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Title: FY2016 ILAW Glass Corrosion Testing with the Single-Pass Flow-Through Method

Abstract

The inventory of immobilized low-activity waste (ILAW) produced at the Hanford Tank Waste Treatment and Immobilization Plant (WTP) will be disposed of at the near-surface, on-site Integrated Disposal Facility (IDF). When groundwater comes into contact with the waste form, the glass will corrode and radionuclides will be released into the near-field environment. Because the release of the radionuclides is dependent on the dissolution rate of the glass, it is important that the performance assessment (PA) model accounts for the dissolution rate of the glass as a function of various chemical conditions. To accomplish this, an IDF PA model based on Transition State Theory (TST) can be employed. The model is able to account for changes in temperature, exposed surface area, and pH of the contacting solution as well as the effect of silicon concentrations in solution, specifically the activity of orthosilicic acid (H4SiO4), whose concentration is directly linked to the glass dissolution rate. In addition, the IDF PA model accounts for the alkali-ion exchange process as sodium is leached from the glass and into solution. The effect of temperature, pH, H4SiO4 activity, and the rate of ion-exchange can be parameterized and implemented directly into the PA rate law model. Themore » rate law parameters are derived from laboratory tests with the single-pass flow-through (SPFT) method. To date, rate law parameters have been determined for seven ILAW glass compositions, thus additional rate law parameters on a wider range of compositions will supplement the existing body of data for PA maintenance activities. The data provided in this report can be used by ILAW glass scientists to further the understanding of ILAW glass behavior, by IDF PA modelers to use the rate law parameters in PA modeling efforts, and by Department of Energy (DOE) contractors and decision makers as they assess the IDF PA program.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1365447
Report Number(s):
PNNL-26169; RPT-IGTP-013 Rev. 0.0
830403000
DOE Contract Number:
AC05-76RL01830
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE WASTES FROM NUCLEAR FACILITIES

Citation Formats

Neeway, James J., Asmussen, Robert M., Parruzot, Benjamin PG, Cordova, Elsa, Williams, Benjamin D., Leavy, Ian I., Stephenson, John R., and McElroy, Erin M.. FY2016 ILAW Glass Corrosion Testing with the Single-Pass Flow-Through Method. United States: N. p., 2017. Web. doi:10.2172/1365447.
Neeway, James J., Asmussen, Robert M., Parruzot, Benjamin PG, Cordova, Elsa, Williams, Benjamin D., Leavy, Ian I., Stephenson, John R., & McElroy, Erin M.. FY2016 ILAW Glass Corrosion Testing with the Single-Pass Flow-Through Method. United States. doi:10.2172/1365447.
Neeway, James J., Asmussen, Robert M., Parruzot, Benjamin PG, Cordova, Elsa, Williams, Benjamin D., Leavy, Ian I., Stephenson, John R., and McElroy, Erin M.. Fri . "FY2016 ILAW Glass Corrosion Testing with the Single-Pass Flow-Through Method". United States. doi:10.2172/1365447. https://www.osti.gov/servlets/purl/1365447.
@article{osti_1365447,
title = {FY2016 ILAW Glass Corrosion Testing with the Single-Pass Flow-Through Method},
author = {Neeway, James J. and Asmussen, Robert M. and Parruzot, Benjamin PG and Cordova, Elsa and Williams, Benjamin D. and Leavy, Ian I. and Stephenson, John R. and McElroy, Erin M.},
abstractNote = {The inventory of immobilized low-activity waste (ILAW) produced at the Hanford Tank Waste Treatment and Immobilization Plant (WTP) will be disposed of at the near-surface, on-site Integrated Disposal Facility (IDF). When groundwater comes into contact with the waste form, the glass will corrode and radionuclides will be released into the near-field environment. Because the release of the radionuclides is dependent on the dissolution rate of the glass, it is important that the performance assessment (PA) model accounts for the dissolution rate of the glass as a function of various chemical conditions. To accomplish this, an IDF PA model based on Transition State Theory (TST) can be employed. The model is able to account for changes in temperature, exposed surface area, and pH of the contacting solution as well as the effect of silicon concentrations in solution, specifically the activity of orthosilicic acid (H4SiO4), whose concentration is directly linked to the glass dissolution rate. In addition, the IDF PA model accounts for the alkali-ion exchange process as sodium is leached from the glass and into solution. The effect of temperature, pH, H4SiO4 activity, and the rate of ion-exchange can be parameterized and implemented directly into the PA rate law model. The rate law parameters are derived from laboratory tests with the single-pass flow-through (SPFT) method. To date, rate law parameters have been determined for seven ILAW glass compositions, thus additional rate law parameters on a wider range of compositions will supplement the existing body of data for PA maintenance activities. The data provided in this report can be used by ILAW glass scientists to further the understanding of ILAW glass behavior, by IDF PA modelers to use the rate law parameters in PA modeling efforts, and by Department of Energy (DOE) contractors and decision makers as they assess the IDF PA program.},
doi = {10.2172/1365447},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Fri Apr 21 00:00:00 EDT 2017},
month = {Fri Apr 21 00:00:00 EDT 2017}
}

