CN104926345A - Alumina fiber-reinforced silicon carbide-aluminum silicate ceramic and preparation method thereof - Google Patents
Alumina fiber-reinforced silicon carbide-aluminum silicate ceramic and preparation method thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 113
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000010703 silicon Substances 0.000 title claims abstract description 22
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 56
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- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 10
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- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims abstract description 7
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- DWAWYEUJUWLESO-UHFFFAOYSA-N trichloromethylsilane Chemical compound [SiH3]C(Cl)(Cl)Cl DWAWYEUJUWLESO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 36
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Abstract
一种氧化铝纤维增强碳化硅-硅酸铝陶瓷,其是以氧化铝纤维织物作为增强体,以碳化硅陶瓷和硅酸铝陶瓷作为基体,碳化硅陶瓷主要是采用化学气相渗透法成型得到,硅酸铝陶瓷是通过溶胶-凝胶工艺引入;该制备方法包括以下步骤:以氧化铝纤维织物、三氯甲基硅烷、氢气、氩气为原料,采用化学气相渗透法制备Al2O3f/SiC陶瓷坯体;对制得的陶瓷坯体进行表面加工,将表面的大量闭孔变为开孔;利用硅铝复合溶胶真空浸渍陶瓷坯体,经凝胶化、高温陶瓷化后转变为中间产品;重复至少4次,最终制得氧化铝纤维增强碳化硅-硅酸铝陶瓷。本发明的产品力学性能、耐高温和抗氧化性能优异,且制备周期短、成本低、可以近净尺寸成型。
An alumina fiber-reinforced silicon carbide-aluminosilicate ceramic, which uses an alumina fiber fabric as a reinforcement, and uses silicon carbide ceramics and aluminum silicate ceramics as a matrix. The silicon carbide ceramics are mainly formed by chemical vapor infiltration. Aluminum silicate ceramics are introduced through a sol-gel process; the preparation method includes the following steps: using alumina fiber fabrics, trichloromethylsilane, hydrogen, and argon as raw materials, and using chemical vapor infiltration to prepare Al 2 O 3f / SiC ceramic body; surface processing of the prepared ceramic body to change a large number of closed cells on the surface into open pores; use silicon-aluminum composite sol to vacuum impregnate the ceramic body, and transform it into an intermediate after gelation and high-temperature ceramicization product; repeat at least 4 times to finally obtain alumina fiber-reinforced silicon carbide-aluminosilicate ceramics. The product of the invention has excellent mechanical properties, high temperature resistance and oxidation resistance, and has short preparation period, low cost and can be molded to a near-net size.
Description
技术领域technical field
本发明涉及纤维增强陶瓷材料领域,尤其涉及一种纤维增强碳化硅-硅酸铝陶瓷及其制备方法。The invention relates to the field of fiber-reinforced ceramic materials, in particular to a fiber-reinforced silicon carbide-aluminum silicate ceramic and a preparation method thereof.
背景技术Background technique
氧化物纤维增强碳化硅陶瓷具有优异的力学性能、介电性能、抗氧化性能和耐环境性能,是一类重要的高温结构功能材料。然而,碳化硅的高温耐环境性能较差,如在高温有氧的水汽环境中容易发生氧化而失效,极大地限制了其应用。Oxide fiber reinforced silicon carbide ceramics have excellent mechanical properties, dielectric properties, oxidation resistance and environmental resistance, and are an important class of high-temperature structural functional materials. However, silicon carbide has poor high-temperature environmental resistance, such as easy oxidation and failure in a high-temperature aerobic water vapor environment, which greatly limits its application.
