Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “CORROSIVE”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 523 records · Page 29

Fractal coatings of Ni and NiYSZ for high-temperature corrosion mitigation in solar salt

This paper introduces a novel approach to corrosion mitigation using electrodeposited, fractal Ni and NiYSZ coatings. Highly adherent, durable multiscale coatings with fractal dimensions above 1.80 were fabricated. Corrosion characteristics of coated plain and etched surfaces of In800H, SS310, SS316 and SS347, in comparison to Ha230, were studied in molten 60% NaNO 3 + 40% KNO 3 at 600 °C. The corrosion rate of coated Fe-based alloys reduced by up to 68% compared to uncoated alloys and was on par with or lower than the corrosion rate of Ha230. Furthermore, the corrosion-resistant coatings provide for use of low-cost alloys in high temperature corrosive environments.

36 MATERIALS SCIENCE↗

Discovering the nanoscale origins of localized corrosion in additive manufactured stainless steel 316L by liquid cell transmission electron microscopy

Here, we use liquid cell scanning transmission electron microscopy (STEM) to directly characterize the nanoscale origins of corrosion initiation in Additive manufacturing (AM) 316 L stainless steel. Under applied anodic potentials, we found that the dislocation cellular boundaries were preferentially corroded and that regions of localize corrosion occurred along the cellular boundaries. We directly observed the earliest stages of corrosion by controlling the biasing parameters to decelerate the corrosion processes. The results show that highly localized corrosion occurs via inclusion dissolution along dislocation cell boundaries. More widespread corrosion initiates at the dislocation cell boundaries and spreads throughout the dislocation networks.

36 MATERIALS SCIENCE↗

Mechanistic transition of stainless steel 304L corrosion in MgCl 2 phase change material under thermal cycling

Magnesium chloride (MgCl 2 )-based molten salt phase change materials (PCMs) are promising candidates for thermal energy storage (TES) owing to their advantageous thermophysical properties, however, their high corrosivity in the molten state limits material compatibility. In this study, the corrosion behavior of 304?L stainless steel (SS304L) exposed to MgCl2 PCM was investigated as a function of thermal cycling (up to 9000 cycles) relevant to PCM-based TES systems. Microstructural changes and elemental redistribution at the alloy-salt interface under thermal cycling conditions were characterized using synchrotron-based X-ray fluorescence (XRF) and scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDS). Results show that corrosion is governed by selective Cr-dissolution and elemental diffusion near the interface and grain boundaries. A clear transition in the dominant corrosion mechanism is observed with increasing thermal cycles. Surface corrosion is the dominant mechanism up to 1000 cycles, whereas intergranular corrosion becomes the primary degradation mode beyond 2000 cycles. These mechanistic changes are interpreted in terms of evolving interfacial chemistry, microstructure and the diffusion-driven redistribution of alloying elements.

36 MATERIALS SCIENCE↗

Microbeam synchrotron radiation diffraction and fluorescence of oxide layers formed on zirconium alloys at different corrosion temperatures

Autoclave corrosion tests of Zircaloy-4 were performed at temperatures ranging from 274°C to 427 °C to determine how the characteristics of the oxide layer changed with corrosion temperature. Corroded samples were prepared in cross-section and examined at the Advanced Photon Source using x-ray diffraction and fluorescence with sub-micron spatial resolution. These measurements provide high fidelity data for characterization of the oxide layer grown on zirconium alloys over a range of temperatures to better understand the fundamental mechanisms of corrosion. It was found that the size of the monoclinic oxide grains increases with distance from the metal-oxide interface, while the average grain size of the tetragonal oxide phase decreases. This is consistent with the continuous nucleation of a mixture of equiaxed tetragonal and monoclinic grains at the metal-oxide interface, of which only the monoclinic oxide grains that are properly aligned to minimize stresses grow into long columnar oxide grains. The tetragonal phase oxide grains transform to monoclinic oxide once a critical size is reached. While the monoclinic oxide grain size increases with corrosion temperature, the tetragonal phase grain size remains below a maximum value. Evolution of the tetragonal fraction, calculated with the Garvie-Nicholson formula, was observed, with local maxima seen just before transition and local minima seen at oxide locations corresponding to the oxide kinetic transition. No difference was observed in the tetragonal phase fraction in the oxide layers formed at different corrosion temperatures. Detailed fluorescence and diffraction mapping of one sample showed the evolution of the diffraction intensity over a short range in the oxide. In conclusion, this work provides a systematic study revealing fundamental characteristics of the microstructure of Zircaloy-4 oxide layers to further understanding of corrosion resistance of these materials.

