CN101522949B - 烧绿石材料和具有这些烧绿石材料的热障涂层 - Google Patents

烧绿石材料和具有这些烧绿石材料的热障涂层 Download PDF

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CN101522949B
CN101522949B CN2007800368219A CN200780036821A CN101522949B CN 101522949 B CN101522949 B CN 101522949B CN 2007800368219 A CN2007800368219 A CN 2007800368219A CN 200780036821 A CN200780036821 A CN 200780036821A CN 101522949 B CN101522949 B CN 101522949B
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T·马洛
M·奥克斯纳
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Abstract

现有技术中已知烧绿石材料可被用在陶瓷热障涂层中。通过添加镁和/或钛(Ti)和特别是采用使用这些材料的双层陶瓷层，可以实现散裂特性和热膨胀系数的进一步改进。

Description

烧绿石材料和具有这些烧绿石材料的热障涂层
本发明涉及烧绿石材料和具有这些烧绿石材料的热障涂层。
暴露于高温的金属部件必须加以防热和防腐蚀。对于燃气涡轮部件如燃烧室、涡轮叶片或轮叶来说更是如此。这些部件通常镀有MCrAlY中间层和施加在所述中间层上的陶瓷热障涂层(TBC)。
已知可以使用Gd2Zr2O7或Gd2Hf2O7作为热障涂层。
EP0992603A1公开了(Gd，La，Y)2(Ti，Zr，Hf)2O7烧绿石结构。
EP1321542A1公开了Gd2O3与HfO2的氧化物混合物，其中可以用诸如氧化锆、氧化钐、氧化铕、氧化镱或氧化钕之类的氧化物替代二氧化铪或氧化钆。
这些现有技术已知的材料还可根据其热膨胀系数和散裂特性加以进一步改进。
因此本发明的目标在于解决上述问题。
通过权利要求1中给出的烧绿石材料和权利要求17、19中给出的热障涂层可以解决所述问题。
在从属权利要求中列出了本发明的进一步有利条件，而且为了实现更多的有利条件所述从属权利要求可以彼此结合。
在附图中：
图1、2显示了层体系的例子，
图3显示了燃气涡轮，
图4显示了涡轮叶片或轮叶，
图5显示了燃烧室，
图6显示了超级合金列表。
本发明的烧绿石材料包括：
Gd2-xMgxZr2O7-a或
Gd2-xMgxHf2O7-a或
Gd2-xMgxTi2O7-a或
Gd2-xMgxZr2-yTiyO7-a或
Gd2-xMgxZr2-yHfyO7-a或
Gd2-xMgxHf2-yTiyO7-a或
Gd2-xMgxHf2-y-zZrzTiyO7-a或
Gd2Hf2-yTiyO7-a或
Gd2Hf2-y-zZryTizO7-a，
其中Gd优选地可用Sm替代，特别是全部用Sm替代：
Sm2-xMgxHf2O7-a或
Sm2-xMgxTi2O7-a或
Sm2-xMgxZr2-yTiyO7-a或
Sm2-xMgxZr2-zHfzO7-a或
Sm2-xMgxHf2-yTiyO7-a或
Sm2-xMgxHf2-y-zZrzTiyO7-a或
Sm2Zr2-yTiyO7-a或
Sm2Hf2-yTiyO7-a或
Sm2Hf2-y-zZrzTiyO7-a，
其中0＜x＜2；0＜y＜2；0≤a≤1；0＜z＜2；y+z＜2。
镁(Mg)优选地可用钙(Ca)替代。钛(Ti)优选地可用铝(Al)替代。
Gd2Zr2-xTixO7和Sm2-xMgxZr2O7-a不被称作烧绿石材料。
