液态五元Zr57Cu20Al10Ni8Ti5合金的微观结构演变与非晶形成机制

徐山森; 常健; 翟斌; 朱先念; 魏炳波

doi:10.7498/aps.72.20231169

摘要

利用电磁悬浮无容器处理技术实现了液态五元Zr₅₇Cu₂₀Al₁₀Ni₈Ti₅合金的深过冷与快速凝固, 同时通过分子动力学模拟计算揭示了非晶形成的微观机制. 实验发现, 凝固组织具有明显的核-壳结构特征, 核区为非晶相, 壳区主要由ZrCu, Zr₂Cu和Zr₈Cu₅晶体相组成. 非晶体积分数随合金过冷度的升高逐渐增大, 当达到实验最大过冷度300 K (0.26T_L)时, 非晶体积分数增至81.3%. 由此导出完全非晶凝固所需临界过冷度为334 K. TEM分析显示, 过冷度增大并接近临界过冷度时, 合金凝固组织中晶体相主要为Zr₈Cu₅相, 而ZrCu和Zr₂Cu相的生长被抑制. 在达到临界过冷度后, 过冷液相的凝固路径由Zr₈Cu₅结晶生长转变为非晶凝固. 此外, 合金的晶体壳中存在少量的晶间非晶相, 而非晶核中亦有微量的非晶间Zr₈Cu₅纳米晶团簇. 模拟结果表明, 晶间非晶相的形成主要源于近临界过冷度下偏析行为诱发的成分过冷, 而非晶间纳米晶团簇的出现则主要归因于深过冷液相中的微观热起伏效应.

关键词:

Abstract

The substantial undercooling and rapid solidification of liquid quinary Zr₅₇Cu₂₀Al₁₀Ni₈Ti₅ alloy are achieved by electromagnetic levitation (EML) technique. The amorphous solidification mechanism is revealed with molecular dynamics (MD) simulation. It is observed in EML experiment that the containerlessly solidified alloy is characterized by a core-shell structure, with mainly amorphous phase becoming the core and crystalline ZrCu, Zr₂Cu and Zr₈Cu₅ phases forming the shell. The volume fraction of amorphous core structure increases with undercooling and attains a value up to 81.3% at the maximum experimental undercooling of 300 K, which indicates that the critical undercooling required for complete amorphous solidification is 334 K. TEM analyses show that the alloy microstructure is mainly composed of Zr₈Cu₅ phase, whereas the ZrCu phase and Zr₂Cu phase are suppressed when liquid undercooling approaches this threshold. Once the critical undercooling is reached, amorphous solidification prevails over the crystallization of Zr₈Cu₅ phase. In addition, a small quantity of amorphous phases are found in the crystalline shell and a little trace of Zr₈Cu₅ nano-cluster is detected among the amorphous core. It is further verified by MD simulation that the formation of amorphous phase in the shell is caused by the microsegregation-induced solutal undercooling when liquid alloy attains the critical undercooling, while the nano-clusters within the core is mainly ascribed to the micro-thermal fluctuation effect inside highly undercooled liquid phase.

Keywords:

作者及机构信息

西北工业大学物理科学与技术学院, 西安　710072

通信作者: 魏炳波, bbwei@nwpu.edu.cn

基金项目: 国家重点研发计划(批准号: 2021YFA0716301)、国家自然科学基金(批准号: 52088101, 51771154)和陕西省重点研发计划(批准号: 2023-YBGY-437)资助的课题.

Authors and contacts

School of Physical Science and Technology, Northwestern Polytechnical University, Xi’an 710072, China

Corresponding author: Wei Bing-Bo, bbwei@nwpu.edu.cn

Funds: Project supported by the National Key R＆D Program of China (Grant No. 2021YFA0716301), the National Natural Science Foundation of China (Grant Nos. 52088101, 51771154), and the Key R&D Program of Shaanxi Province, China (Grant No. 2023-YBGY-437).

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参考文献

[1]	Liu X F, Wang R J, Zhao D Q, Pan M X, Wang W H 2007 Appl. Phys. Lett. 91 041901 Google Scholar
[2]	Sniadecki Z, Mielniczuk B, Idzikowski B, Greneche J M, Robler U K 2010 J. Appl. Phys. 108 073516 Google Scholar
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[35]	周边, 杨亮 2020 69 116101 Google Scholar Zhou B, Yang L 2020 Acta Phys. Sin. 69 116101 Google Scholar

施引文献

图 1 电磁悬浮条件下液态五元Zr₅₇Cu₂₀Al₁₀Ni₈Ti₅合金的深过冷与快速凝固　(a) ΔT = 200 K; (b) ΔT = 250 K; (c) ΔT = 300 K; (d) 核-壳界面形貌

Fig. 1. High undercooling and rapid solidification of liqud quinary Zr₅₇Cu₂₀Al₁₀Ni₈Ti₅ alloy under electromagnetic levitation condition: (a) ΔT = 200 K; (b) ΔT = 250 K; (c) ΔT = 300 K; (d) core-shell interface morphology.

