CN103748266A - 合金、保护层和构件 - Google Patents

合金、保护层和构件 Download PDF

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Publication number
CN103748266A
CN103748266A CN201280039088.7A CN201280039088A CN103748266A CN 103748266 A CN103748266 A CN 103748266A CN 201280039088 A CN201280039088 A CN 201280039088A CN 103748266 A CN103748266 A CN 103748266A
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Prior art keywords
alloy
protective layer
tantalum
described alloy
cobalt
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CN201280039088.7A
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CN103748266B (zh
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沃纳·斯塔姆
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Siemens Energy Global GmbH and Co KG
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Siemens AG
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D25/00—Component parts, details, or accessories, not provided for in, or of interest apart from, other groups
    • F01D25/007—Preventing corrosion
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    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
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    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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    • C22C19/007—Alloys based on nickel or cobalt with a light metal (alkali metal Li, Na, K, Rb, Cs; earth alkali metal Be, Mg, Ca, Sr, Ba, Al Ga, Ge, Ti) or B, Si, Zr, Hf, Sc, Y, lanthanides, actinides, as the next major constituent
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Abstract

具有高的Cr含量的已知的保护层和附加的硅形成脆性相，所述脆性相在碳的影响下在使用期间附加地脆化。根据本发明的保护层具有下述成分：22%至24%的钴（Co）、10.5%至11.5%的铝（Al）、0.2%至0.4%的钇（Y）和/或出自包括钪和稀土元素的组中的至少一种等价的金属、14%至16%的铬（Cr）、可选地0.3%至0.9%的钽、其余是镍（Ni）。

Description

合金、保护层和构件
技术领域
