CN104010992A - 制造陶瓷基质复合材料的方法和由此形成的陶瓷基质复合材料 - Google Patents

制造陶瓷基质复合材料的方法和由此形成的陶瓷基质复合材料 Download PDF

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CN104010992A
CN104010992A CN201280064845.6A CN201280064845A CN104010992A CN 104010992 A CN104010992 A CN 104010992A CN 201280064845 A CN201280064845 A CN 201280064845A CN 104010992 A CN104010992 A CN 104010992A
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silicon
cmc
goods
preformed member
slurry
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G.H.科比
J.D.斯泰贝尔
N.D.戈斯
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General Electric Co
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General Electric Co
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Abstract

本发明涉及制造含硅CMC制品的方法。所述方法需要在碳化硅(SiC)纤维上沉积一个或多个涂层，牵拉所述涂布的SiC纤维穿过浆料以产生涂有浆料的纤维材料，且随后加工所述涂有浆料的SiC纤维材料以形成单向预浸渍带。将所述带堆叠且随后烧制以产生多孔预成型件。随后所述多孔预成型件通过浸渗其中的孔隙而进一步致密化，从而产生CMC制品。浸渗可通过一系列聚合物浸渗和热解(PIP)步骤、通过在用碳或一种或多种难熔金属填充在所述预成型件中的孔隙之后而熔体浸渗(MI)、通过化学气相浸渗(CVI)或通过这些浸渗技术的组合来实现。

Description

制造陶瓷基质复合材料的方法和由此形成的陶瓷基质复合材料
相关申请的交叉引用
本申请要求2011年12月29日提交的美国临时申请第61/581,129号的权益，其内容通过引用结合到本文中来。
关于联邦资助的研究的声明
本发明是在由Navy颁发的合同N00421-08-C-0041号下在政府支持下完成。该政府对本发明具有一定的权利。
发明背景
概括地讲，本发明涉及陶瓷基质复合(ceramic matrix composite, CMC)制品及其制造方法。更具体地讲，本发明涉及制造含硅CMC制品的方法，其包括能够产生在高温下表现示出合乎需要的物理、机械和微结构性质的CMC制品的加工步骤。
为了增加燃气涡轮发动机的效率，不断地探索用于燃气涡轮发动机的较高操作温度。虽然已经通过铁、镍和钴基超合金的配制实现了在高温性能方面的重大进步，但还是研究了供选的材料。CMC材料由于它们的高温性能可显著降低冷却空气需求是值得注意的实例。CMC材料通常包含包埋在陶瓷基质材料中的陶瓷纤维增强材料。该增强材料可为分散在基质材料中的不连续的短纤维或在基质材料内定向的连续纤维或纤维束，且充当CMC的载荷成分。继而，该陶瓷基质保护该增强材料、维持其纤维的定向且用来消散对该增强材料的荷载。单根纤维(长丝)常常用诸如氮化硼(BN)的脱模剂涂布，以形成允许在纤维和陶瓷基质材料之间的受限且受控的滑动的脱粘层。
