CN109312445A - 保护不含铪的镍基单晶超合金部件免受腐蚀和氧化的方法 - Google Patents

保护不含铪的镍基单晶超合金部件免受腐蚀和氧化的方法 Download PDF

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CN109312445A
CN109312445A CN201780035884.6A CN201780035884A CN109312445A CN 109312445 A CN109312445 A CN 109312445A CN 201780035884 A CN201780035884 A CN 201780035884A CN 109312445 A CN109312445 A CN 109312445A
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艾玛尔·撒伯恩德吉
维尔日妮·杰凯特
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Abstract

本发明涉及一种用于保护不含铪的镍基单晶超合金部件(1)免受腐蚀和氧化的方法。所述方法的特征在于其涉及至少以下步骤：制造不含铪的镍基单晶超合金部件(1)；在所述部件(1)上沉积包含铪的第一层(2)，沉积由包含至少10原子％铝的合金制成的底涂层以及包含铪的第二层来形成混合层(3)，以及在所述部件(1)上沉积包含铪的第三层(4)；进行扩散处理以使第一层(2)和第三层(4)扩散，从而在所述部件(1)的顶部形成第一相互扩散区(21)，在所述混合层(3)的表面上形成第二相互扩散区(41)；对所述第二相互扩散区(41)进行氧化处理以获得掺杂铪的氧化铝层(42)。

