强穿透能力，其能轻易穿透预涂层到达C/C基底并且发生反应在界面处形成锯齿状SiC过渡层，提升涂层与C/C基体的结合强度和涂层的致密度。The present invention provides a C/C composite material anti-oxidation ablation coating prepared by polymer conversion ceramics, and a preparation method and application thereof. The method first adopts Schlenk technology to prepare a silicon-based single-source polymer containing transition metal elements, and then obtains a ceramic powder with a unique "capsule-like" nanostructure through low-temperature crosslinking, cracking and high-temperature heat treatment in sequence; secondly, the anti-oxidation ablation coating is prepared on the surface of the C/C composite material by slurry coating combined with high-temperature gas phase siliconization. The slurry coating process regulates the structure and thickness of the anti-oxidation ablation coating by regulating the slurry components, the content of the slurry components and the number of coatings. With the strong penetration ability of silicon vapor in the high-temperature gas phase siliconization process, it can easily penetrate the pre-coating layer to reach the C/C substrate and react to form a jagged SiC transition layer at the interface, thereby improving the bonding strength between the coating and the C/C substrate and the density of the coating.
本发明提出一种利用聚合物转化陶瓷制备C/C复合材料抗氧化烧蚀涂层的方法。首先采用Schlenk技术制备多元素单源聚合物，经过一定温度下的交联固化处理，制备非晶聚合物转化陶瓷粉体。接着，通过料浆涂覆结合高温气相渗硅法将聚合物转化超高温陶瓷引入C/C复合材料表面制备得到富硅陶瓷涂层。The present invention proposes a method for preparing an anti-oxidation ablation coating of a C/C composite material by using polymer-converted ceramics. First, a multi-element single-source polymer is prepared by using Schlenk technology, and an amorphous polymer-converted ceramic powder is prepared by cross-linking and curing at a certain temperature. Then, the polymer-converted ultra-high temperature ceramic is introduced into the surface of the C/C composite material by slurry coating combined with high-temperature vapor phase siliconization to prepare a silicon-rich ceramic coating.
本发明提供的方法制备工艺成本低、工艺简单、质量可靠性高、可设计性强。The method provided by the invention has low preparation process cost, simple process, high quality reliability and strong designability.
本发明采用高温气相渗硅法能够为硅块转变为硅蒸汽提供合适的高温环境，得益于气态硅的强穿透性，它可以轻易穿透多孔的预涂层抵达C/C基体发生反应，同时预涂层中引入聚合物转化陶瓷粉体颗粒外部的无定形碳层也能够与气态硅发生原位反应。上述反应不仅能够解决抗氧化烧蚀涂层与C/C复合材料间的界面难相容的问题，并且由于上述反应的发生均伴随着预涂层中组分的体积膨胀，还能有助于最终制备致密的抗烧蚀涂层。The present invention adopts a high-temperature gas phase siliconization method to provide a suitable high-temperature environment for converting silicon blocks into silicon vapor. Thanks to the strong penetrability of gaseous silicon, it can easily penetrate the porous pre-coating layer to reach the C/C matrix for reaction. At the same time, the amorphous carbon layer on the outside of the polymer-converted ceramic powder particles introduced into the pre-coating layer can also react in situ with the gaseous silicon. The above reaction can not only solve the problem of poor compatibility between the interface of the anti-oxidation ablation coating and the C/C composite material, but also help to finally prepare a dense anti-ablation coating because the occurrence of the above reaction is accompanied by the volume expansion of the components in the pre-coating layer.
本发明借助涂层中多成分的氧化膨胀“结痂”效应，能够对高温有氧环境中涂层产生的裂纹、孔隙等缺陷进行快速修复，进而提升C/C复合材料的防氧化烧蚀性能，为满足苛刻环境稳定服役奠定基础。The present invention utilizes the "scab" effect of oxidation expansion of multiple components in the coating to quickly repair defects such as cracks and pores produced in the coating in a high-temperature aerobic environment, thereby improving the anti-oxidation and ablation performance of the C/C composite material and laying the foundation for stable service in harsh environments.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为本发明工艺流程图：(a)制备单源聚合物转化陶瓷粉体，(b)制备C/C复合材料表面聚合物转化陶瓷制备抗氧化烧蚀涂层；FIG1 is a process flow chart of the present invention: (a) preparing a single-source polymer-converted ceramic powder, (b) preparing a polymer-converted ceramic on the surface of a C/C composite material to prepare an anti-oxidation ablation coating;
图2为不同温度热处理后得到的单源聚合物转化陶瓷的SEM照片：(a)900℃,(b)1900℃；Figure 2 shows SEM images of single-source polymer-converted ceramics obtained after heat treatment at different temperatures: (a) 900°C, (b) 1900°C;
图3为实施例1提供的固化及碳化后得到的预涂层试样的SEM照片：(a)表面SEM照片，(b)截面SEM照片；FIG3 is a SEM photo of the pre-coating sample obtained after curing and carbonization provided in Example 1: (a) surface SEM photo, (b) cross-sectional SEM photo;
图4为实施例1浆料涂覆结合高温气相渗硅后得到的涂层试样的SEM照片：(a)表面SEM照片，(b)截面SEM照片；FIG4 is an SEM photograph of a coating sample obtained after slurry coating combined with high-temperature vapor siliconization in Example 1: (a) surface SEM photograph, (b) cross-sectional SEM photograph;
图5为实施例1提供的涂层等离子烧蚀后的表面宏观形貌照片。FIG5 is a photograph of the surface macroscopic morphology of the coating provided in Example 1 after plasma ablation.
具体实施方式Detailed ways
为了使本领域技术人员更好地理解本发明的技术方案能予以实施，下面结合具体实施例和附图对本发明作进一步说明，但所举实施例不作为对本发明的限定。In order to enable those skilled in the art to better understand and implement the technical solution of the present invention, the present invention is further described below in conjunction with specific embodiments and drawings, but the embodiments are not intended to limit the present invention.
