Les dispersions de nanocomposite à base aqueuse sont produites pour des applications diverses telles que les adhésifs, les revêtements et plus récemment les encres. Ce projet consiste à réaliser des encres conductrices nanocomposites comprenant des particules de polymère (latex) à basse température de transition vitreuse, Tg, pour la formation de films à température ambiante, et des plaquettes de graphène, en raison de leurs excellentes propriétés conductrices. Les charges conductrices, appelées multi-feuillets de graphène, sont réalisées par broyage en voie aqueuse de graphite (1-10 µm) stabilisées par différents tensio-actifs et/ou stabilisants. Cette méthode sans solvant et à bas coût permet de produire des suspensions de multi-feuillets (1-10 feuillets) de graphène. Les particules de polymères utilisées sont synthétisées par polymérisation en émulsion de monomères acrylates. Dans un second temps, des mélanges physiques de suspensions de graphène et de latex acrylates ont permis d’obtenir des encres nanocomposites. L’ajout de graphène permet l’obtention d’un seuil de percolation à bas taux de charge et une nette amélioration des propriétés électriques et du renfort. Le diamètre des billes de latex a une influence importante sur ces propriétés et a également été étudié. Afin d’augmenter la stabilité des suspensions et les interactions graphène/latex, des nanocomposites structurés ont été synthétisés par polymérisation in situ en émulsion, miniemulsion ou dispersion en présence de graphène. Les excellentes propriétés électriques associées à leur flexibilité font de ces matériaux des candidats adaptés pour la réalisation d’encres conductrices pour impression sur textile. / Printed electronics, particularly on flexible and textile substrates, raised a strong interest during the past decades. This project presents a procedure that provides a complete and consistent candidate for conductive inks based on a graphene/polymer nanocomposite material. It consists in the synthesis of conductive inks nanocomposites comprising polymer particles (latex) with low glass transition temperature, Tg, and graphene platelets, for the conductive properties. The conductive particles, named Nanosize Multilayered Graphene (NMG), are prepared by wet grinding delamination of micro-graphite suspensions stabilized by various surfactants and/or polymeric stabilizers. This solvent-free procedure allows the formation of NMG suspensions with low thickness (1-10 sheets). Polymer particles are synthetized by surfactant-free emulsion polymerization with acrylates monomers.Physical blending of latex particles and NMG platelets are performed to obtain conductive nanocomposites inks. Adding NMG induce a low percolation threshold and a sharp increase of the electrical and mechanical properties of the nanocomposites. Moreover, the polymer particles diameters have an impact on these properties.To increase the formation of a well-defined cellular microstructure, the nanocomposites are also synthetized by in situ polymerization in presence of NMG platelets, using emulsion, miniemulsion or dispersion polymerization. The excellent electrical properties of these nanocomposites associated to their flexibility make these materials suitable candidates for the production of conductive inks for textile printing applications.

