CN100350075C - 高温防护层 - Google Patents

高温防护层 Download PDF

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CN100350075C
CN100350075C CNB038023121A CN03802312A CN100350075C CN 100350075 C CN100350075 C CN 100350075C CN B038023121 A CNB038023121 A CN B038023121A CN 03802312 A CN03802312 A CN 03802312A CN 100350075 C CN100350075 C CN 100350075C
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D·埃卡德特
K·E·施奈德
C·滕内斯
H·－P·波斯曼
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Abstract

本发明公开了一种高温防护层，其含有(重量%)23至27%的Cr、4至7%的Al、0.1至3%的Si、0.1至3%的Ta、0.2至2%的Y、0.001至0.01%的B、0.001至0.01%的Mg和0.001至0.01%的Ca，其余为Ni和不可避免的杂质。优选Al的含量在大于5至6重量%的范围内。

Description

高温防护层
技术领域
本发明涉及一种高温防护层。
背景技术
这类高温防护层首先用于保护由耐热钢和/或合金制成的建筑构件的基材，它们都是在超过600℃的温度下使用的。
通过使用这类高温防护层就能延缓或完全抑制主要是硫、油灰、氧、碱土金属和钒的高温腐蚀作用。这类高温防护层都被设计成能直接涂覆于待保护建筑构件的基材上。
高温防护层对于燃气涡轮机的结构元件有着极其特殊的意义。它们主要涂覆在转轮轮叶和导向叶片，以及燃气涡轮机的蓄热片上。
优选用镍、钴或铁基奥氏体金属制这些结构元件。在制备燃气涡轮机结构元件的过程中主要使用镍-超合金作为基材。
到目前为止，通常都要在用于组成燃气涡轮机的结构元件上设置防护层，该涂层由合金构成，其主要成分是镍、铬、铝和钇。这种高温防护层具有一种嵌入含铝相的基体。
用于高温的涂层大部分都来自于NiCrAlY、CoCrAlY或NiCoCrAlY类物质。各种涂层的不同点在于“同族元素”镍、钴、铬、铝和钇的浓度以及是否添加其他元素。涂层的成分在很大程度上确定了高温、氧化或腐蚀气氛下，以及当温度变化和承受机械负载时的性质。另外，涂层成分也决定了材料和生产的成本。许多已知的涂层只能部分地体现出卓越的性质。尽管在世界范围内广泛使用，但是一些试验表明，添加的钴会对耐腐蚀性和生产成本均产生消极影响。
在文献JP-A-53-085736，US-A-3620693，US-A-4477538，US-A-4537744，US-A-3754903，US-A-4013424，US-A-4022587和US-A-4743514中公开了众多“不含钴的NiCrAlY”系合金。在这些合金的相成分的温度范围为800℃到1050℃时的热力学模拟试验表明，这种特殊成分会使得微结构含有不理想的相或是具有热活化的相转变，即σ-和/或β-NiAl非常不利地具有很大的体积份数。
发明内容
从上述现有技术出发，本发明的任务在于提供一种高温防护层，该防护层廉价、耐氧化、耐腐蚀并耐温度变化。
本发明的任务可以通过本发明的高温防护层来解决。
本发明的这种合金组成含有(重量％)23至27％的铬、4至7％的铝、0.1至3％的硅、0.1至3％的钽、0.2至2％的钇、0.001至0.01％的硼、0.001至0.01％的镁和0.001至0.01％的钙，所有的重量含量都是按每种合金的总重量计的。该合金的其余部分由镍和不可避免的杂质组成。Al的含量优选在大于5至6重量％的范围内。
本发明的防护层是一种NiCrAlY合金。相对于已经公开的那些高温防护层，其具有明显改善的抗氧化和抗腐蚀性。可以肯定的是，本发明的高温防护层，在高温(各根据高于800℃时的实施方式、优选800℃-1050℃)下所具有的含铝γ和γ′相的体积含量为50％以上，并且其可以构成含氧化铝的防护层；而在低温和中温下(各根据低于900℃时的实施方式、优选800℃-900℃)含有大于5％的α-Cr相(图1中标记为BCC)，并且其可以构成含氧化铬的防护层。
如果向构成高温防护层的合金中添加硅和硼，就能改善高温下含氧化铝的覆盖层的粘结性，这显著提高了高温防护层和位于其下的结构元件的防护性。如果再添加镁和钙，首先便能结合掉在生产中天然存在的杂质并且由此而提高温度在850-950℃以下的耐腐蚀性。铬与铝的用量比限制在3.6至6.5，以抑制易碎的β-相的生成。而镍与铬的用量比也限定在2.3至3.0，由此抑制易碎的σ-相的生成，这样就能改善耐温度变化性。在温度频繁变化的情况下，防护层与其覆盖层之间的牢固持久的粘结可以通过对于合金而特定的钇含量来实现。
这里所选择的组成没有或只有很微量体积份数的σ-相或β-NiAl-相(图1)，从而在需要变化温度的情况下也能获得显著的优点。图2中的对比合金具有类似的若干元素的组成情况，但是由于其他元素的不同就出现了一种极不相同的微结构，根据我们的经验，对于燃气涡轮机来说，这种结构不具有足够的耐温度变化性并且由于超过900℃即会开始熔融，因此是不适合使用的。
受限于产品的那些固有的杂质硫，通常其浓度小于10ppm，但在个别情况下也会大至50ppm，该杂质会降低抗氧化和抗腐蚀性。根据本发明，在涂层的制备过程中要添加微量元素Mg和Ca，用以吸收硫。
直接将该合金涂覆于由第三种组成构成的结构元件基材上或中间层上。根据涂覆方法的不同，层厚度在0.03mm至1.5mm间变化。
本发明的高温防护层可用于绝热层下作为粘结层。
附图说明
以下将根据附图来阐述本发明，其中
图1为如上所述的组成的相平衡(摩尔份数Φ[％]对温度[℃])图，
图2为如专利US-A-4973445中所述组成的相平衡(摩尔份数Φ[％]对温度[℃])图。
这里只是针对发明的基本要素进行论述。
具体实施方式
以下将根据一个记载了如何生产经涂覆过的燃气涡轮机结构元件或是如何生产热涡轮机的其他结构元件的实施例来更为详尽地阐释本发明。待涂覆的燃气涡轮机结构元件由奥氏体金属，特别是由镍超合金制成。在涂覆前首先要利用化学方法清洁元件，然后利用喷射工艺进行粗糙化处理。结构元件的涂覆在真空中、保护气氛或空气的条件下，借助热喷镀法(LPPS，VPS，APS)、高速喷镀法(HVOF)、电化学法、物理/化学蒸镀法(PVD，CVD)或另一种现有技术公开的涂覆方法来进行。
将一种NiCrAlY合金用于涂层，根据本发明，该合金含有(重量％)23至27重量％的铬、4至7重量％的铝、0.1至3重量％的硅、0.1至3重量％的钽、0.2至2重量％的钇、0.001至0.01重量％的硼、0.001至0.01重量％的镁和0.001至0.01重量％的钙。该合金的其余量由镍和不可避免的杂质构成。优选铝的含量在大于5至6重量％的范围内。所有重量份数都是以所用合金的总重量来计的。
相对于已知的那些高温防护层，本发明的合金有着明显改善了的抗氧化性和抗腐蚀性。可以肯定的是，本发明的高温防护层，在高温(各根据高于800℃时的实施方式)下所具有的含铝γ和γ′相的体积含量为至少50％，并且其可以构成含氧化铝的防护层；而在低温和中温下(各根据低于900℃时的实施方式)含有大于5％的含铬α-Cr-相，并且其可以构成含氧化铬的防护层。
如图1所示，这里所选择的组成没有或只显示出了很小体积份数的σ-相或β-NiAl相或硼化物相(图1中标记为M2B_ORTH)，从而在需要温度变化时也能预期获得显著的优点。图2中的对比合金具有类似的若干元素的组成情况，但是由于其他元素的不同就出现了一种极不相同的微结构，根据我们的经验，对于燃气涡轮机来说，这种结构不具有足够的耐温度变化性并且由于超过900℃即会开始熔融，因此是不适合使用的。
为了改善高温下含氧化铝覆盖层的粘结性，就要向构成高温防护层的基材中熔合硅和硼。由此就能显著提高高温防护层和位于其下的结构元件的防护性。
受限于产品的那些固有的杂质硫，通常其浓度小于10ppm，但在个别情况下也会大至50ppm，该杂质会降低抗氧化和抗腐蚀性。在本发明中，在涂层的制备过程中要添加微量元素Mg和Ca，用以吸收硫并由此而提高在低于850至950℃的温度下的耐腐蚀性。
铬与铝的用量比限制在3.6至6.5，以抑制易碎的β-相的生成。而镍与铬的用量比也限定在2.3至3.0，由此抑制易碎的σ-相的生成，这样就能改善耐温度变化性。
在温度频繁变化的情况下，防护层与其覆盖层之间的牢固持久的粘结可以通过对于合金而特定的钇含量来实现。
为适于热喷镀加工，构成合金的材料要以粉末形式存在并优选具有5至90μm的粒径。在其他或类似的方法中则要将合金制成靶或悬浮体的形式。可以将合金直接涂覆在结构元件的基材上或由第三组成构成的中间层上。根据涂覆方法的不同，层厚度在0.03mm至1.5mm之间变化。在涂覆了合金之后，要对结构元件进行热处理。处理在1000至1200℃的温度下进行约10分钟至24小时。

