CN111448339A - 用于燃气轮机的涡轮叶片的防腐耐蚀涂层 - Google Patents

用于燃气轮机的涡轮叶片的防腐耐蚀涂层 Download PDF

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CN111448339A
CN111448339A CN201880078346.XA CN201880078346A CN111448339A CN 111448339 A CN111448339 A CN 111448339A CN 201880078346 A CN201880078346 A CN 201880078346A CN 111448339 A CN111448339 A CN 111448339A
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尤尔根·拉姆
H·博瓦蒂
奥利弗·雅里
林尚
本诺·维德里格
卡门·耶尔格
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Oerlikon Surface Solutions AG Pfaeffikon
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Abstract

涡轮机尤其是燃气轮机的部件，其中该部件上有用于增强防腐耐蚀性的涂层，其中该涂层优选直接被施加在该部件上，其中，该涂层由功能层和中间层构成，其中该中间层布置在涡轮叶片基材和功能层之间，且其中该功能层由元素Al、Cr、O和N构成。

Description

用于燃气轮机的涡轮叶片的防腐耐蚀涂层
本发明涉及具有提供更好防腐耐蚀性的涂层的燃气轮机用叶片以及具有这种涂层的其它燃气轮机部件。
背景技术
燃气轮机部件遇到腐蚀介质。为了防腐保护所述部件而公开了施加涂层。尤其是，在此采用从气相中沉积的物理涂层。
根据常见的现有技术，采用TiN/Ti、TiN/TiAlN和TiAlN层系。它们显示出更好的耐蚀性，但例如在应用在高铬含量的钢基材时耐蚀性不足。
DE102015212588展示一种改进方案。它描述了一种涂层体系，用于受到腐蚀作用的基材，其具有至少包括第一、第二和第三层的表面，其中，
-设置在基材表面与第二层之间的第一层作为增附层构成，
-第二层是具有柱状结构的延展性金属层，和
-设置在第二层的背对基材的一侧上的第三层是具有至少20GPa硬度的陶瓷氧化物层。
以单位GPa算的硬度数据涉及压力，涂层能以该压力抵抗物体入侵。
根据现有技术将第一层设计成增附层有助于获得在基底材料与涂层体系的第二层之间的更好附着。
第二层通过其起到牺牲阳极的作用按照阴极方式来保护基材。第二层的延展性用于阻截在振动载荷下的伸展，而没有出现层膜开裂。第二层的柱状结构用于平衡由第三层造成的固有应力。
涂层体系的第三层最好具有氧化铝和/或氧化铬和/或以混晶结构形式的铝铬氧化物。它也可以完全由这些氧化物构成。通过所述氧化物，第三层耐氧化，因为它已经由至少一种氧化物构成并为此可被应用在高温下。第三层具有很致密的结构。第三层通常作为第二层的防腐保护。另外，第三层因为其陶瓷特性而起到绝缘作用，由此有利地抑制导电作用。另外，第三层比基底材料硬许多，因此对于其下方的层和基底材料有利地起到耐蚀保护作用，特别是防止滴蚀和颗粒腐蚀。优选地，所述第三层的硬度约为25GPa。
还知道了一种制造针对受到腐蚀的基材的涂层体系的方法，包括对应于本发明的涂层体系的三个层，其中，所有层的材料通过物理气相沉积(PVD)来施加。该方法之所以有利，是因为不需要热处理。另外，通过PVD所施加的层具有有利的表面粗糙度，其造成良好的空气动力学特性。
该涂层体系的PVD层根据现有技术通过阴极火花蒸发和/或溅射来施加。
但在根据现有技术的包括三层的层系中不利的是以下事实：很硬的第三氧化物层具有过小的弹性，使该层系在受到颗粒冲击时保持无损。由此，它可能在局部丧失其作为针对第二层的保护层的作用。
发明任务
本发明因此任务是提出一种用于燃气轮机部件的涂层***，其具有更好的防腐耐蚀性。
根据本发明的解决方案
根据本发明，该任务通过一种根据权利要求1的部件完成。根据本发明的部件具有耐蚀防腐的涂层，其包括功能层和中间层，中间层布置在所述涡轮叶片基材和功能层之间。
人们可以具体说，本发明提供一种涡轮机特别是燃气轮机的部件且优选是涡轮叶片，其如下所述地具有用于增强耐蚀防腐性的涂层。
