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At least 73 records · Page 4

Analysis of tank 7 surface supernatant sample (FTF-7-15-26) in support of corrosion control program

This report provides the results of analyses on Savannah River Site Tank 7 surface supernatant liquid sample in support of the Corrosion Control Program (CCP). The measured nitrate, nitrite and free-hydroxide concentrations for the Tank 7 surface sample averaged, 3.74E-01 ± 1.88E-03, 4.17E-01 ± 9.01E-03 and 0.602 ± 0.005 M, respectively. The Tank 7 surface cesium-137, sodium and silicon concentrations were, respectively, 3.99E+08, ± 3.25E+06 dpm/mL, 2.78 M and <3.10 mg/L. The measured aluminum concentration in the Tank 7 surface sample averaged 0.11 M.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Analysis of Tank 30H (HTF-30-18-54, -55), Tank 32H (HTF-32-18-56, -57), and Tank 37H (HTF-37-18-58, -59) Samples for Support of the Evaporator Feed Qualification and Corrosion Control Programs for the 3H-Evaporator

SRNL analyzed samples from Tank 30H, Tank 32H, and Tank 37H to support the Evaporator Feed Qualification and Corrosion Control Programs for the 3H-Evaporator system. The six samples from Tanks 30H, 32H, and 37H all contain highly concentrated salt solution s with sodium concentrations ranging from 7.89 M to 15.0 M. The samples from Tank 30H show small differences in the concentrations of the major cations and anions between the surface sample and VDS. The two Tank 32H samples show significant differences in the concentrations of the major anions and cations with the VDS being nearly twice as concentrated as the surface sample. The surface sample and VDS from Tank 37H contain very similar compositions.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Analysis of Tank 30H (HTF-30-18-96, -97), Tank 32H (HTF-32-18-98, -99), and Tank 37H (HTF-37-18-100, -101) Samples for Support of the Evaporator Feed Qualification and Corrosion Control Programs for the 3H-Evaporator

SRNL analyzed samples from Tank 30H, Tank 32H, and Tank 37H to support the Evaporator Feed Qualification and Corrosion Control Programs for the 3H-Evaporator system. The six samples from Tanks 30H, 32H, and 37H all contain highly concentrated salt solutions with sodium concentrations ranging from 11.8 M to 15.7 M. The samples from Tank 30H show somewhat higher concentrations of the major cations and anions in the sub-surface sample than the surface sample indicating some stratification within the tank. The two Tank 32H samples show similar concentrations of the major anions and cations between the surface and sub-surface samples. The sub-surface sample from Tank 37H shows higher concentrations for most species than the surface sample indicating some stratification within this tank as well. For all six samples, the sum of the major cations versus the sum of the major anions shows a difference of <10% providing an indication of good data quality. The VDS and surface samples from Tank 30H, Tank 32H, and Tank 37H all show silicon concentrations below 30 mg/L except for the Tank 30H VDS with a concentration of 87 mg/L.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Analysis of Tank 30H (HTF-30-19-33, -34), Tank 32H (HTF-32-19-35, -36), and Tank 37H (HTF-37-19-53, -54) Samples for Support of the Evaporator Feed Qualification and Corrosion Control Programs for the 3H-Evaporator

SRNL analyzed samples from Tank 30H, Tank 32H, and Tank 37H to support the Evaporator Feed Qualification and Corrosion Control Programs for the 3H-Evaporator system. The six samples from Tanks 30H, 32H, and 37H all contain highly concentrated salt solutions with sodium concentrations ranging from 13.8 M to 16.9 M. Hydroxide is the dominant anion in all of the samples followed by nitrate and nitrite. The preponderance of the analytical determinations (density, anions, cations) on all three tanks show slightly higher concentrations of solute in the sub-surface sample than in the surface sample, indicating some stratification within the tanks. With the exception of the Tank 30H VDS, all of the samples are somewhat more concentrated compared with the compositions of the previous samples. The sum of the major cations versus the sum of the major anions show a difference of <5% for all of the samples indicating good data quality for the non-radioactive analytes in the table. The silicon concentrations measured in the VDS and surface samples from Tank 30H, Tank 32H, and Tank 37H were all below detection.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Analysis of Tank 30H (HTF-30-19-33, -34), Tank 32H (HTF-32-19-35, -36), and Tank 37H (HTF-37- 19-53, -54) Samples for Support of the Evaporator Feed Qualification and Corrosion Control Programs for the 3H-Evaporator

SRNL analyzed samples from Tank 30H, Tank 32H, and Tank 37H to support the Evaporator Feed Qualification and Corrosion Control Programs for the 3H-Evaporator system. The six samples from Tanks 30H, 32H, and 37H all contain highly concentrated salt solutions with sodium concentrations ranging from 13.8 M to 16.9 M. Hydroxide is the dominant anion in all of the samples followed by nitrate and nitrite. The preponderance of the analytical determinations (density, anions, cations) on all three tanks show slightly higher concentrations of solute in the sub-surface sample than in the surface sample, indicating some stratification within the tanks. With the exception of the Tank 30H VDS, all of the samples are somewhat more concentrated compared with the compositions of the previous samples. The sum of the major cations versus the sum of the major anions show a difference of <5% for all of the samples indicating good data quality for the non-radioactive analytes in the table. The silicon concentrations measured in the VDS and surface samples from Tank 30H, Tank 32H, and Tank 37H were all below detection.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Review of corrosion causes and corrosion control in a technical facility

Causes of corrosion of metals and their alloys are reviewed. The corrosion mechanism is explained by electrochemical reaction theory. The causes and methods of controlling of both physiochemical corrosion and biological corrosion are presented. Factors which influence the rate of corrosion are also discussed.

