CN101248214B - 提供热障涂层的方法和具有所述涂层的衬底 - Google Patents

提供热障涂层的方法和具有所述涂层的衬底 Download PDF

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CN101248214B
CN101248214B CN2006800267459A CN200680026745A CN101248214B CN 101248214 B CN101248214 B CN 101248214B CN 2006800267459 A CN2006800267459 A CN 2006800267459A CN 200680026745 A CN200680026745 A CN 200680026745A CN 101248214 B CN101248214 B CN 101248214B
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赛思·朱斯特·尼基丹姆
拉兹·彼彻斯·亨里克斯·约根斯
威伦·格雷特·斯鲁夫
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Abstract

发明涉及一种提供热障涂层的方法和衬底。所述热障涂层是提供于在所述衬底上所提供的金属粘结涂层上生长的热生长氧化物上。所述粘结涂层与热生长氧化物涂层之间的粘附通过在界面处提供氧化钇-氧化铝石榴石复合物突起来改进。所述热生长氧化物涂层在相对高温下的使用寿命通过具有相对较大尺寸的氧化铝颗粒来改进。这些都是通过在惰性气体气氛中预退火所述粘结涂层随后进行受控预氧化而获得。

Description

提供热障涂层的方法和具有所述涂层的衬底
技术领域
本发明涉及一种用于在衬底上提供热障涂层的方法，其包含在所述衬底上提供金属粘结涂层，随后在所述金属涂层上提供热生长氧化物，此后涂覆陶瓷涂层，其中所述热生长氧化物是通过对所述粘结涂层的预氧化处理而实现。
背景技术
通常，本领域熟知的方法是，涡轮叶片以及经受高温的其它物件都可以通过提供陶瓷涂层来进行保护。由于氧化物和衬底具有不同的热膨胀系数且相关组件的温度条件改变，因此陶瓷涂层与下层衬底的粘附就存在问题。一种解决方法是在所述衬底上提供粘结涂层。这种粘结涂层优选为能够在其上热生长氧化物的金属涂层。此类氧化物对于陶瓷障涂层来说是极佳的粘附表面。
为成功构造这种分层结构，粘结涂层与热生长氧化物之间的粘附是相当重要的。此外，粘结涂层中金属的损耗应尽可能的少以增加相关组件的使用寿命。所生长的氧化物主要为氧化铝。旨在不形成尖晶石的情况下实现α-Al2O3层。而且，最后还应尽可能地防止亚稳态氧化铝的存在。
如上文所述构造热障涂层的优势为相对较低的成本和提供所述涂层的方式简易。然而，在迅速改变温度的环境下，使用寿命相对有限，这将使得制造所述涂层比制造其它现有技术涂层昂贵。
EP-0567252 A1揭示一种晶须锚定的热障涂层(whisker-anchoredthermal barrier coating)。所述晶须优选延伸穿过粘结涂层。所述粘结涂层的厚度通常为约100μm。已发现，所述结构会导致过早产生裂缝。
EP-0992612 A2涉及一种含铝粘结涂层，其包含30-60原子％的铝。
发明内容
本发明旨在提供一种热障涂层，利用这种涂层，可改进粘结涂层与热生长氧化物之间的粘附，从而使陶瓷涂层损坏的几率降低。此外，本发明旨在显著增加所述热障涂层的使用寿命。
根据本发明，这可以用技术方案实现。
一种在衬底上提供热障涂层的方法，其包含在所述衬底上提供金属粘结涂层，随后在所述金属涂层上提供热生长氧化铝，此后涂覆陶瓷涂层，其中所述热生长氧化铝通过对所述粘结涂层的预氧化处理而实现，所述方法的特征在于，在提供所述粘结涂层后并且在对其进行所述预氧化处理之前，通过使所述粘结涂层在低于10-3Pa的压力下经受1000-1200℃的温度达5-60分钟来使其退火
通过在预氧化提供于衬底上的粘结涂层之前使用退火步骤，可以通过蒸发去除应实现热生长氧化物的表面处所存在的铬。由于表面处不再存在相当多的铬，故能够促进氧化铝的生长。
如果粘结涂层包含钇(用于清除杂质)，那么通过退火处理将在粘结涂层的外表面处存在有氧化钇。在氧化处理过程中，将产生氧化钇氧化铝石榴石小微晶，其充当将热生长氧化物固定在粘结涂层上的栓钉。
粘结涂层优选包含MCrAlX粘结涂层，其中M为Ni、Co，其中X为用于清除杂质的反应性元素，诸如钇、锆或铪。
在退火处理期间，使用相对较低的如低于10-3Pa的压力来提高纯度。这种方法可以在5-60分钟内实现并且更尤其在约10分钟内实现。所述处理相对简单，并且可以容易地并入所述过程中以提供热生长氧化物。
在退火步骤后，优选在同一熔炉内实现预氧化步骤。也就是说，将氧气或氧气-惰性气体混合物注入所述熔炉中。优选这是在受控环境下、诸如在介于1000℃与1200℃之间的温度和介于10-104Pa之间的氧分压下实现。在这些条件下，能够保证主要形成α-Al2O3。归因于先前的退火步骤，故粘结涂层的外表面相对清洁并且富集铝。已发现，使用如上文所述的方法，氧化铝的颗粒尺寸相对较大。α-Al2O3颗粒的横向尺寸应相对较大，即，大于1μm。这是重要的，因为通过氧化铝的氧扩散主要是沿着颗粒边界进行。通过具有相对较大尺寸的氧化铝颗粒，颗粒边界的总长度将降低。氧化时间优选在1与5小时之间。
据观察，具有根据本发明的热障涂层的衬底具有比不具有根据本发明的热障涂层的衬底长200-400％的使用寿命。
这意味着，例如飞机涡轮的保养间隔可增加，从而减少非操作时间。
氧分压不应增加到104Pa以上，这是因为超过104Pa的压力将产生尖晶石。如果压力低于10Pa，那么氧化钇氧化铝石榴石将不再起到将热生长氧化物固定于粘结涂层上的栓钉的作用。
