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Nuclear criticality safety standard for a fuel reprocessing plant assuming burnup credit published by the atomic energy society of Japan - 14591

In this paper an outline of the standard published in April 2015 by the Atomic Energy Society of Japan (AESJ) is presented. The standard gives basis of nuclear safety management of a spent fuel reprocessing plant that assumed burnup credit in nuclear criticality safety evaluation. Ten years ago the AESJ published Basic Items of Criticality Safety Control: 2004, AESJ-SC-F004:2004, which prescribed basic ideas, requirements and methods on nuclear criticality safety controls of facilities handling with nuclear fuel materials in general for preventing a nuclear criticality accident. However, it did not include any specific procedures for adopting burnup credit. Therefore, a new standard was envisaged as the first Standard for fuel reprocessing plants, which clarified the specific procedures to apply burnup credit to designers, operators, maintenance persons and administrators. The Standard, Procedures for Applying Burnup Credit to Criticality Safety Control of a Reprocessing Facility: 2014, AESJ-SC-F025: 2014, was developed by the AESJ after vital discussions of the Working Group on Nuclear Criticality Safety Control, which were followed by critical reviews of the Special Committee on Nuclear Fuel Cycle and those of the Standard Committee, where both committees were established under the AESJ. The followings are some features of the standard: 1. In many countries, application of burnup credit has been considered especially in transportation and storage of spent fuel. The standard applies to a reprocessing plant, especially to the Rokkasho Reprocessing Plant in Japan. The present edition of the Standard assumes the first phase of burnup credit, i.e., burnup credit considering reduction in {sup 235}U, production of {sup 239}Pu and changes in other actinides, but not considering neutron absorption effect of fission products. 2. This standard covers nuclear criticality safety management including safety design and safety control stages. It prescribes each procedure of nuclear safety management with emphasis on its necessity rather in detail. Attached to the standard are seven appendices, which give reference to it, and explanations, which provide supplemental information to the readers. Future needs of AESJ standards in the field of nuclear criticality safety will be discussed in the presentation. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

ON-LINE MONITORING FOR PROCESS CONTROL AND SAFEGUARDING OF RADIOCHEMICAL STREAMS AT SPENT FUEL REPROCESSING PLANTS

The International Atomic Energy Agency (IAEA) has established international safeguards standards for fissionable material at spent nuclear fuel reprocessing plants to ensure that significant quantities of weapons-grade nuclear material are not diverted from these facilities. Currently, methods to verify material control and accountancy (MC&A) at these facilities require time-consuming and resource-intensive destructive assay (DA). Leveraging new on-line non-destructive assay (NDA) techniques in conjunction with the traditional and highly precise DA methods may provide a more timely, cost-effective and resource-efficient means for MC&A verification at such facilities. Pacific Northwest National Laboratory (PNNL) is developing on-line NDA process monitoring technologies, including a spectroscopy-based monitoring system, to potentially reduce the time and resource burden associated with current techniques. The spectroscopic monitor continuously measures chemical compositions of the process streams including actinide metal ions (U, Pu, Np), selected fission products, and major non-radioactive flowsheet chemicals using UV-vis-near infrared and Raman spectroscopy. This paper provides an overview of the methods and reports our on-going efforts to develop and demonstrate the technologies. Our ability to identify material intentionally diverted from a liquid-liquid extraction contactor system was successfully tested using on-line process monitoring as a means to detect the amount of material diverted. A chemical diversion and detection of that diversion, from a solvent extraction scheme was demonstrated using a centrifugal contactor system operating a tributyl phosphate based extraction. A portion of the feed from a counter-current extraction system was diverted while a continuous extraction experiment was underway; the spectroscopic on-line process monitoring system was simultaneously measuring the feed, raffinate and organic products streams. The amount observed to be diverted by on-line spectroscopic process monitoring was in excellent agreement with values based from the known mass of sample directly diverted from system feed solution.

