A low-cost titanium production process, the CSIR-Ti powder process, which aims to produce titanium powder directly by metallothermic reduction of titanium tetrachloride with lithium, has been under development at the Council for Industrial and Scientific Research (CSIR). Crude titanium powder produced using the CSIR-Ti process is inevitably contaminated with by-products such as lithium chloride, lithium and titanium dichloride. These by-products tend to become sources of impurities in titanium powder, specifically oxygen and chloride impurities. The presence of oxygen and chloride impurities has marked effects on the mechanical properties of titanium finished products. Consequently, for the crude titanium powder to be rendered useful downstream, it must be purified and the by-products reduced to concentrations specified in the commercial standards. The present study was undertaken to examine whether acid leaching could be used to selectively dissolve and prevent hydrolysis of the by-products—specifically excess lithium and unreacted titanium dichloride in the crude titanium powder produced by the CSIR-Ti process. A further objective was to determine whether a purified product that meets both oxygen and total residual chloride content as specified by the standards can be achieved. The effects of key leaching variables and their interaction were also investigated to gain fundamental understanding of these effects on the by-products leaching behaviour. A literature study to select a suitable lixiviant and to establish the aqueous chemistry of the byproducts and their effect on the leaching conditions was undertaken. It showed that of the various acids suggested in the literature, hydrochloric acid was the cheapest and that it was more suited for the CSIR-Ti leaching process than nitric acid, due to the common ion chloride. This simplifies the leachate purification process downstream. The literature study established that Ti(II) has no aqueous chemistry but instead is oxidised to Ti(III) in solution. It was found that Ti(III) is easily oxidised to TiO2+ by dissolved oxygen and water. However, the oxidation rate was slow in hydrochloric acid solutions with the advantage that hydrolysis of the ions could be minimised and the precipitation of the oxides or oxychlorides prevented. It was further revealed that the lithium neutralisation reaction is highly exothermic, with the possibility of raising the leachate temperature to 60°C, resulting in the contamination of the titanium powder particles by the oxide layer and precipitated hydrolysis products. Batch leaching tests were carried out using factorial design of experiments to investigate the effect of initial hydrochloric acid concentration, which was estimated by varying the concentration between 0.032 M and 1 M; particle size, which was varied between −10 mm and +10 mm; and the initial temperature, varied between 14°C and 30°C. The resulting data were modelled and analysed using the analysis of variance statistical method. The solid residues were analysed for oxygen and total residual chloride content. The solid residue was also characterised by scanning electron microscopy (SEM) to examine the morphology of the leached particles. Leaching kinetics model fitting was also conducted. The statistical analysis showed that of the three factors investigated, temperature was the factor with the most statistical significance on both the oxygen and chloride concentration in the purified product, followed by particle size. The effect of acid concentration proved to be minimal, a phenomenon attributed to low concentrations of acid-consuming impurities, specifically excess lithium in the crude product. Thus, the two concentrations of hydrochloric acid investigated were found to be efficient to prevent hydrolysis product formation. Scanning electron micrographs revealed that crushing the crude product with a jaw crusher occluded crude titanium pores, thus locking in some by-products in addition to the pores locked by sintering during the metallothermic reduction. The observation showed that residual chloride impurities in the purified product are not just a consequence of hydrolysis products but also byproducts locked deeper in the pores of the product. Based on the parameter ranges evaluated in the study, a product that satisfied both oxygen and chloride standard specifications was achieved when the crude product was leached in both 1 M and 0.032 M initial HCl concentrations, temperature of 30°C and particle size of +10 mm. The combination of (−10 mm and 14°C) at all concentrations also yielded acceptable oxygen and chloride content levels. Overall, it was concluded from the present work that purification of crude CSIR-Ti product by leaching in dilute HCl is technically feasible. / Dissertation (MSc Applied Sciences (Metallurgy))--University of Pretoria, 2014. / Materials Science and Metallurgical Engineering / MSc (Applied Sciences (Metallurgy)) / Unrestricted

Final publication is available at http://onlinelibrary.wiley.com/doi/10.1002/term.2060/abstract;jsessionid=F0849D98381EEF9E83401A02B9042F4D.f04t02 / 京都大学 / 0048 / 新制・課程博士 / 博士(医学) / 甲第19602号 / 医博第4109号 / 新制||医||1014(附属図書館) / 32638 / 京都大学大学院医学研究科医学専攻 / (主査)教授 別所 和久, 教授 伊佐 正, 教授 川口 義弥 / 学位規則第4条第1項該当 / Doctor of Medical Science / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(医学) / 甲第20807号 / 医博第4307号 / 新制||医||1025(附属図書館) / 京都大学大学院医学研究科医学専攻 / (主査)教授 椛島 健治, 教授 瀬原 淳子, 教授 上杉 志成 / 学位規則第4条第1項該当 / Doctor of Medical Science / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21743号 / 工博第4560号 / 新制||工||1711(附属図書館) / 京都大学大学院工学研究科都市社会工学専攻 / (主査)教授 田中 茂信, 准教授 田中 賢治, 教授 中北 英一 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

No description available.

