Simulated Nuclear Waste Glass Research Articles

Laboratory-based correlated X-ray imaging and scattering of inhomogeneous glass-ceramics

Nuclear waste glasses often contain complex microstructures, and understanding these are key to predicting and engineering glass durability, since heterogeneity may exist over multiple length scales. Here we use laboratory-based, spatially-resolved X-ray characterization methods that span length scales (10-10-10-2 m): Wide angle X-ray Scattering (WAXS) provides atomic-scale crystallography; Small Angle X-ray Scattering (SAXS) provides nanoscale phase data; X-ray Computed Tomography and projection X-ray radiography map the materials structure over the micrometer and millimeter scales. The pairing of X-ray radiography with SAXS/WAXS in the same instrument enables specific regions on the sample to be characterized with precise spatial resolution. Two molybdenum- and lanthanum-containing simulated nuclear waste glasses were examined, enabling exploration of hierarchal glassy phase separation and spatial partitioning of crystals of powellite and zircon of different morphologies and sizes 10 nm to 1 mm. The tools described in this study offer means of broadly understanding multi-scale structural attributes of multi-phase materials.

Model validation and interpretation of the interaction between glass and cement in an integrated glass dissolution experiment

This article presents the modeling results from the interaction between simulated nuclear waste glasses and ordinary Portland cement (OPC). In general, the modeling results are in good agreement with the experimental results. A diffusion-based glass dissolution model well describes the release of B and Li from the glass, and a reactive transport model well describes the profiles of dissolved glass elements in the cement. It is found that the effective diffusion coefficient of Li in the cement is much larger than that of B. Sorption of both Li and B onto the cement is required to better fit their measured diffusion profiles. For B profiles in the cement, one spatially uniform distribution coefficient is needed, while for Li, sorption needs to be linked to the gel-like secondary phase at the surface of the cement. The effective diffusion coefficients for both Li and B are relatively low and can be linked to the pore-filling effects of the gel-like secondary phase. Even though it is generally believed that nuclear waste glass will dissolve faster in cementitious environments, the results show that the gel-like secondary phase can both seal the cement and act as a strong sorbent for dissolved glass species, thus inhibiting the migration of dissolved glass species.

Structural change by phosphorus addition to borosilicate glass containing simulated waste components

Simulated nuclear waste glass samples containing phosphorus, which increase the solubility of molybdenum, were prepared and analyzed using synchrotron X-ray Absorption Fine Structure (XAFS) analysis for some constituent elements and Raman spectroscopic analysis of their complex structure. Changes in local structure and chemical state due to different phosphorus additions and waste loading rates were systematically studied. Consequently, no crystalline phase due to the molybdate compound was observed even at a maximum waste content of 30 wt% (corresponding to 1.87 mol% MoO3). Oxidation proceeded when the waste-loading rate was increased, whereas the reduction proceeded when phosphorus was added. In some cases, the effects of oxidation and reduction were offset. The local structure around specific elements can be classified as follows; Zn that is affected mainly by the waste-loading rate, Ce that is affected by both the waste-loading rate and phosphorus addition, and Zr element that is not affected by either of them. From the comparison between the analytical results of Mo and other elements, it was considered that the added phosphorus exists as a free PO4 structural unit and may deprive the alkali metal coordinated to the molybdate ion.

Conversion kinetics during melting of simulated nuclear waste glass feeds measured by dissolution of silica

We experimentally investigated the batch-to-glass conversion kinetics of two low-activity and two high-level nuclear waste melter feeds that represent widely different behavior during melting; tests comprised thermogravimetric analysis, the feed expansion test, evolved gas analysis, and x-ray diffraction. Our study indicates that the conversion processes, which include gas-evolving reactions, dissolution of crystalline phases, and primary foam expansion and collapse, are interconnected and influenced by the feed's thermal history. The fraction of dissolved silica was adopted as a measure of the extent of conversion inside the cold cap—the floating layer of feed material on the top surface of the melt in an electric melter. The interface between the cold cap and the free-flowing melt below was associated with a constant fraction of dissolved silica. The estimated viscosity of glass-forming melt at this interface lies within a narrow range for the feeds studied.

