Surface Oxidation Research Articles

A facile synthesis of N-doped carbon encapsulated multimetallic carbonitride as a robust electrocatalyst for oxygen evolution reaction

Electrocatalytic water splitting is a promising solution for generating clean hydrogen. Transition metal compounds are among the most extensively investigated catalysts developed to date for water oxidation in alkaline media, a process also known as the oxygen evolution reaction (OER). However, the application of these catalysts was constrained by insufficient stability arising from surface oxidation and metal dissolution under high OER potential. In this work, we developed a facile approach using urea-based gel as the precursor of preparing a series of multimetallic carbonitride particles which were encapsulated by N-doped carbon (NC). In particular, (MoCoFeNiZr)CN@NC core–shell structure delivered a low overpotential of 246 mV at a current density of 10 mA cm−2 in 1 M KOH during OER. Importantly, operando differential electrochemical mass spectrometry (DEMS), together with multiple microscopic and spectroscopic analyses, indicated that the NC shells effectively maintained the crystalline stability of carbonitride via suppressing the surface reconstruction during catalysis. The highly graphitic NC also demonstrates excellent stability against oxidation. This work shows a promising strategy of stabilizing electrocatalyst at high anodic potential, paving the way for the development of robust electrode materials for energy conversion.

Enhancing machinability in free-cutting duplex brass alloys: Isotropic blocky α phase formation via optimized hot extrusion processing

Despite the active utilization of duplex brass alloys in the electronics and automotive industries, optimizing thermomechanical treatment conditions for achieving excellent machinability remains a subject of ongoing debate. In this study, to establish a strategy to achieve enhanced machinability via industrial-scale direct hot extrusion processing, we systematically investigated the effect of hot extrusion processing conditions on microstructural evolution, mechanical properties, and machinability of duplex brass alloys. In particular, the yield strength was effectively interpreted through the extended Hall-Petch relationship, and the machinability was further elucidated through the evaluation of rotational torque during the drilling test as well as the precise analysis of segmented chips produced in the drilling test. As a result, our microstructural analysis of the as-cast Cu58Zn39Pb3 alloy revealed that the cooling process during industrial-scale casting inevitably results in the formation of the Widmanstätten structured α phase and the heterogeneous dispersion of Pb particles. In contrast, 670 ℃ extruded lower part and 730 ℃ extrudates, which were extruded in the single β region that caused complete dynamic recrystallization behavior, exhibited a uniform and isotropic blocky α structure and uniformly redistributed Pb particles, ultimately leading to superior mechanical properties and machinability. Notably, our findings suggest that achieving an isotropic blocky α structure can be attained at temperatures up to 100 ℃ below the β-transus temperature by optimizing extrusion pressure conditions. This approach offers an efficient methodology for minimizing defects caused by high-temperature extrusion, such as surface oxidation and hot shortness cracking, while simultaneously minimizing processing costs.

Investigation of wettability and icing on the steel surface using laser surface treatment

Icing impairs normal functionality for a variety of industries and applications. Research on hydrophobic surfaces is being conducted to solve the icing problem. In this study, a hydrophobic surface was fabricated on SM490A using a nanosecond laser. The change in surface microstructure was observed. Hydrophilicity was immediately observed right after laser irradiation, and the contact angle increased over time, resulting in hydrophobicity. To explain the wettability conversion, X-Ray Photoelectron Spectroscopy (XPS) was used to observe changes in surface chemical composition and element bonding. It was observed that the level of and increased immediately after laser irradiation, resulting in surface oxidation. Since the presence of oxides has high surface energies, they contribute to super hydrophilic surfaces. Since the bond has low surface energy and the content of nonpolar bonds and increased over time, the contact angle subsequently increases over time. When the ice shape was observed after dropping a droplet on the surface, the higher contact angle specimen reduced the attached area. Therefore, the surface treatment using a nanosecond laser can produce a hydrophobic surface on the SM490A specimens so that it may solve ice adhesion problems.

