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At least 703 records · Page 39

Mitigating CO 2 Corrosion of Natural Gas Steel Pipelines by Thermal Spray Aluminum Coatings

We report internal pipeline corrosion due to carbon dioxide (CO 2 ) is a major challenge facing the oil and gas industry. The objective of this study was to investigate the corrosion behavior of aluminum (Al)-based alloys as sacrificial coatings to protect pipelines in a CO 2 -saturated aqueous electrolyte (3.5 wt% NaCl) at 4 bar CO 2 partial pressure (3 bar) and 40°C. The corrosion resistance of Al-based alloys and thermal spray coatings was evaluated in an electrochemical reaction autoclave using electrochemical methods (potentiodynamic polarization, linear polarization resistance, and electrochemical impedance spectroscopy). Post-corrosion surface characterization was performed by scanning electron microscopy equipped with energy-dispersive x-ray spectroscopy. The obtained data show Al-based alloys demonstrated promising protection against CO 2 corrosion with no breakaway degradation issues.

36 MATERIALS SCIENCE↗

Recent Developments on Microencapsulation for Autonomous Corrosion Protection

This work concerns recent progress in the development of a multifunctional smart coating based on microencapsulation for the autonomous control of corrosion. Microencapsulation allows the incorporation of desired corrosion control functionalities, such as early corrosion detection and inhibition through corrosion controlled release of corrosion indicators and inhibitors, as well as self-healing agent release when mechanical damage occurs.While proof-of-concept results have been reported previously, more recent efforts have been concentrated in technical developments to improve coating compatibility, synthesis procedure scalability, as well as fine tuning the release property of encapsulated active agents.

Corrosion↗

Microencapsulation Technologies for Corrosion Protective Coating Applications

Microencapsulation technologies for functional smart Coatings for autonomous corrosion control have been a research area of strong emphasis during the last decade. This work concerns the development of pH sensitive micro-containers (microparticles and microcapsules) for autonomous corrosion control. This paper presents an overview of the state-of-the-art in the field of microencapsulation for corrosion control applications, as well as the technical details of the pH sensitive microcontainer approach, such as selection criteria for corrosion indicators and corrosion inhibitors; the development and optimization of encapsulation methods; function evaluation before and after incorporation of the microcontainers into coatings; and further optimization to improve coating compatibility and performance.

Microencapsulation↗

CORROSION TESTING OF CARBON STEEL IN OXALIC ACID CHEMICAL CLEANING SOLUTIONS

Radioactive liquid waste has been stored in underground carbon steel tanks for nearly 60 years at the Savannah River Site. The site is currently in the process of removing the waste from these tanks in order to place it into vitrified, stable state for longer term storage. The last stage in the removal sequence is a chemical cleaning step that breaks up and dissolves metal oxide solids that cannot be easily pumped out of the tank. Oxalic acid has been selected for this purpose because it is an effective chelating agent for the solids and is not as corrosive as other acids. Electrochemical and immersion studies were conducted to investigate the corrosion behavior of carbon steel in simulated chemical cleaning environments. The effects of temperature, agitation, and the presence of sludge solids in the oxalic acid on the corrosion rate and the likelihood of hydrogen evolution were determined. The testing showed that the corrosion rates decreased significantly in the presence of the sludge solids. Corrosion rates increased with agitation, however, the changes were less noticeable.

08 HYDROGEN↗

Materials corrosion in molten LiF-NaF-KF eutectic salt under different reduction-oxidation conditions

Molten fluoride salts such as FLiNaK (LiF-NaF-KF: 46.5-11.5-42 mol %) have been proposed for use as secondary reactor coolants, media for transfer of high temperature process heat from nuclear reactors to chemical plants, and for concentrated solar power thermal energy storage. In molten fluoride salts, passive oxide films are chemically unstable, and corrosion is driven largely by the thermodynamically driven dissolution of alloying elements into the molten salt environment. Two alloys, Hastelloy{sup R} N and 316L stainless steel were exposed to molten FLiNaK salt in a 316L stainless steel crucible under argon cover gas for 1000 hours at 850 deg. C. Graphite was present in some of the crucibles with the goal of studying corrosion behavior of relevant reactor material combinations. In addition, a technique to reduce alloy corrosion through modification of the reduction-oxidation state was tested by the inclusion of zirconium to the system. Corrosion of 316L stainless steel was noted to occur primarily through surface depletion of chromium, an effect that was enhanced by the presence of graphite. Hastelloy{sup R} N experienced weight gain through electrochemical plating of corrosion products derived from the 316L stainless steel crucible. In the presence of zirconium, both alloys gained weight through plating of zirconium and as a result formed intermetallic layers. (authors)

