Effects of iron oxalate on rhenium incorporation into low-activity waste glass
Not Available
George, Jaime L. (ORCID:0000000218716491)↗
SEARCH · Engineering Papers
Results for “BOROSILICATE GLASS”
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.
Formulation of high-Al2O3 waste glasses from projected Hanford waste compositions
Not Available
Kroll, Jared O.↗
Effects of Sulfate on Rhenium Incorporation into Low-Activity Waste Glass
Technetium-99 (99Tc) is a major radionuclide of concern in the Hanford low-activity waste (LAW), which will be vitrified into borosilicate glass at the Waste Treatment and Immobilization Plant (WTP). Sulfate content in LAW has been known to be a critical factor affecting the volatile loss of 99Tc during melting of the LAW glass feed (a mix of liquid LAW and mineral/chemical additives). We investigated rhenium (a nonradioactive surrogate for 99Tc) incorporation into glass by performing crucible melting tests of two representative simulated LAW glass feeds, each prepared with varied sulfur levels. The sulfate content varied from the original content to half of the original (½S) and to zero (0S), in the range of 0 to 0.8 mass % SO3 in glass if 100% retained. The slurry feeds were dried at 105°C and heated to 400–1100°C. Deionized water leach at room temperature and at 80°C was conducted on the dried feed and heat-treated samples to analyze the chemical compositions of soluble and insoluble phases separately and to profile the partitioning of various components into different phases during the melting process. Different partitioning behavior of rhenium, sulfate, and chlorine is discussed in connection with major feed-to-glass conversion reactions. The mechanism on how sulfate affects rhenium incorporation during feed-to-glass conversion reactions, and so final retention of rhenium in glass, is proposed based on the two hypotheses that segregated sulfate-rich phase forms during feed conversion reactions and Re preferentially partitions to this sulfate-rich phase.
Jin, Tongan↗
Effects of Composition and Oxidation States on the Structures of Chromium-Containing Sodium Silicate Glasses: Molecular Dynamics Simulations using Machine Learning Interatomic Potentials
Chromium represents a significant challenge for the vitrification of high-level nuclear waste into silicate and borosilicate glasses due to its low solubility and variable oxidation states, which can limit the waste loading due to promotion of crystallization or phase separation during processing. In this study, we modeled chromium containing silicate glasses using molecular dynamics simulations with three machine learning interatomic potentials (MLIPs), MACE, CHGNet, and PFP were employed, to gain insights on glass composition and oxidation states on the structures of these glasses. One of the goals is to evaluate their ability of these MLIPs to accurately represent the general structure of silicate glasses and chromium local environments as a function of chromium oxidation states. Density Functional Theory (DFT) based calculations and experimental data such as neutron structure factors were used to validate the structural models. It was found that the foundation models of all three MLIPs are able to reproduce general structural features of the sodium silicate glass structure consistent with experimental and DFT data, but only CHGNet and PFP can accurately capture the oxidation states and local environment of chromium: tetrahedral for Cr6+ and octahedral for Cr3+. Furthermore, we studied the effect of varying Cr3+/ Cr6+ (Cr3+/Crtotal) ratio and total chromium content using PFP. Our results show that Cr6+ enhances network polymerization by reducing non-bridging oxygens through Na? charge compensation required due to the formation of chromate (CrO42-) species, while Cr³? acts as a network modifier that disrupts connectivity. System size effects on the structural characteristics and chromium environments were also tested using the PFP potential. This work highlights the importance of careful validation on the precision, transferability, and potential of MLIPs for modeling glasses containing transition metal elements that can exist in multiple oxidation states. It is also encouraging to see the foundational models are all three MLFFs are able to reproduce the basic sodium silicate glass structures, while suggesting additional training or refining is needed to improve the description of more complex systems containing transition metals.
