Les alliages ferromagnétiques à mémoire de forme (FSMAs: Ferromagnetic shape memory alloys) avec des compositions proches de Ni2MnGa ont attiré beaucoup d’attention en raison de leur effet de mémoire de forme gigantesque et de leur réponse rapide et dynamique. Dans ce travail, une investigation de ces matériaux via des calculs ab initio est effectuée en utilisant la théorie de la fonctionnelle de la densité (DFT) à l’aide du logiciel VASP. Pour la composition stoechiométrique de Ni2MnGa, alliage ferromagnétique à mémoire de forme, l'oscillation du moment magnétique de Ni qui dépend du réarrangement atomique dans la superstructure, domine la distribution du moment magnétique total par unité Ni2MnGa. Le changement de moment magnétique total unité Ni2MnGa associé à la structure a été déterminé comme augmentant de l'austénite cubique à la martensite NM tétragonale à travers les martensites modulées monocliniques. Pour les alliages Ni2MnGa ferromagnétiques à mémoire de forme hors-stoechiométrie, le dopage au Ni stabilise la martensite non modulée (NM) avec la structure cristalline tétragonale simple, tandis que le dopage approprié au Mn stabilise la martensite modulée à sept couches (7M) avec une structure monoclinique. Expériences de La transformation martensitique subit une force motrice nettement plus considérable que celle de la transformation intermartensitique. En outre, le moment magnétique total des trois séries d'alliages est principalement dominé par leur teneur en Mn avec une faible dépendance de l'état de phase. Les moments moyens du Ni et du Mn montrent une dépendance à la fois de la composition et de l’ d'état de phase. La perturbation des moments magnétiques par substitution d'atomes est principalement localisée dans les antisites et ses proches voisins. Elle est principalement dominée par leur environnement en Mn (distance et nombre). L’examen des aspects fondamentaux tels que la stabilité de phase et des propriétés magnétiques des ferromagnétiques à mémoire de forme Ni-Mn-Ga est d'une grande importance pour améliorer les performances fonctionnelles et de concevoir de nouveaux FSMAs prometteurs. / Ni-Mn-Ga ferromagnetic shape memory alloys (FSMAs) with chemical composition close to Ni2MnGa have received great attention due to their giant magnetic shape memory effect and fast dynamic response. In this work, a series of first–principles calculations have been performed within the framework of the Density Functional Theory (DFT) using the Vienna Ab initio Software Package (VASP). For the stoichiometric Ni2MnGa ferromagnetic shape memory alloy, the oscillation of Ni magnetic moment that depends on the atomic shuffling in the superstructure dominates the distribution of the total magnetic moment per Ni2MnGa unit. The structure change-associated total magnetic moment has been found to increase for Ni2MnGa unit from the cubic austenite to the tetragonal NM martensite through the monoclinic modulated martensites. For the off-stoichiometric Ni2MnGa ferromagnetic shape memory alloys, Ni-doping stabilizes the non-modulated martensite (NM) with simple tetragonal crystal structure, whereas proper Mn-doping stabilizes the seven-layered modulated (7M) martensite with monoclinic structure. Martensitic transformation experiences much larger driving force than that of the intermartensitic transformation. Moreover, the total magnetic moment of the three series of alloys is mainly dominated by their Mn content with little phase state dependence. The average Ni and Mn moments display both composition and phase state dependences. The perturbation of the magnetic moments by atom substitution is mainly located in the antisite and its close neighbors. It is mainly dominated by their Mn environment (distance and number). Insights into fundamental aspects such as phase stability and magnetic properties in Ni-Mn-Ga FSMAs are of great significance to improve the functional performances and to design new promising FSMAs

Final thesis, elaborated within the master study in the field of Manufacturing technology, deals with analysis and solving of weld cracking problem in welds of anti-roll bar socket for passenger car. Sockets material is fine-grained low-alloy steel S420MC. For better understanding of the problem, a literary study has been elaborated, describing the issue. Next, an analysis of parts material and its weldability, has been conducted, according to ČSN EN 1011-2 standard. After an analysis of cracks and considering current conditions of sockets welding a series of experiments has been designed to evaluate impact of different process parameters on final weld quality. Experiments results have been used to compile a series of recommendations for adjustment of the welding process and to eliminate weld cracking. The results of the experiments were used as a basis for elaboration of WPS protocol.

