具有异常放热现象的<strong>Fe-Nb-B-Y</strong>非晶合金燃烧机理

doi:10.11900/0412.1961.2020.00420

金属学报

2021, Vol. 57

Issue (4): 542-552 DOI: 10.11900/0412.1961.2020.00420

研究论文

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具有异常放热现象的Fe-Nb-B-Y非晶合金燃烧机理

胡祥¹, 葛嘉城¹, 刘思楠¹, 伏澍¹, 吴桢舵²^,³, 冯涛¹, 刘冬⁴, 王循理², 兰司¹(

)

^1.南京理工大学材料科学与工程学院/格莱特研究院格莱特纳米科技研究所南京 210094
^2.香港城市大学物理系香港 999077
^3.东莞市香港城市大学研究院中子散射应用物理研究中心东莞 523808
^4.南京理工大学能源与动力工程学院南京 210094

Combustion Mechanism of Fe-Nb-B-Y Amorphous Alloys with an Anomalous Exothermic Phenomenon

HU Xiang¹, GE Jiacheng¹, LIU Sinan¹, FU Shu¹, WU Zhenduo²^,³, FENG Tao¹, LIU Dong⁴, WANG Xunli², LAN Si¹(

)

^1.Herbert Gleiter Institute of Nanoscience, School of Materials Science and Engineering/Herbert Gleiter Institute, Nanjing University of Science and Technology, Nanjing 210094, China
^2.Department of Physics, City University of Hong Kong, Hong Kong 999077, China
^3.Applied Physics Centre of Neutron Scattering, Dongguan University of Hong Kong Research Institute, Dongguan 523808, China
^4.School of Energy and Power Engineering, Nanjing University of Science and Technology, Nanjing 210094, China

引用本文:

胡祥, 葛嘉城, 刘思楠, 伏澍, 吴桢舵, 冯涛, 刘冬, 王循理, 兰司. 具有异常放热现象的Fe-Nb-B-Y非晶合金燃烧机理[J]. 金属学报, 2021, 57(4): 542-552.
Xiang HU, Jiacheng GE, Sinan LIU, Shu FU, Zhenduo WU, Tao FENG, Dong LIU, Xunli WANG, Si LAN. Combustion Mechanism of Fe-Nb-B-Y Amorphous Alloys with an Anomalous Exothermic Phenomenon[J]. Acta Metall Sin, 2021, 57(4): 542-552.

全文: PDF(3567 KB) HTML

摘要:

通过同步辐射原位高能X射线衍射，结合差式扫描量热、热重分析、X射线光电子能谱等检测手段，对具有异常放热现象的铁基非晶合金条带的燃烧机理进行了系统研究。结果表明，相比不具有异常放热现象、无法自蔓延燃烧的Fe-Nb-B-Y非晶合金成分，具有异常放热现象的(Fe_0.72B_0.24Nb_0.04)_95.5Y_4.5非晶条带由于快速晶化放热过程的催化，能够实现低着火点及自蔓延燃烧。与液-液相变相关联的异常放热现象诱导了升温过程中的快速晶化，并导致高温下的多步氧化反应。同时液-液相变导致高温氧化阶段的激活能降低，从而降低反应能垒，促进高温下的氧化反应。研究表明异常放热现象及其关联的液-液相变对铁基非晶合金的燃烧有“诱导活化”作用。

