CN102971440A - 具有高γ/γ’转变温度的金属粘合层以及部件 - Google Patents
具有高γ/γ’转变温度的金属粘合层以及部件 Download PDFInfo
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- 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
- C22C19/056—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%
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Abstract
镍基涂层中的新型添加剂稳定了高温下的γ/γ’相,导致了局部应力的降低。
Description
本发明涉及一种具有γ和γ’相的金属粘合层以及一种部件。
燃气轮机中的高温气体通路部件由Ni基或Co基材料制成。这些材料经过了强度优化,却不能承受在较高温度下的氧化和/或腐蚀侵袭。因此,这些类型的材料必须要用MCrAIY涂层进行防氧化保护,所述MCrAIY涂层也可用作热阻挡涂层(TBC)系统(system)的粘合层。在TBC系统,一方面需要MCrAIY涂层阻挡高温气体的侵袭,另一方面需要该涂层将TBC粘附在基体上。保护该系统不被氧化可使粘合层服役温度提高且寿命增长。
为保护所述材料不被热腐蚀/氧化,MCrAIY涂覆层通常通过如下方法涂覆:低压等离子喷涂(LPPS)、空气等离子喷涂(APS)、电子束物理气相沉积(EBPVD)、冷喷涂(CS)或高速氧燃料(HVOF)法。所述MCrAIY涂层是基于镍和/或钴、铬、铝、硅、铼以及稀土元素如钇。随着粘合层温度升高,该涂层会失效,其会导致热阻挡涂层的开裂。因而,随着服役温度的提高,需要改良的涂层以抵御氧化侵袭。此外,这类涂层需要具有可接受的热机械性能。这些需求只可能通过优化粘合层的组成而达成。
因此本发明的目的就是解决上述的问题。
该问题通过根据权利要求1的金属涂层而解决。
在从属权利要求中公开了进一步的改善,所述改善可以任意相互组合以产生更多的优点。
如所示
图1 合金中γ’、γ相的分数
图2 涡轮叶片
图3 燃气轮机,和
图4 一系列超级合金(super alloy)
附图和描述仅为本发明的实施例。
图2示出沿纵轴121延伸的涡轮机(组)的转子叶片120或导流轮叶(guide vane)130的透视图。
涡轮机(组)可以是航行器或用于发电的发电设备的燃气轮机,蒸汽轮机或压缩机。
叶片或轮叶120、130具有沿着纵轴121相继排列的固定区400,相邻的叶片或轮叶平台403,和主叶片或轮叶部件406,以及叶片或轮叶的末端415。
作为导流轮叶130,轮叶130可在其轮叶末端415处具有另外的平台(未示出)。
用于将转子叶片120、130固定在轴杆或盘(未示出)上的叶片或轮叶根部183形成在固定区400中。
叶片或轮叶根部183被设计为例如锤头形状。其他构型如杉树或楔形的根部也是可能的。
叶片或轮叶120、130具有用于流经主叶片或轮叶部件406的介质的前缘409和后缘412。
在传统的叶片或轮叶120、130的情况下,举例来说,固体金属材料,特别是超级合金,被用于叶片或轮叶120、130的所有区域400、403、406。
这类超级合金可从例如EP 1204776B1、EP 1306454、EP 1319729A1、WO 99/67435或WO 00/44949中获知。
在该情况下,叶片或轮叶120、130可通过铸造方法生产,也可依靠定向凝固,通过锻造(forging)方法,通过切削(milling)方法或它们组合的方法生产。
具有单晶结构的工件被用作运转过程中暴露于高机械、热和/或化学应力中的机器部件。
这类单晶工件通过例如熔融材料的定向凝固生产。这涉及液态金属合金凝固形成单晶结构(即单晶工件)或定向凝固的铸造方法。在该情况下,树枝状晶体沿热流方向定向,形成柱状晶粒结构(即具有工件全长的晶粒,按照常用说法,这里称为定向凝固)或单晶结构,即整个工件为一个单晶。在这些方法中,需要避免向球形(多晶)凝固的转变,因为非定向的生长不可避免的形成横向和纵向晶界,其会有害于定向凝固部件或单晶部件良好的特性。
文中一般性地提及定向凝固显微组织(directionally solidified microstructures)时,其应被理解为含义上同时包括单晶,其不具备任何晶界或至多有小角度晶界,以及柱状晶体结构,其具有纵向延伸的晶界但没有任何横向晶界。所述第二种晶体结构形式也被称为定向凝固显微组织(定向凝固组织)。
这类方法可由US A 6024792和EP 0892090A1中获知。
叶片或轮叶120、130同样可具有抗腐蚀性和抗氧化的涂层,例如MCrAIX(M是选自铁(Fe)、钴(Co)、镍(Ni)中的至少一种,X是一种活性元素,并表示钇(Y)和/或硅和/或至少一种稀土元素或铪(Hf))。这类合金由EP 0486489B1、EP 0786017B1、EP 0412397B1或EP1306454A1可获知,所述专利文件在涉及所述合金化学组成的方面构成本发明公开的一部分。
其密度优选为理论密度的95%。
氧化铝保护层(TGO=热生长氧化层)形成在MCrAIX层上(作为中间层或最外层)。
