Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Fuel Reprocessing”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Radiation stability test on multiphase glass ceramic and crystalline ceramic waste forms

A radiation stability study was performed on glass ceramic and crystalline ceramic waste forms. These materials are candidate host materials for immobilizing alkali/alkaline earth (Cs/Sr-CS) + lanthanide (LN) + transition metal (TM) fission product waste streams from nuclear fuel reprocessing. In this study, glass ceramics were fabricated using a borosilicate glass as a matrix in which to incorporate CS/LN/TM combined waste streams. The major phases in these multiphase materials are powellite, oxyaptite, pollucite, celsian, and durable residual glass phases. Al2O3 and TiO2 were combined with these waste components to produce multiphase crystalline ceramics containing hollandite-type phases, perovskites, pyrochlores and other minor metal titanate phases. For the radiation stability test, selected glass ceramic and crystalline ceramic samples were exposed to different irradiation environments including low fluxes of high-energy (~1–5 MeV) protons and alpha particles generated by an ion accelerator, high fluxes of low-energy (hundreds of keV) krypton particles generated by an ion implanter, and in-situ electron irradiations in a transmission electron microscope. These irradiation experiments were performed to simulate self-radiation effects in a waste form. Ion irradiation-induced microstructural modifications were examined using X-ray diffraction and transmission electron microscopy. Our preliminary results reveal different radiation tolerance in different crystalline phases under various radiation damage environments. However, their stability may be rate dependent which may limit the waste loading that can be achieved.

Crystalline ceramic↗
DOE OSTI2019

Probing activated radioprotection of simple hydrophilic phosphonic acids in aqueous solution

Prior exploration into the radiation chemistry of the ligand octylphenyl-N,N-diisobutylcarbamoylmethyl phosphine oxide (CMPO) and its analogues demonstrated their ability to undergo activated radioprotection in an organic solvent – a feature most advantageous for spent nuclear fuel reprocessing scenarios. This phenomenon was dependent on these organophosphorus compounds forming a sacrificial complex involving extracted nitric acid and the presence of an adjacent phenylphosphine oxide motif in the molecule. However, the hydrophobic nature of these compounds prevented elucidation of which components were essential for activated radioprotection; for example, does the phenylphosphine oxide motif only require protonation, or simply the presence of complexed nitrate anion(s), or both? To begin to address these questions, we report on the effect of dissolved nitrate on the radiation chemistry of a series of simple hydrophilic phosphonic acids (methyl, ethyl, phenyl, and benzyl) in aqueous solution. An extensive suite of gamma irradiations supported by high performance liquid chromatography and nuclear magnetic resonance techniques was used to demonstrate that all four compounds were unable to undergo activated radioprotection. While some nitrate protection was observed, this was attributed to changes in the available suite of radiolysis products, and not to the formation of nitrate-phosphonic acid sacrificial complexes. The absence of activated radioprotection and evidence for the formation of a [PhPA•NO 3 -] complex further supports the necessity of complex formation to activate the radioprotection mechanism.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2016

Nuclear forensic analysis of a non-traditional actinide sample

Nuclear forensic publications, performance tests, and research and development efforts typically target the bulk global inventory of intentionally safeguarded materials, such as plutonium (Pu) and uranium (U). Other materials, such as neptunium (Np), pose a nuclear security risk as well. Trafficking leading to recovery of an interdicted Np sample is a realistic concern especially for materials originating in countries that reprocesses fuel. Using complementary forensic methods, potential signatures for an unknown Np oxide sample were investigated. Measurement results were assessed against published Np processes to present hypotheses as to the original intended use, method of production, and origin for this Np oxide.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Chalcogenide Aerogels as Sorbents for Radioactive Iodine

