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At least 343 records · Page 19

Corrosion Engineering: Challenges in a Spaceport Environment

The overarching theme of this internship at NASA's Kennedy Space Center (KSC) was corrosion engineering and control, a subset of materials engineering located under the NE-L4 branch. KSC, as a costal launch facility, is subjected to incredibly corrosive conditions in the form of high salt content from the nearby ocean, high temperatures and humidity, and frequent storms. As such, corrosion control is a vital part of operations here at KSC. To tackle these issues, this internship focused on three main projects; creating a corrosion control database, revamping KSC's Corrosion Lab website, and running corrosion studies in the lab and in the field.

MacWatters, Matthew↗

Corrosion evaluation of metal foams in eutectic molten salts for high temperature latent heat energy storage application

High-temperature Thermal Energy Storage (TES) has drawn great attention as a technology that can increase the role and profitability of micro nuclear reactors in the decentralized clean energy market. Various research needs have been proposed by Idaho National Laboratory (INL) in "the Integrated Energy Systems: 2020 Roadmap" with the goal of utilizing the high temperature of 550 degrees or more generated in the 4th generation reactor to industrial purposes from the standpoint of integrated energy systems [1]. With the recent development of the 4th generation nuclear power plant, including micro nuclear reactor, there is a great deal of interest in researching how to efficiently couple a heat source to an industrial process through thermal processing. Texas A&M University (TAMU) and INL are currently collaborating to develop a novel latent heat storage design called HITB (Heat pipe-Integrated Thermal Battery). As part of the small-scale experimental demonstration research for HITB, a study for storage medium selection was conducted at TAMU. Eutectic salts have attracted interest as high-temperature heat storage medium for HITB. Especially, chloride molten salts and fluoride molten salts are considered promising candidates due to their high melting temperature, thermal stability, and high latent heat of fusion. Since eutectic salts have poor thermal conductivity in general, it is critical to distribute materials with high thermal conductivity evenly to facilitate the charging and discharging of heat. In this study, metal foam was considered in the HITB system to overcome the poor heat transfer characteristics of eutectic salts. In order to improve heat transfer, it is necessary to study materials with high thermal conductivity, corrosion resistant to molten salts, such as fins, extended surfaces, particles, microcapsulation, or foam structure. Porous structure of copper or aluminum can increase heat transfer area, form a thermal transfer network, and increase the effective thermal conductivity of thermal storage medium [2]. Since the melting temperature is required to be at least 450? in the current HITB design, various eutectic salts are being considered. FLiNaK and FLiBe, which are famous for fluoride salts, are good candidates, but due to the sharp rise in the price of LiF recently, they are excluded for economic reasons to be applied to large-capacity thermal energy storage. On the other hand, chloride salts are very cheap and easy to obtain, have a high melting temperature, and have a high latent heat of fusion, so they are recently in the spotlight as a phase change material. However, because of the hygroscopic nature of chloride salts, HCl gas due to impurity is easy to be released and is particularly vulnerable to corrosion. Chloride eutectic salts have been tested and suggested for metal alloys that are particularly resistant to corrosion, such as SS304, SS316, Hastelloy, Inconel 625, Incoloy 800H, which has low thermal conductivity, and is very expensive [3-6]. Porous materials with high thermal conductivity such as copper and aluminum have been tested for stability in fluids such as paraffin or water as metal foam or metal fin structures, but high temperature corrosion tests were not performed on various eutectic salts yet. Therefore, this study investigated the high temperature corrosion characteristics of metal alloys, such as C10100 foam, C10100 plate, 6101 alloy foam, and SS316 plate, while immersed in the candidate eutectic salts. A total of 20 tests for SS316 coupons and 10 tests for C10100 coupons were performed to ensure the repeatability of the present measurements. Since it is difficult to completely remove the salt inside metal foam due to the complex inner structure of the metal foam, only the surface condition was observed with a microscopy and scanning electron microscopy (SEM) image, except for measuring the corrosion rate and average mass loss.

