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金属学报  2025, Vol. 61 Issue (7): 1049-1059    DOI: 10.11900/0412.1961.2023.00275
  研究论文 本期目录 | 过刊浏览 |
一种低成本第三代单晶高温合金的高温氧化行为
李永梅1,2, 谭子昊1,2, 王新广2(), 陶稀鹏2, 杨彦红2, 刘纪德2, 刘金来2, 李金国2, 周亦胄2, 孙晓峰2()
1 中国科学技术大学 材料科学与工程学院 沈阳 110016
2 中国科学院金属研究所 师昌绪先进材料创新中心 沈阳 110016
Oxidation Behavior of a Low-Cost Third-Generation Ni-Based Single-Crystal Superalloy
LI Yongmei1,2, TAN Zihao1,2, WANG Xinguang2(), TAO Xipeng2, YANG Yanhong2, LIU Jide2, LIU Jinlai2, LI Jinguo2, ZHOU Yizhou2, SUN Xiaofeng2()
1 School of Materials Science and Engineering, University of Science and Technology of China, Shenyang 110016, China
2 Shi -changxu Innovation Center for Advanced Materials, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
引用本文:

李永梅, 谭子昊, 王新广, 陶稀鹏, 杨彦红, 刘纪德, 刘金来, 李金国, 周亦胄, 孙晓峰. 一种低成本第三代单晶高温合金的高温氧化行为[J]. 金属学报, 2025, 61(7): 1049-1059.
Yongmei LI, Zihao TAN, Xinguang WANG, Xipeng TAO, Yanhong YANG, Jide LIU, Jinlai LIU, Jinguo LI, Yizhou ZHOU, Xiaofeng SUN. Oxidation Behavior of a Low-Cost Third-Generation Ni-Based Single-Crystal Superalloy[J]. Acta Metall Sin, 2025, 61(7): 1049-1059.

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摘要: 

为了应对先进航空发动机中材料研发成本大幅攀升的实际问题,亟需研发新型低成本高性能的镍基单晶高温合金。本工作以一种仅含3%Re (质量分数)的新型低成本第三代镍基单晶高温合金为研究对象,分析该合金1120 ℃高温下的氧化动力学行为与γ′相退化规律。结果表明:氧化前5 h,样品表面形成连续且均匀的三层氧化膜结构,此时氧化膜较薄(厚度仅约5 µm),合金的氧化增重遵循次抛物线动力学规律;氧化10~100 h,Al2O3层间裂纹的萌生与扩展加速表面保护性氧化膜的剥落,导致样品内部的氧化加剧,反应形成AlN以及大面积的氧化反应区(ORD),合金的氧化增重遵循线性动力学规律;氧化150 h后,ORD底部形成连续且曲折的Al2O3层,有效阻碍合金元素与O元素的扩散,并随着Al2O3层的增厚,合金的氧化增重逐渐接近抛物线动力学规律。此外,样品表面的高温氧化反应会加速合金中近表面γ′相的退化以及有害TCP相的析出。合金表面氧化膜与基体之间结合强度不足,是该基础合金非连续氧化条件下抗氧化性能低于连续氧化条件下的主要原因。