目前,氧化物纤维增强碳化硅陶瓷的制备工艺主要有先驱体转化法(PIP)和化学气相渗透法(CVI)。PIP法烧结温度低、基体可设计性强、可近净尺寸成型,但PIP制备的材料孔隙率较高、纤维损伤较大且纤维/基体界面结合较强。此外,PIP法制备的SiC陶瓷中通常含有游离碳和玻璃相SiOxCy等杂质,其抗氧化性能不及纯SiC陶瓷。CVI法制备温度低、得到的SiC基体纯度较高、亦可近净尺寸成型。然而,在CVI制备过程中,由于缺陷的产生和热失配引起的基体裂纹会使其抗氧化性能大大降低。通过基体改性和后致密化处理,进一步提高复合材料致密度,可以在一定程度上提高SiC基体的抗氧化性能。At present, the preparation techniques of oxide fiber reinforced silicon carbide ceramics mainly include precursor transformation method (PIP) and chemical vapor infiltration method (CVI). The PIP method has low sintering temperature, strong designability of the matrix, and near-net size molding, but the material prepared by PIP has high porosity, large fiber damage, and strong fiber/matrix interface bonding. In addition, SiC ceramics prepared by PIP usually contain impurities such as free carbon and glass phase SiO x C y , and their oxidation resistance is inferior to that of pure SiC ceramics. The preparation temperature of the CVI method is low, the purity of the obtained SiC matrix is high, and it can also be formed into a near-net size. However, during the preparation of CVI, the oxidation resistance of CVI will be greatly reduced due to the generation of defects and the cracks in the matrix caused by thermal mismatch. Through matrix modification and post-densification treatment, further increasing the density of the composite material can improve the oxidation resistance of the SiC matrix to a certain extent.
我们前期利用PIP工艺制备了氧化铝纤维增强碳化硅(Al2O3f/SiC)陶瓷基复合材料,对其力学性能和微观形貌进行了研究,结果表明:未经界面改性的Al2O3f/SiC复合材料中纤维/基体界面结合较强,表现出脆性断裂行为,弯曲强度仅为42.8MPa。此外,还利用CVI工艺制备了Al2O3f/SiC复合材料,研究结果表明:氧化铝纤维和SiC基体间能原位形成一薄层碳涂层,从而削弱了界面结合,复合材料的力学性能较优,弯曲强度达到92.1MPa。然而,由于基体中存在较多的孔隙和裂纹,导致复合材料的抗氧化性能不理想。In the early stage, we used the PIP process to prepare alumina fiber reinforced silicon carbide (Al 2 O 3f /SiC) ceramic matrix composites, and studied its mechanical properties and microscopic morphology. The results showed that: Al 2 O without interface modification The fiber/matrix interface in the 3f /SiC composite is strongly bonded, showing brittle fracture behavior, and the bending strength is only 42.8MPa. In addition, the Al 2 O 3f /SiC composite material was prepared by CVI process. The research results showed that a thin layer of carbon coating could be formed in situ between the alumina fiber and the SiC matrix, thus weakening the interfacial bonding and improving the mechanical properties of the composite material. Better, the bending strength reaches 92.1MPa. However, due to the existence of many pores and cracks in the matrix, the oxidation resistance of the composite is not ideal.
发明内容Contents of the invention
本发明所要解决的技术问题是,克服以上背景技术中提到的不足和缺陷,提供一种力学性能、耐高温和抗氧化性能优异的氧化铝纤维增强碳化硅-硅酸铝陶瓷,并相应提供一种制备周期短、成本低、可以近净尺寸成型的该氧化铝纤维增强碳化硅-硅酸铝陶瓷的制备方法。The technical problem to be solved by the present invention is to overcome the deficiencies and defects mentioned in the above background technology, provide an alumina fiber reinforced silicon carbide-aluminosilicate ceramic with excellent mechanical properties, high temperature resistance and oxidation resistance, and provide correspondingly The invention discloses a preparation method of the alumina fiber reinforced silicon carbide-aluminosilicate ceramics which has short preparation period, low cost and can be molded in near net size.
