Carole Boissard
Petroleum-based polymers and composites are commonly used in a wide variety of application fields. However ecological concerns, increasing oil prices and dwindling natural resources explain why nowadays industrial and public interest is more than ever focused on new bio-based – “greener”- products. In order to find viable substitutes for petroleum-based materials, major efforts are devoted to the development of sustainable solutions combining fully compostable matrices and fibres from renewable resources. Polylactide (or polylactic acid) (PLA) is currently one of the most versatile biodegradable polymers derived from renewable resources such as non-food crops of corn or sugar cane. Its transformation into foamed cellular structures would decrease its density and at the same time may improve its specific mechanical properties. This could provide cost-effective and sustainable products for packaging and construction. In the context of developing “green” foams, the focus in the present work has been on a solvent-free process based on physical foaming with supercritical carbon dioxide (ScCO2) as a foaming agent. This foaming process includes thermally driven but kinetically controlled phenomenon. Solubility and diffusion of the gas in the molten polymer, cell nucleation and growth, as well as stabilization of the final foam structures were studied for neat and composite materials. At low processing temperatures and low depressurization rates, homogeneous structures were obtained thanks to a balance between cell growth mechanisms and cell stabilization, thus limiting uncontrolled cell coalescence. The density of the resulting polylactide foams ranged from 0.12 to 0.3 g/cm3 with corresponding compression moduli of 6 to 73 MPa respectively. The processing windows were strongly dependent on the rheological melt properties of the PLAs. PLA is generally considered to be a high strength, high modulus thermoplastic but its brittleness has limited its industrial use. PLA was therefore combined with wood fibres (WF) and microfibrillated cellulose (MFC) in order to improve its mechanical performance without compromising its environmental impact. Two compounding methods, a wet mixing papermaking-like process and a solvent casting process were investigated for the production of WF/PLA and MFC/PLA biocomposites. Degradation of PLA occured during wet-mixing, due to the water used as a dispersant, and to several heating steps applied during compounding. Improvement of the drying and processing conditions and/or the replacement of water by isopropanol limited this degradation. The presence of cellulose fibres considerably modified foaming mechanisms; gas solubility was decreased and the coefficient of diffusion increased, leading to lower quantities of CO2 available for foaming. In addition, stiffness of the fibre network impeded full expansion of the polymer matrix. Thus smaller cells were created. Densities from 0.15 (neat PLA) to 0.37 and 0.55 g/cm3 and moduli ranging from 35 (neat PLA) to 125.5 and 373 MPa were obtained by the addition of 5wt% WF and MFC respectively. Addition of a chain extender enabled viscosity of the matrix to be increased causing increased orientation of the fibre network during flow and hence fibre alignment in the cell walls. Density was thus decreased by 95 % to 0.017 g/cm3 and compression modulus decreased to 0.32 MPa for 5wt% WF composite. Cell wall shrinkage was observed in the neat PLA foams obtained with the chain extender. This was reduced by adding wood fibres while maintaining similar density and modulus. Cellulose fibres act as an extra scaffold in the cellular structures. Industries are currently considering the use of these materials for applications in packaging e.g. as cushioning materials, or in architecture as display panels, or as sandwich core materials for the replacement of expanded polystyrene, polyvinyl chloride or polyurethane foams.
EPFL2012
