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Using Robotic Manipulators for Radioactive Waste Inspection - 20090

The global nuclear industry has a growing volume of nuclear waste which needs to be scanned, sorted according to its activity and material type, then processed into the correct waste packages for long term storage and disposal. It is vital that there is a detailed understanding of the waste inventory stored in long term waste containers, as knowledge of their contents could predict or prevent any adverse effects in storage. The numerous 'scan and sort' tables which are currently used at many different facilities around the world to sort waste into their correct containers are human operated and require very slow gamma scanning procedures combined with educated guesswork to manually sort the waste. This often leads to excessive conservatisms, with placement of lower activity wastes in higher activity containers, which in turn costs significantly more to store. In the United Kingdom it costs UK Pounds 46 k per cubic meter to store intermediate level waste compared to just UK Pound 2.9 k per cubic meter to store low level waste according to a 2008 Department of Energy and Climate Change report in the UK. A proposed solution to this problem, is the use of a robotic manipulator to automatically inspect the 'scan and sort table' in order to produce an accurate 3D model of the table's waste contents and attach an overlaid radiation map. The radiation map contains spectrometry data and can in consequence be used to distinguish and locate specific radioisotopes. The 3D model should be as accurate as possible in order to allow for a second robot arm with an attached gripper to grasp the objects and place them into their designated long-term storage container. Various scanning procedures are explored in this study including basic raster scanning, adaptive raster scanning and point sampling. The optimal solution will in practice be defined by the required application and activity level of the wastes being inspected. The results presented in this study indicate that it is possible to produce a centimeter accurate 3D model of a mixed assortment of components on a nuclear waste 'scan and sort' table. In addition, it was shown that the waste objects emitting radiation could be accurately identified and located, with an overlaid radiation map. This study is applicable across the nuclear waste management sector. Many of the ideas and concepts developed in this study are applicable in other decommissioning settings for example, dismantling of legacy gloveboxes or routine inspection of nuclear waste packages in storage. (authors)

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Integrated DM1200 Melter Testing of HLW C-106/AY-102 Composition Using Bubblers

This report documents melter and off-gas performance results obtained on the DM1200 HLW Pilot Melter during processing of simulated HLW C-106/AY-102 feed. The principal objectives of the DM1200 melter testing were to determine the achievable glass production rates for simulated HLW C-106/AY-102 feed; determine the effect of bubbling rate on production rate; characterize melter off-gas emissions; characterize the performance of the prototypical off-gas system components as well as their integrated performance; characterize the feed, glass product, and off-gas effluents; and to perform pre- and post test inspections of system components.

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R and DE Robotic Sensor Intern Team: Remote 3D Mapping Sensor Suite

The primary goal of the sensor suite is to provide an internal 3D map of the HCAEX tunnel. When looking for a sensor that would provide XYZ point cloud data for mapping the decision was between a stereo camera, a 3D Lidar, or a 2D Lidar that would need to be spun around. The issues with the stereo camera were that it does not have a large field-of-view and that its depth information was not nearly as accurate as even the baseline Lidars. The selection between Lidars is detailed. The Hokuyo UTM-30LX-EW shown provides a 270 deg. FOV with high accuracy and resolution while the largest FOV on a 3D Lidar is 40 deg.. This was the reason a 2D Lidar was chosen over the 3D Lidar. Even though the 2D Lidar requires additional components and software to generate a 3D map, its FOV advantage is too great given that the HCAEX tunnel is a relatively confined space. The rotating planar scan from the 2D Lidar can be stitched into a 3D scan as shown in the graphic below. Along with XYZ data, the Lidar provides return intensity data in color which can be used to distinguish between different materials within the tunnel. To provide visual feedback a camera system needed to be identified. The common solution for this is a high resolution camera with a small FOV mounted on a pan-tilt system. But, given the critical nature of the visual feedback we looked into solutions without the need for moving parts. Two panospheric cameras give a FOV large enough to get a full 360 deg. view.. Camera color data (RGB) can also be combined with the 3D mapping data from the Lidar and overlaid on the map to give the user the ability to see inside the entire length of the tunnel as if they were inside. Situational awareness is required for the crawler in the tunnel in order for it to be able to register the 3D scans to create a final map. For this we procured a Microstrain 3DM-GX5-25 Inertial Measurement Unit (IMU). To perform the Lidar rotation we have two servos driving the pan and tilt. The servo controls and most data processing will be performed via an onboard computer. The sensor components are to be packaged together using 3D printed mounts into a standalone unit.

