Mechanical Properties and Oxidation Resistance of a Refractory Medium-entropy Alloy CrTaTi

doi:10.11901/1005.3093.2022.403

Chinese Journal of Materials Research

2023, Vol. 37

Issue (6): 443-452 DOI: 10.11901/1005.3093.2022.403

ARTICLES

Current Issue | Archive | Adv Search

Mechanical Properties and Oxidation Resistance of a Refractory Medium-entropy Alloy CrTaTi

SHI Chang, DU Yuhang, LAI Liming, XIAO Siming, GUO Ning, GUO Shengfeng(

)

School of Materials and Energy, Southwest University, Chongqing 400715, China

Cite this article:

SHI Chang, DU Yuhang, LAI Liming, XIAO Siming, GUO Ning, GUO Shengfeng. Mechanical Properties and Oxidation Resistance of a Refractory Medium-entropy Alloy CrTaTi. Chinese Journal of Materials Research, 2023, 37(6): 443-452.

Download:

HTML

PDF(14318KB)
Export: BibTeX | EndNote (RIS)

Abstract

A new refractory medium-entropy alloy of CrTaTi has been successfully developed through the reasonably composition design, and the room-temperature mechanical properties and high-temperature oxidation resistance of the alloy were systematically investigated in this paper. The results show that the as-cast alloy is composed of bcc phase matrix and a small amount of Cr₂Ta Laves phase. The solid solution strengthening and precipitation strengthening make the alloy with good comprehensive mechanical properties at room-temperature. During the short-term oxidation test at medium- and high-temperatures a composite oxide scale containing TiO₂ and Cr₂O₃ preferentially formed on the alloy surface, showing excellent oxidation resistance. The oxidation weight gain of CrTaTi alloy is only 8.4 mg/cm² after oxidation in air at 1000℃ for 10 h.

Key words: metallic materials refractory medium entropy alloy microstructure room-temperature mechanical properties high-temperature oxidation resistance

Received: 20 July 2022

ZTFLH:

TB31

Fund: National Natural Science Foundation of China(52071276)

Corresponding Authors: GUO Shengfeng, Tel: 13500330725, E-mail: sfguo@swu.edu.cn

	Service

	E-mail this article
	Add to citation manager
	E-mail Alert
	RSS
	（）
	Articles by authors
	SHI Chang
	DU Yuhang
	LAI Liming
	XIAO Siming
	GUO Ning
	GUO Shengfeng

URL:

https://www.cjmr.org/EN/10.11901/1005.3093.2022.403 OR https://www.cjmr.org/EN/Y2023/V37/I6/443

Fig.1 Calculated mole fraction of equilibrium phases at various temperatures for the CrTaTi (a) and XRD pattern of as-cast CrTaTi refractory medium-entropy alloy (b)

Fig.2 Backscattered SEM images of the as-cast CrTaTi refractory medium-entropy alloy (a) the overall microstructure of the alloy, (b) the interdendritic microstructure, with the presence of the Cr₂Ta second phase in the interdendritic

Table 1 The chemical composition of dendrite and interdendritic regions of CrTaTi refractory medium-entropy alloy (atomic fraction, %)

Fig.3 Room-temperature compressive stress-strain curve of the as-cast CrTaTi refractory entropy alloy (a), the mechanical properties of the as-cast CrTaTi alloy and some typical refractory multi-principal element alloys previously reported^[7,23~33] (b)

Fig.4 Appearance changes (a) and the changes of mass gain (b) of samples after isothermal oxidation at different temperatures with different times, respectively

Table 2 Oxidation weight gain of typical refractory multi-component alloys after oxidation at 1000℃ for 3 h

Table 3 Mixing entropy (ΔS_mix), mixing enthalpy (ΔH_mix), the atomic radius (δ), parameter Ω, electronegativity difference (ΔX), Valence electron concentration (VEC) of the CrTaTi refractory high-entropy alloy

Table 4 The shear modulus (μ) and atomic radius (r) of Cr, Ta and Ti elements^[45]

