CN1665959A - 高耐氧化部件 - Google Patents

高耐氧化部件 Download PDF

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CN1665959A
CN1665959A CN038162326A CN03816232A CN1665959A CN 1665959 A CN1665959 A CN 1665959A CN 038162326 A CN038162326 A CN 038162326A CN 03816232 A CN03816232 A CN 03816232A CN 1665959 A CN1665959 A CN 1665959A
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mcraly
oxidation resistance
layer
high oxidation
described high
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CN100441740C (zh
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沃纳·施塔姆
威廉·J·奎达克尔斯
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Siemens AG
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Abstract

公开一种耐氧化部件1它包括基底4和保护层17。保护层17由与基底4邻接的内MCrAlY层16和外MCrAlY层19构成。外层19的特征在于具有至多达6.5wt％的铝含量和具有纯γ－Ni相的结构。

Description

高耐氧化部件
发明领域
本发明涉及一种高耐氧化性的部件，尤其是燃气轮机的浆叶或轮片。
发明背景
暴露于高温下的金属部件必须保护以防热和腐蚀作用。
特别是对具有其燃烧室或其轮机浆叶或轮片的燃气轮机，通常采用一种提供耐氧化性的中间体、保护性的MCrAlY层(M＝Fe、Co、Ni)和陶瓷热绝缘涂层来保护部件，它能保护金属部件的基底免遭热的作用。
由于氧化作用，所以在MCrAlY-和热绝缘涂层之间形成氧化铝层。
为了使涂敷的部件寿命长，必须使MCrAlY层和热绝缘涂层间有良好的连接性，而这可以通过热绝缘涂层和MCrAlY层上的氧化物层的粘接来维持。
若两种相互连接的涂层经常出现热失配，或者陶瓷层与MCrAlY层上形成的氧化铝层粘接不好时，热绝缘涂层将出现剥落。
根据US-PS6287644知道了连续的阶梯式的MCrAlY层粘结涂层，随着与下面基底的距离增加它具有连续增加量的铬、硅或锆，为的是通过调节热膨胀系数降低粘结涂层和热绝缘涂层之间的热失配。
US-PS5792521显示了一种多层的热绝缘涂层。
US-PS5514482公开了一种用于超级耐热合金部件的热绝缘涂层***，该***使用铝化物涂层如NiAl消除了MCrAlY层，但这必须具有足够高的厚度，以获得想要的性能。由US-PS6255001也可以知晓类似的技术。
NiAl层有缺点，它非常脆，这导致涂敷的热绝缘涂层易于剥落。
EP1082216B1描述了一种在其外层上具有γ-相的MCrAlY层。然而铝含量高并且外层的这种γ-相只能通过以昂贵的方法的再熔融或从液相中沉积的方法获得，因为再熔融或以液相涂敷的工艺需要另外的设备。
发明概述
