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Aplicação da equação de Paisson-Boltzmann com condição de contorno para regulação carga-potencial a sistemas polieletrolíticosPazianotto, Ricardo Antonio Almeida [UNESP] 21 September 2007 (has links) (PDF)
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pazianotto_raa_me_sjrp.pdf: 946780 bytes, checksum: d9dd8103ed5cc8d44a4385ab65ab3dfa (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / No presente trabalho, foram avaliados modelos teóricos para a descrição da autodissociação de poliácido fraco, e para a formação de complexos entre polieletrólitos de cargas opostas. Os modelos descritos utilizam simetria cilíndrica e o modelo celular para representar a solução polieletrolítica. A equação de Poisson-Boltzmann, com condições de contorno que levam em conta a regulação carga-potencial, é utilizada nos modelos teóricos para descrever as interações eletrostáticas. Para auto-dissociação de poliácidos fracos, foram obtidos valores teóricos de pH, calculados em função da concentração de polímeros e de sal, os quais estão em boa concordância com resultados experimentais da diluição do ácido poligalacturônico e alginato. Na formação de complexos, a energia livre eletrostática e energia livre de mistura de Flory-Huggins foram combinadas para obter diagramas de estabilidade teóricos, em diferentes condições, para analisar alguns parâmetros críticos. Estes diagramas apresentam boa concordância quando comparados com resultados experimentais da complexação entre: goma arábica e gelatina, alginato e quitosana, DNA e quitosana, poli-L-lisina e sulfato de condroitina. / In the present work, theoretical models for the weak polyacid self-dissociation and polyelectrolyte complexation were evaluated. The models described use cylindrical symmetry and the polyelectrolyte solution is represented by the cell model. The Poisson-Boltzmann equation with boundary conditions which take into account the charge-potential regulation were used to describe the electrostatic interactions. For weak polyacid self-dissociation, theoretical values of pH, calculated as a function of polymer and salt concentrations, were obtained, and are in good agreement with experimental data of dilution of polygalacturonic acid and alginate. In the complex formation the electrostatic and the Flory- Huggins mixture free energies were combined to obtain stability diagrams in different conditions in order to analyze some critical parameters. The theoretical diagrams have shown good agreement when compared with experimental data for the complexation of: arabic gum/gelatin, alginate/chitosan, DNA/chitosan, poly-L-lysine/chondroitin sulfate.
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Aplicação da equação de Paisson-Boltzmann com condição de contorno para regulação carga-potencial a sistemas polieletrolíticos /Pazianotto, Ricardo Antonio Almeida. January 2007 (has links)
Orientador: João Ruggiero Neto / Banca: Sergio Paulo Campana Filho / Banca: Márcio José Tiera / Resumo: No presente trabalho, foram avaliados modelos teóricos para a descrição da autodissociação de poliácido fraco, e para a formação de complexos entre polieletrólitos de cargas opostas. Os modelos descritos utilizam simetria cilíndrica e o modelo celular para representar a solução polieletrolítica. A equação de Poisson-Boltzmann, com condições de contorno que levam em conta a regulação carga-potencial, é utilizada nos modelos teóricos para descrever as interações eletrostáticas. Para auto-dissociação de poliácidos fracos, foram obtidos valores teóricos de pH, calculados em função da concentração de polímeros e de sal, os quais estão em boa concordância com resultados experimentais da diluição do ácido poligalacturônico e alginato. Na formação de complexos, a energia livre eletrostática e energia livre de mistura de Flory-Huggins foram combinadas para obter diagramas de estabilidade teóricos, em diferentes condições, para analisar alguns parâmetros críticos. Estes diagramas apresentam boa concordância quando comparados com resultados experimentais da complexação entre: goma arábica e gelatina, alginato e quitosana, DNA e quitosana, poli-L-lisina e sulfato de condroitina. / Abstract: In the present work, theoretical models for the weak polyacid self-dissociation and polyelectrolyte complexation were evaluated. The models described use