This work discusses the microstructure evolution observed in a quenching and partitioning (Q&P)-processed martensite/austenite stainless steel during the partitioning step at 400 °C for 300 s, where distinct microstructural bands rich in austenite due to elemental segregation, evolve into a uniform distribution of austenite grains. This phenomenon is characterised and investigated using a model for the carbon partitioning from martensite to austenite coupled with the movement of the martensite-austenite interface. The observed elimination of microstructural bands is found to be related to the topological distribution of austenite grains and the heterogeneity of the thermodynamic equilibrium regime at the various interfaces governing the partitioning process. Furthermore, the concurrence of banding elimination (local equilibrium) and phase growth towards the global equilibrium phase fractions is investigated in the simulations in terms of the role of Mn. It is found that the local equilibrium-negligible partitioning (LENP) conditions lead to the most realistic outcome.

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In this work, four different techniques were concurrently applied to study the interplay between local electroactivity and electrode surface characteristics of free-standing, polycrystalline boron-doped diamond (BDD). Scanning electron microscopy, electron back-scatter diffraction, Raman mapping and scanning electrochemical microscopy were used to probe the electrode morphology, grain orientation and boundaries, composition, and local electrochemical activity, respectively. Both nucleation and growth BDD surfaces together with the cross-section area were carefully investigated for the first time in a single study using the combination of all four techniques. This enabled us to obtain significant insights into the highly heterogeneous nature of the polycrystalline BDD material. Notably, boron dopants were confirmed to be non-uniformly distributed over the BDD material, which is characterized by a distinct columnar structure and composition of grains of various orientations. Particularly, the highest electrochemical activity was recorded on the highest doped (111) crystal orientation. In contrast, the averagely boron-doped (100)-oriented facet showed non-conductive nature. This highlights that the local electrochemical activity of the BDD surface is strongly grain-dependent and the most significant factors governing the obtained responses are crystallographic orientation and boron doping. Moreover, increased boron and sp² carbon content in the boundary regions was recognized by Raman mapping. However, such localized enrichment in impurities did not translate into enhanced electrochemical activity, which implies that boron atoms at the inter-grain areas are predominantly inactive. Finally, it is crucial to consider all characteristics of the polycrystalline BDD including crystal orientation, which is particularly relevant if micro- and nanoscale probing is intended.

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In this work we present the pulsed current (PC) electrodeposition of Sn-Cu-Ni alloy as lead-free solder candidate, from choline chloride – ethylene glycol eutectic mixtures (1:2 molar ratio) onto copper metallic substrates. Electrolytes containing Sn²⁺, Cu²⁺ and Ni²⁺ salts in the selected deep eutectic solvent have been considered. The effect of the applied frequency of PC on the morphology, composition and melting point of the alloy is discussed and compared to the ones obtained using direct current (DC) plating mode. A refinement of the grain size and lower melting temperature of the alloy were noticed when pulsed current was applied. A comparative analysis of the electrochemical corrosion behaviour at macro- and micro- scale has been performed in 0.5 M and 0.1 M NaCl solutions involving potentiodynamic polarization curves, electrochemical impedance spectroscopy (EIS) and scanning vibrating electrode (SVET) techniques. Furthermore, an analysis after 96 h of exposure to salt mist test simulating a corrosive attack in harsh environment is presented, too. The obtained results showed enhanced corrosion resistance of the ternary alloys electrodeposited under PC conditions (the best for 1.67 Hz frequency) as compared to those using DC. Additionally, Raman spectroscopy evidenced the presence of tin oxi/hydroxy chloride and tin oxides as surface corrosion products. A corrosion mechanism has been proposed.

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Al-Mg-Si alloys are known as structural materials and are primary alloys in the automotive industry to achieve weight reduction. Shifting toward sustainability, lower energy consumption, and less CO2 emission necessitates recycling. However, the unavoidable accumulation of scrap-related impurities, e.g., Cu and Zn, during the recycling process can influence corrosion resistance of recycled alloys. The results show that Al-Mg-Si alloys containing 0.05 wt% Cu exhibit low intergranular corrosion resistance. The intergranular corrosion resistance of these alloys is notably improved by adding 0.06 wt% Zn. Low concentrations of Cu and Zn are found to strongly affect the crystal structure of hardening precipitates.@en

