Comments on “CARS probe of RDX decomposition”

Recent CARS data from a solid propellant flame that purported to show resonances from the bending modes of HCN are analyzed to demonstrate that the spectral features in question are vibrational transitions of CO₂.     

Thermal decomposition of RDX from reactive molecular dynamics

We use the recently developed reactive force field ReaxFF with molecular dynamics to study thermal induced chemistry in RDX [cyclic-[CH(2)N(NO(2))](3)] at various temperatures and densities. We find that the time evolution of the potential energy can be described reasonably well with a single exponential function from which we obtain an overall characteristic time of decomposition that increases with decreasing density and shows an Arrhenius temperature dependence. These characteristic timescales are in reasonable quantitative agreement with experimental measurements in a similar energetic material, HMX [cyclic-[CH(2)N(NO(2))](4)]. Our simulations show that the equilibrium population of CO and CO(2) (as well as their time evolution) depend strongly of density: at low density almost all carbon atoms form CO molecules; as the density increases larger aggregates of carbon appear leading to a C deficient gas phase and the appearance of CO(2) molecules. The equilibrium populations of N(2) and H(2)O are more insensitive with respect to density and form in the early stages of the decomposition process with similar timescales.     

Shock wave induced decomposition of RDX: time-resolved spectroscopy

Time-resolved optical spectroscopy was used to examine chemical decomposition of RDX crystals shocked along the [111] orientation to peak stresses between 7 and 20 GPa. Shock-induced emission, produced by decomposition intermediates, was observed over a broad spectral range from 350 to 850 nm. A threshold in the emission response of RDX was found at about 10 GPa peak stress. Below this threshold, the emission spectrum remained unchanged during shock compression. Above 10 GPa, the emission spectrum changed with a long wavelength component dominating the spectrum. The long wavelength emission is attributed to the formation of NO2 radicals. Above the 10 GPa threshold, the spectrally integrated intensity increased significantly, suggesting the acceleration of chemical decomposition. This acceleration is attributed to bimolecular reactions between unreacted RDX and free radicals. These results provide a significant experimental foundation for further development of a decomposition mechanism for shocked RDX (following paper in this issue).     

Shock wave induced decomposition of RDX: quantum chemistry calculations

Quantum chemical calculations on single molecules were performed to provide insight into the decomposition mechanism of shocked RDX. These calculations complement time-resolved spectroscopy measurements on shock wave compressed RDX crystals (previous paper, this issue). It is proposed that unimolecular decomposition is the primary pathway for RDX decomposition in its early stages and at stresses lower than approximately 10 GPa. This decomposition leads to the generation of broadband emission from 350 to 850 nm. Chemiluminescence from (2)B1 and (2)B2 excited states of NO2 radicals is associated with a major portion of the experimentally observed emission spectrum (>400 nm). The remaining portion (<400 nm) of the emission spectrum primarily results from excited HONO intermediates. It is proposed that for stresses higher than 10 GPa, bimolecular reactions between radical decomposition products and unreacted RDX molecules become the dominant pathway. This radical assisted homolysis pathway is cyclic and leads to the acceleration of decomposition, with increased production of low energy NO2 radicals. These radicals produce emission that is stronger in the long wavelength portion of the spectrum. Finally, a comprehensive chemical decomposition mechanism is put forward that is consistent with the experimental observations of shock-induced emission in RDX crystals.     

Theoretical study on initial decomposition paths of energetic materials featuring RDX ring

The molecular properties of RDX are affected by the introduction of different functional groups, and the decomposition process of these analogues is studied in this paper. DFT method is used to study the initial decomposition reaction paths of 30 high energy materials based RDX skeleton. In the nitro cleavage reaction, the energy barrier become relatively low by introducing CH(NO₂)₂ or  C(NO₂)₃ groups on the C site of the six membered ring. In the ring opening reaction, the ring opening process is easier to proceed by introducing  NH₂ or  NHNH₂ groups on the C site of the six membered ring.     

Nonadiabatic decomposition of gas-phase RDX through conical intersections: an ONIOM-CASSCF study

