CN104230367A - A kind of SiC-ZrC-ZrB2 nanocomposite ceramics modified C/C composite material and preparation method thereof - Google Patents

Abstract

Translated fromChinese

本发明涉及一种SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C复合材料及其制备方法。其技术方案是：将1~5wt％的有机硼、5~10wt％的有机硅、10~20wt％的ZrC前驱体和65~84wt％的沥青甲苯可溶组份混合，加入溶剂使混合物溶解，得到的溶液在300~450°C反应1~4h，得到硼硅锆掺杂沥青；用硼硅锆掺杂沥青对炭纤维预制体进行浸渍，随后进行热解处理，得到SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体；用硼硅锆掺杂沥青对C/C坯体重复进行浸渍和热解循环处理，直至密度达到1.9~2.5g/cm³，即得SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C复合材料。本发明制备的复合材料具有较好的机械性能、较宽温度范围的自愈合抗氧化能力和超高温抗烧蚀性能。

The invention relates to a SiC-ZrC-_ZrB2 nano-composite ceramic modified C/C composite material and a preparation method thereof. The technical solution is: mix 1~5wt% organoboron, 5~10wt% organosilicon, 10~20wt% ZrC precursor and 65~84wt% asphalt toluene soluble components, add solvent to dissolve the mixture, The obtained solution was reacted at 300-450°C for 1-4 hours to obtain borosilicate-zirconium-doped pitch; the carbon fiber preform was impregnated with borosilicate-zirconium-doped pitch, followed by pyrolysis treatment to obtain SiC-ZrC-ZrB₂ Nano-composite ceramics modify the C/C green body; the C/C green body is repeatedly impregnated and pyrolyzed with borosilicate-zirconium-doped pitch until the density reaches 1.9~2.5g/cm³ to obtain SiC-ZrC -ZrB₂ nano-composite ceramics modified C/C composites. The composite material prepared by the invention has good mechanical properties, self-healing and anti-oxidation ability in a wide temperature range and ultra-high temperature anti-ablation performance.

Description

Translated fromChinese

一种SiC-ZrC-ZrB2纳米复相陶瓷改性C/C复合材料及其制备方法A kind of SiC-ZrC-ZrB2 nanocomposite ceramics modified C/C composite material and preparation method thereof

技术领域technical field

本发明属于C/C复合材料技术领域。涉及一种SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C复合材料及其制备方法。The invention belongs to the technical field of C/C composite materials. The invention relates to a SiC-ZrC-_ZrB2 nano-composite ceramic modified C/C composite material and a preparation method thereof.

背景技术Background technique

C/C复合材料具有低密度、高比强度、高比模量、低热膨胀系数、耐热冲击和耐烧蚀等一系列优良性能，在航空、航天、核能及民用领域具有广阔的应用前景。然而，由于C/C复合材料在450°C以上的有氧环境就开始氧化，氧化直接导致C/C复合材料的孔隙增加、机械性能降低，且随着温度的升高，复合材料的氧化程度呈现显著上升趋势，如果不采取有效的氧化防护措施，在高温氧化环境长时间使用C/C复合材料将会产生灾难性的后果。随着我国航空航天领域发展对超高温材料性能要求的不断提升，解决C/C复合材料的高温氧化防护问题就显得尤为重要。 C/C composite materials have a series of excellent properties such as low density, high specific strength, high specific modulus, low thermal expansion coefficient, thermal shock resistance and ablation resistance, and have broad application prospects in aviation, aerospace, nuclear energy and civil fields. However, since the C/C composite material begins to oxidize in an aerobic environment above 450°C, the oxidation directly leads to the increase of the pores of the C/C composite material and the decrease of mechanical properties, and as the temperature increases, the degree of oxidation of the composite material It shows a significant upward trend. If effective oxidation protection measures are not taken, the long-term use of C/C composites in high-temperature oxidizing environments will have disastrous consequences. With the continuous improvement of the performance requirements of ultra-high temperature materials in the development of my country's aerospace field, it is particularly important to solve the problem of high temperature oxidation protection of C/C composite materials.

目前，提高C/C复合材料高温抗氧化能力的方法主要有两种：一种是在复合材料表面制备抗氧化涂层，利用涂层来阻隔氧化性气氛，达到抗氧化的目的；另一种是对复合材料基体进行改性(李贺军, 薛晖, 付前刚, 等. C/C复合材料高温抗氧化涂层的研究现状与展望. 无机材料学报, 2010, 25(4): 339-42.)，通过在基体内部引入抗氧化组分提高其自身的抗氧化能力。对表面涂层法而言，由于涂层材料与C/C复合材料之间的热膨胀系数匹配问题很难得到根本解决，在制备与使用过程中，材料中的热应力会使涂层产生微裂纹甚至脱落；机械损伤也会使涂层出现创伤面，失去对C/C复合材料的保护作用。这一缺陷大大限制了抗氧化涂层技术向更高工作温度、更长工作寿命的方向发展(杨星, 崔红, 闫联生. C/C复合材料基体改性研究现状. 材料导报, 2007, 21(8):22-9)。 At present, there are two main methods to improve the high-temperature oxidation resistance of C/C composite materials: one is to prepare an anti-oxidation coating on the surface of the composite material, and use the coating to block the oxidative atmosphere to achieve the purpose of anti-oxidation; It is to modify the matrix of composite materials (Li Hejun, Xue Hui, Fu Qiangang, et al. Research status and prospects of high-temperature oxidation-resistant coatings for C/C composite materials. Journal of Inorganic Materials,2010, 25(4): 339-42.), by introducing antioxidant components into the matrix to improve its own antioxidant capacity. For the surface coating method, it is difficult to fundamentally solve the problem of matching the thermal expansion coefficient between the coating material and the C/C composite material. During the process of preparation and use, the thermal stress in the material will cause microcracks in the coating. Even fall off; mechanical damage will also cause the coating to have a traumatic surface and lose its protective effect on the C/C composite material. This defect greatly limits the development of anti-oxidation coating technology towards higher working temperature and longer working life (Yang Xing, Cui Hong, Yan Liansheng. Research status of C/C composite matrix modification. Materials Herald, 2007, 21 (8):22-9).

基体改性法是通过不同方式在C/C复合材料基体中引入碳化物、硼化物、硅化物等陶瓷相作为阻氧剂，这些阻氧剂在高温和氧化性气氛中能够氧化成可流动的玻璃态固熔体，进而形成具有自愈合功能的保护膜，能有效掩蔽材料表面缺陷和微裂纹，减少氧化活性点部位，同时阻止氧气向材料内部扩散，从而在很大程度上抑制或完全阻止氧化反应的发生。大量研究表明，在C/C复合材料基体中同时引入SiC、ZrC、ZrB₂等陶瓷相，可以大大提高材料的抗氧化、抗烧蚀性能(李厚补，张立同，成来飞，王一光. C/ZrB₂–SiC复合材料的不同结构涂层在氧乙炔焰下的抗烧蚀性. 国际应用陶瓷技术，2009, 6(2):145-50；李照谦，李贺军，张守阳，李克智.采用两步法制备的整体毡增强C/C–SiC–ZrC复合材料的微结构和烧蚀行为. 陶瓷国际，2012, 38(4): 3419-25)。目前将SiC、ZrC、ZrB₂等陶瓷相引入到C/C复合材料基体中的方法主要有气相法和固相法。气相法通常采用化学气相渗透技术(CVI)将陶瓷相引入，由于CVI过程多发生在预制体表面附近，中心区域通常不易沉积而表面容易出现封孔现象，影响进一步的致密化。此外，CVI过程中通常会产生大量腐蚀性气体，对设备的要求较高，而且制备周期长，生产成本高，这些因素都限制了它的大规模应用。固相法通过浆料浸渗(汤素芳，邓景屹，王石军，杨柯. 超高温陶瓷复合材料的烧蚀行为. 材料科学与工程 A. 2007, 465(1-2):1-7；汤素芳，邓景屹，刘文川，杨柯. 预浸SiC填充物的二维C/C复合材料的机械和烧蚀性质. 炭，2006，44(14)：2877-82)或浆料涂刷(李厚补，张立同，成来飞，王一光. C/ZrB₂–SiC 复合材料的不同结构涂层在氧乙炔焰下的抗烧蚀性. 国际应用陶瓷技术，2009, 6(2):145-50)将陶瓷微粉引入到炭纤维预制体或C/C复合材料中。但在具体实施过程中存在以下两个问题：(1)很难实现陶瓷颗粒在基体炭和炭纤维束内的均匀分布，因而在很大程度上限制了各种陶瓷组分之间协同抗氧化能力的充分发挥(Paul P. P., Schwab S.T. 通过沥青的金属有机修饰得到炭材料及其抗氧化性. 炭, 1996, 34 (1): 89-95)；(2)抗氧化陶瓷颗粒的加入通常是以降低C/C复合材料的高温性能为代价的。加入量过多会使复合材料的机械性能明显下降，而加入量太少，不足以形成满足要求的玻璃层，起不到完全隔离氧，防止其扩散进入材料基体的作用(弭群，曹丽云，黄剑锋. 碳/碳复合材料基体抗氧化改性研究进展. 兵器材料科学与工程, 2010, 33(2): 98-102)。The matrix modification method is to introduce ceramic phases such as carbides, borides, and silicides into the matrix of C/C composites in different ways as oxygen inhibitors. Glassy solid solution, and then form a protective film with self-healing function, which can effectively cover the surface defects and microcracks of the material, reduce the active spots of oxidation, and prevent oxygen from diffusing into the material, thereby inhibiting or completely inhibiting the prevent oxidation reactions from occurring. A large number of studies have shown that introducing SiC, ZrC,_ZrB2 and other ceramic phases into the C/C composite matrix can greatly improve the anti-oxidation and anti-ablation properties of the material (Li Houbu, Zhang Litong, Cheng Laifei, Wang Yiguang. C Ablation resistance of different structural coatings of /ZrB₂ -SiC composites under oxyacetylene flame. International Applied Ceramic Technology, 2009, 6(2):145-50; Li Zhaoqian, Li Hejun, Zhang Shouyang, Li Kezhi. Two-step Microstructure and Ablation Behavior of Integral Mat Reinforced C/C–SiC–ZrC Composites Prepared by Method. Ceramics International, 2012, 38(4): 3419-25). At present, the methods for introducing ceramic phases such as SiC, ZrC,_{and ZrB2} into the C/C composite matrix mainly include gas phase method and solid phase method. The gas phase method usually uses chemical vapor infiltration technology (CVI) to introduce the ceramic phase. Since the CVI process mostly occurs near the surface of the preform, the central area is usually not easy to deposit and the surface is prone to sealing, which affects further densification. In addition, the CVI process usually produces a large amount of corrosive gas, which requires high equipment, and the preparation cycle is long and the production cost is high. These factors limit its large-scale application. Solid phase method through slurry infiltration (Tang Sufang, Deng Jingyi, Wang Shijun, Yang Ke. Ablation behavior of ultra-high temperature ceramic composites. Materials Science and Engineering A. 2007, 465(1-2):1-7; Tang Sufang, Deng Jingyi, Liu Wenchuan, Yang Ke. Mechanical and ablative properties of two-dimensional C/C composites pre-impregnated with SiC fillers. Carbon, 2006, 44(14): 2877-82) or slurry brushing (Li Houbu, Zhang Litong, Cheng Laifei, Wang Yiguang. Ablation resistance of different structural coatings of C/ZrB₂ -SiC composites under oxyacetylene flame. International Applied Ceramic Technology, 2009, 6(2):145-50) Micropowder is introduced into carbon fiber preforms or C/C composites. However, there are two problems in the specific implementation process: (1) It is difficult to achieve a uniform distribution of ceramic particles in the matrix carbon and carbon fiber bundles, thus limiting the synergistic oxidation resistance between various ceramic components to a large extent. (Paul PP, Schwab ST obtained carbon materials and their oxidation resistance through the metal-organic modification of asphalt. Charcoal, 1996, 34 (1): 89-95); (2) The addition of anti-oxidation ceramic particles is usually At the expense of reducing the high temperature performance of the C/C composite. Too much added amount will significantly reduce the mechanical properties of the composite material, and too little added amount will not be enough to form a glass layer that meets the requirements, and it will not be able to completely isolate oxygen and prevent it from diffusing into the material matrix (Mi Qun, Cao Liyun, Huang Jianfeng. Research Progress on Oxidative Modification of Carbon/Carbon Composite Matrix. Weapon Materials Science and Engineering, 2010, 33(2): 98-102).

