<div>A combined experimental and computational study has been performed in order to understand the effect of interface chemical composition on the shock induced mechanical behavior of an energetic material (EM) system consisting of Hydroxyl-Terminated Polybutadiene (HTPB) binder and an oxidizer, Ammonium Perchlorate (AP), particle embedded in the binder. The current study focuses on the effect of interface chemical composition between the HTPB binder material and the AP particles on the high strain rate mechanical behavior. The HTPB-AP interface chemical composition was changed by adding cyanoethylated polyamine (HX-878 or Tepanol) as a binding agent. A power law viscoplastic constitutive model was fitted to nanoscale impact based experimental stress-strain-strain rate data in order to obtain the constitutive behavior of the HTPBAP interfaces, AP particle, and HTPB binder matrix. An in-situ mechanical Raman spectroscopy framework was used to analyze the effect of binding agent on cohesive separation properties of the HTPB-AP interfaces, AP particle, and HTPB binder matrix. In addition, a combined mechanical Raman spectroscopy and laser impact set up was used to study the effect of strain rate, as well as the interface chemical composition on the interface shock viscosity. Finally, high velocity strain rate impact simulations were performed using an explicit cohesive finite element method framework to predict the effect of strain rate, interface strength, interface friction, and interface shock viscosity on possible strain rate dependent temperature rises at high strain rates approaching shock velocities. </div><div><br></div><div>A modified stress equation was used in the cohesive finite element framework in order to include the effect of shock viscosity on the shock wave rise time and shock pressure during impact loading with strain rates corresponding to shock impact velocities. It is shown that increasing the interface shock viscosity, which can be altered by changing the interface chemical composition, increases the shock wave rise time at the analyzed interfaces. It is shown that the interface shock viscosity also plays an important role in determining the temperature increase within the microstructure. Interface shock viscosity leads to a decrease in the overall density of the possible hot-spots which is caused by the increase in dissipation at the shock front. This increase in shock dissipation is accompanied by a decrease in the both the maximum temperature, as well as the plastic dissipation energy, within the microstructure during shock loading.</div>

This document details original numerical studies performed by the author pertaining to the propellant oxidizer, ammonium perchlorate (AP). Detailed kinetic mechanisms have been utilized to model the combustion of the monopropellants AP and ADN, and a two-dimensional diffusion flame model has been developed to examine the flame structure above an AP/HTPB composite propellant. This work was part of an ongoing effort to develop theoretically based, a priori combustion models. The improved numerical model for AP combustion utilizes a “universal” gas-phase kinetic mechanism previously applied to combustion models of HMX, RDX, GAP, GAP/RDX, GAP/HMX, NG, BTTN, TMETN, GAP/BTTN, and GAP/RDX/BTTN. The universal kinetic mechanism has been expanded to include chlorine reactions, thus allowing the numerical modeling of AP. This is seen as a further step in developing a gas-phase kinetic mechanism capable of modeling various practical propellants. The new universal kinetic mechanism consists of 106 species and 611 reactions. Numerical results using this new mechanism provide excellent agreement with AP's burning rate, temperature sensitivity, and final species data. An extensive literature review has been conducted to extract experimental data and qualitative theories concerning ADN combustion. Based on the literature review, the first numerical model has also been developed for ADN that links the condensed and gas phases. The ADN model accurately predicts burning rates, temperature and species profiles, and other combustion characteristics of ADN at pressures below 20 atm. Proposed future work and modifications to the present model are suggested to account for ADN's unstable combustion at pressures between 20 and 100 atm. A two-dimensional model has been developed to study diffusion in composite propellant flames utilizing a vorticity formulation of the transport equations. This formulation allows for a more stable, robust, accurate, and faster solution method compared to the Navier-Stokes formulations of the equations. The model uses a detailed gas-phase kinetic mechanism consisting of 37 species and 127 reactions. Numerical studies have been performed to examine particle size, pressure, and formulation effects on the flame structure above an AP/HTPB propellant. The modeled flame structure was found to be qualitatively similar to the BDP model. Results were consistent with experimental observations. Three different combustion zones, based on particle size and pressure, were predicted: the AP monopropellant limit, the diffusion flame, and a premixed limit. Mechanistic insights are given into AP's unique combustion properties.

