CN101351576A - 用于燃气轮机热气区内构件的绝热保护层 - Google Patents

用于燃气轮机热气区内构件的绝热保护层 Download PDF

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CN101351576A
CN101351576A CNA2006800414617A CN200680041461A CN101351576A CN 101351576 A CN101351576 A CN 101351576A CN A2006800414617 A CNA2006800414617 A CN A2006800414617A CN 200680041461 A CN200680041461 A CN 200680041461A CN 101351576 A CN101351576 A CN 101351576A
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S·钱德拉
N·捷克
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Abstract

一种用于燃气轮机热气区内构件的绝热保护层，其由粘合层、扩散层和陶瓷层构成，其涂覆于构件的耐高温的基体金属上。粘合层由含Ni，Co，Cr，Al，Y的金属合金[MCrAlY(M＝Ni，Co)]构成，扩散层通过粘合层的渗铝产生，并且陶瓷层由ZrO2构成，ZrO2通过氧化钇部分地稳定。具有大原子半径的Re，W，Si，Hf和/或Ta这组元素中的一种或多种金属元素被作为合金成分加入粘合层材料。粘合层在涂覆后具有如下化学组成：Co 15～30％，Cr 15～25％，Al 6～13％，Y 0.2～0.7％，Re不超过5％，W不超过5％，Si不超过3％，Hf不超过3％，Ta不超过5％，其余为Ni。

Description

用于燃气轮机热气区内构件的绝热保护层
本发明涉及一种用于在燃气轮机热气区内的构件上的绝热保护层，其具有按照权利要求1的前序部分的特征。
在现代的燃气轮机中，热气区的表面几乎完全地涂覆有涂层。在某些情况下，例外存在于后涡轮机组的叶片中。绝热保护层用于降低冷却构件材料的温度。这样能够延长其使用寿命，减少冷却空气或燃气轮机能够以更高的进口温度运转。在燃气轮机中的绝热保护层体系总是由通过扩散与基材粘接的金属粘合层和其上的具有差的导热性的陶瓷层构成，该陶瓷层显示出对热气流真正的阻隔和保护构件的基体金属避免高温腐蚀和高温侵蚀。
二氧化锆(ZrO2)被普遍接受为用于绝热涂层的陶瓷材料，其通常可借助于约7重量％的氧化钇部分地稳定(国际缩写：“YPSZ”，由Yttria PartiallyStabilised Zirconia得)。根据各自涂覆方法，绝热涂层被划分为两个基本的种类：
——热喷涂涂层(通常借助于气体等离子体法，APS)，其中孔隙率视期望的层厚度和应力分布而定，在陶瓷层中约在10和25体积％之间。与(粗喷涂的)粘合层的连接通过机械的锚接实现。
——借助于电子束气相沉积的EB-PVD涂层(电子束-等离子体气相扩散)，其在保证确定的沉积条件下具有柱状的或圆柱状的抗膨胀的结构。此涂层通过形成Al/Zr混合氧化物化学地粘接在一个纯的氧化铝层(热生长氧化物，TGO)上，该氧化铝层由粘合层在涂覆时并随后在使用时形成，这对在粘合层上的氧化物生长提出了特殊要求。
原则上，不仅扩散层而且覆层可作为粘合层。
对粘合层的要求是复杂的，并需考虑如下几点：
——低的静态和循环氧化速率，
——形成尽可能纯的氧化铝层作为TGO(在EB-PVD法中)——足够的抗高温腐蚀性，
——低的脆性、延展性和转化温度，
——高蠕变强度，
——与基材相似的物理性能，好的化学相容性，
——好的粘接性，
——最少的与基材之间的长时间相互扩散，
——以能再现的品质的经济可涂覆性。
基于MCrAlY(M＝Ni，Co)的粘合层或覆层为稳态的燃气轮机的特殊要求提供了最好的可能性，以满足化学的和物理的前提要求。MCrAlY层在NiCoCr(‘γ’)基体中包含金属间β-相NiCoAl作为铝源。β-相的NiCoAl自然也有变脆的影响，所以实际可实现的Al含量为≤12重量％。为进一步提升抗氧化能力，可以用Al扩散层覆盖MCrAlY层。由于有脆化的危险，往往限制其为贫铝的(Al≤8％)起始涂层。
渗铝的MCrAlY层的结构由内部的通常不变的γ，β混相、一个扩散区(其中Al含量上升至约20％)以及一个外部的Al约占30％的β-NiAl相组成。就脆性和裂纹敏感性而言，NiAl相表现出该涂层体系的弱点。
随着使用温度的上升，除氧化特性和机械性能之外，在基材和MCrAlY层之间——在特殊情况下也包括在MCrAlY层和渗铝层之间——的(相互)扩散现象变得对使用寿命起决定性的作用。在极端情况下，MCrAlY层中有效氧化的铝由扩散引起的损失超过了由形成氧化物导致的损失。由于不对称扩散(其中局部的损失大于后期补偿)，有可能导致缺陷和孔隙的形成，甚至在极端情况下导致涂层的脱层。
本发明的任务在于，避免上述的缺陷，并在按照此类的绝热保护层中延缓扩散，而不损害渗铝层的抗氧化特性以及涂层体系的延展性和抗蠕变性能。
在按照此类的绝热保护层中，此任务根据本发明通过权利要求1的特征解决。本发明有利的实施形式为权利要求2和3的主题。
现已表明，通过以给定浓度优选添加Re和W，Si，Hf和/或Ta来对特定组成的NiCoAlY粘合层进行改性，扩散被延缓。通过对向基材和向渗铝层的扩散稳定性，绝热保护层的——尤其是通过EB-PVD法涂覆的涂层的——使用寿命被显著地延长。当绝热保护层过早失效时，例如由于被杂质击中或腐蚀，更久的“应急运行”是可能的。
绝热保护层的制备由如下方式实现。在热气区内冷却构件(例如汽轮机的叶片)的基体金属上，例如通过热喷涂涂覆上一层粘合层。为此使用一种预合金化的和雾化的粉末，其具有如下的化学组成：Co 15～30重量％，Cr 15～25重量％，Al6～13重量％，Y 0.2～0.7重量％，其余为Ni。此粉末还包含以下元素的一种或多种：Re不超过5重量％，W不超过5重量％，Si不超过3重量％，Hf不超过3重量％，Ta不超过5重量％。使用的粉末优选具有如下化学组成：Co 25重量％，Cr 21重量％，Al 8重量％，Y 0.5重量％，Re 1.5重量％，其余为Ni。在涂覆后，粘合层具有所用粉末的化学组成。
在涂覆粘合层后，为提高粘合层的Al含量，粘合层用Al扩散层覆盖或渗铝。覆盖通过渗铝实现，即通过一种处理，其中一种含Al的反应性气体在更高的温度下引起Al的向内扩散，伴随着Ni的向外扩散，此气体通常为Al的卤化物(AlX2)。
通过渗铝，在扩散层内通常不变的粘合层上产生了一个内部的扩散区和一个在其上由脆性的β-NiAl相构成的外部结构层。根据在(尚未公开的)德国专利申请102004045049.8中描述的方法，通过用硬质粒子，如金刚砂，碳化硅，金属丝或其它公知的磨料或抛光剂进行喷砂处理而除去外部结构层直至扩散层的内部扩散区。持续进行研磨处理，直至剩余扩散层的表面具有大于18％和小于30％的Al含量。
最后，根据开始提及的方法涂覆由氧化钇部分稳定的氧化锆构成的陶瓷层。

