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Study and Development of Nonwovens made of Electrospun Composite Nanofibers / Etude et développement de non-tissés fait en nanofibres composites obtenues par électrofilageAlmuhamed, Sliman 14 December 2015 (has links)
L’électrofilage est actuellement la méthode la plus utilisée pour la production de nanofibres grâce à sa simplicité, sa reproductibilité et la possibilité d’être industrialisée. Grâce à leurs propriétés particulières telles qu’un grand rapport surface-volume, une porosité inter-fibre élevée et une grande capacité d’adsorption, les nanofibres électrofilées sont de bons candidats pour de nombreuses applications telles que la filtration, les masques respiratoires, les matériaux composites, etc. Cependant, certaines applications particulières, telles que les capteurs, les systèmes d'administration contrôlée de médicaments ou les super condensateurs, exigent que les nanofibres doivent présenter des propriétés complémentaires telles que la conductivité électrique, la porosité de surface de nanofibres, l’hydrophobicité, ou d’autres propriétés particulières. Certains nanomatériaux comme les nanotubes de carbone, la silice mésoporeuse ordonnée, les argiles, ont des propriétés particulières comme la conductivité électriques élevée des nanotubes de carbone, la porosité des matériaux de silice mésoporeuse ordonnée ou de l’argile. Ces propriétés des nanomatériaux peuvent être les fonctions complémentaires cherchées. Dans notre étude, des non-tissés composés de nanofibres de polyacrylonitrile chargées par nanotubes de carbone à multi-parois (MWNT), de la montmorillonite sodique (MMT-Na) ou de la silice mésoporeuse ordonnée (de type SBA-15), sont produits par électrofilage. Les résultats montrent que l’insertion de MWNT rend le non-tissé conducteur en augmentant la conductivité électrique volumique par six ordres de grandeur (de ~ 2×10-12 à ~ 3×10-6 S/m) avec un très faible seuil de percolation de 0.5 % massique. Lorsque le non-tissé est soumis à une compression, la conductivité électrique volumique augmente en augmentant la pression (jusqu’à ~ 2 kPa). Ces non-tissés conducteurs sont très intéressants pour le développement des capteurs à faible amplitude. Les résultats montrent aussi que l’accessibilité des pores des particules inorganiques (c’est-à-dire, les mésopores de SBA-15 et l’espace interfoliaire de MMT-Na) insérées dans la structure nano fibreuse est encore possible. Il a été trouvé que plus de 50% des mésopores de SBA-15 insérées sont encore accessibles quelles que soit les conditions de l’électrofilage et la fraction massique de SBA-15. En outre, l’insertion de ces particules inorganiques apporte plus de stabilité thermique aux nanofibres composites. / Electrospinning is the most common method for the production of nanofibres due to its simplicity, repeatability, and the ability to be scaled up. Owing to their advanced properties like the high surface-to-volume ratio, high interfibrous porosity, high adsorption capacity, etc. electrospun nanofibers are good candidates for many applications such as filtration, respiratory masks, composite materials and others. However, some specific applications including sensors, controlled drug delivery systems, supercapacitors, etc. still require complimentary functions that do not exist in pristine nanofibers in their basic structure like the electrical conductivity, surface porosity of the nanofibers, hydrophobicity, and others.Nanomaterials like carbon nanotubes, ordered mesoporous silica, layered silicate, etc. are characterized by particular properties like the high electrical conductivity of carbon nanotubes, the porosity of ordered mesoporous silica or layered silicate. These particular properties of nanomaterials can fulfill of the targeted functions.In our study, nonwovens made from nanofibers of polyacrylonitrile incorporated with multiwalled carbon nanotubes (MWNT), layered silicate type Na-montmorillonite (Na-MMT) or ordered mesoporous silica type SBA-15 are successfully produced by electrospinning.Results reveal that the incorporation of MWNT altered the electrical state of the nonwoven from insolent to conductor where the volume electrical conductivity increased by six order of magnitude (from ~ 2×10-12 to ~ 3×10-6 S/m) with a very low percolation threshold of about 0.5 wt%. The application of mechanical pressure to the conductive nonwoven causes an increase in the volume electrical conductivity with the increase of the applied pressure (up to ~ 2 kPa). Such conductive nonwoven is very interesting for the development of sensor with low amplitude.Results also show that accessibility of the pores of the inorganic particles (i.e. mesopores of SBA-15 and interlayer space of Na-MMT) incorporated into the nanofibers is still possible. It is found that at least 50% of SBA-15 mesopores are still accessible whatever is the electrospinning conditions and SBA-15 mass fraction. In addition, the incorporation of the studied inorganic particles yields higher thermal stability for the composite nanofibers.
