Historically, hypergolic propellants have utilized fuels based on hydrazine and its<br>derivatives due to their good performance and short ignition delays with the commonly used<br>hypergolic oxidizers. However, these fuels are highly toxic and require special handling<br><div>precautions for their use.</div><div><br></div><div>In recent years, amine-boranes have begun receiving attention as potential alternatives to<br>these more conventional fuels. The simplest of these materials, ammonia borane (AB, NH3BH3)<br>has been shown to be highly hypergolic with white fuming nitric acid (WFNA), with ignition<br>delays as short as 0.6 milliseconds being observed under certain conditions. Additionally,<br>thermochemical equilibrium calculations predict net gains in specific impulse when AB based<br>fuels are used in place of the more conventional hydrazine-based fuels. As such, AB may serve as<br>a relatively less hazardous alternative to the more standard hypergolic fuels.</div><div><br></div><div>Presented in this work are the results of five major research efforts that were undertaken<br>with the objective of developing high performance fuels based on ammonia borane as well as<br>characterizing their combustion behavior. The first of these efforts was intended to better<br>characterize the ignition delay of ammonia borane with WFNA as well as investigate various fuel<br>binders for use with ammonia borane. Through these efforts, it was determined that Sylgard-184<br>silicone elastomer produced properly curing fuel samples. Additionally, a particle size dependency<br>was observed for the neat material, with the finer particles resulting in ignition delays as short as<br>0.6 milliseconds, some of the shortest ever reported for a hypergolic solid fuel with WFNA.</div><div><br></div><div>The objective of the second area of research was intended to adapt and demonstrate a<br>temperature measurement technique known as phosphor thermography for use with burning solid<br>propellants. Using this technique, the surface temperature of burning nitrocellulose (a homogeneous solid propellant) was successfully measured through a propellant flame. During the<br>steady burning period, average surface temperatures of 534 K were measured across the propellant<br>surface. These measured values were in good agreement with surface temperature measurements<br>obtained elsewhere with embedded thermocouples (T = 523 K). While not strictly related to<br>ammonia borane, this work demonstrated the applicability of this technique for use in studying<br>energetic materials, setting the groundwork for future efforts to adapt this technique further to<br>studying the hypergolic ignition of ammonia borane.</div><div><br></div><div>The third research area undertaken was to develop a novel high-speed multi-spectral<br>imaging diagnostic for use in studying the ignition dynamics and flame structure of ammonia<br>borane. Using this technique, the spectral emissions from BO, BO2, HBO2, and the B-H stretch<br>mode of ammonia borane (and its decomposition products) were selectively imaged and new<br>insights offered into the combustion behavior and hypergolic ignition dynamics of ammonia<br>borane. After the fuel and oxidizer came into contact, a gas evolution stage was observed to<br>precede ignition. During this gas evolution stage, emissions from HBO2 were observed, suggesting<br>that the formation of HBO2 at the AB-nitric acid interface may help drive the initial reactant<br>decomposition and thermal runaway that eventually results in ignition. After the nitric acid was<br>consumed/dispersed, the AB samples began burning with the ambient air, forming a quasi-steady<br>state diffusion controlled flame. Emission intensity profiles measured as a function of height above<br>the pellet revealed the BO/BO2-based emissions to be strongest in the flame zone (corresponding<br>to the highest gas temperatures). Within the inner fuel-rich region of the flame, the HBO2 emission<br>intensity peaked closer to the fuel surface after which it unexpectedly began to decrease across the<br>flame zone. This is seemingly in contradiction to the current understanding that HBO2 is a stable product species and may suggest that for this system it is consumed to form BO2 and other boron oxides.</div><div><br></div><div>The fourth area of research undertaken during this broader research effort investigated the<br>use of ammonia borane and other amine borane additives on the ignition delay and predicted<br>performance of novel hypergolic fuels based on tetramethylethylenediamine (TMEDA). Despite<br>these materials being in some cases only sparingly soluble in TMEDA, solutions of ammonia<br>borane, ethylenediamine bisborane, or tetramethylethylenediamine bisborane in TMEDA resulted<br>in reductions of the mean ignition delays of 43-51%. These ignition delay reductions coupled with<br>the significantly reduced toxicity of these fuels compared to the conventional hydrazine-based<br>hypergolic fuels make them promising, safer alternatives to the more standard hypergolic fuels.<br>Attempts were made to improve these ignition delays further by gelling the TMEDA, allowing for<br>amine borane loadings beyond their respective solubility limits. Moving to these higher loadings<br>had mixed results however, with the ignition delays of the AB/EDBB-based fuels increasing<br>significantly with higher AB/EDBB loadings. The ignition delays of the TMEDABB-based fuels<br>on the other hand decreased with increasing TMEDABB loadings, though the shortest were still<br>comparable to those found with the saturated fuel solutions.</div><div><br></div><div>The final research area that was undertaken was focused on scaling up and developing fuel<br>formulations based on ammonia borane for use in a small-scale hypergolic hybrid rocket motor.<br>Characterization of the regression rate behavior of these fuels under motor conditions suggested<br>the fuel mass flow rate was driven primarily by the thermal decomposition of the ammonia borane.<br>This mechanism is fundamentally different from that which governs the regression rate of most<br>conventional solid fuels used in hybrid rockets as well as that of ethylenediamine bisborane, a<br>similar material in the amine borane family of fuels. Understanding this governing mechanism further may allow for its exploitation to enable high, nearly constant fuel mass flow rates<br>independent of oxidizer mass fluxes. If successful, this would enable further optimization of the<br>design for rocket systems utilizing these fuels, resulting in levels of performance that rival that of<br>the more conventional hydrazine-based fuels.<br></div>

