CN102695818A - 纳米和微米结构的陶瓷绝热涂层 - Google Patents

纳米和微米结构的陶瓷绝热涂层 Download PDF

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CN102695818A
CN102695818A CN2010800596293A CN201080059629A CN102695818A CN 102695818 A CN102695818 A CN 102695818A CN 2010800596293 A CN2010800596293 A CN 2010800596293A CN 201080059629 A CN201080059629 A CN 201080059629A CN 102695818 A CN102695818 A CN 102695818A
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弗里德黑尔姆·施米茨
沃纳·斯塔姆
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Abstract

通过具有纳米结构的内陶瓷层(10)改进了陶瓷层(16)的延展性。

Description

纳米和微米结构的陶瓷绝热涂层
本发明涉及具有纳米结构层和微米结构层的陶瓷绝热涂层。
绝热涂层必须具有低的热导率以及与基材或与金属粘合层的良好粘合。
特别地，应该提高所述绝热涂层的延展性。
因此，本发明的目的是提高所述陶瓷绝热涂层的延展性。
通过根据权利要求1的绝热涂层解决了该问题。
附图表示如下
图1本发明的示意图；
图2气轮机；
图3涡轮叶片；
图4燃烧室；
图5高温合金的列表。
下列实例和图仅为本发明的一些实施方案。
在图1中示出组件1、120、130、155。它显示特别是在如图5中给出的镍基高温合金制成的气轮机100(图2)的组件如叶片或叶120、130(图3)的情况下的金属基材4。
在基材4上，优选施加特别是MCrAlY型的金属粘合层7。
在一些情况下，能够在基材4上直接施加陶瓷绝热涂层TBC16。
在施加陶瓷TBC期间或至少在涂层系统操作期间，在基材4上或在粘合层7上形成氧化铝层8(TGO)。
粘合层7优选为分两层的金属层，在上部区域中具有减少量的铝和/或铬。优选地，该上部的金属层具有约16％至18％的铬(Cr)和4％至5％的铝(Al)。
这改进了直接面向陶瓷层的金属层的延展性。
陶瓷绝热涂层16为分两层的陶瓷层的涂层10、13。特别地，陶瓷TBC16仅由两个层10、13组成。
在金属粘合层7上的内陶瓷涂层10(在基材4的上方或之上)为纳米结构的，并且特别地比上部设置的陶瓷层13薄得多。这提高了陶瓷涂层的延展性和粘着性。
纳米结构的表示陶瓷层10的约70％、特别地至少90％的晶粒尺寸小于500nm，特别地≤300nm。
避免烧结的最小晶粒尺寸大于(≥)100nm并且非常特别地≥200nm。
仅内陶瓷涂层10为纳米结构的。外层13为微米结构的。
微米结构的表示至少70％、特别地至少90％的晶粒的晶粒尺寸大于1μm，特别地大于20μm。
特别地，下层10比上部陶瓷绝热涂层10薄得多。
这表示上层13的厚度包含陶瓷层13的总厚度的至少60％，特别是70％。
特别地，下陶瓷层10具有最小10μm、特别地为20μm，至多100μm的厚度。
特别地，内陶瓷涂层10的孔隙率至多为14体积％，特别地为9体积％至14体积％。
特别地，上陶瓷层13具有比内陶瓷涂层10高得多的孔隙率(相差至少10％，特别地≥20％)，特别地高于15体积％的孔隙率和至多30体积％的孔隙率。
能够通过任何涂覆方法(如等离子喷涂、HVOF或冷气喷涂)来施加上层13。
优选地，通过悬浮液、等离子喷涂或溶液前体等离子喷涂或任何溶胶凝胶技术来施加纳米结构的陶瓷层10。
两个陶瓷层10、13的材料可相同，特别地该材料为钇稳定的氧化锆。此外，内陶瓷涂层10可为纳米结构的部分稳定的氧化锆，并且上层13具有不同的组成以及特别地为具有烧绿石的结构的陶瓷层，其特别为锆酸钆(如Gd2Zr2O7)或铪酸钆(如Gd2Hf2O7)。
