Engineering Papers⌕ Search

Engineering topics

Boerstler, Joshua T.

Publications and source records attributed to Boerstler, Joshua T..

Refinement of Pitting Factor Basis to Evaluate Minimum Nitrite Requirement in Dilute Waste Chemistries

Considering that chloride concentrations are an order of magnitude lower at SRS than the maximum chloride previously tested to evaluate pitting susceptibility of carbon steel, it has been proposed that the Pitting Factor methodology be refined to determine if a reduction in the minimum nitrite requirement is warranted in more dilute solutions and those with chloride concentrations more indicative of waste tank chemistries at SRS. Through the use of cyclic potentiodynamic polarization, the susceptibility of A537 carbon steel to pitting corrosion was evaluated. The Pitting Factor was shown to accurately predict pitting susceptibility throughout the chemistry envelope evaluated. In addition, it was shown that nitrite is not required for inhibition of pitting corrosion in tank conditions with chloride concentrations observed at SRS and up to 4 M nitrate. Based upon these findings, new control limits were proposed that removed the minimum nitrite requirement within the chemistry envelope evaluated up to 50 °C.

36 MATERIALS SCIENCE↗

Hanford Double Shell Waste Tank Corrosion Studies (Final Report)

For fiscal year (FY) 2022, the Savannah River National Laboratory (SRNL) focused on two experimental tasks related to Hanford Double Shell Tank (DST) chemistry and integrity. The first task focused on understanding risk of corrosion due to formation of either continuous layers or discrete patches of solids on the tanks' inner sidewalls and bottoms. The tank bottom solids contact corrosion testing focused on studying the effects of forming a dry adherent solids layer on a carbon steel substrate. Long-term exposure tests and electrochemical tests were performed to investigate the effect of drying (i.e., removing water) from the solids phase. The second task focused on corrosion of the exterior of the secondary liner. In previous years, vapor corrosion inhibitors (VCIs) were investigated as a means of mitigating corrosion of the exterior of the secondary liner. During FY22 the utilization of nitrogen was explored as a means of corrosion mitigation. The corrosion test results with nitrogen were compared with the corrosion mitigation performance of the VCIs.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

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↗

Development of electrostatic precipitator (ESP) technology to remove elemental mercury vapor, HG(0)

The presence of mercury vapor or other forms of mercury presents issues with worker safety, decommissioning facilities, and environmental impacts. As such, it is desired to develop a strategy to either remove or reduce mercury levels in Oak Ridge’s Y-12 Complex facilities. A testing methodology was developed to evaluate electrostatic precipitator technology for removal of mercury vapor. This methodology involved supplying mercury vapor-containing air to the ESP device by flowing air through a column containing alternating layers of sand and liquid mercury droplets. Initial attempts at quantifying the efficacy of the ESP device in removing mercury vapor were plagued with difficulties in controlling the flow of mercury into the ESP device due to poor performance of the generator column and the contamination of these experiments with mercury from an unknown source. These issues were resolved by creating a new generator column with slower air velocity and higher surface area of liquid mercury, along with moving the air intake for the ESP device to outside of the chemical hood in which testing took place. This resulted in a steady, quantified flow of mercury vapor from the generator column and no observation of unintended mercury sources. A final test of the ESP device under these controlled conditions showed that for a certain amount of time (on the order of 20-30 minutes) mercury concentrations were reduced by approximately 33 - 67% of the inlet concentration. However, episodic releases or pulses of mercury observed only at the outlet indicated that the mercury accumulated in the ESP device is periodically expelled. As a result, it was not deemed to be an efficient strategy for the removal of elemental mercury vapor.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Refinement of Salt Dissolution Inhibitor Requirements (Final Report)

