Rozprawy doktorskie na temat „Fluorescentorganic materials; Explosives materials”

Thesis (M. S.)--Aerospace Engineering, Georgia Institute of Technology, 2009.
Committee Chair: Hanagud, Sathya; Committee Member: Kardomateas, George; Committee Member: McDowell, David; Committee Member: Ruzzene, Massimo; Committee Member: Thadhani, Naresh.

A low cost Cook-Off experimental facility has been established to provide a convenient method of ranking explosives in their response to Cook-Off by the time to event under two widely different heating rates and at two different scales. This thesis describes the literature review undertaken as preparation for the purposed study and all the experimental work developed comprising the design of the trials vehicles, the demonstration of their suitability for Fast and Slow Cook-Off trials with confined explosive systems, the preparation of the samples and test vehicles to be trialled as well as the set-up of adequate facilities to undertake the scheduled firing programme. Results are reported for Cook-Off tests on TNT, RDX, and their mixtures. The emphasis of the study is on time to event, and temperature at event, and in addition a qualitative assessment of the violence of the event was made by examination of the fragments of the vehicles, although it is accepted that the relatively light and low cost design of the vehicle may lead to variable confinement in the early stages of the explosive event, and hence to a wider spread of responses than would be obtained from a more heavily confined and more costly vehicle. The test vehicles give results, which differentiate between the various explosives and explosive mixtures trialled and between the scales. More experiments are required to establish the reproducibility of the measurements. The design of the equipment makes this a relatively inexpensive undertaking. The experiment was modelled using published kinetic data, but the calculated time to event differed from that observed to different extents at the two scales. It is hypothesised that the mechanism may change over the prolonged heat soaks and that quantitative scaling is not possible with the available information. Further work is also suggested using a different type of Cook-Off test vehicle, which will in our opinion reduce even further the cost of Cook-Off testing, due to reduction in man-hours of preparation involved and manufacture cost of the Cook-Off test vehicles, and consequently of ranking of explosives.

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2006.
Vita.
Includes bibliographical references.
Optical chemosensing, especially using amplifying fluorescent polymers, can allow for the highly sensitive and selective vapor-phase detection of both explosives and highly toxic chemicals, including chemical warfare agents. There are varieties of analyte targets, however, that remain challenging for detection by these methods. Research towards improving this technology has obvious implications for homeland security and soldier survivability. This dissertation details the development of new molecules, materials, and transduction schemes aimed at improving both the versatility and sensitivity of optical chemical detection. Chapter One provides an introduction to the field of fluorescent polymer sensors, principally focusing on their utility in the detection of nitroaromatic explosives. Brief descriptions of other analytical methods used for explosives detection are also included. Chapter Two describes the synthesis and optical properties of a new class of conjugated polymers that contain alkyl-amino groups directly bound to the arene rings of poly(phenylene ethynylene)s and poly(fluorene)s. These materials displayed red-shifted absorption and emission spectra, large Stokes Shifts, as well as long excited state lifetimes.
(cont.) Also described is the use of films of these readily oxidized polymers in the vapor-phase detection of hydrazine down to a concentration of 100 parts-per-billion. This new scheme for the detection of hydrazine vapor relies on the analyte's reduction of oxidized traps ("unquenching") within the polymer film to give a fluorescence "turn-on" signal. Chapter Three begins with an introduction to the various classes of explosive molecules, as well as to the concept of "tagging" plastic explosives with higher vapor pressure dopants in order to make them easier to detect. This is followed by a description of how the taggant DMNB was successfully detected using high band-gap poly(fluorene)s. The higher energy conduction bands of these materials allowed for exergonic electron transfer to DMNB and fluorescence quenching in both the solution and solid states. Phosphorescence is the theme of Chapter Four, in which two research projects based on highly phosphorescent cyclometalated Pt(II) complexes are summarized. This includes the synthesis and optical characterization of a phosphorescent poly(fluorene), one of the repeat units of which is a Pt(ppy)(acac)-type complex. Comparisons of its intrinsic photophysical properties and oxygen-induced quenching behavior to model compounds are also summarized.
(cont.) Chapter Four also details investigations into using oxidative addition reactions of new bis-cyclometalated Pt(II) complexes for the dark-field turn-on chemical detection of cyanogen halides. Incorporating substituents on the ligands that force steric crowding in the square plane accelerated the addition of cyanogen bromide to these complexes, which also correlated with the room-temperature phosphorescence efficiency of these complexes. Exposure of polymer films doped with these complexes gave a dark-field turn on signal to the blue of the reactant that corresponded to the phosphorescence of the Pt(IV) oxidative addition product. Finally, Chapter Five focuses on iptycenes, a very useful structural moiety in the field of optical chemosensing. The development of an improved synthetic procedure for the preparation of the iptycene group is described. This procedure has been showed to be effective in the preparation of a series of new iptycene-containing molecules, including a poly(iptycene). To conclude, the unique counter-aspect ratio alignment behavior of a poly(iptycene) in a stretch-aligned polymer film is summarized. This is rationalized by a "threading" model, in which the chains of the poly(vinyl chloride) matrix occupy the internal-free-volume defined by the poly(iptycene).
by Samuel William Thomas, III.
Ph.D.

A tetrazole is a 5-membered ring containing 4 nitrogens and 1 carbon. Due to its energetic potential and structural similarity to carboxylic acids, this ring system has a wide number of applications. In this thesis, a new and safe sustainable process to produce tetrazoles was designed that acheived high yields under mild conditions. Also, a technique was developed to form a trityl-protected tetrazole in situ. The rest of this work involved the exploitation of the energetic potential of tetrazoles. This moiety was successfully applied in polymers, ionic liquids, foams, and gels. The overall results from these experiments illustrate the fact that tetrazoles have the potential to serve as a stable alternative to the troublesome azido group common in many energetic materials. Due to these applications, the tetrazole moiety is a very important entity.

