CN102482757A - 超合金元件和其改进方法 - Google Patents

超合金元件和其改进方法 Download PDF

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CN102482757A
CN102482757A CN2010800160231A CN201080016023A CN102482757A CN 102482757 A CN102482757 A CN 102482757A CN 2010800160231 A CN2010800160231 A CN 2010800160231A CN 201080016023 A CN201080016023 A CN 201080016023A CN 102482757 A CN102482757 A CN 102482757A
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P·M·沃克
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Abstract

本发明涉及通过选自Hf，La，Y的至少一种添加剂来改进元件(1)的方法。所述至少一种添加剂引入元件(1)的表面层(7)中。

Description

超合金元件和其改进方法
本发明涉及超合金元件和改进超合金元件的方法。
暴露于热腐蚀性气体的元件，如暴露于热和腐蚀性燃烧气体的燃气轮机(gas turbine)元件，一般都采用在升高的温度具有高强度的超合金制备。此类超合金一般为基于镍(Ni)，钴(Co)或铁(Fe)。虽然超合金在高达1200℃或更高具有高强度，它们仍然需要防止氧化和/或腐蚀。通常采用形成于超合金元件表面或所谓MCrAlY-覆盖涂层(overlay coating)的氧化铝皮(alumina scale)来提供该保护，其中M代表镍，钴或铁，Y代表钇(Y)，铪(Hf)，或稀土元素。在制备覆盖涂层期间，铝被氧化并形成紧密粘连的氧化铝皮，其保护元件不被氧化和/或腐蚀。此类涂层为，比如在EP0 486 489B1，EP 0 786 017B1，或EP 1306 456A1中公开。从US 4 615 864中可知，在MCrAlY组合物中添加铪，钇或镧(La)是有利，因为这些物质的氧化物协助销入(spinning)氧化铝皮。
如果涂层能够提供隔热(如燃气轮机的涡轮机螺旋桨的隔热)，其也可称为热障涂层(Thermal Barrier Coating)(TBC)。
鉴于前述的现有技术，本发明的目的为提供一种改进超合金元件如燃气轮机元件的方法和提供如此改进的元件。
该目的通过如权利要求1限定的改进超合金元件的方法和如权利要求14限定的超合金元件来实现。从属权利要求包含本发明的进一步扩展。
在本发明的方法中，超合金元件，尤其是基于镍的超合金元件，基于钴的超合金元件或基于铁的超合金元件通过选自Hf，La和Y的组的至少一种添加剂改进。根据本发明，至少一种添加剂引入元件的表面层。表面层深度可为0.5mm或更小，优选0.25mm或更小。
引入至少一种选自铪，镧和钇的组的添加剂进入超合金元件的表面层中改进了元件，在于后续施加的包括MCrAlY涂层的热障涂层(TBC)由于所述添加剂而显示出改进的抗氧化性。抗氧化性的改进提高了涂层的寿命。另外，MCrAlY涂层中保护性氧化物皮的销入也得到了改进，其也改进了涂层的寿命。当在超合金元件的大块铸件材料中以大的量加入添加剂时，热障涂层施加可能会带来困难，而通过仅在表面层中添加添加剂，添加剂在此因此可以展现其益处而在热障涂层施加时避免该问题的产生。
值得注意的是，在本发明范围内只需要有一种选自铪，镧和钇的组的添加剂存在。然而，本发明的范围也可包括至少两种选自铪，镧和钇的组的添加剂存在，或者全部三种元素都存在。如果存在至少两种选自上述组的添加剂，所述添加剂可以依次引入元件的表面层，或者它们可以同时引入。在全部三种元素都存在的情况下，全部三种添加剂可以依次引入或者同时引入。进一步的变型为，同时引入两种元素，而第三种元素在其它两种之前或之后引入。
如果铪用作添加剂，引入表面层的量为表面层材料组成的至多5重量％，优选为至多1重量％。如果钇用作添加剂，引入表面层的量为表面层材料组成的至多0.2重量％，优选是至多0.05重量％。如果镧用作添加剂，引入表面层的量为表面层材料组成的至多0.2重量％，优选是至多0.05重量％。
所述至少一种添加剂可通过将其熔融进入表面而引入到表面层中。可选地，所述至少一种添加剂可通过将其扩散至表面中而引入表面层。
将添加剂熔融进入表面层可通过加热表面层实现，尤其是局部加热表面，比如，激光加热方法。局部加热表面使得能够局部熔融该表面及使熔融的表面以定向(directionally oriented)的方式固化，由此，如果本发明的方法将要应用于单晶或定向固化的超合金元件，则添加剂引入的该方法是有益的。在这样的局部加热方法中，表面将通过加热方法扫描，如通过上述的激光。
在添加剂将扩散到超合金元件的表面中的情况下，扩散可以通过本领域技术人员所熟知的常见加热处理实现。
为了实现熔融或扩散工艺，能够将包含至少一种添加剂的浆料基质施加至表面。随后局部或全局加热在其上施加了所述浆料的表面。此类浆料基质可有利地含有超合金的基体材料，即镍(在基于镍的超合金情况下)、钴(在基于钴的超合金情况下)和铁(在基于铁的超合金情况下)，和有机粘合剂。有机粘合剂可以特别是铬酸盐/酯和磷酸盐/酯有机粘合剂。
