Anodic Polarization Research Articles

Effect of operating temperature on ammonia decomposition behavior and cell performance of direct ammonia solid oxide fuel cells

Direct ammonia solid oxide fuel cells (DA-SOFC) are regarded as a promising power generation technology. Nevertheless, the catalytic reaction of ammonia on the anode surface significantly affects DA-SOFC performance. This study explores the deterioration of DA-SOFC performance in the 550–700 °C and the interaction between NH3 decomposition and electrochemical reactions. The findings indicate that, at 550 °C, compared to H2, the reduction in power density of NH3 18.58% exceeds 4.56%t of NH3 d.s.g. (mixtures, 0.75H2 + 0.25N2). The anodic polarization impedance of NH3 exceeds that of H2 and NH3 d.s.g. by 51.1% and 28.9%, respectively. Cathode utilizing O2 has a dual impact on NH3 decomposition, at lower temperatures, oxidizing the anode's active site, decreasing NH3 decomposition rate, resulting in insufficient H2 supply, reducing electron transfer coefficient. Conversely, at higher temperatures, O2 promotes NH3 decomposition by boosting H2 consumption. However, more N2 is produced, increasing the concentration loss.

Electrochemical synthesis, physical properties and corrosion behavior of electropolymerized polyaniline films developed on 316L stainless steel

AbstractPolyaniline (PANI) films may be developed on metallic substrates by a variety of electrochemical techniques. In the present work, PANI films were electrodeposited on AISI 316L stainless steel substrates by cyclic voltammetry (CV), chronoamperometry (CA), and chronopotentiometry (CP) with the objective of comparing the efficacy of each method, based on the integrity of the developed films. Cyclic voltammetry and anodic polarization were used to determine optimal electrodeposition parameters for the development PANI films using the CA and CP methods. The structure and morphology of the coatings were characterized by scanning electron microscopy, energy‐dispersive x‐ray spectroscopy, Fourier‐transform infrared spectroscopy, and ultraviolet–visible spectroscopy. Among the evaluated techniques, CV led to the formation PANI films with the best homogeneity as well as the lowest number of defects, such as cracks or pores. Subsequently, the corrosion resistance of AISI 316L steels with and without PANI was compared in a physiological saline solution (0.9% NaCl). Potentiodynamic polarization tests indicated that the PANI‐coated samples exhibited lower corrosion current density values (0.012 vs. 0.018 μA/cm2) and lower passive current density values (0.04 vs. 0.06 μA/cm2) in comparison to the bare AISI 316L steel. Additionally, long‐term monitoring by electrochemical impedance spectroscopy revealed that PANI films consistently exhibited superior polarization resistance up to 32 days of exposure in the 0.9%NaCl solution (233,000 vs. 207,000 Ωcm2).

Poly(o-anisidine) and poly(o-anisidine-co-aniline) polymers synthesized on the ZnFeNi alloy coated steel surface

Abstract ZnFeNi alloy was synthesized on the carbon steel surface in a sulfate bath using the galvanostatic method at a constant current of 1.5 mA for 300 seconds. Poly(o-anisidine) homopolymer and poly(o-anisidine-co-aniline) copolymer were synthesized on the ZnFeNi coated electrode surface. Poly(o-anisidine) homopolymer was synthesized in 0.05 M o-anisidine+0.2 M sodium oxalate medium, and poly(o-anisidine-co-aniline) copolymer was synthesized in 0.05 M o-anisidine+0.05 M aniline+0.2 M sodium oxalate medium. Electrochemical synthesis was carried out by cyclic voltammetry technique. The synthesized materials were characterized by electrochemical impedance spectroscopy, linear sweep voltammetry, open circuit potential-time and anodic polarization curves. Open circuit potential-time curves showed that polymer coatings had higher open circuit potential. By linear sweep voltammetry measurements, it was determined that ZnFeNi alloys were present at the base of the polymer layers after polymer synthesis. It was understood from the anodic polarization curves that the polymer coated electrodes had lower current values ​​than the uncoated ZnFeNi coated electrode, and the poly(o-anisidine) coated electrode had lower current values ​​than the poly(o-anisidine-co-aniline) coated electrode. From electrochemical impedance spectroscopy measurements, it was determined that the polarization resistance of polymer-coated electrodes was higher than the polymer-free electrode during long periods of waiting in 3.5% corrosive solution. Among the polymer-coated electrodes, it was understood that the homopolymer poly(o-anisidine) showed better corrosion performance than the poly(o-anisidine-co-aniline) copolymer.

