CN103130501A - Multi-element stable zirconium oxide corrosion-resistant thermal barrier coating material - Google Patents
Multi-element stable zirconium oxide corrosion-resistant thermal barrier coating material Download PDFInfo
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- 238000005260 corrosion Methods 0.000 title abstract description 137
- 239000012720 thermal barrier coating Substances 0.000 title abstract description 128
- 230000007797 corrosion Effects 0.000 title description 41
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title 1
- 229910001928 zirconium oxide Inorganic materials 0.000 title 1
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- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 34
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 34
- 238000000498 ball milling Methods 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 20
- 230000004888 barrier function Effects 0.000 claims description 9
- 230000000087 stabilizing effect Effects 0.000 claims description 8
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- 229910002076 stabilized zirconia Inorganic materials 0.000 abstract description 65
- 150000003839 salts Chemical class 0.000 abstract description 39
- 239000003381 stabilizer Substances 0.000 abstract description 29
- -1 calcium magnesium aluminum Chemical compound 0.000 abstract description 23
- 239000003795 chemical substances by application Substances 0.000 abstract description 18
- 239000006060 molten glass Substances 0.000 abstract description 17
- 230000000052 comparative effect Effects 0.000 description 20
- 238000000576 coating method Methods 0.000 description 12
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 12
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- 239000005368 silicate glass Substances 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 4
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- 229910052715 tantalum Inorganic materials 0.000 description 3
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- 229910021193 La 2 O 3 Inorganic materials 0.000 description 2
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明提供了一种多元稳定氧化锆抗腐蚀热障涂层材料，由主剂和稳定剂混合球磨而成，所述主剂为ZrO2，所述稳定剂为Nb2O5、TiO2和稀有金属氧化物的混合物，所述多元稳定氧化锆抗腐蚀热障涂层材料中Nb2O5、TiO2、稀有金属氧化物和ZrO2的摩尔比为x︰1.5x︰x︰（100-3.5x），其中x满足：3≤x≤7；所述稀有金属氧化物为Lu2O3或In2O3。本发明多元稳定氧化锆抗腐蚀热障涂层材料具有优异的抗Na2SO4-V2O5熔盐腐蚀性能，以及优异的抗钙镁铝硅酸盐熔融玻璃腐蚀性能。
The invention provides a multi-component stabilized zirconia anti-corrosion thermal barrier coating material, which is formed by ball milling a main agent and a stabilizer, the main agent is ZrO 2 , and the stabilizer is Nb 2 O 5 , TiO 2 and A mixture of rare metal oxides, the molar ratio of Nb 2 O 5 , TiO 2 , rare metal oxides and ZrO 2 in the multi-component stabilized zirconia anti-corrosion thermal barrier coating material is x: 1.5x: x: (100- 3.5x), where x satisfies: 3≤x≤7; the rare metal oxide is Lu 2 O 3 or In 2 O 3 . The multi-component stabilized zirconia anti-corrosion thermal barrier coating material of the present invention has excellent anti-corrosion performance of Na 2 SO 4 -V 2 O 5 molten salt, and excellent anti-corrosion performance of calcium magnesium aluminum silicate molten glass.
Description
技术领域technical field
本发明属于热障涂层材料技术领域，具体涉及一种多元稳定氧化锆抗腐蚀热障涂层材料。The invention belongs to the technical field of thermal barrier coating materials, in particular to a multi-component stabilized zirconia anti-corrosion thermal barrier coating material.
背景技术Background technique
YSZ热障涂层（即采用Y2O3稳定的ZrO2）具有高熔点、低热传导系数（其热传导系数为2W/m·k～3W/m·k）、高断裂韧性(其断裂韧性为6MPa·m-1/2～9MPa·m-1/2)和高热膨胀系数（其热膨胀系数为9×10-6K-1～11×10-6K-1，与高温合金匹配）等优异的综合性能，目前广泛应用于航空发动机和燃气轮机的涡轮叶片热障涂层。YSZ thermal barrier coating (that is, ZrO 2 stabilized by Y 2 O 3 ) has high melting point, low thermal conductivity (the thermal conductivity is 2W/m·k～3W/m·k), high fracture toughness (the fracture toughness is 6MPa·m -1/2 ～9MPa·m -1/2 ) and high thermal expansion coefficient (its thermal expansion coefficient is 9×10 -6 K -1 ～11×10 -6 K -1 , matching with superalloys) etc. Its comprehensive properties are currently widely used in thermal barrier coatings for turbine blades of aero-engines and gas turbines.
然而，低质量的燃料中通常含有Na、V杂质，这些杂质会形成Na2SO4和V2O5并附着在叶片上，Na2SO4和V2O5熔盐会与稳定剂Y2O3发生反应，导致发生四方相ZrO2（即t-ZrO2）至单斜相ZrO2（即m-ZrO2）的相变，相变伴随3%～5%的体积膨胀，导致热障涂层开裂和脱粘失效。此外，空气中的砂子微粒在叶片上的沉积将形成钙镁铝硅酸盐。钙镁铝硅酸盐将溶解ZrO2晶粒，渗入至叶片基体并与其反应；此外，被钙镁铝硅酸盐腐蚀的热障涂层具有低的应变损伤容限，化学反应和热力耦合作用将导致热障涂层失效。However, low-quality fuel usually contains Na and V impurities, which will form Na 2 SO 4 and V 2 O 5 and attach to the blades, Na 2 SO 4 and V 2 O 5 molten salt will interact with the stabilizer Y 2 O 3 reacts, resulting in a phase transition from tetragonal ZrO 2 (i.e. t-ZrO 2 ) to monoclinic phase ZrO 2 (i.e. m-ZrO 2 ). The phase transition is accompanied by a volume expansion of 3% to 5%, resulting in a thermal barrier Coating cracking and debonding failure. In addition, the deposition of airborne sand particles on the blades will form calcium magnesium aluminum silicates. Calcium magnesium aluminum silicate will dissolve the ZrO2 grains, penetrate into the blade matrix and react with it; moreover, the thermal barrier coating corroded by calcium magnesium aluminum silicate has low strain damage tolerance, chemical reaction and thermal-mechanical coupling will cause the thermal barrier coating to fail.
文献1（公开号为CN1635178A的中国发明专利“一种抗海洋性气氛腐蚀热障涂层”）通过采用电子束物理气相沉积的方法在热障涂层表面制备一定厚度的α-Al2O3涂层来提高YSZ热障涂层的抗熔盐腐蚀性能。然而，热膨胀系数差导致α-Al2O3涂层存在裂纹，稳定剂Y2O3与扩渗进入的Na2SO4和V2O5盐发生反应，导致YSZ热障涂层相变失效。Document 1 (Chinese Invention Patent "An Anti-Marine Atmosphere Corrosion Thermal Barrier Coating" with publication number CN1635178A) prepares a certain thickness of α-Al 2 O 3 on the surface of the thermal barrier coating by using electron beam physical vapor deposition. coating to improve the molten salt corrosion resistance of YSZ thermal barrier coatings. However, the difference in thermal expansion coefficient leads to cracks in the α-Al 2 O 3 coating, and the stabilizer Y 2 O 3 reacts with the Na 2 SO 4 and V 2 O 5 salts infiltrated, resulting in the failure of the phase change of the YSZ thermal barrier coating .
