CN108350560A - 制造用于由空心的氧化铝球和最外部的玻璃层构成的隔热层的防腐蚀保护层的方法和构件以及材料混合物 - Google Patents

制造用于由空心的氧化铝球和最外部的玻璃层构成的隔热层的防腐蚀保护层的方法和构件以及材料混合物 Download PDF

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Publication number
CN108350560A
CN108350560A CN201680064538.6A CN201680064538A CN108350560A CN 108350560 A CN108350560 A CN 108350560A CN 201680064538 A CN201680064538 A CN 201680064538A CN 108350560 A CN108350560 A CN 108350560A
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layer
component
ceramics
aluminium
corrosion protective
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马蒂亚斯·加勒茨
夏比尔·蒙特罗
维尔纳·施塔姆
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Siemens AG
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Siemens AG
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    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495—Thickness [relative or absolute]

Abstract

本发明涉及用于陶瓷的隔热层的特别的防腐蚀保护，其通过将空心的氧化铝颗粒和最外部的玻璃层结合产生，所述玻璃层尤其通过热处理产生。

Description

制造用于由空心的氧化铝球和最外部的玻璃层构成的隔热层 的防腐蚀保护层的方法和构件以及材料混合物
技术领域
本发明涉及保护隔热层免受腐蚀，所述隔热层具有空心的氧化铝球并且还能够具有玻璃状的最外部的保护层。
背景技术
在热气路径中存在如下构件，所述构件为了降低金属温度用由部分稳定的锆或锆酸钆构成的隔热层来覆层。陶瓷的当今的表面温度结合污染物、如CMAS导致陶瓷的化学侵蚀并且也导致液相进入到陶瓷的孔中。同时，压缩机可磨耗部的磨损能够导致层上一次性的镍沉积。由于热膨胀减少，这也导致TBC(涡轮叶片覆层)剥落。迄今，不存在抵抗这种多重侵蚀的长期稳定的系统。
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的方法与根据权利要求2的构件来实现。
在从属权利要求中列举了其他有利措施，所述措施能够彼此任意组合，以便实现其他优点。
附图说明
附图示出：
图1、图2、图3示意地示出根据本发明的、具有防腐蚀保护层的层系统。
附图和说明书仅描述本发明的实施例。
具体实施方式
根据本发明的步骤在于尤其通过浆料来施加由铝颗粒构成的层。
以如下方式解决当前的问题：将由纯的铝颗粒或铝/钛族金属或金属氧化物颗粒构成的层通过喷涂浆料施加到隔热层上，所述铝/钛族金属或金属氧化物颗粒具有2％至20％的钛族金属、优选锆、铪或钛和直至5％的半金属、尤其硼、硅或锗的添加物。铝颗粒/氧化锆颗粒能够具有在1μm和125μm之间的直径，然而其中主要是在较小的直径范围中(大约2μm至40μm)的颗粒是值得期望的。施加的颗粒层的厚度能够在5μm和150μm之间。该层最优地作为浆料施加。但是其他方法也是可行的。通过适当的热处理(匹配于由基本材料、增附剂层和TBC构成的相应的覆层系统)，由铝颗粒构成空心的铝球，所述铝球具有其他的氧化物作为复合结构，所述复合结构由于其构造在运行时具有良好的延展性。现在，添加硼、硅和/或锗提高元素的扩散活性并且最终导致附加的保护层的提高的附着性。钛族氧化物提高机械兼容性和抗CMAS侵蚀的稳定性。
可选的第二层具有低熔点的、粘性的玻璃的组成，所述玻璃的熔点优选较低或在位于其下的层中的扩散的金属的熔点的范围中。玻璃尤其基本上具有SiO2并且优选包含对于调节熔点重要的伴随元素，如镁(Mg)、钙(Ca)或还有硼(B)和/或钠(Na)。
玻璃也能够在含氧的氛围中进行热处理期间才由作为前体的硅氮烷、硅氧烷或硅树脂聚合物形成。所述前体能够包含无机的填充材料，以调节收缩和降解性能或抗CMAS侵蚀的抗力。