La presente tesis doctoral titulada ¿Materiales funcionales híbridos para el reconocimiento óptico de explosivos nitroaromáticos mediante interacciones supramoleculares¿ se basa en la combinación de principios de Química Supramolecular y de Ciencia de los Materiales para el diseño y desarrollo de nuevos materiales híbridos orgánico-inorgánicos funcionales capaces de detectar explosivos nitroaromáticos en disolución. En primer lugar se realizó una búsqueda bibliográfica exhaustiva de todos los sensores ópticos (cromogénicos y fluorogénicos) descritos en la bibliografía y que abarca el periodo desde 1947 hasta 2011. Los resultados de la búsqueda están reflejados en el capítulo 2 de esta tesis. El primer material híbrido preparado está basado en la aplicación de la aproximación de los canales iónicos y, para ello, emplea nanopartículas de sílice funcionalizadas con unidades reactivas y unidades coordinantes (ver capítulo 3). Este soporte inorgánico se funcionaliza con tioles (unidad reactiva) y una poliamina lineal (unidad coordinante) y se estudia el transporte de una escuaridina (colorante) a la superficie de la nanopartícula en presencia de diferentes explosivos. En ausencia de explosivos, la escuaridina (color azul y fluorescencia intensa) es capaz de reaccionar con los tioles anclados en la superficie decolorando la disolución. En presencia de explosivos nitroaromáticos se produce una inhibición de la reacción escuaridinatiol y la suspensión permanece azul. Esta inhibición es debida a la formación de complejos de transferencia de carga entre las poliaminas y los explosivos nitroaromáticos. En la segunda parte de esta tesis doctoral se han preparado materiales híbridos con cavidades biomiméticas basados en el empleo de MCM-41 como soporte inorgánico mesoporoso (ver capítulo 4). Para ello se ha procedido al anclaje de tres fluoróforos (pireno, dansilo y fluoresceína) en el interior de los poros del soporte inorgánico y, posteriormente, se ha hidrofobado el interior de material mediante la reacción de los silanoles superficiales con 1,1,1,3,3,3-hexametildisilazano. Mediante este procedimiento se consiguen cavidades hidrófobas que tienen en su interior los fluoróforos. Estos materiales son fluorescentes cuando se suspenden en acetonitrilo mientras que cuando se añaden explosivos nitroaromáticos a estas suspensiones se observa una desactivación de la emisión muy marcada. Esta desactivación de la emisión es debida a la inclusión de los explosivos nitroaromáticos en la cavidad biomimética y a la interacción de estas moléculas (mediante interacciones de ¿- stacking) con el fluoróforo. Una característica importante de estos materiales híbridos sensores es que pueden ser reutilizados después de la extracción del explosivo de las cavidades hidrofóbicas. En la última parte de esta tesis doctoral se han desarrollado materiales híbridos orgánicoinorgánicos funcionalizados con ¿puertas moleculares¿ que han sido empleados también para detectar explosivos nitroaromáticos (ver capítulo 5). Para la preparación de estos materiales también se ha empleado MCM-41 como soporte inorgánico. En primer lugar, los poros del soporte inorgánico se cargan con un colorante/fluoróforo seleccionado. En una segunda etapa, la superficie externa del material cargado se ha funcionalizado con ciertas moléculas con carácter electrón dador (pireno y ciertos derivados del tetratiafulvaleno). Estas moléculas ricas en electrones forman una monocapa muy densa (debida a las interacciones dipolo-dipolo entre estas especies) alrededor de los poros que inhibe la liberación del colorante. En presencia de explosivos nitroaromáticos se produce la ruptura de la monocapa, debido a interacciones de ¿-stacking con las moléculas ricas en electrones, con la consecuencia de una liberación del colorante atrapado en el interior de los poros observándose una respuesta cromo-fluorogénica
Salinas Soler, Y. (2013). Functional hybrid materials for the optical recognition of nitroaromatic explosives involving supramolecular interactions [Tesis doctoral]. Editorial Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/31663
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First-principles calculations employing density functional theory (DFT) were performed on the energetic materials PETN, HMX, RDX, nitromethane, and a recently discovered material, nitrate ester 1 (NEST-1). The aims of the study were to accurately predict the isothermal equation of state for each material, improve the description of these molecular crystals in DFT by introducing a correction for dispersion interactions, and perform uniaxial compressions to investigate physical properties that might contribute to anisotropic sensitivity. For each system, hydrostatic-compression simulations were performed. Important properties calculated from the simulations such as the equilibrium structure, isothermal equation of state, and bulk moduli were compared with available experimental data to assess the agreement of the calculation method. The largest contribution to the error was believed to be caused by a poor description of van der Waals (vdW) interactions within the DFT formalism. An empirical van der Waals correction to DFT was added to VASP to increase agreement with experiment. The average agreement of the calculated unit-cell volumes for six energetic crystals improved from approximately 9% to 2%, and the isothermal EOS showed improvement for PETN, HMX, RDX, and nitromethane. A comparison was made between DFT results with and without the vdW correction to identify possible advantages and limitations.  Uniaxial compressions perpendicular to seven low-index crystallographic planes were performed on PETN, HMX, RDX, nitromethane, and NEST-1. The principal stresses, shear stresses, and band gaps for each direction were compared with available experimental information on shock-induced sensitivity to determine possible correlations between physical properties and sensitivity. The results for PETN, the only system for which the anisotropic sensitivity has been thoroughly investigated by experiment, indicated a possible correlation between maximum shear stress and sensitivity. The uniaxial compressions that corresponded to the greatest maximum shear stresses in HMX, RDX, solid nitromethane, and NEST-1 were identified and predicted as directions with possibly greater sensitivity. Experimental data is anticipated for comparison with the predictions.

Structural energetic materials (SEM) are a class of multicomponent materials which may react under various conditions to release energy. Fragmentation and impact induced reaction are not well characterized phenomena in SEMs. The structural energetic systems under consideration here combine aluminum with one or more of the following: nickel, tantalum, tungsten, and/or zirconium. These metal+Al systems were formulated with powders and consolidated using explosive compaction or the gas dynamic cold spray process. Fragment size distributions of the indicated metal+Al systems were explored; mean fragment sizes were found to be smaller than those from homogeneous ductile metals at comparable strain rates, posing a reduced risk to innocent bystanders if used in munitions. Extensive interface failure was observed which suggested that the interface density of these systems was an important parameter in their fragmentation. Existing fragmentation models for ductile materials did not adequately capture the fragmentation behavior of the structural energetic materials in question. A correction was suggested to modify an existing fragmentation model to expand its applicability to structural energetic materials. Fragment data demonstrated that the structural energetic materials in question provided a significant mass of combustible fragments. The potential combustion enthalpy of these fragments was shown to be significant. Impact experiments were utilized to study impact induced reaction in the indicated metal+Al SEM systems. Mesoscale parametric simulations of these experiments indicated that the topology of the microstructure constituents, particularly the stronger phase(s), played a significant role in regulating impact induced reactions. Materials in which the hard phase was topologically connected were more likely to react at a lower impact velocity due to plastic deformation induced temperature increases. When a compliant matrix surrounded stronger, simply connected particles, the compliant matrix accommodated nearly all of the deformation, which limited plastic deformation induced temperature increases in the stronger particles and reduced reactivity. Decreased difference between the strength of the constituents in the material also increased reactivity. The results presented here demonstrate that the fragmentation and reaction of metal+Al structural energetic materials are influenced by composition, microstructure topology, interface density, and constituent mechanical properties.

Shock waves create a unique environment of high pressure, high temperature and high strain-rates. It has been observed that chemical reactions that occur in this regime are exothermic and can lead to the synthesis of new materials that are not possible under other conditions. The exothermic reaction is used in the development of binary energetic materials. These materials are of significant interest to the energetic materials community because of its capability of releasing high heat content during a chemical reaction and the relative insensitivity of these types of energetic materials. Synthesis of these energetic materials, at nano grain sizes with structural reinforcements, provides an opportunity to develop a dual functional material with both strength and energetic characteristics. Shock-induced chemical reactions pose challenges in experiment and instrumentation. This thesis is addressed to the theoretical development of constitutive models of shock-induced chemical reactions in energetic composites, formulated in the framework of non-equilibrium thermodynamics and mixture theories, in a continuum scale. Transition state-based chemical reaction models are introduced and incorporated with the conservation equations that can be used to calculate and simulate the shock-induced reaction process. The energy that should be supplied to reach the transition state has been theoretically modeled by considering both the pore collapse mechanism and the plastic flow with increasing yield stress behind the shock wave. A non-equilibrium thermodynamics framework and the associated evolution equations are introduced to account for time delays that are observed in the experiments of shock-induced or assisted chemical reactions. An appropriate representation of the particle size effects is introduced by modifying the initial energy state of the reactants. Numerical results are presented for shock-induced reactions of mixtures of Al, Fe2O3 and Ni, Al with epoxy as the binder. The theoretical model, in the continuum scale, requires parameters that should be experimentally determined. The experimental characterization has many challenges in measurement and development of nano instrumentation. An alternate approach to determine these parameters is through ab-initio calculations. Thus, this thesis has initiated ab-initio molecular dynamics studies of shock-induced chemical reactions. Specifically, the case of thermal initiation of chemical reactions in aluminum and nickel is considered.

