CN106947902B - 燃气涡轮机部件和用于制造这种燃气涡轮机部件的方法 - Google Patents

燃气涡轮机部件和用于制造这种燃气涡轮机部件的方法 Download PDF

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CN106947902B
CN106947902B CN201610994411.6A CN201610994411A CN106947902B CN 106947902 B CN106947902 B CN 106947902B CN 201610994411 A CN201610994411 A CN 201610994411A CN 106947902 B CN106947902 B CN 106947902B
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gas turbine
turbine component
range
max phase
phase
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CN106947902A (zh
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H-P.博斯曼恩
M.巴赖尼哈萨尼
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Ansaldo Energia IP UK Ltd
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Abstract

本发明涉及燃气涡轮机部件和用于制造这种燃气涡轮机部件的方法。所述燃气涡轮机部件，其尤其暴露于燃气涡轮机内的高温和离心力，具有由金属和称为MAX相的三元陶瓷构成的结构，MAX相具有分子式Mn+1AXn，其中n=1、2、或3，M是前过渡金属诸如Ti、V、Cr、Zr、Nb、Mo、Hf、Sc、Ta，并且A是A族元素诸如Al、Si、P、S、Ga、Ge、As、Cd、In、Sn、Tl、Pb，并且X是C和/或N，其中M在40‑60 at‑%范围内，A在10‑30 at‑%范围内并且X在20‑40 at‑%范围内，因此M+A+X在80‑100%范围内，以及0‑20%是上面没有列出且由于杂质或氧化引入的其他元素。