At Savannah River Site (SRS), High-Level Waste is stored in below-grade carbon steel tanks. This waste in part consists of sludge, salt cake, and/or supernate. 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 localized corrosion. The salt to be dissolved contains high concentrations of nitrate, that once released, create an environment that may be conducive to pitting corrosion and/or stress corrosion cracking (SCC) of carbon steel. The salt dissolution process also liberates interstitial liquid trapped between the salt crystals. This liquid is initially high in nitrite and hydroxide concentration. High pH and greater ratios of nitrite to nitrate act as inhibitors to minimize corrosion of carbon steel in high nitrate environments. However, as dissolution proceeds, the concentration of nitrate will increase, while the hydroxide and nitrite concentration of the interstitial liquid will deplete and become insufficient to prevent the onset of corrosion attack. Tank blending and addition of inhibitors are used to ensure adequate concentrations of hydroxide and nitrite. However, this is not desirable during salt dissolution as it can reduce process efficiency and increase the amount of waste that needs processing. It has been proposed that these corrosion control limits be revisited to evaluate the corrosion susceptibility of carbon steel in environments that more closely resemble current operating conditions at SRS. An experimental matrix was designed to evaluate the use of the pitting factor for supernate chemistries characteristic to SRS, particularly during the salt dissolution process. Two electrochemical methods were identified to determine the susceptibility of A537 and A285 low-carbon steels to pitting corrosion with this chemistry envelope at temperatures up to 75 °C. The predominant electrochemical test method was Cyclic Potentiodynamic Polarization (CPP) studies. Through CPP, the pitting factor was used, based on Hanford Site corrosion studies, to accurately identify pitting susceptibility within the compositional range studied with some conservatism. Additionally, sulfate was determined to have no statistically significant influence, at concentrations up to 0.6 M, on pitting behavior in more concentrated solutions where other aggressive species govern pitting susceptibility. Where CPP was inconclusive, Modified ASTM G192 was successfully used to evaluate pitting susceptibility conditions and allowed for a pass/fail result to be determined. In all cases, the pitting factor was determined to be applicable to the simulants tested, with this metric accurately predicting incidences in which pitting occurred. Based upon the findings in this work, a pitting factor of 1.2 is being proposed to build in a safety factor and remain consistent with the Hanford Site approach. Additionally, a minimum pH limit of 12 is proposed to ensure carbon steel passivity and localized corrosion the primary degradation mechanism. Susceptibility to SCC was evaluated using a reduced matrix of tests at 75 °C. No failures due SCC were observed at open circuit. In addition, tests polarized anodically by 200 mV only resulted in failures for trials with pitting factors less than 0.86. However, a test with a passing condition based upon the pitting factor metric (pitting factor = 1.40) did exhibit a failure with an applied potential of +300 mV vs. OCP. This result is contrary to the prediction based upon the pitting factor, however, a polarization of 300 mV, or even 200 mV, from open circuit is substantial. The relationship between these testing parameters and service environment/conditions and the desired level of conservatism in the metric should be further evaluated in the determination of the significance of this result. While the pitting factor accurately predicted susceptibility to SCC at temperatures up to 75 °C and with positive overpotentials up to 200 mV, the relatively small sample matrix and failure of a passing pitting factor with a 300 mV polarization resulted in an inconclusive determination of whether the pitting factor may be used for predicting susceptibility to SCC at temperatures between 50 °C and 75 °C. As such, additional testing is recommended to evaluate the validity of the pitting factor for SCC susceptibility prediction at temperatures between 50 °C and 75 °C.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Refinement of Salt Dissolution Inhibitor Requirements (Interim Report)

At Savannah River Site, High-Level Waste is stored in below-grade carbon steel tanks. This waste in part consists of sludge, salt cake, and/or supernate. 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 localized corrosion. 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. The salt dissolution process also liberates interstitial liquid trapped between the salt crystals. This liquid is initially high in nitrite and hydroxide concentration. High pH and greater ratios of nitrite to nitrate act as inhibitors to minimize corrosion of carbon steel in high nitrate environments. However, as dissolution proceeds, the concentration of nitrate increases while the hydroxide and nitrite concentration of the interstitial liquid depletes and becomes insufficient to prevent the onset of corrosion attack. While tank blending and the addition of inhibitors are used to ensure adequate concentrations of hydroxide and nitrite during normal operation, this is not desirable during salt dissolution as it can reduce process efficiency and increase the amount of waste that needs processed.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Augmented Monitoring and Condition Assessment Program (AMCAP) Material Test Reactor (MTR) (Fuel Inspection Program Report)