Effects of ultraviolet sterilization exposure on the structural and surface properties of graphite-/polymer-like carbon films

Existing research on the biological responses of amorphous carbon films has not adequately explored the influences of exposure to ultraviolet (UV) sterilization at 253.7 nm before cell culture. Thus, in this study, two types of amorphous carbon films, namely hydrogen-rich graphite-like carbon (GLC) and hydrogen-free polymer-like carbon (PLC) films, were deposited on Si substrates. The influences of different doses of UV sterilization exposure (at 253.7 nm) on the structures and surface properties of the amorphous carbon films were investigated. Spectroscopic ellipsometry and Raman analysis showed that there is no significant change in the optical constants and Raman spectra of GLC and PLC films. The surface properties of the amorphous carbon films, characterized by water contact angle measurements and X-ray photoelectron spectroscopy analysis, indicated that both types of films exhibited hydrophilicity and surface oxidation in response to UV sterilization. However, the effects of UV sterilization on PLC were more notable than those on GLC. Our findings highlight the need for standardization and optimization of UV sterilization conditions for specific films to promote the application of amorphous carbon film coatings in the medical domain.

Effect of Carbon Nanotubes Functionalization on the Chemical Composition and Electrochemical Characteristics of Composites with Layered Potassium Manganese Oxide

The influence of pretreatment of multiwalled carbon nanotubes (MWCNTs) in oxidizers (solutions of H2O2 and HNO3) on the structure and electrochemical properties of composites with layered potassium-manganese oxide (KxMnO2) was studied. Composites were obtained by soaking carbon nanotubes in an aqueous solution of KMnO4 at 60 °C. The electrochemical performance of the composites was evaluated by cyclic voltammetry and galvanostatic charge‒discharge methods. It has been established that stronger oxidation of the MWCNTs surface at the functionalization stage leads to a noticeable increase in the reaction rate as well as the optimal potassium content in the KxMnO2 composition, which provides higher capacitive characteristics of the composite (a maximum specific capacitance of 150 F g−1 and a rate capability of 43% with increasing density current from 0.1 to 2.0 A g−1). The resulting composites are promising active components for increasing the capacitive characteristics of conductive carbon black (CB). Compared with an electrode based only on CB, electrodes based on a combination of the composite and CB at a mass ratio of 1:1 showed specific capacitance values approximately 1.5 to 3 times greater, as well as a twofold increase in rate capability (from 35 to 70%) in the range of discharge current density 0.1 to 2.0 A g−1.

Synthesis and characterizations of nanohybrids based on amino silane-graphene oxide decorated by zirconium oxide nanoparticles

This study aims to synthesize graphene oxide using the modified Hummers method and subsequently functionalize the surface of graphene oxide with amino silane N-(b-aminoethyl)-c-aminopropyltrimethoxysilane (AEAPTMS), resulting in silane-graphene oxide (SGO). The surface of SGO is then decorated with zirconium oxide (ZrO2) nanoparticles, generating SGO-ZrO2 nanohybrids. All the synthetized materials GO, SGO and SGO-ZrO2 were subjected to various characterization techniques, including Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), Thermogravimetric analysis (TGA), Zeta potential measurement and Scanning electron microscope (SEM). The results revealed that GO nanosheets were decorated with ZrO2 nanoparticles through covalent bonding with AEAPTMS.

Synergistic effect of graphene oxide and silica nanocomposites towards multifunctional biomedical applications

