Yes / While achieving the spatial organization of cells within 3D assembled nanofiber/cell constructs via nanofiber-enabled cell layering, the small sizes of inter-fiber pores of the electrospun nanofiber mats could significantly limit cell penetration across the layers for rapid formation of an integrated tissue construct. To address this challenge, efforts were made to improve cell-infiltration of electrospun nanofiber mats by modulating the density distribution and spatial organization of the fibers during electrospinning. Collection of collagen-containing electrospun nanofibers (300–600 nm in diameter) onto the surface of a stainless steel metal mesh (1 mm × 1 mm in mesh size) led to the periodic alternation of fiber density from densely packed to loosely arranged distribution within the same mat, in which the densely packed fibers maintained the structural integrity while the region of loose fibers allowed for cell penetration. Along with improved cell infiltration, the distinct fiber organization between dense and loose fiber regions also induced different morphology of fibroblasts (stellate vs. elongated spindle-like). Assembly of cell-seeded nanofiber sheets into 3D constructs with such periodically organized nanofiber mats further demonstrated their advantages in improving cell penetration across layers in comparison to either random or aligned nanofiber mats. Taken together, modulation of nanofiber density to enlarge the pore size is effective to improve cell infiltration through electrospun mats for better tissue formation. / NSF-IIP. Grant Numbers: 1338958, 1346430; NSF-DMR. Grant Number: 1508511; NSF-CBET. Grant Number: 1033742; and NIAMS. Grant Number: 1R21 AR056416

The Sustainable Water Interactive for Tomorrow (SWIFT) project in eastern Virginia is a Managed Aquifer Recharge project designed to alleviate the depletion of the Potomac Aquifer System due to unsustainable groundwater withdrawals. At the SWIFT Research Center (SWIFTRC) in Nansemond, VA, a pilot testing well (TW-1) has been implemented to help determine the feasibility of full-scale implementation. The pumping data from TW-1 and observation head data from surrounding monitoring wells (MW) at the SWIFTRC were used to calculate hydrogeological parameters (transmissivity, hydraulic conductivity, specific storage, and storage coefficient). Two sets of data were analyzed from before and after TW-1 was rehabilitated to account for the change in the flow distribution to each screen in TW-1. Comparing the results to past literature, the calculated (Theis and Cooper-Jacob methods) hydraulic conductivity/transmissivity values are within the same order of magnitude. Using borehole logs as well as apparent conductance and resistivity logs, multiple single and multi-layered models for both the upper and middle Potomac aquifers were produced with MODFLOW. Parameter estimation using MODFLOW and PEST and the two sets of observation data resulted in hydrogeological parameters similar to those calculated using Theis and Cooper-Jacob methods. The change in the hydraulic conductivity and specific storage between the pre and post rehabilitation flow distributions is proportional to that change in the flow distribution. For future modeling of the aquifer system, the hydrogeological parameters from the model using the 4/26/19 data set with the post rehabilitation flow distribution is recommended. Drawdown results from a multi-layered MODFLOW model were compared to results using the Theis method using both the Theis-calculated and MODFLOW-PEST modeled hydrogeological parameters. The results were nearly identical except for the Upper Potomac Aquifer (UPA) layer 1, as the model has a large change in aquifer thickness with distance from TW-1 that the Theis-based calculations do not consider. Travel times from the monitoring wells to TW-1 were calculated with the single and multi-layered models pumping 700 GPM from TW-1. Travel times from the SWIFT MW within the UPA sublayers ranged from 204 to 597 days depending on the sublayer, while travel times from the USGS MW within the UPA sublayers ranged from 2,395 to 7,859 days. For the single layer model of the UPA, the travel time from the SWIFT MW to TW-1 was 372 days while the travel time from the USGS MW was 4,839 days. Travel times from the SWIFT MW within the MPA sublayers were 416 and 1,195 days, while travel times from the USGS MW within the MPA sublayers were 4,339 and 11,245 days. For the single layer model of the MPA, the travel time from the SWIFT MW to TW-1 was 743 days while the travel time from the USGS MW was 7,545 days. / Master of Science / The Sustainable Water Interactive for Tomorrow (SWIFT) project in eastern Virginia is a project designed to help slow the depletion of the Potomac Aquifer System due to unsustainable groundwater