EM-21 HIGHER WASTE LOADING GLASSES FOR ENHANCED DOE HIGH-LEVEL WASTE MELTER THROUGHPUT STUDIES - 10194

Supplemental validation data has been generated that will be used to determine the applicability of the current Defense Waste Processing Facility (DWPF) liquidus temperature (T{sub L}) model to expanded DWPF glass regions of interest based on higher waste loadings. For those study glasses which had very close compositional overlap with the model development and/or model validation ranges (except TiO{sub 2} and MgO concentrations), there was very little difference in the predicted and measured TL values, even though the TiO{sub 2} contents were above the 2 wt% upper limit. The results indicate that the current T{sub L} model is applicable in these compositional regions. As the compositional overlap between the model validation ranges diverged from the target glass compositions, the T{sub L} data suggest that the model under-predicted the measured values. These discrepancies imply that there are individual oxides or their combinations that were outside of the model development and/or validation range over which the model was previously assessed. These oxides include B{sub 2}O{sub 3}, SiO{sub 2}, MnO, TiO{sub 2} and/or their combinations. More data is required to fill in these anticipated DWPF compositional regions so that the model coefficients could be refit to account for these differences

ENHANCED DOE HIGH LEVEL WASTE MELTER THROUGHPUT STUDIES: SRNL GLASS SELECTION STRATEGY

The Department of Energy has authorized a team of glass formulation and processing experts at the Savannah River National Laboratory (SRNL), the Pacific Northwest National Laboratory (PNNL), and the Vitreous State Laboratory (VSL) at Catholic University of America to develop a systematic approach to increase high level waste melter throughput (by increasing waste loading with minimal or positive impacts on melt rate). This task is aimed at proof-of-principle testing and the development of tools to improve waste loading and melt rate, which will lead to higher waste throughput. Four specific tasks have been proposed to meet these objectives (for details, see WSRC-STI-2007-00483): (1) Integration and Oversight, (2) Crystal Accumulation Modeling (led by PNNL)/Higher Waste Loading Glasses (led by SRNL), (3) Melt Rate Evaluation and Modeling, and (4) Melter Scale Demonstrations. Task 2, Crystal Accumulation Modeling/Higher Waste Loading Glasses is the focus of this report. The objective of this study is to provide supplemental data to support the possible use of alternative melter technologies and/or implementation of alternative process control models or strategies to target higher waste loadings (WLs) for the Defense Waste Processing Facility (DWPF)--ultimately leading to higher waste throughputs and a reduced mission life. The glass selection strategy discussed in this report was developed to gain insight into specific technical issues that could limit or compromise the ability of glass formulation efforts to target higher WLs for future sludge batches at the Savannah River Site (SRS). These technical issues include Al-dissolution, higher TiO{sub 2} limits and homogeneity issues for coupled-operations, Al{sub 2}O{sub 3} solubility, and nepheline formation. To address these technical issues, a test matrix of 28 glass compositions has been developed based on 5 different sludge projections for future processing. The glasses will be fabricated and characterized based on the protocols outlined in the SRNL Task and Quality Assurance (QA) plan

SLUDGE BATCH 5 VARIABILITY STUDY WITH FRIT 418

The Defense Waste Processing Facility (DWPF) is preparing to initiate processing Sludge Batch 5 (SB5) in early FY 2009. In support of the upcoming processing, the Savannah River National Laboratory (SRNL) provided a recommendation to utilize Frit 418 as a transitional frit to initiate processing of SB5. This recommendation was based on the results of assessments on the compositional projections for SB5 available at that time from both the Liquid Waste Organization (LWO) and SRNL (using a model-based approach). To support qualification of the Frit 418-SB5 system, SRNL executed a variability study to assess the acceptability of the Frit 418-SB5 glasses with respect to durability and the applicability of the current durability models. Twenty one glasses were selected for the variability study based on the available SB5 projections primarily spanning a waste loading (WL) range of 25-37%. In order to account for the addition of caustic to Tank 40, which occurred in July 2008, 3 wt% Na2O was added to the original Tank 40 heel projections. The addition of the Actinide Removal Process (ARP) stream to the blend composition was also included. Two of the glasses were fabricated at 25% and 28% WL in order to challenge the homogeneity constraint of the Product Composition Control System (PCCS) for SB5 coupled operations. These twenty one glasses were fabricated and characterized using chemical composition analysis, X-ray Diffraction (XRD) and the Product Consistency Test (PCT). The results of this study indicate that Frit 418 is a viable option for sludge-only and coupled operations. The addition of ARP did not have any negative impacts on the acceptability and predictability of the variability study glasses. Based on the measured PCT response, all of the glasses were acceptable as compared to the Environmental Assessment (EA) reference glass regardless of the thermal history and were also predictable using the current PCCS model for durability. The homogeneity constraint can be ignored for SB5 for coupled operations (based on the Appendix J compositional information), as both of the glasses targeting lower WLs (SB5VS-18 and SB5VS-19) had durabilities that were acceptable with respect to the reference EA glass

