abstract: In the nano-regime many materials exhibit properties that are quite different from their bulk counterparts. These nano-properties have been shown to be useful in a wide range of applications with nanomaterials being used for catalysts, in energy production, as protective coatings, and in medical treatment. While there is no shortage of exciting and novel applications, the world of nanomaterials suffers from a lack of large scale manufacturing techniques. The current methods and equipment used for manufacturing nanomaterials are generally slow, expensive, potentially dangerous, and material specific. The research and widespread use of nanomaterials has undoubtedly been hindered by this lack of appropriate tooling. This work details the effort to create a novel nanomaterial synthesis and deposition platform capable of operating at industrial level rates and reliability. The tool, referred to as Deppy, deposits material via hypersonic impaction, a two chamber process that takes advantage of compressible fluids operating in the choked flow regime to accelerate particles to up several thousand meters per second before they impact and stick to the substrate. This allows for the energetic separation of the synthesis and deposition processes while still behaving as a continuous flow reactor giving Deppy the unique ability to independently control the particle properties and the deposited film properties. While the ultimate goal is to design a tool capable of producing a broad range of nanomaterial films, this work will showcase Deppy's ability to produce silicon nano-particle films as a proof of concept. By adjusting parameters in the upstream chamber the particle composition was varied from completely amorphous to highly crystalline as confirmed by Raman spectroscopy. By adjusting parameters in the downstream chamber significant variation of the film's density was achieved. Further it was shown that the system is capable of making these adjustments in each chamber without affecting the operation of the other. / Dissertation/Thesis / Masters Thesis Electrical Engineering 2015

abstract: X-ray crystallography is the most widely used method to determine the structure of proteins, providing an understanding of their functions in all aspects of life to advance applications in fields such as drug development and renewable energy. New techniques, namely serial femtosecond crystallography (SFX), have unlocked the ability to unravel the structures of complex proteins with vital biological functions. A key step and major bottleneck of structure determination is protein crystallization, which is very arduous due to the complexity of proteins and their natural environments. Furthermore, crystal characteristics govern data quality, thus need to be optimized to attain the most accurate reconstruction of the protein structure. Crystal size is one such characteristic in which narrowed distributions with a small modal size can significantly reduce the amount of protein needed for SFX. A novel microfluidic sorting platform was developed to isolate viable ~200 nm – ~600 nm photosystem I (PSI) membrane protein crystals from ~200 nm – ~20 μm crystal samples using dielectrophoresis, as confirmed by fluorescence microscopy, second-order nonlinear imaging of chiral crystals (SONICC), and dynamic light scattering. The platform was scaled-up to rapidly provide 100s of microliters of sorted crystals necessary for SFX, in which similar crystal size distributions were attained. Transmission electron microscopy was used to view the PSI crystal lattice, which remained well-ordered postsorting, and SFX diffraction data was obtained, confirming a high-quality, viable crystal sample. Simulations indicated sorted samples provided accurate, complete SFX datasets with 3500-fold less protein than unsorted samples. Microfluidic devices were also developed for versatile, rapid protein crystallization screening using nanovolumes of sample. Concentration gradients of protein and precipitant were generated to crystallize PSI, phycocyanin, and lysozyme using modified counterdiffusion. Additionally, a passive mixer was created to generate unique solution concentrations within isolated nanowells to crystallize phycocyanin and lysozyme. Crystal imaging with brightfield microscopy, UV fluorescence, and SONICC coupled with numerical modeling allowed quantification of crystal growth conditions for efficient phase diagram development. The developed microfluidic tools demonstrated the capability of improving samples for protein crystallography, offering a foundation for continued development of platforms to aid protein structure determination. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2016