特别地烧绿石材料由以下材料之一构成：
Gd2-xMgxZr2O7-a或
Gd2-xMgxHf2O7-a或
Gd2-xMgxTi2O7-a或
Gd2-xMgxZr2-yTiyO7-a或
Gd2-xMgxZr2-yHfyO7-a或
Gd2-xMgxHf2-yTiyO7-a或
Gd2-xMgxHf2-y-zZrzTiyO7-a或
Gd2Hf2-yTiyO7-a或
Gd2Hf2-y-zZryTizO7-a，
其中Gd优选地可用Sm替代，特别是全部用Sm替代：
Sm2-xMgxHf2O7-a或
Sm2-xMgxTi2O7-a或
Sm2-xMgxZr2-yTiyO7-a或
Sm2-xMgxZr2-zHfzO7-a或
Sm2-xMgxHf2-yTiyO7-a或
Sm2-xMgxHf2-y-zZrzTiyO7-a或
Sm2Hf2-yTiyO7-a或
Sm2Zr2-yTiyO7-a或
Sm2Hf2-y-zZrzTiyO7-a，
其中0＜x＜2；0＜y＜2；0≤a≤1；0＜z＜2；y+z＜2。
钆(Gd)或钐(Sm)可用钕(Nd)或铕(Eu)、镱(Yb)替代，特别是全部用Nd、Eu或Yb替代。
没有要求保护用于烧绿石材料本身或含Gd和Sm作为主要成分的涂层的组合物。
在图1中，显示了包含基底4的部件1、120、130(图3，4)、155(图5)。
基底4可以为镍基或钴基超级合金。特别是采用镍基超级合金(图6)。
在此基底4上，特别是直接在基底4上，施加有粘结层和/或保护层7，特别是采用MCrAlX层，其形成或具有氧化物层(TGO)。特别是采用了钇(X＝Y)。
在此中间层7上施加有单层的外陶瓷热障涂层(TBC)10。
此热障涂层10优选地包含下列材料之一：
Gd2-xMgxZr2O7-a或
Gd2-xMgxHf2O7-a或
Gd2-xMgxTi2O7-a或
Gd2-xMgxZr2-yTiyO7-a或
Gd2-xMgxZr2-yHfyO7-a或
Gd2-xMgxHf2-yTiyO7-a或
Gd2-xMgxHf2-y-zZrzTiyO7-a或
Gd2Hf2-yTiyO7-a或
Gd2Hf2-y-zZryTizO7-a，
其中Gd可用Sm替代，特别是全部用Sm替代：
Sm2-xMgxHf2O7-a或
Sm2-xMgxTi2O7-a或
Sm2-xMgxZr2-yTiyO7-a或
Sm2-xMgxZr2-zHfzO7-a或
Sm2-xMgxHf2-yTiyO7-a或
Sm2-xMgxHf2-y-zZrzTiyO7-a或
Sm2Hf2-yTiyO7-a或
Sm2Zr2-yTiyO7-a或
Sm2Hf2-y-zZrzTiyO7-a，
其中0＜x＜2；0＜y＜2；0≤a≤1；0＜z＜2；y+z＜2，
钆(Gd)或钐(Sm)可用钕(Nd)、铕(Eu)或镱(Yb)替代。
也可以是这些材料的混合物。
在单层体系中，Gd2Zr2-xTixO7和Sm2-xMgxZr2O7-a不被称作烧绿石材料。
特别地，热障涂层10优选地由下列材料之一构成：
Gd2-xMgxZr2O7-a或
Gd2-xMgxHf2O7-a或
Gd2-xMgxTi2O7-a或
Gd2-xMgxZr2-yTiyO7-a或
Gd2-xMgxZr2-yHfzO7-a或
Gd2-xMgxHf2-yTiyO7-a或
Gd2-xMgxHf2-y-zZrzTiyO7-a或
Gd2Hf2-yTiyO7-a或
Gd2Hf2-y-zZryTizO7-a，
其中Gd优选地可用Sm替代，特别是全部用Sm替代：
Sm2-xMgxHf2O7-a或
Sm2-xMgxTi2O7-a或
Sm2-xMgxZr2-yTiyO7-a或
Sm2-xMgxZr2-zHfzO7-a或
Sm2-xMgxHf2-yTiyO7-a或
Sm2-xMgxHf2-y-zZrzTiyO7-a或
Sm2Hf2-yTiyO7-a或
Sm2Zr2-yTiyO7-a或
Sm2Hf2-y-zZrzTiyO7-a，
