On account of the high temperatures and pressures experienced by energetic materials during deflagration and detonation, it is important to know not only the physical properties of these materials at ambient temperatures and pressures, but also to understand how their structure and properties are affected by extreme conditions. Combined computational and experimental investigations of the effects of high pressures on the structure and properties of several energetic materials are described herein. A comparison of the performances of different pseudopotentials and density functional theory (DFT) dispersion correction schemes in calculating crystal geometries and vibrational frequencies of crystalline ammonium perchlorate at high pressure is described. The results highlight the fact that care must be taken when choosing pseudopotentials for high-pressure studies. A comprehensive comparison of calculated vibrational modes (including symmetry) with experiment has been performed, with the frequencies of all internal modes predicted to lie within 5% of experimental values. This study established that no significant improvements in the calculation of crystal geometries of ammonium perchlorate are obtained by employing DFT-D corrections. The enthalpy of fusion (ΔHfus) of the highly metastable β-form of RDX (cyclotrimethylenetrinitramine) was determined to be 12.63 ± 0.28 kJ mol-1. DFT-D calculations of the lattice energies of the α- and β-forms of RDX are described. Furthermore, the response of the lattice parameters and unit-cell volumes to pressure for the α-, γ- and ε-forms of RDX calculated using DFT-D are in very good agreement with experimental data. Phonon calculations provide good agreement with vibrational frequencies obtained from Raman spectroscopy, and a predicted inelastic neutron scattering (INS) spectrum of α-RDX shows excellent agreement with experimental INS data recorded as part of this study. The results of the high-pressure phonon calculations have been used to show that the heat capacities of the α-, γ- and ε- forms of RDX are only weakly affected by pressure. DFT-D calculations have been utilised to describe accurately the structure and properties of both β-HMX (Cyclotetramethylenetetranitramine) and α-FOX-7 (1,1-Diamino-2,2-dinitroethylene) as a function of pressure. This work presents data for the experimental hydrostatic compression of both deuterated β-HMX and α-FOX-7 performed using neutron powder diffraction at the ISIS Neutron and Muon facility, in addition to experimental determinations of the INS spectra of both β-HMX and α-FOX-7. The DFT-D hydrostatic compression studies for both materials reproduce the experimental compression trends. Furthermore, the calculated vibrational properties as a function of pressure were in very good agreement with available experimental data. The results of the phonon calculations were then used to predict the effect of pressure on the heat capacities of β-HMX and α-FOX-7. These predictions suggest a very weak pressure dependence of heat capacities (approximately -1 J K-1 mol-1 GPa-1) for these materials. This work demonstrates that the DFT-D model performs extremely well over a range of conditions, and is able to describe accurately intramolecular and intermolecular interactions, and thus the structure and properties of organic molecular nitramine crystals. The computational model was therefore used to predict the high-pressure hydrostatic compression behaviour of a related nitramine, CL-20 (2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane), the results of which highlighted possible discrepancies in the experimental high-pressure X-ray diffraction data recorded for ε-CL-20. This prompted a high-pressure neutron powder diffraction study, which showed good agreement with the computational results, thereby highlighting radiation damage in the X-ray experiments.

