CN103003472A - 多孔的陶瓷层系统 - Google Patents

多孔的陶瓷层系统 Download PDF

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CN103003472A
CN103003472A CN2011800347308A CN201180034730A CN103003472A CN 103003472 A CN103003472 A CN 103003472A CN 2011800347308 A CN2011800347308 A CN 2011800347308A CN 201180034730 A CN201180034730 A CN 201180034730A CN 103003472 A CN103003472 A CN 103003472A
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layer
ceramic layer
zirconium white
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blade
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沃纳·斯塔姆
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Siemens AG
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Abstract

具有两层多孔层的所提出的层系统具有在狭窄范围内调节的并且相互匹配的孔隙率。

Description

多孔的陶瓷层系统
技术领域
本发明涉及一种具有两个不同的、多孔的陶瓷层的层系统。
背景技术
陶瓷保护层通常应用于在高温中使用的构件中，以便保护金属基底免于更高的温度。在此，陶瓷层具有一定的孔隙率，以便一方面降低导热能力并且以便规定一定的延展性。
发明内容
本发明的目的是，优化热特性和机械特性。
所述目的通过根据权利要求1所述的层系统来实现。在从属权利要求中列出其他有利的措施，所述措施能够任意地相互组合。
附图说明
附图示出：
图1示出层系统，
图2示出燃气轮机，
图3示出涡轮叶片，
图4示出燃烧室，
图5示出超合金列表。
附图和描述仅代表本发明的实施例。
具体实施方式
在图1中示意地示出层系统。层系统1优选是用于静态运行的或者用于飞行器的涡轮机、蒸汽轮机、燃气轮机100（图2）的涡轮叶片120、130。
优选地，基底4具有选自图5的合金的、基于镍的或者基于钴的超合金。优选地，基底是基于镍的超合金。
在基底4上优选存在尤其是MCrAl或者MCrAlX类型的金属的应用层（M=Ni、Co、Fe，优选是Ni、Co）。同样，在基底4内能够存在扩散层，在所述扩散层上能够施加陶瓷层16。
将陶瓷层16施加到金属层7上或者施加到基底4上，其中在界面处或者有意产生氧化层（TGO）或者施加氧化层，在进行陶瓷覆层期间或者在具有金属层7的层系统工作期间形成该氧化层。
陶瓷层16具有至少两个、尤其仅两个不同的陶瓷层10、13。下部的陶瓷层10与外部的陶瓷层13相比具有更低的孔隙率。下部的陶瓷层10的孔隙率为8%至14%，尤其为11%至12%（优选为体积百分比）。
优选地，内部的陶瓷层10的层厚度与外部的陶瓷层13的层厚度相比薄至少10%，尤其20%，更尤其50%地构成。下部的层具有100±25μm的厚度，而外部的层具有>100μm的厚度。
外部的陶瓷层13具有14%至18%的孔隙率并且优选为直接地暴露于热气中的最外部的层。
下部的陶瓷层10的材料是部分稳定的、尤其钇稳定的氧化锆。优选地，所述材料也用于外部的陶瓷层13，但是其中也能够应用烧绿石材料。
令人惊讶的是，陶瓷层的孔隙率选择引起相对于相同厚度的高度多孔的层的更长的寿命。
图2以局部纵剖面图举例地示出燃气轮机100。燃气轮机100在内部具有带有轴的、可围绕旋转轴线102转动地安装的转子103，该转子也称为涡轮机转子。沿着转子103依次为进气壳体104、压缩机105、带有多个同轴设置的燃烧器107的尤其为环形燃烧室的例如环面状的燃烧室110、涡轮机108和排气壳体109。环形燃烧室110与例如环形的热气体通道111连通。在那里例如四个相继连接的涡轮级112形成涡轮机108。每个涡轮级112例如由两个叶片环形成。沿工质113的流动方向观察，在热气体通道111中，由转子叶片120形成的排125跟随导向叶片排115。
在此，导向叶片130固定在定子143的内壳体138上，相对地，该排125的转子叶片120例如借助涡轮盘133安装在转子103上。发电机或者做功机械（未示出）耦接于转子103。
在燃气轮机100工作期间，压缩机105通过进气壳体104将空气135吸入并且压缩。在压缩机105的涡轮侧端部处提供的压缩空气被引至燃烧器107并且在那里与燃料混合。接着混合物在燃烧室110中燃烧，从而形成工质113。工质113从那里起沿着热气体通道111流过导向叶片130和转子叶片120。工质113在转子叶片120处以传递动量的方式膨胀，使得转子叶片120驱动转子103，并且该转子驱动耦接在其上的做功机械。
暴露于热工质113的构件在燃气轮机100工作期间承受热负荷。除了加衬于环形燃烧室110的热屏蔽元件之外，沿工质113的流动方向观察的第一涡轮机级112的导向叶片130和转子叶片120承受最高的热负荷。为了经受住那里存在的温度，可借助冷却剂来冷却第一涡轮机级的导向叶片和转子叶片。同样，构件的基质可以具有定向结构，这就是说它们是单晶的（SX结构）或仅具有纵向定向的晶粒（DS结构）。例如，铁基、镍基或钴基超合金用作构件的材料，特别是用作涡轮叶片120、130和燃烧室110的构件的材料。例如由EP 1 204 776 B1、EP 1 306 454、EP 1 319 729 A1、WO 99/67435或WO 00/44949已知这样的超合金。
导向叶片130具有朝向涡轮机108的内壳体138的导向叶片根部（这里未示出），以及与导向叶片根部相对置的导向叶片顶部。导向叶片顶部朝向转子103并固定在定子143的固定环140处。
图3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（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 776B1、EP 1 306 454、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（directionally solidified structures）。由US-PS6,024,792和EP 0 892 090 A1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）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EP 0 486 489 B1、EP 0 786 017 B1、EP 0 412 397 B1或EP 1 306 454A1已知这样的合金。密度优选地是理论密度的95%。在MCrAlX层上形成保护性氧化铝层（TGO=thermal grown oxide layer（热生长氧化层））（作为中间层或最外层）。
优选地，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，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。
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）。
图4示出燃气轮机100的燃烧室110。燃烧室110例如构成为所谓环形燃烧室，其中多个在周向上围绕旋转轴线102设置的燃烧器107通到共同的燃烧室腔154中，所述燃烧器产生火焰156。为此，燃烧室110以其整体构成为环形的结构，所述环形的结构围绕旋转轴线102定位。
为了实现相对高的效率，针对为大约1000°C至1600°C的工作介质M的相对高的温度来设计燃烧室110。为了还在这些对材料不利的工作参数的情况下实现相对长的工作持续时间，燃烧室壁153在其朝向工作介质M的侧上设有由热屏蔽元件155形成的内衬。
由于在燃烧室110的内部中的高温，此外可为热屏蔽元件155或者为所述热屏蔽元件的保持元件设置冷却系统。那么，热屏蔽元件155例如是空心的或者必要时还具有通到燃烧室腔154中的冷却孔（未示出）。
每个由合金构成的热屏蔽元件155在工作介质侧配备有尤其耐热的保护层（MCrAlX层和/或陶瓷覆层）或者由耐高温的材料（实心陶瓷石）制成。保护层能够类似涡轮叶片，于是MCrAlX例如表示：M是铁（Fe）、钴（Co）、镍（Ni）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）。从EP 0 486 489 B1、EP 0 786 017 B1、EP 0 412 397 B1或EP 1 306 454 A1中已知这种合金。
在MCrAlX上还可以有例如陶瓷的隔热层，并且隔热层例如由ZrO2、Y2O3-ZrO2构成，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。通过例如电子束气相淀积（EB-PVD）的适当的覆层工艺在隔热层中产生柱状晶粒。其他覆层工艺，例如气相等离子喷涂（APS）、LPPS、VPS或CVD也是可行的。隔热层可以具有多孔的、有微观裂缝或宏观裂缝的晶粒，用于更好的耐热冲击性。
再处理（Refurbishment）意味着在使用涡轮叶片120、130和热屏蔽元件155之后，必要时必须将保护层从涡轮叶片120、130和热屏蔽元件155上去除（例如通过喷砂）。接着，去除腐蚀层和/或氧化层或者腐蚀产物和/或氧化产物。必要时，还修复在涡轮叶片120、130或热屏蔽元件155中的裂缝。然后，进行涡轮叶片120、130和热屏蔽元件155的再覆层以及涡轮叶片120、130或热屏蔽元件155的重新使用。