36 MATERIALS SCIENCE↗

First steps toward predicting corrosion behavior of structural materials in molten salts

To address the need for physics-based models to predict corrosion behavior of materials in molten salts, here we propose potential methods to aid in selection of optimum materials for structural components in molten salt powered technologies. In the present work, the role of alloy thermodynamics and kinetics on governing corrosion rates of Ni-based alloys will be discussed combining experimental and computational methods. A few strategies are presented to quantify corrosion rates of Ni-based materials isothermally exposed in purified KCl-MgCl 2 salts at 600° C-800° C. The influence of capsule material, potential corrosion products and role of alloy composition on the observed corrosion rates was discussed with coupled thermodynamic-kinetic models. Larger depths of corrosion attack were observed in alloy 230 specimens compared to other alloys under similar conditions was attributed to the much higher chemical activity of Cr in the alloy that results in a larger Cr chemical potential gradient.

36 MATERIALS SCIENCE↗

Two new supramolecular metal diphosphonates: Synthesis, characterization, crystal structure and inhibiting effects on metallic corrosion

Two new divalent metal(II) aminodiphosphonates with layered structure, namely, Cu(H{sub 3}L{sup 1}){sub 2}·2H{sub 2}O (1), [H4L{sup 1}=methyl-N(CH{sub 2}PO{sub 3}H{sub 2}){sub 2}] and Cd{sub 2}(H{sub 2}L{sup 2}){sub 4}(2), [H{sub 4}L{sup 2}=n-propyl-N(CH{sub 2}PO{sub 3}H{sub 2}){sub 2}] were synthesized and characterized. The Cu(II) ions in complex 1 are octahedrally coordinated by four oxygen atoms from two chelating ligands and two phosphonate oxygen atoms from two neighboring Cu(H{sub 3}L{sup 1}){sub 2} units. The Cu(H{sub 3}L{sup 1}){sub 2} units are interconnected by bridging phosphonate groups, forming a 2-D metal phosphonate layer. The structure of complex 2 contains two unique Cd(II) ions octahedrally-coordinated by six phosphonate oxygen atoms from four H{sub 2}L{sup 2} diphosphonate anions. Corrosion inhibition performances of 1 and 2 were also compared with each other in order to study the effect of combinations of externally added Cd/H{sub 4}L{sup 2} and Cu/H{sub 4}L{sup 1} (1:1 ratio) on corrosion rates of carbon steel. It was found that at pH 3.0, Cd/H{sub 4}L{sup 2} or Cu/H{sub 4}L{sup 1} combinations do not have noticeable corrosion inhibition efficiency for carbon steel. In contrast, at pH 7.0, higher corrosion inhibition efficiency was achieved for Cd/H{sub 4}L{sup 2}. Physical characterizations such as scanning electron microscopy (SEM), Energy-dispersive X-ray spectroscopy (EDS) and Fourier transform infrared spectroscopy (FTIR) were applied to study the corrosion specimens and film material. - Graphical abstract: Two new metal phosphonates have been synthesized and characterized by single-crystal X-ray diffraction and thermogravimetric analysis. corrosion inhibition performances 1 and 2 are also compared.

