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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.

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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Using polymerization, glass structure, and quasicrystalline theory to produce high level radioactive borosilicate glass remotely: a 20+ year legacy

Vitrification is currently the most widely used technology for the treatment of high level radioactive wastes (HLW) throughout the world. Most of the nations that have generated HLW are immobilizing in borosilicate glass. One of the primary reasons that glass has become the most widely used immobilization media is the relative simplicity of the vitrification process, e.g. melt a highly variable waste with some glass forming additives such as SiO 2 and B 2 O 3 in the form of a premelted frit and pour the molten mixture into a stainless steel canister. Seal the canister before moisture can enter the canister (10’ tall by 2’ in diameter) so the canister does not corrode from the inside out. Glass has also become widely used for HLW is that due to the fact that the short range order (SRO) and medium range order (MRO) found in the structure of glass atomistically bonds the radionuclides and hazardous species in the waste. The SRO and MRO have also been found to govern the melt properties such as viscosity and resistivity of the melt and the crystallization potential and solubility of certain species. Furthermore, the molecular structure of the glass also controls the glass durability, i.e. the contaminant/radionuclide release, by establishing the distribution of ion exchange sites, hydrolysis sites, and the access of water to those sites. The molecular structure is flexible and hence accounts for the flexibility of glass formulations to HLW waste variability. Nuclear waste glasses melt between 1050-1150°C which minimizes the volatility of radioactive components such as 99 Tc, 137 Cs, and 129 I. Nuclear waste glasses have good long term stability including irradiation resistance. Process control models were developed based on the molecular structure of glass, polymerization theory of glass, and quasicrystalline theory of glass crystallization. These models create a glass which is durable, pourable, and processable with 95% accuracy without knowing from batch to batch what the composition of the waste coming out of the storage tanks will be. These models have operated the Savannah River Site Defense Waste Processing Facility (SRS DWPF), which is the world’s largest HLW Joule heated ceramic melter, since 1996. This unique “feed forward” process control, which qualifies the durability, pourability, and processability of the waste plus glass additive mixture before it enters the melter, has enabled ~8000 tons of HLW glass and 4242 canisters to be produced since 1996 with only one melter replacement.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2024

Application of the immobilized low-activity waste glass corrosion model to the static dissolution of 24 statistically-designed alkali-borosilicate waste glasses

Glass corrosion models that capture the complex mechanisms of the glass-water reaction enable the prediction of nuclear waste glass durability in disposal scenarios. Parameterization of such models is challenging because of the need to capture changes in corrosion behavior with time, reaction conditions, and glass composition. In this report we describe and employ the immobilized low activity waste (ILAW) glass corrosion model (IGCM) in geochemical simulations of static dissolution tests, at two temperatures (40 °C and 90 °C), for a matrix of 24 enhanced low activity waste (eLAW) glasses statistically designed to cover a processable composition space defined by 8 major glass components (Al 2 O 3 , B 2 O 3 , CaO, Na 2 O, SiO 2 , SnO 2 , ZrO 2 , and Others as defined in the text). The IGCM includes a first-order chemical affinity term and an ion-exchange term that represents the net exchange of Na+ ions in the pristine glass with protons in aqueous solution. Constant, time-dependent, and time- and pH-dependent functional forms of the ion-exchange term are evaluated to reproduce the change in corrosion behavior with time in saturated, static dissolution tests. The agreement with measured aqueous concentrations of the main glass components (B, Na, and Si) improved significantly upon addition of a time-dependent term, which therefore constitutes a simple representation of the glass-water reaction progress. Due to the limited changes in pH in the static dissolution tests, past a short initial period of rapid increase, addition of a pH dependent term did not appreciably improve the fits, indicating that comprehensive model parameterization requires more than one type of glass corrosion test to capture a wide range of solution chemistries. IGCM parameters were found to be dependent on glass composition, and the parameter sets generated in this work will enable the development of composition–parameter correlation models that offer the promise of predicting IGCM parameters, and thus glass corrosion behavior, solely based on glass composition.