本发明涉及一种根据权利要求1所述的合金、一种根据权利要求13所述的用于尤其在高温下防止构件被腐蚀和/或氧化的保护层以及一种根据权利要求15所述的构件。
背景技术
用于金属构件的应提高金属构件的耐腐蚀性和/或耐氧化性的保护层在现有技术中是大量已知的。大多数的所述保护层以通用名称MCrAlY已知，其中M表示出自包括铁、钴和镍的组中的元素的至少一个并且其他主要的组分是铬、铝和钇。
这种类型的典型的覆层从US专利4,005,989和4,034,142中已知。
在固定式燃气轮机中和在飞机发动机中努力提高进气温度在燃气轮机的专业领域中具有重大的意义，因为进气温度是用于能借助于燃气轮机实现的热力学的效率的重要的决定参数。通过将专门研发的合金用作用于要高热负荷的构件的、如导向叶片和转子叶片的基本材料，尤其通过使用单晶的超合金，明显高于1000℃的进气温度是可能的。在此期间，现有技术允许950℃的进气温度，以及在固定式燃气轮机中更高的进气温度即1100℃，以及在飞机发动机的燃气轮机中允许更高的进气温度。
用于构造具有单晶的基底的就此而言能复杂地构造的涡轮叶片的示例从WO91/01433A1中得知。
而在此期间研发的用于高负荷的构件的基本材料的物理耐抗性在进气温度的可能的进一步的提高方面是尽可能无问题的，但是为了实现防止被氧化和腐蚀的足够的耐抗性必须采取保护层。除了保护层的对于在1000℃的数量级的温度下的废气所预期的侵蚀而言足够的化学耐抗性以外，保护层也必须具有足够好的机械特性，尤其是在保护层和基本材料之间的机械的相互作用方面。保护层尤其必须是具有足够延展性的，以便能够跟随基本材料的可能的变形并且不会断裂，因为以这种方式可能会提供氧化和腐蚀的侵蚀点。在此，典型地出现的问题是：能够改善保护层的对于氧化和腐蚀的耐抗性的如铝和铬的元素的份额的提高造成保护层的可延展性变差，使得要考虑在燃气轮机中通常出现的机械负荷的情况下的机械失效、尤其裂缝的形成。
发明内容
相应于此，本发明基于的目的是，提出一种合金和一种保护层，其具有在腐蚀和氧化方面的良好的高温耐抗性、良好的长时间稳定性并且此外，所述合金和保护层特别好地匹配于在高温下尤其在燃气轮机中预期的机械应力。
所述目的通过根据权利要求1所述的合金和根据权利要求10所述的保护层来实现。
本发明的另一目的在于，提出一种具有防腐蚀和防氧化的改进的保护的构件。
所述目的同样通过根据权利要求12所述的构件，尤其燃气轮机或蒸汽轮机的构件来实现，所述构件为了防止在高温下被腐蚀和氧化而具有上述形式的保护层。
在从属权利要求中列举其他有利的措施，所述措施能够以有利的方式和方法任意彼此组合。
附图说明
在下文中，详细阐述本发明。
附图和说明仅描述本发明的实施例。
附图示出：
图1示出具有保护层的层***，
图2示出超合金的成分，
图3示出燃气轮机，
图4示出涡轮叶片，以及
图5示出燃烧室。
具体实施方式
根据本发明，用于在高温下保护构件免受腐蚀和氧化的保护层7（图1）基本上由下述元素（份额以重量%来说明）：
镍
Co：22%-24%
Cr：14%-16%
Al：10.5%-11.5%
0.2%-0.4%的稀土元素（钇、……）和/或钪（Sc）:
可选地
Ta：0.3%-0.9%。
合金元素Ni、Co、Cr、Al、Y、Ta的列举优选不是最终的。
镍优选形成基质。
优选地，Ni、Co、Cr、Al、Y、Ta的列举是最终的。
合金元素Co、Cr、Al、Y的含量具有下述优点：
中等高的Co含量：
扩展的贝塔/伽马场、避免例如是阿尔法相的脆性相。
中等的Cr含量：
足够高用于提高Al的活性以用于形成Al2O3；
足够低，以避免脆性相（阿尔法铬或西格玛相）。
中等高的Al含量：
对于Al活性而言足够高，以用于形成稳定的Al2O3层；
足够低，以避免脆化效应。
低的Y含量：
足够高，以便在低的氧污染下仍足以形成用于形成含Y的“柄（pegs）”的Y铝酸盐；
足够低，以便使Al2O3层的氧化层生长变慢。
钽对于γ’相的相稳定性具有正面影响或者将过渡移至更高的温度进而减慢在层中的由于铝的消耗而引起的相降低。
要指出的是，各个元素的份额特别地根据其尤其结合元素硅来看的作用来调整。当将所述份额确定为使得没有硅沉积物形成时，有利地在使用保护层期间不形成脆性相，以至于改善并且延长了运行时间特性。
这不仅由于低的铬含量而发生，而且也在考虑铝对相形成的影响下，通过准确地确定铝的含量而发生。