Puga, Christina L.↗
Impact of non‐framework cation mixing on the structure and crystallization behavior of model high‐level waste glasses
Abstract Spinel crystallization is known to be detrimental to the operation of Joule heated ceramic melters during the vitrification of iron‐rich high‐level nuclear wastes (HLW) into borosilicate glasses. The literature on this subject focuses on tackling the problem by developing empirical constraints to design compositions, which limit the fraction of spinels formed in the melter or by developing empirical models to predict the settling behavior of spinels in the melter as a function of the glass composition. While these empirical models can predict the behavior of most of the compositions, they are not failsafe as there are always some compositions, whose behavior is beyond the predictive ability of these models. This can lead to undesirable situations during the vitrification of the nuclear waste, and therefore an in‐depth investigation of the chemo‐structural descriptors controlling the crystallization behavior in these glasses is warranted. Accordingly, the present study aims to understand the impact of non‐framework cation mixing (i.e., Li + /Na + and Ca 2+ /Na + ) on the structure (through Raman spectroscopy and Mössbauer spectroscopy) and crystallization behavior (through XRD, SEM‐EDS, and vibrating sample magnetometry) of iron‐rich model HLW glasses in the system: (mol.%) x M y O–(25− x ) Na 2 O–9.12 B 2 O 3 –6.4 Al 2 O 3 –51.25 SiO 2 –7.22 Fe 2 O 3 –0.38 MnO–0.08 Cr 2 O 3 –0.55NiO (M y O = Li 2 O or CaO).
Balasubramanya, Nikhila↗
Contribution of atom-probe tomography to a better understanding of glass alteration mechanisms: Application to a nuclear glass specimen altered 25 years in a granitic environment
Here, we report and discuss results of atom probe tomography (APT) and energy-filtered transmission electron microscopy (EFTEM) applied to a borosilicate glass sample of nuclear interest altered for nearly 26 years at 90°C in a confined granitic medium in order to better understand the rate-limiting mechanisms under conditions representative of a deep geological repository for vitrified radioactive waste. The APT technique allows the 3D reconstruction of the elemental distribution at the reactive interphase with sub-nanometer precision. Profiles of the B distribution at pristine glass/hydrated glass interface obtained by different techniques are compared to show the challenge of accurate measurements of diffusion profiles at this buried interface on the nanometer length scale. Our results show that 1) Alkali from the glass and hydrogen from the solution exhibit anti-correlated 15 ± 3 nm wide gradients located between the pristine glass and the hydrated glass layer, 2) boron exhibits an unexpectedly sharp profile located just at the outside of the alkali/H interdiffusion layer; this sharp profile is more consistent with a dissolution front than a diffusion-controlled release of boron. The resulting apparent diffusion coefficients derived from the Li and H profiles are D Li = 1.5 × 10 -22 m 2 .s -1 and D H = 6.8 × 10 -23 m 2 .s -1 . These values are around two orders of magnitude lower than those observed at the very beginning of the alteration process, which suggests that interdiffusion is slowed at high reaction progress by local conditions that could be related to the porous structure of the interphase. As a result, the accessibility of water to the pristine glass could be the rate-limiting step in these conditions. More generally, these findings strongly support the importance of interdiffusion coupled with hydrolysis reactions of the silicate network on the long-term dissolution rate, contrary to what has been suggested by recent interfacial dissolution-precipitation models for silicate minerals.
36 MATERIALS SCIENCE↗
Modelling the local atomic structure of molybdenum in nuclear waste glasses with ab initio molecular dynamics simulations
The nature of chemical bonding of molybdenum in high level nuclear waste glasses has been elucidated by ab initio molecular dynamics simulations. Two compositions, (SiO2)57.5 – (B2O3)10 – (Na2O)15 – (CaO)15 – (MoO3)2.5 and (SiO2)57.3 – (B2O3)20 – (Na2O)6.8 – (Li2O)13.4 – (MoO3)2.5 , were considered in order to investigate the effect of ionic and covalent components on the glass structure and the formation of the crystallisation precursors (Na2MoO4 and CaMoO4). The coordination environments of Mo cations and the corresponding bond lengths calculated from our model are in excellent agreement with experimental observations. The analysis of the first coordination shell reveals two different types of molybdenum host matrix bonds in the lithium sodium borosilicate glass. Based on the structural data and the bond valence model, we demonstrate that the Mo cation can be found in a redox state and the molybdate tetrahedron can be connected with the borosilicate network in a way that inhibits the formation of crystalline molybdates. These results significantly extend our understanding of bonding in Mo-containing nuclear waste glasses and demonstrate that tailoring the glass composition to specific heavy metal constituents can facilitate incorporation of heavy metals at high concentrations. K.K. was supported through the Impact Studentship scheme at UCL co-funded by the IHI Corporation and UCL. P.V.S. thanks the Royal Society, which supported preliminary work on this project, and the Laboratory Directed Research and Development program at PNNL, a multiprogram national laboratory operated by Battelle for the U.S. Department of Energy. Via our membership of the UK's HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202), this work used the ARCHER UK National Supercomputing Service (http://www.archer.ac.uk).