Iodine ( 129 I and 131 I) is one of the radionuclides released in nuclear fuel reprocessing and poses a risk to public safety due to its involvement in human metabolic processes. In order to prevent the release of hazardous radioactive iodine into the environment, its effective capture and sequestration is pivotal. In the context of finding a suitable matrix for capturing radioactive iodine, several sulfidic chalcogels were explored as iodine sorbents including NiMoS 4 , CoMoS 4 , Sb 4 Sn 3 S 12 , Zn 2 Sn 2 S 6 , and K 0.16 CoS x (x = 4–5). All of the chalcogels showed high uptake, reaching up to 225 mass % (2.25 g/g) of the final mass owing to strong chemical and physical iodine–sulfide interactions. Analysis of the iodine-loaded specimens revealed that the iodine chemically reacted with Sb 4 Sn 3 S 12 , Zn 2 Sn 2 S 6 , and K 0.16 CoS x to form the metal complexes SbI 3 , SnI 4 , and, KI, respectively. In this study, the NiMoS 4 and CoMoS 4 chalcogels did not appear to undergo a chemical reaction with iodine since iodide complexes were not observed with these samples. Once heated, the iodine-loaded chalcogels released iodine in the temperature range of 75 to 220 °C, depending on the nature of iodine speciation. In the case of Sb 4 Sn 3 S 12 and Zn 2 Sn 2 S 6 , iodine release was observed around 150 °C mainly in the form of SnI 4 and SbI 3 , respectively. The NiMoS 4 , CoMoS 4 , and K 0.16 CoS x released elemental iodine at ~75 °C, which is consistent with physisorption. Preliminary investigations on consolidation of iodine-loaded Zn 2 Sn 2 S 6 chalcogel with Sb 2 S 3 as a glass forming additive produced glassy material whose iodine content was around 25 mass %.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Investigations into Plasma-Mediated Decomposition of Organoiodide Species as a Pretreatment for Mitigation of Radioiodine Emissions

A plasma-mediated pretreatment step is proposed to decompose methyl iodide (CH 3 I) for facilitating the capture of the iodine radioisotopes present in off-gas streams from used nuclear fuel reprocessing operations. Simulated CH 3 I gas streams were exposed to dielectric barrier discharge (DBD) plasma in a quartz glass continuous-flow reactor using copper electrodes. The kinetics of decomposition of CH 3 I in nitrogen was investigated by varying the applied voltage, inlet concentration, and residence time. The rate of decomposition was proportional to CH 3 I concentration and increased as the applied potential was increased. This effect was incorporated in the kinetics through the dependence of the rate constant on the applied electric field. Decomposition of CH 3 I was not affected by moisture, and the DBD pretreatment is likely to be similarly effective in an air environment as well; however, the results were confounded by a plasma-mediated reaction between nitrogen and oxygen.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2015

Isotherms for Water Adsorption on Molecular Sieve 3A: Influence of Cation Composition

This study is part of our continuing efforts to address engineering issues related to the removal of tritiated water from off-gases produced in used nuclear fuel reprocessing facilities. In the current study, adsorption equilibrium of water on molecular sieve 3A beads was investigated. Adsorption isotherms for water on the UOP molecular sieve 3A were measured by a continuous-flow adsorption system at 298, 313, 333, and 353 K. Experimental data collected were analyzed by the Generalized Statistical Thermodynamic Adsorption (GSTA) isotherm model. The K + /Na + molar ratio of this particular type of molecular sieve 3A was ~4:6. Our results showed that the GSTA isotherm model worked very well to describe the equilibrium behavior of water adsorption on molecular sieve 3A. The optimum number of parameters for the current experimental data was determined to be a set of four equilibrium parameters. This result suggests that the adsorbent crystals contain four energetically distinct adsorption sites. In addition, it was found that water adsorption on molecular sieve 3A follows a three-stage adsorption process. This three-stage adsorption process confirmed different water adsorption sites in molecular sieve crystals. In addition, the second adsorption stage is significantly affected by the K + /Na + molar ratio. In this stage, the equilibrium adsorption capacity at a given water vapor pressure increases as the K + /Na + molar ratio increases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Adsorption Equilibrium and Modeling of Water Vapor on Reduced and Unreduced Silver-Exchanged Mordenite

This work is related to the removal of tritiated water and radioactive iodine from off-gases released during spent nuclear fuel reprocessing. Specifically, it is focused on the adsorption equilibrium of water on reduced silver mordenite (Ag 0 Z), which is the state-of-art solid adsorbent for iodine retention in the off-gas treatment. As the off-gases contain different gas species, including iodine and water, Ag 0 Z would take up iodine and water simultaneously during the adsorption process. Therefore, understanding the adsorption of water on Ag 0 Z is important and necessary for studying the performance of Ag 0 Z in off-gas treatment processes. The isotherms of water (nonradioactive water) on Ag 0 Z were obtained at temperatures of 25, 40, 60, 100, 150, and 200 °C with a continuous-flow adsorption system. The data were analyzed using the Heterogeneous Langmuir and generalized statistical thermodynamic adsorption (GSTA) models, and thermodynamic parameters of the isotherms were obtained from both models. Both models were found capable of describing the isotherms. Isotherms of water on the unreduced silver mordenite (AgZ) were also obtained at 25, 40, and 60 °C and parametrized by the GSTA model. Through the comparison of the isotherms of Ag 0 Z and AgZ, it was found that Ag 0 Z had a higher water adsorption capacity than AgZ. The comparison of their thermodynamic parameters suggested that the interaction of water molecules with the H + in Ag 0 Z was stronger than that with the Ag + in AgZ.

