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All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

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

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

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2015

Charge-Coupled Substituted Garnets (Y 3-x Ca 0.5x M 0.5x )Fe 5 O 12 (M = Ce, Th): Structure and Stability as Crystalline Nuclear Waste Forms

The garnet structure has been proposed as a potential crystalline nuclear waste form for accommodation of actinide elements, especially uranium (U). In this study, yttrium iron garnet (YIG) as a model garnet host was studied for the incorporation of U analogs, cerium (Ce) and thorium (Th), incorporated by a charge-coupled substitution with calcium (Ca) for yttrium (Y) in YIG, namely, 2Y 3+ = Ca 2+ + M 4+ , where M 4+ = Ce 4+ or Th 4+ . Single-phase garnets Y 3–x Ca 0.5x M 0.5x Fe 5 O 12 (x = 0.1–0.7) were synthesized by the citrate–nitrate combustion method. Ce was confirmed to be tetravalent by X-ray absorption spectroscopy and X-ray photoelectron spectroscopy. X-ray diffraction and 57 Fe–Mössbauer spectroscopy indicated that M 4+ and Ca 2+ cations are restricted to the c site, and the local environments of both the tetrahedral and the octahedral Fe 3+ are systematically affected by the extent of substitution. The charge-coupled substitution has advantages in incorporating Ce/Th and in stabilizing the substituted phases compared to a single substitution strategy. Enthalpies of formation of garnets were obtained by high temperature oxide melt solution calorimetry, and the enthalpies of substitution of Ce and Th were determined. The thermodynamic analysis demonstrates that the substituted garnets are entropically rather than energetically stabilized. This suggests that such garnets may form and persist in repositories at high temperature but might decompose near room temperature.

Guo, Xiaofeng↗
DOE OSTI2019

Leach Testing of Laboratory-Scale Melter Evaporator Condensate Cementitious Waste Forms

Cementitious waste forms immobilizing evaporated AP-105 off-gas condensate were used to determine radionuclide and contaminant leachability in deionized water over a 63-day period. The off-gas condensate was collected during the actual tank AP-105 low activity waste continuous laboratory-scale melter (LSM)) run performed in fiscal year 2018 and was then solidified as a cementitious waste form using the Cast Stone formulation (8 weight percent [wt%] ordinary Portland cement, 45 wt% class F fly ash, 47 wt% blast furnace slag). Here, using the U.S. Environmental Protection Agency Method 1315 leach testing procedure, the release rate of technetium 99 (Tc), iodine-129 (I), nitrate (NO 3 - ), and sodium (Na + ) from two Cast Stone specimens was measured. From these measurements, observed diffusivity values for each constituent were calculated and can be used in future iterations and maintenance of the Integrated Disposal Facility performance assessments. Furthermore, by testing Cast Stone specimens immobilizing off-gas produced while vitrifying actual tank waste, the results of this effort improve the technical defensibility of long-term waste form performance estimates for the Cast Stone formulation. Finally, 99 Tc distribution within a representative waste form at the end of the 63-day leach period as well as bulk mineralogy were determined using solid phase characterization methods.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2013

Crystalline Ceramic Waste Forms: Comparison Of Reference Process For Ceramic Waste Form Fabrication

