CN101300374B - 具有烧绿石相的双层热防护层系统 - Google Patents

具有烧绿石相的双层热防护层系统 Download PDF

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CN101300374B
CN101300374B CN2006800410175A CN200680041017A CN101300374B CN 101300374 B CN101300374 B CN 101300374B CN 2006800410175 A CN2006800410175 A CN 2006800410175A CN 200680041017 A CN200680041017 A CN 200680041017A CN 101300374 B CN101300374 B CN 101300374B
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E·舒曼
R·素布拉马尼安
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Abstract

除了良好的绝热性能,绝热层体系必须还具备绝热层的长使用寿命。本发明的层体系(1)包括具有特定彼此适配的层顺序:金属粘附层(7),其由NiCoCrAlX构成,陶瓷内层(10)和陶瓷外层(13),陶瓷外层含有至少80%的烧绿石相Gd2Zr2O7或Gd2Hf2O7

Description

具有烧绿石相的双层热防护层系统
本发明涉及根据权利要求1的含烧绿石的层体系。
这样的层体系具有包括基于镍或钴的金属合金的基材。这样的产品特别用作燃气轮机的组件,特别是用作燃气轮机桨叶或者隔热板。该部件暴露于腐蚀性的燃烧气体的热气流。因此,它们必须能经受高热负荷状态。此外,要求这些部件是耐氧化和耐腐蚀的。特别是对于移动部件,例如燃气轮机叶片,还有静态部件,还存在机械要求。其中有部件暴露于热气体的燃气轮机的功率和效率随工作温度升高而增加。为了实现高效率和高功率,用陶瓷材料涂覆特别是暴露于高温的那些燃气轮机部件。这些陶瓷材料用作热气流和金属基材之间的绝热层。
通过涂覆,金属基底受到保护以免遭腐蚀性的热气流损害。在这里,现代的部件通常包含分别实现特定功能的多个涂料。因此,该体系是多层系统。
燃气轮机的功率和效率随工作温度上升而增加,因此总是试图通过改善涂层系统来提高燃气轮机的性能。
EP 0 944 746 B1公开了烧绿石作为绝热层的用途。但是,用作绝热层的材料不仅要求良好的绝热性能,而且要求对基材良好的粘附性。
EP0992603A1公开了氧化钆和氧化锆的绝热层体系,其据称并不含烧绿石型结构。
因此,本发明的一个主题是提供具有良好的绝热性能和良好的对基材粘附性因而具有整个层体系的长使用期限的层体系。
本发明基于如下发现:为了实现长使用期限,整个体系必须作为整体考虑,而不应当作为单层或者彼此分开的某些层分开考虑,和相对彼此进行分别优化。
该目的是通过本发明的层体系实现的,其包括
基材(4),
金属粘附层(7),其由NiCoCrAlX合金构成,
在金属粘附层(7)上的陶瓷内层(10),特别是经稳定化的氧化锆层,特别是钇稳定化的氧化锆层,
其中
在陶瓷内层(10)上存在陶瓷外层(13),该陶瓷外层(13)含至少80重量%、特别是100重量%的烧绿石相Gd2Zr2O7,其中内层(10)的层厚为内层(10)和外层(13)的总层厚的10%至50%。
从属权利要求描述了进一步的有益的措施,其可以以任何期望的方式组合。
附图说明
图1示出了本发明的层体系。
图2示出了一片高温合金,
图3示出了涡轮机叶片的透视图,
图4示出了燃烧室的透视图,
图5示出了燃气轮机。
图1示出了本发明的层体系1。
层体系1包括金属基材4,特别对于处于高温下的部件,其由基于镍或钴的高温合金构成(图2)。
直接在基材4上,优选存在特别是NiCoCrAlX类型的金属粘附层7,所述金属粘附层7优选由下列组成:
(11-13)重量%钴,特别是12重量%Co,
(20-22)重量%铬,特别是21重量%Cr,
(10.5-11.5)重量%铝,特别是11重量%Al,
(0.3-0.5)重量%钇,特别是0.4重量%Y,
(1.5-2.5)重量%铼和特别是2.0重量%Re,
和余量的镍,
或者,优选由下列组成:
(24-26)重量%钴,特别是25重量%Co,
(16-18)重量%铬,特别是17重量%Cr,
(9.5-10.5)重量%铝,特别是10重量%Al,
(0.3-0.5)重量%钇,特别是0.4重量%Y,
(1.0-2.0)重量%铼和特别是1.5重量%Re,
和余量的镍,
或者,优选由下列组成:
29重量%-31重量%镍,特别是30重量%镍,
27重量%-29重量%铬,特别是28重量%铬,
7重量%-9重量%铝,特别是8重量%铝,