Technical Report:

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  • This status report provides a FY2016 update on work performed to collect information on the corrosion behavior of LAW glasses to support the IDF PA. In addition to the development of the baseline operating envelope for the WTP, since 2003, VSL has developed a wide range of LAW formulations that achieve considerably higher waste loadings than the WTP baseline formulations.
  • An international interlaboratory study (ILS) was conducted to evaluate the precision with which single-pass flow-through (SPFT) tests can be conducted by following a method to be standardized by the American Society for Testing and Materials - International. Tests for the ILS were conducted with the low-activity reference material (LRM) glass developed previously for use as a glass test standard. Tests were conducted at 70 {+-} 2 C using a LiCl/LiOH solution as the leachant to impose an initial pH of about 10 (at 70 C). Participants were provided with LRM glass that had been crushed and sieved to isolate themore » -100 +200 mesh size fraction, and then washed to remove fines. Participants were asked to conduct a series of tests using different solution flow rate-to-sample mass ratios to generate a range of steady-state Si concentrations. The glass dissolution rate under each test condition was calculated using the steady-state Si concentration and solution flow rate that were measured in the test. The glass surface area was estimated from the mass of glass used in the test and the Si content of LRM glass was known. A linear relationship between the rate and the steady-state Si concentration (at Si concentrations less than 10 mg/L) was used to estimate the forward dissolution rate, which is the rate in the absence of dissolved Si. Participants were asked to sample the effluent solution at least five times after reaction times of between 3 and 14 days to measure the Si concentration and flow rate, and to verify that steady-state was achieved. Results were provided by seven participants and the data sets provided by five participants were sufficient to determine the forward rates independently.« less
  • This report summarizes our findings from pressurized unsaturated flow (PUF) and single-pass flow-through (SPFT) experiments to date. Results from the PUF test of a Pu-bearing ceramic with enclosing surrogate high-level waste glass show that the glass reacts rapidly to alteration products. Glass reaction causes variations in the solution pH in contact with the ceramic materials. We also document variable concentrations of Pu in solution, primarily in colloidal form, which appear to be related to secular variations in solution composition. The apparent dissolution rate of the ceramic waste form, based on Ba concentrations in the effluent, is estimated at {le} 10{supmore » {minus}5} g/(m{sup 2} {center_dot} d). Pu-bearing colloids were recovered in the size range of 0.2 to 2 {micro}m, but it is not clear that such entities would be transported in a system that is not advective-flow dominated. Results from SPFT experiments give information on the corrosion resistance of two surrogate Pu-ceramics (Ce-pyrochlore and Ce-zirconolite) at 90 C over a pH range of 2 to 12. The two ceramics were doped with minor quantities ({approximately}0.1 mass%) of MoO{sub 3}, so that concentrations of Mo in the effluent solution could be used to monitor the reaction behavior of the materials. The data obtained thus far from experiments with durations up to 150 d do not conclusively prove that the solid-aqueous solution systems have reached steady-state conditions. Therefore, the dissolution mechanism cannot be determined. Apparent dissolution rates of the two ceramic materials based on Ce, Gd, and Mo concentrations in the effluent solutions from the SPFT are nearly identical and vary between 1.1 to 8.5 x 10{sup {minus}4} g/(m{sup 2} {center_dot} d). In addition, the data reveal a slightly amphoteric dissolution behavior, with a minimum apparent rate at pH = 7 to 8, over the pH range examined. Results from two related ceramic samples suggest that radiation damage can have a measurable effect on the dissolution of titanium-based ceramics. The rare earth pyrochlores, Gd{sub 2}Ti{sub 2}O{sub 7} and Lu{sub 2}Ti{sub 2}O{sub 7}, are being studied as part of the DOE Environmental Management Science Program, and the results are germane to this study. The corrosion resistances of both heavy-ion bombarded and pristine (non-bombarded) specimens are being examined with the SPFT test. Initial data indicate that the dissolution rate may increase by a factor of 3 times or more when these materials become amorphous from radiation damage.« less