cylindrical symmetry and the polyelectrolyte solution is represented by the cell model. The Poisson-Boltzmann equation with boundary conditions which take into account the charge-potential regulation were used to describe the electrostatic interactions. For weak polyacid self-dissociation, theoretical values of pH, calculated as a function of polymer and salt concentrations, were obtained, and are in good agreement with experimental data of dilution of polygalacturonic acid and alginate. In the complex formation the electrostatic and the Flory- Huggins mixture free energies were combined to obtain stability diagrams in different conditions in order to analyze some critical parameters. The theoretical diagrams have shown good agreement when compared with experimental data for the complexation of: arabic gum/gelatin, alginate/chitosan, DNA/chitosan, poly-L-lysine/chondroitin sulfate. / Mestre
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Avaliação do desempenho de flotação por ar dissolvido no tratamento de efluente de refinaria de óleo de soja / Valuation of performance of dissolved air flotation on treatment of wastewaters of soybean oil refiningCecchet, Juliana 06 July 2007 (has links)
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Previous issue date: 2007-07-06 / The aim of this work was to value the performance of three types of coagulants,
two of them of polichlorate of alum class and one of them was organic,
combined to three polyelectrolytes class (anionic, cationic and no ionic)
applying the dissolved air flotation (DAF), to viability their use on treatment of
effluents of soybean oil refinery. The study was conducted on laboratory scale
where first was tested the coagulants on several dosages combined to several
bands of pH and three ascension velocities (Va), finding a optimum band of this
combination for one of each three batteries. For this, was fixed parameters how
time and fast mixed gradient (1 min / 150 s-1), time and slow mixed gradient (10
min / 40 s-1 5 min / 20 s-1), pressure on saturation chamber (450 kPa) and
recirculation ratio (30%). Finding the optimum concentration of coagulant (Cc
ótima), optimum coagulation pH (pHcoag ótimo) and optimum ascension velocities
(Vaótima), fix those parameters and then goes for a variation of polyelectrolyte,
testing several dosages and finding a optimum concentrate of polyelectrolyte (Cf
ótimo). Finally, with junction of all optimized parameters, was varied de
recirculation rate (R) (10, 20 e 30%), choosing the best R and collecting
samples for the determination of levels of turbidity, total suspended solids
(TSS), volatile suspended solids (VSS), oil and greases (O&G) and chemical
oxygen demand (COD) remaining on treated effluent presenting a percentage
of remotion COD of 95,4%, 93,7% and 95,1% and O&G of 100%, 94,2% e
99,8% for the batteries 1, 2 e 3 respectively. Despite of being excellent
efficiencies of remotion, the treated effluent was not present characteristics for
the reuse on the cooling water towers, because its organics load on the raw
effluent its too much higher and even with so good levels of remotion, still was
necessary a pos treatment to think on reuse. / Este trabalho foi desenvolvido com o objetivo de avaliar o desempenho de três
tipos de coagulantes, dois da classe dos PACs (cloreto de polialumínio) e um
orgânico, combinados a três classes de polieletrólitos (aniônico, catiônico e não
iônico), aplicando o uso de Flotação por Ar Dissolvido (FAD), para viabilizar seu
uso em tratamento de efluentes de refinaria de óleo de soja. O experimento foi
conduzido em escala de laboratório e primeiramente foram testados os
coagulantes em diversas dosagens combinados a diversas faixas de pH e três
velocidades ascensionais (Va), encontrando uma faixa ótima dessa
combinação para cada uma das três baterias. Para tanto foram fixados
parâmetros como tempo e gradiente de mistura rápida (1 min / 150 s-1) tempo e
gradiente de mistura lenta (10 min / 40 s-1 5 min / 20 s-1), pressão na câmara
de saturação (450 kPa) e razão de recirculação (30%). Encontrando-se a
concentração de coagulante ótima (Cc ótima), pH de coagulação ótimo
(pHcoag ótimo) e velocidade ascensional ótima (Vaótima). Fixados esses
parâmetros foi verificada a variação do polieletrólito, testando-se em diversas
dosagens e encontrando uma concentração de floculante ótima (Cf ótimo).