Np↗

Development of On-Line Spectroscopic pH Monitoring for Nuclear Fuel Reprocessing Plants: Weak Acid Schemes

Knowledge of real-time solution properties and composition is a necessity for any spent nuclear fuel reprocessing method. Metal-ligand speciation in aqueous solutions derived from the dissolved commercial spent fuel is highly dependent upon the acid concentration/pH, which influences extraction efficiency and the resulting speciation in the organic phase. Spectroscopic process monitoring capabilities, incorporated in a counter current centrifugal contactor bank, provide a pathway for on-line real-time measurement of solution pH. The spectroscopic techniques are process-friendly and can be easily configured for on-line applications, while classic potentiometric pH measurements require frequent calibration/maintenance and have poor long-term stability in aggressive chemical and radiation environments. Our research is focused on developing a general method for on-line determination of pH of aqueous solutions through chemometric analysis of Raman spectra. Interpretive quantitative models have been developed and validated under the range of chemical composition and pH using a lactic acid/lactate buffer system. The developed model was applied to spectra obtained on-line during solvent extractions performed in a centrifugal contactor bank. The model predicted the pH within 11% for pH > 2, thus demonstrating that this technique could provide the capability of monitoring pH on-line in applications such as nuclear fuel reprocessing.

pH, spectroscopic monitoring, on-line monitoring, ↗

Overcoming challenges in delivering 5 Avantech water treatment systems at Fukushima - 15544

The Great East Japan Earthquake has left the Fukushima Daiichi Nuclear Station with many challenges related to water treatment. This paper will provide information on three systems provided for the treatment of [1] accumulated water associated with the Circulated Water Cooling System, [2] sub-drain water removed from wells adjacent to the Unit 1-4 Reactor and Turbine Buildings, and [3] wash water from decontamination of vehicles and equipment. Specific information will be presented on work that was completed to overcome process, installation and logistical challenges associated with these water streams including the following: - Selection of technology and equipment for removal of specific radionuclides - Performance results of highly selective adsorbents used for removing radionuclides in the presence of varying concentrations of chlorides and other natural constituents - Description of process flowsheets and equipment configuration - Discussion of the post-accident work environment and the related work site restrictions Results show that the customized solutions will enable the utility to clean-up the wastewater for cooling, reuse and potential discharge. The technologies used for the three water treatment systems are directly applicable to the treatment of similarly challenging water streams at commercial nuclear power plants, fuel reprocessing plants and governmental nuclear facilities worldwide. The use of these technologies will aid in the lowering of radioactivity released to the environment, worker radiation exposure and the amount of secondary waste requiring long term storage and/ or disposal. (authors)

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Assembly and Testing of a Tritium and Iodine Removal System for Use with Advanced Tritium Pretreatment

US regulations will require the removal of iodine and tritium, along with other volatile and semivolatile radionuclides, from the off-gas streams of nuclear fuel reprocessing plants. Tritium pretreatment is a head-end operation that could be incorporated within nuclear fuel reprocessing plants for the upfront removal and trapping of these volatiles species. Quantitative, up-front removal in a single compact system is of significant advantage because otherwise tritium and iodine distributes to other unit operations, each of which have associated off-gas streams also requiring treatment. Oak Ridge National Laboratory is presently developing an advanced tritium pretreatment process based on the oxidation of used nuclear fuel at low temperature using NO 2 /O 2 mixtures, which produces a fine powder. This process can result in the quantitative volatilization of both tritium and iodine. The powder product can be selected to be U 3 O 8 , UO 3 , or a nitrate by adjusting the processing conditions and the process can be readily interfaced to either conventional aqueous-based or advanced pyrochemical–based reprocessing plants. In preparation for a planned kilogram-scale hot cell demonstration of the advanced tritium pretreatment process with used nuclear fuel (UNF), an integrated iodine and tritium capture system was designed and assembled. Three experimental runs of this system were completed successfully. All the samples were submitted for analysis. The results and data analysis will be covered in a subsequent report to be issued by the Off-Gas Sigma Team. Several additional tests should be undertaken to provide additional information on the system’s performance. The objectives for the additional tests and test conditions are presented in this report.