关键词 ：非晶合金, 液-液相变, 燃烧, 含能材料

Abstract：

The functional groups in traditional energetic materials typically contain C, N, and O. These elements are usually unstable and sensitive to external stimuli. Moreover, the chemicals used during the preparation process of traditional energetic materials are toxic and pose many safety and environmental issues. As one of the metastable materials, high-energy-state amorphous alloys are potential candidates for new energetic materials with high combustion heat, low ignition temperature, non-toxicity, and improved safety. In this work, the combustion mechanism of Fe-based amorphous ribbons with an anomalous exothermic phenomenon was systematically studied using in situ synchrotron X-ray diffraction, differential scanning calorimetry, thermogravimetric analysis, and X-ray photoelectron spectroscopy. Experimental results show that compared to Fe-Nb-B-Y amorphous alloys with normal thermophysical and combustion behaviors, (Fe_0.72B_0.24Nb_0.04)_95.5Y_4.5 amorphous ribbons with anomalous exothermic phenomena possess low ignition temperature and self-propagating combustion behavior due to the catalysis of the rapid crystallization exothermic process. The anomalous exothermic phenomenon and associated liquid-liquid phase transitions can cause rapid crystallization at elevated temperatures during heating, followed by multi-step oxidation. On the other hand, it was possible to significantly reduce the activation energy of high-temperature oxidation. The liquid-liquid phase transition can lower the energy barrier of the oxidation reaction. In this way, the oxidation reaction at high temperatures can be promoted. The results suggest that the liquid-liquid phase transition has an “induced activation” effect on the combustion of Fe-based amorphous alloys.

Key words： amorphous alloy liquid-liquid phase transition combustion energetic material

收稿日期: 2020-10-26

ZTFLH:

TG146.4

基金资助:国家自然科学基金项目(51871120);江苏省自然科学基金-杰出青年基金项目(BK20200019)

作者简介: 胡祥，男，1996年生，硕士生

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https://www.ams.org.cn/CN/10.11900/0412.1961.2020.00420 或 https://www.ams.org.cn/CN/Y2021/V57/I4/542

图1 Fe-Nb-B-Y非晶合金在空气中的点火和燃烧过程光学摄像记录照片(a) 0 s (b) 1 s (c) 2 s (d) 3 s (e) 4 s (f) 5 s

图2 Fe-Nb-B-Y非晶合金的热分析结果(a) DSC curves of Fe-Nb-B-Y MGs showing Y4.5 MGs have an anomalous exothermic phenomenon (AEP) in the supercooled liquid region, while Y0, Y3, and Y7 MGs do not have (Inset shows the enlarged region of AEP for Y4.5. T—absolute temperature, Tg—glass transition temperature, TC—valley temperature of the AEP, TX—crystallization temperature, Tm—melting temperature, Tl—liquidus temperature)(b) ignition temperature (Ti) of Y0, Y3, and Y4.5 MGs calculated by the TG-DTG tangent method(c) DTG curves of Fe-Nb-B-Y MGs(d) calculation of the activation energy of Fe-Nb-B-Y MGs during oxidation (Ea—activation energy, R—gas constant, dW /dt—mass change rate, w—residule mass during oxidation)

表1 Fe-Nb-B-Y非晶合金的热物理参数 (K)

表2 Fe-Nb-B-Y非晶合金不同氧化阶段的激活能 (kJ·mol-1)

图3 Y4.5块体非晶合金在同步辐射原位加热实验中出现的自放热现象(a) heating process (b) heating rate

图4 Y4.5样品不同温度下以0.33 K/s的升温速率加热时有自放热过程、无自放热过程和以1.67 K/s的升温速率快速加热过程的结构因子S(Q)和约化对分布函数G(r)(a, d) plots for the sample with a self-heating process with heating rate 0.33 K/s (b, e) plots for the sample without self-heating during a normal slow heating process with heating rate 0.33 K/s (c, f) plots for the sample with a fast-heating rate (1.67 K/s)

图5 Y4.5非晶合金在惰性气体保护气氛下慢速加热无自放热过程、快速加热有自放热过程和在空气中燃烧后产物的HE-XRD结构精修结果以及Y4.5燃烧产物的OM像

图6 Y0、Y3和Y7燃烧产物的HE-XRD结构精修结果

图7 Y0、Y3、Y4.5和Y7燃烧产物的XPS结果

图8 潮湿环境下传统专业棉线包裹火药引火线和Y4.5非晶合金条带的燃烧现象光学摄像记录照片(a) 0 s (b) 1 s (c) 2 s (d) 3 s (e) 4 s (f) 5 s

图9 Fe-Nb-B-Y非晶合金在空气中燃烧过程示意图

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