In this work we develop a Blast-Propellant-Facility integrated analysis study, which evaluates, by using two different approaches, the blast-related impact of an explosive accident of the Space Shuttle during the first ten seconds after launch at Kennedy Space Center. The blast-related risk associated with an explosion at this stage is high because of the quantity of energy involved in both multiple and complex processes. To do this, one of our approaches employed BlastFX®, a software system that facilitates the estimation of the level of damage to people and buildings, starting from an explosive device and rendering results through a complete report that illustrates and facilitates the evaluation of consequences. Our other approaches employed the Hopkinson-Cranz Scaled Law for estimating similar features at a more distant distance and by evaluating bigger amounts of TNT equivalent. Specifically, we considered more than 500 m and 45,400 kg, respectively, which are the range and TNT content limits that our version of BlastFX® can cover. Much research has been done to study the explosion phenomena with respect to both solid and liquid propellants and the laws that underlie the blast waves of an explosion. Therefore our methodology is based on the foundation provided by a large set of literature review and the actual capacities of an application like BlastFX®. By using and integrating the lessons from the literature and the capabilities of the software, we have obtained very useful information for evaluating different scenarios that rely on the assumption, which is largely studied, that the blast waves' behavior is affected by the distance. All of this has been focused on the Space Shuttle system, in which propellant mass represents the source of our analysis and the core of this work. Estimating the risks involved in it and providing results based on different scenarios augments the collective knowledge of risks associated with space exploration.

<p>In an AP-HTPB propellant microstructure, the local strain rate depends on the AP crystal size and the material, while the local temperature rate depends on the impact velocity, AP crystal size, and the material.  Larger AP crystals lead to higher local strain rates and higher local temperature rates, which means hot spots are more likely to occur in AP-HTPB propellants with more large AP crystals.</p>

Fertile White Leghorn (Gallus gallus) and Bobwhite Quail (Colinus virginianus) were subjected to 15 min exposures produced by burning solid rocket motor (SRM) fuel. Comparative mortality data were collected. Chicken eggs were further used to study the effects of exposure on water relations and blood gas parameters. Chicken embryos exposed once on day 19 or incubation demonstrated and LD50 of 204 ppm; the LD50 for quail embryos was 175 ppm. When mortality was regressed on the final exposure concentration, chicken and quail embryos exposed on days 12 and 19 showed LD50's of 127 and 86 ppm respectively, and embryos exposed on days 4, 12, and 19 had LD50's of 75 and 56 ppm. Quail embryos appeared to be more sensitive to SRM exhausts than chicken embryos, probably owing to the larger surface area to volume ration of the egg. Embryos exposed to a small daily concentration had an MLC of 117 ppm and an LD50 of approximately 200 ppm for cumulative exposure concentrations. This suggested that individual exposures were additive in effect. Eggs exposed at temperatures less than 37.5 C showed reduced lethality, while exposures at greater temperatures increased lethality. The rate of water loss from chicken eggs measured over an eight hour period increased 5 times because of a 15 min exposure. Since the increased rate of dehydration occurred during the exposure, the hydroscopic effects of exposure were extreme. When eggs lose the 18% of the initial weight normally lost from evaporation during incubation due to exposure, no more water loss was seen to occur. Blood gas analyses on 12 day embryos showed decreased pH at cumulative exposure concentrations greater than 200 ppm. Carbon monoxide in the exhausts probably increased carboxyhemoglobin, reducing buffering capacity. The acidosis was partially compensated by increased HCO3-, Exogenously derived C1-, plus increased HCO3- may shift intracellular K+, making the serum hyperkatremic. Dehydration effects further increased serum hypertonicity.

