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At least 199 records · Page 11

Corrosion Behavior of Alloy Structural Steels in Catechol and Biomass-Derived Pyrolysis Oils

Electrochemical impedance spectroscopy (EIS) was used to assess the corrosion behavior of three steels, 2.25Cr-1Mo, 5Cr-1Mo and 9Cr-1Mo (UNS K21590, S50200 and K90941) in bio-oils and catechol, an organic constituent commonly found in bio-oils. Two types of biomass pyrolysis oils produced from selected forest residue feedstocks, classified as high-ash and high-moisture (HAHM) and low-ash and low-moisture (LALM) types and 10 wt.% catechol, were used to test the alloys. According to previous results, 10 wt.% catechol in a water and methanol mixture was corrosive to 2.25Cr-1Mo but not to 9Cr-1Mo, highlighting that increasing Cr content in the steels resulted in improved corrosion resistance. 5Cr-1Mo, a steel with an intermediate Cr content, was tested in catechol solutions to better estimate the critical value of Cr for corrosion resistance under these conditions. Also, the three alloys were tested in both HAHM and LALM bio-oils to assess corrosion susceptibility. For EIS measurements, a customized electrochemical setup was employed to minimize the ohmic path through the bio-oils. The corrosion susceptibility was evaluated by determining the resistance at the alloy-corrosive medium interface.

Jun, Jiheon↗

Electrochemical Corrosion Analysis of Stainless Steels in LALM Pyrolysis Bio-Oil with Organic Corrodents

Pyrolysis bio-oils are corrosive to low alloy steels, e.g., 2.25Cr-1Mo, 5Cr-1Mo, and 9Cr-1Mo grades. To identify the alloys with sufficient bio-oil compatibility, several commercial stainless steels were examined in bio-oil using electrochemical impedance spectroscopy to semi quantitatively assess their corrosion resistance. Low-Ash Low-Moisture (LALM) bio-oil, produced from a forest residue feedstock by the National Renewable Energy Laboratory in Golden, CO, was used as a test liquid for electrochemical impedance spectroscopy measurements. Three organic corrodents, formic acid, catechol, and lactobionic acid, were added into LALM bio-oil to produce test liquids with intentionally increased corrosivity. Corrosion reaction resistance, determined from the impedance data, was used to evaluate the corrosion compatibility of each stainless steel in LALM bio-oil and LALM bio-oil + organic corrodent(s). The results from corrosion reaction resistance indicated that the critical Cr content of stainless steels for corrosion resistance would be greater than 14 wt % if Ni and Mo contents are low but can be as low as 12–13 wt % with appreciable amounts of Ni and Mo.

Jun, Jiheon↗

CFD modeling and simulation for corrosive wear of refractory in molten slag

The development of high-wear resistant refractories having minimal production costs is facilitated by characterizing the wear mechanisms associated with their corrosive wear. Static cup testing is a commonly used method for comparing the corrosion resistance performance of two or more refractory materials. Although the static cup test conditions are not as severe as dynamic tests, this study shows that the thermal gradient present within the system during heating and cooling stages serves to generate movement of the slag leading to mechanical wear. The thermal gradient within the refractory, and between the slag and the refractory, occurs during the ramp stage of the test and lasts until the soaking stage is reached bringing the system to a thermal equilibrium. Using computational fluid dynamics (CFD) capabilities embedded within ANSYS software, this study modelled and quantified the convection currents within the slag and associated shear stresses generated on the refractory walls due to the thermal gradient. A traditional ladle furnace was employed as a case study to verify the results of the studied CFD model. The corrosion rate of the refractory lining was found to depend on the mass transfer coefficient of the refractory dissolution into the slag, and a velocity term which governs the extent of corrosion at any given location. This velocity term is a function of slag viscosity, as well as the concentration gradient and/or temperature gradient at the triple points. In this study, wall shear stress was used as a reliable proxy for identifying high-velocity regions prone to excessive corrosive wear. Elevated wall shear stress near the slag/air and slag/molten steel interfaces align with observed corrosion grooves, which reflects the intensified corrosive wear at these locations.

