An investigation is presented of the behavior of time-reversal focusing in soils. Initial numerical models demonstrate time-reversal focusing to be effective in elastic media, including when a large number of scattering objects were present in the medium. When scattering objects are present, time-reversal focusing demonstrates superior focusing ability when compared to other excitation methods such as uniform excitation or time-delay focusing. Multiple experimental investigations of experimental time-reversal focusing performed in sand evaluate time-reversal focusing effectiveness when multiple near-surface scattering objects are present in the medium. Experimental results demonstrate that time-reversal focusing is effective in the experimental context as well as the numerical models. Further experiments examine time-reversal focusing in more extreme cases where the entire ballistic wave is blocked, and the only energy reaching the focus point is reflected from scattering objects in the medium. A comparison to other focusing methods demonstrates that under these conditions, most focusing attempts with traditional methods will fail completely while time-reversal focusing does not. Additional configurations of time-reversal focusing examine its effectiveness when scattering is caused by an asymmetrical surface layers. The impact of an asymmetrical or non-uniform excitation array is also examined for time-reversal focusing in the presence of scattering objects. An investigation of the effects of scattering object geometry on focusing resolution in time-reversal focusing is also presented. Scattering object field density is found to have a strong, but diminishing effect on focusing resolution as the scattering object field density increased. Loss of surface wave energy available for focusing due to mode-conversion is found to be correlated with the density of the scattering object field. The impact of the weak non-linear nature of the soil on time-reversal focusing is examined through a study of time-reversal focusing behavior for a variety of amplitudes that generate different levels of non-linearity in the soil. This study of nonlinearity is coupled with a study of the impact of noise on time-reversal focusing. It appears that both non-linearity and noise have an impact on time-reversal focusing effectiveness. Further, the loss from these mechanisms seems to be interrelated. Noise seems to enhance non-linear loss in the soil.

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.

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.

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

Dissertation submitted in fulfilment of the requirements for the Masters Degree in Technology: Chemical Engineering in the Department of Chemical Engineering of Cape Peninsula University ofTechnology, 2005 / The emulsion used for this study is a new thermodynamically unstable multi-component waterin- oil (w/o) explosive type with an internal phase ratio of approximately 94%, i.e. far beyond the close packing limit of spherical droplets of 74%. Economic considerations and the ongoing need for continuous drilling, loading and blasting in the mining industry, has made long-distance pipeline transportation of these emulsion explosive systems a viable economic option. Presently, rheological characterization of emulsion explosives is well documented (Bampfield & Cooper, 1988, Utracki, 1980). However, very little or none has been done for this system, pertaining to the use of rheometry for prediction of pumping characteristics of these systems in long-distance pipeline transport. This Master's dissertation is devoted to develop rheological methods of testing, characterization and correlation in order to develop a basis for predicting the pumping characteristics of highly concentrated w/o emulsion explosives from rheometry. The literature and theory pertinent to the pipeline flow of high internal phase ratio emulsion explosives are presented, as well as the fundamentals of both concentric cylinder rheometry and pipe viscometry. The most relevant is the work of Bampfield and Cooper (1988), Utracki (1980) and Pal (1990). Two experimental test facilities were used for data collection. Pipeline experiments were done using an experimental test facility at African Explosives Limited (AEL), and rheometry was conducted at the Rheology Laboratory of the Cape Peninsula University of Technology Flow Process Research Centre. The AEL experimental test facility consisted of a four-stage Orbit progressive cavity pump, two fluid reservoirs, (a mixing tank and a discharge reservoir), five 45m HOPE (high density polyethylene) pipes of internal diameters of 35.9 mm, 48.1 mm, 55.9 mm, 65.9 mm and 77.6 mm pipes. The test work was done over a wide range of laminar flow rates ranging from 3 kg.min-I to 53 kg.min-I . Rheometry was done using a PaarPhysica MCR300 rheometer, and only standard rotational tests (i.e. flow curve) at 30 °c in controlled rate mode were done. Rheological characterisation was done using three rheological models, i.e. the Herschel-Bulkley, the Power Law and the Simplified Cross models. The coefficients obtained from these models were then used to predict pumping characteristics. The performances of these models were then evaluated by comparing the pipeline flow prediction to the actual pipeline data obtained from pipeline test experiments. It was found that the flow behaviour depicted by this explosive emulsion system was strongly non-Newtonian, and was characterized by two distinct regions of deformation behaviour, a lower Newtonian region of deformation behaviour in the shear rate region lower than 0.001 S-I and a strong shear thinning region in the shear rate range greater than 0.001 S-l. For all the models used for this study, it was evident that rheometry predicts the pumping characteristics of this high internal phase ratio emulsion reasonably well, irrespective of the choice of the model used for the predictions. It was also seen that the major difference between these models was in the lower shear rate domain. However, the Simplified Cross model was preferred over the other two models, since its parameter (the zero shear viscosity denoted by 110) can in general be correlated to the structure of the emulsion systems (i.e. mean droplet size, bulk modulus, etc.). Thus, structural changes induced by shearing (either inside the pump or when flowing inside a pipe) can be detected from changes in the value of the 110. The above statement implies that Tlo can be used as a quality control measure. Different pumping speeds were found to cause different degrees of shear-induced structural changes which were manifested by two opposing processes. These two opposing processes were the simultaneous coalescence and flocculation of droplets encountered at low rates of shear, and the simultaneous refinement and deflocculation of droplets encountered at high rates of shear. These two droplet phenomena were associated with a decrease or an increase in viscous effects, leading to both lower and higher viscous stresses and pumping pressures during pump start-up respectively.

