<Superscript>14</Superscript>N Nuclear Quadrupole Resonance Study of Polymorphism in Trinitrotoluene Samples Obtained from Old Ordnances

The field application of a ¹⁴N nuclear quadrupole resonance (NQR) detector needed for the detection of different explosives, including trinitrotoluene (TNT), requires the examination of the distribution of ¹⁴N NQR lines stemming from the monoclinic and/or orthorhombic modifications of TNT, as well as from a mixture of both. In this work, 30 different TNT samples up to 70 years old were measured. The main result of this study is that the measured ¹⁴N NQR spectrum is strongly influenced by the environmental conditions to which the explosive was subject during its history.     

New Methods for Detection of 14N NQR Frequencies

Nitrogen atoms are present in a number of solid explosives and illicit substances. The nuclear quadrupole resonance (NQR) spectra and spin?Clattice relaxation of the nitrogen atomic nucleus ¹⁴N can be used to characterize these compounds and to distinguish between possible crystal polymorphs. After the characteristic ¹⁴N NQR frequencies and spin?Clattice relaxation rates in a compound are determined, NQR can be used to detect this compounds and, in case of crystal polymorphs, also to determine the method of preparation. The ¹⁴N NQR frequencies and spin?Clattice relaxation rates are measured either by pulse NQR or by nuclear quadrupole double resonance (NQDR) based on magnetic field cycling. Here, we discuss several ¹H?C¹⁴N NQDR techniques which can be used to measure the ¹⁴N NQR frequencies and spin?Clattice relaxation rates under various experimental conditions. Some characteristic applications of these techniques are presented and discussed in details.     

Temperature dependence of17O and14N NQR frequencies in commercial TNT

The temperature dependence of the¹⁷O nuclear quadrupole resonance (NQR) frequencies has been measured in commercial trinitrotoluene by highly sensitive nuclear quadrupole double resonance techniques. The¹⁴N NQR frequencies have been measured in the same sample for comparison. In contrast to the¹⁴N quadrupole coupling constant, the¹⁷O quadrupole constant increases with increasing temperature.     

NQR investigation and characterization of cocrystals and crystal polymorphs

The application of ¹⁴N NQR to the study of cocrystals and crystal polymorphs is reviewed. In ferroelectric and antiferroelectric organic cocrystals ¹⁴N NQR is used to determine proton position in an N-H...O hydrogen bond and proton displacement below T_C. In cocrystal isonicitinamide – oxalic acid (2:1) ¹⁴N NQR is used to distinguish between two polymorphs and to determine the type of the hydrogen bond (N^?...H-O). The difference in the ¹⁴N NQR spectra of cocrystal formers and cocrystal is investigated in case of carbamazepine, saccharin and carbamazepine - saccharin (1:1). The experimental resolution allows an unambiguous distinction between the ¹⁴N NQR spectrum of the cocrystal and the ¹⁴N NQR spectra of the cocrystal formers. The possibility of application of NQR and double resonance for the determination of the inhomogeneity of the sample and for the study of the life time of an unstable polymorph is discussed.     

14N Study of Aromatic Nitroso Compounds

The ¹⁴N NQR frequencies of selected aromatic C-nitroso compounds were measured using cross relaxation double resonance. The monomers have high ¹⁴N NQR frequencies with Χ and η values of 5700 to 6100 kHz and 0.5 ± 0.1, respectively. The dimers and polymer show lower frequencies with values of 2300 to 2600 kHz and 0.8 ± 0.05. Benzofuroxan has values typical of both the monomer and dimer.     

14N NQR study of selected 1,4-benzoquinonedioximes

The ¹⁴N NQR frequencies of selected 1,4-benzoquinonedioximes were measured using cross relaxation double resonance. As the number of substituents increase, a significant shift in the NQR values is observed. Comparison of unsubstituted and tri-substituted 1,4-benzoquinonedioximes shows that the quadrupole coupling constant (χ) increases by about 1000 kHz and the asymmetry parameter (η) decreases from ≈0.7 to 0.3 respectively. Ab-initio calculations show that for the unsubstituted compound hydrogen bonding between oxime groups and pi-ring stacking is possible which cannot be accommodated for in heavily methyl substituted dioximes and this results in distinct NQR parameters.     

Improving N nuclear quadrupole resonance detection of trinitrotoluene using off-resonance effects

The off-resonance dependence of the amplitudes of the six dominant ¹⁴N nuclear quadrupole resonance (NQR) lines in commercial polymorphic trinitrotoluene (TNT) sample were experimentally determined for a wide range of experimental parameters when irradiated with the spin-lock spin-echo (SLSE) pulse sequence. We find that the amplitudes off-resonance dependence follows a sinc-like function with an additional modulation due to the spacing between the RF pulses. This dependence can be very well modeled with expressions we have derived for a single site ¹⁴N NQR in paranitrotoluene (PNT). The results can be immediately used for the reduction of the number of free parameters used in the robust signal processing models for the TNT NQR detectors.     

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.     

Application of the spherical tensor method for Two-Frequency pure NQR of spinI=1 nuclei

The results of a theoretical investigation of two-frequency excitation in pure nuclear quadrupole resonance (NQR) for a spinI=1 nucleus with a nonaxial elecric field gradient are presented. The multipole tensor operator technique is used for the treatment of the one- and two-frequency pulse excitations. The results are applied to the characterization of the two-frequency signal of nitrogen¹⁴N nuclei. The experiments on sodium nitrite, NaNO₂, confirm the presence of additional (two-frequency) echo in the NQR signal. The effect of resonance offsets on two-frequency NQR is also considered.     

