Synthesis, characterisation, luminescence and defect centres in solution combustion synthesised CaZrO3:Tb3+ phosphor

Tb3+ doped CaZrO3 has been prepared by an easy solution combustion synthesis method. The combustion derived powder was investigated by X-ray diffraction, Fourier-transform infrared spectrometry and scanning electron microscopy techniques. A room temperature photoluminescence study showed that the phosphors can be efficiently excited by 251 nm light with a weak emission in the blue and orange region and a strong emission in green light region. CaZrO3:Tb3+ exhibits three thermoluminescence (TL) glow peaks at 126 degrees C, 200 degrees C and 480 degrees C. Electron Spin Resonance (ESR) studies were carried out to study the defect centres induced in the phosphor by gamma irradiation and also to identify the centres responsible for the TL peaks. The room temperature ESR spectrum of irradiated phosphor appears to be a superposition of two distinct centres. One of the centres (centre I) with principal g-value 2.0233 is identified as an O- ion. Centre II with an axial symmetric g-tensor with principal values g(parallel to) = 1.9986 and g(perpendicular to) = 2.0023 is assigned to an F+ centre (singly ionised oxygen vacancy). An additional defect centre is observed during thermal annealing experiments and this centre (assigned to F+ centre) seems to originate from an F centre (oxygen vacancy with two electrons). The F centre and also the F+ centre appear to correlate with the observed high temperature TL peak in CaZrO3:Tb3+ phosphor. (c) 2012 Elsevier B.V. All rights reserved.

A numerical methodology for the multi-objective optimization of the DI Diesel engine combustion

DI Diesel engine are widely used both for industrial and automotive applications due to their durability and fuel economy. Nonetheless, increasing environmental concerns force that type of engine to comply with increasingly demanding emission limits, so that, it has become mandatory to develop a robust design methodology of the DI Diesel combustion system focused on reduction of soot and NOx simultaneously while maintaining a reasonable fuel economy. In recent years, genetic algorithms and CFD three-dimensional combustion simulations have been successfully applied to that kind of problem. However, combining GAs optimization with actual CFD three-dimensional combustion simulations can be too onerous since a large number of calculations is usually needed for the genetic algorithm to converge, resulting in a high computational cost and, thus, limiting the suitability of this method for industrial processes. In order to make the optimization process less time-consuming, CFD simulations can be more conveniently used to generate a training set for the learning process of an artificial neural network which, once correctly trained, can be used to forecast the engine outputs as a function of the design parameters during a GA optimization performing a so-called virtual optimization. In the current work, a numerical methodology for the multi-objective virtual optimization of the combustion of an automotive DI Diesel engine, which relies on artificial neural networks and genetic algorithms, was developed.

Revision of a Liquid Fuel Airblast Atomizer and Installation of a Laser Extinction System for Measurement of Soot Produced During Liquid Fuel Combustion

Studying liquid fuel combustion is necessary to better design combustion systems. Through more efficient combustors and alternative fuels, it is possible to reduce greenhouse gases and harmful emissions. In particular, coal-derived and Fischer-Tropsch liquid fuels are of interest because, in addition to producing fewer emissions, they have the potential to drastically reduce the United States' dependence on foreign oil. Major academic research institutions like the Pennsylvania State University perform cutting-edge research in many areas of combustion. The Combustion Research Laboratory (CRL) at Bucknell University is striving to develop the necessary equipment to be capable of both independent and collaborative research efforts with Penn State and in the process, advance the CRL to the forefront of combustion studies. The focus of this thesis is to advance the capabilities of the Combustion Research Lab at Bucknell. Specifically, this was accomplished through a revision to a previously designed liquid fuel injector, and through the design and installation of a laser extinction system for the measurement of soot produced during combustion. The previous liquid fuel injector with a 0.005" hole did not behave as expected. Through spray testing the 0.005" injector with water, it was determined that experimental errors were made in the original pressure testing of the injector. Using data from the spray testing experiment, new theoretical hole sizes of the injector were calculated. New injectors with 0.007" and 0.0085" orifices were fabricated and subsequently tested to qualitatively validate their behavior. The injectors were installed in the combustion rig in the CRL and hot-fire tested with liquid heptane. The 0.0085" injector yielded a manageable fuel pressure and produced a broad flame. A laser extinction system was designed and installed in the CRL. This involved the fabrication of a number of custom-designed parts and the specification of laser extinction equipment for purchase. A standard operating procedure for the laser extinction system was developed to provide a consistent, safe method for measuring soot formation during combustion.

