CN103403225A - 生产用于保护金属部件的多层系统热障的方法和装配有这种保护系统的部件 - Google Patents
生产用于保护金属部件的多层系统热障的方法和装配有这种保护系统的部件 Download PDFInfo
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- HKRXOWGILGJWPT-UHFFFAOYSA-N oxygen(2-) yttrium(3+) zirconium(4+) Chemical compound [O-2].[Y+3].[Zr+4] HKRXOWGILGJWPT-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
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- 229910052719 titanium Inorganic materials 0.000 description 1
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- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明目的是生产一种装配有保护系统的金属部件,特别地用于航空器涡轮发动机叶片,具有在热特性,部件的粘合和对氧化/腐蚀的抗性方面改进的热障。为此,本发明的方法在单个步骤中,根据SPS技术,从特定陶瓷生产涂层。根据一个实施方式,根据SPS快速烧结方法生产金属部件,并且该金属部件包括超级合金基质(22)、金属亚层(21)、TGO氧化物层(25)和通过所述方法由至少两层陶瓷(2a、2b)形成的热障(23),它们是化学地和机械地相容的。第一陶瓷(2a)称作内陶瓷,能够具有明显更高的膨胀系数。外陶瓷(2b)能够具有至少更低的热传导率,明显地更高的烧结温度和/或最高的工作温度。热障(23)具有从金属亚层(21)到外陶瓷(2b)组分梯度、孔隙率(3)梯度。
Description
技术领域
本发明涉及用于生产用于保护由超级合金所制造的金属部件的多层系统热障的方法。本发明还涉及装配有这种保护系统的超级合金所制造的金属部件。
本发明的领域是耐火材料的研发,该耐火材料能够构成热机械部件,特别是HP(高压)涡轮机部件,诸如转子叶片或分配器。
对现代燃气涡轮机性能正在进行的改进需要使用越来越高的涡轮机输入温度,由此需要使用具有更高耐火特性的材料。
背景技术
为此,已经开发了镍(Ni)和铝(Al)基超级合金,诸如等轴超级合金,然后是定向凝固的超级合金,最后是单晶超级合金。然而,目前,这些超级合金的开发都不足以满足日益增加的高温部件使用寿命方面的要求。通常地,超级合金的最高工作温度约是1100℃,而燃烧进气或涡轮机排气的温度可以明显地超过1600℃。
在本发明上下文中,已经出现了这些超级合金的热绝缘涂层,允许降低通过内部对流所冷却的部件金属的温度。这些热绝缘涂层,称为热障,或者TBs,通常由在金属接合亚层上所沉积的钇氧化物(或氧化钇)所稳定的外部锆氧化物(氧化锆)基陶瓷层,也称为氧化钇化氧化锆所组成。亚层设计为提供与陶瓷层的粘合,同时保护部件的金属抗氧化和腐蚀。
通过铂的电沉积,接着通过汽相镀铝可以形成金属亚层。通过热喷镀(在所获得的沉积的显微结构具有层状类型的情况下)或者通过材料的电子束汽化(在所获得的沉积的显微结构具有柱状类型的情况下),然后在该亚层上沉积氧化钇化氧化锆的绝缘陶瓷层。
为了改进TB涂层在高温下对氧化/腐蚀抗性方面的性能,已经研发了金属亚层组分,诸如Ni(1-x)PtxAl(镍-铂-铝)组分类型的亚层。通过电解,铂沉积在部件上,通过化学汽相沉积(CVD)或通过物理汽相沉积(PVD)沉积铝。
其它的研发已经集中于改进陶瓷层,特别是集中于使用溶胶凝胶方法或冷等离子体处理,氧化钇化氧化锆层的形成。
本发明的描述