Investigations of motor performance with neuromodulation and exoskeleton using leader-follower modality: a tDCS study.

This study investigates how the combination of robot-mediated haptic interaction and cerebellar neuromodulation can improve task performance and promote motor skill development in healthy individuals using a robotic exoskeleton worn on the index finger. The authors propose a leader-follower type of mirror game where participants can follow a leader in a two-dimensional virtual reality environment while the exoskeleton tracks the index finger motion using an admittance filter. The game requires two primary learning phases: the initial phase focuses on mastering the pinching interface, while the second phase centers on predicting the leader's movements. Cerebral transcranial direct current stimulation (tDCS) with anodal polarity is applied to the subjects during the game. It is shown that the subjects' performance improves as they play the game. The combination of tDCS with finger exoskeleton significantly enhances task performance. Our research indicates that modulation of the cerebellum during the mirror game improves the motor skills of healthy individuals. The results also indicate potential uses for motor neurorehabilitation in hemiplegia patients.

Shattering the Water Window: Comprehensive Mapping of Faradaic Reactions on Bioelectronics Electrodes.

It is generally accepted that for safe use of neural interface electrodes, irreversible faradaic reactions should be avoided in favor of capacitive charge injection. However, in some cases, faradaic reactions can be desirable for controlling specific (electro)physiological outcomes or for biosensing purposes. This study aims to systematically map the basic faradaic reactions occurring at bioelectronic electrode interfaces. We analyze archetypical platinum-iridium (PtIr), the most commonly used electrode material in biomedical implants. By providing a detailed guide to these reactions and the factors that influence them, we offer a valuable resource for researchers seeking to suppress or exploit faradaic reactions in various electrode materials. We employed a combination of electrochemical techniques and direct quantification methods, including amperometric, potentiometric, and spectrophotometric assays, to measure O2, H2, pH, H2O2, Cl2/OCl-, and soluble platinum and iridium ions. We compared phosphate-buffered saline (PBS) with an unbuffered electrolyte and complex cell culture media containing proteins. Our results reveal that the "water window"─the potential range without significant water electrolysis─varies depending on the electrolyte used. In the culture medium that is rich with redox-active species, a window of potentials where no faradaic process occurs essentially does not exist. Under cathodic polarizations, significant pH increases (alkalization) were observed, while anodic water splitting competes with other processes in media, preventing prevalent acidification. We quantified the oxygen reduction reaction and accumulation of H2O2 as a byproduct. PtIr efficiently deoxygenates the electrolyte under low cathodic polarizations, generating local hypoxia. Under anodic polarizations, chloride oxidation competes with oxygen evolution, producing relatively high and cytotoxic concentrations of hypochlorite (OCl-) under certain conditions. These oxidative processes occur alongside PtIr dissolution through the formation of soluble salts. Our findings indicate that the conventional understanding of the water window is an oversimplification. Important faradaic reactions, such as oxygen reduction and chloride oxidation, occur within or near the edges of the water window. Furthermore, the definition of the water window significantly depends on the electrolyte composition, with PBS yielding different results compared with culture media.

