Submitted by Automação e Estatística (sst@bczm.ufrn.br) on 2018-05-02T23:09:41Z No. of bitstreams: 1 MakeziaMayaraDaCostaFreitas_DISSERT.pdf: 3584915 bytes, checksum: 2f3f3a402eff4c59732f7ae096cc95c8 (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2018-05-07T22:35:24Z (GMT) No. of bitstreams: 1 MakeziaMayaraDaCostaFreitas_DISSERT.pdf: 3584915 bytes, checksum: 2f3f3a402eff4c59732f7ae096cc95c8 (MD5) / Made available in DSpace on 2018-05-07T22:35:24Z (GMT). No. of bitstreams: 1 MakeziaMayaraDaCostaFreitas_DISSERT.pdf: 3584915 bytes, checksum: 2f3f3a402eff4c59732f7ae096cc95c8 (MD5) Previous issue date: 2017-10-27 / Diferentemente de estudos acerca da formação de micelas diretas, que podem ser avaliadas com técnicas simples como condutividade e tensão superficial, há dificuldade na obtenção de dados bons e reprodutíveis quando se trata da formação de micelas reversas. Nas últimas décadas as micelas reversas têm sido sistematicamente utilizadas como moldes para síntese de nanomateriais, devido a sua capacidade de se auto agregar em estruturas diversas, repassando essas características para o material desejado. Portanto, o presente trabalho teve como objetivo estudar o efeito da variação de comprimento da cadeia carbônica do solvente, do grau de etoxilação dos tensoativos e da temperatura na formação de micelas reversas, no que toca as características estruturais e concentração micelar crítica (c.m.c.). A técnica utilizada para as análises foi o espalhamento de raios X à baixo ângulo e foram escolhidos solventes orgânicos apolares de cadeias lineares e tensoativos não iônicos do tipo nonilfenol etoxilado, ambos obtidos comercialmente. Uma vasta gama de combinações solvente-tensoativo foi analisada, os principais resultados mostram que o aumento do grau de etoxilação do tensoativo provoca uma diminuição na c.m.c. dos sistemas, esta tendência também foi observada com o aumento da temperatura, já o aumento da cadeia carbônica dos solventes induziu ao aumento da c.m.c.. As dimensões máximas dos agregados micelares seguiram um aumento tanto com a variação positiva do grau de etoxilação tensoativo, quanto com o comprimento da cadeia carbônica do solvente e da temperatura. No que diz respeito aos formatos adquiridos pelos agregados, houve uma predominância de variação de estrutura achatada, passando por estrutura esférica sólida e esférica oca em uma escala decrescente de concentração de tensoativo no sistema. / Unlike studies about the formation of direct micelles, which can be evaluated with simple techniques such as conductivity and surface tension, it is difficult to obtain good and reproducible data when it comes to the formation of reverse micelles. In recent decades, reverse micelles have been systematically used as templates for the synthesis of nanomaterials, due to their ability to self-aggregate in diverse structures, passing these characteristics to the desired material. Therefore, the present work had the objective of studying the effect of carbon chain length variation of the solvent, the degree of ethoxylation of the surfactants and the temperature in the formation of reverse micelles, with respect to the structural characteristics and micelar concentration critical (c.m.c.). Small angle X-ray scattering was used to evaluate the micellar systems and nonylphenol ethoxylate surfactant was chosen as solute, being used solvents of different carbon chain length. A wide range of solvent-surfactant combinations were analyzed, the main results show that increasing the ethoxylation degree of the surfactant causes a decrease in c.m.c.. The maximum dimensions of the micellar aggregates followed an increase both with the positive variation of the degree of surfactant ethoxylation with: the increase of the carbon chain of the solvents, and the carbon chain length of the surfactant and the temperature. As regards the formats acquired by the aggregates, there was a predominance of flat structure variation, passing through a solid spherical and hollow spherical structure when concentration surfactant was reduced in the system.

Microcalorimetric measurements and contact angle measurements were conducted to assess the surface chemistry of the mineral talc. The contact angles were performed on both flat and powdered samples and the results were used to determine the surface free energy components and parameters (SFEC) using the acid-base theory for solids, according to the van Oss-Chaudhury-Good approach. It was found that the surface hydrophobicity of talc increases with decreasing particle size up to a limit after which hydrophilicity (polarity) increases. The increase in hydrophobicity was attributed to the increase of the delamination of the lamellar talc particles. Delamination is a comminution mechanism that preferentially exposes talc's hydrophobic basal planes, while fracture is another mechanism that breaks the lamellae, rupturing covalent bonds thus exposing more hydrophilic edge surfaces. The decrease in hydrophobicity, beyond a given particle size, could be related to the prevail of fracture over delamination during grinding which generated more hydrophilic edge surfaces. The flow microcalorymetry combined with thin layer wicking allowed the separate estimation of the SFEC at the basal plane and edge surfaces of talc. The results suggested that the basal surface of talc is monopolar basic, while the edge surface is monopolar acidic, which are in agreement with the crystal structure of the mineral. The combination of two particle size distribution techniques, which are based on different physical principles, permitted the quantitative determination of the aspect ratio of highly anisometric particles, such as talc. The same trend obtained using flow microcalorimetry was observed for the evolution of the aspect ratio as a function of particle fineness, i.e. the fracture prevails over delamination after achieving a maximum aspect ratio value of about 35. The agreement between two distinct methods was considered rather encouraging. / Master of Science

