Konstantin Borodianskiy

Titanium alloys are widely employed in structural and electrochemical applications owing to their excellent mechanical properties and inherent corrosion resistance. However, their stability in harsh acidic environments, such as those encountered in energy storage systems, remains a critical issue. In this study, composite ceramic coatings were synthesized on a Ti6Al4V alloy using plasma electrolytic oxidation (PEO) in silicate-, phosphate-, and sulfate-based electrolytes, with and without the addition of α-alumina nanoparticles. The resulting coatings were comprehensively characterized to assess their surface morphology, chemical and phase compositions, and corrosion performance. Thus, the corrosion current density decreased from 9.7 × 10⁴ for bare Ti6Al4V to 143 nA/cm² for the coating fabricated in phosphate electrolyte with alumina nanoparticles, while the corrosion potential shifted anodically from –0.68 to +0.49 V vs. silver chloride electrode in 5 M H₂SO₄. Among the tested electrolytes, coatings produced in the phosphate-based electrolyte with Al₂O₃ showed the highest polarization resistance (113 kΩ·cm²), outperforming those fabricated in silicate- (71.6 kΩ·cm²) and sulfate-based (89.0 kΩ·cm²) systems. The composite coatings exhibited a multiphase structure with reduced surface porosity and the incorporation of crystalline oxide phases. Notably, titania–alumina nanoparticle composites demonstrated significantly enhanced corrosion resistance. These findings confirm that PEO-derived composite coatings provide an effective surface engineering strategy for enhancing the stability of the Ti6Al4V alloy in aggressive acidic environments relevant to advanced electrochemical systems.

This study investigates the synthesis and characterization of boron-modified nanotubular titania (NTO) arrays fabricated via a single-step anodizing process with varying concentrations of boric acid (BA). Following anodization, a reductive heat treatment was applied to facilitate the crystallization of the anatase phase in the boron-modified NTO. The effect of the BA concentration on the structural, morphological, and photoelectrochemical (PEC) properties of the NTOs was systematically explored through scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), luminescence, and UV-Vis spectrometry. The introduction of boron during anodization facilitated the formation of sub-bandgap states, thereby enhancing the light absorption and electron mobility. This study revealed the optimal BA concentration that yielded a 3.3-fold enhancement of the PEC performance, attributed to a reduction in the bandgap energy. Notably, the highest incident photon-to-current conversion efficiency (IPCE) was observed for NTO samples anodized at a 0.10 M BA concentration. These findings underscore the promise of boron-modified NTOs for advanced photocatalytic applications, particularly in solar-driven water-splitting processes.

Titanium alloys are frequently subjected to surface treatments to enhance their biocompatibility and corrosion resistance in biological environments. Plasma electrolytic oxidation (PEO) is an environmentally friendly electrochemical technique capable of forming oxide layers characterized by high corrosion resistance, biocompatibility, and strong adhesion to the substrate. In this study, the PEO process was performed using a low-melting-point ternary eutectic electrolyte composed of Ca(NO₃)₂–NaNO₃–KNO₃ (41–17–42 wt.%) with the addition of ammonium dihydrogen phosphate (ADP). The use of this electrolyte system enables a reduction in the operating temperature from 280 to 160 °C. The effects of applied voltage from 200 to 400V, current frequency from 50 to 1000 Hz, and ADP concentrations of 0.1, 0.5, 1, 2, and 5 wt.% on the growth of titanium oxide composite coatings on a Ti-6Al-4V substrate were investigated. The incorporation of Ca and P was confirmed by phase and chemical composition analysis, while scanning electron microscopy (SEM) revealed a porous surface morphology typical of PEO coatings. Corrosion resistance in Hank’s solution, evaluated via Tafel plot fitting of potentiodynamic polarization curves, demonstrated a substantial improvement in electrochemical performance of the PEO-treated samples. The corrosion current decreased from 552 to 219 nA/cm², and the corrosion potential shifted from −102 to 793 mV vs. the Reference Hydrogen Electrode (RHE) compared to the uncoated alloy. These findings indicate optimal PEO processing parameters for producing composite oxide coatings on Ti-6Al-4V alloy surfaces with enhanced corrosion resistance and potential bioactivity, which are attributed to the incorporation of Ca and P into the coating structure.

Ammonia has emerged as a promising fuel for solid oxide fuel cells (SOFCs) owing to its high energy density, high hydrogen content, and carbon-free nature. Herein, the electrocatalytic potential of a novel Ni-doped SFM double-perovskite (Sr_1.9Fe_0.4Ni_0.1Mo_0.5O_6-δ) is studied, for the first time, as an alternative anode material for symmetrical direct-ammonia SOFCs. Scanning and transmission electron microscopy characterization has revealed the exsolution of Ni-Fe nanoparticles (NPs) from the parent Sr₂Fe_1.5Mo_0.5O₆ under anode conditions, and X-ray diffraction has identified the FeNi₃ phase after exposure to ammonia at 800 °C. The active-exsolved NPs contribute to achieving a maximal ammonia conversion rate of 97.9% within the cell's operating temperatures (550-800 °C). Utilizing 3D-printed symmetrical cells with SFNM-GDC electrodes, the study demonstrates comparable polarization resistances and peak power densities of 430 and 416 mW cm^-2 for H₂ and NH₃ fuels, respectively, with long-term stability and a negligible voltage loss of 0.48% per 100 h during ammonia-fed extended galvanostatic operation. Finally, the ammonia consumption mechanism is elucidated as a multistep process involving ammonia decomposition, followed by hydrogen oxidation. This study provides a promising avenue for improving the performance and stability of ammonia-based SOFCs for potential applications in clean energy conversion technologies.

Anodization is a method to fabricate a tunable nanoporosity and thickness of alumina coating. This research is devoted to large-area hard anodization (HA), ultrahard anodization (UHA), and transitional modes. The phenomenon and challenges of UHA and the transition from HA are studied on large-area samples using linear-sweep voltammetry. The findings indicate that a uniform large-area thick coating can be achieved by utilizing pre-UHA modes. The study’s results indicate that UHA leads only to coatings with non-uniform thickness in large-area anodization. The peculiarities of pre-UHA are studied using different temperatures (0, 5, 10, and 15 °C) and processing times (1, 2, 4, 6, and 12 h) in a 0.3 M oxalic acid electrolyte. The current study shows the possibility for the fast growth of thick nanoporous alumina up to 235 ± 4 µm for only 12 h.

Nanotubular titanium oxide is widely known as a prospective semiconductor photocatalyst for the process of water splitting. Its photoelectrochemical (PEC) efficiency can be improved by doping with 3d metal. In this work, the synthesis of nanotubular titanium oxide (NTO) was carried out by anodizing titanium substrates using two doping techniques. First, Ni-doped TiO₂ was obtained by immersion in Ni salt solution; second, an ethylene glycol-based fluoride electrolyte containing Ni²⁺ ions solution was used. The obtained samples were analyzed using SEM, XRD, and photoelectrochemical methods. The produced Ni-doped NTO exhibited photocatalytic activity twice as high as that of nondoped NTO. Additionally, it was found that the immersion technique initiated a shift of the incident photon to converted electron (IPCE) spectra to the visible part of the spectrum.