Energetic materials encompass a wide range of chemical compounds all associated with a significant risk of fire and explosion. They include explosives, fireworks, pyrotechnics, powders, propellants and other unsteady chemicals. These materials store a high level of chemical energy and are able to release it rapidly without external contribution of oxygen or any other oxidizer. The behaviour of these materials in case of explosive detonations is relatively wellknown from empirical and practical points of view. However, fundamental scientific questions remain unanswered related to the mechanisms of heat release. The current understanding of these mechanisms lacks appropriate thermochemical characterisation. The aim of the study is the analysis of thermal and chemical characteristics of energetic materials under conditions that exclude detonations. Detonation is excluded in order to better isolate the thermal and chemical mechanisms involved in the burning process. The experimental work has been conducted using the FM Global Fire Propagation Apparatus (FPA) [ASTM E2058‐03]. One of the benefits of using this experimental apparatus rather than the Cone Calorimeter is that it allows controlling the feed of heat and oxidizer to the reaction zone. The material chosen to conduct experiments on is a ternary smoke powder based on a mixture of starch and lactose as fuel components and potassium nitrate as oxidizer. This product is currently used by fire brigades to assess smoke venting systems efficiency of buildings. The kinetics associated with the combustion of the material was assessed slow enough to allow measuring instruments to capture the thermal and chemical evolution during combustion reaction. Thermal analysis has first been carried out by means of DSC, TGA, DTA, MS and FTIR data in order to understand the decomposition of the material and its energetic evolution when undergoing heating. However, if the latter methods help defining the decomposing path of the material, they do not provide an integral view of its combustion behaviour, in particular, the emissions of toxics which are kinetic path dependent. Subsequently, combustion tests have been carried out using the FPA. Its ability to capture the evolution of gases emissions formed during the reaction has been proved. The influence of two configuration parameters on the combustion behaviour and on the gaseous emissions of the material has been investigated. The proportion fuel/oxidizer has been varied as well as the composition of the reacting atmosphere. Results shows that the quantity of oxidizer in the material affects the kinetics of the reactions taking place in the condense phase. Increasing the concentration of potassium nitrate in the mixture enhanced the reaction rate of the smouldering combustion. Higher quantity of volatiles is released which favoured the initiation of a diffusion flame regime in the gaseous phase, above the sample. While the kinetics of the condense phase is governed by the oxidizer concentration, experiments show that the flaming regime is influenced by the concentration of oxygen (O2) in the reacting atmosphere. A transition from diffusion to premixed flame is found when the concentration of O2 surrounding the sample is reduced below 18%. An analytical model has been used to explain the existence of a transition for a critical O2 concentration. Finally, thermal and combustion analyses have allowed to characterise the behaviour of the material under critical conditions, in terms of decomposition taking place in the condense phase but also potential toxic emissions that can be released. Toxicity, kinetics, temperature evolution do not provide a complete view of the combustion phenomenon. Beside these elements that characterise the behaviour of a material for given conditions as well as also the degree of fire hazard encountered, the energetic issue holds as an essential feature that cannot be neglected. The heat release rate (HRR) is a critical parameter that defines a fire. It does not constitute an intrinsic material property but it describes the energetic response of the couple formed by the material and its environment. Oxygen Consumption calorimetry (OC) and Carbon Dioxide Generation calorimetry (CDG) are widespread methods to calculate the HRR resulting from a combustion reaction. Apparatuses such as the FPA or the cone calorimeter have already proved their potential to qualify the burning behaviour of common fuels in addition to polymers when their data are combined with an adapted calorimetric procedure. The same approach has been applied to energetic materials. However, prior to using these techniques, it is fundamental to have identified their restrictions. These techniques provide approximate estimations of the HRR. Results are affected by the propagation of uncertainties. Several sources of uncertainties can be found. One can cite: 1. Uncertainties associated with the sample material; 2. Uncertainties associated with the test conditions; 3. Uncertainties associated with the measurements; 4. Uncertainties associated with calculation assumptions. If uncertainties cannot always be estimated, the three first sources cited have received attention in the past from the scientific community, alike the last one. The restrictions associated with the assumptions developed for using the OC and CDG principles have to be clarified. The limits of validity of the hypotheses have to be clearly defined. In particular, the present dissertation questions the relevance of the energy constants that have been specified for OC and CDG as well as their related uncertainties. One of the purposes of the research deals with the ability to estimate accurate error bars for the calculation of the HRR. Once uncertainties related to the calorimetric methods are assessed, a method adapted from the basic OC and CDG principles is introduced that allows estimating the HRR of energetic materials. The approach is based on considering the chemical decomposition of the burning compound and defining a fictitious molecule for which energy coefficients can be calculated. Nevertheless, it requires the material to be known. Finally, the question of the advantage brought by these techniques over others, in terms of accuracy, is discussed within the framework of unconventional products, such as energetic materials or compounds whose composition is ignored. The results from this work will contribute to the development of fireanalysis methodologies and validate their use with energetic materials.

<p>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. </p>

<p>Investigation of laser-matter interaction has been an important research topic which is closely related to applications in various fields including industry, military, electronics, photonics, etc. With the advent of ultrafast transmission electron microscope (UTEM), in situ investigation of the interaction between pulsed laser and nanostructured materials becomes accessible, with unprecedented spatial and temporal resolution. Here, we studied two categories of materials with the help of UTEM, namely, energetic materials and plasmonic nanostructures. The results demonstrate that UTEM provides a novel and convenient way for the investigation the structural and morphological change of energetic materials under external stimuli at nanoscale. Also, UTEM makes it possible to visualize the light-induced welding between plasmonic nanostructures at real time, which helps to reveal more details about the mechanisms involved. Furthermore, we studied the formation of some novel structures by combing different gold and silver nanostructure.</p>

