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DOE OSTI2015

Closed Fuel Cycle Waste Treatment Strategy

This study is aimed at evaluating the existing waste management approaches for nuclear fuel cycle facilities in comparison to the objectives of implementing an advanced fuel cycle in the U.S. under current legal, regulatory, and logistical constructs. The study begins with the Global Nuclear Energy Partnership (GNEP) Integrated Waste Management Strategy (IWMS) (Gombert et al. 2008) as a general strategy and associated Waste Treatment Baseline Study (WTBS) (Gombert et al. 2007). The tenets of the IWMS are equally valid to the current waste management study. However, the flowsheet details have changed significantly from those considered under GNEP. In addition, significant additional waste management technology development has occurred since the GNEP waste management studies were performed. This study updates the information found in the WTBS, summarizes the results of more recent technology development efforts, and describes waste management approaches as they apply to a representative full recycle reprocessing flowsheet. Many of the waste management technologies discussed also apply to other potential flowsheets that involve reprocessing. These applications are occasionally discussed where the data are more readily available. The report summarizes the waste arising from aqueous reprocessing of a typical light-water reactor (LWR) fuel to separate actinides for use in fabricating metal sodium fast reactor (SFR) fuel and from electrochemical reprocessing of the metal SFR fuel to separate actinides for recycle back into the SFR in the form of metal fuel. The primary streams considered and the recommended waste forms include; Tritium in low-water cement in high integrity containers (HICs); Iodine-129: As a reference case, a glass composite material (GCM) formed by the encapsulation of the silver Mordenite (AgZ) getter material in a low-temperature glass is assumed. A number of alternatives with distinct advantages are also considered including a fused silica waste form with encapsulated nano-sized AgI crystals; Carbon-14 immobilized as a CaCO3 in a cement waste form; Krypton-85 stored as a compressed gas; An aqueous reprocessing high-level waste (HLW) raffinate waste immobilized by the vitrification process; An undissolved solids (UDS) fraction from aqueous reprocessing of LWR fuel either included in the borosilicate HLW glass or immobilized in the form of a metal alloy or titanate ceramics; Zirconium-based LWR fuel cladding hulls and stainless steel (SS) fuel assembly hardware super-compacted for disposal or purified for reuse (or disposal as low-level waste, LLW) of Zr by reactive gas separations; Electrochemical process salt HLW incorporated into a glass bonded Sodalite waste form; and Electrochemical process UDS and SS cladding hulls melted into an iron based alloy waste form. Mass and volume estimates for each of the recommended waste forms based on the source terms from a representative flowsheet are reported. In addition to the above listed primary waste streams, a range of secondary process wastes are generated by aqueous reprocessing of LWR fuel, metal SFR fuel fabrication, and electrochemical reprocessing of SFR fuel. These secondary wastes have been summarized and volumes estimated by type and classification. The important waste management data gaps and research needs have been summarized for each primary waste stream and selected waste process.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2012

HLW Return from France to Germany - 15 Years of Experience in Public Acceptance and Technical Aspects - 12149

Since in 1984 the national reprocessing concept was abandoned the reprocessing abroad was the only existing disposal route until 1994. With the amendment of the Atomic Energy Act in 2001 spent fuel management changed completely since from 1 June 2005 any delivery of spent fuel to reprocessing plants was prohibited and the direct disposal of spent fuel became mandatory. Until 2005 the total amount of spent fuel to be reprocessed abroad added up to 6080 t HM, 5309 t HM thereof in France. The waste generated from reprocessing - alternatively an equivalent amount of radioactive material - has to be returned to the country of origin according to the commercial contracts signed between the German utilities and COGEMA, now AREVA NC, in France and BNFL, now INS in UK. In addition the German and the French government exchanged notes with the obligation of both sides to enable and support the return of reprocessing residues or equivalents to Germany. The return of high active vitrified waste from La Hague to the interim storage facility at Gorleben was demanding from the technical view i. e. the cask design and the transport. Unfortunately the Gorleben area served as a target for nuclear opponents from the first transport in 1996 to the latest one in 2011. The protection against sabotage of the railway lines and mass protests needed highly improved security measures. In France and Germany special working forces and projects have been set up to cope with this extraordinary situation. A complex transport organization was established to involve all parties in line with the German and French requirements during transport. The last transport of vitrified residues from France has been completed successfully so far thus confirming the efficiency of the applied measures. Over 15 years there was and still is worldwide no comparable situation it is still unique. Summing up, the exceptional project handling challenge that resulted from the continuous anti-nuclear civil disobedience in Germany over the whole 15-year long project running time could be faced efficiently. It has to be concluded that despite of all problems the anti-nuclear activities have caused so far, all transports of vitrified HLW have always been completed successfully by adapting the commonly established safety, security and public acceptance measures to the special conditions and needs in Germany and coordinating the activities of all parties involved but at the expense of high costs for industry and government and a challenging operational complexity. Apart from an anticipatory project planning a good communication between all involved industrial parties and the French and the German government was the key to the effective management of such shipments and to minimize the radiological, economic, environmental, public and political impact. The future will show how efficiently the gained experience can be used for further return projects which are to be realized since no reprocessed waste has yet been returned from UK and neither the medium-level nor the low-level radioactive waste has been transferred from France to Germany. (author)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2015

