Polymer and organic electronic memory devices offer the potential for cheap, simple memories that could compete across the whole spectrum of digital memories, from low cost, low performance applications, up to universal memories capable of replacing all current market leading technologies, such as hard disc drives, random access memories and Flash memories. Polymer memory devices (PMDs) are simple, two terminal metal-insulator-metal (MIM) bistable devices that can exist in two distinct conductivity states, with each state being induced by applying different voltages across the device terminals. Currently there are many unknowns and much ambiguity concerning the working mechanisms behind many of these PMDs, which is impeding their development. This research explores some of these many unanswered questions and presents new experimental data concerning their operation. One prevalent theory for the conductivity change is based on charging and charge trapping of nanoparticles and other species contained in the PMD. The work in this research experimentally shows that gold nanoparticle charging is possible in these devices and in certain cases offers an explanation of the working mechanism. However, experimental evidence presented in this research, shows that in many reported devices the switching mechanism is more likely to be related to electrode effects, or a breakdown mechanism in the polymer layer. Gold nanoparticle charging via electrostatic force microscopy (EFM) was demonstrated, using a novel device structure involving depositing gold nanoparticles between lateral electrodes. This allowed the gold nanoparticles themselves to be imaged, rather than the nanoparticle loaded insulating films, which have previously been investigated. This method offers the advantages of being able to see the charging effects of nanoparticles without any influence from the insulating matrix and also allows charging voltages to be applied via the electrodes, permitting EFM images to capture the charging information in near real-time. Device characteristics of gold nanoparticle based PMDs are presented, and assessed for use under different scenarios. Configurations of memory devices based on metal-insulator-semiconductor (MIS) structures have also been demonstrated. Simple interface circuitry is presented which is capable of performing read, write and erase functions to multiple memory cells on a substrate. Electrical properties of polystyrene thin films in the nanometre thickness range are reported for the first time, with insulator trapped charges found to be present in comparable levels to those in silicon dioxide insulating films. The dielectric breakdown strength of the films was found to be significantly higher than bulk material testing would suggest, with a maximum dielectric strength of 4.7 MV•cm-1 found, compared with the manufacturers bulk value of 0.2 – 0.8 MV•cm-1. Conduction mechanisms in polystyrene were investigated with the dominant conduction mechanism found to be Schottky emission.

Ce manuscrit décrit l'utilisation de particules de silice colloïdale de taille et de fonctionnalité définies pour élaborer des matériaux aux propriétés spécifiques. Dans un premier temps, nous avons comparé différentes méthodes de synthèse de particules de silice à partir d'un précurseur moléculaire selon un procédé sol-gel. Celles-ci nous ont permis de fabriquer des objets sphériques de fonction de surface contrôlée et avec une taille moyenne régulière comprise entre 50 nm et 2 microns. Une fois ces particules synthétisées, nous avons étudié leur comportement à l'interface air-eau grâce à la technique de Langmuir puis fabriqué des cristaux colloïdaux d'épaisseur contrôlée par dépositions successives de monocouches de particules sur des substrats hydrophiles selon le principe de la technique de Langmuir-Blodgett. Ce contrôle nous a permis d'étudier l'influence de l'épaisseur des cristaux sur leurs propriétés spectroscopiques. Le second axe de notre recherche concernait l'élaboration de particules à morphologie originale et en particulier d'objets dissymétriques. L'utilisation de différentes techniques impliquant des phénomènes interfaciaux a d'abord été envisagée (interfaces planes puis courbes à l'échelle macroscopique). Nous avons également élaboré de particules organiques-inorganiques grâce à un procédé de polymérisation en émulsion de styrène en présence de particules de silice modifiées en surface. La maîtrise des différents paramètres expérimentaux nous a ainsi permis d'obtenir des objets hybrides aux morphologies originales mais prédictibles et variées, qu'elles soient dissymétriques (± haltère a, ± bonhomme de neige a, ± cœur-écorce décentré a) ou non (± marguerite a, ± multipode a ou ± framboise a). Ces nouveaux types de particules colloïdales pourraient présenter des propriétés innovantes dans de nombreux domaines tels que la catalyse, l'affichage électronique ou la stabilisation de milieux complexes

