988 resultados para Secondary phase


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The work described in this thesis had two objectives. The first objective was to develop a physically based computational model that could be used to predict the electronic conductivity, Seebeck coefficient, and thermal conductivity of Pb1-xSnxTe alloys over the 400 K to 700 K temperature as a function of Sn content and doping level. The second objective was to determine how the secondary phase inclusions observed in Pb1-xSnxTe alloys made by consolidating mechanically alloyed elemental powders impact the ability of the material to harvest waste heat and generate electricity in the 400 K to 700 K temperature range. The motivation for this work was that though the promise of this alloy as an unusually efficient thermoelectric power generator material in the 400 K to 700 K range had been demonstrated in the literature, methods to reproducibly control and subsequently optimize the materials thermoelectric figure of merit remain elusive. Mechanical alloying, though not typically used to fabricate these alloys, is a potential method for cost-effectively engineering these properties. Given that there are deviations from crystalline perfection in mechanically alloyed material such as secondary phase inclusions, the question arises as to whether these defects are detrimental to thermoelectric function or alternatively, whether they enhance thermoelectric function of the alloy. The hypothesis formed at the onset of this work was that the small secondary phase SnO2 inclusions observed to be present in the mechanically alloyed Pb1-xSnxTe would increase the thermoelectric figure of merit of the material over the temperature range of interest. It was proposed that the increase in the figure of merit would arise because the inclusions in the material would not reduce the electrical conductivity to as great an extent as the thermal conductivity. If this were to be true, then the experimentally measured electronic conductivity in mechanically alloyed Pb1-xSnxTe alloys that have these inclusions would not be less than that expected in alloys without these inclusions while the portion of the thermal conductivity that is not due to charge carriers (the lattice thermal conductivity) would be less than what would be expected from alloys that do not have these inclusions. Furthermore, it would be possible to approximate the observed changes in the electrical and thermal transport properties using existing physical models for the scattering of electrons and phonons by small inclusions. The approach taken to investigate this hypothesis was to first experimentally characterize the mobile carrier concentration at room temperature along with the extent and type of secondary phase inclusions present in a series of three mechanically alloyed Pb1-xSnxTe alloys with different Sn content. Second, the physically based computational model was developed. This model was used to determine what the electronic conductivity, Seebeck coefficient, total thermal conductivity, and the portion of the thermal conductivity not due to mobile charge carriers would be in these particular Pb1-xSnxTe alloys if there were to be no secondary phase inclusions. Third, the electronic conductivity, Seebeck coefficient and total thermal conductivity was experimentally measured for these three alloys with inclusions present at elevated temperatures. The model predictions for electrical conductivity and Seebeck coefficient were directly compared to the experimental elevated temperature electrical transport measurements. The computational model was then used to extract the lattice thermal conductivity from the experimentally measured total thermal conductivity. This lattice thermal conductivity was then compared to what would be expected from the alloys in the absence of secondary phase inclusions. Secondary phase inclusions were determined by X-ray diffraction analysis to be present in all three alloys to a varying extent. The inclusions were found not to significantly degrade electrical conductivity at temperatures above ~ 400 K in these alloys, though they do dramatically impact electronic mobility at room temperature. It is shown that, at temperatures above ~ 400 K, electrons are scattered predominantly by optical and acoustical phonons rather than by an alloy scattering mechanism or the inclusions. The experimental electrical conductivity and Seebeck coefficient data at elevated temperatures were found to be within ~ 10 % of what would be expected for material without inclusions. The inclusions were not found to reduce the lattice thermal conductivity at elevated temperatures. The experimentally measured thermal conductivity data was found to be consistent with the lattice thermal conductivity that would arise due to two scattering processes: Phonon phonon scattering (Umklapp scattering) and the scattering of phonons by the disorder induced by the formation of a PbTe-SnTe solid solution (alloy scattering). As opposed to the case in electrical transport, the alloy scattering mechanism in thermal transport is shown to be a significant contributor to the total thermal resistance. An estimation of the extent to which the mean free time between phonon scattering events would be reduced due to the presence of the inclusions is consistent with the above analysis of the experimental data. The first important result of this work was the development of an experimentally validated, physically based computational model that can be used to predict the electronic conductivity, Seebeck coefficient, and thermal conductivity of Pb1-xSnxTe alloys over the 400 K to 700 K temperature as a function of Sn content and doping level. This model will be critical in future work as a tool to first determine what the highest thermoelectric figure of merit one can expect from this alloy system at a given temperature and, second, as a tool to determine the optimum Sn content and doping level to achieve this figure of merit. The second important result of this work is the determination that the secondary phase inclusions that were observed to be present in the Pb1-xSnxTe made by mechanical alloying do not keep the material from having the same electrical and thermal transport that would be expected from “perfect" single crystal material at elevated temperatures. The analytical approach described in this work will be critical in future investigations to predict how changing the size, type, and volume fraction of secondary phase inclusions can be used to impact thermal and electrical transport in this materials system.