Fig.5 XRD pattern of the oxidation products on the sample surface after 10 h oxidation at 1000℃

Fig.6 Cross-sectional SEM images and element distribution of oxide layer for CrTaTi alloys isothermally exposed to the air at 1000℃ for 3 h (a) and 10 h (b), respectively

Fig.7 SEM and EDS results of CrTaTi alloys after 5 min (a), 10 min (b) and 30 min (c) oxidation

Fig.8 XPS results of oxidized CrTaTi alloy at 1000℃ for 0, 5, 10 and 30 min: the peak fitting of Cr2p fine spectrum on the sample surface (a), Ti2p fine spectrum peak fitting (b), Ta4f fine spectrum peak fitting (c), and the proportion of oxides of Cr, Ta and Ti after oxidation with different times (d)

Table 5 Standard Gibbs free energy of oxidation products of Cr, Ta and Ti at 1000℃

1	Yeh J W, Chen S K, Lin S J, et al. Nanostructured high-entropy alloys with multiple principal elements: novel alloy design concepts and outcomes [J]. Adv. Eng. Mater., 2004, 6(5): 299 doi: 10.1002/(ISSN)1527-2648
2	Cantor B, Chang I T H, Knight P, et al. Microstructural development in equiatomic multicomponent alloys [J]. Mater. Sci. Eng., 2004, 375C: 213
3	Miracle D B, Senkov O N. A critical review of high entropy alloys and related concepts [J]. Acta Mater., 2017, 122: 448 doi: 10.1016/j.actamat.2016.08.081
4	Fu W J, Huang Y J, Sun J F, et al. Strengthening CrFeCoNi-Mn_0.75Cu_0.25 high entropy alloy via laser shock peening [J]. Int. J. Plast., 2022, 154: 103296 doi: 10.1016/j.ijplas.2022.103296
5	Gludovatz B, Hohenwarter A, Catoor D, et al. A fracture-resistant high-entropy alloy for cryogenic applications [J]. Science, 2014, 345(6201): 1153 doi: 10.1126/science.1254581 pmid: 25190791
6	Senkov O N, Senkova S V, Dimiduk D M, et al. Oxidation behavior of a refractory NbCrMo_0.5Ta_0.5TiZr alloy [J]. J. Mater. Sci., 2012, 47: 6522 doi: 10.1007/s10853-012-6582-0
7	Senkov O N, Wilks G B, Scott J M, et al. Mechanical properties of Nb₂₅Mo₂₅Ta₂₅W₂₅ and V₂₀Nb₂₀Mo₂₀Ta₂₀W₂₀ refractory high entropy alloys [J]. Intermetallics, 2011, 19: 698 doi: 10.1016/j.intermet.2011.01.004
8	Guo Z M, Zhang A J, Han J S, et al. Microstructure, mechanical and tribological properties of CoCrFeNiMn high entropy alloy matrix composites with addition of Cr₃C₂ [J]. Tribol. Int., 2020, 151: 106436 doi: 10.1016/j.triboint.2020.106436
9	Kumar N A P K, Li C, Leonard K J, et al. Microstructural stability and mechanical behavior of FeNiMnCr high entropy alloy under ion irradiation [J]. Acta Mater., 2016, 113: 230 doi: 10.1016/j.actamat.2016.05.007
10	Zhang W, Wang M, Wang L, et al. Interface stability, mechanical and corrosion properties of AlCrMoNbZr/(AlCrMoNbZr)N high-entropy alloy multilayer coatings under helium ion irradiation [J]. Appl. Surf. Sci., 2019, 485: 108 doi: 10.1016/j.apsusc.2019.04.192
11	Jayaraj J, Thinaharan C, Ningshen S, et al. Corrosion behavior and surface film characterization of TaNbHfZrTi high entropy alloy in aggressive nitric acid medium [J]. Intermetallics, 2017, 89: 123 doi: 10.1016/j.intermet.2017.06.002
