CN101611171B - 具有高孔隙度的层状热障涂层和部件 - Google Patents

具有高孔隙度的层状热障涂层和部件 Download PDF

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CN101611171B
CN101611171B CN2007800122030A CN200780012203A CN101611171B CN 101611171 B CN101611171 B CN 101611171B CN 2007800122030 A CN2007800122030 A CN 2007800122030A CN 200780012203 A CN200780012203 A CN 200780012203A CN 101611171 B CN101611171 B CN 101611171B
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thermal barrier
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porosity
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W·斯塔姆
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Abstract

现有技术的陶瓷热障涂层往往并不能承受热应力和机械应力。本发明的陶瓷热障涂层(10)包括两个具有不同孔隙度的陶瓷热障层(11、13)，其中甚至内陶瓷热障层(11)也具有高孔隙度。

Description

具有高孔隙度的层状热障涂层和部件
本发明涉及根据权利要求1所述的高孔隙度层状热障涂层和根据权利要求11所述的部件。
US4,299,865公开了包括具有20vol％-33vol％的极高孔隙度的外层和致密陶瓷热障内层的双层陶瓷热障涂层。
专利EP0816526B1公开了只包括孔隙度为20vol％-35vol％的单层的热障涂层体系。
US4,936,745公开了孔隙度为20vol％-35vol％的单陶瓷层。
US2004/0126599A1公开了具有不同显微结构的双层热障涂层。
热障涂层实质上是功能层，用于保护基材，例如防止其过热。基材具有充分高的机械强度。热障涂层同样暴露于热应力和/或机械应力，且可能由于裂纹而导致失效。
因此，本发明目的在于提供一种热障涂层和一种其中各层能更好地承受热应力和机械应力的部件。
此目的是通过根据权利要求1所述的热障涂层和根据权利要求11所述的部件实现的。
示范性实施方案显示在附图中。
图1显示了热障涂层的一个例子，
图2显示了热障涂层的另一个例子，
图3列举一些用于所述热障涂层的基材的超级合金，
图4显示了一个燃气涡轮，
图5显示了涡轮叶片或轮叶，
图6显示了燃烧室。
在图1中，显示了热障涂层体系1的一个例子。
该热障涂层体系1包括金属基材4，金属基材4是钴基或镍基的且是燃气涡轮100(图4)的部件120、130(图5)、155(图6)。所述金属基材4由超级合金(图3)制成。
优选地向此基材4上施加MCrAlX型金属粘结层7。在操作过程中或在施加进一步涂层(10)之前在此金属粘结层7上形成热生长的氧化物层(TGO)(未显示)。
向金属粘结层7上施加含至少两个层的陶瓷热障涂层10。陶瓷热障涂层10具有内陶瓷热障层11和外陶瓷热障层13，其中外陶瓷热障层13面向热介质，特别是燃气涡轮100的热气体通路。
所述内陶瓷热障涂层11不是陶瓷TGO。
特别地所述内陶瓷热障涂层11具有与所述外陶瓷热障涂层13相同的化学组成。
外陶瓷层13的孔隙度高于内陶瓷层11。
内陶瓷层11和外陶瓷层13的孔隙度范围不重叠也不具有相同值。
一种有利的实施例为：内陶瓷热障层11的孔隙度为5vol％-11vol％，特别是9vol％-11vol％，外陶瓷热障层13的孔隙度为20vol％-27vol％，特别是21vol％-27vol％，更特别是23vol％-27vol％。
显然，内陶瓷热障层11的孔隙度最大值远小于外陶瓷热障层13的孔隙度最小值。
在图2中显示了有利的热障涂层10的另一个例子。
在内陶瓷热障层11与外陶瓷热障层13之间存在中间陶瓷热障层12，其中所述外陶瓷热障层13面向热介质，特别是燃气涡轮100的热气体通路。
所述内陶瓷热障涂层11不是陶瓷TGO。
特别地所述内陶瓷热障涂层11具有与所述中间陶瓷热障涂层12和所述外陶瓷热障涂层13相同的化学组成。
一种有利的实施例为：内陶瓷热障层11的孔隙度为5vol％-11vol％，特别是9vol％-11vol％，外陶瓷热障层13的孔隙度为20vol％-27vol％，特别是23vol％-27vol％。
