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Activated carbons are used widely for the adsorption of environmentally unfriendly species from both liquid and gas phases, the separation of gases and adsorption of species from aqueous solution. Examples of the processes are the adsorption of Au(CN)2 and Ag(CN)2 from aqueous solution for the recovery of precious metals, the treatment of waste water containing organic chemicals and toxic metal species and the preparation of metal catalysts supported on carbon. This investigation has involved the study of the influence of porous structure and surface functional groups on the adsorption of both anionic and cationic metal species in order to understand the mechanism of adsorption of these species on active carbon from aqueous solution. Various types of oxygen functional groups were introduced onto the surface of coconut shell derived activated carbon through oxidation using nitric acid. Fourier transform infrared spectroscopy (FTIR), temperature programmed desorption (TPD) and selective neutralisation were used to characterise the surface oxygen functional groups. The oxidised carbons were also heat treated to provide a suite of carbons where the oxygen functional groups of various thermal stability were varied progressively. It was found that acidic oxygen functional groups mainly as carboxylic acid groups were incorporated into activated carbon by HNO3 oxidation. The phenol and quinone groups were also introduced by the oxidation process while the lactone groups were formed during heat treatment. The oxygen functional groups had a range of thermal stabilities with carboxylic acid groups being the least stable. A coconut shell derived active carbon was treated with ammonia and nitric acid followed by ammonia to incorporate nitrogen functional groups into the carbon. Active carbon with high nitrogen content was also prepared from nitrogen-rich precursor polyacrylonitrile (PAN). X-ray absorption near edge structure spectroscopy (XANES) and FTIR were used to investigate the structures of the nitrogen functional groups in carbons. The possible nitrogen functional groups present on carbon surface were pyridinic, pyrrolic (or indolic), pyridonic and aromatic amine-like structures. The adsorption characteristics of gold and silver cyanide anionic species on a suite of active carbons derived from coconut shell, polyacrylonitrile and chemical modification of the coconut shell carbon were investigated. The gold and silver cyanide adsorption capacities for coconut shell derived carbons correlate with total pore volume. Nitric acid oxidation treatment of the carbon was detrimental to gold adsorption in spite of the incorporation of oxygen content of carbon. The influence of nitrogen functional groups in the carbon structure on gold and silver adsorption was investigated using carbons derived from polyacrylonitrile. The addition of ethanol and butanol to the solution had an adverse effect on gold adsorption. Adsorption of silver cyanide ionic species on the active carbon was suppressed in the presence of excess free cyanide ions in solution whereas gold cyanide adsorption was not greatly affected at room temperature. The adsorption of gold cyanide was suppressed by the excess free cyanide and sodium sulphide at 70 °C. The adsorption of cadmium ions was enhanced dramatically by oxidation of the carbon. The ratio of released proton to adsorbed cadmium on oxidised carbon was approximately 2 indicating cation exchange was involved in the adsorption process. Na+ exchange studies with the oxidised carbon gave a similar ratio. After heat treatment of the oxidised carbons to remove oxygen functional groups, the ratio of H+/Cd2+ decreased significantly as well as the adsorption capacity. Both reversible and irreversible adsorption were involved in the process of cadmium adsorption with reversible adsorption having higher enthalpy. The irreversible adsorption resulted from cation exchange with carboxylic acid groups whereas the reversible adsorption probably involved physisorption of the partially hydrated cadmium ion. The nitrogen functional groups may act as ligands which can coordinate with transition metal cations. The adsorption of transition metal cations such as Cd 2+, Ni2+ and Cu2+ on active carbon was appreciably increased by the nitrogen functional groups present on carbon surface whereas ammonia treatment of the carbon showed little effect on the adsorption of alkali earth metal cation Cat+. There is little difference in the adsorption capacities of cadmium ions on coconut shell derived carbon at pH 4.1 and pH 7 whereas the adsorption of cadmium ions was significantly enhanced with increasing pH for the carbons with high nitrogen content. The nitrogen rich carbons show selectivity towards various transition metal cations reflected by adsorbing more Cu 2+ than Cd2+. This is consistent with the fact that the coordination compound of Cu 2+ with pyridine has higher stability constant than that of cadmium.

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第15334号 / 工博第3213号 / 新制||工||1484(附属図書館) / 27812 / 京都大学大学院工学研究科化学工学専攻 / (主査)教授 大嶋 正裕, 教授 田門 肇, 教授 宮原 稔 / 学位規則第4条第1項該当

