CN114585769A - 由包含铼和/或钌的高温合金制成的飞行器部件及其制造方法 - Google Patents
由包含铼和/或钌的高温合金制成的飞行器部件及其制造方法 Download PDFInfo
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- CN114585769A CN114585769A CN202080070810.8A CN202080070810A CN114585769A CN 114585769 A CN114585769 A CN 114585769A CN 202080070810 A CN202080070810 A CN 202080070810A CN 114585769 A CN114585769 A CN 114585769A
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- substrate
- mass fraction
- average mass
- ruthenium
- rhenium
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Links
- 229910000601 superalloy Inorganic materials 0.000 title claims abstract description 54
- 229910052702 rhenium Inorganic materials 0.000 title claims abstract description 45
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 title claims abstract description 45
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 117
- 239000011253 protective coating Substances 0.000 claims abstract description 42
- 230000002378 acidificating effect Effects 0.000 claims abstract description 15
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 238000000151 deposition Methods 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 35
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 27
- 239000011651 chromium Substances 0.000 claims description 26
- 229910052804 chromium Inorganic materials 0.000 claims description 25
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 22
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052735 hafnium Inorganic materials 0.000 claims description 7
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 238000003487 electrochemical reaction Methods 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims 1
- 238000003486 chemical etching Methods 0.000 abstract description 4
- 238000005530 etching Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 26
- 239000012071 phase Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 14
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000004888 barrier function Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000011241 protective layer Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000005488 sandblasting Methods 0.000 description 3
