CN105263887A - 用于包含硅的耐火衬底的环境屏障 - Google Patents
用于包含硅的耐火衬底的环境屏障 Download PDFInfo
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Abstract
通过一种环境屏障(20)保护一种包括衬底(10)的部件,邻近该衬底的表面的至少一部分衬底由一种包含硅的耐火材料制成,该环境屏障在所述衬底的表面上形成并且具有包含稀土硅酸盐的至少一个自愈层(22)。至少90mol%的该自愈层(22)由一种包括30mol%到最多80mol%的至少一种稀土硅酸盐RE2Si2O7(RE是稀土)以及至少20mol%到70mol%的氧化锰(MnO)的体系形成;以及最多10mol%的该自愈层(22)由除MnO之外的一种或多种氧化物形成,所述一种或多种氧化物与SiO2的共晶点小于或等于1595℃,该自愈层(22)在至少从1200℃到1400℃的整个温度范围中呈现具有自愈功能的液相,同时保存主要固相。
Description
背景技术
本发明涉及提供一种包括衬底的部件,在所述衬底中与表面相邻的至少一部分由一种包含硅的耐火材料制成,在所述部件在高温下在氧化介质中使用时具有保护,通过在所述衬底的表面上形成一个环境屏障获得所述保护。
本发明特别地涉及由耐火复合材料制成的保护部件,耐火复合材料为诸如包含硅的陶瓷基复合(CMC)材料,特别地一种具有由陶瓷纤维制成的纤维增强物的CMC,如碳化硅(SiC)纤维或基于碳化硅的纤维,以及一种至少局部地由碳化硅制成的基质。
本发明应用的特定领域是保护形成燃气轮机的热部的CMC部件,诸如用于航空发动机以及用于工业涡轮机的燃烧室壁,或涡轮环,或涡轮喷嘴,或涡轮叶片。
文献WO2010/072978描述了形成一种具有基于氧化物体系的至少一个自愈层的环境屏障,该氧化物体系由至少一种稀土氧化物、二氧化硅和氧化铝形成。选择该自愈层的成分以使之在达到至少约1400℃时保存主要固相,同时在等于或高于约1400℃的温度下呈现至少一个液相,足够数量下的该液相在这种温度下实施自愈功能。
然而,需要保护在维护中暴露到位于低于1400℃的温度范围内的温度的CMC部件。当该CMC材料的纤维增强物由SiC纤维或基于SiC的纤维制成时,这特别地适用,该基于SiC的纤维具有在1400℃变得明显退化的属性,但其成本比无损害地能够承受1400℃或以上的温度的碳化硅纤维明显更少。
发明目的和内容
在第一方面,本发明提供了一种包括衬底和环境屏障的部件,在所述衬底中与所述衬底的表面相邻的至少一部分由一种包含硅的耐火材料制成,所述环境屏障在所述衬底的表面上形成并且具有包含稀土硅酸盐的至少一个自愈层,在所述部件中,所述自愈层的:
·至少90的摩尔百分数(mol%)由一种体系形成,该体系由30mol%到最多80mol%的至少一种稀土硅酸盐RE2Si2O7以及至少20mol%到70mol%的氧化锰(MnO)构成,RE是稀土;以及
·最多10mol%由除MnO之外的一种或多种氧化物形成,该一种或多种氧化物与SiO2的共晶点小于或等于1595℃;
所述自愈层至少在1200℃到1400℃的温度范围中呈现具有自愈功能的液相,同时保存主要固相。
在本文中使用术语“具有自愈功能的液相”是指存在的液相数量足以有效封闭可能出现在所述环境屏障中的裂缝,即在所述成分中,所述自愈层至少5mol%但不超过40mol%,从而保存良好的抗吹走性能。
所述稀土可从钇、钪和镧系元素(例如镱和铒)中选择。
所述环境屏障也可包括一种插入在所述衬底的表面和所述自愈层之间的衬层,并且从以下选择:
·基本上由至少一种稀土硅酸盐RE2Si2O7构成的衬层;
·基本上由沉积在硅涂层上的至少一种稀土硅酸盐RE2Si2O7构成的衬层,所述硅涂层形成在所述衬底上;
·基本上由莫来石构成的衬层;
·基本上由沉积在硅涂层上的莫来石构成的衬层,所述硅涂层形成在所述衬底上;以及
·基本上具有硅-莫来石成分梯度的衬层,所述成分梯度从所述衬底旁边的硅开始并以所述自愈层旁边的莫来石结束。
在一个实施方式中,所述自愈层插入在所述衬底和一个如由耐火材料或耐磨材料制成的外层之间。