The major goal of this PhD project is to investigate the fundamental properties of energetic materials, including their atomic and electronic structures, as well as mechanical properties, and relate these to the fundamental mechanisms of shock wave and detonation propagation using state-of-the-art simulation methods. The first part of this PhD project was aimed at the investigation of static properties of energetic materials (EMs) with specific focus on 1,3,5-triamino-2,4,6-trinitrobenzene (TATB). The major goal was to calculate the isotropic and anisotropic equations of state for TATB within a range of compressions not accessible to experiment, and to make predictions of anisotropic sensitivity along various crystallographic directions. The second part of this PhD project was devoted to applications of a novel atomic-scale simulation method, referred to as the moving window molecular dynamics (MW-MD) technique, to study the fundamental mechanisms of condensed-phase detonation. Because shock wave is a leading part of the detonation wave, MW-MD was applied to demonstrate its effectiveness in resolving fast non-equilibrium processes taking place behind the shock-wave front during shock-induced solid-liquid phase transitions in crystalline aluminum. Next, MW-MD was used to investigate the fundamental mechanisms of detonation propagation in condensed energetic materials. Due to the chemical complexity of real EMs, a simplified AB model of a prototypical energetic material was used. The AB interatomic potential, which describes chemical bonds, as well as chemical reactions between atoms A and B in an AB solid, was modified to investigate the mechanism of the detonation wave propagation with different reactive activation barriers. The speed of the shock or detonation wave, which is an input parameter of MW-MD, was determined by locating the Chapman-Jouguet point along the reactive Hugoniot, which was simulated using the constant number of particles, volume, and temperature (NVT) ensemble in MD. Finally, the detonation wave structure was investigated as a function of activation barrier for the chemical reaction AB+B ⇒ A+BB. Different regimes of detonation propagation including 1-D laminar, 2-D cellular, and 3-D spinning and turbulent detonation regimes were identified.

The effects of reactive metal particles on the microstructure and mechanical properties of epoxy-based composites are investigated in this work. To examine these effects castings of epoxy reinforced with 20-40 vol.% Al and 0-10 vol.% Ni were prepared, while varying the aluminum particle size from 5 to 50 microns and holding the nickel particle size constant at 50 microns. In total eight composite materials were produced, possessing unique microstructures. The microstructure is quantitatively characterized and correlated with the composite constitutive response determined from quasi-static and dynamic compressive loading conditions at strain-rates from 1e-4 to 5e3 /s. Microstructures from each composite and at each strain rate were analyzed to determine the amount of particle strain as a function of bulk strain and strain rate. Using computational simulations of representative microstructures of select composites, the epoxy matrix-metallic particle and particle-particle interactions at the mesoscale under dynamic compressive loading conditions were further examined. From computational simulation data, the stress and strain localization effects were characterized at the mesoscale and the bulk mechanical behavior was decomposed into the individual contributions of the constituent phases. The particle strain and computational analysis provided a greater understanding of the mechanisms associated with particle deformation and stress transfer between phases, and their influence on the overall mechanical response of polymer matrix composites reinforced with metallic particles. The highly heterogeneous composite microstructure and the high contrasting properties of the individual constituents were found to drive localized deformations that are often more pronounced than those in the bulk material. The strain rate behavior of epoxy is shown to cause a strain rate dependent deformation response of reinforcement particle phases that are typically strain rate independent. Additionally, the epoxy matrix strength behavior was found to have a higher dependence on strain rate due to the presence of metal particle fillers. Discrepancies between experimental and simulation mechanical behavior results and these findings indicate a need for epoxy constitutive models to incorporate effects of particle reinforcement on the mechanical behavior.

The detection of explosives and their derivatives is crucial for security, defence and safety. However, detection of low levels and vapour phase of explosives are a serious challenge for forensic practitioners. Scientists and researchers continue to improve sensitive detection methods with reasonable cost and portability. One of the promising techniques for such applications is Surface Enhanced Raman spectroscopy (SERS) due to its high sensitivity and ease of use. Several approaches were applied to improve the sensitivity of explosives detection based on the SERS technique. A wide range of materials were prepared, characterized and used as SERS substrates, including metals such as gold, silver, copper nanostructures, and semiconductors such as TiO2, ZnO. SERS activity of these materials was evaluated, and high quality detection of explosives was achieved at ultra-trace levels. Sensors with high selectivity, reproducibility, reusability and low limit of detection LOD were made. A new sensitive method for enhancement of Raman signals was demonstrated, whereby pre-irradiation (photo-excitation) of a semiconductor such as TiO2 coated with gold/silver nanoparticles, enables strong Raman enhancement at the nanoparticle sites, increasing sensitivity beyond the normal SERS effect. We call this effect photo-induced enhanced Raman spectroscopy— PIERS. In this system the molecules can be directly adsorbed onto the metallic particle, allowing controlled enhancement by both the electromagnetic and chemical enhancement factor. Various analytes were detected by PIERS including dyes, explosives and biomolecules with high sensitivity, reproducibility, and the substrate was reusable for self-cleaning by UV-irradiation. Further investigations were carried out for photo-induced enhancement including creation of oxygen vacancies on semiconductors surface by annealing in vacuum and etching, and a series of SERS measurements were performed of molecules on treated substrates. Silver nanocubes showed high SERS sensitivity of explosives with good specificity, and showed an important role for the preparation of SERS samples. The shape of AgNC contributed significantly to obtained high SERS enhancement. SERS measurements of vapour explosives were performed and showed to be an order of magnitude greater than reported enhancement, where the detection specificity was strongly improved. Free-metal ZnO nanostructures showed charge transfer enchantment, where ZnO nanocrystals exhibited better enhancement than ZnO thin films. The enhancement is further improved in the presence of copper species in the ZnO thin film structure.

Nanoenergetic composite materials have been synthesized by a sol-gel chemical process where the addition of a weak base molecule induces the gelation of a hydrated metal salt solution. A proposed proton scavenging mechanism, where a weak base molecule extracts a proton from the coordination sphere of the hydrated iron (III) complex in the gelation process to form iron (III) oxide/hydroxide, FeIIIxOyHz, has been confirmed for the weak base propylene oxide (PO), a 1,2 epoxide, as well as for the weak bases tetrahydrofuran (THF), a 1,4 epoxide, and pyridine, a heterocyclic nitrogen-containing compound. THF follows a similar mechanism as PO; the epoxide extracts a proton from the coordination sphere of the hydrated iron complex forming a protonated epoxide which then undergoes irreversible ring-opening after reaction with a nucleophile in solution. Pyridine also extracts a proton from the hydrated metal complex, however, the stable six-membered molecule has low associated ring strain and does not endure ring-opening. Fe2O3/Al energetic systems were synthesized from the epoxides PO, trimethylene oxide (TMO) and 3,3 dimethyl oxetane (DMO). Surface area analysis of the synthesized matrices shows a direct correlation between the surface area of the iron (III) oxide matrix and the quantified exothermic heat of reaction of the nano-scaled aluminum-containing energetic material due to the magnitude of the interfacial surface area contact between the iron (III) oxide matrix and the aluminum particles. The Fe2O3(PO)/Al systems possess the highest heat of reaction values due to the oxide interfacial surface area available for contact with the aluminum particles. Also, reactions containing nano-scale aluminum react differently than those containing micron-scale aluminum. RuO2/Al energetic systems behave differently dependent on the atmosphere the sample is heated. Heating the RuO2/Al samples in an inert atmosphere results in the complete reduction of the ruthenium oxide matrix to Ru(0) before reaction with the aluminum particles, resulting in the exothermic formation of RuxAly intermetallics, with the stoichiometry dependent on the initial Ru:Al concentration. However, heating the samples in an oxygen-rich atmosphere results in an exothermic reaction between RuO2 and Al.