Claims (10)

1.结构元件的高温防护层，其特征在于该层中含有按重量％计为23至27％的Cr、4至7％的Al、0.1至3％的Si、0.1至3％的Ta、0.2至2％的Y、0.001至0.01％的B、0.001至0.01％的Mg和0.001至0.01％的Ca，其余为Ni和不可避免的杂质。
2.如权利要求1的高温防护层，其特征在于该防护层含有按重量％计为大于5％至6％的Al。
3.如权利要求1或2的高温防护层，其特征在于Cr与Al的用量比在3.6至6.5的范围内。
4.如权利要求1或2的高温防护层，其特征在于Ni与Cr的用量比在2.3至3.0的范围内。
5.如权利要求1或2的高温防护层，其特征在于在800℃到1050℃的温度范围内，含铝相γ和γ′的体积比总和为50％以上。
6.如权利要求1或2的高温防护层，其特征在于当温度为800℃至900℃时，α-Cr相的体积比为5％以上。
7.如权利要求1或2的高温防护层，其特征在于涂层是在真空、保护气氛或空气中，借助热喷镀法、高速喷镀法、电化学沉积、物理蒸镀法或化学蒸镀法制得。
8.如权利要求1或2的高温防护层，其特征在于该层是热涡轮机结构元件上的涂层。
9.如权利要求1或2的高温防护层，其特征在于以0.03mm到1.5mm之间的层厚度将涂层直接涂覆于结构元件的基材上或中间层上。
10.如权利要求1或2的高温防护层，其特征在于将该涂层用于绝热层下作为粘结层。
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DE50300758D1 (de) 2005-08-18
CA2473565A1 (en) 2003-07-24
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CA2473565C (en) 2010-12-07
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US20050042474A1 (en) 2005-02-24
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US7052782B2 (en) 2006-05-30
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