The development of advanced nanomaterials (NMs) has recently gained significant attention because of their potential in addressing various biomedical and healthcare challenges. This study focuses on the synthesis of silica (SiO2) nanoparticles (NPs) and their nanocomposite with graphene oxide (GO-SiO2), using a multifunctional approach to enhance antibacterial, antibiofilm, antioxidant, and antidiabetic properties. The synthesis of the GO-SiO2 involves the controlled growth of SiO2 NPs on the surface of the graphene oxide (GO) sheets. The synthesized NPs were characterized by UV–Visible spectroscopy, Fourier-Transform Infrared (FTIR) Spectroscopy, X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), and Energy Dispersive X-ray (EDX) Spectroscopy. The crystallite sizes of SiO2 and GO-SiO2 were found to be 23.07 nm and 32.07 nm, respectively, by XRD analysis and 27.03 nm and 43.11 nm, respectively, by SEM. The Band gap of SiO2 was decreased from 3.76eV to 3.45eV in GO-SiO2. Disc diffusion method was used to perform antibacterial activity whereas ampicillin and moxifloxacin were taken as reference drugs. Biofilm inhibitions and minimum inhibitory concentrations were measured by microtiter plate method. The composite has shown higher antimicrobial activities against S. aureus, S. aureus MDR, K. pneumoniae, P. aeruginosa, P. aeruginosa MDR, E. coli, and P. vulgaris as compared to SiO2 NPs and GO. When IC50 values were compared with those of control (acarbose), GO-SiO2 and SiO2 demonstrated the highest and lowest antidiabetic activities, respectively. A 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical scavenging process was used to evaluate the antioxidant potential of NMs using ascorbic acid as a reference. GO-SiO2 displayed the negligible IC50 value compared to both SiO2 and GO. The nanocomposite (GO-SiO2) has shown higher antibacterial, antibiofilm, antioxidant, and antidiabetic potential as compared to those of GO and SiO2NPs.

Near-surface reconstruction strategy stabilizing high-voltage redox reactions in single crystal Li-rich Mn-based oxides

Li-rich Mn-based oxides (LRMO) greatly increase its output energy density due to its additional oxygen redox activity. However, the inherent oxygen loss and irreversible phase transition induce low initial coulombic efficiency and serious voltage decay, further seriously impeding its industrial application. Herein, a near-surface in-situ reconstruction strategy has been proposed, which constructs the oxygen vacancies and spinel phase coating on the surface of single-crystal Li-rich Mn-based oxide (SC-LRMO) concurrently to improve Li+ storage performance via the oxalic acid induction method. Intensive exploration based on structure characterizations demonstrates that such a near-surface in-situ reconstruction strategy not only accelerates the transmission of Li+, but also stabilizes high-voltage redox reactions by trapping the escaping On− within the newly formed spinel phase coating. Impressively, the modified sample exhibit 91.1% capacity retention ratio after 300 cycles, superior to the SC-LRMO (74.5% capacity retention ratio after 300 cycles). Additionally, even at a high cut-off voltage of 5 V, the acid etched sample exhibits significantly enhanced cycling stability, delivering 200 mAh g−1 with a 94% capacity retention ratio after 300 cycles. This surface self-reconstruction strategy provides profound insights into regulating the surface structure of LRMO for high-energy-density lithium-ion batteries.

Valorization of carbon soot ash for the selective capture of lead ions from industrial waste water–A waste to resource approach

Landfills are struggling to accommodate the increasing amounts of carbon soot ash waste from oil refineries. Due to extensive industrial productions, large quantities of lead ions are released into the environment, which not only pollutes the environment but also affects flora and fauna. In this work, these urgent environmental issues will be tackled by studying the use of modified carbon soot ash for specific heavy metal adsorption. Carbon soot ash modified with chemical leaching and physical ball-milling was loaded onto the surface of graphene oxide. This adsorbent was found to selectively adsorb and remove toxic lead ions (>99%) from a mixed heavy metal solution. The adsorption efficiency was found to increase with temperature (20–60 °C) and pH (2–8). Langmuir isotherm and pseudo-second order kinetics were found to fit the adsorption process through curve fitting, where the adsorbent reached a maximum capacity of 194.55 mg/g. Potential mechanisms for lead adsorption and metal specificity are also discussed here. This work aligns with the waste-to-resource pathway, where waste carbon soot ash is diverted from landfilling and is formulated as a specific heavy metal adsorbent, that shows promise for environmental remediation.