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FY16 Annual Accomplishments - Waste Form Development and Performance: Evaluation Of Ceramic Waste Forms - Comparison Of Hot Isostatic Pressed And Melt Processed Fabrication Methods

FY16 efforts were focused on direct comparison of multi-phase ceramic waste forms produced via melt processing and HIP methods. Based on promising waste form compositions previously devised at SRNL, simulant material was prepared at SRNL and a portion was sent to the Australian Nuclear Science and Technology Organization (ANSTO) for HIP treatments, while the remainder of the material was melt processed at SRNL. The microstructure, phase formation, elemental speciation, and leach behavior, and radiation stability of the fabricated ceramics was performed. In addition, melt-processed ceramics designed with different fractions of hollandite, zirconolite, perovskite, and pyrochlore phases were investigated. for performance and properties.

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Synthesis of results for Brine Availability Test in Salt (BATS) DECOVALEX-2023 Task E

In the 2023 phase of the international collaborative DECOVALEX modeling project, Task E focused on understanding thermal, hydrological, and mechanical (THM) processes related to predicting brine migration in the excavation damaged zone around a heated excavation in salt. Salt is attractive as a disposal medium for radioactive waste because it is self-healing and is essentially impermeable and non-porous in the far field. Investigation of the short-term, near-field behavior is important for radioactive waste disposal because this early period strongly controls the amount of inflowing brine. Brine leads to corrosion of waste forms and waste packages, and possible dissolution of radionuclides with brine transport being a potential transport vector to the accessible environment.The Task was divided into steps. Step 0 included matching unheated brine inflow data from boreholes at the Waste Isolation Pilot Plant (WIPP) and matching temperature observations during a Brine Availability Test in Salt (BATS) heater test. Step 1 included validation of models against a thermo-poroelastic analytical solution, and two-phase flow around an excavation. Finally, Step 2 required all the individual components covered in steps 0 and 1 to come together to match observed brine inflow behavior during the same BATS heater test.There were a range of approaches from the teams, from mechanistic to prescriptive. Given the uncertainties in the problem, some teams used one- or two-dimensional models of the processes, while other teams included more geometrical complexity in three-dimensional models. Task E was a learning experience for the teams involved, and feedback from the modeling teams has led to changes in follow-on BATS experiments at WIPP. The primary Task E lessons learned were the impact of hydrologic initialization methods (wetting up vs. drying down), the difference between confined and unconfined thermal expansion, and the large changes in permeability associated with heating and cooling.

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Anaerobic digestion of solid agroindustrial waste in semi-continuous mode: Evaluation of mono-digestion and co-digestion systems

Highlights: • Agroindustrial waste were co-digested with an artificial organic fraction. • Variations in organic loading rate and hydraulic retention time were studied. • Sequential feeding of the substrates based on their seasonality was investigated. • Co-digestion resulted in higher methane yields compared with mono-digestion. • Applying sequential feeding led to a more equilibrated system operation. - Abstract: The present study aimed at investigating the anaerobic digestion of four agroindustrial waste, namely cotton gin waste, winery waste, olive pomace and juice industry waste, in semi-continuous mode, conducting mono-digestion and co-digestion assays, using an artificial organic fraction sample as co-substrate. These assays were divided into two groups, in which different conditions were applied. Group I investigated the variation in two operational parameters, i.e. the organic loading rate (OLR) and the hydraulic retention time (HRT), while in Group II, the assays were fed with different substrates in a sequential order. Results showed more elevated specific methane yields for co-digestion assays compared with mono-digestion assays. Maximum yields were achieved at an OLR of 1.0 gVS/(L·d) and a HRT reduced to half of the initial. Further reduction of the HRT coupled to an increase of the OLR generally caused a significant decrease of specific methane yields, as well as one case of severe overloading, i.e. the mono-digestion of juice industry waste, which resulted in instability and ultimately system failure. Sequential feeding with different substrates led to a more equilibrated operation, especially for co-digestion systems, with higher specific methane yields being observed during the phases corresponding to winery waste and juice industry waste substrates. Overall more positive results were obtained in the cases in which the latter substrates were fed to the reactors at process startup.