在任何情况下，能够通过玻璃的附加的层进行铝颗粒的氧化，而沿着系统的表面移动的纯的铝颗粒在时效处理期间不堵塞构件的孔。
附加地，在热处理期间通过两个过程能够防止铝/钛族金属颗粒(所述铝/钛族金属颗粒能够导致冷却空气孔的堵塞)在隔热层的表面上的“迁移”。一方面，该情形能够通过钻孔的聚合物掩模来防止，但或者也能够通过在颗粒层上施加SiO2防止。SiO2层仅在初始状态下具有促进氧化铝/氧化锆层的形成并且防止这种颗粒到处移动的目的。由于脆性，SiO2层在运行时绝大部分会分层，并且真正的保护层能够承担保护作用。
根据本发明的步骤在于铝/钛族金属颗粒结合半金属添加物的组成和施加，并且在于施加由SiO2构成的另一附加子层。＞20％的较高的Zr含量也导致层的较低的附着性。由此，铝/锆颗粒的氧化能够进行，而沿着系统表面移动的纯的铝颗粒在时效处理期间不堵塞冷却空气孔。替选地，也能够进行聚合物掩模的利用。硼加强附加层的化学键合。浓度范围：Al；Zr＜20重量％，B＜6重量％
图1示出根据本发明的层系统1，所述层系统具有基底4。
基底4尤其是金属的，其中所述基底尤其具有镍基超合金或钴基超合金。
在基底4上存在可选的金属的增附剂层7。尤其地，这是尤其基于NiCoCrAlY的覆盖层。
在继续覆层时，或通过已知的氧化或至少在运行时，在该增附剂层7上形成氧化层(TGO)，所述氧化层在此未详细示出。
在该热生长的氧化层(TGO)或金属的增附剂层7上存在陶瓷的隔热层10。所述隔热层能够是单层的，尤其由氧化锆构成，或者双层地构成为具有氧化锆和烧绿石或“DVC”层。
根据本发明，在陶瓷的隔热层10上存在由氧化铝、尤其氧化铝空心球14构成的外部的陶瓷的防腐蚀保护层13’(图1)，其中然而粘性的玻璃可选地作为最外层16施加(图2)。
为了制造，尤其通过浆料、蒸镀、溅射等，将由尤其具有1μm至50μm的粒度的铝颗粒构成的层施加到陶瓷的隔热层10上。
该层能够具有在几微米至300μm之间、尤其最大200μm、更尤其最大100μm的层厚度。
铝(Al)的添加物优选是：尤其选自第I组硼(B)、镓(Ga)和/或锗(Ge)的至少一种元素Z，和/或除了铝(Al)之外，选自第II组锆(Zr)、钛(Ti)、钽(Ta)、铌(Nb)和/或铪(Hf)的至少一种元素为防腐蚀保护层(13’，13”，13”’)作为材料混合物施加和/或氧化或是氧化的。
附加地，可选地硅(Si)和/或镁(Mg)能够一起施加和/或存在于材料混合物中。
下列组合至少是可行的：
Al+Zr
Al+Zr+Si
Al+Zr+B
Al+Zr+Ge/Ga
Al+Zr+B+Si
Al+Hf+Si
Al+Hf+B
Al+Hf+Ge/Ga
Al+Hf+B+Si
Al+Ti+Si
Al+Ti+B
Al+Ti+Ge/Ga
Al+Ti+B+Si
Al+Ta+Si
Al+Ta+B
Al+Ta+Ge/Ga
Al+Ta+B+Si
Al+Nb+Si
Al+Nb+B
AL+Nb+Ge/Ga
Al+Nb+B+Si
Al+Mg+B
Al+Mg+Ge/Ga
Al+Mg+Ge/Ga+B
Al+Si+Zr
Al+Si+B
Al+Mg+Ti
Al+Mg+Ta
Al+Mg+Zr
Ge/Ga表示：锗和/或镓、即Ge，Ga或Ge+Ga。
第I组和第II组的元素能够分别作为第I组、第II组的两个、三个……或全部元素的混合物存在和使用。
该层应防止CMAS(CMAF)层的进入以及与CMAS(CMAF)反应。通过热处理，在隔热层和铝层之间形成氧化铝和反应层。这样施加的氧化铝具有较小的膨胀系数，并且结合源自压缩机可磨耗部的镍(Ni)，氧化铝的一部分剥落。那么剩余的层抵抗液相沉积物的进入。
根据本发明的步骤也在于施加不同颗粒大小的氧化铝，这使得一方面具有抗镍沉积的保护，但是也具有抗CMAS的保护。因为镍(Ni)的沉积仅短暂地并且在运行时间开始时出现，因此存在如下层，所述层在此短暂地起作用，并且具有如下层，所述层具有抗CMAS或类似侵蚀的长期作用。
由氧化铝或氧化物和/可选地玻璃构成的层分别比陶瓷的层系统10薄至少20％。
玻璃尤其能够是氧化硅，尤其SiO2。
替代铝(Al)，也能够使用铝(Al)和锆(Zr)(图3)。通过热处理，对于防腐蚀保护层13”’，在隔热层和铝/锆层之间形成具有氧化锆中间层的氧化铝和反应层。
通过锆(Zr)改进保护层在隔热层上的附着性。附加地，锆(Zr)降低CMAS的粘性，并且防止或减缓CMAS的渗透，从而提高层系统的使用寿命。
此外，附加地存在选自硼(B)、镓(Ga)和/或锗(Ge)和可选的硅(Si)中的至少一种元素。
在由氧化铝/氧化锆构成的层上方或在金属的铝/锆上方或在铝和元素Z上方，能够施加如上述的玻璃层。
用于形成氧化铝或氧化铝/氧化锆或氧化铝和元素Z的氧化物的热处理能够通过第一次使用构件来进行，或者在第一次使用之前或在将所述构件安装到用于高温应用的机器中之后通过前置的热处理来进行。