连续纤维增强陶瓷复合材料(continuous fiber reinforced ceramic composite, CFCC)是一种针对多种高温载荷应用提供轻质、高强度和高硬度的CMC，这些高温载荷应用包括燃气涡轮发动机的遮板、燃烧室衬套、静叶、动叶及其他高温部件。CFCC材料通常以连续纤维(长丝)为特征，这些连续纤维可配置形成单向纤维阵列，或集束成配置形成单向纤维束阵列的纤维束，或集束成织造形成二维织物或者织造或编织形成三维织物的纤维束。对于三维织物，单向纤维束组可例如彼此垂直交织。对于高温应用特别重要的是作为基质和/或增强材料的基于硅的复合材料，诸如碳化硅(SiC)。SiC纤维还用作用于包括碳化钛(TiC)、氮化硅(Si3N4)和氧化铝(Al2O3)的多种其他陶瓷基质材料的增强材料。
CMC材料且特别是SiC/Si-SiC (纤维/基质)连续纤维增强陶瓷复合(CFCC)材料的实例和方法公开在美国专利5,015,540号、5,330,854号、5,336,350号、5,628,938号、6,024,898号、6,258,737号、6,403,158号和6,503,441号及美国专利申请公告2004/0067316号中，其内容通过引用结合到本文中来。所述方法通常需要使用多个预浸渍层制造CMCs，其各自以包含所要陶瓷纤维增强材料、CMC基质材料的一种或多种前体和有机树脂粘合剂的“带”的形式。根据常规实践，预浸渍带可通过用含有一种或多种陶瓷前体和粘合剂的浆料浸渍增强材料来形成。用于该前体的优选材料将取决于CMC部件的陶瓷基质所希望的特定组成，例如SiC粉末和/或一种或多种最终在与熔融Si反应时将转化成SiC的含碳材料。其他典型浆料成分包括促进预浸渍带的柔韧性的有机粘合剂和促进浆料的流动性以能够浸渍纤维增强材料的用于所述粘合剂的溶剂。
在让浆料部分地干燥且如果合适，则部分地固化粘合剂(B-阶段)之后，将所得预浸渍带与其他带一起铺叠，且随后压实，且如果合适的话，则固化，同时使其经受高压和高温以制造预成型件。随后将该预成型件在真空或惰性气氛中加热(烧制)以分解粘合剂，除去溶剂，并将前体转化成所要陶瓷基质材料。由于粘合剂的分解，生成多孔CMC体，该多孔CMC体可经历熔体浸渗(MI)以填充孔隙并产生CMC部件。用于产生SiC基质的熔体浸渗过程通常需要用外部供应的熔融硅浸渗多孔CMC体。该熔融硅浸渗到孔隙中，与基质的碳内含物反应以形成碳化硅，并填充孔隙以产生所要的CMC部件。用于上述方法的特定加工技术和参数将取决于材料的特定组成。
CFCC材料10的实例示意性表示在图1中，其包括多个薄层(laminae)12，各薄层源于包括用陶瓷基质前体浸渍的单向对准的增强材料14的各个预浸渍带。结果，各薄层12含有嵌入在烧制和熔体浸渗期间通过转化陶瓷基质前体完全或部分地形成的陶瓷基质18中的增强材料14。
以上文论述的方式生产以在碳化硅基质中含有碳化硅纤维的CMCs和CFCCs制品含有元素硅和/或硅合金，因此不能在超过该基质中的硅熔点(约1405℃)或任何低熔点硅合金的熔点(例如，约1360℃)的温度下使用，因为熔融硅可与纤维/纤维束上的诸如氮化硼的脱模剂反应，导致复合材料脆化。此外，熔融硅趋于从复合制品的表面渗出，在此其可与保护制品的环境阻挡涂层(environmental barrier coating, EBC)和接触或非常接近制品的可能的任何金属或其他陶瓷组分反应并损坏。