Description

燃气涡轮机部件和用于制造这种燃气涡轮机部件的方法
技术领域
本发明涉及燃气涡轮机的技术。本发明涉及燃气涡轮机部件。
本发明进一步涉及用于制造这种燃气涡轮机部件的方法。
背景技术
如今，高效燃气涡轮机在非常高的热气体温度下操作。用于热燃气涡轮机部件的实际材料是密度为大约8 g/cm3的镍超合金。该相对高的密度在各种转子部件（例如叶片）上产生高的离心力。当燃气涡轮机变得更大时，该问题变得更严重。
另一方面，所谓的MAX相的三元陶瓷是已知的，其能够具有大约4 g/cm3的低密度。
该材料的详情例如公开在M. Radovic和M. W. Barsoum的下述文章中：MAXphases: Bridging the gap between metals and ceramics, American CeramicSociety Bulletin, Vol. 92, Nr. 3, p. 20-27（2013年4月）。
文献US 2010/0055492 A1公开了包括具有分子式Mn+1AXn的MAX相材料和金属成分的合成物，其中，M是前过渡金属，A是A族元素，X是C和N中的一者或两者，并且n=1-3，其中，MAX相材料限定多个孔；并且所述金属成分包括低熔点金属，其中，该金属占据所述孔中的至少一些。还公开了一种方法，其包括：提供多孔坯体，该坯体包括具有分子式Mn+1AXn的颗粒材料，其中，M是前过渡金属，A是A族元素，X是C和N中的一者或两者，并且n=1-3；以及用低熔点金属渗透坯体的至少一些孔，从而提供复合材料。
在过去，已经考虑在燃气涡轮机的技术领域中使用MAX相。
文献US 8,192,850 B2公开了包括燃烧涡轮机构件基底和在燃烧涡轮机构件基底上的粘结涂层的燃烧涡轮机构件。粘结涂层可包括Mn+1AXn（n=1、2、3），其中，M选自元素周期表的IIIB、IVB、VB、VIB和VII族及其混合物，其中，A选自元素周期表的IIIA、IVA、VA和VIA族及其混合物，并且其中，X包括碳和氮中的至少一者。热障涂层可在粘结涂层上。
文献WO 2014/149097 A2公开了包括具有翼型部分和尖端的涡轮发动机构件的涡轮发动机系统，该涡轮发动机构件具有结合到尖端的MAXMET复合材料。MAXMET复合材料具有在金属基体中的MAX相。
文献WO 2014/143266 A1描述了用于燃气涡轮发动机的抗振风扇导叶。风扇导叶包括由MAXMET复合材料制成的振动阻尼构件。阻尼构件可以是覆盖风扇导叶主体的一些或全部的盖子。替代性地，风扇导叶主体的部分或整个叶主体可由MAXMET复合材料制成。该公开利用MAXMET复合材料在循环弹性变形期间展现的超高、完全可逆、非线性弹性滞后行为以便阻尼振动。
文献EP 2 905 271 A1涉及包括嵌入在陶瓷基体中的陶瓷纤维的陶瓷基复合材料CMC。纤维包括由MAX相制成的涂层。MAX相涂层能够直接涂布在纤维的表面上，或例如在额外涂覆层之间。改进了CMC的性质，优选的高温性能。
发明内容
本发明的目的是实现非常大的燃气涡轮机而不改变转子材料。
本发明的另一目的是提供用于燃气涡轮机的新材料的应用和用于制造具有降低的比密度和稳健机械强度的燃气涡轮机的构件的新过程。
这些和其他目的通过根据本发明的燃气涡轮机部件和方法实现。
根据本发明的燃气涡轮机部件（其尤其暴露于燃气涡轮机内的高温和离心力）的特征在于，所述燃气涡轮机部件具有由金属和被称为MAX相的三元陶瓷构成的结构，所述MAX相具有分子式Mn+1AXn，其中，n=1、2、或3，M是前过渡金属，诸如Ti、V、Cr、Zr、Nb、Mo、Hf、Sc、Ta，并且A是A族元素，诸如Al、Si、P、S、Ga、Ge、As、Cd、In、Sn、Tl、Pb，并且X是C和/或N，因此 M在40-60 at-%（原子数百分比）的范围内，A在10-30 at-%的范围内并且X在20-40 at-%的范围内，并且因此M+A+X在80-100%的范围内，以及0-20%是上面没有列出且由于杂质或氧化引入的其他元素。
根据本发明的实施例，所述MAX相是单相Ti2AlC或两相Ti2AlC和Ti3AlC2的合成物，其中，Ti2AlC相的范围是60-95%。
根据本发明的另一实施例，所述MAX相是单相Ti3SiC2或两相Ti3SiC2和Ti4SiC3的合成物，其中，Ti3SiC2相的范围是60-95%。
根据本发明的又另一实施例，所述MAX相是两个主相Ti3SiC2和Ti2AlC的混合物，其中，Ti3SiC2相的范围是40-90%，并且因此两个MAX相在50-100%的范围内，以及0-20%是其他MAX相或元素。
根据本发明的又一实施例，所述金属是Ni或Co基超合金，或者属于合成物MCrAlYX，其中M表示Ni、Co或Fe，并且X表示少于20%的其他元素。
根据本发明的又另一实施例，所述燃气涡轮机部件具有包括一个或多个腔的中空金属结构，所述腔填充有所述MAX相材料。
根据本发明的又一实施例，所述燃气涡轮机部件包括块体MAX相，所述块体MAX相涂覆有所述金属。
用于制造根据本发明的燃气涡轮机部件的本发明方法包括如下步骤：
a）提供适合于在燃气涡轮机环境中使用的金属：
b）提供被称为MAX相的三元陶瓷，其具有分子式Mn+1AXn，其中，n=1、2、或3，M是前过渡金属，诸如Ti、V、Cr、Zr、Nb、Mo、Hf、Sc、Ta，并且A是A族元素，诸如Al、Si、P、S、Ga、Ge、As、Cd、In、Sn、Tl、Pb，并且X是C和/或N，因此 M在40-60 at-%的范围内，A在10-30 at-%的范围内并且X在20-40 at-%的范围内，并且因此M+A+X在80-100%的范围内，以及0-20%是上面没有列出且由于杂质或氧化引入的其他元素；以及
c）通过粉末技术过程和/或喷涂方法将所述金属和所述MAX相结合以构造所述燃气涡轮机部件。
根据本发明方法的实施例，所述金属是Ni或Co基超合金或MCrAlYX，其中M表示Ni、Co或Fe，并且X表示少于20%的其他元素。
根据本发明方法的另一实施例，所述燃气涡轮机部件在步骤c）之后进行热处理或热等静压（HIP）过程。