Au cours de ces travaux de thèse, la synthèse et le comportement électrophorétiquede particules hybrides dispersées en présence d'un nouveau contrôleur de charge, latridodécylamine, en milieu électrophorétique (non-polaire), ont été étudiés pour des applicationsde type papier électronique. Dans le but de contrôler et comprendre les interactions présentesdans ce système, la tridodécylamine a tout d'abord été examinée seule dans le milieu souhaité.Il a été observé que ce tensioactif, solubilisé dans un milieu type huile paraffine, a uneconcentration micellaire critique approximative de 250 mM et apporte des charges dans lemilieu. Ensuite, la synthèse par polymérisation en dispersion ou par voie sol gel a permisd'obtenir des particules inorganiques, polymères ou hybrides type framboise, stables en milieunon-polaire. Leur comportement électrophorétique en présence du nouveau contrôleur decharge a été élucidé. En outre, il a été montré que des interactions acido-basiques avec lesgroupements hydroxyles des pigments inorganiques et le tensioactif donnent des particuleshybrides chargées négativement. Celles-ci ont par la suite été intégrées dans une encreélectrophorétique et testées dans un dispositif prototype innovant, le contrôle del'électrophorèse étant géré via un polymère ferroélectrique. / In this work, the synthesis and the electrophoretic behavior of hybrid particlesdispersed in apolar media, in the presence of a new charge control agent, the tridodecylamine,have been investigated for electronic paper applications. In order to control and to understandinteractions present in the system, the tridodecyamine was studied in the apolar medium. It hasbeen observed that this surfactant, solubilized in a non-polar medium, has a critical micelleconcentration of approximately 250mM and creates charges in the medium. Then, the synthesisby polymerisation in dispersion or by using a sol-gel process gave rise to the creation ofinorganic, polymeric or raspberry type hybrid particles, stable in non-polar media. Theirelectrophoretic behavior in the presence of tridodecylamine was elucidated. Acid-baseinteractions between hydroxyl groups from inorganic material surfaces and surfactant led to thecreation of negatively charged hybrid particles. These particles were integrated into anelectrophoretic ink and tested into an innovative electrophoretic device where theelectrophoresis is monitored via a ferroelectric polymer.

Microcalorimetric measurements and contact angle measurements were conducted to study the surface chemistry of powdered minerals. The contact angle measurements were conducted on both flat and powdered talc samples, and the results were used to determine the surface free energy components using Van Oss-Chaudhury-Good (OCG) equation. It was found that the surface hydrophobicity of talc increases with decreasing particle size. At the same time, both the Lifshitz-van der Waals (gSLW) and the Lewis acid-base (gSAB) components (and, hence, the total surface free energy (gS)) decrease with decreasing particle size. The increase in the surface hydrophobicity and the decrease in surface free energy (gS) can be attributed to preferential breakage of the mineral along the basal plane, resulting in the exposure of more basal plane surfaces to the aqueous phase. Heats of immersion measurements were conducted using a flow microcalorimeter on a number of powdered talc samples. The results were then used to calculate the contact angles using a rigorous thermodynamic relation. The measured heat of immersion values in water and calculated contact angles showed that the surface hydrophobicity of talc samples increase with decreasing particle size, which agrees with the direct contact angle measurements. A relationship between advancing water contact angle qa, and the heat of immersion (-DHi) and surface free energies was established. It was found that the value of -DHi decrease as qa increases. The microcalorimetric and direct contact angle measurements showed that acid-base interactions play a crucial role in the interaction between talc and liquid. Using the Van Oss-Chaudhury-Good's surface free energy components model, various talc powders were characterized in terms of their acidic and basic properties. It was found that the magnitude of the Lewis electron donor, gS-, and the Lewis electron acceptor, gS+, components of surface free energy is directly related to the particle size. The gS- of talc surface increased with decreasing particle size, while the gS+ slightly decreased. It was also found that the Lewis electron-donor component on talc surface is much higher than the Lewis electron-acceptor component, suggesting that the basal surface of talc is basic. The heats of adsorption of butanol on various talc samples from n-heptane solution were also determined using a flow microcalorimeter. The heats of adsorption values were used to estimate % hydrophilicity and hydrophobicity and the areal ratios of the various talc samples. In addition, contact angle and heat of butanol adsorption measurements were conducted on a run-of-mine talc sample that has been ground to two different particle size fractions, i.e., d50=12.5 mm and d50=3.0 mm, respectively. The results were used to estimate the surface free energy components at the basal and edge surfaces of talc. It was found that the total surface free energy (gS) at the basal plane surface of talc is much lower than the total surface free energy at the edge surface. The results suggest also that the basal surface of talc is monopolar basic, while the edge surface is monopolar acidic. The results explain why the basicity of talc surface increases with decreasing particle size as shown in the contact angle and microcalorimetric measurements. Furthermore, the effects of the surface free energies of solids during separation from each other by flotation and selective flocculation were studied. In the present work, a kaolin clay sample from east Georgia was used for the beneficiation tests. First, the crude kaolin was subjected to flotation and selective flocculation experiments to remove discoloring impurities (i.e., anatase (TiO2) and iron oxides) and produce high-brightness clay with GE brightness higher than 90%. The results showed that a clay product with +90% brightness could be obtained with recoveries (or yields) higher than 80% using selective flocculation technique. It was also found that a proper control of surface hydrophobicity of anatase is crucially important for a successful flotation and selective flocculation process. Heats of immersion, heats of adsorption and contact angle measurements were conducted on pure anatase surface to determine the changes in the surface free energies as a function of the surfactant dosage (e.g. hydroxamate) used for the surface treatment. The results showed that the magnitude of the contact angle and, hence, the surface free energy and its components on anatase surface varies significantly with the amount of surfactant used for the surface treatment. / Ph. D.