Standoff infrared and Raman spectroscopy (SIRS and SRS) detection systems were designed from commercial instrumentation and successfully tested in remote detection of high explosives (HE). The SIRS system was configured by coupling a Fourier-transform infrared interferometer to a gold mirror and detector. The SRS instrument was built by fiber coupling a spectrograph to a reflective telescope. HE samples were detected on stainless steel surfaces as thin films (2-30 microg/cm(2)) for SIRS experiments and as particles (3-85 mg) for SRS measurements. Nitroaromatic HEs: TNT, DNT, RDX, C4, and Semtex-H and TATP cyclic peroxide homemade explosive were used as targets. For the SIRS experiments, samples were placed at increasing distances and an infrared beam was reflected from the stainless steel surfaces coated with the target chemicals at an angle of approximately 180 degrees from surface normal. Stainless steel plates containing TNT and RDX were first characterized for coverage distribution and surface concentration by reflection-absorption infrared spectroscopy. Targets were then placed at the standoff distance and SIRS spectra were collected in active reflectance mode. Limits of detection (LOD) were determined for all distances measured for the target HE. LOD values of 18 and 20 microg/cm(2) were obtained for TNT and RDX, respectively, for the SIR longest standoff distance measured. For SRS experiments, as low as 3 mg of TNT and RDX were detected at 7 m source-target distance employing 488 and 514.5 nm excitation wavelengths. The first detection and quantification study of the important formulation C4 is reported. Detection limits as function of laser powers and acquisition times and at a standoff distance of 7 m were obtained.
A laser-mediated methodology for standoff infrared detection of threat chemicals is described in this article. Laser-induced thermal emissions (LITE) from vibrationally excited residue of highly energetic material (HEM) deposited on substrates were detected remotely. Telescope-based Fourier transform infrared (FT-IR) spectroscopy measurements were carried out on substrates containing small amounts of HEM at surface concentrations of 5-200 μg/cm(2). Target substrates of various thicknesses were heated remotely using a carbon dioxide laser, and their mid-infrared (mid-IR), thermally stimulated emission spectra were recorded after heating. The telescope was configured from reflective optical elements to minimize emission losses in the mid-IR frequencies. Spectral replicas were acquired at distances from 4 to 64 m using an FT-IR interferometer at 4 cm(-1) resolution. The laser power, laser exposure times, and acquisition time of the FT-IR interferometer were adjusted to improve the detection and identification of samples. The advantages of increasing the thermal emission were easily observed in the results. The signal intensities were proportional to the thickness of the coated surface (a function of the surface concentration) as well as the laser power and laser exposure time. The limits of detection obtained for the HEM studied were 140-21 μg/cm(2) at 4 m. Detection was achieved at 64 m for a surface concentration of 200 μg/cm(2).
The highly energetic
material (HEM) hexahydro-1,3,5-trinitro-s-triazine,
also known as RDX, has two stable conformational
polymorphs at room temperature: α-RDX (molecular conformation
of −NO2 groups: axial–axial–equatorial)
and β-RDX (molecular conformation of −NO2 groups:
axial–axial–axial). Both polymorphs can be formed by
deposition on stainless steel substrates using spin coating methodology.
α-RDX is the most stable crystal form at room temperature and
ambient pressure. However, β-RDX, which has been reported to
be difficult to obtain in bulk form at room temperature, was readily
formed. Reflection–absorption infrared spectroscopy measurements
for RDX-coated stainless steel substrates provided spectral markers
that were used to distinguish between the conformational polymorphs
on large surface areas of the substrates. Raman microspectroscopy
was employed to examine small areas where the intensity was proportional
to the height of the structures of RDX. Spectral features were interpreted
and classified by using principal component analysis (PCA). The results
from these spectral analyses provided good correlation with the values
reported in the literature. Conditions to generate predominantly β-RDX
crystalline films as a function of the spin coating rotational speed
on these substrates were obtained. PCA was also applied to predict
percentages of polymorphs present in experimental samples. Applications
of the results obtained suggest the modification of existing vibrational
spectroscopy based spectral libraries for defense and security applications.
Understanding the effects of polymorphism in HEMs will result in the
attainment of higher confidence limits in the detection and identification
of explosives, especially at trace or near trace levels.
Fiber Optic Coupled Reflection/Absorption Infrared Spectroscopy (RAIRS) has been investigated as a potential technique for developing methodologies of detection and quantification of explosive residues on metallic surfaces. TNT, DNT, HMX, PETN, and Tetryl were detected at loading concentrations less than 400 ng/cm 2 . Data were analyzed using Chemometrics statistical analysis routines. In particular, partial least squares multivariate analysis (PLS) was used for quantification studies. Peak areas were also used for data analysis to compare with linear multivariate analysis. The measurements resulted in intense absorption bands in the fingerprint region of the infrared spectrum that were used to quantify the target threat chemicals and to calculate the limit of detection for each compound. Micro-RAIRS vibrational imaging was also used for characterization of the distribution and form of layers of explosives deposited on stainless steel sheets. The degree of homogeneity depended strongly on the method of deposition. The images were generated by calculating the area under vibrational signals of 15 lm 9 15 lm grids with a separation of 15 lm. Histograms of the maps were generated and the homogeneity was evaluated by using standard deviations, mean kurtosis, skewness, and moments of distributions obtained. Methanol solutions of High Explosives (HE) resulted in the optimum distributions on the stainless steel surfaces tested and therefore, Methanol selected as the preferred solvent for the Fiber Optics Coupled-RAIRS experiments.
A standoff detection system was assembled by coupling a reflecting telescope to a Fourier transform infrared spectrometer equipped with a cryo-cooled mercury cadmium telluride detector and used for detection of solid-phase samples deposited on substrates. Samples of highly energetic materials were deposited on aluminum substrates and detected at several collector-target distances by performing passive-mode, remote, infrared detection measurements on the heated analytes. Aluminum plates were used as support material, and 2,4,6-Trinitrotoluene (TNT) was used as the target. For standoff detection experiments, the samples were placed at different distances (4 to 55 m). Several target surface temperatures were investigated. Partial least squares regression analysis was applied to the analysis of the intensities of the spectra obtained. Overall, standoff detection in passive mode was useful for quantifying TNT deposited on the aluminum plates with high confidence up to target-collector distances of 55 m.
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