CN109476552B - 复合材料部件 - Google Patents
复合材料部件 Download PDFInfo
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- CN109476552B CN109476552B CN201780029402.6A CN201780029402A CN109476552B CN 109476552 B CN109476552 B CN 109476552B CN 201780029402 A CN201780029402 A CN 201780029402A CN 109476552 B CN109476552 B CN 109476552B
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Abstract
本发明提供一种复合材料制成的部件,其至少包含:‑包含碳化硅纤维的纤维增强体,以原子百分比计,其氧含量小于或等于1%;和‑基质,其存在于纤维增强体的孔中并包含至少一种稀土硅酸盐、莫来石、或莫来石和至少一种稀土硅酸盐的混合物。
Description
背景技术
本发明涉及由复合材料制成的部件,其可在较高的温度、高于或等于1300℃、例如1300℃至1450℃下使用本发明还涉及制造这样的部件的方法以及使用其的方法。
现有技术中已经提出了各种材料用于制造涡轮发动机部件。
特别是,已知使用陶瓷基质复合(CMC)材料,其包括由碳化硅纤维制成的纤维增强体以及通过化学气相渗透(CVI)形成的基于碳化硅的基质。该材料在1300℃或1400℃的温度下具有非常好的寿命特性,但由于使用CVI方法,其具有相对较高的生产成本。已经研发了其它方法以降低由CMC制成的部件的生产成本。
在本文中,提出了形成复合材料部件的建议,该复合材料部件包括基于涂覆在界面涂层中的碳化硅的纤维增强体以及通过非反应性或反应性熔体渗透(MI或RMI)形成的基质。然而,这样的材料可能因为基质中存在残留硅而被限制在低于1300℃的温度下使用。还提出了具有氧化物基质的氧化物纤维增强体。该材料具有相对较低的生产成本,但是其也受限于使用温度。
因此,需要提供一种材料,其与在高于或等于1300℃、或甚至1450℃的温度下使用相兼容,并且可以通过相对低成本的方法制造。
本发明旨在满足该需要。
发明目的和概述
为此,在本发明的一个方面中,本发明提供了一种由复合材料制成的部件,其至少包含:
-包含碳化硅纤维的纤维增强体,以原子百分比计,其氧含量小于或等于1%;和
-基质,其存在于纤维增强体的孔中并包含至少一种稀土硅酸盐、莫来石(3Al2O3.2SiO2)、或莫来石和至少一种稀土硅酸盐的混合物。
本发明有利地用于提供一种部件,其与在高于或等于1300℃、或甚至1450℃的温度下使用相兼容,并且可以通过相对有限的生产成本制造。此外,由于部件的基质包含环境阻隔材料,本发明的部件可以在氧化性和潮湿的气氛中使用
因此,基质包含至少一个硅酸盐相。硅酸盐相可以包含至少一种稀土硅酸盐、莫来石、或可以实际上包含莫来石和至少一种稀土硅酸盐的混合物。
在一实施方式中,所述稀土硅酸盐可以具有如下化学式:RE2SiO5或RE2Si2O7,其中RE表示稀土元素。优选地,稀土硅酸盐具有化学式RE2Si2O7。
例如,稀土元素RE可以选自:Y(钇);Er(铒);Yb(镱);Lu(镥);和Dy(镝)。优选地,稀土元素RE可以选自:Y;Yb;和Lu。
在一实施方式中,基质可以至少包含第一相和不同于第一相的第二相,所述第一相包含莫来石,所述第二相包含至少一种稀土硅酸盐。
从在基质中加入莫来石比加入稀土硅酸盐便宜的角度,使用该基质有利于进一步降低生产部件的成本。
在一实施方式中,第一相可以位于碳化硅纤维和第二相之间。换言之,在该情况下,包含莫来石的第一相位于纤维旁边,并且含有稀土硅酸盐的第二相位于部件的外表面旁边。
在一实施方式中,所述基质包含:
-至少一个硅酸盐相,其包含至少一种稀土硅酸盐、莫来石、或莫来石和至少一种稀土硅酸盐的混合物;以及
-不同于硅酸盐相的另一基质相,其由陶瓷材料制成,位于碳化硅纤维和硅酸盐相之间。
该另一基质相的存在有利于进一步提高复合材料部件的机械性能。
在一实施方式中,所述部件可以构成航空发动机部件。
该部件可以是工业涡轮或航空发动机的燃气涡轮的热部件。特别是,所述部件可以构成下述部件的至少一部分:分配器、燃烧室的壁、涡轮环区段、或者涡轮发动机叶片或叶。
本发明还提供了一种制造如上所述部件的方法,所述方法至少包括在纤维增强体的孔中形成基质的步骤。
在一实施方式中,可以通过烧结形成基质的至少一部分。
该特征有利于使用降低实施成本的技术来制造部件。
在一实施方式中,所有基质都可以通过烧结形成,或者在一变体中,可以通过烧结仅形成基质的一部分。
特别是,在烧结期间施加高于或等于1200℃的温度。
该特性是有利的,因为这使得可以进行显著的烧结,从而进一步改进所得部件的机械性能。
在一实施方式中,可以至少通过进行如下步骤来形成基质:
-将莫来石的至少一种粉末或莫来石的至少一种溶胶-凝胶前体的至少一种粉末引入纤维增强体的孔中;
-将被引入的莫来石或在溶胶-凝胶前体转化后获得的莫来石进行烧结,以形成包含莫来石的第一基质相;
-将稀土硅酸盐的至少一种粉末或稀土硅酸盐的至少一种溶胶-凝胶前体的至少一种粉末引入用第一基质相致密化的纤维增强体的孔中;
-将被引入的稀土硅酸盐或在溶胶-凝胶前体转化后获得的稀土硅酸盐进行烧结,以形成包含稀土硅酸盐的第二基质相。
这样的方法使得可以制造包含莫来石和稀土硅酸盐的基质,并且其构成了一种能够以特别低的实施成本获得具有所需性能的部件的方案。
本发明还提供了使用如上所述部件的方法,其中,所述部件在高于或等于1300℃、例如1300℃至1450℃的温度下使用。特别是,该部件可以在氧化性和潮湿的气氛中使用。
考虑到用于形成基质的材料的性质,部件可以有利地在使用时不具有环境阻隔涂层。具体来说,基质为部件提供了所需的耐腐蚀性。然而,如果在设置有环境阻隔涂层的同时使用该部件,也不会超出本发明的范围。
附图简要说明
参考附图,通过阅读在下文中通过非限制性标记可以更好地理解本发明,其中:
-图1显示制造本发明部件的方法的第一实施例中的连续步骤;并且
-图2显示制造本发明部件的方法的第二实施例中的连续步骤。
具体实施方式
例如,以原子百分比计,氧含量小于或等于1%的碳化硅纤维可以是由日本供应商NGS以“Hi-Nicalon-S”名字提供的纤维。这些纤维在下文中被称为“SiC纤维”。
纤维增强体可以通过三维或多层编织制成单件,或者由多个二维纤维层制成,或者实际上由多个一维织物层制成。
术语“三维编织”或“3D编织”应当理解为一种编织技术,其中,至少部分经纱与多个纬层上的纬纱互连。在本说明书中,经纱和纬纱之间可以互换角色,并且也应认为被本发明权利要求书所覆盖。
例如,纤维增强体可以具有多缎纹编织,即,通过用多层纬纱三维编织获得的织物,其中各层的编织与常规的缎纹型编织等同,但是编织的某些点与纬纱层连在一起。在一变体中,纤维增强体具有互锁编织。术语"互锁"应当理解为3D编织,其中经纱的各层与多层纬纱连在一起,其中相同经列中的所有纱线在编织平面中同样地移动。适用于形成纤维增强体的各种多层编织技术具体描述于文件WO 2006/136755中。
还可以使用纤维织构,如SiC纤维的二维织物或SiC纤维的单向片材,并通过将这种纤维织构铺设在成形机上来获得纤维增强体。这些织构可以可选地彼此连接,例如,通过缝合或通过植入纱线可选地彼此连接,以形成纤维增强体。
SiC纤维可以通过存在于SiC纤维和基质之间的中间相进行涂覆。中间相可包括单层或多层。中间相可以包括至少一层热解碳(PyC)、氮化硼(BN)、硅掺杂的氮化硼(BN(Si),硅的存在量以重量百分比计为5%至40%,余量为氮化硼)或硼掺杂的碳(BC,硼的存在量以原子百分比计为5%至20%,余量为碳)。在该情况下,中间相的作用是通过帮助蔓延穿过基质后到达中间相的任何裂缝进行偏转来为复合材料提供脆性释放(embrittlementrelief),从而防止或阻止纤维通过这种裂缝破裂。