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WTP Waste Feed Qualification: Glass Fabrication Unit Operation Testing Report

The waste feed qualification program is being developed to protect the Hanford Tank Waste Treatment and Immobilization Plant (WTP) design, safety basis, and technical basis by assuring waste acceptance requirements are met for each staged waste feed campaign prior to transfer from the Tank Operations Contractor to the feed receipt vessels inside the Pretreatment Facility. The Waste Feed Qualification Program Plan describes the three components of waste feed qualification: 1. Demonstrate compliance with the waste acceptance criteria 2. Determine waste processability 3. Test unit operations at laboratory scale. The glass fabrication unit operation is the final step in the process demonstration portion of the waste feed qualification process. This unit operation generally consists of combining each of the waste feed streams (high-level waste (HLW) and low-activity waste (LAW)) with Glass Forming Chemicals (GFCs), fabricating glass coupons, performing chemical composition analysis before and after glass fabrication, measuring hydrogen generation rate either before or after glass former addition, measuring rheological properties before and after glass former addition, and visual observation of the resulting glass coupons. Critical aspects of this unit operation are mixing and sampling of the waste and melter feeds to ensure representative samples are obtained as well as ensuring the fabrication process for the glass coupon is adequate. Testing was performed using a range of simulants (LAW and HLW simulants), and these simulants were mixed with high and low bounding amounts of GFCs to evaluate the mixing, sampling, and glass preparation steps in shielded cells using laboratory techniques. The tests were performed with off-the-shelf equipment at the Savannah River National Laboratory (SRNL) that is similar to equipment used in the SRNL work during qualification of waste feed for the Defense Waste Processing Facility (DWPF) and other waste treatment facilities at the Savannah River Site. It is not expected that the exact equipment used during this testing will be used during the waste feed qualification testing for WTP, but functionally similar equipment will be used such that the techniques demonstrated would be applicable. For example, the mixing apparatus could use any suitable mixer capable of being remoted and achieving similar mixing speeds to those tested.

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Optimization of salt-cake removal flowsheet at SRS through incorporation of testing and in-tank waste experience - 15263

Salt-cake removal at SRS may be performed for several reasons: to provide space for evaporator operation (i.e., to precipitate more salt in the drop tank), to provide feed for salt processing (i.e. immobilize the waste), or to remove the salt for tank closure. Many different salt dissolution techniques have been employed in the 40 years that SRS has been performing salt removal, from a basic 'Add, Sit, Remove' method (water is added on top of the salt-cake and time is allowed for diffusion), to performing interstitial liquid removal, or using mixing devices to promote contact with the liquid. Lessons learned from previous salt-cake removal campaigns, in addition to testing and modeling, have led to opportunities for improvements to the overall salt-cake removal process. This includes better understanding of salt properties and behavior during dissolution; the primary concerns for salt dissolution are the release of radiolytic hydrogen and criticality prevention (post-dissolution). Recent developments in salt dissolution include the reuse of dilute supernate and a semi-continuous dissolution (SCD) process, where low volume mixing eductors are used to deliver water near the surface of the salt-cake at the same rate as the salt solution is removed and transferred to a receipt tank. (authors)

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Iron Phosphate Glass-Containing Hanford Waste Simulant (Rev. 1)

Resolution of the nation's high-level tank waste legacy requires the design, construction, and operation of large and technically complex one-of-a-kind processing waste treatment and vitrification facilities. While the ultimate limits for waste loading and melter efficiency have yet to be defined or realized, significant reductions in glass volumes for disposal and mission life may be possible with advancements in melter technologies and/or glass formulations. This test report describes the experimental results from a small-scale test using the research-scale melter (RSM) at Pacific Northwest National Laboratory (PNNL) to demonstrate the viability of iron-phosphate-based glass with a selected waste composition that is high in sulfate (4.37 wt% SO 3 ). The primary objective of the test was to develop data to support a cost-benefit analysis related to the implementation of phosphate-based glasses for Hanford low-activity waste (LAW) and/or other high-level waste streams within the U.S. Department of Energy complex. The testing was performed by PNNL and supported by Idaho National Laboratory, Savannah River National Laboratory, Missouri University of Science and Technology, and Mo-Sci Corporation.

