DEPOSITION TANK CORROSION TESTING FOR ENHANCED CHEMICAL CLEANING POST OXALIC ACID DESTRUCTION

An Enhanced Chemical Cleaning (ECC) process is being developed to aid in the high level waste tank closure at the Savannah River Site. The ECC process uses an advanced oxidation process (AOP) to destroy the oxalic acid that is used to remove residual sludge from a waste tank prior to closure. The AOP process treats the dissolved sludge with ozone to decompose the oxalic acid through reactions with hydroxyl radicals. The effluent from this oxalic acid decomposition is to be sent to a Type III waste tank and may be corrosive to these tanks. As part of the hazardous simulant testing that was conducted at the ECC vendor location, corrosion testing was conducted to determine the general corrosion rate for the deposition tank and to assess the susceptibility to localized corrosion, especially pitting. Both of these factors impact the calculation of hydrogen gas generation and the structural integrity of the tanks, which are considered safety class functions. The testing consisted of immersion and electrochemical testing of A537 carbon steel, the material of construction of Type III tanks, and 304L stainless steel, the material of construction for transfer piping. Tests were conducted in solutions removed from the destruction loop of the prototype ECC set up. Hazardous simulants, which were manufactured at SRNL, were used as representative sludges for F-area and H-area waste tanks. Oxalic acid concentrations of 1 and 2.5% were used to dissolve the sludge as a feed to the ECC process. Test solutions included the uninhibited effluent, as well as the effluent treated for corrosion control. The corrosion control options included mixing with an inhibited supernate and the addition of hydroxide. Evaporation of the uninhibited effluent was also tested since it may have a positive impact on reducing corrosion. All corrosion testing was conducted at 50 C. The uninhibited effluent was found to increase the corrosion rate by an order of magnitude from less than 1 mil per year (mpy) for an inhibited waste to a range of 5 to 23.4 mpy, depending on sludge chemistry. F-area-based effluents were, in general, more corrosive. Effective corrosion control measures included evaporation, hydroxide additions and mixing with supernates containing a representative supernate chemistry (5 M hydroxide and 1.5 M nitrite). Corrosion rates with these measures were generally 0.2 mpy. The A537 carbon steel was found to be susceptible to pitting when the corrosion control measure involved mixing the ECC effluent with a supernate chemistry having minimal inhibitor concentrations (0.5 M hydroxide and 0.3 M nitrite). Corrosion rates in this case were near 1 mpy

Material compatibility evaluation for DWPF nitric-glycolic acid-literature review

Glycolic acid is being evaluated as an alternative for formic and nitric acid in the DWPF flowsheet. Demonstration testing and modeling for this new flowsheet has shown that glycolic acid and glycolate has a potential to remain in certain streams generated during the production of the nuclear waste glass. A literature review was conducted to assess the impact of glycolic acid on the corrosion of the materials of construction for the DWPF facility as well as facilities downstream which may have residual glycolic acid and glycolates present. The literature data was limited to solutions containing principally glycolic acid. The reported corrosion rates and degradation characteristics have shown the following for the materials of construction. For C276 alloy, the primary material of construction for the CPC vessels, corrosion rates of either 2 or 20 mpy were reported up to a temperature of 93 C. For the austenitic stainless steels, 304L and 316L, variable rates were reported over a range of temperatures, varying from 2 mpy up to 200 mpy (at 100 C). For 690, G30, Allcorr, Ultimet and Stellite alloys no data were available. For relevant polymers where data are available, the data suggests that exposure to glycolic acid is not detrimental. The literature data had limited application to the DWPF process since only the storage and feed vessels, pumps and piping used to handle the glycolic acid are directly covered by the available data. These components are either 304L or 316L alloys for which the literature data is inconsistent (See Bullet 2 above). Corrosion rates in pure glycolic acid solutions also are not representative of the DWPF process streams. This stream is complex and contains aggressive species, i.e. chlorides, sulfates, mercury, as well as antifoaming agents which cumulatively have an unknown effect on the corrosion rates of the materials of construction. Therefore, testing is recommended to investigate any synergistic effects of the aggressive species and to verify the performance of materials in the key process vessels as well as downstream vessels and processes such as the evaporator where heating is occurring. The following testing would provide data for establishing the viability of these components. Electrochemical testing - evaluate the corrosion rate and susceptibility to localized corrosion within the SRAT, SME, OGCT, Quencher and Evaporator. Testing would be conducted at operational temperatures in simulants with ranges of glycolic acid, iron, chloride, sulfate, mercury, and antifoaming agents. Hot-wall testing – evaluate the corrosion under heat transfer conditions to simulate those for heating coils and evaporator coil surfaces. Testing would be at nominal chemistries with concentration of glycolic acid, chloride, sulfate and mercury at high expected concentrations. Some tests would be performed with antifoaming agents. Melter coupon testing – evaluate the performance of alloy 690 in melter feeds containing glycolic acid. This testing would be conducted as part of the melter flammability testing. Polymer testing – evaluate changes in polymer properties in immersion testing with DWPF simulants to provide product-specific data for service life evaluation and analyze the Hansen solubility parameters for relevant polymers in glycolic vs. formic acid. During this literature review process, the difficulties associated with measuring the liquid level in formic acid tanks were revealed. A test is recommended to resolve this issue prior to the introduction of glycolic acid into the DWPF. This testing would evaluate the feasibility of using ultrasonic inspection techniques to determine liquid level and other desirable attributes of glycolic acid in DWPF storage tanks and related equipment

