CN105143498B - 铬基的氧化保护层 - Google Patents

铬基的氧化保护层 Download PDF

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CN105143498B
CN105143498B CN201480021676.7A CN201480021676A CN105143498B CN 105143498 B CN105143498 B CN 105143498B CN 201480021676 A CN201480021676 A CN 201480021676A CN 105143498 B CN105143498 B CN 105143498B
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尤尔根·拉姆
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Oerlikon Surface Solutions AG Pfaeffikon
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Abstract

本发明涉及用于经历高温的基材的铬基氧化保护层，其中该层包括含铬的层体系，该层体系包括基底层和功能层，其中该基底层位于基材和功能层之间，并且该基底层至少大部分包含氮化铬，该功能层包含氧化铬。本发明还涉及用于经历高温的基材的铬基氧化保护层，该层包括含铬的层体系，该层体系包括功能层，该功能层具有包括交替沉积的单层A和单层B的多层的层结构，其中该单层A的组成不同于该单层B的组成，并且单层A至少大部分包含氮化铝铬或最好是氮化铬，而单层B至少大部分包含氧化铝铬或氧化铬、或者最好是氮氧化铝铬或更优选的是氮氧化铬。

Description

铬基的氧化保护层
本发明涉及用于基材的铬基氧化保护层，所述基材是经历高温的。
现有技术
根据DE 102005061060，氧化保护层例如被用在汽轮机部件、汽轮机叶片、燃烧室板等中。在那里描述了如何借助所谓的等离子体喷射从悬浮液中将层施加到基材上。但这样施加的层尤其有以下缺点，只能施加相对厚的层膜并且所述层膜也具有会不利影响到附着能力的应力。但是，也可以与活塞有关地采用抗氧化的且导热性差的材料，例如就像DE10 2009 035841公开的那样。
因而，人们需要这样的层，其针对在应用中经历高温的基材提供良好的氧化保护。
发明内容
因此，本发明的任务是提出这样的层及其制造方法。
发明说明
根据本发明，通过一种含铬的层体系来完成该任务。铬能以金属铬形式或以化合物形式例如以氧化铬和或氮化铬形式存在。该层和/或层体系可以包含其它化学元素例如铝，金属铝或化合物中的铝。最好在基材上首先沉积一个中间层，接着将顶层施加至其上。
该层体系借助气相沉积来施加。在此情况下，例如考虑使用PVD法和/或CVD法。也可能的是，该层体系的多层中的一些是利用PVD来施加的，而该层体系的多层中的另一些是利用CVD来施加的。例如，作为PVD法可以采用真空条件下的溅射和/或蒸发。在蒸发时尤其优选提到电弧蒸发，此时借助电弧从靶表面局部蒸发出材料。
现在将结合多个例子来举例详述本发明。
根据第一实施方式，在基材上施加3μm厚的氮化铬(CrN)中间层，在氮化铬中间层上施加3μm厚的氧化铝铬(AlCrO)层。
根据本发明，氧化铝铬(AlCrO)层也可以作为复层来沉积，例如能针对各个单层以不同的组成来沉积。
根据本发明的第二实施方式，在基材上施加3.5μm厚的氮化铬中间层，在氮化铬中间层上施加3.5μm厚的氧化铝铬层。
根据本发明的第三实施方式，在基材上施加1.7μm厚的氮化铬中间层，在氮化铬中间层上施加1.7μm厚的氧化铝铬层。
根据本发明的第四实施方式，在基材上施加5μm厚的氮化铬中间层，在氮化铬中间层上施加5μm厚的CrO/N复层(CrO/CrN复层)。
在前述实施方式中，涂覆温度例如可以在450℃。
根据第五优选实施方式，在施加于基材上的氮化铬中间层上施加氮化铬(CrN)/氮氧化铬(CrON)复层(为此参见图1中的球痕研磨)。如图2的电子显微镜照片所示，氮化铬中间层的厚度约为2.4μm，复层的厚度约为3μm。
该复层例如是由36个单层构成的复层，其中的18个是氮化铬单层，而18个是氮氧化铬单层(见图1)。为了施加所述层，每个单层需要约2分钟，因此复层涂覆的持续时间约为72分钟。在涂覆时，遵守约230℃的涂覆温度。
在此，单层的数量以及其厚度可根据应用来选择。结果得到薄而耐受性强的防氧化保护层，其尤其适用于以下基材，所述基材在应用中经历高温且应该防止被氧化。
在这些例子中，氮化铬作为中间层。但根据本发明也可行的是，采用其它层作为中间层，因此例如采用金属铬。也可能的是，首先将金属铬施加到基材表面，接着将较厚的氮化铬层施加到随后由若干较薄单层构成的CrN/CrON复层上。
已经公开了一种铬基氧化保护层，其用于要经历高温的基材，其中，该层包括含铬的层体系，该层体系包括基底层和功能层，并且该基底层位于基材和功能层之间，并且该基底层至少大部分包含氮化铬，而该功能层包含氧化铬。
根据本发明的一个优选实施方式，该基底层由氮化铬构成，但对于大多数应用来说，其也可以由氮化铝铬构成。
根据另一个实施方式，该功能层至少大部分包含氧化铝铬，或者该功能层最好由氧化铝铬构成。
根据一个特别优选的实施方式，该功能层具有多层的层结构，其上交替沉积有单层A和单层B，其中，单层A的组成不同于单层B的组成。
该基底层的层厚最好大于1μm，对于某些应用而言最好在1.5μm至10μm之间，还更好的是在2μm至7μm之间。
该功能层的层厚与基底层的层厚之比最好在0.5至2之间，或者对于某些应用来说最好在0.25至1.5之间。
本发明的氧化保护层也可以是铬基氧化保护层，其用于经历高温的基材，其中，该层包括含铬的层体系，该层体系包含功能层，并且该功能层具有多层的层结构，该多层的层结构包括交替沉积的单层A和单层B，其中，单层A的组成不同于单层B的组成，并且单层A至少大部分包含氮化铝铬或最好是氮化铬，而单层B至少大部分包含氧化铝铬或氧化铬或者最好是氮氧化铝铬或更好是氮氧化铬。
一般，根据本发明，这些单层A至少大部分包含氮化铝铬或最好是氮化铬，而单层B至少大部分包含氧化铝铬或氧化铬或最好是氮氧化铝铬或更好是氮氧化铬。
根据本发明氧化层的其它优选实施方式：
·这些单层A由氮化铝铬构成，这些单层B由氧化铝铬或最好是氮氧化铝铬构成，或者
·这些单层A由氮化铬构成，这些单层B由氧化铝铬或最好是氮氧化铝铬构成，或者尤其优选地，
·这些单层A由氮化铬构成，这些单层B由氧化铬或最好是氮氧化铬构成。
该多层的层结构也可以包括单层C，单层C沉积在单层A和单层B之间，在这里，单层C的组成分别不同于单层A的组成和单层B的组成，并且单层C至少大部分包含氮氧化铝铬或最好是氮氧化铬。
这样的单层C最好由氮氧化铝铬或更优选由氮氧化铬构成。
根据一个优选实施方式，该多层的层结构分别在相互交替沉积的每个单层A和每个单层B之间包括一个单层C，单层C的氮含量大于在紧邻的单层B内的氮含量并小于在紧邻的单层A内的氮含量。
每个单层A和/或B的层厚最好在50nm至100nm之间。
另外，也公开了一种涂覆基材，其具有根据本发明前述实施方式之一的氧化层。
另外，公开了一种用于制造根据本发明前述实施方式的氧化层的方法，在这里，该方法最好是PVD方法，例如溅射法，或者对于某些应用来说最好是电弧蒸发方法。在涂覆过程中的工作温度应该最好不高于450℃。