Claims (3)

1.用于燃气轮机热气区内构件的绝热保护层，其由粘合层、扩散层和陶瓷层构成，并涂覆在构件的耐高温的基体金属上，其中粘合层由含Ni、Co、Cr、Al、Y的金属合金[MCrAlY(M＝Ni，Co)]构成，扩散层通过粘合层的渗铝产生，并且陶瓷层由ZrO2构成，ZrO2通过氧化钇部分地稳定，其特征在于，具有大原子半径的Re、W、Si、Hf和/或Ta这组元素中的一种或多种金属元素被作为合金成分加入粘合层材料中，并且粘合层在涂覆后具有如下化学组成：Ni为其余
Co     15～30％
Cr     15～25％
Al     6～13％
Y      0.2～0.7％
Re不超过5％
W不超过5％
Si不超过3％
Hf不超过3％
Ta不超过5％。
2.按照权利要求1的绝热保护层，其特征在于，Re被作为合金成分加入粘合层材料，并且粘合层在涂覆后具有如下化学组成：
Ni为其余
Co        25％
Cr        21％
Al        8％
Y         0.5％
Re        1.5％。
3.按照权利要求1或2的绝热保护层，其特征在于，MCrAlY层以渗铝的方式涂覆在基体金属上，渗铝的MCrAlY层具有这样一种结构，该结构由内部的基本不变的γ，β混相、由具有约20％的Al的内部扩散区组成的扩散层以及由Al约占30％的β-NiAl相构成的外部结构层构成，由β-NiAl相构成的外部结构层通过研磨处理而基本上去除至扩散层的内部扩散区，剩余扩散层的表面具有大于18％和小于30％的Al含量。
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CN103060747A (zh) * 2012-12-13 2013-04-24 北京航空航天大学 一种采用包埋渗工艺在Ni基高温合金上制备Y改性CoAlNi涂层的方法
CN104511590A (zh) * 2013-10-01 2015-04-15 通用电气公司 用于3d打印用于涡轮护罩的表面的图案的方法
CN105189819A (zh) * 2013-03-13 2015-12-23 通用电气公司 用于金属基底的涂层
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CN111893363A (zh) * 2020-07-31 2020-11-06 西安交通大学 一种具有优异强度塑性匹配的NiCoCr基中熵合金及制备方法
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CN114086101A (zh) * 2021-11-19 2022-02-25 华能国际电力股份有限公司 一种抗高温氧化和热腐蚀热障涂层及制备方法
CN114262859A (zh) * 2021-12-29 2022-04-01 矿冶科技集团有限公司 一种双界面性能强化的MCrAlYX粘结层和热障涂层及其制备方法
CN114262859B (zh) * 2021-12-29 2023-01-31 矿冶科技集团有限公司 一种双界面性能强化的MCrAlYX粘结层和热障涂层及其制备方法

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CA2629066A1 (en) 2007-05-18
US20090011260A1 (en) 2009-01-08
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