Uncovering the electrochemical stability and corrosion reaction pathway of Mg (0001) surface: Insight from first-principles calculation

An understanding of the anomalously enhanced hydrogen evolution reaction (HER) of magnesium (Mg) under anodic polarisation in aqueous corrosion is paramount for a predictive theory of its corrosion and metal electrocatalysis. Previous theoretical and experimental studies have proposed that sub-surface hydride phases play a role in this behaviour but the underlying atomic mechanisms remain unclear. By constructing theoretical surface Pourbaix diagrams, based on density functional theory (DFT) calculations, we have identified the atomic structure of a sub-surface hydride phase on the Mg (0001) surface that remains electrochemically stable under significant anodic overpotentials across a wide pH range. Specifically, this stability persists up to 0.38 VSHE under mildly alkaline conditions (e.g., pH = 8), thus providing thermodynamic support for the proposed hydride-enhanced HER under anodic conditions. Reaction barrier analysis establishes that the proposed sub-surface hydride phase could promote anodic HER via a Heyrovsky pathway, based on hydrogen outward diffusion, with an energy barrier of 1.54 eV as the rate-limiting step, showing an anodic characteristic and significantly favouring external anodic polarisation. Furthermore, we have established that the surface adsorption condition, contingent on both the pH and potential, significantly influences the mechanism and kinetics of the initial corrosion of Mg.

Anticorrosive Properties of Different ZnFeNi Alloys Synthesized on Carbon Steel Surface

ZnFeNi alloys were synthesized galvanostatically in a sulfate bath at constant current values of 1, 1.5, and 2 mA on the carbon steel surface. The synthesized alloys were characterized by scanning electron microscopy, energy-dispersive X-ray analysis, and linear sweep voltammetry methods. The corrosion performances of the alloys were examined by electrochemical impedance spectroscopy, anodic polarization curves, and open-circuit potential-time techniques. Based on the anodic polarization curves, it was determined that the alloy with the lowest corrosion current was the ZnFeNi-1.5 alloy synthesized at a constant current value of 1.5 mA. The electrochemical impedance spectroscopy results showed that the alloy with the highest polarization resistance during long exposure to a corrosive environment was ZnFeNi-1.5. By examining the anticorrosive properties, it was understood that the alloy that showed the best protective properties against the corrosion of carbon steel was ZnFeNi-1.5.

Is the oxygen plasma cleaning technique indicated for any electrochemical purpose?: The case of FTO electrodes

Fluorine-doped tin oxide (FTO) is among the most used transparent conductive oxides (TCOs) in phototovoltaic devices such as photoelectrochemical and solar cells. Preparation of films on these TCOs can be achieved by several deposition techniques including electrodeposition. Among the several cleaning and activation procedures before a thin film deposition there is the oxygen plasma treatment, which has been successfully applied on several kind of substrate materials. Surprisingly, the use of this step on TCOs previously to the electrodeposition of a film is not a usual practice. Here we present a detailed study on the consequences of oxygen plasma process over FTO electrodes that are subsequently employed in several electrochemical reactions of practical importance. Open circuit potential (OCP) measurements from oxygen plasma treated FTO have proven the resorption of ions and/or solvent molecules in aqueous electrolyte following a pseudo-second order kinetic. Electrochemical reactions were quite sensible to the oxygen plasma treatment, even under mild conditions. In all cases FTO become deactivated for such electrochemical processes independently of the plasma set up employed except for metal electrodeposition. Partial recovering of the electrochemical response of FTO in the ferri/ferro system after annealing at 450 °C explains why oxygen plasma process is worthy only for other deposition techniques such as spray pyrolysis where similar temperatures are employed. Electrochemical Impedance Spectroscopy (EIS) analysis revealed a decrease of the majority carrier density (ND). This is mainly attributed to the oxyanion implantation on oxygen vacancies sites during the plasma process thus explaining the loss of activation of FTO. Energy level diagrams reveal the decrease of degeneracy of FTO towards an n-type semiconducting SnO2 film which is also supported by ultraviolet photoelectron spectroscopy (UPS). A band gap energy dependence with the plasma conditions allowed to check the filling of oxygen vacancies on the FTO surface without discard the loss of fluorine. Anodic polarization in acid media proved the impossibility of oxygen vacancies restitution, being the dominating process the partial etching of FTO.