12	Hua X J, Hu P, Xing H R, et al. Development and property tuning of refractory high-entropy alloys: a review [J]. Acta Metall. Sin. (Engl. Lett.), 2022, 35: 1231 doi: 10.1007/s40195-022-01382-x
13	Lv Z P, Lei Z F, Huang H L, et al. Deformation behavior and toughening of high-entropy alloys [J]. Acta Metall. Sin., 2018, 54(11): 1553 doi: 10.11900/0412.1961.2018.00372
	吕昭平, 雷智锋, 黄海龙等. 高熵合金的变形行为及强韧化 [J]. 金属学报, 2018, 54(11): 1553 doi: 10.11900/0412.1961.2018.00372
14	Senkov O N, Wilks G B, Miracle D B, et al. Refractory high-entropy alloys [J]. Intermetallics, 2010, 18: 1758 doi: 10.1016/j.intermet.2010.05.014
15	Du Y H, Ding D Y, Guo N, et al. The progress of high-entropy alloys with the functional properties [J]. Mater. Rev., 2021, 35(17): 17051
	杜宇航, 丁德渝, 郭宁等. 高熵合金功能特性研究进展 [J]. 材料导报, 2021, 35(17): 17051
16	Chang C H, Titus M S, Yeh J W. Oxidation behavior between 700 and 1300 C of refractory TiZrNbHfTa high-entropy alloys containing aluminum [J]. Adv. Eng. Mater., 2018, 20(6): 1700948 doi: 10.1002/adem.v20.6
17	Yan X H, Zhang Y. A body-centered cubic Zr₅₀Ti₃₅Nb₁₅ medium-entropy alloy with unique properties [J]. Scripta Mater., 2020, 178: 329 doi: 10.1016/j.scriptamat.2019.11.059
18	Zhao Y L, Yang T, Tong Y, et al. Heterogeneous precipitation behavior and stacking-fault-mediated deformation in a CoCrNi-based medium-entropy alloy [J]. Acta Mater., 2017, 138: 72 doi: 10.1016/j.actamat.2017.07.029
19	Sohn S S, Kim D G, Jo Y H, et al. High-rate superplasticity in an equiatomic medium-entropy VCoNi alloy enabled through dynamic recrystallization of a duplex microstructure of ordered phases [J]. Acta Mater., 2020, 194: 106 doi: 10.1016/j.actamat.2020.03.048
20	Wang H, He Q F, Yang Y. High-entropy intermetallics: from alloy design to structural and functional properties [J]. Rare Met., 2022, 41: 1989 doi: 10.1007/s12598-021-01926-7
21	Lv Z P, Jiang S H, He J Y, et al. Second phase strengthening in advanced metal materials [J]. Acta Metall. Sin., 2016, 52(10): 1183
	吕昭平, 蒋虽合, 何骏阳等. 先进金属材料的第二相强化 [J]. 金属学报, 2016, 52(10): 1183
22	Gorr B, Schellert S, Müller F, et al. Current status of research on the oxidation behavior of refractory high entropy alloys [J]. Adv. Eng. Mater., 2021, 23(5): 2001047 doi: 10.1002/adem.v23.5
23	Wang S P, Xu J. (TiZrNbTa)-Mo high-entropy alloys: dependence of microstructure and mechanical properties on Mo concentration and modeling of solid solution strengthening [J]. Intermetallics, 2018, 95: 59 doi: 10.1016/j.intermet.2018.01.017
24	Wang W, Zhang Z T, Niu J Z, et al. Effect of Al addition on structural evolution and mechanical properties of the Al _x HfNbTiZr high-entropy alloys [J]. Mater. Today Commun., 2018, 16: 242