The present study investigated a new configuration of friction stir welded joints from two aluminum alloys. Dissimilar welds AA6082/AA1350 were examined, whereas, for AA1350, two states were investigated—coarse-grained (CG) and ultrafine-grained (UFG). Changes in the mechanical and electrochemical properties regarding the microstructure evolution across the welds were discussed. The average grain size in the stir zone (SZ) for all materials equaled 4 to 5 µm with a fraction of high-angle grain boundaries of about 77 pct, indicating the occurrence of continuous dynamic recrystallization. Changes in the microhardness across the welds were connected with differences in grain size (AA1350) and dissolution of β″ precipitates in the SZ of AA6082. As a result, the tensile strength of the welds decreased compared to base materials AA6082 and AA1350 UFG; however, there was an increase when compared to the base material AA1350 CG. Electrochemical experiments revealed that pitting corrosion occurred for AA1350, while for AA6082, it was a combination of pitting and intergranular corrosion. The depth of corrosion attack was higher for AA1350, with a maximum value of ~ 70 µm for base materials, while in the SZ, a depth decreased to 50 µm. For the AA6082, the maximum depth was measured in the SZ and did not exceed 30 µm.

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A detailed microstructural and electrochemical analysis of electroless nickel phosphorous (NiP) coatings with P contents of 13.2 ± 1.2 wt%, 12.9 ± 0.7 wt%, and 8.3 ± 0.8 wt% on a copper substrate was performed to study the corrosion behaviour of electroless NiP/Cu systems. The P content of the electroless NiP coatings plays an essential role in the microstructure of the coatings in terms of crystallinity. The crystallinity variations, representing the extent of crystalline and amorphous phases within the material, with P content, affect the local electrochemical characteristics and, hence, the corrosion protection behaviour of electroless NiP coatings. The coatings with the highest P content showed the best corrosion performance in a 3.5 wt-% NaCl solution. In contrast, the surface of the electroless NiP coatings with low P content is more susceptible to corrosion due to the presence of locations with heterogeneous electronic properties that initiate localised corrosion. Microgalvanic interactions with a high cathode-to-anode surface ratio govern the localised corrosion kinetics of the low P-content samples. A high concentration of nodule boundaries and/or other existing structural defects on the surface serve as anodic sites, whereas the remainder of the surface serves as cathodic sites.

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The authors regret that an error occurred in the description of equation 3 in the published version of the above-mentioned article, which should be as follows: [Formula presented] The correct equation was implemented for calculating all the results presented in the article, so all results, discussions and conclusions presented in the manuscript remain fully valid > The authors would like to apologise for any inconvenience caused.

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Utilizing a dedicated micro-sized three-electrode cell, this study systematically investigates early-stage electrochemical properties and corrosion behavior of pure iron under single droplets. Various volumes and NaCl concentrations were considered during the evaporation-driven shape and concentration evolution of single droplets. The measurements disclosed that reducing the droplet size from 5 µL to 1.5 µL at 0.01 M NaCl concentration, increased noise resistance (R_n) and polarization resistance (R_p) values. However, at 0.1 M and 0.2 M NaCl concentrations, reducing droplet size led to the domination of relatively high chloride ion concentration over oxygen diffusion, resulting in a very low R_n and R_p and hence enhanced localized corrosion.

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Mg and its alloys are promising biodegradable materials for orthopedic implants and cardiovascular stents. The first interactions of protein molecules with Mg alloy surfaces have a substantial impact on their biocompatibility and biodegradation. We investigate the early-stage electrochemical, chemical, morphological, and electrical surface potential changes of alloy WE43 in either 154 mM NaCl or Hanks’ simulated physiological solutions in the absence or presence of bovine serum albumin (BSA) protein. WE43 had the lowest electrochemical current noise (ECN) fluctuations, the highest noise resistance (Zn = 1774 Ω·cm2), and the highest total impedance (|Z| = 332 Ω·cm2) when immersed for 30 min in Hanks’ solution. The highest ECN, lowest Zn (1430 Ω·cm2), and |Z| (49 Ω·cm2) were observed in the NaCl solution. In the solutions containing BSA, a unique dual-mode biodegradation was observed. Adding BSA to a NaCl solution increased |Z| from 49 to 97 Ω·cm2 and decreased the ECN signal of the alloy, i.e., the BSA inhibited corrosion. On the other hand, the presence of BSA in Hanks’ solution increased the rate of biodegradation by decreasing both Zn and |Z| while increasing ECN. Finally, using scanning Kelvin probe force microscopy (SKPFM), we observed an adsorbed nanolayer of BSA with aggregated and fibrillar morphology only in Hanks’ solution, where the electrical surface potential was 52 mV lower than that of the Mg oxide layer.@en

This paper presents a novel approach to investigate atmospheric corrosion kinetics of carbon steel under multi-droplet conditions. A homemade climate chamber has been developed to accurately control and monitor environmental conditions, including temperature (T) and relative humidity (RH), during exposure. Carbon steel corrosion kinetics are monitored with a custom-designed Electrical Resistance (ER) sensor pair. Savitzky-Golay (S-G) based filtering technique has been used for the corrosion signal processing. In parallel, top-view droplet temporal evolution has been recorded by microscopic imaging and analyzed for both droplet size distribution and the solid-liquid contact angle. The droplet size distribution can typically be described with a power-law form curve. The curve shows a decrease in height and a concurrent expansion in width with progressive drying. The introduction of NaCl into the electrolyte and surface roughness variations have also been identified to substantially influence the carbon steel corrosion rate. A strong correlation between the corrosion rate derived from the ER monitoring method and the RH can be observed. This correlation is further analyzed to incorporate the impact of droplet-based electrolyte conditions. This study offers valuable insights into the development of mechanistic and kinetic prediction models for atmospheric corrosion.

