Engineering topics

Fox, K

Publications and source records attributed to Fox, K.

At least 19 records

DOE OSTI2012

IMPACT OF URANIUM AND THORIUM ON HIGH TIO2 CONCENTRATION NUCLEAR WASTE GLASSES

This study focused on the potential impacts of the addition of Crystalline Silicotitanate (CST) and Monosodium Titanate (MST) from the Small Column Ion Exchange (SCIX) process on the Defense Waste Processing Facility (DWPF) glass waste form and the applicability of the DWPF process control models. MST from the Salt Waste Processing Facility (SWPF) is also considered in the study. The KT08-series of glasses was designed to evaluate any impacts of the inclusion of uranium and thorium in glasses containing the SCIX components. All but one of the study glasses were found to be amorphous by X-ray diffraction (XRD). One of the slowly cooled glasses contained a small amount of trevorite, which is typically found in DWPF-type glasses and had no practical impact on the durability of the glass. The measured Product Consistency Test (PCT) responses for the study glasses and the viscosities of the glasses were well predicted by the current DWPF models. No unexpected issues were encountered when uranium and thorium were added to the glasses with SCIX components.

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DOE OSTI2011

IMPACT OF THE SMALL COLUMN ION EXCHANGE PROCESS ON THE DEFENSE WASTE PROCESSING FACILITY - 12112

The Savannah River Site (SRS) is investigating the deployment of a parallel technology to the Salt Waste Processing Facility (SWPF, presently under construction) to accelerate high activity salt waste processing. The proposed technology combines large waste tank strikes of monosodium titanate (MST) to sorb strontium and actinides with two ion exchange columns packed with crystalline silicotitanate (CST) resin to sorb cesium. The new process was designated Small Column Ion Exchange (SCIX), since the ion exchange columns were sized to fit within a waste storage tank riser. Loaded resins are to be combined with high activity sludge waste and fed to the Defense Waste Processing Facility (DWPF) for incorporation into the current glass waste form. Decontaminated salt solution produced by SCIX will be fed to the SRS Saltstone Facility for on-site immobilization as a grout waste form. Determining the potential impact of SCIX resins on DWPF processing was the basis for this study. Accelerated salt waste treatment is projected to produce a significant savings in the overall life cycle cost of waste treatment at SRS.

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DOE OSTI2011

DEVELOPMENT OF CRYSTALLINE CERAMICS FOR IMMOBILIZATION OF ADVANCED FUEL CYCLE REPROCESSING WASTES

The Savannah River National Laboratory (SRNL) is developing crystalline ceramic waste forms to incorporate CS/LN/TM high Mo waste streams consisting of perovskite, hollandite, pyrochlore, zirconolite, and powellite phase assemblages. Simple raw materials, including Al{sub 2}O{sub 3}, CaO, and TiO{sub 2} were combined with simulated waste components to produce multiphase crystalline ceramics. Fiscal Year 2011 (FY11) activities included (i) expanding the compositional range by varying waste loading and fabrication of compositions rich in TiO{sub 2}, (ii) exploring the processing parameters of ceramics produced by the melt and crystallize process, (iii) synthesis and characterization of select individual phases of powellite and hollandite that are the target hosts for radionuclides of Mo, Cs, and Rb, and (iv) evaluating the durability and radiation stability of single and multi-phase ceramic waste forms. Two fabrication methods, including melting and crystallizing, and pressing and sintering, were used with the intent of studying phase evolution under various sintering conditions. An analysis of the XRD and SEM/EDS results indicates that the targeted crystalline phases of the FY11 compositions consisting of pyrochlore, perovskite, hollandite, zirconolite, and powellite were formed by both press and sinter and melt and crystallize processing methods. An evaluation of crystalline phase formation versus melt processing conditions revealed that hollandite, perovskite, zirconolite, and residual TiO{sub 2} phases formed regardless of cooling rate, demonstrating the robust nature of this process for crystalline phase development. The multiphase ceramic composition CSLNTM-06 demonstrated good resistance to proton beam irradiation. Electron irradiation studies on the single phase CaMoO{sub 4} (a component of the multiphase waste form) suggested that this material exhibits stability to 1000 years at anticipated self-irradiation doses (2 x 10{sup 10}-2 x 10{sup 11} Gy), but that its stability may be rate dependent, therefore limiting the activity of the waste for which it can be employed. Overall, these preliminary results indicate good radiation damage tolerance for the crystalline ceramic materials. The PCT results showed that, for all of the waste forms tested, the normalized release values for most of the elements measured, including all of the lanthanides and noble metals, were either very small or below the instrument detection limits. Elevated normalized release values were measured only for Cs, Mo, and Rb. It is difficult to draw further conclusions from these data until a benchmark material is developed for the PCT with this type of waste form. Calcined, simulated CS/LN/TM High Mo waste without additives had relatively low normalized release values for Cs, Mo, and Rb. A review of the chemical composition data for this sample showed that these elements were well retained after the calcination. Therefore, it will be useful to further characterize the calcined material to determine what form these elements are in after calcining. This, along with single phase studies on Cs containing crystal structures such as hollandite, should provide insight into the most ideal phases to incorporate these elements to produce a durable waste form.

