L'alumine, utilisée comme support de catalyseurs pour la réaction de Fischer-Tropsch ou pour la conversion de la biomasse, se transforme partiellement en présence d'eau en phases (oxy)hydroxydes à l'origine de fines qui posent problème dans la mise en ¿uvre de procédés en réacteurs de type slurry. Afin de concevoir des catalyseurs plus stables et plus résistants, ce travail de thèse visait à identifier le mécanisme d'hydratation et de dégradation des alumines de transition en phase aqueuse, et à étudier la façon dont des additifs organiques (alcools, polyols) ou inorganiques (Mg, Zr, Ni et Si) permettent de limiter cette dégradation. La conduite d'une étude systématique sur l'hydratation des alumines à 70°C à pression atmosphérique, ou à 150°C en conditions hydrothermales, a permis de définir un mécanisme général en deux étapes: une dissolution de la surface de l'alumine, suivie d'une précipitation, respectivement, d'hydroxydes d'aluminium Al(OH)3 ou de boehmite AlOOH sur les grains d'alumine. Par ailleurs, la dégradation chimique tend à favoriser la dégradation sous contraintes mécaniques. La présence de polyols en phase aqueuse, principalement des molécules à 5 ou 6 atomes de carbone, ralentit la dissolution de l'alumine et inhibe la précipitation de la boehmite. Les ions métalliques utilisés comme dopants de l'alumine ont tous un effet similaire sur la diminution de l'hydratation. Une inhibition totale de l'hydratation est obtenue par greffage de silicium à partir de TEOS. Une étude DRIFT dans la région des vibrations OH suggère que les additifs inorganiques inhibent la dissolution de l'alumine en bloquant des sites Al-OH localisés sur les faces latérales des particules. / Alumina, used as a catalyst support for the Fischer-Tropsch reaction or for the conversion of biomass, partially transforms in presence of water into (oxy)hydroxides phases. The formation of the latter leads to the production of fine particles that may cause plugging problems in the implementation of processes based on slurry bubble column reactors. In order to design more stable and more resistant catalysts, this PhD work aimed at identifying the mechanism of hydration and degradation of transition aluminas in aqueous phase, and to study how organic (alcohols, polyols) or inorganic (Mg, Zr, Ni and Si) additives can limit this degradation. The conduct of a systematic study on the hydration of alumina at 70°C under atmospheric pressure, or at 150°C in hydrothermal conditions, allowed defining a general two-step mechanism: a dissolution of the surface of alumina, followed by a precipitation of, respectively, aluminum hydroxides (Al(OH)3) or boehmite (AlOOH) on alumina grains. Furthermore, the chemical degradation tends to promote the degradation under mechanical stress. The presence of polyols in aqueous phase, mainly molecules with 5 or 6 carbon atoms, slows down the dissolution of alumina and inhibit the precipitation of boehmite. Metal ions used as dopants of alumina all have a similar effect on the decrease of hydration. A total inhibition of hydration is obtained by grafting silicon using TEOS. A DRIFTS study in the OH vibration region suggests that inorganic additives inhibit the dissolution of alumina by blocking Al-OH sites located on the lateral facets of the particles.