This research aims to contribute to the safe methodology for additive manufacturing (AM) of energetic materials. Coating formulation processes were investigated to find a suitable method that may enable selective laser sintering (SLS) as the safe method for fabrication of high explosive (HE) compositions. For safety and convenience reasons, the concept demonstration was conducted using inert explosive simulants with properties quasi-similar to the real HE. Coating processes for simulant RDX-based microparticles by means of PCL and 3,4,5- trimethoxybenzaldehyde (as TNT simulant) are reported. These processes were evaluated for uniformity of coating the HE inert simulant particles with binder materials to facilitate the SLS as the adequate binding and fabrication method. The critical constraints being the coating effectiveness required, spherical particle morphology, micron size range (>20 μm) and a good powder deposition and flow, and performance under SLS to make the method applicable for HEs. Of the coating processes investigated, suspension system and single emulsion methods gave required particle near spherical morphology, size and uniform coating. The suspension process appears to be suitable for the SLS of HE mocks and potential formulation methods for active HE composites. The density was estimated to be comparable with the current HE compositions and plastic bonded explosives (PBXs) such as C4 and PE4, produced from traditional methods. The formulation method developed and the understanding of the science behind the processes paves the way toward safe SLS of the active HE compositions and may open avenues for further research and development of munitions of the future.
Dissertation (MSc)--University of Pretoria, 2019.
Chemical Technology
MSc
Unrestricted

La détection de très faibles quantités de Matériaux Energétiques (ME) est un challenge important dans la lutte contre le terrorisme. En plus des méthodes de détection des ME par affinité chimique, il est aussi intéressant d'utiliser les variations enthalpiques dues à la décomposition des ME pour les détecter par analyse thermique. Cependant, la sensibilité des methodes classiques est insuffisante pour la détection des particules dont la masse se situe dans le domaine des nanogrammes. En revanche, la nanocalorimétrie est parfaitement adaptée pour la caractérisation de très faibles quantités d'échantillons et est de ce fait adaptée aux exigences de la détection. Afin d'explorer la possibilité de détecter et d'identifier des micro-particules solides de ME à l'aide de l'analyse thermique, nous avons élaboré des protocols optimisés pour la détection et l'identification de particules pures unitaires de quelques nanogrammes de ME ainsi que leurs mélanges. Les résultats montrent que la limite de détection se situe environ à quelques centaines de picrogrammes. Les expériences ont été complétées par de l'analyse structurale in-situ en utilisant sa combinaison avec de la DRX par faisceau nanofocus synchrotron
Being able to sense the minuscule amounts of energetic materials is crucial in the context of the fight against terrorism. Apart from the methods of detection of EM, which are specific to the chemical structure, one could use the enthalpy variations of the EM decomposition process for their detection by means of thermal analysis. However, the sensitivity of classical methods would be still insufficient to sense particles in the nanogram range. By contrast, the recently developed technique of chip calorimetry is perfectly suited for characterizing small amounts of samples and is therefore fully adequate for this task.In order to explore the possibilities of detection and identification of solid micro-particles of EM with thermal analysis, we discuss on the protocols optimized for the detection and identification of nanogram-size particles of EM and its mixtures with the chip calorimeter accessory. The results obtained on pure EM and its mixtures show that the detection threshold can be put at approximately several hundred picograms. The experiments were completed by the in-situ structural analysis using a combination with nanofocus synchrotron XRD

The research described in this thesis seeks to explore a concept that has the potential to make a step-change for the control of the properties of energetic materials (sensitivity, long-term storage, processability, performance, etc.), resulting in safer munitions with enhanced performance. This concept is co-crystallisation and involves crystallisation of the energetic material with one or more molecular components in order to modify the properties of the composition. The concept has been demonstrated in the pharmaceutical sector as a successful means of altering the physical properties of active pharmaceutical ingredients, e.g. solubility, bioavailability, stability to humidity. This project therefore aims to exploit the concepts of crystal engineering and co-crystallisation as applied to selected energetic materials in order to achieve the following objectives: (i) develop an enhanced understanding of how structure influences key properties such as sensitivity, (ii) control the sensitivity of existing, approved energetic materials, and (iii) identify new energetic materials with enhanced properties, e.g. reduced sensitivity, higher performance, and increased thermal stability. The compound 3,5-nitrotriazolone (NTO) was crystallised with a selection of co-formers to produce salts and co-crystals. The structure properties of these materials were explored using single-crystal and powder X-ray diffraction, and structural features were correlated with properties such as crystal density, difference in pKa of co-formers, thermal properties, and sensitivity to impact. Detonation velocities of the co-crystals were calculated based on densities, chemical composition, and heats of formation. Co-former molecules included a series of substituted anilines, substituted pyridines (including 4,4’-bipyridine, 2-pyridone), and substituted triazoles. A co-crystal was formed between NTO and 4,4’-bipyridine on crystallisation from ethanol, whilst a salt was formed when crystallised from water. Upon heating the salt to 50ºC, the co-crystal was formed. Structural differences between the salts formed by NTO with 3,5-DAT and 3,4- DAT were correlated with structural features. 3,5-DAT.NTO is substantially less impact sensitive than 3,4-DAT.NTO, and this is attributed to the layered structure of 3,5-DAT.NTO. An investigation into triazole-based NTO salts under high pressure was conducted. A new polymorph of 3,5-DAT.NTO was discovered upon increasing the pressure to 2.89 GPa. The high-pressure phase appears to retain the layered structure and remains in this phase up to 5.33 GPa, although it was not recoverable upon decompression to atmospheric pressure. The compression behaviour of the unit cell volume for phase I of 3,5-DAT.NTO has been fitted to a 3rd-order Birch- Murnaghan equation of state (EoS) with V0 = 957.7 Å3, B0 = 8.2 GPa and B’0 = 14.7. The unit cell was found to be most compressible in the a and c directions. Under high pressure 3,4-DAT.NTO does not give any indication of a phase change occurring up to 6.08 GPa. The coefficients of the 3rd-order Birch-Murnaghan EoS have been determined to be V0 = 915.9 Å3, B0 = 12.6 GPa and B’0 = 6.5.

There is an increase in bombing assaults in recent years in our country. Determining the explosive material used in these cases by the quick and correct analysis of the evidence obtained after the explosions, is an important starting point for the investigations which are done to reach the perpetrators. The forensic chemistry investigations have to be correct, exact and rapid in order to reach the right criminal. In this study, the Gas Chromatography-Mass Spectrometry (GC-MS) and Gas Chromatography-Thermal Energy Analyser (GC-TEA) methods which are being used for the determination of the explosive materials&rsquo
residues used in bombing attacks are optimized with the standard solutions of 2,4,6-Trinitrotoluene (TNT) and 1,3,5-trinitro-1,3,5-triazocyclohexane (RDX) and standard mixture solution. The two methods were compared by analysing the postexplosion soil samples. Also an efficient and applicable sample preparation procedure was developed. The results showed that both methods are efficient and sensitive for the postexplosion investigations. It is seen that GC-TEA has lower detection limit and simple chromatograms due to its selectivity against only nitro group containing explosives. However it is concluded that there is a need for a reliable and sensitive method like GC-MS which provides identification and library search, for the determination of the organic components which can not be identified with GC-TEA

The objective of this work is to evaluate the reaction initiation characteristics of quasi-statically compressed intermetallic-forming aluminum-based reactive materials upon impact initiation, consisting of equi-volumetric tantalum-aluminum, tungsten-aluminum, nickel-aluminum, and pure aluminum. A modified Taylor rod-on-anvil setup was employed to determine the reaction initiation threshold kinetic energy and actual energy for plastic deformation and subsequent reaction. Experimental sample remnants were recovered and examined through X-ray diffraction to determine reaction products.The overall results indicate that of the various intermetallic-forming systems investigated, Ta+Al was the most reactive and was the only system where any reaction products were retrieved. While all of the intermetallic systems reacted in air, only Ta+Al and W+Al reacted in vacuum environment suggesting differences in reaction mechanisms influencing the reactivity of intermetallic mixtures. Based on the threshold energy for onset of reaction it appears that the Ta-Al compacts show reaction conditions below those required for reaction of Al in air. This combined with the fact that Ta+Al compacts also react in vacuum implies that the Ta+Al undergoes anaerobic intermetallic reaction while the other systems react with the oxidation of Al. The effect of compact packing density on the kinetic energy threshold for reaction initiation were also evaluated. It was observed more densely packed Ta+Al and Ni+Al powder compacts react more easily than less densely packed samples. While the effect of packing density is not as obvious in the case of pure Al and W+Al powder compacts. Finally, a particle size effect is seen on Ni+Al on samples of < 92% density where coarser (+325 -200 mesh) equal-volumetric powder mixtures were observed to be more reactive than finer Ni+Al (-325 mesh).