Biomineralized lattice materials with have high mineral contents (~ 99 wt%), usually "conceal" multiscale structural arrangements for unique mechanical or functional performance, such as the remarkable damage tolerance despite of the brittle nature of the constituents (e.g., biogenic silica and calcite). However, the quantitative explorations of the structure-mechanics relationships in multiscale of biomineralized lattices remain insufficient and hence hinder the leverage of the functional benefits to design architected cellular materials. In this dissertation, I selected two groups of marine animals (i.e., Hexactinellid sponges and Echinoderms) for systematic structural-mechanical study. Their biomineralized lattice skeletons exhibit three representative types of multiscale structures: 1) multiscale hierarchical structure: skeleton of Hexactinellid sponge such as Euplectella aspergillum; 2) multiscale functionally graded structure: spine of sea urchin Heterocentrotus mammillatus; and 3) dual-scale (atomic and microlattice scales) periodic structure: ossicle of starfish Protoreaster nodosus. This dissertation develops quantitatively the structural-mechanical/functional correlations in biomineralized cellular materials for bio-inspired material design. Four different species of Hexactinellid sponges have been studied with particular focus on the species E. aspergillum. As an example of the multiscale hierarchical biomineralized lattice, the extremely lightweight skeleton (~99% porosity) of E. aspergillum exhibits 1) amorphous nanoparticular biogenic silica; 2) micron-sized fibrous spicule with cylindrically laminated silica layers separated by organic interfaces; 3) spicule bundles where the individual spicules merged by secondary silica deposition; 4) a centimeter-sized Voronoi-like cellular dome known as sieve plate; and 5) a centimeter-sized cylindrically arranged rectangular lattice with double-diagonal reinforcement and external helical ridge. Here, we discovered a series of mechanical or functional properties or formation process of structures in different length scales: 1) for the biogenic silica in three different species of Hexactinellid sponge, consistent modulus and hardness of the biogenic silica throughout the cross section of the spicule are found via substantial correlation between the measured values and locations; 2) for the sieve plate, the Voronoi-like cellular dome constructed by porous branch with increased height achieves balance between improved mechanical stiffness and large pore opening for sponge's current pumping mechanism; 3) via microstructural study, the formation process of the sieve plate is proposed; and 4) for the cylindrical skeletal body, the double-diagonal configuration and the ridge structure are found to provide tendency to optimize torsional rigidity, and enhanced radial stiffening and improved permeability, respectively. The cellular structure in the spine of the H. mammillatus (i.e., stereom) made of ~99wt% of single-crystalline calcite shows a multiscale functionally graded structure. We developed and optimized a cellular network analysis workflow on the large-volume 3D lattice structure obtained from the synchrotron-based micro-Computed Tomography scan. The analysis provides quantitative descriptions of the branch, ring structure, and septum which reveals a functionally graded structure in multiscale from the center region to the edge region of the spine: 1) in microscale, the branch thickness and length increases, resulting in a significantly decreased porosity; and 2) in macroscale, the center region of the spine with galleried stereom of highly aligned branches transits to the edge region with laminar stereom of radially arranged septa and interconnecting branches. The multiscale structural variations lead to the mechanical variations the increased elastic modulus and mechanical isotropy from the center to the edge of the spine. This provides a biological pathway for designing the lightweight, strong, and tough beam with multiscale structural gradient. In previous work, we discovered that ossicle in starfish P. nodosus possesses a unique dual-scale periodic lattice structure, which means periodic single crystal calcite in nanoscale and diamond triply periodic minimal surface (diamond-TPMS) lattice in microscale. It has three unique structural features: 