Evaluation of Iron‐Phosphate Glass–Ceramic Waste Form for Electrorefiner Salt Waste Simulant Dechlorinated With Phosphoric Acid

High-level nuclear waste immobilization with ceramics

Cerium, uranium, and plutonium behavior in glass-bonded sodalite, a ceramic nuclear waste form

This report describes the scientific basis underlying the approach being followed to design and develop “advanced” glass-bonded sodalite ceramic waste form (ACWF) materials that can (1) accommodate higher salt waste loadings than the waste form developed in the 1990s for EBR-II waste salt and (2) provide greater flexibility for immobilizing extreme waste salt compositions. This is accomplished by using a binder glass having a much higher Na2O content than glass compositions used previously to provide enough Na+ to react with all of the Cl– in the waste salt and generate the maximum amount of sodalite. The phase compositions and degradation behaviors of prototype ACWF products that were made using five new binder glass formulations and with 11-14 mass% representative LiCl/KCl-based salt waste were evaluated and compared with results of similar tests run with CWF products made using the original binder glass with 8 mass% of the same salt to demonstrate the approach and select a composition for further studies. About twice the amount of sodalite was generated in all ACWF materials and the microstructures and degradation behaviors confirmed our understanding of the reactions occurring during waste form production and the efficacy of the approach. However, the porosities of the resulting ACWF materials were higher than is desired. These results indicate the capacity of these ACWF waste forms to accommodate LiCl/KCl-based salt wastes becomes limited by porosity due to the low glass-to-sodalite volume ratio. Three of the new binder glass compositions were acceptable and there is no benefit to further increasing the Na content as initially planned. Instead, further studies are needed to develop and evaluate alternative production methods to decrease the porosity, such as by increasing the amount of binder glass in the formulation or by processing waste forms in a hot isostatic press. Increasing the amount of binder glass to eliminate porosity will decrease the waste loading from about 12% to 10% on a mass basis, but this will not significantly impact the waste loading on a volume basis. It is likely that heat output will limit the amount of waste salt that can be accommodated in a waste canister rather than the salt loading in an ACWF, and that the increase from 8 mass% to about 10 mass% salt loadings in ACWF materials will be sufficient to optimize these waste forms. Although the waste salt composition used in this study contained a moderate amount of NaCl, the test results suggest waste salts with little or no NaCl can be accommodated in ACWF materials by using the new binder glass, albeit at waste loadings lower than 8 mass%. The higher glass contents that will be required for ACWF materials made with salt wastes that do not contain NaCl are expected to result in much lower porosities in those waste forms.

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) as a general strategy and associated Waste Treatment Baseline Study (WTBS). 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 both a nominal case study and near-term target reprocessing flowsheets. Many of the waste management technologies discussed also apply to other potential flowsheets that involve reprocessing. 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 separated from either a low volume gas stream or a high volume water stream. The recommended waste form is low-water cement in high integrity containers (HICs). • Iodine-129 separated from off-gas streams in aqueous processing. There are a range of potentially suitable waste forms. 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 separated from LWR fuel treatment off-gases and immobilized as a CaCO3 in a cement waste form. • Krypton-85 separated from LWR and SFR fuel treatment off-gases and stored as a compressed gas. • An aqueous reprocessing high-level waste (HLW) raffinate waste which is immobilized by the vitrification process in one of three forms: a single phase borosilicate glass, a borosilicate based glass ceramic, or a multi-phased crystalline synthetic rock (Synroc). • An undissolved solids (UDS) fraction from aqueous reprocessing of LWR fuel that is either included in the borosilicate HLW glass or is immobilized in the form of a metal alloy in the case of glass ceramics or Synroc. • Zirconium-based LWR fuel cladding hulls and stainless steel (SS) fuel assembly hardware that are washed and super-compacted for disposal or as an alternative with high promise the purification and reuse (or disposal as low-level waste, LLW) of Zr by reactive gas separations. • Electrochemical process salt HLW which is incorporated into a glass bonded Sodalite waste form known as the ceramic waste form (CWF). • Electrochemical process UDS and SS cladding hulls which are 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 the reference mass balances 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.

