Rheology is proposed as a tool to explore plasticized poly(vinyl chloride) (PVC) formulations to be used in the fused filament fabrication (FFF) 3D printing process and so manufactures flexible and ductile objects by this technique. The viscoelastic origin of success/failure in FFF of these materials is investigated. The analysis of buckling of the filament is based on the ratio between compression modulus and viscosity, but for a correct approach the viscosity should be obtained under the conditions established in the nozzle. As demonstrated by small amplitude oscillatory shear (SAOS) measurements, PVC formulations have a crystallites network that provokes clogging in the nozzle. This network restricts printing conditions, because only vanishes at high temperatures, at which thermal degradation is triggered. It is observed that the analysis of the relaxation modulus G(t) is more performing than the G″/G′ ratio to get conclusions on the quality of layers welding. Models printed according to the established conditions show an excellent appearance and flexibility, marking a milestone in the route to obtain flexible objects by FFF.

The impact of plastics on the environment can be mitigated by employing biobased and/or biodegradable materials (i.e., bioplastics) instead of the traditional “commodities”. In this context, poly (butylene succinate) (PBS) emerges as one of the most promising alternatives due to its good mechanical, thermal, and barrier properties, making it suitable for use in a wide range of applications. Still, the PBS has some drawbacks, such as its high crystallinity, which must be overcome to position it as a real and viable alternative to “commodities”. This contribution covers the actual state-of-the-art of the PBS through different sections. The first section reviews the different synthesis routes, providing a complete picture regarding the obtained molecular weights and the greener alternatives. Afterward, we examine how different strategies such as random copolymerization and the incorporation of fillers can effectively modulate PBS properties to satisfy the needs for different applications. The impact of these strategies is evaluated in the crystallization behavior, crystallinity, mechanical and barrier properties, and biodegradation. The biodegradation is carefully analyzed, highlighting the wide variety of methodologies existing in the literature to measure PBS degradation through different routes (hydrolytic, enzymatic, and soil).

New auto-plasticised copolymers of poly(vinyl chloride)-r-(acrylate) and polyvinylchloride, obtained by radical polymerization, are investigated to analyse their capacity to be processed by 3D printing. The specific microstructure of the copolymers gives rise to a phase-separated morphology constituted by poly(vinyl chloride) (PVC) domains dispersed in a continuous phase of acrylate-vinyl chloride copolymer. The analysis of the rheological results allows the suitability of these copolymers to be assessed for use in a screw-driven 3D printer, but not by the fused filament fabrication method. This is due to the high melt elasticity of the copolymers, caused by interfacial tension between phases. A relationship between the relaxation modulus of the copolymers and the interlayer adhesion is established. Under adequate 3D-printing conditions, flexible and ductile samples with good dimensional stability and cohesion are obtained, as is proven by scanning electron microscopy (SEM) and tensile stress-strain tests.

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