abstract: Proton beam therapy (PBT) is a state-of-the-art radiotherapy treatment approach that uses focused proton beams for tumor ablation. A key advantage of this approach over conventional photon radiotherapy (XRT) is the unique dose deposition characteristics of protons, resulting in superior healthy tissue sparing. This results in fewer unwanted side effects and improved outcomes for patients. Current available dosimeters are intrinsic, complex and expensive; hence cannot be used to determine the dose delivered to the tumor routinely. Here, we report a hydrogel based plasmonic nanosensor for measurements of clinical doses in ranges between 2-4 GyRBE. In this nanosensor, gold ions, encapsulated in a hydrogel, are reduced to gold nanoparticles following irradiation with proton beams. Formation of gold nanoparticles renders a color change to the originally colorless hydrogel. The intensity of the color can be used to calibrate the hydrogel nanosensor in order to quantify different radiation doses employed during treatment. The potential of this nanosensor for clinical translation was demonstrated using an anthropomorphic phantom mimicking a clinical radiotherapy session. The simplicity of fabrication, detection range in the fractionated radiotherapy regime and ease of detection with translational potential makes this a first-in-kind plasmonic colorimetric nanosensor for applications in clinical proton beam therapy. / Dissertation/Thesis / Masters Thesis Chemical Engineering 2017

Orientador: Ivana Cesarino / Abstract: A new biosensor was developed by a simple electrocodeposition of reduced graphene oxide (rGO), polypyrrole (PPy) and the enzyme acetylcholinesterase (AChE) on surface of platinum (Pt) electrode. In potential range of -0.2 to +0.5 V vs. Ag/AgCl/KCl (3.0 mol L-1), using differential pulse voltammetry (DPV), it was observed a process in + 0.1 V and this corresponds to the dimerization of electrochemical oxidation products of thiocholine, resulting in ditio-bis-choline. The biosensor developed was evaluated using DPV in the analysis of carbaryl, which inhibits the AChE enzyme action. The best results achieved were with the followings optimized conditions: 75 mV pulse amplitude, step potential of 4 mV, and a phosphate buffer solution (PBS) 0.2 mol L-1 and pH 6.0. Using these parameters was observed a linear response to carbaryl in a range of 0.1 to 0.5 µmol L-1, with a detection limit of 11.6 nmol L-1 (2.3 µg/kg), which is an appropriate limit for determination of carbaryl in the cultures which these pesticide is applied, considering the maximum reside limit allowed by Brazilian legislation. The biosensor proposed, Pt/rGO/PPy/AChE, was applied successfully in the determination of carbaryl in samples of cabbage and tomato. / Resumo: Um novo biossensor foi desenvolvido baseado na simples eletrocodeposição do óxido de grafeno reduzido (rGO), polipirrol (PPy) e da enzima acetilcolinesterase (AChE) na superfície do eletrodo de platina (Pt). No intervalo de potencial -0,2 a +0,5 V vs. Ag/AgCl/KCl (3,0 mol L-1), utilizando voltametria de pulso diferencial (DPV), observou-se um processo em +0,1 V e este corresponde a dimerização dos produtos de oxidação eletroquímica da tiolcolina, formando ditio-bis-colina. O biossensor desenvolvido foi avaliado utilizando DPV na análise do pesticida carbaril, o qual inibe a ação da enzima AChE. Os melhores resultados obtidos foram com as seguintes condições otimizadas: 75 mV amplitude de pulso, incremento de potencial de 4 mV, e uma solução tampão fosfato (PBS) 0,2 mol L-1 pH 6,0. Usando tais parâmetros observou-se uma resposta linear para o carbaril no intervalo de 0,1 a 0,5 mol L-1, com um limite de detecção de 11,6 nmolL-1 (2,3 µg/kg), que é um limite adequado para determinar carbaril nas culturas em que este pesticida é aplicado considerando o limite máximo de resíduo permitido pelas legislações brasileiras. O biossensor proposto, Pt/rGO/PPy/AChE, foi aplicado com sucesso na determinação de carbaril em amostras de tomate e repolho. / Mestre

