Optimisation of ultrasound assisted extraction of phenolic compounds from Sparganii rhizoma with response surface methodology

The present study reports on the extraction of phenolic compounds from sparganii rhizome. Box–Behnken Design (BBD), a widely used form of response surface methodology (RSM), was used to investigate the effect of process variables on the ultrasound-assisted extraction (UAE). Three independent variables including ethanol concentration (%), extraction time (min) and solvent-to-material ratio (mL/g) were studied. The results showed that the optimal UAE condition was obtained with an ethanol concentration of 75.3%, an extraction time of 40 min and a solvent-to-material ratio of 19.21 mL/g for total phenols, and an ethanol concentration of 80%, an extraction time of 33.54 min and solvent-to-material ratio of 22.72 mL/g for combination of ρ-hydroxybenzaldehyde, ρ-coumaric acid, vanillic acid, ferulic acid, rutin and kaempferol. The experimental values under optimal conditions were in good consistent with the predicted values, which suggested UAE is more efficient process as compared to solvent extraction.     

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.     

On the rate constants of OH + HO2 and HO2 + HO2: A comprehensive study of H2O2 thermal decomposition using multi-species laser absorption

Hydrogen peroxide (H₂O₂) and hydroperoxy (HO₂) reactions present in the H₂O₂ thermal decomposition system are important in combustion kinetics. H₂O₂ thermal decomposition has been studied behind reflected shock waves using H₂O and OH diagnostics in previous studies (Hong et al. (2009) [9] and Hong et al. (2010) [6,8]) to determine the rate constants of two major reactions: H₂O₂ + M → 2OH + M (k₁) and OH + H₂O₂ → H₂O + HO₂ (k₂). With the addition of a third diagnostic for HO₂ at 227 nm, the H₂O₂ thermal decomposition system can be comprehensively characterized for the first time. Specifically, the rate constants of two remaining major reactions in the system, OH + HO₂ → H₂O + O₂ (k₃) and HO₂ + HO₂ → H₂O₂ + O₂ (k₄) can be determined with high-fidelity.No strong temperature dependency was found between 1072 and 1283 K for the rate constant of OH + HO₂ → H₂O + O₂, which can be expressed by the combination of two Arrhenius forms: k₃ = 7.0 × 10¹² exp(550/T) + 4.5 × 10¹⁴ exp(?5500/T) [cm³ mol^?1 s^?1]. The rate constants of reaction HO₂ + HO₂ → H₂O₂ + O₂ determined agree very well with those reported by Kappel et al. (2002) [5]; the recommendation therefore remains unchanged: k₄ = 1.0 × 10¹⁴ exp(?5556/T) + 1.9 × 10¹¹⁺exp(709/T) [cm³ mol^?1 s^?1]. All the tests were performed near 1.7 atm.     

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.     

A normalised residence time transport equation for the numerical simulation of combustion with high-temperature air

This study concerns the numerical simulation of turbulent non-premixed combustion in highly preheated air streams. One of the objectives is to settle an efficient computational procedure to proceed with the numerical simulation of large-scale industrial devices. It is also expected that the availability of such a computational framework may facilitate comprehensive sensitivity analyses as well as the development of mathematical models able to represent turbulence-chemistry interactions (TCI) in such conditions. Based on the salient physical ingredients that characterise scalar mixing, propagation, and self-ignition processes, a turbulent combustion modelling framework is thus introduced and applied to the numerical simulation of well-documented laboratory flames. In the corresponding geometries, the bulk flow velocities of the reactants streams can reach rather large values, which lead the flame to lift from the burner rim. Partially premixed flame edges thus stabilise the whole flame structure and the temperature of the oxidising stream can be increased by vitiation with burned gases so as to promote the corresponding flame-stabilisation processes. For sufficiently large values of the vitiated airstream temperature, self-ignition mechanisms may be triggered thus leading to a competition between mixing, propagation, and ignition processes. In this context, the ratio of the residence time to the self-ignition delay is thought to be a relevant variable to delineate the possible influence of ignition phenomena. Therefore, a modelled transport equation for this normalised residence time is considered. The performance of the corresponding modelling proposal is analysed with special emphasis placed on its ability to reproduce ‘memory’ or ‘lagrangian’ effects related to thermal aging processes. In this respect, it is noteworthy that the present set of computations makes use of tabulated quantities associated to (i) steady laminar one-dimensional diffusion flamelets, so as to describe the composition of combustion products, (ii) steady laminar one-dimensional premixed flamelets, to describe the flame brush propagation, and (iii) temporal evolution of zero-dimensional homogeneous mixtures to account for the possible occurrence of self-ignition phenomena. In particular, the tabulated self-ignition time value is used to evaluate the increase in the normalised residence time. Finally, two modelling parameters are put into evidence and studied through a detailed sensitivity analysis.     

