CN103526099A - 具有带有不同的铬含量的NiCoCrAlY双保护层的层系统和合金 - Google Patents

具有带有不同的铬含量的NiCoCrAlY双保护层的层系统和合金 Download PDF

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CN103526099A
CN103526099A CN201310281935.7A CN201310281935A CN103526099A CN 103526099 A CN103526099 A CN 103526099A CN 201310281935 A CN201310281935 A CN 201310281935A CN 103526099 A CN103526099 A CN 103526099A
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layer
nicocraly
content
weight
chromium
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维尔纳·施塔姆
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Siemens AG
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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Abstract

通过应用双层的NiCoCrAlY层能够减少在热生长氧化层中的裂纹的形成，所述热生长氧化层由于NiCoCrAlY层的保护作用而形成。

Description

具有带有不同的铬含量的NiCoCrAlY双保护层的层系统和合金
技术领域
本发明涉及一种层系统，所述层系统具有双层的NiCoCrAlY层，其中降低了在热生长氧化层（TGO）中的易于开裂性；以及涉及一种用于层系统的合金。
背景技术
在燃气轮机的热气体路径中使用镍基材料和钴基材料。然而所述材料因为其对尽可能高的强度的优化常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，所述材料必须借助适宜的保护覆层来保护免于遭受热气体侵袭。此外，为了提高涡轮进气温度，在承受极高的热负荷的部件上还附加地施加一基于氧化锆的陶瓷层以用于隔热。为了实现被热气体加载的部件的尽可能高的工作温度和长的使用寿命，需要由附着层和隔热层构成的最优地匹配的保护层系统。在此，附着层的成分极为重要。
为了解决所述问题，将保护层施加到最热的部件上，部分地也作为用于隔热层的附着层。所述保护层通常由所谓的NiCoCrAlY覆盖层构成，除了镍和/或钴，所述NiCoCrAlY覆盖层还能够包含有铬、铝、硅、铼、钽和稀土元素，如钇、铪等。然而，在保护层上的表面温度进一步提升的情况下，可能会导致损坏，所述损坏会导致层的失效或导致隔热层的剥落。常常使用铼。
然而，铼具有下述缺点，即由于其份额，成本显著提高。这在过去几年中尤为显著并且在未来也具有重要意义。
在层表面的提升的温度的情况下或为了保护层的较长的使用时间而研发适宜的保护层，所述保护层在这个边界条件下具有改良的抗氧化性，在比含铼的层具有更低的成本的同时结合足够好的热机械耐抗性。这能够仅通过保护层的非常均衡的化学成分获得。在此，元素镍、钴、铬、铝、钇尤其是重要的。
因为所述元素由于扩散也与基础材料相互作用，这同样要高度重视。
发明内容
因此，本发明的目的是解决上述问题。
所述目的通过根据本发明的层系统和根据本发明的合金得以实现。
在下文中列出其它有利的措施，所述措施能够任意地相互组合，以便获得其它优点。
说明书和附图仅示出本发明的实施例。
通常假定，因为铬从所述层中相对强地相互扩散到通常具有比所述层更低的铬含量的基础材料中，并且在所述层和基础材料中的铬含量之间的差不应大于约5%。否则会或多或少地出现柯肯达尔多孔性
Figure BDA00003471403200021
，所述柯肯达尔多孔性会导致具有基础材料的层复合结构的过早失效。这通过相应地实施的模型计算来证实。所述性能在实验上已被证实，如已证实低的和高的铬含量的基于IN738LC的层的对比。
另一方面，在层的铬含量的上限情况下要考虑的是，在层中约为13重量%的铬（Cr）的低的铬含量的情况下，在表面上常常形成具有“多裂纹”的尖晶石，其同样会导致保护层系统的缩短的使用寿命。虽然保护层的非常均衡的成分已经引起好的结果，然而还不是最优的。
出于上述原因找到一种结合所有优点的解决方案。
这里提出的解决方案提出层成分的组合作为双重层，相比于至今为止的层成分，其具有在上述问题方面的改进。
提出一种保护层，所述保护层相比于至今为止应用的层具有更好的抗氧化性和良好的热机械性能并且由于铼的取代具有显著的成本优势。此外，相互扩散性能应是相同的或更好的。与常见的层的成分相反，双重层的上层具有>20%的铬的，尤其是>22%的铬（Cr）的铬含量。因此避免了在TGO中的尖晶石形成和“多裂纹”。在最上方的层中的铬的较高的含量具有两个原因：一方面尽管铬（Cr）在固溶退火处理中的蒸发，在最上方的层中仍存在足够的铬（Cr），以便将铝的活性保持为高的，并且另一方面，所述铬用作为用于稳定的α-氧化铝的成核剂。
