Tamay, D; Gokyer, S.; Schmidt, J.; Vladescu, A.; Yilgor Huri, P.; Hasirci, V.; Hasirci, N. (2022) Corrosion Resistance and Cytocompatibility of Magnesium-Calcium Alloys Modified with Zinc- or Gallium- Doped Calcium Phosphate Coatings, ACS Applied Materials & Interfaces, (IF: 9.229), 2022, 14:1, 104–122. DOI: 10.1021/acsami.1c16307

In orthopedic surgery, metals are preferred to support or treat damaged bones due to their high mechanical strength. However, the necessity for a second surgery for implant removal after healing creates problems. Therefore, biodegradable metals, especially magnesium (Mg), gained importance, although their extreme susceptibility to galvanic corrosion limits their applications. The focus of this study was to control the corrosion of Mg and enhance its biocompatibility. For this purpose, surfaces of magnesium–calcium (MgCa₁) alloys were modified with calcium phosphate (CaP) or CaP doped with zinc (Zn) or gallium (Ga) via microarc oxidation. The effects of surface modifications on physical, chemical, and mechanical properties and corrosion resistance of the alloys were studied using surface profilometry, goniometry, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), nanoindentation, and electrochemical impedance spectroscopy (EIS). The coating thickness was about 5–8 μm, with grain sizes of 43.1 nm for CaP coating and 28.2 and 58.1 nm for Zn- and Ga-doped coatings, respectively. According to EIS measurements, the capacitive response (Y_c) decreased from 11.29 to 8.72 and 0.15 Ω^–1 cm^–2 sⁿ upon doping with Zn and Ga, respectively. The E_corr value, which was −1933 mV for CaP-coated samples, was found significantly electropositive at −275 mV for Ga-doped ones. All samples were cytocompatible according to indirect tests. In vitro culture with Saos-2 cells led to changes in the surface compositions of the alloys. The numbers of cells attached to the Zn-doped (2.6 × 10⁴ cells/cm²) and Ga-doped (6.3 × 10⁴ cells/cm²) coatings were higher than that on the surface of the undoped coating (1.0 × 10³ cells/cm²). Decreased corrosivity and enhanced cell affinity of the modified MgCa alloys (CaP coated and Zn and Ga doped, with Ga-doped ones having the greatest positive effect) make them novel and promising candidates as biodegradable metallic implant materials for the treatment of bone damages and other orthopedic applications.