Biodegradation and Antimicrobial Properties of Zinc Oxide-Polymer Composite Materials for Urinary Stent Applications

Research advancements in the field of urinary stents have mainly been in the selection of materials and coatings to address commonly faced problems of encrustation and bacterial adhesion. In this study, polylactic acid (PLA) and polypropylene (PP) were evaluated with zinc oxide (ZnO) coating to assess its ability to reduce or eliminate the problems of encrustation and bacteria adhesion. PLA and PP films were prepared via twin screw extrusion. ZnO microparticles were prepared using sol-gel hydrothermal synthesis. The as-prepared ZnO microparticles were combined in the form of a functional coating and deposited on both polymer substrates using a doctor blade technique. The ZnO-coated PP and PLA samples as well as their uncoated counterparts were characterized from the physicochemical standpoints, antibacterial and biodegradation properties. The results demonstrated that both the polymers preserved their mechanical and thermal properties after coating with ZnO, which showed a better adhesion on PLA than on PP. Moreover, the ZnO coating successfully enhanced the antibacterial properties with respect to bare PP/PLA substrates. All the samples were investigated after immersion in simulated body fluid and artificial urine. The ZnO layer was completely degraded following 21 days immersion in artificial urine irrespective of the substrate, with encrustations more evident in PP and ZnO-coated PP films than PLA and ZnO-coated PLA films. Overall, the addition of ZnO coating on PLA displayed better adhesion, antibacterial activity and delayed the deposition of encrustations in comparison to PP substrates.

Durability of Nanosized Oxygen-Barrier Coatings on Polymers

Yves Leterrier

Research on silicon oxide thin films developed as gas-barrier protection for polymer-based components is reviewed, with attention paid to the relations between (i) coating defects, cohesive strength and internal stress state, and (ii) interfacial interactions and related adhesion to the substrate. The deposition process of the oxide from a vapor or a plasma phase leads in both cases to the formation of covalent bonds between the two materials, with high adhesion levels. The oxide coating contains nanoscopic defects and microscopic flaws, and their respective effect on the barrier performance and mechanical resistance of the coating is analyzed. Potential improvements are discussed, including the control of internal stresses in the coating during deposition. Controlled levels of compressive internal stresses in the coating are beneficial to both the barrier performance and the mechanical reliability of the coated polymer. An optimal coating thickness, with low oxygen permeation and high cohesive strength, is determined from experimental and theoretical analyses of the failure mechanisms of the coating under mechanical load. These investigations are found relevant to tailor the interactions and stress state in the interfacial region, in order to improve the reliability of the coating/substrate assembly.

2003

Functionally graded polymer nanocomposites using magnetic fields

Tommaso Nardi

Functionally Graded Materials (FGM) are a class of materials in which the composition and the properties gradually change over the volume. The present PhD project aims to generate a full understanding of a novel synthetic strategy for polymeric FGMs based on the magnetophoretic motion of magnetic nanofillers in a polymer matrix under the application of an external magnetic field gradient. Due to its high rate, costâeffectiveness and lowâtoxicity, UV polymerization was considered as the first curing option for the magnetic nanocomposites. The curability problem deriving from the presence of opaque particles was tackled by studying two different systems based on the same hyperbranched acrylated polymer matrix (HBP): one containing bare Fe3O4 nanoparticles whereas the other loaded with Fe3O4@SiO2 coreâshell nanoparticles. The employment of Fe3O4@SiO2 NPs for the synthesis of magnetic polymeric films showed to be effective towards the inclusion of 10âtimes higher particle volume fractions compared to formulations including bare Fe3O4. By adding Fe3O4@SiO2 nanoparticles to the UVâcurable matrix, the motion of the magnetic responsive filler was induced upon the application of magnetic field gradients generated by permanent magnets. The process was speeded up through the employment of a simple setâup composed of two block magnets in repulsion configuration and through the functionalization of the particle surfaces with an acrylated silane. From the experimental analysis of the photocuring process, the residual stresses arising during the photopolymerization of functionally graded composite coatings based on the UVâcurable HBP matrix and Fe3O4@SiO2 nanoparticles were evaluated with a Finite Element Method approach. These coatings were able to consistently decrease the residual stresses at the coatingâsubstrate interface compared to those encountered either in composites with homogeneous compositions or in the pure polymer, provided that reinforcing fillers were concentrated at the coatingâsubstrate interface. If instead nanoparticles were concentrated at the free surface, graded nanocomposite coatings could reduce by as much as 40% the interfacial stress arising from thermal variations, as demonstrated through numerical simulations. Nanoindentation tests were carried out on the surface of polymer nanocomposites exhibiting either graded or homogeneous distributions of Fe3O4@SiO2 nanoparticles in the UVâcurable matrix. It was experimentally shown how only at relatively small indentation depths, large increases in modulus and hardnesswere obtained for graded composites with respect to their homogeneous counterparts. Through a Material Point Method approach, experimental nanoindentation tests were successfully simulated. Finally, nanocomposite systems based on epoxy matrices were considered. In particular, composites with gradients in permittivity were synthesized through the application of a magnetic field to suspensions of highâpermittivity Fe3O4@TiO2 particles in an epoxy resin. The application of the magnetic force not only induced the movement of the particles, but also caused their alignment in high aspect ratio structures, resulting in rather steep permittivity gradients. Numerical simulations clarified how the asâsynthesized materials, employed as insulators, have the potential to efficiently reduce the electric field stress at the electrodeâinsulator interface and have intrinsic durability advantages over their homogeneous counterparts.

EPFL2015

Functionally graded polymer nanocomposites using magnetic fields

Tommaso Nardi

EPFL2015