基质通过存在于纤维增强件的孔中而使得增强件致密化。基质包含覆盖纤维增强件纤维的至少一个连续硅酸盐相。SiC纤维存在于基质中。基质可占纤维增强件中的可进入孔的体积的大部分(即,超过50%)。特别是,基质可以占可进入孔的超过75%的体积,或实际上占可进入孔的基本所有体积。
基质包含至少一个硅酸盐相,其包含:
至少一种稀土硅酸盐;或
-莫来石;或
-莫来石和至少一种稀土硅酸盐的混合物。
基质还可以有利地包含位于纤维(或中间相)和硅酸盐相之间的陶瓷材料的另一基质相。该另一相用于进一步改善复合材料部件的机械性能。该另一相由不同于构成硅酸盐相的材料构成。该另一相可以包含碳化物或氮化物。例如,另一相可以包含:SiC、Si3N4、SiN(O)、SiC(B)、或该化合物的混合物。当然,当存在这样的另一基质相时,在制备另一相后纤维增强体中剩余的残留孔足以能够使硅酸盐相形成。在一变体中,基质不需要具有这样的另一相。
至少50%重量的基质可以由至少一种稀土硅酸盐、莫来石、或莫来石和至少一种稀土硅酸盐的混合物构成。至少80%重量的基质可以由至少一种稀土硅酸盐、莫来石、或莫来石和至少一种稀土硅酸盐的混合物构成。具体来说,忽略不可避免的杂质,基质可以完全由至少一种稀土硅酸盐、莫来石、或莫来石和至少一种稀土硅酸盐的混合物构成。
在一实施方式中,基质包含单一稀土硅酸盐或具有多种相同稀土或不同稀土的硅酸盐。稀土硅酸盐可以具有如下形式:RE2SiO5或RE2Si2O7,其中RE表示稀土元素。例如,RE可以选自:钇Y;钪Sc和镧系元素,例如,镱Yb;镥Lu;镝Dy;铒Er;和镧La。如上所述,稀土硅酸盐可以有利得具有RE2Si2O7形式,其中RE选自:Y;Yb;和Lu。
制造本发明部件的方法的第一实施例参考图1在下文中进行说明。
第一步10可以包括用SiC制备纤维增强件。在步骤10期间,部件的纤维增强件可以通过使用SiC纤维进行至少一个纺织操作来获得。纤维增强件可以通过SiC纤维的三维编织或多层来获得。
优选在形成中间相前进行对SiC纤维的表面处理的步骤20,具体是为了消除纤维上存在的胶料(sizing)。
步骤30由如下所述组成:在形成纤维增强件的SiC纤维上通过CVI形成脆性释放中间相。该中间相可以由PyC制成。例如,中间相的厚度可以在10纳米(nm)至1000nm的范围内,例如在10nm至100nm的范围内。在形成中间相之后,纤维增强件保持多孔,其中只有少数部分的初始可进入孔由中间相进行填充。
然后进行步骤35,其中,在之前形成的中间相上,另一陶瓷基质相形成于纤维增强件的孔中。该另一相可以通过CVI形成。
随后,在步骤40期间,通过本身已知的方法(如,通过注射)将浸渍组合物(例如,浆料形式的浸渍组合物)引入纤维增强件的孔中。浸渍组合物可以包含悬浮在液体介质中的粉末,或者其可以是溶液形式的。浸渍组合物用于递送形成基质的硅酸盐相的成分。浸渍组合物可以已知方式包含结合剂。浸渍组合物的组成根据将要获得的硅酸盐相的组成的变化来确定。浸渍组合物可包含以下成分中的至少一种:稀土硅酸盐粉末、稀土硅酸盐的溶胶-凝胶前体、莫来石粉末、莫来石的溶胶-凝胶前体、或这些化合物的混合物。具体而言,浸渍组合物可以包含:a)莫来石粉末和莫来石的溶胶-凝胶前体的混合物;或b)莫来石粉末或稀土硅酸盐的溶胶-凝胶前体的混合物;或c)稀土硅酸盐粉末和稀土硅酸盐的溶胶-凝胶前体的混合物;或d)稀土硅酸盐粉末和莫来石的凝胶-溶胶前体的混合物;或e)莫来石粉末和稀土硅酸盐粉末的混合物;或者实际上是f)稀土硅酸盐的溶胶-凝胶前体和莫来石的溶胶-凝胶前体的混合物。存在于浸渍组合物中的粉末的平均粒度(D50)为低于或等于5微米(μm)或实际上低于或等于1μm。
一旦纤维增强件进行浸渍,使其干燥并进行脱粘(debinding),然后通过烧结形成硅酸盐相(步骤50)。当在浸渍组合物中使用一种或多种溶胶-凝胶前体时,在进行烧结的热处理之前,在较低的温度下进行第一热处理,用于将溶胶-凝胶前体转化为莫来石粉末和/或稀土硅酸盐粉末。
