Resumen El poli (ácido lactico) (PLA) es un termoplástico biodegradable ampliamente utilizado en la fabricación de aditivos, principalmente en productos fabricados mediante impresión 3D. Sin embargo, el PLA es muy frágil y tiene baja resistencia al impacto; por lo tanto, las mejoras en este sentido son industrial y tecnológicamente importantes. Con el fin de desarrollar una metodología adecuada para un PLA de mayor rendimiento, este trabajo investigó los efectos del recocido térmico en las propiedades mecánicas (impacto, tracción, dureza de la Shore D), temperatura de desviación térmica (HDT), temperatura de ablandamiento de Vicat (TAV) y cristalinidad (difracción de rayos X) del PLA. Las muestras inyectadas fueron recocidos en horno a 70, 80, 90 y 100 oC. El recocido a 70 oC no fue efectivo, sin cambios significativos verificados. Por otro lado, el recocido a 80, 90 y 100 oC proporciono picos cristalinos en la DRX, lo que indica el desarrollo de la organización estructural. Los resultados expresivos se lograron a 90 oC para resistencia al impacto, HDT, VST, dureza Shore D y resistencia a la tracción, relacionados con PLA sin recocido. Los resultados presentados en este trabajo son de importancia científica y tecnológica, ya que las propiedades mecánicas y termomecánicas del PLA se han mejorado utilizando una metodología simple que puede producir productos de mayor rendimiento principalmente para la industria de impresión 3D de PLA.

Abstract Poly (lactic acid) (PLA) is widely used biodegradable thermoplastic in the additive manufacturing, mainly on manufactured products through 3D printing. However, PLA is highly fragile and presents low impact strength; hence improvements on this way are industrially and technologically important. Aiming to develop proper methodology for higher PLA performance, this work investigated the effects of thermal annealing on the mechanical properties (impact, tensile, Shore D hardness), heat deflection temperature (HDT), Vicat softening temperature (VST) and crystallinity (X-ray diffraction) of PLA. Injected specimens were annealed in greenhouses at 70, 80, 90 and 100 oC. Annealing at 70 oC was not effective, without verified significant changes. On the other hand, annealing at 80, 90 and 100 oC provided crystalline peaks in DRX, indicating development of structural organization. Expressive results were achieved, at 90 oC, for impact strength, HDT, VST, Shore D hardness and tensile strength, related to non-annealed PLA. Provided results in this work have scientific and technological importance, since the mechanical and thermomechanical properties of PLA were improved using a simple methodology which may render higher performance products mainly for the 3D printing industry of PLA.

Poly(3-hydroxybutyrate) (PHB) was compounded with three different Bentonite clays: natural, purified by ultrasound/sonicated and organically modified with hexadecyltrimethylammonium bromide. PHB/Bentonite masterbatches with 30% clay were prepared in a laboratory internal mixer and letdown with pure matrix to 1% and 3% w/w clay. Test samples were injection molded and characterized by x-ray diffraction (XRD), differential scanning calorimetry (DSC), infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). Increase in Bentonite hydrophobic character was evinced by FTIR for organoclays. XRD of composites showed increase in clay interlayer distance and peak broadening, suggesting formation of intercalated nanocomposites. DSC showed increase in crystallinity and crystallization rate for compounds, especially for PHB/organoclay formulations. Thermal aging was conducted by exposing specimens at 115ºC for up to 120 hours, and mechanical properties were measured according to ASTM standards. Elastic modulus increased and impact strength decreased with time and clay content; clay purification had little effect on the tensile properties. Tensile strength of thermal aged samples showed little variation, except for the organoclay nanocomposites, for which it significantly decreased with exposure time. SEM images displayed a whitened honeycomb structure and detachment of PHB/Bentonite layers which may be connected to cold crystallization and degradation processes taking place during thermal aging.

