Structural studies of cyclic ureas: 3. Enthalpy of formation of barbital

A thermochemical and thermophysical study has been carried out for crystalline barbital [5,5′-diethylbarbituric acid]. The thermochemical study was made by static bomb combustion calorimetry, from which the standard () molar enthalpy of formation of the crystalline barbital, at T = 298.15 K, was derived as −(753.0 ± 1.8) kJ · mol⁻¹. The thermophysical study was made by differential scanning calorimetry over the temperature interval (265 to 470) K. A solid–solid phase transition was found at T = 413.3 K. The vapour pressures of the crystalline barbital were measured at several temperatures between T = (355 and 377) K, by the Knudsen mass-loss effusion technique, from which the standard molar enthalpy of sublimation, at T = 298.15 K was derived as (117.3 ± 0.6) kJ · mol⁻¹. The combination of the experimental results yielded the standard molar enthalpy of formation of barbital in the gaseous phase, at T = 298.15 K, as −(635.8 ± 1.9) kJ · mol⁻¹. This value is compared and discussed with our theoretical calculations by several methods (Gaussian-n theories G2 and G3, complete basis set CBS-QB3, density functional B3P86 and B3LYP) by means of atomization and isodesmic reaction schemes.     

Energetics of flavone and flavanone

In this work, we have determined the experimental standard (p° = 0.1 MPa) molar enthalpies of formation, in gas phase, of flavone and flavanone.These results were obtained by combining the standard molar enthalpies of formation in the condensed phase with the standard molar enthalpies of sublimation. The former values were derived from combustion experiments in oxygen, at T = 298.15 K, in a static bomb calorimeter. The values of the standard molar enthalpies of sublimation were obtained by Calvet microcalorimetry and corrected to T = 298.15 K.High-level density functional theory calculations using the B3LYP hybrid exchange–correlation energy functional with extended basis sets and more accurate correlated computational techniques of the MCCM/3 suite have been performed for the compounds.The obtained results, experimental and computational, for flavone and flavanone were compared with those obtained for chromone and chromanone, respectively.     

Synthesis of nanosized silicon particles by a rapid metathesis reaction

A solid-state rapid metathesis reaction was performed in a bed of sodium silicofluoride (Na₂SiF₆) and sodium azide (NaN₃) powders diluted with sodium fluoride (NaF), to produce silicon nanoparticles. After a local ignition of Na₂SiF₆+4NaN₃+kNaF mixture (here k is mole number of NaF), the reaction proceeded in a self-sustaining combustion mode developing high temperatures (950–1000 °C) on very short time scales (a few seconds). Silicon nanoparticles prepared by the combustion process was easily separated from the salt byproducts by simple washing with distilled water. The structural and morphological studies on the nanoparticles were carried out using X-ray diffractometer (XRD) and field emission scanning electron microscope (FESEM). The mean size of silicon particles calculated from the FESEM image was about 37.75 nm. FESEM analysis also shows that the final purified product contains a noticeable amount of silicon fibers, dendrites and blocks, along with nanoparticles. The mechanism of Si nanostructures formation is discussed and a simple model for interpretation of experimental results is proposed.     

AN ANALYTICAL DESIGN METHODOLOGY FOR AN ANNULAR COMBUSTOR

SUMMARY

This paper describes a computational procedure for the optimization of the performance parameters of a simulated annular combustor. This method has been applied to analyze the influence of the performance parameters and geometries on the annular combustor characteristics and provide a good understanding of combustor internal flow fields, and therefore it can be used for guiding the combustor design process. The approach is based on the solution of governing nonlinear, elliptic partial differential equations for 3-D axisymmetric recirculating turbulent reacting swirling flows and the modelling of turbulence, combustion, thermal radiation and pollutant formation. The turbulence effects are introduced via the modified two-equation κ-ε model. Turbulent combustion is modelled using the κ-ε-g model and a two-step turbulent combustion model is employed for the excess emission of carbon monoxide CO. For the evaluation of the NO pollutant formation rate, the NO pollutant formation model, which takes into account the influence of turbulence, presented here. The radiative heat transfer is handled by the heat flux model. The predictions of the combustor character-istics and performance parameters are made using the present approach.

Predictions of velocity, length of the recirculation zone, combustion efficiency and wall temperature are compared with measurements. Agreement between the predictions and experimental data is very satisfactory.     

结合吸收光谱与互相关法的燃气速度测量方法研究

针对可调谐半导体激光器吸收光谱(TDLAS)基于多普勒效应测速方法在燃气流速测量中频移量小、误差较大的问题,提出了结合固定波长吸收光谱法与互相关法的燃气速度测量方法。考虑碳氢燃料燃烧产物特点,选取H₂O分子7 185.597 cm-1吸收谱线,通过布置上下游两束固定波长吸收光谱测点,分析两信号的互相关特性来计算得到燃气速度。利用平面火焰炉实验系统对该方法测量燃气速度开展实验研究,获得了变工况下燃气速度随时间的变化情况。在相同工况下开展数值计算,将测量结果与数值模拟计算结果进行对比,相对偏差不超过8%。同时将该方法初步应用于煤油燃料火箭基组合循环发动机(RBCC)的高速羽流速度测量,获得了上下游探测器脉动信号,通过互相关分析计算得到了羽流速度,验证了该方法的可行性。实验结果表明,该燃气速度测量方法具有测量范围宽、测量精度高,环境干扰小等优点。提出的方法为发动机燃气速度测量提供一种简单可靠的测量方法。     

Effect of glycine–starch mixing ratio on the structural characteristics of MgAl2O4 nano-particles synthesized by sol–gel combustion

Sol–gel auto-ignition was used to prepare nano-scale magnesium aluminate spinel, using nitrate salts as an oxidizer and glycine–starch mixtures as the fuel. The glycine–starch mixture was varied to understand the effect of fuel mixing ratio on the structural characteristics of the resulting magnesium aluminate. The products were characterized by thermogravimetric-differential thermal analyses, Fourier-transform infrared spectroscopy, X-ray diffraction, Brunauer–Emmett–Teller surface area measurements, and transmission electron microscopy. The phase purity and crystallite size of the powder products depended on the fuel mixing ratio. The presence of starch in the fuel facilitated the preparation of pure nano-particles. To prepare nano-particles of uniform spherical morphology and diameter of <13 nm, the starch content should be optimized to avoid agglomeration.     