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

Seeded Stage III glass dissolution behavior of a statistically designed glass matrix

The glass dissolution rate of some glasses accelerates after prolonged time spent at a slow, residual glass dissolution rate. This phenomenon is referred to as Stage III behavior. Here, the acceleration in glass dissolution rate linked to Stage III behavior is significant and may be the most impactful to long-term performance of glass in a repository. This work is aimed at understanding the effect of glass composition on Stage III behavior to add a level of technical defensibility to glass disposal. To this end, a set of twenty-four glass compositions were statistically designed, where eight glass components (SiO 2 , B 2 O 3 , Al 2 O 3 , CaO, Na 2 O, SnO 2 , ZrO 2 , and Others) have been independently varied in order to study the individual effects of each. These glasses have been subjected to static dissolution tests at 90 °C in deionized water and then seeded with zeolite Na-P2 28 days into the testing to induce Stage III behavior. The response of the glasses to the zeolite seeds fell into four primary types: 1) no response to seeds; 2) an immediate linear sustained acceleration in the rate; 3) an immediate linear acceleration in the rate followed by a decrease; and, 4) a progressive acceleration in the rate that is concurrent with the addition of the seeds. The main glass components observed to influence these behaviors were CaO, Al 2 O 3 , B 2 O 3 , and ZrO 2 , where: 1) CaO influenced which glasses showed a Stage III response to seeds (high CaO: Types 2, 3, and 4) or did not respond to seeds (low CaO: Type 1), 2) Al 2 O 3 and B 2 O 3 influenced which glasses showed a sustainable Stage III response (high Al 2 O 3 : Types 2 and 4) versus transitory response (low Al 2 O 3 and high B 2 O 3 : Type 3), and 3) ZrO 2 concentration influenced whether glasses showed a linear (high ZrO 2 : Type 2) versus progressive (low ZrO 2 : Type 4) response to seeds.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Chemical speciation of U, Fe, and Pu in melt glass from nuclear weapons testing

Nuclear weapons testing generates large volumes of glassy materials that influence the transport of dispersed actinides in the environment and may carry information on the composition of the detonated device. We determine the oxidation state of U and Fe (which is known to buffer the oxidation state of actinide elements and to affect the redox state of groundwater) in samples of melt glass collected from three U.S. nuclear weapons tests. For selected samples, we also determine the coordination geometry of U and Fe, and we report the oxidation state of Pu from one melt glass sample. We find significant variations among the melt glass samples and, in particular, find a clear deviation in one sample from the expected buffering effect of Fe(II)/Fe(III) on the oxidation state of uranium. In the first direct measurement of Pu oxidation state in a nuclear test melt glass, we obtain a result consistent with existing literature that proposes Pu is primarily present as Pu(IV) in post-detonation material. In addition, our measurements imply that highly mobile U(VI) may be produced in significant quantities when melt glass is quenched rapidly following a nuclear detonation, though these products may remain immobile in the vitrified matrices. The observed differences in chemical state among the three samples show that redox conditions can vary dramatically across different nuclear test conditions. The local soil composition, associated device materials, and the rate of quenching are all likely to affect the final redox state of the glass. The resulting variations in glass chemistry are significant for understanding and interpreting debris chemistry and the later environmental mobility of dispersed material.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Quantitative Structure–Property Relationship (QSPR) Analysis of ZrO 2 -Containing Soda-Lime Borosilicate Glasses

