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At least 19 records

Galvanic corrosion of AZ31B joined to dual-phase steel with and without Zn layer by ultrasonic and friction stir welding

Galvanic corrosion of AZ31B joined with bare or Zn-coated DP590 steel by ultrasonic spot welding or linear friction stir welding was quantitatively studied by pre-defining anode and cathode in the lap joint samples. Corrosion volume and depth from Mg anode surfaces exposed to 0.1 M sodium chloride solution was analyzed as functions of cathode surface type and welding method. Characterization of as-welded joints was performed to identify any microstructural feature of the bonding zone that could impact galvanic corrosion behavior. COMSOL modeling with modified user subroutine was conducted to simulate the progression of Mg corrosion in the same joint and electrode configurations used for the corrosion experiments. The experimental results indicated that Zn-coated cathode surface can reduce Mg galvanic corrosion significantly as galvanic polarization and cathodic current on Zn-coated surface remained relatively low for Mg in the weld joints. COMSOL modeling described the growth of Mg galvanic corrosion in a reasonable manner but showed limitation by underestimating the corrosion volume as it did not capture self-corrosion.

36 MATERIALS SCIENCE↗

Mitigation of Galvanic Corrosion in Bolted Joint of AZ31B and Carbon Fiber-Reinforced Composite Using Polymer Insulation

The use of polymer insulation to mitigate galvanic corrosion was examined for bolted joints of AZ31B Mg alloy and carbon fiber-reinforced composite. To assess the corrosion behaviors of bolted joints with and without polymer insulation, solution immersion and salt spray exposure (ASTM B117) tests were conducted, and the corrosion depths and volumes were determined for the joint specimens after the tests. The polymer-insulated bolted joints exhibited much lower corrosion depths and volumes, highlighting the effective mitigation of galvanic corrosion. The reductions of joint strength in the post-corrosion joint specimens were relatively small (up to ~10%) in the polymer-insulated group but greater (up to 90%) in the group with no insulation. Cross-sectional characterization of post-corrosion joints with polymer insulation revealed local pits developed on AZ31B under galvanic influence, indicating that limited galvanic attack (that did not decrease the joining integrity significantly) could still occur during a long salt spray exposure (~1264 h) owing to the permeation of an aqueous corrosive medium.

36 MATERIALS SCIENCE↗

Galvanic Corrosion of Carbon Steel and Stainless Steel Couples: Effects of γ-Radiation and Solution Environment - 20348

Galvanic corrosion between carbon steel (CS) and stainless steel (SS) in different aqueous environments was investigated using a combination of electrochemical measurements and surface characterizations. In a basic environment (pH 10.6), the galvanic effect is negligible due to the high corrosion resistance of both alloys. In an acidic to near neutral environment (pH 6.0), the galvanic effect is more significant. Coupling to SS, increasing temperature, and irradiation at this pH have a synergistic effect on the corrosion progression of CS, and their effects vary with time. Initially, the oxidation rate of CS increases after galvanic coupling to SS. Increasing temperature or applying γ-radiation accelerates this oxidation process. However, at a longer time when the saturation limits of metal cations are reached, they also lead to the formation and growth of oxides on CS at a much faster rate, resulting in the suppression of the subsequent Fe dissolution. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Galvanic Transformation Dynamics in Heterostructured Nanoparticles

Corrosion is a significant problem for the stability of structural metals and potentially for functional nanomaterials in operating environments. When two metals with different electrochemical potentials form a junction, galvanic corrosion occurs, resulting in the sacrificial dissolution of the metal with a higher oxidation potential (lower electrode potential). In this report it is shown that bimetallic hetero-nanostructures composed of phase-segregated metals undergo galvanic corrosion in aqueous environments. Such selective etching of the sacrificial metal in heterojunction particles leads to the formation of unusual and kinetically stabilized half-spheroid particles. By using a fluid cell and in situ scanning transmission electron microscopy, a two-stage corrosion process can be observed where the Cu experiences a fractal breakdown before the Ag corrodes due to the lack of a protective oxide layer. However, when treated with a mild Ar plasma, the stability of these structures against corrosion is enhanced due to the conversion of the amorphous native oxide to a denser, thin layer of CuO on the Cu surface. Taken together, this work highlights the importance of considering the effects of galvanic corrosion on the stability of multicomponent nanoparticles, and it shows how mass transport in a nanoscale system is influenced by redox processes.

