CN101198713B - 用于包含热障层和金属防蚀层的构件的层体系、制造工艺以及操作蒸汽涡轮的方法 - Google Patents

用于包含热障层和金属防蚀层的构件的层体系、制造工艺以及操作蒸汽涡轮的方法 Download PDF

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CN101198713B
CN101198713B CN200680021099.7A CN200680021099A CN101198713B CN 101198713 B CN101198713 B CN 101198713B CN 200680021099 A CN200680021099 A CN 200680021099A CN 101198713 B CN101198713 B CN 101198713B
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coating systems
thermal barrier
barrier coatings
corrosion resistant
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J·巴尼克尔
F·施米茨
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Abstract

本发明涉及蒸汽涡轮(300，303)的构件(333，366)，包括热障层(7)和位于所述热障层10(7)上的金属防蚀层(13)，其中防蚀层(13)的材料与金属粘合层(10)相同。

Description

用于包含热障层和金属防蚀层的构件的层体系、制造工艺以及操作蒸汽涡轮的方法
本发明涉及如权利要求书1所述的具有热障层和金属防蚀层的构件、如权利要求31所述的制造工艺以及如权利要求32所述的操作蒸汽涡轮的方法。
施加在构件上的热障层在燃气涡轮领域是已知的，例如在EP1029115中所述。
热障层可以使构件能被用于比基体材料所容许的更高的温度，或者延长使用寿命。
用于燃气涡轮的已知的基体材料(基材)能容许最高1000℃-1100℃的使用温度，而具有热障层的涂覆层能容许高达1350℃的使用温度。
在蒸汽涡轮中的构件使用温度要低得多，因此在这种应用中并没有这些要求。
由EP1029104A已知了向燃气涡轮叶片的陶瓷热障层上施加陶瓷防蚀层。
由DE19535227A1已知了在蒸汽涡轮中提供热障层以容许将机械性能较差但价格较便宜的材料用于其上施加了热障层的基材。
美国专利US5,350,599公开了一种抗蚀的陶瓷热障层。
US2003/0152814A1公开了一种热障层体系，其由超级合金基材、位于基材上的氧化铝层和作为外陶瓷热障层的陶瓷构成。
EP0783043A1公开了一种由位于陶瓷热障层上的氧化铝或碳化硅构成的防蚀层。
美国专利US5,683,226公开了一种具有提高的耐蚀性的蒸汽涡轮部件。
US4,405,284公开了一种外金属层，其与下面的陶瓷热障层相比多孔性显著更高。
在其对现有技术的讨论中，EP0783043A1公开了分两层形成耐蚀涂层，即由内金属层和外陶瓷层构成。
US5,740,515公开了一种其上施加了硬陶瓷硅化物外涂层的陶瓷热障层。
WO00/70190公开了一种施加了外金属层的构件，该外金属层包含铝以增强构件的抗氧化性。
由于介质中的杂质和/或流过带热障层构件的流动介质的高流速，热障层受到强烈腐蚀。
因此，本发明的目的在于提供一种构件、制造这种构件的工艺以及能克服此问题的层体系的适合应用。
此目的是通过如权利要求1中的构件、如权利要求31中的工艺和如权利要求32中的方法实现的。
从属权利要求列出了本发明构件的其它有利结构。
从属权利要求中所列的特征可以有利的方式彼此结合。
特别是对于为驱动目的而暴露于热流体中的涡轮构件来说，去氧化皮常常会导致脱落的氧化皮颗粒对脆性陶瓷层的机械冲击，这可能会导致材料断裂即导致腐蚀。尽管陶瓷层被设计成能承受热冲击，但它却容易受到局部非常有限出现的机械应力的影响，因为热冲击具有对整个层的更广泛的影响。
因此，特别优选金属防蚀层，因为由于其延展性金属防蚀层是可以弹性和塑性变形的。
