Abstract This work presents the results obtained in the production of poly (vinyl alcohol) (PVA) nanofibers with different concentrations of polypyrrole (PPy) doped with dodecylbenzene sulfonic acid (DBSA) - PPy.DBSA. The morphology of the nanofibers was studied by scanning electron microscopy (SEM) technique. The nanofibers were deposited on interdigitated electrodes (IDEs) for direct current electrical characterization (DC) and tested as ammonia gas sensors. The results showed a rapid detection of ammonia gas for higher concentrations of PPy.DBSA and for several alternating cycles in atmospheric N2.

A novel pressure sensing material composed of poly (butylene adipate-co-terephthalate) (PBAT) and montmorillonite-polypyrrole (Mt-PPy) was prepared using melt mixing and injection molding. The structure and properties of the PBAT/Mt-PPy composites were evaluated and compared with those of the PBAT/PPy blends. The PBAT/Mt-PPy displays a very sharp insulator-conductor transition and its percolation threshold was reached at 6.5 wt% of Mt-PPy, which was lower than that for PBAT/PPy (11.0 wt% of PPy). The transmission electron microscopy analysis shows that Mt-PPy displays a high aspect ratio and was better distributed and dispersed into PBAT compared to PPy. PBAT/Mt-PPy exhibits a decrease in the electrical resistivity with an applied compressive stress due to the formation of new conducting pathways. The electromechanical response was dependent on Mt-PPy and the maximum sensitivity was observed for the composite containing 10 wt% of Mt-PPy. In this system, the electrical resistivity drops from 9 x 106 to 2 x 106 Ω cm when a compressive stress of 0.25 MPa was applied. The electrical resistivity changes with applied compressive stress, the reproducibility and the reversibility makes PBAT/Mt-PPy a suitable material for the development of pressure sensors.

In this study, composites based on polyurethane (PU) derived from castor oil and montmorillonite/polypyrrole doped with dodecylbenzenesulfonic acid (MMt-PPy.DBSA) were developed. In order to investigate the potential use of these materials for electromagnetic shielding applications, the electrical and mechanical properties of PU/MMt-PPy.DBSA composites were determined and compared with composites containing neat PPy.DBSA. The electrical conductivity of PU/MMt-PPy.DBSA composites was found to be higher than those for PU/PPy.DBSA with a similar filler content. Additionally, with a higher conductive additive content, significant increases in the tensile stress (σ) and elastic modulus (E) were observed, suggesting that MMt-PPy.DBSA acts as reinforcing agent for the PU matrix. The electromagnetic interference shielding effectiveness (EMI SE) of composites is mainly dependent on the morphology and filler content. The PU/MMt-PPy.DBSA composite containing 25 wt % of MMt-PPy.DBSA showed a maximum EMI SE of -21 dB, which is similar to the value required for commercial applications (-20 dB). The results revealed that PU/MMt-PPy.DBSA composites are promising materials for electromagnetic shielding applications.

RESUMO A Impressão 3D baseada em extrusão se popularizou muito nos últimos anos devido ao surgimento de projetos de código aberto e máquinas de baixo custo, que tornaram a tecnologia acessível a todos os níveis de usuários. Paralelamente, novos materiais, em geral filamentos termoplásticos, são inseridos no mercado para aplicação neste tipo de técnica de fabricação, tornando cada vez mais necessário o desenvolvimento de estudos de caraterização experimentais dos materiais para fornecer dados técnicos aos utilizadores. Neste trabalho estudou-se o poli(tereftalato de etileno glicol) (PETG), polímero de recente adoção neste contexto, comparando-o ao poli(ácido lático) (PLA), o mais popular no âmbito da tecnologia. Ambos os materiais foram analisados mecanicamente à tração, através de amostras fabricadas por Impressão 3D variando os ângulos de deposição do material extrudado. Para a mesma análise, visando comparação, foram construídas peças por moldagem por injeção. Os materiais em seu estado inicial filamentar foram avaliados termicamente por TGA e DSC, e quimicamente por FTIR. As duas últimas técnicas de caracterização também foram aplicadas aos polímeros após o processamento por injeção e impressão. Os resultados obtidos mostraram que as propriedades mecânicas à tração dos componentes impressos são fortemente influenciadas pela orientação dos filamentos depositados nas camadas e pela mesoestrutura das peças. O PLA dispõe de superioridade mecânica, maior tensão máxima e elevada rigidez em relação ao PETG, nas amostras injetadas e impressas. O PETG, por sua vez, demostrou ser um material mais resistente à degradação térmica, mais estável termicamente (por não apresentar alterações significativas em seu comportamento térmico após ser processado), e flexível, propriedade esta que o torna muito interessante para aplicações na Impressão 3D. Por fim, a estrutura química molecular dos polímeros foi semelhante à descrita em outros estudos da literatura e pouco alterada pelos processos de fabricação.

