CN104169469A - 具有铬含量不同的NiCoCrAlY双保护层的层系统和合金 - Google Patents
具有铬含量不同的NiCoCrAlY双保护层的层系统和合金 Download PDFInfo
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Abstract
本发明通过使用两层的NiCoCrAlY层能够减少在基于NiCoCrAlY层的保护作用而形成的热生长氧化层中形成裂纹。
Description
技术领域
本发明涉及一种层系统和用于其的合金,所述层系统具有两层的NiCoCrAlY层,其中减少热生长氧化层(TGO)中的开裂敏感度。
背景技术
在燃气轮机的热气体路径中使用镍基和钴基材料。然而,这些材料由于其优化到尽可能高的强度而通常在热气体中不具有足够的抗氧化性和抗高温腐蚀性。因此,材料必须由适当的保护覆层保护以免受热气体侵蚀。此外,为了提高涡轮机入口温度,还附加地将基于氧化锆的陶瓷层施加到最高热负荷的部件上以用于隔热。为了实现尽可能高的运行温度和以热气体来加载的部件的长的使用寿命,需要一种由附着层和隔热层组成的、优化适应的层系统。附着层的组成在此具有核心意义。
为了解决该问题,将保护层施加到最热的部件上,部分作为用于隔热层的附着层。这些层通常由所谓的NiCoCrAlY覆盖层构成,所述NiCoCrAlY覆盖层除了镍和/或钴之外还能够包含铬、铝、硅、铼、钽和稀土金属元素、如钇、铪等。然而,在表面温度继续升高的情况下,会在保护层上造成损伤,所述损伤导致层失效或导致隔热层剥落。通常使用铼。
然而,铼具有下述缺点:成本因其份额而明显提高。这在过去几年中是尤其重要的并且也在今后具有大的意义。
在层表面的温度升高的情况下或者在保护层的较长的使用时间内开发一种合适的保护层,所述保护层在该边界条件下与含铼的层相比具有改进的、结合有足够好的热机械稳定性的抗氧化性,同时具有更低的成本。这仅能够通过保护层的非常均衡的化学组分来实现。尤其地,在此元素Ni、Co、Cr、Al、Y是重要的。
因为这些元素由于扩散也与基本材料相互作用,所以同样需要着重考虑这种情况。
发明内容
因此,本发明的目的是解决上述问题。
所述目的通过根据权利要求1所述的层系统和根据权利要求14所述的合金来实现。
在从属权利要求中列举其它有利的措施,所述措施能够任意彼此组合,以便实现其它优点。
说明书和附图仅代表本发明的实施例。
通常假设:由于铬从层到与所述层相比通常具有更低的铬含量的基本材料中的相对强的相互扩散,所以层中的和基本材料中的铬含量之间的差异不应大于大约5%。否则会出现或多或少严重的柯肯达尔多孔性,所述柯肯达尔多孔性导致具有基本材料的复合层提早失效。这已经根据所执行的模型计算得到证实。根据实验已经证实了所述表现,如对基于IN 738 LC的低铬含量的和高铬含量的层进行比较所表明的那样。
另一方面,在层的铬含量的上限的情况下需考虑的是,在层中存在为大约13重量%铬(Cr)的低的铬含量的情况下,在表面上通常出现伴随着“多缝开裂(Multiple Cracking)”的尖晶石形成,这同样导致保护层系统的缩短的使用寿命。保护层的非常均衡的组成虽然已经带来良好的结果,但是仍不是最优的。
由于上述原因,寻找一种兼具所有优点的解决方案。
在此所提出的解决方案提出将层组成作为双重层的组合,所述双重层相对于迄今为止的层组成在上述问题方面具有改进。
所描述的说明在附件中示意性地并且作为金相图像示出。
提出一种保护层,所述保护层相对于迄今为止所使用的层具有更好的抗氧化性和良好的热学性能并且由于替换铼而具有明显的成本优势。除此之外,相互扩散行为应是相同的或者是更好的。相对于通常的层组成,双重层的上层具有>20%铬、特别是>22%铬(Cr)的铬含量。因此,避免了TGO中的尖晶石形成和“多缝开裂”。最上方的层中的铬(Cr)的较高的含量具有两个原因:一方面,虽然在固溶退火时铬(Cr)蒸发,但是在最上方的层中保持足够Cr存在,以便将铝的活性保持为高的,并且另一方面铬用作为用于稳定的α-氧化铝的成核剂。
双重层的下层(朝向基本材料的边界层)反之具有明显更低的铬含量,优选为大约11重量%至16重量%铬(Cr)。这防止在与基本材料的边界面上的降低使用寿命的柯肯达尔多孔性。
层的其它的组成部分基于最优份额的镍(Ni)、钴(Co)、铝(Al)、稀土元素(Y,…)等,但是不包括铼(Re)。
示例:
双重保护层至少具有:
下方的NiCoCrAlY层下层(10):
具有如下组分(以重量%说明)的NiCoCrAlY保护层
Ni含量:其余
钴(Co):22%至26%、尤其是23%至25%,
铬(Cr):11%至16%、尤其是13%,
铝(Al):10.5%至12.0%、尤其是11.5%,