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Obtenção de filme adsorvente de celulose/SBA-15 para limpeza de superfícies policromadas em obras de arte / Achievement of cellulose/SBA-15 adsorbent film for cleaning polychrome surfaces in works of artRizzo, Marcia de Mathias 11 June 2015 (has links)
O verniz acrílico Paraloid B72TM é um termoplástico que atua como um bom adesivo formando filmes claros. Tem sido usado em conservação e restauração de bens culturais desde os anos 50. Por apresentar Tg próximo a 40°C, no Brasil, algumas substâncias podem ficar adsorvidas à superfície de camadas pictóricas envernizadas. Nesse caso, a limpeza tradicional (palito com algodão e solventes) pode acarretar danos (penetração do solvente, abrasão, etc.) à obra de arte. A limpeza por métodos aquosos (géis e emulsões) pode deixar resíduos que interagem com os materiais originais. Por outro lado, a utilização de nano-géis magnéticos é bastante restrita e de difícil acesso. Esse trabalho tem por objetivo o desenvolvimento de filmes adsorventes de celulose/SBA-15 para retirada do verniz Paraloid B72TM, onde se fizer necessário. Esses filmes foram empregados sobre miméticos (pinturas originais de diferentes técnicas e obras confeccionadas para estudo envernizadas com Paraloid B72TM) para verificação de sua eficácia. As matérias primas, os miméticos e os filmes adsorventes, antes e após a aplicação, foram caracterizadas por técnicas físico-química e analíticas [análise térmica (TG/DTG e DTA); espectroscopia no infravermelho (FTIR); microscopia eletrônica de varredura (MEV); microscopia eletrônica de transmissão (MET); espectroscopia de fluorescência de raios X (XRF), microscopia digital de superfície e estereoscopia]. A microscopia digital de superfície e a estereoscopia foram usadas para inspeção do micro morfologia da superfície e possibilitaram identificar a presença de partículas adsorvidas na superfície das obras. A MEV, a MET permitiram observar a micromorfologia das superfícies e a FTIR caracterizar as matérias primas e os filmes adsorventes. O comportamento térmico das matérias primas e dos filmes adsorventes, antes e após a aplicação, foi avaliado por TG/DTG e DTA. A avaliação dos miméticos e dos filmes de adsorção, antes e depois da aplicação, por XRF evidenciou que não houve danos aos miméticos. O filme de celulose/SBA-15 como adsorvedor da resina acrílica na limpeza de superfícies policromadas em obras de arte, por meio de um solvente, se mostrou eficaz. Esse método é alternativo e não pretende substituir qualquer outro já existente. Visto que, em restauração de obras de arte cada caso é especifico e nada substitui o conhecimento, discernimento e destreza do restaurador. / The acrylic varnish Paraloid B72TM is a thermoplastic, which acts as an adhesive forming clear films. It has been used in conservation and restoration of cultural property since the 50ths. By presenting Tg near 40°C, some substances can become adsorbed on the surface of varnished paintng layers, for example in Brazil. In this case, the traditional cleaning (stick with cotton and solvents) can cause damage (penetration of the solvent, abrasion,...) to the artwork. The cleaning of aqueous methods (gels and emulsions) can leave residues that interact with the original materials. Already, the use of magnetic nano-gels is restricted and difficult to access. This paper aims at developing cellulose/SBA-15 adsorbent films for withdrawal of Paraloid B72TM varnish, where it becomes necessary. These films were employed on mimetic (original paintings of different techniques and works made for study varnished with Paraloid B72TM) to verify its effectiveness. The raw materials, adsorbents and mimetic films before and after application were characterized by physico-chemical and analytical techniques [thermal analysis (TG/DTG and DTA); infrared spectroscopy (FTIR); scanning electron microscopy (SEM); transmited electron microscopy (TEM); fluorescent X-ray spectroscopy (XRF), digital microscopy and surface stereoscopic]. The digital microscopy and surface stereoscopy were used to inspect the surface micro morphology and it was possible to identify the presence of particles adsorbed on the surface of the artwork. The SEM, the TEM showed the micro morphology of the surfaces and FTIR characterized the raw materials and adsorbents films. The thermal behavior of materials and adsorbents films before and after application was evaluated by TG/DTG and DTA. Assessment of adsorption and mimetics films before and after application by XRF showed that there was no damage to the mimetic. The cellulose/SBA-15 film as adsorbent in the acrylic resin in polychrome surface cleaning artwork by means of a solvent, is effective. This method is alternative and not intended to replace any existing one. Since, in restoration of works of art each case is specific and nothing replaces the knowledge, insight and conservator dexterity.