- 229910052594 sapphire Inorganic materials 0.000 description 3
- 238000010517 secondary reaction Methods 0.000 description 3
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910000734 martensite Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 230000002028 premature Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910001011 CMSX-4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005328 electron beam physical vapour deposition Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004439 roughness measurement Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 1
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
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- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
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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
- C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
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- C—CHEMISTRY; METALLURGY
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- 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
- F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
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- F01D5/28—Selecting particular materials; Particular measures relating thereto; Measures against erosion or corrosion
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- C22C19/03—Alloys based on nickel or cobalt based on nickel
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- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/057—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being less 10%
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Abstract
本发明涉及用于制造部件的方法，包括在湿酸性介质中对由单晶高温合金制成的衬底的表面的至少部分进行化学蚀刻的步骤，该基底包含选自铼和钌的至少一种元素，该基底具有γ‑γ’相，该基底具有平均质量分数大于或等于3％的铼和/或钌，该化学蚀刻以使得在该基底的表面的该部分中铼和/或钌的平均质量分数小于2％的方式进行；和在基底的该部分上沉积保护涂层的步骤，并且该保护涂层具有γ‑γ’相以及平均质量分数小于1％的铼和/或钌。
Description
技术领域
本发明涉及飞行器部件，举例来说，诸如涡轮叶片或分配器轮叶。
背景技术
在涡轮喷气发动机中，燃烧室产生的排气可以达到例如超过1200℃，甚至1600℃的高温。因此，涡轮喷气发动机的与这些排气接触的部件，例如涡轮叶片，必须能够在如此高温下保持它们的机械性能。
为此目的，已知采用“高温合金”制造涡轮喷气发动机的某些部件。高温合金是一类高抗性的金属合金，其可以在相对接近它们的熔点的温度(通常是它们的熔点温度的0.7到0.8倍)下工作。
