共晶高熵合金高温腐蚀的研究进展

doi:10.11902/1005.4537.2024.005

中国腐蚀与防护学报

2024, Vol. 44

Issue (6): 1377-1388 CSTR: 32134.14.1005.4537.2024.005 DOI: 10.11902/1005.4537.2024.005

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共晶高熵合金高温腐蚀的研究进展

李开洋¹, 翟蕴龙¹, 胡新宇¹, 吴宏², 刘彬², 邢少华³, 侯健³, 张繁³, 张乃强¹(

)

1.华北电力大学能源动力与机械工程学院北京 102206
2.中南大学粉末冶金研究院长沙 410083
3.中国船舶集团有限公司第七二五研究所海洋腐蚀与防护全国重点实验室青岛 266237

Research Progress on High Temperature Corrosion of Eutectic High Entropy Alloys

LI Kaiyang¹, ZHAI Yunlong¹, HU Xinyu¹, WU Hong², LIU Bin², XING Shaohua³, HOU Jian³, ZHANG Fan³, ZHANG Naiqiang¹(

)

1. College of Energy Power and Mechanical Engineering, North China Electric Power University, Beijing 102206, China
2. School of Powder Metallurgy Research Institute, Central South University, Changsha 410083, China
3. National Key Laboratory of Marine Corrosion and Protection, Luoyang Ship Material Research Institute, Qingdao 266237, China

引用本文:

李开洋, 翟蕴龙, 胡新宇, 吴宏, 刘彬, 邢少华, 侯健, 张繁, 张乃强. 共晶高熵合金高温腐蚀的研究进展[J]. 中国腐蚀与防护学报, 2024, 44(6): 1377-1388.
Kaiyang LI, Yunlong ZHAI, Xinyu HU, Hong WU, Bin LIU, Shaohua XING, Jian HOU, Fan ZHANG, Naiqiang ZHANG. Research Progress on High Temperature Corrosion of Eutectic High Entropy Alloys[J]. Journal of Chinese Society for Corrosion and protection, 2024, 44(6): 1377-1388.

全文: PDF(6084 KB) HTML

摘要:

共晶高熵合金由基体相和强化相交替组成，因兼具共晶与高熵的优点而表现出极为优异的力学性能，有望突破传统合金的强度-塑性兼容极限，在工程领域得到广阔应用。然而，在服役过程中，共晶高熵合金的双相结构可能会导致氧化膜异质结构，对其抗腐蚀性能产生影响。但相关影响机制并不明确，影响了其在高温环境中的应用。本文系统分析了不同体系共晶高熵合金的高温氧化行为，梳理了温度、氧化时间、合金元素等因素对腐蚀过程的影响，总结了高温氧化机理，比较了共晶高熵合金与传统合金的抗氧化性能，指出了未来的研究方向，为共晶高熵合金的理论研究和实际应用提供了基础和指导。

关键词 ：共晶高熵合金, 高温氧化, 扩散, 双相, 氧化速率

Abstract：

Eutectic high entropy alloy (EHEA) is made up of alternatively ranged matrix and strengthening phases. The combination of eutectic and high entropy features endows EHEA extremely excellent mechanical properties, which may break the limit for strength-ductility compatibility and show a broad application prospects in various engineering fields. However, during the real service, the dual-phase structure of EHEA may result in a heterogeneous oxide scale, thus affecting its corrosion performance. The unknown effect of such heterogeneity affects the further application in high temperature application. Therefore, this study systematically analyzes the high-temperature oxidation behavior of different EHEAs, identify the factors (temperature, oxidation time, alloying elements) that affects corrosion, summarizes the high-temperature oxidation mechanism, compares the oxidation resistance between EHEA and conventional alloys and points out the future research direction, all of which may provide a reference for the future study and practical application of EHEA.

