CN1689800A - 薄7ysz界面层作为低导tbc的循环耐久性（剥落）寿命的增强 - Google Patents

薄7ysz界面层作为低导tbc的循环耐久性（剥落）寿命的增强 Download PDF

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CN1689800A
CN1689800A CNA2005100762684A CN200510076268A CN1689800A CN 1689800 A CN1689800 A CN 1689800A CN A2005100762684 A CNA2005100762684 A CN A2005100762684A CN 200510076268 A CN200510076268 A CN 200510076268A CN 1689800 A CN1689800 A CN 1689800A
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N·E·尤利安
M·F·特鲁贝尔亚
M·J·马洛尼
D·A·利顿
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Abstract

一种抗剥落的金属制品，包括金属基底，至少一种含有氧化锆基和至少一种选自La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Sc、In、Y、Mo和C、稀土氧化物、钪和铟的其它元素的陶瓷绝热涂层；和位于至少一部分基底上并且在所述金属基底和所述至少一种陶瓷绝热涂层之间的陶瓷粘合层，其中该陶瓷粘合层由氧化钇稳定的氧化锆(YSZ)构成。

Description

薄7YSZ界面层作为低导 TBC的循环耐久性(剥落)寿命的增强
技术领域
本发明涉及一种涂于金属零件的绝热涂层用陶瓷材料，其中在零件和涂层之间插入稳定氧化锆的界面层。
背景技术
燃气轮机发动机是发展得非常好的机械装置，其将燃料形式的化学势能转化成热能，然后转化成机械能，用于推动航空器，产生电力，泵抽流体等。目前，提高燃气轮机发动机效率的主要可行途径看来就是使用更高的操作温度。但是，当前用于燃气轮机发动机的金属材料非常接近于它们热稳定性的上限。在现代燃气轮机发动机的最热部分中，金属材料都在高于它们熔点的气体温度下使用。由于经过空气冷却，它们才得以维持。但是，提供空气冷却会降低发动机效率。
因此，用于冷却的燃气轮机飞行器硬件的绝热涂层已经有了广泛的发展。通过使用绝热涂层(TBC)，能使需要的冷却空气的量大大减少，相应地效率也得到了提高。一种用来保护燃气轮机发动机零件的常用TBC包括59wt％Gd2O3-41ZrO2。虽然这种Gd-Zr基TBC具有低的热导性能，但是其抗剥落性能低于常规的氧化钇稳定的氧化锆，例如7YSZ。人们认为：这种对剥落的敏感性是由于Gd-Zr体系具有较低的断裂韧性特征产生的。
相应地，已经发现：结合不同稳定氧化锆例如7YSZ的初始薄层(标称0.5-1密尔)会增强Gd-Zr体系的抗剥落性能。尽管没有完全明白，但是有可能是由于7YSZ的较高断裂韧性导致这种增加的抗剥落性能，使其抵抗TBC/粘合层(或更尤其是氧化铝层)界面上形成的应力。7YSZ层的另外一个可能有益的作用是可能与在基底合金或粘合层表面上形成的氧化钆和氧化铝表皮之间不具有潜在有害的相互作用有关。不管其工作机理，已经发现：添加薄7YSZ中间层补偿了Gd-Zr基TBC较低的断裂韧性，以致于增强了抗剥落性能。
除了抗剥落性能外，同样需要生产具有耐腐蚀性能的TBC。发动机工作过程中，当被发动机吸收或释放的细颗粒以非常高的速度撞击TBC时，发生腐蚀。这导致TBC从其表面向下磨损。一般，在给定撞击作用下，仅仅腐蚀掉非常小的TBC颗粒，因为仅仅是细颗粒才容易进入涡轮，而大颗粒在压缩机中被离心分离。这种腐蚀作用每次释放小块TBC，局部轻微地减少TBC的厚度。具有较低断裂韧性的低热导性能的TBC(例如59GdZr)易于腐蚀。
