Fe含量对Zr60Cu40-xFex相分离非晶合金组织结构、电阻性能和纳米压痕行为的影响

doi:10.11900/0412.1961.2020.00137

金属学报

2021, Vol. 57

Issue (5): 675-683 DOI: 10.11900/0412.1961.2020.00137

研究论文

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Fe含量对Zr₆₀Cu₄₀_-_xFe_x相分离非晶合金组织结构、电阻性能和纳米压痕行为的影响

孙小钧¹^,², 何杰¹^,²(

), 陈斌¹^,², 赵九洲¹^,², 江鸿翔¹, 张丽丽¹, 郝红日¹

^1.中国科学院金属研究所师昌绪先进材料创新中心沈阳 110016
^2.中国科学技术大学材料科学与工程学院沈阳 110016

Effect of Fe Content on the Microstructure, Electrical Resistivity, and Nanoindentation Behavior of Zr₆₀Cu₄₀_-_xFe_x Phase-Separated Metallic Glasses

SUN Xiaojun¹^,², HE Jie¹^,²(

), CHEN Bin¹^,², ZHAO Jiuzhou¹^,², JIANG Hongxiang¹, ZHANG Lili¹, HAO Hongri¹

^1.Shi -Changxu Innovation Center for Advanced Materials, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
^2.School of Materials Science and Engineering, University of Science and Technology of China, Shenyang 110016, China

引用本文:

孙小钧, 何杰, 陈斌, 赵九洲, 江鸿翔, 张丽丽, 郝红日. Fe含量对Zr₆₀Cu₄₀_-_xFe_x相分离非晶合金组织结构、电阻性能和纳米压痕行为的影响[J]. 金属学报, 2021, 57(5): 675-683.
Xiaojun SUN, Jie HE, Bin CHEN, Jiuzhou ZHAO, Hongxiang JIANG, Lili ZHANG, Hongri HAO. Effect of Fe Content on the Microstructure, Electrical Resistivity, and Nanoindentation Behavior of Zr₆₀Cu₄₀_-_xFe_x Phase-Separated Metallic Glasses[J]. Acta Metall Sin, 2021, 57(5): 675-683.

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摘要:

在Zr₆₀Cu₄₀单相非晶合金中引入与合金次要组元Cu具有正混合焓的Fe元素，设计了Zr₆₀Cu_40-_xFe_x相分离非晶合金，研究了Zr₆₀Cu_40-_xFe_x三元合金的液-液相分离行为。结果表明，二元Cu-Fe合金的液态组元不混溶区域可以延伸至三元Zr₆₀Cu_40-_xFe_x合金中；在快速凝固条件下，该合金在冷却过程中会发生液-液相分离，形成富Cu和富Fe两液相；基于Zr₆₀Cu_40-_xFe_x合金液-液相分离凝固特征，考察了Fe含量对Zr₆₀Cu_40-_xFe_x合金组织及相结构的影响，讨论了Zr₆₀Cu_40-_xFe_x体系组织演变及相形成机制。Zr₆₀Cu₂₀Fe₂₀合金在冷却过程中液-液相分离形成的富Zr-Cu和富Zr-Fe两液相分别发生玻璃转变，最终形成了高数量密度(10²⁴/m³数量级)的纳米富Cu非晶粒子(尺寸为2~10 nm)分布在富Fe非晶基体上的相分离非晶合金组织。研究了该合金样品的电阻性能和纳米压痕行为，讨论了Zr₆₀Cu₂₀Fe₂₀合金晶化过程的电阻反常变化行为，并分析了Zr₆₀Cu₂₀Fe₂₀合金的纳米尺度相分离组织结构对剪切转变区的影响。

