Afin de pallier aux problèmes dus aux limites de détection des capteurs et des détecteurs usuels, un système de préconcentration est indispensable. Ce microcomposant permet d’accumuler le ou les vapeur(s) à détecter à l’aide d’un adsorbant et permet de les libérer sous l’effet d’une montée brutale de la température vers un détecteur. Une amplification de la concentration et donc du signal est ainsi obtenue.Cette thèse poursuit le développement d’un préconcentrateur pour la détection de vapeurs toxiques et d’explosifs. Ce préconcentrateur sera constitué d’un microcomposant en silicium rempli d’un adsorbant et muni d’une résistance de chauffage sur sa face inférieure. Des capillaires métalliques permettent d’assurer la circulation du gaz dans le dispositif. Différents types de préconcentrateurs ont été développés avec différents adsorbants afin satisfaire les conditions pour des applications concernant les composés organiques volatils (COV) et les explosifs. L’optimisation des phases d’adsorption et de désorption est cruciale pour le procédé.Le couplage entre un micro-chromatographe et un préconcentrateur a été réalisé et a montré l’apport de ce microcomposant pour la chromatographie. L’analyse d’un mélange de COV a pu être réalisée avec des concentrations initiales de l’ordre de 40 ppb alors que la limite de détection de l’appareillage était de quelques ppm. Un facteur d’enrichissement de 800 a été atteint.L’avantage de l’utilisation du silicium poreux a également été mis en évidence pour l’adsorption de gaz avec des faibles pressions de vapeur saturante. Cette propriété est intéressante pour la préconcentration de vapeur d’explosifs. / In order to overcome problems due to the conventional sensors detection limits, a preconcentration system is required. Accumulation of vapor(s) for detection is possible with an adsorbent and allows releasing them toward a detector, under the effect of a sudden rise of the temperature. Amplification of the concentration and the signal are obtained.This thesis continues the development of a preconcentrator for the detection of toxic gas and explosives. This preconcentrator is made of a silicon microcomponent filled with an adsorbent and a heater at its back. Two metal capillary allow ensuring the gas flow into the device. Various designs of preconcentrators were developed with different adsorbents to satisfy the requirements for volatile organic compounds (VOCs) and explosives applications.The optimization of adsorption and desorption phases is very important for the process.The coupling between a micro-chromatograph and a preconcentrator was conducted and showed the contribution of the microcomponent to the chromatography. Analysis of a VOCs mixture was achieved with initial concentrations in the order of 40 ppb, whereas the detection limit was of a few ppm. An enrichment factor of 800 was achieved.The advantage of using porous silicon was also demonstrated for the gas adsorption with low saturation vapor pressure. This result is interesting for explosive vapor préconcentration.

Thesis (S.M.)--Joint Program in Applied Ocean Science and Engineering (Massachusetts Institute of Technology, Dept. of Mechanical Engineering; and the Woods Hole Oceanographic Institution), 2005. / Includes bibliographical references (leaves 96-98). / The changing state of warfare has driven the US Navy's area of operations closer to shore into littoral coastal waters. Mine Warfare has been proven as an extremely effective means of battlespace control in these waters. Mines can be inexpensively mass produced and rapidly deployed over large areas. The most common type of mine in use is the bottom placed mine, an object with simple geometry that sits on the seafloor. These mines often exhibit scour induced burial below the seafloor, making detection through traditional mine hunting methods difficult or impossible, while the mines themselves remain lethal. The Office of Naval Research (ONR) has developed a computer model that predicts the extent of mine burial to aid mine hunting and mine clearing operations. Investigations under ONR's Mine Burial Program are presently being conducted to calibrate and validate this model. This thesis uses data from the deployment of an acoustically instrumented model mine near the Martha's Vineyard Coastal Observatory in part of a larger, 16 total object investigation. A 2-axis pencil beam sonar was deployed concurrently with the mine to obtain microbathymetric measurements of the scour pit development and the progression of mine burial. Data correction techniques to correct for beam pattern induced bathymetry errors and a transformed coordinate system are detailed within. / (cont.) An analysis of scour pit dimensions includes scour depth, area, and volume as well as a look into percent burial by depth as a characteristic measurement important for operational mine hunting. The progression of mine burial is related to the wave climate, unsteady flow hydrodynamic forcing, and bed-load transport. The analysis examines the relative roles of these mechanisms in the scour-infill-bury process. / by Brendan Reed Gotowka. / S.M.

