The aim of this work was to evaluate the photo degradation of PP films containing photo stabilizers, a ultraviolet absorber and a hindered amine light stabilizer (HALS), and a red pigment. The films were produced by extrusion and exposed to the UV radiation in the laboratory for up to 15 weeks. The results obtained from FTIR, UV-vis and colorimetry showed that the pigment reduced the rate of chemical degradation both in non-stabilized and photo stabilized films, and the influence was more significant for the combination of pigment and HALS. However, the color shift was more evident when the pigment was present, suggesting that this additive may suffer chemical rearrangements during exposure but do not generate free radicals that can initiate degradation of the polymer. The mechanical properties of the films followed the same trend as the other results, but the unexposed films showed a peculiar behaviour, with much higher tensile strength when the pigments were present. X-ray diffraction and DSC analyses suggested that this might be related to differences in crystal structure.

Ultra high molecular weight polyethylene (UHMWPE) is one of the most important engineering materials owing to outstanding properties like impact strength and abrasion resistance. However, the relatively low Young´s modulus restricts some application and the use of fillers may be a suitable way to overcome this. The fillers can influence the photo stabilization of the compound, as it occurs to other polymers. Neat UHMWPE and its composites with 1 and 10% of iron ore fine were exposed to ultraviolet radiation for up to 33 days and then tested for mechanical properties. The stress-strain behaviour changed with degradation, with an evident necking and strain hardening region that was not observed before exposure, due to a reduction in entanglements density. From the tensile results, the filler may have a protection action against UV, particularly when a loading of 10% was present. Complementary analyses were performed, including X-ray diffraction, DSC and SEM.

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.

<title>Abstract</title><p>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.</p>

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.

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.

O presente estudo investiga a falha por stress cracking em polímeros contendo argila montmorilonítica. Ensaios de tração e de relaxação de tensão foram conduzidos para avaliar a resistência ao stress cracking do PET puro e dos híbridos PET/argila em contato com soluções aquosas de hidróxido de sódio. As análises por difratometria de raios-X evidenciaram que a argila adicionada não gerou uma estrutura esfoliada e sim a obtenção de microcompósitos. Os resultados mostraram que a presença de argila dispersa no PET causa concentração de tensão, o que exerce forte influência no comportamento de stress cracking, com os efeitos sendo afetados pela ordenação lamelar e ao teor de carga, resultando em maiores taxas de relaxação de tensão. A argila com menor regularidade no empilhamento lamelar, embora ocasione menor concentração de tensão, favorece mais o fissuramento superficial da matriz, sugerindo que o efeito de barreira ao fluido não foi efetivo. Medidas de massa molar evidenciaram que a argila acelera o ataque químico da matriz quando elevadas concentrações de solução são utilizadas, porém diminui o efeito da tensão mecânica na degradação.

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.

Samples of polypropylene (PP) and low-density polyethylene (LDPE) were submitted to ultraviolet radiation, in the natural environment and also in the laboratory. Chemical modifications were quantified by the carbonyl index (CI), mechanical properties and melt flow index. The degradation in the laboratory was comparatively faster than in the environment for both types of polymers. The accelerating factor was determined for the various properties investigated. This parameter, however, showed a large variation with the degradation criteria and the type of polymer. The existence of a "universal accelerating factor", therefore, was not observed in the current study.