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Matyas, Josef

Publications and source records attributed to Matyas, Josef.

17 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Semi-Dynamic Leach Testing of Densified Silicon-based Iodine Waste Forms

Iodine waste forms (IWF) require a conceptual corrosion release model (CCRM) to provide iodine (I) release rates for performance modeling nuclear waste disposal repositories. To develop a CCRM, an understanding of the corrosion mechanisms of the IWF are required along with data from consistent test methods to parameterize the model. The present study has advanced both areas by providing and assessing the corrosion resistance of IWF types based on their processing history in minor variations of semi-dynamic leach tests. The test included a series of semi-dynamic leach tests using monolithic IWFs in deionized water (leachant). Several experiments were conducted under alternate test conditions with changes to temperature, leachant replacement, leachant pH, leachant volume, masking, and surface finish to elucidate if varying these conditions impacted IWF corrosion behavior. Tests were conducted on two classes of IWFs: (1) I-bearing silver-mordenite (AgZ) materials processed by hot isostatic pressing (HIP) at different temperatures, pressures, sizes, and times; and (2) I-bearing silver-functionalized silica aerogels (SFA) processed by either HIP or spark plasma sintering (SPS). The corrosion susceptibility of AgZ samples was influenced by HIP temperature and pressure. The SPS SFAs retained I far better than HIP SFAs. Additional findings in this study include: (1) The iodine dissolution rate decreased with decreasing temperature, (2) a common ion effect may occur and slow dissolution of the host phase if the leachant is not regularly replaced, (3) pH controls the dissolution rate, and (4) the iodine dissolution rate slows with extended test time (up to 224 days). Based on this work, these parameters should thus be represented when developing a CCRM.

corrosion↗
DOE OSTI2023

Technology Development Roadmap for Volatile Radionuclide Capture and Immobilization

An “Off-Gas and Waste Forms Strategy Workshop” was held in Washington, D.C. on January 31, and February 1, 2023, to review the current state of the art (baseline) technologies for capturing and immobilizing these volatile radionuclides in waste forms (WFs). The discussions in that workshop were used to develop a roadmap for future research and development to mature technologies that are presently not ready for use in a commercial reprocessing facility and develop and demonstrate technologies that provide more safety, more simplicity, or lower costs compared to the current baseline.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Roadmap to Iodine and Mercury Abatement Materials Selection in Nuclear Waste Processing Off-Gas Streams

This work provides a guide for candidate mercury (Hg) and iodine-129 (129I) abatement material identification, screening, evaluation, technical gap identification, and bench-scale testing prioritization while also conceptualizing a materials deployment roadmap for implementation of new materials in the Hanford Waste Treatment and Immobilization Plant (WTP) Low-Activity Waste (LAW) Facility at Hanford in Richland, Washington, and elsewhere in the U.S. Department of Energy (DOE) complex for similar applications. The study was prompted by the need to replace the Kombisorb BAT-37 due to uncertainties in Hg and 129I capture performance and future availability for use in the WTP LAW Facility secondary off-gas system, specifically the Carbon Adsorber units. However, replacement of this material could also mitigate two other issues with Kombisorb BAT-37 (and its successor BAT II 37): (1) fire safety risk due to exothermic heat generated by adsorption reactions between the carbon material and Hg and (2) the risk of low retention of 129I in glass and subsequent downstream impacts on secondary liquid waste treatment at the Effluent Treatment Facility.

