Abstract In this work eggshell membrane was added as biobased curing catalyst to epoxy (DGEBA), for comparison purposes the synthetic catalyst DEH 35 data was reported, the curing of compounds was followed through differential scanning calorimetry (DSC) under dynamic conditions and their kinetics were modeled using Kissinger, Friedman, Friedman model based and Málek approaches. From evaluated Ea and l n A two steps of curing were verified, for the synthetic catalyst compound (S5) Ea abruptly increased for the degree of conversion α > 0.7 the opposite trend was observed for the eggshell membrane compound (M10). It is supposed for S5 Ea increases due to the competitive reactions leading to viscosity increase until reach the solid phase with decrease of the reactive groups availability, hampering the cross-linking, whereas for M10 Ea decreases at α > 0.7, hence invalidating the Kissinger model which assumes constant Ea.

Abstract Compounds of poly(3-hydroxybutyrate) (PHB) and titanium dioxide (TiO2) with filler content between 1% and 10% were prepared in a laboratory internal mixer. The effect of heating and cooling rates on the crystallization and melting of PHB/TiO2 compounds was investigated by differential scanning calorimetry (DSC). Melt and cold crystallization rates rise with increasing cooling/heating rates. A higher cooling rate translates to a lower melt crystallization temperature, while a higher heating rate results in a higher cold crystallization temperature. TiO2 promotes melt crystallization of PHB, behaving as a nucleant agent. The total crystallinity developed after melt and cold crystallization decreases for low levels of TiO2, i.e. 2% per weight, and is almost independent of the heating/cooling rate. The melting temperatures and rates are minimally affected by both the heating rate and filler content. The results suggest that the desired PHB microstructure can be controlled by filler content and adjusted heating/cooling rate.

RESUMO Foram preparados compósitos PHB/TiO2 e PHB/ZnO num misturador interno de laboratório, a cristalização foi investigada por calorimetria exploratória diferencial (DSC), com taxas de aquecimento e resfriamento entre 5 e 30 °C/min e a superfície de fratura de seletas composições analisada por microscopia eletrônica de varredura (MEV). Através das imagens de MEV foi observado que as nanopartículas de ZnO e TiO2 estão bem dispersas na matriz de PHB. Por DSC, observou-se que a adição de TiO2 e ZnO modificou a temperatura e taxa de cristalização do PHB, sem afetar significativamente a cristalinidade total. Em geral, a adição da carga TiO2 promoveu alterações mais significativas na matriz de PHB, comportando-se como um agente nucleante.

ABSTRACT PHB/TiO2 and PHB/ZnO compounds were prepared in a laboratory internal mixer. Crystallization was investigated by differential scanning calorimetry (DSC) with heating and cooling rates ranging from 5 to 30 °C/min. Fractured surface of selected samples was analysed by scanning electron microscopy (SEM). From the SEM images, it was observed that ZnO and TiO2 nanoparticles were properly dispersed in the PHB matrix. DSC studies revealed that the addition of TiO2 and ZnO changed the temperature and crystallization rate but did not affect the total crystallinity significantly. In general, TiO2 behaved as nucleating agent greatly influencing the PHB crystallization.