36 MATERIALS SCIENCE↗

Complementing Nanoscale Galvanic Exchange with Redox Manipulation toward Architectural Control of Multimetallic Hollow Nanostructures

Galvanic exchange occurring within the confinement by nanoparticulate templates provides a unique pathway to controllably transform solid metallic nanoparticles into architecturally more sophisticated multimetallic hollow nanostructures under facile reaction conditions. As such, in this Minireview, we elaborately discuss how the nanoparticle-templated galvanic exchange can be deliberately coupled with redox manipulation to synthesize a large library of complex multimetallic hollow nanostructures exhibiting precisely tailored architectures and compositions, with a particular emphasis on important mechanistic insights concerning the dynamic interplay among multiple structure-remodeling processes that synergistically dictate the versatile nanoparticle transforming behaviors during kinetically and regioselectively modulated galvanic exchange reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Assessment of Galvanic Corrosion in Molten Salts

Molten salts are an excellent choice for thermal energy storage materials in concentrated solar power (CSP) plants, yet some salts can cause corrosion of containment alloys that damage plants and increase maintenance costs. Corrosion rates have been characterized for many salt/alloy combinations. However, corrosion rates at junctions of dissimilar alloys in molten salts are relatively poorly characterized. At such junctions, which are common in CSP plants, it is possible that galvanic interactions or other mechanisms could increase corrosion above the industry standard of 20 µm/year. Preliminary reports measured corrosion at dissimilar alloy junctions with a variety of methods, but the results are not uniform. Additionally, some reports have shown that corrosion rates are higher for single alloys than for the same alloys when paired in a galvanic couple, suggesting complex corrosion mechanisms. Here we present a discussion on measuring galvanic corrosion in molten salts that accounts for differences in results between methods and explores the possibility of other mechanisms of corrosion in the system.

Massimi, Scott Edward (ORCID:0000000244008093)↗

Accelerating effects of galvanic corrosion and dissimilar materials on the corrosion of 316H in NaCl-MgCl2 salt

Corrosion of materials presents a significant challenge for the long-term operation of molten salt reactors. This study aims to identify the most effective techniques for evaluating the corrosion performance of materials in molten salts, with a focus on the effects of galvanic corrosion and dissimilar materials. A reliable testing methodology for assessing material corrosion in molten chloride salts has been successfully developed. The corrosion of Alloy 316H in molten NaCl-MgCl2 salt was found to be significantly accelerated by galvanic corrosion. Additionally, the presence of dissimilar materials resulted in a slight increase in the corrosion rate of Alloy 316H in NaCl-MgCl2 salt. Microstructural characterization was utilized to understand the corrosion behavior of test samples under different conditions. Common trends observed across samples include chromium depletion and iron enrichment near corroded surfaces. Molybdenum enrichment along grain boundaries and corrosion surfaces was also frequently noted.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Combined Rotating Disk Slurry Electrodeposition–Spontaneous Galvanic Displacement for Pt-M (M = Co, Ni, and Cu) Catalyst Synthesis for the Oxygen Reduction Reaction in Alkaline Media

Here, platinum-modified first-row transition-metal catalyst (M = Ni, Co, and Cu) nanoparticles on a carbon black Vulcan XC-72R (CBV) support were synthesized using rotating disk slurry electrodeposition (RoDSE) followed by spontaneous galvanic displacement (SGD) reactions. These RoDSE–SGD catalysts were evaluated for the oxygen reduction reaction (ORR) in 0.1 M KOH using rotating disk electrode techniques. The Ni and Co RoDSEs were done by using an electrochemical applied potential of -0.75 V versus the RHE and for Cu, -0.80 V versus the RHE using a CBV slurry solution containing 0.1 M KClO 4 . These metal nanoparticles on CBV (M/CBV) catalysts were modified with a Pt precursor via a spontaneous galvanic displacement (SGD) reaction, producing a Pt-M/CBV material to catalyze the ORR in an alkaline medium. High-resolution scanning transmission electron microscopy (HR-STEM) analysis indicates that the PtM/CBV samples include M clusters and Pt single atoms. The ORR characterization measurements were done under a controlled temperature (25.0 °C) and with a mass loading of 100 μg/cm 2 on a glassy carbon (GC) rotating disk electrode at 1600 rpm. The PtCo/CBV showed the highest ORR mass activity of 0.741 A/mgPt at 0.90 V versus the reversible hydrogen electrode (RHE) compared with commercial Pt/CBV. The M/CBV RoDSE catalysts were also tested for the oxygen evolution reaction (OER), and Ni/CBV provided the lowest overpotential of 450 mV at 10 mA/cm 2 disk in 0.1 M KOH.

