27 resultados para theoretical investigation


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The formation of nitrogen oxides (NOx) during a combustion process is difficult to avoid because of the large exotherm and the consequent problem of avoiding local high-temperature spikes. Consequently, for many applications, such as for automotive power generation, there will be a continuing need to use catalytic after-treatment to reduce harmful emissions. The investigation of the mechanisms of the key catalytic reactions in environmental catalysis can provide an insight into the action of the catalyst, and time-resolved methods offer a powerful means to study these processes under realistic conditions. The use of Temporal Analysis of Products (TAP) and Steady State Isotopic Transient Kinetic Analysis (SSITKA) methods to investigate the reduction of NOx under various experimental conditions is described. From a detailed analysis of the SSITKA profiles, it is shown that at low temperatures the mechanism for the formation of N-2 and N2O from NO may differ from the conventional high-temperature mechanism. This is supported by density functional theory calculations, which show that the barrier to the formation of N2O from the reaction of N(ads) and NO(ads) may be too high to allow this process to occur at low temperatures. The alternative reaction of NO(ads) + NO(ads) = N2O(g) + O(ads) is shown to be much more favorable and is consistent with the SSITKA analysis. The remarkable effect of hydrogen as a reductant at low temperatures is described, and alternative interpretations of the role of hydrogen are discussed.

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In the last 50 years, many bridges have been built as composite structures with decks of reinforced concrete that are supported by longitudinal steel beams. The presence of the longitudinal steel beams and the unloaded area of concrete slab cause the loaded deck slabs to be restrained against lateral expansion. As a result, a compressive membrane thrust is developed. In experimental tests, the authors built a series of one-third scale steel-concrete composite bridge models with several varying structural parameters, including concrete compressive strength, reinforcement percentage, and the size of steel supporting beams. After comparing the results of different models, the influence of these structural parameters on the amount of compressive membrane action in the deck slab was evaluated. Furthermore, the improvement of an existing theoretical model provided accurate predictions for the loading-carrying capacities.

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Drawing upon interviews with procedural actants from Public Inquiry and Examination in Public fora, I draw upon relevant theoretical frameworks to evaluate modes of discourse in inquisitorial planning practice. In the investigation, which is based primarily upon an empirical study, I focus upon the role of evidence, the selection and handling of multiple knowledges, the behaviour of participants, and the methodology underpinning the process. It is established that such arenas can be effective mechanisms for testing complex evidence; and suggestions are made for improved practice, procedure, and future research. I conclude by raising serious ethical questions concerning participant behaviour, particularly on the part of advocates and especially chartered town planners.

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The effects of four process factors: pH, emulsifier (gelatin) concentration, mixing and batch, on the % w/w entrapment of propranolol hydrochloride in ethylcellulose microcapsules prepared by the solvent evaporation process were examined using a factorial design. In this design the minimum % w/w entrapments of propranolol hydrochloride were observed whenever the external aqueous phase contained 1.5% w/v gelatin at pH 6.0 (0.71-0.91% w/w) whereas maximum entrapments occurred whenever the external aqueous phase was composed of 0.5% w/v gelatin at pH 9.0,(8.9-9.1% w/w). The theoretical maximum loading was 50% w/w. Statistical evaluation of the results by analysis of variance showed that emulsifer (gelatin) concentration and pH, but not mixing and batch significantly affected entrapment. An interaction between pH and gelatin concentration was observed in the factorial design which was accredited to the greater effect of gelatin concentration on % w/w entrapment at pH 9.0 than at pH 6.0. Maximum theoretical entrapment was achieved by increasing the pH of the external phase to 12.0. Marked increases in drug entrapment were observed whenever the pH of the external phase exceeded the pK(2) of propranolol hydrochloride. It was concluded that pH, and hence ionisation, was the greatest determinant of entrapment of propranolol hydrochloride into microcapsules prepared by the solvent evaporation process.

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We present a study on the transport properties through conductivity (s), viscosity (?), and self-diffusion coefficient (D) measurements of two pure protic ionic liquids—pyrrolidinium hydrogen sulfate, [Pyrr][HSO4], and pyrrolidinium trifluoroacetate, [Pyrr][CF3COO]—and their mixtures with water over the whole composition range at 298.15 K and atmospheric pressure. Based on these experimental results, transport mobilities of ions have been then investigated in each case through the Stokes–Einstein equation. From this, the proton conduction in these PILs follows a combination of Grotthuss and vehicle-type mechanisms, which depends also on the water composition in solution. In each case, the displacement of the NMR peak attributed to the labile proton on the pyrrolidinium cation with the PILs concentration in aqueous solution indicates that this proton is located between the cation and the anion for a water weight fraction lower than 8%. In other words, for such compositions, it appears that this labile proton is not solvated by water molecules. However, for higher water content, the labile protons are in solution as H3O+. This water weight fraction appears to be the solvation limit of the H+ ions by water molecules in these two PILs solutions. However, [Pyrr][HSO4] and [Pyrr][CF3COO] PILs present opposed comportment in aqueous solution. In the case of [Pyrr][CF3COO], ?, s, D, and the attractive potential, Epot, between ions indicate clearly that the diffusion of each ion is similar. In other words, these ions are tightly bound together as ion pairs, reflecting in fact the importance of the hydrophobicity of the trifluoroacetate anion, whereas, in the case of the [Pyrr][HSO4], the strong H-bond between the HSO4– anion and water promotes a drastic change in the viscosity of the aqueous solution, as well as on the conductivity which is up to 187 mS·cm–1 for water weight fraction close to 60% at 298 K.

