An experimental and modeling study of the autoignition of 3-methylheptane

An experimental and kinetic modeling study of the autoignition of 3-methylheptane, a compound representative of the high molecular weight lightly branched alkanes found in large quantities in conventional and synthetic aviation kerosene and diesel fuels, is reported. Shock tube and rapid compression machine ignition delay time measurements are reported over a wide range of conditions of relevance to combustion engine applications: temperatures from 678 to 1356 K; pressures of 6.5, 10, 20, and 50 atm; and equivalence ratios of 0.5, 1.0, and 2.0. The wide range of temperatures examined provides observation of autoignition in three reactivity regimes, including the negative temperature coefficient (NTC) regime characteristic of paraffinic fuels. Comparisons made between the current ignition delay measurements for 3-methylheptane and previous results for n-octane and 2-methylheptane quantifies the influence of a single methyl substitution and its location on the reactivity of alkanes. It is found that the three C₈ alkane isomers have indistinguishable high-temperature ignition delay but their ignition delay times deviate in the NTC and low-temperature regimes in correlation with their research octane numbers. The experimental results are compared with the predictions of a proposed kinetic model that includes both high- and low-temperature oxidation chemistry. The model mechanistically explains the differences in reactivity for n-octane, 2-methylheptane, and 3-methylheptane in the NTC through the influence of the methyl substitution on the rates of isomerization reactions in the low-temperature chain branching pathway, that ultimately leads to ketohydroperoxide species, and the competition between low-temperature chain branching and the formation of cyclic ethers, in a chain propagating pathway.     

Combustion characteristics in a small-scale reactor with catalyst segmentation and cavities

Hydrogen–air combustion characteristics of a small-scale reactor with different catalyst layouts and configurations are experimentally and numerically investigated. Four different platinum catalyst layouts are used to investigate the effect of catalyst segmentation on combustion performance. It is found that combustion phenomena are strongly related to the variations of inflow velocity, equivalence ratio, and length of catalyst segment. The existence of hetero- and homogeneous reactions in the combustor relies on sufficient catalytically induced exothermicity as well as sufficient hydrogen in the remaining mixture. Besides, the multi-segment catalyst with cavities appreciably extends the stable operating range of catalytic combustion in a small-scale combustor for a wide range of inflow velocities. Nevertheless, gas-phase reaction can be sustained and anchored by the existence of cavity in a small-scale system. The reactor with proposed mechanisms can be applied to various small-scale power, heat generation, and propulsion systems.     

Effects of γ rays irradiation on structure and property of TiO2 thin films

TiO₂ thin films were deposited on a glass substrate by the radio frequency magnetron sputtering method, and annealed for 2 h at temperatures of 550°C. Then, ⁶⁰Co γ rays with different doses were used to irradiate the resulting TiO₂ thin films. The surface features of films before and after irradiation were observed by scanning electron microscope (SEM). Simultaneously, the crystal structure and optical properties of films before and after irradiation were studied by X-ray diffraction (XRD), UV–VIS transmission spectrum and Photoluminescence (PL) spectrum, respectively. The SEM analysis shows that the film is smooth with tiny particles on the film surface, and non-crystallization trend was clear after irradiated with γ rays. The XRD results indicated that the structure of the film at the room temperature mainly exists in the form of amorphous and mixed crystal at a sputtering power of 200 W, and non-crystallinity was more obvious after irradiation. Obvious difference can be found for the transmissibility of the irradiated and pre irradiation TiO₂ films by the UV-VIS spectra. The color becomes light yellow, and the new absorption edge also appeared at about 430 nm. PL spectra and photocatalysis experiments indicate that the photocatalysis degradation rate of the TiO₂ films on methylthionine chloride solution irradiated with the maximum dose can be increased to 90%.     

Radiation-induced changes in electrical conductivity and structure of BaPbO3 after γ-irradiation

Several barium plumbate (BaPbO₃) solid samples, made from PbO and BaCO₃ powder by chemistry liquid-phase coprecipitation, were investigated before and after γ-irradiation. The solid samples were irradiated by a ⁶⁰Co γ-irradiation source whose dose rate is about 0.7?kGy per hour. The irradiation times were 0, 72, 144, 216, 288 and 360?h. Then, the four-probe method, X-ray diffraction (XRD), scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS) were used to indicate the changes in electrical conductivity and microstructure of BaPbO₃ after γ-irradiation. The XRD results indicated that the content of PbO was reduced as the irradiation dose was increased and eventually vanished from the surface of samples. However, there was no new obvious substance phase found from the XRD atlas. It seems that the PbO transformed into nearly amorphous Pb₅O₈. The conjecture could be proved by the results of annealing experiment and SEM. The XPS results seem to show that the microstructure of BaPbO₃ was slightly changed.     

