An Ab Initio Theoretical Study of 2,4,6‐Trinitro‐1,3,5‐Triazine, 3,6‐Dinitro‐1,2,4,5‐Tetrazine,and 2,5,8‐Trinitro‐Tri‐s‐Triazine

In order to evaluate 2,4,6‐trinitro‐1,3,5‐triazine (TNTAz), 3,6‐dinitro‐1,2,4,5‐tetrazine (DNTAz), and 2,5,8‐trinitro‐tri‐s‐triazine (TNTsTAz), the geometries of these compounds have been fully optimized employing the B3LYP density functional method and the AUG‐cc‐pVDZ basis set. The accurate gas phase enthalpies of formation have been obtained by using the atomization procedure and designing isodesmic reactions in which the parent rings are not destroyed. Based on B3LYP/AUG‐cc‐pVDZ calculated geometries and natural charges, the crystal structures have been predicted using the Karfunkel–Gdanitz method. Computed results show that there exists extended conjugation over the parent rings of these compounds. More energy content is reserved in DNTAz than in both TNTAz and TNTsTAz. The title compounds are much more sensitive than 1,3,5‐trinitrobenzene. The calculated detonation velocity of DNTAz reaches 9.73–9.88 km s⁻¹, being larger than those of CL‐20 and TNTAz. TNTsTAz has no advantage over the widely used energetic compounds such as RDX and HMX.     

The Low‐Temperature High‐Pressure Phase Diagram of Energetic Materials: I. Hexahydro‐1,3,5‐Trinitro‐s‐Triazine

The reaction phase diagram of hexahydro‐1,3,5‐trinitro‐s‐triazine (RDX) has been studied as a function of temperature and pressure by Raman spectroscopy to 29 GPa and temperatures ranging from 4 to 298 K. Three stable phases (α, γ, and δ) have been found and their phase stabilities have been investigated. Phase boundaries were studied as a function of pressure and temperature, permitting a delineation of the various polymorph stability fields. A pressure–temperature reaction/phase diagram is constructed from the results of this study and compared to previous high temperature work.     

1,3,5‐Trinitroperhydro‐1,3,5‐triazine (RDX)‐Based Sheet Explosive Formulation with a Hybrid Binder System

A plastic‐bonded explosive (PBX) in the form of a sheet was formulated comprising of 1,3,5‐trinitroperhydro‐1,3,5‐triazine (RDX) and an hybrid binder system containing a linear thermoplastic polyurethane and a fluoroelastomer (Viton). The effect of a fluoroelastomer on the explosive as well as mechanical properties and thermal behavior of sheet explosive formulations were investigated and compared with a control formulation containing 90 % of RDX and 10 % of natural rubber (ISNR‐5). The replacement of 10 % natural rubber by a hybrid binder system led to an increase in the velocity of detonation (VOD) of the order of 250–950 m s⁻¹ and better mechanical properties in terms of tensile strength (1.9–2.5 MPa) compared to the control formulation (RDX/ISNR‐5 (90/10)). The compatibility of ingredients and thermal decomposition kinetics of selected sheet explosive formulations were investigated by vacuum stability tests and differential scanning calorimetry (DSC). The results suggested better compatibility of RDX with the hybrid binder system (polyurethane/Viton), which is useful to reduce potential hazards in handling, processing, and storage.     

Degradation of hexahydro‐1,3,5‐trinitro‐1,3, 5‐triazine (RDX) by anaerobic mesophilic granular sludge from a UASB reactor