Assessment of the inhibition performance of ZIF-8 on corrosion Mitigation of API 5L X65 steel in 3.5 wt% NaCl: Experimental and theoretical insight

The synthesis and application of ZIF-8 as an effective corrosion inhibitor for the corrosion of API 5L X65 steel in 3.5 wt% NaCl have been studied. The synthesized ZIF-8 was characterized using some surface probe approaches, which include field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HR TEM), and X-ray photoelectron spectroscopy (XPS), respectively. The results showed that ZIF-8 exhibited regular hexagonal and orthorhombic-shaped nanoparticles. An approximately 62% yield was achieved. Electrochemical studies such as open circuit potential (OCP), potentiodynamic polarization (PDP), and electrochemical impedance spectroscopy (EIS) were performed. The polarization results show that ZIF-8 is a mixed-type inhibitor, revealing a strong impact on both the anodic and cathodic polarization current values. The EIS studies reveal an increase in the charge transfer resistance upon the introduction of ZIF-8. The existence of a strong protective film adsorbed on X65 steel was recognized via XPS and FT-IR analysis. The highest inhibition efficiency value of 98.1% was recorded at a concentration of 0.120 wt% ZIF-8. Quantum chemical computations in the framework of DFT and molecular dynamic simulation were used to determine the reaction sites on the inhibitor, and as such, in-depth insight into the reaction mechanism was revealed.

Electrochemical impedance spectroscopy measurements on time-variant systems: the case of the Volmer-Heyrovský corrosion reaction. Part I: theoretical description

One of the theoretical requirements of electrochemical impedance spectroscopy measure­ments is that the studied system should not be varying with time. Unfortunately, this is rarely the case of physical systems. In the literature, quite a few methods exist to check and correct a posteriori the effect of time-variance, allowing to use conventional equivalent circuit models to fit and interpret the data. We suggest a different approach where, for a given electro­chemical mechanism and specific experimental conditions, assuming stationarity during each measurement, a time- and frequency-dependent expression of the Faradaic impe­dance is derived from the kinetic equations. The case of a potential relaxation at zero current following an anodic steady-state polarization is considered for a system where a Volmer-Heyrovský corrosion mechanism is supposed to take place.

Investigation of the Surface Characteristics of GCr15 in Electrochemical Machining.

Bearing steel (GCr15) is widely used in key parts of mechanical transmission for its excellent mechanical properties. Electrochemical machining (ECM) is a potential method for machining GCr15, as the machining process is the electrochemical dissolution of GCr15 regardless of its high hardness (>50 HRC). In ECM, NaNO3 solution is a popular electrolyte, as it has the ability to help in the nonlinear dissolution of many metallic alloy materials, making it useful for precision machining. However, due to high carbon content of GCr15, the electrochemical dissolution of GCr15 is unique, and there is always a black layer with high roughness on the machined surface, reducing the surface quality. In order to improve the electrochemical machining of GCr15 with a high surface quality, the surface characteristics of GCr15 in ECM were investigated. The anodic polarisation curve in the NaNO3 electrolyte was measured and electrochemical dissolution experiments were conducted with different current densities. SEM, XRD, and XPS were employed to analyse the surface morphology and composition formed on the machined surface at different current densities. The initial results showed that there were two parts (black part and bright part) formed on the machined surface when a short circuit occurred, and the test results suggested that the black part contained a mass of Fe3O4 while the bright part was composed of mainly Fe and Fe3C. Further investigation uncovered that a black flocculent layer (Fe3O4) always formed in a low current density (32 A/cm2) with high roughness. With the current density increased, the amount of black flocculent layer was reduced, and Fe3C particles appeared on the machined surface. When the current density reached 81 A/cm2, the entire flocculent oxide layer was removed, only some spherical Fe3C particles were inserted on the machined surface, and the roughness was reduced from Ra7.743 μm to Ra1.783 μm. In addition, due to exposed Fe3C particles on the machined surface, the corrosion resistance of the machined surface was significantly improved. Finally, circular arc grooves of high quality were well manufactured with current density of 81 A/cm2 in NaNO3 electrolyte.

