Abstract The use of natural antimicrobial additives, such as orange essential oil (OO), can be a promising possibility to increase food shelf life with the aid of active packaging. This study aimed to develop an active packaging using orange oil and PBAT - poly (butylene adipate co- terephthalate) to store mozzarella cheese produced by a fine film extruder with 5, 10, and 15% OO (w/w). In the results, D-limonene was oil’s main constituent with antimicrobial activity against E. aerogenes, E. coli, and S. aureus. The addition of the oil did not alter the thermal stability of the film. The water vapor permeability increased with increasing oil concentration. All films presented high strength. However, films with higher OO concentrations favored the degradation process, as observed in the activation energy. The active packaging added with 15% OO (PBAT15) was efficient, reducing microbial growth up to 6 days of storage of mozzarella cheese.

RESUMO Os parâmetros da cristalização a partir do fundido de um composto de fibras lignocelulósicas de côco dispersas em poli (butileno adipato tereftalato) (PBAT), uma matriz de copoliéster totalmente biodegradável, foi estudada por calorimetria exploratória diferencial (DSC). Os compostos de PBAT/fibra de côco com 10% e 20% de fibra foram preparados num misturador interno de laboratório; a reometria de torque mostrou degradação insignificante durante o processamento. A cristalização não-isotérmica a partir do fundido da matriz foi estudada por DSC em compostos com 10% de fibra com taxas de resfriamento entre 2 e 32°C/min, e informações quantitativas foram fornecidas em temperaturas e taxas de cristalização, bem como a cristalinidade desenvolvida, que apresentou valor maior do que o esperado nas altas taxas de resfriamento. Os resultados cinéticos da cristalização foram correlacionados usando modelos clássicos macrocinéticos: Pseudo-Avrami, Ozawa e Mo, para obter expressões analíticas quantitativas apropriadas para o processamento. Os modelos Pseudo-Avrami e Mo representaram bem os dados experimentais. Uma análise detalhada da modelagem é apresentada, a fim de avaliar as incertezas esperadas. Apesar de desvios observados no início e no final do processo de cristalização, o modelo Mo é recomendado como a melhor correlação empírica geral dos dados experimentais para o propósito pretendido.

ABSTRACT The melt crystallization characteristics of a compound of coconut lignocellulosic fibers dispersed in poly(butylene adipate terephthalate) (PBAT), a fully biodegradable copolyester matrix, was studied by differential scanning calorimetry (DSC). PBAT/coconut fiber compounds with 10% and 20% filler content were prepared in a laboratory internal mixer; torque rheometry showed negligible degradation during processing. Nonisothermal melt crystallization of the matrix was thoroughly studied by DSC in 10% compounds at cooling rates between 2 and 32°C/min, and quantitative information was provided on crystallization temperatures and rates, as well as the crystallinity developed, which turned out to be higher than expected at the high cooling rates. Crystallization kinetic results were correlated using classical macrokinetic Pseudo-Avrami, Ozawa, and Mo models, in order to obtain quantitative analytical expressions appropriate for processing applications. Pseudo-Avrami and Mo models were found to represent well the experimental data. A detailed analysis of the model fitting is presented, in order to assess the expected uncertainties. Despite its failings at the onset and end of the crystallization process, Mo model is recommended as best overall empirical correlation of the experimental data for the intended purpose.

PHB has interesting features such as biodegradability, sustainability and durability. However, it has a high cost, in addition to being hard, brittle and thermally unstable during processing. Therefore, it was found convenient to study the crystallization of PHB/20% babassu compounds, with the intention of reducing the cost of the composite, in addition to seeking improvements in thermal properties. In this work, the parameters of melt crystallization were studied for PHB/20% babassu compounds driven at different cooling rates under a nitrogen flow. Subsequently, crystallization parameters were compared for different cooling rates. A kinetic analysis of data obtained for melt crystallization was performed. Among the models studied, Pseudo-Avrami showed the best correlation with experimental data, with discrepancy between +6% and -4%. The Mo model presented a discrepancy between +15% and -8%. A modified Mo model discrepancies are reduced to +3% and -4% within the range of validity of the model.

PET - poly (ethylene terephthalate) - bottle surfaces were exposed to chemical agents and evaluated with middle infrared spectroscopy (MIR) and near infrared hyperspectral imaging (HSI-NIR). Images (928-2.524 nm) were acquired at different times from bottle surfaces exposed to alkaline, acidic and ethanolic media. Savitzky-Golay smoothing (2nd order polynomial and 5-point window) combined with Standard Normal Variate (SNV) was used for pre-processing data. Scores from principal component analysis (PCA) on images showed discrimination of PET according to exposure time, particularly when employing NaOH. After the first two hours of chemical exposure, significant contribution of the (-C-O + OH) combination band indicated formation of glycol ethylene on the PET surface, which was confirmed from PCA loading plots. MIR reflectance spectra ranged from 4.000 to 650 cm-1. Changes in spectral intensities could be associated with depolymerization of PET when exposed to NaOH. These were confirmed with PCA and attributed to the carboxylate group of terephthalate.

Due to its ester bonds, poly(lactic acid) (PLA) undergoes biodegradation in humid environments, attracting market attention. The goal of this work was to observe the biodegradation in garden soil of PLA nanocomposites with neat (PLA/CNW) and surfactant modified cellulose nanowhiskers (PLA/CNW/S). Three types of surfactants were tested: poly(ethylene glycol) monooleate (PEGMONO) and poly(ethylene glycol) with molecular weight of 300 and 1000 Da. The films were obtained by solution casting, cut in strips of (2x2) cm and buried in garden soil, monitoring the temperature and humidity. After 90, 120 and 150 days changes were observed in the films by visual inspection, polarized light microscopy, thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FTIR). The results showed that the addition of surfactant favored the biodegradation of nanocomposites and that PLA/CNW/PEG1000 showed the fastest biodegradation rate.

