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 1,081 records · Page 60

Study on corrosion migrations within catalyst-coated membranes of proton exchange membrane electrolyzer cells

The corrosion of low-cost, easily manufactured metallic components inside the electrochemical environment of proton exchange membrane electrolyzer cells (PEMECs) has a significant effect on their performance and durability. Here, 316 stainless steel (SS) mesh was used as a model liquid/gas diffusion layer material to investigate the migration of corrosion products in the catalyst-coated membrane of a PEMEC. Iron and nickel cation particles were found distributed throughout the anode catalyst layer, proton exchange membrane, and cathode catalyst layer, as revealed by scanning transmission electron microscopy and energy dispersive X-ray spectroscopy. Our results indicate the corrosion products of 316 SS are transported from anode to cathode through the nanochannels of the Nafion membrane, resulting in impeded proton transport and overall PEMEC performance loss.

08 HYDROGEN↗

Hydroxide melt induced corrosion of Ni at elevated temperatures under steam electrolysis conditions

Molten alkali electrolyte based high temperature water electrolysis (HTWE) process offers an efficient pathway to integrate renewable energy resources for large scale and economic hydrogen production. Long term and stable operation of these systems require an in-depth understanding of materials stability under anodic and cathodic exposure conditions of the cell and cell stacks. In the present study, we report our findings on the corrosion of Ni in the presence and absence of (LieNa) hydroxide melt at 600 °C under oxidizing and reducing conditions representative of HTWE. While the Ni electrode was found to remain thermodynamically stable in metallic form under cathodic (reducing) exposure conditions, the corrosion rate in molten hydroxide under oxidizing conditions was found to be nonparabolic in nature. A cyclic voltammetry study provides the breakdown of the passive metal-oxide surface layer at the anodic overpotential region between 0.45 V and 2 V in molten hydroxide under oxidizing conditions. As a result, a thermochemical process for accelerated corrosion based on the oxide scale fluxing in hydroxide melt has been developed.

08 HYDROGEN↗

Controlled thermal pre-treatment of ZMG232G10® for corrosion mitigation under simulated SOFC interconnect exposure conditions

The IT-SOFC candidate interconnect material ZMG232G10® was thermally pre-treated in air and in H 2 – 3% H 2 O to mitigate dual atmosphere corrosion. Bare and pre-treated steel samples were exposed to a dual atmosphere exposure condition (dry air/metal/4% H 2 – N 2 (bal.) + 3% H 2 O) for 500h at 600°C. Corrosion products and oxide morphology developed on the air-exposed surfaces were analyzed. Pre-treatments of the metal in oxidizing (air) and reducing (H 2 – 3% H 2 O) gas atmospheres provide improved passivation against dual atmosphere corrosion compared to bare steel. Further, the uniform and iron-free oxide scale developed during the pre-treatment of alloy in the low pO 2 H 2 – 3% H 2 O gas atmosphere provides an effective diffusion barrier against the outward transport of cations and oxidation of iron observed under dual atmosphere conditions.

36 MATERIALS SCIENCE↗

Mechanical, corrosion, and wear properties of biomedical Ti–Zr–Nb–Ta–Mo high entropy alloys

The microstructures, mechanical, corrosion, and wear behaviors of the Ti x ZrNbTaMo (x = 0.5, 1, 1.5, and 2, molar ratio) high entropy alloys (HEAs) were studied in this work. It was found that the Ti–Zr–Nb–Ta–Mo HEAs showed a dendrite structure with two body-centered-cubic (BCC) solid solution phases. The Ti 0.5 ZrNbTaMo HEA exhibited a high hardness of about 500 HV, high compressive strength approaching 2,600 MPa, and large plastic strain of over 30%. Furthermore, the highly-protective oxide films formed on the surface of Ti–Zr–Nb–Ta–Mo HEAs in the phosphate buffer saline (PBS) solution, which resulted in the high corrosion resistance of the HEAs. The Ti–Zr–Nb–Ta–Mo HEAs exhibited the greater dry- and wet-wear resistance than that of the traditional biomedical Ti6Al4V alloy. The results also indicated that with the decrease in the Ti content, the wear resistance of the Ti–Zr–Nb–Ta–Mo HEAs in the PBS solution improved. Finally, the Ti 0.5 ZrNbTaMo alloy presented the highest corrosive wear resistance among the four HEAs owing to its combination of good mechanical properties and high chemical stability.

