Research paper

Supercooled Liquid Characteristics and Crystallization Decoupling of Zr61Ti2Cu25Al12 Amorphous Alloy

  • LI Xiaocheng ,
  • KOU Shengzhong ,
  • LI Chunling ,
  • LI Chunyan ,
  • ZHAO Yanchun
Expand
  • 1 School of Materials Science and Engineering, Lanzhou University of Technology, Lanzhou 730050, China
    2 State Key Laboratory of Advanced Processing and Recycling of Nonferrous Metals, Lanzhou University of Technology, Lanzhou 730050, China
    3 School of Mechanical and Electrical Engineering, Lanzhou University of Technology, Lanzhou 730050, China
LI Xiaocheng, Tel: (0931)2976702, E-mail: lixc@lut.edu.cn
KOU Shengzhong, professor, Tel: (0931)2976702, E-mail: kousz@lut.cn

Received date: 2023-07-11

  Revised date: 2023-10-11

  Online published: 2023-12-27

Supported by

National Natural Science Foundation of China(51971103);National Natural Science Foundation of China(51861021);Key Research and Development Program of Gansu Province(20YF8GA052)

Abstract

Plastic deformation of amorphous alloys below the glass transition temperature is inhomogeneous and highly localized within narrow shear bands. However, the processing and manufacturing of amorphous alloys in their supercooled liquid state exhibit unique advantages for engineering application. Although the discovery of bulk metallic glasses has substantially expanded the processing time and temperature window, experimental research on the supercooled liquid states of amorphous alloys remains widely limited to narrow regions near either their glass transition temperature or melting point. The crystallization of supercooled liquids severely limits the characterization of their kinetic behavior in the high-temperature region. Therefore, an enhanced comprehensive understanding of supercooled liquid characteristics and crystallization kinetic behavior of metallic glasses is necessary. Zr61Ti2Cu25Al12 amorphous alloy shows broad application prospects in the fabrication of flexible mechanism components and biological implants because of its high fracture toughness, high elastic strain limit, and good biocompatibility properties. Six orders of magnitude (10-2-104 K/s) of heating rate changes were achieved for Zr61Ti2Cu25Al12 metallic glass by combining flash differential scanning calorimetry (FDSC) with conventional DSC. This implies that the kinetic characteristics of the alloy supercooled liquid is dependent on the heating rate of the alloy over an ultra-extensive temperature range. The kinetic behavior of the alloy supercooled liquid lags behind the rapid changes in temperature, and both follow the Vogel-Fulcher-Tammann equation. The small variation in the fragility index (m = 35-47) indicates that the supercooled liquid structure changes gently with temperature, thereby showing a “strong” liquid behavior. An average m ≈ 45 is obtained over the entire temperature range from the glass transition temperature to the melting point via time dimension coordinate translation. The dependence of crystal growth on temperature during the crystallization process of the Zr61Ti2Cu25Al12 amorphous alloy indicates that the activation energy of crystal growth gradually decreases with increasing temperature, and the reduction in activation energy per unit temperature obtained here is approximately 0.5 kJ/(mol·K). Near the glass transition temperature, decoupling occurs between crystal growth kinetics and viscous flow. The kinetics coefficient for crystal growth (Ukin) follows a power law relationship with viscosity (η) over a wide temperature range when an exponent ξ = 0.84 is introduced: Ukinη-ξ.

Cite this article

LI Xiaocheng , KOU Shengzhong , LI Chunling , LI Chunyan , ZHAO Yanchun . Supercooled Liquid Characteristics and Crystallization Decoupling of Zr61Ti2Cu25Al12 Amorphous Alloy[J]. Acta Metall Sin, 2025 , 61(6) : 900 -908 . DOI: 10.11900/0412.1961.2023.00299