Modeling of particle transport and combustion phenomena in a large-scale circulating fluidized bed boiler using a hybrid Euler-Lagrange approach

The constantly developing fiuidized combustion technology has become competitive with a conventional pulverized coal （PC） combustion. Circulating fluidized bed （CFB） boilers can be a good alternative to PC boilers due to their robustness and lower sensitivity to the fuel quality. However, appropriate engineering tools that can be used to model and optimize the construction and operating parameters of a CFB boiler still require development. This paper presents the application of a relatively novel hybrid Euler-Lagrange approach to model the dense gas-solid flow combined with a combustion process in a large-scale indus- trial CFB boiler. In this work, this complex flow has been resolved by applying the ANSYS FLUENT 14.0 commercial computational fluid dynamics （CFD） code. To accurately resolve the multiphase flow, the original CFD code has been extended by additional user-defined functions. These functions were used to control the boiler mass load, particle recirculation process （simplified boiler geometry）, and interphase hydrodynamic properties. This work was split into two parts. In the first part, which is referred to as pseudo combustion, the combustion process was not directly simulated. Instead, the effect of the chemi- cal reactions was simulated by modifying the density of the continuous phase so that it corresponded to the mean temperature and composition of the flue gases, In this stage, the particle transport was simu- lated using the standard Euler-Euler and novel hybrid Euler-Lagrange approaches, The obtained results were compared against measured data, and both models were compared to each other. In the second part, the numerical model was enhanced by including the chemistry and physics of combustion. To the best of the authors＇ knowledge, the use of the hybrid Euler-Lagrange approach to model combustion is a new engineering application of this model, In this work, the combustion process was modeled for air-fuel combustion. The simulation results were compared with experimental data.     

Synthesis and characterization of BaAl2O4:Eu co-doped with different rare earth ions

Combustion method was used in this study to prepare BaAl₂O₄:Eu²⁺ phosphors co-doped with different trivalent rare-earths (Re³⁺=Dy³⁺, Nd³⁺, Gd³⁺, Sm³⁺, Ce³⁺, Er³⁺, Pr³⁺ and Tb³⁺) ions at an initiating temperature of 600 °C. The phosphors were annealed at 1000 °C for 3 h. As confirmed from the X-ray diffraction (XRD) data, both as prepared and post annealed samples crystallized in the well known hexagonal structure of BaAl₂O₄. All samples exhibited bluish-green emission associated with the 4f⁶5d¹→4f⁷ transitions of Eu²⁺ at ∼500 nm. Although the highest intensity was observed from Er³⁺ co-doping, the longest afterglow (due to trapping and detrapping of charge carriers) was observed from Nd³⁺ followed by Dy³⁺ co-doping. The traps responsible for the long afterglow were studied using thermoluminescence (TL) spectroscopy.     

EPR and photoluminescence properties of green light emitting LaAl11O18:Mn phosphors

The LaAl₁₁O₁₈:Mn²⁺ powder phosphor has been prepared using a self-propagating synthesis. Formation and homogeneity of the LaAl₁₁O₁₈:Mn²⁺ phosphor has been verified by X-ray diffraction and energy dispersive X-ray analysis respectively. The EPR spectra of Mn²⁺ ions exhibit resonance signals with effective g values at g≈4.8 and g≈1.978. The signal at g≈1.978 exhibits six-line hyperfine structure and is due to Mn²⁺ ions in an environment close to tetrahedral symmetry, whereas the resonance at g≈4.8 is attributed to the rhombic surroundings of the Mn²⁺ ions. It is observed that the number of spins participating in resonance for g≈1.978 increases with decreasing temperature obeying the Boltzmann law. Upon 451 nm excitation, the photoluminescence spectrum exhibits a green emission peak at 514 nm due to ⁴T₁ (G)→⁶A₁ (S) transition of Mn²⁺ ions. The crystal field parameter Dq and Racah inter-electronic repulsion parameters B and C have been evaluated from the excitation spectrum.     

Numerical investigation on the flowfield of ＂swallowtail＂ cavity for supersonic mixing enhancement

A ＂swallowtail＂ cavity for the supersonic combustor was proposed to serve as an efficient flame holder for scramjets by enhancing the mass exchange between the cavity and the main flow. A numerical study on the ＂swallow- tail＂ cavity was conducted by solving the three-dimensional Reynolds-averaged Navier-Stokes equations implemented with a k-e turbulence model in a multi-block mesh. Turbu- lence model and numerical algorithms were validated first, and then test cases were calculated to investigate into the mechanism of cavity flows. Numerical results demonstrated that the certain mass in the supersonic main flow was sucked into the cavity and moved spirally toward the combustor walls. After that, the flow went out of the cavity at its lateral end, and finally was efficiently mixed with the main flow. The comparison between the ＂swallowtail＂ cavity and the conventional one showed that the mass exchanged between the cavity and the main flow was enhanced by the lateral flow that was induced due to the pressure gradient inside the cavity and was driven by the three-dimensional vortex ring generated from the ＂swallowtail＂ cavity structure.