ABSTRACT In this work, the role of the degree of acetalization of polyvinylbutyral (PVB) on the dynamic mechanical properties of PVB nanocomposites was evaluated. Nanocomposites reinforced with carbon nanoparticles (pristine or oxidized multiwalled carbon nanotubes, graphene oxide and graphene nanoplatelets) were prepared by in situ addition during the synthesis of PVB from polyvinyl alcohol. It was found that the presence of nanoreinforcements during the synthesis considerably alters the degree of acetalization (AD) of PVB (ca. 65 mol% for the neat polymer), which values ranged from 50 to 77 mol%. Dynamic mechanical analyses were used to calculate the storage modulus and other parameters such as: factor C, degree of entanglement and adhesion factor, which were correlated with scanning electron microscopy images. There was a tendency to decrease AD with the increase in the degree of oxidation of the nanoreinforcements, however this contributed to a better dispersion and adhesion of these to the polymer matrix and, consequently, altered positively the nanocomposite properties.

This work aimed to synthesize bacterial cellulose (BC) membranes functionalized with Ce(NO3)3 and silver nanoparticles (AgNPs) heat-treated in oven and autoclave. The AgNPs were characterized by TEM and the membranes were characterized by their rehydration capacity, Thermogravimetric Analysis (TGA), Scanning Electron Microscopy with Dispersive Energy Spectroscopy (SEM/EDS), Wide-angle X-ray Diffractometry (XRD), Atomic Absorption Spectroscopy (AAS), antimicrobial activity and cytotoxicity. The BC membranes were white to light yellow or brown indicating functionalization with AgNps with 20 nm. XRD detected a decrease in the degree of crystallinity in functionalized membranes. The autoclaved samples exhibited the largest porosity and good rehydration capacity. AAS showed Ag presence in all samples. The best antibacterial activity was achieved for the membrane’s oven treated with 40 ppm of AgNPs. Among the functionalized membranes, the most recommended to be used as burn dressing is the Ag40A and Ag20CN1.1A since they showed good porosity, good antimicrobial activity, and better suitable cell viability.

The present work developed an experimental and simulation study to evaluate the influence of some operational conditions and mold design on the efficiency of an injection process used to produce polystyrene parts. The software SolidWorks Plastic was used to simulate the injection process and assess the performance of the mold considering the absence and the presence of venting. Experimental results obtained by varying the injection pressure, injection temperature as well as the mold temperature were used to validate the simulation data generated considering both mold designs. The findings revealed air entrapment at the end of the mold cavity and low process efficiency when the mold was operated with no venting, regardless the processing conditions. Simulation results indicated a remarkable increase of the process efficiency when vents were included on the parting line of the mold. In addition, the range of processing conditions which led to the highest process efficiency was virtually identified and tested in the real modified mold (with venting system). The findings revealed that the injection cycle time reduced in approximately 35% and the waste generation diminished from 65% to less than 1% when venting was included in the mold design and the optimal operational conditions were used.

Resumo A importância da preservação dos recursos hídricos tem resultado na aplicação de tecnologias, tais como o uso de materiais nanoestruturados, para minimizar o impacto associado à contaminação da água. Neste trabalho, foi avaliada a aplicação de pellets de poliamida-66 (PA) funcionalizados com nanopartículas de prata (AgNPs), em percentuais de 0.05; 0.10 e 0.50% em relação à massa de polímero, na desinfecção de água para consumo. O presente estudo teve como principal objetivo sintetizar as nanopartículas de prata, e avaliar a atividade antibacteriana destas nanoestruturas em relação à bactéria Gram negativa Escherichia coli quando incorporadas numa matriz de PA. A síntese das nanopartículas de prata foi realizada empregando o nitrato de prata como sal do metal precursor e o borohidreto de sódio como agente redutor. A dispersão coloidal foi caracterizada por espectrofotometria na região UV-Vis e microscopia eletrônica de transmissão. Posteriormente, foi realizada a quantificação de íons prata lixiviada da matriz polimérica para a água no período de 3 horas, de forma a avaliar comparativamente ao limite estabelecido pela Resolução do Conama 357/2005, que impõe um limite de concentração da prata de 0.010 mg L-1. O melhor resultado consistiu na aplicação de 0.05% de AgNPs na matriz polimérica, lixiviando uma quantidade equivalente a uma concentração média de íons prata de 0.008 mg L-1. A última etapa foi a utilização da matriz polimérica funcionalizada com as AgNPs em ensaios microbiológicos para mensurar a atividade antibacteriana do produto obtido contra o microrganismo E. coli. Os resultados ilustram que após 24 h de incubação, sob agitação e temperatura de 25°C, as amostras com 0.05% de AgNPs apresentaram uma redução antibacteriana de 97,89%.