Parametric combustion modeling for ethanol-gasoline fuelled spark ignition engines

Ethanol-gasoline fuel blends are increasingly being used in spark ignition (SI) engines due to continued growth in renewable fuels as part of a growing renewable portfolio standard (RPS). This leads to the need for a simple and accurate ethanol-gasoline blends combustion model that is applicable to one-dimensional engine simulation. A parametric combustion model has been developed, integrated into an engine simulation tool, and validated using SI engine experimental data. The parametric combustion model was built inside a user compound in GT-Power. In this model, selected burn durations were computed using correlations as functions of physically based non-dimensional groups that have been developed using the experimental engine database over a wide range of ethanol-gasoline blends, engine geometries, and operating conditions. A coefficient of variance (COV) of gross indicated mean effective pressure (IMEP) correlation was also added to the parametric combustion model. This correlation enables the cycle combustion variation modeling as a function of engine geometry and operating conditions. The computed burn durations were then used to fit single and double Wiebe functions. The single-Wiebe parametric combustion compound used the least squares method to compute the single-Wiebe parameters, while the double-Wiebe parametric combustion compound used an analytical solution to compute the double-Wiebe parameters. These compounds were then integrated into the engine model in GT-Power through the multi-Wiebe combustion template in which the values of Wiebe parameters (single-Wiebe or double-Wiebe) were sensed via RLT-dependence. The parametric combustion models were validated by overlaying the simulated pressure trace from GT-Power on to experimentally measured pressure traces. A thermodynamic engine model was also developed to study the effect of fuel blends, engine geometries and operating conditions on both the burn durations and COV of gross IMEP simulation results.

DEVELOPMENT OF A PREDICTIVE COMBUSTION MODEL OF A SPARK IGNITED ENGINE WITH GASOLINE DIRECT INJECTION, VARIABLE VALVE TIMING, DURATION AND LIFT TECHNOLOGIES

There is a need by engine manufactures for computationally efficient and accurate predictive combustion modeling tools for integration in engine simulation software for the assessment of combustion system hardware designs and early development of engine calibrations. This thesis discusses the process for the development and validation of a combustion modeling tool for Gasoline Direct Injected Spark Ignited Engine with variable valve timing, lift and duration valvetrain hardware from experimental data. Data was correlated and regressed from accepted methods for calculating the turbulent flow and flame propagation characteristics for an internal combustion engine. A non-linear regression modeling method was utilized to develop a combustion model to determine the fuel mass burn rate at multiple points during the combustion process. The computational fluid dynamic software Converge ©, was used to simulate and correlate the 3-D combustion system, port and piston geometry to the turbulent flow development within the cylinder to properly predict the experimental data turbulent flow parameters through the intake, compression and expansion processes. The engine simulation software GT-Power © is then used to determine the 1-D flow characteristics of the engine hardware being tested to correlate the regressed combustion modeling tool to experimental data to determine accuracy. The results of the combustion modeling tool show accurate trends capturing the combustion sensitivities to turbulent flow, thermodynamic and internal residual effects with changes in intake and exhaust valve timing, lift and duration.

STUDY OF SPARK IGNITION ENGINE COMBUSTION MODEL FOR THE ANALYSIS OF CYCLIC VARIATION AND COMBUSTION STABILITY AT LEAN OPERATING CONDITIONS

A fundamental combustion model for spark-ignition engine is studied in this report. The model is implemented in SIMULINK to simulate engine outputs (mass fraction burn and in-cylinder pressure) under various engine operation conditions. The combustion model includes a turbulent propagation and eddy burning processes based on literature [1]. The turbulence propagation and eddy burning processes are simulated by zero-dimensional method and the flame is assumed as sphere. To predict pressure, temperature and other in-cylinder variables, a two-zone thermodynamic model is used. The predicted results of this model match well with the engine test data under various engine speeds, loads, spark ignition timings and air fuel mass ratios. The developed model is used to study cyclic variation and combustion stability at lean (or diluted) combustion conditions. Several variation sources are introduced into the combustion model to simulate engine performance observed in experimental data. The relations between combustion stability and the introduced variation amount are analyzed at various lean combustion levels.

