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.

<div>This work investigates several uses of additive manufacturing to meet modern security-related needs. All energetic materials when integrated in a practical system require an ignition device, e.g. a bridgewire or spark gap igniter, which is traditionally fabricated from metal components. A conductive polymer, polyaniline,</div><div>was chosen to create metal-free spark gap igniters in a process that lends itself well to large-scale manufacturing. The igniters proved consistent in terms of breakdown</div><div>voltage, as well as their effectiveness in igniting nanothermite, a representative energetic material. This work also establishes a simple and effective approach suitable for the precise material deposition of CL-20. This is relevant for the development of trace detection calibration standards. This work shows that CL-20 is compatible with inkjet</div><div>printing for this purpose. Furthermore, the need to secure sensitive information that is stored locally on electronic devices led to the study of the use of confined nanothermite to damage substrates used in electronics. The maximum thickness of PCB that permitted destruction with repeatable results was investigated o suggest a baseline for future system integration and production. In addition, the stress of the board was modeled using measured thrust data. In brief, this work has proven that the use of additive manufacturing with energetic materials is both a possible and effective means to secure devices, should a device containing sensitive material be unintentionally misplaced.</div>

<div>Understanding the fundamental physics involved in the high strain rate deformation of high explosives (HE) is critical for developing more efficient, reliable, and safer energetic materials. When HE are impacted at high velocities, several thermo-mechanical processes are activated, which are responsible for the ignition of these materials. These processes occur at different time and length scales, some of them inaccessible by experimentation. Therefore, computational modeling is an excellent alternative to study multiscale phenomena responsible for the ignition and initiation of HE. This thesis aims to develop a continuum model of HMX to study the anisotropic behavior of HE at the mesoscale, including fracture evolution and plastic deformation. This thesis focus on three types of simulations. First, we investigate dynamic fracture and hotspot formation in HMX particles embedded in Sylgard binder undergoing high strain rate compression and harmonic excitation. We use the phase field damage model (PFDM) to simulate dynamic fracture. Also, we implement a thermal model to capture temperature increase due to fracture dissipation and friction at both cracks and debonded HMX/Sylgard interface. In our simulations, we observe that crack patterns are strongly dominated by initial defects such as pre-existing cracks and interface debonding. Regions with initial debonding between HMX particles and the polymer are critical sites where cracks nucleate and propagate. Heating due to friction generates in these regions too and caused the formation of critical hotspots. We also run simulations of a HMX particle under high-frequency harmonic excitation. As expected, higher frequencies and larger amplitudes lead to an increase in the damage growth rate. The simulations suggest that the intensity of the thermal localization can be controlled more readily by modifying the bonding properties between the particle and the binder rather than reducing the content of bulk defects in the particle. </div><div><br></div><div>Second, we present simulations of shock compression in HMX single crystals. For this purpose, we implemented a constitutive model that simulates the elastoplastic anisotropic response of this type of material. The continuum model includes a rate-dependent crystal plasticity model and the Mie-Gruneisen equation of state to obtain the pressure due to shock. Temperature evolves in the material due to plastic dissipation, shock, and thermo-elastic coupling. The model is calibrated with non-reactive atomistic simulations to make sure the model obeys the Rankine-Hugoniot jump conditions. We compare finite element (FE) and molecular dynamic (MD) simulations to study the formation of hot spots during the collapse of nano-size void in a HMX energetic crystal. The FE simulations captured the transition from viscoelastic collapse for relatively weak shocks to a hydrodynamic regime for strong shocks. The overall temperature distributions and the rate of pore collapse are similar to MD simulations. We observe that the void collapse rate and temperature field are strongly dependent on the plasticity model, and we quantify these effects. We also studied the collapse of a micron size void in HMX impacted at different crystal orientations and impact velocities. The simulation results of void collapse are in good agreement with a gas gun void collapse experiment. While the void size and crystal orientation do not affect the area ratio rate, they strongly affect the void collapse regime and temperature. Also, increased plastic activity when the crystal is impacted on the plane (110) renders higher temperature fields.</div><div><br></div><div>Finally, we studied shock compression and dynamic fracture in polycrystalline HMX using the same model implemented for shocks in single crystals. The goal of this study is to understand the role of crystal anisotropy and how it affects other hotspot formation mechanisms such as frictional heating. To simulate fracture, we used a phase field damage model implemented for large deformations. We first perform simulations of sustained shocks in polycrystalline HMX, where the grains are perfectly bonded to understand the effect of plastic deformation and hotspot formation due to plastic heating. Then, we simulate shocks in polycrystalline HMX with dynamic fracture. Simulations capture fracture evolution and frictional heating at cracks. In the polycrystalline case, we study heat generation due to shock and plastic deformation. A heterogeneous temperature field forms when the shock wave travels in the material. Temperature increases more in crystals that showed a higher magnitude of accumulated slip. When weak grain boundaries are included in the simulations, frictional heating becomes the dominant hotspot formation mechanism. As the crystals' interfaces break and crack surface sliding occurs, temperature increases due to friction at cracks. Hotspots tend to form at cracks oriented 45 deg from the shock direction. For this case, crystal anisotropy does not play an important role in temperature generation due to plastic dissipation. However, the random orientation of the crystals creates heterogeneous deformation and stress fields that cause the formation of a higher number of hotspots than the case where all the grains are oriented in the same direction.</div>

