Chain-branching reactions represent a general motif in chemistry, encountered in atmospheric chemistry, combustion, polymerization, and photochemistry; the nature and amount of radicals generated by chain-branching are decisive for the reaction progress, its energy signature, and the time towards its completion. In this study, experimental evidence for two new types of chain-branching reactions is presented, based upon detection of highly oxidized multifunctional molecules (HOM) formed during the gas-phase low-temperature oxidation of a branched alkane under conditions relevant to combustion. The oxidation of 2,5-dimethylhexane (DMH) in a jet-stirred reactor (JSR) was studied using synchrotron vacuum ultra-violet photoionization molecular beam mass spectrometry (SVUV-PI-MBMS). Specifically, species with four and five oxygen atoms were probed, having molecular formulas of C8H14O4 (e.g., diketo-hydroperoxide/keto-hydroperoxy cyclic ether) and C8H16O5 (e.g., keto-dihydroperoxide/dihydroperoxy cyclic ether), respectively. The formation of C8H16O5 species involves alternative isomerization of OOQOOH radicals via intramolecular H-atom migration, followed by third O2 addition, intramolecular isomerization, and OH release; C8H14O4 species are proposed to result from subsequent reactions of C8H16O5 species. The mechanistic pathways involving these species are related to those proposed as a source of low-volatility highly oxygenated species in Earth's troposphere. At the higher temperatures relevant to auto-ignition, they can result in a net increase of hydroxyl radical production, so these are additional radical chain-branching pathways for ignition. The results presented herein extend the conceptual basis of reaction mechanisms used to predict the reaction behavior of ignition, and have implications on atmospheric gas-phase chemistry and the oxidative stability of organic substances. © 2015 The Combustion Institute.

Hot-press molding of glass-fiber-reinforced polypropylene (GFPP) laminates was monitored using longitudinally and transversely embedded fiber Bragg gratings (FBGs) at different locations in unidirectional laminates. The optical sensors proved to efficiently characterize some material properties; for example, strain variations could be related physical change of the laminate, revealing key transition points such as the onset of melt or solidification. These results were confirmed through some comparison with traditional techniques such as differential scanning calorimetry. After the GFPP plate was released from the mold, residual strains were estimated. Because cooling rate is an important process parameter in thermoplastics, affecting crystallinity and ultimately residual strain, two different conditions (22 and 3 °C/min) were investigated. In the longitudinal direction, results were nearly identical while in the transverse direction results showed a 20% discrepancy. Coefficients of thermal expansion (CTE) were also identified during a post-process heating procedure using the embedded FBGs and compared to the results of a thermo-mechanical analysis. Again, dissimilarities were observed for the transverse direction. With regards to through the thickness properties, no differences were observed for residual strains or for CTEs.

Detailed measurements are presented of the turbulent flow field, gas species concentrations and temperature field in a non-premixed methane swirl flame. Attention is given to the effect of the quarl geometry on the flame structure and emission characteristics due to its importance in gas turbine and industrial burner applications. Two different quarls were fitted to the burner exit, one a straight quarl and the other a diverging quarl of 15° half cone angle. Stereoscopic Particle Image Velocimetry (SPIV) was applied to obtain the three components of the instantaneous velocity on a vertical plane immediately downstream of the quarl exit. Temperature and gaseous species measurements were made both inside and downstream of the quarls, using a fine wire thermocouple and sampling probe, respectively. This work provides experimental verification by complementary techniques. The results showed that although the main flame structures were governed by the swirl motion imparted to the air stream, the quarl geometry, fuel loading and air loading also had a significant effect on the flow pattern, turbulence intensity, mixture formation, temperature distribution, emissions and flame stabilization. Particularly, in the case of the straight quarl flame, the flow pattern leads to strong, rapid mixing and reduces the residence time for NO formation within the internal recirculation zone (IRZ). However, for the diverging quarl flames, the recirculation zone is shifted radially outward, and the turbulent interaction between the central fuel jet and the internal recirculation zone IRZ induces another small vortex between these two flow features. Less mixing near the diverging quarl exit is observed, with a higher concentration of NO and CO in the post-combustion zone. The instantaneous flow field for both flames showed the existence of small scale vortical structure near the shear layers which were not apparent in the time averaged flow field. These structures, along with high levels of turbulence present in the shear layer, result in the enhancement of the mixing, especially with straight quarl. This article outlines results that yield deeper insight into the combustion of swirling flames stabilized within the quarl and to establish an experimental data base for modelers.

