CN100482864C - 高耐氧化部件 - Google Patents

高耐氧化部件 Download PDF

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CN100482864C
CN100482864C CNB038162334A CN03816233A CN100482864C CN 100482864 C CN100482864 C CN 100482864C CN B038162334 A CNB038162334 A CN B038162334A CN 03816233 A CN03816233 A CN 03816233A CN 100482864 C CN100482864 C CN 100482864C
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mcraly
oxidation resistance
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沃纳·施塔姆
威廉·J·奎达克尔斯
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Abstract

公开一种耐氧化部件(1)，该部件包括基底(4)和保护层(17)。保护层(17)是由与基底邻接的内MCrAlY层(16)和由至少Ni和Al构成并具有β-NiAl结构的外层(19)构成。

Description

高耐氧化部件
发明领域
本发明涉及一种具有高耐氧化性的部件，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加以保护以防热和腐蚀的作用。
尤其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的、保护的MCrAlY层(M＝Fe、Co、Ni)和陶瓷热障涂层保护部件，它能保护金属部件的基底免遭热的作用。
由于氧化作用，在MCrAlY-和热障涂层间形成一层氧化铝层。
为了使涂敷部件的使用寿命长，必须使MCrAlY层和热障涂层之间具有良好的连接性，而这可以通过热障涂层和MCrAlY层上的氧化物层的粘接来达到。
当两种相互连接的层之间经常发生热失配时，或者陶瓷层与MCrAlY层上形成的氧化铝层粘接差时，热障涂层将会发生剥落。
根据US-PS6287644知道了连续阶梯式MCrAlY粘接涂层，随着与下面基底的距离的增加它具有连续增长量的铬、硅或锆，为的是通过调节热膨胀系数降低粘接涂层和热障涂层之间的热失配。
US-PS5792521表明了一种多层的热障涂层。
US-PS5514482公开了一种用于超级耐热合金部件的热障涂层系统，该系统通过使用铝化物涂层如NiAl而消除MCrAlY层，但是，这必须具有足够高的厚度以获得所期望的性能。由US-PU6255001也可以了解到类似的技术。
NiAl层有缺点，它非常脆，这将导致涂敷(onlaying)的热障涂层易于剥落。
EP1082216B1公开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沉积才能获得，因为对于再熔融或用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障涂层具有良好粘接的保护层。
本发明的任务是通过保护层来解决，该保护层具有一下面的常规MCrAlY层，在其上MCrAlY的不同组合物和/或其它的组合物作为外层。
一种可能性是外层区具有经过选择要使其具有β-NiAl-结构的组成。
尤其是选择由γ-Ni固溶体组成的MCrAlY层以使MCrAlY层的材料能通过例如等离子体喷镀法进行涂敷。这样是有优点的，因为外层可以在内层(MCrAlY)沉积后直接使用同一涂敷设备进行沉积，无须以另外的设备再熔融表面。
保护层可以是连续阶梯式的、两层或多层的涂层。
附图的简要说明
图1表示根据现有技术的状态所已知的耐热部件。
图2、3是本发明耐氧化部件的实例。
发明的详细描述
本发明可以许多不同形式表现，并且不应视为限于本文所列举的实施方案。相反地，所提供这些实施方案，是为了能彻底和完全地公开本发明，并且对于所属技术领域的技术人员来说将充分报导本发明的范围。
图1表示现有技术已知的耐热部件。
高耐氧化部件具有基底4，在该基底上的MCrAlY层7，在该MCrAlY层上形成或涂敷热生长的氧化物层10(TGO)，而最后是外热障涂层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，特别是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％)为：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)。
代替至少一部分钇或另外这种MCrAlY层还可以含有铪(Hf)和/或锆(Zr)和/或镧(La)和/或铈(Ce)或镧系元素的其它元素。
这种常规层16的厚度在100-500微米的范围内，并且可以通过等离子体喷镀(VPS，APS)，或者其它的常规涂敷方法涂敷。
在本实施例中，本发明的高耐氧化部件1揭示一种在顶部具有另外的外层区19的MCrAlY层16，它与层区16一起构成保护层17。
例如，外层区19由相β-NiAl组成。该层19的厚度在1-75微米的范围内，特别是至多达50微米。β-NiAl相的脆性的缺点可以通过与MCrAlY层16相比β-NiAl层19是薄的事实而得到克服。
外层19可仅由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32-50原子(at)％的Al)。
然而这种β-NiAl相能够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。铬的最大浓度是由在相关的温度下的Ni-Al-Cr三元相图中的β-相面积确定的。钴在β-NiAl相中的溶解度很高，并且几乎能完全置换NiAl-相中的镍。
可以选择类似的另外的合金元素，如Si(硅)、Re(铼)、Ta(钽)。
合金元素浓度的主要必要条件是，它不会导致新的多相的显微组织产生。
另外，也可在β-相层中添加元素(添加剂)如铪、锆、镧、铈或镧系元素的其它元素，这些元素常常加入以改进MCrAlY涂层的性能。
在外层区19添加Hf、Zr、La、Ce或镧系元素的其它元素中的至少一种另外元素，其中添加的元素的最大量为1wt％。
NiAl基涂层可以使用等离子体喷镀(VPS、APS)和/或其它的常规涂敷方法涂敷。
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TGO 10(例如氧化铝层)具有理想的针状结构，并因此导致TGO 10和陶瓷热障涂层13间的优良锚固。
在常规的MCrAlY涂层上，通常氧化铝的稳定α-相是在涂层经受高温下形成的。然而，在使用具有外层19的耐热部件1的过程中，在高温暴露过程中使亚稳态的氧化铝10转变成稳定的α相，从而导致TGO中所要求的微孔性。
本发明部件1的另外一个可能性是这样给出，要使标准的MCrAlY层16是NiCoCrAlY型的，并且使铝的含量在8％-14wt％之间，其厚度为50-600微米，特别是在100-300微米之间。
在这种MCrAlY层16上涂敷NiCoCrAlY型的第二MCrAlY层区19。第二层的组成要这样选择，以使作为外层19的改性MCrAlY层19能在高的使用温度下(900-1100℃)显示一种纯γ-Ni基体。第二层(19)的合适组成可以从已知的Ni-Al、Ni-Cr、Co-Al、Co-Cr、Ni-Cr-Al、Co-Cr-Al的相图中产生。
与常规的MCrAlY涂层比较，这改性的MCrAlY层19具有铝浓度介于3-6.5wt％较低铝浓度，这能通过仅变更等离子体喷镀装置的粉末进料，而可用等离子体喷镀法容易地进行涂敷。
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的典型组成为；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，10-30wt％的Co，5-6wt％Al和Ni基本成分。
这种MCrAlY层区19还可以含有另外所谓活性元素，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，这些元素一般是用于改进MCrAlY涂层的氧化性能。
这些活性元素的总浓度可在0.01-1wt％之间的范围内，尤其是0.03-0.5wt％之间。
改性MCrAlY层19的厚度在1-80微米之间，尤其是在3-20微米。可以选择另外的合金元素，如Sc(钪)、钛(Ti)、Re(铼)、Ta(钽)、Si(硅)。
在涂敷热障涂层之前的热处理，是可在低氧分压，尤其是10-7-10-15巴的分压下进行的。
在改性的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障涂层反面前在850℃-1000℃的温度下，尤其是在875℃-925℃下进行改性的MCrAlY层19的氧化2-100小时，特别是5-15小时而获得。
在上面提到的氧化过程中这些亚稳态氧化铝的形成，可通过在800℃-1100℃，尤其是介于850℃-1050℃的温度下，往氧化性气氛中添加水蒸气(0.2-50vol％，特别是20-50vol％)，或者使用非常低的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。
由于改性的MCrAlY层19是薄的，来自内部或者标准MCrAlY层16的铝可通过改性的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这不能完成，因为其铝浓度低。
图2显示两层的保护层17。
图3表示具有本发明高耐氧化性的另一种部件1。
MCrAlY层16的浓度呈这样的连续阶梯式：靠近基底4的MCrAlY层16的组成由图2或1所说明的标准MCrAlY层16确定，而靠近热障涂层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)上涂敷一种热障涂层(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并且TBC与TGO(10)具有良好的粘接，使部件1的使用寿命延长。