The research conducted in this work package is aimed at taking advantage of the long term thermodynamic stability of crystalline ceramics to create more durable waste forms (as compared to high level waste glass) in order to reduce the reliance on engineered and natural barrier systems. Durable ceramic waste forms that incorporate a wide range of radionuclides have the potential to broaden the available disposal options and to lower the storage and disposal costs associated with advanced fuel cycles. Assemblages of several titanate phases have been successfully demonstrated to incorporate radioactive waste elements, and the multiphase nature of these materials allows them to accommodate variation in the waste composition. Recent work has shown that they can be produced from a melting and crystallization process. The objective of this report is to explore the phase formation and microstructural differences between lab scale melt processing in varying gas environments with alternative densification processes such as Hot Pressing (HP) and Spark Plasma Sintering (SPS). The waste stream used as the basis for the development and testing is a simulant derived from a combination of the projected Cs/Sr separated stream, the Trivalent Actinide - Lanthanide Separation by Phosphorous reagent Extraction from Aqueous Komplexes (TALSPEAK) waste stream consisting of lanthanide fission products, the transition metal fission product waste stream resulting from the transuranic extraction (TRUEX) process, and a high molybdenum concentration with relatively low noble metal concentrations. Melt processing as well as solid state sintering routes SPS and HP demonstrated the formation of the targeted phases; however differences in microstructure and elemental partitioning were observed. In SPS and HP samples, hollandite, pervoskite/pyrochlore, zirconolite, metallic alloy and TiO 2 and Al 2 O 3 were observed distributed in a network of fine grains with small residual pores. The titanate phases that incorporate M +3 rare earth elements were observed to be distinct phases (ex. Nd 2 Ti 2 O 7 with less degree of substitution as compared to the more homogeneous melt processed samples where a high degree of substitution and variation of composition within grains was observed. Liquid phase sintering was enhanced in reducing gas environments and resulted in large (10-200 microns) irregular shaped grains along with large voids associated with the melt process; SPS and HP samples exhibited finer grain size with smaller voids. Metallic alloys were observed in the bulk of the sample for SPS and HP samples, but were found at the bottom of the crucible in melt processed trials. These results indicate that for a first melter trial, the targeted phases can be formed in air by utilizing Ti/TiO 2 additives which aid phase formation and improve the electrical conductivity. Ultimately, a melter run in reducing gas environments would be beneficial to study differences in phase formation and elemental partitioning.

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DOE OSTI2019

Thermodynamic assessment of the hollandite high‐level radioactive waste form

Abstract Hollandite has been studied as a candidate ceramic waste form for the disposal of high‐level radioactive waste due to its inherent leach resistance and ability to immobilize alkaline‐earth metals such as Cs and Ba at defined lattice sites in the crystallographic structure. The chemical and structural complexity of hollandite‐type phases developed for high‐level waste immobilization limits the systematic experimental research that is required to understand phase development due to the large number of potential additives and compositional ranges that must be evaluated. Modeling the equilibrium behavior of the complex hollandite‐forming oxide waste system would aid in the design and processing of hollandite waste forms by predicting their thermodynamic stability. Thus, a BaO–Cs 2 O–TiO 2 –Cr 2 O 3 –Al 2 O 3 –Fe 2 O 3 –FeO–Ga 2 O 3 thermodynamic database was developed in this work according to the CALPHAD methodology. The compound energy formalism was used to model solid solution phases such as hollandite while the two‐sublattice partially ionic liquid model characterized the oxide melt. Results of model optimizations are presented and discussed including a 1473 K isothermal BaO–Cs 2 O–TiO 2 pseudo‐ternary diagram that extrapolates phase equilibrium behavior to regions not experimentally explored.

Utlak, Stephen A.↗
DOE OSTI2020

Epsilon Metal: A Waste Form for Noble Metals from Used Nuclear Fuel

Epsilon metal (e-metal) is the metallic phase that forms as inclusions at the grain boundaries in the UO2 fuel during reactor operation. This metal is composed of Pd, Mo, Rh, Ru, and Tc. These metallic inclusions are insoluble in strong acid and remnants of these metallic inclusions have been found in the UO2 matrix that remains from the natural reactors in Gabon that were active 1.8 billion years ago, therefore e-metal should be an excellent waste form for the immobilization of the long-lived isotopes 107Pd (6.5 ? 106 a) and 99Tc (2.13 ? 105 a), with 99Tc being the isotope of interest for repository performance. Therefore, the chemical durability of this potential waste form is assessed in this study. Typically, corrosion rates for metallic materials are measured electrochemically because they are quick, inexpensive, and can reveal the mechanism by which a metal corrodes, at least initially. However, in a repository the waste form would be subjected to slowly flowing water without an applied electrical potential over long time periods. Therefore, the corrosion rates of e-metal specimens were measured with both electrochemical tests and the single-pass flow-through test (SPFT). Potentiodynamic and potentiostatic polarization results suggest that a thin passive film exists on the alloy surface, which seems to be responsible for its high corrosion resistance. Additionally, X-Ray photoelectron spectroscopic results suggest that Pd oxides are significantly enriched in the passive film Results from the SPFT show that the dissolution rates were weakly dependent on pH. Only Mo and Re were found in solution and were used for the calculation of the dissolution rates. In general, the electrochemically determined corrosion rates agree reasonably well with the initial dissolution rate measured with the SPFT test, but they are about one or two orders of magnitude higher than the steady state rates. The causes for this discrepancy are discussed.