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The Countermeasure for the Noble Metal in the HLW Vitrification - the Removal Technology of Ru, Rh and Pd from the System - 16118

In this study, the system to separate ruthenium (Ru) in High-level radioactive liquid waste (HLLW), which has negative impact for the vitrification system, was investigated. It consists of three main parts. One is the process to remove Ru in HLLW by oxidizing Ru to RuO{sub 4} using ozone (O{sub 3}) and by heating to make RuO{sub 4} vaporize. Second one is the process collecting gas RuO{sub 4} vaporized from HLLW in the previous process. Final one is a degradation process of O{sub 3} which still remains. Several experiments were carried out to evaluate each process using the liquid waste simulating HLLW (SHLLW). As results of them, we found out bellows. (1) Approximately 100% of Ru could be removed from SHLLW by adding O{sub 3} to heated SHLLW in 80 degree C. (2) Over 80% of gas RuO{sub 4} was destructed to RuO{sub 2} particle in over 300 degree C without O{sub 2}/O{sub 3}. And nearly 100 % O{sub 3} gas was also degraded in the same condition. From those results, the system to remove Ru from HLLW before putting it into the glass melter must be realized by setting additional HLLW heating process with O{sub 3} supplying equipment and additional heating process of gas exhausted from the previous HLLW heating process. In the system, additional waste is not generated because of no additional solid and liquid chemicals. Moreover, we confirmed that DBP (di-butyl phosphate) which was added in SHLLW, was also degraded adding O{sub 3}. In addition, it was found that rhodium (Rh) and palladium (Pd) remained in glass make a low melting point alloy by adding TeO{sub 2} and its fluidity can be improved. (authors)

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Control Decision and Control Development of Hanford Tank Farms First Two ISA-84 Safety Instrumented Systems - 17370

Hanford's 242-A Evaporator has had the mission of reducing waste volume in the Hanford Tank Farms since the late 1970's. Until 2014, the Documented Safety Analysis for the 242-A facility considered protection and controls of the collocated worker (workers outside the facility) and the public. In 2010, Tank Farms Nuclear Safety engineers initiated a significant revision of the Documented Safety Analysis to implement DOE-STD-3009, Change Notice 3, which requires the protection of the facility worker in addition to the collocated worker and public. Through the use of an extensive process hazards analysis performed on the facility, it was concluded that it was essential to control conditions in the primary evaporation vessel (C-A-1) such that flammable gasses could not build up to the Lower Flammability Limit, and that another control was necessary to ensure that the C-A-1 vessel could not overflow. Early control decision meetings held during the development of the Documented Safety Analysis revision yielded no simple solution to the protection of workers from a flammable gas deflagration. Controls selected for the waste overflow accident were all mitigative in nature (i.e. the detection of a waste overflow after it already happened). Engineering could not replace the mitigative controls with preventive controls without attempting to credit some of the existing facility interlocks associated with the C-A-1 vessel operations. Software and hard-wired interlocks had been used at the facility to prevent overheating of the waste and overfilling of the C-A-1 vessel. These interlocks were considered useful to the prevention of the flammable gas deflagration and vessel overfilling accidents, but lacked the pedigree and reliability necessary to credit the interlocks as safety significant. It was at this stage of the Documented Safety Analysis control decision and control development that engineering became aware of the DOE's acceptance of the ISA-84 instrumented system standard. It became apparent that the ideal solution was not to attempt to credit existing interlock systems, but to develop a new system of 'safety interlocks' to the ISA-84 standard. A meeting was held with upper management of both engineering and operations to propose the use of safety instrumented systems at the 242-A facility. URS Corporation (now AECOM), who had recently supported the Savanah River site in developing ISA-84 controls, was consulted to support the development of two new instrumented systems for the 242-A facility. In addition to the use of the newly adopted ISA-84 standard, the failure modes and effect analysis process was implemented in a very effective manner to support the development of the new safety instrumented systems. Through a brand new methodology, and through a very dedicated and hard-working engineering, projects, and operations team, the new controls were designed, built, tested, and commissioned. At this time, five successful waste reduction campaigns have been performed at the facility with the new safety instrumented systems. During these waste processing campaigns, trips and spurious trips of the SIS have occurred - all of which acted properly. (authors)