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Experience is lacking with mineral scaling and corrosion in enhanced geothermal systems (EGS) in which surface water is circulated through hydraulically stimulated crystalline rocks. As an aid in designing EGS projects we have conducted multicomponent reactive-transport simulations to predict the likely characteristics of scales and corrosion that may form when exploiting heat from granitoid reservoir rocks at ∼200 °C and 5 km depth. The specifications of an EGS project at Basel, Switzerland, are used to constrain the model. The main water–rock reactions in the reservoir during hydraulic stimulation and the subsequent doublet operation were identified in a separate paper (Alt-Epping et al., 2013b). Here we use the computed composition of the reservoir fluid to (1) predict mineral scaling in the injection and production wells, (2) evaluate methods of chemical geothermometry and (3) identify geochemical indicators of incipient corrosion. The envisaged heat extraction scheme ensures that even if the reservoir fluid is in equilibrium with quartz, cooling of the fluid will not induce saturation with respect to amorphous silica, thus eliminating the risk of silica scaling. However, the ascending fluid attains saturation with respect to crystalline aluminosilicates such as albite, microcline and chlorite, and possibly with respect to amorphous aluminosilicates. If no silica-bearing minerals precipitate upon ascent, reservoir temperatures can be predicted by classical formulations of silica geothermometry. In contrast, Na/K concentration ratios in the production fluid reflect steady-state conditions in the reservoir rather than albite–microcline equilibrium. Thus, even though igneous orthoclase is abundant in the reservoir and albite precipitates as a secondary phase, Na/K geothermometers fail to yield accurate temperatures. Anhydrite, which is present in fractures in the Basel reservoir, is predicted to dissolve during operation. This may lead to precipitation of pyrite and, at high exposure of anhydrite to the circulating fluid, of hematite scaling in the geothermal installation. In general, incipient corrosion of the casing can be detected at the production wellhead through an increase in H2(aq) and the enhanced precipitation of Fe-bearing aluminosilicates. The appearance of magnetite in scales indicates high corrosion rates.

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In this paper we describe textural relationships in hydrated upper mantle peridotites emplaced at a nonconstructive ridge segment. Development of serpentinites and partially serpentinized peridotites takes place in four main stages: (1) pervasive serpentinization forming mainly lizardite, (2) a tensional stage forming chrysotile + talc + chlorite, (3) a deformational stage forming antigorite + tremolite, and (4) a late local tensional stage forming another generation of chrysotile veinlets. Mineral chemistry of serpentine pseudomorphs reflects in part primary mineral compositions. Olivine pseudomorphs are typically nickeliferous and depleted in aluminum and chromium. Orthopyroxene pseudomorphs have lower nickel contents and relatively high iron, aluminum, and chromium contents. Clinopyroxene pseudomorphs have very low nickel contents and relatively high aluminum and chromium contents. These chemical patterns in the serpentinites can be used to help discriminate between harzburgitic and lherzolitic protoliths. Oxygen isotopes and mineral parageneses suggest serpentine is derived from circulation of hydrothermal (200?C) fluids through the peridotite body. Crystallization of tremolite, talc, and chlorite may have occurred at temperatures up to 525?C if C02/H20 ratios were less than 0.25. Open fissures developing in aging upper mantle provide paths for important seawater circulation through a thin basaltic carapace down to shallow mantle rocks.

