In a homeland security setting, the ability to detect explosives at a distance is a top security priority. Consequently, the development of remote, noncontact detection systems continues to represent a path forward. In this vein, a remote detection system for excitation of infrared emissions using a CO2 laser for generating laser-induced thermal emission (LITE) is a possible solution. However, a LITE system using a CO2 laser has certain limitations, such as the requirement of careful alignment, interference by the CO2 signal during detection, and the power density loss due to the increase of the laser image at the sample plane with the detection distance. A remote chopped-laser induction system for LITE detection using a CO2 laser source coupled to a focusing telescope was built to solve some of these limitations. Samples of fixed surface concentration (500 μg / cm2) of 1,3,5-trinitroperhydro-1,3,5-triazine (RDX) were used for the remote detection experiments at distances ranging between 4 and 8 m. This system was capable of thermally exciting and capturing the thermal emissions (TEs) at different times in a cyclic manner by a Fourier transform infrared (FTIR) spectrometer coupled to a gold-coated reflection optics telescope (FTIR-GT). This was done using a wheel blocking the capture of TE by the FTIR-GT chopper while heating the sample with the CO2 laser. As the wheel moved, it blocked the CO2 laser and allowed the spectroscopic system to capture the TEs of RDX. Different periods (or frequencies) of wheel spin and FTIR-GT integration times were evaluated to find dependence with observation distance of the maximum intensity detection, minimum signal-to-noise ratio, CO2 laser spot size increase, and the induced temperature increment (ΔT).
Active mode standoff measurement using infrared spectroscopy were carried out in which the angle between target and the source was varied from 0-70° with respect to the surface normal of substrates containing traces of highly energetic materials (explosives). The experiments were made using three infrared sources: a modulated source (Mod-FTIR), an unmodulated source (UnMod-FTIR) and a scanning quantum cascade laser (QCL), part of a dispersive mid infrared (MIR) spectrometer. The targets consisted of PENT 200 μg/cm2 deposited on aluminum plates placed at 1 m from the sources. The evaluation of the three modalities was aimed at verifying the influence of the highly collimated laser beam in the detection in comparison with the other sources. The Mod-FTIR performed better than QCL source in terms of the MIR signal intensity decrease with increasing angle.
Terrorists conceal highly energetic materials (HEM) as Improvised Explosive Devices (IED) in various types of materials such as PVC, wood, Teflon, aluminum, acrylic, carton and rubber to disguise them from detection equipment used by military and security agency personnel. Infrared emissions (IREs) of substrates, with and without HEM, were measured to generate models for detection and discrimination. Multivariable analysis techniques such as principal component analysis (PCA), soft independent modeling by class analogy (SIMCA), partial least squares-discriminant analysis (PLS-DA), support vector machine (SVM) and neural networks (NN) were employed to generate models, in which the emission of IR light from heated samples was stimulated using a CO2 laser giving rise to laser induced thermal emission (LITE) of HEMs. Traces of a specific target threat chemical explosive: PETN in surface concentrations of 10 to 300 ug/cm2 were studied on the surfaces mentioned. Custom built experimental setup used a CO2 laser as a heating source positioned with a telescope, where a minimal loss in reflective optics was reported, for the Mid-IR at a distance of 4 m and 32 scans at 10 s. SVM-DA resulted in the best statistical technique for a discrimination performance of 97%. PLS-DA accurately predicted over 94% and NN 88%.
A standoff multivariate calibration for detection of highly energetic materials (HEM) using Fourier transform infrared
spectroscopy is presented in this report. The procedure consists in standoff sensing at 1 m distance and the variation of
three parameters of detection. The first variable considered was the angular dependence: 0° to 45‡ from source-target with respect to alignment of target-detector. The second variable consisted on the use of several surfaces on which the material was deposited. The substrates used were polished aluminum and anodized aluminum. The third variable studied was the dependence on some specific analyte loading surface concentration: from 10 μg/cm2 to200 μg/cm2. The HEM
used in this work was PETN, synthesized in our lab. Calibration curves were based on the use of chemometrics routines
such as partial least squares (PLS) regression analysis. This algorithm was used to evaluate the impact of the angular
dependence about the limits of detection of different HME loadings on aluminum substrates.