钇(Y):0.2%至0.6%、尤其是0.3%至0.5%,
中等高的Co含量:
扩宽β/γ场,避免脆性相;
中等的Cr含量:
足够低,以便避免脆性相(α-铬相或者σ相)并且避免柯肯达尔多孔性并且仍然保持在长时间内的保护作用;
中等高的Al含量:
足够高,以便附加提供Al用于保持稳定的TGO;足够低,以便实现好的延展性并且避免脆化倾向;
低的Y含量:
足够高,以便在低的氧污染的情况下仍足以形成Y-铝酸盐以用于形成含Y的“柄(pegs)”;
足够低,以便使Al2O3层的氧化层生长变慢;
以及上方的NiCoCrAlY层(13):
具有如下组分(以重量%说明)的NiCoCrAlY保护层
Ni含量:其余
钴(Co):22%至26%、优选为23%至25%,
铬(Cr):23%至25%、优选为24%,
铝(Al):10.5%至12.0%、优选为10.5%,
钇(Y):0.2%至0.6%、优选为0.3%至0.5%,
高的Cr含量:
用于避免TGO中的尖晶石和“多缝开裂”并且改进Al2O3的具有低的氧化率的氧化层形成;
中等高的Al含量:
Al含量相对于下层轻微下降,以便使由高的Cr含量造成的延展性的恶化最小化。
NiCoCrAlY层/合金也能够具有其它的元素,不同的或者其它的稀土元素或者Ta、Ti、Fe…,但是不具有铼(Re)。
不为上方的NiCoCrAlY层13执行单层的铬化处理,使得因此也不存在铬梯度,因为使用均匀粉末来施加层。
对各个单层的试验结果以及热力学的相计算已经证实:在氧化、TGO的构成和机械特性方面存在良好的结果。
叶片上的金属层7的整体层厚度优选应为180μm至300μm。
下方的层7优选由细粉末喷涂并且上方的层13由高铬含量的具有较粗的粉末微粒的粉末构成,以便除了改进氧化层构成之外也提供必要的为Ra=9μm至14μm的高的粗糙度,以用于陶瓷层的最佳附着。
该处理方法也具有如下优点:不需要增加新的成本的工艺步骤。
附图说明
附图示出:
图1示出层系统,
图2示出涡轮叶片,
图3示出超合金列表。
具体实施方式
图1示出由基底4和两层的NiCoCrAlY层7构成的层系统,所述两层的NiCoCrAlY层由两个不同的层组成10、13组成。
在外部的NiCoCrAlY层13上的陶瓷的隔热层16是可选的。
能够使用镍基或者钴基超合金、特别是根据图3的合金作为基底4。
图2在立体图中示出流体机械的沿着纵轴线121延伸的转子叶片120或导向叶片130。
所述流体机械可以是飞机的或用于发电的发电厂的燃气轮机,也可以是蒸汽轮机或压缩机。
叶片120、130沿着纵轴线121相继具有:固定区域400、邻接于固定区域的叶片平台403以及叶身406和叶片梢部415。作为导向叶片130,叶片130可以在其叶片梢部415处具有另一平台(没有示出)。
在固定区域400中形成有用于将转子叶片120、130固定在轴或盘上的叶片根部183(没有示出)。叶片根部183例如构造成锤头形。作为枞树形根部或燕尾形根部的其它设计方案是可行的。
叶片120、130对于流过叶身406的介质具有迎流棱边409和出流棱边412。
在传统叶片120、130中,在叶片120、130的所有区域400、403、406中使用例如实心的金属材料、尤其是超合金。例如由EP 1 204 776 B1、EP1 306 454、EP 1 319 729 A1、WO 99/67435或WO 00/44949已知这样的超合金。在这种情况下,叶片120、130可以通过铸造法,也可以借助定向凝固、通过锻造法、通过铣削法或其组合来制造。
将带有一个或多个单晶结构的工件用作机器的在运行中承受高的机械的、热的和/或化学的负荷的构件。这种单晶工件的制造例如通过由熔融物的定向凝固来进行。在此,这涉及一种浇注法,其中液态金属合金凝固为单晶结构、即单晶工件,或者定向凝固。在这种情况下,枝状晶体沿热流定向,并且形成柱状晶体的晶粒结构(柱状地,这就是说在工件的整个长度上分布的晶粒,并且在此根据一般的语言习惯称为定向凝固),或者形成单晶结构,这就是说整个工件由唯一的晶体构成。在这些方法中,必须避免过渡成球形(多晶的)凝固,因为通过非定向的生长不可避免地构成横向和纵向晶界,所述横向和纵向晶界使定向凝固的或单晶的构件的良好特性不起作用。
如果一般性地提到定向凝固组织,则是指不具有晶界或最多具有小角度晶界的单晶和确实具有沿纵向方向分布的晶界但不具有横向晶界的柱状晶体结构。第二种所提到的晶体结构也称为定向凝固组织(directionallysolidified structures)。由US-PS 6,024,792和EP 0 892 090 A1已知这样的方法。