Topographical exploration of nonadiabatically coupled ground- and excited-electronic-state potential energy surfaces (PESs) of the isolated RDX molecule was performed using the ONIOM methodology: Computational results were compared and contrasted with the previous experimental results for the decomposition of this nitramine energetic material following electronic excitation. One of the N-NO(2) moieties of the RDX molecule was considered to be an active site. Electronic excitation of RDX was assumed to be localized in the active site, which was treated with the CASSCF algorithm. The influence of the remainder of the molecule on the chosen active site was calculated by either a UFF MM or RHF QM method. Nitro-nitrite isomerization was predicted to be a major excited-electronic-state decomposition channel for the RDX molecule. This prediction directly corroborates previous experimental results obtained through photofragmentation-fragment detection techniques. Nitro-nitrite isomerization of RDX was found to occur through a series of conical intersections (CIs) and was finally predicted to produce rotationally cold but vibrationally hot distributions of NO products, also in good agreement with the experimental observation of rovibrational distributions of the NO product. The ONIOM (CASSCF:UFF) methodology predicts that the final step in the RDX dissociation occurs on its S(0) ground-electronic-state potential energy surface (PES). Thus, the present work clearly indicates that the ONIOM method, coupled with a suitable CASSCF method for the active site of the molecule, at which electronic excitation is assumed to be localized, can predict hitherto unexplored excited-electronic-state PESs of large energetic molecules such as RDX, HMX, and CL-20. A comparison of the decomposition mechanism for excited-electronic-state dimethylnitramine (DMNA), a simple analogue molecule of nitramine energetic materials, with that for RDX, an energetic material, was also performed. CASSCF pure QM calculations showed that, following electronic excitation of DMNA to its S(2) surface, decomposition of this molecule occurs on its S(1) surface through a nitro-nitrite isomerization producing rotationally hot and vibrationally cold distributions of the NO product.     

Kinetics of initial thermal decomposition and detonation parameters-studies on RDX:TNT system

The initial low temperature thermal decomposition of various compositions in the binary system—1,3,5 trinitro-1,3,5 triazacyclohexane (RDX) and 2,4,6 trinitro toluene (TNT) has been studied using thermogravimetry, high temperature infrared spectroscopy and photomicroscopy. A linear correlation has been observed between the activation energies for the initial stage of thermal decomposition and velocity of detonation in this system.

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Zusammenfassung Mittels Thermogravimetrie, Hochtemperatur-IR-Spektroskopie und Fotomikroskopie wurde die einleitende thermische Zersetzung bei niedriger Temperatur von verschiedenen Gemischen des binären Systems von 1,3,5-Trinitro-1,3,5-triazazykIohexan (RDX) und 2,4,6 Trinitrotoluol (TNT) untersucht. Zwischen der Aktivierungsenergie des Anfangsschrittes der thermischen Zersetzung und der Detonationsgeschwindigkeit in diesem System konnte einer lineare Korrelation nachgewiesen werden.

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, 1,3,5--1,3,5 2,4,6- . .

     

Thermal behavior and decomposition kinetics of ETN and its mixtures with PETN and RDX

Erythritol tetranitrate (butane-1,2,3,4-tetrayl tetranitrate, ETN) has become one of the most synthesized improvised explosives nowadays as it can be found on public internet discussion boards. However, the low melting point, nitrocellulose gelling ability, high energy content, and availability of its precursor make the substance potentially useful in industry as an energetic component or additive in certain gun propellants. Mixtures of ETN with other high explosives are also frequently discussed on web pages dealing with improvised explosives. This article describes thermal behavior and decomposition kinetics of pure ETN and its mixtures with pentaerythritol tetranitrate and cyclonite (1,3,5-trinitro-1,3,5-triazinane, RDX). The thermal behavior and decomposition kinetics of such mixtures are described using non-isothermal DSC and TG techniques. Kissinger method, Soviet manometric method, and modified Kissinger–Akahira–Sunose method were used for data evaluation.     

Hydrogen-deuterium exchange experiments to probe the decomposition reaction of sodium alanate

NaAlH(4) is the archetypical complex hydride for hydrogen storage. The extraordinary effect of dopants on the sorption kinetics triggered the investigation of this empirical finding. In this paper, a short review of the state of the art is given. To gain further understanding of the mechanisms involved we label the interacting species during the sorption process. This was experimentally realized by hydrogen-deuterium exchange measurements during the decomposition of NaAlH(4) followed by thermogravimetry, Raman spectroscopy and mass spectrometry. By these experiments we are able to obtain specific information on the diffusing species and formation of intermediates. The activation energy of tracer diffusion in NaAlH(4) is found to be 0.28 eV. The results are evidence for a vacancy-mediated desorption process of NaAlH(4).     

Time-resolved spectroscopic measurements of shock-wave induced decomposition in cyclotrimethylene trinitramine (RDX) crystals: anisotropic response

Plate impact experiments on the (210), (100), and (111) planes were performed to examine the role of crystalline anisotropy on the shock-induced decomposition of cyclotrimethylenetrinitramine (RDX) crystals. Time-resolved emission spectroscopy was used to probe the decomposition of single crystals shocked to peak stresses ranging between 7 and 20 GPa. Emission produced by decomposition intermediates was analyzed in terms of induction time to emission, emission intensity, and the emission spectra shapes as a function of stress and time. Utilizing these features, we found that the shock-induced decomposition of RDX crystals exhibits considerable anisotropy. Crystals shocked on the (210) and (100) planes were more sensitive to decomposition than crystals shocked on the (111) plane. The possible sources of the observed anisotropy are discussed with regard to the inelastic deformation mechanisms of shocked RDX. Our results suggest that, despite the anisotropy observed for shock initiation, decomposition pathways for all three orientations are similar.     