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The environmental impact of systems managing large (kg) tritium amount represents a public scrutiny issue for the next coming fusion facilities as ITER and DEMO. Furthermore, potentially new dose limits imposed by international regulations (ICRP) shall impact next coming devices designs and the overall costs of fusion technology deployment. Refined environmental tritium dose impact assessment schemes are then overwhelming. Detailed assessments can be procured from the knowledge of the real boundary conditions of the primary tritium discharge phase into atmosphere (low levels) and into soils. Lagrangian dispersion models using real-time meteorological and topographic data provide a strong refinement. Advance simulation tools are being developed in this sense. The tool integrates a numerical model output records from European Centre for Medium range Weather Forecast (ECMWF) with a lagrangian atmospheric dispersion model (FLEXPART). The composite model ECMWF/FLEXTRA results can be coupled with tritium dose secondary phase pathway assessment tools. Nominal tritium discharge operational reference and selected incidental ITER-like plant systems tritium form source terms have been assumed. The realtime daily data and mesh-refined records together with lagrangian dispersion model approach provide accurate results for doses to population by inhalation or ingestion in the secondary phase

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CaCu3(Ti4xHfx)O12 ceramics (JC = 0.04, 0.1 and 0.2) were prepared by conventional synthesis (CS) and through reactive sintering (RS), in which synthesis and sintering of the material take place in one single step. The microstructure and the dielectric properties of Hf-doped CCTO (CCTOHf) have been studied by XRD, FE-SEM, AFM, Raman and impedance spectroscopy (IS) in order to correlate the structure, microstructure and the electrical properties. Samples prepared by reactive sintering show slightly higher dielectric constant than those prepared by conventional synthesis in the same way than the pure CCTO. Dielectric constant and dielectric losses decrease slightly increasing Hf content. For CCTOHf ceramics with x> 0.04 for CS and x> 0.1 for RS, a secondary phase HfTi04 appears. As expected, the reactive sintering processing method allows a higher incorporation of Hf in the CCTO lattice than the conventional synthesis one.

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This thesis is concerned with the development of hydrogels that adhere to skin and can be used for topical or trans dermal release of active compounds for therapeutic or cosmetic use. The suitability of a range of monomers and initiator systems for the production of skin adhesive hydro gels by photopolymerisation was explored and an approximate order of monomer reactivity in aqueous solution was determined. Most notably, the increased reactivity of N-vinyl pyrrolidone within an aqueous system, as compared to its low rate of polymerisation in organic solvents, was observed. The efficacy of a series of photoinitiator systems for the preparation of sheet hydrogels was investigated. Supplementary redox and thermal initiators were also examined. The most successful initiator system was found to be Irgacure 184, which is commonly used in commercial moving web production systems that employ photopolymerisation. The influence of ionic and non-ionic monomers, crosslinking systems, water and glycerol on the adhesive and dynamic mechanical behaviour of partially hydrated hydrogel systems was examined. The aim was to manipulate hydrogel behaviour to modify topical and transdermal delivery capability and investigated the possibility of using monomer combinations that would influence the release characteristics of gels by modifying their hydrophobic and ionic nature. The copolymerisation of neutral monomers (N-vinyl pyrrolidone, N,N-dimethyl acrylamide and N-acryloyl morpholine) with ionic monomers (2-acrylamido-2-methylpropane sulphonic acid; sodium salt, and the potassium salt of 3-sulphopropyl acrylate) formed the basis of the study. Release from fully and partially hydrated hydrogels was studied, using model compounds and a non-steroidal anti-inflammatory drug, Ibuprofen. Release followed a common 3-stage kinetic profile that includes an initial burst phase, a secondary phase of approximate first order release and a final stage of infinitesimally slow release such that the compound is effectively retained within the hydrogel. Use of partition coefficients, the pKa of the active and a knowledge of charge-based and polar interactions of polymer and drug were complementary in interpreting experimental results. In summary, drug ionisation, hydrogel composition and external release medium characteristics interact to influence release behaviour. The information generated provides the basis for the optimal design of hydrogels for specific dermal release applications and some understanding of the limitations of these systems for controlled release applications.