THE IMPACT OF A TANK 40H DECANT ON THE PROJECTED OPERATING WINDOWS FOR SB4 AND GLASS SELECTION STRATEGY IN SUPPORT OF THE VARIABILITY STUDY

The Liquid Waste Organization (LWO) has requested that the Savannah River National Laboratory (SRNL) to assess the impact of a 100K gallon decant volume from Tank 40H on the existing sludge-only Sludge Batch 4 (SB4)-Frit 510 flowsheet and the coupled operations flowsheet (SB4 with the Actinide Removal Process (ARP)). Another potential SB4 flowsheet modification of interest includes the addition of 3 wt% sodium (on a calcined oxide basis) to a decanted sludge-only or coupled operations flowsheet. These potential SB4 flowsheet modifications could result in significant compositional shifts to the SB4 system. This paper study provides an assessment of the impact of these compositional changes to the projected glass operating windows and to the variability study for the Frit 510-SB4 system. The influence of the compositional changes on melt rate was not assessed in this study nor was it requested. Nominal Stage paper study assessments were completed using the projected compositions for the various flowsheet options coupled with Frit 510 (i.e., variation was not applied to the sludge and frit compositions). In order to gain insight into the impacts of sludge variation and/or frit variation (due to the procurement specifications) on the projected operating windows, three versions of the Variation Stage assessment were performed: (1) the traditional Variation Stage assessment in which the nominal Frit 510 composition was coupled with the extreme vertices (EVs) of each sludge, (2) an assessment of the impact of possible frit variation (within the accepted frit specification tolerances) on each nominal SB4 option, and (3) an assessment of the impact of possible variation in the Frit 510 composition due to the vendor's acceptance specifications coupled with the EVs of each sludge case. The results of the Nominal Stage assessment indicate very little difference among the various flowsheet options. All of the flowsheets provide DWPF with the possibility of targeting waste loadings (WLs) from the low 30s to the low 40s with Frit 510. In general, the Tank 40H decant has a slight negative impact on the operating window, but DWPF still has the ability to target current WLs (34%) and higher WLs if needed. While the decant does not affect practical WL targets in DWPF, melt rate could be reduced due to the lower Na{sub 2}O content. If true, the addition of 3 wt% Na{sub 2}O to the glass system may regain melt rate, assuming that the source of alkali is independent of the impact on melt rate. Coupled operations with Frit 510 via the addition of ARP to the decanted SB4 flowsheet also appears to be viable based on the projected operating windows. The addition of both ARP and 3 wt% Na{sub 2}O to a decanted Tank 40H sludge may be problematic using Frit 510. Although the Nominal Stage assessments provide reasonable operating windows for the SB4 flowsheets being considered with Frit 510, introduction of potential sludge and/or frit compositional variation does have a negative impact. The magnitude of the impact on the projected operating windows is dependent on the specific flowsheet options as well as the applied variation. The results of the traditional Variation Stage assessments indicate that the three proposed Tank 40H decanted flowsheet options (Case No.2--100K gallon decant, Case No.3--100K gallon decant and 3 wt% Na{sub 2}O addition and Case No.4--100K gallon decant and ARP) demonstrate a relatively high degree of robustness to possible sludge variation over WLs of interest with Frit 510. However, the case where the addition of both ARP and 3 wt% Na{sub 2}O is considered was problematic during the traditional Variation Stage assessment. The impact of coupling the frit specifications with the nominal SB4 flowsheet options on the projected operating windows is highly dependent on whether the upper WLs are low viscosity or liquidus temperature limited in the Nominal Stage assessments. Systems that are liquidus temperature limited exhibit a high degree of robustness to the applied frit and sludge variation, while those that are low viscosity limited show significant reductions (6 percentage points) in the upper WLs that can be obtained. When both frit and sludge variations are applied, the paper study results indicate that DWPF could be severely restricted in terms of projected operating windows for the ARP and Na{sub 2}O addition options. An experimental variability study was not performed using the final SB4 composition and Frit 510 since glasses in the ComPro{trademark} data base were identified that bounded the potential operating window of this system. The bounding ARP case was not considered in that assessment. After the flowsheet cases were identified, an electronic search of ComPro{trademark} identified approximately 12 historical glasses within the compositional regions defined by at least one of the five flowsheet options, but the compositional coverage did not appear adequate to bound all cases