Finalmente, com a junção de todos os parâmetros otimizados, efetua-se a
variação da razão de recirculação (R) (10, 20 e 30%), escolhendo a melhor R e
coletando-se amostras para a determinação dos níveis de turbidez, sólidos
suspensos totais (SST), sólidos suspensos voláteis (SSV), óleos e graxas
(O&G) e demanda química de oxigênio (DQO) remanescentes no efluente
tratado apresentando um grau de remoção de DQO de 95,4%, 93,7% e 95,1%
e de O&G de 100%, 94,2% e 99,8% para as baterias 1, 2 e 3 respectivamente.
Apesar de serem eficiências excelentes de remoção, o efluente tratado não
apresentou características de reuso em torres de resfriamento, pois sua carga
orgânica no efluente bruto é muito alta e mesmo com níveis tão bons de
remoção ainda seria necessário um pós-tratamento para se avaliar a
possibilidade de reuso.
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Polyelectrolyte conformation in layer-by-layer assembled nanoscale films / Conformation des polyélectrolyes dans des films nanométriques assemblés couche par coucheHigy, Christophe 01 April 2015 (has links)
L’assemblage couche-par-couche permet de fabriquer des films multimatériaux aux propriétés variées présentant une structure stratifiée. Ce travail décrit les études structurelles des films multicouches de polyélectrolytes à l’aide de mesures de diffusion de neutrons.L’effet du vieillissement des films a été déterminé par réflectométrie des neutrons. Nous avons observé un léger tassement des films après 5 ans et une forte expansion après 15 ans.Nous avons aussi montré que le substrat et l’air en surface ont une influence sur la structure des couches proches des extrémités des films, conduisant à une structure inhomogène perpendiculairement à la surface.Nous avons finalement étudié la conformation des chaînes de polyélectrolytes dans les films multicouches ; nous avons déterminé que les chaînes de PSS dans des films préparés par trempage ont une conformation en pelotes aplaties, contrairement aux chaînes de polyélectrolytes en solution qui présentent une conformation sphérique. / The Layer-by-Layer assembly allows the build-up of multimaterial films with various properties showing a stratified structure. This work describes the structural strudies of multilayer films of polyelectrolytes with neutron scattering measurements.Ageing effect on films was determined by neutron reflectometry. We observed a slight shrink of the films after 5 years and a strong expansion after 15 years.We also showed that the proximity of the substrate and the air at the surface have an influence on the structure of the layers at the extremities of the films, leading to an inhomogeneous structure perpendicularly to the surface.Finally, we studied the conformation of polyelectrolyte chains in the multilayer films ; we determined that PSS chains in dipped films have a flattened coil conformation, whereas the polyelectrolyte chains in solution have a spherical conformation.
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Polymer multilayers : fundamental aspects and application for biomaterials / Multicouches de polymères : aspects fondamentaux et application dans le domaine des biomatériauxSéon, Lydie 30 September 2014 (has links)
La surface d'un matériau est le lieu privilégié des interactions entre le matériau et son environnement. La technique couche-par-couche, qui consiste en un dépôt alterné de polyanions et de polycations, ouvre de nouvelles perspectives dans le domaine des biomatériaux pour le contrôle de ces interactions. La cohésion des films multicouches de polyélectrolytes est principalement assurée par des interactions électrostatiques mais a été étendue à d'autres forces motrices telles que les interactions hôte-invité. Nos travaux s’articulent autour de deux axes principaux. D’une part, nous nous sommes intéressés aux films multicouches de polymères neutres basés sur des interactions hôte-invité et en particulier à l'influence de la force du complexe d’inclusion b-cyclodextrine/ferrocène sur la topographie de ces films. La force de l’interaction hôte-invité a d’abord été modulée en associant différents invités (l’adamantane, le ferrocène et le pyrène) avec la β-cyclodextrine. La force du complexe b-cyclodextrine/ferrocène a été ensuite modulée par la présence de différents