ABSTRACT The extrusion-based 3D printing has become popular in recent years due to the emergence of open source projects and low-cost machines that have made the technology accessible to all levels of users. In parallel, new materials, in general thermoplastic filaments, are inserted in the market for application in this type of manufacturing technique, making it increasingly necessary to develop experimental characterization studies to provide technical data to users. Thus, we sought to study poly(ethylene terephthalate glycol) (PETG), a polymer of recent adoption in this context, and compare it to poly(lactic acid) (PLA), the most popular one in this field. Both materials were mechanically analyzed by traction through samples made by 3D printing varying the angles of deposition of the extruded material. The same type of analysis was made using parts built by injection molding, for comparison purposes. The materials in their initial filamentary state were thermally evaluated by TGA and DSC, and chemically evaluated by FTIR. The last two characterization techniques were also applied to the polymers after the injection and 3D printing processing. The results showed that the tensile mechanical properties of the printed components are strongly influenced by the orientation of the filaments deposited in the layers and by the mesostructure of the parts. PLA has mechanical superiority, greater maximum tension and high rigidity, in relation to PETG, in the injected and printed samples. PETG, in turn, has shown to be more resistant to thermal degradation, more thermally stable (because it does not show significant changes in its thermal behavior after being processed), and more flexible, which is very interesting for 3D printing applications. Finally, the molecular chemical structure of both polymers was similar to that described in other studies found in the literature and was slightly altered by the manufacturing processes.

Nanocompósitos de montmorilonita/polipirrol (MMT/PPy) foram preparados a partir da polimerização in situ do pirrol na presença de argila, bentonita sódica natural, (MMT-Na+) em solução aquosa com ou sem surfactante aniônico, dodecil sulfato de sódio (SDS), utilizando-se o cloreto de ferro (III) hexahidratado (FeCl3.6H2O), como oxidante. A estrutura e propriedades dos nanocompósitos obtidos pela polimerização in situ do pirrol na presença de SDS (MMT/PPy.SDS) e sem surfactante (MMT/PPy) foram avaliadas e comparadas a partir da espectroscopia de infravermelho com transformada de Fourier (FTIR), difração de raios X (DRX), microscopia eletrônica de varredura (MEV), microscopia eletrônica de transmissão (MET), análise termogravimétrica (TG) e método padrão quatro pontas. Os difratogramas dos nanocompósitos revelaram que o espaçamento basal d001 da MMT (1,42 nm) foi alterado para valores maiores, indicando a intercalação do PPy na MMT para ambos os nanocompósitos obtidos. Os difratogramas e as imagens de MET e MEV dos nanocompósitos de MMT/PPy.SDS confirmaram que a presença do SDS na reação promoveu, além da intercalação, esfoliação parcial da argila. Os nanocompósitos MMT/PPy.SDS apresentaram condutividade elétrica (9,50 S/cm) maior do que o nanocompósito de MMT/PPy (4,44 S/cm). A presença da argila melhorou de forma significativa a estabilidade térmica do PPy.