withdrawals. At the SWIFT Research Center (SWIFTRC) in Nansemond, VA, a testing well (TW-1) has been implemented to help determine if the full-scale implementation of the SWIFT project is feasible. The pumping data from TW-1 and observation head data from surrounding monitoring wells (MW) at the SWIFTRC were used to calculate hydrogeological parameters (transmissivity, hydraulic conductivity, specific storage, and storage coefficients). These parameters help describe the behavior of the aquifer system. Two sets of data were analyzed from before and after TW-1 was rehabilitated to account for the change in the flow distribution within TW-1. Comparing the results to past literature, the calculated (using analytical methods, Theis and Cooper-Jacob methods) hydraulic conductivity/transmissivity values are within the same order of magnitude. Using data from the boreholes, multiple single and multi-layered models for both the upper and middle Potomac aquifers were produced with MODFLOW, a groundwater modeling software. Estimating parameters using observation data within MODFLOW resulted in hydrogeological parameters similar to those calculated using the Theis and Cooper-Jacob methods. The change in the hydraulic conductivity and specific storage between the pre and post rehabilitation flow distributions within TW-1 is proportional to that change in the flow distribution. For future modeling of the aquifer system, the hydrogeological parameters from the model using the 4/26/19 (most recent) data set with the post rehabilitation (more current) flow distribution is recommended. Drawdown (decrease in the water table) results from a multi-layered MODFLOW model were compared to results using the Theis method using both the Theis-calculated and MODFLOW modeled hydrogeological parameters. The results were nearly identical except for the Upper Potomac Aquifer (UPA) layer 1, as the model has a large change in aquifer thickness with distance from TW-1 that the Theis-based calculations do not consider. The time it took for a particle of water to travel from the monitoring wells to TW-1 were calculated with the single and multi-layered models pumping 700 GPM from TW-1. Travel times from the SWIFT MW within the UPA sublayers ranged from 204 to 597 days depending on the sublayer, while travel times from the USGS MW within the UPA sublayers ranged from 2,395 to 7,859 days. For the single layer model of the UPA, the travel time from the SWIFT MW to TW-1 was 372 days while the travel time from the USGS MW was 4,839 days. Travel times from the SWIFT MW within the MPA sublayers were 416 and 1,195 days, while travel times from the USGS MW within the MPA sublayers were 4,339 and 11,245 days. For the single layer model of the MPA, the travel time from the SWIFT MW to TW-1 was 743 days while the travel time from the USGS MW was 7,545 days.

A number of different aspects of the chemistry of layered double hydroxides and similar materials have been explored in this thesis. The intercalation chemistry of these compounds, in both aqueous and mixed solutions, has been explored to synthesise over forty new hybrid layered materials by ion-exchange and rehydration-reconstruction methods. The host used include both previously-reported layered hydroxide compounds, and novel host materials synthesised by the extension of heterogeneous reactions of solid oxides. The synthesis of these novel materials provides insights into the factors that control the compatibility of the metal ions that may form hydrotalcite-like structures, in addition to providing compounds that may act as the precursors of catalysts and other functional materials. The new intercalation compounds synthesised show interlayer distances ranging from 7.1Å to 23.6Å, and demonstrate a variety of interlayer alignments as determined by powder X ray diffraction, dependent upon both the metallic content and the degree of hydration of the host compound. The anionic contents of the interlayer regions have been further characterised through infra-red spectroscopy, elemental microanalysis, solid-state NMR and thermogravimetric analysis techniques. The mechanism and kinetics of the release of the intercalated anions from the hosts have been studied in situations approximating their real-world applications, and the degree of release quantified by UV/Visible spectroscopy. Both the rates and mechanisms of anion release have been found to be dependent on the anion, the host, the temperature and the solution into which the anions are released; as such, the release timescales of the anions may be fined tuned through modifications of the host materials. In addition, an explanation has been suggested for the observed change in mechanism observed in instances of release in which the host compound is in only partial contact with the release medium.