为解决上述技术问题,本发明提出的技术方案为一种氧化铝纤维增强碳化硅-硅酸铝陶瓷(简称Al2O3f/SiC-AS),所述陶瓷是以氧化铝纤维织物(Al2O3f)作为增强体,以碳化硅陶瓷(SiC)和硅酸铝陶瓷(AS)作为基体,所述碳化硅陶瓷主要是采用化学气相渗透法成型得到,所述硅酸铝陶瓷是通过溶胶-凝胶工艺引入。In order to solve the above technical problems, the technical solution proposed by the present invention is an alumina fiber reinforced silicon carbide-aluminum silicate ceramic (referred to as Al 2 O 3f /SiC-AS), the ceramic is made of alumina fiber fabric (Al 2 O 3f ) as a reinforcement, with silicon carbide ceramics (SiC) and aluminum silicate ceramics (AS) as substrates, the silicon carbide ceramics are mainly formed by chemical vapor infiltration, and the aluminum silicate ceramics are formed by sol- The gel process is introduced.
上述的氧化铝纤维增强碳化硅-硅酸铝陶瓷,优选的:所述基体包含20%~40%体积分数(占整个氧化铝纤维增强碳化硅-硅酸铝陶瓷的体积分数,下同)的碳化硅陶瓷和10%~20%体积分数的硅酸铝陶瓷(其余的体积空间主要为孔隙)。The above-mentioned alumina fiber reinforced silicon carbide-aluminum silicate ceramics, preferably: the matrix contains 20% to 40% volume fraction (accounting for the volume fraction of the entire alumina fiber reinforced silicon carbide-aluminum silicate ceramics, the same below) Silicon carbide ceramics and aluminum silicate ceramics with a volume fraction of 10% to 20% (the rest of the volume space is mainly pores).
上述的氧化铝纤维增强碳化硅-硅酸铝陶瓷,优选的:所述陶瓷的弯曲强度在125MPa以上,且经过1000℃的高温氧化100h后的弯曲强度在110MPa以上;所述陶瓷的弹性模量在70GPa以上,且经过1000℃的高温氧化100h后的弹性模量在60GPa以上。The above alumina fiber reinforced silicon carbide-aluminosilicate ceramics, preferably: the bending strength of the ceramic is above 125MPa, and the bending strength after high temperature oxidation at 1000°C for 100h is above 110MPa; the elastic modulus of the ceramic It is above 70GPa, and the elastic modulus after high temperature oxidation at 1000°C for 100h is above 60GPa.
作为一个总的技术构思,本发明还提供一种上述氧化铝纤维增强碳化硅-硅酸铝陶瓷的制备方法,包括以下工艺步骤:As a general technical concept, the present invention also provides a method for preparing the above-mentioned alumina fiber reinforced silicon carbide-aluminosilicate ceramics, comprising the following process steps:
(1)Al2O3f/SiC陶瓷坯体的制备:以氧化铝纤维织物、三氯甲基硅烷、氢气、氩气为原料,采用化学气相渗透法(CVI)制备Al2O3f/SiC陶瓷坯体;(1) Preparation of Al 2 O 3f /SiC ceramic body: Al 2 O 3f /SiC ceramics were prepared by chemical vapor infiltration (CVI) using alumina fiber fabric, trichloromethylsilane, hydrogen, and argon as raw materials Body;
(2)Al2O3f/SiC陶瓷坯体的加工:对上述步骤(1)制得的Al2O3f/SiC陶瓷坯体进行表面加工,将表面的大量闭孔变为开孔以便于进行后续致密化;(2) Processing of Al 2 O 3f /SiC ceramic body: Surface processing is carried out on the Al 2 O 3f /SiC ceramic body prepared in the above step (1), and a large number of closed pores on the surface are changed into open pores for easy processing. subsequent densification;
(3)AS陶瓷后续致密化:利用硅铝复合溶胶真空浸渍上述步骤(2)后的Al2O3f/SiC陶瓷坯体,经凝胶化、高温陶瓷化后转变为中间产品;(3) Subsequent densification of AS ceramics: the Al 2 O 3f /SiC ceramic body after the above step (2) is vacuum impregnated with silicon-aluminum composite sol, and transformed into an intermediate product after gelation and high-temperature ceramicization;
(4)重复上述步骤(3)的过程至少4次(优选4~8次),最终制得氧化铝纤维增强碳化硅-硅酸铝陶瓷。(4) Repeat the process of the above step (3) at least 4 times (preferably 4-8 times), and finally obtain alumina fiber reinforced silicon carbide-aluminosilicate ceramics.
