CN117720342A - 陶瓷材料、粉末以及包括陶瓷材料的层系统 - Google Patents

陶瓷材料、粉末以及包括陶瓷材料的层系统 Download PDF

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CN117720342A
CN117720342A CN202311644960.7A CN202311644960A CN117720342A CN 117720342 A CN117720342 A CN 117720342A CN 202311644960 A CN202311644960 A CN 202311644960A CN 117720342 A CN117720342 A CN 117720342A
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oxide
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ceramic
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阿尔图罗·弗洛勒斯伦特里亚
迪米特里奥斯·佐伊斯
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Siemens Energy Global GmbH and Co KG
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Abstract

通过选择特定的稳定剂和经调整的比例来获得用于隔热的改进的陶瓷材料：0.2重量％至8.0重量％的氧化锆，基本稳定剂：氧化镱(Yb2O3)、氧化铪(HfO2)、氧化铈(CeO2)、氧化钙(CaO)和/或氧化镁(MgO)，其中至少使用氧化钇(Y2O3)，以及可选地至少一种附加稳定剂：0.2重量％至20重量％的氧化铒(Er2O3)和/或氧化镱(Yb2O3)。

Description

陶瓷材料、粉末以及包括陶瓷材料的层系统
本发明是申请日为2020年03月18日、申请号为202080078253.4(PCT/EP2020/057029)、发明名称为“陶瓷材料、粉末以及包括陶瓷材料的层系统”的发明专利申请的分案申请。
技术领域
本发明涉及一种陶瓷材料和借助所述陶瓷材料制备的粉末，所述粉末能够用于陶瓷层系统。
背景技术
陶瓷通常具有高的温度稳定性进而常常用作为在高温构件如涡轮机尤其是燃气轮机上的陶瓷覆层。
发明内容
始终致力于改进陶瓷材料的隔热特性。
因此，本发明的目的是，能够解决上述问题。
所述目的通过根据本发明的陶瓷、根据本发明的陶瓷粉末和根据本发明的层系统来实现。
基于具有稳定剂的氧化锆的陶瓷层是已知的，其中在此完全稳定的氧化锆由于其更好的热稳定性常常被使用。
但是，该想法的目的是，使用具有改进的、尤其热稳定性的部分稳定的氧化锆。
附图说明
图1至4示出本发明的实施例。
具体实施方式
用0.2重量％至8重量％，尤其0.2重量％至6.0重量％的基本稳定剂：氧化钇、氧化铪、氧化铈、氧化钙和/或氧化镁来稳定氧化锆，以及可选地用附加稳定剂即0.2重量％至20重量％的氧化铒和/或氧化镱来稳定氧化锆。
在任何情况下都使用氧化钇，并且使用基本稳定剂即氧化铪、氧化铈、氧化钙和/或氧化镁中的至少一种。
这种陶瓷成分能够制备为粉末，使得还具有其它添加剂，如在使用磨料层时的立方氮化硼或其它磨料颗粒。
在层系统1I(图1)中，陶瓷层10I施加到金属上，其中在优选使用的镍基或钴基超合金作为基材4时存在金属附着层7，氧化铝(TGO，未示出)形成所述金属附着层，其中金属增附剂层优选为铝化物、铝化铂或作为基底是NiCoCrAlY合金，其中可选地x＝Ta、Re、Fe和/或Si。
