A fundamental requirement in agricultural trade is that imported products are safe, and do not pose a risk to human, animal and plant health. To address this issue, all countries maintain measures to ensure that imported food is safe for consumers, and to prevent the spread of disease among animals and plants. These measures, by their nature, can affect competitiveness by increasing the costs of imports or prohibiting them altogether. To ensure that these measures are used for their intended purpose and not as protectionist measures, WTO member countries signed the Agreement on the Application of Sanitary and Phytosanitary measures. A growing number of studies attempt to quantify the effects of SPS regulations on international trade flows. However, precious little research is dedicated to determining the effects of specific phytosanitary regulations on trade flows and, more importantly, questions regarding SPS regulations and their impact as "trade barriers" or "trade catalysts" remain to be settled. This thesis contributes to existing literature in two ways. First, a comprehensive and user friendly database on specific phytosanitary regulations faced by U.S. exports of onions, peas, walnuts, apples, cherries, grapes, peaches/nectarines, oranges and strawberries to 176 countries is developed for the period 1999-2009. Second, this database is used for an empirical investigation to determine how existing SPS regulations affect U.S. fruit and vegetable exports. The results indicate that initially, phytosanitary treatments act as "barriers" to trade. However, as exporters' experience grows, the negative impact of treatments is reduced and eventually eliminated. / Master of Science

Nanostructured ferritic alloy and silicon carbide composite materials (NFA-SiC) were sintered with spark plasma sintering (SPS) method and systematically investigated through X-ray diffraction (XRD), scanning electron microscopy (SEM), as well as density and Vickers hardness tests. Pure NFA, pure SiC, and their composites NFA-SiC with different compositions (2.5 vol% NFA-97.5 vol% SiC, 5 vol% NFA-95 vol% SiC, 97.5 vol% NFA-2.5 vol% SiC, and 95 vol% NFA-5 vol% SiC) were successfully sintered through SPS. In the high-NFA samples, pure NFA and NFA-SiC, minor gamma-Fe phase formation from the main alfa-Fe matrix occurred in pure NFA 950 degree C and 1000 degree C. The densities of the pure NFA and NFA-SiC composites increased with sintering temperature but decreased with SiC content. The Vickers hardness of the pure NFA and NFA-SiC composites was related to density and phase composition. In the high-SiC samples, NFA addition of 2.5 vol% can achieve full densification for the NFA-SiC samples at relative low temperatures. With the increase in sintering temperature, the Vickers hardness of the pure SiC and NFA-SiC composite samples were enhanced. However, the NFA-SiC composites had relative lower hardness than the pure SiC samples. A carbon layer was introduced in the NFA particles to prevent the reaction between NFA and SiC. Results indicated that the carbon layer was effective up to 1050 degree C sintering temperature. Green samples of gradient-structured NFA-SiC composites were successfully fabricated through slip casting of an NFA-SiC co-suspension. / Master of Science

Darknet markets have emerged due to technological advancements, decreasing the likelihood of violence by facilitating remote purchasing interactions. However, the absence of traditional legal frameworks makes maintaining order in these illegal online markets challenging. Without a legitimate state to enforce property rights or quality standards, sustaining order becomes increasingly complex. Despite its illicit nature and the absence of a legitimate state to protect market transactions, the darknet market has proven to be a resilient environment where user satisfaction rivals that of traditional e-commerce platforms such as eBay. How is this possible? Howcan social order emerge in such a context? Existing studies have primarily approached the issue from neo-institutionalist and social network perspectives, examining the emergence of social order through informal institutions and repeated interactions. A notable gap remains in understanding the cognitive aspects shaping decision-making processes in these illicit markets. This dissertation aims to fill this gap by examining the role of social influence in establishing the social order of the market in the absence of legal safeguards from a socio-cognitive lean.