这些研发所提供的TB涂层在性能和使用寿命,特别地涉及氧化/腐蚀抗性方面受到限制。而且,不能保证所使用方法的再现性,特别地是用于生产具有Ni(1-x)PtxAl亚层的涂层的方法的再现性。此外,所实施的方法要求相当数量的精密和长时间的操作。
本发明的特定目的是通过提出用于生产改进的TB组分的方法,克服这些缺点,该改进的组分具有更高的耐火特性和基本上更好的氧化和腐蚀抗性。
为了达到该目的,本发明的方法通过应用场辅助烧结技术(FAST),在这种情况下是火花等离子体烧结(SPS)技术,在单步骤中,从特定的陶瓷层堆叠生产涂层的层,该特定的陶瓷层中每个层都具有与下一个层不同,甚至相反的特定的特性和功能。
在可控环境(真空或特定气体)中,SPS技术同时联合单向压力和DC脉冲。该技术在粉末冶金领域是已知的,因为它允许通过压制和烧结从粉末产生金属部件或氧化物。特别地,SPS技术的使用允许制造显微结构的部件,后者在颗粒尺寸和孔隙率方面受到控制。
更特别地,本发明的目的是一种用于生产用于保护由超级合金所制造的金属部件的多层系统热障的方法。该方法包括在SPS机械套中,通过快速烧结叠置层中保护材料,产生热处理。这些层包括在超级合金基质上至少两层锆基耐火陶瓷,第一陶瓷层,其称作内层和与基质化学地和热地相容,和称作外层的最后的陶瓷层,其设置在其它层之上。该外层具有对CMAS类型的外部污染物更高的物理化学抗性特性,和/或比内层更高的热抗性特性。
物理化学抗性的作用特别是污染物和外层之间的湿润系数,其足以防止熔化的污染物在外层上的扩散和渗透。有利地,外层可以包括特别地铈元素或来自于稀土元素族的另一种元素,如果发生与污染物的化学反应,该元素增加外层的熔化温度。
优选地,选择材料,这样膨胀系数足够高以符合保持最冷的超级合金的膨胀。
有利地,形成金属亚层的金属片的组件可以设置在超级合金基质和陶瓷层之间。
优选地,内层可以具有明显高于最后陶瓷层的热膨胀系数的热膨胀系数,特别地基质的热膨胀系数和最后陶瓷层的热膨胀系统之间的热膨胀系数,并且热障的外层可以具有自然烧结温度以及最高工作温度,其显著地高于内层的最高工作温度。
更特别地,外层的物理化学抗性特性涉及烧结、腐蚀、侵蚀和/或空气动力学特性,通过陶瓷的选择实现这些特性,分别地涉及热传导率、孔隙率、硬度和/或粗糙度,它们适于通过SPS机械的热处理和由热处理加强。因此,相对于内层,外层具有选自下列的至少一个特征:更低的热膨胀、更高的硬度、更低的热传导率、明显更高的烧结温度、更少的开放孔隙率和/或更低的粗糙度。
特别地,优选地,外层的15%和25%之间的热障孔隙率,小于15%的孔隙率。外层的粗糙度优选地小于10微米。
实际上,由于组分的形成和孔隙率梯度,热障具有在陶瓷层中每层所发挥的功能之间的通道梯度,该陶瓷层相对于它们相关特性采用独立形式:内层有利于锚定金属亚层上,特别地在金属亚层表面上形成的氧化铝层上,利用的是其膨胀系数与该亚层的热特性和铝层的热特性一致。结果是接纳了亚层、氧化铝层和内陶瓷层之间的限制。利用比内层更耐火性和具有更高的烧结抗性和最高的工作温度,外层提供了在工作条件下,特别是在涡轮机中更大的热保护。
通过选择外层的材料或附加的适合的层也可以实现通过使外层光滑而改进其它抗性特性(侵蚀、腐蚀)和空气动力学。特别地,更硬的材料提供了对侵蚀更好的抗性。具有低开放孔隙率的材料提供了对高温腐蚀(例如,对CMAS污染(钙-镁-铝-硅酸盐氧化物))类型更好的抗性。小颗粒的材料提供了更小的粗糙度和由此改进空气动力学特性。
根据特定的实施方式,根据是温度、压力和时间控制的快速烧结循环,使用装配有加压装置和用于通过脉冲电流的电装置的套,在生产步骤中进行加压和脉冲电流的通过,使用的温度阈值在1000℃和1600℃之间,优选地1100℃和1400℃之间,并且压力阈值在15Mpa和150Mpa之间,优选地10Mpa和100Mpa之间,这样热障具有组分、孔隙率和用于一方面锚定到金属亚层,另一方面用于外部保护和/或平滑(换而言之,粗糙度)的功能梯度。