Calorimetry is one of the main techniques of thermal analysis. Most of physical or chemical modifications of material are associated with thermal effects whereby heat is absorbed (i.e., melting) or released (i.e., thermal decomposition). Typically, calorimetric experiments are performed with Differential Scanning Calorimetry (DSC), which measures the heat flux absorbed or released by the sample following the same temperature program as a reference material. In these experiments, measurements are typically carried out on a few milligrams of sample. However, for many applications one has to handle nanograms or even picograms of sample. One of such applications is relevant to studies of materials which can release a significant amount of energy during their decomposition (energetic materials). Calorimetry able to handle nanograms of sample could find potential applications in the field of explosives detection. Nanocalorimetry allows to heat small amounts of sample (a few nanograms to a few hundred picograms) at extreme heating rates, i.e. up to one million °C/s. The temperature increase can initiate several phenomena in energetic materials, therefore the calorimetry could be an appropriate technique to characterize and to detect energetic materials. The energetic materials used in this study are nitrocellulose (NC), hexogen (RDX), 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-ltexaazaisowurtzitane (CL-20) and penthrite (PETN). The manuscript presents our results on the nanocalorimeter calibration, on the thermal behaviour of the explosives studied with nanocalorimetry and also includes an evaluation of nanocalorimetry as a tool for explosives detection.

Several metal honeycombs, termed Linear Cellular Alloys (LCAs), were fabricated via a paste extrusion process and thermal treatment. Two Fe-Ni based alloy compositions were evaluated. Maraging steel and Super Invar were chosen for their compatibility with the process and the wide range of properties they afforded. Cell wall material was characterized and compared to wrought alloy specifications. The bulk alloy was found to compare well with the more conventionally produced wrought product when porosity was taken into account. The presence of extrusion defects and raw material impurities were shown to degrade properties with respect to wrought alloys. The performance of LCAs was investigated for several alloys and cell morphologies. The results showed that out-of-plane properties exceeded model predictions and in-plane properties fell short due to missing cell walls and similar defects. Strength was shown to outperform several existing cellular metals by as much as an order of magnitude in some instances. Energy absorption of these materials was shown to exceed 150 J/cc at strains of 50% for high strength alloys. Finally, the suitability of LCAs as an energetic capsule was investigated. The investigation found that the LCAs added significant static strength and as much as three to five times improvement in the dynamic strength of the system. More importantly, it was shown that the pressures achieved with the LCA capsule were significantly higher than the energetic material could achieve alone. High pressures, approaching 3 GPa, coupled with the fragmentation of the capsule during impact increased the likelihood of initiation and propagation of the energetic reaction. This multi-functional aspect of the LCA makes it a suitable capsule material.

In this study, all possible mono, di and trinitro-substituted triazine compounds as potential candidates for high energy density materials (HEDMs) have been investigated by using quantum chemical treatment. Computational chemistry is a valuable tool for estimating the potential candidates for high energy density materials. Geometric features and electronic structures of these nitro-substituted triazines have been systematically studied using ab initio and density functional theory (DFT, B3LYP) at the level of 6-31G(d,p), 6-31+G(d,p), 6-311G(d,p), 6-311+G(d,p), cc-pVDZ. Detonation performances were evaluated by the Kamlet-Jacobs equations based on the calculated densities and heats of formation. It is found that 2G derivative with the predicted densities of 1.9 g/cm3, detonation velocities of 9.43 km/s, and detonation pressures of 40.68 GPa may be novel potential candidates of high energy density materials (HEDMs). Moreover, thermal stabilities were investigated by calculating bond dissociation energies (BDE) at B3LYP/6-311G(d,p) level. Detailed molecular orbital (MO) investigation have been performed on these potential HEDMs.

