Cecile Courgneau

Local demixion in plasticized polylactide probed by electron spin resonance

Improving the barrier properties to gas and organic compounds of biosourced polyesters, such as polylactides (PLAs), by increasing their crystallinity has been suggested by several authors. This paper investigates the risk of microphase separation for a technological approach that would involve a plasticization of PLA, to further its crystallization kinetics, with common plasticizers: Acetyl tributyl citrate (ATBC) and Poly(ethylene glycol) (PEG). Overplasticization effects following microphase separation were monitored along the film thickness by exposing dynamically thermo-compressed films to nitroxide spin-probes. The method enabled a scan of the local polymer mobility for different concentration profiles in spin-probes, with in particular a maximum moving continuously in time towards the geometric center. The results were interpreted as excess local temperatures that would give similar ESR spectra motion in the bulk. It was shown that measured excess temperatures could be related to local shifts in the glass transition temperature along the film thickness.

The effect of the stretching of PLA extruded films on their crystallinity and gas barrier properties

Driven by environmental concerns, new polymers based on renewable resources are arriving on the market to replace conventional polymers, obtained from petroleum, for different applications like food packaging. One of the most prominent polymers among these materials is poly(lactic acid) (PLA), a biodegradable, thermoplastic, aliphatic polyester derived from renewable resources, such as corn starch (in the USA) or sugarcanes (in the rest of the world). However this polymer presents different disadvantages and especially low gas barrier properties [1]. Thermal crystallization can be used to increase its gas barrier properties but long times are necessary [2] and are not compatible with an industrial process. Another way to increase the gas barrier properties consists in stretching the film in order to increase its crystallinity and so its diffusion coefficient. We have prepared stretched PLA films with different stretch ratio and we have studied the effect of the stretching parameters on the gas barrier properties of PLA films. Finally we compared this process with the isothermal crystallization process by taking into account the crystallinity degree and the crystalline morphology.