0.5重量%-0.7重量%钇,特别是0.6重量%钇,
0.6重量%-0.8重量%硅,特别是0.7重量%硅,和
余量的钴,
或者,优选由下列组成:
27重量%-29重量%镍,特别是28重量%镍,
23重量%-25重量%铬,特别是24重量%铬,
9重量%-11重量%铝,特别是10重量%铝,
0.3重量%-0.7重量%钇,特别是0.6重量%钇,和
余量的钴。
在施加进一步的陶瓷层之前,优选已经在该金属粘附层7上存在氧化铝层,或者在运行期间形成这样的氧化铝层(TGO)。
在所述金属粘附层7上或者在氧化铝层(未示出)上通常存在内部陶瓷层10,优选完全或者部分稳定化的氧化锆层。优选使用钇稳定化的氧化锆,其中优选使用6重量%-8重量%的钇。氧化钙、二氧化铈和/或二氧化铪同样可以用于稳定化氧化锆。
氧化锆优选作为等离子体喷雾层施加,尽管其还优选作为柱状结构借助电子束沉积(EBPVD)施加。
将陶瓷外层13施加到经稳定化的氧化锆层10上,其中所述陶瓷外层13大部分由烧绿石相构成,也就是说其包含至少80重量%的烧绿石相,所述烧绿石相由Gd2Hf2O7或者Gd2Zr2O7构成。
优选地,100重量%的所述外层13由所述两种烧绿石相之一组成。在这种情况下,不合烧绿石相的非晶质相、纯的GdO2、纯的ZrO2或者纯的HfO2、GdO2和ZrO2或者HfO2的混合相是不理想的,并应该最小化。
内层10的层厚优选为内层10加上外层13的总层厚的10%至50%。
陶瓷内层10优选具有40μm到60μm的厚度,特别是50μm±10%。
内层10加上外层13的总层厚优选为300μm或优选400μm。最大总层厚有利地为800μm或者优选至多600μm。
内层10的层厚优选为总层厚的10%至40%或者10%-30%。
对于内层10的层厚而言,同样有利的是,其占总层厚的10%到20%。
对于内层10的层厚而言,同样优选的是,其占总层厚的20%-50%,或者优选20%-40%。
如果内层10占总层厚的20%-30%,同样得到了有利的结果。
内层10的层厚优选为总层厚的30%-50%。
对于内层10的层厚而言,同样有利的是,其占总层厚的30%到40%。
对于内层10的层厚而言,同样优选的是,其占总层厚的40%-50%。
尽管烧绿石相具有比ZrO2层更好的绝热性,但是ZrO2层可以被配置为刚好与烧绿石相等厚。
图3示出了涡轮机的转子叶片120或导向叶片130的透视图,所述涡轮机沿纵轴121延伸。
所述涡轮机可以是飞行器或者用于发电的发电厂的燃气轮机,蒸汽轮机或者压缩机。
沿着纵轴121,桨叶(Schaufeln)120、130先后包括紧固区400、邻近紧固区的桨叶台403以及桨叶叶片(Schaufelblatt)406。
作为导向叶片130,桨叶130可以在其叶片尖端415具有另一个台(未示出)。
在紧固区400内形成叶根183,其用于紧固在轴或盘(未示出)上的转子叶片120、130。
叶根183经配置为例如锤头。作为枞树状或者燕尾根部状的配置也是可行的。
桨叶120、130包括针对流过桨叶叶片406的前缘409和后缘412。
在常规的桨叶120、130中,例如实心金属材料,特别是高温合金,用于桨叶120、130的所有区域400、403、406。
这样的高温合金是例如由下列文献众所周知的:EP1204776B1、EP1306454、EP1319729A1、WO99/67435或者WO00/44949;就合金的化学组成而言,这些文件是本公开的一部分。
在这种情况下,桨叶120、130可以通过铸造方法制造,也即借助定向凝固、锻造法、铣削法或其组合。
具有单晶结构(多个单晶结构)的工件用作机器的在运转期间暴露于高机械、热和/或化学负荷的部件。
这样的单晶工件例如通过定向凝固由熔体制造。所述定向凝固是这样的铸造方法,其中液态金属合金经凝固形成单晶结构,也即形成单晶工件,或者经定向凝固。
在这种情况下,树枝状晶体沿着热通量对准,并形成棒晶粒结构(柱状的,也就是说沿着工件的整个长度延伸,且在这种情况下,根据通用性术语用法,被称为定向凝固)或者单晶结构,也就是说,整个工件由单晶构成。在这些方法中,必须避免向球状(globulitisch)(多晶)凝固转变,因为不定向生长必然形成横向和纵向的晶界,这抵消了定向凝固或单晶部件的优异性能。
通常,当提及定向凝固结构时,既表示这样的单晶,其一没有晶界或者极小角度晶界;也表示这样的单晶,其为棒状晶体结构,尽管其具有沿着纵向延伸的晶界,但是没有任何横向晶界。后一种晶体结构也被称为定向凝固结构。
这样的方法由US-PS 6,024,792和EP0892090A1中已知,这些文件是本公开的一部分。
桨叶120、130同样可以具有抗腐蚀或抗氧化涂层,例如(MCrAlX;M是选自下列的至少一种元素:铁(Fe)、钴(Co)、镍(Ni),X是活性元素并表示钇(Y)和/或硅和/或至少一种稀土元素或者铪(Hf))。这样的合金是例如由下列文献所公知的:EP0486489B1、EP0786017B1、EP0412397B1或者EP1306454A1;就该合金的化学组成而言,这些文献构成本公开的一部分。