A síntese de nanopartículas com morfologia controlada vem sendo objeto de interesse crescente no campo da Ciência dos Materiais. Devido a essa motivação, o principal objetivo desse trabalho foi a síntese e caracterização de pseudoboemita e boemita apresentando uma ou duas dimensões nanométricas. O método de síntese utilizado para a obtenção de pseudoboemita fibrilar é baseado na reação de um alcóxido de alumínio, em solução aquosa de ácido acético. Para a preparação de boemita, um único método de síntese, a síntese hidrotérmica, foi utilizado, com o emprego de três precursores: uma pseudoboemita, um sal orgânico (o monohidróxido diacetato de alumínio) e o trihidróxido de alumínio gibsita, este último em duas formas: uma gibsita comercial e uma gibsita sintetizada que utiliza iodo como ativador. As pseudoboemitas e as boemitas obtidas foram caracterizadas por difração de raios-X e microscopia eletrônica de varredura. Algumas amostras de pseudoboemita e de boemita foram caracterizadas por análise térmica diferencial e por espectroscopia vibracional na região do infravermelho. Foram obtidas pseudoboemitas com morfologia fibrilar (partículas anisométricas alongadas); no caso das boemitas foram produzidas distintas morfologias (de acordo com o precursor e com as condições de síntese empregadas em sua obtenção): fibrilar (duas dimensões em escala nanométrica), nanoplacas (uma dimensão em escala nanométrica) e partículas com simetria cúbica (nenhuma dimensão em escala nanométrica). A presença do íon acetato na síntese hidrotérmica foi determinante na formação de boemita com morfologia de placas. / The synthesis of nanoparticles with controlled morphology is of increasing interests in the field of Materials Science. Due to this motivation, the main objective was the synthesis and characterization of boehmite pseudoboehmite presenting one or two nanoscale dimensions. The method of synthesis used to obtain fibrillar pseudoboehmite is based on the reaction of an aluminum alkoxide in aqueous acetic acid. For the preparation of boehmite, a single synthesis method, the hydrothermal synthesis, was used with three different precursors: a pseudoboehmite, an organic salt (aluminum monohydroxide diacetate) and the aluminum trihydroxide gibbsite, the latter in two forms: a commercial gibbsite and a gibbsite synthesized that utilizes iodine as activator. The pseudoboehmites and boehmites obtained were characterized by X-ray diffraction and scanning electron microscopy. Some samples of pseudoboehmite and boehmite were characterized by differential thermal analysis and by vibrational spectroscopy in the infrared region. Pseudoboehmites were obtained with fibrillar morphology (anisometric elongated particles); for boehmites, different morphologies were produced (according to the precursor and the synthesis conditions employed in their production): fibrillar (two dimensions in nanoscale), nanoplates (one dimension in nanoscale) and particles with cubic symmetry (no dimensions in nanoscale). The presence of acetate ion in hydrothermal synthesis was instrumental in the formation of boehmite with plate morphology.

L'empilement maîtrisé de granules de différentes tailles est un concept utilisé dans la plupart de procédés de mise en forme de matériau. Cette organisation hiérarchique est connue pour améliorer les propriétés d'écoulement à l'étape de mise en forme et les caractéristiques mécaniques du matériau final. Il est apparu intéressant d'appliquer ce concept à la mise en forme par extrusion de supports de catalyseurs avec des petites (2 µm) et grosses (19 µm) granules d'alumine poreuse dont l'assemblage est assurée par un liant traditionnel, la boehmite peptisée et neutralisée, ou par un liant plus original, le phosphate d'aluminium. L'étude vise ainsi à évaluer l'effet du liant et de la microstructure multi-échelles apportée par l'organisation hiérarchique des granules, sur les propriétés texturales et mécaniques des supports. Le contrôle des conditions de mise en forme et l'optimisation de la formulation des deux liants ont permis d'obtenir des extrudés à microstructure comparable entre la boehmite et le phosphate d'aluminium et variable en fonction de la proportion de petites. Cette population remplit les espaces entre les grosses granules de manière optimale entre 40 et 60% pds et les desserre aux plus fortes teneurs. La rétraction du liant au cours des traitements thermiques génère un volume de macropores qui est minimisé lorsque les petites granules comblent les espaces formés par les grosses. La macroporosité minimale conduit à de meilleures résistances à la rupture (par tests d'écrasement de type brésilien) et les matériaux les plus résistants sont ceux mis en forme avec le phosphate d'aluminium. Ce résultat est expliqué