CN107254659A - 超级合金组件以及浆料组合物 - Google Patents

超级合金组件以及浆料组合物 Download PDF

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CN107254659A
CN107254659A CN201710493043.1A CN201710493043A CN107254659A CN 107254659 A CN107254659 A CN 107254659A CN 201710493043 A CN201710493043 A CN 201710493043A CN 107254659 A CN107254659 A CN 107254659A
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paste compound
yttrium
hafnium
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silicon
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P.M.沃克
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Siemens Energy Global GmbH and Co KG
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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
    • C23C28/02—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 only coatings only including layers of metallic material
    • C23C28/023—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 only coatings only including layers of metallic material only coatings of metal elements only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • 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
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    • 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.]
    • Y10T428/12674—Ge- or Si-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
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    • 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.]
    • Y10T428/12736—Al-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
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    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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    • Y10T428/12736—Al-base component
    • Y10T428/12764—Next to Al-base component

Abstract

提供用于对超级合金组件渗铝(aluminising)的浆料组合物，其中该浆料包含有机粘结剂和包括铝在内的固态成分。该浆料进一步包含铪和钇。此外，还提供了包括铝化物涂层的超级合金组件(1)。该涂层材料包括至少一层(3)，该层除了铝之外还包含铪和钇。

Description

超级合金组件以及浆料组合物
本申请是申请号为201080016021.2（PCT/EP2010/051922）、申请日为2010年2月16日的发明专利申请的分案申请。
技术领域
本发明涉及一种用于对超级合金组件渗铝(aluminisng)的浆料组合物，以及一种包括铝化物涂层的超级合金组件。
背景技术
暴露于热腐蚀性气体的组件，例如暴露于热腐蚀性燃气的燃气涡轮组件，通常由在高温下可提供高强度的超级合金制成。这些超级合金特别是镍基超级合金，铁基超级合金和钴基超级合金。