A laser mediated methodology for remote thermal excitation of analytes followed by standoff IR detection is proposed. The goal of this study was to determine the feasibility of using laser induced thermal emission (LITE) from vibrationally excited explosives residues deposited on surfaces to detect explosives remotely. Telescope based FT-IR spectral measurements were carried out to examine substrates containing trace amounts of threat compounds used in explosive devices. The highly energetic materials (HEM) used were PETN, TATP, RDX, TNT, DNT and ammonium nitrate with concentrations from 5 to 200 μg/cm2. Target substrates of various thicknesses were remotely heated using a high power CO2 laser, and their mid-infrared (MIR) thermally stimulated emission spectra were recorded. The telescope was configured from reflective optical elements in order to minimize emission losses in the MIR frequencies and to provide optimum overall performance. Spectral replicas were acquired at a distance of 4 m with an FT-IR interferometer at 4 cm- 1 resolution and 10 scans. Laser power was varied from 4-36 W at radiation exposure times of 10, 20, 30 and 60 s. CO2 laser powers were adjusted to improve the detection and identification of the HEM samples. The advantages of increasing the thermal emission were easily observed in the results. 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. For samples of RDX and PETN, varying the power and time of induction of the laser, the calculated low limit of detections were 2 and 1 μg/cm2, respectively.
A remote infrared spectroscopy (RIRS) detection system was assembled using a mid infrared (MIR) Fourier
Transform interferometer useful in open-path (OP) mode, a reflective infrared telescope and a cryocooled wide
band, MCT detector. The system was used for passive mode IR thermal emission measurements and was also
coupled to another Newtonian telescope in conjunction with a globar source for active mode measurements. The
operation of the system was validated by measuring RIRS spectra of gases (NH3) and condensable vapors: acetone,
dichloromethane, methyl ether and acetonitrile. Solid samples were measured by smearing small amounts on
aluminum plates after dissolving in appropriate solvents. Highly energetic compounds: TNT, DNT, PETN and RDX
were also detected. Experiments of solids on metal surfaces were carried out in passive and active modes. The
analyzed samples were placed at different standoff distances up to a maximum of 30 m in active mode and 60 m in
passive mode.
The DoD Center for Chemical Sensors Development at the University of Puerto Rico-Mayagüez has worked in
developing sensors for threat agents for over 8 years. Work has continued under the ALERT DHS Center of
Excellence. The approaches for sensing have covered many types of threat chemicals and some types of biological
simulants, including high energetic materials, homemade explosives, mixtures and formulations, chemical agents
simulants, toxic industrial chemicals and spore forming microorganisms. Sensing in the far field has been based in
vibrational spectroscopy: Raman and infrared. Near field detection has been mainly based on nanotechnology
enabled sensing platforms for Surface Enhanced Raman Scattering. Initial use of colloidal suspensions of silver and
gold nanospheres eventually evolved to metallic and metal oxide nanorods and to particle immobilization, including
sample smearing on substrates and drop-on-demand thermal inkjet printing of nanoparticles. Chemical reduction of
metal ions has been substituted by clean photonic physical reduction that leaves the nanoactive surface highly
exposed and overcomes the physico-chemical problem of double electrical layers posed by colloidal suspensions of
nanoparticles. New avenues have open wide research endeavors by using laser techniques to form nanoprisms and
interference based metallic nano-images and micro-images. UV based metal reduction on top of metal oxides
nanostructures promises to provide the selectivity and sensitivity expected for the last 30-40 years. Various
applications and experimental setups will be discussed.
