Renate Maria Ramos Wellen

Melting and crystallization of poly(3-hydroxybutyrate): effect of heating/cooling rates on phase transformation

We studied the crystallization and melting phenomena of poly (3- hydroxybutyrate) (PHB), a biodegradable and biocompatible semi-crystalline thermoplastic, obtained from renewable resources. Its high crystallinity motivated several studies on crystallization and melting behavior, and also on ways to increase the amorphous polymer fraction. The effect of heating and cooling rates on the crystallization and melting of commercial PHB was investigated by differential scanning calorimetry. Several rates, ranging from 2.5 to 20 °C min –1 , were used to study the phase changes during heating/cooling/reheating cycles. The results showed that PHB partially crystallizes from the melt during the cooling cycle and partially cold crystallizes on reheating, and that the relative amount of polymer crystallizing in each stage strongly depends on the cooling rate. The melt and cold crystallization temperatures, as well as the rates of phase change, depend strongly on the cooling and heating rates.

Redução da velocidade de cristalização a frio do PET na presença de poliestireno

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.

Effect of polystyrene on poly(ethylene terephthalate) crystallization

Blends of poly(ethylene terephthalate) (PET) and polystyrene (PS) with PS content ranging from 0% to 60% by weight, were compounded in a laboratory internal mixer, followed by quenching into iced water, resulting in substantially amorphous compounds. Blend morphology was analyzed by scanning electron microscopy (SEM). Standard differential scanning calorimetry (DSC) was used to study the cold crystallization and melting behavior of PET and PET/PS blends. SEM micrographs show a two-phase structure made up with spherical PS particles dispersed in a PET matrix. DSC scans showed that crystallization of PET is affected by the heating rate and by the addition of even small amounts of PS. In particular, the rate of cold crystallization of PET is significantly reduced by the incorporation of 1% of PS, attributed to the anti-nucleating effect of PS on PET. The amount of PET crystallized and the melting characteristics (temperature, rate) are not significantly affected by either PS content or heating rate.

The Effect of Polystyrene on the Crystallization of Poly(3-hydroxybutyrate)

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.

Environmental Stress Cracking of Poly(3-hydroxibutyrate) Under Contact with Sodium Hydroxide

Environmental stress cracking (ESC) is one of the most important causes of polymer premature failure, occurring when a combination of mechanical load and an aggressive fluid is applied. The phenomenon is well know by polymer producers and product designers but its mechanisms are not very well understood. Although the ESC effects of many commercial polymers are well known, this type of failure in biopolymers were not studied yet. In the current work, the stress cracking behaviour of poly(3-hydroxybutyrate) (PHB) with 4,0 and 6,2% of hydroxyvalerate (HV) was investigated in injection-moulded bars under contact with sodium hydroxide (NaOH) solutions. The experiments were conducted using two different types of stress arrangements: (i) an ordinary tensile testing and (ii) a relaxation experiment. In both situations the injection-moulded bars were exposed to the NaOH solution and some testing conditions where varied, like the cross-head speed of the tensile test and the maximum load of the relaxation arrangement. The results showed that NaOH acted as a strong stress cracking agent for PHB, causing surface cracking and reducing significantly the mechanical properties. Catastrophic failure with an extensive surface damage was also observed by photographed and scanning electron microscopy (SEM) images. The magnitude of the effects increased with decreasing crosshead speed and increasing loading level.

Efeito da adição de PHB na cristalização a frio 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 Avramis 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.