热障层并不一定只是用于将使用温度范围往上移的目的，还可以有利的方式匀化和/或降低由于在构件上产生或者存在于构件上的温差引起的热膨胀。由此可以消除或至少降低热机械应力。
附图中列举了一些实施例，其中：
图1显示了构件上的本发明的热障层的排列可能性，
图2，3显示了根据本发明所形成的构件的热障层之内的孔隙率梯度，
图4，5显示了一种蒸汽涡轮，
图6，7，8显示了根据本发明所形成的构件的其它示实施例。
图1显示了用于构件的根据本发明所形成的层体系1的第一种实施例。在下文中，当构件包含层体系1时术语层体系1和构件作为同义词使用。
构件1优选地是燃气或蒸汽涡轮300，303(图4)的构件，特别是蒸汽涡轮300的蒸汽流入区333、涡轮叶片342、354、357(图4)或外壳部件334、335、366(图4，5)，并且由基材4(支撑结构)和施加在所述基材上的热障层7以及位于所述热障层7上的外金属防蚀层13构成。在基材4与热障层7之间设有至少一个金属粘合层10。粘合层10用于保护基材4免受腐蚀和/或氧化和/或用于提高热障层7到基材4的结合。当热障层7由陶瓷构成而基材4由金属构成时更是如此。
防蚀层13由金属或金属合金构成，保护构件免受侵蚀和/或磨损，特别是对于易起氧化皮的蒸汽涡轮300，303(图4)就是如此，其中会出现约50m/s的平均流速(即20m/s-100m/s)和350-400bar的压力。
外金属防蚀层13(即最外层)优选地比热障层7更密。
在此，术语更密是指外金属防蚀层13的孔隙率按绝对值计算比热障层7的孔隙率(例如p(7)＝90％，即p(13)≥91％，特别是≥93％)高至少1％、特别是至少3％。
热障层7的密度优选地为理论密度的80％-95％，而金属防蚀层13的密度p优选地为理论密度的至少96％、优选地98％。
术语金属应理解为不仅包括单质金属，还包括合金、固溶体或金属间化合物。
根据本发明，粘合层10与防蚀层13具有相同或相似的组成。
相同的组成是指两个层10、13含有相同量的相同元素，优选地由MCrAlX合金或SC21、SC23或SC24构成。通过优选地使防蚀层13采用相同的组成，简化了采购还显著提高了基材4的腐蚀性能。
相似的组成是指两个层10、13含有相同的元素但比例稍有不同，即每种元素相差最多3％(例如层10的铬含量为30％，此时层13的铬含量可以为至少27％(30-3)或最多33％(30+3)，而且可以存在最多1wt％的至少一种其它元素。
SC21由(以wt％计)29％-31％镍、27％-29％铬、7％-8％铝、0.5％-0.7％钇、0.3％-0.7％硅和余量的钴组成。
SC23由(以wt％计)11％-13％钴、20％-22％铬、10.5％-11.5％铝、0.3％-0.5％钇、1.5％-2.5％铼和余量的镍组成。
SC24由(以wt％计)24％-26％钴、16％-18％铬、9.5％-11％铝、0.3％-0.5％钇、1.0％-1.8％铼和余量的镍组成。
耐磨/防蚀层13优选地由铁基、铬基、镍基和/或钴基合金或例如NiCr80/20或含硼(B)和硅(Si)的掺合物的NiCrSiB或NiAl(例如：Ni95wt％，Al 5wt％)组成。
特别地，金属防蚀层13可用于蒸汽涡轮300、303，因为在蒸汽涡轮中蒸汽流入区333处的使用温度最高为450℃、550℃、650℃、750℃或850℃。
优选地采用750℃的温度。
对于这些温度范围，有足够的在构件1的使用寿命内具有足够高的必要耐蚀性并同时具有良好抗氧化性的金属层。
燃气涡轮中位于陶瓷热障层7上的金属防蚀层13并不适合用在涡轮的第一级或燃烧室之内，因为金属防蚀层13作为外层并不能承受高达1350℃的使用温度。
用于保护基材4免于在高温下腐蚀和氧化的粘合层10大致包含例如以下元素(具体含量为重量百分比wt％)：
11.5-20.0％铬，
0.3-1.5％硅，
0.0-1.0％铝，
0.0-0.7％钇和/或选自钪和稀土元素的至少一种等价金属，余量为铁、钴和/或镍以及由制造过程导致的杂质。
特别地金属粘合层10由下列成分构成：
12.5-14.0％铬，
0.5-1.0％硅，
0.1-0.5％铝，
0.0-0.7％钇和/或选自钪和稀土元素的至少一种等价金属，