在与特别是在较高的机械特性下产生负面影响的脆性相的减少相互作用中，通过减少由于所选择的镍含量而引起的机械应力来改进机械特性。
保护层在良好的耐腐蚀性情况下具有特别好的防氧化的耐抗性并且其特征也在于特别好的可延展特性，使得所述保护层在进气温度进一步升高时特别适合于应用在燃气轮机100（图3）中。在运行期间，几乎不引起脆化，因为所述层几乎不具有在使用过程中脆化的铬硅沉积物。
粉末例如通过等离子喷涂（大气等离子喷涂APS、低压等离子喷涂LPPS、真空等离子喷涂VPS、……）来施加，以便形成保护层。同样也能够考虑其他方法（物理气相沉积PVD、化学气相沉积CVD、冷气喷涂SPPS、……）。
所描述的保护层7也作用为用于超合金的增附剂层。
能够将其他的层、尤其是陶瓷的隔热层10施加到所述保护层7上。
在构件1中，保护层7有利地施加到由镍基的或钴基的超合金构成的基底4上（图2）。
所述类型的成分作为名称为GTD222、IN939、IN6203和Udimet500的铸造合金已知。在图2中列举构件1、120、130、155的基底4的其他的替选方案（图2）。
构件1上的保护层7的厚度优选被确定为位于大约100μm和300μm之间的数值。
保护层7尤其适合于保护构件1、120、130、155免受腐蚀和氧化，而构件在材料温度大约为950℃时、在飞机涡轮机中也在大约为1100℃时加载有废气。
因此，根据本发明的保护层7尤其适合于保护燃气轮机100的构件，尤其是导向叶片120、转子叶片130或热屏蔽元件155，所述热屏蔽元件在燃气轮机100的或蒸汽轮机的涡轮机之前或之中加载有热气体。
保护层7能够用作覆盖层（保护层是最外层）或用作粘合层（保护层是中间层）。
图1示出作为构件的层***1。层***1具有基底4。基底4能够是金属的和/或陶瓷的。尤其在涡轮机构件中，例如在涡轮机转子叶片120（图4）或涡轮机导向叶片130（图3、4）、热屏蔽元件155（图5）以及蒸汽轮机的或燃气轮机100（图3）的其他壳体部件中，基底4具有镍基、钴基或铁基的超合金，尤其是由上述材料制成。优选地使用镍基超合金（图2）。
在基底4上存在根据本发明的保护层7。优选地，所述保护层7通过等离子喷涂（真空等离子喷涂、低压等离子喷涂、大气等离子喷涂、……）来施加。所述保护层能够用作外部层（没有示出）或中间层（图1）。
优选地，在保护层7上存在陶瓷隔热层10。
优选地，层***由基底4、保护层7和陶瓷隔热层10、可选地在隔热层10之下的TGO（热生长氧化层）构成。
能够将保护层7施加到新制造的构件和再处理的构件上。再处理（Refurbishment）意味着，将构件1在其使用之后在必要时与层（隔热层）分开并且例如通过酸处理（酸剥离）来移除腐蚀产物和氧化产物。必要时，还必须修复裂缝。随后能够对这样的构件进行再覆层，因为基底4是极其昂贵的。
图3示例性地示出燃气轮机100的局部纵向剖面图。燃气轮机100在内部中具有带有轴101的、可围绕旋转轴线102转动地安装的转子103，该转子也称为涡轮机转子。沿着转子103依次为：进气壳体104；压缩机105；例如环状的燃烧室110，尤其为环形燃烧室，带有多个同轴设置的燃烧器107；涡轮机108；和排气壳体109。环形燃烧室110与例如环形的热气体通道111连通。在那里例如四个相继设置的涡轮级112形成涡轮机108。
每个涡轮级112例如由两个叶片环形成。沿工作介质113的流动方向观察，在热气体通道111中，由转子叶片120形成的排125跟随导向叶片排115。
在此，导向叶片130固定在定子143的内壳体138上，而该排125的转子叶片120例如借助涡轮盘133安装在转子103上。发电机或者做功机械（没有示出）耦联在转子103上。
在燃气轮机100工作期间，压缩机105通过进气壳体104将空气135吸入并且压缩。在压缩机105的涡轮侧端部处提供的压缩空气被引至燃烧器107并且在那里与燃料混合。接着混合物在燃烧室110中燃烧，从而形成工作介质113。工作介质113从那里起沿着热气体通道111流过导向叶片130和转子叶片120。工作介质113在转子叶片120处以传递动量的方式膨胀，使得转子叶片120驱动转子103，并且该转子驱动耦联在其上的做功机械。