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Final Report DM1200 Tests with AZ-101 HLW Simulants

This report documents melter and off-gas performance results obtained on the DM 1200 HLW Pilot Melter during processing of simulated HLW AZ-101 feed. The principal objectives of the DM1200 melter testing were to determine the achievable glass production rates for simulated HLW AZ-101 feed; determine the effect of bubbling rate and feed solids content on production rate; characterize melter off-gas emissions; characterize the performance of the prototypical off-gas system components as well as their integrated performance; characterize the feed, glass product, and off-gas effluents; and to perform pre- and post-test inspections of system components. The test objectives (including test success criteria), along with how they were met, are outlined in a table.

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Considerations of the Differences between Bedded and Domal Salt Pertaining to Disposal of Heat-Generating Nuclear Waste

Salt formations hold promise for eternal removal of nuclear waste from our biosphere. Germany and the United States have ample salt formations for this purpose, ranging from flat-bedded formations to geologically mature dome structures. As both nations revisit nuclear waste disposal options, the choice between bedded, domal, or intermediate pillow formations is once again a contemporary issue. For decades, favorable attributes of salt as a disposal medium have been extoled and evaluated, carefully and thoroughly. Yet, a sense of discovery continues as science and engineering interrogate naturally heterogeneous systems. Salt formations are impermeable to fluids. Excavation-induced fractures heal as seal systems are placed or natural closure progresses toward equilibrium. Engineering required for nuclear waste disposal gains from mining and storage industries, as humans have been mining salt for millennia. This great intellectual warehouse has been honed and distilled, but not perfected, for all nuances of nuclear waste disposal. Nonetheless, nations are able and have already produced suitable license applications for radioactive waste disposal in salt. A remaining conundrum is site location. Salt formations provide isolation and geotechnical barriers reestablish impermeability after waste is placed in the geology. Between excavation and closure, physical, mechanical, thermal, chemical, and hydrological processes ensue. Positive attributes for isolation in salt have many commonalities independent of the geologic setting. In some cases, specific details of the environment will affect the disposal concept and thereby define interaction of features, events and processes, while simultaneously influencing scenario development. Here we identify and discuss high-level differences and similarities of bedded and domal salt formations. Positive geologic and engineering attributes for disposal purposes are more common among salt formations than are significant differences. Developing models, testing material, characterizing processes, and analyzing performance all have overlapping application regardless of the salt formation of interest.

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Considerations of the Differences between Bedded and Domal Salt Pertaining to Disposal of Heat-Generating Nuclear Waste

Salt formations hold promise for eternal removal of nuclear waste from our biosphere. Germany and the United States have ample salt formations for this purpose, ranging from flat-bedded formations to geologically mature dome structures. As both nations revisit nuclear waste disposal options, the choice between bedded, domal, or intermediate pillow formations is once again a contemporary issue. For decades, favorable attributes of salt as a disposal medium have been extoled and evaluated, carefully and thoroughly. Yet, a sense of discovery continues as science and engineering interrogate naturally heterogeneous systems. Salt formations are impermeable to fluids. Excavation-induced fractures heal as seal systems are placed or natural closure progresses toward equilibrium. Engineering required for nuclear waste disposal gains from mining and storage industries, as humans have been mining salt for millennia. This great intellectual warehouse has been honed and distilled, but not perfected, for all nuances of nuclear waste disposal. Nonetheless, nations are able and have already produced suitable license applications for radioactive waste disposal in salt. A remaining conundrum is site location. Salt formations provide isolation, and geotechnical barriers reestablish impermeability after waste is placed in the geology. Between excavation and closure, physical, mechanical, thermal, chemical, and hydrological processes ensue. Positive attributes for isolation in salt have many commonalities independent of the geologic setting. In some cases, specific details of the environment will affect the disposal concept and thereby define interaction of features, events and processes, while simultaneously influencing scenario development. Here we identify and discuss high-level differences and similarities of bedded and domal salt formations. Positive geologic and engineering attributes for disposal purposes are more common among salt formations than are significant differences. Developing models, testing material, characterizing processes, and analyzing performance all have overlapping application regardless of the salt formation of interest.