关键词 镍基单晶高温合金高温氧化氧化层剥落氧化动力学γ′相退化    
Abstract

At present, the development of low-cost Ni-based single-crystal (SX) superalloys with excellent properties is urgently needed to address the increasing cost of advanced aero-engines. In this study, a novel low-cost, third-generation Ni-based SX superalloy containing 3%Re (mass fraction) was investigated to assess its oxidation behavior and γ′ phase degradation at 1120 oC. Results showed that during the first 5 h of oxidation, a continuous and uniform three-layer oxide film was formed on the surface of samples. Given the relatively thin oxide film, measured at approximately 5 μm, the experimental alloy followed sub-parabolic kinetics. Between 10 and 100 h of oxidation, the nucleation and propagation of cracks in the Al2O3 interlayer accelerated the spallation of protective oxide films. This event resulted in the increased oxidation of the matrix alloy, along with the formation of AlN and large areas in the oxidation reaction domain (ORD). These phenomena caused the transformation from sub-parabolic kinetics to linear kinetics. After 150 h of oxidation, a continuous and zigzagging Al2O3 layer was formed at the bottom of the ORD that could hinder the outward diffusion of alloy elements and the inward diffusion of oxygen. Consequently, the alloy gradually approached parabolic kinetics as the Al2O3 layer was thickened. In addition, the intense oxidation reaction on the surface accelerated the degradation of the γ′ phase and the precipitation of the topologically close pack phase near the surface. Therefore, the low bond strength between the surface oxide film and the alloy matrix primarily contributed to the deficiency of high-temperature oxidation resistance of this experimental alloy.

Key wordsNi-based single-crystal superalloy    oxidation    scale spallation    kinetic behavior    γ′ degradation
收稿日期: 2023-07-03     
ZTFLH:  TG132.32  
基金资助:辽宁省优秀青年基金项目(2021-YQ-02);沈阳市中青年科技创新人才支持计划项目(RC220440)
通讯作者: 王新广,xgwang11b@imr.ac.cn,主要从事镍基单晶高温合金研发与应用研究
孙晓峰,xfsun@imr.ac.cn,主要从事铸造高温合金研发与工程化应用研究
作者简介: 李永梅,女,1998年生,硕士生
图1  标准热处理工艺流程图
图2  合金在1120 ℃下氧化10和200 h的氧化增重曲线
图3  合金经1120 ℃氧化不同时间后氧化产物的XRD谱
图4  合金经1120 ℃氧化不同时间后样品表面宏观形貌与氧化产物SEM像
Oxidation productONiAlCrCoTaWMo
NiO59.2637.64--3.10---
Spinel A152.8017.1520.845.273.94---
Spinel A260.168.0914.6811.925.99---
(Ni, Co)(W, Mo)O465.5015.40-1.731.251.0015.11-
Spinel B72.0014.200.802.852.8972.00--
表1  样品表面氧化产物的EPMA化学成分分析 (atomic fraction / %)
图5  合金经1120 ℃氧化不同时间后样品纵截面的氧化层结构演化
Oxidation productLabelNONiAlCrCoTaWMoRe
(Ni, Co)(W, Mo)O4A-66.6514.240.621.072.712.5210.451.7066.65
NiOB-47.9846.810.530.454.14----
(Ni, Co)(Al, Cr)2O4C-57.7512.0224.271.853.230.80---
Re-richD-45.68-4.561.13--4.246.6837.55
Al2O3E1-61.772.2534.370.820.66----
Al2O3E2-71.27-27.82------
AlNF33.63-28.0048.140.991.73-0.42--
表2  样品纵截面氧化产物的EPMA化学成分分析 (atomic fraction / %)
图6  合金经1120 ℃氧化不同时间后近贫Al层20~40 µm区域与样品表面2 mm区域(样品内部)的组织演变
图7  合金经1120 ℃氧化200 h的氧化动力学曲线
Alloy