发明内容Contents of the invention

本发明旨在克服现有技术的不足，目的是提供一种SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C复合材料的制备方法，用该方法制备的SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C复合材料具有较好的机械性能、较宽温度范围的自愈合抗氧化能力和超高温抗烧蚀性能。The present invention aims to overcome the deficiencies in the prior art, and the purpose is to provide a preparation method of SiC-ZrC-_ZrB2 nano-composite ceramics modified C/C composite material, and the SiC-ZrC-_ZrB2 nano-composite material prepared by this method Phase ceramics modified C/C composites have good mechanical properties, self-healing and oxidation resistance in a wide temperature range, and ultra-high temperature ablation resistance.

为实现上述目的，本发明采用的技术方案是： In order to achieve the above object, the technical scheme adopted in the present invention is:

步骤一、炭纤维预制体的预处理Step 1. Pretreatment of carbon fiber preform

将炭纤维预制体用丙酮清洗30~60min，在70~100°C条件下干燥1~2h，得到预处理炭纤维预制体。The carbon fiber preform was washed with acetone for 30-60 minutes, and dried at 70-100°C for 1-2 hours to obtain a pretreated carbon fiber preform.

步骤二、硼硅锆掺杂沥青的制备Step 2, preparation of borosilicate zirconium doped pitch

先将沥青溶于甲苯中，在室温条件下静置1~2h，固液分离，在110~150°C条件下对固液分离后的溶液进行蒸馏，得到沥青甲苯可溶组份。Dissolve the asphalt in toluene first, let it stand at room temperature for 1~2h, separate the solid and liquid, and distill the solution after the solid-liquid separation at 110~150°C to obtain the asphalt toluene soluble component.

将1~5wt％的有机硼、5~10wt％的有机硅、10~20wt％的ZrC前驱体和65~84wt％的沥青甲苯可溶组份混合，即得混合物。向混合物中加入溶剂，混合物与溶剂的质量比为1︰(1~2)，磁力搅拌0.5~1h，即得混合液。再将混合液转入反应釜中，通入惰性气体，在机械搅拌条件下以2~10°C/min的升温速率将反应釜升温至300~450°C，保温1~4h，自然冷却至室温，得到硼硅锆掺杂沥青。Mix 1-5wt% organic boron, 5-10wt% organic silicon, 10-20wt% ZrC precursor and 65-84wt% asphalt toluene soluble components to obtain the mixture. Add a solvent to the mixture, the mass ratio of the mixture to the solvent is 1:(1~2), stir magnetically for 0.5~1h, and the mixture is obtained. Then the mixed solution is transferred to the reaction kettle, and the inert gas is introduced, and the reaction kettle is heated to 300~450°C at a heating rate of 2~10°C/min under the condition of mechanical stirring, kept for 1~4h, and naturally cooled to At room temperature, borosilicate zirconium doped pitch was obtained.

步骤三、预处理炭纤维预制体的浸渍和热解Step 3. Impregnation and pyrolysis of pretreated carbon fiber preform

按硼硅锆掺杂沥青与预处理炭纤维预制体的质量比为1︰(0.2~0.5)，将预处理炭纤维预制体置于金属圆筒内，用硼硅锆掺杂沥青将预处理炭纤维预制体覆盖。将装有硼硅锆掺杂沥青和预处理炭纤维预制体的金属圆筒置于高压反应釜内，先抽真空至0.02~0.08MPa，再将高压反应釜内温度升至250~300°C，充惰性气体至高压反应釜内的压力为3~5MPa，保温保压0.5~2 h。然后在相同的压力条件下升温至350~500°C，保温保压4~6h，自然冷却至室温，泄压。再将金属圆筒从高压反应釜内取出，放入高温炭化炉中，在氩气气氛保护下，以2~10°C/min的升温速率升温至1400~1600 °C，保温1~3h，冷却至室温，得到SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体。将所述C/C坯体表面打磨抛光，在介质中超声波清洗，烘干。According to the mass ratio of borosilicate zirconium doped pitch to pretreated carbon fiber prefabricated body is 1: (0.2~0.5), the pretreated carbon fiber prefabricated body is placed in a metal cylinder, and the pretreated carbon fiber prefabricated Carbon fiber preform covering. Put the metal cylinder containing borosilicate-zirconium-doped pitch and pretreated carbon fiber prefabricated body in the autoclave, first evacuate to 0.02~0.08MPa, and then raise the temperature in the autoclave to 250~300°C , fill inert gas to the pressure in the autoclave is 3~5MPa, heat preservation and pressure for 0.5~2 h. Then raise the temperature to 350~500°C under the same pressure conditions, keep the temperature and hold the pressure for 4~6h, cool down to room temperature naturally, and release the pressure. Then take the metal cylinder out of the high-pressure reaction kettle, put it into a high-temperature carbonization furnace, and under the protection of an argon atmosphere, raise the temperature to 1400-1600 °C at a heating rate of 2-10 °C/min, and keep it for 1-3 hours. Cool to room temperature to obtain a SiC-ZrC-ZrB₂ nanocomposite ceramic modified C/C green body. The surface of the C/C green body is polished, ultrasonically cleaned in a medium, and dried.

步骤四、SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体的致密化Step 4. Densification of SiC-ZrC-ZrB₂ nanocomposite ceramic modified C/C body

按硼硅锆掺杂沥青与SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体的质量比为1︰(0.2~0.5)，将SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体置于金属圆筒内，用硼硅锆掺杂沥青将SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体覆盖。将装有硼硅锆掺杂沥青和SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体的金属圆筒置于高压反应釜内，抽真空至0.02~0.08MPa，再将高压反应釜内温度升至250~300°C，充惰性气体至反应釜内的压力为3~5MPa，保温保压0.5~2h。然后在相同的压力条件下升温至350~500°C，保温保压4~6h，自然冷却至室温，泄压，完成一次浸渍。将金属圆筒从高压反应釜内取出，放入高温炭化炉中，在氩气气氛保护下，以2~10°C/min的升温速率升温至1400~1600°C，保温1~3h，冷却至室温，完成一次热解，得到增密的SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体。将所述C/C坯体表面打磨抛光，在介质中超声波清洗，烘干。According to the mass ratio of borosilicate-zirconium-doped pitch to SiC-ZrC-ZrB₂ nano-composite ceramics modified C/C green body is 1: (0.2~0.5), SiC-ZrC-ZrB₂ nano-composite ceramics modified The C/C green body is placed in a metal cylinder, and the SiC-ZrC-ZrB₂ nanocomposite ceramic modified C/C green body is covered with borosilicate zirconium doped pitch. Put the metal cylinder containing borosilicate-zirconium-doped pitch and SiC-ZrC-ZrB₂ nano-composite ceramic modified C/C green body in the high-pressure reaction kettle, vacuumize to 0.02~0.08MPa, and then put the high-pressure reaction The temperature in the kettle is raised to 250~300°C, filled with an inert gas until the pressure in the reactor is 3~5MPa, and the temperature is maintained for 0.5~2h. Then raise the temperature to 350~500°C under the same pressure conditions, keep the temperature and pressure for 4~6h, cool down to room temperature naturally, release the pressure, and complete the impregnation once. Take the metal cylinder out of the high-pressure reaction kettle, put it into a high-temperature carbonization furnace, and under the protection of an argon atmosphere, raise the temperature to 1400-1600°C at a heating rate of 2-10°C/min, keep it warm for 1-3 hours, and cool To room temperature, complete a pyrolysis to obtain a densified SiC-ZrC-ZrB₂ nanocomposite ceramic modified C/C green body. The surface of the C/C green body is polished, ultrasonically cleaned in a medium, and dried.

重复上述浸渍、热解、打磨抛光和烘干处理过程，直至SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体的密度达到1.9~2.5g/cm³，即得SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C复合材料。Repeat the above impregnation, pyrolysis, polishing and drying process until the density of the SiC-ZrC-ZrB₂ nano-composite ceramic modified C/C green body reaches 1.9~2.5g/cm³ , that is, SiC-ZrC- ZrB₂ nano-composite ceramics modified C/C composites.

所述炭纤维预制体为整体毡炭纤维预制体、炭布/网胎叠层针刺炭纤维预制体和三维编织炭纤维预制体中的一种，炭纤维预制体的密度为0.2~0.6 g/cm³。The carbon fiber prefabricated body is one of an integral felt carbon fiber prefabricated body, a carbon cloth/net tire laminated needle-punched carbon fiber prefabricated body and a three-dimensional woven carbon fiber prefabricated body, and the density of the carbon fiber prefabricated body is 0.2-0.6 g /cm³ .

所述沥青为煤沥青或为石油沥青。 The pitch is coal pitch or petroleum pitch.

所述有机硼为聚硼氮烷、吡啶硼烷和2-甲基吡啶硼烷中的一种。 The organic boron is one of polyborazane, pyridine borane and 2-picoline borane.

所述有机硅为聚碳硅烷、聚二甲基硅烷和氯代三甲基硅烷中的一种。 The organosilicon is one of polycarbosilane, polydimethylsilane and chlorotrimethylsilane.

所述ZrC前驱体的制备步骤是：将反应器抽真空至0.06~0.08MPa，通入氩气至常压，再依次向反应器中加入甲苯、锆盐和无水乙醇，搅拌均匀。其中：锆盐∶甲苯∶无水乙醇的摩尔比为1∶(3~5)∶(4~10)；然后在−10~10°C条件下通入氨气，通入氨气的流量为40~60ml/min，反应2~6h，过滤，得到醇锆的甲苯溶液。 The preparation steps of the ZrC precursor are as follows: vacuumize the reactor to 0.06-0.08MPa, feed argon to normal pressure, then add toluene, zirconium salt and absolute ethanol to the reactor in sequence, and stir evenly. Wherein: the molar ratio of zirconium salt:toluene:absolute ethanol is 1:(3~5):(4~10); then feed ammonia gas under the condition of −10~10°C, and the flow rate of feeding ammonia gas is 40~60ml/min, react for 2~6h, and filter to obtain a toluene solution of zirconium alkoxide.

将反应器抽真空至0.06~0.08MPa，通入氩气至常压，再依次向反应器加入醇锆的甲苯溶液、β-二酮和酚，搅拌均匀，其中：β-二酮∶酚∶锆盐的摩尔比为(1~4)∶(2~4)∶1；然后按2~4°C/min的升温速率将反应体系加热至120~300°C，保温1~10h，减压蒸馏，冷却至室温，得到ZrC前驱体。 The reactor is evacuated to 0.06~0.08MPa, argon is introduced to normal pressure, and then the toluene solution of zirconium alkoxide, β-diketone and phenol are sequentially added to the reactor, and stirred evenly, wherein: β-diketone: phenol: The molar ratio of zirconium salt is (1~4):(2~4):1; then the reaction system is heated to 120~300°C at a heating rate of 2~4°C/min, kept for 1~10h, and depressurized Distill and cool to room temperature to obtain the ZrC precursor.

所述溶剂为甲苯或为二甲苯。 The solvent is toluene or xylene.

所述机械搅拌的转速为200~600r/min。 The rotating speed of the mechanical stirring is 200~600r/min.

所述惰性气体为氩气或为氮气。 The inert gas is argon or nitrogen.

所述介质为丙酮、无水乙醇和去离子水中的一种。 The medium is one of acetone, absolute ethanol and deionized water.