余量为铁和/或钴和/或镍以及由制造过程导致的杂质。
优选地在这两种粘合层10中余量全为铁。
基于铁的粘合层10的组成具有特别出色的性能，从而使粘合层10极其适合应用于施加在铁素体基材4上。
基材4和粘合层10的热膨胀系数可以彼此十分相配(只相差至多10％)甚至相同，因此在基材4与粘合层10之间不产生热应力(热失配)，而热应力会导致粘合层10剥落。这点尤其重要，因为对于铁素体材料，通常没有为扩散结合而进行热处理，粘合层10(铁素体)主要或完全通过粘合结合在基材4上。
选择外防蚀层13的组成使其具有高延展性。在此，术语高延展性是指在使用温度下断裂伸长率为5％(5％的伸长导致形成裂缝)。
具有这样的延展性的这种防蚀层13可以直接存在于基材4或陶瓷热障层7上，其中粘合层10的组成将不再重要。
热障层7特别地是一种陶瓷层，其例如至少部分地由氧化锆(由氧化钇和/或氧化镁部分稳定或完全稳定)和/或至少部分地由二氧化钛组成，且例如厚度大于0.1mm。例如，可以使用100％由氧化锆或二氧化钛构成的热障层7。
陶瓷层7可以通过已知的涂覆工艺如大气等离子喷涂(APS)、真空等离子喷涂(VPS)、低压等离子喷涂(LPPS)和通过化学或物理涂覆方法(CVD，PVD)施加。
基材4优选地是钢基或其它铁基合金(例如1％CrMoV或10-12％铬钢)或者是镍基或钴基超级合金。
特别地，基材4是一种铁素体基础合金、钢基或镍基或钴基超级合金，特别是1％CrMoV钢或10-12％铬钢。
层体系1的其它有利的铁素体基材4由下列成分构成：
用于轴(309，图4)的1％-2％Cr钢：
例如30CrMoNiV5-11或23CrMoNiWV8-8，或
用于外壳(例如335，图4)的1％-2％Cr钢：
G17CrMoV5-10或G17CrMo9-10，或
用于轴(309，图4)的10％Cr钢：
XI2CrMoWVNbN10-1-1，
用于外壳(例如335，图4)的10％Cr钢：
GX12CrMoWVNbN10-1-1或CX12CrMoVNbN9-1。
为实现热障层7的尽可能好的功效，热障层7至少部分地具有一定开气孔率和/或闭气孔率。
防蚀层13优选地具有比热障层7更高的密度，由此其13具有更高的耐蚀性。
金属防蚀层13具有极低的孔隙率并特别地具有较低的粗糙度，以便产生良好的抗侵蚀性损害能力。
金属防蚀层的较低孔隙率和粗糙度可以采用不同方法实现：
1.在热喷涂防蚀层13时使用具有尽可能小的粒径的喷雾粉末，
2.在喷涂之后通过喷射操作，例如通过用玻璃珠或钢砂喷射或其它机械致密化或平整工艺(滚压，振动修整)，使外金属防蚀层13致密化，
3.通过渗透剂封闭开孔，
4.对整个体系进行热处理，
5.熔融或再熔化顶层或整个金属防蚀层。
与此相反，位于基材与热障层之间的粘合层10是以使其具有充分高的粗糙度并带咬边(Hinterschneidungen)的方式实施的，以实现热障层向粘合层10的牢固粘合。在这种情况下，喷雾操作过程中所用的粉末可以比防蚀层13使用的粗得多。
图2显示了具有孔隙率梯度的多孔热障层7。
热障层7中存在气孔16。热障层7的密度ρ在外表面方向上增大。
因此，层7在孔隙度较大的区可被用作热屏障，而适当时在孔隙率较低的区可被用于防蚀。
因此，优选地在朝粘合层10方向比在外表面或与防蚀层13的接触面附近存在更大的孔隙率。
在图3中，热障层7的密度ρ的梯度与图2所示的相反。
防蚀层13优选地只局部施加，并优选地在腐蚀性颗粒撞击构件1的角度为60°-120°，优选70°-110°或更优选80°-100°处施加在构件1上。涂覆在腐蚀性颗粒的碰撞角为90°+/-2°的位置尤其有用。在腐蚀性颗粒以这种几乎垂直的角度撞击在构件1表面上时，金属防蚀层13提供了最好的保护。构件1表面的垂直线构成90°轴。
图4举例显示了一种具有沿旋转轴306延伸的涡轮轴309的蒸汽涡轮300，303。