ELECTROCHEMICAL STUDIES ON THE CORROSION OF CARBON STEEL IN OXALIC ACID CLEANING SOLUTIONS

The Savannah River Site (SRS) will disperse or dissolve precipitated metal oxides as part of radioactive waste tank closure operations. Previously SRS has utilized oxalic acid to accomplish this task. Since the waste tanks are constructed of carbon steel, a significant amount of corrosion may occur. Although the total amount of corrosion may be insignificant for a short contact time, a significant amount of hydrogen may be generated due to the corrosion reaction. Linear polarization resistance and anodic/cathodic polarization tests were performed to investigate the corrosion behavior during the process. The effect of process variables such as temperature, agitation, aeration, sample orientation, light as well as surface finish on the corrosion behavior were evaluated. The results of the tests provided insight into the corrosion mechanism for the iron-oxalic acid system

RELATIVE HUMIDITY TESTS IN SUPPORT OF THE 3013 STORAGE AND SURVEILLANCE PROGRAM

Techniques to control the initial relative humidity over oxide/salt mixtures have been developed using cerium oxide as a surrogate for plutonium oxide. Such control is required to validate certain assumptions in the Department of Energy Standard DOE-STD-3013, and to provide essential information to support field surveillance at the storage sites for excess plutonium oxides. Concern over the validity of the assumption that corrosion induced degradation in 3013 containers could be controlled by assuring that the moisture content of any stored oxide/salt mixture was below 0.5 w t% arose when stress corrosion cracks were found in test samples exposed at room temperature to plutonium oxide/salt mixtures having a moisture content only marginally above 0.5 wt %. Additionally, analysis of the stress corrosion cracking observations suggests that the initial relative humidity over the oxide/salt mixture may play a major role in the cracking process. The investigations summarized in this report provide the procedures necessary to control the initial relative humidity to selected values within the range of 16 to 50% by controlling the loading relative humidity (18 to 60%) and the oxide/salt mixture water content (0.05 to 0.45 wt %). The studies also demonstrated that the initial relative humidity may be estimated by calculations using software EQ3/6. Cerium oxide/salt mixtures were used in this study because qualification tests with non-radioactive materials will reduce costs while increasing the breadth of the test programs required to support field surveillances of stored 3013 containers

EVALUATION AND RECOMMENDATION OF SALTSTONE MIXER AUGER/PADDLES MATERIALS OF CONSTRUCTION FOR IMPROVED WEAR RESISTANCE

Wear and corrosion testing were conducted to evaluate alternate materials of construction for the Saltstone mixer auger and paddles. These components have been degraded by wear from the slurry processed in the mixer. Material test options included PVD coatings (TiN, TiCN, and ZrN), weld overlays (Stellite 12 and Ultimet) and higher hardness steels and carbides (D2 and tungsten carbide). The corrosion testing demonstrated that the slurry is not detrimental to the current materials of construction or the new candidates. The ASTM G75 Miller wear test showed that the high hardness materials and the Stellite 12 weld overlay provide superior wear relative to the Astralloy and CF8M stainless steel, which are the current materials of construction, as well as the PVD coatings and Ultimet. The following recommendations are made for selecting new material options and improving the overall wear resistance of the Saltstone mixer components: A Stellite 12 weld overlay or higher hardness steel (with toughness equivalent to Astralloy) be used to improve the wear resistance of the Saltstone mixer paddles; other manufacturing specifications for the mixer need to be considered in this selection. The current use of the Stellite 12 weld overlay be evaluated so that coverage of the 316 auger can be optimized for improved wear resistance of the auger. The wear surfaces of the Saltstone mixer auger and paddles be evaluated so that laboratory data can be better correlated to actual service. The 2-inch Saltstone mixer prototype be used to verify material performance