36 MATERIALS SCIENCE↗

Corrosion Control during Closure Activities at the Savannah River Site - 13514

Liquid radioactive wastes from the Savannah River Site (SRS) separation process are stored in large underground carbon steel tanks. Until the waste is removed from storage, transferred, and processed, the materials and structures of the tanks must maintain a confinement function by providing a barrier to the environment and by maintaining acceptable structural stability during normal service and design basis events (e.g., earthquake conditions). A corrosion control program is in place to ensure that degradation of the steel does not impact the structural and leak integrity functions of these waste tanks. The SRS is currently retrieving waste from older waste tanks and processing the waste through the vitrification for long term stabilization. The retrieval processes prepare the tanks for ultimate closure (i.e., grouting) by removing sludge by mechanical and/or sluicing methods, dissolving salt cake by adding water, and chemical cleaning of the residual sludge with oxalic acid. Each of these retrieval methods will result in waste chemistry that does not meet the requirements of the current corrosion control program. Given the short-term exposure and limited remaining service life for the tanks in which retrievals are being performed, an assessment of the need for corrosion controls in these tanks was performed. The assessment reviewed the corrosion rates in the more aggressive environments and the postulated loads on the structure during the closure activities. The assessment concluded that the current corrosion control program may be suspended for a short period of time while final retrieval of the waste is performed. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Zirconium Alloy Corrosion and Hydrogen Pickup

During operation nuclear fuel rods are immersed in the primary water, causing waterside corrosion and consequent hydrogen ingress. The mechanisms of corrosion and hydrogen pickup and the role of alloy selection in minimizing both phenomena are considered, based on two principal characteristics: the pre-transition kinetics and the loss of oxide protectiveness at transition. In zirconium alloys very small changes in composition or microstructure can cause significant corrosion differences, so that corrosion performance is strongly alloy dependent. The alloys show different, but reproducible sub-parabolic pre-transition kinetics and transition thicknesses. A mechanism for oxide growth and breakup based on a detailed study of the oxide structure can explain these results. Using the recently developed Coupled Current Charge Compensation model of corrosion kinetics and hydrogen pickup, the sub-parabolic kinetics and the hydrogen fraction can be rationalized: hydrogen pickup increases when electron transport decreases, requiring hydrogen ingress to close the reaction. (authors)

36 MATERIALS SCIENCE↗

Development of neural network force fields for corrosion studies

To fully understand the chemistry and physics of corrosion, novel methods of simulation must be developed. One approach is designing machine learning (ML) algorithms integrated with density functional theory to develop adaptive force fields to gain insight into corrosion behavior namely at the surface of metal oxides. Current methods of modeling corrosion are slow due to the computational cost of resolving both reaction mechanics and mass transport processes. Machine learning methods can be implemented to obtain structure-activity relationships at both the molecular and bulk scale while still retaining the accuracy of density functional theory (DFT) and significantly decreasing the time needed for simulations of complex chemical processes in the various environments of corrosion. Multiscale models are needed for corrosion studies to fully understand its processes not only at the atomic length scale (chemical bonding, energies, and forces), but also at the nano and meso length scales (solid-state physics and material science processes). Current methods of study include DFT, molecular dynamics, and Monte Carlo. The limitation of DFT is that only a small number of atoms or molecules can be simulated at that level of theory. Density functional theory is used to study the electronic structure of atoms and molecules, and calculate the force component of each atom. However, these calculations are limited to about 1000 atoms. Custom periodic boundary conditions (PBC) can be used to describe the various environments and defects that affect the atomic forces to produce a large data set from which a training set can be derived. Machine learning can be utilized to overcome the barrier of modeling macroscopic and multi-scale processes from ab initio calculations through the development of adaptive force fields. Local environments determine the atomic forces of a given system, therefore adaptive force fields must be created to produce reliable quantum mechanical calculations. This can be achieved by developing a learning algorithm that uses the mapped atomic forces or fingerprint as an input to produce energies and magnetic moments as output. A systematic approach was used to begin to build a data set in order to accurately describe the atomic forces in various environments. In Figure 4 below, a simple PBC cell of Fe{sub 2}O{sub 3} was first optimized. A surface optimization was performed next, followed by a hydroxylated surface optimization. Once this calculation has converged, the adsorption of halide species to the hydroxylated surface will be investigated. TensorFlow is an open source platform for machine learning developed by Google. Using a high level application program interface (API) such as Keras allows for building and training ML models easily in a number of different environments and languages. For this project, a neural network was developed within Anaconda in Python. Future Work: Further development of reference data set; Refining neural network and learning algorithm; Fingerprinting atomic environment to enable mapping of atomic force components; Choosing appropriate training set from reference data; Learning from training set and enabling non-linear mapping of training set fingerprints and the atomic forces; Estimation of uncertainty to identify ranges of outside applicability; Testing and analysis of molecular dynamic simulations.