Separation of Plutonium from Irradiated Fuels and Targets

Spent nuclear fuel from power production reactors contains moderate amounts of transuranium (TRU) actinides and fission products in addition to the still slightly enriched uranium. Originally, nuclear technology was developed to chemically separate and recover fissionable plutonium from irradiated nuclear fuel for military purposes. Military plutonium separations had essentially ceased by the mid-1990s. Reprocessing, however, can serve multiple purposes, and the relative importance has changed over time. In the 1960’s the vision of the introduction of plutonium-fueled fast-neutron breeder reactors drove the civilian separation of plutonium. More recently, reprocessing has been regarded as a means to facilitate the disposal of high-level nuclear waste, and thus requires development of radically different technical approaches. In the last decade or so, the principal reason for reprocessing has shifted to spent power reactor fuel being reprocessed (1) so that unused uranium and plutonium being recycled reduce the volume, gaining some 25% to 30% more energy from the original uranium in the process and thus contributing to energy security and (2) to reduce the volume and radioactivity of the waste by recovering all long-lived actinides and fission products followed by recycling them in fast reactors where they are transmuted to short-lived fission products; this reduces the volume to about 20%, reduces the long-term radioactivity level in the high-level waste, and complicates the possibility of the plutonium being diverted from civil use – thereby increasing the proliferation resistance of the fuel cycle. In general, reprocessing schemes can be divided into two large categories: aqueous/hydrometallurgical systems, and pyrochemical/pyrometallurgical systems. Worldwide processing schemes are dominated by the aqueous (hydrometallurgical) systems. This document provides a historical review of both categories of reprocessing.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2017

Multivariate analysis of gamma spectra to characterize used nuclear fuel

Abstract—The Multi-Isotope Process (MIP) Monitor provides an efficient approach to monitoring the process conditions in used nuclear fuel reprocessing facilities to support process verification and validation. The MIP Monitor applies multivariate analysis to gamma spectroscopy of reprocessing streams in order to detect small changes in the gamma spectrum, which may indicate changes in process conditions. This research extends the MIP Monitor by characterizing a used fuel sample after initial dissolution according to the type of reactor of origin (pressurized or boiling water reactor), initial enrichment, burn up, and cooling time. Simulated gamma spectra were used to develop and test three fuel characterization algorithms. The classification and estimation models employed are based on the partial least squares regression (PLS) algorithm. A PLS discriminate analysis model was developed which perfectly classified reactor type. Locally weighted PLS models were fitted on-the-fly to estimate continuous fuel characteristics. Burn up was predicted within 0.1% root mean squared percent error (RMSPE) and both cooling time and initial enrichment within approximately 2% RMSPE. This automated fuel characterization can be used to independently verify operator declarations of used fuel characteristics and inform the MIP Monitor anomaly detection routines at later stages of the fuel reprocessing stream to improve sensitivity to changes in operational parameters and material diversions.

