CN1231544C - 具有抗氧化性和抗疲劳性的金属涂料 - Google Patents

具有抗氧化性和抗疲劳性的金属涂料 Download PDF

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CN1231544C
CN1231544C CNB031360645A CN03136064A CN1231544C CN 1231544 C CN1231544 C CN 1231544C CN B031360645 A CNB031360645 A CN B031360645A CN 03136064 A CN03136064 A CN 03136064A CN 1231544 C CN1231544 C CN 1231544C
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chromium
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R·A·贝尔斯
A·A·内策尔
A·坎
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Abstract

本发明涉及一种沉积在汽轮机组件上的金属涂料。该金属涂料含有：至多18wt%的钴；3.0～18wt%的铬；5.0～15wt%的铝；0.1～1.0wt%的钇；至多0.6wt%的铪；至多0.3wt%的硅；3.0～10wt%的钽；至多9.0wt%的钨；1.0～6.0wt%的铼；至多10wt%的钼和余量的镍。

Description

具有抗氧化性和抗疲劳性的金属涂料
技术领域
本发明涉及一种保护高温燃气轮机组件的抗氧化和抗疲劳金属涂料。
背景技术
在过去，研制出了各种对高温燃气轮机组件进行氧化保护的金属涂料。这些涂料通常是基于含镍或钴贱金属材料的各种不同铝合物(aluminide)组合物。另一选择，它们基于带有MCrAlY基底的涂覆沉积物，其中M是镍、钴、铁或者它们的结合物。这些涂料体系存在缺陷，阻碍了其在更新的先进轮机组件中的使用。虽然铝合物具有良好的抗疲劳性，但扩散后的铝合物通常缺少抗高温氧化性(华氏2000度以上)。涂覆的MCrAlY涂层具有严重的疲劳缺陷，这限制了它们的应用。在MCrAlY涂料中添加活泼的元素，不仅能提供优良的抗氧化性，而且能使其成为良好的绝热陶瓷涂层用粘合层。虽然铝合物涂料与MCrAlY涂料应用广泛，但是，要将一种新的兼具以上两种涂料最佳特性的涂料很快应用到先进的轮机组件上，就要使疲劳生、拉伸性(pull weight)和氧化性都减少到最低。
发明内容
本发明的一个目的在于提供一种具有优良抗氧化性和抗疲劳性的金属涂料组合物。
本发明的另一目的在于提供一种涂料组合物，它能减少涂料与普通轮机合金之间的热膨胀失调。
以上所述的两个目的通过本发明的涂料都将实现。
本发明提供的金属涂料含有：至多18wt％的钴；3.0～18wt％的铬；5.0～15wt％的铝；0.1～1.0wt％的钇；至多0.6wt％的铪；至多0.3wt％的硅；3.0～10wt％的钽；至多9.0wt％的钨；1.0～6.0wt％的铼；至多10wt％的钼和余量的镍。本发明的涂料组合物中钽和钨的总含量为3.0～16wt％。
关于本发明中兼具抗氧化和抗疲劳性能的金属涂料的其他具体内容，及其他相关目的和优点，将在下文中给予具体的描述。
具体实施方式
轮机的组件是由镍基合金、钴基合金和铁基合金制成。由于这些器件需在特别高的温度下工作，因此为它们提供保护涂层是很有必要的。该涂料必须是这样一种组合物，它能最大限度地减少施用了它的轮机组件所受的疲劳影响，同时又要尽可能地提供最大的抗氧化性。并且这种涂料能使涂层和形成轮机组件的合金之间的热膨胀失调达到最小。这种热膨胀失调正是导致MCrAlY涂层产生差的疲劳性能的原因之一。
依照本发明所提供的金属涂料，它能减少热失调，并具备所期望的抗氧化性和抗疲劳性。这些金属涂料具有基本构成如下的组成：至多18wt％的钴；3.0～18wt％的铬；5.0～15％wt的铝；0.1～1.0wt％的钇；至多0.6wt％的铪；至多0.3wt％的硅；3.0～10wt％的钽；至多9.0wt％的钨；1.0～6.0wt％的铼；至多10wt％的钼和余量的镍。在这些涂料中钽和钨的总含量为3.0～16wt％。
在上文提到的宽泛定义的涂料组合物中，第一组特别适用于轮机组件的涂料组合物的基本构成是：至多15wt％，优选为2.0wt％或更少的钴；5.0～18wt％，优选为10～15wt％的铬；5.0～12wt％，优选为6.0～10wt％的铝；0.1～1.0wt％，优选为0.2～0.7wt％的钇；至多0.6wt％，优选为0.2～0.6wt％的铪；至多0.3wt％，优选为0.1wt％或更少，更优选为0.001～0.1wt％的硅；3.0～10wt％，优选为5.0～7.0wt％的钽；至多5.0wt％，优选为1.0～4.0wt％的钨；1.0～6.0wt％，优选为1.0～3.5wt％的铼；至多10wt％，优选为4.0wt％或更少的钼和余量的镍。在这些金属涂料中钽和钨的总含量为3.0～12wt％，优选为5.0～9.0wt％。