Modeling nongray gas-phase and soot radiation in luminous turbulent nonpremixed jet flames

Much progress has been made in radiative heat transfer modeling with respect to treatment of nongray radiation from both gas-phase species and soot particles, while radiation modeling in turbulent flame simulations is still in its infancy. Aiming at reducing this gap, this paper introduces state-of-the-art models of gas-phase and soot radiation to turbulent flame simulations. The full-spectrum k-distribution method (Modest, M.F., 2003, Journal of Quantitative Spectroscopy & Radiative Transfer, 76, 69–83) is implemented into a three-dimensional unstructured CFD code for nongray radiation modeling. The mixture full-spectrum k-distributions including nongray absorbing soot particles are constructed from a narrow-band k-distribution database created for individual gas-phase species, and an efficient scheme is employed for their construction in CFD simulations. A detailed reaction mechanism including NO _x and soot kinetics is used to predict flame structure, and a detailed soot model using a method of moments is employed to determine soot particle size distributions. A spherical-harmonic P₁ approximation is invoked to solve the radiative transfer equation. An oxygen-enriched, turbulent, nonpremixed jet flame is simulated, which features large concentrations of gas-phase radiating species and soot particles. Nongray soot modeling is shown to be of greater importance than nongray gas modeling in sooty flame simulations, with gray soot models producing large errors. The nongray treatment of soot strongly influences flame temperatures in the upstream and the flame-tip region and is essential for accurate predictions of NO. The nongray treatment of gases, however, weakly influences upstream flame temperatures and, therefore, has only a small effect on NO predictions. The effect of nongray soot radiation on flame temperature is also substantial in downstream regions where the soot concentration is small. Limitations of the P₁ approximation are discussed for the jet flame configuration; the P₁ approximation yields large errors in the spatial distribution of the computed radiative heat flux for highly anisotropic radiation fields such as those in flames with localized, near-opaque soot regions.     

Spin Hamiltonian parameters and local structures for tetragonal and orthorhombic Ir2+ centers in AgCl

The perturbation formulae of the spin Hamiltonian parameters (the anisotropic g factors, hyperfine structure constants and superhyperfine parameters) are established for a 5d⁷ ion in an orthorhombically elongated octahedron based on the cluster approach. These formulae are applied to the theoretical studies of the EPR spectra and the local structures for the tetragonal and orthorhombic Ir²⁺ centers in AgCl. For the tetragonal Ir²⁺ center, the uncompensated substitutional [IrCl₆]⁴ cluster is found to experience a relative elongation of about 0.08 Å along the C ₄ axis due to the Jahn–Teller effect. For the orthorhombic center, the ligand octahedron also suffers Jahn–Teller elongation (by about 0.08 Å) along the [001] (or Z) axis. Meanwhile, the ligand Cl intervening in the impurity Ir²⁺ and the next nearest neighbor silver vacancy V_Ag along the [100] (or X) axis may undergo an inward displacement of 0.004 Å towards the center of the octahedron due to electrostatic repulsion of the V_Ag. The calculated spin Hamiltonian parameters based on the above local structures show good agreement with experimental data for both centers.     

Indications of bulk property changes from surface ion implantation

In the majority of cases, the effects of ion implantation are confined close to the implant zone but, potentially, the resultant distortions and chemical modifications could catalyse relaxations extending into the bulk substrate. Such possibilities are rarely considered but the present data suggest that high dose ion implantation of ZnO has induced bulk changes. Surface implants with Cu and Tb strongly modified the low temperature bulk thermoluminescence properties generated by X-ray irradiation. Suggestions are proposed for the possible mechanisms for bulk relaxations and structural characteristics, which may indicate where such instability may occur in other lattice structures.     

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.     

Structure and stability of Σ3 grain boundaries in face centered cubic metals

Σ3 grain boundaries form as a result of either growth twinning or deformation twinning in face centered cubic (fcc) metals and play a crucial role in determining the mechanical and electrical properties and microstructural stability. We studied the structure and stability of Σ3 grain boundaries (GBs) in fcc metals by using topological analysis and atomistic simulations. Atomistic simulations were performed for Cu and Al with empirical interatomic potentials to reveal the influence of stacking fault energy on the morphology of the twinned grains. Three sets of tilt Σ3 GBs were studied with respect to the tilt axis parallel to ?111?, ?112?, and ?110?, respectively. We showed that Σ3{111} and Σ3{112} GBs are thermodynamically stable and the others will dissociate into terraced interfaces regardless of the stacking fault energy. The morphology of the nano-twinned grains in Cu is predicted from the above analysis and found to match with experiments.