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DOE OSTI2011

ADDITIVE TESTING FOR IMPROVED SULFUR RETENTION: PRELIMINARY REPORT

The Savannah River National Laboratory is collaborating with Alfred University to evaluate the potential for additives in borosilicate glass to improve sulfur retention. This preliminary report provides further background on the incorporation of sulfur in glass and outlines the experiments that are being performed by the collaborators. A simulated waste glass composition has been selected for the experimental studies. The first phase of experimental work will evaluate the impacts of BaO, PbO, and V{sub 2}O{sub 5} at concentrations of 1.0, 2.0, and 5.0 wt % on sulfate retention in simulated high level waste borosilicate glass. The second phase of experimental work will evaluate the effects of time at the melt temperature on sulfur retention. The resulting samples will be characterized to determine the amount of sulfur remaining as well as to identify the formation of any crystalline phases. The results will be used to guide the future selection of frits and glass forming chemicals in vitrifying Department of Energy wastes containing high sulfur concentrations.

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DOE OSTI2011

SUMMARY REPORT ON POTENTIAL IMPACTS OF SMALL COLUMN ION EXCHANGE ON DWPF GLASS FORMULATION

This report summarizes a large amount of experimental work completed to identify the potential impacts of material from Small Column Ion Exchange (SCIX) on glass formulation at the Defense Waste Processing Facility (DWPF). The results show no significant issues with the predicted values of chemical durability and viscosity using the current Product Composition Control System (PCCS) models when the SCIX components are added to projected DWPF glass compositions. No modifications to the viscosity and durability models appear to be necessary at this time in order to incorporate the SCIX streams at DWPF. It is recommended that the Savannah River National Laboratory (SRNL) continue to verify the durability and viscosity models as the projected compositions for DWPF processing evolve. It is also recommended that the data generated thus far be reviewed and a determination be made as to how best to extend the validation ranges of the durability and viscosity models. The liquidus temperatures for the experimental glasses are also reported and discussed in this report. The results show that the measured or estimated (based on measured data) liquidus temperature values for the glasses with SCIX components added are consistently higher than those predicted by the current model. Therefore, the PCCS liquidus temperature model will need to be modified in order to incorporate the SCIX streams at DWPF. It is recommended that SRNL carry out full measurements of the liquidus temperatures for those KT-series glasses where estimates have been made. These data should then be used to support an evaluation of whether a refitting of the liquidus temperature model coefficients will be sufficient to correctly predict the liquidus temperature of glasses containing the SCIX components (particularly higher TiO{sub 2} concentrations), or whether additional modifications to the model are required. While there are prediction issues with the current liquidus temperature model, they are not at this time expected to hamper the incorporation of SCIX streams at DWPF. The estimated liquidus temperatures, while higher than the model predicted values, remain below the current DWPF limit of 1050 C for most of the study glasses. Note that the properties and performance of the glasses in this study are highly dependent on glass composition. Therefore, should significant changes be made to the projected compositions or processing rates for SCIX or DWPF, many of the assessments and experiments may have to be revisited.