Montmorillonite/polypyrrole (MMT/PPy) nanocomposites were prepared by the in situ polymerization of pyrrole in the presence of clay, natural sodium bentonite, (MMT-Na+) in aqueous solutions with or without an anionic surfactant, sodium dodecyl sulfate (SDS), using Iron (III) chloride hexahydrate (FeCl3.6H2O) as oxidant. The structure and properties of the nanocomposites obtained by the in situ polymerization of pyrrole in the presence of SDS (MMT/PPy.SDS) and without surfactant (MMT/PPy) were compared and evaluated by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis and the four-point probe method. The XRD patterns of the MMT/PPy composites shows that the d001 spacing in MMT (1.42 nm) was changed to higher values, indicating the intercalation of PPy on MMT for both nanocomposites. The XRD pattern, SEM and TEM images of the MMT/PPy.SDS nanocomposites confirmed that the presence of SDS in the reaction medium promoted, beyond intercalation, the partial exfoliation of the clay. The MMT/PPy.SDS nanocomposites showed electrical conductivity (9.50 S/cm) higher than the MMT/PPy nanocomposites (4.44 S/cm). The presence of the clay significantly improved the thermal stability of PPy.

The aim of this study was to obtain and evaluate the electrical, thermal and mechanical properties of iron oxide-filled castor oil polyurethane (PU/Fe2O3). The iron oxide used in this study was a residue derived from the steel pickling process of a Brazilian steel rolling industry. Polymeric composites with different iron oxide volume fractions (2.5, 5.0, 7.5, 10.0 and 12.5%) were prepared through the casting process followed by compression molding at room temperature. The composites were analyzed by FTIR, XRD and densities, tensile strength, Young's modulus, electrical and thermal conductivities measurements. By increasing the iron oxide content, the apparent density, tensile strength, Young's modulus and electrical conductivity values of the composites were also increased. The iron oxide additions did not change significantly the value of thermal conductivity (from 0.191 W.mK-1 for PU up to 0.340 W.mK-1 for PU enriched with 12.5% v/v of iron oxide). Thus, even at the higher iron oxide concentration, the compounds as well as the pure polyurethane can be classified as thermal insulators.

Neste trabalho foi avaliada a influência do tratamento químico de fibras vegetais nas propriedades mecânicas e dinâmico-mecânicas de resina epóxi reforçada com tecidos de fibras de juta. As fibras foram modificadas a partir de solução de hidróxido de sódio, e caracterizadas por microscopia eletrônica de varredura (MEV), espectrometria no infravermelho com transformada de Fourier (FTIR) e resistência à tração. As análises de FTIR e MEV evidenciaram, respectivamente, que o tratamento alcalino promoveu a remoção parcial da hemicelulose e modificou a morfologia das fibras de juta. Amostras dos compósitos com fibras tratadas e não tratadas foram confeccionadas a partir da laminação manual seguida da moldagem por compressão. Compósitos com fibras tratadas apresentaram propriedades mecânicas e módulo de armazenamento maiores do que as da resina epóxi sem reforço e compósitos com fibras sem tratamento. As micrografias de microscopia eletrônica de varredura (MEV) revelaram que compósitos com fibras tratadas possuem menor quantidade de vazios e menor quantidade de pull-out, sugerindo maior adesão com a matriz polimérica do que os compósitos com fibras sem tratamento.

This study was aimed at evaluating the efficiency of chemical treatment on the dynamic mechanical and mechanical properties of composite materials with jute fibers and epoxy matrix resin. The surfaces of the jute fibers were modified by contact with sodium hydroxide solutions, and characterized through scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and tensile strength testing. The FTIR and SEM analysis evidenced that the alkaline treatment promoted removal of the hemicellulose and modification in the morphology of the jute fibers, respectively. Polymeric composites with untreated and treated jute fiber were prepared through hand lay-up process followed by compression molding. The treated jute fiber composites displayed higher mechanical properties and storage modulus values than the epoxy resin and untreated fiber composites. The scanning electron micrographs (SEM) revealed that treated jute fiber composites have less voids and pull-out, suggesting a better adhesion with the polymeric matrix than untreated fiber composites.