Le domaine de nanocomposites polymères conducteurs a fait l’objet de nombreux travaux et recherches, vu que ces matériaux présentent un fort potentiel pour de nombreuses applications concernant différents secteurs. Toutefois, malgré les progrès et les résultats obtenus pour l’instant, les performances de ce type des matériaux restent insuffisantes pour certaines applications qui peuvent requérir l’association de diverses propriétés (électriques, thermiques, blindage électromagnétique…). Dans cette thèse, on détaille l’élaboration et la caractérisation de nanocomposites polymères conducteurs. Deux types de nanocharges conductrices (nanotubes de carbone (MWCNTs) et nanoparticules d’argent (Ag-NPs)) ont été dispersées soit dans un polymère thermoplastique (polyéthylène PE), soit dans une matrice thermodurcissable (résine époxy amine). Les nanocomposites polymères conducteurs obtenus ont présenté de bonnes propriétés électriques et thermiques ainsi qu’une bonne tenue mécanique favorisée par des taux de charges relativement faibles. La thèse a non seulement étudié des propriétés fondamentales d’un point de vue expérimental mais aussi plus théorique avec de la modélisation. Entre autres, on a pu analyser les mécanismes de conduction à très basses température dans ce type de composites. Les propriétés en termes de conductivité thermique se sont révélées cohérentes avec celles obtenues en conductivité électrique. Des propriétés de blindage électromagnétique de nos composites à base de PE ont été mis en évidence par résonance magnétique nucléaire (RMN). / Conductive polymer nanocomposites have been the object of intense researches and investigations recently. In fact, these materials have shown a great potential to be useful for many applications including different sectors. However, despite the promising results reported at the moment in this area, there is still a lack in the performance which can be improved by synchronization of their properties. In this PhD work, we present the preparation and full characterization of conductive polymer nanocomposites. Two kinds of conductive nanofillers (carbon nanotubes (MWCNTs) and silver nanoparticles (Ag-NPs)) have been dispersed either in a thermoplastic polymer (polyethylene PE), or in a thermoset matrix (epoxy amine). The conductive polymer nanocomposites obtained exhibit good electrical and/or thermal properties with conserving the mechanical properties ensured by low fillers fraction. The study was not only based on experimental characterizations but also on modulation to analyze the charge carrier transport at very low temperature in these systems to provide successful understanding to some basic properties which are still actually not fully investigated. Electrical properties are in good agreement with thermal properties. Electromagnetic shielding of our PE based nanocomposites have been studied by Nuclear Magnetic Resonance (NMR).

Initial research in the field of organic electronics focused primarily on the improvements in material performance. Significant progress has been achieved in the case of organic field effect transistors, where reported mobility values are now over 5 orders of magnitude higher than those of early devices. As a consequence, the use of organic transistors is now being considered for real-world applications in the form of integrated logic circuits. This in turn presents many new challenges, as the logic circuit requirements are more demanding on the transistor characteristics and corresponding fabrication processes. This thesis investigates the feasibility of organic technology for its potential use in future low-cost, high-volume electronic applications. The research objectives were accomplished by practical evaluation of an organic logic circuit fabrication process. First, recent advances in the fabrication of organic circuits in terms of transistor structure, material usage and fabrication techniques are reviewed. Next, a lithographic logic circuit fabrication process using PVP gate dielectric and TIPS-pentacene organic semiconductor adapted from state of the art fabrication process is presented. The logic circuit design decisions and the methodology for the fabrication process are thoroughly documented. Using this process, zero-Vgs and diode-load inverter circuits were successfully fabricated. However, the process is in need of further refinement for more complex circuit designs, as the fabrication of a comparator circuit consisting of 11 transistors was unsuccessful. Two optimisation techniques that are compatible with the logic circuit fabrication process were also explored in this work. To improve the capacitive coupling of the dielectric layer, the use of a polymer nanocomposite dielectric was investigated. The nanocomposite is prepared by blending PVP solution with a high-k inorganic nanoparticle filler, barium strontium titanate. Using the nanocomposite dielectric, both single transistors and integrated logic circuits were successfully fabricated. This is the first report on the use of PVP and barium strontium titanate nanocomposite dielectric with a lithographic based logic circuit fabrication process. The use of PFBT modified Au contacts for the fabrication process was investigated to improve theperformance of the contact electrode layer. Using PFBT, mobility increased by one order of magnitude over untreated Au electrodes for the PVP and TIPS-pentacene transistors.

