相调控视角下AlCrFeNiNb<sub><i>x</i></sub>高熵合金的强化机制及磨损行为

黄潘毅; 刘郅澄; 周永强; 彭文屹; 瞿玉海; 章爱生; 邓晓华; 张龙鹤; 周诗逸; 周杰

doi:10.7498/aps.74.20250978

摘要
为了探索Nb元素对AlCrFeNi合金的相调控机制, 本研究将实验与第一性原理计算相结合, 系统探究了不同Nb含量对AlCrFeNiNb_x高熵合金微观组织、力学性能及耐磨性的影响. 结果表明, AlCrFeNiNb_0.4高熵合金具有良好的力学性能与最佳的耐磨性. Nb的掺杂改变了AlCrFeNi合金的磨损机制, 并提高了合金的耐磨性. 这归因于Nb对AlCrFeNi合金的相调控作用: 一方面诱导高硬度的Laves相析出, 另一方面固溶于合金的BCC相及B2相, 并显著地提升两相的力学性能. 此外, Nb的掺杂细化了合金的微观组织, 促使其相界面密度提升, 从而综合提升了合金的硬度, 屈服强度以及耐磨性. 第一性原理计算表明Nb原子改变了AlCrFeNi合金中BCC相与B2相的电子结构, 从而提升了两相的稳定性, 印证了Nb对两相的的固溶强化作用. 而Nb原子与两相中大部分原子会形成较强的反键, 进一步解释了Nb掺杂后合金的微观组织中大量Laves相生成的本质原因.

关键词:
AlCrFeNiNb_x高熵合金 /

第一性原理 /

力学性能 /

磨损行为
Abstract
AlCoCrFeNi high-entropy alloys have consistently attracted attention due to their outstanding strength-to-ductility ratio. However, the substantial content of expensive cobalt in these alloys has somewhat limited their engineering applications. Consequently, there is an urgent need to design and develop high-performance, low-cost cobalt-free high-entropy alloys. AlCrFeNi alloys exhibit microstructures and properties similar to AlCoCrFeNi alloys. Simultaneously, the absence of Co significantly reduces costs and markedly improves casting performance. These alloys represent a potential structural material for harsh environments, demonstrating promising engineering applications. In order to explore the phase modulation mechanism of Nb element on AlCrFeNi alloy, this study combines experiments with first principles calculations to systematically investigate the effects of Nb on the microstructure, mechanical properties and wear resistance of AlCrFeNi alloy. The research results show that the AlCrFeNiNb_0.4 high-entropy alloy has the best mechanical properties and wear resistance.The doping of Nb changes the wear mechanism of the AlCrFeNi alloy and improves the wear resistance of the alloy. This is attributed to the phase modulation effect of Nb on AlCrFeNi alloy. On the one hand, it induces the precipitation of Laves phase, which has high hardness, and on the other hand, it solidly dissolves in the BCC and B2 phases of the alloy, significantly improving the mechanical properties of the two phases. In addition, Nb doping refines the microstructure of the AlCrFeNi alloy, which leads to an increase in the phase interface density, thus enhancing the hardness, yield strength and wear resistance of the alloy. First principles calculations show that the Nb atoms change the electronic structures of the BCC and B2 phases in the AlCrFeNi alloy, thereby enhancing the stability of the two phases and confirming the solid solution strengthening effect of Nb on the two phases. The Nb atoms form strong antibonds with most of the atoms in the two phases, which further explains the nature of the generation of a large number of Laves phases in the microstructure of the alloy after Nb doping.

Keywords:
AlCrFeNiNb_x high-entropy alloys /

first principles /

mechanical properties /

wear behavior
文章全文

施引文献

图 1 晶体模型与等效位点　(a) Al₂Cr₈Fe₈Ni₂; (b) Al₂Cr₇Fe8 Ni₂Nb; (c) Al₈Cr₂Fe₂Ni₈;(d) Al₈Cr₂FeNi₈Nb

Fig. 1. Crystal models and equivalents for points: (a) Al₂Cr₈Fe₈Ni₂; (b) Al₂Cr₇Fe₈Ni₂Nb; (c) Al₈Cr₂Fe₂Ni₈; (d) Al₈Cr₂FeNi₈Nb.