The topic of the diploma thesis is fast separation of explosives by HPLC and development of miniaturized liquid chromatograph for application in a handheld explosives detection device. In this work the retention of some nitrated explosives and selectivity in reversed phase system as a function of mobile phase composition is studied while methanol, acetonitrile and acetone as an organic solvent is used. Best selectivity and good retention can be observed in methanol mobile phase. Acetonitrile and acetone are not suitable for fast isocratic separation of mixture containing pentaerythritol tetranitrate because of its strong retention. Efficiency and permeability of monolithic column (Chromolith CapRod RP-18e) and columns filled with superficially porous particles are compared (Kinetex 2,6 µm C-18, Poroshell 120 SB-C18). Monolithic column with satisfying efficiency and high column permeability is the most suitable solution for fast separation of explosives. Assuming use of explosives detection device in different conditions the separation was optimized on temperature 50 °C. Under these conditions the 35% v/v methanol gives good retention and selectivity. For very fast scan analysis of pentaerythritol tetranitrate or other nitroaromatics use of 70% v/v acetone mobile phase is suitable. Construction of miniaturized liquid chromatograph that enables preconcentration of explosives from aqueous solutions and fast separation in less than 1 minute is described. This concept will be incorporated into the handheld explosives detection device where the explosives vapor will be absorbed into the water and after the separation detected by chemiluminescence.

Laser Induced Breakdown Spectroscopy (LIBS) is showing great potential as an atomic analytical technique. With its ability to rapidly analyze all forms of matter, with little-to-no sample preparation, LIBS has many advantages over conventional atomic emission spectroscopy techniques. With the maturation of the technologies that make LIBS possible, there has been a growing movement to implement LIBS in portable analyzers for field applications. In particular, LIBS has long been considered the front-runner in the drive for stand-off detection of trace deposits of explosives. Thus there is a need for a better understanding of the relevant processes that are responsible for the LIBS signature and their relationships to the different system parameters that are helping to improve LIBS as a sensing technology. This study explores the use of LIBS as a method to detect random trace amounts of specific organic materials deposited on organic or non-metallic surfaces. This requirement forces the limitation of single-shot signal analysis. This study is both experimental and theoretical, with a sizeable component addressing data analysis using principal components analysis to reduce the dimensionality of the data, and quadratic discriminant analysis to classify the data. In addition, the alternative approach of ‘target factor analysis’ was employed to improve detection of organic residues on organic substrates. Finally, a new method of characterizing the laser-induced plasma of organics, which should lead to improved data collection and analysis, is introduced. The comparison between modeled and experimental measurements of plasma temperatures and electronic density is discussed in order to improve the present models of low-temperature laser induced plasmas.

L’étude des polymorphes, soit des composés qui peuvent cristalliser avec plus d’une forme cristalline, est un centre d’intérêt pour nombreux domaines scientifiques. Dans certains cas, les variations structurales ont pour effet de causer de majeurs changements aux propriétés physicochimiques des composés, donnant la possibilité de préparer des matériaux possédant des caractéristiques précises pour une application donnée. Le domaine des explosifs est en continuelle évolution afin de combler les besoins militaires et civils. Des matériaux détenant un bon équilibre entre une haute performance énergétique et la sécurité sont recherchés. La 6-azidotétrazolo[5,1- a]phtalazine (ATPH) est une molécule riche en azote étroitement lié aux substances conçues comme explosifs. Dans le cadre de ce mémoire, le criblage polymorphique de l’ATPH entraine la découverte et l’isolation de six nouvelles formes solides de l’ATPH. Les motifs d’empilement à feuillets et à chevrons sont retrouvés dans l’ensemble des structures par des interactions polarisées N…N/C-H…N. Les polymorphes ont été caractérisés par IR, Raman, DSC, PXRD, SC-XRD et des études de stabilité relative en solution. Le caractère hautement polymorphique de l’ATPH est supporté par les résultats d’une étude computationnelle de prédiction des structures cristallines. / The study of polymorphs, or compounds that can crystallize in more than one crystal form, is a focus of interest for many scientific fields. In some cases, structural variations cause major changes in the physicochemical properties of the compounds, making it possible to prepare materials with specific characteristics for a given application. The development of explosive materials is a continuously evolving field for military and civilian purposes. Materials with a fine balance between high energy performance and safety are sought. 6-Azidotetrazolo[5,1-a]phthalazine (ATPH) is a nitrogen-rich molecule closely related to substances designed as explosives. In this dissertation, polymorphic screening of ATPH resulted in the discovery and isolation of six new solid forms of ATPH. Sheets and chevron stacking motifs directed by polarized C-N···N/C-H···N interactions were observed in all structures. The polymorphs were characterized by IR, Raman, DSC, PXRD, SC-XRD, and relative stability studies in solution. The highly polymorphic character of ATPH is consistent with the results of computational crystal structure prediction.

