Methane–oxygen detonation characteristics at elevated pre-detonation pressures

The detonation characteristics of methane–oxygen mixtures at pre-detonation pressures of 101–1,013 kPa were investigated in a detonation tube. Both pure methane–oxygen mixtures and mixtures with argon dilution were explored. Measurements made include cell sizes via soot foil, wave speed via high speed ion probes / pressure transducers, and temperature / H₂O molar concentration profiles via 100 kHz absorption spectroscopy. Measured cell widths agreed with predicted cell widths based on a ZND length correlation. In addition, the power law fit of cell width with pre-detonation pressure agreed with previous data at less than 101 kPa. Measured detonation wave speeds agreed within 3% of Chapmen-Jouguet for all cases. H₂O molar density and temperature were successfully captured up to 507 kPa. However, above 507 kPa pre-detonation pressure, low signal to noise ratio and poor spectral fits at the extreme conditions of the von Neumann spike resulted in unacceptable uncertainty. These results provide a unique dataset to validate kinetics models and high-fidelity computation fluid dynamics codes for methane-oxygen detonations at elevated pre-detonation pressures relevant to rotating detonation rocket engines.     

Deflagration-to-detonation transition in mixtures of finely divided ammonium perchlorate with submicron aluminum powder

Deflagration-to-detonation transition in binary mixtures of fine ammonium perchlorate (20-μm grains) with submicron ALEX-L aluminum powder (0.2-μm particles) is studied using high-speed photography and pressure recording with quartz crystal sensors. The test mixtures were loaded in thin-walled quartz tubes of inner diameter 10 mm. The charges had a porosity of ~50%. It has been shown that, even under very mild conditions (low-strength shell and a weak source of initiation), the deflagration mode of mixture combustion easily transforms into the detonation mode. The shortest length of the region of transition from deflagration to normal detonation (not more than 30 mm) was observed for a lean mixture, with an aluminum content of ~5%. The mechanism of transition to detonation involves the stage of convective combustion, resulting in the formation of a brightly luminescent crescent-shaped area behind the primary flame front, which, in turn, generates a forward (in the direction of propagation) and a backward wave. The forward wave gives rise to low-speed detonation, which later transforms into normal detonation. The pressure profile within the region of low speed detonation is measured. A comparison with similar experiments in which ALEX-L alu- minum powder was replaced by ASD-4 aluminum (4 μm particles) shows that ALEX-L sensitizes the mixture, resulting in a dramatic reduction of the length of the transition region, making it possible to produce normal detonation in low-strength shells.     

Initiation of combustion of a methane-air mixture in a supersonic flow behind a shock wave during laser excitation of O<Subscript>2</Subscript> molecules

The possibility of initiating detonation of CH₄ + air in a supersonic flow behind an oblique shock wave under the exposure of the mixture to laser radiation with wavelengths λ_I=1.268 μm and 762 nm is analyzed. It is shown that this irradiation leads to excitation of O₂ molecules to the a ¹Δ_g and b ¹Σ _g ⁺ states, which intensifies the chain mechanism of combustion of CH₄/O₂ (air) mixtures. Even for a small value of the laser radiation energy absorbed by an O₂ molecule (∼0.05–0.1 eV), detonation mode of combustion in a poorly inflammable mixture such as CH₄/air can be realized at a distance of only 1 m from the primary shock wave front for relatively small values of temperature (∼1100 K) behind the front under atmospheric pressure.     