文献2（C.Batista,A.Portinha,R.M.Ribeiro,et al.Evaluation oflaser-glazed plasma-sprayed thermal barrier coatings under high temperatureexposure to molten salts.Surface and Coatings Technology,2006,200:6783-6791.）研究采用激光重熔表面密封处理来提高热障涂层的抗熔盐腐蚀性能。然而，表面处理不能降低裂纹密度和改变材料性质，未明显提高热障涂层抗腐蚀寿命。Document 2 (C.Batista, A.Portinha, R.M.Ribeiro, et al.Evaluation oflaser-glazed plasma-sprayed thermal barrier coatings under high temperature exposure to molten salts.Surface and Coatings Technology, 2006,200:6783-6791.) research adopts Laser remelting surface sealing treatment to improve the molten salt corrosion resistance of thermal barrier coatings. However, surface treatment cannot reduce crack density and change material properties, and does not significantly improve the corrosion resistance life of thermal barrier coatings.
文献3（C.Ramachandra,K.N.Lee,S.N.Tewari,et al.Durability ofTBCs with a surface environmental barrier layer under thermal cycling in airand in molten salt.Surface and Coatings Technology,2003,172:150-157.）研究采用等离子喷涂BAS（BaO·Al2O3·2SiO2）和Mullite（3Al2O3·2SiO2）涂层来提高热障涂层的抗熔盐腐蚀性能。Document 3 (C.Ramachandra, KNLee, SNTewari, et al. Durability of TBCs with a surface environmental barrier layer under thermal cycling in air and in molten salt. Surface and Coatings Technology, 2003, 172:150-157.) research using plasma spraying BAS (BaO · Al 2 O 3 · 2SiO 2 ) and Mullite (3Al 2 O 3 · 2SiO 2 ) coatings to improve the molten salt corrosion resistance of thermal barrier coatings.
文献4（X.L.Chen,Y.Zhao,L.J.Gu,et al.Hot corrosion behaviour ofplasma sprayed YSZ/LaMgAl11O19composite coatings in moltensulfate-vanadate salt.Corrosion Science,2011,53:2335-2343.）研究采用LaMgAl11O19涂层来提高YSZ热障涂层的抗熔盐腐蚀性能。然而，施加LaMgAl11O19涂层后，并未明显提高YSZ热障涂层抗腐蚀寿命。Document 4 (XLChen, Y.Zhao, LJGu, et al.Hot corrosion behavior of plasma sprayed YSZ/LaMgAl 11 O 19 composite coatings in moltensulfate-vanadate salt. Corrosion Science, 2011,53:2335-2343.) research using LaMgAl 11 O 19 coatings to improve the molten salt corrosion resistance of YSZ thermal barrier coatings. However, after applying LaMgAl 11 O 19 coating, the anti-corrosion life of YSZ thermal barrier coating was not significantly improved.
文献5（S.Raghavan,M.J.Mayo.The hot corrosion resistance of20mol%YTaO4stabilized tetragonal zirconia and14mol%Ta2O5stabilizedorthorhombic zirconia for thermal barrier coating applications.Surface andCoatings Technology,2002,160:187-196.）研究采用10mol%Y2O3、10mol%Ta2O5以及14mol%Ta2O5作为ZrO2的稳定剂。然而，Na2SO4-V2O5熔盐会与稳定剂发生反应，导致熔盐沿热障涂层渗入，与粘结层发生反应使热障涂层脱粘失效。Document 5 (S.Raghavan, MJMayo. The hot corrosion resistance of 20mol%YTaO 4 stabilized tetragonal zirconia and 14mol%Ta 2 O 5 stabilized orthorhombic zirconia for thermal barrier coating applications. Surface and Coatings Technology, 2002, 110mol. 187) research- %Y 2 O 3 , 10mol% Ta 2 O 5 and 14mol% Ta 2 O 5 were used as stabilizers for ZrO 2 . However, the Na 2 SO 4 -V 2 O 5 molten salt will react with the stabilizer, causing the molten salt to permeate along the thermal barrier coating and react with the bonding layer to debond and fail the thermal barrier coating.
文献6（公开号为CN101012123A的中国发明专利“一种Yb2O3和Gd2O3掺杂YSZ的高热膨胀率热障涂层材料”）介绍了一种Yb2O3和Gd2O3掺杂YSZ的热障涂层材料。然而，稳定剂Y2O3和掺杂剂Yb2O3、Gd2O3都会与Na2SO4-V2O5熔盐发生反应，导致该热障涂层材料的抗熔盐腐蚀性能差。Document 6 (Chinese Invention Patent Publication No. CN101012123A "A Yb 2 O 3 and Gd 2 O 3 Doped YSZ High Thermal Expansion Thermal Barrier Coating Material") introduces a Yb 2 O 3 and Gd 2 O 3 Thermal barrier coating materials doped with YSZ. However, both the stabilizer Y 2 O 3 and the dopants Yb 2 O 3 and Gd 2 O 3 will react with the Na 2 SO 4 -V 2 O 5 molten salt, resulting in the molten salt corrosion resistance of this thermal barrier coating material Difference.
文献7（公开号为CN101397214A的中国发明专利“多元共稳定氧化锆热障涂层材料及制备方法”）介绍了一种8mol%～9mol%Y2O3、8mol%～9mol%Nb2O5(或Ta2O5)和0.1mol%～3mol%Nd2O3(或Sm2O3，或Gd2O3，或La2O3)作为稳定剂的热障涂层材料。Y2O3、Ta2O5和Nd2O3(或Sm2O3，或Gd2O3，或La2O3)等稳定剂与Na2SO4-V2O5熔盐反应，导致Na2SO4-V2O5熔盐沿热障涂层渗入，与粘结层发生反应使热障涂层脱粘失效。Document 7 (Chinese Invention Patent "Multiple Co-stabilized Zirconia Thermal Barrier Coating Material and Preparation Method" with publication number CN101397214A) introduces a 8mol%～9mol%Y 2 O 3 , 8mol%～9mol%Nb 2 O 5 (or Ta 2 O 5 ) and 0.1mol% to 3mol% Nd 2 O 3 (or Sm 2 O 3 , or Gd 2 O 3 , or La 2 O 3 ) as a stabilizer thermal barrier coating material. Stabilizers such as Y 2 O 3 , Ta 2 O 5 and Nd 2 O 3 (or Sm 2 O 3 , or Gd 2 O 3 , or La 2 O 3 ) react with Na 2 SO 4 -V 2 O 5 molten salt, As a result, the Na 2 SO 4 -V 2 O 5 molten salt penetrates along the thermal barrier coating and reacts with the bonding layer to make the thermal barrier coating debond and fail.
文献8(A.Aygun,A.L.Vasiliev,N.P.Padture,et al.Novel thermalbarrier coatings that are resistant to high-temperature attack by glassy deposits.Acta Materialia,2007,55:6734-6745.)采用在7wt%YSZ基体中固溶20mol.%Al2O3和5mol.%TiO2来提高抗沉积砂子形成的钙镁铝硅酸盐玻璃腐蚀性能。相对于7wt%YSZ，该热障涂层材料抗沉积砂子形成的钙镁铝硅酸盐玻璃腐蚀性能提高约4倍。然而，该热障涂层材料采用Y2O3作为稳定剂，抗Na2SO4-V2O5熔盐腐蚀性能差。Document 8 (A.Aygun, ALVasiliev, NPPadture, et al. Novel thermal barrier coatings that are resistant to high-temperature attack by glassy deposits. Acta Materialia, 2007, 55:6734-6745.) adopts solid solution in 7wt% YSZ matrix 20mol.%Al 2 O 3 and 5mol.%TiO 2 to improve the anti-corrosion performance of calcium magnesium aluminum silicate glass formed by deposited sand. Compared with 7wt% YSZ, the corrosion resistance of the thermal barrier coating material to calcium magnesium aluminum silicate glass formed by deposited sand is about 4 times higher. However, the thermal barrier coating material uses Y 2 O 3 as a stabilizer, and its corrosion resistance to Na 2 SO 4 -V 2 O 5 molten salt is poor.
