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At least 19 records

Spatial distribution of crystalline corrosion products formed during corrosion of stainless steel in concrete

The mineralogy and spatial distribution of nano-crystalline corrosion products that form in the steel/concrete interface were characterized using synchrotron X-ray micro-diffraction (μ-XRD). Two types of low-nickel high-chromium reinforcing steels embedded into mortar and exposed to NaCl solution were investigated. Corrosion in the samples was confirmed by electrochemical impedance spectroscopy (EIS). μ-XRD revealed that goethite (α-FeOOH) and akaganeite (β-FeOOH) are the main iron oxide–hydroxides formed during the chloride-induced corrosion of stainless steel in concrete. Goethite is formed closer to the surface of the steel due to the presence of chromium in the steel, while akaganeite is formed further away from the surface due to the presence of chloride ions. Detailed microstructural analysis is shown and discussed on one sample of each type of steel. - Highlights: • Synchrotron micro-diffraction used to map the distribution of crystalline phases. • Goethite and akaganeite are the main corrosion products during chloride induced corrosion in mortar. • Layers of goethite and akaganeite are negatively correlated. • EDS showed Cr present in corrosion products identified by SEM.

36 MATERIALS SCIENCE↗

Corrosion products of carbonation induced corrosion in existing reinforced concrete facades

Active corrosion in reinforced concrete structures is controlled by environmental conditions and material properties. These factors determine the corrosion rate and type of corrosion products which govern the total achieved service life. The type and critical amount of corrosion products were studied by electron microscopy and X-ray diffractometry on concrete and reinforcement samples from existing concrete facades on visually damaged locations. The corrosion products in outdoor environment exposed concrete facades are mostly hydroxides (Feroxyhite, Goethite and Lepidocrocite) with a volume ratio to Fe of approximately 3. The results can be used to calibrate calculation of the critical corrosion penetration of concrete facade panels.

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↗

The Effect of Jet Flow Impingement on the Corrosion Products Formed on a Pipeline Steel in Naturally Aerated Sour Brine

Corrosion was generated by the action of a jet impingement flow of sour brine on pipeline steel samples of X70. Flow-assisted corrosion affected nature, number and peak intensity of the chemical species formed as corrosion products. Iron sulfides predominated in static and low flow rate conditions (1.1 m/s), whereas at 2.4 m/s iron oxides were mainly formed, which led to higher corrosion rates and suggested that oxides are less protective than sulfides. On inhibition, imidazoline seems to mitigate oxide formation and support sulfide formation balancing both species on steel surface. Ferrite phase in laminar pearlite was preferentially dissolved with/without inhibitor, and mackinawite (FeS{sub 2}) was formed at every flow rate, angle with and without inhibitor. Theoretical stresses determined by computational flow dynamics for corrosion product removal showed a fair approximation to those proposed in the literature.

36 MATERIALS SCIENCE↗

Characterization of wellbore casing corrosion product as a permeable porous medium

Leakage along wellbores is of concern for a variety of applications, including sub-surface fluid storage facilities, geothermal wells, and CO 2 storage wells. We have investigated whether corroded casing is permeable to gas and can serve as a leakage pathway along wellbores. Three specimens were prepared from laboratory steel plates corroded using different mechanisms to reflect different possible field conditions and produce a variety of corrosion rates. Single-phase gas flow measurements were made under a range of gas pressures to investigate flow in both the viscous and visco-inertial flow regimes. Tests were conducted at different confining stresses (range from 3.45 to 13.79 MPa) following both loading and unloading paths. The gas flow test results imply corroded casing can serve as a significant leakage path along the axis of a wellbore. Transmissivity was discovered to be sensitive to the variation in confining stress suggesting that the corrosion product is deformable. Gas slip factors and the coefficients of inertial resistance of the corrosion product were comparable to those available in the literature for other porous media. Post-test examination of the corrosion product revealed it to be a heterogeneous, mesoporous material with mostly non-uniform slit type porosity. There was no discernable difference in the composition of corrosion product from specimens corroded by different mechanisms.