Decontamination of Zircaloy Spent Fuel Cladding Hulls

The reprocessing of commercial spent nuclear fuel (SNF) generates a Zircaloy cladding hull waste which requires disposal as a high level waste in the geologic repository. The hulls are primarily contaminated with fission products and actinides from the fuel. During fuel irradiation, these contaminants are deposited in a thin layer of zirconium oxide (ZrO{sub 2}) which forms on the cladding surface at the elevated temperatures present in a nuclear reactor. Therefore, if the hulls are treated to remove the ZrO{sub 2} layer, a majority of the contamination will be removed and the hulls could potentially meet acceptance criteria for disposal as a low level waste (LLW). Discard of the hulls as a LLW would result in significant savings due to the high costs associated with geologic disposal. To assess the feasibility of decontaminating spent fuel cladding hulls, two treatment processes developed for dissolving fuels containing zirconium (Zr) metal or alloys were evaluated. Small-scale dissolution experiments were performed using the ZIRFLEX process which employs a boiling ammonium fluoride (NH{sub 4}F)/ammonium nitrate (NH{sub 4}NO{sub 3}) solution to dissolve Zr or Zircaloy cladding and a hydrofluoric acid (HF) process developed for complete dissolution of Zr-containing fuels. The feasibility experiments were performed using Zircaloy-4 metal coupons which were electrochemically oxidized to produce a thin ZrO{sub 2} layer on the surface. Once the oxide layer was in place, the ease of removing the layer using methods based on the two processes was evaluated. The ZIRFLEX and HF dissolution processes were both successful in removing a 0.2 mm (thick) oxide layer from Zircaloy-4 coupons. Although the ZIRFLEX process was effective in removing the oxide layer, two potential shortcomings were identified. The formation of ammonium hexafluorozirconate ((NH{sub 4}){sub 2}ZrF{sub 6}) on the metal surface prior to dissolution in the bulk solution could hinder the decontamination process by obstructing the removal of contamination. The thermal decomposition of this material is also undesirable if the cladding hulls are melted for volume reduction or to produce waste forms. Handling and disposal of the corrosive off-gas stream and ZrO{sub 2}-containing dross must be addressed. The stability of Zr{sup 4+} in the NHF{sub 4}/NH{sub 4}NO{sub 3} solution is also a concern. Precipitation of ammonium zirconium fluorides upon cooling of the dissolving solution was observed in the feasibility experiments. Precipitation of the solids was attributed to the high fluoride to Zr ratios used in the experiments. The solubility of Zr{sup 4+} in NH{sub 4}F solutions decreases as the free fluoride concentration increases. The removal of the ZrO{sub 2} layer from Zircaloy-4 coupons with HF showed a strong dependence on both the concentration and temperature. Very rapid dissolution of the oxide layer and significant amounts of metal was observed in experiments using HF concentrations {ge} 2.5 M. Treatment of the coupons using HF concentrations {le} 1.0 M was very effective in removing the oxide layer. The most effective conditions resulted in dissolution rates which were less than approximately 2 mg/cm{sup 2}-min. With dissolution rates in this range, uniform removal of the oxide layer was obtained and a minimal amount of Zircaloy metal was dissolved. Future HF dissolution studies should focus on the decontamination of actual spent fuel cladding hulls to determine if the treated hulls meet criteria for disposal as a LLW

RESULTS OF EXPERIMENT TO DETERMINE CORROSION RATES FOR 304L IN HB-LINE DISSOLVER VESSEL VENTILATION SYSTEM

Radioactive material being processed as part of the DE3013 program for HB-Line will result in the presence of chlorides, and in some cases fluorides, in the dissolver. Material Science and Technology developed an experimental plan to evaluate the impact of chloride on corrosion of the dissolver vessel ventilation system. The plan set test variables from the proposed operating parameters, previous test results, and a desired maximum chloride concentration for processing. The test variables included concentrations of nitric acid, fluorides and chlorides, and the presence of a welded and stressed metal coupon. Table 1 contains expected general corrosion rates in the HB-Line vessel vent system from dissolution of 3013 contents of varying nitric acid and chloride content. These general corrosion rates were measured upstream of the condenser in the experiment's offgas system near the entrance to the dissolver. However, they could apply elsewhere in the offgas system, depending on factors not simulated in the testing, including offgas system temperatures and airflow. Localized corrosion was significant in Tests One, Two, and Three. This corrosion is significant because it will probably be the first mode of penetration of the 304L steel in several places in the system. See Table 2. For Tests One and Three, the penetration rate of localized corrosion was much higher than that for general corrosion. It was approximately four times higher in Test One and at least 45 times higher in Test Three, penetrating an entire coupon thickness of 54 mils in 186 hours or less. There was no significant difference in corrosion between welded areas and un-welded areas on coupons. There was also no significant attack on stressed portions of coupons. It is probable that the lack of corrosion was because the stressed areas were facing downwards and offered no place for condensation or deposits to form. Had deposits formed, pitting may have occurred and led to stress corrosion cracking. The significant localized corrosion observed was usually associated with deposits. General corrosion on the offgas coupons was extremely high for the test containing 10,000 ppm chloride in the dissolver solution. Localized corrosion caused deep penetration of coupon surfaces with a solution of 2000 ppm chloride, both at 12 M and 8 M nitric acid. We recommend that when processing chloride-containing solutions, the pre-condenser side of the vessel vent system be inspected at a frequency calculated from acceptable material losses and expected general corrosion rate. The presence of deposits and heavy condensation during inspection should be taken as indicators of possibly severe localized corrosion