消除或至少降低CMC制品中元素硅或低熔点硅合金的含量的一些方法公开在Kebbede等的美国公开专利申请2010/0279845号中，其内容通过引用结合到本文中来。根据Kebbede等，从CMC制品中除去游离硅和/或硅合金产生内部空腔，且任何剩余的硅和/或硅合金可通过与反应性气态物质反应转化成难熔的陶瓷材料。空腔的通路可通过用难熔固体至少部分地填充空腔和/或堵塞到空腔的表面进入路径来阻塞。虽然并不意欲提出任何特定的解释，但是看来Kebbede等描述熔体浸渗CMC体，该CMC体已自其除去了低熔点硅或硅合金，使得它们不能与纤维或脱模剂反应，且提供防止由于因缺乏硅或硅合金而产生的孔隙引起的材料内部氧化的方法。然而，认为用以分配应力到纤维束内的许多单根纤维的硅或硅合金的缺乏还引起机械特性显著负债。机械特性的该负债可妨碍CMC满足涡轮发动机部件甚至在低温下所必需的设计要求。
鉴于上述，应当了解，持续需要在高温下且特别是在超过硅熔点的温度下表现出合适的物理、机械和微结构性质的CMC制品。
发明简述
本发明提供了制造含硅CMC制品的方法，其包括使得所述CMC制品能够在高温下且特别是在超过硅熔点的温度下表现出合适的物理、机械和微结构性质的加工步骤。
根据本发明的第一方面，提供了制造含硅CMC制品的方法。所述方法需要在碳化硅(SiC)纤维上沉积一个或多个涂层，牵拉所述涂布的SiC纤维穿过浆料以产生涂有浆料的纤维材料，且随后加工所述涂有浆料的SiC纤维材料以形成单向预浸渍带。将所述带堆叠且随后烧制以产生多孔预成型件。随后所述多孔预成型件通过浸渗其中的孔隙而进一步致密化，从而产生CMC制品。
根据本发明的第二方面，CMC制品包含用涂布的碳化硅纤维增强的陶瓷基质。所述基质包含至少90体积%的基于硅的难熔化合物、至多5体积%的孔隙和至多5体积%的选自元素硅、硅合金、基于硅的化合物及其组合的一种或多种低熔点相。
本发明的技术效果在于能够生产基于SiC的CMC和CFCC制品，所述基于SiC的CMC和CFCC制品能够在超过元素硅和硅合金的熔点的温度下使用。虽然先前方法已经设法从CMC制品中消除元素硅和低熔点硅合金以产生完全由难熔的基于硅的材料形成的基质相，但该方法使得所产生的基质含有孔隙，且因此不是完全致密的。相比之下，本发明涉及制造不仅基本上不含元素硅和低熔点硅合金而且含有基本不含孔隙、例如含有小于5体积%孔隙的致密基质的CMC制品。
从以下发明详述中可以更好地理解本发明的其他方面和优势。
附图简述
图1示意性表示CFCC制品的不完整的横截面图。
图2为通过在本发明的范围内的方法制造的CFCC制品的扫描图像。
发明详述
将根据用于制造包括CFCC制品的CMC制品的方法描述本发明，所述CMC制品可在超过低熔点硅合金的熔点(例如，约1357℃)的温度下且优选高至至少1480℃且因此大大超过硅及其低熔点合金的熔点的温度下使用。本发明特别感兴趣的CMC材料是含有硅的那些材料，诸如含有碳化硅作为增强和/或基质材料的CMC，其特定实例为在碳化硅基质中的连续碳化硅纤维。然而，其他含硅材料也在本发明的范围内，包括陶瓷，诸如氮化硅；和硅化物(金属间化合物)，诸如硅化铌和硅化钼。虽然可以预见各种应用，但是部件10的特定应用包括燃气涡轮发动机的部件，诸如在燃气涡轮机的涡轮段内的燃烧室衬套、静叶、动叶和遮板。