Resumo Filmes de Poli(3-hidroxibutirato) (PHB) foram produzidos com a adição de óxido de zinco nanoestruturado (ZnOnano) em diferentes proporções (1%, 3%, 5% m/m). Os filmes foram caracterizados por TGA, DSC, MEV e infravermelho. A atividade antimicrobiana dos filmes na presença da bactéria E. coli também foi avaliada. Foram obtidos filmes homogêneos com boa dispersão das nanopartículas na matriz polimérica. A estabilidade do polímero não foi comprometida pelas nanopartículas, que funcionaram como agentes nucleantes aumentando a cristalinidade do polímero. A análise por componentes principais (PCA) mostrou que a nanocarga alterou as vibrações dos grupos funcionais indicando a existência de interações entre o ZnO e o polímero. O filme nanocompósito contendo 5% do óxido inibiu o crescimento da bactéria patogênica E. coli, mostrando-se, portanto, promissor em aplicações na indústria de embalagens para alimentos.

Summary Industrial Poly(hydroxybutyrate) PHB films were produced with the addition of nanostructured zinc oxide (ZnOnano) in different proportions (1, 3, 5% w/w). The films were characterized by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and infrared spectroscopy (FTIR). The antimicrobial activity against the bacteria E. coli was also evaluated. Homogeneous films with good dispersion of the nanoparticles in the polymer matrix were obtained. The stability of the polymer was not compromised by the nanoparticles, which functioned as nucleating agents to increase the crystallinity of the polymer. The principal component analysis (PCA) showed that the nanoclay modified the vibrations of the functional groups, indicating the existence of interactions between the polymer and ZnOnano. The nanocomposite film containing 5% of ZnOnano inhibited the growth of pathogenic E. coli., thus showing promise for applications in the food packaging industry.

Mechanical properties, morphology and nonisothermal crystallization of poly(3-hydroxybutyrate) (PHB) and blends of PHB and polystyrene (PS) were studied by tensile tests, scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). A two-phase structure composed by a PHB matrix and nearly spherical particles of PS was clearly noticed in SEM images. The presence of small amounts (0.5% to 3%) of amorphous PS affected the crystallinity of PHB, being more evident when high cooling rates were applied. The kinetics of nonisothermal crystallization was modeled according to Ozawa equation. The dependence of Ozawa parameters on temperature followed the same trend for PHB and PHB/PS blends; model parameters were found to be lower for the blends than for the neat PHB.

Samples of LDPE/modified starch blends 80/20 m/m before and after exposure to gamma rays were examined by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction. The effect of gamma radiation is clearly seen in the samples irradiated at a dose of 25 kGy. The main alteration in the polymeric material after exposure at the radiation range was a decrease in the mechanical properties, alterations in the chemical structure of the blend with an increase in the carbonyl and vinyl indices and the appearance of new crystalline symmetry generating a crystalline domain not existing before in the blend.

Nesse trabalho foi realizado um estudo sobre diferentes tipos de amido quanto ao crescimento, e a atividade amilolítica de culturas mistas e isoladas dos fungos Phanerochaete chrysosporium e Talaromyces wortmannii. Avaliaram-se também as propriedades térmicas e mecânicas das blendas de polietileno/amido anfótero (na proporção 80/20 (m/m)) antes e apos a inoculação das culturas mistas desses fungos.O amido regular Amidex 3 e o amido modificado Fox5901 foram os que se destacaram quanto ao crescimento celular e produção da enzima amilase. Apesar do pouco tempo de exposição dos filmes com os fungos, pode-se concluir que os microrganismos promovem mudanças físicas e químicas na estrutura da blenda, modificando suas propriedades térmicas e mecânicas. A alteração do grau de cristalinidade e das propriedades mecânicas das blendas podem ser indícios da modificação provocada pelo processo de biodegradação.

This study evaluated in relation the growth, and the amylolytic activity of mixed and isolated cultures of Phanerochaete chrysosporium and Talaromyces wortmanni on different types of starch. The thermal and mechanical properties in polyethylene/starch blends (proportion: 80/20 (w/w) before and after inoculation of the mixed cultures were evaluated. The regular starch Amidex 3 and the modified starch Fox5901 stood out in relation to the cellular growth and production of the amylase enzyme. In spite of the short time that the blends were exposed to the fungi, the microorganisms promoted physical and chemical changes in the structure of the blend, modifying its thermal and mechanical properties. The alteration of the degree of crystallinity and mechanical properties of the blends could be indications of the modification caused by the biodegradation process.

Poly (vinyl chloride), PVC, is a rigid polymer and for several of its applications must be compounded with plasticizing agents. The plasticizers minimize the dipolar interactions, which exist between the polymer's chains, promoting their mobility. In this work we studied the properties of PVC/plasticizer systems submitted to different doses of gamma radiation. We have used four commercial plasticizers amongt them di(2-ethylhexyl) phthalate, DEHP, which is present in a great number of commercial applications. The PVC/plasticizer systems have been studied as films made by the solvent evaporation technique. Irradiated and non-irradiated films have been characterized by viscosimetric analysis, mechanical essays and infrared spectroscopy. The results have shown that the rigid, non plasticized, PVC film presented the greatest degradation index, while among the plasticized films the one which presented the larger degradation index due to chain scission was the DEHP plasticized PVC.