Key words： eutectic high entropy alloy high temperature oxidation diffusion dual phase oxidation rate

收稿日期: 2024-01-02 32134.14.1005.4537.2024.005

ZTFLH:

TG171

基金资助:北京市自然科学基金青年基金(2244104);技术基础科研计划项目

通讯作者: 张乃强，E-mail: zhnq@ncepu.edu.cn，研究方向为金属高温腐蚀防护

Corresponding author: ZHANG Naiqiang, E-mail: zhnq@ncepu.edu.cn

作者简介: 李开洋，男，1989年生，博士，讲师

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图1 共晶高熵合金AlCoCrFeNi2.1的组织与相分析[5]

图2 共晶高熵合金研究路线及添加元素的作用

图3 CoCr2FeNb0.5NiSi0.2在800℃下N2-44%CO2-6%H2O气氛中的氧化机理图[48]

图4 TiNbMoAlSi共晶高熵合金在1000℃的氧化机理示意图[49]

Material	Preparing Method	Phase	T^oC	th	Corrosion product	Direct mass change mg·cm^-2	Environment	Ref.
AlCoCrFeNi_2.1	Casting	B2 + L1₂	950	500	Fe₂O₃ + Al₂O₃	51	air	^[39]
AlCoCrFeNi_2.1	Casting	B2 + L1₂	1000	500	Fe₂O₃ + Al₂O₃	133	air	^[39]
Al₀CoCrCuFeNi	Arc	FCC	1000	100	Cr₂O₃ + spinel + (Co, Ni, Cu)O	1.32	air	^[47]
Al_0.5CoCrCuFeNi	melting				Al₂O₃ + Cr₂O₃ + spinel +(Co, Ni, Cu)O	0.73
Al_0.5CoCrCuFeNi	melting				Al₂O₃ + Cr₂O₃ + spinel +(Co, Ni, Cu)O	0.73
Al₁CoCrCuFeNi		FCC +			Al₂O₃ + Cr₂O₃ + spinel +(Co, Ni, Cu)O	0.33
Al₁CoCrCuFeNi		BCC			Al₂O₃ + Cr₂O₃ + spinel +(Co, Ni, Cu)O	0.33
Al_1.5CoCrCuFeNi					Al₂O₃ + Cr₂O₃ + spinel +(Co, Ni, Cu)O	0.25
Al_1.5CoCrCuFeNi					Al₂O₃ + Cr₂O₃ + spinel +(Co, Ni, Cu)O	0.25
Al₂CoCrCuFeNi					Al₂O₃ + Cr₂O₃ + spinel +(Co, Ni, Cu)O	0.235
Al₂CoCrCuFeNi					Al₂O₃ + Cr₂O₃ + spinel +(Co, Ni, Cu)O	0.235
FeCoCrNiAl	MAS and	FCC +	1050	100	Al₂O₃	0.38	air	^[49]
FeCoCrNiAlTi_0.1	hot	BCC				0.37
FeCoCrNiAlTi_0.1Si_0.1	pressing					0.34
FeCoCrNi₂Al						0.4
FeCoCrNi₂AlTi_0.1						0.36
FeCoCrNi₂AlTi_0.1Si_0.1						0.31
MCrAlY						0.63
Al₁₉Fe₂₀Co₂₀Ni₄₁	Arc	B2 + FCC	800	100	spinel1 + spinel2	4.25	air	^[46]
Al₁₉Fe₁₉Co₁₉Ni₄₁Mo₂	melting				spinel2 + spinel3	1.95
Al₁₉Fe₁₈Co₁₈Ni₄₁Mo₄					spinel2 + spinel3 + CoO	1.3
AlCoCrFeNi_2.1	Arc melting	BCC +	500	0.17	Cr₂O₃ + Al₂O₃	-	air	^[40]
	+ chill	FCC	600			-
	casting		700			-
			800			-
			900			-
