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

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

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

Poly(vinyl chloride), a historical polymer still evolving

Poly(vinyl chloride) (PVC) is one of the commodity polymers of the highest worldwide consumption still in continuous evolution. The recent demonstration of the adaptability of this material for extrusion-based 3D printing techniques opens the possibility of manufacturing a large-scale of tailored flexible and ductile PVC objects, apart from those already registered in the market. The most important characteristics of this polymer from a scientific and technological point of view are described here; i.e., some figures and facts concerning the production and applications and, the two main drawbacks of the polymer: thermal degradation and plasticizer exudation. The most recent efforts and advances to overcome polymer limitations and develop new fields of applications based on modification reactions, in solution, at the surface and in the melt state, as well as the use of PVC formulations in the emerging processing technology of additive manufacturing are addressed.The continuous collaboration of ERCROS with academia on the subject of PVC along last decades and the supply of samples is acknowledged. CM acknowledges the Spanish Ministry of Science, Innovation and Universities, grant number MAT 2020 -83014-C2-2-P

Searching for Rheological Conditions for FFF 3D Printing with PVC Based Flexible Compounds

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

Shedding light on the viscoelastic behavior of artificial and human tears: A microrheological approach

12 pags., 9 figs., 3 tabs.This study conducts research on the viscoelastic properties of biological fluids, including both hyaluronic acid-containing lubricating eye drops and human tears, by means of passive microrheology. By tracking the Brownian motion of tracer particles of various sizes in the fluids, we were able to probe their viscoelastic properties. The results showed that the viscoelastic properties of artificial tears, such as Newtonian viscosity and relaxation time, scale to the concentration and macromolecular size of hyaluronic acid, resembling unentangled semidiluted solutions. Moreover, human tears were found to have a viscosity that is 50% greater than that of pure water, comparable to artificial tears containing 0.1% hyaluronic acid, but with a relaxation time one order of magnitude longer than ophthalmic solutions. This behavior was attributed to their intricate composition. The distinctive aspect of this study lies in demonstrating the feasibility of measuring the rheological properties of human tears, a biofluid of great interest, using extremely small sample volumes and microrheology, providing comprehensive information across a wide range of frequencies approaching those corresponding to blinking upon the application of the Cox–Merz rule. These findings are of significant value as they pave the way for future research on small volumes of tears from ophthalmic patientsThis research was supported by the CSIC, Spain—Project No. PIE202250E035, by the Basque Government—Project G.V. SAN 22/11–2022333039, and by the MICINN (Ministerio de Ciencia e Innovacion), Spain—Project No. FISS-21-RD21/0002/0041.Peer reviewe