This Thesis covers work conducted to understand the mechanisms underpinning the operation of the electrothermal-chemical gun. The initial formation of plasma from electrically exploding wires, through to the development of plasma venting from the capillary and interacting with a densely packed energetic propellant bed is included. The prime purpose of the work has been the development and validation of computer codes designed for the predictive modelling of the elect rothe rmal-ch em ical (ETC) gun. Two main discussions in this Thesis are: a proposed electrically insulating vapour barrier located around condensed exploding conductors and the deposition of metallic vapour resulting in a high energy flux to the surface of propellant, leading to propellant ignition. The vapour barrier hypothesis is important in a number of fields where the passage of current through condensed material or through plasma is significant. The importance may arise from the need to disrupt the fragments by applying strong magnetic fields (as in the disruption of metallic shaped charge jets); in the requirement to generate a metallic vapour efficiently from electrically exploding wires (as per ETC ignition systems); or in the necessity to re-use the condensed material after a discharge (as with lightning divertor strips). The ignition by metallic vapour deposition hypothesis relies on the transfer of latent heat during condensation. It is important for the efficient transfer of energy from an exploded wire (or other such metallic vapour generating device) to the surface of energetic material. This flux is obtained far more efficiently through condensation than from radiative energy transfer, because the energy required to evaporate copper is far less than that required to heat it to temperatures at which significant radiative flux would be emitted

This Thesis covers work conducted to understand the mechanisms underpinning the operation of the electrothermal-chemical gun. The initial formation of plasma from electrically exploding wires, through to the development of plasma venting from the capillary and interacting with a densely packed energetic propellant bed is included. The prime purpose of the work has been the development and validation of computer codes designed for the predictive modelling of the elect rothe rmal-ch em ical (ETC) gun. Two main discussions in this Thesis are: a proposed electrically insulating vapour barrier located around condensed exploding conductors and the deposition of metallic vapour resulting in a high energy flux to the surface of propellant, leading to propellant ignition. The vapour barrier hypothesis is important in a number of fields where the passage of current through condensed material or through plasma is significant. The importance may arise from the need to disrupt the fragments by applying strong magnetic fields (as in the disruption of metallic shaped charge jets); in the requirement to generate a metallic vapour efficiently from electrically exploding wires (as per ETC ignition systems); or in the necessity to re-use the condensed material after a discharge (as with lightning divertor strips). The ignition by metallic vapour deposition hypothesis relies on the transfer of latent heat during condensation. It is important for the efficient transfer of energy from an exploded wire (or other such metallic vapour generating device) to the surface of energetic material. This flux is obtained far more efficiently through condensation than from radiative energy transfer, because the energy required to evaporate copper is far less than that required to heat it to temperatures at which significant radiative flux would be emitted

This work focuses on understanding the impact-initiated combustion of aluminum powder compacts. Aluminum is typically one of the components of intermetallic-forming structural energetic materials (SEMs), which have the desirable combination of rapid release of thermal energy and high yield strength. Aluminum powders of various sizes and different levels of mechanical pre-activation are investigated to determine their reactivity under uniaxial stress rod-on-anvil impact conditions, using a 7.62 mm gas gun. The compacts reveal light emission due to combustion upon impact at velocities greater than 170 m/s. Particle size and mechanical pre-activation influence the initiation of aluminum combustion reaction through particle-level processes such as localized friction, strain, and heating, as well as continuum-scale effects controlling the amount of energy required for compaction and deformation of the powder compact during uniaxial stress loading. Compacts composed of larger diameter aluminum particles (~70µm) are more sensitive to impact initiated combustion than those composed of smaller diameter particles. Additionally, mechanical pre-activation by high energy ball milling (HEBM) increases the propensity for reaction initiation. Direct imaging using high-speed framing and IR cameras reveals light emission and temperature rise during the compaction and deformation processes. Correlations of these images to meso-scale CTH simulations reveal that initiation of combustion reactions in aluminum powder compacts is closely tied to mesoscale processes, such as particle-particle interactions, pore collapse, and particle-level deformation. These particle level processes cannot be measured directly because traditional pressure and velocity sensors provide spatially averaged responses. In order to address this issue, quantum dots (QDs) are investigated as possible meso-scale pressure sensors for probing the shock response of heterogeneous materials directly. Impact experiments were conducted on a QD-polymer film using a laser driven flyer setup at the University of Illinois Urbana-Champaign (UIUC). Time-resolved spectroscopy was used to monitor the energy shift and intensity loss as a function of pressure over nanosecond time scales. Shock compression of a QD-PVA film results in an upward shift in energy (or a blueshift in the emission spectra) and a decrease in emission intensity. The magnitude of the shift in energy and the drop in intensity are a function of the shock pressure and can be used to track the particle scale differences in the shock pressure. The encouraging results illustrate the possible use of quantum dots as mesoscale diagnostics to probe the mechanisms involved in the impact initiation of combustion or intermetallic reactions.

A low cost Cook-Off experimental facility has been established to provide a convenient method of ranking explosives in their response to Cook-Off by the time to event under two widely different heating rates and at two different scales. This thesis describes the literature review undertaken as preparation for the purposed study and all the experimental work developed comprising the design of the trials vehicles, the demonstration of their suitability for Fast and Slow Cook-Off trials with confined explosive systems, the preparation of the samples and test vehicles to be trialled as well as the set-up of adequate facilities to undertake the scheduled firing programme. Results are reported for Cook-Off tests on TNT, RDX, and their mixtures. The emphasis of the study is on time to event, and temperature at event, and in addition a qualitative assessment of the violence of the event was made by examination of the fragments of the vehicles, although it is accepted that the relatively light and low cost design of the vehicle may lead to variable confinement in the early stages of the explosive event, and hence to a wider spread of responses than would be obtained from a more heavily confined and more costly vehicle. The test vehicles give results, which differentiate between the various explosives and explosive mixtures trialled and between the scales. More experiments are required to establish the reproducibility of the measurements. The design of the equipment makes this a relatively inexpensive undertaking. The experiment was modelled using published kinetic data, but the calculated time to event differed from that observed to different extents at the two scales. It is hypothesised that the mechanism may change over the prolonged heat soaks and that quantitative scaling is not possible with the available information. Further work is also suggested using a different type of Cook-Off test vehicle, which will in our opinion reduce even further the cost of Cook-Off testing, due to reduction in man-hours of preparation involved and manufacture cost of the Cook-Off test vehicles, and consequently of ranking of explosives.

Thermal dissipation of mechanical energy from periodic loading in energetic materials (EMs) leads to the creation of areas of intense, localized heating, called hot spots. The impact and shock conditions for the hot spot initiation of solid explosives have been extensively explored, but little work has focused on high-frequency contact loading. In order to design formulations to address unintentional initiation by mitigating heating in polymer-bonded explosives (PBXs) and other heterogeneous EMs, the mechanisms of heat generation which lead to the thermal initiation of energetic composites under ultrasonic excitation were explored. Heat generation mechanisms which may lead to unintentional initiation were identified through the diagnostic techniques of second harmonic generation (SHG) of δ-HMX (1,3,5,7-tetranitro-1,3,5,7-tetrazocine) crystals; X-ray phase contrast imaging (PCI) performed at the Argonne National Laboratory Advanced Photon Source; infrared (IR) thermography; and optical microscopy. This work concludes with high-speed mesoscale observations of dense layers of PETN (pentaerythritol tetraniterate), CL-20 (hexanitrohexaazaisowurtzitane), RDX (1,3,5-trinitro-1,3,5-triazine), and HMX which were damaged or driven to decomposition under acoustic insult using the non-intrusive imaging technique of shadowgraphy to detect hot spots within the transparent binder. Recommendations are formed which address binder adhesion, energetic material properties, and particle morphology on the vibration sensitivity of a PBX formulation.

