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This study investigates a new approach for quantifying the ignition sensitivity of energetic materials from electrostatic discharge (ESD). The intensities from photo receivers were used to assist in determining whether or not ignition of the energetic materials was achieved from the ESD. The results show that the photo receivers captured an increase in light intensity for the samples that experienced ignition, suggesting that they can be used to quantify ESD sensitivity of energetic materials.

Since the Royal Society Discussion Meeting on in 2000, the laboratory spectroscopy of has entered a new regime. For the first time, transitions of above the barrier to linearity have been observed. A highly sensitive near-infrared spectrometer based on a titanium:sapphire laser and incorporating a dual-beam, double-modulation technique with bidirectional optical multi-passing has been developed in order to detect these transitions, which are more than 4600 times weaker than the fundamental band. We discuss our recent work on the , , , and combination bands and the , , and overtone bands. Experimentally determined energy levels provide a critical test of ab initio calculations in this challenging energy regime (greater than 10 000 cm −1 ). By comparing the experimental energy levels and theoretical energy levels from ab initio calculations in which the adiabatic and relativistic corrections are incorporated, the extent of higher-order effects such as non-adiabatic and radiative corrections is revealed.

A review of recent results of the studies of double laser pulse plasma and ablation for laser induced breakdown spectroscopy applications is presented. The double pulse laser induced breakdown spectroscopy configuration was suggested with the aim of overcoming the sensitivity shortcomings of the conventional single pulse laser induced breakdown spectroscopy technique. Several configurations have been suggested for the realization of the double pulse laser induced breakdown spectroscopy technique: collinear, orthogonal pre-spark, orthogonal pre-heating and dual pulse crossed beam modes. In addition, combinations of laser pulses with different wavelengths, different energies and durations were studied, thus providing flexibility in the choice of wavelength, pulse width, energy and pulse sequence. The double pulse laser induced breakdown spectroscopy approach provides a significant enhancement in the intensity of laser induced breakdown spectroscopy emission lines up to two orders of magnitude greater than a conventional single pulse laser induced breakdown spectroscopy. The double pulse technique leads to a better coupling of the laser beam with the plasma plume and target material, thus providing a more temporally effective energy delivery to the plasma and target. The experimental results demonstrate that the maximum effect is obtained at some optimum separation delay time between pulses. The optimum value of the interpulse delay depends on several factors, such as the target material, the energy level of excited states responsible for the emission, and the type of enhancement process considered. Depending on the specified parameter, the enhancement effects were observed on different time scales ranging from the picosecond time level (e.g., ion yield, ablation mass) up to the hundred microsecond level (e.g., increased emission intensity for laser induced breakdown spectroscopy of submerged metal target in water). Several suggestions have been proposed to explain the mechanism of double pulse enhancement.

The first H3+ transitions above the barrier to linearity have been observed in absorption in the near infrared using a highly sensitive dual-beam, double-modulation technique with bidirectional optical multipassing. A total of 22 rovibrational transitions of H3+ have been detected and assigned to the fourth and fifth overtone and combination bands (5ν21, 5ν25, 2ν1+2ν22, 3ν1+ν21, ν1+4ν22, 2ν1+3ν21, and 6ν22). These transitions, which are more than 4600 times weaker than the fundamental band, probe energy levels above 10 000 cm−1, the regime in which H3+ has enough energy to sample linear configurations. Experimentally determined energy levels above the barrier to linearity provide a critical test of ab initio calculations in this challenging regime. The comparison between experimental energy levels and theoretical energy levels from ab initio calculations in which the adiabatic and relativistic corrections are incorporated reveals the extent of higher-order effects such as nonadiabatic and radiative correc...

Differences in the excitation of non-energetic and energetic residues with a 900 mJ, 6 ns laser pulse (1064 nm) have been investigated. Emission from the laser-induced plasma of energetic materials (e.g. triaminotrinitrobenzene [TATB], cyclotrimethylene trinitramine [RDX], and hexanitrohexaazaisowurtzitane [CL-20]) is significantly reduced compared to non-energetic materials (e.g. sugar, melamine, and l-glutamine). Expansion of the resulting laser-induced shock wave into the air above the sample surface was imaged on a microsecond timescale with a high-speed camera recording multiple frames from each laser shot; the excitation of energetic materials produces larger heat-affected zones in the surrounding atmosphere (facilitating deflagration of particles ejected from the sample surface), results in the formation of additional shock fronts, and generates faster external shock front velocities (750 m s(-1)) compared to non-energetic materials (550-600 m s(-1)). Non-explosive materials that undergo exothermic chemical reactions in air at high temperatures such as ammonium nitrate and magnesium sulfate produce shock velocities which exceed those of the inert materials but are less than those generated by the exothermic reactions of explosive materials (650-700 m s(-1)). The most powerful explosives produced the highest shock velocities. A comparison to several existing shock models demonstrated that no single model describes the shock propagation for both non-energetic and energetic materials. The influence of the exothermic chemical reactions initiated by the pulsed laser on the velocity of the laser-induced shock waves has thus been demonstrated for the first time.