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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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Development of a Semi-autonomous Miniature Rover for Inspection of Double Shell Tank Floors - 19575

Leaks in the primary liner of double-shell tank (DST) 241-AY-102 at Hanford have prompted the need for the development of inspection tools that are able to access confined spaces around and underneath the tanks. Last year, Florida International University (FIU) has continued to improve inspection tools that were developed in the previous years, to ensure that the resultant tools are able to overcome the challenges posed by the DSTs. Experimental testing conducted last year at the full-scale sectional mock-up of the DST's refractory slots revealed some shortcomings of the miniature rover, particularly in traversing over weld seams of different heights. The weld seams are the results of welded steel plate-joints for the DST. It was advised by the site engineers that the weld seams height could range from 6.35 mm - 9.525 mm (1/4 to 3/8 inches), and with 12.7 mm (1/2 inches) width. As the rover traverses over a weld seam, the gap between the rover's magnets and tank surface increases, causing the adhesive force to drop. The rover loses its surface contact if this adhesive force drops below its weight, jeopardizing the inspection tasks. In this paper, we present the numerical studies to calculate the minimum magnetic force required for the miniature rover to traverse over weld seams with different heights and the corresponding modifications to the rover design. Initial bench scale tests were conducted using a steel bar with 5 welds of varying heights. The testing validated the results from the simulation studies and established the rover's capability in traversing weld seams. Another challenge for the miniature rover is the use of a joystick or keypad for manual control. Utilizing these controls will likely be difficult for the operators due to the tight channels underneath the tank. Having a semi-autonomous navigational capability would alleviate the complexity of the inspection tasks and allow the operator to focus on the channel inspection. The goal is to implement lane-keeping capability, akin to that of a driverless car, for the inspection tool, so that it will maintain its relative position with respect to the wall of the channels. Am image processing pipeline has been developed using both the Robot Operating System (ROS) and OpenCV to process the image stream coming from the onboard camera, for the purpose of lane identification. Additionally, a PID controller has been implemented to navigate the miniature rover along the central location of the detected lane, while allowing the operator to control the tool's forward and backward motion. (authors)

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Crystalline Ceramic Waste Forms: Report Detailing Data Collection In Support Of Potential FY13 Pilot Scale Melter Test

The research conducted in this work package is aimed at taking advantage of the long term thermodynamic stability of crystalline ceramics to create more durable waste forms (as compared to high level waste glass) in order to reduce the reliance on engineered and natural barrier systems. Durable ceramic waste forms that incorporate a wide range of radionuclides have the potential to broaden the available disposal options and to lower the storage and disposal costs associated with advanced fuel cycles. Assemblages of several titanate phases have been successfully demonstrated to incorporate radioactive waste elements, and the multiphase nature of these materials allows them to accommodate variation in the waste composition. Recent work has shown that they can be successfully produced from a melting and crystallization process. The objective of this report is to summarize the data collection in support of future melter demonstration testing for crystalline ceramic waste forms. The waste stream used as the basis for the development and testing is a combination of the projected Cs/Sr separated stream, the Trivalent Actinide - Lanthanide Separation by Phosphorous reagent Extraction from Aqueous Komplexes (TALSPEAK) waste stream consisting of lanthanide fission products, the transition metal fission product waste stream resulting from the transuranic extraction (TRUEX) process, and a high molybdenum concentration with relatively low noble metal concentrations. The principal difficulties encountered during processing of the “reference ceramic” waste form by a melt and crystallization process were the incomplete incorporation of Cs into the hollandite phase and the presence of secondary Cs-Mo non-durable phases. In the single phase hollandite system, these issues were addressed in this study by refining the compositions to include Cr as a transition metal element and the use of Ti/TiO 2 buffer to maintain reducing conditions. Initial viscosity studies of ceramic waste forms indicated that the pour spout must be maintained above 1400°C to avoid flow blockages due to crystallization. In-situ electron irradiations simulate radiolysis effects indicated hollandite undergoes a crystalline to amorphous transition after a radiation dose of 10 13 Gy which corresponds to approximately 1000 years at anticipated doses (2 10 10 -2 10 11 Gy). Dual-beam ion irradiations employing light ion beam (such as 5 MeV alpha) and heavy ion beam (such as 100 keV Kr) studies indicate that reference ceramic waste forms are radiation tolerant to the α-particles and β-particles, but are susceptible to a crystalline to amorphous transition under recoil nuclei effects. A path forward for refining the processing steps needed to form the targeted phase assemblages is outlined in this report. Processing modifications including melting in a reducing atmosphere with the use of Ti/TiO 2 buffers, and the addition of Cr to the transition metal additives to facilitate Cs-incorporation in the hollandite phase. In addition to melt processing, alternative fabrication routes are being considered including Spark Plasma Sintering (SPS) and Hot Isostatic Pressing (HIP).