图3示出涡轮机的沿着纵轴121延伸的转子叶片120或导叶130的透视图。
涡轮机可以是用于发电的发电站或飞机的气轮机、汽轮机或压缩机。
叶片或叶120、130具有沿着纵轴121连续的固定区域400、邻接叶片或叶平台403以及主要叶片或主要部分406。作为导叶130，叶130在其叶端415可具有另外的平台(未示出)。
用于将转子叶片120、130固定至轴或盘(未示出)的叶片或叶的根部183形成在固定区域400中。例如，叶片或叶的根部183设计成锤头形状。也可能是其它的结构如杉树或者燕尾形根。叶片或叶120、130具有用于流经主要叶片或叶部分406的介质的前缘409和后缘412。
在常规的叶片或叶120、130的情况下，作为实例，固体金属材料(特别是高温合金)用于叶片或叶120、130的所有区域400、403、406中。例如，由EP 1 204 776 B1、EP 1 306 454、EP 1 319 729 A1、WO 99/67435或WO 00/44949中已知该类型的高温合金。这些文献形成关于该合金的化学成的本公开内容的部分。在这种情况下，可以通过铸造方法，还可以通过定向凝固的方式、通过锻造方法、通过碾磨方法或其组合来生成叶片或叶120、130。
将具有单晶结构的工件用作在操作期间暴露于高的机械负荷、热负荷和/或化学负荷的机械组件。例如，通过由熔体的定向凝固生成该类型的单晶工件。这涉及铸造方法，其中液态金属合金凝固以形成单晶结构，即单晶工件，即定向地。在该方法中，在热流的方向上形成枝状晶体，并且形成柱状晶体的晶粒结构(即具有遍布工件整个长度的晶粒，并且根据标准术语，在本文中称为定向凝固)或单晶结构，即整个工件由单晶组成。在该方法中，需要避免转变为球状(多晶)凝固，因为非定向的生长不可避免地会引起横向晶界和纵向晶界的形成，这不利地影响定向凝固的或者单晶的组件的良好性能。通常当涉及定向凝固微结构时，将其理解为包括单晶和柱状晶体结构二者，单晶不具有任何晶界或至多具有小角晶界；柱状晶体结构具有在纵向上分布的晶界，但是不具有任何横向晶界。在这些后者的晶体结构的情况下，也可能涉及定向凝固微米结构(定向凝固结构)。由US 6,024,792和EP 0 892 090 A1中已知该类型的方法。
叶片或叶120、130还可具有防止腐蚀或氧化的涂层，例如(MCrAlX；M为选自下列中的至少一种元素：铁(Fe)、钴(Co)、镍(Ni)，X为活性元素并且代表钇(Y)和/或硅和/或至少一种稀土元素，或蛤(Hf))。由EP 0 486 489 B1、EP 0 786 017 B1、EP 0 412 397 B1或EP 1 306 454 A1中已知该类型的合金。
在MCrAlX上可能存在由没有、部分地或全部地由氧化钇和/或氧化钙和/或氧化镁稳定的例如ZrO2、Y2O4-ZrO2组成的绝热涂层。通过适当的涂覆方法(例如电子束物理气相沉积(EB-PVD))在绝热涂层中生成柱状晶粒。
术语整修(refμrbishment)表示在保护层被使用之后可能不得不将它们从组件120、130去除(例如通过喷砂)。然后，去除腐蚀和/或氧化层或产物。如果必要，根据本发明也使用软钎料修复组件120、130中的裂缝。接着重新涂覆该组件120、130，其后能够再次使用该组件120、130。
叶片或叶120、130可为实心或空心设计。如果该叶片或叶120、130待冷却，其为空心并且还可包括膜冷却孔418(用虚线表示)。
图4示出气轮机100(图2)的燃烧室110。
例如，燃烧室110构造为所谓的环形燃烧室，其中以周边方向排列在旋转轴102周围的多个燃烧器107打开到共用的燃烧室空间154中，利用燃烧器107产生火焰156。为此，位于旋转轴102周围的燃烧室110整体为环形构造。
为了实现相对高的效率，设计燃烧室110用于约为1000℃至1600℃的工作介质M的相对高的温度。为了允许相对长的操作时间(即使使用这些对材料不利的操作参数)，燃烧室壁153提供有由在其面向工作介质M侧上的热屏蔽元件155形成的内衬。由合金制成的每个热屏蔽元件155配备在具有特别抗热的保护层(MCrAlX层和/或陶瓷涂层)的工作介质侧上，或者每个热屏蔽元件155由能够耐受高温的材料(固体陶瓷砖)制成。这些保护层可与涡轮叶片或叶相似，即表示例如MCrAlX：M为选自下列中的至少一种元素：铁(Fe)、钴(Co)、镍(Ni)，X为活性元素并且代表钇(Y)和/或硅和/或至少一种稀土元素，或蛤(Hf)。由EP 0 486489 B1、EP 0 786 017 B1、EP 0 412 397 B1或EP 1 306 454 A1中已知该类型的合金，其意在形成关于该合金的化学组成的本公开内容的部分。