par la nature très cohésive de ce liant formée in situ par réaction de l'acide phosphorique avec la boehmite et la périphérie des granules d'alumine. Dans ce cas, la rupture a lieu au sein des granules différemment des supports mis en forme avec la boehmite peptisée à l'acide nitrique qui présentent une rupture à l'interface granule-liant. Les matériaux à microstructure multi-échelles présentent également une meilleure ténacité déterminée par des essais de flexion trois points. Le phosphate d'aluminium étant un liant non-poreux conduit à des supports avec une mésoporosité plus faible. Les nouveaux supports à microstructure multi-échelles semblent prometteurs pour des nombreuses applications catalytiques sensibles aux propriétés diffusionnelles et mécaniques. / The controlled packing of different sized-granules is a concept widely used in most of the shaping material processes. This hierarchical organization is known to improve the flow properties during shaping and the mechanical characteristics of the finished material. It seemed interesting to apply this concept in order to prepare catalyst supports by extrusion containing small (2 µm) and large (19 µm) porous alumina granules assembled by a traditional binder, the peptized and neutralized boehmite, or by a more original, an aluminum phosphate binder. This study aims to investigate the effect of binder type and of the multiscale microstructure achieved by the packing of different granules size on textural and mechanical support properties. The control of kneading and extrusion conditions associated with the optimized binder formulation, conducted to similar microstructures with both binders according to the amount of each granular population. Small granules fills better the residual spaces between the larges between 40 and 60 wt.% and loosens them with strongest contents. Binder shrinkage during heat treatment generates a macroporosity which is minimized when small granules fills the voids formed by the larger ones. Minimal macroporosity leads to better crushing resistance (by Brazilian test) and the most resistant materials are the ones shaped with the aluminum phosphate. This result is explained by the high cohesive capacity of this binder obtained in situ by reaction of the phosphoric acid with the boehmite and the border of the alumina granules. In this case, the breakage takes place inside the granules differently from the supports shaped with the peptized boehmite by nitric acid which present a breakage at the granule-binder interface. Also, the multiscale microstructure materials present a better tenacity determined by three point bending. Aluminum phosphate being a non-porous binder, leads to supports with a weaker mesoporosity. The new multiscale microstructure supports seem interesting for several catalytic applications that are sensitive to diffusivity and mechanical properties.

L'influence de la température et de la pression de vapeur d'eau sur la déshydratation de la boéhmite et sa transformation en alumine de transition a été étudiée. La boéhmite n'est pas un monohydrate d'alumine mais un oxyhydroxide d'aluminium dont la maille contient deux ions aluminium en positions cationiques trivalentes, deux ions oxygènes en positions anioniques divalentes et deux hydroxyles en positions anioniques monovalentes. Lors d'une augmentation modérée de la température (inférieure à 300°C), la boéhmite subit une déshydratation partielle qui conduit à un composé sous stœchiométrique en hydroxyles et qui est provoquée par l'association des hydroxyles deux par deux qui s'éliminent sous forme d'eau en laissant dans le réseau une position anionique monovalente vide et une autre occupée par un ion oxygène (en substitution de l'hydroxyle). C'est une réaction non renversable avec la diminution de la température. La déshydratation de la boéhmite en alumine de transition est le résultats de la succession et superposition partielle de trois équilibres : la déshydratation partielle de la boéhmite sans changement de phase, la transformation du réseau de la boéhmite (au-delà d'un certain degré de déshydratation) en réseau d'alumine de transition (spinelle) partiellement hydratée, la déshydratation de l'alumine de transition qui se poursuit jusqu'à 900°C ou plus. Les trois réactions sont endothermiques et leurs chaleurs de réaction ont été calculées. Il existe un domaine de température et de pression de vapeur d'eau où la boéhmite et l'alumine de transition coexistent. La température de déshydratation et de transformation, en alumine de transition de la boéhmite augmente avec la pression de vapeur d'eau appliquée. A une température donnée l'alumine de transition contient un plus grand nombre d'hydroxyles lorsqu'elle est formée sous une pression de vapeur d'eau supérieure.

