Nowadays there is research into molten salt reactors. The use of chlorine-based salts, which would be more available than known fluoride salts, is envisaged. The subject of research is not only the chemical and physical properties of chloride salts, but also their behavior in the neutron field and the influence of neutron balance inside the reactor. Many properties can also be determined using calculations that draw information from scientific nuclear libraries (endf). The purpose of this work is to compare important nuclear libraries with each other, and also to compare the reaction rates calculated from the library data with the reaction rates obtained by self-measurement. The preview will include a description of the necessary activities associated with the preparation of measurements, instructions for compiling the computer program NJOY and the process of the measurement itself. At the end of the work will be summarized the results and statements of which nuclear library is the closest in its values to the results of experiments.

Cette thèse a été réalisée initialement dans le cadre du projet Stockage Thermique Appliqué à l’extension de Production d’énergie Solaire thermodynamique (STARS) soutenu par l'Agence De l'Environnement et de la Maîtrise de l'Energie (ADEME).L’objectif du projet est de développer une solution de stockage thermique adaptée à la technologie Fresnel à génération directe de vapeur avec une zone de stockage de chaleur latente. Dans une unité de stockage latent, le nitrate de sodium (NaNO3) a été choisi comme matériau à changement de phase (MCP) et l’acier faiblement allié a été envisagé comme matériau de structure du conteneur et de l’échangeur thermique. La contribution de la thèse se positionne au niveau de l’étude de la corrosion et de la durabilité des matériaux de structure (conteneur et échangeur) en contact avec le MCP. L’objectif est de déterminer une loi de vitesse de corrosion qui permettrait de dimensionner les parois de l’échangeur et de développer des protocoles utilisant les techniques électrochimiques afin de suivre in-situ l’état de la corrosion au sein de l’unité de stockage. Les travaux présentés dans ce manuscrit portent sur l’étude expérimentale de la corrosion de l’acier dans le nitrate de sodium fondu à 340°C en fonction des paramètres expérimentaux tels que la présence d’impuretés (oxydes, chlorures), l’atmosphère gazeuse et le cyclage thermique. L’étude par mesures gravimétriques met en évidence la formation d’une couche de corrosion protectrice en surface de l’acier et la production de nitrite de sodium (NaNO2) par la réaction de corrosion. Cette couche constituée principalement de Fe2O3 (insoluble dans NaNO3 fondu) a été caractérisée par différentes méthodes d’analyse de surface (DRX, XPS). L’évolution de l’épaisseur de la couche de corrosion obtenue par cette technique montre une cinétique de corrosion logarithmique dans NaNO3 pur et une cinétique linéaire en présence d’une teneur importante en impuretés chlorures (10 mol%). L’étude électrochimique a apporté des indications sur le comportement du fer (et de l’acier) dans NaNO3 fondu. En combinant ces données avec les observations expérimentales issues des essais de corrosion nous avons pu proposer un mécanisme réactionnel pour la corrosion de l’acier en milieu nitrate fondu. L’étude par spectroscopie d’impédance électrochimique a permis de valider le mécanisme réactionnel proposé. A l’aide de ce mécanisme, les paramètres cinétiques puis la valeur du courant de corrosion ont été déduits par simulation des diagrammes d’impédance. L’analyse de la variation du courant de corrosion en fonction du temps permet de calculer l’épaisseur de la couche de corrosion et de la comparer à celle obtenue par gravimétrie. Un bon accord entre les valeurs obtenues par différentes techniques a été observé.Au cours de ce travail, nous avons également montré la possibilité d’utiliser les techniques électrochimiques pour l’instrumentalisation des installations industrielles afin de suivre in-situ l’évolution de la composition du MCP et l’état d’avancement de la corrosion de l’acier.Enfin, ce travail a montré que l’acier faiblement allié est adapté pour être utilisé dans une unité de stockage latent avec le nitrate de sodium comme matériau à changement de phase. / This thesis was originally performed as part of the STARS project (Stockage Thermique Appliqué à l’extension de Production d’énergie Solaire thermodynamique) which was supported by ADEME (l'Agence De l'Environnement et de la Maîtrise de l'Energie). The objective is to develop a thermal storage system using latent heat from a phase change material (PCM) in order to match with Fresnel technology using direct steam generation. Sodium nitrate (NaNO3) has been selected as PCM and low-alloy steel has been considered as candidate material to build the container and the heat exchanger of a latent heat storage system. The contribution of this thesis is to provide better understanding of the corrosion of the candidate material in contact with the PCM. This thesis aims to determine a corrosion rate law which helps design the thickness of the heat exchanger’s wall and to develop protocols using electrochemical technics to follow in-situ corrosion process in the latent heat storage system. The work presented in this manuscript focuses on experimental study of corrosion of low-alloy steel in molten NaNO3 (340°C) in function of different parameters: presence of impurities (oxides, chlorides), atmosphere and thermal cycling. Gravimetric measurements reveal the formation of a protective corrosion layer on the steel’s surface and the production of sodium nitrite (NaNO2) by corrosion reaction. The corrosion layer consisting mainly of Fe2O3 (insoluble in molten NaNO3) was characterized by surface analytical methods (XRD, XPS). Variation of the thickness of corrosion layer obtained by gravimetric methods shows logarithmic kinetics in pure NaNO3 and linear kinetics in the presence of 10mol% of impurity chlorides. Electrochemical study has provided indications on the iron (and steel) behavior in molten NaNO3. By combining results of this study with experimental observations from gravimetric study, we were able to propose a corrosion mechanism of the steel in molten NaNO3. This mechanism was then validated by electrochemical impedance spectroscopy study. Kinetics parameters and value of corrosion current were deduced by the simulation of impedance diagrams using the proposed mechanism. The thickness of corrosion layer was calculated by analyzing the variation of the corrosion current with time. These values present a good agreement with values obtained by gravimetric study.In this work, we also show the possibility of using electrochemical measurements at industrial scale to follow in-situ the evolution of the PCM's composition and the corrosion state. Finally, this work has shown that low-alloy steel is suitable for using in a latent heat storage system with NaNO3 as phase change material.