中间陶瓷热障层12的孔隙度低于外陶瓷热障层13的孔隙度。特别是，中间陶瓷热障层12的孔隙度在内陶瓷热障层11与外陶瓷热障层13的孔隙度范围之间。更有利地，此层12的孔隙度在内陶瓷热障层11的孔隙度值与外陶瓷热障层13的孔隙度值之间逐渐变化。
中间陶瓷热障涂层12的层厚优选值为最高150μm，特别是最高75μm。
特别地，在图1、2所示的实施例中，内陶瓷热障层11的厚度为100μm-150μm，特别是125μm。
在图1、2所示的实施例中，外陶瓷热障涂层13的厚度为150μm-2mm，特别是1mm-2mm。
用于陶瓷涂层11、12、13的材料可以随意选择，特别是使用氧化钇稳定的氧化锆(Y2O3-ZrO2)。
甚至涂层11、12、13可以使用不同材料。
特别地，内、中间和外陶瓷热障涂层是等离子体喷涂的。
这意味着通常所述内、中间或外陶瓷热障涂层的形态不具有类似于EB-PVD层的柱状结构，而是具有平面粒状结构(flattened grainstructure)。
特别地，热障涂层10由两个层构成：内陶瓷热障涂层11和最外陶瓷热障层13。
更特别地，热障涂层10由三个层构成：内陶瓷热障层11、中间陶瓷热障层12和最外陶瓷热障层13。
图4举例显示了穿过燃气轮机100的局部纵截面。
在其内部，燃气轮机100具有转子103，转子103的安装使得其可以绕旋转轴102转动，具有轴101并被称作涡轮转子。进气室104、压缩机105、具有多个同轴排列的燃烧器107的例如曲面燃烧室110，特别是环形燃烧室，涡轮108和排气室109沿转子103彼此相继排列。
所述环形燃烧室110与例如环形热气通道111相连通，在所述环形热气通道111中例如有四个连续涡轮级112构成涡轮108。
每个涡轮级112例如由两个叶片或轮叶环构成。在热气通道111中，在工作介质113的流动方向上看，一排导叶115后接着由转子叶片120构成的一排125。
所述导叶130被固定在定子143的内套138上，而一排125的转子叶片120通过例如涡轮盘133配合到转子103上。
发电机(未显示)联结在所述转子103上。
燃气涡轮100工作时，压缩机105通过进气室104吸入空气135并对其进行压缩。在压缩机105的涡轮侧端提供的压缩空气被送往燃烧器107，在那里与燃料混合。然后该混合物在燃烧室110中燃烧，形成工作介质113。工作介质113从那里沿热气通道111流动通过导叶130和转子叶片120。工作介质113在转子叶片120上扩张，传递其动量，从而转子叶片120驱动转子103而后者接着驱动与其联结在一起的发电机。
在燃气涡轮100工作时，暴露于热工作介质113的部件受到热应力。第一涡轮级112的导叶130和转子叶片120，在工作介质113的流动方向上看，连同衬在环形燃烧室110内的热屏蔽砖一起，受到最高的热应力。
为了能经受住那里的温度，可以用冷却剂对它们进行冷却。
部件的基材同样可以具有定向结构，即它们是单晶形式的(SX结构)或只具有纵向取向的晶粒(DS结构)。例如，铁基、镍基或钴基超级合金被用作所述部件特别是涡轮机叶片或轮叶120、130和燃烧室110的部件的材料。
此类超级合金从例如EP1204776B1、EP1306454、EP1319729A1、WO99/67435或WO00/44949已知；这些文献在所述合金的化学组成方面构成本公开的一部分。
导叶130具有面向涡轮108的内套138的导叶根(在这里未显示)，还具有位于与导叶根相反端的导叶头。导叶头面向转子103并被固定到定子143的固定环140上。
图5显示了涡轮机的转子叶片120或导叶130的透视图，其沿纵轴121延伸。
所述涡轮机可以为飞行器的或发电厂用于发电的燃气轮机、蒸汽涡轮或压缩机。
叶片或轮叶120、130沿纵轴121依次具有固定区400、邻接叶片或轮叶平台403、和主叶片或轮叶部分406、以及叶片或轮叶尖端415。作为导叶130，可以在其轮叶尖端415具有另一个平台(未显示)。
在所述固定区400内形成用于将转子叶片120、130固定在轴或盘(未显示)上的叶片或轮叶根183。叶片或轮叶根183设计成，例如，锤头形状。也可采用其它构型，如枞树或鸽尾形根。
叶片或轮叶120、130具有用于流过主叶片或轮叶部分406的介质的前缘409和后缘412。
对于普通的叶片或轮叶120、130，在该叶片或轮叶120、130的所有区域400、403、406中都使用例如固体金属材料，特别是超级合金。
此类超级合金从例如EP1204776B1、EP1306454、EP1319729A1、WO99/67435或WO00/44949已知；这些文献在所述合金的化学组成方面构成本公开的一部分。