本发明进一步涉及由超级合金所制造的金属部件,其装配有包括热障的保护系统,并且根据前述烧结方法生产。当通过快速烧结生产部件时,金属部件由此包括由镍基超级合金构成的基质,具有铂富集β-(Ni,Pt)Al和/或α-NiPtAl相的金属亚层,通过热生长或TGO(“热生长氧化物”)形成的氧化铝层,通过所述方法由至少两个化学地和热-机械地相容锆基陶瓷层所形成和具有外面的热障。第一陶瓷层,称为内层,尽可能靠近金属亚层设置,其与该亚层化学地和热地相容,和最后的外层陶瓷层,尽可能地靠近热障的外面设置,其设计为比内层具有更高的物理化学和/或热抗性特性。
优选地,内陶瓷设计为具有明显高于外陶瓷层的膨胀系数的膨胀系数,该外陶瓷层设置为尽可能靠近热障的外面。该外陶瓷有利地具有明显低于内陶瓷的热传导率的热传导率,和自然烧结温度和/或明显高于内陶瓷的最高工作温度的最高工作温度。热屏障从金属亚层到外面具有组分和孔隙率梯度,和一方面用于锚定到金属亚层上以及另一方面用于保护/和平滑外面的功能梯度。
在这些情况下,热障除了具有热稳定特性外,还具有低的热传导率,接近基质膨胀系数的热膨胀系数和良好的烧结抗性,以及利用其带有各向同性孔隙率的粒状显微结构,由于化学惰性对钙-、镁-和铝-硅酸盐-氧化物腐蚀的抗性,对侵蚀的抗性和良好的空气动力学特性以及在TGO层上优良的粘合。
更具体地,但是不是唯一的,目标金属部件是涡轮机部件或燃气涡轮机压气机部件,特别是整形器、分配器或燃烧室叶片。
根据特定的方式:
-陶瓷选自氧化钇(Y2O3)部分稳定的氧化锆(ZrO2)的“YSZ”化合物,掺杂有氧化钆(Gd2O3)的YSZ的化合物“GYSZ”,锆酸镧(La2Zr2O7)的“LZ”化合物和部分地氧化铈化锆酸镧的“LZC”化合物;
-内/外陶瓷有利地选自下面一对:氧化钇的质量百分比x大于或等于7%的xYSZ/LZ,xYSZ/LZC和xYSZ/GYSZ,特别地,x=7和x=8;
-LZC化合物是LZyC(1-y),其中y=70%,y和1-y表示另外百分比的锆和部分地氧化铈化的锆酸铈,并且掺杂YSZ的化合物是tGvYSZ,其中氧化钆的质量百分比等于2%和YYSZ的质量的百分比v等于8%。
附图的简要说明
通过阅读涉及一个实施方式和参考附图的下面说明书,本发明的进一步特征和优点将会变得更明显。
图1是SPS工具的部分示意截面图,其包括基体和活塞,其中已经引入本发明金属部件样品的层的组件的实施例,以完成快速烧结;
图2表示根据前述组件的快速烧结时间,温度和压力调整循环图示实施例;
图3是快速烧结完成后图1样品的截面图。
详细描述
术语“垂直的”和“水平的”,“上”或“下”以及它们的派生词涉及附图中所示,即操作模式期间的元件。
图1表示使用期间放置在真空中SPS工具1的部分垂直的截面。该工具1包括中空的石墨基体10,其围绕圆柱形室11。本发明金属部件样品的层2的组件已经引入到该室中,用于进行快速烧结。这里所示的层是圆形的,用于形成销钉,以加强烧结后所获得的结构。通过使用具有适合几何形状的室或铸模,本发明延伸到任何类型部件的生产,该部件具有适合它们用途的几何形状。
在组件2的任一侧,在室11中布置电接触12a、12b和14a、14b。接触12a和14a以及12b和14b分别地设置在电屏障13a或13b的任一侧,在这种情况下由氧化铝粉末构成。这些接触由柔性石墨,例如制造。这种材料防止铸模污染和方便从铸模移除。电屏障限制电流流过组件2,该电流主要流过铸模10。
工具还包括石墨接线柱16a和16b,用于垂直的纵向轴线的电力加电。这些接线柱也作为活塞,通过施加外部负载(F箭头)压制组件2任一侧的接触14a和14b。
组件2特别地由构成超级合金22和陶瓷层2a、2b之间的金属亚层21的堆叠的金属片和作为陶瓷粉末沉积在构成亚层21的片上的热障23组成,以形成用于保护基质22的系统24。
在实施例中,基质22是“AM1”镍基超级合金和包括钽(Ta)、铬(Cr)、钴(Co)、钨(W)、铝(Al)、钼(Mo)和钛(Ti)。在该基质上,金属亚层21由连续的5μm厚的铂片和2μm厚的铝片构成。热障23由连续地添加到亚层21上粉末形式的两个陶瓷层2a和2b所构成。
在实施例中,层2a,称作内层,由8YSZ陶瓷粉末,即,由8%质量的氧化钇所稳定的氧化锆所构成。层2b,称为外层,由2G8YSZ陶瓷粉末,即,(8%质量的)氧化钇部分稳定和掺杂有氧化钆(GdO2)或2%质量的Gd的氧化锆(ZrO2)所构成。