发明内容Contents of the invention
本发明所要解决的技术问题在于针对上述现有技术的不足，提供一种不仅具有优异的抗Na2SO4-V2O5熔盐腐蚀性能，而且具有优异的抗钙镁铝硅酸盐熔融玻璃腐蚀性能的多元稳定氧化锆抗腐蚀热障涂层材料。The technical problem to be solved by the present invention is to address the above-mentioned deficiencies in the prior art, to provide an anti-corrosion method that not only has excellent Na 2 SO 4 -V 2 O 5 molten salt corrosion resistance, but also has excellent anti-calcium magnesium aluminum silicate melting performance. Multi-component stabilized zirconia anti-corrosion thermal barrier coating material with glass corrosion properties.
为解决上述技术问题，本发明采用的技术方案是：一种多元稳定氧化锆抗腐蚀热障涂层材料，其特征在于，由主剂和稳定剂混合球磨而成，所述主剂为ZrO2，所述稳定剂为Nb2O5、TiO2和稀有金属氧化物的混合物，所述多元稳定氧化锆抗腐蚀热障涂层材料中Nb2O5、TiO2、稀有金属氧化物和ZrO2的摩尔比为x︰1.5x︰x︰（100-3.5x），其中x满足：3≤x≤7；所述稀有金属氧化物为Lu2O3或In2O3。In order to solve the above technical problems, the technical solution adopted in the present invention is: a multi-component stabilized zirconia anti-corrosion thermal barrier coating material, which is characterized in that it is formed by mixing and ball milling a main agent and a stabilizer, and the main agent is ZrO 2 , the stabilizer is a mixture of Nb 2 O 5 , TiO 2 and rare metal oxides, and the multi-component stabilized zirconia anti-corrosion thermal barrier coating material includes Nb 2 O 5 , TiO 2 , rare metal oxides and ZrO 2 The molar ratio is x:1.5x:x:(100-3.5x), where x satisfies: 3≤x≤7; the rare metal oxide is Lu 2 O 3 or In 2 O 3 .
上述的一种多元稳定氧化锆抗腐蚀热障涂层材料，其特征在于，所述多元稳定氧化锆抗腐蚀热障涂层材料中Nb2O5、TiO2、稀有金属氧化物和ZrO2的摩尔比为5︰7.5︰5︰82.5。The above-mentioned multi-element stabilized zirconia anti-corrosion thermal barrier coating material is characterized in that the Nb 2 O 5 , TiO 2 , rare metal oxides and ZrO 2 in the multi-element stabilized zirconia anti-corrosion thermal barrier coating material are The molar ratio is 5:7.5:5:82.5.
上述的一种多元稳定氧化锆抗腐蚀热障涂层材料，其特征在于，所述多元稳定氧化锆抗腐蚀热障涂层材料中Nb2O5、TiO2、稀有金属氧化物和ZrO2的摩尔比为4︰6︰4︰86。The above-mentioned multi-element stabilized zirconia anti-corrosion thermal barrier coating material is characterized in that the Nb 2 O 5 , TiO 2 , rare metal oxides and ZrO 2 in the multi-element stabilized zirconia anti-corrosion thermal barrier coating material are The molar ratio is 4:6:4:86.
上述的一种多元稳定氧化锆抗腐蚀热障涂层材料，其特征在于，所述球磨的速率为100r/min～400r/min，所述球磨的时间为1h～4h。The above-mentioned multi-component stabilized zirconia anti-corrosion thermal barrier coating material is characterized in that the speed of the ball milling is 100r/min-400r/min, and the time of the ball milling is 1h-4h.
将本发明多元稳定氧化锆抗腐蚀热障涂层材料采用等离子喷涂工艺或电子束物理气相沉积工艺制备抗腐蚀热障涂层。等离子喷涂制备多元稳定氧化锆抗腐蚀热障涂层的工作原理为：等离子喷枪形成高温高速等离子射流，送粉气流推动本发明多元稳定氧化锆抗腐蚀热障涂层材料进入等离子射流后，本发明多元稳定氧化锆抗腐蚀热障涂层材料被迅速加热到熔融或半熔融状态，并被等离子射流加速，形成飞向基材的喷涂粒子束，粒子束中ZrO2与Lu2O3(或In2O3)、Nb2O5及TiO2之间发生扩散，形成Lu2O3(或In2O3)、Nb2O5与TiO2晶格掺杂ZrO2的粒子束，粒子束撞击到经过预处理的基材表面，形成Lu2O3(或In2O3)、Nb2O5与TiO2多元稳定氧化锆（四方相和亚稳四方相）抗腐蚀热障涂层。电子束物理气相沉积制备多元稳定氧化锆抗腐蚀热障涂层的工作原理为：将本发明多元稳定氧化锆抗腐蚀热障涂层材料经冷等静压制成坯体，然后在温度为1400℃的马弗炉中烧结4h制成Lu2O3(或In2O3)、Nb2O5与TiO2多元稳定氧化锆（四方相和亚稳四方相）靶材，将靶材放入电子束物理气相沉积设备（如俄罗斯电机械股份公司制造的L2型电子束物理气相沉积设备，对于改型设备，靶材尺寸为Φ70mm×100mm）坩埚中，高能电子束（L2型电子束物理气相沉积设备的电子束功率为60KW）将靶材熔化，并使靶材发生蒸发，蒸发的靶材原子沉积到靶材上方经过预处理的基材表面，形成Lu2O3(或In2O3)、Nb2O5与TiO2多元稳定氧化锆（四方相和亚稳四方相）抗腐蚀热障涂层。The multi-component stabilized zirconia anti-corrosion thermal barrier coating material of the present invention is used to prepare the anti-corrosion thermal barrier coating by using a plasma spraying process or an electron beam physical vapor deposition process. The working principle of plasma spraying to prepare the multi-component stabilized zirconia anti-corrosion thermal barrier coating is as follows: the plasma spray gun forms a high-temperature and high-speed plasma jet, and the powder feeding airflow pushes the multi-component stabilized zirconia anti-corrosion thermal barrier coating material of the present invention into the plasma jet. The multi-component stabilized zirconia anti-corrosion thermal barrier coating material is rapidly heated to a molten or semi-molten state, and is accelerated by a plasma jet to form a sprayed particle beam flying to the substrate. In the particle beam, ZrO 2 and Lu 2 O 3 (or In 2 O 3 ), Nb 2 O 5 and TiO 2 diffuse to form Lu 2 O 3 (or In 2 O 3 ), Nb 2 O 5 and TiO 2 lattice-doped ZrO 2 particle beams, and the particle beams hit To the pretreated substrate surface, form Lu 2 O 3 (or In 2 O 3 ), Nb 2 O 5 and TiO 2 multi-component stabilized zirconia (tetragonal phase and metastable tetragonal phase) anti-corrosion thermal barrier coating. The working principle of the multi-component stabilized zirconia anti-corrosion thermal barrier coating prepared by electron beam physical vapor deposition is as follows: the multi-component stabilized zirconia anti-corrosion thermal barrier coating material of the present invention is cold isostatically pressed into a green body, and then heated at a temperature of 1400 Sinter in a muffle furnace at ℃ for 4 hours to make Lu 2 O 3 (or In 2 O 3 ), Nb 2 O 5 and TiO 2 multi-component stabilized zirconia (tetragonal and metastable tetragonal phase) targets, and put the targets into Electron beam physical vapor deposition equipment (such as L2 type electron beam physical vapor deposition equipment manufactured by Russian Electric Machinery Co., Ltd., for modified equipment, the target size is Φ70mm×100mm) in the crucible, high-energy electron beam (L2 type electron beam physical vapor deposition equipment) The electron beam power of the deposition equipment is 60KW) to melt the target material and evaporate the target material, and the evaporated target material atoms are deposited on the surface of the pretreated substrate above the target material to form Lu 2 O 3 (or In 2 O 3 ), Nb 2 O 5 and TiO 2 multi-component stabilized zirconia (tetragonal phase and metastable tetragonal phase) anti-corrosion thermal barrier coating.