A Nanotecnologia trouxe alguns novos desafios, como o desenvolvimento de qualidade e processos de síntese relativa a nanoestruturas baseado em substâncias inorgânicas e orgânicas. O desenvolvimento de novos materiais com compostos orgânicos e inorgânicos, em escala nanométrica, tem recebido destaque em primeiro plano na Ciência dos Materiais devido à grande potencialidade para aplicações, tais como compósitos, catálise, óptica não linear, sensores e sistemas microeletrônicos [1, 2]. O desenvolvimento de materiais nanoestruturados tem atraído grande interesse para a nova realidade tecnológica, devido ao amplo alcance de aplicações incluindo as propriedades catalíticas, magnéticas e fotônicas [3, 4]. Contudo o objetivo dessa dissertação foi obter filmes automontados de polieletrólitos fabricados através da adsorção sequencial de soluções aquosas de polieletrólitos fracos baseados na interação eletrostática de polímeros com cargas opostas e posteriormente analisar a incorporação de nanopartículas de ouro (NPs Au) estabilizadas por citrato de sódio e por poli(vinilpirrolidona) (PVP). Neste trabalho foram utilizados os seguintes polieletrólitos, o PEI (poli(etileno imina)) e o PAH hidrocloreto de poli(alilamina) como policátions e o PAA (poli(ácido acrílico)) como poliânion. A presença das nanopartículas de ouro foi confirmada por Espectroscopia UV VIS NIR e Difração de Raios X (DRX). A morfologia e distribuição dos filmes automontados com nanopartículas de ouro foram analisadas por Microscopia de Força Atômica (MFA) e Microscopia Eletrônica de Transmissão (MET). A quantificação e espessura das amostras foram analisadas por Espectrometria de Retroespalhamento Rutherford (RBS) e posteriormente avaliadas em conjunto com as técnicas de espectroscopia UV VIS NIR e MET. As abordagens experimentais utilizadas neste trabalho mostraram a grande importância do pH para a fabricação de filmes automontados, devido à sua influência nos grupos funcionais dos polieletrólitos, afetando a interação eletrostática entre os mesmos e também entre as nanopartículas posteriormente difundidas. Quanto menor a densidade de carga da molécula de polieletrólito, maior será o número necessário das mesmas para compensar uma determinada carga superficial do substrato e/ou camada inferior. Com o aumento desse número, maior será a quantidade de sítios presentes passíveis de interação eletrostática. Dentre os sistemas estudados, o que mostrou-se mais eficiente foi o (PAH7/PAA4)20, o qual apresentou uma maior incorporação de NPs Au, e consequentemente a maior quantidade de NPs Au no sistema. / Submitted by Marcelo Teixeira (mvteixeira@ucs.br) on 2014-06-05T18:02:35Z No. of bitstreams: 1 Dissertacao Tatiane Michele Popiolski.pdf: 2153136 bytes, checksum: f652e5b4987e2b788d4f0b04b47b7844 (MD5) / Made available in DSpace on 2014-06-05T18:02:35Z (GMT). No. of bitstreams: 1 Dissertacao Tatiane Michele Popiolski.pdf: 2153136 bytes, checksum: f652e5b4987e2b788d4f0b04b47b7844 (MD5) / Nanotechnology has brought some new challenges such as the development of quality and synthesis processes on nanostructures based on inorganic and organic substances. The development of new materials with organic and inorganic compounds on the nanometer scale, has been featured at the forefront of materials science due to the large potential for applications such as composites, catalysis, nonlinear optics, sensors and microelectronic systems [1, 2, 3]. The development of nanostructured materials has attracted great interest for the new technological reality, due to the wide range of applications including catalytic properties, magnetic and photonic [4, 5, 6]. However the objective of this dissertation was to obtain self-assembled polyelectrolyte films fabricated by sequential adsorption of aqueous solutions of weak polyelectrolytes based on electrostatic interaction of polymers with opposite charges and analyze the distribution of gold nanoparticles (Au NPs) stabilized by sodium citrate and poly (vinylpyrrolidone) (PVP). In this work we used the following polymers, PEI (poly (ethylene imine)) and PAH hydrochloride poly (allylamine) as polycations and PAA (poly (acrylic acid) as polyanion. The presence of gold nanoparticles was confirmed by UV VIS NIR spectroscopy and X-ray Diffraction (XRD). The morphology and distribution of films with self-assembled gold nanoparticles was analyzed by Atomic Force Microscopy (AFM) and transmission electron microscopy (TEM). Quantification and thickness of the samples were analyzed by Rutherford backscattering spectrometry (RBS), and then evaluated in conjunction with the techniques of UV VIS NIR spectroscopy and TEM. The experimental approaches used in this work showed the great importance of pH for the fabrication of LbL self-assembled films due to its influence on the functional groups of polyelectrolytes, affecting the electrostatic interaction between them and between the nanoparticles subsequently disseminated. Smaller the charge density of the polyelectrolyte molecule, greater the required number of them to compensate a given surface charge of the substrate and/or lower layer. With the increase of that number, the greater the amount of sites present subject of electrostatic interactions. Among the systems studied, the most efficient was (PAH7/PAA4)20, which showed a greater incorporation of Au NPs, and consequently the greatest amount of Au NPs in the system.

