Soot Formation in Combustion Processes (Review)

A review is given of recent papers on the phenomenology, kinetics, and mechanism of soot formation in hydrocarbon combustion; the effects of various factors on the formation of polycyclic aromatic hydrocarbons, fullerenes, and soot, low-temperature soot formation in cool flames, combustion in electric field, and the paramagnetism of soot particles from an ecological viewpoint are considered. __________ Translated from Fizika Goreniya i Vzryva, Vol. 41, No. 6, pp. 137–156, November–December, 2005.     

Soot and carbon deposition mechanisms in ethene/air flames

Deposition of soot particles during any combustion process is very undesirable and can cause both mechanical and environmental problems. An investigation has been carried out of the deposition of soot on to both cooled and uncooled metal probes in rich ethene/air flames (φ = 2.76 and 2.52) using a flat-flame, water-cooled burner. The processes by which soot particles move to the surface of deposition probes, and the way in which they adhere to the surface, have been explored. The results have shown that the temperature of the probe can have a significant effect on the deposition rates and the chemical nature of the deposits.     

Molecular beam studies of fullerenes

A number of molecular beam experiments with the fullerenes are described. Such experiments allow a detailed probing of the interactions between fullerenes and other species and among the fullerenes themselves. Emphasis is placed on work involving photophysics and collisional interactions of the fullerenes.     

Enantioanalysis of S-deprenyl using enantioselective, potentiometric membrane electrodes based on C60 derivatives

Enantioselective, potentiometric membrane electrodes based on (1,2-methanofullerene C₆₀)-61-carboxylic acid, diethyl (1,2-methanofullerene C₆₀)-61-61-dicarboxylate and tert-butyl (1,2-methanofullerene C₆₀)-61-carboxylic acid were proposed for the enantioanalysis of S-deprenyl in pharmaceutical compounds. Molecular modeling calculations were performed to prove the reliability of the proposed electrodes. The different characteristics involved in this analysis were explained, namely (i) the stability of each molecule using total energy, hardness and dipole moment, and (ii) the explanation of the mechanism of interaction using intermolecular forces (moderate hydrogen bond interactions), atomic charges and electrostatic potential. Electronic structures as well as molecular interaction have been investigated using Hartree-Fock theory, 3-21G(*) basis set. Stability and feasibility of all the generated structures were supported by their respective energy minima and fundamental frequencies.     

PAHs and Mutagenicity of Inhalable and Respirable Diesel Particulate Matter in Santiago,Chile

Delayed human effects such as cancer could be a consequence of chronic exposure, over long periods of time, to inhalable (PM₁₀) and respirable (PM_2.5) particles containing environmental carcinogen mixtures. Air pollution in Santiago, Chile, is a major public health problem due to the high levels of regulated pollutants such as PM₁₀, CO, and ozone. In this work, we studied the levels of polycyclic aromatic hydrocarbons (PAHs) onto PM₁₀ and PM_2.5 collected in diesel revision plants, in an urban area with a high flow of buses and trucks and in a rural area not exposed to diesel emissions. The PM₁₀ average levels in diesel emission plants were higher than the Chilean PM₁₀ standard and higher than those found in the urban and rural areas. In the urban area the PM₁₀ average levels were lower than the Chilean PM₁₀ standard, although some 24 h levels surpassed the levels established to decree preemergency or emergency and in some cases were higher than the levels reported by all the official monitoring stations. The levels of total PAHs onto PM₁₀ were higher in the diesel plants than in the urban area and rural area, but the levels of six carcinogenic PAHs were similar in the diesel plants to those found in the urban area. Organic extracts from PM₁₀ collected in diesel plants in Salmonella typhimurium TA98 in the presence and in the absence of an S9 activation system were significantly higher than in the urban area and rural area. Mutagenic activity with and without S9 in diesel plants and the urban area showed that indirect (PAHs) and direct (nitro-PAHs) mutagenic compounds are present in organic extracts from PM₁₀. In conclusion, these results showed that in Santiago diesel emission particles were highly mutagenic and contain carcinogenic PAHs. This might represent a risk for long-term respiratory effects in Santiago's inhabitants.     

