Particle size reduction of RDX by sequential application of solvent–antisolvent recrystallization and mechanical methods

ABSTRACT

Solvent–antisolvent recrystallization produced ~8 µm average size RDX particles (UF-RDX) that were subsequently subjected to mechanical methods of ultrasonication and ball-milling to find further achievable reduction in particle size. Long duration ultrasonication for 20 h and 300 rpm ball milling for 4 h of UF-RDX decreased its average particle size to ~2 µm. RDX produced by all the three processes (solvent–antisolvent recrystallization, ultrasonication and ball-milling) was similar to coarser RDX in structure and thermal decomposition behavior. However, UF-RDX produced by solvent–antisolvent recrystallization was significantly less impact sensitive than that produced by ball-milling and ultrasonication. The issues of residual solvent and the metal contamination during RDX processing were addressed by process parameter optimization. Solvent–antisolvent recrystallization and mechanical methods even when used sequentially could not bring average particle size of RDX to nano-scale.     

几种多态含能材料构型转变的DFT研究

为了从分子层面上对含能材料不同分子构型间的转变情况有一个直观认识,借助Gaussian 09软件,运用密度泛函理论(DFT),采用TS算法搜寻β-RDX→α-RDX、γ-HMX→β-HMX、ε-CL-20→β-CL-20及β-FOX-7→α-FOX-7在分子构型转变过程中的过渡态结构,确定了它们的构型转变过程;并通过计算吉布斯自由能随构型转变路径的变化,比较多态含能材料分子构型转变的难易程度。结果表明,由亚稳晶型到稳定晶型的转变首先会越过过渡态,克服自由能能垒转变为亚稳态结构,实现β-RDX→α-RDX、γ-HMX→β-HMX、ε-CL-20→β-CL-20及β-FOX-7→α-FOX-7分子构型转变分别需要克服的自由能能垒分别为5.25、22.21、9.69和10.24kJ/mol。因此,常温常压下β-RDX→α-RDX、γ-HMX→β-HMX、ε-CL-20→β-CL-20及β-FOX-7→α-FOX-7构型转变的难度大小排序为:HMX>>FOX-7>CL-20>RDX。     

RDX热分解研究

为了更加全面的探究黑索今(RDX)热安全性,利用绝热加热法及DSC-TG-DTG法两种实验方法分析了RDX的热分解过程。通过对比两种实验方法可以总结出RDX在密闭条件下热分解初始速度比在开放系统中低5.4℃,实验条件对分解过程及相关参数影响较大。     

Fe2O3-Al纳米铝热剂与超细RDX复合物的制备与性能

采用溶胶-凝胶方法,制备出了纳米铝热剂nano-Fe2O3-Al,并获得了其与超细RDX的复合含能材料nanoFe2O3-Al/SFRDX。采用BET法、SEM、XRD综合表征了nano-Fe2O3-Al的结构,采用TG/DSC联用技术测试了nano-Fe2O3-Al的热性能,结果表明气凝胶铝热剂的反应温度更低;nano-Fe2O3-Al的静电火花感度测试结果表明纳米铝热剂对静电十分敏感。对nano-Fe2O3-Al/SFRDX在无约束条件和密闭条件下的燃烧行为进行了研究,高速相机照片法发现在无约束条件下,nanoFe2O3-Al燃烧高达300 m/s,且nano-Fe2O3-Al/SFRDX具有在无约束条件下由燃烧转为爆轰的趋势。     

黑索今的合成工艺最新研究进展

综述了国内外合成RDX的最新方法及改进工艺。对各种工艺的原理和优缺点进行了归纳总结。系统介绍了RDX制备中的新技术应用,并对今后的研究重点进行了展望。     

单质炸药连续干燥工艺试验

介绍了一种RDX/HMX连续干燥工艺,过程包括连续定量加料、搅拌溢流配浆、过滤、干燥和冷却,可将RDX/HMX的水质量分数由6.7%~12.3%干燥到≤0.02%。该工艺具有人机隔离操作、连续干燥和高安全性的优点;除能够安全干燥含能材料外,还可用于民用粉状化工原材料的连续干燥。     

Removing low ppb level perchlorate, RDX, and HMX from groundwater with cetyltrimethylammonium chloride (CTAC) pre-loaded activated carbon

