Corrosion and Materials Degradation

Since 2011, there has been an international effort to evaluate the behavior of newer fuel rod materials for the retrofitting of existing light water reactors (LWR). These materials include concepts for the cladding of the fuel and for the fuel itself. The materials can be broadly categorized into evolutionary or improved existing materials and revolutionary or innovative materials. The purpose of the newer materials or accident-tolerant fuels (ATF) is to make the LWRs more resistant to loss-of-coolant accidents and thus increase their operation safety. The benefits and detriments of the three main concepts for the cladding are discussed. These include (i) coatings for existing zirconium alloys; (ii) monolithic iron–chromium–aluminum alloys; and (iii) composites based on silicon carbide. The use of ATF materials may help extend the life of currently operating LWRs, while also being a link to material development for future commercial reactors. Full article

This research article explores the potential of optical fibers as sensors, highlighting their ability to measure various parameters such as temperature, pressure, stress, and radiation dose. The study focuses on investigating the material compatibility of optical fibers in challenging sensing environments like Gen II/II+ and advance nuclear reactors, as well as concentrated solar power (CSP) plants. Material compatibility tests were conducted to determine the feasibility of using fluorine and germanium optical fiber sensors in these environments. The study found that raw fibers were corrosion-resistant to lead bismuth eutectic at 600 °C, regardless of the coating. In molten salt environments, raw fibers were incompatible with FLiNaK but showed corrosion resistance to MgCl₂-NaCl-KCl. However, the survivability of raw fiber optics improved with a gold coating in FLiNaK. Raw fiber optics were found to be incompatible in high-temperature steam at 1200 °C and in a pressurized water reactor (PWR) at 300 °C. Full article

The alkali–aggregate reactivity (AAR) of concrete, long known for mass concrete, can also induce corrosion of steel in reinforced concrete structures. Several examples are given for which the origin of observed reinforcement corrosion and loss of concrete cover originally was attributed to chloride-induced or to carbonation-induced reinforcement corrosion. Critical reviews of these cases, using available information, suggest that, more likely, the observed crack patterns and concrete deterioration are the result of long-term AAR-induced concrete matrix expansion and loss of concrete strength and that these effects occurred prior to the eventual initiation of reinforcement corrosion. This proposition is supported by finite element and other stress analyses of various concrete–steel ensembles. They show that concrete expansion produces tensile stresses localised at and near exterior concrete surfaces or relative to the reinforcement. The locations of high-stress and -strain zones so produced correlate with field observations of long-term concrete cracking and delamination. The present interpretations highlight that AAR may be a significant contributor to initiation and subsequent long-term development of reinforcement corrosion in structurally reinforced concretes. Full article

The destruction of the passive oxide can be caused by the action of a radionuclide, which collides with the surface of the oxide. In this case, the ${\beta }^{-}$ nuclear particle produced by the decay of tritiated water is considered for corrosion, and it follows that the ${\beta }^{-}$ energy is absorbed first into the oxide. The penetration depth is sufficient for all the passive oxides to be destabilized. Destabilization was examined by voltammetry and by the electrochemical circuit in the passive potential. The corresponding pathway leads to the destruction of oxide. Tests carried out using a chaos data analyzer are an aid for expertise. Different behavior may occur depending on the passive potential and the ${\beta }^{-}$ density. The synchronization of phase space spectra and tests realized sector by sector make possible the interpretation of divergence leading to unstable oxide and oxide destruction at different passive potentials and for different ${\beta }^{-}$ particle densities. Full article

The biocorrosion of carbon steel poses a risk for ships combining seawater and fuel in metal ballast tanks. Ballast tanks were simulated by duplicate reactors containing carbon steel coupons and either petroleum F76 (petro-F76), Fischer–Tropsch F76 (FT-F76), or a 1:1 mix of both fuels, to investigate whether the alternative fuel FT-F76 influenced this risk. The polycarbonate reactors were inoculated with seawater, and the control reactors did not receive fuel. The reactors were monitored for 400 days, and they all reached a pH and open circuit potential where elemental iron was oxidized, indicating corrosion. The reactors containing petro-76 or fuel mix had higher levels of dissolved iron; one of each replicate had lower concentrations of sulfate than the original seawater, while the sulfate concentration did not decrease in the other incubations. The high sulfate reactors, but not the low sulfate reactors, had a high relative abundance of microaerophilic sulfide-oxidizing bacteria. The FT-F76 and the no-fuel reactors had a high relative abundance of iron-sequestering Magnetovibrio. Although dissolved iron and loss of sulfate under anoxic conditions are associated with biocorrosion, our results suggest that in our reactors these indicators were altered by iron-sequestering and sulfide-oxidizing microbes, which is consistent with the slow diffusion of oxygen across the polycarbonate reactors. Full article