The AMCAP MTR Fuel Inspection Program, a special inspection program comprised of four inspection campaigns, examined a total of ten (10) pre-selected aluminum-clad, aluminum-based fuel core spent nuclear fuel assemblies (ASNF) stored in the L Area Disassembly Basin (L Basin) at the Savannah River Site. A full description of the inspections and the results are reported. The fuel had been stored in bundled-tube storage (Vertical Tube Storage) for periods of 18 to 21 years. The prior service experience of the individual 10 assemblies varies, but all included irradiation followed by wet storage at international research reactor sites prior to shipment to the US and storage in L Basin. The 10 assemblies were expected to be among the “worst"’ in terms of prior corrosion damage of the entire inventory of the direct-bundle-stored ASNF in L Basin. The inventory of MTR ASNF in L Basin will continue to be stored in the bundled-tube configuration or in slug-storage buckets with inserts pending retrieval for ultimate disposition. The MTR fuel inspections focused on collecting information for characterization of the material condition of the ASNF considering various types of aluminum fuel corrosion degradation of its assembled materials in water storage. A custom-designed Fuel Inspection Table was used to stage the fuel for remote, enhanced visual examination (close-up video imaging & recording) with controlled lighting and positioning that enables reproducibility of imaging conditions. The inspections were conducted by fuel subject matter expert staff from Spent Fuel Project Engineering (SFPE) and the Savannah River National Laboratory (SRNL). Stills captured from the video records were used to compare the corrosion evolution from previous records, as available. This evaluation of the inspection results including the comparison to the previous inspection results demonstrate that the water quality and the storage configuration of ASNF in L Basin do not cause aggressive corrosion degradation of the fuel; mitigation of the prior corrosion degradation of the fuel also appears to have been achieved with the good water quality conditions of L Basin. Recommendations are made for future inspection of the fuel to trend corrosion degradation and demonstrate continued safe wet storage of the ASNF in L Basin. The next fuel examination is recommended to be performed in 5 years.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Augmented Monitoring and Condition Assessment Program for SNF Wet Storage Life Extension - 20489

Approximately 27 MTHM of spent nuclear fuel (SNF) owned and managed by the U.S. Department of Energy, Office of Environmental Management is stored in the L Basin at the Savannah River Site (SRS). This 'DOE SNF' is comprised of approximately 12,000 aluminum-clad, aluminum-based fuel assemblies (∼7 MTHM), and approximately 2000 non-aluminum fuel assemblies (∼20 MTHM). A program is in progress to perform Non-Destructive Examination (NDE) of the fuel and their storage containers to characterize the materials' condition, and to evaluate the effects of service to enable continued safe wet storage of the SNF. The Augmented Monitoring and Condition Assessment Program (AMCAP), a two-part program to develop and implement remote underwater Non-Destructive Examination of the aluminum SNF, and of the containers of the non-aluminum SNF, respectively, is aimed at the characterization and evaluation of corrosion degradation of aluminum fuel and container materials. The predominant design of the aluminum SNF (ASNF) stored in L Basin is the Materials Test Reactor (MTR) equivalent design, a plate fuel design. These SNF are stored in 5'' diameter tubes or 5'' x 5'' squares (called bundles) that are nominally 12' or up to 14' long. The SNF is de-bundled and inspected using a custom-designed MTR Fuel Inspection Table. The inspection table provides for indexed fuel positioning for a video camera examination with controlled lighting. A total of 10 of the SNF originating from foreign research and test reactors were selected for examination based on burnup, enrichment, and prior damage caused by service/storage history. A special inspection campaign of these 10 assemblies is in progress. The observed corrosion damage included minor to moderate attack from general corrosion, pitting, crevice, end grain and galvanic corrosion. Example results from the completed inspections are shown and discussed. The focus is a comparison of the as-received condition versus the as-found current storage condition that will serve to validate Water Chemistry and Corrosion Monitoring Programs. The non-aluminum SNF (NASNF) stored in L Basin are of diverse design that includes various geometries with claddings of stainless steel, Zircaloy, and Hastelloy. The fuel core materials include uranium alloys, oxides/mixed oxides, and carbides. These SNF materials, originating from early experimental and test reactors, are in various physical forms including single fuel elements and cut pieces. The fuel is stored in L Basin in various configurations including in direct bundled storage in aluminum tubes and in isolation cans that are in the bundles or in a larger over-size storage container (OSC). Concern with inside-out corrosion and the potential loss of configuration control and ability to handle the storage containers prompted the development of remote NDE methods that include visual and UT technologies to assess the condition of the containers. Candidate stored materials were selected for a special inspection campaign; the development of the NDE methods for the inspection for galvanic, crevice and sediment-induced corrosion (inside-out) are discussed. A summary of the SNF storage in L Basin at the SRS, and an overview of the AMCAP to enable continued safe storage of DOE SNF are described. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