暴露于热工作介质113的构件在燃气轮机100工作期间承受热负荷。除了加衬于环形燃烧室110的热屏蔽元件之外，沿工作介质113的流动方向观察的第一涡轮机级112的导向叶片130和转子叶片120承受最高的热负荷。为了经受住那里存在的温度，能够借助于冷却剂来冷却所述第一涡轮机级的导向叶片和转子叶片。同样，构件的基底能够具有定向结构，也就是说它们是单晶的（SX结构）或仅具有纵向定向的晶粒（DS结构）。例如，铁基超合金、镍基超合金或钴基超合金用作构件的材料，尤其是用作涡轮叶片120、130的和燃烧室110的构件的材料。例如由EP1204776B1、EP1306454、EP1319729A1、WO99/67435或WO00/44949已知这样的超合金。
导向叶片130具有朝向涡轮机108的内壳体138的导向叶片根部（这里没有示出），以及与导向叶片根部相对置的导向叶片顶部。导向叶片顶部朝向转子103并固定在定子143的固定环140处。
图4在立体图中示出流体机械的沿着纵轴线121延伸的转子叶片120或导向叶片130。
所述流体机械能够是飞机的或用于发电的发电厂的燃气轮机、蒸汽轮机或压缩机。
叶片120、130沿着纵轴线121相继具有：固定区域400、邻接于固定区域的叶片平台403以及叶身406和叶片梢部415。
作为导向叶片130，叶片130能够在其叶片梢部415处具有另一平台（没有示出）。
在固定区域400中形成有用于将转子叶片120、130固定在轴或盘（没有示出）上的叶片根部183。叶片根部183例如构成为锤头形。作为枞树形根部或燕尾形根部的其他设计方案是可行的。
叶片120、130对于流过叶身406的介质具有迎流棱边409和出流棱边412。
在传统的叶片120、130中，在叶片120、130的所有区域400、403、406中使用例如实心的金属材料、尤其是超合金。
例如由EP1204776B1、EP1306454、EP1319729A1、WO99/67435或WO00/44949已知这样的超合金。
在这种情况下，叶片120、130能够通过铸造法，也能够借助定向凝固、通过锻造法、通过铣削法或其组合来制造。
将带有一个或多个单晶结构的工件用作机器的在运行时承受高的机械的、热的和/或化学的负荷的构件。
这种单晶工件的制造例如通过由熔融物的定向凝固来进行。在此，这涉及一种浇注法，其中液态金属合金凝固为单晶结构、即单晶工件，或者定向凝固。在这种情况下，枝状晶体沿热流定向，并且形成柱状晶体的晶粒结构（柱状地，也就是说在工件的整个长度上分布的晶粒，并且在此根据一般的语言习惯称为定向凝固），或者形成单晶结构，也就是说整个工件由唯一的晶体构成。在这些方法中，必须避免过渡成球形（多晶的）凝固，因为通过非定向的生长不可避免地构成横向和纵向晶界，所述横向和纵向晶界使定向凝固的或单晶的构件的良好特性不起作用。
如果一般性地提到定向凝固组织，则是指不具有晶界或最多具有小角度晶界的单晶和确实具有沿纵向方向分布的晶界但不具有横向晶界的柱状晶体结构。第二种所提到的晶体结构也称为定向凝固组织（directionally solidified structures）。由US-PS6,024,792和EP0892090A1已知这样的方法。
叶片120、130同样能够具有根据本发明的抗腐蚀或抗氧化的保护层7。密度优选地是理论密度的95%。在（作为中间层或最外层的）MCrAlX层上形成保护性氧化铝层（TGO=thermal grown oxide layer（热生长氧化层））。
在MCrAlX上还能够存在隔热层，隔热层优选是最外层并例如由ZrO2、Y2O3-ZrO2组成，即隔热层通过氧化钇和/或氧化钙和/或氧化镁非稳定、部分稳定或完全稳定。隔热层覆盖整个MCrAlX层。通过例如电子束气相淀积（EB-PVD）的适当的覆层方法在隔热层中产生柱状晶粒。
其他覆层方法也是可以考虑的，例如大气等离子喷涂（APS）、LPPS（低压等离子喷涂）、VPS（真空等离子喷涂）或CVD（化学气相沉积）。隔热层能够具有多孔的、有微观裂缝或宏观裂缝的晶粒，以达到更好的耐热冲击性。因此，隔热层优选地比MCrAlX层更为多孔。
叶片120、130能够实施成空心的或实心的。如果要冷却叶片120、130，则叶片为空心的并且必要时还具有薄膜冷却孔418（由虚线表示）。
图5示出燃气轮机100的燃烧室110。燃烧室110例如构成为所谓环形燃烧室，其中多个在周向上围绕旋转轴线102设置的燃烧器107通到共同的燃烧室腔154中，所述燃烧器产生火焰156。为此，燃烧室110以其整体构成为环形的结构，所述环形的结构围绕旋转轴线102定位。