Charng, T.↗

Interactions between phosphate and arsenic in iron/biochar-treated groundwater: Corrosion control insights from column experiments

An increasing number of studies have reported the coexistence of arsenic (As) and phosphorus at high concentrations in groundwater, which threatens human health and increases the complexity of groundwater remediation. However, limited work has been done regarding As interception in the presence of phosphate in flowing systems. In this study, a series of experiments were conducted to evaluate the interactions between phosphate and As during As removal by iron (Fe)-based biochar (FeBC). The addition of phosphate promoted As removal by FeBC in the batch and column experiments. X-ray absorption near edge structure (XANES) analysis provided evidence of simultaneous oxidation and reduction of trivalent arsenic in the FeBC column experiment, accompanied by corrosive Fe oxidation. However, the addition of phosphate enhanced As stabilization, attributed to the As-incorporated Fe-Ca-phosphates precipitates. The involvement of phosphate decelerated the Fe corrosion and the formation of secondary minerals in the column, mediating the risk of passivation and clogging. The As retained by Fe-Ca-phosphate precipitates was more readily oxidized, resulting in higher proportions of pentavalent arsenic. In conclusion, the results of this work identify the corrosion control and sustained-release roles of phosphate in FeBC application, informing the perspective of FeBC in As-contaminated groundwater remediation and providing new insights into the interactions between phosphate and As.

54 ENVIRONMENTAL SCIENCES↗

PROBABILITY BASED CORROSION CONTROL FOR LIQUID WASTE TANKS - PART III

The liquid waste chemistry control program is designed to reduce the pitting corrosion occurrence on tank walls. The chemistry control program has been implemented, in part, by applying engineering judgment safety factors to experimental data. However, the simple application of a general safety factor can result in use of excessive corrosion inhibiting agents. The required use of excess corrosion inhibitors can be costly for tank maintenance, waste processing, and in future tank closure. It is proposed that a probability-based approach can be used to quantify the risk associated with the chemistry control program. This approach can lead to the application of tank-specific chemistry control programs reducing overall costs associated with overly conservative use of inhibitor. Furthermore, when using nitrite as an inhibitor, the current chemistry control program is based on a linear model of increased aggressive species requiring increased protective species. This linear model was primarily supported by experimental data obtained from dilute solutions with nitrate concentrations less than 0.6 M, but is used to produce the current chemistry control program up to 1.0 M nitrate. Therefore, in the nitrate space between 0.6 and 1.0 M, the current control limit is based on assumptions that the linear model developed from data in the <0.6 M region is applicable in the 0.6-1.0 M region. Due to this assumption, further investigation of the nitrate region of 0.6 M to 1.0 M has potential for significant inhibitor reduction, while maintaining the same level of corrosion risk associated with the current chemistry control program. Ongoing studies have been conducted in FY07, FY08, FY09 and FY10 to evaluate the corrosion controls at the SRS tank farm and to assess the minimum nitrite concentrations to inhibit pitting in ASTM A537 carbon steel below 1.0 molar nitrate. The experimentation from FY08 suggested a non-linear model known as the mixture/amount model could be used to predict the probability of corrosion in ASTM A537 in varying solutions as shown in Figure 1. The mixture/amount model takes into account not only the ratio (or mixture) of inhibitors and aggressive species, but also the total concentration (or amount) of species in a solution. Historically, the ratio was the only factor taken into consideration in the development of the current chemistry control program. During FY09, an experimental program was undertaken to refine the mixture/amount model by further investigating the risk associated with reducing the minimum molar nitrite concentration required to confidently inhibit pitting in dilute solutions. The results of FY09, as shown in Figure 2, quantified the probability for a corrosion free outcome for combinations of nitrate and nitrite. The FY09 data predict probabilities up to 70%. Additional experimental data are needed to increase the probability to an acceptable percentage.

36 MATERIALS SCIENCE↗

Relationship Between the Marginal Probability of Failure for a CPP Test and the Recommended Corrosion Control Requirements for Hanford Double Shell Waste Tanks

The Hanford Site in Washington State currently stores millions of gallons of radioactive waste in underground, carbon steel, double shell tanks (DSTs) that were constructed between 1968 and 1986. A chemistry control and monitoring program has been established mitigate corrosion in order to extend the service life for the DSTs. The current waste temperatures in the DSTs are at historical lows (i.e., typically less than 50 °C). The previous chemistry control requirements were determined for conditions at temperatures significantly higher. SRNL undertook a statistically based investigation of the role of nitrate and halide ion (i.e., chloride and fluoride) induced pitting corrosion. The objective was to develop a comprehensive waste chemistry envelope for the simultaneous minimization of the pitting and SCC risks caused by halide and nitrate ions at the lower temperature conditions. On the basis of these tests, new chemistry control requirements were proposed and have since been implemented for pitting corrosion control.