在第一组涂料中，特别适用的涂料组合物由：12.5wt％的铬；8.0wt％的铝；0.4～0.7wt％的钇；0.4wt％的铪；6.0wt％的钽；2.0wt％的钨；2.0wt％的铼和余量的镍组成。
第二组特别有用的金属涂料组合物含：2.0～18wt％，优选为8.0～12wt％的钴；3.0～10wt％，优选为4.0～6.5wt％的铬；5.5～15wt％，优选为7.5～12.5wt％的铝；0.1～1.0wt％，优选为0.2～0.7wt％的钇；至多0.6wt％，优选为0.2～0.6wt％的铪；至多0.3wt％的硅；3.0～10wt％，优选为5.0～7.0wt％的钽；1.0～9.0wt％，优选为4.2～5.8wt％的钨；1.0～5.0wt％，优选为2.3～3.7wt％，更优选3.0wt％的铼；0.2～4.0wt％，优选为1.4～2.0wt％，更优选1.7wt％的钼和余量的镍。在这些涂料中钽和钨的总含量为3.0～12wt％，优选为5.0～9.0wt％。
在本发明优选的金属涂料中，所述的钴的含量为10.5wt％；铬的含量为5.0wt％；所述铝的含量为9.0wt％；所述钇的含量为0.4～0.7wt％；所述铪的含量为0.4wt％；所述钽的含量为6.0wt％。
在第二组涂料中，特别有用的涂料组合物由：10.5wt％的钴；5.0wt％的铬；9.0wt％的铝；0.4～0.7wt％的钇；0.4wt％的铪；0.1wt％的硅；6.0wt％的钽；5.0wt％的钨；3.0wt％的铼；1.7wt％的钼和余量的镍组成。
—种导致涂料抗疲劳性能差的原因是涂层过厚。典型的覆盖涂层沉积方法包括热喷镀法，如低压等离子喷镀法(LPPS)，用这种方法所产生的涂层厚度在0.004～0.012英寸之间。利用阴极电弧等离子气相沉积技术，可以使如前所述组合物的涂层厚度达到0.002英寸。在美国专利5,972,185；5,632,078；6,036,828；5,792,267和6,224,726中，对采用阴极电弧等离子气相沉积法施涂本发明涂料的技术进行了讨论，所有这些专利在此引入作为参考。备选的沉积方法包括如磁控管阴极溅射等离子气相沉积法和电子束等离子气相沉积法之类其它等离子气相沉积法，都可在本发明中使用。当涂层厚度的影响不存在时，各种热喷镀技术如低压等离子喷镀技术和HVOF(高速氧燃料)技术都可以使用。
含有本发明组合物的涂层已被证明具有和最佳抗疲劳的扩散铝合物涂料一样的抗热疲劳性。下面将用图表说明在华氏2100度利用燃烧装置，将本发明组合物与其他涂料组合物进行循环氧化实验所得的结果。
              在华氏2100度燃烧装置中的循环氧化实验
样品编号#     厚度(密耳)     涂层寿命(小时)   涂层寿命**  系统失效(小时) 系统失效**
    701     2.95     2320     1573     2713     1839
    702     3.1     4105     2648     6285     4055
    703     2.7     1591     1179     1932     1431
    699     3.3     3060     1855     3622     2195
    700     2.15     1170     1088     1399     1301
    697     2.4     982     818     1045     871
    695     2.8     826     590     1315     939
    696     2.45     676     552     805     657
    PWA275     2     115     115     366     366
**涂料厚度统一为2密耳。
编号为701的样品是由以下成分构成：12.5wt％的铬；8.0wt％的铝；0.4～0.7wt％的钇；0.4wt％的铪；6.0wt％的钽；2.0wt％的钨；2.0wt％的铼和平衡量的镍。编号为702的样品的组成成分：10.5wt％的钴；5.0wt％的铬；9.0wt％的铝；0.4～0.7wt％的钇；0.4wt％的铪；0.1wt％的硅；6.0wt％的钽；5.0wt％的钨；3.0wt％的铼；1.7wt％钼和平衡量的镍。
编号为703的样品组成为：7.0wt％的铬；6.0wt％的铝；5.5wt％的钨；4.0wt％的钽；2.0wt％的铼；4.0wt％的钌；0.5wt％的钼；0.4wt％的铪；0.25wt％的钇和平衡量的镍。
编号为699的样品是NiCoCrAlY与铼和钽的组合物。编号为700，697，695和696的样品是NiAl与2～4wt％铬，0.2～0.6wt％钇和0.4wt％铪的组合物。标为PWA275的样品是传统的低活性NiAl铝合物。
实验条件是：每小时在华氏2100度下保持57分钟，然后强制通空气冷却3分钟。燃烧装置使用了预热的混有JP8喷射燃料的压缩空气，以在动态环境中加热样品。
显而易见，本发明所提供的抗氧化和抗疲劳金属涂料将完全满足上文所提到的各种目的、装置和优点。尽管在上文的具体实施方案中对本发明进行了描述，但是，本领域技术人员阅读了上述的描述后，很容易对本发明作出其它选择、修改和变化。故这些选择、修改和变化也落入本发明的附属权利要求书范围内。