The present doctoral thesis summarises results of investigation focused on the characterisation of materials involved in Solid Oxide Cell technology. The main topic of investigation was the ceramic cell, also known as MEA. Particular attention was given to the role that bi-material interfaces, co-sintering effects and residual stresses play in the resulting mechanical response. The first main goal was to investigate the effects of the manufacturing process (i.e. layer by layer deposition) on the mechanical response; to enable this investigation, electrode layers were screen-printed one by one on the electrolyte support and experimental tests were performed after every layer deposition. The experimental activity started with the measurement of the elastic characteristics. Both elastic and shear moduli were measured via three different techniques at room and high temperature. Then, uniaxial and biaxial flexural strengths were determined via two loading configurations. The analysis of the elastic and fracture behaviours of the MEA revealed that the addition of layers to the electrolyte has a detrimental effect on the final mechanical response. Elastic characteristics and flexural strength of the electrolyte on the MEA level are sensibly reduced. The reasons behind the weakening effect can be ascribed to the presence and redistribution of residual stresses, changes in the crack initiation site, porosity of layers and pre-cracks formation in the electrode layers. Finally, the coefficients of thermal expansion were evaluated via dilatometry on bulk materials serving as inputs for finite elements analyses supporting experiments and results interpretation. The second most important goal was to assess the influence of operating conditions on the integrity of the MEA. Here interactions of ceramic–metal interfaces within the repetition unit operating at high temperatures and as well at both oxidative and reductive atmospheres were investigated. The elastic and fracture responses of MEA extracted from SOC stacks after several hours of service were analysed. Layer delamination and loss of mechanical strength were observed with increasing operational time. Moreover, SEM observations helped to detect significant microstructural changes of the electrodes (e.g. demixing, coarsening, elemental migration and depletion), which might be responsible for decreased electrochemical performances. All the materials presented in this work are part of SOC stacks produced and commercialised by Sunfire GmbH, which is one of the world leading companies in the field.

O presente trabalho trata da preparação e caracterização de três tipos de materiais, todos envolvendo hidróxidos duplos lamelares (HDLs) contendo íons cobalto e alumínio na composição das lamelas. Primeiramente, avaliou-se a influência de parâmetros de síntese na obtenção de HDLs intercalados com os ânions inorgânicos carbonato, cloreto e nitrato. Segundo dados de espectroscopia eletrônica UV-VIS, ressonância paramagnética eletrônica (EPR) e espectroscopia de fotoelétrons excitados por raios X (XPS), ocorre a oxidação parcial do Co2+ em Co3+ na lamela de HDL e, no caso do material contendo íon carbonato, observa-se a presença de radical carbonato, demonstrando a reatividade redox das matrizes com íons cobalto. A segunda parte do trabalho consistiu na intercalação do ânion derivado do ácido 2- aminotereftálico (ATA) em HDL. A presença do cátion cobalto nas lamelas e do grupo amino na espécie orgânica promoveu alterações significativas nas propriedades eletrônicas e térmicas do material (abreviado Co2Al-ATA). Assim como na primeira parte desta tese, as transformações ocorridas com o íon ATA devem incluir a formação inicial de um radical orgânico (de modo similar à polimerização da anilina), para o qual o agente oxidante é o íon Co3+ lamelar. Os dados de espectroscopia vibracional (no infravermelho e Raman) e de XPS mostram a presença de segmentos reduzidos (benzenóide) e oxidados (quinóides) na espécie intercalada. A solubilização do HDL em meio ácido permitiu isolar um material orgânico de cor preta que possui segmentos semiquinóides (radical orgânico) em sua estrutura, além dos reduzidos. A última etapa da presente tese consistiu em pirolisar o material Co2Al-ATA mencionado acima. Verificou-se que a alteração no procedimento de pirólise, como a temperatura, o desenho do forno, a forma do cadinho (cilíndrico