This paper investigated carbon steel corrosion in an enclosed environment, where one set of steel was immersed in 3.5 wt.% NaCl solution and another exposed to humid (condensation) conditions. The study employed electrochemical noise and electrochemical impedance spectroscopy techniques to monitor real time corrosion behaviour. The samples were evaluated with surface characterisation techniques including optical light microscope, scanning electron microscope with energy dispersive X-ray spectroscopy, and Raman spectroscopy. The results showed that carbon steel immersed in the liquid phase at a constant temperature exhibited the highest weight loss. However, the carbon steel exposed to water condensation (gas phase) at 80 °C manifested extensive localised corrosion. EN results agreed with the microscopy findings. Full article

Most regulations on the manufacturing of concrete for reinforced concrete structures rest on durability models that consider the corrosion of reinforcements. Those models are based on factors such as humidity, frost, presence of chlorides, and internal characteristics of the concrete itself, like resistance, porosity, type of cement, water/cement ratio, etc. No regulations, however, adopt a purely constructive perspective when evaluating the risk of corrosion, i.e., the relative position of the reinforced concrete in buildings. The present work focuses on the relationship between the position of the damaged element and the building envelope. A total of 84 elements (columns and reinforced concrete beams) across twenty buildings were analysed in the provinces of Alicante and Murcia (Spain). The reinforcement concrete of these elements underwent carbonation-induced corrosion according to their positions in the buildings: (A) façade columns in contact with the ground; (B) interior columns in contact with the ground; (C) columns of walls in contact with the ground; (D) columns and external beams protected from rain; (E) columns and external beams exposed to rain; (F) columns and beams in air chambers under sanitary slabs; and (G), columns and interior beams. Of all types, elements (E) and (F) suffered carbonation-induced corrosion faster than the models used in the regulations, and type (G) underwent slower carbonation. Full article

The AA 2198-T851 is a third-generation Al-Li alloy developed for use in the aircraft industry. Al-Li alloys are susceptible to localized corrosion due to their complex microstructure resulting from the used thermomechanical treatment. In order to prevent localized corrosion, these alloys are usually protected by anodizing in order to avoid a corrosive environment. Subsequently, for anodizing, a sealing treatment is usually performed for parts. Some sealing treatments use hexavalent-chromium-ion-containing solutions. In this investigation, a chromium-free sealing treatment in a solution with cerium ions has been carried out, and the effect on the corrosion resistance of the AA2198-T851 alloy was investigated. Hydrothermally sealed or unsealed samples were also tested for corrosion resistance for comparison reasons. The corrosion resistance of the anodized aluminum alloy, either hydrothermally sealed or in a cerium-ion-containing solution, was evaluated in a sodium chloride solution by electrochemical impedance spectroscopy as a function of immersion time. The samples sealed in a cerium-containing solution increased their corrosion resistance when compared to the hydrothermally sealed. The effectiveness of the sealing process with cerium that was observed in the electrochemical tests indicated that after the corrosive attack of the barrier layer, there was a “sealing” process of the sample surface. Full article

We address here an important issue related to sensitization effects in Al5083 by mitigating the grain boundary precipitation of the beta phase and demonstrate that the addition of a small amount of boron to Al5083 impedes the precipitation of the beta phase, Al₃Mg₂, also known as the Samson phase. In Al–Mg alloys, the precipitation of Al₃Mg₂ usually occurs at grain boundaries in the temperature range of 50 to 200 °C from a supersaturated solid solution of Al–Mg and makes these alloys susceptible to intergranular corrosion and stress corrosion cracking. Upon boron addition, we show, using transmission electron microscopy, that a diboride phase, AlMgB₂, forms at grain boundaries instead of the beta phase upon extended annealing at 150 °C. This diboride phase does not dissolve in saltwater, suggesting it is less anodic relative to the matrix. To quantify and compare the dissolution characteristics, we carried out nitric acid mass loss test for Al5083 samples containing 3 wt.% boron treated at 190 h at 150 °C, and fully sensitized Al5083 samples containing 0.0 wt.% boron. We estimate the mass loss to be 4 mg/cm² for boron containing samples as compared to the mass loss of 45 mg/cm² for samples without boron, indicating that the addition of boron is highly effective in suppressing the susceptibility to intergranular corrosion in Al5000 series alloys. This provides a potential route to minimize the longstanding problem of ship structure sensitization. Full article