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

Organic and Aqueous Redox Speciation of Cu(III) Periodate Oxidized Transuranium Actinides

A hexavalent group actinide separation process could streamline used nuclear fuel recycle and waste management. The limiting factor to such a process compatible with current fuel dissolution practices is obtaining and maintaining hexavalent Am, in molar nitric acid due to the high reduction potential of the Am(VI)/Am(III) couple (1.68 V vs SCE). Two strong oxidants, sodium bismuthate and Cu(III) periodate, have demonstrated quantitative oxidation of Am under molar acid conditions and better than 50% recovery by diamyl amylphosphonate (DAAP) is possible under these same conditions. This work considers the use of Cu(III) periodate to oxidize Np(V) to Np(VI) and Pu(IV) to Pu(VI) and recover these elements by extraction with DAAP. A metal:oxidant ratio of 1:1.2 and 1:3 was necessary to quantitatively oxidize Np(V) and Pu(IV), respectively, to the hexavalent state. Extraction of hexavalent Np, Pu, and Am by 1 M DAAP in n-dodecane was measured using UV-Vis [Pu(VI), Am (VI)] and NIR [Np(VI)]. Distribution values of Am(VI) were found to match previous tracer level studies. The organic phase spectra of Np, Pu, and Am are presented and molar absorptivities are calculated for characteristic peaks. Hexavalent Pu was found to be stable in the organic phase while Np(VI) showed some reduction to Np(V) and Am was present as Am(III), Am(V), and Am(VI) species in aqueous and organic phases during the extraction experiments. These results demonstrate, for the first time, the ability to recover macroscopic amounts of americium that would be present during fuel reprocessing and are the first characterization of Am organic phase oxidation state speciation relevant to a hexavalent group actinide separation process under acidic conditions.

americium↗
DOE OSTI2020

Crystal and Electronic Structures of A 2 NaIO 6 Periodate Double Perovskites (A = Sr, Ca, Ba): Candidate Wasteforms for I-129 Immobilization

The synthesis, structure, and thermal stability of the periodate double perovskites A 2 NaIO 6 (A= Ba, Sr, Ca) were investigated in the context of potential application for the immobilization of radioiodine. A combination of X-ray diffraction and neutron diffraction, Raman spectroscopy, and DFT simulations were applied to determine accurate crystal structures of these compounds and understand their relative stability. The compounds were found to exhibit rock-salt ordering of Na and I on the perovskite B-site; Ba 2 NaIO 6 was found to adopt the Fm- 3 m aristotype structure, whereas Sr 2 NaIO 6 and Ca 2 NaIO 6 adopt the P 2 1 / n hettotype structure, characterized by cooperative octahedral tilting. DFT simulations determined the Fm- 3 m and P 2 1 / n structures of Ba 2 NaIO 6 to be energetically degenerate at room temperature, whereas diffraction and spectroscopy data evidence only the presence of the Fm- 3 m phase at room temperature, which may imply an incipient phase transition for this compound. The periodate double perovskites were found to exhibit remarkable thermal stability, with Ba 2 NaIO 6 only decomposing above 1050 °C in air, which is apparently the highest recorded decomposition temperature so far recorded for any iodine bearing compound. As such, these compounds offer some potential for application in the immobilization of iodine-129, from nuclear fuel reprocessing, with an iodine incorporation rate of 25–40 wt%. The synthesis of these compounds, elaborated here, is also compatible with both current conventional and future advanced processes for iodine recovery from the dissolver off-gas.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Elucidating Actinide–Pertechnetate and Actinide–Perrhenate Bonding via a Family of Th–TcO 4 and Th–ReO 4 Frameworks and Solutions