Perchlorate contaminates vast amounts of groundwater throughout the United States which could potentially be used as potable water. Activated carbon pre-loaded with cetyltrimethylammonium chloride has been shown in this research to be an effective adsorbent for removing perchlorate from three low conductivity (50-66 microS/cm) groundwaters containing perchlorate (ClO(4)(-)) concentrations of 0.85, 1.0, and 5.6 parts per billion (ppb), respectively. In rapid small-scale column tests (RSSCTs), the virgin granular activated carbon (GAC) (used as a control) treated between 20,000 and 40,000 bed volumes (BV) of water. In contrast, the activated carbon that was pre-loaded with CTAC processed 170,000-270,000 BV before perchlorate was detected above 0.25 ppb in the effluent. Though this pre-loading significantly increased the capacity for perchlorate, it also diminished the GAC's capacity to remove organics. The groundwater containing 1 ppb ClO(4)(-) also contained the nitro-organics HMX (0.6 ppb) and RDX (5.5-6.6 ppb). RDX was detected in the effluent from the CTAC-pre-loaded bed after only 8000 BV had been processed whereas 308,000 BV could be processed through the virgin bed before RDX was detected. Likewise, HMX breakthrough was observed after 116,000 BV in the CTAC-pre-loaded bed while the virgin RSSCT exhibited no breakthrough of HMX during a test that was operated for 309,000 BV. However, by combining a CTAC-pre-loaded bed followed by a virgin GAC bed in series, both perchlorate and RDX could be removed for the same length of time.     

Stimulating the anaerobic biodegradation of explosives by the addition of hydrogen or electron donors that produce hydrogen

The anaerobic biodegradation of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), and 2,4,6-trinitrotoluene (TNT) by a methanogenic mixed culture was investigated. Microcosms containing a basal medium and the mixed culture were amended with ethanol, propylene glycol (PG), butyrate or hydrogen gas as the electron donor and a mixture of TNT (50 microM), RDX (25 microM), and HMX (8 microM). After 29 days TNT and RDX were completely transformed to unidentified endproducts in the bottles amended with ethanol, hydrogen, or PG, while 53%, 40%, and 22% of the HMX was transformed, respectively. There was no loss of RDX or HMX in the electron donor unamended control bottles. The ethanol and PG were transformed to near stoichiometric amounts of acetate and propionate, suggesting the immediate electron donor supporting the transformation of the explosives was the H2 evolved during the metabolism of the parent substrate. Our findings suggest that the addition of H2 or electron donors that produce H2 may be a useful strategy for enhancing the anaerobic biodegradation of explosives in contaminated groundwater and soils.     

Confocal Scanning Laser Microscopic Study of the RDX Defect Structure in Deformed Polymer‐Bonded Explosives

The influence of an explosion‐driven deformation on the defect structure in RDX crystals embedded in a polymer‐bonded explosive was investigated by means of confocal scanning laser microscopy. The images were compared to the defect structure in the as‐received RDX grades, embedded in an epoxy resin. In this way it is possible to qualitatively analyze the changes in defect structure of the RDX crystals that were induced by the explosion‐driven deformation. For the first time, these data therefore provide experimental confirmation of how shock waves mechanically interact with energetic crystals – a topic that, up to now, was only explored by means of simulations.     

Theoretical Study of Mechanism and Kinetics of the Reaction of NO2 with s‐Triazine

The decomposition of nitramines explosives have been of great interest for a long time. However, theoretical investigations have concentrated mainly on unimolecular decomposition whereas bimolecular reactions have received only little attention. In this paper, the bimolecular reaction between NO₂ with s‐triazine (TAZ), which is an initial product during the decomposition process of hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine (RDX) is investigated. The structures and potential energy surface (PES) are explored at B3LYP/6‐31G(d,p) and B3P86/6‐31G(d,p) levels, and the energies are refined using the CCSD(T)/cc‐pVTZ methods. The mechanism of the reaction is analyzed. Quantum chemistry calculations reveal that the title reactions possess small barriers that can be similar to, or smaller than that of initial decomposition reactions of RDX, which suggests that bimolecular reactions are also of great importance, and should be further investigated. Moreover, the kinetics were investigated to verify the proposed mechanism of the reaction.