CN101356302B - 含两个烧绿石相的层体系 - Google Patents
含两个烧绿石相的层体系 Download PDFInfo
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- CN101356302B CN101356302B CN2006800506943A CN200680050694A CN101356302B CN 101356302 B CN101356302 B CN 101356302B CN 2006800506943 A CN2006800506943 A CN 2006800506943A CN 200680050694 A CN200680050694 A CN 200680050694A CN 101356302 B CN101356302 B CN 101356302B
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- coating systems
- coating
- zirconate
- layer
- hafnates
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- 239000000919 ceramic Substances 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims description 58
- 239000011248 coating agent Substances 0.000 claims description 52
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 17
- 229910052727 yttrium Inorganic materials 0.000 claims description 17
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 16
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 15
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 239000010941 cobalt Substances 0.000 claims description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 229910052804 chromium Inorganic materials 0.000 claims description 12
- 239000011651 chromium Substances 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- 239000004411 aluminium Substances 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052735 hafnium Inorganic materials 0.000 claims description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 10
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 6
- 229910052702 rhenium Inorganic materials 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 4
- 239000010410 layer Substances 0.000 description 42
- 239000007789 gas Substances 0.000 description 21
- 238000002485 combustion reaction Methods 0.000 description 14
- 239000012720 thermal barrier coating Substances 0.000 description 12
- 239000013078 crystal Substances 0.000 description 10
- 229910045601 alloy Inorganic materials 0.000 description 9