由于采用上述技术方案，本发明与现有技术相比具有如下积极效果：Owing to adopting above-mentioned technical scheme, the present invention has following positive effect compared with prior art:

(1)本发明通过沥青甲苯可溶组份与有机硼、有机硅和ZrC前驱体的共裂解将硼、硅和锆原子引入沥青的稠环芳烃分子中，使硼、硅和锆杂原子在沥青中达到分子级别的均匀分散，硼硅锆掺杂沥青经高温热处理后能够在基体炭中原位生成均匀弥散的ZrB₂、SiC和ZrC纳米复相陶瓷。(1) The present invention introduces boron, silicon and zirconium atoms into the condensed ring aromatic hydrocarbon molecules of pitch through co-cracking of pitch toluene soluble components and organoboron, organosilicon and ZrC precursors, so that boron, silicon and zirconium heteroatoms are in the The asphalt is evenly dispersed at the molecular level, and the borosilicate-zirconium-doped asphalt can in-situ generate uniformly dispersed ZrB₂ , SiC and ZrC nanocomposite ceramics in the matrix carbon after high-temperature heat treatment.

(2)由于ZrB₂、SiC和ZrC纳米复相陶瓷在基体炭中分布均匀，SiC-ZrC-ZrB₂纳米复相陶瓷在氧化过程中形成的B₂O₃、SiO₂、ZrO₂等氧化物在不同的温度范围内能够互相反应和相互溶解，形成连续而稳定的保护膜，因此只需在C/C复合材料中引入少量的ZrB₂、SiC和ZrC纳米复相陶瓷就能显著提高材料较宽温度范围的自愈合抗氧化能力和超高温抗烧蚀性能。(2) Due to the uniform distribution of ZrB₂ , SiC and ZrC nanocomposite ceramics in the matrix carbon, oxides such as B₂ O₃ , SiO₂ , and ZrO₂ formed during the oxidation process of SiC-ZrC-ZrB₂ nanocomposite ceramics They can react and dissolve each other in different temperature ranges to form a continuous and stable protective film. Therefore, only a small amount of ZrB₂ , SiC and ZrC nanocomposite ceramics can be introduced into the C/C composite material to significantly improve the material's relatively high temperature. Self-healing anti-oxidation ability and ultra-high temperature anti-ablation performance in a wide temperature range.

(3)在基体炭内原位生成的ZrB₂和ZrC与碳之间具有很好的物理和化学相容性，能大大提高C/C复合材料的机械性能。(3) ZrB₂ and ZrC generated in situ in matrix carbon have good physical and chemical compatibility with carbon, which can greatly improve the mechanical properties of C/C composites.

(4)本发明制备的SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C复合材料在静态空气气氛和1100°C条件下氧化10h，试样增重0.2~0.5 wt% ；在1600°C氧化10 h，氧化失重仅0.1~0.3 wt%；在3000°C的氧乙炔焰中氧化烧蚀120s，其线烧蚀率仅为0.001~0.0015mm/s。(4) SiC-ZrC-_ZrB2 nano-composite ceramics modified C/C composite material prepared by the present invention is oxidized 10h under static air atmosphere and 1100 DEG C of conditions, and sample weight gain is 0.2～0.5 wt%; At 1600 DEG C C oxidation for 10 h, oxidation weight loss is only 0.1~0.3 wt%; oxidative ablation in 3000°C oxyacetylene flame for 120s, the line ablation rate is only 0.001~0.0015mm/s.

因此，本发明有效地解决了固相法制备SiC-ZrC-ZrB₂复相陶瓷改性C/C复合材料存在的SiC-ZrC-ZrB₂复相陶瓷在基体炭中分散不均匀的问题，制备的SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C复合材料具有较好的机械性能以及较宽温度范围的自愈合抗氧化能力和超高温抗烧蚀性能。Therefore, the present invention effectively solves the problem of uneven dispersion of SiC-ZrC-_ZrB composite ceramics in matrix carbon in the preparation of SiC-ZrC-_ZrB composite ceramics modified C/C composite materials by solid phase method, and prepares The SiC-ZrC-ZrB₂ nanocomposite ceramic modified C/C composite material has good mechanical properties, self-healing oxidation resistance and ultra-high temperature ablation resistance in a wide temperature range.

附图说明Description of drawings

图１是本发明制备的一种SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C复合材料的XRD谱图；Fig. 1 is the XRD spectrogram of a kind of SiC-ZrC-ZrB_nano- composite ceramics modified C/C composite material prepared by the present invention;

图２是图1所述SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C复合材料表面的SEM照片；Figure 2 is a SEM photo of the surface of the SiC-ZrC-ZrB₂ nanocomposite ceramic modified C/C composite material described in Figure 1;

图３是图2所示SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C复合材料表面碳元素的分布图；Figure 3 is a distribution diagram of carbon elements on the surface of the SiC-ZrC-ZrB₂ nanocomposite ceramics modified C/C composite material shown in Figure 2;

图４是图2所示SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C复合材料表面硼元素的分布图；Fig. 4 is the distribution diagram of boron element on the surface of SiC-ZrC-ZrB₂ nanocomposite ceramics modified C/C composite material shown in Fig. 2;

图5是图2所示SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C复合材料表面硅元素的分布图；Fig. 5 is the distribution figure of silicon element on the surface of SiC-ZrC-ZrB₂ nano-composite ceramics modified C/C composite material shown in Fig. 2;

图6是图2所示SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C复合材料表面锆元素的分布图。Fig. 6 is a distribution diagram of zirconium elements on the surface of the SiC-ZrC-ZrB₂ nanocomposite ceramic modified C/C composite material shown in Fig. 2 .

具体实施方式Detailed ways

下面结合附图和具体实施方式对本发明作进一步描述，并非对其保护范围的限制。 The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments, which is not intended to limit its protection scope.

为避免重复，先将本具体实施方式中的ZrC前驱体的制备步骤统一描述如下，实施例中不再赘述： In order to avoid repetition, the preparation steps of the ZrC precursor in this specific embodiment are first described in a unified manner as follows, and will not be repeated in the examples:

所述ZrC前驱体的制备步骤是：将反应器抽真空至0.06~0.08MPa，通入氩气至常压，再依次向反应器中加入甲苯、锆盐和无水乙醇，搅拌均匀。其中：锆盐∶甲苯∶无水乙醇的摩尔比为1∶(3~5)∶(4~10)；然后在−10~10°C条件下通入氨气，通入氨气的流量为40~60ml/min，反应2~6h，过滤，得到醇锆的甲苯溶液。 The preparation steps of the ZrC precursor are as follows: vacuumize the reactor to 0.06-0.08MPa, feed argon to normal pressure, then add toluene, zirconium salt and absolute ethanol to the reactor in sequence, and stir evenly. Wherein: the molar ratio of zirconium salt:toluene:absolute ethanol is 1:(3~5):(4~10); then feed ammonia gas under the condition of −10~10°C, and the flow rate of feeding ammonia gas is 40~60ml/min, react for 2~6h, and filter to obtain a toluene solution of zirconium alkoxide.

将反应器抽真空至0.06~0.08MPa，通入氩气至常压，再依次向反应器加入醇锆的甲苯溶液、β-二酮和酚，搅拌均匀，其中：β-二酮∶酚∶锆盐的摩尔比为(1~4)∶(2~4)∶1；然后按2~4°C/min的升温速率将反应体系加热至120~300°C，保温1~10h，减压蒸馏，冷却至室温，得到ZrC前驱体。 The reactor is evacuated to 0.06~0.08MPa, argon is introduced to normal pressure, and then the toluene solution of zirconium alkoxide, β-diketone and phenol are sequentially added to the reactor, and stirred evenly, wherein: β-diketone: phenol: The molar ratio of zirconium salt is (1~4):(2~4):1; then the reaction system is heated to 120~300°C at a heating rate of 2~4°C/min, kept for 1~10h, and depressurized Distill and cool to room temperature to obtain the ZrC precursor.

实施例Example11

一种SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C复合材料及其制备方法。所述制备方法的具体步骤是：A SiC-ZrC-ZrB₂ nanometer composite ceramic modified C/C composite material and a preparation method thereof. The concrete steps of described preparation method are:

步骤一、炭纤维预制体的预处理Step 1. Pretreatment of carbon fiber preform

将炭纤维预制体用丙酮清洗30~60min，在70~100°C条件下干燥1~2h，得到预处理炭纤维预制体。The carbon fiber preform was washed with acetone for 30-60 minutes, and dried at 70-100°C for 1-2 hours to obtain a pretreated carbon fiber preform.

步骤二、硼硅锆掺杂沥青的制备Step 2, preparation of borosilicate zirconium doped pitch

先将沥青溶于甲苯中，在室温条件下静置1~2h，固液分离，在110~150°C条件下对固液分离后的溶液进行蒸馏，得到沥青甲苯可溶组份。Dissolve the asphalt in toluene first, let it stand at room temperature for 1~2h, separate the solid and liquid, and distill the solution after the solid-liquid separation at 110~150°C to obtain the asphalt toluene soluble component.

将1~2wt％的有机硼、5~6wt％的有机硅、10~12wt％的ZrC前驱体和80~84wt％的沥青甲苯可溶组份混合，即得混合物。向混合物中加入溶剂，混合物与溶剂的质量比为1︰(1~2)，磁力搅拌0.5~1h，即得混合液。再将混合液转入反应釜中，通入惰性气体，在机械搅拌条件下以2~5°C/min的升温速率将反应釜升温至300~350°C，保温1~2h，自然冷却至室温，得到硼硅锆掺杂沥青。Mix 1-2wt% organic boron, 5-6wt% organic silicon, 10-12wt% ZrC precursor and 80-84wt% asphalt toluene soluble components to obtain the mixture. Add a solvent to the mixture, the mass ratio of the mixture to the solvent is 1:(1~2), stir magnetically for 0.5~1h, and the mixture is obtained. Then the mixed solution is transferred to the reaction kettle, and an inert gas is introduced, and the reaction kettle is heated to 300~350°C at a heating rate of 2~5°C/min under the condition of mechanical stirring, kept for 1~2h, and naturally cooled to At room temperature, borosilicate zirconium doped pitch was obtained.

步骤三、预处理炭纤维预制体的浸渍和热解Step 3. Impregnation and pyrolysis of pretreated carbon fiber preform

按硼硅锆掺杂沥青与预处理炭纤维预制体的质量比为1︰(0.2~0.3)，将预处理炭纤维预制体置于金属圆筒内，用硼硅锆掺杂沥青将预处理炭纤维预制体覆盖。将装有硼硅锆掺杂沥青和预处理炭纤维预制体的金属圆筒置于高压反应釜内，先抽真空至0.02~0.08MPa，再将高压反应釜内温度升至250~300°C，充惰性气体至高压反应釜内的压力为3~3.5MPa，保温保压0.5~1 h。然后在相同的压力条件下升温至350~400°C，保温保压4~4.5h，自然冷却至室温，泄压。再将金属圆筒从高压反应釜内取出，放入高温炭化炉中，在氩气气氛保护下，以2~5°C/min的升温速率升温至1400~1450 °C，保温1~1.5h，冷却至室温，得到SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体。将所述C/C坯体表面打磨抛光，在介质中超声波清洗，烘干。According to the mass ratio of borosilicate-zirconium-doped pitch to pretreated carbon fiber prefabricated body is 1: (0.2~0.3), the pre-treated carbon fiber prefabricated body is placed in a metal cylinder, and borosilicate-zirconium-doped pitch is pretreated Carbon fiber preform covering. Put the metal cylinder containing borosilicate-zirconium-doped pitch and pretreated carbon fiber prefabricated body in the autoclave, first evacuate to 0.02~0.08MPa, and then raise the temperature in the autoclave to 250~300°C , fill inert gas to the pressure in the autoclave is 3~3.5MPa, heat preservation and pressure holding for 0.5~1 h. Then raise the temperature to 350~400°C under the same pressure conditions, hold the heat for 4~4.5 hours, cool down to room temperature naturally, and release the pressure. Then take the metal cylinder out of the autoclave, put it into a high-temperature carbonization furnace, and under the protection of argon atmosphere, raise the temperature to 1400~1450 °C at a rate of 2~5°C/min, and keep it warm for 1~1.5h , and cooled to room temperature to obtain a SiC-ZrC-ZrB₂ nanocomposite ceramic modified C/C green body. The surface of the C/C green body is polished, ultrasonically cleaned in a medium, and dried.

