Different sample preparation steps prior to a detection method are often essential in analytical chemistry. In this thesis, both static extractions and on-line coupled solid-phase extractions have been studied in combination with different detection techniques. Aspects of performing sample preparations in miniaturized analytical devices and the development of poly(dimethylsiloxane) (PDMS) microchips are discussed. Polypyrrole was also evaluated as an electrochemically controllable stationary phase for solid-phase microextraction (SPME) and solid-phase extraction (SPE). The first part of this thesis describes the extraction of an organic compound from a very complex solid matrix utilizing the pressurized-fluid extraction (PFE) technique. The presented results show that PFE is easily optimized and enables rapid extractions and extracts relatively free from interferences. An integrated three-electrode device, which enabled electrochemical (EC) SPME under potential control, was developed. With this device, both anions and cations could be extracted employing two types of polypyrrole films. Planar micro band electrodes positioned at the end of a capillary were also used to electrochemically extract and detect anions in a miniaturized flow system. Different analyte concentrations and preconcentration times were examined, and good linear correlations were found between the extraction time and the detection response. The on-line coupling of a thin layer EC cell, with a polypyrrole coated working electrode, to different mass spectrometric (MS) techniques is also described and evaluated. The results show that EC-SPE, employing polypyrrole as stationary phase, can be used as a preconcentration step prior to detection. In addition, this thesis describes the development and on-line coupling of a microelectrode array equipped PDMS microchip with an integrated graphite electrospray emitter to electrospray ionization (ESI) MS. The system enabled short transfer times and an EC conversion efficiency of 30% at a flow rate of 0.5 μL/min. The on-line EC/ESI-MS experiments were significantly simplified using a wireless Bluetooth battery-powered EC instrument.

This thesis covers a wide range of analytical method development for lipid analysis in complex biological samples; from sample preparation using pressurized fluid extraction (PFE) and separation with reversed phase capillary liquid chromatography (RP-LC) to detection by electrospray ionization mass spectrometry (ESI/MS) and tandem MS. The requirements for fast, reliable and selective extraction methods with minimal usage of solvents have accelerated the development of new extraction techniques. PFE is one of the new automated, fast and efficient liquid extraction techniques which use elevated temperature and pressure with standard liquid solvents. In this thesis the reliability and efficiency of the PFE technique was investigated for the extraction of total lipid content from cod, herring muscle and human brain tissue as well as for pesticides from fatty foodstuffs. Improved or comparable efficiencies were achieved with reduced time and solvent consumption as compared to traditional methods. A RP-LC coupled online to ESI/MS for the analysis of phosphatidylcholine (PC) and sphingomyelin (SM) molecular species was developed and used for the analysis of brain lipids from eight groups of mice treated with vehicle and various neuroleptics. The effect of postnatal iron administration in lipid composition and behavior was investigated. Whether or not these effects could be altered by subchronic administration of the neuroleptics (clozapine and haloperidol) were examined. The results support the hypothesis that an association between psychiatric disorders, behavior abnormalities and lipid membrane constitution in the brain exists. Finally, a tandem MS precursor ion scan was used to analyze the developmental profile of brain sulfatide accumulation in arylsulfatase A (ASA) deficient (ASA -/-) as compared to wild type control (ASA +/+) mice. The ASA -/- mice were developed as a model of the monogenic disease metachromatic leukodystrophy with an established deficiency of the lysosomal enzyme ASA. The results showed that an alteration in the composition of sulfatide molecular species was observed between the ASA -/- and ASA +/+ mice. This thesis shows that modern analytical methods can provide new insights in the extraction and analysis of lipids from complex biological samples.