- 239000000956 alloy Substances 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910000601 superalloy Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000007750 plasma spraying Methods 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000008646 thermal stress Effects 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 238000005566 electron beam evaporation Methods 0.000 description 2
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 206010011376 Crepitations Diseases 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005328 electron beam physical vapour deposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
- C23C28/3215—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer at least one MCrAlX layer
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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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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- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Laminated Bodies (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Furnace Housings, Linings, Walls, And Ceilings (AREA)
- Chemically Coating (AREA)
Abstract
热障层体系除良好的热障性能之外，还须具有长的使用寿命。本发明的层体系(1)具有陶瓷层(13)，该层含有两种烧绿石相的混合物。
Description
本发明涉及一种如权利要求1所述的含有烧绿石的层体系。
这种层体系具有含有基于镍或钴的金属合金的基材。这类产品尤其用作燃气涡轮的零件，特别是用作燃气涡轮的叶片或耐热护壳。这些零件暴露于腐蚀性燃气的热气流中。因此，它们必须能够承受很高的热应力。另外，这些零件还必须能够耐氧化和耐腐蚀。此外，尤其是对于运动零件，例如燃气涡轮叶片，以及对静止零件还有机械要求。对于其中利用了可暴露于热气体的零件的燃气涡轮，其功率和效率会随着工作温度的升高而增大。因此人们为通过改善涂层体系实现更高的燃气涡轮效率进行了不断尝试。
为实现高效率和大功率，人们在特别是暴露于高温的燃气涡轮零件上涂覆了陶瓷材料。其能充当所述热气流与所述金属基材之间的热障层。
涂层能保护所述金属基体不受所述腐蚀性热气流的腐蚀。现代的零件通常都具有多个涂层，其各自执行特定的任务。因此，采用了一种多层体层。
EP0944746B1公开了使用烧绿石作为热障层。
但是，对于用作热障层的材料来说，其不仅需要具有良好的隔热性能，还需要对基材具有很好的粘合力。
EP0992603A1公开了由氧化钆和氧化锆制成的热障层体系，其应该不具有烧绿石结构。
因此，本发明的目的在于提供一种层体系，其具有良好的隔热性能和对基材的良好粘合力以及由此整个层体系的长使用寿命。
所述目的是通过如权利要求1所述的层体系实现的。
从属权利要求列出了进一步的有利措施，它们可以有利的方式彼此任意结合。
本发明基于以下发现，即为实现长使用寿命整个体系必须视为整体，而不可视为独立的层或彼此分离的独立层并进行优化。
本发明的层体系具有外陶瓷层，其包括两个烧绿石相的混合物，该混合物具有极好的热性能(与构件的基材相适配的膨胀系数，低导热系数)且能与中间层和构件的基材很好地协调。可以通过这两个烧绿石相的混合比来使所述陶器层的性能适应所述基材和中间层。
下面参照附图详细说明了本发明的实施例。
其中：
图1显示了一种根据本发明的层体系，
图2显示了一系列超级合金，
图3显示了一个燃气涡轮，
图4显示了涡轮叶片的透视图，
图5显示了燃烧室的透视图。
图1显示了一种根据本发明的层体系。
该层体系1由金属基材4构成，该基材特别是对于在高温下使用的构件来说由镍基或钴基超级合金(图2)构成。优选地直接在所述基材4上有金属粘结层7MCrAlX，优选为NiCoCrAlX型，其优选地含：
(11-13)wt％钴，特别是12％Co
(20-22)wt％铬，特别是21％Cr