Comparative study of Ni nanoparticles synthetized using electroless Ni plating waste and an analytical Ni reagent. Characterization and possible application in magnetic fluids

Wastewater from the electroless industry represents a potential danger to the environment and health, mainly due to its heavy metal content. In this study, nickel nanoparticles were synthesized through chemical reduction precipitation by using an electroless nickel plating waste and hydrazine sulfate as reducing agent. The aim of the present work is twofold. First we want to extract the metal from the aqueous medium, minimizing its content to levels allowed by environmental regulations. Second, we aim to valorize the residue by recovering the precipitated nickel to be applied as a solid phase in a magnetic fluid (MF). It is found that the present synthesis method using N2H4 as reducing agent, allowed us to minimize the Ni concentration in the aqueous waste in 97.49 %. The properties of the recovered Ni precipitate is compared with the Ni nanoparticles (NPs) obtained from a solution prepared with analytical grade nickel sulfate. The synthesized materials from both the waste (Ni-R) and analytical reagent (Ni-A) were characterized by comparing their chemical, physical, and morphological properties. In both cases, the Ni-R and Ni-A precipitates, spherical Ni NPs of 8–10 nm crystallite sizes are obtained, agglomerated in a bimodal size distribution centered at 174.6 and 383.4 nm, and a monomodal size distribution centered at 63.6 nm, respectively. Both Ni precipitated samples are ferromagnetic, but the Ni-R sample has a higher magnetic saturation of 40 emu/g compared to 8 emu/g of the Ni-A sample. The difference in the rheological behavior of both precipitates could be attributed to the presence of surface oxidation having a relatively less contribution in the case of the Ni-R particles due to the higher average size of the particles. The Fe content, probably coming from the nickel-plated parts in spent baths, is slightly higher in the Ni-R sample. Thus, the present work shows that it is possible to valorize an industrial Ni-based residue, by obtaining Ni precipitates that in magnetic fluids give even better results than those expected under more rigorous experimental conditions, i.e., in cases where the quality of the chemical precursors is usually a determining factor.

Clarifying the Relationship Between Chemical States of P in Fe–P Alloys and Pitting Corrosion Resistance

Fe–0.002 P, Fe–0.05 P, Fe–0.2 P, and Fe–2 P alloys (numbers indicate the mass%) were fabricated, and their pitting potentials, depassivation pH values, and active dissolution rates were measured. The order of pitting potentials was (high) Fe–0.002 P ≥ Fe–0.05 P ≥ Fe–0.2 P ≫ Fe–2 P (low), and that of depassivation pH values was (low) Fe–0.002 P ≤ Fe–0.05 P ≤ Fe–0.2 P ≪ Fe–2 P (high). Both parameters changed significantly between the Fe–0.2 P and Fe–2 P alloys. No evidence of grain boundary segregation of P was observed in the Fe–0.05 P alloy. In the Fe–0.2 P alloy, grain boundary segregation of P was observed, but no pitting occurred at the grain boundaries. In the Fe–2 P alloy, Fe3P precipitated at the grain boundaries and in grains, but pitting corrosion occurred in the alloy matrix and not in Fe3P. This indicated that P in the solid solution was the main cause of the decrease in pitting corrosion resistance. The P concentration in the surface oxide film on Fe–2 P was higher than that on Fe–0.2 P, and the P in the films was determined to be FePO4. The decrease in the pitting resistance with an increasing P concentration was due to FePO4.

Assessing the sustainability and safety of Polyethylene Terephthalate (PET) liners for Lead Service Lines (LSL) Upgrades

Polyethylene Terephthalate (PET) liners have been proposed by industry as a more cost effective and less disruptive alternative to lead service lines (LSL) replacement. However, concerns have been raised about their aging under real-use conditions and their potential health and environmental impacts. In this study, two approaches were implemented. First, bench and pilot scale experiments were carried out to investigate the aging of a PET liner under conditions that simulate normal usage. Results show early surface oxidation and leaching of potentially hazardous metals (lead, zinc and titanium). No short-term fragmentation of the PET liner into microplastics was observed. Next, a life cycle assessment (LCA) compared the health and environmental impacts of three LSL upgrades alternatives: PET liners and full LSL replacement using either copper or PEX pipes. The installation phase was shown to be the main contributor to impact scores, while the benefits of PET liners are highly dependent on its lifespan. PEX installed by torpedoing lowers impacts as compared to PET liners and copper pipes for equal lifespan, while the use of PET liners remains less impactful regarding human health and ecosystem quality when a complete excavation is needed. LCA derived global human health effects due to ingestion of leached metals from PET liners, copper pipes, and unreplaced LSL and showed that PET liners and copper pipes significantly reduce health impacts by 14 and 80 DALY respectively compared to unreplaced LSL. Finally, the Integrated Exposure Uptake Biokinetic (IEUBK) model was used to assess the impact of lead exposure specifically for drinking water ingestion. Estimated Blood Lead Levels (BLL) in children and infants in households with long unreplaced LSL was up to 263.7% and 207.8% greater compared to either replacement with copper pipes or rehabilitation with PET liners, showing the clear benefits of corrective action. Combining experimental results, LCA and biokinetic modelling provides actionable information for utilities to select the best upgrade options, considering environmental, health and practical constraints, whilst identifying remaining data gaps. The relative benefits of the PET liner should be carefully evaluated considering its lifespan under real-life conditions, the complete replacement costs after failure, and the growing evidence of micro- and nanoplastics (MNP) risks.