Technetium-99, a β-emitter produced from 235 U fission, poses a challenge for the nuclear industry due to co-extraction of pertechnetate (TcO 4 – ) with the actinides (An) during nuclear fuel reprocessing. Previous studies suggested that direct coordination of pertechnetate with An plays an important role in the coextraction process. However, few studies have provided direct evidence for An–TcO 4 – bonding in the solid state, and even fewer in solution. The present study describes synthesis and structural elucidation of a family of thorium(IV)-pertechnetate/perrhenate (ReO 4 – , nonradioactive surrogate) compounds, which is obtained by dissolution of thorium oxyhydroxide in perrhenic/pertechnic acid followed by crystallization, with or without heating. For reaction ratios of 3:1, 4:1, and 6:1 MO 4 – /Th(IV) (M = Tc, Re), the crystallized compounds reflect the same ratio, suggesting facile and flexible coordination. Furthermore, nine structures reveal 1-dimensional and 2-dimensional frameworks with varying topologies. While a multitude of compounds isolated from 4:1 (and 6:1) reaction solutions feature Th monomers linked by MO 4 – , the 3:1 reaction solution yielded the well-known dihydroxide-bridged thorium dimer, linked, and capped by MO 4 – . Density functional theory calculations on ReO 4 – /TcO 4 – isomorphs suggest similar bonding characteristics in the solid state, but experimental solution characterization noted differences. Specifically, small-angle X-ray scattering studies suggest the bonding of Th–TcO 4 – persists in solution, while Th–ReO 4 – bonding is less apparent.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Actinide Separation Inspired by Self-Assembled Metal–Polyphenolic Nanocages

The separation of actinides has a vital place in nuclear fuel reprocessing, recovery of radionuclides, and remediation of environmental contamination. Here we propose a new paradigm of nanocluster-based actinide separation, namely, nanoextraction, that can achieve efficient sequestration of uranium in an unprecedented form of giant coordination nanocages using a cone-shaped macrocyclic pyrogallol[4]arene as the extractant. The U 24 -based hexameric pyrogallol[4]arene nanocages with distinctive [U 2 (PG) 2 ] binuclear units (PG = pyrogallol) that rapidly assembled in situ in monophasic solvent were identified by single-crystal X-ray diffraction, MALDI-TOF mass spectrometry, NMR spectroscopy, and small-angle X-ray and neutron scattering. Furthermore, comprehensive biphasic extraction studies showed that this novel separation strategy has enticing advantages such as fast kinetics, high efficiency, and good selectivity over lanthanides, thereby demonstrating its potential for efficient separation of actinide ions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Functionalized metal organic frameworks for effective capture of radioactive organic iodides

Highly efficient capture of radioactive organic iodides (ROIs) from off-gas mixtures remains a substantial challenge for nuclear waste treatment. Current materials utilized for ROI sequestration suffer from low capacity, high cost ( e.g. use of noble metals), and poor recyclability. Recently, we have developed a new strategy to tackle this challenge by functionalizing MOF materials with tertiary amines to create molecular traps for the effective capture and removal of ROIs ( e.g. radioactive methyl iodide) from nuclear wastes. To further enhance the uptake capacity and performance of CH 3 I capture by ROI molecular traps, herein, we carry out a systematic study to investigate the effect of different amine molecules on ROI capture. The results demonstrate a record-high CH 3 I saturation uptake capacity of 80% for MIL-101–Cr–DMEDA at 150 °C, which is 5.3 times that of Ag 0 @MOR (15 wt%), a leading adsorbent material for capturing ROIs during nuclear fuel reprocessing. Furthermore, the CH 3 I decontamination factors (DFs) for MIL-101–Cr–DMEDA are as high as 5000 under simulated reprocessing conditions, largely exceeding that of facility regulatory requirements (DF = 3000). In addition, MIL-101–Cr–DMEDA can be recycled without loss of capacity, illustrating yet another advantage compared to known industrial adsorbents, which are typically of a “single-use” nature. Our analysis also shows that both physisorption and chemisorption of CH 3 I occur at the three amine-grafted MOFs. While chemisorption takes place at the amine functionalized sites, the amount of physisorption correlates with the MOF porosity. A possible binding site of amine–CH 3 I interaction has been identified via an in situ IR spectroscopic study. The results suggest that CH 3 I interacts strongly and directly with the tertiary nitrogen of the amine molecules. The CH 3 I uptake amount decreases as the amine chain length increases, in trend with the decreasing pore space of the corresponding framework. The strategy to build MOF-based molecular traps developed in this work not only leads to a new record-high performance for ROI capture, but also offers an effective way of systematically tuning the porosity by varying the length of functionalized amine molecules. This study also demonstrates that MOFs represent a promising new platform for selective capture and removal of radioactive nuclear waste.

