Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2015-04-10T14:21:53Z No. of bitstreams: 0 / Made available in DSpace on 2015-04-10T14:21:53Z (GMT). No. of bitstreams: 0 / O alto nível de poluição gerado pelo descarte inadequado de materiais poliméricos vem motivando pesquisas por sistemas e técnicas ambientalmente corretos, tais como a aplicação de polímeros biodegradáveis e a substituição dos sistemas de pintura à base de solventes por aqueles com alto teor de sólidos, à base de água ou, praticamente isentos de compostos orgânicos voláteis (VOCs) e curáveis por radiação. Todavia, os revestimentos poliméricos curados são insolúveis e infusíveis, aumentando o grau de complexidade do seu reprocessamento, da sua reciclagem e da degradação desejável. Assim, este trabalho apresenta, como objeto de contribuição científica, a obtenção de tintas modificadas com agentes pró-degradantes, curadas por reações químicas induzidas por radiação ultravioleta ou feixe de elétrons (UV/EB), para impressão em embalagens plásticas, biodegradáveis ou não, para produtos de baixa vida útil. Foram estudadas combinações de seis revestimentos, sendo um verniz não pigmentado e cinco tintas nas cores amarela, azul, branca, preta e vermelha; três agentes pró-degradantes (estearatos de cobalto, cério e manganês), cinco substratos poliméricos (Ecobras®, polietileno de baixa densidade e suas respectivas modificações com os agentes pró-degradantes). Os revestimentos foram aplicados nos substratos e curados por radiação UV ou EB, resultando em 180 amostras. Estes materiais foram, então, expostos ao envelhecimento acelerado em câmara tipo QUV e à compostagem em ambiente natural. De modo a se compreender o efeito dos revestimentos poliméricos no processo de degradação das amostras, foram selecionadas aquelas com valores extremos de grau de conversão, a saber: amarela e preta, as quais foram expostas à compostagem em ambiente controlado via respirometria, reduzindo de 180 para 16 o número de amostras. O composto orgânico gerado pelo processo de biodegradação foi analisado por testes de ecotoxicidade. Foi observado que a camada de revestimento atua como barreira que inibe a degradação do plástico quando exposto às intempéries. Adicionalmente, constatou-se que quanto maior o grau de conversão das formulações pigmentadas pastosas em sólidas durante a cura por radiação ultravioleta, maior foi sua mineralização em ambiente de compostagem. As amostras curadas por EB apresentaram menor taxa de biodegradação do que as curadas por UV. Isso se deu em virtude da rede de ligações cruzadas entre as cadeias poliméticas, geradas na cura por EB. A adição dos agentes pró-degradantes promoveu uma aceleração no processo de degradação, ocasionando, inclusive, a migração do íon metálico para o meio, porém sem afetar a qualidade do meio de compostagem. / Tese (Doutorado em Tecnologia Nuclear) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Cu2ZnSnSSe4 (CZTSSe) est un matériau prometteur comme absorbant de cellules photovoltaïques. Le développement à grande échelle de cellules solaires CZTSSe est conditionné au développement de procédés bas coût et soucieux de l'environnement. Dans ce contexte, le développement de films de CZTSSe à partir d'encres tout aqueuses de nanoparticules de CZTS constitue un challenge intéressant. Une stratégie haute température en présence d'un agent texturant gaz a été définie pour synthétiser des nanocristaux de CZTS présentant des surfaces polaires. Notre procédé agent texturant gaz met en œuvre la formation simultanée de nucléis de CZTS et de bulles de gaz. Nous montrons que la production en conditions de forte sursaturation d'une très forte concentration de nucléis de CZTS en association à un très grand nombre de petites bulles de gaz représente les conditions optimales de formation de nanocristaux. Par une étude électrocinétique, une condensation régulée par la taille de l'ion alcalin est observée dans la série des alcalins Li+ < Na+ < K+ < Rb+ < Cs+, démontrant la stabilité chimique des surfaces de Cu2ZnSnS4 en dispersion toute aqueuse. Par mise en œuvre des dispersions tout aqueuses, nous avons