Nanoporous gold (np-Au) has attracted significant attention for biomedical and electrochemical applications due to its high surface area, tunable morphology, and excellent biocompatibility. In this study, polycrystalline gold surfaces were modified by anodization in 0.3-0.9 M oxalic acid to produce np-Au layers. The influence of anodization conditions on surface morphology, chemical composition, electronic properties, and corrosion resistance in artificial saliva was systematically investigated. Surface morphology and porosity were analyzed by scanning electron microscopy combined with image analysis, revealing a transition from fine and uniform porosity to highly developed but structurally heterogeneous nanoporous structures with increasing oxalic acid concentration. Energy-dispersive spectroscopy confirmed surface oxidation and adsorption of oxygen- and carbon-containing species after anodization, while gold remained the dominant component. Scanning Kelvin probe measurements demonstrated significant modifications of surface electronic properties, including changes in contact potential difference, governed by nanostructure geometry and surface chemistry. Electrochemical tests in artificial saliva showed that increasing nanoporousness led to reduced thermodynamic stability, with the sample anodized in 0.3 M oxalic acid providing the most favorable balance between corrosion resistance and surface activity. These results demonstrate that oxalic acid anodization is a simple and effective approach for tailoring gold surfaces for biomedical applications, particularly in dentistry.
This work investigates the structural evolution and electrocatalytic activity of the amorphous metal alloy Al87Y4Gd1Ni4Fe4 during short-term annealing and its effect on the kinetics of the hydrogen evolution reaction (HER) in 1 M KOH. It is shown that a 5 min heat treatment at 647 ± 2 K initiates controlled nanocrystallisation with the formation of AlFe2Ni, GdFe2 and Al(X) (X = Gd, Ni, Y, Fe) phases, which are uniformly dispersed in the amorphous matrix. According to XRD, DSC and HRTEM data, it was established that the formation of intermetallic nanodomains leads to a decrease in charge transfer energy barriers and the appearance of additional active centres of H* adsorption. Electrochemical studies have shown an increase in cathode current density, an increase in i0 by 2-3 orders of magnitude, and a decrease in Rct after annealing, confirming the improvement in HER kinetics. Potentiostatic tests showed an increase in the volumetric hydrogen evolution rate from 35.1 to 106.0 mL/(g·min) during the first immersion and up to 217.9 mL/(g·min) during reuse. SEM/EDS analysis revealed surface reconstruction and Ni enrichment after HER, which contributes to the acceleration of the H* recombination stage. The synergy of the amorphous matrix and nanophases ensures high electrocatalytic activity and stability of the system, making annealed AMA a promising low-cost catalyst for alkaline hydrogen evolution.
Amorphous metal alloys (AMAs) are characterized by good mechanical and electrochemical properties. However, due to crystallization processes occurring at higher temperatures (Ta ˃ 600 K), these properties may deteriorate. The aim of this work was to investigate the effects of short-term annealing at T3 = 611 ± 1 K and to determine the risks of such thermal modifications for the electrochemical properties of the material. A comprehensive analysis shows that short-term isothermal annealing (5 min) of the amorphous metal alloy Al87Y4Gd1Ni8 at a temperature of 611 ± 1 K improves the tribological properties of the material. However, it has been established that heat treatment for 5 min is optimal and leads to temporary thickening of the film and the formation of an almost ideal double layer, but annealing for 15-60 min negatively affects the electrochemical properties of this material, indicating a decrease in the protective properties of the passivating layers.
NiTi alloys are widely used in biomedical applications due to their shape memory and superelastic properties. However, their surface reactivity requires protective, biofunctional coatings. To enhance NiTi performance, its surface was modified with an Ag-SiO2-TiO2 nanocoating containing small amounts of silica and silver. The coating’s primary phase was rutile with structural defects and a silver solid solution. It showed good adhesion, high scratch resistance, and improved corrosion behavior in Ringer’s solution, as demonstrated by EIS and cyclic polarization. EIS revealed high low-frequency impedance and two time constants, suggesting both barrier protection and slower electrochemical processes. Despite low breakdown and repassivation potentials, the coating effectively limited uniform corrosion. SEM/EDS confirmed localized degradation and partial substrate exposure, while elemental mapping showed well-dispersed silica and silver in a TiO2-rich matrix. The proposed pitting mechanism involves chloride-induced depassivation and galvanic effects. Surface potential mapping indicated electrostatic heterogeneity, mitigated by silica. The coating offers a balanced combination of corrosion protection and biofunctionality, supporting its potential for implant use.
