One of the key challenges the world will need to face during the 21st century is global warming and the consequent climate change. Its presence is indisputable, and decarbonizing the gird emerges as one of the required pathways to achieve global sustainable objectives. Solar energy power plants have the potential to revert this situation and solve the problem. One way to harness this energy is through Concentrated Solar Power plants. The major advantage and potential of this technology is its ability to integrate cost-effective Thermal Energy Storage (TES), which is key with such an inherently intermittent resource. On the other hand, the drawback is the high current Levelized Cost of Energy (LCOE). The other main way to harness that highlighted solar energy is the use of Photovoltaic panels, which have recently achieved very competitive LCOE values. On the other hand, the storage integration is still a very pricey option, normally done with Battery Energy Storage Systems (BESS). As a conclusion, a hybrid power plant combining the LCOE of the PV and the TES of the CSP emerges as the key way of achieving a very competitive solution with a big potential. This master thesis aims at exploring the possibilities of a hybrid CSP and PV power plant with a sCO2 power cycle, integrated in the primary, secondary and tertiary electricity markets. To achieve this purpose, firstly, a Python-based Energy Dispatcher was developed to control the hybrid power plant. Indeed, the Dispatcher is the tool that decides when to produce, when to store… following an optimization problem. This can be formulated mathematically, and that was done and integrated into the Python code using Pyomo, a software for optimization problems. As a result, the Dispatcher achieved an effective control of the plant, showing intelligent decisions in detailed hourly analyses. The results were very promising and included optimization functions as maximizing the profitability of the plant or the total production, among others. To proceed with the Techno-economic assessment of the hybrid plant, the electricity markets were studied. The main source of income of any power plant is normally the revenue from selling electricity to the grid, but since there are several markets, there are also other possibilities. In this thesis, it was assessed from a Techno-Economic perspective how the performance and optimal design of the plants vary when providing different services extra to selling electricity to the grid. The conclusion was that even though the Net Present Value (NPV) achieved working on the spot market was already very high, the extra value added from participating in the secondary or tertiary markets was indisputable. Indeed, the profits attained in those markets were between two and four times higher than the ones of the spot market. This is a specific case, but a trend was identified: these hybrid power plants have a huge possibility and a bright future on the service markets. As a consequence, this thesis shows the huge potential of hybrid power plants integrated in the grid participating in several markets. It also lays the foundation for future studies in other locations, under different conditions and with different technologies, among others.

Le développement de comportements sexuels problématiques (CSP) pendant l’enfance est un sujet de plus en plus étudié. Les chercheurs et les cliniciens ont souvent fait référence à l’agression sexuelle (AS) pour l’expliquer. Bien que le lien entre les CSP et l’AS soit bien documenté dans la littérature scientifique, il reste que la présence de CSP semble liée à plusieurs autres facteurs. Les auteurs s’intéressent de plus en plus à la relation entre les CSP et l’exposition à d’autres types de victimisation, incluant la maltraitance. La cooccurrence de différentes formes de victimisation s’avère donc être un angle important à explorer, en raison de sa relation avec différents indices de détresse psychologique incluant les comportements extériorisés. Objectif. L’objectif principal de ce mémoire est d’identifier les facteurs qui permettent d’estimer la probabilité qu’un enfant victime d’agression sexuelle (VAS) présente des CSP. Méthode. L’échantillon est composé de 372 enfants VAS (M âge enfant = 9,4 ans ; É-T = 2,2 ; 32,3% garçons) ayant fait l’objet d’une évaluation des besoins, dans un centre de services d’intervention spécialisés entre 2007 et 2016. Des analyses bivariées (chi-carré, anova, U de Mann-Whitney) et un modèle d’analyse de régression logistique hiérarchique ont été réalisés. Résultats. Les résultats des analyses