Claims (34)

1、一种具有抗氧化性和抗疲劳性的金属涂料，它含有由：至多18wt％的钴；3.0～18wt％的铬；5.0～15wt％的铝；0.1～1.0wt％的钇；至多0.6wt％的铪；至多0.3wt％的硅；3.0～10wt％的钽；至多9.0wt％的钨；1.0～6.0wt％的铼；至多10wt％的钼和余量的镍组成的组合物。
2、如权利要求1所述的金属涂料，其中所述的钽和钨的总含量在3.0～16.0wt％之间。
3、如权利要求1所述的金属涂料，其中所述的钴的含量少于15wt％；所述铬的含量为5.0～18wt％；所述铝的含量为5.0～12wt％；所述钨的含量少于5.0wt％。
4、如权利要求1所述的金属涂料，其中所述的钴的含量为2.0～18wt％；所述铬的含量为3.0～10wt％；所述铝的含量为5.5～15wt％；所述铼的含量为1.0～5.0wt％；所述钼的含量为0.2～4.0wt％。
5、如权利要求1所述的金属涂料，其中所述的钽和钨的总含量在4.0～16wt％之间。
6、如权利要求1所述的金属涂料，其含有由：至多15wt％的钴；5.0～18wt％的铬；5.0～12wt％的铝；0.1～1.0wt％的钇；至多0.6wt％的铪；至多0.3wt％的硅；3.0～10wt％的钽；至多5.0wt％的钨；1.0～6.0wt％的铼；至多10wt％的钼和余量的镍组成的组合物。
7、如权利要求6所述的金属涂料，其中所述的钽和钨的总含量在3.0～12wt％之间。
8、如权利要求6所述的金属涂料，其中所述的钽和钨的总含量在5.0～9.0wt％之间。
9、如权利要求6所述的金属涂料，其中所述的钴的含量少于2.0wt％；所述铬的含量为10～15wt％；所述铝的含量为6.0～10wt％；所述钇的含量为0.2～0.7wt％；所述铪的含量为0.2～0.6wt％；所述硅的含量至多为0.1wt％；所述钽的含量为5.0～7.0wt％。
10、如权利要求6所述的金属涂料，其中所述的铬的含量为12.5wt％；铝的含量为8.0wt％。
11、如权利要求9所述的金属涂料，其中所述的钇的含量为0.4～0.7wt％；所述铪的含量为0.4wt％。
12、如权利要求6所述的金属涂料，其中所述的铼的含量为1.0～3.5wt％。
13、如权利要求12所述的金属涂料，其中所述的铼的含量为2.0wt％。
14、如权利要求6所述的金属涂料，其中所述的钼的含量至多为4.0wt％。
15、如权利要求1所述的金属涂料，其由：至多2.0wt％的钴；10～15wt％的铬；6.0～10wt％的铝；0.2～0.7wt％的钇；0.2～0.6wt％的铪；0.001～0.1wt％的硅；5.0～7.0wt％的钽；1.0～4.0wt％的钨；1.0～3.5wt％的铼；至多4.0wt％的钼和余量的镍组成。
16、如权利要求15所述的金属涂料，其中所述的钨和钽的总含量在5.0～9.0wt％之间。
17、如权利要求1所述的金属涂料，其由：12.5wt％的铬；8.0wt％的铝；0.4～0.7wt％的钇；0.4wt％的铪；6.0wt％的钽；2.0wt％的钨；2.0wt％的铼和余量的镍组成。
18、如权利要求1所述的金属涂料，其由：2.0～18wt％的钴；3.0～10wt％的铬；5.5～15wt％的铝；0.1～1.0wt％的钇；至多0.6wt％的铪；至多0.3wt％的硅；3.0～10wt％的钽；1.0～9.0wt％的钨；1.0～5.0wt％的铼；0.2～4.0wt％的钼和余量的镍组成。
19、如权利要求18所述的金属涂料，其中所述的钽和钨的总含量在4.0～16wt％之间。
20、如权利要求18所述的金属涂料，其中所述的钽和钨的总含量在7.0～12wt％之间。
21、如权利要求18所述的金属涂料，其中所述的钽和钨的总含量为11wt％。
