高温蒸汽环境下<strong>K444</strong>和<strong>K452</strong>合金及涂层的氧化行为

doi:10.11902/1005.4537.2025.120

中国腐蚀与防护学报

2026, Vol. 46

Issue (2): 500-510 CSTR: 32134.14.1005.4537.2025.120 DOI: 10.11902/1005.4537.2025.120

研究报告

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高温蒸汽环境下K444和K452合金及涂层的氧化行为

张超¹^,², 何闯³, 夏凯¹, 郭亭山³, 梁志远³(

)

^1.中国船舶集团有限公司第七〇三研究所哈尔滨 150078
^2.先进船舶发动机技术全国重点实验室哈尔滨 150078
^3.西安交通大学能源与动力工程学院西安 710049

Oxidation Behavior of K444 and K452 Alloys with and Without Thermal Barrier Coatings in High- temperature Steam Environment

ZHANG Chao¹^,², HE Chuang³, XIA Kai¹, GUO Tingshan³, LIANG Zhiyuan³(

)

^1.No. 703 Research Institute of CSSC, Harbin 150078, China
^2.National Key Laboratory of Advanced Marine Engine Technology, No. 703 Research Institute of CSSC, Harbin 150078, China
^3.School of Energy and Power Engineering, Xi'an Jiaotong University, Xi'an 710049, China

引用本文:

张超, 何闯, 夏凯, 郭亭山, 梁志远. 高温蒸汽环境下K444和K452合金及涂层的氧化行为[J]. 中国腐蚀与防护学报, 2026, 46(2): 500-510.
Chao ZHANG, Chuang HE, Kai XIA, Tingshan GUO, Zhiyuan LIANG. Oxidation Behavior of K444 and K452 Alloys with and Without Thermal Barrier Coatings in High- temperature Steam Environment[J]. Journal of Chinese Society for Corrosion and protection, 2026, 46(2): 500-510.

全文: PDF(21565 KB) HTML

摘要:

通过蒸汽氧化实验与热力学理论计算研究了K444、K452燃气轮机用典型高温合金在高温蒸汽中的氧化行为，并对K444和K452合金分别进行不同的表面涂层处理，分别为CoCrAlY和PtAl涂层材料。研究表明，在1000 ℃、含10% (体积分数) H₂O的空气中，PtAl涂层材料氧化增重遵循抛物线氧化规律，K444和K452合金及CoCrAlY涂层样品均出现失重现象。K444和K452合金表面形成了Al₂O₃、Cr₂O₃和TiO₂氧化物。4种样品的抗蒸汽氧化性能排序为：PtAl涂层> CoCrAlY涂层> K452合金> K444合金。两种涂层均能够提升材料的抗氧化性能，而PtAl涂层具有更优的抗蒸汽氧化性能。

关键词 ： K444和K452合金, 涂层, 燃烧工况, 蒸汽氧化

Abstract：

The oxidation behavior of two super-alloys K444 and K452 with and without two TBCs (thermal barrier coatings) PtAl bond coat + YSZ (Yttria-stabilized zirconia) top coat and CoCrAlY bond coat + YSZ top coat, respectively was studied in high-temperature steam, i.e. flowing air +10%H₂O at 1000 ℃ via intermittent weighing of mass, and thermodynamic theoretical calculation. Results show that the oxidation mass gain of the alloys with PtAl+YSZ followed the parabolic oxidation law, and K444, K452 alloys and the alloys with CoCrAlY + YSZ exhibited mass loss. Oxides Al₂O₃, Cr₂O₃ and TiO₂ were formed on the surface of K444 and K452 alloys. It follows that the anti-steam oxidation performance of the tested alloys and coatings may be ranked as follows: PtAl + YSZ coating/alloys > CoCrAlY + YSZ coating/alloys > K452 alloy > K444 alloy. The two coating systems can improve the anti-corrosion performance of the two alloys, however the PtAl+YSZ coating has better anti-steam corrosion performance.