The development of active, stable, earth -abundant, and cheap catalysts is crucial for renewable energy conversion devices. Catalysts for electrochemical water splitting are prepared using cold uniaxial pressing and consist of a superficial ferrite coating on a nickel substrate. The activity and mechanism of the oxygen (OER) and hydrogen (HER) evolution reactions on powder compacts are investigated. It is found that powder compacts are efficient catalysts for oxygen and hydrogen evolution in a 1 M KOH solution. For Ni/NiFe2O4, the current density of 10 mAcm- 2 in OER and -10 mAcm- 2 in HER shows overpotentials of 272 mV and -43 mV, respectively. In turn, for Ni/CoFe2O4, those overpotentials are 279 mV and -37 mV. Furthermore, using the same material for the anode and cathode in a two -electrode cell configuration, one can achieve a 10 mAcm- 2 water splitting current at only 1.55 V for over 48 h without coating degradation. It is stated that the high activity towards OER and HER results from the large electrochemically active surface area and high electrical conductivity of powder compacts. The results also indicate that the most probable rate -determining steps for OER and HER are the formation of the adsorbed oxide atom and H2 molecule, respectively.
Developments in engineering and medicine have allowed patients' health and quality of life to be supported by implants. Unfortunately, widely used titanium -based alloys with aluminum and vanadium are not ideal materials. The first problem is a mechanical mismatch between human bone and the implant material, and the second issue is the presence of Al or V, which are harmful for the human body and health. This article focuses on the holistic design and production of titanium -based materials with vital elements. The zoned, gradient element can exhibit better mechanical properties and improve the connection between the implant and the bone. The samples in two constructions were built with two different zones. The powders for samples were prepared using the powder metallurgy technique with sieve separation. Phillips X-ray X ' Pert diffractometer and PDF4 + database performed the phase composition analysis. The Scanning electron microscope allow the samples observation. Stereological methods assessed porosity and PAR M370 Scanning Electrochemical Workstation. The designed technology based on the powder metallurgy method allows for producing functional, two -zoned graded materials with variable porosity. The phase composition analysis confirmed partially synthesis. Additionally, the observation of the microstructure of the sintered samples revealed the presence of two permanently connected zones. Preliminary mechanical research was conducted to evaluate the potential use of the material as an implant material. The proposal to use two -zone construction of components for implants is dictated by the possibility of personalizing implants for patients, taking into account personal characteristics and needs.
To functionalize the NiTi alloy, multifunctional innovative nanocoatings of Ag-TiO2 and Ag-TiO2 doped with hydroxyapatite were engineered on its surface. The coatings were thoroughly characterized, focusing on surface topography and key functional properties, including adhesion, surface wettability, biocompatibility, antibacterial activity, and corrosion resistance. The electrochemical corrosion kinetics in a simulated body fluid and the mechanisms were analyzed. The coatings exhibited hydrophilic properties and were biocompatible with fibroblast and osteoblast cells while also demonstrating antibacterial activity against E. coli and S. epidermidis. The coatings adhered strongly to the NiTi substrate, with superior adhesion observed in the hydroxyapatite-doped layers. Conversely, the Ag-TiO2 layers showed enhanced corrosion resistance.
This study describes the properties of electroactive polypyrrole and its applications, with a focus on the roughness of the material. This parameter is crucial as it influences the applicability of coated layers, leading to highly adherent coatings or programmed wettability. The first raised aspect covers the electrodeposition procedure, which can help tailor the desired smoothness determined by roughness parameters. Features such as the deposition method, synthetic solution components, potential boundaries, substrate type, and utilized additives are evaluated. In the following section, the application aspects are discussed with a focus on modern, currently developed subjects such as medical applications, including cell-adherent coatings, antibacterial coatings, and drug delivery modules, as well as more technological fields like improved adhesion to the substrate and the improved mechanical properties of the deposited coating.