在其它实施例中,层2a和2b分别由7YSZ/LZ和7YSZ/LZ7C3的陶瓷粉末(即,具有70%氧化锆,并且以补充方式,具有30%铈)构成。
在快速烧结操作期间,根据时间“t”的温度“T”和压力“P”的调整循环符合图2的图示。温度图示DT在温度增加T1后,达到700℃的第一阈值P1,具有每分钟100℃的匀变。第一阈值P1持续大约10分钟,接着是第二温度增加T2,具有相同的匀变,持续大约10分钟。
第二次增加之后是第三次增加T3,其具有更少的节距(50℃/min)和持续期间(大约5分钟),以达到第二阈值或主阈值P2。该第二阈值P2位于1100-1200℃的间隔,和持续大约15分钟。进行温度可控的冷却R1大约30分钟,用每分钟20℃节距的数量级,以达到大约500℃。该循环持续大约1小时。该第一温度下降之后,接着是第二自然冷却阶段,以达到环境温度。
压力图示Dp表示实施例中从大气压力0.1Mpa达到100Mpa的极快压力增加A1。维持压力阈值P3,并且持续操作的大部分时间,例如40到50分钟。压力下降A2进行非常短的时间,以返回到大气压。
通过快速烧结所提供的,根据本发明的涂覆有保护系统的金属部件的3维样品如在图3的截面中所示。它包括涂覆有保护系统的超级合金基质22,该保护系统最初在快速烧结操作之前由分离的层所制造,包括连续层的金属亚层21、氧化铝层25,称作“TGO”层和由内陶瓷2a和外陶瓷2b所组成的热障23。
外陶瓷2b具有相对低的热传导率,在压实之前是在0.8和1.7Wm-1K-1之间,工作之后小于0.8。
此外,陶瓷2b和2a的最高工作温度分别地等于1200℃和1600℃和更高。而且,当温度达到1600℃或更高时,外陶瓷2b不会显示自然烧结。
而且,外陶瓷2b有利地具有明显地高于内陶瓷2a的膨胀系数的膨胀系数,其是10.4.10-6K-1。这两个膨胀系数之间的差异控制组件的使用寿命,特别地陶瓷粘合到SPS烧结期间所形成的TGO氧化物上。
而且,选择两个陶瓷的原始粉末的粒度测定,这样内层最终没有外层密实。那么,更密实的外层更容易阻止CMAS污染物(钙-镁-铝-硅酸盐氧化物)类型,后者不能穿透所述外层。不密实的内层由此更容易接纳基质和亚层的变形。
此外,外陶瓷2b的热特性在工作条件下,特别是在其中燃气温度可以达到1600℃或更高的涡轮机中提供了良好的抗性。
图3也表示热障23的孔隙率梯度G1,从外层2a到TGO层,热障23的层的小孔3的尺寸增加。也示出了热障23的陶瓷组分梯度G2,在热障23的中间区域中原始陶瓷层2a和2b互相渗透。这些梯度引起TGO层和外面2e之间两个陶瓷原始特性的渐进梯度变化,其中在TGO层,该特性是原始内层2a的特性,以及在外面2e中,该特性是原始层2b的特性。符合热障23特性和由此功能的渐进梯度,范围从与外面2e上金属亚层相容到热保护功能。
本发明不限于已经描述和这里所示的实施例。例如,可以组合两个以上原始陶瓷层,例如三或四层化学地和热-机械地相容的陶瓷。有利地,这些层在最接近金属亚层的第一内层和沉积在其它层上的外层之间,具有在相同方向变化的特性和热功能。第一内层具有与金属亚层的热-机械特性相容的热-机械特性,最后的外层在等于或高于约1600℃的温度条件下使用方面,具有最大的抗热特性。可以添加层,该层仅设计为保护组件免受CMAS腐蚀和/或通过平滑热障来改进空气动力学。
Claims (11)
1.一种用于生产用于保护由超级合金所制造的金属部件的多层系统(24)热障(23)的方法,其特征在于:该方法包括在SPS机械套(1)中,通过快速烧结所述金属件(22)上叠置的层中保护材料(24),产生热处理,所述层包括在超级合金基质(22)上至少两层锆基耐火陶瓷(2a、2b),第一陶瓷层(2a),其称作内层和与所述基质(22)化学地和热地相容,和称作外层的最后的陶瓷层(2b),其设置在其它层之上,所述外层(2b)具有对CMAS类型污染物更高的物理化学抗性特性,和/或比所述内层(2a)更高的热抗性特性。