V práci je zkoumán vliv podmínek na průběh hydrolýzy alkoxidů titanu a vlastností připravovaných nanočástic oxidu titaničitého s důrazem na teplotu a množství vody přítomné v systému. Připravované hydrolyzáty alkoxidů titanu a nanočástice oxidu titaničitého připravené z hydrolyzátů jsou studovány metodami XRD, DTA – TGA, SEM – EDS, BET a PCCS. Nanočástice magnetitu byly syntetizovány pomocí precipitační reakce z roztoku Mohrovy soli a jejich krystalová struktura, velikost a povrchové vlastnosti byly sledovány s vyhodnocením vlivu teploty a při modifikaci povrchu polykarboxyletherovým superplastifikátorem. Pro upevnění TiO2 na povrch magnetitu byla použita kombinovaná metoda aplikace vybraných nanočástic TiO2 s hydrolýzou TiO2 pomocí alkoxidů titanu za účelem přípravy fotokatalyticky aktivního core-shell práškového katalyzátoru s vylepšenými vlastnostmi adsorpce na povrchu. Studovány byly možnosti aplikace TiO2 na povrch Mn-Zn feritu, kdy byl studován vliv depozice tenkých vrstev C a Au na morfologii povrchu. Fotokatalytická aktivita vybraných připravených materiálů byla studována pomocí dekompozice methylenové modři v roztoku a par isopropanolu a ethanolu rozkládaných pomocí Mn-Zn feritu v experimentálním chemickém reaktoru s magnetickým polem stabilizovaným ložem nosiče katalyzátoru.

Magnetic Shape Memory (MSM) alloys show a superelastic behaviour with possible deformation rates up to 6% until 12% and a sufficient lifetime performance [1, 2]. In this paper, a passive application for a superelastic Ni-Mn-Ga-alloy is presented by using the MSM element as an accurately defined inner friction in a system of a multistable actuator, in particular a multistable proportional valve. The multistable valve is characterized by a currentless holding of the valve displacement in any position of the stroke. This circumstance makes the concept a very low energy consumption valve, compared to conventional proportional valves with solenoid actuators. The new aspect of a rigid connection of MSM Materials enables an absorption of tension as well as compressive forces. To realize an applicable controlling valve, a simple and effective controlling strategy has been implemented. Due to the stabilizing effect of the MSM element, an accurate controlling of the valve stroke and the usage for example as a pressure-, mass-flow or temperature-controlling valve was made possible. Furthermore, some potential applications in pneumatics as well as in hydraulics are presented.

Ce travail est consacré à la conception, à la synthèse et à l’étude de catalyseurs d’oxydation à base de métaux 3d en association avec des ligands non-innocents. Tout d’abord, le développement de complexes dérivés de deux ligands rédox-actifs tétra-azotés originaux (motifs o-phénylènediamine, aniline et dipyrrine) a été étudié. Plusieurs espèces dans différents états d’oxydation ont été préparées. L’élucidation de leurs structures électroniques a été réalisée par des techniques complémentaires (diffraction des rayons X, électrochimie, spectroscopies UV-Vis-NIR, EPR et Mössbauer). Un complexe de fer biradicalaire basé sur le ligand bis(2-aminophényl)-o-phénylènediamine a été synthétisé. Parallèlement, une architecture innovante bis(2-aminophényl)dipyrrine a été développée. En réaction avec du nickel, du cuivre et du cobalt, elle a conduit à trois complexes isostructuraux présentant un caractère radicalaire anilinyle-dipyrrinyle jamais mis en évidence auparavant. La complexation de cette dipyrrine au manganèse a formé un singulier complexe dinucléaire radicalaire avec une valence mixte inhabituellement localisée sur le ligand.Dans un second temps, les complexes de fer, de cuivre et de manganèse ont été évalués dans des applications d’oxydation. L’étude de la réactivité du biradicalaire de fer a entraîné l’observation d’une espèce à haute valence en spectroscopie Mössbauer. D’autre part, le complexe de cuivre a montré une activité en oxydation d’un alcool. Enfin, une activité en catalyse d’oxygénation aérobie a été identifiée avec le complexe dinucléaire radicalaire de manganèse. / This work is devoted to the design, the synthesis and the study of oxidation catalysts, based on 3d metals and non-innocent ligands. First, the development of complexes derived from two unprecedented tetra-nitrogenated redox-active ligands (o-phenylenediamine, aniline and dipyrrin motifs) has been investigated. A number of species at various oxidation states has been prepared. The elucidation of their electronic structures was performed by complementary techniques (X-Ray diffraction, electrochemistry, UV-Vis-NIR, EPR and Mössbauer spectroscopy). A biradical iron complex based on the bis(2-aminophenyl)-o-phenylenediamine ligand was synthesized. In parallel, an innovative bis(2-aminophenyl)dipyrrin architecture was developed. Its reactions with nickel, copper and cobalt led to three isostructural complexes, showing an unprecedented anilinyl-dipyrrinyl radical character. The complexation of the dipyrrin to manganese afforded a unique dinuclear radical complex with a rare ligand-based mixed valence.In a second phase, iron, copper and manganese complexes were assessed in oxidation applications. The reactivity study of the biradical iron resulted in the observation of a high-valent species thanks to Mössbauer spectroscopy. On the other hand, the copper complex has shown an activity in the oxidation of an alcohol. Finally, a catalytic aerobic activity in oxygenation catalysis was identified with the dinuclear manganese radical complex.