本发明的CMC制品的以下论述将参考图1，其如先前所提到表示包括多个薄层12的CFCC部件10，各薄层源于最初包括用陶瓷基质前体浸渍的单向对准的纤维束14的各个预浸渍体。作为压实、固化并烧制通过堆叠的预浸渍体形成的薄层预成型件的结果，各薄层12含有包埋在包含碳化硅相的基质18中的单向对准的纤维16，该碳化硅相可通过在烧制和熔体浸渗期间部分转化陶瓷基质前体而形成。然而，作为本发明的一个特定方面，在包括如下所述的另外加工步骤的情况下，基质18优选不含如先前归因于通过硅熔体浸渗过程生产的CMCs的元素硅或硅合金相。事实上，基质18优选完全由一种或多种陶瓷材料形成。
作为CFCC部件10，纤维束14优选在各薄层12中单向，即彼此并排且平行定向。合适的纤维直径、纤维束直径和中心间纤维束间隔将取决于特定的应用、薄层12的厚度及其他因素，且因此在图1中没有按标度表示。根据已知实践，纤维束14的单根纤维16优选用一种或多种脱模剂涂布以形成允许在基质18和纤维束14及它们的单根纤维16之间受限且受控滑动的脱粘纤维涂层(未示出)。用于纤维涂层的合适材料包括氮化硼(BN)、硅掺杂的BN、氮化硅(Si3N4)、碳化硅(SiC)、碳化铪(HfC)、氮化铪(HfN)、碳化锆(ZrC)、氮化锆(ZrN)、碳化钽(TaC)、氮化钽(TaN)及其混合物。优选的纤维涂层包括这些化合物中的一种或多种的多层。随着裂缝在部件10中发展，桥接裂缝的纤维16用以将荷载再分布到基质18的邻近纤维16和区域，由此抑制或至少减慢裂缝的进一步蔓延。
如先前所提，在制造部件10期间，所要数目的预浸渍带铺叠成型以形成预成型件，该预成型件经历进一步加工以产生部件10。形成各个带以含有包埋到用于基质18的所要材料如SiC的前体内的增强结构(由纤维16形成)。本领域普通技术人员应了解本发明的一个重要方面在于使用单向纤维预浸渍带以积聚复合结构。源于单向预浸渍体的CMC结构在高于硅的熔点的高温下提供改善的机械性质。认为，因为各纤维经由难熔基质相而很好地隔离，所以机械荷载可更有效地转移到各单根纤维，这继而促进改善的机械性质。根据常规实践，这类预浸渍带可在一次操作中形成，例如通过在将纤维束16的连续丝束卷绕到辊筒上期间施用含前体的浆料来形成。在该卷绕操作之后，使浆料部分地干燥且将所得预浸渍带从辊筒上移开，与其他带一起铺叠成型，且随后压实并固化(如果合适的话)，同时经受高压和高温以形成固化的预成型件。随后将该预成型件在真空中或在惰性气氛中加热以分解有机粘合剂并产生多孔的刚性预成型件。
以下加工技术是用来通过减少或完全消除在CMC制品内的孔隙以及通过减少或完全消除在CMC制品中的任何残留元素硅和/或低熔点硅合金来大大改善通过上述类型的加工步骤制造的CMC制品的温度性能。
根据本发明的一个优选方面，降低孔隙含量可经由包括一个或多个浸渗步骤的致密化方法来完成。例如，可使用一系列聚合物浸渗和热解(polymer infiltration and pyrolysis, PIP)步骤来填充孔隙且同时消除具有任何残留硅或低熔点硅合金的可能性。这种PIP方法利用聚合前体，该聚合前体在热解(优选在惰性气氛中，例如在真空或氩气中)时单独地形成所要的陶瓷。合乎需要的陶瓷的实例包括碳化硅、氮化硅、氧碳化硅、氧氮化硅、碳氮化硅、氧碳氮化硅或其混合物。这些化合物具有比硅及其低熔点合金高的熔点(高于1480℃)。
可使用的另外或供选的浸渗技术包括化学气相浸渗(CVI)和熔体浸渗(MI)。如先前在本领域中所实践，MI方法已经在其中预成型件用浆料形成的情况下使用，该预成型件在烧制时产生优选与熔融硅反应以形成碳化硅的含碳预成型件。在本发明中，碳加入也可通过使多孔预成型件经受碳黑颗粒的直接浸渗或烧掉已经浸渗到孔隙空间中的产碳树脂来实现。在另一方法中，该孔隙空间可用难熔金属或在与熔融硅反应时形成难熔硅化物相的含难熔金属的化合物填充。
