Keith S. Matlack

X-ray absorption studies of vanadium valence and local environment in borosilicate waste glasses using vanadium sulfide, silicate, and oxide standards

X-ray absorption spectroscopic data were collected and analyzed to characterize vanadium in borosilicate glasses used for immobilization of sulfur-containing nuclear wastes. Data are presented for borosilicate glasses, some with and some without sulfur, that have V2O5 concentrations as high as 12 wt%, and for the sulfides: sulvanite and patronite, the silicates: cavansite, hadaraite, and roscoelite, and the oxide: vanadinite. X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) data for the glasses have no sulfur dependent features, but do show changes that parallel various redox conditions for the corresponding melts. EXAFS data for the glasses indicate V–O distances near 1.70 A that are considerably shorter than typical V–S distances found in the sulfides. Both XANES and EXAFS indicate that most or all vanadium in these glasses is in the form of V5+O4 tetrahedra; glasses synthesized under reducing conditions can have penta-coordinated V4+ populations up to approximately 20–25% of all vanadium present.

Effect of Fluoride on Crystallization in High Calcium and Magnesium Glasses

Glasses containing fixed mutual ratios of Al, B, Ca, Fe, Mg, Na, and Si were melted while varying the fluoride content. The effect of fluoride was to suppress the formation of non-fluoride-containing crystals in the composition range from 0 to 11 wt. % F; above 11 wt. % F, the formation of fluoride containing crystals began to define the liquidus temperature. The effect of fluoride on the liquidus temperature was quantified and used to predict the liquidus temperature of melts made from real radioactive wastes. Although the liquidus temperatures of the surrogate and radioactive glasses agreed well, the types of crystals formed differed due to slight compositional differences introduced by the waste stream.

Final Report - DuraMelter 100 Tests to Support LAW Glass Formulation Correlation Development, VSL-06R6480-1, Rev. 0

This report describes the results of work and testing specified by Test Specifications 24590-LAW-TSP-RT-04-004, Rev. 0, Test Plans VSL-05T5480-1, Rev. 0 and Text Exceptions 24590-LAW-TEF-RT-05-00002. The work and any associated testing followed established quality assurance requirements and was conducted as authorized. The descriptions provided in this test report are an accurate account of both the conduct of the work and the data collected. Results required by the Test Plan are reported. Also reported are any unusual or anomalous occurences that are different from the starting hypotheses. The test results and this report have been reviewed and verified.

Final Report - Testing of Optimized Bubbler Configuration for HLW Melter VSL-13R2950-1, Rev. 0, dated 6/12/2013

The principal objective of this work was to determine the glass production rate increase and ancillary effects of adding more bubbler outlets to the current WTP HLW melter baseline. This was accomplished through testing on the HLW Pilot Melter (DM1200) at VSL. The DM1200 unit was selected for these tests since it was used previously with several HLW waste streams including the four tank wastes proposed for initial processing at Hanford. This melter system was also used for the development and optimization of the present baseline WTP HLW bubbler configuration for the WTP HLW melter, as well as for MACT testing for both HLW and LAW. Specific objectives of these tests were to: Conduct DM1200 melter testing with the baseline WTP bubbling configuration and as augmented with additional bubblers. Conduct DM1200 melter testing to differentiate the effects of total bubbler air flow and bubbler distribution on glass production rate and cold cap formation. Collect melter operating data including processing rate, temperatures at a variety of locations within the melter plenum space, melt pool temperature, glass melt density, and melter pressure with the baseline WTP bubbling configuration and as augmented with additional bubblers. Collect melter exhaust samples to compare particulate carryover for different bubbler configurations. Analyze all collected data to determine the effects of adding more bubblers to the WTP HLW melter to inform decisions regarding future lid re-designs. The work used a high aluminum HLW stream composition defined by ORP, for which an appropriate simulant and high waste loading glass formulation were developed and have been previously processed on the DM1200.

Final Report - High Level Waste Vitrification System Improvements, VSL-07R1010-1, Rev 0, dated 04/16/07

This report describes work conducted to support the development and testing of new glass formulations that extend beyond those that have been previously investigated for the Hanford Waste Treatment and Immobilization Plant (WTP). The principal objective was to investigate maximization of the incorporation of several waste components that are expected to limit waste loading and, consequently, high level waste (HLW) processing rates and canister count. The work was performed with four waste compositions specified by the Office of River Protection (ORP); these wastes contain high concentrations of bismuth, chromium, aluminum, and aluminum plus sodium. The tests were designed to identify glass formulations that maximize waste loading while meeting all processing and product quality requirements. The work included preparation and characterization of crucible melts in support of subsequent DuraMelter 100 (DM100) tests designed to examine the effects of enhanced glass formulations, increased glass processing temperature, increased crystallinity, and feed solids content on waste processing rate and product quality.