O uso de energias renováveis como a energia solar para a produção de gás hidrogênio (H2), por meio do processo fotocatalítico da quebra da molécula de água, é uma alternativa promissora às fontes de energias convencionais. Neste contexto, a produção de filmes finos nanoestruturados de diferentes materiais é uma aplicação que pode aliar a fotocatálise e a nanotecnologia. Assim, o principal objetivo deste trabalho foi avaliar o efeito de diferentes concentrações de ácido tetracloroaurico (HAuCl4) para incorporação de nanopartículas de ouro (NPs Au) na produção de H2, a partir de filmes finos suportados em celulose bacteriana (CB), produzidos através da técnica camada por camada utilizando os polieletrólitos fracos, hidrocloreto de polialilamina (PAH) e poli(ácido acrílico) (PAA), combinados com dióxido de titânio (TiO2). Por meio das técnicas de espectroscopia de absorção molecular na região do ultravioleta e visível (UV-Vis), difração de raios X (DRX), microscopia eletrônica de varredura (MEV) e espectroscopia de infravermelho foi possível verificar a absorção da CB na região do UV, os picos em 14,6º, 16,6º e 22,6º, a superfície constituída de fibras e as bandas características da CB, respectivamente. A área superficial específica de 1,57 m2 g-1 foi encontrada para a CB. A absorção na região do UV das soluções de HAuCl4 e TiO2 foram determinadas por UV-Vis. Através da técnica de DRX, calculou-se o tamanho médio do cristalito do TiO2 que foi de ~5 nm corroborando com a microscopia eletrônica de transmissão (MET). O TiO2 também foi caracterizado por fluorescência molecular, MEV e área superficial específica. O potencial zeta foi utilizado para analisar as soluções poliméricas (PAH e PAA) e a solução de TiO2. Os filmes de diferentes concentrações de HAuCl4 (1,25 mmol L-1, 2,5 mmol L-1 e 5 mmol L-1) e com diferentes tempos de luz UV (6h, 12h, 24h, 24h, 48h e 96h) foram analisados por cromatografia gasosa (CG). Destes filmes, os que mais produziram H2 em cada concentração de HAuCl4 (c1-24 / concentração de 1,25 mmol L-1 e 24h de luz UV), (c2- 6 / concentração de 2,5 mmol L-1 e 6h de luz UV) e (c3-24 / concentração de 5 mmol L-1 e 24h de luz UV), foram caracterizados antes e depois da fotocatálise. Através do UV-Vis, foi possível observar a presença de NPs Au e TiO2 nos filmes. Por DRX, notou-se os picos da CB, do TiO2 (25,3º) e do Au (38,18º e 44,5º) nos filmes. No MEV foi possível observar que o filme (c1-24) possuia grãos de Au dispersos na matriz e a presença de Ti em toda a superfície sem aglomerações, revelando-se como um filme homogêneo comparado aos filmes (c2-6) e (c3-24). Pela técnica de MET, analisou-se a morfologia, tamanho e distribuição das NPs Au nos filmes revelando valores em escala manométrica. O filme (c1-24) apresentou menores tamanhos de NPs Au (9 nm). Área superficial específica, perfilometria, Espectroscopia de Emissão Óptica de Descarga Luminescente e Espectrometria de emissão óptica com plasma também foram analisados para avaliar o efeito das concentrações e tamanhos de NPs Au nos filmes. O filme com menor concentração de HAuCl4 (c1-24), o qual tinha NPs Au menores que em maior contato com a superfície do TiO2 produziu mais H2, foi analisado por CG para aperfeiçoar o melhor desempenho na produção de H2 variando alguns parâmetros como reutilização do filme (c1-24a) e (c1-24b), alteração de substrato (c1-24d), aumento de camadas (c1-24f) e filme sem polímeros (c1-24g). Analisando todas as variações dos parâmetros foi concluído que o filme (c1-24) produziu 29,12 μmol h-1cm2 de H2 apresentando uma melhor atividade fotocatalítica. / Submitted by Ana Guimarães Pereira (agpereir@ucs.br) on 2017-05-10T16:47:00Z No. of bitstreams: 1 Tese Nicolle Dal Acqua.pdf: 2359937 bytes, checksum: 79a564bfa513c80ed882f203002fc4ca (MD5) / Made available in DSpace on 2017-05-10T16:47:00Z (GMT). No. of bitstreams: 1 Tese Nicolle Dal Acqua.pdf: 2359937 bytes, checksum: 79a564bfa513c80ed882f203002fc4ca (MD5) Previous issue date: 2017-05-10 / Fundação de Amparo à Pesquisa do Estado do Rio Grande do Sul, FAPERGS. / The use of renewable energy such as solar energy to produce hydrogen gas (H2), through the photocatalytic process of breaking the water molecule, is a promising alternative to conventional energy sources. In this context, the production of nanostructured thin films of different materials is an application that can combine photocatalysis and nanotechnology.Thus, the main objective of this work was to evaluate the effect of different concentrations of tetrachlorouric acid (HAuCl4) for the incorporation of gold nanoparticles (Au NPs) in H2 production from thin films supported on bacterial cellulose (BC), produced through of the technique layer by layer using the weak polyelectrolytes, polyallylamine hydrochloride (PAH) and polyacrylic acid (PAA) combined with titanium dioxide (TiO2). Through the techniques of molecular absorption spectroscopy in the ultraviolet and visible (UV-Vis), X-ray diffraction (XRD), scanning electron microscopy (SEM) and infrared spectroscopy (FTIR), it was possible to verify the absorption of BC in the UV region, the peaks at 14.6º, 16.6º and 22.6º, the fiber surface and the characteristic bands of BC, respectively. The specific surface area of 1.57 m2 g-1 was found for CB. Absorption in the UV region of the HAuCl4 and TiO2 solutions were determined by UV-Vis. By means of the XRD technique, the average crystallite size of the TiO2 was calculated which was ~5 nm corroborating with transmission electron microscopy (TEM). TiO2 was also characterized by molecular fluorescence, SEM and specific surface area. The zeta potential was used to analyze the polymer solutions (PAH and PAA) and the TiO 2 solution. The films with different concentrations of