Polymer-based coatings are a long-established category of protective coatings for metals and alloys regarding corrosion inhibition. The polymer films can degrade, and when coated on metallic substrates, the degradation facilitates moisture and oxygen penetration, reducing the polymer film’s adhesion to the metallic substrate and exposing the substrate to extreme conditions capable of corrosion. For this reason, pigments, inhibitors, and other compatible blends are added to the polymer coating formulations to enhance adhesion and protection. To prevent the possible deterioration of inhibitor-spiked polymer coatings, inhibitors are encapsulated through diverse techniques to avoid leakage and to provide a controlled release in response to the corrosion trigger. This review discusses polymer-based coating performance in corrosion-causing environments to protect metals, focusing more on commercial steels, a readily available construction-relevant material used in extensive applications. It further beams a searchlight on advances made on polymer-based coatings that employ metal–organic frameworks (MOFs) as functional additives. MOFs possess a tailorable structure of metal ions and organic linkers and have a large loading capacity, which is crucial for corrosion inhibitor delivery. Results from reviewed works show that polymer-based coatings provide barrier protection against the ingress of corrosive species and offer the chance to add several functions to coatings, further enhancing their anti-corrosion properties. Full article

Magnesium (Mg) and its alloys are promising materials for temporary bone implants due to their mechanical properties and biocompatibility. The most challenging aspect of Mg-based implants involves adapting the degradation rate to the human body, which requires extensive in vitro and in vivo testing. Given that in vivo tests are significantly more labour-intensive than in vitro and ethics prohibit direct experiments on animals or humans, attempts are commonly undertaken to infer conclusions on in vivo degradation behavior from in vitro experiments. However, there is a wide gap between these tests, and in vitro testing is often a poor predictor of in vivo outcomes. In the development of biodegradable Mg-based implants, considerable efforts are being made to reduce the overall time and cost of in vitro and in vivo testing. Finding a suitable alternative to predict the degradation of Mg alloys, however, remains challenging. We present computational modelling as a possible alternative to bridge the gap between in vitro and in vivo testing, thus reducing overall cost, duration and number of experiments. However, traditional modelling approaches for complex biodegradable systems are still rather time-consuming and require a clear definition of the relations between input parameters and the model result. In this study, Kriging surrogate models based on the peridynamic in vitro degradation model were developed to simulate the degradation behavior for two main alloys, Mg-5Gd and Mg-10Gd, for both in vitro and in vivo cases. Using Kriging surrogate models, the simulation parameters were calibrated to the volume loss data from in vitro and in vivo experiments. In vivo degradation of magnesium has one order of magnitude higher apparent diffusion coefficients than in vitro degradation, thus yielding the higher volume loss observed in vivo than in vitro. On the basis of the diffusivity of the Mg${}^{2+}$ ions modeled under in vitro degradation, Kriging surrogate models were able to simulate the in vivo degradation behavior of Mg-xGd with a ratio between 0.46 and 0.5, indicating that the surrogate-modelling approach is able to bridge the gap between in vitro and in vivo degradation rates for Mg-xGd implants. Full article

