In the present work, a hybrid hierarchical coating (HHC) system comprising a plasma electrolytic oxidation (PEO) coating and a homogeneously porous structured polycaprolactone (PCL) top-coat layer, loaded with ciprofloxacin (CIP), was developed on Mg3Zn0.4Ca alloy. According to the findings, the HHC system avoided burst release and ensured gradual drug elution (64% over 240 h). The multi-level protection of the magnesium alloy is achieved through sealing of the PEO coating pores by the polymer layer and the inhibiting effect of CIP (up to 74%). The corrosion inhibition effect of HHC and the eluted drug is associated with the formation of insoluble CIP-Me (Mg/Ca) chelates that repair the defects in the HHC and impede the access of corrosive species as corroborated by FTIR spectra, EIS and SEM images after 24 h of immersion. Therefore, CIP participates in an active protection mechanism by interacting with cations coming through the damaged coating.

Bioactive Plasma Electrolytic Oxidation (PEO) coatings enriched in Ca, P and F were developed on Mg0.6Ca and Mg0.6Ca2Ag alloys with the aim to impede their fast degradation rate. Different characterization techniques (SEM, TEM, EDX, SKPFM, XRD) were used to analyze the surface characteristics and chemical composition of the bulk and/or coated materials. The corrosion behaviour was evaluated using hydrogen evolution measurements in Simulated Body Fluid (SBF) at 37 °C for up to 60 days of immersion. PEO-coated Mg0.6Ca showed a 2–3-fold improved corrosion resistance compared with the bulk alloy, which was more relevant to the initial 4 weeks of the degradation process. In the case of the Mg0.6Ag2Ag alloy, the obtained corrosion rates were very high for both non-coated and PEO-coated specimens, which would compromise their application as resorbable implants. The amount of F⁻ ions released from PEO-coated Mg0.6Ca during 24 h of immersion in 0.9% NaCl was also measured due to the importance of F⁻ in antibacterial processes, yielding 33.7 μg/cm², which is well within the daily recommended limit of F⁻ consumption.

A hierarchical hybrid coating (HHC) comprising a ceramic oxide layer and two biodegradable polymeric (polycaprolactone, PCL) layers has been developed on Mg3Zn0.4Ca cast alloy in order to provide a controlled degradation rate and functionality by creating a favorable porous surface topography for cell adhesion. The inner, ceramic layer formed by plasma electrolytic oxidation (PEO) has been enriched in bioactive elements (Ca, P, Si). The intermediate PCL layer sealed the defect in the PEO layer and the outer microporous PCL layer loaded with the appropriate active molecule, thus providing drug-eluting capacity. Morphological, chemical, and biological characterizations of the manufactured coatings loaded with ciprofloxacin (CIP) and paracetamol (PAR) have been carried out. In vitro assays with cell lines relevant for cardiovascular implants and bone prosthesis (endothelial cells and premyoblasts) showed that the drug-loaded coating allows for cell proliferation and viability. The study of CIP and PAR cytotoxicity and release rate indicated that the porous PCL layer does not release concentrations detrimental to the cells. However, complete system assays revealed that corrosion behavior and increase of the pH negatively affects cell viability. H₂ evolution during corrosion of Mg alloy substrate generates blisters in PCL layer that accelerate the corrosion locally in crevice microenvironment. A detailed mechanism of the system degradation is disclosed. The accelerated degradation of the developed system may present interest for its further adaptation to new cancer therapy strategies.

Bioactive plasma electrolytic oxidation (PEO) coatings were developed on a wrought Mg0.5Zn0.2Ca alloy using a transparent electrolyte for easy maintenance and waste disposal, compared to a conventional suspension-based solution. Treatment times of 300, 600, and 900 s were evaluated for their effects on coating morphology, composition, and corrosion resistance. A short-time electrochemical impedance spectroscopy (EIS) screening was utilized to identify coatings with optimal corrosion protection. To assess the degradation rate and corrosion mechanisms, hydrogen evolution was monitored under pH-controlled quasi-in vivo conditions over extended immersion periods. Coating thickness increased by only 3% from 300 to 900 s of treatment (13 and 18 µm, respectively), with pore bands formed near the barrier layer at 900 s. The short-term EIS screening revealed that the coatings produced at 600 and 900 s were less protective and consistent than those at 300 s due to the presence of pore bands, which increased permeability. Hydrogen evolution measurements during 5 days of immersion at pH 7.4 indicated a tenfold higher degradation rate of the PEO-coated alloy compared to the bare substrate. Therefore, none of the PEO coatings provided effective corrosion protection after 24 h of immersion, which is attributed to crack formation at the PEO/corrosion products interface. This highlights the importance of crevices in the corrosion of Mg-Zn-Ca alloys. The presence of ZnO exacerbates the corrosion of magnesium in crevice areas.