例如，在MCrAlX上也能够存在例如由没有、部分地或者全部地由氧化钇和/或氧化钙和/或氧化镁稳定的ZrO2、Y2O4-ZrO2组成的绝热涂层。
通过适当的涂覆方法(例如电子束物理气相沉积(EB-PVD))在绝热涂层中生成柱状晶粒。
术语整修表示在保护层使用之后可能不得不将在它们从热屏蔽元件155去除(例如通过喷砂)。然后，去除腐蚀和/或氧化层或产物。如果必要，根据本发明也使用软钎料修复热屏蔽元件155中的裂缝。接着重新涂覆该热屏蔽元件155，其后能够再次使用该热屏蔽元件155。
此外，考虑到在燃烧室110的内部中的高温，可能为热屏蔽元件155和/或为它们的保持元件提供冷却系统。在这种情况下，例如该热屏蔽元件155为空心并且还可包括打开到燃烧室空间154中的膜冷却孔(未示出)。
作为实例，图2以纵向部分截面的形式示出气轮机100。在其内部，该气轮机100具有也称为涡轮转子的安装为使得其能够围绕旋转轴102旋转的转子103并且具有轴。入口壳体104、压缩机105、具有多个同轴排列的燃烧器107的燃烧室110(例如曲面，特别是环状燃烧室)、涡轮108和排气缸109沿着转子103逐个排列。环状燃烧室110与例如环状的热气管道111相连通，例如在环状热气管道111中，四个连续的涡轮级112形成涡轮108。
例如，每个涡轮级112由两个叶片环或叶环形成。如在工作介质113的流动方向上所见，由转子叶片120形成的一排(roW)125跟着在热气管道111中的一排115的导叶。
例如通过涡轮盘133，将导叶130固定至定子143的内壳体138上，而将一排125的转子叶片120装配到转子103上。将发电机或机械(未示出)耦接到转子103。
当气轮机100运行时，压缩机105通过入口壳体104吸入空气135并且将空气压缩。在压缩机105的涡轮侧端提供的压缩空气被送到燃烧器107，在此处其与燃料混合。然后，混合物在燃烧室110中燃烧以形成工作介质133。从那里，工作介质133沿着热气管道111流经导叶130和转子叶片120。工作介质113在转子叶片120处膨胀，传递其动量，以使转子叶片120驱动转子103并且该转子驱动与其耦接的机械。
当气轮机100运行时，暴露于热工作介质113的组件要承受热负荷。如在工作介质113的流动方向上所见，第一涡轮级112的导叶130和转子叶片120连同与环状燃烧室110排成一行的热屏蔽元件一起承受最高的热负荷。为了耐受那里普遍的温度，能够通过冷却剂来冷却这些组件。
组件的基材同样可能具有定向结构，即它们为单晶形式(SX结构)或者仅包括纵向定向的晶粒(DS结构)。作为实例，将铁基、镍基或钴基高温合金作为用于组件、特别是用于涡轮叶片和叶120、130以及燃烧室110的组件的材料。例如，由EP 1 204 776 B1、EP 1 306 454、EP 1 319 729A1、WO 99/67435或WO 00/44949中已知该类型的高温合金。
叶片和叶120、130同样也可以具有防止腐蚀的涂层(MCrAlX；M为选自下列中的至少一种元素：铁(Fe)、钴(Co)、镍(Ni)，X为活性元素并且代表钇(Y)和/或硅和/或至少一种稀土元素或蛤)。由EP 0 486489 B1、EP 0 786 017 B1、EP 0 412 397 B1或EP 1 306 454 A1中已知该类型的合金。
在MCrAlX上也可存在例如由没有、部分地或者全部地由氧化钇和/或氧化钙和/或氧化镁稳定的ZrO2、Y2O4-ZrO2组成的绝热涂层。通过适当的涂覆方法(例如电子束物理气相沉积(EB-PVD))在绝热涂层中生成柱状晶粒。
导叶130具有面向涡轮108的内壳体138的导叶根(这里未示出)以及在导叶根的对侧上的导叶头。该导叶头面向转子103并且固定至定子143的固定环140。