然而，尽管Gd-Zr基TBC尤其是59wt％Gd2O3-41 ZrO2，具有相对低的热导率系数，但是仍然需要TBC具有更低的热导性能。这种TBC可具有比目前体系更低的抗剥落性能和耐腐蚀性能。这种抗剥落性能理想地通过抵抗TBC从下面零件上分离出来以及抵抗包括TBC的不同层相互分离而得到证明。
一般而言，金属材料的热膨胀系数超过陶瓷材料的热膨胀系数。因此，在开发成功的绝热涂层中必须解决的一个问题是：使陶瓷材料的热膨胀系数与金属基底更加紧密匹配，以致于当基底由于被加热而膨胀时，陶瓷涂层材料不破裂。氧化锆具有高的热膨胀系数，并且这是氧化锆成功作为金属基底上的绝热材料的主要原因。
尽管目前利用电子束物理气相沉积氧化锆基涂层取得成功，但继续希望改善涂层，使其具有优异的绝热性能，尤其是当规范化涂层密度时在绝热性能方面的那些改善。当设计燃气轮机发动机，尤其是旋转零件时，重量总是关键因素。陶瓷绝热涂层不是载荷支撑材料，并且因此，它们增加重量而不增加强度。非常需要能增加最小重量同时具有最大绝热性能的陶瓷绝热材料。除此以外，很显然，通常希望具有长的寿命、稳定性、经济性等等。
因此，所需要的是：所涂覆的零件包括绝热涂层，其提供更低的热导性能但是具有合适的抗剥落性能。
发明内容
因此，本发明的目的是提供一种涂于金属零件的绝热涂层用陶瓷材料，其中在零件和涂层之间插入7YSZ的界面层，以增加涂层的抗剥落性能。
根据本发明，抗剥落金属制品包括金属基底、至少一种含有氧化锆基和至少一种选自La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Sc、In、Y、Mo和C、稀土氧化物、钪和铟的其它元素的陶瓷绝热涂层、和位于至少一部分基底上的并且在金属基底和至少一种陶瓷绝热涂层之间的陶瓷粘合层，其中该陶瓷粘合层由氧化钇稳定的氧化锆(YSZ)构成。
进一步根据本发明，抗剥落性能的金属制品包括至少一种热导率小于约1.5W/m℃的陶瓷绝热涂层。
进一步根据本发明，减少金属制品中剥落的方法包括步骤：提供一种金属基底；用至少一种含有氧化锆基和至少一种选自La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Sc、In、Y、Mo和C、稀土氧化物、钪和铟的其它元素的陶瓷绝热涂层涂覆金属基底，和在金属基底和至少一种陶瓷绝热涂层之间插入陶瓷粘合层，其中陶瓷粘合层由氧化钇稳定的氧化锆(YSZ)构成。
进一步根据本发明，抗剥落性能的金属制品包括金属基底、至少一种含有氧化锆基和至少一种选自La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Sc、In、Y、Mo和C、稀土氧化物、钪和铟的其它元素的陶瓷绝热涂层、在金属基底和至少一种陶瓷绝热涂层之间的陶瓷粘合层，其中陶瓷粘合层由氧化钇稳定的氧化锆(YSZ)构成、插入在金属基底和陶瓷粘合层之间的热生长氧化物(TGO)层、和在TGO层和金属基底之间的金属粘合层。
结合附图和以下描述来说明本发明的一个或多个实施方案的具体细节。从说明书和附图，以及从权利要求书中可以理解本发明的其它特征、目的和优点。
附图说明
图1说明插入在本发明的陶瓷涂层和金属基底之间的陶瓷粘合层。
图2说明插入在本发明的陶瓷涂层和热生长氧化物(TGO)涂层之间的陶瓷粘合层。
图3说明本发明的实施方案，其中涂有外层陶瓷涂层。
图4说明本发明的实施方案，其中YSZ陶瓷层插入在两种陶瓷绝热涂层之间。
图5说明插入在本发明的TGO涂层和金属基底之间的金属粘合层。
在不同的附图中，相同的参考数字和名称是指相同的元件。
具体实施方式
