The application of chemical reduction methods to a combustion system exhibiting complex dynamics

A number of chemical model reduction techniques have been developed over recent years with a growing range of applications in combustion. The following work demonstrates the application of such reduction techniques for a combustion system describing the oxidation of carbon monoxide + hydrogen in a continuously stirred tank reactor (CSTR) at very low pressure. The system exhibits complex dynamics including oscillatory glow, oscillatory ignition and mixed mode oscillations. It is demonstrated that a range of local reduction methods can be applied to such complex systems, as long as sufficient coverage of the accessed regions of phase space are included in the reduction analysis. The methods include sensitivity analysis, the quasi-steady state approximation (QSSA) and repro-modelling based on the concept of an intrinsic low dimensional manifold (ILDM). The system is qualitatively different from some previous applications of ILDM methods where trajectories tend towards a fixed equilibrium. The underlying dimension of the system is seen to vary throughout selected trajectories with rapid increases occurring over very short time-scales during oscillatory ignition. Nevertheless, a final reduced model of only four variables is developed using fitted orthonormal polynomials describing the system dynamics on a slow manifold. The application serves to demonstrate that the relationship between local reduced model error and global errors can be complex for systems exhibiting complex dynamics, with regions of seemingly small local mapping gradients requiring tighter error control in order to control global errors. This feature may be common in cases where nearby trajectories are seen to diverge within the slow manifold over time.     

A detailed chemical kinetic reaction mechanism for oxidation of four small alkyl esters in laminar premixed flames

A detailed chemical kinetic reaction mechanism has been developed for a group of four small alkyl ester fuels, consisting of methyl formate, methyl acetate, ethyl formate, and ethyl acetate. This mechanism is validated by comparisons between computed results and recently measured intermediate species mole fractions in fuel-rich, low-pressure, premixed laminar flames. The model development employs a principle of similarity of functional groups in constraining the H atom abstraction and unimolecular decomposition reactions for each of these fuels. As a result, the reaction mechanism and formalism for mechanism development are suitable for extension to larger oxygenated hydrocarbon fuels, together with an improved kinetic understanding of the structure and chemical kinetics of alkyl ester fuels that can be extended to biodiesel fuels. Variations in concentrations of intermediate species levels in these flames are traced to differences in the molecular structure of the fuel molecules.     

The study of optimal oxidation time and different temperatures for high quality VO2 thin film based on the sputtering oxidation coupling method

The high quality Vanadium dioxide (VO₂) thin films have been fabricated successfully on sapphire by a simple novel sputtering oxidation coupling (SOC) method. All VO₂ thin film samples exhibit a good metal-insulator transition (MIT) at about 340 K. The optimal oxidation time at different temperatures has been experimentally investigated. We report on the relationship between optimal oxidation time and different temperatures of metal vanadium thin film samples of 101 nm thickness by oxidation in air. It is found that the optimal oxidation time ln(t) as a function of temperature 1/T shows a significant linear relationship among 703 K-783 K, in good agreement with the Wagner's high-temperature oxidation model.     

The influence of polytetrafluorethylene reduction on the capacity loss of the carbon anode for lithium ion batteries

To date, the lithium ion battery has become the focus of secondary battery studies. A considerable capacity loss during the first lithiation of its carbon electrode is a severe drawback of this kind of battery. It has been suggested frequently that the capacity loss was caused by the decomposition of the electrolyte on the surface of the carbon electrode. However, the contribution of binder reduction to this capacity loss has never been considered until now. This paper deals with the binder polytetrafluorethylene (PTFE) reduction and finds that it plays an important part in the capacity loss. It is found that (1) the capacity loss increased with increasing PTFE binder content, (2) the X-ray diffraction peaks corresponding to the PTFE, binder became weaker, while more of the lithium was consumed by the carbon electrode, and disappeared when the consumed amount of lithium exceeded the theoretical value of 1070 mAh per gram of PTFE and (3) the height of the high voltage plateau of the electrochemical titration curves was just a function of storage time, and the length of the plateau was a function of the PTFE content.     

A physical model for dimensional reduction and its effects on the observable parameters of the universe

We construct a physical model to study the effects of dimensional reduction that might have taken place during the inflationary phase of the universe. The model we propose is a (1 + D)-dimensional (D > 3), nonsingular, spatially homogeneous and isotropic Friedmann model. We consider dimensional reduction to take place in a stepwise manner and interpret each step as a phase transition. Independent of the details of the process of dimensional reduction, we impose suitable boundary conditions across the transitions and trace the effects of dimensional reduction to the currently observable parameters of the universe. In order to exhibit the cosmological features of the proposed model, we construct a (1 + 4)-dimensional toy model for both closed and open cases of Friedmann geometries. It is shown that in these models the universe makes transition into the lower dimension when the critical length parameter l _4,3, which signals dimensional reduction, reaches the Planck length in D = 3. The numerical models we present in this paper have the capability of making definite predictions about the cosmological parameters of the universe such as the Hubble parameter, age and density.     