Using n-butane, n-heptane and iso-octane as representative fuels exhibiting NTC (negative temperature coefficient) behavior, comprehensive computational studies with detailed mechanisms and theoretical analysis were performed to investigate the upper stationary point, denoted as turnover states, on the NTC curve near the higher temperature regime, where the ignition delay τ exhibits a local maximum. It is found that the global behavior of the turnover states exhibits distinctive thermodynamic and kinetic characteristics under different pressures, in that the ignition delay at the turnover states shows an Arrhenius dependence on the temperature T and an approximate inverse quadratic power law dependence on the pressure P. These global behaviors imply that the temperature and pressure of the turnover states are not independent and can be correlated by Arrhenius dependence, as ln P ∝ 1/T. Further theoretical analyses demonstrate that such turnover states result from the competition between the low-temperature chain branching reactions and the decomposition of the intermediate species, and therefore correspond to a critical value, α, of the ratio of OH production from low-temperature chemistry. In addition, the ignition delay at the turnover state can be well correlated by the analytical expression derived by Peters et al., with the further demonstration that the pressure dependence of the turnover ignition delay mainly result from the H2O2 decomposition reaction. Comparison of the present results with the literature experimental data of n-heptane ignition delay time shows very good agreement.

The effects of temperature and composition stratifications on the ignition of a lean n-heptane/air mixture at three initial mean temperatures under elevated pressure are investigated using direct numerical simulations (DNSs) with a 58-species reduced mechanism. Two-dimensional DNSs are performed by varying several key parameters: initial mean temperature, T0, and the variance of temperature and equivalence ratio (T' and φ') with different T-φcorrelations. It is found that for cases with φ' only, the overall combustion occurs more quickly and the mean heat release rate (HRR) increases more slowly with increasing φ' regardless of T0. For cases with T' only, however, the overall combustion is retarded/advanced in time with increasing T' for low/high T0 relative to the negative-temperature coefficient (NTC) regime resulting from a longer/shorter overall ignition delay of the mixture. For cases with uncorrelated T-φfields, the mean HRR is more distributed over time compared to the corresponding cases with T' or φ' only. For negatively-correlated cases, however, the temporal evolution of the overall combustion exhibits quite non-monotonic behavior with increasing T' and φ' depending on T0. All of these characteristics are found to be primarily related to the 0-D ignition delays of initial mixtures, the relative timescales between 0-D ignition delay and turbulence, and the dominance of the deflagration mode during the ignition. These results suggest that an appropriate combination of T' and φ' together with a well-prepared T-φdistribution can alleviate an excessive pressure-rise rate (PRR) and control ignition-timing in homogeneous charge compression-ignition (HCCI) combustion. In addition, critical species and reactions for the ignition of n-heptane/air mixture through the whole ignition process are estimated by comparing the temporal evolution of the mean mass fractions of important species with the overall reaction pathways of n-heptane oxidation mechanism. The chemical explosive mode analysis (CEMA) verifies the important species and reactions for the ignition at different locations and times by evaluating the explosive index (EI) of species and the participation index (PI) of reactions. © 2015 The Combustion Institute.