In this thesis the interactions in cellulose systems havebeen studied with emphasis on surface forces and adsorptionphenomenon. The study was limited to surfaces and polymers ofinterest for papermaking. During papermaking both therunability of the paper machine as well as the properties ofthe final paper will depend on the molecular interactionsbetween the components present in the suspension. The objectiveof this work was to gain a better understanding of theseinteraction forces and how they are affected by solutionconditions like pH and electrolyte concentration. The maintechniques employed for this purpose were direct surface forcemeasurements using both the interferometric surface forceapparatus (SFA) and the atomic force microscopy (AFM)colloidal-probe technique. In addition, both electronspectroscopy for chemical analysis (ESCA) and AFM imaging wereused for surface characterisation and to study adsorptionbehaviour. Since a smooth and transparent surface is needed forsurface force studies using SFA, Langmuir-Blodgett films ofcellulose were employed. The interactions between cellulose surfacesand xylansurfaces were studied. Cellulose is the main constituent of thewood fibre. In close association with cellulose in the cellwall are the hemicelluloses, xylan being a commonhemicellulose. Steric forces were found to dominate theinteractions between these substances in aqueous solutions.Still factors like charge density, solution pH and electrolyteconcentration were important. The adhesion between cellulosesurfaces in air depended on the contact area. The effect of acationic polyelectrolyte on the forces between cellulosesurfaces and between cellulose and mineral surfaces wasinvestigated to obtain a better understanding of the effects ofcationic retention and strength additives. In the presence of acationic polyelectrolyte the forces at large distances weredominated by double-layer repulsion. Bridging attraction was insome cases observed, but the presence and magnitude of thisforce was dependent on the properties of the substratesurface. Lignin on the fibre surface affects brightness, swelling andstrength of paper. In addition, dissolved lignin interfereswith added polymers during papermaking. For this reason theadsorption of lignin on cellulose fibre surfaces was explored.The adsorption of lignin was influenced by the concentration oflignin in solution and by the electrolyte composition of thesolution. The retention of lignin was affected by the presenceof a cationic polyelectrolyte and particularly by how thepolyelectrolyte was added. The AFM imaging revealed thestructure of the adsorbed lignin, which varied with the way ofadding the polyelectrolyte, and gave an idea about theadsorption mechanism. The effect of lignin on strengthproperties of paper sheets was also evaluated. Keywords: cellulose, hemicellulose, xylan, lignin, surfaceforces, adsorption, polyelectrolyte, SFA, AFM, ESCA,Langmuir-Blodgett films, chitosan, steric forces,bridging,adhesion

Ce travail porte sur la formation et la caractérisation de nouveaux systèmes organiques-inorganiques par l'utilisation de films de Langmuir et de la technique de Langmuir-Blodgett. Plusieurs voies ont ainsi été explorées afin d'obtenir des films minces hybrides aux propriétés multiples, en particulier magnétiques. L'utilisation de l'interaction entre monocouches cationiques et des anions présents en sous-phase a ainsi permis l'organisation de différents polyanions inorganiques en structure lamellaire. Cette stratégie a ensuite été généralisée au cas de colloïdes de Bleu de Prusse, composés bimétalliques étendus. Une large étude (de la préparation à la caractérisation) a été consacrée à ces matériaux mixtes Bleu de Prusse-dérivé amphiphile de Ru(bpy)3 2+. Il a été également montré que la cristallisation du Bleu de Prusse et de ses analogues est favorisée en-dessous des films de Langmuir. Finalement, la coordination d'ions dissous en sous-phase avec des molécules amphiphiles à l'interface permet d'élaborer de nouveaux systèmes pouvant former des films LB, ce qui est notamment le cas d'agencements à base de cyanures métalliques.