Investigating Layered Topological Magnetic Materials as Efficient Electrocatalysts for the Hydrogen Evolution Reaction under High Current Densities

Despite considerable progress, high-performing durable catalysts operating under large current densities (i.e., >1000 mA/cm2) are still lacking. To discover platinum group metal-free (PGM-free) electrocatalysts for sustainable energy, our research involves investigating layered topological magnetic materials (semiconducting ferromagnets) as highly efficient electrocatalysts for the hydrogen evolution reaction under high current densities and establishes the novel relations between structure and electrochemical property mechanisms. The materials of interest include transition metal trihalides, i.e., CrCl3, VCl3, and VI3, wherein a structural unit, the layered structure, is formed by Cr (or V) atoms sandwiched between two halides (Cl or I), forming a tri-layer. A few layers of quantum crystals were exfoliated (~50−60 nm), encapsulated with graphene, and electrocatalytic HER tests were conducted in acid (0.5M H2SO4) and alkaline (1M KOH) electrolytes. We find a reasonable HER activity evolved requiring overpotentials in a range of 30–50 mV under 10 mA cm−2 and 400−510 mV (0.5M H2SO4) and 280−500 mV (1M KOH) under −1000 mA cm−2. Likewise, the Tafel slopes range from 27 to 36 mV dec−1 (Volmer–Tafel) and 110 to 190 mV dec−1 (Volmer–Herovsky), implying that these mechanisms work at low and high current densities, respectively. Weak interlayer coupling, spontaneous surface oxidation, the presence of a semi-oxide subsurface (e.g., O–CrCl3), intrinsic Cl (or I) vacancy defects giving rise to in-gap states, electron redistribution (orbital hybridization) affecting the covalency, and sufficiently conductive support interaction lowering the charge transfer resistance endow the optimized adsorption/desorption strength of H* on active sites and favorable electrocatalytic properties. Such behavior is expedited for bi-/tri-layers while exemplifying the critical role of quantum nature electrocatalysts with defect sites for industrial-relevant conditions.

Evaluation of electrodeposition synthesis of gold nanodendrite on screen-printed carbon electrode for nonenzymatic ascorbic acid sensor

Gold nanodendrite (AuND) is a type of gold nanoparticles with dendritic or branching structures that offers advantages such as large surface area and high conductivity to improve electrocatalytic performance of electrochemical sensors. AuND structures can be synthesized using electrodeposition method utilizing cysteine as growth directing agent. This method can simultaneously synthesize and integrate the gold nanostructures on the surface of the electrode. We conducted a comprehensive study on the synthesis of AuND on screen-printed carbon electrode (SPCE)-based working electrode, focusing on the optimization of electrodeposition parameters, such as applied potential, precursor solution concentration, and deposition time. The measured surface oxide reduction peak current and electrochemical surface area from cyclic voltammogram were used as the optimization indicators. We confirmed the growth of dendritic gold nanostructures across the carbon electrode surface based on FESEM, EDS, and XRD characterizations. We applied the SPCE/AuND electrode as a nonenzymatic sensor on ascorbic acid (AA) and obtained detection limit of 16.8 μM, quantification limit of 51.0 μM, sensitivity of 0.0629 μA μM−1, and linear range of 180–2700 μM (R2 value = 0.9909). Selectivity test of this electrode against several interferences, such as uric acid, dopamine, glucose, and urea, also shows good response in AA detection.