36 MATERIALS SCIENCE↗

Effects of transient thermal shock on the microstructures and corrosion properties of a reduced activation high-entropy alloy

The devices would subject transient thermal shocks (TTS) during operation under extremely harsh conditions of nuclear fusion reactors, which inevitably exert significant impact on the microstructure and performance of structural materials. Here, a reduced activation VCrFeTa 0.2 W 0.2 high-entropy alloy (HEA) was developed by vacuum arc melting. The effects of electron beam induced TTS on its microstructure, microhardness, and corrosion properties were investigated. The results indicate that the weight fraction of each phase changes after TTS, showing a significant decrease in the content of BCC1 phase and an increase in the content of BCC2 and Laves phases. The content of BCC1 phase continues to decrease slightly with increasing the power of TTS. Besides, the microhardness of the alloy increases from ~673 HV to ~714 HV after TTS treatments. In the reduced activation HEA, TTS results in a relatively low corrosion current density of ~0.472 μA/cm 2 in 3.5 wt% NaCl solution, around one-third of the current density observed in the as-cast sample. Furthermore, the VCrFeTa 0.2 W 0.2 HEA after TTS exhibits a pitting potential of ~1.165 V SCE , which is much higher than that of the as-cast sample. The refined composite multiscale entropy method is employed to analyze the influence of TTS on current fluctuation behavior during the corrosion process. The reduced activation VCrFeTa 0.2 W 0.2 HEA exhibits excellent properties in harsh environments after TTS, thereby showing advantageous property in the field of nuclear structural materials. Furthermore, TTS is an efficient and controllable strategy for the improvement of the HEAs’ microstructures and performances.

36 MATERIALS SCIENCE↗

Multiphysics modeling of two-phase film boiling within porous corrosion deposits

Porous corrosion deposits on nuclear fuel cladding, known as CRUD, can cause multiple operational problems in light water reactors (LWRs). CRUD can cause accelerated corrosion of the fuel cladding, increase radiation fields and hence greater exposure risk to plant workers once activated, and induce a downward axial power shift causing an imbalance in core power distribution. In order to facilitate a better understanding of CRUD's effects, such as localized high cladding surface temperatures related to accelerated corrosion rates, we describe an improved, fully-coupled, multiphysics model to simulate heat transfer, chemical reactions and transport, and two-phase fluid flow within these deposits. Our new model features a reformed assumption of 2D, two-phase film boiling within the CRUD, correcting earlier models' assumptions of single-phase coolant flow with wick boiling under high heat fluxes. This model helps to better explain observed experimental values of the effective CRUD thermal conductivity. Finally, we propose a more complete set of boiling regimes, or a more detailed mechanism, to explain recent CRUD deposition experiments by suggesting the new concept of double dryout specifically in thick porous media with boiling chimneys. - Highlights: • A two-phase model of CRUD's effects on fuel cladding is developed and improved. • This model eliminates the formerly erroneous assumption of wick boiling. • Higher fuel cladding temperatures are predicted when accounting for two-phase flow. • Double-peaks in thermal conductivity vs. heat flux in experiments are explained. • A “double dryout” mechanism in CRUD is proposed based on the model and experiments.