本发明与现有技术相比具有以下优点：Compared with the prior art, the present invention has the following advantages:
1、本发明采用Lu2O3(或In2O3)、Nb2O5和TiO2作为稳定剂稳定ZrO2，获得四方相ZrO2即t-ZrO2。由于Lu3+(或In3+)、Nb5+和Ti4+的离子半径与Na2SO4-V2O5熔盐中V5+的离子半径相近，稳定剂Lu2O3(或In2O3)、Nb2O5和TiO2与Na2SO4-V2O5熔盐难以发生化学反应；当本发明多元稳定氧化锆抗腐蚀热障涂层在长期服役过程中开始发生腐蚀时，仍为四方相ZrO2，不产生导致热障涂层开裂和脱粘的相变应力。所以，本发明多元稳定氧化锆抗熔盐腐蚀热障涂层材料具有优异的抗Na2SO4-V2O5熔盐腐蚀性能。在950℃、70mg/cm2浓度的Na2SO4-V2O5熔盐中进行抗腐蚀性能测试，结果表明本发明多元稳定氧化锆抗腐蚀热障涂层材料的抗Na2SO4-V2O5熔盐腐蚀寿命比传统YSZ抗腐蚀热障涂层材料提高了12倍以上。1. In the present invention, Lu 2 O 3 (or In 2 O 3 ), Nb 2 O 5 and TiO 2 are used as stabilizers to stabilize ZrO 2 to obtain tetragonal ZrO 2 ie t-ZrO 2 . Since the ionic radius of Lu 3+ (or In 3+ ), Nb 5+ and Ti 4+ is similar to that of V 5+ in Na 2 SO 4 -V 2 O 5 molten salt, the stabilizer Lu 2 O 3 (or In 2 O 3 ), Nb 2 O 5 and TiO 2 are difficult to chemically react with Na 2 SO 4 -V 2 O 5 molten salt; When corroded, it is still tetragonal ZrO 2 , and does not produce phase transition stress that causes cracking and debonding of the thermal barrier coating. Therefore, the multi-component stabilized zirconia molten salt corrosion resistant thermal barrier coating material of the present invention has excellent Na 2 SO 4 -V 2 O 5 molten salt corrosion resistance. The corrosion resistance test was carried out in Na 2 SO 4 -V 2 O 5 molten salt at 950°C and 70 mg/cm 2 concentration. The results showed that the multi-component stabilized zirconia anti-corrosion thermal barrier coating material of the present invention has an anti-Na 2 SO 4 - The corrosion life of V 2 O 5 molten salt is more than 12 times higher than that of traditional YSZ anti-corrosion thermal barrier coating materials.
2、本发明采用Lu2O3(或In2O3)、Nb2O5和TiO2作为稳定剂稳定ZrO2，获得四方相ZrO2即t-ZrO2。由于Lu3+(或In3+)、Nb5+和Ti4+的离子半径较小、价态较高，具有较高的场强，能够增加沉积砂子形成的钙镁铝硅酸盐玻璃粘度；同时，TiO2作为玻璃形核剂能够促进沉积砂子形成的钙镁铝硅酸盐玻璃结晶。这两种作用导致熔融的钙镁铝硅酸盐玻璃结晶凝固，不能再继续渗入热障涂层。所以，本发明多元稳定氧化锆抗腐蚀热障涂层材料具有优异的抗沉积砂子形成的钙镁铝硅酸盐腐蚀性能。在1100℃、65mg/cm2浓度的钙镁铝硅酸盐中进行抗钙镁铝硅酸盐熔融玻璃腐蚀性能测试，结果表明本发明多元稳定氧化锆抗腐蚀热障涂层材料的抗钙镁铝硅酸盐熔融玻璃腐蚀寿命比传统的YSZ抗腐蚀热障涂层材料提高了7倍以上。2. The present invention uses Lu 2 O 3 (or In 2 O 3 ), Nb 2 O 5 and TiO 2 as stabilizers to stabilize ZrO 2 to obtain tetragonal ZrO 2 ie t-ZrO 2 . Due to the smaller ionic radius and higher valence state of Lu 3+ (or In 3+ ), Nb 5+ and Ti 4+ , they have higher field strength, which can increase the viscosity of calcium magnesium aluminum silicate glass formed by deposited sand ; At the same time, TiO 2 as a glass nucleating agent can promote the crystallization of calcium magnesium aluminum silicate glass formed by deposited sand. These two effects cause the crystalline calcium-magnesium-aluminosilicate glass to solidify and cannot continue to penetrate the thermal barrier coating. Therefore, the multi-component stabilized zirconia anti-corrosion thermal barrier coating material of the present invention has excellent anti-corrosion properties of calcium magnesium aluminum silicate formed by deposited sand. The anti-calcium magnesium aluminum silicate molten glass corrosion performance test was carried out in calcium magnesium aluminum silicate with a concentration of 65 mg/ cm2 at 1100 ° C. The results showed that the multi-component stabilized zirconia anti-corrosion thermal barrier coating material of the present invention has an anti-calcium magnesium The corrosion life of aluminosilicate fused glass is more than 7 times higher than that of traditional YSZ corrosion-resistant thermal barrier coating materials.
下面结合附图和实施例对本发明作进一步详细说明。The present invention will be described in further detail below in conjunction with the accompanying drawings and embodiments.
附图说明Description of drawings
图1为本发明实施例1多元稳定氧化锆抗腐蚀热障涂层材料和对比例1YSZ抗腐蚀热障涂层材料的X-射线衍射谱图对比曲线。Figure 1 is a comparison curve of X-ray diffraction spectra of the multi-component stabilized zirconia anti-corrosion thermal barrier coating material of Example 1 of the present invention and the comparative example 1YSZ anti-corrosion thermal barrier coating material.
