skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Comparison of the results of short-term static tests and single-pass flow-through tests with LRM glass.

Abstract

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 the 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 themore » 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

Authors:
;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
925334
Report Number(s):
ANL-06/51
TRN: US200809%%666
DOE Contract Number:
DE-AC02-06CH11357
Resource Type:
Technical Report
Country of Publication:
United States
Language:
ENGLISH
Subject:
36 MATERIALS SCIENCE; BOROSILICATE GLASS; DISSOLUTION; SURFACE AREA; MATERIALS TESTING

Citation Formats

Ebert, W. L., and Chemical Engineering. Comparison of the results of short-term static tests and single-pass flow-through tests with LRM glass.. United States: N. p., 2007. Web. doi:10.2172/925334.
Ebert, W. L., & Chemical Engineering. Comparison of the results of short-term static tests and single-pass flow-through tests with LRM glass.. United States. doi:10.2172/925334.
Ebert, W. L., and Chemical Engineering. Mon . "Comparison of the results of short-term static tests and single-pass flow-through tests with LRM glass.". United States. doi:10.2172/925334. https://www.osti.gov/servlets/purl/925334.
@article{osti_925334,
title = {Comparison of the results of short-term static tests and single-pass flow-through tests with LRM glass.},
author = {Ebert, W. L. and Chemical Engineering},
abstractNote = {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 the 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.},
doi = {10.2172/925334},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Mon Jan 29 00:00:00 EST 2007},
month = {Mon Jan 29 00:00:00 EST 2007}
}

Technical Report:

Save / Share:
  • 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
  • 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 onmore » 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.« less
  • A single-pass continuous-flow leach test of PNL 76-68 glass beads (7 mm dia) was concluded after 420 days of uninterrupted operation. Variables included in the experimental matrix were flow-rate, leachant composition, and temperature. Analysis was conducted on all leachate samples for /sup 237/Np and /sup 239/Pu as well as a number of nonradioactive elements. Results indicated that flow-rate and leachant systematically affected the leach rate, but only slightly. Temperature effects were significant. Plutonium leach rate was lower at higher temperature suggesting that Pu sorption onto the beads was enhanced at the higher temperature. The range of leach rates for allmore » analyzed elements (except Pu), at both temperatures, at all three flow rates, and with all three leachant compositions varied over only three orders of magnitude. The range of variables used in this experiment covered those expected in many proposed repository environments.« less
  • This report updates work on measurements of the dissolution rates of single-phase and multi-phase ceramic waste forms in flow-through reactors at Lawrence Livermore National Laboratory. Previous results were reported in Bourcier (1999). Two types of tests are in progress: (1) tests of baseline pyrochlore-based multiphase ceramics; and (2) tests of single-phase pyrochlore, zirconolite, and brannerite (the three phases that will contain most of the actinides). Tests of the multi-phase material are all being run at 25 C. The single-phase tests are being run at 25, 50, and 75 C. All tests are being performed at ambient pressure. The as-made bulkmore » compositions of the ceramics are given in Table 1. The single pass flow-through test procedure [Knauss, 1986 No.140] allows the powdered ceramic to react with pH buffer solutions traveling upward vertically through the powder. Gentle rocking during the course of the experiment keeps the powder suspended and avoids clumping, and allows the system to behave as a continuously stirred reactor. For each test, a cell is loaded with approximately one gram of the appropriate size fraction of powdered ceramic and reacted with a buffer solution of the desired pH. The buffer solution compositions are given in Table 2. All the ceramics tested were cold pressed and sintered at 1350 C in air, except brannerite, which was sintered at 1350 C in a CO/CO{sub 2} gas mixture. They were then crushed, sieved, rinsed repeatedly in alcohol and distilled water, and the desired particle size fraction collected for the single pass flow-through tests (SPFT). The surface area of the ceramics measured by BET ranged from 0.1-0.35 m{sup 2}/g. The measured surface area values, average particle size, and sample weights for each ceramic test are given in the Appendices.« less