Spectroscopy based standoff detection systems: Raman and FTIR have been tested for detection of threat chemicals,
including highly energetic materials, homemade explosives, explosives formulations and high explosives mixtures.
Other threat chemicals studied included toxic industrial compounds (TIC) and chemical agent simulants.
Microorganisms and biological threat agent simulants have also been detected at standoff distances. Open Path FTIR
has been used to detect vapors and chemicals deposited on metal surfaces at μg/cm2 levels at distances as far as 30
m in active mode and 60 m in passive mode. In the case of Raman telescope, standoff distances for acetonitrile and
ammonium nitrate were 140 m.
Fiber optics coupled-grazing angle probe Fourier transform infrared (FTIR) spectroscopy and infrared microspectroscopy have been used for characterization of the distribution and form of layers of some explosives deposited on stainless steel sheets. Among the explosives tested were trinitrobenzene, HMX and Tetryl. Various solvents were used to deposit the films on stainless steel slides. Isopropyl alcohol was the preferred solvent because it produced more homogeneous mass distributions of target explosives on the substrates. The film thickness, analyte distribution and the relation of thickness to infrared absorption/reflection response of these explosives were compared with those previously reported for TNT, 2,4-DNT and RDX. This comparison was used for described the general optical behavior of the explosives studied.
With heightened awareness of Homeland Security issues, the detection of explosive has become a pressing priority. Explosives detection is a very important task for National Security: threat compounds need to be detected on a variety of surfaces. Every surface will interact with the target compounds in a very unique manner and the degree of adhesion will vary from surface to surface. The formidable task includes development of new probes and methods for detection of concealed explosives. Fiber Optic Coupled Infrared Spectroscopy has been used as a potential technique to develop new methodologies for detection of explosives on surfaces. On one of such proposed methodologies involves a Grazing Angle Probe rendering the latter as a remote sensed, in situ and capability of detecting nanograms/cm2 of the compounds. In this research a smearing technique was used for transferring the target analytes onto the substrates to be used as standards. Smearing was also used as a sample transfer method of the threat agents to target surfaces. One of the most relevant areas of investigation is to analyze 2,4,6-trinitrotoluene (TNT) on various non traditional surfaces such as plastics. The work also centered in to obtaining an optimization method where a more accurate spectrum could be obtained and a better spectroscopic preprocessing routine could be applied. A series of statistical methods can be used for quantification of TNT on plastic surfaces, among these are: peak height analysis and peak areas integration. Both of these can be coupled to Partial least squares regression, which is an extension of multiple linear regression models. Using peak areas in the range from 1380 to 1273 cm-1, the method was found to be linear for loading concentration lower than 5.0 μg/cm2. A loading concentration of 0.62 μg/cm2 (620 ng/cm2) was considered as limit of quantification and 0.16 μg/cm2 (160 ng/cm2) as limit of detection.
The use of liquid explosives by terrorists has raised the attention to the use of hazardous liquids as threats to people,
buildings and transportation systems. Hazardous liquids such as explosive mixtures, flammables or even chemical
warfare agents (CWA) can be concealed in common containers and pass security checks undetected. This work
presents three non invasive, non destructive detection approaches that can be used to characterize the content of
common liquid containers and detect if the liquid is the intended or a concealed hazardous liquid. Fiber optic
coupled Raman spectroscopy and Stand off Raman spectroscopy were used to inspect the content of glass and
plastic bottles and thermal conductivity was used to asses the liquid inside aluminum cans. Raman spectroscopy
experiments were performed at 532 nm, 488 nm and 785 nm excitation wavelengths. The hazardous liquids under
consideration included CWA simulant DMMP, hydrogen peroxide, acetone, cyclohexane, ethanol and nitric acid.
These techniques have potential use as a detector for hazardous liquids at a check point or to inspect suspicious
bottles from a distance.
