Engineering topics

Edwards, T

Publications and source records attributed to Edwards, T.

At least 37 records · Page 2

DOE OSTI2011

Analyses by the Defense Waste Processing Facility Laboratory of Thorium Glasses from the Sludge Batch 6 Variability Study

The Savannah River Remediation (SRR) Defense Waste Processing Facility (DWPF) is currently processing Sludge Batch 6 (SB6) with Frit 418. At times during the processing of this glass system, thorium is expected to be at concentrations in the final wasteform that make it a reportable element for the first time since startup of radioactive operations at the DWPF. The Savannah River National Laboratory (SRNL) supported the qualification of the processing of this glass system at the DWPF. A recommendation from the SRNL studies was the need for the DWPF Laboratory to establish a method to measure thorium by Inductively Coupled Plasma - Atomic Emission Spectroscopy (ICPAES). This recommendation led to the set of thorium-bearing glasses from the SB6 Variability Study (VS) being submitted to the DWPF Laboratory for chemical composition measurement. The measurements were conducted by the DWPF Laboratory using the sodium peroxide fusion preparation method routinely employed for analysis of samples from the Slurry Mix Evaporator (SME). These measurements are presented and reviewed in this report. The review indicates that the measurements provided by the DWPF Laboratory are comparable to those provided by Analytical Development's laboratory at SRNL for these same glasses. As a result, the authors of this report recommend that the DWPF Laboratory begin using its routine peroxide fusion dissolution method for the measurement of thorium in SME samples of SB6. The purpose of this technical report is to present the measurements generated by the DWPF Laboratory for the SB6 VS glasses and to compare the measurements to the targeted compositions for these VS glasses as well as to SRNL's measurements (both sets, targeted and measured, of compositional values were reported by SRNL in [2]). The goal of these comparisons is to provide information that will lead to the qualification of peroxide fusion dissolution as a method for the measurement by the DWPF Laboratory of thorium in SME glass samples.

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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

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

Evaluation of Glass Density to Support the Estimation of Fissile Mass Loadings from Iron Concentrations in SB6 Glasses

The Department of Energy - Savannah River (DOE-SR) previously provided direction to Savannah River Remediation (SRR) to maintain fissile concentration in glass below 897 g/m{sup 3}. In support of the guidance, the Savannah River National Laboratory (SRNL) provided a technical basis and a supporting Microsoft{reg_sign} Excel{reg_sign} spreadsheet for the evaluation of fissile loading in Sludge Batch 5 glass based on the Fe concentration in glass as determined by the measurements from the Slurry Mix Evaporator (SME) acceptability analysis. SRR has since requested that SRNL provide the necessary information to allow SRR to update the Excel spreadsheet so that it may be used to maintain fissile concentration in glass below 897 g/m{sup 3} during the processing of Sludge Batch 6 (SB6). One of the primary inputs into the fissile loading spreadsheet includes a bounding density for SB6-based glasses. Based on the measured density data of select SB6 variability study glasses, SRNL recommends that SRR utilize the 99/99 Upper Tolerance Limit (UTL) density value at 38% WL (2.823 g/cm{sup 3}) as a bounding density for SB6 glasses to assess the fissile concentration in this glass system. That is, the 2.823 g/cm{sup 3} is recommended as a key (and fixed) input into the fissile concentration spreadsheet for SB6 processing. It should be noted that no changes are needed to the underlying structure of the Excel based spreadsheet to support fissile assessments for SB6. However, SRR should update the other key inputs to the spreadsheet that are based on fissile and Fe concentrations reported from the SB6 Waste Acceptance Product Specification (WAPS) sample. The purpose of this technical report is to present the density measurements that were determined for the SB6 variability study glasses and to conduct a statistical evaluation of these measurements to provide a bounding density value that may be used as input to the Excel{reg_sign} spreadsheet to be employed by SRR to maintain the fissile concentration in its SB6 glass below 897 g/m{sup 3}. It should be noted that no changes are needed to the underlying structure of the Excel{reg_sign} based spreadsheet to support fissile assessments for SB6.