Este trabalho teve como objetivo estudar e caracterizar filmes de nanocompósitos de polipirrol dopado com índigo carmim e dodecilsulfato combinados com nanopartículas de ouro para aplicação como biossensores eletroquímicos de pesticida. Primeiramente sintetizou-se três filmes a 10 e 25 ºC por voltametria cíclica: polipirrol dopado com índigo carmim (PPi-IC), polipirrol dopado com índigo carmim contendo nanopartículas de ouro (PPi-IC-NPAu) e polipirrol dopado com índigo carmim e dodecilsulfato de sódio, contendo nanopartículas de ouro (PPi-IC-DS-NPAu). Nesses filmes foram realizadas caracterizações estruturais, morfológicas, ópticas e eletroquímicas, utilizando espectroscopia no infravermelho, espectroscopia Raman, microscopia eletrônica de varredura, espectroscopia UV-VIS-NIR e voltametria cíclica. Os filmes sintetizados a 10 ºC foram modificados com a enzima acetilcolinesterase (AChE), sendo posteriormente caracterizados por microscopia eletrônica de varredura, espectroscopia Raman e voltametria cíclica. Os resultados obtidos mostraram que a interação da enzima com os filmes de polipirrol é dependente de sua composição. A presença de DS não favoreceu a sua imobilização, sendo assim, os filmes de PPi-IC e PPi-IC-NPAu foram os materiais mais adequados para a imobilização física da AChE, sendo capazes de detectar o pesticida metil paration (MP) através da porcentagem de pesticida inibido pela ação da AChE em relação ao cloreto de acetiltiocolina (ATCl). Essa detecção foi realizada por voltametria cíclica, onde a resposta do biossensor é medida a partir da diminuição da corrente produzida. Isso ocorre porque o MP se encontra em contato com a AChE e inibe a ação da mesma, impedindo a hidrólise da ATCl, o que faz diminuir a corrente, pois não há produção de tiocolina, que é produto da hidrólise e uma espécie eletroativa. Os filmes apresentaram sensibilidades (% de inibição por mmol L-1 de pesticida) de 1,9×106 (R2 0,976) e 2,7×106 (R2 0,964) e limites de detecção de 4,15 e 14,8 ng L-1, para PPi-IC-AChE e PPi-IC-NPAu-AChE respectivamente. / The goal of this work was to study and characterize nanocomposite films of gold nanoparticles with indigo carmine and dodecylsulfate doped polypyrrole for application as electrochemical biosensor for pesticide. Initially, three films were synthesized by cyclic voltammetry at 10 and 25 ºC: polypyrrole doped with indigo carmine (PPy-IC), polypyrrole doped with indigo carmine containing gold nanoparticles (PPy-IC-AuNP) and polypyrrole doped with indigo carmine and sodium dodecylsulfate containing gold nanoparticles (PPy-IC-DS-AuNP). These films were studied by structural, morphological, optical and electrochemical characterization, using infrared spectroscopy, Raman spectroscopy, scanning electron microscopy, UV-VIS-NIR spectroscopy and cyclic voltammetry. The films synthesized at 10 ºC were modified with acetylcholinesterase (AChE) enzyme; followed by characterization with scanning electron microscopy, Raman spectroscopy and cyclic voltammetry The results showed a preferential immobilization of the enzymes on films without DS, therefore, PPy-IC and PPy-IC-AuNP were the most suitable materials for the physical immobilization of AChE and for detection of methyl parathion (MP) pesticide through the percentage of pesticide inhibited by the action of AChE on acetylthiocholine chloride (ATCl). This detection was carried out by cyclic voltammetry, where the biosensor response is measured as a decrease of the produced current. The decrease in current occurs because MP reaches the AChE, inhibiting the action of the enzyme, avoiding the hydrolysis of ATCl, leading to the decrease of current as no thiocholine (an electroactive specie, product of the hydrolysis) is produced. The films presented sensitivities (inhibition percentage per mmol L-1) of 1.9×106 (R2 0.976) and 2.7×106 (R2 0.964) and detection limits of 4.15 and 14.8 ng L-1 for PPy-IC-AChE and PPy-IC-AuNP-AChE respectively.

