L'utilisation industrielle ou militaire des explosifs est largement répandue. La sécurité est devenue un axe majeur avec notamment l'ignition involontaire des explosifs composés de HMX lors des impacts à basse vitesse. L'objectif de cette thèse est de contribuer à la compréhension des mécanismes dissipatifs à l'origine des échauffements locaux dans le matériau. Le développement d'un essai aux barres d'Hopkinson a permis de coupler de grandes vitesses de déformations à des pressions élevées pour compléter les données expérimentales. Cet essai a montré un angle de frottement quasiment identique à celui obtenu en quasistatique mais une contrainte de cohésion supérieure d'environ 25 MPa. Ensuite, pour observer les mécanismes pouvant être sources d'échauffement, un essai de compression dans la tranche a été développé avec des observations en temps réel. Celles-ci ont permis de conclure qu'il y a très peu de frottements entre les gros grains et la matrice (l'ensemble des petits grains, du liant et de la porosité). De la plasticité des grains de HMX a pu être observée mais surtout beaucoup d'endommagement dans certaines zones y compris dans la matrice. Une microfissuration très intense de certains grains a été observée. Parallèlement, une représentation numérique biphasique (gros grains de HMX et matrice) de toute la microstructure du matériau a été considérée. Une confrontation entre les observations expérimentales et les simulations a permis de déterminer le seuil de plasticité du HMX. Le comportement de la matrice a été identifié pour prendre en compte l'effet de vitesse et l'endommagement observé. Enfin, les confrontations entre les essais et les simulations de ceux-ci ont montré que les échauffements devraient plutôt se localiser dans la matrice que dans les gros grains de HMX et que le mécanisme le plus probable est le frottement de lèvres de microfissures.

The initiation of high explosives (HEs) under shock loading lacks a comprehensive understanding: particularly at the particle scale. One common explanation is hot spot theory, which suggests that energy in the material resulting from the impact event is localized in a small area causing an increase in temperature that can lead to ignition. This study focuses on the response of HMX particles (a common HE) within a polymer matrix (Sylgard-184^®), a simplified example of a polymer bonded explosive (PBX). A light gas gun was used to load the samples at impact velocities ranging from 370 to 520 m/s. The impact events were visualized using X-ray phase contrast imaging (PCI) allowing real-time observation of the impact event. The experiments used three subsets of PBX samples: multiple particle (production grade and single crystal), drilled hole, and milled slot. Evidence of damage and deformation occurred in all of the sample types. While the necessary impact velocity for consistent hot spot formation leading to reactions was not reached, the damage (particularly cracking) that occurred provides a useful indication of where hot spots may occur when higher velocities are reached. With the multiple particle samples, evidence of cracking and debonding occurred throughout. One sample showed significant volume expansion due to possible reaction. The samples containing drilled holes demonstrated the expected pore collapse behavior at these velocities, as well as damage downstream from the holes under various two-hole arrangements. Milled slot samples were tested to simulate existing cracks in the HMX. These samples showed increased damage at the site of the milled slot, as well as unique cracking behavior in one of the samples.

This work presents findings in the combined experimental and computational study of the effects of anisotropy and microstructure on the behavior of HMX-based energetic materials. Large single crystal samples of β-HMX were meticulously created by solvent evaporation for experimental purposes, and respective orientations were identified via x-ray diffraction. Indentation modulus and hardness values were obtained for different orientations of β-HMX via nanoindentation experiments. Small-scale dynamic impact experiments were performed, and a viscoplastic power law model fit, to describe the anisotropic viscoplastic properties of the crystal. The anisotropic fracture toughness and surface energy of β-HMX were calculated by studying indentation-nucleated crack system formations and fitting the corresponding data to two different models, developed by Lawn and Laugier. It was found that the {011} and {110} planes had the highest and lowest fracture toughnesses, respectively. Drop hammer impact tests were performed to investigate effects of morphology on the impact-induced thermal response of HMX. Finally, the anisotropic properties obtained in this work were applied in a cohesive finite element simulation involving the impact of a sample of PBX containing HMX crystals with varying orientations. Cohesive finite element models were generated of separate microstructure containing either anisotropic (locally isotropic) or global isotropic properties of HMX particle. In comparison, the isotropic model appeared to be more deformation resistant.