36 MATERIALS SCIENCE↗

Influence of alloying element Zn on the microstructural, mechanical and corrosion properties of binary Mg-Zn alloys after severe plastic deformation

Highlights: • Mg-Zn alloys are processed by equal channel angular pressing with back-pressure. • The α-Mg matrix consists of highly deformed and partially recrystallized areas. • Zn concentration varies in the α-Mg matrix by up to 2 at.%. • The alloys exhibit mechanical anisotropy and a significant increase in strength. • Equal channel angular pressing increases corrosion rate of Mg-Zn alloys. - Abstract: This work presents an analysis of the microstructural, mechanical and corrosion properties of two binary Mg-Zn alloys. Mg-6 wt%Zn and Mg-12 wt%Zn cast alloys were subjected to annealing followed by quenching and processed via equal channel angular pressing with applied back-pressure (ECAP-BP). After ECAP-BP, both alloys were thoroughly examined and showed partially recrystallized and highly deformed areas. High-angle annular dark-field imaging revealed a difference in Zn content across the α-Mg matrix of the Mg-12 wt%Zn after ECAP-BP due to the growth of MgZn{sub 2} nanoparticles. Electron energy-loss spectroscopy (EELS) was carried out to qualify an average Zn content in these areas, and a variation in Zn content up to 2 at.% was found. Compression tests revealed mechanical anisotropy and a significant increase in the strength of both alloys after ECAP-BP. The yield strength, σ{sub 02}, was in the range from 269 to 385 MPa depending on the composition and compression axis. The initial state alloys showed yield strengths, σ{sub 02}, of only 75–150 MPa but improved ductility. The corrosion rates of the Mg-Zn alloys in the initial state, evaluated using a hydrogen evolution method in NaCl solution, were higher for Mg-12 wt%Zn. The corrosion rates of both alloys after ECAP-BP were higher than those of the initial state. Light microscopy observations did not reveal any preference for corrosion propagation, including transcrystalline, intercrystalline or interphase corrosion, in any of the materials.

36 MATERIALS SCIENCE↗

Corrosion of Ferrous Structural Alloys in Biomass Derived Fuels and Organic Acids

This work investigated the corrosivity of biomass-derived liquid fuels and organic acids associated with bio-oils and conducted a corrosion compatibility evaluation of several structural ferrous alloys in the fuels and acids. Here, the acidity parameters and solution conductivity values were higher in raw pyrolysis bio-oils than postprocessed oils with significant corrosion attack for carbon steel and Fe-2.25Cr-1Mo. However, higher-grade stainless steels, ferritic Fe-15Cr (15Cb) and austenitic types 304L and 316L, showed negligible corrosion loss, whereas lower-Cr ferritic grades 409, 410, and 416 were attacked. Metal leaching tests and electrochemical impedance spectroscopy measurements revealed superior corrosion resistance of 316 over 410 stainless steels in solutions of formic and oxalic acids that can be present in bio-oils. The corrosion evaluation methods utilized in this work provide effective screening tools to identify the compatible structural alloys for bio-oils.

09 BIOMASS FUELS↗

Use of Carbon Steel for Construction of Post-combustion CO 2 Capture Facilities: A Pilot-Scale Corrosion Study

Corrosion studies were carried out on metal coated and noncoated carbon steel as well as stainless steel in a pilot-scale post-combustion CO 2 capture process. Aqueous 30 wt % monoethanolamine (MEA) solvent was used without any chemical additive for antioxidation to examine a worst-case scenario where corrosion is not mitigated. The corrosion rate of all carbon steels was almost zero in the absorber column and CO 2 lean amine piping except for Ni-coated carbon steel (<1.8 mm/yr). Ni 2 Al 3 /Al 2 O 3 precoated carbon steels showed initial protection but lost their integrity in the stripping column and CO 2 rich amine piping, and severe corrosion was eventually observed for all carbon steels at these two locations. Stainless steel was found to be stable and corrosion resistant in all of the sampling locations throughout the experiment. This study provides an initial framework for the use of carbon steel as a potential construction material for process units with relatively mild operating conditions (temperature less than 80 °C), such as the absorber and CO 2 lean amine piping of a post-combustion CO 2 capture process. As a result, it also warrants further investigation of using carbon steel with more effective corrosion mitigation strategies for process units where harsh environments are expected (such as temperatures greater than 100 °C).