Multivariate Analysis for Characterization of Used↗

DOE OSTI2021

Blending Polyurethane Thermosets Using Dynamic Urethane Exchange

Recycling crosslinked polyurethanes (PUs) is accomplished through mechanical or chemical processes that are energy-intensive or produce plastics of lesser value. Polymer recycling processes are notably intolerant of polymer mixtures, yet the ability to reprocess and compatibilize two or more crosslinked PUs together will make this process more amenable to mixed waste streams while offering an opportunity to tune the properties of the recycled polymer products. Here, we blend a rigid polyester PU and a soft polyether PU using twin-screw extrusion to yield materials with tunable mechanical properties based on the feed composition. Their material properties were compared to those of compression-molded reprocessed blends and blends where the monomers were mixed prior to synthesis. The extruded materials showed similar mechanical and thermal properties to newly prepared blends and had higher-value mechanical properties compared to the samples reprocessed via compression molding. The morphologies of the blends were observed using phase imaging via atomic force microscopy to show that there is less phase separation in the extruded materials compared to compression-molded blends. The mechanical properties of these materials were tunable from soft to elastomeric to rigid based on the feed composition, and this tunability was demonstrated through four consecutive reprocessing cycles, through which the mechanical properties were steadily varied from rigid to soft by incorporating increasing amounts of soft polyether PU material. Here, this blending method for reprocessing mixed waste compatibilizes different PUs and provides a means to tune the mechanical properties of a PU product, even if starting from waste streams of varying compositions. As such, this process represents an intriguing new approach for polymer reprocessing.

Extrusion↗

DOE OSTI2025

Generation and Study of Am(IV) by Temperature-Controlled Electron Pulse Radiolysis

Used nuclear fuel (UNF) separation techniques that strive to separate radiotoxic americium (Am) from trivalent lanthanide fission products through oxidation state control have increased research efforts surrounding Am(V) and Am(VI). However, equivalent knowledge of the tetravalent state, Am(IV), has remained elusive, particularly in conditions more representative of UNF reprocessing, i.e., in concentrated nitric acid (HNO3). With this in mind, we have used electron pulse radiolysis to study the radiation-induced redox reaction of Am(III) with the oxidizing nitrate radical (NO3?) in 6 M HNO3: Am(III) + NO3? ? Am(IV) + NO3? . These experiments enabled us to observe the growth and decay of Am(IV) in a concentrated acidic solution for the first time. The transient Am(IV) species was found to have a lifetime of ~16 µs?sufficiently long-lived to play a critical mechanistic role in UNF reprocessing systems. Additionally, we performed the first-ever temperature-dependent kinetics study of an actinide element, elucidating unprecedented Arrhenius and Eyring activation parameters for the reaction of Am(III) with NO3?. This new knowledge provides much-needed molecular-level insights into the radiation-induced behavior of Am.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2021

Microfluidic Liquid-Liquid Extraction Chip with Integrated Raman Sensors (Phase I and Phase II Final Report)

As demand for electricity continues to increase worldwide, the world’s nuclear power generating capacity will continue to grow. Nuclear power is the most environmentally benign way of producing electricity on a large scale. The long-term successful use of nuclear power, however, is critically dependent upon adequate and safe processing and disposal of spent nuclear fuels. A very important feature of nuclear energy is that spent fuels can be reprocessed to recover fissile and fertile materials that can then be used as fresh fuel for nuclear power plants. The DOE-NE Fuel Cycle Research and Development (FCR&D) is currently developing nuclear material reprocessing technologies. In a typical nuclear fuel reprocessing system, centrifugal contactors are used as liquid-liquid extraction devices where two immiscible liquids are mixed at high speeds using a rotor, which creates a fine dispersion of droplets of organic phase in an aqueous phase that contains the analyte. Understanding the extraction efficiency at these contactors through modeling and simulation is important in the development of reprocessing technologies and the optimization of current technologies such as the PUREX process. The outcome of this program will be a liquid-liquid microfluidic flow cell chip with embedded spectroscopic sensors for the analysis of extracted analytes. This device will be useful in the optimization of new fuel reprocessing schemes as well as existing reprocessing processes by providing a microfluidic modeling platform to optimize extraction parameters. The Phase I and Phase II work developed a microfluidic chip design that allows integration of Raman and absorption fiber optic probes and successfully demonstrated the feasibility of using Raman and absorption probes to detect key analytes that partition into the aqueous and organic phases.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

DOE OSTI2020

Performance Criteria for Capture and/or Immobilization Technologies (Revision 1)