在这种情况下，叶片或轮叶120、130可以通过浇铸法制造，也可通过定向凝固、锻造法、粉碎法或其组合制造。
具有单晶结构的工件被用作在工作中暴露于高机械、热和/或化学应力的机器的部件。此类单晶工件是通过例如熔体的定向凝固制造的。这涉及其中液态金属合金凝固形成单晶结构即单晶工件或定向凝固的浇铸过程。在这种情况下，枝晶沿热流方向取向并形成柱状晶粒结构(即晶粒遍及工件的整个长度且在这里，根据常用的语言，被称作定向凝固)或单晶结构，即整个工件由一个单晶构成。在这些过程中，需要避免转化成球状(多晶)凝固，因为不定向的生长不可避免地会形成横向和纵向的晶粒边界，其将消除定向凝固的或单晶的部件的有利性质。
在本文一般性提及定向凝固显微结构时，应理解为既指不具有任何晶界或最多具有小角度晶界的单晶，又指具有沿纵向的晶界但不具有任何横向晶界的柱状晶体结构。第二种晶体结构也被称作定向凝固显微结构(定向凝固结构)。此类工艺由US-A6,024,792和EP0892090A1已知；这些文献在凝固工艺方面构成本公开的一部分。
叶片或轮叶120、130可以同样具有保护它们不受腐蚀或氧化的涂层，例如MCrAlX(M为选自铁(Fe)、钴(Co)、镍(Ni)中的至少一种元素，X为活性元素且代表钇(Y)和/或硅和/或至少一种稀土元素、或铪(Hf))。此类合金从EP0486489B1、EP0786017B1、EP0412397B1或EP1306454A1中已知，它们在合金的化学组成方面构成本公开的一部分。
密度优选地为理论密度的95％。在所述MCrAlX层上形成保护性氧化铝层(TGO＝热生长的氧化物层)(作为中间层或最外层)。
在所述MCrAlX上还可以存在由例如ZrO2、Y2O3-ZrO2，即不稳定的、用氧化钇和/或氧化钙和/或氧化镁部分稳定的或完全稳定的ZrO2，构成的热障涂层，其优选地为最外层。
所述热障涂层覆盖整个MCrAlX层。通过适当的涂覆工艺，例如电子束物理汽相沉积(EB-PVD)，在所述热障涂层中形成了柱状晶粒。也可采用其它涂覆工艺，例如大气等离子体喷镀(APS)、LPPS、VPS或CVD。所述热障涂层可以包含具有微裂纹或宏观裂纹的多孔颗粒，用于改善其耐热震性。因此所述热障涂层优选地比所述MCrAlX层更加多孔。
所述叶片或轮叶120、130形式上可以是中空或实心的。如果所述叶片或轮叶120、130将会被冷却，则其是中空的且还可具有膜冷却孔418(由虚线表示)。
图6显示了燃气涡轮100的燃烧室110。燃烧室110成形为，例如，所谓的环形燃烧室，其中绕旋转轴102圆周排列的多个燃烧器107向公用燃烧室空间154中开口并产生火焰156。为此，燃烧室110总地说来是位于旋转轴102周围的环形构造。
为实现较高的效率，燃烧室110针对约1000℃-1600℃的较高工作介质M温度设计。为即使是在这些对所述材料不利的工作参数下实现较长的使用寿命，在燃烧室壁153的面向工作介质M一侧提供有由热屏蔽元件155构成的内衬。
由于燃烧室110内部的高温，还可以向热屏蔽元件155和/或它们的固定元件提供冷却系统。此时，热屏蔽元件155是，例如，中空的并适当时可同时具有向燃烧室空间154中开口的冷却孔(未显示)。
由合金制成的每个热屏蔽元件155在工作介质一侧都具备特别耐热的保护层(MCrAlX层和/或陶瓷涂层)或由耐高温材料(实心陶瓷砖)制成。
这些保护层可以与用于涡轮叶片或轮叶的那些类似，即例如是指MCrAlX：M为选自铁(Fe)、钴(Co)、镍(Ni)中的至少一种元素，X为活性元素且代表钇(Y)和/或硅和/或至少一种稀土元素、或铪(Hf))。此类合金从EP0486489B1、EP0786017B1、EP0412397B1或EP1306454A1中已知，它们在合金的化学组成方面构成本公开的一部分。
在所述MCrAlX上还可以存在一个例如由ZrO2、Y2O3-ZrO2，即不稳定的、用氧化钇和/或氧化钙和/或氧化镁部分稳定的或完全稳定的ZrO2，构成的陶瓷热障涂层。
通过适当的涂覆工艺，例如电子束物理汽相沉积(EB-PVD)，在所述热障涂层中形成了柱状晶粒。也可采用其它涂覆工艺，例如大气等离子体喷镀(APS)、LPPS、VPS或CVD。所述热障涂层可以包含具有微裂纹或宏观裂纹的多孔颗粒，用于改善其耐热震性。
修复是指，保护层在使用之后可能不得不从涡轮叶片或轮叶120、130、热屏蔽元件155上去除(例如通过喷砂)。然后，腐蚀和/或氧化层以及产物被除去。适当时，涡轮机叶片或轮叶120、130或热屏蔽元件155内的裂纹也被修复。接着重新涂覆涡轮叶片或轮叶120、130、热屏蔽元件155，之后涡轮叶片或轮叶120、130、热屏蔽元件155可被重新使用。