步骤四、SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体的致密化Step 4. Densification of SiC-ZrC-ZrB₂ nanocomposite ceramic modified C/C body

按硼硅锆掺杂沥青与SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体的质量比为1︰(0.3~0.4)，将SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体置于金属圆筒内，用硼硅锆掺杂沥青将SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体覆盖。将装有硼硅锆掺杂沥青和SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体的金属圆筒置于高压反应釜内，抽真空至0.02~0.08MPa，再将高压反应釜内温度升至250~300°C，充惰性气体至反应釜内的压力为3.5~4.5MPa，保温保压1~1.5h。然后在相同的压力条件下升温至400~450°C，保温保压4.5~5.5h，自然冷却至室温，泄压，完成一次浸渍。将金属圆筒从高压反应釜内取出，放入高温炭化炉中，在氩气气氛保护下，以5~8°C/min的升温速率升温至1450~1550°C，保温1.5~2.5h，冷却至室温，完成一次热解，得到增密的SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体。将所述C/C坯体表面打磨抛光，在介质中超声波清洗，烘干。According to the mass ratio of borosilicate-zirconium-doped pitch to SiC-ZrC-ZrB₂ nano-composite ceramics modified C/C green body is 1: (0.3~0.4), SiC-ZrC-ZrB₂ nano-composite ceramics modified The C/C green body is placed in a metal cylinder, and the SiC-ZrC-ZrB₂ nanocomposite ceramic modified C/C green body is covered with borosilicate zirconium doped pitch. Put the metal cylinder containing borosilicate-zirconium-doped pitch and SiC-ZrC-ZrB₂ nano-composite ceramic modified C/C green body in the high-pressure reaction kettle, vacuumize to 0.02~0.08MPa, and then put the high-pressure reaction The temperature in the kettle is raised to 250~300°C, filled with inert gas until the pressure in the reactor is 3.5~4.5MPa, and the temperature is kept for 1~1.5h. Then raise the temperature to 400~450°C under the same pressure conditions, keep the temperature and pressure for 4.5~5.5h, cool down to room temperature naturally, release the pressure, and complete the impregnation once. Take the metal cylinder out of the high-pressure reaction kettle, put it into a high-temperature carbonization furnace, and under the protection of an argon atmosphere, raise the temperature to 1450-1550°C at a heating rate of 5-8°C/min, and keep it warm for 1.5-2.5h. Cool to room temperature and complete a pyrolysis to obtain a densified SiC-ZrC-ZrB₂ nanocomposite ceramic modified C/C green body. The surface of the C/C green body is polished, ultrasonically cleaned in a medium, and dried.

重复上述浸渍、热解、打磨抛光和烘干处理过程，直至SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体的密度达到1.9~2.5g/cm³，即得SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C复合材料。Repeat the above impregnation, pyrolysis, polishing and drying process until the density of the SiC-ZrC-ZrB₂ nano-composite ceramic modified C/C green body reaches 1.9~2.5g/cm³ , that is, SiC-ZrC- ZrB₂ nano-composite ceramics modified C/C composites.

本实施例中：所述炭纤维预制体为整体毡炭纤维预制体，炭纤维预制体的密度为0.2~0.6 g/cm³。In this embodiment: the carbon fiber preform is an integral felt carbon fiber preform, and the carbon fiber preform has a density of 0.2-0.6 g/cm³ .

所述沥青为煤沥青。 The pitch is coal tar pitch.

所述有机硼为聚硼氮烷。 The organoboron is polyborazane.

所述有机硅为聚碳硅烷。 The organosilicon is polycarbosilane.

所述溶剂为甲苯。 Described solvent is toluene.

所述机械搅拌的转速为200~300r/min。 The rotating speed of the mechanical stirring is 200~300r/min.

所述惰性气体为氩气。 The inert gas is argon.

所述介质为丙酮。 The medium is acetone.

实施例Example22

一种SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C复合材料及其制备方法。所述制备方法的具体步骤是：A SiC-ZrC-ZrB₂ nanometer composite ceramic modified C/C composite material and a preparation method thereof. The concrete steps of described preparation method are:

步骤一、同实施例一的步骤一。Step 1 is the same as Step 1 in Embodiment 1.

步骤二、硼硅锆掺杂沥青的制备Step 2, preparation of borosilicate zirconium doped pitch

先将沥青溶于甲苯中，在室温条件下静置1~2h，固液分离，在110~150°C条件下对固液分离后的溶液进行蒸馏，得到沥青甲苯可溶组份。Dissolve the asphalt in toluene first, let it stand at room temperature for 1~2h, separate the solid and liquid, and distill the solution after the solid-liquid separation at 110~150°C to obtain the asphalt toluene soluble component.

将2~3wt％的有机硼、6~7wt％的有机硅、12~14wt％的ZrC前驱体和76~80wt％的沥青甲苯可溶组份混合，即得混合物。向混合物中加入溶剂，混合物与溶剂的质量比为1︰(1~2)，磁力搅拌0.5~1h，即得混合液。再将混合液转入反应釜中，通入惰性气体，在机械搅拌条件下以2~5°C/min的升温速率将反应釜升温至300~350°C，保温1~2h，自然冷却至室温，得到硼硅锆掺杂沥青。Mix 2-3wt% organoboron, 6-7wt% organosilicon, 12-14wt% ZrC precursor and 76-80wt% asphalt toluene soluble components to obtain the mixture. Add a solvent to the mixture, the mass ratio of the mixture to the solvent is 1:(1~2), stir magnetically for 0.5~1h, and the mixture is obtained. Then the mixed solution is transferred to the reaction kettle, and an inert gas is introduced, and the reaction kettle is heated to 300~350°C at a heating rate of 2~5°C/min under the condition of mechanical stirring, kept for 1~2h, and naturally cooled to At room temperature, borosilicate zirconium doped pitch was obtained.

步骤三、预处理炭纤维预制体的浸渍和热解Step 3. Impregnation and pyrolysis of pretreated carbon fiber preform

按硼硅锆掺杂沥青与预处理炭纤维预制体的质量比为1︰(0.2~0.3)，将预处理炭纤维预制体置于金属圆筒内，用硼硅锆掺杂沥青将预处理炭纤维预制体覆盖。将装有硼硅锆掺杂沥青和预处理炭纤维预制体的金属圆筒置于高压反应釜内，先抽真空至0.02~0.08MPa，再将高压反应釜内温度升至250~300°C，充惰性气体至高压反应釜内的压力为3~3.5MPa，保温保压0.5~1 h。然后在相同的压力条件下升温至350~400°C，保温保压4~4.5h，自然冷却至室温，泄压。再将金属圆筒从高压反应釜内取出，放入高温炭化炉中，在氩气气氛保护下，以2~5°C/min的升温速率升温至1400~1450 °C，保温1~1.5h，冷却至室温，得到SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体。将所述C/C坯体表面打磨抛光，在介质中超声波清洗，烘干。According to the mass ratio of borosilicate-zirconium-doped pitch to pretreated carbon fiber prefabricated body is 1: (0.2~0.3), the pre-treated carbon fiber prefabricated body is placed in a metal cylinder, and borosilicate-zirconium-doped pitch is pretreated Carbon fiber preform covering. Put the metal cylinder containing borosilicate-zirconium-doped pitch and pretreated carbon fiber prefabricated body in the autoclave, first evacuate to 0.02~0.08MPa, and then raise the temperature in the autoclave to 250~300°C , fill inert gas to the pressure in the autoclave is 3~3.5MPa, heat preservation and pressure holding for 0.5~1 h. Then raise the temperature to 350~400°C under the same pressure conditions, hold the heat for 4~4.5 hours, cool down to room temperature naturally, and release the pressure. Then take the metal cylinder out of the autoclave, put it into a high-temperature carbonization furnace, and under the protection of argon atmosphere, raise the temperature to 1400~1450 °C at a rate of 2~5°C/min, and keep it warm for 1~1.5h , and cooled to room temperature to obtain a SiC-ZrC-ZrB₂ nanocomposite ceramic modified C/C green body. The surface of the C/C green body is polished, ultrasonically cleaned in a medium, and dried.

步骤四、SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体的致密化Step 4. Densification of SiC-ZrC-ZrB₂ nanocomposite ceramic modified C/C body

按硼硅锆掺杂沥青与SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体的质量比为1︰(0.3~0.4)，将SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体置于金属圆筒内，用硼硅锆掺杂沥青将SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体覆盖。将装有硼硅锆掺杂沥青和SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体的金属圆筒置于高压反应釜内，抽真空至0.02~0.08MPa，再将高压反应釜内温度升至250~300°C，充惰性气体至反应釜内的压力为3.5~4.5MPa，保温保压1~1.5h。然后在相同的压力条件下升温至400~450°C，保温保压4.5~5.5h，自然冷却至室温，泄压，完成一次浸渍。将金属圆筒从高压反应釜内取出，放入高温炭化炉中，在氩气气氛保护下，以5~8°C/min的升温速率升温至1450~1550°C，保温1.5~2.5h，冷却至室温，完成一次热解，得到增密的SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体。将所述C/C坯体表面打磨抛光，在介质中超声波清洗，烘干。According to the mass ratio of borosilicate-zirconium-doped pitch to SiC-ZrC-ZrB₂ nano-composite ceramics modified C/C green body is 1: (0.3~0.4), SiC-ZrC-ZrB₂ nano-composite ceramics modified The C/C green body is placed in a metal cylinder, and the SiC-ZrC-ZrB₂ nanocomposite ceramic modified C/C green body is covered with borosilicate zirconium doped pitch. Put the metal cylinder containing borosilicate-zirconium-doped pitch and SiC-ZrC-ZrB₂ nano-composite ceramic modified C/C green body in the high-pressure reaction kettle, vacuumize to 0.02~0.08MPa, and then put the high-pressure reaction The temperature in the kettle is raised to 250~300°C, filled with inert gas until the pressure in the reactor is 3.5~4.5MPa, and the temperature is kept for 1~1.5h. Then raise the temperature to 400~450°C under the same pressure conditions, keep the temperature and pressure for 4.5~5.5h, cool down to room temperature naturally, release the pressure, and complete the impregnation once. Take the metal cylinder out of the high-pressure reaction kettle, put it into a high-temperature carbonization furnace, and under the protection of an argon atmosphere, raise the temperature to 1450-1550°C at a heating rate of 5-8°C/min, and keep it warm for 1.5-2.5h. Cool to room temperature and complete a pyrolysis to obtain a densified SiC-ZrC-ZrB₂ nanocomposite ceramic modified C/C green body. The surface of the C/C green body is polished, ultrasonically cleaned in a medium, and dried.

重复上述浸渍、热解、打磨抛光和烘干处理过程，直至SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体的密度达到1.9~2.5g/cm³，即得SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C复合材料。Repeat the above impregnation, pyrolysis, polishing and drying process until the density of the SiC-ZrC-ZrB₂ nano-composite ceramic modified C/C green body reaches 1.9~2.5g/cm³ , that is, SiC-ZrC- ZrB₂ nano-composite ceramics modified C/C composites.

本实施例中：所述炭纤维预制体为炭布/网胎叠层针刺炭纤维预制体，炭纤维预制体的密度为0.2~0.6 g/cm³。In this embodiment: the carbon fiber preform is a carbon cloth/net tire laminated needle-punched carbon fiber preform, and the density of the carbon fiber preform is 0.2-0.6 g/cm³ .