Conventional energetic materials which are based on monomolecular compounds such as trinitrotoluene (TNT) have relatively low volumetric energy density. The energy density can be significantly enhanced by the addition of metal particulates. Among all metals, aluminum is popular because of its high oxidation enthalpy, low cost, and relative safety. Micron-sized aluminum particles, which have relatively high ignition temperatures and burning times, have been most commonly employed. Ignition of micron-sized aluminum particles is typically achieved only upon melting of the oxide shell at 2350 K, thereby resulting in fairly high ignition delay. Novel approaches to reduce the ignition temperatures and burning times and enhance the energy content of the particle are necessary. Recently, there has been an enormous interest in nano-materials due to their unique physicochemical properties such as lower melting and ignition temperatures and shorter burning times. Favorably, tremendous developments in the synthesis technology of nano-materials have also been made in the recent past. Several metal-based energetic materials with nano-sized particles such as nano-thermites, nano-fluids, and metalized solid propellants are being actively studied. The “green” reactive mixture of nano-aluminum particles and water/ice mixture (ALICE) is being explored for various applications such as space and underwater propulsion, hydrogen generation, and fuel-cell technology. Strand burning experiments indicate that the burning rates of nano-aluminum and water mixtures surpass those of common energetic materials such as ammonium dinitramide (ADN), hydrazinium nitroformate (HNF), and cyclotetramethylene tetranitramine (HMX). Sufficient understanding of key physicochemical phenomena is, however, not present. Furthermore, the most critical parameters that dictate the burning rate have not been identified. A multi-zone theoretical framework is established to predict the burning properties and flame structure by solving conservation equations in each zone and enforcing the mass and energy continuities at the interfacial boundaries. An analytical expression for the burning rate is derived and physicochemical parameters that dictate the flame behavior are identified. An attempt is made to elucidate the rate-controlling combustion mechanism. The effect of bi-modal particle size distribution on the burning rate and flame structure are investigated. The results are compared with the experimental data and favorable agreement is achieved. The ignition and combustion characteristics of micron-sized aluminum particles can also be enhanced by replacing the inert alumina layer with favorable metallic coatings such as nickel. Experiments indicate that nickel-coated aluminum particles ignite at temperatures significantly lower than the melting point of the oxide film, 2350 K due to the presence of inter-metallic reactions. Nickel coating is also attractive for nano-sized aluminum particles due to its ability to maximize the active aluminum content. Understanding the thermo-chemical behavior of nickel-aluminum core-shell structured particles is of key importance to both propulsion and material synthesis applications. The current understanding is, however, far from complete. In the present study, molecular dynamics simulations are performed to investigate the melting behavior, diffusion characteristics, and inter-metallic reactions in nickel-coated nano-aluminum particles. Particular emphasis is on the effects of core size and shell thickness on all important phenomena. The properties of nickel-coated aluminum particles and aluminum-coated nickel particles are also compared. Considerable uncertainties pertaining to the ignition characteristics of nano-aluminum particles exist. Aluminum particles can spontaneously burn at room temperature, a phenomenon known as pyrophoricity. This is a major safety issue during particle synthesis, handling, and storage. The critical particle size below which nascent particles are pyrophoric is not well known. Energy balance analysis with accurate evaluation of material properties (including size dependent properties) is performed to estimate the critical particle size for nascent particles. The effect of oxide layer thickness on pyrophoricity of aluminum particles is studied. The ignition delay and ignition temperature of passivated aluminum particles are also calculated. Specific focus is placed on the effect of particle size. An attempt is made to explain the weak dependence of the ignition delay on particle size at nano-scales.

Energetic structural materials (ESMs) constitute a new class of materials that provide dual functions of strength and energetic characteristics. ESMs are typically composed of micron-scale or nano-scale intermetallic mixtures or mixtures of metals and metal oxides, polymer binders, and structural reinforcements. Voids are included to produce a composite with favorable chemical reaction characteristics. In this thesis, a continuum approach is used to simulate gas-gun or explosive loading experiments where a strong shock is induced in the ESM by an impacting plate. Algorithms are developed to obtain equations of state of mixtures. It is usually assumed that the shock loading increases the energy of the ESM and causes the ESM to reach the transition state. It is also assumed that the activation energy needed to reach the transition state is a function of the temperature of the mixture. In this thesis, it is proposed that the activation energy is a function of temperature and the stress state of the mixture. The incorporation of such an activation energy is selected in this thesis. Then, a multi-scale chemical reaction model for a heterogeneous mixture is introduced. This model incorporates reaction initiation, propagation, and extent of completed reaction in spatially heterogeneous distributions of reactants. A new model is proposed for the pore collapse of mixtures. This model is formulated by modifying the Carol, Holt, and Nesterenko spherically symmetric model to include mixtures and compressibility effects. Uncertainties in the model result from assumptions in formulating the models for continuum relationships and chemical reactions in mixtures that are distributed heterogeneously in space and in numerical integration of the resulting equations. It is important to quantify these uncertainties. In this thesis, such an uncertainty quantification is investigated by systematically identifying the physical processes that occur during shock compression of ESMs which are then used to construct a hierarchical framework for uncertainty quantification.

Le développement de nouvelles compositions propulsives, pour applications stratégique et spatiale par exemple, conduit à élaborer des charges énergétiques de plus en plus puissantes... / The development of new compositions of propellants, for strategic and space applications for instance, leads to synthesis of more and more powerful energetic materials...