上述的制备方法,优选的,所述步骤(1)中,所述氧化铝纤维织物为2.5D结构、三维四向结构、三维五向结构、三维六向结构或三维正交结构;所述氧化铝纤维织物中纤维体积分数为35%~45%。In the above preparation method, preferably, in the step (1), the alumina fiber fabric is a 2.5D structure, a three-dimensional four-way structure, a three-dimensional five-way structure, a three-dimensional six-way structure or a three-dimensional orthogonal structure; The fiber volume fraction in the aluminum fiber fabric is 35% to 45%.
上述的制备方法,优选的,所述步骤(1)中,所述化学气相渗透法的工艺参数条件包括:沉积温度为1000℃~1200℃,沉积压力为1kPa~5kPa,氢气和氩气流速比为3:1~1:1,沉积时间为6h~10h。In the above-mentioned preparation method, preferably, in the step (1), the process parameter conditions of the chemical vapor infiltration method include: the deposition temperature is 1000°C to 1200°C, the deposition pressure is 1kPa to 5kPa, and the flow rate ratio of hydrogen and argon is It is 3:1~1:1, and the deposition time is 6h~10h.
上述的制备方法,优选的,所述步骤(3)中,所述真空浸渍的工艺过程包括:利用硅铝复合溶胶真空浸渍所述Al2O3f/SiC陶瓷坯体4h~8h,然后取出在空气中晾置1h~2h;所述硅铝复合溶胶的固含量为18.2wt%~25.3wt%。In the above-mentioned preparation method, preferably, in the step (3), the vacuum impregnation process includes: vacuum impregnating the Al 2 O 3f /SiC ceramic body with a silicon-aluminum composite sol for 4h to 8h, and then taking it out in the The solid content of the silicon-aluminum composite sol is 18.2wt%-25.3wt%.
上述的制备方法,优选的,所述步骤(3)中,所述凝胶化是采用干燥方式完成,其干燥工艺过程包括:将经真空浸渍后的陶瓷坯体放入烘箱中,以2℃/min~3℃/min的升温速率升温至150℃~200℃,干燥4h~6h,然后自然冷却到室温取出。In the above-mentioned preparation method, preferably, in the step (3), the gelation is completed by drying, and the drying process includes: putting the vacuum-impregnated ceramic body into an oven at 2°C /min~3℃/min heating rate to 150℃~200℃, dry for 4h~6h, then cool naturally to room temperature and take out.
上述的制备方法,优选的,所述步骤(3)中,所述高温陶瓷化是采用高温裂解的方式完成,其具体的工艺过程包括:将所述凝胶化后的陶瓷坯体放入裂解炉中,在空气中以5℃/min~10℃/min的升温速率升至900℃~1100℃,保温0.5h~1.5h,自然冷却至100℃以下取出。In the above preparation method, preferably, in the step (3), the high-temperature ceramization is completed by high-temperature cracking, and its specific process includes: putting the gelled ceramic body into cracking In the furnace, raise the temperature to 900°C-1100°C at a rate of 5°C/min-10°C/min in the air, keep it warm for 0.5h-1.5h, cool naturally to below 100°C and take it out.