The transformation of mechanical energy into thermal energy within composite energetic materials through various thermomechanical mechanisms is thought to lead to the creation of localized areas of intense heating. The growth of these “hot spots” is responsible for the bulk reaction or decomposition of the energetic material. Understanding the formation and growth of these hot spots has been an active area of research particularly for high-speed impact and shock conditions, but further work remains to be done in particular with respect to hot spot formation due to periodic mechanical excitation. Previous literature has established that many potential thermomechanical mechanisms may act at the interface between the constituent components of a composite energetic material. In order to provide further insight and guidance into the design of safer and more resilient energetic materials, the role of adhesion on hot spot formation for polymer bonded explosives (PBXs), a subset of composite energetic materials, was explored. Single HMX (1,3,5,7-tetranitro-1,3,5,7-tetrazocane) crystals in polymer blocks were subjected to ultrasonic excitation and subsequent heating was captured via infrared thermography. Subsequent testing of HMX PBXs using a drop weight tower captured changes in the sensitivity of the energetic material. Variation of the polymer binder allowed for a range of adhesive and mechanical properties to be examined. These experiments on the role of adhesion under these kinds of excitations provided insight into how mechanical energy is being transformed into localized heating.

The initiation of high explosives (HEs) under shock loading lacks a comprehensive understanding: particularly at the particle scale. One common explanation is hot spot theory, which suggests that energy in the material resulting from the impact event is localized in a small area causing an increase in temperature that can lead to ignition. This study focuses on the response of HMX particles (a common HE) within a polymer matrix (Sylgard-184^®), a simplified example of a polymer bonded explosive (PBX). A light gas gun was used to load the samples at impact velocities ranging from 370 to 520 m/s. The impact events were visualized using X-ray phase contrast imaging (PCI) allowing real-time observation of the impact event. The experiments used three subsets of PBX samples: multiple particle (production grade and single crystal), drilled hole, and milled slot. Evidence of damage and deformation occurred in all of the sample types. While the necessary impact velocity for consistent hot spot formation leading to reactions was not reached, the damage (particularly cracking) that occurred provides a useful indication of where hot spots may occur when higher velocities are reached. With the multiple particle samples, evidence of cracking and debonding occurred throughout. One sample showed significant volume expansion due to possible reaction. The samples containing drilled holes demonstrated the expected pore collapse behavior at these velocities, as well as damage downstream from the holes under various two-hole arrangements. Milled slot samples were tested to simulate existing cracks in the HMX. These samples showed increased damage at the site of the milled slot, as well as unique cracking behavior in one of the samples.

碩士
國防大學中正理工學院
應用化學碩士班
99
In this study, aimed at using quantum mechanical theory, i.e., electronic density functional theory (DFT) B3LYP/6-31G (d,p) in the latest version of Gaussian 09 program, to analyze the inter-molecule hydrogen bonding(or ven der Waals force), bound energy, and coulomb attraction energy between Polydimethylsiloxane (PDMS), Polyethylene glycol (PEG), poly 1,2methylenedioxy-4-propenyl benzene (PISAF), and poly 4-Methyl-5-vinylthiazole (PMV), those are oligomers of stationary phase packing material and usually used in solid-phase microextraction (SPME) or high-performance liquid chromatography (HPLC) to separate or analyze a mixture of compounds, and 11 kinds of explosive molecules respectively (including explosive compound of military explosives octogen (HMX), hexogen (RDX), ethylene glycol dinitrate (EGDN), pentaerythrite tetranitrate (PETN), nitroglycerin (NG), trinitrotoluene (TNT) and its derivatives (2-MNT, 3-MNT, 4-MNT, 2,4-DNT, 2,6-DNT)). Furtherore, the results of our study can be applied in the analysis or separation of explosives.