2.根据权利要求1的用于生产热障的方法,其中所述内层(2a)具有明显地高于所述最后陶瓷层(2b)的热膨胀系数的热膨胀系数。
3.根据权利要求1或权利要求2中任一的用于生产热障的方法,其中所述外层(2)的物理化学抗性特性涉及烧结、腐蚀、侵蚀和/或空气动力学特性,通过陶瓷的选择实现这些特性,分别地涉及热传导率、孔隙率、硬度和/或粗糙度,它们适于通过SPS机械的热处理和由热处理加强,这样相对于所述内层(2a),所述外层(2b)具有选自下列的至少一个特征:更低的热膨胀、更高的硬度、更低的热传导率、明显更高的烧结温度、更少的开放孔隙率和/或更低的粗糙度。
4.根据前述权利要求之一的用于生产热障的方法,其中形成金属亚层(21)的金属片的组件设置在所述超级合金基质(22)和所述陶瓷层(2a、2b)之间。
5.根据前述权利要求之一的用于生产热障的方法,其中所述套(11)装配有加压装置和电力加电装置(16a、16b)和用于脉冲电流通过所述室(11)的电接触(12a、14a;12b、14b),并且其中在生产步骤中,根据温度、压力和时间可控的快速烧结循环(DT、DP)进行加压和同时脉冲电流的通过,使用的温度阈值(P2)在1000℃和1600℃之间,优选地1100℃和1400℃之间,并且压力阈值(P3)在15Mpa和150Mpa之间,优选地10Mpa和100Mpa之间,这样所述热障(23)具有组分(G)、孔隙率(G1)和用于一方面锚定到所述金属亚层(21),另一方面用于保护和/或外部平滑的功能梯度。
6.一种由超级合金所制造的金属部件,其装配有包括热障的和根据前述权利要求中任一权利要求的方法所产生的保护系统,其特征在于所述金属部件由此包括由镍基超级合金所构成的基质(22)、具有铂富集β-(Ni,Pt)Al和/或α-NiPtAl相的金属亚层(21),通过快速烧结的部件生产期间,通过热生长所形成的TGO氧化物层(25),以及通过所述方法由至少两个化学地和热-机械地相容的锆基陶瓷层(2a、2b)所形成的和具有外面(2e)的热障(23),第一陶瓷层(2a),称为内层,尽可能靠近所述金属亚层(21)设置,其与所述亚层(21)化学地和热地相容,和最后的外陶瓷层(2b),尽可能地靠近所述热障(23)的所述外面(2e)设置,其中设计所述最后的层(2b)以比内层(2a)具有更高的物理化学和/或热抗性特性。
7.根据前述权利要求的金属部件,其中所述内陶瓷(2a)比所述外陶瓷(2b)具有更高的热膨胀系数,并且所述外陶瓷(2b)比所述内陶瓷(2a)具有明显低的热传导率,并且具有比所述内层(2a)明显更高的自然烧结温度和/或最高工作温度。
8.根据权利要求6或权利要求7中任一权利要求的金属部件,其中所述热障(23)具有从所述金属亚层(21)到所述外面(2e)的组成和孔隙率梯度(3),和一方面用于锚定到所述金属亚层(21)上以及另一方面用于保护/和平滑所述外面(2e)的功能梯度。
9.根据前述权利要求所述的金属部件,其中所述陶瓷(2a、2b)选自氧化钇部分稳定的氧化锆的“YSZ”化合物,掺杂有氧化钆的YSZ的化合物“GYSZ”,锆酸镧(La2Zr2O7)的“LZ”化合物和部分地氧化铈化锆酸镧的“LZC”化合物。
10.根据前述权利要求所述的金属部件,其中所述内/外陶瓷(2a、2b)有利地选自下面一对:氧化钇的质量百分比x大于或等于7%质量的xYSZ/LZ,xYSZ/LZC和xYSZ/GYSZ,特别地,x=7和x=8%质量。
11.根据权利要求9或权利要求10所述的金属部件,其中LZC化合物是LZyC(1-y),其中y=70%,y和1-y表示另外百分比的锆和部分地氧化铈化的锆酸铈,并且掺杂YSZ的化合物是tGvYSZ,其中氧化钆的质量百分比t等于2%和YSZ的质量百分比v等于8%。
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US10161262B2 (en) | 2018-12-25 |
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