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No description available.

This thesis presents work performed on explosively driven magnetic flux compression generators. This kind of devices converts the chemically stored energy in a high explosive into electromagnetic energy in the form of a powerful current pulse. The high energy density of the high explosives makes flux compression generators attractive as compact power sources. In order to study these devices a generator was designed at FOI in the mid-90ies. Two generators remained unused and became available for this licentiate work. The thesis reports experiments with, and simulations of, the operation of the two remaining generators. The aim was to fully understand the performance of the generator design and be able to accurately simulate its behaviour. The generators were improved and fitted with various types of diagnostics to monitor the generator operation. Two experiments were performed of which the first generator was operated well below its current capability limits while the second was stressed far above its limits. Since the generator generates a rapidly increasing current, a current measurement is the most important diagnostic revealing the current amplification of the generator and its overall performance. Further it is important to measure the timing of various events in the generator. With a common time reference it is possible to combine data from different probes and extract interesting information which cannot be directly obtained with a single measurement. Two types of numerical simulations have been performed: Hydrodynamic simulations of the high explosive interaction with the armature were used to verify the measured armature dynamics. A zero-dimensional code was used to perform circuit simulations of the generator. The model takes into account the inductance reduction due to the compression of the generator as well as the change in conductivity due to heating of the conductors in the generators. / QC 20101103

Um Terroranschläge zu verhindern, werden schnelle, hochempfindliche Detektoren für Sprengstoffe benötigt. Neben Sprengstoffen ist auch der Drogenhandel ein großes gesellschaftliches Problem, welcher kriminelle Organisationen finanziert. Da bereits geringe Mengen an TNT oder Kokain einen Hinweis auf einen Anschlag oder auf Drogenschmuggel darstellen, muss der verwendete Detektor schnell aber dabei gleichzeitig sensitiv und selektiv sein. In dieser Arbeit wurde daher ein Biosensor zur Drogen und Sprengstoff Detektion, der auf auf einem Immunoassay basiert, entwickelt. Um die Performance sicherzustellen, wurden die genutzten Antikörper gründlich auf Eignung untersucht. Für die Affinitätssäule wurden monolithische Säulen hergestellt, welche eine hohe Oberfläche aufweisen. Zur Beschichtung der Säulen wurden Protein-Konjugate synthetisiert. Die Affinitätssäulen waren robust und zeigten eine sehr hohe Binde-Effizienz. Als Detektor wurde ein Fluoreszenz-Mikroskop aus kommerziellen Bauteilen konstruiert. Für den genutzten Fluoreszenzfarbstoff wurde eine Nachweisgrenze von 2 pM sowie ein dynamischer Bereich bis 1000 pM erreicht. Für die Fluidik wurden eine Spritzenpumpe sowie mikrofluidische Bauteile genutzt, welche eine Detektionszeit von 1.5 Minuten ermöglichten. Für TNT wurde mit dem Biosensor eine Nachweisgrenze von 130 pM erzielt. Der Biosensor zeigte außerdem keine Kreuzreaktivität mit gängigen Sprengstoffen. Für Kokain wurde eine Nachweisgrenze von 15 pM im Biosensor erreicht. Zusätzlich wurde für Kokain ein Wischtest entwickelt, welcher in drei Minuten Kokainmengen von 300 pg detektieren kann. Der entwickelte Biosensor gehört zu den besten Sensoren zur TNT- und Kokaindetektion und zeigt eine vergleichbare oder bessere Performance als Flüssigchromatographie mit Massenspektrometrie-Kopplung. Die Flexibilität beim Analyten sowie der Verzicht auf Lösungsmittel machen diesen Biosensor zu einem interessanten Kandidaten für hochempfindliche Messsysteme. / The fast detection of explosives is essential to prevent terror attacks. Besides explosives, the trafficking of illegal drugs is a major problem, which must be addressed to reduce criminal organizations’ revenue streams. As low amounts of these substances may indicate trafficking or a bomb threat, sensitive, selective and fast detection methods are required. Therefore, a biosensor was developed in this work, which relies on an immunoassay. To ensure sensitive and selective performance the used antibodies were characterized in depth. To obtain affinity columns, glass columns were manufactured and used. As column coating affinity conjugates were synthesized. The