按照前述，本发明的目的在于描述一种具有良好的耐氧化性和与热绝缘涂层具有良好粘接的保护层。
本发明的任务由作为外层的保护层解决，该保护层具有一层下面的常规MCrAlY层，在其上具有MCrAlY的不同组成和/或其它的组成。
一个可能性在于外层区具有经过选择要使其具有β-NiAl-结构的组成。
尤其是由γ-Ni固溶体组成的MCrAlY层的选择要使MCrAlY层的材料能通过例如等离子体喷镀方法进行涂敷。这样是有优点的，因为外层可在内层(MCrAlY)沉积后直接采用同一涂敷设备进行沉积，无须以另外的设备中再熔融表面。
保护层是连续的阶梯式的两层或多层的涂层。
附图简述
图1表示根据现有技术的状态所已知的耐热部件。
图2、3是本发明的耐氧化部件的实例。
本发明的详细说明
本发明可以许多不同的形式表现，并且不应视为限于本发明所列举的实施方案。相反，所提供这些实施方案，是为了能彻底并完全公开本发明，并且对所述技术领域的技术人员来说，将充分地报导本发明的范围内。
图1表示现有技术的已知的耐热部件。
高耐氧化部件具有基底4，在该基底上的MCrAlY层7，在MCrAlY层上形成或涂敷的热生长的氧化物层10(TGO)，最后是外热绝缘涂层13。
图2表示本发明的高耐氧化部件1。
部件1可以是燃气轮机的一种零件，尤其是气轮机浆叶或轮片或热防护屏。
基底4是金属的，例如超级耐热合金(例如Ni-Al-基的)。
在基底4上，MCrAlY层区16是一种例如NiCoCrAlY型的常规MCrAlY层16，其典型的组成(wt％)：10％-50％的钴(Co)，10％-40％的铬(Cr)，6％-15％的铝(Al)，0.02％-0.5％的钇(Y)和镍(Ni)作基本成分或其余部分。
这种MCrAlY层16还可含有另外的元素如：0.1％-2％的硅(Si)，0.2％-8％的钽(Ta)，0.2％-5％的铼(Re)。
代替至少部分钇或者另外这种MCrAlY层区16还可含有铪(Hf)和/或锆(Zr)和/或镧(La)和/或铈(Ce)或镧系的其它元素。
这种常规层16的厚度在100-500微米的范围内，并可以通过等离子体喷镀(VPS，APS)或其它的常规涂敷方法进行涂敷。
在本实施例中，本发明高耐氧化部件1揭示一种在其顶部具有另外的外层区19的MCrAlY层16，它与层区16一起形成了保护层17。
例如，外层区19由β相-NiAl组成。该层19的厚度在1-75微米的范围内，尤其是至多达50微米。β-NiAl相的脆性缺点可以通过β-NiAl层19较MCrAlY层16更薄的这一事实得到克服。
外层19仅由Ni和Al两种元素组成。这两种元素的浓度由Ni-Al二元相图确定，并且必须按这种方式加以选择，以使外层19在层19氧化的温度下是由纯β-NiAl相组成的，从而形成TGO 10(21-37wt％的Al或32-50wt％的Al)。
不管这种β-NiAl相能含有另外的合金元素，只要这些元素不破坏β-NiAl相的相结构。这种合金元素的例子是铬和/或钴。铬的最大浓度是在相关的温度下的Ni-Al-Cr三元相图中的β-相面积决定的。钴在β-NiAl相中的溶解度很高，并且几乎可以完全置换NiAl-相中的镍。
可以选择同样的另外的合金元素，如Si(硅)、Re(铼)、Ta(钽)。
合金元素浓度的主要必要条件是，它不能导致新的多相显微组织产生。
另外也可以往β-相层中加入元素(添加剂)如铪、锆、镧、铈或镧系的其它元素，这些元素经常加入以改进MCrAlY涂层的性能。
NiAl基的涂层可以使用等离子体喷镀(VPS，APS)和/或其它常规的涂敷方法涂敷。
β-NiAl相结构的优点在于亚稳态氧化铝(θ-或与γ-相的混合物)在层19氧化开始时形成。