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The comprehensive study on the coupling of magnetism, electrical polarization and the crystalline lattice with the off-stoichiometric effects in self-doped multiferroic hexagonal h-LuMnxO3±δ (0.92≤x≤1.12) ceramic oxides was carried out for the PhD work. There is a complex coupling of the three ferroic degrees. The cancelation of the magnetic moments of ions in the antiferromagnetic order, electric polarization with specific vortex/antivortex topology and lattice properties have pushed researchers to find out ways to disclose the underlying physics and chemistry of magneto-electric and magneto-elastic couplings of h-RMnO3 multiferroic materials. In this research work, self-doping of Lu-sites or Mn-sites of h-LuMnxO3±δ ceramics prepared via solid state route was done to pave a way for deeper understanding of the antiferromagnetic transition, the weak ferromagnetism often reported in the same crystalline lattices and the ferroelectric properties coupled to the imposed lattice changes. Accordingly to the aim of the PhD thesis, the objectives set for the sintering study in the first chapter on experimental results were two. First, study of sintering off-stoichiometric samples within conditions reported in the bibliography and also extracted from the phase diagrams of the LuMnxO3±δ, with a multiple firings ending with a last high temperature step at 1300ºC for 24 hours. Second, explore longer annealing times of up to 240 hours at the fixed temperature of 1300 ºC in a search for improving the properties of the solid solution under study. All series of LuMnxO3±δ ceramics for each annealing time were characterized to tentatively build a framework enabling comparison of measured properties with results of others available in literature. XRD and Rietveld refinement of data give the evolution the lattice parameters as a function to x. Shrinkage of the lattice parameters with increasing x values was observed, the stability limit of the solid solution being determined by analysis of lattice parameters. The evolution of grain size and presence of secondary phases have been investigated by means of TEM, SEM, EDS and EBSD techniques. The dependencies of grain growth and regression of secondary phases on composition x and time were further characterized. Magnetic susceptibility of samples and magnetic irreversibility were extensively examined in the present work. The dependency of magnetic susceptibility, Neel ordering transition and important magnetic parameters are determined and compared to observation in other multiferroics in the following chapter of the thesis. As a tool of high sensitivity to detect minor traces of the secondary phase hausmannite, magnetic measurements are suggested for cross-checking of phase diagrams. Difficulty of previous studies on interpreting the magnetic anomaly below 43 K in h-RMnO3 oxides was discussed and assigned to the Mn3O4 phase, with supported of the electron microscopy. Magneto-electric coupling where AFM ordering is coupled to dielectric polarization is investigated as a function of x and of sintering condition via frequency and temperature dependent complex dielectric constant measurements in the final chapter of the thesis. Within the limits of solid solubility, the crystalline lattice of off-stoichiometric ceramics was shown to preserve the magneto-electric coupling at TN. It represents the first research work on magneto-electric coupling modified by vacancy doping to author’s knowledge. Studied lattices would reveal distortions at the atomic scale imposed by local changes of x dependent on sintering conditions which were widely inspected by using TEM/STEM methods, complemented with EDS and EELS spectroscopy all together to provide comprehensive information on cross coupling of distortions, inhomogeneity and electronic structure assembled and discussed in a specific chapter. Internal interfaces inside crystalline grains were examined. Qualitative explanations of the measured magnetic and ferroelectric properties were established in relation to observed nanoscale features of h-LuMnxO3±δ ceramics. Ferroelectric domains and topological defects are displayed both in TEM and AFM/PFM images, the later technique being used to look at size, distribution and switching of ferroelectric domains influenced by vacancy doping at the micron scale bridging to complementary TEM studies on the atomic structure of ferroelectric domains. In support to experimental study, DFT simulations using Wien2K code have been carried out in order to interpret the results of EELS spectra of O K-edge and to obtain information on the cation hybridization to oxygen ions. The L3,2 edges of Mn is used to access the oxidation state of the Mn ions inside crystalline grains. In addition, rehybridization driven ferroelectricity is also evaluated by comparing the partial density of states of the orbitals of all ions of the samples, also the polarization was calculated and correlated to the off-stoichiometric effect.