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Objective: The aim of this study was to investigate the effect of pre-treatment verification imaging with megavoltage (MV) X-rays on cancer and normal cell survival in vitro and to compare the findings with theoretically modelled data. Since the dose received from pre-treatment imaging can be significant, incorporation of this dose at the planning stage of treatment has been suggested.

Methods: The impact of imaging dose incorporation on cell survival was investigated by clonogenic assay, irradiating DU-145 prostate cancer, H460 non-small cell lung cancer and AGO-1522b normal tissue fibroblast cells. Clinically relevant imaging-to-treatment times of 7.5 minutes and 15 minutes were chosen for this study. The theoretical magnitude of the loss of radiobiological efficacy due to sublethal damage repair was investigated using the Lea-Catcheside dose protraction factor model.

Results: For the cell lines investigated, the experimental data showed that imaging dose incorporation had no significant impact upon cell survival. These findings were in close agreement with the theoretical results.

Conclusions: For the conditions investigated, the results suggest that allowance for the imaging dose at the planning stage of treatment should not adversely affect treatment efficacy.

Advances in Knowledge: There is a paucity of data in the literature on imaging effects in radiotherapy. This paper presents a systematic study of imaging dose effects on cancer and normal cell survival, providing both theoretical and experimental evidence for clinically relevant imaging doses and imaging-to-treatment times. The data provide a firm foundation for further study into this highly relevant area of research.

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This paper presents the results of an experimental investigation, carried out in order to verify the feasibility of a ‘drive-by’ approach which uses a vehicle instrumented with accelerometers to detect and locate damage in a bridge. In theoretical simulations, a simplified vehicle-bridge interaction model is used to investigate the effectiveness of the approach in detecting damage in a bridge from vehicle accelerations. For this purpose, the accelerations are processed using a continuous wavelet transform and damage indicators are evaluated and compared. Alternative statistical pattern recognition techniques are incorporated to allow for repeated vehicle passes. Parameters such as vehicle speed, damage level, location and road roughness are varied in simulations to investigate the effect. A scaled laboratory experiment is carried out to assess the effectiveness of the approach in a more realistic environment, considering a number of bridge damage scenarios.

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Background: The Prenatal Distress Questionnaire (PDQ) is a short measure designed to assess specific worries and concerns related to pregnancy. The aim of this study was to confirm the factor structure of the PDQ in a group of pregnant women with a small for gestational age infant (< 10th centile). Methods: The first PDQ assessment for each of 337 pregnant women participating in the Prospective Observational Trial to Optimise paediatric health (PORTO) study was analysed. All women enrolled in the study were identified as having a small for gestational age foetus (< 10th centile), thus representing an 'elevated risk' group. Data were analysed using confirmatory factor analysis (CFA). Three models of the PDQ were evaluated and compared in the current study: a theoretical uni-dimensional measurement model, a bi-dimensional model, and a three-factor model solution. Results: The three-factor model offered the best fit to the data while maintaining sound theoretical grounds(χ2 (51df) = 128.52; CFI = 0.97; TLI = 0.96; RMSEA = 0.07). Factor 1 contained items reflecting concerns about birth and the baby, factor 2 concerns about physical symptoms and body image and factor 3 concerns about emotions and relationships. Conclusions: CFA confirmed that the three-factor model provided the best fit, with the items in each factor reflecting the findings of an earlier exploratory data analysis. © 2013 Society for Reproductive and Infant Psychology.