由根据本发明的陶瓷材料制备的陶瓷层能够借助于EB-PVD、等离子喷涂(APS、...)、...制备，并且具有柱状结构或分区段的结构。
层10I、10”、10”’、10IV(图2-4)优选具有100μm至1000μm的层厚度。
如在图2中示出的那样，陶瓷层10II如在图1中那样也能够具有陶瓷子层13II，然而其层厚度比作为陶瓷层10II的根据本发明的陶瓷材料的层厚度薄至少20％。
陶瓷子层13II优选具有8YSZ，即具有3mol％至4mol％的钇稳定的氧化锆进而明显不同于陶瓷层10II的材料。
图3和4示出根据本发明的层结构1III、1IV的其它示例。
根据图3，与图1相比存在层系统1III的分区段的陶瓷层10III，所述陶瓷层从最外部的陶瓷层10III的表面18开始具有许多较长且竖直的裂纹15、15I，所述裂纹绝大部分在整个陶瓷层厚度上延伸，在此尤其延伸至金属附着层7或其TGO(未示出)。
同样地，层系统1IV也能够具有用于最外部的TBC 10IV的陶瓷连接层13IV(图4)，其中连接层13IV能够如在图2中所描述的那样构成。
最外部的陶瓷层10IV尤其图在图2中的最外部的层10III那样构成。
然而，优选同样竖直的裂纹14在陶瓷连接层13IV中延伸，所述裂纹延伸穿过这两个陶瓷层10IV、13IV。
较长的裂纹通过专门的方法参数或制造方法产生并且并非是多个晶粒之间的裂纹。
实施例(粗体＝特别优选)：
ZrO2+Y2O3+CeO2
ZrO2+Y2O3+MgO
ZrO2+Y2O3+HfO2
ZrO2+Y2O3+CaO
ZrO2+Y2O3+CeO2+MgO
ZrO2+Y2O3+MgO+HfO2
ZrO2+Y2O3+HfO2+CaO
ZrO2+Y2O3+CeO2+HfO2
ZrO2+Y2O3+MgO+CaO
ZrO2+Y2O3+CeO2+CaOZrO2+Y2O3+CaO+CeO2+HfO2
ZrO2+Y2O3+HfO2+MgO+CaO
ZrO2+Y2O3+CeO2+MgO+CaOZrO2+Y2O3+CeO2+MgO+HfO2
ZrO2+Y2O3+HfO2+CaO+CeO2+MgO
ZrO2+Y2O3+CeO2+Yb2O3
ZrO2+Y2O3+MgO+Yb2O3
ZrO2+Y2O3+HfO2+Yb2O3
ZrO2+Y2O3+CaO+Yb2O3
ZrO2+Y2O3+CeO2+MgO+Yb2O3
ZrO2+Y2O3+MgO+HfO2+Yb2O3
ZrO2+Y2O3+HfO2+CaO+Yb2O3
ZrO2+Y2O3+CeO2+HfO2+Yb2O3ZrO2+Y2O3+MgO+CaO+Yb2O3ZrO2+Y2O3+CeO2+CaO+Yb2O3ZrO2+Y2O3+CaO+CeO2+HfO2+Yb2O3ZrO2+Y2O3+HfO2+MgO+CaO+Yb2O3ZrO2+Y2O3+CeO2+MgO+CaO+Yb2O3ZrO2+Y2O3+CeO2+MgO+HfO2+Yb2O3ZrO2+Y2O3+HfO2+CaO+CeO2+MgO+Yb2O3ZrO2+Y2O3+CeO2+Er2O3
ZrO2+Y2O3+MgO+Er2O3
ZrO2+Y2O3+HfO2+Er2O3
ZrO2+Y2O3+CaO+Er2O3ZrO2+Y2O3+CeO2+MgO+Er2O3ZrO2+Y2O3+MgO+HfO2+Er2O3ZrO2+Y2O3+HfO2+CaO+Er2O3
ZrO2+Y2O3+CeO2+HfO2+Er2O3ZrO2+Y2O3+MgO+CaO+Er2O3
ZrO2+Y2O3+CeO2+CaO+Er2O3