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Manufacturing and Reliability Science for CIGS Photovoltaics
The purpose of this program was to overcome the largest challenges to investor confidence and long product lifetime in CuIn x Ga 1-x Se 2 (CIGS)-based photovoltaic products: metastability, shading-induced hot spots, and potential-induced degradation. Key findings were made in each of these areas by studying CIGS reliability at the cell level, which very few groups are currently doing. Metastability was thought to be a function of the CIGS absorber. We have challenged the state-of-the-art by showing that the metastability seen in commercial products is likely to be caused by the buffer layer. SCAPS device modeling confirmed that the buffer layer has a significant influence on metastability in CIGS devices, and also led to a processing change - the introduction of CdS islands to Zn(O,S) buffer layers - that dramatically reduced metastability in CIGS solar cells. In the reverse-bias shading task, modeling showed us that 19% solar cells are possible with thin CIGS layers of 0.5 µm. We were able to fabricate 15.2% solar cells in this project, which is the highest reported efficiency of devices in the ultra-thin class. We also discovered that the best way to dissipate less power in reverse bias was to eliminate the intrinsic ZnO layer that is often used in CIGS devices. Lower power dissipation led to devices that allowed two times the maximum power point current density in reverse without damage. Potential-induced degradation (PID) is caused by the drift of Na+ ions from the back glass to the CIGS/Mo interface, followed by diffusion into the solar cells and to the CdS region. We found that PID can be slowed by using low-conductivity borosilicate glass that contains higher K and lower Na than soda-lime glass. Based on significant progress in each of the three reliability challenges, the CIGS cell-level reliability project was very successful. We have also proved that module-level degradation mechanisms can be tested and solved at the cell level.
14 SOLAR ENERGY↗
A Predictive Model for Offgas Composition in Waste Glass Melters - Spring 2021 SULI General Audience Abstract
Approximately 56 million gallons of nuclear waste are currently stored in 177 underground storage tanks at the Hanford site in Washington state. A portion of the tank waste is targeted for immobilization by converting the nuclear waste to borosilicate glass through a process called vitrification. During vitrification, emissions are produced in addition to the intended glass product. These emissions, contained in a volume above the molten glass called the plenum, are composed of water vapor, air components, aerosols, particulates, and other gaseous species that result from evaporation, reactions, and air influx. The formation of these gasses causes the surface of the glass to foam. To reduce foaming, sucrose is added to the waste stream before the conversion to glass. Sucrose also reduces the formation of hazardous gasses in the plenum including nitrous oxides, NOx, and carboxides, COx. However, if excess sucrose is present, the reactions that produce the gasses in the plenum will be incomplete, and increased levels of NOx and COx can be observed. The Waste Treatment and Immobilization Plant at the Hanford site is equipped with the technology to treat the plenum emissions. Though many tests have been run to determine the presence of particulates in the plenum emissions, there is does not exist an established method to confidently predict the composition of the gaseous species in the plenum prior to treatment without physical testing. A model was created in the process modeling software Aspen Plus to predict the composition of NOx and COx in the plenum. The model employs a constant stirred tank reactor and user-defined reaction chemistry to determine the plenum composition. To verify the model, the offgas predicted by the model were compared to available offgas data for ten different feed compositions. It is demonstrated that the developed Aspen Plus model is capable of predicting the composition of NOx and COx in the plenum.
