目的 研究DD10/NiCoCrAlYHf（HY5）涂层体系在温度1 150、1 200 ℃下的抗氧化性能。方法 采用多弧离子镀（AIP）技术在第3代单晶高温合金DD10表面沉积HY5涂层,在1 150、1 200 ℃下对HY5涂层进行200 h的高温氧化测试。通过扫描电镜（SEM）、能谱仪（EDS）和X射线衍射仪（XRD）对涂层氧化前后的微观形貌、元素组成、物相进行表征。结果 在2种温度下,HY5涂层在氧化初期均迅速生成了一层连续的α-Al2O3（TGO）。随着氧化时间的延长,TGO逐渐增厚。在1 150 ℃下氧化200 h后,涂层的氧化增量约为1.16 mg/cm2,TGO厚度约为8 µm,未出现氧化膜开裂或剥落现象。在TGO内形成了纳米级弥散分布的Y2Hf2O7相,涂层与基体之间形成了约80 µm的互扩散区。相比之下,在1 200 ℃下的氧化行为更剧烈。在氧化60 h后,TGO厚度为7.5 µm左右,并出现了局部剥落现象。当氧化时间延长至100 h后,涂层表面生成了Co、Al、Cr的混合氧化物,并向涂层内部延伸。在氧化200 h后,氧化增量约为1.38 mg/cm2,高于1 150 ℃时的氧化增量,混合氧化物延伸深度超过100 µm,直至合金基体。结论 DD10/HY5涂层体系在1 150 ℃下表现出优异的抗氧化性能。在1 200 ℃下,由于TGO快速生长和过早剥落,因此涂层的抗氧化性能显著降低。
Abstract
NiCoCrAlYHf coatings (HY5 coatings) are extensively applied on turbine blades to enhance the oxidation resistance of underlying superalloys. This work systematically investigates the high-temperature oxidation behavior and degradation mechanisms of HY5 coatings deposited on DD10, a third-generation single-crystal superalloy, substrates via multi-arc ion plating (AIP). The as-deposited coatings are subsequently subject to a vacuum annealing treatment at 1 050 ℃ for 2 h to promote microstructural homogenization and relieve residual stresses. The chemical composition of the coatings is precisely measured as 54.5Ni-13.9Co-23.5Cr-7.5Al-0.7Hf with an average thickness of ~25 µm. Microstructural analysis reveals that the annealed coatings primarily consist of β-NiAl and γ'-Ni3Al. Isothermal oxidation tests are conducted at 1 150 ℃ and 1 200 ℃ for 200 h, respectively. Then oxidation curves are obtained by plotting weight gains of coatings against oxidation time. The results reveal that a continuous, adherent, and protective α-Al2O3 scale, known as the thermally grown oxide (TGO), forms rapidly on the surface of both coatings during the initial oxidation stage. This is accompanied by a rapid weight gain within the first 15 h, amounting to ~0.47 mg/cm2 at 1 150 ℃ and ~0.51 mg/cm2 at 1 200 ℃, which is directly attributable to the swift nucleation and lateral growth of the TGO. Subsequently, the oxidation rate decreases markedly, transitioning to parabolic kinetics, indicating that the dense TGO effectively serves as a diffusion barrier against oxygen ingress and cation outdiffusion. After 200 h of oxidation at 1 150 ℃, the coatings exhibit a total weight gain of ~1.16 mg/cm2 and the TGO reaches a stable thickness of ~8 µm, with no evidence of microcracking or spallation observed, demonstrating excellent scale adhesion. Nanoscale Y2Hf2O7 phases form within the TGO, which not only enhance the adhesion of the TGO but also reduce its growth rate. An interdiffusion zone (IDZ) of ~80 µm forms beneath the coatings, characterized by gradually smoothed elemental concentration profiles. It confirms the significant interdiffusion of elements that act to mitigate the initial sharp compositional gradient between the substrates and the coatings. In contrast, the oxidation behavior at 1 200 ℃ is more severe and leads to accelerated degradation. After 60 h of oxidation, the TGO thickness already reaches ~7.5 µm with localized spallation, which is nearly comparable to the TGO thickness after 200 h of oxidation at 1 150 ℃; as the oxidation time extends to 100 h, non-protective, fast-growing mixed oxides of Co, Al, and Cr form on the surface and penetrate inward. EDS analysis indicates that the Al content in the coating matrix severely depletes to below 4%, compromising its ability to reform the protective Al2O3 scale. After 200 h of oxidation, the oxidation weight gain reaches ~1.38 mg/cm2, and the destructive inward growth of mixed oxides exceeds a depth of 100 µm, penetrating to the alloy substrate. In summary, the HY5 coating exhibits excellent oxidation resistance at 1150 ℃, whereas at 1200 ℃, rapid TGO growth and premature spallation lead to a significant decline in its protective performance.