Energetic materials (i.e., explosives, propellants, and pyrotechnics) have been used for centuries in a wide variety of applications that include celebratory firework displays, the demolition of ‘immovable’ structures, mining resources from the earth’s crust, launching humans into outer space, and propelling munitions across the battlefield. Many different scientific and engineering domains have found unique value in their characteristic release of significant heat and pressure. While the rate at which energetic materials react is often dependent on the source of initiation, surrounding thermodynamic conditions, and formulation sensitivity, many applications aim for a controlled combustion process to produce large amounts of work output – solid and liquid rocket motors and gun-launched projectiles are a few key examples. Other energetic material systems are often inadvertently exposed to thermal insults, which can result in similar combustion behavior. To accurately model these systems, it is important to have a fundamental understanding of the chemical kinetics that control various aspects of the combustion process (e.g., changes in temperature (T), pressure (P), and species mole fractions (X)). Detailed chemical kinetic models are often used to understand and subsequently predict such behavior. Understanding the gas-phase reaction kinetics of energetic materials is essential when trying to predict critical performance parameters such as flame speeds, temperature and pressure profiles, and heat flux between material phases. These parameters can have significant impact on predictions of system-level performance (e.g., the specific impulse of solid rocket motors, propellant burn rates in projectile systems, and munition responses to thermal insult and extended temperature cycling). While the gas-phase reaction kinetics of energetic material combustion were heavily studied from the late 1970’s to the early 2000’s, research efforts beyond this time frame have primarily focused on condensed-phase chemistry as it is thought to be less understood. Over the past two decades, however, there have been significant advances in our understanding of small molecule reactions that have not yet been accounted for in many energetic material models. One such example are chemically termolecular reactions – a new class of phenomenological reactions that have not yet been considered for inclusion in any energetic material kinetic models. Recent studies have indicated that chemically termolecular reactions, mediated through ephemeral collision complexes, have significant impact on the global kinetics of certain combustion systems. This discovery has since prompted the question of which systems are significantly influenced by chemically termolecular reactions and should therefore account for their presence in gas-phase phenomenological models. Although a select number of systems have already been investigated, such as flame speed and ignition delay predictions in common hydrocarbon combustion scenarios, the influence of chemically termolecular reactions on the kinetics of energetic materials has not yet been explored. As an initial investigation into energetic materials, a case study for RDX was performed, for which abundant computational and experimental data are available. To aid in assessing the impact of chemically termolecular reactions, for which almost no data are available, this study leveraged an automated procedure to identify and estimate rate constants for potential chemically termolecular reactions based exclusively on data available for related reactions. Four detailed kinetics models for RDX were independently screened for potential chemically termolecular reactions. Model predictions including these chemically termolecular reactions revealed that they have significant potential impact on profiles of major species, radicals, and temperatures. T he analysis pinpointed ∼20-40 chemically termolecular reactions, out of the thousands of possibilities, estimated to have the largest impact. These reactions, including many mediated by ephemeral HNO** and NNH** complexes, are therefore worthwhile candidates for more accurate quantification via master equation calculations. More generally, just as the importance of including chemically termolecular reactions in hydrocarbon combustion models is becoming recognized, the present results show compelling evidence for the need for their inclusion in energetic material models as well. The investigation into chemically termolecular reactions yielded a secondary conclusion based on the observed influence of the small molecule C/H/N/O chemistry on overall predictions of energetic material combustion – updating the small molecule chemistry in RDX models produced significant changes to predictions of major species and temperature, suggesting that the development of a comprehensive gas-phase energetic material combustion model would be of great value and have broad utility as a foundational model for a great variety of C/H/N/O energetic materials. To begin developing such a model, all small molecule chemistry in current kinetic models was reviewed with the intent of identifying a sub-model in need of revisions and subsequently addressing its uncertainties using targeted experiments to improve overall predictions. The ammonia sub-model was selected as it is both highly uncertain and highly influential in many energetic material models. Ammonia (NH₃) has garnered substantial attention in recent years due to its importance across many scientific domains – including its potential use as a carbon-free fuel and long-term energy storage option, its use in reducing combustion-generated nitrogen oxide emissions, its role as a decomposition fragment of many energetic materials, and its presence as an important impurity during biofuel and biomass combustion that can affect overall system kinetics, among others. Yet, it is generally recognized that there are still significant gaps in the present understanding of ammonia kinetics -– in both experimental data sets and sub-models within the overall ammonia kinetic mechanism. For example, most experimental studies of ammonia oxidation have used molecular oxygen as the primary or sole oxidizer. While large mole fractions of molecular oxygen are encountered in many combustion scenarios, there are select systems where ammonia is more likely to be oxidized via nitrogen-containing species (e.g. N₂O and NO₂) and, more generally, there are relatively untested reaction sets that would be accentuated in such conditions. To address these gaps in available experimental data needed for the validation of ammonia kinetics models, jet-stirred reactor experiments were performed for mixtures of NH₃/N₂O/N₂ over an intermediate temperature range (850-1180 K). In these experiments, the mole fractions of NH₃, N₂O, and NO were measured using a combination of gas chromatography, chemiluminescence, electrochemical detection, and infrared absorption – where agreement among the different diagnostics (within 3% for N₂O and 7% for NO) ensured high confidence in the experimental measurements. Comparison of the experimental results and model predictions suggested deficiencies in commonly used models for nitrogen kinetics. Various modeling analyses pointed to the central role of the N₂O + NH₂ = N₂H₂ + NO reaction, on which recent kinetic models all rely on the same rate constant estimate that appears to have not been tested in previous validation data sets for NH₃ kinetics. A second set of jet-stirred reactor experiments were performed for mixtures of NH₃/NO₂/O₂/N₂ over a slightly different temperature range (700–1100 K). Agreement among different diagnostics (≤7% for NO₂ and ≤4% for NH₃) and excellent experimental repeatability confirmed high confidence in all species measurements. Measured mole fractions were compared to predictions from five recently developed kinetic models using flux analysis and uncertainty-weighted kinetic sensitivity analysis, both of which pointed to the importance of reactions involving H₂NO that are both influential in this system and highly uncertain. The measurements from the jet-stirred reactor experiments presented here were combined with comprehensive sets of experimental data and high-level theoretical kinetics calculations using the MultiScale Informatics (MSI) approach to unravel the large uncertainties present in current NH3 oxidation kinetic sub-models. Emphasis was placed on NH₃ oxidation via nitrogen-containing species as this chemistry has been shown to accentuate influential reactions (e.g., the NO₂+NH₂ and NH₂+NO reactions) that are known to be important during the combustion of many energetic materials (e.g., AN, ADN, and AP). The resulting MSI model accurately predicted nearly all of the experimental and theoretical target data within estimated or reported uncertainties. Additional predictions of two NH₃/NO₂ validation data sets, which were not included in the MSI framework, demonstrated its ability to accurately extrapolate predictions to untested T/P/X conditions, indicating that the converged MSI model demonstrates truly predictive behavior. The MSI NH₃ oxidation model presented here should be considered for inclusion in many energetic material models as the NH₃/NOₓ kinetic system is known to be important to the combustion of various propellant and explosive formulations. This sub-model will help to form a foundational gas-phase kinetic model relevant to many different energetic materials, including those that contain inorganic additives for increased energy density and blast effects.