Diagnosis of deactivation sources for vanadium catalysts used in SO2 oxidation reaction and optimization of vanadium extraction from deactivated catalysts

Physico-chemical analysis (X-ray, FTIR) and/or methanol oxidation reaction test were performed on fresh and deactivated vanadium catalysts used in H₂SO₄ manufacturing. It allowed the diagnosis of catalyst deactivation sources, as well as the processes of regenerating and recycling the worn out catalyst in converter. One of these processes is hydrometallurgical method. It consists in treating the deactivated catalyst with alkaline or acidic reagents and forming vanadate solution. A simple and non-costly operation of chemical attack permits the extraction of vanadium from silica in deactivated catalyst. The extracted vanadium can be used for the confection of regenerated catalysts or metallic tools. After optimization, this method can be used for industrial application.     

Near-infrared spectroscopy as a rapid tool for water content analysis in the partial oxidation of ethanol

Abstract

The oxidation of ethanol to acetaldehyde was previously investigated in a continuous flow bench scale reactor using a zirconium-oxide-supported vanadium catalyst. Products were analyzed by near-infrared spectroscopy, a fast and accurate tool for the determination of water, ethanol, and acetaldehyde content. Water content was calibrated by Karl Fischer titration while gas chromatography was used to calibrate ethanol and acetaldehyde contents. Near-infrared spectroscopy is a fast, cost-effective method for the determination of water, ethanol, and acetaldehyde products from partial ethanol oxidation.     

The prediction of the vibration reduction index Kij for brick and concrete rigid junctions

The vibration reduction index, K_ij, is related to the transmission of the vibrational power over a junction between structural elements. Two empirical models are proposed to evaluate K_ij, on the basis of statistical evaluations of numerous in-field tests carried out on rigid junctions between floors made by concrete beams and ribbed slab with brick blocks and brickwork walls, a type of junction that is frequently encountered in Southern European and Mediterranean buildings. These models can be applied in order to calculate the sound insulation properties, such as the normalized impact sound pressure level, , and the apparent sound reduction index, R′, of walls and floors in buildings.The first model allows the single number value of the vibration sound reduction index of a junction to be calculated, on the basis of the real properties of the materials that constitute the junction. A new quantity, the “essential” mass per unit area, was introduced to implement the model.The second model provides an estimation of the K_ij as a function of frequency, subdivided between BB-junction, as ribbed slab with brick blocks floor-brick wall, and CB-junction, i.e. concrete beam-brick wall.     

A method for determining the sound reduction index of precast panels based on point mobility measurements

Precast panels are widely used for the construction of large industrial buildings, trade centres and apartment houses. These buildings have to comply with prescribed noise and thermal requirements, so the possibility to accurately estimate the sound reduction index of such panels is of vital importance. The sound reduction index can be determined through measurements carried out in a laboratory or on an already mounted real-scale panel, but both solutions present problems. For example, precast structures consisting of two concrete panels coupled via an interlayer can be very bulky and heavy, and measurements in standard sound transmission laboratories may be impossible to carry out. In some countries, predictions based on theoretical models are accepted in lieu of measurements. Following this approach, the application of simple models, not accounting for the influence of coincidence and of losses, is not sufficient to make acceptable predictions. In this paper, an alternative method to estimate the sound reduction index of precast panels is proposed. Different panels have been considered in the study, each of which has been modelled by a mathematical representation found in the literature. It will be shown that all of these models can be synthesised by a common mathematical formulation, allowing the sound reduction index to be determined from point mobility measurements. The effectiveness of the new method has been investigated by comparing predicted and measured results, obtained in a sound transmission laboratory satisfying existing ISO standards.     