关键词
第3代单晶高温合金 /
NiCoCrAlYHf /
高温防护涂层 /
抗氧化性能 /
多弧离子镀 /
氧化动力学
Key words
third-generation single-crystal superalloy /
NiCoCrAlYHf /
thermal barrier coatings /
oxidation resistance /
arc ion plating /
oxidation kinetics
{{custom_sec.title}}
{{custom_sec.title}}
{{custom_sec.content}}
参考文献
[1] LONG H B, MAO S C, LIU Y N, et al.Microstructural and Compositional Design of Ni-Based Single Crystalline Superalloys-A Review[J]. Journal of Alloys and Compounds, 2018, 743: 203-220.
[2] XIA W S, ZHAO X B, YUE L, et al.A Review of Composition Evolution in Ni-Based Single Crystal Superalloys[J]. Journal of Materials Science & Technology, 2020, 44: 76-95.
[3] YUE Q Z, LIU L, YANG W C, et al.Stress Dependence of the Creep Behaviors and Mechanisms of a Third-Generation Ni-Based Single Crystal Superalloy[J]. Journal of Materials Science & Technology, 2019, 35(5): 752-763.
[4] XU R D, LI Y, YU H C.Creep Behavior and Deformation Mechanism of a Third-Generation Single Crystal Ni-Based Superalloy at 980 ℃[J]. Metals, 2023, 13(9): 1541.
[5] PADTURE N P, GELL M, JORDAN E H.Thermal Barrier Coatings for Gas-Turbine Engine Applications[J]. Science, 2002, 296(5566): 280-284.
[6] 郑蕾, 郭洪波, 郭磊, 等. 新一代超高温热障涂层研究[J]. 航空材料学报, 2012, 32(6): 14-24.
ZHENG L, GUO H B, GUO L, et al.New Generation Thermal Barrier Coatings for Ultrahigh Temperature Applications[J]. Journal of Aeronautical Materials, 2012, 32(6): 14-24.
[7] OSKAY C, RUDOLPHI M, AFFELDT E E, et al.Evolution of Microstructure and Mechanical Properties of NiAl-Diffusion Coatings after Thermocyclic Exposure[J]. Intermetallics, 2017, 89: 22-31.
[8] HOSSEINI Y, KERMANPUR A, ASHRAFIZADEH F, et al.Oxidation Behavior of Overlay NiCoCrAlY and Diffusion Aluminide Coatings Deposited on a Directionally Solidified Nickel-Based Superalloy: A Comparative Study[J]. JOM, 2023, 75(1): 64-75.
[9] BOZZA F, BOLELLI G, GIOLLI C, et al.Diffusion Mechanisms and Microstructure Development in Pack Aluminizing of Ni-Based Alloys[J]. Surface and Coatings Technology, 2014, 239: 147-159.
[10] RABIEI A, EVANS A G.Failure Mechanisms Associated with the Thermally Grown Oxide in Plasma-Sprayed Thermal Barrier Coatings[J]. Acta Materialia, 2000, 48(15): 3963-3976.
[11] HE J, ZHANG Z, PENG H, et al.The Role of Dy and Hf Doping on Oxidation Behavior of Two-Phase (Γ′+Β) Ni-Al Alloys[J]. Corrosion Science, 2015, 98: 699-707.
[12] GUO H B, ZHANG T, WANG S X, et al.Effect of Dy on Oxide Scale Adhesion of NiAl Coatings at 1 200 ℃[J]. Corrosion Science, 2011, 53(6): 2228-2232.
[13] LI D Q, GUO H B, WANG D, et al.Cyclic Oxidation of Β-NiAl with Various Reactive Element Dopants at 1 200 ℃[J]. Corrosion Science, 2013, 66: 125-135.
[14] SVENSSON H, CHRISTENSEN M, KNUTSSON P, et al.Influence of Pt on the Metal-Oxide Interface during High Temperature Oxidation of NiAl Bulk Materials[J]. Corrosion Science, 2009, 51(3): 539-546.
[15] KANG J, LIU Y, GENG L L, et al.Microstructure and Performance Properties of 1 200 ℃-Servicing Gradiently Aluminized NiCrAlYSi Coating for Single-Crystal Nickel-Based Superalloy[J]. Journal of Alloys and Compounds, 2022, 924: 166619.
[16] PENG H, GUO H B, YAO R, et al.Improved Oxidation Resistance and Diffusion Barrier Behaviors of Gradient Oxide Dispersed NiCoCrAlY Coatings on Superalloy[J]. Vacuum, 2010, 85(5): 627-633.
[17] BARRETT C A, LOWELL C E.Resistance of Ni-Cr-Al Alloys to Cyclic Oxidation at 1 100 and 1 200 ℃[J]. Oxidation of Metals, 1977, 11(4): 199-223.
[18] ANSARI M, SHOJA-RAZAVI R, BAREKAT M, et al.High-Temperature Oxidation Behavior of Laser-Aided Additively Manufactured NiCrAlY Coating[J]. Corrosion Science, 2017, 118: 168-177.
[19] 余春堂, 阳颖飞, 鲍泽斌, 等. 先进高温热障涂层用高性能粘接层制备及研究进展[J]. 中国腐蚀与防护学报, 2019, 39(5): 395-403.