本发明主要遵循以下技术思路:在不改变CVI工艺制备的Al2O3f/SiC复合材料性能的前提下,通过对基体进行改性和后续致密化处理,以进一步弥合基体中的裂纹缺陷,进而提升复合材料的力学性能和抗氧化性能。在具体的制备过程中,我们首先通过CVI工艺制备Al2O3f/SiC陶瓷坯体,然后以硅铝复合溶胶为先驱体,采用溶胶-凝胶工艺对Al2O3f/SiC陶瓷坯体进行后致密化处理,制得力学性能和抗氧化性能优异的氧化铝纤维增强碳化硅-硅酸铝陶瓷。The present invention mainly follows the following technical ideas: on the premise of not changing the properties of the Al 2 O 3f /SiC composite material prepared by the CVI process, the matrix is modified and subsequently densified to further bridge the crack defects in the matrix, and then Improve the mechanical properties and oxidation resistance of composite materials. In the specific preparation process, we firstly prepared the Al 2 O 3f /SiC ceramic body by the CVI process, and then used the silicon-aluminum composite sol as the precursor, and used the sol-gel process to prepare the Al 2 O 3f /SiC ceramic body. After post-densification treatment, alumina fiber reinforced silicon carbide-aluminosilicate ceramics with excellent mechanical properties and oxidation resistance were obtained.
与现有技术相比,本发明的优点在于:Compared with the prior art, the present invention has the advantages of:
1.本发明的Al2O3f/SiC-AS陶瓷的制备方法为气相法结合液相法,可在较低温度下无压烧结制备SiC-AS陶瓷基体,制备周期短;1. The preparation method of the Al 2 O 3f /SiC-AS ceramics of the present invention is a gas phase method combined with a liquid phase method, and the SiC-AS ceramic substrate can be prepared by pressureless sintering at a relatively low temperature, and the preparation cycle is short;
2.本发明的方法可通过纤维编织方式制备结构复杂的构件,产品外形尺寸可通过数控机床加工精确控制;选取的原料广泛易得,可广泛应用于工业化生产。2. The method of the present invention can prepare components with complex structures through fiber weaving, and the external dimensions of the products can be precisely controlled by CNC machine tools; the selected raw materials are widely available and can be widely used in industrial production.
本发明的Al2O3f/SiC-AS陶瓷,具有一般陶瓷基复合材料的常见优点,如高比强度和比模量、优异的抗热震性能等。此外,与Cf/SiC、SiCf/SiC和Al2O3f/SiC陶瓷基复合材料相比,本发明的Al2O3f/SiC-AS陶瓷具有更优异的抗氧化性能和耐环境性能。The Al 2 O 3f /SiC-AS ceramic of the present invention has common advantages of general ceramic matrix composite materials, such as high specific strength and specific modulus, excellent thermal shock resistance and the like. In addition, compared with C f /SiC, SiC f /SiC and Al 2 O 3f /SiC ceramic matrix composites, the Al 2 O 3f /SiC-AS ceramics of the present invention have more excellent oxidation resistance and environmental resistance.
附图说明Description of drawings
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following will briefly introduce the drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are For some embodiments of the present invention, those skilled in the art can also obtain other drawings based on these drawings without creative work.
图1是本发明实施例1中制得的Al2O3f/SiC-AS陶瓷的光学照片。Fig. 1 is an optical photograph of Al 2 O 3f /SiC-AS ceramics prepared in Example 1 of the present invention.
图2是本发明实施例1中制得的Al2O3f/SiC-AS陶瓷中基体的能谱分析。Fig. 2 is an energy spectrum analysis of the matrix in Al 2 O 3f /SiC-AS ceramics prepared in Example 1 of the present invention.
图3是本发明实施例1中制得的Al2O3f/SiC-AS陶瓷的微观形貌图。Fig. 3 is a microscopic morphology diagram of Al 2 O 3f /SiC-AS ceramics prepared in Example 1 of the present invention.
具体实施方式Detailed ways
为了便于理解本发明,下文将结合说明书附图和较佳的实施例对本发明作更全面、细致地描述,但本发明的保护范围并不限于以下具体的实施例。In order to facilitate the understanding of the present invention, the present invention will be described in more detail below in conjunction with the accompanying drawings and preferred embodiments, but the protection scope of the present invention is not limited to the following specific embodiments.