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DOE OSTI2011

IMPACTS OF SMALL COLUMN ION EXCHANGE STREAMS ON DWPF GLASS FORMULATION: KT08, KT09, AND KT10-SERIES GLASS COMPOSITIONS

This report is the fourth in a series of studies of the impacts of the addition of Crystalline Silicotitanate (CST) and Monosodium Titanate (MST) from the Small Column Ion Exchange (SCIX) process on the Defense Waste Processing Facility (DWPF) glass waste form and the applicability of the DWPF process control models. MST from the Salt Waste Processing Facility (SWPF) is also considered in the study. The KT08-series of glasses was designed to evaluate any impacts of the inclusion of uranium and thorium in glasses containing the SCIX components. The KT09-series of glasses was designed to study the effect of increasing Al{sub 2}O{sub 3} and K{sub 2}O concentrations on the propensity for crystallization of titanium containing phases in high TiO{sub 2} concentration glasses. Earlier work on the KT05-series glasses recommended that the impact of these two components be studied further. Increased Al{sub 2}O{sub 3} concentrations have been shown to improve the properties and performance of high waste loading glasses, and K{sub 2}O has been reported to improve the retention of TiO{sub 2} in silicate glasses. The KT10-series of compositions was designed to evaluate any impacts of the SCIX components at concentrations 50% higher than currently projected.a The glasses were fabricated in the laboratory and characterized to identify crystallization, to verify chemical compositions, to measure viscosity, and to measure durability. Liquidus temperature measurements for the KT10-series glasses are underway and will be reported separately. All but one of the KT08-series glasses were found to be amorphous by X-ray diffraction (XRD). One of the slowly cooled glasses contained a small amount of trevorite, which had no practical impact on the durability of the glass and is typically found in DWPF-type glasses. The measured Product Consistency Test (PCT) responses for the KT08-series glasses are well predicted by the DWPF models. The viscosities of the KT08-series glasses were generally well predicted by the DWPF model. No unexpected issues were encountered when uranium and thorium were added to the glasses with SCIX components. Increased Al{sub 2}O{sub 3} concentrations were not successful in preventing the formation of iron titanate crystals in the KT09-series glasses. Increased K{sub 2}O concentrations were successful in hindering the formation of iron titanates in some of the glasses after the canister centerline cooled (CCC) heat treatment. However, this result did not apply to all of the CCC versions of the glasses, indicating a compositional dependence of this effect. In addition, high concentrations of K{sub 2}O have been shown to hinder the ability of the DWPF durability and viscosity models to predict the performance of these glasses. The usefulness of increased K{sub 2}O concentrations in preventing the formation of iron titanates may therefore be limited. Further characterization was not performed for the KT09-series glasses since the type of crystallization formed was the characteristic of interest for these compositions. All of the KT10-series glasses were XRD amorphous, regardless of heat treatment. Chemical composition measurements showed that the glasses met the targeted concentrations for each oxide. In general, the measured PCT responses of the KT10-series glasses were well predicted by the DWPF models. The measured, normalized release values for silicon for some of the glasses fell above the 95% confidence interval for the predicted values; however, the PCT responses for these glasses remain considerably lower than that of the benchmark Environmental Assessment (EA) glass. The viscosities of the KT10-series glasses were generally well predicted by the DWPF model. The next step in this study will be to compile all of the data developed and further compare the measured properties and performance with those predicted by the current DWPF Product Composition Control System (PCCS) models. Recommendations will then be made as to which models, if any, may need to be modified in order to accommodate the material from SCIX into DWPF glass production.

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DOE OSTI2011

IMPACT OF SMALL COLUMN ION EXCHANGE STREAMS ON DWPF GLASS FORMULATION MELT RATE STUDIES

This study was undertaken to evaluate the potential impacts of the Small Column Ion Exchange (SCIX) streams - particularly the addition of Monosodium Titanate (MST) and Crystalline Silicotitanate (CST) - on the melt rate of simulated feed for the Defense Waste Processing Facility (DWPF). Additional MST was added to account for contributions from the Salt Waste Processing Facility (SWPF). The Savannah River National Laboratory (SRNL) Melt Rate Furnace (MRF) was used to evaluate four melter feed compositions: two with simulated SCIX and SWPF material and two without. The Slurry-fed Melt Rate Furnace (SMRF) was then used to compare two different feeds: one with and one without bounding concentrations of simulated SCIX and SWPF material. Analyses of the melter feed materials confirmed that they met their targeted compositions. Four feeds were tested in triplicate in the MRF. The linear melt rates were determined by using X-ray computed tomography to measure the height of the glass formed along the bottom of the beakers. The addition of the SCIX and SWPF material reduced the average measured melt rate by about 10% in MRF testing, although there was significant scatter in the data. Two feeds were tested in the SMRF. It was noted that the ground CST alone (ground CST with liquid in a bucket) was extremely difficult to resuspend during preparation of the feed with material from SCIX and SWPF. This feed was also more difficult to pump than the material without MST and CST due to settling occurring in the melter feed line, although the yield stress of both feeds was high relative to the DWPF design basis. Steady state feeding conditions were maintained for about five hours for each feed. There was a reduction in the feed and pour rates of approximately 15% when CST and MST were added to the feed, although there was significant scatter in the data. Analysis of samples collected from the SMRF pour stream showed that the composition of the glass changed as expected when MST and CST were added to the feed. These reductions in melt rate are consistent with previous studies that showed a negative impact of increased TiO{sub 2} concentrations on the rate of melting. The impact of agitating the melt pool via bubbling was not studied as part of this work, but may be of interest for further testing. It is recommended that additional melt rate testing be performed should a potential reduction in melt rate of 10-15% be considered an issue of concern, or should the anticipated composition of the glass with the addition of material from salt waste processing be modified significantly from the current projections, either due to changes in sludge batch preparation or changes in the composition or volume of SCIX and SWPF material.

