Flow reactor studies of non-equilibrium plasma-assisted oxidation of n-alkanes.

The oxidation of n-alkanes (C1-C7) has been studied with and without the effects of a nanosecond, non-equilibrium plasma discharge at 1 atm pressure from 420 to 1250 K. Experiments have been performed under nearly isothermal conditions in a flow reactor, where reactive mixtures are diluted in Ar to minimize temperature changes from chemical reactions. Sample extraction performed at the exit of the reactor captures product and intermediate species and stores them in a multi-position valve for subsequent identification and quantification using gas chromatography. By fixing the flow rate in the reactor and varying the temperature, reactivity maps for the oxidation of fuels are achieved. Considering all the fuels studied, fuel consumption under the effects of the plasma is shown to have been enhanced significantly, particularly for the low-temperature regime (T<800 K). In fact, multiple transitions in the rates of fuel consumption are observed depending on fuel with the emergence of a negative-temperature-coefficient regime. For all fuels, the temperature for the transition into the high-temperature chemistry is lowered as a consequence of the plasma being able to increase the rate of fuel consumption. Using a phenomenological interpretation of the intermediate species formed, it can be shown that the active particles produced from the plasma enhance alkyl radical formation at all temperatures and enable low-temperature chain branching for fuels C3 and greater. The significance of this result demonstrates that the plasma provides an opportunity for low-temperature chain branching to occur at reduced pressures, which is typically observed at elevated pressures in thermal induced systems.

Molecular Aluminum Additive for Burn Enhancement of Hydrocarbon Fuels.

Additives to hydrocarbon fuels are commonly explored to change the combustion dynamics, chemical distribution, and/or product integrity. Here we employ a novel aluminum-based molecular additive, Al(I) tetrameric cluster [AlBrNEt3]4 (Et = C2H5), to a hydrocarbon fuel and evaluate the resultant single-droplet combustion properties. This Al4 cluster offers a soluble alternative to nanoscale particulate additives that have recently been explored and may mitigate the observed problems of particle aggregation. Results show the [AlBrNEt3]4 additive to increase the burn rate constant of a toluene-diethyl ether fuel mixture by ∼20% in a room temperature oxygen environment with only 39 mM of active aluminum additive (0.16 wt % limited by additive solubility). In comparison, a roughly similar addition of nano-aluminum particulate shows no discernible difference in burn properties of the hydrocarbon fuel. High speed video shows the [AlBrNEt3]4 to induce microexplosive gas release events during the last ∼30% of the droplet combustion time. We attribute this to HBr gas release based on results of temperature-programmed reaction (TPR) experiments of the [AlBrNEt3]4 dosed with O2 and D2O. A possible mechanism of burn rate enhancement is presented that is consistent with microexplosion observations and TPR results.

Enhanced thermal decomposition of nitromethane on functionalized graphene sheets: ab initio molecular dynamics simulations.

The burning rate of the monopropellant nitromethane (NM) has been observed to increase by adding and dispersing small amounts of functionalized graphene sheets (FGSs) in liquid NM. Until now, no plausible mechanisms for FGSs acting as combustion catalysts have been presented. Here, we report ab initio molecular dynamics simulations showing that carbon vacancy defects within the plane of the FGSs, functionalized with oxygen-containing groups, greatly accelerate the thermal decomposition of NM and its derivatives. This occurs through reaction pathways involving the exchange of protons or oxygens between the oxygen-containing functional groups and NM and its derivatives. FGS initiates and promotes the decomposition of the monopropellant and its derivatives, ultimately forming H(2)O, CO(2), and N(2). Concomitantly, oxygen-containing functional groups on the FGSs are consumed and regenerated without significantly changing the FGSs in accordance with experiments indicating that the FGSs are not consumed during combustion.

ReaxFF reactive force field development and applications for molecular dynamics simulations of ammonia borane dehydrogenation and combustion.