réalisé l'acquisition de données de base permettant de produire une preuve de concept de la formation d'un film sans fissures. Un autre point important à considérer lors de l'utilisation de matières premières bas coût est l'élimination des impuretés inhibitrices de la croissance des grains. Un profil spécifique de recuit des films est proposé mettant en œuvre une purification haute température pour l'élimination du carbone. En effet, notre stratégie met en œuvre la décomposition des domaines amorphes en carbone sp2 qui est ultérieurement éliminé via la formation de CSe2 gazeux. Finalement, des cellules solaires ont été fabriquées avec succès à partir d'encres tout aqueuses avec des rendements de conversion préliminaires jusqu'à 2,6 %. / Recently more attention is devoted to Cu2ZnSnS4 (CZTSSe) for photovoltaic applications due to their non-toxic, earth-abundant components and good optoelectronic properties. Large scale fabrication of CZTSSe solar cells will rely on the development of low-cost and environmentally-friendly approach. In this context, development of CZTSSe films from all-aqueous CZTS nanocrystals inks represents an interesting challenge. A high temperature, gas-templating strategy has been defined to synthesize highly crystallized CZTS nanocrystals displaying polar surfaces. Our gas-templating process involves the simultaneous formation of CZTS nucleis and gas bubbles. We demonstrate that production of a high rate of small gas bubbles, as well as a high concentration of nucleis, depict optimal conditions for nanocrystal synthesis. By an electrokinetic investigation, a condensation regulation by the alkali ion size is observed in the alkali series Li+ < Na+ < K+ < Rb+ < Cs+, demonstrating the chemical stability of CZTS surfaces in aqueous basic dispersions. By using all-aqueous chalcogenide nanocrystals dispersions, we determined a critical cracking thickness of 250 nm and an average thickness of 100 nm to fabricate micron crack-free films using a multilayer procedure. Having in mind these results, we give the proof of concept of crack-free film formation from all aqueous CZTS nanocrystals inks. Another important consideration, when employing low-cost materials, is the removal of impurities, inhibitors of grain growth. A specific annealing profile is proposed involving a high temperature purification step in order to remove carbon. Indeed, our strategy involves the decomposition of amorphous domains into sp2 carbon which will be further removed via the CSe2gas formation. Finally, CZTSSe solar cells are successfully fabricated from all-aqueous CZTS inks with preliminary devices efficiencies up of 2.6%.

The aim of this work was focused on the determination of pesticides concentration in water solution. Pesticides are indissoluble in aqueous solutions and impedance or voltametric/amperometric response of the pure water and water with pesticides is identical. Therefore was necessary find a way how rapidly, effectively and economically measure the pesticides concentration. One way is measurement of conductivity with electrochemical microsensors after enzymatic reaction.

Cette thèse est consacrée à l'étude d'encres, de composites et de dépôts de nanotubes de carbone monofeuillets (SWNT). Le contrôle de la dispersion et de l'orientation des nanotubes dans ces matériaux composites nanostructurés vise à optimiser leurs propriétés, en particulier électriques et optiques.La première partie du travail est consacrée à l'optimisation de la dispersion des SWNT dans des suspensions aqueuses stabilisées par des tensio-actifs, des sels biliaires, et à l'étude de leurs propriétés optiques, et en particulier de leur photoluminescence (PL) dans le proche infrarouge. La spectroscopie d'absorption nous permet de sonder la dispersion des SWNT et de mesurer leur coefficient d'absorption. Nous montrons que ce dernier est très sensible au degré d'individualisation des nanotubes. Par ailleurs, nous revisitons l'interprétation des spectres de PL excités dans le proche infrarouge (en particulier à 1,17 et 1,58 eV) et attribuons les différents pics mesurés à différents mécanismes : transitions