Structural evolution and self-reconstruction of nickel hexacyanoferrate Prussian blue analogues for long-lasting ampere-current seawater oxidation

The commercial success of hydrogen (H2) production via seawater electrolysis largely depends on overcoming anode corrosion caused by chloride (Cl−), a critical challenge for scaling up renewable energy storage. Herein, we present the synthesis of nickel hexacyanoferrate Prussian blue analogues via anodic polarization for efficient alkaline seawater oxidation (ASO). Electrochemical experiments and in situ Raman studies unveil that leaching of Fe(CN)63− from the electrode facilitates a dynamic self-reconstruction process and leads to the formation of high-valence metal reaction specie, and appropriate Fe(CN)63− effectively shields active sites from Cl− interference even at ampere-level current density (j). In experiments, our electrode demonstrates an overpotential of merely 349 mV to reach a j of 1 A cm−2 and maintains stable operation for over 1000 h with protective Fe(CN)63−. This work showcases the potential of Prussian blue analogues for efficient and long-lasting ASO, protecting against Cl− in large-scale seawater H2 electrolysis.

Boosting the performance of La0.5Sr0.5Fe0.9Mo0.1O3-δ oxygen electrode via surface-decoration with Pr6O11 nano-catalysts

Cobalt-free La0.5Sr0.5Fe0.9Mo0.1O3-δ (LSFM) oxide is particularly investigated as a durable and efficient oxygen electrode material for the reversible solid oxide cells (RSOCs) in this study. Pr6O11 nano-catalysts are introduced into LSFM oxygen electrode as synergistic catalysts to enhance and optimize the electrode reactions. Results demonstrate an effectively promoted oxygen reduction and evolution reaction kinetics of the Pr6O11 decorated LSFM electrode. Polarization resistances (Rp) of LSFM electrode are dramatically reduced with the increasing Pr6O11 nano-catalysts and the lowest Rp of 0.039 Ω cm2 is obtained at 800 °C, which is ∼97% lower than that of the LSFM electrode. The Pr6O11 decorated LSFM oxygen electrode also displays a superior durability under cyclic anodic and cathodic polarizations. Furthermore, both the maximum power density and electrolytic current density of the Pr6O11 decorated cell are more than 2 times that of the LSFM cell. Results make clear reliability of the Pr6O11 decorated LSFM to be a promising oxygen electrode for RSOCs.

Inhibitory Effect of Fennel Fruit Essential Oil and Its Main Component Anethole of Corrosion on Steel Plates in 1 M HCL

Corrosion worldwide causes large losses of metal, which is why various ways are being sought to slow it down. The aim of this study was to investigate the inhibitory effect of fennel fruit essential oil (Foeniculum vulgare Mill.) and its main component anethole. The inhibitory effect of three different concentrations of the fennel essential oil and anethole (1.0 mL/L, 1.5 mL/L, and 2.5 mL/L) in a solution of 1 M HCl at 298 K for 6 h on a sheet of low-carbon steel was investigated. The inhibitory effect was established using gravimetric methods evaluating weight loss, corrosion rate, and inhibition efficiency, as well as electrochemical methods. In gravimetric studies, the inhibition effect of the inhibitors fennel essential oil and isolate anethole at a concentration of 2.0 mL/L was 70.85% and 45.86%, respectively. The anodic polarization curve data at 298 K demonstrate that the anethole and fennel essential oil adsorption on the metal surface creates a barrier that hinders hydrogen ions’ access and prevents them from being reduced on the steel surface’s cathode sites. Fennel essential oil acting as a mixed type-inhibitor can replace synthetic organic substances and could become an alternative to be used as environmental corrosion inhibitors.

A comparison of the corrosion behaviour over time in 0.5 M NaCl environment of TiCN spark plasma sintered with and without Si aids

The corrosion behaviour over time in 0.5 M NaCl of TiCN spark plasma sintered at low temperature (1400°C) with 5 vol% Si aids and its reference pure TiCN spark plasma sintered at high temperature (2100°C) were investigated by electrochemical techniques (i.e., open circuit potential, current-potential curves, and electrochemical impedance spectroscopy) and microstructural characterisation (i.e., optical microscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy), and compared. It is shown that both TiCN materials are very resistant to corrosion in 0.5 M NaCl. After two months of immersion the surfaces remained pristine, without any signs of attack. Their impedance responses revealed capacitive behaviour and very high impedance at low frequencies. The protective passive films strengthened during anodic polarisation and the samples withstood considerable overpotentials before film rupture. The TiCN material fabricated with Si aids is preferable due to its slightly higher corrosion resistance and much lower sintering temperature.