02 PETROLEUM↗

Literature Review on the Sorption of Plutonium, Uranium, Neptunium, Americium and Technetium to Corrosion Products on Waste Tank Liners

The Savannah River Site (SRS) has conducted performance assessment (PA) calculations to determine the risk associated with closing liquid waste tanks. The PA estimates the risk associated with a number of scenarios, making various assumptions. Throughout all of these scenarios, it is assumed that the carbon-steel tank liners holding the liquid waste do not sorb the radionuclides. Tank liners have been shown to form corrosion products, such as Fe-oxyhydroxides (Wiersma and Subramanian 2002). Many corrosion products, including Fe-oxyhydroxides, at the high pH values of tank effluent, take on a very strong negative charge. Given that many radionuclides may have net positive charges, either as free ions or complexed species, it is expected that many radionuclides will sorb to corrosion products associated with tank liners.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Plutonium Oxidation State Distribution in the Presence of WIPP-Relevant Organics and Iron Corrosion Products

The oxidation state and solubility of plutonium (Pu) in high ionic strength synthetic WIPP (Waste Isolation Pilot Plant) brines as a function of pC H+ in the presence and absence of WIPP-relevant organic ligands (EDTA [Ethylenediaminetetraacetic acid], oxalate, citrate, acetate) and iron corrosion products (magnetite and metallic iron) at 𝑇 = 23 ± 2 ∘C was thoroughly studied by long-term batch solubility experiments (between approximately 800-1,100 days) from an undersaturation approach. The oxidation state of Pu in the WIPP environment has been a topic of interest since the initial Compliance Certification Application (CCA). This study aims to investigate the solubility of Pu under the expected WIPP conditions and to determine the oxidation state of the solid phase that will control the solubility. One of the most important results of this study is that the Pu oxidation state was analyzed both from the surface area of the corrosion products and in the precipitated solid. The analysis of the Pu oxidation state on the surface of the iron mineral from the ongoing undersaturated experiments is more relevant to the performance assessment of nuclear waste disposal than short term batch (plutonium-iron phase) experiments. The X-ray Absorption Near-Edge Spectroscopy (XANES) analysis showed that Pu oxidation state is different on the metal surface and in the precipitated solid. Pu(III) is the dominant oxidation state in the metallic iron (Fe 0 ) system in the presence and absence of organics. Pu(IV) is the dominant oxidation state in the magnetite system in the presence and absence of organics. Also, organics stabilize Pu(IV) in the magnetite system. Analysis of Pu in the precipitated solid by Extended X-ray Absorption Fine Structure (EXAFS) analysis showed that Pu formed an inner-sphere complex with iron with minor amounts of PuO 2 present. X-ray diffraction (XRD) results indicate that metallic iron and magnetite did not oxidize in three years in the alkaline and high ionic strength system. Under these conditions (8 < pC H+ < 10 at T = (22 ± 2) °C under nitrogen atmosphere, the solubility of Pu changes by up to three orders of magnitude (10 -5 and 10 -8 M). The spread in solubility is highest at pC H+ = 9. Pu(III) and Pu(IV) showed different solubility behavior in the synthetic WIPP brine. A summary of the data collected in this report will be submitted to Sandia National Laboratories as part of a parameter update report which will outline the changes to the OXSTAT parameter for the 2026 Compliance Recertification Application (CRA-2026). The experiments performed were done according to the U.S. Department of Energy (DOE) approved Test Plan entitled “Effects of Radiolysis, Organic Complexation, and Redox Conditions on the Speciation and Oxidation State Distribution of Pu(III/IV)” (LCO-ACP-25). All data reported were obtained under the Los Alamos National Laboratory-Carlsbad Office (LANL-CO) Quality Assurance Program, which is compliant with the DOE Carlsbad Field Office, Quality Assurance Program Document (CBFO/QAPD).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Specific corrosion product on interior surface of a bronze wine vessel with loop-handle and its growth mechanism, Shang Dynasty, China