En la presente investigación realizada se evaluaron las propiedades físicas de los agregados, para el cual se ejecutó diseños de mezclas con la finalidad de determinar las propiedades mecánicas del concreto adicionado con viruta de acero fundido en porcentajes de 3% ,6% y 9% como reemplazo parcial del agregado fino. La finalidad de evaluar las propiedades mecánicas del concreto adicionado con viruta de acero fundido, es comprobar la resistencia a la compresión, tracción y flexión en los diferentes porcentajes y edades. Para los ensayos se realizaron diseños de concreto patrón y concreto con adición de viruta acero fundido, según la norma (ACI 211, 2009) para una resistencia a la comprensión de 210 kg/cm2. El estudio estimo la evaluación de las propiedades mecánicas del diseño de concreto patrón en estado fresco (temperatura, slump, peso unitario), y en estado endurecido (resistencia a la compresión, flexión y tracción), evaluación que se realizó también en el diseño de concreto con adición de viruta de acero fundido al 3%, 6% y 9%. Al finalizar los ensayos se observó que el diseño de estudio de concreto con adición de viruta de acero fundido aumenta su resistencia a la compresión, flexión y tracción. / In the present investigation carried out, the physical properties of the aggregates were evaluated, for which mixture designs were executed in order to determine the mechanical properties of the concrete added with molten steel shavings in percentages of 3%, 6% and 9% as partial replacement of fine aggregate. The purpose of evaluating the mechanical properties of concrete added with molten steel shavings is to check the resistance to compression, traction and bending in the different percentages and ages. For the tests, designs of standard concrete and concrete with addition of cast steel shavings were made, according to the (ACI 211, 2009) standard for a resistance to compression of 210 kg / cm2. The study estimated the evaluation of the mechanical properties of the pattern concrete design in the fresh state (temperature, slump, unit weight), and in the hardened state (resistance to compression, bending and traction), evaluation that was also carried out in the design of concrete with addition of 3%, 6% and 9% cast steel shavings. At the end of the tests, it was observed that the concrete study design with the addition of molten steel shavings increases its resistance to compression, bending and traction. / Tesis

Gegenstand der vorliegenden Arbeit war es, die Grundlagen für ein mögliches technisches Verfahren zur Aromatennitrierung mit Salzhydratschmelzen (M(NO3)3 · n H2O, M = Fe, Cr, Bi, In, Al; n = 4 - 9) zu untersuchen. Es sollte geklärt werden, ob Toluol quantitativ zu Dinitrotoluol bzw. Benzol zu Nitrobenzol umgesetzt werden kann. In Screening-Versuchen wurden geeignete, nitrierend wirkende Salzhydrate ermittelt, sowie Wege untersucht, die Reaktivität der eingesetzten Salzhydratschmelzen durch Variation von Wasser- bzw. Säuregehalt, Durchmischung, verschiedenen Schmelzenzusätzen bzw. Reaktionstemperatur zu steigern. Das entstehende Verhältnis der Isomeren der Mono- und Dinitrierung wurde hinsichtlich einer möglichen Beeinflussung untersucht. Das Spektrum an Nebenprodukten wurde bestimmt, sowie Möglichkeiten aufgezeigt, diese zu vermeiden. Dabei konnte gezeigt werden, dass im Gegensatz zum etablierten Mischsäureverfahren beim Einsatz von Salzhydratschmelzen keine kresolischen Nebenprodukte gebildet werden. Weiterhin wurden Möglichkeiten zur Präparation wasserarmer Salzhydratschmelzen durch thermische Entwässerung bzw. Reaktion mit flüssigem N2O4 untersucht, die Löslichkeit der isomeren Zwischen- und Endprodukte in der Salzhydratschmelze bestimmt sowie das thermische Verhalten von Dinitrotoluol in Gegenwart der Salze betrachtet.