在MCrAlX层上,可以另外存在根据本发明的陶瓷绝热层13。
绝热层中的棒状晶粒是通过合适的涂覆方法,例如电子束沉积(EB-PVD)产生的。
整修是指部件120、130在使用后视需要脱去保护层(例如通过喷砂)。然后去除腐蚀层和/或氧化层或者腐蚀产物和/或氧化产物。视需要,还修补组件120、130中的裂缝。然后再重新涂覆组件120、130,并将它们重新使用。
桨叶120、130可以被设计为空心的或实心的。如果打算对桨叶120、130进行冷却,那么其将是空心的,和视需要还包含膜冷却孔418(用虚线表示)。
图4示出了燃气轮机100(图5)的燃烧室110。
燃烧室110例如被设计成所谓的环形燃烧室,其中多个产生火焰156并在圆周方向绕旋转轴102排列的燃烧器107通向公共燃烧室空间154。为此目的,燃烧室110整体上被设计为绕着旋转轴102的环状结构。
为了实现比较高的效率,燃烧室110被设计用于相对高的工作介质M的温度,也即大约1000℃-1600℃。为了允许即使在这样的对于材料不利的工作参数下比较长的运行时间,燃烧室壁153在其面向工作介质M的一侧配有由热屏蔽元素155形成的内衬。
由合金制备的各热屏蔽元件155特别在其工作介质侧配有耐热保护层(MCrAlX层和/或陶瓷涂层),或者由耐高温材料(实心陶瓷块)制备。
保护层可以类似于涡轮机叶片,也就是说,例如MCrAlX,其中M是至少一种选自下列的元素:铁(Fe)、钴(Co)、镍(Ni)、X是活性元素并表示钇(Y)和/或硅和/或至少一种稀土元素或者铪(Hf)。这样的合金是例如由下列众所周知的:EP0486489B1、EP0786017B1、EP0412397B1或者EP1306454A1;就该合金的化学组成而言,这些文献构成本公开的一部分。
整修是指热屏蔽元件155视需要在使用后必须脱去保护层(例如通过喷砂)。然后去除腐蚀层和/或氧化层或者腐蚀产物和/或氧化产物。视需要,还修补热屏蔽元件155中的裂缝。然后,所述热屏蔽元件155被重新涂覆和再使用。
由于燃烧室110内部的高温,还可以给热屏蔽元件155或者它们的固定元件配备冷却系统。所述热屏蔽元件155例如是中空的,和视需要还具有通向燃烧室空间154的膜冷却孔(未示出)。
图5以例如在部分纵截面的形式示出了燃气轮机100。
燃气轮机100内部包括绕着旋转轴102旋转安装的转子103(也被称为涡轮转子),所述转子具有轴101。
沿着转子103,先后是进气壳体104,压缩机105,例如环状的燃烧室110,特别是环形燃烧室(具有多个同轴排列的燃烧器107),涡轮108和排气壳体109。
该环形燃烧室110与例如环形的热气体通道111连通。在此,例如四个先后连接的涡轮机级112形成涡轮108。
各涡轮机级112例如由两个叶片环形成。正如工作介质113的流向所示,在热气体通道111中导向叶片排(Leitschaufelreihe)115之后是由转子叶片120形成的排(Reihe)125。
导向叶片130固定于定子143的内套138上,而排125的转子叶片120则连接到转子103上,例如通过涡轮盘133。
连接到转子103的是发电机或做功机械(未示出)。
在燃气轮机100运转期间,空气135被压缩机105吸入并压缩通过进气壳体104。在压缩机105的涡轮侧端提供的压缩空气被递送到燃烧器107,并在那里与燃料混合。然后该混合物燃烧形成燃烧室110中的工作介质113。工作介质113从那里沿着热气体通道111流动通过导向叶片130和转子叶片120。在转子叶片120处,工作介质113通过冲量转移(impulsübertragend)而膨胀,使得转子叶片120驱动转子103和与其连接的做功机械。
在燃气轮机100运转期间,暴露于热工作介质113的部件经历热负荷。除了内衬环形燃烧室110的热屏蔽元件之外,第一个涡轮机级112的导向叶片130和转子叶片120(如工作介质113的流向所示)受热最多。
为了经受此处的温度,可以借助冷却剂对它们进行冷却。
所述部件的基材同样可以包括定向结构,也就是说它们是单晶的(SX结构)或者仅含纵向定向的晶粒(DS结构)。
例如基于铁、镍或钴的高温合金是用于该部件(特别是涡轮叶片120、130)和燃烧室110的部件的材料。
这样的高温合金是例如由下列文件众所周知的:EP1204776B1、EP1306454、EP1319729A1、WO99/67435或者WO00/44949;就合金的化学组成而言,这些文件是本公开的一部分。
导向叶片130包含面向涡轮108内套138的导向叶根(在此未示出)和与导向叶根反向布置的导向叶片顶部。导向叶片顶部面向转子103并固定在定子143的紧固环140上。