根据本发明的涂层优选被直接施加在该部件上。它的特点是，它由功能层和中间层构成。在此，该中间层布置在所述涡轮叶片基材和功能层之间。该功能层基本上由元素Al、Cr、O和N构成，它们全都必须出现。功能层最好只需由这些元素构成。在本发明的进一步理解的方面，可以有一种或多种其它元素，但仅是这样的类型和以这样的量，即，它们没有影响或者没有不利地影响到防腐性和耐蚀性。
通过本发明，尤其可以获得燃气轮机涡轮叶片的使用寿命的延长，因为其磨损被减轻并且同时在所需维修间隙之间的时间被延长。
根据本发明，基材对于固体颗粒冲击、滴穿和还有气泡形成的耐蚀性提高。
功能层含有面心立方(Fm-3m)CrN和AlN。这导致在增强的弹性模量同时的“高”层硬度。因此，本发明的解决方案重叠在脆性第三层(其由DE102015212588迄今作为外层所提出)。如随后还将详述地，本发明还基于以下认识，呈单纯Al-Cr-N层形式的功能层在洒盐试验中未显示出良好的防腐性。只在Al-Cr-O-N合成时添加氧才增强防腐性，这造成本发明的最终效力。
为了增强防腐性，可以在基材和功能层之间施加中间层，其不仅适配于具体基材材料如钢的铬含量，也适配于应该对此获得保护的具体腐蚀环境，即例如相对于氯或硫。
优选改进可能性
存在以下可选的可以更进一步简化本发明的可行方式：
-中间层可以包含由Cr和/或AlCr和/或Al-Cr-O构成的层系，其中，Cr层(如果有)的厚度总是小于1微米。
-中间层优选由由AlCr和Al-Cr-O构成的层系构成。
-功能层可以是单层膜或多层膜。明显优选地，本发明意义上的多层膜是指一叠多个直接前后相继的层，其中的每一层具有由权利要求1针对功能层所要求的组成。仅例外地，为了避免专利法意义上的规避设计而要说明的是：即便当在具有所需成分的多个功能层之间以规避侵权的方式设有一个未明显有损功能的层时，也还是可以得到本发明意义上的多层膜。
-在就中间层涉及多层膜的情况下，含义相同之定义也适于套用。明显优选地，本发明意义上的形成中间层的多层膜于是指一叠多个直接前后相继的层，其中的每个层具有由相关权利要求针对中间层所要求的组成。
-如果功能层是多层结构，则有利的是在其中的Al/Cr比和/或O/N比在至少一部分层厚上周期性变化和/或至少在一部分层厚上非周期性地变化。
-特别优选的是，功能层中的Al:Cr原子比(Al/Cr)在4和1之间，更优选在2和1.5之间。
-还优选的是，功能层中的O:N原子比(O/N)在0.2和1.5之间，尤其最好在0.4和1之间，
-有利的是，该功能层具有至少25GPa、最好大于30GPa的压痕硬度(HIT)，其中，该压痕硬度(HIT)在室温下通过马氏硬度测量在Fisherscope H100c上根据ISO14577-1规范来确定。
-功能层有利地具有至少280GPa、最好大于300GPa的弹性模量(EIT)，其中，该弹性模量(EIT)在室温下通过马氏硬度测量在Fisherscope H100c上根据ISO14577-1规范来确定。
-粗糙度最好以Ra在0.1微米至0.6微米之间和/或以Rz在1微米至8微米之间。
发明的一般信息
于是，关于本发明的工作方式，描述如下：
一个优点尤其是，功能层的X射线衍射谱除了在X射线衍射中的立方(fcc)CrN和立方(fcc)AlN峰外，还具有至少一种氧化物的附加峰，就像图1所示的那样。特别有利的是，所述峰源自Cr-O和/或源自具有六方结构的Al-Cr-O。
为此作为解释可以提出，例如合成的Al-Cr-O-N层的X射线衍射图的特点是：面心立方(Fm-3m)CrN(03-065-9001)和面心立方(Fm-3m)AlN(00-025-1495)的反射，如图1所示。已经发现，这两种立方峰的存在对于高的层硬度和大的弹性模量值是重要的。这两个特征确定了层的高耐蚀性。但在试验中也发现了这对于良好的防腐性而言尚不充足。单纯的Al-Cr-N层在洒盐试验中未示出良好的防腐性。只有在Al-Cr-O-N合成时添加氧才增强防腐性。在图1中，除了单纯Al-Cr-N层的X射线衍射图外，还举例说明了用于一个具有12原子％O(Al-Cr-O-N等于100原子％)的层和一个具有24原子％O的层的值。在12原子％O的层上的洒盐腐蚀试验确实已经表明防腐性改善，但只有加入24原子％O才得到如下层，该层在试验中具有出色的防腐性。基于X射线衍射(图1)，这估计是因为氧不仅因置换氮而移入氮化物中，而且也形成氧化物，如在X射线衍射中能在具有24原子％O的层中看到的，此处形成Cr2O3。还估计出现非晶态氧化铝分量，但其在X射线衍射中是看不到的。换言之，具有高的防腐耐蚀性的Al-Cr-O-N层应该除了CrN和AlN立方相外，还具有Cr2O3相。
