Factors affecting the NQR line width in nitramine explosives

A number of factors associated with crystal quality contribute to the nuclear quadrupole resonance (NQR) line width. Imperfections such as dislocations, voids, strain and impurities can be electrical sources that distort the electric field gradient at nearby quadrupolar nuclei and broaden the observed NQR line. We measured the¹⁴N NQR line widths in powdered samples of the nitramine explosives hexahydro-1,3,5-trinitro-s-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) and 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane and show correlations with sample purity, particle size distribution and density. Cast plastic-bonded explosives containing either RDX or HMX were also studied and their line widths compared with those of the powdered samples.     

Comparison of simplified models for nitramine propellant combustion

Although 1,3,5-Trinitroperhydro-1,3,5-triazine (RDX) and Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) are very similar molecularly and their burning rates as a function of pressure are nearly identical, it is well known that they differ significantly in temperature sensitivity, especially at low pressures. To understand these differences better, three simple models were applied to HMX and RDX combustion. Both the Denison–Baum–Williams and Li–Williams–Margolis models have previously been calibrated for use with RDX. However, the RDX calibration of the Ward–Son–Brewster model was developed in the present work. All three models were compared with relevant measured data including: burning rate, flame stand-off/thickness, combustion stability, and temperature sensitivity. It was shown that all models are capable of accurately determining the burning rate of HMX and RDX as a function of pressure at the baseline initial temperature, but only two of the models are capable of capturing the variation in temperature sensitivity for both HMX and RDX, and only one model can replicate all the other measured characteristics within experimental uncertainty. Analysis using this model suggests that the surface reaction of RDX is much less exothermic than HMX and that there is a shifting between the gas phase and surface reaction dominance with pressure for HMX. This explains why the temperature sensitivity for RDX is nearly flat for low pressures while the temperature sensitivity for HMX increases significantly as the pressure decreases. Importantly, these trends are achieved without adding significant model complexity or having parameters change with pressure or initial temperature.     

Unreacted equation of states of typical energetic materials under static compression:A review

The unreacted equation of state(EOS) of energetic materials is an important thermodynamic relationship to characterize their high pressure behaviors and has practical importance. The previous experimental and theoretical works on the equation of state of several energetic materials including nitromethane, 1,3,5-trinitrohexahydro-1,3,5-triazine(RDX),1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane(HMX), hexanitrostilbene(HNS), hexanitrohexaazaisowurtzitane(HNIW or CL-20), pentaerythritol tetranitrate(PETN), 2,6-diamino-3,5-dinitropyrazine-1-oxide(LLM-105), triamino-trinitrobenzene(TATB), 1,1-diamino-2,2-dinitroethene(DADNE or FOX-7), and trinitrotoluene(TNT) are reviewed in this paper. The EOS determined from hydrostatic and non-hydrostatic compressions are discussed and compared. The theoretical results based on ab initio calculations are summarized and compared with the experimental data.     

基于核四极矩共振原理的炸药探测方法研究与实验

介绍了一种基于核四极矩共振（Nuclear Quadrupole Resonance, NQR）原理的炸药探测方法及其基本原理和其用于炸药探测的依据,提出了一种可行的基于核四极矩共振原理的炸药检测系统,描述了其结构组成、工作原理及实验方法,并给出了对黑索金（RDX）、梯恩梯（TNT）、奥克托今（HMX）、太恩（PETN）和特屈儿（TETRYL）炸药的测试实验结果. 实验表明该方法可行,能实现对以上炸药的探测.     

Theoretical studies on the structure,sensitivity, density,thermodynamic properties and detonation performance of dinitrobitriazoles

Azodinitro- and dinitroethylene-bridged bitriazoles are of interest in the contest of high explosives, and were found to have true local energy minima at the B3LYP/aug-cc-pVDZ level of theory. The optimised structures, vibrational frequencies and thermodynamic quantities for bitriazoles were obtained in the ground state. Kamlet–Jacobs equations were used to evaluate the performance of bitriazoles based on the predicted density and the calculated heat of explosion. Detonation properties (D = 8.12 to 9.23 km s^?1 and P = 28.0 to 39.83 GPa) of bitriazoles were found to be promising compared with those of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX, D = 8.75 km s^?1 and P = 34.7 GPa) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX, D = 8.96 km s^?1 and P = 35.96 GPa). The fusion of azoles particularly appears to be a promising area for investigation, since it may lead to the desirable consequences of higher heat of explosion, higher density and thus improved detonation performance.     