所述沥青为煤沥青。 The pitch is coal tar pitch.

所述有机硼为吡啶硼烷。 The organic boron is pyridine borane.

所述有机硅为聚碳硅烷。 The organosilicon is polycarbosilane.

所述溶剂为甲苯。 Described solvent is toluene.

所述机械搅拌的转速为300~400r/min。 The rotating speed of the mechanical stirring is 300~400r/min.

所述惰性气体为氮气。 The inert gas is nitrogen.

所述介质为丙酮。 The medium is acetone.

实施例Example33

一种SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C复合材料及其制备方法。所述制备方法的具体步骤是：A SiC-ZrC-ZrB₂ nanometer composite ceramic modified C/C composite material and a preparation method thereof. The concrete steps of described preparation method are:

步骤一、同实施例一的步骤一。Step 1 is the same as Step 1 in Embodiment 1.

步骤二、硼硅锆掺杂沥青的制备Step 2, preparation of borosilicate zirconium doped pitch

先将沥青溶于甲苯中，在室温条件下静置1~2h，固液分离，在110~150°C条件下对固液分离后的溶液进行蒸馏，得到沥青甲苯可溶组份。Dissolve the asphalt in toluene first, let it stand at room temperature for 1~2h, separate the solid and liquid, and distill the solution after the solid-liquid separation at 110~150°C to obtain the asphalt toluene soluble component.

将3~4wt％的有机硼、7~8wt％的有机硅、14~16wt％的ZrC前驱体和72~76wt％的沥青甲苯可溶组份混合，即得混合物。向混合物中加入溶剂，混合物与溶剂的质量比为1︰(1~2)，磁力搅拌0.5~1h，即得混合液。再将混合液转入反应釜中，通入惰性气体，在机械搅拌条件下以5~8°C/min的升温速率将反应釜升温至350~400°C，保温2~3h，自然冷却至室温，得到硼硅锆掺杂沥青。Mix 3-4wt% organic boron, 7-8wt% organic silicon, 14-16wt% ZrC precursor and 72-76wt% asphalt toluene soluble components to obtain the mixture. Add a solvent to the mixture, the mass ratio of the mixture to the solvent is 1:(1~2), stir magnetically for 0.5~1h, and the mixture is obtained. Then the mixed solution is transferred to the reaction kettle, and an inert gas is introduced, and the reaction kettle is heated to 350~400°C at a heating rate of 5~8°C/min under the condition of mechanical stirring, kept for 2~3h, and naturally cooled to At room temperature, borosilicate zirconium doped pitch was obtained.

步骤三、预处理炭纤维预制体的浸渍和热解Step 3. Impregnation and pyrolysis of pretreated carbon fiber preform

按硼硅锆掺杂沥青与预处理炭纤维预制体的质量比为1︰(0.3~0.4)，将预处理炭纤维预制体置于金属圆筒内，用硼硅锆掺杂沥青将预处理炭纤维预制体覆盖。将装有硼硅锆掺杂沥青和预处理炭纤维预制体的金属圆筒置于高压反应釜内，先抽真空至0.02~0.08MPa，再将高压反应釜内温度升至250~300°C，充惰性气体至高压反应釜内的压力为3.5~4.5MPa，保温保压1~1.5 h。然后在相同的压力条件下升温至400~450°C，保温保压4.5~5.5h，自然冷却至室温，泄压。再将金属圆筒从高压反应釜内取出，放入高温炭化炉中，在氩气气氛保护下，以5~8°C/min的升温速率升温至1450~1550°C，保温1.5~2.5h，冷却至室温，得到SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体。将所述C/C坯体表面打磨抛光，在介质中超声波清洗，烘干。According to the mass ratio of borosilicate zirconium doped pitch to pretreated carbon fiber prefabricated body is 1: (0.3~0.4), the pretreated carbon fiber prefabricated body is placed in a metal cylinder, and the pretreated carbon fiber prefabricated Carbon fiber preform covering. Put the metal cylinder containing borosilicate-zirconium-doped pitch and pretreated carbon fiber prefabricated body in the autoclave, first evacuate to 0.02~0.08MPa, and then raise the temperature in the autoclave to 250~300°C , fill inert gas to the pressure in the autoclave is 3.5~4.5MPa, heat preservation and pressure holding for 1~1.5h. Then raise the temperature to 400~450°C under the same pressure conditions, keep the temperature and hold the pressure for 4.5~5.5h, cool down to room temperature naturally, and release the pressure. Then take the metal cylinder out of the autoclave and put it into a high-temperature carbonization furnace. Under the protection of argon atmosphere, raise the temperature to 1450-1550°C at a heating rate of 5-8°C/min, and keep it warm for 1.5-2.5h , and cooled to room temperature to obtain a SiC-ZrC-ZrB₂ nanocomposite ceramic modified C/C green body. The surface of the C/C green body is polished, ultrasonically cleaned in a medium, and dried.

步骤四、SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体的致密化Step 4. Densification of SiC-ZrC-ZrB₂ nanocomposite ceramic modified C/C body

按硼硅锆掺杂沥青与SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体的质量比为1︰(0.4~0.5)，将SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体置于金属圆筒内，用硼硅锆掺杂沥青将SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体覆盖。将装有硼硅锆掺杂沥青和SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体的金属圆筒置于高压反应釜内，抽真空至0.02~0.08MPa，再将高压反应釜内温度升至250~300°C，充惰性气体至反应釜内的压力为4~5MPa，保温保压1.5~2h。然后在相同的压力条件下升温至450~500°C，保温保压5.5~6h，自然冷却至室温，泄压，完成一次浸渍。将金属圆筒从高压反应釜内取出，放入高温炭化炉中，在氩气气氛保护下，以8~10°C/min的升温速率升温至1550~1600°C，保温2.5~3h，冷却至室温，完成一次热解，得到增密的SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体。将所述C/C坯体表面打磨抛光，在介质中超声波清洗，烘干。According to the mass ratio of borosilicate-zirconium-doped pitch to SiC-ZrC-ZrB₂ nano-composite ceramics modified C/C green body is 1: (0.4~0.5), SiC-ZrC-ZrB₂ nano-composite ceramics modified The C/C green body is placed in a metal cylinder, and the SiC-ZrC-ZrB₂ nanocomposite ceramic modified C/C green body is covered with borosilicate zirconium doped pitch. Put the metal cylinder containing borosilicate-zirconium-doped pitch and SiC-ZrC-ZrB₂ nano-composite ceramic modified C/C green body in the high-pressure reaction kettle, vacuumize to 0.02~0.08MPa, and then put the high-pressure reaction The temperature in the kettle is raised to 250~300°C, filled with inert gas until the pressure in the reactor is 4~5MPa, and the temperature is kept for 1.5~2h. Then raise the temperature to 450~500°C under the same pressure conditions, keep the temperature and pressure for 5.5~6h, cool down to room temperature naturally, release the pressure, and complete the first impregnation. Take the metal cylinder out of the high-pressure reaction kettle, put it into a high-temperature carbonization furnace, and under the protection of an argon atmosphere, raise the temperature to 1550-1600°C at a heating rate of 8-10°C/min, keep it warm for 2.5-3h, and cool To room temperature, complete a pyrolysis to obtain a densified SiC-ZrC-ZrB₂ nanocomposite ceramic modified C/C green body. The surface of the C/C green body is polished, ultrasonically cleaned in a medium, and dried.

重复上述浸渍、热解、打磨抛光和烘干处理过程，直至SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体的密度达到1.9~2.5g/cm³，即得SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C复合材料。Repeat the above impregnation, pyrolysis, polishing and drying process until the density of the SiC-ZrC-ZrB₂ nano-composite ceramic modified C/C green body reaches 1.9~2.5g/cm³ , that is, SiC-ZrC- ZrB₂ nano-composite ceramics modified C/C composites.

本实施例中：所述炭纤维预制体为三维编织炭纤维预制体，炭纤维预制体的密度为0.2~0.6 g/cm³。In this embodiment: the carbon fiber preform is a three-dimensional braided carbon fiber preform, and the density of the carbon fiber preform is 0.2-0.6 g/cm³ .

所述沥青为煤沥青。 The pitch is coal tar pitch.

所述有机硼为2-甲基吡啶硼烷。 The organoboron is 2-picoline borane.

所述有机硅为聚二甲基硅烷。 The organosilicon is polydimethylsilane.

所述溶剂为甲苯。 Described solvent is toluene.

所述机械搅拌的转速为400~500r/min。 The rotating speed of the mechanical stirring is 400~500r/min.

所述惰性气体为氩气。 The inert gas is argon.

所述介质为无水乙醇。 The medium is absolute ethanol.

实施例Example44

一种SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C复合材料及其制备方法。所述制备方法的具体步骤是：A SiC-ZrC-ZrB₂ nanometer composite ceramic modified C/C composite material and a preparation method thereof. The concrete steps of described preparation method are:

步骤一、同实施例一的步骤一。Step 1 is the same as Step 1 in Embodiment 1.

步骤二、硼硅锆掺杂沥青的制备Step 2, preparation of borosilicate zirconium doped pitch

先将沥青溶于甲苯中，在室温条件下静置1~2h，固液分离，在110~150°C条件下对固液分离后的溶液进行蒸馏，得到沥青甲苯可溶组份。Dissolve the asphalt in toluene first, let it stand at room temperature for 1~2h, separate the solid and liquid, and distill the solution after the solid-liquid separation at 110~150°C to obtain the asphalt toluene soluble component.

将4~5wt％的有机硼、8~9wt％的有机硅、16~18wt％的ZrC前驱体和68~72wt％的沥青甲苯可溶组份混合，即得混合物。向混合物中加入溶剂，混合物与溶剂的质量比为1︰(1~2)，磁力搅拌0.5~1h，即得混合液。再将混合液转入反应釜中，通入惰性气体，在机械搅拌条件下以5~8°C/min的升温速率将反应釜升温至350~400°C，保温2~3h，自然冷却至室温，得到硼硅锆掺杂沥青。Mix 4-5wt% organoboron, 8-9wt% organosilicon, 16-18wt% ZrC precursor and 68-72wt% asphalt toluene soluble components to obtain the mixture. Add a solvent to the mixture, the mass ratio of the mixture to the solvent is 1:(1~2), stir magnetically for 0.5~1h, and the mixture is obtained. Then the mixed solution is transferred to the reaction kettle, and an inert gas is introduced, and the reaction kettle is heated to 350~400°C at a heating rate of 5~8°C/min under the condition of mechanical stirring, kept for 2~3h, and naturally cooled to At room temperature, borosilicate zirconium doped pitch was obtained.

步骤三、预处理炭纤维预制体的浸渍和热解Step 3. Impregnation and pyrolysis of pretreated carbon fiber preform

按硼硅锆掺杂沥青与预处理炭纤维预制体的质量比为1︰(0.3~0.4)，将预处理炭纤维预制体置于金属圆筒内，用硼硅锆掺杂沥青将预处理炭纤维预制体覆盖。将装有硼硅锆掺杂沥青和预处理炭纤维预制体的金属圆筒置于高压反应釜内，先抽真空至0.02~0.08MPa，再将高压反应釜内温度升至250~300°C，充惰性气体至高压反应釜内的压力为3.5~4.5MPa，保温保压1~1.5 h。然后在相同的压力条件下升温至400~450°C，保温保压4.5~5.5h，自然冷却至室温，泄压。再将金属圆筒从高压反应釜内取出，放入高温炭化炉中，在氩气气氛保护下，以5~8°C/min的升温速率升温至1450~1550°C，保温1.5~2.5h，冷却至室温，得到SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体。将所述C/C坯体表面打磨抛光，在介质中超声波清洗，烘干。According to the mass ratio of borosilicate zirconium doped pitch to pretreated carbon fiber prefabricated body is 1: (0.3~0.4), the pretreated carbon fiber prefabricated body is placed in a metal cylinder, and the pretreated carbon fiber prefabricated Carbon fiber preform covering. Put the metal cylinder containing borosilicate-zirconium-doped pitch and pretreated carbon fiber prefabricated body in the autoclave, first evacuate to 0.02~0.08MPa, and then raise the temperature in the autoclave to 250~300°C , fill inert gas to the pressure in the autoclave is 3.5~4.5MPa, heat preservation and pressure holding for 1~1.5h. Then raise the temperature to 400~450°C under the same pressure conditions, keep the temperature and hold the pressure for 4.5~5.5h, cool down to room temperature naturally, and release the pressure. Then take the metal cylinder out of the autoclave and put it into a high-temperature carbonization furnace. Under the protection of argon atmosphere, raise the temperature to 1450-1550°C at a heating rate of 5-8°C/min, and keep it warm for 1.5-2.5h , and cooled to room temperature to obtain a SiC-ZrC-ZrB₂ nanocomposite ceramic modified C/C green body. The surface of the C/C green body is polished, ultrasonically cleaned in a medium, and dried.