25 ENERGY STORAGE↗

Effect of Minor Ce Additions on Corrosion Behavior of Experimental Pipeline Steel

Minor additions of rare earth elements (REEs) have been shown to improve various steel properties. In particular, Cerium (Ce), as a relatively abundant and inexpensive element, has received attention as a potentially beneficial minor alloying addition for a variety of steel applications, including pipelines materials. The objective of this work is to investigate the effect of Ce on corrosion performance of experimental high-strength pipeline steel. Electrochemical corrosion experiments were carried out on steel without and with 0.006, 0.018, and 0.03 wt.% of Ce in 3.5 wt.% NaCl saturated with CO2 at 20 oC. For comparison purposes, X100 carbon steel specimens machined from an experimental pipe with a yield strength of 731 MPa were tested under the same conditions. The electrochemical techniques employed included: potentiodynamic polarization (PDP), linear polarization resistance (LPR), and electrochemical impedance spectroscopy (EIS). In addition, post-corrosion surface characterization was performed using scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectroscopy (EDS), while crystalline phases were determined by X-ray diffraction (XRD). The corrosion of base metal without Ce was lower (0.15 mm/y) compared to carbon steel X100 (0.9 mm/yr). The electrochemical results showed that adding Ce accelerates corrosion rates compared to base metal without Ce. No pitting corrosion of tested steel was detected.

Belarbi, Zineb↗

Effectiveness of Vapor Corrosion Inhibitors Under Elevated Chloride Conditions for Aboveground Storage Tank Application

The sand quality used to construct the tank pad is an important contributing factor to the rate of corrosion that occurs on the soil-side of the aboveground storage tanks (ASTs) floor plates. Clean sand that meets specific criteria provides the first line of defense for mitigation of tank floor corrosion. However, it has been observed that the sand quality used for some existing tanks differ greatly from the specifications provided in the API 651 standard; this could be partially due to initial sand quality not meeting the specification, and partially due to the environmental effects over time. For example, rain-water intrusion could lead to higher than the specified contents of corrosive species such as chloride. Tank operators are increasingly using vapor corrosion inhibitors (VCIs) either as a stand alone or in combination with cathodic protection (CP) for ASTs to mitigate soil-side corrosion. VCIs are delivered either through-thefloor or injected through the ports in the ring wall. Experimental studies were conducted to evaluate VCIs’ performance at elevated chloride concentrations and to study the effectiveness of the delivery methods under extreme chloride conditions. The experimental work found that VCI performance is robust and not compromised due to high chloride levels, such as 300 ppm or more. The work also showed that the through-the-floor VCI delivery method is more beneficial compared to the through-the-sand-pad method when tank pad corrosivity is elevated.

Shukla, Pavan K.↗

Effectiveness of Vapor Corrosion Inhibitors Under Bacterial Activity for Aboveground Storage Tank Application

Bacterial activity is known to influence corrosion and can result in increasing soil-side corrosion of the aboveground storage tanks (ASTs) floor plates. Association for Materials Protection and Performance (AMPP) defines this phenomenon as Microbiologically Influenced Corrosion (MIC). It has been hypothesized that vapor corrosion inhibitors (VCIs) can not only function in presence of bacterial activity but can also function as biocides. Experiments were conducted to study the effect of bacterial activity on corrosion in the sand pad conditions and effect of VCIs in mitigating MIC. Various bacteria cultures were grown using commercially available culture media, and coupon exposure tests were performed with field sand mixed with the culture media. To this end, control and VCI-dosed electrolytes were prepared using the field sand plus bacteria cultures. Pre- and post-test bacteria concentration estimation and measurements, respectively, in the VCI-dosed electrolytes indicated that VCIs do not function as biocides, however, VCIs are highly effective for mitigating corrosion in presence of bacterial activity.

Shukla, Pavan K.↗

Time-Dependent Corrosion Behavior of Aluminum Using Advanced Electrochemical and Characterization Techniques

The time-dependent corrosion behavior of pure aluminum (Al) in a chloride-containing environment was investigated using various electrochemical and characterization techniques for up to 336 h. Transmission electron microscopic and secondary ion mass spectroscopic analysis revealed the continuous dissolution of the surface film over the immersion time. In the meantime, the increasing passive oxide thickness resulted in the surface film resistance enhancement over the immersion time, as indicated by the electrochemical impedance spectroscopic analysis. The electrochemical noise measurements showed an increase in the corrosion kinetics with immersion time until 60 h because of the accelerated localized corrosion in the early stage of immersion. However, an inhibition in corrosion kinetics occurred after longer immersion times due to corrosion product deposition inside the pit.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Corrosivity Screening of Pyrolysis Bio-Oils by Short-Term Alloy Exposures. Laboratory Analytical Procedure (LAP), Issue Date: May 12, 2022

