Corrosion of steel canisters containing buried high-level radioactive waste is a relevant issue for the long-term integrity of repositories. The purpose of the present study was to evaluate this issue by examining two differently corroded blocks originating from a full-scale in situ test of the FEBEX bentonite site in Switzerland. The FEBEX experiment was designed initially as a feasibility test of an engineered clay barrier system and was recently dismantled after 18 years of activity. Samples were studied by ‘spatially resolved’ and ‘bulk’ experimental methods, including Scanning Electron Microscopy, Elemental Energy Dispersive Spectroscopy (SEM-EDX), μ-Raman spectroscopy, X-ray Fluorescence (XRF), X-ray Diffraction (XRD), and 57Fe Mössbauer spectrometry, with a focus on Fe-bearing phases. In one of the blocks, corrosion of the steel liner led to diffusion of Fe into the bentonite, resulting in the formation of large (width > 140 mm) red, orange, and blue colored halos. Goethite was identified as the main corrosion product in the red and orange zones while no excess Fe2+ (compared to the unaffected bentonite) was observed there. Excess Fe2+ was found to have diffused further into the clay (in the blue zones) but its speciation could not be unambiguously clarified. The results indicate the occurrence of newly formed octahedral Fe2+ either as Fe2+ sorbed on the clay or as structural Fe2+ inside the clay (following electron transfer from sorbed Fe2+). No other indications of clay transformation or newly formed clay phases were found. The overall pattern indicates that diffusion of Fe was initiated when oxidizing conditions were still prevailing inside the bentonite block, resulting in the accumulation of Fe3+ close to the interface (up to three times the original Fe content), and continued when reducing conditions were reached, allowing deeper diffusion of Fe2+ into the clay (inducing an increase of 10–12% of the Fe content).

The morphology and composition of the corrosion products of archaeological arsenical copper alloys buried in a specific environment for a long time were investigated using optical microscopy (OM), scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDS), micro X-ray fluorescence (μ-XRF), and X-ray diffraction (XRD). The analyses demonstrated that the alloy composition of the artifacts was copper-arsenic (Cu-AS) with significant amounts of lead in some samples. Cuprite, malachite, and copper (II) hydroxychlorides were observed on a completely mineralized matrix. The surface of the objects was covered by two main corrosion layers formed on the internal cuprous oxide. However, several successive layers of corrosion products were recognized on the artifacts in some cases. Furthermore, phosphatic corrosion products including, mimetite [Pb5(AsO4)3Cl], and pyromorphite [Pb5(PO4)3Cl] were identified. Conichalcite [CaCu(AsO4)](OH), which grew in the form of Liesegang rings, was also identified as a corrosion product of one of the objects. As and Pb exhibited some enrichment in the corrosion crusts of the artifacts. Environmental changes in burial conditions, particularly due to seasonal streams and consequent changes in soil corrosivity, vicinity of objects to bone material, along with the migration of alloy elements, especially lead and arsenic, can explain the morphological features of these archaeological objects.

The interaction of NCC-A (no cement content, with tabular corundum) refractory castable with corrosive refining steel slag CaO–Al2O3–SiO2–MgO–(FeO, MnO) was studied with static crucible corrosion tests. The corrosion process was evaluated using chemical and phase analyses, and the macro- and microstructures on the corrosion boundary of slag–refractory materials were investigated. We describe the corrosion progress and explain the NCC-A corrosion mechanism by oxide metallurgical slags. The alumina refractory material surface was wetted with molten oxide slag (contact angle θ1390°C from 10° to 20°). The slag penetrated through dissolution of the matrix (fine alumina cement), and the Ca–Si–Al slag, enriched with alumina, attacked the corundum grog. Marked changes in the chemical composition of the slag had an impact on the primary crystallization temperature. As the concentration of Al–O complexes increased in the slag, the binding parameters in Si–O complexes changed and complex tetrahedral units (Al–O–Si) and (Al–O–Mg) were created. Analyses of the corrosion interface grog show that calcium ions diffuse through structural defects in the corundum but Mg2+ diffusion was not observed. A sharp interface is observed between the slag and the corroded corundum layer. Differences in the chemical composition of the slag in the corrosion zone affected the convention stream, and formed the concave corrosion profile of the crucible.

