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At least 1,171 records · Page 65

Ce nanoparticles and sol-gel hybrid organic-inorganic coatings maximize corrosion protection in the anodized AA2024-T3

Herein we demonstrate that the corrosion resistance of the AA2024-T3 alloy can be maximized with the application of top protective sol-gel hybrid organic-inorganic coatings. Samples combining Ce nanoparticles within the pores of the anodic layer with the top sol-gel coatings were observed to outperform samples featuring only the coating. This research unravels the self-healing capability against corrosion of the sol-gel coating when Ce nanoparticles are present, as well as a good coverage of defective regions within the oxide by the hybrid layer. This research opens a paradigm aiming at maximizing the corrosion resistance for non-ferrous anodized alloys.

36 MATERIALS SCIENCE↗

Effect of HCO 3 - on electrochemical kinetics of carbon steel corrosion in CO 2 -saturated brines

The effect of HCO 3 – (aq) on CO 2 corrosion of carbon steel was investigated in deaerated 3.5 wt% NaCl solutions at 30 °C from pH 3.96 to 7.15. In the CO 2 -saturated solutions, the pH was adjusted with different HCO 3 – (aq) concentrations, c[HCO 3 – (aq)]. The corrosion rate decreased by a factor of 2 as the pH and c[HCO 3 – (aq)] increased. The cathodic current density during polarization increased at higher pH with higher c[HCO 3 – (aq)], indicating that HCO 3 – (aq) acted as an additional hydrogen source for the hydrogen evolution reaction. As the pH increased, the active dissolution regions displayed similar anodic Tafel slopes and suggested a modified Bockris mechanism for the Fe oxidation reaction. The exchange current densities for the half reactions were calculated to study kinetics of the anodic and cathodic half reactions independently. The anodic exchange current density ( j 0,a ) increased by one order of magnitude in the presence of CO 2 , indicating the involvement of CO 2 (aq) in the Fe oxidation reaction. As the pH and c[HCO 3 – (aq)] increased, the cathodic exchange current density ( j 0,c ) decreased by a factor of 50 because the increase in j 0,c [HCO 3 – (aq)] was not high enough to compensate the decline from the other hydrogen sources, especially j 0,c [H + (aq)]; and j 0,a decreased by a factor of 2.4 because HCO 3 – (aq) may have competed with CO 2 (aq) for the surface coverage and the increase in j 0,a [CO 2 (aq)] could not compensate the decrease in j 0,a [CO 2 (aq)]. It suggests that the reaction rate constant of HCO 3 – (aq) was smaller than CO 2 (aq) for the anodic half reaction and was smaller than H + (aq) for the cathodic half reaction. The XPS results verified that the corrosion products transitioned from iron carbonate to hydroxide as the pH increased while iron carbonate remained the major product. As the pH increased with HCO 3 – (aq), a second time constant was observed at lower frequencies of the electrochemical impedance spectroscopy (EIS) results.

36 MATERIALS SCIENCE↗

Self-re-adhering alkali-activated cement composite and its ability to mitigate corrosion of carbon steel in 300 °C hydrothermal environment

Cement-steel interface is a weak point of cement sheath integrity under the environments of high-temperature geothermal wells. This paper presents carbon steel (CS) adherence behaviors of 300 °C-autoclaved alkali-activated Calcium-Aluminate-Cement (CAC)/fly ash F (FAF) (Thermal Shock Resistant Cement, TSRC), granulated blast furnace slag (GBFS)/SiO 2 , and Ordinary Portland Cement (OPC)/SiO 2 blends. The composites’ ability to preserve the bond under the conditions of thermal shock (TS) and strong acid attack (pH 0.6 H 2 SO 4 /brine at 90 °C) as well as their ability to recover the damaged bond and provide steel corrosion protection after additional short-time 5-day curing at 300 °C were evaluated. GBFS/SiO 2 sheath underwent catastrophic failure in the first TS cycle; OPC/SiO 2 lost 78 % and TSRC 51 % of the bond strength in 6 cycles. Only TSRC-CS bond survived 30 days of strong acid exposure; OPC/SiO 2 bond failed after 18 days and GBFS/SiO 2 after 20 days. Addition of micro-glass fibers (MGF) to TSRC further improved its bond strength and CS corrosion protection. Samples of TSRC-CS cured for 30 days at 300 °C before the bond damage recovered 49 % of the damaged bond strength after additional short-time curing. The CS protected by the re-adhered TSRC showed low corrosion rate of 0.13 mm/year (TSRC-MGF), 0.2 mm/year (TSRC) vs. 0.64 mm/year for OPC/SiO 2 protected CS.