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

Developing a Fundamental Knowledge Base for the Interaction of Ruthenium with Natural and Engineered Iron-Bearing Materials

The intent of this project is to build a fundamental knowledge base concerning the redox coupling between Ru and Fe in heterogeneous systems with predictive applications towards the fate, speciation, and transport of Ru in the environment and its capture using available technologies. RuNOCl 3 and Fe 3+ are redox active over a broad range of pH. Initial assessment of effect of redox coupling between Ru and Fe indicates that Fe(III) in ferrihydrite can oxidize Ru 2+ in RuNOCl3 to Ru(IV) during coprecipitation at ambient conditions and alkaline pH. Further, evidence suggests that Ru(IV) is incorporated in the structure of fh. Likewise, Fe 3+ (aq) also reduces Ru 2+ in RuNOCl 3 in the homogenous system at acidic pH although the kinetics of reaction appear to be slow. Rufh annealed to 500 0C transforms to Ru(III) doped hematite. AIMD informed EXAFS indicates that Ru substitutes for Fe(III) in regular octahedral sites of hematite but requires three distinct configurations involving edge-sharing protonated Fe vacancies and straight substitution with no local defects. Fe 2+ (aq) appears to oxidize at the surface of RuO 2 , but the amount is too low to reasonably expect detectable reduced Ru. Future experiments at higher pH are warranted to make Fe 2+ (aq) less stable (i.e., make more redox active). We also demonstrated that we can functionalize Si aerogels with Fe(II) and Fe(III) but likely need to go to higher T to make Feo nanoparticles.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Investigating the Durability of Iodine Waste Forms in Dilute Conditions

To prevent the release of radioiodine during the reprocessing of used nuclear fuel or in the management of other wastes, many technologies have been developed for iodine capture. The capture is only part of the challenge as a durable waste form is required to ensure safe disposal of the radioiodine. This work presents the first durability studies in dilute conditions of two AgI-containing waste forms: hot-isostatically pressed silver mordenite (AgZ) and spark plasma sintered silver-functionalized silica aerogel (SFA) iodine waste forms (IWF). Using the single-pass flow-through (SPFT) test method, the dissolution rates respective to Si, Al, Ag and I were measured for variants of the IWFs. By combining solution and solid analysis information on the corrosion mechanism neutral-to-alkaline conditions was elucidated. The AgZ samples were observed to have corrosion preferentially occur at secondary phases with higher Al and alkali content. These phases contained a lower proportion of I compared with the matrix. The SFA samples experienced a higher extent of corrosion at Si-rich particles, but an increased addition of Si to the waste led to an improvement in corrosion resistance. The dissolution rates for the IWF types are of similar magnitude to other Si-based waste form materials measured using SPFT.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Nitride-based controlled-release fertilizers and process for making same

A controlled-release solid nitride fertilizer from fly ash and a method for making are described. The fertilizer includes a nitrogen source including at least one solid nitride combined with at least one precipitation-inhibiting agent and with at least one moisture-retention agent, all compressed together to form a porous release structure that in contact with water releases ammonium ions as a nitrogen nutrient at a substantially uniform release rate over a selected release period and thereby maximizes nitrogen-use efficiency by plants.

Amonette, James E.↗
DOE OSTI2018

Silver-functionalized silica aerogels and their application in the removal of iodine from aqueous environments

Here, one of the key challenges for radioactive waste management is the efficient capture and immobilization of radioiodine, because of its radiotoxicity, high mobility in the environment, and long half-life (t 1/2 = 1.57 × 10 7 years). Silver-functionalized silica aerogel (AgAero) represents a strong candidate for safe sequestration of radioiodine from various nuclear waste streams and subsurface environments. Batch sorption experiments up to 10 days long were carried out in oxic and anoxic conditions in both deionized water (DIW) and various Hanford Site Waste Treatment Plant (WTP) off-gas condensate simulants containing from 5 to 10 ppm of iodide (I – ) or iodate (IO 3 – ). Also tested was the selectivity of AgAero towards I – in the presence of other halide anions. AgAero exhibited fast and complete removal of I – from DIW, slower but complete removal of I – from WTP off-gas simulants, preferred removal of I – over Br – and Cl – , and it demonstrated ability to remove IO 3 – through reduction to I – .