epsilon-metal, nuclear waste form, corrosion, sing↗
DOE OSTI2015

Melt Processed Crystalline Ceramic Waste Forms for Advanced Nuclear Fuel Cycles: CRP T21027 1813: Processing technologies for high level waste, formulation of matrices and characterization of waste forms, Task 17208 (Final Report)

A multi-phase ceramic waste form is being developed at the Savannah River National Laboratory (SRNL) for treatment of secondary waste streams generated by reprocessing commercial spent nuclear. The envisioned waste stream contains a mixture of transition, alkali, alkaline earth, and lanthanide metals. Ceramic waste forms are tailored (engineered) to incorporate waste components as part of their crystal structure based on knowledge from naturally found minerals containing radioactive and non-radioactive species similar to the radionuclides of concern in wastes from fuel reprocessing. The ability to tailor ceramics to mimic naturally occurring crystals substantiates the long term stability of such crystals (ceramics) over geologic timescales of interest for nuclear waste immobilization [1]. A durable multi-phase ceramic waste form tailored to incorporate all the waste components has the potential to broaden the available disposal options and thus minimize the storage and disposal costs associated with aqueous reprocessing. This report summarizes results from three years of work on the IAEA Coordinated Research Project on “Processing technologies for high level waste, formulation of matrices and characterization of waste forms” (T21027), and specific task “Melt Processed Crystalline Ceramic Waste Forms for Advanced Nuclear Fuel Cycles” (17208).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2015

Melt Processed Crystalline Ceramic Waste Forms for Advanced Nuclear Fuel Cycles CRP T21027 1813: Processing technologies for high level waste, formulation of matrices and characterization of waste forms, Task 17208 (Final Report)

A multi-phase ceramic waste form is being developed at the Savannah River National Laboratory (SRNL) for treatment of secondary waste streams generated by reprocessing commercial spent nuclear. The envisioned waste stream contains a mixture of transition, alkali, alkaline earth, and lanthanide metals. Ceramic waste forms are tailored (engineered) to incorporate waste components as part of their crystal structure based on knowledge from naturally found minerals containing radioactive and non-radioactive species similar to the radionuclides of concern in wastes from fuel reprocessing. The ability to tailor ceramics to mimic naturally occurring crystals substantiates the long term stability of such crystals (ceramics) over geologic timescales of interest for nuclear waste immobilization. A durable multi-phase ceramic waste form tailored to incorporate all the waste components has the potential to broaden the available disposal options and thus minimize the storage and disposal costs associated with aqueous reprocessing. This report summarizes results from three years of work on the IAEA Coordinated Research Project on “Processing technologies for high level waste, formulation of matrices and characterization of waste forms” (T21027), and specific task “Melt Processed Crystalline Ceramic Waste Forms for Advanced Nuclear Fuel Cycles” (17208).

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DOE OSTI2016

Mineral assemblage transformation of a metakaolin-based waste form after geopolymer encapsulation

Current plans for nuclear waste vitrification at the Hanford Tank Waste Treatment and Immobilization Plant (WTP) lack the capacity to treat all of the low activity waste (LAW) that is not encapsulated in the vitrified product. Fluidized Bed Steam Reforming (FBSR) is one of the supplemental technologies under consideration to fill this gap. The FBSR process results in a granular product mainly composed of feldspathoid mineral phases that encapsulate the LAW and other contaminants of concern (COCs). In order to better understand the characteristics of the FBSR product, characterization testing has been performed on the granular product as well as the granular product encapsulated in a monolithic geopolymer binder. The non-radioactive simulated tank waste samples created for use in this study are the result of a 2008 Department of Energy sponsored Engineering Scale Technology Demonstration (ESTD) in 2008. These samples were created from waste simulant that was chemically shimmed to resemble actual tank waste, and rhenium has been used as a substitute for technetium. Another set of samples was created by the Savannah River Site Bench-Scale Reformer (BSR) using a chemical shim of Savannah River Site Tank 50 waste in order to simulate a blend of 68 Hanford tank wastes. This paper presents results from coal and moisture removal tests along with XRD, SEM, and BET analyses showing that the major mineral components are predominantly sodium aluminosilicate minerals and that the mineral product is highly porous. Results also show that the materials pass the short-term leach tests: the Toxicity Characteristic Leaching Procedure (TCLP) and Product Consistency Test (PCT).

