Chemical and phase compositions of the combustion products of thermit-type mixtures based on chromium, lanthanum, and calcium oxides

The effect of a CaO₂-Al high-caloricity additive on the combustion of a CrO₃-La₂O₃-Cr low caloric mixture is studied. The resultant mixture can burn at an additive content above 20%, with the combustion products having a cast appearance at an additive content above 30%. The additive content and gas pressure produce a significant effect on the phenomenology and regularities of combustion, the process of structure formation, and chemical and phase composition of the autowave synthesis products. The mutual high-temperature dissolution of oxides yields an lanthanum-chromite-based oxide material containing CaO and Al₂O₃, components that have a stabilizing effect and make it possible to modify the physical and chemical properties of lanthanum chromite.     

Effect of nitride additives (AlN and Si3N4) on the combustion of Fe2O3/Al mixtures and the formation of the chemical composition of the combustion products

The method of self-propagating high-temperature synthesis (SHS) is applied to prepare cast oxynitride ceramics using a Fe₂O₃ + 4Al thermite mixture. The nitrogen-containing components of the mixture were AlN and Si₃N₄ additives. The synthesis was performed in a reactor at an initial nitrogen pressure of 8MPa. The nitrogen-containing additives are demonstrated to influence the burning rate and combustion limits of the mixtures, as well as the yield and chemical composition of the cast ceramics.     

Synthesis of nano-size BaMgAl10O17:Eu blue phosphor by a rapid exothermic reaction

Ultrafine particles of BaMgAl₁₀O₁₇:Eu²⁺ (BAM) phosphor were synthesized by a solid-state combustion reaction in a powder bed of 0.9BaCO₃+MgO+5Al₂O₃+0.05Eu₂O₃+k(KClO₃+1.5C) composition. A large exothermic reaction of the mixture (KClO₃+1.5C) leads to a self-sustaining combustion mode. Under optimized combustion conditions, the product consisted of BAM powder and KCl was obtained. BAM ultrafine particles resulting from the combustion process were easily obtained by simply washing the salt by-product with water. Combustion-processed BAM phosphor shows a homogeneous grain size of 100-500 nm, good dispersity, regular morphology, and improved luminescence properties.     

Synthesis and cation distribution of copper-substituted spinel-related lithium ferrite

Single-phased Cu²⁺-substituted spinel-related Li_0.5Fe_2.5O₄ was synthesized by sintering a mixture of Cu²⁺-substituted corundum-related α-Fe₂O₃ and Li₂CO₃ at 700 °C which is ∼325-400 °C lower than the temperature at which the material is prepared by the conventional ceramic methods. X-ray powder diffraction, X-ray photoelectron spectroscopy, Mössbauer spectroscopy and magnetic measurements were used to characterize the material. In contrast to high-temperature synthetic routes, the present one leads to a Cu⁺-and Fe²⁺-cation free material, thereby optimizing its technological value. Rietveld refinement of the XRD data favors a structural model in which Cu²⁺ substitutes for both Fe³⁺ and Li⁺ at the octahedral sites. Mössbauer and magnetic data are consistent with this model if spin thermal reversal and/or spin canting are taken into account for the later.     

In-water gas combustion in linear and annular gas bubbles

A new pulsed-cyclic method of in-water gas combustion was developed with separate feed of fuel gas and oxygen with the focus on development of new technologies for heat generators and submerged propellers. The results of calorimetric and hydrodynamic measurements are presented. In-water combustion of acetylene, hydrogen, and propane was tested with the operation frequency of 2–2.5 Hz and with a linear injector. The combustion dynamics of combustion of stoichiometric mixture with propane (C₃H₈+5O₂) was studied for a bubble near a solid wall; the produced gas bubble continues expansion and oscillations (for the case of linear and annular bubbles). It was demonstrated that gas combustion in annular bubbles produces two same-magnitude pulses of force acting on the wall. The first pulse is produced due to expansion of combustion products, and the second pulse is produced due to axial cumulative processes after bubble collapse. This process shapes an annular vortex which facilitates high-speed convective processes between combustion products and liquid; and this convection produces small-size bubbles.     