This thesis analyses two strategies for decreasing anthropogenic carbon dioxide (CO2) emissions: to capture and store CO2, and to increase the use of biomass. First, two concepts for CO2 capture with low capture penalties are evaluated. The concepts are an integrated gasification combined cycle where the oxygen is supplied by a membrane reactor, and a hybrid cycle where the CO2 is captured at elevated pressure. Although the cycles have comparatively high efficiencies and low penalties, they illustrate the inevitable fact that capturing CO2 will always induce significant efficiency penalties. Other strategies are also needed if CO2 emissions are to be forcefully decreased. An alternative is increased use of biomass, which partially could be used for production of motor fuels (biofuels). This work examines arguments for directing biomass to the transport sector, analyses how biofuels (and also some other means) may be used to reduce CO2 emissions and increase security of motor fuel supply. The thesis also explores the possibility of reducing CO2 emissions by comparatively easy and cost-efficient CO2 capture from concentrated CO2 streams available in some types of biofuel plants. Many conclusions of the thesis could be associated with either of three meanings of the word sense: First, there is reason in biofuel production – since it e.g. reduces oil dependence. From a climate change mitigation perspective, however, motor fuel production is often a CO2-inefficient use of biomass, but the thesis explores how biofuels’ climate change mitigation effects may be increased by introducing low-cost CO2 capture. Second, the Swedish promotion of biofuels appears to have been governed more by a feeling for attaining other goals than striving for curbing climate change. Third, it seems to have been the prevalent opinion among politicians that the advantages of biofuels – among them their climate change mitigation benefits – are far greater than the disadvantages and that they should be promoted. Another conclusion of the thesis is that biofuels alone are not enough to drastically decrease transport CO2 emissions; a variety of measures are needed such as fuels from renewable electricity and improvements of vehicle fuel economy. / QC 20100823

The challenge for the future was defined by the Brundtland Commission (1987) and by the Rio Declaration (1992), in which the fundamental principles for achieving a sustainable development were provided. Sustainable chemistry can be defined as the contribution of chemistry to the implementation of the Rio Declaration. This thesis shows how Pressurized Fluid Extraction (PFE) can be utilized in chemical analysis, and how this correlates to Green Chemistry. The reliability and efficiency of the PFE technique was investigated for a variety of analytes and matrices. Applications discussed include: the extraction of the antioxidant Irganox 1076 from linear low density polyethylene, mobile forms of phosphorus in lake sediment, chlorinated paraffins from source-separated household waste, general analytical method for pesticide residues in rape seed, total lipid content in cod muscle, and squalene in olive biomass. Improved or comparable extraction yields were achieved with reduced time and solvent consumption. The decrease in use of organic solvents was 50-90%, resulting in minimal volatile organic compounds emissions and less health-work problem. Due to higher extraction temperatures and more efficient extractions, the selection of solvent is not as important as at lower temperatures, which makes it possible to choose less costly, more environmentally and health beneficial solvents. In general, extraction times are reduced to minutes compared to several hours. As a result of the very short extraction times, the amount of co-extracted material is relatively low, resulting in fewer clean-up step and much shorter analysis time. Selective extractions could be obtained by varying the solvent or solvent mixture and/or using adsorbents. In this thesis, the PFE technique was compared to the twelve principles of Green Chemistry, and it was shown that it follows several of the principles, thus giving a major contribution to sustainable chemistry.

Axial offset anomaly (AOA) in pressurized water reactors (PWR) refers to deviation of the measured neutron flux in the top half of the core from the predicted values. Among other difficulties, AOA reduces the shutdown margin, and may force the plant to reduce power output. AOA is believed to be caused by three related phenomena occurring in the core while operating at full power: sub-cooled nucleate boiling concentrated mainly in the upper half of the core, corrosion product deposition on the cladding surface (crud), and the deposition of boron within the porous crud layer in regions of vigorous sub-cooled boiling. This study replicates the conditions within the PWR primary coolant; specifically, the temperature, pressure, peak surface heat flux, coolant velocity and water chemistry are simulated in order to produce prototypical crud on an electrically heated Zircaloy-4 test element. At the conclusion of each test run, the heated Zircaloy-4 test element is rapidly isolated from the coolant in order to trap any soluble boron species that may be present in the crud layer. The results of this investigation indicate that prototypical crud with significant boron deposition can be produced. The deposited boron compound has been determined to be lithium tetraborate (Li2B4O7). Comparative experiments have been run to determine the effect of coolant pH, concentration and type of additives, and duration of exposure on the thickness of the crud deposit. The data obtained in this investigation can be used to validate mechanistic models for crud deposition and AOA in pressurized water reactors.

