Marta Mohedano

The present work compares the corrosion performance of additively manufactured (AM) Ti-6Al-4V ELI (Extra-Low Interstitials) alloy manufactured by Laser-Powder Bed Fusion (L-PBF) using virgin powder (Cycle 1/C1 sample) and reused powder feedstock after up to 34 cycles (Cycle 34/C34 sample) of manufacturing. The effect of powder reuse is also evaluated for anodizing and Flash-PEO-coated specimens in Harrison’s (25 °C) and Hanks’ solutions (37 °C), representing simulated atmospheric precipitation and physiological conditions, respectively. Specimens were characterized using common metallographic techniques, X-ray diffraction, scanning electron microscopy and optical profilometry. Corrosion resistance was evaluated using cyclic potentiodynamic polarization (PDP) tests. The oxygen content in the Ti-6Al-4V reaches 0.14 wt.% after 34 cycles (C34) of powder reuse, enhancing its passivity in both Harrison’s and Hanks’ solutions. Both virgin and reused powder builds are susceptible to localized corrosion in Hanks’ solution at potentials above 1.75 V. Melt pool borders are thought to be the preferential sites for localized corrosion, as indicated by Volta potential measurements (ΔV = 100 mV). The number of cycles does not significantly affect the current–voltage responses for anodizing and flash-Plasma Electrolytic Oxidation (Flash-PEO) treatments, although anodizing is slightly more responsive to variations in surface roughness (i.e., real specimen area). Anodizing and Flash-PEO reduce the passive current density by nearly two orders of magnitude. Even after surface treatment, the alloy printed with reused powder revealed better passivity. Flash-PEO coatings yielded significant protection against localized corrosion. This unlocks Flash-PEO processing as a successful protection approach for AM biomedical components.

Organic coatings are used as one of the most effective strategies for the corrosion protection of metals. Nowadays, due to environmental regulations, the use of water-based coatings has become essential compared to solvent-based ones. However, their application to magnesium alloys remains largely unexplored due to their high reactivity with water. In the present work, a phosphate-functionalized waterborne binder is applied to AZ31B magnesium alloy. The surface has been modified by four different pre-treatments, respectively: (i) mechanical grinding, (ii) pickling, (iii) conventional conversion treatment, and (iv) a novel conversion treatment based on layered double hydroxides (LDH). The most promising pre-treatments are selected to explore their synergy with a biobased waterborne binder, containing CeO₂ nanoparticles as a corrosion inhibitor. The morphology and composition of the different systems are studied, prior to and after corrosion tests in NaCl solution, by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS). Results obtained by electrochemical impedance spectroscopy (EIS) in NaCl solution have revealed not only that LDH performs better than the conventional conversion treatment but also the synergy between LDH pre-treatment and CeO₂ nanoparticles when two organic layers are used.

There is a knowledge gap about the effect of pharmaceutical agents on the biodegradation of Mg-based resorbable implants. The present work investigates how three common antibiotics and three anti-inflammatory drugs affect the corrosion of high-purity Mg, with and without ceramic and hybrid ceramic/polymeric coatings, using electrochemical impedance spectroscopy and hydrogen evolution tests. A Ca-P-Si-based ceramic coating is developed using plasma electrolytic oxidation (PEO), after the AC voltage and frequency parameters are optimized. A hybrid coating included a PEO and a poly(ε-caprolactone) (PCL) top layer formed by dip coating. High-purity Mg exhibited an instantaneous onset of corrosion with a corrosion rate of 90 μm/year after 24 h of immersion in a modified α-MEM. A hybrid PEO/PCL coating prevents the onset of corrosion for at least 5 h and reduces the H₂ evolution during the following 90 h by two times by the precipitation of 5–40 μm thick Ca-P surface deposits. Gentamicin, naproxen, streptomycin, ciprofloxacin and paracetamol were found to be corrosion accelerators with respect to bare h.p. Mg, whereas aspirin was found to be an inhibitor. Streptomycin-functionalized PEO/PCL system exhibited an active protection mechanism, triggered upon the release of the coating and substrate cations, associated with the coating defect-blocking action of the insoluble Me(II)-streptomycin chelates.

In this work, silicon oxide based coatings with embedded graphene nanoplatelets (content ranging from 1.8 wt.% to 7.2 wt.%) have been developed following the sol-gel route, using AISI430 stainless steel as substrate and dip and roll-to-roll as coating techniques. The tribological and corrosion behaviour of these coatings have been evaluated and compared to bare steel. Concerning tribological behaviour, the coefficient of friction and wear print were significantly reduced with increasing the graphene nanoplatelets content. Regarding corrosion, all coatings showed improved corrosion behaviour compared to bare steel. However, higher concentration of nanoplatelets revealed a negative effect on the corrosion resistance, probably due to aggregation. Taking into account these two counteracting effects, as final part of this work, a bilayer coating with different graphene content has been proposed and fabricated. A top layer, with high graphene nanoplatelets concentration has allowed enhanced tribological properties whereas bottom layer, with no graphene nanoplatelets assures corrosion inhibition under harsh environments.

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.

The present work aims to provide corrosion performance data for an additively manufactured Ti6Al4V alloy in saline and polluted environments. The as-received additively manufactured material underwent heat treatment at 850 °C for 3 h to transform the acicular α’ microstructure into a lamellar α microstructure. Comparative corrosion assessments were conducted between the heat-treated substrates, the as-received condition, and a conventionally mill-annealed alloy. Potentiodynamic polarization experiments were carried out in saline (3.5 wt.% NaCl) and acid aqueous media ((NH₄)₂SO₄ containing Harrison’s solution). The corrosion performance of additively manufactured substrates matched or surpassed that of the conventional alloy in Harrison’s solutions while remaining inferior in saline medium, despite forming a thicker passive film. Overall, the XY plane showed better corrosion performance, particularly after the elimination of the acicular α’ martensite by the applied heat treatment. The results also suggested that the presence of the coarse β phase was beneficial in 3.5 wt.% NaCl solution and detrimental in Harrison’s solutions, more so in acidified and fluorinated conditions.

In this investigation, the sol–gel method is employed along with a corrosion inhibitor to seal a plasma electrolytic oxidation (PEO) coating, aiming to improve the long-term corrosion resistance of the AZ31 Mg alloy. Following an initial screening of corrosion inhibitors, 8-hydroxyquinoline (8HQ) is incorporated into the hybrid PEO/sol–gel system using two methods: (i) post-treatment of the PEO layer through immersion in an inhibitor-containing solution; (ii) loading the inhibitor into the sol–gel precursor. The characterization includes scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), ultraviolet-visible spectroscopy (UV-vis), and water drop contact angle measurements. The rheological properties of the inhibitor-loaded sol–gel precursors are assessed by measuring flow curves. The corrosion processes are evaluated in a saline solution through electrochemical impedance spectroscopy (EIS) and immersion tests with unscratched and scratched specimens, respectively. The results demonstrate the successful incorporation of the inhibitor for both loading strategies. Regardless of the loading approach, systems containing 8HQ exhibit the most favourable long-term corrosion resistance.