This paper explores the roles of empiricism and determinism in science and concludes that the intellectual exercise that we call “science” is best described as the transition from empiricism (i.e., observation) to determinism, which is the philosophy that the future can be predicted from the past based on the natural laws that are condensations of all previous scientific knowledge. This transition (i.e., “science”) is accomplished by formulating theories to explain the observations and models that are based on those theories to predict new phenomena. Thus, models are the computational arms of theories, and all models must possess a theoretical basis, but not all theories need to predict. The structure of a deterministic model is reviewed, and it is emphasized that all models must contain an input, a model engine, and an output, together with a feedback loop that permits the continual updating of the model parameters and a means of assessing predictions against new observations. This latter feature facilitates the application of the “scientific method” of cyclical prediction/assessment that continues until the model can no longer account for new observations. At that point, the model (and possibly the theory, too) has been “falsified” and must be discarded and a new theory/model constructed. In this regard, it is important to stress that no amount of successful prediction can prove a theory/model to be “correct”, because theories and models are merely the figments of our imagination as developed through imperfect senses and imperfect intellect and, hence, are invariably wrong at some level of detail. Contrariwise, a single failure of a model to predict an observation invalidates (“falsifies”) the theory/model. The impediment to model building is complexity and its impact on model building is discussed. Thus, we employ instruments such as microscopes and telescopes to extend our senses to examining smaller and larger objects, respectively, just as we now employ computers to extend our intellects as reflected in our computational prowess. The process of model building is illustrated with reference to the deterministic Coupled Environment Fracture Model (CEFM) that has proven to be highly successful in predicting crack growth rate in metals and alloys in contact with high-temperature aqueous environments of the type that exist in water-cooled nuclear power reactor primary coolant circuits. Full article

Magnesium (Mg) has been explored during the last few decades in the biomedical industry as a biodegradable implant. However, mechanical properties and corrosion resistance are still big concerns for clinical use. Therefore, this study proposes a suitable surface modification of the Mg by plasma electrolytic oxidation (PEO) to improve its corrosion resistance and biological performance. Mg samples were processed in a galvanostatic mode using an electrolytic solution of a phosphate compound supplemented with either potassium pyrophosphate or sodium-potassium tartrate. The obtained coatings were physiochemically characterized by SEM, XRD, EDS, and micro-Raman spectroscopy. The corrosion resistance of the coatings was studied using a hydrogen evolution setup and electrochemical tests. Finally, the biological performance of the material was evaluated by using an indirect test with osteoblasts. Obtained coatings showed a porous morphology with thicknesses ranging from 2 to 3 µm, which was closely dependent on the PEO solution. The corrosion resistance tests improved the degradation rate compared to the raw material. Additionally, an unreported active–passive corrosion behavior was evidence of a protective layer of corrosion products underneath the anodic coating. Indirect in vitro cytotoxicity assays indicated that the coatings improved the biocompatibility of the material. In conclusion, it was found that the produced coatings from this study not only lead to material protection but also improve the biological performance of the material and ensure cell survival, indicating that this could be a potential material used for bone implants. Full article

In the present study, Mg-Al layered double hydroxide (Mg-Al/LDH) was synthesized on the surface of AZ31 Mg alloy substrate via in-situ hydrothermal treatment. Synthesis parameters were changed to determine their effect on the lateral size of LDH. For this purpose, etching in nitric acid and anodizing in sodium hydroxide solution were performed as surface pretreatments. Moreover, the influence of LDH solution pH (10 and 11) on the lateral size of LDH coating was investigated. Morphology, chemical composition, and crystalline structure were characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), Fourier transform infrared (FTIR) spectroscopy, and X-ray diffraction (XRD). The corrosion resistance of the coatings was investigated by H₂ measurements, salt spray, and electrochemical impedance spectroscopy (EIS). Moreover, the epoxy coating was applied on the best anti-corrosive LDH sample for assessing the compatibility and effectiveness of LDH on the corrosion properties of the substrate with the epoxy layer. At pH = 11, the lateral size of LDH was smaller than samples at pH = 10. In addition, small-sized LDH, as well as LDH/epoxy coating, revealed enhanced corrosion protection. Full article

Hydrogen, due to corrosion processes, can degrade high strength steels (HSS) through embrittlement and stress corrosion cracking mechanisms. Scanning Kelvin probe (SKP) mapping of surface potential was applied, to visualize the locations with an increased subsurface concentration of hydrogen in mild steel and martensitic HSS. This work can help to determine the reasons behind hydrogen localization in a steel microstructure, leading to embrittlement and hydrogen-assisted cracking. Cathodic charging was used to insert hydrogen, which decreased the steel potential. Hydrogen effusion in air passivates steel, increasing the potential of HSS and mild steel. The passivation of steels was monitored depending on different conditions of cathodic pre-charging and the amount of absorbed hydrogen. The SKP could determine the area of diffusible hydrogen and the area of cracks. In addition, low potential locations linked to the hydrogen trapped in the deformed HSS microstructure were also determined, which delayed the steel passivation. Mild steel showed a uniform potential distribution related to interstitial hydrogen, without potential extremes attributed to locally accumulated hydrogen. Thus, SKP sensing can detect locations containing increased concentrations of hydrogen and sensitive to steel cracking. Full article