A prototype laser ignition chamber was used to measure the pressure-time behavior of black powder ignited by a continuouswave laser (355 nm). The time to ignition of the black powder using the ultraviolet laser was significantly longer (seconds) than previous studies using near-infrared lasers (milliseconds). A linear relationship between the Mylar diaphragm thickness and the maximum peak pressure was observed. Differences in the behavior of the Mylar blowout disk based on the thicknesses of the individual sheets have also been observed.

Laser-induced breakdown spectroscopy is a promising approach for explosive residue detection, but several limitations to its widespread use remain. One issue is that the emission spectra of the residues are dependent on the substrate composition because some of the substrate is usually entrained in the laser-induced plasma and the laser-material interaction can be significantly affected by the substrate type. Here, we have demonstrated that despite the strong spectral variation in cyclotrimethylenetrinitramine (RDX) residues applied to various metal substrates, classification of the RDX residue independent of substrate type is feasible. Several approaches to improving the chemometric models based on partial least squares discriminant analysis (PLS-DA) have been described: classifying the RDX residue spectra together in one class independent of substrate, using selected emission intensities and ratios to increase the true positive rate (TPR) and decrease the false positive rate (FPR), and fusing the results from two PLS-DA models generated using the full broadband spectra and selected intensities and ratios. The combination of these approaches resulted in a TPR of 97.5% and a FPR of 1.0% for RDX classification on metal substrates.

A new technique for automatic detection of elements in LIBS spectra is presented. The proposed model automatically determines the number of elements present in the spectra, and mitigates variations from unknown changes in plasma temperature.

A focused, nanosecond-pulsed laser has been used to ablate, atomize, ionize, and excite milligram quantities of metal-doped energetic materials that undergo exothermic reactions in the laser-induced plasma. The subsequent shock wave expansion in the air above the sample has been monitored using high-speed schlieren imaging in a recently developed technique, laser-induced air shock from energetic materials (LASEM). The method enables the estimation of detonation velocities based on the measured laser-induced air-shock velocities and has previously been demonstrated for organic military explosives. Here, the LASEM technique has been extended to explosive formulations with metal additives. A comparison of the measured laser-induced air-shock velocities for TNT, RDX, DNTF, and LLM-172 doped with Al or B to the detonation velocities predicted by the thermochemical code CHEETAH for inert or active metal participation demonstrates that LASEM has potential for predicting the early time (

Recent advances in laser-induced breakdown spectroscopy (LIBS) such as double pulse LIBS and advanced chemometric analysis have enabled discrimination between explosive and non-explosive residues on various surfaces at standoff distances.

The potential of laser-induced breakdown spectroscopy (LIBS) to discriminate biological and chemical threat simulant residues prepared on multiple substrates and in the presence of interferents has been explored. The simulant samples tested include Bacillus atrophaeus spores, Escherichia coli, MS-2 bacteriophage, α-hemolysin from Staphylococcus aureus, 2-chloroethyl ethyl sulfide, and dimethyl methylphosphonate. The residue samples were prepared on polycarbonate, stainless steel and aluminum foil substrates by Battelle Eastern Science and Technology Center. LIBS spectra were collected by Battelle on a portable LIBS instrument developed by A3 Technologies. This paper presents the chemometric analysis of the LIBS spectra using partial least-squares discriminant analysis (PLS-DA). The performance of PLS-DA models developed based on the full LIBS spectra, and selected emission intensities and ratios have been compared. The full-spectra models generally provided better classification results based on the inclusion of substrate emission features; however, the intensity/ratio models were able to correctly identify more types of simulant residues in the presence of interferents. The fusion of the two types of PLS-DA models resulted in a significant improvement in classification performance for models built using multiple substrates. In addition to identifying the major components of residue mixtures, minor components such as growth media and solvents can be identified with an appropriately designed PLS-DA model.

