Recently there has been interest in determining what happens to the human brain during a traumatic brain injury (TBI). The blast wave created by explosive devices, such as landmines, is one of the most common causes of TBI. The purpose of this study is to investigate the link between an explosion and a cells reaction to a blast wave on a time scale of a few hours. Three different types of cells were tested by pressure waves exposure, fibroblasts (3T3), epithelial cervical cancer (HeLa), and canine epithelial kidney cells (MDCK). Fluorescent images of the cells before and after pressure wave exposure were used to determine how much damage cells have suffered. 3T3 cells showed the most cellular modification while HeLa and MDCK were more resilient. A simple scaling model is proposed to relate the cellular modification to the shock strength.

Recently, the use of thermite-based pressure waves for applications in cellular transfection and drug delivery have shown significant improvements over previous technologies. In the present study, a new technique for producing thermite-generated pressure pulses using fully-dense nano-scale thermite mixtures was evaluated. This was accomplished by evaluation of a stoichiometric mixture of aluminium (Al) and copper(II)-oxide (CuO) prepared by mechanical alloying. Flame propagation speeds, constant-volume pressure characteristics and underwater pressure characteristics of both a micron-scale and mechanically alloyed mixture were measured experimentally and compared with conventional nano-scale thermites. It was determined that mechanically alloyed mixtures are capable of attaining flame propagation speeds on the same order as nano-scale mixtures, with flame speeds reaching as high as approximately 100 m/s. Constant-volume pressure experiments indicated that mechanically alloyed mixtures result in lower pressurization rates compared with conventional nano-scale mixtures, however, an improvement by as much as an order of magnitude was achieved compared with micron-scale mixtures. Thermochemical equilibrium predictions for pressures observed in constant-volume reactions were found to capture relatively well the equilibrium pressure for both low and high values of relative density. Generally, the predictions over-estimated the measured pressures by approximately 60%. Results from underwater experiments indicated that the mechanically alloyed samples produced peak shock pressures and waveforms similar to those for a nano-scale Al-Bi2O3 mixture reported by Apperson et al. (2008). In an effort to model the pressure signal obtained from the underwater reaction, calculations were performed based on the rate of expansion of the high pressure gas sphere. Predicted pressures were found to agree fairly well in terms of both the peak pressure and pressurization rate. The present study has thus identified the ability for mechanically alloyed thermite mixtures to produce underwater pressure profiles that may be conducive for applications in cellular transfection and drug delivery. Récemment, l'utilisation d'ondes de pression produite par des mélanges de thermite pour des applications dans la transfection cellulaire et l'administration de médicaments ont démontré des améliorations importantes par rapport aux technologies précédentes. Dans l'étude ci jointe, une nouvelle technique pour produire des impulsions de pression générée par un mélange thermite, soumit a de l'alliage mécanique, a été évaluée. Ceci a été accompli par l'évaluation d'un mélange stoechiométrique d' aluminium (Al) et de l'oxyde de cuivre(II) (CuO), préparé par mécanosynthèse. Les vitesses de propagation de la flamme, les caractéristiques de pression pour la combustion à volume constant et les caractéristiques de pression pour la combustion sous l'eau ont été mesurées expérimentalement et comparés avec les thermites conventionnel à l'échelle nano. Nous avons déterminé que les mélanges alliés mécaniquement sont capables d'atteindre des vitesses de propagation de flamme du même ordre que les mélanges à l'échelle nanométrique, atteignant jusqu'à environ 100 m/s. Les expériences de combusition à volume constant, indique que les mélanges alliés mécaniquement induit des taux de pressurisation inférieures à celles des mélanges de nano-échelle conventionnel, cependant, une amélioration de près d'un ordre de grandeur a été atteint par rapport aux mélanges d'échelle micronique. Prédictions thermochimiques des pression de compbustion se sont révélés capable de relativement bien saisir les valeurs observées dans les expériences à volume constant. En règle générale, les prévisions sur-estimé les pressions mesurées par environ 60%. Les résultats des expériences sous-marines ont indiqué que les échantillons alliés mécaniquement ont produit des pressions et des profils d'onde similaires à celles produit par un mélange de Al-Bi2O3 de nano-échelle, comme indiqué par Apperson et al. (2008). Pour modéliser les pressions obtenues dans les expériences sous-marines, des calculs basés sur le taux d'expansion de la bulle de gaz à haute pression ont été obtenus. Les pressions prédites ont été trouvés d'être relativement en accord avec la pression maximale et le taux de pressurisation observé. Cette étude a ainsi identifié la possibilité pour l'utilisation des mélanges de thermites alliés mécaniquement pour produire des profils de pression sous l'eau propices pour des applications de transfection cellulaire et l'administration de médicaments.