叶片120、130例如同样能够具有抗腐蚀或抗氧化的覆层(MCrAlX:M是铁(Fe)、钴(Co)、镍(Ni)的组中的至少一种元素,X是活性元素并且代表钇(Y)和/或硅和/或至少一种稀土元素或铪(Hf))。这样的合金从EP 0 486 489 B1、EP 0 786 017 B1、EP 0 412 397 B1或者EP 1 306 454 A1中已知。
密度优选地是理论密度的95%。在(作为中间层或最外层的)MCrAlX层上形成保护性氧化铝层(TGO=thermal grown oxide layer(热生长氧化层))。
优选地,层组成具有Co-30Ni-28Cr-8Al-0.6Y-0.7Si或者Co-28Ni-24Cr-10Al-0.6Y。除了这些钴基的保护覆层之外,优选也使用镍基的保护层如Ni-10Cr-12Al-0.6Y-3Re或者Ni-12Co-21Cr-11Al-0.4Y-2Re或者Ni-25Co-17Cr-10Al-0.4Y-1.5Re。
在MCrAlX上还可以有隔热层,所述隔热层优选是最外层并例如由ZrO2、Y2O3-ZrO2组成,即,隔热层通过氧化钇和/或氧化钙和/或氧化镁非稳定、部分稳定或完全稳定。隔热层覆盖整个MCrAlX层。通过例如电子束气相淀积(EB-PVD)的适当的覆层方法在隔热层中产生柱状晶粒。其它覆层方法也是可以考虑的,例如大气等离子喷涂(APS)、LPPS(低压等离子喷涂)、VPS(真空等离子喷涂)或CVD(化学气相沉积)。隔热层可以具有多孔的、有微观裂缝或宏观裂缝的晶粒,用于更好地耐热冲击。因此,隔热层优选地比MCrAlX层更为多孔。
再处理(Refurbishment)意味着在使用构件120、130之后,必要时必须将保护层从构件120、130上去除(例如通过喷砂)。接着,去除腐蚀层和/或氧化层及腐蚀产物和/或氧化产物。必要时,还修复在构件120、130中的裂缝。然后,进行构件120、130的再覆层以及构件120、130的重新使用。
叶片120、130可以设计成空心的或实心的。如果叶片120、130应被冷却,则叶片为空心的并且必要时还具有薄膜冷却孔418(由虚线表示)。
Claims (14)
1.一种层系统(1),所述层系统至少具有:
基底(4);
两层的NiCoCrAlY层(7)、尤其是仅两层的NiCoCrAlY层,所述两层的NiCoCrAlY层具有下方的NiCoCrAlY层(10),
其中下方的层(10)的铬(Cr)的含量与外部的NiCoCrAlY层(13)的铬(Cr)的含量相比更小,尤其小至少3重量%、更尤其是小至少5重量%。
2.根据权利要求1所述的层系统,
其中所述下方的NiCoCrAlY层(10)的钴(Co)的含量与所述外部的NiCoCrAlY层(13)的钴(Co)的含量相同或者相似,尤其其中钴(Co)的含量相同,更尤其为22重量%至26重量%。
3.根据权利要求1或2中一项或两项所述的层系统,
其中铬(Cr)的含量的差别为3重量%至13重量%、尤其为至少7重量%、更尤其为至少11重量%。
4.根据权利要求1至3中一项或多项所述的层系统,
其中所述下方的NiCoCrAlY层(10)的铝(Al)的含量与所述外部的NiCoCrAlY层(13)的铝(Al)的含量相同或者相似,尤其相同,更尤其为10.5重量%至12.0重量%。
5.根据权利要求1至4中一项或多项所述的层系统,
其中所述下方的NiCoCrAlY层(10)的钇(Y)的含量与所述外部的NiCoCrAlY层(13)的钇(Y)的含量相同或者相似,尤其为0.2重量%至0.6重量%。
6.根据权利要求1至5中一项或多项所述的层系统,
其中所述下方的NiCoCrAlY层(10)具有下述组分(以重量%说明):
钴(Co):22%至26%、尤其是23%至25%,
铬(Cr):11%至16%、尤其是13%,
铝(Al):10.5%至12.0%、尤其是11.5%,
钇(Y):0.2%至0.6%、尤其是0.3%至0.5%,
镍,
尤其是由其构成。
7.根据权利要求1至6中一项或多项所述的层系统,
其中所述上方的NiCoCrAlY层(13)具有下述组分(以重量%说明):
钴(Co):22%至26%、尤其是23%至25%,
铬(Cr):23%至25%、尤其是24%,
铝(Al):10.5%至12.0%、尤其是10.5%,
钇(Y):0.2%至0.6%、尤其是0.3%至0.5%,
镍,
尤其是由其构成。
8.根据权利要求1至7中一项或多项所述的层系统,
所述层系统在所述层(7)中不具有铬(Cr)的含量的梯度、尤其是在所述外部的NiCoCrAlY层(13)中不具有铬(Cr)的含量的梯度、更尤其是不经过铬化处理的。
9.根据权利要求1至8中一项或多项所述的层系统,
其中热生长氧化层在所述外部的NiCoCrAlY层(13)上形成或者存在于所述外部的NiCoCrAlY层(13)上。
10.根据权利要求1至9中一项或多项所述的层系统,