22、如权利要求18所述的金属涂料，其中所述的钴的含量为8.0～12wt％；所述铬的含量为4.0～6.5wt％；所述铝的含量为7.5～12.5wt％；所述钇的含量为0.2～0.7wt％；所述铪的含量为0.2～0.6wt％；所述硅的含量至多为0.1wt％；所述钽的含量为5.0～7.0wt％。
23、如权利要求18所述的金属涂料，其中所述的钴的含量为10.5wt％；铬的含量为5.0wt％；所述铝的含量为9.0wt％；所述钇的含量为0.4～0.7wt％；所述铪的含量为0.4wt％；所述钽的含量为6.0wt％。
24、如权利要求18所述的金属涂料，其中所述的钨的含量为4.2～5.8wt％；所述铼的含量为2.3～3.7wt％；所述钼的含量为1.4～2.0wt％。
25、如权利要求18所述的金属涂料，其中所述的钨的含量为5.0wt％；所述铼的含量为3.0wt％；所述钼的含量为1.7wt％。
26、如权利要求1所述的金属涂料，其含有由：8.0～12wt％的钴；4.0～6.5wt％的铬；7.5～12.5wt％的铝；0.2～0.7wt％的钇；0.2～0.6wt％的铪；至多0.3wt％的硅；5.0～7.0wt％的钽；4.2～5.8wt％的钨；2.3～3.7wt％的铼；1.4～2.0wt％的钼和余量的镍组成的组合物。
27、如权利要求26所述的金属涂料，其中所述的钽和钨的总含量在7.0～12wt％之间。
28、如权利要求1所述的金属涂料，其由：10.5wt％的钴；5.0wt％的铬；9.0wt％的铝；0.4～0.7wt％的钇；0.4wt％的铪；0.1wt％的硅；6.0wt％的钽；5.0wt％的钨；3.0wt％的铼；1.7wt％的钼和余量的镍组成。
29、一种在基底上沉积覆盖涂层的方法，它包括：
提供由至少一种镍基、钴基和铁基的金属材料形成的基底材料；并
在所述基底上沉积涂料，该涂料含有由：至多18wt％的钴；3.0～18wt％的铬；5.0～15wt％的铝；0.1～1.0wt％的钇；至多0.6wt％的铪；至多0.3wt％的硅；3.0～10wt％的钽；至多9.0wt％的钨；1.0～6.0wt％的铼；至多10wt％的钼和余量的镍组成的组合物。
30、如权利要求29所述的沉积覆盖涂层的方法，其中所述的沉积步骤采用阴极电弧法或低压等离子喷涂法进行。
31、如权利要求29所述的方法，其中所述的沉积步骤包括：沉积含有由以下成分组成的组合物的涂料：至多15wt％的钴；5.0～18wt％的铬；5.0～12wt％的铝；0.1～1.0wt％的钇；至多0.6wt％的铪；至多0.3wt％的硅；3.0～10wt％的钽；至多5.0wt％的钨；1.0～6.0wt％的铼；至多10wt％的钼和余量的镍。
32、如权利要求29所述的方法，其中所述的沉积步骤包括：沉积含有由以下成分组成的组合物的涂料：至多2.0wt％的钴；10～15wt％的铬；6.0～10wt％的铝；0.2～0.7wt％的钇；0.2～0.6wt％的铪；至多0.1wt％的硅；5.0～7.0wt％的钽；1.0～4.0wt％的钨；1.0～3.5wt％的铼；至多4.0wt％的钼和余量的镍。
33、如权利要求29所述的方法，其中所述的沉积步骤包括：沉积含有由以下成分组成的组合物的涂料：2.0～18wt％的钴；3.0～10wt％的铬；5.5～15wt％的铝；0.1～1.0wt％的钇；至多0.6wt％的铪；至多0.3wt％的硅；3.0～10wt％的钽；1.0～9.0wt％的钨；1.0～5.0wt％的铼；0.2～4.0wt％的钼和余量的镍。
34、如权利要求29所述的方法，其中所述的沉积步骤包括：沉积含有由以下成分组成的组合物的涂料：8.0～12wt％的钴；4.0～6.5wt％的铬；7.5～12.5wt％的铝；0.2～0.7wt％的钇；0.2～0.6wt％的铪；至多0.3wt％的硅；5.0～7.0wt％的钽；4.2～5.8wt％的钨；2.3～3.7wt％的铼；1.4～2.0wt％的钼和余量的镍。
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