sels de sodium à différentes forces ioniques au cours de la construction du film. Une force d'interaction intermédiaire du complexe semble être nécessaire pour former des films continus, tandis que, si elle est trop faible, la force d'interaction limite la construction du film.D’autre part, motivé par le fait que la prévention des infections microbiennes des dispositifs médicaux implantables constitue un problème médical et financier majeur, nous avons développé de nouveaux revêtements antimicrobiens grâce à la technique couche-par-couche. Des films multicouches à base de polysaccharides contenant la cateslytine, un peptide antimicrobien, permettent l’inhibition en 24h du développement de Candida albicans et Staphylococcus aureus, qui sont des agents pathogènes communs et virulents rencontrés dans les maladies nosocomiales. La libération des peptides antimicrobiens est déclenchée par la dégradation enzymatique du film en présence des agents pathogènes. Le revêtement est ainsi qualifié d’auto-défensif. La non-cytotoxicité du film vis-à-vis des cellules humaines permet une application cliniquement pertinente pour prévenir les infections sur les cathéters. Des dimères à base de cateslytine de différentes longueurs et un dendrimère ont été synthétisés afin d'améliorer l'activité biologique du peptide d'origine, i.e. ses propriétés antimicrobiennes et antiinflammatoires. Afin d’élaborer des films antimicrobiens mécaniquement robustes, le polyuréthane (polymère entrant dans la composition des cathéters) a été fonctionnalisé par une couche de polydopamine qui peut ensuite réagir avec des groupements thiol ou amine, permettant la fixation covalente des films de polysaccharides antimicrobiens réticulés étape par étape. / The surface of a material is the privileged location, where the interactions between the material and its environment take place. In the field of biomaterials, the challenge is to control these interactions. A very versatile coating technique is the layer-by-layer deposition, which consists in the alternated deposition of polyanions and polycations. The cohesion of polyelectrolyte multilayer films is primarily ensured by electrostatic interactions but was extended to other driving forces such as host-guest interactions. Our work was constituted of two main parts.In the first part, the buildup of neutral polymer multilayer films based on host-guest interactions was studied and in particular the influence of β-cyclodextrin/ferrocene interaction strength on the topography of these films. The host-guest interaction strength was first modulated by involving different guests (adamantane, ferrocene and pyrene) in the buildup. Then, β -cyclodextrin/ferrocene interaction strength was tuned by the presence of different types and concentrations of salts during the multilayer buildup. Intermediate interaction strength seems to be required to form continuous films, whereas, if too low, the interaction strength limits the film buildup.In the second part, motivated by the fact that the prevention of pathogen colonization of implantable medical devices constitutes a major medical and financial issue, polyelectrolyte multilayers were used as tools to develop new antimicrobial coatings. Polysaccharide multilayer films containing cateslytin, an antimicrobial peptide, fully inhibited in 24h the development of Candida albicans and Staphylococcus aureus, which are common and virulent pathogens agents encountered in care-associated diseases. The release of the antimicrobial peptides was triggered by the enzymatic degradation of the film due to the pathogens themselves introducing the concept of self-defensive coating. The non-cytotoxicity of the film, towards human cells, highlights a medically relevant application to prevent infections on catheters. Different cateslytin based dimers with various lengths and one dendrimer were synthesized in order to improve the bioactivity of the original peptide, i.e. antimicrobial and anti-inflammatory properties. In order to obtain mechanically robust antimicrobial films, polyurethane (polymer that composes catheters) was functionalized with a polydopamine layer that can further react with thiol or amine groups, allowing the covalent attachment of step-by-step cross-linked antimicrobial polysaccharide films.