affinity columns showed efficient antibody trapping and were long-term stable. As a detector an epi-fluorescence microscope was built to monitor the sample. The sensor features consumer-grade parts rendering it easily accessible. For the used fluorophore a limit of detection (LOD) of 2 ppt with a linear range up to 1000 pM was achieved. Due to the use of a syringe pump and an injection valve a continuous fluidic for the biosensor was obtained. The used microfluidic parts resulted in detection times of only 1.5 min. For TNT a LOD of 130 pM was achieved. Additionally, the biosensor showed no cross-reactivity with common high explosives. For cocaine a LOD of 15 pM in solution was achieved and a surface wipe sampling method was demonstrated, which was able to detect 300 pg cocaine on surfaces within three minutes reliably. This biosensor belongs to the fastest and most sensitive cocaine and TNT detectors with sensitivity on par or better than liquid chromatography coupled with mass spectroscopy. Furthermore, the biosensor is affordable, very modular analyte-wise and requires no solvents or microplastic carriers. Therefore, it is a fascinating approach for future high-sensitivity monitoring applications.

<p dir="ltr">Tailorable energetics are energetic materials that can be modified to alter their performance and sensitivity. Examples of tailoring energetic materials include additive manufacturing, manufactured hot spots, switchable energetics, and cocrystallization. Developing novel energetic material is a difficult and cost intensive process, because of this, tailoring the performance and sensitivity of existing energetic materials is critical for continued improvement. Additive manufacturing has provided new methods for generating complex geometries of composite materials. Additive manufacturing of composite materials through direct-ink-write (DIW) experiences extrusion limitations due to the high viscosities of highly solids loaded mixtures; the limitations being more severe with smaller syringe tip diameter. A novel printing technique called vibration-assisted printing (VAP) was developed as a method to extend the extrudability limits and extrusion speeds observed with direct-ink-write systems. Printability envelopes were shown in previous work to extend extrudability of monomodal glass bead composites in VAP systems over conventional DIW systems. This study compares the mass flowrates and extrudability limits for bimodal mixtures of glass beads suspended in a hydroxyl-terminated polybutadiene (HTPB) binder for both VAP and DIW printing as a function of volume percent solids loading. The bimodal glass bead mixtures showed a linear response in extrusion rate versus solids loading for both VAP and DIW systems. The VAP system was able to print higher volume loadings than the direct-ink-write system. In addition to extending the extrudability limits, the mass flowrate for the VAP system was significantly higher at all volume loadings tested compared to the DIW. Interestingly, bimodal mixtures were shown to extrude quicker than the monomodal mixtures at all volume loadings and across both printing systems.</p><p><br></p><p dir="ltr">Inhomogeneities within explosives affect the sensitivity and detonation wave shape of energetic materials. The influence of voids on explosive initiation has been well documented; however, the effects that voids between 0.1 mm and 10 mm have on a propagating detonation wave remains largely unexplored. The effect of single cylindrical voids on detonation wave shape and re-initiation was examined here using manufactured voids in a rubberized 1,3,5-trinitro-1,3,5-triazinane (RDX) explosive. Two streak imaging techniques were fielded to investigate void influence. For the first, back-surface streak imaging, the location of the void on the samples was changed and the resulting change in detonation wave shape at the downstream breakout was captured using a streak camera in cut-back experiments. The results from this experiment showed the effects of an initial jet form for short cut-back distances and as shock propagation progressed, the jet formation was absorbed by the unaffected portions of the wave front. The second method, top-surface streak imaging, was used to investigate the re-initiation/downstream propagation of the detonation front and the detonation velocity of the rubberized explosive. These experiments were compared to similar experimental results from machined voids in PBX 9501, a 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX)-based explosive, to investigate the interaction of a detonation wave with a 0.5 mm void for different explosives. The