Die Sicherstellung der Versorgung mit Trinkwasser ist von entscheidender Bedeutung für das Funktionieren unserer Gesellschaft. Dieses Paper untersucht mit einem ganzheitlichen Blick Maßnahmen, die für die Sicherheit in der Trinkwasserversorgung erforderlich sind. Zu Beginn wird ein Einblick in die gesetzlichen Rahmenbedingungen für KRITIS-Betreiber gegeben. Anschließend erfolgt die Betrachtung eines Fallbeispiels bei einem regionalen Trinkwasserversorger im Kontext von kritisch anzusehenden Einrichtungen. Es wird dargestellt, wie Sicherheitsmaßnahmen in der Praxis nach dem Stand der Technik umgesetzt werden. Das Paper verfolgt das Ziel, ein Verständnis für die Bedeutsamkeit von Schutzmaßnahmen in derWasserversorgung zu schaffen und stellt dabei in der Praxis eingesetzte Methodiken vor. In Bezug auf kleine und mittlere Unternehmen soll ein Ansatz geboten werden, um die wesentlichen Empfehlungen, welche im „SektorWasser“ gelten, zu prüfen und kritisch zu bewerten.

OPTIMUS MOTUS (R) ist ein grafischer Editor, um komplexe Bewegungsabläufe zu modellieren, zu optimieren, zu testen und schließlich als Funktionsbausteine für die SPS-Welt zu exportieren. So können SPS-Bewegungsprogramme erheblich schneller entwickelt und geändert werden als bei manueller Programmentwicklung. Die aus der Kurventechnik bekannte Bewegungsqualität kommt damit auch bei Servoantrieben zum Tragen. Das Debugging entfällt, weil die Quelltexte maschinell erzeugt werden.

La criminalità organizzata ha aumentato la propria presenza nell’economia legale attraverso l’infiltrazione in aziende, generando così delle conseguenze negative per il sistema economico e alterando le relazioni tra attori economici. Molti paesi europei hanno adottato dei sistemi di recupero di capitali illeciti, ma l’Italia è la sola che prevede anche il recupero di aziende come misura di contrasto efficace. La politica di recupero dei capitali illeciti dovrebbe ridurre l’infiltrazione della criminalità organizzata nelle aziende, ma ad oggi è assente una valutazione la politica di recupero delle aziende infiltrate da gruppi criminali. Questa tesi intende valutare la politica di recupero delle aziende infiltrate dalla criminalità organizzata in Italia. L’analisi riguarda la valutazione dell’efficacia, efficienza e impatto di questa politica e, attraverso lo studio di nove casi, propone un nuovo quadro di analisi che combina diversi metodi (es. analisi degli indici di bilancio) e fonti (es. casi giudiziari e bilanci). Lo studio dei casi mostra che il recupero delle aziende è efficace se l’amministratore giudiziario ha esperienze manageriali; è efficiente se i procedimenti di recupero sono brevi e l’azienda viene destinata ad uso sociale; ed ha un impatto positivo se i media e le associazioni locali si interessano alle sorti dell’azienda. / By misusing legitimate businesses, organised crime is increasingly present in legal economies, generating serious consequences for legal systems and distorting relationships among legal actors. Several European countries have adopted asset-recovery regimes, but Italy is the only one that foresees the confiscation of companies as an effective countermeasure. Taking profits out of crime should curtail its infiltration into legitimate businesses, but there are no evaluations of the recovery of companies once infiltrated by organised crime. This study aims to evaluate the recovery of confiscated companies infiltrated by organised crime in Italy. It measures the effectiveness, efficiency and impact of this policy, and, analysing nine cases to assess the achievement of the policy objectives, proposes a new analytical framework that combines different methods (e.g. financial ratio analysis) and sources (e.g. judicial files and balance sheets) to evaluate asset-recovery policies. The results from case studies show that the recovery of companies is effective if the legal administrator has managerial skills; it is efficient if the proceedings are short and the company is disposed to social reuse; and it has a positive impact if media and local associations show an interest in the company.