25	Zhang J, Hu Y Y, Wei Q Q, et al. Microstructure and mechanical properties of Re_xNbMoTaW high-entropy alloys prepared by arc melting using metal powders [J]. J. Alloys Compd., 2020, 827: 154301 doi: 10.1016/j.jallcom.2020.154301
26	Yang X, Zhang Y, Liaw P K. Microstructure and compressive properties of NbTiVTaAl_x high entropy alloys [J]. Proc. Eng., 2012, 36: 292 doi: 10.1016/j.proeng.2012.03.043
27	Qiao D X, Jiang H, Jiao W N, et al. A novel series of refractory high‑entropy alloys Ti₂ZrHf_0.5VNb _x with high specific yield strength and good ductility [J]. Acta Metall. Sin. (Engl. Lett.), 2019, 32: 925 doi: 10.1007/s40195-019-00921-3
28	Tsakiropoulos P. Alloys for application at ultra-high temperatures: Nb-silicide in situ composites: challenges, breakthroughs and opportunities [J]. Prog. Mater. Sci., 2022, 123: 100714 doi: 10.1016/j.pmatsci.2020.100714
29	Yao H W, Qiao J W, Gao M C, et al. NbTaV-(Ti,W) refractory high-entropy alloys: experiments and modeling [J]. Mater. Sci. Eng., 2016, 674A: 203
30	Lee C, Song G, Gao M C, et al. Lattice distortion in a strong and ductile refractory high-entropy alloy [J]. Acta Mater., 2018, 160: 158 doi: 10.1016/j.actamat.2018.08.053
31	Feng R, Feng B J, Gao M C, et al. Superior high-temperature strength in a supersaturated refractory high-entropy alloy [J]. Adv. Mater., 2021, 33(48): 2102401 doi: 10.1002/adma.v33.48
32	Li Q Y, Zhang H, Li D C, et al. Comparative study of the microstructures and mechanical properties of laser metal deposited and vacuum arc melted refractory NbMoTa medium-entropy alloy [J]. Int. J. Refract. Met. Hard Met., 2020, 88: 105195
33	Wei Q Q, Shen Q, Zhang J, et al. Microstructure and mechanical property of a novel ReMoTaW high-entropy alloy with high density [J]. Int. J. Refract. Met. Hard Mater., 2018, 77: 8 doi: 10.1016/j.ijrmhm.2018.05.006
34	Waseem O A, Lee J, Lee H M, et al. The effect of Ti on the sintering and mechanical properties of refractory high-entropy alloy Ti_xWTaVCr fabricated via spark plasma sintering for fusion plasma-facing materials [J]. Mater. Chem. Phys., 2018, 210: 87 doi: 10.1016/j.matchemphys.2017.06.054
35	Butler T M, Chaput K J, Dietrich J R, et al. High temperature oxidation behaviors of equimolar NbTiZrV and NbTiZrCr refractory complex concentrated alloys (RCCAs) [J]. J. Alloys Compd., 2017, 729: 1004 doi: 10.1016/j.jallcom.2017.09.164
36	Gorr B, Mueller F, Christ H J, et al. High temperature oxidation behavior of an equimolar refractory metal-based alloy 20Nb-20Mo-20Cr-20Ti-20Al with and without Si addition [J]. J. Alloys Compd., 2016, 688: 468
37	Butler T M, Chaput K J. Native oxidation resistance of Al₂₀Nb₃₀Ta₁₀Ti₃₀Zr₁₀ refractory complex concentrated alloy (RCCA) [J]. J. Alloys Compd., 2019, 787: 606 doi: 10.1016/j.jallcom.2019.02.128
38	Gorr B, Azim M, Christ H J, et al. Phase equilibria, microstructure, and high temperature oxidation resistance of novel refractory high-entropy alloys [J]. J. Alloys Compd., 2015, 624: 270 doi: 10.1016/j.jallcom.2014.11.012