This work provides a review of the capabilities and applications of laser-induced breakdown spectroscopy (LIBS) at the U.S. Army Research Laboratory (ARL). By coupling advances in LIBS hardware and analysis software, ARL has expanded the capabilities of LIBS significantly. LIBS uses a focused, pulsed laser to ablate a target material, generating a transient microplasma which emits light characteristic of the sample composition. It is a real-time sensor technology which requires no sample preparation and provides universal materials detection for solids, liquids, and aerosols. Applications investigated at ARL in recent years include the standoff detection of explosive residues and other hazardous materials, plastic landmine discrimination, and material characterization of various metal alloys and polymers.

The feasibility of a novel approach for studying the chemical reactions between metallic nanoparticles and molecular explosives has been demonstrated. This method is based on the production of nanoparticles in a laser-induced plasma and the simultaneous observation of the atomic and molecular emission characteristic of the species involved in the intermediate chemical reactions of the nanoenergetic material in the plasma. Time-resolved, broadband emission of chemical species involved in the reaction of RDX and various metal nanoparticles was observed. The increase in diatomic carbon (C2) and aluminum monoxide (AlO) emission with increasing aluminum (Al) content previously observed during an aluminized-RDX explosion in a shock tube was confirmed using this method. The time-evolution of species formation in the plasma, the effects of laser pulse energy, and the effects of trace metal content on chemical reactions were also studied.

The LIBS group at ARL/APG continues to advance the use of Laser Induced Breakdown Spectroscopy (LIBS) for standoff detection and identification of various residue materials, both hazardous and benign. Progress will be presented.

The ability to interrogate objects buried in soil and ascertain their chemical composition in-situ would be an important capability enhancement for both military and humanitarian demining. Laser Induced Breakdown Spectroscopy (LIBS) is a simple spark spectrochemical technique using a pulsed laser. Recent developments in broadband and man-portable LIBS provide the capability for the real-time detection at very high sensitivity of all elements in any target material because all chemical elements emit in the 200-940 nm spectral region. This technological advance offers a unique potential for the development of a rugged and reliable man-portable or robot-deployable chemical sensor that would be capable of both in-situ point probing and chemical sensing for landmine detection. Broadband LIBS data was acquired under laboratory conditions for more than a dozen different types of anti-personnel and anti-tank landmine casings from four countries plus a set of antitank landmine simulants. Subsequently, a statistical classification technique (partial least squares discriminant analysis, PLS-DA) was used to discriminate landmine casings from the simulants and to assign "unknown" spectra to a mine type based upon a library classification approach. Overall, a correct classification success of 99.0% was achieved, with a misclassification rate of only 1.8%. This performance illustrates the potential that LIBS has to be developed into a field-deployable device that could be utilized as a confirmatory sensor in landmine detection. The operational concept envisioned is a small LIBS system that is either man-portable or robot-deployed in which a micro-laser is contained in the handle of a deminer's probe, with laser light delivered and collected through an optical fiber in the tapered tip of the probe. In such a configuration, chemical analysis could be readily accomplished by LIBS after touching the buried object that one is interested in identifying and using real-time statistical signal processing techniques to accomplish "mine/no-mine" discrimination and even object identification if a material library could be constructed prior to analysis.

A technique being evaluated for standoff explosives detection is laser-induced breakdown spectroscopy (LIBS). LIBS is a real-time sensor technology that uses components that can be configured into a ruggedized standoff instrument. The U.S. Army Research Laboratory has been coupling standoff LIBS spectra with chemometrics for several years now in order to discriminate between explosives and nonexplosives. We have investigated the use of partial least squares discriminant analysis (PLS-DA) for explosives detection. We have extended our study of PLS-DA to more complex sample types, including binary mixtures, different types of explosives, and samples not included in the model. We demonstrate the importance of building the PLS-DA model by iteratively testing it against sample test sets. Independent test sets are used to test the robustness of the final model.

Laser Induced Breakdown Spectroscopy (LIBS) is an emerging technology that has great potential for a wide variety of civilian and military applications. Recent history and progress of LIBS will be presented.

Publisher Summary Lasers offer multiple approaches for explosive detection that are not possible with other techniques. In general, these can be separated into two types: those based on the unique properties of lasers for long-distance propagation of intense energy and those that are based on the actual molecular and atomic spectroscopy, and as such utilize the high wavelength specificity that most lasers offer. Of course, the field of laser explosive detection is somewhat new, given the fact that lasers were invented fairly recently in 1958. As such, it is fair to say that laser explosive detection is still a work in progress, with much having been discovered in recent years and still more to be discovered in the near future, particularly as more exotic laser sources, for example, fem to second lasers, become more common, less expensive, more rugged, and generally more readily available. The expected dramatic improvements in probability of detection and reduction of false alarm rates suggest that laser-based explosive detection methods may evolve into a major new technology area in the next 1–3 years.