上文提到的致密化方法可受益于在浸渗之前使用某些预浸渍浆料，优选所述预浸渍浆料在多孔预成型件中不留下残留元素硅或硅合金，且优选产生碳化硅或碳的连续网络以在多孔预成型件内提供强度。已经将各种含前体的浆料施用到连续纤维和纤维束上以制造预浸渍带。典型的浆料组成除了所要的陶瓷前体之外还含有基质的陶瓷成分(例如，碳化硅)、充当加工助剂的有机树脂(例如，聚乙烯基丁醛和聚甲基丙烯酸异丁酯)、溶剂(例如，甲苯、MIBK、乙苯等)和用于粘合剂的增塑剂(例如，邻苯二甲酸二丁酯)。在本发明中使用的浆料组合物可含有在预成型件在约1430℃-约1460℃的温度下的烧制期间反应的元素硅和碳黑的约1:1化学计量混合物。所述浆料组合物另外可含有可热解以形成碳焦网络的一种或多种有机粘合剂(例如，呋喃型树脂(furanic resin)和/或酚醛树脂)。在任何情况下，结果优选为可基本不含元素硅和硅合金且其中纤维包埋在碳化硅长丝或碳焦(根据如上所述的实施方案的特定情节)的多孔仍然连续的网络中的固化且刚性的预成型件。该孔隙随后可通过上文论述的致密化方法消除，使得碳化硅长丝或碳焦的网络提供用于增强以防止由于在聚合前体的热解中、特别是在第一致密化循环期间设计的应力而开裂的支架。
可进行另外的加工步骤以提取在CMC制品内的任何残留元素硅和/或低熔点硅合金相。如果使用含有相对于元素硅和碳黑的1:1的化学计量混合物所需要过量的元素硅的浆料，或如果使用不含任何元素硅的浆料但使用元素硅或硅合金的外部来源作为浸渗剂进行熔体浸渗步骤，则特别需要提取步骤。对于后者，典型的浆料组合物含有碳化硅、碳黑、充当加工助剂的有机树脂(例如，聚乙烯基丁醛)、热解以形成碳焦网络的有机树脂、溶剂(例如，甲苯、MIBK、醇和丙酮)等)和用于粘合剂的增塑剂(例如，邻苯二甲酸二丁酯)。可将涂布的碳化硅纤维牵引穿过该浆料并卷绕到辊筒上以形成预浸渍带。将这些带以所要定向铺叠成型并在热和压力下凝固以形成薄层。将该薄层在氮气、氩气或真空中加热以烧掉一部分有机溶剂和树脂，同时还将一部分粘合剂和树脂转化成碳焦。该烧过的多孔薄层随后可通过加热硅或硅合金的外部来源使得其熔融并流入薄层中而熔体浸渗。该熔融硅或硅合金的第一部分与在该多孔薄层中的前体碳反应以形成碳化硅，且该熔融硅或硅合金的第二部分填充在该薄层中的孔隙。在冷却时，填充孔隙空间的硅或硅合金凝固。该硅或硅合金为从熔体浸渗的CMC中提取以形成多孔预成型件的所要相。
在使用不含硅的预浸渍浆料且熔体浸渗在使用硅或硅合金的外部来源作为浸渗剂的情况下进行的情况下，除碳化硅和碳黑之外，该浆料还可任选含有难熔金属或化合物。该难熔金属与残留的元素硅和/或低熔点硅合金反应以形成难熔硅化物且用来降低在MI CMC中将需要提取的总残留硅或硅合金含量。合适的难熔金属和化合物包括钼、硅化钼(Mo5Si3)、碳化钼、氮化钼、钽、碳化钽、硅化钽、氮化钽、铌、碳化铌、硅化铌、氮化铌或其组合。任选这些材料可掺入硅或硅合金的外部来源中，使得一旦熔体中的硅含量通过与碳黑反应而充分地贫化，则形成难熔硅化物。该方法将确保难熔硅化物在冷却时沉淀在残留硅内，由此降低将需要提取的低熔点硅或硅合金的体积。
合适的提取技术为包括用多孔材料包围CMC制品并加热直至硅或硅合金熔融的粉末填料提取法。多孔材料可包括但不限于碳黑；石墨；工业金刚石；碳化硅；氮化硅；钼及其硅化物、碳化物和氮化物；钨及其硅化物、碳化物和氮化物；钽及其硅化物、碳化物和氮化物；和/或铌及其硅化物、碳化物和氮化物。优选的多孔材料包括提供化学推动力以提出硅或硅合金、而不与熔体浸渗体中的碳化硅强烈反应且如果存在浅表反应层则通过研磨或喷砂容易地除去以保证留下的孔隙网络对于随后的浸渗开放的那些多孔材料。优选的多孔材料包括钼、钨、钽、铌金属及硅化铌。这些材料能够充分地提取残留硅和硅合金并在CMC制品的表面上形成金属硅化物，这些金属硅化物通过喷砂容易地除去以暴露CMC制品内的孔隙通道。一旦暴露，孔隙通道则可用可通过PIP、MI或CVI技术转化成碳化硅的一种或多种前体填充。