To safely transport and use energetic materials, it is important that their response to mechanical excitation at various temperatures be well understood. In order to better understand the thermomechanical response of these materials, samples of inert and live PBXN-109 are fabricated and excited between 10-20 kHz. The resonance of the system is found using a Laser Doppler Vibrometer and the temperature at the surface of the sample is measured with an infrared camera. Samples are loaded into an environmental chamber and tested at -10, 22, 55, and 120 ˚C. Using multiple procedures, the shift in resonant frequency caused by changing material properties can be predicted and followed to elicit the greatest thermal response. Twelve samples are excited using a fluctuating sinusoidal input at each temperature range. The samples are shown to generate significantly less heat from mechanical excitation as ambient temperature increases. Heating rates are also severely affected by temperature. Samples tested at 120 ˚C heat at a rate of ~0.5 ˚C/min, while samples at -10 ˚C heat at ~ 5.7 ˚C/min. Despite the large difference in heating rates samples tested at higher ambient temperatures reached higher peak temperatures. This indicates that the strong temperature dependence of the material properties is likely key to reducing heating caused by mechanical excitation. It also indicates that proper control of ambient temperature should be considered when transporting or using munition systems to ensure safety and proper functionality.

Balancing increased safety against detonation performance is paramount for new explosive energetic materials in the development process. Often these two requirements are in opposition to each other. Sensitivity tests to external stimuli are used to determine how safe an energetic material is to phenomena such as impact, heat, or friction. Meanwhile, detonation performance is assessed by the maximum pressure and shock velocity induced from chemical reactions. Tailoring the performance while maintaining safety of the explosive would be possible with knowledge of the chemical reactions that functional groups provide during detonation. Current knowledge of the chemical reactions that occur during detonation is limited. Several mechanisms have been suggested for first step reactions throughout the detonation process for energetic molecules; however, no single chemical pathway has been irrefutably substantiated by experiments. Alternatively, models can provide insight into the types of reactions that may transpire, but lack direct experimental comparisons. If experiments and models could be compared at the equivalent time and length scales, then measurements could guide the physics and chemistry assumptions present in models. Experiments presented in this document bridge that gap by using an ultrafast laser system to generate shocks in samples and spectroscopically probe vibrational and electronic absorption changes that occur during shock compression. A review of how to turn a benchtop chirped pulse amplifier into a shock physics and chemistry laboratory is first presented. Applications of the spectroscopic techniques developed were then applied to trinitrotoluene (TNT) and pentaerythritol tetranitrate (PETN) during shock compression. Mid-infrared absorption results for shock compressed TNT and PETN were compared to current suggestions on chemical pathways and inconsistencies were present for both materials. It is suggested that a carbon-carbon bond breaking mechanism is present for PETN, and a hydrogenic stretch like hydroxyl or amide bond formation mechanism is suggested for TNT based on the MIR absorption measurements. Recommendations for future experimental thrusts are also provided. The results provided in this document could be directly compared to simulations to refine the assumptions present in models.

<p> The following document is a compilation of four manuscripts which were peer-reviewed and accepted for publication in the following scientific journals: <em>Propellants, Explosives, Pyrotechniques</em>, <em>Crystal Growth & Design</em>, <em>Zeitschrift für Anorganische und Allgemeine Chemie ZAAC</em>, and <em>Energetic Materials Frontiers</em>. This work, also, includes excerpts from the author’s review of energetic materials synthesized via reactions with nitroacetonitrile published by <em>RSC Advances</em>. The research presented is the result of a four-year graduate program in the School of Materials Engineering and as part of the Purdue Energetics Research Center (PERC). </p> <p>  </p> <p><em>1,2,4-Triazine Based Energetic Materials and Improved Nitro-Compound Synthesis</em> briefly addresses the history of energetic materials, key requirements, and ways to modify materials to meet those requirements before transitioning to the research synthesis and characterization. The discussion sections address the synthesis methods of the heterocyclic 1,2,4-triazine structure and alternative routes for the formation of nitro moieties. Also discussed are the methods for chemical characterization, thermal stability, mechanical sensitivity, and the theoretical calculations used to obtain energetic performances for comparison with traditional known explosive materials.</p> <p><br></p>