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2018

Evaluation of Crystal Accumulation in High Level Waste Glasses with Research-Scale Melter

The report summarizes the experimental results from a long term Research Scale Melter (RSM) test which was performed at Pacific Northwest National Laboratory (PNNL) in FY16 to answer questions on the effects of spinel crystal accumulation on melter performance and operational longevity. The RSM was used to vitrify a surrogate waste material of the Hanford AZ-101 tank waste composition. This waste contains a high concentration of Fe and Ni and is susceptible to precipitation of a large quantity of spinel crystals during vitrification. The RSM test was run over a period of 11 weeks and consisted of eleven feeding/pouring and idling periods. The feeding/pouring periods were 36 h long while the idling periods ranged from 4 to 7 days. Approximately 509 kg of feed was processed, producing ~159 kg of glass. The main goal of this test was to determine if the riser of the melter can be clogged by accumulated layer of spinel crystals which precipitated from glass during multiple idling’s. In addition, the glass samples were collected during each pouring to evaluate a possibility of a partial or complete removal of crystal deposits accumulated during idling. Furthermore, an electrical conductivity probe was tested for monitoring the crystal accumulation in the riser of the melter during idling’s. The test was concluded by dissecting the melter and preparing cross-sections to determine layer thickness, crystal size and morphology of spinel crystals in the bulk of the melter and in the glass riser.

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

Apatite and sodalite based glass-bonded waste forms for immobilization of 129I and mixed halide radioactive wastes

The goal of the project was to utilize the knowledge accumulated by the team, in working with minerals for chloride wastes and biological apatites, toward the development of advanced waste forms for immobilizing 129I and mixed-halide wastes. Based on our knowledge, experience, and thorough literature review, we had selected two minerals with different crystal structures and potential for high chemical durability, sodalite and CaP/PbV-apatite, to form the basis of this project. The focus of the proposed effort was towards: (i) low temperature synthesis of proposed minerals (iodine containing sodalite and apatite) leading to the development of monolithic waste forms, (ii) development of a fundamental understanding of the atomic-scale to meso-scale mechanisms of radionuclide incorporation in them, and (iii) understanding of the mechanism of their chemical corrosion, alteration mechanism, and rates. The proposed work was divided into four broad sections. deliverables. 1. Synthesis of materials 2. Materials structural and thermal characterization 3. Design of glass compositions and synthesis glass-bonded minerals, and 4. Chemical durability testing of materials.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2015

Efficacy of a Solution-Based Approach for Making Sodalite Waste Forms for an Oxide Reduction Salt Utilized in the Reprocessing of Used Uranium Oxide Fuel

This paper describes various approaches for making sodalite with a LiCl-Li2O oxide reduction salt used to recover uranium from used oxide fuel. The approaches include sol-gel and solution-based synthesis processes. As-made products were mixed with 5 and 10 mass% of a Na2O-B2O3-SiO2 glass binder and these, along with product without a binder, were heated using either a cold-press-and-sinter method or hot uniaxial pressing. The results demonstrate the limitation of sodalite yield due to the fast intermediate reactions between Na+ and Cl- to form halite in solution and Li2O and SiO2 to form lithium silicates (e.g., Li2SiO3 or Li2Si2O5) in the calcined and sintered pellets. The results show that pellets can be made with high sodalite fractions (~92 mass%) and low porosities using a solution-based approach and this LiCl-Li2O salt.

electrochemical↗
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) 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.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2014

The effects of glass doping, temperature and time on the morphology, composition, and iron redox of spinel crystals

Precipitation of large crystals/agglomerates of spinel and their accumulation in the pour spout riser of a Joule-heated ceramic melter during idling can plug the melter and prevent pouring of molten glass into canisters. Thus, there is a need to understand the effects of spinel-forming components, temperature, and time on the growth of crystals in connection with an accumulation rate. In our study, crystals of spinel [Fe, Ni, Mn, Zn, Sn][Fe, Cr]₂O₄ were precipitated from simulated high-level waste borosilicate glasses containing different concentrations of Ni, Fe, and Cr by heat treating at 850 and 900°C for different times. These crystals were extracted from the glasses and analyzed with scanning electron microscopy and image analysis for size and shape, with inductively coupled plasma-atomic emission spectroscopy and atom probe tomography for concentration of spinel-forming components, and with wet colorimetry and Mössbauer spectroscopy for Fe²⁺/Fe total ratio. High concentrations of Ni, Fe, and Cr in glasses resulted in the precipitation of crystals larger than 100 µm in just two days. Crystals were a solid solution of NiFe₂O₄, NiCr₂O₄, and -Fe₂O₃ (identified only in the high-Ni-Fe glass) and also contained small concentrations of less than 1 at% of Li, Mg, Mn, and Al.