Key words： K444 and K452 super-alloys coating combustion conditions steam oxidation

收稿日期: 2025-04-17 32134.14.1005.4537.2025.120

ZTFLH:

TG132

基金资助:创新工程(211-XXXX-N106-01-04);上海市市场监督管理局科技项目(2025KJ48)

通讯作者: 梁志远，E-mail：liangzy@xjtu.edu.cn，研究方向为材料环境行为

作者简介: 张超，男，1985年生，硕士

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https://www.jcscp.org/CN/10.11902/1005.4537.2025.120 或 https://www.jcscp.org/CN/Y2026/V46/I2/500

表1 K444和K452合金的化学成分 (mass fraction / %)

表2 涂层成分及热处理工艺

图1 高温蒸汽氧化实验系统图

图2 高温蒸汽环境下材料氧化增重曲线

图3 K444、K452合金和涂层材料分别氧化100、200 和300 h后的XRD谱

图4 K444合金在氧化100、200和300 h后氧化产物表面SEM形貌

表3 K444合金在氧化100、200和300 h后氧化产物表面点扫描结果 (mass fraction / %)

图5 K452合金氧化100、200和300 h后的氧化产物表面SEM形貌

表4 K452合金氧化100、200和300 h后氧化产物表面EDS元素分析结果 (mass fraction / %)

图6 K444合金的涂层样品在氧化100、200和300 h后氧化产物表面SEM形貌

表5 K444合金涂层样品在氧化100、200和300 h后氧化产物表面EDS元素分析结果 (mass fraction / %)

图7 涂覆CoCrAlY涂层的K452合金样品在氧化100、200和300 h后表面SEM形貌。

表6 K452合金的涂层样品氧化100、200和300 h后氧化产物表面EDS元素分析结果 (mass fraction / %)

图8 K444、K452合金和涂层样品氧化300 h后的氧化产物断面的SEM形貌及EDS分析结果

表7 1000 ℃下金属和H2O反应的Gibbs自由能(ΔG)

No.	Reaction equation	P $O 2$ / Pa
1	2Ni + O₂ (g) = 2NiO	4.54 × 10^-6
2	4/3Cr+O₂ (g) = 2/3Cr₂O₃	1.36 × 10^-17
3	Ti + O₂ (g) = TiO₂	4.85 × 10^-25
4	4/3Al + O₂ (g) = 2/3Al₂O₃	1.73 × 10^-30

