Optimizing fused deposition modelling: the impact of geometrical slicing parameters on mechanical properties

This comprehensive study explores the intricate world of 3D printing, with a focus on Fused Deposition Modelling (FDM). It sheds light on the critical factors that influence the quality and mechanical properties of 3D printed objects. Using an optical microscope with 40X magnification, the shapes of the printed beads is correlated to specific slicing parameters, resulting in a 2D parametric model. This mathematical model, derived from real samples, serves as a tool to predict general mechanical behaviour, bridging the gap between theory and practice in FDM printing. The study begins by emphasising the importance of geometric parameters such as layer height, line width and filament tolerance on the final printed bead geometry and the resulting theoretical effect on mechanical properties. The introduction of VPratio parameter (ratio between the area of the voids and the area occupied by printed material) allows the quantification of the variation of geometric slicing parameters on the improvement or reduction of mechanical properties. The study also addresses the effect of overhang and the role of filament diameter tolerances. The research continues with the introduction of 3D FEM (Finite Element Analysis) models based on the RVE (Representative Volume Element) to verify the results obtained from the 2D model and to analyse other aspects that affect mechanical properties and not directly observable with the 2D model. The study also proposes a model for the examination of 3D printed infill structures, introducing also an innovative methodology called “double RVE” which speeds up the calculation of mechanical properties and is also more computationally efficient. Finally, the limitations of the RVE model are shown and a so-called Hybrid RVE-based model is created to overcome the limitations and inaccuracy of the conventional RVE model and homogenization procedure on some printed geometries.

Study of the activity and enantioselectivity of alginate-based catalysts in Friedel-Crafts reactions

This thesis is part of a long-term project which aims to demonstrate for the first time that alginate gel beads can be used as chiral heterogeneous catalysts for enantioselective reactions. Alginate barium beads were prepared as previously optimized and applied to the Friedel-Crafts reaction between indoles and nitroalkenes. New substrates were tested, showing that the reaction can accommodate different nitroalkenes and indoles, affording the corresponding products with moderate yields and good enantioselectivities. However, aliphatic nitroalkenes cannot be used as they degrade under the catalytic reaction conditions. Preliminary study on the recyclability of the heterogeneous catalyst indicated a moderate stability of the catalyst, which can be used for few cycles with a slight erosion of enantioinducing power. Some directions for future improvements (storage and work-up solvent, use of ultrasonic bath) have been suggested.