Synthesis and characterization of thin film metallic glasses for biomedical applications
Résumé
Bioimplants are usually made of a corrosion-resistant metal such as stainless steels, cobalt chromium and titanium alloys [1]. Extensive research has been done on degradable stents, either polymer-based [2] or metal-based [3]. The search for biodegradable metals showing uniform corrosion and mechanical properties equal or higher to those of currently used permanent biomaterials is still an open challenge. Among the latter, Zn-based alloys obtained by melding and extrusion appear promising in terms of biodegradability, biocompatibility and mechanical properties [4,5]. In addition, the degradation rate should be adapted to complete arterial remodelling and tissue healing. This work aims to investigate corrosion behavior and mechanical properties as well as the aging in simulated biological medium and the endothelial cytotoxicity of ZnZr and ZnMg thin films deposited by magnetron co-sputtering on silicon substrates.
ZnxZr1-x and ZnxMg1-x thin film alloys were prepared on silicon substrate by RF magnetron co-sputtering using pure metallic targets. The structural and chemical properties were investigated by SEM, XRD and EDS techniques. Young’s modulus and hardness were assessed from nanoindentation tests with a continuous stiffness measurement. Degradability test were performed in simulated body fluid (SBF) at 37°C under gentle shaking. Electrochemical experiments were conducted in a standard three electrodes cell. Cell viability was analyzed after 72 h using a resazurin-based assay of the metabolic activity.
XRD patterns of ZnZr thin film alloys (Fig.1a) are characterized by the presence of a broad hump peak between low (30 at.%) and high (92 at. %) of Zn concentration. the average interatomic distance showed a continuous decrease from Zr-rich to Zn-rich films (Fig. 1b), as predicted by the Zen’s rule [6]. Large softening of Young’s modulus 150-100 GPa (-30%) is observed for the crystalline to amorphous phase transition at xc1, followed by a continuous increase as a function of x, in the amorphous region, in agreement with the binding distance shortening. Hardness mostly decreases from 8.5 GPa to 3.5 GPa with increasing Zn addition. Moreover, films with a Zn concentration higher than 80% do not exhibit any cytotoxicity for human endothelial cells. Fig. 1: (a) XRD patterns of the ZnZr films deposited at room temperature and (b) Average interatomic distance vs. Zn concentration x. Empty squares are theoretical calculations according to Zen’s law [6].
Amorphous ZnZr alloys films deposited by magnetron co-sputtering with zinc content in the 30 to 92 % atomic range exhibit smooth surface. Substituting Zr by Zn atoms decreased the average interatomic distances resulting in a shortening of binding distances, hence a stiffening of Young’s modulus. A quick corrosion rate in SBF was evidenced for Zn rich films. Analysis of cytotoxicity versus human endothelial cells indicate a good cytocompatibility for ZnZr films with 80 at.% Zn content. Thus, thin metallic amorphous layers obtained by magnetron co-sputtering on Si substrate could be further considered for the development of novel Zn-based degradable implants