Surface reconstruction of hierarchical CoNiP@Ni2P nanoarray to promote overall water splitting

Efficient water splitting remains a challenge to produce clean and pure H2 in an industrial scale for the lack of high-performance cost-effective stable electrocatalysts of hydrogen and oxygen evolution (HER and OER). Surface engineering is a novel proposal to upgrade the electrocatalytic performances of HER and OER catalysts. Herein, a hierarchical architecture composed of carbon-supported CoNiP nanoplates (NPs) on Ni2P nanowire was constructed. The nanoarray of CoNiP@Ni2P heterostructure shows a high bifunctional activity of HER and OER. The overpotential is 46 mV required for HER at 10 mA·cm−2 and 292 mV for OER at 100 mA·cm−2 in 1 mol·L−1 KOH. In addition, the nanoarray of CoNiP@Ni2P heterostructure also shows a high stability for HER. The HER activity can be maintained at 11 mA·cm−2 without loss after 50 h cathode polarization at the overpotential of 100 mV, while the OER activity continuously increases from 26 to 64 mA·cm−2 at an overpotential of 400 mV after 50 h anode polarization. The enhancement of the oxygen evolution performance can be ascribed to the surface reconstruction of CoNiP/Ni2P heterostructure nanoarray, which can offer more active sites to OER. Density functional theory (DFT) reveals surface reconstruction can create an oxygen-rich surface in favor of intermediate adsorption, thus enabling a fast OER kinetics at the interface of NiCoOOH/Ni2P heterostructure. This work highlights surface reconstruction adaptability to design advanced catalysts of efficient water splitting for commercial H2 production.

Non-Stationary Effects of Current-Load on Electrochemical Behavior of La0.8Sr0.2MnO3- δ in Solid Oxide Electrolysis Cell

High-temperature solid oxide water electrolysis is a highly efficient and carbon-free technology employed for energy conversion, offering numerous advantages over traditional low-temperature water electrolysis methods. These benefits include fast electrode kinetics without the need for Pt group metals and the potential to operate in reversible regimes (fuel cell/steam electrolysis), attributed to the elevated operating temperature (i.e., 600-800 °C). However, the high operating temperature imposes stringent material requirements.While recent attention has been directed towards developing and characterizing new materials for both electrodes and electrolytes, a comprehensive understanding of the underlying reaction mechanisms remains incomplete, hindering the further advancement of the solid oxide cells.Despite the emergence of more advanced materials in recent years, the lanthanum-strontium-manganite La1-xSrxMnO3-δ (LSM) remains to be widely used for an oxygen electrode construction. This preference is due to its cost-effectiveness, high electrical conductivity, thermal and chemical stability, and compatibility with various solid electrolytes. Although LSM has been known for several decades, the reaction mechanism occurring on this oxygen electrode in a broad range of electrode potentials is inadequately described, with discrepancies arising among different authors. These inconsistencies are often linked to the evolving understanding of the non-stationary properties of the LSM lattice – the inner defect chemistry of LSM.Contemporary studies increasingly adopt the concept of ionic conductivity of LSM enabled by cathodic polarization to describe the oxygen reduction reaction. This shift from exclusive electron to ionic-electron conductivity enhances the performance of the LSM electrode, potentially causing discrepancies in the literature as experimental data may not align with theoretical descriptions. Conversely, for the oxygen evolution reaction during anodic polarization, a reversed reaction mechanism is considered without accounting for ionic conductivity of LSM under either stationary or non-stationary conditions. This approach may oversimplify the defect chemistry of LSM, particularly during transitions between operational regimes (i.e., fuel cell and electrolyser regimes). However, such changes are difficult to describe only by experimental approach. Here a combination with mathematical modelling seems to be promising approach allowing to gain deeper understanding.The primary objective of this study is to further investigate the impact of LSM defect chemistry on electrode performance, proposing a reaction scheme during both operating regimes and, crucially, during transitions between them.To address this goal, a series of experiments were conducted under both current-less and current-load conditions using laboratory button single cells. Various gas compositions and operating temperatures were used to determine whether LSM becomes a mixed ionic-electron conductor. Potentiostatic or potentiodynamic methods were used to clarify how this altered property influences individual operating regimes. The results indicate that cathodic polarization leads to a partial reduction of Mn4+ to Mn2+ in the crystalline lattice of LSM, creating oxygen vacancies through which oxide ions can be transported. Additionally, these lattice changes, though temporary, impact the oxygen evolution reaction region under certain conditions. A mathematical model incorporating parallel reaction pathways for both operating regimes supports these experimental results, predicting a cathodic potential at which ionic conductivity becomes viable and identifying conditions where partial reduction of Mn ions is no longer possible.This work contributes to understanding solid oxide cells, providing a solid foundation for more complex mathematical modeling of electrolysis cells. It underscores the necessity to fully comprehend the electrochemical behavior of electrode materials for the continued development of this technology.This work was supported by the Technology Agency of the Czech Republic under project no. TK04030143 (Advanced reversible system for hydrogen production on base of the high temperature solid oxide cell).