(10.5-11.5)wt％铝，特别是11％Al
(0.3-0.5)wt％钇，特别是0.4％Y
(1.5-2.5)wt％铼，特别是2.0％Re
余量镍，
或优选地含：
(24-26)wt％钴，特别是25％Co
(16-18)wt％铬，特别是17％Cr
(9-11)wt％铝，特别是10％Al
(0.3-0.5)wt％钇，特别是0.4％Y
(1-2)wt％铼，特别是1.5％Re
余量镍，
或优选地含：
29％-31％镍，特别是30％镍
27％-29％铬，特别是28％铬
7％-9％铝，特别是8％铝
0.5％-0.7％钇，特别是0.6％钇
0.6％-0.8％硅，特别是0.7％硅
和余量钴，
或优选地含：
27％-29％镍，特别是28％镍
23％-25％铬，特别是24％铬
9％-11％铝，特别是10％铝
0.5％-0.7％钇，特别是0.6％钇，和
余量钴。
优选地，所述保护层7由这些合金之一构成。
在此金属粘结层7上，在涂覆进一步的陶瓷层之前就已形成了氧化铝层，或者在操作中形成这样一个氧化铝层(TGO)。
优选地在所述金属粘结层7上或所述氧化铝层(未显示)上有陶瓷内层10，其优选地为完全或部分稳定的氧化锆层。优选地使用钇稳定的氧化锆(YSZ)，其优选地含6wt％-8wt％钇。同样可以使用氧化钙、二氧化铈和/或二氧化铪来稳定氧化锆。
所述氧化锆优选地以等离子体喷镀层施加，但也可优选地通过电子束物理蒸发(EBPVD)以柱状结构施加。
内层10的层厚优选地为内层10和外层13的总层厚D的10％-50％(图1)。内层10的层厚优选地为所述总层厚D的10％-40％或10％-30％。
同样有利的是内层10的层厚为所述总层厚D的10％-20％。
内层10的层厚还优选地为所述总层厚D的20％-50％或20％-40％。
如果内层10构成总层厚D的20％-30％同样可以获得有利的结果。
内层10的层厚优选地为所述总层厚D的30％-50％。
同样有利的是内层10的层厚构成所述总层厚D的30％-40％。
同样优选地内层10的层厚构成所述总层厚D的40％-50％。
尽管所述烧绿石相具有优于所述ZrO2层的隔热性能，但可使所述ZrO2层的厚度也与所述烧绿石相相等。
陶瓷内层10的厚度优选地为40μm-60μm，特别是50μm±10％。
内层10与外层13的总层厚D优选地为300μm或优选地为400μm。最大总层厚有利地为800μm或优选地最多600μm。
然后，向所述经稳定化的氧化锆层10上施加陶瓷外层13；根据本发明，此陶瓷外层13包括通式为AxByOz的两个不同烧绿石相，其中x，y≈2，z≈7，即容许有少量的缺陷或掺杂物，O＝氧。特别地，x，y＝2且z＝7。
因此，所述陶瓷层包括烧绿石AxByOz和CrDsOt，其中r，s≈2，t≈7，O＝氧。特别是，r，s＝2且t＝7。
元素A、B、C和D可以彼此都不相同。
如果A和C相同，则B和D不相同。如果B和D相同，则A和C不相同。
排除了A＝C且B＝D的组合。
A＝D，B≠C或C＝B，A≠D两种组合原则上是可能的。
A，C优选地使用钆(Gd)。
A，C的进一步的例子包括镧(La)、钇(Y)、钕(Nd)、镱(Yb)、铈(Ce)或铝(Al)。
B，D的例子包括铪(Hf)、锆(Zr)、钛(Ti)、铈(Ce)或锡(Sn)。
优选地使用铪酸盐或锆酸盐，即B使用铪和/或锆，优选地Gd2Hf2O7(GHO)和/或Gd2Zr2O7(GZO)。
所述陶瓷外层13优选地由两个烧绿石相构成。
优选地使用Gd2Hf2O7和Gd2Zr2O7。
在这种情况下不存在所述两个烧绿石相的固溶体，即例如不存在Gdx(HfyZrw)Oz，其中x＝2、y+w＝2、z＝7(固溶体也包含烧绿石相，但在晶格位置(A，B)具有两个不同元素；除非特指一种固溶体，否则不存在固溶体)。
所述固溶体Ax(ByDw)Oz、Cs(DtBq)Ot或A、B、C、D(即例如Gd、Hf、Zr)的氧化物所占的比例最多为20wt％，特别地最多为10wt％。
所述两个烧绿石相的含量优选地为至少80wt％，特别是至少90wt％。
不过，也可以使两种固溶体彼此混合，或一种固溶体与一种非固溶体混合，即例如Ax(ByEw)Oz与Cx(DyFw)Oz，其中E≠D且F≠B，或AxByOz与Cx(DyFw)Oz，其中F≠B。
因此，陶瓷外层13例如按如下所述制造：以某一混合比将由两个烧绿石相例如由锆酸钆构成的粉末和铪酸钆的粉末彼此混合并供应给等离子体喷涂装置的喷头。也可采用其它涂覆方法，例如PVD方法，其中采用由锆酸钆和铪酸钆构成的两个坯料。
可以采用锆酸钆与铪酸钆的任意混合比例。优选地锆酸钆的份额较大。还优选地使用铪酸钆/锆酸钆为10∶90、20∶80、30∶70或40∶60的混合比例。还优选地使用铪酸钆/锆酸钆为50∶50、60∶40、70∶30、80∶20或90∶10的混合比例。
优选地使用Gd2Hf2O7与Gd2Zr2O7的混合物，二者优选地彼此均匀混合或具有梯度。即例如在向外朝向热气一侧方向上Gd2Zr2O7的含量更高。