O presente trabalho investigou o efeito da adição de baixas concentrações (0,5 e 1,0%) de poli(3-hidroxibutirato) (PHB) na cristalização isotérmica a frio do poli(tereftalato de etileno) (PET). As curvas de energia foram obtidas por calorimetria exploratória diferencial (DSC) e a cinética de cristalização foi analisada pelo método de Avrami. Dois estágios de cristalização foram observados. Os resultados mostraram que o PHB promove alterações na taxa de cristalização do PET, como verificado por mudanças nos tempos para se atingir 1, 10, 30, 50 e 99% de cristalinidade relativa. As energias de ativação para o primeiro e segundo estágios da cristalização foram determinadas através das curvas de Arrhenius, sendo praticamente independentes da presença de PHB nas misturas PET/PHB. As temperaturas de fusão de equilíbrio foram determinadas de acordo com o procedimento de Hoffman e Weeks; as misturas PET/PHB apresentaram valores mais elevados deste parâmetro sugerindo que o PHB altera a estrutura cristalina do PET.

The present work is concerned with the effect of low concentrations (0.5 e 1.0%) of poly(3-hydroxybutirate) (PHB) on the isothermal cold crystallization of poly(ethylene terephthalate) (PET). Energy curves were obtained by differential scanning calorimetry (DSC) and the kinetics of the crystallization was analyzed using Avrami's method. Two crystallization stages were observed. Results showed that the presence of PHB affects the crystallization rate of PET, as verified by changes in the time needed to reach 1, 10, 30, 50 and 99% of crystallinity. Activation energies for the two crystallization stages were computed using Arrhenius plots; PET/PHB mixtures showed slightly smaller values. The equilibrium melting temperatures were estimated according to the procedure of Hoffman and Weeks; the higher values obtained for the PET/PHB mixtures suggest that PHB affects the crystalline structure of PET.

A cristalização a frio do poli(tereftalato de etileno) (PET) e de suas blendas com poliestireno (PS) foi estudada utilizando calorimetria exploratória diferencial (DSC), análise dinâmico-mecânica (DMA), microscopia eletrônica de varredura (MEV) e propriedades mecânicas. As blendas PET/PS formam misturas bifásicas, como confirmado por MEV e por DMA, onde fases distintas e duas Tg s foram observadas. Por outro lado, a determinação da temperatura de fusão de equilíbrio (Tmº) do PET por DSC indicou uma diminuição neste parâmetro com a presença do PS, sugerindo que uma solubilidade limitada do PS no PET deve ocorrer. A presença de um componente não cristalizável como o PS, parcialmente solúvel em uma fase cristalizável como PET, reduz a habilidade de cristalização. Isto foi observado nas análises de DSC através do deslocamento dos picos de cristalização a frio do PET para temperaturas maiores e por uma redução na velocidade de cristalização a frio. A abordagem de Avrami foi utilizada para os estudos cinéticos em condições isotérmicas, mostrando que o processo de cristalização ocorre em dois estágios e que a constante de cristalização K diminuiu significativamente com a presença de poliestireno. Nas blendas PET/PS a presença de apenas 1% de PS retardou significantemente a cristalização do PET, em magnitude semelhante ao que ocorreu quando concentrações mais elevadas de PS foram utilizadas. Este comportamento é de grande importância industrial já que em baixa concentração de PS as propriedades mecânicas do PET não são afetadas, como também mostrado neste estudo.

The cold crystallization of PET and its blends with polystyrene (PS) was investigated by differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMA), scanning electron microscopy (SEM) and mechanical properties. PET/PS blends form separate phases, as confirmed by SEM and DMA, showing distinct phases and two glass transition temperatures. On the other hand, the determination of the equilibrium melting temperature of PET indicated that this parameter decreased when PS was added, suggesting that a limited solubility should exist. The presence of non crystallizable molecules like polystyrene, partially soluble in the PET crystallizable phase, reduces the driving force for crystallization. In the current study this effect was observed as a shifting of the cold crystallization DSC peaks to higher temperatures and also by the reduction in the rate of cold crystallization. The approach developed by Avrami was applied to study the kinetics of cold crystallization under isothermal conditions. It was shown that the crystallization occurs in two stages and that the rate constant K decreased significantly when PS was present. The blends containing only 1% of PS had the same magnitude of reduction in the rate of crystallization as the blends with higher PS content. This behaviour has a high practical significance since in low concentrations of PS the mechanical properties of PET are not affected, as also shown in this study.