Chemistry↗
DOE OSTI2021

Curium(iii) radiation-induced reaction kinetics in aqueous media

Insight into the effects of radiolytic processes on the actinides is critical for advancing our understanding of their solution chemistry because the behaviour of these elements cannot be easily separated from the influence of their inherent radiation field. However, minimal information exists on the radiation-induced redox behaviour of curium (Cm), a key trivalent transuranic element present in used nuclear fuel and frequently used as an alpha radiation source. Here we present a kinetic study on the aqueous redox reactions of Cm(III) with radicals generated through the radiolysis of aqueous media. In particular, we probe reaction kinetics in nitric acid solutions that are used as the aqueous phase component of used nuclear fuel reprocessing solvent systems. Second-order rate coefficients (k) were measured for the reaction of Cm(III) with the hydrated electron (e aq - , k = (1.25 ± 0.03) × 10 10 M -1 s -1 ), hydrogen atom (H˙, k = (5.16 ± 0.37) × 10 8 M -1 s -1 ), hydroxyl radical (˙OH, k = (1.69 ± 0.24) × 10 9 M -1 s -1 ), and nitrate radical (NO 3 ˙, k = (4.83 ± 0.09) × 10 7 M -1 s -1 ). Furthermore, the first-ever Cm(II) absorption spectrum (300–700 nm) is also reported. These kinetic data dispel the status quo notion of Cm(III) possessing little to no redox chemistry in aqueous solution, and suggest that the resulting Cm(II) and Cm(IV) transients could exist in irradiated aqueous solutions and be available to undergo subsequent redox chemistry with other solutes.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2026

Elemental analysis of air-sensitive frozen molten salt samples using an inert transfer chamber for LIBS/LA-ICP-TOF-MS analysis

A novel inert sample transfer system was developed and employed to enable, for the first time, the analysis of air-sensitive salt samples in a two-volume ablation cell using simultaneous laser-induced breakdown spectroscopy (LIBS) and laser ablation (LA)-inductively coupled plasma (ICP)-time-of-flight (TOF)-mass spectrometry (MS) analysis. Molten salts are of growing interest as a medium for advanced nuclear reactors and nuclear fuel reprocessing technologies continue to be developed around their use. However, compositional analysis of molten salt samples can be challenging because of their air-sensitive nature and varying solubilities leading to inaccurate measurements when digested. LA-based analysis provides an alternate method to digestion and can provide rapid elemental information with little sample preparation. In this study, LIBS and LA-ICP-TOF-MS were used to analyze the Ce content in frozen salt samples taken from a series of electrochemical experiments. Calibrations were built for each technique, and the resulting limits of detection for Ce were estimated to be 107 and 58 µg g −1 for LIBS and LA-ICP-TOF-MS, respectively. Test samples from the electrochemical experiments were analyzed using these calibrations. The results matched bulk digestion-based ICP-optical emission spectroscopy values, and daily trends in Ce concentration changes were identified. Additionally, the LIBS and LA-ICP-TOF-MS analysis was demonstrated for identifying microgram per gram levels of components and detecting trace contaminants. The impurities detected by LIBS included Al, Mg, Ca, and Na. The impurities detected by LA-ICP-TOF-MS included W, Ag, Al, Fe, Ni, Mo, Nd, Sm, Th, and U.

Andrews, Hunter B. [Oak Ridge National Laboratory ↗
DOE OSTI2019

Dissolution of used nuclear fuel using a tributyl phosphate/n-paraffin solvent

The complete recycle of used nuclear fuel (UNF) is necessary to recover the energy value from the remaining U and higher actinides; yet, construction of a large-scale facility is extremely expensive. To address this issue, a hybrid process was evaluated in which UNF pretreated for tritium removal is dissolved in a tributyl phosphate (TBP) solvent. The distribution of the actinides and selected fission products was measured between the solvent and residual solids. Dissolution of these elements in the surrogate fuels was very effective. Most fission products from fuel irradiation except for the lanthanide elements would remain in the undissolved solids.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2019

In Situ Monitoring and Kinetic Analysis of the Extraction of Nitric Acid by Tributyl Phosphate in n-Dodecane using Raman Spectroscopy

