Ce travail de thèse a porté sur l’étude des propriétés d’adsorption et de séparation en milieu humide par des polymères de coordination poreux. Nous avons utilisé les techniques de volumétrie d’adsorption, de séparation par chromatographie en phase gaz, de spectroscopie de fluorescence ainsi que et de la modélisation Monte Carlo afin de comprendre les mécanismes qui gouvernent l’adsorption de ces matériaux. Les molécules adsorbables étudiées sont l’eau et des vapeurs d’hydrocarbures linéaires (pentane et n-hexane), cycliques (cyclohexane et cyclohexène) et polycycliques (anthracène). Les adsorbants étudiés sont les Analogues de Bleu de Prusse (ABP) ainsi que deux matériaux organométalliques poreux de référence, le ZIF8 et le CuBTC. Parmi les résultats principaux apportés par ce travail, nous avons montré que les Analogues de Bleu de Prusse ont une stabilité hydrothermale remarquable leur conférant des propriétés d’adsorption en milieu humide très prometteuses. Parmi les ABP étudiés, le Co[CoIII(CN)6]0.66 ⊡0.33 .5.2H2O a montré des propriétés d’adsorption et de séparation très supérieures à celles d’autres ABPs. Par exemple, il a été possible de moduler sa balance hydrophobe/hydrophile par le contrôle de la coordination de l’eau sur le centre métallique insaturé, tout en préservant son caractère lipophile. Nous avons aussi montré que cet analogue de bleu de Prusse est capable de séparer des mélanges d’hydrocarbures secs ou très humides de façon répétée. Sur un aspect plus fondamental, nous avons montré que le confinement d’anthracène par le ZIF-8, qui est un composé organométallique poreux possédant des cavités de taille ajustée à celle du fluorophore, pouvait induire une extinction complète de certaines bandes d’absorption de celui-ci. / This PhD thesis is focused on the study of wet adsorption and separation properties by porous coordination polymers. We used adsorption volumetry, gas chromatography separation techniques, fluorescence spectroscopy techniques and Monte Carlo modeling to understand the mechanisms governing the adsorption of these materials. The adsorbable molecules studied are water and hydrocarbon vapors linear (pentane and n-hexane), cyclic (cyclohexane and cyclohexene) and polycyclic (anthracene). The adsorbents studied are the Prussian Blue Analogues (ABP) as well as two reference porous organometallic materials, ZIF8 and CuBTC. Among the main results provided by this work, we have shown that Prussian Blue Analogues have remarkable hydrothermal stability conferring them very promising wet adsorption properties. Among the ABPs studied, Co [CoIII (CN)6] 0.66 ⊡0.33 .5.2H2O showed adsorption and separation properties far superior to those of other ABPs. For example, it has been possible to modulate its hydrophobic / hydrophilic balance by controlling the coordination of water on the unsaturated metal center, while preserving its lipophilic character. We have also shown that this Prussian blue analogue is capable of separating mixtures of dry or very wet hydrocarbons repeatedly. On a more fundamental aspect, we have shown that the confinement of anthracene by ZIF-8, which is a porous organometallic compound with cavities of size adjusted to that of the fluorophore, could induce a complete extinction of certain absorption bands of this one.

(anglicky) The goal of my diploma thesis is to analyze Yury Buida`s prose mainly focusing on his cycle Prussian Bride, in which I will be looking for the elements typical for magical realism literature. Another question I will be exploring in this work is going to be a reflection of a historical memory of Kaliningrad Oblast inhabitants. I will be working with the works about magical realism including the one about the magical realism in Yury Buida`s work specifically, as well as with a selection of materials about historical and traumatic collective memory. The contribution of this work will be in a form of Yury Buida`s work analysis (which has not been properly studied until now) and its` representation in a context of a modern European literature studies. Key words: cycle, magical realism, memory, trauma, Yury Buida, Russian Literature of the 20th century

