放电等离子烧结<strong>Ni20Cr-<i>x</i>Al</strong>合金的高温氧化行为

doi:10.11900/0412.1961.2022.00240

金属学报

2024, Vol. 60

Issue (4): 485-494 DOI: 10.11900/0412.1961.2022.00240

研究论文

本期目录 | 过刊浏览

放电等离子烧结Ni20Cr-xAl合金的高温氧化行为

刘丞济, 孙文瑶(

), 陈明辉, 王福会

东北大学沈阳材料科学国家研究中心东北大学联合研究分部沈阳 110819

High-Temperature Oxidation Behavior of Spark Plasma Sintered Ni20Cr-xAl Alloys

LIU Chengji, SUN Wenyao(

), CHEN Minghui, WANG Fuhui

Shenyang National Laboratory for Materials Science, Northeastern University, Shenyang 110819, China

引用本文:

刘丞济, 孙文瑶, 陈明辉, 王福会. 放电等离子烧结Ni20Cr-xAl合金的高温氧化行为[J]. 金属学报, 2024, 60(4): 485-494.
Chengji LIU, Wenyao SUN, Minghui CHEN, Fuhui WANG. High-Temperature Oxidation Behavior of Spark Plasma Sintered Ni20Cr-xAl Alloys[J]. Acta Metall Sin, 2024, 60(4): 485-494.

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摘要:

高温氧化是限制镍基高温合金服役寿命的主要因素之一。本工作旨在通过调控Al含量来提升Ni20Cr合金的抗氧化性能。采用机械合金化(MA)和放电等离子烧结(SPS)的方法制备了Al含量(质量分数)分别为1.5%、3.0%、5.0%的Ni20Cr-xAl合金，对比研究了SPS制备合金与相同成分铸态合金在900℃空气中的高温氧化行为。结果表明，SPS制备合金成分、组织均匀且晶粒细小，大量晶界显著加速了元素的扩散，在Al含量为1.5%时，Al内氧化严重，Cr快速外氧化生成含有大量孔隙和裂纹的Cr₂O₃膜，而在Al含量为3.0%和5.0%时，形成了保护性的连续致密的α-Al₂O₃薄膜，合金内部弥散的Al₂O₃颗粒为外Al₂O₃膜提供了形核位点并起到了钉扎作用，因此2者表现出优异的抗氧化性能，氧化速率分别为1.06 × 10^-7和4.92 × 10^-8 mg²/(cm⁴·s)。铸态合金都发生了内氧化，而且无法形成连续的外Al₂O₃膜，氧化膜的主要成分为疏松多孔的Cr₂O₃，因而氧化速率快且发生了氧化膜开裂和剥落。

关键词 ：高温合金, 细晶结构, 高温氧化, 放电等离子烧结

Abstract：

As a high-performance structural material, nickel-based superalloy has excellent comprehensive properties, such as high-temperature mechanical properties, thermal stability, and corrosion resistance. It is widely used in hot-end parts, including the combustion chamber, turbine blades, and turbine disks, among others. Due to severe working environments, oxidation has become a major life-limiting factor for the nickel-based superalloy. However, the high-temperature oxidation behavior of a superalloy is complex, related to many factors, such as chemical composition and preparation technology. Many advances have been achieved through improving alloy compositions to meet the anti-oxidation requirements, and others have been accomplished using major innovations in processing. As a new powder metallurgy technology, spark plasma sintering (SPS) has the advantages of a fast heating rate, low sintering temperature, and short sintering time. However, there are few studies on the oxidation behavior of alloys prepared by this technology. In this study, Ni20Cr-xAl alloys with Al content (mass fraction) of 1.5%, 3.0%, and 5.0% were prepared by mechanical alloying and SPS. Oxidation kinetics, XRD, SEM, and TEM were used to compare and investigate the isothermal oxidation behaviors of the SPSed and the as-cast alloys with the same composition in air at 900^oC. Results indicate that the SPSed alloys have uniform microstructures and fine grains, and abundant grain boundaries significantly accelerate the diffusion of elements. When the Al content is 1.5%, severe internal oxidation of Al occurs, and a Cr₂O₃ scale containing large pores and cracks is formed due to rapid external oxidation of Cr. Al₂O₃ particles dispersed in the alloy serve as nucleation sites for the exterior Al₂O₃ scale and have a pinning effect. However, when the Al content reaches 3.0% and 5.0%, a protective, continuous, and dense α-Al₂O₃ thin scale emerges. Therefore, both alloys display excellent oxidation resistance, the oxidation weight gain is 0.25 and 0.20 mg/cm², respectively, and the corresponding oxidation rate is 1.06 × 10^-7 and 4.92 × 10^-8 mg²/(cm⁴·s). Internal oxidation occurs in all the as-cast alloys, and no continuous external Al₂O₃ scale can be formed. The main component of the oxide scales is porous Cr₂O₃, which results in high oxidation rates and crack and spallation of the oxide scales.

