Pollution of nature by plastics is a major environmental problem and the challenge for the future is to manage the lifetime of polymers better. The aim of this study is to establish a baseline on degradation mechanism and degradation kinetics for lifetime prediction of polylactide (PLA) in a marine environment. The ageing of PLA was accelerated by raising temperature in distilled water, filtered and renewed seawater and natural seawater. Samples were immersed in distilled water for six months at different temperatures (25, 30, 40 and 50°C) in order to evaluate the influence of temperature on PLA degradation kinetics and to predict lifetime. Then, samples were immersed in seawater both in the laboratory and at sea, in order to compare the effects of environment, marine organisms and salt, on degradation. The different degradation steps were followed by gravimetry, tensile tests, scanning electron microscopy (SEM), steric exclusion chromatography (SEC) and differential scanning calorimetry (DSC). In distilled water, accelerated ageing of PLA is complex with deviation from Fickian behaviour at higher temperature. Moreover, immersion in distilled water induces morphological changes, in particular holes, which are absent in seawater at 40°C for the same immersion time. Indeed, seawater has little impact on the diffusion kinetics but affects M ∞ values, which are slightly lower compare to the distilled water uptake.
Thermal ageing of thin films of unstabilized polydicyclopentadiene (pDCPD) at several temperatures ranging from 120 to 30°C was investigated by means of carbonyl build up by FTIR with ammonia derivatization, double bond titration, mass uptake measurement, hydroperoxides titration by iodometry and DSC coupled with sulfur dioxide treatment. In the temperature range under investigation, pDCPD is in glassy state and it oxidizes faster than common polymers oxidized at rubbery state (e.g. polydienic elastomers). Using the kinetic analysis, these results were ascribed to increased initiation rate due to catalyst residues, some possible intramolecular processes favoring propagation, or a very low termination rate of oxidation radical chains because of the control of termination reactions by macroradical diffusion.
This paper investigates the water absorption of polyamide 6. The high amount of absorbed water in the polymer and the large resulting decrease in the glass transition temperature (Tg) leads to a non Fickian water diffusion when samples are immersed, which is a significant difficulty when trying to model the water profile in thick specimens. The aim of this study is to be able to model this particular behaviour based on physical considerations. First, it is shown that the non Fickian water diffusion is caused by an increase in the diffusivity during water absorption. Two cases are then identified; one below Tg where the diffusivity is described using an Arrhenius law and one above Tg based on the free volume theory. Then, these two laws are implemented in a specific model that is able to describe the non Fickian water diffusion over a wide range of temperatures.
Ocean pollution by microplastics, i.e. small pieces of plastic of less than 5 mm, is one of the major concerns for the future of our planet. Secondary microplastics formation is due to fragmentation of macroplastic waste. This fragmentation can be attributed to environmental loadings such as waves, winds and tides, coupled with a change in mechanical properties of polymers induced by UV and seawater ageing. This study aims to characterize and understand changes in the mechanical behaviour of Polyethylene Terephthalate (PET) induced by hydrolysis, especially for high degradation levels. Thin films (200 microns) of PET were aged in water at temperatures from 110 °C to 80 °C for up to 150 days. Embrittlement occurs with chain scission during hydrolysis when molar mass of the polymer falls below 17 kg/mol. When the polymer is brittle, i.e. for high levels of degradation, the stress at break decreases linearly with the molar mass, and can be described by a simple mathematical expression.
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