BACKGROUND: This study investigated the performance of anaerobic mesophilic granular sludge for the degradation of hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine (RDX). Batch tests were conducted to investigate the effects of different supplements on the RDX degradation ability of anaerobic granular sludge, as well as the contributions of both physicochemical and biological processes involved in RDX removal from aqueous solution. RESULTS: Anaerobic granular sludge exhibited good performance in treating RDX as the sole substrate. Biodegradation was the main mechanism responsible for RDX removal. Ammonium had no significant promoting effect on the degradation process. The presence of glucose was found to enhance the degradation of RDX by anaerobic granular sludge, while the addition of sulfate and nitrate had adverse effects on the reductive transformation of RDX. CONCLUSIONS: Anaerobic granular sludge is capable of removing RDX from aqueous solution with high efficiency. This study showed good prospects for high‐rate anaerobic processes in the treatment of munition wastewater. The results can be used for the design and optimization of high rate anaerobic systems for the elimination of RDX. Copyright © 2010 Society of Chemical Industry     

Degradation of TNT,RDX, and HMX Explosive Wastewaters Using Zero‐Valent Iron Nanoparticles

The high‐energy explosives 2,4,6‐trinitrotoluene (TNT), hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine (RDX), and the high melting explosive octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine (HMX) are common groundwater contaminants at active and abandoned munitions production facilities causing serious environmental problems. A highly efficient and environmentally friendly method was developed for the treatment of the explosives‐contaminated wastewaters using zero‐valent iron nanoparticles (ZVINs). ZVINs with diameters of 20–50 nm and specific surface areas of 42.56 m² g⁻¹ were synthesized by the co‐precipitation method. The explosives degradation reaction is expressed to be of pseudo first‐order and the kinetic reaction parameters are calculated based on different initial concentrations of TNT, RDX, and HMX. In addition, by comparison of the field emission scanning electron microscopy (FE‐SEM) images for the fresh and reacted ZVINs, it was apparent that the ZVINs were oxidized and aggregated to form Fe₃O₄ nanoparticles as a result of the chemical reaction. The X‐ray diffraction (XRD) and X‐ray absorption near edge structure (XANES) measurements confirmed that the ZVINs corrosion primarily occurred due to the formation of Fe₃O₄. Furthermore, the postulated reaction kinetics in different concentrations of TNT, RDX, and HMX, showed that the rate of TNT removal was higher than RDX and HMX. Furthermore, by‐products obtained after degradation of TNT (long‐chain alkanes/methylamine) and RDX/HMX (formaldehyde/methanol/hydrazine/dimethyl hydrazine) were determined by LC/MS/MS, respectively. The high reaction rate and significant removal efficiencies suggest that ZVINs might be suitable and powerful materials for an in‐situ degradation of explosive polluted wastewaters.     

Preparation and Characterization of Hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine/Ammonium Perchlorate Intermolecular Explosives

Hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine/ammonium perchlorate/glycidyl azide polymer (RDX/AP/GAP) intermolecular explosives (IMX) with different proportions of RDX to AP were prepared by sol‐gel method, and the structure and performance was characterized by Brunauer‐Emmett‐Teller measurements (BET), X‐ray diffraction (XRD), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The results showed that the specific surface area of RDX/AP/GAP IMX decreased with the addition of AP. The crystals of AP and RDX in RDX/AP/GAP intermolecular explosives were in the range of 20–48 nm and 23–55 nm, respectively. In addition, RDX/AP/GAP intermolecular explosives had the largest heat release at zero balance.     

Micro Videographic Analysis of the Melt Layer of Self‐Deflagrating HMX and RDX

Micro videographic analysis of the thin molten layer on the surface of HMX (Octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine) and RDX (Hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine) during self deflagration were performed. This was done to gain a better understanding of the physical structure present in this 100–300 μm layer and give a visual picture for the development of computational models. During steady‐state combustion, RDX had a consistent melt layer with vigorous bubble formation. There was a continuous liquid layer throughout combustion and no foam was formed. The surface of HMX during steady‐state combustion at ambient initial temperatures was an uneven layer of foam. Foam appeared to convect across the surface in undulating waves. At elevated initial temperatures, the HMX molten layer was a consistent foam layer in both time and space. Micro videography was also done with a diagnostic laser sheet as illumination to measure the melt layer thickness. The RDX bubbling layer was about 217±30 μm thick. The HMX foam thickness varied from almost nothing to 660 μm, with an average value of about 234±106 μm.     