Studies on aluminum powder combustion in detonation environment

The combustion mechanism of aluminum particles in a detonation environment characterized by high temperature (in unit 10³ K), high pressure (in unit GPa), and high-speed motion (in units km/s) was studied, and a combustion model of the aluminum particles in detonation environment was established. Based on this model, a combustion control equation for aluminum particles in detonation environment was obtained. It can be seen from the control equation that the burning time of aluminum particle is mainly affected by the particle size, system temperature, and diffusion coefficient. The calculation result shows that a higher system temperature, larger diffusion coefficient, and smaller particle size lead to a faster burn rate and shorter burning time for aluminum particles. After considering the particle size distribution characteristics of aluminum powder, the application of the combustion control equation was extended from single aluminum particles to nonuniform aluminum powder, and the calculated time corresponding to the peak burn rate of aluminum powder was in good agreement with the experimental electrical conductivity results. This equation can quantitatively describe the combustion behavior of aluminum powder in different detonation environments and provides technical means for quantitative calculation of the aluminum powder combustion process in detonation environment.     

Analysis of the influence of nanometric aluminium particle vaporisation on flame propagation in bulk powder media

The combustion of nanometric aluminium (Al) powder with an oxidiser such as molybdenum trioxide (MoO₃) is studied analytically. The analysis was performed to correlate individual Al particle gasification rates to macroscopic flame propagation rates observed in flame tube experiments. Examination of various characteristic times relevant to propagation of a deflagration reveals that particles below about 1.7 nm in diameter evaporate before appreciable chemical reactions occur. Experimental studies used Al particles greater than 1.7 nm in diameter such that a diffusion flame model was developed to better understand the combustion dynamics of multiphase Al particles greater than 1.7 nm diameter relative to experimentally measured macroscopic flame propagation rates. The diffusion flame model predicted orders of magnitude slower propagation rates than experimentally observed. These results imply that (1) another reaction mechanism is responsible for promoting reaction propagation and/or (2) modes other than diffusion play a more dominant role in flame propagation.     

Droplet combustion in standing sound waves

Interaction between droplet combustion and acoustic oscillation is clarified. As the simplest model, an isolated fuel droplet is combusted in a standing sound wave. Apart from the conventional idea that oscillatory component of flow influences heat and mass transfer and promotes combustion, a new model that a secondary flow dominates combustion promotion is examined. The secondary flow, found by the authors in the previous work, is driven by acoustic radiation force due to Reynolds normal stress, and named as thermo-acoustic streaming. Since the force is described by the same equation as buoyancy, i.e., F = ΔρVg, the nature of the streaming is thought to be the same as natural convection. The flow patterns of the streaming are analyzed and its influence on burning rate of a droplet is predicted. Experimental investigation was mainly done with burning droplets located in the middle of node and anti-node of standing sound waves. This location realizes the strongest streaming. By varying sound pressure level, ambient pressure, and acoustic frequency, the strength of the streaming was controlled. Flame configuration including soot and burning rate were examined. Microgravity conditions were employed to clarify the influence of acoustic field through the streaming, since it is similar to and must be distinguished from natural convection. Experiments using microgravity conditions confirmed the new combustion promotion model and the way to quantify it. By introducing a new non-dimensional number Gr_a, that is the ratio of acoustic radiation force to viscosity, burning rate constants for various ambient and sound conditions are rearranged. As a result, it was found that the excess burning rate (k/k₀ − 1) is proportional to or , for weak sound and for strong sound, respectively.     

Chemical control of combustion and detonation in carbon oxide and hydrogen mixtures with air

The paper presents data on the control of combustion and detonation in CO and H₂ mixtures with air by small additives. The dependence of the kinetics of combustion and detonation characteristics on the initial mixture composition observed experimentally is in agreement with the predictions of theory taking into account the special features of reaction chains of the combustion of carbon monoxide in the presence of hydrogen-containing impurities. Works ignoring the chain character of the combustion of H₂ and CO are critically reviewed.     