所述HIP或热处理过程可以在比所述金属和MAX相的熔点更低的温度下完成，以便在高温下致密化和/或应力松弛。
根据本发明方法的又一实施例，在步骤c）中，所述金属的金属中空金属结构填充有所述MAX相。
可对所述金属中空结构进行预氧化以形成薄TGO（热生长氧化物），从而避免氧化和与所述MAX相的相互扩散。
根据本发明方法的又另一实施例，在步骤c）中，使用喷涂过程用所述金属涂覆块体MAX相。
可对所述MAX相进行预氧化以形成薄TGO（热生长氧化物），从而避免氧化和与所述金属的相互扩散。
所述喷涂过程可包括冷等离子喷涂和超音速火焰喷涂（HVOF）中的一者。
根据本发明方法的又一实施例，在步骤c）中，所述金属的金属中空金属结构填充有MAX相和金属粉末的混合物，其中，所述MAX相占50-100 %wt，并且所述金属粉末具有比所述MAX相和金属中空结构更低的熔点。
附图说明
现在借助于不同实施例并参考附图来更详细地解释本发明。
图1示出根据本发明的燃气涡轮机部件的实施例；
图2示出用于制造图1的燃料涡轮机部件的过程的主要步骤；
图3示出用于在MAX相中产生压应力的热处理过程的示例；
图4示出在热屏蔽件的顶部上具有独立部件（翅部）的转子热屏蔽件，该翅部由MAX相制成并被插入到在热屏蔽件的顶部上的凹部中；
图5示出根据本发明的燃气涡轮机部件的又一实施例；以及
图6示出用于制造图5的燃料涡轮机部件的过程的主要步骤。
具体实施方式
本发明关于使用新材料、设计和工艺过程来生产燃气涡轮机部件、尤其是燃气涡轮机的转子热屏蔽件，其中，新材料提供低密度并且因此降低转子上的离心力，并且新设计和工艺过程方法促进部件的制造。
这允许在不改变转子材料的情况下构造非常大的燃气涡轮机。这能够通过应用新材料和工艺过程以制造具有降低的比密度和稳健机械强度的构件来完成。
在这一点上，所谓的MAX相（三元陶瓷）是能够满足该要求的极其令人关注的选择，其密度为大约4-4.5 g/cm3、热膨胀系数＞8x10-6 K-1、700 ℃时的热导率>50 W/mK、断裂韧性>5 MPa.m1/2、以及高抗氧化性。
使用MAX相的所提出的解决方案将解决氧化问题，尤其是在转子热屏蔽件的顶部上的翅部上的氧化问题（参见图4）。
MAX相（其用于通过粉末冶金过程来生产热涡轮机部件）是具有Mn+1AXn分子式的陶瓷族，其中，n=1、2、或3，M是前过渡金属，诸如Ti、V、Cr、Zr、Nb、Mo、Hf、Sc、Ta，并且A是A族元素，诸如Al、Si、P、S、Ga、Ge、As、Cd、In、Sn、Tl、Pb，并且X是C和/或N。M在40-60 at-%的范围内，A在10-30 at-%的范围内并且X在20-40 at-%的范围内。并且M+A+X在80-100%的范围内以及0-20 %的元素，所述元素在上面没有列出且是由于杂质或氧化引入的。
MAX相的一个优选合成物是单相Ti2AlC，或两相Ti2AlC和Ti3AlC2（211和312），其中，211相的范围是60-95%。
MAX相的另一优选合成物是单相Ti3SiC2，或两相Ti3SiC2和Ti4SiC3（312和413），其中，312相的范围是60-95%。
MAX相的另一优选合成物是两个主相Ti3SiC2和Ti2AlC的混合物，其中，Ti3SiC2相的范围是40-90%，并且因此两个MAX相在50-100%的范围内，以及0-20%为其他MAX相或元素。
当燃气涡轮机部件尤其是燃气涡轮机的转子热屏蔽件时，其通过粉末技术过程和/或喷涂方法由MAX相和金属生产，并且金属是Ni或Co基超合金或MCrAlYX，其中，M表示Ni、Co或Fe，并且X表示少于20%的其他元素。
如在图1和图2中所示，例如具有T形横截面的燃气涡轮机部件10a由中空金属结构11制成，其腔12填充有MAX相并将进行热处理和/或热等静压（HIP）过程。用以避免部件开裂的当前方法是使用诸如喷丸加工的方法来引起压应力。
本发明提出一种引起压应力的不同解决方案。其将诸如MAX相和金属的材料与特定热处理方法结合（参见图3）。与所述金属相比，MAX相具有更低的热膨胀系数。如在图3中的示例中所示，通过应用某热处理，在操作温度下在块体中产生压应力。热处理过程将在比操作温度更高的温度下完成，以便在MAX相中产生压应力。MAX相将在热处理温度下无应力，并且在室温到操作温度的范围内处于压应力下。
填充有MAX相的金属中空结构11与块体金属部件相比有助于减轻重量，并且与中空金属部件相比有助于提高强度。
金属中空结构11填充有MAX相和金属粉末的混合物，其中，MAX相占50-100 %wt，并且金属粉末具有比MAX相和金属中空结构11更低的熔点。
HIP或热处理在比金属和MAX相的熔点更低的温度下完成以便在高温下致密化和/或应力松弛。低于HIP或热处理温度的操作温度使MAX相处于压应力下并增大部件的拉伸负载能力。
如在图5和图6中所示，燃气涡轮机部件10b由块体MAX相15制成，该块体MAX相15使用喷涂方法（例如，冷等离子喷涂、HVOF）涂覆有金属（金属涂层16）并且然后对整个部件进行热处理或经受HIP。HIP或热处理在比金属和MAX相的熔点更低的温度下完成以便在高温下致密化和/或应力松弛（在室温下，MAX相由于较低的热膨胀系数而处于压应力下）。操作温度低于HIP或热处理温度；MAX相15保持在压应力下，这进而增大部件10b的拉伸负载能力。通过使用MAX相减小部件10b的重量并且利用外部金属层（金属涂层16）改善了可机加工性。
能够对MAX相15进行预氧化以形成薄TGO（热生长氧化物），从而避免氧化和与所述金属的相互扩散。
能够对金属中空结构11进行预氧化以形成薄TGO（热生长氧化物），从而避免氧化和与MAX相的相互扩散。
此外，根据本发明的另一实施例，如在图4中所示，转子热屏蔽件13的顶部上的单独部件（翅部14）可由这样的MAX相制成，该翅部14可插入到在热屏蔽件13的顶部上的相应凹部中。
参考数字列表
10a、10b 燃气涡轮机部件
11 中空金属结构
12 腔
13 转子热屏蔽件
14 翅部
15 块体MAX相
16 金属涂层。