陶瓷前驱体通常为聚合物，因其在溶剂中具有良好的分子相溶性，液态悬浮稳定性强，可用于解决陶瓷料浆的均匀性和稳定性问题。而且，料浆涂敷后的热解处理，能够使聚合物转化为陶瓷(PDCs)，成为均匀分散的纳米固体粉末，易于得到厚度和孔隙可控的固体涂层或薄膜。Ceramic precursors are usually polymers, which can be used to solve the uniformity and stability problems of ceramic slurries because of their good molecular solubility in solvents and strong liquid suspension stability. Moreover, the pyrolysis treatment after slurry coating can convert polymers into ceramics (PDCs) and become uniformly dispersed nano solid powders, making it easy to obtain solid coatings or films with controllable thickness and pores.
聚合物转化陶瓷法(PDCs)是指将合成的聚合物前驱体，经过交联固化、高温热解而实现其陶瓷化转变的方法。通过向有机高分子中引入异质元素合成单源前驱体，再经过PDCs法可制备纳米复相陶瓷。与直接在浆料中引入两种及以上前驱体粉末使其在高温气相渗硅的过程中反应形成目标陶瓷不同，此法可提前对引入浆料中的聚合物前驱体在分子水平上进行结构设计，通过用金属醇盐或乙酰丙酮酸盐等有机分子改性聚合物，发生脱水、加成等缩聚反应，整合各金属元素至硅烷类聚合物结构，提升聚合物的结构稳定性，裂解后即可得到晶粒尺寸小、氧含量低的纳米复相陶瓷。进一步高温退火后，PDCs呈现出一种特殊的微观结构，表现为以无定形碳层为壳、以结晶度良好的陶瓷相为核的“类胶囊”式核壳结构。基于此，若结合高温气相渗硅过程，气态硅可与预涂层中的PDC非晶碳层发生原位反应形成SiC，既可以提升涂层的致密度，又能确保涂层具备优异的抗氧化烧蚀性能。The polymer conversion ceramics method (PDCs) refers to a method of converting a synthesized polymer precursor into a ceramic by crosslinking, curing, and high-temperature pyrolysis. By introducing heterogeneous elements into organic polymers to synthesize a single-source precursor, nanocomposite ceramics can be prepared by the PDCs method. Unlike directly introducing two or more precursor powders into the slurry to react and form the target ceramics during high-temperature gas-phase siliconization, this method can design the structure of the polymer precursor introduced into the slurry at the molecular level in advance, modify the polymer with organic molecules such as metal alkoxides or acetylacetonates, undergo dehydration, addition, and other condensation reactions, integrate various metal elements into the silane polymer structure, improve the structural stability of the polymer, and obtain nanocomposite ceramics with small grain size and low oxygen content after cracking. After further high-temperature annealing, PDCs present a special microstructure, which is a "capsule-like" core-shell structure with an amorphous carbon layer as the shell and a ceramic phase with good crystallinity as the core. Based on this, if combined with the high-temperature vapor phase siliconization process, gaseous silicon can react in situ with the PDC amorphous carbon layer in the pre-coating to form SiC, which can not only improve the density of the coating, but also ensure that the coating has excellent anti-oxidation and ablation properties.
本发明第一方面提供一种利用聚合物转化陶瓷制备C/C复合材料抗氧化烧蚀涂层的方法，包括以下步骤：The first aspect of the present invention provides a method for preparing a C/C composite material anti-oxidation ablation coating by using polymer-converted ceramics, comprising the following steps:
制备聚合物转化陶瓷粉体；Preparation of polymer-converted ceramic powders;
将SiC粉体均匀混合于酚醛树脂乙醇溶液中，获得浆料A；The SiC powder is uniformly mixed in the phenolic resin ethanol solution to obtain slurry A;
将SiC粉体以及聚合物转化陶瓷粉体均匀混合于酚醛树脂乙醇溶液中，获得浆料B；The SiC powder and the polymer-converted ceramic powder are uniformly mixed in the phenolic resin ethanol solution to obtain slurry B;
其中，所述酚醛树脂乙醇溶液是按照酚醛树脂与无水乙醇按照质量比为1：5～7混合制得的；The phenolic resin ethanol solution is prepared by mixing phenolic resin and anhydrous ethanol in a mass ratio of 1:5 to 7;
将浆料A、浆料B依次涂覆于C/C复合材料表面后，依次进行固化、碳化，在C/C复合材料表面获得预涂层；其中，将浆料A涂覆于C/C复合材料表面经干燥后，再涂覆浆料B；其中，固化的温度为200～300℃，固化时长为2～4h；碳化的温度为900～1100℃，碳化时长为2～4h；After slurry A and slurry B are sequentially applied to the surface of the C/C composite material, they are cured and carbonized in sequence to obtain a pre-coating layer on the surface of the C/C composite material; wherein slurry A is applied to the surface of the C/C composite material and dried, and then slurry B is applied; wherein the curing temperature is 200-300°C, and the curing time is 2-4h; the carbonization temperature is 900-1100°C, and the carbonization time is 2-4h;
将带有预涂层的C/C复合材料，在惰性气氛中，于1800～2150℃，处理15～30min，即在C/C复合材料表面获得抗氧化烧蚀涂层。The C/C composite material with the pre-coating is treated in an inert atmosphere at 1800-2150° C. for 15-30 minutes to obtain an anti-oxidation and ablation coating on the surface of the C/C composite material.