ÉCe travail porte sur la formation et la caractérisation de nouveaux systèmes organiques-inorganiques par l'utilisation de films de Langmuir et de la technique de Langmuir-Blodgett. Plusieurs voies ont ainsi été explorées afin d'obtenir des films minces hybrides aux propriétés multiples, en particulier magnétiques. L'utilisation de l'interaction entre monocouches cationiques et des anions présents en sous-phase a ainsi permis l'organisation de différents polyanions inorganiques en structure lamellaire. Cette stratégie a ensuite été généralisée au cas de colloïdes de Bleu de Prusse, composés bimétalliques étendus. Une large étude (de la préparation à la caractérisation) a été consacrée à ces matériaux mixtes Bleu de Prusse-dérivé amphiphile de Ru(bpy)32+. Il a été également montré que la cristallisation du Bleu de Prusse et de ses analogues est favorisée en-dessous des films de Langmuir. Finalement, la coordination d'ions dissous en sous-phase avec des molécules amphiphiles à l'interface permet d'élaborer de nouveaux systèmes pouvant former des films LB, ce qui est notamment le cas d'agencements à base de cyanures métalliques. / El trabajo presentado como Tesis Doctoral trata sobre la formación y la caracterización de nuevos sistemas orgánicos-inorgánicos en películas de Langmuir y Langmuir-Blodgett. El método semi-anfifílico ha sido utilizado para obtener películas delgadas donde las dos entidades pueden participar en las propiedades del material híbrido. Así, un amplio estudio (desde la preparación hasta la caracterización) ha sido dedicado a las películas moleculares de Azul de Prusia y un derivado anfifílico de Ru(bpy)32+. Además, otras estrategias han sido desarrolladas para obtener sistemas extendidos. La coordinación de iones disueltos en la subfase con las moléculas anfifílicas en la interfase permite elaborar nuevos sistemas que pueden formar posteriormente multicapas, como es el caso de los compuestos a base de cianuros. Se ha demostrado también que la cristalización del Azul de Prusia y sus análogos a partir de sus iones precursores está favorecida en la interfase bajo las películas de Langmuir. Las películas de Langmuir han sido estudiadas a partir de las isotermas de compresión y de la difracción de rayos X a ángulos rasantes y las películas de Langmuir-Blodgett han sido caracterizadas por espectroscopías infrarroja y UV-visible, difracción de rayos X a ángulos pequeños, magnetismo, electroquímica y Microscopía Electrónica a Transmisión.

<p>In this thesis the interactions in cellulose systems havebeen studied with emphasis on surface forces and adsorptionphenomenon. The study was limited to surfaces and polymers ofinterest for papermaking. During papermaking both therunability of the paper machine as well as the properties ofthe final paper will depend on the molecular interactionsbetween the components present in the suspension. The objectiveof this work was to gain a better understanding of theseinteraction forces and how they are affected by solutionconditions like pH and electrolyte concentration. The maintechniques employed for this purpose were direct surface forcemeasurements using both the interferometric surface forceapparatus (SFA) and the atomic force microscopy (AFM)colloidal-probe technique. In addition, both electronspectroscopy for chemical analysis (ESCA) and AFM imaging wereused for surface characterisation and to study adsorptionbehaviour. Since a smooth and transparent surface is needed forsurface force studies using SFA, Langmuir-Blodgett films ofcellulose were employed.</p><p>The interactions between cellulose surfacesand xylansurfaces were studied. Cellulose is the main constituent of thewood fibre. In close association with cellulose in the cellwall are the hemicelluloses, xylan being a commonhemicellulose. Steric forces were found to dominate theinteractions between these substances in aqueous solutions.Still factors like charge density, solution pH and electrolyteconcentration were important. The adhesion between cellulosesurfaces in air depended on the contact area. The effect of acationic polyelectrolyte on the forces between cellulosesurfaces and between cellulose and mineral surfaces wasinvestigated to obtain a better understanding of the effects ofcationic retention and strength additives. In the presence of acationic polyelectrolyte the forces at large distances weredominated by double-layer repulsion. Bridging attraction was insome cases observed, but the presence and magnitude of thisforce was dependent on the properties of the substratesurface.</p><p>Lignin on the fibre surface affects brightness, swelling andstrength of paper. In addition, dissolved lignin interfereswith added polymers during papermaking. For this reason theadsorption of lignin on cellulose fibre surfaces was explored.The adsorption of lignin was influenced by the concentration oflignin in solution and by the electrolyte composition of thesolution. The retention of lignin was affected by the presenceof a cationic polyelectrolyte and particularly by how thepolyelectrolyte was added. The AFM imaging revealed thestructure of the adsorbed lignin, which varied with the way ofadding the polyelectrolyte, and gave an idea about theadsorption mechanism. The effect of lignin on strengthproperties of paper sheets was also evaluated.</p><p>Keywords: cellulose, hemicellulose, xylan, lignin, surfaceforces, adsorption, polyelectrolyte, SFA, AFM, ESCA,Langmuir-Blodgett films, chitosan, steric forces,bridging,adhesion</p>