Mitigating the Corrosion of Anodized 304 and 316 Stainless Steel with GOx/PEDOT Coating for Bioelectrochemical Saline Water Applications

Steels are the most used alloys worldwide as they have superior mechanical properties, such as ductility and elasticity. Stainless steel (SS) is used far and wide from infrastructure, households, vehicles, surgical equipment, and medical implants, to electrochemical applications such as supercapacitors, fuel cells, lithium-ion batteries, aqueous rechargeable batteries, and bioelectrochemical systems (BES)1 such as microbial fuel cells (MFCs)2 and microbial electrolysis cells (MECs)3. Even though oxidized stainless steel is a very effective electrode material for BES, it has a high risk of corrosion due to the removal of the protective Cr-based passive oxide layer4.Hereby, this research aims to investigate the corrosion behavior of anodized stainless steel (SS) 304 and 316 mesh in saline water for potential use in BES with high salinity and try to mitigate that corrosion behavior using biocompatible materials. The tested electrodes include SS304 and SS316 mesh before and after anodization (anodized SS, AN-SS), in comparison to AN-SS coated with double layers of graphene oxide (GOx) and poly(3,4-ethylenedioxythiophene) (PEDOT). SS 304 and 316 were anodized using selective leaching protocol to enhance the removal of the bioincompatible and insulating Cr-based layer. The removal of that layer makes SS more susceptible to dissolution and hence further protection is needed. Both GOx and PEDOT were selected to enhance the surface conductivity, biocompatibility, and corrosion resistance. GOx was synthesized using the electro-exfoliation of a graphite sheet at a constant voltage of 10.0 V in terephthalic acid + NaOH solution, followed by centrifuging at 3000 rpm to remove the large particles.5 After several cycles of washing, the freeze-dried GOx was mixed with Nafion for ink preparation, which was used to coat the An-SS using the spray coating method. The coated electrode was further covered with a PEDOT layer, using the chronpotentiometry electropolymerization method (2 mA/cm2, for 10, 30, or 60 min). Several characterization techniques such as SEM, EDX, XPS, FT-IT, Raman spectroscopy, XRD, and TEM, were used to characterize the physical and chemical structure of the coating materials and the the fabricated electrodes. The corrosion behavior was evaluated using potentiodynamic and potentiostatic methods. Based on the anodic polarization results, the corrosion, passivation, and breakdown (due to dissolution) regions were identified. In this presentation, the corrosion behavior (Ecorr, Icorr, breakdown potential, etc) of the studied electrodes will be correlated with their chemical and physical structures. References K.-B. Pu, J.-R. Bai, Q.-Y. Chen, and Y.-H. Wang, in Novel Catalyst Materials for Bioelectrochemical Systems: Fundamentals and Applications, ACS Symposium Series., vol. 1342, p. 165–184, American Chemical Society (2020) https://doi.org/10.1021/bk-2020-1342.ch008.A. A. Abbas, H. H. Farrag, E. El-Sawy, and N. K. Allam, Journal of Cleaner Production, 285, 124816 (2021).Y. Zhang, M. D. Merrill, and B. E. Logan, International Journal of Hydrogen Energy, 35, 12020–12028 (2010).P. Ledezma, B. C. Donose, S. Freguia, and J. Keller, Electrochimica Acta, 158, 356–360 (2015).H. S. Wang et al., Green Chem., 20, 1306–1315 (2018).

