Marcelo S. Rabello

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.

Heterogeneities and physical properties of ethylene-vinyl acetate foams containing calcium carbonates

This work investigated the effect of type (natural or precipitated) and content of calcium carbonate in ethylene-vinyl acetate foams produced by compression moulding. This processing technique generates various types of heterogeneities in the product, like differences between the skin and the core. The differences in temperature on the mould surface also have a major influence in foam properties. The hardness was shown to vary widely from place to place in moulded samples, and this was related to local variations in temperature. The analysis of the effect of calcium carbonate showed that the precipitated one yield better physical properties like density, hardness and elastic modulus.

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.

Photodegradation and Photostabilization of Poly(3-Hydroxybutyrate)

The present work is concerned with the photodegradation and photostabilization of poly(3-hydroxybutyrate) (PHB) biopolymer. Two commercial grades of PHB were investigated, containing of 4.0% and 6.2% of hydroxyvalerate (HV) comonomer, named PHB1 and PHB2, respectively. Injection moulded specimens were exposed to ultraviolet radiation (UV-A) in the laboratory for periods of up to 12 weeks and then characterized by tensile testing, surface appearance, size exclusion chromatography (SEC), and scanning electron microscopy (SEM). The exposure to UV radiation caused great damaged on the surface color, reduction of molecular size and mechanical properties. The effects were more pronounced on PHB2, probably due a lighter surface color and less packed macromolecular structure which facilitates the transmission of light throughout the samples. Specimens of PHB1 were also injected with the addition of a UV absorber and antioxidant, resulting in a higher UV stability of PHB, as shown by a low reduction in molar mass and better mechanical properties.

Falha por Stress Cracking em Híbridos PET/Argila

This study investigates stress-cracking failure of polymer/clay composites. Tensile and stress relaxation tests were conducted to evaluate the stress cracking resistance of PET and PET/clay in the presence of sodium hydroxide aqueous solution. The X-ray diffraction analyses showed that the clay formed a typical structure of a microcomposite, and not an exfoliated structure. The presence of clay causes stress concentration, with a strong consequence to the stress cracking behavior, but the effects depend on the lamellar ordering and the content of clay. When the clay lamellae are less ordered the rise in stress concentration is lower, but causes more surface cracks on the polymer, suggesting that the barrier effect was not very effective. Molar mass measurements showed that the clay accelerates the chemical attack of the matrix when higher concentrations of NaOH are used, but reduces the effect of mechanical stress on degradation.