ZrO2+Y2O3+CaO+CeO2+HfO2+Er2O3ZrO2+Y2O3+HfO2+MgO+CaO+Er2O3ZrO2+Y2O3+CeO2+MgO+CaO+Er2O3ZrO2+Y2O3+CeO2+MgO+HfO2+Er2O3ZrO2+Y2O3+HfO2+CaO+CeO2+MgO+Er2O3ZrO2+Y2O3+CeO2+Yb2O3+Er2O3ZrO2+Y2O3+MgO+Yb2O3+Er2O3
ZrO2+Y2O3+HfO2+Yb2O3+Er2O3
ZrO2+Y2O3+CaO+Yb2O3+Er2O3
ZrO2+Y2O3+CeO2+MgO+Yb2O3+Er2O3
ZrO2+Y2O3+MgO+HfO2+Yb2O3+Er2O3
ZrO2+Y2O3+HfO2+CaO+Yb2O3+Er2O3
ZrO2+Y2O3+CeO2+HfO2+Yb2O3+Er2O3
ZrO2+Y2O3+MgO+CaO+Yb2O3+Er2O3
ZrO2+Y2O3+CeO2+CaO+Yb2O3+Er2O3
ZrO2+Y2O3+CaO+CeO2+HfO2+Yb2O3+Er2O3
ZrO2+Y2O3+HfO2+MgO+CaO+Yb2O3+Er2O3
ZrO2+Y2O3+CeO2+MgO+CaO+Yb2O3+Er2O3
ZrO2+Y2O3+CeO2+MgO+HfO2+Yb2O3+Er2O3
ZrO2+Y2O3+HfO2+CaO+CeO2+MgO+Yb2O3+Er2O3
陶瓷材料优选具有2.5重量％至5.5重量％的氧化钇(Y2O3)，尤其3.0重量％至5.0重量％的氧化钇(Y2O3)，更尤其3.5重量％至4.0重量％的氧化钇(Y2O3)。
陶瓷材料同样能够优选具有1.5重量％至3.0重量％的氧化钇(Y2O3)，尤其2.0重量％至2.5重量％的氧化钇(Y2O3)。
陶瓷材料优选具有：0.2重量％至4.0重量％的氧化铪(HfO2)，尤其0.5重量％至4.0重量％的氧化铪(HfO2)，更尤其0.6重量％至4.0重量％的氧化铪(HfO2)。
为了更好的、即更低的导热性，陶瓷材料优选具有：0.2重量％至2.0重量％的氧化铪(HfO2)，尤其0.6重量％至2.0重量％的氧化铪(HfO2)，更尤其0.8重量％至2.0重量％的氧化铪(HfO2)。
为了更好的热稳定性，陶瓷材料优选具有：2.0重量％至4.0重量％的氧化铪(HfO2)，尤其2.4重量％至4.0重量％氧化铪(HfO2)，更尤其4.0重量％至4.0重量％氧化铪(HfO2)。
陶瓷材料优选具有5.5重量％至8.5重量％的氧化镱(Yb2O3)，尤其6.0重量％至8.0重量％的Yb2O3，更尤其6.5重量％至7.5重量％的Yb2O3。
陶瓷材料优选具有3.0重量％至4.5重量％的氧化镱(Yb2O3)，尤其是3.5重量％至4.0重量％的氧化镱(Yb2O3)。
同样优选地，陶瓷材料具有2.0重量％至4.0重量％的Er2O3，尤其2.5重量％至3.5重量％的Er2O3。
此外优选地，陶瓷材料具有(6.0-x)重量％的Y2O3+(2-4)x重量％的Yb2O3/Er2O3，亦即：在4.0重量％的Y2O3的情况下，对应于x＝2并且Yb2O3/Er2O3的比例为(2-4)*2，即位于4重量％和8重量％之间。
根据本公开的实施例，还公开了以下附记：
附记1.一种陶瓷材料，
所述陶瓷材料基于氧化锆(ZrO2)，
所述陶瓷材料具有0.2重量％至8.0重量％的基本稳定剂；尤其具有0.2重量％至6.0重量％的基本稳定剂：
氧化钇(Y2O3)、氧化铪(HfO2)、氧化铈(CeO2)、氧化钙(CaO)和/或氧化镁(MgO)，
其中至少使用氧化钇(Y2O3)，以及可选地
至少一种附加稳定剂：
0.2重量％至20重量％的氧化铒(Er2O3)和/或氧化镱(Yb2O3)。