Hypergolic hybrid motors are advantageous for rocket propulsion due to their simplicity, reliability, low weight, and safety. Many hypergolic hybrid fuels with promising theoretical performance are not practical due to their sensitivity to temperature or moisture. Ammonia borane (AB) has been proposed and studied as a potential hypergolic hybrid fuel that provides both excellent performance and storability. This study investigates the effect of droplet impact velocity, pellet composition, and storage humidity on ignition delay of AB with white fuming nitric acid as the oxidizer. Most ignition delays measured were under 50 ms with many under 10 ms and some even under 2 ms, which is extremely short for hybrid systems. Higher droplet velocities led to slightly shorter ignition delays, and exposing samples to humidity slightly increased ignition delay. An AB pellet composition of at least 20% epoxy binder was found to minimize ignition delay. The epoxy facilitates ignition by absorbing or adhering the oxidizer and slowing the reaction with the fuel, preventing oxidizer expulsion and holding it close to the fuel. These results emphasize the importance of binder properties in hypergolic hybrids. Pellets varying in composition and storage method were extinguished and reignited with the oxidizer to demonstrate reignition capability.

<div>When combined with common fuel binders, solid hypergolic fuels can simplify the overall complexity of hybrid rocket systems, as the fuel grain can be ignited and reignited without an external power source or external fluid. In addition, with the hypergolic additive embedded in the binder, the flame zone can be placed at the surface of the grain itself, thereby providing heat to the fuel, improving fuel regression rate, and combustion stability and sustainability. Coupled with high grades of mixed oxides of nitrogen (MON), such hypergolically ignited hybrid configurations are considered a potential propulsion system for a robotic Mars Ascent Vehicle (MAV). Use of the fuel additives and a suitable choice of oxidizer allows for low temperature stability and operation of the propellants, making it an appealing candidate for a simple and storable hybrid propulsion system.</div><div>The first half of this work is dedicated to a very application based study of paraffin based hypergolic hybrids, while the second half of this work, independent from the first, focuses on how theory could help in developing future hypergolic propulsion systems.</div><div>The process undertaken to develop a paraffin based hypergolic hybrid relied heavily on experimental testing of a wide variety of additive loaded fuels with MON to optimize hybrid motor grain parameters with the goals of minimizing ignition delay, improving combustion stability, and promoting sustainment of the flame. MON 3 and MON 25 (3 wt.% or 25 wt.% nitric oxide mixed with nitrogen tetroxide) were used as oxidizers. Through an initial screening process, we selected two solid hypergolic propellants, sodium amide and potassium bis(trimethylsilyl)amide (PBTSA), as additives to promote hypergolic ignition given their low ignition delays with both grades of MON. Iterations on the grain configuration consisted in minimizing the additive loading to simplify the casting process and increase performance, without losing hypergolicity of the grain or hampering combustion sustainability. Using a 90 wt.% hypergolic additive front segment, we were able to light the grain three times using the hypergolic reaction between the additives and MON 3. Once relights achieved, we mainly focused on demonstrating sustained combustion, and determined that, once the front segment depleted, the lack of heat in the system lead the motor to shut down prior to the end of the targeted burn. This led us to add a reactive additive, sodium borohydride, in the main grain, as a way to generate heat in the motor once the front segment was depleted. With the objective of testing relevant conditions for an actual Mars Ascent Vehicle, one of our final tests was done in an altitude chamber, at a 100,000 ft targeted simulated altitude (equivalent to the atmospheric pressure on Mars), with MON 25 as the oxidizer. Using a mixture of sodium amide, PBTSA, and sodium borohydride, we were able to achieve hypergolic ignition in 425 ms (delay to reach 90% of the maximum chamber pressure) at 102,000 ft simulated altitude, for an average chamber pressure of 113 psia.</div><div>During testing we determined that an ideal solid additive should exhibit both low ignition delay with the oxidizer considered, to minimize the motor start up time, and a high heat of combustion, to maximize the energy release and therefore maximize performance. However, the lack of data and theoretical understanding of the reactivity of MONs with non hydrazine based fuels made it challenging to find such an ideal solid additive. Historically, screening processes for new fuel candidates, liquids or solids, have followed a “hit or miss” approach, in which potential fuels were selected based on common characteristics with known hypergols, which is the approach we followed during the development of the hypergolic hybrid. A more robust approach, typically used in the biology and chemistry fields, can be used to predict reactivity of chemicals using statistical analysis. A quantitative structure activity relationship (QSAR) analysis is a statistical analysis used to correlate reactivity to selected molecular descriptors, or properties. Using this approach, one can create models, determined during the QSAR analysis, to predict reactivity of fuel candidates, solely based on their properties. Combined with the recent advancements in computational chemistry and computation of properties, this simple approach has the potential to greatly simplify screening processes for new fuel candidates, as experimental data is not needed anymore. With this method, we were able to fit the logarithmic of the minimum ignition delay for 30 different amines using seven molecular descriptors (heat of formation, heat of vaporization, highest occupied molecular orbital, charge on the nitrogen, rotatable bond count, and ovality), for an R² value of 0.70. While the main motivation behind starting this theoretical work was to optimize for solid additives properties for the hypergolic hybrid configuration described previously, the potential of such model extends to a wider range of propulsion systems (reaction control systems, orbital maneuvering, etc.), and could be expanded to a wider range of oxidizers using machine learning.</div>