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Obtenção de filme adsorvente de celulose/SBA-15 para limpeza de superfícies policromadas em obras de arte / Achievement of cellulose/SBA-15 adsorbent film for cleaning polychrome surfaces in works of artMarcia de Mathias Rizzo 11 June 2015 (has links)
O verniz acrílico Paraloid B72TM é um termoplástico que atua como um bom adesivo formando filmes claros. Tem sido usado em conservação e restauração de bens culturais desde os anos 50. Por apresentar Tg próximo a 40°C, no Brasil, algumas substâncias podem ficar adsorvidas à superfície de camadas pictóricas envernizadas. Nesse caso, a limpeza tradicional (palito com algodão e solventes) pode acarretar danos (penetração do solvente, abrasão, etc.) à obra de arte. A limpeza por métodos aquosos (géis e emulsões) pode deixar resíduos que interagem com os materiais originais. Por outro lado, a utilização de nano-géis magnéticos é bastante restrita e de difícil acesso. Esse trabalho tem por objetivo o desenvolvimento de filmes adsorventes de celulose/SBA-15 para retirada do verniz Paraloid B72TM, onde se fizer necessário. Esses filmes foram empregados sobre miméticos (pinturas originais de diferentes técnicas e obras confeccionadas para estudo envernizadas com Paraloid B72TM) para verificação de sua eficácia. As matérias primas, os miméticos e os filmes adsorventes, antes e após a aplicação, foram caracterizadas por técnicas físico-química e analíticas [análise térmica (TG/DTG e DTA); espectroscopia no infravermelho (FTIR); microscopia eletrônica de varredura (MEV); microscopia eletrônica de transmissão (MET); espectroscopia de fluorescência de raios X (XRF), microscopia digital de superfície e estereoscopia]. A microscopia digital de superfície e a estereoscopia foram usadas para inspeção do micro morfologia da superfície e possibilitaram identificar a presença de partículas adsorvidas na superfície das obras. A MEV, a MET permitiram observar a micromorfologia das superfícies e a FTIR caracterizar as matérias primas e os filmes adsorventes. O comportamento térmico das matérias primas e dos filmes adsorventes, antes e após a aplicação, foi avaliado por TG/DTG e DTA. A avaliação dos miméticos e dos filmes de adsorção, antes e depois da aplicação, por XRF evidenciou que não houve danos aos miméticos. O filme de celulose/SBA-15 como adsorvedor da resina acrílica na limpeza de superfícies policromadas em obras de arte, por meio de um solvente, se mostrou eficaz. Esse método é alternativo e não pretende substituir qualquer outro já existente. Visto que, em restauração de obras de arte cada caso é especifico e nada substitui o conhecimento, discernimento e destreza do restaurador. / The acrylic varnish Paraloid B72TM is a thermoplastic, which acts as an adhesive forming clear films. It has been used in conservation and restoration of cultural property since the 50ths. By presenting Tg near 40°C, some substances can become adsorbed on the surface of varnished paintng layers, for example in Brazil. In this case, the traditional cleaning (stick with cotton and solvents) can cause damage (penetration of the solvent, abrasion,...) to the artwork. The cleaning of aqueous methods (gels and emulsions) can leave residues that interact with the original materials. Already, the use of magnetic nano-gels is restricted and difficult to access. This paper aims at developing cellulose/SBA-15 adsorbent films for withdrawal of Paraloid B72TM varnish, where it becomes necessary. These films were employed on mimetic (original paintings of different techniques and works made for study varnished with Paraloid B72TM) to verify its effectiveness. The raw materials, adsorbents and mimetic films before and after application were characterized by physico-chemical and analytical techniques [thermal analysis (TG/DTG and DTA); infrared spectroscopy (FTIR); scanning electron microscopy (SEM); transmited electron microscopy (TEM); fluorescent X-ray spectroscopy (XRF), digital microscopy and surface stereoscopic]. The digital microscopy and surface stereoscopy were used to inspect the surface micro morphology and it was possible to identify the presence of particles adsorbed on the surface of the artwork. The SEM, the TEM showed the micro morphology of the surfaces and FTIR characterized the raw materials and adsorbents films. The thermal behavior of materials and adsorbents films before and after application was evaluated by TG/DTG and DTA. Assessment of adsorption and mimetics films before and after application by XRF showed that there was no damage to the mimetic. The cellulose/SBA-15 film as adsorbent in the acrylic resin in polychrome surface cleaning artwork by means of a solvent, is effective. This method is alternative and not intended to replace any existing one. Since, in restoration of works of art each case is specific and nothing replaces the knowledge, insight and conservator dexterity.
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