The capture and subsequent immobilization of regulated volatile radionuclides from the off-gas streams of a used nuclear fuel (UNF) reprocessing facility has been a topic of substantial research interest for the US Department of Energy and its international counterparts. Removal of specific radionuclides from the plant effluent streams before discharge to the environment is required to meet regulations set forth by the US Environmental Protection Agency. Upon removal, the radionuclides, as well as associated sorbents that cannot be regenerated in a cost-effective manner, are destined for conversion to a waste form. Research in separation and capture methodologies has included a wide range of technology types, and studies of waste forms are correspondingly diverse. In considering the future development and implementation of both sorbents and waste forms, it is necessary to identify benchmark measures of performance to objectively evaluate each sorbent system or waste form. Sets of performance criteria and associated metrics have been developed for sorbent and waste form evaluation. These criteria address physical, radiological, and chemical characteristics, technical practicality, technical maturity, cost, and, for sorbents, system performance. The criteria and metrics appear to be robust and should be applicable despite the eventual waste classification (as either high- or low-level waste). They are flexible enough to address both aqueous reprocessing and electrochemical reprocessing of UNF. These criteria sets can serve as tools to evaluate performance at multiple stages within the development process, and in this revision (Revision 1) they have been used to assess technologies relating to krypton/xenon separations and iodine capture from off-gas streams arising from UNF reprocessing. Assessment of krypton/xenon separations using engineered forms of two zeolite minerals (silver mordenite and hydrogen mordenite in a polyacrylonitrile-based binder [AgZ-PAN/HZ-PAN]) found that the zeolite-based separation is relatively advanced in its development, but several key issues require resolution. First, desorption processes for both krypton and xenon require refinement to provide an understanding of the product purity that can be achieved. Second, adsorption rate data is needed in order to calculate the bed depth required for effective separation. Finally, it is strongly recommended that a technical review of krypton/xenon separation by AgZ-PAN/HZ-PAN be performed to synergize available data and assess the cost savings and operational benefits that may be realized from implementation of this technology. Assessment of metal organic frameworks (MOFs) for their use in the separation of krypton/xenon found that the ideal separation would be performed using a single-column system with a MOF selective for krypton over xenon. A robust research effort should work to identify a krypton-selective MOF designed to operate at temperatures of approximately 0°C or higher, which could be preferred over cryogenic krypton/xenon capture for used fuel reprocessing off-gas streams. In the case of the CaSDB-MOF (the most well-understood xenon sorbent to date), two issues are judged of high importance. First, xenon breakthrough capacity for the CaSDB-MOF in prototypical conditions should be determined. Preliminary research indicates that breakthrough may be near immediate, presenting a substantial obstacle in separative system design. Second, development of desorption methodology should be performed to determine regeneration time, energy requirements, and the product stream composition. Silver-based sorbents (AgZ and AgAero) for use in iodine capture from the dissolver off-gas were evaluated against the established criteria. These sorbents are significantly better understood for this application as a result of research efforts over the past decade. The potential implementation of AgAero at a large scale is hindered by its physical degradation by components of the dissolver off-gas stream. Less is known about the adsorption of iodine by these sorbents from other off-gas streams in the plant. Initial experimental efforts have been closely coordinated in an effort to understand organic iodine (such as would be found in the vessel off-gas) adsorption by AgZ and AgAero. Future work should expand this experimental program, and analysis of other reprocessing facility off-gas streams such as the vitrification off-gas stream should be conducted to better understand other potential applications for iodine sorbents. A review of iodine waste form development shows that this area is diverse and that multiple promising waste forms have been identified for the immobilization of radioactive iodine. Efforts related to the direct conversion of iodine sorbents (including AgZ and AgAero) should be continued because of the advantages of direct conversion in a waste management strategy and other sorbents should continue to be advanced as merited.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2019

A Preliminary Probabilistic Performance Assessment Model for Radiological and Chemical Contamination at the West Valley Site, New York - 19295