图2为本发明实施例1多元稳定氧化锆抗腐蚀热障涂层材料经26hNa2SO4-V2O5熔盐腐蚀后和对比例1YSZ抗腐蚀热障涂层材料经2hNa2SO4-V2O5熔盐腐蚀后的X-射线衍射谱图对比曲线。Figure 2 shows the multi-component stabilized zirconia anti-corrosion thermal barrier coating material in Example 1 of the present invention after being corroded by 26hNa 2 SO 4 -V 2 O 5 molten salt and the anti-corrosion thermal barrier coating material in Comparative Example 1YSZ after 2hNa 2 SO 4 - Comparison curves of X-ray diffraction spectra after V 2 O 5 molten salt corrosion.
图3为本发明实施例1多元稳定氧化锆抗腐蚀热障涂层材料经26hNa2SO4-V2O5熔盐腐蚀后的表面形貌扫描电镜照片。Fig. 3 is a scanning electron micrograph of the surface morphology of the multi-component stabilized zirconia anti-corrosion thermal barrier coating material in Example 1 of the present invention after being corroded by 26h Na 2 SO 4 -V 2 O 5 molten salt.
图4为本发明对比例1YSZ抗腐蚀热障涂层材料经2h Na2SO4-V2O5熔盐腐蚀后的表面形貌扫描电镜照片。Fig. 4 is a scanning electron micrograph of the surface morphology of the YSZ corrosion-resistant thermal barrier coating material of the comparative example 1 of the present invention after being corroded by Na 2 SO 4 -V 2 O 5 molten salt for 2 hours.
图5为本发明实施例1多元稳定氧化锆抗腐蚀热障涂层材料在温度为1100℃的条件下经20h钙镁铝硅酸盐熔融玻璃腐蚀后的断面Zr元素面分布图。Fig. 5 is a diagram showing the distribution of Zr elements on the cross-section of the multi-component stabilized zirconia anti-corrosion thermal barrier coating material in Example 1 of the present invention after being corroded by calcium magnesium aluminum silicate molten glass for 20 hours at a temperature of 1100°C.
图6为本发明对比例1YSZ抗腐蚀热障涂层材料在温度为1100℃的条件下经20h钙镁铝硅酸盐熔融玻璃腐蚀后的断面Zr元素面分布图。Fig. 6 is a Zr element surface distribution diagram of the cross-section of the YSZ anti-corrosion thermal barrier coating material in the comparative example 1 of the present invention after being corroded by calcium-magnesium-aluminosilicate molten glass for 20 hours at a temperature of 1100°C.
图7为本发明实施例1多元稳定氧化锆抗腐蚀热障涂层材料在温度为1100℃的条件下经20h钙镁铝硅酸盐熔融玻璃腐蚀后的断面Si元素面分布图。Fig. 7 is a cross-sectional Si element surface distribution diagram of the multi-component stabilized zirconia anti-corrosion thermal barrier coating material in Example 1 of the present invention after being corroded by calcium magnesium aluminum silicate molten glass for 20 hours at a temperature of 1100°C.
图8为本发明对比例1YSZ抗腐蚀热障涂层材料在温度为1100℃的条件下经20h钙镁铝硅酸盐熔融玻璃腐蚀后的断面Si元素面分布图。Fig. 8 is a graph showing the distribution of Si element on the cross-section of the YSZ anti-corrosion thermal barrier coating material of the comparative example 1 of the present invention after being corroded by calcium magnesium aluminum silicate molten glass for 20 hours at a temperature of 1100°C.
具体实施方式Detailed ways
实施例1Example 1
本实施例多元稳定氧化锆抗腐蚀热障涂层材料由主剂和稳定剂混合球磨而成，所述主剂为ZrO2，所述稳定剂为Nb2O5、TiO2和稀有金属氧化物的混合物，所述多元稳定氧化锆抗腐蚀热障涂层材料中Nb2O5、TiO2、稀有金属氧化物和ZrO2的摩尔比为5︰7.5︰5︰82.5，所述稀有金属氧化物为Lu2O3或In2O3，本实施例优选为Lu2O3；所述球磨的速率为200r/min，所述球磨的时间为3h。The multi-component stabilized zirconia anti-corrosion thermal barrier coating material in this embodiment is formed by ball milling a main agent and a stabilizer, the main agent is ZrO 2 , and the stabilizer is Nb 2 O 5 , TiO 2 and rare metal oxides The mixture of Nb 2 O 5 , TiO 2 , rare metal oxides and ZrO 2 in the multi-component stabilized zirconia anti-corrosion thermal barrier coating material is 5:7.5:5:82.5, and the rare metal oxides Lu 2 O 3 or In 2 O 3 , preferably Lu 2 O 3 in this embodiment; the speed of the ball milling is 200r/min, and the time of the ball milling is 3h.
实施例2Example 2
本实施例多元稳定氧化锆抗腐蚀热障涂层材料由主剂和稳定剂混合球磨而成，所述主剂为ZrO2，所述稳定剂为Nb2O5、TiO2和稀有金属氧化物的混合物，所述多元稳定氧化锆抗腐蚀热障涂层材料中Nb2O5、TiO2、稀有金属氧化物和ZrO2的摩尔比为4︰6︰4︰86，所述稀有金属氧化物为Lu2O3或In2O3，本实施例优选为In2O3；所述球磨的速率为300r/min，所述球磨的时间为2h。The multi-component stabilized zirconia anti-corrosion thermal barrier coating material in this embodiment is formed by ball milling a main agent and a stabilizer, the main agent is ZrO 2 , and the stabilizer is Nb 2 O 5 , TiO 2 and rare metal oxides The mixture of Nb 2 O 5 , TiO 2 , rare metal oxides and ZrO 2 in the multi-component stabilized zirconia anti-corrosion thermal barrier coating material is 4:6:4:86, and the rare metal oxides Lu 2 O 3 or In 2 O 3 , preferably In 2 O 3 in this embodiment; the speed of the ball milling is 300r/min, and the time of the ball milling is 2h.
实施例3Example 3
本实施例多元稳定氧化锆抗腐蚀热障涂层材料由主剂和稳定剂混合球磨而成，所述主剂为ZrO2，所述稳定剂为Nb2O5、TiO2和稀有金属氧化物的混合物，所述多元稳定氧化锆抗腐蚀热障涂层材料中Nb2O5、TiO2、稀有金属氧化物和ZrO2的摩尔比为6︰9︰6︰79，所述稀有金属氧化物为Lu2O3或In2O3，本实施例优选为Lu2O3；所述球磨的速率为300r/min，所述球磨的时间为2.5h。The multi-component stabilized zirconia anti-corrosion thermal barrier coating material in this embodiment is formed by ball milling a main agent and a stabilizer, the main agent is ZrO 2 , and the stabilizer is Nb 2 O 5 , TiO 2 and rare metal oxides The mixture of Nb 2 O 5 , TiO 2 , rare metal oxides and ZrO 2 in the multi-component stabilized zirconia anti-corrosion thermal barrier coating material is 6:9:6:79, and the rare metal oxides Lu 2 O 3 or In 2 O 3 , preferably Lu 2 O 3 in this embodiment; the speed of the ball milling is 300r/min, and the time of the ball milling is 2.5h.