15 GEOTHERMAL ENERGY↗

Uniform corrosion of FeCrAl alloys in LWR coolant environments

The corrosion behavior of commercial and model FeCrAl alloys and type 310 stainless steel was examined by autoclave tests and compared to Zircaloy-4, the reference cladding materials in light water reactors. The corrosion studies were carried out in three distinct water chemistry environments found in pressurized and boiling water reactor primary coolant loop conditions for up to one year. The structure and morphology of the oxides formed on the surface of these alloys was consistent with thermodynamic predictions. Spinel-type oxides were found to be present after hydrogen water chemistry exposures, while the oxygenated water tests resulted in the formation of very thin and protective hematite-type oxides. Unlike the alloys exposed to oxygenated water tests, the alloys tested in hydrogen water chemistry conditions experienced mass loss as a function of time. This mass loss was the result of net sum of mass gain due to parabolic oxidation and mass loss due to dissolution that also exhibits parabolic kinetics. Finally, the maximum thickness loss after one year of LWR water corrosion in the absence of irradiation was ~2 μm, which is inconsequential for a ~300–500 μm thick cladding.

36 MATERIALS SCIENCE↗

Hydrothermal corrosion of silicon carbide joints without radiation

In this paper, hydrothermal corrosion of four types of the silicon carbide (SiC) to SiC plate joints were investigated under pressurized water reactor and boiling water reactor relevant chemical conditions without irradiation. The joints were formed by metal diffusion bonding using molybdenum or titanium interlayer, reaction sintering using Ti—Si—C system, and SiC nanopowder sintering. Most of the joints withstood the corrosion tests for five weeks. The recession of the SiC substrates was limited. Based on the recession of the bonding layers, it was concluded that all the joints except for the molybdenum diffusion bond are promising under the reducing environments without radiation. Finally, the SiC nanopowder sintered joint was the most corrosion tolerant under the oxidizing environment among the four joints.

36 MATERIALS SCIENCE↗

Deformation band corrosion as a result of applied stress and cold-work in 304 stainless steel in simulated pressurized water reactor primary water conditions

Stainless steels like 304SS are commonly used in pressurized water reactor primary water environments due to their excellent resistance to stress corrosion cracking (SCC). However, SCC susceptibility has been observed in cold-worked 304SS. Cold-rolling introduces a high density of defects, such as deformation bands or dislocations, into the microstructure; applied stress, even if macroscopically below the yield stress, can result in regions with high localized stresses. Cold-worked and non-cold-worked samples were exposed to 360 °C simulated PWR primary water for 1500 h with and without active loading. Corrosion susceptibility of dislocations and deformation bands induced by cold-rolling and/or applied stress was studied using high-resolution (analytical) transmission electron microscopy. Deformation bands were generated in all specimens examined in the study. Penetrative oxidation was observed in some deformation bands in each specimen. The depth of penetrative deformation band oxidation frequently exceeded the depth of grain boundary oxidation in all specimens. However, deformation band oxides generally were narrowly confined to the deformation band plane. Highly Ni-rich regions were observed beyond all oxidation fronts. Surface oxides were thicker in the specimens exposed under active loading. In conclusion, the implications of these findings at surfaces for deformation bands intersecting stress corrosion crack paths are discussed.

EFTEM↗

A Kinetic Model of the Long-Term Corrosion of Glass-Ceramic Materials

Multiphase waste forms show promise for increased waste loading and for the ability to dispose of contaminated solid and particulate waste through direct densification. However, achieving predictive capability for long-term durability of multiphase waste forms, and thus assessing their possible deployment, requires expanding the current, limited knowledge base. Here, we describe the development of a corrosion model of a two-phase waste form consisting of crystals of known volume fraction embedded in a glass matrix. This model accounts for the dissolution of both the crystalline and glass phases as well as the hydration of the glass phase through an ion exchange reaction. Because of the large difference in solubility between the two phases, the reactive surface of the crystalline phase is a function of the extent of dissolution of the glass phase in this model. Model parameterization was performed using corrosion data, such as from single-pass flow-through tests, for the individual phases. The parameterized corrosion model was evaluated against static dissolution test data for a glass-ceramic multiphase waste form. This evaluation demonstrated the model’s ability to reproduce the time-dependent release of key tracers of glass and crystalline phase dissolution. Hence, the development of a kinetic model provides a pathway for long-term durability predictions and thus the use of multiphase waste forms in nuclear cleanup missions.