层体系1优选地由基材4、粘结层7(MCrAlY)、任选的TGO和单外层(例如GZO和/或GHO)或双外层热障涂层13(YSZ与GZO或GHO)构成。
图3举例显示了燃气涡轮100的部分纵截面。
在内部，燃气涡轮100具有绕旋转轴102转动设置的带轴101的转子103，所述转子103又称作涡轮转子。
吸进壳体104、压缩机105、具有多个共轴排列的燃烧器107的例如圆环形的燃烧室110，特别是环形燃烧室，涡轮108和排气壳体109沿转子103相继排列。
所述环形燃烧室110与例如环形热气通道111相连通，在所述环形热气通道111中例如有四个相继连接的涡轮级112构成所述涡轮108。
每个涡轮级112例如由两个叶片环构成。由工作介质113的流动方向上看，在热气通道111中一排导叶115后接着由转子叶片120构成的一排125。
所述导叶130被固定在定子143的内壳138上，而那排125的转子叶片120通过涡轮盘133装在转子103上。
发电机或做功机器(未显示)联结在所述转子103上。
燃气涡轮100工作时，压缩机105通过吸进壳体104吸入空气135并对其进行压缩。在压缩机105的涡轮侧端提供的压缩空气被送往燃烧器107，在那里与燃料混合。然后该混合物在燃烧室110中燃烧，形成工作介质113。工作介质113从那里沿热气通道111流出经过导叶130和转子叶片120。工作介质113在转子叶片120上膨胀并传递动量，从而使转子叶片120驱动转子103而后者驱动与其联结在一起的做功机器。
在燃气涡轮100工作时，暴露于热工作介质113的零件受到热应力。除镶衬环形燃烧室110的热屏蔽元件之外，在工作介质113的流动方向上看的第一涡轮级112的导叶130和转子叶片120受到最高的热应力。
为了能够承受那里的温度，可以用冷却剂对它们进行冷却。
零件的基材同样可以具有定向结构，即它们是单晶形式的(SX结构)或只具有纵向取向的晶粒(DS结构)。
例如，铁基、镍基或钴基超级合金被用作所述零件特别是涡轮机叶片120、130和燃烧室110的零件的材料。
此类超级合金从例如EP1204776B1、EP1306454、EP1319729A1、WO99/67435或WO00/44949已知；这些文献有关所述合金的化学组成的内容为本公开的一部分。
导叶130具有面对涡轮108的内壳138的导叶根(在这里未显示)和与导叶根相对置的导叶头。导叶头面对转子103并被固定到定子143的固定环140上。
图4显示了涡轮机的转子叶片120或导叶130的透视图，其沿纵轴121延伸。
所述涡轮机可以为飞行器或发电厂用于发电的燃气涡轮、蒸汽涡轮或压缩机。
叶片120、130沿纵轴121顺次具有固定区域400、邻接该固定区域的叶片平台403以及叶片406和叶片尖端415。
作为导叶130，该叶片130可以在其叶片尖端415具有另一个平台(未显示)。
在所述固定地区400内构成用于将转子叶片120、130固定在轴或盘上的叶片根183(未显示)。
叶片根183设计成例如锤头形状。也可采用其它构型，如枞树或鸽尾根形。
叶片120、130具有用于流过叶片406的介质的流入缘409和流出缘412。
对于传统的叶片120、130，在该叶片120、130的所有区域400、403、406中都使用例如实心金属材料，特别是超级合金。
此类超级合金从例如EP1204776B1、EP1306454、EP1319729A1、WO99/67435或WO00/44949已知；这些文献有关所述合金的化学组成的内容为本公开的一部分。
在这种情况下，叶片120、130可以通过浇铸法制造，也可通过定向凝固、锻造法、铣切法或它们的组合制造。
具有一种或多种单晶结构的工件被用作在工作中暴露于高机械、热和/或化学应力的机器的零件。
此类单晶工件通过例如由熔体定向凝固制造。这包括其中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浇铸工艺。
在这种情况下，枝晶沿热流方向取向并形成柱状晶粒结构(即晶粒延伸到工件的整个长度且在这里，根据常用的语言，称作定向凝固)或单晶结构，即整个工件由一个单晶构成。在这些工艺中，需要避免转化成球状(多晶)凝固，因为不定向的生长不可避免地会形成横向和纵向的晶粒边界，其将消除定向凝固的或单晶的零件的有利性质。
若泛指定向凝固结构时，应理解为既指不具有任何晶界或最多具有小角度晶界的单晶，又指具有纵向走向的晶界但不具有任何横向晶界的柱状晶体结构。第二种晶体结构也被称作定向凝固结构。
此类过程由US-PS6,024,792和EP0892090A1已知；这些文献有关凝固工艺的内容为本公开的一部分。
叶片120、130可以同样提供有根据本发明所述的层体系1或具有其它涂层来保护它们不受腐蚀或氧化，例如(McrAlX；M为选自铁(Fe)、钴(Co)、镍(Ni)的至少一种元素，X为活性元素且代表钇(Y)和/或硅和/或至少一种稀土元素或铪(Hf))。此类合金从EP0486489B1、EP0786017B1、EP0412397B1或EP1306454A1中已知，这些文献关于所述合金的化学组成的内容为本公开的一部分。密度优选地为理论密度的95％。