Final Report - LAW Envelope A and B Glass Formulations Testing in Increase Waste Loading. VSL-06R6900-1

This report describes the results of testing specified by the Test Plan VSL-06R6900-1 Rev 0. The work was performed in compliance with quality assurance requirements specified in the Test Plan. Results required by the Test Plan are reported. The test results and this report have been reviewed for correctness, technical adequacy, completeness, and accuracy.

Final Report - LAW Envelope C Glass Formulation Testing to Increase Waste Loading, VSL-05R5900-1

This report describes the results of testing specified by Test Plan VSL-05R5900-1 Rev.0. The work was performed in compliance with the quality assurance requirements specified in the Test Plan. Results required by the Test Plan are reported. The test results and this report have been reviewed for correctness, technical adequacy, completeness, and accuracy.

Final Report - Enhanced LAW Glass Formulation Testing, VSL-07R1130-1, Rev. 0, dated 10/05/07

The principal objective of this work was to extend the glass formulation methodology developed in the earlier work [2, 5, 6] for Envelope A, B and C waste compositions for development of compliant glass compositions targeting five high sodium-sulfur waste loading regions. This was accomplished through a combination of crucible-scale tests, and tests on the DM10 melter system. The DM10 was used for several previous tests on LAW compositions to determine the maximum feed sulfur concentrations that can be processed without forming secondary sulfate phases on the surface of the melt pool. This melter is the most efficient melter platform for screening glass compositions over a wide range of sulfate concentrations and therefore was selected for the present tests. The tests were conducted to provide information on melter processing characteristics and off-gas data, including sulfur incorporation and partitioning. As described above, the main objective was to identify the limits of waste loading in compliant glass formulations spanning the range of expected Na{sub 2}O and SO{sub 3} concentrations in the LAW glasses.

Final Report - Effects of High Spinel and Chromium Oxide Crystal Contents on Simulated HLW Vitrification in DM100 Melter Tests, VSL-09R1520-1, Rev. 0, dated 6/22/09

The principal objective of the work was to evaluate the effects of spinel and chromium oxide particles on WTP HLW melter operations and potential impacts on melter life. This was accomplished through a combination of crucible-scale tests, settling and rheological tests, and tests on the DM100 melter system. Crucible testing was designed to develop and identify HLW glass compositions with high waste loadings that exhibit formation of crystalline spinel and/or chromium oxide phases up to relatively high crystal contents (i.e., > 1 vol%). Characterization of crystal settling and the effects on melt rheology was performed on the HLW glass formulations. Appropriate candidate HLW glass formulations were selected, based on characterization results, to support subsequent melter tests. In the present work, crucible melts were formulated that exhibit up to about 4.4 vol% crystallization.

Final Report - Melt Rate Enhancement for High Aluminum HLW Glass Formulation, VSL-08R1360-1, Rev. 0, dated 12/19/08

The principal objective of the work reported here was to develop and identify HLW glass compositions that maximize waste processing rates for the aluminum limted waste composition specified by ORP while maintaining high waste loadings and acceptable glass properties. This was accomplished through a combination of crucible-scale tests, confirmation tests on the DM100 melter system, and demonstration at pilot scale (DM1200). The DM100-BL unit was selected for these tests since it was used previously with the HLW waste streams evaluated in this study, was used for tests on HLW glass compositions to support subsequent tests on the HLW Pilot Melter, conduct tests to determine the effect of various glass properties (viscosity and conductivity) and oxide concentrations on glass production rates with HLW feed streams, and to assess the volatility of cesium and technetium during the vitrification of an HLW AZ-102 composition. The same melter was selected for the present tests in order to maintain comparisons between the previously collected data. These tests provide information on melter processing characteristics and off-gas data, including formation of secondary phases and partitioning. Once DM100 tests were completed, one of the compositions was selected for further testing on the DM1200; the DM1200 system has been used for processing a variety of simulated Hanford waste streams. Tests on the larger melter provide processing data at one third of the scale of the actual WTP HLW melter and, therefore, provide a more accurate and reliable assessment of production rates and potential processing issues. The work focused on maximizing waste processing rates for high aluminum HLW compositions. In view of the diversity of forms of aluminum in the Hanford tanks, tests were also conducted on the DM100 to determine the effect of changes in the form of aluminum on feed properties and production rate. In addition, the work evaluated the effect on production rate of modest increases in melter operating temperature. Glass composition development was based on one of the HLW waste compositions specified by ORP that has a high concentration of aluminum. Small-scale tests were used to provide an initial screening of various glass formulations with respect to melt rates; more definitive screening was provided by the subsequent DM100 tests. Glass properties evaluated included: viscosity, electrical conductivity, crystallinity, gross glass phase separation and the 7- day Product Consistency Test (ASTM-1285). Glass property limits were based upon the reference properties for the WTP HLW melter. However, the WTP crystallinity limit (< 1 vol% at 950oC) was relaxed slightly as a waste loading constraint for the crucible melts.