Claims (20)

1.一种用于制造陶瓷的层系统(1’，1”，1”’)的方法，所述层系统具有附加的外部的陶瓷的防腐蚀保护层(13’，13”，13”’)，其中可选地将金属的增附剂层(7)至少施加到基底(4)、尤其金属的基底(4)上，将至少一个陶瓷的隔热层(10)施加在所述基底(4)或金属的所述增附剂层(7)上，并且将至少含铝的层、尤其由铝(Al)构成的颗粒施加到陶瓷的所述隔热层(10)上，所述颗粒通过热处理形成氧化铝、尤其形成空心的氧化铝球，所述氧化铝形成外部的陶瓷的所述防腐蚀保护层(13’，13”，13”’)，尤其最外部的防腐蚀保护层(13’，13”’)，
其中外部的陶瓷的所述防腐蚀保护层尤其至少薄50％地构成，
其中除铝(Al)之外，为外部的陶瓷的所述防腐蚀保护层(13’，13”，13”’),施加和/或氧化选自硼(B)、锗(Ge)、镓(Ga)中的至少一种元素，和/或施加和/或氧化选自锆(Zr)、钛(Ti)、钽(Ta)、铌(Nb)和/或铪(Hf)中的至少一种元素，并且可选地进行热处理。
2.一种尤其根据权利要求1制造的构件，所述构件至少具有：
尤其由镍基超合金或钴基超合金构成的基底(4)，
可选地，尤其基于NiCoCrAlY的金属的增附剂层(7)，
用于在所述基底(4)上隔热的陶瓷的隔热层(10)，
在陶瓷的所述隔热层(10)上的与陶瓷的所述隔热层(10)相比尤其至少薄50％的、外部的陶瓷的防腐蚀保护层(13’，13”，13”’)，
所述防腐蚀保护层至少具有氧化铝和选自锆(Zr)、钛(Ti)、钽(Ta)、铌(Nb)和/或铪(Hf)中的至少一种金属或氧化物，
和/或
选自硼(B)、锗(Ge)和/或镓(Ga)中的至少一种元素或化合物，
用于外部的陶瓷的所述防腐蚀保护层(13’，13”，13”’)。
3.根据权利要求1所述的方法，
其中将所述铝(Al)和用于陶瓷的所述防腐蚀保护层(13’，13”，13”’)的至少一种另外的元素通过浆料、蒸镀或溅射施加。
4.根据权利要求1、2或3所述的方法或构件，
其中施加或施加有由铝(Al)和锆(Zr)构成的混合物，
尤其其中锆的份额最大为20重量％。
5.根据权利要求1、2、3或4中一项或多项所述的方法或构件，
其中用于陶瓷的所述防腐蚀保护层(13’，13”，13”’)的金属粉末具有直至50μm的粒度，尤其1μm至50μm的粒度。
6.根据权利要求1、2、3、4或5所述的方法或构件，
其中将低熔点的、粘性的玻璃(16)尤其通过浆料施加到所述铝层、所述铝/锆层或其氧化层上，或者低熔点的、粘性的玻璃(16)是尤其通过浆料施加到所述铝层、所述铝/锆层或其氧化层上的。
7.根据权利要求6所述的方法或构件，
其中低熔点的、粘性的所述玻璃具有氧化硅，尤其SiO2。
8.根据权利要求6或7中一项或两项所述的方法或构件，
其中低熔点的、粘性的所述玻璃具有如镁(Mg)、钙(Ca)、硼(B)和/或钠(Na)的添加物。
9.根据上述权利要求6至8中一项或多项所述的方法或构件，
其中为用于所述防腐蚀保护层的所述玻璃施加或施加有含硅的前体，尤其硅氮烷聚合物、硅氧烷聚合物或硅树脂聚合物。