附记2.根据附记1所述的陶瓷材料，所述陶瓷材料具有0.5重量％至6.0重量％的氧化钇(Y2O3)。
附记3.根据附记1或2所述的陶瓷材料，所述陶瓷材料具有2.5重量％至5.5重量％的氧化钇(Y2O3)，尤其3.0重量％至5.0重量％的氧化钇(Y2O3)，更尤其3.5重量％至4.0重量％的氧化钇(Y2O3)。
附记4.根据附记1或2所述的陶瓷材料，所述陶瓷材料具有1.5重量％至3.0重量％的氧化钇(Y2O3)，尤其2.0重量％至2.5重量％的氧化钇(Y2O3)。
附记5.根据附记1、2、3或4中一项或多项所述的陶瓷材料，所述陶瓷材料至少具有氧化钇(Y2O3)和氧化铪(HfO2)作为基本稳定剂，尤其仅具有氧化钇(Y2O3)和氧化铪(HfO2)作为基本稳定剂。
附记6.根据附记1、2、3、4或5中任一项或多项所述的陶瓷材料，其中氧化铪(HfO2)的含量为0.2重量％至4.0重量％，尤其0.6重量％至4.0重量％的氧化铪(HfO2)，更尤其0.8重量％至4.0重量％的氧化铪(HfO2)。
附记7.根据附记1、2、3、4、5或6中一项或多项所述的陶瓷材料，所述陶瓷材料具有至少一种附加稳定剂：氧化铒(Er2O3)和/或氧化镱(Yb2O3)。
附记8.根据附记1、2、3、4、5、6或7中一项或多项所述的陶瓷材料，所述陶瓷材料具有ZrO2-HfO2-Y2O3-Yb2O3，尤其由ZrO2-HfO2-Y2O3-Yb2O3构成。
附记9.根据附记1、2、3、4、5、6或7中一项或多项所述的陶瓷材料，所述陶瓷材料具有ZrO2-HfO2-Y2O3-Yb2O3-Er2O3，尤其由ZrO2-HfO2-Y2O3-Yb2O3-Er2O3构成。
附记10.根据附记1、2、3、4、5、6、7、8或9中一项或多项所述的陶瓷材料，所述陶瓷材料具有5.5重量％至8.5重量％的氧化镱(Yb2O3)，尤其6.0重量％至8.0重量％的氧化镱(Yb2O3)，更尤其6.5重量％至7.5重量％的氧化镱(Yb2O3)。
附记11.根据附记1、2、3、4、5、6、7、8或9中一项或多项所述的陶瓷材料，所述陶瓷材料具有3.0重量％至4.5重量％的氧化镱(Yb2O3)，尤其3.5重量％至4.0重量％的氧化镱(Yb2O3)。
附记12.根据附记1、2、3、4、5、6、7、8、9、10或11中一项或多项所述的陶瓷材料，所述陶瓷材料具有2.0重量％至4.0重量％的氧化铒(Er2O3)，尤其2.5重量％至3.5重量％的氧化铒(Er2O3)。
附记13.根据附记1、2、3、4、5、6、7、8、9、10、11或12中一项或多项所述的陶瓷材料，所述陶瓷材料具有(8.0-x)重量％的Y2O3+(2-4)x重量％的Yb2O3/Er2O3，尤其(6.0-x)重量％的Y2O3+(2-4)x重量％的Yb2O3/Er2O3。
附记14.根据上述附记中一项或多项所述的陶瓷材料，其中氧化铪(HfO2)的含量为0.2重量％至2.0重量％，尤其0.6重量％至2.0重量％的氧化铪(HfO2)，更尤其0.8重量％至2.0重量％的氧化铪(HfO2)。
附记15.根据上述附记1至13中一项或多项所述的陶瓷材料，其中氧化铪(HfO2)的含量为2.0重量％至4.0重量％，尤其2.4重量％至4.0重量％的氧化铪(HfO2)，更尤其3.0重量％至4.0重量％的氧化铪(HfO2)。
附记16.一种陶瓷粉末，所述陶瓷粉末具有根据附记1至15中一项或多项所述的材料的成分，尤其由根据附记1至15中任一项或多项所述的材料的成分构成。
附记17.一种层系统(1)，所述层系统至少具有金属基材(4)，