Transported PDF simulation of turbulent CH4/H2 flames under MILD conditions with particle-level sensitivity analysis

Transported probability density function (TPDF) simulation with sensitivity analysis has been conducted for turbulent non-premixed CH₄/H₂ flames of the jet-into-hot-coflow (JHC) burner, which is a typical model to emulate moderate or intense low oxygen dilution combustion (MILD). Specifically, two cases with different levels of oxygen in the coflow stream, namely HM1 and HM3, are simulated to reveal the differences between MILD and hot-temperature combustion. The TPDF simulation well predicts the temperature and species distributions including those of OH, CO and NO for both cases with a 25-species mechanism. The reduced reaction activity in HM1 as reflected in the peak OH concentration is well correlated to the reduced oxygen in the coflow stream. The particle-level local sensitivities with respect to mixing and chemical reaction further show dramatic differences in the flame characteristics. HM1 is less sensitive to mixing and reaction parameters than HM3 due to the suppressed combustion process. Specifically, for HM1 the sensitivities to mixing and chemical reactions have comparable magnitude, indicating that the combustion progress is controlled by both mixing and reaction in MILD combustion. For HM3, there is however a change in the combustion mode: during the flame initialization, the combustion progress is more sensitive to chemical reactions, indicating that finite-rate chemistry is the controlling process during the autoignition process for flame stabilization; at further downstream where the flame has established, the combustion progress is controlled by mixing, which is characteristic of nonpremixed flames. An examination of the particles with the largest sensitivities reveals the difference in the controlling mixtures for flame stabilization, namely, the stoichiometric mixtures are important for HM1, whereas, fuel-lean mixtures are controlling for HM3. The study demonstrates the potential of TPDF simulations with sensitivity analysis to investigate the effects of finite-rate chemistry on the flame characteristics and emissions, and reveal the controlling physio-chemical processes in MILD combustion.     

Preparation of Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles for superthermites by the detonation of an explosive nanocomposite material

This article reports on the preparation of chromium(III) oxide nanoparticles by detonation. For this purpose, a high explosive—hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX)—has been solidified from a solution infiltrated into the macro- and mesoporosity of Cr₂O₃ powder obtained by the combustion of ammonium dichromate. The resulting Cr₂O₃/RDX nanocomposite material was embedded in a cylindrical charge of pure explosive and detonated in order to fragment the metallic oxide into nanoparticles. The resulting soot contains Cr₂O₃ nanoparticles, nanodiamonds, amorphous carbon species and inorganic particles resulting from the erosion by the blast of the detonation tank wall. The purification process consists in (i) removing the carbonaceous species by an oxidative treatment at 500 °C and (ii) dissolving the mineral particles by a chemical treatment with hydrofluoric acid. Contrary to what could be expected, the Cr₂O₃ particles formed during the detonation are twice larger than those of initial Cr₂O₃. The detonation causes the fragmentation of the porous oxide and the melting of resulting particles. Nanometric droplets of molten Cr₂O₃ are ejected and quenched by the water in which the charge is fired. Despite their larger size, the Cr₂O₃ nanoparticles prepared by detonation were found to be less aggregated than those of the initial oxide used as precursor. Finally, the Cr₂O₃ synthesized by detonation was used to prepare a superthermite with aluminium nanoparticles. This material possesses a lower sensitivity and a more regular combustion compared to the one made of initial Cr₂O₃.     

Influence of Small Xe Additives on the Detonation Threshold for O<Subscript>2</Subscript>−H<Subscript>2</Subscript>−He Mixtures

The effect of a small Xe additive on the conditions of detonation initiation in incident shock waves of various intensities is studied. The experiments are carried out on a shock tube facility with 10% H₂ + 5% O₂ + 85% He, 10% H₂ + 5% O₂ + 84.75% He + 0.25% Xe, and 10% H₂ + 5% O₂ + 84.5% He + 0.5% Xe mixtures. The addition of Xe led to a shift in the detonation threshold toward weaker shock waves. This effect is probably due to a significant increase in the frequency of high-energy collisions between O₂ and Xe molecules in the shock wave front in comparison with that characteristic of the equilibrium behind the wave, a factor that significantly accelerates the chemical reaction between O₂ and H₂ behind the front. The effect is a consequence of the formation of a specific translational nonequilibrium in the wave front. A previously performed numerical study of the distributions of pairs of O₂ and Xe molecules in the shock wave front shows that this effect can be enhanced by decreasing the Xe concentration from 0.5 to 0.25%. The experiment performed indirectly confirms this conclusion. It turns out that, for the mixture with 0.25% Xe, the detonation threshold shifts more strongly to the region of weaker shock waves than for the mixture with 0.5% Xe. This result gives additional arguments in favor of the assumption that this effect is due to the specifics of the translational nonequilibrium in the wave front.     