其中0＜x＜2；0＜y＜2；0≤a≤1；0＜z＜2；y+z＜2。
镁(Mg)优选地可用钙(Ca)替代。钛(Ti)优选地可用铝(Al)替代。
图2显示了分层的陶瓷阻挡涂层19，特别是包含、尤其是由内陶瓷热障13和外陶瓷热障16构成的两层体系。
特别地，所述陶瓷热障涂层16是所述分层体系的最外涂层。
所述内陶瓷热障涂层13包含以下材料之一：
Sm2-xMgxZr2O7-a或
Sm2-xMgxHf2O7-a或
Sm2-xMgxTi2O7-a或
Sm2-xMgxZr2-yTiyO7-a或
Sm2-xMgxZr2-zHfzO7-a或
Sm2-xMgxHf2-yTiyO7-a或
Sm2-xMgxHf2-y-zZrzTiyO7-a或
Sm2Hf2-yTiyO7-a或
Sm2Zr2-yTiyO7-a或
Sm2Hf2-y-zZrzTiyO7-a，
其中0＜x＜2；0＜y＜2；0≤a≤1；0＜z＜2；y+z＜2。
特别地，所述内TBC13由以下材料之一构成：
Sm2-xMgxZr2O7-a或
Sm2-xMgxHf2O7-a或
Sm2-xMgxTi2O7-a或
Sm2-xMgxZr2-yTiyO7-a或
Sm2-xMgxZr2-zHfzO7-a或
Sm2-xMgxHf2-yTiyO7-a或
Sm2-xMgxHf2-y-zZrzTiyO7-a或
Sm2Hf2-yTiyO7-a或
Sm2Zr2-yTiyO7-a或
Sm2Hf2-y-zZrzTiyO7-a，
其中0＜x＜2；0＜y＜2；0≤a≤1；0＜z＜2；y+z＜2。
特别是选择a＝x/2。
镁(Mg)优选地可用钙(Ca)替代。
钛(Ti)优选地可用铝(Al)替代。
钛(Ti)使得陶瓷涂层的散裂减少。
Mg使得热膨胀系数与所述超级合金和/或金属层的热膨胀系数相适应。
所述内陶瓷热障涂层13还可以包含或由YSZ构成。
所述外陶瓷热障涂层16包含
Gd2-xMgxZr2O7-a或
Gd2-xMgxHf2O7-a或
Gd2-xMgxTi2O7-a或
Gd2-xMgxZr2-yTiyO7-a或
Gd2-xMgxZr2-yHfzO7-a或
Gd2-xMgxHf2-yTiyO7-a或
Gd2-xMgxHf2-y-zZrzTiyO7-a或
Gd2Hf2-y-zZryTizO7-a或
Gd2Zr2-xTixO7-a或
Gd2Hf2-yTiyO7-a。
特别地，所述外TBC16由以下材料之一构成：
Gd2-xMgxZr2O7-a或
Gd2-xMgxHf2O7-a或
Gd2-xMgxTi2O7-a或
Gd2-xMgxZr2-yTiyO7-a或
Gd2-xMgxZr2-yHfzO7-a或
Gd2-xMgxHf2-yTiyO7-a或
Gd2-xMgxHf2-y-zZrzTiyO7-a或
Gd2Hf2-y-zZryTizO7-a或
Gd2Zr2-xTixO7-a或
Gd2Hf2-yTiyO7-a。
钛(Ti)优选地可用铝(Al)替代。
在类似于图1或图2的层体系中，陶瓷阻挡涂层10、13、16的组成可以具有梯度。组成中的梯度可以通过增大或减小参数x、y、z的值来实现。
组成可以特别是从Gd2-xMgxHf2O7-a逐渐变成Gd2-xMgxHf2-yTiyO7-a，并最终在最外层表面区域变成Gd2Hf2-yTiyO7-a。
图1显示了一种本发明的层体系1。
所述层体系1包括金属基底4，其特别是对于在高温下使用的部件来说由镍基或钴基超级合金构成。
直接在所述基底4上有金属粘结层7，其由11wt％-13wt％钴、20wt％-22wt％铬、10.5wt％-11.5wt％铝、0.3wt％-0.5wt％钇、1.5wt％-2.5wt％铼和余量镍构成，或由24wt％-26wt％钴、16wt％-18wt％铬、9.5wt％-11wt％铝、0.3wt％-0.5wt％钇、0.5wt％-2wt％铼和余量镍构成。