Claims (8)

1.层系统，具有
基底（4），
可选地，在所述基底（4）上的金属的结合层（7），
可选地，在所述结合层（7）上的或者在所述基底（4）上的氧化层，
在所述基底（4）上的内部的陶瓷层（10），所述内部的陶瓷层具有8%至14%的孔隙率，尤其为9%至14%的孔隙率，更特别为11%至12%的孔隙率，
和在所述内部的陶瓷层（10）上的外部的陶瓷层（13），尤其是最外部的陶瓷层（13），所述最外部的陶瓷层具有14%至18%的孔隙率，尤其为16%至18%的孔隙率。
2.根据权利要求1所述的层系统，其中所述金属的结合层（7）具有MCrAl合金或者MCrAlX合金，尤其是由MCrAl合金或者MCrAlX合金组成。
3.根据权利要求1或2所述的层系统，其中下部的陶瓷层（10）的材料具有氧化锆、尤其部分稳定的氧化锆、更特别是钇部分稳定的氧化锆，尤其是由氧化锆、尤其部分稳定的氧化锆、更特别是钇部分稳定的氧化锆组成。
4.根据权利要求1、2或3所述的层系统，其中外部的层（13）具有氧化锆、尤其部分稳定的氧化锆、更特别是钇部分稳定的氧化锆，尤其是由氧化锆、尤其部分稳定的氧化锆、更特别是钇部分稳定的氧化锆组成。
5.根据权利要求1、2、3或4所述的层系统，其中所述基底（4）具有基于镍的超合金或者基于钴的超合金，尤其是由基于镍的超合金或者基于钴的超合金组成。
6.根据权利要求1、2、3、4或5所述的层系统，其中所述陶瓷层（10、13）的材料是不同的并且尤其所述外部的陶瓷层（13）具有烧绿石结构。
7.根据权利要求1、2、3、4、5或6所述的层系统，其中所述内部的陶瓷层（10）与所述最外部的陶瓷层相比至少薄10%地构成。
8.根据权利要求1、2、3、4、5、6或7所述的层系统，其中所述层系统由下列组成：
基底（4），
可选地，金属的结合层（7），
可选地，在所述结合层（7）上的氧化层，
内部的陶瓷层（10），
最外部的陶瓷层（13）。
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