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Synthèse et caractérisation de membranes conductrices anioniques pour la protection d'électrode à air dans une batterie Zinc-Air fonctionnant sous air ambiant / Synthesis and characterization of anionic conducting membranes for the air electrode protection in a Zinc-Air battery operating under ambient airMessaoudi, Houssam mohammed 10 May 2016 (has links)
Différentes membranes conductrices anioniques ont été développées pour protéger une électrode à air fonctionnant dans une batterie Zinc-Air alimentée par de l’air ambiant. Dans ces conditions, le dioxyde de carbone contenu dans l’air, en contact avec l’électrolyte basique, se transforme en carbonate de potassium qui précipite dans la structure poreuse de l’électrode. Cela provoque l’augmentation de sa résistance et la perte de son étanchéité, et l’électrode n’est alors stable que 80 heures. L’objectif de cette étude est donc de rendre stable une électrode à air pendant 3000 heures de fonctionnement.Pour cela, différents réseaux (semi-)interpénétrés de polymères ont donc été développés en associant un polyélectrolyte et un réseau partenaire neutre. La polyépichlorhydrine greffée avec du 1,4-diazabicyclo(2,2,2)octane et un polyélectrolyte fluoré ont été choisis comme polymère conducteur anionique. Des réseaux neutres à base de poly(méthacrylate de 2-hydroxyéthyle), d’alcool polyvinylique et de perfluoropolyéther leur ont été, tour à tour, associés. Les propriétés physico-chimiques des différentes membranes développées ont été caractérisées selon leur densité de charges et leur composition. Les membranes présentant les meilleures propriétés requises (conductivité anionique, prise en masse limitée, sélectivité, …) ont ensuite été assemblées sur des électrodes à air dont le potentiel et la stabilité ont été évalués au cours du fonctionnement en demi-cellule. Ainsi, une électrode à air modifiée avec de telles membranes peut présenter un potentiel stable pendant 6800 heures de fonctionnement à -30mA/cm². / Different anionic conducting membranes have been developed to protect an air electrode operating in a Zinc-Air battery fed with ambient air. Under those conditions, carbon dioxide from atmospheric air reacts with the alkaline electrolyte, and is then transformed into potassium carbonate. The precipitate of this carbonate inside the electrode porous structure leads to the increase of the system resistance and the loss of its sealing after 80 h of operation. The objective of this study focuses on the improvement of the stability of an air electrode for 3000 h of operation, by protecting it from carbonation reaction with a polymer membrane.For this, different (semi-)interpenetrating polymer networks have therefore been developed combining a polyelectrolyte and a neutral network partner. Polyepichlorohydrin grafted with 1,4-diazabicyclo (2,2,2) octane and a fluorinated polyelectrolyte were chosen as anionic conductive polymer. Neutral networks based on poly (2-hydroxyethyl methacrylate), polyvinyl alcohol and perfluoropolyether were then, alternately, associated to the polyelectrolyte. The physico-chemical properties of the various developed membranes were characterized according to their charge density and composition. The membranes with the best required properties (anionic conductivity, limited weight uptake, selectivity ...) were then assembled on air electrodes whose potential and stability have been evaluated during the operation in half-cell. Thus, an air electrode modified with such membranes maintains a stable potential during 6800 hours of running at -30mA / cm².
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Croissance et propriétés de films minces conducteurs par auto-assemblage de polyélectrolytes / Growth and properties of thin conductive films obtained by self-assembly of polyelectrolytesJurin, Florian 05 December 2014 (has links)
L'auto-assemblage de polymères a été étudié afin d'élaborer des films multicouches possédant des propriétés conductrices. Dans un premier temps, l'influence de différents paramètres physico-chimiques (pH , force ionique, nature et charge des ions, concentrations en polymères...) sur la croissance de couche polymères isolants (PSS ou PDDA) / polymères conducteurs ( PEDOT : PSS ou P3HT-R) a été étudiée par des mesures in-situ de réflectométrie laser à angle fixe. La compréhension de ses paramètres a permis de contrôler l'assemblage des matériaux afin d'obtenir des films multicouches aux propriétés souhaitées ( épaisseur, morphologie, conductivité électrique...)les épaisseurs des films obtenus ont été déterminées par ellipsométrie ou profilométrie, la morphologie de la morphologie de la surface de ces films a été observé par MEB et leur conductivité a été mesurée par la méthode de van Pauw. Dans un second temps, des films multicouches polymères / particules composites ont été construits après avoir optimisé les conditions d'élaboration des particules composites Al2-PEDOT : PSSph ou SiO2-P3HT-R).Les films multicouches obtenus présentent des conductivités équivalentes à celles des films à base de polymères mais sont construits avec moins d'étapes d'adsorption. Enfin des couches multicouches à bases de deux polymères conducteurs (P3HT-R et PEDOT:PSS) ont été construits sur substrats souples. Ils présentent la plus haute conductivité mesurée (1,5 S.m-1) et conservent leurs propriétés électriques lorsqu'ils sont soumis à des contraintes mécaniques de flexion , ce qui est prometteur quant à leur utilisation dans le domaine de l'électronique déformable. / Self-assembly of polymers has been studied in order to produce multilayer films having conductive properties. First, the influence of various physicochemical parameters (pH, ionic strength, nature and charge of ions, polymer concentrations, etc.) on the growth of insulating polymer (PSS or PDDA) / conductive polymers (PEDOT : PSS or P3HT-R) was studied by in-situ measurements of fixed-angle laser reflectometry. The understanding of its parameters allowed to control the assembly of the materials in order to obtain multilayer films with the desired properties (thickness, morphology, electrical conductivity...) The thicknesses of the films obtained were determined by ellipsometry or profilometry, morphology Of the surface morphology of these films was observed by SEM and their conductivity was measured by the method of van Pauw. Second, polymer multilayer films / composite particles were built after optimizing the conditions for the production of the composite particles Al2-PEDOT: PSSph or SiO2-P3HT-R). The multilayer films obtained have conductivities equivalent to those of Films are based on polymers but are constructed with fewer adsorption steps. Finally, multilayer layers based on two conductive polymers (P3HT-R and PEDOT: PSS) were built on flexible substrates. They have the highest conductivity measured (1.5 Sm-1) and retain their electrical properties when subjected to mechanical bending stresses, which is promising for their use in the field of deformable electronics.