Alumina (Al2O3) is one of the most widely used engineering ceramic. It can be used in a wide range of applications like electrical/thermal insulation, wear resistance, structural refractories, cutting tools, abrasives, catalyst carriers and coatings. A traditional ceramic process has several steps (i.e. powder synthesis and processing, shape forming, drying, organic burnout and densification). Accessing powders with sizes in the range of a couple of micrometers down to several tens of nanometers is considered critical in attaining higher densities in the final ceramic bodies. Besides since significant shrinkage can be observed in the thermal treatment steps due to the excessive use of additives (e.g. binders, solvents and plasticizers) in the powder processing and forming steps, it is important to take remedies that would increase the solids loading in the initial mixtures. In addition, most of the conventional additives and solvents used in these steps are toxic and it is necessary to replace them with the environmentally benign aqueous-based alternatives. Alumoxanes could be used as a benign aqueous-based alternative to be used as a ceramic precursor or an agent. They are a group of compounds that have nano sized boehmite cores encapsulated with the organic groups used in its production steps. In this research work, alumoxane nano particles which can be used as precursors for nano-alumina were developed starting from aluminum trihydroxide. As a preconditioning step, grinding was applied to decrease the aluminum hydroxide particle size (&amp / #8804 / 60 &amp / #956 / m) to submicron sizes. This process was followed by the glycothermal ageing step, and organic derivative of boehmite was obtained. The amorphous particles thus obtained were further treated mechanochemically in a high energy ball mill with organic chemicals like acetic acid, methoxy acetic acid, stearic acid and L-lysine. After this step the observed sizes of the particles were as low as 10-100 nm. The effects of organic molecules used in each step were studied by FTIR spectroscopy and their effectiveness in exfoliation of hydroxide layers were identified with dynamic light scattering from processing solutions dispersed in aqueous medium. Moreover, in each step, structural analyses were carried out by XRD.

Thesis (M.S.)--Mississippi State University. Dave C. Swalm School of Chemical Engineering. / Title from title screen. Includes bibliographical references.

Ένας συναρπαστικός τομέας της σύγχρονης έρευνας είναι αυτός των νάνο-συνθέτων υλικών. Το πεδίο αυτό περιλαμβάνει τη μελέτη πολυφασικών υλικών, στα οποία μία ή περισσότερες από τις χωρικές διαστάσεις κάποιας φάσης βρίσκεται στην περιοχή των νανομέτρων (1 nm = 10-9 m = 10 ). Αυτό που ξεχωρίζει τα νανοσύνθετα από τα άλλα συμβατά σύνθετα υλικά είναι η ικανότητα τους να συνδυάζουν ιδιότητες, οι οποίες είναι απαγορευτικές για τα παραδοσιακά υλικά, αλλά και η μεγάλη λειτουργικότητα που παρουσιάζουν. Η εισαγωγή των νάνο-σύνθετων υλικών και οι πολλές επιστημονικές μελέτες που έγιναν τα τελευταία χρόνια στόχευαν και προσδοκούσαν σε μία δραματική βελτίωση των μηχανικών ιδιοτήτων, πράγμα που πολλές φορές δεν επαληθεύθηκε. Τα νάνο-σύνθετα πολυμερικής μήτρας των οποίων η θερμομηχανική συμπεριφορά μελετήθηκε περισσότερο είναι τα συστήματα που περιέχουν ως εγκλείσματα νάνο-σωλήνες άνθρακα (carbon nanotubes), νάνο-σωματίδια αλούμινας και στρωματικά άλατα πυριτίου (layered silicates). Στις μέρες μας υπάρχει ένα αυξανόμενο ενδιαφέρον για τη μελέτη της διηλεκτρικής συμπεριφοράς και αγωγιμότητας των νάνο-σύνθετων πολυμερικής μήτρας - ανόργανων νάνο-εγκλεισμάτων. Στην παρούσα εργασία εξετάσθηκε η διηλεκτρική απόκριση των συστημάτων: (α) πολυμερικής μήτρας (polyurethane rubber, PU) και νάνο-σωματιδίων αλούμινας (alumina- boehmite), (β) πολυμερικής μήτρας (PU ή Natural Rubber, NR ή PU/NR) με στρωματικά άλατα πυριτίου (layered silicates), με παραμέτρους την περιεκτικότητα σε νανοεγκλείσματα, τη θερμοκρασία και τη συχνότητα του εφαρμοζόμενου πεδίου. Η διηλεκτρική φασματοσκοπία (Broadband Dielectric Spectroscopy) έχει αποδειχθεί ως ένα ισχυρό εργαλείο για την έρευνα της μοριακής κινητικότητας, των αλλαγών φάσεων, τους μηχανισμούς αγωγιμότητας και τα διεπιφανειακά φαινόμενα στα πολυμερή και τα σύνθετα πολυμερικά συστήματα. Η διηλεκτρική απόκριση