No description available.

Thesis (PhD (Chemistry and Polymer Science))--University of Stellenbosch, 2010. / ENGLISH ABSTRACT: The distribution of different free chemical functional groups on wood and pulp fibres was determined by means of atomic force microscopy (AFM) with chemically modified tips. Because these functional groups show a higher affinity to similar groups on the substrate surface during scanning, AFM images were recorded using an additional digital pulsed-force mode (DPFM) controller. This allowed the distribution of the chemical components to be imaged and to a degree, also to be quantified. The investigated tip coatings showed different sensitivities towards the major chemical components present in wood fibres. These components were determined on spin-coated films as well as wood fibres. It was possible to make a clear distinction between cellulose and lignin in both cases. This technique could therefore be used to differentiate between cellulose and lignin present on pulp fibre surfaces and to confirm the successful removal of lignin by pulping. The chemical composition of wood fibres and fibre surfaces of several acacia and eucalyptus species, and hybrids originating from various growth sites in South Africa, are compared. The objective was to determine the differences in chemical surface composition due to genetics or site. The motivation for this was to eventually facilitate a tailor-made supply of wood for pulping which results in an optimal blend of fibres that can be pulped together with similar yields. This, however, first requires a sound knowledge of the fibre properties. The surface functionality on the single fibre level is a key property because it determines how good inter-fibre bonding will be when paper is formed, which in turn depends to a large degree on the amount of free hydroxyl groups that are available and therefore on the cellulose content on the fibre surface. The cellulose and lignin contents on the fibre surface were determined with chemical force microscopy (CFM), a variation of AFM. CFM involves the use of chemically modified tip using selected functional groups. Since, the general bulk composition of the fibre and the surface composition differ, both parameters were determined. Significant differences in the cellulose and lignin content on fibre surfaces were found, with regard to genotype and site, respectively. In some, but not all, cases the surface composition of wood fibres followed the bulk composition and differences were generally more pronounced. Differences due to genotype were significant, especially with regards to the surface lignin content - but variation due to site was also distinctly recognisable. This variation in surface functionality could be the reason why some pulpwood blends result in a lower pulp yield and different quality. / AFRIKAANSE OPSOMMING: Die verspreiding van verskillende vrye chemiese funksionele groepe op hout en pulpvesels is bepaal deur middel van atoomkragmikroskopie (AFM), met chemies-gemodifiseerde punte (tips). Omdat hierdie funksionele groepe 'n hoër verwantskap tot soortgelyke groepe op die substraat se oppervlak gedurende skandering toon, kan AFM-beelde wat met 'n addisionele digitalepulskragmodusbeheerstel bepaal word dit moontlik maak om die verspreiding van die chemiese komponente uit te beeld en tot op ‘n sekere vlak te kwantifiseer. Die ondersoekte punt-oppervlakmiddels het verskillende sensitiwiteite teenoor die hoof chemiese komponente in die houtvesels en spin-bestrykte films getoon. 'n Duidelike onderskeid kon in beide gevalle tussen sellulose en lignien gemaak word. Hierdie tegniek kon dus gebruik word om te onderskei tussen sellulose en lignien wat op die pulpveseloppervlak teenwoordig was en om die suksesvolle verwydering van lignien gedurende die pulpproses (pulping) te bevestig. In hierdie studie is die chemiese samestelling van houtvesels en die veseloppervlaktes van verskeie akasia en eucalyptus spesies, asook dié van gekruisde spesies wat van verskeie werfliggings in Suid-Afrika afkomstig is, vergelyk. Die doel was om te toets vir verskille in chemiese oppervlaksamestellings, wat veroorsaak kan word deur genetika of werf verskille, met die uiteindelike mikpunt om ‘n spesiaal-gemaakte voorraad van hout vir pulping te fasiliteer, wat kan lei tot 'n optimale mengsel van vesels wat saam gepulp kan word met soortgelyke opbrengs. Dit vereis natuurlik 'n goeie kennis van die veseleienskappe. Die oppervlakfunksionering van enkel vesels is ‘n kritiese eienskap omdat dit bepaal hoe goed interveselverbindings sal wees wanneer papier gevorm word. Dit hang tot ‘n groot mate af van die hoeveelheid vry hydroksielgroepe wat beskikbaar is en dus ook van die sellulose inhoud op die veseloppervlak. Die sellulose- en lignieninhoud op die veseloppervlak is bepaal met chemiese kragmikroskopie – 'n variasie van atoomkragmikroskopie. Omdat die algemene grootmaat samestelling van die vesel en die oppervlaksamestelling mag verskil, is altwee parameters bepaal. Beduidende verskille in die sellulose- en lignieninhoud, met betrekking tot genotipe en werfligging, op veseloppervlaktes is gevind. In sommige, maar nie alle, gevalle het die oppervlaksamestelling van houtvesels ooreengestem met die grootmaatsamestelling, en verskille was oor die algemeen meer beduidend. Verskille as gevolg van genotipe was beduidend, veral met betrekking tot die oppervlak lignieninhoud, maar variasie as gevolg van werfligging was ook duidelik herkenbaar. Hierdie variasie in oppervlakfunksionering kan die rede wees hoekom sommige pulp–hout mengsels lei tot 'n laer pulpopbrengs en verskille in kwaliteit.