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DOE OSTI2010

PROBABILITY BASED CORROSION CONTROL FOR LIQUID WASTE TANKS - PART III

The liquid waste chemistry control program is designed to reduce the pitting corrosion occurrence on tank walls. The chemistry control program has been implemented, in part, by applying engineering judgment safety factors to experimental data. However, the simple application of a general safety factor can result in use of excessive corrosion inhibiting agents. The required use of excess corrosion inhibitors can be costly for tank maintenance, waste processing, and in future tank closure. It is proposed that a probability-based approach can be used to quantify the risk associated with the chemistry control program. This approach can lead to the application of tank-specific chemistry control programs reducing overall costs associated with overly conservative use of inhibitor. Furthermore, when using nitrite as an inhibitor, the current chemistry control program is based on a linear model of increased aggressive species requiring increased protective species. This linear model was primarily supported by experimental data obtained from dilute solutions with nitrate concentrations less than 0.6 M, but is used to produce the current chemistry control program up to 1.0 M nitrate. Therefore, in the nitrate space between 0.6 and 1.0 M, the current control limit is based on assumptions that the linear model developed from data in the <0.6 M region is applicable in the 0.6-1.0 M region. Due to this assumption, further investigation of the nitrate region of 0.6 M to 1.0 M has potential for significant inhibitor reduction, while maintaining the same level of corrosion risk associated with the current chemistry control program. Ongoing studies have been conducted in FY07, FY08, FY09 and FY10 to evaluate the corrosion controls at the SRS tank farm and to assess the minimum nitrite concentrations to inhibit pitting in ASTM A537 carbon steel below 1.0 molar nitrate. The experimentation from FY08 suggested a non-linear model known as the mixture/amount model could be used to predict the probability of corrosion in ASTM A537 in varying solutions as shown in Figure 1. The mixture/amount model takes into account not only the ratio (or mixture) of inhibitors and aggressive species, but also the total concentration (or amount) of species in a solution. Historically, the ratio was the only factor taken into consideration in the development of the current chemistry control program. During FY09, an experimental program was undertaken to refine the mixture/amount model by further investigating the risk associated with reducing the minimum molar nitrite concentration required to confidently inhibit pitting in dilute solutions. The results of FY09, as shown in Figure 2, quantified the probability for a corrosion free outcome for combinations of nitrate and nitrite. The FY09 data predict probabilities up to 70%. Additional experimental data are needed to increase the probability to an acceptable percentage.

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DOE OSTI2010

PROBABILITY BASED CORROSION CONTROL FOR WASTE TANKS - PART II

As part of an ongoing study to evaluate the discontinuity in the corrosion controls at the SRS tank farm, a study was conducted this year to assess the minimum concentrations below 1 molar nitrate, see Figure 1. Current controls on the tank farm solution chemistry are in place to prevent the initiation and propagation of pitting and stress corrosion cracking in the primary steel waste tanks. The controls are based upon a series of experiments performed with simulated solutions on materials used for construction of the tanks, namely ASTM A537 carbon steel (A537). During FY09, an experimental program was undertaken to investigate the risk associated with reducing the minimum molar nitrite concentration required to confidently inhibit pitting in dilute solutions (i.e., less than 1 molar nitrate). The experimental results and conclusions herein provide a statistical basis to quantify the probability of pitting for the tank wall exposed to various solutions with dilute concentrations of nitrate and nitrite. Understanding the probability for pitting will allow the facility to make tank-specific risk-based decisions for chemistry control. Based on previous electrochemical testing, a statistical test matrix was developed to refine and solidify the application of the statistical mixture/amount model to corrosion of A537 steel. A mixture/amount model was identified based on statistical analysis of recent and historically collected electrochemical data. This model provides a more complex relationship between the nitrate and nitrite concentrations and the probability of pitting than is represented by the model underlying the current chemistry control program, and its use may provide a technical basis for the utilization of less nitrite to inhibit pitting at concentrations below 1 molar nitrate. FY09 results fit within the mixture/amount model, and further refine the nitrate regime in which the model is applicable. The combination of visual observations and cyclic potentiodynamic polarization scans indicates a potential for significant inhibitor reductions at nitrate concentrations near 1.0 M without a significant increase in corrosion risk. The complete data sets from FY08 and FY09 testing have determined the statistical basis to confidently inhibit against pitting using nitrite inhibition with the current pH controls. Future testing will complete the spectrum of nitrate concentrations around 1 molar. These results will be combined to provide a complete spectrum for corrosion controls with a risk based component.