Key words： superalloy fine-grain structure high-temperature oxidation spark plasma sintering

收稿日期: 2022-05-12

ZTFLH:

TG178

基金资助:国家自然科学基金项目(51871051);中国博士后科学基金项目(2022M720678)

通讯作者: 孙文瑶，sunwenyao@mail.neu.edu.cn，主要从事金属的高温氧化与防护研究

Corresponding author: SUN Wenyao, associate professor, Tel: 17824032549, E-mail: sunwenyao@mail.neu.edu.cn

作者简介: 刘丞济，女，1997年生，博士生

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图1 放电等离子烧结(SPS)制备Ni20Cr-xAl合金微观组织的SEM像

图2 SPS制备Ni20Cr-xAl合金的XRD谱

图3 SPS制备Ni20Cr-xAl合金的EBSD像和晶粒尺寸分布图

图4 SPS制备Ni20Cr-3.0Al合金的TEM像和元素面扫图

图5 铸态和SPS制备Ni20Cr-xAl合金在900℃恒温氧化100 h的动力学曲线

表1 铸态和SPS制备Ni20Cr-xAl合金在900℃恒温氧化100 h的氧化增重(Δw)和氧化速率常数(kp)

图6 铸态和SPS制备Ni20Cr-xAl合金在900℃恒温氧化100 h后的XRD谱

图7 铸态和SPS制备Ni20Cr-xAl合金在900℃恒温氧化20 h后表面形貌的SEM像

图8 铸态和SPS制备Ni20Cr-xAl合金在900℃恒温氧化100 h后表面形貌的SEM像

图9 铸态Ni20Cr-xAl合金在900℃恒温氧化100 h后局部截面的SEM像和元素面扫图

图10 SPS制备Ni20Cr-xAl合金在900℃恒温氧化100 h后局部截面形貌的SEM像和元素面扫图

图11 SPS制备Ni20Cr-5.0Al合金在900℃恒温氧化100 h后氧化膜的TEM像和晶粒1、晶粒2的选区电子衍射花样

1	Yancheshmeh D A, Esmailian M, Shirvani K. Microstructural and oxidation behavior of NiCrAl super alloy containing hafnium at high temperature[J]. Int. J. Hydrogen Energy, 2018, 43: 5365 doi: 10.1016/j.ijhydene.2017.08.039
2	Llewelyn S C H, Chater R J, Jones N G, et al. The effect of systematic variation of Ni:Co ratio on the oxidation behaviour of γ-γ′ Ni-Co-Al-Ti-Cr alloys[J]. Corros. Sci., 2021, 178: 109087 doi: 10.1016/j.corsci.2020.109087
3	Ju J, Shen Z, Kang M D, et al. On the preferential grain boundary oxidation of a Ni-Co-based superalloy[J]. Corros. Sci., 2022, 199: 110203 doi: 10.1016/j.corsci.2022.110203
4	Wang J, Wang L Z, Li J Q, et al. Effects of aluminum and titanium additions on the formation of nonmetallic inclusions in nickel-based superalloys[J]. J. Alloys Compd., 2022, 906: 164281 doi: 10.1016/j.jallcom.2022.164281
5	Hobbs R A, Zhang L, Rae C M F, et al. The effect of ruthenium on the intermediate to high temperature creep response of high refractory content single crystal nickel-base superalloys[J]. Mater. Sci. Eng., 2008, A489: 65
6	Zhai Y D, Chen Y H, Zhao Y S, et al. Initial oxidation of Ni-based superalloy and its dynamic microscopic mechanisms: The interface junction initiated outwards oxidation[J]. Acta Mater., 2021, 215: 116991 doi: 10.1016/j.actamat.2021.116991
7	Sun W Y, Chen M H, Bao Z B, et al. Breakaway oxidation of a low-Al content nanocrystalline coating at 1000^oC[J]. Surf. Coat. Technol., 2019, 358: 958 doi: 10.1016/j.surfcoat.2018.12.034
8	Fu L B, Zhang W L, Li S M, et al. Oxidation behavior of NiCrAlYSi coatings with Re-based diffusion barriers on two superalloys[J]. Corros. Sci., 2022, 198: 110096 doi: 10.1016/j.corsci.2022.110096