步骤四、SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体的致密化Step 4. Densification of SiC-ZrC-ZrB₂ nanocomposite ceramic modified C/C body

按硼硅锆掺杂沥青与SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体的质量比为1︰(0.4~0.5)，将SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体置于金属圆筒内，用硼硅锆掺杂沥青将SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体覆盖。将装有硼硅锆掺杂沥青和SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体的金属圆筒置于高压反应釜内，抽真空至0.02~0.08MPa，再将高压反应釜内温度升至250~300°C，充惰性气体至反应釜内的压力为4~5MPa，保温保压1.5~2h。然后在相同的压力条件下升温至450~500°C，保温保压5.5~6h，自然冷却至室温，泄压，完成一次浸渍。将金属圆筒从高压反应釜内取出，放入高温炭化炉中，在氩气气氛保护下，以8~10°C/min的升温速率升温至1550~1600°C，保温2.5~3h，冷却至室温，完成一次热解，得到增密的SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体。将所述C/C坯体表面打磨抛光，在介质中超声波清洗，烘干。According to the mass ratio of borosilicate-zirconium-doped pitch to SiC-ZrC-ZrB₂ nano-composite ceramics modified C/C green body is 1: (0.4~0.5), SiC-ZrC-ZrB₂ nano-composite ceramics modified The C/C green body is placed in a metal cylinder, and the SiC-ZrC-ZrB₂ nanocomposite ceramic modified C/C green body is covered with borosilicate zirconium doped pitch. Put the metal cylinder containing borosilicate-zirconium-doped pitch and SiC-ZrC-ZrB₂ nano-composite ceramic modified C/C green body in the high-pressure reaction kettle, vacuumize to 0.02~0.08MPa, and then put the high-pressure reaction The temperature in the kettle is raised to 250~300°C, filled with inert gas until the pressure in the reactor is 4~5MPa, and the temperature is kept for 1.5~2h. Then raise the temperature to 450~500°C under the same pressure conditions, keep the temperature and pressure for 5.5~6h, cool down to room temperature naturally, release the pressure, and complete the first impregnation. Take the metal cylinder out of the high-pressure reaction kettle, put it into a high-temperature carbonization furnace, and under the protection of an argon atmosphere, raise the temperature to 1550-1600°C at a heating rate of 8-10°C/min, keep it warm for 2.5-3h, and cool To room temperature, complete a pyrolysis to obtain a densified SiC-ZrC-ZrB₂ nanocomposite ceramic modified C/C green body. The surface of the C/C green body is polished, ultrasonically cleaned in a medium, and dried.

重复上述浸渍、热解、打磨抛光和烘干处理过程，直至SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体的密度达到1.9~2.5g/cm³，即得SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C复合材料。Repeat the above impregnation, pyrolysis, polishing and drying process until the density of the SiC-ZrC-ZrB₂ nano-composite ceramic modified C/C green body reaches 1.9~2.5g/cm³ , that is, SiC-ZrC- ZrB₂ nano-composite ceramics modified C/C composites.

本实施例中：所述炭纤维预制体为整体毡炭纤维预制体，炭纤维预制体的密度为0.2~0.6 g/cm³。In this embodiment: the carbon fiber preform is an integral felt carbon fiber preform, and the carbon fiber preform has a density of 0.2-0.6 g/cm³ .

所述沥青为煤沥青。 The pitch is coal tar pitch.

所述有机硼为聚硼氮烷。 The organoboron is polyborazane.

所述有机硅为氯代三甲基硅烷。 The organosilicon is chlorotrimethylsilane.

所述溶剂为二甲苯。 The solvent is xylene.

所述机械搅拌的转速为500~600r/min。 The rotating speed of the mechanical stirring is 500~600r/min.

所述惰性气体为氮气。 The inert gas is nitrogen.

所述介质为无水乙醇。 The medium is absolute ethanol.

实施例Example55

一种SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C复合材料及其制备方法。所述制备方法的具体步骤是：A SiC-ZrC-ZrB₂ nanometer composite ceramic modified C/C composite material and a preparation method thereof. The concrete steps of described preparation method are:

步骤一、同实施例一的步骤一。Step 1 is the same as Step 1 in Embodiment 1.

步骤二、硼硅锆掺杂沥青的制备Step 2, preparation of borosilicate zirconium doped pitch

先将沥青溶于甲苯中，在室温条件下静置1~2h，固液分离，在110~150°C条件下对固液分离后的溶液进行蒸馏，得到沥青甲苯可溶组份。Dissolve the asphalt in toluene first, let it stand at room temperature for 1~2h, separate the solid and liquid, and distill the solution after the solid-liquid separation at 110~150°C to obtain the asphalt toluene soluble component.

将4~5wt％的有机硼、9~10wt％的有机硅、18~20wt％的ZrC前驱体和65~69wt％的沥青甲苯可溶组份混合，即得混合物。向混合物中加入溶剂，混合物与溶剂的质量比为1︰(1~2)，磁力搅拌0.5~1h，即得混合液。再将混合液转入反应釜中，通入惰性气体，在机械搅拌条件下以8~10°C/min的升温速率将反应釜升温至400~450°C，保温3~4h，自然冷却至室温，得到硼硅锆掺杂沥青。Mix 4-5wt% organic boron, 9-10wt% organic silicon, 18-20wt% ZrC precursor and 65-69wt% asphalt toluene soluble components to obtain the mixture. Add a solvent to the mixture, the mass ratio of the mixture to the solvent is 1:(1~2), stir magnetically for 0.5~1h, and the mixture is obtained. Then the mixed solution is transferred to the reaction kettle, and the inert gas is introduced, and the reaction kettle is heated to 400~450°C at a heating rate of 8~10°C/min under the condition of mechanical stirring, kept for 3~4h, and naturally cooled to At room temperature, borosilicate zirconium doped pitch was obtained.

步骤三、预处理炭纤维预制体的浸渍和热解Step 3. Impregnation and pyrolysis of pretreated carbon fiber preform

按硼硅锆掺杂沥青与预处理炭纤维预制体的质量比为1︰(0.4~0.5)，将预处理炭纤维预制体置于金属圆筒内，用硼硅锆掺杂沥青将预处理炭纤维预制体覆盖。将装有硼硅锆掺杂沥青和预处理炭纤维预制体的金属圆筒置于高压反应釜内，先抽真空至0.02~0.08MPa，再将高压反应釜内温度升至250~300°C，充惰性气体至高压反应釜内的压力为4~5MPa，保温保压1.5~2 h。然后在相同的压力条件下升温至450~500°C，保温保压5.5~6h，自然冷却至室温，泄压。再将金属圆筒从高压反应釜内取出，放入高温炭化炉中，在氩气气氛保护下，以8~10°C/min的升温速率升温至1550~1600 °C，保温2.5~3h，冷却至室温，得到SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体。将所述C/C坯体表面打磨抛光，在介质中超声波清洗，烘干。According to the mass ratio of borosilicate zirconium doped pitch to pretreated carbon fiber prefabricated body is 1: (0.4~0.5), the pretreated carbon fiber prefabricated body is placed in a metal cylinder, and the pretreated carbon fiber prefabricated Carbon fiber preform covering. Put the metal cylinder containing borosilicate-zirconium-doped pitch and pretreated carbon fiber prefabricated body in the autoclave, first evacuate to 0.02~0.08MPa, and then raise the temperature in the autoclave to 250~300°C , fill the autoclave with inert gas until the pressure in the autoclave is 4~5MPa, keep the temperature and hold the pressure for 1.5~2 hours. Then raise the temperature to 450~500°C under the same pressure conditions, hold the heat for 5.5~6 hours, cool down to room temperature naturally, and release the pressure. Then take the metal cylinder out of the high-pressure reaction kettle, put it into a high-temperature carbonization furnace, and under the protection of an argon atmosphere, raise the temperature to 1550-1600 °C at a heating rate of 8-10 °C/min, and keep it for 2.5-3 hours. Cool to room temperature to obtain a SiC-ZrC-ZrB₂ nanocomposite ceramic modified C/C green body. The surface of the C/C green body is polished, ultrasonically cleaned in a medium, and dried.

步骤四、SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体的致密化Step 4. Densification of SiC-ZrC-ZrB₂ nanocomposite ceramic modified C/C body

按硼硅锆掺杂沥青与SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体的质量比为1︰(0.2~0.3)，将SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体置于金属圆筒内，用硼硅锆掺杂沥青将SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体覆盖。将装有硼硅锆掺杂沥青和SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体的金属圆筒置于高压反应釜内，抽真空至0.02~0.08MPa，再将高压反应釜内温度升至250~300°C，充惰性气体至反应釜内的压力为3~3.5MPa，保温保压0.5~1h。然后在相同的压力条件下升温至350~400°C，保温保压4~4.5h，自然冷却至室温，泄压，完成一次浸渍。将金属圆筒从高压反应釜内取出，放入高温炭化炉中，在氩气气氛保护下，以2~5°C/min的升温速率升温至1400~1450°C，保温1~1.5h，冷却至室温，完成一次热解，得到增密的SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体。将所述C/C坯体表面打磨抛光，在介质中超声波清洗，烘干。According to the mass ratio of borosilicate-zirconium-doped pitch to SiC-ZrC-ZrB₂ nano-composite ceramics modified C/C green body is 1: (0.2~0.3), SiC-ZrC-ZrB₂ nano-composite ceramics modified The C/C green body is placed in a metal cylinder, and the SiC-ZrC-ZrB₂ nanocomposite ceramic modified C/C green body is covered with borosilicate zirconium doped pitch. Put the metal cylinder containing borosilicate-zirconium-doped pitch and SiC-ZrC-ZrB₂ nano-composite ceramic modified C/C green body in the high-pressure reaction kettle, vacuumize to 0.02~0.08MPa, and then put the high-pressure reaction The temperature in the kettle is raised to 250~300°C, filled with inert gas until the pressure in the reactor is 3~3.5MPa, and the temperature is kept for 0.5~1h. Then raise the temperature to 350~400°C under the same pressure conditions, keep the temperature and pressure for 4~4.5h, cool down to room temperature naturally, release the pressure, and complete the impregnation once. Take the metal cylinder out of the high-pressure reaction kettle, put it into a high-temperature carbonization furnace, and under the protection of an argon atmosphere, raise the temperature to 1400-1450°C at a rate of 2-5°C/min, and keep it warm for 1-1.5h. Cool to room temperature and complete a pyrolysis to obtain a densified SiC-ZrC-ZrB₂ nanocomposite ceramic modified C/C green body. The surface of the C/C green body is polished, ultrasonically cleaned in a medium, and dried.

重复上述浸渍、热解、打磨抛光和烘干处理过程，直至SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体的密度达到1.9~2.5g/cm³，即得SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C复合材料。Repeat the above impregnation, pyrolysis, polishing and drying process until the density of the SiC-ZrC-ZrB₂ nano-composite ceramic modified C/C green body reaches 1.9~2.5g/cm³ , that is, SiC-ZrC- ZrB₂ nano-composite ceramics modified C/C composites.