The New York State Energy Research and Development Authority (NYSERDA) is the owner of the Western New York Nuclear Service Center (WNYNSC), a 1,351-ha site located approximately 48 km south of Buffalo, New York. In 1962, Nuclear Fuel Services, Inc. (NFS) entered into agreements with the Atomic Energy Commission and New York State to construct the first commercial reprocessing plant of nuclear fuel in the United States at the WNYNSC. NFS built and operated the spent fuel reprocessing plant and waste disposal facilities, processing 640 Mg (640 metric tons) of spent nuclear fuel from 1966 to 1972 under an Atomic Energy Commission license. Nuclear fuel reprocessing operations halted in 1972 and never restarted, leaving behind radioactive and chemical wastes. The reprocessing wastes include high-level waste (HLW), so U.S. Department of Energy (DOE) was compelled to complete certain waste management activities under the West Valley Demonstration Project (WVDP) Act of 1980, including decommissioning of WVDP facilities. As collaborating agencies, NYSERDA and the DOE are tasked with making decisions about decommissioning and risk reduction for the West Valley Site. Neptune and Company, Inc. (Neptune) was contracted to develop a probabilistic performance assessment (PPA) model to assist the agencies in their decision making process for decommissioning the WVDP and WNYNSC. One important tool that is needed in order to inform the decision-making process is a science-based model of the contamination at the West Valley Site and its potential implications for human health and the environment. The West Valley PPA Model (the Model), developed using the GoldSim modeling software, is a tool intended to provide support for decision making with uncertainty, in a manner that is transparent, defensible, and robust. The PPA Model includes contaminant transport and health effects components, and is organized around geographically-organized contaminated facilities. These include the waste disposal areas licensed by the U.S. Nuclear Regulatory Commission and the State of New York, a waste tank farm for storage of HLW resulting from reprocessing operations, and several areas contaminated with radioactive and chemical constituents. The Model evaluates contaminant transport from these sources to points of exposure across the site and into receiving surface waters and sediments. Hypothetical people and wildlife are exposed to contamination at these locations, and the effects of these exposures are evaluated. Contaminant transport processes to be evaluated in the Model include groundwater and surface water transport, contaminant translocation by plants and animals, diffusion in subsurface air and water, and erosion of the Site. The evaluation of exposures to people in this preliminary model is limited to a resident farmer scenario, and ecological assessment is performed at the level of a screening analysis. The results of these preliminary evaluations inform future model developments. Model results are subjected to sensitivity analysis in order to determine those pathways and parameters that are most significant in influencing the results. This information allows analysts and decision makers to focus on those aspects of Site behavior and processes that contribute most to overall uncertainty. With this information, the Supplemental Environmental Impact Statement (SEIS) can inform defensible decisions regarding remediation of the Site. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2018

An Alternative to the Continued Accumulation of Separated Plutonium in Japan: Dry Cask Storage of Spent Fuel

As of the end of 2017, Japan had a stockpile of 48 tons of separated plutonium. It will take more than a decade for Japan to convert most of that plutonium into “mixed-oxide” (MOX) fuel and load it into power reactors licensed to use such fuel. This is a very costly program. Including the cost of reprocessing, MOX fuel costs about ten times more than the low-enriched-uranium fuel that otherwise would be used by these reactors. Yet Japan has a policy to start separating more plutonium from spent reactor fuel as soon as the Rokkasho Reprocessing Plant can be put into operation – currently projected for 2021 after 24 years of delay due to a variety of technical problems and upgrades in safety requirements. Japan’s government remains committed to this costly and troubled program primarily because, pending the availability of additional spent-fuel storage space on or off site, reprocessing is seen as the only way to get spent fuel out of reactor pools that are getting full. Because of concerns about the safety of dense-packed spent-fuel pools, however, the prefectures and towns hosting Japan’s power reactors are beginning to accept on-site storage of spent fuel in dry casks. This is the option the United States and many other countries chose after they cancelled their reprocessing programs and their powerplant pools filled up. Its increasing availability in Japan, if backed by a determined policy to accelerate its introduction, should make it possible to cancel reprocessing in Japan as well.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2011