36 MATERIALS SCIENCE↗

One dimensional wormhole corrosion in metals

Corrosion is a ubiquitous failure mode of materials. Often, the progression of localized corrosion is accompanied by the evolution of porosity in materials previously reported to be either three-dimensional or two-dimensional. However, using new tools and analysis techniques, we have realized that a more localized form of corrosion, which we call 1D wormhole corrosion, has previously been miscategorized in some situations. Using electron tomography, we show multiple examples of this 1D and percolating morphology. To understand the origin of this mechanism in a Ni-Cr alloy corroded by molten salt, we combined energy-filtered four-dimensional scanning transmission electron microscopy and ab initio density functional theory calculations to develop a vacancy mapping method with nanometer-resolution, identifying a remarkably high vacancy concentration in the diffusion-induced grain boundary migration zone, up to 100 times the equilibrium value at the melting point. Deciphering the origins of 1D corrosion is an important step towards designing structural materials with enhanced corrosion resistance.

36 MATERIALS SCIENCE↗

Directly monitoring the shift in corrosion mechanisms of a model FeCrNi alloy driven by electric potential

Abstract Stainless steels are used in a myriad of engineering applications, including construction, automobiles, and nuclear reactors. Developing accurate, predictive mechanistic models for corrosion and electrochemical corrosion kinetics of stainless steels has been a topic of research studies over many decades. Herein, we quantified the aqueous corrosion kinetics of a model austenitic Fe–18Cr–14Ni (wt%) alloy in the presence and absence of applied potential using systematic in situ electrochemical atomic force microscopy (EC-AFM) and transmission electron microscopy (TEM). Without an applied bias, vertical dissolution of corrosion pits is controlled by the surface kinetics/diffusion hybrid mechanism, whereas lateral dissolution is diffusion controlled. When an electric bias is applied, the increase in corrosion rate is dominated by the nucleation of new pits. These insights gained by the in situ EC-AFM will allow applications of this method for a quantitative understanding of corrosion of a wider class of materials.

36 MATERIALS SCIENCE↗

Simulated fireside corrosion of T91 in oxy-combustion systems with an emphasis on coal/biomass environments

Oxy-combustion is the burning of a fuel in oxygen rather than air for the ease of capture of CO2 for reuse or sequestration. Corrosion issues associated with the change in heat exchanger tube operating environment (replacement of most of the N 2 with CO 2 and potentially higher SO x levels) from air- to oxy-combustion were examined. The ferritic-martensitic alloy T91 was used in accelerated fireside corrosion tests using several different gas compositions and ash deposit overcoats to simulate air-fired, oxy-fired coal, and oxy-fired co-fired coal/biomass conditions. Initial corrosion was observed after 240 h of exposure by examining cross-sections with retained ash. Metal section losses were determined after exposures of up to 1440 h at 600-700 °C. Severe corrosion was observed, and a corrosion response with respect to ash deposit chemistry was observed. Corrosion response differences with respect to gas phase chemistry were minimal. Alloy-oxide scale-ash morphologies were consistent with oxide fluxing mechanisms.

01 COAL, LIGNITE, AND PEAT↗

Corrosion Behavior of Steels in Supercritical CO 2 for Power Cycle Applications

In order to understand issues with corrosion of heat exchanger materials in direct supercritical carbon dioxide (sCO 2 ) power cycles, a series of autoclave exposure experiments and electrochemical experiments have been conducted. Corrosion behaviors of 347H stainless steel and P91 martensitic-ferrtic steel in sCO 2 environment have been compared. In autoclave exposure tests performed at 50°C- 245°C and 80 bar. Mass change measurements, surface characterization, and corrosion product analysis have been conducted to understand the corrosion behavior of steels in sCO 2 containing H 2 O and O 2 . Electrochemical tests performed at room temperature and 50°C, a simulation environment of water condensation phase with dissolved CO 2 was prepared to evaluate the corrosion resistance of materials. From both types of experiments, generally 347H showed higher corrosion resistance than P91.