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 (Applied Science:Chemical Technology))--University of Pretoria, 2019. / Chemical Engineering / MSc (Applied Science:Chemical Technology) / Unrestricted

10ABSTRACTEnergetic materials are widely used as rocket propellants and explosives in the field of aerospace and defense. Understanding the nature of impact in polymer-bonded explosives is crucial safety and transportation of energetic materials. The formation of hotpots in energetic materials leads to unexpected initiations, posing a safety hazard. An attempt was made to study the mechanical behavior of energetic materials under different shapes of impactors. In particular, the likelihood of hotspot formations was discussed in spherical and Spherical Impactors(SI). Spherical and planar-shaped impactors were modeled with a cohesive finite element frame work to simulate the behavior of granular energetic materials with cyclo-tetramethylene-tetranitramine(HMX) embedded in a hydroxyl-polybutadiene binder. Temperature distribution and stresses induced around crystals on expanding stress profile of SI and uniform pressure profile from a SI are compared to determine the possibility of detonation.<div><br></div><div>In this work, the dependence of sample morphology on induced stresses in the microstructure is highlighted by using three different microstructures. A digitized polymer-bonded-explosive microstructure was analyzed for possible initiations with different impact velocities. The effect of the shape of grains and volume fractions on the likeliness of hotspot formation were studied using rounded and sharp-edged idealized crystals. Impactor behavior on samples was compared based on force chains, temperature profiles, and stress distributions</div>

<p>This thesis presents work on two major areas of research. The first area of research involves the use of a dual-nozzle piezoelectric inkjet printing system to print bilayer aluminum bismuth (III) oxide nanothermite samples. The combinatorial printing method allows for separate fuel and oxidizer inks to be printed adjacent to each other at prescribed offset distances. The effect of the bilayer thickness on the burning rate of the samples is investigated using high-speed imaging. Analysis of the burning rate data revealed that there is no statistically significant relationship between these two parameters. This result was used to determine the dominant processes that control the propagation rate in nanothermite systems. It was concluded that convective processes dominate the burning rate rather than diffusive processes. The second area of research involved synthesizing inks suitable for inkjet printing using two promising high nitrogen energetic materials called BTATz and DAATO_3.5. The performance of the developed inks was characterized using four experiments. The thermal stability and exothermic behavior of the inks were determined using DSC and TGA analysis. The results revealed that the inks are more thermally stable than the base materials. The inks were used to print lines that were subsequently used to determine burning rates. DAATO_3.5 samples were determined to have faster burning rates than BTATz. Closed pressure bomb experiments were conducted to determine the gas producing capability of the high nitrogen inks. BTATz samples showed better performance in terms of peak static pressures and pressurization rates. 3D printed microthrusters were developed to test the thrust performance of the inks. Peak thrust, total impulse, and specific impulse values are reported and were determined to be suitable for use with Class 1 micro-spacecraft. Finally, a microthruster array prototype was developed to demonstrate the capability to use additive manufacturing to create high packing density arrays.</p>

<p>  </p> <p>The additive manufacturing of energetic materials is a novel way to alter the properties of an energetic material without necessarily changing its chemical structure. There are many methods of additive manufacturing which can be applied to energetic material fabrication, each of which have unique advantages and disadvantages. The most well characterized additive manufacturing method is the commercially refined technique of fused filament fabrication (FFF) printing. FFF manufacturing techniques can be applied to additively manufacture thermoplastic energetic materials. The thermoplastic aluminum and polyvinylidene difluoride (Al/PVDF) system is suitable for manufacture with FFF techniques, shapeable into pyrotechnics with custom geometries using commonly available FFF printers. This theoretically allows Al/PVDF systems to be tailored for a wide variety of multifunctional needs, such as reactive structures. Following a literature review describing energetic material additive manufacturing techniques, this thesis focuses on the creation of outwardly identical Al/PVDF samples and the use of a geometric correction factor to control for uneven feedstock diameter. By varying the infill pattern, infill density, and interior geometry, different sample energy densities were obtained and observed during combustion. High speed videography measurements and the mass of individual samples were used to estimate the overall energy release rate. An Ashby plot contrasting the energy density and energy release rate was obtained. While full density printed samples burned similar to cast propellant strands in a linear burn, the energy release rates of additively manufactured Al/PVDF could be increased via convective combustion by varying the infill type and density. These results have significance for the fields of structural energetic materials and for additive manufacturing studies of energetic materials.</p>