Huestis Patricia L, Lease Nicholas, Freye Chris E, Huber Daniel L, Brown Geoffrey W, McDonald Daniel L, Nelson Tammie, Snyder Christopher J, Manner Virginia W
Los Alamos National Laboratory USA
RSC Adv. 2023 Mar 21;13(14):9304-9315. doi: 10.1039/d3ra00998j. eCollection 2023 Mar 20.
Explosives exist in and are expected to withstand a variety of harsh environments up to and including ionizing radiation, though little is known about the chemical consequences of exposing explosives to an ionizing radiation field. This study focused on the radiation-induced chemical changes to a variety of common energetic functional groups by utilizing a consistent molecular backbone. Dodecane was substituted with azide, nitro, nitrate ester, and nitramine functional groups and γ-irradiated with Co in order to study how the functional group degraded along with what the relative stability to ionizing radiation was. Chemical changes were assessed using a combination of analysis techniques including: nuclear magnetic resonance (NMR) spectroscopy, gas chromatography of both the condensed and gas phases, Raman spectroscopy, and Fourier transform infrared (FTIR) spectroscopy. Results revealed that much of the damage to the molecules was on the energetic functional group and often concentrated on the trigger linkage, also known as the weakest bond in the molecule. The general trend from most to least susceptible to radiolytic damage was found to be D-ONO → D-N → D-NHNO → D-NO. These results also appear to be in line with the relative stability of these functional groups to things such as photolysis, thermolysis, and explosive insults.
炸药存在于各种恶劣环境中，并有望承受包括电离辐射在内的各种恶劣环境，不过对于将炸药暴露于电离辐射场的化学后果知之甚少。本研究通过使用一致的分子骨架，聚焦于辐射诱导的各种常见含能官能团的化学变化。用叠氮基、硝基、硝酸酯和硝胺官能团取代十二烷，并使用钴进行γ辐照，以研究官能团如何降解以及对电离辐射的相对稳定性如何。使用多种分析技术相结合来评估化学变化，这些技术包括：核磁共振（NMR）光谱、凝聚相和气相的气相色谱、拉曼光谱以及傅里叶变换红外（FTIR）光谱。结果表明，分子的大部分损伤发生在含能官能团上，并且通常集中在引发键上，引发键也被称为分子中最弱的键。发现从最易受到辐射分解损伤到最不易受到辐射分解损伤的一般趋势是：D-ONO → D-N → D-NHNO → D-NO。这些结果似乎也与这些官能团对光解、热解和爆炸冲击等情况的相对稳定性一致。