Claims (11)

1.一种燃气涡轮机部件，其暴露于燃气涡轮机内的高温和离心力，其特征在于，所述燃气涡轮机部件具有由金属和被称为MAX相的三元陶瓷构成的结构，所述MAX相具有分子式Mn+1AXn，其中，n=1、2、或3，M是前过渡金属，并且A是A族元素，并且X是C和/或N，因此M在40-60 at-%的范围内，A在10-30 at-%的范围内并且X在20-40 at-%的范围内，并且因此M+A+X在80-100at-%的范围内，以及0-20at-%是上面没有列出且由于杂质或氧化引入的其他元素;
其中所述燃气涡轮机部件具有包括一个或多个腔的中空金属结构，所述腔填充有所述MAX相材料。
2.如权利要求1所述的燃气涡轮机部件，其特征在于，所述MAX相是单相Ti2AlC或两相Ti2AlC和Ti3AlC2的合成物，其中，所述Ti2AlC相的范围是60-95%。
3.如权利要求1所述的燃气涡轮机部件，其特征在于，所述MAX相是单相Ti3SiC2或两相Ti3SiC2和Ti4SiC3的合成物，其中，所述Ti3SiC2相的范围是60-95%。
4.如权利要求1所述的燃气涡轮机部件，其特征在于，所述MAX相是两个主相Ti3SiC2和Ti2AlC的混合物，其中，所述Ti3SiC2相的范围是40-90%，并且因此两个MAX相在50-100%的范围内，以及0-20%是其他MAX相或元素。
5.如权利要求1所述的燃气涡轮机部件，其特征在于，所述金属是Ni或Co基超合金，或者属于合成物MCrAlYX，其中，M表示Ni、Co或Fe，并且X表示少于20at-%的其他元素。
6.一种用于制造如权利要求1所述的燃气涡轮机部件的方法，其包括如下步骤：
a）提供适合于在燃气涡轮机环境中使用的金属；
b）提供被称为MAX相的三元陶瓷，所述MAX相具有分子式Mn+1AXn，其中，n=1、2、或3，M是前过渡金属，并且A是A族元素，并且X是C和/或N，因此 M在40-60 at-%的范围内，A在10-30at-%的范围内并且X在20-40 at-%的范围内，并且因此M+A+X在80-100at-%的范围内，以及0-20at-%是上面没有列出且由于杂质或氧化引入的其他元素；以及
c）通过粉末技术工艺和/或喷涂方法结合所述金属和所述MAX相以构造所述燃气涡轮机部件；
其中所述燃气涡轮机部件具有包括一个或多个腔的中空金属结构，在步骤c）中，用所述MAX相材料填充所述腔。
7.如权利要求6所述的方法，其特征在于，所述金属是Ni或Co基超合金或MCrAlYX，其中，M表示Ni、Co或Fe，并且X表示少于20at-%的其他元素。
8.如权利要求6所述的方法，其特征在于，所述燃气涡轮机部件在步骤c）之后进行热处理或热等静压过程。
9.如权利要求8所述的方法，其特征在于，所述HIP或热处理过程在比所述金属和MAX相的熔点更低的温度下完成以便在高温下致密化和/或应力松弛。
10.如权利要求6所述的方法，其特征在于，对所述中空金属结构进行预氧化以形成薄TGO，从而避免氧化和与所述MAX相的相互扩散。
11.如权利要求6所述的方法，其特征在于，在步骤c）中，所述金属的中空金属结构填充有MAX相和金属粉末的混合物，其中，所述MAX相占50-100 %wt，并且所述金属粉末具有比所述MAX相和所述中空金属结构更低的熔点。
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