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).

文章全文 : translate this paragraph

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
[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 物理学报 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 物理学报 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 物理学报 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.

下载: 全尺寸图片幻灯片

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.

下载: 全尺寸图片幻灯片

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.

下载: 全尺寸图片幻灯片

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.

下载: 全尺寸图片幻灯片

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.

下载: 全尺寸图片幻灯片

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).

下载: 全尺寸图片幻灯片

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.

下载: 全尺寸图片幻灯片

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.

下载: 全尺寸图片幻灯片

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.

下载: 全尺寸图片幻灯片

[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 物理学报 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 物理学报 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 物理学报 69 116101 Google Scholar Zhou B, Yang L 2020 Acta Phys. Sin. 69 116101 Google Scholar

[1]	糜晓磊, 胡亮, 武博文, 龙强, 魏炳波. 钆含量对Fe-B-Nb-Gd非晶合金磁学性能和氧化机制的影响规律. 物理学报, 2024, 73(9): 097102. doi: 10.7498/aps.73.20232040
[2]	金英捷, 耿德路, 林茂杰, 胡亮, 魏炳波. 静电悬浮条件下液态Zr₆₀Ni₂₅Al₁₅合金的热物理性质与快速凝固机制. 物理学报, 2024, 73(8): 086401. doi: 10.7498/aps.73.20232002
[3]	武博文, 胡亮, 耿德路, 魏炳波. 液态Zr₃₅Al₂₃Ni₂₂Gd₂₀合金的亚稳相分离与双相非晶形成机理. 物理学报, 2023, 72(21): 216401. doi: 10.7498/aps.72.20231002
[4]	周边, 杨亮. 分子动力学模拟冷却速率对非晶合金结构与变形行为的影响. 物理学报, 2020, 69(11): 116101. doi: 10.7498/aps.69.20191781
[5]	徐山森, 常健, 吴宇昊, 沙莎, 魏炳波. 液态五元Ni-Zr-Ti-Al-Cu合金快速凝固过程的高速摄影研究. 物理学报, 2019, 68(19): 196401. doi: 10.7498/aps.68.20190910
[6]	吴博强, 刘海蓉, 刘让苏, 莫云飞, 田泽安, 梁永超, 关绍康, 黄昌雄. 冷速对液态金属Mg凝固过程中微观结构演变的影响. 物理学报, 2017, 66(1): 016101. doi: 10.7498/aps.66.016101
[7]	孙川琴, 黄海深, 毕庆玲, 吕勇军. 非晶态合金表面的水润湿动力学. 物理学报, 2017, 66(17): 176101. doi: 10.7498/aps.66.176101
[8]	陈克萍, 吕鹏, 王海鹏. 微重力条件下Cu-Zr共晶合金的液固相变研究. 物理学报, 2017, 66(6): 068101. doi: 10.7498/aps.66.068101
[9]	谷倩倩, 阮莹, 代富平. 微重力下Fe-Al-Nb合金液滴的快速凝固机理及其对显微硬度的影响. 物理学报, 2017, 66(10): 106401. doi: 10.7498/aps.66.106401
[10]	朱海哲, 阮莹, 谷倩倩, 闫娜, 代富平. 落管中Ni-Fe-Ti合金的快速凝固机理及其磁学性能. 物理学报, 2017, 66(13): 138101. doi: 10.7498/aps.66.138101
[11]	林茂杰, 常健, 吴宇昊, 徐山森, 魏炳波. 电磁悬浮条件下液态Fe50Cu50合金的对流和凝固规律研究. 物理学报, 2017, 66(13): 136401. doi: 10.7498/aps.66.136401
[12]	魏绍楼, 黄陆军, 常健, 杨尚京, 耿林. 液态Ti-Al合金的深过冷与快速枝晶生长. 物理学报, 2016, 65(9): 096101. doi: 10.7498/aps.65.096101
[13]	杨尚京, 王伟丽, 魏炳波. 深过冷液态Al-Ni合金中枝晶与共晶生长机理. 物理学报, 2015, 64(5): 056401. doi: 10.7498/aps.64.056401
[14]	王小娟, 阮莹, 洪振宇. Al-Cu-Ge合金的热物理性质与快速凝固规律研究. 物理学报, 2014, 63(9): 098101. doi: 10.7498/aps.63.098101
[15]	殷涵玉, 鲁晓宇. 深过冷Cu60Sn30Pb10偏晶合金的快速凝固. 物理学报, 2008, 57(7): 4341-4346. doi: 10.7498/aps.57.4341
[16]	翟秋亚, 杨扬, 徐锦锋, 郭学锋. 快速凝固Cu-Sn亚包晶合金的电阻率及力学性能. 物理学报, 2007, 56(10): 6118-6123. doi: 10.7498/aps.56.6118
[17]	梅策香, 阮莹, 代富平, 魏炳波. 深过冷Ag-Cu-Ge三元共晶合金的相组成与凝固特征. 物理学报, 2007, 56(2): 988-993. doi: 10.7498/aps.56.988
[18]	臧渡洋, 王海鹏, 魏炳波. 深过冷三元Ni-Cu-Co合金的快速枝晶生长. 物理学报, 2007, 56(8): 4804-4809. doi: 10.7498/aps.56.4804
[19]	杨弘, 陈民. 深过冷液态Ni2TiAl合金热物理性质的分子动力学模拟. 物理学报, 2006, 55(5): 2418-2421. doi: 10.7498/aps.55.2418
[20]	张蜡宝, 代富平, 熊予莹, 魏炳波. 深过冷Ni-15％Sn合金熔体表面张力研究. 物理学报, 2006, 55(1): 419-423. doi: 10.7498/aps.55.419

计量

文章访问数: 2601
PDF下载量: 68
被引次数: 0

姓名
邮箱
手机号码
标题
留言内容
验证码

搜索

留言板

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