Plasma spectroscopy + chemometrics: An ideal approach for the spectrochemical analysis of iron phosphate glass samples

AbstractThe penultimate aim of all analytical techniques is to provide best quantitative information with high sensitivity and accuracy. Such techniques then can be ideal to estimate the concentration of different species in a sample or to measure the surface concentration and so on. The preliminary step involved in quantitative analysis is evaluation of the system response for a given amount of the analyte under investigation. Different methodologies are proposed and executed for the above mentioned purpose. In this work, we have demonstrated the performance of chemometric methods to study the atomic emissions from simulated nuclear waste glasses. Five samples of iron‐phosphate glasses were synthesized by doping Cr, Sr, and Ti at various concentrations. The spectra recorded using laser‐induced breakdown spectroscopy (LIBS) system were analyzed using principal component analysis (PCA), partial least square‐discriminant analysis (PLS‐DA), and support vector machines (SVM) for the classification. As compared with the PLS‐DA, SVM provided better results for classification with accuracy of 100% on both calibration and validation sets, respectively. The quantitative analysis of glass samples is carried out using partial least square regression (PLSR) and support vector regression (SVR). The root mean squared error of prediction (RMSEP) is found to be 0.16, 0.20, and 0.08 (wt%) for Cr, Sr, and Ti using PLSR. The detailed investigation elucidates the advantages of chemometrics in handling the complex LIBS spectrum of glass samples and their significance in process control of nuclear waste, nuclear forensics, and so on.

In situ characterization of foam morphology during melting of simulated waste glass using x-ray computed tomography

During batch-to-glass conversion, a glass-forming melt connects, creating a foam layer between the batch and the glass melt. Due to its transience and opacity, investigation of this foam layer presents a formidable challenge. In this work, we use in situ x-ray computed tomography to characterize the foam morphology that evolves during batch-to-glass conversion of a simulated nuclear waste glass. Rapid 1-min scans with 38 μm voxels were performed to capture the foam structure during heating. Geometric volume, total porosity, and bubble size distribution are reported. Using evolved gas analysis and combining the temperature-dependent melt viscosity with x-ray data, we describe the evolution of foam structure during the foam growth and subsequent collapse.

Nonlinear logistic regression mixture experiment modeling for binary data using dimensionally reduced components

AbstractThis article motivates, presents, and illustrates an approach using nonlinear logistic regression (NLR) for modeling binary response data from a mixture experiment when the components can be partitioned into groups used to form dimensionally reduced components (DRCs). A DRC is formed from a linear combination of the components in a group having similar roles and/or effects of the same sign, where the linear combinations over all groups are normalized so that the DRC proportions sum to one. Linear combinations of a particular form provide for quantifying the effects of the remaining components in a group relative to a chosen component. This reason, plus dimensional reduction, are the primary motivations for the proposed DRC mixture experiment modeling approach. NLR is required because models expressed in terms of the DRCs are nonlinear in the parameters that specify the linear combinations. A method for obtaining nonparametric tolerance limits on the probability of a “success” for the binary response variable using a bootstrap approach is also presented. Finally, the article shows how DRCs provide for visualizing data and modeling results that otherwise would be impossible. A real database on the presence or absence of nepheline crystals in simulated nuclear waste glass is used to illustrate the NLR modeling and nonparametric tolerance limit approaches. The methodology is general and can be applied to other applications.