在所述MCrAlX层上(作为中间层或最外层)形成有保护性氧化铝层(TGO，即热生长氧化物层)。
在所述MCrAlX上还有根据本发明所述的层体系1的热障层13。
热障层13覆盖整个MCrAlX层。
通过适当的涂覆工艺，例如电子束蒸发(EB-PVD)，在所述热障层中形成了柱状晶粒。
也可采用其它涂覆工艺，例如大气等离子体喷镀(APS)、LPPS、VPS或CVD。所述热障层可以具有含微裂纹或宏观裂纹的多孔晶粒，以改善耐热震性。因此，所述热障层优选地比所述MCrAlX层更为多孔。
所述叶片120、130可以是中空或实心的。
如果所述叶片120、130应被冷却，则其是中空的且可以视需要具有膜冷却孔418(由虚线表示)。
图5显示了燃气涡轮100的燃烧室110。
燃烧室110设置为，例如，所谓的环形燃烧室，其中绕旋转轴102圆周排列的多个燃烧器107通入公用燃烧室空间154，所述燃烧器产生火焰156。为此，燃烧室110整体上被设置成位于旋转轴102周围的环形构造。
为实现较高的效率，燃烧室110针对约1000℃-1600℃的较高工作介质M的温度设计。为了即使是在这些对所述材料不利的工作参数下都能实现较长的使用寿命，在燃烧室壁153的面对工作介质M一侧提供有由热屏蔽元件155构成的内衬。
此外，由于燃烧室110内部的高温，还可以向所述热屏蔽元件155或它们的支撑元件提供冷却系统。热屏蔽元件155例如是中空的，并可任选地具有通向燃烧室空间154的冷却孔(未显示)。
在工作介质一侧，由合金制成的每个热屏蔽元件155都具备一个特别耐热的保护层(MCrAlX层和/或陶瓷涂层)，并由此构成本发明的层体系1，或由能承受高温的材料(实心陶瓷砖)制成。
这些保护层可以与涡轮叶片类似，即例如为MCrAlX：M为选自铁(Fe)、钴(Co)、镍(Ni)的至少一种元素，X为活性元素且代表钇(Y)和/或硅和/或至少一种稀土元素或铪(Hf)。此类合金从EP0486489B1、EP0786017B1、EP0412397B1或EP1306454A1中已知，这些文献有关合金的化学组成的内容为本公开的一部分。
在所述MCrAlX上还可以存在本发明所述的陶瓷热障层13。
通过适当的涂覆工艺，例如电子束蒸发(EB-PVD)，在所述热障层中形成了柱状晶粒。
也可采用其它涂覆工艺，例如大气等离子体喷镀(APS)、LPPS、VPS或CVD。所述热障层可以具有含微裂纹或宏观裂纹的多孔颗粒，以改善其耐热震性。
再加工(修复)是指，涡轮叶片120、130、热屏蔽元件155在使用之后可能需去除保护层(例如通过喷砂)。然后，腐蚀层和/或氧化层和/或腐蚀和/或氧化产物被除去。适当时，涡轮叶片120、130或热屏蔽元件155内的裂纹也被修复。接着重新涂覆涡轮叶片120、130、热屏蔽元件155，并重新使用涡轮叶片120、130或热屏蔽元件155。
Claims (1)
1.层体系，其包括：
基材(4)，
在基材（4）上存在陶瓷外层(13)，该陶瓷外层（13）含有通式为AxByOz的两种烧绿石相的混合物，其中x,y≈2，z≈7，A为钆，烧绿石相为铪酸盐和锆酸盐，
其中所述陶瓷外层(13)包含最多20wt%的固溶体，和所述两个烧绿石相占所述陶瓷外层(13)的至少80wt%。
2. 权利要求1的层体系，其中一个烧绿石相为锆酸钆(Gd2Zr2O7)。
3. 权利要求1的层体系，其中一个烧绿石相为铪酸钆(Gd2Hf2O7)。
4. 权利要求1、2或3的层体系，其中在所述陶瓷外层(13)下有陶瓷内层(10)。
5. 权利要求4的层体系，其中所述内层(10)的层厚为所述陶瓷内层(10)和所述陶瓷外层(13)的总层厚(D)的10%-50%。
6. 权利要求4的层体系，其中所述内层(10)与所述外层(13)的总层厚为300μm。
7. 权利要求4的层体系，其中所述内层(10)与所述外层(13)的总层厚为400μm。
8. 权利要求1的层体系，其中所述层体系（1）在所述基材(4)上有金属粘结层(7)。
9. 权利要求8的层体系，其中所述金属粘结层(7)的组成以wt%计为：
11%-13%钴，
20%-22%铬，
10.5%-11.5%铝，
0.3%-0.5%钇，
1.5%-2.5%铼，
余量镍。
10. 权利要求8的层体系，其中所述金属粘结层(7)的组成以wt%计为：
24%-26%钴，
16%-18%铬，
9%-11%铝，
0.3%-0.5%钇，
1%-2%铼，和
余量镍。
11. 权利要求8的层体系，其中所述金属粘结层(7)的组成以wt%计为：
29%-31%镍，
27%-29%铬，
7%-9%铝，
0.5%-0.7%钇，
0.6%-0.8%硅，和
余量钴。
12. 权利要求8的层体系，其中所述金属粘结层(7)的组成以wt%计为：
27%-29%镍，
23%-25%铬，
9%-11%铝，
0.5%-0.7%钇，和
余量钴。
13. 权利要求1、2或3的层体系，其中所述陶瓷外层(13)包含最多10wt%的固溶体。