蒸汽涡轮具有高压部分涡轮300和中压部分涡轮303，它们各自具有内壳312和环绕该内壳的外壳315。高压部分涡轮300是例如罐状设计的。中压部分涡轮303是双流设计的。中压部分涡轮303也可以是单流设计的。沿旋转轴306，在高压部分涡轮300与中压部分涡轮303之间设置有轴承318，涡轮轴309在轴承318中具有一个轴承区321。涡轮轴309安装在紧挨高压部分涡轮300的另一轴承324上。在此轴承324附近，高压部分涡轮300具有轴密封装置345。涡轮轴309相对于中压部分涡轮303的外壳315由另两个轴密封装置345封闭。在高压蒸汽流入区348与蒸汽出口区351之间，涡轮轴309在高压部分涡轮300内具有高压转子叶片354，357。此高压转子叶片354，357与相联的转动叶片(未更具体显示)一起构成第一叶片区360。中压部分涡轮303具有中央蒸汽流入区333。在属于蒸汽流入区333内，涡轮轴309具有径向对称的轴罩363，即护板，一方面用于将蒸汽流分隔成中压部分涡轮303的两个流，另一方面用于防止热蒸汽与涡轮轴309直接接触。在中压部分涡轮303中，涡轮轴309具有第二叶片区366，此区内包含中压转子叶片354，342。流过第二叶片区366的热蒸汽由流出连接件369流出中压部分涡轮303，进入连接在流下游的低压部分涡轮(未显示)。
涡轮轴309由两个涡轮部分轴309a和309b组成，它们在轴承318区彼此固定地相连。
特别地，蒸汽流入区333具有热障层7和防蚀层13。
图5显示了蒸汽涡轮300、303的一个区的放大图。
在流入区333附近，蒸汽涡轮300、303包含外壳334，其暴露于250-350℃的温度。
在作为内壳335一部分的流入区333内，温度为450-800℃。
这造成了至少200℃的温差。在暴露于所述高温的内壳335上，带防蚀层13的热障层7被施加到内侧336(例如不施加于外侧337)。
热障层7只局部地存在于内壳335上(例如不存在于叶片区366)。
带防蚀层13的热障层7的施加减少了进入内壳335的热量，从而影响热膨胀性能。由此，内壳335和蒸汽流入区333的总体变形性能都可以可控地进行设定。这可以通过改变热障层7的厚度或在内壳335表面的不同部位涂覆不同的材料来实现。
也可以使内壳335不同部位的孔隙率不同。
热障层7可以局部地施加，例如施加在内壳335内的流入区333附近。
热障层7也可以只局部地施加在叶片区366(图6)。
特别是在流入区333，需要使用防蚀层13。
如果在流入区333存在带防蚀层13的热障层7(TBC)，则在叶片区366和/或涡轮叶片中可以存在不带防蚀层的热障层7。
    流入区     叶片区     涡轮叶片
    TBC     有+13     无     无
    TBC     有+13     有     无
    流入区     叶片区     涡轮叶片
    TBC     有+13     无     有
    TBC     有+13     有+13     无
    TBC     有     有+13     无
    TBC     有     无     有+13
图7显示了本发明的构件1的另一种实施例。
在此情形下，热障层7的厚度在蒸汽涡轮300、303的流入区333比在叶片区366厚。
热障层7的局部不同厚度用于可控地调节热量的传入并从而调节热膨胀和由此调节内壳334(由流入区333和叶片区366构成)的膨胀性能。
由于流入区333存在高于叶片区366的温度，在流入区333内的所述较厚的热障层7与在温度较低的叶片区相比能更大程度的降低热量向基材4的输入。因此，流入区333和随后叶片区366内的热输入可被保持在大致相同的水平，从而产生大致相等的热膨胀。
也可以在流入区333附近使用不同于叶片区366的材料。本文中，热障层7被施加在整个热区，即每一处，且包括防蚀层13。
图8显示了热障层7的应用的另一实施例。
构件1，特别是外壳部件，在这里是阀套31，热蒸汽通过流入口46流入其中。
流入口46削弱了阀套的机械性能。
阀套31由例如罐状外壳部件34和盖37构成。
在外壳部件31之内有一个由阀锥40和芯轴43构成的阀门。
构件蠕动造成外壳31和盖37的不均匀轴向形变。阀套31在开口46附近轴向膨胀程度较大，导致盖子与芯轴43一起侧斜，如虚线所示。从而，阀锥不再正确落位，这降低了阀门的密闭性。
向阀套31的内侧49施加热障层7可以匀化变形性能，从而使阀套31和盖子37的两端52、55能均匀地膨胀。
总地来说，热障层7的施加用来控制变形性能并由此确保阀门的密闭性。
上述热障层7同样包括防蚀层13。