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Milestone Report - M4FT-17OR030107025 - Design of a tritium and iodine removal system for use with advanced TPOG

US regulations will require the removal of iodine and tritium, along with other volatile and semi-volatile radionuclides, from the off-gas streams of nuclear fuel reprocessing plants. Advanced tritium pretreatment (TPT) is an additional head-end operation that could be incorporated within nuclear fuel reprocessing plants. It utilizes nitrogen dioxide (NOR2R) as an oxidant to convert UOR2R to UR3ROR8R prior to traditional aqueous dissolution. Advanced TPT can result in the quantitative volatilization of both tritium and iodine. Up-front removal of iodine is of significant advantage because otherwise it distributes to several unit operations and the associated off-gas streams. The off-gas streams will then require treatment to comply with US regulations. Advanced TPT is currently under development at Oak Ridge National Laboratory, and a kilogram-scale hot cell demonstration with used nuclear fuel (UNF) is planned for fiscal year (FY) 2018.

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Sampling and Analysis Plan for Investigation of Undeclared Nuclear Activities - 20104

The nuclear-centered energy policy in South Korea is moving towards a nuclear-free era. It also facilitates an action or progress on the denuclearization of the Korean peninsula. The Nuclear Safety and Security Commission (NSSC) launched a new R and D project which attempts to verify nuclear activities via analyzing environmental samples. Environmental samples possibly contain significant radiological information relevant to past undeclared activities. In order to precisely verify them, it is essential to provide 1) the concrete information of target facilities, 2) appropriate methodologies and procedures, and 3) well-suited instrumentation and equipment corresponding to sample signatures. It is also important to provide scientific reliability or validity in any process such as sample collection, handling, transportation and laboratory analysis. Therefore, the information of nuclear facilities (fuel fabrication plant, graphite moderated reactor, reprocessing plant) in North Korea are reviewed in order to determine parameters for appropriate sampling methods representing a facility's characteristics. Secondly, a sampling procedure for radioactive elements is being developed based on international and domestic standards such as ASTM (American Society for Testing and Materials), KS (Korean industrial Standards), and International Atomic Energy Agency (IAEA) manuals. The procedure contains some specific information including sampling process, sampling tools, amount of sample, sample identification, and other related information. Developing the qualified national guidelines is most important since sampling and analyzing results can be used as evidences of nuclear activities. The guideline developed through this work will clearly define various methodologies such as document verification, sampling procedures, collection methods, sample storage criteria, chain of custody, and transportation conditions. The final objective of this work is to establish the infrastructure and regulatory framework for assessment of nuclear activities, and provide a national guideline for sampling and analysis. This will bring confidence in the results and play a critical role in complete denuclearization progress in South Korea. (authors)

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗

Magnox Reprocessing TDN Reactors: Utilising 3D Printing and X-Ray Imaging to Re-Design and Test Fluidising Air Nozzles - 16402

One of the key final steps in reprocessing spent nuclear fuel is the conversion of highly concentrated uranyl nitrate hexahydrate liquor [> 1000 gU/litre] into uranium trioxide (UO{sub 3}) powder by thermal decomposition using Thermal Denitration (TDN) reactors. The TDN reactors in the Magnesium non-oxidising (Magnox) fuel reprocessing plant are high aspect ratio fluidising beds, which suffer from poor fluidization and UO{sub 3} powder blockages. It is widely understood that these issues arise from the inadequate design of the fluidising air distributors (nozzles), which are located around the base of the TDN reactors. A non-active test rig was constructed at the National Nuclear Laboratory (NNL) experimental facility in Workington, Cumbria (UK) which used compressed air at ambient temperature to assess the performance of the current fluidising air nozzle designs (datum) against a range of new nozzle designs. Full-scale nozzle designs were manufactured using a 3-Dimensional (3D) printer and tested to obtain data of both quantitative and qualitative nature. NNL then collaborated with the Chemical Engineering Department at University College London (UCL) to further assess the fluidising potential of the new nozzle designs. Images of inside the fluidized bed were taken utilising a unique X-Ray facility. The results from this study will allow new nozzle designs to be recommended, manufactured and installed, which will ensure improved fluidization of the TDN reactor bed and prevent blockages with UO{sub 3} powder. (authors)

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A Brief User's Guide to the Excel ® -Based DF Calculator

To understand the importance of capturing penetrating forms of iodine as well as the other volatile radionuclides, a calculation tool was developed in the form of an Excel ® spreadsheet to estimate the overall plant decontamination factor (DF). The tool requires the user to estimate splits of the volatile radionuclides within the major portions of the reprocessing plant, speciation of iodine and individual DFs for each off-gas stream within the Used Nuclear Fuel reprocessing plant. The Impact to the overall plant DF for each volatile radionuclide is then calculated by the tool based on the specific user choices. The Excel ® spreadsheet tracks both elemental and penetrating forms of iodine separately and allows changes in the speciation of iodine at each processing step. It also tracks 3 H, 14 C and 85 Kr. This document provides a basic user's guide to the manipulation of this tool.