因此，本发明的教导是提供一种具有金属基底的金属制品，优选燃气轮机发动机部件，包括陶瓷绝热涂层(TBC)和插入在陶瓷TBC和金属基底之间的稳定氧化锆的陶瓷粘合层。优选的陶瓷粘合层是7YSZ，尽管其它氧化钇稳定的氧化锆，例如包含约1-20重量％氧化钇的稳定的氧化锆。在所有情况下，陶瓷TBC包含添加有一种或多种以下元素的氧化锆基：La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Sc、In、Y、Mo和C、稀土氧化物、钪和铟，其中这些元素存在的量为M2O3氧化物的1-50，并且优选为2-40摩尔％，其中M是指上述所列的元素。氧化钇稳定的氧化锆(YSZ)显示理想的机械完整性，使其能经受住当其所附的金属制品在热循环时所产生的应力。结果是：YSZ的陶瓷粘合层在金属制品和陶瓷TBC之间起到稳定过渡的作用，从而增加了陶瓷TBC的抗剥落性能。
参考图1，说明本发明的金属零件10的构造，其由形成金属制品的金属基底11、陶瓷TBC、和陶瓷粘合层组成。该制品也可以在金属基底和陶瓷粘合层之间包括金属粘合层，如覆层(MCrAlY)粘合层或一种铝化物，其也可以包括贵金属。可选择的是，基底可以包括能形成粘附的氧化铝层的材料，并且这样不需要金属粘合层。金属基底11形成需要用陶瓷TBC 15涂覆的零件。优选，金属基底11由钢、超级合金、钛合金和铜合金形成。如所述，由氧化钇稳定的氧化锆(YSZ)构成的陶瓷粘合层13沉积到金属基底11的外表面。陶瓷粘合层13的厚度优选在0.5和3密尔之间，最优选厚度为约1密尔。同样，陶瓷TBC涂到陶瓷粘合层13的最外层上。
可以通过各种方法将陶瓷TBC 15涂覆到陶瓷粘合层13。这种方法包括，但是不局限于：热喷涂方法如以空气等离子喷涂(APS)、低压等离子喷涂(LPPS)、高速氧气燃料过程(HVOF)、经爆炸喷枪(D Gun)、和溅射。沉积陶瓷TBC 15的优选方法包括电子束物理气相沉积(EBPVD)。使用EBPVD具有一些优点，因为使用EBPVD产生一种适合于极端温度应用的结构，并且因此更适合涂覆高温段的涡轮部件。热喷涂处理能提供涂覆形状复杂的大部件的优点，并且更加适合涂覆诸如燃烧器等部件。
在燃气轮机应用中，金属基底11的背部19将通过冷却空气(未显示)进行冷却，并且陶瓷TBC 15的外表面21将暴露在高温下。热流将从外表面21流到所冷却的表面背部19，并且热流的量被陶瓷TBC 15充分减少。
参考图2，说明本发明的金属零件10的另外可选实施方案。金属零件10由于添加插入在金属基底11和陶瓷粘合层13之间的热生长氧化物(TGO)17而增强。如前面所述，陶瓷粘合层13的厚度优选约为0.5和3.0密尔之间，更优选厚度为约1.0密尔。
参考图5，说明另外的可选实施方案，其中将金属粘合层51涂在金属基底11和陶瓷粘合层13之间。金属粘合层51由含铝涂层构成。这种金属涂层的组成如此选择以致于在操作过程中在金属粘合层上形成一层连续的、薄的、生长缓慢的氧化铝层。在本领域中，众所周知：这种氧化铝作为热生长氧化物或TGO。典型的金属粘合层51包括通过APS、LPPS、阴极电弧和其它技术形成的NiCoCrAlY覆层、以及通过电镀Pt形成的(Ni、Pt)Al涂层，然后蒸发涂覆NiAl并且扩散热处理该涂层以便形成(Ni、Pt)Al。如上所述，在没有金属粘合层51的情况下，在金属基底11和陶瓷粘合层13之间形成TGO层17。在具有金属粘合层51的体系中，在金属粘合层51和陶瓷粘合层13之间形成这种TGO层17。在类似陶瓷涂覆的零件上，TGO层17的厚度一般为0.1-0.5微米，并且在运行中生长到10微米厚。TGO层17负责给超级合金零件提供抗氧化性能，因为氧通过氧化铝扩散非常慢。
参考图3，说明本发明金属零件10的另外可选的实施方案。除了在陶瓷TBC15和金属基底11之间插入由7YSZ构成的陶瓷粘合层13以外，还额外涂一种外层陶瓷涂层31。外层陶瓷涂层31形成金属基底11的最外层涂层。由于它由YSZ构成，外层陶瓷涂层31拥有固有的良好的机械完整性，并且对于由操作中的金属零件10受到的应力起到进一步增强抗剥落性能。此外，外层陶瓷涂层31降低金属零件10最外层表面腐蚀的倾向。外层陶瓷涂层31的厚度优选为约0.5和3.0密尔之间，更优选厚度为约1.0密尔。