42 ENGINEERING↗

Effects of crystallization on mechanical behavior and corrosion performance of a ductile Zr 68 Al 8 Ni8Cu 16 bulk metallic glass

Here, we studied the effects of heat treatment on the microstructures, crystallization kinetics, mechanical performance, and anti-corrosion behavior of a hypoeutectic Zr 68 Al 8 Ni 8 Cu 16 bulk metallic glass (BMG). Through annealing, the precipitated phases were crystalline Zr 2 Cu and Zr 2 Ni. The total crystallinity was determined to be 10% and 77% for the samples annealed at 673 K and 713 K, respectively. The partial crystallization of the alloy leads to a dramatic deterioration in the ductility as compared to the as-cast BMG. Furthermore, the decrease in the ductility was accompanied by an increase in the crystallinity. The as-cast Zr-based BMG exhibited a greater corrosion resistance in the HCl solution than that of the annealed alloy. The depletion in the Zr and Al cation fractions of the surface oxidation film, which resulted from the precipitation of reactive nanocrystalline phases from the glassy matrix, is responsible for the reduced corrosion resistance.

36 MATERIALS SCIENCE↗

Ultra-High Temperature Steam Corrosion of Complex Silicates for Nuclear Applications: A Computational Study

Stability of materials under extreme conditions is an important issue for safety of nuclear reactors. Presently, silicon carbide (SiC) is being studied as a cladding material candidate for fuel rods in boiling-water and pressurized water-cooled reactors (BWRs and PWRs) that would substitute or modify traditional zircaloy materials. The rate of corrosion of the SiC ceramics in hot vapor environment (up to 2200 degrees C) simulating emergency conditions of light water reactor (LWR) depends on many environmental factors such as pressure, temperature, viscosity, and surface quality. Using the paralinear oxidation theory developed for ceramics in the combustion reactor environment, we estimated the corrosion rate of SiC ceramics under the conditions representing a significant power excursion in a LWR. It was established that a significant time – at least 100 h – is required for a typical SiC braiding to significantly degrade even in the most aggressive vapor environment (with temperatures up to 2200 °C) which is possible in a LWR at emergency condition. This provides evidence in favor of using the SiC coatings/braidings for additional protection of nuclear reactor rods against off-normal material degradation during power excursions or LOCA incidents. Additionally, we discuss possibilities of using other silica based ceramics in order to find materials with even higher corrosion resistance than SiC. In particular, we found that zircon (ZrSiO4) is also a very promising material for nuclear applications. Thermodynamic and first-principles atomic-scale calculations provide evidence of zircon thermodynamic stability in aggressive environments at least up to 1535 degrees C.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Analysis of stress corrosion cracking in alloy 718 following commercial reactor exposure

Alloy 718 is generally considered a highly corrosion-resistant material but can still be susceptible to stress corrosion cracking (SCC). The combination of factors leading to SCC susceptibility in the alloy is not always clear enough. In this paper, alloy 718 leaf spring (LS) materials that suffered stress corrosion damage during two 24-month cycles in pressurized water reactor service, operated to >45 MWd/mtU burn-up, was investigated. Compared to archival samples fabricated through the same processing conditions, little microstructural and property changes occurred in the material with in-service irradiation, contrary to high dose rate laboratory-based experiments reported in literature. Though the lack of delta phase formation along grain boundaries would suggest a more SCC resistant microstructure, grain boundary cracking in the material was extensive. Crack propagation routes were explored through focused ion beam milling of specimens near the crack tip for transmission electron microscopy as well as in polished plan view and cross-sectional samples for electron backscatter diffraction analysis. It has been shown in this study that cracks propagated mainly along random high-angle grain boundaries, with the material around cracks displaying a high local density of dislocations. The slip lines were produced through the local deformation of the leaf spring material above their yield strength. Also, the cause for local SCC appears to be related to oxidation of both slip lines and grain boundaries, which under the high in-service stresses resulted in crack development in the material.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Corrosion of copper and authigenic sulfide mineral growth in hydrothermal bentonite experiments