本实施例中：所述炭纤维预制体为炭布/网胎叠层针刺炭纤维预制体，炭纤维预制体的密度为0.2~0.6 g/cm³。In this embodiment: the carbon fiber preform is a carbon cloth/net tire laminated needle-punched carbon fiber preform, and the density of the carbon fiber preform is 0.2-0.6 g/cm³ .

所述沥青为煤沥青。 The pitch is coal tar pitch.

所述有机硼为2-甲基吡啶硼烷。 The organoboron is 2-picoline borane.

所述有机硅为聚二甲基硅烷。 The organosilicon is polydimethylsilane.

所述溶剂为二甲苯。 The solvent is xylene.

所述机械搅拌的转速为300~400r/min。 The rotating speed of the mechanical stirring is 300~400r/min.

所述惰性气体为氩气。 The inert gas is argon.

所述介质为去离子水。 The medium is deionized water.

实施例Example66

一种SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C复合材料及其制备方法。所述制备方法的具体步骤是：A SiC-ZrC-ZrB₂ nanometer composite ceramic modified C/C composite material and a preparation method thereof. The concrete steps of described preparation method are:

步骤一、同实施例一的步骤一。Step 1 is the same as Step 1 in Embodiment 1.

步骤二、硼硅锆掺杂沥青的制备Step 2, preparation of borosilicate zirconium doped pitch

先将沥青溶于甲苯中，在室温条件下静置1~2h，固液分离，在110~150°C条件下对固液分离后的溶液进行蒸馏，得到沥青甲苯可溶组份。Dissolve the asphalt in toluene first, let it stand at room temperature for 1~2h, separate the solid and liquid, and distill the solution after the solid-liquid separation at 110~150°C to obtain the asphalt toluene soluble component.

将3~4wt％的有机硼、7~8wt％的有机硅、13~15wt％的ZrC前驱体和73~77wt％的沥青甲苯可溶组份混合，即得混合物。向混合物中加入溶剂，混合物与溶剂的质量比为1︰(1~2)，磁力搅拌0.5~1h，即得混合液。再将混合液转入反应釜中，通入惰性气体，在机械搅拌条件下以8~10°C/min的升温速率将反应釜升温至400~450°C，保温3~4h，自然冷却至室温，得到硼硅锆掺杂沥青。Mix 3-4wt% organic boron, 7-8wt% organic silicon, 13-15wt% ZrC precursor and 73-77wt% asphalt toluene soluble components to obtain the mixture. Add a solvent to the mixture, the mass ratio of the mixture to the solvent is 1:(1~2), stir magnetically for 0.5~1h, and the mixture is obtained. Then the mixed solution is transferred to the reaction kettle, and the inert gas is introduced, and the reaction kettle is heated to 400~450°C at a heating rate of 8~10°C/min under the condition of mechanical stirring, kept for 3~4h, and naturally cooled to At room temperature, borosilicate-zirconium doped pitch was obtained.

步骤三、预处理炭纤维预制体的浸渍和热解Step 3. Impregnation and pyrolysis of pretreated carbon fiber preform

按硼硅锆掺杂沥青与预处理炭纤维预制体的质量比为1︰(0.4~0.5)，将预处理炭纤维预制体置于金属圆筒内，用硼硅锆掺杂沥青将预处理炭纤维预制体覆盖。将装有硼硅锆掺杂沥青和预处理炭纤维预制体的金属圆筒置于高压反应釜内，先抽真空至0.02~0.08MPa，再将高压反应釜内温度升至250~300°C，充惰性气体至高压反应釜内的压力为4~5MPa，保温保压1.5~2 h。然后在相同的压力条件下升温至450~500°C，保温保压5.5~6h，自然冷却至室温，泄压。再将金属圆筒从高压反应釜内取出，放入高温炭化炉中，在氩气气氛保护下，以8~10°C/min的升温速率升温至1550~1600 °C，保温2.5~3h，冷却至室温，得到SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体。将所述C/C坯体表面打磨抛光，在介质中超声波清洗，烘干。According to the mass ratio of borosilicate zirconium doped pitch to pretreated carbon fiber prefabricated body is 1: (0.4~0.5), the pretreated carbon fiber prefabricated body is placed in a metal cylinder, and the pretreated carbon fiber prefabricated Carbon fiber preform covering. Put the metal cylinder containing borosilicate-zirconium-doped pitch and pretreated carbon fiber prefabricated body in the autoclave, first evacuate to 0.02~0.08MPa, and then raise the temperature in the autoclave to 250~300°C , fill the autoclave with inert gas until the pressure in the autoclave is 4~5MPa, keep the temperature and hold the pressure for 1.5~2 hours. Then raise the temperature to 450~500°C under the same pressure conditions, hold the heat for 5.5~6 hours, cool down to room temperature naturally, and release the pressure. Then take the metal cylinder out of the high-pressure reaction kettle, put it into a high-temperature carbonization furnace, and under the protection of an argon atmosphere, raise the temperature to 1550-1600 °C at a heating rate of 8-10 °C/min, and keep it for 2.5-3 hours. Cool to room temperature to obtain a SiC-ZrC-ZrB₂ nanocomposite ceramic modified C/C green body. The surface of the C/C green body is polished, ultrasonically cleaned in a medium, and dried.

步骤四、SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体的致密化Step 4. Densification of SiC-ZrC-ZrB₂ nanocomposite ceramic modified C/C body

按硼硅锆掺杂沥青与SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体的质量比为1︰(0.2~0.3)，将SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体置于金属圆筒内，用硼硅锆掺杂沥青将SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体覆盖。将装有硼硅锆掺杂沥青和SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体的金属圆筒置于高压反应釜内，抽真空至0.02~0.08MPa，再将高压反应釜内温度升至250~300°C，充惰性气体至反应釜内的压力为3~3.5MPa，保温保压0.5~1h。然后在相同的压力条件下升温至350~400°C，保温保压4~4.5h，自然冷却至室温，泄压，完成一次浸渍。将金属圆筒从高压反应釜内取出，放入高温炭化炉中，在氩气气氛保护下，以2~5°C/min的升温速率升温至1400~1450°C，保温1~1.5h，冷却至室温，完成一次热解，得到增密的SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体。将所述C/C坯体表面打磨抛光，在介质中超声波清洗，烘干。According to the mass ratio of borosilicate-zirconium-doped pitch to SiC-ZrC-ZrB₂ nano-composite ceramics modified C/C green body is 1: (0.2~0.3), SiC-ZrC-ZrB₂ nano-composite ceramics modified The C/C green body is placed in a metal cylinder, and the SiC-ZrC-ZrB₂ nanocomposite ceramic modified C/C green body is covered with borosilicate zirconium doped pitch. Put the metal cylinder containing borosilicate-zirconium-doped pitch and SiC-ZrC-ZrB₂ nano-composite ceramic modified C/C green body in the high-pressure reaction kettle, vacuumize to 0.02~0.08MPa, and then put the high-pressure reaction The temperature in the kettle is raised to 250~300°C, filled with inert gas until the pressure in the reactor is 3~3.5MPa, and the temperature is kept for 0.5~1h. Then raise the temperature to 350~400°C under the same pressure conditions, keep the temperature and pressure for 4~4.5h, cool down to room temperature naturally, release the pressure, and complete the impregnation once. Take the metal cylinder out of the high-pressure reaction kettle, put it into a high-temperature carbonization furnace, and under the protection of an argon atmosphere, raise the temperature to 1400-1450°C at a rate of 2-5°C/min, and keep it warm for 1-1.5h. Cool to room temperature and complete a pyrolysis to obtain a densified SiC-ZrC-ZrB₂ nanocomposite ceramic modified C/C green body. The surface of the C/C green body is polished, ultrasonically cleaned in a medium, and dried.

重复上述浸渍、热解、打磨抛光和烘干处理过程，直至SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C坯体的密度达到1.9~2.5g/cm³，即得SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C复合材料。Repeat the above impregnation, pyrolysis, polishing and drying process until the density of the SiC-ZrC-ZrB₂ nano-composite ceramic modified C/C green body reaches 1.9~2.5g/cm³ , that is, SiC-ZrC- ZrB₂ nano-composite ceramics modified C/C composites.

本实施例中：所述炭纤维预制体为三维编织炭纤维预制体，炭纤维预制体的密度为0.2~0.6 g/cm³。In this embodiment: the carbon fiber preform is a three-dimensional braided carbon fiber preform, and the density of the carbon fiber preform is 0.2-0.6 g/cm³ .

所述沥青为石油沥青。 The asphalt is petroleum asphalt.

所述有机硼为聚硼氮烷。 The organoboron is polyborazane.

所述有机硅为氯代三甲基硅烷。 The organosilicon is chlorotrimethylsilane.

所述溶剂为二甲苯。 The solvent is xylene.

所述机械搅拌的转速为400~500r/min。 The rotating speed of the mechanical stirring is 400~500r/min.

所述惰性气体为氮气。 The inert gas is nitrogen.

所述介质为去离子水。 The medium is deionized water.

本具体实施方式与现有技术相比具有如下积极效果：Compared with the prior art, this specific embodiment has the following positive effects:

(1)本具体实施方式通过沥青甲苯可溶组份与有机硼、有机硅和ZrC前驱体的共裂解将硼、硅和锆原子引入沥青的稠环芳烃分子中，使硼、硅和锆杂原子在沥青中达到分子级别的均匀分散，硼硅锆掺杂沥青经高温热处理后能够在基体炭中原位生成均匀弥散的ZrB₂、SiC和ZrC纳米复相陶瓷。图1是实施例1制备的一种SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C复合材料的XRD谱图，由图1可以看出，硼硅锆掺杂沥青经高温热处理形成的复相陶瓷主要由ZrC、ZrB₂和SiC组成，XRD谱图中没有出现碳的特征衍射峰，这主要是由于基体炭以无定形碳的形式存在所致。(1) In this specific embodiment, boron, silicon and zirconium atoms are introduced into the condensed ring aromatic hydrocarbon molecules of pitch through co-cracking of the pitch toluene soluble components and organoboron, organosilicon and ZrC precursors, so that boron, silicon and zirconium hetero Atoms are uniformly dispersed in the pitch at the molecular level, and the borosilicate-zirconium-doped pitch can in-situ generate uniformly dispersed ZrB₂ , SiC and ZrC nanocomposite ceramics in the matrix carbon after high-temperature heat treatment. Fig. 1 is the XRD spectrogram of a kind of SiC-ZrC-ZrB_nano- composite ceramics modified C/C composite material that embodiment 1 prepares, as can be seen from Fig. Composite ceramics are mainly composed of ZrC, ZrB₂ and SiC, and there is no characteristic diffraction peak of carbon in the XRD spectrum, which is mainly due to the existence of matrix carbon in the form of amorphous carbon.