AlCoCrFeNi_2.1	Arc melting	FCC(L1₂) + BCC(B2)	450	24	CrCl₂ + AlCl₂	20	Molten NaCl-KCl-MgCl₂	^[5]
AlCoCrFeNi_2.1	Arc melting	FCC(L1₂) + BCC(B2)	650	24	CrCl₂ + AlCl₂	39	Molten NaCl-KCl-MgCl₂	^[5]
TiNbMo_0.5Al_0.225Si_0.1	Vacuum	BCC + γ- (Nb, Ti)₅Si₃	1000	60	TiO₂ + TiNb₂O₇ + SiO₂	68.5	air	^[49]
TiNbMo_0.5Al_0.225Si_0.25	melting				110.93
TiNbMo_0.5Al_0.225S_0.4		Si+BCC+ γ-Nb,Ti)₅Si₃			TiO₂ + TiNb₂O₇ + Al₂O₃	75.71
TiNbMo_0.5Al_0.225S_0.4		Si+BCC+ γ-Nb,Ti)₅Si₃			TiO₂ + TiNb₂O₇ + Al₂O₃	75.71
TiNbMo_0.5Al_0.225Si_0.55		BCC + β- (Nb,Ti)₅Si₃				102.64
FeCoNiAlCrB	Ball	BCC +	1000	6	spinel + α-Al₂O₃ + Cr₂O₃	-	air	^[51]
	milling +	borides		48		-
FeCoNiAlCrBY_0.1	SPS			6		-
				48		-
Al₂₃Cr₂₀Nb₁₅Ti₃₂Zr₁₀	Arc	B2 +	800	100	Al₂O₃ + CrO₂ +	8	air	^[50]
	melting	C14 Laves	900	100	Ti_0.4Al_0.3Nb_0.3O₂ + TiO₂ +	22
	melting	1000	10	Zr_0.5Al_0.5O₂	20
Al₂₈Cr₂₀Nb₁₅Ti₂₇Zr₁₀			800	100		-59
			900	100		-62
			1000	10		-15
Al₃₃Cr₂₀Nb₁₅Ti₂₂Zr₁₀			800	100		-18.5
			900	100		-38
			1000	10		-29
AlCoCrFeNi₂	Arc melting	FCC + BCC	1050	55	Al₂O₃ + Cr₂O₃ + Fe₂O₃· AB₂O₄	-0.07	air	^[42]
Al_1.5CoCrFeNi₂		FCC + B2			(A = Fe/Co/Ni, B = Al/Cr)	0.36
AlCoCr_1.5FeNi₂		FCC + BCC				0.29
Al_1.5CoCr_1.5FeNi₂		BCC/B2				0.56
CoCr₂FeNb_0.5Ni	Laser cladding	FCC + Laves	800	320	Cr₂O₃ + Cr₃O	1.55	N₂-44CO₂-6H₂O gas	^[48]
CoCr₂FeNb_0.5NiSi_0.2						1.34
AlCrFeNiTi	Arc melting	BCC1 + BCC2 + Laves	900	100	TiO₂ + Al₂O₃ + Mn₂O₃ + complex	1.31	air	^[45]
					Fe-O (Fe₂TiO₅, Mn(FeTi))	1.31

AlCrFeNiTiMn_0.5		BCC1				1.66
		BCC2 +
		Laves
AlCoCrFeNi_2.1	Arc melting	FCC (γ') + BCC (β)	1000	500	Al₂O₃ + spinel	-	air	^[43]
AlCoCrFeNi_2.1	Arc melting	FCC (γ') + BCC (β)	1100	500	Al₂O₃	-	air	^[43]
AlCoCrFeNi_2.1	Arc melting	L1₂ (γ') +	1100	1008	Al₂O₃	-	air	^[44]
AlCoCrFeNi_2.1	Arc melting	B2 (β)	1200	1008	Al₂O₃	-	air	^[44]
NiCoCrAlYHf			1100			-
NiCoCrAlYHf			1200			-

表1 不同体系共晶高熵合金的高温腐蚀总结

图5 多种共晶高熵合金以及Co基、Fe基、Ni基、Ti基合金在550~1100℃下静态空气中的氧化速率常数对比

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