bivariées révèlent que les enfants VAS manifestant des CSP se distinguent des enfants VAS n’ayant pas de CSP sur plusieurs variables : ils présentent plus de symptômes de dissociation, de dépression et d’anxiété; ils ont une plus faible estime de soi; ils perçoivent aussi recevoir moins de soutien à la suite de l’AS et présentent davantage des troubles de comportement extériorisés, de même que des stratégies de résolution de problème extériorisées; ils sont aussi plus souvent polyvictimes, ils sont notamment plus souvent exposés à la violence conjugale, plus susceptibles de vivre de la violence psychologique et d’avoir vécu une AS plus grave. Alors qu’ils reçoivent des services pour leur victimisation sexuelle; ils sont aussi plus susceptibles d’avoir un dossier actif en vertu de la Loi de la Protection de la Jeunesse (LPJ), ils vivent plus de placements, puis une médication leur est plus souvent prescrite. Lorsque l’ensemble de ces variables est considéré dans le modèle de régression logistique, l’analyse révèle que les facteurs suivants augmentent la probabilité qu’un enfant VAS présente des CSP : être un garçon (2,2 fois plus de risque), avoir une médication prescrite (2,2 fois plus de risque) et présenter un niveau de dissociation atteignant le seuil clinique (2,5 fois plus de risque). À l’inverse, la perception d’avoir reçu du soutien à la suite de l’AS diminue le risque que l’enfant VAS présente des CSP (0,8 fois moins de risque). Conclusion. Les résultats révèlent que l’apparition de CSP chez les enfants VAS semble liée à une accumulation de facteurs de vulnérabilité parmi lesquels la détresse psychologique (médication, dissociation) et la victimisation s’avèrent être des composantes particulièrement importantes. / The development of sexual behavior problems (SBP) during childhood is increasingly studied. While researchers and clinicians have often associated SBP to child sexual abuse (SA), the presence of SBP also seems to be linked to several other factors. Most recent works are exploring, among other factors, the frequent association between SBP and exposure to other forms of victimization, including child maltreatment. The cooccurrence of different forms of violence therefore turns out to be an important angle to explore because of its relationship with different indices of psychological distress, including externalizing behaviors. Objective. The main objective of this Masters’ thesis is to identify factors allowing to estimate the probability that a sexually abused child presents inappropriate sexual behaviors and SBP (referred to as SBP). Method. The sample was composed of 372 SA children (M child’s age = 9.4 years; SD = 2.2; 32.3% boys) who were assessed in a specialized intervention center between 2007 and 2016. Bivariate analysis (chi-square, one-way ANOVA, Mann Whitney U) and a hierarchical linear regression analysis were performed. Results. Bivariate analyses reveal that SA children with SBP show more symptoms of dissociation, depression, and anxiety than SA children without SBP. They also report receiving less support with regard to their SA experience and show more externalized behaviors and externalized problem solving strategies than SA children without SBP. Further, SA children with SBP are more frequently polyvictimized. For instance, compared to children without SBP more children in this group have been exposed to domestic violence, to psychological abuse and to more severe SA. While they are receiving services for their SA experience, they were are also more likely to have an active file under the Youth Protection Act (YPA), to experience placement, and to be prescribed medication for ADHD or behavior and emotion regulation problems. Taken together, multivariable analyses conducted with the regression model reveals that the following factors increase the probability of presenting SBP in SA victims: the child's gender (being a male, 2,2 times more likely to present SBP), being prescribed medication (2,2 times more likely to present SBP) and presenting a level of dissociation reaching the clinical threshold (2,5 times more likely to present SBP). Conversely, perceiving to have received less support in relation to the sexual abuse experienced decreases the risk that the AS child will present SBP (0,8 times less likely to present SBP). Conclusion. The results reveal that the development of SBP in child victims of SA appears associated to an accumulation of vulnerability factors, among which psychological distress (e.g.: dissociation and medication) and victimization prove to be particularly important components.