HAuCl4 (1.25 mmol L-1, 2.5 mmol L-1 and 5 mmol L-1) and with different UV light times (6h, 12h, 24h, 24h, 48h and 96h) were analyzed by gas chromatography (GC). Of these films, the ones that most produced H2 at each concentration of HAuCl4 (c1-24 / concentration of 1.25 mmol L-1 and 24h of UV light), (c2-6 / concentration of 2.5 mmol L-1 and 6h of UV light) and (c3-24 / concentration of 5 mmol L-1 and 24h of UV light) were characterized before and after photocatalysis. Through the UV-Vis, it was possible to observe the presence of Au and TiO2 NPs in the films. By XRD, the peaks were noted of CB, TiO2 (25.3 °) and Au (38.18 ° and 44.5 °) in the films. In the SEM it was observed that the film (c1-24) had Au grains dispersed in the matrix and the presence of Ti on the whole surface without agglomerations, revealing as a homogeneous film compared to the films (c2-6) and (c3-24). Using the MET technique, the morphology, size and distribution of Au NPs were analyzed in the films revealing values in manometric scale. The film (c1-24) presented smaller sizes of Au NPs (9 nm). Specific surface area, perfilometry, Glow-discharge optical emission spectroscopy (GD-OES) and inductively coupled plasma (ICP-OES) were also analyzed to evaluate the effect of concentrations and sizes of Au NPs in the films.The film with lower concentration of HAuCl4 (c1-24), which had Au NPs less than in greater contact with the surface of TiO2 produced more H2, was analyzed by CG to improve the best performance in H2 production varying some parameters as reuse of the film (c1-24a) and (c1-24b), substrate change (c1-24d), increase of layers (c1-24f) and film without polymers (c1-24g). Analyzing all the variations of the parameters it was concluded that the film (c1-24) produced 29.12 μmol h-1 cm2 of H2 presenting a better photocatalytic activity.

O controle e a redução de atrito podem auxiliar na elaboração de estratégias de eficiência energética e na redução da emissão de dióxido de carbono (CO2). Apesar de existirem leis fenomenológicas bem estabelecidas para o atrito, não há uma definição da relação das propriedades macroscópicas/microscópicas com as propriedades fundamentais e nanoscópicas. O entendimento dessas correlações e dos mecanismos de dissipação de energia envolvidos no fenômeno de atrito podem ajudar no maior controle do coeficiente de atrito. Neste trabalho, o coeficiente de atrito de sistemas de óxidos na camada mais externa de ferro puro (99,99%) previamente nitretado são investigados visando encontrar relações entre as leis fenomenológicas, propriedades mecânicas e modelos teóricos envolvendo a dissipação energética via fônons. Para isso as amostras foram caracterizadas utilizando espectroscopia de emissão óptica de descarga luminescente (GD-OES), difração de raios X (DRX), tomografia de ponta atômica (APT), microscopia eletrônica de varredura (MEV), microscopia eletrônica de varredura por transmissão (STEM), nanoindentação e deslizamento unidirecional. Na caracterização experimental foi observada uma redução gradativa do coeficiente de atrito, a qual foi acompanhada por um aumento do teor de óxido na superfície. Apesar disso, essa tendência não foi observada na evolução das propriedades mecânicas. Logo, os cálculos teóricos baseados em mecanismos de dissipação fonônica aplicados para calcular o coeficiente de atrito representaram bem os valores experimentais. De forma geral, a mudança do coeficiente de atrito pode ser explicada mediante contribuições fonônicas, porém as forças de atrito do presente sistema não são totalmente determinadas por mecanismos fonônicos (sic). / Submitted by Ana Guimarães Pereira (agpereir@ucs.br) on 2017-11-20T19:05:37Z No. of bitstreams: 1 Tese Caren Machado Menezes.pdf: 4117143 bytes, checksum: bdf9c6981c075262a20f692e4bcab86e (MD5) / Made available in DSpace on 2017-11-20T19:05:37Z (GMT). No. of bitstreams: 1 Tese Caren Machado Menezes.pdf: 4117143 bytes, checksum: bdf9c6981c075262a20f692e4bcab86e (MD5) Previous issue date: 2017 / Control and reduction of friction can help in the elaboration of strategies of energy efficiency and in the reduction of carbon dioxide (CO2) emission. Although there are well established phenomenological laws for friction, there is no definition of the relationship of macroscopic / microscopic properties to fundamental and nanoscopic properties. The understanding of these correlations as well the mechanisms of energy dissipation involved in the friction phenomenon can help in a greater control of the coefficient of friction. In this work, the coefficient of friction of oxide systems in the outermost layer of pure iron (99.99%) previously nitrided is investigated aiming to find relationships between the phenomenological laws, mechanical properties and theoretical models involving energy dissipation via phonons. For this purpose, samples were characterized using glow discharge optical emission spectroscopy (GD-OES), X-ray diffraction (XRD), atomic probe tomography (APT), scanning electron microscopy (SEM), transmission scanning electron microscopy (STEM), nanoindentation and unidirectional sliding. In the experimental characterization, a gradual reduction of the coefficient of friction was observed, which was accompanied by an increase of the surface oxide content. Despite this, the same trend was not observed in the evolution of the mechanical properties. Therefore, the theoretical calculations based on the mechanisms of phononic dissipation applied to calculate the coefficient of friction well represent the experimental values. In general, the change in the coefficient of friction can be explained by phononic contributions, but the frictional forces of the present system are not totally determined by phononic mechanisms (sic).