Results of an estimate of the waste management costs of the commercial high-level waste from a 3000 metric ton per year reprocessing plant show that the judicious use of the ceramic waste form can save about $2 billion during a 20-year operating campaign relative to the use of the glass waste form. This assumes PWR fuel is processed and the waste is encapsulated in 0.305-m-diam canisters with ultimate emplacement in a BWIP-type horizontal-borehole repository. The estimated total cost (capital and operating) of the management in the ceramic form is $2.0 billion, and that of the glass form is $4.0 billion. Waste loading and waste form density are the driving factors in that the low-waste loading (25%) and relatively low density (3.1 g/cm/sup 3/) characteristic of the glass form require several times as many canisters to handle a given waste throughput than is needed for the ceramic waste form whose waste loading capability exceeds 60% and whose waste density is nominally 5.2 g/cm/sup 3/) characteristic of the glass form requires several times as many canisters to handle a given waste throughput than is needed for the ceramic waste form whose waste loading capability exceeds 60% and whose waste density is nominally 5.2 g/cm/sup 3/. The minimum-cost ceramic waste form has a 60 wt. % waste loading of commercial high-level waste and requires 25 years storage before emplacement in basalt with delayed backfill. Because of the process flexibility allowed by the availability of the high-waste loading of the ceramic form, the intermediate-level liquid waste stream can be mixed with the high-level liquid waste stream and economically processed and emplaced. The cost is greater by $0.3 billion than that of the best high-level liquid waste handling process sequence ($2.3 billion vs $2.0 billion), but this difference is less than the cost of the separate disposal of the intermediate-level liquid waste.

Glass–ceramic nuclear waste forms obtained by crystallization of SiO 2–Al 2O 3–CaO–ZrO 2–TiO 2 glasses containing lanthanides (Ce, Nd, Eu, Gd, Yb) and actinides (Th): Study of the crystallization from the surface

Glass binder development for a glass-bonded sodalite ceramic waste form

Glass ceramic waste forms have been investigated as alternatives to borosilicate glasses for the immobilization of high-level radioactive waste at Pacific Northwest Laboratory (PNL). Three glass ceramic systems were investigated, including basalt, celsian, and fresnoite, each containing 20 wt % simulated high-level waste calcine. Static leach tests were performed on seven glass ceramic materials and one parent glass (before recrystallization). Samples were leached at 90/sup 0/C for 3 to 28 days in deionized water and silicate water. The results, expressed in normalized elemental mass loss, (g/m/sup 2/), show comparable releases from celsian and fresnoite glass ceramics. Basalt glass ceramics demonstrated the lowest normalized elemental losses with a nominal release less than 2 g/m/sup 2/ when leached in polypropylene containers. The releases from basalt glass ceramics when leached in silicate water were nearly identical with those in deionized water. The overall leachability of celsian and fresnoite glass ceramics was improved when silicate water was used as the leachant.

Innovative approach for efficient extraction of Nd from electrorefining waste salt into nuclear waste forms