Claims (16)

1.层体系,其包括
基材(4),
金属粘附层(7),其由NiCoCrAlX合金构成,
在金属粘附层(7)上的陶瓷内层(10),
其中
在陶瓷内层(10)上存在陶瓷外层(13),该陶瓷外层(13)含至少80重量%的烧绿石相Gd2Zr2O7,其中内层(10)的层厚为内层(10)和外层(13)的总层厚的10%至40%。
2.权利要求1所述的层体系,
其中,
代替Gd2Zr2O7,存在的是Gd2Hf2O7
3.权利要求1所述的层体系,
其中,
内层(10)的层厚为内层(10)和外层(13)的总层厚的10%至30%。
4.权利要求1所述的层体系,
其中,
内层(10)的层厚为内层(10)和外层(13)的总层厚的10%至20%。
5.权利要求1所述的层体系,
其中,
内层(10)的层厚为内层(10)和外层(13)的总层厚的20%至40%。
6.权利要求1所述的层体系,
其中,
内层(10)的层厚为内层(10)和外层(13)的总层厚的20%至30%。
7.权利要求1所述的层体系,
其中,
内层(10)的层厚为内层(10)和外层(13)的总层厚的30%至40%。
8.权利要求1所述的层体系,
其特征在于,
内层(10)的层厚为40μm至60μm。
9.权利要求1所述的层体系,
其中,
所述金属粘附层(7)具有下列组成(重量%):
11%-13%钴,
20%-22%铬,
10.5%-11.5%铝,
0.3%-0.5%钇,
1.5%-2.5%铼,
余量的镍。
10.权利要求1所述的层体系,
其中,
所述金属粘附层(7)具有下列组成(重量%):
24%-26%钴
16%-18%铬,
9.5%-10.5%铝,
0.3%-0.5%钇,
1.0%-2.0%铼,
余量的镍。
11.权利要求1所述的层体系,
其中,
所述金属粘附层(7)具有下列组成(重量%):
29%-31%镍,
27%-29%铬,
7%-9%铝,
0.5%-0.7%钇,
0.6%-0.8%硅,和
余量的钴。
12.权利要求1所述的层体系,
其中,
所述金属粘附层(7)具有下列组成(重量%):
27%-29%镍,
23%-25%铬,
9%-11%铝,
0.3%-0.7%钇,和
余量的钴。
13.权利要求1所述的层体系,
其中,
所述钇稳定化的氧化锆层含6重量%-8重量%的钇。
14.权利要求1所述的层体系,
其中,
内层(10)和外层(13)的总层厚为300μm。
15.权利要求1所述的层体系,
其特征在于,
内层(10)和外层(13)的总层厚为400μm。
16.权利要求1、18或19所述的层体系,
其特征在于,
总层厚为至多800μm。
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