References

1 Wang W H. The nature and properties of amorphous matter [J]. Prog. Phys., 2013, 33: 177
  汪卫华. 非晶态物质的本质和特性 [J]. 物理学进展, 2013, 33: 177
2 Johnson W L. Bulk glass-forming metallic alloys: Science and technology [J]. MRS Bull., 1999, 24: 42
3 Li M X, Zhao S F, Lu Z, et al. High-temperature bulk metallic glasses developed by combinatorial methods [J]. Nature, 2019, 569: 99
4 Wang W H. The elastic properties, elastic models and elastic perspectives of metallic glasses [J]. Prog. Mater. Sci., 2012, 57: 487
5 Li C Y, Zhu F P, Ding J Q, et al. Nanoindentation investigation on creep behavior of Zr-based bulk metallic glass [J]. Rare Met. Mater. Eng., 2020, 49: 3353
6 Zhao Y C, Mao X J, Li W S, et al. Microstructure and corrosion behavior of Fe-15Mn-5Si-14Cr-0.2C amorphous steel [J]. Acta Metall. Sin., 2020, 56: 715
  赵燕春, 毛雪晶, 李文生 等. Fe-15Mn-5Si-14Cr-0.2C非晶钢微观组织与腐蚀行为 [J]. 金属学报, 2020, 56: 715
7 He Q, Cheng Y Q, Ma E, et al. Locating bulk metallic glasses with high fracture toughness: Chemical effects and composition optimization [J]. Acta Mater., 2011, 59: 202
8 He Q, Xu J. Locating malleable bulk metallic glasses in Zr-Ti-Cu-Al alloys with calorimetric glass transition temperature as an indicator [J]. J. Mater. Sci. Technol., 2012, 28: 1109
9 Li D F, Yang Y L, Shen Y, et al. Bending fatigue behavior of thin Zr61Ti2Cu25Al12 bulk metallic glass beams for compliant mechanisms application [J]. J. Mater. Sci. Technol., 2021, 89: 1
10 Li J, Shi L L, Zhu Z D, et al. Zr61Ti2Cu25Al12 metallic glass for potential use in dental implants: Biocompatibility assessment by in vitro cellular responses [J]. Mater. Sci. Eng., 2013, C33: 2113
11 Liu S S, Hou C N, Wang E G, et al. Plastic rheological behaviors of Zr61Cu25Al12Ti2 and Zr52.5Cu17.9Ni14.6Al10Ti5 amorphous alloys in the supercooled liquid region [J]. Acta Metall. Sin., 2021, 58: 807
  刘帅帅, 侯超楠, 王恩刚 等. Zr61Cu25Al12Ti2和Zr52.5Cu17.9Ni14.6Al10-Ti5块体非晶合金过冷液相区的塑性流变行为 [J]. 金属学报, 2021, 58: 807
12 Kissinger H E. Reaction kinetics in differential thermal analysis [J]. Anal. Chem., 1957, 29: 1702
13 Brüning R, Samwer K. Glass transition on long time scales [J]. Phys. Rev., 1992, 46B: 11318
14 Bai F X, Yao J H, Wang Y X, et al. Crystallization kinetics of an Au-based metallic glass upon ultrafast heating and cooling [J]. Scripta Mater., 2017, 132: 58
15 Yang Q, Peng S X, Bu Q Z, et al. Revealing glass transition and supercooled liquid in Ni80P20 metallic glass [J]. Acta Metall. Sin., 2021, 57: 553
  杨 群, 彭思旭, 卜庆周 等. 非晶态Ni80P20合金的玻璃转变和过冷液体性质 [J]. 金属学报, 2021, 57: 553
16 Yang Q, Huang J, Qin X H, et al. Revealing hidden supercooled liquid states in Al-based metallic glasses by ultrafast scanning calorimetry: Approaching theoretical ceiling of liquid fragility [J]. Sci. China Mater., 2020, 63: 157
17 Orava J, Greer A L, Gholipour B, et al. Characterization of supercooled liquid Ge2Sb2Te5 and its crystallization by ultrafast-heating calorimetry [J]. Nat. Mater., 2012, 11: 279
18 Chen Y X, Zhou D S, Hu W B. Progress of differential scanning calorimetry and its application in polymer characterization [J]. Acta Polym. Sin., 2021, 52: 423
  陈咏萱, 周东山, 胡文兵. 示差扫描量热法进展及其在高分子表征中的应用 [J]. 高分子学报, 2021, 52: 423