36 MATERIALS SCIENCE↗

Elucidating the corrosion mechanism of commercial Ni-based Superalloys in UCl3 containing-chloride Molten Salt Systems

Molten salt reactors (MSRs) have gained renewed interest, providing several advantages over their predecessors, including the capability to consume spent fuels, enhancing the environmental sustainability of the uranium fuel cycle. For example, molten chloride fast reactors (MCFRs) can reach criticality with molten chloride spent fuel containing high concentrations of impurities, such as actinide products like uranium chloride (UCl3). However, the redox potential of chloride molten salt fuels may change in the presence of these impurities, dictating their corrosivity and in turn the corrosion performance of structural components, such as those constructed from nickel (Ni)-based alloys. The purpose of this investigation is to assess the extent of corrosion of Ni-based alloy, Inconel 617, when exposed to UCl3-LiCl-KCl eutectic salt. Inconel 617 one of only six structural materials that are fully qualified by the American Society for Mechanical Engineers (ASME) Boiler and Pressure Vessel Code for high-temperature nuclear reactor components, making it a technologically mature material to consider for constructing MCFRs. Inconel 617 specimens were submerged in a static LiCl-KCl-UCl3 eutectic salt mixture heated at 700 C for 1000 h under an inert atmosphere. Upon completion, the extent of corrosion was analyzed through a multi-modal characterization approach spanning the engineering to nanoscale, employing computed tomography, focused-ion beam, and transmission electron microscopy techniques. Results from this investigation will enhance our understanding of property-to-performance relationships of candidate structural materials for MSRs with respect to corrosion resistance and interactions between the salt and alloy interface.

36 MATERIALS SCIENCE↗

Elucidating the corrosion mechanism of commercial Ni-based superalloys in UCl3 containing-chloride molten salt systems

Elucidating the role of UCl3 in the corrosion mechanism of Ni-based superalloys exposed to chloride molten salts Trishelle Copeland-Johnson1, Michael Woods1, Ruchi Gakhar1, Daniel J. Murray1, Guoping Cao1, Lingfeng He1 1Idaho National Laboratory, Idaho Falls, ID, United States The United States Department of Energy (DOE) aims to diversify the domestic energy portfolio towards more sustainable options, including implementation of molten salt reactor (MSR) technology. Chloride molten salts have been investigated as an appropriate MSR coolant and fuel because their relatively inexpensive, abundant, and exhibit favorable thermophysical properties. However, the corrosivity of chloride molten salts have not been extensively studied, especially with the inclusion of actinide products, such as UCl3. Accordingly, the development of nuclear structural materials with excellent corrosion performance is critical to the successful implementation of MSRs, particularly from a mechanistic perspective. In this investigation, we attempt to elucidate the interfacial corrosion mechanism between Ni-based structural materials, such as Inconel 617, and UCl3-containing salt systems through a multi-modal advanced characterization approach, including electron microscopy techniques. The findings from this investigation will expand the knowledgebase of chloride molten salt corrosion of MSR structural materials for strategic property-to-performance design.

36 - MATERIALS SCIENCE↗

Corrosion Behavior of Wire Electrical Discharge Machined Surfaces of P91 Steel

The extensive usage of P91 steel in certain reactor components requires its precision fabrication by wire electrical discharge machining (WEDM). The WEDM cut surfaces consist of primarily re-melted and solidified layer (recast layer) of 2-8 µm. The recast layer is a result of fast removal of heat by unaffected metallic substrate and dielectric medium leading to rapid cooling. The WEDM surface is expected to affect the component performance in terms of its corrosion properties. The microstructural changes taking place due to EDM cutting of P91 steel bring about a drastic change in the electrochemical response of surface as compared to that for bulk P91 steel. The surface microstructure is shown to alter the passivation behavior and resistance to localized corrosion. Electrochemical polarization studies were done to evaluate passivation, pitting and intergranular corrosion (IGC) behavior and field emission gun—scanning electron microscopy was used for microstructural characterization of P91 steel surfaces. The passivation behavior for P91 steel WEDM cut surfaces was better than that for diamond polished surface. But pitting corrosion resistance decreased for the P91 steel WEDM surface which is a result of inhomogeneities in the microstructure of recast layer. The IGC resistance though increased due to the decreased grain size in the surface layer.