On the corrosion resistance of the CoCrFeMnNi high entropy alloys in chloride-containing sulfuric acid solutions

The electrochemical reactivity of the high entropy Cantor alloy (CoCrFeMnNi) was investigated via potentiodynamic polarization curves, electrochemical impedance spectroscopy (EIS), and surface analysis as a function of chloride content, in sulfuric acid solutions. The results revealed that corrosion mechanism of the CoCrFeMnNi alloy at the corrosion potential, is a two-step mechanism, involving one adsorbed intermediate, similar to that of pure iron in the H2SO4, and this model provided a good description of the impedance data. X-ray photoelectron spectroscopy (XPS) surface characterization and impedance data fitting revealed that chloride ions do not alter the corrosion mechanism or the thickness of the surface oxide film. Instead, they affect the corrosion resistance by changing the composition of the oxide film. Additionally, this work demonstrated that the corrosion mechanism of the CoCrFeMnNi alloy varies with the applied potential, as evidenced by impedance measurements under potentiostatic polarization. Surface observations using scanning electron microscopy (SEM) and XPS analysis provided insights into the morphology and composition of the surface oxide film at different applied potentials, explaining the observed changes in impedance.

Sonocatalytic degradation of furazolidone using a heterogeneous triple ion synergy system of ZnFe2O4@ZIF-67 nanostructures: Physicochemical Characterization and degradation pathway

Heterogeneous sonocatalysis coupled with peroxydisulfate (PDS) activation is considered as a rapid advanced oxidation process for the degradation of emerging pharmaceutical pollutants. ZnFe2O4@ZIF-67 nanostructures (NSs) with commendable features including a high crystallinity, a narrow bandgap, and an outstanding specific surface, showed excellent sonocatalytic performance, PDS activation and stability. A novel triple ion synergistic system was used for the swift degradation of 60 mg/L furazolidone (FZD) from real contaminated water sources. A superior sonocatalytic degradation performance of FZD (94 %) by ZnFe2O4@ZIF-67/PDS/Ultrasound system was achieved under the optimal conditions of 20 mmol/L PDS and 0.4 g/L of the nanocomposite within 60 min. The e-/h+ pairs produced as a result of the sonoluminescence phenomenon in the ZnFe2O4@ZIF-67 NSs, with a bandgap of 1.86 eV, accelerated the redox reduction transform cycle of the Zn2+ /Zn, Fe3+/ Fe2+ and Co3+/ Co2+ pairs by generating a large number of oxidative radicals, leading to the enhanced degradation efficiency. Quenching tests illustrated that SO4•-,1O2, •OH radicals and surface oxidation–reduction reactions played a crucial role during FZD degradation. FZD degradation by-products were put forward using the LC-MS technique, and a plausible degradation pathway was suggested. The mineralization tests and the toxicity of generated intermediates of FZD degradation were also examined. Also, the stability and reusability results underscored the substantial proficiency of the above system to remediate real-pharmaceutical-contaminated-water sources, providing a practical approach for its industrial applications.

Clarifying the effects of composition and phase stabilization on the oxidation resistance in AlCoCrFeNiTi series high-entropy alloys at 1100 °C

The application of high entropy alloys in thermal barrier coating (TBC) systems offers a viable solution for mitigating interfacial instability arising from the elevated-temperature interdiffusion within the bonding layer/matrix. Nevertheless, the elucidation of phase stability under elevated temperatures and the intricate interplay among thermal-mechanical-chemical factors in HEAs remain lacks clarity. Herein, a set of AlxCo10.5Cr10Fe25Ni(50-x)Ti4.5 HEAs featuring desirable high-temperature phase stability, oxidation resistance, and spalling resistance at 1100 °C were meticulously designed. And the effects of phase composition and thermodynamics on the evolution of surface oxides in these HEAs were investigated. Specifically, the formation of the unfavorable σ phase between 860-1200 °C is avoided through the composition adjustment. The oxidation resistance is governed by the presence of large-size columnar grains and the spalling resistance of the Al2O3 oxide film. The spalling resistance is mainly linked to the configuration sequence (Spinel→FeAlTiO5→TiO2) of the outer oxide layer and the phase transition of the matrix either to FCC or BCC. Meanwhile, the formation of FeAlTiO5 assumes a crucial role in the optimization of spalling (>770h) and oxidation resistance (2.6×10-12g·cm-2·s-1) within an Al20Co10.5Cr10Fe25Ni30Ti4.5 alloy. These findings provide guidance for the development of TBC systems endowed with exceptional properties tailored for engineering applications.

