<p>The thesis describes an investigation into the interaction between the conducting polymer and cellulosic materials, and the preparation of electroconductive paper. The adsorption behavior of the conducting polymer onto cellulosic materials was characterized. Poly(3,4-ethylenedioxythiophene) doped with poly(4-styrene sulfonate) (PEDOT:PSS) was used as conducting polymer because of its attractive properties in terms of conductivity, water solubility, and environmental stability. The model substrate used for adsorption was microcrystalline cellulose (MCC). Various pH levels and salt concentrations were explored to completely understand the adsorption behavior of PEDOT:PSS. The variation in surface charge characteristics when the pH and salt concentration were changed was monitored by polyelectrolyte titration and zeta potential measurement. The adsorption isotherm showed a broad molecular distribution of the conducting polymer and considerable interaction between the polymer and MCC. As the pH of the solution was increased, the adsorbed amount decreased. With varying salt concentrations, the adsorption passed through a maximum. The extent of deposition of PEDOT:PSS on the surface of cellulosic fibers was investigated using X-ray Photoelectron Spectroscopy (XPS) with a commercial base paper as substrate. XPS analysis of dip-coated paper samples showed PEDOT enrichment on the surface. The degree of washing the dip-coated paper with acidic water did not significantly affect the PEDOT enrichment on the surface.</p><p> </p><p>A base paper was coated with PEDOT:PSS blends to produce electroconductive papers. The bulk conductivities (σ_dc) of the coated papers were measured using a four-probe technique and impedance spectroscopy. One-side and two-side coating gave comparable conductivity levels. Various organic solvents added to the PEDOT:PSS dispersion at different concentrations showed various effects on the bulk conductivity of the coated paper. Blends containing sorbitol and isopropanol did not enhance the bulk conductivity of the coated paper, and at high concentrations these organic solvents lowered the conductivity. Paper samples coated with a PEDOT:PSS blend containing N-methylpyrrolidinone (NMP) and dimethyl sulfoxide (DMSO) exhibited a higher conductivity than when coated with pure PEDOT:PSS, due to conformational changes and their plasticizing effect. The effect of calendering was investigated and only the sample subjected to 174 kN/m line load after coating showed significant conductivity enhancement. The addition of TiO₂ pigment lowered the bulk conductivity of the paper. Contact angle measurements were made to monitor the effect of coating the paper with PEDOT:PSS blends on the hydrophilicity of the paper samples. The amount of PEDOT:PSS deposited in the fiber network was determined using total sulfur analysis. Thus, this study makes use of conventional paper surface treatment as method for achieving bulk conductivity of paper in the semi-conductor range without significantly decreasing the paper strength.</p> / Printed Polymer Electronics

The thesis describes an investigation into the interaction between the conducting polymer and cellulosic materials, and the preparation of electroconductive paper. The adsorption behavior of the conducting polymer onto cellulosic materials was characterized. Poly(3,4-ethylenedioxythiophene) doped with poly(4-styrene sulfonate) (PEDOT:PSS) was used as conducting polymer because of its attractive properties in terms of conductivity, water solubility, and environmental stability. The model substrate used for adsorption was microcrystalline cellulose (MCC). Various pH levels and salt concentrations were explored to completely understand the adsorption behavior of PEDOT:PSS. The variation in surface charge characteristics when the pH and salt concentration were changed was monitored by polyelectrolyte titration and zeta potential measurement. The adsorption isotherm showed a broad molecular distribution of the conducting polymer and considerable interaction between the polymer and MCC. As the pH of the solution was increased, the adsorbed amount decreased. With varying salt concentrations, the adsorption passed through a maximum. The extent of deposition of PEDOT:PSS on the surface of cellulosic fibers was investigated using X-ray Photoelectron Spectroscopy (XPS) with a commercial base paper as substrate. XPS analysis of dip-coated paper samples showed PEDOT enrichment on the surface. The degree of washing the dip-coated paper with acidic water did not significantly affect the PEDOT enrichment on the surface.   