<p>This dissertation, while sometimes broad in scope, attempts to tie together the author’s work with the goal of better understanding the phenomenon of explosives initiation at the mesoscale. Discussion of the need for such an investigation will be covered, including how mesoscale phenomena and the dominant theory of explosives initiation–hot spot theory–are intimately related. Furthermore, some difficulties in designing mesoscale experiments will be mentioned. Sample preparation–one of the more difficult tasks in this regime–will be covered, including single crystal growth, mechanical machining with a quasi-CNC machine, laser machining, and hacks to a tungsten wire saw for novel sample production. The author will go on to show work done in a quasi-static regime, at low strain rates, and at medium- high strain rates. These novel experiments start to show how pore collapse functions in single-crystal HMX. Additional work with thermophosphors, which may be relevant to future experiments, is also presented. New experimental diagnostics designed and constructed by the author are laid out for future reference, along with improvements to a gas gun apparatus.</p>

La cristallisation en continu de nanoparticules énergétiques est un défi de longue date. Le Spray Flash Evaporation (SFE) est une technique majeure développée et brevetée en interne, pour la production en continu de matériaux énergétiques submicroniques ou nanométriques ; la technologie se base sur la surchauffe d’un solvant pulvérisé dans le vide et s’évaporant de manière flash. Ce présent travail de recherche a pour but de comprendre et contrôler la cristallisation au sein du procédé SFE. Le RDX et le cocristal CL-20:HMX 2:1 sont étudiés. La sursaturation, concernant le SFE, est une fonction du temps et de l’espace liée aux tailles et vitesses de gouttes : elle fut variée par un anti-solvant et par l’amélioration du SFE avec un système double buse. Ensuite, PVP 40K et PEG 400 ont été utilisés afin de contrôler la nucléation et la croissance. Les particules ont pu être ajustées d’une taille de 160 nm à 5 µm, avec des morphologies facettées ou sphériques et avec des sensibilités moindres. / The continuous formation of nanosized energetic material is a long-standing challenge. Spray Flash Evaporation (SFE) is a major technique, internally developed and patented, for continuously producing energetic materials at submicron or nano scale; it relies on the superheating of a solvent sprayed into vacuum and thus flashing. This present research project aims to understand and control the crystallisation occurring in the SFE process. RDX and the cocrystal CL-20:HMX 2:1 was studied overcome the limited in situ characterizations also. The supersaturation is a function of time and space in SFE, linked to the size distribution and velocity of droplets. Supersaturation was raised with an anti-solvent and by the enhancement of the SFE with a dual nozzle system. Then PVP 40K and PEG 400 were successfully used to alter the nucleation and the growth. The particles were subsequently tuned from 160 nm spheres to 5 µm grains and were less sensitive, especially toward electrostatic discharge.

A compatibilidade química de explosivos é estudada para avaliar potenciais riscos quando os mesmos são colocados em contato com outros materiais durante a produção, armazenamento e manuseio. Esta compatibilidade pode ser estudada por vários métodos, tais como DSC (Calorimetria Exploratória Diferencial), TG (Termogravimetria), Estabilidade química a vácuo, microcalorimetria, calorimetria de fluxo de calor, etc. Os métodos de ensaios e a definição de critérios de avaliação são elementos importantes quando um estudo de compatibilidade está sendo realizado. Nesse trabalho, a compatibilidade química de dois importantes explosivos utilizados em armamentos, RDX (ciclotrimetilenotrinitroamina) e HMX (ciclotetrametilenotetranitroamina), foi estudada com polímero fluorado (Viton B) e alumínio em pó (Al 123), usando os métodos DSC, TG e Estabilidade química a vácuo. Os três métodos forneceram informações importantes sobre a compatibilidade química dos materiais, através dos parâmetros térmicos e volume de gás liberado. Observou-se que o HMX apresenta compatibilidade com Viton B e Al, da mesma forma que o RDX apresenta compatibilidade com Viton, porém no estudo de compatibilidade do RDX com Al, com os métodos DSC e TG, nota-se um pico adicional, após o pico de decomposição, o que é um indicativo de incompatibilidade. Os métodos foram comparados em relação aos fatores que podem influenciar o resultado, servindo de base para futuros estudos de compatibilidade química. A conclusão é que, quando se utilizam os métodos DSC e TG, os sistemas HMX - Al, HMX - Viton e RDX - Viton são compatíveis, porém o sistema RDX - Al apresenta um grau de incompatibilidade. Entretanto, todos são compatíveis quando se utiliza o método da estabilidade química a vácuo.