  • Static dissolution tests were conducted to measure the forward dissolution rate of LRM glass at 70 C and pH(RT) 11.7 {+-} 0.1 for comparison with the rate measured with single-pass flow-through (SPFT) tests in an interlaboratory study (ILS). The static tests were conducted with monolithic specimens having known geometric surface areas, whereas the SPFT tests were conducted with crushed glass that had an uncertain specific surface area. The error in the specific surface area of the crushed glass used in the SPFT tests, which was calculated by modeling the particles as spheres, was assessed based on the difference in themore » forward dissolution rates measured with the two test methods. Three series of static tests were conducted at 70 C following ASTM standard test method C1220 using specimens with surfaces polished to 600, 800, and 1200 grit and a leachant solution having the same composition as that used in the ILS. Regression of the combined results of the static tests to the affinity-based glass dissolution model gives a forward rate of 1.67 g/(m{sup 2}d). The mean value of the forward rate from the SPFT tests was 1.64 g/(m{sup 2}d) with an extended uncertainty of 1.90 g/(m{sup 2}d). This indicates that the calculated surface area for the crushed glass used in the SPFT tests is less than 2% higher than the actual surface area, which is well within the experimental uncertainties of measuring the forward dissolution rate using each test method. These results indicate that the geometric surface area of crushed glass calculated based on the size of the sieves used to isolate the fraction used in a test is reliable. In addition, the C1220 test method provides a means for measuring the forward dissolution rate of borosilicate glasses that is faster, easier, and more economical than the SPFT test method.« less
  • Two samples of fluidized-bed steam reforming (FBSR) mineral waste form product were subjected to single-pass flow-through (SPFT) testing. Sample LAW 1123 resulted from pilot-scale FBSR processing with a Hanford Envelope A low-activity waste (LAW) simulant. Sample SBW 1173 resulted from pilot-scale FBSR processing with an Idaho National Laboratory (INL) simulant commonly referred to as sodium-bearing waste (SBW). The pilot-scale waste forms were made at the Science and Technology Applications Research (STAR) facility in Idaho Falls, Idaho. The durability of the two FBSR waste forms was assessed via the SPFT test in this study. Both samples were multiphase mineral waste forms,more » so the SPFT test results provide an overall release rate from the multiple mineral species in each sample and are dependent on the amount of each phase present and the mineralogy of the phases present. SPFT testing was performed at temperatures of 25, 40, 70, and 90 C on LAW 1123, while SBW 1173 was only tested at 70 and 90 C. The 70 and 90 C data were compared to each other and the LAW-1123 results were compared to previous testing performed by the Pacific Northwest National Laboratory (PNNL) on a LAW Envelope C (high organic content) waste simulant. The objectives of this study were to obtain forward dissolution rate data for both STAR FBSR bed products (using SPFT tests). Also, a qualitative comparison of the FBSR bed products to a glass waste form (specifically the low-activity reference material (LRM) glass) was performed. For these comparisons, the relative surface areas of the FBSR and glass products had to be measured. Due to the more porous and irregular surface of FBSR bed products, the surface area of the bed products was determined using the Brunauer, Emmett, and Teller (BET) measurement method. The surface area of a glass is much smoother and the calculated geometric surface area is typically used for determining dissolution behavior. Presently there are no specifications or standard release rates that the FBSR tested materials have to meet, e.g. the data from the FBSR testing is normally used during subsequent Performance Assessment (PA) calculations. Since a PA calculation is not part of this study, the LAW and SBW steam reforming samples were compared to each other, to previous LAW FBSR SPFT results, and to the results from the LRM reference glass. The experimental durability data generated from this study suggests that an FBSR mineral waste form product would be an adequate alternative form to borosilicate glass. The tested FBSR mineral waste forms showed normalized release rates for matrix elements such as Si to be more than 200X slower than the LRM glass. However, further durability testing and mineral phase information is recommended to further substantiate these findings.« less