PREPARATION AND CHARACTERIZATION OF POROUS WALLED HOLLOW GLASS MICROSPHERES

Porous-walled hollow glass microspheres (PWHGMs) of a modified alkali borosilicate composition have been successfully fabricated by combining the technology of producing hollow glass microspheres (HGMs) with the knowledge associated with porous glasses. HGMs are first formed by a powder glass--flame process, which are then transformed to PWHGMs by heat treatment and subsequent treatment in acid. Pore diameter and pore volume are most influenced by heat treatment temperature. Pore diameter is increased by a factor of 10 when samples are heat treated prior to acid leaching; 100 {angstrom} in non-heat treated samples to 1000 {angstrom} in samples heat treated at 600 C for 8 hours. As heat treatment time is increased from 8 hours to 24 hours there is a slight shift increase in pore diameter and little or no change in pore volume

IMPACT OF COMPOSITION AND HEAT TREATMENT ON PORE SIZE IN POROUS WALLED HOLLOW GLASS MICROSPHERES

The Savannah River National Laboratory (SRNL) developed a new geometric form: hollow glass microspheres (HGMs), with unique porous walls. The new geometric form combines the existing technology of HGMs with basic glass science knowledge in the realm of glass-in-glass phase separation. Conceptually, the development of a HGM with porous walls (referred to as a PWHGM) provides a unique system in which various media or filling agents can be incorporated into the PWHGM (via transport through the porous walls) and ultimately has the capacity to serve as a functional delivery system in various industrial applications. Applications of these types of systems could range from hydrogen storage, molecular sieves, drug and bioactive delivery systems, to environmental, chemical and biological indicators, relevant to Energy, Environmental Processing and Homeland Security fields. As a specific example, previous studies at SRNL have introduced materials capable of hydrogen storage (as well as other materials) into the interior of the PWHGMs. The goal of this project was to determine if the microstructure (i.e., pore size and pore size distribution) of a PWHGM could be altered or tailored by varying composition and/or heat treatment (time and/or temperature) conditions. The ability to tailor the microstructure through composition or heat treatments could provide the opportunity to design the PWHGM system to accommodate different additives or fill agents. To meet this objective, HGMs of various alkali borosilicate compositions were fabricated using a flame forming apparatus installed at the Aiken County Technical Laboratory (ACTL). HGMs were treated under various heat treatment conditions to induce and/or enhance glass in glass phase separation. Heat treatment temperatures ranged from 580 C to 620 C, while heat treatment times were either 8 or 24 hours. Of the two primary variables assessed in this study, heat treatment temperature was determined to be most effective in changing the porosity of PWHGMs. Pore diameter in a non-heat treated baseline sample is approximately 100 {angstrom} and with heat treatment at 600 C for 8 hours, the diameter is approximately 1000 {angstrom}; an increase of a factor of 10. The results of this study also indicate significant microstructural differences with only a 20 C difference in heat treatment temperature (580 C and 600 C) for constant times. The microstructural changes observed via electron microscopy as a function of heat treatment temperature were confirmed by mercury porosimetry measurements, where considerable increases in pore volume were measured. Under constant heat treatment conditions, composition may impose a secondary effect on the resulting microstructure as micrographs indicate variations in the degree of porosity. Although microstructural differences were observed among the compositions assessed, the magnitude of the impact (i.e., difference in pore size or pore volume) appears to be smaller than that associated with heat treatment temperature. With respect to heat treatment time, the results suggest that the change in the degree of porosity is minimal for samples heat treated between 8 and 24 hours (it should be noted that the assessment of the impact of time on the resulting microstructure was limited to two compositions). The minimal impact of heat treatment time (on the two glasses evaluated) was confirmed by mercury porosimetry measurements indicating that there was a very slight shift in pore diameter and very little increase in pore volume in the baseline sample. Another important parameter, which will need to be considered under manufacturing or operational conditions, is the yield of the HGM and/or PWHGM and the characteristics of the final product (i.e., not only microstructure characteristics, but perhaps strength of the PWHGM for use under certain applications). In this report, yield is defined as the percentage of feed material converted to HGMs or the percentage of HGMs converted to PWHGMs. The yield of HGM formation was found to be a strong function of composition. As the SiO{sub 2} and B{sub 2}O{sub 3} contents are increased or decreased from the baseline composition, the yield is reduced. PWHGM yield doesn't appear to be influenced by composition, but there is a noticeable increase in yield when comparing the non-heat treated samples to those that were heat treated prior to acid leaching. The results of this study suggest that PWHGM microstructures (pore size and pore volume) can be tailored or specifically designed to meet different end-user needs within certain limitations. The primary effect on the resulting microstructure is heat treatment temperature, which can produce a significant shift in pore size or volume even with a very small difference in heat treatment temperature (20 C). The ability to control the microstructure of PWHGMs provides the opportunity to design the PWHGM system to accommodate different additives or fill agents as required