Feldspathoid Minerals↗
DOE OSTI2026

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

The importance of glass and glass–ceramic nuclear waste forms has been reaffirmed in recent years by the growing interest in nuclear power as a reliable energy source. Determination of processing methods for the disposal of halide-containing wastes will be essential for the advancement of nuclear technologies such as non-aqueous fuel reprocessing. Phosphate-based dechlorination and subsequent vitrification of radioactive salt waste into an iron-phosphate waste form have been identified as a potential processing scheme for electrochemical processing waste. The impact of H 3 PO 4 -based dechlorination of complex salt mixtures on the vitrification process and structure of the final iron-phosphate waste form has not yet been investigated. In this work, iron-phosphate glass–ceramics were made from simulant salt waste (48LiCl–33KCl–19NaCl mol%) dechlorinated with the H3PO4-based method. The glass-forming region was compared to that of traditionally prepared Na 2 O–Fe 2 O 3 –P 2 O 5 systems. For a candidate glass-forming composition, the processing scheme presented here was determined to favor Fe 3+ species. The O/P molar ratio was consistent for the candidate composition when dechlorinated at 400°C and 600°C in air and argon environments, indicating glass network connectivity was maintained despite variations in processing parameters. The results presented here validate processing schemes requiring iron-phosphate waste form synthesis following H 3 PO 4 -based dechlorination.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

Immobilization of cesium and iodine into Cs 3 Bi 2 I 9 perovskite-silica composites and core-shell waste forms with high waste loadings and chemical durability

Cs$_3$Bi$_2$I$_9$, a defect perovskite derivative, is a potential host phase to immobilize iodine and cesium with high waste loadings. In this work, two strategies were explored to form Cs$_3$Bi$_2$I$_9$-silica composites and a core-shell structure in order to improve chemical durability of waste form materials meanwhile maintaining high waste loadings. Cs$_3$Bi$_2$I$_9$ loadings as high as 70 wt.% were incorporated into a silica matrix to form silica-ceramic composites, and 20 wt.% Cs$_3$Bi$_2$I$_9$ was encapsulated into silica to form a core–shell structure by low temperature spark plasma sintering. Chemical durability of the composite and core-shell waste forms was evaluated by semi-dynamic leaching experiments, and Cs and I were incongruently released from waste form matrices. A BiOI alteration layer formed, acting as a passivation layer to reduce the release of radionuclides. The long-term iodine release rate was low (30 mg m$^{-2}$ day$^{-1}$) for the 70 wt.%Cs$_3$Bi$_2$I$_9$–silica composite leached in deionized water at 90 °C, which can be further reduced to 5 × 10$^{-3}$ mg m$^{-2}$ day$^{-1}$ for the 20 wt.% core-shell structure. This work highlights a robust way to immobilize the highly mobile radionuclides with high waste loadings through encapsulation into durable matrices and a surface passivating mechanism that can greatly reduce the elemental transport from waste form materials and significantly enhance their chemical durability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Cold crucible induction melter studies for making glass ceramic waste forms: A feasibility assessment

Glass ceramics are being developed to immobilize fission products, separated from used nuclear fuel by aqueous reprocessing, into a stable waste form suitable for disposal in a geological repository. This work documents the glass ceramic formulation at bench scale and for a scaled melter test performed in a pilot-scale (approximately 1/4 scale) cold crucible induction melter (CCIM). Melt viscosity, electrical conductivity, and crystallization behavior upon cooling were measured on a small set of compositions to select a formulation for melter testing. Property measurements also identified a temperature range for melter operation and cooling profiles necessary to crystallize the targeted phases in the waste form. Bench scale and melter run results successfully demonstrate the processability of the glass ceramic using the CCIM melter technology.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2016

Designing Advanced Ceramic Waste Forms for Electrochemical Processing Salt Waste

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 Na 2 O 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.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2012

Radioactive Bench-scale Steam Reformer Demonstration of a Monolithic Steam Reformed Mineralized Waste Form for Hanford Waste Treatment Plant Secondary Waste - 12306