36 MATERIALS SCIENCE↗

Few-Layers Graphene Film and Copper Surface Morphology for Improved Corrosion Protection of Copper

Graphene has shown excellent corrosion protection of copper (Cu). The corrosion protection of Cu is governed by the characteristics of the deposited graphene and Cu surface morphology underneath. In this work, graphene films (1-2, 4-5 layers) were deposited on Cu using a chemical vapor deposition by changing hydrogen (H{sub 2}) concentration during the annealing stage. The chemical structure and surface microstructural features of graphene/Cu were inspected by Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, and atomic force microscopy. The electrochemical corrosion performance of graphene/Cu was studied in 0.5 M sodium chloride solution using potentiodynamic polarization and electrochemical impedance spectroscopic measurements. The 1-2 layers of graphene and rough Cu surface were obtained for low H{sub 2} concentrations (0 and 2.5%), whereas high H{sub 2} concentrations, 20 and 50%, resulted in a smooth Cu surface and 4-5 layers of graphene. Our results showed that Cu with a smooth surface and multilayer graphene film exhibited the best corrosion resistance against electrochemical degradation. Tafel analysis revealed that Cu with 4-5 layers of graphene coating corroded nearly three orders of magnitude slower than the annealed Cu, without graphene coating. The results of this study can be useful for several applications where Cu is in close contact with salt species.

36 MATERIALS SCIENCE↗

Corrosion resistance of ZrO{sub 2}–TiO{sub 2} nanocomposite multilayer thin films coated on carbon steel in hydrochloric acid solution

This work reports the achievement of preparing of x% zirconia (ZrO{sub 2})–titania (TiO{sub 2}) composite coatings with different ZrO{sub 2} percent on the carbon steel by dipping substrates in sol–gel solutions. The prepared coated samples were investigated by various surface techniques including X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDAX). Open-circuit potential (OCP), potentiodynamic polarization, and electrochemical impedance spectroscopy (EIS) methods were employed to investigate the corrosion resistance of the coated carbon steel substrates in 1.0 M HCl solution at 50 °C. The data showed that, the corrosion protection property is not always proportional to the percent of ZrO{sub 2}. It can be inferred that there is an optimum percent (10%ZrO{sub 2}) for beneficial effects of loading ZrO{sub 2} on the protection efficiency (98.70%), while higher loading percent of ZrO{sub 2} in the sol–gel coating leads to the formation of a fragile film with poor barrier properties. EDAX/SEM suggests that the metal surface was protected through coating with ZrO{sub 2}–TiO{sub 2} composite films. - Highlights: • Sol–gel TiO{sub 2} doped with ZrO{sub 2} films deposited on carbon steel substrate • XRD measurements of x wt.% ZrO{sub 2}–TiO{sub 2} showed the (101) peaks broader than that of TiO{sub 2}. • SEM results proved that, the cracking decreases with the number of layers. • The prepared films can improve the corrosion resistance of the carbon steel substrate. • 10%ZrO{sub 2} loading is the optimal percent for useful effects on the corrosion resistance.

36 MATERIALS SCIENCE↗

Elevated-Temperature Corrosion of CoCrCuFeNiAl0.5Bx High-Entropy Alloys in Simulated Syngas Containing H2S

High-entropy alloys are formed by synthesizing five or more principal elements in equimolar or near equimolar concentrations. Microstructure of the CoCrCuFeNiAl{sub 0.5}B{sub x} (x = 0, 0.2, 0.6, 1) high-entropy alloys under investigation is composed of a mixture of disordered bcc and fcc phases and borides. These alloys were tested gravimetrically for their corrosion resistance in simulated syngas containing 0, 0.01, 0.1, and 1 % H{sub 2}S at 500 °C. The exposed coupons were characterized using XRD and SEM. No significant corrosion was detected at 500 °C in syngas containing 0 and 0.01 % H{sub 2}S while significant corrosion was observed in syngas containing 0.1 and 1 % H{sub 2}S. Cu{sub 1.96}S was the primary sulfide in the external corrosion scale on the low-boron high-entropy alloys, whereas FeCo{sub 4}Ni{sub 4}S{sub 8} on the high-boron high-entropy alloys. Multi-phase Cu-rich regions in the low-B high-entropy alloys were vulnerable to corrosive attack.

