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Zr57.5Cu27.3Al8.5Ni6.7非晶合金的非等温和等温晶化动力学研究

2016-03-05陈振华赵秀媛王辉平张昊

湖南大学学报·自然科学版 2015年12期

陈振华++赵秀媛++王辉平++张昊++陈鼎

摘要:对制备的Zr57.5Cu27.3Al8.5Ni6.7非晶合金的等温与非等温晶化动力学通过差式扫描量热法(DSC)进行了研究,根据Kisinger方程计算出Zr57.5Cu27.3Al8.5Ni6.7非晶合金在非等温条件下的激活能Eg,Ex,Ep1和Ep2,分别为409.70 kJ/mol(± 60.07 kJ/mol),335.53 kJ/mol(± 39.94 kJ/mol),323.95 kJ/mol(± 15.21 kJ/mol)和187.75 kJ/mol(± 13.27 kJ/mol).在718 K,723 K,728 K和733 K等温条件下得到的晶化体积分数与时间的关系曲线呈“S”型,表明晶化过程为典型的形核长大型转变.Avrami指数n的范围为3≤n≤4,表明晶化过程由界面控制的二维长大转变为界面控制的三维长大,形核率随时间逐渐降低至稳定,等温晶化过程得到的激活能平均值434.81 kJ/mol,高于非等温晶化过程的有效激活能.

关键词:大块非晶;晶化动力学;激活能; Avrami指数

中图分类号:TG139.8 文献标识码:AIsochronal and Isothermal Crystallization

in Zr57.5Cu27.3Al8.5Ni6.7 Bulk Metallic Glass

CHEN Zhenhua1, ZHAO Xiuyuan1, WANG Huiping2,ZHANG Hao3,CHEN Ding1,

(1. College of Materials Science and Engineering, Hunan Univ, Changsha, Hunan410082, China;

2. Zhuzhou Cemented Carbide Group Co, Ltd, Zhuzhou,Hunan412000, China;

3. Dept of Electromechanical Engineering, Changsha Univ,Changsha, Hunan410022, China)Abstract:Nonisothermal crystallization transformation kinetics and isothermal crystallization kinetics of prepared Zr57.5Cu27.3Al8.5Ni6.7 bulk metallic glass (BMG) were investigated with differential scanning calorimetry (DSC). In isochronal mode, the values of activation energy, Eg, Ex, Ep1 and Ep2, calculated by Kisinger method are 409.70 kJ/mol (± 60.07 kJ/mol), 335.53 kJ/mol (± 39.94 kJ/mol), 323.95 kJ/mol (± 15.21 kJ/mol) and 187.75 kJ/mol (± 13.27 kJ/mol), respectively. In isothermal mode, the Sshape relation curves of crystalline volume fraction and temperature reveal the typical transition of nucleation and growth. The Avrami exponent n ranges from 3.0 to 4, indicating the crystallization mechanism in the Zr57.5Cu27.3Al8.5Ni6.7 BMG is mainly interfacecontrolled. The crystal growth way changes from twodimensional growth with decreased nucleation rate to threedimensional growth in the isothermal crystallization process. In isothermal mode, the mean value of activation energy is 434.81 kJ/mol, which is higher than that in the isochronal mode.

Key words:BMG; crystallization kinetics; activation energy; Avrami exponent

与晶态物质相比,大块非晶合金呈短程有序长程无序排列,没有晶体结构、晶界以及其他的晶体缺陷.因而大块非晶合金(BMG)具有一系列优异的性能,比如具有较高的屈服极限,较大的弹性应变极限,高耐磨性,高抗疲劳强度和较强的耐腐蚀性[1-3].但非晶合金在热力学上处于亚稳态,受热时会发生向稳定晶态的转变,使其结构和性能发生改变[4-5].因此研究大块非晶的晶化过程和晶化动力学对于评估其热稳定性以防止其晶化有非常重要的意义.因为非晶合金的晶化是通过形核和长大过程发生,这为研究晶体向各向同性价值生长提供了机会.此外此过程也为在大过冷条件下检验经典的形核长大理论提供了较好的机会.

湖南大学学报(自然科学版)2015年第12期陈振华等:Zr57.5Cu27.3Al8.5Ni6.7非晶合金的非……

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