abstract: In the United States, 95% of the industrially produced hydrogen is from natural gas reforming. Membrane-based techniques offer great potential for energy efficient hydrogen separations. Pd77Ag23 is the bench-mark metallic membrane material for hydrogen separation at high temperatures. However, the high cost of palladium limits widespread application. Amorphous metals with lower cost elements are one alternative to replace palladium-based membranes. The overall aim of this thesis is to investigate the potential of binary and ternary amorphous metallic membranes for hydrogen separation. First, as a benchmark, the influence of surface state of Pd77Ag23 crystalline metallic membranes on the hydrogen permeability was investigated. Second, the hydrogen permeability, thermal stability and mechanical properties of Cu-Zr and Ni60Nb35M5 (M=Sn, Ti and Zr) amorphous metallic membranes was evaluated. Different heat treatments were applied to commercial Pd77Ag23 membranes to promote surface segregation. X-ray photoelectron spectroscopy (XPS) analysis indicates that the membrane surface composition changed after heat treatment. The surface area of all membranes increased after heat treatment. The higher the surface Pd/(Pd+Ag) ratio, the higher the hydrogen permeability. Surface carbon removal and surface area increase cannot explain the observed permeability differences. Previous computational modeling predicted that Cu54Zr46 would have high hydrogen permeability. Amorphous metallic Cu-Zr (Zr=37, 54, 60 at. %) membranes were synthesized and investigated. The surface oxides may result in the lower experimental hydrogen permeability lower than that predicted by the simulations. The permeability decrease indicates that the Cu-Zr alloys crystallized in less than two hours during the test (performed at 300 °C) at temperatures below the glass transition temperature. This original experimental results show that thermal stability of amorphous metallic membranes is critical for hydrogen separation applications. The hydrogen permeability of Ni60Nb35M5 (M=Sn, Ti and Zr) amorphous metallic membranes was investigated. Nanoindentation shows that the Young’s modulus and hardness increased after hydrogen permeability test. The structure is maintained amorphous after 24 hours of hydrogen permeability testing at 400°C. The maximum hydrogen permeability of three alloys is 10-10 mol m-1 s-1 Pa-0.5. Though these alloys exhibited a slight hydrogen permeability decreased during the test, the amorphous metallic membranes were thermally stable and did not crystalize. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2015

No description available.

L’oxyde de graphène est un nanomatériau prometteur grâce à ses caractéristiques physicochimiques. Cependant, jusqu’à aujourd’hui, sa composition exacte reste encore inconnue. Ceci est dû à la complexité et au caractère non-stoechiométrique de ce matériau. Nous avons commencé par étudier sa composition de surface et sa réactivité. Nous avons utilisé des échantillons synthétisés de manière différente pour explorer la relation entre la méthode de synthèse et la composition de surface. En outre, nous avons préparé un dérivé fonctionnalisé avec un agent chélatant de radionucléides pour étudier sa biodistribution et l’impact de la taille latérale.Par la suite, nous avons essayé plusieurs stratégies de multi-fonctionnalisation. L’avantage est de pouvoir combiner différentes propriétés. Nous avons observé que, souvent après la fonctionnalisation, la dispersabilité de l’oxyde de graphène diminue. Ainsi, nous avons développé un échantillon fonctionnalisé par un polymère soluble dans l’eau. Enfin, nous avons exploré et amélioré les méthodes de caractérisation de l’oxyde de graphène. Une caractérisation approfondie par différentes techniques est fondamentale pour comprendre les modifications que le matériau a subies. / Graphene oxide is a promising nanomaterial thanks to its physicochemical characteristics. However, until today its exact composition remains still unknown. This is due to the complexity and non-stoichiometric character of this material.We started by investigating the surface composition of graphene oxide and its reactivity. We used differently synthesized samples to explore the relationship between the synthesis method and the surface composition. Furthermore, we functionalized graphene oxide with a chelating agent of radionuclides to study its biodistribution, and the impact of the lateral size. Afterwards, we tried different strategies for multifunctionalization with the aim to combine different properties. We observed that the dispersibility of graphene oxide often decreased after functionalization. Thus, we developed a highly water-stable graphene oxide sample by grafting awater-soluble polymer on its surface. Finally, we explored and improved the characterization methods for graphene oxide. Athorough investigation using different characterization techniques is fundamental to understand the modifications that the material underwent.