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DOE OSTI2010

SLUDGE BATCH VARIABILITY STUDY WITH FRIT 418

The Defense Waste Processing Facility (DWPF) initiated processing Sludge Batch 6 (SB6) in the summer of 2010. In support of processing, the Savannah River National Laboratory (SRNL) provided a recommendation to utilize Frit 418 to process SB6. This recommendation was based on assessments of the compositional projections for SB6 available at the time from the Liquid Waste Organization (LWO) and SRNL (using a model-based approach). To support qualification of SB6, SRNL executed a variability study to assess the applicability of the current durability models for SB6. The durability models were assessed over the expected Frit 418-SB6 composition range. Seventeen glasses were selected for the variability study based on the sludge projections used in the frit recommendation. Five of the glasses are based on the centroid of the compositional region, spanning a waste loading (WL) range of 32 to 40%. The remaining twelve glasses are extreme vertices (EVs) of the sludge region of interest for SB6 combined with Frit 418 and are all at 36% WL. These glasses were fabricated and characterized using chemical composition analysis, X-ray diffraction (XRD) and the Product Consistency Test (PCT). After initiating the SB6 variability study, the measured composition of the SB6 Tank 51 qualification glass produced at the SRNL Shielded Cells Facility indicated that thorium was present in the glass at an appreciable concentration (1.03 wt%), which made it a reportable element for SB6. This concentration of ThO{sub 2} resulted in a second phase of experimental studies. Five glasses were formulated that were based on the centroid of the new sludge compositional region combined with Frit 418, spanning a WL range of 32 to 40%. These glasses were fabricated and characterized using chemical composition analysis and the PCT. Based on the measured PCT response, all of the glasses (with and without thorium) were acceptable with respect to the Environmental Assessment (EA) reference glass regardless of thermal history. All of the normalized boron releases were less than 1 g/L. While all of the targeted glass compositions were predictable with respect to the Product Composition Control System (PCCS) models for durability, a small number of the measured glass compositions were located outside of the lower prediction limit indicating poorer durability than what was actually measured. These unpredictable glasses were in the same lithium metaborate (LM) preparation block during the chemical analyses, which resulted in measured compositions that were not representative of the target compositions. A review of the data did not indicate a clear cause for the problem. Re-digestion and re-measurement of three glasses from this preparation block yielded glass compositions closer to the target values and predicted PCT responses within the PCCS model uncertainty. Therefore, it is believed that the glasses were correctly fabricated and the targeted compositions are closer representations of the true compositions. Per the requirements of the DWPF Glass Product Control Program, the PCCS durability models have been shown to be applicable for the SB6/Frit 418 glass system. PCT results from the glasses fabricated as part of the variability study were shown to be predictable and/or acceptable with respect to the DWPF PCCS models. In addition, the inclusion of ThO{sub 2} was shown to have minimal impact on the acceptability and predictability of the variability study glasses.

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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

IMPACT OF REDUCING THE 100 C LIQUIDUS TEMPERATURE OFFSET ON WASTE LOADING TARGETS

The objective of this report is to assess the potential impact of reducing conservatism in the implementation of the current liquidus temperature (TL) model in the Product Composition Control System (PCCS) on the ability to target higher waste loadings (WLs) for future sludge batches. No changes to the TL model or the associated uncertainties (model or measurement) are proposed, rather only changes in the magnitude of the offset used between the nominal melt pool temperature (1150 C) and the Property Acceptance Region (PAR) value (1050 C). This strategy is consistent with that outlined and initially assessed by Brown et al. (2001). In that report, the authors stated even a fairly conservative change in this safety factor could have a significant impact on waste loading. The results of this study clearly indicate that the implementation of an 1100 C TL PAR criterion (which translates into a reduction in the TL offset from 100 C to 50 C) can have significantly positive impacts on the ability to gain access to WLs exceeding 45%. This is especially true for those frit and sludge systems that are TL limited using the current 1050 C TL criterion, and are not limited by a second constraint (such as viscosity, nepheline, or durability) until much higher WLs. Examples of various glass forming systems are provided that are currently limited to maximum WLs in the mid-40s, but could be processed in the lower 50s through implementation of this new strategy. One example is in the Sludge Batch 10 (SB10) system, where for a specific glass forming system the projected operating window of 38-41% WL (using the current constraints) became 38-52% WL with the use of an 1100 C TL PAR value. This change both provided access to significantly higher WLs, and transitioned a once infeasible flowsheet to a system that could potentially be processed in the Defense Waste Processing Facility (DWPF). This potential change in the TL constraint also provides access to frit compositions (or glass forming regions) that are not accessible under the current limitations. These new composition regions not only provide access to higher WLs, but may also allow frit development efforts to target other specific properties to support enhanced melter operations. It should be noted that under certain flowsheet conditions, the implementation of the 1100 C TL PAR must be accompanied by a shifting categorization of what is deemed an acceptable operating window for DWPF operation. For example, the use of a 50 C offset may not be effective if access to WLs < 30% are still required. Assuming the intent of implementing the 1100 C PAR criterion is to gain access to higher WLs (> 45%), the need to identify frit and sludge systems that are predicted to form acceptable glasses at these lower WLs (< 30%) should no longer be of concern. Although this strategy could have a significant impact on DWPF's ability to target higher WLs (> 45%), its implementation is not risk free. The reduction in the TL offset does reduce the conservatism currently implemented, which is aimed at minimizing or eliminating the potential for massive devitrification within the melt pool. Prior to implementation of this alternative strategy, DWPF should perform a risk-based assessment or review of this alternative approach to ensure it aligns with needs and processing strategies.