Bio-oils contain organic acids and oxygenated compounds that can lead to corrosion issues during bio-oil processing and storage. This Laboratory Analytical Procedure (LAP) allows for rapid screening of a bio-oil's corrosivity without the need for complex equipment and long-term exposures. A robust and repeatable method for assessing the corrosivity of bio-oils is necessary in order to remove materials degradation as an obstacle to research, upgrading, use and storage of bio-oils. This LAP involves the incubation of a representative alloy, 410 stainless steel (410 SS), specimen in bio-oil over a period of 48 hours at 50 degrees C in a sealed container. The corrosive species in the bio-oil react with and deplete alloy elements such as iron (Fe) and/or chromium (Cr) from the specimen into the bio-oil solution. The depletion of Fe and Cr from the specimen results in a significant mass loss that can be recorded. The mass loss is directly correlated to the corrosivity of a bio-oil. Examples of bio-oils in scope include the ones produced by fast pyrolysis and catalytic fast pyrolysis, as well as liquids produced from hydrothermal liquefaction.

09 BIOMASS FUELS↗

Effect of Carboxylic Acids on Corrosion of Type 410 Stainless Steel in Pyrolysis Bio-Oil

Biomass-derived oils are renewable fuel sources and commodity products and are proposed to partially or entirely replace fossil fuels in sectors generally considered difficult to decarbonize such as aviation and maritime propulsion. Bio-oils contain a range of organic compounds with varying functional groups which can lead to polarity-driven phase separation and corrosion of containment materials during processing and storage. Polar compounds, such as organic acids and other oxygenates, are abundant in bio-oils and are considered corrosive to structural alloys, particularly to those with a low-Cr content. To study the corrosion effects of small carboxylic acids present in pyrolysis bio-oils, type 410 stainless steel (SS410) specimens were exposed in bio-oils with varying formic, acetic, propionic and hexanoic acid contents at 50 °C during 48 h exposures. The specific mass change data show a linear increase in mass loss with increasing formic acid concentration. Interestingly, a mild corrosion inhibition effect on the corrosion of SS410 specimens was observed with the addition of acetic, propionic and hexanoic acids in the bio-oil.

09 BIOMASS FUELS↗

Laser Surface Processing of Alloys for Corrosion Protection (Final Project Report of Marine Energy Seedling Project)

This is the final project report for the MHK Seedling project. The report describes use of laser surface processing (LSP) to modify the surface of test materials (Al, steel) and the corrosion testing performed on the resulting samples in different corrosion environments. Data shows that LSP improved the corrosion resistance of Al and steel used in this work relative to respective non-LSP samples. The data also showed that each material had a specific range of laser processing conditions where the beneficial effects of LSP (i.e. improvement in corrosion protection) were observed. Application of LSP to enable low-cost materials in marine environments, additional microstructural analysis and long-term testing are proposed to further develop this technology for marine renewable energy and systems.

36 MATERIALS SCIENCE↗

Variation of the Passive Film on Compositionally Concentrated Dual-Phase Al 0.3 Cr 0.5 Fe 2 Mn 0.25 Mo 0.15 Ni 1.5 Ti 0.3 and Implications for Corrosion

The passive film on a dual-phase Al 0.3 Cr 0.5 Fe 2 Mn 0.25 Mo 0.15 Ni 1.5 Ti 0.3 FCC + Heusler (L2 1 ) compositionally concentrated alloy formed during extended exposure to an applied potential in the passive range in dilute chloride solution was characterized. Each phase, with its own distinct composition of passivating elements, formed unique passive films separated by a heterophase interface. High-resolution, surface sensitive characterization enabled chemical analysis of the passive film formed over individual phases. The film formed over the L2 1 phase had a higher concentration of Al, Ni, and Ti, while the film formed over FCC phase was of similar thickness but contained comparatively higher Cr, Fe, and Mo concentrations, consistent with the differences in bulk microstructure composition. The passive film was continuous across phase boundaries and the distribution of passivating elements (Al, Cr, and Ti) indicated both phases were independently passivated. Spatially resolved analysis of the surface chemistry of the dual-phase CCA revealed that the cation with the highest composition in passive film formed on the FCC phase was Cr (52.4 at. pct) and for the L2 1 phase was Ti (53.1 at. pct) despite the bulk concentration of each element being below 20 at. pct in their respective phases. Al, Cr, and Ti were enriched in both phases within the passive film relative to their respective bulk compositions. In parallel studies, single-phase alloys with compositions representative of the FCC and L2 1 phases were synthesized to evaluate the corrosion behavior of each phase in isolation. The corrosion behavior of the dual-phase alloy showed passivity evidenced by a pitting potential of 0.615 V SCE in 0.01 M NaCl. The pitting potential and other electrochemical parameters suggested a combination of behaviors of both single-phase samples, suggesting that the global corrosion behavior may be represented by a composite theory applied to phases, their area fractions, and interphase length. However, the interphase in the dual-phase CCA was a local corrosion initiation site and may limit localized corrosion protectiveness. The alloy design implications for optimization of second phase structure and morphology are discussed.