19 Angell C A. Formation of glasses from liquids and biopolymers [J]. Science, 1995, 267: 1924
20 Ashkenazy Y, Averback R S. Kinetic stages in the crystallization of deeply undercooled body-centered-cubic and face-centered-cubic metals [J]. Acta Mater., 2010, 58: 524
21 Sun Y, Xi H M, Chen S, et al. Crystallization near glass transition: Transition from diffusion-controlled to diffusionless crystal growth studied with seven polymorphs [J]. J. Phys. Chem., 2008, 112B: 5594
22 Ediger M D, Harrowell P, Yu L. Crystal growth kinetics exhibit a fragility-dependent decoupling from viscosity [J]. J. Chem. Phys., 2008, 128: 034709
23 Nascimento M L F, Zanotto E D. Does viscosity describe the kinetic barrier for crystal growth from the liquidus to the glass transition? [J]. J. Chem. Phys., 2010, 133: 174701
24 Zhuravlev E, Schick C. Fast scanning power compensated differential scanning nano-calorimeter: 1. The device [J]. Thermochim. Acta, 2010, 505: 1
25 Zhuravlev E, Schick C. Fast scanning power compensated differential scanning nano-calorimeter: 2. Heat capacity analysis [J]. Thermochim. Acta, 2010, 505: 14
26 Kelton K F. Analysis of crystallization kinetics [J]. Mater. Sci. Eng., 1997, A226-228: 142
27 Lasocka M. The effect of scanning rate on glass transition temperature of splat-cooled Te85Ge15 [J]. Mater. Sci. Eng., 1976, 23: 173
28 Vogel H. The law of the relation between the viscosity of liquids and the temperature [J]. Phys. Zeit., 1921, 22: 645
29 Fulcher G S. Analysis of recent measurements of the viscosity of glasses [J]. J. Am. Ceram. Soc., 1925, 8: 339
30 Tammann G, Hesse W. Die abh?ngigkeit der viscosit?t von der temperatur bei unterkühlten flüssigkeiten [J]. Z. Anorg. Allg. Chem., 1926, 156: 245
31 Bohmer R, Angell C A. Correlations of the nonexponentiality and state dependence of mechanical relaxations with bond connectivity in Ge-As-Se supercooled liquids [J]. Phys. Rev., 1992, 45B: 10091
32 Perera D N, Tsai A P. Thermal and viscoelastic properties of a strong bulk metallic glass former [J]. J. Phys., 2000, 33D: 1937
33 Chen H S. A method for evaluating viscosities of metallic glasses from the rates of thermal transformations [J]. J. Non-Cryst. Solids, 1978, 27: 257
34 Cohen M H, Grest G S. Liquid-glass transition a free-volume approach [J]. Phys. Rev., 1979, 20B: 1077
35 Angell C A, Sichina W. Thermodynamics of the glass transition: Empirical aspects [J]. Ann. N. Y. Acad. Sci., 1976, 279: 53
36 Busch R, Schroers J, Wang W H. Thermodynamics and kinetics of bulk metallic glass [J]. MRS Bull., 2007, 32: 620
37 Waniuk T A, Busch R, Masuhr A, et al. Equilibrium viscosity of the Zr41.2Ti13.8Cu12.5Ni10Be22.5 bulk metallic glass-forming liquid and viscous flow during relaxation, phase separation, and primary crystallization [J]. Acta Mater., 1998, 46: 5229
38 Busch R, Gallino I. Kinetics, thermodynamics, and structure of bulk metallic glass forming liquids [J]. JOM, 2017, 69: 2178
39 Alba C, Busse L E, List D J, et al. Thermodynamic aspects of the vitrification of toluene, and xylene isomers, and the fragility of liquid hydrocarbons [J]. J. Chem. Phys., 1990, 92: 617
Outlines

/