Claims (14)

1.一种铬基的氧化保护层，所述氧化保护层被用在汽轮机部件或燃烧室板中，其中，该层包括含铬的层体系，该层体系包括基底层和功能层，并且该基底层位于基材和该功能层之间，其特征是，该基底层由氮化铬构成，
其中，该功能层具有复层的层结构，该复层的层结构包括交替沉积的单层A和单层B，其中，所述单层A的组成不同于所述单层B的组成，
其中，所述单层A由氮化铬构成，所述单层B由氧化铬或氮氧化铬构成，
其中，该复层的层结构分别在相互交替沉积的每个单层A和每个单层B之间包括一个单层C，该单层C的氮含量大于紧邻的单层B中的氮含量且小于紧邻的单层A中的氮含量。
2.根据权利要求1的铬基的氧化保护层，其特征是，该基底层的层厚大于1μm。
3.根据权利要求1的铬基的氧化保护层，其特征是，该基底层的层厚在1.5μm至10μm之间。
4.根据权利要求1的铬基的氧化保护层，其特征是，该基底层的层厚在2μm至7μm之间。
5.根据权利要求1至4之一的铬基的氧化保护层，其特征是，该功能层的层厚与该基底层的层厚之比在0.5和2之间。
6.根据权利要求1至4之一的铬基的氧化保护层，其特征是，该功能层的层厚与该基底层的层厚之比在0.25和1.5之间。
7.根据权利要求1的铬基的氧化保护层，其特征是，该复层的层结构包括至少一个单层C，该单层C沉积在单层A和单层B之间，其中，该单层C的组成分别不同于该单层A的组成和该单层B的组成，并且其中，该单层C由氮氧化铝铬或氮氧化铬构成。
8.根据权利要求1至4之一的铬基的氧化保护层，其特征是，每个单层A和/或单层B的层厚在50nm至100nm之间。
9.一种铬基的氧化保护层，所述氧化保护层被用在汽轮机部件或燃烧室板中，其中，该层包括含铬的层体系，该层体系包括功能层，其特征是，该功能层具有复层的层结构，该复层的层结构包括交替沉积的单层A和单层B，其中，所述单层A的组成不同于所述单层B的组成，并且所述单层A由氮化铬构成，而所述单层B由氧化铬或氮氧化铬构成，
其中，该复层的层结构分别在相互交替沉积的每个单层A和每个单层B之间包括一个单层C，该单层C的氮含量大于紧邻的单层B中的氮含量且小于紧邻的单层A中的氮含量。
10.根据权利要求9的铬基的氧化保护层，其特征是，该复层的层结构包括至少一个单层C，该单层C沉积在单层A和单层B之间，其中，该单层C的组成分别不同于该单层A的组成和该单层B的组成，并且其中，该单层C由氮氧化铝铬或氮氧化铬构成。
11.根据权利要求9的铬基的氧化保护层，其特征是，每个单层A和/或单层B的层厚在50nm至100nm之间。
12.一种涂覆的基材，其具有根据前述权利要求之一的铬基的氧化保护层。
13.一种用于制造根据权利要求1至11之一的铬基的氧化保护层的方法，其特征是，该方法是PVD方法，并且采用不高于450℃的工作温度。
14.根据权利要求13的方法，其特征是，该方法是溅射法或电弧蒸发法。
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