01 COAL, LIGNITE, AND PEAT↗

Effect of Soluble Corrosion Products on Electrical Double Layer in LiCl-KCl Molten Salts

Corrosion in molten salts greatly hampers the application for renewable energy applications like molten salt reactors. To develop effective strategies for corrosion mitigation, understanding the interfacial structures and properties such as specific ion adsorption and electrical double layer capacitance are crucial. Using cyclic voltammetry and electrochemical impedance spectroscopy, we systematically studied the interfaces on various model electrodes including W (solid), Bi (liquid), and the stainless steel 316 in LiCl-KCl eutectic molten salts with the addition of corrosion species CrCl 2 and FeCl 2 . Both Cr 2+ and Fe 2+ ions increased electrical double layer capacitance, with Cr 2+ showing specific adsorption behavior and shifting the potential of zero charge, while Fe 2+ had minimal effect on point of zero charge. Two-working electrode measurements revealed increasing open-circuit potential and electrical double layer capacitance during the exposure of stainless steel 316, indicating its progressive corrosion and ion accumulation at the interface. X-ray photoelectron spectroscopy and Raman confirmed Cr enrichment at the interface. This work highlights the strong correlation between electrical double layer behavior and corrosion dynamics in molten salts and suggests electrical double layer capacitance as a sensitive, in situ indicator for corrosion monitoring.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

HVOF Thermal Spray TiC/TiB 2 Coatings for AUSC Boiler/Turbine Components for Enhanced Corrosion Protection

The high temperatures of operations still pose significant risk of degradation and fatigue from oxidizing, corroding and eroding environment. In addition to unused O 2 , water from combustion and SO x from the coal sulfur oxidation that result in highly corrosive environment, acid gases such as HCl and other sulfur compounds may also be present. These adverse effects are further accelerated due to the elevated temperatures. In addition, ash particulates and unburnt carbon and pyritic sulfur can cause erosion of the surface and thus loss of material. Unburnt carbon and pyritic sulfur may also cause localized reduction sites. Thus, fireside corrosion protection and steam oxidation protection alternatives to currently used Ni-Cr overlays need to be identified and evaluated. Titanium carbide (TiC) is a suitable alternative on account of the material features such as the high hardness, the high melting point, the high strength and the low density for the substitution or to be used in conjunction with NiCr for enhancing the fireside corrosion and erosion of the materials. Another alternative is the use of titanium boride as a coating for chemical stability required for long-term service and high erosion resistance over the state-of-the-art, high fracture toughness (K 1C ~12 MPam 1/2 ) and excellent corrosion resistance (kp~1.9X10 -11 g 2 /cm 4 /s at 800°C in air). The overarching aim of the research endeavor was to synthesize oxidation, corrosion and wear resistant TiC and TiB 2 coating powders, apply thermal spray coating on existing boiler materials and characterize the coated substrates for corrosion resistance for applications at high temperatures (500 -750 °C) and high pressures (~350 bars) using the HVOF process and to demonstrate the feasibility of these coating to be used in AUSC boilers and turbines.

20 FOSSIL-FUELED POWER PLANTS↗

Corrosion Control in Carbon Fiber Reinforced Plastic (CFRP) Composite-Aluminum Closure Panel Hem Joints

This project targeted the implementation of CFRP/Al closure panels as a drop-in replacement for all-aluminum closures used in automobile production today. The project focused on the development of corrosion fundamentals involving CFRP materials and the use of those materials in mixed-material joints. Numerous studies were completed to benchmark current materials and test mixed metal joints. Good correlation was found between outdoor exposures and laboratory cyclic corrosion testing. The insights from the corrosion testing fundamentals and benchmarking phases informed the development of low-cure adhesive and electrocoats and conductive primers for the CFRP. Adhesive and electrocoat materials were successfully developed meeting low-cure targets for bake (150C/10min). These materials were scaled-up and used to produce 5 prototype liftgates to further evaluate CFRP/Al joints in a full-scale part. The lower cure materials enabled mitigation of CTE mismatch and reduced the required bake temperature, resulting in reduced part distortion. Corrosion testing of the liftgates revealed unexpected increases in corrosion relative to the standard bake materials. While rigorous evaluation of the parts was not possible due to numerous complexities associated with prototype testing, the results provided significant insights into the material behavior of CFRP/Al joints. Key learnings from the project included a better understanding of the system complexity (interplay of substrate/primer conductivity, production of full-scale prototypes), advances in coating/adhesive design for low-cure applications involving CFRP, and advancement of corrosion test protocols for CFRP.