Quantitative structure–property relationship (QSPR) analysis is a promising approach to correlate structural features with properties of glass materials that lack long-range order and usually have complex structures. By using carefully chosen descriptors based on structural models generated from molecular dynamics (MD) simulations, correlations with properties and insights on glass behaviors can be obtained. Zirconia can significantly alter glass properties including chemical durability, even in a small amount, and hence plays an important role in vitrification of nuclear waste where long-term chemical durability is desired. In this study, borosilicate glasses with the composition of xZrO 2 –(61 – x)SiO 2 –17B 2 O 3 –18Na 2 O–4CaO with x = 0, 1, 2, 4, 6, and 8 were simulated using classical MD simulations with the recently developed composition-dependent potentials. Short-range (e.g., bond distance and coordination numbers) and medium-range (e.g., Qn distribution, network connectivity, and ring-size distribution) structural features altered by ZrO 2 were obtained and analyzed. The use of a descriptor (Fnet descriptor) that combines short-range structural characteristics, from MD simulations, and the cation-oxygen single bond strength was found to provide excellent linear correlations with the density and initial dissolution rate of these glasses. Furthermore, the results show that by combining MD simulations and QSPR analysis the composition and structural effect on the properties of complex multicomponent glasses can be elucidated, thus suggesting that this is a promising approach for future glass research and new composition design.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Reentrant glass transition leading to ultrastable metallic glass

Polyamorphs are often observed in amorphous matters, and a representative example is the reentrant glass transition in colloid systems. For metallic amorphous alloys, however, the cases reported so far are limited to metallic glasses (MGs) that undergo electronic transitions under gigapascal applied pressure, or the presence of two liquids at the same composition. In this paper, we report the first observation of a reentrant glass transition in MGs. This unusual reentrant glass transition transforms an MG from its as-quenched state (Glass I) to an ultrastable state (Glass II), mediated by the supercooled liquid of Glass I. Specifically, upon heating to above its glass transition temperature under ambient pressure, Glass I first transitions into its supercooled liquid, which then transforms into a new Glass II, accompanied by an exothermic peak in calorimetric scan, together with a precipitous drop in volume, electrical resistance and specific heat, as well as clear evidence of local structural ordering on the short-to-medium-range scale revealed via in-situ synchrotron X-ray scattering. Atomistic simulations indicate enhanced ordering of locally favored motifs to establish correlations in the medium range that resemble those in equilibrium crystalline compounds. The resulting lower-energy Glass II has its own glass transition temperature higher than that of Glass I by as much as 50 degrees. This route thus delivers a thermodynamically and kinetically ultrastable MG that can be easily retained to ambient conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Toward Understanding the Effect of Low-Activity Waste Glass Composition on Sulfur Solubility

The concentration of sulfur in nuclear waste glass melter feed must be maintained below the point where salt accumulates on the melt surface. The allowable concentrations may range from 0.37 to over 2.05 weight percent (of SO3 on a calcined oxide basis). If the amount of sulfur exceeds its tolerance level a molten salt will accumulate and upset melter operations and potentially shorten melter useful life. Therefore relatively conservative limits have been placed on sulfur loading in melter feed which in-turn significantly impacts the amount of glass that will be produced, in particular at the Hanford site. Crucible-scale sulfur solubility data and scaled melter sulfur tolerance data have been collected on simulated Hanford waste glasses over the last 15 years. These data were compiled and analyzed. A model was developed to predict the solubility of SO3 in glass based on 312 individual glass compositions. This model was shown to well represent the data, accounting for over 80% of the variation in data and was well validated. The model was also found to accurately predict the tolerance for sulfur in melter feed based on 19 scaled melter tests. The model is appropriate for control of waste glass processing which includes uncertainty quantification. The model also gives quantitative estimates of component concentration effects on sulfur solubility. The components that most increase sulfur solubility are Li2O > V2O5 ≈ TiO2 < CaO < P2O5 ≈ ZnO. The components that most decrease sulfur solubility are Cl > Cr2O3 > SiO2 ≈ ZrO2 > Al2O3.