<p>  </p> <p>Concentrated solar power (CSP) is a technology that utilizes focused sunlight to heat a high-temperature medium (such as a molten salt). Heat from this medium can be transferred to a working fluid (such as supercritical CO2) that is then used to drive a turbine to generate electricity. Alternatively, the hot medium/fluid can be pumped into tanks for thermal energy storage (TES), for heat extraction later to generate dispatchable electricity and/or for electricity production at night or on cloudy days. By increasing the fluid temperature to <u>></u>750oC and utilizing TES, CSP can become more cost competitive with fossil-based electricity production. Current CSP systems utilize molten nitrate salts for heat transfer and TES that are known to thermally degrade at temperatures >600oC. To achieve temperatures <u>></u>750oC, molten chloride salts, such as ternary MgCl2-KCl-NaCl compositions, are being considered as heat transfer and thermal energy fluids for next generation CSP plants due to their higher temperature stability, low cost, and availability. </p> <p>In this work, it was demonstrated that MgCl2-containing molten salts are prone to oxidation in ambient air at 750oC, which can enhance corrosion of the containment materials and alter the thermophysical properties of the fluid. An alternative, low-cost, earth-abundant, MgCl2-free, oxidation-resistant molten salt, a eutectic CaCl2-NaCl composition, was developed, along with a corrosion mitigation strategy, to enable the slow growth of protective oxide layers on metals that are resistant to dissolution by such MgCl2-free molten chloride salts. </p> <p>This strategy was expanded to other low-cost, oxidation resistant compositions, such as eutectic BaCl2-CaCl2-KCl-NaCl with tailored chemical and thermophysical properties for CSP and TES. The melting temperature, heat capacity, oxidation resistance, and crystallization behavior were measured for eutectic a BaCl2-CaCl2-KCl-NaCl(17.5-47.8-3.3-31.4 mol%) (BCKN) salt and a MgCl2-KCl-NaCl (40-40-20 mol%) salt. BCKN salt was shown to have a similar melting temperature while having a higher heat capacity and far better oxidation resistance. </p> <p>The corrosion of the nickel-based superalloy Haynes 214 was studied in molten MgCl2-KCl-NaCl (40-40-20 mol%) salt at 750oC under inert atmosphere conditions using a custom-built rotating-disc corrosion testing apparatus that maintained laminar fluid flow on the sample. Non-protective external Cr-, Al-, and Mg- oxide layers were formed on Haynes 214 that were prone to spallation. Internal oxidation of Al was also observed along with Cr depletion zones within Haynes 214.  Corrosion kinetics were evaluated to quantify the role of fluid flow for application of this alloy for use in containment and transportation of this molten chloride salt. </p>

The global need to eliminate CO2 emissions and its consequent reduction in the use of fossil fuels drives the ongoing energy transition that highly involves the research achievements of the scientific community to reach the goals of this purpose. Renewable sources like photovoltaic and wind energy, are central to this endeavor, however, the intermittency of natural resources makes it non-dispatchable and energy storage is fundamental. According to the European Roadmap [1] just a 60% of the CO2 emissions reduction goal can be achieved with available technologies and existing energy. However, the production, use and specially storage opportunities that hydrogen offers can drive non-dispatchable renewable sources to achieve its full potential by clearing up the intermittency problem as well as covering the remained 40% gap. This master's thesis aims to investigate the techno-economic feasibility of integrating a Solid Oxide Electrolyzer Cell (SOEC) into a hybrid PV-CSP(sCO2) plant. The study focuses on assessing various indicators related to electricity, energy, and hydrogen production prices. To achieve this, three different integration strategies within the hybrid PV-CSP(sCO2) plant were selected for analysis: Soec using heat from the particles coming from the receiver, soec using heat coming from the particles available in the thermal energy storage (TES) and soec recovering heat from the sCO2 power block. A sensitivity analysis was conducted on different PV sizes (MWp), battery capacities (MWh), and SOEC installed capacities (MWh) to investigate the technology's potential in the plant and determine optimal sizing of subsystems. However, the individual optimization of economic indicators presented technical and economic challenges. Scenarios allowing individual optimization of hydrogen production prices (€/kg H2) resulted in 10.9, 11.7, and 14.6 €/kg h2 for receiver, TES, and sCO2 