1) microlattice dislocations in ossicles similar to those found in crystals with diamond cubic lattice; 2) a diamond-TPMS microlattice with ca. 50% relative density; and 3) dual-scale crystallographic coalignment between c-axis of the single-crystalline constituent calcite and the [111] direction of the diamond-TPMS microlattice. Based on this work, this dissertation mainly reveals: 1) unique type and core structures of the dislocations in the ossicle for stiffness, strength, and toughness; 2) the 3D property compensation of dual-scale crystallographic coalignment for improved mechanical isotropy; and 3) mechanical benefits (improved mechanical isotropy and effective fragment jamming) and morphological benefits (minimal surface and highest surface area to volume ratio) for 50% relative density. / Doctor of Philosophy / Architected lattice materials, featured by their tailorable 3D multiscale architectures, achieve unique mechanical properties such as breaking the trade-off between strength and toughness, and mechanical isotropy reaching theoretical limit. In nature, as a result of evolutionary driving force, the biomineralized skeletons of the animals such as sea sponge, sea urchin, and starfish usually delicately control the architectural arrangements in different length scales and provide excellent templates for the design of architected lattices with desirable properties. Quantitative understanding of the 3D multiscale structures and mechanics of these natural biomineralized lattices allows the development of bio-inspired materials that are, for example, simultaneously stiff, strong, and tough. This dissertation establishes the quantitative structural-mechanical/functional relationships in multiscale of three biomineralized lattices with high mineral contents (~99 wt%) and a wide range of porosity (50~99 vol%) in Hexactinellid sponges with main emphasis on species (Euplectella aspergillum), sea urchin Heterocentrotus mammillatus, and starfish Protoreaster nodosus. They are selected for their representative multiscale structures, i.e., multiscale hierarchical structure, multiscale functionally graded structure, and dual-scale (i.e., atomic and microlattice scales) periodic structure, respectively. Study of these biomineralized lattices significantly improve our understanding of the biological strategies in structural arrangement and pave the way towards bio-inspired modeling to leverage the mechanical benefits.

No description available.

Production of fine sediments in reef environments is a poorly understood but probably significant process. On the Great Barrier Reef, Cliona viridis is locally abundant. The sponge has been found from Lizard Island in the north, down to the southern part of the Central Region, and it is likely even more widespread. Although on individual reefs the sponge may occur almost anywhere, it is most abundant on lagoon path reefs ("bommies" in Australian), where it overgrows the substrate and bores to a constant depth of about 1.3cm. Sponge infestation reaches a maximum at a depth of 4 m covering almost 8% of the vertical sides of bommies. It is frequently the dominant benthic organism. Serial underwater photography demonstrates that colonies can expand laterally at a rate of about 1 cm yr⁻¹ removing approximately 40% of the substrate. This species is a major producer of fine sediment on the Great Barrier Reef. / Thesis / Master of Science (MS)

Ces travaux portent sur l’étude du transfert de l’arôme viennoiserie encapsulé dans une matrice constituée du mélange gomme acacia – maltodextrines et incorporé dans une génoise emballée (plastiques et papier), dans des conditions contrôlées de stockage (humidité relative et température). Le procédé d’encapsulation utilisé dans cette étude est la lyophilisation. Les propriétés physicochimiques des molécules volatiles influencent leur rétention. Ainsi, les molécules hydrophobes à haut poids moléculaire sont mieux conservées dans ce système. L’incorporation de capsules d’arômes dans les génoises influence leurs propriétés physiques (la couleur et la texture) et favorise la formation d’une croûte pouvant jouer un rôle barrière sur les transferts d’arômes. Au cours du stockage des génoises emballées, l’apport positif de l’encapsulation sur la rétention des arômes a été révélé. Le type d’emballage peut influencer la perte en composés d’arôme