Submitted by Marilene Donadel (marilene.donadel@unioeste.br) on 2018-04-26T20:42:12Z No. of bitstreams: 1 Caroline_Ribeiro_2018.pdf: 4186138 bytes, checksum: e15fcfac07f7fe535fcafad4cba066dd (MD5) / Made available in DSpace on 2018-04-26T20:42:12Z (GMT). No. of bitstreams: 1 Caroline_Ribeiro_2018.pdf: 4186138 bytes, checksum: e15fcfac07f7fe535fcafad4cba066dd (MD5) Previous issue date: 2018-02-27 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / This work focused on the characterization of an effluent of a recycling and recovery industry of automotive batteries and on the feasibility evaluation of different materials, a biosorbent (fish scales - FS), a mineral (dolomite - DL) and a commercial material (cationic resin - CR) combined use in the removal of heavy metals. The studied materials were physico-chemically and morphologically characterized (pHpzc, MEV-EDS, FTIR and XRD) before and after their use in the removal processes in order to understand the structural modifications of the materials. In addition, the elemental composition of the liquid and solid phases after the treatment process were evaluated by TXRF analysis. The effluent presented an extremely acidic characteristic (pH = 1) and the incidence of heavy metals above the legislation discharging limits (Fe, Zn and Pb). Due to the structural characteristics and its respective functional groups, each adsorbent material presented different functional groups and different behavior in solution, which led to different removal and neutralization capacities. The CR presented the highest removal capacity of the metallic ions, mainly governed by an ion exchange process. Whilst the FS and DL presented lower removal capacities following complex simultaneous phenomena such as dissolution, complexation, precipitation and adsorption. On spite of that, the FS and DL presented a great neutralization capacity (i.e. pH elevation of the extremely acidic medium), related to the leaching of its alkaline constituents. By considering the generation of chemical sludge as a key factor in the work, aiming its mitigation and the better quality of the treated effluent, it was verified that the sequential application of these materials in hybrid process could be a promising and feasible alternative, by taking advantage of the particular characteristics of each material both in the neutralization and heavy metals’ removal. In this way, the use of DL, FS and CR in combined hybrid processes was evaluated, initially in batch system. Amongst the evaluated ones, the DL-CR hybrid process, in which the dolomite was used for the effluent neutralization up to pH = 5 followed by CR for the metallic ions removal presented better results. Therefore, the DL-CR hybrid process showed the highest percentages of metal removal (99, 73 and 100%, respectively, for Fe, Zn and Pb), as well as the lowest generation of chemical sludge by the end of the processes. In addition, the pre-neutralization (pH = 5 achieved by the DL) provided greater chemical stability of the CR. Subsequently, the DL-RC hybrid process was employed in fixed bed, evaluating the possibility of adsorption-desorption cycles aiming at the resin reuse and recovery of heavy metals. Different affinities of each metal ions by the RC for the multicomponent system (Pb> Fe> Zn) were identified, which were associated with the properties of each species as radius of hydration, valence and electron affinity. The possibility of the RC use in recycle was verified, in which similar removal capacities to the previous cycle and compatible with the levels of disposal of legislation - in terms of concentration of heavy metals as well as pH - was reached. These results demonstrate the potential of the hybrid treatment process, however, the fixed bed operating conditions such as bed height and volumetric flow still can be optimized in order to maximize mass transfer efficiency in the bed. Therefore, considering that the DL-RC hybrid process was able to overcome the treatment drawbacks of such type of effluent, due to its extremely acidic character and the complex multicomponent composition of heavy metals in solution, the process can be