Integrated chemical process for exothermic wave synthesis of high luminance YAG:Ce phosphors

In this paper, high-luminance yellow-emitting Y₃Al₅O₁₂:Ce³⁺ phosphor (YAG:Ce) microparticles were prepared in a solid flame using a 1.425Y₂O₃+2.5Al₂O₃+0.15CeO₂+k(KClO₃+urea)+mNH₄F precursor mixture (here k is the number of moles of the KClO₃+urea red-ox mixture, and m is the number of moles of NH₄F). The self-sustaining combustion process for the entire reaction sample was provided by the heat generated from the KClO₃+urea mixture. Parametric studies demonstrated that the maximum temperature in the combustion wave varied from 885 to 1200 °C for k=2.0-3.0 mole and m=0-1.5 mole. X-ray analysis results showed that the product obtained in the solid flame consisted of Y₃Al₅O₁₂:Ce³⁺ and KCl phases. Therefore, after dissolving potassium chloride in distillated water, pure-phase YAG:Ce phosphor powder was obtained. The as-prepared YAG:Ce phosphor particles had diameters of 10-25 μm and good dispersity and exhibited luminescence properties comparable to those of YAG:Ce phosphor powders prepared by conventional high-temperature processing.     

Enhanced Al-H2O-based fuels combustion characteristics with polyacrylamide at low pressures

The combustion behavior of nano-aluminum-water (n-Al-H₂O) mixture with addition of polyacrylamide (PAM) was investigated in argon at 0.1～1.5 MPa using a constant-pressure strand burner. The burning rates of n-Al-H₂O mixture were measured. The results show that PAM addition can not only help improve the burning rate of n-Al-H₂O mixture, but also decrease the pressure index of burning rate. The mixture of n-Al powder and H₂O cannot be ignited in argon at 0.1 MPa, but the mixture of n-Al powder and H₂O with the 3 wt % PAM can be ignited, and the mixture can support the self-sustaining combustion. The burning rate is 7.64 mm/s. Moreover, the burning rate increases with increasing the pressure. In addition, the combustion process and flame image characteristics were obtained by a high-speed photography technique, and the element composition and surface morphology of the condensed combustion products were evaluated using a scanning electron microscopy combined with energy dispersive X-ray system.     

Thermoluminescence study of aluminum oxide doped with therbium and thulium

In this work, α-Al₂O₃ doped either with Tb³⁺ or Tm³⁺ was prepared by combustion synthesis techniques for thermoluminescent (TL) ionizing radiation dosimetry applications. In this method, the reactants (aluminum nitrate, urea and therbium or thulium nitrate) are ignited in a muffle furnace at temperatures as low as 500 °C. This synthesis route is an alternative technique to the conventional fabrication methods of materials based on α-Al₂O₃ (Czochralsky, Vernuil), where high melting temperatures and reducing atmospheres are required. After combustion, the samples were annealed at temperatures ranging from 1000 to 1400 °C for 4 h in order to obtain the pure α-phase structure and were then irradiated with a Co-60 gamma radiation source. The annealed samples present a well defined TL glow peak with a maximum at approximately 200 °C and linear TL response in the dose range 0.5–5 Gy. It was observed that a 0.1 mol% concentration of Tb³⁺ or Tm³⁺ and annealing at 1400 °C optimize the TL sensitivity. The highest sensitivity was found for Tm³⁺ doped samples which were approximately 25 times more sensitive than Tb³⁺ doped samples. These results strongly suggest that combustion synthesis is a suitable technique to prepare doped aluminum oxide material and that Tm³⁺ doped aluminum oxide is a potential material for TL radiation dosimetry.     