虽然超级合金在直到1200℃或更高的温度下具有高强度，但仍需要保护其免受氧化和/或腐蚀。这种保护通常通过形成氧化铝的涂层例如所谓MCrAlY-覆盖涂层来完成，其中M代表铁(Fe)，钴(Co)或镍(Ni)，同时Y代表钇(Y)，铪(Hf)或稀土元素。在覆盖涂层的制备期间，铝被氧化并形成牢固附着的氧化铝鳞片(scale)，从而可以保护组件免受氧化和腐蚀。例如可以从EP 0486489B1，EP0786017B1或EP1306456A1中获知这些涂层。
另一种形成耐腐蚀和/或氧化的氧化铝鳞片的方法被称之为浆料渗铝。在浆料渗铝工艺中，在组件的表面涂覆含铝浆料。接着对组件热处理从而导致铝的熔化。熔化的铝与组件材料进行反应并且形成具有氧化铝鳞片的铝化物(aluminide)涂层，保护组件免受氧化和/或腐蚀。除了铝之外，浆料还可以含有硅从而形成铝化物-硅化物涂层，其比单独的铝化物涂层具有更好的抗氧化性。通过浆料工艺形成铝化物涂层和铝化物-硅化物涂层在例如US 5,547,770，US 6,080,246，EP 1 820 875A2，US 2007/0298269A1和US 6,126,758中被披露。
除此之外，由美国专利US 3,720,537已知浆料技术可被用于在合金基体上进行涂覆。细分散的钴-铝合金，镍-铝合金和/或铁-铝合金与铬-铝合金混合。钇可作为合金被添加。
发明内容
本发明的目的是提供一种有利的用于对超级合金组件渗铝的浆料组合物，其中的超级合金组件特别为镍(Ni)基，钴(Co)或铁(Fe)基超级合金组件。本发明的另一目的是提供一种有利的包括铝化物涂层的超级合金组件。
第一目的通过如权利要求1所要求保护的用于对超级合金组件渗铝的浆料组合物得到解决。第二目的通过如权利要求7所要求保护的包括铝化物涂层的超级合金组件得到解决。从属权利要求包含本发明的进一步改进。
本发明的用于对超级合金组件渗铝的浆料组合物包含有机粘结剂，即具有粘结剂盐的溶剂例如水，以及固态成分。固态成分包括铝。根据本发明，浆料组合物进一步包含铪(Hf)和/或钇(Y)，特别是铪和钇。铪和/或钇可以以粉末形式、片状、屑状或类似形式加入到浆料的固态成分中，或以盐的形式加入到有机粘结剂中。
作为本发明浆料中使用的有机粘结剂，在本发明中特别使用铬酸盐和/或磷酸盐有机粘结剂。
已经发现向浆料中加入铪和/或钇会改善对于氧化和腐蚀的保护，这种保护通过对具有本发明浆料的超级合金组件进行热处理后而形成的铝化物涂层来提供。有利的铪含量最多为浆料重量的大约2.5%，优选最多为浆料重量的大约1%。有利的钇含量最多为浆料重量的大约0.1%，特别是最多为浆料重量的大约0.05%(5ppm)。
除了铝，固态成分中可包括占固态成分总重量1%至40%的硅。与铪和/或钇类似，通过形成铝化物-硅化物涂层而不是单独的铝化物涂层，硅改善了具有涂覆后的超级合金组件的抗氧化和耐腐蚀性。
在本发明浆料组合物的进一步改进中，该浆料包含最多为浆料重量5ppm的硫(S)含量。由于硫对超级合金材料具有腐蚀性，因此浆料中硫的存在会在具有浆料涂层的组件的热处理过程中形成氧化铝鳞片时削弱超级合金组件。通过尽可能的降低浆料中的硫含量，可以避免热处理期间硫对组件的削弱。
本发明的超级合金组件包括铝化物涂层。该涂层材料包括至少一层，该层除了铝之外还包括铪和/或钇-特别是铪和钇。
已经发现除了铝之外如果含有铪和/或钇，铝化物涂层的耐腐蚀性和/或抗氧化性可以得到改善。
在本发明超级合金组件的特殊实施方式中，该涂层包括至少两层，其中一层的涂层材料包括铝而没有铪和钇。另一层的涂层材料包括铪和/或钇。在进一步的改进中，该涂层包括至少三层，其中两层的涂层材料包括铝而没有铪和钇。第三层的涂层材料除了铝之外还包括铪和/或钇。特别是该第三层可夹在没有铪和/或钇的两层之间。应当指出，尽管在本发明的所述改进中存在具有铪和/或钇的层和没有铪和/或钇的层，本发明并不限于存在没有铪和钇的层的情形。特别地，在本发明的上下文中，两个层均可以含有铪和/或钇，或者在三个层的情形中，两个层或全部三个层可以含有铪和/或钇。
如果本发明的超级合金组件的涂层除了铝之外还包括铪，则铪含量优选最多为该层组分重量的大约3%。这样的层例如可以通过包含占浆料重量70%的粘结剂和最多1%的铪的浆料来得到。
如果该层除了铝之外还包括钇，则钇含量优选最多为该层组分重量的大约0.17%。这样的层可以通过使用包含占浆料重量最多70%的粘结剂和0.05%(5ppm)的钇的浆料来得到。
根据本发明进一步发展，该涂层材料包括至少一层。该至少一层的涂层材料除了铝之外还包括硅。该层的硅含量可为该层组分重量的1%-40%。需要注意的是，所有含铝层也可以含有硅。
通过对本发明接下来的实施方式的说明以及结合附图可以更清晰的了解本发明进一步的特点，性能和优点。
附图说明
图1显示了本发明组件的第一实施方式。
图2显示了本发明组件的第二实施方式。
图3显示了本发明组件的第三实施方式。
具体实施方式