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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

DEVELOPMENT AND DEPLOYMENT OF VACUUM SALT DISTILLATION AT THE SAVANNAH RIVER SITE

The Savannah River Site has a mission to dissolve fissile materials and disposition them. The primary fissile material is plutonium dioxide (PuO{sub 2}). To support dissolution of these materials, the Savannah River National Laboratory (SRNL) designed and demonstrated a vacuum salt distillation (VSD) apparatus using both representative radioactive samples and non-radioactive simulant materials. Vacuum salt distillation, through the removal of chloride salts, increases the quantity of materials suitable for processing in the site's HB-Line Facility. Small-scale non-radioactive experiments at 900-950 C show that >99.8 wt % of the initial charge of chloride salt distilled from the sample boat with recovery of >99.8 wt % of the ceric oxide (CeO{sub 2}) - the surrogate for PuO{sub 2} - as a non-chloride bearing 'product'. Small-scale radioactive testing in a glovebox demonstrated the removal of sodium chloride (NaCl) and potassium chloride (KCl) from 13 PuO{sub 2} samples. Chloride concentrations were distilled from a starting concentration of 1.8-10.8 wt % to a final concentration <500 mg/kg chloride. Initial testing of a non-radioactive, full-scale production prototype is complete. A designed experiment evaluated the impact of distillation temperature, time at temperature, vacuum, product depth, and presence of a boat cover. Significant effort has been devoted to mechanical considerations to facilitate simplified operation in a glovebox.

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DOE OSTI2010

THE SUITABILITY OF SODIUM PEROXIDE FUSION FOR PRODUCTION-SCALE PLUTONIUM PROCESSING OPERATIONS

Sodium peroxide (Na{sub 2}O{sub 2}) fusion is a method that offers significant benefits to the processing of high-fired plutonium oxide (PuO{sub 2}) materials. Those benefits include reduction in dissolution cycle time, decrease in residual solids, and reduction of the potential for generation of a flammable gas mixture during dissolution. Implementation of Na{sub 2}O{sub 2} fusion may also increase the PuO{sub 2} throughput in the HB-Line dissolving lines. To fuse a material, Na{sub 2}O{sub 2} is mixed with the feed material in a crucible and heated to 600-700 C. For low-fired and high-fired PuO{sub 2}, Na{sub 2}O{sub 2} reacts with PuO{sub 2} to form a compound that readily dissolves in ambient-temperature nitric acid without the use of potassium fluoride. The Savannah River National Laboratory (SRNL) demonstrated the feasibility of Na{sub 2}O{sub 2} fusion and subsequent dissolution for the processing of high-fired PuO{sub 2} materials in HB-Line. Testing evaluated critical dissolution characteristics and defined preliminary process parameters. Based on experimental measurements, a dissolution cycle can be complete in less than one hour, compared to the current processing time of 6-10 hours for solution heating and dissolution. Final Pu concentrations of 30-35 g/L were produced without the formation of precipitates in the final solution.

