目的 热生长氧化物（TGO）增厚是导致热障涂层（TBCs）失效的主要因素之一。前期制备的含双层结构黏结层的TBCs虽可有效减缓TGO的生长,但尚未明确该体系下TGO缓慢生长的机理,故开展相关研究,以揭示其近指数缓慢生长的内在机制。方法 采用高温氧化、拉曼光谱内应力评估等技术,表征双层结构黏结层表面TGO的形貌、完整性,以及内应力随氧化时间的演变规律,揭示其近指数缓慢生长机理。结果 双层结构黏结层具有梯度热膨胀系数特征,靠近基体的多孔黏结层的热膨胀系数约为12.0×10-6 K-1,靠近陶瓷的氧化黏结层的热膨胀系数约为11.6×10-6 K-1,有效降低了涂层间的热膨胀失配应力。与传统涂层相比,双层结构黏结层能够降低其表面TGO内部应力约50%。经500 h高温氧化后,传统TBCs 黏结层表面TGO出现贯穿性微裂纹,而双层结构黏结层表面TGO未出现贯穿性微裂纹,厚度均匀性和完整性优异,有效抑制了高温元素的扩散。结论 在缓冲热膨胀失配应力、阻隔元素扩散双重机制协同作用下,双层结构黏结层表面的TGO生长动力学曲线显著低于传统涂层TGO,呈现近指数生长。
Abstract
Thermally grown oxide (TGO) growth is a critical failure mechanism of thermal barrier coatings (TBCs) for hot-section component in gas turbines. In our previous work, TBCs with double bond coat was developed, and TGO exhibited a roughly exponential growth with the thermal exposure duration. As a result, the durability of the TBCs is improved by about 100%. However, this slow growth mechanism of TGO is still not clear yet. This study aims to address the roughly exponential growth of TGO on the double bond coat, according to TGO evolution and the synergistic mechanism of stress buffering and diffusion barriers. The double bond coat was fabricated via two thermal spraying technologies. The atmospheric plasma spraying (APS) was used to deposit a porous bond coat (Por-BC, (50±5) μm, (12±3)% porosity) by Ni-23Co-20Cr-8.5Al-5.0Ta-0.6Y powder. The high-velocity oxygen fuel (HVOF) spraying then was used to prepare a dense oxidized bond coat (Oxi-BC, 100 μm thick) on Por-BC (15% Al2O3 dispersed in Oxi-BC). 40 μm-thick 8% Y2O3-ZrO2 (YSZ) topcoat was deposited by APS with hollow spherical YSZ powder. Samples underwent pre-oxidation (Ar atmosphere, <10 μmol/mol O2, from 1 000 ℃/4 h to 1 080 ℃/4 h, furnace cooling) and high-temperature oxidation at 1 000 ℃ in static air for 5 h, 20 h, 50 h, 100 h, 200 h, and 500 h. TGO morphology/thickness was observed via SEM (10 random regions averaged). In-plane compressive stress in TGO was evaluated via Raman spectroscopy (514 nm laser, R2 peak shift). Results showed that the double bond coat had a gradient coefficient of thermal expansion (CTE): the Por-BC (adjacent to the Inconel 738 substrate) had a CTE of 12.0×10-6 K-1, and the Oxi-BC (near the YSZ topcoat) had a CTE of 11.6×10-6 K-1, which could reduce thermal mismatch stress between the substrate and the topcoat. Therefore, the double bond coat could significantly improve the durability of TBCs because of the decrease of the interior stress. TGO thickness on the double bond coat was about (1.26±0.11) μm and (1.71±0.17) μm, when the thermal exposure time was 100 h and 500 h, respectively. In comparison, the TGO thickness in traditional TBCs was about (1.53±0.19) μm and (6.32±0.31) μm, respectively, when the thermal exposure time was 100 h and 500 h. Raman analysis showed the compressive stress in TGO on the double bond coat was about -1.75 GPa (5 h), -1.93 GPa (20 h), -2.03 GPa (50 h), -2.07 GPa (100 h), -2.28 GPa (500 h), which was over 50% lower than that in traditional TBCs. SEM at 200 h showed β-NiAl phases (Al-rich) adjacent to TGO in the double bond coat (no Al-depleted zone), while traditional bond coat had β-NiAl 10 μm from TGO with a clear Al-depleted zone (severe Al diffusion). The near-exponential slow TGO growth on the double bond coat was resulted from two synergistic effects. Firstly, gradient CTE in TBCs alleviated thermomechanical stress, reducing in-plane compressive stress in TGO by about 50%. Subsequently, the number of micro-flaws, such as interface separations and micro-cracks in TGO in new TBCs, was significantly lower than that in TGO in in traditional TBCs. Secondly, a dense, crack-free TGO inhibited O/Al diffusion, avoiding the rapid oxidation.