L’étude a pour objectif l’amélioration de la fiabilité des assemblages électroniques à travers la mise en œuvre de drains composites aluminium/fibres de carbone. Le travail a consisté à 1) modéliser, par la méthode des éléments finis, l’influence des propriétés thermiques et mécaniques du matériau de semelle sur l’assemblage életronique ; 2) élaborer (par frittage sous charge uniaxiale, frittage flash et extrusion à chaud) des matériaux composites aluminium/fibres de carbone ; et 3) lier les microstructures observées aux paramètres des procédés d’élaboration ainsi qu’aux propriétés thermiques et mécaniques mesurées. / This study has been done in order to improve power electronic devices reliability using aluminium/carbon fibres composites. This work has consisted in 1) determining, using finite elements method, the thermal and mechanical influence of the electronic base plate material; 2) elaborating (using hot pressing, spark plasma sintering and hot extrusion) aluminium/carbon fibres composites; and 3) linking the microstructures observed to the elaboration parameters and to the thermomechanical properties measured.

O objetivo desse trabalho foi desenvolver um compósito cerâmico de zircônia-grafeno para aplicação odontológica. Este estudo avaliou o efeito do pó de partida, concentração de grafeno e da temperatura de sinterização sobre as propriedades mecânicas (dureza e tenacidade à fratura) do compósito desenvolvido. Para isto foram sintetizados os pós de Y-TZP a partir de soluções de óxido-cloreto de zircônio e cloreto de ítrio na proporção desejada de 3mol% através da rota de co-precipitação em solução de hidróxido de amônio seguido por uma série de lavagens em água, etanol e butanol com posterior destilação azeotrópica, secagem, moagem e calcinação. O grafeno foi obtido a partir da exfoliação química de grafite pelo método de Hummers [40] modificado por Marcano [39], o que resultou em um gel acastanhado que foi submetido a lavagem por centrifugação, secagem e desaglomeração em almofariz de ágata, resultando, por fim, no óxido de grafeno. Uma segunda etapa foi o processo de redução química com ácido ascórbico para obtenção de óxido de grafeno reduzido, um pó de coloração escura que foi adicionado à Y-TZP para a obtenção do compósito nas diversas concentrações (em mol%) que foram estudadas: (0,01%, 0,05%, 0,10%, 0,50%, 1,00% e 2,00%). Os pós foram caracterizados por termogravimetria, difração de raios X e espectroscopia (FT-IR). Os espécimes foram confeccionados em matriz metálica cilíndrica e sinterizados em forno tubular em atmosfera inerte. Outros espécimes foram confeccionados em matriz de grafite de alta densidade e sinterizados por Spark Plasma Sintering (SPS). Todas as amostras foram caracterizadas por meio de ensaios de densidade, dureza Vickers, tenacidade à fratura e microscopia eletrônica de varredura. Os maiores valores de densidade relativa foram observados para as amostras sinterizadas em SPS, sendo que se obteve valor de densidade relativa de 98,7 % para a concentração de 0,50% de grafeno e 98,4% para a Y-TZP pura. Por outro lado, o maior valor encontrado em sinterização em atmosfera a 1400°C sem a presença de H2 para Y-TZP pura foi da ordem de 96,76%. Os valores de dureza foram maiores nas amostras sinterizadas em SPS, no entanto a tenacidade à fratura mostrou não se alterar em função do conteúdo de grafeno. As fotomicrografias de MEV mostraram que houve uma variação de tamanho de grão de acordo com a presença do grafeno e do método de sinterização. De acordo com os resultados obtidos neste trabalho foi possível concluir que o processamento desenvolvido permitiu a criação de um compósito cerâmico zircônia-grafeno que pôde ser caracterizado por diversos métodos analíticos. A densidade teórica do compósito desenvolvido não foi alcançada por meio de nenhum dos métodos de sinterização utilizados (Tubular ou SPS) e nem variando-se a temperatura. Para espécimes sinterizados em atmosfera inerte, a maior temperatura de sinterização (1400°C) e a presença do gás H2 não melhorou a densificação. Além disso, esses espécimes tiveram aumento da dureza com o