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DOE OSTI2011

SUMMARY OF 2010 DOE EM INTERNATIONAL PROGRAM STUDIES OF WASTE GLASS STRUCTURE AND PROPERTIES

Collaborative work between the Savannah River National Laboratory (SRNL) and SIA Radon in Russia was divided among three tasks for calendar year 2010. The first task focused on the study of simplified high level waste glass compositions with the objective of identifying the compositional drivers that lead to crystallization and poor chemical durability. The second task focused on detailed characterization of more complex waste glass compositions with unexpectedly poor chemical durabilities. The third task focused on determining the structure of select high level waste glasses made with varying frit compositions in order to improve models under development for predicting the melt rate of the Defense Waste Processing Facility (DWPF) glasses. The majority of these tasks were carried out at SIA Radon. Selection and fabrication of the glass compositions, along with chemical composition measurements and evaluations of durability were carried out at SRNL and are described in this report. SIA Radon provided three summary reports based on the outcome of the three tasks. These reports are included as appendices to this document. Briefly, the result of characterization of the Task 1 glasses may indicate that glass compositions where iron is predominantly tetrahedrally coordinated have more of a tendency to crystallize nepheline or nepheline-like phases. For the Task 2 glasses, the results suggested that the relatively low fraction of tetrahedrally coordinated boron and the relatively low concentrations of Al{sub 2}O{sub 3} available to form [BO{sub 4/2}]{sup -}Me{sup +} and [AlO{sub 4/2}]{sup -}Me{sup +} tetrahedral units are not sufficient to consume all of the alkali ions, and thus these alkali ions are easily leached from the glasses. All of the twelve Task 3 glass compositions were determined to be mainly amorphous, with some minor spinel phases. Several key structural units such as metasilicate chains and rings were identified, which confirms the current modeling approach for the silicate phase. The coordination of aluminum and iron was found to be mainly tetrahedral, with some octahedral iron ions. In all samples, trigonally-coordinated boron was determined to dominate over tetrahedrally-coordinated boron. The results further suggested that BO{sub 4} tetrahedra and BO{sub 3} triangles form complex borate units and may be present as separate constituents. However, no quantification of tetrahedral-to-trigonal boron ratio was made.

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DOE OSTI2011

SUMMARY OF 2010 DOE EM INTERNATIONAL PROGRAM STUDIES OF WASTE GLASS MELT RATE ENHANCEMENT

A collaborative study has been established under the U.S. Department of Energy (DOE) Office of Environmental Management International Program between the Savannah River National Laboratory (SRNL) and the V. G. Khlopin Radium Institute (KRI) in St. Petersburg, Russia, to investigate potential improvements in melt rate via chemical additions to the glass frit. Researchers at KRI suggested a methodology for selecting frit additives based on empirical coefficients for optimization of glass melting available in the Russian literature. Using these coefficients, KRI identified B{sub 2}O{sub 3}, CuO, and MnO as frit additives that were likely to improve melt rate without having adverse effects on crystallization of the glass or its chemical durability. The results of the melt rate testing in the SMK melter showed that the slurry feed rate (used as a gauge of melt rate) could be significantly increased when MnO or CuO were added to Frit 550 with the SMR-2 sludge. The feed rates increased by about 27% when MnO was added to the frit and by about 26% when CuO was added to the frit, as compared to earlier results for Frit 550 alone. The impact of adding additional B{sub 2}O{sub 3} to the frit was minor when added with CuO. The additional B{sub 2}O{sub 3} showed a more significant, 39% improvement in melt rate when added with MnO. The additional B{sub 2}O{sub 3} also reduced the viscosity of the glasses during pouring. Samples of the glasses from the melt rate testing characterized at SRNL showed that there were no significant impacts on crystallization of the glasses. All of the glasses had very good chemical durability. Chemical composition measurements showed that the frit additives were present in concentrations below the targeted values in some of the glasses. Therefore, it is possible that higher concentrations of these additives may further improve melt rate, although the impacts of higher concentrations of these components on crystallization and durability would need to be determined. Overall, the results show an excellent potential for these additives to significantly improve waste throughput for DOE vitrification facilities. A complete report from KRI is included as an appendix to this document.