Os explosivos compósitos desenvolvidos no CTA utilizam HMX, que pode existir em 4 formas polimórficas denominadas a, b, g e d. O HMX produzido no IAE cristaliza-se na forma a, que é mais sensível ao atrito e choque durante o manuseio, sendo necessário a recristalização para a forma b-HMX, que é a forma mais estável para utilização. Neste trabalho foi feita a caracterização do b-HMX, quanto a pureza, forma cristalina e formato em várias granulometrias, com a utilização das técnicas Cromatografia líquida de alta eficiência (HPLC), Espectroscopia no infravermelho com transformada de Fourier (FTIR), Microscopia ótica, Calorimetria exploratória diferencial (DSC), Microscopia eletrônica de varredura (MEV) e Difração de raios-X. Foi observado que o tamanho da partícula e sua distribuição afetam a temperatura da transição bd-HMX medida por DSC, sendo que quanto mais fina a granulometria mais alta a temperatura da transição. A microscopia ótica e MEV mostraram que as frações não são uniformes quanto ao tamanho e o formato das partículas, com a existência de partículas mal formadas, "clusters". A análise DSC mostrou que o comportamento do "cluster" é diferente dos cristais pequenos, obtendo a transição em temperatura mais baixa do que cristais maiores. MEV mostrou que após a conversão para forma d, as partículas maiores apresentam trincas , o que pode explicar picos múltiplos observados no DSC. O efeito da granulometria sobre a decomposição acompanhou o efeito sobre a transição cristalina, embora de forma pouco significativa.

A majority of research within the field of energetic materials have been centered around the stable crystalline phase, whilst there has been less about the amorphous phase and the implications of these types of material. In this study, Molecular Dynamics simulations with the General Amber Force Field (GAFF) is used to predict fundamental properties of the nitramine explosives HMX and CL-20 in the amorphous phase. Amorphous structures are obtained by compressing a molecular gas to 4 GPa followed by relaxation and equilibration. The simulations indicate that the amorphous phases of HMX and CL-20 have lower densities than the corresponding crystal phases, 12.7% and 7.3% respectively. Both HMX and CL-20 was found to compress more easily when subject to external pressure, the difference was most significant for HMX.As a second part of this study an amorphous composition of CL-20/HMX/Polyvinylacetate(PVAc) (50/45/5 -wt%) was studied. This was obtained by compressing a molecular gas to varying pressures followed by relaxation and equilibration. Results indicate that the simulated density around 1.64 [g/cm3 ] fall close to experimental observations of 1.7 [g/cm3 ]. The density was observed to not vary significantly for pressures higher than 0.4 [GP a] in accordance to experimental data.

Information on the sensitivity of explosives is highly valuable, and the short time scales in which chemical reactions occur in explosives, along with the ability of microstructure to have significant effects on sensitivity, often make this information difficult and expensive to acquire and interpret. Significant changes in impact and shock sensitivity are expected as a result of inducing structural damage in an explosive sample, and thermally damaged HMX-based samples can incur a solid-solid phase transition from beta to delta with non-extreme thermal inputs. Changes in sensitivity due to this phase transition, as well as the simultaneously induced damage, and their relative influence on sensitivity, are of interest to determine experimentally. <div><br></div><div>Drop-weight impact tests are a commonly used measure of explosive impact sensitivity. Often, simply the L50 of a given material is reported and compared with that of other materials to give a sense of its impact sensitivity. The practice of reporting the impact sensitivity as a single number, the L50, is likely inadequate. It is important to additionally report a measure of the spread of the distribution of reaction probabilities in order to assess the hazard of reaction in situations that may induce a stimulus level well below the L50 of a material. Additionally, multiple distribution forms have been suggested previously for fitting of binary sensitivity data; these distributions typically deviate from each other most near the tails (low and high stimulus levels). The consequences of choosing one distribution form over another in the analysis of explosive drop-weight impact results is explored.<br></div><div><br></div><div>Changes in impact sensitivity due to phase change have received some previous exploration, though the phase change influence is generally conflated with the induced damage upon said phase transition; however, sensitivity changes in the shock regime due to beta to delta-phase change have received little attention. Work is shown which includes methods to isolate variables of HMX phase transition and damage typically incurred upon said phase transition.<br></div>

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