本发明通过料浆涂覆结合高温气相渗硅法将聚合物转化超高温陶瓷引入C/C复合材料表面制备得到富硅陶瓷涂层。其制备工艺成本低、工艺简单、质量可靠性高、可设计性强。高温气相渗硅法，能够使得气态硅具有强烈的穿透性，它可以轻易穿透多孔的预涂层抵达C/C基体发生反应，同时预涂层中引入聚合物转化陶瓷粉体颗粒外部的无定形碳层也能够与气态硅发生原位反应。该反应的发生均伴随着预涂层中组分的体积膨胀，还能有助于最终制备致密的抗烧蚀涂层。The present invention introduces polymer-converted ultra-high temperature ceramics into the surface of a C/C composite material through slurry coating combined with a high-temperature vapor phase siliconization method to prepare a silicon-rich ceramic coating. The preparation process has low cost, simple process, high quality reliability, and strong designability. The high-temperature vapor phase siliconization method can make gaseous silicon have strong penetrability. It can easily penetrate the porous pre-coating layer to reach the C/C matrix to react. At the same time, the amorphous carbon layer on the outside of the polymer-converted ceramic powder particles introduced into the pre-coating layer can also react in situ with gaseous silicon. The occurrence of this reaction is accompanied by the volume expansion of the components in the pre-coating layer, and can also help to finally prepare a dense anti-ablation coating.
需要说明的是，采用密度为1.60-1.85g/cm3的C/C复合材料作为基体材料。It should be noted that a C/C composite material with a density of 1.60-1.85 g/cm3 is used as the matrix material.
其中，所述聚合物转化陶瓷粉体是按照以下步骤制得：Wherein, the polymer-converted ceramic powder is prepared according to the following steps:
将硅烷类聚合物和过渡金属聚合物以一定比例混合，并溶于二甲苯溶液中，于70～90℃下混合均匀后，在惰性气氛中，于250～400℃，处理2～4h，即得聚合物转化陶瓷粉体。制备聚合物转化陶瓷粉体时，采用Schlenk技术制备多元素单源聚合物，经过一定温度下的交联固化处理，制备非晶聚合物转化陶瓷粉体。The silane polymer and the transition metal polymer are mixed in a certain proportion and dissolved in a xylene solution. After being mixed evenly at 70-90°C, they are treated at 250-400°C in an inert atmosphere for 2-4 hours to obtain a polymer-converted ceramic powder. When preparing the polymer-converted ceramic powder, the Schlenk technique is used to prepare a multi-element single-source polymer, and after cross-linking and curing at a certain temperature, an amorphous polymer-converted ceramic powder is prepared.
具体的，所述过渡金属聚合物中的过渡金属元素为Hf、Zr、Ti或Ta。Specifically, the transition metal element in the transition metal polymer is Hf, Zr, Ti or Ta.
所述过渡金属聚合物可为乙酰丙酮铪、四(二乙基酰胺)铪等含铪有机聚合物，乙酰丙酮锆、四(二甲基胺基)锆等含锆有机聚合物以及钛酸四丁酯等。The transition metal polymer may be an organic polymer containing hafnium such as hafnium acetylacetonate and tetrakis(diethylamide)hafnium, an organic polymer containing zirconium such as zirconium acetylacetonate and tetrakis(dimethylamino)zirconium, or tetrabutyl titanate.
所述硅烷类聚合物可为聚碳硅烷(PCS)、聚硅氮烷(PSZ)、硅硼碳氮(SiBCN)等。The silane-based polymer may be polycarbosilane (PCS), polysilazane (PSZ), silicon boron carbon nitride (SiBCN), or the like.
所述过渡金属聚合物和硅烷类聚合物质量比1：1.5～2。The mass ratio of the transition metal polymer to the silane polymer is 1:1.5-2.
所述浆料A中，所述SiC粉体的质量分数为30～50wt％。In the slurry A, the mass fraction of the SiC powder is 30-50wt%.
所述浆料B中，所述SiC的质量分数为10～20wt％，所述聚合物转化陶瓷粉体的质量分数为20～40wt％。In the slurry B, the mass fraction of the SiC is 10-20wt%, and the mass fraction of the polymer-converted ceramic powder is 20-40wt%.
在一实施例中，利用聚合物转化陶瓷制备C/C复合材料抗氧化烧蚀涂层的方法，参见图1所示，具体包括：In one embodiment, a method for preparing a C/C composite material anti-oxidation ablative coating by using polymer-converted ceramics, as shown in FIG1 , specifically includes:
步骤1：将硅烷类聚合物和过渡金属聚合物以一定比例混合并溶于二甲苯溶液中，在70～90℃区间内充分搅拌3h以上，随后在250～400℃区间内交联固化处理2h以上，所述处理均在Schlenk装置内氩气气氛下进行，最后得到可以满足涂覆要求的单源聚合物粉体；Step 1: Mix a silane polymer and a transition metal polymer in a certain proportion and dissolve them in a xylene solution, fully stir them at a temperature of 70 to 90° C. for more than 3 hours, and then crosslink and cure them at a temperature of 250 to 400° C. for more than 2 hours. The treatment is carried out in an argon atmosphere in a Schlenk device, and finally a single-source polymer powder that meets the coating requirements is obtained;
步骤2：将C/C复合材料用去离子水进行超声清洗，并在温度为80～100℃的电热鼓风干燥箱中烘干4h以上；Step 2: ultrasonically clean the C/C composite material with deionized water, and dry it in an electric hot air drying oven at a temperature of 80 to 100° C. for more than 4 hours;
步骤3：将C/C复合材料浸入到料浆A中静置5～10s，取出后干燥，该过程重复多次后，制得SiC内涂层；Step 3: Immerse the C/C composite material into slurry A and let it stand for 5 to 10 seconds, take it out and dry it. After repeating this process several times, the SiC inner coating is obtained;
步骤4：将带有SiC内涂层的C/C复合材料浸入到料浆B中静置5～10s后干燥，该过程重复多次后，制得外涂层；Step 4: Immerse the C/C composite material with SiC inner coating into slurry B, let it stand for 5 to 10 seconds and then dry. Repeat this process several times to obtain the outer coating.
