Supercooled Liquid Characteristics and Crystallization Decoupling of Zr61Ti2Cu25Al12 Amorphous Alloy

doi:10.11900/0412.1961.2023.00299

Acta Metall Sin

2025, Vol. 61

Issue (6): 900-908 DOI: 10.11900/0412.1961.2023.00299

Research paper

Current Issue | Archive | Adv Search

Supercooled Liquid Characteristics and Crystallization Decoupling of Zr₆₁Ti₂Cu₂₅Al₁₂ Amorphous Alloy

LI Xiaocheng¹(

), KOU Shengzhong¹^,²(

), LI Chunling³, LI Chunyan¹^,², ZHAO Yanchun¹^,²

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

Cite this article:

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

Download:

HTML

PDF(1611KB)
Export: BibTeX | EndNote (RIS)

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 (U_kin) follows a power law relationship with viscosity (η) over a wide temperature range when an exponent ξ = 0.84 is introduced: U_kin ∝ η^-^ξ.

Key words: amorphous alloy flash DSC supercooled liquid viscosity fragility crystallization

Received: 11 July 2023

ZTFLH:

TG139

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

Corresponding Authors: LI Xiaocheng, Tel: (0931)2976702, E-mail: lixc@lut.edu.cn
KOU Shengzhong, professor, Tel: (0931)2976702, E-mail: kousz@lut.cn

	Service

	E-mail this article
	Add to citation manager
	E-mail Alert
	RSS
	（）
	Articles by authors
	LI Xiaocheng
	KOU Shengzhong
	LI Chunling
	LI Chunyan
	ZHAO Yanchun

URL:

https://www.ams.org.cn/EN/10.11900/0412.1961.2023.00299 OR https://www.ams.org.cn/EN/Y2025/V61/I6/900

Fig.1 XRD spectrum (a) and HRTEM image (Inset shows selected area electron diffraction (SAED) pattern) (b) of Zr₆₁Ti₂Cu₂₅Al₁₂ as-cast rod with a diameter of 3 mm

Fig.2 Heat flow curves of conventional DSC at low heating rate (Φ_h) from 0.05 K/s to 1.33 K/s (As a comparison, 500 K/s is also included in Fig.2a) (a) and FDSC at high Φ_h from 100 K/s to 5.5 × 10⁴ K/s (Φ_h = 100, 200, 400, 600, 800, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 6000, 7000, 8000, 9000, 10000, 15000, 20000, 25000, 30000, 35000, 40000, 45000, 50000, 55000 K/s) (b) for Zr₆₁Ti₂Cu₂₅Al₁₂ metallic glass (DSC—differential scanning calorimetry, FDSC—fast differential scanning calorimetry, Φ_c─cooling rate, T─temperature, T_g─glass transition temperature, T_x─crystallization temperature, T_p─crystallization peak temperature, ΔH_m─melting enthalpy)

Fig.3 Changes in activation energy for glass transition (a) and crystallization (b) of Zr₆₁Ti₂Cu₂₅Al₁₂amorphous alloy and corresponding Kissinger plots (E─activation energy, E_g─activation energy relative to T_g, E_p─activation energy relative to T_p)

Fig.4 Dependence of the characteristic temperatures in Zr₆₁Ti₂Cu₂₅Al₁₂ alloy on the natural logarithm of the Φ_h (a) and adjusted with proper time dimension shift (b) (m─fragility index; $m T g$ ─fragility relative to T_g; $m T X$ ─fragility relative to T_x; $m T P$ ─fragility relative to T_p; r²─determination coefficient; 4 denotes the relative scale on the y-axis, the same below)

Table 1 lnΦ_h-T fitting parameters (B₀, D₀, T₀) and r² for characteristic temperatures of Zr₆₁Ti₂Cu₂₅Al₁₂ alloy

Fig.5 Kissinger plots for characteristic temperatures of Zr₆₁Ti₂Cu₂₅Al₁₂ metallic glass (a) and adjusted with proper time dimension shift (b) (U─crystal growth rate; η─viscosity; U_kin─kinetic coefficient for crystal growth; T_c─characteristic temperatures T_g, T_x, and T_p)

Table 2 lnU-1000 / T and lnU_kin-1000 / T fitting parameters and determination coefficients for characteristic temperatures of Zr₆₁Ti₂Cu₂₅Al₁₂ alloy

Table 3 -lnη-1000 / T fitting parameters and determination coefficient for characteristic temperatures of Zr₆₁Ti₂Cu₂₅Al₁₂ alloy

Fig.6 Angell plot for reduced temperature dependence of viscosity in several representative glass forming liquids^[36~38] (The strongest SiO₂ and the most fragile o-terphenyl as the upper and lower limits are also included)

Fig.7 Decoupling exponent (ξ) representing the decoupling of crystal growth kinetics from viscous flow plotted as a function of the supercooled liquid m (GST—Ge₂Sb₂Te₅)

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 doi: 10.11900/0412.1961.2019.00275
	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 doi: 10.11900/0412.1961.2019.00275
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 Zr_52.5Cu_17.9Ni_14.6Al₁₀Ti₅ 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Zr_52.5Cu_17.9Ni_14.6Al₁₀-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 doi: 10.1038/nmat3275 pmid: 22426461
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 pmid: 17770101
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 abhängigkeit der viscosität 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 Zr_41.2Ti_13.8Cu_12.5Ni₁₀Be_22.5 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