Since the Royal Society Discussion Meeting on H3+ in 2000, the laboratory spectroscopy of H3+ has entered a new regime. For the first time, transitions of H3+ above the barrier to linearity have been observed. A highly sensitive near-infrared spectrometer based on a titanium:sapphire laser and incorporating a dual-beam, double-modulation technique with bidirectional optical multi-passing has been developed in order to detect these transitions, which are more than 4600 times weaker than the fundamental band. We discuss our recent work on the 2v1 + 2v2(2)-- 0, 3v1 + v2(1)-- 0, v1 + 4v2(2)-- 0, v1 + 4V2(4)-- 0 and 2v1 + 3v2(1)-- 0 combination bands and the 5v2(1)-- 0, 5v2(3)-- 0, 52(5)-- 0 and 6v2(2)-- 0 overtone bands. Experimentally determined energy levels provide a critical test of ab initio calculations in this challenging energy regime (greater than 10,000 cm(-1)). By comparing the experimental energy levels and theoretical energy levels from ab initio calculations in which the adiabatic and relativistic corrections are incorporated, the extent of higher-order effects such as non-adiabatic and radiative corrections is revealed.

Four vibronic bands of the A 2B1(Piu)

Standoff laser induced breakdown spectroscopy (LIBS) has previously been used to classify trace residues as either hazardous (explosives, biological, etc.) or benign. Correct classification can become more difficult depending on the surface/substrate underneath the residue due to variations in the laser-material interaction. In addition, classification can become problematic if the substrate material has a similar elemental composition to the residue. We have evaluated coupling multivariate analysis with standoff LIBS to determine the effectiveness of classifying thin explosive residue layers on painted surfaces. Good classification results were obtained despite the fact that the painted surface contributes to the LIBS emission signal.

The feasibility of exploiting plasma chemistry to study the chemical reactions between metallic nanoparticles and molecular explosives such as cyclotrimethylenetrinitramine (RDX) has been demonstrated. This method, based on laser-induced breakdown spectroscopy, involves the production of nanoparticles in a laser-induced plasma and the simultaneous observation of time-resolved atomic and molecular emission characteristic of the species involved in the intermediate chemical reactions of the nanoenergetic material in the plasma. Using this method, it has been confirmed that the presence of aluminum promotes the ejection process of carbon from the intermediate products of RDX. The time evolution of species formation, the effects of laser pulse energy, and the effects of trace metal content on the chemical reactions were also studied.

Laser-induced breakdown spectroscopy (LIBS) is an analytical technique real-time geochemical analysis that is being developed for portable use outside of the laboratory. In this study, statistical signal processing and classification techniques were applied to single-shot, broadband LIBS spectra, comprising measured plasma light intensities between 200 and 960 nm, for a suite of 157 garnets of different composition from 92 locations worldwide. Partial least squares discriminant analysis was applied to sets of 25 LIBS spectra for each garnet sample and used to classify the garnet samples based on composition and geographic origin. Careful consideration was given to the cross-validation procedure to ensure that the classification algorithm is robust to unseen data. The results indicate that broadband LIBS analysis can be used to discriminate garnets of different composition and has the potential to discern geographic origin.

Over the past quarter century, multielement chemical analysis has become a common means for attributing the provenance of archaeological materials. The Coso Volcanic Field (CVF) in California, USA, contains at least 38 high-silica rhyolite domes, many of which contain obsidian glass that has been quarried for tools by the indigenous population for more than 12,000 years. Artifacts made from CVF obsidian are found throughout the southwestern United States and geochemical sourcing of CVF obsidian has been an important tool in understanding prehistoric Native American trading patterns. Laser-induced breakdown spectroscopy (LIBS) is a simple atomic emission spectroscopic technique that has the potential for real-time man-portable chemical analysis in the field. Because LIBS is simultaneously sensitive to all elements, a single laser shot can be used to record the broadband emission spectra, which provides a “chemical fingerprint” of a material. Single-shot broadband LIBS spectra were collected using a commercial benchtop LIBS system for 27 obsidian samples from major sites across the CVF and four additional sites in California and western Nevada outside of CVF. Classification of the samples was performed using partial least-squares discriminant analysis (PLSDA), a common chemometric technique suitable for performing regression on high-dimensional data. Provenance identification for the obsidian samples was evaluated for three separate labeling frameworks. The first framework consisted of a binary classification problem to distinguish CVF samples from non-CVF samples. The second approach focused on the CVF samples with labels that corresponded to the eight separate Coso sites encompassed by the 27 samples. In the third analysis, non-CVF samples were excluded, and the remaining 27 CVF samples were labeled based on groupings defined from previous major and trace element chemical studies, which reduces the number of possible classes from eight to four. Different aspects of the classifier setup considered in this study include the training/testing routine (a 27-fold leave-one-sample-out setup versus a simple split of the data into separate sets for training and evaluation), the number of latent variables used in the regression model, and whether PLSDA operating on the entire broadband LIBS spectrum is superior to that using only a selected subset of LIBS emission lines. The results point to the robustness of the PLSDA technique and suggest that LIBS analysis combined with the appropriate statistical signal processing has the potential to be a useful tool for chemical analysis of archaeological artifacts and geological specimens.