(2)由于ZrB₂、SiC和ZrC纳米复相陶瓷在基体炭中分布均匀，SiC-ZrC-ZrB₂纳米复相陶瓷在氧化过程中形成的B₂O₃、SiO₂、ZrO₂等氧化物在不同的温度范围内能够互相反应和相互溶解，形成连续而稳定的保护膜，因此只需在C/C复合材料中引入少量的ZrB₂、SiC和ZrC纳米复相陶瓷就能显著提高材料较宽温度范围的自愈合抗氧化能力和超高温抗烧蚀性能。图2是图1所示SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C复合材料表面的SEM照片。从图2可以看出，材料表面由基体炭和陶瓷颗粒组成，结构较为致密。图3、图4、图5和图6依次是碳、硼、硅和锆元素在图2所示的SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C复合材料表面的分布图。从图3~图6可以看出，碳、硼、硅和锆元素均匀地分布在所述复合材料的表面，硼、硅和锆主要以ZrB₂、SiC和ZrC的形式存在。(2) Due to the uniform distribution of ZrB₂ , SiC and ZrC nanocomposite ceramics in the matrix carbon, oxides such as B₂ O₃ , SiO₂ , and ZrO₂ formed during the oxidation process of SiC-ZrC-ZrB₂ nanocomposite ceramics They can react and dissolve each other in different temperature ranges to form a continuous and stable protective film. Therefore, only a small amount of ZrB₂ , SiC and ZrC nanocomposite ceramics can be introduced into the C/C composite material to significantly improve the material's relatively high temperature. Self-healing anti-oxidation ability and ultra-high temperature anti-ablation performance in a wide temperature range. Figure 2 is a SEM photo of the surface of the SiC-ZrC-ZrB₂ nanocomposite ceramic modified C/C composite material shown in Figure 1 . It can be seen from Figure 2 that the surface of the material is composed of matrix carbon and ceramic particles, and the structure is relatively dense. Figure 3, Figure 4, Figure 5 and Figure 6 are the distribution diagrams of carbon, boron, silicon and zirconium elements on the surface of the SiC-ZrC-ZrB₂ nanocomposite ceramic modified C/C composite material shown in Figure 2. It can be seen from Figures 3 to 6 that carbon, boron, silicon and zirconium elements are evenly distributed on the surface of the composite material, and boron, silicon and zirconium mainly exist in the form of ZrB₂ , SiC and ZrC.

(3)在基体炭内原位生成的ZrB₂和ZrC与碳之间具有很好的物理和化学相容性，能大大提高C/C复合材料的机械性能。(3) ZrB₂ and ZrC generated in situ in matrix carbon have good physical and chemical compatibility with carbon, which can greatly improve the mechanical properties of C/C composites.

(4)本具体实施方式制备的SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C复合材料在静态空气气氛和1100 °C条件下氧化10 h，试样增重0.2~0.5 wt% ；在1600°C氧化10 h，氧化失重仅0.1~0.3 wt%；在3000 °C的氧乙炔焰中氧化烧蚀120 s，其线烧蚀率仅为0.001~0.0015 mm/s。(4) The SiC-ZrC-_ZrB2 nano-composite ceramics modified C/C composite material prepared by this specific embodiment is oxidized for 10 h under static air atmosphere and 1100 ° C conditions, and the sample weight gain is 0.2 ~ 0.5 wt%; Oxidation at 1600 °C for 10 h, the oxidation weight loss is only 0.1-0.3 wt%; oxidative ablation in oxyacetylene flame at 3000 °C for 120 s, the linear ablation rate is only 0.001-0.0015 mm/s.

因此，本具体实施方式有效地解决了固相法制备SiC-ZrC-ZrB₂复相陶瓷改性C/C复合材料存在的SiC-ZrC-ZrB₂复相陶瓷在基体炭中分散不均匀的问题，所制备的SiC-ZrC-ZrB₂纳米复相陶瓷改性C/C复合材料具有较好的机械性能、较宽温度范围的自愈合抗氧化能力和超高温抗烧蚀性能。Therefore, this specific embodiment effectively solves the problem of uneven dispersion of SiC-ZrC-ZrB₂ composite ceramics in the matrix carbon in the preparation of SiC-ZrC-ZrB₂ composite ceramics modified C/C composite materials by solid phase method , the prepared SiC-ZrC-ZrB₂ nanocomposite ceramic modified C/C composite material has good mechanical properties, self-healing and anti-oxidation ability in a wide temperature range and ultra-high temperature ablation resistance.

Claims (11)

1. a SiC-ZrC-ZrB₂the preparation method of nano heterogeneous ceramic modification C/C matrix material, is characterized in that the concrete steps of described preparation method are:

The pre-treatment of step one, Carbon fibe precast body

By Carbon fibe precast body acetone cleaning 30 ~ 60min, under 70 ~ 100 ° of C conditions, dry 1 ~ 2h, obtains pre-treatment Carbon fibe precast body;

The preparation of step 2, borosilicate zirconium doping pitch

First be dissolved in toluene by pitch, leave standstill 1 ~ 2h at ambient temperature, solid-liquid separation, distills the solution after solid-liquid separation under 110 ~ 150 ° of C conditions, obtains pitch toluene soluble fraction;

The pitch toluene soluble fraction of the ZrC presoma of the organosilicon of the organic boron of 1 ~ 5wt%, 5 ~ 10wt%, 10 ~ 20wt% and 65 ~ 84wt% is mixed, obtains mixture; In mixture, add solvent, the mass ratio of mixture and solvent is 1 ︰ (1 ~ 2), and magnetic agitation 0.5 ~ 1h, obtains mixed solution; Proceed in reactor by mixed solution again, pass into rare gas element, under mechanical agitation, with the temperature rise rate of 2 ~ 10 ° of C/min, reactor is warming up to 300 ~ 450 ° of C, insulation 1 ~ 4h, naturally cools to room temperature, obtains borosilicate zirconium doping pitch;

The dipping of step 3, pre-treatment Carbon fibe precast body and pyrolysis

Be 1 ︰ (0.2 ~ 0.5) by the mass ratio of the doping of borosilicate zirconium pitch and pre-treatment Carbon fibe precast body, pre-treatment Carbon fibe precast body is placed in metallic cylinder, with the borosilicate zirconium pitch that adulterates, pre-treatment Carbon fibe precast body is covered; The metallic cylinder that borosilicate zirconium doping pitch and pre-treatment Carbon fibe precast body are housed is placed in autoclave, first be evacuated to 0.02 ~ 0.08MPa, again reaction under high pressure temperature in the kettle is risen to 250 ~ 300 ° of C, filling with inert gas to the pressure in autoclave is 3 ~ 5MPa, heat-insulation pressure keeping 0.5 ~ 2 h; Then under identical pressure condition, be warming up to 350 ~ 500 ° of C, heat-insulation pressure keeping 4 ~ 6h, naturally cools to room temperature, pressure release; Metallic cylinder taken out in autoclave, put into high temperature carbonization furnace, under argon gas atmosphere protection, be warming up to 1400 ~ 1600 ° of C with the temperature rise rate of 2 ~ 10 ° of C/min, insulation 1 ~ 3h, is cooled to room temperature, obtains SiC-ZrC-ZrB₂nano heterogeneous ceramic modification C/C base substrate; By described C/C billet surface sanding and polishing, ultrasonic cleaning in media as well, dries;

Step 4, SiC-ZrC-ZrB₂the densification of nano heterogeneous ceramic modification C/C base substrate

By borosilicate zirconium doping pitch and SiC-ZrC-ZrB₂the mass ratio of nano heterogeneous ceramic modification C/C base substrate is 1 ︰ (0.2 ~ 0.5), by SiC-ZrC-ZrB₂nano heterogeneous ceramic modification C/C base substrate is placed in metallic cylinder, with borosilicate zirconium doping pitch by SiC-ZrC-ZrB₂nano heterogeneous ceramic modification C/C base substrate covers; Borosilicate zirconium doping pitch and SiC-ZrC-ZrB will be housed₂the metallic cylinder of nano heterogeneous ceramic modification C/C base substrate is placed in autoclave, is evacuated to 0.02 ~ 0.08MPa, then reaction under high pressure temperature in the kettle is risen to 250 ~ 300 ° of C, and filling with inert gas to the pressure in reactor is 3 ~ 5MPa, heat-insulation pressure keeping 0.5 ~ 2h; Then under identical pressure condition, be warming up to 350 ~ 500 ° of C, heat-insulation pressure keeping 4 ~ 6h, naturally cools to room temperature, and pressure release completes single-steeping; Metallic cylinder taken out in autoclave, put into high temperature carbonization furnace, under argon gas atmosphere protection, be warming up to 1400 ~ 1600 ° of C with the temperature rise rate of 2 ~ 10 ° of C/min, insulation 1 ~ 3h, is cooled to room temperature, completes a pyrolysis, obtain the SiC-ZrC-ZrB of density₂nano heterogeneous ceramic modification C/C base substrate; By described C/C billet surface sanding and polishing, ultrasonic cleaning in media as well, dries;

Repeat above-mentioned dipping, pyrolysis, sanding and polishing and drying and processing process, until SiC-ZrC-ZrB₂the density of nano heterogeneous ceramic modification C/C base substrate reaches 1.9 ~ 2.5g/cm³, obtain SiC-ZrC-ZrB₂nano heterogeneous ceramic modification C/C matrix material.

2. SiC-ZrC-ZrB according to claim 1₂the preparation method of nano heterogeneous ceramic modification C/C matrix material, it is characterized in that described Carbon fibe precast body is the one in overall felt Carbon fibe precast body, charcoal cloth/net tire lamination needle-punched carbon fiber precast body and 3 D weaving Carbon fibe precast body, the density of Carbon fibe precast body is 0.2 ~ 0.6 g/cm³.

3. SiC-ZrC-ZrB according to claim 1₂the preparation method of nano heterogeneous ceramic modification C/C matrix material, is characterized in that described pitch is coal-tar pitch or is petroleum pitch.

4. SiC-ZrC-ZrB according to claim 1₂the preparation method of nano heterogeneous ceramic modification C/C matrix material, is characterized in that described organic boron is the one in polyborazine, pyridine borane and 2-picoline borine.

5. SiC-ZrC-ZrB according to claim 1₂the preparation method of nano heterogeneous ceramic modification C/C matrix material, is characterized in that described organosilicon is the one in Polycarbosilane, polydimethylsiloxane and trimethysilyl chloride.

6. SiC-ZrC-ZrB according to claim 1₂the preparation method of nano heterogeneous ceramic modification C/C matrix material, it is characterized in that the preparation process of described ZrC presoma is: reactor is evacuated to 0.06 ~ 0.08MPa, pass into argon gas to normal pressure, toluene, zirconates and dehydrated alcohol is added successively again in reactor, stir, wherein: zirconates: toluene: the mol ratio of dehydrated alcohol is 1: (3 ~ 5): (4 ~ 10); Then under 10 ~ 10 ° of C conditions, pass into ammonia, the flow passing into ammonia is 40 ~ 60ml/min, and reaction 2 ~ 6h, filters, obtain the toluene solution of alcohol zirconium;

Reactor is evacuated to 0.06 ~ 0.08MPa, pass into argon gas to normal pressure, add the toluene solution of alcohol zirconium, beta-diketon and phenol to reactor successively again, stir, wherein: beta-diketon: phenol: the mol ratio of zirconates is (1 ~ 4): (2 ~ 4): 1; Then by the temperature rise rate of 2 ~ 4 ° of C/min, reaction system is heated to 120 ~ 300 ° of C, insulation 1 ~ 10h, underpressure distillation, is cooled to room temperature, obtains ZrC presoma.

7. SiC-ZrC-ZrB according to claim 1₂the preparation method of nano heterogeneous ceramic modification C/C matrix material, is characterized in that described solvent is toluene or is dimethylbenzene.

8. SiC-ZrC-ZrB according to claim 1₂the preparation method of nano heterogeneous ceramic modification C/C matrix material, is characterized in that described churned mechanically rotating speed is 200 ~ 600r/min.

9. SiC-ZrC-ZrB according to claim 1₂the preparation method of nano heterogeneous ceramic modification C/C matrix material, is characterized in that described rare gas element is argon gas or is nitrogen.

10. SiC-ZrC-ZrB according to claim 1₂the preparation method of nano heterogeneous ceramic modification C/C matrix material, is characterized in that described medium is the one in acetone, dehydrated alcohol and deionized water.

11. 1 kinds of SiC-ZrC-ZrB₂nano heterogeneous ceramic modification C/C matrix material, is characterized in that described SiC-ZrC-ZrB₂nano heterogeneous ceramic modification C/C matrix material is SiC-ZrC-ZrB according to any one of claim 1 ~ 9₂the SiC-ZrC-ZrB prepared by preparation method of nano heterogeneous ceramic modification C/C matrix material₂nano heterogeneous ceramic modification C/C matrix material.