参考图4，说明本发明的金属零件10的另外可选实施方案，其中，在金属基底11上沉积至少两层陶瓷TBC 15、15′，并且更具体地沉积在将金属基底11与陶瓷TBC 15、15′分离的陶瓷粘合层13上。分离两层陶瓷TBC 15、15′的是由YSZ构成的陶瓷层33。在两层陶瓷TBC 15之间，由YSZ优选7YSZ构成的陶瓷层33起到增加机械完整性的作用，借此使陶瓷TBC 15、15′相互粘附在一起。结果是，多重陶瓷TBC 15、15′的抗剥落性能整体增加。陶瓷层33优选在0.5和3.0密尔之间，更优选厚度为约1.0密尔。
利用两个电子束枪进行EB-PVD涂覆试验，其中对陶瓷基底11涂覆多种组合物以形成陶瓷绝热涂层。测量每一种组合物的抗剥落性以致于得到每一种组合物的剥落基准值。接着，在金属基底11和陶瓷绝热涂层之间插入厚度约为1密尔的YSZ的陶瓷粘合层，具体地为7YSZ粘合层。再次测量抗剥落性能，并与基准值比较。包括EBPVD涂覆的TBC的组合物和其形成方法如下：
-用Mo分层的7YSZ(一个枪恒速蒸发7YSZ，另一个枪在7YSZ和Mo之间交换)。
-具有均匀Mo的7YSZ(一个枪恒速蒸发7YSZ，另一个枪恒速蒸发Mo)。
-用C分层的7YSZ(一个枪恒速蒸发7YSZ，另一个枪在7YSZ和C之间交换)。
-具有均匀C的7YSZ(一个枪恒速蒸发7YSZ，另一个枪恒速蒸发C)。
-用Mo分层的59GdZr(一个枪恒速蒸发59GdZr，另一个枪在59GdZr和Mo之间交换)。
-具有均匀Mo的59GdZr(一个枪恒速蒸发59GdZr，另一个枪恒速蒸发Mo)。
-用C分层的59GdZr(一个枪恒速蒸发59GdZr，另一个枪在7YSZ和C之间交换)。
-具有均匀C的59GdZr(一个枪恒速蒸发59GdZr，另一个枪恒速蒸发C)。
在所有情况下，使用厚度约为1密尔的纯7YSZ陶瓷粘合层将抗剥落性能改进到等于或者优于基准。测量7YSZ陶瓷粘合层增强的组合物的抗剥落性能在150到300小时之间。
已经描述了本发明的一个或者多个实施方案。然而，应该理解为：可以在不背离本发明的精神和范围的前提下作出各种改进。因此，其它实施方案落在以下权利要求书的范围内。

Claims (29)

1.一种抗剥落的金属制品，包括：
金属基底；
至少一种含有氧化锆基和至少一种选自La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Sc、In、Y、Mo和C、稀土氧化物、钪和铟的其它元素的陶瓷绝热涂层；和
在所述金属基底和所述至少一种陶瓷绝热涂层之间的陶瓷粘合层，其中所述陶瓷粘合层由氧化钇稳定的氧化锆(YSZ)构成。
2.权利要求1的制品，其中金属基底选自钢、超级合金、钛合金和铜合金。
3.权利要求1的制品，其中热生长氧化物(TGO)层插入在所述金属基底和所述陶瓷粘合层之间。
4.权利要求1的制品，其中所述陶瓷粘合层厚度在约0.5和3.0密尔之间，优选约1.0密尔。
5.权利要求1的制品，其中所述至少一种陶瓷绝热涂层的外表面涂有外层陶瓷涂层，所述外层陶瓷粘合层包括氧化锆基和至少一种选自Sm、La、Yb、Ce、Lu、Mo、稀土氧化物、钇、钪、铟及其组合的其它元素。
6.权利要求1的制品，其中在所述至少一种陶瓷绝热涂层的两层之间插入陶瓷层，所述陶瓷层由YSZ构成。
7.权利要求6的制品，其中所述陶瓷层厚度在约0.5和3.0密尔之间，优选约1.0密尔。
8.权利要求1的制品，其中通过选自热喷涂、溅射和电子束物理气相沉积(EBPVD)中的方法涂覆所述至少一种陶瓷绝热涂层，并且其中所述至少一种陶瓷绝热涂层的热导率小于约1.5W/m℃。
9.权利要求1的制品，其中该制品是燃气轮机发动机部件。
10.权利要求1的制品，在所述TGO层和所述金属基底之间还包括金属粘合层。
11.权利要求10的制品，其中所述金属粘合层是由选自覆层(MCrAlY)和铝化物的原料形成的，并且其中所述金属基底是由能形成氧化铝层的镍基超级合金形成的。