在MCrAIX上也可以存在热阻挡涂层,该涂层由例如ZrO2、Y2O3-ZrO2组成,即没有、部分或全部通过氧化钇和/或氧化钙和/或氧化镁和/或一种或多种稀土元素(镧、钆、钇等)稳定,所述涂层优选为最外层。
热阻挡涂层覆盖整个MCrAIX层。通过适当的涂覆方法在热阻挡涂层中形成柱状晶粒,例如通过电子束物理气相沉积法(EB-PVD)形成。
可以是其它的涂覆方法,例如大气等离子喷涂(APS)、LPPS、VPS、溶液前驱体等离子喷涂(SPPS)或CVD。热阻挡涂层可包含多孔颗粒,其具有显微裂纹或宏观裂纹以改善其抗热冲击性。因此,热阻挡涂层优选比MCrAIX层更加多孔。
叶片或轮叶120、130可为中空或实心形式。如果要冷却叶片或轮叶120、130,它是空心的且可能还包含薄膜冷却孔418(由虚线表示)。
图3以示例方式示出纵向部分截面形式的燃气轮机100。
在其内部,燃气轮机100具有转子103,也被称为涡轮转子,其被安装为可围绕转动轴102旋转且具有一个轴杆101。
进气壳(intake housing)104、压缩机105、燃烧室例如涡流(toroidal) 燃烧室110、特别是环形燃烧室,其具有多个同轴排列的燃烧器107、涡轮108以及排气壳(exhaust-gas housing)109沿转子103依次排列。
环形燃烧室110与通路例如环形高温气体通路111相连,所述高温气体通路111中,举例来说,四个相继的涡轮级112形成涡轮108。
每个涡轮级112由例如两个叶片或轮叶环形成。从工作介质113流动的方向看去,在高温气体通路111中,由转子叶片120形成的排(row)125设置在导流轮叶排115之后。
导流轮叶130固定在定子143的内壳体138,而排125的转子叶片120安装在转子103上,例如,利用涡轮盘133安装。
发电机(未示出)耦接至转子103。
当燃气轮机100运行的时候,压缩机105通过进气壳104吸入空气135并对其进行压缩。在压缩机105涡轮侧末端供给的压缩空气通至燃烧器107,在其中与燃料混合。然后混合物在燃烧室110里燃烧形成工作介质113。从那里,工作介质113沿高温气体通路111流动经过导流轮叶130和转子叶片120。工作介质113在转子叶片120处膨胀,传送其动量,从而转子叶片120驱动转子103,后者进而驱动与其相连的发电机。
当燃气轮机100运行的时候,暴露于热工作介质113的部件经历热应力。从工作介质113流动的方向看,第一涡轮级112的导流轮叶130和转子叶片120,与衬在环形燃烧室110里面的隔热砖一起,经历最高热应力。为耐受那里普遍的温度,其可通过冷却剂冷却。
部件的基底同样可具有定向结构,即,它们是单晶形态(SX结构)或只包含纵向晶粒(DS结构)。
举例来说,使用铁基、镍基或钴基的超级合金作为部件的材料,特别是作为涡轮叶片或轮叶120、130和燃烧室110部件的材料。
这类超级合金,例如,从EP 1204776B1、EP 1306454、EP1319729A1、WO 99/67435或WO 00/44949中可获知。
导流轮叶130具有面向涡轮108的内壳体138的导流轮叶根部(此处未示出),以及在与导流轮叶根部相反端的导流轮叶头部。导流轮叶头部面向转子103,且固定至定子143的固定环140。
开发出一种新改良的可满足上述要求的涂层。该涂层具有良好的长期寿命,可接受的机械性能和改良了的抗氧化性能。这基于向镍基合金或涂 层中添加铁(Fe)和可选的钽(Ta),而不添加铼(Re)(所列举的元素不是封闭式的)。
所述涂层或合金具有良好的长期寿命,可接受的机械性能和改良了的抗氧化性能。这基于γ及γ’混合相组成的形成。
从含有24%~26%的Co、15%~21%的Cr、9%~11.5%的Al、0.5%~2%的Re、0.05%~0.7%的Y以及镍的β涂层中也知道,本发明的γ’系统中的铝(Al)的释放与该β涂层相比,其在较慢的速率下。
为获得所建议的该系统的两相结构,一个非常优选的相组成为:
Ni-14.4Cr-6Ta-7.75AI-2.7Fe-0.3Y(所列举的元素不是封闭式的)。优选的合金或涂层由Ni、Cr、Al、Fe和任选的Y和/或Ta组成。
相组成随温度而变化,示出在图1中。
含有钽(Ta)和铁(Fe)而不含铼(Re)的NiCoCrAIY组合物可提高γ/γ’转变温度。
如果添加钽(Ta)元素,则其增强了γ’在高温下的稳定性。钽还有助于稳定γ’相的高转变温度,所述γ’相的转变温度高于粘合层的服役温度。
铁(Fe)的添加防止了在>1100℃的高温下在涂层中形成少量的β相。
α-铬的量同样很少。工作时,释放的Al(其会形成TGO)可为其它元素如Ti或Ta替换,这支持γ’的形成。这导致剩余Al随时间的释放减少,另外高γ/γ’转变温度抑制了粘合层在服役温度区域的膨胀系数峰。这导致系统中的应力降低。
粘合层优选为添加了铬(Cr)、铝(Al)、铁(Fe)和可选的钽(Ta)和/或钇(Y)的镍基超级合金,且非常特别是由这些元素组成。
钴在高温下稳定β相,因而其优选不含在组合物中。
Claims (20)
1.一种金属涂层或合金
其为镍基,且
含有γ和γ’相,
其特征在于
所述涂层或所述合金包含铁(Fe)
以及可选的钽(Ta)。
2.根据权利要求1的金属涂层或合金,
其中所述钽(Ta)的量至少为1wt%。
3.根据权利要求1或2的金属涂层或合金,