FTIR, Raman spectroscopy and Surface Enhanced Raman Scattering (SERS) requires a minimum of sample allows
fast identification of microorganisms. The use of this technique for characterizing the spectroscopic signatures of
these agents and their stimulants has recently gained considerable attention due to the fact that these techniques can
be easily adapted for standoff detection from considerable distances. The techniques also show high sensitivity and
selectivity and offer near real time detection duty cycles. This research focuses in laying the grounds for the
spectroscopic differentiation of Staphylococcus spp., Pseudomonas spp., Bacillus spp., Salmonella spp.,
Enterobacter aerogenes, Proteus mirabilis, Klebsiella pneumoniae, and E. coli, together with identification of their
subspecies. In order to achieve the proponed objective, protocols to handle, cultivate and analyze the strains have
been developed. Spectroscopic similarities and marked differences have been found for Spontaneous or Normal
Raman spectra and for SERS using silver nanoparticles have been found. The use of principal component analysis
(PCA), discriminate factor analysis (DFA) and a cluster analysis were used to evaluate the efficacy of identifying
potential threat bacterial from their spectra collected on single bacteria. The DFA from the bacteria Raman spectra
show a little discrimination between the diverse bacterial species however the results obtained from the SERS
demonstrate to be high discrimination technique. The spectroscopic study will be extended to examine the spores
produced by selected strains since these are more prone to be used as Biological Warfare Agents due to their
increased mobility and possibility of airborne transport. Micro infrared spectroscopy as well as fiber coupled FTIR
will also be used as possible sensors of target compounds.
This work was focused in the measurement of spectroscopic signatures of Chemical Warfare Agent Simulants (CWAS)
and degradation products of chemical agents using vibrational spectroscopy for the generation of spectroscopic libraries.
The chemicals studied were: DMMP, DIMP, 2-CEES, 2-BAET, 1,4-thioxane, thiodiglycol sulfoxide, dihexylamine,
cyclohexylamine, among others. Raman microscopy experiments were performed at different excitation wavelengths
that spanned from NIR at 1064 and 785 nm to the VIS at 532, 514.5 and 488 nm and even the deep ultraviolet region at
244 nm. For the compounds studied the optimum excitation lines were 488 nm and 532 nm with a laser power of 25
mW. Among the most prominent bands were at these incident wavelengths were located ca. 652 and 1444 cm-1. Fourier
Transform Infrared Spectroscopy in liquid and gas phase and Fiber Optics Coupled-Grazing Angle Probe-FTIR (FOCGAP-
FTIR) were used to characterize the spectroscopic signature of target threat agents. The surface experiments were
performed at detection levels of about 1 &mgr;g/cm2 suggest that limits of detection (LOD) achievable could be as low as
nanograms/cm2. Remote sensing experiments were performed using a telescope coupled with a Raman
spectrophotometer as a function of power and acquisition time. Characterization of compounds by vibrational
spectroscopy and the early stages of the transition from the lab based experiments to remote detection experiments will
be presented.
Deep Ultra Violet Raman Spectroscopy (DUV-RS) is an emerging tool for vibrational spectroscopy analysis and can be used in Point Detection mode to detect explosive components of landmines and Improvised Explosive Devices (IED). Interactions of explosives with different substrates can be measured by using quantitative vibrational signal shift information of scattered Raman light associated with these interactions. In this research, grounds were laid for detection of explosives using UV-Raman Spectroscopy equipped with 244 nm laser excitation line from a 488 nm frequency doubled Coherent FreD laser. In other experiments, samples of 2,4-DNT were allowed to interact with Ottawa Sand and were studied using DUV-RS. Characteristic vibrational signals of energetic compounds were analyzed in the ranges: 400-1200 cm-1, 1200-1800 cm-1, and 2800-3500 cm-1. In addition these Raman spectra were compared with dispersive spectra that were acquired using Raman Microscopy equipped with 514.5 nm (VIS) 785 nm (NIR) and 1064 nm (NIR) excitation lasers.