Not all the nuclear waste destined for Yucca Mountain is in the form of spent fuel. Some of it will be radioactive waste generated from the production of nuclear weapons. This so-called defense waste exists mainly as corrosive liquids and sludge in underground tanks. An essential task of the U.S. high-level radioactive waste program is to process these defense wastes into a solid material--called a waste form. An ideal waste form would be extremely durable and unreactive with other repository materials. It would be simple to fabricate remotely so that it could be safely transported to a repository for permanent storage. What's more, the material should be able to tolerate exposure to intense radiation without degradation. And to minimize waste volume, the material must be able to contain high concentrations of radionuclides. The material most likely to be used for immobilization of radioactive waste is glass. Glasses are produced by rapid cooling of high-temperature liquids such that the liquid-like non-periodic structure is preserved at lower temperatures. This rapid cooling does not allow enough time for thermodynamically stable crystalline phases (mineral species) to form. In spite of their thermodynamic instability, glasses can persist for millions of years. An alternate to glass is a ceramic waste form--an assemblage of mineral-like crystalline solids that incorporate radionuclides into their structures. The crystalline phases are thermodynamically stable at the temperature of their synthesis; ceramics therefore tend to be more durable than glasses. Ceramic waste forms are fabricated at temperatures below their melting points and so avoid the danger of handling molten radioactive liquid--a danger that exists with incorporation of waste in glasses. The waste form provides a repository's first line of defense against release of radionuclides. It, along with the canister, is the barrier in the repository over which we have the most control. When a waste form is designed, the atomic environment of the radionuclides is chosen to maximize chemical durability. Elements such as zirconium and phosphorus can be included in the waste form that react with and make some radionuclides less soluble and therefore less likely to be released. The long-term performance assessment of radionuclide containment requires the development of models for each part of the barrier system. It is almost certainly easier to model the corrosion and alteration of waste forms than it is to develop coupled hydrologic, chemical, and geophysical models of radionuclide transport away from a repository. Therefore, much time and effort has been spent optimizing the chemical durability of both glass and ceramic waste forms for radionuclide containment. This has not been an easy task. Three problems in particular posed the greatest challenges. The first is that radionuclides decay, transmuting into daughter elements that may have different chemical properties. These new elements might degrade the existing mineral by making it unstable. A good waste form that works well for uranium may work poorly for lead, its final decay product. The second problem is that the radioactive decay itself damages the solid over time. Radioactive decay is an energetic process in which ejected particles and the recoiling nucleus disrupt the surrounding atoms. A single alpha-decay event can displace thousands of atoms in the surrounding volume. We know from laboratory measurements that radionuclides are more easily released from radiation-damaged structures than from materials that do not sustain radiation damage. The third problem is that radioactive waste, particularly the high level waste from reprocessing of spent nuclear fuel to extract plutonium and uranium, contains a variety of elements with widely varying chemistry. The waste form must incorporate the radionuclides, as well as non-radioactive elements such as silicon and sodium that are present in the waste stream as a result of waste processing. A number of ceramic waste forms have been developed that minimize these problems and provide a potentially useful host for radionuclides. For ceramics, the mineralogy can be tailored to the waste stream by selecting solid mineral phases with structural sites that can accommodate the waste elements, as well as newly formed radioactive decay elements. Radiation damage can be minimized by selecting mineral phases that allow atoms to renew or regain their original crystalline structure, a process known as annealing. For example, actinide phosphate minerals anneal more readily than actinide silicate minerals. Despite the superior thermodynamic stability of crystalline materials, borosilicate glasses have become the preferred waste forms. One reason is that the processing technologies associated with this glass are believed to be easier to adapt to handling highly radioactive material.

Ceramic waste forms are designed to immobilize radionuclides for permanent disposal in geological repositories. One of the principal criteria for the effective incorporation of waste elements is their compatibility with the host material. In terms of performance under environmental conditions, the resistance of the waste forms to degradation over long periods of time is a critical concern when they are exposed to natural environments. Due to their unique crystallographic features and behavior in nature environment as exemplified by their natural analogues, ceramic waste forms are capable of incorporating problematic nuclear waste elements while showing promising chemical durability in aqueous environments. Recent studies of apatite- and hollandite-structured waste forms demonstrated an approach that can predict the compositions of ceramic waste forms and their long-term dissolution rate by a combination of computational techniques including machine learning, first-principles thermodynamics calculations, and modeling using kinetic rate equations based on critical laboratory experiments. By integrating the predictions of elemental incorporation and degradation kinetics in a holistic framework, the approach could be promising for the design of advanced ceramic waste forms with optimized incorporation capacity and environmental degradation performance. Such an approach could provide a path for accelerated ceramic waste form development and performance prediction for problematic nuclear waste elements.