烧结期间施加的温度有利地是高于或等于1200℃,例如在1200℃至1400℃的范围内。构成纤维增强件的SiC纤维具有热稳定性,该热稳定性达到在该温度下进行烧结的步骤期间SiC纤维不会破损所需的程度。在高于1200℃的温度下对纤维增强件中的粉末进行烧结用于进一步改进由所得到的硅酸盐相呈现的机械性能。例如,烧结可以在空气中进行。
如上所述图1解释了基质仅具有一个硅酸盐相的情况。然而,如下文参考图2所述,基质包含多个不同硅酸盐相也不会超出本发明的范围。
在图2所示示例性方法中,步骤10、20、30和35与上文参考图1所述的那些相同。在形成另一基质相后,将第一浸渍组合物引入纤维增强件的孔中(步骤140)。第一浸渍组合物为如上文所述的。第一浸渍组合物用于递送可用于在烧结后形成基质的第一硅酸盐相的成分(步骤150)。
在形成第一硅酸盐相后,将不同于第一浸渍组合物的第二浸渍组合物引入纤维增强件的孔中(步骤160)。第二浸渍组合物如上文所述。第二浸渍组合物用于递送在烧结后用于形成基质的第二硅酸盐相的成分(步骤170)。第二硅酸盐相由不同于构成第一硅酸盐相的材料构成。
第一和第二硅酸盐相可以占纤维增强件的可进入孔的超过50%的体积,例如,可进入孔的超过75%的体积,例如,可进入孔的基本所有体积。
有利的是,第一和二硅酸盐相中的至少一个包含莫来石,以进一步降低生产复合材料部件的成本。因此,第一硅酸盐相可以包含莫来石,并且第二硅酸盐相可以包含至少一种稀土硅酸盐。在一变体中,第一硅酸盐相可以包含至少一种稀土硅酸盐,并且第二硅酸盐相可以包含莫来石。莫来石可以占复合材料部件体积的10%至25%。稀土硅酸盐可以占复合材料部件体积的5%至30%。
在未显示的变体中,在形成一个或多个硅酸盐相后,可以制造用于进一步改进所获得基质的内聚性的加固基质相。为此,可以用溶胶-凝胶前体来浸渍硅酸盐相,然后进行热处理。热处理开始于将溶胶-凝胶前体转变成将要获得的加固基质相的材料,然后对以这种方式获得的材料进行烧结,以形成加固基质相。
部件可以是涡轮发动机的静态部件或旋转部件。本发明的示例性涡轮发动机部件为如上所述。
此外,如上所述,不需要在所得到的复合部件的外表面上制造环境阻隔涂层。这可以进一步简化制造部件的方法,所述部件适用于在具有高温并包含水蒸气的气氛中使用。所得部件可以在高于或等于1,300℃的温度下使用,例如在1300℃至1450℃范围内的温度下使用,例如在1300℃至1400℃范围内的温度下使用。当然,部件在低于1300℃的温度下使用也不会超出本发明的范围。
在图1和图2所示的实施方式中,首先形成纤维增强件,然后将至少一种浸渍组合物引入其孔中。然而,不同方式形成的部件也不会超出本发明的范围。
因此,在一变体中,SiC可以用如上所述的浸渍组合物进行浸渍,并且随后通过缠绕以这种方式浸渍的SiC纤维的丝来制备纤维增强件。随后,纤维增强件可以进行干燥和脱粘步骤,然后可以按如上所述进行烧结,以获得复合材料部件。
而且,在一变体中,可以使用用如上所述浸渍组合物浸渍的SiC纤维来形成单向片材。然后,可以通过铺设以此方式形成的单向片材来获得纤维增强件,并且随后可以通过如上所述的烧结形成部件。
在另一变体中,可以通过铺设多层用浸渍组合物浸渍的二维纤维层来形成纤维增强件。
在所有三个上述变体中,当然可以在用浸渍组合物浸渍前在SiC纤维上任选地形成中间相,所述中间相如上所述。
术语"在…至…范围内"应理解为包括端值。
Claims (11)
1.一种由复合材料制成的部件,其至少包含:
- 包含碳化硅纤维的纤维增强体,以原子百分比计,其氧含量小于或等于1%;和
- 基质,其存在于纤维增强体的孔中并包含至少一个烧结的硅酸盐相,所述硅酸盐相包含至少一种稀土硅酸盐、莫来石、或莫来石和至少一种稀土硅酸盐的混合物,所述基质至少包含第一相和不同于第一相的第二相,所述第一相包含莫来石,所述第二相包含至少一种稀土硅酸盐,其中至少80%重量的基质由莫来石和至少一种稀土硅酸盐的混合物构成,
