Jacob Rohit J, Ortiz-Montalvo Diana L, Overdeep Kyle R, Weihs Timothy P, Zachariah Michael R
Department of Chemical and Biomolecular Engineering and Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20706, USA.
Materials Measurement Science Division, National Institute of Standards and Technology, Gaithersburg, Maryland 20899, USA.
J Appl Phys. 2017;121(5). doi: 10.1063/1.4974963.
Exothermic reactions between oxophilic metals and transition/ post transition metal-oxides have been well documented owing to their fast reaction time scales (≈ 10 μs). This article examines the extent of reaction in nano-aluminum based thermite systems through a forensic inspection of the products formed during reaction. Three nanothermite systems (Al/CuO, Al/BiO and Al/WO) were selected owing to their diverse combustion characteristics thereby providing sufficient generality and breadth to the analysis. Microgram quantities of the sample were coated onto a fine platinum wire, which was resistively heated at high heating rates (≈ 10 K/s) to ignite the sample. The subsequent products were captured/quenched very rapidly (≈ 500 μs) in order to preserve the chemistry/morphology during initiation and subsequent reaction and were quantitatively analyzed using electron microscopy (EM), focused ion beam (FIB) cross-sectioning followed by energy dispersive X-ray spectroscopy (EDX). Elemental examination of the cross-section of the quenched particles show oxygen predominantly localized in the regions containing aluminum, implying the occurrence of redox reaction. The Al/CuO system, which has simultaneous gaseous oxygen release and ignition ( ≈ ), shows substantially lower oxygen content within the product particles as opposed to Al/BiO and Al/WO thermites, which are postulated to undergo a condensed phase reaction ( << ). An effective Al:O composition for the interior section was obtained for all the mixtures, with the smaller particles generally showing higher oxygen content than the larger ones. The observed results were further corroborated with the reaction temperature, obtained using a high-speed spectro-pyrometer, and bomb calorimetry conducted on larger samples (≈ 15 mg). The results suggest that thermites that produce sufficient amounts of gaseous products generate smaller product particles and achieve higher extents of completion.
由于亲氧金属与过渡/后过渡金属氧化物之间的放热反应时间尺度很快(约10微秒),因此已有充分的文献记载。本文通过对反应过程中形成的产物进行法医检验,研究了纳米铝基铝热剂体系中的反应程度。选择了三种纳米铝热剂体系(Al/CuO、Al/BiO和Al/WO),因为它们具有不同的燃烧特性,从而为分析提供了足够的通用性和广度。将微克量的样品涂覆在细铂丝上,以高加热速率(约10 K/s)进行电阻加热以点燃样品。随后的产物在非常短的时间内(约500微秒)被捕获/淬灭,以保留引发和后续反应过程中的化学性质/形态,并使用电子显微镜(EM)、聚焦离子束(FIB)横截面分析以及能量色散X射线光谱(EDX)进行定量分析。对淬灭颗粒横截面的元素检查表明,氧主要集中在含铝区域,这意味着发生了氧化还原反应。Al/CuO体系同时释放气态氧并点火(约 ),与Al/BiO和Al/WO铝热剂相比,其产物颗粒中的氧含量要低得多,据推测Al/BiO和Al/WO铝热剂会发生凝聚相反应(远小于 )。获得了所有混合物内部截面的有效Al:O组成,较小的颗粒通常比较大的颗粒显示出更高的氧含量。使用高速光谱高温计获得的反应温度以及对较大样品(约15毫克)进行的弹式量热法进一步证实了观察结果。结果表明,产生足够量气态产物的铝热剂会产生较小的产物颗粒,并实现更高的反应完成程度。