甚至在施加进一步的陶瓷层之前，在此金属粘结层7上就形成了氧化铝层，或者在工作期间形成此类的氧化铝层。
在所述金属粘结层7或所述氧化铝层(未显示)上可以存在完全稳定或部分稳定的氧化锆层作为内陶瓷层10。优选地使用钇稳定的氧化锆。也可以使用氧化钙、二氧化铈或二氧化铪来稳定氧化锆。
所述氧化锆优选地作为等离子喷镀层施加，也可借助于电子束物理气相沉积作为柱状结构施加。
图3举例显示了穿过燃气涡轮100的部分纵截面。
在其内部，燃气涡轮100具有转子103，转子103的安置使得其可以绕旋转轴102旋转，转子103具有轴101且又被称作涡轮转子。
沿转子103依次为进气壳体104、压缩机105、具有多个共轴排列的燃烧器107的例如环形的燃烧室110，特别是环状燃烧室、涡轮108和排气壳体109。
环状燃烧室110与例如环状热气体通道111连通，在所述热气体通道111内，例如，四个相继的涡轮级112构成涡轮108。每个涡轮级112由，例如，两个叶片或轮叶环构成。从工作介质113的流动方向上看，在热气体通道111内一排导叶115之后是由转子叶片120构成的一排125。
导叶130被固定在定子143的内壳138上，而排125中的转子叶片120被例如通过涡轮盘133安装在转子103上。发电机(未显示)被连接在转子103上。
当燃气涡轮100工作时，压缩机105通过进气壳体104吸入空气135并对其进行压缩。在压缩机105的涡轮侧一端提供的压缩空气被送往燃烧器107，在燃烧器107压缩空气与燃料混合。然后混合物在燃烧室110中燃烧，形成工作介质113。从那里，工作介质113沿热气体通道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上扩展，传递其动量，使得转子叶片120驱动转子103，而后者接着驱动与其连接在一起的发电机。
在燃气涡轮100工作时，暴露于所述热工作介质113的部件受到热应力。第一涡轮级112中的导叶130和转子叶片120，从工作介质113的流动方向看，连同衬在环状燃烧室110中的热屏蔽元件受到最高的热应力。
为了能够承受那里的温度，可用冷却剂对它们进行冷却。部件的基底同样可以具有定向构造，即它们呈单晶形式(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、特别是涡轮叶片或轮叶120、130以及燃烧室110的部件的材料。
这类超级合金从例如EP1204776B1、EP1306454、EP1319729A1、WO99/67435或WO00/44949已知；这些文献在合金的化学组成方面构成本公开的一部分。
叶片或轮叶120、130还可具有防腐涂层(MCrAlX；M为选自铁(Fe)、钴(Co)、镍(Ni)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和/或铪)。
这类合金由EP0486489B1、EP0786017B1、EP0412397B1或EP1306454A1已知，它们在化学组成方面构成本公开的一部分。
在所述MCrAlX上还可存在由例如ZrO2，Y2O3-ZrO2，即不稳定的、用氧化钇和/或氧化钙和/或氧化镁部分稳定或完全稳定的氧化锆构成的热障涂层。
通过适当的涂覆工艺，例如电子束物理气相沉积(EB-PVD)，在热障涂层中产生了柱状晶粒。
导叶130具有面向涡轮108的内壳138的导叶根(此处未显示)和在与导叶根相对一端的导叶头。导叶头面向转子103，并被固定在定子143的固定环140上。
图4显示了涡轮机的转子叶片120或导叶130沿纵轴121延伸的透视图。
所述涡轮机可以是飞行器或发电厂用于发电的燃气涡轮、蒸汽涡轮或压缩机。
所述叶片或轮叶120、130沿纵轴121依次具有固定区域400、邻接叶片或轮叶平台403和主叶片或轮叶部分406。作为导叶130，轮叶130可以在其叶片尖端415具有进一步的平台(未显示)。
