The focus of the present work is on the empirical characterization and modeling of ignition trends of ternary blends of three distinct hydrocarbon classes, namely a methyl ester (C9H18O2), a linear alkane (n-C9H20), and a cycloalkane (MCH). Numerous surrogate biofuel formulations have been proposed in the literature, yet specific blending of these species has not been studied. Moreover, the effects of blending biofuel compounds with conventional hydrocarbons are not widely studied and a further point is the lack of studies paying specific attention to the effects of fuel variation within a given blended biofuel. To this end, a statistical Design of Experiments L9 array, comprised of 4 parameters (%MO, %MCH, pressure, and equivalence ratio) with 3 levels of variation, constructed in order to systematically study the effects of relative fuel concentrations within the ternary blend enabled variations in fuel concentration for methyl octanoate and MCH of 10% - 30% and 20% - 40%, respectively. Variation in pressure of 1 atm, 5 atm, and 10 atm and in equivalence ratio of 0.5, 1.0, and 2.0 were used, respectively. The fuel-volume percentage of n-nonane varied from 30% - 70%. In total, 10 ternary blends were studied. Ignition delay times for the ternary blends and for the three constituents were obtained by monitoring excited-state OH or CH transitions, A2Epsilon+ -> X2Pi or A2Delta -> X2Pi, respectively, behind reflected shock waves using a heated shock tube facility. Dilute conditions of 99% Ar (vol.) were maintained in all shock tube experiments with the exception of a separate series of n-nonane and MCH experiments under stoichiometric conditions which used 4% oxygen (corresponding to ~ 95% Ar dilution). Temperatures behind reflected shock waves were varied over the range 1243 < T (K) < 1672. From over 450 shock tube experiments, empirical ignition delay time correlations were constructed for all three pure fuels and a master correlation equation for the blended fuels. Ignition experiments conducted on the pure fuels at 1.5 atm indicated the following ignition delay time order, from shortest to longest: methyl octanoate < n-nonane < MCH. With increased pressure to 10 atm (nominal) the order remained, in general, consistent. Under fuel-lean conditions, ignition trends between methyl octanoate and n-nonane exhibited overlap at temperatures below 1350 K, below which the trends diverged with methyl octanoate having shorter ignition delay times. Similar behavior was observed under fuel-rich conditions, yet with the overlap occurring above 1450 K. Stoichiometric ignition trends did not display overlapping behavior under either 1.5 atm or 10 atm pressure. Laminar flame speed measurements were performed at 1 atm and an initial temperature of 443 K on the pure fuel constituents. Additional flame speed measurements of MCH were conducted at 403 K to compare with literature values and were shown to agree strongly with experiments conducted in a constant-volume apparatus. The experiments conducted herein, for the first time, measure laminar flame speeds methyl octanoate. A detailed chemical kinetics mechanism was compiled from three independent, well-validated models for the constituent fuels, where the sub-mechanisms for methyl octanoate and MCH were extracted for integration into a base n-nonane model. The compiled mechanism in the present study (4785 reactions and 1082 species) enables modeling of oxidation processes of the ternary fuel blends of interest. Calculations were performed using the compiled model relative to the base models to assess the impact of utilizing different base chemistry sets. In general, results were reproduced well relative to base models for both n-nonane and MCH, however results for methyl octanoate from both the compiled model and the base model are in disagreement with the results measured herein. Ignition delay times of the fuel blends are well-predicted for several conditions, specifically for blends at lean/high-pressure and stoichiometric/high-pressure conditions, however are not accurately modeled at fuel-rich, high-pressure conditions.

The practical applications of surfactant solutions in confined geometries require a thorough understanding of the system properties. Coarse-grained simulation techniques are useful for studying the qualitative behaviour of these systems, whereas the atomistic molecular dynamics (MD) technique can be used to obtain a molecular-level description. In this work, canonical MD simulations were performed using GROMACS version 4.0 to investigate the self-assembling behaviour of sodium octanoate (SO) confined between two parallel walls. In particular, the effects of gap size, wall type, and surfactant concentrations on the morphology of the surfactant aggregates were studied to gain in-depth knowledge of the system. The simulation results reveal that the morphology of the micelles formed between two parallel walls are affected not only by the gap size and surfactant concentration, but also by the nature and characteristics of the confining walls. With the graphite walls, most octanoate molecules are adsorbed at lower concentrations, but they form micellar aggregates as the surfactant concentration increases. Spherical micelles were found in the larger gaps (4 nm and 5 nm) but not in the smaller gap (3 nm), and the micellar shape also changes with increasing surfactant concentration. SO forms bilayer structures instead of spherical micelles between two silica walls. Interestingly, in the hydrophilic silica confinement, the orientation of these bilayers changes with gap sizes, whereas in the hydrophobic silica confinement, these bilayers remain perpendicular to the wall in all cases. Potentials of mean force between different molecules and atomic groups were determined under different conditions in order to develop a better understanding of the simulation results. It reveals, the presence of the confinement can alter the intermolecular interactions among the surfactant molecules, which, in turn, directly affects the self-assembling process, particularly the size and shape of the aggregates. Indeed, the formation of bilayers in silica wall confinement, as opposed to spherical micelles in graphite confinement, is caused by the enhanced electrostatic interactions between the charged atoms in the solution. The results of this study are expected to provide further insight into the self-assembling behaviour of confined surfactant systems, and may ultimately lead to the development of novel nanomaterials.