其中所述钽(Ta)的量为4wt%至8wt%,
特别是5wt%至7wt%,
尤其特别是6wt%。
4.根据权利要求1、2或3的涂层或合金,
其中所述铁(Fe)的量为0.5wt%至5wt%,
特别是1wt%至4wt%,
尤其特别是2.7wt%。
5.根据权利要求1、2、3或4的涂层或合金,
其中所述钴(Co)的量至少为1wt%。
6.根据权利要求5的金属涂层或合金,
其中所述钴(Co)的量在15wt%至30wt%的范围间。
7.根据权利要求1、2、3或4的涂层或合金,
其中不包含钴(Co)。
8.根据权利要求1、2、3、4、5、6或7的金属涂层或合金,
其中所述(Cr)的量至少为1wt%。
9.根据权利要求1、2、3、4、5、6、7或8的金属涂层或合金,
其中所述(Al)的量至少为1wt%。
10.根据权利要求8的金属涂层或合金,
其中所述铬(Cr)的量为12wt%至16wt%,
特别是14.4wt%。
11.根据权利要求1、2、3、4、5、6、7、8、9或10的金属涂层或合金,
其中所述铝(Al)的量为7wt%至8wt%,
特别是7.75wt%。
12.根据上述权利要求中一项或多项的金属涂层或合金,
其中所述钇(Y)的量为0.1wt%至0.7wt%,
特别是0.3wt%。
13.根据上述权利要求中一项或多项的金属涂层或合金,
其中所述金属涂层或所述合金不含铼(Re)。
14.根据上述权利要求1至12中的一项或多项的金属涂层或合金,
其中所述涂层或合金包含0.1wt%至2wt%的铼(Re)。
15.根据上述权利要求中一项或多项的金属涂层或合金,
其中所述金属涂层或所述合金为MCrAIY涂层或合金,其中M=镍(Ni)和/或钴(Co)。
16.根据上述权利要求中一项或多项的金属涂层或合金,
其与含有铼(Re)且不含铁(Fe)和/或不含钽(Ta)的NiCoCrAIY合金或涂层相比具有更高的γ/γ’转变。
17.根据上述权利要求中一项或多项的金属涂层或合金,
其不包含
硅(Si),和/或
钛(Ti),和/或
铪(Hf),和/或
锆(Zr)。
18.根据上述权利要求中一项或多项的金属涂层或合金,
其中所述合金或涂层由镍(Ni)、铝(A1)、铬(Cr)、铁(Fe)以及可选的钽(Ta)和/或钇(Y)组成。
19.一种部件,
其含有根据权利要求1至18中任一项的金属涂层。
20.根据权利要求19的所述部件,
其中所述金属涂层由所述权利要求1至18的任一项的合金组成。
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EP (1) | EP2550375B1 (zh) |
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US20120128526A1 (en) * | 2010-11-24 | 2012-05-24 | Kulkarni Anand A | Metallic Bondcoat or Alloy with a High y/y' Transition Temperature and a Component |
US20120128525A1 (en) * | 2010-11-24 | 2012-05-24 | Kulkarni Anand A | Metallic Bondcoat or Alloy with a High y/y' Transition Temperature and a Component |
US9598774B2 (en) | 2011-12-16 | 2017-03-21 | General Electric Corporation | Cold spray of nickel-base alloys |
EP2961860A1 (en) * | 2013-03-01 | 2016-01-06 | Siemens Aktiengesellschaft | High temperature bond coating with increased oxidation resistance |
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RU2012144795A (ru) | 2014-04-27 |
US9856545B2 (en) | 2018-01-02 |
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WO2011119147A1 (en) | 2011-09-29 |
JP2013522475A (ja) | 2013-06-13 |
KR101460424B1 (ko) | 2014-11-10 |
EP2550375A1 (en) | 2013-01-30 |
US20150259770A1 (en) | 2015-09-17 |
KR20120139832A (ko) | 2012-12-27 |
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US9074268B2 (en) | 2015-07-07 |
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