Ramteke, Rajat Rajat Durgesh Ramteke [University o↗

Electrochemical Corrosion Behavior of 5083 Aluminum Alloy Subjected to Laser Shock Peening

This paper investigates the effect of ablative coating used during laser shock peening (LSP) on corrosion behavior of 5083 aluminum alloy in artificial seawater. Micro-hardness, residual stress, and surface morphology of the specimens were measured. The corrosion behavior was investigated by electrochemical test. Surface corrosion morphologies after electrochemical tests were examined by SEM and EDS. The results show that surface roughness and surface compressive residual stress of the specimen treated by LSP without ablative coating (LSPwC) are lower than that of the specimen treated by LSP with ablative coating under the same laser energy. The open-circuit potentials and self-corrosion potentials of the specimens treated by LSP and LSPwC both shift positively, and the diameters of the capacitor arcs were larger after LSP and LSPwC. The corrosion resistance of 5083 aluminum alloy is improved by LSP and LSPwC. Moreover, superior corrosion resistance is achieved without using the ablative coating during LSP.

36 MATERIALS SCIENCE↗

Corrosion Behavior of Fe-7Cr-1Mo-12Zr Metal Waste Form Alloy in Simulated Repository Environment

Metal waste forms (MWF) are solid metallic waste categorized as high-level radioactive waste generated during pyro-reprocessing of spent metallic fuels and geologically disposed off. This waste form generated requires an excellent corrosion resistance in a geological repository environment. In the present work, Fe-7Cr-1Mo-12Zr MWF alloy was developed by casting in an arc melting furnace. The x-ray diffraction analysis revealed the formation of stable phases of α-Fe solid solution and the intermetallic phases of Fe{sub 2}Zr and Fe{sub 23}Zr{sub 6}. The corrosion behavior of Fe-7Cr-1Mo-12Zr alloy was investigated using electrochemical techniques in aggressive (highly acidic with Cl{sup −}) and nominal repository pH environment. Cyclic potentiodynamic polarization studies indicated the shift in corrosion potential toward cathodic potential in highly acidic solution with Cl{sup −}. The corrosion mechanism of pitting is associated with acidified pH medium with more Cl{sup −}, whereas uniform corrosion or transpassive dissolution is resultant of mild acidity or mild alkaline medium. The passive region is wider in pH 5 and 8 when compared to pH 1 and 3. Electrochemical impedance spectroscopic (EIS) analysis revealed the lowering of passive film stability in the highly acidic medium in the presence of Cl{sup −}. The role of passive oxide layers on the corrosion resistance of the Fe-7Cr-1Mo-12Zr MWF alloy is discussed.

36 MATERIALS SCIENCE↗

Corrosion integrity of oil cement modified by environment responsive microspheres for CO2 geologic sequestration wells

In order to ensure the safe and effectiveness of CO{sub 2} geological storage, an environmental responsive polymer microspheres (ERPM) was prepared to improve the corrosion resistance of cement stone. The structure and environmental response characteristics of ERPM were characterized, and then the anti-corrosion performance and anti-corrosion mechanism for ERPM were discussed. The results shown that ERPM had good environmental response characteristics and temperature resistance. ERPM could effectively suppressed the corrosion rate and the damage degree of mechanical properties of cement stone. The corrosion integrity of cement stone was improved due to the acidic response characteristic and form polymer films of ERPM, which effectively shield the direct contact between corrosion medium and hydration products.

36 MATERIALS SCIENCE↗

Enhanced crevice corrosion of stainless steel 316 by degradation of Cr-containing hollandite crevice former

This study explores the corrosion interactions between stainless steel 316 (SS316), a candidate nuclear waste canister material, and Cr-containing hollandite (Ba 1.15 Cr 2.3 Ti 5.7 O 16 ), a model ceramic nuclear waste form. The two materials were corroded in close proximity in 0.6 M NaCl solution at 90 °C for 28 days. Severe crevice corrosion was observed on the stainless steel surface after the corrosion experiment, which is likely associated with the rapid accumulation of Cr 3+ cations originating from both SS316 and the Cr-containing hollandite. Furthermore, the enhanced corrosion of SS316 by the corrosion products of hollandite is quantitatively explained using a classical crevice corrosion model.