Kerisit, Sebastien N.↗

Interactions between phosphate and arsenic in iron/biochar-treated groundwater: Corrosion control insights from column experiments

An increasing number of studies have reported the coexistence of arsenic (As) and phosphorus at high concentrations in groundwater, which threatens human health and increases the complexity of groundwater remediation. However, limited work has been done regarding As interception in the presence of phosphate in flowing systems. In this study, a series of experiments were conducted to evaluate the interactions between phosphate and As during As removal by iron (Fe)-based biochar (FeBC). The addition of phosphate promoted As removal by FeBC in the batch and column experiments. X-ray absorption near edge structure (XANES) analysis provided evidence of simultaneous oxidation and reduction of trivalent arsenic in the FeBC column experiment, accompanied by corrosive Fe oxidation. However, the addition of phosphate enhanced As stabilization, attributed to the As-incorporated Fe-Ca-phosphates precipitates. The involvement of phosphate decelerated the Fe corrosion and the formation of secondary minerals in the column, mediating the risk of passivation and clogging. The As retained by Fe-Ca-phosphate precipitates was more readily oxidized, resulting in higher proportions of pentavalent arsenic. In conclusion, the results of this work identify the corrosion control and sustained-release roles of phosphate in FeBC application, informing the perspective of FeBC in As-contaminated groundwater remediation and providing new insights into the interactions between phosphate and As.

54 ENVIRONMENTAL SCIENCES↗

Molecular Imaging of Microbially Induced Corrosion of Synthetic Archeological Glasses by a Rhizosphere Bacterium

Microbially induced corrosion (MIC) focuses on the degradation of solid materials, such as glass or metal. Soil microbes are often associated with the corrosion of foreign objects in the rhizosphere. Paenibacillus polymyxa SCE2, a facultative anaerobic bacterium in soil, is of the same genus as bacteria found near nuclear waste disposal sites. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used for imaging surface changes induced by P. polymyxa SCE2 cultured on two synthetic glass coupons to represent natural analogs of materials that were studied in relation to the vitrification of nuclear waste. Multimodal imaging was used to verify bacterial coverage across the glass surface after long-term growth. ToF-SIMS spectral analysis showed detection of glass component ions, such as silicon oxide (m/z – 59.96 SiO 2 – ) and aluminum oxide (m/z – 101.95 Al 2 O 3 – ), and biofilm’s extracellular polymeric substance (EPS) components, such as pentadecanoic acid (m/z – 241.22 C 15 H 29 O 2 – ) and sterol lipids (m/z – 311.16 C 20 H 23 O 3 – ). ToF-SIMS spectral, imaging, and depth profiling analyses showed that the glass rich in silica and other light elements (“granite glass”) had more “corrosion related” peaks than the glass that was less silica-rich and contained more iron (“dike glass”). Furthermore, these surface and interface compositional and spatial differences observed in the mass spectra and imaging were attributed to bacterial metabolism and an electron transfer mechanism influenced by morphological and compositional differences between the two types of glasses. ToF-SIMS is effective in studying microbial effects, bringing new molecular insights into MIC in a broader context of materials degradation.

Amorphous materials↗

Recent Advances in Corrosion Science Applicable To Disposal of High-Level Nuclear Waste

High level radioactive waste is accumulating at temporary storage locations around the world and will eventually be placed in deep geological repositories. Many different types of geological formation are under consideration, but all will eventually allow water to contact the metallic waste containers considering that the period of performance required to allow sufficient decay of dangerous radionuclides is on the order of 105 – 106 years. Corrosion of the containers and waste forms in the aqueous repository environment is therefore a concern. This review describes the recent advances of the field of materials corrosion based on the work of the Center for Performance and Design of Nuclear Waste Forms and Containers (WastePD) to address the issues associated with the long-term performance assessment and the design of materials with improved performance, where performance is defined as resistance to aqueous corrosion. Glass, crystalline ceramics, and metals are discussed separately, and then the near field interactions of these different materials classes are addressed. Recommendations for future directions are provided.