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
CHEMICAL ANALYSIS OF SIMULATED HIGH LEVEL WASTE GLASSES TO SUPPORT SULFATE SOLUBILITY MODELING
The U.S. Department of Energy (DOE), Office of Environmental Management (EM) is sponsoring an international, collaborative project to develop a fundamental model for sulfate solubility in nuclear waste glass. The solubility of sulfate has a significant impact on the achievable waste loading for nuclear waste forms both within the DOE complex and to some extent at U.K. sites. The development of enhanced borosilicate glass compositions with improved sulfate solubility will allow for higher waste loadings and accelerated cleanup missions. Much of the previous work on improving sulfate retention in waste glasses has been done on an empirical basis, making it difficult to apply the findings to future waste compositions despite the large number of glass systems studied. A more fundamental, rather than empirical, model of sulfate solubility in glass, under development at Sheffield Hallam University (SHU), could provide a solution to the issues of sulfate solubility. The model uses the normalized cation field strength index as a function of glass composition to predict sulfate capacity, and has shown early success for some glass systems. The objective of the current scope is to mature the sulfate solubility model to the point where it can be used to guide glass composition development for DOE waste vitrification efforts, allowing for enhanced waste loadings and waste throughput. A series of targeted glass compositions was selected to resolve data gaps in the current model. SHU fabricated these glasses and sent samples to the Savannah River National Laboratory (SRNL) for chemical composition analysis. SHU will use the resulting data to enhance the sulfate solubility model and resolve any deficiencies. In this report, SRNL provides chemical analyses for simulated waste glasses fabricated SHU in support of sulfate solubility model development. A review of the measured compositions revealed that there are issues with the B{sub 2}O{sub 3} and Fe{sub 2}O{sub 3} concentrations missing their targeted values by a significant amount for several of the study glasses. SHU is reviewing the fabrication of these glasses and the chemicals used in batching them to identify the source of these issues. The measured sulfate concentrations were all below their targeted values. This is expected, as the targeted concentrations likely exceeded the solubility limit for sulfate in these glass compositions. Some volatilization of sulfate may also have occurred during fabrication of the glasses. Measurements of the other oxides in the study glasses were reasonably close to their targeted values
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Graphite fiber reinforced glass matrix composites for aerospace applications
The graphite fiber reinforced glass matrix composite system is described. Although this composite is not yet a mature material, it possesses low density, attractive mechanical properties at elevated temperatures, and good environmental stability. Properties are reported for a borosilicate glass matrix unidirectionally reinforced with 60 volume percent HMS graphite fiber. The flexural strength and fatigue characteristics at room and elevated temperature, resistance to thermal cycling and continuous high temperature oxidation, and thermal expansion characteristics of the composite are reported. The properties of this new composite are compared to those of advanced resin and metal matrix composites showing that graphite fiber reinforced glass matrix composites are attractive for aerospace applications.
Prewo, K. M.↗
Application of atomic layer deposited microchannel plates to imaging photodetectors with high time resolution
Novel microchannel plates have been constructed using borosilicate glass micro-capillary array substrates with 20 mu m and 10 mu m pores and coated with resistive, and secondary electron emissive, layers by atomic layer deposition. Microchannel plates in 33 mm, 50 mm and 20 cm square formats have been made and tested. Although their amplification, imaging, and timing properties are comparable to standard glass microchannel plates, the background rates and lifetime characteristics are considerably improved. Sealed tube detectors based on the Planacon tube, and a 25 mm cross delay line readout tube with a GaN(Mg) opaque photocathode deposited on borosilicate microchannel plates have been fabricated. Considerable progress has also been made with 20 cm microchannel plates for a 20 cm format sealed tube sensor with strip-line readout that is being developed for Cherenkov light detection.