其中,第一相位于碳化硅纤维和第二相之间。
2.如权利要求1所述的部件,其中,所述稀土硅酸盐具有如下化学式:RE2SiO5或RE2Si2O7,其中RE表示稀土元素。
3.如权利要求2所述的部件,其中,RE选自:Y;Yb;和Lu。
4.如权利要求1所述的部件,其中,所述基质包含:
- 至少一个硅酸盐相,其包含至少一种稀土硅酸盐、莫来石、或莫来石和至少一种稀土硅酸盐的混合物;以及
- 不同于所述硅酸盐相的另一基质相,其由陶瓷材料制成,位于碳化硅纤维和硅酸盐相之间。
5.如权利要求1所述的部件,所述部件构成涡轮发动机部件。
6.如权利要求5所述部件,所述部件构成下述的至少一部分:分配器、燃烧室的壁、涡轮环区段、或者涡轮发动机叶片或叶。
7.一种制造如权利要求1所述的部件的方法,所述方法至少包括在所述纤维增强体的孔中形成所述基质的步骤,其中硅酸盐相通过烧结形成。
8.如权利要求7所述的方法,其中,在烧结期间施加高于或等于1200℃的温度。
9.如权利要求7所述的方法,其中,所述基质至少通过进行如下步骤形成:
- 将莫来石的至少一种粉末或莫来石的至少一种溶胶-凝胶前体的至少一种粉末引入所述纤维增强体的孔中;
- 对被引入的莫来石或在溶胶-凝胶前体转化后获得的莫来石进行烧结,以形成包含莫来石的第一基质相;
- 将稀土硅酸盐的至少一种粉末或稀土硅酸盐的至少一种溶胶-凝胶前体的至少一种粉末引入用第一基质相致密化的纤维增强体的孔中;
- 对被引入的稀土硅酸盐或在溶胶-凝胶前体转化后获得的稀土硅酸盐进行烧结,以形成包含稀土硅酸盐的第二基质相。
10.一种使用如权利要求1所述部件的方法,其中,部件在高于或等于1300℃的温度下使用。
11.如权利要求10所述的方法,其中,所述部件在氧化性和潮湿的气氛中使用。
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FR1654200A FR3051187B1 (fr) | 2016-05-11 | 2016-05-11 | Piece en materiau composite |
PCT/FR2017/051128 WO2017194886A1 (fr) | 2016-05-11 | 2017-05-11 | Pièce en matériau composite a matrice céramique |
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WO2021075411A1 (ja) * | 2019-10-17 | 2021-04-22 | 株式会社Ihi | セラミックス基複合材料及びその製造方法 |
CN113526972A (zh) * | 2021-07-28 | 2021-10-22 | 中国科学院上海硅酸盐研究所 | 一种抗强烧蚀的稀土改性超高温陶瓷基复合材料及其制备方法 |
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US10988417B2 (en) | 2021-04-27 |
WO2017194886A1 (fr) | 2017-11-16 |
FR3051187A1 (fr) | 2017-11-17 |
US20190152861A1 (en) | 2019-05-23 |
CN109476552A (zh) | 2019-03-15 |
FR3051187B1 (fr) | 2018-06-01 |
JP6987785B2 (ja) | 2022-01-05 |
EP3455192A1 (fr) | 2019-03-20 |
JP2019522608A (ja) | 2019-08-15 |
EP3455192B1 (fr) | 2023-05-10 |
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