Detection of explosives has always been a challenging issue all over the world. Different analytical techniques and instrumentation methods have been explored to obtain a 100% fail proof detector. Some technologies have matured and have been deployed in the field already. However, active research is still being pursued to make the ultimate explosive detection device. The present thesis broadly addresses the development of Raman spectroscopy based techniques for the detection of explosives. Although Raman spectroscopy has technologically developed and has become a regular tool for chemical identification, its use in the field of detection of explosives has been limited. Two aspects of detection were addressed in this thesis. The first part consists of the detection of minute quantities or traces of explosives using a Raman based method. In order to approach this problem, surface enhanced Raman spectroscopy (SERS), an offshoot of Raman spectroscopy was explored. Chapters 2-4 deal with developing efficient SERS substrates. In this endeavour, the first and the most obvious choice as SERS substrates were silver (Ag) nanoparticles (NPs). However, we were exploring methods that could be simple one-pot synthesis methods, cost-effective and without employing strong reducing agents (green). Therefore, Ag NPs were synthesized using biosynthetic route. These nanoparticles were used to study their SERS efficiency. Sub-nano molar concentration of dye as well explosive like trinitrotoluene (TNT) and hexanitrohexaazaisowurtzitane (CL-20) could be obtained for both the clove reduced as well as pepper Ag nanoparticles. Hence Ag NPs are very efficient SERS substrates. In the second part of the work on SERS, bimetallic nanoparticles with core-shell (Agcore-Aushell) architecture were synthesized, characterized and tested for SERS activity. After successful synthesis and characterization of the bimetallic nanoparticles, these were tested for their SERS activities using a dye molecule and an explosive molecule. SERS spectra could be obtained for the bimetallic nanoparticles. It was observed that the sensitivity of these NPs were almost at par with the mono-metallic Ag NPs. In order to bring SERS from laboratory to field, a more practical approach was to prepare solid SERS substrates or SERS substrates on solid platform. In the next chapter, we ventured into the most abundant material which forms the backbone of the organic world, carbon. Various carbonaceous materials ranging from chemically synthesized graphene, graphene oxide, multi-walled carbon nanotube (MWCNT), graphite and activated charcoal were explored as potential substrates for surface enhanced Raman spectroscopic applications. The analytes chosen for this particular study were some fluorescent molecules such as rhodamine B (RB), rhodamine 6G (R6G), crystal violet (CV), Nile blue A (NBA) and a non-fluorescent molecule acetaminophen, commonly known as paracetamol. Enhanced Raman signals were observed for the fluorescent molecules, especially for the molecules whose absorbance maxima are near the excitation wavelength of the laser (514.5 nm). The most interesting outcome of this work was obtaining enhanced Raman signals of nanomolar concentration of R6G on activated charcoal. However, for the non-fluorescent molecule, paracetamol, Raman spectra could not be observed beyond -5 10M concentration for all the carbon substrates including chemically synthesized graphene and MWCNT. This study was crucial in our quest for an ideal SERS substrate. Our observations let us to conclude that chemically synthesized graphene was not the only candidate for the preparation of SERS substrates. Since carbon materials efficiently adsorb and also provide a separate channel for energy decay (fluorescence quenching), even activated charcoal could be employed as a SERS platform. However, carbon alone could not provide an effective solution for the preparation of SERS substrates. Therefore, combining the plasmonic effect of the metal nanoparticles with the efficient adsorption and fluorescence quenching of carbon materials would be ideal. In the next part of the carbon studies, graphene-Ag composites which were either prepared by in situ reduction process or physically mixed were studied for SERS activity. An ideal SERS substrate should possess the following properties: (i) Support plasmon, thereby provide SERS enhancement (ii) Easy to fabricate or synthesize (large scale/bulk) (iii) Ensure high reproducibility and sensitivity (iv) Low false alarm from matrix chemicals (v) Cost effective (vi) Solid substrate (in the form of chip, pellet, slide etc.) Hence, as a final study, carbon silver based composites were explored. R6G was chosen as an analyte again and SERS experiments were conducted. Raman signals at low concentration could be obtained for the carbon-Ag composites as well. In addition, feasibility experiments were also conducted for an explosive molecule, FOX-7. From these preliminary experiments we observed that carbon-metal NP composites can be efficient, cost-effective SERS substrates that will overcome the current issue. The previous chapters dealt with the trace detection of explosives. The next part of the thesis deals with the development of the Raman spectroscopic methods for non-invasive detection of concealed objects. Chapters 4 and 5 primarily focus on explosives detection. Spatially offset Raman spectroscopy (SORS) instrumentation was developed in the laboratory for non-invasive detection solid and liquid explosives. Several experiments were carried out to detect concealed materials inside high density polyethylene (HDPE) containers, coloured glass bottles, envelopes etc. with this technique, Raman signals of materials could be retrieved even within 4 mm thick outer-layer. SORS imaging experiments were also performed on bilayered compounds, tablets etc. However, while performing the SORS experiments, it was observed that due to the restriction in geometry imposed by the method, the signals from the inner-layers could be obtained only up to a certain depth. This posed a serious limitation of SORS for practical scenarios, where the thickness of the outer layer may be tens of mm. In such situation, SORS may not be an effective method. We then performed Raman experiments using a transmission geometry using a series of samples. The transmission Raman (TR) experiments yielded better SNR for the inner (concealed) material as compared to the outer material. Although transmission Raman experiments yielded better signal but these experiments were again geometry dependent, hence, less flexible and TR experiments did not provide information about the position of the underlying materials. In order to obtain complete information, it was necessary to understand photon migration in a multiple scattering medium. It is known that a photon in a multiple scattering medium may be approximated to undergo a random-walk. Statistically, the photon that undergoes multiple scattering in a medium loses its sense of origin (direction), hence, there is a finite probability to observe the exiting photon in any direction. Rayleigh and NIR based imaging modalities have been conducted using this model. Diffuse optical tomographic (DOT) measurements also deal with measuring the photons that have exited the sample after undergoing multiple scattering in a turbid medium. If it was possible to collect the Rayleigh photons or the diffuse photons in DOT experiments, in principle, Raman photons could also be collected from several directions. It was then proposed that if Rayleigh scattered photons can exit at 4π solid angle from a sample, then it can be assumed that some Rayleigh photons may convert to Raman photons, which in turn, shall have a finite probability to exit the sample from all the sides (4π solid angles). This idea of collecting Raman photons has never been discussed before! Thus, as expected based on the above principles, we were able to record Raman scattered photons at all angles and on all sides. This new technique has been termed as ‘Universal Multiple Angle Raman Spectroscopy (UMARS)’. Monte Carlo simulation studies were also performed to understand the distribution of photons in a multiple scattering medium. Simulation studies also revealed that Raman photons exited from all sides of the medium at varying percentages. Hence, several fiber optic probes were designed for illumination and collection to perform the UMARS experiments for samples concealed at depths beyond 20 mm. UMARS was not only applied successfully for the detection of concealed explosives, but also for biologically relevant samples as well. In fact a pharmaceutical tablet as thick as 7 mm was also tested with UMARS and signals could be successfully obtained. Since the UMARS signals were obtained from all possible angles, imaging experiments were also conducted to obtain sample specific information. Frequency-specific images of bilayer materials could be obtained. In the case where one material was concealed within another, the reconstruction of the frequency-specific intensities in a contour plot revealed the position of the concealed layer. One of the most challenging and exciting studies that was conducted was to use UMARS to obtain shapes of hidden materials. Several shapes such as dumbbell, ellipsoid etc were fabricated (made of glass) and were filled with a test chemical, trans-stilbene (TS). This shape was placed inside an outer material like ammonium nitrate (AN) that was taken in a glass beaker. The diameter of the beaker was varied from 25 mm to 60 mm. A series of UMARS measurement was carried out with 10 collection fiber optic probes. The spatial resolution (vertical) was varied from 200 μm to 1 mm. Series of UMARS images were obtained which were then processed and the intensity of the individual fibers were averaged (CCD row pixels) based on the image of the individual fiber on the CCD. The frequency specific intensity of the materials was utilized to reconstruct 2D or a 3D shape. The shapes of the objects could be clearly discerned using UMARS imaging. This marks a major step for the development of UMARS as a 3D imaging modality. UMARS experiments conducted so far have affirmed our belief that this technology can be used as an effective technique for screening solid and liquid samples at airports, railway stations and other entry points. 3D imaging for biomedical diagnostics will provide molecular information in addition to the location and shape of an object inside a tissue such as calcified masses and bones. In the final part of the thesis, 2D Raman correlation spectroscopic method was applied to understand the dynamics of a system that was subjected to external perturbation. In the field of explosive processing and formulations, large batches are generally prepared. However, it is very difficult to ascertain the molecular or structural changes that occur during the processing of these formulations in situ. Analytical methods to monitor the changes online are limited. Raman spectroscopy can be an effective technique for such measurements. This process however, generates a large number of spectra. In such cases, it becomes cumbersome to handle such large number of data and obtain meaningful information. 2D correlation spectroscopy can be applied under such situations. 2D correlation analysis generates essentially two maps, synchronous and asynchronous. In this study, 2D Raman correlation spectroscopy was applied to ammonium nitrate that was subjected to temperature variations. 2D maps were constructed to obtain information about the structural changes associated with temperature. The synchronous map reveals the overall similarity of the intensity changes. Whereas, the 2D asynchronous maps provide the sequence of changes that occur. Based on the set of well defined rules proposed by Isao Noda, the synchronous and the asynchronous correlation maps were analysed. Hence, generalized 2D correlation spectroscopy can be extended to any kind of perturbation and will prove useful in understanding the structural dynamics. The objective of the thesis was to explore various facets of Raman spectroscopy that would be useful in the field of high energy materials specifically in the detection of explosives. Attempts were made for the development of trace detection of explosives using Raman based technique, SERS. In addition, bulk detection of concealed explosives was performed non-invasively using SORS and UMARS. In the field of high energy materials, these techniques will find immense applications. Raman spectroscopy, as we saw is a very important technique that can be used as a stand-alone method and can also be interfaced with other analytical or imaging modalities. This treatise is an example where the strength of this powerful spectroscopic method has been explored to some extent.