关键词 ：液-液相分离, 难混溶合金, 金属玻璃, 电阻行为, 纳米压痕

Abstract：

Liquid-liquid phase separation was used to design phase-separated metallic glasses with special properties. In this work, Zr₆₀Cu_40-_xFe_x phase-separated metallic glasses were designed by partial substitution of Cu by Fe in Zr₆₀Cu₄₀ metallic glass. The liquid-liquid phase separation behavior of Zr₆₀Cu_40-_xFe_x alloy was investigated. The results show that the miscibility gap of the binary Cu-Fe system can be extended into the Zr₆₀Cu_40-_xFe_x system and that liquid-liquid phase separation into Cu-rich and Fe-rich liquids occurred during rapid cooling. On the basis of the behavior of liquid-liquid phase separation of the Zr₆₀Cu_40-_xFe_x system, the effect of partial substitution of Cu by Fe on the microstructure and phase formation of the Zr₆₀Cu_40-_xFe_x alloys was investigated. The microstructure evolution and the competitive mechanism of phase formation in the as-quenched Zr₆₀Cu_40-_xFe_x alloy were discussed. For the Zr₆₀Cu₂₀Fe₂₀ alloy, liquid-liquid phase separation into Cu-rich and Fe-rich liquids and then liquid-glass transition occurred during rapid cooling and resulted in a heterogeneous structure with glassy Fe-rich matrix embedded with glassy Cu-rich nanoparticles. Considering this structure, the electrical properties and nanoindentation behavior of the as-quenched Zr₆₀Cu₂₀Fe₂₀ alloy were examined. The abnormal change in electrical resistivity during crystallization and the effect of nanoscale phase separation on the shear transformation zone of the Zr₆₀Cu₂₀Fe₂₀ alloy were analyzed.

Key words： liquid-liquid phase separation immiscible alloy metallic glass electrical resistivity behavior nanoindentation

收稿日期: 2020-04-30

ZTFLH:

TG113.11

基金资助:国家自然科学基金项目(51774264);辽宁省自然科学基金项目(2019-MS-332)

作者简介: 孙小钧，男，1993年生，博士

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链接本文:

https://www.ams.org.cn/CN/10.11900/0412.1961.2020.00137 或 https://www.ams.org.cn/CN/Y2021/V57/I5/675

图1 Zr60Cu40-xFex合金薄带样品的XRD谱及DTA曲线

表1 Zr60Cu40-xFex合金热力学参数

图2 Zr60Cu40-xFex合金薄带样品微观组织的TEM像和SAED花样

图3 计算的Zr60Cu40-xFex合金的组元液态不混溶区

图4 合金匀速升温过程中约化电阻和DSC曲线

图5 Zr60Cu20Fe20合金在673、713和813 K等温退火0.5 h前后的XRD谱

图6 Zr60Cu20Fe20合金富Zr-Fe基体及富Zr-Cu粒子在673 K等温退火0.5 h后的HRTEM像(a) glassy Fe-rich matrix (the rectangular areas indicate the formation of nanocrystals)(b) glassy Cu-rich sphere

图7 纳米压痕力-位移(P-h)曲线

表2 合金条带的纳米压痕硬度、模量、应变速率敏感系数(m)及剪切转变区体积(Ω)