integration strategy, respectively. These scenarios, however, require high SOEC installed capacities, leading to elevated electricity and energy production prices. On the other hand, the individual optimization of electricity and energy production prices led to better and lower results when no hydrogen production presence within the plant. However, this analysis also showed that soec capacities below 5MWh together with no installation of batteries and a new definition for calculating hydrogen production prices (LCOH) allows feasible integration of hydrogen production within the plant. LCOH(€/kg h2) results were 10.2€/kg h2, 7.6€/kg h2, and 9.4€/kg h2 for receiver, TES, and sCO2, respectively, for a soec installed capacity of 0.5MWh (119m2 size) along with energy production values not exceeding 101€/MWh. While the results present a favorable outlook for SOEC installations based on literature review data [2] [3] [4] they still face challenges when competing with the cost-efficient PEM technology, which offers 4.5-5.5€/kg H2 [5] without storage. Nonetheless, this research contributes valuable insights into the integration of SOEC technology within hybrid renewable energy systems and provides a comprehensive analysis of the techno-economic aspects related to hydrogen production following different integration strategies. The findings may inform decision-making processes and promote further advancements in sustainable energy solutions. / Det globala behovet av att eliminera CO2utsläpp och därmed minska användningen av fossila bränslen driver pågående energiomställning, som starkt involverar forskningsresultaten från vetenskapssamhället för att nå syftet med detta mål. Förnybara källor som solceller och vindkraft är centrala i detta arbete, men intermittensen hos naturliga resurser gör dem icke disponibla och energilagring är grundläggande. Enligt den europeiska vägkartan [1] kan endast 60% av målet att minska CO2-utsläppen uppnås med tillgängliga teknologier och befintlig energi. Produktionen, användningen och särskilt lagringsmöjligheterna som väte erbjuder kan emellertid driva icke-disponibla förnybara källor att nå sin fulla potential genom att lösa intermitt ensproblemet och täcka den återstående 40% klyftan. Detta examensarbete syftar till att undersöka den tekniskekonomiska genomförbarheten av att integrera en fastoxid elektrolysör (SOEC) i en hybrid PV CSP(sCO2)-anläggning. Studien fokuserar på att utvärde ra olika indikatorer relaterade till el-, energi- och vätgasproduktionspriser. För att uppnå detta har tre olika integrationsstrategier inom hybrid PV CSP(sCO2) anläggningen valts för analys: SOEC med hjälp av värme från partiklar som kommer från mottagaren, SOEC med hjälp av värme från partiklar som finns i termisk energilagring (TES) och SOEC som återvinner värme från sCO2-kraftblocket. En känslighetsanalys har genomförts för olika PVstorlekar (MWp), batterikapaciteter (MWh) och SOEC installerade kapacit eter (MWh) för att undersöka teknologins potential i anläggningen och bestämma optimal dimensionering av delsystem. Resultaten från individuell optimering av ekonomiska indikatorer ledde dock till flera tekniska och ekonomiska utmaningar. Scenarier som tillåter individuell optimering av vätgasproduktionspriser (€/kg H2) resulterade i 10, 9, 11, 7 respektive 14,6 €/kg H2 för mottagare, TES och sCO2 integrationsstrategi. Dessa scenarier kräver dock höga SOEC installerade kapaciteter, vilket leder till höga el och energipriser. Å andra sidan ledde individuell optimering av el och energiproduktionspriser till bättre och lägre resultat när ingen vätgasproduktion fanns i anläggningen. Denna analys visade också att SOEC kapaciteter under 5MWh tillsammans med ingen installation av batterier och en ny definition för beräkning av vätgasproduktionspriser (LCOH) möjliggör genomförbar integration av vätgasproduktion i anläggningen. LCOH (€/kg H2) resultaten var 10,2 €/kg h2 , 7 ,6 €/kg h2 respektive 9,4 €/kg h2 för mottagare, TES och sCO2, för en SOEC installerad kapacitet på 0,5 MWh (storlek 119m2) tillsammans med energiproduktionsvärden som inte överstiger 101 €/MWh. Medan resultaten visar en gynnsam utsikt för SOECinstallationer baserat på data från litteraturöversikter [2] [3] [4], står de ändå inför utmaningar när de konkurrerar med den kostnadseffektiva PEM teknologin, som erbjuder 4,5-5,5 €/kg H2 [5] utan lagring. Trots detta bidrar forskningen med värdefulla insikter i integrationen av SOEC teknologi i hybrid förnybara energisystem och ger en omfattande an alys av de teknisk-ekonomiska aspekterna relaterade till vätgasproduktion enligt olika integrationsstrategier. Resultaten kan informera beslutsprocesser och främja ytterligare framsteg inom hållbara energilösningar.