用于制造本发明的部件的涂层可以借助PVD方法、最好用反应火花蒸发和溅射来施加。
待涂覆的部件表面可以是高含铬量的钢表面和/或含Ni-Cr、含Ni-Co、含Ni-Cr-Co的基材表面和/或含一种或多种超合金的、最好是含铝化物(Al-Ni、Al-Ti、Al-Hf)的基材表面。
优选实施例
现在，结合不同的实施方式并借助附图来举例详述本发明。
图1示出本发明的层的功能层的X光谱。
图2示意性示出本发明的第一实施方式A的层结构，其具有如下结构：基材/Cr/AlCr/AlCrO/Al-Cr-O-N，其中，最外层是单层膜。
图3示意性示出本发明的第二实施方式B的层结构，其具有如下结构：基材/Cr/AlCr/AlCrO/Al-Cr-O-N，其中，最外层是由多个具有本发明特性的单层构成的多层膜，这些单层共同形成靠外的功能层。
图4示意性示出本发明的第三实施方式C的层结构，其具有以下结构：基材/AlCr/AlCrO/Al-Cr-O-N，其中，最外层是单层膜。
图5示出根据第三实施方式的层系的球痕研磨。
图6以SEM照片示出根据第三实施方式的层系的横截面。
图7示意性示出本发明的第四实施方式D的层结构，其具有以下结构：基材/AlCr/AlCrO/Al-Cr-O-N，其中，最外层是多层膜。
图8示出被称为TurbinPro的常见的涂覆有TiAlN的部件与实施方式C在洒盐试验中的对比。TurbinPro是瑞士Oerlikon Surface Solutions AG公司的可商业购得的层产品。
图9a示出针对不同表面的用于90°颗粒入射角度的耐固体腐蚀性。
图9b示出针对不同表面的用于20°颗粒入射角度的耐固体腐蚀性。
图10示出本发明层系的一个例子的化学组成。
借助PVD，本发明的层系(实施方式A-D)被施加至部件(燃气轮机叶片)。变型A和B具备附加的含铬的相对基材的层界面，而变型C和D没有该界面也行。耐腐性(根据ASTM G76的固体颗粒腐蚀试验)和耐蚀性(如根据DIN EN ISO 9227的洒盐试验)的优化是通过Al-Cr-O-N层中的氧分量进行的。对于耐蚀性，层硬度和弹性模量的最小值是决定性的，对于防腐性，层中的氧最小含量是决定性的。
其它
原则上要说明的是，完全与已经提出的权利要求无关地、但也与之组合地，也要求保护一种具有以下段落之一的特征的部件：
涡轮机尤其是燃气轮机的部件，其中，该部件例如可以是涡轮叶片且该部件具有防腐耐蚀性涂层，其中该部件的特点是：该涂层被施加至部件基材并且包含功能层和中间层，该中间层布置在涡轮叶片基材和功能层之间(第1段)。
根据在先第1段的部件，其中，该部件的特点是该中间层包含由Cr和/或AlCr和/或Al-Cr-O构成的层系。
根据刚好上面第2段的部件，其中，该部件的特点是该中间层由由AlCr和Al-Cr-O构成的层系组成。
根据在先第2段的部件，其中，该部件的特点是该功能层基本上包含元素Al、Cr、O和N。
根据本主题的在先段落之一的部件，其中，该部件的特点是该功能层是单层膜或多层膜。
根据第5段的部件，其中，该部件的特点是该功能层包含多层结构，在该多层结构中，Al/Cr比和/或O/N比在该层厚的至少一部分上周期性变化和/或至少在一部分层厚上非周期性地变化。
根据第5段的部件，其中，该部件的特点是在该功能层中的Al:Cr原子比(Al/Cr)在4和1之间，最好在2和1.5之间。
根据第5段的部件，其中，该部件的特点是在该功能层中的O:N原子比(O/N)在0.2和1.5之间，最好在0.4和1之间。
根据第5段的部件，其中，该部件的特点是该功能层具有至少25GPa、最好大于30GPa的压痕硬度。
根据第5段的部件，其中，该部件的特点是该功能层具有至少280GPa、最好大于300GPa的弹性模量。
根据第5段的部件，其中，该部件的特点是该功能层除了在X射线衍射中的立方CrN和立方AlN峰外，还具有至少一种氧化物的附加峰。
根据第11段的部件，其中，该部件的特点是至少其中一个所述附加峰是六方(例如像绿铬矿和/或刚玉石)相的峰。
一种制造根据第1段的部件或涂层的方法，其中，该方法的特点是为了其制造而采用阴极火花蒸发和/或溅射法。
根据第13段的方法，其中，待涂覆表面是高铬含量的钢表面和/或含Ni-Cr、含Ni-Co、含Ni-Cr-Co的基材表面和/或含一种或多种超合金的、最好是含铝化物(Al-Ni、Al-Ti、Al-Hf)的基材表面。