Furniture Rack Corrosion Coupon Surveillance - 2012 Update

Under the L Basin corrosion surveillance program furniture rack coupons immersed for 14 years (FY2009 coupons) and 16 years (FY2011 coupons) were analyzed and the results trended with coupons exposed for shorter times. In addition, a section harvested from an actual furniture rack that was immersed for 14 years was analyzed for pitting in the weld and heat-affected-zone (HAZ) regions. The L Basin operations maintained very good water quality over the entire immersion period for these samples. These results for FY2009 and FY2011 coupons showed that the average pit depths for the 6061 and 6063 base metal are 1 and 2 mils, respectively, while those for the weld and HAZ are 3 and 4 mils, respectively. The results for the weld and HAZ regions are similar to coupons removed during the period of FY2003 to FY2007. These similarities indicate that the pit development occurred quickly followed by slow kinetics of increase in pit depth. For the actual furniture rack sample average pits of 5 and 2 mils were measured for the HAZ and weld, respectively. These results demonstrate that pitting corrosion of the aluminum furniture racks used to support the spent fuel occurs in waters of good quality. The corrosion kinetics or pit depth growth rate is much less that 1 mil/year, and would not impact long-term use of this material system for fuel storage racks in L Basin if good water quality is maintained

DETERMINATION OF CORROSION INHIBITOR CRITERIA FOR TYPE III/IIIA TANKS DURING SALT DISSOLUTION OPERATIONS INTERIM REPORT

Preparation of high level waste for vitrification involves in part the dissolution of salt cake from the carbon steel storage tanks. During dissolution, a point is reached in which the corrosion inhibitors, hydroxide and nitrite, are diluted below established guidelines, and nitrate stress corrosion cracking (SCC) is possible. Because the addition of inhibitors may be counterproductive to process efficiency and waste minimization, corrosion testing was initiated to revisit and possibly revise the guidelines for inhibitor limits. The bases for the work summarized in this status report are results from previously-completed phases of study. In the first two phases of study, several reduced-inhibitor levels were tested in HLW simulants with nitrate concentrations ranging from 4.5 M to 8.5 M. The first two phases of work determined, among other things, the reduced-inhibitor levels and solution chemistries in which heat-treated and non-heat-treated A537 carbon steel is susceptible to SCC, crevice corrosion, and pitting. The work covered in this current task both builds on and verifies the conclusions of the previous work. The current work involves testing of low levels of inhibitors in HLW simulants with 5.5 M to 8.5 M nitrate concentrations. Stressed U-bend specimens, both polarized and non-polarized, were tested. Non-polarized U-bend testing is ongoing, with the U-bends currently in test for 100 days. The purpose of the testing is to determine SCC susceptibility in the vapor space (VS) and liquid air interface (LAI) regions of the HLW tanks under conditions expected during salt dissolution, and also to verify previous accelerated testing. The simulated wastes being tested have nitrate concentrations of 5.5 M and 8.5 M and inhibitor levels of 0.01 M/0.01 M hydroxide/nitrite and 0.1 M/ 0.1 M hydroxide/nitrite. The open circuit potential measurements being monitored and the corrosion morphology of the U-bends are in agreement with results and observations of previous phases of work. No SCC has occurred in the first 100 days of testing. The LAI specimens experienced minor corrosion at the liquid line with corrosion products visible on the weld material and in the heat-affected zones on either side of the welds. The VS specimens are more evenly and slightly more corroded. Polarized U-bend testing is complete after approximately 80 days of testing. No SCC occurred, but the results are inconclusive due to a competing, unexpected galvanic corrosion mechanism that interfered in the last 50 days of testing. No cracking was indicated during the first month. The tests will be repeated in order to satisfy the original objective which was to determine the effect of grinding HLW tank welds and heat treating the tanks had on corrosion. Both the non-polarized and polarized U-bend tests will continue. Additionally, cyclic polarization (CP) testing will be performed to examine the effects of surface oxides on corrosion and the differences in corrosion susceptibility between welded and un-welded areas