An electrochemical cell was designed to enable in situ atomic force microscopy (AFM) measurements. The finite-element method was implemented using COMSOL Multiphysics to simulate the electrical field within the cell and to find the current and potential distribution. A comparative three-dimensional simulation study was made to compare two different designs and to elucidate the importance of the geometry on the electrical field distribution. The design was optimized to reduce the uncertainty in the measurement of the electrochemical impedance. Then, an in situ, simultaneous electrochemical and time-resolved AFM experiments were conducted to study the surface evolution of the aluminum alloy AA2024-T3 exposed to 0.5 M NaCl. The temporal change of the surface topography was recorded during the application of chrono-amperometric pulses using a newly designed electrochemical cell. Electrochemical impedance spectroscopy was conducted on the sample to confirm the recorded topographical change. The newly developed cell made it possible to monitor the surface change and the growth of the oxyhydroxide layer on the AA2024-T3 with the simultaneous application of electrochemical methods.

We extend our recent 2D trajectory (x–y plane) and diffusion coefficient data of ceria particles near a glass surface obtained at pH 3, 5, and 7 using evanescent wave microscopy and video imaging to 3D trajectories by analyzing the separation distance between the particles and the glass surface in the vertical z-direction. Mean squared displacement (MSD3D) of ceria particles was calculated to quantify 3D trajectories. Three-dimensional diffusion coefficients were obtained from the MSD3D curves and were compared with two-dimensional diffusion coefficients. By analyzing the MSD curves, we found that ceria particles exhibited only confined motion at pH 3 and 5, while both confined and Brownian motion were showed at pH 7. We also evaluated the cleaning ability of DI water adjusted to pH 10 and 12 to remove ceria particles from glass surfaces and related the results to the calculated trajectory, diffusion coefficient, and interaction potential data.

As the minimum feature size of integrated circuit elements has shrunk below 7 nm, chemical mechanical planarization (CMP) technology has grown by leaps and bounds over the past several decades. There has been a growing interest in understanding the fundamental science and technology of CMP, which has continued to lag behind advances in technology. This review paper provides a comprehensive overview of various chemical and mechanical phenomena such as contact mechanics, lubrication models, chemical reaction that occur between slurry components and films being polished, electrochemical reactions, adsorption behavior and mechanism, temperature effects, and the complex interactions occurring at the wafer interface during polishing. It also provides important insights into new strategies and novel concepts for next-generation CMP slurries. Finally, the challenges and future research directions related to the chemical and mechanical process and slurry chemistry are highlighted.

The corrosion behavior of uncoated, nickel (Ni) and nickel–phosphorous (Ni–P)-coated AISI 430 alloy was investigated in Ar–3%H2 and Ar–3%H2–3%H2O atmosphere at 800 °C for 100 h. Microstructure, chemical composition, and reaction products were analyzed by scanning electron microscopy, energy-dispersive spectroscopy, and X-ray diffraction techniques. The corrosion extent of Ni–P-coated AISI 430 is higher than Ni-coated AISI 430. Oxidation promotes corrosion in the uncoated and coated alloy. The oxidation rate of Ni-coated alloy is the lowest in Ar–3%H2 but Ni–P-coated alloy in Ar–3%H2–3%H2O for initial 20 h. The oxidation rate of the Ni–P-coated sample is ~14 times higher in 20–100 h in Ar–3%H2–3%H2O. External growth of Cr2O3 is observed for Ni-coated alloy in Ar–3%H2 and for Ni–P-coated alloy in both the atmospheres. Inward growth of Cr2O3 by AISI 430 alloy consumption attributes to the lowest oxidation rate and the corrosion extent of Ni-coated sample in Ar–3%H2–3%H2O.

Calcium–magnesium–alumino-silicate (CMAS) reaction and infiltration behavior were studied in phase pure and mixed phase ytterbium silicate environmental-barrier coating (EBC) materials at 1300 °C. Phase pure Yb2Si2O7 (YbDS) was infiltrated by CMAS via grain boundaries/pores, resulting in loss of its structural integrity. Phase pure Yb2SiO5 (YbMS) reacted with CMAS to form either apatite (Ca2Yb8(SiO4)6O2) or YbDS, depending on the initial glass composition. Both reactions in YbMS slowed infiltration kinetics considerably compared to YbDS. Samples having a YbDS matrix with controlled amounts and dispersions of YbMS were also investigated as a model for air plasma spray coatings. Samples containing ≥20 vol% coarse YbMS showed dramatically improved infiltration behavior compared to phase pure YbDS. YbDS samples containing a fine dispersion of YbMS displayed a new mode of CMAS attack in which glass spread on the sample surfaces. The results of this study suggest that EBC phase compositions and microstructures may be tailored for optimized CMAS resistance.