已知将铼和/或钌引入高温合金中，以提高其在高温下的机械抗性能力，尤其是抗蠕变能力。尤其，相对于不含铼和/或钌的高温合金，铼和/或钌的引入使这些高温合金的使用温度提高约100℃。
然而，高温合金中铼和/或钌的平均质量分数的增加需要高温合金中铬的平均质量分数的降低，以便保持高温合金的稳定的同素异形结构，尤其是稳定的γ-γ’相。然而，高温合金中的铬促进了氧化物Cr2O3的生成，Cr2O3具有与α-Al2O3相同的晶体结构，从而使α-Al2O3的层能够成核。该α-Al2O3的稳定层有助于保护高温合金免受氧化。因此，与不含铼和/或钌的高温合金相比，铼和/或钌的平均质量分数的增加导致高温合金的抗氧化性降低。
为了增强这些高温合金的耐热性，并且保护它们免受氧化和腐蚀，还已知采用热屏障覆盖它们。
参照图1和图2，现有技术的飞行器部件1可以例如包括由单晶金属高温合金制成的基底2’，基底2’覆盖有涂层，例如包括热屏障的环境屏障。
环境屏障通常包括在基底2’和热屏障之间的保护涂层3’。保护涂层3’优选地为金属结合层3’。结合层3’覆盖由金属高温合金制成的基底2’。结合层3’本身通常由保护层覆盖，保护层由金属结合层3’的氧化形成。保护层保护由高温合金制成的基底2’免受腐蚀和/或氧化。热屏障覆盖保护层。热屏障可以由陶瓷，例如氧化钇稳定的氧化锆制成。
亚层3’的铝的平均质量分数足以专门形成氧化铝(Al2O3)保护层，该保护层保护由高温合金2’制成的基底免受氧化和腐蚀。
然而，当部件经受高温时，由高温合金2’制成的基底和金属结合层3’之间的镍，尤其是铝的平均质量分数的差异导致各种元素，尤其是基底中所含的镍向金属结合层扩散，以及金属结合层中所含的铝向高温合金扩散。这种现象称为“相互扩散”。
相互扩散可以导致在与结合层3’接触的衬底2’的一部分中形成初级和次级反应区(SRZ)。这些区域通常称为“相互扩散区”。
图1是现有技术中覆盖部件1’的基底2’的结合层3’的截面的显微图。显微图在部件经受了一系列模拟部件1’在使用过程中的温度条件的热循环后产生。基底2’富含铼，换言之，铼的平均质量分数大于或等于3％，优选地大于或等于4％。已知在高温合金组成中使用铼以提高高温合金部件的抗蠕变性。通常，基底2’具有γ-γ’相，尤其是γ-Ni相。基底2’在基底的直接由结合层3’覆盖的部分中具有初级相互扩散区5’。基底2’还具有直接由初级相互扩散区5’覆盖的次级相互扩散区6’。
参照图2，相互扩散现象导致结合层3’中的铝过早贫化，这促进了结合层3’的相变(例如马氏体转变)。这些转变改变了结合层3’和/或互扩散区的同素异形结构，在蠕变型热力学应力之后在那里产生裂纹8，通过包括高温合金和涂层的***的蠕变促进了过早劣化。
因此，在由高温合金制成的基底2’和结合层3’之间的相互扩散会对高温合金部件的使用寿命产生有害的影响。
发明内容
本发明的目的是提出一种解决方案，以有效地保护由高温合金制成的涡轮部件在使用期间免受氧化和腐蚀，同时与已知部件相比，增加其使用寿命。
本发明的另一个目的是限制或防止次级反应区的形成，同时能够在部件的使用期间形成氧化铝。
最后，本发明的另一个目的是至少部分地防止在经受高温条件(例如大于1000℃)的部件的基底中形成裂纹，以及防止氧化铝保护层的剥落。
在本发明的上下文中，这些目的通过一种用于制造部件的方法来实现，该方法包括以下步骤：
a)在湿酸性介质中，对由单晶高温合金制成的基底的表面的至少部分进行化学侵蚀，所述基底包含选自铼和钌的至少一种元素，所述基底具有γ-γ’相，所述基底具有平均质量分数大于或等于3％，优选地大于或等于4％的铼和/或钌，所述化学侵蚀以使得在所述基底的表面的该部分中铼和/或钌的平均质量分数小于2％的方式进行，
b)在所述基底的该部分上沉积保护涂层，该保护涂层具有γ-γ’相以及平均质量分数小于1％的铼和/或钌。
本发明有利地由以下被单独地采用或以它们的任何可能的技术组合采用的特征来补充：
基底由镍基单晶高温合金制成，
所述基底包含铬，铬的平均质量分数小于5％，优选地小于3％，
化学侵蚀是化学蚀刻，
进行化学侵蚀，使得基底表面的该部分的算术平均粗糙度Ra在0.5μm-5μm之间，并且优选地最大粗糙度RZ在5.5μm-50μm之间，粗糙度Ra和RZ在大于1mm2的面积上测量，
在酸性介质中的化学侵蚀通过与基底表面的该部分接触的浸泡液(bath)进行，所述浸泡液包括氢氟酸、硝酸与氯化铁和盐酸、盐酸与氯化铁、盐酸与过氧化氢，以及硝酸与盐酸中的至少一种，
在酸性介质中的化学侵蚀通过与基底表面的该部分接触的浸泡液进行，控制浸泡液的电位以便在表面的该部分上引起电化学反应，浸泡液优选地包括硝酸与乙酸、硫酸和磷酸中的至少一种。
本发明的另一个方面是一种部件，该部件包括：
由单晶高温合金制成的基底，所述基底包含选自铼和钌的至少一种元素，所述基底具有γ-γ’相，以及平均质量分数大于或等于3％，优选地大于或等于4％的铼和/或钌，
保护涂层，所述保护涂层覆盖基底表面的至少部分，
基底表面的该部分上的铼和/或钌的平均质量分数小于2％，和
所述保护涂层具有γ-γ’相以及平均质量分数小于1％的铼和/或钌。
本发明有利地由以下被单独地采用或以它们的任何可能的技术组合采用的特征来补充：