Opus Alchemicum explores the fabrication of “reality” upon imagination, and the affective relation between ideas and matter in the built environment. Like an alchemic experiment, through the manipulation of real facts and their transformation into myth, stories, rituals and objects, the project tries to demonstrate how myths are not just produced but also produce “real” by creating a collective understanding and a pattern of relations, roles and ideas. This project’s attempt is to reveal the mechanisms of reality in an act of analogy. The role of architecture, buildings and objects is investigated in its transfigured correspondent. Myths are both constructed and revealed as the language code of a discourse. The result is a work of alchemy, a product of imagination as a path of understanding. The project starts with traveling to Romania as a study case, in a journey where encounters and empathy win over maps and scheduled visits. What I bring back with me is a series of situations, assemblages, a pattern of history, places, culture and affections belonging to the very present of Romania.These situations are plunged in another larger assemblage, the European one, with Sweden as a partaker. In this country’s desires and metamorphoses we can discover those myths that belong and affect our culture and our spaces.  Opus Alchemicum is a tale about myths, behavior and built environment. About Romania, or somewhere else. About ruins and gold. About invisible values and material affects. About a vanished land, about desire and nostalgia. About displacement, diaspora and costumes. About migration. About a journey and the gas station at the mid of the road. About metamorphoses, gypsy palaces and dowries. About matter, produced, traded and extinguished. About Prussian Blue and honey. About a tower, a fountain and a secret garden. About the alchemic process of making reality out of ideas. / Opus Alchemicum utforskar fabricering av verklighet genom fantasi, den affektiva relationen mellan ide och materia i en bygg omgivning. Ett alkemiskt experiment, genom manipulation av verkliga fakta och deras transformation till myter, berättelser, ritualer och objekt, försöker detta projekt att påvisa hur myter inte bara är producerade utan hur de också producerar en ”verklighet” genom att skapa en kollektiv förståelse och ett mönster av relationer, roller och föreställningar. Projektet försöker att avslöja mekanismerna av verklighet i en handling av analogi. Rollen av arkitektur, byggnader och objekt undersöks i sin förvandlade korrespondens. Myter är både konstruerade och avslöjade genom språkkoden för en diskurs. Resultatet är ett verk av alkemi, en produkt av inbillningsförmåga längst en väg för förståelse. Projektet startar med en resa till Rumänien som studie fall, i en färd där möten och empati segrar över kartor och schemalagda möten. Det jag tog med mig tillbaka var en serie av situationer, samlingar och mönster av historien. Platser, kultur och känslor som representerar det nuvarande Rumänien. Situationer som störtar in till ett större sammanhang i form av det Europeiska med Sverige som deltagare. I detta lands önskningar och metamorfoser kan vi upptäcka de myter som tillhör och påverkar vår kultur och dess rum. Opus Alchemicum är en berättelse om myter, beteenden och byggd omgivning. Om Rumänien eller någon annanstans. Om ruiner och guld. Om osynliga värden och materiell inverkan. Om ett försvunnet land av begär och nostalgi. Om förskjutningar, förskingringar och kostymer. Om migration. Om färder och bensinstationen i mitten av resan. Om metamorfoser, romerska palats och hemgifter. Om materia, producerad, handlad och utsläckt. Om preussiskt blått och honung. Om ett torn en fontän och en hemlig trädgård. Om den alkemiska processen av att skapa verklighet genom idéer.

Na-ion batteries (NIBs) are expected to revolutionise the battery sector by promising an affordable technology while capitalising on sustainable development. To compete with Li-ion batteries, however, electrode materials with higher capacities need to be developed. Transition metal nitroprussides (TM-NPs), NaxM[Fe(CN)5NO]1-y ·zH2O, is a material class derived from one of the most popular positive electrode materials for NIBs, Prussian blue analogues (PBAs), where one of the cyano ligands have been replaced by an electroactive nitrosyl (NO) ligand. Thus, in theory TM-NPs should be able to reach higher capacities than PBAs and therefore be attractive candidates for high-capacity electrodes. However, if the nitrosyl is redox active in NIBs and how the cycling behaviour may be affected by the M cation is unknown. The focus in this thesis is therefore to explore the charge-discharge behaviour of four different TM-NPs (M=Fe, Ni, Mn, and Cu) in Na-ion half-cell batteries to gain an initial understanding of their electrochemical behaviour and to set up research questions to be pursued in the future. Based on our observations and previous studies, we propose that the nitrosyl is electrochemically active in all four TM-NPs, and that it contributes with a considerable amount of capacity, although with a large voltage hysteresis. It is further concluded that all M cations apart from Ni were redox active, but to varying degrees on charging and discharging. We argue that both the redox and the voltage hysteresis is caused by anisotropic charge transfer within the materials, and that it needs to be understood before commercialisation of TM-NPs can be realised. Though there are challenges to overcome, the many interesting attributes of TM-NPs, including anionic redox, anisotropic charge transfer and structural diversity, makes them promising as a new type of cheap and sustainable electrode material for NIBs.