Frankel, Gerald↗

An Unexpected Role of H During SiC Corrosion in Water

During aqueous corrosion, atoms in the solid react chemically with oxygen, leading either to the formation of an oxide film or to the dissolution of the host material. Commonly, the first step in corrosion involves an oxygen atom from the dissociated water that reacts with the surface atoms and breaks near-surface bonds. In contrast, hydrogen on the surface often functions as a passivating species. Here, we discovered that the roles of O and H are reversed in the early corrosion stages on a Si-terminated SiC surface. O forms stable species on the surface, and chemical attack occurs by H that breaks the Si–C bonds. Here, this so-called hydrogen scission reaction is enabled by a newly discovered metastable bridging hydroxyl group that can form during water dissociation. The Si atom that is displaced from the surface during water attack subsequently forms H 2 SiO 3 , which is a known precursor to the formation of silica and silicic acid. This study suggests that the roles of H and O in oxidation need to be reconsidered.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Integrated computational materials engineering of corrosion resistant alloys

Structure, composition and surface properties dictate corrosion resistance in any given environment. The degrees of freedom in alloy design are too numerous in emerging materials such as high entropy alloys and bulk metallic glasses for the use of high-throughput methods or trial and error. We review three domains of knowledge that can be applied towards the goal of corrosion resistant alloy (CRA) design: (a) the aggregation of knowledge gained through experience in developing CRAs empirically, (b) data-driven approaches that use descriptive metrics for alloy composition optimization, and (c) first-principles models of elementary processes that regulate corrosion informed by theory and inspired by phenomenological models in the literature. A path forward for integrated computational materials engineering (ICME) of CRAs that unites these three knowledge domains is introduced.

36 MATERIALS SCIENCE↗

Spectroscopic ellipsometry study of thickness and porosity of the alteration layer formed on international simple glass surface in aqueous corrosion conditions

The porosity and pore-size distribution in the glass play an important role in glass corrosion; however, such information is difficult to be obtained non-destructively. Here we report the use of spectroscopic ellipsometry (SE) under controlled humidity environments to determine those structural parameters in the alteration layers formed on international simple glass (ISG), a model nuclear waste glass, in aqueous corrosion conditions. The SE results show that the ISG sample corroded for nearly 4.5 years develops pores larger than 2 nm in diameter, while the alteration layers formed initially in less than 1 month do not have such large pores. The development of larger pores over a long period of corrosion time, while the overall thickness remains relatively constant, implies structural rearrangements of the silicate network occurring within the alteration layer, which could eventually affect the transport of reactants and products as well as the structural stability.

36 MATERIALS SCIENCE↗

An active learning framework for the rapid assessment of galvanic corrosion

The current present in a galvanic couple can define its resistance or susceptibility to corrosion. However, as the current is dependent upon environmental, material, and geometrical parameters it is experimentally costly to measure. To reduce these costs, Finite Element (FE) simulations can be used to assess the cathodic current but also require experimental inputs to define boundary conditions. Due to these challenges, it is crucial to accelerate predictions and accurately predict the current output for different environments and geometries representative of in-service conditions. Machine learned surrogate models provides a means to accelerate corrosion predictions. However, a one-time cost is incurred in procuring the simulation and experimental dataset necessary to calibrate the surrogate model. Therefore, an active learning protocol is developed through calibration of a low-cost surrogate model for the cathodic current of an exemplar galvanic couple (AA7075-SS304) as a function of environmental and geometric parameters. The surrogate model is calibrated on a dataset of FE simulations, and calculates an acquisition function that identifies specific additional inputs with the maximum potential to improve the current predictions. This is accomplished through a staggered workflow that not only improves and refines prediction, but identifies the points at which the most information is gained, thus enabling expansion to a larger parameter space. The protocols developed and demonstrated in this work provide a powerful tool for screening various forms of corrosion under in-service conditions.