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DOE OSTI2011

IMPACTS OF SMALL COLUMN ION EXCHANGE STREAMS ON DWPF GLASS FORMULATION KT07-SERIES GLASS COMPOSITIONS

This report is the third in a series of studies of the impacts of the addition of Crystalline Silicotitanate (CST) and Monosodium Titanate (MST) from the Small Column Ion Exchange (SCIX) process on the Defense Waste Processing Facility (DWPF) glass waste form and the applicability of the DWPF process control models. MST from the Salt Waste Processing Facility is also considered in the study. The KT07-series glasses were selected to evaluate any potential impacts of noble metals on their properties and performance. The glasses characterized thus far for the SCIX study have not included noble metals since they are not typically tracked in sludge batch composition projections. However, noble metals can act as nucleation sites in glass melts, leading to enhanced crystallization. This crystallization can potentially influence the properties and performance of the glass, such as chemical durability, viscosity, and liquidus temperature. The noble metals Ag, Pd, Rh, and Ru were added to the KT07-series glasses in concentrations based on recent measurements of Sludge Batch 6, which was considered to contain a high concentration of noble metals. The KT04-series glasses were used as the baseline compositions. After fabrication, the glasses were characterized to determine their homogeneity, chemical composition, durability, and viscosity. Liquidus temperature measurements are also underway but were not complete at the time of this report. The liquidus temperature results for the KT07-series glasses, along with several of the earlier glasses in the SCIX study, will be documented separately. All of the KT07-series glasses, both quenched and slowly cooled, were found to be amorphous by X-ray diffraction. Chemical composition measurements showed that all of the glasses met their targeted compositions. The Product Consistency Test (PCT) results showed that all of the glasses had chemical durabilities that were far better than that of the Environmental Assessment benchmark glass. The measured PCT responses were well predicted by the current DWPF Product Composition Control System (PCCS) durability models. The measured viscosity values for each KT07-series glass were acceptable for DWPF processing and were well predicted by the current PCCS model. Overall, the results show that the inclusion of relatively high concentrations of noble metals (in terms of expected values for a DWPF sludge batch) had no significant impact on the properties and performance of these glass compositions. There were no significant differences in the measured properties when compared to those of the KT04-series glasses, which did not contain noble metals. Liquidus temperature measurements are still underway and there may be an impact of the noble metals on those measurements. However, no adverse effects were noted in terms of crystallization after slow cooling. At the completion of these studies, all of the data generated will be reviewed with regard to the applicability of the DWPF PCCS models and recommendations will be made as to whether the validation ranges of the current models can be extended, or whether some or all of the models need to be refit to allow for the incorporation of the SCIX streams. As changes are made to the projected sludge compositions and the volume of the SCIX material, additional evaluations should be performed.

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DOE OSTI2011

PLUTONIUM SOLUBILITY IN HIGH-LEVEL WASTE ALKALI BOROSILICATE GLASS

The solubility of plutonium in a Sludge Batch 6 (SB6) reference glass and the effect of incorporation of Pu in the glass on specific glass properties were evaluated. A Pu loading of 1 wt % in glass was studied. Prior to actual plutonium glass testing, surrogate testing (using Hf as a surrogate for Pu) was conducted to evaluate the homogeneity of significant quantities of Hf (Pu) in the glass, determine the most appropriate methods to evaluate homogeneity for Pu glass testing, and to evaluate the impact of Hf loading in the glass on select glass properties. Surrogate testing was conducted using Hf to represent between 0 and 1 wt % Pu in glass on an equivalent molar basis. A Pu loading of 1 wt % in glass translated to {approx}18 kg Pu per Defense Waste Processing Facility (DWPF) canister, or about 10X the current allowed limit per the Waste Acceptance Product Specifications (2500 g/m{sup 3} of glass or about 1700 g/canister) and about 30X the current allowable concentration based on the fissile material concentration limit referenced in the Yucca Mountain Project License Application (897 g/m{sup 3}3 of glass or about 600 g Pu/canister). Based on historical process throughput data, this level was considered to represent a reasonable upper bound for Pu loading based on the ability to provide Pu containing feed to the DWPF. The task elements included evaluating the distribution of Pu in the glass (e.g. homogeneity), evaluating crystallization within the glass, evaluating select glass properties (with surrogates), and evaluating durability using the Product Consistency Test -- Method A (PCT-A). The behavior of Pu in the melter was evaluated using paper studies and corresponding analyses of DWPF melter pour samples.The results of the testing indicated that at 1 wt % Pu in the glass, the Pu was homogeneously distributed and did not result in any formation of plutonium-containing crystalline phases as long as the glass was prepared under 'well-mixed' conditions. The incorporation of 1 wt % Pu in the glass did not adversely impact glass viscosity (as assessed using Hf surrogate) or glass durability. Finally, evaluation of DWPF glass pour samples that had Pu concentrations below the 897 g/m{sup 3} limit showed that Pu concentrations in the glass pour stream were close to targeted compositions in the melter feed indicating that Pu neither volatilized from the melt nor stratified in the melter when processed in the DWPF melter.