36 MATERIALS SCIENCE↗

Refinement of Pitting Factor Basis to Support the Corrosion Control Program (Interim Report)

At Savannah River Site (SRS), High-Level Waste is stored in below-grade tanks constructed of carbon steel. This waste is composed of sludge, salt cake, and/or supernate. In part, preparation of this waste for future processing involves dissolution of the salt cake layer. The salt dissolution process can create conditions that leave the carbon steel tanks susceptible to a number of corrosion processes. The salt to be dissolved contains high concentrations of nitrate, that once released, create an environment that may be conducive to pitting corrosion or stress corrosion cracking (SCC) of carbon steel. Additionally, during the salt dissolution process, in the absence of mixing, stratification of the supernatant liquid may occur. This can result in less dense, more dilute waste layers occurring higher in the tank. In these more dilute waste layers, the susceptibility to localized corrosion could potentially differ from that of the more concentrated salt solutions evaluated in previous testing, as the amount of inhibiting and aggressive species, not just the ratios, can affect susceptibility. Evaluation of the susceptibility to localized corrosion in these more dilute waste chemistries could provide insight into the amount of inhibitors required to effectively mitigate pitting corrosion in stagnant salt dissolution environments, as well as other tank farm operations involving dilute waste streams.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Electrochemical Control for Corrosion in Molten Chlorides During CSP Plant Operation

The Liquid Pathway of the Concentrating Solar Power Generation 3 (CSP Gen3) program proposed low-cost molten chloride salt for energy storage. However, online corrosion control was identified as a remining major risk of the Liquid Pathway approach. This project addressed that risk. Electrochemical solutions for corrosion mitigation during CSP plant operation were investigated and their feasibility and scalability were evaluated. The leading cause of corrosion in molten chloride salt systems was identified as corrosive impurities that form within the salt upon exposure to trace amounts of air and moisture. Leveraging electrochemistry, reduction/oxidation reactions can be employed to remove these corrosive impurities. In Phase 1 of this project, a bench-scale batch electrochemical reactor was designed, fabricated, and used to assess the kinetics and thermodynamics of electrochemical salt purification. In Phase 2, a laboratory-scale flow reactor was designed, fabricated, and used to assess the efficacy of the electrochemical method under flowing conditions. Results show that under proposed operating conditions for the Liquid Pathway Gen3 Pilot Plant, the electrochemical method is significantly more effective at removing impurities than alternative chemical and thermal methods, and that the electrochemical method produces less harmful byproducts. A key advance made in the course of this project was the development of a 2-electrode method for electrochemical purification that is more scalable than previously developed 3 electrode methods. This novel method is based on Magnesium (Mg) electrowinning. A provisional patent based on this invention has been submitted (USPTO Application No. 63/480,355). Additional key advances made during this project include assessment of the effect of dissimilar alloys on corrosion, kinetic and thermodynamic evaluation of thermolysis reactions of impurities within the molten salt, characterization of byproducts of purification reactions, and generation of IP focused on isolating value-added products using molten salt-based electrochemistry that could be deployed to valorize the process (USPTO Application No. 63/478,806). Ultimately, this project represented a step toward feasibility of Liquid Pathway Gen3 CSP. The method developed under this project could significantly reduce capital expenses and operating costs and increase plant profitability by enabling use of less expensive alloys, decreasing maintenance, and increasing plant longevity. Key focus areas for follow-on work have been identified as 1) evaluation of the efficacy of the electrochemical method under turbulent conditions in a larger flow system, such as the FASTR loop, 2) development of methods for removal of purification byproducts, 3) modeling pilot and industrial scale performance of electrochemical salt purification during plant operation and 4) further assessment of the effect of impurities on salt vapor phase.

14 SOLAR ENERGY↗