除了在与实现退火处理的熔炉相同的熔炉中实现预氧化处理外，还有利地在同一熔炉中提供陶瓷层。由于具有清洁的气氛，所以杂质的影响将得到抑制。可以通过电子束物理气相沉积或大气等离子喷涂来提供陶瓷涂层。然而，还可使用沉积陶瓷涂层的其它现有技术方法。
本发明还涉及一种通过上文所述的方法获得的衬底，其中在粘结涂层与热生长氧化物层之间提供包含由氧化铝包围的杂质清除元素氧化物的栓钉，诸如氧化钇氧化铝石榴石，其中所述热生长氧化物层中所述铝氧化物的颗粒尺寸大于1μm。优选在界面的1-10％表面积处包含所述栓钉，从而提供粘结涂层与热生长氧化物之间的优良粘附。这种粘结涂层优选为镍、钴、铬、铝合金，而不存在大量的铁。钇优选是以低于1原子％且更尤其以约0.5原子％的量存在于所述合金中。铝含量优选低于25原子％。
上述栓钉的尺寸应相对较小，即，小于5μm。已发现，如果栓钉的尺寸实质上增加到超过5μm，那么将会引起破裂的开始。
附图说明
本发明提供一种生长相对缓慢的α-氧化铝层，其是通过机械方式固定于粘结涂层上。以此方式，可获得优良的粘附。
将参考图式中所示的实例进一步阐述本发明，其中：
图1示意性展示热障涂层的提供；且
具体实施方式
图2提供具有涂层的所述衬底的截面细节。
图1展示经热障涂层(TBC)覆盖的衬底，诸如叶片。所述热障涂层为陶瓷涂层，其应粘附于通常为超合金(super alloy)(即，以镍/钴为基础的合金)的衬底上。为提供陶瓷涂层与衬底之间的粘附，提供粘结涂层，诸如MCrAlX粘结涂层。M为Ni或Co，而X为所谓的反应性元素，诸如钇。在这种涂层系统上提供热生长氧化物，其将保护下层衬底免于高温氧化和腐蚀。
根据本发明，由衬底1起始，在其上提供粘结涂层3。这可以利用所属领域中已知的任何方法实现。随后，使覆盖有粘结涂层3的衬底1进入温度介于1000-1200℃之间且压力相对较低(低于10-3Pa)的熔炉2中。所用气氛相对清洁，并且优选在约10分钟的时间内，使粘结涂层经受退火。这将导致铬从涂层的自由端表面去除。这是如步骤A所示。随后，在同一熔炉中，在大致相同温度下导入氧气，从而产生热生长氧化物。这是在10-104Pa的氧分压下在1000-1200℃的温度范围内且于1-5小时的时间内实现。这是在步骤B中实现并且热生长氧化物层由4表示。
此后，优选在同一熔炉中进行步骤C，其中将陶瓷层沉积于热生长氧化物上。
在图2中，展示所得复合层的细节。可看出，在粘结涂层3上，热生长氧化物4是通过氧化钇氧化铝石榴石栓钉6固定。栓钉的总表面积为总界面表面积的约1-10％。各栓钉具有小于5μm的尺寸。热生长氧化物层实质上包含具有约1μm的相对较大横向颗粒尺寸的α-氧化铝。
已发现，在相对较高温度下，在叶片正常使用期间，这种α-氧化铝层生长极慢。由于来自粘结涂层的Al的损耗相对较慢，故而导致相当长的使用寿命。缓慢生长的氧化物使得陶瓷涂层机械损坏的时间得以延长。由于存在栓钉6，故粘结涂层与热生长氧化物的粘附得以优化，从而使得使用寿命进一步提高。
实例
通过电子束物理气相沉积，在具有标准碳含量的钢板上产生1mm厚的双相γ-Ni+β-NiAl Ni-21Co-18Cr-22A1-0.2Y(原子％)，随后将其从所述钢板移出。在将粘结涂层表面抛光后，进行以下四个预退火和/或预氧化处理(参看表1)：
(I)在UHV室中在流动氩气中于1373K下预退火1小时(基础压力＜1O-7 Pa)。
(II)在平管炉中，在氩和20体积％氧气流中于20 kPa的pO2下，在1373 K下预氧化1小时。
(III)在UHV室中在流动氩气中于1373 K下预退火5分钟，随后立即在纯净的流动氧气中于1373 K的温度和1OO Pa的pO2下预氧化1小时。
(IV)在UHV室中在流动氩气中于1373 K下预退火5分钟，随后立即在纯净的流动氧气中于1373 K的温度和O.1Pa的pO2下预氧化1小时。
Figure DEST_PATH_GA20173858200680026745901D00041
对于预退火或预氧化后所得氧化物层的详细分析揭示，对于在不进行预退火的情况下于20 kPa下进行预氧化处理来说，氧化物层除α-Al2O3外还含有NiAl2O4尖晶石，并且沿氧化物/粘结涂层界面，存在作为氧化钇氧化铝石榴石大微晶的钇。在随后不进行预氧化的情况下预退火会使Cr从粘结涂层蒸发，并且在粘结涂层表面处同时形成氧化钇小微晶。只有在应用组合预退火和预氧化处理时，所述氧化物层才只由α-Al2O3组成。对于在0.1Pa下进行的预氧化处理来说，α-Al2O3几乎是在开始氧化后立即成核。在这种情况下，预退火后形成的氧化钇位于预氧化后氧化  物表面处的氧化钇氧化铝石榴石小微晶内。对于在100Pa下进行的预氧化处理来说，α-Al2O3是从最初成核的亚稳态θ-Al2O3转化而来。只有在这种情况中，(i)氧化物层具有较大颗粒尺寸并且生长极慢，并且(ii)所得氧化钇氧化铝石榴石微晶位于沿氧化物/粘结涂层界面的多个小YAl氧化物突起(即，栓钉)内。
接下来，将如上文所述的类似NiCoCrAlY粘结涂层沉积于RenéN5超合金衬底上。在抛光BC表面后，如表1中所列的相同预退火、预氧化或组合预退火和预氧化处理提供这些NiCoCrAlY涂层。最后，将由7重量％经氧化钇稳定的氧化锆组成的陶瓷涂层沉积于预氧化的粘结涂层表面顶部。随后，在1373K下，使所制备的热障涂层热循环直到损坏，达1小时循环。这一热循环测试揭示，如果在陶瓷涂层沉积之前进行在100Pa下进行的组合预退火和预氧化处理，那么陶瓷涂层从粘结涂层损坏将延缓2到4倍。已确定，氧化物/粘结涂层界面处氧化钇氧化铝石榴石突起的存在和低α-Al2O3生长速率是使在100Pa下用组合预退火和预氧化处理制备的热障涂层系统具有长使用寿命的主要因素。