In this study the applicability of Carbon-13 NMR and XPS to the detection of chemical changes in a solid composite rocket propellant was studied. Storage at elevated temperatures was used to simulate the propellant ageing process. In the XPS analysis, changes in the sources for the N(1s) and Cl(2p) photopeaks were investigated. The propellant loses "organic" nitrogen as it ages. Changes in the amount of Cl⁻ present are in doubt due to instrumental considerations. Carbon-13 NMR analysis showed that with increasing age of a sample there is a corresponding loss of vinylic groups from the binder. This loss of vinylic character is preferential in the order pendant>>cis>trans. Due to the long scan times involved this method is of limited utility for ageing analysis. / Master of Science

A dual-frequency microwave bum rate measurement system for solid rocket motors has been developed and is described. The system operates in the X-band (8.2-12.4 Ghz) and uses two independent frequencies operating simultaneously to measure the instantaneous bum rate in a solid rocket motor. Modeling of the two frequency system was performed to determine its effectiveness in limiting errors caused by secondary reflections and errors in the estimates of certain material properties, particularly the microwave wavelength in the propellant. Computer simulations based upon the modeling were performed and are presented. Limited laboratory testing of the system was also conducted to determine its ability perform as modeled. Simulations showed that the frequency ratio and the initial motor geometry (propellant thickness and combustion chamber diameter) determined the effectiveness of the system in reducing secondary reflections. Results presented show that higher frequency ratios provided better error reduction. Overall, the simulations showed that a dual frequency system can provide up to a 75% reduction in burn rate error over that returned by a single frequency system. The hardware and software for dual frequency measurements was developed and tested, however, further instrumentation work is required to increase the rate at which data is acquired using the methods presented here. The system presents some advantages over the single frequency method but further work needs to be done to realize its full potential. / Master of Science