Modelling detonation of heterogeneous explosives with embedded inert particles using detonation shock dynamics: Normal and divergent propagation in regular and simplified microstructure

This paper discusses the mathematical formulation of Detonation Shock Dynamics (DSD) regarding a detonation shock wave passing over a series of inert spherical particles embedded in a high-explosive material. DSD provides an efficient method for studying detonation front propagation in such materials without the necessity of simulating the combustion equations for the entire system. We derive a series of partial differential equations in a cylindrical coordinate system and a moving shock-attached coordinate system which describes the propagation of detonation about a single particle, where the detonation obeys a linear shock normal velocity-curvature (D_n–κ) DSD relation. We solve these equations numerically and observe the short-term and long-term behaviour of the detonation shock wave as it passes over the particles. We discuss the shape of the perturbed shock wave and demonstrate the periodic and convergent behaviour obtained when detonation passes over a regular, periodic array of inert spherical particles.     

The effects of mixture preburning on detonation wave propagation

Pressure gain combustion in the form of continuous detonations can provide a significant increase in the efficiency of a variety of propulsion and energy conversion devices. In this regard, rotating detonation engines (RDEs) that utilize an azimuthally-moving detonation wave in annular systems are increasingly seen as a viable approach to realizing pressure gain combustion. However, practical RDEs that employ non-premixed fuel and oxidizer injection need to minimize losses through a number of mechanisms, including turbulence-induced shock-front variations, incomplete fuel-air mixing, and premature deflagration. In this study, a canonical stratified detonation configuration is used to understand the impact of preburning on detonation efficiency. It was found that heat release ahead of the detonation wave leads to weaker shock fronts, delayed combustion of partially-oxidized fuel-air mixture, and non-compact heat release. Furthermore, large variations in wave speeds were observed, which is consistent with wave behavior in full-scale RDEs. Peak pressures in the compression region or near triple points were considerably lower than the theoretically-predicted values for ideal detonations. Analysis of the detonation structure indicates that this deflagration process is parasitic in nature, reducing the detonation efficiency but also leading to heat release far behind the wave that cannot directly strengthen the shock wave. This parasitic combustion leads to commensal combustion (heat release far downstream of the wave), indicating that it is the root cause of combustion efficiency losses.     

Thermally nonequilibrium processes occurring during the ignition of hydrocarbon-air mixtures behind shock waves

The effect of a nonequilibrium vibrational excitation of the reactants on the ignition of methane-air mixtures in a supersonic flow behind the front of an incline shock wave. It was demonstrated that the equilibrium kinetic models give incorrectly predict the induction zone length (within a factor of 3) and the final pressure in the combustion products. Even a moderate preliminary vibrational excitation of N₂ molecules makes it possible to substantially (by a factor 10 to 15) decrease the length of the induction zone behind the shock wave front (to ～1–2 m) at even moderate temperatures of the shocked gas (1400–1500 K).     