36 MATERIALS SCIENCE↗

A percolation theory for designing corrosion-resistant alloys

Iron-chromium and nickel-chromium binary alloys containing sufficient quantities of chromium serve as the prototypical corrosion-resistant metals owing to the presence of a nanometre-thick protective passive oxide film. Should this film be compromised by a scratch or abrasive wear, it reforms with little accompanying metal dissolution, a key criterion for good passive behaviour. This is a principal reason that stainless steels and other chromium-containing alloys are used in critical applications ranging from biomedical implants to nuclear reactor components. Unravelling the compositional dependence of this electrochemical behaviour is a long-standing unanswered question in corrosion science. Herein, we develop a percolation theory of alloy passivation based on two-dimensional to three-dimensional crossover effects that accounts for selective dissolution and the quantity of metal dissolved during the initial stage of passive film formation. We validate this theory both experimentally and by kinetic Monte Carlo simulation. Our results reveal a path forward for the design of corrosion-resistant metallic alloys.

36 MATERIALS SCIENCE↗

Atomic-scale decoration for improving the pitting corrosion resistance of austenitic stainless steels

Stainless steels are susceptible to the localized pitting corrosion that leads to a huge loss to our society. Studies in the past decades confirmed that the pitting events generally originate from the local dissolution in MnS inclusions which are more or less ubiquitous in stainless steels. Although a recent study indicated that endogenous MnCr 2 O 4 nano-octahedra within the MnS medium give rise to local nano-galvanic cells which are responsible for the preferential dissolution of MnS, effective solutions of restraining the cells from viewpoint of electrochemistry are being tantalizingly searched. Here we report such a galvanic corrosion can be greatly resisted via bathing the steels in Cu 2+ -containing solutions. This chemical bath generates Cu 2–δ S layers on the surfaces of MnS inclusions, invalidating the nano-galvanic cells. Our study provides a low-cost approach via an atomic scale decoration to improve the pitting corrosion resistance of stainless steels in a volume-treated manner.

36 MATERIALS SCIENCE↗

Dissolution of silica component of glass network at early stage of corrosion in initially silica-saturated solution

Corrosion of glass in silica-saturated solution has been performed with the assumption that dissolution of silicate species from the glass network would not occur. Using surface-sensitive analytical techniques, we report experimental evidence suggesting the dissolution of silicate network species from a model nuclear waste glass, called international simple glass (ISG), in an aqueous solution initially saturated with soluble silica species. Results from low energy ion scattering and X-ray photoelectron spectroscopy reveal a complete depletion of mobile element species (B, Na) from the ISG surface and an enrichment of Zr on the outmost surface. In support of spectroscopic analyses, results from topographic imaging with atomic force microscopy show a stochastic dissolution of glass surface resulting in a higher surface roughness with increasing corrosion time in aqueous solution. This study shows that a true equilibrium between soluble silica species in the solution phase and silicate species in the glass network could not be warranted by performing corrosion experiments in the solution where dissolved silica species are initially equilibrated with amorphous silica in the presence of KOH. The leaching of mobile species (B, Na) could affect the saturation level of aqueous solution and induce further dissolution of the glass surface.

36 MATERIALS SCIENCE↗

First-Principles Modeling of the Repassivation of Corrosion Resistant Alloys: Part I. O and Cl Adsorption Energy

To understand the mechanism of repassivation, a key process that controls the performance of corrosion resistant alloys (CRAs), it is useful to obtain some fundamental parameters that describe the atomistic processes. Oxygen and chlorine adsorption energies were systematically calculated with density functional theory for Ni-22Cr alloys with seven different solute elements: Co, Cu, Fe, Mn, Mo, Ru and W. All elements other than Cu enhance both O and Cl adsorption to alloy surfaces. Cr has the strongest effect among these elements. Surface configurations that give stronger O adsorption also tend to give stronger Cl adsorption. While this makes it difficult to differentiate the effect of these solute elements on the oxidation/repassivation tendency of alloys, these fundamental properties provide the foundation for higher scale models that could be used to study the oxidation process during corrosion and potentially inform the design of CRAs. Bader charge analysis reveals a strong relationship between the adatom adsorption energy and the Bader charges of both O and Cl adatom. In conclusion, the work function of alloy surfaces is increased by O while decreased by Cl, suggesting that Cl adsorption can have an intrinsic negative impact on corrosion resistance by decreasing the barrier to electron transfer.

36 MATERIALS SCIENCE↗