excitoniques directes, à des couplages exciton-phonon ou à des transferts d'énergie entre nanotubes. Nous montrons que l'évolution de l'intensité de PL avec l'individualisation permet de distinguer ces différents mécanismes.La seconde partie du travail est dédiée à la préparation de suspensions aqueuses stabilisées par des polymères hydrosolubles (PVA et PVP), et de composites SWNT/polymère, sans tensio-actifs. Les suspensions de nanotubes sont mélangées à des solutions de polymère, puis dialysées pour éliminer le tensio-actif. Le rendement, i.e. la concentration de la suspension finale, est de l'ordre de 75 fois plus élevée que pour une suspension préparée directement avec des polymères. Par ailleurs, les spectres de PL sont sensibles à l'environnement diélectrique des nanotubes et leur étude permet de mettre en évidence un échange entre les agents dispersants tensio-actifs/PVA à la surface des nanotubes, échange qui n'est pas observé dans le cas du PVP. Dans la troisième partie de la thèse, nous utilisons la technique d'impression jet d'encre pour imprimer des lignes continues micrométriques de SWNT, et proposons des méthodes originales pour étudier leur morphologie et leur anisotropie. La morphologie des dépôts peut varier entre deux cas limites, le dépôt homogène et la ‘‘paire de rails'', en faisant varier la concentration de nanotubes dans les encres, la distance entre gouttes et la température du substrat. L'orientation des nanotubes au bord des dépôts est très élevée (paramètre d'ordre orientationnel S entre 0,6 et 0,9), les nanotubes sont également bien orientés dans les rails (S~0.5) et dans une moindre mesure dans les lignes homogènes S~0.3. / This thesis focus on the study of inks, composites and deposits of single-wall carbon nanotubes (SWNT). The control of dispersion and orientation of nanotubes in such nanostructured composites materials allows to optimize their properties, and especially their electrical and optical properties.The first part of the work is devoted to the optimization of dispersion of SWNT in aqueous suspensions stabilized by bile salts surfactants, and to the study of their optical properties, and especially their near infrared photoluminescence (PL). Dispersion of the nanotubes is probed by absorption spectroscopy. We show that their absorption coefficient is very sensitive to the individualization of the nanotubes. On the other hand, we revisit the interpretation of the PL spectra excited in the near infrared (especially at 1.17 and 1.58 eV), and we assign the different peaks to different mechanisms, namely direct excitonic transitions, exciton-phonon coupling, and energy transfer between nanotubes. We show that the evolution of PL intensity as a function of individualization allows to distinguish the different mechanisms.The second part of the work is dedicated to the preparation of aqueous suspensionsstabilized by hydrosoluble polymers (PVA and PVP), and SWNT/polymer composites, without surfactants. SWNT suspensions are mixed with polymer solutions, and then the surfactant is removed by dialysis. The yield, i.e. the relative concentration of SWNT in the dialyzed suspension, is ~75 times higher than for a suspension prepared directly with polymers. On the other hand, PL signatures are sensitive to the dielectric environment of the nanotubes which allows to evidence an exchange between the dispersing agents bile salts/PVA on the nanotube surface, such an exchange is not observed in the case of PVP.In the third part of the thesis, we use the inkjet printing technique to print continuous micrometric lines of SWNT, and we propose original methods to study their morphology and their anisotropy. The morphology of the deposits varies between two limit cases, an homogeneous deposit and a ‘‘pair of tracks'', by varying nanotube concentration in the inks, inter-drop distance and substrate temperature. The orientation of the nanotubes is very high at the edge of the deposits (orientational order parameter S between 0.6 y 0.9), the nanotubes are well-oriented as well in the tracks (S~0.5) and to a lesser extent in the homogeneous lines (S~0.3).