ou barca), o tempo de resfriamento do sistema ou a atmosfera dinâmica ou estática, por exemplo, afetam as propriedades do produto final de decomposição. Nos compósitos obtidos, as fases inorgânicas provenientes da decomposição do HDL foram uma mistura de óxidos mistos de cobalto e alumínio (Co(CoxAl1-x)2O4), óxido de cobalto (CoO) e cobalto metálico. A fase de carbono apresentou perfil espectral de carbono grafítico nanocristalino e foi obtida em valores de temperatura de pirólise superiores a 800°C. Os compósitos contendo nanopartículas de cobalto metálico são ferromagnéticos. A reatividade redox dos HDLs de cobalto e as propriedades de seus produtos de decomposição apresentam potencial para aplicação em dispositivos eletroquímicos. / The present work reports the preparation and characterization of three types of materials, all involving layered double hydroxides (LDHs) containing cobalt and aluminum ions in the layer composition. First, the influence of synthetic parameters on the production of LDHs intercalated with the inorganic anions carbonate, chloride and nitrate was evaluated. According to UV-VIS electronic spectroscopy, electron paramagnetic resonance (EPR) and x-ray photoelectron spectroscopic (XPS) data, the partial oxidation of Co2+ to Co3+ occurs in the LDH layer and, in the case of the material containing carbonate ion, the presence of carbonate radical species demonstrates the redox reactivity of the matrices with cobalt ions. The second part of the work comprised the intercalation of the anion derived from 2- aminoterephthalic acid (ATA) in to LDH. The presence of the cobalt cation in the layer and the amino group in the organic species promoted significant changes in the electronic and thermal properties of the material (abbreviated Co2Al-ATA). As in the first part of this thesis, transformations occurring with the ATA ion should include the initial formation of an organic radical (similar to aniline polymerization), for which the oxidizing agent is the Co3+ ion in the layer. The vibrational (infrared and Raman) spectroscopy and XPS data show the presence of reduced (benzenoid) and oxidized (quinoids) segments in the intercalated species. The solubilization of HDL in acid medium allowed the isolation of a black organic material that has semiquinoid (organic radical) segments in its structure besides the reduced one. The last stage of the present thesis consisted of pyrolysis of the Co2Al-ATA material mentioned above. It was observed that the change in pyrolysis procedure, such as temperature, furnace design, crucible shape (bark or cylinder), system cooling time or dynamic or static atmosphere, for example, affects the properties of the final product of decomposition. In the obtained composites, the inorganic phases from the HDL decomposition were a mixture of mixed oxides of cobalt and aluminum (Co(CoxAl1-x)2O4), cobalt oxide (CoO) and metallic cobalt. The carbon phase showed nanocrystalline graphite carbon spectral profile and was obtained at pyrolysis temperature values above 800 °C. The composites containing metallic cobalt nanoparticles are ferromagnetic. The redox reactivity of HDLs containing cobalt and the properties of their decomposition products present potential for application in electrochemical devices

O estudo apresentado nesta Tese diz respeito à química dos niobatos lamelares e aborda a síntese, caracterização, avaliação da reatividade intracristalina e das propriedades luminescentes desses materiais. Os niobatos lamelares utilizados foram o hexaniobato K4Nb6O17, o triniobato KNb3O8 e as perovskitas lamelares K1-xLnxCa2-xNb3O10 (Ln = La, Eu e x = 0,02; 0,25; 0,50; 0,75 e 1,00). Esses materiais são constituídos de lamelas que apresentam cargas negativas e a região interlamelar é preenchida por íons de potássio que mantêm a neutralidade dos sistemas. A reatividade intracristalina dos niobatos lamelares foi avaliada frente à intercalação de espécies simples como a butilamina e volumosas como o macrociclo porfirínico, o polioxocátion de alumínio e compostos orgânicos de silício. A alta densidade de carga lamelar dos niobatos lamelares dificulta a intercalação direta de espécies volumosas, o que fez com que novas rotas sintéticas fossem desenvolvidas a fim de permitir a imobilização de tais espécies na região interlamelar. As metodologias sintéticas desenvolvidas foram baseadas, principalmente, no uso de