<p dir="ltr">Reported herein is a brief summary regarding the previous syntheses of borane-amines, newly developed protocols to synthesize borane-amines, and the material and synthetic applications utilizing borane-amines. Methods to generate borane-amines typically relied on a metathesis-dehydrogenation reaction between ammonium salts and metal borohydrides in organic solvent, typically hazardous tetrahydrofuran (THF). However, due to the poor solubility of inorganic salts in organic solvent, stirring of the reaction mixture becomes difficult and, in turn, scalability is made challenging. We report two new methods to generate borane-amines that both rely on the hydroboration of sodium borohydride and a carbonyl activator, followed by the S_N2-type reaction with the amine to form the requisite borane-amine. The activator for our procedures are either 1) gaseous carbon dioxide or 2) water/ethyl acetate system. The CO₂ mediated protocol was applied to a variety of 1°-, 2°-, 3°-, and heteroaromatic amines as well as phosphines to form the corresponding borane adducts (73-99%). Water was also found to be a green, compatible activator. Interestingly, we had swapped environmentally and health hazardous THF with ethyl acetate (EtOAc) and found the reaction had still proceeded with competitive conversion of amines to the borane-amines (72-97%). The robustness of this reaction was demonstrated with a 1.1 mol scale synthesis of borane pyridine with 87% yield. With increased accessibility of borane-amines established, we sought to investigate their potential applications, including testing their hypergolic properties. Additionally, we utilized borane-ammonia for a sequential reduction/Friedel-Crafts alkylation of benzyl carbonyls. Traditionally an alkyl halide, the scope of the electrophilic aromatic substitution reaction has widened to include alcohols and carbonyls as potential Friedel-Crafts reactants. Few reports exist for the arylation of aldehydes and ketones, while no precedence exists for the arylation of carboxylic acids and esters. Our group previously reported that TiCl₄ is capable of eliminating oxygen from benzyl alcohols, forming a carbocation intermediate. Theoretically, the carbocation formed from TiCl₄ and benzyl alcohols would be vulnerable from attacks from other nucleophiles, including pi bonds from arenes. This was indeed proven to be the case when benzyl alcohol was reacted in 1 equiv. TiCl₄with benzene as the solvent and diphenylmethane was obtained as the sole product. By including borane-ammonia as a hydride source, various aryl carbonyls and aryl carbinols were also reduced to the corresponding alcohol <i>in situ</i>, enabling these substrates to participate in Friedel-Crafts alkylation.</p>

Structural energetic materials (SEM) are a class of multicomponent materials which may react under various conditions to release energy. Fragmentation and impact induced reaction are not well characterized phenomena in SEMs. The structural energetic systems under consideration here combine aluminum with one or more of the following: nickel, tantalum, tungsten, and/or zirconium. These metal+Al systems were formulated with powders and consolidated using explosive compaction or the gas dynamic cold spray process. Fragment size distributions of the indicated metal+Al systems were explored; mean fragment sizes were found to be smaller than those from homogeneous ductile metals at comparable strain rates, posing a reduced risk to innocent bystanders if used in munitions. Extensive interface failure was observed which suggested that the interface density of these systems was an important parameter in their fragmentation. Existing fragmentation models for ductile materials did not adequately capture the fragmentation behavior of the structural energetic materials in question. A correction was suggested to modify an existing fragmentation model to expand its applicability to structural energetic materials. Fragment data demonstrated that the structural energetic materials in question provided a significant mass of combustible fragments. The potential combustion enthalpy of these fragments was shown to be significant. Impact experiments were utilized to study impact induced reaction in the indicated metal+Al SEM systems. Mesoscale parametric simulations of these experiments indicated that the topology of the microstructure constituents, particularly the stronger phase(s), played a significant role in regulating impact induced reactions. Materials in which the hard phase was topologically connected were more likely to react at a lower impact velocity due to plastic deformation induced temperature increases. When a compliant matrix surrounded stronger, simply connected particles, the compliant matrix accommodated nearly all of the deformation, which limited plastic deformation induced temperature increases in the stronger particles and reduced reactivity. Decreased difference between the strength of the constituents in the material also increased reactivity. The results presented here demonstrate that the fragmentation and reaction of metal+Al structural energetic materials are influenced by composition, microstructure topology, interface density, and constituent mechanical properties.