9	Ye X J, Yang B B, Nie Y, et al. Influence of Nb addition on the oxidation behavior of novel Ni-base superalloy[J]. Corros. Sci., 2021, 185: 109436 doi: 10.1016/j.corsci.2021.109436
10	Sun X Y, Zhang L F, Pan Y M, et al. Microstructural evolution during cyclic oxidation of a Ni-based singe crystal superalloy at 1100^oC[J]. Corros. Sci., 2020, 162: 108216 doi: 10.1016/j.corsci.2019.108216
11	Yu S Y, Zhan X, Liu F, et al. 900°C oxidation resistance of Ni-base superalloys alloyed with different refractory elements[J]. J. Alloys Compd., 2022, 904: 164071 doi: 10.1016/j.jallcom.2022.164071
12	Zhang Y Y, Wu H B, Yu X P, et al. Role of Cr in the high-temperature oxidation behavior of Cr _x MnFeNi high-entropy alloys at 800^oC in air[J]. Corros. Sci., 2022, 200: 110211 doi: 10.1016/j.corsci.2022.110211
13	Brumm M W, Grabke H J. The oxidation behaviour of NiAl-I. Phase transformations in the alumina scale during oxidation of NiAl and NiAl-Cr alloys[J]. Corros. Sci., 1992, 33: 1677 doi: 10.1016/0010-938X(92)90002-K
14	Ul-Hamid A. A TEM study of the oxide scale development in Ni-Cr-Al alloys[J]. Corros. Sci., 2004, 46: 27 doi: 10.1016/S0010-938X(03)00100-8
15	Yu Y, Cai X P, Jiao X Y, et al. Oxidation resistance at 900^oC of porous Ni-Al-Cr intermetallics synthesized via rapid thermal explosion reaction[J]. J. Alloys Compd., 2022, 906: 164374 doi: 10.1016/j.jallcom.2022.164374
16	Nijdam T J, Jeurgens L P H, Sloof W G. Promoting exclusive α-Al₂O₃ growth upon high-temperature oxidation of NiCrAl alloys: Experiment versus model predictions[J]. Acta Mater., 2005, 53: 1643 doi: 10.1016/j.actamat.2004.12.014
17	Chyrkin A, Pillai R, Galiullin T, et al. External α-Al₂O₃ scale on Ni-base alloy 602 CA-Part I: Formation and long-term stability[J]. Corros. Sci., 2017, 124: 138 doi: 10.1016/j.corsci.2017.05.017
18	Ismail F B, Vorontsov V A, Lindley T C, et al. Alloying effects on oxidation mechanisms in polycrystalline Co-Ni base superalloys[J]. Corros. Sci., 2017, 116: 44 doi: 10.1016/j.corsci.2016.12.009
19	Wagner C. Theoretical analysis of the diffusion processes determining the oxidation rate of alloys[J]. J. Electrochem. Soc., 1952, 99: 369 doi: 10.1149/1.2779605
20	Ko Y S, Kim B K, Jung W S, et al. Effect of the microstructure of Haynes 282 nickel-based superalloys on oxidation behavior under oxy-fuel combustion conditions[J]. Corros. Sci., 2022, 198: 110110 doi: 10.1016/j.corsci.2022.110110
21	Sasaki T T, Ohkubo T, Hono K. Microstructure and mechanical properties of bulk nanocrystalline Al-Fe alloy processed by mechanical alloying and spark plasma sintering[J]. Acta Mater., 2009, 57: 3529 doi: 10.1016/j.actamat.2009.04.012