Two-dimensional14N NQR spectra for two-frequency excitation programs

We have determined expressions for the complex amplitudes of signals in the two-dimensional¹⁴N NQR spectrum for different two-frequency excitation programs. We have established a correspondence between the two-dimensional NQR spectra and various methods for excitation of the spin system.Kaliningrad State University. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, pp. 54–57, July, 1992.     

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.     

A New Highly Sensitive 1H-14N Nuclear-Quandrupole Double-Resonance Technique

A new highly sensitive ¹H-¹⁴N nuclear-quadrupole double-resonance technique using magnetic field cycling is presented. It is based on a resonant proton-nitrogen coupling at ν_H = ν₀ and on the excitations of the two other ¹⁴N NQR transitions by a two-frequency irradiation or by a train of frequency sweeps. The sensitivity and resolution of the new technique are estimated. Some typical examples of its application are presented.     

Increasing 14N NQR signal by 1H-14N level crossing with small magnetic fields

NQR detection of materials, such as TNT, is hindered by the low signal-to-noise ratio at low NQR frequencies. Sweeping small (0-26 mT) magnetic fields to shift the (1)H NMR frequency relative to the (14)N NQR frequencies can provide a significant increase of the (14)N NQR signal-to-noise ratio. Three effects of (1)H-(14)N level crossing are demonstrated in diglycine hydrochloride and TNT. These effects are (1) transferring (1)H polarization to one or more of the (14)N transitions, including the use of an adiabatic flip of the (1)H polarization during the field sweep, (2) shortening the effective (14)N T(1) by the interaction of (1)H with the (14)N transitions, (3) "level transfer" effect where the third (14)N (spin 1) energy level or other (14)N sites with different NQR frequency are used as a reservoir of polarization which is transferred to the measured (14)N transition by the (1)H. The (14)N NQR signal-to-noise ratio can be increased by a factor of 2.5 for one (14)N site in diglycine hydrochloride (and 2.2 in TNT), even though the maximum (1)H frequency used in this work, 111 6 kHz, is only 30% larger than the measured (14)N frequencies (834 kHz for diglycine hydrochloride and 843 kHz for TNT).     

Two-frequency saturation in pulsed NQR of14N

The potentialities of variation of the signal/noise ratio in pulsed NQR for spin I=1 with saturation of the quadrupole system at an adjacent transition are examined. A method is proposed for correlating the lines in the¹⁴N NQR spectra at the frequencies ₊ and _–. Calculations are carried out for the two limiting cases by the kinetic-equation and density-matrix method. The experiment was performed with¹⁴N nuclei in sodium nitrite (NaNO₂) at 77 K.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 8, pp. 48–51, August, 1988.     

The noise immunity of gradiometer coils for14N NQR land mine detection: Practical limitations

Magnetic resonance measurements in the field, such as for land mine detection using¹⁴N nuclear quadrupole resonance (NQR), must deal with large levels of environmental radio-frequency interference. One approach to minimize the level of interference which enters the NQR receiver is the use of a coil with no magnetic dipole moment. Such a coil is, ideally, sensitive only to spatial gradients of the magnetic fields and is referred to as a gradiometer. It is straightforward to estimate the amount of reduction one can expect for an ideal gradiometer. Here it is shown that for¹⁴N NQR land mine detection in practice, the ultimate level of interference received can be expected to be significantly greater than what one would expect solely due to these spatial gradients. This is due to the fact that it is quite difficult to construct an ideal gradiometer.     

2D NQR imaging and its application

A new pulse technique for the NQR imaging of the disordered solids is presented and its possibilities in comparison with the known techniques are discussed. It is shown that this technique makes it possible to obtain 2D images of the density of the⁶³Cu,¹²¹Sb and¹⁴N nuclei. The possibility to measure the internal stress distribution in the composites is also proved.     

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.     

Study of 14N NQR response to SORC pulse sequence

The behavior of nuclear quadrupole resonance (NQR) signals between RF pulses of the strong off-resonance comb (SORC) as well as the spin-locking spin-echo (SLSE) pulse sequences was studied as for ¹⁴N NQR line ν _?+? of dimethylnitramine (CH₃)₂NNO₂ at 77 K. The periodic variation of the signal amplitude observed by using SORC pulse sequence could be reasonably explained by the theoretical expression reported in the literature.     

Pulsed 14N NQR Device Designed to Detect Substances in the Presence of Environmental Noise

A new device designed for both volumetric and surface NQR detection of substances spatially located in several positions, and in the presence of environmental interference, is described. The device consists of two probe coils, placed on the same detection plane, for excitation and detection of NQR signals. Experimental results obtained using Strong Off Resonance Comb (SORC) pulse sequences, for the excitation of the ν- transition in samples of Sodium Nitrite (NaNO ₂), are presented. It is shown that, when the total signals induced in each coil are properly combined, the interference commonly detected in both coils is attenuated relative to the NQR signal detected by either one or both probe coils. NQR signal can be detected by either one or both coils, but in both cases the noise induced by distant environmental sources is attenuated. These files correspond to the revised version of the paper N° O-G-6, entitled “Pulsed ¹⁴N NQR device designed to detect substances in the presence of environmental noise” presented at the XVII International symposium on Nuclear Quadrupole Interactions, held in Bonn, Germany in 2004. Argentinian and International patents pending.     

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%.