Nanoenergetic composite materials have been synthesized by a sol-gel chemical process where the addition of a weak base molecule induces the gelation of a hydrated metal salt solution. A proposed proton scavenging mechanism, where a weak base molecule extracts a proton from the coordination sphere of the hydrated iron (III) complex in the gelation process to form iron (III) oxide/hydroxide, FeIIIxOyHz, has been confirmed for the weak base propylene oxide (PO), a 1,2 epoxide, as well as for the weak bases tetrahydrofuran (THF), a 1,4 epoxide, and pyridine, a heterocyclic nitrogen-containing compound. THF follows a similar mechanism as PO; the epoxide extracts a proton from the coordination sphere of the hydrated iron complex forming a protonated epoxide which then undergoes irreversible ring-opening after reaction with a nucleophile in solution. Pyridine also extracts a proton from the hydrated metal complex, however, the stable six-membered molecule has low associated ring strain and does not endure ring-opening. Fe2O3/Al energetic systems were synthesized from the epoxides PO, trimethylene oxide (TMO) and 3,3 dimethyl oxetane (DMO). Surface area analysis of the synthesized matrices shows a direct correlation between the surface area of the iron (III) oxide matrix and the quantified exothermic heat of reaction of the nano-scaled aluminum-containing energetic material due to the magnitude of the interfacial surface area contact between the iron (III) oxide matrix and the aluminum particles. The Fe2O3(PO)/Al systems possess the highest heat of reaction values due to the oxide interfacial surface area available for contact with the aluminum particles. Also, reactions containing nano-scale aluminum react differently than those containing micron-scale aluminum. RuO2/Al energetic systems behave differently dependent on the atmosphere the sample is heated. Heating the RuO2/Al samples in an inert atmosphere results in the complete reduction of the ruthenium oxide matrix to Ru(0) before reaction with the aluminum particles, resulting in the exothermic formation of RuxAly intermetallics, with the stoichiometry dependent on the initial Ru:Al concentration. However, heating the samples in an oxygen-rich atmosphere results in an exothermic reaction between RuO2 and Al.

Estimation of the total mission life of a spacecraft is an important issue for the communication satellite industries. For accurate determination of the remaining mission life of the satellite it is essential to estimate the amount of propellant present in the propellant tank of the spacecraft at various stages of its mission life. Because the annual revenue incurred from a typical communication satellite operating at its full capacity is on the order of millions of dollars, premature removal of spacecraft from their orbits results in heavy losses. Various techniques such as the bo okkeeping method, the gas law method, numerical modeling techniques, and use of capacitive sensors have been employed in the past for accurate determination of the amount of propellant present in a spacecraft. First half of the thesis is concerned with sensitivity analysis of the various propellant gauging techniques, that is, estimating the e ects of the uncertainty in the instruments employed in the propellant gauging system on the onboard propellant estimation. This sensitivity analysis is done for three existing propellant gauging techniques – gas injection method, book-keeping method and the propellant tank heating method. A comparative study of the precision with which the onboard propellant is estimated by the three techniques is done and the primary source of uncertainty for all the three techniques is identified. It is illustrated that all the three methods — the gas injection method, the book-keeping method and the propellant tank heating method — are inherently indirect methods of propellant gauging, as a consequence of which, the precision with which the three techniques estimate the residual propellant decreases towards the end of mission life of the spacecraft. The second half of the thesis explores the possibility of using a new propellant tank configuration, consisting of a truncated cone centrally mounted within a spherical propellant tank, to measure the amount of liquid propellant present within the tank. The liquid propellant present within the propellant tank orients itself in a geometry, by virtue of its dominant surface tension force in zero-g condition, which minimizes its total surface energy. Study reveals that the amount of liquid propellant present in the tank can thus be estimated by measuring the height of the propellant meniscus within the central cone. It is also observed that, unlike gas law metho d, bookkeeping method or the propellant tank heating metho d, where the precision of the estimated propellant fill-fraction decreases towards the end-of-life of the spacecraft, for the proposed new configuration the precision increases.