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Etude de dispersions de nanotubes de carbone par des polymères pour l’élaboration de composites conducteurs et structurésSaint-Aubin, Karell 04 May 2010 (has links)
Cette thèse rapporte l’étude de dispersions de nanotubes de carbone par des polymères, la mise en forme de films composites et l’étude de leurs propriétés mécaniques ou de conduction électrique. La première partie est centrée autour de l’utilisation de l’acide poly-acrylique (PAA), qui se révèle un excellent agent dispersant des nanotubes dans l’eau. Une étude des interactions entre le polyélectrolyte et les nanotubes en fonction du pH est réalisée afin d’identifier les conditions de dispersion optimales. La réalisation de composites pour de potentielles applications dans les encres et peintures conductrices révèle qu’un contrôle suffisamment fin de l’adsorption du PAA et de la stabilité de la dispersion permet l’obtention de films à la fois homogènes et conducteurs électriques. La seconde partie de ce travail concerne l’utilisation d’un copolymère à blocs, le SBM, possédant des propriétés remarquables d’auto-organisation pour la réalisation de composites par voie solvant à base de nanotubes. L’originalité du système réside dans le fait que le SBM est à la fois agent dispersant des nanotubes mais également matrice structurante. Ce travail montre que la structure adoptée par le copolymère, qui dépend beaucoup du solvant employé, influence directement les propriétés mécaniques du matériau. De plus, l’addition de nanotubes améliore sensiblement les performances du composite. / This thesis deals with the study of carbon nanotube dispersions by polymers, the processing of composite films and the study of their mechanical and electrical properties. The first part of the work focuses on the use of poly(acrylic) acid (PAA), which proves to be an excellent dispersing agent in water. A study of the interactions between the PAA and the nanotubes is realised, tuned by the pH conditions. The fabrication of composite films, for future applications in the field of conductive inks and paints, shows that a fine control of the PAA adsorption and the dispersion stability allows the formation of homogeneous and conductive composites. In a second part, nanotube composites are elaborated from a block copolymer, the SBM, well-known for its remarkable self organization properties. Interestingly, the copolymer is at the same time the nanotube dispersing agent in the solvent and the structuring matrix of the final composite. This thesis shows that the copolymer structure, which strongly depends on the solvent used, influences the mechanical properties of composite films, and that the addition of nanotubes noticeably improves the performances.
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Time-dependent chemo-electromechanical behavior of hydrogelbased structuresLeichsenring, Peter, Wallmersperger, Thomas 13 August 2020 (has links)
Charged hydrogels are ionic polymer gels and belong to the class of smart materials. These gels are multiphasic materials which consist of a solid phase, a fluid phase and an ionic phase. Due to the presence of bound charges these materials are stimuli-responsive to electrical or chemical loads. The application of electrical or chemical stimuli as well as mechanical loads lead to a viscoelastic response. On the macroscopic scale, the response is governed by a local reversible release or absorption of water which, in turn, leads to a local decrease or increase of mass and a respective volume change.