所述基底包含铬，铬的平均质量分数小于5％，优选地小于3％，
基底表面的该部分的算术平均粗糙度Ra在0.5μm-5μm之间，并且优选地最大粗糙度RZ在5.5μm-50μm之间，粗糙度Ra和RZ在大于1mm2的面积上测量，并且通过在酸性介质中对所述基底表面的该部分进行化学侵蚀来获得，
所述保护涂层以体积计主要为γ’相，
所述保护涂层包含至少镍、铝、铬、铪和硅，
所述保护涂层具有：
平均质量分数占大多数的镍，
平均质量分数在5％-15％之间的铝，
平均质量分数在7％-15％之间的铬，
平均质量分数在0.5％-2％之间的铪，
和
平均质量分数在0.5％-3％之间的硅。
本发明的另一方面是根据本发明的飞行器部件。
本发明的另一方面是包括根据本发明的部件的飞行器涡轮。
本发明的另一方面是包括根据本发明的部件的飞行器。
附图说明
本发明的其他特征、目的和优点将从以下描述中体现，以下描述纯粹是以说明的方式给出，而非限制性的，并且应该参照附图来阅读，在附图中：
[图1]已经讨论过的图1是现有技术的基底和结合层在部件经受表示该部件的使用的热工况之后的微观结构的扫描电子显微镜照片；
[图2]已经讨论过的图2是现有技术的基底和结合层在部件经受表示该部件的使用的热力学应力之后的细节的微观结构的扫描电子显微镜照片，所述基底包括裂纹；
[图3]图3示意性地示出了飞行器部件，例如涡轮叶片或分配器轮叶的截面；
[图4]图4示意性地示出了根据本发明的实施方式的用于制造部件的方法；
[图5]图5是根据本发明的实施方式的基底和结合层的微观结构的扫描电子显微镜照片；
[图6]图6是根据本发明的实施方式的基底和结合层的微观结构的扫描电子显微镜照片；
[图7]图7是根据本发明的实施方式的基底和结合层的微观结构的扫描电子显微镜照片。
在这套图中，相似的元件具有相同的附图标记。
定义
术语“高温合金”是指在高温高压下具有很好的抗氧化、抗腐蚀、抗蠕变和抗循环应力(尤其是机械或热循环应力)性能的合金。高温合金在用于航空的部件，例如涡轮叶片的制造中有特殊的应用，因为它们构成了可以在相对接近它们的熔点的温度(通常是它们的熔点温度的0.7至0.8倍)下工作的一类高抗性合金。
高温合金可以具有双相微观结构，包括形成基体的第一相(称为“γ相”)和在基体中形成硬化析出物的第二相(称为“γ’相”)。这两相的共存用“γ-γ’相”来表示。
高温合金的“基本成分”表示基体的主要金属成分。在大多数情况下，高温合金包括基本成分铁、钴或镍，但有时也包括基本成分钛或铝。高温合金的基本成分优选地为基本成分镍。
“镍基高温合金”的优点是在高温和高重量下的抗氧化性和抗断裂性之间提供了良好的折衷，这证明了它们可在涡轮喷气发动机的最热部分中使用。
镍基高温合金由以下组成：具有面心γ-Ni的立方奥氏体型γ相(或基体)，该γ相可选地含有α置换的固溶体添加物(Co、Cr、W、Mo)；以及γ’-Ni3X型的γ’相(或析出物)，其中X＝Al、Ti或Ta。γ’相具有源自面心立方结构的有序的L12结构，与基体共格，换言之，具有与基体非常接近的原子间距。
就其有序性质而言，γ’相具有以下显著性质：机械强度随温度升高至约800℃而增大。γ相和γ’相之间非常强的共格赋予镍基高温合金以非常高的热机械强度，该热机械强度本身取决于γ/γ’比和硬化析出物的大小。
在本发明的所有实施方式中，高温合金富含铼和/或钌，换言之，高温合金中铼和钌的平均质量分数大于或等于3％，优选地大于或等于4％，相较于由不含铼的高温合金制成的部件，提高了高温合金部件的抗蠕变性。
高温合金优选地具有低的平均铬含量，换言之，在高温合金整体中铬的平均质量分数小于5％，优选地小于3％。实际上，在高温合金的铼和/或钌的富集期间，铬的贫化能保持高温合金的稳定的同素异形结构，尤其是γ-γ’相。
术语“质量分数”是指一种元素或一组元素相对于总质量以质量计的比。
表面粗糙度的方面可以优选地由在大于1mm2的面积上测量的算术平均粗糙度(称为Ra)，和/或通过在大于1mm2的面积上测量的最大粗糙度(称为RZ)来定义。一个或多个粗糙度测量可以通过光学或机械轮廓曲线仪进行。
基底表面在“湿酸性介质中的化学侵蚀”是指将基底表面与包含酸的液相，例如以浸泡液的形式的液相接触。液相可以是水性相，具有预定的酸浓度。替代性地，液相可以包含液态形式的纯酸。化学侵蚀尤其可以是电化学侵蚀。
“保护涂层”是指覆盖基底并对其进行化学和/或机械保护的层。保护涂层优选地防止基底腐蚀和/或氧化。所述保护涂层优选地为在基底和热保护层之间的结合层。
具体实施方式
参照图3，部件1，优选地为飞行器部件1，包括由单晶高温合金制成的基底2。单晶高温合金优选地为镍基高温合金，但也可以是钴基高温合金，例如通过等轴铸造方法或通过定向凝固获得。基底2包含铬和选自铼和钌的至少一种元素。基底2具有γ-γ’相，以及平均质量分数大于或等于3％，优选地大于或等于4％的铼和/或钌。基底2优选地具有平均质量分数小于或等于5％，优选地小于或等于3％的铬。基底2例如可以以CMSX4 plus(注册商标)制造，具有表1中所述的化学组成，以平均质量分数计。
[表1]