Claims (13)

1.一种在衬底上提供热障涂层的方法，其包含在所述衬底上提供金属粘结涂层，随后在所述金属涂层上提供热生长氧化铝，此后涂覆陶瓷涂层，其中所述热生长氧化铝通过对所述粘结涂层的预氧化处理而实现，所述方法的特征在于，在提供所述粘结涂层后并且在对其进行所述预氧化处理之前，通过使所述粘结涂层在低于10-3Pa的压力下经受1000-1200℃的温度达5-60分钟来使其退火。
2.根据权利要求1所述的方法，其中所述粘结涂层为MCrAlX粘结涂层，其中M为Ni或Co，并且X为杂质清除元素。
3.根据前述权利要求中任一权利要求所述的方法，其中所述预氧化处理包含使所述衬底和所述粘结涂层在10-104Pa的氧分压下经受1000-1200℃的温度。
4.根据权利要求3所述的方法，其中所述预氧化处理是在所述退火后立即实现。
5.根据权利要求4所述的方法，其中所述预氧化处理是在与所述退火相同的熔炉中实现。
6.根据权利要求1、2、4和5中任一权利要求所述的方法，其中提供所述陶瓷层是在与实现所述预氧化处理相同的熔炉中实现。
7.根据权利要求3所述的方法，其中提供所述陶瓷层是在与实现所述预氧化处理相同的熔炉中实现。
8.一种衬底(1)，其包含具有粘结涂层(3)、热生长氧化铝层(4)和陶瓷层的热障涂层，其中在所述粘结涂层与所述热生长氧化铝层之间的界面处提供突起，所述突起包含由氧化铝包围的杂质清除元素氧化物，其中所述热生长氧化铝层中所述铝氧化物的颗粒尺寸大于1μm。
9.根据权利要求8所述的衬底，其中所述突起为氧化钇氧化铝石榴石。
10.根据权利要求8所述的衬底，其中所述界面的表面积的1-10％包含所述突起。
11.根据权利要求10所述的衬底，其中所述杂质清除元素氧化物突起是排列在尺寸小于5μm的突起中。
12.根据权利要求8至11中任一权利要求所述的衬底，其中所述粘结涂层包含MCrAlX粘结涂层，其中M为Ni或Co，并且X为杂质清除元素。
13.一种涡轮叶片，其包含具有根据权利要求8至11中任一权利要求所述的涂层的以Ni或Co为基础的衬底。
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