Y. Gonzalez Garcia
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73 records found
1
From electrostatics to electrochemistry
Rethinking volta potential in nowadays and future in-situ kelvin probe studies
Understanding localized corrosion under atmospheric droplets is critical, yet previous studies have mostly focused on single-droplet systems or general trends, leaving the role of individual droplets within multi-droplet environments yet to be explored. Here, we present a fully automated, image-based, data-driven framework for analyzing corrosion progression under thousands of droplets simultaneously. Using time-resolved optical imaging and pre-trained large vision models for droplet segmentation, we construct per-droplet color features and propose a probability-based representation of corrosion product formation in inner and outer regions of interest. This approach overcomes the limitations of binary classification by capturing the continuous and spatially heterogeneous nature of corrosion product formation. Applied to carbon steel exposed to over 1500 pre-sprayed 1 M NaCl droplets of various sizes, the method reveals that the probability of corrosion product presence strongly depends on droplet size, with larger droplets more likely to exhibit products both under and around the droplet footprint. Moreover, corrosion products in the outer region can appear independently of under-droplet corrosion, suggesting a role for inter-droplet interactions. By transforming raw imaging data into physically meaningful per-droplet metrics, this work offers a scalable platform for investigating localized corrosion kinetics and morphology in complex, real-world droplet populations, opening new opportunities for connecting droplet formation and population behavior to local and overall atmospheric corrosion rates.
Recycling Al alloys promotes greater sustainability, as the energy required to produce recycled alloys is only about 5 % of that needed to produce the same amount of primary alloys. However, the build-up of impurities, such as Zn, during the recycling process can negatively affect the corrosion resistance of recycled alloys. The results show that the susceptibility to intergranular corrosion increased with minor additions of zinc (≤ 0.06 wt%). Zn was found to segregate along the grain boundaries, and the STEM-EDS results indicate that the Zn incorporates into the structure of Mg-Si containing grain boundary precipitates.
Corrosion and environmental sensor response delays during monitored multi-droplet wetting
Unraveling time lags in atmospheric corrosion
This study investigates time lags between environmental changes, electrolyte formation, and atmospheric corrosion sensor responses under controlled multi-droplet wetting. A commercial corrosion and environmental sensor was combined with in-situ microscopy, and an Artificial Intelligence (AI)-based segmentation approach was applied to track droplet growth. A cross-correlation analysis identified and quantified time lags between Surface Relative Humidity (SRH), droplet radius, and sensor responses based on Interdigitated Electrodes (IDE) measuring conductance, galvanic corrosion, and free corrosion. This approach ultimately aids in understanding how environmental fluctuations affect the dynamic behaviour of the electrolyte layer and, in turn, influence atmospheric corrosion sensor responses.
This study investigates the localised corrosion mechanisms in laboratory-processed Q&P-treated martensitic stainless steels. Two steel variants, one NbTi-free (alloy B) and the other micro-alloyed with Nb and Ti (alloy M) were investigated to elucidate the influence of microalloying on corrosion behaviour. Both NbTi-free and NbTi-micro alloyed martensitic stainless steels were examined using a combination of electrochemical methods (potentiodynamic polarisation and double-loop electrochemical potentiokinetic reactivation) and microstructural analysis (Transmission Electron Microscopy and scanning Kelvin probe force microscopy). Potentiodynamic polarisation results showed no significant differences between the alloys and no clear evidence of pitting corrosion. Optical analysis of the specimens showed preferential attack at grain boundaries. Double-loop electrochemical potentiokinetic reactivation measurements revealed a higher degree of sensitisation to intergranular corrosion in the microalloyed steel compared to the NbTi-free variant. Transmission Electron Microscopy showed that intergranular corrosion in both steels originated from chromium depletion zones adjacent to chromium carbides along grain boundaries. The increased susceptibility in the microalloyed steel was linked to the presence of TiN(Nb) particles. Scanning Kelvin probe force microscopy further revealed variations in surface potential at grain boundary precipitates and depleted zones, emphasising their role in intergranular corrosion initiation. These findings emphasise the critical influence of processing routes on the corrosion mechanisms of Q&P-treated martensitic stainless steel.
In this research, three types of super austenitic stainless steel (SASS) with nitrogen levels of 0.2, 0.28, and 0.38 wt.% were developed. By maintaining a relatively high manganese content of approximately 1.5 wt.% and nickel content of around 18 wt.%, nitrogen was fully incorporated into the austenite, resulting in alloy samples designated as 0.2N, 0.3N and 0.4N. The hot-rolled plates of these alloys underwent a solution treatment at 1180°C for 30 min, followed by aging at 950°C for durations of 30 min, 2 h and 6 h, respectively. The influence of nitrogen content on phase precipitation behaviour was examined through various micro-structure characterisation techniques. The corrosion resistance of the samples was further evaluated using potentiodynamic polarisation experiments, Electrochemical impedance spectroscopy (EIS) and double loop-electrochemical potentiokinetic reactivation (DL-EPR) method. The results indicated that with an increase in nitrogen (N) addition, the quantity of σ phases decreased while and the formation of Cr2N phases increased during the same aging period. Furthermore, at the same aging duration, the 0.3N SASS exhibited the highest pitting resistance and the lowest degree of sensitization (DOS) value compared to all other steels, attributed to the minimal precipitates present along the grain boundaries.
Nickel coatings are widely used for corrosion and wear resistance, often undergoing post-treatment to enhance performance. Depending on their final application, Ni-coated steel may be subjected to mechanical forming processes to produce cylindrical can shapes, commonly used as battery cases or food storage containers where corrosion resistance is critical. Before mechanical forming, a key thermomechanical process called temper rolling is applied to improve coating adhesion, reduce residual stress, and minimize surface defects. This study systematically investigates the corrosion mechanisms of Ni-electroplated steel after annealing and temper rolling, demonstrating that both processes enhance localized corrosion resistance by modifying microstructure, surface morphology, and surface oxide evolution. These treatments promote passivity by increasing NiO content relative to Ni(OH)2, significantly improving charge transfer resistance. Additionally, iron diffusion from the steel substrate generates an electrical surface potential gradient within the coating, affecting nobility variations across different regions. Post-corrosion analysis of temper-rolled samples reveals that corrosion initiation occurs at submicron grains, where structural gaps facilitate substrate exposure, underscoring the role of processing routes in enhancing coating durability.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
Atmospheric corrosion of iron under a single droplet
A new systematic multi-electrochemical approach
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 (Rn) and polarization resistance (Rp) 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 Rn and Rp and hence enhanced localized corrosion.