Mg_(17)Al_(12)合金燃烧合成过程动力学
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摘要
采用非模型拟合法研究了Mg_(17)Al_(12)储氢合金燃烧合成过程动力学,为今后规模化制备该合金提供理论指导。首先比较不同样品燃烧合成过程热效应及产物相组分,指出压片预处理方法及小尺寸Al粉均有利于促进合金化反应;然后分别采用Kissinger法和Flynn-Wall-Ozawa法计算出该反应活化能分别为140.5和142 k J/mol,对应的最概然机制函数为G(α)=[-ln(1-α)]1/3,符合Avrami-Erofeev方程的随机成核和随后生长机制。最后通过反应前后期产物相组成分析,揭示该燃烧合成过程中Mg-Al合金化反应机制。
The kinetics for the combustion synthesis process of Mg_(17)Al_(12) hydrogen storage alloy was investigated using model-free methods,it could provide an important theoretical guidance for the industrial production of the alloy. The effects of different pretreatment methods on the thermal behavior and phase compositions of the products were also investigated. Results showed that the pressed samples with smaller Al particle size were more effective to facilitate the alloying kinetics. The formation activation energies of Mg-Al alloy calculated by Kissinger and Flynn-Wall-Ozawa methods were 140. 5 k J / mol and 142 k J / mol,respectively. The fitted most probable mechanism function for the process G( α) = [- ln( 1- α) ]1 /3,it was in accord with the random nucleation and subsequent growth mechanism of the Avrami-Erofeev equation. And the alloying mechanism of Mg-Al alloy for the combustion synthesis process was revealed by analyzing the phase composition of the products before and after the reaction.
The kinetics for the combustion synthesis process of Mg_(17)Al_(12) hydrogen storage alloy was investigated using model-free methods,it could provide an important theoretical guidance for the industrial production of the alloy. The effects of different pretreatment methods on the thermal behavior and phase compositions of the products were also investigated. Results showed that the pressed samples with smaller Al particle size were more effective to facilitate the alloying kinetics. The formation activation energies of Mg-Al alloy calculated by Kissinger and Flynn-Wall-Ozawa methods were 140. 5 k J / mol and 142 k J / mol,respectively. The fitted most probable mechanism function for the process G( α) = [- ln( 1- α) ]1 /3,it was in accord with the random nucleation and subsequent growth mechanism of the Avrami-Erofeev equation. And the alloying mechanism of Mg-Al alloy for the combustion synthesis process was revealed by analyzing the phase composition of the products before and after the reaction.
引文
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[13]张桂敏,陈阳波,傅正义,等.莫来石单相胶前驱体结晶动力学[J].功能材料,2013,44(24):3571.
[2]MORSI K.The diversity of combustion synthesis processing:a review[J].Journal of materials science,2011,47:68.
[3]张树格.燃烧合成技术研究的进展[J].粉末冶金技术,2011,29(6):452.
[4]ISOGAI H,AKIYAMA T,YAGI J.Combustion synthesis of Mg2Ni and Mg2Ni H4[J].Journal of the Japan institute of matals,1996,60(3):338.
[5]TANWAR N,SARASWAT V K.A study of kinetics of phase transformation of Ge10Se75Sb15chalcogenide glass[J].Journal of non-crystalline solids,2014,394:1.
[6]HE Z Y,ZHAO B J,ZHU S F,et al.Thermal properties and optimization of process parameter for the growth of silver thiogallate crystal by differential scanning calorimetry[J].Journal of crystal growth,2014,402:9.
[7]FAN R H,LIU B,ZHANG J D,et al.Kinetic evaluation of combustion synthesis 3Ti O2+7Al→3Ti Al+2Al2O3using nonisothermal DSC method[J].Materials chemistry and physics,2005,91:140.
[8]BLAINE R L,KISSINGER H E.Homer Kissinger and the Kissinger equation[J].Thermochimica acta,2012,540:1.
[9]GUAN Y C,ZHOU W.Calorimetric analysis of AZ91D magnesium alloy[J].Materials letters,2008,62:4494.
[10]YAN S,LU Y,LIU G,et al.The kinetic analysis of formation behavior for the Mg B2phase[J].Journal of alloys and compounds,2007,443:161.
[11]TANGUEP N E M,SALAMON M,MEHRER H.Growth of intermetallic phases in the Al-Mg system[J].Defect and diffusion forum,2001,199:1581.
[12]BRENNAN S,BERMUDEZ K,KULKARNI N S,et al.Interdiffusion in the Mg-Al system and intrinsic diffusion inβ-Mg2Al3[J].Metallurgical and materials transactions A,2012,43:4043.
[13]张桂敏,陈阳波,傅正义,等.莫来石单相胶前驱体结晶动力学[J].功能材料,2013,44(24):3571.