关键词
热障涂层 /
双层黏结层 /
梯度热膨胀系数 /
高温氧化 /
TGO生长机理
Key words
thermal barrier coatings /
double bond coat /
gradient thermal expansion coefficient /
high temperature oxidation /
TGO growth mechanism
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参考文献
[1] ZHANG Z Y, XUE Z L, PARK Y, et al.High- Temperature Performance of Thermal Environmental Barrier Coatings in 90% H2O-10% O2 Conditions at 1 475 ℃[J]. Corrosion Science, 2023, 224: 111535.
[2] VAGGE S T, GHOGARE S.Thermal Barrier Coatings: Review[J]. Materials Today: Proceedings, 2022, 56: 1201-1216.
[3] LI Z, CHEN K Y, JIN T.Finite Element Simulations of the Thermomechanically Coupled Responses of Thermal Barrier Coating Systems Using an Unconditionally Stable Staggered Approach[J]. Applied Mathematical Modelling, 2025, 138: 115750.
[4] BOGDAN M, PETER I.A Comprehensive Understanding of Thermal Barrier Coatings (TBCS): Applications, Materials, Coating Design and Failure Mechanisms[J]. Metals, 2024, 14(5): 575.
[5] FU Y Y, YAO Z H, CHEN Y, et al.Progress in the Deposition Mechanisms and Key Performance Evaluation of Thermal Barrier Coatings for Turbine Blades: A Review[J]. Acta Metallurgica Sinica (English Letters), 2025, 38(2): 177-204.
[6] YANG M, WANG X Y, FENG W, et al.Effects of TGO Growth on the Interface Stress Distribution Based on 3D Pores in TBC Ceramics Layer[J]. Materials Today Communications, 2024, 38: 107878.
[7] 韩志勇, 卢博文, 王仕成. Ni-Al-Pt黏结层的制备及微观组织演变分析[J]. 材料导报, 2021, 35(4): 4144-4149.
HAN Z Y, LU B W, WANG S C.Preparation and Microstructure Evolution of Ni-Al-Pt Bond Coatings[J]. Materials Reports, 2021, 35(4): 4144-4149.
[8] THOUTAM A K, LI X H, KJELLMAN B, et al.Microstructure Influence on Functional Properties of HVOF Deposited NiCoCrAlY Bond Coat - SPS YSZ Topcoat Systems[J]. Surface and Coatings Technology, 2025, 508: 132157.
[9] JOUNAKI A, ANVARI S Z, TOROGHINEJAD M R, et al.Microstructural Evolution of Bi-Layered NiCrAlY/ CeO2 - Graphene Nanoplatelet Coatings by Air Plasma Spray and Spark Plasma Sintering[J]. Heliyon, 2025, 11(6): e42951.
[10] YANG K H, SHI J M, TIAN F Q, et al.Lanthanide Co-Doped YSZ Double-Ceramic-Layer Thermal Barrier Coatings: Unlocking Superior Sintering Resistance, Thermal Durability, and Insulation for Extreme Environments[J]. Surface and Coatings Technology, 2025, 504: 132069.
[11] GONG S K, ZHANG D B, XU H B, et al.Thermal Barrier Coatings with Two Layer Bond Coat on Intermetallic Compound Ni3Al Based Alloy[J]. Intermetallics, 2005, 13(3/4): 295-299.
[12] PENG H, GUO H B, HE J, et al.Oxidation and Diffusion Barrier Behaviors of Double-Layer NiCoCrAlY Coatings Produced by Plasma Activated EB-PVD[J]. Surface and Coatings Technology, 2011, 205(19): 4658-4664.
[13] ZHANG X W, MAO Q Z, YU Z F, et al.Multi-Layer Structure Improves Wear and Corrosion Resistance of Chromium[J]. Surface and Coatings Technology, 2025, 508: 132165.
[14] ZHOU X, XU Z H, MU R D, et al.Thermal Barrier Coatings with a Double-Layer Bond Coat on Ni3Al Based Single-Crystal Superalloy[J]. Journal of Alloys and Compounds, 2014, 591: 41-51.
[15] 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.
[16] 张晗, 刘轩溱, 黄爱辉, 等. 热障涂层金属黏结层制备与研究进展[J]. 中国腐蚀与防护学报, 2025, 45(1): 20-32.
ZHANG H, LIU X Z, HUANG A H, et al.Manufacturing and Research Progress in Metallic Bond Coats for Thermal Barrier Coatings[J]. Journal of Chinese Society for Corrosion and Protection, 2025, 45(1): 20-32.