36 MATERIALS SCIENCE↗

Corrosion of Magnesium in Multimaterial System

The TMS Magnesium Committee has been actively involved in presenting cutting-edge research and development and the latest trends related to magnesium and its alloys to industry and academia. Topics including magnesium alloy development, applications, mechanism of deformation and corrosion, thermomechanical processing, modelling, etc. have been captured year after year through the Magnesium Technology symposium and conference proceedings at TMS and through special topics in JOM. Every year, based on the unanimous endorsement from the industry and academia, a topic is selected to address the latest developments within this subject in JOM. In continuation with last year’s coverage of Advances and Achievements in In-Situ Analysis of Corrosions and Structure–Property Relationship in Mg Alloys,[1] this year’s topic focuses on the Corrosion of Magnesium in Multimaterial Systems. Magnesium, the lightest of all the structural materials, has garnered much interest in the transportation, electronics packaging, defense equipments and industries alike and are more commonly being incorporated in multimaterial design concepts.[2-4] However, the application of the same is limited due to its highly corrosive nature, and understanding and mitigating the corrosion of magnesium has been a major research challenge.

Joshi, Vineet V.↗

Spatial mapping of the localized corrosion behavior of a magnesium alloy AZ31B tungsten inert gas weld

Sections of a magnesium alloy, AZ31B, joined with tungsten inert gas (TIG) welding, were examined with scanning electrochemical microscopy (SECM) and scanning Kelvin probe force microscopy (SKPFM) to investigate corrosion mechanisms by correlating observed corrosion behavior with weld-affected microstructural variations. Insight into the changing nature of the galvanic couples between weld zones and at localized microgalvanic sites were investigated using SECM and SKPFM to map both electrochemically active regions and Volta potential differences across the weld-affected zones. The formation of an Al-Zn solidification network in the fusion zone (FZ) at and near the TIG weld epicenter differs from the outer heat-affected zone (HAZ), where intermetallic particles (IMPs) are the notable secondary phase from the magnesium matrix. These microstructures were mapped with SKPFM before and after brief exposure to a salt solution, revealing micro-galvanic couples as the main driving force to corrosion initiation and propagation within each zone. The IMPs and Al-Zn solidification network act as strong cathodes and govern the corrosion processes. The galvanic coupling and evolution of the intrinsic corrosion behavior between the weld zones is explained by monitoring the hydrogen evolution reaction (HER) with SECM over time. Anodically induced cathodic activation is confirmed for this welded material, as micro-galvanic couples between microstructural features are found to transition over time to broad electrochemically active areas within the weld-affected zones, resulting in polarity reversal as time of exposure proceeds.

Anodically induced cathodic activation↗

Degradation of HT9 under simultaneous ion beam irradiation and liquid metal corrosion

A potentially promising coolant/structural material pair for a liquid-metal-cooled fast reactors is lead bismuth eutectic (LBE) coolant with the ferritic/martensitic steel HT9. The challenge of deploying LBE, however, is the corrosive environment it creates for structural materials. This corrosion can be mitigated with precise oxygen content control in the LBE to allow for the growth of passive protective oxide layers on the surface of the steel. In this paper, results are reported from the Irradiation Corrosion Experiment II (ICE-II), which allowed the simultaneous irradiation of a sample while in contact with LBE. It was found that a characteristic multilayer structure with an outer Fe 3 O 4 oxide and inner FeCr 2 O 4 spinel was grown and the oxidation was significantly larger in the irradiated region when compared to the region that was only exposed to LBE corrosion. As a result, a possible mechanisms are discussed to help understand this irradiation enhanced corrosion behavior.

36 MATERIALS SCIENCE↗

Method for identification of redox control parameters for corrosion mitigation in molten fluoride salts

Structural material corrosion is a significant concern for the development of molten salt-cooled reactors (MSR) and redox control was proposed to mitigate the corrosion. This study presents an efficient approach to identify the partial pressure of F 2 gas for fluorine driven corrosion, the concentration ratios of UF 4 /UF 3 and ZrF 4 /ZrF 2 , and the partial pressure ratio of HF/H 2 needed to limit metal corrosion and its subsequent dissolution in molten fluoride salts. The identification procedure is made by simply using auxiliary axes in Ellingham diagrams. This approach greatly simplifies the optimization of redox control methods in studying the material corrosion in molten salts.

36 MATERIALS SCIENCE↗