Orientador: Fauze Ahmad Aouada / Resumo: Neste trabalho, primeiramente foram desenvolvidos hidrogéis nanocompósitos baseados em poli(ácido metacrílico) (PMAA) e nanoargilas cloisita-Na+, laponitas RD (Lpt RD) e RDS (Lpt RDS) por meio de polimerização via radical livre. A formação do nanocompósito e o grau de dispersão das nanoargilas junto a matriz polimérica foram investigados por análise de FTIR, MEV e DRX. A presença do argilomineral se apresentou um fator importante no que diz respeito ao aumento da capacidade de absorver água (Q) dos hidrogéis, atingindo um máximo em 5% de incorporação das Lpts no PMAA, além de uma melhora na estabilidade térmica dos nanocompósitos comprovada por TG. Assim como as nanocargas, o pH do meio também é um fator determinante para o controle do intumescimento. Pois, os grupos carboxílicos do PMAA sofrem ionização dependendo do pH da solução, aumentando assim o intumescimento do hidrogel. Segundo, foi realizado um estudo relativo à eficiência da adsorção pelos nanocompósitos (nanoargilas Lpt RD, Lpt RDS e cloisita-Na+) do herbicida paraquat (PQ) e sua posterior liberação em solução aquosa. Mais uma vez a presença do argilomineral se mostrou relevante, aumentando para 100% de eficiência no carregamento para nanocompósitos constituídos por 20% de nanoargilas. As adsorções em todas as formulações dos nanocompósitos se ajustaram à isoterma de Langmuir. Enquanto o modelo de isoterma de Freundlich foi o melhor modelo para a matriz sem nanoargila. Todas as isotermas apresentaram perfil de ads... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: In this work, initially, nanocomposite hydrogels based on poly(methacrylic acid) (PMAA), closite-Na+, laponite RD (Lpt RD) and laponite RDS (Lpt RDS) nanoclays were synthesized from free radical polymerization. The formation of the nanocomposite and the degree of dispersion of the nanoclays into polymeric matrices were investigated by FTIR, SEM, and XRD techniques. The presence of the clay mineral was a significant factor because it increased the capacity of water absorption (SD) of the hydrogels, reaching a maximum of 5% of Lpts into PMAA. Besides, the thermal stability of the nanocomposites, confirmed by TG, was increased by clay presence. As the nanofillers, the pH of the environment is also a determinant factor for the control of swelling. Because the carboxyl groups of the PMAA undergo ionization depending on the pH of the solution, increasing the swelling of the hydrogel. Then, a study was carried out on the adsorption efficiency of the herbicide paraquat (PQ) using hydrogel nanocomposites (with Lpt RD, Lpt RDS, and cloisite-Na+ nanoclays) as adsorbent materials. After, its release properties were investigated in aqueous solution. The presence of nanoclay was again relevant, increasing to 100% its loading efficiency for nanocomposites made up of 20% nanoclays. Adsorption in all nanocomposite formulations fitted the Langmuir isotherm. Already, the paraquat sorption results followed the Freundlich isotherm model. All isotherms had favorable adsorption profiles, and it pre... (Complete abstract click electronic access below) / Doutor

Orientador: José Antônio Malmonge / Resumo: O uso de nanocargas de carbono tais como nanotubos de carbono e nanolâminas de grafite (NLG), e/ou polímeros condutores em uma matriz polimérica, tem atraído à atenção de inúmeros pesquisadores que buscam sintetizar elastômeros eletricamente condutivos com amplo potencial aplicacional como dissipadores eletrostáticos, blindagem eletromagnética, sensores piezorresistivos, etc. Nesse trabalho, foram obtidos: (1) nanocompósitos de polianilina (PAni)/NLG com razão mássica anilina (An)/NLG entre 0 e 250%, utilizando ácido clorídrico como dopante (nanocompósitos PHN), e com razão mássica anilina An/NLG entre 0 e 950%, utilizando ácido dodecilbenzeno sulfônico (DBSA) como dopante (nanocompósitos PDN); (2) Blendas de borracha natural (BN)/PAni com diferentes razões BN/An, utilizando BN in natura (blendas BNP) e borracha pré-vulcanizada (BV), blendas BVP; e (3) Nanocompósitos de BN/PAni-NLG (BNP/NLG) e BV/PAni-NLG (BVP/NLG) com diferentes razões BN/An e 15% de NLG em relação a An (relação m/m). Em todas as sínteses a polimerização da anilina foi realizada in situ. Nos nanocompósitos de PAni/NLG a polimerização da PAni ocorreu sobre a superfície lisa das NLG sendo sua morfologia e grau de intercalação nas NLG influenciados pelo tipo de dopante utilizado. A condutividade elétrica máxima obtida para os nanocompósitos foi de 627 S.cm-1 e 582 S.cm-1 para nanocompósitos PHN contendo 200% de NLG e para nanocompósitos PDN contendo 600% de NLG, respectivamente. O aumento na estabilidade térmic... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The use of carbon nanofiller such as carbon nanotube and graphite nanosheet (GNS), and/or conductive polymers as filler to a polymer matrix, has attracted the attention of numerous researchers who seek to synthesize electrically conductive elastomers with broad application potential such as electrostatic dissipator, piezoresistive sensor and electromagnetic interference shielding . In this work were synthesized: (1) nanocomposites of polyaniline (PAni)/NLG with aniline (An)/NLG mass ratio between 0 and 250%, using hydrochloric acid as a dopant (PHN nanocomposites) and aniline An/NLG between 0 and 950%, using dodecylbenzene sulfonic acid (DBSA) as a dopant (PDN nanocomposites); (2) Natural rubber blends (BN)/PAni with different BN/An mass ratio, using BN in nature (BNP blends) and pre-vulcanized rubber BV, BVP blends; and (3) BN/PAni-NLG (BNP/NLG) and BV/PAni-NLG (BVP/NLG) nanocomposites with different BN/An mass ratios and 15% NLG with respect to An (m/m ratio). In all syntheses the polymerization of aniline was performed in situ. In the nanocomposites PAni/GNS the polymerization of PAni occurred on the GNS surface and their morphology and degree of intercalation in NLGs were influenced by the type of dopant. The higher electrical conductivity obtained for PHN and PDN composites were 627 S.cm-1 and 582 S.cm-1, respectively. The increase in the thermal stability of PAni in PAni/NLG nanocomposites was attributed to the intercalation of PAni among GNS and barrier properties pres... (Complete abstract click electronic access below) / Doutor

This thesis focused on the synthesis and characterization of novel functional materials based on cellulose and graphene derivatives. Cellulose/GO hydrogels were produced as the starting material by dissolving cellulose and dispersing GO in NaOH/urea solution. This method is considered as an efficient, simple, environmentally friendly, and low-cost method. Novel functionalities, such as sensing, catalytic and EMI shielding properties have been “built-in” to cellulose/GO hydrogels. Cellulose/rGO composite films and aerogels were successfully fabricated by dissolving cellulose and dispersing GO in NaOH/urea solution, followed by the chemical reduction with vitamin C as the reducing agent. The cellulose/rGO films and aerogels with various rGO contents were prepared by air-drying and freeze-drying of the prepared cellulose/rGO composite hydrogels. The resultant cellulose/rGO composites prepared by this efficient and simple method show high resistance sensitivity to environmental stimuli like temperature, humidity, liquids, vapours, and strain stress. Thus, the cellulose/rGO films can be applied in detecting human motions and human breath cycles. Liquid temperature, liquid type, and ion concentration also be determined by our cellulose/rGO films. Moreover, the composite aerogels are fast responding and extremely sensitive sensors for vapour detection and testing with good repeatability. It was also revealed that discriminating and quantitative responses can be obtained when analyzing various vapours and different vapour concentrations. For methanol vapour, the aerogel shows linear response to the vapour concentration. Thus cellulose/rGO composite aerogel can be used to quantify methanol vapour concentrations. The efficient, scalable, and environmentally friendly preparation of novel and high-performance of vapour sensing materials with well reproducibility is promising to achieve practical vapour sensing applications. We have successfully presented an effective, facial, simple, and scalable method to form Fe3O4 nanoparticles onto cellulose/GO hydrogels. XRD, FTIR, XPS and TEM indicated that Fe3O4 nanoparticles with good dispersion and uniform size are successfully coated on cellulose matrix and GO sheets. This material was tested as catalyst for the cleaning of dye-contaminated water by oxidation with H2O2.The optimized experiment conditions for AO7 degradation are: [AO7] = 0.1 mM, T = 298 K, [H2O2] = 22 mM, and pH = 3. Under these conditions, the resulting hydrogels display 97 % AO7 removal within 120 min and retained strong degradation performance after twenty consecutive cycles of reuse. Especially, the detailed XPS analysis of cellulose/GO/Fe3O4 and cellulose/Fe3O4 composites indicated that the cellulose/GO/Fe3O4 hydrogel retain its high degradation activity by keeping the ratio of Fe3+/Fe2+ at 2 during the 20 heterogeneous Fenton-like reaction cycles. Therefore, the cellulose/GO/Fe3O4 hydrogel is recommended to test the treatment of other dye-contaminated wastewaters. Cellulose/rGO/Fe3O4 films and aerogels were successfully fabricated by the in-situ grown of Fe3O4 nanoparticles within a cellulose matrix containing rGO sheets. Cellulose/rGO (8 wt.