Sensitivity and selectivity remain the central technical requirement for analytical devices, detectors and sensors. Especially in the gas phase, concentrations of threat substances can be very low (e.g. explosives) or have severe effects on health even at low concentrations (e.g. benzene) while it contains many potential interferents. Preconcentration, facilitated by active or passive sampling of air by an adsorbent, followed by thermal desorption, results in these substances being released in a smaller volume, effectively increasing their concentration. Traditionally, a wide range of adsorbents, such as active carbons or porous polymers, are used for preconcentration. However, many adsorbents either show chemical reactions due to active surfaces, serious water retention or high background emission due to thermal instability. Metal-organic frameworks (MOFs) are a hybrid substance class, composed inorganic and organic building blocks, being a special case of coordination polymers containing pores. They can be tailored for specific applications such as gas storage, separation, catalysis, sensors or drug delivery. This thesis is focused on investigating MOFs for their use in thermal preconcentration for airborne detection systems. A pre-screening method for MOF-adsorbate interactions was developed and applied, namely inverse gas chromatography (iGC). Using this pulse chromatographic method, the interaction of MOFs and molecules from the class of explosives and volatile organic compounds was studied at different temperatures and compared to thermal desorption results. In the first part, it is shown that archetype MOFs (HKUST-1, MIL-53 and Fe-BTC) outperformed the state-of-the-art polymeric adsorbent Tenax® TA in nitromethane preconcentration for a 1000 (later 1) ppm nitromethane source. For HKUST-1, a factor of more than 2000 per g of adsorbent was achieved, about 100 times higher than for Tenax. Thereby, a nitromethane concentration of 1 ppb could be increased to 2 ppm. High enrichment is addressed to the specific interaction of the nitro group as by iGC, which was determined by comparing nitromethane’s free enthalpy of adsorption with the respective saturated alkane. Also, HKUST-1 shows a similar mode of sorption (enthalpy-entropy compensation) for nitro and saturated alkanes. In the second part, benzene of 1 ppm of concentration was enriched with a similar setup, using 2nd generation MOFs, primarily UiO-66 and UiO-67, under dry and humid (50 %rH) conditions using constant sampling times. Not any MOF within the study did surpass the polymeric Tenax in benzene preconcentration. This is most certainly due to low sampling times – while Tenax may be highly saturated after 600 s, MOFs are not. For regular UiO-66, four differently synthesized samples showed a strongly varying behavior for dry and humid enrichment which cannot be completely explained. iGC investigations with regular alkanes and BTEX compounds revealed that confinement factors and dispersive surface energy were different for all UiO-66 samples. Using physicochemical parameters from iGC, no unified hypothesis explaining all variances could be developed. Altogether, it was shown that MOFs can replace or add to state-of-the-art adsorbents for the enrichment of specific analytes with preconcentration being a universal sensitivity-boosting concept for detectors and sensors. Especially with iGC as a powerful screening tool, most suitable MOFs for the respective target analyte can be evaluated. iGC can be used for determining “single point” retention volumes, which translate into partition coefficients for a specific MOF × analyte × temperature combination
Empfindlichkeit und Selektivität bleiben die zentralen technischen Anforderungen an analytische Geräte, Detektoren und Sensoren. Speziell in der Gasphase können die Konzentrationen von Gefahrstoffen sehr niedrig sein (z. B. Explosivstoffe) oder bereits bei niedrigen Konzentrationen schädigende Auswirkungen auf die Gesundheit aufweisen (z. B. Benzol) während sie viele potenzielle Interferenzien enthält. Präkonzentration, die durch aktives oder passives Sampling von Luft durch ein Adsorbens, gefolgt von einer Thermodesorption realisiert wird, setzt diese Substanzen effektiv in einem kleineren Volumen frei, was zu einer Erhöhung der Konzentration führt. Üblicherweise wird hierfür eine breite Auswahl an Adsorbentien wie Aktivkohlen oder poröse Polymere verwendet. Jedoch weisen viele Adsorbentien entweder chemische Reaktionen wegen aktiver Oberflächen, starke Wasserretention oder hohe Hintergrundemission wegen thermischer Instabilität auf. Metal-organic frameworks (MOFs) sind eine hybride Substanzklasse, ein Spezialfall der porösen Koordinationspolymere, die aus anorganischen und organischen Baugruppen aufgebaut sind. Sie können für spezifische Anwendungen wie Gasspeicherung, Trennung, Katalyse, Sensorik oder Wirkstofftransport maßgeschneidert werden. Diese Arbeit befasst sich hauptsächlich mit der Untersuchung von MOFs bei der thermischen Anreicherung für luftgetragene Detektionssysteme. Eine Methode zur schnellen Untersuchung von MOF-Analyt Interaktionen wurde entwickelt und angewendet, die inverse Gaschromatographie (iGC). Mit dieser pulschromatographischen Methode wurde die Interaktion von MOFs und Molekülen aus der Klasse der Explosivstoffe sowie Klasse der flüchtigen organischen Verbindungen (VOCs) in der Gasphase bei verschiedenen Temperaturen untersucht und mit Thermodesorptionsmessungen verglichen. Im ersten Teil der Arbeit würde gezeigt das Modell-MOFs (HKUST-1, MIL-53 und Fe-BTC) den polymeren Standard Tenax® TA beim Anreichern von Nitromethan an einer 1000 (später 1) ppm Nitromethan Quelle übertrafen. Im Fall von HKUST-1 konnte ein Faktor von 2000 pro Gramm erreicht werden, etwa 100-fach höher als für Tenax. Auf diese Weise könnte eine Nitromethan Konzentration von 1 ppb auf 2 ppm erhöht werden. Diese hohen Anreicherungsfaktoren entstammen vermutlich der hohen spezifischen Wechselwirkung der Nitrogruppe mit den MOFs. Diese wurden durch iGC beim Vergleich von Nitromethans freier Adsorptionsenthalpie mit dem entsprechenden gesättigten Alkan ermittelt. HKUST-1 weist auch einen ähnlichen Adsorptionsmodus (Enthalpie-Entropie Kompensation) für Nitro- und gesättigte Alkane auf. Im zweiten Teil der Arbeit wurde die Anreicherung von 1 ppm Benzol, mit einem ähnlichen Aufbau und anderen MOFs, hauptsächlich UiO-66 und UiO-67, unter trockenen und feuchten (50 %rF) Bedingungen bei konstanten Samplingzeiten, untersucht. Hierbei konnte kein MOF das polymere Tenax beim Anreichern von Benzol übertreffen. Dies liegt vermutlich an den niedrigen Samplingzeiten – während Tenax nach 600 s bereits stark gesättigt ist, gilt dies nicht für MOFs. Im Fall von UiO-66 zeigten vier Proben unterschiedlicher Herkunft ein stark unterschiedliches Verhalten bei trockener und feuchter Anreicherung welches nicht vollständig erklärt werden kann. iGC Untersuchungen mit gesättigten Alkanen und BTEX-Verbindungen konnten aufzeigen, dass räumliche Beschränktheitsfaktoren und dispersive Oberflächenenergien für alle vier Proben unterschiedlich waren. Mit physikochemischen Parametern aus iGC-Messungen konnte jedoch keine einheitliche Hypothese zum Unterscheiden der Proben entwickelt werden. Insgesamt konnte gezeigt werden, dass MOFs bestehende Adsorbens-Standards zum Anreichern von bestimmten Analyten ersetzen oder erweitern können, wobei Präkonzentration ein Konzept ist, welches universell die Empfindlichkeit eines Detektors oder Sensors steigern kann. Insbesondere mit iGC als mächtiges Werkzeug zur Vorselektion können passende MOFs für die entsprechenden Zielanalyten evaluiert werden. Ebenso kann iGC auch zur Bestimmung von Einzelpunkt Retentionsvolumen, welche Verteilungskoeffizienten für eine bestimmte MOF × Analyt × Temperatur Kombination entsprechen, genutzt werden

No
A novel dispersive system operating at 1064-nm excitation and coupled with transfer electron InGaAs photocathode and electron bombardment CCD technology has been evaluated for the analysis of drugs of abuse and explosives. By employing near-IR excitation at 1064-nm excitation wavelength has resulted in a significant damping of the fluorescence emission compared to 785-nm wavelength excitation. Spectra of street samples of drugs of abuse and plastic explosives, which usually fluoresce with 785-nm excitation, are readily obtained in situ within seconds through plastic packaging and glass containers using highly innovative detector architecture based upon a transfer electron (TE) photocathode and electron bombarded gain (EB) technology that allowed the detection of NIR radiation at 1064nm without fluorescence interference. This dispersive near-IR Raman system has the potential to be an integral part in the armoury of the forensic analyst as a non-destructive tool for the in-situ analysis of drugs of abuse and explosives. Copyright (c) 2015 John Wiley & Sons, Ltd.