12.减少金属制品中剥落的方法，包括步骤：
提供一种金属基底；
用至少一种含有氧化锆基和至少一种选自La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Sc、In、Y、Mo和C、稀土氧化物、钪和铟的其它元素的陶瓷绝热涂层涂覆所述金属基底；和
在所述金属基底和所述至少一种陶瓷绝热涂层之间插入陶瓷粘合层，其中所述陶瓷粘合层由氧化钇稳定的氧化锆(YSZ)构成。
13.权利要求12的方法，其中所述的插入所述陶瓷粘合层包括插入所述的厚度在约0.5和3.0密尔之间，优选为约1.0密尔的陶瓷粘合层。
14.权利要求12的方法，其中所述的提供步骤包括提供选自钢、超级合金、钛合金和铜合金的所述金属基底。
15.权利要求12的方法，还包括提供插入在所述金属基底和所述陶瓷粘合层之间的热生长氧化物(TGO)层的步骤。
16.权利要求12的方法，还包括对所述至少一种陶瓷绝热涂层的外表面涂一外层陶瓷涂层的步骤，所述外层陶瓷粘合层包括氧化锆基和至少一种选自La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Sc、In、Y、Mo和C、稀土氧化物、钪、铟及其组合的其它元素。
17.权利要求12的方法，还包括在所述的至少一种陶瓷绝热涂层的两层之间插入陶瓷层的步骤，所述陶瓷层由YSZ构成。
18.权利要求17的方法，其中所述的插入所述陶瓷层包括插入所述的厚度在约0.5和3.0密尔之间，优选为约1.0密尔的陶瓷层。
19.权利要求12的方法，其中所述的用所述至少一种陶瓷绝热涂层涂覆所述金属基底包括通过选自热喷涂、溅射和电子束物理气相沉积(EBPVD)中的方法涂覆所述至少一种陶瓷绝热涂层。
20.权利要求12的方法，其中所述的用所述至少一种陶瓷绝热涂层涂覆所述金属基底包括用所述至少一种热导率小于约1.5W/m℃的陶瓷绝热涂层涂覆。
21.一种抗剥落性能的金属制品，包括：
金属基底；
至少一种含有氧化锆基和至少一种选自La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Sc、In、Y、Mo和C、稀土氧化物、钪和铟的其它元素的陶瓷绝热涂层；
在所述金属基底和所述至少一种陶瓷绝热涂层之间的陶瓷粘合层，其中所述陶瓷粘合层由氧化钇稳定的氧化锆(YSZ)构成；
插入在所述金属基底和所述陶瓷粘合层之间的热生长氧化物(TGO)层；和
在所述TGO层和所述金属基底之间的金属粘合层。
22.权利要求21的制品，其中所述金属基底选自钢、超级合金、钛合金和铜合金。
23.权利要求21的制品，其中所述陶瓷粘合层厚度在约0.5和3.0密尔之间，优选约1.0密尔。
24.权利要求21的制品，其中所述至少一种陶瓷绝热涂层的外表面涂有一外层陶瓷涂层，所述外层陶瓷粘合层包括氧化锆基和至少一种选自Sm、La、Yb、Ce、Lu、Mo、稀土氧化物、钇、钪、铟及其组合的其它元素。
25.权利要求21的制品，其中在所述至少一种陶瓷绝热涂层的两层之间插入陶瓷层，所述陶瓷层由YSZ构成。
26.权利要求25的制品，其中所述陶瓷层厚度在约0.5和3.0密尔之间，优选约1.0密尔。
27.权利要求21的制品，其中所述至少一种陶瓷绝热涂层通过选自热喷涂、溅射和电子束物理气相沉积(EBPVD)中的方法涂覆，并且其中所述至少一种陶瓷绝热涂层的热导率小于约1.5W/m℃。
28.权利要求21的制品，其中该制品是燃气轮机发动机部件。
29.权利要求21的制品，其中所述金属粘合层是由选自覆层(MCrAlY)和铝化物的材料形成的，并且其中所述金属基底是由能形成氧化铝层的镍基超级合金形成的。
CNA2005100762684A 2004-04-28 2005-04-27 薄7ysz界面层作为低导tbc的循环耐久性（剥落）寿命的增强 Pending CN1689800A (zh)

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