Topical inquiries for the Swedish Defence Research Agency (FOI) include analysis of explosive substances in different sample types. Research into explosives in complex matrixes can provide an analytical support function for forensic investigation i.e. tools for areas such as finding bomb factories, identification and risk analysis of home-made explosives (HME) and improvised explosive devices (IED) as well as preventive measures against maliciously intended use of explosives. Additionally, the research may lay the groundwork for indications of health- and environmental hazards. Utilizing state-of-the-art equipment and years of extensive expertise, FOI is able to carry out these types of research tasks to provide security and sustainability for society. The aim of this thesis project is to establish and validate developed methods for collecting, extracting, separating, and detecting trace amounts of explosives in various bodies of water using a solid-phase extraction (SPE) robot and a high-resolution (HR) mass spectrometer (MS) connected to an ultra-high-performance liquid chromatograph (UHPLC). Particular areas of interest include locations in the Stockholm archipelago where experimental detonations of explosives have taken place. Overall, UHPLC-HRMS analysis provides a powerful tool for analyzing explosives in complex matrixes with unambiguous and reliable measurement data. The compounds of investigation were hexogen (RDX), octogen (HMX), pentyl (PETN), and trotyl (TNT). To summarize, during the course of the thesis, trace amounts of some explosives were detected and quantified in various bodies of water. Furthermore, the applied method for the project was successful in qualitatively and quantitatively analyze the compounds of interest with limit of detection ranging between 0.33–11 μg/L (ppb) in various water sources.

Mesoscale models are needed to predict the effect of changes to the microstructure of plastic-bonded explosives on their shock initiation and detonation behaviour. This thesis describes the considerable progress that has been made towards a mesoscale model for two HMX-based explosives PBX9501 and EDC37. In common with previous work in the literature, the model is implemented in hydrocodes that have been designed for shock physics and detonation modelling. Two relevant physics effects, heat conduction and Arrhenius chemistry, are added to a one-dimensional Lagrangian hydrocode and correction factors are identified to improve total energy conservation. Material models are constructed for the HMX crystals and polymer binders in the explosives, and are validated by comparison to Hugoniot data, Pop-plot data and detonation wave profiles. One and two-dimensional simulations of PBX9501 and EDC37 microstructures are used to investigate the response of the bulk explosive to shock loading. The sensitivity of calculated temperature distributions to uncertainties in the material properties data is determined, and a thermodynamic explanation is given for time-independent features in temperature profiles. Hotspots are widely accepted as being responsible for shock initiation in plastic-bonded explosives. It is demonstrated that, although shock heating of crystals and binder is responsible for temperature localisation, it is not a feasible hotspot mechanism in PBX9501 and EDC37 because the temperatures generated are too low to cause significant chemical reaction in the required timescales. Critical hotspot criteria derived for HMX and the binders compare favourably to earlier studies. The speed of reaction propagation from hotspots into the surrounding explosive is validated by comparison to flame propagation data, and the temperature of the gaseous reaction products is identified as being responsible for negative pressure dependence. Hotspot size, separation and temperature requirements are identified which can be used to eliminate candidate mechanisms in future.

<p>  </p> <p>Polymer bonded explosives (PBX) are a particle reinforced composite containing a high solids loading of explosive particulates bound in a polymer matrix. Commercially produced energetic particulates contain some percentage of flaws in the form of contaminants, porosity, and preexisting fractures. Additional large-scale porosity within the composite is generated during PBX formulation. The introduction of novel additive manufacturing techniques to the energetics field alters the known composite structure and introduces a porosity variable that has not been fully characterized. Porosity collapse during deformation is believed to be a predominant mechanism for hotspot formation, which dominates shock initiation behaviors. These phenomena are difficult to experimentally characterize due to inherent small spectral and temporal scales, and as such numerical and computational models are relied upon to inform fundamental physics. Experimental characterization of the behaviors of energetic materials during deformation is necessary to better inform computational studies and improve our understanding of hotspot formation mechanisms. </p> <p>This dissertation experimentally evaluates the high-rate deformation of porosity in individual explosive particulates and within the overall composite structure. This has included the development of a novel micromachining technique for pore generation in energetic single crystals using the focused ion beam (FIB), resulting in precise and controllable porosity generation that is easily reproducible in collaboration with computational studies. FIB was shown to be an effective pore generation technique, verified by assessing surface roughness and pore quality compared to contemporary manufacturing methods. Three experimental subsets are evaluated: surface cracks in HMX single crystals, polygonal pores in HMX single crystals, and large-scale porosity variations in mock vibration assisted print (VAP) produced composites of borosilicate glass beads and Sylgard 184® binder. A single stage light gas gun was used to impact the samples at 400 m/s and the impact event and resultant material response were observed in real time using x-ray phase contrast imaging (PCI). Machined surface cracks were shown to have negligible effect on the final fracture behaviors of HMX crystals. In polygonal pores fractures were shown to originate due to stress concentration during impact followed by otherwise expected brittle fracture behaviors. For wedge-like pores, the shockwave culminates on the front face of the pore and contributed to early fracture in some samples as well as a consistent open fracture opposite the impact along the shockwave direction in later stages of impact. For the blunt rectangular-like pores two differing behaviors were observed, wherein either the pore condensed and fracture at the pore was not seen during the impact event or large open fractures formed at the pore corners opposite the shockwave. The variance in response is attributed to the energy of fracture dissipating somewhere else in the material bulk, like the behaviors observed in the milled slot samples. Finally, additively manufactured PBX deformation behaviors were observed to be dominated by the collapse of the existing ordered porosity in the bulk which occurred at an increased rate relative to the bulk material compression. This resulted in a three-stage progression of deformation, consisting of a rapid collapse of large-scale ordered porosity, followed by the densification of the remaining features, and ultimately ending in compaction of the bulk as the impact projectile fully compressed the samples. Future work includes exploration of further FIB produced pore effects on dynamic fractures, evaluation of printed material deformation behaviors at additional rates, as well as application and evaluation of additional VAP printed material formulations.  </p>