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图 2 AlCrFeNiNb_x高熵合金磨损性能测试　(a) 摩擦系数; (b) 磨损率

Fig. 2. Wear performance test of AlCrFeNiNb_x HEAs: (a) Friction coefficient; (b) wear rate.

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图 3 AlCrFeNiNb_x磨损SEM及EDS图　(a) x = 0; (b) x = 0.1; (c) x = 0.2; (d) x = 0.3; (e) x = 0.4

Fig. 3. SEM and EDS plots of AlCrFeNiNb_x HEA wear: (a) x = 0; (b) x = 0.1; (c) x = 0.2; (d) x = 0.3; (e) x = 0.4.

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图 4 AlCrFeNiNb_x高熵合金的XRD图谱　(a) 10°—90°; (b) 44°—45°

Fig. 4. XRD patterns of AlCrFeNiNb_x HEAs: (a) 10°–90°; (b) 44°–45°

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图 5 AlCrFeNiNb_x高熵合金微观组织BSE图及EDS图　(a) x = 0; (b) x = 0.1; (c) x = 0.2; (d) x = 0.3; (e) x = 0.4.

Fig. 5. BSEM and EDS plots of microstructure of AlCrFeNiNb_x HEAs: (a) x = 0; (b) x = 0.1; (c) x = 0.2; (d) x = 0.3; (e) x = 0.4

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图 6 AlCrFeNiNb_x高熵合金的(a)显微维氏硬度与(b)室温压缩曲线

Fig. 6. (a) Microhardness and (b) room temperature compression curves of AlCrFeNiNb_x HEAs.

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图 7 掺杂前后BCC相与B2相的(a)载荷-位移曲线和(b)纳米硬度以及弹性模量

Fig. 7. (a) Load-displacement curves and (b) nanohardness and Young's modulus of BCC phase and B2 phase before and after doping.

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图 8 体系态密度图　(a) Al₂Cr₈Fe₈Ni₂; (b) Al₂Cr₇Fe₈Ni₂Nb; (c) Al₈Cr₂Fe₂Ni₈; (d) Al₈Cr₂FeNi₈Nb

Fig. 8. Density of state of systems: (a) Al₂Cr₈Fe₈Ni₂; (b) Al₂Cr₇Fe₈Ni₂Nb; (c) Al₈Cr₂Fe₂Ni₈; (d) Al₈Cr₂FeNi₈Nb.

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图 9 体系差分电荷密度图　(a) Al₂Cr₈Fe₈Ni₂; (b) Al₂Cr₇Fe₈Ni₂Nb; (c) Al₈Cr₂Fe₂Ni₈; (d) Al₈Cr₂FeNi₈Nb

Fig. 9. Electron density difference of systems: (a) Al₂Cr₈Fe₈Ni₂; (b) Al₂Cr₇Fe₈Ni₂Nb; (c) Al₈Cr₂Fe₂Ni₈; (d) Al₈Cr₂FeNi₈Nb.

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表 1 各相成分值

Table 1. Component values at each phase.

Alloys	Phases	Al/%	Cr/%	Fe/%	Ni/%	Nb/%
Nb0	BCC	10.41	44.02	37.57	7.99	0
Nb0	B2	37.96	9.03	13.15	39.86	0
Nb0.1	BCC	10.77	46.23	35.73	6.70	0.57
	B2	32.70	13.13	16.97	35.86	1.34
	Laves	9.33	22.83	31.60	10.86	25.37
Nb0.2	BCC	9.13	46.35	36.03	6.23	2.26
	B2	32.27	13.85	16.60	35.92	1.36
	Laves	10.41	23.43	29.39	11.05	25.72
Nb0.3	BCC	10.30	42.97	36.25	7.04	3.45
	B2	37.34	10.14	13.26	37.81	1.45
	Laves	10.73	23.36	29.40	10.84	25.67
Nb0.4	BCC	10.79	39.49	35.14	7.36	7.23
	B2	34.32	12.44	15.00	36.80	1.47
	Laves	11.45	23.53	27.58	11.20	26.24

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表 2 体系的总能量、缺陷形成能、形成热与结合能

Table 2. Total energy, defect formation energy, heat of formation and binding energy of the systems.