36 MATERIALS SCIENCE↗

Application of the immobilized low-activity waste glass corrosion model to the static dissolution of 24 statistically-designed alkali-borosilicate waste glasses

Glass corrosion models that capture the complex mechanisms of the glass-water reaction enable the prediction of nuclear waste glass durability in disposal scenarios. Parameterization of such models is challenging because of the need to capture changes in corrosion behavior with time, reaction conditions, and glass composition. In this report we describe and employ the immobilized low activity waste (ILAW) glass corrosion model (IGCM) in geochemical simulations of static dissolution tests, at two temperatures (40 °C and 90 °C), for a matrix of 24 enhanced low activity waste (eLAW) glasses statistically designed to cover a processable composition space defined by 8 major glass components (Al 2 O 3 , B 2 O 3 , CaO, Na 2 O, SiO 2 , SnO 2 , ZrO 2 , and Others as defined in the text). The IGCM includes a first-order chemical affinity term and an ion-exchange term that represents the net exchange of Na+ ions in the pristine glass with protons in aqueous solution. Constant, time-dependent, and time- and pH-dependent functional forms of the ion-exchange term are evaluated to reproduce the change in corrosion behavior with time in saturated, static dissolution tests. The agreement with measured aqueous concentrations of the main glass components (B, Na, and Si) improved significantly upon addition of a time-dependent term, which therefore constitutes a simple representation of the glass-water reaction progress. Due to the limited changes in pH in the static dissolution tests, past a short initial period of rapid increase, addition of a pH dependent term did not appreciably improve the fits, indicating that comprehensive model parameterization requires more than one type of glass corrosion test to capture a wide range of solution chemistries. IGCM parameters were found to be dependent on glass composition, and the parameter sets generated in this work will enable the development of composition–parameter correlation models that offer the promise of predicting IGCM parameters, and thus glass corrosion behavior, solely based on glass composition.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Molten chloride salts for next generation CSP plants: Electrolytical salt purification for reducing corrosive impurity level

In this study, electrolysis with a Mg anode is presented to purify the molten chloride salt (MgCl 2 /KCl/NaCl 60/20/20 mol.%) for reducing its corrosivity. Using a Mg anode, the production of toxic gases like Cl 2 on an inert anode (e.g., tungsten) can be avoided. Moreover, compared to an inert anode, a lower over-potential is required to remove the corrosive impurity MgOH + in the molten salt due to the high reactivity of Mg. In order to evaluate the effect of the salt purification, the cyclic voltammetry (CV) method developed in our previous work is used to in-situ measure the concentration of the corrosive MgOH + impurity in the molten salt. The CV measurements indicate that the corrosive impurity is efficiently removed by electrolysis. For decreasing the cathode inactivation due to produced MgO on the surface, a pulsed potential applied on the tungsten cathode during electrolysis shows to be promising. This electrochemical salt purification method has shown to be promising by efficiently controlling the corrosivity of the molten chloride salt. The potentiodynamic polarization (PDP) measurements on a commercial high-temperature alloy (Incoloy 800 H) immersed in the molten salt indicate that the corrosion rate of the alloy is significantly reduced due to the salt purification. It could also lead to a reduction of the cost of the conventional salt purification step, structural container materials, and piping in next generation concentrated solar power (Gen3 CSP) plants.

14 SOLAR ENERGY↗

Assessment of dissimilar metal corrosion in molten chloride salt

Dissimilar metal corrosion between high nickel alloys and stainless steel was tested in purified molten chloride salt. Preliminary results have shown that corrosion rates are significantly affected for samples both when electrically connected and isolated. Suggesting that galvanic corrosion as well as non-galvanic dissimilar metal corrosion play a role in corrosion processes for multi component systems. Finally, these results suggest that even if efforts to prevent electrical contact are taken, close proximity of structural materials can still change corrosion rates in molten salt environments.

14 SOLAR ENERGY↗

Genesis of Nanogalvanic Corrosion Revealed in Pearlitic Steel

Nanoscale, localized corrosion underpins billions of dollars in damage and material costs each year; however, the processes responsible have remained elusive due to the complexity of studying degradative material behavior at nanoscale liquid–solid interfaces. Recent improvements to liquid cell scanning/transmission electron microscopy and associated techniques enable this first look at the nanogalvanic corrosion processes underlying this widespread damage. Nanogalvanic corrosion is observed to initiate at the near-surface ferrite/cementite phase interfaces that typify carbon steel. In minutes, the corrosion front delves deeper into the material, claiming a thin layer of ferrite around all exposed phase boundaries before progressing laterally, converting the ferrite to corrosion product normal to each buried cementite grain. Over the following few minutes, the corrosion product that lines each cementite grain undergoes a volumetric expansion, creating a lateral wedging force that mechanically ejects the cementite grains from their grooves and leaves behind percolation channels into the steel substructure.