步骤5：将带有以上料浆预涂覆并且干燥后的C/C复合材料在200～300℃下固化2h以上，接着在900～1100℃下碳化2h以上，处理气氛为氩气气氛，制得预涂层；Step 5: Curing the C/C composite material pre-coated with the above slurry and dried at 200-300° C. for more than 2 hours, and then carbonizing at 900-1100° C. for more than 2 hours in an argon atmosphere to obtain a pre-coating layer;
步骤6：将带有预涂层的C/C复合材料置于多孔石墨板上，整体放入底部置有一定数量硅块的石墨坩埚中，在氩气气氛的保护下进行气相渗硅处理，温度为1800～2150℃，处理时间为15～30min，即可在C/C复合材料表面制得双层抗氧化烧蚀涂层。Step 6: Place the C/C composite material with the pre-coating on a porous graphite plate, and place the whole into a graphite crucible with a certain number of silicon blocks at the bottom, and perform vapor phase siliconization treatment under the protection of an argon atmosphere at a temperature of 1800 to 2150°C for 15 to 30 minutes, so that a double-layer anti-oxidation and ablation coating can be obtained on the surface of the C/C composite material.
其中，所述步骤1中的混合溶液包括：含过渡金属聚合物和硅烷类聚合物以质量比1：1.5～2混合，二甲苯作为溶剂，所述混合溶液中溶质的质量浓度为50wt％。其中，过渡金属元素可为Hf、Zr、Ti或Ta等。The mixed solution in step 1 comprises: a transition metal-containing polymer and a silane polymer mixed in a mass ratio of 1:1.5-2, xylene is used as a solvent, and the mass concentration of the solute in the mixed solution is 50wt%. The transition metal element can be Hf, Zr, Ti or Ta.
所述步骤3中的料浆A包括：将酚醛树脂与无水乙醇按照质量比1：6混合，经超声处理后得到搅拌均匀的酚醛树脂溶液；向酚醛树脂溶液中加入SiC粉体，经充分搅拌后得到SiC-酚醛树脂浆料A，其中SiC粉体的质量分数为30～50wt％。The slurry A in step 3 comprises: mixing phenolic resin and anhydrous ethanol in a mass ratio of 1:6, and obtaining a uniformly stirred phenolic resin solution after ultrasonic treatment; adding SiC powder to the phenolic resin solution, and obtaining SiC-phenolic resin slurry A after sufficient stirring, wherein the mass fraction of SiC powder is 30-50wt%.
所述步骤4中的料浆B包括：向酚醛树脂溶液中加入SiC粉体和步骤1中制得的单源聚合物粉体，搅拌均匀后得到料浆B，其中SiC的质量分数为10～20wt％，单源聚合物粉体的质量分数为20～40wt％。The slurry B in step 4 comprises: adding SiC powder and the single-source polymer powder obtained in step 1 to the phenolic resin solution, stirring evenly to obtain slurry B, wherein the mass fraction of SiC is 10-20wt%, and the mass fraction of the single-source polymer powder is 20-40wt%.
本发明第二方面提供一种C/C复合材料抗氧化烧蚀涂层。该涂层为双层结构，由SiC内涂层和抗氧化烧蚀外涂层组成。其中，SiC内涂层用于缓解涂层与基体间的热失配。The second aspect of the present invention provides a C/C composite material anti-oxidation ablation coating. The coating is a double-layer structure, consisting of a SiC inner coating and an anti-oxidation ablation outer coating. The SiC inner coating is used to alleviate the thermal mismatch between the coating and the substrate.
本发明第三方面提供一种涂层在C/C复合材料抗氧化烧蚀中的应用。A third aspect of the present invention provides an application of a coating in anti-oxidation and ablation of a C/C composite material.
需要说明的是，本发明中采用的实验方法如无特殊说明，均为常规方法；采用的试剂和材料，如无特殊说明，均可在市场上购买得到。It should be noted that the experimental methods used in the present invention are all conventional methods unless otherwise specified; the reagents and materials used are all commercially available unless otherwise specified.
实施例1Example 1
一种利用聚合物转化陶瓷制备C/C复合材料抗氧化烧蚀涂层的方法，包括以下步骤：A method for preparing a C/C composite material anti-oxidation ablation coating by using polymer-converted ceramics comprises the following steps:
步骤一，参见图1中(a)所示，制备单源聚合物转化陶瓷粉体：Step 1, as shown in FIG1 (a), a single-source polymer-converted ceramic powder is prepared:
1)首先，将磁子和适量沸石加入三颈瓶，接着称量40g聚硅氮烷于三颈瓶中，并继续添加称量好的20gZrC聚合物前驱体，随后向三颈瓶内添加60g二甲苯得到混合溶液。然后，将Schlenk设备各接口处均涂抹上真空油脂以确保装置连接后具有良好的气密性。1) First, add the magnet and an appropriate amount of zeolite into a three-necked bottle, then weigh 40g of polysilazane into the three-necked bottle, and continue to add the weighed 20g of ZrC polymer precursor, and then add 60g of xylene into the three-necked bottle to obtain a mixed solution. Then, apply vacuum grease to each interface of the Schlenk device to ensure good airtightness after the device is connected.
2)接着，打开真空泵开关阀门除去装置中的空气和残余的水汽，当真空表显示真空度到-0.9MPa时关闭真空泵静待5min进行保压操作，若静置期间真空表示数未发生变化，则视装置气密性良好，可以继续下一步操作。此时缓慢转动Schlenk装置中双排管上的阀门填充氩气进行第一次洗气处理。重复上述抽真空充氩气的步骤反复三次以确保装置内为无水无氧的环境。2) Next, open the vacuum pump switch valve to remove the air and residual water vapor in the device. When the vacuum gauge shows that the vacuum degree reaches -0.9MPa, turn off the vacuum pump and wait for 5 minutes to maintain the pressure. If the vacuum gauge number does not change during the static period, the air tightness of the device is good and you can proceed to the next step. At this time, slowly turn the valve on the double-row pipe in the Schlenk device to fill argon gas for the first gas washing treatment. Repeat the above steps of vacuuming and filling argon gas three times to ensure that the device is a water-free and oxygen-free environment.