而所述双重层的下层（相对于基础材料的分界层）具有明显较低的铬含量，优选12重量%至14重量%的铬（Cr）。这防止了在相对于基础材料的分界层上的缩短使用寿命的柯肯达尔多孔性。
层的其它成分基于镍（Ni）、钴（Co）、铝（Al）、稀土元素（Y、……）等的最优的份额，然而不基于铼（Re）。
示例：
双重保护层至少具有：
下方的NiCoCrAlY层的下层（10）：
NiCoCrAlY保护层具有下述成分（单位：重量%）
Ni含量：剩余
钴（Co）：24%-25.5%；
铬（Cr）：12%-14%；
铝（Al）：10.0%-12.0%，尤其是11.0%；
钇（Y）：0.2%-0.4%，尤其是0.3%
中等高的Co含量：
β/γ场变宽，避免了脆性相
平均的Cr含量：
足够低到以便避免脆性相（α铬或σ相）并且避免柯肯达尔多孔性以及仍然在长时间内保持保护作用
中等高的Al含量：
足够高到以便补充提供Al，以用于保持稳定的TGO。足够低到以便实现良好的延展性并且避免脆性倾向
低的Y含量：
足够高到以便在低的氧污染的情况下还构成足够的Y-铝酸盐，以用于构成含有Y的“钉”
足够低到以便负加速Al2O3层的氧化层生长，
以及上方的NiCoCrAlY层（13）：
NiCoCrAlY保护层具有如下成分（单位：重量%）：
Ni含量：剩余
钴（Co）：24％-25.5％；
铬（Cr）：23％-25％，优选24％；
铝（Al）：9.5％-11.5％，优选为10.5％；
钇（Y）：0.2％-0.4％，优选为0.3％
高的Cr含量：
用于避免在TGO中的尖晶石和“多裂纹”，并且改进具有低氧化率的由Al2O3层构成的氧化层的形成
中等高的Al含量：
Al含量相比于下层略微降低，以便通过高的Cr含量使延展性的变差最小化。
NiCoCrAlY层/合金也能够具有其它元素、其它或另外的稀土元素或者Ta、Ti、Fe……，但是不具有铼（Re）。
对于上方的NiCoCrAlY层13而言，不对单独的层进行镀铬，以至于因此也不存在铬梯度，因为使用统一的粉末来涂覆所述层。
相应的单个层的热力学相计算以及实验结果证实，存在氧化、构造TGO和机械特性方面的良好的结果。
金属层7在基底上的总层厚应优先为180μm至300μm。
下方的层7优先用细的粉末喷射，并且上方的层13由具有较粗的粉末部分的高铬含量的粉末构成，以便除了改进地构成氧化层以外也能够提供Ra=9μm至14μm的必要的高的粗糙度，以用于优化陶瓷层的附着。
所述方式方法也具有优点，即不需要新的提高成本的工艺步骤。
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示出超合金的列表。
具体实施方式
图1示出由基底4和双层的NiCoCrAlY层7构成的层系统，所述NiCoCrAlY层由两个不同的层成分10、13组成。
可选的是在靠外的NiCoCrAlY层13上的陶瓷隔热层16。
能够应用镍基或钴基的超合金，尤其是根据图3的合金作为基底4。
图2示出流体机械的转子叶片120或导向叶片130的立体图，所述动叶片或导向叶片沿着纵轴线121延伸。
流体机械能够是飞机的或用于产生电力的发电站的燃气轮机、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（未示出）。
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（未示出）。
叶片根部183例如构成为锤头形。作为枞树形根部或燕尾形根部的其他构形是可能的。
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EP1204776B1、EP1306454、EP1319729A1、WO99/67435或WO00/44949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成。
将带有单晶结构的工件用作为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，也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，也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）。
从US-PS6,024,792和EP0892090A1中已知这样的方法。
叶片120、130同样可以具有抗腐蚀或抗氧化的覆层，例如（MCrAlX；M是铁（Fe）、钴（Co）、镍（Ni）的组中的至少一种元素，X是活性元素并代表钇（Y）和/或硅和/或至少一种稀土元素，或铪（Hf））。由EP0486489B1、EP0786017B1、EP0412397B1或EP1306454A1已知这样的合金。