Research on bainite and martensite structures has indicated that lower bainite needles have a refining effect on the lath martensitic structure. Lower bainte needles partitions prior austenite grains and will consequently have a refining effect on the subsequent formed lath martensite. Smaller austenite grains will result in smaller lath martensitic packets and blocks and will result in enhanced mechanical properties.   In order to create a variation of lower bainte structure in a matrix of martensite, two different heat treating methods were tested. The work was focused towards the formation of lower bainite during isothermal heat treating in molten salt, above and below the MS-temperature. Both un-tempered and tempered samples were analyzed .Two different materials were tested, both were AISI 4140 but with a slightly difference in hardenability. The material provided by Ovako Steel is 326C and 326F the later had a higher hardenability. In order to better distinguish the two structures from each other when studied under a microscope, a variation of etching methods were tested.  It was possible to create a variation of lower bainite structures in a matrix of martensite.  326F shows less amount of lower bainite and provides a higher average surface hardness before tempering.

<p>U ovoj doktorskoj disertaciji proučavano je građenje&nbsp;kompleksa kobalta(II) sa hloridnim i &nbsp;bromidnim jonima u&nbsp;rastopima koji sadrže jednu neorgansku so i jedno organsko&nbsp;jedinjenje i/ili vodu pri različitom sastavu sistema i na različitim&nbsp;temperaturama. Jedan od sistema je amonijum-nitrat &ndash;&nbsp;acetamid &ndash; voda sastava NH₄NO₃∙(2,61-z)CH₃CONH₂∙zH₂O (z =&nbsp;0,0 1,61 i 2,61), a drugi sistem je amonijum&ndash;nitrat &ndash; dimetilsulfoksid&nbsp;(DMSO) sastava NH₄NO₃∙zDMSO (z = 1 &ndash; 6), &nbsp;na&nbsp;različitim temperaturama (35, 45, 55 i 65 ^oC).&nbsp;Cilj ovog istraživanja je bio određivanje stabilnosti&nbsp;kompleksa kobalta koji se grade sa sa halogenidnim jonima i&nbsp;komponentama rastvarača, pronalaženje kvalitativne i kvantitativne&nbsp;zavisnosti konstanti stabilnosti kompleksa kobalta(II) sa&nbsp;halogenidnim jonima od temperature i molskog odnosa&nbsp;komponenti sistema NH₄NO₃∙(2,61-z)CH₃CONH₂∙zH₂O odnosno &nbsp;NH₄NO₃∙zDMSO, određivanje termodinamičkih parametara koji&nbsp;karakteri&scaron;u reakcije asocijacije u ovim sistemima.</p> / <p>In this dissertation the complex formation between cobalt(II) and halide ions in the melts consisting of one inorganic salt, an organic compound and/or water has been studied at different temperatures. Two molten salt systems have been investigated: 1) &nbsp;ammonium nitrate-acetamide-water system NH₄NO₃∙(2,61-z)CH₃CONH₂∙zH₂O (z = 0.0 1.61 2.61) and 2) ammonium nitratedimethyl sulfoxide NH₄NO₃∙zDMSO (z = 1 &ndash; 6), at four different temperatures: 35, 45, 55 and 65 ^oC. The purpose of this work was to determine stability of cobalt(II) complexes formed with the halide ions and the components of the solvents, to discribe the qualitative and quantitative relationships between the stability of the complexes and the melt composition, as well as the changes in the cobalt(II) coordination due to a complex formation. Thermodynamic parameters for cobalt(II) &ndash; halide association process in these melts were alsodetermined.</p>