NH_3和ClO_3对RDX初始热裂解的影响

用B3LYP/6-31G(d)方法,优化得到RDX及其与高氯酸铵(AP)裂解产物NH3、ClO3形成复合物的稳定构型,计算了RDX及各复合物的N-NO2键解离能.结果表明,复合物中RDX构型变化不是很大,但其CS对称性遭到破坏.RDX与NH3、ClO3结合后其N-NO2键解离能与RDX相比变化不大, NH3、ClO3的存在不影响RDX硝基裂解A位优先于E位的顺序.但一旦复合物裂解,生成的NO2极易与NH3发生反应,放出大量热,从而可引发RDX的后续裂解反应.     

Production and Characterization of Composite Nano‐RDX by RESS Co‐Precipitation

Nanoscale composites of hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine (RDX) and polymeric binders were produced by co‐precipitation using rapid expansion of supercritical solutions (RESS). The binders used in this study are poly (vinylidene fluoride‐co‐hexafluoropropylene) (VDF‐HFP₂₂) and polystyrene (PS). The RDX/VDF‐HFP₂₂ and RDX/PS co‐precipitated nanoparticles were characterized by Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). The average size of produced nanoparticles is ca. 100 nm. TEM analysis of RDX/PS nanocomposite shows a core‐shell structure with RDX as the core material and the shell consisting of the polymeric binder. X‐ray Powder Diffraction (XRPD) analysis indicates polycrystalline structure of RDX in the product with a crystallite size of 42 nm. The content of RDX in the composite particles is in the range of 70–73 % by mass as determined by Gas Chromatography Mass Spectroscopy (GCMS) and by XRPD.     

Assessment of aged biodegradable polymer‐coated nano‐zero‐valent iron for degradation of hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine (RDX)

BACKGROUND: This study reports on the effects of aging on suspension behavior of biodegradable polymer‐coated nano‐zero‐valent iron (nZVI) and its degradation rates of hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine (RDX) under reductive conditions. The polymers investigated included guar gum, potato starch, alginic acid (AA), and carboxymethyl cellulose (CMC). Polymer coating was used to mitigate nZVI delivery hindrance for in situ treatment of RDX‐contaminated groundwater. RESULTS: The RDX degradation rates by bare nZVI and starch‐coated nZVI suspensions were least affected by aging although these suspensions exhibited the least favorable dispersion behavior. CMC, AA, and guar gum coating improved nZVI rates of degradation of RDX but these rates decreased upon aging. The best suspension stability upon aging was achieved by CMC and AA. Guar gum with loadings rates one order of magnitude lower than that of CMC and AA achieved good iron stabilization but significantly higher RDX degradation rates. CONCLUSION: It is demonstrated that both migration and reactivity of polymer‐stabilized nZVI should be explicitly evaluated over a long period before application in the field. Guar gum coated nZVI appeared best suited for in situ application because it maintained good suspension stability, with RDX degradation rates least affected by aging compared with the other polymers tested. © 2012 Society of Chemical Industry     

An Improved Process Towards Hexahydro‐1,3,5‐trinitroso‐1,3,5‐triazine (TNX)

Hexahydro‐1,3,5‐trinitroso‐1,3,5‐triazine (TNX) is mostly known as a by‐product in the environmental decomposition of RDX. The original chemistry to TNX was never optimized and thus resulted in low yields due to competitive degradation of the starting material. Enabled conditions to TNX were developed by optimizing pH effects and mitigating foaming by reactor geometry and stirring. The conditions presented herein allow for the inexpensive and simple production of multi‐gram quantities of TNX. The isolated TNX obtained by our new method was characterized by ¹H NMR, ¹³C NMR, DSC, and X‐ray crystallography. A preliminary evaluation of the sensitivity of TNX towards impact and friction is also presented.     