Description

保护不含铪的镍基单晶超合金部件免受腐蚀和氧化的方法
技术领域
本发明属于镍基单晶超合金的领域。
更具体地，本发明涉及一种用于保护不含铪的镍基单晶超合金部件免受腐蚀和氧化的方法。
背景技术
术语“超合金”是指在高温和高压下对氧化、腐蚀、蠕变和循环应力(特别是机械应力或热应力)表现出极好耐性的复合合金。这些超合金的具体应用在于制造航空用部件。
从内部到外部依次包括镍基单晶超合金基材、底涂层和绝热层的部件是现有技术中已知的。
已知的是，添加铪来改善超合金的耐腐蚀性和耐氧化性，以及绝热层的粘附性。
存在将铪添加到上述部件中的若干种技术。
第一种技术包括将少量铪直接加入到基材中，即在生产构成基材的超合金的过程中。然而，这使得这种超合金更加难以固溶化。
超合金经历热处理，包括固溶化阶段和回火阶段。这种处理包括将合金加热到低于共晶温度的合适温度，并在该温度下保持足够长的时间以使组成的元素浓度均匀化并控制金属间沉淀物的尺寸。从而优化了材料的微观结构特性。
然而，超合金中铪的存在使得共晶体难以完全或接近完全固溶化并且导致燃烧型缺陷
此外，第一种技术不会改善绝热层对基材的粘附性，因为超合金中铪的含有量较低并且扩散到底涂层中的铪的量甚至更低。然而，第一种技术改善了由此获得的部件的耐氧化性。
第二种技术是在沉积底涂层时将铪添加到该底涂层中。然而，该技术仅改善了绝热层对基材的粘附性。实际上，铪主要扩散到底涂层的晶界中，并因此不能改善超合金基材的耐腐蚀性和耐氧化性。
最后，第三种已知技术是既向基材中添加少量的铪，又在底涂层沉积期间添加少量的铪。
然而，该解决方案具有与第一种技术中提及的问题相同的问题。
发明内容
因此，本发明的目的是克服现有技术的上述缺点。
特别地，本发明的目的是改善由不含铪的镍基单晶超合金制成的部件的耐腐蚀性和耐氧化性。
进一步地，当部件涂有绝热层时，本发明的目的还在于改善绝热层对部件的粘附性并增加由此形成的整个部件的使用寿命。
为此，本发明涉及一种用于保护不含铪的镍基单晶超合金部件免受腐蚀和氧化的方法。
根据本发明，该方法至少包括以下步骤：
制造不含铪的镍基单晶超合金部件，
在所述部件上沉积包含铪的第一层，然后同时或交替地沉积包含至少10原子％铝的合金的底涂层和包含铪的第二层以形成混合层，且最后沉积包括铪的第三层，
使所述包含铪的第一层扩散，以在所述不含铪的镍基单晶超合金部件的上部形成第一相互扩散区，并且使所述包含铪的第三层扩散，以在所述混合层的表面上形成第二相互扩散区，
在扩散处理之后，对所述第二相互扩散区进行氧化处理，以在所述第二相互扩散区的表面上获得掺杂铪的氧化铝层。
由于本发明的这些特征，所获得的部件具有更好的耐腐蚀性和耐氧化性。
本发明单独或以组合出现的其他有利和非限制性特征如下：
所述方法包括在进行扩散处理之前，首先沉积各个层和底涂层，
所述方法包括至少以下步骤：
制造不含铪的镍基单晶超合金部件，
在所述部件上沉积包含铪的第一层，
使所述包含铪的第一层扩散，以在所述不含铪的镍基单晶超合金部件的表面形成第一相互扩散区，
在所述第一相互扩散区上同时或交替沉积包含至少10原子％铝的合金的底涂层和包含铪的第二层以形成混合层，
在所述混合层上沉积包含铪的第三层，
使所述包含铪的第三层扩散，以在所述混合层的表面上形成第二相互扩散区，
对所述第二相互扩散区进行氧化处理，以在所述第二相互扩散区的表面上获得掺杂铪的氧化铝层，
所述方法包括在所述掺杂铪的氧化铝层上沉积绝热层的步骤，
至少一个沉积步骤通过物理气相沉积(PVD)，优选通过阴极溅射来进行，
沉积在100℃至900℃的温度、0.1Pa至1Pa的压力、2至15W/cm2的功率密度和-500V至-150V的阴极化、-200V至500V的离子轰击下通过阴极溅射持续进行10分钟到30分钟，
扩散处理在真空下或在氩气和5％(体积)氦气的混合物存在下通过热处理来进行，该热处理包括升高温度直至达到800℃至1200℃的温度的步骤，保持该温度1小时至4小时的步骤，以及降低温度直至达到室温的冷却步骤，
对第二相互扩散区(41)进行的氧化处理通过在氧气分压或氩气分压下通过热处理来进行，该热处理包括升高温度直至达到900℃至1200℃的温度的步骤，保持该温度不到1小时的步骤，以及进行冷却直到达到室温的步骤。
附图说明
根据下文参照附图进行的描述，本发明的其他特征和优点将更加明显，其中，附图以非限制性说明的方式来表示一个可能的实施方案。
在这些图中：
图1至图8是根据本发明方法的第一实施方案的各个步骤的图，以及
图9至图15是表示根据本发明方法的第二实施方案的各个步骤的图。
具体实施方式
现在将参考附图描述根据本发明方法的各个步骤。
图1表示该方法的第一步，制造不含铪的镍基单晶超合金部件1。
该部件1例如通过铸造或增材制造来获得的，并且具有期望的形状。
下表1显示了可用于本发明方法的几种示例性超合金。它们由字母A到F表示。
表1
示例性不含铪的镍基单晶超合金
对于每种超合金，术语“余量”对应于与所提及的各种其他组分一起达到100％的剩余质量百分比。
图2示出了该方法的第二步，为在所述部件1上沉积包含铪的第一层2。优选地，该第一层具有50nm至800nm，更优选50nm至300nm的厚度。