Made available in DSpace on 2014-10-09T12:51:06Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:05:22Z (GMT). No. of bitstreams: 1 11245.pdf: 3839008 bytes, checksum: 2374cc538329b29558236be14950ccdf (MD5) / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Made available in DSpace on 2014-10-09T12:51:06Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:05:22Z (GMT). No. of bitstreams: 1 11245.pdf: 3839008 bytes, checksum: 2374cc538329b29558236be14950ccdf (MD5) / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Inkjet printing technology became a popular technology for printing digital photographs in the last decade. There is a big variety of both original and alternative (cheaper) inks and print media for the consumers. But there is a question if the cheaper material provides also comparable printout quality. For this reason, it is important to test the properties of such inkjet printouts. There are several ways how to test the lightfastness of the printouts: long term storage under environmental conditions, or short, accelerated ageing tests. The stability of printouts is affected by many factors, such as ink-receiving layer, ink composition, UV and visible light intensity and air pollutants concentration in the environment. Some inkjet printouts exposed to light usually undergo surprisingly fast fading, but light is not the only dangerous condition for inkjet printout. The two types of test targets printed with dyebased inkjet inks on various paper types were subjected to both accelerated test in a xenon test chamber and light and environmental pollutants long-term test in a sunny indoor corridor. The values of light intensity were continuously monitored and samples properties were regularly measured with a spectrophotometer. Another type of testing included accelerated ozone ageing of inkjet dyes. The colour gamuts and gamut volumes were calculated from collected spectral data. Total colour difference E*ab was also evaluated, its increase served as a tool for finding the formal printout degradation rate constant. It was found out that the dyes in ink-receiving layers of printouts underwent significant degradation in all tested conditions. The degradation rate depended on the type of used print media. The reciprocity behaviour of printouts was also studied. Recent inkjet printouts testing miss some actual ISO norm which should show the way of effective lightfastness evaluation. One of the main aims of this work was to find some new and alternative ways of inkjet printouts lightfastness evaluation. The method of printed inks concentration determination from the test charts spectrophotometric measurements was also proposed.

No description available.

<p>This thesis describes solutions to many of the challenges in the development of paper-based biosensors. Coupling techniques in analytical biochemistry with knowledge of paper science and technology, advances are described in the areas of: the influence of paper surface chemistry on bioactivity; optimizing bioactive ink formulation; the printing of paper supported microfluidic channels; and, the characterization of complex sensors based on printed sol-gel material layers.</p> <p>The stability of paper-immobilized antibodies under various conditions was first studied using both untreated filter paper and PAE-treated paper. Antibody stability decreased with increasing temperature and relative humidity. Paper treated with PAE had no significant influence on antibody stability under the experimental conditions. The experimental result was also encapsulated in an empirical equation to predict the impact of printing and coating operations on antibody activity.</p> <p>The influence of paper sizing agent (AKD) on the adsorption and inactivation of antibody was also investigated. The preliminary study showed that the small amount of AKD improved the antibody adsorption on paper and also did not interfere antibody activity. Therefore, packaging papers containing sizing agents can be used as a substrate for antibody immobilization.</p> <p>Two strategies to fabricate hydrophobic barriers were developed, based on sol-gel derived MSQ material. The first method is based on ink-jet printing a highly basic solution onto MSQ-impregnated filter paper to re-exposing the cellulose and producing a hydrophilic patterned region. The second method is direct ink-jet printing of MSQ onto paper to outline the hydrophobic walls bordering the hydrophilic channels. The resistance of the barriers to surfactants and organic solvents was tested. The functionality of MSQ-based devices was further demonstrated by using a colorimetric assay for <em>E. coli </em>detection.</p> <p>Multiple-stage inkjet printing of sol-gel based bioink onto porous filter paper for enzyme immobilization was characterized by various methods. Confocal microscope and SEM/TEM images confirmed the formation of sol-gel and enzyme composite material on the paper fibers without cracking. The protease assay proved that the entrapment of enzyme molecules improved with the increasing amount of the sol-gel derived material printed on paper. The top layer of sol-gel ink was found to play a major role in protection against enzyme proteolysis, while the bottom layer of sol-gel ink was found to be necessary to prevent the potential inhibition of enzyme by the cationic polymer.</p> / Doctor of Philosophy (PhD)

Self-assembled microsphere monolayers (SMMs) hold significant promise for micro- and nanopatterning. Here we exploit, for the first time, SMMs as stamps for microcontact printing (μCP) and demonstrate this to fabricate patterned initiator templates that can subsequently be amplified into polymer brushes by surface initiated atom transfer radical polymerization (SI-ATRP). SMM stamps avoid the need for expensive and sophisticated instrumentation in pattern generation, and provide a broad range of accessible surface chemistries and pitch size control.