Hanford currently has 212,000 m{sup 3} (56 million gallons) of highly radioactive mixed waste stored in the Hanford tank farm. This waste will be processed to produce both high-level and low-level activity fractions, both of which are to be vitrified. Supplemental treatment options have been under evaluation for treating portions of the low-activity waste, as well as the liquid secondary waste from the low-activity waste vitrification process. One technology under consideration has been the THOR{sup R} fluidized bed steam reforming process offered by THOR Treatment Technologies, LLC (TTT). As a follow-on effort to TTT's 2008 pilot plant FBSR non-radioactive demonstration for treating low-activity waste and waste treatment plant secondary waste, TTT, in conjunction with Savannah River National Laboratory, has completed a bench scale evaluation of this same technology on a chemically adjusted radioactive surrogate of Hanford's waste treatment plant secondary waste stream. This test generated a granular product that was subsequently formed into monoliths, using a geo-polymer as the binding agent, that were subjected to compressibility testing, the Product Consistency Test and other leachability tests, and chemical composition analyses. This testing has demonstrated that the mineralized waste form, produced by co-processing waste with kaolin clay using the TTT process, is as durable as low-activity waste glass. Testing has shown the resulting monolith waste form is durable, leach resistant, and chemically stable, and has the added benefit of capturing and retaining the majority of Tc-99, I-129, and other target species at high levels. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2017

Cesium incorporation in hollandite-rich multiphasic ceramic waste forms

Hollandite-rich multiphase waste form compositions processed by melt-solidification and spark plasma sintering (SPS) were characterized, compared, and validated for nuclear waste incorporation. Phase identification by x-ray diffraction (XRD) and electron back-scattered diffraction (EBSD) confirmed hollandite as the major phase present in these samples along with perovskite, pyrochlore and zirconolite. Distribution of selected elements observed by wavelength dispersive spectroscopy (WDS) maps indicated that Cs formed a secondary phase during SPS processing, which was considered undesirable. On the other hand, Cs partitioned into the hollandite phase in melt-processed samples. Further analysis of hollandite structure in melt-processed composition by selected area electron diffraction (SAED) revealed ordered arrangement of tunnel ions (Ba/Cs) and vacancies, suggesting efficient Cs incorporation into the lattice.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Direct Processing of Lithium Chloride Based Waste Salt in a Ceramic Waste Form

Ceramic waste form materials were fabricated with a LiCl based salt mixture to demonstrate the suitability of direct processing of waste salt from an all LiCl pyroprocessing flow sheet on the formation, microstructure, and durability of ceramic waste forms. Materials were successfully synthesized by using the simplified direct processing technique with salt loadings of 5, 7.5, and 10 wt% at the laboratory scale. Materials fabricated with LiCl based salt indicated full conversion of zeolite to sodalite occurred to form products with low open porosity. This indicates that the Na 2 O content of NBS4 glass is suitable for processing salt chemistries which do not contain NaCl. Generated sodalite was microencapsulated by the glass binder, halite occlusions were detected within sodalite domains at all salt loadings, and a Cs-rich phase believed to be Cs-pollucite was detected in the material made with the lowest salt loading (5 wt%). Salt inclusions were encapsulated within the binder glass at all loadings, and found to consist primarily of NaCl with Cs present. A small amount of salt was found at the surface of the wasteform made with the highest salt loading of 10 wt%, which may indicate an upper limit to the amount of salt that can be accommodated or incomplete mechanical mixing of the reagents. Durability testing by using the ASTM C1308 method indicated that initial rapid dissolution of exposed halite inclusion phases was directly correlated to salt loading. Wasteform degradation during all tests occurred primarily due to dissolution of the sodalite phase. Durability of the binder glass was found to increase as the waste salt loading increased. Results for the release of cations from the salt indicate the changes in wasteform durability and halite inclusion chemistry are strongly influenced by ion exchange phenomena between the salt and the glass. This appears to be the result of the relatively stronger affinity for the glass phase of Li, compared to that of other cations such as Na and Cs. The effects from cation exchange were diminished at lower salt loadings.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2013

Radioactive Demonstration Of Mineralized Waste Forms Made From Hanford Low Activity Waste (Tank Farm Blend) By Fluidized Bed Steam Reformation (FBSR)