The success of implant treatment is dependent on the osseointegration of the implant. The main goal of this work was to improve the biofunctionality of the Ti-13Nb-13Zr implant alloy by the production of oxide nanotubes (ONTs) layers for better anchoring in the bone and use as an intelligent carrier in drug delivery systems. Anodization of the Ti-13Nb-13Zr alloy was carried out in 0.5% HF, 1 M (NH4)2SO4 + 2% NH4F, and 1 M ethylene glycol + 4 wt.% NH4F electrolytes. Physicochemical characteristics of ONTs were performed by high-resolution electron microscopy (HREM), X-ray photoelectron spectroscopy (XPS), and scanning Kelvin probe (SKP). Water contact angle studies were conducted using the sitting airdrop method. In vitro biological properties and release kinetics of ibuprofen were investigated. The results of TEM and XPS studies confirmed the formation of the single-walled ONTs of three generations on the bi-phase (α + β) Ti-13Nb-13Zr alloy. The ONTs were composed of oxides of the alloying elements. The proposed surface modification method ensured good hemolytic properties, no cytotoxity for L-929 mouse cells, good adhesion, increased surface wettability, and improved athrombogenic properties of the Ti-13Nb-13Zr alloy. Nanotubular surfaces allowed ibuprofen to be released from the polymer matrix according to the Gallagher–Corrigan model.
This work concerns the search for new ways to modify the surface of the biomedical Ti–13Zr–13Nb alloy for applications in regenerative medicine and personalized medicine. Obtained for the first time, oxide nanotubes (ONTs) layers of first-generation (1G) on a Ti–13Zr–13Nb alloy were produced by anodizing in 0.5% HF electrolyte at 20 V for 120 min. The physico-chemical characterization of the obtained bamboo-inspired 1G ONTs was conducted using TEM and ATR-FTIR methods. In vitro corrosion resistance of the 1G ONTs and comparative Ti–13Zr–13Nb substrate in saline solution at 37 °C was conducted by open-circuit potential, Tafel curves, anodic polarization curves, and EIS methods. LEIS and SVET study of local corrosion resistance was also carried out. It was found that surface modification by anodizing of the Ti–13Zr–13Nb alloy under proposed conditions allowed to obtain porous ONTs highly resistant to pitting corrosion. The obtained results give a new insight into the relationship between the morphological parameters of first-generation oxide nanotubes and in vitro corrosion resistance of the Ti–13Zr–13Nb alloy in saline solution at the macro- and microscale.
We determined the in vitro corrosion resistance of the composite chitosan-silver(I) [Ag(I)] ion coating on the cobalt-chromium-molybdenum (CoCrMo) dental alloy in a 0.9% sodium chloride (NaCl) solution at 37°C. We obtained the novel composite chitosan–Ag(I) ion coating by electrophoretic deposition at 20 V for 30 s at room temperature in a 2% (v/v) aqueous solution of acetic acid with 1 g dm–3 chitosan and 10 g dm–3 silver nitrate. We evaluated the chemical composition with energy dispersive spectroscopy and Fouriertransform infrared spectroscopy. We investigated surface topography and electronic properties with a scanning Kelvin probe. We determined the mechanism and kinetics of the electrochemical corrosion of the obtained coatings by electrochemical impedance spectroscopy. The Ag content in the composite chitosan–Ag(I) ion coating was 1.9 ± 1 wt.%. The cataphoretic co-deposition of chitosan and Ag(I) ions in an aqueous solution can be used to modify the CoCrMo alloy surface to obtain new coatings with antibacterial properties.
In the present work, we successfully used electrophoretic deposition to produce a new composite chitosan-copper(II) [Cu(II]) ion coating on grade 4 titanium (Ti). We prepared the coating with an environmentally friendly in situ chemical reduction process from a 2% (v/v) aqueous acetic acid solution with 1 g dm–3 chitosan and 10 g dm–3 copper acetate at 20 V for 300 s at room temperature. We evaluated the relationship between physicochemical properties and corrosion resistance of the coatings with energy dispersive spectroscopy, Fourier-transform infrared spectroscopy, a scanning Kelvin probe, and electrochemical methods. The composite coating contained 2.1 ± 0.1 wt.% of Cu, which ensures antibacterial activity. We determined the mechanism and kinetics of the electrochemical corrosion of the composite chitosan–Cu(II) ion coating on grade 4 Ti in saline solution (0.9% sodium chloride) at 37°C. The surface modification makes grade 4 Ti a more attractive material for use in dentistry.