PAH occurrence during combustion of biodiesel from various feedstocks

PAHs are pollutants of concern since they are known carcinogenic compounds. Their occurrence is mainly related to combustion or pyrolysis of organic matter such as fossil fuels. In the current scenario where biofuels are growingly important, it is also necessary to characterize PAH emissions due to their combustion. There are a number of works concerning PAH emissions from biodiesel combustion in Diesel engines, however, there are few regarding the difference between them depending on the feedstock and type of alcohol used in the transesterification. The authors have processed and characterized biodiesel from several feedstocks (Le. tallow, palm, rapeseed, soy-bean, coconut, peanut and linseed oils) to obtain FAME and FAEE and they have developed a method to measure the PAHs originated during their combustion in a bomb calorimeter. The tests have been carried out under different oxygen pressure conditions, and samples have been c1eaned from the bomb after each one of these tests. The samples have been prepared for GC-MS analysis, where PAH quantities among some other combustion products have been assessed. This work shows statistical relations obtained between the measured amounts of 18 PAHs of concern and the composition (oil and type of alcohol) used to obtain the biodiesel, and also the oxygen pressure during combustion.

Numerical simulation of group combustion of pulverized coal

A mathematical model for the group combustion of pulverized coal particles was developed in a previous work. It includes the Lagrangian description of the dehumidification, devolatilization and char gasification reactions of the coal particles in the homogenized gaseous environment resulting from the three fuels, CO, H2 and volatiles, supplied by the gasification of the particles and their simultaneous group combustion by the gas phase oxidation reactions, which are considered to be very fast. This model is complemented here with an analysis of the particle dynamics, determined principally by the effects of aerodynamic drag and gravity, and its dispersion based on a stochastic model. It is also extended to include two other simpler models for the gasification of the particles: the first one for particles small enough to extinguish the surrounding diffusion flames, and a second one for particles with small ash content when the porous shell of ashes remaining after gasification of the char, non structurally stable, is disrupted. As an example of the applicability of the models, they are used in the numerical simulation of an experiment of a non-swirling pulverized coal jet with a nearly stagnant air at ambient temperature, with an initial region of interaction with a small annular methane flame. Computational algorithms for solving the different stages undergone by a coal particle during its combustion are proposed. For the partial differential equations modeling the gas phase, a second order finite element method combined with a semi-Lagrangian characteristics method are used. The results obtained with the three versions of the model are compared among them and show how the first of the simpler models fits better the experimental results.

Preparation, characterisation and testing of CuO/Ce0.8Zr0.2O2 catalysts for NO oxidation to NO2 and mild temperature diesel soot combustion

CuO/ceria-zirconia catalysts have been prepared, deeply characterised (N2 adsorption–desorption isotherms at −196 °C, XRD, Raman spectroscopy, XPS, TEM and H2-TPR) and tested for NO oxidation to NO2 in TPR conditions, and for soot combustion at mild temperature (400 °C) in a NOx/O2 stream. The behaviour has been compared to that of a reference Pt/alumina commercial catalyst. The ceria-zirconia support was prepared by the co-precipitation method, and different amounts of copper (0.5, 1, 2, 4 and 6 wt%) were loaded by incipient wetness impregnation. The results revealed that copper is well-dispersed onto the ceria-zirconia support for the catalysts with low copper loading and CuO particles were only identified by XRD in samples with 4 and 6% of copper. A very low loading of copper increases significantly the activity for the NO oxidation to NO2 with regard to the ceria-zirconia support and an optimum was found for a 4% CuO/ceria-zirconia composition, showing a very high activity (54% at 348 °C). The soot combustion rate at 400 °C obtained with the 2% CuO/ceria-zirconia catalyst is slightly lower to that of 1% Pt/alumina in terms of mass of catalyst but higher in terms of price of catalyst.