Combustion rates of graphite rods in the forward stagnation field of the high-temperature, humid airflow

Relevant to High-Temperature Air Combustion, an experiment has been conducted to study carbon combustion in the high-temperature oxidizer-flow, by use of a graphite rod set in the forward stagnation field. Effects of humid air and O₂-reduced oxidizer have been examined, after re-confirming that the combustion rate in the high-temperature oxidizer-flow is enhanced, because of elevated transport properties when the mass flow rate of oxidizer is the same, and that it is suppressed, because of reduced mass transfer rates through the thickened boundary layer when the velocity gradient is the same. It is found that high H₂O mass-fraction is favorable for the enhancement of combustion rate at high surface temperatures (>2000 K), because of its participation in the surface C–H₂O reaction, while it is not the case at medium surface temperatures (1400–1700 K), because of the suppressing effect, caused by the establishment of CO flame. As for O₂ and CO₂ concentrations in the high-temperature oxidizer-flow, it is found that O₂ mass-fraction can be reduced without reducing combustion rate in the room-temperature airflow, and that it can further be reduced in existence of enough CO₂ that can be an oxidizer in carbon combustion. Theoretical works have also been conducted for the system with three surface reactions and two global gas-phase reactions. It is found that the Frozen mode without CO flame and the Flame-detached mode with infinitely fast gas-phase reaction can fairly represents combustion behavior before and after the establishment of CO flame, respectively, as far as the trend and the approximate magnitude are concerned. It is also shown that a new mode with suppressing H₂ ejection from the surface can fairly represent the combustion rate, experimentally obtained in humid airflow with relatively low velocity gradient when the surface temperature is high.     

Oxidation and combustion of stabilized lithium metal powder (SLMP)

Power systems based on combustion are of interest for space missions where the use of solar and nuclear energy is impractical. A novel design of such systems involves the so-called filtration combustion of metal powders with oxygen supplied by a chemical oxygen generator. In missions to Mars and Venus, the atmospheric CO₂ could be added to the oxygen flow. A stabilized lithium metal powder (SLMP) is a promising fuel for this application, but its oxidation and combustion in O₂ and CO₂ has not been studied yet. In the present work, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) have been used to investigate high-temperature oxidation of SLMP in O₂/Ar and CO₂ environments. Further, combustion of SLMP in vertical quartz tubes with two open ends at natural infiltration of O₂ and CO₂ has been studied in a laser ignition facility. The TGA has revealed the formation of lithium peroxide (Li₂O₂) in addition to lithium monoxide (Li₂O) at temperatures below 400 °C. Scanning electron microscopy has shown that the oxidized particles are hollow shells, which implies that the oxidation process includes growth of a solid oxide layer on the surface of the lithium droplet and simultaneous growth of a cavity inside the droplet. The laser ignition of SLMP in O₂ results in vigorous combustion of the top layer followed by the downward propagation of a counterflow combustion wave. The TGA and DSC have shown that the reaction of SLMP with CO₂ is a multi-stage process, which includes the formation of lithium oxide and its subsequent conversion into lithium carbonate (Li₂CO₃). Self-sustained combustion of SLMP was not achieved in a CO₂ environment, apparently because the formed products hinder the transport of CO₂.     

An experimental realization of an unstrained, planar diffusion flame

A unique burner was constructed to experimentally realize a one-dimensional unstrained planar non-premixed flame, previously considered only in idealized theoretical models. One reactant, the fuel mixture in the current experiments, is supplied through a porous plug at the bottom of the combustion chamber and flows vertically up towards the horizontal flame. The crux of the design is the introduction of the oxidizer from above in such a way that its diffusion against the upward product flow is essentially one-dimensional, i.e., uniform over the burner cross-section. This feature was implemented by introducing the oxidizer into the burner chamber from the top through an array of 625 closely spaced hypodermic needles, and allowing the hot products to escape vertically up through the space between the needles. Due to the injection of oxidizer through discrete tubes, a three-dimensional “injection layer” exists below the exit plane of the oxidizer supply tubes. Experimental evidence suggests that this layer is thin and that oxidizer is supplied to the flame by 1-D counterdiffusion, producing a nearly unstrained flame. To characterize the burner, flame position measurements were conducted for different compositions and flowrates of H₂–CO₂ and O₂–CO₂ mixtures. The measured flame locations are compared to an idealized one-dimensional model in which only diffusion of oxidizer against the product flow is considered. The potential of the new burner is demonstrated by a study of cellular structures forming near the extinction limit. Consistent with previous investigations, cellular instabilities are shown to become more prevalent as the initial mixture strength and/or the Damköhler number are decreased. As the extinction limit is approached, the number of cells was observed to decrease progressively.     