39	Waseem O A, Auyeskhan U, Lee H M, et al. A combinatorial approach for the synthesis and analysis of Al _x Cr _y Mo _z NbTiZr high-entropy alloys: oxidation behavior [J]. J. Mater. Res., 2018, 33(19): 3226 doi: 10.1557/jmr.2018.241
40	Xiao Y F, Kuang W H, Xu Y F, et al. Microstructure and oxidation behavior of the CrMoNbTaV high-entropy alloy [J]. J. Mater. Res., 2019, 34: 301 doi: 10.1557/jmr.2018.340
41	Zhang Y, Zhou Y J, Lin J P, et al. Solid-solution phase formation rules for multi-component alloys [J]. Adv. Eng. Mater., 2008, 10(6): 534 doi: 10.1002/(ISSN)1527-2648
42	Yang X, Zhang Y. Prediction of high-entropy stabilized solid-solution in multi-component alloys [J]. Mater. Chem. Phys., 2012, 132: 233 doi: 10.1016/j.matchemphys.2011.11.021
43	Guo S, Ng C, Lu J, et al. Effect of valence electron concentration on stability of fcc or bcc phase in high entropy alloys [J]. J. Appl. Phys., 2011, 109(10): 103505 doi: 10.1063/1.3587228
44	Toda-Caraballo I, Rivera-Díaz-del-Castillo P E J. Modelling solid solution hardening in high entropy alloys [J]. Acta Mater., 2015, 85: 14 doi: 10.1016/j.actamat.2014.11.014
45	Warlimont H, Martienssen W. Springer Handbook of Materials Data [M]. 2nd ed. Cham: Springer, 2018
46	Von Nembach E. Particle Strengthening of Metals and Alloys [M]. New York: John Wiley & Sons, 1997
47	Raman L, Anupam A, Karthick G, et al. Strengthening mechanisms in CrMoNbTiW refractory high entropy alloy [J]. Mater. Sci. Eng., 2021, 819A: 141503
48	Georg F M. Thermodynamik Für Werkstoffwissenschaftler [M]. Weinheim: Leipzig, 2009
49	Müller F, Gorr B, Christ H J, et al. On the oxidation mechanism of refractory high entropy alloys [J]. Corros. Sci., 2019, 159: 108161 doi: 10.1016/j.corsci.2019.108161
50	Ren W L, Ouyang F F, Ding B, et al. The influence of CrTaO₄ layer on the oxidation behavior of a directionally-solidified nickel-based superalloy at 850~900℃ [J]. J. Alloys Compd., 2017, 724: 565 doi: 10.1016/j.jallcom.2017.07.066
51	Lo K C, Chang Y J, Murakami H, et al. An oxidation resistant refractory high entropy alloy protected by CrTaO₄-based oxide [J]. Sci. Rep., 2019, 9: 7266 doi: 10.1038/s41598-019-43819-x
52	Gorr B, Müller F, Schellert S, et al. A new strategy to intrinsically protect refractory metal based alloys at ultra high temperatures [J]. Corros. Sci., 2020, 166: 108475 doi: 10.1016/j.corsci.2020.108475
53	Huang D, Lu J S, Zhuang Y X, et al. The role of Nb on the high temperature oxidation behavior of CoCrFeMnNb _x Ni high-entropy alloys [J]. Corros. Sci., 2019, 158: 108088 doi: 10.1016/j.corsci.2019.07.012
54	Xu L J, Zong L, Luo C Y, et al. Toughening pathways and regulatory mechanisms of refractory high-entropy alloys [J]. Acta Metall. Sin., 2022, 58(3): 257 doi: 10.11900/0412.1961.2021.00286
	徐流杰, 宗乐, 罗春阳等. 难熔高熵合金的强韧化途径与调控机理 [J]. 金属学报, 2022, 58(3): 257 doi: 10.11900/0412.1961.2021.00286

