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玻璃形成液体在温度变化过程中会表现出独特的动力学转变行为, 在降温过程中, 系统会经历从脆性液体到强性液体的转变, 称为强脆转变. 本研究以Fe-Zr-B-M四元体系为研究对象, 通过黏度实验揭示该体系存在显著的强脆转变行为, 并以晶化激活能作为评价指标, 建立Fe-Zr-B-M体系中强脆转变程度与玻璃形成能力之间的负相关性. 结果表明, 类晶团簇在Fe-Zr-B-M体系金属玻璃的凝固过程中起关键作用, 据此提出了基于二十面体团簇向类晶团簇结构转变的强脆转变机理, 并确立了混合焓和错配熵在调控Fe基非晶合金液体强脆转变过程中的重要作用.Glass-forming liquids exhibit unique dynamic transition behavior during temperature changes. The system undergoes a transition from the fragile liquid to the strong liquid, which is known as the fragile-to-strong transition as the temperature decreases. In order to address the issue of poor glass-forming ability (GFA) in Fe-based alloys, through studying the kinetic behavior of the Fe-Zr-B-M (M = Nb, Ti, Al) alloy system, the mechanism of ductile-brittle transition is revealed and the relationship between the degree of ductile-brittle transition and the GFA is established. In this study, through viscosity measurements, a pronounced fragile-to-strong transition behavior in this system is revealed. By using crystallization activation energy as an evaluation criterion, a negative correlation between the degree of the fragile-to-strong transition and the GFA in the Fe-Zr-B-M system is established. The results indicate that the crystal-like clusters play a critical role in the solidification process of the Fe-Zr-B-M metallic glasses. Based on this, a fragile-to-strong transition mechanism involving the structural transformation from the icosahedral clusters to the crystal-like clusters is proposed. Through theoretical calculations of mixing enthalpy and mismatch entropy and by combining microstructural characterization, it is found that alloy compositions with more negative mixing enthalpy and higher mismatch entropy can effectively suppress the tendency of icosahedral structures to transform into crystal-like structures, thereby hindering crystallization and promoting the formation of a more disordered amorphous structure. This structural feature not only corresponds to superior glass-forming ability but also exhibits a weak fragile-to-strong transition phenomenon. In this work, the intrinsic correlation between viscosity characteristics and the GFA is revealed, providing a theoretical basis for developing Fe-based metallic glasses with high GFA.
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Keywords:
- metallic glass /
- fragile-to-strong transition /
- viscosity /
- glass-forming ability
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图 1 (Fe0.84Zr0.09B0.07)100-xMx (x = 0, 3; M = Nb, Ti, Al)金属玻璃条带的(a) XRD曲线和(b) HRTEM图像, 插图为相应的选区电子衍射图像
Fig. 1. (a) X-ray diffraction patterns and (b) HRTEM images of (Fe0.84Zr0.09B0.07)100-xMx (x = 0, 3; M = Nb, Ti, Al) metallic glass ribbons, the inset of panel (b) is the corresponding selected area electron diffraction images.
图 2 (Fe0.84Zr0.09B0.07)100-xMx (x = 0, 3; M = Nb, Ti, Al)金属玻璃条带的DSC曲线, 升温速率为20 K/min
Fig. 2. DSC curves of (Fe0.84Zr0.09B0.07)100-xMx (x = 0, 3; M = Nb, Ti, Al) metallic glass ribbons with heating rate is 20 K/min.
图 3 降温过程中黏度变化 (a) Fe84Zr9B7; (b) (Fe0.84Zr0.09B0.07)97Nb3; (c) (Fe0.84Zr0.09B0.07)97Al3
Fig. 3. Temperature dependence of the viscosity values (η) during cooling: (a) Fe84Zr9B7; (b) (Fe0.84Zr0.09B0.07)97Nb3; (c) (Fe0.84Zr0.09B0.07)97Al3.
图 4 (a) Fe84Zr9B7金属玻璃条带不同热扫描速率下的DSC曲线; (b) FeZrB, Nb3, Ti3和Al3的Kissinger公式拟合曲线
Fig. 4. DSC curves of Fe84Zr9B7 metallic glass ribbons with different heating rates; (b) the fitting curses of Kissinger’s formula for FeZrB, Nb3, Ti3 and Al3.
图 5 (Fe0.84Zr0.09B0.07)100-xMx (x = 0, 3; M = Nb, Ti, Al)金属玻璃液体黏度对数随温度的变化趋势
Fig. 5. Vscosities of (Fe0.84Zr0.09B0.07)100-xMx (x = 0, 3; M = Nb, Ti, Al) as functions of temperature.
图 6 (a) Fe-Zr-B-M强脆转变系数f与晶化激活能E的关系; (b) CuZr合金玻璃形成的临界厚度Dmax、强脆转变系数f随Cu含量的变化[19]
Fig. 6. (a) Correlation between the activation energy of crystallization (E) and the fragile-to-strong trasition parameter (f) of Fe-Zr-B-M; (b) the critical sample thickness (Dmax) for glass formation, the fragile-to-strong trasition parameter (f) versus the fraction of Cu in CuZr alloy series.