Glass structure and crystallization in boro-alumino-silicate glasses containing rare earth and transition metal cations: a US-UK collaborative program

ABSTRACTNuclear wastes generated from reprocessing of used nuclear fuel tend to contain a large fraction of rare earth (RE, e.g., Nd3+), transition (TM, e.g., Mo6+, Zr4+), alkali (A, e.g., Cs+), and alkaline earth cations (AE, e.g., Ba2+, Sr2+). Various strategies have been considered for immobilizing such waste streams, varying from nominally crystal-free glass to glass-ceramic to multi-phase ceramic waste forms. For glass and glass-ceramic waste forms, the added glass-forming system is generally alkali-alkaline earth-aluminoborosilicate (i.e., Na-Ca-Al-B-Si oxide). In a US-UK collaborative project, summarized here, we investigated the glass structure and crystallization dependence on compositional changes in simulated nuclear waste glasses and glass-ceramics. Compositions ranged in complexity from five – to – eight oxides. Specifically, the roles of Mo and rare earths are investigated, since a proposed glass-ceramic waste form contains crystalline phases such as powellite [(AE,A,RE)MoO4] and oxyapatite [(RE,AE,A)10Si6O26], and the precipitation of molybdenum phases is known to be affected by the rare earth concentration in the glass. Additionally, the effects of other chemical additions have been systematically investigated, including Zr, Ru, P, and Ti. A series of studies were also undertaken to ascertain the effect of the RE size on glass structure and on partitioning to crystal phases, investigating similarities and differences in glasses containing single RE oxides of Sc, Y, La, Ce, Nd, Sm, Er, Yb, or Lu. Finally, the effect of charge compensation was investigated by considering not only the commonly assessed peralkaline glass but also metaluminous and peraluminous compositions. Glass structure and crystallization studies were conducted by spectroscopic methods (i.e., Raman, X-ray absorption, nuclear magnetic resonance (NMR), optical absorption, photoluminescence, photoluminescence excitation, X-ray photoelectron spectroscopy), microscopy (i.e., scanning electron microscopy, transmission electron microscopy, electron probe microanalysis), scattering (i.e., X-ray and neutron diffraction, small angle measurements), and physical characterization (i.e., differential thermal analysis, liquidus, viscosity, density). This paper will give an overview of the research program and some example unpublished results on glass-ceramic crystallization kinetics, microstructure, and Raman spectra, as well as some examples of the effects of rare earths on the absorption, luminescence, and NMR spectra of starting glasses. The formal collaboration described here has resulted in the generation of a large number of results, some of which are still in the process of being published as separate studies.

Non-linear effects of alumina concentration on Product Consistency Test response of waste glasses

The effect of alumina mole fraction on the 7-day Product Consistency Test (PCT) responses, ln[NLα], of simulated nuclear waste glasses was examined. It was found that the effect is highly non-linear. At low mole fractions of Al2O3 (xAl2O3 ≤ 0.035) the effect of Al2O3 additions is highly negative (dlnNLαdxAl2O3 = −72). At intermediate concentrations (0.035 <xAl2O3 ≤ 0.19) the effect of Al2O3 additions is moderately negative (dlnNLαdxAl2O3 = −11). At high concentrations (0.19 <xAl2O3) the effect of Al2O3 additions is highly positive (dlnNLαdxAl2O3 = +21). This variable impact of Al2O3 on ln[NLα] is speculated to be caused by the rates at which the glass corrosion process changes through various reaction regimes in static conditions at 90 °C. A model for prediction of ln[NLα] as a function of glass composition is presented. This model represents the data from 2669 glass compositions spanning a broad nuclear waste glass composition region and it is useful up to much higher Al2O3 concentrations than previous models (from ∼10 to 25 mol% Al2O3). The model was validated using data subset validation methods and shown to predict validation data in the same composition region with roughly equal certainty as the model fit data. The potential causes for non-linear effects of Al2O3 on ln[NLα] were discussed in context of the progression of glass corrosion rates. Time resolved static corrosion data is needed to better understand these non-linear effects.

Wet chemical processing for nuclear waste glass to retrieve radionuclides.