为了实现相对高的效率，针对为大约1000℃至1600℃的工作介质M的相对高的温度来设计燃烧室110。为了即使在这些对材料不利的工作参数的情况下也能够实现相对长的工作持续时间，燃烧室壁153在其朝向工作介质M的一侧上设有由热屏蔽元件155形成的内衬。
由于在燃烧室110的内部中的高温，此外能够为热屏蔽元件155或者为其保持元件设有冷却***。那么，热屏蔽元件155例如是空心的或者必要时还具有通到燃烧室腔154中的冷却孔（没有示出）。
每个由合金构成的热屏蔽元件155在工作介质侧配备有尤其耐热的保护层（MCrAlX层和/或陶瓷覆层）或者由耐高温的材料（实心陶瓷石）制成。所述保护层7能够类似涡轮叶片。
在MCrAlX上还能够存在例如陶瓷的隔热层，并且隔热层例如由ZrO2、Y2O3-ZrO2构成，即隔热层通过氧化钇和/或氧化钙和/或氧化镁非稳定、部分稳定或完全稳定。通过例如电子束气相淀积（EB-PVD）的适当的覆层工艺在隔热层中产生柱状晶粒。其他覆层工艺，例如气相等离子喷涂（APS）、LPPS、VPS或CVD也是可行的。隔热层能够具有多孔的、有微观裂缝或宏观裂缝的晶粒，以达到更好的耐热冲击性。
再处理（Refurbishment）意味着，在使用涡轮叶片120、130和热屏蔽元件155之后，必要时必须将保护层从涡轮叶片120、130和热屏蔽元件155上去除（例如通过喷砂）。接着，去除腐蚀层和/或氧化层或腐蚀产物和/或氧化产物。必要时，还修复在涡轮叶片120、130或热屏蔽元件155中的裂缝。然后，进行涡轮叶片120、130和热屏蔽元件155的再覆层以及涡轮叶片120、130或热屏蔽元件155的重新使用。

Claims (12)

1.一种合金，
所述合金至少包含下述元素（以重量百分比来说明）：
22%至24%的钴（Co），
尤其是23%的钴（Co）；
14%至16%的铬（Cr），
尤其是15%至16%的铬（Cr），
更尤其是15%的铬（Cr）；
10.5%至11.5%的铝（Al），
尤其是11重量%的铝（Al）；
0.2%至0.4%、
尤其是0.3%的出自包括钪（Sc）和/或稀土元素的组中的至少一种金属，
尤其是钇（Y）；
可选地，0.3%至0.9%的钽（Ta），
尤其是0.4%至0.7%的钽（Ta），
更尤其是0.5%的钽（Ta）；
镍（Ni），
尤其其余是镍（Ni）。
2.根据权利要求1所述的合金，
所述合金包含0.3重量%的钇（Y）。
3.根据权利要求1或2所述的合金，
所述合金不包含铼（Re）。
4.根据上述权利要求中一项或多项所述的合金，
所述合金不包含硅（Si）。
5.根据权利要求1、2、3、4或5所述的合金，
所述合金包含钽（Ta），
尤其包含至少0.4重量%的钽（Ta），
更尤其包含0.5重量%的钽（Ta）。
6.根据上述权利要求中一项或多项所述的合金，
所述合金不包含锆（Zr）和/或不包含钛（Ti）和/或不包含镓（Ga）和/或不包含锗（Ge）和/或不包含铂（Pt）和/或不包含铪（Hf）和/或不包含铈（Ce）和/或不包含铁（Fe）和/或不包含钯（Pd）和/或不包含硼（B）和/或不包含碳（C）。
7.根据上述权利要求中一项或多项所述的合金，
所述合金由钴、铬、铝、钇、镍以及可选的组分钽构成。
8.根据上述权利要求1至7中一项或多项所述的合金，
所述合金由钴、铬、铝、钇、镍和钽构成。
9.根据上述权利要求中一项或多项所述的合金，
其中镍（Ni）形成基质。
10.一种用于尤其在高温下保护构件（1）免受腐蚀和/或氧化的保护层（7），
所述保护层具有根据权利要求1至9中一项或多项所述的合金的成分。
11.根据权利要求10所述的保护层（7），
所述保护层通过等离子喷涂、尤其APS或高速喷涂（HVOF）来施加。
12.一种构件，
尤其燃气轮机（100）的构件（120，130，155），
尤其其中所述构件（120，130，155）的基底（4）是镍基的或者是钴基的，
所述构件为了防止在高温下被腐蚀和氧化而具有根据权利要求10或11所述的保护层（7），
其中尤其在所述保护层（7）上施加有陶瓷的隔热层（10）。
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