VARIABILITY STUDY WITH FRIT 510 TO SUPPORT A SECOND TANK 40 DECANT

Sludge Batch 4 (SB4) is currently being processed in the Defense Waste Processing Facility (DWPF) using Frit 510. The slurry pumps in Tank 40 are experiencing in-leakage of bearing water, which is causing the sludge slurry in Tank 40 to become dilute at a rapid rate. Currently, the DWPF is removing this dilution water by performing caustic boiling during the Sludge Receipt and Adjustment Tank (SRAT) cycle. In order to alleviate prolonged SRAT cycle times, which may eventually impact canister production rates, the Liquid Waste Organization (LWO) performed a 100K gallon supernate decant of Tank 40 in April 2008. SRNL performed a supplemental glass variability study to support the April 2008 100K gallon decant incorporating the impact of coupled operations (addition of the Actinide Removal Process (ARP) stream). Recently LWO requested that SRNL assess the impact of a second decant (up to 100K gallon) to the Frit 510-SB4 system. This second decant occurred in June 2008. LWO provided nominal compositions on May 6, 2008 representing Tank 40 prior to the second decant, following the second decant, and the SB4 Heel prior to blending with Tank 51 to constitute SB5. Paper study assessments were performed for these options based on sludge-only and coupled operations processing (ARP addition), as well as possible Na{sub 2}O additions (via NaOH additions) to both flowsheets. A review of the ComProTM database relative to the compositional region defined by the projections after the second decant coupled with Frit 510 identified only a few glasses with similar glass compositions. These glasses were acceptable from a durability perspective, but did not sufficiently cover the new glass compositional region. Therefore, SRNL recommended that a supplemental variability study be performed to support the June 2008 Tank 40 decant. Glasses were selected for the variability study based on three sludge compositional projections (sludge-only, coupled and coupled + 2 wt% Na{sub 2}O) at waste loadings (WLs) of interest to DWPF (32%, 35% and 38%). These nine glasses were fabricated and characterized using chemical composition analysis, X-ray Diffraction (XRD) and the Product Consistency Test (PCT). All of the glasses that were selected for this study satisfy the Product Composition Control System (PCCS) criteria and are deemed processable and acceptable for the DWPF, except for the SB4VS2-03 (sludge-only at 38% WL) target composition. This glass fails the T{sub L} criterion and would not be considered processable based on Slurry Mix Evaporator (SME) acceptability decisions. The durabilities of all of the study glasses (both quenched and ccc) are well below that of the normalized leachate for boron (NL [B]) of the reference EA glass (16.695 g/L) and are predictable using the current PCCS models. Very little variation exists between the NL [B] of the quenched and ccc versions of the glasses. There is some evidence of a trend toward a less durable glass as WL increases for some of the sludge projections. Frit 510 is a viable option for the processing of SB4 after a second Tank 40 decant with or without the addition of products from the ARP stream as well as the 2 wt% Na{sub 2}O addition. The addition of ARP had no negative impacts on the acceptability and predictability of the variability study glasses