Filtration of grape juice was investigated. Effects of process parameters of filtration were examined. The usage of precoating material and filter aid were found to be necessary to prolong the filter life. Filter cake was found to be incompressible with the effect of increasing pressure. Increase in temperature caused increase in flow rate due to the reduction in viscosity. The influences of depectinization and clarification on filtration process were also examined. Depectinization and clarification decreased the resistance and increased the flow rate. Improvement in the quality of the grape juice was observed when these pretreatments were employed. The effects of temperature and soluble solid concentration on physical properties of clarified fruit juices were investigated. High temperature and soluble solid content dependencies of density, viscosity and heat capacity were detected. Experimental data were fitted as a function of temperature and soluble solid content. Models being valid for studied clarified fruit juices were achieved for density and viscosity with the regression coefficients (R2) higher than 0.90. Optimization of the solid-liquid extraction conditions for trans-resveratrol, trans-&amp / #949 / -viniferin, ferulic acid, and total phenolics from milled grape canes has been investigated. Temperature and ethanol concentration were found to be major process variables for all responses. Maximum yields of trans-resveratrol, trans-&amp / #949 / -viniferin, ferulic acid, and total phenolics were predicted as 4.25 mg/g dw, 2.03 mg/g dw, 1.05 mg/g dw, and 9.28 mg/g dw, respectively. Optimization of extraction conditions for antioxidant activity of grape cane extracts measured by the Trolox equivalent antioxidant capacity (TEAC) and the oxygen radical absorbance capacity (ORACFL) assays was carried out using solid-liquid extraction and response surface methodology. Ethanol concentration and temperature employed for the extraction of antioxidant agents from grape cane samples were found to be statistically significant process variables affecting antioxidant activity measured by the TEAC and ORAC methods. trans-Resveratrol and trans-&amp / #949 / -viniferin were extracted from milled grape canes using pressurized low polarity water (PLPW). The extraction temperature was significant for both compounds: extraction at 160oC resulted in a 40% loss of trans-resveratrol compared to 95oC while reduction of trans-&amp / #949 / -viniferin at both temperatures remained at 30%. Increasing ethanol concentration from 0 to 25% increased the extraction of total phenolics and trans-&amp / #949 / -viniferin by 44% and 489%, respectively. Solvent flow rate also influenced trans-&amp / #949 / -viniferin extraction. Effective diffusivities of trans-resveratrol increased by three times with increasing temperature. The modified Gompertz equation satisfactorily explained the extraction of the stilbenes investigated.

In the most of the drilling operations it is obvious that a considerable amount of money is spent for drilling related problems / including stuck pipe, lost circulation, and excessive mud cost. In order to decrease the percentage of non-productive time (NPT) caused by these kind of problems, the aim is to control annular frictional pressure losses especially in the fields where pore pressure and fracture pressure gradient is too close which is called narrow drilling window. If we can solve these problems, the budget spent for drilling the wells will fall, therefore enabling the industry to be able to drill wells that were previously uneconomical. Managed Pressure Drilling (MPD) is a new technology that allows us to overcome these kinds of drilling problems by controlling the annular frictional pressure losses. As the industry remains relatively unaware of the full spectrum of benefits, this thesis involves the techniques used in Managed Pressure Drilling with an emphasis upon revealing several of its lesser known and therefore less appreciated applications.

This study is conducted for the design and analysis of pressure vessels and associated pressurized equipment using various codes and methods. A computer software is developed as the main outcome of this study, which provides a quick and comprehensive analysis by using various methods utilized in codes and standards together with theoretical and empirical methods which are widely accepted throughout the world. Pressure vessels are analyzed using ASME Boiler and Pressure Vessel Code, whereas auxiliary codes, especially ASCE and AISC codes are utilized for structural analyses of these equipment. Effect of wind, seismic, and other types of loadings are also taken into consideration in detail, with dynamic analyses. Support structures and their auxiliary components are also items of analysis. Apart from pressure vessels, many pressurized process equipments that are commonly used in the industy are also included in the scope of the study. They include safety valves which are an integral part of those kinds of pressurized or enclosed systems, two of the heat exchanger components with great importance -tubesheets and expansion joints-, and API 650 tanks for oil or water storage. The computer software called as VESSELAID is written in Microsoft Visual Basic 6.0 using SI units. Design and analysis methods of VESSELAID are based on various code rules, recommended design practices and alternative approaches.