除非另有定义,下文中所使用的所有专业术语与本领域技术人员通常理解的含义相同。本文中所使用的专业术语只是为了描述具体实施例的目的,并不是旨在限制本发明的保护范围。Unless otherwise defined, all professional terms used hereinafter have the same meaning as commonly understood by those skilled in the art. The terminology used herein is only for the purpose of describing specific embodiments, and is not intended to limit the protection scope of the present invention.
除非另有特别说明,本发明中用到的各种原材料、试剂、仪器和设备等均可通过市场购买得到或者可通过现有方法制备得到。Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods.
实施例1:Example 1:
一种如图1所示本发明的氧化铝纤维增强碳化硅-硅酸铝陶瓷(简写为Al2O3f/SiC-AS),包含有约41%体积分数的氧化铝纤维、约33%体积分数的SiC陶瓷和约12%体积分数的AS陶瓷。A kind of aluminum oxide fiber reinforced silicon carbide-aluminosilicate ceramics (abbreviated as Al 2 O 3f /SiC-AS) of the present invention as shown in Figure 1, comprises the alumina fiber of about 41% volume fraction, about 33% volume Fraction of SiC ceramics and about 12% volume fraction of AS ceramics.
一种制备上述本实施例Al2O3f/SiC-AS陶瓷的方法,具体包括以下步骤:A method for preparing the above-mentioned Al 2 O 3f /SiC-AS ceramics in this embodiment, specifically comprising the following steps:
(1)Al2O3f/SiC陶瓷坯体的制备:以三维正交氧化铝纤维织物为增强体、三氯甲基硅烷-氢气-氩气为原料,采用CVI制备Al2O3f/SiC陶瓷坯体;CVI工艺参数为:沉积温度为1100℃、沉积压力为1.5kPa、氢气和氩气流速比为1.5∶1、沉积时间为10h;(1) Preparation of Al 2 O 3f /SiC ceramic body: Using three-dimensional orthogonal alumina fiber fabric as reinforcement and trichloromethylsilane-hydrogen-argon as raw material, Al 2 O 3f /SiC ceramics were prepared by CVI Green body; CVI process parameters are: deposition temperature is 1100°C, deposition pressure is 1.5kPa, hydrogen and argon gas flow ratio is 1.5:1, deposition time is 10h;
(2)Al2O3f/SiC陶瓷坯体的加工:对上述步骤(1)制得的Al2O3f/SiC陶瓷坯体进行表面加工,将表面的大量闭孔变为开孔以便于进行后续致密化;(2) Processing of Al 2 O 3f /SiC ceramic body: Surface processing is carried out on the Al 2 O 3f /SiC ceramic body prepared in the above step (1), and a large number of closed pores on the surface are changed into open pores for easy processing. subsequent densification;
(3)AS陶瓷后续致密化:首先,以固含量为19.5wt%的硅铝复合溶胶为先驱体,对上述步骤(2)制得的Al2O3f/SiC陶瓷坯体进行真空浸渍6h,取出在空气中晾置2h;然后,将经真空浸渍后的陶瓷坯体放入烘箱中进行凝胶化处理,以2℃/min的升温速率升温至200℃,干燥5h,自然冷却到室温取出;最后,将凝胶化后的陶瓷坯体放入裂解炉中,在空气中以8℃/min的升温速率升至1000℃,保温1h,自然冷却至100℃以下取出;(3) Subsequent densification of AS ceramics: first, the Al 2 O 3f /SiC ceramic green body prepared in the above step (2) was vacuum impregnated for 6 hours with the silicon-alumina composite sol with a solid content of 19.5 wt% as the precursor, Take it out and leave it in the air for 2 hours; then, put the vacuum-impregnated ceramic body into an oven for gelation treatment, heat up to 200°C at a heating rate of 2°C/min, dry for 5h, and cool naturally to room temperature. ; Finally, put the gelled ceramic body into the cracking furnace, raise the temperature to 1000°C in the air at a rate of 8°C/min, keep it warm for 1 hour, and cool it naturally to below 100°C to take it out;
(4)重复上述步骤(3)4次,制得Al2O3f/SiC-AS陶瓷。(4) Repeat the above step (3) four times to prepare Al 2 O 3f /SiC-AS ceramics.