Au cours de ce travail, nous avons étudié la dynamique des phospholipides constitutifs des bicouches lipidiques supportées sur des substrats solides. A l'aide d'un dispositif de retour de fluorescence après photoblanchiment (FRAPP : Fluorescence Recovery After Patterned Photobleaching), nous avons mis en évidence différents comportements diffusifs suivant la nature du substrat (rugosité et chimie), le phospholipide et la méthode de préparation de la bicouche. La mesure du coefficient de diffusion en fonction de la température nous a permis d'établir un ensemble de données fiables et reproductibles sur la transition de phase gel-fluide de ces systèmes. Il est apparu que leur diffusion dépendait de la nature du substrat. En effet, sur le verre, où les deux feuillets ont la même dynamique, on observe une transition couplée. Au contraire, sur le mica, le feuillet proximal a une dynamique plus lente que le feuillet distal qui est quasiment libre de toute interaction avec le support. La méthode de préparation s'est également révélée être un paramètre crucial puisque nous avons obtenu une plus grande dispersion des mesures en préparant les bicouches par éclatement de vésicules par rapport à la technique de Langmuir-Blodgett / Langmuir-Schaeffer qui donnent des échantillons sans microdomaines. Nous avons également déterminé les énergies d'activation des différentes phases ainsi que les enthalpies de transition pour les deux phospholipides étudiés. Ce travail constitue une étape primordiale dans la compréhension des mécanismes diffusifs de systèmes plus complexes.

Les puroindolines (isoformes a et b) sont des protéines extraites du grain de blé et dont la structure est stabilisée par cinq ponts disulfure. La pin-a possède un domaine unique riche en tryptophane (WRWWKWWK) qui est tronqué dans le cas de la pin-b (WPTKWWK). Les deux galactolipides majeurs de l'endosperme du blé, MGDG et DGDG, ont été extraits et purifiés. Les études ont été réalisées à l'interface liquide/air et en dispersion aqueuse grâce à des techniques appropriées : tensiométrie, ellipsométrie, microscopies à l'angle de Brewster et à force atomique, techniques spectroscopiques (PM-IRRAS, Raman, ATR), et diffraction des rayons X. Les lipides ainsi que leur mélange équimolaire montrent des propriétés spécifiques attribuées aux fortes interactions entre les têtes polaires galactosyl. La pin-a et la pin-b présentent des propriétés similaires, en particulier une forte activité à l'interface. Finalement, l'étude des interactions protéine/lipide montre que la pin-a interagit plus fortement avec les galactolipides en formant des structures (réseaux) qui pourraient être à l'origine de la forte stabilité des mousses pin-a/lipide.

Supercapacitors are well known for their improvised power density compared to batteries. Ongoing research is mainly focused on improving the energy density of supercapacitors by using different electrode material nanocomposites. The recent research has revealed that graphene (G)-polyaniline (PANI) nanocomposite could be a promising material for supercapacitor applications. The supercapacitor is also associated with self-leakage current regardless of any electrode material. The main objectives of the project are to: (i) synthesize highly fabricate supercapacitor based of G-PANI electrode; (ii) improve the energy density of supercapacitor by applying ultrathin monolayer/monolayers film electrode surface. It is crucial to either improve or retain the effective capacitance of the dielectric film. The dielectric material chosen is polyvinylidene fluoride (PVDF) due to its dielectric constant and electrochemical properties. Langmuir-Schaefer (LS) technique is used to deposit the PVDF film onto the substrate. The optical properties of electrode materials were measured by UV-vis spectrophotometer. The surface morphology of the fabricated electrode material has been investigated using scanning electron microscopic (SEM) and atomic force microscopic (AFM) studies. The supercapacitor with and without dielectric layer have been studied using cyclic voltammetry, charging and discharging, and electrochemical impedance techniques, respectively. The specific capacitance has been found to increase by application of one monolayer of PVDF film of G-PANI electrode. However, the LS film of PVDF does not show the minimization of leakage current but revealed an increase in the specific capacitance due to enhancement in surface area associated with the electrode besides PVDF is also an electrochemical active material. The electrochemical investigation of various layers of PVDF on G-PANI in symmetric and asymmetric supercapacitor configuration has been presented in thesis. The future scope of the project could be designing the electrode with various number of layers of dielectric material that could reduce the leakage current, and retaining the specific capacitance of G-PANI nanocomposite electrodes.