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DOE OSTI2011

IMPACTS OF SMALL COLUMN ION EXCHANGE STREAMS ON DWPF GLASS FORMULATION: KT05- AND KT06-SERIES GLASS COMPOSITIONS

This report is the second in a series of studies of the impacts of the addition of Crystalline Silicotitanate (CST) and Monosodium Titanate (MST) from the Small Column Ion Exchange (SCIX) process on the Defense Waste Processing Facility (DWPF) glass waste form and the applicability of the DWPF process control models. The KT05-series glasses were selected, fabricated, and characterized to further study glass compositions where iron titanate crystals had been previously found to form. The intent was to better understand the mechanisms and compositions that favored the formation of crystals containing titanium. Formation of these crystalline phases was confirmed. Increased Na{sub 2}O concentrations had little if any impact on reducing the propensity for the formation of the iron titanate crystalline phases. Other physical properties of these glasses were not measured since the intent was to focus on crystallization. Additional studies are suggested to investigate the potential impacts of Al{sub 2}O{sub 3} and K{sub 2}O on crystallization in glasses with high TiO{sub 2} concentrations. The KT06-series glasses were selected, fabricated, and characterized to further study glass compositions that, while broader than the current projections for DWPF feeds with SCIX material, are potential candidates for future processing (i.e., the compositions are acceptable for processing by the Product Composition Control System (PCCS) with the exception of the current TiO{sub 2} concentration constraint). The chemical compositions of these glasses matched well with the target values. The chemical durabilities of all the glasses were acceptable relative to the Environmental Assessment (EA) benchmark. Minor crystallization was identified in some of the slowly cooled glasses, although this crystallization did not impact chemical durability. Several of the KT06-series compositions had durability values that, while acceptable, were not accurately predicted by the current durability models. It was shown that for these high TiO{sub 2} concentration glasses, relatively high Fe{sub 2}O{sub 3} concentrations combined with relatively high Al{sub 2}O{sub 3} concentrations led to durabilities that were unpredictable. Several of the KT06-series glasses also had measured viscosity values that were not well predicted by the current model. A statistical partitioning routine showed that the measured viscosities became unpredictable by the current model when the Fe{sub 2}O{sub 3} concentration in the glasses was less than about 8.2 wt % at the elevated TiO{sub 2} concentrations. The current durability and viscosity models will have to be further evaluated should compositions in these regions become necessary for DWPF processing. Overall, the results presented for the KT06-series glasses show that TiO{sub 2} from the SCIX streams can be incorporated into DWPF-type glasses at concentrations of 6 wt % (in glass) without any detrimental impacts on crystallization or chemical durability that are of practical importance. The measured values for chemical durability and viscosity were acceptable for processing; however, not all of the values were predictable by the current PCCS models. Since the compositions selected for the KT06-series glasses were outside the current projections for DWPF processing with the SCIX streams (in terms of waste components other than TiO{sub 2}), these results help identify compositional regions that, if necessary for processing, would require modifications to the current models. Additional experiments are currently underway. Once completed, all of the measured data will be reviewed and compared to model predictions to better determine whether the validation range of the DWPF process control models can be confidently extended, or whether refitting of the models will be necessary.

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DOE OSTI2010

DEVELOPMENT OF CERAMIC WASTE FORMS FOR AN ADVANCED NUCLEAR FUEL CYCLE

A series of ceramic waste forms were developed and characterized for the immobilization of a Cesium/Lanthanide (CS/LN) waste stream anticipated to result from nuclear fuel reprocessing. Simple raw materials, including Al{sub 2}O{sub 3} and TiO{sub 2} were combined with simulated waste components to produce multiphase ceramics containing hollandite-type phases, perovskites (particularly BaTiO{sub 3}), pyrochlores and other minor metal titanate phases. Three fabrication methodologies were used, including melting and crystallizing, pressing and sintering, and Spark Plasma Sintering (SPS), with the intent of studying phase evolution under various sintering conditions. X-Ray Diffraction (XRD) and Scanning Electron Microscopy coupled with Energy Dispersive Spectroscopy (SEM/EDS) results showed that the partitioning of the waste elements in the sintered materials was very similar, despite varying stoichiometry of the phases formed. Identification of excess Al{sub 2}O{sub 3} via XRD and SEM/EDS in the first series of compositions led to a Phase II study, with significantly reduced Al{sub 2}O{sub 3} concentrations and increased waste loadings. The Phase II compositions generally contained a reduced amount of unreacted Al{sub 2}O{sub 3} as identified by XRD. Chemical composition measurements showed no significant issues with meeting the target compositions. However, volatilization of Cs and Mo was identified, particularly during melting, since sintering of the pressed pellets and SPS were performed at lower temperatures. Partitioning of some of the waste components was difficult to determine via XRD. SEM/EDS mapping showed that those elements, which were generally present in small concentrations, were well distributed throughout the waste forms.