在第二方面,本发明提供了一种提供衬底的方法,在所述衬底中与表面相邻的至少一部分由一种包含硅的耐火材料制成,通过在如上所限定的衬底的表面上形成环境屏障,当所述衬底在高温下在氧化介质中使用时具有保护。
附图说明
在阅读通过非限制性表示给出的以下描述后,可以更好地理解本发明。参考附图,其中:
·图1是由包含硅的复合材料制成的部件的非常图解的视图,该部件提供有本发明的一个实施方式中的环境屏障;以及
·图2至17是通过扫描电子显微镜获得的照片,示出了根据本发明以及不根据本发明的环境屏障的表面状态。
具体实施方式
在以下的详细描述中,环境屏障在一种包含硅的CMC材料的衬底上形成。然而应该记住的是,本发明适用于由包含硅的单片耐火材料制成的衬底,以及更通常地适用于与表面相邻的至少一部分由包含硅的耐火材料(该材料为复合或单片的)制成的衬底。
图1是一种在本发明的一个实施方式中具有环境屏障20的衬底10的高度图解视图。
衬底10由一种包含硅的CMC材料制成并且包括可由碳(C)纤维或陶瓷纤维制成的纤维增强物,所述碳(C)纤维或陶瓷纤维为例如SiC纤维或基本由SiC制成的纤维,包括Si-C-O或Si-C-O-N纤维,即还包含氧以及可能地氮。这种纤维由日本供应商NipponCarbon以“Nicalon”或“HiNicalon”或“Hi-NicalonTypeS”商品名生产,或由日本供应商UbeIndustries以“Tyranno-ZMI”商品名生产。陶瓷纤维可被涂敷有热解碳(PyC)、氮化硼(BN)或硼掺杂碳(BC,具有5到20个原子百分比(at%)的B,余量为C)的薄的相间层。
该纤维增强物由一种基质强化,该基质全部或至少在外基质相中由一种包含硅的材料构成,诸如硅化合物,如SiC,或例如三元Si-B-C体系。使用术语“外基质相”是指最后形成的基质相,所述相距离该纤维增强物最远。在这种情况下,该基质可由不同种类的多个层组成,例如:
混合的C-SiC基质(该SiC在外侧上);
一种具有SiC和低刚度的基质相的交替相的顺序基质,如热解碳(PyC)、氮化硼(BN)或硼掺杂碳(BC)的,该基质的终端相由SiC制成;或
一种自愈基质,具有由碳化硼(B4C)制成的或由Si-B-C三元系统制成的基质相,可能具有自由碳(B4C+C,Si-B-C+C),以及具有Si-B-C或SiC的终端相。
特别地是在以下文件中描述了这种CMC材料:US5246736、US5965266、US6291058以及US6068930,该基质相通过化学气相渗透(CVI)形成。
该基质也可至少局部地通过引入粉末形成,特别地引入碳粉末以及可能还有陶瓷的粉末,并且也可通过用基于熔融状态的硅的金属成分渗透,从而形成SiC-Si类型的基质。这种过程是已知的并且通常称为熔体渗透(MI)。
环境屏障20在该衬底10的整个外表面上或仅在该表面的一部分(例如当该表面的仅一部分需要保护时)上形成。该环境屏障20包括自愈层22。内层或衬层24可插入在衬底10和自愈层22之间。外层26可在自愈层上形成。
该自愈层22基本上为一种以下体系的形式,即在该示例中为至少90mol%含量的该体系,该体系由30mol%到80mol%以上的至少一种硅酸盐RE2Si2O7,以及至少20mol%到70mol%的氧化锰(MnO)构成,其中RE是稀土。该稀土从Y、Sc和镧系元素(例如Yb和Er)中选择。除了这种体系以外,该自愈层可以包括次要的除MnO之外的一种或多种其他氧化物,即在该示例中为不超过10mol%含量的除MnO之外的所述一种或多种其他氧化物,并且所述一种或多种其他氧化物与SiO2的共晶点小于或等于1595℃,例如从氧化铝Al2O3、Ga2O3、In2O3、Nb2O5、ZnO和Ta2O5中选择所述的一种或多种氧化物。添加这些其他的氧化物特别地用于调制自愈温度或热膨胀系数。
然而,忽略不可避免的杂质,该自愈层22优选地由一种RE2Si2O7-MnO体系构成。
从以下示例可以看到的,该层22的成分中明显存在MnO可以形成在最低1200℃到至高1400℃的整个温度范围中具有自愈功能的液相,同时保存主要固相。这并不排除在低于1200℃(如从1150℃)的温度下以及在高于1400℃的温度下具有自愈功能的液相的存在。