Ce travail de thèse porte sur la compréhension et la modélisation de la combustion de mélange de nanoparticules composée d'aluminium et d'oxydes métallique. Dans ce cadre, nous avons développé un modèle cinétique, reposant sur un ensemble de phénomènes élémentaires : diffusion, réactions, condensations, évaporations et décompositions. Nous avons montré que ce modèle permet de prédire l'évolution de la pression généré en fonction de nombreux paramètres : la compaction, la proportion d'aluminium et d'oxyde métallique et la taille des particules du mélange. Enfin, ce modèle a été couplé à une description des transferts thermiques lors de la combustion, afin d'étudier l'effet des pertes thermiques dans une chambre de combustion. / This thesis work deals with understanding and modeling the combustion of a mixture of nanoparticle made of aluminum and metal oxide. In this context, we developed a kinetic model, based on multiple elementary phenomena : diffusion, reaction, condensation, vaporization and decomposition. We showed that this model allows to predict the evolution of the pressure generated during the combustion as a function of multiple parameters : packing, proportion of aluminum and metal oxide, and particle sizes. Finally, this model have been coupled with a description of the thermal transport, in order to study the effect of heat losses in a combustion chamber.

The ignition temperature of the aluminium copper oxide (Al-CuO) thermite was measured using differential thermal analysis (DTA) at a scan rate of 50 °C/min in an inert nitrogen atmosphere. Thermite reactions are difficult to start as they require very high temperatures for ignition, e.g. for the Al-CuO thermite comprising micron particles it is ca. 940 °C. It was found that the ignition temperature is significantly reduced when the binary Si-Bi2O3 system is used as sensitiser. Further improvement is achieved when nano-sized particles are used. For the composition CuO + Al + Bi2O3 + Si (65.5:14.5:16:4 wt %), when all components except the aluminium fuel are nano-sized, the observed ignition temperature is reduced to ca. 615 °C and results in a thermal runaway. / Dissertation (MSc)--University of Pretoria, 2011. / Chemical Engineering / unrestricted

Recently, the use of thermite-based pressure waves for applications in cellular transfection and drug delivery have shown significant improvements over previous technologies. In the present study, a new technique for producing thermite-generated pressure pulses using fully-dense nano-scale thermite mixtures was evaluated. This was accomplished by evaluation of a stoichiometric mixture of aluminium (Al) and copper(II)-oxide (CuO) prepared by mechanical alloying. Flame propagation speeds, constant-volume pressure characteristics and underwater pressure characteristics of both a micron-scale and mechanically alloyed mixture were measured experimentally and compared with conventional nano-scale thermites. It was determined that mechanically alloyed mixtures are capable of attaining flame propagation speeds on the same order as nano-scale mixtures, with flame speeds reaching as high as approximately 100 m/s. Constant-volume pressure experiments indicated that mechanically alloyed mixtures result in lower pressurization rates compared with conventional nano-scale mixtures, however, an improvement by as much as an order of magnitude was achieved compared with micron-scale mixtures. Thermochemical equilibrium predictions for pressures observed in constant-volume reactions were found to capture relatively well the equilibrium pressure for both low and high values of relative density. Generally, the predictions over-estimated the measured pressures by approximately 60%. Results from underwater experiments indicated that the mechanically alloyed samples produced peak shock pressures and waveforms similar to those for a nano-scale Al-Bi2O3 mixture reported by Apperson et al. (2008). In an effort to model the pressure signal obtained from the underwater reaction, calculations were performed based on the rate of expansion of the high pressure gas sphere. Predicted pressures were found to agree fairly well in terms of both the peak pressure and pressurization rate. The present study has thus identified the ability for mechanically alloyed thermite mixtures to produce underwater pressure profiles that may be conducive for applications in cellular transfection and drug delivery. Récemment, l'utilisation d'ondes de pression produite par des mélanges de thermite pour des applications dans la transfection cellulaire et l'administration de médicaments ont démontré des améliorations importantes par rapport aux technologies précédentes. Dans l'étude ci jointe, une nouvelle technique pour produire des impulsions de pression générée par un mélange thermite, soumit a de l'alliage mécanique, a été évaluée. Ceci a été accompli par l'évaluation d'un mélange stoechiométrique d' aluminium (Al) et de l'oxyde de cuivre(II) (CuO), préparé par mécanosynthèse. Les vitesses de propagation de la flamme, les caractéristiques de pression pour la combustion à volume constant et les caractéristiques de pression pour la combustion sous l'eau ont été mesurées expérimentalement et comparés avec les thermites conventionnel à l'échelle nano. Nous avons déterminé que les mélanges alliés mécaniquement sont capables d'atteindre des vitesses de propagation de flamme du même ordre que les mélanges à l'échelle nanométrique, atteignant jusqu'à environ 100 m/s. Les expériences de combusition à volume constant, indique que les mélanges alliés mécaniquement induit des taux de pressurisation inférieures à celles des mélanges de nano-échelle conventionnel, cependant, une amélioration de près d'un ordre de grandeur a été atteint par rapport aux mélanges d'échelle micronique. Prédictions thermochimiques des pression de compbustion se sont révélés capable de relativement bien saisir les valeurs observées dans les expériences à volume constant. En règle générale, les prévisions sur-estimé les pressions mesurées par environ 60%. Les résultats des expériences sous-marines ont indiqué que les échantillons alliés mécaniquement ont produit des pressions et des profils d'onde similaires à celles produit par un mélange de Al-Bi2O3 de nano-échelle, comme indiqué par Apperson et al. (2008). Pour modéliser les pressions obtenues dans les expériences sous-marines, des calculs basés sur le taux d'expansion de la bulle de gaz à haute pression ont été obtenus. Les pressions prédites ont été trouvés d'être relativement en accord avec la pression maximale et le taux de pressurisation observé. Cette étude a ainsi identifié la possibilité pour l'utilisation des mélanges de thermites alliés mécaniquement pour produire des profils de pression sous l'eau propices pour des applications de transfection cellulaire et l'administration de médicaments.