Thesis (MTech (Business Administration))--Cape Peninsula University of Technology, 2005 / After 1994, when South African was welcomed back into the world economy, companies had to deal with increased international competition, not only on the traditional local markets, but also on the competitive global market. This trend is also applicable to the South African Explosives Industry, Companies in the South African Explosives Indusrty must therefore ensure operational excellence and manufacture products that confonm to world class standards, Superior product quality is becoming increasingly important as a decision-making criterion in the global explosives market, which implies a high demand on bringing products faster to the market at a lower cost. To place world class products on the market, the challenge for companies like Somchem, a division of Denel (pty) Ltd, is to adopt a manufacturing perfonmance model that ensures compliance to world class manufacturing standards, This research study evaluates different successful manufacturing models, and provides a benchmark for the current manufacturing model utilised by Somchem - Denel as evaluated against these models. The result of a gap analysis undertaken between the manufacturing performance at Somchem and the world class manufacturing standards is provided with a recommended strategy to reduce this gap in order to ensure compliance with these world class manufacturing standards. An internal and external benchmark exercise was performed, The internal benchmark was based on the perception of the internal customers using the rapid plant assessment technique. The external benchmark was conducted with the practical programme for revolutions in factories (PPORF) technique. An analysis of the results of both exercises was conducted so as to recommend amendments to the existing manufacturing model at Somchem - Denel so as to ensure that world class manufacturing standards would be attained in a reasonably short period namely three (3) years

Que ce soit lors de la prévention d'actes malveillants ou l'expertise post-attentat, les techniques de prélèvement par frottis et d'analyse d'explosifs se doivent d'être à la fois fiables et sensibles. La méthode par chromatographie en phase liquide (HPLC) couplée à la spectrométrie de masse (MS) présente les caractéristiques requises mais nécessite une étape importante de préparation de l'échantillon et un temps d'analyse conséquent. L'évaluation des performances du couplage HPLC-MS pour l'analyse de frottis réalisés sur des matrices textiles et le développement d'une méthode d'analyse directe et quasi-instantanée de la surface de l'échantillon constituent l'objet de ce mémoire. Pour ce second objectif, les sources d'ionisation ambiante DESI et DART, couplées à la spectrométrie de masse haute résolution (HRMS) ont été utilisées. Une part importante de ce travail a été consacrée à l'étude des mécanismes CID des explosifs, lors de laquelle la HRMS a montré tout son intérêt. Si l'utilisation de la source DESI est plus délicate pour l'étude des surfaces textiles hydrophiles et absorbantes, le potentiel qualitatif de la source DART a été démontré avec succès sur des échantillons simulés et réels. Des résultats prometteurs illustrent la validité de cette approche analytique à la fois sensible, rapide et facile à mettre en ¿uvre, et encouragent à poursuivre les travaux vers une analyse quantitative. / Swabbing and analysis protocols for trace explosives detection have to be both reliable and sensitive, either for prevention measures against bomb attacks or for post-blast scene investigations. The coupling of mass spectrometry (MS) with liquid chromatography (HPLC) offers the required features but important sample preparation steps are often needed and chromatographic separations can require long run times. The evaluation of an LC-MS coupling for the analysis of fabric swabs and the development of a direct and nearly instantaneous method for sample surface analysis are the subjects of this dissertation. DESI and DART ion sources coupled with high resolution mass spectrometry (HRMS) were used for this second method. Part of this work was devoted to the study of CID mechanisms of explosives, in which HRMS appears to present a great interest. Even though the use of DESI source for hydrophilic and absorbent fabric samples analysis is tricky, DART source was successfully applied to qualitative analysis of simulated as well as real samples. Very promising results strengthen the relevance of this direct approach both sensitive, rapid and easily implementable, and encourage pursuing the studies toward quantitative analysis. Keywords: Forensic, explosives, fabrics, extraction, high resolution mass spectrometry, ESI, ambient ionization/desorption (DESI, DART), CID mechanisms, negative ions.