Characterization of Cr/SiO2 catalysts and ethylene polymerization by XPS

Cr/SiO₂ catalysts with 1 or 3 wt.% Cr loadings and different chromium precursors were characterized by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). A method to determine chromium species in the sample was developed through the decomposition of the Cr 2p XPS spectrum in Cr⁶⁺ and Cr³⁺ standard spectra. The results of the binding energy from the Cr 2p region and of the distribution of chromium species allowed to evaluate the dynamic photo-reduction of the surface chromium species during XPS analysis. Photo-reduction of surface Cr⁶⁺ to Cr³⁺ species was verified for all samples supported in silica, depending on the precursor and chromium content. Bulk CrO₃ and Cr₂O₃ standards did not reveal variation in the binding energy of Cr 2p_3/2, but a physical mixture of CrO₃ with SiO₂ presented photo-reduction. The behavior of this mixture resembled to the catalysts and suggests the participation of the surface hydroxyls of silica in the photo-reduction process. XPS intensity measurements for assessing dispersion of chromium oxide were used to compare the calcined and reduced catalysts to different chromium precursors. Polyethylene chains were detected by in situ XPS, while oligomerization products were not observed.     

Dynamically evaluating mixture effects on multi-channel reactions in flames: A case study for the CH3 + OH reaction

Complex-forming reactions, whose rate constants depend on pressure and collisional energy transfer characteristics of the surrounding bath gas, play a major role in the kinetics of combustion. In most realistic combustion environments, multiple species of distinct collisional energy transfer characteristics are present in significant quantities and thus contribute to collisional energy transfer involved in such systems. Recent studies have indicated that certain representations of multi-component pressure dependence (i.e. “mixture rules”) and/or a failure to implement a mixture rule can result in errors reaching an order of magnitude, whereas recently proposed mixture rules yield errors less than 10%. The present study compares the performance of various mixtures rules for representing multi-component pressure dependence of the multi-channel CH₃ + OH reaction in flames, using a novel dynamic procedure for evaluating mixture effects as a function of reaction progress (viz. local temperature, pressure, and mixture composition). This procedure enables mixture effects to be simulated in current combustion codes despite codes not yet having functional forms intended to capture these mixture dependence effects. Results from this procedure, combining master equation simulations and kinetic-transport simulations, indicate that recently proposed mixture rules based on the reduced pressure provide a considerably more accurate representation of mixture effects for CH₃ + OH than previous mixture rules based on the absolute pressure. Furthermore, the present results demonstrate that mixture effects for the CH₃ + OH reaction, which are not accounted for in many models, have a significant effect on predictions of the laminar flame speed – of comparable magnitude to differences motivating parameter adjustments in model development studies.     

The Fe1−xCoxS system (x < 0.25); transition and the high temperature phase

The α-transition in Fe_1−xCo_xS materials is examined based on electrical, magnetic and structural properties. A decrease of the transition temperature is observed with increasing alloying rate up to x_co = 0.24, where the transition is completely cancelled. Beyond this critical concentration the materials exhibit a high-temperature FeS type behavior.The existence of hk0 reflections, with h and/or k = 2n + 1 in the cobalt-stabilized superstructure, the high-temperature phase of FeS, establishes that the structure is hexagonal, space group P6₃mc, with two independent metal positions, in contrast to the previously proposed tri-twinned MnP type model.The physical and structural results are discussed within the framework of conductivity by polarons. The α-transition occurs when the polaron concentration, thermally created or introduced by impurities, reaches the critical value x_p ≅ 0.08. The driving mechanism for the α-transition is a reduction of the polaron dissociation energy by a temperature increase or by cobalt alloying.     