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DOE OSTI2010

SLURRY MIX EVAPORATOR BATCH ACCEPTABILITY AND TEST CASES OF THE PRODUCT COMPOSITION CONTROL SYSTEM WITH THORIUM AS A REPORTABLE ELEMENT

The Defense Waste Processing Facility (DWPF), which is operated by Savannah River Remediation, LLC (SRR), has recently begun processing Sludge Batch 6 (SB6) by combining it with Frit 418 at a nominal waste loading (WL) of 36%. A unique feature of the SB6/Frit 418 glass system, as compared to the previous glass systems processed in DWPF, is that thorium will be a reportable element (i.e., concentrations of elemental thorium in the final glass product greater than 0.5 weight percent (wt%)) for the resulting wasteform. Several activities were initiated based upon this unique aspect of SB6. One of these was an investigation into the impact of thorium on the models utilized in DWPF's Product Composition and Control System (PCCS). While the PCCS is described in more detail below, for now note that it is utilized by Waste Solidification Engineering (WSE) to evaluate the acceptability of each batch of material in the Slurry Mix Evaporator (SME) before this material is passed on to the melter. The evaluation employs models that predict properties associated with processability and product quality from the composition of vitrified samples of the SME material. The investigation of the impact of thorium on these models was conducted by Peeler and Edwards [1] and led to a recommendation that DWPF can process the SB6/Frit 418 glass system with ThO{sub 2} concentrations up to 1.8 wt% in glass. Questions also arose regarding the handling of thorium in the SME batch acceptability process as documented by Brown, Postles, and Edwards [2]. Specifically, that document is the technical bases of PCCS, and while Peeler and Edwards confirmed the reliability of the models, there is a need to confirm that the current implementation of DWPF's PCCS appropriately handles thorium as a reportable element. Realization of this need led to a Technical Task Request (TTR) prepared by Bricker [3] that identified some specific SME-related activities that the Savannah River National Laboratory (SRNL) was requested to conduct. SRNL issued a Task Technical and Quality Assurance (TT&QA) plan [4] in response to the SRR request. The conclusions provided in this report are that no changes need to be made to the SME acceptability process (i.e., no modifications to WSRC-TR-95-00364, Revision 5, are needed) and no changes need to be made to the Product Composition Control System (PCCS) itself (i.e. the spreadsheet utilized by Waste Solidification Engineering (WSE) for acceptability decisions does not require modification) in response to thorium becoming a reportable element for DWPF operations. In addition, the inputs and results for the two test cases requested by WSE for use in confirming the successful activation of thorium as a reportable element for DWPF operations during the processing of SB6 are presented in this report.

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DOE OSTI2010

PLUTONIUM SOLUBILITY IN SIMULATED SAVANNAH RIVER SITE WASTE SOLUTIONS

To address the accelerated disposition of the supernate and salt portions of Savannah River Site (SRS) high level waste (HLW), solubility experiments were performed to develop a predictive capability for plutonium (Pu) solubility. A statistically designed experiment was used to measure the solubility of Pu in simulated solutions with salt concentrations and temperatures which bounded those observed in SRS HLW solutions. Constituents of the simulated waste solutions included: hydroxide (OH{sup -}), aluminate (Al(OH){sub 4}{sup -}), sulfate (SO{sub 4}{sup 2-}), carbonate (CO{sub 3}{sup 2-}), nitrate (NO{sub 3}{sup -}), and nitrite (NO{sub 2}{sup -}) anions. Each anion was added to the waste solution in the sodium form. The solubilities were measured at 25 and 80 C. Five sets of samples were analyzed over a six month period and a partial sample set was analyzed after nominally fifteen months of equilibration. No discernable time dependence of the measured Pu concentrations was observed except for two salt solutions equilibrated at 80 C which contained OH{sup -} concentrations >5 mol/L. In these solutions, the Pu solubility increased with time. This observation was attributed to the air oxidation of a portion of the Pu from Pu(IV) to the more soluble Pu(V) or Pu(VI) valence states. A data driven approach was subsequently used to develop a modified response surface model for Pu solubility. Solubility data from this study and historical data from the literature were used to fit the model. The model predicted the Pu solubility of the solutions from this study within the 95% confidence interval for individual predictions and the analysis of variance indicated no statistically significant lack of fit. The Savannah River National Laboratory (SRNL) model was compared with predicted values from the Aqueous Electrolyte (AQ) model developed by OLI Systems, Inc. and a solubility prediction equation developed by Delegard and Gallagher for Hanford tank waste. The agreement between measured or values predicted by the SRNL model and values predicted by the OLI AG model was very poor. The much higher predicted concentrations by the OLI AQ model appears to be the result of the model predicting the predominate Pu oxidation state is Pu(V) which is reported as unstable below sodium hydroxide (NaOH) concentrations of 6 M. There was very good agreement between the predicted Pu concentrations using the SRNL model and the model developed by Delegard and Gallagher with the exception of solutions that had very high OH{sup -} (15 M) concentrations. The lower Pu solubilities in these solutions were attributed to the presence of NO{sub 3}{sup -} and NO{sub 2}{sup -} which limit the oxidation of Pu(IV) to Pu(V).