[17] WANG Y Q, SAYRE G.Commercial Thermal Barrier Coatings with a Double-Layer Bond Coat on Turbine Vanes and the Process Repeatability[J]. Surface and Coatings Technology, 2009, 203(16): 2186-2192.
[18] 李霄, 彭芯钰, 张世虎, 等. 热障涂层双层黏结层的高温氧化行为[J]. 金属热处理, 2019, 44(1): 157-161.
LI X, PENG X Y, ZHANG S H, et al.High Temperature Oxidation Behavior of Double-Layer Bond Coat in Thermal Barrier Coating[J]. Heat Treatment of Metals, 2019, 44(1): 157-161.
[19] 刘嘉航,吕哲,徐振,等. NiAl 和 MCrAlY 热障涂层黏结层的成分设计与制备技术研究进展[J/OL]. 中国表面工程,2025, 1-26.
LIU J H, LYU Z, XU Z, et al.Research Progress in Composition design and preparation technology of NiAl and MCrAlY bond coats for thermal barrier coatings[J/OL]. China Surface Engineering, 2025, 1-26.
[20] 成波,王玉,楚倩倩,等. La2Zr2O7热障涂层中 Y2O3:Eu3+应力检测单元的高温稳定性及响应机制[J]. 中国有色金属学报,2023, 33(2): 455-467.
CHENG B, WANG Y, CHU Q Q, et al.High-Temperature Stability and Response Mechanism of Y2O3:Eu3+ Stress Sensing Units in La2Zr2O7 Thermal Barrier Coatings[J]. The Chinese Journal of Nonferrous Metals, 2023, 33(2): 455-467.
[21] 朱建国, 谢惠民, 刘战伟. 热障涂层力学性能的实验测试方法研究进展[J]. 力学学报, 2013, 45(1): 45-60.
ZHU J G, XIE H M, LIU Z W.Research Progress on the Experimental Measurement Methods of Mechanical Properties of Thermal Barrier Coatings[J]. Chinese Journal of Theoretical and Applied Mechanics, 2013, 45(1): 45-60.
[22] 温强, 李向成, 花银群, 等. 强流脉冲电子束表面改性技术及其在热障涂层改性中的研究进展[J]. 材料导报, 2025, 39(3): 180-190.
WEN Q, LI X C, HUA Y Q, et al.High-Current Pulsed Electron Beam Surface Modification Technology and Its Modifications in Thermal Barrier Coatings[J]. Materials Reports, 2025, 39(3): 180-190.
[23] 杨焜, 邓子谦, 牛少鹏, 等. 低压等离子喷涂CoNiCrAlY粉末颗粒沉积行为及涂层性能[J]. 中国表面工程, 2024, 37(5): 361-372.
YANG K, DENG Z Q, NIU S P, et al.Splat-Deposition Behavior and Coating Properties of Low-Pressure Plasma-Sprayed CoNiCrAlY Powder[J]. China Surface Engineering, 2024, 37(5): 361-372.
[24] 王志平, 费宇杰, 刘延宽. 热障涂层失效机理、改进方法及未来发展方向[J]. 表面技术, 2021, 50(7): 126-137.
WANG Z P, FEI Y J, LIU Y K. Failure Mechanism, Improvment Method and Future Development Direction of Thermal Barrier Coatings[J]. Surface Technology, 2021, 50(7): 126-137.
[25] 曾婧, 彭超群, 王日初, 等. 电子封装用金属基复合材料的研究进展[J]. 中国有色金属学报, 2015, 25(12): 3255-3270.
ZENG J, PENG C Q, WANG R C, et al.Research and Development of Metal Matrix Composites for Electronic Packaging[J]. The Chinese Journal of Nonferrous Metals, 2015, 25(12): 3255-3270.
[26] 刘雨薇, 李淳, 冯世钊, 等. 长寿命热障涂层失效机制、材料选择及结构设计研究进展[J]. 中国表面工程, 2024, 37(5): 220-237.
LIU Y W, LI C, FENG S Z, et al.Research Progress on Failure Mechanism, Material Selection and Structural Design of Long-Life Thermal Barrier Coatings[J]. China Surface Engineering, 2024, 37(5): 220-237.
[27] 刘德林, 薛齐齐, 杨文慧, 等. 热障涂层热力耦合条件下的应力仿真计算[J]. 材料工程, 2024, 52(7): 162-172.
LIU D L, XUE Q Q, YANG W H, et al.Stress Simulation Calculation of Thermal Barrier Coatings under Thermal- Mechanical Coupling Conditions[J]. Journal of Materials Engineering, 2024, 52(7): 162-172.