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图 2 合金的相组成与非晶核的形成　(a) XRD曲线; (b) 非晶核体积分数

Fig. 2. Alloy phase constitution and amorphous core formation: (a) XRD curves; (b) volume fraction of amorphous core.

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图 3 深过冷液态Zr₅₇Cu₂₀Al₁₀Ni₈Ti₅合金快速凝固特征　(a) 冷却曲线; (b) 合金外壳的平均生长速率

Fig. 3. Rapid solidification characteristics of highly undercooled liquid Zr₅₇Cu₂₀Al₁₀Ni₈Ti₅ alloy: (a) Cooling curves; (b) alloy shell average growth rate.

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图 4 液态Zr₅₇Cu₂₀Al₁₀Ni₈Ti₅合金的微观结构特征　(a) 计算系统总能量; (b) 合金原子的扩散系数; (c) $\langle0, 0, 12, 0\rangle $二十面体结构在多面体团簇中的比例

Fig. 4. Microstructure characteristics of highly undercooled liquid Zr₅₇Cu₂₀Al₁₀Ni₈Ti₅ alloy: (a) Calculated system total energy; (b) calculated atom diffusion coefficient; (c) calculated $\langle0, 0, 12, 0\rangle $ icosahedron ratio in Voronoi polyhedral clusters.

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图 5 过冷液态Zr₅₇Cu₂₀Al₁₀Ni₈Ti₅合金的形核能力　(a) 液态合金的黏度; (b)各相的形核率

Fig. 5. Nucleation capability of the undercooled liquid Zr₅₇Cu₂₀Al₁₀Ni₈Ti₅ alloy: (a) Calculated liquid alloy viscosity; (b) calculated nucleation rates of ZrCu, Zr₂Cu and Zr₈Cu₅ phases.

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图 6 Zr₅₇Cu₂₀Al₁₀Ni₈Ti₅合金的微观结构 (ΔT = 250 K)　(a) 图1(d)中D区域放大; (b) 图1(d)中E区域放大

Fig. 6. Microstructures of Zr₅₇Cu₂₀Al₁₀Ni₈Ti₅ alloy (ΔT = 250 K): (a) D enlarged in Fig. 1(d); (b) E enlarged in Fig. 1(d).

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图 7 过冷度250 K时Zr₅₇Cu₂₀Al₁₀Ni₈Ti₅合金壳区的元素分布　(a) 壳区微观组织; (b) Ni元素含量; (c) Ti元素含量; (d) 总双体分布函数; (e) Zr-Ni偏双体分布函数; (f) Zr-Ti偏双体分布函数

Fig. 7. Element distribution of Zr₅₇Cu₂₀Al₁₀Ni₈Ti₅ alloy shell under 250 K undercooling: (a) Microstructure of alloy shell; (b) Ni content; (c) Ti content; (d) calculated total pair distribution function; (e) calculated Zr-Ni partial bipartite distribution function; (f) calculated Zr-Ti partial bipartite distribution function.

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图 8 Zr₈Cu₅相的微观结构演变　(a) 图6(a)中A区域放大; (b) Zr₈Cu₅相晶格间距随与非晶相距离的变化; (c) Zr₈Cu₅相的XRD曲线

Fig. 8. Microstructure evolution of Zr₈Cu₅ phase: (a) A enlarged in Fig. 6(a); (b) lattice spacing of Zr₈Cu₅ structure versus distance from amorphous phase; (c) calculated Zr₈Cu₅ XRD curves.

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图 9 非晶凝固对合金平均显微硬度的影响　(a) Zr₈Cu₅结晶生长与非晶凝固的系统总体积; (b) Zr₈Cu₅结晶生长与非晶凝固的系统自由体积; (c) 非晶核平均显微硬度

Fig. 9. Effect of amorphous solidification on alloy average microhardness: (a) System total volume of Zr₈Cu₅ crystal growth and amorphous solidification; (b) system free volume of Zr₈Cu₅ crystal growth and amorphous solidification; (c) average microhardness of alloy amorphous core.