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Evaluation of high resolution X-ray monochromatic wavelength dispersive X-ray fluorescence instrument for determining Pu and U in nuclear reprocessing streams

In this study, an alpha-prototype benchtop instrument was developed and tested for measuring Pu and U in spent fuel dissolver tanks in a nuclear fuel reprocessing plant. The high resolution X-ray (hiRX) instrument was designed with the aim of providing a new capability to measure samples with high radiation background with selectivity, accuracy, and precision using ultra-low volumes (7 μL) of liquid. The instrument was tested with specimens from the operational reprocessing facility at Savannah River National Laboratory. The results showed that bias was <6% for Pu nitrate process solution and < 18% for Pu in U/HNO 3 matrix. Instrumental precision was <1% RSD while between microcell repeatability was <6% RSD. The limit of detection for Pu in HNO 3 matrix was 3 × 10 -5 g/L (100 s, 35 W). Finally, this study demonstrates that hiRX technology has the potential to provide rapid and simultaneous quantification of Pu and U without sample preparation, making it suitable for process monitoring and materials control and accountability applications.

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Bismuth-Functionalized Silica Aerogels for Iodine Capture

The U.S. Department of Energy is looking into alternative sorbents for the removal of radioiodine from off-gas streams in a used nuclear fuel reprocessing plant. One class of sorbents considered are bismuth-functionalized silica aerogels which offer an efficient capture of iodine from off-gas streams and are environmentally friendly and lower cost when compared to silver-functionalized sorbents. Two types of bismuth-functionalized silica aerogels were successfully manufactured using a hierarchical synthesis approach:1) The Bi 3+ -aerogel with bismuth oxide nitrate hydroxide hydrate particles and 2) Bi-aerogel with bismuth metal and bismuth sulfide nanoparticles. Both sorbents exhibited high sorption capacity for iodine. However, presence of particles of different composition, size, and distribution on aerogel support resulted in different iodine loadings. The Bi 3+ -aerogel exhibited sorption capacity of 289 mg/g. In contrast, Bi-aerogel exhibited more that 20% higher sorption capacity. The heat-treatment of Bi 3+ -aerogel at 225? under hydrogen atmosphere increased iodine loading capacity to 351 mg/g.

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Complete Iodine Loading of NO-Aged Ag 0 -Functionalized Silica Aerogel (Milestone Report)

In off-gas treatment systems within a nuclear fuel reprocessing plant, capture materials will be exposed to a gas stream for extended periods during their lifetime. This gas stream may be at elevated temperature and could contain water, NO x gas, or a variety of other constituents. For this reason, it is important to understand the effects of long-term exposure, or aging, on proposed capture materials. One material under consideration for iodine sequestration is silver-functionalized silica aerogel (Ag 0 -aerogel). The aim of this study was to determine the effect of extended exposure at 150°C to an air stream containing NO on the iodine capture capacity of Ag 0 -aerogel. Ag 0 -aerogel was provided by the Pacific Northwest National Laboratory (PNNL), which manufactures the material at a lab scale. Prior to aging, the material has an iodine loading capacity of approximately 290 mg I/g Ag 0 -aerogel. Previous studies have aged the material in a dry air stream or in a moist air stream for up to 6 months. Both tests resulted in a 22% loss in iodine capacity. Aging the material in a static 2% NO 2 environment for up to 2 months results in a 15% loss of iodine capacity.3 In this study, exposure of Ag 0 -aerogel to 1% NO at 150°C for 2 months produced a loss of 43% in iodine loading capacity. This is largest loss observed for aerogel aging studies to date. The performance of Ag 0 -aerogel in this study was compared to the performance of reduced silver mordenite (Ag 0 Z) in similar studies. Ag 0 Z is a zeolite mineral considered to be the current standard technology for iodine removal from off-gas streams of a potential US used fuel processing plant. In an aging study exposing Ag 0 Z to 1% NO for 2 months, an iodine capacity loss of over 80% was observed. This corresponds to a silver utilization of 13.5% for 2 month NO-aged Ag 0 Z, compared to 57% silver utilization for 2 month NO-aged aerogel. While iodine loading capacity and silver utilization are critical parameters in evaluating these materials, other properties must also be considered when selecting the appropriate material (e.g., relative material densities and potential waste form production technology). The resistance of Ag 0 -aerogel to NO is promising, and investigations of this material for use in iodine capture should continue to be pursued.