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SOLIDIFICATION OF THE HANFORD LAW WASTE STREAM PRODUCED AS A RESULT OF NEAR-TANK CONTINUOUS SLUDGE LEACHING AND SODIUM HYDROXIDE RECOVERY

The U.S. Department of Energy (DOE), Office of River Protection (ORP), is responsible for the remediation and stabilization of the Hanford Site tank farms, including 53 million gallons of highly radioactive mixed wasted waste contained in 177 underground tanks. The plan calls for all waste retrieved from the tanks to be transferred to the Waste Treatment Plant (WTP). The WTP will consist of three primary facilities including pretreatment facilities for Low Activity Waste (LAW) to remove aluminum, chromium and other solids and radioisotopes that are undesirable in the High Level Waste (HLW) stream. Removal of aluminum from HLW sludge can be accomplished through continuous sludge leaching of the aluminum from the HLW sludge as sodium aluminate; however, this process will introduce a significant amount of sodium hydroxide into the waste stream and consequently will increase the volume of waste to be dispositioned. A sodium recovery process is needed to remove the sodium hydroxide and recycle it back to the aluminum dissolution process. The resulting LAW waste stream has a high concentration of aluminum and sodium and will require alternative immobilization methods. Five waste forms were evaluated for immobilization of LAW at Hanford after the sodium recovery process. The waste forms considered for these two waste streams include low temperature processes (Saltstone/Cast stone and geopolymers), intermediate temperature processes (steam reforming and phosphate glasses) and high temperature processes (vitrification). These immobilization methods and the waste forms produced were evaluated for (1) compliance with the Performance Assessment (PA) requirements for disposal at the IDF, (2) waste form volume (waste loading), and (3) compatibility with the tank farms and systems. The iron phosphate glasses tested using the product consistency test had normalized release rates lower than the waste form requirements although the CCC glasses had higher release rates than the quenched glasses. However, the waste form failed to meet the vapor hydration test criteria listed in the WTP contract. In addition, the waste loading in the phosphate glasses were not as high as other candidate waste forms. Vitrification of HLW waste as borosilicate glass is a proven process; however the HLW and LAW streams at Hanford can vary significantly from waste currently being immobilized. The ccc glasses show lower release rates for B and Na than the quenched glasses and all glasses meet the acceptance criterion of < 4 g/L. Glass samples spiked with Re{sub 2}O{sub 7} also passed the PCT test. However, further vapor hydration testing must be performed since all the samples cracked and the test could not be performed. The waste loading of the iron phosphate and borosilicate glasses are approximately 20 and 25% respectively. The steam reforming process produced the predicted waste form for both the high and low aluminate waste streams. The predicted waste loadings for the monolithic samples is approximately 39%, which is higher than the glass waste forms; however, at the time of this report, no monolithic samples were made and therefore compliance with the PA cannot be determined. The waste loading in the geopolymer is approximately 40% but can vary with the sodium hydroxide content in the waste stream. Initial geopolymer mixes revealed compressive strengths that are greater than 500 psi for the low aluminate mixes and less than 500 psi for the high aluminate mixes. Further work testing needs to be performed to formulate a geopolymer waste form made using a high aluminate salt solution. A cementitious waste form has the advantage that the process is performed at ambient conditions and is a proven process currently in use for LAW disposal. The Saltstone/Cast Stone formulated using low and high aluminate salt solutions retained at least 97% of the Re that was added to the mix as a dopant. While this data is promising, additional leaching testing must be performed to show compliance with the PA. Compressive strength tests must also be performed on the Cast Stone monoliths to verify PA compliance. Based on testing performed for this report, the borosilicate glass and Cast Stone are the recommended waste forms for further testing. Both are proven technologies for radioactive waste disposal and the initial testing using simulated Hanford LAW waste shows compliance with the PA. Both are resistant to leaching and have greater than 25% waste loading.

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