Removal of 2,4,6-trinitrotoluene (TNT) and 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) from aqueous solutions with surfactants

2,4,6-Trinitrotoluene (TNT) was found to react in aqueous solution with surfactants containing amino and quaternary ammonium groups at pH 10–11 at ambient temperature. The surfactants investigated included N-tallow 1,3-diaminopropane, trimethyl N-tallow ammonium chloride and N,N,N′,N′,N′-pentamethyl N-tallow 1,3-propane diammonium dichloride. The reaction products were insoluble in water and readily separated through filtration. The dried solids were not explosive and the solids burned without explosion. The results showed that TNT can be reduced to less than 0.1 ppm from the initial concentration of 110 ppm in 2–3 hours. The wastewater of Composition B contains TNT and 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX). Treatment of the wastewater with the ammonium cationic surfactants showed that TNT was removed quantitatively by precipitation and RDX was simultaneously hydrolyzed. The mechanism of this treatment is discussed.     

Study of Plastic Explosives based on Attractive Cyclic Nitramines Part I. Detonation Characteristics of Explosives with PIB Binder

Four plastic explosives based on energetic nitramines and a non‐energetic binder were prepared and studied. The nitramines were RDX (1,3,5‐trinitro‐1,3,5‐triazine), HMX (1,3,5,7‐tetranitro‐1,3,5,7‐tetrazine), BCHMX (cis‐1,3,4,6‐tetranitro‐octahydroimidazo‐[4,5‐d]imidazole) and HNIW (ε‐2,4,6,8,10,12‐hexanitro‐2,4,6,8,10,12‐hexaazaisowurtzitane, ε‐CL‐20). The binder was in all cases polyisobutylene (PIB) as in the standard composition C‐4. These powerful plastic explosives were compared to standard PETN‐based commercially available explosives Semtex 1A and Sprängdeg m/46. The detonation velocities were experimentally measured and compared to the ones calculated by the Kamlet–Jacobs method, CHEETAH and EXPLO5 Codes. The experimental detonation velocities as well as the calculated detonation parameters decrease in the following order: HNIW‐PIB>HMX‐PIB≥BCHMX‐PIB>RDX‐PIB>Sprändeg m/46≥Semtex 1A. Urizar coefficients for the various binders were calculated from experimental data.     

Engineered Biomolecular Recognition of RDX by Using a Thermostable Alcohol Dehydrogenase as a Protein Scaffold

There are many biotechnology applications that would benefit from simple, stable proteins with engineered biomolecular recognition. Here, we explored the hypothesis that a thermostable alcohol dehydrogenase (AdhD from Pyrococcus furiosus) could be engineered to bind a small molecule instead of a cofactor or molecules involved in the catalytic transition state. We chose the explosive molecule 1,3,5‐trinitro‐1,3,5‐triazine (royal demolition explosive, RDX) as a proof‐of‐concept. Its low solubility in water was exploited for immobilization for biopanning by using ribosome display. Docking simulations were used to identify two potential binding sites in AdhD, and a randomized library focused on tyrosine or serine mutations was used to determine that RDX was binding in the substrate binding pocket of the enzyme. A fully randomized binding pocket library was selected, and affinity maturation by error‐prone PCR led to the identification of a mutant (EP‐16) that gained the ability to bind RDX with an affinity of (73±11) μm . These results underscore the way in which thermostable enzymes can be useful scaffolds for expanding the biomolecular recognition toolbox.     

Quire Interaction of Certain Nitramine Type Explosives with Proton——A DFT Study

The composites of certain nitramine type explosives, TETRYL, RDX and EDNA, with proton in vacuum have been considered within the constraints of density functional theory at the level of B3LYP/6-31++G(d,p) (restricted and unrestricted).The results indicate that unexpectedly hydrogen molecule production occurs by the interaction of proton and a hydrogen of CH3 (TETRYL) and CH2 (RDX and EDNA) groups.As a result, a carbocation is generated on the explosive molecules.Thereafter, TETRYL which potentially has many protonation sites were investigated in more detail in vacuum and aqueous conditions.The data reveals that the composite system (TETRYL+proton) is less stable than TETRYL protonated on nitramine NH or oxygen of the nitro groups.     