dans l’espace de tête génoise – emballage. Ainsi, les emballages plastiques offrent une meilleure conservation des molécules volatiles par rapport aux papiers traités / This study deals with transfer of viennoiserie aroma encapsulated in a acacia gum - maltodextrines matrix and incorporated in a packaged sponge cake (plastic and treated-paper), under controlled storage conditions (temperature and relative humidity). The process of encapsulation used in this work is freeze-drying. The physicochemical properties of the volatiles molecules influence their retention in the matrix. Thus, the hydrophobic molecules with high molecular weight are more retained. The incorporation of capsules in the sponge cake matrix influences the physical properties of food matrix (color and texture) and supports the formation of a crust which acts as a barrier in the flavour transfer. It was noted that encapsulation contributed in retaining flavour compounds during the storage of packaged sponge cake. Also, the type of packaging can influence the loss of flavour in the headspace between sponge cake and packaging. Indeed, plastic packaging offers a better conservation of volatiles molecules compared to treated-papers

La reparation de defauts osseux par les techniques de l’ingenierie tissulaire osseuse (ITO) est consideree comme une alternative aux greffes conventionnelles. L’objectif de ce projet de these fut de developper des materiaux destines a servir de scaffolds pour le comblement et la regeneration osseuse, ces derniers etant sous la forme d’hydrogels injectables d’une part, et d’eponges, d’autre part. Ces deux types de materiaux ont ete obtenus par melange de chitosane (CHT, cationique), et de polymere de cyclodextrine reticule par l’acide citrique (PCD, anionique), interagissant via des liaisons ioniques et formant des complexes polyélectrolytes. La premiere partie de la these a ete consacree au developpement et caracterisation d’une eponge CHT/PCDs qui a ete chargee avec le facteur de croissance de l’endothelium vasculaire (VEFG) dans le but de favoriser sa vascularisation. Le second volet de la these a eu pour objectif d’optimiser la formulation d’un hydrogel injectable destine a la chirurgie mini-invasive, compose de CHT et de PCD sous sa forme soluble (PCDs) et insoluble (PCDi) [CHT/PCDi/PCDs]. L'etude a ete concentree sur l’optimisation et la caracterisation des proprietes rheologiques de l’hydrogel. Enfin, une etude prospective sur le developpement de l'hydrogel/eponge composite en ajoutant une phase minerale - l'hydroxyapatite (HAp) dans la formulation a ete realisee afin d'ameliorer les proprietes mecaniques et osteoconductrices.L’eponges CHT/PCDs a ratio 3 :3 a ete obtenue par lyophilisation des hydrogels et a subi un traitement thermique (TT) afin d’ameliorer leur stabilite par la formation des liaisons covalentes. L’eponge CHT/PCDs avec un TT a 160°C a montre des proprietes de gonflement eleve (~600%) et une biodegradation ralenti induite par le lysozyme (~12% perte masse dans un mois). Sa microstructure, ses proprietes mecaniques de compression et sa cytocompatibilite avec deux types de cellules (pre-osteoblastes (MC3T3-E1) et endotheliales primaires (HUVECs) ont ete etudiees. Une porosite elevee (~87%) avec des pores interconnectes a ete observee par microtomographie de rayons X, ainsi qu’une bonne adhesion et colonisation cellulaire au sein de l’eponge par microscopie electronique a balayage (MEB). Le VEGF a ete incorpore dans l’eponge, et son profil de liberation a ete suivi, ainsi que la bio-activite du VEGF libere. La liberation du VEGF a ete rapide pendant les trois premiers jours, puis ralenti jusqu'a devenir non-detectable par la methode ELISA jusqu’a 7 jours. Le VEGF libere pendant les deux premiers jours a montre un effet pro-proliferation et pro-migration significatif sur les HUVECs.Les hydrogels injectables de CHT/PCDi/PCDs a differents ratios ont ete optimises et caracterises en fonction de leurs proprietes rheologiques, leur injectabilite, et leur cytotoxicite. L’impact de l’ajoute du PCDi dans l’hydrogel a ete clairement observe par analyses rheologiques Ainsi, l'hydrogel CHT/PCD, compose a parts egales de PCDi et de PCDs, a demontre le meilleur compromis entre stabilite structurelle, proprietes rheofluidifiantes et autoreparantes, et injectabilite. En plus, l’hydrogel a montre une excellente