RESUMO A produção de blendas de PLA/ PBAT tem por objetivo superar as desvantagens que cada polímero possui individualmente, como fragilidade, limitações de processabilidade e custo. Neste estudo, investigamos a miscibilidade e as propriedades de filmes biodegradáveis de PLA - Poli (ácido lático), PBAT- Poli (butileno adipato-co-tereftalato) e de suas blendas com proporções de 95/5, 70/30, 30/70 e 5/95 de PLA/PBAT, respectivamente, produzidos pelo método de evaporação de solvente. As blendas produzidas foram caracterizadas pelas técnicas de espectroscopia Raman, calorimetria exploratória diferencial (DSC), termogravimetria (TGA), microscopia eletrônica de varredura (MEV), viscosimetria de soluções diluídas e ensaio mecânico de tração. A análise dos espectros Raman, temperatura de transição vítrea (Tg), e TGA indicaram imiscibilidade dos polímeros em todas as composições estudadas. As análises mecânicas apontaram para diminuição da rigidez das blendas com a adição do PBAT. Os valores dos parâmetros de interação obtido pela análise de viscosimetria de soluções diluídas, sugerem miscibilidade parcial da blenda contendo 5% de PBAT. O estudo da miscibilidade e das propriedades das blendas de PLA/PBAT obtidas por evaporação de solvente possibilitarão a produção de novos materiais por diferentes técnicas visando novas aplicação para este material.

ABSTRACT The production of PLA / PBAT blends aims to overcome the disadvantages that each polymer had individually, such as fragility, processability and cost limitations. In this study, we investigated the miscibility and properties of biodegradable films of PLA - Poli (lactic acid), PBAT-Poli (butylene adipate-co-terephthalate) and their blends with proportions of 95/5, 70/30, 30/70 and 5/95 PLA / PBAT, respectively, produced by the casting method. The blends produced were characterized by the techniques of Raman spectroscopy, differential scanning calorimetry (DSC), thermogravimetry (TGA), scanning electron microscopy (SEM), diluted solutions viscosimetry and mechanical tensile testing. The Raman spectra, glass transitions temperature (Tg), and TGA analysis indicated that the polymers are immiscible in the compositions studied. Mechanical analyzes point to a decrease in the stiffness of the blend with the addition of PBAT. The interaction parameters, obtained by viscosimetry analysis of diluted solutions, suggest partial miscibility of the blend with 5% of PBAT. The study of the miscibility and properties of the PLA / PBAT blends obtained by solvent evaporation will enable the production of new materials by different techniques aiming at new applications for this material.

Abstract Modification of composite components has been proposed as a tool to improve their functional properties. The present work studied crosslinking of a starch/oat hull mixture by reactive extrusion with sodium trimetaphosphate (STMP), for application in composites with polylactic acid (PLA). The treated mixture was characterized regarding degree of substitution, FT-IR, and thermal properties. The native and modified mixtures were processed by injection molding, together with PLA and glycerol. The microstructure, mechanical properties, shrinkage, density, and thermal properties of the composites were determined. The FT-IR results, increase in phosphorus content and thermal stability after starch/fiber mixture treatment with STMP suggested the occurrence of crosslinking. Better interfacial adhesion between oat hulls and the polymeric matrix was observed in electron micrographs of the composites containing the modified components. Slight decreases in tensile strength and modulus were observed in the modified composites, suggesting that extrusion and subsequent milling may have broken some structures/linkages.

Abstract The modification of lignocellulosic fibers can enhance their interaction with other materials and alkaline hydrogen peroxide (AHP) is a reagent widely used to promote such modification. This work aimed to modify oat hulls fibers by reactive extrusion using AHP (7 g 100 g-1 of hulls). The modified oat hulls displayed performances comparable to those observed by other researchers using conventional AHP method (without extrusion). The AHP treated oat hulls showed increased luminosity compared to the extruded ones. Fourier transform infrared spectroscopy showed differences between the modified and unmodified structures. The removal of surface compounds resulted in a more open morphology, with greater surface area and greater porosity. Reactive extrusion can be an alternative method for fiber modification with several advantages, such as short processing time and no wastewater generation.

Rice hull is a residue from agro-industry that can be used to produce nanocellulose. We produced nanocellulose from rice hulls through bleaching (with a 5% NaOH solution followed by a peracetic acid solution) and acid hydrolysis at a mild temperature (45ºC) followed by ultrasonication. We investigated the microstructure, crystallinity and thermal stability of these materials and studied their effects on the properties of starch films. After bleaching, the compact structure around the cellulosic fibers was removed, and the lignin content of the residue decreased from 7.22 to 4.22%. The obtained nanocellulose presented a higher crystallinity (up 70%), higher thermal stability than the raw material and lignin contents below 0.35%. The nanocellulose formed interconnected webs of tiny fibers (< 100 nm in diameter), which decreased the opacity, water vapor permeability and improved the mechanical properties when added as reinforcement in the starch films.