图 7 Fe-Zr-B-M体系的(a)强脆转变系数f; (b)晶化激活能E及(c)混合焓和错配熵乘积的绝对值${|\Delta }{{H}}^{\text{chem}}\times $ $ {{S}}_{\sigma}/{{k}}_{\text{B}}\text{|} $
Fig. 7. (a) The fragile-to-strong trasition parameter (f); (b) the activation energy of crystallization (E); (c) $ {|\Delta }{{H}}^{\text{chem}}\times{{S}}_{\sigma}/{{k}}_{\text{B}}\text{|} $ of Fe-Zr-B-M system.
图 8 (a) 正方形的划分方法; (b)—(e) Fe84Zr9B7, (Fe0.84Zr0.09B0.07)97Nb3, (Fe0.84Zr0.09B0.07)97Ti3及(Fe0.84Zr0.09B0.07)97Al3自相关分析图像
Fig. 8. (a) Method of dividing the HRTEM images into cells; (b)–(e) autocorrelation images of Fe84Zr9B7, (Fe0.84Zr0.09B0.07)97Nb3, (Fe0.84Zr0.09B0.07)97Ti3 and (Fe0.84Zr0.09B0.07)97Al3.
图 9 Fe-Zr-B-M体系在冷却过程中的团簇演变示意图, 蓝色圆点和红色圆点分别代表类晶团簇和二十面体团簇, 灰色圆点代表自由原子或者其他局域结构
Fig. 9. Schematic diagram of clusters evolution of Fe-Zr-B-M during the cooling process, the blue and red dots represent the crystal-like and the icosahedra clusters in the liquid, respectively, while the gray dots represent the free atoms or other local structural configurations.
表 1 (Fe0.84Zr0.09B0.07)100-xMx (x = 0, 3; M = Nb, Ti, Al)合金的高温脆性系数m′和过冷液体脆性系数m
Table 1. Fragility index for high temperature (m′) liquid and supercooled liquid (m) of (Fe0.84Zr0.09B0.07)100-xMx (x = 0, 3; M = Nb, Ti, Al).
成分 高温脆性m′ E/(kJ·mol–1) R2 过冷液体脆性系数m Fe84Zr9B7 129.3 413.8 0.976 25.2 (Fe0.84Zr0.09B0.07)97Nb3 127.6 512.3 0.962 30.3 (Fe0.84Zr0.09B0.07)97Ti3 — 489.5 0.976 29.1 (Fe0.84Zr0.09B0.07)97Al3 126.7 436.6 0.90 26.4 
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表 2 (Fe0.84Zr0.09B0.07)100-xMx (x = 0, 3; M = Nb, Ti, Al)金属玻璃条带在不同升温速率(10—40 K/min)下的初始晶化温度Tx
Table 2. Initial crystallization temperatures of (Fe0.84Zr0.09B0.07)100-xMx (x = 0, 3; M = Nb, Ti, Al) metallic glass ribbons at different heating rate (10–40 K/min).
成分 升温速率/ (K·min–1) 初始晶化温度Tx /K 升温速率/ (K·min–1) 初始晶化温度Tx/K Fe84Zr9B7 10 854.5 20 859.3 30 866.1 40 868.4 (Fe0.84Zr0.09B0.07)97Nb3 10 879.8 20 885.2 30 893.1 40 897.1 (Fe0.84Zr0.09B0.07)Ti973 10 875.0 20 881.7 30 886.5 40 889.2 (Fe0.84Zr0.09B0.07)97Al3 10 840.7 20 846.1 30 852.3 40 854.3
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表 3 (Fe0.84Zr0.09B0.07)100-xMx (x = 0, 3; M = Nb, Ti, Al)的强脆转变系数f, 晶化激活能E, 混合焓$ {\Delta }{{H}}^{\text{chem}} $, 错配熵$ {{S}}_{\sigma}/{{k}}_{\text{B}} $, 混合焓和错配熵乘积的绝对值$ {|\Delta }{{H}}^{\text{chem}}\times{{S}}_{\sigma}/{{k}}_{\text{B}}\text{|} $
Table 3. The fragile-to-strong trasition parameter (f), the activation energy of crystallization (E), mixing enthalpy (∆Hchem), mismatch entropy (${{S}}_{\sigma}/{{k}}_{\text{B}} $) and their absolute multiplication of (Fe0.84Zr0.09B0.07)100-xMx (x = 0, 3; M = Nb, Ti, Al).
成分 强脆转变系数f 晶化激活能E 混合焓$ {\Delta }{{H}}^{\text{chem}} $/(kJ·mol–1) 错配熵$ {{S}}_{\sigma}/{{k}}_{\text{B}} $ $ {|\Delta }{{H}}^{\text{chem}}\times{{S}}_{\sigma}/{{k}}_{\text{B}}\text{|} $ Fe84Zr9B7 5.13 413.8 –12.9 0.219 2.82 (Fe0.84Zr0.09B0.07)97Nb3 4.21 512.3 –14.1 0.227 3.20 (Fe0.84Zr0.09B0.07)97Ti3 4.29—4.46 489.5 –14.2 0.227 3.22 (Fe0.84Zr0.09B0.07)97Al3 4.80 436.6 –13.6 0.219 2.97
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