This dissertation documents the building of computational propellant/ingredient models toward predicting AP/HTPB/Al cookoff events. Two computer codes were used to complete this work; a steady-state code and a transient ignition code Numerous levels of verification resulted in a robust set of codes to which several propellant/ingredient models were applied. To validate the final cookoff predictions, several levels of validation were completed, including the comparison of model predictions to experimental data for: AP steady-state combustion, fine-AP/HTPB steady-state combustion, AP laser ignition, fine-AP/HTPB laser ignition, AP/HTPB/Al ignition, and AP/HTPB/Al cookoff. A previous AP steady-state model was updated, and then a new AP steady-state model was developed, to predict steady-state combustion. Burning rate, temperature sensitivity, surface temperature, melt-layer thickness, surface species at low pressure and high initial temperature, final flame temperature, final species fractions, and laser-augmented burning rate were all predicted accurately by the new model. AP ignition predictions gave accurate times to ignition for the limited experimental data available. A previous fine-AP/HTPB steady-state model was improved to predict a melt layer consistent with observation and avoid numerical divergence in the ignition code. The current fine-AP/HTPB model predicts burning rate, surface temperature, final flame temperature, and final species fractions for several different propellant formulations with decent success. Results indicate that the modeled condensed-phase decomposition should be exothermic, instead of endothermic, as currently formulated. Changing the model in this way would allow for accurate predictions of temperature sensitivity, laser-augmented burning rate, and surface temperature trends. AP/HTPB ignition predictions bounded the data across a wide range of heat fluxes. The AP/HTPB/Al model was based upon the kinetics of the AP/HTPB model, with the inclusion of aluminum being inert in both the solid and gas phases. AP/HTPB/Al ignition predictions bound the data for all but one source. AP/HTPB/Al cookoff predictions were accurate when compared to the limited data, being slightly low (shorter time) in general. Comparisons of AP/HTPB/Al ignition and cookoff data showed that the experimental data might be igniting earlier than expected.

Les explosifs sont des matériaux qui, bien que potentiellement sensibles, sont conçus pour être stables en conditions normales, ainsi que lors de sollicitations mécaniques, chimiques ou thermiques « faibles ». Pourtant, sous sollicitations mécaniques de faible intensité, comme les impacts basse vitesse, ils peuvent réagir de manière intempestive. Les propergols, et plus particulièrement la butalite, objet de notre étude, présentent ce caractère : on observe des « réactions » pour des vitesses d'impacts inférieurs à 100 m.s-1, dont l'origine est probablement liée à l'endommagement microstructural du matériau.Dans ce contexte, le but ultime du CEA2 Gramat est d'obtenir un outil de prédiction de la vulnérabilité des matériaux énergétiques pour les impacts à basse vitesse de type tour de chute. Pour ce faire, il est essentiel de disposer de données sur la morphologie et le comportement (thermo)mécanique macroscopique du matériau considéré, de ses phases constitutives à l'échelle mésoscopique et de ses interfaces.Ainsi l'objectif de la thèse est de déterminer le type et le niveau de(s) endommagement(s) apparaissant(s) dans une « butalite inerte » suite à un impact mécanique dit « à basse vitesse » (i.e., inférieure à 100 m.s-1) réalisé à l'aide d'un dispositif de type tour de chute modifié, associant un suivi par vidéo numérique rapide et une analyse microtomographique ante- et post-essai, en étudiant le ou les phénomènes physiques à l'origine des réactions sous « faibles » sollicitations, leur évolution et leur(s) origine(s) physique(s). Les grains sont modélisés par une loi de comportement purement élastique et la matrice en PBHT est décrite par une loi visco-hyper-élastique (couplage d'une série de Prony et du modèle de Mooney-Rivlin). / Although they are potentially sensitive, energetic materials are designed to be stable under normal conditions, as well as “weak” mechanical, chemical or thermal loadings. However, under low mechanical loadings, such as low velocity impacts, they may react untimely. Propellants and especially the butalite, object of our study, show "reactions" to impact velocities below 100 m.s-1, whose origin is probably related to the material microstructural damage.In this context, the ultimate goal of CEA2 Gramat is to obtain a predicting tool for the vulnerability of energetic materials for low velocity impacts as drop weight test. So it is essential to have data on the morphology and macroscopic (thermo)mechanical behavior, its component phases at the mesoscopic scale and its interfaces.Thus, the objective of the thesis is to determine the type and the damage(s) level(s) generating in an "inert butalite", during a low velocity mechanical impact (i.e., less than 100 m.s-1), using a fast camera recording and ante- and post-test microtomographic analysis, or by studying the physical phenomena which are at the origin of reactions, their evolution and physical origin(s). Grains are represented by a purely elastic model and HTPB matrix is described by a visco-hyper-elastic model (coupling a Prony serie and Mooney-Rivlin model).