3)此时将氩气流量调大，打开三颈瓶底部的磁力搅拌器进行加热搅拌。上述加热搅拌的温度为80℃，反应时间为3h。3) At this time, the argon flow rate was increased, and the magnetic stirrer at the bottom of the three-necked flask was turned on for heating and stirring. The temperature of the heating and stirring was 80° C., and the reaction time was 3 h.
4)加热搅拌结束后，将三颈瓶底部的加热台温度降至60℃并保持，同时向其顶部连接的冷凝器内通入冷凝水进行冷却，缓慢打开真空泵阀门除去瓶中剩余的溶剂。4) After heating and stirring, the temperature of the heating platform at the bottom of the three-necked flask was lowered to 60°C and maintained, and condensed water was introduced into the condenser connected to the top of the flask for cooling, and the vacuum pump valve was slowly opened to remove the remaining solvent in the flask.
5)将除去溶剂的反应物从三颈瓶中取出，置于管式炉在温度为300℃时交联固化并且保温处理2h，处理气氛为氩气气氛，之后收集固化后的聚合物转化陶瓷粉体。5) The reactant after the solvent is removed is taken out from the three-necked flask, placed in a tube furnace at a temperature of 300° C. for cross-linking and curing and heat preservation for 2 hours in an argon atmosphere, and then the cured polymer-converted ceramic powder is collected.
步骤二，参见图1中(b)所示，浆料涂覆结合高温气相渗硅法制备涂层：Step 2, as shown in FIG1(b), slurry coating combined with high temperature vapor phase siliconization method is used to prepare the coating:
1)将密度为1.75g/cm3的C/C块体加工成尺寸为φ20mm×5mm的圆柱形试样，经去离子水超声清洗并在温度为90℃的电热鼓风干燥箱中烘干后得到用于之后制备涂层的C/C基体。1) A C/C block with a density of 1.75 g/cm3 was processed into a cylindrical sample with a size of φ20 mm×5 mm, and after ultrasonic cleaning with deionized water and drying in an electric heated forced air drying oven at a temperature of 90°C, a C/C substrate for subsequent coating preparation was obtained.
2)将30wt％的SiC，10wt％的酚醛树脂溶于60wt％的无水乙醇，经过充分搅拌和超声后得到浆料A。2) 30 wt % of SiC and 10 wt % of phenolic resin were dissolved in 60 wt % of anhydrous ethanol, and slurry A was obtained after sufficient stirring and ultrasonic treatment.
3)将C/C基体浸入到料浆A中静置5s，取出后干燥，重复该过程4次。3) Immerse the C/C substrate in slurry A and let it stand for 5 seconds. Take it out and dry it. Repeat this process 4 times.
4)将15wt％的SiC，30wt％的聚合物转化陶瓷粉体，5wt％的酚醛树脂溶于50wt％的无水乙醇，经过充分搅拌和超声后得到浆料B。4) 15 wt% of SiC, 30 wt% of polymer-converted ceramic powder, and 5 wt% of phenolic resin were dissolved in 50 wt% of anhydrous ethanol, and slurry B was obtained after sufficient stirring and ultrasonic treatment.
5)将带有浆料A涂覆并干燥后的C/C基体浸入到料浆B中静置5s，取出后干燥，重复该过程4次。5) Immerse the C/C substrate coated with slurry A and dried into slurry B and let it stand for 5 seconds. Take it out and dry it. Repeat this process 4 times.
6)将涂覆结束的试样在300℃下固化2h，再于900℃氩气气氛保护下碳化2h，得到预涂层试样。6) The coated sample was cured at 300° C. for 2 h, and then carbonized at 900° C. for 2 h under argon atmosphere protection to obtain a pre-coated sample.
7)将带有预涂层的C/C复合材料放于多孔石墨板上，再放入底部置有一定量的硅块的石墨坩埚中；然后在氩气气氛的保护下升温至1880℃保温20min进行气相渗硅处理；即在C/C复合材料表面获得抗氧化烧蚀涂层。7) The C/C composite material with the pre-coating layer is placed on a porous graphite plate, and then placed in a graphite crucible with a certain amount of silicon blocks at the bottom; then, the temperature is raised to 1880° C. and kept for 20 minutes under the protection of an argon atmosphere for vapor phase siliconization treatment; that is, an anti-oxidation and ablation coating is obtained on the surface of the C/C composite material.
步骤三，等离子火焰烧蚀考核涂层：Step 3: Plasma flame ablation test coating:
在热流密度为6.65MW/m2的等离子火焰下烧蚀30s，涂层试样的线烧蚀率为0.33μm/s。所述过程中氩气的气体流量为60slpm，氢气的气体流量为1slpm，火焰喷枪口与试样表面垂直距离为40mm，此时涂层试样表面温度超过3000℃。The coating sample was ablated for 30 seconds under a plasma flame with a heat flux density of 6.65 MW/m2 , and the linear ablation rate was 0.33 μm/s. During the process, the gas flow rate of argon was 60 slpm, the gas flow rate of hydrogen was 1 slpm, the vertical distance between the flame spray gun and the sample surface was 40 mm, and the surface temperature of the coating sample exceeded 3000°C.
实施例2Example 2
一种利用聚合物转化陶瓷制备C/C复合材料抗氧化烧蚀涂层的方法，包括以下步骤：A method for preparing a C/C composite material anti-oxidation ablation coating by using polymer-converted ceramics comprises the following steps:
步骤一，制备单源聚合物转化陶瓷粉体：Step 1: Preparation of single-source polymer-converted ceramic powder:
1)首先，将磁子和适量沸石加入三颈瓶，接着称量40g聚硅氮烷于三颈瓶中，并继续添加称量好的20gHfC聚合物前驱体，随后向三颈瓶内添加60g二甲苯得到混合溶液。然后，将Schlenk设备各接口处均涂抹上真空油脂以确保装置连接后具有良好的气密性。1) First, add the magnet and an appropriate amount of zeolite into a three-necked bottle, then weigh 40g of polysilazane into the three-necked bottle, and continue to add the weighed 20g of HfC polymer precursor, and then add 60g of xylene into the three-necked bottle to obtain a mixed solution. Then, apply vacuum grease to each interface of the Schlenk device to ensure good airtightness after the device is connected.