INITIAL SLUDGE BATCH 4 TANK 40 DECANT VARIABILITY STUDY WITH FRIT 510

Sludge Batch 4 (SB4) is currently being processed in the Defense Waste Processing Facility (DWPF) using Frit 510. The slurry pumps in Tank 40 are experiencing in-leakage of bearing water, which is causing the sludge slurry feed in Tank 40 to become dilute at a rapid rate. Currently, the DWPF is removing this dilution water by performing caustic boiling during the Sludge Receipt and Adjustment Tank (SRAT) cycle. In order to alleviate prolonged SRAT cycle times that may eventually impact canister production rates, decant scenarios of 100, 150, and 200 kilogallons of supernate were proposed for Tank 40 during the DWPF March outage. Based on the results of the preliminary assessment issued by the Savannah River National Laboratory (SRNL), the Liquid Waste Organization (LWO) issued a Technical Task Request (TTR) for SRNL to (1) perform a more detailed evaluation using updated SB4 compositional information and (2) assess the viability of Frit 510 and determine any potential impacts on the SB4 system. As defined in the TTR, LWO requested that SRNL validate the sludge--only SB4 flowsheet and the coupled operations flowsheet using the 100K gallon decant volume as well as the addition of 3 wt% sodium on a calcined oxide basis. Approximately 12 historical glasses were identified during a search of the ComProTM database that are located within at least one of the five glass regions defined by the proposed SB4 flowsheet options. While these glasses meet the requirements of a variability study there was some concern that the compositional coverage did not adequately bound all cases. Therefore, SRNL recommended that a supplemental experimental variability study be performed to support the various SB4 flowsheet options that may be implemented for future SB4 operations in DWPF. Eighteen glasses were selected based on nominal sludge projections representing the current as well as the proposed flowsheets over a WL interval of interest to DWPF (32-42%). The intent of the experimental portion of the variability study is to demonstrate that the glasses of the Frit 510-modified SB4 compositional region (Cases No.1-5) are both acceptable relative to the Environmental Assessment (EA) reference glass and predictable by the current DWPF process control models for durability. Frit 510 is a viable option for the processing of SB4 after a Tank 40 decant and the addition of products from the Actinide Removal Process (ARP). The addition of ARP did not have any negative impacts on the acceptability and predictability of the variability study glasses. The results of the variability study indicate that all of the study glasses (both quenched and centerline canister cooled (ccc)) have normalized releases for boron that are well below the reference EA glass (16.695 g/L). The durabilities of all of the study glasses are predictable using the current Product Composition Control System (PCCS) durability models with the exception of SB4VAR24ccc (Case No.2 at 41%). PCCS is not applicable to non-homogeneous glasses (i.e. glasses containing crystals such as acmite and nepheline), thus SB4VAR24ccc should not be predictable as it contains nepheline. The presence of nepheline has been confirmed in both SB4VAR13ccc and SB4VAR24ccc by X-ray diffraction (XRD). These two glasses are the first results which indicate that the current nepheline discriminator value of 0.62 is not conservative. The nepheline discriminator was implemented into PCCS for SB4 based on the fact that all of the historical glasses evaluated with nepheline values of 0.62 or greater did not contain nepheline via XRD analysis. Although these two glasses do cause some concern over the use of the 0.62 nepheline value for future DWPF glass systems, the impact to the current SB4 system is of little concern. More specifically, the formation of nepheline was observed in glasses targeting 41 or 42% WL. Current processing of the Frit 510-SB4 system in DWPF has nominally targeted 34% WL. For the SB4 variability study glasses targeting these lower WLs, nepheline formation was not observed and the minimal difference in PCT response between quenched and ccc versions supported its absence

Two different charge-separation pathways in photosystem II

Charge separation is an essential step in the conversion of solar energy into chemical energy in photosynthesis. To investigate this process, we performed transient absorption experiments at 77 K with various excitation conditions on the isolated Photosystem II reaction center preparations from spinach. The results have been analyzed by global and target analysis and demonstrate that at least two different excited states, (Ch