根据本发明方法的进一步，在添加剂已经引入元件的表面层中之后，将抗氧化和/或抗腐蚀涂层，如以热障涂层的形式，施加到超合金元件的表面上。这样的热障涂层有利地包含MCrAlY涂层，从而通过引入所述超合金元件表面层中的添加剂实现上述的协助氧化铝皮销入的效果。
本发明的超合金元件具有包含选自铪，镧和钇的组的表面层。该表面层可具有0.5mm或更小，优选0.25mm或更小的深度。由此类超合金元件能够实现的优点已经关于本发明方法进行了论述。因此，本发明超合金元件可达到的优点可参照说明书涉及本发明方法的部分。
该超合金元件可在表面层上包含抗氧化和/或抗腐蚀涂层。该涂层可以特别地是包含MCrAlY涂层的热障涂层。
另外，本发明的超合金元件特别地可由作为单晶材料或定向固化材料的超合金材料制备。
本发明的其它特征、性能和优点将根据以下本发明具体实施方案结合附图的描述变得清晰。
图1，概要显示了改进超合金元件的本发明方法的实施方案。
图2，显示了本发明超合金元件的实施方案。
参照图1说明本发明通过至少一种选自铪，镧和钇的组的添加剂来改进超合金元件的本发明方法的一个实施方案。在本发明方法中，所述至少一种添加剂引入元件1的表面层，该元件可以是燃气轮机元件，如涡轮机轮叶或叶片或燃气轮机中热气通道的管线元件。根据图1描述的实施方案，添加剂通过包含该添加剂的浆料3的方式引入超合金元件1的表面层7中。浆料施加到元件1的表面上，随后加热浆料3以使添加剂熔融进入元件的表面层7中。本实施方案中，通过局部加热工艺实施加热，其中局部加热的位置在表面上移动。
在本发明方法所述实施方案的第一步中，浆料形成为包含固体内含物和有机粘合剂。所述固体内含物包括例如粉末形式、薄片形式等的该超合金元件的基体材料和一定含量的铪和/或镧和/或钇。如果，例如该超合金元件由基于镍的超合金制备，该固体内含物将包含镍，其将作为固体内含物的主要部分。该有机粘合剂可为例如有机粘合剂，包括铬酸盐/酯和磷酸盐/酯。有机粘合剂可以以浆料的40重量％-70重量％的量存在。
铪的量为浆料的0-2.5重量％，优选0-1重量％。钇的量可以为浆料的0-0.1重量％，优选0-0.05重量％。镧的量可为浆料的0-0.1重量％，优选0-0.05重量％。浆料的余量将基本上为超合金的基体材料。制备该浆料通过将固体内含物加入有机粘合剂随后彻底混合形成均一的浆料而进行。
形成浆料后，该浆料施加到超合金元件1的表面上以形成浆料层3，如图1所示。可以通过任何合适的方法将浆料施加到超合金元件1的表面上，如通过将浆料喷洒到元件1的表面上，并将其上施加了所述浆料的元件在300-400℃之间(如大约350℃)进行热处理以固化所述浆料。
当已经通过加热处理的方式在超合金元件1的表面上形成固化的浆料层3后，通过激光束5扫描所述表面以局部熔融所述浆料的固体内含物和超合金元件1的表面层7。
在本实施方案中，超合金元件1是定向固化的元件，其中结晶晶粒沿共同的择优取向延伸。但是，其也可以是单晶元件或没有任何择优晶向的元件。
在加热过程中，激光束5在超合金元件1的表面上沿着由超合金材料中晶体优选的扩展方向所决定的方向移动。图1中的箭头示意性地显示了该移动。通过谨慎选择移动的方向和加热斑单位表面积的激光束5的能量，本领域技术人员能够实现通过激光束5产生的熔体适应于晶体结构和下层固体晶体在固化过程中的取向，来适应超合金元件1主体的定向固化结构。
注意，虽然本实施方案的超合金元件1是定向固化元件，它也可以是单晶元件，因为局部加热单晶超合金元件的表面能以如上所述相同的方式使用，使得熔体固化，且所述超合金元件1的主体材料具有连续晶体结构，以使固化后表面层7与元件1的主体形成单晶。另外，应当注意的，上述的工艺步骤原则上也可以用于不具有定向固化或单晶结构的超合金元件。
在熔融的浆料固体内含物和超合金元件1的表面层7的再固化的过程中，将铪和/或镧和/或钇引入到表面层7中。
在通过激光束5加热的过程中，浆料中的有机成分挥发或(如果它们不挥发的话)变脆以使其能够很容易地从表面去除，如通过对表面稍加喷砂。
在本发明方法的所述实施方案中，添加剂即铪和/或镧和/或钇，熔融进入到超合金元件的表面层7中。然而，也可以通过扩散工艺将添加剂引入到表面层7中。在此情况中，在表面上具有固化的浆料层3的超合金元件1将经受热处理，其温度将选择为例如引起添加剂扩散进入超合金元件1的表面层7中。当不需要表面层7具有定向固化或单晶结构时，将添加剂引入表面层7中的该方法是特别有用的。
在铪和/或镧和/或钇已经引入到超合金元件1的表面层7中后，将包含陶瓷涂层11的热障涂层9施加到元件表面上。该热障涂层可以是，例如，晶体结构至少部分地由钇稳定的氧化锆层11以及位于氧化锆层11和超合金元件1的表面层7之间的MCrAlY涂层13。MCrAlY涂层和钇稳定的氧化锆涂层以及施加此类涂层的方法，为本领域所公知，因此不在此处说明。在施加MCrAlY涂层13的过程中，形成保护性的氧化铝皮，其销入至超合金元件1的表面。铪和/或钇和/或镧协助销入该保护性皮。
依据所述实施方案，本发明方法的结果是本发明的超合金元件1，如图2所示。可以看出，超合金元件1具有包含铪和/或钇和/或镧的表面层7以及施加在其上的热障涂层9。然而，本发明的超合金元件不需要具有所述热障涂层或可以具有不同种类的抗氧化和/或抗腐蚀涂层系统，形成氧化铝皮。
依据本发明，通过引入铪和/或铪和/或钇和/或镧到元件的表面层中，改进了超合金元件。特别地，这使得能够改进施加在此类改进的超合金元件上的抗氧化和/或抗腐蚀涂层性涂层。