We have demonstrated the detection and discrimination of explosive residues on a variety of surfaces using laser-induced breakdown spectroscopy and partial least squares discriminant analysis. The correlation between the hardness of a substrate and the ability to discriminate residues on that substrate is discussed. We have also shown that while using the full spectra in the chemometric model improves the classification of sample types in the model, the use of intensities and ratios specific to explosive residues improves the classification of sample types that are not part of the model. In the first case, differences in the laser-induced plasma (and resulting spectral features) attributable to the laser-material interaction contribute to the sample discrimination, while using intensities and ratios specific to explosive residues focuses on the chemical composition of the sample for discrimination. Combining the results of the two models for a given sample set decreases the overall false positive rate for all test samples.

Laser-induced breakdown spectroscopy (LIBS) was used to discern between two biological agent surrogates (Bacillus atrophaeus and ovalbumin) and potential interferent compounds (mold spores, humic acid, house dust, and Arizona road dust). Multiple linear regression and neural network analysis models were constructed by using B. atrophaeus and ovalbumin spectra, and limits of detection were calculated. Classification of the agent surrogates' LIBS spectra was attempted by using a neural network model. False negative rates of 0% were observed for B. atrophaeus (100 colony forming units) spore spectra with the neural network model used for classification.

The performance of a man-portable laser induced breakdown spectrometer was evaluated for the detection of biological powders on indoor office surfaces and wipe materials. Identification of pure unknown powders was performed by comparing against a library of spectra containing biological agent surrogates and confusant materials, such as dusts, diesel soot, natural and artificial sweeteners, and drink powders, using linear correlation analysis. Simple models constructed using a second technique, partial least squares discriminant analysis, successfully identified Bacillus subtilis (BG) spores on wipe materials and office surfaces. Furthermore, these models were able to identify BG on materials not used in the training of the model.

Laser-induced breakdown spectroscopy (LIBS) is a promising technique for real-time chemical and biological warfare agent detection in the field. We have demonstrated the detection and discrimination of the biological warfare agent surrogates Bacillus subtilis (BG) (2% false negatives, 0% false positives) and ovalbumin (0% false negatives, 1% false positives) at 20 meters using standoff laser-induced breakdown spectroscopy (ST-LIBS) and linear correlation. Unknown interferent samples (not included in the model), samples on different substrates, and mixtures of BG and Arizona road dust have been classified with reasonable success using partial least squares discriminant analysis (PLS-DA). A few of the samples tested such as the soot (not included in the model) and the 25% BG:75% dust mixture resulted in a significant number of false positives or false negatives, respectively. Our preliminary results indicate that while LIBS is able to discriminate biomaterials with similar elemental compositions at standoff distances based on differences in key intensity ratios, further work is needed to reduce the number of false positives/negatives by refining the PLS-DA model to include a sufficient range of material classes and carefully selecting a detection threshold. In addition, we have demonstrated that LIBS can distinguish five different organophosphate nerve agent simulants at 20 meters, despite their similar stoichiometric formulas. Finally, a combined PLS-DA model for chemical, biological, and explosives detection using a single ST-LIBS sensor has been developed in order to demonstrate the potential of standoff LIBS for universal hazardous materials detection.

Recently laser-induced breakdown spectroscopy (LIBS) has been investigated as a potential technique for trace explosive detection. Typically LIBS is performed using nanosecond laser pulses. For this work, we have investigated the use of femtosecond laser pulses for explosive residue detection at two different fluences. Femtosecond laser pulses have previously been shown to provide several advantages for laser ablation and other LIBS applications. We have collected LIBS spectra of several bulk explosives and explosive residues at different pulse durations and energies. In contrast to previous femtosecond LIBS spectra of explosives, we have observed atomic emission peaks for the constituent elements of explosives - carbon, hydrogen, nitrogen, and oxygen. Preliminary results indicate that several advantages attributed to femtosecond pulses are not realized at higher laser fluences.