| Cr | Co | Mo | Ta | W | Cb | Re | Al | Ti | Hf | Ni |
| 3.5 | 10 | 0.6 | 8 | 6 | 0 | 4.8 | 5.7 | 0.85 | 0.1 | 余量 |
部件1还包括保护涂层3。保护涂层3覆盖基底2表面的至少一部分。保护涂层以体积计主要为γ-γ’相。因此，保护涂层3的同素异形结构与基底2的同素异形结构相似，这防止或减少在部件1的使用期间在基底2中形成次级反应层。
保护涂层3可以通过物理或化学沉积形成。优选地可以通过物理气相沉积(PVD)在真空下形成。可以使用各种PVD方法来制造富集层11，诸如阴极喷涂、电子枪蒸鍍、激光烧蚀和电子束物理气相沉积。替代性地，保护涂层3可以通过热喷涂形成，更具体地通过高速氧燃料喷涂(HVOF)形成。
保护涂层3的铼和/或钌的平均质量分数小于1％，优选地不含铼或钌。因此，有可能避免在基底2中形成次级反应区。保护涂层3优选地由MCrAlY型材料制造，其中M表示选自Ni、Co和Fe的至少一种元素。
替代性地，保护涂层3由NiAlCrHfSi型材料制成，换言之，保护涂层3包含至少镍、铝、铬、铪和硅。尤其，保护涂层3具有平均质量分数占大多数的镍，平均质量分数在5％至15％之间的铝、平均质量分数在7％至15％之间的铬、平均质量分数在0.5％至2％之间的铪，以及平均质量分数在0.5％至3％之间的硅。因此，保护涂层3的同素异形结构是稳定的，并且在部件1的使用期间可以保持γ-γ’型。因此可以避免马氏体型转变。尤其，保护涂层3可以具有基本成分镍，平均质量分数为大约6％的铝、平均质量分数为大约12％的铬、平均质量分数为大约1.7％的铪，以及平均质量分数为大约0.3％的硅。
发明人已发现，通过减小基底2和保护涂层3之间的铼和/或钌的平均质量分数差，可以提高保护涂层3在部件1的使用期间的稳定性。因此，基底2在表面，更具体地说在基底2表面的预期与保护涂层3接触的部分上，具有平均质量分数小于2％，优选地小于1％的铼和/或钌。
以已知的方式，在基底2上形成保护涂层3之前，可以通过喷砂来控制基底2的表面状况。发明人已发现，由喷砂造成的粗糙度太高，以致无法在部件1的使用期间确保基底2和保护涂层3之间的可接受的粘着力。基底2表面的部分的算术平均粗糙度Ra在0.5μm-5μm之间，并且优选地最大粗糙度RZ在5.5μm-50μm之间，粗糙度Ra和RZ在大于1mm2的面积上测量。粗糙度Ra和RZ通过将基底2表面的部分在湿酸性介质中进行化学侵蚀而获得。除了对基底表面的部分进行喷砂之外，还可以进行化学侵蚀。这些粗糙度范围减小了沉积保护涂层3时基底2表面的机械应力，从而提高了基底2和保护涂层3之间的粘着力。
参照图4，制造部件1的方法可以包括提供由单晶高温合金制成的基底2的步骤801，该单晶高温合金优选地为镍基的，基底2包含铬和选自铼和钌的至少一种元素，该基底2具有平均质量分数大于或等于3％，优选地大于或等于4％的铼和/或钌，以及平均质量分数小于或等于5％，优选地小于或等于3％的铬。
该方法可以包括机械地控制基底2的表面状况的步骤802，优选地为对表面进行喷砂的步骤。
该方法包括在湿酸性介质中对基底2表面的至少一部分进行化学侵蚀的步骤803，优选地为在湿酸性介质中进行化学蚀刻的步骤。发明人已发现，在湿酸性介质中对基底表面进行化学侵蚀降低了基底2表面的铼和/或钌的平均质量分数，和/或还能够将基底2表面的粗糙度控制在上述列举的粗糙度Ra和RZ的范围内。在基底2的从基底2表面延伸到距离基底2表面10μm的深度的部分的层中，铼和/或钌的平均质量分数可以优选地平均小于2％。
在湿介质中的化学侵蚀可以通过将基底2表面的该部分浸泡在氢氟酸、硝酸与氯化铁和盐酸、盐酸与氯化铁盐酸与过氧化氢以及硝酸与盐酸中的至少一种中来进行。
替代性地或组合地，在酸性介质中的化学侵蚀可以通过控制与基底2表面的部分接触的浸泡液的电位以引起电化学反应来进行。该浸泡液优选地包括硝酸与乙酸、硫酸以及磷酸中的至少一种。
化学侵蚀实施例
实施例1
基底2的化学侵蚀可以包括将基底2浸泡在盐酸和氯化铁的混合物中。盐酸的体积可以在氯化铁体积的7％-15％之间。浸泡液通过压缩空气来搅拌。将浸泡液在65℃的温度下保持250s-3000s之间的时间。然后用冷水从基底2的表面上冲洗浸泡液5分钟。然后在75℃的温度下，用重量浓度为300g/L的氢氧化钠溶液中和基底2表面5分钟。中和溶液通过压缩空气来搅拌。然后用冷水从基底2表面上冲洗中和溶液5分钟。在超声波浴中用冷水再次冲洗基底2表面5分钟。在用80℃的水冲洗表面5分钟后，将基底2表面干燥。
实施例2
将基底2在室温下用水冲洗1-2分钟。化学侵蚀包括将基底2浸泡在由H3PO4(按体积计70％)和水(按体积计30％)组成的溶液中。将浸泡液在30℃-70℃之间的温度下保持180s-3000s之间的时间。在基底上施加2-10A之间的电流，对应于0.2-2A.cm2的表面电流。然后用冷水从衬底2表面上冲洗浸泡液5分钟。然后在50℃-80℃之间的温度下，用重量浓度为300g/L的氢氧化钠溶液中和基底2表面5分钟。中和溶液通过压缩空气来搅拌。然后用冷水从基底2表面上冲洗中和溶液5分钟。在超声波浴中用冷水再次冲洗基底2表面5分钟。在用80℃的水冲洗表面5分钟后，将基底2表面干燥。