表8 1000 ℃反应下金属氧化平衡氧分压

图9 1000 ℃下Ni-Cr-Ti-H-O体系的热力学相图

图10 1000 ℃下水分子在Cr原子表面的吸附过程

图11 1000 ℃合金在H2O中的氧化机理

[1]	Kubik M L, Coker P J, Barlow J F. Increasing thermal plant flexibility in a high renewables power system [J]. Appl. Energy, 2015, 154: 102
[2]	Yin S Y, Zhang S F, Andrews-Speed P, et al. Economic and environmental effects of peak regulation using coal-fired power for the priority dispatch of wind power in China [J]. J. Cleaner Prod., 2017, 162: 361
[3]	Eaton-Mckay J, Yan K, Zhong X, et al. Oxidation and carburization behaviour of two type 316H stainless steel casts in simulated AGR gas environment at 550 and 600 ℃ [J]. J. Nucl. Mater., 2021, 552: 152999
[4]	Tian S Y, Zhu Z J, Jiang J, et al. Research and development status and the latest technological progress of hydrogen fuel gas turbine research [J]. Energy Res. Manag., 2021, (4): 10
[4]	田书耘, 朱志劼, 蒋俊等. 氢燃料燃气轮机研发现状和最新技术进展 [J]. 能源研究与管理, 2021, (4): 10
[5]	Brittan A, Mahaffey J, Anderson M. Corrosion and mechanical performance of Grade 92 Ferritic-Martensitic Steel after exposure to supercritical carbon dioxide [J]. Metall. Mater. Trans., 2020, 51A: 2564
[6]	Yin K J, Qiu S Y, Tang R, et al. Characterization of the porosity of the oxide scales on ferritic-martensitic steel P91 and P92 exposed in supercritical water [J]. J. Chin. Soc. Corros. Prot., 2010, 30: 1
[6]	尹开锯, 邱绍宇, 唐睿等. 铁素体-马氏体钢P91和P92在超临界水中腐蚀后氧化膜多孔性分析 [J]. 中国腐蚀与防护学报, 2010, 30: 1
[7]	Chen K, Zhang L F, Shen Z. Understanding the surface oxide evolution of T91 ferritic-martensitic steel in supercritical water through advanced characterization [J]. Acta Mater., 2020, 194: 156
[8]	Lu J T, Gu Y F. High-temperature steam oxidation behavior of alloys used for key parts of the power plant boiler [J]. J. Chin. Soc. Corros. Prot., 2014, 34: 19
[8]	鲁金涛, 谷月峰. 电站锅炉关键部件材料高温蒸汽氧化研究进展 [J]. 中国腐蚀与防护学报, 2014, 34: 19
[9]	Viswanathan R, Sarver J, Tanzosh J M. Boiler materials for ultra-supercritical coal power plants-steamside oxidation [J]. J. Mater. Eng. Perform., 2006, 15: 255
[10]	Guo J F, Cao T S, Cheng C Q, et al. Effect of carburization (pyrolysis furnace tube main failure factor) on the microstructure and properties of HPNb alloy tube [J]. Eng. Failure Anal., 2020, 115: 104610
[11]	Dryepondt S N, Lehmusto J, Pint B A. Effect of annealing and supercritical CO₂ exposure at 750 ℃ on the tensile properties of stainless steel and Ni‐based structural alloys [J]. Mater. Corros., 2021, 73: 497
[12]	Fujii C T, Meussner R A. The mechanism of the high-temperature oxidation of iron-chromium alloys in water vapor [J]. J. Electrochem. Soc., 1964, 111: 1215
[13]	Shen J N, Zhou L J, Li T F. High-temperature oxidation of Fe-Cr alloys in wet oxygen [J]. Oxid. Met., 1997, 48: 347
[14]	Rapp R A. The high-temperature oxidation of metals forming cation-diffusion scale [J]. Metall. Trans., 1984, 15A: 765
[15]	Asteman H, Svensson J E, Johansson L G, et al. Indication of chromium oxide hydroxide evaporation during oxidation of 304L at 873 K in the presence of 10% water vapor [J]. Oxid. Met., 1999, 52: 95
[16]	Panicaud B, Grosseau-Poussard J L, Dinhut J F. General approach on the growth strain versus viscoplastic relaxation during oxidation of metals [J]. Comput. Mater. Sci., 2008, 42: 286
[17]	Zhang W, Smith J R, Evans A G. The connection between ab initio calculations and interface adhesion measurements on metal/oxide systems: Ni/Al₂O₃ and Cu/Al₂O₃ [J]. Acta Mater., 2002, 50: 3803
[18]	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 Mater., 1998, 46: 927
[19]	Suo Y H, Yang X X, Shen S P. Residual stress analysis due to chemomechanical coupled effect, Intrinsic strain and creep deformation during oxidation [J]. Oxid. Met., 2015, 84: 413
[20]	Evans H E, Huntz A M. Methods of measuring oxidation growth stresses [J]. Mater. High Temp., 1994, 12: 111
[21]	Saunders S R J, Monteiro M, Rizzo F. The oxidation behaviour of metals and alloys at high temperatures in atmospheres containing water vapour: A review [J]. Prog. Mater. Sci., 2008, 53: 775
[22]	Meschter P J, Opila E J, Jacobson N S. Water vapor-mediated volatilization of high-temperature materials [J]. Annu. Rev. Mater. Res., 2013, 43: 559
[23]	Liang Z Y, Xu Y M, Wang S, et al. Corrosion behavior of heat-resistant alloys in high temperature CO₂ environment [J]. J. Chin. Soc. Corros. Prot., 2022, 42: 613
[23]	梁志远, 徐一鸣, 王硕等. 高等级合金CO₂环境下的腐蚀行为研究 [J]. 中国腐蚀与防护学报, 2022, 42: 613
[24]	Pint B A, Brese R G, Keiser J R. Effect of pressure on supercritical CO₂ compatibility of structural alloys at 750 ℃ [J]. Mater. Corros., 2017, 68: 151
[25]	Wang L, Liu C Y, Han Z Y, et al. Hot corrosion behavior and evaluation of turbine components and materials used for gas turbine engine [J]. J. Chin. Soc. Corros. Prot., 2011, 31: 399
[25]	王理, 刘春阳, 韩振宇等. 燃气轮机涡轮零部件及材料热腐蚀行为与评价方法研究 [J]. 中国腐蚀与防护学报, 2011, 31: 399
[26]	Parthiban K, Bysakh S, Ghosh S. Novel oxide based anti-corrosion composite coating for gas turbines [J]. Surf. Coat. Technol., 2024, 484: 130822
[27]	Li Z, Taheri M, Torkamany P, et al. Laser cladding of NiCrCoFeNb-Mo _X high-entropy alloy to increase resistance to corrosion of gas turbine blades [J]. Vacuum, 2024, 219: 112749

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