The focus of this experimental paper is to characterize interaction of bentonite with possible used-fuel waste container materials. Experiments were performed up to 300 °C at 150–160 bars for five to six weeks. Bentonite was saturated with a 1900 ppm K-Ca-Na-Cl-bearing water with Cu-foils. Copper rapidly degrades into chalcocite (CuS 2 ) and minor covellite (CuS) in the presence of H 2 S. Chalcocite growth and corrosion pit depths were measured for four different experimental runs yielding corrosion rates between 8.8 and 116 μm/yr depending on duration of experiment, brine composition, and clay type (bentonite vs. Opalinus Clay). Results of this research show that although pit-corrosion is demonstrated on Cu substrates, experiments show that the reactions that ensue, and the formation of minerals that develop, are extraordinarily slow. Finally, this supports the use of Cu in nuclide-containment systems as a possible engineered barrier system material.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Role of microstructure on CO corrosion of SiC layer in UO₂-TRISO fuel

The Advanced Gas Reactor Fuel Qualification and Development (AGR) program has focused on qualification of UCO kernel tristructural-isotropic (TRISO) particle fuel relative to UO₂ kernel TRISO particle fuel. However, a UO₂ kernel variant was included in the second AGR irradiation experiment (AGR-2) for comparison and to connect to historic fuel irradiation data. The development of a multiscale, post-irradiation examination (PIE) analysis approach through the AGR Program has allowed for a comprehensive understanding of individual particle failure. This approach has been applied to gain an understanding of SiC layer failure in UO₂ kernel TRISO fuel from AGR-2 after safety testing at 1600–1700 °C. Particle failure by intergranular CO corrosion, facilitated by a compromised inner pyrolytic carbon layer, has been confirmed through the combined application of modern x-ray computed tomography and electron microscopy techniques. In addition, a relationship between grain boundary character and CO corrosion has been identified. This finding provides an opportunity to develop mitigating strategies to improve the resilience of the SiC layer to CO corrosion in UO₂ TRISO fuel.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Effect of Li metal addition on corrosion control of Hastelloy N and stainless steel 316H in molten LiF-NaF-KF

Molten fluoride salts are used in various energy harvesting applications such as solar collectors and molten salt nuclear reactors (MSRs). Thermodynamically driven selective dissolution of alloying elements due to impurities present within the fluoride salts have been identified to be the main corrosion mechanism for structural alloys in molten fluoride salts. Impurities in these salts, during salt preparation as well as during operation, can be difficult to control. One way to prevent the selective dissolution of active alloying elements is to make the molten salt reducing by either purifying it to remove impurities or to add some reactive metal that will react with the impurities and make the salt reducing. Here this study is focused on the corrosion behaviour of Hastelloy N and 316H stainless steel in molten LiF-NaF-KF eutectic mixture (FLiNaK) at 700°C and how this behaviour changes with the addition of Li metal as a reducing impurity. Our results indicate that the active metal addition like Li can be very effective in controlling the redox behaviour of salt, which in-turn can mitigate corrosion. Even the addition of small quantities of Li metal can mitigate the selective dissolution of active alloying elements for the tested structural materials in FLiNaK. Our results also suggest that the presence of excess amounts of Li, above the minimum concentration required to react with the impurities in FLiNaK, does not have any detrimental effect in terms of formation of new intermetallic phases at the surface of the selected alloys under tested conditions.

36 MATERIALS SCIENCE↗

Interface stability of ultrasonic additively manufactured Zircaloy-4 during hydrothermal corrosion

Simulated pressurized water reactor conditions (330 °C, 15.6 MPa, ~20 ppb oxygen) without irradiation were used to investigate the hydrothermal corrosion behavior of ultrasonic additively manufactured Zircaloy-4 up to 1000 h. X-ray computed tomography allowed for visualization of defects from processing and their progression after corrosion experiments. The specimens were found to have clear variability in the mass change data, compared to typical wrought Zircaloy-4 specimens. The variation in the mass change after exposure was attributed to weld defects connected to the specimen surface which allowed ingress of oxidant into the samples. Defects visualized by computed tomography were found via metallography and characterized. In conclusion, ultrasonic additively manufactured Zircaloy-4 was found to have comparable corrosion behavior as wrought Zircaloy-4 for specimens which did not have clear surface defects along weld interfaces.