No description available.

Die vorliegende Arbeit untergliedert sich in drei aufeinander aufbauende Themenkomplexe. Der erste Komplex umfasst Untersuchungen zum Nachweis und zur Quantifizierung von Beugungsanteilen in der ioneninduzierten Elektronenemission (IILEED). Dazu wurden bei der streifenden Streuung schneller He und H -Ionen an Cu(001) energiedispersive zweidimensionale Winkelverteilungen emittierter Elektronen aufgenommen. Es konnten reflexartige Intensitäten in der ioneninduzierten Elektronenemission nachgewiesen werden, deren Raumwinkeländerungen in Abhängigkeit von Anregungsrichtung und Detektionsenergie mittels einer modifizierten Ewaldkonstruktion quantitativ nachvollziehbar sind. Die beobachteten Beugungsstrukturen geben Aufschluss über den ursächlichen elektronischen Anregungsprozess an der Oberfläche. Im zweiten Teil wird die ioneninduzierten Elektronenemission beim Wachstum ultradünner 3d-Übergangsmetallfilme (Co, Fe, Mn) auf Cu(001) untersucht. Die streng zum jeweiligen Wachstumsstadium korrelierten Änderungen der Energiespektren und Anzahlverteilungen emittierter Elektronen (SEE-Oszillationen), sind hauptsächlich auf binäre Stossprozesse der Projektile mit Stufenkanten zurückzuführen. Die SEE-Oszillationen können zur in-situ Wachstumsanalyse und Bedeckungsbestimmung ultradünner Filme herangezogen werden. Im dritten Abschnitt wird eine neue Messmethode zur Analyse komplex rekonstruierter Oberflächenstrukturen vorgestellt. Die Methode der „Ionenstrahltriangulation“ (IST) basiert auf der relativen Änderung der Anzahlverteilung emittierter Elektronen bei azimutaler Drehung der Probenoberfläche. Bestimmt werden die azimutale Richtung und die relative Breite von Oberflächenkanälen in der obersten atomaren Lage. Die Registrierung der pro Streuprozess emittierten Elektronenanzahl eröffnet erstmalig eine quantitative Simulation von IST-Messkurven. Auf dieser Grundlage können mittels IST die lateralen Atompositionen langreichweitig geordneter Oberflächenstrukturen auf mehrere hundertstel Angström genau festgelegt werden. Das hohe strukturanalytische Potential dieser Messmethode demonstrieren IST-Untersuchungen an den Strukturphasen der Systeme Mn/Cu(001) und Fe/Cu(001). / H+ and He+ ions with an energy of 25 keV are scattered under a grazing angle of incidence from a clean and flat Cu(001) surface. For specific azimuthal orientations of the crystal surface with respect to low index directions in the surface plane we observe the ion induced emission of electrons with a conventional LEED (low energy electron diffraction) setup. By operating the instrument in an energy dispersive mode we find intensity distributions of emitted electrons which can unequivocally be ascribed to diffraction effects at the target surface. From this ion induced LEED-reflexes (IILEED) we get important information about the electron excitation- and emission effects during the scattering process. In the second part of this work we investigate the correlation between thin-film growth (Co, Fe, Mn on Cu(001)) and electron emission in the regime of grazing ion scattering. The “rough” surface of uncompleted layers increase the probability of binary collisions of incident ions with individual atoms at the surface. The energy spectras and the number distribution of emitted electrons are substantially influenced by these “violent” collisions and allow us to monitor growth of thin films via simple measurements of target current or from energy spectra of emitted electrons. The method provides excellent signals and is also applicable in the regime of poor layer growth. By making use of ion beam triangulation (IBT), direct information on the atomic structure of thin films and substrate surfaces is obtained. We discuss in the third part of this work a new variant of this method based on the detection of the number of emitted electrons. The data are analyzed via computer simulations using classical mechanics which provides a quantitative analysis with respect to projectile trajectories. This new detection scheme allows the determination of the in-plane structure of reconstructed thin films and surfaces with high precision. The impressed potential of this method is demonstrated by quantitative analysis of the structural phases of Fe and Mn on Cu(001).