在图1中显示了本发明超级合金组件的第一实施方式。图中显示了该组件的截面粗略示意图，该组件可以是燃气涡轮组件，例如涡轮叶片，或者高温气体流通路径的衬板元件。附图显示了超级合金1，其上涂覆有涂层3。超级合金1可以特别是EP 1204776B1，EP1306454B1，EP 1319729A1，WO 99/67435A1或WO 00/44949A1中披露的超级合金中的一个。
具体根据EP 1204776B1，超级合金1可以由镍基超级合金制成，其组成包括以下元素，以重量百分比计：11-13%铬，3-5%钨，0.5-2.5%钼，3-5%铝，3-5%钛，3-7%钽，0-12%钴，0-1%铌，0-2%铪，0-1%锆，0-0.05%硼，0-0.2%碳，1-5%铼，0-5%钌，其余为镍和杂质。
从EP 1306454B1中已知一种用于在高温下保护组件抗腐蚀和抗氧化的保护性涂层，其由以下元素(详细为重量百分比)构成：0.5-2%铼，15-21%铬，9-11.5%铝，0.05-0.7%钇和/或至少一种由钪和稀土构成的组中的等效金属，0-1%钌，以及其余为钴和/或镍以及与生产相关的杂质。
根据EP 1319729A1，超级合金1可以由镍基超级合金制成，其组成包括以下元素，以重量百分比计：9-10.75%铬，3-5%钨，0.5-2.5%钼，3-5%铝，3-5%钛，3-7%钽，0-12%钴，0-1%铌，0-2%铪，0-1%锆，0-0.05%硼，0-0.2%碳，选自由铼、钌构成的组的至少一种元素，其中使用1-5%铼和/或0.1-5%钌，其余为镍和杂质。
镍铝合金涂层也可以通过Sermatech® International公司下的品牌“SermaLoy® J”和“SermaLoy® 1515”来提供。“SermaLoy® J”为浆料用铝化物扩散涂层，其用于保护燃气轮机热段组件和承受热腐蚀的工业组件。其涂覆于组件表面，接着进行扩散。结果获得紧密附着于部件表面的涂层。“SermaLoy® 1515”被设计用于保护高强度低铬镍基合金制成的组件能够极好地抵抗高温和低温的热腐蚀以及氧化。其专门设计来保护涡轮叶片的内部冷却通道。
涂层3为铝化物-硅化物涂层，其包含铪和钇。铪含量为层组分重量的大约3%，而钇含量为层组分重量的大约0.17%。
对应于根据权利要求的“第一层”，涂层3通过浆料渗铝工艺形成。在该工艺中，固体成分与有机粘结剂混合从而形成能够涂覆于超级合金1表面的浆料，其中固态成分包括铝以及任选地包括含量为固体成分总重量1%-40%的硅，有机粘结剂包括铬酸盐和磷酸盐。浆料中加入含量为浆料重量1%的铪粉末。更进一步，浆料中加入含量为浆料重量0.05%的钇粉末。当形成浆料时，仔细控制浆料中的硫含量为低于5ppm的非常低的痕量。
浆料随后被涂覆于超级合金组件的表面，例如喷涂浆料于接收部分。将其涂覆于组件表面之后，通过大约300℃的热处理固化浆料。然后通过在700℃至1100℃温度下的扩散热处理，固化浆料中含有的铝，任选的硅，铪和钇扩散到超级合金1的表面中。通过使用扩散热处理，铝，任选的硅，钇和铪纳入到超级合金1的表面层中，同时有机粘结剂的的溶剂得到挥发。粘结剂的未挥发残留成分可以很容易地通过机械手段例如对表面轻微喷砂来去除。
图2显示了本发明组件的第二实施方式。该实施方式与第一实施方式的不同之处在于第二涂层5涂覆于第一实施方式的涂层3上。因此，涂层3被设置在超级合金1和第二涂层5之间。对于第二实施方式，涂层3也可以被称为第一涂层3。第二涂层5原则上可以为对于第一实施方式的第一涂层3所述的涂层。然而，也可以提供既不含钇也不含铪的涂层作为第二涂层5。
在第二实施方式的变体中，第一涂层3只含有铪和钇元素中的一种，而第二涂层含有这些元素中的另一种。例如，第一涂层3可以含有铪，而第二涂层5含有钇。这些层可以通过对于第一实施方式所述的用于制备涂层3的方法来制备，如果只有铪或钇被加入到各自的浆料中的话。
图3中显示了本发明超级合金组件的第三实施方式，第三实施方式的涂层为三层涂层，其中从超级合金基体1看起，第一涂层7（对应于根据权利要求的“第二层”）既不含铪也不含钇，第二涂层9（对应于根据权利要求的“第一层”）含钇和铪，第三涂层11（对应于根据权利要求的“第三层”）既不含钇也不含铪。所有的层可以通过上述的工艺来制备，只需向各自的浆料中添加或不添加钇和/或铪。
图3所示的实施方式可以更改为第一涂层7、第二涂层9和第三涂层11中的任意一个可以含有元素铪和钇中的至少一种。特别是所有三层可以含有钇和/或铪。另一方面也可以例如第一涂层7既不含钇也不含铪，第二涂层9含有钇，而第三涂层11含有铪。
应注意对每一涂层，上述的热处理或激光处理将在所述涂层包括超过一个涂层时进行实施。
在全部三个实施方式中，铪含量优选最多为该层组分重量的大约3%和/或钇含量最多为层组分重量的大约0.17%，这例如可以通过使用含下列组分的浆料来实现：按浆料重量计70%的有机粘结剂，1%重量的铪和/或0.05%重量的钇，其余为固体成分，其中固体成分包括铝以及可以进一步包括占固体含量重量的1%至40%、特别是占固态重量的1%至大约20%、以及在特殊实施方式中占固态含量重量的大约10%至15%的硅。