实施例4Example 4
本实施例多元稳定氧化锆抗腐蚀热障涂层材料由主剂和稳定剂混合球磨而成，所述主剂为ZrO2，所述稳定剂为Nb2O5、TiO2和稀有金属氧化物的混合物，所述多元稳定氧化锆抗腐蚀热障涂层材料中Nb2O5、TiO2、稀有金属氧化物和ZrO2的摩尔比为7︰10.5︰7︰75.5，所述稀有金属氧化物为Lu2O3或In2O3，本实施例优选为In2O3；所述球磨的速率为250r/min，所述球磨的时间为3h。The multi-component stabilized zirconia anti-corrosion thermal barrier coating material in this embodiment is formed by ball milling a main agent and a stabilizer, the main agent is ZrO 2 , and the stabilizer is Nb 2 O 5 , TiO 2 and rare metal oxides The mixture of Nb 2 O 5 , TiO 2 , rare metal oxides and ZrO 2 in the multi-component stabilized zirconia anti-corrosion thermal barrier coating material is 7:10.5:7:75.5, and the rare metal oxides Lu 2 O 3 or In 2 O 3 , preferably In 2 O 3 in this embodiment; the speed of the ball milling is 250r/min, and the time of the ball milling is 3h.
实施例5Example 5
本实施例多元稳定氧化锆抗腐蚀热障涂层材料由主剂和稳定剂混合球磨而成，所述主剂为ZrO2，所述稳定剂为Nb2O5、TiO2和稀有金属氧化物的混合物，所述多元稳定氧化锆抗腐蚀热障涂层材料中Nb2O5、TiO2、稀有金属氧化物和ZrO2的摩尔比为6.5︰9.75︰6.5︰77.25，所述稀有金属氧化物为Lu2O3或In2O3，本实施例优选为Lu2O3；所述球磨的速率为400r/min，所述球磨的时间为1h。The multi-component stabilized zirconia anti-corrosion thermal barrier coating material in this embodiment is formed by ball milling a main agent and a stabilizer, the main agent is ZrO 2 , and the stabilizer is Nb 2 O 5 , TiO 2 and rare metal oxides The mixture of Nb 2 O 5 , TiO 2 , rare metal oxides and ZrO 2 in the multi-component stabilized zirconia anti-corrosion thermal barrier coating material is 6.5:9.75:6.5:77.25, and the rare metal oxides Lu 2 O 3 or In 2 O 3 , preferably Lu 2 O 3 in this embodiment; the speed of the ball milling is 400r/min, and the time of the ball milling is 1h.
实施例6Example 6
本实施例多元稳定氧化锆抗腐蚀热障涂层材料由主剂和稳定剂混合球磨而成，所述主剂为ZrO2，所述稳定剂为Nb2O5、TiO2和稀有金属氧化物的混合物，所述多元稳定氧化锆抗腐蚀热障涂层材料中Nb2O5、TiO2、稀有金属氧化物和ZrO2的摩尔比为3︰4.5︰3︰89.5，所述稀有金属氧化物为Lu2O3或In2O3，本实施例优选为In2O3；所述球磨的速率为100r/min，所述球磨的时间为4h。The multi-component stabilized zirconia anti-corrosion thermal barrier coating material in this embodiment is formed by ball milling a main agent and a stabilizer, the main agent is ZrO 2 , and the stabilizer is Nb 2 O 5 , TiO 2 and rare metal oxides The mixture of Nb 2 O 5 , TiO 2 , rare metal oxides and ZrO 2 in the multi-component stabilized zirconia anti-corrosion thermal barrier coating material is 3:4.5:3:89.5, and the rare metal oxides Lu 2 O 3 or In 2 O 3 , preferably In 2 O 3 in this embodiment; the speed of the ball milling is 100r/min, and the time of the ball milling is 4h.
实施例7Example 7
本实施例多元稳定氧化锆抗腐蚀热障涂层材料由主剂和稳定剂混合球磨而成，所述主剂为ZrO2，所述稳定剂为Nb2O5、TiO2和稀有金属氧化物的混合物，所述多元稳定氧化锆抗腐蚀热障涂层材料中Nb2O5、TiO2、稀有金属氧化物和ZrO2的摩尔比为4.5︰6.75︰4.5︰84.25，所述In2O3稀有金属氧化物为Lu2O3或In2O3，本实施例优选为Lu2O3；所述球磨的速率为280r/min，所述球磨的时间为3h。The multi-component stabilized zirconia anti-corrosion thermal barrier coating material in this embodiment is formed by ball milling a main agent and a stabilizer, the main agent is ZrO 2 , and the stabilizer is Nb 2 O 5 , TiO 2 and rare metal oxides The mixture of Nb 2 O 5 , TiO 2 , rare metal oxides and ZrO 2 in the multi-component stabilized zirconia anti-corrosion thermal barrier coating material is 4.5:6.75:4.5:84.25, and the In 2 O 3 The rare metal oxide is Lu 2 O 3 or In 2 O 3 , preferably Lu 2 O 3 in this embodiment; the speed of the ball milling is 280r/min, and the time of the ball milling is 3h.
对比例1Comparative example 1
本对比例采用Y2O3和ZrO2按照8∶92的质量比混合球磨，球磨速率为200r/min，球磨时间为3h，得到YSZ抗腐蚀热障涂层材料。In this comparative example, Y 2 O 3 and ZrO 2 were mixed and ball-milled according to the mass ratio of 8:92, the ball-milling rate was 200r/min, and the ball-milling time was 3h to obtain the YSZ anti-corrosion thermal barrier coating material.
将本发明实施例1多元稳定氧化锆抗腐蚀热障涂层材料和对比例1YSZ抗腐蚀热障涂层材料均压制成尺寸为Φ12mm×2mm的坯体，再在温度为1600℃的马弗炉中烧结4小时，之后进行抗腐蚀性能对比测试，具体测试方法和测试结果如下：Both the multi-component stabilized zirconia anti-corrosion thermal barrier coating material in Example 1 of the present invention and the YSZ anti-corrosion thermal barrier coating material in Comparative Example 1 were pressed into a green body with a size of Φ12mm×2mm, and then heated in a muffle furnace at a temperature of 1600°C After sintering for 4 hours, the corrosion resistance performance comparison test was carried out. The specific test methods and test results are as follows:
一、抗Na2SO4-V2O5熔盐腐蚀性能测试1. Anti-Na 2 SO 4 -V 2 O 5 molten salt corrosion performance test
将Na2SO4和V2O5按照3∶2的质量比混合球磨，得到Na2SO4-V2O5混合粉末。分别将Na2SO4-V2O5混合粉末涂刷至实施例1多元稳定氧化锆抗腐蚀热障涂层材料表面，以及对比例1YSZ抗腐蚀热障涂层材料表面，且Na2SO4-V2O5混合粉末的涂刷量均为70mg/cm2，然后将涂刷有Na2SO4-V2O5混合粉末的多元稳定氧化锆抗腐蚀热障涂层材料和涂刷有Na2SO4-V2O5混合粉末的YSZ抗腐蚀热障涂层材料同时置于温度为950℃的电炉中，使Na2SO4-V2O5混合粉末在950℃温度下熔融成Na2SO4-V2O5熔盐，从而对多元稳定氧化锆抗腐蚀热障涂层材料和YSZ抗腐蚀热障涂层材料进行抗Na2SO4-V2O5熔盐腐蚀试验。Na 2 SO 4 and V 2 O 5 were mixed and ball-milled according to a mass ratio of 3:2 to obtain Na 2 SO 4 -V 2 O 5 mixed powder. Brush Na 2 SO 4 -V 2 O 5 mixed powder on the surface of the multi-component stabilized zirconia anti-corrosion thermal barrier coating material in Example 1 and the surface of the YSZ anti-corrosion thermal barrier coating material in Comparative Example 1, and Na 2 SO 4 The coating amount of -V 2 O 5 mixed powder is 70mg/cm 2 , and then the multi-component stabilized zirconia anti-corrosion thermal barrier coating material coated with Na 2 SO 4 -V 2 O 5 mixed powder and coated with The YSZ anti-corrosion thermal barrier coating material of Na 2 SO 4 -V 2 O 5 mixed powder is placed in an electric furnace at a temperature of 950°C at the same time, and the Na 2 SO 4 -V 2 O 5 mixed powder is melted at a temperature of 950°C to form Na 2 SO 4 -V 2 O 5 molten salt, so the anti-corrosion test of Na 2 SO 4 -V 2 O 5 molten salt was carried out on multi-component stabilized zirconia anti-corrosion thermal barrier coating materials and YSZ anti-corrosion thermal barrier coating materials.