Here, we show unexpected and significant elution behavior of various elements from simulated nuclear waste glass (NWG) in ∼10° mol dm-3 acidic solutions below 100 °C, where a borosilicate-based glass matrix has been believed to be chemically durable. Most elements like glass main components (Li, B, Na, Ca, Al, and Zn, but except for Si) and simulated radionuclides (Rb, Cs, Sr, Ba, Se, Te, Mn, Pd, Mo, rare earths, Cr, Fe, and Ni) were remarkably eluted from the simulated NWG in ∼10° M HNO3 aq with Cl- at 90 °C. Especially, the elution of Pd is governed by its coordination chemistry including a redox reaction, because Pd(0) present in the simulated NWG has to be oxidized to Pd2+ which forms [PdCl4]2- for its dissolution. While Zr in simulated NWG is sparingly eluted even in this treatment, its elution actually proceeds in 1-3 M H2SO4 aq at 90 °C thanks to strong coordination of Zr(IV) with SO42-. Through design and optimization of the leaching conditions, a protocol of the wet chemical process to retrieve the radionuclides from simulated NWG has been proposed and demonstrated.

Effect of clayey groundwater on the dissolution rate of SON68 simulated nuclear waste glass at 70 °C

To predict the long-term behavior of high-level radioactive waste glass, it is necessary to study aqueous dissolution of the glass matrix under geological repository conditions. The present article focuses on SON68 (an inactive surrogate of the R7T7 glass) glass alteration in synthetic clayey groundwater at 70 °C. Experiments in deionized water as reference were also performed in the same conditions. Results are in agreement with those of previous studies showing that magnesium present in the solution is responsible for higher glass alteration. This effect is transient and pH-dependent: Once all the magnesium is consumed, the glass alteration rate diminishes. Precipitation of magnesium silicate of the smectite group seems to be the main factor for the increased glass alteration. A pH threshold of 7.5–7.8 was found, above which precipitation of these magnesium silicates at 70 °C is possible. TEM observations reveal that magnesium silicates grow at the expense of the passivating gel, which partly dissolves, forming large pores which increase mass transfer between the reacting glass surface and the bulk solution.

Dissolution of Accumulated Spinel Crystals in Simulated Nuclear Waste Glass Melts

AbstractCurrently, efforts are being made to increase the waste loading in vitrified waste forms for the Hanford Tank Waste Treatment and Immobilization Plant, which could result in the formation o...

Investigation of high‐level waste glass melting using X‐ray computed tomography

AbstractA method has been developed to quantitatively assess the melting behavior of simulated nuclear waste glasses in a 5‐cm‐diameter stainless steel beaker heated from the bottom. The method applies X‐ray scanning and computed tomography to build three‐dimensional volumetric data of a heat‐treated sample and performs an adaptive segmentation analysis of the volumetric data to identify morphologically distinct regions in the sample matrix and quantify the amount of material in each region based on computed tomography density. The method was applied to two different series of simulated high‐level waste glass melter feeds, and the results showed that it provides detailed images of samples at various stages of melting, including distribution of gas bubbles of varying sizes within the sample matrix, as well as a quantitative measure of how fast various waste/frit feeds melted relative to each other. The results show that the melting rate is influenced by the rate of calcine gas evolution, melt viscosity, and the presence of modifier ions in the feed.

Understanding of the mechanical and structural changes induced by alpha particles and heavy ions in the French simulated nuclear waste glass