Electrophoretic deposition consisting of bioglass (BG)–chitosan (CS)–iron oxide nanoparticles (Fe3O4 NPs) on the Ti–13Nb–13Zr substrate was described. The bioactive coating was embedded in a CS matrix. The Fe3O4 NPs collected using the co-precipitation method varied at three different levels (1, 3, and 5 wt%) in the BG coating. The formulated coatings exhibited a hydrophilic character due to higher surface roughness values. The pull-off tape test was performed to check the adhesion strength of coatings. The composite coatings displayed adhesion strength of 5B class. The corrosion behavior was evaluated in Ringer's solution by the electrochemical test. The corrosion results showed that the composite coatings were more impressive as compared to pure BG and Fe3O4 coatings. The hemocompatibility results showed a hemolytic ratio (<5%), which validates them as favorable blood compatible nature of the deposited coatings. The findings exhibited that the BG–Fe3O4–CS coating can be widely employed as a favorable material for orthopedic applications.

An Al–Cu–Li aerospace alloy has been investigated to determine the order in which corrosion at different types of sites occurs in AA2099-T83. Specifically, the sequence of galvanic attack on intermetallic (IM) particles and other sites of AA2099-T83 was determined as a function of time, in 0.1 M NaCl, through the use of scanning electron microscopy and electron backscatter diffraction characterization techniques. The earliest attack occurred at isolated grains and grain boundaries and on Li-containing dispersoids. Similarly, some constituent IM particles showed evidence of trenching in the surrounding alloy matrix. These IM particles included Al7Cu2Fe and another group of unidentified particles which displayed complete trenching within the first 10 min of exposure. Al13(Fe, Mn)4 were next most active followed by Al37Fe12Cu2 with Al6(Fe,Mn) and large TiB2 particles being the least active.

Dissolution of oxides in aqueous solutions is fundamentally important for a range of applications and a critical process that determines the chemical durability of industrial ceramics, the performance of nuclear waste forms, and the chemical weathering of minerals. The thermodynamic equilibrium and kinetics of dissolution reactions are key to determining the rate at which oxides dissolve. The increase in collaborative research across disciplines in materials research necessitates a common background to tackle shared scientific problems across different fields. This review selectively examines the fundamentals of dissolution theories that have been developed in chemistry, geochemistry, and materials science, and assembles them into a single collective document for the broader materials science community. Applications of the theories are highlighted using examples from specific areas, but can be similarly applied to other areas. Challenges and future research needs for a predictive-level understanding are discussed in light of the current literature.

In microstructural corrosion studies, knowledge on the initiation of corrosion on an nm-scale is lacking. In situ transmission electron microscope (TEM) studies can elucidate where/how the corrosion starts, provided that the proper corrosive conditions are present during the investigation. In wet corrosion studies with liquid cell nanoreactors (NRs), the liquid along the electron beam direction leads to strong scattering and therefore image blurring. Thus, a quick liquid removal or thickness control of the liquid layer is preferred. This can be done by the use of a Peltier element embedded in an NR. As a prelude to such in situ work, we demonstrate the local wetting of a TEM sample, by creating a temperature decrease of 10 ± 2°C on the membrane of an NR with planar Sb/BiSb thermoelectric materials for the Peltier element. TEM samples were prepared and loaded in an NR using a dual-beam focused ion beam scanning electron microscope. A mixture of water vapor and carrier gas was passed through a chamber, which holds the micro-electromechanical system Peltier device and resulted in quick formation of a water layer/droplets on the sample. The TEM analysis after repeated corrosion of the same sample (ex situ studies) shows the onset and progression of O2 and H2S corrosion of the AA2024-T3 alloy and cold-rolled HCT980X steel lamellae.

Surfaces of polycrystalline ferritic Fe–Cr steel with grain sizes of about 13 µm in diameter were investigated with surface sensitive techniques. Thin oxide layers, with a maximum thickness of about 100 nm, were grown by oxidation in air at temperatures up to 450°C and were subsequently characterized using time-of-flight secondary ion mass spectrometry (TOF-SIMS) and atomic force microscopy. Correlative microscopy was applied, which allows for element-specific depth profiles on selected grains with a particular crystal orientation. A strong correlation between the grain orientation and the thickness of the oxide layer was found. The sequence in the oxidation growth rate of ferritic Fe–Cr steel crystal planes is found to be {011} > {111} > {001}, which is unexpectedly opposed to known Fe-based systems. Moreover, for the first time, the Cr/Fe ratio throughout the oxide layer has been determined per grain orientation. A clear order from high to low of {001} > {111} > {011} was detected.

