Orientador: Edvaldo Sabadini / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-27T18:09:34Z (GMT). No. of bitstreams: 1 Creatto_EduardoJose_M.pdf: 2495128 bytes, checksum: 6912961c15614521a8e45f4e9139f99f (MD5) Previous issue date: 2015 / Resumo: A química supramolecular envolve estruturas mantidas por interações intermoleculares. Neste contexto, sistemas que apresentam estruturas auto organizadas são de interesse devido importância como ciência de base bem como aplicabilidade. Neste trabalho foram utilizadas micelas de brometo de hexadeciltrimetilamônio (CTAB) como reticulantes de hidroxietilceluloses hidrofobicamente modificadas. Como as micelas estão em constante quebra e recombinação, reticulações transientes são obtidas. Tais sistemas apresentam comportamento reológico característico, dependente da concentração do surfactante. Obervou-se que a celulose que apresenta maior ramificação hidrofóbica resulta em aumento mais efetivo da viscosidade como consequência do maior grau de reticulação. A Técnica de calorimetria de titulação isotérmica (ITC) foi utilizada de modo a compreender os processos energéticos envolvidos na agregação. Com esta pôde-se obter parâmetros do sistema como cmc, cac e ?H°mic . Elucidou-se também que as interações polímero-surfactante são de origem hidrofóbica. A adição de salicilato de sódio (NaSal) em solução de CTAB leva a formação de micelas gigantes. Determinou-se por ITC a razão, [CTAB]/[NaSal], em que ocorre a formação de micelas gigantes, bem como a variação de entalpia deste processo. Sistemas contendo micelas gigantes e na presença de celulose hidrofóbicamente modificada foram estudados por reologia. Variações em seu comportamento foram claramente observadas / Abstract: Supramolecular chemistry involves structures maintained by the intermolecular interactions. In this context, systems that have self-assembled structures are of interest because of importance as basic science as well as applicability. In this study, we used micelles formed by hexadecyltrimethylammonium bromide (CTAB) as crosslinking agents of hydrophobically modified hydroxyethylcelluloses. As the micelles are constantly breaking and recombination, transient crosslinks are obtained. Such systems have characteristic rheological behavior, dependent on the surfactant concentration. It was observed that the cellulose which is more hydrophobic branching results in more effective increase in viscosity as a result of the higher degree of crosslinking. Isothermal titration Calorimetry (ITC) technique was used to understand the energy involved in the aggregation process. With this it was possible to obtain system parameters such as cmc, cac and ?H°mic. It is also elucidated that the interaction polymer-surfactant are of hydrophobic origin. The addition of sodium salicylate (NaSal) into CTAB solutions leads to formation of giant micelles. It was determined by ITC the ratio [CTAB]/[NaSal] in what occurs the formation of giant micelle, and the enthalpy change of the process. Systems containing giant micelles in the presence of hydrophobically modified cellulose were studied by rheology. Variations in their behavior were clearly observed / Mestrado / Físico-Química / Doutor em Ciências

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第21580号 / 理博第4487号 / 新制||理||1644(附属図書館) / 京都大学大学院理学研究科地球惑星科学専攻 / (主査)准教授 宮﨑 真一, 教授 福田 洋一, 教授 橋本 学 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22474号 / 工博第4735号 / 新制||工||1740(附属図書館) / 京都大学大学院工学研究科化学工学専攻 / (主査)教授 山本 量一, 教授 渡辺 宏, 准教授 谷口 貴志 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

This thesis pursues monitoring of pH changes and description of properties in phase–separated hydrogels prepared by interaction of polyelectrolyte and oppositely charged surfactants. For the purposes of this work, all hydrogels were prepared by the interaction of hyaluronan with Septonex. All hydrogels were exposed to pH changes (4–9). Changes in pH were being monitored using spectroscopic indicators, methyl orange, methyl red, bromothymol blue and phenolphtalein. The pre– and post– pH changes in properties were compared using rheological methods. Additional information was gathered through thermogravimetric analysis. By these methods it was proved that the changes in the pH can modify the mechanical properties and partly the internal structure of the hydrogels. Rheological tests show, that from the application point of view, the most interesting hydrogels are observed at pH 9 which have the strongest bonds but have low permeability and hydrogels described at pH 7 which are much softer and are capable of absorbing large amounts of water.