considered viable in technical and operational terms. In general, the cooperative use between DL and RC in hybrid process presents a remarkable potential in the neutralization and treatment of heavy metals from the battery recycling industry. / Este trabalho enfocou na caracterização de um efluente de uma indústria de reciclagem-recuperação de baterias automotivas e na avaliação de viabilidade de utilização combinada de diferentes materiais, um biossorvente (escamas de peixe - ES), um mineral (dolomita - DL) e uma material comercial (resina catiônica - RC) na remoção de metais pesados. Os materiais estudados foram caracterizados físico-química e morfologicamente (pHpzc, MEV-EDS, FTIR e DRX) antes e após sua utilização nos processos de remoção visando compreender as modificações ocorridas na sua estrutura. Além disso, a composição elementar das fases líquida e sólida após o processo de tratamento foram avaliadas por análise TXRF. O efluente apresentou caráter extremamente ácido (pH=1) e presença de metais pesados acima dos limites da legislação de descarte (Fe, Zn e Pb). Devido às características estruturais e seus respectivos grupos funcionais, cada material adsorvente apresentou comportamentos distintos em solução, o que levou a diferentes capacidades de remoção e neutralização. A RC apresentou a maior capacidade de remoção dos íons metálicos, governada majoritariamente por um processo de troca iônica. enquanto que a ES e a DL apresentaram menores capacidades de remoção seguindo fenômenos simultâneos complexos como dissolução, complexação, precipitação e adsorção. Por outro lado, a ES e a DL, apresentaram uma grande capacidade de elevação do pH dos meios extremamente ácidos, relacionado à lixiviação dos seus constituintes alcalinos. Ao considerar a geração de lama química como um fator chave no trabalho, visando sua mitigação e o a melhor qualidade do efluente tratado, verificou-se que a aplicação desses materiais de forma sequencial em processo híbrido poderia ser viável e promissora, considerando as características particulares de cada um desses materiais, tanto na neutralização quanto para remoção de metais pesados. Neste sentido, avaliou-se o uso da DL, ES e RC em processos híbridos combinados em sistema batelada, sendo o processo híbrido DL-RC, o qual empregou a dolomita na neutralização do efluente até o pH = 5 seguido pela RC para remoção dos íons metálicos a combinação que apresentou melhores resultados. O processo híbrido DL-RC apresentou as maiores porcentagens de remoção dos metais (99, 73 e 100%, respectivamente, para Fe, Zn e Pb), bem como a menor geração de lama química ao final dos processos. Além disso, a pré-neutralização (pH = 5 alcançado pela DL) proporcionou uma maior estabilidade química da RC. Posteriormente, empregou-se o processo híbrido DL-RC em leito fixo avaliando-se, ainda, a possibilidade de ciclos de adsorção-dessorção visando a reutilização da resina e recuperação dos metais pesados. Identificou-se diferentes afinidades de cada íon metálico com a RC para o sistema multicomponente (Pb > Fe > Zn), associadas às propriedades de cada espécie como raio de hidratação, valência e eletroafinidade. Verificou-se a possibilidade do uso da RC em reciclo, atingindo-se capacidades de remoção similares ao ciclo anterior e compatíveis com os níveis de descarte de legislação em termos de concentração de metais pesados bem como de pH. Tais resultados evidenciam o potencial do processo híbrido de tratamento, no entanto, as condições operacionais do leito fixo como a altura do leito e vazão volumétrica ainda podem ser otimizadas visando a maximização da eficiência de transferência de massa no leito. Desta forma, considerando-se que o processo híbrido DL-RC foi capaz de contornar a problemática do tratamento de tais efluentes dado seu caráter extremamente ácido e a complexa composição multicomponente de metais pesados em solução o processo pode ser considerado viável em termos técnico-operacionais. No geral, o uso cooperativo entre DL e RC em processo híbrido apresenta notável potencial na neutralização e tratamento de metais pesados provenientes da indústria de reciclagem de baterias.