在固定区域400形成有用于将转子叶片120、130固定到轴或盘(未显示)上的叶片或轮叶根183。所述叶片或轮叶根183被设计成例如锤头形式的。也可采用其它构型如枞树根或鸽尾形根。
叶片或轮叶120、130具有前沿409和后沿412，供流过主叶片或轮叶部分406的介质使用。
就传统的叶片或轮叶120、130来说，例如实心金属材料、特别是超级合金被用于所述叶片或轮叶120、130的所有区域400、403、406。
这类超级合金从例如EP1204776B1、EP1306454、EP1319729A1、WO99/67435或WO00/44949已知；这些文献在合金的化学组成方面构成本公开的一部分。在这种情形下，叶片或轮叶120、130可以通过浇铸工艺制造，也可通过定向凝固、锻造工艺、研磨工艺或其结合制造。
具有单晶结构的工件被用作在工作时暴露于高机械、热和/或化学应力的设备的部件。此类单晶工件可通过例如定向凝固由熔体制造。这涉及其中液态金属合金凝固形成单晶结构，即单晶工件，或定向凝固的浇铸工艺。在这种情形下，树枝状晶体沿热流方向取向并形成柱状晶粒结构(即遍布工件全部长度的晶粒，按照通常使用的语言在此被称作定向凝固)或单晶结构，即整个工件由一个单晶构成。在这些工艺中，需要避免向小球状(多晶)凝固的转变，因为非定向的生长不可避免地会形成横向和纵向晶粒边界，这会使所述定向凝固的或单晶的部件的有利特性消失。
在文字上一般性涉及定向凝固的微观结构的地方，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，又指具有纵向的晶界但不具有任何横向的晶界的柱状晶体结构。所述第二种形式的晶体结构又被描述为定向凝固的微观结构(定向凝固的结构)。
这类工艺由US-A6,024,792和EP0892090A1已知；这些文献构成本公开的一部分。
叶片或轮叶120、130还可具有防腐或抗氧化涂层，例如(MCrAlX；M为选自铁(Fe)、钴(Co)、镍(Ni)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))。这类合金由EP0486489B1、EP0786017B1、EP0412397B1或EP1306454A1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氧化锆构成的热障涂层。通过适当的涂覆工艺，例如电子束物理气相沉积(EB-PVD)，在热障涂层中产生了柱状晶粒。
修复是指保护层在被使用之后，它们可能必须被从部件120、130上除去(例如通过喷砂)。然后，腐蚀和/或氧化层和产物被除去。适当时，部件120、130中的裂纹也被修复。之后继之以重新涂覆部件120、130，然后部件120、130就能被重新使用了。
叶片或轮叶120、130的形式可以为中空或实心的。如果叶片或轮叶120、130需要冷却，则其是中空的且可以具有膜冷却孔418(以虚线表示)。

Claims (30)

1.热障涂层(10、19)，其包含烧绿石材料，所述烧绿石材料包括Gd2-xMgxZr2O7-a，其中0＜x＜2和0≤a≤1，其中排除a＝0的方案。
2.热障涂层(10、19)，其包含烧绿石材料，所述烧绿石材料包括Gd2-xMgxZr2-yTiyO7-a，其中0＜y＜2和0＜x＜2和0≤a≤1，其中排除a＝0的方案。
3.权利要求1的热障涂层，其中锆(Zr)被铪(Hf)部分替代。
4.权利要求2的热障涂层，其中锆(Zr)被铪(Hf)部分替代。
5.权利要求1的热障涂层，其中锆(Zr)被铪(Hf)全部替代。
6.权利要求1的热障涂层，其中锆(Zr)被钛(Ti)部分替代。
7.权利要求1的热障涂层，其中锆(Zr)被钛(Ti)全部替代。
8.权利要求1的热障涂层，其中钆(Gd)被钕(Nd)、铕(Eu)或镱(Yb)替代。