Temperature

oC

Time

h

kp

g2·cm-4·s-1

Alloy

Temperature

oC

Time

h

kp

g2·cm-4·s-1

Experimental11200-404.67 × 10-102[8]11000-59.44 × 10-13
60-2003.28 × 10-920-2001.95 × 10-12
1[20]11000-255.50 × 10-123[9]11000-1007.22 × 10-13
50-1008.06 × 10-124[21]11000-162.76 × 10-10
130-2002.77 × 10-1220-1003.14 × 10-11
表3  本实验合金与其他合金[8,9,20,21]的抛物线氧化速率常数统计
AlloyAlTaCrCoMoWReYCNi
1[20]6.04.04.59.01.88.54.00.0030.15Bal.
2[8]6.3*6*10****
3[9]5.76.75.39.008.02.000Bal.
4[21]7.132.207010.050Bal.
表4  4种合金[8,9,20,21]的参考合金成分 (mass fraction / %)
图8  合金在1120 ℃条件下的氧化机理示意图
图9  合金1150 ℃连续氧化增重曲线与合金经1120 ℃非连续氧化100 h后的剥落氧化皮形貌
1 Caron P, Khan T. Evolution of Ni-based superalloys for single crystal gas turbine blade applications [J]. Aerosp. Sci. Technol., 1999, 3: 513
2 Tan Z H, Wang X G, Song W, et al. Oxidation behavior of a novel nickel-based single crystal superalloy at elevated temperature [J]. Vacuum, 2000, 175: 109284
3 Xiao J H, Xiong Y, Wang L, et al. Oxidation behavior of high Hf nickel-based superalloy in air at 900, 1000 and 1100 oC [J]. Int. J. Miner. Metall. Mater., 2021, 28: 1957
4 Liu C T, Ma J, Sun X F, et al. Mechanism of the oxidation and degradation of the aluminide coating on the nickel-base single-crystal superalloy DD32M [J]. Surf. Coat. Technol., 2010, 204: 3641
5 Pfennig A, Fedelich B. Oxidation of single crystal PWA 1483 at 950 oC in flowing air [J]. Corros. Sci., 2008, 50: 2484
6 Li M H, Sun X F, Li J G, et al. Oxidation behavior of a single-crystal Ni-base superalloy in Air. I: At 800 and 900 oC [J]. Oxid. Met., 2003, 59: 591
7 Ma J X, Jiang W X, Wang J, et al. Initial oxidation behavior of a single crystal superalloy during stress at 1150 oC [J]. Sci. Rep., 2020, 10: 3089
8 Li M H, Sun X F, Jin T, et al. Oxidation behavior of a single-crystal Ni-base superalloy in Air—II: At 1000, 1100, and 1150 oC [J]. Oxid. Met., 2003, 60: 195
9 Li P, Jin X C, Zhao J C, et al. Oxidation behaviors and compressive strength evolution of DD6 Ni-based single-crystal superalloy at 1100 oC [J]. Corros. Sci., 2022, 208: 110684
10 Brumm M W, Grabke H J. The oxidation behaviour of NiAl—I. Phase transformations in the alumina scale during oxidation of NiAl and NiAlCr alloys [J]. Corros. Sci., 1992, 33: 1677
11 Smialek J L, Garg A, Gabb P T, et al. Cyclic oxidation of high Mo, reduced density superalloys [J]. Metals, 2015, 5: 2165
12 Hu Y B, Cheng C Q, Cao T S, et al. A study on the multiple stages of oxidation kinetics in a single crystal nickel-based superalloy [J]. Corros. Sci., 2021, 188: 109512
13 Akhtar A, Hook M S, Reed R C. On the oxidation of the third-generation single-crystal superalloy CMSX-10 [J]. Metall. Mater. Trans., 2005, 36A: 3001
14 Mallikarjuna H T, Richards N L, Caley W F. Effect of alloying elements and microstructure on the cyclic oxidation performance of three nickel-based superalloys [J]. Materialia, 2018, 4: 487
15 Wang X G, Li J R, Shi Z X, et al. Effect of W content on oxidation resistance of experimental third generation single crystal superalloys [J]. Rare Met. Mater. Eng., 2017, 46: 2493
15 王效光, 李嘉荣, 史振学 等. W对第三代单晶高温合金抗氧化性能的影响 [J]. 稀有金属材料与工程, 2017, 46: 2493
16 Liu C T, Sun X F, Guan H R, et al. Effect of rhenium addition to a nickel-base single crystal superalloy on isothermal oxidation of the aluminide coating [J]. Surf. Coat. Technol., 2005, 194: 111