Effect of surface treatment on oxidation film of 55SiCr spring steel wire

Abstract In this work, the surface pretreatments of 55SiCr spring steel wire rods were conducted using shot blasting and phosphating. After drawing, the steel wire was heated at 950°C × 15 s, followed by oxidation treatment with high-temperature steam or air for 3 seconds, and tempering treatment at 520°C. The effects of different surface treatment methods on the surface oxide film of spring steel wire were studied using stereomicroscopy, SEM, EDS, and XRD. The results showed that the steel wire surface oxide film with phosphating pretreatment was thicker and easy to fall off. The thickness of the oxide film formed by phosphating pretreatment samples increased by 2.1 um (high-temperature steam) and 0.3 um (air) compared to the shot-blasting samples under different oxidation atmospheres. High-temperature steam oxidation treatment significantly increased the thickness of the oxide film by 0.65 um (shot blasting) and 2.45 um (phosphating) under different surface pretreatment conditions. The outer surface of the oxide film turned black with high-temperature steam oxidation treatment and turned yellowish brown with air oxidation treatment. By both above oxidation treatments, the oxide film showed a multilayer structure, with enrichment of Cr and Si on the inner side.

Corrosion of Copper, Cupronickel, Nickel Aluminium Bronze and Super-Duplex Stainless Steel Rotating Cylinder Electrodes in Seawater under Turbulent Flow Conditions

The corrosion of uncoated metals in a marine environment restricts the choice of suitable engineering metals and alloys. Anodic dissolution of metal and cathodic reduction of oxygen are important processes and formation of a surface oxide film can affect both electrode reactions. Charge transfer and mass transfer data can provide information on corrosion rate and mechanism. Several metals and alloys having a history of use in marine engineering are considered, including copper, two copper alloys (cupronickel and nickel aluminium bronze) plus a more recent addition to strong, corrosion resistant alloys (a super duplex stainless steel). The rotating cylinder electrode offers the benefits of a controlled, turbulent flow of electrolyte, facilitating controlled mass transfer in a compact cell geometry which is well-suited to bench-top operation. These features are illustrated using a variety of electrochemical techniques, including open-circuit potential vs time monitoring, linear sweep voltammetry, rotation speed step- or potential step current transients and linear polarisation resistance measurements. Seawater taken from Langstone Harbour, Hampshire, UK, was filtered, air-saturated, pH 8.0 and maintained at 25 °C. Dimensionless group correlations and graphical plots (using an analogous approach to the Koutecky-Levich equation for an RDE) enabled contributions of charge transfer-, mixed- and mass transfer- controlled data to be appreciated, allowing the Tafel slopes of electrode reactions, the diffusion coefficient of dissolved oxygen, the mass transfer coefficient for oxygen reduction and the mean corrosion rate to be estimated.

Creep-to-rupture of T91 steel in static liquid lead-bismuth eutectic: Effects of cyclic temperature and oxygen environment

The creep-to-rupture behavior of T91 steel in static liquid lead–bismuth eutectic (LBE) is investigated, focusing on the impacts of cyclic temperature and oxygen condition. The results indicate that thermal cycling, oxygen deficiency, and high applied stress levels significantly accelerate creep deformation and reduce the creep-to-rupture lifetime of T91 steel in LBE. Surface oxide scales on T91 steel and their self-healing mechanisms play a crucial role in enhancing the creep resistance by isolating the LBE contact and delaying crack initiation and propagation. However, the integrity of this oxide scale is compromised under cyclic thermal conditions and low oxygen levels, leading to premature failure. Microstructural examinations reveal the evolution of oxide scale damage and self-healing mechanisms. The findings suggest that oxide scale failure mechanisms should be considered when designing the long-term operational performance of advanced LBE-based reactors.