2)接着，打开真空泵开关阀门除去装置中的空气和残余的水汽，当真空表显示真空度到-0.9MPa时关闭真空泵静待5min进行保压操作，若静置期间真空表示数未发生变化，则视装置气密性良好，可以继续下一步操作。此时缓慢转动Schlenk装置中双排管上的阀门填充氩气进行第一次洗气处理。重复上述抽真空充氩气的步骤反复三次以确保装置内为无水无氧的环境。2) Next, open the vacuum pump switch valve to remove the air and residual water vapor in the device. When the vacuum gauge shows that the vacuum degree reaches -0.9MPa, turn off the vacuum pump and wait for 5 minutes to maintain the pressure. If the vacuum gauge number does not change during the static period, the air tightness of the device is good and you can proceed to the next step. At this time, slowly turn the valve on the double-row pipe in the Schlenk device to fill argon gas for the first gas washing treatment. Repeat the above steps of vacuuming and filling argon gas three times to ensure that the device is a water-free and oxygen-free environment.
3)此时将氩气流量调大，打开三颈瓶底部的磁力搅拌器进行加热搅拌。上述加热搅拌的温度为70℃，反应时间为3h。3) At this time, the argon flow rate was increased, and the magnetic stirrer at the bottom of the three-necked flask was turned on for heating and stirring. The temperature of the heating and stirring was 70° C., and the reaction time was 3 h.
4)加热搅拌结束后，将三颈瓶底部的加热台温度降至60℃并保持，同时向其顶部连接的冷凝器内通入冷凝水进行冷却，缓慢打开真空泵阀门除去瓶中剩余的溶剂。4) After heating and stirring, the temperature of the heating platform at the bottom of the three-necked flask was lowered to 60°C and maintained, and condensed water was introduced into the condenser connected to the top of the flask for cooling, and the vacuum pump valve was slowly opened to remove the remaining solvent in the flask.
5)将除去溶剂的反应物从三颈瓶中取出，置于管式炉在温度为250℃时交联固化并且保温处理2h，处理气氛为氩气气氛，之后收集固化后的聚合物转化陶瓷粉体。5) The reactant after the solvent is removed is taken out from the three-necked flask, placed in a tube furnace at a temperature of 250° C. for cross-linking and curing and heat preservation for 2 hours in an argon atmosphere, and then the cured polymer-converted ceramic powder is collected.
步骤二，浆料涂覆结合高温气相渗硅法制备涂层：Step 2: Slurry coating combined with high temperature vapor phase siliconization method to prepare the coating:
1)将密度为1.80g/cm3的C/C块体加工成尺寸为φ20mm×5mm的圆柱形试样，经去离子水超声清洗并在温度为90℃的电热鼓风干燥箱中烘干后得到用于之后制备涂层的C/C基体。1) A C/C block with a density of 1.80 g/cm3 was processed into a cylindrical sample with a size of φ20 mm×5 mm, and after ultrasonic cleaning with deionized water and drying in an electric heated forced air drying oven at a temperature of 90°C, a C/C substrate for subsequent coating preparation was obtained.
2)将30wt％的SiC，10wt％的酚醛树脂溶于60wt％的无水乙醇，经过充分搅拌和超声后得到浆料A。2) 30 wt % of SiC and 10 wt % of phenolic resin were dissolved in 60 wt % of anhydrous ethanol, and slurry A was obtained after sufficient stirring and ultrasonic treatment.
3)将C/C基体浸入到料浆A中静置5s，取出后干燥，重复该过程4次。3) Immerse the C/C substrate in slurry A and let it stand for 5 seconds. Take it out and dry it. Repeat this process 4 times.
4)20wt％的SiC，40wt％的聚合物转化陶瓷粉体，3wt％的酚醛树脂溶于37wt％的无水乙醇，经过充分搅拌和超声后得到浆料B。4) 20 wt% of SiC, 40 wt% of polymer-converted ceramic powder, and 3 wt% of phenolic resin are dissolved in 37 wt% of anhydrous ethanol, and slurry B is obtained after sufficient stirring and ultrasonic treatment.
5)将带有浆料A涂覆并干燥后的C/C基体浸入到料浆B中静置5s，取出后干燥，重复该过程5次。5) Immerse the C/C substrate coated with slurry A and dried into slurry B and let it stand for 5 seconds. Take it out and dry it. Repeat this process 5 times.
6)将涂覆结束的试样在300℃下固化2h，再于900℃氩气气氛保护下碳化2h，得到预涂层试样。6) The coated sample was cured at 300° C. for 2 h, and then carbonized at 900° C. for 2 h under argon atmosphere protection to obtain a pre-coated sample.
7)将带有预涂层的C/C复合材料放于多孔石墨板上，再放入底部置有一定量的硅块的石墨坩埚中；然后在氩气气氛的保护下升温至1900℃保温15min进行气相渗硅处理，即在C/C复合材料表面获得抗氧化烧蚀涂层。7) The C/C composite material with the pre-coating layer is placed on a porous graphite plate, and then placed in a graphite crucible with a certain amount of silicon blocks at the bottom; then, the temperature is raised to 1900° C. under the protection of an argon atmosphere and kept for 15 minutes for vapor phase siliconization treatment, so that an anti-oxidation and ablation coating is obtained on the surface of the C/C composite material.
步骤三，等离子火焰烧蚀考核涂层：Step 3: Plasma flame ablation test coating:
在热流密度为6.65MW/m2的等离子火焰下烧蚀90s，涂层试样的线烧蚀率为-0.167μm/s。所述过程中氩气的气体流量为60slpm，氢气的气体流量为1slpm，火焰喷枪口与试样表面垂直距离为40mm，此时涂层试样表面温度超过3000℃。The coating sample was ablated for 90 seconds under a plasma flame with a heat flux of 6.65 MW/m2 , and the linear ablation rate was -0.167 μm/s. During the process, the gas flow rate of argon was 60 slpm, the gas flow rate of hydrogen was 1 slpm, the vertical distance between the flame spray gun and the sample surface was 40 mm, and the surface temperature of the coating sample exceeded 3000°C.