可选衬层24可基本上由至少一种稀土硅酸盐RE2Si2O7形成以及可沉积在硅涂层上,该硅涂层形成在衬底上,该稀土例如从Y、Sc和镧系元素(诸如例如Yb、Dy、Er和La)中选择。该衬层24中的稀土可相同于或不同于自愈层22的稀土。
衬层24也可基本上由沉积在衬底10上的莫来石直接形成,或由沉积在衬底10上的莫来石与在衬底上形成的插入硅涂层一起形成,从而增强该莫来石的粘着性。也可以通过基本上为硅-莫来石成分梯度的涂层形成该衬层,该成分梯度从在该衬底旁边的硅开始并以在该自愈层22旁边的莫来石终止。
衬层24可以包括其他次要组分,如用于调制热膨胀系数的一种或多种氧化物。这些其他组分最多为30mol%,并且优选衬层24的组分的最多10%。对于该衬层24重要的是,在使用条件下保持化学和热稳定,以及重要的是其与衬底以及与硅化学地和热机械地兼容。换句话说,需要该衬层24在该自愈层22的所寻求自愈温度下保持固态和避免在衬底10和自愈层22之间的任何直接接触,以及需要其避免与衬底以及包含在该自愈层22中的硅一起形成任何液相,或来自衬底10的硅的氧化。也需要该衬层24的热膨胀系数与衬底10和自愈层22的热膨胀系数相对接近。
衬层24可选择地包括与在自愈层的成分中所包括的相同的稀土硅酸盐RE2Si2O7。
可选的外层26可由耐火材料制成,例如对于需要表面处理的CMC部件,诸如需要呈现光滑表面状态的涡轮叶片。该外层然后可由莫来石、硅酸盐(如硅酸铝)或当然耐火氧化物形成。表面光滑状态可通过加工或通过抛光获得。在一变型中,在这种应用中,自愈层22可构成该环境屏障的外层,然后在自愈层22上进行任何表面加工或抛光。
可选的外层26也可由耐磨材料制成,例如对于形成涡轮环的CMC部件。这种耐磨材料可由多孔陶瓷以已知方式构成,从而能够在移动叶片末端的刮片无损害的渗透到该耐磨材料内,从而减少在叶片末端和涡轮环之间的间隙。
衬层24可使用RE2O3和SiO2的固体粉末和/或RE2Si2O7化合物粉末通过等离子喷涂在衬底10上形成,并且可能包括其他次要组分的粉末。
以类似方式,自愈层22可在衬层24上通过等离子喷涂由RE2O3、SiO2或RE2Si2O7的固体粉末与MnO以及可能地如前所述的其他次要氧化物的粉末一起形成,喷涂粉末各自的量根据所需最终成分选择。
外层26也可在衬底10上通过等离子喷涂由陶瓷粉末形成。
可以设想其他方法用于形成衬层24、自愈层22和外层26,如以溶胶-凝胶形式提供粒子,以泥釉形式施加粉末、通过电泳、物理气相沉积(PVD)或当然化学气相沉积(CVD)沉积。还可以使用先前沉积粉末的快速烧结或放电等离子烧结(SPS)方法。
任何衬层24的厚度被选择为相对较薄,如位于10微米(μm)到300μm的范围中。自愈层22的厚度也可选择为相对较薄,如位于10μm到300μm的范围中。任何外层26的厚度应当根据需求选择并且可位于500μm到1500μm的范围中。这些层的厚度也可取决于沉积方法的能力,所述沉积方法用于形成基本均匀厚度的均匀薄层。因此,例如,对于小厚度,可优选地使用PVD和CVD沉积方法。
自愈层的存在可具有一种在自愈温度下有效、密封和长期的环境屏障。在返回到低于自愈温度的温度的情况下,该液相结晶并且通过以并列颗粒形式的涂层继续确保密封。一旦出现裂缝,提高温度到自愈温度能够封闭该裂缝。
示例1
为了评估在不同温度下各种成分的自愈潜能,制备小丸,每个形成硅酸钇Y2Si2O7的衬层,该硅酸钇Y2Si2O7的衬层由Y2Si2O7和MnO粉末的混合物形成的层覆盖。这两个层通过快速烧结粉末形成,并且它们具有大致1毫米(mm)的厚度。该小丸然后在空气中加热处理50个小时,然后在用扫描电子显微镜(SEM)观察之前被空气淬火。
对于1200℃的热处理温度,应该观察到的是,液相以所需数量形成用于提供自愈功能,在Y2Si2O7-MnO混合物中提供MnO的摩尔百分比为至少20%,该比例优选位于20mol%到70mol%的范围中,从而在被稳定在表面上时获得在1200℃到1400℃的液相涂层,即存在足够的固相以提供良好的抗吹走性能。