36 MATERIALS SCIENCE↗

Evaluation of corrosion coupons exposed to molten-chloride electrorefiner salts long term

Corrosion mitigation has long been considered a challenge in long-term service of both pyrochemical reprocessing and molten salt reactor applications. Corrosion coupons consisting of 2.25Cr 1Mo ASME SA387 Grade 22 Class 2 steel, were installed in a uranium electrorefiner containing molten chloride salt at 500°C. This electrorefiner went into service at Idaho National Laboratory in 1994. Seven of these coupons were removed in 2019 (i.e., submerged in molten salt for 25 years) for analysis and characterization including neutron imaging, optical microscopy, scanning electron microscopy, and wave/energy dispersive x-ray spectroscopy. The results showed that all seven coupons experienced between 30 to 175 µm of surface degradation without evidence of brittle fracture. Meaning there was no evidence of accelerated corrosion or fractures, and the average steel surface loss was of less than 5 µm per year. All indications were that the environmental conditions inside the electrorefiner were favorable for the steel alloy.

36 - MATERIALS SCIENCE↗

Analysis of the magnetic corrosion product deposits on a boiling water reactor cladding

The buildup of corrosion product deposits (CRUD) on the fuel cladding of the boiling water reactor (BWR) before and after zinc injection has been investigated by applying local experimental analytical techniques. Under the BWR water chemistry conditions, Zn addition together with the presence of Ni and Mn induce the formation of (Zn,Ni,Mn)[Fe{sub 2}O{sub 4}] spinel solid solutions. X-ray absorption spectroscopy (XAS) revealed inversion ratios of cation distribution in spinels deposited from the solid solution. Based on this information, a two-site ferrite spinel solid solution model is proposed. Electron probe microanalysis (EPMA) and extended X-ray absorption fine structure (EXAFS) findings suggest the zinc-rich ferrite spinels formation on BWR fuel cladding mainly at lower pin. - Graphical Abstract: Analysis of spinels in corrosion product deposits on boiling water reactor fuel rod. Combining EPMA and XAFS results: schematic representation of the ferrite spinels in terms of the end members and their extent of inversion. Note that the ferrites are represented as a surface between the normal (upper plane, M[Fe{sub 2}]O{sub 4}) and the inverse (lower plane, Fe[MFe]O{sub 4}). Actual compositions red Black-Small-Square for the specimen at low elevation (810 mm), blue Black-Small-Square for the specimen at mid elevation (1800 mm). The results have an impact on the properties of the CRUD material. Highlights: Black-Right-Pointing-Pointer Buildup of corrosion product deposits on fuel claddings of a boiling water reactor (BWR) are investigated. Black-Right-Pointing-Pointer Under BWR water conditions, Zn addition with Ni and Mn induced formation of (Zn,Ni,Mn)[Fe{sub 2}O{sub 4}]. Black-Right-Pointing-Pointer X-Ray Adsorption Spectroscopy (XAS) revealed inversion of cations in spinel solid solutions. Black-Right-Pointing-Pointer Zinc-rich ferrite spinels are formed on BWR fuel cladding mainly at lower pin elevations.

36 MATERIALS SCIENCE↗

Effect of heat input on the microstructure, residual stresses and corrosion resistance of 304L austenitic stainless steel weldments