[1]	CAI Zhengqing, YIN Dawei, YANG Liang, WANG Wenxiang, WANG Feilong, WEN Yongqing, MA Mingzhen. Effect of Ag Substitution of Cu on Properties of Zr-Ti-Cu-Al Amorphous Alloys[J]. 金属学报, 2025, 61(4): 572-582.
[2]	BAO Chengli, LI Hao, HU Li, ZHOU Tao, TANG Ming, HE Qubo, LIU Xiangguo. Construction of Hot Processing Map of Solutionized Mg-10Gd-6Y-1.5Zn-0.5Zr Alloy and Microstructure Evolution[J]. 金属学报, 2025, 61(4): 632-642.
[3]	PENG Zichao, LUO Junpeng, ZHAO Yu, ZHOU Lei, WANG Xuqing, ZOU Jinwen. Evolution of Microstrucutre During Static Recrystallization in FGH96 Superalloy[J]. 金属学报, 2025, 61(2): 235-242.
[4]	LIU Guanghui, WANG Weiguo, Rohrer Gregory S, CHEN Song, LIN Yan, TONG Fang, FENG Xiaozheng, ZHOU Bangxin. {111}/{111} Near Singular Boundaries in a Dynamically Recrystallized Al-Zn-Mg-Cu Alloy Compressed at Elevated Temperature[J]. 金属学报, 2024, 60(9): 1165-1178.
[5]	DONG Weixia, YAO Zhongzheng, LIU Sinan, CHEN Guoxing, WANG Xun-Li, WU Zhenduo, LAN Si. Evolution of Short-to-Medium Range Orders During the Liquid-Liquid Phase Transition of a Pd-Si Metallic Glass[J]. 金属学报, 2024, 60(8): 1119-1129.
[6]	YANG Ruize, ZHAI Ruzong, REN Shaofei, SUN Mingyue, XU Bin, QIAO Yanxin, YANG Lanlan. Evolution and Healing Mechanism of 1Cr22Mn16N High Nitrogen Austenitic Stainless Steel Interface Microstructure During Plastic Deformation Bonding[J]. 金属学报, 2024, 60(7): 915-925.
[7]	XIONG Yi, LUAN Zewei, MA Yunfei, LI Yong, ZHA Xiaoqin. Effect of Surface Nanocrystallization Induced by Supersonic Fine Particles Bombardment on Corrosion Fatigue Behavior of 300M Steel[J]. 金属学报, 2024, 60(5): 627-638.
[8]	JIANG Haowen, PENG Wei, FAN Zengwei, WANG Yangxin, LIU Tengshi, DONG Han. Effect of Ag on Microstructure and Mechanical Properties of Austenitic Stainless Steel[J]. 金属学报, 2024, 60(4): 434-442.
[9]	TIAN Teng, ZHA Min, YIN Haoliang, HUA Zhenming, JIA Hailong, WANG Huiyuan. Enhanced Mechanical Properties and Thermal Stability Mechanism of a High Solid Solution Al-Mg Alloy Processed by Cryogenic High-Reduction Hard-Plate Rolling[J]. 金属学报, 2024, 60(4): 473-484.
[10]	CHEN Shenghu, WANG Qiyu, JIANG Haichang, RONG Lijian. Effect of δ-Ferrite on Hot Deformation and Recrystallization of 316KD Austenitic Stainless Steel for Sodium-Cooled Fast Reactor Application[J]. 金属学报, 2024, 60(3): 367-376.
[11]	HU Baojia, ZHENG Qinyuan, LU Yi, JIA Chunni, LIANG Tian, ZHENG Chengwu, LI Dianzhong. Recrystallization Controlling in a Cold-Rolled Medium Mn Steel and Its Effect on Mechanical Properties[J]. 金属学报, 2024, 60(2): 189-200.
[12]	ZHAI Xinya, HE Zhenghua, SHA Yuhui, ZHU Xiaofei, LI Feng, CHEN Lijia, ZUO Liang. Inhibitor and Secondary Recrystallization Behavior of Giant Magnetostriction of Fe-Ga Thin Sheet[J]. 金属学报, 2024, 60(11): 1559-1570.
[13]	ZHAO Peng, XIE Guang, DUAN Huichao, ZHANG Jian, DU Kui. Recrystallization During Thermo-Mechanical Fatigue of Two High-Generation Ni-Based Single Crystal Superalloys[J]. 金属学报, 2023, 59(9): 1221-1229.
[14]	CHANG Songtao, ZHANG Fang, SHA Yuhui, ZUO Liang. Recrystallization Texture Competition Mediated by Segregation Element in Body-Centered Cubic Metals[J]. 金属学报, 2023, 59(8): 1065-1074.
[15]	LI Fulin, FU Rui, BAI Yunrui, MENG Lingchao, TAN Haibing, ZHONG Yan, TIAN Wei, DU Jinhui, TIAN Zhiling. Effects of Initial Grain Size and Strengthening Phase on Thermal Deformation and Recrystallization Behavior of GH4096 Superalloy[J]. 金属学报, 2023, 59(7): 855-870.

No Suggested Reading articles found!

Viewed

Full text

Abstract

Cited

Shared

Discussed