Fusion-fission hybrid for fissile fuel production without processing

Two scenarios are typically envisioned for thorium fuel cycles: “open” cycles based on irradiation of 232 Th and fission of 233 U in situ without reprocessing or “closed” cycles based on irradiation of 232 Th followed by reprocessing, and recycling of 233 U either in situ or in critical fission reactors. This study evaluates a third option based on the possibility of breeding fissile material in a fusion-fission hybrid reactor and burning the same fuel in a critical reactor without any reprocessing or reconditioning. This fuel cycle requires the hybrid and the critical reactor to use the same fuel form. TRISO particles embedded in carbon pebbles were selected as the preferred form of fuel and an inertial laser fusion system featuring a subcritical blanket was combined with critical pebble bed reactors, either gas-cooled or liquid-salt-cooled. The hybrid reactor was modeled based on the earlier, hybrid version of the LLNL Laser Inertial Fusion Energy (LIFE) system, whereas the critical reactors were modeled according to the Pebble Bed Modular Reactor (PBMR) and the Pebble Bed Advanced High Temperature Reactor (PB-AHTR) design. An extensive neutronic analysis was carried out for both the hybrid and the fission reactors in order to track the fuel composition at each stage of the fuel cycle and ultimately determine the plant support ratio, which has been defined as the ratio between the thermal power generated in fission reactors and the fusion power required to breed the fissile fuel burnt in these fission reactors. It was found that the maximum attainable plant support ratio for a thorium fuel cycle that employs neither enrichment nor reprocessing is about 2. This requires tuning the neutron energy towards high energy for breeding and towards thermal energy for burning. A high fuel loading in the pebbles allows a faster spectrum in the hybrid blanket; mixing dummy carbon pebbles with fuel pebbles enables a softer spectrum in the critical reactors. This combination consumes about 20% of the thorium initially loaded in the hybrid reactor (~200 GWd/tHM), partially during hybrid operation, but mostly during operation in the critical reactor. The plant support ratio is low compared to the one attainable using continuous fuel chemical reprocessing, which can yield a plant support ratio of about 20, but the resulting fuel cycle offers better proliferation resistance as fissile material is never separated from the other fuel components.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2015

A Literature Survey to Identify Potentially Volatile Iodine-Bearing Species Present in Off-Gas Streams

Four radionuclides have been identified as being sufficiently volatile in the reprocessing of nuclear fuel that their gaseous release needs to be controlled to meet regulatory requirements (Jubin et al. 2011, 2012). These radionuclides are 3H, 14C, 85Kr, and 129I. Of these, 129I has the longest half-life and potentially high biological impact. Accordingly, control of the release of 129I is most critical with respect to the regulations for the release of radioactive material in stack emissions. It is estimated that current EPA regulations (EPA 2010) would require any reprocessing plant in the United States to limit 129I release to less than 0.05 Ci/MTIHM for a typical fuel burnup of 55 gigawatt days per metric tonne (GWd/t) (Jubin 2011). The study of inorganic iodide in off-gas systems has been almost exclusively limited to I2 and the focus of organic iodide studies has been CH3I. In this document, we provide the results of an examination of publically available literature that is relevant to the presence and sources of both inorganic and organic iodine-bearing species in reprocessing plants. We especially focus on those that have the potential to be poorly sequestered with traditional capture methodologies. Based on the results of the literature survey and some limited thermodynamic modeling, the inorganic iodine species hypoiodous acid (HOI) and iodine monochloride (ICl) were identified as potentially low-sorbing iodine species that could present in off-gas systems. Organic species of interest included both short chain alkyl iodides such as methyl iodide (CH3I) and longer alkyl iodides up to iodododecane (C10H21I). It was found that fuel dissolution may provide conditions conducive to HOI formation and has been shown to result in volatile long-chain alkyl iodides, though these may not volatilize until later in the reprocessing sequence. Solvent extraction processes were found to be significant sources of various organic iodine-bearing species; formation of these was facilitated by the presence of radiolytic decomposition products resulting from radiolysis of tri-n-butyl phosphate and dodecane. Primarily inorganic iodine compounds were expected from waste management processes, including chlorinated species such as ICl. Critical knowledge gaps that must still be addressed include confirmation of the existence and quantification of low-sorbing species in the off-gas of reprocessing facilities. The contributions from penetrating forms of iodine to the plant DF are largely unknown and highly dependent on the magnitude of their presence. These species are likely to be more difficult to remove and it is likely that their sequestration could be improved through the use of different sorbents, through design modifications of the off-gas capture system, or through chemical conversion prior to iodine abatement that would produce more easily captured forms.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2012

Effects of cooling time on a closed LWR fuel cycle

In this study, the effects of cooling time prior to reprocessing spent LWR fuel has on the reactor physics characteristics of a PWR fully loaded with homogeneously mixed U-Pu or U-TRU oxide (MOX) fuel is examined. A reactor physics analysis was completed using the CASM04e code. A void reactivity feedback coefficient analysis was also completed for an infinite lattice of fresh fuel assemblies. Some useful conclusions can be made regarding the effect that cooling time prior to reprocessing spent LWR fuel has on a closed homogeneous MOX fuel cycle. The computational analysis shows that it is more neutronically efficient to reprocess cooled spent fuel into homogeneous MOX fuel rods earlier rather than later as the fissile fuel content decreases with time. Also, the number of spent fuel rods needed to fabricate one MOX fuel rod increases as cooling time increases. In the case of TRU MOX fuel, with time, there is an economic tradeoff between fuel handling difficulty and higher throughput of fuel to be reprocessed. The void coefficient analysis shows that the void coefficient becomes progressively more restrictive on fuel Pu content with increasing spent fuel cooling time before reprocessing. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2013