Effect of <Superscript>14</Superscript>N Nucleus Capture in Nuclear Quadrupole Resonance at Small Relaxation Parameters

Experiments on detecting induction signals of nuclear quadrupole resonance (NQR) on ¹⁴N nuclei in hexahydro-1,3,5-trinitro-s-triazine C₃H₆N₆O₆ (RDX) with preliminary changed population densities of NQR energy levels upon exposure to a saturating pulse are described. It is demonstrated that this actually causes the induction signal amplitude to change; however, complete saturation of the transition cannot be reached because of the NQR relaxation time. It is also demonstrated that the results of calculations without regard for the relaxation processes in RDX lack experimental support. Experimental data demonstrate the feasibility of application of the methods of preliminary change of the population densities (by pumping) for multifrequency experiments in NQR and explosive detection.__________Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 4, pp. 49–52, April, 2005.     

The two-frequency nuclear quadrupole resonance for explosives detection

The two-frequency nuclear quadrupole resonance (NQR) of¹⁴N nuclei is described for purposes of explosives detection. Two applications are known: two-frequency NQR for increasing the signal intensity, two-frequency NQR for improved reliability of explosives detection. The two-frequency experiments were carried out in hexahydro-1,3,5-trinitro-s-triazine C₃H₆N₆O₆ and sodium nitrite NaNO₂ as a substitute for octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocycine C₄H₈N₈O₈. The two-frequency sequences for NQR are proposed for increasing the amplitude of NQR signal and improvement of detection condition.     

环五甲撑五硝胺(CRX)结构和性质的DFT预示

用密度泛函理论 (DFT)B3LYP方法 ,在 6 31G 基组水平下 ,全优化计算了环五甲撑五硝胺 (CRX)的分子几何和优化构型下的电子结构 .环C -N键长为 0 .144～ 0 .148nm ,N -NO2 键长为 0 .139～ 0 .142nm ;CRX的最高占有MO(HOMO)能级和最低未占MO(LUMO)能级之间的差值ΔEg(5 .2 0 5 4eV)较大 ,预示CRX较稳定 .基于简谐振动分析求得IR谱频率和强度 .运用统计热力学方法 ,求得在 2 0 0～ 12 0 0K的热力学性质C0p ,m、S0 m 和H0 m.还运用Kamlet公式预示了它的爆速和爆压分别为 916 9m/s和 37.88GPa .     

Zeeman shift--a tool for assignment of 14N NQR lines of nonequivalent 14N atoms in powder samples

The use of Zeeman perturbed 14N nuclear quadrupole resonance (NQR) to determine the ν+ and ν-14N lines in polycrystalline samples with several nonequivalent nitrogen atoms was investigated. The 14N NQR line shift due to a weak external Zeeman magnetic field was calculated, assuming isotropic distribution of EFG tensor directions. We calculated the broad line distribution of the ν+ and ν- line shifts and experimentally confirmed the calculated Zeeman field dependence of singularities (NQR peaks) in cyclotrimethylenetrinitramine (RDX) and aminotetrazole monohydrate (ATMH). The calculated and measured frequency shifts agreed well. The proposed measurement method enabled determination of which 14N NQR lines in ATMH belong to ν+ and which to ν- transitions.     

Raman spectroscopy as a tool for long‐term energetic material stability studies

Raman spectroscopy is shown to be useful as a tool for long‐term stability studies. The stability of a novel submicron‐size γ‐polymorph form of the explosive HMX (octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine) was monitored up to 1 year using Raman spectroscopy. The preparation and characterization of this submicron HMX has been previously discussed. It is important to know the long‐term stability of this submicron γ‐polymorph material under ambient conditions for its eventual utilization. This submicron HMX material has been found to be stable both chemically and polymorphically (to the order of 1% impurity level), even though HMX normally converts to the β‐polymorph at ambient conditions. Copyright © 2007 John Wiley & Sons, Ltd.     