对于在该Y2Si2O7-MnO体系中位于30%到50%范围中的MnO的摩尔含量,从1150℃开始,液相出现。
图2-17是Y2Si2O7-MnO混合物的各种成分以及在如下表所列出的各种热处理温度的SEM照片,其提到了是否存在适用于实施自愈功能的液相(S-H相):
在图5至17中,可以看到在晶界存在液相,如图9通过示例示出。在图15中,该液相是过多的,即可能导致该材料溶解在液相中,从而导致由于吹走减少该材料。
示例2
方法与示例1相同,除MnO由氧化镓Ga2O3取代外,Ga2O3在Y2Si2O7-Ga2O3混合物中的摩尔含量等于5%、10%、25%以及53%,并且热处理温度为1300℃、1350℃和1400℃。没有观察到能够实施自愈功能的液相的存在。
示例3
方法与示例1相同,除了MnO由氧化铌Nb2O5取代外,Nb2O5在Y2Si2O7-Nb2O5混合物中的摩尔含量等于5%、10%、25%以及48%、60%和85%,并且热处理温度为1300℃、1350℃和1400℃。没有观察到能够实施自愈功能的液相的存在。
示例4
方法与示例1相同,除了MnO由氧化锌ZnO取代外,ZnO在Y2Si2O7-ZnO混合物的摩尔含量等于5%、10%、15%、50%、60%和85%,并且热处理温度为1200℃、1300℃、1350℃和1400℃。没有观察到能够实施自愈功能的液相的存在。
示例2-4示出了当用氧化物Ga2O3、Nb2O5或ZnO替代MnO与Y2Si2O7混合时无法获得上述种类的自愈层,所述氧化物同样具有降低熔点的能力。
Claims (10)
1.一种包括衬底和环境屏障的部件,在所述衬底中与所述衬底的表面相邻的至少一部分由一种包含硅的耐火材料制成,所述环境屏障在所述衬底的表面上形成并且具有包含稀土硅酸盐的至少一个自愈层,所述部件的特征在于,所述自愈层的:
·至少90mol%由一种体系形成,该体系由30mol%到最多80mol%的至少一种稀土硅酸盐RE2Si2O7以及至少20mol%到70mol%的氧化锰MnO构成,RE是稀土;以及
·最多10mol%由除MnO之外的一种或多种氧化物形成,该除MnO之外的一种或多种氧化物与SiO2的共晶点小于或等于1595℃;
所述自愈层至少在1200℃到1400℃的整个温度范围中呈现具有自愈功能的液相,同时保存主要固相。
2.根据权利要求1所述的部件,其特征在于,RE从钇、钪和镧系元素中选择,镧系元素特别地为镱和铒。
3.根据权利要求1或2所述的部件,其特征在于,所述环境屏障进一步包括一种插入在所述衬底的表面和所述自愈层之间的衬层,该衬层选自:
·一种基本上由至少一个稀土硅酸盐RE2Si2O7构成的衬层;
·一种由沉积在硅涂层上的至少一种稀土硅酸盐RE2Si2O7构成的衬层,所述硅涂层在所述衬底上形成;
·一种基本上由莫来石构成的衬层;
·一种基本上由沉积在硅涂层上的莫来石构成的衬层,所述硅涂层在所述衬底上形成;以及
·一种基本上具有硅-莫来石成分梯度的衬层,所述成分梯度从所述衬底旁边的硅开始并以所述自愈层旁边的莫来石结束。
4.根据权利要求1到3任一所述的部件,其特征在于,所述自愈层插入在所述衬底和耐火材料的外层之间。
5.根据权利要求1到3任一所述的部件,其特征在于,所述自愈层插入在所述衬底和耐磨材料的外层之间。
6.一种提供衬底的方法,在所述衬底中与表面相邻的至少一部分由一种包含硅的耐火材料制成,通过在所述衬底的表面上形成环境屏障,当所述衬底在高温下在氧化介质中使用时具有保护,所述屏障具有包含稀土硅酸盐的至少一个自愈层,并且所述方法的特征在于,所述自愈层的:
·至少90mol%由一种体系形成,该体系由30mol%到最多80mol%的至少一种稀土硅酸盐RE2Si2O7以及至少20mol%到70mol%的氧化锰MnO构成,RE是稀土;以及
·最多10mol%由除MnO之外的一种或多种氧化物形成,该除MnO之外的一种或多种氧化物与SiO2的共晶点小于或等于1595℃;
从而获得一个自愈层,所述自愈层至少在1200℃到1400℃的整个温度范围中呈现具有自愈功能的液相,同时保存主要固相。