Claims (15)

1.通过选自Hf，La，Y的组的至少一种添加剂改进超合金元件(1)的方法，其中将所述至少一种添加剂引入所述元件的表面层(7)中。
2.如权利要求1所述的方法，其中将选自Hf，La，Y的组的至少两种添加剂引入所述元件(1)的表面层(7)中。
3.如权利要求2所述的方法，其中将所述添加剂依次引入所述元件(1)的表面层(7)中。
4.如权利要求2所述的方法，其中至少两种添加剂同时引入所述元件(1)的表面层(7)中。
5.如权利要求1-4任一项所述的方法，其中将所述至少一种添加剂引入表面层(7)中，深度为0.5mm或更少。
6.如权利要求1-5任一项所述的方法，其中将Hf用作添加剂，且Hf以所述表面层(7)的材料组成的至多5重量％的量引入所述表面层(7)中。
7.如权利要求1-6任一项所述的方法，其中将La和/或Y用作添加剂，且La和/或Y以所述表面层(7)的材料组成的至多0.2重量％的量引入所述表面层(7)中。
8.如权利要求1-7任一项所述的方法，其中将所述至少一种添加剂引入所述表面层(7)中通过使所述至少一种添加剂熔融进入所述表面进行。
9.如权利要求8所述的方法，其中使所述至少一种添加剂熔融进入所述表面通过局部加热所述表面进行。
10.如权利要求1-7任一项所述的方法，其中将所述至少一种添加剂引入所述表面层(7)中通过使所述至少一种添加剂扩散进入所述表面进行。
11.如权利要求8-10任一项所述的方法，其中所述熔融或扩散通过将包含所述至少一种添加剂的浆料基质施加在所述表面上并加热在其上具有施加的所述浆料的所述表面进行。
12.如权利要求11所述的方法，其中所述浆料基质包含所述超合金的基体材料和有机粘合剂。
13.如权利要求1-12任一项所述的方法，其中，在添加剂引入所述元件(1)的表面层(7)后，将抗氧化和/或抗腐蚀涂层(13)施加到所述超合金元件(1)的所述表面上。
14.具有表面层(7)的超合金元件(1)，包含选自Gf，La，Y的组的添加剂。
15.如权利要求14所述的超合金元件(1)，其中表面层的深度为0.5mm或更小。
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