Slice with angulated non-parallel boundaries

The explosive hexahydro-1,3,5-trinitro-s-triazine (CH2-N-NO2)3, commonly known as RDX, has been studied by 14N NQR and 1H NMR. NQR frequencies and relaxation times for the three ν+ and ν- lines of the ring 14N nuclei have been measured over the temperature range 230-330 K. The 1H NMR T1 dispersion has been measured for magnetic fields corresponding to the 1H NMR frequency range of 0-5.4 M Hz. The results have been interpreted as due to hindered rotation of the NO2 group about the N-NO2 bond with an activation energy close to 92 kJ mol(-1). Three dips in the 1H NMR dispersion near 120, 390 and 510 kHz are assigned to the ν0, ν- and ν+ transitions of the 14NO2 group. The temperature dependence of the inverse line-width parameters T2? of the three ν+ and ν- ring nitrogen transitions between 230 and 320 K can be explained by a distribution in the torsional oscillational amplitudes of the NO2 group about the N-NO2 bond at crystal defects whose values are consistent with the latter being mainly edge dislocations or impurities in the samples studied. Above 310 K, the 14N line widths are dominated by the rapid decrease in the spin-spin relaxation time T2 due to hindered rotation of the NO2 group. A consequence of this is that above this temperature, the 1H T1 values at the quadrupole dips are dominated by the spin mixing time between the 1H Zeeman levels and the combined 1H and 14N spin-spin levels.     

Secondary signals in two-frequency nuclear quadrupole resonance on (14)N nuclei with I=1

Our experimental and theoretical studies show that using two-frequency excitation of (14)N nuclei it is possible to observe secondary NQR signals at one of the three possible transitions due to irradiation of another adjacent transition. As a result of the pulse sequence applied to the adjacent transition the spin-echo signals on the detected transition are observed after essential time interval from the initial single pulse on this frequency. Experiments have been performed on the (14)N nuclei in the sodium nitrite (NaNO(2)) and the military explosive hexahydro-1,3,5-trinitro-s-triazine C(3)H(6)N(6)O(6) (RDX).     

DFT studies on a high-energy density cage compound 1, 3, 5, 7, 9, 11-hexo(N(CH3)NO2)-2, 4, 6, 8, 10, 12-hexaazatetracyclo[5, 5, 0, 0, 0] dodecane

The infrared and Raman spectra, heat of formation (HOF) and thermodynamic properties were investigated by B3LYP/6-31G^** method for a new designed polynitro cage compound 1,3,5,7,9,11-hexo(N(CH₃)NO₂)-2,4,6,8,10,12-hexaazatetracyclo[5,5,0,0,0]dodecane. The detonation velocity (D) and pressure (P) were predicted by the Kamlet–Jacobs equations based on the theoretical density and condensed HOF. The bond dissociation energies and bond orders for the weakest bonds were analysed to investigate the thermal stability of the title compound. The computational result shows that the detonation velocity and pressure of the title compound are superior to those of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), but inferior to those of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX) and hexanitrohexaazaisowurtzitane (HNIW). And the analysis of thermal stability shows that the first step of pyrolysis is the rupture of the N₇–NO₂ bond. The crystal structure obtained by molecular mechanics belongs to the P2₁ space group, with the lattice parameters Z = 2, a = 11.8246 Å, b = 10.4632 Å, c = 15.9713 Å, ρ = 1.98 g cm^?3.     

Detection of plastic explosives in luggage with14N nuclear quadrupole resonance spectroscopy

Nuclear quadrupole resonance (NQR) of¹⁴N nuclei has many advantages as a method for detecting nitrogen-containing explosives, the most important are very high chemical specificity, true noninvasive operation and detection of bulk explosive in situ only (no vapor or particular capture needed). One of the most high explosives is hexogen (RDX) often used by terrorists in plasticized forms. The ring nitrogen nuclei in an RDX molecule generate three sets of NQR frequencies corresponding to three physically nonequivalent positions of the molecule in the crystal lattice. The prototype device we have constructed is intended for inspection of suitcases for the presence of plastic explosives containing RDX or octogen by¹⁴N quadrupole resonance. It is essentially a fully automated PC-controlled pulsed FT NQR spectrometer equipped with a large volume (70 1) radio-frequency (RF) sample coil to accommodate a typical suitcase. The device consists of a measure chamber with an RF coil, tuning and matching box, an RF pulse transmitter and a control PC with dedicated cards like digital receiver, frequency synthesizer, pulse programmer and probe-tuning controller. The control software finds the NQR lines and measures their frequencies. An alarm is produced if any of these frequencies matches the characteristic NQR frequency of the explosive and the signal-tonoise ratio exceeds the preset threshold. Multipulse sequences of the type SORC (strong off-resonance comb) or SLSE (spin-locked spin echo) were used in order to increase the allowed data acquisition rate. We could detect 230 g of PMW-8, a plastic explosive (containing 81% of RDX) in 10 s or 100 g in 30 s. Detection probability was not less than 90%.     