The stabilization characteristics of laminar non-premixed jet flames of pre-vaporized iso-octane, one of the primary reference fuels for octane rating, have been studied experimentally in heated coflow air. Non-autoignited and autoignited lifted flames were analyzed. With the coflow air at relatively low initial temperatures below 940 K, an external ignition source was required to stabilize the flame. These lifted flames had tribrachial edge structures and their liftoff heights correlated well with the jet velocity scaled by stoichiometric laminar burning velocity, indicating the importance of the edge propagation speed on flame stabilization. At high initial temperatures over 940 K, the autoignited flames were stabilized without requiring an external ignition source. These autoignited lifted flames exhibited either tribrachial edge structures or mild combustion behaviors depending on the level of fuel dilution. Two distinct transition behaviors were observed in the autoignition regime from a nozzle-attached flame to a lifted tribrachial-edge flame and then to lifted mild combustion as the jet velocity increased at a certain fuel dilution level. The liftoff data of the autoignited flames with tribrachial edges were analyzed based on calculated ignition delay times. Analysis of the experimental data suggested that ignition delay time may be much less sensitive to initial temperature under atmospheric pressure conditions as compared with predictions. © 2015 Elsevier Ltd. All rights reserved.

Interactions of turbulence, molecular transport, and energy transport, coupled with chemistry play a crucial role in the evolution of flame surface geometry, propagation, annihilation, and local extinction/re-ignition characteristics of intensely turbulent premixed flames. This study seeks to understand how these interactions affect flame surface annihilation of lean hydrogen–air premixed turbulent flames. Direct numerical simulations (DNSs) are conducted at different parametric conditions with a detailed reaction mechanism and transport properties for hydrogen–air flames. Flame particle tracking (FPT) technique is used to follow specific flame surface segments. An analytical expression for the local displacement flame speed (Sd) of a temperature isosurface is considered, and the contributions of transport, chemistry, and kinematics on the displacement flame speed at different turbulence-flame interaction conditions are identified. In general, the displacement flame speed for the flame particles is found to increase with time for all conditions considered. This is because, eventually all flame surfaces and their resident flame particles approach annihilation by reactant island formation at the end of stretching and folding processes induced by turbulence. Statistics of principal curvature evolving in time, obtained using FPT, suggest that these islands are ellipsoidal on average enclosing fresh reactants. Further examinations show that the increase in Sd is caused by the increased negative curvature of the flame surface and eventual homogenization of temperature gradients as these reactant islands shrink due to flame propagation and turbulent mixing. Finally, the evolution of the normalized, averaged, displacement flame speed vs. stretch Karlovitz number are found to collapse on a narrow band, suggesting that a unified description of flame speed dependence on stretch rate may be possible in the Lagrangian description.

We develop a simplified model to better explain electric current response when direct current (DC) is applied to a flame. In particular, different current responses have been observed by changing the polarity of the DC in a sub-saturated current regime that results from the presence of ions and electrons in the flame zone. A flame zone was modeled as a thin, ionized layer located in one-dimensional DC electric fields. We derived simplified model-governing equations from species equations by implementing mobility differences dependent on the type of charged particle, particularly between ions and electrons; we performed experiments to substantiate the model. Results showed that the sub-saturated current and local field intensity were significantly influenced by the polarity of the DC because of the combined effect of unequal mobility of charged particles and the position of the ionized layer in the gap relative to two electrodes. When an energized electrode is close to the ionized layer, applying a negative DC causes a more rapid increase in current than by applying a positive DC to the same electrode. Results from our experimental measurement of current using counterflow diffusion flames agreed qualitatively well with the model predictions. A sensitivity analysis using dimensional and non-dimensional parameters also supported the importance of the mobility difference and the relative location of the ionized layer on the electric current response.

Pentane isomers are important constituents of distillate gasoline, compressed natural gas and liquefied petroleum gas. Pentane chemistry is integral component of the chemical kinetic mechanisms of larger hydrocarbons. Existing kinetic mechanisms differ in their predictions of the oxidative and pyrolysis behavior of pentane isomers. This work provides new species time-history data to validate and improve pentane chemistry models. Methane, acetylene and ethylene are measured during the high-temperature pyrolysis of n-pentane and iso-pentane. Experiments are performed behind reflected shock waves over 1400–2100 K and pressures near 1 atm. Methane and acetylene are measured using a quantum cascade laser operating near 8 µm, whereas ethylene is measured with a CO2 gas laser operating near 10.6 µm. A two-color technique is used to eliminate broadband interference caused by large hydrocarbons. Measurements are compared with predictions of existing chemical kinetic mechanisms which underpredict the formation of methane and acetylene but overpredict ethylene formation.