System	Site	E_f	H	E	E_total
Al₂Cr₈Fe₈Ni₂	—	—	–0.11667	–3.62827	–29079.07198
AlCr₈Fe₈Ni₂Nb	Al site	1.17184	–0.05808	–3.84808	–30623.59838
Al₂Cr₇Fe₈Ni₂Nb	Cr site	–0.00317	–0.11683	–3.90007	–28335.21599
Al₂Cr₈Fe₇Ni₂Nb	Fe site	1.10657	–0.06134	–3.85692	–29872.04588
Al₂Cr₈Fe₈NiNb	Ni site	0.76522	–0.07841	–3.92992	–29358.95247
Al₈Cr₂Fe₂Ni₈	—	—	–0.34288	–3.47834	–18426.86037
Al₇Cr₂Fe₂Ni₈Nb	Al site	0.51441	–0.31716	–3.73102	–19972.04421
Al₈CrFe₂Ni₈Nb	Cr site	–0.67442	–0.37660	–3.78370	–17683.67563
Al₈Cr₂FeNi₈Nb	Fe site	–1.45347	–0.41555	–3.83498	–19222.39432
Al₈Cr₂Fe₂Ni₇Nb	Ni site	–1.26742	–0.40625	–3.88161	–18708.77351

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表 3 Nb掺杂前后BCC相键的布居数

Table 3. Bond populations in the BCC phase before and after Nb doping.

System	Bond	Population	Length
Al₂Cr₈Fe₈Ni₂	Ni—Ni	0.01	3.54777
	Fe—Ni	0.11	3.24825
	Fe—Fe	0.07	3.34922
	Cr—Ni	–0.03	3.48801
	Cr—Fe	–0.05	3.15932
	Cr—Cr	–0.37	3.28039
	Al—Ni	0.11	3.42543
	Al—Fe	0.11	3.20017
	Al—Cr	0.08	3.05610
	Al—Al	0.00	4.80639
Al₂Cr₇Fe₈Ni₂Nb	Ni—Ni	–0.02	3.73872
	Fe—Ni	0.10	3.32775
	Fe—Fe	0.07	3.34938
	Cr—Ni	–0.09	3.65638
	Cr—Fe	–0.05	3.13931
	Cr—Cr	–0.39	3.12486
	Al—Ni	0.13	3.40228
	Al—Fe	0.11	3.23175
	Al—Cr	0.10	2.99913
	Al—Al	0.00	4.85985
	Ni—Nb	0.57	2.58120
	Fe—Nb	–0.03	3.32742
	Cr—Nb	–0.31	3.75318
	Al—Nb	–0.14	3.66437

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表 4 Nb掺杂前后B2相键的布居数

Table 4. Bond populations in the BCC phase before and after Nb doping.

System	Bond	Population	Length
Al₈Cr₂Fe₂Ni₈	Al—Al	0.01	3.20558
	Al—Cr	–0.44	3.07520
	Al—Fe	0.24	2.47738
	Al—Ni	0.27	2.70429
	Cr—Fe	–1.00	2.44941
	Cr—Ni	–0.40	2.50288
	Fe—Ni	–0.15	3.07799
	Ni—Ni	–0.20	3.21284
Al₈Cr₂FeNi₈Nb	Al—Al	–0.02	3.23276
	Al—Cr	–0.26	3.24161
	Al—Fe	0.21	2.84415
	Al—Nb	0.00	2.65091
	Al—Ni	0.24	2.87858
	Cr—Fe	–0.73	2.46354
	Cr—Nb	–2.36	2.45989
	Cr—Ni	–0.19	2.74444
	Fe—Ni	–0.14	3.22725
	Ni—Nb	–0.33	3.26054

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表 5 各体系的弹性刚度常数

Table 5. Elastic stiffness constants of systems.