Abstract The importance of the preservation of water resources has resulted in the application of technologies such as nanostructured materials, which are able to minimize the impact associated with water contamination. This work evaluated the application of polyamide-66 (PA) pellets functionalized with silver nanoparticles (AgNPs) at polymer mass percentages of 0.05, 0.10 and 0.50% to disinfect of drinking water. Studies were carried out in three stages. The first stage was the synthesis of the silver nanoparticles by using silver nitrate as a metal precursor and sodium borohydrate as a reduction agent. The colloidal dispersion was characterized by UV-Vis spectrophotometry and transmission electron microscopy (MET). Afterwards, the nanostructures were incorporated into a polyamide-66 polymeric matrix. In the second stage, the silver ions leached from the polymer matrix in the water after a three-hour period were quantified in order to evaluate the limit established by Conama Resolution 357/2005, which imposes a concentration limit of 0.010 mg L-1. The best results were obtained with the application of 0.05% AgNPs in the polymeric matrix, yielding an average concentration of silver ions lixiviated of 0.008 mg L-1. The last step comprised the quantification of the antibacterial activity of the polymer matrix containing 0.05% of AgNPs against the microorganism E. coli using the Standard Test Method for Determining the Antimicrobial Agents Under Dynamic Contact Conditions. The samples containing 0.05% of AgNPs exhibited an antibacterial reduction of 97.89% after 24 h of incubation under stirring at room temperature (25°C).

RESUMO Queimaduras causam lesões do revestimento epitelial, a partir de um agente externo, podendo variar desde uma pequena bolha flictena até formas mais graves, capazes de desencadear respostas sistêmicas. O uso de curativos contendo substâncias cicatrizantes e antimicrobianas é uma opção para terapia local. Os curativos de nanocelulose bacteriana (BNC) já demonstraram seu grande potencial de aplicação devido às suas propriedades como alto teor de pureza, alto poder de absorção de água e ótima adaptabilidade biológica. A incorporação de metais na membrana de nanocelulose é bastante promissora. Nanopartículas de prata (NPAgs) têm sido objeto de vários estudos devido às suas propriedades antibacterianas; nitrato de cério, Ce(NO3)3, por sua vez, aumenta a eficácia no tratamento por apresentar propriedades imunomoduladoras. O objetivo deste trabalho foi sintetizar e caracterizar membranas de nanocelulose bacteriana funcionalizadas com nitrato de cério e nanopartículas de prata visando aplicação no tratamento de pele humana lesionada por queimadura. O comportamento térmico, interações entre a BNC, Ce(NO3)3 e NPAg, bem como a morfologia, capacidade de retenção de água, reidratação e potencial antimicrobiano foram analisadas por termogravimentria (TGA), microscopia eletrônica de varredura (MEV), análise de conteúdo de capacidade de água, capacidade de reidratação e atividade antimicrobiana. A membrana formada pela incorporação de Ce(NO3)3 e NPAgs simultaneamente, e submetida ao tratamento térmico, conservou as propriedades térmicas de ambos os materiais, assim como também boa capacidade de reidratação e um potencial de redução microbiana de 98% para Staphylococcus aureus. A análise de MEV apresentou alteração na morfologia, redução de poros e a presença de partículas, o que sugere adequada incorporação dos compostos.

ABSTRACT Burns cause lesions of the epithelial lining, from an external agent, and can range from a small injury to more severe forms, capable of triggering systemic responses. The use of dressings containing healing and antimicrobial substances are options for local therapy. Bacterial nanocellulose (BNC) dressings have already demonstrated their great potential due to their properties such as high purity, high water absorption capacity and optimum biological adaptability. The incorporation of metals in the nanocellulose membrane is quite promising. Silver nanoparticles (AgNPs) have been studied because of their antibacterial properties; cerium nitrate, Ce(NO3)3, on the other hand, increases the efficacy of the treatment because of its immunomodulatory properties. The objective of this work was to synthesize and characterize bacterial nanocellulose membranes functionalized with cerium nitrate and silver nanoparticles aiming the treatment of human skin that has been subject to burning injuries. Thermal behavior, interactions between BNC, Ce(NO3)3 and AgNP, as well as morphology, water retention capacity, rehydration capacity and antimicrobial potential were analyzed by thermogravimetry (TGA), scanning electron microscopy (SEM), analysis of water content, rehydration capacity and antimicrobial activity. Membranes formed by incorporation of Ce(NO3)3 and AgNPs simultaneously, and submitted to heat treatment, preserved thermal properties of both materials, as well as a good rehydration capacity and a microbial reduction potential of 98% for Staphylococcus aureus. SEM analysis showed changes in morphology, pore size reduction and the presence of particles, what suggest successful incorporation of the compounds.