experiments were also compared to simulations using a multi-dimensional and multi-material hydrodynamic code (CTH). These results showed the influence that small features can have on detonation wave shaping and how explosive properties play a key role in that interaction. In addition to air-filled voids, this study examined the effects of 0.5 mm diameter voids filled with different inert metals on the detonation wave shape for an RDX-based rubberized explosive. The metals selected for experiments were 1066 aluminum, brass, copper, and tungsten. Experimental results showed that the extent of detonation wave shaping was closely tied to the density differential between the bulk explosive and metal insert. Simulations were performed using CTH to further analyze material inclusions. Forty-four different filler materials were simulated to isolate the driving factors for wave shaping of the detonation front. The main factors of interest were bulk sound speed, shock impedance, and filler material density. Understanding the influence of material inclusions on detonation performance and wave shape allows for tailoring of detonations as well as characterizing how unintentional defects will alter the explosive.</p><p><br></p><p dir="ltr">Improving the safety of explosive materials through the synthesis of insensitive explosives has been studied extensively. However, little work has focused on creating switchable explosives. A switchable explosive is normally insensitive to detonation, and therefore safe to handle and transport, but can be sensitized when needed to create a functional explosive. Similarly, it may be desired to desensitize an explosive to prevent its function. This study examined the ability to create a switchable RDX-based rubberized explosive using thermally-expandable microspheres (TEMs). The addition of TEMs to the explosive formulation allowed for microstructural changes and potential hot spot locations such as voids to form as the microspheres expanded. Small voids (less than about 10 µm) are more likely to be critical hot spots when shocked, and likewise larger voids are less likely to ignite successfully (sub-critical) when shocked. Consequently, both sensitization and desensitization are possible. The rubberized explosive considered here with unexpanded microspheres was unable to sustain a detonation for the size used, but after specific heating followed by cooling to produce small voids, a detonation was achieved. That is, the TEMs addition to the RDX-based rubberized explosive resulted in an explosive that is detonation insensitive when unheated but becomes a functional explosive after it is sensitized through heating. This paves the way to create insensitive explosive formulations with on-demand switchable detonation function through the incorporation of thermally-expandable microspheres. Desensitization was also demonstrated with specific heating of TEMs in an initially detonable explosive charge. And finally, we also demonstrated that deflagration can be affected by heating TEMs.</p><p><br></p><p dir="ltr">Energetic cocrystallization is a technique that produces a cocrystal that is formed using two known explosives to potentially gain the benefits of one or both without the drawbacks for a particular application. A comparison of cocrystals to a physical mixture of the same coformers can be considered. Cocrystals have unique material properties and crystal structure, whereas a physical mixture is just a mixed combination of the known materials at the same molar ratio. This study used photon Doppler velocimetry (PDV) to compare the particle velocity for 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) and 1-methyl-3,5-dinitro-1,2,4-triazole (MDNT) at a 1:1 molar ratio for both a cocrystal and a physical mixture of the two energetic materials. This cocrystal was previously shown to detonate faster than a physical mixture. However, the PDV results here were not consistent with this result. In addition to measuring output particle velocity with PDV, the cocrystal was characterized to examine phase purity and possible signs of deterioration of the material over time. Evaluating the cocrystal with Fourier-transform infrared spectroscopy (FT-IR), bomb calorimetry, and powder X-ray diffraction (PXRD) allowed for more accurate comparison and greater confidence in the particle velocity measurements obtained in these experiments. The most significant difference in the material characterization results was the difference in enthalpy of formation, as the material tested in this study had a substantially lower enthalpy of formation than previously measured for a CL-20/MDNT cocrystal.</p>