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DOE OSTI2010

TIME-TEMPERATURE-TRANSFORMATION (TTT) DIAGRAMS FOR FUTURE WASTE COMPOSITIONS

As a part of the Waste Acceptance Product Specifications (WAPS) for Vitrified High-Level Waste Forms defined by the Department of Energy - Office of Environmental Management, the waste form stability must be determined for each of the projected high-level waste (HLW) types at the Savannah River Site (SRS). Specifically, WAPS 1.4.1 requires the glass transition temperature (T{sub g}) to be defined and time-temperature-transformation (TTT) diagrams to be developed. The T{sub g} of a glass is an indicator of the approximate temperature where the supercooled liquid converts to a solid on cooling or conversely, where the solid begins to behave as a viscoelastic solid on heating. A TTT diagram identifies the crystalline phases that can form as a function of time and temperature for a given waste type or more specifically, the borosilicate glass waste form. In order to assess durability, the Product Consistency Test (PCT) was used and the durability results compared to the Environmental Assessment (EA) glass. The measurement of glass transition temperature and the development of TTT diagrams have already been performed for the seven Defense Waste Processing Facility (DWPF) projected compositions as defined in the Waste Form Compliance Plan (WCP) and in SRNL-STI-2009-00025. Additional phase transformation information exists for other projected compositions, but overall these compositions did not cover composition regions estimated for future waste processing. To develop TTT diagrams for future waste types, the Savannah River National Laboratory (SRNL) fabricated two caches of glass from reagent grade oxides to simulate glass compositions which would be likely processed with and without Al dissolution. These were used for glass transition temperature measurement and TTT diagram development. The glass transition temperatures of both glasses were measured using differential scanning calorimetry (DSC) and were recorded to be 448 C and 452 C. Using the previous TTT diagrams as guidance, subsamples of each glass were isothermally heat treated for 1 to 768 hours at temperatures between 500 C to 1000 C. Each of the heat treated samples, along with quenched and centerline canister cooled (CCC) treated samples, were analyzed using X-ray diffraction (XRD) and the PCT. Maximum crystallization was detected in samples treated at 700 C and 600 C for more than 96 hours in both glasses. Phases crystallized were similar in composition if not the same as those found in the previous TTT studies. Six different crystalline phases were detected, including nepheline, aegirine, lithium silicate, trevorite (spinel based), krinovite, and calcium magnesium iron silicon oxide. Overall, phases were spinel (iron) based, lithium metasilicate, sodium aluminosilicate or alkali transition metal silicate in composition. No new crystalline families were detected. Durability, as measured by the PCT, decreased when lithium silicate or nepheline crystals were present. The conclusions of this study were consistent with previous studies. In order to continue to meet the requirements of the WCP, a simplified strategy is suggested for the generation of future TTT diagrams. Only extremely significant changes in composition resulting from processing strategy changes would require generating more TTT diagrams.

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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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DOE OSTI2010