36 MATERIALS SCIENCE↗

Mechanistic modeling of copper corrosions in data center environments

Air-side economizers are increasingly used to take advantage of “free-cooling” in data centers with the intent of reducing the carbon footprint of buildings. However, they can introduce outdoor pollutants to indoor environment of data centers and cause corrosion damage to the information technology equipment. Here, to evaluate the reliability of information technology equipment under various thermal and air-pollution conditions, a mechanistic model based on multi-ion transport and chemical reactions was developed. The model was used to predict Cu corrosion caused by Cl2-containing pollutant mixtures. It also accounted for the effects of temperature (25 °C and 28 °C), relative humidity (50%, 75%, and 95%), and synergism. It also identified higher air temperature as a corrosion barrier and higher relative humidity as a corrosion accelerator, which agreed well with the experimental results. The average root mean square error of the prediction was 13.7 Å. The model can be used to evaluate the thermal guideline for data centers design and operation when Cl2 is present based on pre-established acceptable risk of corrosion in data centers’ environment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Localized corrosion at nm-scale hardening precipitates in Al-Cu-Li alloys

The localized corrosion of Li-containing nm hardening precipitates in the 3rd generation of Al-Cu-Li alloys was investigated based on a quasi in situ approach by sequentially exposing the material to NaCl solution and characterizing the structural, chemical, and electrochemical evolution at atomic scale using electron microscopy, spectroscopy, 3D tomography, electrochemical measurements, and DFT calculations. Localized corrosion of Al 7.5 Cu 4 Li (TB phase) initiated along {001} family of planes through the dealloying of Al and Li due to a low surface work function. Cu was enriched along the Cu (110) // T B (011) // Al (100) orientations on and around corroded T B precipitates. No strong galvanic interactions were observed at the T B and Al matrix interface due to the formation of a Li-C-O rich passivation layer during electrolyte exposure. Similarities and differences between T B and other common Al-Cu-Li precipitates (Al 2 CuLi, Al 6 CuLi 3 , and Al 3 Li) with respect to corrosion are discussed. Overall, the reported corrosion mechanism can assist in the assessment of the localized corrosion susceptibility of precipitation-hardened Al alloys and assist in the design of new alloys.

36 MATERIALS SCIENCE↗

Cathodic corrosion: 21st century insights into a 19th century phenomenon

Cathodic corrosion is an enigmatic electrochemical process that etches metallic electrodes at potentials below 0 V versus the normal hydrogen electrode. Although this phenomenon was discovered in the late 1800s by Fritz Haber, it remained mostly unnoticed during the 20th century and only attracted increased attention in the past decade. This recent attention has generated marked improvements in both the fundamental knowledge and the applications of cathodic corrosion. Fundamental new insights were gained into the effects and possible reaction intermediates of cathodic corrosion. Complementing these insights, recent advances involve applications of cathodic corrosion for nanoparticle synthesis and electrocatalyst modification. Both these applied and fundamental advances will be discussed in this short review on cathodic corrosion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of substrate orientation and anisotropic strength on corrosion pits

The complexities of pitting corrosion and its associated pit morphologies are critical for predicting and preventing pit-related failure in materials. With the advances in computational tools, modeling of pitting corrosion has lately gained momentum. We recently developed a phase field model for 3-D pit morphology, and in the current work, the model is utilized to gain insight into the role of substrate orientation and anisotropic strength on crystallographic pits. The influence of these parameters on pit morphology and corrosion metrics such as pit volume, current, pit area, current density, and pit depth are studied. The crystallographic pit morphology changes with substrate orientation but not significantly with anisotropic strength. Finally, the anisotropic strength strongly influences the corrosion metrics whereas most corrosion metrics remain unaffected by substrate orientation.