<div>Despite the abundant current applications for ionic hydrogels, much about the stimuli-responsive behavior of these materials remains poorly understood. Due to the soft nature of these materials, the number of traditional characterization methods which can be applied to these systems is limited. Many studies have been conducted to characterize bulk property responses of these materials, and experimental studies have been produced examining the distribution of free ions around single polyelectrolyte chains. However, little experimental work has been published in which molecular-scale interactions are elucidated in confined polyelectrolyte networks. Furthermore, the way in which responsive properties, other than bulk swelling capacity, scale with ionic fraction in mixed polyelectrolyte-non-polyelectrolyte hydrogel systems has not been thoroughly investigated.</div><div>The distribution and strength of polymer-counter-ion bonds has a remarkable effect on hydrogel properties such as absorption capacity, mechanical strength, and size and chemical selectivity. In order to tailor these properties for targeted applications in ionic environments, it is imperative that we thoroughly understand the character of these polymer-ion interactions and their arrangement within the bulk hydrogel. In order to do so, however, non-traditional methods of analysis must be employed.</div><div>This dissertation focuses on a model part-ionic hydrogel system, poly(sodium acrylate-co-acrylamide), in order to assess not only the polymer-counter-ion interactions but also the impact of gel ionic fraction on these interactions and the responses which they induce in gel performance properties. A model alkali (NaCl), alkaline earth (CaCl2), and transition (CuSO4) metal salt are employed to investigate changes in polymer properties from the macroscale to the nanoscale. The aim of this dissertation is to lay the foundation for the development of fundamental structure-property relationships by which we may fully understand the ionically-induced performance properties of polyelectrolyte networks.</div>

Fundação Carlos Chagas Filho de Amparo a Pesquisa do Estado do Rio de Janeiro / A espectroscopia fotoacústica (PAS) é uma técnica não destrutiva e muito utilizada na caracterização óptica e térmica de materiais. Ela é baseada no efeito fotoacústico que consiste, basicamente, na absorção de onda eletromagnética modulada e na geração de calor no interior do material em estudo (amostra), via processo de desexcitação não-radiativa. Dentre as muitas aplicações relacionadas à caracterização de materiais, recentemente, a técnica PAS vem sendo desenvolvida para estudos de transição de fase de segunda ordem. Entretanto, poucos trabalhos são encontrados na literatura com relação à aplicação da técnica PAS ao estudo da transição vítrea. Neste contexto, o objetivo deste trabalho é o de aplicar a técnica PAS na determinação da temperatura de transição vítrea de materiais poliméricos, de uma maneira inovadora com relação à célula fotoacústica e ao sistema de aquecimento. Para isso foi projetada e construída uma célula fotoacústica que possibilita a variação de temperatura da amostra, sem afetar a curva de resposta do microfone. Foi desenvolvido um sistema de aquecimento baseado no efeito Peltier, possibilitando fazer rampas de subida de temperatura, com várias velocidades, da temperatura ambiente até 130 C, de forma linear. Todo o aparato experimental foi testado e aplicado em várias amostras poliméricas: poliamida 6.0 (Nylon); poliestireno (PS-n1921 e PS-n2380); e poli(tereftalato de etileno) (PET). Os resultados obtidos foram: para o Nylon, ; para o PS-n1921, ; para o PS-n2380, ; e para o PET, . Estes resultados estão de acordo com os respectivos valores da temperatura de transição vítrea encontrados na literatura e mostram a potencialidade da técnica PAS ao estudo da transição vítrea de materiais poliméricos. / Photoacoustic spectroscopy (PAS) is a non-destructive technique and it has been largely applied to the thermal and optical characterization of materials. PAS technique is based on the photoacoustic effect which consist, basically, absorption of a modulated electromagnetic radiation and generation of heat inside of the material studied (sample), by a nonradiative deexcitation processes. Nowadays, among many PAS applications, effort are carried out to apply PAS technique for second-order phase transitions. However, only a few works can be found in the literature about glass transition studies with PAS technique. In this context, the main goal of this work is to apply PAS technique to determine glass transition temperature of the polymeric materials, based on the new photoacoustic cell configuration and on the new heating system. In this way, a photoacoustic cell was builted up for monitoring temperature variation of the sample, where the performance of the microphone was not affected. A heating system was developed based on the Peltier effect, in such way that it is possible to scan the temperature from the environment one up to 130 C, linearly at several speeds. The experimental apparatus was tested and applied to some polymeric materials: polyamide 6.0 (Nylon); polystyrene (PS-n1921 e PS-n2380); and poli(tereftalato de etileno) (PET). The results obtained were: Nylon, ; PS-n1921, ; PS-n2380, ; and PET, . These results are in a good agreement with the respective values of glass transition temperature found in the literature and show the PAS technique potentiality for glass transition studies in polymeric materials.