O petróleo é uma matéria-prima de grande valor econômico. Buscando a substituição de matérias-primas não-renováveis, óleos vegetais vêm sendo usados cada vez mais como matéria-prima para combustíveis e polímeros. Derramamentos durante o manuseio de óleos são graves problemas ambientais. Fibras vegetais são usadas há muito tempo para a sorção de óleos em derramamentos. Resíduos de madeira na forma de serragem já são usados como sorventes de óleos, sendo um recurso barato e disponível. Entretanto, as características hidrofílicas das fibras vegetais reduzem sua capacidade de sorção de óleos. Os aerogéis de celulose tornaram-se um produto de grande interesse nessa área devido à sua alta porosidade (95 a 99%), baixa massa específica (0,004 to 0,15 g.cm-3) e alta área superficial (>60,m².g-1), além da abundância e sustentabilidade da celulose. O objetivo deste trabalho foi desenvolver um aerogel hidrofóbico de nanofibras de celulose a partir de resíduos da indústria moveleira (Pinus elliottii var. elliottii) processados por hidrólise ácida com explosão a vapor para a sorção de petróleo e óleos vegetais. No processo de explosão a vapor a melhor condição experimental foi observada para uma razão volumétrica de ácido acético e ácido nítrico 15:2:1 a 120°C e 30 minutos com rendimento superior a 90% em celulose e a remoção completa da hemicelulose e da lignina. Após a liofilização foi obtido um aerogel com massa específica 0,046 0,0013 g.cm-3 e porosidade 97,08 0,08%. A hidrofobização do aerogel gerou um ângulo de contato de 138,78º 0,78º. O aerogel mostrou capacidade de sorção máxima experimental (CSME) de 19,55 0,10 góleo.gaerogel-1 para petróleo e 13,73 0,62 góleo.gaerogel-1 para o óleo vegetal. A produção de nanofibras de celulose deu-se através de meios físicos (moagem) e a hidrofobização foi efetuada por modificação superficial das fibras com organosilanos (MTMS) por deposição a vapor. Na hidrólise do resíduo da indústria moveleira dois reagentes ácidos (ácido acético e ácido nítrico) foram testados individual e simultaneamente, com variações de temperatura, tempos e quantidade de reagente. A fração sólida rica em celulose obtida foi cominuída em moinho de pedras por 5 horas a 2500 rpm em uma suspensão com 1,5% m/m. O gel obtido foi congelado por 48 horas a -20ºC para posterior liofilização a -40ºC por 50 horas. Os aerogéis obtidos na liofilização foram tratados com o organosilano via deposição em fase vapor por 5 horas a 70ºC. O resíduo da indústria moveleira foi caracterizado quanto ao teor de celulose, hemicelulose, lignina, cinzas, extrativos e umidade. O processo de explosão a vapor foi caracterizado através do rendimento individual dos seus componentes (celulose e hemicelulose). Ensaios de massa específica aparente, ângulo de contato, porosidade, caracterização morfológica por microscopia eletrônica de varredura de emissão de campo, ensaios de sorção de óleos e cinética de sorção em meio homogêneo e heterogêneo de sorção de petróleo e óleo de soja foram realizados para caracterizar o aerogel. Modelos cinéticos de pseudoprimeira, pseudossegunda e pseudoenésima ordem foram ajustados aos dados experimentais em suas formas lineares e não-lineares. A sorção em meio homogêneo de petróleo foi bem ajustada com o modelo linear de pseudoprimeira ordem. A sorção de óleo vegetal foi bem ajustada tanto pelo modelo de pseudoprimeira ordem quanto pelo modelo de pseudossegunda ordem. Os modelos na forma não-linear indicaram um melhor ajuste dos dados experimentais pelo modelo de pseudoenésima ordem (n=0,95) para o petróleo e pelo modelo de pseudoprimeira ordem para o óleo vegetal. Os ajustes cinéticos mostraram que em meio heterogêneo a CSME se mantém constante em relação ao meio homogêneo, mas foi observada uma menor taxa de sorção. / Submitted by cmquadros@ucs.br (cmquadros@ucs.br) on 