dispersões coloidais dos niobatos esfoliados que, a partir da reestruturação na presença da espécie convidada de interesse, tornou possível a intercalação de espécies volumosas. As propriedades luminescentes dos niobatos lamelares são extremamente dependentes da estrutura do material. Os niobatos com estrutura tipo perovskita não apresentam emissão enquanto que o hexaniobato apresenta emissão apenas a 77 K e o triniobato, à temperatura ambiente. Neste estudo foram avaliadas as propriedades luminescentes dos niobatos EuxK4-3xNb6O17, EuxK1-3xNb3O8 e KCa2Nb3O10 (intercalado com Eu3+ e dopado com 1 % de Eu3+ ou La3+). Foram observados processos de transferência de energia tanto nos niobatos intercalados com Eu3+ quanto nos dopados. A dopagem também provocou mudanças nas propriedades fotofísicas dos niobatos com estrutura perovskita, os quais passaram a apresentar emissão da matriz de niobato mesmo à temperatura ambiente. / The study described in this Thesis is related to the synthesis and evaluation of some chemical properties of layered niobates with formulas K4Nb6O17 (hexaniobate), KNb3O8 (triniobate) and K1-xLnxCa2-xNb3O10 (layered perovskites - Ln = La, Eu and x = 0.02; 0.25; 0.50; 0.75 and 1.00). These niobates are constituted of negative layers and an interlayer region filled with potassium ions that maintain the system charge neutrality. The reactivity of these niobates was evaluated through intercalation reactions of simple species such as butylamine and bulky species such as porphyrin, aluminum polyoxocation and organosilanes. The high charge density of the niobate layer makes the direct intercalation of bulky guest species more difficult. Therefore, to overcome this situation, new synthetic routes were developed. The intercalation of bulky species was achieved by using colloidal dispersions of exfoliated niobates that, upon restaking, incorporate the guest species into the interlayer region. The luminescent properties of the lamellar niobates are very dependent on the structure. Niobates that present a perovskite structure do not show emission even at liquid helium temperature. The hexaniobate presents emission at nitrogen liquid temperature and triniobate at both room and 77 K temperatures. In this study the luminescent properties of EuxK4-3xNb6O17, EuxK1-3xNb3O8 e KCa2Nb3O10 (intercalated with Eu3+ and doped with 1 % of Eu3+ or La3+) were evaluated. Charge transfers processes were observed in both intercalated and doped niobates with Eu3+ ion. The lanthanide doping also promoted changes in the photophysical properties of niobates with perovskite structure, which become to show emission of the niobate group even at room temperature.

O estudo apresentado nesta Tese diz respeito à química dos niobatos lamelares e aborda a síntese, caracterização, avaliação da reatividade intracristalina e das propriedades luminescentes desses materiais. Os niobatos lamelares utilizados foram o hexaniobato K4Nb6O17, o triniobato KNb3O8 e as perovskitas lamelares K1-xLnxCa2-xNb3O10 (Ln = La, Eu e x = 0,02; 0,25; 0,50; 0,75 e 1,00). Esses materiais são constituídos de lamelas que apresentam cargas negativas e a região interlamelar é preenchida por íons de potássio que mantêm a neutralidade dos sistemas. A reatividade intracristalina dos niobatos lamelares foi avaliada frente à intercalação de espécies simples como a butilamina e volumosas como o macrociclo porfirínico, o polioxocátion de alumínio e compostos orgânicos de silício. A alta densidade de carga lamelar dos niobatos lamelares dificulta a intercalação direta de espécies volumosas, o que fez com que novas rotas sintéticas fossem desenvolvidas a fim de permitir a imobilização de tais espécies na região interlamelar. As metodologias sintéticas desenvolvidas foram baseadas, principalmente, no uso de dispersões coloidais dos niobatos esfoliados que, a partir da reestruturação na presença da espécie convidada de interesse, tornou possível a intercalação de espécies volumosas. As propriedades luminescentes dos niobatos lamelares são extremamente dependentes da estrutura do material. Os niobatos com estrutura tipo perovskita não apresentam emissão enquanto que o hexaniobato apresenta emissão apenas a 77 K e o triniobato, à temperatura ambiente. Neste estudo foram avaliadas as propriedades luminescentes dos niobatos EuxK4-3xNb6O17, EuxK1-3xNb3O8 e KCa2Nb3O10 (intercalado com Eu3+ e dopado com 1 % de Eu3+ ou La3+). Foram observados processos de transferência de energia tanto nos niobatos intercalados com Eu3+ quanto nos dopados. A dopagem também provocou mudanças nas propriedades fotofísicas dos niobatos com estrutura perovskita, os quais passaram a apresentar emissão da matriz de niobato mesmo à temperatura ambiente. / The study described in this Thesis is related to the synthesis and evaluation of some chemical properties of layered niobates with formulas K4Nb6O17 (hexaniobate), KNb3O8 (triniobate) and K1-xLnxCa2-xNb3O10 (layered perovskites - Ln = La, Eu and x = 0.02; 0.25; 0.50; 0.75 and 1.00). These niobates are constituted of negative layers and an interlayer region filled with potassium ions that maintain the system charge neutrality. The reactivity of these niobates was evaluated through intercalation reactions of simple species such as butylamine and bulky species such as porphyrin, aluminum polyoxocation and organosilanes. The high charge density of the niobate layer makes the direct intercalation of bulky guest species more difficult. Therefore, to overcome this situation, new synthetic routes were developed. The intercalation of bulky species was achieved by using colloidal dispersions of exfoliated niobates that, upon restaking, incorporate the guest species into the interlayer region. The luminescent properties of the lamellar niobates are very dependent on the structure. Niobates that present a perovskite structure do not show emission even at liquid helium temperature. The hexaniobate presents emission at nitrogen liquid temperature and triniobate at both room and 77 K temperatures. In this study the luminescent properties of EuxK4-3xNb6O17, EuxK1-3xNb3O8 e KCa2Nb3O10 (intercalated with Eu3+ and doped with 1 % of Eu3+ or La3+) were evaluated. Charge transfers processes were observed in both intercalated and doped niobates with Eu3+ ion. The lanthanide doping also promoted changes in the photophysical properties of niobates with perovskite structure, which become to show emission of the niobate group even at room temperature.

The presented research report deals with the investigation of magnesium aluminum based layered double hydroxide (LDH) as a potential nanofiller and flame-retardant for polymers with special reference to polyethylene. LDH is a mixed hydroxide of di- and trivalent metal ions that crystallizes in the form of mineral brucite. The basic reason for selecting LDH or more specifically magnesium-aluminum based LDH (Mg-Al LDH) is their typical metal hydroxide-like chemistry and conventional clay-like layered crystalline structure. The former is helpful in the direct participation in flame inhibition through endothermic decomposition and stable char formation. On the other hand, the later makes LDH suitable for polymer nanocomposite preparation, which can address the poor dispersibility problem associated with conventional metal hydroxide type fillers in polyolefin matrix. Besides, unlike layered silicate type clays (often reported for their capability to improve flame retardancy of polymers), LDH being reactive during combustion has higher efficiency to reduce the heat released during combustion of the composites. LDH clay with fixed Al:Mg ratio was synthesized using urea hydrolysis method and characterized. The organic modification of Mg-Al LDH using anionic surfactants has been studied in details. The main purpose of such modification is to enlarge the interlayer distance and to render it more organophilic. The surfactants were selected based on their functionality, chain length, etc and the modification was carried out by regeneration method. In the modified LDHs, the surfactants anions are arranged as a monolayer in the interlayer region and expand the interlayer distance according to their tail size. PE/LDH nanocomposites were prepared by melt-compounding method using a co-rotating tightly intermeshed twin-screw extruder and the morphological, mechanical and flammability properties of the nanocomposites were investigated in details. The X-ray diffraction analysis and electron microscopic analysis show a complex LDH particle morphology with hierarchy of particle size and shape starting from exfoliated particles fragments to particle aggregates over few hundred nm size. The exfoliated LDH platelets are distributed both in the vicinity of large particles and also in the bulk matrix. The melt rheological