The energetics of cast calcium sulfate dihydrate-aluminium thermites was explored and its use as a potential metal-cutting tool was investigated. Thermite is a pyrotechnic composition that undergoes a highly exothermic reaction that burns relatively slowly. It is often used in cutting, welding and incendiary devices. Consolidation of thermite by casting was chosen to enable control of the burning front. The base case thermite comprised 60 wt-% calcium sulfate dihydrate oxidiser and 40 wt-% aluminium fuel. Addition of additives were considered for their effect on the cast thermite’s setting time, density, surface temperature, reaction products and burn rate. EKVI and FactSage thermodynamic simulations were used to determine optimum compositions for the various systems. The thermite powder compositions were sieved before mixing with water and casting in a mould. The casts were allowed to set for 3 days to form calcium sulfate dihydrate-aluminium compositions. The copper sulfate pentahydrate additive was found to significantly decrease the setting time of the casts. The heat of hydration of the base case was 59 ± 8 J g−1 . The compressive strength reached 2.9 ± 0.2 MPa, the open air burn rate was 12.0 ± 1.6 mm s −1 and a maximum surface temperature of 1370 ± 64 °C was recorded using a pyrometer. Bomb calorimetry indicated an energy output of 7.96 ± 1.07 MJ kg−1 , slightly lower than predicted by the EKVI simulation. The density of the castings was varied by either adding hollow sodium borosilicate glass spheres or by adding excess water. The glass spheres resulted in a burn rate that decreased nonlinearly with decreasing cast density. The excess water made no changes to the burning, except for increasing the burn rate of the copper sulfate pentahydrate-based thermite. Calcium sulfate in the casts was also dehydrated by thermal treatments at 155 °C and 200 °C. This resulted in significant increases in the burn rate due to the porosity created by the evaporation of the hydration waters. Castings that were thermally treated in an oven at 155 °C were successful in puncturing part of an aluminium block in confined burn tests. A hole with a diameter of ~13.6 mm and depth of ~7 mm was produced. It is recommended that the composition with copper sulfate pentahydrate be used as a binder in further tests. / Dissertation (MEng)--University of Pretoria, 2018. / Chemical Engineering / MEng / Unrestricted