In this paper, a kind of specific stalactitic product was found on the interior surface of a covered bronze wine vessel with loop-handle (Chinese name is you), which was fabricated in Shang Dynasty (1700 B.C.-1100 B.C.) and now is collected in Xiaogan Museum, Hubei province of China. The microstructures of the product were characterized systematically by using optical microscopy, scanning electron microscope, transmission electron microscope, X-ray diffraction, and Raman microscopy. The experimental results revealed that the product belonged to a kind of malachite with high purity and high crystallinity. The growth of the product was considered to be a possible reason that the vessel was overly airtight within a museum display cabinet besides a lid of the vessel, which made the excess of H{sub 2}O and CO{sub 2} gas concentrations inside the vessel during long-term storage. This corrosion product is very harmful to bronze cultural relics, because of a large amount of copper consumption from the matrix which will reduce its life. The growth mechanism of the specific stalactitic product and the suggestions for preservation of the similar bronze relics in museum were proposed. - Highlights: Black-Right-Pointing-Pointer The stalactitic product was the high purity and good crystallinity malachite. Black-Right-Pointing-Pointer Its growth was related to the excess of H{sub 2}O and CO{sub 2} gas concentrations in museum. Black-Right-Pointing-Pointer It is harmful to the bronzes, because copper will be consumed from the matrix. Black-Right-Pointing-Pointer The suggestions for preservation of the similar bronzes in museum were proposed.

36 MATERIALS SCIENCE↗

Characterization of Localized Filament Corrosion Products at the Anodic Head on a Model Mg-Zn-Zr Alloy Surface

In this study, localized filament corrosion products at the anodic head on a model Mg-1%Zn-0.4%Zr alloy surface were characterized by electron microscopy techniques of site-specific lamella prepared by focused ion beam milling. It is revealed that the anodic head propagates underneath a largely intact thin and dense MgO surface film and comprises dense aggregates of nano-crystalline MgO within a nano-porous Mg(OH) 2 network. In conclusion, the findings contribute new supportive direct imaging insight into the source of the enhanced H 2 evolution that accompanies anodic dissolution of Mg and its alloys.

36 MATERIALS SCIENCE↗

Property Measurements of LiF-NaF-KF Molten Salts Doped with Corrosion Products and Oxygen

Measurements of thermophysical properties of molten salts are needed for modeling and simulation activities that support the development of molten salt reactor (MSR) technologies. Properties of interest including transition temperatures, phase behavior, heat capacity, density, volumetric thermal expansion, surface tension, viscosity, thermal diffusivity, thermal conductivity, and vapor pressure are being performed at Argonne. Results of these property measurements are suitable for use in evaluating reactor performance during startup and the early operating life of the reactor. Ingressions of oxygen and moisture into the fuel salt are expected to occur at different times during the operating life of the reactor due to system leaks, maintenance, and refueling activities. The presence of these environmental contaminants induces corrosion of structural materials. The introduction of corrosion-derived species, oxygen and moisture is expected to affect the physical and chemical properties of the salt and operation of the reactor. Previous work performed at Argonne evaluated the effects of fission product dopants on the thermal properties of eutectic LiF-NaF-KF (FLiNaK). Properties of FLiNaK are commonly used to represent those of fluoride-bearing fuel salts. Metallic corrosion products such as chromium and nickel ions together with dissolved oxygen are expected to affect system redox differently than the accumulation of fission products. Work summarized in this report was performed to measure the effects of corrosion products and dissolved oxygen on the phase transitions, and specific heat capacity of FLiNaK. Thermophysical property measurements were made using four salts that were prepared by doping aliquots of a eutectic mixture of FLiNaK with surrogate corrosion products. Controlled additions of CrF 3 and NiF 2 were used as surrogates for corrosion product contamination anticipated during extended reactor operations in which fuel salt is in contact with steel reactor components. Controlled additions of UF 4 from two sources containing known amounts of UO 2 at different concentrations were used to represent oxygen contamination. The phase transitions and specific heat capacities of the four salts were measured by using differential scanning calorimetry. Measurements were made at temperatures spanning the range of 500−900 °C, which is the expected operating range of MSRs. Measured property values were compared to values measured previously with eutectic FLiNaK without dopants. Differences between property values measured for the doped and non-doped salts were compared with the uncertainties of the measurements to determine the significance of the effect of corrosion products and oxygen on salt properties.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