Siegmund, O. H. W.↗
Corrosion Behavior and Microstructure Influence of Glass-Ceramic Nuclear Waste Forms
Glass ceramic waste forms present a potentially viable technology for the long term immobilization and disposal of liquid nuclear wastes. Through control of chemistry during fabrication, such waste forms can have designed secondary crystalline phases within a borosilicate glass matrix. In this work, a glass ceramic containing powellite and oxyapatite secondary phases was tested for its corrosion properties in dilute conditions using single pass flow through testing (SPFT). Three glass ceramic samples were prepared using different cooling rates to produce samples with varying microstructure sizes. In testing at 90 °C in buffered pH 7 and pH 9 solutions, it was found that increasing pH and decreasing microstructure size (resulting from rapid cooling during fabrication) both led to a reduction in overall corrosion rate. The phases of the glass ceramic were found, using a combination of solutions analysis, SEM and AFM, to corrode preferably in the order of powellite > bulk glass matrix > oxyapatite.
Environmental Molecular Sciences Laboratory↗
Effect of decades of corrosion on the microstructure of altered glasses and their radiation stability
Understanding the microstructural evolution of glasses during their interaction with water and radiation is of fundamental importance in addressing the corrosion of nuclear waste forms under geological disposal conditions. Here we report the results of more than 21 years of corrosion of two borosilicate glasses showing the formation of mesoporous C–S–H gels in Ca-bearing glasses and a mainly microporous microstructure in Al-bearing glasses. These porous corroded glasses were then irradiated with heavy ions to simulate the effects of recoil nucleus damage and monitored in real time using transmission electron microscopy with in situ ion irradiation. The ballistic collisions remarkably healed the porous corroded glasses to a pore-free homogeneous microstructure. Besides providing new insights and predictions about how doped glasses and actual waste forms may evolve under corrosion and irradiation, the results highlight the non-universal nature of the existing corrosion models and the important role that the glass composition and radiation damage play in the evolution of the microstructure during corrosion.
36 MATERIALS SCIENCE↗
Silicon-on-glass pore network micromodels with oxygen-sensing fluorophore films for chemical imaging and defined spatial structure
Pore network microfluidic models were fabricated by a silicon-on-glass technique that provides the precision advantage of dry etched silicon while creating a structure that is transparent across all microfluidic channels and pores, and can be imaged from either side. A silicon layer is bonded to an underlying borosilicate glass substrate and thinned to the desired height of the microfluidic channels and pores. The silicon is then patterned and through-etched by deep reactive ion etching (DRIE), with the underlying glass serving as an etch stop. After bonding on a transparent glass cover plate, one obtains a micromodel in oxygen impermeable materials with water wet surfaces where the microfluidic channels are transparent and structural elements such as the pillars creating the pore network are opaque. The micromodel can be imaged from either side. The advantageous features of this approach in a chemical imaging application are demonstrated by incorporating a Pt porphyrin fluorophore in a PDMS film serving as the oxygen sensing layer and a bonding surface, or in a polystyrene film coated with a PDMS layer for bonding. The sensing of a dissolved oxygen gradient was demonstrated using fluorescence lifetime imaging, and it is shown that different matrix polymers lead to optimal use in different ranges dissolved oxygen concentration. Imaging with the opaque pillars in between the observation direction and the continuous fluorophore film yields images that retain spatial information in the sensor image.
chemical imaging↗
Iron phosphate glass for immobilization of 99Tc
Technetium-99 (99Tc) can bring serious environmental threats because of its long half-life (t1/2 = ~2.1 x 105 years), high fission yield (~6%), and high solubility and mobility in the ground water. The high volatility makes it difficult to immobilize 99Tc in continuous melters vitrifying 99Tc-containing nuclear wastes in borosilicate glasses. This work explores a possibility of incorporating a high concentration of 99Tc, surrogated by the non-radioactive Re, in an iron phosphate glass by melting mixtures of iron phosphate glass frits with 1.5-6 mass% KReO4 at ~1000 C. The retention of Re achieved was ~1.1 mass%. The normalized Re release by the 7-day Product Consistency Test was <10*2 g/m2. Surprisingly, the Re escaped from the melt within a short time of heating, especially when the temperature was increased. Therefore, 99Tc volatilization would still be a challenging task for its immobilization in iron phosphate glasses.