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Complete NO and NO 2 Aging Study for AgZ (Milestone Report)

In an off-gas system within a nuclear fuel reprocessing plant, any capture material will be exposed to a gas stream for months at a time. This gas stream may be at elevated temperature and could contain water, NO x gas, or a variety of other constituents that comprise the off-gas stream. For this reason, it is important to understand the effects of long-term exposure, or aging, on proposed capture materials. One material under consideration is silver-exchanged mordenite (AgZ). The aim of this study was to determine the effect of extended exposure at 150°C to an air stream containing NO on the iodine capture capacity of the hydrogen reduced form of AgZ designated as Ag 0 Z. The study was originally also intended to expand on the static NO 2 aging studies by exposing Ag 0 Z to a flowing stream of NO 2 for an extended period of time, but those tests were delayed due to NO 2 production schedules by the gas vendor. Unreduced silver mordenite has a loading capacity of approximately 25 mg I/g AgZ and that capacity is increased to 100 mg I/g Ag 0 Z upon reduction. It appears that extended exposure of AgZ to 1% NO at 150°C may not only neutralize the increased capacity gained by reduction, but perhaps degrade the sorbent even further. Loss of 80% of sorbent capacity and surface area was observed after 8 weeks of exposure to a 1% NO stream at 150°C. Investigations continue into the effects of aging by off-gas components on iodine sorbents. Future work will age silver mordenite with streams containing NO 2 . As the simulated off-gas streams become more complex and more corrosive, the ability of AgZ to withstand conditions present in off-gas streams will be more fully known.

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Process optimization of caustic scrubber and iodine-129 immobilization in sodalite-based waste forms

Caustic scrubbers are proposed to remove vaporized iodine from nuclear fuel reprocessing plants. Resulting caustic slurries of radioactive iodine ( 129 I) and other anions can be captured and immobilized into the cage structures of sodalite-type minerals. Here, mixed anion sodalites were hydrothermally synthesized from a simulated caustic scrubber solution containing hydroxide/water, carbonate, chlorine, bromine, iodine, nitrate, and nitrite ions with added kaolinite. Experiments were conducted with twenty-five different sets of process conditions. Resulting powders were characterized by quantitative X-ray diffraction (XRD) and multi-functional thermal analysis, including gravimetry, calorimetry, and mass spectrometry. Using statistical analysis, process variables were tailored to maximize conversion of kaolinite into cage silicates, immobilize caustic scrubber anions, and minimize amorphous content. Further, chemical analysis showed the incorporation of all the targeted ions into the solids. Detailed investigation of a batch characterized after washing (creating secondary waste) and one without washing but subsequent calcination is given. This work contributes to defining the constraints required for subsequent consolidation process steps of the waste form to avoid volatilization.

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Separation of tritiated water using graphene oxide membrane