实施例3Example 3
一种利用聚合物转化陶瓷制备C/C复合材料抗氧化烧蚀涂层的方法，包括以下步骤：A method for preparing a C/C composite material anti-oxidation ablation coating by using polymer-converted ceramics comprises the following steps:
步骤一，制备单源聚合物转化陶瓷粉体：Step 1: Preparation of single-source polymer-converted ceramic powder:
1)首先，将磁子和适量沸石加入三颈瓶，接着称量40g聚硅氮烷于三颈瓶中，并继续添加称量好的20g钛酸四丁酯，随后向三颈瓶内添加60g二甲苯得到混合溶液。然后，将Schlenk设备各接口处均涂抹上真空油脂以确保装置连接后具有良好的气密性。1) First, add the magnet and an appropriate amount of zeolite into a three-necked bottle, then weigh 40g of polysilazane into the three-necked bottle, and continue to add the weighed 20g of tetrabutyl titanate, and then add 60g of xylene into the three-necked bottle to obtain a mixed solution. Then, apply vacuum grease to each interface of the Schlenk device to ensure good airtightness after the device is connected.
2)接着，打开真空泵开关阀门除去装置中的空气和残余的水汽，当真空表显示真空度到-0.9MPa时关闭真空泵静待5min进行保压操作，若静置期间真空表示数未发生变化，则视装置气密性良好，可以继续下一步操作。此时缓慢转动Schlenk装置中双排管上的阀门填充氩气进行第一次洗气处理。重复上述抽真空充氩气的步骤反复三次以确保装置内为无水无氧的环境。2) Next, open the vacuum pump switch valve to remove the air and residual water vapor in the device. When the vacuum gauge shows that the vacuum degree reaches -0.9MPa, turn off the vacuum pump and wait for 5 minutes to maintain the pressure. If the vacuum gauge number does not change during the static period, the air tightness of the device is good and you can proceed to the next step. At this time, slowly turn the valve on the double-row pipe in the Schlenk device to fill argon gas for the first gas washing treatment. Repeat the above steps of vacuuming and filling argon gas three times to ensure that the device is a water-free and oxygen-free environment.
3)此时将氩气流量调大，打开三颈瓶底部的磁力搅拌器进行加热搅拌。上述加热搅拌的温度为80℃，反应时间为3h。3) At this time, the argon flow rate was increased, and the magnetic stirrer at the bottom of the three-necked flask was turned on for heating and stirring. The temperature of the heating and stirring was 80° C., and the reaction time was 3 h.
4)加热搅拌结束后，将三颈瓶底部的加热台温度降至70℃并保持，同时向其顶部连接的冷凝器内通入冷凝水进行冷却，缓慢打开真空泵阀门除去瓶中剩余的溶剂。4) After heating and stirring, the temperature of the heating platform at the bottom of the three-necked flask was lowered to 70°C and maintained, and condensed water was introduced into the condenser connected to the top of the flask for cooling, and the vacuum pump valve was slowly opened to remove the remaining solvent in the flask.
5)将除去溶剂的反应物从三颈瓶中取出，置于管式炉在温度为250℃时交联固化并且保温处理2h，处理气氛为氩气气氛，之后收集固化后的聚合物转化陶瓷粉体。5) The reactant after the solvent is removed is taken out from the three-necked flask, placed in a tube furnace at a temperature of 250° C. for cross-linking and curing and heat preservation for 2 hours in an argon atmosphere, and then the cured polymer-converted ceramic powder is collected.
步骤二，浆料涂覆结合高温气相渗硅法制备涂层：Step 2: Slurry coating combined with high temperature vapor phase siliconization method to prepare the coating:
1)将密度为1.85g/cm3的C/C块体加工成尺寸为φ20mm×5mm的圆柱形试样，经去离子水超声清洗并在温度为90℃的电热鼓风干燥箱中烘干后得到用于之后制备涂层的C/C基体。1) A C/C block with a density of 1.85 g/cm3 was processed into a cylindrical sample with a size of φ20 mm×5 mm, and after ultrasonic cleaning with deionized water and drying in an electric heated forced air drying oven at a temperature of 90°C, a C/C substrate for subsequent coating preparation was obtained.
2)将30wt％的SiC，10wt％的酚醛树脂溶于60wt％的无水乙醇，经过充分搅拌和超声后得到浆料A。2) 30 wt % of SiC and 10 wt % of phenolic resin were dissolved in 60 wt % of anhydrous ethanol, and slurry A was obtained after sufficient stirring and ultrasonic treatment.
3)将C/C基体浸入到料浆A中静置5s，取出后干燥，重复该过程4次。3) Immerse the C/C substrate in slurry A and let it stand for 5 seconds. Take it out and dry it. Repeat this process 4 times.
4)18wt％的SiC，36wt％的聚合物转化陶瓷粉体，6wt％的酚醛树脂溶于40wt％的无水乙醇，经过充分搅拌和超声后得到浆料B。4) 18 wt% of SiC, 36 wt% of polymer-converted ceramic powder, and 6 wt% of phenolic resin are dissolved in 40 wt% of anhydrous ethanol, and slurry B is obtained after sufficient stirring and ultrasonic treatment.
5)将带有浆料A涂覆并干燥后的C/C基体浸入到料浆B中静置5s，取出后干燥，重复该过程5次。5) Immerse the C/C substrate coated with slurry A and dried into slurry B and let it stand for 5 seconds. Take it out and dry it. Repeat this process 5 times.
6)将涂覆结束的试样在300℃下固化2h，再于900℃氩气气氛保护下碳化2h，得到预涂层试样。6) The coated sample was cured at 300° C. for 2 h, and then carbonized at 900° C. for 2 h under argon atmosphere protection to obtain a pre-coated sample.