aumento da concentração de grafeno, entretanto, a sua tenacidade à fratura não foi afetada pelo teor de grafeno. Para espécimes sinterizados por meio de SPS, a temperatura de sinterização de 1350°C resultou em melhores valores de densificação. Além disso, para este tipo de sinterização, tanto a dureza como a tenacidade à fratura foram afetadas pelo teor de grafeno. / The objective of this work was to develop a zirconia-graphene ceramic composite for dental application. The study evaluated the effect of the starting powder effect, graphene concentration and sintering temperature on the mechanical properties of the composite. For this, the Y-TZP powders were synthesized from zirconium chloride and yttrium chloride solutions in the desired ratio of 3 mol% through the co-precipitation route in ammonium hydroxide solution followed by a series of washes in water, ethanol and butanol with subsequent azeotropic distillation, drying, grinding and calcination. Graphene was obtained from the chemical exfoliation of graphite by the method of Humans modified by Marcano, which resulted in a brownish gel that was subjected to washing by centrifugation, drying and deagglomeration in agate mortar, resulting finally in the graphene oxide. A second step was the chemical reduction with ascorbic acid to obtain reduced graphene oxide, a dark-colored powder that was added to the Y-TZP to obtain the composite in the various concentrations (in mol%) that were studied (0, 01%, 0.05%, 0.10%, 0.50%, 1.00% and 2.00%). The powders were characterized by thermogravimetry, X-ray diffraction and spectroscopy (FT-IR). The specimens were made in cylindrical metallic matrix and sintered in a tubular oven. Other samples were made in high density graphite matrix and sintered by Spark Plasma Sintering (SPS). All samples were characterized by means of density tests, Vickers hardness, fracture toughness and scanning electron microscopy. The highest values of relative density were observed for the sintered samples in SPS. A relative density of 98.7% was obtained for the 0.50% concentration of graphene and 98.4% for the pure Y-TZP. On the other hand, the highest value found in tubular sintering at 1400 ° C without the presence of H2 for pure Y-TZP was of the order of 96.76%. The hardness values were higher in the sintered samples in SPS, however the fracture toughness showed not to change as a function of the content of graphene. SEM images showed that there was a variation of grain size according to the presence of graphene and the sintering method. According to the results of this study it was concluded that the process developed allowed the creation of a graphene-zirconia ceramic composite which can be characterized by various analytical methods. The theoretical density of the composite developed was not achieved by any of the sintering methods used (tubular or SPS) nor by varying the temperature. For tubular sintered specimens, the higher sintering temperature (1400 ° C) and the presence of H2 gas did not improve densification. In addition, these specimens had increased hardness with increasing graphene concentration, however, their fracture toughness was not affected by graphene content. For sintered specimens by SPS, the sintering temperature of 1350 ° C resulted in better densification values. In addition, for this type of sintering, both hardness and fracture toughness were affected by the content of graphene

Comprendre les mécanismes de spéciation des Produits de Fission (PF) dans le combustible nucléaire est un enjeu majeur pour pouvoir estimer précisément le terme source d’un accident grave. Parmi les nombreux PF créés, certains sont très réactifs et peuvent avoir un impact radiologique important en cas de relâchement dans l’atmosphère. C’est notamment le cas du césium (Cs), du molybdène (Mo) et du baryum (Ba). C’est dans ce contexte que s’inscrit le travail de thèse qui propose d’apporter des données expérimentales sur l’effet du potentiel oxygène sur la spéciation du Cs, du Mo et du Ba dans des combustibles nucléaires, à différents stades d’un accident grave.Une approche thermodynamique a été