characterization of the nanocomposites also reflects the similar complex particle morphology. The dynamic oscillatory shear experiments showed that with increasing LDH concentration, the rheological behavior of the nanocomposite melts deviates strongly from that of the unfilled polyethylene. Thermogravimetric analysis (TGA) shows that LDH significantly improves the thermal stability of the polymer matrix in comparison to the unfilled polymer. The flammability studies of the PE/LDH nanocomposites have been reported in terms of various standard methods, like limited oxygen index (LOI), cone-calorimetry and UL-94 vertical and horizontal burn tests. The cone-calorimetric investigation shows that the nanocomposites have significantly lower burning rate and heat released during combustion. With increasing concentration of LDH though the LOI value of the nanocomposite increases marginally, the burning behavior, like dripping, rate of burning, etc are significantly improved. The flammability performance of LDH in combination with other commonly used flame-retardant (magnesium hydroxide) was also investigated. It has been observed that in polyethylene, a 50 wt% combination filler (4:1 weight ratio of magnesium hydroxide and LDH) can provide similar flammability ratings (like V0 rating in UL94 test, no dripping, etc) as that observed with 60 wt% magnesium hydroxide alone.

O presente trabalho trata da preparação e caracterização de três tipos de materiais, todos envolvendo hidróxidos duplos lamelares (HDLs) contendo íons cobalto e alumínio na composição das lamelas. Primeiramente, avaliou-se a influência de parâmetros de síntese na obtenção de HDLs intercalados com os ânions inorgânicos carbonato, cloreto e nitrato. Segundo dados de espectroscopia eletrônica UV-VIS, ressonância paramagnética eletrônica (EPR) e espectroscopia de fotoelétrons excitados por raios X (XPS), ocorre a oxidação parcial do Co2+ em Co3+ na lamela de HDL e, no caso do material contendo íon carbonato, observa-se a presença de radical carbonato, demonstrando a reatividade redox das matrizes com íons cobalto. A segunda parte do trabalho consistiu na intercalação do ânion derivado do ácido 2- aminotereftálico (ATA) em HDL. A presença do cátion cobalto nas lamelas e do grupo amino na espécie orgânica promoveu alterações significativas nas propriedades eletrônicas e térmicas do material (abreviado Co2Al-ATA). Assim como na primeira parte desta tese, as transformações ocorridas com o íon ATA devem incluir a formação inicial de um radical orgânico (de modo similar à polimerização da anilina), para o qual o agente oxidante é o íon Co3+ lamelar. Os dados de espectroscopia vibracional (no infravermelho e Raman) e de XPS mostram a presença de segmentos reduzidos (benzenóide) e oxidados (quinóides) na espécie intercalada. A solubilização do HDL em meio ácido permitiu isolar um material orgânico de cor preta que possui segmentos semiquinóides (radical orgânico) em sua estrutura, além dos reduzidos. A última etapa da presente tese consistiu em pirolisar o material Co2Al-ATA mencionado acima. Verificou-se que a alteração no procedimento de pirólise, como a temperatura, o desenho do forno, a forma do cadinho (cilíndrico ou barca), o tempo de resfriamento do sistema ou a atmosfera dinâmica ou estática, por exemplo, afetam as propriedades do produto final de decomposição. Nos compósitos obtidos, as fases inorgânicas provenientes da decomposição do HDL foram uma mistura de óxidos mistos de cobalto e alumínio (Co(CoxAl1-x)2O4), óxido de cobalto (CoO) e cobalto metálico. A fase de carbono apresentou perfil espectral de carbono grafítico nanocristalino e foi obtida em valores de temperatura de pirólise superiores a 800°C. Os compósitos contendo nanopartículas de cobalto metálico são ferromagnéticos. A reatividade redox dos HDLs de cobalto e as propriedades de seus produtos de decomposição apresentam potencial para aplicação em dispositivos eletroquímicos. / The present work reports the preparation and characterization of three types of materials, all involving layered double hydroxides (LDHs) containing cobalt and aluminum ions in the layer composition. First, the influence of synthetic parameters on the production of LDHs intercalated with the inorganic anions carbonate, chloride and nitrate was evaluated. According to UV-VIS electronic spectroscopy, electron paramagnetic resonance (EPR) and x-ray