Fuente: Polymers Polymers, Vol. 17, Pages 3263: TiO2, GO, and TiO2/GO Coatings by APPJ on Waste ABS/PMMA Composite Filaments Filled with Carbon Black, Graphene, and Graphene Foam: Morphology, Wettability, Thermal Stability, and 3D Printability
Polymers doi: 10.3390/polym17243263
Authors:
Alejandra Xochitl Maldonado Pérez
Alma Delfina Arenas Flores
José de Jesús Pérez Bueno
Maria Luisa Mendoza López
Yolanda Casados Mexicano
José Luis Reyes Araiza
Alejandro Manzano-Ramírez
Salomón Ramiro Vásquez García
Nelly Flores-Ramírez
Carlos Montoya Suárez
Edain Belén Pérez Mendoza

This work presents a multifactorial strategy for reusing waste thermoplastics and generating multifunctional filaments for additive manufacturing. Acrylonitrile–butadiene–styrene (ABS) waste and commercial poly(methyl methacrylate) (PMMA) were compounded with carbon black (CB), graphene (G), or graphene foam (GF) at different loadings and extruded into composite filaments. The aim is to couple filler-induced bulk modifications with atmospheric pressure plasma jet (APPJ) surface coatings of TiO2 and graphene oxide (GO) to obtain waste-derived filaments with tunable morphology, wettability, and thermal stability for advanced 3D-printed architectures. The filaments were subsequently coated with TiO2 and/or GO using an APPJ process, which tailored surface wettability and enabled the formation of photocatalytically relevant interfaces. Digital optical microscopy and SEM revealed that CB, G, and GF were reasonably well dispersed in both polymer matrices but induced distinct surface and cross-sectional morphologies, including a carbon-rich outer crust in ABS and filler-dependent porosity in PMMA. For ABS composites, static contact-angle measurements show that APPJ coatings broaden the apparent wettability window from ~60–80° for uncoated filaments to ~40–50° (TiO2/GO) up to >90° (GO), corresponding to a ≈150% increase in contact-angle span. For PMMA/CB composites, TiO2/GO coatings expand the accessible contact-angle range to ~15–125° while maintaining surface energies around 50 mN m−1. TGA/DSC analyses confirm that the composites and coatings remain thermally stable within typical extrusion and APPJ processing ranges, with graphene showing only ≈3% mass loss over the explored temperature range, compared with ≈65% for CB and ≈10% for GF. Fused deposition modeling trials verify the printability and dimensional fidelity of ABS-based composite filaments, whereas PMMA composites were too brittle for reliable FDM printing. Overall, combining waste polymer reuse, tailored carbonaceous fillers, and APPJ TiO2/GO coatings provides a versatile route to design surface-engineered filaments for applications such as photocatalysis, microfluidics, and soft robotics within a circular polymer manufacturing framework.