των νάνο-συνθέτων εξετάστηκε με τη βοήθεια της διηλεκτρικής φασματοσκοπίας (BDS) στο εύρος συχνοτήτων 10-1-10 6 Hz και στο εύρος θερμοκρασιών από -100οC έως +70οC. Από τα πειραματικά αποτελέσματα προκύπτει πως παρατηρούνται διηλεκτρικές χαλαρώσεις που οφείλονται τόσο στην πολυμερική μήτρα, όσο και στην ενισχυτική φάση. Τέσσερις διακριτοί τρόποι χαλάρωσης καταγράφηκαν στα φάσματα των συστημάτων που μελετήθηκαν και αποδίδονται στη διεπιφανειακή πόλωση (IP) μήτρας/εγκλεισμάτων, στην υαλώδη μετάβαση (α-mode) των πολυμερών NR και PU, στην κίνηση πλευρικών πολικών ομάδων (β-mode) των αλυσίδων του PU και σε τοπικές κινήσεις εύκαμπτων τμημάτων των αλυσίδων του PU (γ–mode). Στο σύστημα πολυουρεθάνης (PU)–νάνο-σωματιδίων αλούμινας ερευνήθηκε η επίδραση του μέσου μεγέθους των σωματιδίων στην ηλεκτρική απόκριση των υλικών. Από τα αποτελέσματα φαίνεται πως η μείωση του μέσου μεγέθους των νάνο-εγκλεισμάτων οδηγεί σε αύξηση της διεπιφάνειας και των αντίστοιχων φαινομένων που τη συνοδεύει. Τέλος, από τη θερμοκρασιακή εξάρτηση της θέσεως των κορυφών διηλεκτρικών απωλειών, κάθε διεργασίας, προσδιορίστηκαν οι αντίστοιχες ενέργειες ενεργοποίησης. / The impact of nano-materials and nano-structured materials is well known in our days. Nano-composites consists an exciting modern field of scientific research. Nano-composites are multiphase materials where at least one of the dimensions of the reinforcing phase is in nano-scale. The main difference of nano-composites with compatible composites is their ability to achieve superior performance at a very low concentration of the filler. The majority of the active or potential applications of nano-systems is based on their thermo-mechanical behaviour, flame resistance and electrical properties. Under this point of view nano-composites exhibit properties or functions, which seem to be prohibited for traditional materials. Recently, there is an increased interest in studying the dielectric behaviour of polymer matrix – inorganic nano-filler composites. Polymer matrix nano-composites are expected to be useful in replacing conventional insulating materials providing tailored performance, by simply controlling the type and the concentration of nano-inclusions. In the present study is investigated the dielectric behaviour of composites consisted of a polymer matrix and inorganic nano-filler. Natural rubber (NR) and polyurethane rubber (PU) as well as their blend are used as matrices. Nano-composites were prepared by adding synthetic layered silicates (LS) via the latex compounding route. Further, the dielectric response of polyurethane rubber – alumina particles nano-composites, varying the mean particle diameter, is also examined. The dielectric properties of all systems are studied with parameters the temperature and the frequency of the applied field. Broadband Dielectric Spectroscopy (BDS) has been proved to be a powerful tool for the investigation of molecular mobility, phase changes, conductivity mechanisms and interfacial effects in polymers and complex systems. The dielectric response of nano-composites was examined by means of Broadband Dielectric Spectroscopy (BDS) in the frequency range10-1-106 Hz and temperature interval from -100 o C to +70 o C. Experimental results include relaxation phenomena arising from both the polymeric matrix and the filler. Four distinct relaxation modes were recorded in the spectra of all systems containing PU. They were attributed to interfacial polarization, glass transition (α-relaxation), motion of polar side groups and probably motions of the (CH2)n sequence of the PU chain (β and γ-relaxation). NR is a non polar polymer and thus only its glass/rubber transition is recorded in the low temperature range. Interfacial polarization is present in all composites systems. The dielectric response of polyurethane/boehmite alumina nano-composites was examined with an additional parameter, the size of the mean boehmite particle diameter. In order of ascending relaxation rate the following modes were recorded: interfacial polarization, glass/rubber transition (α-mode), motion of polar side groups (β-mode) and re-arrangements of small parts of the PU chain (γ-mode). The intensity and the position of these relaxations appear to vary with the size of the nano-filler. Finally, the activation energies of all the recorded processes were determined via the loss peak dependence on temperature.