<p>U ovoj doktorskoj disertaciji proučavano je građenje kompleksa&nbsp;kobalta(II) sa hloridnim i &nbsp;bromidnim jonima u vodenim&nbsp;rastopima tipa&nbsp;xCa(NO3)2&middot;zH₂O&nbsp;&ndash; (1-x)NH₄NO_3&nbsp;pri različitom sastavu soli (x= 0,3 &ndash; 0,9), različitom sadržaju vode (z= 2,67 &ndash; 6,67) i na različitim temperaturama (45, 55 i 65^oC).</p><p>Istraživanja su imala za cilj proučavanje reakcije građenja&nbsp;kompleksa kobalta(II) sa hloridnim i bromidnim jonima u&nbsp;vodenim rastopima xCa(NO₃)₂&middot;zH₂O &ndash; (1&ndash;x)NH₄NO₃, &nbsp;uticaja&nbsp;temperature, sastava elektrolita i sadržaja vode na proces&nbsp;kompleksiranja, kao i određivanje termodinamičkih parametara&nbsp;koji karakteri&scaron;u reakcije asocijacije u ovim sistemima. Ovakvi&nbsp;rastopi soli su posebno interesantni zbog svoje niske tačke&nbsp;topljenja i visoke latentne toplote topljenja pa se mogu koristiti&nbsp;kao fazno-promenljivi materijali za skladi&scaron;tenje toplotne&nbsp;energije.</p> / <p>In this thesis absorption spectra of cobalt(II) chloride and&nbsp;bromide in calcium nitrate &ndash; ammonium nitrate &ndash; water&nbsp;system of the composition&nbsp; xCa(NO₃)₂&middot;zH₂O &ndash; (1&ndash;x)NH₄NO_3&nbsp;(x= 0.30 - 0.90 and z= 2.67 &ndash; 6.67) have been&nbsp;investigated in the wavelength range 400-800 nm at three&nbsp;different temperatures: 45, 55 and 65^oC.</p><p>Temparature, composition of the melt and water&nbsp;content influence on complex formation reactions between&nbsp;cobalt(II) and halide ions in aqueous xCa(NO₃)₂&middot;zH₂O &ndash;<br />(1&ndash;x)NH₄NO₃ melts have been studied. Thermodynamic&nbsp;parameters for cobalt(II) &ndash; halide association process in&nbsp;different solvents also were determined.</p><p>Investigated systems are interesting because of&nbsp;their high values of latent heat of fusion and low melting&nbsp;points. Due to these reasons, some melts are proposed for&nbsp;<br />heat energy storage materials, usually known as phase&nbsp;change materials (PCM).</p>

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Die Brennstoffzelle ist ein elektrochemischer Reaktor und wandelt chemisch gebundene Energie direkt in elektrische Energie um. In der stationären Energieerzeugung ist der Brennstoffzellenstapel selbst nur ein kleiner Bestandteil des vollständigen Systems. Die Integration aller zusätzlichen Bestandteile, der Peripheriegeräte (Balance-of-Plant) (BoP), ist eine der Hauptaufgaben in der Studie der Brennstoffzellenkraftwerke. Diese Untersuchung betrifft die Systemstudie des auf der Schmelz-Karbonat-Brennstoffzelle (MCFC) basierten Kraftwerks. Die Systemstudie ist mit dem Simulationprogramm Aspen PlusTM durchgeführt worden. Artikel I beschreibt die Implementierung eines in Aspen PlusTM entwickelten MCFC Stapelmodells, um ein MCFC Kraftwerk zu studieren, das Erdgas als Brennstoff verwendet. Artikel II beschreibt, wie unterschiedliche Prozeßparameter, wie Brenngasnutzung und dieWahl des Brennstoffes, die Leistung eines MCFC Kraftwerks / A fuel cell is an electrochemical reactor, directly converting chemically bound energy to electrical energy. In stationary power production the fuel cell stack itself is only a small component of the whole system. The integration of all the auxiliary components, the Balance-of-Plant (BoP), is one of the main issues in the study of fuel cell power plants. This thesis concerns the systems studies of molten carbonate fuel cell (MCFC) based power plants. The system studies has been performed with the simulation software Aspen PlusTM. Paper I describes on the implementation of a developed MCFC stack model into Aspen PlusTM in order to study an MCFC power plant fueled with natural gas. Paper II describes how different process parameters, such as fuel cell fuel utilization, influence the performance of an MCFC power plant. / Bränslecellen är en elektrokemisk reaktor som kan direkt omvandla kemiskt bunden energi till elektrisk energi. I stationär kraftproduktion är själva bränslecellsstapeln endast en mindre komponent i systemet. Integrationen av kringutrustningen, den s.k. Balance-of-Plant (BoP), som tex. pumpar, kompressorer och värmeväxlare är en av huvudfrågeställningarna i studierna av bränslecellskraftverk. Denna avhandling avser systemstudier av mältkarbonatbränslecellsbaserade (MCFC) kraftverk. Systemstudierna har utförts med processimuleringprogramet Aspen PlusTM. Artikel I beskriver en utvecklad MCFC-cellmodell, som implementeras som "user model" i Aspen Plus, för att studera ett naturgasbaserat bränslecellskraftverk. Artikel II beskriver hur olika processparametrar, som tex bränsleutnyttjande och val av bränsle, påverkar ett MCFC-kraftverks prestanda. / QC 20101129