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In this work, the corrosion mechanism of AA2024-T3 covered by a lithium-based conversion layer is studied with high spatial and temporal resolution. Although the aluminium alloy surface is protected by a multi-layered conversion layer, areas around intermetallic phases (IMPs) represent weak spots due to an insufficient generation of a protective inner dense layer. For the freshly formed conversion layer, both the top and the inner layer undergo a gradual dissolution upon exposure to relatively dilute NaCl solution within 2 h due to their chemical instability. For the ambiently-aged conversion layer, most corrosion activity around IMPs is related to the S-phase and large constituent phases, due to their active nature and the lower local conversion layer quality, respectively. Moreover, S-phase-related corrosion activity lasts approximately 8 h due to fast dissolution whereas reactions induced by large constituent particles remain active over the entire re-immersion period of 12 h.

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The quest for novel alternatives to hexavalent-chromium-based corrosion inhibitors is of utmost significance and urgency. Strict international health and safety regulations, due to growing concerns regarding the impact of hexavalent chromium on human health and the environment, have pushed the commercial introduction of many alternative inhibitor types, but the implementation of alternative active protective primers for structural parts in the aerospace industry is still pending. This endeavour has proven to be remarkably challenging, as the potential replacement coating types must meet numerous functional requirements encompassing cost-effectiveness and exceptional corrosion protection for intrinsically corrosion susceptible aerospace aluminium alloys. In recent years, considerable attention has been drawn to lithium salts as environmentally friendly corrosion inhibitors forming the basis for a novel active protective coating technology. The involvement of lithium ions has been shown to play a pivotal role in the conversion process of aluminium alloy surfaces by stabilizing the reaction products, thereby facilitating the gradual development of a protective layer with a multi-layered configuration, which exhibits considerable variability in morphology, depending on local chemical and electrochemical conditions. The versatility of the lithium-based corrosion protection extends to their application as corrosion inhibiting pigments in organic coatings or as a pre-treatment, directly forming conversion layers, thereby enhancing their practical implementation. However, previous chromate replacement reviews only introduced the promising outcomes provided by the lithium technology, omitting key details of its development and formation mechanism. This paper critically reviews and summarizes the studies conducted to date on lithium-based inhibitor technologies for the corrosion protection of aluminium alloys as well as topics to be investigated in the future.

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The effect of friction stir welding (FSW) on the microstructure and localised corrosion behaviour of the dissimilar weld of AA2099 T83 and AA2060 T8E30 alloys is investigated. FSW results in a drastic change in the microstructure thus altering their corrosion behaviour. The heat-affected region exhibits similar attack morphology to their respective base metal but is the most protected region. The stir zone (SZ) is the most susceptible to attack. During immersion of the entire weld, attack initiation occurs from the AA2060 SZ due to galvanic activity within the region caused by the overlap of the grains in the weld zone.

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The inhibition of Mo segregation and phase precipitation is vital for improving the hot workability and corrosion resistance of superaustentic stainless steels (SASS). The boron non-equilibrium segregation of S31254 SASS was implemented through solid solution, air cooling, and diffusion at low-temperature treatment (SADT). The precipitation process and intergranular corrosion (IGC) of S31254 SASS with various boron distributions were researched at a sensitive temperature. The second phases were observed and identified by SEM and TEM. IGC susceptibility was evaluated by double-loop potentiodynamic reactivation (DL-EPR) measurements. The SADT treatment promoted more segregation of B at the grain boundary, leading to lower amounts of grain boundary precipitation before aging for 6 h. The decrease of σ phases in B-regulated samples enhances the IGC resistance, compared with the samples without B addition specimens.