An actively operated standoff infrared detection system was designed from commercial infrared equipment: VECTOR 22 FTIR (Bruker Optics), an external mirror and an external MCT detector. One type of experiment was done for IR detection of high explosives RDX and TNT on reflective surfaces. In the detection on surface, the samples were move to different distances and a beam of infrared light was reflect on surface in angle of ~ 0° (backward collection from surface normal). First the samples: 2 to 30 μg/cm2 of high explosives TNT and RDX were characterized after depositing on stainless steel reflective surfaces using Reflection-Absorption Infrared Spectroscopy (RAIS). Then targets were moved to increasing distances: 3 to 12 feet and remote-sensed spectra were collected in active reflectance mode. The limits of detection were determined for all distances measured in both nitroexplosives. Limit of detection of 18 and 20 μg/cm2 for TNT and RDX respectively in the longest distances measured.
We report the preparation of explosives nanoparticles of RDX and TNT in a variety of substrates that include glass,
silicon and stainless steel. The explosive nanoparticles were prepared by means of pneumatically assisted
nebulization (PAN) using an electrospray (ESI) needle, which allowed for the direct deposit of the energetic material
onto the substrate. The deposited nanoparticles were characterized by optical microscopy, Scanning Electron
Microscopy (SEM), Energy Dispersive X-ray analysis (EDX) and Raman Microscopy. SEM micrographs showed
that the process produced particles with a mean size in the range of 80-500 nm and a narrow size distribution. For
TNT, the process produced smaller particles with a narrower size distribution. The EDX spectrum showed the
presence of carbon, nitrogen and oxygen consistent with the elemental composition of the energetic materials. The
chemical properties of the nanoparticles were also determined by vibrational spectroscopy.
Fourier Transform Infrared Spectroscopy coupled to Grazing Angle Probe and operating in Reflection Absorption Infrared Spectroscopy mode has been demonstrated that can be used as a potential technique to develop new methodologies for detection of explosives on surfaces in Phase I of this research. The methodology is remote sensed, in situ and can detect nanograms of most target compounds. It is solvent free technique and requires no sample preparation. In this work detection of traces of neat explosives and lab made mixtures equivalent to the important explosive formulation Pentolyte has been addressed. The sample set consisted of TNT, PETN and Pentolyte mixture present in various loading concentrations. The spectral data collected was subjected to a number of statistical pre-treatment methods, including first derivative and normalization transformations to make the data more suitable for analysis. Principal Component Analysis combined with Linear Discriminant Analysis was used to classify and discriminate the target analytes.
Peroxide-based explosives have become of increased interest mainly because they are easily prepared and are not detected by traditional detection devices. The thermal behavior of triacetone triperoxide (TATP), a cyclic peroxide explosive was characterized by Differential Scanning Calorimetry (DSC) and Thermal Gravimetric Analysis (TGA). Dynamic and isothermal methods were used to characterize the sublimation process and to measure the vapor pressure at a temperature range under exothermic decomposition. The enthalpy of sublimation and kinetic parameters were estimated from direct mass loss rate measurements. Melting point, decomposition temperature and enthalpies of transitions were determined and compared to other known materials. The values were also compared to other recently reported values. The results of this study will help in the development of standoff detection technologies for improvised explosive devices using peroxide based materials.
Fourier transform infrared (FTIR) spectroscopy has been established as well suited for work outside the confinement of the sample compartment, provided the excitation source and the reflected light can be transported to the interferometer. Fiber optic cables that transmit in the Mid-IR range have made this possible by allowing the development of a series of spectroscopic probes for in situ analysis. In previous work it was established that surface concentrations of TNT as low as 0.3 μg/cm2 (300 ng/cm2) could be detected with high confidence level. This detection limit varies according to macro properties. Properties such vapor pressure, physical adsorption, sublimation rate and surface-adsorbate thermodynamics can influence the detection limit. A close relation between vapor pressure and limit detection is shown for nitroexplosives. The amount of explosive and the residence time on stainless steel depends on this property, because at low surface concentrations the explosive goes to the vapor phase fast. Loading concentrations near the limits of detection were prepared and spectra were recorded at different temperatures in the range of 14-30°C. The nitro band was monitored for the experiments and the data was analyzed by using peak areas and Chemometrics. A close relationship between the detection limit and temperature was observed.