Austenitic stainless steels are widely used in high performance pressure vessels, nuclear, chemical, process and medical industry due to their very good corrosion resistance and superior mechanical properties. However, austenitic stainless steels are prone to sensitization when subjected to higher temperatures (673 K to 1173 K) during the manufacturing process (e.g. welding) and/or certain applications (e.g. pressure vessels). During sensitization, chromium in the matrix precipitates out as carbides and intermetallic compounds (sigma, chi and Laves phases) decreasing the corrosion resistance and mechanical properties. In the present investigation, 304L austenitic stainless steel was subjected to different heat inputs by shielded metal arc welding process using a standard 308L electrode. The microstructural developments were characterized by using optical microscopy and electron backscattered diffraction, while the residual stresses were measured by X-ray diffraction using the sin{sup 2}ψ method. It was observed that even at the highest heat input, shielded metal arc welding process does not result in significant precipitation of carbides or intermetallic phases. The ferrite content and grain size increased with increase in heat input. The grain size variation in the fusion zone/heat affected zone was not effectively captured by optical microscopy. This study shows that electron backscattered diffraction is necessary to bring out changes in the grain size quantitatively in the fusion zone/heat affected zone as it can consider twin boundaries as a part of grain in the calculation of grain size. The residual stresses were compressive in nature for the lowest heat input, while they were tensile at the highest heat input near the weld bead. The significant feature of the welded region and the base metal was the presence of a very strong texture. The texture in the heat affected zone was almost random. - Highlights: • Effect of heat input on microstructure, residual stresses and corrosion is studied. • HAZ and width of dendrite in the welded region increase with heat input. • Residual stresses are tensile near the welded region after the highest heat input. • Welded region has the highest pit density after highest heat input. • Dendrites and δ-ferrite were highly oriented in the welded region.

36 MATERIALS SCIENCE↗

The role of frequency on fretting corrosion of Alloy 690TT against 304 stainless steel in high temperature high pressure water

Highlights: • Delamination, material transfer and oxidation dominated fretting corrosion behavior in HTHP water. • Delamination was pure mechanical wear to produce fresh surface exposed to HTHP water for oxidation. • Increased frequency enhanced the maximum thickness of oxide film in worn surface. • Increased frequency accelerated the formation of tribologically transformed structure (TTS). • Increased frequency accelerated the escape of wear debris, which originated from the TTS and crushed oxide particles. - Abstract: In high temperature high pressure (HTHP) water, the role of frequency in fretting corrosion behavior and mechanism of Alloy 690TT against Type 304 stainless steel were investigated. Results indicated that wear mechanisms of delamination, material transfer and oxidation collectively dominated the fretting corrosion behavior. The delamination was related to pure mechanical wear to produce fresh surface exposed to HTHP water for oxidation, resulting in the increase of wear depth and volume. The increasing frequency played little role in oxide type of worn surfaces, which consisted of (Ni,Fe)(Fe,Cr){sub 2}O{sub 4} and Cr{sub 2}O{sub 3}. However, it enhanced the maximum thickness of oxide film in the worn surface. The increasing frequency resulted in the acceleration of the formation of nanostructured tribologically transformed structure (TTS) layer because it could aggravate the plastic deformation and increase the contact temperature for dynamic recrystallization. The increasing frequency accelerated the escape of the ultra-fine grained wear debris, which originated from not only the damage of TTS layer but also the crushed oxide particles generated in the contact gap.

36 MATERIALS SCIENCE↗

Effect of aging treatment on microstructures, tensile properties and intergranular corrosion behavior of Al–Cu–Li alloy

Highlights: • T8 duplex aging greatly promoted the precipitation of strengthening phases. • Heavy precipitation of strengthening phases led to enhancing of tensile properties. • Intergranular corrosion sensibility can be reduced by T8 duplex aging greatly. - Abstract: The influence of aging treatment on microstructures, tensile properties and corrosion properties of Al–Cu–Li alloy was investigated. The results show that the T8 duplex aging treatment was more effective than T6 and T8 single aging treatment in enhancing the tensile properties and improving the intergranular corrosion (IGC) resistance. Based on the microstructure observation, tensile test, electrochemical experiment and IGC measurement, the factors which affect the microstructures, tensile properties and IGC behavior changing of Al–Cu–Li alloy during aging treatments were discussed in detail.

36 MATERIALS SCIENCE↗