	Al₂Cr₈Fe₈Ni₂	Al₂Cr₇Fe₈Ni₂Nb	Al₈Cr₂Fe₂Ni₈	Al₈Cr₂FeNi₈Nb
C₁₁	128.29975	736.29805	270.3648	127.11465
C₂₂	177.42665	215.33585	691.93215	203.93235
C₃₃	267.0162	–375.11635	250.2832	1766.9252
C₁₂	178.20038	343.45855	93.53145	74.19628
C₂₃	160.14022	–33.38788	81.9077	256.06083
C₁₃	177.82828	304.61232	97.42585	345.99403
C₄₄	–92.7819	167.42425	31.8253	59.76855
C₅₅	–22.91365	–568.51245	53.94125	71.5073
C₆₆	81.31915	333.01795	64.64615	31.13195

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表 6 各体系的弹性柔顺常数

Table 6. Elastic flexibility constants of systems.

	Al₂Cr₈Fe₈Ni₂	Al₂Cr₇Fe₈Ni₂Nb	Al₈Cr₂Fe₂Ni₈	Al₈Cr₂FeNi₈Nb
S₁₁	–0.0156972	0.0004691	0.00475	0.0242321
S₂₂	0.0010798	0.0025236	0.0015446	0.0065644
S₃₃	0.005798	0.0088133	0.0054491	0.0021923
S₁₂	0.0131561	0.0029681	–0.0004152	–0.0019679
S₂₃	–0.0082161	–0.0063358	–0.0003173	–0.0007382
S₁₃	0.0026282	–0.0003899	–0.002034	–0.0055097
S₄₄	0.0106177	–0.0063815	0.0665176	0.0392295
S₅₅	0.0225751	0.006832	0.0391124	0.0261333
S₆₆	0.0115169	–0.0040258	0.0181006	0.038512

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表 7 各体系的弹性常数

Table 7. Elastic constants of systems.

Systems	B/GPa	G/GPa	E/GPa	H_V/GPa
Al₂Cr₈Fe₈Ni₂	168.320	107.811	266.529	15.356
Al₂Cr₇Fe₈Ni₂Nb	216.860	137.470	340.468	17.906
Al₈Cr₂Fe₂Ni₈	178.191	63.838	171.084	5.431
Al₈Cr₂FeNi₈Nb	221.891	79.373	212.751	6.325

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[19]	李腾, 李卫, 潘伟, 李岫梅. Fe40—45Cr30—35Co20—25Mo0—4Zr0—2合金微观结构对力学性能的影响. 物理学报, doi: 10.7498/aps.54.4395
[20]	郑立静, 李树索, 李焕喜, 陈昌麒, 韩雅芳, 董宝中. 7050铝合金等通道转角挤压过程中显微结构和力学性能演化的小角x射线散射研究. 物理学报, doi: 10.7498/aps.54.1665

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相调控视角下AlCrFeNiNb_x高熵合金的强化机制及磨损行为

Strengthening mechanism and wear behavior of AlCrFeNiNb_x high-entropy alloys from the perspective of phase modulation

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相调控视角下AlCrFeNiNbx高熵合金的强化机制及磨损行为

Strengthening mechanism and wear behavior of AlCrFeNiNbx high-entropy alloys from the perspective of phase modulation

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相调控视角下AlCrFeNiNb_x高熵合金的强化机制及磨损行为

Strengthening mechanism and wear behavior of AlCrFeNiNb_x high-entropy alloys from the perspective of phase modulation