9.权利要求1的热障涂层，其中钆(Gd)被钐(Sm)部分替代。
10.权利要求1的热障涂层，其中钆(Gd)被钐(Sm)全部替代。
11.权利要求1的热障涂层，其中镁(Mg)被钙(Ca)部分替代。
12.权利要求2、6或7的热障涂层，其中钛(Ti)被铝(Al)部分替代。
13.权利要求2、6或7的热障涂层，其中钛(Ti)被铝(Al)全部替代。
14.由权利要求1中所述的材料的单一种构成的热障涂层。
15.由权利要求1、2、3、4、6、7和8-13的任一项中所述的材料构成的热障涂层(10、19)。
16.热障涂层，其中热障涂层(19)包含两层(13、16)材料，所述材料选自权利要求1、2、3、4、6、7和8-13的任一项中所述的材料，所述材料为陶瓷材料。
17.权利要求16的热障涂层，其中热障涂层(10)由两层(13、16)选自权利要求1、2、3、4、6、7和8-13的任一项中所述的材料的材料构成，所述材料为陶瓷材料。
18.权利要求16或17的热障涂层，其中内陶瓷热障涂层(13)包含权利要求9或10中所述的材料。
19.权利要求16或17的热障涂层，其中内陶瓷热障涂层(13)包含Sm2-xMgxZr2O7-a，所述Sm2-xMgxZr2O7-a中的x和a的定义是：
0＜x＜2和0≤a≤1，其中排除a＝0的方案。
20.权利要求17的热障涂层，其中内陶瓷热障涂层(13)由权利要求10或11中所述的材料构成。
21.权利要求17的热障涂层，其中内陶瓷热障涂层(13)由Sm2-xMgxZr2O7-a构成，所述Sm2-xMgxZr2O7-a中的x和a的定义是：
0＜x＜2和0≤a≤1，其中排除a＝0的方案。
22.权利要求18的热障涂层，其中钐(Sm)被钆(Gd)部分替代。
23.权利要求19的热障涂层，其中钐(Sm)被钆(Gd)部分替代。
24.权利要求18的热障涂层，其中钐(Sm)被钆(Gd)全部替代。
25.权利要求19的热障涂层，其中钐(Sm)被钆(Gd)全部替代。
26.权利要求16或17的热障涂层，其中内陶瓷热障涂层(13)包含氧化锆。
27.权利要求16、17、20或21的热障涂层，其中外陶瓷热障涂层(16)包含权利要求1、2、3、4、6、7、8和11-13之一的一种材料。
28.权利要求16、17、20或21的热障涂层，其中外陶瓷热障涂层(16)包含Gd2Zr1-yTiyO7-a，所述Gd2Zr1-yTiyO7-a中的y和a的定义是：
0＜y＜2和0≤a≤1。
29.权利要求28的热障涂层，其中外陶瓷热障涂层(16)由权利要求1、2、3、4、6、7、8和11-13之一的一种材料构成。
30.权利要求28的热障涂层，其中外陶瓷热障涂层(16)由Gd2Zr1-yTiyO7-a构成，所述Gd2Zr1-yTiyO7-a中的y和a的定义是：
0＜y＜2和0≤a≤1。
CN2007800368219A 2006-10-02 2007-06-21 烧绿石材料和具有这些烧绿石材料的热障涂层 Expired - Fee Related CN101522949B (zh)

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CN101522949A (zh) 2009-09-02
EP2302101A1 (en) 2011-03-30
ATE549432T1 (de) 2012-03-15
WO2008040574A1 (en) 2008-04-10
US8278232B2 (en) 2012-10-02
EP2069552B1 (en) 2012-03-14
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EP2309031A2 (en) 2011-04-13
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