photoelectron spectroscopic (XPS) data, the partial oxidation of Co2+ to Co3+ occurs in the LDH layer and, in the case of the material containing carbonate ion, the presence of carbonate radical species demonstrates the redox reactivity of the matrices with cobalt ions. The second part of the work comprised the intercalation of the anion derived from 2- aminoterephthalic acid (ATA) in to LDH. The presence of the cobalt cation in the layer and the amino group in the organic species promoted significant changes in the electronic and thermal properties of the material (abbreviated Co2Al-ATA). As in the first part of this thesis, transformations occurring with the ATA ion should include the initial formation of an organic radical (similar to aniline polymerization), for which the oxidizing agent is the Co3+ ion in the layer. The vibrational (infrared and Raman) spectroscopy and XPS data show the presence of reduced (benzenoid) and oxidized (quinoids) segments in the intercalated species. The solubilization of HDL in acid medium allowed the isolation of a black organic material that has semiquinoid (organic radical) segments in its structure besides the reduced one. The last stage of the present thesis consisted of pyrolysis of the Co2Al-ATA material mentioned above. It was observed that the change in pyrolysis procedure, such as temperature, furnace design, crucible shape (bark or cylinder), system cooling time or dynamic or static atmosphere, for example, affects the properties of the final product of decomposition. In the obtained composites, the inorganic phases from the HDL decomposition were a mixture of mixed oxides of cobalt and aluminum (Co(CoxAl1-x)2O4), cobalt oxide (CoO) and metallic cobalt. The carbon phase showed nanocrystalline graphite carbon spectral profile and was obtained at pyrolysis temperature values above 800 °C. The composites containing metallic cobalt nanoparticles are ferromagnetic. The redox reactivity of HDLs containing cobalt and the properties of their decomposition products present potential for application in electrochemical devices

Detta arbete handlar om att undersöka hur vi kan använda oss av det visuella i ett spel för att motivera till samarbete och locka till gemenskap. Vårt intresse låg i att undersöka kring tanken med att inte tänka sig ett spel som enbart en passiv flykt från verkligheten, utan som ett verktyg som kan användas till att motivera till samarbete. Det spel som vi valt att utveckla var bestämt att vara anpassat för barn runt 10-års ålder. Vi valde att använda oss av en metod som heter Layered Elaboration för att lära känna vår målgrupp tydligare, samt få idéer och inspiration till hur vi kan anpassa ett spel för denna målgrupp. Efter att vi haft en workshop tillsammans med barnen på en skola, där vi lät barnen rita vad de kom att tänka på kring olika teman de fått, utvecklade vi en spelbar prototyp som vi sedan lät barnen på samma skola testa för att få en utvärdering. Efter genomfört speltest fick vi reda på att grafiken i vårt spel måste vara tydlig nog för att man ska veta vad målet är, men samtidigt ändå ha en viss otydlighet, inom en viss gräns, för att tvinga spelare till att samarbeta med varandra för att de ska förstå hur de ska gå tillväga för att nå målet. / This work is about how we can make use of the visuals in a game to motivate cooperation and attract community. Our interest was to explore around the idea of not imagining a game only as a passive escape from reality, but as a tool that can be used to motivate cooperation. The game that we have chosen to develop was determined to be suitable for children around the age of 10. We chose to use a method called Layered Elaboration as a way to learn about our target audience more clearly, and also as a tool to get ideas and inspiration on how we can adapt a game for this target group. After we had a workshop with the children at a school, where we let the children draw what they came to think of about different themes they received, we developed a playable prototype we then let the children in the same school test to get an evaluation. After the gaming test was over we found out that the graphics in our game must be clear enough that you should know what the goal is, yet still have a certain ambiguity, within certain limits, to force players to cooperate with each other in order to understand how to proceed in order to reach the goal.