chemical analysis↗
DOE OSTI2014

Road Map for Development of Crystal-Tolerant High Level Waste Glasses

This road map guides the research and development for formulation and processing of crystal-tolerant glasses, identifying near- and long-term activities that need to be completed over the period from 2014 to 2019. The primary objective is to maximize waste loading for Hanford waste glasses without jeopardizing melter operation by crystal accumulation in the melter or melter discharge riser. The potential applicability to the Savannah River Site (SRS) Defense Waste Processing Facility (DWPF) is also addressed in this road map.

Accumulation↗
DOE OSTI2014

Polyacrylonitrile-Chalcogel Hybrid Sorbents for Radioiodine Capture

Powders of a Sn2S3 chalcogen-based aerogel (chalcogel) were combined with powdered polyacrylonitrile (PAN) in different mass ratios (SnS33, SnS50, and SnS70 in mass% of chalcogel), dissolved into dimethyl sulfoxide, and dropped into deionized water to form pellets of a porous PAN-chalcogel hybrid material. Pellets of these hybrid sorbents, along with pure powdered (SnSp) and granular (SnSg) forms of the chalcogel, were then used to adsorb iodine gas under both concentrated and dilute conditions. Both the SnSp and SnSg chalcogels showed very high maximum iodine loadings at 67.2 and 68.3 mass%. The maximum iodine loadings in the SnS33 and SnS50 were high at 32.8 and 53.5 mass%. In all cases, X-ray diffraction results showed the formation of Sn-I phases of SnI4 and SnI4(S8)2 revealing that the iodine binding in these materials is mainly due to a chemisorption process although some evidence also exists that supports a physisorption process.

chalcogel↗
DOE OSTI2014

Alternative Electrochemical Salt Waste Forms, Summary of FY11-FY12 Results

The Fuel Cycle Research and Development Program, sponsored by the U.S. Department of Energy Office of Nuclear Energy, is currently investigating alternative waste forms for wastes generated from nuclear fuel processing. One such waste results from an electrochemical separations process, called the “Echem” process. The Echem process utilizes a molten KCl-LiCl salt to dissolve the fuel. This process results in a spent salt containing alkali, alkaline earth, lanthanide halides and small quantities of actinide halides, where the primary halide is chloride with a minor iodide fraction. Pacific Northwest National Laboratory (PNNL) is concurrently investigating two candidate waste forms for the Echem spent-salt: high-halide minerals (i.e., sodalite and cancrinite) and tellurite (TeO2)-based glasses. Both of these candidates showed promise in fiscal year (FY) 2009 and FY2010 with a simplified nonradioactive simulant of the Echem waste. Further testing was performed on these waste forms in FY2011 and FY2012 to assess the possibility of their use in a sustainable fuel cycle. This report summarizes the combined results from FY2011 and FY2012 efforts.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2014

The effect of high-level waste glass composition on spinel liquidus temperature

Spinel crystals precipitate in high-level waste glasses containing Fe, Cr, Ni , Mn, Zn, and Ru. The liquidus temperature (TL) of spinel as the primary crystallization phase is a function of glass composition and the spinel solubility (c0) is a function of both glass composition and temperature (T). Previously reported models of TL as a function of composition are based on TL measured directly, which requires laborious experimental procedures. Viewing the curve of c0 versus T as the liquidus line allows a significant broadening of the composition region for model fitting. This paper estimates TL as a function of composition based on c0 data obtained with the X-ray diffraction technique.

crystal fraction↗