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Due to their intriguing dielectric, pyroelectric, elasto-electric, or opto-electric properties, oxide ferroelectrics are vital candidates for the fabrication of most electronics. However, these extraordinary properties exist mainly in the temperature regime around the ferroelectric phase transition, which is usually several hundreds of K away from room temperature. Therefore, the manipulation of oxide ferroelectrics, especially moving the ferroelectric transition towards room temperature, is of great interest for application and also basic research. In this thesis, we demonstrate this using examples of NaNbO3 films. We show that the transition temperature of these films can be modified via plastic strain caused by epitaxial film growth on a structurally mismatched substrate, and this strain can be fixed by controlling the stoichiometry. The structural and electronic properties of Na1+xNbO3+δ thin films are carefully examined by among others XRD (e.g. RSM) and TEM and cryoelectronic measurements. Especially the electronic features are carefully analyzed via specially developed interdigitated electrodes in combination with integrated temperature sensor and heater. The electronic data are interpreted using existing as well as novel theories and models, they are proved to be closely correlated to the structural characteristics. The major results are: -Na1+xNbO3+δ thin films can be grown epitaxially on (110)NdGaO3 with a thickness up to 140 nm (thicker films have not been studied). Plastic relaxation of the compressive strain sets in when the thickness of the film exceeds approximately 10 – 15 nm. Films with excess Na are mainly composed of NaNbO3 with minor contribution of Na3NbO4. The latter phase seems to form nanoprecipitates that are homogeneously distributed in the NaNbO3 film which helps to stabilize the film and reduce the relaxation of the strain. -For the nominally stoichiometric films, the compressive strain leads to a broad and frequency-dispersive phase transition at lower temperature (125 – 147 K). This could be either a new transition or a shift in temperature of a known transition. Considering the broadness and frequency dispersion of the transition, this is actually a transition from the dielectric state at high temperature to a relaxor-type ferroelectric state at low temperature. The latter is based on the formation of polar nano-regions (PNRs). Using the electric field dependence of the freezing temperature, allows a direct estimation of the volume (70 to 270 nm3) and diameter (5.2 to 8 nm, spherical approximation) of the PNRs. The values confirm with literature values which were measured by other technologies. -In case of the off-stoichiometric samples, we observe again the classical ferroelectric behavior. However, the thermally hysteretic phase transition which is observed around 620 – 660 K for unstrained material is shifted to room temperature due to the compressive strain. Beside to the temperature shift, the temperature dependence of the permittivity is nearly identical for strained and unstrained materials. -The last but not least, in all cases, a significant anisotropy in the electronic and structural properties is observed which arises automatically from the anisotropic strain caused by the orthorhombic structure of the substrate. However, this anisotropy cannot be explained by the classical model which tries to fit an orthorhombic film onto an orthorhombic substrate. A novel “square lattice” model in which the films adapt a “square” shaped lattice in the plane of the film during the epitaxial growth at elevated temperature (~1000 K) nicely explains the experimental results. In this thesis we sketch a way to manipulate the ferroelectricity of NaNbO3 films via strain and stoichiometry. The results indicate that compressive strain which is generated by the epitaxial growth of the film on mismatched substrate is able to reduce the ferroelectric transition temperature or induce a phase transition at low temperature. Moreover, by adding Na in the NaNbO3 film a secondary phase Na3NbO4 is formed which seems to stabilize the main phase NaNbO3 and the strain and, thus, is able to engineer the ferroelectric behavior from the expected classical ferroelectric for perfect stoichiometry to relaxor-type ferroelectric for slightly off-stoichiometry, back to classical ferroelectric for larger off-stoichiometry. Both strain and stoichiometry are proven as perfect methods to optimize the ferroelectric properties of oxide films.

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Gas-phase ozonolysis of alpha-pinene was studied in static chamber experiments under 'OH-free' conditions. A range of multifunctional products-in particular low-volatility carboxylic acids-were identified in the condensed phase using gas chromatography coupled to mass spectrometry after derivatisation. The dependence of product yields on reaction conditions (humidity, choice of OH radical scavengers, added Criegee intermediate scavengers, NO2 etc.) was investigated to probe the mechanisms of formation of these products; additional information was obtained by studying the ozonolysis of an enal and an enone derived from alpha-pinene. On the basis of experimental findings, previously suggested mechanisms were evaluated and detailed gas-phase mechanisms were developed to explain the observed product formation. Atmospheric implications of this work are discussed.