cytocompatibilite vis-avis les cellules pre-osteoblastes MC3T3-E1.Bases sur la formulation optimisee, l’HAp a ete incorporee a differentes concentrations dans l’hydrogel. L’ajout de la phase minerale n’a pas perturbe la formation ni la stabilite structurelle des hydrogels, mais a ameliore les proprietes viscoelastiques. Les eponges composites, elaborees par lyophilisation de ces hydrogels, ont montre que les particules de HAp etaient dispersees de maniere homogene dans la structure macroporeuse de l'eponge. Ces resultats encourageants ont montre qu'il etait possible de fournir un hydrogel injectable ou une eponge composite comme scaffold pour l’ITO [...] / Repair of bone defects by bone tissue engineering (BTE) methods is considered as an alternative to conventional grafts. The aim of this PhD project was to develop two types of BTE scaffolds for bone regeneration: one is in the form of injectable hydrogel, and the other is in the form of sponge. Both scaffolds based on the formation of polyelectrolyte complexes by mixing chitosan (CHT, cationic) and polymer of cyclodextrin (PCD, anionic). Besides developing the sponge scaffold, the vascularization of 3D scaffold (a challenge of BTE) was specially investigated in the first part of the work, for which vascular endothelial growth factor (VEFG) was loaded on the CHT/PCDs sponge to promote the vascularization. The second part of the thesis was dedicated to the elaboration of an injectable CHT/PCD hydrogel, which was intended for minimally invasive surgery. The formulation optimization of hydrogel was performed by tuning the composition ratios of two PCD components: soluble-form PCD (PCDs) and insoluble-form PCD (PCDi), in order to better reach the specific requirement (e.g. rheological properties) of injectable hydrogel for regenerative medicine. Finally, a prospective study on developing the composite hydrogel/sponge by adding a mineral phase - hydroxyapatite (HAp) in the formulation was realized to improve the mechanical and osteoconductive properties.CHT/PCDs sponges were obtained by freeze-drying the hydrogels CHT/PCDs 3:3. The thermal treatment (TT) at different temperatures was further applied on the sponge to improve the mechanical stability. The CHT/PCDs sponge treated at 160°C was opted for further study thanks to high swelling capacity (~ 600%) and moderate lysozyme-induced biodegradation rate in vitro (~ 12% mass loss 21 days). This sponge of choice was further evaluated for the microstructure, the mechanical property (compressive strength) and the cytocompatibility with pre-osteoblasts (MC3T3-E1) and endothelial cells (HUVEC). Results of X-ray microtomography showed a high porosity (~87%) in the sponge with interconnected pores. Good cell adhesion and in-growth (colonization) in the sponge were observed by scanning electron microscopy (SEM). After loading VEGF on the sponge, the release profile of VEGF and the bioactivity of released VEGF were thoroughly studied. It showed that the release of VEGF was rapid (burst) during the first two days, then slowed down up to non-detectable by ELISA method after 7 days. The released VEGF during the first two days showed a significant pro-proliferation and pro-migration effect on HUVECs.For the injectable CHT/PCDi/PCDs hydrogels, optimization of composition ratio was based on evaluating their rheological properties, injectability, and cytotoxicity. The beneficial effect of combining both PCDi and PCDs in the formula of the hydrogel was clearly observed on the properties of hydrogel. Namely, the CHT/PCD hydrogel, composed of equal quantity of PCDi and PCDs, demonstrated the best compromise between structural stability, shearthinning and self-healing properties, and injectability. An excellent cytocompatibility with preosteoblast cells (MC3T3-E1) was also confirmed for the hydrogel with this composition.Based on the optimized formulation, HAp was incorporated at different concentrations, which didn’t disturb the formation or the structural stability of the hydrogels, but improved the viscoelastic properties. The composite sponges, elaborated by lyophilization of these hydrogels, showed that the HAp particles homogeneously dispersed within the macroporous structure of the sponge. These encouraging results showed the feasibility of providing an injectable hydrogel or a composite sponge for BTE scaffold [...]