The U.S. Department of Energy’s Office of River Protection (ORP) is responsible for the retrieval, treatment, immobilization, and disposal of Hanford’s tank waste. A key aspect of the River Protection Project (RPP) cleanup mission is to construct and operate the Hanford Tank Waste Treatment and Immobilization Plant (WTP). The WTP will separate the tank waste into high-level and low-activity waste (LAW) fractions, both of which will subsequently be vitrified. The projected throughput capacity of the WTP LAW Vitrification Facility is insufficient to complete the RPP mission in the time frame required by the Hanford Federal Facility Agreement and Consent Order, also known as the Tri-Party Agreement (TPA), i.e. December 31, 2047. Supplemental Treatment is likely to be required both to meet the TPA treatment requirements as well as to more cost effectively complete the tank waste treatment mission. The Supplemental Treatment chosen will immobilize that portion of the retrieved LAW that is not sent to the WTP’s LAW Vitrification facility into a solidified waste form. The solidified waste will then be disposed on the Hanford site in the Integrated Disposal Facility (IDF). Fluidized Bed Steam Reforming (FBSR) offers a moderate temperature (700-750°C) continuous method by which LAW can be processed irrespective of whether the waste contain organics, nitrates, sulfates/sulfides, chlorides, fluorides, volatile radionuclides or other aqueous components. The FBSR technology can process these wastes into a crystalline ceramic (mineral) waste form. The mineral waste form that is produced by co-processing waste with kaolin clay in an FBSR process has been shown to be comparable to LAW glass, i.e. leaches Tc-99, Re and Na at <2g/m 2 during ASTM C1285 (Product Consistency) durability testing. Monolithing of the granular FBSR product was investigated to prevent dispersion during transport or burial/storage. Monolithing in an inorganic geopolymer binder, which is amorphous, macro-encapsulates the granules, and the monoliths pass ANSI/ANS 16.1 and ASTM C1308 durability testing with Re achieving a Leach Index (LI) of 9 (the Hanford Integrated Disposal Facility, IDF, criteria for Tc-99) after a few days and Na achieving an LI of >6 (the Hanford IDF criteria for Na) in the first few hours. The granular and monolithic waste forms also pass the EPA Toxicity Characteristic Leaching Procedure (TCLP) for all Resource Conservation and Recovery Act (RCRA) components at the Universal Treatment Standards (UTS). Two identical Benchscale Steam Reformers (BSR) were designed and constructed at SRNL, one to treat non-radioactive simulants and the other to treat actual radioactive wastes. The results from the non-radioactive BSR were used to determine the parameters needed to operate the radioactive BSR in order to confirm the findings of non-radioactive FBSR pilot scale and engineering scale tests and to qualify an FBSR LAW waste form for applications at Hanford. Radioactive testing commenced using SRS LAW from Tank 50 chemically trimmed to look like Hanford’s blended LAW known as the Rassat simulant as this simulant composition had been tested in the non-radioactive BSR, the non-radioactive pilot scale FBSR at the Science Applications International Corporation-Science and Technology Applications Research (SAIC-STAR) facility in Idaho Falls, ID and in the TTT Engineering Scale Technology Demonstration (ESTD) at Hazen Research Inc. (HRI) in Denver, CO. This provided a “tie back” between radioactive BSR testing and non-radioactive BSR, pilot scale, and engineering scale testing. Approximately six hundred grams of non-radioactive and radioactive BSR product were made for extensive testing and comparison to the non-radioactive pilot scale tests performed in 2004 at SAIC-STAR and the engineering scale test performed in 2008 at HRI with the Rassat simulant. The same mineral phases and off-gas species were found in the radioactive and non-radioactive testing. The granular ESTD and BSR products (radioactive and non-radioactive) were analyzed for total constituents and durability tested as a granular waste form. A subset of the granular material was stabilized in a clay based geopolymer matrix at 42% and 65% FBSR loadings and durability tested as a monolith waste form. The 65 wt% FBSR loaded monolith made with clay (radioactive) was more durable than the 67-68 wt% FBSR loaded monoliths made from fly ash (non-radioactive) based on short term PCT testing. Long term, 90 to 107 day, ASTM C1308 testing (similar to ANSI/ANS 16.1 testing) was only performed on two fly ash geopolymer monoliths at 67-68 wt% FBSR loading and three clay geopolymer monoliths at 42 wt% FBSR loading. More clay geopolymers need to be made and tested at longer times at higher FBSR loadings for comparison to the fly ash monoliths. Monoliths made with metakaolin (heat treated) clay are of a more constant composition and are very reactive as the heat treated clay is amorphous and alkali activated. The monoliths made with fly ash are subject to the inherent compositional variation found in fly ash as it is a waste product from burning coal and it contains unreactive components such as mullite. However, both the fly ash and the clay based monoliths perform well in long term ASTM C1308 testing.

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