其中在所述两层的NiCoCrAlY层(7)上施加有外部的陶瓷层。
11.根据权利要求1至10中一项或多项所述的层系统,
其中NiCoCrAlY层(7)具有180μm至300μm的厚度。
12.根据上述权利要求中一项或多项所述的层系统,
其中用于所述上方的NiCoCrAlY层(13)的粉末与用于所述下方的NiCoCrAlY层(10)的粉末的粒度相比更粗糙、尤其是粗糙20%,使得上方的层(13)与所述下方的层(10)相比具有更大的粒度,使得尤其实现Ra=9μm至14μm的粗糙度。
13.根据上述权利要求中一项或多项所述的层系统,所述层系统在层(7,10,13)中不具有铼(Re)。
14.一种合金,所述合金具有(以重量%说明):
钴(Co):22%至26%、尤其是23%至25%,
铬(Cr):23%至25%、尤其是24%,
铝(Al):10.5%至12.0%、尤其是10.5%,
钇(Y):0.2%至0.6%、尤其是0.3%至0.5%,
镍,
尤其是由其构成。
Applications Claiming Priority (3)
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EP12159894.0 | 2012-03-16 | ||
EP12159894.0A EP2639336A1 (de) | 2012-03-16 | 2012-03-16 | Schichtsystem mit NiCoCrAlY-Doppelschutzschicht mit unterschiedlichem Chromgehalt und Legierung |
PCT/EP2012/075883 WO2013135326A1 (de) | 2012-03-16 | 2012-12-18 | Schichtsystem mit nicocraly-doppelschutzschicht mit unterschiedlichem chromgehalt und legierung |
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US (1) | US20150030876A1 (zh) |
EP (2) | EP2639336A1 (zh) |
JP (1) | JP5932066B2 (zh) |
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CN103526099A (zh) * | 2012-07-05 | 2014-01-22 | 西门子公司 | 具有带有不同的铬含量的NiCoCrAlY双保护层的层系统和合金 |
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US9506140B2 (en) | 2013-03-15 | 2016-11-29 | United Technologies Corporation | Spallation-resistant thermal barrier coating |
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- 2012-12-18 CN CN201280071489.0A patent/CN104169469B/zh not_active Expired - Fee Related
- 2012-12-18 JP JP2014561302A patent/JP5932066B2/ja not_active Expired - Fee Related
- 2012-12-18 EP EP12812931.9A patent/EP2788530A1/de not_active Withdrawn
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EP2788530A1 (de) | 2014-10-15 |
JP5932066B2 (ja) | 2016-06-08 |
WO2013135326A1 (de) | 2013-09-19 |
CN104169469B (zh) | 2016-11-16 |
EP2639336A1 (de) | 2013-09-18 |
US20150030876A1 (en) | 2015-01-29 |
KR101662416B1 (ko) | 2016-10-04 |
KR20140129151A (ko) | 2014-11-06 |
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