Catalytic performance of CuO/Ce0.8Zr0.2O2 loaded onto SiC-DPF in NOx-assisted combustion of diesel soot

This work presents a comparative study between the catalytic performance of the 2% CuO/ceria-zirconia powder catalyst and the same catalyst supported on silicon carbide DPF (Diesel Particulate Filter) towards NO oxidation reaction and soot combustion reaction. The ceria-zirconia catalyst was prepared by the co-precipitation method and 2 wt% copper was incorporated by the incipient wetness impregnation method. The catalyst was incorporated onto the ceramic support using a simple and organic solvent-free procedure by a simply dipping the DPF into an aqueous solution of the catalyst. The powder catalyst has been characterized using N2 adsorption at −196 °C, XRD and Raman Spectroscopy; whereas the catalytic coating morphology has been evaluated by SEM and the mechanical stability by an adherence test. Both catalyst configurations were tested for NO oxidation to NO2 and for soot combustion under NOx/O2. The results revealed that incorporation of the very active copper/ceria-zirconia catalyst onto SiC-DPF has been successfully achieved by a simple coating procedure. Furthermore, the catalytic coating has shown suitable mechanical, chemical and thermal stability. A satisfactory catalytic performance of the catalytic-coated filter was reached towards the NO oxidation reaction. Moreover, it was proved that the catalytic coating is stable and the corresponding coated DPF can be reused for several cycles of NO oxidation without a significant decrease in its activity. Finally, it was verified that the loose-contact mode is a good choice to simulate the catalytic performance of this active phase in a real diesel particulate filter.

ASTM manual for rating diesel fuels by the cetane method.

Mode of access: Internet.

The application of numerical modelling to the assessment of the potential for, and the detection of, spontaneous combustion in coal mines

Numerical modelling has been used to examine the relationship between the results of two commonly used methods of assessing the propensity of coal to spontaneous combustion, the R70 and Relative Ignition Temperature tests, and the likely behaviour in situ. The criticality of various parameters has been examined and a method of utilising critical self-heating parameters has been developed. This study shows that on their own, the laboratory test results do not provide a reliable guide to in situ behaviour but can be used in combination to considerably increase the ability to predict spontaneous combustion behaviour.

Nonlinear Time-Fractional Differential Equations in Combustion Science

MSC 2010: 34A08 (main), 34G20, 80A25

Formation of Polycyclic Aromatic Hydrocarbons and Nitrogen Containing Polycyclic Aromatic Compounds in Titan's Atmosphere, the Interstellar Medium and Combustion

Several different mechanisms leading to the formation of (substituted) naphthalene and azanaphthalenes were examined using theoretical quantum chemical calculations. As a result, a series of novel synthetic routes to Polycyclic Aromatic Hydrocarbons (PAHs) and Nitrogen Containing Polycyclic Aromatic Compounds (N-PACs) have been proposed. On Earth, these aromatic compounds originate from incomplete combustion and are released into our environment, where they are known to be major pollutants, often with carcinogenic properties. In the atmosphere of a Saturn's moon Titan, these PAH and N-PACs are believed to play a critical role in organic haze formation, as well as acting as chemical precursors to biologically relevant molecules. The theoretical calculations were performed by employing the ab initio G3(MP2,CC)/B3LYP/6-311G** method to effectively probe the Potential Energy Surfaces (PES) relevant to the PAH and N-PAC formation. Following the construction of the PES, Rice-Ramsperger-Kassel-Markus (RRKM) theory was used to evaluate all unimolecular rate constants as a function of collision energy under single-collision conditions. Branching ratios were then evaluated by solving phenomenological rate expressions for the various product concentrations. The most viable pathways to PAH and N-PAC formation were found to be those where the initial attack by the ethynyl (C2H) or cyano (CN) radical toward a unsaturated hydrocarbon molecule led to the formation of an intermediate which could not effectively lose a hydrogen atom. It is not until ring cyclization has occurred, that hydrogen elimination leads to a closed shell product. By quenching the possibility of the initial hydrogen atom elimination, one of the most competitive processes preventing the PAH or N-PAC formation was avoided, and the PAH or N-PAC formation was allowed to proceed. It is concluded that these considerations should be taken into account when attempting to explore any other potential routes towards aromatic compounds in cold environments, such as on Titan or in the interstellar medium.

Utilization of coal combustion residues in glass manufacturing process

The focus of paper is to asses and evaluate new utilisation method of coals combustion resides in glass manufacturing process. Mathematical model of glass manufacturing material balance was used to find favourable proportion of normally used batch materials and coal ash. It was found that possible to substitute up to 20 % of batch with coal ash. On the world glass production scale there is a potential to save 8,4 million tons of silica sand, 6 million tons of dolomite, 3 million tons of clay and 0,2 million tons of lime borate. Furthermore, potential to utilize 2 % of coal combustion products with suggested method.