The stoichiometric Self-propagating High-temperature Synthesis (SHS) thermite reaction involving magnesium oxide (MgO), titanium dioxide (TiO₂), and boron oxide (B₂O₃) forms titanium diboride (TiB₂) and MgO as final products. Selective acid leaching is used to remove the MgO leaving high purity TiB₂ powder. The SHS method to produce TiB₂ is attractive because of the relatively low temperature required to initiate the reaction, fast reaction time, and product purity. This study investigates the acid leaching of SHS produced MgO/TiB2 and a stoichiometric mixture of commercial MgO and TiB₂ powders. Leaching was conducted at 90° C, 60° C, and 30° C at pH levels of 4.0, 2.5, and 1.0 by introduction of concentrated aliquots of HNO₃. This method maintains a minimum pH target throughout the leaching process, thereby sustaining a dynamic concentration to remove the oxide. The optimal leaching conditions were determined to be at 90° C at a minimum pH target of 2.5 for the SHS produced product. At these conditions, conversion percentages of 83%-84% of MgO were measured with only trace amounts of TiB2 measured in the solution (less than 100 ppm). Conversion percentages for each leaching condition and dissolution mass of solid MgO and TiB₂ at each pH are also reported. Results from powder XRD confirm the removal of MgO and minimal dissolution of TiB₂, and indicate the formation of unidentified compounds. Inductively coupled plasma mass spectrometry (ICP) was used to analyze the ionic composition and extent of leaching. Scanning electron microscopy (SEM) was used to observe the particle morphology of the leached powders. / Master of Science

The worldwide preferred method for rail joining is welding; flash butt welding (FBW) and thermite welding (TW) are the two main welding methods used for joining continuous welded rail (CWR) tracks. However, the welds still represent a discontinuity in the track structure due to variations in microstructure, mechanical properties and residual stress levels with respect to the parent rail. These variations can play significant roles in increasing the risk of weld failure under service conditions. In order to better understand how FBW parameters affect these variations, the two main parameters; number of preheating cycles and upsetting forces were varied in three 56E1 rail welds, welded by a stationary FBW machine. Besides, these variations were systematically compared with those that occur in a standard thermite 60E2 rail weld. The thermite weld showed a heat affected zone (HAZ) extent much greater than those measured in the flash butt welds. The flash butt rail weld with a greater upsetting force (Standard Crushed) showed a HAZ extent larger than those in the other two welds (Standard Uncrushed and Narrow-HAZ Crushed), while the weld with fewer preheating cycles (Narrow-HAZ Crushed) showed a smaller extent of the HAZ.All welds showed pearlite colonies with proeutectoid ferrite at the prior austenite grain boundaries in the weld centre, and in the thermite weld zone. The rest zones across the welds exhibited almost fully pearlitic microstructures, but the pearlite at nearly the visible HAZ extents was partially spheroidised. The partially spheroidization zone had the minimum hardness across each of the thermite and flash butt welds. The Narrow-HAZ Crushed weld showed hardness in the weld centre, on average, higher than that of the parent metal. Moreover, the averaged hardness levels in this weld were significantly higher than those in the other two welds. However, these levels in the Standard Crushed weld were slightly lower than those in the Standard Uncrushed weld. Although the visible HAZ extent coincided with the point of minimum hardness, the residual stresses arising from the welds seem to extend much further. Contour Method and laboratory X-ray diffraction techniques were used together to measure the residual stress components across the thermite and flash butt rail welds. The longitudinal residual stress distribution showed tension in the web region along with compression in the head and foot regions of the rail welds. The vertical stress distribution across the flash butt welds was generally similar, and the maximum tensile stress values were comparable to those in the longitudinal direction. While the maximum values of the longitudinal tensile stress increased with decreasing the HAZ widths, these values in the vertical direction were significantly unaffected. However, the longitudinal and vertical tensile residual stresses typically promote the vertical straight-break and horizontal split web failure modes respectively.

This dissertation focuses on developing a predictive method for determining the dynamic densification behavior of thermite powder mixtures consisting of equivolumetric mixtures of Ta + Fe₂O₃ and Ta + Bi₂O₃. Of primary importance to these highly reactive powder mixtures is the ability to characterize the stress at which full compaction occurs, the crush strength, which can significantly influence the stress required to initiate reaction during dynamic or impact loading. Examined specifically are the quasi-static and dynamic compaction responses of these mixtures. Experimentally obtained compaction responses in the quasi-static regime are analyzed using available compaction models, and an analysis technique is developed that allows for a correct measurement of the apparent yield strength of the powder mixtures. The correctly determined apparent yield strength is combined with an equation of state to yield a prediction of the shock densification response, including the dynamic crush strength of the thermite powder mixtures. The validated approach is also extended to the Al + Fe₂O₃ thermite system. It is found that accurate predictions of the crush strength can be obtained through determination of the apparent yield strength of the powder mixture when incorporated into the equation of state. It is observed that the predictive ability in the incomplete compaction region is configurationally dependent for highly heterogeneous thermite powder systems, which is in turn influenced by particle morphology and differences in intrinsic properties of constituents (density, strength, etc.).

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.