Nuclear fuel debris generated at the Fukushima Daiichi nuclear power plant during the loss of coolant accident in 2011, still resides within the reactor units, constantly cooled by water. Until it is retrieved, the fuel debris will corrode, releasing radioactive elements into the coolant water and the ground surrounding the reactors. To predict the corrosion behaviour of these materials, and to establish parameters for experiments with U-containing and real fuel debris, the corrosion of two surrogate fuel debris materials, with a composition of Ce(1-x)ZrxO2 (x = 0.2 and 0.4), was investigated. Materials were synthesised by a wet chemistry route and pellets were sintered at 1700°C in air atmosphere. Due to the slow corrosion kinetics, aggressive conditions were applied, and corrosion experiments were performed in 9 mol.L-1 HNO3 under static conditions. The incorporation of Zr into the structure of Ce reduced the normalised dissolution rate; from (3.75 ± 0.15) × 10-6 g.m-2.d-1 to (4.96 ± 0.28) × 10-6 g.m-2.d-1 for RL(Ce) of Ce0.8Zr0.2O2 and Ce0.6Zr0.4O2, respectively.

To improve the corrosion resistance and to increase the hardness of copper substrate in marine environment, the Cu-Ni/Ni-P composite coatings were prepared on the copper substrate using the galvanostatic electrolytic deposition method. The deposition current densities were explored to find the optimized deposition conditions for forming the composite coatings. Corrosion resistance properties were analyzed using the polarization curves and electrochemical impedance spectroscopy (EIS). Considering the corrosion resistance and hardness, the −20 mA/cm2 was selected to deposit Cu-Ni coatings on copper substrate and the −30 mA/cm2 was selected to deposit Ni-P coating on the Cu-Ni layer. The Cu-Ni/Ni-P composite coatings not only exhibited superior corrosion resistance compared to single Cu-Ni coating in 3.5 wt.% NaCl solution, but also showed much better mechanical properties than single Cu-Ni coating.

Hybrid coatings for cavitation erosion protection of aluminum alloys, have been developed, based on a sol-gel process and applied by the dip coating technique. This work aims to investigate established hybrid sol-gel coatings synthesized using organically modified silicon precursor 3-methacryloxypropyltrimethoxysilane (MAPTMS) mixed with zirconium (IV) propoxide. In the present research, the established baseline coatings were modified by adding different concentrations (1%, 1.5% and 2%) of cross-linkable hexamethylenediisocyanate (HMDI) diluted in 60% ethanol. The influences of the amount of crosslinker incorporated into the coatings on abrasion, corrosion and cavitation erosion protection were studied. The hydrophobic nature, thermal and electrochemical properties of the coatings were evaluated using Water Contact Angle (WCA), Differential Scanning Calorimetry (DSC), Open Circuit Potential (OCP) and Potentiodynamic polarization (PDS) techniques. Furthermore, cavitation erosion and abrasion tests were completed on all coatings and rankings of these were produced based on mass loss measurements and derived mean depth of erosion.

We divide the corrosion products on ancient bronzes into two categories, i.e., "inward growth" and “outward growth” corrosions. Several selected Chinese ancient bronzes with the "inward growth” corrosion are studied; and their chemical compositions, microstructures and morphologies are characterized systematically. According to the results, it is found that the “inward growth” corrosion can be further divided into three types, i.e., "noble patina", "noble-like patina" and "lamellar peeling patina". We propose that the growth mechanism of the “inward growth” corrosion is that the corrosion initiates at and develops along α-Cu phase. Furthermore, the effect of alloy Sn content on the “inward growth” corrosion is also studied.

The dissolution of the United Kingdom’s vitrified high-level-waste simulant, CaZn MW28, was investigated following the Product Consistency Test-B protocol for 112 d at 90 °C and in ultra-high-quality water. Residual rate dissolution (stage II) and rate resumption (stage III), after 28 d, was observed. Thermodynamic modelling suggested that solutions were saturated with respect to Mg- and Zn-bearing phases, and the presence of Mg- and Zn-smectite clays was tentatively observed. The formation of these phases was concurrent with a significant increase in the dissolution rate, similar to Stage III behavior seen in other nuclear waste simulant glass materials, indicating that the addition of Mg and Zn to high-level-waste glass (7.3 wt. % combined) significantly influences the dissolution rate.