密度优选是理论密度的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，层成分具有Co-30Ni-28Cr-8Al-0.6Y-0.7Si或Co-28Ni-24Cr-10Al-0.6Y。除这些钴基保护覆层外，也优选地使用镍基保护层，例如Ni-10Cr-12Al-0.6Y-3Re或Ni-12Co-21Cr-11Al-0.4Y-2Re或Ni-25Co-17Cr-10Al-0.4Y-1.5Re。
在MCrAlX上还可以有隔热层，隔热层优选是最外层并例如由ZrO2、Y2O3-ZrO2组成，也就是说，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。
其他覆层方法也是可以考虑的，例如气相等离子喷涂（APS）、LPPS（低压等离子喷涂）、VPS或CVD。隔热层可以具有多孔的、有微观裂纹或宏观裂纹的晶粒，用于更好地耐热冲击。因此，隔热层优选地比MCrAlX层更为多孔。
再加工（Refurbishment）意味着在使用构件120、130之后，必要时必须将保护层去除（例如通过喷砂）。然后，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中的裂纹。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可以构造成空心的或实心的。如果要冷却叶片120、130，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.层系统（1），所述层系统至少具有：
基底（4）；
具有下方的NiCoCrAlY层（10）的双层的NiCoCrAlY层（7），尤其是仅双层的NiCoCrAlY层，
其中，所述下方的NiCoCrAlY层（10）的铬（Cr）含量比在下方的层（10）上的靠外的NiCoCrAlY层（13）的铬（Cr）含量低10重量%至12重量%。
2.如权利要求1所述的层系统，其中，
所述下方的NiCoCrAlY层（10）的钴（Co）含量与所述靠外的NiCoCrAlY层（13）的钴（Co）含量相等或近似，尤其其中钴（Co）含量相等，所述钴含量更尤其为24重量%至25.5重量%。
3.如权利要求1或2中的一项或两项所述的层系统，其中，所述下方的NiCoCrAlY层（10）的铝（Al）含量与所述靠外的NiCoCrAlY层（13）的铝（Al）含量近似，尤其至少相差0.5重量%，并且最多相差1重量%，所述下方的NiCoCrAlY层（10）的铝含量更尤其为10.5重量%至11.5重量%。
4.如权利要求1至3中的一项或多项所述的层系统，其中，
所述下方的NiCoCrAlY层（10）的钇（Y）含量与所述靠外的NiCoCrAlY层（13）的钇（Y）含量是相等的或近似的，所述下方的NiCoCrAlY层（10）的钇（Y）含量尤其为0.2重量%至0.6重量%。
5.如权利要求1至4中的一项或多项所述的层系统，其中，
所述下方的NiCoCrAlY层（10）具有下述成分（单位：重量%），尤其是由下述成分构成：
钴（Co）：24%-25.5%；
铬（Cr）：12%-14%；
铝（Al）：10.0%-12.0%，尤其是11.0%；
钇（Y）：0.2%-0.4%，尤其是0.3%；
镍。
6.如权利要求1至5的一项或多项所述的层系统，其中，
上方的NiCoCrAlY层（13）具有下述成分（单位：重量%），尤其是由下述成分构成：
钴（Co）：24％-25.5％；
铬（Cr）：23％-25％，尤其为24％；
铝（Al）：9.5％-11.5％，尤其为10.5％；
钇（Y）：0.2％-0.4％，尤其为0.3％；
镍。
7.如权利要求1至6中的一项或多项所述的层系统，其中，
所述层系统在所述层（7）中在铬（Cr）含量方面不具有梯度，尤其是在所述靠外的NiCoCrAlY层（13）中不具有梯度，更尤其所述层系统不被镀铬。
8.如前述权利要求1至7中的一项或多项所述的层系统，其中，
在所述靠外的NiCoCrAlY层（13）上形成或存在有热生长氧化层。
9.如前述权利要求1至8中的一项或多项所述的层系统，其中，在所述双层的NiCoCrAlY层（7）上施加有靠外的陶瓷层。
10.如权利要求1至9中的一项或多项所述的层系统，其中，
所述双层的NiCoCrAlY层（7）具有180μm至300μm的厚度。
11.如前述权利要求中的一项或多项所述的层系统，其中，
应用于上方的NiCoCrAlY层（13）的粉末的粒度与用于所述下方的NiCoCrAlY层（10）的粉末的粒度相比更粗，尤其是粗20%，
以至于上方的层（13）具有比所述下方的层（10）更大的颗粒，
以至于尤其是所述上方的层获得Ra=9μm至14μm的粗糙度。
12.如前述权利要求中的一项或多项所述的层系统，其中，
所述层系统在所述层（7、10、13）中不具有铼（Re）。
13.如前述权利要求中的一项或多项所述的层系统，其中，
所述层系统（1）的基底（4）具有至少8重量%的铬（Cr）含量。
14.合金，所述合金具有下述成分（单位：重量%），尤其是由下述成分构成：
钴（Co）：24%-25.5%，尤其是25%；
铬（Cr）：23%-25%，尤其是24%；
铝（Al）：10.5%-11.0%，尤其是10.5%；
钇（Y）：0.2%-0.4%，尤其是0.3%；
镍。
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