Low-temperature solution combustion synthesis of high performance LiNi0.5Mn1.5O4

High-voltage LiNi_0.5Mn_1.5O₄ spinels were synthesized by a low temperature solution combustion method at 400 °C, 600 °C and 800 °C for 3 h. The phase composition, structural disordering, micro-morphologies and electrochemical properties of the products were investigated by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM) and constant current charge–discharge test. XRD analysis indicated that single phase LiNi_0.5Mn_1.5O₄ powders with disordered Fd-3m structures were obtained by the method at 400 °C, 600 °C and 800 °C. The crystallinity increased with increasing preparation temperatures. XRD and FTIR data indicated that the degree of structural disordering in the product prepared at 800 °C was the largest and in the product prepared at 600 °C was the least. SEM investigation demonstrated that the particle size and the crystal perfection of the products were increased with increasing temperatures. The particles of the product prepared at 600 °C with ~200 nm in size are well developed and homogeneously distributed. Charge/discharge curves and cycling performance tests at different current density indicated that the product prepared at 600 °C had the largest specific capacity and the best cycling performance, due to its high purity, high crystallinity, small particle size as well as moderate amount of Mn³⁺ ions.     

Rapid synthesis of nanocrystalline Co3O4 by a microwave-assisted combustion method

A facile and rapid microwave-assisted combustion method was developed to synthesize the nanocrystalline Co₃O₄. The study suggested that application of microwave heating to produce the homogeneous porous Co₃O₄ was achieved in a few minutes. The structure and morphology of the as-prepared nanocrystalline Co₃O₄ were investigated by means of X-ray diffraction (XRD), Fourier transform infrared spectra (FTIR), Raman spectra, UV-vis absorbance spectra and scanning electron microscopy (SEM). The XRD, FTIR and Raman spectra confirmed the formation of spinel structural Co₃O₄, and the SEM results indicated the porous surface characteristic of the products. Magnetic measurement was carried out using a vibrating sample magnetometer (VSM). The field dependence of the magnetization at room temperature showed a tiny hysteresis loop with a coercivity of 56.7 Oe.     

Effects of Si source and high gravity on combustion synthesis of Ti3SiC2 in air

Abstract

Combustion synthesis of Ti₃SiC₂ was carried out in air with Si₃N₄, SiC, and Si as Si sources respectively, and the effect of Si source on the phase composition of the products was investigated. With Si₃N₄ as Si source, the major product was TiC_xN_1?x and no Ti₃SiC₂ was synthesised. When SiC and Si were used, Ti₃SiC₂ was synthesised. Such effect of Si source is thought to be connected with the formation mechanism of Ti₃SiC₂, where the presence of a Ti–Si melt is required. The combustion synthesis was also performed under high gravity condition instead of common gravity. The apparent density of the product prepared under high gravity was ～60% higher than that obtained under normal gravity. It is proposed that, the high gravity can facilitate the permeation of Ti–Si melt and enlarge the interface between the melt and carbide phases, which is helpful for the formation of Ti₃SiC₂.     

POLYCYCLIC AROMATIC HYDROCARBON BOWLS,BASKETS, BALLS,AND TUBES: CHALLENGING TARGETS FOR CHEMICAL SYNTHESIS

The number of unique chemical substances registered by the Chemical Abstracts Service passed the 50 million mark in September 2009. The vast majority of these substances were brought into existence by chemical synthesis, a human activity that has grown immensely powerful and continues to advance at an ever-accelerating pace. It would not be unreasonable for the average layman to assume that chemists must now be able to synthesize everything imaginable; however, that Utopian level of success has not been achieved. Some molecular targets remain beyond the reach of chemical synthesis by present day methods. When fullerenes and carbon nanotubes were discovered near the end of the 20th century, for example, scientists quickly recognized that chemical methods to synthesize such large, curved, polycyclic aromatic structures simply did not exist. Since that time, progress has been made on the development of methods for this purpose, and the present article recounts some of the advances along those lines that have been made in the author’s laboratory.     

The role of C2 intermediates in Fischer-Tropsch synthesis over ruthenium

The C₂ products formed over Ru during Fischer-Tropsch synthesis often lie well below the Anderson-Schulz-Flory line describing the C₄₊ products. This has led to speculation that either the surface precursor to C₂ hydrocarbons is exceptionally long lived, or that the ethylene formed by CO hydrogenation readsorbs and thereby reenters the chain growth process. In this study, the role of ethylene readsorption on the dynamics of chain initiation and growth is investigated using¹³CO/H₂ and¹²C₂H₄ to differentiate between the carbon sources. Ethylene addition is found to suppress the rate of methanation and increase the rates of formation of C₃₊ hydrocarbons. Ethylene serves as an effective chain initiator, as well as a source of C₁ monomer species which participate in chain propagation. No evidence is seen, though, for the participation of C₂ species in chain propagation.     