M4SF-20LL010302042: Process Model for Radionuclide Incorporation into Corrosion Products

This progress report (Level 4 Milestone Number M4SF-20LL010302042) summarizes research conducted at Lawrence Livermore National Laboratory (LLNL) within the Crystalline Activity Number SF-20LL010302041. The research is focused on actinide and radionuclide sequestration in steel corrosion products. Fuel matrix degradation models suggest that the near field is likely to be reducing at the time of canister breaching, steel corrosion, and radionuclide release, but more oxidizing conditions may prevail in the far field. The incorporation of radionuclides into corrosion phases may limit the rate of radionuclide release by sequestering a portion of the radionuclide source term. For these reasons there is a need to evaluate the incorporation of Pu and other radionuclides into various Fe-oxide phases, and to understand the behavior of coprecipitated phases during mineral recrystallization processes and during re-oxidation events. Radionuclide coprecipitation with Fe minerals may impact long-term repository performance and is an ongoing research focus at Lawrence Livermore National Laboratory.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

M4SF-22LL010302052-Radionuclide Incorporation Model for Corrosion Products

This progress report (Level 4 Milestone Number M4SF-22LL010302052) summarizes research conducted at Lawrence Livermore National Laboratory (LLNL) within the Crystalline Activity Number SF-22LL01030205. The research is focused on actinide and radionuclide sequestration in steel corrosion products.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

M4SF-18LL010302082-Thermodynamic Database Development and Identification of Actinide Sequestration in Corrosion Products

This progress report (Level 4 Milestone Number M4SF-18LL010302082) summarizes research conducted at Lawrence Livermore National Laboratory (LLNL) within the Crystalline International Collaborations Activity Number SF-18LL010302081. The activity is focused on our long-term commitment of engaging our partners in international nuclear waste repository research. This includes participation in the following activities: actinide sequestration in steel corrosion products (Enrica Balboni), Nuclear Energy Agency Thermochemical Database (NEA TDB) Project (Cindy Atkins-Duffin), thermodynamic database collaborations (Tom Wolery), and surface complexation model international collaborations (Mavrik Zavarin).

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

The TRANSCEND Consortium - In-situ Identification of Surface Corrosion Products on Spent Nuclear Fuels - 20276

The management of spent nuclear fuel is a major ongoing concern for the UK owing to the cessation of reprocessing operations at Sellafield and the large, complex inventory arising from Magnox, AGR, PWR and prototype reactors. Retrieval and relocation operations for legacy fuels are imminent and therefore, any models that enhance our understanding of fuel evolution will help mitigate the risks associated with fuel storage and disposal. The TRANSCEND Consortium on nuclear waste management comprises four work packages, within this current paper we provide a summary overview of progress to date and illustrative results from Theme 3: Spent Nuclear Fuels. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

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↗

Rapid Quenching of Molten Salts as an Approach for the Coordination Characterization of Corrosion Products

A new apparatus was built to rapidly cool molten salts in liquid argon to prevent contamination during quenching and enable new insight into the structure in the liquid state. To test the applicability of the apparatus, several industrially relevant chloride salt compositions were first melted, rapidly solidified, and then characterized. The design proved applicable for the rapid quenching of molten salt. Furthermore, the structure of the apparatus prevented exposure of the rapidly quenched salt to impurities (humidity, oxygen, etc.). X-ray diffraction of salt specimens cooled with and without liquid argon showed differences including a structure further from the expected stoichiometric equilibrium with rapid cooling. Of particular interest is the chemical state of metallic impurities, and this may be probed using electron paramagnetic resonance.

36 MATERIALS SCIENCE↗