Influence of plasticizers on thermal properties and crystallization behaviour of poly(lactic acid) films obtained by compression moulding

[EN] Neat and plasticized poly(lactic acid) (PLA) films were obtained by compression moulding. Three different plasticizers, at concentrations of 5 and 10%, were used: poly(ethylene glycol) (PEG) of 1000 and 4000gmol(-1) molecular weights and a commercial plasticizer, Palamoll (R) 638. Crystallization behaviour and glass transition of PLA films were analysed using differential scanning calorimetry and X-ray diffraction. Films were also characterised in terms of structural, tensile, barrier and optical properties. The addition of the three plasticizers reduced the glass transition temperature (T-g) while promoting the crystallization of PLA in the compression-moulded films, depending on their type and concentration. PEG 4000 enhanced the crystallization more than PEG 1000 and Palamoll (R) 638, the latter being that which induced the lowest degree of crystallization. The T-g value of the PLA amorphous phase was reduced by the addition of plasticizers, proportionally to their concentration. Nevertheless, all of the plasticized films exhibited similar elastic modulus and were less resistant to break and less extensible due to the greater induced crystallinity. PEG 4000 markedly reduced the film stretchability whereas this effect was less marked when Palamoll (R) 638 was used. (c) 2016 Society of Chemical IndustryMuller, J.; Jiménez Marco, A.; González Martínez, MC.; Chiralt, A. (2016). Influence of plasticizers on thermal properties and crystallization behaviour of poly(lactic acid) films obtained by compression moulding. Polymer International. 65(8):970-978. doi:10.1002/pi.5142S97097865

A Study of the Crystallization, Melting, and Foaming Behaviors of Polylactic Acid in Compressed CO2

The crystallization and melting behaviors of linear polylactic acid (PLA) treated by compressed CO2 was investigated. The isothermal crystallization test indicated that while PLA exhibited very low crystallization kinetics under atmospheric pressure, CO2 exposure significantly increased PLA’s crystallization rate; a high crystallinity of 16.5% was achieved after CO2 treatment for only 1 min at 100 °C and 6.89 MPa. One melting peak could be found in the DSC curve, and this exhibited a slight dependency on treatment times, temperatures, and pressures. PLA samples tended to foam during the gas release process, and a foaming window as a function of time and temperature was established. Based on the foaming window, crystallinity, and cell morphology, it was found that foaming clearly reduced the needed time for PLA’s crystallization equilibrium

Thermo-oxidative stabilization of poly(lactic acid)-based nanocomposites through the incorporation of clay with in-built antioxidant activity

In this work, an innovative approach to overcome the issue of the poor thermo-oxidative stability of polymer/clay nanocomposites is proposed. Specifically, biodegradable polylactic acid (PLA)-based nanocomposites, containing organo-modified clay with in-built antioxidant activity, were prepared. Through a two-step chemical protocol, a hindered phenol antioxidant was chemically linked to the ammonium quaternary salt which was then intercalated between the clay platelets [(AO)OM-Mt]. The nanocomposites were characterized and their thermo-oxidative stability during melt processing and under long-term thermal test conditions was investigated. PLA nanocomposites containing the (AO)OM-Mt showed higher oxidative stability, along with better clay dispersion, compared to PLA-nanocomposites containing commercial clay and a free hindered phenol antioxidant. Obtained results can be explained considering that (AO)OM-Mt may act locally, at the interface, between the silicate layers and the polymer macromolecules, thus contributing to the observed improved stability of the polymer both during processing and under long-term thermal-oxidative conditions

Mechanical recycling of polylactide, upgrading trends and combination of valorization techniques

The upcoming introduction of polylactides in the fractions of polymer waste encourages technologists to ascertain its valorization at the best quality conditions. Mechanical recycling of PLA represents one of the most cost-effective methodologies, but the recycled materials are usually directed to downgraded applications, due to the inherent thermomechanical degradation affecting its mechanical, thermal and rheological performance. In this review, the current state of mechanical recycling of PLA is reported, with special emphasis on a multi-scale comparison among different studies. Additionally, the applications of physical and chemical upgrading strategies, as well as the chances to blend and/ or composite recycled PLA are considered. Moreover, the different valorization techniques that can be combined to optimize the value of PLA goods along its life cycle are discussed. Finally, a list of different opportunities to nurture the background of the mechanical recycling of PLA is proposed, in order to contribute to the correct waste management of PLA wastes

Circadian Disruption Accelerates Tumor Growth and Angio/Stromagenesis through a Wnt Signaling Pathway

Epidemiologic studies show a high incidence of cancer in shift workers, suggesting a possible relationship between circadian rhythms and tumorigenesis. However, the precise molecular mechanism played by circadian rhythms in tumor progression is not known. To identify the possible mechanisms underlying tumor progression related to circadian rhythms, we set up nude mouse xenograft models. HeLa cells were injected in nude mice and nude mice were moved to two different cases, one case is exposed to a 24-hour light cycle (L/L), the other is a more “normal” 12-hour light/dark cycle (L/D). We found a significant increase in tumor volume in the L/L group compared with the L/D group. In addition, tumor microvessels and stroma were strongly increased in L/L mice. Although there was a hypervascularization in L/L tumors, there was no associated increase in the production of vascular endothelial cell growth factor (VEGF). DNA microarray analysis showed enhanced expression of WNT10A, and our subsequent study revealed that WNT10A stimulates the growth of both microvascular endothelial cells and fibroblasts in tumors from light-stressed mice, along with marked increases in angio/stromagenesis. Only the tumor stroma stained positive for WNT10A and WNT10A is also highly expressed in keloid dermal fibroblasts but not in normal dermal fibroblasts indicated that WNT10A may be a novel angio/stromagenic growth factor. These findings suggest that circadian disruption induces the progression of malignant tumors via a Wnt signaling pathway

Characterization and modelling the mechanical behaviour of poly (l-lactic acid) for the manufacture of bioresorbable vascular scaffolds by stretch blow moulding

Bioresorbable Vascular Scaffolds (BVS) manufactured from poly (l-lactic acid) (PLLA) offer an alternative to metal scaffolds for the treatment of coronary heart disease. One of the key steps in the manufacture of these scaffolds is the stretch blow moulding process where the PLLA is biaxially stretched above glass transition temperature (Tg), inducing biaxial orientation and thus increasing ductility, strength and stiffness. To optimise the manufacture and performance of these scaffolds it is important to understand the influence of temperature and strain rate on the constitutive behaviour of PLLA in the blow moulding process. Experiments have been performed on samples of PLLA on a custom built biaxial stretch testing machine to replicate conditions typically experienced during blow moulding i.e. in a temperature range from 70 °C to 100 °C and at strain rates of 1 s−1, 4 s−1 and 16 s−1 respectively. The data is subsequently used to calibrate a nonlinear viscoelastic material model to represent the deformation behaviour of PLLA in the blow moulding process. The results highlight the significance of temperature and strain rate on the yielding and strain hardening behaviour of PLLA and the ability of the selected model to capture it