<p dir="ltr">Emission and absorption spectroscopy diagnostics are useful for providing non-invasive,<br>quantitative measurements of various gas properties in combustion environments, including<br>temperature and species concentrations. These measurements become even more useful<br>when they are applied with high spatial and temporal resolution. This dissertation describes<br>several ways that both emission and absorption diagnostics were advanced through leveraging<br>improvements in mid-IR camera and laser technology and through refining the use of existing<br>techniques.<br>A literature review is provided for both laser absorption and emission spectroscopy. Previous advancements in spatially resolved techniques are explained. The fundamental equations<br>of spectroscopic diagnostics are reviewed, starting from statistical mechanics.<br>A spectrally-resolved emission imaging diagnostic is presented. This diagnostic provided<br>1-dimensional measurements of gas temperature and relative mole fraction of CO₂ and HCl<br>in flames. An imaging spectrometer and a high-speed mid-infrared camera were used to<br>provide 1D measurements of CO₂and HCl emission spectra with a spectral resolution of<br>0.46 cm^-1 at rates up to 2 kHz. Measurements were acquired in HMX and AP-HTPB flames<br>burning in air at 1 atm. This diagnostic was applied to characterize how the path-integrated<br>gas temperature of HMX flames varies in time and with distance above the burning surface.<br>Additionally, Abel inversion with Tikhonov regularization was applied to determine the radial<br>distribution of temperature and relative concentration of CO₂ and HCl within the core of<br>AP-HTPB flames.<br>Next, a similar emission imaging diagnostic is presented which uses spectrally-resolved<br>measurements of emission spectra at visible wavelengths, unlike the mid-infrared measure-<br>ments in the rest of this dissertation. This diagnostic provided 1D temperature measure-<br>ments of aluminum oxide (AlO), an intermediate product of aluminum combustion. While<br>this author created the AlO diagnostic, these measurements were performed alongside a CO<br>absorption diagnostic used by a different researcher to compare the flame bath gas (via CO)<br>and the region immediately around aluminum particles (via AlO) when varying forms of<br>aluminum powder were used in a propellant. This comparison allows analysis of the burning regime of aluminum particles. Evidence was found that nano-aluminum particles burn in<br>the kinetically controlled combustion regime, while micron-aluminum particles burn in the<br>diffusion-controlled regime.<br>Multi-spectral emission imaging of hypergolic ignition of ammonia borane (AB) is then<br>presented. Three high-speed cameras with multiple optical filters were used to capture<br>infrared and visible wavelength videos of four individual species during AB ignition: BO,<br>BO₂, HBO₂, and the B-H stretch mode of AB were imaged. The ignition process was<br>observed to act in two steps: gas evolution and then propagation of a premixed flame. The<br>evolution of the species and flame front revealed that boranes may continue to complete<br>combustion to a further degree than other boron fuels. This author performed the infrared<br>camera imaging and also ran infrared spectrograph measurements to confirm which species<br>were viewed through the optical filters.