Submitted by Vinicíus Jessé Rodrigues de Oliveira null (vinijro@gmail.com) on 2018-03-20T20:23:10Z No. of bitstreams: 1 DISSERTAÇÃO FINAL JESSE 2018.pdf: 6372777 bytes, checksum: 1bb0391cd590635dcecd1727ee43665e (MD5) / Approved for entry into archive by Maria Marlene Zaniboni null (zaniboni@bauru.unesp.br) on 2018-03-21T17:01:53Z (GMT) No. of bitstreams: 1 oliveira_vjr_me_bauru.pdf: 6372777 bytes, checksum: 1bb0391cd590635dcecd1727ee43665e (MD5) / Made available in DSpace on 2018-03-21T17:01:53Z (GMT). No. of bitstreams: 1 oliveira_vjr_me_bauru.pdf: 6372777 bytes, checksum: 1bb0391cd590635dcecd1727ee43665e (MD5) Previous issue date: 2018-02-16 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Os polímeros conjugados aplicados como camada ativa, em dispositivos optoeletrônicos têm alto potencial tecnológico e tem sido amplamente estudados nas últimas décadas. Estes materiais podem ser processados na forma de filmes finos e dependendo da técnica utilizada pode-se obter filmes organizados e altamente reprodutíveis. Uma das técnicas de deposição que pode proporcionar estas propriedades é a de Langmuir Blodgett (LB) e Langmuir Schaefer (LS). Este trabalho de mestrado teve como objetivo fabricar e caracterizar materiais/filmes com capacidade para aplicação em dispositivos fotovoltaicos Os materiais caracterizados, com este objetivo, foram polímeros de baixo valor de band gap:poli[(4,4-bis(2-etilhexil)-ciclopenta-[2,1-b:3,4-b’]ditiofeno)2,6-diil-alt-(2,1,3-benzotiadiazol)-4,7-diil], PCPDTBT e poli[(4,4’-dioctilditieno[3,2-b:2’,3’d]silol-2,6-diil)-alt-(2,1,3-benzotiadiazol)-4,7-diil)], PDTSBT. Para a fabricação dos filmes ultrafinos foi realizado um estudo de isotermas de pressão superficial por área do monómero (π-A) em uma cuba de Langmuir. As técnicas de LB e LS permitiram o processamento molecular dos materiais através das informações obtidas das isotermas (π-A). As caracterizações ópticas (UV-Vis) foram realizadas para análise de crescimento e da organização das camadas dos filmes finos. Para as medidas elétricas foi utilizado uma fonte de corrente continua para se obter a condutividade e fotocondutividade elétrica dos filmes depositados por LB e LS sobre eletrodos interdigitados. Os filmes fabricados foram utilizados como camadas ativas dos dispositivos fotovoltaicos em uma heterojunção planar, com estrutura basicamente formada por ITO/Polímero/PCBM/Alumínio. Foram realizadas medidas de densidade de corrente versus tensão (J vs V) sob iluminação de um Simulador Solar para o cálculo de eficiência da célula. / The conjugated polymers applied as active layer in optoelectronic devices, have high technological potential and have been widely studied in recent decades. These materials can be processed in the form of thin films, and depending on the technique used one can obtain organized and highly reproducible films. One of the deposition techniques that can provide these properties is Langmuir Blodgett (LB) and Langmuir Schaefer (LS). This master 's work was designed to manufacture and characterize materials / films with potential for application in photovoltaic devices. The materials characterized for this purpose, were low bandgap value polymers: poly [(4,4-bis (2-ethylhexyl) cyclopenta- [2,1-b: 3,4-b '] dithiophene) 2,6-diyl-al- (2,1,3-benzothiadiazole) - 4,7-diyl] PCPDTBT and poly [(4,4'-dioctyldithieno [3,2-b: 2 ', 3'd] silol-2,6-diyl) -alt- (2,1,3-benzothiadiazol) -4,7- ] PDTSBT. For the production of ultrafine films, a study of surface pressure isotherms by area of the monomer (π-A) in a Langmuir trough was performed. The LB and LS techniques allowed the molecular processing of the materials through the information obtained from the isotherms (π-A). The optical characterizations (UV-Vis) were performed for analysis of the growth and organization of thin film layers. For the electrical measurements, a DC current source was used to obtain the electrical conductivity and photoconductivity of the films deposited by LB and LS on interdigitated electrodes. The films manufactured were used as active layers of the photovoltaic devices in a planar heterojunction, with structure basically formed by ITO / Polymer / PCBM / Aluminum. Measurements of current versus voltage density (J vs V) were performed under illumination of a Solar Simulator to calculate cell efficiency. / 1578726