36 MATERIALS SCIENCE↗

From Micro-environments to Macroscopic Effects: How the Alkaline Hydrogen Evolution Reaction Drives Cu Cathodic Corrosion

Cathodic corrosion of copper (Cu) has posed a significant challenge for over a century, impeding various technological progresses such as electrochemical conversion of CO 2 (eCO 2 RR) into fuels and other value-added carbon products. Here, in this study, employing a combined Density Functional Theory (DFT) and kinetic Monte Carlo (kMC) simulation approach, we delve into the atomistic level mechanism driving this phenomenon in Cu. Our hypothesis posits the pivotal role of alkaline hydrogen evolution reaction (HER) in facilitating cathodic corrosion in Cu. We rigorously develop a pH-dependent hydroxide (OH) adsorption mechanism and calculate the equilibrium OH coverage (𝜃 OH ) at varying pH levels, the thermodynamic stability of subsurface oxygen (O sub ), as well as the Cu-vacancy mediated diffusion of subsurface oxygens (O sub ). Through comprehensive analysis, we establish correlation among various microenvironments, including oxygen diffusion in subsurface layers, pH-dependent OH adsorption, and Cu dissolution into the electrolyte as (Cu-OH) complexes. Furthermore, our investigation explores the correlation between surface coordination environment of active sites and cathodic corrosion of Cu. Finally, by integrating DFT-derived thermodynamic data into a kMC model, we successfully predict the formation of experimentally observed corrosion pits on Cu-surfaces. This combined approach not only advances our fundamental understanding of Cu cathodic corrosion but also offers insights crucial for developing effective corrosion mitigation strategies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of V Content on Corrosion Behavior of Al-V Alloys Produced by Mechanical Alloying and Subsequent Spark Plasma Sintering

Al-V alloys produced via high-energy ball milling have been reported to show simultaneous improvement of corrosion resistance and mechanical properties compared to traditional Al alloys. In these alloys, V content plays a crucial role in increasing or decreasing the corrosion resistance. Therefore, the effect of V and microstructure on corrosion of high-energy ball milled and subsequently spark plasma sintered Al-xV alloys (x = 2, 5, 10 at%) has been studied. Cyclic potentiodynamic polarization tests and electrochemical impedance spectroscopic analysis revealed the increment of V content up to 5 at% enhanced the corrosion resistance of the alloy. However, highly heterogeneous microstructure in Al-10 at%V resulted in significant localized corrosion over the immersion time. The electrochemical impedance spectroscopy studies over 14 days of immersion revealed underlying corrosion mechanisms.

36 MATERIALS SCIENCE↗

Investigation of Corrosion of 304 Stainless, Inconel 625, and Haynes 230 in a Chloride-Salt-Based Thermal Storage Medium

One of the critical challenges for latent heat thermal energy storage systems in concentrating solar power applications is corrosion of metallic alloys as containment and heat transfer fluid tube materials in corrosive salts at high temperatures. In this study, the effects of MgCl 2 on the corrosion of stainless steel 304, Inconel 625, and Haynes 230 alloys were investigated through embedded metal samples in the graphite foam/MgCl 2 storage medium. Four experimental testing modules were fabricated, and experimental tests were conducted under controlled environment by heating the testing modules to and keeping them at 750 °C for 100, 200, 500, and 1000 h. The estimated corrosion rates based on the weight losses for stainless steel 304, Inconel 625, and Haynes 230 were 94, 9, and 8 μm/year, respectively. The fitted equations for the loss of the thickness as functions of the exposure time show that the corrosion rates decrease with the exposure time. Additionally, the results on the corrosion zones or depths and chromium segregation ranges of the experimental samples are also presented.