Claims (11)

1.高耐氧化部件(1)，具有
基底(4)，
保护层(17)，
该保护层由位于基底(4)上或靠近基底(4)的中间MCrAlY层区(16)和
外层区(19)两层组成，
式中M是Co、Fe、Ni中的至少一种元素，
其中外层区(19)是在中间MCrAlY层区(16)上，并且外层区(19)至少由元素Ni和Al构成并具有相β-NiAl结构，外层区(19)还含有合金元素铬和/或钴，它不破坏相β-NiAl，
由此使在外层区(19)中铝的含量定位在21wt％和37wt％之间。
2.按权利要求1所述的高耐氧化部件，其中保护层(17)是由两层分离的层(16、19)组成。
3.按权利要求1所述的高耐氧化部件，保护层(17)内的中间MCrAlY层区(16)和外层区(19)的组成具有连续阶梯式的浓度。
4.按权利要求1所述的高耐氧化部件，其中外层区(19)比位于基底(4)上或靠近基底(4)的中间MCrAlY层区(16)更薄。
5.按权利要求1所述的高耐氧化部件，其中中间MCrAlY层区(16)具有的组成为：10％-50wt％的Co，10％-40wt％的铬，6％-15wt％的Al，0.02％-0.5wt％的Y，Ni为基本成分。
6.按权利要求1所述的高耐氧化部件，其中中间MCrAlY层区(16)或外层区(19)含有至少一种另外的元素，0.1wt％-2wt％的Si，0.2％-8wt％的Ta或0.2wt％-5wt％的Re。
7.按权利要求1所述的高耐氧化部件，其中中间MCrAlY层区(16)的MCrAlY的钇部分被Hf、Zr、La、Ce和/或镧系的其它元素中的至少一种元素所代替。
8.按权利要求1所述的高耐氧化部件，其中在外层区(19)添加Hf、Zr、La、Ce或镧系元素的其它元素中的至少一种另外元素。
9.按权利要求8所述的高耐氧化部件，其中添加的元素的最大量为1wt％。
10.按权利要求1所述的高耐氧化部件，其中在外层区(19)上形成热障涂层(13)。
11.按权利要求10所述的高耐氧化部件，其中在涂敷热障涂层前的热处理是在具有低氧分压10-7-10-15巴的分压下进行的。
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