Primary water stress corrosion cracking (SCC) of metals in pressurized water reactors (PWRs) is known to be one of the most challenging and cost intensive modes of failure in the nuclear industry. Even though it is known that cracking in Ni-base alloys proceeds mainly intergranular (IG), the initiation and propagation of cracks in ductile metals are not yet understood and a much-desired accurate prediction of SCC related failure seems unobtainable. In this thesis, a combination of microcantilever fracture experiments, scanning electron- (SEM) and transmission electron microscopy (TEM) techniques was employed to study and compare the failure of oxidized grain boundaries of Ni-base Alloy 600 with high and low intergranular carbide coverage and different sample history. A new technique for lifting-out whole cantilevers after testing and for performing 3D focussed ion beam sequencing (3D FIB-SEM) while preserving a thin central region of the cantilever for further TEM sample preparation was developed and is presented. In lieu with recent efforts of the main project sponsor Électricité de France (EDF) to build a predictive model for IGSCC based on localized/microscopic information, one of the main objectives was the extraction of the stress at failure of individual oxidized GBs. Supported by finite element simulations, microcantilever fracture tests revealed that surface oxides on top of individual GBs have the capability to alter the mechanical response by delaying/suppressing the onset of failure. An overestimation of the failure stress (> 230 MPa) was observed, proving that the presence of the surface oxide on top of the test structures cannot be neglected. The failure stress on both samples, tested without influence of the surface oxide, was found to cover a range of 300 - 600 MPa, which agreed well with finite element simulations of the tests and further demonstrates the reliability of the obtained data. The second objective was to gain a better understanding of the observed fracture behaviour and the role of local microstructure. Using the gathered microscopy data, it was found that the crack clearly favours a progression along the IG oxide-metal interface in the presence of carbide precipitates. Electron energy loss spectroscopy (EELS) revealed that the observed crack path can be linked to compositional and density variations of the IG oxide. In the presence of carbides the oxide was layered. An oxide close to the stoichiometry of chromia was located at the original GB and next to the carbides. Next to this Cr-rich oxide, Fe-rich mixed spinel oxides of varying composition and density were found. An explanation for density variations based on the possible formation of defective spinel oxides of the type A²⁺B³⁺₂O₄, due to an unavailability of certain cation species is presented. No clear interface preference was observed in the absence of precipitation, where the IG oxide was found to be thin and often incomplete with Cr-richer oxides preferentially located at the original GB. While these observations were consistent on both samples (high and low carbide coverage), bigger void-like defects were located at the Fe-richer oxide-metal interface of the cold worked sample with high IG carbide precipitation only. These weak spots seemed to be the preferred path for crack propagation on this sample. The sample with low intergranular carbide coverage showed no obvious porosities at this interface but a Cr- depleted region was seen. Introducing a multi-faceted investigation strategy, supported by finite element simulations, the presented thesis provides the most accurate determination of the failure stress of oxidized GBs on Alloy 600 to date and and adds new valuable insights to our understanding of IGSCC and the future prediction of SCC related failures.