No description available.

Les catalyseurs Pt-Rh supportés ont montré des propriétés intéressantes en ouverture sélective des naphtènes. Les performances catalytiques de ces catalyseurs dépendent, entre autres, de l'interaction entre le rhodium et le platine. L'objectif de ces travaux portait sur l'étude de l'influence de la méthode de préparation sur les interactions Pt-Rh. Dans ce but, plusieurs voies reposant sur des stratégies de synthèse différentes ont été sélectionnées, des plus classiques, comme l'imprégnation, aux plus sophistiquées, comme la modification d'un catalyseur monométallique parent par ajout d'un second métal par réaction de surface, la formation des particules Pt-Rh au sein de microémulsion ou de microsuspension ou encore la réduction des précurseurs métalliques assistée par radiolyse. Les catalyseurs ont été caractérisés par diverses techniques telles que la chimisorption d'hydrogène, la microscopie électronique en transmission, la réduction en température programmée, l'adsorption de molécules sondes (CO ou NO puis CO) suivie par infrarouge ou encore par réactions modèles. Ces caractérisations ont permis de mettre en évidence que (i) les imprégnations classiques ou assistées par radiolyse mènent à un mélange de particules monométalliques et bimétalliques, (ii) les méthodes de modification de surface permettent le dépôt du second métal sur les sites spécifiques des particules métalliques préformées, (iii) la synthèse des particules métalliques en microsuspension ou microémulsion permet également l'obtention de particules bimétalliques, mais avec la présence d'alliages Pt-Rh de surface. / Pt-Rh supported catalysts have demonstrated interesting properties in selective ring opening of naphthenic molecules. Their catalytic performances depend on several properties like platinum-rhodium interaction. The aim of this work was to study the influence of the preparation method on Pt-Rh interactions. For this purpose, several preparation ways were selected, from the most classical ones, such as impregnation, to more sophisticated ways such as (1) surface modification of monometallic catalyst by addition of a second metal (surface reactions), (2) formation of Pt-Rh particles in microemulsion or in microsuspension, or (3) impregnation assisted by radiolysis. Catalysts were characterized by various techniques such as hydrogen chemisorption, transmission electron microscopy, temperature programmed reduction, adsorption of probe molecules (CO or NO then CO) followed by infrared spectroscopy, or model reactions.These characterizations allowed demonstrating that (i) the classical impregnation or the one assisted by radiolysis leads to monometallic and bimetallic particles, (ii) metal deposition on specific sites of preformed metallic particles can be obtained by surface modification of monometallic catalysts, (iii) the synthesis of metallic particles in microemulsion or microsuspension yields bimetallic entities with Pt-Rh alloy at the particle surface.

For several decades, the idea of flying and landing a less-than-man-rated nuclear reactor for planetary surface applications has been considered. This approach promises significant mass savings and therefore reduction in launch cost. To compensate for the lack of shielding, it has been suggested the use of in-situ materials for providing radiation protection. This would take the form of either raw dirt walls or processed soil materials into blocks or tile elements. As a first step in determining the suitability of this approach, it is necessary to understand the neutron activation characteristics of these soils. A simple assessment of these activation characteristics was conducted for both Martian and Lunar soils using ORIGEN2.2. An average composition for these soils was assumed. As a baseline material, commonly used NBS-03 concrete was compared against the soils. Preliminary results indicate that over 2.5 times more gamma-radiation production of these soils vs. concrete took place during the irradiation phase (a baseline of 2.4 x 1011 neutrons/sec-cm2 was assumed). This was due primarily to radiative capture on Na23 and Mn55 and subsequent decay of their activation products. This is does not necessarily disqualify these materials as potential shielding material since the -radiation output was only in the order of 4.2 x 108 photons/cm3-sec. Furthermore, these soils did not show any significant activity after shutdown of the neutron source (the reactor), since all activation products had very short half lives. Their performance in this area was comparable to that of NBS-03 concrete. / text