7)将带有预涂层的C/C复合材料放于多孔石墨板上，再放入底部置有一定量的硅块的石墨坩埚中；然后在氩气气氛的保护下升温至1860℃保温25min进行气相渗硅处理，即在C/C复合材料表面获得抗氧化烧蚀涂层。7) The C/C composite material with the pre-coating layer is placed on a porous graphite plate, and then placed in a graphite crucible with a certain amount of silicon blocks at the bottom; then, the temperature is raised to 1860° C. under the protection of an argon atmosphere and kept for 25 minutes for vapor phase siliconization treatment, so that an anti-oxidation and ablation coating is obtained on the surface of the C/C composite material.
步骤三，等离子火焰烧蚀考核涂层：Step 3: Plasma flame ablation test coating:
在热流密度为6.65MW/m2的等离子火焰下烧蚀120s，涂层试样的线烧蚀率为-0.25μm/s。所述过程中氩气的气体流量为60slpm，氢气的气体流量为1slpm，火焰喷枪口与试样表面垂直距离为40mm，此时涂层试样表面温度超过3000℃。The coating sample was ablated for 120 seconds under a plasma flame with a heat flux density of 6.65 MW/m2 , and the linear ablation rate was -0.25 μm/s. During the process, the gas flow rate of argon was 60 slpm, the gas flow rate of hydrogen was 1 slpm, the vertical distance between the flame spray gun and the sample surface was 40 mm, and the surface temperature of the coating sample exceeded 3000°C.
所有实施例中的涂层均具有较低的线烧蚀率，表现出优异的抗烧蚀性能。The coatings in all examples have lower linear ablation rates and exhibit excellent anti-ablation performance.
为了说明本发明提供的在C/C复合材料表面获得抗氧化烧蚀涂层的相关性能，结合附图，以实施例1为例进行说明。In order to illustrate the relevant performance of the anti-oxidation and ablation coating obtained on the surface of the C/C composite material provided by the present invention, Example 1 is taken as an example for description in conjunction with the accompanying drawings.
图2为不同温度热处理后得到的单源聚合物转化陶瓷的SEM照片：(a)900℃,(b)1900℃；从图2可知，随着热处理温度的升高，单源聚合物转化陶瓷粉末的形貌发生显著改变。陶瓷颗粒表面由光滑致密转变为分布大量微孔(孔隙直径约为1μm)的粗糙结构，这是单源聚合物在该温度区间内发生了裂解，释放了大量小分子以及气态产物造成的。Figure 2 shows the SEM photos of the single-source polymer-converted ceramics obtained after heat treatment at different temperatures: (a) 900℃, (b) 1900℃; As shown in Figure 2, the morphology of the single-source polymer-converted ceramic powder changes significantly with the increase of the heat treatment temperature. The surface of the ceramic particles changes from smooth and dense to a rough structure with a large number of micropores (pore diameter is about 1μm), which is caused by the cracking of the single-source polymer in this temperature range, releasing a large number of small molecules and gaseous products.
图3为实施例1提供的固化及碳化后得到的预涂层试样的SEM照片：(a)表面SEM照片，(b)截面SEM照片；从图3可知，预涂层厚度约270μm，具有明显的双层结构，并且整体结构疏松多孔。预涂层的表面分布着许多微裂纹和孔隙，这些缺陷可以为后续高温气相渗硅过程中气态硅致密化涂层提供渗入通道。FIG3 is an SEM photo of the pre-coating sample obtained after curing and carbonization provided in Example 1: (a) surface SEM photo, (b) cross-sectional SEM photo; As can be seen from FIG3, the pre-coating thickness is about 270 μm, with an obvious double-layer structure, and the overall structure is loose and porous. There are many microcracks and pores on the surface of the pre-coating, and these defects can provide infiltration channels for the gaseous silicon densification coating in the subsequent high-temperature gas phase siliconization process.
图4为实施例1浆料涂覆结合高温气相渗硅后得到的涂层试样的SEM照片：(a)表面SEM照片，(b)截面SEM照片；从图4可知，高温气相渗硅后，在图3得知的预涂层内存在的缺陷几乎完全消失。同时涂层双层结构消失，在硅渗的辅助下形成了致密的SiC-PDCs涂层。此外，气态硅具有强渗透能力，能够轻易穿过多孔预涂层到达C/C基体与涂层之间的界面并且发生反应，最终在界面处生成一层锯齿状SiC-Si过渡层。FIG4 is an SEM photo of the coating sample obtained after slurry coating combined with high-temperature vapor phase siliconization in Example 1: (a) surface SEM photo, (b) cross-sectional SEM photo; As can be seen from FIG4, after high-temperature vapor phase siliconization, the defects existing in the pre-coating shown in FIG3 almost completely disappear. At the same time, the double-layer structure of the coating disappears, and a dense SiC-PDCs coating is formed with the assistance of siliconization. In addition, gaseous silicon has a strong permeability and can easily pass through the porous pre-coating to reach the interface between the C/C substrate and the coating and react, eventually forming a jagged SiC-Si transition layer at the interface.
图5为实施例1提供的涂层等离子烧蚀后的表面宏观形貌照片。从图5可知，经过等离子烧蚀30s、90s和120s后，试样表面涂层结构依然完整，同时表面未出现明显凹坑和宏观裂纹等缺陷，说明该试样抗烧蚀性能良好。Figure 5 is a macroscopic surface morphology photograph of the coating after plasma ablation provided in Example 1. As can be seen from Figure 5, after 30s, 90s and 120s of plasma ablation, the coating structure on the sample surface is still intact, and no obvious pits and macroscopic cracks appear on the surface, indicating that the sample has good anti-ablation performance.
尽管已经示出和描述了本发明的实施例，对于本领域的普通技术人员而言，可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型，本发明的范围由所附权利要求及其等同物限定。Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.
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