经上述步骤制得的本实施例的Al2O3f/SiC-AS陶瓷的光学照片如图1所示,其基体能谱分析如图2所示,由图2可见,本实施例制备的Al2O3f/SiC-AS陶瓷基体中含有C、Si、Al和O元素,与SiC和AS所含元素一致。The optical photo of the Al 2 O 3f /SiC-AS ceramics of this example prepared through the above steps is shown in Figure 1, and its matrix energy spectrum analysis is shown in Figure 2. It can be seen from Figure 2 that the Al 2 O 3f/SiC-AS ceramics prepared in this example The 2 O 3f /SiC-AS ceramic matrix contains C, Si, Al and O elements, which are consistent with those contained in SiC and AS.
本实施例制备的Al2O3f/SiC-AS陶瓷的截面形貌如图3所示,由图3可见,Al2O3f/SiC-AS陶瓷复合材料中束丝内部存在少量的微孔,而束丝之间的孔隙较大;此外,纤维和基体之间的界面较为清晰,表明纤维和基体的相容性较好。The cross-sectional morphology of the Al 2 O 3f /SiC-AS ceramics prepared in this example is shown in Figure 3. It can be seen from Figure 3 that there are a small amount of micropores inside the bundles of the Al 2 O 3f /SiC-AS ceramic composites. The pores between the bundles are larger; in addition, the interface between the fiber and the matrix is clearer, indicating that the compatibility of the fiber and the matrix is better.
参照上述本实施例的工艺参数条件,采用CVI工艺制备Al2O3f/SiC陶瓷作为对照样1;同时,利用硅铝复合溶胶致密化氧化铝纤维织物,制备Al2O3f/AS陶瓷作为对照样2。对上述本实施例得到的Al2O3f/SiC-AS陶瓷和对照样进行力学性能对比测试,得到如下表1所示的主要性能参数。Referring to the above-mentioned process parameter conditions of this example, Al 2 O 3f /SiC ceramics were prepared by CVI process as control sample 1; at the same time, Al 2 O 3f /AS ceramics were prepared by densifying alumina fiber fabrics with silicon-aluminum composite sol. 2 as usual. The comparative test of the mechanical properties of the Al 2 O 3f /SiC-AS ceramic obtained in the above-mentioned embodiment and the control sample was carried out, and the main performance parameters shown in Table 1 below were obtained.
表1:实施例1中对比测试得到的三种复合材料的主要性能参数Table 1: The main performance parameters of the three composite materials obtained by comparative testing in Example 1
实施例2:Example 2:
一种本发明的氧化铝纤维增强碳化硅-硅酸铝陶瓷(简写为Al2O3f/SiC-AS),包含有约43%体积分数的氧化铝纤维、约25%体积分数的SiC陶瓷和约18%体积分数的AS陶瓷。An alumina fiber reinforced silicon carbide-aluminosilicate ceramic (abbreviated as Al 2 O 3f /SiC-AS) of the present invention comprises about 43% volume fraction of alumina fiber, about 25% volume fraction of SiC ceramic and about 18% volume fraction of AS ceramics.
