An Advanced Surface Treatment Technique for Coating Three-Dimensional-Printed Polyamide 12 by Hydroxyapatite

Abstract

Polymer 3D printing has is used in a wide range of applications in the medical field. Polyamide 12 (PA12) is a versatile synthetic polymer that has been used to reconstruct bony defects. Coating its surface with calcium phosphate compounds, such as hydroxyapatite (HA), could enhance its bonding with bone. The aim of this study was to coat 3D-printed polyamide 12 specimens with hydroxyapatite by a simple innovative surface treatment using light-cured resin cement. Polyamide 12 powder was printed by selective laser sintering to produce 80 disc-shaped specimens (15 mm diameter × 1.5 mm thickness). The specimens were divided randomly into two main groups: (1) control group (untreated), where the surface of the specimens was left without any modifications; (2) treated group, where the surface of the specimens was coated with hydroxyapatite by a new method using a light-cured dental cement. The coated specimens were characterised by both Fourier transform infrared spectroscopy (FTIR) and Transmission Electron Microscopy (TEM), (n = 10/test). The control and treated groups were further randomly subdivided into two subgroups according to the immersion in phosphate-buffered saline (PBS). The first subgroup was not immersed in PBS and was left as 3D-printed, while the second subgroup was immersed in PBS for 15 days (n = 10/subgroup). The surfaces of the control and treated specimens were examined using an environmental scanning electron microscope (SEM) and energy dispersive X-ray analysis (EDXA) before and after immersion in PBS. Following the standard American Society for Testing and Materials (ASTM D3359), a cross-cut adhesion test was performed. The results of the FTIR spectroscopy of the coated specimens were confirmed the HA bands. The TEM micrograph revealed agglomerated particles in the coat. The SEM micrographs of the control 3D-printed polyamide 12 specimens illustrated the sintered 3D-printed particles with minimal porosity. Their EDXA revealed the presence of carbon, nitrogen, and oxygen as atomic%: 52.1, 23.8, 24.1 respectively. After immersion in PBS, there were no major changes in the control specimens as detected by SEM and EDXA. The microstructure of the coated specimens showed deposited clusters of calcium and phosphorus on the surface, in addition to carbon, nitrogen, and oxygen, with atomic%: 9.5, 5.9, 7.2, 30.9, and 46.5, respectively. This coat was stable after immersion, as observed by SEM and EDXA. The coat adhesion test demonstrated a stable coat with just a few loose coating flakes (area removed <5%) on the surface of the HA-coated specimens. It could be concluded that the 3D-printed polyamide 12 could be coated with hydroxyapatite using light-cured resin cement.