2018-02-01T18:30:09Z No. of bitstreams: 1 Dissertacao Pablo Beluck de Oliveira.pdf: 3113740 bytes, checksum: c1c0b51adf3c34f0f55f7579081223d8 (MD5) / Made available in DSpace on 2018-02-01T18:30:10Z (GMT). No. of bitstreams: 1 Dissertacao Pablo Beluck de Oliveira.pdf: 3113740 bytes, checksum: c1c0b51adf3c34f0f55f7579081223d8 (MD5) Previous issue date: 2018-02-01 / Ministério do Trabalho e Emprego, MTE. / Petroleum is a feedstock of great economic value. Due to the aim for non-renewable feedstocks substitution, vegetable oils have been used ever more as a feedstock for fuels and polymers. Spills during oil handling are serious environmental problems. Vegetable fibers have been used for a long time now as oil sorbents during spills. Wood residues as sawdust are currently used as oil sorbents, being a cheap and available resource. However, the hydrophilic profile of vegetable fibers reduce their capacity of oil sorption. Cellulose aerogels have become a product of great interest in the oil spill remediation field due to their high porosity (95 to 99%), low specific mass (0,004 to 0,15 g.cm-3) and high surface area (>60,m².g-1), besides cellulose abundance and sustainability. The objective of this work was to develop a hydrophobic aerogel from nanocellulose nanofibers obtained from furniture industry residues (Pinus elliottii var. elliottii) processed via steam explosion acid hydrolysis for petroleum and vegetable oil sorption. In the steam explosion process the best experimental condition was observed for a volumetric acetic acid and nitric acid ratio of 15:2:1 at 120ºC and 30 minutes with a cellulose yield higher than 90% and complete removal of hemicellulose and ligning. After lyophilization an aerogel of specific mass 0,046 0,0013 g.cm-3 and porosity 97,08 0,08% was obtained. Aerogel hydrophobization yielded a contact angle of 138,78º 0,78º. The aerogel exhibited a top experimental sorption capacity (CSME) of 19,55 0,10 goil.gaerogel-1 for petroleum and 13,73 0,62 goil.gaerogel-1 for vegetable oil. Cellulose nanofibers were produced by physical means (grinding) and hydrophobization was accomplished via vapor-phase deposition of organosilane (MTMS). In wood residue hydrolysis two acids were tested (nitric acid and acetic acid) simultaneously and individually, with variations of temperature, time and reagent amount. The solid fraction rich in cellulose was grinded in a rock mill for 5 hours at 2500 rpm in a 1,5% m/m suspension in water. The obtained gel was frozen for 48 hours at -20ºC for lyophilization at -40ºC for 50 hours. The aerogels obtained by lyophilization were treated with organosilane via vapor-phase deposition for 5 hours at 70ºC. The furniture industry residue was characterized as for its amounts of cellulose, hemicellulose, lignin, ashes, extractives and humidity. The process of steam explosion was characterized through the yields of individual components (cellulose and hemicellulose). Procedures like specific mass, contact angle, porosity, morphological characterization by scanning electron microscope with field emission gun, oil absorption tests and absorption kinetic in homogeneous and heterogeneous medium of petroleum and soy oil absorption were performed to characterize the aerogel. Kinetic models of pseudo-first, pseudo-second and pseudo-nth order were fitted to experimental data in their linear and non-linear forms. The absorption in homogeneous medium of petroleum was well fitted by pseudo-first linear kinetic model. Absorption of vegetable oil was well fitted by both pseudo-first and pseudo-second models. Models in non-linear form indicated a better fit for experimental data by the pseudo-nth order model (n=0,95) for petroleum and by pseudo-first order for vegetable oil. Kinetic adjusts showed that in heterogeneous medium CSME is maintained, but sorption rate is smaller.