Theoretical explanation of optical absorption spectra and covalent effect of Ni2+ ions in octahedral sites of Ca3Sc2Ge3O12 crystal

The optical absorption spectra (d-d transition bands) and covalent effect of Ni²⁺ ions in octahedral sites of Ca₃Sc₂Ge₃O₁₂ crystal have been investigated by the full energy matrix based on the two spin–orbit coupling parameters model. The bond length of octahedral site is R_i?=?2.19 Å, which can be determined by the cubic crystal-field parameter and optical spectral data. The lattice distortion of the Ni²⁺ center in Ca₃Sc₂Ge₃O₁₂ crystal is also obtained from the calculations. In addition, the result has shown that the covalent effect of Ni²⁺ ion in the octahedral site of Ga₃Sc₂Ge₃O₁₂ is obvious and cannot be ignored. The calculated d-d transition bands agree well with that of the experimental findings, suggesting that the present methods can explain reasonably the optical spectral data and covalent effect of 3d⁸ ions in octahedral lattices.     

Theoretical investigations of the EPR parameters and local structure for Cu2+ in BeO

The electron paramagnetic resonance (EPR) parameters (the anisotropic g factors, the hyperfine structure parameters and the quadrupole coupling constant Q) and local structure for Cu²⁺ in BeO are theoretically investigated from the perturbation formulas of these parameters for a 3d⁹ ion under trigonally distorted tetrahedra. The ligand orbital and spin-orbit coupling contributions are included in the basis of the cluster approach, in view of the strong covalency of the [CuO₄]^6? cluster. From the calculations, the impurity Cu²⁺ is suggested not to occupy exactly the ideal Be²⁺ site but to suffer a slight inward displacement (≈0.024 Å) toward the ligand triangle along the C₃ axis. The theoretical EPR parameters show good agreement with the experimental data.     

3-D simulation of soot formation in a direct-injection diesel engine based on a comprehensive chemical mechanism and method of moments

Here, we propose both a comprehensive chemical mechanism and a reduced mechanism for a three-dimensional combustion simulation, describing the formation of polycyclic aromatic hydrocarbons (PAHs), in a direct-injection diesel engine. A soot model based on the reduced mechanism and a method of moments is also presented. The turbulent diffusion flame and PAH formation in the diesel engine were modelled using the reduced mechanism based on the detailed mechanism using a fixed wall temperature as a boundary condition. The spatial distribution of PAH concentrations and the characteristic parameters for soot formation in the engine cylinder were obtained by coupling a detailed chemical kinetic model with the three-dimensional computational fluid dynamic (CFD) model. Comparison of the simulated results with limited experimental data shows that the chemical mechanisms and soot model are realistic and correctly describe the basic physics of diesel combustion but require further development to improve their accuracy.     

Basic solution of four parallel non-symmetric permeable Mode-III cracks in a piezoelectric/piezomagnetic composite plane

The interaction of four parallel non-symmetric permeable cracks in a piezoelectric/piezomagnetic composite plane subjected to anti-plane shear stress loading was studied by the Schmidt method. The problem was formulated through a Fourier transform into four pairs of dual integral equations, in which unknown variables are jumps of displacements across the crack surfaces. To solve the dual integral equations, the jumps of displacements across the crack surfaces were directly expanded as a series of Jacobi polynomials. Finally, the relationships among the electric displacement, magnetic flux and stress fields near the crack tips were obtained. The results show that the stress, the electric displacement and the magnetic flux intensity factors at the crack tips depend on the lengths and spacing of cracks. It was also revealed that the crack shielding effect is present in piezoelectric/piezomagnetic composites.     

The interaction between a screw dislocation and an interfacial cruciform crack and collinear linear cracks

The interaction between a screw dislocation and an interfacial cruciform crack and collinear linear cracks under loads at infinity was investigated. General solutions of complex potentials to this problem were derived by using complex potential theory. As illustrative examples, the closed form solution for a screw dislocation interacting with an interfacial cruciform crack and a linear crack is obtained. The stress intensity factor and critical stress intensity factor for dislocation emission are also calculated. The results show that the shielding effect increases with the increase of the shear modulus and the distance between the two cracks, but it decreases with the increase of dislocation azimuth and the distance between the dislocation and the cruciform crack tip. The critical loads at infinity for dislocation emission increase with the increment of the emission angle, the distance the two cracks and the vertical length of the cruciform crack.     

Electroelastic behaviour of an annular interfacial crack between dissimilar piezoelectric layers

An annular interfacial crack between dissimilar piezoelectric layers subjected to electroelastic loadings was investigated under an electrically impermeable boundary condition on the crack surface by using the Hankel transform technique and the Cauchy singular integral equation method. The stress intensity factors and energy release rates were determined. Numerical results reveal the effects of crack configuration, electric loads and material parameters on crack propagation and growth. The results should be useful for the design of piezoelectric composite structures and devices of high performance.