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Duplex and superduplex stainless steels are class of materials of a high importance for engineering purposes, since they have good mechanical properties combination and also are very resistant to corrosion. It is known as well that the chemical composition of such steels is very important to maintain some desired properties. In the past years, some works have reported that γ 2 precipitation improves the toughness of such steels, and its quantification may reveals some important information about steel quality. Thus, we propose in this work the automatic segmentation of γ 2 precipitation using two pattern recognition techniques: Optimum-Path Forest (OPF) and a Bayesian classifier. To the best of our knowledge, this if the first time that machine learning techniques are applied into this area. The experimental results showed that both techniques achieved similar and good recognition rates. © 2012 Taylor & Francis Group.

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This secondary analysis was performed to identify predictive factors for severe late radiotherapy (RT)-related toxicity after treatment with hyperfractionated RT +/- concomitant cisplatin in locally advanced head and neck cancer.

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OBJECTIVES To analyze the prognostic value of clinical tumor response during chemoradiation for locally advanced head and neck cancer. PATIENTS AND METHODS The locoregional response at 50.4Gy was assessed by physical examination (PE) in patients treated within the randomized trial SAKK 10/94 using hyperfractionated radiotherapy (RT), median total dose 74.4Gy with or without cisplatin 20mg/m(2) chemotherapy on 5 consecutive days during weeks 1 and 5 or 6 of RT. Response was classified as a complete response (CR), complete response with uncertainty (Cru), partial response (PR), stable disease (SD), or progressive disease (PD). The primary endpoint was time to treatment failure (TTF) due to any cause. Secondary endpoints included locoregional-recurrence-free survival (LRRFS), distant metastasis-free survival (DMFS) and overall survival (OS). Univariate and multivariate Cox proportional hazards (PH) models were applied to analyze the associations between survival endpoints and clinical tumor response. RESULTS A total of 136, 131 and 97 patients were evaluable for response at the primary tumor, lymph nodes and both sites combined, respectively. At 50.4Gy 57/136 (42%), 46/131 (35%) and 21/97 (22%) patients had a good response (CR/Cru vs. PR/SD) at the primary tumor, the lymph nodes, and both sites combined, respectively. The median follow-up times were 11.4, 9.6 and 11.4years for the three groups. Good responses were all significantly associated with improved TTF, LRRFS, DMFS and OS in univariate analysis whereas good response at the primary tumor and lymph nodes remained significantly associated with TTF and OS after multivariate Cox PH models. CONCLUSIONS Locoregional response at 50.4Gy was identified as predictor of oncologic outcome. PE during treatment should not be underestimated in clinical practice.

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Based on common aspects of recent models of career decision-making (CDM) a sixphase model of CDM for secondary students is presented and empirically evaluated. The study tested the hypothesis that students who are in later phases possess more career choice readiness and consider different numbers of career alternatives. 266 Swiss secondary students completed measures tapping phase of CDM, career choice readiness, and number of considered career options. Career choice readiness showed an increase with phase of CDM. Later phases were generally associated with a larger increase in career choice readiness. Number of considered career options showed a curve-linear development with fewer options considered at the beginning and at the end of the process. Male students showed a larger variability in their distribution among the process with more male than female students in the first and last phase of the process. Implications for theory and practice are presented.

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BACKGROUND To analyze the impact of weight loss before and during chemoradiation on survival outcomes in patients with locally advanced head and neck cancer. METHODS From 07/1994-07/2000 a total of 224 patients with squamous cell carcinoma of the head and neck were randomized to either hyperfractionated radiation therapy alone or the same radiation therapy combined with two cycles of concomitant cisplatin. The primary endpoint was time to any treatment failure (TTF); secondary endpoints were locoregional recurrence-free survival (LRRFS), distant metastasis-free survival (DMFS) and overall survival (OS). Patient weight was measured 6 months before treatment, at treatment start and treatment end. RESULTS The proportion of patients with >5% weight loss was 32% before, and 51% during treatment, and the proportion of patients with >10% weight loss was 12% before, and 17% during treatment. After a median follow-up of 9.5 years (range, 0.1 - 15.4 years) weight loss before treatment was associated with decreased TTF, LRRFS, DMFS, cancer specific survival and OS in a multivariable analysis. However, weight loss during treatment was not associated with survival outcomes. CONCLUSIONS Weight loss before and during chemoradiation was commonly observed. Weight loss before but not during treatment was associated with worse survival.

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