Made available in DSpace on 2014-06-11T19:29:10Z (GMT). No. of bitstreams: 0 Previous issue date: 2012-02-28Bitstream added on 2014-06-13T20:59:19Z : No. of bitstreams: 1 santos_mv_me_araiq.pdf: 5715657 bytes, checksum: 38ac3d8aa310bc3c29043a541d2ddce0 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Neste trabalho membranas de biocelulose ou celulose bacteriana (CB), obtidas de meios de cultura da bactéria Gluconacetobacter xylinus, foram utilizadas como matriz para preparação de novos compósitos, a saber, celulose - colóides metálicos, celulose - sílica e celuloses - composto de európio. Nanopartículas (NP) esféricas de prata, ouro e prata-ouro, foram preparadas utilizando-se citrato de sódio e/ou pectina como agentes ao mesmo tempo redutores e estabilizantes. As propriedades ópticas de suspensões aquosas das NP´s foram avaliadas por espectrofotometria. A morfologia e composição das NP´s foram avaliadas por Microscopia Eletrônica de Transmissão (MET), energia dispersiva de raios X (EDS) e difração de elétrons. As membranas CB-NP foram preparadas pela incorporação das suspensões de NP´s às membranas hidratadas. Após secagem foram obtidas membranas de CB/NP´s com NP´s dispersas homogeneamente no meio. A morfologia das membranas compósitas foi avaliada por Microscopia eletrônica de Varredura (MEV) e também MET. As membranas CB-sílica foram preparadas pela hidrólise “in situ” (membranas hidratadas) do tetraetóxido de silício (TEOS). As membranas CB-NP e CB-sílica foram preparadas contendo o corante luminescente Rodamina 6G. As propriedades de luminescência das membranas sob excitação de pulsos de laser de 532 nm foram avaliadas em função da energia do pulso. Observou-se emissão laser a partir de determinado limiar de energia sem a presença de cavidade óptica, configurando o que na literatura é conhecido como “laser aleatório”. Observou-se que a presença de NP´s metálicas ou de sílica aumentam a eficiência do processo de emissão devido ao efeito de plasmons de superfície no primeiro caso e de espalhamento no segundo caso. Finalmente membranas luminescentes de CB foram... / In this work biocellulose or bacterial cellulose (BC) membranes obtained from culture media of bacteria Gluconacetobacter xylinus were used as templates for preparation of new composites, namely cellulose/metallic colloids, cellulose/silica and cellulose/europium compounds. Nanoparticles (NP) of spherical silver, gold, silver and gold, were prepared using sodium citrate and / or pectin as reducing agents and stabilizers at the same time. The optical properties of aqueous suspensions of NP's were evaluated by spectrophotometry. The morphology and composition of the NP's were evaluated by transmission electron microscopy (TEM), energy dispersive X-ray (EDS) and electron diffraction. BC-NP membranes were prepared by incorporating the NP's suspensions in the hydrated BC membranes. After drying the BC/NP´s membranes containing homogeneously dispersed NP's in the medium were obtained. The morphology of composite membranes was evaluated by electron microscopy (SEM and TEM). BC-silica membranes were prepared by in situ hydrolysis (hydrated membranes) of silicon tetraethoxide (TEOS). BC/NP and BC-silica membranes were prepared containing the luminescent dye Rhodamine 6G. The luminescence properties of the membranes under excitation laser pulses of 532 nm were measured as a function of pulse energy. Laser emission was observed from a certain threshold of energy without the presence of optical cavity and forms the well known in the literature random laser. It was observed that the presence of metallic or silica NP's increase the efficiency of the emission due to the effect of surface plasmons in the first case and scattering in the second case. Finally luminescent BC membranes were prepared by in situ” synthesis of europium complexes. The thermal profile was evaluated by thermogravimetric measurements and the... (Complete abstract click electronic access below)

Thesis (DTech (Science))--Peninsula Technikon, Cape Town, 2003. / The impetus for the refinement and renewal of daily-used products has spurred international interest in investigating the small in homogeneities that might exist in these products. This interest has become an important part in the design philosophy, which is based on structural information gained by the analysis of these products. It is this drive that initiated the study to investigate the simultaneous use of novel nuclear analytical techniques such as micro proton induced X-ray emission( u-PlXE), micro proton induced gamma-ray emission (u-PlGE) and micro proton backscattering (u-RBS) to achieved a broader and yet deeper insight into the fine structure of products. The fundamental underlying physical principles of these techniques are discussed to gain in-depth knowledge on how to them to obtain the desired information. Also determined was the degree of accuracy that could be attained in the application of this knowledge. These principles were evaluated in conjunction with the instrumentation with which the applicability of these techniques could then be further extended. More so is the use of sophisticated software that facilitated the use of both physical and instrumental parameters. After describing the necessary implements to achieve this further know-how, products of industrial origin were investigated to determine in homogeneities that existed in those products and compared those theoretical values. The first application was made to ceramic-based sorption electrodes to be used in the purification of wastewater.