30 DIRECT ENERGY CONVERSION↗

Absolute Templating of M(111) Cluster Surrogates by Galvanic Exchange

The precise preparation of monodisperse nanomaterials is among the most fundamental tasks in inorganic synthesis and materials science. Achieving this goal by galvanic exchange is hardly predictable, and often results in major structural changes and polydisperse mixtures. Here, taking advantage of the enhanced stability imparted by ambiphilic carbenes, we report and rationalize the absolute templating — the complete exchange of metals in a template — of group 11 clusters across the entire coinage metal family by means of galvanic exchange. We further delineate that these species provide a molecular model for better understanding the reduction of CO 2 at M(111) coinage metal surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Giant topological longitudinal circular photo-galvanic effect in the chiral multifold semimetal CoSi

The absence of mirror symmetry, or chirality, is behind striking natural phenomena found in systems as diverse as DNA and crystalline solids. A remarkable example occurs when chiral semimetals with topologically protected band degeneracies are illuminated with circularly polarized light. Under the right conditions, the part of the generated photocurrent that switches sign upon reversal of the light’s polarization, known as the circular photo-galvanic effect, is predicted to depend only on fundamental constants. The conditions to observe quantization are non-universal, and depend on material parameters and the incident frequency. In this work, we perform terahertz emission spectroscopy with tunable photon energy from 0.2 –1.1 eV in the chiral topological semimetal CoSi. We identify a large longitudinal photocurrent peaked at 0.4 eV reaching ~550 μ A/V 2 , which is much larger than the photocurrent in any chiral crystal reported in the literature. Using first-principles calculations we establish that the peak originates only from topological band crossings, reaching 3.3 ± 0.3 in units of the quantization constant. Our calculations indicate that the quantized circular photo-galvanic effect is within reach in CoSi upon doping and increase of the hot-carrier lifetime. The large photo-conductivity suggests that topological semimetals could potentially be used as novel mid-infrared detectors.

79 ASTRONOMY AND ASTROPHYSICS↗

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↗

Editors’ Choice—Natural Convection Boundary Layer Thickness at Elevated Chloride Concentrations and Temperatures and the Effects on a Galvanic Couple

The natural convection boundary layer ( δ n c ) and its influence on cathodic current in a galvanic couple under varying electrolytes as a function of concentration (1 − 5.3 M NaCl) and temperature (25 °C−45 °C) were understood. Polarization scans were obtained under quiescent conditions and at defined boundary layer thicknesses using a rotating disk electrode on platinum and stainless steel 304L (SS304L); these were combined to determine δ n c . With increasing chloride concentration and temperature, δ n c decreased. Increased mass transport (Sherwood number) results in a decrease in δ n c , providing a means to predict this important boundary. Using Finite Element Modeling, the cathodic current was calculated for an aluminum alloy/SS304L galvanic couple as a function of water layer ( WL ) thickness and cathode length. Electrolyte domains were delineated, describing (i) dominance of ohmic resistance over mass transport under thin WL , (ii) the transition from thin film to bulk conditions at δ n c , and (iii) dominance of mass transport under thick WL . With increasing chloride concentration, cathodic current decreased due to decreases in mass transport. With increasing temperature, increased cathodic current was related to increases in mass transport and solution conductivity. This study has implications for sample sizing and corrosion prediction under changing environments.

25 ENERGY STORAGE↗

Excitation dynamics in galvanically coupled fluxonium circuits

We propose a near-term quantum simulator based on the fluxonium qubits galvanically coupled to form a chain. This system provides long coherence time, large anharmonicity, and strong coupling, making it suitable to study strongly interacting Ising spin models. At half-flux quantum sweet spot, the system is described by the transverse field Ising model (TFIM). We evaluate the propagation of qubit excitations through the system. As disorder increases, the excitations become localized. A single qubit measurement using the circuit QED methods is sufficient to identify localization transition without introducing tunable couplers. We argue that galvanically coupled fluxoniums provide opportunities to study localization and many-body effects in highly coherent quantum systems.