A base paper was coated with PEDOT:PSS blends to produce electroconductive papers. The bulk conductivities (σdc) of the coated papers were measured using a four-probe technique and impedance spectroscopy. One-side and two-side coating gave comparable conductivity levels. Various organic solvents added to the PEDOT:PSS dispersion at different concentrations showed various effects on the bulk conductivity of the coated paper. Blends containing sorbitol and isopropanol did not enhance the bulk conductivity of the coated paper, and at high concentrations these organic solvents lowered the conductivity. Paper samples coated with a PEDOT:PSS blend containing N-methylpyrrolidinone (NMP) and dimethyl sulfoxide (DMSO) exhibited a higher conductivity than when coated with pure PEDOT:PSS, due to conformational changes and their plasticizing effect. The effect of calendering was investigated and only the sample subjected to 174 kN/m line load after coating showed significant conductivity enhancement. The addition of TiO2 pigment lowered the bulk conductivity of the paper. Contact angle measurements were made to monitor the effect of coating the paper with PEDOT:PSS blends on the hydrophilicity of the paper samples. The amount of PEDOT:PSS deposited in the fiber network was determined using total sulfur analysis. Thus, this study makes use of conventional paper surface treatment as method for achieving bulk conductivity of paper in the semi-conductor range without significantly decreasing the paper strength. / Printed Polymer Electronics

Comprendre et modéliser le comportement des matériaux sous irradiation électronique est un enjeu important pour l’industrie spatiale. La fiabilité des satellites nécessite de maîtriser et prédire les potentiels de surface s'établissant sur les diélectriques. Ce travail de doctorat a donc pour objectif de caractériser et de modéliser les différents mécanismes physiques (en surface et en volume) gouvernant le potentiel de charges dans les matériaux polymères spatiaux tels que le Téflon® FEP et le Kapton® HN. La mise au point d'un nouveau dispositif et d'un protocole expérimental a permis de corroborer l'existence d’une conductivité latérale des charges, souvent négligée dans les modèles physiques et numériques. Les études paramétriques, révélant l’influence de l’énergie et le flux des électrons incidents, ont permis de brosser un portrait des processus mis en jeu pour le transport (par saut ou par piégeage/dépiégeage) de charges en surface. A la lumière de cette étude, une conductivité équivalente est extraite, assimilant le matériau à un système prenant en compte les mécanismes de transport volumique et surfacique. L'analyse des évolutions non-monotones de potentiel mesurées sur les polymères spatiaux en condition spatiale a permis de révéler une dépendance de la conductivité volumique induite sous irradiation avec la dose reçue. L'étude paramétrique réalisée sur les mécanismes de transport en volume révèle une influence minoritaire du déplacement du barycentre de charges et du vieillissement physicochimique. Un modèle «0D» à un seul niveau de pièges, prenant en compte les mécanismes de piégeage/dépiégeage et recombinaison entre les porteurs de charges, a été développé. Ce modèle simplifié permet de reproduire qualitativement les évolutions de potentiel expérimentales en fonction du débit de dose et lors d'irradiations successives. / Charging behaviours of space dielectric materials, under electron beam irradiation, is of special interest for future spacecraft needs, since this mechanism could induce electrostatic discharges and consequently damages on the sensitive systems on board. In order to assess the risks of charging and discharging, this work aims at understanding the overall charge transport mechanisms and predicting the electrical behaviour of the insulator materials, especially Teflon® FEP and Kapton® HN. For an optimized prediction, the first part of our work is thus to check whether lateral conduction process can take place in the overall charge transport mechanism. Through the definition of a new experimental set-up and protocol, we have been able to discriminate between lateral and bulk conductivity and to reveal the presence of lateral conductivity that is enhanced by radiation ionization processes. We have been able to demonstrate as well that lateral intrinsic conductivity is enhanced with the increase current density and when approaching the sample surface. The second part of our work deals with the characterization of the electrical charging behaviour of Teflon® FEP under multi-energetic electron beam irradiation and the modelling of the overall bulk charge transport mechanisms. An experimental study on charge potential evolution as a function of electron spectrum, electric field, relaxation time, dose and dose rate, was performed. A numerical model has been developed to describe the effect of the different abovementioned mechanisms on the evolution of the surface potential. This model agrees correctly with the experimental phenomenology at qualitative level and therefore allows understanding the physical mechanisms steering charge transport in Teflon® and Kapton®.