一种制备上述本实施例Al2O3f/SiC-AS陶瓷的方法,具体包括以下步骤:A method for preparing the above-mentioned Al 2 O 3f /SiC-AS ceramics in this embodiment, specifically comprising the following steps:
(1)Al2O3f/SiC陶瓷坯体的制备:以三维正交氧化铝纤维织物为增强体、三氯甲基硅烷-氢气-氩气为原料,采用CVI制备Al2O3f/SiC陶瓷坯体;CVI工艺参数为:沉积温度为1050℃、沉积压力为2kPa、氢气和氩气流速比为2∶1、沉积时间为8h;(1) Preparation of Al 2 O 3f /SiC ceramic body: Using three-dimensional orthogonal alumina fiber fabric as reinforcement and trichloromethylsilane-hydrogen-argon as raw material, Al 2 O 3f /SiC ceramics were prepared by CVI Green body; CVI process parameters are: deposition temperature is 1050°C, deposition pressure is 2kPa, hydrogen and argon flow ratio is 2:1, deposition time is 8h;
(2)Al2O3f/SiC陶瓷坯体的加工:对上述步骤(1)制得的Al2O3f/SiC陶瓷坯体进行表面加工,将表面的大量闭孔变为开孔以便于进行后续致密化;(2) Processing of Al 2 O 3f /SiC ceramic body: Surface processing is carried out on the Al 2 O 3f /SiC ceramic body prepared in the above step (1), and a large number of closed pores on the surface are changed into open pores for easy processing. subsequent densification;
(3)AS陶瓷后续致密化:首先,以固含量为21.2wt%的硅铝复合溶胶为先驱体,对上述步骤(2)制得的Al2O3f/SiC陶瓷坯体进行真空浸渍7h,取出在空气中晾置1.5h;然后,将经真空浸渍后的陶瓷坯体放入烘箱中进行凝胶化处理,以2.5℃/min的升温速率升温至180℃,干燥6h,自然冷却到室温取出;最后,将凝胶化后的陶瓷坯体放入裂解炉中,在空气中以10℃/min的升温速率升至1050℃,保温0.5h,自然冷却至100℃以下取出;(3) Subsequent densification of AS ceramics: first, the Al 2 O 3f /SiC ceramic green body prepared in the above step (2) was vacuum impregnated for 7 hours using the silicon-alumina composite sol with a solid content of 21.2 wt% as a precursor, Take it out and let it dry in the air for 1.5h; then, put the vacuum-impregnated ceramic body into an oven for gelation treatment, raise the temperature to 180°C at a heating rate of 2.5°C/min, dry for 6h, and naturally cool to room temperature Take it out; finally, put the gelled ceramic body into the cracking furnace, raise the temperature to 1050°C in the air at a rate of 10°C/min, keep it warm for 0.5h, cool naturally to below 100°C and take it out;
(4)重复上述步骤(3)6次,制得Al2O3f/SiC-AS陶瓷。(4) Repeat the above step (3) 6 times to prepare Al 2 O 3f /SiC-AS ceramics.
参照上述本实施例的工艺参数条件,采用CVI工艺制备Al2O3f/SiC陶瓷作为对照样1;同时,利用硅铝复合溶胶致密化氧化铝纤维织物,制备Al2O3f/AS陶瓷作为对照样2。对上述本实施例得到的Al2O3f/SiC-AS陶瓷和对照样进行力学性能对比测试,得到如下表2所示的主要性能参数。Referring to the above-mentioned process parameter conditions of this example, Al 2 O 3f /SiC ceramics were prepared by CVI process as control sample 1; at the same time, Al 2 O 3f /AS ceramics were prepared by densifying alumina fiber fabrics with silicon-aluminum composite sol. 2 as usual. The comparative test of the mechanical properties of the Al 2 O 3f /SiC-AS ceramic obtained in the above-mentioned embodiment and the control sample was carried out, and the main performance parameters shown in Table 2 below were obtained.
表2:实施例2中对比测试得到的三种复合材料的主要性能参数Table 2: The main performance parameters of the three composite materials obtained by comparative testing in Example 2
由上可见,上述本发明制得的氧化铝纤维增强碳化硅-硅酸铝陶瓷的弯曲强度在129MPa以上,且经过1000℃的高温氧化100h后的弯曲强度仍在115MPa以上;陶瓷的弹性模量在72GPa以上,且经过1000℃的高温氧化100h后的弹性模量仍在61GPa以上。It can be seen from the above that the bending strength of the aluminum oxide fiber reinforced silicon carbide-aluminosilicate ceramics prepared by the present invention is above 129MPa, and the bending strength after high temperature oxidation at 1000°C for 100h is still above 115MPa; the elastic modulus of ceramics It is above 72GPa, and the elastic modulus after high temperature oxidation at 1000°C for 100h is still above 61GPa.
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