图1为本发明实施例1多元稳定氧化锆抗腐蚀热障涂层材料和对比例1YSZ抗腐蚀热障涂层材料的X-射线衍射谱图对比曲线。图1中曲线a为本发明实施例1多元稳定氧化锆抗腐蚀热障涂层材料的X-射线衍射谱图曲线，曲线b为本发明对比例1YSZ抗腐蚀热障涂层材料的X-射线衍射谱图曲线。由图1可知，本发明实施例1多元稳定氧化锆抗腐蚀热障涂层材料和对比例1YSZ抗腐蚀热障涂层材料中的ZrO2均为四方相ZrO2，即t-ZrO2。Figure 1 is a comparison curve of X-ray diffraction spectra of the multi-component stabilized zirconia anti-corrosion thermal barrier coating material of Example 1 of the present invention and the comparative example 1YSZ anti-corrosion thermal barrier coating material. Curve a in Fig. 1 is the X-ray diffraction spectrum curve of the multi-component stabilized zirconia anti-corrosion thermal barrier coating material of Example 1 of the present invention, and curve b is the X-ray of the YSZ anti-corrosion thermal barrier coating material of Comparative Example 1 of the present invention Diffraction spectrum curve. It can be seen from Fig. 1 that the ZrO 2 in the multi-component stabilized zirconia anti-corrosion thermal barrier coating material in Example 1 of the present invention and in the comparative example 1YSZ anti-corrosion thermal barrier coating material is tetragonal ZrO 2 , namely t-ZrO 2 .
图2为本发明实施例1多元稳定氧化锆抗腐蚀热障涂层材料经26hNa2SO4-V2O5熔盐腐蚀后和对比例1YSZ抗腐蚀热障涂层材料经2hNa2SO4-V2O5熔盐腐蚀后的X-射线衍射谱图对比曲线。图2中曲线c为实施例1多元稳定氧化锆抗腐蚀热障涂层材料在温度为950℃的条件下经26h Na2SO4-V2O5熔盐腐蚀后的X-射线衍射谱图曲线，曲线d为对比例1YSZ抗腐蚀热障涂层材料在温度为950℃的条件下经2h Na2SO4-V2O5熔盐腐蚀后的X-射线衍射谱图曲线。Figure 2 shows the multi-component stabilized zirconia anti-corrosion thermal barrier coating material in Example 1 of the present invention after being corroded by 26hNa 2 SO 4 -V 2 O 5 molten salt and the anti-corrosion thermal barrier coating material in Comparative Example 1YSZ after 2hNa 2 SO 4 - Comparison curves of X-ray diffraction spectra after V 2 O 5 molten salt corrosion. Curve c in Figure 2 is the X-ray diffraction spectrum of the multi-component stabilized zirconia anti-corrosion thermal barrier coating material in Example 1 after being corroded by Na 2 SO 4 -V 2 O 5 molten salt for 26 hours at a temperature of 950°C Curve, curve d is the X-ray diffraction spectrum curve of the YSZ anti-corrosion thermal barrier coating material of Comparative Example 1 after being corroded by Na 2 SO 4 -V 2 O 5 molten salt for 2 hours at a temperature of 950°C.
图3为本发明实施例1多元稳定氧化锆抗腐蚀热障涂层材料经26hNa2SO4-V2O5熔盐腐蚀后的表面形貌扫描电镜照片。图4为本发明对比例1YSZ抗腐蚀热障涂层材料经2h Na2SO4-V2O5熔盐腐蚀后的表面形貌扫描电镜照片。Fig. 3 is a scanning electron micrograph of the surface morphology of the multi-component stabilized zirconia anti-corrosion thermal barrier coating material in Example 1 of the present invention after being corroded by 26h Na 2 SO 4 -V 2 O 5 molten salt. Fig. 4 is a scanning electron micrograph of the surface morphology of the YSZ corrosion-resistant thermal barrier coating material of the comparative example 1 of the present invention after being corroded by Na 2 SO 4 -V 2 O 5 molten salt for 2 hours.
结合图1、图2和图3可知，本发明实施例1多元稳定氧化锆抗腐蚀热障涂层材料在温度为950℃的条件下经26h Na2SO4-V2O5熔盐腐蚀后表面仅发生微弱腐蚀，没有发生ZrO2相变，仍为t-ZrO2，微弱腐蚀生成少量的腐蚀产物LuVO4，且生成的LuVO4的尺寸微小（LuVO4如图3所示）。结合图1、图2和图4可知，对比例1YSZ抗腐蚀热障涂层材料在温度为950℃的条件下经2h Na2SO4-V2O5熔盐腐蚀后表面发生明显腐蚀，t-ZrO2全部相变为m-ZrO2（m-ZrO2如图4中I所示），明显腐蚀生成腐蚀产物YVO4（YVO4如图4中II所示），且生成的YVO4的形貌粗大。由此证实本发明多元稳定氧化锆抗腐蚀热障涂层材料的抗Na2SO4-V2O5熔盐腐蚀性能明显优于YSZ抗腐蚀热障涂层材料，并且本发明多元稳定氧化锆抗腐蚀热障涂层材料的抗Na2SO4-V2O5熔盐腐蚀寿命比YSZ抗腐蚀热障涂层材料提高了12倍以上。Combining Figure 1, Figure 2 and Figure 3, it can be seen that the multi-component stabilized zirconia anti-corrosion thermal barrier coating material in Example 1 of the present invention is corroded by Na 2 SO 4 -V 2 O 5 molten salt for 26 hours at a temperature of 950°C Only weak corrosion occurs on the surface, no ZrO 2 phase transformation occurs, and it is still t-ZrO 2 . The weak corrosion generates a small amount of corrosion product LuVO 4 , and the size of the generated LuVO 4 is small (LuVO 4 is shown in Figure 3). Combining Figure 1, Figure 2 and Figure 4, it can be seen that the corrosion-resistant thermal barrier coating material of Comparative Example 1YSZ was corroded by Na 2 SO 4 -V 2 O 5 molten salt for 2 hours at a temperature of 950°C, and the surface was corroded obviously, t The entire phase of -ZrO 2 changes to m-ZrO 2 (m-ZrO 2 is shown as I in Figure 4), and the corrosion product YVO 4 is obviously corroded (YVO 4 is shown as II in Figure 4), and the generated YVO 4 Bold in appearance. It is thus confirmed that the corrosion resistance of the multi-component stabilized zirconia anti-corrosion thermal barrier coating material of the present invention is significantly better than that of the YSZ anti-corrosion thermal barrier coating material, and that the multi- component stabilized zirconia anti -corrosion thermal barrier coating material of the present invention The Na 2 SO 4 -V 2 O 5 molten salt corrosion life of the anti-corrosion thermal barrier coating material is more than 12 times higher than that of the YSZ anti-corrosion thermal barrier coating material.