Fiber Optic Coupled/Grazing Angle Probe Fourier Transform Infrared Spectroscopy has made possible to develop new methods for detection of traces of chemical compounds on surfaces. Thermal Inkjet Technology is able to deposit very small amounts of chemical compounds, including energetic materials, in a specific location on a surface. Aliquots of TNT solutions were deposited on stainless steel film. A thin coating of TNT can be produced by controlling the concentration of TNT, the number of drops dispensed and the distribution of drops over the surface. A Vector 22, a Bruker Optics FTIR fiber coupled to a Remspec Corp. grazing angle head was used for the experiments. The spectra were recorded at 4 cm-1 resolution and 50 scans. The results of the experiments gave intense absorption bands in the fingerprint region of the infrared spectra that were used for quantification. Chemometrics routines were applied in the enhancement of the quantitative analysis.
Surface Enhanced Raman Scattering (SERS) is normally obtained from nanoactive surfaces or colloids of group II-B metals, in particular of silver and gold. In this study another type of nanosurface has been explored seeking more reproducible Raman spectra than those obtained from metallic substrates. Compounds of elements of the fourth transition period were tested for SERS analysis of nitroexplosives. Titanium (IV) oxides were found to give good Raman Enhanced signals of target molecules. TNT and DNT increased their signal intensities for this technique and were evaluated for the increase in different excitation sources. Laser lines at 785, 532 and 514.5 nm were evaluated to determine relative SERS cross sections for various vibrational bands of the target nitroexplosives. Polymorphism seems to play an important role in the Raman signal enhancement when using metal oxides: high rutile percent mixtures with anatase gave higher Raman scattered signal enhancement.
The objective of this research is to design and develop a multi-sensor capable of fast detection and of recognition optimization of the techniques for used for quantification of TATP by Pattern Recognition. In particular, the long range goal of the research is to use sensor fusion and sensor “talking” modalities to couple Stand Off detectors with Chemical Point detectors for detection of airborne chemical agents and detection of Improvised Explosive Devices (IEDs). Vibrational spectroscopy techniques are very fast and can be used for real time detection. Good results have been obtained with various target molecular (chemical) systems such as TATP, TNT and DNT. Samples of TATP were detected and quantified in air, in solution and in solid phase on surfaces by different techniques. FTIR Spectroscopy and GS-MS were used to generate new analytical procedures for detection and analysis of the organic peroxide. These procedures were compared and taken to their limits by optimization with Chemometrics, Partial Least Squares (PLS), and Discriminant Analysis (DA).
The characterization of Tetracetone Tetraperoxide (TRATRP), Triacetone Triperoxide (TATP), Diacetone Diperoxide (DADP), Tricyclohexylidene Triperoxide and Dibenzo Diperoxide using GC-MS, GC-FTIR, FTIR, FT-NMR and Raman Spectroscopy is reported. These compounds were synthesized, purified and characterized in the laboratory in order to develop methodologies for their trace detection. During this study, TATP has been synthesized by different methods obtaining high purity and good yields, even using common household products. DADP synthetic routes reported in the literature were verified. The methods described, including those that produce mixtures with TATP and other peroxides forms were also tested. This study will also focused in the preparation of other cyclic peroxides, including Hexamethelene Triperoxide Diamine (HMTD) and different forms of cyclic peroxides from ketones. This issue of thermodynamic versus kinetic control of secondary products of all syntheses and the effect of temperature in the distribution sub products of the syntheses was also addressed. A vibrational differentiation study of was carried out. Differences were found computationally in the υ(O-O), υ(C-O), δ(CH3-C) and δ(C-O) for Raman and IR bands and retention time and fragment patron for GC-MS and GC-FT-IR.