Claims (16)

1.一种层系统，其包含：
基材(4)，
任选的金属粘合层(7)，和
具有内陶瓷层(10)和外陶瓷层(13)的分两层的陶瓷层(16)，其中仅所述内陶瓷层(10)是纳米结构的。
2.根据权利要求1所述的层系统，
其中所述内陶瓷层(10)比所述外陶瓷层(13)薄，
特别地薄至少10％，
非常特别地薄至少20％。
3.根据权利要求1或2所述的层系统，
其中所述内陶瓷层(10)具有至多100μm的厚度。
4.根据权利要求1、2或3所述的层系统，
其中所述内陶瓷层(10)的厚度为至少10μm、特别地为至少20μm。
5.根据权利要求1、2、3或4所述的层系统，
其中所述内陶瓷层(10)的孔隙率为3体积％至14体积％，特别地为9体积％至14体积％。
6.根据权利要求1、2、3、4或5所述的层系统，
其中所述上层(13)的孔隙率高于所述内层(10)的孔隙率，
特别地高出至少10％，
非常特别地高出至少20％。
7.根据权利要求1、2、3、4、5或6所述的层系统，
其中所述上层(13)的孔隙率至多为30体积％，特别地为＞15体积％至30体积％。
8.根据权利要求1、2、3、4、6或7所述的层系统，
其中所述两个陶瓷层(10、13)的材料相同，
特别地为稳定的氧化锆，
非常特别地为钇稳定的氧化锆。
9.根据权利要求1、2、3、4、5、6、7或8所述的层系统，
其中所述内陶瓷层(10)的材料包括氧化锆，
特别地存在钇稳定的氧化锆。
10.根据权利要求1、2、3、4、5、6、7或9所述的层系统，
其中所述外陶瓷层(13)的材料与所述内陶瓷层(10)的材料不同，
特别地它(13)具有烧绿石结构。
11.根据前述权利要求中任一项所述的层系统，
其中所述纳米结构层(10)中至少90％的晶粒的最大晶粒尺寸为500nm，
特别地，所有晶粒尺寸小于500nm，
非常特别地小于300nm。
12.根据前述权利要求中任一项所述的层系统，
其中所述内层(10)的晶粒尺寸为至少50nm，
特别地为≥100nm，
非常特别地为≥200nm。
13.根据前述权利要求中任一项所述的层系统，
其中所述陶瓷层(16)由两个层(10、13)组成。
14.根据前述权利要求中任一项所述的层系统，
其中所述外陶瓷层(13)的至少70％的晶粒尺寸大于10μm，
特别地至少90％大于10μm。
15.根据前述权利要求中任一项所述的层系统，其中所述粘合层(7)为分两层的金属层，
特别地在上部区域中具有减少量的铝(Al)和/或铬(Cr)。
16.根据权利要求15所述的层系统，
其中关于铬(Cr)的量为16重量％至18重量％的铬(Cr)和/或4重量％至5重量％的铝(Al)。
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