Borosilicate glasses are considered for the long-term confinement of high-level nuclear wastes. External irradiations with 1 MeV He+ ions and 7 MeV Au5+ ions were performed to simulate effects produced by alpha particles and by recoil nuclei in the simulated SON68 nuclear waste glass. To better understand the structural modifications, irradiations were also carried out on a 6-oxides borosilicate glass, a simplified version of the SON68 glass (ISG glass). The mechanical and macroscopic properties of the glasses were studied as function of the deposited electronic and nuclear energies. Alpha particles and gold ions induced a volume change up to −0.7% and −2.7%, respectively, depending on the glass composition. Nano-indentations tests were used to determine the mechanical properties of the irradiated glasses. A decrease of about −22% to −38% of the hardness and a decrease of the reduced Young's modulus by −8% were measured after irradiations. The evolution of the glass structure was studied by Raman spectroscopy, and also 11B and 27Al Nuclear Magnetic Resonance (MAS-NMR) on a 20 MeV Kr irradiated ISG glass powder. A decrease of the silica network connectivity after irradiation with alpha particles and gold ions is deduced from the structural changes observations. NMR spectra revealed a partial conversion of BO4 to BO3 units but also a formation of AlO5 and AlO6 species after irradiation with Kr ions. The relationships between the mechanical and structural changes are also discussed.

High-temperature viscosity of many-component glass melts

In this article, we argue that 1) the activation energy for viscous flow becomes independent of temperature when the viscosity of molten glass is sufficiently low at high enough temperatures, such as those that exist in a glass-melting furnace, and 2) the intercept of the linear function lnη versus T−1 (η is the viscosity and T is the temperature) is independent of glass composition. This hypothesis, which is hardly new and is well supported by experimental data, allows minimization of the number of fitting parameters. A new dataset of meticulously measured viscosities of a large composition region of simulated nuclear waste glasses that recently became available provided an excellent opportunity to test this hypothesis to verify it again. Also, we used this dataset to demonstrate that some popular functions designed for representing the high-viscosity segment (where the activation energy changes with temperature) are not recommendable for approximating the low-viscosity segment (where the activation energy is constant). Fitting such functions produces overparameterization and leads to physically meaningless (or at least esthetically unsatisfactory) outcomes, or, if the functions are constrained by the glass-transition viscosity and the high-temperature asymptote, the result is a significant lack of fit.

Melter Feed Reactions at T ≤ 700°C for Nuclear Waste Vitrification

To understand feed‐to‐glass conversion for the vitrification of nuclear waste, we investigated batch reactions and phase transitions in a simulated nuclear waste glass melter feed heated at 5 K/min up to 700°C using optical microscopy, scanning electron microscopy with energy‐dispersive X‐ray spectroscopy, and X‐ray diffraction. To determine the content and composition of leachable phases, we performed leaching tests; the leachates were analyzed by inductively coupled plasma atomic emission spectroscopy. By 400°C, gibbsite and sodium borates lost water and converted to amorphous phase, whereas other metallic hydroxides dehydrated to oxides. Between 400°C and 700°C, carbonates decomposed before 500°C; amorphous aluminum oxide and calcium oxide reacted with the sodium borate and formed the more durable amorphous borate phase along with intermediate crystalline products; above 500°C, quartz began to dissolve, and hematite started to convert to trevorite.

Argon Cluster Sputtering Source for ToF-SIMS Depth Profiling of Insulating Materials: High Sputter Rate and Accurate Interfacial Information.

The use of an argon cluster ion sputtering source has been demonstrated to perform superiorly relative to traditional oxygen and cesium ion sputtering sources for ToF-SIMS depth profiling of insulating materials. The superior performance has been attributed to effective alleviation of surface charging. A simulated nuclear waste glass (SON68) and layered hole-perovskite oxide thin films were selected as model systems because of their fundamental and practical significance. Our results show that high sputter rates and accurate interfacial information can be achieved simultaneously for argon cluster sputtering, whereas this is not the case for cesium and oxygen sputtering. Therefore, the implementation of an argon cluster sputtering source can significantly improve the analysis efficiency of insulating materials and, thus, can expand its applications to the study of glass corrosion, perovskite oxide thin film characterization, and many other systems of interest.