Thermal degradation in bulk and thin films of 2-, 4-, and 6-arm polystyrene stars with a C60 core

The thermal stability (TS) of hexa-, tetra-, and di-arm polystyrene (PS) stars with a C₆₀ core was studied by thermal gravimetric analysis and mass-spectrometry. The quantitative production of volatile products, their composition and their formation kinetics during heating of (PS_xC₆₀) are reported. A bimodal release of styrene is observed. The first release takes place about 100 °C before the depolymerization temperature of styrene and all the C₆₀ comes out at this lower temperature. That results from a complete breaking of the weak PS-C₆₀ bonds followed by a partial depolymerization of the PS arms initiated by the so formed radicals. The amount of PS ‘surviving’ this first depolymerization step increases with the length of the arms and its TS is close to that of pure PS. The thermal stability of the PS_xC₆₀ stars decreases if the number of arms increases and, from the activation energy of the release of styrene and C₆₀, it was possible to estimate the PS-C₆₀ bond strength for these three adducts.     

Selective synthesis of C2-C4 hydrocarbons from CO + H2 on composite catalysts

A copper-zinc-aluminum methanol synthesis catalyst has been prepared using a precipitated hydrotalcite-type precursor that decomposes to a mixture of the corresponding amorphous oxides at a low temperature. TPR studies show that such a mixture is easy to reduce giving a highly dispersed catalyst. When this is mixed with a zeolite, the resulting hybrid catalyst gives C₂-C₄ hydrocarbons with very high selectivity. This may be useful in obtaining LPG from synthesis gas.     

The influence of mechanochemical activation on combustion synthesis of Si3N4

This study addresses itself in the performance of Si₃N₄ combustion synthesis, occurred in the presence of Si₃N₄ and NH₄Cl powders in N₂ atmosphere of 6 MPa. Mechanochemical activation of Si powder, achieved via high-energy attrition milling up to 24 h, increases the intensity and the efficiency of the reactions between Si and N₂ as well as combustion temperature. Benign processing conditions, anticipated with lower mechanochemical activation of Si powder, low N₂ pressures, and low combustion temperatures, favor formation of α-Si₃N₄.     

Lithium ion-exchanged zeolite faujasite as support of iron catalyst for Fischer-Tropsch synthesis

Among various microporous and mesoporous materials investigated, the Li⁺-exchanged zeolite faujasite has been found to be the most efficient support of iron catalyst for producing C₅⁺ hydrocarbon fuels via Fischer-Tropsch synthesis. The location of iron species in the catalyst is a key issue in obtaining high selectivities to C₅⁺ hydrocarbons. It is proposed that the Li⁺ cation and the supercage structure of zeolite faujasite both play important roles in improving the selectivities to C₅⁺ hydrocarbons over the Fe catalyst.     

MOLECULAR ORBITAL TREATMENT OF SOME ENDOHEDRALLY DOPED C60 SYSTEMS

The present review article is a collection of the theoretical studies about some endohedrally doped C ₆₀ systems, based on density functional theory and ab initio calculations. The energies of the composite system, as well as molecular orbital energies depend on the type of dopant, symmetry of the system and the spin state. In the case of C@C ₆₀ , the dopant interacts with the cage depending on the symmetry and spin state, whereas in Be@C ₆₀ , Be is found to be unbound. In certain cases (as Ca, Sc and Y) the interaction results in electron transfer from the dopant to the cage.     

Synthesis and solid-state studies of self-assembled C60 microtubes

C₆₀ microtubes were fabricated by a modified solution evaporation method, evaporating a solution of C₆₀ in toluene in an atmosphere of m-xylene at room temperature. The C₆₀ microtubes have outer diameters ranging from 2 to 8 μm. IR spectra, TG analysis and X-ray diffraction showed a solvated structure for the as-grown C₆₀ microtubes. Through a gentle heat-treatment in vacuum, pure C₆₀ microtubes with single crystalline fcc structure were obtained after the elimination of solvents. It is suggested that the C₆₀ microtubes form through self-assembly from several individual C₆₀ nanorods.     