Ultrafast photodissociation dynamics of HMX and RDX from their excited electronic states via femtosecond laser pump–probe techniques

Femtosecond laser pump–probe techniques are employed to investigate the mechanisms and dynamics of the photodissociation of HMX and RDX from their excited electronic states at three wavelengths (230 nm, 228 nm, and 226 nm). The only observed product is the NO molecule. Parent HMX and RDX ions are not observed. The NO molecule has a resonant A²Σ ← X²Π (0, 0) transition at 226 nm and off-resonance two-photon absorption at 228 nm and 230 nm. Pump–probe transients of the NO product at both off-resonance and resonance absorption wavelengths indicate the decomposition dynamics of HMX and RDX falls into the timescale of our laser pulse duration (180 fs).     

Enhanced thermal decomposition,laser ignition and combustion properties of NC/Al/RDX composite fibers fabricated by electrospinning

Cellulose - Nano aluminum (Al) has always been the research hotspot in the field of energetic materials because of its high energy density and combustion temperature, and has been considered to be...     

Determination of the photolytic decomposition pathways of benzylchlorodiazirine by C60 probe technique

By employing C₆₀ as a chemical probe, the photolysis of benzylchlorodiazirine has been proposed to form carbene and the rearranged products via the excited state.     

Thermal analysis of RDX with contaminants

Many investigations and researches studied the reaction ability between high explosive RDX and RDX with other chemicals. However, accidents still occur and operating problems exist among the RDX manufacturing process. This study utilized inherent safety concepts and DSC thermal analysis to assess the incompatible reaction hazards of RDX during usage, handling, storage, transporting and manufacturing. This assessment includes thermal curve observations and kinetic evaluations. A decomposition mechanism of the incompatible reaction is proposed. Among all the contaminants evaluated in this study, the existence of ferrous chloride tetrahydrate, ferric chloride hexahydrate and nitric acid shifted the main endothermic and exothermic reactions of RDX. These contaminants further advanced the exothermic temperature onset average by about 53, 46 and 61°C, respectively. The summarized results suggest that ferric oxide, ferrous chloride tetrahydrate, ferric chloride hexahydrate, acetone solution and nitric acid can influence the reaction and thermokinetic properties of RDX. These chemicals could induce potential hazards by causing temperature control instability, heating and cooling systems failure, and produce an unexpected secondary explosion. According to the conclusions of this study, potential incompatible RDX hazards during usage and manufacturing could be avoided.     

Crystal defects and stability of RDX

NQR studies demonstrated that structure imperfection of RDX crystals is affected by impurities, the particle size, and the modes of crystallization and pressing of the sample. The initial rate of RDX decomposition depends on the same factors. In pure samples, the rate varies 1.5—2 times and is proportional to imperfection. In spite of crystal destruction, the rate of thermal decomposition in pressed samples decreases due, apparently, to strengthening of the cell effect.     

Reduction as a probe for benzothiirene intermediates: Thermal and photochemical decomposition of 1,2,3 -benzothiadiazoles.

Four benzothiadiazoles were either heated at reflux or irradiated at room temperature in tetrahydronaphthalene. The base soluble thiols which were obtained were converted to thiolacetates and analyzed by use of infrared and nmr shift-reagent spectroscopy.     

The chemical ionization mass spectrometry of RDX

The fragmentation pathways of RDX in chemical ionization mass spectrometry have been rationalized, using data from different reagent gases, including CD₄ and iso-C₄D₁₀. The dependence of spectra taken with different gases on the acid strength of the reactant ions in the gases is accounted for.     

Thermal decomposition and sensitivities of RDX/SiO<Subscript>2</Subscript> nanocomposite prepared by an improved supercritical SEDS method

A kind of classic nanocomposite, in which nano-RDX (~60 nm) was embedded inside as the core and nano-SiO₂ (~6 nm) compactly coated on its surface, was successfully prepared by an improved supercritical SEDS method. Therein, a special design of the nozzle made the fabrication realized. Analyses, such as SEM, TEM, XRD, IR, and XPS, were employed to investigate the micron morphology and structure of the nanocomposite. Thermal analysis was also conducted, and the DSC traces collected at different heating rate were obtained. Using these DSC data, we calculated the kinetic and thermodynamic parameters for thermal decomposition of raw RDX, RDX/SiO₂ nanocomposite, and a simple mixture ([RDX + SiO₂]), by which the characteristic of the decomposition was depicted clearly. It was confirmed that for different samples, the parameters such as E _K, ΔH ^≠, and T _b changed remarkably. Meanwhile, the decomposition products were also probed with DSC-IR analysis. The results indicated that the main products for both raw RDX and RDX/SiO₂ were CO₂, N₂O, and NO₂. However, the detected signal intensity of NO₂ for RDX/SiO₂ was much stronger than that for raw RDX. In addition, testing of mechanical sensitivity disclosed that RDX/SiO₂ was far more insensitive than raw RDX, and then the mechanism about this was discussed.