在外层19上形成或涂敷的TGO10(例如氧化铝层)具有理想的针状结构，并因此导致TGO与陶瓷热绝缘涂层13之间的优良锚固。
在常规的MCrAlY涂层上，通常氧化铝的稳定α-相是在该涂层经受高温下形成。然而在使用具有外层19的耐热部件1时，在高温暴露过程中使亚稳态氧化铝10转化成稳定的α相，从而导致TGO中出现所希望的显微孔性。
本发明部件1的另外一个可能性是以这样给出，要使标准的MCrAlY层16是NiCoCrAlY型的，并且使铝的含量为8％-14wt％之间其厚度为50-600微米，尤其是100-300微米之间。
在这种MCrAlY层16上涂敷NiCoCrAlY型的第二层MCrAlY层区19。这第二层的组成要这样选择，以使作为外层19的改性MCrAlY层19能在高的使用(900℃-1100℃)度下显示一种纯γ-Ni基体。第二层(19)合适的组成可以从已知的Ni-Al、Ni-Cr、Co-Al、Co-Cr、Ni-Cr-Al、Co-Cr-Al的相图中得到的。
与常规的MCrAlY涂层对比，这改性MCrAlY层19具有铝浓度介于3-6.5wt％的较低铝浓度，这能使其通过仅改变等离子体喷镀设备的粉末进料而可用等离子体喷镀法容易地进行喷镀。
然而，层19也可以通过其它的常规涂敷方法进行涂敷。
由γ-相组成的这种改性MCrAlY层19的典型组成是：15-40wt％的铬(Cr)、5-80wt％的钴(Co)、3-6.5wt％的铝(Al)和Ni基本成分，尤其是20-30wt％的Cr，10-306wt％的Co，5-6wt％的Al和Ni基本成分。
这种MCrAlY层区19还可以含有所谓活性元素的另外元素，如铪(Hf)和/或锆(Zr)和或镧(La)和/或铈(Ce)或镧系的其它元素取代钇，通常这些元素是用于改进MCrAlY涂层的氧化性能。
这些活性元素的总浓度在0.01-1wt％之间，尤其是在0.03-0.5-wt％之间。
改性MCrAlY层19的厚度介于1-80微米之间，尤其是在3-20微米之间。可以选择另外的合金元素如Sc(钪)、钛(Ti)、Re(铼)、Ta(钽)Si(硅)。
在涂敷热绝缘涂层之前的热处理是可以在低氧分压，特别是10-17-10-15巴的分压下进行。
在改性γ-相基的MCrAlY层19的顶部形成想要的亚稳态氧化铝可通过在热绝缘涂层反面前在850℃-1000℃的温度下，特别是在875℃-925℃下氧化改性MCrAlY层2-100小时，尤其是持续5-15小时而获得。
在上面提到的氧化过程中这些亚稳态的氧化铝的形成，可通过在800℃-1100℃，尤其是在850℃-1050℃的温度下，往氧化气氛中加水蒸气(0.2-50vol％，尤其是20-50vol％)，或者使用很低氧分压的气氛而进行促进。除了水蒸气外，气氛还可以含有非氧化性气体，如氮、氩或氦。
因为改性MCrAlY层19是薄的，来自内部或标准MCrAlY层16的铝通过改性的MCrAlY层19扩散，以便在长期使用过程中支持氧化铝在层19的外表面上的形成，仅通过改性MCrAlY层19这是不能完成的，因为其铝浓度低。
图2表示两层的保护层17。
图3表示具有本发明高耐氧化的另一种部件1。
MCrAlY层16的浓度呈这样的连续阶梯状：靠近基底4的MCrAlY层16的组成由图2或1中所述的标准MCrAlY层16指定，而靠近热绝缘涂层13的外层19的组成表示如图2所述的层19的组成。
在外层区(19)上涂敷一种热绝缘涂层(TBC)(13)。由于因调节结构、相和显微组织，保护层(17)具有良好的耐氧化性和TBC与TGO(10)良好的粘接，使部件1的使用寿命延长。