Beam induced reduction of U(VI) during X-ray photoelectron spectroscopy: The utility of the U4f satellite structure for identifying uranium oxidation states in mixed valence uranium oxides

Reduction of U^VI by the beam during X-ray photoelectron spectroscopy (XPS) is a commonly observed phenomenon. This can affect the determination of the U oxidation state, or states, in U oxides (or U compounds in general) and compromise the validity of peak parameters derived from U^VI oxide standards. However, there is little quantitative information on the reduction kinetics and species produced. The objective of this contribution is to investigate and quantify the effects of X-ray beam reduction of U^VI during XPS analysis. Successive U4f XPS spectra were taken over a 26 h period during the X-ray induced reduction of U^VI oxy-hydroxide that was precipitated onto the basal plane of mica. In addition, valence band XPS spectra, including the U5f region, were recorded. Factor analysis identified three dominant and, by definition, linearly independent components. Consequently, we fit the U4f level, including the satellite structure, with three components that represented U^VI, U^V, and U^IV. Peak parameters were remarkably stable and consistent with U^VI, U^V, and U^IV over the entire reduction sequence despite the likely formation of a partially covalent mixed-valence U oxide. Although the satellite features for U^IV and U^V were modified by their bonding environment, they still served well as diagnostic tools for identifying U oxidation states. In particular, the 8 eV satellite appears to be a robust indicator of U^V over a range of bonding environments. This is important because the presence of U^V might not be necessarily obvious in the primary peak envelope if XPS energy resolution is low and/or U^IV-U^V binding energy separations are appreciably less than 1 eV. We also discuss insights obtained from modeling the kinetic data for the time evolution of U^VI, U^V, and U^IV.     

The application of incoherent light for the study of femtosecond-picosecond relaxation in condensed phase

A convenient technique for the ultrashort-relaxation-time measurement using temporally incoherent light instead of short pulses can be applied to the studies of relaxation processes. Theoretical studies on measuring various types of relaxation times by this method are summarized. We have applied this technique to the studies of the electronic dephasing in a polydiacetylene film, the vibrational dephasing in dimethylsulfoxide and the relaxation of optical Kerr effect in CS₂ and nitrobenzene.     

n维相对论粒子的量子态密度及其应用

利用半经典近似的方法,推导出了n维相对论自由粒子量子态密度以及黑体辐射中两类粒子的辐射公式的统一表达式,并且给出了低维情况下的表达式,所得结果与三维空间的预期结果一致.这对于深化低维体系的教学与研究具有重要的意义.     

The approximate ABCD matrix for a parabolic lens of revolution and its application in calculating the coupling efficiency

Using ray optics, we present an explicit formulation of the ABCD matrix for reflection and refraction of light beams at a parabolic interface separating media of different refractive indices under paraxial approximation. Based on the formulated ABCD matrix for refraction by a parabolic lens tip, we present a simple theoretical investigation of the coupling efficiency between a laser diode and a single-mode fiber with a parabolic lens formed on the fiber tip. The results show that this technique is effective and will be of benefit to designing suitable microlenses applying the laser-coupling technique.     

The application of proton nuclear magnetic resonance imaging for the in vivo characterisation of chemically induced renal lesions in rats over a prolonged time study

Renal cortical and medullary spin-lattice (T₁) relaxation times were measured at various time points over a period of 56 days following the administration of a single i.p. injection of 100 mg/kg 2-bromoethanamine hydrobromide (BEA), 200 mg/kg hexachloro-1,3-butadiene (HCBD) or 100 mg/kg puromycin aminonucleoside (PAN) to male Wistar rats. Administration of a single injection of HCBD caused a dramatic, immediate rise in the cortical T₁ values above control values, and these levels remained elevated until, by Day 28 postinjection the levels were back to control values. Administration of BEA also caused an elevation in cortical T₁ values, but in this case these values remained above control values for the rest of the study. The administration of PAN did not produce any significant increases in cortical T₁ values until 14 days postinjection. The elevated T₁ values remained above control values for the rest of the study. These increases observed in cortical T₁ values appeared to be mirrored by decreases in medullary T₁ values. Increases in cortical T₁ values were accompanied by visual changes in the NMR images and enlargement of the kidneys. The histological findings were consistent with the NMR data, confirming that morphologically the tissues did show a full recovery by Day 28 in the HCBD-treated animals. This was not the case following injection of both BEA and PAN, where necrosis was not reversible and there was no recovery of the tissues.     

The use of symmetry in the search for canted ferromagnetism, its application to the molecular magnets Mn[N(CN)2]2 and Fe[N(CN)2]2

Canted ferromagnets present a important class of molecular magnets. In these materials the uncompensated magnetisation, created by the DzyaloshinskyMoriya interaction, has the particular property of being compatible with the symmetry of the underlying antiferromagnetic Hamiltonian. If the ordering transition is continuous, Landau theory and simple symmetry arguments about the crystal structure can be used to determine whether such parasitic ferromagnetism is possible, and therefore to aid the systematic search for new molecular ferromagnets.