Friction stir welded (FSW) aluminum–magnesium lightweight vehicle joints have gained significant interest due to their high strength-to-weight ratio. In this work, the corrosion resistance of this material is analyzed through electrochemical tests, which include open circuit potential (OCP) inspection and potentiodynamic polarization (PD) scanning. Weight loss measurements tested the corrosion rate of the FSW weld through cyclic corrosion testing (CCT) according to the standard SAEJ 2334. Mechanical properties were also investigated, including lap-shear strength, micro- and nano-hardness mapping, and true stress–strain curves as a function of local processing history. The electrochemical results indicate that the center weld zone’s corrosion property stays between the two base alloys. Indentation-based testing demonstrated that the weld zone behaves differently from base alloys. Lap shear strength surprisingly did not drop much even after eight weeks of cyclic corrosion tests, indicating that the joint did not allow any ingress of the electrolyte. Full article

The lifespan of low-carbon steel petroleum pipelines can often be shortened by the erosion–corrosion damage caused by their service conditions. Applying electroless Ni-P coating is a promising option to protect the steel from the environment due to its high hardness and corrosion resistance. However, electroless Ni-P has a low toughness but can be increased by the addition of NiTi ductile particles. This work produced electroless Ni-P and Ni-P-NiTi coatings of different thicknesses on AISI 1018 substrates and compared their erosion, corrosion, and erosion–corrosion behaviors. The methodology involved conducting slurry pot erosion–corrosion tests on AISI 1018 steel substrate, the monolithic Ni-P coatings, and the composite Ni-P-NiTi coatings. Erosion resistance was highly influenced by coating thickness, presumably because of the relationship between the erosion-induced compressive stresses and the coating’s as-plated internal stresses. The NiTi nanoparticle addition was highly effective at improving the erosion–corrosion resistance of the coating. Pitting corrosion and cracking were present after erosion–corrosion on the monolithic Ni-P coatings. However, the Ni-P-NiTi composite coating had a relatively uniform material loss. Overall, the AISI 1018 steel substrate had the worst erosion–corrosion resistance and 25 μm thick Ni-P-NiTi coating had the best. Full article

In order to investigate the electrochemical pitting corrosion in more detail, a micro-corrosion cell was developed, allowing real-time in situ optical observations of steel surfaces in direct correlation with electrochemical measurement results. In this study, the austenitic 1.4301–X5CrNi18-10 and the ferritic 1.4016–X6Cr17 stainless steel grades were examined in electrolytes containing chloride ions. The micro-corrosion cell revealed a stable pitting corrosion of the ferritic 1.4016 and metastable pitting corrosion of the austenitic 1.4301. The pits were characterized by means of scanning electron microscopy (SEM) and atomic force microscopy (AFM) in detail. A clear correlation between current peaks in the current density-potential curve and the growth of many small pits on the test surface was established and was identified as metastable pit growth. In general, the pitting corrosion potential increased as the diameter of the test surface decreased for both stainless steels. In contrast to the complex precipitates of 1.4301, chromium precipitates with a significantly higher amount was detected on the entire surface of the 1.4016. The corrosion initiation was identified at the interface between the precipitates and the base material for both stainless steels. By comparing both materials, the ferritic 1.4016 had a lower pitting corrosion potential than the austenitic 1.4301 under all test conditions. Full article

India’s growing power demands and emission norms require more efficient coal-based power plants. The shifting of power plants from subcritical to ultra-supercritical (USC) steam conditions could improve efficiency by 12% and reduce CO${}_2$ emissions by 35%. There is a need to develop and qualify materials under ultra-supercritical steam conditions with high temperatures and high pressures in laboratory scale. The sample materials were exposed to high temperatures of 700 °C under air and high pressure steam at 700 °C/243 bars for 1000 h in as-received and grain-boundary-enhanced conditions. Grain boundary enhancement included optimization of a thermo-mechanical process involving cold rolling and annealing of samples. The effect of air and steam oxidation on IN 617, a nickel-based candidate superalloy, was analysed. Steam oxidation was performed on a custom-built PARR 4650 series autoclave, and the oxidized samples were characterised under scanning electron microscopy, to evaluate the oxide scales. The grain-boundary-engineered material performed better than the as-received samples. IN 617 overall fared better under both air and steam conditions, with far less weight gains. Full article