Understanding the fundamental rates of transfer and complex formation is crucial in maintaining optimal efficiency and effectivity in solvent extraction. Methodologies to effectively analyze solvent extraction systems are lacking in that they are commonly off-line. Thus, a method to effectively investigate solvent extraction systems in a Lewis cell using in situ Raman spectroscopy paired with chemometric modelling has been developed to allow for on-line analysis and monitoring. Kinetic parameters of interfacial mass transfer for the extraction of nitric acid by tributyl phosphate, a process crucial to used nuclear fuel reprocessing, were measured in by spectroscopic monitoring of both phases simultaneously in a two-phase solvent extraction system. Resulting concentration data, derived from a chemometric model using Raman spectra as the base set, allowed for the calculation of kinetic parameters in the system when paired with extraction time. The forward and reverse interfacial mass transfer coefficients, kf and kr, were determined for solutions that were process relevant and of pro-cess interest, where kf was calculated as 5.3 (± 0.3) × 10-3 cm min 1 and kr was calculated as 2.9 (± 0.2) × 10-2 cm min-1. The information obtained regarding solvent extraction parameters and transfer can be applied in the further study of systems of higher complexity involving complex formation and their transfer across a liquid:liquid interface.

extraction, interfacial transport, Lewis Cell, Liq↗
DOE OSTI2022

Radiation effects on the structure and alteration behavior of an SiO 2 –Al 2 O 3 –B 2 O 3 –Na 2 O glass

As borosilicate glasses are used in many countries to immobilize fission products and minor actinides after spent fuel reprocessing before storage in a deep geological repository, assessing that their chemical durability is of paramount importance. Here, pristine and preirradiated (952 MeV, 136Xe) SiO 2 –B2O 3 –Al2O 3 –Na 2 O glasses with the same molar ratios as in the French SON68 and ISG glasses have been subjected to aqueous corrosion in deionized water and in silica-saturated solution to measure the initial and longer term alteration rates. Pristine and preirradiated glasses corrode following the same mechanisms, but the preirradiation has a strong impact on the initial dissolution rate (increase by a factor of 5.6), and on the alteration layer depth in silica-saturated conditions (by two- to threefolds). The later result is related to the formation of a more porous, less passivating gel on the preirradiated glass specimen. Using both experimental spectroscopies (NMR, IR, and SFG) and classical molecular dynamics, the radiation effects on the glass structure and water diffusion have been assessed. After preirradiation, the density and the polymerization degree of the glass decrease, whereas the topological disorder increases. In consequence, water diffusion accelerates. These observations allow to correlate the radiation impact on the alteration behavior to the structural changes.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Development and Durability Testing of a Low‐Temperature Sintering Bi–Si–Zn Oxide Glass Composite Material (GCM) 129 I Waste Form

The capture and safe storage of radiological iodine ( 129 I) from nuclear fuel reprocessing is of concern due to its long half‐life and potential mobility in the environment. The development of durable waste forms in which to store captured iodine requires materials that are both compatible with the iodine capture phases and durable to repository environments. To that end, Sandia is developing a low‐temperature sintering Bi–Si–Zn oxide glass composite material (GCM) waste form and herein presents results of durability testing. Furthermore, durability studies were extended to both the occluded iodine capture material Ag‐Zeolite (Mordenite, MOR) as well as the GCM, synthesized with compositional variations including: amount of Ag flake added, AgI‐MOR particle size in the GCM, and mass loading of I within the AgI‐MOR. Product consistency test (PCT‐B), chemical durability (MCC‐1) tests, and single‐pass flow‐through (SPFT) tests, were performed on both the individual components of the GCM and the completed GCMs. Durability tests indicate low GCM dissolution rates (<10 −3 g/m 2 ·d) across wide variable ranges including: pH, AgI‐MOR loading, I loading, and AgI‐MOR particle size. Results indicate that the Bi–Si–Zn oxide glass matrix sharply limits the release of iodine from the otherwise relatively fast degrading AgI‐MOR getter material. Furthermore, the formation of an amorphous AgI phase during sintering of the GCM results in the limitation of iodine release during waste form degradation. Durability of GCM and release rates approximate those of established nuclear waste glasses, or analogues such as basaltic glass. This suggests that the Bi–Si–Zn GCM is a viable candidate as a repository iodine waste form.

Mowry, Curtis D.↗