图8 蠕变拟合曲线，应变速率及硬度随蠕变时间的变化关系，及线性拟合得到的m值

1	Ratke L, Diefenbach S. Liquid immiscible alloys [J]. Mater. Sci. Eng., 1995, R15: 263
2	He J, Kaban I, Mattern N, et al. Local microstructure evolution at shear bands in metallic glasses with nanoscale phase separation [J]. Sci. Rep., 2016, 6: 25832
3	Sun Q, Jiang H X, Zhao J Z, et al. Microstructure evolution during the liquid-liquid phase transformation of Al-Bi alloys under the effect of TiC particles [J]. Acta Mater., 2017, 129: 321
4	Chen S Q, Hui K Z, Dong L Z, et al. Excellent long-term reactivity of inhomogeneous nanoscale Fe-based metallic glass in wastewater purification [J]. Sci. China Mater., 2020, 63: 453
5	Wang C P, Liu X J, Ohnuma I, et al. Formation of immiscible alloy powders with egg-type microstructure [J]. Science, 2002, 297: 990
6	Xian A P, Zhu Y X. The development of manufacture processing for Cu-Cr contact alloy [J]. Acta Metall. Sin., 2003, 39: 225
6	冼爱平, 朱耀宵. Cu-Cr触头合金制备技术的发展 [J]. 金属学报, 2003, 39: 225
7	He J, Jiang H X, Chen S, et al. Liquid phase separation in immiscible Ag-Ni-Nb alloy and formation of crystalline/amorphous composite [J]. J. Non-Cryst. Solids, 2011, 357: 3561
8	Xi Y Y, He J, Sun X J, et al. Ni-based metallic glass composites containing Cu-rich crystalline nanospheres [J]. Acta Metall. Sin. (Engl. Lett.), 2018, 31: 1130
9	He J, Mattern N, Kaban I, et al. Enhancement of glass-forming ability and mechanical behavior of zirconium-lanthanide two-phase bulk metallic glasses [J]. J. Alloys Compd., 2015, 618: 795
10	Wang Z Y, He J, Yang B J, et al. Liquid-liquid phase separation and formation of two glassy phases in Zr-Ce-Co-Cu immiscible alloys [J]. Acta Metall. Sin., 2016, 52: 1379
10	王中原, 何杰, 杨柏俊等. Zr-Ce-Co-Cu难混溶合金的液-液相分离和双非晶相形成 [J]. 金属学报, 2016, 52: 1379
11	Kündig A A, Ohnuma M, Ping D H, et al. In situ formed two-phase metallic glass with surface fractal microstructure [J]. Acta Mater., 2004, 52: 2441
12	Park B J, Chang H J, Kim D H, et al. In situ formation of two amorphous phases by liquid phase separation in Y-Ti-Al-Co alloy [J]. Appl. Phys. Lett., 2004, 85: 6353
13	Chang H J, Yook W, Park E S, et al. Synthesis of metallic glass composites using phase separation phenomena [J]. Acta Mater., 2010, 58: 2483
14	Mattern N, Kühn U, Gebert A, et al. Microstructure and thermal behavior of two-phase amorphous Ni-Nb-Y alloy [J]. Scr. Mater., 2005, 53: 271
15	Han X L, Qin Y S, Qin K, et al. Glass-forming ability and early crystallization kinetics of novel Cu-Zr-Al-Co bulk metallic glasses [J]. Metals, 2016, 6: 225
16	Sun X J, He J, Chen B, et al. Microstructure formation and electrical resistivity behavior of rapidly solidified Cu-Fe-Zr immiscible alloys [J]. J. Mater. Sci. Technol., 2020, 44: 201
17	Sun X J, He J, Wang Z Y, et al. Liquid-liquid phase separation and two-phase bulk metallic glasses of Ce-Zr based alloys [J]. Sci. Sin. Technol., 2018, 48: 1413
17	孙小钧, 何杰, 王中原等. Ce-Zr基合金液-液相分离机制及双相块体非晶合金研究 [J]. 中国科学: 技术科学, 2018, 48: 1413
18	Qiao J C, Wang Q, Pelletier J M, et al. Structural heterogeneities and mechanical behavior of amorphous alloys [J]. Prog. Mater. Sci., 2019, 104: 250