The new forms of superabsorbent polymers (SAP) on the base of acrylic acid were developed and studied in this thesis. The SAP are focused on agricultural and environmental applications. While they are applied to the soil, SAP can prevent water losing and they become a reservoir of humidity in case of dry season, moreover in combination with fertiliser they play role of controlled release medium. Eight various samples of SAP were experimentally prepared by networking of partially neutralized acrylic acid. Potassium peroxydisulfate was used as the initiator and N,N–methylenebisacrylamide as the crossing agent. Some of samples contained addition of second monomer of acrylamide. All of them were enriched by fertilisers – natural lignohumate or synthetic NPK or combination of both. The swelling characteristics of prepared samples were investigated in conditions of various ionic strength. The influence of xerogels’ particles size on swelling properties was also observed. The viscoelastic characteristics of hydrogel form of all SAP were determined by using of rotation rheometer. The changing of viscoelastic properties were studied in dependence on time, on freezing and on repeating swelling cycles. On top of that the controlled releasing ability of SAP was tested due to three modelling experiments. The biological activity of all polymer products was tested at the end of the thesis. All samples of SAP were incorporated into the artificial soil and the ability of the water retention in the soil was observed. The growing experiments were running by using of corn plants. The size and the mass of each plant were measured and branching of the root was objectively evaluated by programme Harmonic and Fractal Image Analyzer.

This project consists of two parts. One area of focus in the first part is understanding the interactions between a non-ionic, block copolymer type dispersant and hydrophobically-modified, ethoxylated urethane (HEUR) associative thickeners in water. The dispersant was mixed at various concentrations (0-2% by weight) with HEUR thickeners at 1% by weight concentration in the aqueous medium. This study is an integral part of our attempts to determine mechanisms of viscosity drop when colorant dispersions are added to latex tint base formulations thickened with associative thickeners. One of the HEUR thickeners is a product that has been available for over three decades (HEUR RM-825), whereas the other, HEUR RM-995 is a product recently introduced to minimize the tint base viscosity drop. The old HEUR showed a definitive viscosity maximum as a function of the dispersant concentration. However, the new generation product did not indicate a viscosity maximum within the dispersant concentration range studied; instead it showed a small, but linear increase in viscosity as dispersant level was increased. The next area of focus was on understanding the phase behavior, rheology, and interactions between polymer latex particles and a hydrophobically-modified, ethoxylated urethane (HEUR) associative thickener in water. The influence of the addition of surfactant in some of the systems was also studied. Several types of dispersions were made using two types of polymer latex, two associative thickeners, and two surfactants. Mixtures containing a small particle size acrylic latex and HEUR RM-825 exhibited the most interesting and complex phase behavior and rheology. In experiments wherein the latex particle volume fraction was kept constant, the addition of HEUR caused stable, followed by phase separated (syneresis) and stable mixtures as HEUR concentration was increased. The observed phase behavior is consistent with previous work reported by other investigators. However, detailed rheological data on systems such as these have not been reported, and this report presents the rheological data and correlate rheology with the phase behavior. The stable latex-HEUR mixtures at low HEUR levels show shear-thinning viscosity with well-defined low-shear Newtonian plateaus. As HEUR level is increased wherein syneresis is observed, erratic rheological profiles with shear-thickening are observed. When HEUR level is increased to a region where no syneresis is observed, low shear Newtonian plateaus re-appeared albeit at higher viscosities. The effects of added non-ionic and anionic surfactants on the dispersion are also studied. The main focus of the second part of this project is hybrid organic-inorganic photovoltaics. They have been the focus of recent studies due to their promising use in low-cost, flexible electronics, which can be processed from solution by printing and coating techniques. Understanding the rheology of these nanocomposites is essential in controlling shear flows during printing and application processes. Through rheology, we can determine different properties of poly(3-hexylthiophene) and dodecanethiol (DDT) modified zinc oxide (ZnO-DDT). Semiconductor nanowires such as ZnO have rigid or rod-like macromolecule geometry. Therefore, they have a tendency to have a lytropic liquid crystal (LLC) phase. LLC orders occur spontaneously in solutions with rod-shaped or anistropic objects from isotropic phase to nematic phase above a critical volume fraction which was studied using ZnO-DDT. The shear-induced alignment of the liquid crystal molecules was analyzed, serving as a guide for LLC printing. Furthermore by using this nanocomposite we are able to induced gelation using the ZnO-DDT nanowires in what is considered as a “good solvent,” dichlorobenzene. The kinetics of this gelation process was determined to be of first-order reaction kinetics. Furthermore, a mechanism of this gelation process is also presented.