Effect of Callovo-Oxfordian clay rock on the dissolution rate of the SON68 simulated nuclear waste glass

Long-term storage of high-level nuclear waste glass in France is expected to occur in an engineered barrier system (EBS) located in a subsurface Callovo-Oxfordian (COx) clay rock formation in the Paris Basin in northeastern France. Understanding the behavior of glass dissolution in the complex system is critical to be able to reliably model the performance of the glass in this complex environment. To simulate this multi-barrier repository scenario in the laboratory, several tests have been performed to measure glass dissolution rates of the simulated high-level nuclear waste glass, SON68, in the presence of COx claystone at 90°C. Experiments utilized a High-Performance Liquid Chromatography (HPLC) pump to pass simulated Bure site COx pore water through a reaction cell containing SON68 placed between two COx claystone cores for durations up to 200days. Silicon concentrations at the outlet were similar in all experiments, even the blank experiment with only the COx claystone (∼4mg/L at 25°C and ∼15mg/L at 90°C). The steady-state pH of the effluent, measured at room temperature, was roughly 7.1 for the blank and 7.3–7.6 for the glass-containing experiments demonstrating the pH buffering capacity of the COx claystone. Dissolution rates for SON68 in the presence of the claystone were elevated compared to those obtained from flow-through experiments conducted with SON68 without claystone in silica-saturated solutions at the same temperature and similar pH values. Additionally, through surface examination of the monoliths, the side of the monolith in direct contact with the claystone was seen to have a corrosion thickness 2.5× greater than the side in contact with the bulk glass powder. Results from one experiment containing 32Si-doped SON68 also suggest that the movement of Si through the claystone is controlled by a chemically coupled transport with a Si retention factor, Kd, of 900mL/g.

Wet Chemical and UV-Vis Spectrometric Iron Speciation in Quenched Low and Intermediate Level Nuclear Waste Glasses

ABSTRACTIn this study wet chemical methods combined with UV-Vis spectroscopy were performed to quantify Fe(II)/Fe(III) ratios and total iron content of quenched alkali alumino-boro-silicate (simulated nuclear waste) glasses, applying a colorimetric method. We report lessons learned from experimental challenges encountered associated with the colorimetric method, where 1,10 phenanthroline method is complexed with dissolved glass powder and the resulting solution measured for absorbance at 520 nm to determine Fe(II). To obtain total iron, the solution was then equilibrated with a mild reducing agent to chance all Fe to Fe(II), and the absorbance measured again at 520 nm. These absorbance values allowed for calculation of the Fe(II)/Fe(III) ratio, and the total iron content in the glasses. Total Fe measured is somewhat higher than as-batched target values for waste glasses, but very accurate for reference BCR-2G glass. All quenched alumino-boro-silicate glasses analyzed showed a Fe(II)/Fe(III) ratio between 0.06 (± 0.01) and 0.04 (± 0.01). These values are consistent with those obtained for similar glass compositions melted under analogous conditions, indicating a composition of ca. 94-96% Fe(III).

A Sampling Method for Semi-Quantitative and Quantitative Electron Microprobe Analysis of Glass Surfaces

ABSTRACTThe determination of the long-term stability and corrosion of vitrified nuclear waste is an important aspect of research for the U.S. Department of Energy (DOE). It is necessary to understand the rate and mechanisms of Nuclear Waste Glass (NWG) corrosion to determine whether or not the glassy matrix will be able to retain radionuclides for the required repository performance time period. Glass corrosion and the rate of glass corrosions is determined by both chemical and microscopy. Electron Microprobe Analysis (EPMA) is a common and powerful method utilized in the examination of the chemographic difference between corroded and uncorroded NGWs. In this work, two forms of quantitative and semi-quantitative EPMA methods are defined by optimizing the instruments counting statistics against a standard glass and NIST minerals that have compositions similar to the glasses under examination. Data collected on both the planar and cross-sectioned surfaces of an unaltered simulated NWG by Standard based Wavelength Dispersive Spectroscopy (WDS) was found to be comparable to the theoretical composition of the glass. Conventional standardless Energy Dispersive Spectroscopy (EDS) data collected on the same surfaces was not comparable. However, standard-based EDS analysis is shown to be able to discriminate between unaltered and corroded glass surfaces.