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Getting incorrect website content has increased in recent years, which is a reflection of the web security status on the Internet. However, when It comes to government and other professional organisations websites, they should have the best security requirements and follow security recommendations. This research will study websites located in the SE zone. The total number of investigated websites is 1166. The testing process was done in two ways. The firstway is a Dutch test website tool called Internet.nl. The second is using a tool developed as part of the research. The investigation focuses on Swedish websites and nine security extensions. These extensions prevent Man in the middle attack(MITM), downgrade attacks, Cross-Site Scripting (XSS), Click-jacking, and ensure that the correct information is obtained when a client requests a website. The paper evaluated the security between 2014 and 2022. What are the types of security taken and which sector has the best security awareness. The using of security headers had increased in 2022, the total use of tested security standards in the SE zone is around 50%, and banks have the best security awareness.

Hoy en día, muchos problemas reales pueden modelarse como problemas de satisfacción de restricciones (CSPs) y se resuelven usando técnicas específicas de satisfacción de restricciones. Estos problemas pertenecen a áreas tales como Inteligencia Artificial, investigación operativa, sistemas de información, bases de datos, etc. La mayoría de estos problemas pueden modelarse de forma natural mediante CSPs. Sin embargo, algunos de estos problemas son de naturaleza distribuida, bien por motivos de seguridad, por requerimientos de privacidad, o por restricciones espaciales. Ello requiere que este tipo de problemas sean modelados como problemas de satisfacción de restricciones distribuidos (DCSPs), donde el conjunto de variables y restricciones del problema está distribuido entre un conjunto de agentes que se encargan de resolver su propio sub-problema y deben coordinarse con el resto de agentes para alcanzar una solución al problema global. En la literatura de satisfacción de restricciones, la necesidad de manejar DCSP comenzó a tratarse a principios de los 90. No obstante, la mayoría de los investigadores que trabajan en este campo centran su atención en algoritmos en los que cada agente maneja una única variable. Estos algoritmos pueden ser transformados para que cada agente maneje múltiples variables. Sin embargo, los algoritmos resultantes no son escalables para manejar grandes sub-problemas locales debido tanto a requerimientos espaciales como a su coste computacional. Por lo tanto, la resolución de problemas reales mediante este tipo de algoritmos resulta prácticamente inviable. En esta tesis presentamos nuevos algoritmos para la resolución de problemas de satisfacción de restricciones distribuidos capaces de manejar multiples variables por agente. Estos algoritmos realizan un manejo eficiente de la información obtenida mediante la comunicación entre los agentes, consiguiendo con ello una mayor eficiencia durante el proceso de resolución. Además, sus requerimientos / Abril López, M. (2007). Particionamiento y resolución distribuida multivariable de problemas de satisfacción de restricciones [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/1946

Corporate social responsibility (CSR) är ett aktuellt ämne som syftar till att företag ska ta ett större samhällsansvar, både ur ett ekonomiskt, miljömässigt och socialt perspektiv. Den globalisering som råder i världen påverkar inte bara ett internt företagsklimat, det ger även effekter på omgivande samhälle och individer, vilket tillsammans med sociala påtryckningar skapar ett behov av CSR. Ansvaret till samhället innebär inte bara ekonomiska och lagliga aspekter, dock ska ett etiskt och filantropiskt perspektiv också antas. Idag är CSR ett frivilligt åtagande och för att kunna motivera företag till ett större ansvarstagande för sitt agerande ämnar denna studie att undersöka, ur ett nordiskt sammanhang, om ett företags hållbarhetsarbete genererar lönsamhet. Studien utgår från nordiska börsnoterade företag som ingår i Dow Jones Sustainability Index (DJSI). Indexet representeras av de bäst presterande hållbarhetsföretagen i världen som kvalificerat sig till att ingå. Genom en deduktiv kvantitativ metod studeras sambandet mellan CSR och lönsamhet för att förklara vilken effekt variabeln Corporate Social Performance (CSP) har på variabeln Corporate Financial Performance (CFP) under tidsperioden 2010-20162010–2016. Fortsättningsvis undersöks skillnaden i lönsamhet mellan företag som inkluderats i DJSI och matchade likartade nordiska företag som inte ingår i indexet. Undersökningen baseras på sekundärkällor ur ett naturvetenskapligt perspektiv. Studien erhåller ett resultat som påvisar att företag som ingår i hållbarhetsindexet tenderar att vara