No description available.

<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>

Synthèse et étude de nouveaux NHC-Boranes pour leurs propriétés énergétiques et leurs rôles en tant que photo co-amorceurs pour la photopolymérisation en émulsion.Depuis la première synthèse de complexes N-Hétérocycliques Boranes (NHC-Borane) stables en 1993, une étude plus générale de propriétés et réactivité n’a débuté que dans le milieu des années 2000. Les domaines d’applications de ces composés qui sont des paires de Lewis vont de la synthèse organique (agent réducteur, hydroboration de liaisons multiples) en passant par la chimie radicalaire (remplacement de l’hydrure de tributylétain, hydroboration) ou même en tant qu’amorceur ou co-amorceur de polymérisations.L’objet de cette thèse était d’étendre l’application des NHC-Boranes dans deux domaines précis. Un premier axe porte sur les propriétés hypergoliques amenées par leurs structures inédites. Un second est consacré à l’amorçage de réactions de polymérisations en émulsion et l’obtention de particules hybrides sous irradiation visible.Nous avons choisi et synthétisé de nouvelles cibles polyazotées qui ont montré des propriétés énergétiques potentiellement intéressantes pour l’usage de NHC-Boranes en propulsion solide. L’étude mis en évidence des différentes de réactivités en fonction du squelette du carbène utilisé. De plus, un nouveau type de carbène borane pouvant être utilisé dans différents domaines a été synthétisé.Nous avons aussi amélioré la compréhension du système de photoamorçage déjà proposé en polymérisation en émulsion dans le visible. Des points clés, sur la conception du système et du réacteur ont été améliorés. Nous avons aussi pu remplacer le tensioactif utilisé pour proposer la première photopolymérisation en émulsion Pickering. Il en résulte des latex stables, composés de particules hybrides pouvant former des films potentiellement anti-UV. L’excitation dans le visible, pourrait être utilisée dans le but de réduire les coûts énergétiques et même former d’autres particules inédites en évitant la dégradation de composés thermo ou UV-sensibles / Study and synthesis of new NHC-Boranes usable as hypergolic fuels and as photo co-initiators for radical emulsion photopolymerizationsThe first N-Heterocyclic Carbene Borane complex (NHC-Borane) was synthetized in 1993, but we had to wait until the mid-2000s before chemists investigated their properties and reactivity. The applications of NHC-Boranes range from organic chemistry (where they are used as reducing agents or for the hydroboration of multiple bonds) to radical chemistry (as replacement of te tributyltin hydride) and radical polymerizations (initiators and co-initiators). We designed and synthetized new Nitrogen-rich NHC-Boranes. The latter are hypergolic and might serve as fuels for solid propulsion. We managed to synthetize several new classed of NHC-Borane which was or could be used in different fields. We also deepened our understanding of the visible light-induced emulsion polymerization, where the NHC-Boranes serve as co-initiators. We could optimize the process and then replaced the surfactant by an inorganic sol to propose the first Pickering emulsion photopolymerization. Stable latexes of hybrid particles have been generated which might be used as sunscreen films, to reduce the energetic footprint of the reactions and/or to access particles made of heat- or UV-sensitive materials