可通过化学气相沉积(CVD)来沉积铪的第一层2。
然而，优选地，通过物理气相沉积(PVD)进行，更优选通过阴极溅射进行，以能够良好地控制沉积的厚度。
PVD在容纳有部件1和对应于待沉积材料(这里，特别是铪)的一个或多个靶的壳体内进行。在反应器壁和靶之间施加电势差的情况下，形成等离子体，其正粒子被吸引到阴极(靶)并与之碰撞。靶的原子被溅射，然后凝结在部件1上。
优选地，沉积条件如下：
沉积期间加热：100℃至900℃
压力：0.1Pa至1Pa，
功率密度：2W/cm2至15W/cm2，
极化：-500V至-150V。
离子轰击在-200V至500V下进行10分钟到30分钟。
然后进行使铪的第一层2扩散的步骤(参见图3)，从而在所述部件1的表面上形成存在铪的第一相互扩散区21。尽管未在这些图中示出，但是铪的整个层可能没有扩散，并且在该相互扩散层21上方保留有铪的薄层。
优选地，通过将涂有铪的第一层2的部件1置于壳体内，使壳体处于真空下或在其中引入含有氩气和5体积％氦气的混合物的气氛来进行扩散处理。
该壳体优选地不同于用于沉积的壳体，但也可以是相同的。
然后优选如下所述进行扩散。
接下来是热处理，包括升高温度直至达到800℃至1200℃的温度的阶段，该温度阶段保持1小时至4小时的时间。
在该阶段之后，通过将壳体内的温度降低直至恢复到室温进行冷却步骤。
由此形成的第一相互扩散区21保护不含铪的镍基单晶超合金部件1免受腐蚀和氧化。
该方法的第四步如图4所示，为在第一相互扩散区21上同时或交替地沉积合金的底涂层和包含铪的第二层以形成混合层3，所述合金包含至少10原子％铝且优选小于50原子％铝，优选选自NiAlCrSi、NiAlCrSiPt、NiCoAlCrSiPt、NiAl、NiPtAl或MCrAlY，其中，M为钴、镍或钴-镍的合金。
优选地，包含至少10原子％铝的底涂层具有5μm至30μm的厚度。还优选地，包含铪的第二层具有20nm至700nm的厚度。
当同时沉积时，获得合金。因此，例如，如果底涂层是NiAlPt，则获得的混合层3将是NiAlPtHf。
该沉积可以通过上述沉积技术之一进行。
优选地，沉积在上述条件下通过阴极溅射来进行。
这种同时沉积可以使用用于沉积铪层的铪靶和合金靶(即含有待沉积合金的各种组分)来进行，以形成底涂层。
根据另一个实施方案，该沉积可以使用待沉积的每种化学元素的靶来进行，例如用于同时沉积NiCrAlY和铪的五个靶(共溅射沉积)。
下表给出了可以使用的底涂层和铪的厚度组合的不同实例。
表2
通过阻挡底涂层中含有的金属阳离子的扩散并通过减缓其中氧的扩散并因此减缓底涂层的氧化动力学，在底涂层沉积期间，第二次沉积铪增强了底涂层晶界。该混合层3的作用是增加铝储层的寿命和绝热层(如果后续形成)的寿命。
该方法的第五步如图5所示，为在所述混合层3上沉积包含铪的第三层4，其具有优选为10nm至100nm的厚度。
有利地，该沉积使用上述沉积铪的第一层2时所述的相同技术且在相同条件下进行。
最后，如图6所示，该方法包括使部件1经受扩散处理然后经受氧化处理。
铪的第三层4的扩散产生第二相互扩散区41。扩散处理有利地在与上述用于铪的第一层2的扩散处理的条件相同的条件下进行。
氧化处理如图7所示，产生氧化铝和铪的层42。
其厚度优选地为200nm至700nm。
更确切地说，其是在其晶界中包含铪的氧化铝的层，即在晶界处掺杂铪的氧化铝的层。
氧化处理在氧气分压或氩气分压下于壳体内进行。
氧化处理的各个步骤优选如下：
升高温度：优选80℃/min至100℃/min，
氧化阶段：0.5小时至1小时，温度为900℃至1200℃，
冷却，温度降低：优选80℃/min至100℃/min。
最后，还可以在掺杂铪的氧化铝的层42上沉积绝热层5(参见图8)。该层5例如是钇稳定的氧化锆(yttriated zirconia)或包含陶瓷和钇稳定的氧化锆的多层。
应该注意的是，铪的沉积以及使底涂层扩散和氧化的各个步骤可以在相同的沉积机器中进行，以简化制造。
现在将结合图9至图15描述根据本发明方法的第二个实施方案。它是第一实施方案的变型。因此，相同的层或底涂层具有相同的附图标记。
图9至图10中示出的该方法的前两个步骤与图1和图2中示出的第一个实施方案的前两个步骤相同。
接下来形成如上所述的混合层3，但是该混合层3直接在包含铪的第一层2上形成(如图11中所示的步骤)。
接下来在所述混合层3上沉积包含铪的第三层4(如图12所示)，如前面实施方案中所述。
在已经形成或沉积所有层2、层3和层4之后，进行扩散处理，以使第一层2在部件1的上部扩散并上部形成第一相互扩散区21；并且使包含铪的第三层4在所述混合层3的表面上扩散，形成第二相互扩散区41(参见图13)。扩散处理与上述第一个实施方案中的扩散处理相同。该步骤如图13所示。
最后，根据对第一个实施方案步骤进行描述，进行对第二相互扩散区41进行氧化处理，然后可选地在先前形成的氧化铝层42沉积绝热层5的最后两个步骤。这些步骤分别如图14和图15所示。
通常，根据本发明的方法因此包括沉积或形成各个层2、3、4并进行上述扩散处理。这种扩散处理可以在沉积第一层2之后进行，然后在沉积第三层4之后重复进行，或者在所有层沉积之后在单个步骤中进行。