Claims (20)

1.用于对超级合金组件渗铝的浆料组合物，其包含：
包括铬酸盐或磷酸盐中的至少一种的有机粘结剂，和
包括铝和硅以及铪或钇二者中的至少一种的固体成分。
2.权利要求1的浆料组合物，其中该浆料组合物包含铪和钇二者。
3.权利要求1的浆料组合物，其中该浆料组合物包含铪，且其中铪的含量最多为浆料组合物重量的2.5%。
4.权利要求3的浆料组合物，其中铪的含量最多为浆料组合物重量的1%。
5.权利要求1的浆料组合物，其中该浆料组合物包含钇，且其中钇的含量最多为浆料组合物重量的0.1%。
6.权利要求5的浆料组合物，其中钇的含量最多为浆料组合物重量的0.05%。
7.权利要求1的浆料组合物，其中硅的含量为总共固体成分重量的1%至40%。
8.权利要求6的浆料组合物，其中硅的含量为总固体成分重量的1%至20%。
9.权利要求8的浆料组合物，其中硅的含量为总固体成分重量的10%至15%。
10.权利要求1的浆料组合物，其中有机粘结剂的含量最多为浆料组合物重量的70%。
11.权利要求1的浆料组合物，其中铪或钇中的至少一种为选自粉末、片状、屑状及其组合的形式。
12.权利要求1的浆料组合物，其进一步包含不大于浆料组合物的5ppm的硫含量。
13.权利要求1的浆料组合物，其中所述固体成分由铝和硅以及铪或钇二者中的至少一种组成。
14.权利要求1的浆料组合物，其中所述固体成分由铝、硅、铪和钇组成。
15.权利要求1的浆料组合物，其中所述固体成分由铝、硅、铪、钇和硫组成，其中硫含量不大于浆料组合物重量的5ppm。
16.权利要求1的浆料组合物，其中有机粘结剂包括铬酸盐和磷酸盐二者。
17.通过一种或多种浆料组合物在基材上形成涂层的方法，该方法包括；
向基材上施加第一浆料组合物，该第一浆料组合物包含包括铬酸盐或磷酸盐中的至少一种的有机粘结剂和包括铝和硅以及铪或钇二者中的至少一种的固体成分；和
将所述第一浆料组合物加热到能有效形成含铝和硅以及铪或钇二者中的至少一种的第一层的程度。
18.权利要求17的方法，其进一步包括；
向基材上施加第二浆料组合物，该第二浆料组合物包含包括铬酸盐或磷酸盐中的至少一种的有机粘结剂和包括铝和硅但不包括铪或钇的固体成分；和
将所述第二浆料组合物加热到能有效地在所述第一层上形成含铝和硅但不含铪或钇的第二层的程度。
19.权利要求17的方法，其中第一浆料组合物包含铪和钇二者，且其中第一浆料组合物中的硅含量为总固体成分重量的1%-40%。
20.权利要求17的方法，其中所述加热第一浆料组合物包括：
加热第一浆料组合物到至少约300℃的温度，以固化第一浆料组合物；和
加热第一浆料组合物到700℃至1100℃的温度，以使铝和硅以及铪或钇二者中的至少一种扩散到基材的表面层中。
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