Cu46Zr50Al4金属玻璃结晶过程动力学模型

Anastasiya A. Ryltseva, T. Kulikova, V. Bykov, R. Ryltsev
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摘要

基于Cu-Zr玻璃形成体系的纳米复合材料是一种含有CuZr化合物立方B2相结晶夹杂物的非晶基体,由于其独特的力学性能,是一种很有前途的结构材料。生产这种材料的方法之一是对非晶样品进行热处理。为了确定最佳工艺条件,有必要对非晶铜锆的结晶动力学进行研究。本文首次在室温~ 600℃的较宽温度范围内研究了吸力铸造Cu46Zr50Al4非晶合金的结晶过程、组织和热性能。我们揭示了该合金结晶过程的复杂特征,描述了一个三步顺序反应。采用量热分析、x射线相分析和多元非线性回归动力学建模等综合方法,建立了合金结晶过程的动力学模型并估计了动力学参数。我们发现,当使用自催化方程来模拟结晶过程时,实验数据得到了最好的描述:具有自催化的n级非均相反应,以及Prout-Tompkins方程。合金的结晶活化能为Ea = 387.59 kJ/mol。基于所获得的结果,我们提出了一种通过将非晶合金加热至约420-460°C来制备纳米复合材料的方法。
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Kinetic model of the crystallization process of Cu46Zr50Al4 metallic glass
Nanocomposite materials based on the Cu-Zr glass-forming system, which are an amorphous matrix with crystalline inclusions of the cubic B2 phase of the CuZr compound, are promising structural materials due to their unique mechanical properties. One of the methods for producing such materials is the heat treatment of amorphous samples. To develop optimal conditions for such processing, it is necessary to study the kinetics of crystallization of amorphous copper-zirconium. In this work, the crystallization processes, structure and thermal properties of the amorphous Cu46Zr50Al4 alloy, obtained by suction casting were studied for the first time in a wide temperature range from room temperature up to 600 °C. We reveal the complex character of the crystallization process of this alloy described by a three-step sequential reaction. Using a comprehensive approach, including calorimetric studies, X-ray phase analysis and kinetic modeling by multivariate nonlinear regression, we develop the kinetic model and estimate kinetic parameters of the crystallization processes in the alloy. We find that the best description of the experimental data is achieved when autocatalytic equations are used to model crystallization processes: a heterogeneous n-th order reaction with autocatalysis, as well as the Prout-Tompkins equation. The found activation energy of crystallization of the alloy is Ea = 387.59 kJ/mol. Based on the results obtained, we propose a procedure for fabricating the nanocomposite materials by heating an amorphous alloy up to temperatures of about 420-460 °C.
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