No description available.

Les solutions de micelles géantes sont utilisées dans plusieurs domaines industriels pour augmenter la viscosité d'une solution. Elles présentent un caractère viscoélastique bénéfique pour la fracturation hydraulique des roches pétrolifères car elles permettent de transporter le sable et de le maintenir en suspension. Cette thèse étudie les propriétés rhéologiques d’une solution commerciale destinée à la fracturation hydraulique. Cette solution est particulièrement délicate à caractériser car ses écoulements semblent être toujours instables. Nous avons mis au point une méthodologie permettant de la caractériser en régime laminaire, et avons montré que ce régime n’existe à température ambiante que pour des très faibles valeurs de taux de cisaillement. Habituellement, le comportement rhéologique dans le régime linéaire de ce type de solution est prédit par le modèle de Maxwell. Nous mettons en évidence que le comportement rhéologique de la solution étudiée ne correspond pas à ce modèle. Nous avons établi un modèle viscoélastique compatible avec les données expérimentales.Les instabilités d’écoulement de ces solutions sont d’origine élastique. Ce phénomène est largement étudié dans la littérature. Le comportement rhéologique dans le domaine non linéaire possède des caractéristiques propres à ces solutions. Notamment l’apparition d’un plateau de contrainte dans la courbe d’écoulement, précédé par une augmentation linéaire de la contrainte avec le cisaillement. Le début de ce plateau coïncide avec le déclenchement des instabilités, on parle de taux de cisaillement critique. La particularité de cette solution est la valeur faible de la contrainte plateau ainsi que du taux de cisaillement critique. Les valeurs observées sont cohérentes avec la valeur des paramètres rhéologiques obtenus dans les régimes d’écoulement laminaire. L’effet de certains paramètres physico-chimiques sur la rhéologie est également exploré. / Giant micelle solutions are used in several industrial domains to increase the viscosity of solution. Their viscoelastic characteristic is beneficial for hydraulic fracturing of oil rocks because these solutions are able to transport sand and to keep it in suspension. This thesis examines the rheological properties of a commercial solution, designed for hydraulic fracturing. This solution is particularly difficult to characterize because its flows seem to be always unstable. We have developed a methodology to characterize it in the laminar regime and we have shown that this regime exists at room temperature only for very low shear rate values. Usually, the rheological behavior of this type of solution, in the linear regime, is predicted by the Maxwell model. We prove that the rheological behavior of the studied solution doesn’t match this model. We have designed a viscoelastic model that is compatible with experimental data.The origin of flow instabilities of these solutions is elastic. This phenomenon is widely studied in the literature. The rheological behavior in the nonlinear regime has characteristics specific to these solutions. In particular, the appearance of a stress plateau in the flow curve, preceded by a linear increase of stress with shear. The beginning of this plateau match the onset of instabilities at a critical shear rate. The feature of this solution is the low value of the stress plateau as well as the critical shear rate value. They are consistent with the value of rheological parameters obtained in laminar flow regimes. The effect of some physico-chemical parameters on rheology is also explored.