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DOE OSTI2010

INCORPORATION OF MONO SODIUM TITANATE AND CRYSTALLINE SILICOTITANATE FEEDS IN HIGH LEVEL NUCLEAR WASTE GLASS

Four series of glass compositions were selected, fabricated, and characterized as part of a study to determine the impacts of the addition of Crystalline Silicotitanate (CST) and Monosodium Titanate (MST) from the Small Column Ion Exchange (SCIX) process on the Defense Waste Processing Facility (DWPF) glass waste form and the applicability of the DWPF process control models. All of the glasses studied were considerably more durable than the benchmark Environmental Assessment (EA) glass. The measured Product Consistency Test (PCT) responses were compared with the predicted values from the current DWPF durability model. One of the KT01-series and two of the KT03-series glasses had measured PCT responses that were outside the lower bound of the durability model. All of the KT04 glasses had durabilities that were predictable regardless of heat treatment or compositional view. In general, the measured viscosity values of the KT01, KT03, and KT04-series glasses are well predicted by the current DWPF viscosity model. The results of liquidus temperature (T{sub L}) measurements for the KT01-series glasses were mixed with regard to the predictability of the T{sub L} for each glass. All of the measured T{sub L} values were higher than the model predicted values, although most fell within the 95% confidence intervals. Overall, the results of this study show a reasonable ability to incorporate the anticipated SCIX streams into DWPF-type glass compositions with TiO{sub 2} concentrations of 4-5 wt % in glass.

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DOE OSTI2010

IMPACTS OF SMALL COLUMN ION EXCHANGE STREAMS ON DWPF GLASS FORMULATION: KT01, KT02, KT03, AND KT04-SERIES GLASS COMPOSITIONS

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DOE OSTI2010

PRELIMINARY STUDY OF CERAMICS FOR IMMOBILIZATION OF ADVANCED FUEL CYCLE REPROCESSING WASTES

The Savannah River National Laboratory (SRNL) developed a series of ceramic waste forms for the immobilization of Cesium/Lanthanide (CS/LN) and Cesium/Lanthanide/Transition Metal (CS/LN/TM) waste streams anticipated to result from nuclear fuel reprocessing. Simple raw materials, including Al{sub 2}O{sub 3}, CaO, and TiO{sub 2} were combined with simulated waste components to produce multiphase ceramics containing hollandite-type phases, perovskites (particularly BaTiO{sub 3}), pyrochlores, zirconolite, and other minor metal titanate phases. Identification of excess Al{sub 2}O{sub 3} via X-ray Diffraction (XRD) and Scanning Electron Microscopy with Energy Dispersive Spectroscopy (SEM/EDS) in the first series of compositions led to a Phase II study, with significantly reduced Al{sub 2}O{sub 3} concentrations and increased waste loadings. Three fabrication methodologies were used, including melting and crystallizing, pressing and sintering, and Spark Plasma Sintering (SPS), with the intent of studying phase evolution under various sintering conditions. XRD and SEM/EDS results showed that the partitioning of the waste elements in the sintered materials was very similar, despite varying stoichiometry of the phases formed. The Phase II compositions generally contained a reduced amount of unreacted Al{sub 2}O{sub 3} as identified by XRD, and had phase assemblages that were closer to the initial targets. Chemical composition measurements showed no significant issues with meeting the target compositions. However, volatilization of Cs and Mo was identified, particularly during melting, since sintering of the pressed pellets and SPS were performed at lower temperatures. Partitioning of some of the waste components was difficult to determine via XRD. SEM/EDS mapping showed that those elements, which were generally present in small concentrations, were well distributed throughout the waste forms. Initial studies of radiation damage tolerance using ion beam irradiation at Los Alamos National Laboratory (LANL) showed little if any modification of the material after irradiation. Additional study in this area is needed. Chemical durability was briefly studied using the Product Consistency Test (PCT). Most of the elements measured were retained by the ceramic waste forms, indicating good chemical durability. Cs, Mo, and Rb were released at somewhat higher rates as compared to the matrix components, although benchmark compositions and additional characterization are needed in order to qualify the PCT results.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2010