...

It is well known that nanostructures possess unique electronic, optical, magnetic, ferroelectric and piezoelectric properties that are often superior to traditional bulk materials. In particular, one dimensional (1D) nanostructured inorganic materials including nanofibres, nanotubes and nanobelts have attracted considerable attention due to their distinctive geometries, novel physical and chemical properties, combined effects and their applications to numerous areas. Metal ion doping is a promising technique which can be utilized to control the properties of materials by intentionally introducing impurities or defects into a material. γ-Alumina (Al2O3), is one of the most important oxides due to its high surface area, mesoporous properties, chemical and thermal properties and its broad applications in adsorbents, composite materials, ceramics, catalysts and catalyst supports. γ-Alumina has been studied intensively over a long period of time. Recently, considerable work has been carried out on the synthesis of 1D γ-alumina nanostructures under various hydrothermal conditions; however, research on the doping of alumina nanostructures has not been forthcoming. Boehmite (γ-AlOOH) is a crucial precursor for the preparation of γ-Alumina and the morphology and size of the resultant alumina can be manipulated by controlling the growth of AlOOH. Gallium (Ga) is in the same group in the periodic table as aluminum. β-Gallium (III) oxide (β-Ga2O3), a wide band gap semiconductor, has long been known to exhibit conduction, luminescence and catalytic properties. Numerous techniques have been employed on the synthesis of gallium oxide in the early research. However, these techniques are plagued by inevitable problems. It is of great interest to explore the synthesis of gallium oxide via a low temperature hydrothermal route, which is economically efficient and environmentally friendly. The overall objectives of this study were: 1) the investigation of the effect of dopants on the morphology, size and properties of metal ion doped 1D alumina nanostructures by introducing dopant to the AlOOH structure; 2) the investigation of impacts of hydrothermal conditions and surfactants on the crystal growth of gallium oxide nanostructures. To achieve the above objectives, trivalent metal elements such as iron, gallium and yttrium were employed as dopants in the study of doped alumina nanostructures. In addition, the effect of various parameters that may affect the growth of gallium oxide crystals including temperature, pH, and the experimental procedure as well as different types of surfactants were systematically investigated. The main contributions of this study are: 1) the systematic and in-depth investigation of the crystal growth and the morphology control of iron, gallium and yttrium doped boehmite (AlOOH) under varying hydrothermal conditions, as a result, a new soft-chemistry synthesis route for the preparation of one dimensional alumina/boehmite nanofibres and nanotubes was invented; 2) systematic investigation of the crystal growth and morphology and size changes of gallium oxide hydroxide (GaOOH) under varying hydrothermal conditions with and without surfactant at low temperature; We invented a green hydrothermal route for the preparation of α-GaOOH or β-GaOOH micro- to nano-scaled particles; invented a simple hydrothermal route for the direct preparation of γ-Ga2O3 from aqueous media at low temperature without any calcination. The study provided detailed synthesis routes as well as quantitative property data of final products which are necessary for their potential industrial applications in the future. The following are the main areas and findings presented in the study: • Fe doped boehmite nanostructures This work was undertaken at 120ºC using PEO surfactant through a hydrothermal synthesis route by adding fresh iron doped aluminium hydrate at regular intervals of 2 days. The effect of dopant iron, iron percentage and experimental procedure on the morphology and size of boehmite were systematically studied. Iron doped boehmite nanofibres were formed in all samples with iron contents no more than 10%. Nanosheets and nanotubes together with an iron rich phase