mer lönsamma än företag som inte ingår genom att redovisningsbaserade mått, bruttomarginal och avkastning på totalt kapital (ROA), har applicerats. Studiens slutsats blir att CSR-arbete kan öka lönsamheten i nordiska företag genom att bli inkluderade i DJSI, studien visar dock att placeringen i indexet inte har någon betydelse. Därav blir studiens bidrag att motivera företag till ett större åtagande av hållbarhetsarbete eftersom CSR kan generera högre lönsamhet. / Corporate social responsibility (CSR) is a current topic which aims to encourage companies to be more responsible as an societal actor, both from an economic, environmental and social perspective. The consequences of the globalization may not only affect the internal business environment, it will also affect the surrounding society and individuals, which together creates a demand for CSR. As a societal actor, companies needs to include ethical and philanthropic responsibilities, and not only take economic and legal aspects into consideration. Currently, CSR is a voluntary commitment and to motivate companies to embrace the responsibility for the society, this study aims to investigate, from a Nordic context, whether companies’ sustainability work generates profitability.   The study is based on Nordic listed companies included in the Dow Jones Sustainability Index World (DJSI), which is an index where the top performing sustainability companies can qualify for an inclusion. The correlation between CSR and profitability will be studied through a deductive quantitative method to explain what impact Corporate Social Performance (CSP) has on Corporate Financial Performance (CFP) during the years between 2010-2016. Furthermore, the differences in profitability between companies included in DJSI matched Nordic companies that are not included in the index will be investigated. From a scientific perspective, the survey is based on secondary sources. The results of the study indicates that companies included in the sustainability index tend to have an improved profitability than companies that are not included. This by applying the accounting-based measures gross margin and return on assets (ROA). The conclusion of the study is that CSR can improve profitability among the Nordic companies by an inclusion in DJSI, but the study shows that the placement in the index does not have an impact. Hence, the contribution of this study is to motivate companies to a greater commitment to sustainability because CSR can generate improved profitability.

Suite à la première thèse sur le greffage et l’adsorption physique successives de sélecteurs chiraux dans des tubes ouverts en électrochromatographie capillaire (ECC ou CEC) chirale, menée par le Dr Guillaume Pédéhontaa-Hiaa au sein de l’équipe du laboratoire COBRA (IUT d’Evreux), nous avons développé des phases stationnaires chirales covalentes (CSPs) à base de cyclodextrines (CDs) en tubes ouverts et des CSPs sur supports monolithiques pour l’emploi en CEC. Nous avons ainsi évalué les paramètres électrochromatographiques et la stabilité de ces CSPs en séparant une variété de racémiques neutres et chargés. L’influence de la température d’analyse, le potentiel appliqué ainsi que la nature et le pH des électrolytes sur la qualité des électrochromatogrammes ont été étudié en CEC chirale. Cette étude se divise en deux grandes parties. La première concerne les CSPs élaborées sur colonnes à tubes ouverts pour l’OT-CEC. Il s’agit initialement de graver la surface interne d’un capillaire de silice de 50 μm de diamètre interne à l’aide d’une solution de bifluorure d’ammonium dans le but premier d’augmenter considérablement sa surface spécifique et d’immobiliser en surface une grande quantité de sélecteurs chiraux à base de β-CD. Nous avons alors décrit des greffages covalents de CDs anioniques (Scc-β-CD et CM-β-CD) et d’un polymère anionique de CDs (p-CM-β-CD-) en surface de capillaire de gel de silice gravée et modifiée chimiquement par l’aminopropyltriéthoxysilane (APTEOS). Les greffages des sélecteurs ont été reproduits dans les mêmes conditions que dans la thèse rapportée précédemment en électrophorèse. L’originalité de la construction de ces CSPs réside dans la rapidité et la simplicité du couplage dit péptidique à température ambiante, des sélecteurs carboxylés sur des colonnes préalablement gravées. Ce greffage nécessite des agents de couplage peptidique solubles dans l’eau tels que 1-Ethyl-3-(diméthylaminopropyl)carbodiimide (EDC) et le N-Hydroxysuccinimide (NHS). Il peut aussi être obtenu de manière moins efficace avec d’autres agents solubles en milieu organique tels que le O-(Benzotriazol-1-yl)-N,N,N’,N’-tétraméthyluronium tétrafluoroborate et la triéthylamine (TBTU/TEA). Chaque étape menant aux CSPs a été caractérisée par une étude de flux électroosmotique (FEO) en OT-CEC. Des analyses en AFM et en MEB nous renseignent d’avantage sur le succès du procédé « etching » de nos capillaires. La deuxième