Ozguler, A. Baris↗

Non-galvanic mass transport in molten fluoride salt isothermal corrosion cells

Mass transport of corrosion products between Ni-201 test samples and 316 L capsules in a 500-hour FLiNaK corrosion experiment has been investigated. In one experiment, the capsule and samples were electrically connected for galvanic coupling, while in the other they were electrically isolated using boron-nitride. Post-corrosion characterization of Ni-201 from the two experiments did not reveal any remarkable differences. Substantial transport of Fe and Cr from the 316 L to the Ni-201 via the salt was observed, with notable diffusion of these elements in the near-surface regions of the Ni-201 samples, while a Cr-rich film was also observed on their surfaces.

36 MATERIALS SCIENCE↗

Numerical investigation of micro-galvanic corrosion in Mg alloys: Role of the cathodic intermetallic phase size and spatial distributions

Magnesium alloys are of increasing interest in structural applications due to their low-density, moderate specific strength and stiffness, recyclability, and high damping among other properties. However, the wide-scale applicability of magnesium alloys in structural applications has been limited due to many factors including its poor corrosion resistance. In this work, a numerical investigation to simulate the micro-galvanic corrosion behavior was performed to examine the influence of size and distribution of cathodic intermetallic phase (ß-Mg17Al12) in a Mg matrix. The ratio of cathodic to anodic surface area was kept constant in each simulation condition to understand the effect of size and spacing distributions. In general, fragmentation of a larger intermetallic particle into smaller ones was found to enhance the localized current density. However, the uniform distribution of this small intermetallic phase throughout the matrix was found to reduce the overall dissolution current density and hence, pitting corrosion severity.

Beura, Vikrant↗

Stress corrosion cracking mechanism of cold spray coating on a galvanically similar substrate

Here, the chloride-induced stress corrosion cracking (CISCC) mechanism of cold spray (CS) coating on a galvanically similar substrate is investigated. Arc welded 304L stainless steel (SS) specimens are loaded into four-point bend fixtures, cold sprayed with 304L SS, then immersed in boiling MgCl 2 . Interconnected porosity forms through crevice corrosion along CS splat boundaries, allowing corrosive species to penetrate through the CS layer. Nevertheless, the substrate is resistant to CISCC likely because of compressive stress introduced by peening during CS particle impacts. These findings underscore the importance of residual stress in the environmental degradation of CS coatings or repairs of engineering structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Inverse iron oxide/metal catalysts from galvanic replacement

Key chemical transformations require metal and redox sites in proximity at interfaces; however, in traditional oxide-supported materials, this requirement is met only at the perimeters of metal nanoparticles. We report that galvanic replacement can produce inverse FeO x /metal nanostructures in which the concentration of oxide species adjoining metal domains is maximal. The synthesis involves reductive deposition of rhodium or platinum and oxidation of Fe 2+ from magnetite (Fe 3 O 4 ). We discovered a parallel dissolution and adsorption of Fe 2+ onto the metal, yielding inverse FeO x -coated metal nanoparticles. This nanostructure exhibits the intrinsic activity in selective CO 2 reduction that simple metal nanoparticles have only at interfaces with the support. By enabling a simple way to control the surface functionality of metal particles, our approach is not only scalable but also enables a versatile palette for catalyst design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Design and optimization of high temperature optocouplers as galvanic isolation

The commercial InGaN-based (blue and green) and AlGaInP-based (red) multiple quantum well (MQW) lighting emitting diodes (LEDs) were studied in a wide range of temperatures up to 800 K for their light emission and detection (i.e., LEDs operated under reverse bias as photodiodes (PDs)) characteristics. The results indicate the feasibility of integrating a pair of selected LEDs to fabricate high temperature (HT) optocouplers, which can be utilized as galvanic isolation to replace the bulky isolation transforms in the high-density power modules. A detailed study on LEDs and PDs were performed. The external quantum efficiency (EQE) of the LED and PDs were calculated. Higher relative external quantum efficiency (EQE) and lower efficiency droops with temperatures are obtained from the blue and green LEDs for display compared with the blue one for lighting and red LED for display. The blue for lighting and red for display devices show superior responsivity, specific detectivity (D*), and EQE compared with blue and green for display when operated as PDs. The results suggest that red LED devices for display can be used to optimize HT optocouplers due to the highest wavelength overlapping compared with others.

42 ENGINEERING↗