How Is Rheology Involved in 3D Printing of Phase-Separated PVC-Acrylate Copolymers Obtained by Free Radical Polymerization

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

How Is Rheology Involved in 3D Printing of Phase-Separated PVC-Acrylate Copolymers Obtained by Free Radical Polymerization

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

Recyclable Epoxy Resin via Simultaneous Dual Permanent/Reversible Crosslinking Based on Diels-Alder Chemistry

Taking advantage of the reversible Diels-Alder (DA) reaction, a simple strategy to obtain recyclable epoxy resins is presented. For this purpose, blends of furan-functionalized and nonfunctionalized epoxy resin are prepared. After the addition of diamine and bismaleimide, blends are heated at 150 degrees C for 5 min, where the permanent amine/epoxy reaction has taken place and upon cooling to room temperature the reversible DA reaction has happened, giving rise to a dual permanent/nonpermanent network. Both reactions are confirmed by Fourier-transform infrared (FTIR) and C-13-crosspolarization, magic-angle spinning (CP/MAS) nuclear magnetic resonance (NMR). Modulated differential scanning calorimetry (MDSC) shows that the epoxy/amine and bismaleimide/amine curing reaction take place, after the DA reaction, simultaneously with the retroDA reaction and before the bismaleimide homopolymerization. Therefore, under the appropriate curing conditions, the Michael's addition and the bismaleimide homopolymerization do not avoid the formation of a hybrid network, as stated in other reports. The reversibility of the DA reaction in three consecutive cycles is confirmed by DSC. Finally, the dual-cured sample is reprocessed three times without significant loss of mechanical properties.The authors thank the Basque Government (IT1313-19), the University of the Basque Country (GIU19/077), and Mineco (MAT2017-84116-R), for the funding received to develop this work. Technical and human support provided by Macro-Behaviour-Mesostructure and Nanotechnology and NMR SGIker services of UPV/EHU are also gratefully acknowledged. The authors also thank Anne Bravo for the design of the table of contents. Documen

Thermo-rheological effects on succesful 3D printing of biodegradable polyesters

Unformatted preprint version of the submitted articleBiodegradable polybutylene succinate (PBS) and poly (butylene succinate-ran-adipate) (PBSA) were characterized to find the thermo-rheological bases for 3D printing by Fused Filament Fabrication (FFF). In dynamic viscoelastic measurements, the samples fulfilled time-temperature superposition and Cox Merz rule. The viscosity results were linked to the excellent filaments obtained and the observed good flow in the printer nozzle. Using specific tearing experiments, outstanding welding of the printed layers was obtained. Results were discussed considering the values of the entanglements density obtained by SAOS measurements. The main difference between both polymers was observed in the final production of 3D printed parts because the high crystallinity of PBS produced significant warpage, which prevented its use for practical purposes. On the contrary, the less crystalline PBSA random copolymer showed excellent performance during FFF. Thus, dimensionally stable and ductile printed objects were obtained, opening new processing routes for semi-crystalline biodegradable polyesters.This work has received funding from the European Union´s Horizon 2020 research and innovation program under the Marie Sklodowska-Curie grant agreement No 778092, from MINECO, project: MAT2017-83014-C2-1-P and from the Basque Government through grant IT1309-19

Study of the interlayer adhesion and warping during material extrusion-based additive manufacturing of a carbon nanotube/biobased thermoplastic polyurethane nanocomposite

Unformatted preprint version of the submitted articleA thermoplastic bio-polyurethane from renewable sources (TPU) and the nanocomposite developed by mixing it with carbon nanotubes (CNT) are investigated as potentially adequate for Material Extrusion-based Additive Manufacturing (EAM). Thermal and rheological features are studied from the perspective of their liaisons with printing adequacy and conditions. As predicted by rheology, both samples show good performance in filament elaboration and flow in the nozzle. Warpage is observed for TPU, but not for the nanocomposite, which is due to the effect of CNT nanoparticles on polymer chains dynamics. At the studied printing velocities, interlayer adhesion strength is independent of printing velocity implying that there is no significant chain orientation which can induce changes in the TPU entanglements. The nanocomposite shows a lower welding strength, notwithstanding both have the same chain entanglements density. This is explained by considering that the higher viscosity of TPU/CNT, as compared to TPU, reduces the melt diffusion coefficient.We would like to thank the financial support provided by the BIODEST project. This project has received funding from the European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No 778092. This work has also received funding from MINECO through project MAT2017-83014-C2-1-P and from the Basque Government through grant IT1309-19