Claims (18)

1.部件的热障涂层(10)，其具有三个层(11、12、13)，其中内陶瓷热障层(11)最靠近部件的基材(4)且孔隙度为9vol％-11vol％，外陶瓷热障层(13)的孔隙度为20vol％-27vol％，且在所述内陶瓷热障层(11)与所述外陶瓷热障层(13)之间存在中间陶瓷热障层(12)，其中所述中间陶瓷热障层(12)的孔隙度介于内陶瓷热障层(11)的孔隙度最大值与外陶瓷热障层(13)的孔隙度最小值之间。
2.根据权利要求1所述的热障涂层，其中所述中间陶瓷热障层(12)的孔隙度由最小值逐渐变化至最大值。
3.根据权利要求2所述的热障涂层，其中所述中间陶瓷热障层(12)的孔隙度从所述内陶瓷热障层(11)的孔隙度增大到所述外陶瓷热障层(13)的孔隙度。
4.根据权利要求1所述的热障涂层，其中所述中间陶瓷热障层(12)的孔隙度具有恒定值。
5.根据权利要求1所述的热障涂层，其中所述内陶瓷热障层(11)的层厚为100μm-150μm。
6.根据权利要求1所述的热障涂层，其中所述中间陶瓷热障层(12)的层厚为最高150μm。
7.根据权利要求1所述的热障涂层，其中所述外陶瓷热障层(13)的层厚为150μm-2000μm。
8.根据权利要求1所述的热障涂层，其中所述陶瓷热障层(11、12、13)的材料由用氧化钇稳定的氧化锆构成。
9.根据权利要求1所述的热障涂层，其中所述内陶瓷热障涂层(11)是等离子体喷涂的。
10.根据权利要求1或9所述的热障涂层，其中所述中间陶瓷热障涂层(12)是等离子体喷涂的。
11.根据权利要求1或9所述的热障涂层，其中所述外陶瓷热障涂层(13)是等离子体喷涂的。
12.在基材(4)上具有根据权利要求1所述的热障涂层(10)的部件。
13.根据权利要求12所述的部件，其中所述基材(4)上的中间金属层(7)由以wt％计为Ni-12Co-21Cr-11Al-0.4Y-Re制成。
14.根据权利要求12所述的部件，其中所述基材(4)上的中间金属层(7)由以wt％计为Ni-25Co-17Cr-10Al-0.5Y-Re制成。
15.根据权利要求12所述的部件，其中所述基材(4)上的中间金属层(7)由以wt％计为Co-30Ni-28Cr-8Al-0.6Y-0.7Si制成。
16.根据权利要求12、13、14或15所述的部件，其中所述基材(4)是镍基的。
17.根据权利要求12、13、14或15所述的部件，其中所述基材(4)是钴基的。
18.根据权利要求12、13、14或15所述的部件，其为涡轮叶片、涡轮轮叶、热屏蔽或外壳。
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US20090311508A1 (en) 2009-12-17
KR20080110983A (ko) 2008-12-22
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WO2007115839A2 (en) 2007-10-18
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