[1]	MAO Jianjun, FU Tong, PAN Hucheng, TENG Changqing, ZHANG Wei, XIE Dongsheng, WU Lu. Kr Ions Irradiation Damage Behavior of AlNbMoZrB Refractory High-entropy Alloy[J]. 材料研究学报, 2023, 37(9): 641-648.
[2]	SONG Lifang, YAN Jiahao, ZHANG Diankang, XUE Cheng, XIA Huiyun, NIU Yanhui. Carbon Dioxide Adsorption Capacity of Alkali-metal Cation Dopped MIL125[J]. 材料研究学报, 2023, 37(9): 649-654.
[3]	ZHAO Zhengxiang, LIAO Luhai, XU Fanghong, ZHANG Wei, LI Jingyuan. Hot Deformation Behavior and Microstructue Evolution of Super Austenitic Stainless Steel 24Cr-22Ni-7Mo-0.4N[J]. 材料研究学报, 2023, 37(9): 655-667.
[4]	SHAO Hongmei, CUI Yong, XU Wendi, ZHANG Wei, SHEN Xiaoyi, ZHAI Yuchun. Template-free Hydrothermal Preparation and Adsorption Capacity of Hollow Spherical AlOOH[J]. 材料研究学报, 2023, 37(9): 675-684.
[5]	XING Dingqin, TU Jian, LUO Sen, ZHOU Zhiming. Effect of Different C Contents on Microstructure and Properties of VCoNi Medium-entropy Alloys[J]. 材料研究学报, 2023, 37(9): 685-696.
[6]	OUYANG Kangxin, ZHOU Da, YANG Yufan, ZHANG Lei. Microstructure and Tensile Properties of Mg-Y-Er-Ni Alloy with Long Period Stacking Ordered Phases[J]. 材料研究学报, 2023, 37(9): 697-705.
[7]	PAN Xinyuan, JIANG Jin, REN Yunfei, LIU Li, LI Jinghui, ZHANG Mingya. Microstructure and Property of Ti / Steel Composite Pipe Prepared by Hot Extrusion[J]. 材料研究学报, 2023, 37(9): 713-720.
[8]	XU Lijun, ZHENG Ce, FENG Xiaohui, HUANG Qiuyan, LI Yingju, YANG Yuansheng. Effects of Directional Recrystallization on Microstructure and Superelastic Property of Hot-rolled Cu71Al18Mn11 Alloy[J]. 材料研究学报, 2023, 37(8): 571-580.
[9]	XIONG Shiqi, LIU Enze, TAN Zheng, NING Likui, TONG Jian, ZHENG Zhi, LI Haiying. Effect of Solution Heat Treatment on Microstructure of DZ125L Superalloy with Low Segregation[J]. 材料研究学报, 2023, 37(8): 603-613.
[10]	LIU Jihao, CHI Hongxiao, WU Huibin, MA Dangshen, ZHOU Jian, XU Huixia. Heat Treatment Related Microstructure Evolution and Low Hardness Issue of Spray Forming M3 High Speed Steel[J]. 材料研究学报, 2023, 37(8): 625-632.
[11]	YOU Baodong, ZHU Mingwei, YANG Pengju, HE Jie. Research Progress in Preparation of Porous Metal Materials by Alloy Phase Separation[J]. 材料研究学报, 2023, 37(8): 561-570.
[12]	REN Fuyan, OUYANG Erming. Photocatalytic Degradation of Tetracycline Hydrochloride by g-C₃N₄ Modified Bi₂O₃[J]. 材料研究学报, 2023, 37(8): 633-640.
[13]	WANG Hao, CUI Junjun, ZHAO Mingjiu. Recrystallization and Grain Growth Behavior for Strip and Foil of Ni-based Superalloy GH3536[J]. 材料研究学报, 2023, 37(7): 535-542.
[14]	LIU Mingzhu, FAN Rao, ZHANG Xiaoyu, MA Zeyuan, LIANG Chengyang, CAO Ying, GENG Shitong, LI Ling. Effect of Photoanode Film Thickness of SnO₂ as Scattering Layer on the Photovoltaic Performance of Quantum Dot Dye-sensitized Solar Cells[J]. 材料研究学报, 2023, 37(7): 554-560.
[15]	QIN Heyong, LI Zhentuan, ZHAO Guangpu, ZHANG Wenyun, ZHANG Xiaomin. Effect of Solution Temperature on Mechanical Properties and γ' Phase of GH4742 Superalloy[J]. 材料研究学报, 2023, 37(7): 502-510.

No Suggested Reading articles found!

Viewed

Full text

Abstract

Cited

Shared

Discussed