Yehia M, Ismael Shukri, Naeem Ibrahim, Sousa-Castillo Ana, Vázquez-González Margarita, Correa-Duarte Miguel A, Elbasuney Sherif
School of Chemical Engineering, Military Technical College (MTC), Cairo, Egypt.
CINBIO, Universidade de Vigo, 36310, Vigo, Spain.
Sci Rep. 2025 May 22;15(1):17733. doi: 10.1038/s41598-025-99700-7.
The accompanying health and environmental issues have prompted a renewed effort to find more environmentally friendly substitutes for ammonium perchlorate (AP) as a solid rocket propellant oxidizer. AP Propulsion's outstanding performance is complemented by environmental concerns, which search for greener options necessary. Ammonium nitrate (AN) has emerged as a viable alternative that provides cost-effectiveness, non-detectable and tractable properties to the adversary, and cleaner combustion products. Structural instability is one of the problems with AN-based propellants. This work aims to overcome this obstacle by creating green energetic molecular perovskite based on nitrate groups (NO). NH(CHN)(NO) (DAN-4) was synthesized by molecular assembly technique. Scanning electron microscope (SEM), X-ray diffraction (XRD), and Fourier transfer infrared (FTIR) were applied to characterize the structure and morphology of AP, AN, and DAN-4. Thermal decomposition of AP, AN, and DAN-4 were investigated using differential scanning calorimetry (DSC), and thermal gravimetric analysis (TGA). The results show that DAN-4 has one exothermic peak at 201 °C with 1420 J/g heat evolved compared to AN which has two endothermic phase transitions at 54 °C, and 128 °C respectively, melting point at 170 °C, and thermal decomposition at 294 °C with no exothermic peak, and heat evolved. DAN-4 shows higher energy released than common oxidizer (AP) which evolved 836 J/g. Decomposition kinetics was investigated via isoconversional (model free) and model fitting. Kissinger, Kissinger-Akahira-Sunose (KAS), integral isoconversional method of Flynn-Wall-Ozawa (FWO). DAN-4 demonstrated an apparent activation energy of 211.1 ± 1.66 kJ/mol compared with 160.8 ± 1.07 kJ/mol for pure AP, and 143.82 ± 3.3 kJ/mol for pure AN. DAN-4 shows higher thermal stability than AP, and AN. This work could promote the application of DAN-4 in the field of composite solid rocket propellant.
随之而来的健康和环境问题促使人们重新努力寻找更环保的替代品，以替代高氯酸铵（AP）作为固体火箭推进剂氧化剂。AP推进剂的卓越性能伴随着环境问题，因此寻找更环保的选择很有必要。硝酸铵（AN）已成为一种可行的替代品，它具有成本效益、对敌方不可检测且易于处理的特性，以及更清洁的燃烧产物。结构不稳定性是基于AN的推进剂存在的问题之一。这项工作旨在通过创建基于硝酸根（NO）的绿色高能分子钙钛矿来克服这一障碍。通过分子组装技术合成了NH(CHN)(NO)（DAN-4）。应用扫描电子显微镜（SEM）、X射线衍射（XRD）和傅里叶变换红外光谱（FTIR）对AP、AN和DAN-4的结构和形态进行了表征。使用差示扫描量热法（DSC）和热重分析（TGA）研究了AP、AN和DAN-4的热分解。结果表明，DAN-4在201°C时有一个放热峰，放热1420 J/g，而AN分别在54°C和128°C有两个吸热相变，熔点为170°C，在294°C发生热分解，无放热峰且无热量释放。DAN-4显示出比普通氧化剂（AP）更高的能量释放，AP释放836 J/g。通过等转化率（无模型）和模型拟合研究了分解动力学。基辛格法、基辛格-赤平-ose（KAS）法、弗林-沃尔-小泽（FWO）的积分等转化率方法。DAN-4的表观活化能为211.1±1.66 kJ/mol，而纯AP为160.8±1.07 kJ/mol，纯AN为143.82±3.3 kJ/mol。DAN-4显示出比AP和AN更高的热稳定性。这项工作可以促进DAN-4在复合固体火箭推进剂领域的应用。