22	Mondet M, Barraud E, Lemonnier S, et al. Microstructure and mechanical properties of AZ91 magnesium alloy developed by spark plasma sintering[J]. Acta Mater., 2016, 119: 55 doi: 10.1016/j.actamat.2016.08.006
23	Hu Z Y, Zhang Z H, Cheng X W, et al. A review of multi-physical fields induced phenomena and effects in spark plasma sintering: Fundamentals and applications[J]. Mater. Des., 2020, 191: 108662 doi: 10.1016/j.matdes.2020.108662
24	Wen H M, Topping T D, Isheim D, et al. Strengthening mechanisms in a high-strength bulk nanostructured Cu-Zn-Al alloy processed via cryomilling and spark plasma sintering[J]. Acta Mater., 2013, 61: 2769 doi: 10.1016/j.actamat.2012.09.036
25	Muñoz-Saldaña J, Valencia-Ramirez A, Castillo-Perea L A, et al. Oxidation behavior of dense yttrium doped B2-NiAl bulk material fabricated by ball milling self-propagating high-temperature synthesis and densified by spark plasma sintering[J]. Surf. Coat. Technol., 2021, 421: 127448 doi: 10.1016/j.surfcoat.2021.127448
26	Meng J, Jia C C, He Q. Fabrication of oxide-reinforced Ni₃Al composites by mechanical alloying and spark plasma sintering[J]. Mater. Sci. Eng., 2006, A434: 246
27	Wen S H, Zhou C G, Sha J B. Improvement of oxidation resistance of a Mo-62Si-5B (at.%) alloy at 1250^oC and 1350^oC via an in situ pre-formed SiO₂ fabricated by spark plasma sintering[J]. Corros. Sci., 2017, 127: 175 doi: 10.1016/j.corsci.2017.08.019
28	Ikeda A, Goto K, Osada T, et al. High-throughput mapping method for mechanical properties, oxidation resistance, and phase stability in Ni-based superalloys using composition-graded unidirectional solidified alloys[J]. Scr. Mater., 2021, 193: 91 doi: 10.1016/j.scriptamat.2020.10.043
29	Wang K M, Du D, Liu G, et al. High-temperature oxidation behaviour of high chromium superalloys additively manufactured by conventional or extreme high-speed laser metal deposition[J]. Corros. Sci., 2020, 176: 108922 doi: 10.1016/j.corsci.2020.108922
30	Xie Y, Huang Y C, Li Y H, et al. A novel method to promote selective oxidation of Ni-Cr alloys: Surface spreading α-Al₂O₃ nanoparticles[J]. Corros. Sci., 2021, 190: 109717 doi: 10.1016/j.corsci.2021.109717
31	Pillai R, Chyrkin A, Galiullin T, et al. External α-Al₂O₃ scale on Ni-base alloy 602 CA-Part II: Microstructural evolution[J]. Corros. Sci., 2017, 127: 27 doi: 10.1016/j.corsci.2017.07.021
32	Liu H Y, Feng Y J, Li P, et al. Enhanced plasticity of the oxide scales by in-situ formed Cr₂O₃/Cr heterostructures for Cr-based coatings on Zr alloy in 1200^oC steam[J]. Corros. Sci., 2021, 184: 109361 doi: 10.1016/j.corsci.2021.109361

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