A new processing of spectra for pattern recognition was created in order to detect explosives. Partial Least Squares (PLS) was used to create vector for recognition and those were using for discriminant analysis. PLS was adjusted with a discriminant function. IR spectra of TATP, DNT and TNT traces in air were recorded. Spectra of free air of those explosives were measured. NIR and MIR regions were studied and were used for PLS vector. NIR region is statistically significant. Two PLS were necessary for good discrimination for those explosives.
2,4,6-Trinitrotoluene is a high explosive that has been used for military purposes since 1902. Ammunition manufacturing facilities where TNT is made as well as sites across the world used to test military explosives in diverse ways, such as landmines and unexploded ordnance that have been buried in soil; grenades, etc are concerned with the health hazard and environmental problem of TNT. Since TNT is a contaminant that remains in the soil and produces various carcinogenic compounds as a result of photodecomposition and biodegradation, large amounts of the nitroaromatic compounds represent both a threat and a problem. Vibrational spectroscopy is a powerful tool that can be used to characterize TNT in its diverse condensed forms: droplets and crystals of polymorphs. Crystallization of TNT from different solvents: water, methanol, chloroform, acetone, and acetonitrile, was carried out and the vibrational spectra were obtained during crystallization. Crystals produced from evaporation of the mentioned solvent showed a similar crystallization pattern, and their spectroscopic information obtained was found to depend on the physical form of TNT. The nitroaromatic compound exhibits a series of unique characteristic bands that allow its detection and spectroscopic characterization. The spectroscopic signatures of neat TNT samples were determined with Raman Microspectroscopy and used as comparison standards. Strong bands about 1365 and 2956 cm-1 dominate the Raman spectrum of neat TNT. The intensity and even the presence of these bands are found to be remarkably dependent on TNT form and source.
Fully optimized molecular geometry, parameters of reactivity and vibrational spectra of triacetone triperoxide (TATP) and homologue organic peroxides were calculated using B3LYP/6-31G(d,p) method within the Density Functional Theory formalism. Infrared and Raman Spectroscopy were utilized to obtain vibrational spectra of the energetic compound. The model consists in the relation found between the Raman Shift location of the important symmetric stretch ν(O-O) of the organic peroxides and the reactivity of the organic peroxides. A good correlation between the band location in the series studied and the x-y plane polarizability component and the ionization energy was found. Gas phase IR absorption of TATP in air was used for developing stand-off detection schemes of the important organic peroxide in air. The sublimation properties of TATP were measured using two methods: Grazing Angle Probe-Fiber Coupled FTIR and gravimetric on stainless steel surfaces. Sublimation rates, loading concentration values and absorbance band areas were measured and modeled using the persistent IR vibrational signature of the ν(C-O) mode.
TNT and DNT are important explosives used as base charges of landmines and other explosive devices. They are often combined with RDX in specific explosive formulations. Their detection in vapor phase as well as in soil in contact with the explosives is important in landmine detection technology. The spectroscopic signatures of nitroaromatic compounds in neat forms: crystals, droplets, and recrystallized samples were determined by Raman Microspectroscopy (RS), Fourier Transform Infrared Microscopy (FTIR) and Fiber Optics Coupled - Fourier Transform Infrared Spectroscopy (FOC-FTIR) using a grazing angle (GA) probe. TNT exhibits a series of characteristic bands: vibrational signatures, which allow its detection in soil. The spectroscopic signature of neat TNT is dominated by strong bands about 1380 and 2970 cm-1. The intensity and position of these bands were found remarkably different in soil samples spiked with TNT. The 1380 cm-1 band is split into a number of bands in that region. The 2970 cm-1 band is reduced in intensity and new bands are observed about 2880 cm-1. The results are consistent with a different chemical environment of TNT in soil as compared to neat TNT. Interactions were found to be dependent on the physical source of the explosive. In the case of DNT-sand interactions, shifts in vibrational frequencies of the explosives as well as the substrates were found.