10.根据权利要求1至9中至少一项或多项所述的方法或构件，
其中在包含所述氧化铝球的层(13”)上存在最外部的玻璃层(16)，或在包含所述氧化铝球的层上施加最外部的玻璃层(16)。
11.根据上述权利要求中一项或多项所述的方法或构件，
其中外部的陶瓷的所述防腐蚀保护层(13’，13”，13”’)与陶瓷的所述隔热层(10)相比至少薄30％地构成，或是至少薄30％地构成的。
12.根据权利要求1、2、4、5、6、7、8、9、10或11所述的方法或构件，
其中外部的陶瓷的所述防腐蚀保护层(13”’)具有氧化铝和氧化锆，尤其由其构成。
13.根据上述权利要求1或3至12中一项或多项所述的方法，
其中所述热处理通过在高温下第一次使用所述构件来实现。
14.根据上述权利要求1或3至12中一项或多项所述的方法，
其中所述热处理在第一次使用所述构件和/或将所述构件安装到机器中之前进行。
15.根据上述权利要求中一项或多项所述的方法或构件，
其中外部的陶瓷的所述防腐蚀保护层(13’，13”，13”’)最大300μm厚，尤其最大200μm厚，更尤其最大100μm厚。
16.根据上述权利要求1至15中一项或多项所述的方法或构件，
其中为陶瓷的所述防腐蚀保护层(13’，13”，13”’)施加和/或氧化或者施加有和/或氧化了铝(Al)和选自镁(Mg)、锆(Zr)、钛(Ti)、钽(Ta)，铌(Nb)和/或铪(Hf)中的至少一种元素。
17.根据上述权利要求中一项或多项所述的方法或构件，
其中除铝(Al)之外，为陶瓷的所述防腐蚀保护层施加或施加有选自硅(Si)、硼(B)、锗(Ge)和/或镓(Ga)中的至少一种元素。
18.根据上述权利要求中一项或多项所述的方法或构件，
其中在外部的陶瓷的所述防腐蚀保护层(13’，13”，13”’)中施加氧化铈(CeO)、氧化镧(La2O3)和/或氧化钇(Y2O3)，或存在氧化铈(CeO)、氧化镧(La2O3)和/或氧化钇(Y2O3)。
19.一种尤其用于根据权利要求1至18中一项或多项所述的方法或构件的材料混合物，
所述材料混合物至少具有：
铝，
和
选自硼(B)、锗(Ge)和/或镓(Ga)中的至少一种元素，
和/或
选自锆(Zr)、钛(Ti)、钽(Ta)、铌(Nb)和/或铪(Hf)中的至少一种元素。
20.根据权利要求19所述的材料混合物，
所述材料混合物附加地包含硅(Si)和/或镁(Mg)。
CN201680064538.6A 2015-11-05 2016-10-11 制造用于由空心的氧化铝球和最外部的玻璃层构成的隔热层的防腐蚀保护层的方法和构件以及材料混合物 Pending CN108350560A (zh)

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US20180305824A1 (en) 2018-10-25
EP3334851A1 (de) 2018-06-20

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