Closing nuclear fuel cycle with fast reactors: problems and prospects

The closed nuclear fuel cycle (CNFC) with fast reactors (FR) is the most promising way of nuclear energetics development because it prevents spent nuclear fuel (SNF) accumulation and minimizes radwaste volume due to minor actinides (MA) transmutation. CNFC with FR requires the elaboration of safety, environmentally acceptable and economically effective methods of treatment of SNF with high burn-up and low cooling time. The up-to-date industrially implemented SNF reprocessing technologies based on hydrometallurgical methods are not suitable for the reprocessing of SNF with high burn-up and low cooling time. The alternative dry methods (such as electrorefining in molten salts or fluoride technologies) applicable for such SNF reprocessing have not found implementation at industrial scale. So the cost of SNF reprocessing by means of dry technologies can hardly be estimated. Another problem of dry technologies is the recovery of fissionable materials pure enough for dense fuel fabrication. A combination of technical solutions performed with hydrometallurgical and dry technologies (pyro-technology) is proposed and it appears to be a promising way for the elaboration of economically, ecologically and socially accepted technology of FR SNF management. This paper deals with discussion of main principle of dry and aqueous operations combination that probably would provide safety and economic efficiency of the FR SNF reprocessing. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2016

Tritium Content in and Release from Pressurized-Water-Reactor Fuel Cladding

It is expected that tritium pretreatment will be required in future reprocessing plants to prevent the release of tritium to the environment (except for long-cooled fuels; >30 yrs). To design and operate future reprocessing plants in a safe and environmentally compliant manner, the amount and form of tritium in the used nuclear fuel (UNF) must be understood and quantified. Tritium in light water reactor (LWR) fuel is dispersed between the fuel matrix and the fuel cladding, and some tritium may be in the plenum, probably as tritiated water (THO or T{sub 2}O). In a standard processing flowsheet, tritium management would be accomplished by treatment of liquid streams within the plant. Pretreating the fuel prior to dissolution to release the tritium into a single off-gas stream could simplify tritium management, so the removal of tritium in the liquid streams throughout the plant may not be required. The fraction of tritium remaining in the cladding may be reduced as a result of tritium pretreatment. Since Zircaloy'R cladding makes up roughly 25% by mass of UNF in the United States, processes are being considered to reduce the volume of reprocessing waste attributed to Zircaloy'R clad fuel by recovering the zirconium from the cladding for reuse. Treatment options for Zircaloy cladding include recycling to recover the significant value of the zirconium and eliminate costs associated with the disposal of transuranic-contaminated Zircaloy. If LWR fuel is reprocessed and the fuel is dissolved without tritium pretreatment, the tritium in the cladding will remain bound to the cladding. If tritium pretreatment is included in the flow sheet, some portion of the tritium in the cladding may be released along with the tritium from the fuel matrix. To design and operate reprocessing plants in a safe and environmentally compliant manner, the amount and form of tritium in the UNF must be understood and quantified. For Zircaloy-clad fuels from light water reactors, the tritium produced from ternary fission and other sources is expected to be divided between the fuel, where it is generated, and the cladding. It has been previously documented that a fraction of the tritium produced in uranium oxide fuel from LWRs can migrate and become trapped in the cladding. Estimates of the percentage of tritium in the cladding typically range from 0-96%. There is relatively limited data on how the tritium content of the cladding varies with burnup and fuel history (temperature, power, etc.) and how pretreatment impacts its release. The present study was undertaken to understand how tritium pretreatment at standard tritium pretreatment conditions (oxidation in air at 480 to 600 deg. C) affects the tritium content in the Zircaloy cladding and the extent to which the tritium content could be reduced with modest increases in the tritium pretreatment temperature. The data indicate that <20% of the tritium in PWR cladding will be removed by pretreatment at 500-700 deg. C for 24 h. Essentially 100% of the tritium will likely be released if the heating time at 700 deg. C is extended to 96 h. Small amounts of tritium are expected to be released if the cladding is heated at ≤ 600 deg. C for up to 96 h. The results of this study indicate that the amount of tritium released from tritium pretreatment systems will be dependent on both the operating temperature and length of time in the pretreatment system. Under certain conditions, a significant fraction of the tritium could remain bound in the cladding and would need to be considered in any subsequent processing of the cladding to recover/recycle the zirconium. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2023