Synthesis of Buckminsterfullerene C60 functionalised core cross-linked star polymers

Buckminsterfullerene C₆₀ core functionalised core cross-linked star (CCS) polymers have been prepared for the first time, using atom transfer radical polymerisation and the arms-first approach. A simple and efficient method is presented which allows the construction of star polymers consisting of a large number of arms and multiple units of C₆₀ per core, far in excess of that obtained previously. The C₆₀ CCS polymers were characterised by gel permeation chromatography (GPC), UV-vis spectroscopy and cyclic voltammetry (CV). GPC revealed that the C₆₀ CCS polymers possess weight average molecular weights (M_w) ranging from 172-411 kDa and up to 30 arms per macromolecule. The average number of molecules of C₆₀ per CCS polymer core was found to be dependent on the C₆₀/PMMA ratio employed and was determined by UV-vis spectroscopy to range up to 6.2. CV revealed that, like pristine C₆₀, the C₆₀ CCS polymers possessed three reversible one electron reductions. However, the reduction potentials were positively shifted, implying that the electron affinity of these macromolecules is higher than pristine C₆₀.     

In situ preparation of SiC/Si3N4-NW composite powders by combustion synthesis

Large-scale composite powders containing silicon carbide (SiC) particles and silicon nitride nanowires (Si₃N₄-NWs) were synthesized in situ by combustion synthesis (CS). In this process, a mixture of silicon, carbon black, polytetrafluoroethylene (PTFE) and a small amount of iron powders was used as the precursor. The products were characterized by XRD, SEM, EDS and TEM. The particles are equiaxed with diameters in the micron range, and the in situ formed nanowires are straight with uniform diameters of 20-350 nm and lengths of tens of microns. The Si₃N₄-NWs are characterized to be α-phase single crystals grown along the [1 0 1] or [1 0 0] direction. VLS and SLGS processes are proposed as the growth mechanisms of the nanowires. The as-synthesized powders have great potential for use in the preparation of high-performance SiC/Si₃N₄-NW composites.     

Fuel mixture approach for solution combustion synthesis of Ca3Al2O6 powders

Single-phase 3CaO·Al₂O₃ powders were prepared via solution combustion synthesis using a fuel mixture of urea and β-alanine. The concept of using this fuel mixture comes from the individual reactivity of calcium nitrate and aluminum nitrate with respect to urea and β-alanine. It was proved that urea is the optimum fuel for Al(NO₃)₃ whereas β-alanine is the most suitable fuel for Ca(NO₃)₂. X-ray diffraction and thermal analysis investigations revealed that heating at 300 °C the precursor mixture containing the desired metal nitrates, urea and β-alanine triggers a vigorous combustion reaction, which yields single-phase nanocrystalline 3CaO·Al₂O₃ powder (33.3 nm). In this case additional annealing was no longer required. The use of a single fuel failed to ensure the formation of 3CaO·Al₂O₃ directly from the combustion reaction. After annealing at 900 °C for 1 h, the powders obtained by using a single fuel (urea or β-alanine) developed a phase composition comprising of 3CaO·Al₂O₃, 12CaO·7Al₂O₃ and CaO.     

Preparation of tungsten borides by combustion synthesis involving borothermic reduction of WO3

An experimental study on the preparation of two tungsten borides, WB and W₂B₅, was conducted by self-propagating high-temperature synthesis (SHS), during which borothermic reduction of WO₃ and elemental interaction of W with boron proceeded concurrently. Powder mixtures with two series of molar proportions of WO₃:B:W = 1:5.5:x (with x = 1.16–2.5) and 1:7.5:y (with y = 0.5–1.33) were adopted to fabricate WB and W₂B₅, respectively. The starting stoichiometry of the reactant compact substantially affected the combustion behavior and the phase composition of the final product. The increase of metallic tungsten and boron reduced the overall reaction exothermicity, leading to a decrease in both combustion temperature and reaction front velocity. The initial composition of the reactant compact was optimized for the synthesis of WB and W₂B₅. In addition to small amounts of W₂B and W₂B₅, the powder compact of WO₃ + 5.5B + 2 W produced WB dominantly. Optimum formation of W₂B₅ was observed in the sample of WO₃ + 7.5B + 0.85W. Experimental evidence indicates that an excess amount of boron about 10–13% is favorable for the formation of WB and W₂B₅.