Application of the Wavelet Transform for Detecting Signals of Nuclear Quadrupole Resonance

In the present study, the wavelet transform is used to increase the signal-to-noise ratio of nuclear quadrupole resonance (NQR) signals in the direct pulse method. The efficiency of the wavelet and Fourier transforms used for detecting the NQR signal component is compared. The signal consists of noise, magnetoacoustic and piezoelectric signals, noise from external sources, and NQR signal. Signals from ¹⁴ N nuclei in hexahydro-1,3,5-trinitro-s-triazine C₃H₆N₆O₆ (RDX) are investigated at a temperature of 298 K.__________Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 1, pp. 47–50, January, 2005.     

A method to calculate the thermal conductivity of HMX under high pressure

A method based on Debye theory is developed to calculate the thermal conductivity of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX). The phonon–phonon interaction model is built up for solid HMX. The phonon lifetime formula is derived by the phonon–phonon scattering mechanism, and the thermal conductivity tensor is derived by the phonon dispersion model. The thermal conductivities of α/β/δ-HMX are calculated in the temperature range 0–700?K and pressure range of 0–10?GPa. The phonon softening process of HMX is investigated. We have proven that the Debye frequency and thermal conductivity tend to 0 at the phonon softening point. A physical picture of the phonon–phonon interaction, phonon lifetime and phonon softening is built up.     

The pressure-induced phase transition of the solid β–HMX

The structural, vibrational and thermodynamic properties of β-octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (β–HMX) crystal have been studied using the isothermal-isobaric molecular dynamics (NPT-MD) simulations. The variations of cell volume, lattice constants and molecular geometry of solid β–HMX are presented and discussed at different pressure and temperature. It was found that the N–N bond is significantly lengthened with increasing temperature, which suggests that it is relevant to the initial decomposition. An abrupt change at 27 Gpa for the volume and internal geometrical parameters was observed. This is in good accord with the experimental observation that there is a phase transition at 27 GPa, which is clearly due to conformational change, not chemical reaction. The vibrational frequencies at ambient conditions agree well with experimental results, and the pressure/temperature-induced frequency shifts of these modes are discussed. Frequency discontinuity was also observed at pressure when the phase transition occurred. The Grüneisen parameter was obtained using the vibrational frequency.     

Photoelectron angular distribution measurements of 1,3,5-triazine and 1,3,5,7-cyclooctatetraene

He(I) photoelectron angular distributions of 1,3,5-triazine and 1,3,5,7-cyclooctatetraene were measured. These compounds were found to be typical examples which support the former prediction about the extensibility of the new rule of photoelectron angular distributions presented recently.     

Kinetics of reversible polymorphic transitions in high-energy compounds. Phase transformations in octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine

The kinetics of reversible phase transitions (PTs) in various polymorphs (α, β, γ, δ, and ?) of polycrystalline octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) is investigated by means of differential isothermal and scanning calorimetry. The rate of the β → δ PT is limited by the nucleation process occurring during the induction period. In a general case, the distribution density for the induction times is a superposition of continuous and discrete functions. The reverse δ → β PT obeys the first-order kinetic law. The effects of mechanical exposure on the kinetics and the PT products of the different polymorphs of HMX is investigated by FTIR spectroscopy.     

四硝基并哌嗪(TNAD)与一些含能材料混合体系熔点的分子动力学模拟

利用分子动力学模拟方法预测了TNAD/HMX、TNAD/RDX、TNAD/DINA和TNAD/DNP四种混合体系的熔点, 利用比容与温度的曲线拐点决定了四种混合体系的熔点． 结果是TNAD/HMX、TNAD/RDX、TNAD/DINA的熔点分别为500、536、488 K．而TNAD/DNP体系没有明显的熔点,表明此体系是不相容的．利用熔点进一步预测了四种体系的相容性,分析了它们的径向分布函数．TNAD与HMX、RDX、DINA和DNP之间的分子间相互作用是近距离相互作用,且相容性越好,分子间相互作用越强