Ammonia borane (AB) has attracted significant attention due to its high hydrogen content (19.6% by mass). To investigate the reaction mechanism associated with the combustion of AB, a reactive force field (ReaxFF) has been developed for use in molecular dynamics (MD) simulations. The ReaxFF parameters have been derived directly from quantum mechanical data (QM). NVT-MD simulations of single- and polymolecular AB thermolysis were conducted in order to validate the force field. The release of the first equivalent H(2) is a unimolecular reaction, and MD simulations show an activation energy of 26.36 kcal mol(-1), which is in good agreement with experimental results. The release of the second H(2) is also a unimolecular reaction; however, the release of a third H(2) requires the formation of a B-N polymer. Similar simulations were conducted with a boron and oxygen system, since the oxidation of boron will be an integral step in AB combustion, and show good agreement with the established mechanism for this system. At low temperatures, boron atoms agglomerate into a cluster, which is oxidized at higher temperatures, eventually forming condensed and gas phase boron-oxide-species. These MD results provide confidence that ReaxFF can properly model the oxidation of AB and provide mechanistic insight into the AB dehydrogenation and combustion reactions.

A novel electrolytic ignition monopropellant microthruster based on low temperature co-fired ceramic tape technology.

A planar 2-D liquid monopropellant microthruster fabricated from low temperature co-fired ceramic tapes and ignited by electrolysis is reported. The volume of the combustion chamber was 820 nL (0.82 mm(3)). Silver electrodes were screen printed and positioned on the top and bottom surfaces of the combustion chamber. A DC voltage potential applied across the electrodes was used to initiate decomposition of hydroxylammonium nitrate (HAN) based liquid monopropellants. A thrust output of 150 mN was obtained using a voltage input of 45 V. Measured ignition energies were as small as 1.9 J. Ignition delays, as short as a few hundred milliseconds, were found dependent on the type of HAN-based propellant and the voltage potential.

Design, fabrication and analysis of stagnation flow microreactors used to study hypergolic reactions.

A novel method to study the condensed phase reactions that occur during the ignition of hypergolic propellants (very fast liquid reactions) using microreactors is presented. Planar counterflow microreactors are used to isolate liquid-phase reactions and diffusion from secondary gas-phase chemical and transport processes that often occur concurrently during the overall ignition process. The counterflow microreactor has made it possible to achieve valuable insight into the preignition mechanisms of hypergolic propellants hitherto not possible using conventional drop or impinging jet tests. In the present paper, the microreactor fabrication, flow field characterization, and reactivity of 2-dimethylaminoethylazide and nitric acid as hypergols are presented. Particle image velocimetry and numerical simulations were conducted to characterize the laminar velocity flow-field from which stagnation point strain rates and contact residence times along the centerline of the microreactor were evaluated. Temperature measurements at the exit of the reactor (as well as at the stagnation point) were used as a measure for the extent of the reaction or the heat released from the reaction. For the hypergols, an increase in reactant flow (or equivalently strain rate at the stagnation point) was found to initially increase reactivity, but eventually resulted in a decrease in temperature, revealing a maxima in temperature and reactivity. The trends indicated a reaction that was initially diffusion or heat loss controlled, which transitioned towards kinetic control at higher strain (flow) rates. This paper details the first comprehensive measurements and analysis of the effects of diffusion based mixing on the interfacial reactions occurring between hypergols.

Electrostatically self-assembled nanocomposite reactive microspheres.

Nanocomposite reactive microspheres with diameters of approximately 1-5 mum were created via electrostatic self-assembly of aluminum and cupric oxide nanoparticles. The ability to utilize this novel approach of bottom-up assembly to create these reactive materials allows for the potential for a more intimate mixture between the two nanoreactants and, thus, an overall more energetic combustion process. Experiments with the self-assembled material demonstrate the ability to achieve ignition and sustain a combustion wave in rectangular microchannels, which does not occur with material having similar amounts of organics mixed via the traditional sonication method.

Functionalized graphene sheet colloids for enhanced fuel/propellant combustion.

We have compared the combustion of the monopropellant nitromethane with that of nitromethane containing colloidal particles of functionalized graphene sheets or metal hydroxides. The linear steady-state burning rates of the monopropellant and colloidal suspensions were determined at room temperature, under a range of pressures (3.35-14.4 MPa) using argon as a pressurizing fluid. The ignition temperatures were lowered and burning rates increased for the colloidal suspensions compared to those of the liquid monopropellant alone, with the graphene sheet suspension having significantly greater burning rates (i.e., greater than 175%). The relative change in burning rate from neat nitromethane increased with increasing concentrations of fuel additives and decreased with increasing pressure until at high pressures no enhancement was found.