Wirobond® C is a commercial dental casting alloy suitable for the fabrication of crowns, bridges, and metal ceramic restorations. This study aims to investigate the effect of ready-to-use Listerine® and Meridol® mouthwashes and sodium fluoride on the resistance of CoCrMo dental alloys to electrochemical corrosion in artificial saliva at 37 °C. SEM, EDS, SKP, and microhardness investigations were carried out to characterize the material under study. The in vitro corrosion resistance of the CoCrMo alloy was conducted using the open-circuit potential method, electrochemical impedance spectroscopy, and anodic polarization curves. The presence of Co 59.8(8) wt.%, Cr 31.5(4) wt.%, and Mo 8.8(6) wt.% was confirmed. The CoCrMo alloy was characterized by a Vickers microhardness value of 445(31) µHV0.3. Based on the EIS data, the capacitive behavior and high corrosion resistance of the CoCrMo alloy were revealed. The kinetics of pitting corrosion in the artificial saliva were lower after being modified with NaF, Listerine®, and Meridol® mouthwashes. The potentiodynamic characteristics revealed the passive behavior of the CoCrMo alloy in all solutions. Based on the SKP measurements of the CoCrMo alloy after corrosion tests, the effect of artificial saliva modification on the electronic properties of Bego Wirobond® C dental alloy was found.
Progress in dental implant prosthetics largely depends on developing new biomaterials and understanding the complex processes of their tissue adaptation. The related tribological wear phenomena within the dental system determine the durability and quality of the newly developed dental biomaterials. This paper presents an assessment of the tribological wear of the amorphous calcium phosphate (ACP) coatings on the commercially pure titanium Grade 4 (CpTi G4) substrate subjected to sandblasting and autoclaving in artificial saliva. The ACP coatings were produced using electrochemically assisted deposition (ECAD). The tribological properties were studied in a reciprocating motion in the system of ball-on-disc in protein-free artificial saliva. The surface morphology and chemical composition was characterized using the SEM and EDS method, respectively. The surface wettability was tested using the sitting drop in the air. It was found that the presence of the ECAD-derived ACP coating increases surface roughness, local contact potential difference, surface wettability, and resistance to tribological wear of CpTi G4 substrate significantly improving its service life. The tribological wear of CpTi G4/ACP occurred according to the three-body abrasion wear mechanism, in which artificial saliva played a key role as a biological lubricant.
In the group of vanadium-free titanium alloys used for applications for long-term implants, the Ti-13Zr-13Nb alloy has recently been proposed. The production of a porous layer of oxide nanotubes (ONTs) with a wide range of geometries and lengths on the Ti-13Zr-13Nb alloy surface can increase its osteoinductive properties and enable intelligent drug delivery. This work concerns developing a method of electrochemical modification of the Ti-13Zr-13Nb alloy surface to obtain third-generation ONTs. The effect of the anodizing voltage on the microstructure and thickness of the obtained oxide layers was conducted in 1 M C2H6O2 + 4 wt% NH4F electrolyte in the voltage range 5–35 V for 120 min at room temperature. The obtained third-generation ONTs were characterized using SEM, EDS, SKP, and 2D roughness profiles methods. The preliminary assessment of corrosion resistance carried out in accelerated corrosion tests in the artificial atmosphere showed the high quality of the newly developed ONTs and the slight influence of neutral salt spray on their micromechanical properties.
In this paper, two novel procedures based on powder sedimentation, thermal treatment, and galvanostatic deposition were proposed for the preparation of porous cobalt ferrite (CoFe2O4) coatings with a metallic and organic binder for use as catalysts in the oxygen evolution reaction (OER). The electrochemical properties of the obtained electrode materials were determined as well, using both dc and ac methods. It was found that cobalt ferrite coatings show excellent electrocatalytic properties towards the oxygen evolution reaction (OER) with overpotential measured at a current density of 10 mAcm−2 from 287 to 295 mV and a Tafel slope of 35–45 mVdec−1. It was shown that the increase in the apparent activity of the CoFe2O4 coatings with an organic binder results mainly from a large electrochemically active area. Incorporation of the nickel binder between the CoFe2O4 particles causes an increase in both the conductivity and the electrochemically active area. The Tafel slopes indicate that the same rate-determining step controls the OER for all obtained coatings. Furthermore, it was shown that the CoFe2O4 electrodes exhibit no significant activity decrease after 28 h of oxygen evolution. The proposed coating preparation procedures open a new path to develop high-performance OER electrocatalysts.