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Corrosion Control Measures For Liquid Radioactive Waste Storage Tanks At The Savannah River Site

The Savannah River Site has stored radioactive wastes in large, underground, carbon steel tanks for approximately 60 years. An assessment of potential degradation mechanisms determined that the tanks may be vulnerable to nitrate- induced pitting corrosion and stress corrosion cracking. Controls on the solution chemistry and temperature of the wastes are in place to mitigate these mechanisms. These controls are based upon a series of experiments performed using simulated solutions on materials used for construction of the tanks. The technical bases and evolution of these controls is presented in this paper.

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Heat Transfer Salts for Nuclear Reactor Systems - Chemistry Control, Corrosion Mitigation, and Modeling

The concept of a molten salt reactor has existed for nearly sixty years. Previously all work was done during a large collaborative effort at Oak Ridge National Laboratory, culminating in a research reactor which operated for 15,000 hours without major error. This technical success has garnished interest in modern, high temperature, reactor schemes. Research using molten fluoride salts for nuclear applications requires a steady supply of high grade molten salts. There is no bulk supplier of research grade fluoride salts in the world, so a facility which could provide all the salt needed for testing at the University of Wisconsin had to be produced. Two salt purification devices were made for this purpose, a large scale purifier, and a small scale purifier, each designed to clean the salts from impurities and reduce their corrosion potential. As of now, the small scale has performed with flibe salt, hydrogen, and hydrogen fluoride, yielding clean salt. This salt is currently being used in corrosion testing facilities at the Massachusetts Institute of Technology and the University of Wisconsin. Working with the beryllium based salts requires extensive safety measures and health monitoring to prevent the development of acute or chronic beryllium disease, two pulmonary diseases created by an allergic reaction to beryllium in the lungs. Extensive health monitoring, engineering controls, and environment monitoring had to be set up with the University of Wisconsin department of Environment, Health and Safety. The hydrogen fluoride required for purification was also an extreme health hazard requiring thoughtful planning and execution. These dangers have made research a slow and tedious process. Simple processes, such as chemical handling and clean-up, can take large amounts of ingenuity and time. Other work has complemented the experimental research at Wisconsin to advance high temperature reactor goals. Modeling work has been performed in house to re-evaluate thermophysical properties of flibe and flinak. Pacific Northwest National Laboratories has focused on evaluating the fluorinating gas nitrogen trifluoride as a potential salt purification agent. Work there was performed on removing hydroxides and oxides from flinak salt under controlled conditions. Lastly, the University of California Berkeley has spent considerable time designing and simulating reactor components with fluoride salts at high temperatures. Despite the hurdles presented by the innate chemical hazards, considerable progress has been made. The stage has been set to perform new research on salt chemical control which could advance the fluoride salt cooled reactor concept towards commercialization. What were previously thought of as chemical undesirable, but nuclear certified, alloys have been shown to be theoretically compatible with fluoride salts at high temperatures. This preliminary report has been prepared to communicate the construction of the basic infrastructure required for flibe, as well as suggest original research to performed at the University of Wisconsin. Simultaneously, the contents of this report can serve as a detailed, but introductory guide to allow anyone to learn the fundamentals of chemistry, engineering, and safety required to work with flibe salt.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

A corrosion control concept by scale engineering: a novel green inhibitor applied for high temperature and pressure aqueous supercritical CO2 systems

Traditional corrosion inhibitors are bio-toxic chemicals with organic components that bond to the fresh metal surface and thus isolate them from corrosive environments. The shortcoming of these inhibitors is that they are less effective in high-temperature and high-pressure environments, and where corrosion scale is formed or particulates are deposited. In this paper, we describe a novel green inorganic inhibitor made of environmentally friendly and cost-effective geo-material that was developed for high-temperature and high-pressure environments, particularly under scale-forming conditions. It inhibits corrosion by enhancing the protectiveness of corrosion scale. In contrast to traditional corrosion inhibitors which are efficient for bare surface corrosion but not effective with scale, the novel inhibitor has no effect on bare surface corrosion but greatly improves corrosion inhibition under scale-formation conditions. This is because a homogeneous scale doped with inhibitor component forms. This enhanced corrosion scale demonstrated excellent protection against corrosion. In high-pressure CO{sub 2} systems (pCO{sub 2}=10 Mpa, T=50 C and [NaCl]=1 wt%) without inhibitor, the bare-surface corrosion rate decreases from ca. 10 mm/y to 0.3 mm/year due to formation of scale. Application of a six hundred ppm solution ofthe new inorganic inhibitor reduced the corrosion rate to 0.01 mm/year, an additional factor of 30. The current inhibitor product was designed for application to CO{sub 2} systems that form corrosion scale, including but not limited to oil and gas wells, offshore production of oil and gas, CO{sub 2} sequestration and enhanced geothermal production involving CO{sub 2}.

03 NATURAL GAS↗

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↗