No description available.

No description available.

Emerging markets in electrochemical energy storage, such as stationary grid storage, coupled with future concerns over the availability of lithium, places sodium-ion battery (SIB) technologies at a unique position to enter the market as a commercially viable alternative. Current shortcomings in the performance of cathode materials in SIBs would necessarily need to be addressed if this technology is to compete with existing commercial lithium-ion battery counterparts. Prussian White (PW), a promising cathode material currently being produced by Altris AB in Uppsala, Sweden, has been shown in many regards to be a promising candidate as a cathode material. In efforts to improve the lifetime, thermal stability, and rate capability of the material, both zinc oxide (ZnO) and polyaniline (PANI) coatings were applied to the active material powder.  Scanning electron microscopy (SEM) images of the ZnO coated PW showed that the ZnO was concentrated to certain regions, resulting in a rough and compromised coating. Furthermore, the notable presence of iron 2p orbital peaks in XPS spectra for ZnO and PANI coated samples, together with the SEM images, suggests that no method resulted in a conformal coating. Crystallographic information obtained using a capillary X-ray diffractometer showed that the PANI coating process had caused the PW to transition from a monoclinic to a cubic structure. This phase transition, based on subsequent thermogravimetric analysis, is attributed to an increase in both interstitial and lattice water content.  A comparative analysis of particle size and morphology, before and after slurry homogenization, showed that the ball milling technique used resulted in a reduction in size. Moreover, the ball milling process affected the uncoated PW more than the ZnO coated PW.  Findings, based on galvanostatic cycling of both full and half cells, indicate that the ZnO coating method on average results in a 12 mAh g1 loss in discharge capacity. The PANI coated PW showed a drop in capacity of approximately half that of the uncoated reference samples. No significant differences were observed in capacity retention, coulombic efficiency, and thermal stability between ZnO coated and uncoated PW. The better rate capability of the uncoated PW is suggested to be a result of the smaller particle size. Explanations for the observed similarities in electrochemical performance include (i) the breaking up of particles and agglomerates during the ball milling process (exposing uncoated faces), and (ii) the compromised coating. / Framväxande marknader inom elektrokemisk energilagring, såsom stationär nätlagring, i kombination med framtida oro över tillgängligheten av litium, placerar natriumjonbatteriteknik (SIB) i en unik position för att komma in på marknaden som ett kommersiellt lönsamt alternativ. Nuvarande brister i prestanda av katodmaterial i SIB måste nödvändigtvis åtgärdas om denna teknik ska konkurrera med befintliga kommersiella litiumjonbatterier. Prussian White (PW), ett lovande katodmaterial som produceras av Altris AB i Uppsala, Sverige, har i många avseenden visat sig vara en lovande kandidat som katodmaterial. I försök att förbättra materialets livslängd, termiska stabilitet och cyklingshastighetsförmåga applicerades både zinkoxid (ZnO) och polyanilin (PANI) -beläggningar på PW.  Svepelektronmikroskopi (SEM) -bilder av den ZnO-belagda PW visade att ZnO koncentrerades till vissa regioner, vilket resulterade i en grov och komprimerad beläggning. Vidare antyder närvaron av järn 2p orbitaltoppar i XPS-spektra för ZnO- och PANI-belagda prover, tillsammans med SEM-bilderna, att ingen metod resulterade i en lyckad beläggning. Kristallografisk information erhållen med användning av en kapillär röntgendiffraktometer visade att PANI-beläggningsprocessen hade orsakat en fasomvandling från en monoklinisk till en kubisk struktur. Denna fasomvandling, baserad på efterföljande termogravimetrisk analys, tillskrivs en ökning av både interstitiellt och gittervatteninnehåll.  En jämförande analys av partikelstorlek och morfologi före och efter homogenisering visade att den använda kulkvarnstekniken resulterade i en minskning i storlek. Dessutom påverkade kulkvarnsprocessen den obelagda PW mer än den ZnO-belagda PW.  Resultat, baserade på galvanostatisk cykling av både hel- och halvceller, indikerar att ZnO-beläggningsmetoden i genomsnitt resulterar i en 12 mAh g-1-förlust i urladdningskapacitet. Den PANI-belagda PW uppvisade en minskning i kapacitet på ungefär hälften av de obelagda referensproverna. Inga signifikanta skillnader observerades i kapacitetsretention, coulombisk effektivitet och termisk stabilitet mellan ZnO-belagd och obelagd PW. Den bättre hastighetsförmågan hos obelagd PW föreslås vara ett resultat av den mindre partikelstorleken. Förklaringar för de observerade likheterna i elektrokemisk prestanda innefattar (i) uppbrytning av partiklar och agglomerat under kulfräsningsprocessen (exponering av obelagda ytor) och (ii) ofullständig beläggning.