Claims (26)

1.一种用于构件(1，31，334，335，342，354，357，366)的层体系，其至少组成如下：
基材(4)，
金属粘合层(10)，
位于金属粘合层(10)上的热障层(7)，
以及位于热障层(7)上的外金属防蚀层(13)，
特征在于：
粘合层(10)选自如下组成(以wt％计)：
29％-31％镍，
27％-29％铬，
7％-8％铝，
0.5％-0.7％钇，
0.3％-0.7％硅，和
余量的钴，
或选自如下组成：
11％-13％钴，
20％-22％铬，
10.5％-11.5％铝，
0.3％-0.5％钇，
1.5％-2.5％铼，和
余量的镍，
或选自如下组成：
24％-26％钴，
16％-18％铬，
9.5％-11％铝，
0.3％-0.5％钇，
1.0％-1.8％铼，和
余量的镍，
或选自如下组成：
11.5％-20％铬，
0.3％-1.5％硅，
0％-1％铝，
0％-4％钇，和
余量的铁，
或选自如下组成：
12.5％-14％铬，
0.5％-1.0％硅，
0.1％-0.5％铝，
0％-4％钇，和
余量的铁，
特征还在于粘合层(10)与防蚀层(13)具有相同或相似的组成。
2.如权利要求1所述的层体系，特征在于所述粘合层(10)与防蚀层(13)的材料为MCrAlX合金。
3.如权利要求1或2所述的层体系，特征在于，
所述防蚀层(13)与粘合层(10)由铁基、镍基、铬基或钴基合金构成。
4.如权利要求1所述的层体系，特征在于，
所述防蚀层(13)与粘合层(10)由含硅和/或硼掺合物的镍铬合金构成。
5.如权利要求1所述的层体系，特征在于，
所述防蚀层(13)与粘合层(10)由镍铝合金构成。
6.如权利要求1、2、4或5所述的层体系，特征在于，
所述粘合层(10)与防蚀层(13)具有相同的组成。
7.如权利要求1所述的层体系，特征在于，
所述防蚀层(13)具有低于所述热障层(7)的孔隙率，
特征还在于密度差为至少1％。
8.如权利要求1或7所述的层体系，特征在于，
所述防蚀层(13)的密度为防蚀层(13)的理论密度的至少96％。
9.如权利要求1或7所述的层体系，特征在于，
所述热障层(7)的密度为热障层(13)的理论密度的80％-95％。
10.如权利要求1或7所述的层体系，特征在于，
所述热障层(7)至少部分为多孔性的。
11.如权利要求7所述的层体系，特征在于，
所述热障层(7)具有孔隙率梯度。
12.如权利要求11所述的层体系，特征在于，
所述热障层(7)的孔隙率在热障层(7)的外区最高。
13.如权利要求11所述的层体系，特征在于，
所述热障层(7)的孔隙率在热障层(7)的外区最低。
14.如权利要求1、2、4或5所述的层体系，特征在于，
所述金属防蚀层(13)的材料具有高延展性。
15.如权利要求1所述的层体系，特征在于，
所述层体系是燃气涡轮或蒸汽涡轮(300，303)的外壳部件(31，334，335，366)。
16.如权利要求15所述的层体系，特征在于，
所述层体系是涡轮外壳(366)或阀套(31)。
17.如权利要求1所述的层体系，特征在于，
所述层体系是涡轮叶片(342，354，357)。
18.如权利要求1、15、16或17所述的层体系，特征在于，
所述防蚀层(13)在腐蚀性颗粒撞击构件(1)的角度为60°-120°的位置处位于构件(1)上。
19.如权利要求1、15、16或17所述的层体系，特征在于，
所述层体系包括基体(4)，在(4)上有所述热障层(7)，
特征还在于所述基体(4)由镍基、钴基或铁基合金构成。
20.如权利要求1或7所述的层体系，特征在于，
所述热障层(7)至少部分由二氧化锆构成。
21.如权利要求1或7所述的层体系，特征在于，
所述热障层(7)至少部分由二氧化钛构成。
22.如权利要求1所述的层体系，特征在于，
所述层体系施加在蒸汽涡轮(300，303)的流入区(333)和叶片区(366)。
23.如权利要求1所述的层体系，特征在于，
所述层体系仅施加在蒸汽涡轮(300，303)的流入区(333)。
24.如权利要求1所述的层体系，特征在于，
所述层体系仅施加在蒸汽涡轮(300，303)的叶片区(366)。
25.如权利要求1所述的层体系，特征在于，
所述粘合层(10)、热障层(7)和防蚀层(13)施加在翻新的构件(1)上。
26.一种制造如权利要求1-25之一所述的构件的工艺，特征在于
在将所述防蚀层(13)施加到所述热障层(7)上之后将其致密化。
CN200680021099.7A 2005-06-13 2006-03-17 用于包含热障层和金属防蚀层的构件的层体系、制造工艺以及操作蒸汽涡轮的方法 Expired - Fee Related CN101198713B (zh)

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EP05012633.3 2005-06-13
PCT/EP2006/060835 WO2006133980A1 (de) 2005-06-13 2006-03-17 Schichtsystem für ein bauteil mit wärmedämmschicht und metallischer erosionsschutzschicht, verfahren zur herstellung und verfahren zum betreiben einer dampfturbine

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