可选地具有金属增附剂层(7)和至少一个陶瓷层(10I、10II、10III、10IV)，所述陶瓷层基于根据附记1至15所述的根据本发明的材料或通过根据附记16所述的粉末制备。
附记18.根据附记17所述的层系统，所述层系统具有
在陶瓷层(13II、13IV；10I、10III)和金属基材(4)之间的金属增附剂层(7)，
尤其直接在所述基材(4)上，
其中所述增附剂层(7)具有NiCoCrAlY-X型合金，X可选地＝Ta、Re和/或Si，尤其是NiCoCrAlY或NiCoCrAlY-Ta。
附记19.根据附记17或18中一项或两项所述的层系统，其中在所述陶瓷层(10II、10IV)下方存在陶瓷子层(13II、13IV)，
所述陶瓷子层尤其至少20％更薄地构成并且具有钇稳定的氧化锆(YSZ)，尤其具有8YSZ，即具有3mol％至4mol％的钇稳定的氧化锆。
附记20.根据附记17、18或19中一项或多项所述的层系统，所述层系统具有分区段部，尤其通过在一个或多个所述陶瓷层(10III、10IV；13IV)中的较长的竖直裂纹(14；15、15I)引起的分区段部，尤其也在所述陶瓷子层(13IV)中。
附记21.根据附记20所述的层系统，其中通过竖直裂纹(15、15I)引起的所述分区段部仅存在于最外部的陶瓷层(10III、10IV)中。
附记22.根据附记20所述的层系统，其中通过竖直裂纹(14)引起的所述分区段部伸展穿过这两个陶瓷层(10IV、13IV)。
附记23.根据附记20、21或22中一项或多项所述的层系统，其中多个竖直裂纹(15、15I)延伸直至连接层(7)。
附记24.根据附记22或23中一项或多项所述的层系统，其中一些、尤其多个竖直裂纹(14)从表面(18)延伸直至所述连接层(7)。

Claims (19)

1.一种陶瓷材料，
所述陶瓷材料基于氧化锆(ZrO2)，
所述陶瓷材料具有0.2重量％至8.0重量％的基本稳定剂；尤其具有0.2重量％至6.0重量％的基本稳定剂：
氧化钇(Y2O3)、氧化铪(HfO2)、氧化铈(CeO2)、氧化钙(CaO)和/或氧化镁(MgO)，
其中至少使用氧化钇(Y2O3)，以及可选地
至少一种附加稳定剂：
0.2重量％至20重量％的氧化铒(Er2O3)和/或氧化镱(Yb2O3)，
所述陶瓷材料具有2.5重量％至5.5重量％的氧化钇(Y2O3)，尤其3.0重量％至5.0重量％的氧化钇(Y2O3)，更尤其3.5重量％至4.0重量％的氧化钇(Y2O3)，
其中氧化铪(HfO2)的含量为0.2重量％至4.0重量％，尤其0.6重量％至4.0重量％的氧化铪(HfO2)，更尤其0.8重量％至4.0重量％的氧化铪(HfO2)，
所述陶瓷材料具有ZrO2-HfO2-Y2O3-Yb2O3，尤其由ZrO2-HfO2-Y2O3-Yb2O3构成，
所述陶瓷材料具有ZrO2-HfO2-Y2O3-Yb2O3-Er2O3，尤其由ZrO2-HfO2-Y2O3-Yb2O3-Er2O3构成，并且
所述陶瓷材料具有5.5重量％至8.5重量％的氧化镱(Yb2O3)，尤其6.0重量％至8.0重量％的氧化镱(Yb2O3)，更尤其6.5重量％至7.5重量％的氧化镱(Yb2O3)。
2.根据权利要求1所述的陶瓷材料，所述陶瓷材料具有0.5重量％至6.0重量％的氧化钇(Y2O3)。
3.根据权利要求1或2所述的陶瓷材料，所述陶瓷材料具有1.5重量％至3.0重量％的氧化钇(Y2O3)，尤其2.0重量％至2.5重量％的氧化钇(Y2O3)。
4.根据权利要求1、2或3中一项或多项所述的陶瓷材料，所述陶瓷材料至少具有氧化钇(Y2O3)和氧化铪(HfO2)作为基本稳定剂，尤其仅具有氧化钇(Y2O3)和氧化铪(HfO2)作为基本稳定剂。