7.根据权利要求6所述的方法,其特征在于,稀土从钇、钪和镧系元素中选择,所述镧系元素特别地为镱和铒。
8.根据权利要求6或7所述的方法,其特征在于,形成一种还具有一个插入在所述衬底的表面和所述自愈层之间的子层的环境屏障,所述子层选自:
·一种基本上由至少一种稀土硅酸盐RE2Si2O7构成的衬层;
·一种由沉积在硅涂层上的至少一种稀土硅酸盐RE2Si2O7构成的衬层,所述硅涂层在所述衬底上形成;
·一种基本上由莫来石构成的衬层;
·一种基本上由沉积在硅涂层的莫来石构成的衬层,所述硅涂层在所述衬底上形成;以及
·一种基本上具有硅-莫来石成分梯度的衬层,所述成分梯度从所述衬底旁边的硅开始并以所述自愈层旁边的莫来石结束。
9.根据权利要求6到8任一所述的方法,其特征在于,在所述自愈层上形成耐火材料的外层。
10.根据权利要求6到8任一所述的方法,其特征在于,在所述自愈层上形成耐磨材料的外层。
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- 2014-06-11 RU RU2016100239A patent/RU2656638C2/ru active
- 2014-06-11 CA CA2913974A patent/CA2913974C/fr active Active
- 2014-06-11 US US14/897,471 patent/US9926238B2/en active Active
- 2014-06-11 EP EP14734879.1A patent/EP3008033B1/fr active Active
- 2014-06-11 JP JP2016518567A patent/JP6362683B2/ja active Active
- 2014-06-11 CN CN201480032400.9A patent/CN105263887B/zh active Active
- 2014-06-11 WO PCT/FR2014/051405 patent/WO2014199075A1/fr active Application Filing
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CN110284097A (zh) * | 2019-08-13 | 2019-09-27 | 广东省新材料研究所 | 环境障涂层及其涂覆方法与应用 |
CN110284097B (zh) * | 2019-08-13 | 2021-04-09 | 广东省新材料研究所 | 环境障涂层及其涂覆方法与应用 |
Also Published As
Publication number | Publication date |
---|---|
EP3008033B1 (fr) | 2017-03-01 |
EP3008033A1 (fr) | 2016-04-20 |
WO2014199075A1 (fr) | 2014-12-18 |
CA2913974C (fr) | 2021-03-30 |
FR3007028A1 (fr) | 2014-12-19 |
BR112015031469A2 (pt) | 2017-07-25 |
RU2016100239A (ru) | 2017-07-18 |
FR3007028B1 (fr) | 2015-07-03 |
US20160130188A1 (en) | 2016-05-12 |
CA2913974A1 (fr) | 2014-12-18 |
JP6362683B2 (ja) | 2018-07-25 |
RU2656638C2 (ru) | 2018-06-06 |
US9926238B2 (en) | 2018-03-27 |
RU2016100239A3 (zh) | 2018-04-02 |
CN105263887B (zh) | 2018-06-22 |
JP2016528135A (ja) | 2016-09-15 |
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