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map

[1]	Liu X F, Wang R J, Zhao D Q, Pan M X, Wang W H 2007 Appl. Phys. Lett. 91 041901 Google Scholar
[2]	Sniadecki Z, Mielniczuk B, Idzikowski B, Greneche J M, Robler U K 2010 J. Appl. Phys. 108 073516 Google Scholar
[3]	Zhao R, Jiang H Y, Luo P, Sun Y T, Li Z A, Wu W W, Shen L Q, Liu M, Zhao S F, Wen P, Zhang Q H, Gu L, Bai H Y, Wang W H 2020 Appl. Phys. Lett. 117 131903 Google Scholar
[4]	Shao L L, Xue L, Wang Q Q, Ma K L, Huang J D, Shen B L 2021 J. Alloy. Compd. 874 159964 Google Scholar
[5]	Wei B C, Zhang Y, Zhuang Y X, Zhao D Q, Pan M X, Wang W H 2001 J. Appl. Phys. 89 3529 Google Scholar
[6]	Nishiyama N, Takenaka K, Miura H, Saidoh N, Zeng Y Q, Inoue A 2012 Intermetallics 30 19 Google Scholar
[7]	Tang M Q, Zhang H F, Zhu Z W, Fu H M, Wang A M, Li H, Hu Z Q 2010 J. Mater. Sci. Technol. 26 481 Google Scholar
[8]	Haruyama O, Watanabe T, Yuki K, Horiuchi M, Kato H, Nishiyama N 2011 Phys. Rev. B 83 064201 Google Scholar
[9]	Liu C Y, Wang F, Rao F F, Hou Y 2013 J. Appl. Phys. 113 869 Google Scholar
[10]	Turci F, Tarjus G, Royall C P 2017 Phys. Rev. Lett 118 215501 Google Scholar
[11]	陈季香, 周朔瑶 2014 63 066101 Google Scholar Chen J X, Zhou S Y 2014 Acta Phys. Sin. 63 066101 Google Scholar
[12]	Guerdane M, Teichler H 2001 Phys. Rev. B 65 014203 Google Scholar
[13]	Qi L, Zhang H F, Hu Z Q, Liaw P K 2004 Phys. Lett. A 327 506 Google Scholar
[14]	Brillo J, Pommrich A I, Meyer A 2011 Phys. Rev. Lett. 107 165902 Google Scholar
[15]	Wall J J, Weber R, Kim J, Liaw P K, Choo H 2007 Mat. Sci. Eng. A 445 219 Google Scholar
[16]	Lü P, Wang H P 2017 Scripta Mater. 137 31 Google Scholar
[17]	Hong S J, Chun H, Lee J, Kim B H, Seo M H, Kang J, Han B 2021 J. Phys. Chem. Lett. 12 6000 Google Scholar
[18]	Yao N, Chen X, Fu Z H, Zhang Q 2022 Chem. Rev. 122 10970 Google Scholar
[19]	Wang H, Zhang L F, Han J Q, E W N Deep 2018 Comput. Phys. Commun. 228 178 Google Scholar
[20]	Ketkaew R, Creazzo F, Luber S 2022 J. Phys. Chem. Lett. 13 1797 Google Scholar
[21]	徐山森, 常健, 吴宇昊, 沙莎, 魏炳波 2019 68 196401 Google Scholar Xu S S, Chang J, Wu Y H, Sha S, Wei B B 2019 Acta Phys. Sin. 68 196401 Google Scholar
[22]	Xu S S, Chang J, Sha S, Wei B 2022 Metall. Mater. Trans. A 53 762 Google Scholar
[23]	Xing L Q, Ochina P 1997 Mater. Lett. 30 283 Google Scholar
[24]	Baskes M I 1992 Phys. Rev. B 46 2727 Google Scholar
[25]	Sun Q Q, Qin J Y, Li X X, Wang J, Pan S P 2021 J. Phase Equilib. Diff. 42 166 Google Scholar
[26]	Dai Y, Li J H, Liu B X 2011 J. Appl. Phys. 109 053505 Google Scholar
[27]	Garzon I L, Pasada-Amarillas A 1996 Phys. Rev. B 54 796 Google Scholar
[28]	Turnbull D, Fisher J C 1949 J. Chem. Phys. 1771 Google Scholar
[29]	Tsoutsouva M G, Duffar T, Chaussende D, Kamguem M 2016 J. Cryst. Growth 451 103 Google Scholar
[30]	Kim T H, Gangopadhyay A K, Xing L Q, Lee G W, Shen Y T, Kelton K F, Goldman A I, Hyers R W, Rogers J R 2005 Appl. Phys. Lett. 87 251924 Google Scholar
[31]	Kim S J, Kim Y H, Yang Y S 2001 Mat. Sci. Eng. A 304-306 767 Google Scholar
[32]	Bondi A 1964 J. Phys. Chem. Lett. 68 441
[33]	Bondi A 1966 J. Phys. Chem. C 70 3006 Google Scholar
[34]	Launey M E, Kruzic J J, Li C, Busch R 2007 Appl. Phys. Lett. 91 51913 Google Scholar
[35]	周边, 杨亮 2020 69 116101 Google Scholar Zhou B, Yang L 2020 Acta Phys. Sin. 69 116101 Google Scholar

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液态五元Zr₅₇Cu₂₀Al₁₀Ni₈Ti₅合金的微观结构演变与非晶形成机制