Tese de mestrado. Mestrado Integrado em Engenharia Metalúrgica e de Materiais. Faculdade de Engenharia. Universidade do Porto. 2012

Pasture plants already adapted to acidic soil conditions are required as part of an integrated approach (with lime amelioration) to managing acid soils on the Tablelands of New South Wales, Australia. The objective of this thesis is to evaluate the usefulness of Austrodanthonia species for this purpose. The material evaluated in this study was collected during a previous survey of the distribution of Austrodanthonia on the Central, Southern and Monaro Tablelands of New South Wales. It was hypothesised that the genus Austrodanthonia has a wide range of tolerance to acid soils. A series of experiments that provided information on the growth and physiology of Austrodanthonia in relation to soil acidity, with a view to the identification and eventual domestication of the most promising plant material have been conducted through pot, hydroponics and field investigations. Firstly, soils were acidified or limed to obtain a range of soil pH and Al concentrations. This experiment showed that adding aluminium sulfate and calcium carbonate followed by washing excess salts with water is a simple, rapid and convenient method for adjusting soil pH for pot experiments. The pH of the amended soils remained relatively unchanged eight months after treatment. The experimental set-up also resulted in a wide range of soluble Al (2-52 mg/kg) across the soils. The relative Al-tolerance of 183 accessions from 15 Austrodanthonia species was tested in a pot experiment using a range of soil pH. Emergence, survival and growth of all accessions were drastically reduced by high soil acidity (pH 3.9, P < 0.001). About 11% of plants emerged at pH 3.9, whereas at pH 4.4 and 5.3, ~72% of plants emerged. Accessions exhibited large variation within and between species in their tolerance to soil acidity. From the species/accessions tested, 49 accessions from eight species were selected for further study (on the basis of being more acid tolerant). Hydroponic experiments conducted in the glasshouse evaluated: (i) formulation of nutrient solution with a stable pH, (ii) effectiveness of the formulation using tap water and deionised water and (iii) estimation of free ion activities of Al and Mn in the nutrient solution and their effects on Austrodanthonia growth. These experiments showed that a NO3-N/NH4-N ratio of 9:4 is the most appropriate ratio to obtain a stable pH 4.0 without affecting plant growth; that there was little difference between tap water and deionised water on the ionic effects of Al and Mn, and plant-size did not play a role on accession survival and that accessions of Austrodanthonia could grow well within a wide range of pH (3.5-5.5), Al (50-250 �M) and Mn (100-2000 �M). Growth of Austrodanthonia accessions declined under high acidity (pH < 3.5) and Al (300 �M), but tolerated high concentrations of Mn (2000 �M). Root-tips stained with hematoxylin grouped accessions in a similar way to the pot and hydroponic experiments for most of the accessions tested. The intensity of root staining with hematoxylin and the differential distribution of Al in the shoots and roots provided an indication that different tolerance mechanisms may be involved with Austrodanthonia accessions. It appears that both exclusion and internal mechanisms may operate for Al- and Mn-tolerance. A field experiment was conducted at Carcoar (33037�S, 149013�E, elevation 800 m) using gradients in soil pH and Al available on-site to grow selected accessions of Austrodanthonia. The accessions exhibited a range of responses to soil acidity. The accession responses to acidity from the pot and hydroponic experiments were similar to those obtained in the field, especially where Al was present as a low Al-challenge. Overall, this study shows that Austrodanthonia exhibits a wide range of acid tolerance between species and accessions within species. Among the species tested, A. duttoniana and A. fulva appeared to have the greatest commercial potential, because of their productivity and acid tolerance. The variability that exists in the accessions may be exploitable in breeding and selection programs for improved cultivars.

Ce travail de thèse a pour but l'élaboration et la caractérisation microstructurale / magnétique de systèmes multicouches Fe/Mn présentant un couplage d'échange anisotrope. La caractérisation structurale a été effectuée par microscopie électronique en transmission, ce qui a permis d'identifier les structures α-Fe et α-Mn ainsi que l'évolution de la rugosité aux interfaces avec la température de dépôt. Les analyses en sonde atomique tomographique ont permis d'obtenir une analyse locale des interfaces. Les profils linéaires de concentration obtenus ont révélé une asymétrie des interfaces Fe/Mn et Mn/Fe avec la formation de mélange Fe-Mn à concentration modulée aux interfaces, ainsi qu'une augmentation de la largeur de l'interface Fe/Mn avec la température de dépôt. Les mesures de spectroscopie Mössbauer ont permis d'identifier l'environnement local des atomes de Fe. Les zones riches en Fe sont ferromagnétiques avec une distribution de champ hyperfin reflétant la composition modulée, et les zones riches en Mn sont antiferromagnétiques avec une température de Néel sensiblement proche de celle du α-Mn. La caractérisation magnétique a été effectuée dans un premier lieu par magnétométrie à SQUID, ce qui a permis de déterminer l'évolution de l'aimantation globale des échantillons, le champ de d'échange et le champ coercitif. Par ailleurs, les profils d'aimantation en profondeur ont été obtenus par réflectométrie de neutrons polarisés, ce qui a permis d'identifier deux types de couches de Fe, ainsi que l'influence de la température d'élaboration sur le champ coercitif.