Claims (13)

1.一种涡轮机尤其是燃气轮机的部件，其中，该部件有用于增强防腐耐蚀性的涂层，其中，该涂层优选直接被施加在该部件上，其特征是，该涂层由功能层和中间层构成，其中，该中间层布置在涡轮叶片基材和功能层之间，且其中，该功能层由元素Al、Cr、O和N构成。
2.根据权利要求1的部件，其特征是，该中间层包含由Cr和/或AlCr和/或Al-Cr-O构成的层系。
3.根据权利要求2的部件，其特征是，该中间层由由AlCr和Al-Cr-O构成的层系组成。
4.根据前述权利要求之一的部件，其特征是，该功能层是单层膜或多层膜。
5.根据权利要求5的部件，其特征是，该功能层包含多层结构，在该多层结构中，Al/Cr比和/或O/N比在该层厚的至少一部分上周期性变化和/或至少在一部分层厚上非周期性地变化。
6.根据权利要求5的部件，其特征是，在该功能层中的Al:Cr原子比(Al/Cr)在4和1之间，最好在2和1.5之间。
7.根据权利要求5的部件，其特征是，在该功能层中的O:N原子比(O/N)在0.2和1.5之间，最好在0.4和1之间。
8.根据权利要求5的部件，其特征是，该功能层具有至少25GPa、最好大于30GPa的压痕硬度。
9.根据权利要求5的部件，其特征是，该功能层具有至少280GPa、最好大于300GPa的弹性模量。
10.根据权利要求5的部件，其特征是，该功能层除了在X射线衍射中的立方CrN和立方AlN峰外，还具有至少一种氧化物的附加峰。
11.根据权利要求11的部件，其特征是，至少其中一个所述附加峰是六方(例如像绿铬矿和/或刚玉石)相的峰。
12.一种制造根据权利要求1的部件的方法，其特征是，为了其制造而采用阴极火花蒸发和/或溅射法，并且优选直接在经过清洁的部件表面上首先沉积一个中间层且紧随其后沉积一个由元素Al、Cr、O和N构成的功能层。
13.根据权利要求13的方法，其中，待涂覆表面是高铬含量的钢表面和/或含Ni-Cr、含Ni-Co、含Ni-Cr-Co的基材表面和/或含一种或多种超合金的、最好是含铝化物(Al-Ni、Al-Ti、Al-Hf)的基材表面。
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KR20200103019A (ko) 2020-09-01
US20200392629A1 (en) 2020-12-17
ES2929111T3 (es) 2022-11-24
RU2020123141A (ru) 2022-01-25
US11479862B2 (en) 2022-10-25
JP7275449B2 (ja) 2023-05-18
WO2019122229A1 (de) 2019-06-27
EP3728695B1 (de) 2022-08-03
JP2021510179A (ja) 2021-04-15

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