Endowing Polythioester Vitrimer with Intrinsic Crystallinity and Chemical Recyclability

Abstract Technologically important thermosets face a long‐standing end‐of‐life (EoL) problem of non‐reprocessability, a more sustainable solution of which has resolved to nascent vitrimers that can merge the robust material properties of thermosets and the reprocessability of thermoplastics. However, the lifecycle of vitrimers is still finite, as they often suffer from significant deterioration of mechanical performance following multiple reprocessing cycles, analogous to mechanical recycling, and they often show undesired creep under working conditions. To address these two key limitations, we have developed a cross‐linked semi‐crystalline polythioester with both dynamic covalent bonds and intrinsic crystallinity and chemical recyclability, affording a vitrimeric system that exhibits not only reprocessability and crystallinity‐restricted creep but also complete chemical recyclability to initial monomer by catalyzed depolymerization in solution or bulk. Therefore, reported herein is an “infinite” vitrimer system that is empowered with a facile closed‐loop EoL option once serial reprocessing deteriorates performance and the material can no longer meet the application requirements. Specifically, the polythioester vitrimer was constructed by copolymerization of a bicyclic thioester with a bis‐dithiolane, producing dynamically cross‐linked polythioesters with excellent property tunability, from amorphous to semi‐crystalline states and melting transition temperatures from 91 to 178 °C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Correlating processing variables to material properties in recycled polypropylene: A data‐driven approach

Abstract Polypropylene (PP) is one of the most widely used plastics, yet its recycling remains limited, with less than 1% of solid waste PP being reprocessed. Mechanical recycling through extrusion is the most practical method, but inconsistent reprocessing conditions introduce variability in material properties. While temperature, screw speed, and residence time influence the thermomechanical stress applied during reprocessing, there are no standardized guidelines for optimizing these parameters. This study examines how these factors shape the properties of recycled PP, using conditions designed to mimic post‐industrial recycled (PIR) scrap. Residence time was measured using colorimetric tracking and correlated with molecular weight, viscosity, and mechanical properties over multiple extrusion cycles. Data‐driven modeling, including response surface methodology, support vector machines, and artificial neural networks, identified processing temperature as the dominant factor in material degradation, followed by residence time. Mechanical properties remained stable, while viscosity decreased predictably with increasing residence time. By linking reprocessing conditions to property evolution, this study provides a method to optimize processing parameters and reduce variability in recycled PP. These findings help manufacturers improve process control, making recycled PP more predictable for reuse in manufacturing. Highlights Study of PIR‐quality PP without additives or compatibilizers. Residence time analysis shows processing temperature drives PP property changes. Mark‐Houwink enables quick molecular weight checks for quality control. Models predict mechanical and rheological shifts in reprocessing. Optimized processing parameters minimize property degradation in recycling.

Estela‐García, John E. [Polymer Engineering Center↗

DOE OSTI2024

Covalent adaptable polymer networks with CO 2 -facilitated recyclability

Cross-linked polymers with covalent adaptable networks (CANs) can be reprocessed under external stimuli owing to the exchangeability of dynamic covalent bonds. Optimization of reprocessing conditions is critical since increasing the reprocessing temperature costs more energy and even deteriorates the materials, while reducing the reprocessing temperature via molecular design usually narrows the service temperature range. Exploiting CO 2 gas as an external trigger for lowering the reprocessing barrier shows great promise in low sample contamination and environmental friendliness. Herein, we develop a type of CANs incorporated with ionic clusters that achieve CO 2 -facilitated recyclability without sacrificing performance. The presence of CO 2 can facilitate the rearrangement of ionic clusters, thus promoting the exchange of dynamic bonds. The effective stress relaxation and network rearrangement enable the system with rapid recycling under CO 2 while retaining excellent mechanical performance in working conditions. This work opens avenues to design recyclable polymer materials with tunable dynamics and responsive recyclability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