were formed in 20% iron doped boehmite sample. A change in synthesis procedure resulted in the formation of hematite large crystals. The resultant nanomaterials were characterized by a combination of XRD, TEM, EDX, SAED and N2 adsorption analysis. • Growth of pure boehmite nanofibres/nanotubes The growth of pure boehmite nanofibres/nanotubes under different hydrothermal conditions at 100ºC with and without PEO surfactant was systematically studied to provide further information for the following studies of the growth of Ga and Y doped boehmite. Results showed that adding fresh aluminium hydrate precipitate in a regular interval resulted in the formation of a mixture of long and short 1D boehmite nanostructures rather than the formation of relatively longer nanofibres/nanotubes. The detailed discussion and mechanism on the growth of boehmite nanostructure were presented. The resultant boehmite samples were also characterized by N2 adsorption to provide further information on the surface properties to support the proposed mechanism. • Ga doped boehmite nanostructures Based on this study on the growth of pure boehmite nanofibre/nanotubes, gallium doped boehmite nanotubes were prepared via hydrothermal treatment at 100ºC in the presence of PEO surfactant without adding any fresh aluminium hydrate precipitate during the hydrothermal treatment. The effect of dopant gallium, gallium percentage, temperature and experimental procedure on the morphology and size of boehmite was systematically studied. Various morphologies of boehmite nanostructures were formed with the increase in the doping gallium content and the change in synthesis procedure. The resultant gallium doped boehmite nanostructures were characterized by TEM, XRD, EDX, SAED, N2 adsorption and TGA. • Y doped boehmite nanostructures Following the same synthesis route as that for gallium doped boehmite, yttrium doped boehmite nanostructures were prepared at 100ºC in the presence of PEO surfactant. From the study on iron and gallium doped boehmite nanostructures, it was noted both iron and gallium cannot grow with boehmite nanostructure if iron nitrate and gallium nitrate were not mixed with aluminium nitrate before dissolving in water, in particular, gallium and aluminium are 100% miscible. Therefore, it’s not necessary to study the mixing procedure or synthesis route on the formation of yttrium doped boehmite nanostructures in this work. The effect of dopant yttrium, yttrium percentage, temperature and surfactant on the morphology and size of boehmite were systematically studied. Nanofibres were formed in all samples with varying doped Y% treated at 100ºC; large Y(OH)3 crystals were also formed at high doping Y percentage. Treatment at elevated temperatures resulted in remarkable changes in size and morphology for samples with the same doping Y content. The resultant yttrium doped boehmite nanostructures were characterized by TEM, XRD, EDX, SAED, N2 adsorption and TGA. • The synthesis of Gallium oxide hydroxide and gallium oxide with surfactant In this study, the growth of gallium oxide hydroxide under various hydrothermal conditions in the presence of different types of surfactants was systematically studied. Nano- to micro-sized gallium oxide hydroxide was prepared. The effect of surfactant and synthesis procedure on the morphology of the resultant gallium oxide hydroxide was studied. β-gallium oxide nanorods were derived from gallium oxide hydroxide by calcination at 900ºC and the initial morphology was retained. γ-gallium oxide nanotubes up to 65 nm in length, with internal and external diameters of around 0.8 and 3.0 nm, were synthesized directly in solution with and without surfactant. The resultant nano- to micro-sized structures were characterized by XRD, TEM, SAED, EDX and N2 adsorption. • The synthesis of gallium oxide hydroxide without surfactant The aim of this study is to explore a green synthesis route for the preparation of gallium oxide hydroxide or gallium oxide via hydrothermal treatment at low temperature. Micro to nano sized GaOOH nanorods and particles were prepared under varying hydrothermal conditions without any surfactant. The resultant GaOOH nanomaterials were characterized by XRD, TEM, SAED, EDX, TG and FT-IR. The growth mechanism of GaOOH crystals was proposed.