No description available.

No description available.

La guerre franco-prussienne (ou franco-allemande) de 1870-71 fut un conflit majeur dont l’issue changea considérablement l’équilibre des puissances en Europe avec notamment l’émergence de l’Empire allemand. Pourtant, elle a été oubliée. Bien que depuis la fin du XIXe siècle, elle fut largement traitée par l’historiographie, la question des responsabilités relativement à son déclenchement demeure un sujet de débat. Tandis que certains historiens estiment que cette guerre fut sciemment provoquée par Bismarck afin de parachever l’unification allemande, d’autres croient que la responsabilité est partagée et que ce conflit était tout simplement inévitable dans le contexte du refroidissement des rapports franco-allemands depuis la défaite autrichienne de Königgrätz (Sadowa). Le présent mémoire entend se dissocier de ces interprétations en jetant un nouveau regard sur le rôle joué par Bismarck lors des « préliminaires » (Vorgeschichte) de 1870. En s’appuyant sur des sources primaires ainsi que sur ce que les historiographies allemande, française et anglo-saxonne nous apprennent, il sera démontré premièrement que la candidature Hohenzollern pour le trône d’Espagne n’a pas été « fabriquée » volontairement par le chef de la diplomatie prussienne afin de compléter l’unification allemande, mais qu’elle fut promue d’abord et avant tout pour des considérations de prestige politique. Deuxièmement, la fameuse dépêche d’Ems modifiée par Bismarck ne peut être considérée comme l’élément déclencheur de ce conflit, car la décision d’aller en guerre fut prise à Paris avant que les effets de la dépêche ne se fassent sentir. Enfin, par son besoin d’un succès politico-diplomatique qui aurait consolidé le Second Empire en faisant oublier les reculades antérieures, par son refus de se satisfaire du retrait de la candidature Hohenzollern et par les erreurs de sa politique étrangère en général, la France a adopté une position belliqueuse et s’est retrouvée seule dans une guerre qu’elle n’avait su ni prévenir, ni préparer. L’enjeu à Paris n’était finalement pas le règlement pacifique des différends avec la Prusse, mais la pérennisation de la prépondérance française sur le continent européen. / The Franco-Prussian War (or Franco-German War) of 1870-71 was a major conflict, where the outcome dramatically changed the balance of power in Europe, including the emergence of the German Empire. However, it has been forgotten. Although since the late nineteenth century it was widely discussed by historians, the issue of liability with respect to its outbreak remains a matter of debate. While some historians believe that this war was deliberately provoked by Bismarck in order to complete the unification of Germany, others believe that the responsibility was shared and that this conflict was simply inevitable in the context of the worsening of Franco-German relations, since the Austrian defeat at Königgrätz (Sadowa), in 1866. This thesis aims to dissociate itself from these interpretations by providing new insight regarding the role played by Bismarck during the “preliminaries” (Vorgeschichte) of 1870. Through the use of primary sources and German, French and Anglo-Saxon historiography, it will be shown first that the Hohenzollern candidature for the Spanish throne was not “made” voluntarily by the chief of the Prussian diplomacy to complement the German unification, but was promoted first and foremost for reasons of political prestige. Secondly, the famous Ems telegram amended by Bismarck cannot be seen as the trigger of this conflict, as the decision to go to war was taken in Paris before the negative effects of the message were felt. Finally, through its need of a political and diplomatic success that would have consolidated the Second Empire by forgetting earlier setbacks, through its refusal to show full satisfaction with the withdrawal of the Hohenzollern candidature and through the misconduct of its foreign policy in general, France adopted a bellicose position and found itself alone in a war it could neither prevent nor prepare. The issue in Paris was ultimately not the peaceful settlement of disputes with Prussia, but the perpetuation of French dominance on the European continent.