%)/Fe3O4 aerogels with the thickness of 0.5 mm exhibited high EMI shielding performance with the EMI SE value at 32.4-40.1 dB in the 8.2-12.4 GHz frequency range. High loading of rGO and large thickness of the composites are beneficial for the excellent EMI shielding performance of our aerogels. The lightweight aerogel is suitable for the practical application as EMI shielding materials such as spacecraft, aircraft, energy conversion application, and energy storage.

京都大学 / 0048 / 新制・課程博士 / 博士(農学) / 甲第22081号 / 農博第2373号 / 新制||農||1073(附属図書館) / 学位論文||R1||N5235(農学部図書室) / 京都大学大学院農学研究科森林科学専攻 / (主査)教授 矢野 浩之, 教授 和田 昌久, 教授 辻井 敬亘 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第22114号 / 理博第4541号 / 新制||理||1652(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 寺西 利治, 教授 島川 祐一, 教授 若宮 淳志 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

Human knee kinematics, especially during gait, are an important analysis tool. The current "gold standard" for kinematics measurement is a multi-camera, marker-based motion capture system with 3D position tracking. These systems are accurate but expensive and their use is limited to a confined laboratory environment. High deflection strain gauges (HDSG) are a novel class of sensors that have the potential to measure kinematics and can be inexpensive, low profile, and are not limited to measurements within a calibrated volume. However, many HDSG sensors can have a non-linear and non-monotonic response. This thesis explores using a nanocomposite HDSG sensor system for measuring knee kinematics in walking gait and overcoming the non-monotonic sensor response found in HDSGs through advanced modeling techniques. Nanocomposite HDSG sensors were placed across the knee joint in nine subjects during walking gait at three speeds and three inclines. The piezoresistive response of the sensors was obtained by including the sensors in a simple electrical circuit and recorded using a low-cost microcontroller. The voltage response from the system was used in four models. The first two models included a physics-based log-normal model and statistical functional data analysis model that estimated continuous knee angles. The third model was a discrete linear regression model that estimated the inflection points on the knee flexion/extension cycle. Finally, a machine learning approach helped to predict subject speed and incline of the walking surface. The models showed the sensor has the capability to provide knee kinematic data to a degree of accuracy comparable to similar kinematic sensors. The log-normal model had a 0.45 r-squared and was unsuitable as a stand-alone continuous angle predictor. After running a 10-fold cross validation the functional data analysis (FDA) model had an overall RMSE of 3.4° and could be used to predict the entire knee flexion/extension angle cycle. The discrete linear regression model predicted the inflection points on the knee kinematics graph during each gait cycle with an average RMSE of 1.92° for angle measures and 0.0332 seconds for time measures. In every estimate, the discrete linear regression model performed better than the FDA model at those points. The 10-fold cross validation of the machine learning approach using the discrete voltages could predict the categorical incline 90% of the time and the RMSE for the speed model was 0.23 MPH. The use of a HDSG as a knee kinematics sensor was shown as a viable alternative to existing motion capture technology. In future work, it is recommended that a calibration method be developed that would allow this sensor to be used independent of a motion capture system. With these advancements, this inexpensive and low profile HDSG will advance understanding of human gait and kinematics in a more affordable and scope enhancing way.