[28] 韩志勇, 丘珍珍, 史文新, 等. CoCrAlY表面改性后热障涂层高温氧化及热震性能[J]. 焊接学报, 2019, 40(6): 19-22.
HAN Z Y, QIU Z Z, SHI W X, et al.High Temperature Oxidation and Thermal Shock Properties of Thermal Barrier Coating by CoCrAlY Surface Modification[J]. Transactions of the China Welding Institution, 2019, 40(6): 19-22.
[29] 李佐君, 梁伟, 钟舜聪, 等. TGO及初始裂纹对热障涂层裂纹形核与扩展影响的有限元分析[J]. 失效分析与预防, 2021, 16(5): 300-308.
LI Z J, LIANG W, ZHONG S C, et al.Influence of TGO and Initial Crack on Crack Nucleation and Propagation in Thermal Barrier Coatings Based on Finite Element Analysis[J]. Failure Analysis and Prevention, 2021, 16(5): 300-308.
[30] 郝利军, 陆冠雄, 刘彻, 等. QT500表面等离子喷涂8YSZ热障涂层TGO的残余应力状态及数值分析[J]. 稀有金属材料与工程, 2015, 44(4): 1024-1029.
HAO L J, LU G X, LIU C, et al.State of Residual Stress and Numerical Analysis of TGO in Plasma Sprayed 8YSZ Thermal Barrier Coating on QT500[J]. Rare Metal Materials and Engineering, 2015, 44(4): 1024-1029.
[31] TORKASHVAND K, POURSAEIDI E, MOHAMMADI M, et al.Experimental and Numerical Study of TGO- Induced Stresses of Plasma-Sprayed Thermal Barrier Coating[J]. Materials Today Communications, 2023, 35: 105977.
[32] 王瑞涵, 花银群, 叶云霞, 等. 激光冲击金属黏结层高温热循环应力演化规律的有限元模拟[J]. 表面技术, 2024, 53(1): 123-134.
WANG R H, HUA Y Q, YE Y X, et al.Finite Element Simulation of the Stress Evolution of the Laser Shock Peening Metallic Bond Coat in High Temperature Thermal Cycles[J]. Surface Technology, 2024, 53(1): 123-134.
[33] TOLPYGO V K, DRYDEN J R, CLARKE D R.Determination of the Growth Stress and Strain in Α-Al2O3 Scales during the Oxidation of Fe-22Cr-4.8Al-0.3Y Alloy[J]. Acta Materialia, 1998, 46(3): 927-937.
[34] EVANS A G, MUMM D R, HUTCHINSON J W, et al.Mechanisms Controlling the Durability of Thermal Barrier Coatings[J]. Progress in Materials Science, 2001, 46(5): 505-553.
[35] 王者, 王志平, 丁坤英, 等. 某型航空发动机涡轮导向叶片热障涂层可靠性分析[J]. 航空学报, 2024, 45(22): 286-300.
WANG Z, WANG Z P, DING K Y, et al.Reliability Analysis of Thermal Barrier Coatings on Turbine Guide Vanes of a Certain Type of Aero-Engine[J]. Acta Aeronautica et Astronautica Sinica, 2024, 45(22): 286-300.
[36] 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.
[37] WANG L, YANG J S, NI J X, et al.Influence of Cracks in APS-TBCS on Stress around TGO during Thermal Cycling: A Numerical Simulation Study[J]. Surface and Coatings Technology, 2016, 285: 98-112.
[38] SCHLICHTING K W, PADTURE N P, JORDAN E H, et al.Failure Modes in Plasma-Sprayed Thermal Barrier Coatings[J]. Materials Science and Engineering: A, 2003, 342(1/2): 120-130.
[39] 周长海, 张一, 张秋明, 等. 影响热障涂层使用寿命因素的研究现状及展望[J]. 材料保护, 2012, 45(7): 44-48.
ZHOU C H, ZHANG Y, ZHANG Q M, et al.Current Status of Research on Factors Affecting the Lifetime of Thermal Barrier Coatings and Prospect[J]. Materials Protection, 2012, 45(7): 44-48.
[40] 董晓克, 张浩, 檀玉, 等. 燃气轮机热障涂层劣化的阻抗研究[J]. 材料保护, 2024, 57(7): 52-58.
DONG X K, ZHANG H, TAN Y, et al.Impedance Study of Thermal Barrier Coating Deterioration in Gas Turbines[J]. Materials Protection, 2024, 57(7): 52-58.
基金
国家自然科学基金（52474081）; 陕西省自然学科基金重点项目-关键核心技术攻关（2024CY-GJHX-39）; 西安市创新生态优化专项计划（科学家+工程师队伍建设项目,24KGDW0039）; 西安石油大学研究生创新基金（YCS23211007）
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