36 MATERIALS SCIENCE↗

Corrosion mechanism of cold forged 316 stainless steel in molten FLiNaK salt

This study examined how cold forging (CF) affects the corrosion of 316 stainless steel (SS) in molten FLiNaK salt at 700 °C for 48 h. CF samples had two corrosion areas: one near the top and another displaying intergranular corrosion (IGC). Samples with lower CF (5–30 %) showed more IGC, while the 50 % CF sample had less IGC but the shallowest corrosion depth. This was due to the increased number of grain boundaries, which raised the potential corrosion initiation sites, and certain grain boundaries promoting chromium dissolution, thus enhancing IGC.

FLiNaK↗

Effect of MgSO 4 addition on alkali sulphates induced hot corrosion of a β-NiAl coating

The effect of MgSO 4 addition on alkali sulphates induced hot corrosion of a β-NiAl coating was studied by performing a series of tests with deposits of Na 2 SO 4 , Na 2 SO 4 -20 %K 2 SO 4 and Na 2 SO 4 -12 %K 2 SO 4 -35 %MgSO 4 (mol.% for all) at 700 °C in air with addition of SO 2 . For elucidating the observed corrosion phenomena, various salt-oxide/NiAl powder mixtures were exposed to the same hot corrosion test conditions. Two pseudo-binary phase diagrams of the Na, K, Mg-sulphate systems were calculated using an in-house developed thermodynamic database. Addition of MgSO 4 to Na 2 SO 4 -20 %K 2 SO 4 deposit salt inhibited the hot corrosion attack during 24 h exposure, which is related to consumption of aggressive K 2 SO 4 by the formation of solid K 2 Mg 2 (SO 4 ) 3 . However, extending the exposure with Na 2 SO 4 -12 %K 2 SO 4 -35 %MgSO 4 deposit to 100 h resulted in severe corrosion attack. The latter observation is explained by a reaction between K 2 Mg 2 (SO 4 ) 3 and NiAl causing formation of a Mg, Ni and Al containing spinel accompanied by release of the aggressive K 2 SO 4 into the liquid phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Corrosion behavior of ferritic FeCrAl alloys in simulated BWR normal water chemistry

Ferritic iron-chromium-aluminum (FeCrAl) alloys with varying Cr content were subjected to in-situ irradiation-corrosion with energetic protons or electron beams in pure water with various oxygen concentrations. Oxide microstructure and composition were characterized to compare the corrosion under irradiation with the thermal corrosion in the same water conditions. The dominant effect seems to be the production of H 2 O 2 at the surface by the intense proton and electron beams. The corrosion potential of FeCrAl under BWR-NWC condition is somewhat above the Cr 2 O 3 /CrO 4 2- phase boundary, oxidizing the Cr(III) to Cr(VI) in the outer part of the film, but with some Cr(III) remaining in the interior of the oxide. The beam increases the corrosion potential, significantly reducing Cr(III) content throughout the oxide. Finally, the crystallites on the surface, which form by re-precipitation from solution, do not contain Cr because at low potential Cr(III) is not soluble, and at high potential Cr(VI) is quite soluble.

36 MATERIALS SCIENCE↗

Investigation of breakaway corrosion observed during oxide growth in pure and low alloying element content Zr exposed in water at 360°C

The addition of small concentrations of alloying elements to pure zirconium can prevent nuclear fuel cladding material from undergoing unstable oxide growth in aqueous environments at light water reactor operating temperatures. The role of alloying elements in stabilizing the oxide growth is examined in this paper, to better understand the oxide growth stabilization mechanism. To this end, a set of initial, short-duration corrosion experiments were performed, followed by oxide layer characterization. Specifically, ten model Zr alloys were selected to test the effect of small alloying additions on the alloy corrosion rate and corrosion breakaway. Additionally, these alloys were corrosion tested in pure water in an autoclave at 360°C for up to 70 days. The alloys included crystal bar Zr, sponge Zr, and model alloys with small concentrations of Sn, Fe, and Cr. After testing, the alloys were characterized using scanning electron microscopy (SEM) and synchrotron µ-X-ray fluorescence (µXRF) to study how the structure of the oxide and alloying element distribution related to unstable oxide growth. Initial results in the 360°C water environment showed breakaway oxidation may be caused by unstable oxide growth due to heterogeneous distribution of the alloying elements. Heterogeneous distribution of alloying elements was correlated to the occurrence of unstable oxide growth (either nodule-like, grain boundary penetration, or differential grain-to-grain growth). It is possible that this heterogeneity, made possible by low alloying element content, can cause breakaway corrosion, but further study is warranted.

36 MATERIALS SCIENCE↗