Claims (13)

1.高耐氧化部件(1)，具有
基底(4)，
保护层(17)，
该层是由位于基底(4)上或靠近基底的中间层MCrAlY层区(16)和具有相γ-Ni的结构和至多达6.5wt％的铝含量的外McrAlY层区(19)组成，
式中M是Co、Fe、Ni中的至少一种元素，
其中所述外MCrAlY层区(19)是在中间体MCrAlY层区(16)的上面，而
其中外MCrAlY区(19)是由纯γNi相组成。
2.按权利要求1所述的高耐氧化部件，其中保护层(17)由两种分开的层(16，19)组成。
3.按权利要求1所述的高耐氧化部件，在保护层(17)内的中间层和外区(16，19)的组成具有呈连续阶梯状的浓度。
4.按权利要求1所述的高耐氧化部件，其中外层区(19)比在基底(4)上或靠近基底(4)的中间层(16)更薄些。
5.按权利要求1所述的高耐氧化部件，其中中间层MCrAlY层区(16)具有组成(wt％)：10％-15％的Co，10％-40％的Cr，6％-15％的Al，0.02％-0.5％的Y，Ni的基本成分。
6.按权利要求1所述的高耐氧化部件，其中中间层MCrAlY-层(16)或外层区(19)含有至少一种另外的元素如(wt％)：0.1-2％的Si、0.2％-8％的Ta或0.2％-5％的Re。
7.按权利要求1所述的高耐氧化部件，其中加入中间层MCrAlY区(16)或外区(19)的MCrAlY的钇和/或至少部分可被Hf、Zr、La、Ce和/或镧系的其它元素中的至少一种元素所替代。
8.按权利要求1所述的高耐氧化部件，其中外层区(19)具有组成(wt％)：15-40％的Cr，5-80％的Co，3-6.5％的Al和Ni的基本成分。
9.按权利要求1所述的高耐氧化部件，其中外层(19)区具有组成(wt％)：20-30％的Cr，10-30％的Co，5-6％的Al和Ni的基本成分。
10.按权利要求1所述的高耐氧化部件，其中MCrAlY层区(16，19)含有Ti(钛)和/或Sc(钪)。
11.按权利要求1所述的高耐氧化部件，其中在外层区(19)上形成热绝缘涂层(13)。
12.按权利要求8或9所述的高耐氧化部件，其中铼(Re)的含量在0.2wt％-2wt％之间。
13.按权利要求11所述的高耐氧化部件，其中在涂敷热绝缘涂层之前的热处理是在具有低氧分压，尤其是10-17-10-15巴分压下进行。
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CN102933734A (zh) * 2010-06-02 2013-02-13 西门子公司 合金、保护层和构件
CN103003423A (zh) * 2010-06-29 2013-03-27 纳幕尔杜邦公司 在具有另外木糖异构酶活性的重组发酵单胞菌属中改善的木糖利用
CN103003423B (zh) * 2010-06-29 2017-04-19 纳幕尔杜邦公司 在具有另外木糖异构酶活性的重组发酵单胞菌属中改善的木糖利用
CN103748266B (zh) * 2011-08-09 2016-08-24 西门子公司 合金、保护层和构件
CN103748266A (zh) * 2011-08-09 2014-04-23 西门子公司 合金、保护层和构件
US11092034B2 (en) 2011-08-09 2021-08-17 Siemens Energy Global Gmbh & Co, Kg Alloy, protective layer and component
CN103797141A (zh) * 2011-09-12 2014-05-14 西门子公司 合金、保护层和构件
US11092035B2 (en) 2011-09-12 2021-08-17 Siemens Energy Global GmbH & Co. KG Alloy, protective layer and component
CN105209648A (zh) * 2013-05-17 2015-12-30 西门子股份公司 保护涂层和具有所述保护涂层的燃气涡轮机部件
CN105593472A (zh) * 2013-10-02 2016-05-18 西门子公司 用于涡轮机的部件以及制造该部件的方法
CN109844149A (zh) * 2016-09-12 2019-06-04 西门子股份公司 NiCoCrAlY合金、粉末和层体系
CN106987755A (zh) * 2017-06-05 2017-07-28 北京普瑞新材科技有限公司 一种MCrAlY合金及其制备方法
CN111809094A (zh) * 2020-06-03 2020-10-23 上海理工大学 一种耐高温氧化的高熵合金、热障涂层及热障涂层的制备方法
CN111809094B (zh) * 2020-06-03 2021-12-14 上海理工大学 一种耐高温氧化的高熵合金、热障涂层及热障涂层的制备方法

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US20050238893A1 (en) 2005-10-27
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CN100441740C (zh) 2008-12-10
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ATE326559T1 (de) 2006-06-15
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EP2098614A1 (en) 2009-09-09
US20080206595A1 (en) 2008-08-28
EP1534878B1 (en) 2006-05-17
WO2004005581A1 (en) 2004-01-15
JP2005532193A (ja) 2005-10-27
EP1380672A1 (en) 2004-01-14
CN100482864C (zh) 2009-04-29
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US20050238907A1 (en) 2005-10-27
WO2004005580A1 (en) 2004-01-15

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