grande partie de cette étude traite de la synthèse in-situ de CSPs sur des colonnes de type polymères monolithes organiques et un monolithe hybride à base de sol gel. Des post modifications de surface de ces supports monolithiques nous ont permis d’immobiliser de façon covalente et non covalente des sélecteurs de β-CD en surface des volumes macroporeux. Deux collaborations ont vu le jour pour atteindre ces objectifs. La première eut lieu avec le Dr Thuy Tran et le Pr Myriam Taverna de la Faculté de Pharmacie de Chatenay Malabry (UMR 8612), durant laquelle nous avons reproduit une colonne monolithe organique de type méthacrylate, porteuse de groupements phosphate dans l’optique d’adsorber physiquement en surface le polymère cationique de CDs (p-CD+) que nous a transféré le Pr Benjamin Carbonnier et d’évaluer les capacités de discrimination chirale de cette nouvelle CSP en m-CEC. La seconde collaboration a eu lieu avec le Dr Mohamed Guerrouache et le Pr Benjamin Carbonnier au sein du laboratoire ICMPE de Thiais, où nous avons synthétisé des colonnes monolithiques organiques à base d’acrylates dans le but de greffer en surface de façon covalente et non covalente les CDs et polymères de CDs et d’évaluer ces nouvelles CSPs en m-CEC. La troisième phase stationnaire monolithique employée est celle décrite par le Dr Huihui Yang qui décrit un monolithe hybride porteur de groupements sulfonates nous permettant par la suite d’immobiliser électrostatiquement le p-CD+ sur le réseau poreux et d’évaluer cette nouvelle CSP en m-CEC. / New chiral stationary phases have been prepared for Open Tubular and monolithic columns used in electrochromatography capillary. In order to separate racemic mixtures such as flavonoïd, Hidantoïn derivatives, Binaphtalene-2, 2-hydrogenophosphate and others chiral solutes, we use the β-cyclodextrin forms as chiral selector. Besides, β-cyclodextrin seems to be the most efficient chiral selector in chromatography since it is able to complex and dissolve optical organic isomers in an aqueous media, this chiral selector is able to dissolve even lipophilic molecule with high weight. The complexation is based on interactions with β-cyclodextrin. This study aims to elaborate new chiral stationary phase for CEC using β-cyclodextrin polymers and β-cyclodextrin derivatives. Two approaches were used: Firstly, covalent stationary phases coating with carboxymethyl-β-cyclodextrin polymers and oligomers containing carboxyl’s group had been experimented for open tubular and monolithic column in CEC. Then a non-covalent coating cationic polymer of β-cyclodextrin’s derivatives was immobilized (polytrimethyl ammonium β-CD) on continuous organic monoliths bearing anionic’s group. Prior to the covalent coating of the CD’s chiral selector for OT-CEC and m-CEC, we needed to modify the silicate surface and the monolithic surface with a primary amine silicate1,2 (aminopropyltriethoxysilane) and EDA, an amino-organic moiety (Ethylene diamine). The stability of the bonded organic moiety (APTEOS, EDA) were studied by CEC at different pH with constant ionic strength’s buffer. In this way, graft of carboxymethyl-β-cyclodextrin polymer on silica inner surface modified by APTEOS and on NAS-co-EDMA surface modified by EDA succeeded in activating and covalently coupling reagent as EDC and NHS (1-ethyl-3(-3-dimethtylaminopropyl) carbodiimide and N-hydroxysuccinimide, respectively3) with carboxymethyl’s group of carboxymethyl-β-cyclodextrin . The resultant stationary phase lead to stable chiral stationary phases, easier to prepare starting by coupling the selector to the amine’s group using EDC and NHS. In order to optimize enantio-separations by increasing the specific surface of open tubular columns, we reproduce the etching process to bared capillaries with ammonium bifluoride solution, referred to Pesek’s process4. By this mean, we increase dramatically the specific surface of bared capillaries before anchoring CDs polymers to silicate surfaces modified by APTEOS. Finally due to etching process, we obtain a covalent bonded Chiral Stationary Phase (CSP) which led to more efficient and resolvent enantio-separations by CEC. To describe, in another way, the non-covalent coating of CSP, we immobilised a cationic polymer (polytrimethyl ammonium β-CD+) on two kind of continuous organic and silica hybrid monoliths bearing sulfonate5 and phosphate’s groups. Based on precedent results for OT-CEC enantio-separation with LbL stationary phase7, using successive layers charged polymers to separate racemic mixture in CEC, we decided to adsorb a polycationic polymer hydrosoluble onto the silica hybrid monolith column to form chiral stationary phase (CSP) polytrimethyl ammonium β-cyclodextrin. This way of modification for monolithic surface by chiral selectors is nowadays highly efficient and attractive for CEC. The effect of the matrix and the coating’s nature are discussed by comparing the chromatographic parameters.