另一合适的提取技术为通过将CMC制品暴露于对残留硅合金具有腐蚀性、但对CMC制品的任何其他成分没有腐蚀性的液体来进行的液相提取方法。所述液体的实例有氢氟酸(HF)；氢氟酸和其他酸的混合物；强碱性溶液，诸如NaOH、LiOH、KOH等水溶液；液态金属，诸如镓、铟、锡和汞；及包括液态金属、酸和碱的多级沥滤法。可将所述液相加热以增加它们溶解残留硅合金的速率。这特别符合于液态金属，其需要高温来激活硅合金去除过程。可进行热处理以除去任何污染物，例如以蒸发在孔隙通道中的氟或任何金属。照样，暴露的孔隙通道可用可通过PIP、MI或CVI技术转化成碳化硅的一种或多种前体填充。
另一合适的提取技术为在高温下在强真空下蒸发硅或硅合金。照样，暴露的孔隙通道可用可通过PIP、MI或CVI技术转化成碳化硅的一种或多种前体填充。
一旦完成了CMC制品的致密化，则所得CMC制品优选包含至少90体积%的基于硅的难熔化合物，所述难熔化合物可包括一种或多种诸如碳、氮、氧、钼、钽、铌及其混合物的元素的硅化合物。该基质还可含有至多5体积%的孔隙和至多5体积%的低熔点相(在低于1480℃熔融的相)，诸如纯元素硅、低熔点硅合金(例如，硅-硼合金)、低熔点的基于硅的化合物(例如，硅化铁)和/或其组合。更优选所述CMC制品具有含有小于5%的低熔点相和孔隙之和的基质。最优选的CMC制品具有含有小于5体积%孔隙且基本不含低熔点相的基质。
可用本发明获得的致密微结构的实例示于图4中。该微结构基本不含硅和硅合金相，因此该微结构能够在结构上和在化学上耐受高于硅及其低熔点合金的熔点的温度。例如，该微结构适合CMC部件，诸如燃烧室衬套、静叶、动叶和遮板，它们可安装在燃气涡轮发动机中并经受高至大于1480℃且可能更高的温度。
虽然已经关于优选的实施方案描述了本发明，但很明显本领域技术人员可选定其他形式。例如，在上述方法中使用的参数和材料可与所描述的参数和材料不同，且可包括除所提到的那些材料和方法以外的另外的材料和方法。因此，本发明的范围将仅受以下权利要求书限定。

Claims (21)

1. 制造含硅CMC制品的方法，所述方法包括：
在碳化硅纤维上沉积一个或多个涂层；
牵拉所述涂布的碳化硅纤维穿过浆料以产生涂有浆料的纤维材料；
由所述涂有浆料的纤维材料制造单向预浸渍带；
堆叠所述带以形成预成型件；
烧制所述预成型件以产生多孔的烧制预成型件；且随后
通过浸渗其中的孔隙以使所述多孔的烧制预成型件致密化以产生CMC制品。
2. 权利要求1的方法，其中所述浆料的组合物包含在约1430℃-约1460℃的温度下烧制所述预成型件期间反应的元素硅和碳黑的约1:1化学计量混合物。
3. 权利要求1的方法，其中所述浆料的组合物包含在所述烧制步骤期间热解以形成碳焦的网络的一种或多种有机粘合剂。
4. 权利要求1的方法，其中所述浆料的组合物包含一种或多种难熔材料。
5. 权利要求4的方法，其中所述难熔材料组分选自钼、硅化钼(Mo5Si3)、碳化钼、氮化钼、钽、碳化钽、硅化钽、氮化钽、铌、碳化铌、硅化铌、氮化铌及其组合。
6. 权利要求1的方法，其还包含在所述致密化步骤之前提取在所述多孔的烧制预成型件内的残留元素硅和/或低熔点硅合金相。