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The present article investigates the influence of chemical composition and phase fractions on the corrosion behaviour of industrially produced quenching and partitioning (Q&P) martensitic stainless steels. Localised corrosion was analysed by scanning Kelvin probe force microscopy (SKPFM) and scanning electrochemical microscopy (SECM) in 3.5 wt.% NaCl solution. SKPFM revealed a Volta-potential difference of around 40 mV between inclusions and the matrix, which is larger than the Volta potential variations within the matrix. This difference in surface potential is a driving force for selective dissolution (corrosion initiation) at inclusions and inclusion/matrix interfaces. SECM detected early pitting initiation, particularly in alloys containing MnS and TiN inclusions. Results suggest that pitting initiation and propagation occur at those specific regions. This study emphasised that irrespective of chemical composition and phase fraction, localised corrosion initiation in Q&P-processed martensitic stainless steels is predominantly governed by the presence of inclusions.

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This work presents an investigation of the microstructure development during the application of the quenching and partitioning (Q&P) process to two stainless steels with different Mn content. The results are compared with calculations based on the constrained carbon equilibrium theory, paying special attention to the presence of reactions competing for the carbon available for partitioning and to the effect of alloying element segregation. Results show that chromium carbides must be considered when accounting for the carbon available for austenite stabilisation. Moreover, manganese/chromium segregation bands play an important role in the microstructure development, particularly in martensite formation, with important consequences in the microstructure development during the following processing steps.

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Scanning electrochemical microscopy (SECM) is employed to characterize the evolution of local electrochemical surface activity during lithium-based conversion layer formation on legacy aerospace aluminium alloy AA2024-T3. Initially, three types of studied intermetallic particles - S-, θ- and constituent phases - act as active cathodic areas. Subsequently, θ- and constituent phases show passivation preceding that of S-phase particles during the later conversion layer formation stages. The entire surface, including the matrix region, shows a higher reactivity at the beginning and then gradually shows decreasing reactivity. Hydrogen evolution-generated bubbles attach to the alloy surface and locally hinder the conversion layer formation, weakening the corrosion protection the conversion layer provides at those locations.

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Zinc aluminium (Zn-Al) and lithium aluminium (Li-Al) – layered double hydroxides (LDH) coatings with incorporated inhibitors (Li−, Mo− and W−based) were successfully synthesized on AZ31 Mg alloy. Zn−Al LDH W and Li−Al LDH Li showed the highest corrosion resistance and were selected for further evaluation. SEM cross−section examination revealed a bi−layer structure composed of an outer part with loose flakes and a denser inner layer. XRD, FTIR, and XPS analysis confirmed the incorporation of the inhibitors. Post−treatments with corrosion inhibitors containing solutions resulted in the selective dissolution of the most external layer of the LDH coating, reducing the surface roughness, hydrophilicity and paint adhesion of the layers. Active corrosion properties were confirmed by SVET evaluation for the Zn−Al LDH W coating. The proposed active corrosion mechanism involves the ion−exchange of aggressive Cl⁻ ions, deposition of hydroxides and competitive adsorption of W−rich corrosion inhibitors.

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Functional oxide nanoparticles are extensively utilized in the last decades for biomedical purposes due to their unique functional properties. Nevertheless, their biodegradation mechanism by biological species, particularly by proteins at oxide/protein interfaces, still remains limited. Here, a systematic approaches is provided to investigate electrochemical behavior, electronic properties, and biodegradation mechanism of cobalt ferrite (CFO) and cobalt ferrite-bismuth ferrite (CFO-BFO) core-shell nanoparticles in apoferritin-containing media. Scanning Kelvin probe force microscopy results indicate that the presence of a thin shell (≈5 nm) of BFO on CFO causes a significant increase in surface potential. The potentiodynamic polarization measurements in different solutions showed higher anodic current densities for both samples when decreasing pH and increasing apoferritin concentration. Notably, CFO-BFO exhibits lower anodic current densities than CFO due to a slightly higher flat band potential and lower donor density distribution on CFO-BFO than on CFO, which results in lower electrochemical activity. Long-term monitoring reveals that biodegradation of both nanoparticles is accelerated by high apoferritin concentrations and acidic media, resulting in the decrease of electrochemical potentials and impedance values, and enhancement of metal ion release. Thus, this systematic biodegradation study can help to predict the lifespan and toxicity of these functional nanoparticles in biological environments.

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The influence of ageing under ambient conditions on the corrosion protective behaviour of a lithium-based conversion layer on AA2024-T3 is studied in this work. Conversion layers aged at ambient conditions for relatively short times (0 h and 4 h), show an initial high degree of corrosion inhibition but a much lower protectiveness after the inhibition stage terminates. Conversion layers with relatively long ageing times (24 h and 72 h) show a rather stable corrosion resistance which is higher than that of short-time aged samples. It is hypothesized that the freshly-formed conversion layer has trapped a certain amount of lithium ions and water molecules, leading to ongoing and heterogeneous growth of the conversion layer with time under ambient indoor conditions. Moreover, conversion layers with short ageing times show early-stage active corrosion protection by lithium-ion release.

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