该方法包括在化学侵蚀步骤803之后，优选地根据上述方法中的一个来沉积保护涂层3的步骤804。
Claims (16)
1.一种用于制造部件(1)的方法，所述方法包括以下步骤：
a)在湿酸性介质中，对由单晶高温合金制成的基底(2)的表面的至少部分进行化学侵蚀，所述基底包含选自铼和钌的至少一种元素，所述基底(2)具有γ-γ’相，所述基底(2)具有平均质量分数大于或等于3％，优选地大于或等于4％的铼和/或钌，所述化学侵蚀以使得在所述基底(2)的表面的所述部分中铼和/或钌的平均质量分数小于2％的方式进行，
b)在所述基底(2)的所述部分上沉积保护涂层(3)，所述保护涂层具有γ-γ’相以及平均质量分数小于1％的铼和/或钌。
2.根据权利要求1所述的方法，其中，所述基底(2)由镍基单晶高温合金制成。
3.根据权利要求1或2所述的方法，其中，所述基底(2)包含铬，铬的平均质量分数小于5％，优选地小于3％。
4.根据权利要求1至3中任一项所述的方法，其中，所述化学侵蚀为化学蚀刻。
5.根据权利要求1至4中任一项所述的方法，其中，进行所述化学侵蚀，使得所述基底(2)的表面的所述部分的算术平均粗糙度Ra在0.5μm-5μm之间，并且优选地最大粗糙度RZ在5.5μm-50μm之间，粗糙度Ra和RZ在大于1mm2的面积上测量。
6.根据权利要求1至5中任一项所述的方法，其中，在酸性介质中的所述化学侵蚀通过与所述基底(2)的表面的所述部分接触的浸泡液进行，所述浸泡液包括氢氟酸、硝酸与氯化铁和盐酸、盐酸与氯化铁、盐酸与过氧化氢，以及硝酸与盐酸中的至少一种。
7.根据权利要求1至6中任一项所述的方法，其中，在酸性介质中的所述化学侵蚀通过与所述基底(2)的表面的所述部分接触的浸泡液进行，控制所述浸泡液的电位，以便在所述表面的所述部分上引起电化学反应，所述浸泡液优选地包括硝酸与乙酸、硫酸以及磷酸中的至少一种。
8.部件(1)，包括：
由单晶高温合金制成的基底(2)，所述基底包含选自铼和钌的至少一种元素，所述基底(2)具有γ-γ’相，以及平均质量分数大于或等于3％，优选地大于或等于4％的铼和/或钌，
保护涂层(3)，所述保护涂层覆盖所述基底(2)的表面的至少部分，
其特征在于，
所述基底(2)的表面的所述部分上的铼和/或钌的平均质量分数小于2％，和
所述保护涂层(3)具有γ-γ’相，以及平均质量分数小于1％的铼和/或钌。
9.根据权利要求8所述的部件(1)，其中，所述基底(2)包含铬，铬的平均质量分数小于5％，优选地小于3％。
10.根据权利要求8或9所述的部件(1)，其中，所述基底(2)的表面的所述部分的算术平均粗糙度Ra在0.5μm-5μm之间，并且优选地最大粗糙度RZ在5.5μm-50μm之间，粗糙度Ra和RZ在大于1mm2的面积上测量并且通过在湿酸性介质中对所述基底(2)的表面的所述部分进行化学侵蚀来获得。
11.根据权利要求8至10中任一项所述的部件(1)，其中，所述保护涂层(3)以体积计主要具有γ’相。
12.根据权利要求8至11中任一项所述的部件(1)，其中，所述保护涂层(3)包含至少镍、铝、铬、铪和硅。
13.根据权利要求12所述的部件(1)，其中，所述保护涂层(3)具有：
平均质量分数占大多数的镍，
平均质量分数在5％-15％之间的铝，
平均质量分数在7％-15％之间的铬，
平均质量分数在0.5％-2％之间的铪，
和
平均质量分数在0.5％-3％之间的硅。
14.根据权利要求8至13中任一项的飞行器部件。
15.一种飞行器涡轮，所述飞行器涡轮包括根据权利要求8至14中任一项所述的部件。
16.一种飞行器，所述飞行器包括根据权利要求8至14中任一项所述的部件。
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| PCT/FR2020/051775 WO2021069842A1 (fr) | 2019-10-08 | 2020-10-08 | Piece d'aeronef en superalliage comprenant du rhenium et/ou du ruthenium et procede de fabrication associe |
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| FR3101643A1 (fr) | 2021-04-09 |
| US20240093343A1 (en) | 2024-03-21 |
| EP4041930B1 (fr) | 2023-08-02 |
| CN114585769B (zh) | 2024-04-26 |
| WO2021069842A1 (fr) | 2021-04-15 |
| EP4041930A1 (fr) | 2022-08-17 |
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