二、抗钙镁铝硅酸盐熔融玻璃腐蚀性能测试2. Corrosion performance test of calcium magnesium aluminum silicate molten glass
将SiO2、CaO、MgO、Al2O3、Na2O、K2O和Fe2O3按照50︰38︰5︰4︰1︰1︰1的摩尔比混合球磨，得到钙镁铝硅酸盐玻璃粉末。分别将钙镁铝硅酸盐玻璃粉末涂敷至实施例1多元稳定氧化锆抗腐蚀热障涂层材料表面，以及对比例1YSZ抗腐蚀热障涂层材料表面，且钙镁铝硅酸盐玻璃粉末的涂敷量均为65mg/cm2；然后将涂刷有钙镁铝硅酸盐玻璃粉末的多元稳定氧化锆抗腐蚀热障涂层材料和涂刷有钙镁铝硅酸盐玻璃粉末的YSZ抗腐蚀热障涂层材料同时置于温度为1100℃的电炉中，使钙镁铝硅酸盐玻璃粉末在1100℃温度下受热熔融成钙镁铝硅酸盐熔融玻璃，从而对多元稳定氧化锆抗腐蚀热障涂层材料和YSZ抗腐蚀热障涂层材料进行抗钙镁铝硅酸盐熔融玻璃腐蚀试验。Mix and ball mill SiO 2 , CaO, MgO, Al 2 O 3 , Na 2 O, K 2 O and Fe 2 O 3 according to the molar ratio of 50:38:5:4:1:1:1 to obtain calcium magnesium aluminum silicon Salt glass powder. Calcium-magnesium-aluminosilicate glass powder was coated on the surface of the multi-component stabilized zirconia anti-corrosion thermal barrier coating material in Example 1 and the surface of the YSZ anti-corrosion thermal barrier coating material in Comparative Example 1, and the calcium-magnesium-aluminosilicate glass The coating amount of the powder is 65mg/cm 2 ; then the multi-component stabilized zirconia anti-corrosion thermal barrier coating material coated with calcium magnesium aluminum silicate glass powder and the material coated with calcium magnesium aluminum silicate glass powder The YSZ anti-corrosion thermal barrier coating material is placed in an electric furnace at a temperature of 1100°C at the same time, so that the calcium magnesium aluminosilicate glass powder is heated and melted at a temperature of 1100°C to form a calcium magnesium aluminosilicate molten glass, thereby stabilizing the oxidation of multiple elements. Zirconium anti-corrosion thermal barrier coating materials and YSZ anti-corrosion thermal barrier coating materials were tested against corrosion of calcium magnesium aluminum silicate molten glass.
图5为本发明实施例1多元稳定氧化锆抗腐蚀热障涂层材料在温度为1100℃的条件下经20h钙镁铝硅酸盐熔融玻璃腐蚀后的断面Zr元素面分布图。图6为本发明对比例1YSZ抗腐蚀热障涂层材料在温度为1100℃的条件下经20h钙镁铝硅酸盐熔融玻璃腐蚀后的断面Zr元素面分布图。Fig. 5 is a diagram showing the distribution of Zr elements on the cross-section of the multi-component stabilized zirconia anti-corrosion thermal barrier coating material in Example 1 of the present invention after being corroded by calcium magnesium aluminum silicate molten glass for 20 hours at a temperature of 1100°C. Fig. 6 is a Zr element surface distribution diagram of the cross-section of the YSZ anti-corrosion thermal barrier coating material in the comparative example 1 of the present invention after being corroded by calcium-magnesium-aluminosilicate molten glass for 20 hours at a temperature of 1100°C.
图7为本发明实施例1多元稳定氧化锆抗腐蚀热障涂层材料在温度为1100℃的条件下经20h钙镁铝硅酸盐熔融玻璃腐蚀后的断面Si元素面分布图。图8为本发明对比例1YSZ抗腐蚀热障涂层材料在温度为1100℃的条件下经20h钙镁铝硅酸盐熔融玻璃腐蚀后的断面Si元素面分布图。Fig. 7 is a cross-sectional Si element surface distribution diagram of the multi-component stabilized zirconia anti-corrosion thermal barrier coating material in Example 1 of the present invention after being corroded by calcium magnesium aluminum silicate molten glass for 20 hours at a temperature of 1100°C. Fig. 8 is a graph showing the distribution of Si element on the cross-section of the YSZ anti-corrosion thermal barrier coating material of the comparative example 1 of the present invention after being corroded by calcium magnesium aluminum silicate molten glass for 20 hours at a temperature of 1100°C.
由图5、图6、图7和图8可知，本发明实施例1多元稳定氧化锆抗腐蚀热障涂层材料在温度为1100℃的条件下经20h钙镁铝硅酸盐熔融玻璃腐蚀后的腐蚀深度为16μm；对比例1YSZ抗腐蚀热障涂层材料在温度为1100℃的条件下经20h钙镁铝硅酸盐熔融玻璃腐蚀后的腐蚀深度为130μm。由此证实本发明多元稳定氧化锆抗腐蚀热障涂层材料的抗钙镁铝硅酸盐熔融玻璃腐蚀性能明显优于YSZ抗腐蚀热障涂层材料，并且本发明多元稳定氧化锆抗腐蚀热障涂层材料的抗钙镁铝硅酸盐熔融玻璃寿命比YSZ抗腐蚀热障涂层材料提高了7倍以上。It can be seen from Fig. 5, Fig. 6, Fig. 7 and Fig. 8 that the multi-component stabilized zirconia anti-corrosion thermal barrier coating material in Example 1 of the present invention is corroded by calcium magnesium aluminum silicate molten glass for 20 hours at a temperature of 1100°C. The corrosion depth is 16 μm; the corrosion depth of the comparative example 1YSZ corrosion-resistant thermal barrier coating material is 130 μm after being corroded by calcium magnesium aluminum silicate molten glass for 20 hours at a temperature of 1100 ° C. This proves that the anti-calcium magnesium aluminum silicate molten glass corrosion performance of the multi-component stabilized zirconia anti-corrosion thermal barrier coating material of the present invention is obviously better than that of the YSZ anti-corrosion thermal barrier coating material, and the multi-component stabilized zirconia anti-corrosion thermal barrier coating material of the present invention The anti-calcium magnesium aluminum silicate molten glass life of the barrier coating material is more than 7 times higher than that of the YSZ anti-corrosion thermal barrier coating material.
以上所述，仅是本发明的较佳实施例，并非对本发明作任何限制。凡是根据发明技术实质对以上实施例所作的任何简单修改、变更以及等效变化，均仍属于本发明技术方案的保护范围内。The above descriptions are only preferred embodiments of the present invention, and do not limit the present invention in any way. All simple modifications, changes and equivalent changes made to the above embodiments according to the technical essence of the invention still belong to the protection scope of the technical solution of the invention.
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