A study of the characteristics of the combustion of Ti + <Emphasis Type="Italic">x</Emphasis>C (<Emphasis Type="Italic">x</Emphasis> &gt; 0.5) powder and granular compositions in a gas coflow

The characteristics of the combustion of Ti + 0.5C, Ti + 0.75C, and Ti + C powder and granular mixtures in a flow of inert (argon) and reactive (nitrogen) gases at various pressure differences are studied. It is shown that the influence of the pressure difference on the burning velocity of the powder mixture decreases with increasing fraction of carbon in it, but a pressure difference of 1 atm producing practically no effect on the burning rate of the Ti + C mixture. The data obtained are indicative of a nonequilibrium mechanism of the combustion of Ti + xC granular mixtures in a nitrogen coflow, in which case the sequence of chemical reactions in the combustion wave is determined by the kinetic characteristics of the interaction of titanium with nitrogen and carbon. It is concluded that the reactive gas flow ignites the surface of the granules and thereby leads the propagation of the combustion wave. It is established that, for all the mixtures studied, the mechanism of the combustion of a granular charge in a nitrogen flow is fundamentally different from the combustion of a powder charge under the same condition.     

Stabilized,flat iron flames on a hot counterflow burner

Metal powder combustion has traditionally been studied to mitigate the risk of industrial accidents and to determine the contributions of metals as additives to the performance of energetic materials. Recently, there has been growing interest in exploring the potential of metal powders as recyclable, zero-carbon energy carriers as an alternative to the hydrocarbons known to contribute to climate change. The present work introduces, for the first time, a stabilized flat iron flame. The counterflow burner used in this work is comprised of an inverted ceramic nozzle which sits above, and is aligned axially with, a lower nozzle producing a laminar flow of particles suspended in an oxidizing gas. A stabilized methane flame sits inside the top nozzle and the hot combustion products impinge upon the two-phase flow from the bottom nozzle, creating a stagnation plane. Spherical iron powder, with 90% of the particles less than 2.5 µm in size, is pre-loaded into a piston and dispersed using mixtures of 30% and 40% oxygen balanced in argon. Flame speeds are measured using particle image velocimetry (PIV), while flame temperatures are determined using multicolour pyrometry. It is found that flame speeds range between 30 cm/s and 45 cm/s for both oxidizing mixtures. Despite having fuel loadings below stoichiometric concentrations, the observed particle combustion temperatures are close to the adiabatic flame temperature of the stoichiometric mixture, indicating combustion in the diffusion-controlled regime for these small particles. Finally, the independence of the flame speeds with respect to oxygen concentration suggests flame propagation in the discrete regime.     

Initiation of a detonation wave by resonant laser radiation in a hydrogen-oxygen mixture flowing about a wedge

The formation of an oblique detonation wave in a supersonic hydrogen-oxygen flow about a planar wedge is considered. It is shown that the excitation of the electronic state b ¹Σ _g ⁺ in oxygen molecules by resonant laser radiation with a wavelength of 762 nm makes it possible to initiate detonation combustion at a distance of ≈1 m from the tip of the wedge at low temperatures (500–600 K). Notably, it suffices to irradiate the gas in the narrow (0.5–1.0 cm across) paraxial region of the flow near the tip of the wedge. It is found that the laser-induced excitation of molecular oxygen is several times more efficient than ordinary heating of the mixture to initiate a detonation wave.     

Detonation properties of stoichiometric gaseous n-heptane/oxygen/argon mixtures

A study of detonation velocity and cellular structure for stoichiometric heptane/oxygen and for some stoichiometric heptane/oxygen/argon mixtures is carried out in a shock tube at low initial pressure. The critical conditions for the detonation onset and for the propagation of a self-sustained detonation wave are determined. A simplified form of the ZND model used in conjunction with a validated detailed kinetic model leads to the determination of the proportionality factor, A, between the detonation cell width, λ, and the induction distance, Δ, in the detonation wave. This A factor is of practical importance to estimate the detonation properties of n-heptane based mixtures including n-heptane/air. The prediction of detonation cell size λ for n-heptane based mixtures is discussed according to the recent semi-empirical detonation model of Gavrikov et al. The cell sizes predicted according to this detonation model are underestimated by a factor of about 8. The limitations of this model are underlined when applied to n-heptane based mixtures.     