7. 权利要求6的方法，其中所述残留元素硅和/或低熔点硅合金相使用粉末填料提取法提取。
8. 权利要求7的方法，其中所述粉末填料提取法用选自钼、钨、钽、铌金属和硅化铌的多孔材料进行。
9. 权利要求6的方法，其中所述残留元素硅和/或低熔点硅合金相使用液相提取法提取。
10. 权利要求6的方法，其中所述残留元素硅和/或低熔点硅合金相使用蒸发法提取。
11. 权利要求6的方法，其还包括通过使用一系列聚合物浸渗和热解步骤、用元素硅和/或一种或多种硅合金熔体浸渗、化学气相浸渗或其组合浸渗所述多孔的烧制预成型件来使所述多孔的烧制预成型件致密化。
12. 权利要求1的方法，其还包括在所述致密化步骤之前热处理所述多孔的烧制预成型件以除去在所述多孔的烧制预成型件的孔隙通道中的污染物。
13. 权利要求1的方法，其中所述致密化步骤包括使用一系列聚合物浸渗和热解步骤、用元素硅和/或一种或多种硅合金熔体浸渗、化学气相浸渗或其组合浸渗所述多孔的烧制预成型件。
14. 权利要求13的方法，其中所述致密化步骤包括一系列聚合物浸渗和热解步骤，所述聚合物浸渗和热解步骤包括在热解时形成选自碳化硅、氮化硅、氧碳化硅、氧氮化硅、碳氮化硅、氧碳氮化硅及其组合的陶瓷的聚合前体。
15. 权利要求1的方法，其还包括将所述CMC制品安装在燃气涡轮发动机中并使所述CMC制品经受至少约1480℃的温度。
16. CMC制品，其通过权利要求1的方法形成。
17. CMC制品，其包含用涂布的碳化硅纤维增强的陶瓷基质，所述基质包含至少90体积%的基于硅的难熔化合物；至多5体积%的孔隙；和至多5体积%的选自元素硅、硅合金、基于硅的化合物及其组合的一种或多种低熔点相。
18. 权利要求书17的CMC制品，其中所述基于硅的难熔化合物选自碳、氮、氧、钼、钨、钽、铌及其混合物的硅化合物。
19. 权利要求书17的CMC制品，其中所述基质含有小于5体积%的低熔点相和孔隙之和。
20. 权利要求书17的CMC制品，其中所述基质含有小于5体积%的孔隙且基本不含低熔点相。
21. 权利要求书17的CMC制品，其中所述CMC制品为燃气涡轮发动机的部件。
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CN114746380A (zh) * 2019-09-16 2022-07-12 派特欧赛拉米克斯股份公司 在碳纤维增强陶瓷基体复合材料上制备基于一种或多种硅化合物的钝化涂层的方法和具有这种涂层的碳纤维增强陶瓷基体复合材料
CN114746380B (zh) * 2019-09-16 2024-02-09 派特欧赛拉米克斯股份公司 制备基于硅化合物的钝化涂层的方法和具有这种涂层的复合材料
CN113321532A (zh) * 2020-02-28 2021-08-31 通用电气公司 长丝缠绕的高旦尼尔氧化铝纤维组件及其制备方法

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WO2013103469A2 (en) 2013-07-11
US20130167374A1 (en) 2013-07-04
JP2015508382A (ja) 2015-03-19
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JP6411894B2 (ja) 2018-10-24
WO2013103469A3 (en) 2013-12-19

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