Since the end of the 1970s, Synroc at the Australian Nuclear Science and Technology Organisation (ANSTO) has evolved from a focus on titanate ceramics directed at PUREX waste to a platform waste treatment technology to fabricate tailored glass–ceramic and ceramic waste forms for different types of actinide, high- and intermediate level wastes. The particular emphasis for Synroc is on wastes which are problematic for glass matrices or existing vitrification process technologies. In particular, nuclear wastes containing actinides, notably plutonium, pose a unique set of requirements for a waste form, which Synroc ceramic and glass-ceramic waste forms can be tailored to meet. Key aspects to waste form design include maximising the waste loading, producing a chemically durable product, maintaining flexibility to accommodate waste variations, a proliferation resistance to prevent theft and diversion, and appropriate process technology to produce waste forms that meet requirements for actinide waste streams. Synroc waste forms incorporate the actinides within mineral phases, producing products which are much more durable in water than baseline borosilicate glasses. Further, Synroc waste forms can incorporate neutron absorbers and238U which provide criticality control both during processing and whilst within the repository. Synroc waste forms offer proliferation resistance advantages over baseline borosilicate glasses as it is much more difficult to retrieve the actinide and they can reduce the radiation dose to workers compared to borosilicate glasses. Major research and development into Synroc at ANSTO over the past 40 years has included the development of waste forms for excess weapons plutonium immobilization in collaboration with the US and for impure plutonium residues in collaboration with the UK, as examples. With a waste loading of 40–50 wt.%, Synroc would also be considered a strong candidate as an engineered waste form for used nuclear fuel and highly enriched uranium-rich wastes.

An accelerated alpha-decay damage study of a glass-bonded sodalite ceramic waste form has recently been completed. The purpose of this study was to investigate the physical and chemical durability of the waste form after significant exposure to alpha decay. This accelerated alpha-decay study was performed by doping the ceramic waste form with {sup 238}Pu which has a much greater specific activity than {sup 239}Pu that is normally present in the waste form. The alpha-decay dose at the end of the four year study was approximately 1 x 10{sup 18} alpha-decays/gram of material. An equivalent time period for a similar dose of {sup 239}Pu would require approximately 1100 years. After four years of exposure to {sup 238}Pu alpha decay, the investigation observed little change to the physical or chemical durability of the ceramic waste form (CWF). Specifically, the {sup 238}Pu-loaded CWF maintained it's physical integrity, namely that the density remained constant and no cracking or phase de-bonding was observed. The materials chemical durability and phase stability also did not change significantly over the duration of the study. The only significant measured change was an increase of the unit-cell lattice parameters of the plutonium oxide and sodalite phases of the material and an increase in the release of salt components and plutonium of the waste form during leaching tests, but, as mentioned, these did not lead to any overall loss of waste form durability. The principal findings from this study are: (1) {sup 238}Pu-loaded CWF is similar in microstructure and phase composition to referenced waste form. (2) Pu was observed primarily as oxide comprised of aggregates of nano crystals with aggregates ranging in size from submicron to twenty microns in diameter. (3) Pu phases were primarily found in the intergranular glassy regions. (4) PuO phase shows expected unit cell volume expansion due to alpha decay damage of approximately 0.7%, and the sodalite phase unit cell volume has expanded slightly by 0.3% again, presumably due to alpha-decay damage. (5) No bulk sample swelling was observed. (6) No amorphization of sodalite or actinide bearing phases was observed after four years of alpha-decay damage. (7) No microcracks or phase de-bonding were observed in waste form samples aged for four years. (8) In some areas of the {sup 238}Pu doped ceramic waste form material bubbles and voids were found. Bubbles and voids with similar size and density were also found in ceramic waste form samples without actinide. These bubbles and voids are interpreted as pre-existing defects. However, some contribution to these bubbles and voids from helium gas can not be ruled out. (9) Chemical durability of {sup 238}Pu CWF has not changed significantly after four years of alpha-decay exposure except for an increase in the release of salt components and Pu. Still, the plutonium release from CWF is very low at less than 0.005 g/m{sup 2}.