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In this paper, niobium doping is evaluated as a means of enhancing the electrochemical performance of a Sr2Fe1.5Mo0.5O6-δ (SFM) perovskite structure cathode material for intermediate temperature solid oxide fuel cells (IT-SOFCs) applications. As the radius of Nb approximates that of Mo and exhibits +4/+5 mixed valences, its substitution is expected to improve material performance. A series of Sr2Fe1.5Mo0.5-xNbxO6-δ (x = 0.05, 0.10, 0.15, 0.20) cathode materials are prepared and the phase structure, chemical compatibility, microstructure, electrical conductivity, polarization resistance and power generation are systematically characterized. Among the series of samples, Sr2Fe1.5Mo0.4Nb0.10O6-δ (SFMNb0.10) exhibits the highest conductivity value of 30 S cm-1 at 550°C, and the lowest area specific resistance of 0.068 Ω cm2 at 800°C. Furthermore, an anode-supported single cell incorporating a SFMNb0.10 cathode presents a maximum power density of 1102 mW cm-2 at 800°C. Furthermore no obvious performance degradation is observed over 15 h at 750°C with wet H2(3% H2O) as fuel and ambient air as the oxidant. These results demonstrate that SFMNb shows great promise as a novel cathode material for IT-SOFCs.

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Kinetic demixing and decomposition were studied on three La0.6Sr0.4Co0.2Fe0.8O3- δ oxygen-separation hollow fibre membrane modules, which were operated under a 0.21/0.009bar oxygen partial pressure difference at 950°C for 1128, 3672 and 5512h, respectively. The post-operation membranes were characterized by Secondary Ion Mass Spectrometry, Scanning Electronic Microscope, Energy Dispersive Spectrum and X-ray Diffraction. The occurrence of kinetic demixing and decomposition was confirmed through the microstructural evolution of the membranes. Secondary-phase grains were found on the air-side surface of the membranes after the long-term operation and Co and Fe enrichment as well as La depletion was found on the surface and in the bulk at the air side. Cation diffusivities were found to be in the order Co>Fe>Sr>La. Kinetic demixing and decomposition rates of the membranes at the air side were found to be self-accelerating with time; the role of A-site deficiency in the perovskite lattice in the bulk near the air side surface is implicated in the mechanism. The oxygen permeability was not affected by the kinetic demixing and decomposition of the material during long-term operation (up to 5512h), however, we may expect permeability to be affected by secondary phase formation on the air-side surface at even longer operational times. © 2010 Elsevier B.V.

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A selected ion flow tube study of the reactions of a series of gas-phase atomic cations (S+, Xe+, O+, Kr+, N+, Ar+ and Ne+) and molecular ions (SF n+ (n = 1-5), CFn+ (n = 1-3), CF2Cl+, H3O+, NO+, N 2O+, CO2+, CO+, and N2+) spanning a large range of recombination energies (6.3-21.6 eV), with acetone, 1,1,1-trifluoroacetone, and hexafluoroacetone has been undertaken with the objective of exploring the nature of the reaction ion chemistry as the methyl groups in acetone are substituted for CF3. The reaction rate coefficients and product ion branching ratios for all 66 reactions, measured at 298 K, are reported. The experimental reaction rate coefficients are compared to theoretically calculated collisional values. Several distinct reaction processes were observed among the large number of reactions studied, including charge transfer (non-dissociative and dissociative), abstraction, ion-molecule associations and, in the case of the reactions involving the reagent ion H3O+, proton transfer. 

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Graphene with heteroatom doping has found increasing applications in a broad range of catalytic reactions. However, the doping effects accounting for the enhanced catalytic activity still remain elusive. In this work, taking the triiodide electroreduction reaction as an example, we study systematically the intrinsic activity of graphene and explore the origin of doping-induced activity variation using first-principles calculations, in which two typical N and S dopants are tested. The most common graphene structures, basal plane, armchair edge, and zigzag edge, are considered, and it is found that the former two structures show a weak adsorption ability for the iodine atom (the key intermediate in the triiodide electroreduction reaction), corresponding to a low catalytic activity. Doping either N or S can strengthen the adsorption and thus increase the activity, and the codoping of N and S (NS-G) exhibits a synergistic effect. A detailed investigation into the whole process of the triiodide electroreduction reaction at the CH3CN/NS-G interface is also carried out to verify these activity trends. It is found that the zigzag edges which contain spin electrons show a relatively stronger adsorption strength compared with the basal plane and armchair edge, and initial doping would result in the spin disappearance that evidently weakens the adsorption; with the disappearance of spin, however, further doping can increase the adsorption again, suggesting that the spin electrons may play a preliminary role in affecting the intrinsic activity of graphene. We also analyzed extensively the origin of doping-induced adsorption enhancement of graphene in the absence of spin; it can be rationalized from the electronic and geometric factors. Specifically, N doping can result in a more delocalized “electron-donating area” to enhance I adsorption, while S doping provides a localized structural distortion, which activates the nearest sp2-C into coordinatively unsaturated sp3-C. These results explain well the improved activity of the doping and the synergistic effect of the codoping. The understandings are generalized to provide insight into the enhanced activity of the oxygen reduction reaction on heteroatom doped graphene. This work may be of importance toward the design of high-activity graphene based material.