<br>Next, a scanned-wavelength direct-absorption diagnostic for directly measuring NH₃ in<br>high-temperature combustion environments is presented. A quantum cascade laser (QCL)<br>was scanned at 5 kHz over multiple NH₃ transitions between 959.9 cm⁻¹ and 960.3 cm⁻¹ to<br>measure path-integrated NH₃ temperature and mole fraction. Many NH₃ transitions overlap<br>with high-temperature water lines at commonly used diagnostic frequencies, severely limiting<br>those diagnostics’ capabilities in water-rich, high-temperature environments that are typical<br>of combustion applications. The optical frequencies used in this diagnostic are insensitive<br>to water absorption and thus remedy this issue. This diagnostic was demonstrated within<br>the flame of ammonia borane. AB-based fuels were burned in ambient air and translated<br>vertically to effectively scan the measurement line-of-sight vertically through the flame. Ad-<br>ditionally, flames of these fuels were characterized at a stationary height in an opposed-flow<br>burner (OFB) under O₂ flow.<br>The final chapter presents scanned-wavelength direct-absorption measurements of path-<br>integrated temperature and CO mole fraction in opposed-flow diffusion flames of hydroxyl-<br>terminated polybutadiene (HTPB). HTPB strands were held in an opposed-flow burner<br>under an opposed flow of O2 or 50/50 O₂/N₂ to create quasi-steady and quasi-1D diffusion<br>flames above the fuel strand. The opposed-flow burner was translated vertically to effectively<br>scan the measurement line-of-sight vertically through the flame. A quantum-cascade laser (QCL) was scanned across the P(2,20), P(0,31), and P(3,14) absorption transitions in CO’s<br>fundamental vibration bands near 2008 cm⁻¹ at 10 kHz to determine the path-integrated<br>temperature and CO mole fraction. The laser beam was passed through sapphire rods<br>held close to the flame edge to bypass the flame boundary and provide a well defined path<br>length for mole fraction measurements. The measured profiles and fuel regression rates<br>were compared to predictions produced by a steady opposed-flow 1D diffusion flame model<br>produced by researchers at the Army Research Lab. The model was generated with chemical<br>kinetics mechanisms employing two different assumptions for the nascent gaseous product of<br>HTPB pyrolysis: C₄H₆ or C₂₀H₃₂. It was found that the C₂₀H₃₂ model produced temperature<br>and CO profiles along with regression rates that agreed more closely with the measured<br>results.<br></p>

<p>This work investigated the effects of varying the crystal sizes of ammonium perchlorate (AP) when embedded with a polymeric binder, hydroxyl-terminated polybutadiene (HTPB) on impact-induced temperature behavior.  AP and HTPB are the most used oxidizers and fuel binders in the aerospace solid rocket design industry. In this study, samples of 200 µm and 400µm coarse AP crystals in HTPB were constructed using a conventional hand-mixing method. Using a parametric optimization technique such as the Taguchi method, direct-ink-writing as the additive manufacturing process was used for achieving the required shape fidelity in printing HTPB and by introducing ultraviolet polymers to decrease the curing time.</p> <p>A drop hammer experiment in conjunction with an infrared camera was used to study the impact-induced behavior in the conventionally made AP-HTPB samples. The thermal images obtained from the camera at millisecond resolution are invaluable and provide information about distribution across the sample surface, and the evolution of temperature rise observed in the samples which are complex and not easily understood otherwise and therefore help in improving and attaining desired propellant performance. A two-sample t-Test has been utilized to infer the results and statistical nonsignificance has been observed in the highest temperature rises among 200 µm and 400 µm AP-HTPB sample conditions but a difference in temperature distribution has been observed. A much uniform distribution of temperature over the sample surface on impact is observed in thermal images of 200 µm AP-HTPB sample condition compared to 400 µm AP-HTPB sample condition.</p>