36 MATERIALS SCIENCE↗

Corrosion Response of Ni-19Cr-5Fe in Molten NaCl-MgCl 2 Salt

Ni-based alloys are strong candidates for use in high-temperature molten salt reactors due to their superior corrosion resistance and mechanical stability compared to stainless steels. In this study, the static corrosion behavior of a Ni-19Cr-5Fe model alloy was systematically evaluated in a purified molten NaCl-MgCl 2 salt at 700°C for 30, 240, and 500 h. Post-exposure analyses were conducted to assess microstructural evolution, corrosion depth, and elemental depletion profiles. Corrosion rates, quantified by chromium depletion depth, followed an inverse power-law trend with increasing exposure time, indicating diffusion-limited kinetics. This trend is attributed to limitations in mass transport in the static salt and to the progressive local depletion of reactive chromium species. Coupled electron backscatter diffraction and energy dispersive X-ray spectroscopy analysis further revealed that the grain boundary character significantly influences corrosion susceptibility: high-angle grain boundaries exhibited pronounced Cr depletion and pitting, while low-angle and Σ3 boundaries remained comparatively resistant. These results offer valuable insight into the role of microstructure in corrosion processes and reinforce the importance of time-dependent material evaluation in molten salt environments relevant to advanced reactor designs.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Open-air plasma-assisted deposition of organosilicon coating for corrosion protection of AZ91D Mg alloy

As a corrosion barrier layer, open-air plasma-assisted organosilicon coating was applied on AZ91D Mg alloy. Organosilicon-coated AZ91D samples, prepared from two different plasma coating processes, were used for corrosion evaluation based on multistep electrochemical and H 2 collection measurements in 3.5 wt% sodium chloride (NaCl) solution. Some coated AZ91D samples were characterized with and without corrosion exposure in NaCl solution using electron microscopies and X-ray chemical analysis techniques. Further, the results indicate that the organosilicon coatings from open-air plasma processes are effective to delay the initiation of corrosion attack and also reduce the corrosion rate for AZ91D substrate. The corrosion attack was considered to develop after permeation of NaCl solution through the coating layer.

36 MATERIALS SCIENCE↗

Origins of wear-induced tungsten corrosion defects in semiconductor manufacturing during tungsten chemical mechanical polishing

During chemical mechanical polishing (CMP) process optimization, a unique corrosion defect was identified in the tungsten (W) contact plugs, which were investigated to develop practical solutions to improve CMP mass productivity. The corrosion defect occurred in the absence of external incident energy and was observed to occur only at the W plugs connected to the P + /n-well close to the wafer edge. To examine the root cause of the corrosion, a series of experiments was carried out at each W CMP step, using in-line defect inspection. Additional experiments were conducted using on-line inductively coupled plasma mass spectrometry (ICP-MS) to understand pH- and potential-dependent electrochemical dissolution behaviors of W. Experimentally, W corrosion was confirmed to be exacerbated if the surface oxide of the W plugs is removed by the deionized water (DIW) rinsing step under wafer pressurization, then exposed to DIW and alkaline cleaning solution. Although the DIW rinsing step is commonly performed to clean polishing pads right after the main polishing, a small amount of applied pressure (0.5 psi) without slurry supply can lead to corrosion defects. Finally, this wear-induced corrosion of the W plugs can be prevented by removing the applied pressure during the post DIW rinsing step of W CMP.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Approaches to investigate the role of chelation in the corrosivity of biomass-derived oils

The need to provide the U.S. market with a renewable liquid fuel energy source from a non-food feedstock stream has gained considerable traction due to benefits such as improved energy efficiency, reduced environmental impacts, and enhanced national security. Practical achievement of these goals via biomass and bio-waste utilization involves production of liquid intermediates containing corrosive, reactive species like carboxylic acids, ketones, aldehydes, and hydroxyaldehydes. Such mixtures challenge materials of containment, processing, and transport. It is widely recognized that the smaller organic acids, such as acetic and formic, are corrosive and can remove protective surface oxides on alloys used in bio-oil processing infrastructure, and ketones can swell sealing polymers. However, literature shows, and findings herein confirm, larger carboxylic acids and bidentate alcohols are present. This highlights the potential for synergistic, detrimental effects of constituents in bio-oil corrosion, including direct reactivity of small acids compounded with the possibility of mobilization of protective metal oxide layers via chelation by larger acids and oxygenates. The question of whether species beyond small acids can significantly contribute to corrosion requires analytical approaches previously not applied to bio-oil corrosion studies and certainly not previously applied corroboratively. As such, this work introduces a combination of optical, mass spectral, and electrochemical impedance spectroscopies with an incubation approach to study metal mobilization, to facilitate elucidating chelation's role in bio-oil corrosive pathways. To enable systematic study of these oxygenates' material compatibility individually and in combination, a model matrix of bio-oil constituents was also developed based on identification of key components of real bio-oils.

09 BIOMASS FUELS↗