RESUMO A utilização de materiais nanoestruturados sintetizados a partir de sais metálicos tem atraído cada vez mais a atenção de pesquisadores e indústrias no sentido de desenvolver aplicações inovadoras em áreas como a de energia, saúde e alimentos. A prata, o cobre e o óxido de zinco, por apresentarem propriedades antibacterianas, possuem um grande potencial para aplicação como substituintes aos tradicionais agentes antibacterianos organoclorados e derivados de arsênio. O óxido de zinco, por apresentar baixíssima toxicidade às células humanas, não sendo classificado como metal pesado e por ser um material biocompatível, aparece como alternativa em aplicações como na área médica e no tratamento de água para o consumo. O presente trabalho teve como principal objetivo sintetizar nanopartículas de óxido de zinco pelo método do poliol, e avaliar a atividade antibacteriana destas nanoestruturas contra a bactéria Gram negativa Escherichia coli. As sínteses foram conduzidas na presença e ausência da poli(vinil pirrolidona) para investigar a influência deste agente estabilizante nas propriedades morfológicas das nanopartículas obtidas. Todas as amostras foram caracterizadas por espectrofotometria na região do UV-Vis, difratometria de raios-X, microscopia eletrônica de varredura com efeito de campo e microscopia eletrônica de transmissão. Testes para avaliação da atividade antibacteriana com diferentes quantidades de nanopartículas de óxido de zinco sintetizadas sem a poli(vinil pirrolidona) foram conduzidos conforme a norma ASTM E-2149. Os resultados obtidos demonstraram que o método do poliol foi capaz de produzir nanopartículas de óxido de zinco com elevado grau de pureza e diâmetro médio em torno de 20 nm, na ausência ou presença da poli(vinil pirrolidona). Os ensaios microbiológicos comprovaram que as nanopartículas de óxido de zinco produzidas apresentaram excelente atividade antibacteriana contra a bactéria Escherichia coli quando aplicadas em concentrações superiores a 50 mg.L-1.

ABSTRACT The use of nanostructured materials synthesized from metal salts has increasingly attracted the attention of researchers and industries to develop innovative applications in areas such as energy, health and food. Due to the antibacterial properties of silver, copper and zinc oxide, they are potential substituents to the traditional antibacterial agents, such as organochlorines and arsenic derivatives. Once zinc oxide is not classified as heavy meta, has low toxicity, and is biocompatible, it appears as an alternative material for applications in the medical area and water treatment. The main objective of this work was to synthesize zinc oxide nanoparticles by the polyol method and evaluate the antibacterial activity of these nanostructures against the Gram negative bacteria Escherichia coli. The syntheses were carried out in the presence and absence of poly(vinyl pyrrolidone) to investigate the influence of this stabilizing agent on the morphological properties of the nanoparticles. All of the samples were characterized by UV-Vis spectrophotometry, X-ray diffractometry, field emission scanning electron microscopy and transmission electron microscopy. Tests to evaluate the antibacterial activity of different amounts of the zinc oxide nanoparticles were performed according to the ASTM E-2149. The results obtained demonstrated that the polyol method was able to produce zinc oxide nanoparticles with high purity and average diameter around 20 nm, regardless the presence of poly(vinyl pyrrolidone). Microbiological assays showed that zinc oxide nanoparticles produced excellent antibacterial activity against the bacteria Escherichia coli when applied at concentrations higher than 50 mg.L-1.

RESUMO Neste trabalho foram preparados nanocompósitos de polipropileno e montmorilonita organofílica PP/MMTO, nas concentrações de 1, 2, 5 e 7% pela técnica de intercalação fundida diretamente em uma injetora hidráulica monorosca. O material obtido foi processado, obtendo corpos de prova chamados de primários em formato de gravata. O reprocessamento foi realizado com a moagem do material em um moinho de facas. Logo após, o material moído foi injetado novamente obtendo o segundo ciclo do material e, posteriormente, até atingir o quarto ciclo. As amostras foram avaliadas por microscopia eletrônica de varredura (MEV), ensaio mecânico sob tração, análise termogravimétrica (TGA) e calorimetria exploratória diferencial (DSC). Os resultados de resistência à tração e módulo de Young para as formulações contendo nanoargila não apresentaram alterações significativas, fazendo com que a nanoargila atuasse como carga. As análises de TGA mostraram que quando adicionado 2% MMTO, a temperatura de degradação (Tonset) aumentou 17,10% quando comparada com o PP, sendo esse o melhor resultado encontrado. As curvas de DSC não mostraram variação na temperatura de fusão (Tm2) para as formulações contendo MMTO e também não para as formulações reprocessadas. Já o grau de cristalização (αc) apresentou variações significativas, tendo como destaque a formulação com 5% de MMTO, onde o αc foi 66,70%, cerca de 26,80 % superior ao polipropileno.

ABSTRACT In this work, polypropylene and organophilic montmorillonite PP/MMTO nanocomposites were prepared at the concentrations of 1, 2, 5 and 7 % were prepared through the melt intercalation by directly at the single screw hydraulic injector. The obtained material was processed, obtaining specimens called ties in the form of ties. Reprocessing was performed by milling the material in a knife mill. Soon after the ground material was injected again obtaining the second cycle of the material and, later, until reaching the fourth cycle. The samples were evaluated by scanning electron microscopy (SEM), mechanical tensile test, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The results of tensile strength and Young's modulus for the nanoclay containing formulations did not show significant changes, causing the nanoclay to act only as a charge. The TGA analysis showed that when 2% MMTO was added, the degradation temperature (Tonset) increased 17.10% when compared to PP, which was the best result found. The DSC curves did not show variation in the melt temperature (Tm2) for the formulations containing MMTO and also for the reprocessed formulations. On the other hand, the degree of crystallization (αc) showed significant variations, with emphasis on the formulation with 5% MMTO, where αc was 66.70%, about 26.80% higher than PP.