The objectives of this work were to investigate the microstructure, crystallinity and thermal stability of nanofibrillated cellulose obtained from oat hulls using bleaching and acid hydrolysis at a mild temperature (45 ºC) followed by ultrasonication. The oat hulls were bleached with peracetic acid, and after bleaching, the compact structure around the cellulosic fibers was removed, and the bundles became individualized. The extraction time (30 or 60 min) did not affect the properties of the nanofibrillated cellulose, which presented a higher crystallinity index and thermal stability than the raw material (oat hulls). The nanocellulose formed interconnected webs of tiny fibers with diameters of 70-100 nm and lengths of several micrometers, producing nanofibers with a relatively high aspect ratio, thus indicating that these materials are suitable for polymer reinforcement.

The thermal degradation of miscible and immiscible poly (3-hidroxy butyrate) PHB/ poly (ethylene terephthalate) sulphonated (PETs) blends was investigated using thermogravimetric analyses. Model-free kinetic analysis, Vyazovkin and Flynn-Wall-Ozawa's methods, were used to determine the apparent activation energy in the whole interval of degradation of the pure polymers, immiscible blends, and miscible blends. The thermal stability of both polymers in their blends is higher when compared to the pure polymers. The synergistic effect in the thermal stability in the blends is higher for the miscible blend where the formation of the specific interaction between PHB and PETs occurs. The apparent activation energy of the individual polymers is higher in PETs/PHB blends, and this effect is potentiated by the miscibility of the blend.

CO2 supercrítico foi utilizado para preparar compósitos poliméricos com prata, prata/poli álcool vinílico e prata/ poli álcool vinílico/ poli (tereftalato de etileno) sulfonado, pela impregnação de um precursor de prata nas matrizes poliméricas no estado sólido seguida da redução térmica do precursor. Difração de raio X, microscopia eletrônica de varredura, espectroscopia de energia dispersiva, microscopia de força atômica, análise termogravimétrica e espectroscopia no UV/vis dos compósitos indicaram que as condições de preparação e a composição da matriz polimérica influenciam o tamanho e a forma das partículas de prata formadas, assim como, a uniformidade e a distribuição das partículas nas matrizes poliméricas. As partículas de prata nos compósitos ricos em PVA são menores, possuem formas mais uniformes e apresentam distribuição de tamanho mais estreita do que nos compósitos ricos em PETs.

Supercritical CO2 has been used to prepare silver polymer composites, silver/poly(vinyl alcohol) and silver/poly(vinyl alcohol)/sulfonated poly(ethylene terephthalate) through impregnation of a silver precursor in solid-state polymeric matrices followed by thermal reduction of the silver precursor. X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, atomic force microscopy, thermogravimetric analysis and UV/vis spectroscopy indicate that synthesis conditions and polymeric matrix composition affect silver particle size, shape and distribution in polymeric matrices. Silver particles are smaller, have a more uniform shape and present narrower size distribution in PVA-rich than in PETs-rich composites.

PET pós-consumo foi modificado quimicamente através de reação com ácido sulfúrico por diferentes tempos. O material modificado foi caracterizado por DSC e FTIR-PAS e XPS. Verificou-se que a intensidade relativa do isômero trans diminui enquanto do isômero gauche aumenta para tempos de reação entre 0 e 60 minutos. Após 60 minutos de reação observou-se a presença de endotermas múltiplas que podem ser relacionadas com o desenvolvimento de estruturas intermediárias porque as intensidades relativas dos isômeros trans e gauche não apresentam variação significativa. O valor determinado de capacidade de troca iônica do PET pós-consumo modificado (PETS-pc) é comparável com os valores de resinas ácidas comerciais e não é afetado no intervalo de tempo de reação utilizado. Os valores da capacidade máxima de adsorção, qm, e do parâmetro de afinidade entre o adsorvente e o adsorvato, K, (111,18 ppm e 531,91 mg de corante/100g de adsorvente, respectivamente) para a adsorção do corante Remazol vermelho na amostra quimicamente modificada por 30 minutos foram calculados a partir da isoterma de adsorção de Langmuir. Os resultados indicam que esse material possui características adsorventes, podendo vir a ser utilizado para tratamento de efluente de indústria de tingimento têxtil.

Chemical modification of post consumer PET was carried out by reaction with sulfuric acid. The modified material was characterized by DSC, XPS and FTIR-PAS measurements. The relative intensity of trans isomer increases while it decreases for gauche isomer for reaction times from 0 up to 60 min. After 60 minutes of reaction multiple endotherms were observed, which may be related to the development of an intermediated structure, since the relative intensities of the trans and gauche isomers do not change. The ionic exchange capacity of the modified post consumer poly(ethylene terephthalate), PETS-pc, is comparable to commercial acid resins and is not affected by the reaction time. The maximum adsorption capacity, qm, and the affinity parameter, K, (111.18 ppm and 531.91 mg dye/100g adsorvent, respectively) due to the adsorption of Remazol Red were calculated for PET samples chemically modified during 30 minutes from the Langmuir adsorption isotherms. The results indicate that PETS-pc has excellent adsorvent capacity, and can be applied to treatment of textile dye effluents.