17 Wang B, Zhang J, Pan X J, et al. Effects of W on microstructural stability of the third generation Ni-based single crystal superalloys [J]. Acta Metall. Sin., 2017, 53: 298
doi: 10.11900/0412.1961.2016.00379
17 王 博, 张 军, 潘雪娇 等. W对第三代镍基单晶高温合金组织稳定性的影响 [J]. 金属学报, 2017, 53: 298
18 Zhang J, Wang L, Wang D, et al. Recent progress in research and development of nickel-based single crystal superalloys [J]. Acta Metall. Sin., 2019, 55: 1077
18 张 健, 王 莉, 王 栋 等. 镍基单晶高温合金的研发进展 [J]. 金属学报, 2019, 55: 1077
19 Li Y M, Wang X G, Tan Z H, et al. On dislocation networks and superdislocations in Re-containing nickel-based SX superalloy under different creep conditions [J]. Intermetallics, 2022, 148: 107646
20 Huang L, Sun X F, Guan H R, et al. Effect of rhenium addition on isothermal oxidation behavior of single-crystal Ni-based superalloy [J]. Surf. Coat. Technol., 2006, 200: 6863
21 Qin L, Pei Y L, Li S S, et al. Role of volatilization of molybdenum oxides during the cyclic oxidation of high-Mo containing Ni-based single crystal superalloys [J]. Corros. Sci. 2017, 129: 192
22 Park S J, Seo S M, Yoo Y S, et al. Statistical study of the effects of the composition on the oxidation resistance of Ni-based superalloys [J]. J. Nanomater., 2015, 2015: 929546
23 Liu L D, Ding B, Ren W L, et al. Multilayer structure of DZ445 Ni-based superalloy formed by long time oxidation at high temperature [J]. Acta Metall. Sin., 2023, 59: 387
doi: 10.11900/0412.1961.2021.00482
23 刘来娣, 丁 彪, 任维丽 等. DZ445镍基高温合金高温长时间氧化形成的多层膜结构 [J]. 金属学报, 2023, 59: 387
doi: 10.11900/0412.1961.2021.00482
24 Ding Q Q, Shen Z J, Xiang S S, et al. In-situ environmental TEM study of γ′-γ phase transformation induced by oxidation in a nickel-based single crystal superalloy [J]. J. Alloys Compd., 2015, 651: 255
25 Birks N, Meier G H, Pettit F S. Introduction to the High-Temperature Oxidation of Metals [M]. Cambridge: Cambridge University Press, 2006: 1
26 Perez T, Monceau D, Desgranges C. Kinetic oxidation model including the transient regime for a single crystal nickel-based superalloy over the temperature range 750-1300 oC [J]. Corros. Sci., 2022, 206: 110485
27 Hindam H M, Smeltzer W W. Growth and microstructure of α‐Al2O3 on Ni-Al alloys: Internal precipitation and transition to external scale [J]. J. Electrochem. Soc., 1980, 127: 1622
28 Hu Y B, Cheng C Q, Zhang L, et al. Microstructural evolution of oxidation film on a single crystal nickel-based superalloy at 980 oC [J]. Oxid. Met., 2018, 89: 303
29 Sato A, Chiu Y L, Reed R C. Oxidation of nickel-based single-crystal superalloys for industrial gas turbine applications [J]. Acta Mater., 2011, 59: 225
30 Rehman K, Sheng N C, Fan S G, et al. Improved spallation resistance of the oxide scale by Hf/Y Co-doping in Ni-based superalloy at high temperature [J]. Acta Metall. Sin. (Engl. Lett.), 2022, 35: 1744
31 Zhao Y S, Zhang J, Luo Y S, et al. Effects of Hf on high temperature low stress rupture properties of a second generation Ni-based single crystal superalloy DD11 [J]. Acta Metall. Sin., 2015, 51: 1261
doi: 10.11900/0412.1961.2015.00363
31 赵云松, 张 剑, 骆宇时 等. Hf对第二代镍基单晶高温合金DD11高温低应力持久性能的影响 [J]. 金属学报, 2015, 51: 1261
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