Concerning the cation distribution in MnFe2O4 synthesized through the thermal decomposition of oxalates

A single phase manganese ferrite powder have been synthesized through the thermal decomposition reaction of MnC₂O₄·2H₂O-FeC₂O₄·2H₂O (1:2 mole ratio) mixture in air. DTA-TG, XRD, Mössbauer spectroscopy, FT-IR and SEM techniques were used to investigate the effect of calcination temperature on the mixture. Firing of the mixture in the range 300-500 °C produce ultra-fine particles of α-Fe₂O₃ having paramagnetic properties. XRD, Mössbauer spectroscopy as well as SEM experiments showed the progressive increase in the particle size of α-Fe₂O₃ up to 500 °C. DTA study reveals an exothermic phase transition at 550 °C attributed to the formation of a Fe₂O₃-Mn₂O₃ solid solution which persists to appear up to 1000 °C. At 1100 °C, the single phase MnFe₂O₄ with a cubic structure predominated. The Mössbauer effect spectrum of the produced ferrite exhibits normal Zeeman split sextets due to Fe³⁺ions at tetrahedral (A) and octahedral (B) sites. The obtained cation distribution from Mössbauer spectroscopy is (Fe_0.92Mn_0.08)[Fe_1.08Mn_0.92]O₄.     

Mechanism of propagation of the combustion front in a Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> + 2Al + 30% Al<Subscript>2</Subscript>O<Subscript>3</Subscript> mixture

The results of experiments on the combustion of a powdery Fe₂O₃-Al-Al₂O₃ mixture in an argon flow are reported. The process of combustion is perturbed by a pressure drop across the batch created by evacuating one of the end faces of the reaction cell. The effects of gasifiable additives (borax and soda) and a pressure drop on the combustion characteristics are studied. The results obtained are interpreted within the framework of the convection-conduction theory of combustion of heterogeneous condensed systems.     

Large eddy simulation of the low temperature ignition and combustion processes on spray flame with the linear eddy model

Large eddy simulation coupled with the linear eddy model (LEM) is employed for the simulation of n-heptane spray flames to investigate the low temperature ignition and combustion process in a constant-volume combustion vessel under diesel-engine relevant conditions. Parametric studies are performed to give a comprehensive understanding of the ignition processes. The non-reacting case is firstly carried out to validate the present model by comparing the predicted results with the experimental data from the Engine Combustion Network (ECN). Good agreements are observed in terms of liquid and vapour penetration length, as well as the mixture fraction distributions at different times and different axial locations. For the reacting cases, the flame index was introduced to distinguish between the premixed and non-premixed combustion. A reaction region (RR) parameter is used to investigate the ignition and combustion characteristics, and to distinguish the different combustion stages. Results show that the two-stage combustion process can be identified in spray flames, and different ignition positions in the mixture fraction versus RR space are well described at low and high initial ambient temperatures. At an initial condition of 850 K, the first-stage ignition is initiated at the fuel-lean region, followed by the reactions in fuel-rich regions. Then high-temperature reaction occurs mainly at the places with mixture concentration around stoichiometric mixture fraction. While at an initial temperature of 1000 K, the first-stage ignition occurs at the fuel-rich region first, then it moves towards fuel-richer region. Afterwards, the high-temperature reactions move back to the stoichiometric mixture fraction region. For all of the initial temperatures considered, high-temperature ignition kernels are initiated at the regions richer than stoichiometric mixture fraction. By increasing the initial ambient temperature, the high-temperature ignition kernels move towards richer mixture regions. And after the spray flames gets quasi-steady, most heat is released at the stoichiometric mixture fraction regions. In addition, combustion mode analysis based on key intermediate species illustrates three-mode combustion processes in diesel spray flames.     

Numerical simulation of a mixed-mode reaction front in a PPC engine

The ignition process, mode of combustion and reaction front propagation in a partially premixed combustion (PPC) engine running with a primary reference fuel (87% iso-octane, 13% n-heptane by volume) is studied numerically in a large eddy simulation. Different combustion modes, ignition front propagation, premixed flame and non-premixed flame, are observed simultaneously. Displacement speed of CO iso-surface propagation describes the transition of premixed auto-ignition to non-premixed flame. High temporal resolution optical data of CH₂O and chemiluminescence are compared with simulated results. A high speed ignition front is seen to expand through fuel-rich mixture and stabilize around stoichiometry in a non-premixed flame while lean premixed combustion occurs in the spray wake at a much slower pace. A good qualitative agreement of the distribution of chemiluminescence and CH₂O formation and destruction shows that the simulation approach sufficiently captures the driving physics of mixed-mode combustion in PPC engines. The study shows that the transition from auto-ignition to flame occurs over a period of several crank angles and the reaction front propagation can be captured using the described model.