Les générateurs de vapeur des réacteurs à eau pressurisée (REP) sont constitués d'alliage à base nickel. La surface d'échange associée représente environ 75 % de l'aire totale du circuit primaire. Sous l'effet de la corrosion généralisée, des cations nickel sont relâchés dans l'eau de ce circuit. Lorsque ces cations sont exposés au flux neutronique du coeur du réacteur, ils sont activés en éléments radioactifs (58Co). La circulation puis l'incorporation de ces produits de corrosion radioactifs sur les parois du circuit primaire posent alors problème lors des interventions humaines durant les opérations de maintenance.Le but de l'étude présentée ici est de créer par traitement thermomécanique une couche d'oxyde protectrice qui limite fortement le relâchement des cations nickel. L'influence de paramètres tels que la composition de l'atmosphère gazeuse lors du traitement thermique et l'état de surface initial de l'alliage considéré (laminage et rugosité de surface) a été étudiée. Les résultats présentés sont obtenus sur un alliage 690 oxydé à 700 °C sous deux atmosphères gazeuses de pressions partielles en oxygène (P(O2)) différentes.L'étude des cinétiques d'oxydation par analyse thermogravimétrique (ATG), met en avant une cinétique parabolique peu dépendante de la P(O2). Un laminage de 20 % n'affecte pas la cinétique d'oxydation alors qu'un laminage de 40 % et une rugosité de surface plus forte sont responsables d'une prise de masse plus importante. Un marquage à l'or permet de déterminer que la croissance de la couche est majoritairement cationique. L'aspect général de la surface des échantillons oxydés observé par microscopie électronique à balayage (MEB) est similaire quelle que soit la P(O2) : une couche d'oxyde continue d'aspect nanostructuré riche en chrome avec oxydation préférentielle du chrome le long des joints de grains de l'alliage sous-jacent. La spectroscopie de photoélectrons-X (XPS), la spectrométrie à décharge luminescente (SDL) et la diffraction des rayons-X (DRX) mettent en évidence la croissance d'une couche de chromine (Cr2O3) et la présence à l'interface gaz/oxyde de cristallites avec une cristallographie de type spinelle. Pour une faible P(O2) (de 1.10 -6 bar à 5.10 -6 bar) cette partie externe est riche en manganèse (MnCr2O4) alors que des cristallites riches en manganèse, chrome, nickel et en fer viennent s'intégrer dans cette configuration lors d'oxydations sous une P(O2) plus élevée (0,2 bar). L'ensemble des résultats obtenus permet de proposer des conditions de prétraitement sur l'alliage 690. Des échantillons ainsi traités sont testés en milieu primaire simulé et leur relâchement en nickel montre une nette baisse par rapport à des échantillons non traités thermiquement. / Steam generator tubes in pressurized water reactors (PWR) are made of nickel based alloy and represent nearly 75 % of the primary coolant loop surface. Due to generalized corrosion phenomena, nickel cations are released in the primary loop water. After neutron flux exposure in the reactor core, nickel cations can turn into radioactive products, such as 58Co. If carried through the circuit, these radioactive products precipitate and contaminate the loop, making maintenance more difficult.The present study goal is to form a very protective scale on the Alloy 690 surface by a pre-oxidation treatment performed at 700 °C. The impact of different parameters such as oxygen partial pressures of the gaz used during high temperature oxidation (low P(O2)=10 -6 bar or high P(O2)=0.2 bar) and the initial surface state of the sample (cold-worked or surface roughness) is studied. To minimize nickel cation release, the scale obtained must be continuous, homogeneous, rich in chromium and nickel free. The oxidation kinetics, studied using thermogravimetric analysis (TGA), show the existence of parabolic law independent of P(O2). The sample's surface aspect, observed using scanning electron microscopy (SEM), is similar for all P(O2). Top views show a preferential chromium oxidation along the grain boundaries and the formation of a chromium rich oxide scale, confirmed by X-ray photoelectron spectroscopy (XPS) and glow discharge optical emission spectrometry (GDOES); cross sectional views of the material exhibit holes beneath the oxide corresponding with the alloy's grain boundaries. The latter observation and an inert marking test with gold plots suggest a cationic growth of the oxide scale. X-ray diffraction (XRD) indicates the presence of chromia (Cr2O3) for low and high P(O2). For low P(O2), a Mn and Cr spinel is observed near the outer surface. For higher P(O2), a similar spinel layer is made up of Ni, Fe, Mn and Cr.Pretreatment conditions set to be applied on alloy 690 can be proposed thanks to the data collected. Samples, pretreated that way, are tested in simulated primary medium water and their nickel release is clearly cropping compared to non-thermaly-treated samples.