In future nuclear fuel reprocessing plants and possibly for nuclear power plants, the cleanup of tritiated water will be needed for hundreds of thousands of gallons of water with low activities of tritium. This cleanup concept utilizes graphene oxide laminar membranes (GOx) for the separation of low-concentration (10 -3 -10 µCi/g) tritiated water to create water that can be released to the environment and a much smaller waste stream with higher tritium concentrations. Graphene oxide membranes consist of hierarchically stacked, overlapping molecular layers and represent a new class of materials. A permeation rate test was performed with a 2-µm-thick cast Asbury membrane using mixed gas permeability testing with zero air (highly purified atmosphere) and with air humidified with either H 2 O or D 2 O to a nominal 50% relative humidity. The membrane permeability for both H 2 O and D 2 O was high with N 2 and O 2 at the system measurement limit. The membrane water permeation rate was compared to a Nafion® membrane and the GOx permeation was approximately twice as high at room temperature. The H 2 O vapor permeation rate was 5.9 × 10 2 cc/m 2 /min (1.2 × 10 -6 g/min-cm 2 ), which is typical for graphene oxide membranes. To demonstrate the feasibility of such isotopic water separation through GOX laminar membranes, an experimental setup was constructed to use pressure-driven separation by heating the isotopic water mixture at one side of the membrane to create steam while cooling the other side. Several membranes were tested and were prepared using different starting materials and by different pretreatment methods. The average separation result was 0.8 for deuterium and 0.6 for tritium. Higher or lower temperatures may also improve separation efficiency but neither has been tested yet. A rough estimate of cost compared to current technology was also included as an indication of potential viability of the process. The relative process costs were based on the rough size of facility to accommodate the large surface area of the membranes and the energy needed to evaporate the water and pass through the membranes as compared to the currently used combined electrolysis and catalytic exchange process.

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Consolidation of iodine-loaded Ag 0 -functionalized silica aerogel with HUP, HIP and SPS

The U.S. Department of Energy is currently investigating alternative sorbents for the removal and immobilization of radioiodine from the gas streams in a nuclear fuel reprocessing plant. One of these new sorbents, silver-functionalized silica aerogel (Ag 0 -aerogel), shows promise as a potential replacement for silver mordenite because of its high selectivity and sorption capacity for iodine. Moreover, a feasible consolidation of iodine-loaded Ag 0 -aerogel to a durable SiO 2 -based waste form makes this aerogel an attractive choice for sequestering radioiodine. The main purpose of the study reported here was to investigate consolidation of Ag 0 -aerogel powders with or without iodine and with or without sintering additives with hot uniaxial pressing (HUP), HIP, and SPS. The selected densified samples were analyzed with a helium gas pycnometer for apparent density, with the Archimedes method for open porosity and apparent density, with scanning electron microscopy and energy dispersive spectroscopy (SEM-EDS) for the extent of densification, macro- and microstructural changes, and distribution of individual elements, and with X-ray diffraction (XRD) for crystalline phases. To convert the iodine-loaded Ag 0 -silica aerogel to a waste form, rapid consolidation with HUP, HIP, and SPS at moderate temperatures and pressures yields a final waste form consisting of AgI particles encapsulated in fused silica. HUP-processing (1200°C for 30 min under 29 MPa pressure) of Ag 0 -aerogel loaded with 20.2 mass% of iodine provided a product with residual open porosity of 16.9%. However, ~93% of sorbed iodine was retained in the sintered material. Densification with HIP at 1200°C for 30 min under 207 MPa pressure resulted in a fully dense silica-based waste form of 3.3 $\times$ 10 3 kg/m 3 bulk density containing ~22 mass% of iodine. Iodine was retained in the form of nano- and micro-inclusions of AgI dispersed in the silica matrix. Additives were not needed to enhance sintering process as depicted from the lack of open porosity and 100% retention of iodine in the consolidated product. The future tests will tell whether additives such as raw silica aerogel or Ag 0 -aerogel are required for HIPing to produce a fully dense waste form from iodine-loaded Ag 0 -aerogel containing higher concentrations of captured iodine. SPS-processing of samples with or without iodine revealed a benefit of additive-enhanced sintering. The samples containing additives (raw silica aerogel, colloidal silica, and Ag 0 -aerogel) shrunk faster and at lower temperatures. In addition, additives significantly improved distribution of silver compounds in the fully densified products, considerably decreasing the number of micron-sized inclusions of AgI, Ag and Ag 2 S at the grain boundaries.

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Classic Nuclear Fuel Reprocessing Flowsheet

This is a flowsheet as well as a series of subsheets to be used for discussion on the standard design of a reprocessing plant. This flowsheet consists of four main sections: offgas handling, separations, solvent wash, and acid recycle. As well as having the main flowsheet, subsections have been broken off into their own sheets to provide for larger font and ease of printing.

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