YU C T, YANG Y F, BAO Z B, et al.Research Progress in Preparation and Development of Excellent Bond Coats for Advanced Thermal Barrier Coatings[J]. Journal of Chinese Society for Corrosion and Protection, 2019, 39(5): 395-403.
[20] ZHONG J Y, LIU J H, ZHOU X, et al.Thermal Cyclic Oxidation and Interdiffusion of NiCoCrAlYHf Coating on a Ni-Based Single Crystal Superalloy[J]. Journal of Alloys and Compounds, 2016, 657: 616-625.
[21] 蔡妍, 李建平, 何利民, 等. NiCoCrAlYHf涂层材料的1200 ℃高温氧化行为[J]. 真空, 2017, 54(6): 12-16.
CAI Y, LI J P, HE L M, et al.1200 ℃ Oxidation Behavior Study of NiCoCrAlYHf Coating[J]. Vacuum, 2017, 54(6): 12-16.
[22] CHEN Z, ZHONG J Y, YANG S L, et al.The Interdiffusion Behavior of NiCoCrAlYHf Coating Deposited by Arc Ion Plating on Carburized Ni-Based Single Crystal Superalloy[J]. Materials, 2021, 14(23): 7401.
[23] CLARKE D R, OECHSNER M, PADTURE N P.Thermal-Barrier Coatings for More Efficient Gas-Turbine Engines[J]. MRS Bulletin, 2012, 37(10): 891-898.
[24] TENG X D, GAO R Q, LI L H, et al.Improved Oxidation Resistance of AIP NiCrAlYSi Coatings by Applying Positive Bias[J]. Surface and Coatings Technology, 2024, 489: 131087.
[25] TENG X D, PENG H, LI L H, et al.Investigation on Crystal Orientations in EB-PVD YSZ Coatings under Different Substrate Rotation Mode[J]. Journal of the European Ceramic Society, 2023, 43(12): 5373-5380.
[26] KEIDAR M, BEILIS I, BOXMAN R L, et al.Macroparticle Interaction with a Substrate in Cathodic Vacuum Arc Deposition[J]. Surface and Coatings Technology, 1996, 86: 415-420.
[27] SHEN Q, YANG L, ZHOU Y C, et al.Models for Predicting TGO Growth to Rough Interface in TBCS[J]. Surface and Coatings Technology, 2017, 325: 219-228.
[28] HUTCHINSON J W, HE M Y, EVANS A G.The Influence of Imperfections on the Nucleation and Propagation of Buckling Driven Delaminations[J]. Journal of the Mechanics and Physics of Solids, 2000, 48(4): 709-734.
[29] MENG G H, GUI P P, LI S S, et al.Oxide Pegs Improved Α-Al2O3 Scale Adhesion on Aluminide Coatings[J]. Corrosion Science, 2025, 249: 112809.
[30] PINT B A, HOBBS L W.The Oxidation Behavior of Y2O3-Dispersed Β-NiAl[J]. Oxidation of Metals, 2004, 61(3): 273-292.
[31] GIL A, NAUMENKO D, VASSEN R, et al.Y-Rich Oxide Distribution in Plasma Sprayed MCrAlY-Coatings Studied by SEM with a Cathodoluminescence Detector and Raman Spectroscopy[J]. Surface and Coatings Technology, 2009, 204(4): 531-538.
[32] SHILLINGTON E A G, CLARKE D R. Spalling Failure of a Thermal Barrier Coating Associated with Aluminum Depletion in the Bond-Coat[J]. Acta Materialia, 1999, 47(4): 1297-1305.
[33] LUO L R, SHAN X, ZOU Z H, et al.A High Performance NiCoCrAlY Bond Coat Manufactured Using Laser Powder Deposition[J]. Corrosion Science, 2017, 126: 356-365.
[34] LU J, CHEN Y, ZHAO C S, et al.Significantly Improving the Oxidation and Spallation Resistance of a MCrAlY Alloy by Controlling the Distribution of Yttrium[J]. Corrosion Science, 2019, 153: 178-190.
[35] WU X X, MAKINENI S K, LIEBSCHER C H, et al.Unveiling the Re Effect in Ni-Based Single Crystal Superalloys[J]. Nature Communications, 2020, 11: 389.
[36] LI J C, WEI L L, HE J, et al.The Role of Re in Improving the Oxidation-Resistance of a Re Modified PtAl Coating on Mo-Rich Single Crystal Superalloy[J]. Journal of Materials Science & Technology, 2020, 58: 63-72.
[37] 李梦奇, 彭徽, 文娇, 等. 粉末冶金靶材多弧离子镀HY3涂层抗氧化性能[J]. 表面技术, 2023, 52(6): 276-284.
LI M Q, PENG H, WEN J, et al.Oxidation Resistance of HY3 Coating Deposited by Arc Ion Plating with Powder Metallurgy Target[J]. Surface Technology, 2023, 52(6): 276-284.
基金
机械工业高温防护涂层技术与装备工程研究中心开放课题（GCZX-2024-KF-07）
PDF(13619 KB)
渝公网安备 50010702501715号 渝ICP备15012534号-3