An experimental investigation was performed to study the confined boiling heat transfer characteristics over a saturated porous structure using distilled water as the working fluid. A thin stainless steel resistive foil stretched between two copper electrodes was used to heat a saturated porous plate with an effective pore size of 50 gm. The temperature distribution on the foil heater was measured using a high speed thermal imaging camera. The effect of the gap height between the heater and the porous plate on the heat transfer was investigated for gap heights ranging from 0 um to 1000 um and for heat fluxes ranging from 11.7 kW/m2 to 58.3 kW/m2. It was observed that the highest heat transfer rate was obtained at a gap height of approximately 600 pm. The main heat transfer mechanism is thought to be confined boiling in the small gap between the heating surface and the saturated porous structure. It was observed that the effect of the subcooled liquid temperature did not have a significant effect on the heat transfer. The effect of the pore size in the porous plate was investigated by repeating the measurements with a porous plate of 200 gm pore size. It was observed that the thermal resistance for the plate with a 200 gm pore size was significantly higher than the plate with 50 gm pores for gaps less than 300 gm. At a larger gap height of 600 gm, similar heat transfer performances were obtained for the two porous media. / Thesis / Master of Applied Science (MASc)

Hierarchical materials offer great promise for high-performance sensors and catalysis carriers. Well-defined hierarchically porous materials are promising candidates for a wide range of applications relating to biosensors, separations, drug delivery, surface-enhanced Raman scattering (SERS), etc. Research on synthetic methodologies is expanding. However, fabrication of hierarchical porous structures with tunable pore dimension and shape, controllable pore distribution and interconnectivity is still a challenging task in materials science. One of the main tasks of this work is to establish a facile and reliable approach of making well-defined hierarchically porous materials. Then, based on those multimodal porous structures, different functions and applications can be realized. This work utilizes a direct hard templating method to obtain hierarchical porous structures with a well-defined bimodal distribution of the pores based on hierarchical templates. The hierarchical templates were prepared by synthetically joining appropriately functionalized commercially available polystyrene (PS) latex spheres together. Two different coupling reactions were used to form the hierarchical templates: carbodiimide-assisted coupling of COOH groups with NH2 groups and base-assisted coupling of epoxy groups with NH2 groups. Two different morphologies of templates, "raspberry-like" and "strawberry-like" were made. The template can be defined by the sizes of both the "core" and the "satellite" spheres, and altering the coverage of "satellites" on the "core". The main advantage of this strategy is the tailorability of the size and shape of the hierarchical templates, which allows an easy and independent adjustment to the multiporosity of the material structure design. Also, the monodispersed hierarchical templates are constructed of only one material, can be isolated, and can be assembled using standard template packing procedures that have been used for unimodal porous material fabrication described in published literature. Based on the predefined monodispersed hierarchical templates, multimodal porous silica, bimodal porous gold film and porous capsules were fabricated in this work as representative 3D, 2D, and 0D hierarchical porous structures, respectively. Because the template was predefined as one whole body, the connectivity between the big pores and small pores is guaranteed. The way the templates are packed together on a surface also ensures connections between each "template-shaped pore cluster". The uniform interconnectivity and ordered arrangement among the pores allows the different modals of pores to communicate with each other. The different hierarchical porous materials made in this work were characterized with SEM, TEM, AFM, XPS, STEM, gas adsorption, and mercury intrusion porosity. The results indicate that the multimodal porous materials can be successfully fabricated using predefined hierarchical templates. The different arrangement (3D, 2D, 0D) of those templates and the independent tailorability of the pore sizes provide more flexibility and control on the hierarchical porous material fabrication. The main parts of this work are as follows: (1) Fabrication and characterization of morphology controllable hierarchical templates (2) Fabrication and characterization of various multimodal porous structures of different materials based on the obtained templates (3) Study of the application of hierarchical porous gold electrode obtained and (4) The comparison between conventional porous structures and hierarchical porous structures.

Orientador: Gustavo Franco Barbosa / Resumo: Há décadas, a engenharia de tecidos passou a ser considerada em diversas aplicações, um tratamento médico adequado, devido suas excelentes vantagens, além da escassez de órgãos e disponibilidade de tecidos para serem transplantados. Conhecida como regeneração de novos tecidos, esse ramo da engenharia biomédica fundamentada nos conhecimentos de Biologia, Química e Física, torna-se uma grande alternativa quando tratamentos farmacêuticos convencionais não são mais aplicáveis, utilizando-se de três tipos básicos de ferramentas: célula, scaffolds e fator de crescimento. Dessa forma, esse trabalho tem como propósito principal a manufatura de scaffolds, utilizando a tecnologia de impressão 3D a partir de polímeros termoplásticos biodegradáveis e fosfatos de cálcio (em escala micrométrica), com o objetivo de se obter estruturas 3D complexas e porosas que apresentem propriedades mecânicas adequadas (em relação a ossos) e interconectividade estruturada entre os poros. Com os modelos 3D dos scaffolds projetados, e a seleção e preparação dos materiais envolvidos, foram realizados ajustes de parâmetros para o processamento dos scaffolds e posterior fabricação dos mesmos, mediante o uso da tecnologia de manufatura aditiva com bioimpressora de microextrusão que utiliza sistema de distribuição pneumático para extrusão contínua do material. Por fim os scaffolds foram caracterizados por técnica de análise de propriedade mecânica por ensaio de compressão e as amostras avaliadas pelo método de M... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: For decades, tissue engineering has come to be considered in several applications, an adequate medical treatment, due to its excellent advantages, in addition to the scarcity of organs and the availability of tissues to be transplanted. Known as regenerating of new tissues, this branch of biomedical engineering grounded in the knowledge of biology, chemistry and physics, becomes a great alternative when conventional pharmaceutical treatments are no longer applicable, using three basic types of tools: cell, scaffolds and growth factor. Thus, the main purpose of this work is the manufacture of scaffolds, using the technology of 3D printing from biodegradable thermoplastic polymers and calcium phosphates (in micrometric scale), with the objective of obtaining complex and porous 3D structures that present properties mechanical (in relation to bones) and structured interconnectivity between the pores. With the 3D models of the scaffolds designed, and the selection and preparation of the materials involved, adjustments were made to the processing parameters of the scaffolds and their subsequent manufacture, using the technology of additive manufacturing with microextrusion bioprinter that uses pneumatic distribution system for continuous extrusion of the material. Finally, the scaffolds were characterized by technique of mechanical property analysis by compression test and the samples evaluated by Scanning Electron Microscopy (SEM) method. / Mestre