RETENTION OF SULFATE IN HIGH LEVEL RADIOACTIVE WASTE GLASS

High level radioactive wastes are being vitrified at the Savannah River Site for long term disposal. Many of the wastes contain sulfate at concentrations that can be difficult to retain in borosilicate glass. This study involves efforts to optimize the composition of a glass frit for combination with the waste to improve sulfate retention while meeting other process and product performance constraints. The fabrication and characterization of several series of simulated waste glasses are described. The experiments are detailed chronologically, to provide insight into part of the engineering studies used in developing frit compositions for an operating high level waste vitrification facility. The results lead to the recommendation of a specific frit composition and a concentration limit for sulfate in the glass for the next batch of sludge to be processed at Savannah River.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2010

PAPER STUDY EVALUATIONS OF THE INTRODUCTION OF SMALL COLUMN ION EXCHANGE WASTE STREAMS TO THE DEFENSE WASTE PROCESSING FACILITY

The objective of this paper study is to provide guidance on the impact of Monosodium Titanate (MST) and Crystalline Silicotitanate (CST) streams from the Small Column Ion Exchange (SCIX) process on the Defense Waste Processing Facility (DWPF) flowsheet and glass waste form. A series of waste processing scenarios was evaluated, including projected compositions of Sludge Batches 8 through 17 (SB8 through SB17), MST additions, CST additions to Tank 40 or to a sludge batch preparation tank (Tank 42 or Tank 51, referred to generically as Tank 51 in this report), streams from the Salt Waste Processing Facility (SWPF), and two canister production rates. A wide array of potential glass frit compositions was used to support this assessment. The sludge and frit combinations were evaluated using the predictive models in the current DWPF Product Composition Control System (PCCS). The results were evaluated based on the number of frit compositions available for a particular sludge composition scenario. A large number of candidate frit compositions (e.g., several dozen to several hundred) is typically a good indicator of a sludge composition for which there is flexibility in forming an acceptable waste glass and meeting canister production rate commitments. The MST and CST streams will significantly increase the concentrations of certain components in glass, such as Nb{sub 2}O{sub 5}, TiO{sub 2}, and ZrO{sub 2}, to levels much higher than have been previously processed at DWPF. Therefore, several important assumptions, described in detail in the report, had to be made in performing the evaluations. The results of the paper studies, which must be applied carefully given the assumptions made concerning the impact of higher Ti, Zr, and Nb concentrations on model validity, provided several observations: (1) There was difficulty in identifying a reasonable number of candidate frits (and in some cases an inability to identify any candidate frits) when a waste loading of 40% is targeted for Sludge Batches 8, 16, and 17, regardless of the addition of SCIX or SWPF streams. This indicates that the blending strategy for these sludge batches should be reevaluated by Savannah River Remediation (SRR). (2) In general, candidate frits were available to accommodate CST additions to either Tank 40 or Tank 51. A larger number of candidate frits were typically available for the sludge batches when CST is added to Tank 51 rather than Tank 40, meaning that more compositional flexibility would be available for frit selection and DWPF operation. Note however that for SB8 and SB17, no candidate frits were available to accommodate CST going to Tank 40 with and without SWPF streams. The addition of SWPF streams generally improves the number of candidate frits available for processing of a given sludge batch. (3) The change in production rate from 40 Sludge Receipt and Adjustment Tank (SRAT) batches per year (i.e., the current production rate) to 75 SRAT batches per year, without SWPF streams included, had varied results in terms of the number of candidate frits available for processing of a given sludge batch. Therefore, this variable is not of much concern in terms of incorporating the SCIX streams. Note that the evaluation at 75 SRAT batches per year (approximately equivalent to 325 canisters per year) is more conservative in terms of the impact of SCIX streams as compared to a production rate of 400 canisters per year. Overall, the outcome of this paper study shows no major issues with the ability to identify an acceptable glass processing window when CST from the SCIX process is transferred to either Tank 40 or Tank 51. The assumptions used and the model limitations identified in this report must be addressed through further experimental studies, which are currently being performed. As changes occur to the planned additions of MST and CST, or to the sludge batch preparation strategy, additional evaluations will be performed to determine the potential impacts. As stated above, the issues with Sludge Batches 8, 16, and 17 should be further evaluated by SRR. A review of Chemical Process Cell (CPC) processing identified no changes to the recommendations from the previous review of the SCIX process impacts. Recommendations for testing were made during the previous review to evaluate the impact of CST on the rheological properties of DWPF process streams and evaluate the impact of CST on catalytic hydrogen generation during CPC processing.

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