Fundação Carlos Chagas Filho de Amparo a Pesquisa do Estado do Rio de Janeiro / A espectroscopia fotoacústica (PAS) é uma técnica não destrutiva e muito utilizada na caracterização óptica e térmica de materiais. Ela é baseada no efeito fotoacústico que consiste, basicamente, na absorção de onda eletromagnética modulada e na geração de calor no interior do material em estudo (amostra), via processo de desexcitação não-radiativa. Dentre as muitas aplicações relacionadas à caracterização de materiais, recentemente, a técnica PAS vem sendo desenvolvida para estudos de transição de fase de segunda ordem. Entretanto, poucos trabalhos são encontrados na literatura com relação à aplicação da técnica PAS ao estudo da transição vítrea. Neste contexto, o objetivo deste trabalho é o de aplicar a técnica PAS na determinação da temperatura de transição vítrea de materiais poliméricos, de uma maneira inovadora com relação à célula fotoacústica e ao sistema de aquecimento. Para isso foi projetada e construída uma célula fotoacústica que possibilita a variação de temperatura da amostra, sem afetar a curva de resposta do microfone. Foi desenvolvido um sistema de aquecimento baseado no efeito Peltier, possibilitando fazer rampas de subida de temperatura, com várias velocidades, da temperatura ambiente até 130 C, de forma linear. Todo o aparato experimental foi testado e aplicado em várias amostras poliméricas: poliamida 6.0 (Nylon); poliestireno (PS-n1921 e PS-n2380); e poli(tereftalato de etileno) (PET). Os resultados obtidos foram: para o Nylon, ; para o PS-n1921, ; para o PS-n2380, ; e para o PET, . Estes resultados estão de acordo com os respectivos valores da temperatura de transição vítrea encontrados na literatura e mostram a potencialidade da técnica PAS ao estudo da transição vítrea de materiais poliméricos. / Photoacoustic spectroscopy (PAS) is a non-destructive technique and it has been largely applied to the thermal and optical characterization of materials. PAS technique is based on the photoacoustic effect which consist, basically, absorption of a modulated electromagnetic radiation and generation of heat inside of the material studied (sample), by a nonradiative deexcitation processes. Nowadays, among many PAS applications, effort are carried out to apply PAS technique for second-order phase transitions. However, only a few works can be found in the literature about glass transition studies with PAS technique. In this context, the main goal of this work is to apply PAS technique to determine glass transition temperature of the polymeric materials, based on the new photoacoustic cell configuration and on the new heating system. In this way, a photoacoustic cell was builted up for monitoring temperature variation of the sample, where the performance of the microphone was not affected. A heating system was developed based on the Peltier effect, in such way that it is possible to scan the temperature from the environment one up to 130 C, linearly at several speeds. The experimental apparatus was tested and applied to some polymeric materials: polyamide 6.0 (Nylon); polystyrene (PS-n1921 e PS-n2380); and poli(tereftalato de etileno) (PET). The results obtained were: Nylon, ; PS-n1921, ; PS-n2380, ; and PET, . These results are in a good agreement with the respective values of glass transition temperature found in the literature and show the PAS technique potentiality for glass transition studies in polymeric materials.

<p>The development of low-cost, and reliable platforms for on-site detection of pathogenic agents, and toxic environmental traces is still a critical need for real-time monitoring of potential environmental pollution and imminent outbreaks. The biosensors market is projected to attain 31.5 billion by 2024. In this landscape, colorimetric and electrochemical devices continue to have significant relevance, with paper-based platforms leading the point-of-care (POC) segment for pathogen detection and environmental monitoring.</p> <p>Despite the true potential of biosensors in general, they have witnessed a slow rate in commercialization, mainly due to cost restrictions, and concerns related to their reliability and repeatability once scaled-up. This research evaluates the implementation of printing techniques as a strong approach for the fabrication of paper-based and flexible electrochemical biosensors. The results obtained demonstrated the ability to control and predict the variables affecting the sensing performance, achieving high precision of the printing parameters, and allowing optimization, and iterations since very early stages of prototype development.</p> <p>Besides the novel fabrication approach, this work introduces the use of truncated aptameric DNA sequences for whole cell detection of E. coli O157:H7 and heavy metals (Hg2+ and As3+), providing evidence of high stability and robustness under harsh conditions. Results obtained demonstrate their equal or even superior performance when compared to antibodies.</p> <p>We established the use of aptamer-functionalized multilayered label particles (PEI-grafted gold decorated polystyrene) with high stability as label particles. These particles address the well known drawback of non-selective aggregation typical of traditional naked Gold nanoparticles. The outstanding stability of these multilayered labels was demonstrated when used in an enhanced version of the lateral flow assay for detection of E. coli O157:H7 (state of the art for paper-based colorimetric detection of whole cell bacteria), and in a multiplexed paper-based microfluidic device for dual detection of Mercury and Arsenic. This work sets the foundation of the development of a next generation of health care and environmental monitoring devices that are portable, sensitive, quantitative, and can reliably detect multiple targets with one single test.</p>