A multiphase waste form referred to as the ceramic waste form (CWF) will be used to immobilize radioactively contaminated salt wastes recovered after the electrometallurgical treatment of spent sodium-bonded nuclear fuel. The CWF is made by first occluding salt in zeolite and then encapsulating the zeolite in a borosilicate binder glass. A variety of surrogate CWF materials were made using pressureless consolidation (PC) methods for comparison with CWF consolidated using a hot isostatic press (HIP) method and to study the effects of glass/zeolite batching ratio and processing conditions on the physical and chemical properties of the resulting materials. The data summarized in this report will also be used to support qualification of the PC CWF for disposal in the proposed federal high-level radioactive waste repository at Yucca Mountain. The phase composition and microstructure of HIP CWF and PC CWF are essentially identical: both are composed of about 70% sodalite, 25% binder glass, and a 5% total of inclusion phases (halite, nepheline, and various oxides and silicates). The primary difference is that PC CWF materials have higher porosities than HIP CWFs. The product consistency test (PCT) that was initially developed to monitor homogeneous glass waste forms was used to measure the chemical durabilities of the CWF materials. Series of replicate tests with several PC CWF materials indicate that the PCT can be conducted with the same precision with CWF materials as with borosilicate glasses. Short-term (7-day) PCTs were used to evaluate the repeatability of making the PC CWF and the effects of the glass/zeolite mass ratio, process temperature, and processing time on the chemical durability. Long-term (up to 1 year) PCTs were used to compare the durabilities of HIP and PC CWFs and to estimate the apparent solubility limit for the PC CWF that is needed for modeling. The PC and HIP CWF materials had similar disabilities, based on the release of silicon in long-term tests. These tests and analyses indicate that CWF made using the PC and HIP methods should be equally acceptable for disposal. The same waste loading can be used in PC CWFs and HIP CWFs. The disposition of radionuclides is the same in PC and HIP CWFs. One minor difference is that radionuclide and halite inclusions are fairly uniformly distributed in the binder glass phase of the PC CWF, whereas they are segregated near the sodalite domains in the HIP CWF. This is an advantage of the PC CWF, since the aggregation of halite inclusion lowers the effective durability of the surrounding glass, due to the greater exposed glass surface area after the halite dissolves.

In this study, glass ceramics were explored as an alternative waste form for glass, the current baseline, to be used for immobilizing alkaline/alkaline earth + lanthanide (CS+LN) or CS+LN+transition metal (TM) fission-product waste streams generated by a uranium extraction (UREX+) aqueous separations type process. Results from past work on a glass waste form for the combined CS+LN waste streams showed that as waste loading increased, large fractions of crystalline phases precipitated upon slow cooling.[1] The crystalline phases had no noticeable impact on the waste form performance by the 7-day product consistency test (PCT). These results point towards the development of a glass ceramic waste form for treating CS+LN or CS+LN+TM combined waste streams. Three main benefits for exploring glass ceramics are: (1) Glass ceramics offer increased solubility of troublesome components in crystalline phases as compared to glass, leading to increased waste loading; (2) The crystalline network formed in the glass ceramic results in higher heat tolerance than glass; and (3) These glass ceramics are designed to be processed by the same melter technology as the current baseline glass waste form. It will only require adding controlled canister cooling for crystallization into a glass ceramic waste form. Highly annealed waste form (essentially crack free) with up to 50X lower surface area than a typical High-Level Waste (HLW) glass canister. Lower surface area translates directly into increased durability. This was the first full year of exploring glass ceramics for the Option 1 and 2 combined waste stream options. This work has shown that dramatic increases in waste loading are achievable by designing a glass ceramic waste form as an alternative to glass. Table S1 shows the upper limits for heat, waste loading (based on solubility), and the decay time needed before treatment can occur for glass and glass ceramic waste forms. The improvements are significant for both combined waste stream options in terms of waste loading and/or decay time required before treatment. For Option 1, glass ceramics show an increase in waste loading of 15 mass % and reduction in decay time of 24 years. Decay times of {approx}50 years or longer are close to the expected age of the fuel that will be reprocessed when the modified open or closed fuel cycle is expected to be put into action. Option 2 shows a 2x to 2.5x increase in waste loading with decay times of only 45 years. Note that for Option 2 glass, the required decay time before treatment is only 35 years because of the waste loading limits related to the solubility of MoO{sub 3} in glass. If glass was evaluated for similar waste loadings as those achieved in Option 2 glass ceramics, the decay time would be significantly longer than 45 years. These glass ceramics are not optimized, but already they show the potential to dramatically reduce the amount of waste generated while still utilizing the proven processing technology used for glass production.