Within the collaborative research center SFB 920 “Multifunctional Filters for Metal Melt Filtration”, the thermally induced formation of metastable aluminum oxides and related microstructural changes were investigated. It was confirmed that the γ-Al₂O₃ phase possesses a defective spinel structure containing Al vacancies that preserve the stoichiometry of this phase. The presence of vacancies fragments apparently the γ-Al₂O₃ crystallites into nanocrystalline domains, which are separated by non-conservative antiphase boundaries (APBs) of the type {100} ¼<110>. These APBs form a 3D network that is randomly distributed over all crystallographically equivalent lattice planes. This phenomenon causes a starlike (and hkl-dependent) broadening of the reciprocal lattice points that correspond to the aluminum sublattice. It was shown that the extent of the broadening of the reciprocal lattice points can be predicted by employing the phase shift factors. With increasing degree of the APBs ordering, the initial streaks representing the broadened reflections start to split, forming superstructure reflections. This superstructure of γ-Al₂O₃ is commonly known as δ-Al₂O₃. Between the ordered APBs, the crystal structure of δ-Al₂O₃ is closely related to the crystal structure of monoclinic θ-Al₂O₃. The phase transition of γ-Al₂O₃/δ-Al₂O₃ to θ-Al₂O₃ proceeds via migration of just three Al³⁺ cations to the neighboring tetrahedral and octahedral sites in the cubic close packed (ccp) oxygen sublattice. The general migration vector is ⅛<111> (γ-Al₂O₃). Diffraction effects associated with different intermediate states can be explained by an improper long-range ordering of equivalent APBs or certain Al³⁺ cations and the local formation of θ-Al₂O₃ within the δ-Al₂O₃ superstructure. The formation of θ-Al₂O₃ is accompanied by an increase of the occupancy of the tetrahedral sites in the oxygen sublattice by the Al³⁺ cations. In surrounding local γ-Al₂O₃ domains, however, some cations migrate from the tetrahedral to the octahedral sites. Thus, the local formation of θ-Al₂O₃ is nearly invisible for the ²⁷Al 1D magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy. Still, it was recognized by the 2D multiple quantum (MQ) MAS NMR spectroscopy. A continuous formation of the θ-Al₂O₃ domains was confirmed by the Raman spectroscopy, X-ray diffraction (XRD) and selected area electron diffraction (SAED). The proposed microstructure and transformation models helped to explain the thermal stabilization of the metastable alumina phases by Si-doping. For investigation of the thermally induced phase transitions in metastable alumina phases, boehmite (γ-AlO(OH)) was chosen as the starting compound. However, the metastable alumina phases were also observed in endogenous inclusions present in solidified steel melts. For identification of these phases, a procedure for reconstruction of spherical Kikuchi maps from recorded EBSD patterns was developed.