Furthermore, the chemo-electro-mechanical equilibrium of a hydrogel depends on the chemical composition of the gel and the surrounding solution bath. Due to the presence of bound charges in the hydrogel, this system can be understood as an osmotic cell where differences in the concentration of mobile ions in the gel and solution domain lead to an osmotic pressure difference.
In the present work, a continuum-based numerical model is presented in order to describe the time-dependent swelling behavior of hydrogels. The numerical model is based on the Theory of Porous Media and captures the fluid-solid, fluid-ion and ion-ion interactions. As a direct consequence of the chemo-electro-mechanical equilibrium, the corresponding boundary conditions are defined following the equilibrium conditions. For the interaction of the hydrogel with surrounding mechanical structures, also respective jump condtions are formulated. Finaly, numerical results of the time-dependent behavior of a hydrogel-based chemo-sensor will be presented.
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Generation and Characterisation of Nanostructures from Single Adsorbed Polyelectrolyte MoleculesGorodyska, Ganna 09 September 2005 (has links)
Visualization and study of reconformation of polyelectrolytes (PEs) of different architecture is of great fundamental and practical interest. Verification of theoretical predictions with experiment is of essential importance. On the other hand, a wide range of bottom-up techniques based on patterning of matter on the length scale of a few nanometers have been recently developed. Particularly interesting is the possibility of using self-assembled single molecule structures as templates for the deposition of inorganic matter, in particular metals. Synthetic "normal-sized" polymers of various architecture, like poly-2-vinylpyridine (P2VP) or polystyrene-poly(2-vynil pyridine) P2VP7-PS7 star-like block copolymer, adsorbed on solid substrates have been visualized for the first time with molecular resolution by AFM in different conformation. This finding allowed us to study largely discussed problem, a coil-to-globule transition of PEs. It was found that PE molecules undergo conformational transitions from stretched worm-like coil to compact globule via set of necklace-like globules, as the fraction of charged monomers decreases with an increase of pH and ionic strength. These results are in good agreement with recently developed DRO theory for weakly charged flexible PEs in poor solvent. The size of the deposited single molecules correlates very well with molecular dimensions in solution obtained in light scattering experiments. PE single molecules of various architectures was mineralized in different conformations that constitutes the route to nanoparticles with desired shape (including wire-shape and star-shaped), size, and composition (including metallic, magnetic and semiconductive nanoparticles). It was shown that molecular details of the adsorbed linear flexible PE molecules determine the dimensions of the nanostructures after metallization and that observed sizes are consistent with the decoration of single molecules with nanoclusters. Thus those metallized nanoparticles (cluster assembles) reflect the conformation of original adsorbed PE molecules. The dimensions of the obtained nanowires are significantly smaller than those previously reported. All of these features are of the potential benefit in applications for nanodevices. Metallization of the PS7-P2VP7 improves AFM resolution due to the selective deposition of Pd clusters along the P2VP chains. For the first time, the number of the P2VP second generation arms of the heteroarm block-copolymer was directly counted in the single molecule AFM experiment. Simple contrasting procedure was developed to improve AFM visualization of positively charged polymer chains deposited on the substrates of relatively high roughness. This method allows increasing the thickness of the resulting structures up to 10 nm, and, consequently, provide visualization of polymer chains on rough surfaces. This innovation is important for the development of single molecule experiments with polymer chains. The reaction of HCF-anion could be used for recognition of polycation molecules, when polycations, polyanions and neutral molecules coexist on the surface. Recently, the study was strongly restricted to atomically smooth surfaces. The contrasting procedure extends the range of substrates (Si-wafers, chemically modified or patterned Si-wafers, polished glasses, polymer films, etc) appropriate for the experiments. Thus, polymer single molecules can be considered not only as representative of the ensemble molecules, but also as individual nanoscale objects which can be used for future nanotechnology for the fabrication of single molecule electronic devices. Also these findings are important from fundamental point of view, since developed approach can be successfully applied for investigation of various "classical" problems in polymer science, such as polymer reconformation, interpolyelectrolyte complex formation, polymer diffusion, adsorption, etc.
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