19	Pan J, Liu L, Chan K C. Enhanced plasticity by phase separation in CuZrAl bulk metallic glass with micro-addition of Fe [J]. Scr. Mater., 2009, 60: 822
20	He J, Zhao J Z, Ratke L. Solidification microstructure and dynamics of metastable phase transformation in undercooled liquid Cu-Fe alloys [J]. Acta Mater., 2006, 54: 1749
21	Chen B, He J, Xi Y Y, et al. Liquid-liquid hierarchical separation and metal recycling of waste printed circuit boards [J]. J. Hazard. Mater., 2019, 364: 388
22	Chen Q, Jin Z P. The Fe-Cu system: A thermodynamic evaluation [J]. Metall. Mater. Trans., 1995, 26A: 417
23	Dreval L A, Agraval P G, Turchanin M A. Enthalpy of mixing of liquid Cu-Fe-Zr alloys at 1873 K (1600^oC) [J]. Metall. Mater. Trans., 2015, 46B: 2234
24	Guo C P, Du Z M, Li C R, et al. Thermodynamic description of the Al-Fe-Zr system [J]. Calphad, 2008, 32: 637
25	Hsiao H M, Liang S M, Schmid-Fetzer R, et al. Thermodynamic assessment of the Ag-Zr and Cu-Zr binary systems [J]. Calphad, 2016, 55: 77
26	Bakke E, Busch R, Johnson W L. The viscosity of the Zr_46.75Ti_8.25Cu_7.5Ni₁₀Be_27.5 bulk metallic glass forming alloy in the supercooled liquid [J]. Appl. Phys. Lett., 1995, 67: 3260
27	Deng C K, Jiang H X, Zhao J Z, et al. Study on the solidification of Ag-Ni monotectic alloy [J]. Acta Metall. Sin., 2020, 56: 212
27	邓聪坤, 江鸿翔, 赵九洲等. Ag-Ni偏晶合金凝固过程研究 [J]. 金属学报, 2020, 56: 212
28	Chung S J, Hong K T, Ok M R, et al. Analysis of the crystallization of Zr₄₁Ti₁₄Cu_12.5Ni₁₀Be_22.5 bulk metallic glass using electrical resistivity measurement [J]. Scr. Mater., 2005, 53: 223
29	Haruyama O, Miyazawa T, Saida J, et al. Change in electrical resistivity due to icosahedral phase precipitation in Zr₇₀Pd₂₀Ni₁₀ and Zr₆₅Al_7.5Cu_7.5Ni₁₀Ag₁₀ glasses [J]. Appl. Phys. Lett., 2001, 79: 758
30	Li M X, Zhao S F, Zhen L, et al. High-temperature bulk metallic glasses developed by combinatorial methods [J]. Nature, 2019, 569: 99
31	Ichitsubo T, Matsubara E, Yamamoto T, et al. Microstructure of fragile metallic glasses inferred from ultrasound-accelerated crystallization in Pd-based metallic glasses [J]. Phys. Rev. Lett., 2005, 95: 245501
32	Cohen M H, Turnbull D. Molecular transport in liquids and glasses [J]. J. Chem. Phys., 1959, 31: 1164
33	Argon A S, Kuo H Y. Plastic flow in a disordered bubble raft (an analog of a metallic glass) [J]. Mater. Sci. Eng., 1979, 39: 101
34	Wang Z, Wang W H. Flow units as dynamic defects in metallic glassy materials [J]. Natl. Sci. Rev., 2019, 6: 304
35	Johnson W L, Samwer K. A universal criterion for plastic yielding of metallic glasses with a (T / T_g)^2/3 temperature dependence [J]. Phys. Rev. Lett., 2005, 95: 195501
36	Pan D, Inoue A, Sakurai T, et al. Experimental characterization of shear transformation zones for plastic flow of bulk metallic glasses [J]. Proc. Natl. Acad. Sci. USA, 2008, 105: 14769
37	Nandam S H, Ivanisenko Y, Schwaiger R, et al. Cu-Zr nanoglasses: Atomic structure, thermal stability and indentation properties [J]. Acta Mater., 2017, 136: 181
38	Şopu D, Ritter Y, Gleiter H, et al. Deformation behavior of bulk and nanostructured metallic glasses studied via molecular dynamics simulations [J]. Phys. Rev., 2011, 83B: 100202

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