Development of a wide range-operable,rich-lean low-NOx combustor for NH3 fuel gas-turbine power generation

Low-NOx NH₃-air combustion power generation technology was developed by using a 50-kWe class micro gas-turbine system at the National Institute of Advanced Industrial Science and Technology (AIST), Japan, for the first time. Based on the global demand for carbon-free power generation as well as recent advances involving gas-turbine technologies, such as heat-regenerative cycles, rapid fuel mixing using strong swirling flows, and two-stage combustion with equivalence ratio control, we developed a low-NOx NH₃-air non-premixed combustor for the gas-turbine system. Considering a previously performed numerical analysis, which proved that the NO reduction level depends on the equivalence ratio of the primary combustion zone in a NH₃-air swirl burner, an experimental study using a combustor test rig was carried out. Results showed that eliminating air flow through primary dilution holes moves the point of the lowest NO emissions to the lesser fuel flow rate. Based on findings derived by using a test rig, a rich-lean low NOx combustor was newly manufactured for actual gas-turbine operations. As a result, the NH₃ single fueled low-NOx combustion gas-turbine power generation using the rich-lean combustion concept succeeded over a wide range of power and rotational speeds, i.e., below 10–40 kWe and 75,000–80,000?rpm, respectively. The NO emissions were reduced to 337?ppm (16% O₂), which was about one-third of that of the base system. Simultaneously, unburnt NH₃ was reduced significantly, especially at the low electrical power output, which was indicative of the wider operating range with high combustion efficiency. In addition, N₂O emissions, which have a large Global Warming Potential (GWP) of 298, were reduced significantly, thus demonstrating the potential of NH₃ gas-turbine power generation with low environmental impacts.     

Effects of radiation heat loss on laminar premixed ammonia/air flames

Ammonia (NH₃) direct combustion is attracting attention for energy utilization without CO₂ emissions, but fundamental knowledge related to ammonia combustion is still insufficient. This study was designed to examine effects of radiation heat loss on laminar ammonia/air premixed flames because of their very low flame speeds. After numerical simulations for 1-D planar flames with and without radiation heat loss modeled by the optically thin model were conducted, effects of radiation heat loss on flame speeds, flame structure and emissions were investigated. Simulations were also conducted for methane/air mixtures as a reference. Effects of radiation heat loss on flame speeds were strong only near the flammability limits for methane, but were strong over widely diverse equivalence ratios for ammonia. The lower radiative flame temperature suppressed the thermal decomposition of unburned ammonia to hydrogen (H₂) at rich conditions. The equivalence ratio for a low emission window of ammonia and nitric oxide (NO) in the radiative condition shifted to a lower value than that in the adiabatic condition.     

Iron Precursor Decomposition in the Magnesium Combustion Flame: A New Approach for the Synthesis of Particulate Metal Oxide Nanocomposites

Powders of Fe–Mg–O nanocomposite particles have been grown using a novel chemical vapor synthesis approach that employs the decomposition of a metalorganic precursor inside the metal combustion flame. After annealing in controlled gas atmospheres composition distribution functions, structure and phase stability of the obtained magnesiowüstite nanoparticles are measured with a combination of techniques such as inductively coupled plasma‐optical emission spectroscopy, energy dispersive X‐ray spectroscopy, X‐ray diffraction, and scanning and transmission electron microscopy. Complementary Mössbauer spectroscopy measurements reveal that depending on Fe loading and temperature of annealing either metastable and superparamagnetic solid solutions of Fe³⁺ ions in periclase (MgO) or phase separated mixtures of MgO and ferrimagnetic magnesioferrite (MgFe₂O₄) nanoparticles can be obtained. The described combustion technique represents a novel concept for the production of mixed metal oxide nanoparticles. Adressing the impact of selected annealing protocols, this study underlines the great potential of vapor phase grown non‐equilibrium solids, where thermal processing provides means to trigger phase separation and, concomitantly, the emergence of new magnetic properties.