La limite théorique de rendement des cellules photovoltaïques simple-jonction est de l’ordre de 33% d’après le modèle de Shockley-Queisser, ce qui reste éloigné de la limite de Carnot, prédisant une limite maximale de conversion énergie solaire → électricité de 93%. L’écart important entre ces deux limites découle des pertes intrinsèques, essentiellement liées à la conversion inefficace du spectre solaire et à la disparité entre les angles solides d’absorption et d’émission. Pour surmonter ces pertes et se rapprocher de la limite de Carnot, trois stratégies sont envisagées dans cette thèse : les cellules multi-jonction àconcentration, la combinaison de la concentration et de la restriction angulaire et les systèmes hybrides PV/CSP. Chacune de ces stratégies est limitée par des mécanismes qui dégradent leur performance.L’objectif de cette thèse est donc de comprendre dans quelle mesure les différents mécanismes limitants sont susceptibles d’affecter les performances des différentes stratégies étudiées, et d’optimiser l’architecture des cellules dans le but d’accroitre leur efficacité de conversion. Dans ce but, un modèle détaillé de cellule solaire tenant compte des principaux mécanismes limitant a été développé. Un outil d’optimisation par algorithme génétique a également été mis au point, afin d’explorer l’espace des différents paramètres étudiés pour identifier les conditions d’opération optimales. Nous démontrons l’importance majeure que revêt l’adaptation des propriétés optoélectroniques des matériaux utilisés aux conditions opératoires, que ce soit dans le cas des cellules solaires à concentration endurant des pertes résistives significatives, ou encore dans le cas de cellules solaires fonctionnant à des niveaux de températures très supérieurs à l’ambiante. Enfin, nous avons déterminé l’effet des principaux facteurs limitant que constituent les pertes résistives et les recombinaisons non-radiatives sur les cellules solairessimultanément soumises au flux solaire concentré et à la restriction angulaire du rayonnement émis. / The maximum efficiency limit attainable with a single-junction PV cell is ~ 33% according to the detailed balance formalism (also known as Shockley-Queisser model), which remains far from the Carnot limit, predicting a solar to electricity efficiency upper value of 93%. The large gap between both limits is due to intrinsic loss mechanisms, including the inefficient conversion of the solar spectrum and the large discrepancy between the solid angles of absorption and emission. To overcome these losses and get closer to the Carnot limit, three different strategies are considered in this thesis: concentrated multi-junction solarcells, the combination of solar concentration and angular confinement, and hybrid PV/CSP systems. Each strategy is inherently limited by several loss mechanisms that degrade their performances. The objective of this thesis is, hence, to better understand the extent to which these strategies are likely to be penalized by these losses, and to tailor the cell properties toward maximizing their efficiencies. To address these questions, a detailed-balance model of PV cell accounting for the main loss mechanisms was developed. A genetic-algorithm optimization tool was also implemented, aiming at exploring the parameter space and identifying the optimal operation conditions. We demonstrate the uttermost importance of tailoring the electronic properties of the materials used with both multi-junction solar cells undergoing significant series resistance losses, and PV cells operating at temperature levels exceeding ambient temperature. We also investigate the extent to which series resistances losses and non-radiative recombination are likely to affect the ability of PV cells simultaneously submitted to concentrated sunlight and angular restriction of the light emitted by band-to-band recombination.