Claims (13)

1.一种保护不含铪的镍基单晶超合金部件(1)免受腐蚀和氧化的方法，其特征在于，所述方法至少包括以下步骤：
制造不含铪的镍基单晶超合金部件(1)；
在所述部件(1)上沉积包含铪的第一层(2)，然后同时或交替沉积包含至少10原子％铝的合金的底涂层和包含铪的第二层以形成混合层(3)，且最后沉积包含铪的第三层(4)；
使所述包含铪的第一层(2)扩散，以在所述不含铪的镍基单晶超合金部件(1)的上部形成第一相互扩散区(21)，并使所述包括铪的第三层(4)扩散，以在所述混合层(3)的表面上形成第二相互扩散区(41)；
在扩散处理之后，对所述第二相互扩散区(41)进行氧化处理，以在所述第二相互扩散区(41)的表面上获得掺杂铪的氧化铝层(42)。
2.根据权利要求1所述的方法，其特征在于，所述方法包括在进行所述扩散处理之前，首先沉积各个层和底涂层。
3.根据权利要求1所述的方法，其特征在于，所述方法包括至少以下步骤：
制造不含铪的镍基单晶超合金部件(1)，
在所述部件(1)上沉积包含铪的第一层(2)，
使所述包含铪的第一层(2)扩散，以在所述不含铪的镍基单晶超合金部件(1)的表面上形成第一相互扩散区(21)，
在所述第一相互扩散区(21)上同时或交替地沉积包含至少10原子％铝的合金的底涂层和包含铪的第二层以形成混合层(3)，
在所述混合层(3)上沉积包含铪的第三层(4)
使所述包含铪的第三层(4)扩散，以在所述混合层(3)的表面上形成第二相互扩散区(41)，
对所述第二相互扩散区(41)进行氧化处理，以在所述第二相互扩散区(41)的表面上获得掺杂铪的氧化铝层(42)。
4.根据前述权利要求中任一项所述的方法，其特征在于，所述方法包括在所述掺杂铪的氧化铝层(42)上沉积绝热层(5)的步骤。
5.根据前述权利要求中任一项所述的方法，其特征在于，至少一个所述沉积步骤通过物理气相沉积(PVD)，优选通过阴极溅射来进行。
6.根据权利要求5所述的方法，其特征在于，所述沉积在100℃至900℃的温度、0.1Pa至1Pa的压力、2W/cm2至15W/cm2的功率密度和-500V至-150V的阴极化、-200V至500V的离子轰击下，通过阴极溅射持续10分钟至30分钟来进行。
7.根据前述权利要求中任一项所述的方法，其特征在于，所述扩散处理在真空下或在氩气和5体积％氦气的混合物存在下通过热处理来进行，该热处理包括升高温度直至达到800℃至1200℃的温度的步骤，保持该温度1小时至4小时的步骤，以及降低温度直至达到室温的冷却步骤。
8.根据前述权利要求中任一项所述的方法，其特征在于，对所述第二相互扩散区(41)进行的氧化处理在氧气分压或氩气分压下通过热处理来进行，该热处理包括升高温度直至达到900℃至1200℃的温度的步骤，保持该温度不到1小时的步骤，以及进行冷却直到达到室温的步骤。
9.根据前述权利要求中任一项所述的方法，其特征在于，所述包含铪的第一层(2)具有50nm至800nm，优选为50nm至300nm的厚度。
10.根据前述权利要求中任一项所述的方法，其特征在于，所述包含至少10原子％铝的合金的底涂层选自NiAlCrSi、NiAlCrSiPt、NiCoAlCrSiPt、NiAl、NiPtAl或MCrAlY，其中M为钴、镍或钴-镍。
11.根据前述权利要求中任一项所述的方法，其特征在于，所述包含至少10原子％铝的合金的底涂层具有5μm至30μm的厚度。
12.根据前述权利要求中任一项所述的方法，其特征在于，所述包含铪的第二层具有20nm至700nm的厚度。
13.根据前述权利要求中任一项所述的方法，其特征在于，所述包含铪的第三层(4)具有10nm至100nm的厚度。
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BR112018075435B1 (pt) 2022-06-14
RU2019100057A3 (zh) 2020-07-13
WO2017212193A1 (fr) 2017-12-14
FR3052464B1 (fr) 2018-05-18
RU2742919C2 (ru) 2021-02-11
JP2019524983A (ja) 2019-09-05
FR3052464A1 (fr) 2017-12-15
EP3469112B1 (fr) 2020-07-22
EP3469112A1 (fr) 2019-04-17
JP6931008B2 (ja) 2021-09-01
BR112018075435A2 (pt) 2019-03-19
CN109312445B (zh) 2021-03-09
RU2019100057A (ru) 2020-07-13
CA3026710A1 (fr) 2017-12-14

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