Corrosion Initiation on Reinforcing Steel with Mill Scale in Mortar

Corrosion of reinforcing steel rebar is the main cause of loss of the long-term reliability of concrete structures. When the rebar is corroded, the rust induces cracks and detachment of the cover concrete. The mill scale, a thick oxide film, is formed on the rebars when the rebar is hot rolled. The role of mill scale on the corrosion resistance of rebars in concrete has not been clarified, yet. This study studied the corrosion behavior of rebars with mill scale in mortar.The samples are commercial rebars with 19 mm diameter, which have a mill scale of several tens of micrometers in thickness. The rebars without mill scale prepared by the electrolytic polishing were used as the comparison samples. A Hyperbaric-oxygen accelerated corrosion test (HOACT) [1] was carried out using the rebars embedded in the mortar with a 5.5 mm cover thickness. To prompt the breakdown of passive film on the rebars, 2.1 M NaCl solution was mixed with the mortar. In the HOACT, pressurized oxygen gas is supplied to the sample, and the oxygen reduction reaction on the steel surface is enhanced, leading to the steel's corrosion acceleration. The oxygen pressure was 0.6 MPa and the test period was 14 days. The corrosion of the rebar with a mill scale was more significant than that without a mill scale. This result shows that the mill scale reduces the corrosion resistance of the steel rebar in concrete [2].To investigate the effect of the mill scale on the corrosion resistance of the rebar, anodic polarization measurements of the rebars with and without the mill scale were carried out in a saturated Ca(OH)2 solution containing Cl-. The pitting potential of the rebar with mill scale was more noble than that of the sample without mill scale. However, when the mill scale was scratched, the pitting potential was significantly shifted to the less noble direction, and it was below that of the rebar without the mill scale. These results show that the mill scale improves the corrosion resistance of the rebar in concrete, in contrast, the corrosion resistance of the rebar with a defective mill scale becomes even worse than that of the rebar without the mill scale [2].[1] K. Doi, S. Hiromoto, H. Katayama, E. Akiyama, J. Electrochem. Soc., 165(9), C582-C589 (2018).[2] K. Doi, S. Hiromoto, T. Shinohara, K. Tsuchiya, H. Katayama, E. Akiyama, Corrosion Science, 177, 108995 (2020).

Electrochemical Dissolution Behavior of ZCuPb10Sn10 Alloy in NaNO3 Solution

Copper alloys, such as ZCuPb10Sn10, have been widely applied to friction pairs in various products. Surface texture, such as micro-dimple array has attracted significant attention from researchers worldwide to improve tribological performance. To generate micro-dimple array on ZCuPb10Sn10 alloy by electrochemical machining, it is essential to investigate the electrochemical dissolution behavior of ZCuPb10Sn10 in NaNO3 solution. In this paper, the electrochemical dissolution behavior of ZCuPb10Sn10 alloy in NaNO3 solution is investigated through experimental tests. Anodic polarization, Tafel polarization, and electrochemical impedance spectroscopy were conducted to investigate its passive and corrosion behavior. The microstructure and composition of the dissolved surfaces were analyzed under various conditions. Additionally, a model was proposed to explain the electrochemical dissolution process of ZCuPb10Sn10 alloy in NaNO3 solution under high pressure hydrostatic conditions. Ultimately, a NaNO3 solution with 10% in concentration and 20 °C in temperature was selected as the electrolyte and a micro-dimple array with an average diameter of 119.7 μm and a depth of 7.4 μm was successfully generated with through-mask electrochemical micromachining on the surface of ZCuPb10Sn10 alloy.