Quantitative Structure-Property Relationships (QSPR) have been determined to predict retention times, explosives weight impact heights (H50) and detonation velocities (DV). Electronic, geometric and topological descriptors were calculated through B3LYP/6-31G** method using Gaussian 03. Descriptors used were: the most positive charge (MPC), the energy of the lowest unoccupied molecular orbital (ELUMO) and the number of nitrogen atoms {N (N)}. A QSPR model was generated by multiple linear regression analysis using reported properties, as dependent variables. The reactivity of the compounds was also modeled. It was found that the reactivity can be drastically affected by the number of nitrogen atoms in the explosive. This QSPR approach offers a good explanation of the reactivity properties. For nitroaromatic explosives reactivities can be drastically affected by the electronic nature of the ring substituents and by their positions in the aromatic ring.
Explosives detection is a very important task for National Security. The formidable task includes development of new probes and methods for detection of concealed explosives which is of utmost priority to Homeland Security and other security enforcing federal agencies. Here we report on the detection of triacetone triperoxide (TATP) on metallic surfaces using a Fiber Optic Coupled FTIR method. FT-IR spectroscopy is well suited to be used outside the confinement of the sample compartment, provided the excitation source and the reflected light can be transported to the interferometer. Fiber optic cables that transmit in the Mid-IR range have made this possible by allowing the development of a range of spectroscopic probes for in situ analysis. In our study we used a specially designed sampling probe that operates at the grazing-angle to detect and to quantify μg/cm2 levels of explosives on stainless steel. Calibration curves were prepared using stainless steel plates, 3 inches wide x 6 inches long. The samples were deposited on the surface using a smearing method. To carry out the experiments, TATP was synthesized in the laboratory. For the calibration curves TATP was dissolved in dichloromethane. The standard solutions (20) μL were transferred on the plates resulting in surface mass concentrations of TATP that ranged from 8 to 150 μg/cm2. The data was analyzed using Chemometrics routines and Discriminant Analysis algorithms. In particular, multivariate Partial Least Squares (PLS) was used to determine the most significant peak for the analysis. In other experiments done with stainless steel plates coated with 150 μg/cm2 TATP, spectra were recorded every 27 seconds. For this concentration TATP sublimates to surface concentrations below detection in 800 s.
Non nitrogen containing, organic peroxides explosives Triacetone triperoxide and diacetone diperoxide have been prepared in the laboratory in order to study various aspects of their synthesis and their experimental and theoretical spectroscopic characteristics. By using different proportions of acetone/hydrogen peroxide (Ac/H2O2), sulfuric, hydrochloric and methanosulfuric acids as catalyzers, it was possible to obtain both compounds in a rapid and simple form. Raman, IR spectroscopy, and GC-MS were used in order to determine the precursors, intermediates and final analytes. Experiments and theoretical studies using density functional theory (DFT) have been used in the elucidation step of the mechanism of the synthesis of the so called "transparent" explosives. The B3LYP functional with the 6-31G** basis set was used to carry out the electronic structure calculation of the intermediates and internal rotations and vibrations of TATP. Raman spectra of solid TATP and FTIR spectra of gas TATP, were recorded in order to assign the experimental spectra. Although full agreement with experiment was not obtained, spectral features of the main TATP bands were assigned.
Access to the requested content is limited to institutions that have purchased or subscribe to SPIE eBooks.
You are receiving this notice because your organization may not have SPIE eBooks access.*
*Shibboleth/Open Athens users─please
sign in
to access your institution's subscriptions.
To obtain this item, you may purchase the complete book in print or electronic format on
SPIE.org.
INSTITUTIONAL Select your institution to access the SPIE Digital Library.
PERSONAL Sign in with your SPIE account to access your personal subscriptions or to use specific features such as save to my library, sign up for alerts, save searches, etc.