14. 权利要求1、2或3的层体系，其中所述陶瓷外层(13)不包含固溶体。
15. 权利要求1、2或3的层体系，其中铪酸盐和锆酸盐的混合比例为10:90。
16. 权利要求1、2或3的层体系，其中铪酸盐和锆酸盐的混合比例为20:80。
17. 权利要求1、2或3的层体系，其中铪酸盐和锆酸盐的混合比例为30:70。
18. 权利要求1、2或3的层体系，其中铪酸盐和锆酸盐的混合比例为40:60。
19. 权利要求1、2或3的层体系，其中铪酸盐和锆酸盐的混合比例为50:50。
20. 权利要求1、2或3的层体系，其中铪酸盐和锆酸盐的混合比例为60:40。
21. 权利要求1、2或3的层体系，其中铪酸盐和锆酸盐的混合比例为70:30。
22. 权利要求1、2或3的层体系，其中铪酸盐和锆酸盐的混合比例为80:20。
23. 权利要求1、2或3的层体系，其中铪酸盐和锆酸盐的混合比例为90:10。
24. 权利要求1、2或3的层体系，其中所述陶瓷外层(13)由两个烧绿石相构成。
25. 权利要求1、2或3的层体系，其中所述两个烧绿石相占所述陶瓷外层(13)的至少90wt%。
26. 权利要求1的层体系，其中x, y = 2且z = 7。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP06000337A EP1806432A1 (de) | 2006-01-09 | 2006-01-09 | Schichtsystem mit zwei Pyrochlorphasen |
| EP06000337.3 | 2006-01-09 | ||
| PCT/EP2006/069766 WO2007080041A1 (de) | 2006-01-09 | 2006-12-15 | Schichtsystem mit zwei pyrochlorphasen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101356302A CN101356302A (zh) | 2009-01-28 |
| CN101356302B true CN101356302B (zh) | 2013-09-18 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2006800506943A Expired - Fee Related CN101356302B (zh) | 2006-01-09 | 2006-12-15 | 含两个烧绿石相的层体系 |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US8057924B2 (zh) |
| EP (2) | EP1806432A1 (zh) |
| JP (1) | JP4994395B2 (zh) |
| CN (1) | CN101356302B (zh) |
| FR (1) | FR2897364B1 (zh) |
| GB (1) | GB2433946B (zh) |
| IT (1) | ITMI20070010A1 (zh) |
| TW (1) | TW200738906A (zh) |
| WO (1) | WO2007080041A1 (zh) |
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Also Published As
| Publication number | Publication date |
|---|---|
| FR2897364A1 (fr) | 2007-08-17 |
| EP1806432A1 (de) | 2007-07-11 |
| FR2897364B1 (fr) | 2010-03-12 |
| ITMI20070010A1 (it) | 2007-07-10 |
| GB2433946A (en) | 2007-07-11 |
| GB2433946B (en) | 2011-03-30 |
| EP1971705B1 (de) | 2012-06-27 |
| WO2007080041A1 (de) | 2007-07-19 |
| JP2009522141A (ja) | 2009-06-11 |
| JP4994395B2 (ja) | 2012-08-08 |
| GB0700206D0 (en) | 2007-02-14 |
| US20090148694A1 (en) | 2009-06-11 |
| TW200738906A (en) | 2007-10-16 |
| EP1971705A1 (de) | 2008-09-24 |
| CN101356302A (zh) | 2009-01-28 |
| US8057924B2 (en) | 2011-11-15 |
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