The corrosion of materials used in the design of metal-air batteries may shorten their cycle life. Therefore, metal-based materials with enhanced electrochemical stability have attracted much attention. The purpose of this work was to determine the corrosion resistance of commercially pure titanium Grade 2 (CpTi G2) cellular lattice with the triply periodic minimal surfaces (TPMS) architecture of G80, D80, I-2Y80 in 0.1 M KOH solution saturated with oxygen at 25 °C. To produce CpTi G2 cellular lattices, selective laser melting technology was used which allowed us to obtain 3D cellular lattice structures with a controlled total porosity of 80%. For comparison, the bulk electrode was also investigated. SEM examination and statistical analysis of the surface topography maps of the CpTi G2 cellular lattices with the TPMS architecture revealed much more complex surface morphology compared to the bulk CpTi SLM. Corrosion resistance tests of the obtained materials were conducted using open circuit potential method, Tafel curves, anodic polarization curves, and electrochemical impedance spectroscopy. The highest corrosion resistance and the lowest material consumption per year were revealed for the CpTi G2 cellular lattice with TPMS architecture of G80, which can be proposed as promising material with increased corrosion resistance for gas diffusion in alkaline metal-air batteries.
Calcium phosphate (CaP) coatings are able to improve the osseointegration process due to their chemical composition similar to that of bone tissues. Among the methods of producing CaP coatings, the electrochemically assisted deposition (ECAD) is particularly important due to high repeatability and the possibility of deposition at room temperature and neutral pH, which allows for the co-deposition of inorganic and organic components. In this work, the ECAD of CaP coatings from an acetate bath with a Ca:P ratio of 1.67, was developed. The effect of the ECAD conditions on CaP coatings deposited on commercially pure titanium grade 4 (CpTi G4) subjected to sandblasting and autoclaving was presented. The physicochemical characteristics of the ECAD-derived coatings was carried out using SEM, EDS, FTIR, 2D roughness profiles, and amplitude sensitive eddy current method. It was showed that amorphous calcium phosphate (ACP) coatings can be obtained at a potential −1.5 to −10 V for 10 to 60 min at 20 to 70 °C. The thickness and surface roughness of the ACP coatings were an increasing function of potential, time, and temperature. The obtained ACP coatings are a precursor in the process of apatite formation in a simulated body fluid. The optimal ACP coating for use in dentistry was deposited at a potential of −3 V for 30 min at 20 °C.
Calcium phosphate coatings are able to improve the osseointegration process due to their chemical composition, which is similar to that of bone tissues. In this work, to increase the long-term corrosion resistance and to improve the osseointegration process of commercially pure titanium Grade 4 (CpTi G4), biomimetic amorphous calcium phosphate (ACP) coatings were electrodeposited for the first time from an acetate bath with a pH level of 7.0 and a Ca:P ratio of 1.67. ACP coatings were obtained on CpTi G4 substrate subjected to sandblasting and autoclaving using electrochemically assisted deposition at a potential of −3 V relative to the open circuit potential for 30 min at room temperature. SEM, EDS, 2D roughness profiles, amplitude-sensitive eddy current method, and Kelvin scanning probe were used for the surface characterization of the biomaterial under study. In vitro corrosion resistance tests were conducted for 21 days in artificial saliva using open circuit potential, polarization curves, and electrochemical impedance spectroscopy measurements. The passive-transpassive behavior was revealed for the obtained ACP coatings. The long-term corrosion resistance test showed a deterioration of the protective properties for CpTi G4 uncoated and coated with ACP with immersion time. The mechanism and kinetics of the pitting corrosion on the CpTi G4|TiO2|ACP coating system are discussed in detail.
The paper presents the study of the corrosion resistance of electrodeposited Pd and its binary alloys with Pt, Rh, and Ru on a polycrystalline Au substrate. The corrosion resistance was tested in 0.5 M sulfuric acid at room temperature using potentiodynamic polarization and electrochemical impedance spectroscopy techniques. The morphology/composition and work function values were determined by scanning electron microscopy/energy–dispersive X–ray spectroscopy and scanning Kelvin probe, respectively. The obtained results revealed that the Pd electrode is the most resistant to corrosion, whereas the Pd-Ru electrode is the most susceptible to dissolution. It was found that the corrosion resistance of Pd-binary alloys decrease in the following order: Pd > Pd-Pt > Pd-Rh > Pd-Ru. This effect was assigned mainly to the difference in surface roughness factor of tested electrodes.