Xu, Kai↗
Development of Tc(IV)-Incorporated Fe Minerals to Enhance 99Tc Retention in Glass Waste Form
Iron minerals have been considered to be good hosts for Tc immobilization because the Tc(IV) ion substitutes for Fe(III) in the crystal structure of the Fe oxide due to similarities in (1) cation size [Tc(IV) = 78.5 pm ; Fe(III) = 69 or 78.5 pm], (2) metal-oxygen interatomic distance (Tc—O = 0.199 nm, Fe—O = 0.203 nm), (3) number of coordinating oxygen atoms (both 6-fold coordinated), and (4) the redox potential (Eh=ca. +20 mV at pH = 7) for a redox couple between Tc(VII)/Tc(IV) and Fe(III)/Fe(II). Magnetite, maghemite, and trevorite are iron oxide minerals and all belong to spinel mineral group. Laboratory testing shows that Tc can be removed from aqueous waste solutions by a process of Tc reduction from Tc(VII) to Tc(IV) followed by co-precipitation with iron oxide minerals during recrystallization of Fe(OH)2(s) used as an initial solid precursor. X-ray absorption near edge structure (XANES) spectroscopy confirmed that Tc was in the +4 oxidation state in final Tc-Fe minerals. The Tc-incorporated Fe minerals were also tested for Tc retention in glass melts at different temperatures between 600 – 1,000 oC in a furnace. After being cooled in air, the solid glass specimens collected at different temperatures were analyzed for Tc oxidation state using XANES and Tc retention using liquid scintillation counting (LSC). Even though Tc(IV) started to reoxidize at 600 oC, Tc retention in the final glass specimen prepared with Tc-incorporated Fe mineral even at high temperatures was at least two times higher than glass prepared with KTcO4 salt. Higher Tc retention in glass is considered to result from limited and delayed Tc volatilization process due to Fe mineral encapsulation for Tc. Therefore, the results showing the presence of Tc(IV) in the Fe mineral structure indicate strong possibility to enhance Tc retention in borosilicate glass as well as to reduce the remediation costs at the Hanford Site.
Environmental Molecular Sciences Laboratory↗
Glass–water interaction: Effect of high-valence cations on glass structure and chemical durability
Borosilicate glass is a durable solid, but it dissolves when in contact with aqueous fluids. The dissolution mechanism, which involves a variety of sequential reactions that occur at the solid-fluid interface, has important implications for the corrosion resistance of industrial and nuclear waste glasses. In this study, spectroscopic measurements, dissolution experiments, and Monte Carlo simulations were performed to investigate the effect of high–valence cations (HVC) on the mechanisms of glass dissolution under dilute and near-saturated conditions. Raman and NMR spectroscopy were used to determine the structural changes that occur in glass, specifically network formers (e.g., Al, Si, and B), with the addition of the HVC element hafnium in the Na2O–Al2O3–B2O3–HfO2–SiO2 system (e.g., Na/[Al+B] = 1.0 and HfO2/SiO2 from 0.0 to 0.42). Spectroscopic measurements revealed that increasing hafnium content decreases N4 (tetrahedral boron/total boron) and increases the amount of Si—O—Hf moieties in the glass. Results from flow–through experiments conducted under dilute and near–saturated conditions show a decrease of approximately 100× or more in the dissolution rate over the series from 0 to 20 mol% HfO2. Comparing the average steady-state rates obtained under dilute conditions to the rates obtained for near-saturated conditions reveals a divergence in the magnitude between the average steady state rates measured in these different conditions. The reason for this divergence was investigated more thoroughly using Monte Carlo simulations. Simulations indicate that the divergence in glass dissolution behavior under dilute and near-saturated conditions result from the stronger binding of Si sites that deposit on the surface from the influent when Hf is present in the glass. As a result, the residence time at the glass surface of these newly-formed Si sites is longer in the presence of Hf, which increases the density of anchor sites from which altered layers with higher Si densities can form. These results illustrate the importance of understanding solid–water/solid-fluid interactions by linking macroscopic reaction kinetics to nanometer scale interfacial processes.
Environmental Molecular Sciences Laboratory↗