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

Improvised explosives may be based on smokeless gunpowder, fertilizers, or inorganic oxidizers such as nitrate (NO3-), chlorate (ClO3-), and perchlorate (ClO4-) salts. Identification is a priority for the military and law enforcement but due to their varying physical properties and complexity, identification can be challenging. Consequently, three methods have been developed to aid in presumptive and confirmatory detection. Smokeless powder contains plasticizers, stabilizers, dyes, opacifiers, flash suppressants, and other compounds. Identification of these additives can narrow down or identify the brands of smokeless powder used in a device. Fourteen organic smokeless powder components were identified by capillary electrochromatography (CEC) using a hexyl acrylate monolithic stationary phase coupled to UV detection and time-of-flight mass spectrometry (TOF-MS). The CEC-UV method efficiently detects all 14 organic components, while TOF-MS provides sensitivity and selectivity. A mixed smokeless powder component standard was analyzed and the composition of the additive package in commercial smokeless powders determined. Detection limits ranged from 1.0 – 3.2 μg/ml and analysis time was 18 minutes. Second, a procedure for the detection of urea nitrate (UN) and ammonium nitrate (AN) by infusion electrospray ionization - mass spectrometry (ESI-MS/MS) was developed. Solubility tests were performed to find a solvent for both UN and AN that did not cause UN to dissociate. Two adduct ions were detected for each explosive: for AN, m/z 178 [2AN+NH4]+ and m/z 258 [3AN+NH4]+ ions, and for UN m/z 185 [UN+NO3]− and m/z 248 [UN+HNO3+NO3]−. Specificity of the analysis was examined by mixing the explosives with various salts and interferents. Gas-phase adduct ions were useful in distinguishing between ion pairs and mixed salts. Finally, a paper microfluidic device (PMD) was developed as a presumptive test using colorimetric reagents for the detection of ions associated with improvised explosives. The device was configured to test for nitrate (NO3-), nitrite (NO2-), chlorate (ClO3-), perchlorate (ClO4-), and urea nitrate (UN). Proof of concept was performed using extracts of soil containing inorganic oxidizers. The development of these analytical methods allows the detection of smokeless powder components, fertilizers, and oxidizers and expands the suite of analytical methods available for the analysis of improvised explosives.

This dissertation utilized electrospray ion mobility mass spectrometry (ESI-IMS-MS) to develop methods necessary for the separation of chiral compounds of forensic interest. The compounds separated included ephedrines and pseudoephedrines, that occur as impurities in confiscated amphetamine type substances (ATS) in an effort to determine the origin of these substances. The ESI-IMS-MS technique proved to be faster and more cost effective than traditional chromatographic methods currently used to conduct chiral separations such as gas and liquid chromatography. Both mass spectrometric and computational analysis revealed the separation mechanism of these chiral interactions allowing for further development to separate other chiral compounds by IMS. Successful separation of chiral compounds was achieved utilizing a variety of modifiers injected into the IMS drift tube. It was found that the modifiers themselves did not need to be chiral in nature and that achiral modifiers were sufficient in performing the required separations. The ESI-IMS-MS technique was also used to detect thermally labile compounds which are commonly found in explosive substances. The methods developed provided mass spectrometric identification of the type of ionic species being detected from explosive analytes as well as the appropriate solvent that enhances detection of these analytes in either the negative or positive ion mode. An application of the developed technique was applied to the analysis of a variety of low explosive smokeless powder samples. It was found that the developed ESI-IMS-MS technique not only detected the components of the smokeless powders, but also provided data that allowed the classification of the analyzed smokeless powders by manufacturer or make.