RESULTS OF THE FY09 ENHANCED DOE HIGH LEVEL WASTE MELTER THROUGHPUT STUDIES AT SRNL

High-level waste (HLW) throughput (i.e., the amount of waste processed per unit time) is a function of two critical parameters: waste loading (WL) and melt rate. For the Waste Treatment and Immobilization Plant (WTP) at the Hanford Site and the Defense Waste Processing Facility (DWPF) at the Savannah River Site (SRS), increasing HLW throughput would significantly reduce the overall mission life cycle costs for the Department of Energy (DOE). The objective of this task is to develop data, assess property models, and refine or develop the necessary models to support increased WL of HLW at SRS. It is a continuation of the studies initiated in FY07, but is under the specific guidance of a Task Change Request (TCR)/Work Authorization received from DOE headquarters (Project Number RV071301). Using the data generated in FY07, FY08 and historical data, two test matrices (60 glasses total) were developed at the Savannah River National Laboratory (SRNL) in order to generate data in broader compositional regions. These glasses were fabricated and characterized using chemical composition analysis, X-ray Diffraction (XRD), viscosity, liquidus temperature (TL) measurement and durability as defined by the Product Consistency Test (PCT). The results of this study are summarized below: (1) In general, the current durability model predicts the durabilities of higher waste loading glasses quite well. A few of the glasses exhibited poorer durability than predicted. (2) Some of the glasses exhibited anomalous behavior with respect to durability (normalized leachate for boron (NL [B])). The quenched samples of FY09EM21-02, -07 and -21 contained no nepheline or other wasteform affecting crystals, but have unacceptable NL [B] values (> 10 g/L). The ccc sample of FY09EM21-07 has a NL [B] value that is more than one half the value of the quenched sample. These glasses also have lower concentrations of Al{sub 2}O{sub 3} and SiO{sub 2}. (3) Five of the ccc samples (EM-13, -14, -15, -29 and -30) completely crystallized with both magnetite and nepheline, and still had extremely low NL [B] values. These particular glasses have more CaO present than any of the other glasses in the matrix. It appears that while all of the glasses contain nepheline, the NL [B] values decrease as the CaO concentration increases from 2.3 wt% to 4.3 wt%. A different form of nepheline may be created at higher concentrations of CaO that does not significantly reduce glass durability. (4) The T{sub L} model appears to be under-predicting the measured values of higher waste loading glasses. Trends in T{sub L} with composition are not evident in the data from these studies. (5) A small number of glasses in the FY09 matrix have measured viscosities that are much lower than the viscosity range over which the current model was developed. The decrease in viscosity is due to a higher concentration of non-bridging oxygens (NBO). A high iron concentration is the cause of the increase in NBO. Durability, viscosity and T{sub L} data collected during FY07 and FY09 that specifically targeted higher waste loading glasses was compiled and assessed. It appears that additional data may be required to expand the coverage of the T{sub L} and viscosity models for higher waste loading glasses. In general, the compositional regions of the higher waste loading glasses are very different than those used to develop these models. On the other hand, the current durability model seems to be applicable to the new data. At this time, there is no evidence to modify this model; however additional experimental studies should be conducted to determine the cause of the anomalous durability data.

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DOE OSTI2010

VERIFICATION OF THE DEFENSE WASTE PROCESSING FACILITY PROCESS DIGESTION METHOD FOR THE SLUDGE BATCH 6 QUALIFICATION SAMPLE

For each sludge batch that is processed in the Defense Waste Processing Facility (DWPF), the Savannah River National Laboratory (SRNL) confirms applicability of the digestion method to be used by the DWPF lab for elemental analysis of Sludge Receipt and Adjustment Tank (SRAT) receipt samples and SRAT product process control samples.1 DWPF SRAT samples are typically dissolved using a room temperature HF-HNO3 acid dissolution (i.e., DWPF Cold Chem (CC) Method, see DWPF Procedure SW4-15.201) and then analyzed by inductively coupled plasma - atomic emission spectroscopy (ICPAES). In addition to the CC method confirmation, the DWPF lab's mercury (Hg) digestion method was also evaluated for applicability to SB6 (see DWPF procedure 'Mercury System Operating Manual', Manual: SW4-15.204. Section 6.1, Revision 5, Effective date: 12-04-03). This report contains the results and comparison of data generated from performing the Aqua Regia (AR), Sodium Peroxide/Hydroxide Fusion (PF) and DWPF Cold Chem (CC) method digestion of Sludge Batch 6 (SB6) SRAT Receipt and SB6 SRAT Product samples. For validation of the DWPF lab's Hg method, only SRAT receipt material was used and compared to AR digestion results. The SB6 SRAT Receipt and SB6 SRAT Product samples were prepared in the SRNL Shielded Cells, and the SRAT Receipt material is representative of the sludge that constitutes the SB6 Batch or qualification composition. This is the sludge in Tank 51 that is to be transferred into Tank 40, which will contain the heel of Sludge Batch 5 (SB5), to form the SB6 Blend composition. In addition to the 16 elements currently measured by the DWPF, this report includes Hg and thorium (Th) data (Th comprising {approx}2.5 - 3 Wt% of the total solids in SRAT Receipt and SRAT Product, respectively) and provides specific details of ICP-AES analysis of Th. Thorium was found to interfere with the U 367.007 nm emission line, and an inter-element correction (IEC) had to be applied to U data, which is also discussed. The results for any one particular element should not be used in any way to identify the form or speciation of a particular element without support from XRD analysis or used to estimate ratios of compounds in the sludge.

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