abstract: This research is a comprehensive study of the sustainable modifiers for asphalt binder. It is a common practice to use modifiers to impart certain properties to asphalt binder; however, in order to facilitate the synthesis and design of highly effective sustainable modifiers, it is critical to thoroughly understand their underlying molecular level mechanisms in combination with micro and macro-level behavior. Therefore, this study incorporates a multi-scale approach using computational modeling and laboratory experiments to provide an in-depth understanding of the mechanisms of interaction between selected modifiers and the constituents of asphalt binder, at aged and unaged conditions. This study investigated the effect of paraffinic wax as a modifier for virgin binder in warm-mix asphalt that can reduce the environmental burden of asphalt pavements. The addition of wax was shown to reduce the viscosity of bitumen by reducing the self-interaction of asphaltene molecules and penetrating the existing nano agglomerates of asphaltenes. This study further examined how the interplay of various modifiers affects the modified binder’s thermomechanical properties. It was found that the presence of wax-based modifiers has a disrupting effect on the role of polyphosphoric acid that is another modifier of bitumen and its interactions with resin-type molecules. This study was further extended to using nanozeolite as a mineral carrier for wax to better disperse wax in bitumen and reduce the wax's adverse effects such as physical hardening at low service temperatures and rutting at high service temperatures. This novel technique showed that using a different method of adding a modifier can help reduce the modifier's unwanted effects. It further showed that nanozeolite could carry wax-based modifiers and release them in bitumen, then acting as a scavenger for acidic compounds in the binder. This, in turn, could promote the resistance of asphalt binder to moisture damage by reducing the quantity of acidic compounds at the interface between the binder and the stone aggregates. Furthermore, this study shows that iso-paraffin wax can reduce oxidized asphaltene molecules self-interaction and therefore, reduce the viscosity of aged bitumen while cause brittleness at low temperatures. Additionally, a cradle to gate life-cycle assessment was performed for a new bio-modifier obtained from swine manure. This study showed that by partially replacing the bitumen with bio-binder from swine manure, the carbon footprint of the binder can be reduced by 10% in conjunction with reducing the cost and environmental impact of storing the manure in lagoons. / Dissertation/Thesis / Doctoral Dissertation Civil, Environmental and Sustainable Engineering 2020

Actin is a highly ubiquitous and evolutionarily conserved protein capable of polymerizing and forming filamentous polymers which play a central role in cell mechanics and motility. Here, we study the in vitro regulation of actin mechanics and dynamics by calponin and caldesmon, two actin binding proteins believed to be involved in regulating cytoskeletal mechanics and structure through mechanisms not currently well understood. Chapters 1 and 2 introduce the reader to actin and its roles in the cell, as well as to the methods and theoretical foundations used in this work. In Chapter 3, we use total internal reflection and confocal fluorescence microscopy to investigate the polymerization dynamics of actin in the presence of a caldesmon C terminal fragment, H32K. We show that H32K stabilizes a nascent structural state of actin without altering the polymerization dynamics of the filament. We also show that H32K stabilized nascent actin has increased affinity for the actin branching protein complex Arp2/3 involved in driving membrane protrusions during cell motility, and propose the nascent state of actin as a possible transient differentiator targeting certain actin binding proteins to actin in vivo. This is to our knowledge the first reported direct functional effect of nascent actin. In Chapter 4, we use fluorescence microscopy to quantify actin bending mechanics in the presence of the binding protein calponin and show that calponin reduces the persistence length of actin. We compare our results to the literature and compare the mechanical change to electron microscopy reconstructions, which suggest that calponin affects actin intermonomer contacts through interactions with actin subdomain 2. In Chapter 5, we expand on the results from Chapter 4 using bulk rheology and show that calponin increases the tensile strength of reconstituted actin networks, similar to the effect seen in whole cells and tissues. We discuss these data within an affine network model and show that the results can be entirely explained in terms of the reduced actin persistence length. We use this to propose a novel physical mechanism for calponin function in vivo. This work elucidates the physical mechanisms of calponin and caldesmon function and their role in regulating the cellular cytoskeleton. / 2031-01-01T00:00:00Z