Corrosion and Materials Degradation

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

Aqueous zinc ions lower the corrosion rate of Alloy 600, which helps lower the radiation dose rate in pressurized water reactors (PWRs). The influence of zinc on the electrochemical behavior of Alloy 600 in PWR primary water (PW) at 320 °C was investigated using a combination of electron microscopy and electrochemical impedance spectroscopy (EIS). Secondary electron microscopy (SEM) and scanning transmission electron microscopy (STEM)/energy-dispersive X-ray spectroscopy (EDS) indicated duplex surface films were formed on the Alloy 600 in PWR PW with and without 100 ppb of zinc. There was no effect of zinc on the chromium-rich inner layer (IL) (of Cr₂O₃ and/or CrOOH). Zinc had a significant effect on the outer layer (OL). In the absence of zinc, a highly porous OL formed that was mostly composed of nickel oxide whiskers. In the presence of zinc, a zinc-containing, denser OL of oxide was formed. The EIS data were acquired in laboratory simulated PWR PW at 320 °C with and without 100 ppb zinc. The spectra were measured at nine different values of potential that spanned a 500 mV-wide range. The EIS indicated there was no effect of zinc on the oxidation rate of metals at the alloy/IL interface nor on the transport of ions through the IL. Zinc lowered the corrosion rate because the dense OL inhibited the release of nickel ions from the IL into the solution. Full article

Polymeric coatings have been widely selected for the corrosion resistance of metallic surfaces. Both the conducting and non-conducting polymers have been applied for corrosion confrontation. The conducting polymers usually possess high electrical conductivity and corrosion resistance features. On the other hand, non-conducting hydrophobic polymers have also been used to avert the metal erosion. To improve the corrosion inhibition performance of the polymer coatings, nanocarbon nanofillers have been used as reinforcement. Graphene, especially, has gained an important position in the research on the corrosion-protecting nanocomposite coatings. Here, graphene dispersion and matrix–nanofiller interactions may significantly improve the anti-corrosion performance to protect the underlying metals. The graphene nanofiller may form an interconnecting percolation network in the polymers to support their electrical conductivity and thus their corrosion confrontation characteristics. Further research on the polymer/graphene nanocomposite and its anti-corrosion mechanism may lead to great advancements in this field. Full article

One of the key urban air quality issues is pollution by nitrogen oxides (NO${}_{\mathrm{x}}$). To reduce NO${}_{\mathrm{x}}$, facade cladding could be provided with photocatalytic properties by incorporating titanium dioxide nanoparticles. For this purpose, a modified phosphoric acid anodizing process (MPAA) was developed for the facade alloy EN AW-5005, in which highly ordered anodized structures with a low degree of arborization and tortuosity were produced. Pore widths between 70 nm and 150 nm and layer thicknesses of about 2–3 $\mathsf{\mu }$m were obtained. The subsequent impregnation was carried out by dip coating from water-based systems. Depending on the dip-coating parameters and the suspension used, the pores can be filled up to 60% with the TiO${}_2$ nanoparticles. Photocatalytic tests according to ISO 22197-1 certify a high photocatalytic activity was obtained with rPCE values > 8 and with rPCE > 2, achieving “photocatalytically active for air purification”. Tests on the corrosion resistance of the anodized coatings with a commercially available aluminum and facade cleaner confirm a protective effect of the anodized coatings when compared with nonanodized aluminum material, as well as with compacted anodized layers. Full article

A rigorous assessment of marine atmospheric corrosion at a controlled NRL test site in Key West Florida was conducted. Certain factors which have been previously implicated in the literature as influencing the corrosion of engineering materials in atmospheric exposure were isolated and explored. In particular, the effect of sample size and orientation was explored. Low carbon steel (C1010) witness coupons were exposed in vertical non-sheltered, vertical sheltered, and tilted non-sheltered conditions. The effect of surface area on measured steel mass loss was also explored to identify the veracity of the so-called “edge effect”. Efforts were made to correlate meteorological atmospheric conditions (temperature, relative humidity, wind speed, wind direction, etc.) to the monthly assessment of corrosion damage. Results were assessed in terms of steel mass loss. Additive composite monthly corrosion damage tended to significantly overshoot the observed cumulative corrosion damage for samples exposed over the same period. This observation, among others presented herein, suggests that exposure of samples for less than 6 months is not an adequate predictor of long-term, natural exposure. Additionally, a smaller sample had a larger area-normalized mass loss than a larger sample. The influence of the sample edge (especially the bottom edge) was implicated in causing this difference. Full article

Anodizing is commonly used for corrosion protection of aluminum and its alloys in the construction industry. The anodic aluminum oxide (AAO) coating has a high ability to prevent the development of extensive pitting corrosion in aluminum substrates, particularly in marine sites, as was observed during a 10-year atmospheric corrosion study carried out in several marine and industrial sites. However, this study also evidenced that this coating can be highly affected by the deposition of particulate material in industrial polluted environments, sometimes in unexpected ways. This study presents information on the atmospheric corrosion of anodized aluminum exposed at two different chemical industrial complexes: a fertilizer production plant and a pulp and paper mill. Visual assessment of surface changes, pitting depth and mass variation with exposure were determined to quantify the degradation suffered. Additionally, SEM/EDS analyses were carried out on the exposed surfaces. Based on the results obtained, the role played by the deposition of airborne particles present in the two environments with respect to the type and level of damage observed is discussed. Deposits of roasted pyrite ash and phosphates or of wood chips and lime particles enhanced pitting corrosion or caused dissolution of the AAO coating. Full article