utilisée en support à l’interprétation des données expérimentales obtenues dans le cadre de ce travail. Deux types d’échantillons ont été étudiés: des combustibles MOX irradiés et des matériaux simulant un combustible UO2 à fort taux de combustion, obtenus par frittage à haute température (SIMFuel). Les échantillons ont été traités thermiquement dans des conditions représentatives d’un accident grave survenant dans un Réacteur à Eau Pressurisée (REP). Les conditions expérimentales ont couvert une gamme de température allant de 400°C à 2530°C et des potentiels oxygène situés entre -470 kJ.mol(O2)-1 et -100 kJ.mol(O2)-1. Les échantillons ont été caractérisés finement avant et après chaque traitement à l’aide de techniques complémentaires comme la microscopie optique et électronique, la microsonde et le SIMS dans le cas de l’irradié. Des mesures de XANES sur synchrotron ont été réalisées sur SIMFuel et ont conduit à des résultats importants en termes de spéciation des PF. Enfin, la technique de Spark Plasma Sintering (SPS) a été explorée avec succès pour la fabrication de SIMFuel contenant du Cs, du Mo et du Ba sous des formes chimiques représentatives d’un combustible REP en fonctionnement nominal.Ce travail a permis de mettre en évidence l’effet de la température en conditions oxydantes sur le comportement du combustible et des PF. Une oxydation du Mo, initialement présent sous forme métallique dans les inclusions blanches du combustible, en MoO2 a été observée dès 1000°C en conditions oxydantes. Une interaction entre le MoO2 formé et le Ba contenu dans la phase oxyde a eu lieu dans les mêmes conditions, menant à la formation de BaMoO4. Le potentiel oxygène joue aussi un rôle important dans le phénomène d’interaction pastille-gaine, en favorisant la diffusion des espèces en conditions oxydantes, diminuant ainsi la température de fusion du combustible. / In the nuclear community, it is a top priority to gain in-depth understanding of fission product (FP) speciation mechanisms occurring in nuclear fuel in order to precisely estimate the source term of a severe accident. Among the FP produced, some are highly reactive and may have a strong radiological impact if released into the environment. This is particularly the case of cesium (Cs), molybdenum (Mo) and barium (Ba). In this context, the objective of this study is to provide experimental data on the effect of the oxygen potential on Cs, Mo and Ba speciation in nuclear fuels at different stages of a severe accident.A thermodynamic approach was coupled with the experimental work to support the interpretation of experimental data. Two types of samples were studied in detail: irradiated MOX fuels and simulated high burn-up UO2 fuels produced through sintering at high temperature (SIMFuel). The samples were submitted to thermal treatments in conditions representative of a pressurised water reactor (PWR) severe accident. This approach made it possible to cover a temperature range from 400°C up to 2530°C and oxygen potentials from -470 kJ.mol(O2)-1 to -100 kJ.mol(O2)-1. The samples were characterized before and after each test using complementary techniques like OM, SEM, EPMA and SIMS in the case of irradiated fuels. XANES measurements using synchrotron radiation facilities were performed on SIMFuels and provided valuable results on FP speciation. Moreover, spark plasma sintering (SPS) was successfully investigated for the production of SIMFuel samples containing Cs, Mo and Ba in a chemical state representative of PWR fuel in normal operating conditions.This work highlighted the effect of oxidizing severe accident conditions on the fuel and FP behavior. Oxidation of Mo initially contained in the fuel’s metallic inclusions into MoO2 was observed to take place around 1000°C in oxidizing conditions. An interaction between MoO2 and the oxide phase containing Ba took place in the same conditions, leading to the formation of BaMoO4. The oxygen potential also plays an important role in fuel-cladding interactions, enhancing the diffusion of species in oxidizing conditions and lowering the temperature at which fuel melting occurs.