Nickel‐catalysed Kumada polycondensation of di‐functionalized Grignard reagent with aryl fluoride

A nickel catalyst promoted the polymerization between various Grignard reagents with 2‐phenyl‐4,6‐bi(4‐fluorophenyl)‐1,3,5‐triazine. The reaction scope was thoroughly investigated and fully characterized. The Sp²‐C ? F bond was successfully activated by the triazine group in Kumada coupling reactions. Also, di‐Grignard reagents showed higher activity than mono‐Grignard reagents. The reaction scope results reveal that a Grignard reagent with strong nucleophilicity and aryl fluoride with strong electrophilicity are necessary to lead to Kumada polycondensation of oligothiophenes with aryl fluoride. In this work, polymerization between di‐functionalized oligothiophene Grignard reagents with aryl fluoride was first conducted. The weight‐average molecular weight is high, up to 14.8 kDa. The π‐conjugated polymers obtained exhibit emission colours of blue, green and yellow with efficient photoluminescence. © 2016 Society of Chemical Industry     

Quantum Chemical Studies on the Structure and Performance Properties of 1,3,4,5‐Tetranitropyrazole: A Stable New High Energy Density Molecule

Molecular orbital calculations were performed for the geometric and electronic structures, band gap, thermodynamic properties, density, detonation velocity, detonation pressure, stability and sensitivity of 1,3,4,5‐tetranitropyrazole ( R23 ). The calculated density (approx. 2060 kg m⁻³), detonation velocity (approx. 9.242 km s⁻¹) and detonation pressure (approx. 41.30 GPa) of the model compound are appearing to be promising compared to hexahydro‐1,3,5‐trinito‐1,3,5‐triazine (RDX) and octahydro‐1,3,5,7‐tetranitro‐l,3,5,7‐tetrazocine (HMX). Bader’s atoms‐in‐molecules (AIM) analysis was also performed to understand the nature of the intramolecular N ⋅⋅⋅ O interactions and the strength of trigger X NO₂ bonds (where XC, N) of the optimized structure computed from the B3LYP/aug‐cc‐pVDZ level.     

2-氢七氟丙烷的热分解性能和机理

采用密度泛函理论(DFT)中的B3LYP/6-31G(d, p)和MP2/6-31G(d, p)算法计算了C3HF7热解反应的焓变、中间态分子模型及活化能. 结果表明,反应温度对C3HF7分解有明显影响,800℃的热分解产物主要为C3F6,伴随一定量C3HF5, CHF3和(CF3)2C=CF2及痕量产物C2F4, C3F8, C2HF5与C4F8. 热解主要产物C3F6主要来自C3HF7发生H转移反应,伴随H转移反应生成CF3C:CF3与CF3CF:卡宾,F转移反应生成CF2:卡宾和CF3CH:自由基,相互反应生成第二、第三和第四产物C3HF5, CHF3和(CF3)2C=CF2; C?F和C?C键断裂生成的自由基与卡宾结合,生成痕量产物C2F4, C3F8, C2HF5和C4F8.     

RDX和HMX的热分解III.分解机理

简述RDX和HM X热分解的各种机理,其热分解的初始过程是N-N和C-N键断裂的竞争反应,试验条件和样品相态等因素影响竞争过程。用DSC-FT IR联用技术和热裂解原位池/FT IR分析了主要分解气相产物和凝聚相中主要官能团的变化。结果表明,RDX和HM X热分解的主要分解气相产物为N2O,CH2O,CO,CO2,H2O和HCN。RDX的分解气相产物CH2O和H2O红外吸收率的温度关系曲线都产生双峰,RDX基团-NNO2的吸收带1 589 cm-1和1 278 cm-1有两个不同速率的变化过程。用N-N键和C-N键竞争断裂的观点解释了RDX与HM X热分析和产物分析的结果。