Concrete is a material of porous nature that, when humidified, becomes an ionic conductor whose apparent conductivity depends on the ionic load (typically based on ${\mathrm{OH}}^{-}$, Ca²⁺, Na⁺, and K⁺) and the amount of available free water. Under conditions of partial pore-saturation, the amount of free water can be modulated by an external load, which leads to observable changes in electrical properties such as conductivity and capacitance. Moreover, metallic reinforcements, either as bars or fibers, represent an additional parallel conduction path but of an electronic nature in this case. The free water develops a double-layer capacitance structure at the metallic interfaces, with associated charge-transfer resistance, representing an additional contribution to the capacitive behavior that can be modulated with an external load. The dependence that the electrical and/or ionic conducting properties of concrete and reinforced concrete elements have on the available free water makes them suitable for transductors in various sensing and self-sensing applications discussed in the text. Full article

The radiolysis of water is a significant cause of corrosion damage in the primary heat transport systems (PHTSs) of water-cooled, fission nuclear power reactors (BWRs, PWRs, and CANDUs) and is projected to be a significant factor in the evolution of corrosion damage in future fusion reactors (e.g., the ITER that is currently under development). In Part I of this two-part series, we reviewed the proposed mechanisms for the radiolysis of water and demonstrate that radiolysis leads to the formation of a myriad of oxidizing and reducing species. In this Part II, we review the role that the radiolysis species play in establishing the electrochemical corrosion potential (ECP) and the development of corrosion damage due to intergranular stress corrosion cracking (IGSCC) in reactor PHTSs. We demonstrate, that the radiolytic oxidizing radiolysis products, such as O₂, H₂O₂, HO₂⁻, and OH, when in molar excess over reducing species (H₂, H, and O₂²⁻), some of which (H₂) are preferentially stripped from the coolant upon boiling in a BWR PHTS, for example, renders the coolant in many BWRs oxidizing, thereby shifting the ECP in the positive direction to a value that is more positive than the critical potential (E_crit = −0.23 V_she at 288 °C) for IGSCC in sensitized austenitic stainless steel (e.g., Type 304 SS). This has led to many IGSCC incidents in operating BWRs over the past five decades that has exacted a great cost on the plant operators and electricity consumers, alike. In the case of PWRs, the primary circuits are pressurized with hydrogen to give a hydrogen concentration of 10 to 50 cm³/kgH₂O (0.89 to 4.46 ppm), such that no sustained boiling occurs, and the hydrogen suppresses the radiolysis of water, thereby inhibiting the formation of oxidizing radiolysis products from water. Thus, the ECP is dominated by the hydrogen electrode reaction (HER), although important deviations from the HER equilibrium potential may occur, particularly at low [H₂]. In any event, the ECP is displaced to approximately −0.85 V_she, which is below the critical potential for IGSCC in sensitized stainless steels but is also more negative than the critical potential for the hydrogen-induced cracking (HIC) of mill-annealed Alloy 600. This has led to extensive cracking of steam generator tubing and other components (e.g., control rod drive tubes, pressurizer components) in PWRs that has also exacted a high cost on operators and power consumers. Although the ITER has yet to operate, the proposed chemistry protocol for the coolant places it close to a BWR operating on Normal Water Chemistry (NWC) without boiling or, if hydrogen is added to the IBED-PHTS, close to a BWR on Hydrogen Water Chemistry (HWC). In the current ITER technology, the concentration of H₂ in the IBED-PHTS is specified to be 80 ppb, which is the concentration that will be experienced in both the Plasma Flux Area (PFA) and in the Out of Plasma Flux Area (OPFA). That corresponds to 0.90 cc(STP) H₂/KgH₂O, compared with 20–50 cc(STP) H₂/KgH₂O employed in a PWR primary coolant circuit and 5.5 to 22 cc(STP) H₂/KgH₂O in a BWR on hydrogen water chemistry (HWC). We predict that a hydrogen concentration of 80 ppb is sufficient to reduce the ECP in the OPFA to a level (−0.324 V_she) that is sufficient to suppress the crack growth rate (CGR) below the practical, maximum level of 10⁻⁹ cm/s (0.315 mm/a) at which SCC is considered not to be a problem in a coolant circuit but, in the PFA, the ECP is predicted to be 0.380 V_she, which gives a calculated standard CGR of 2.7 × 10⁻⁶ cm/s. This is more than three orders in magnitude greater that the desired maximum value of 10⁻⁹ cm/s. We recommend that the HWC issue in ITER be revisited to develop a protocol that is effective in suppressing both the ECP and the CGR in the PFA to levels that permit the operation of the IBED-PHTS in accordance with the experience gained in fission reactor technology. Full article

Machine learning (ML) is providing a new design paradigm for many areas of technology, including corrosion inhibition. However, ML models require relatively large and diverse training sets to be most effective. This paper provides an overview of developments in corrosion inhibitor research, focussing on how corrosion performance data can be incorporated into machine learning and how large sets of inhibitor performance data that are suitable for training robust ML models can be developed through various corrosion inhibition testing approaches, especially high-throughput performance testing. It examines different types of environments where corrosion by-products and electrolytes operate, with a view to understanding how conventional inhibitor testing methods may be better designed, chosen, and applied to obtain the most useful performance data for inhibitors. The authors explore the role of modern characterisation techniques in defining corrosion chemistry in occluded structures (e.g., lap joints) and examine how corrosion inhibition databases generated by these techniques can be exemplified by recent developments. Finally, the authors briefly discuss how the effects of specific structures, alloy microstructures, leaching structures, and kinetics in paint films may be incorporated into machine learning strategies. Full article