L'élaboration de céramiques polycristallines transparentes constitue un défi technologique important. Les matériaux transparents actuellement utilisés (verres ou monocristaux) possèdent des propriétés mécaniques (dureté, résistance à l'usure) et physico-chimiques (résistance à la corrosion) moins intéressantes que celles des céramiques polycristallines. Par ailleurs, le coût de production de ces dernières est inférieur à celui des monocristaux. Les deux principaux paramètres à contrôler afin d'augmenter les propriétés optiques de l'alumine alpha polycristalline sont sa porosité, comme pour tout matériau transparent, et sa taille de grains, du fait de sa biréfringence. Aussi on cherchera à obtenir après frittage un matériau possédant une très faible porosité (inférieure à 0,05%) avec une distribution fine en taille de pores centrée sur des porosités nanométriques, et une taille de grains très fine (plus grand que 0,5 µm). Actuellement, cette microstructure particulière est obtenue en ~ 15 heures en combinant un frittage naturel suivi d'un traitement par Hot Isostatic Pressing (HIP). La technique de Spark Plasma Sintering (SPS) utilisée dans cette étude permet d’obtenir des céramiques denses possédant une microstructure fine en des temps plus courts. Premièrement, un protocole d'élaboration d'une alumine pure transparente a été mis au point. Il repose sur la préparation de crus à microstructure contrôlée avant l'étape de frittage. Principalement, ils doivent présenter une distribution fine en taille de pores avec un empilement particulaire macroscopique homogène dépourvu d'agglomérats. Le cycle de frittage SPS a également été optimisé afin d'obtenir les meilleures transmissions optiques possibles. Ensuite, un protocole de dopage par des inhibiteurs de croissance de grains a été optimisé. La nature du sel dopant influe au second ordre sur les propriétés optiques des échantillons par rapport à une calcination préalable au frittage. La nature et/ou la quantité de dopant induisent un décalage plus ou moins important de la densification vers les hautes températures. Le cycle de frittage SPS doit donc être adapté en conséquence. Le taux de dopant doit être optimisé afin d'obtenir une microstructure fine après frittage sans présence de particules de seconde phase. Différents dopants ont été comparés (magnésium Mg, lanthane La et zirconium Zr) et l'échantillon possédant les meilleures propriétés optiques a été obtenu grâce à un dopage à 200 cat ppm de lanthane. Des optimisations au niveau de la morphologie des poudres (plus fines et plus sphériques) et de la préparation des suspensions d'alumine alpha dopées au lanthane (lavage par centrifugation) ont permis d'obtenir l'un des meilleurs échantillons d'alumine transparente reporté dans la littérature. Il possède une transmission optique de 68% et une taille de grains de l'ordre de 300 nm. Ses propriétés mécaniques (dureté, résistance à l'abrasion) sont supérieures à celles d'un monocristal de saphir. / Obtaining transparent polycrystalline ceramics became an important technological challenge over the last decade. Their high mechanical (hardness, wear resistance) and physico-chemical (corrosion resistance) properties combined with a high transparency and a reasonable price could lead them to replace glasses or monocrystals as sapphire in optical applications. The main parameters to control in order to obtain highly transparent polycrystalline alpha-alumina (PCA) are the porosity size and amount as for the other transparent materials. However, as PCA is a birefringent material, the grain size also needs to be controlled. That’s why PCA should possess after sintering grains as small as possible (bigger than 0.5 µm) and a porosity closed to 0.00% with nanometric pores. This particular microstructure is usually obtained in ~ 15 hours by combining natural sintering in air with a post Hot Isostatic Pressing (HIP) treatment. In our study, the Spark Plasma Sintering (SPS) technique was used as it enables to obtain fully dense ceramics in shorter times while limiting the grain growth. First, a protocol to obtain a pure transparent PCA was established. It consists on preparing green bodies with a controlled particle’s packing before sintering. Mainly, the particle’s packing has to be macroscopically homogeneous and without agglomerates. Moreover, the pore size distribution should be the narrowest. The SPS sintering cycle was also optimised to obtain the highest optical transmission. Then, a doping protocol with grain growth inhibitors was optimised. The nature of the doping salt has a secondary effect on optical properties compared to a thermal treatment applied before sintering. Depending on the doping agent nature and/or amount, the densification temperature changes. The SPS sintering cycle has thus to be adapted. The doping agent amount has to be optimised to obtain a fine microstructure after sintering without second phase particles. Different doping agents have been compared (magnesium Mg, lanthanum La and zirconium Zr). The sample having the highest optical properties was doped with 200 cat ppm of lanthanum. Finally, an optimisation of the powder’s morphology (finer and more spherical) was performed. Moreover, the lanthanum doped alpha-alumina slurry’s preparation was optimized using centrifugation. All these processes have enabled us to obtain one of the most transparent PCA sample ever reported in the literature. It possesses an optical transmission of 68% and a grain size around 300 nm. Its mechanical properties (hardness, wear resistance) are higher than the ones of a sapphire monocrystal.