5.根据权利要求1、2、3或4中一项或多项所述的陶瓷材料，所述陶瓷材料具有至少一种附加稳定剂：氧化铒(Er2O3)和/或氧化镱(Yb2O3)。
6.根据权利要求1、2、3、4或5中一项或多项所述的陶瓷材料，所述陶瓷材料具有3.0重量％至4.5重量％的氧化镱(Yb2O3)，尤其3.5重量％至4.0重量％的氧化镱(Yb2O3)。
7.根据权利要求1、2、3、4、5或6中一项或多项所述的陶瓷材料，所述陶瓷材料具有2.0重量％至4.0重量％的氧化铒(Er2O3)，尤其2.5重量％至3.5重量％的氧化铒(Er2O3)。
8.根据权利要求1、2、3、4、5、6或7中一项或多项所述的陶瓷材料，所述陶瓷材料具有(8.0-x)重量％的Y2O3+(2-4)x重量％的Yb2O3/Er2O3，尤其(6.0-x)重量％的Y2O3+(2-4)x重量％的Yb2O3/Er2O3。
9.根据上述权利要求中一项或多项所述的陶瓷材料，其中氧化铪(HfO2)的含量为0.2重量％至2.0重量％，尤其0.6重量％至2.0重量％的氧化铪(HfO2)，更尤其0.8重量％至2.0重量％的氧化铪(HfO2)。
10.根据上述权利要求1至9中一项或多项所述的陶瓷材料，其中氧化铪(HfO2)的含量为2.0重量％至4.0重量％，尤其2.4重量％至4.0重量％的氧化铪(HfO2)，更尤其3.0重量％至4.0重量％的氧化铪(HfO2)。
11.一种陶瓷粉末，所述陶瓷粉末具有根据权利要求1至10中一项或多项所述的材料的成分，尤其由根据权利要求1至10中任一项或多项所述的材料的成分构成。
12.一种层系统(1)，所述层系统至少具有金属基材(4)，
可选地具有金属增附剂层(7)和至少一个陶瓷层(10I、10II、10III、10IV)，所述陶瓷层基于根据权利要求1至10所述的根据本发明的材料或通过根据权利要求11所述的粉末制备。
13.根据权利要求12所述的层系统，所述层系统具有
在陶瓷层(13II、13IV；10I、10III)和金属基材(4)之间的金属增附剂层(7)，
尤其直接在所述基材(4)上，
其中所述增附剂层(7)具有NiCoCrAlY-X型合金，X可选地＝Ta、Re和/或Si，尤其是NiCoCrAlY或NiCoCrAlY-Ta。
14.根据权利要求12或13中一项或两项所述的层系统，其中在所述陶瓷层(10II、10IV)下方存在陶瓷子层(13II、13IV)，
所述陶瓷子层尤其至少20％更薄地构成并且具有钇稳定的氧化锆(YSZ)，尤其具有8YSZ，即具有3mol％至4mol％的钇稳定的氧化锆。
15.根据权利要求12、13或14中一项或多项所述的层系统，所述层系统具有分区段部，尤其通过在一个或多个所述陶瓷层(10III、10IV；13IV)中的较长的竖直裂纹(14；15、15I)引起的分区段部，尤其也在所述陶瓷子层(13IV)中。
16.根据权利要求15所述的层系统，其中通过竖直裂纹(15、15I)引起的所述分区段部仅存在于最外部的陶瓷层(10III、10IV)中。
17.根据权利要求15所述的层系统，其中通过竖直裂纹(14)引起的所述分区段部伸展穿过这两个陶瓷层(10IV、13IV)。
18.根据权利要求15、16或17中一项或多项所述的层系统，其中多个竖直裂纹(15、15I)延伸直至连接层(7)。
19.根据权利要求17或18中一项或多项所述的层系统，其中一些、尤其多个竖直裂纹(14)从表面(18)延伸直至所述连接层(7)。
CN202311644960.7A 2019-11-12 2020-03-18 陶瓷材料、粉末以及包括陶瓷材料的层系统 Pending CN117720342A (zh)

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