Due to their large internal surface area, microporous materials have been widely used in applications where high surface activity is desired. Example applications are extracellular scaffolds for tissue engineering, porous substrates for catalytic reaction, and permeable media for membrane filtration, etc. To realize these potential applications, various techniques such as TIPS (thermal induced phase separation), particle leaching, and SFF (solid freeform fabrication) were proposed and investigated. Despite of being able to generate microporous for specific applications, these available fabrication techniques have limitations on controlling the inner porous structure and the outer geometry in a cost-effective manner. To address these technical challenges, a systematic study focusing on the generation of microporous structures using co-continuous polymer blend was conducted. Under this topic, five subtopics were explored: 1) generation of gradient porous structures; 2) geometrical confining effect in compression molding of co-continuous polymer blend; 3) microporous composite with high nanoparticle loading; 4) micropatterning of porous structure; 5) simulation strategy for kinetics of co-continuous polymer blend phase coarsening process.

Dans le cadre du conditionnement des déchets nucléaires, les géopolymères représentent une alternative potentielle aux liants hydrauliques classiques. A ce jour, il est admis que la formation des géopolymères procède selon un mécanisme de dissolution - restructuration - polymérisation conduisant à un matériau solide. Cependant, les liens précis entre la composition de la solution d’activation, le déroulement des réactions de géopolymérisation et la microstructure finale doivent être déterminés du point de vue de la texturation et de l’évolution structurale du matériau. Ainsi plusieurs paramètres de formulation ont été étudiés : la nature de l’activateur alcalin, la concentration en silice et l’ajout d’une source d’aluminium. Il apparait que l’environnement chimique des précurseurs silicatés ou alumino-silicatés est contrôlé par les paramètres de formulation constitutifs de la solution d’activation. Lors de la formation du réseau géopolymérique, ces précurseurs jouent un rôle primordial sur la cinétique de dissolution du métakolin, la taille, l’arrangement et l’agrégation des oligomères alumino-silicatés participant à la formation du réseau poreux. A plus long terme, certaines caractéristiques du réseau poreux qui sont-elles même contrôlées par la taille et l’agencement des oligomères, varient légèrement au cours du temps. Le réarrangement de la structure poreuse associé d’une part à la densification du réseau solide, et d'autre part à la fermeture partielle de la porosité conduit à une légère augmentation de la taille des pores et à une diminution du volume poreux accessible. / In the context of conditioning of nuclear waste, geopolymers represent a potential alternative to conventional hydraulic binders. Currently, it is recognized that the formation of geopolymer proceeds according to a mechanism of dissolution - restructuring - polymerization resulting in a solid material. Despite the availability of many studies to understand these mechanisms, the precise relationship between the chemical nature of the activating solution, the geopolymerization process and the final microstructure should be determined from the point of view of the texturing and the structural evolution of the material. In this work, several parameters were studied: the nature of the alkali activator, the silica concentration and the addition of an aluminum source. It appears that the chemical environment of the silicate or aluminosilicate precursors is controlled by the activating solution composition. During the consolidation of the geopolymer network, these precursors play an important role on the dissolution rate of metakaolin, the size, the rearrange¬ment and the aggregation of aluminosilicate oligomers involved in the porous solid network formation. Subsequently, some characteristics of the porous network which are controlled by the size and the rearrangement of oligomers vary slightly over time. The refinement of the porosity associated to first, a densification of the solid network, and secondly, a partial closure of the porosity at the nanometer scale leads to an increase in the pore size and a decrease of the pore volume.

No description available.

Předkládaná práce se zabývá nalezením vhodných podmínek pro výrobu nanaporézní struktury na tenké hliníkové vrstvě. V této práci jsou popsány postupy výroby nanoporézních struktur a jejich přípravou. Vznikly póry o rozměrech 5–20 nm. Byla zkoumána závislosti proudové hustoty v zavislosti na přiloženém pulzu. Všechny výsledky byly zkoumány pomocí SEM analýzy. Byla použita cyklická volatmetrie pro stanovení redukčního napětí při depozici niklu a zlata.