Borosilicate↗
DOE OSTI2025

Corrosion Testing of Refractory inContact with Molten Glasses Designed for Waste Vitrification - VSL Touchpoint Matrix Glasses

It is known that the predictive life of the refractory ceramic liner of nuclear waste glass melters is conservative, as demonstrated by performance of these materials such as in the Defense Waste Processing Facility (DWPF). The motivation for this task is to maximize the useful life of the melters that will be operated at the Waste Treatment and Immobilization Plant (WTP), which will in turn minimize procurement and disposal costs and melter outage times, as well as to identify maximum loadings in the waste glass of those species that corrode melter components. This task was initiated jointly with Pacific Northwest National Laboratory (PNNL) with the objective to develop a methodology and model to enable more accurate prediction of refractory service life under prototypic conditions from laboratory-scale material corrosion tests. Refractory corrosion is generally reported as physical material loss, measured in units of distance (e.g., inch) or as physical material loss rate, measured in units of distance per time (e.g., inch/day). In post-operational melters, the refractory corrosion is measured directly, sometimes reported as corrosion depth. Crucible tests are used in the laboratory to accelerate the refractory corrosion to facilitate a meaningful measurement in a commensurate amount of time. Crucible tests are particularly useful in understanding refractory corrosion across a large glass composition space, where operational testing would be prohibitive. Some of the critical parameters that are known to influence refractory corrosion by molten glass in a crucible test are temperature, system redox, molten salt phases, glass chemistry, and test duration. The majority of data collected for Monofrax® K-3 (hereafter referred to as K-3) corrosion is from crucible tests, but a small amount comes directly from scaled and production melters. Crucible test data has been collected under varying conditions, whereas data collected from operational melters is relatively fewer and represents conditions specific to the melter campaign. The result is that the published data can be grouped and analyzed in multiple ways, not all of which are readily comparable. The Standard Test Method for Isothermal Corrosion Resistance of Refractories to Molten Glass (ASTM C621) outlines the general guidelines used across industry. That method describes a sealed, static test in which the surface area of the refractory coupon and the volume of glass are fixed. A significant portion of the crucible data pertaining to nuclear waste glasses has been collected in a modified configuration; the most notable differences being the surface area of the refractory coupon to volume of the glass and use of a method for bubbling the melt. To our knowledge, the influence of those parameters on the refractory corrosion has not been quantified. In this work, it was determined that static tests and bubbled tests would be performed. Savannah River National Laboratory (SRNL) was tasked with setting up and performing static testing while PNNL was tasked with setting up and performing bubbled testing. Initial activities were performed to establish laboratory methods that reproduce data comparable to existing data sets of K-3 refractory corrosion by low activity waste (LAW) and high-level waste (HLW) glass compositions. Later activities were focused on refining the test parameters to establish a standard test practice to be used between Laboratories and collecting additional data to be used in the enhanced waste glass model development. This document serves primarily to convey the refractory loss measurement results from corrosion testing of K-3 refractory with waste glass compositions developed for use in the WTP melters. The data will be used in the enhanced property/composition models being developed for waste glass vitrification and melter operations.

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

Monte Carlo Simulations of Coupled Diffusion and Surface Reactions during the Aqueous Corrosion of Borosilicate Glasses

Borosilicate nuclear waste glasses develop complex altered layers as a result of coupled processes such as hydrolysis of network species, condensation of Si species, and diffusion. However, diffusion has often been overlooked in Monte Carlo models of the aqueous corrosion of borosilicate glasses. Therefore, three different models for dissolved Si diffusion in the altered layer were implemented in a Monte Carlo model and evaluated for glasses in the compositional range (75-x) mol% SiO2 (12.5+x/2) mol% B2O3 and (12.5+x/2) mol% Na2O, where 0 ≤ x ≤ 20%, and corroded in static conditions at a surface-to-volume ratio of 1000 m-1. The three models considered instantaneous homogenization (M1), linear concentration gradients (M2), and concentration profiles determined by solving Fick’s 2nd law using a finite difference method (M3). Model M3 revealed that concentration profiles in the altered layer are not linear and show changes in shape and magnitude as corrosion progresses, unlike those assumed in model M2. Furthermore, model M3 showed that, for borosilicate glasses with a high forward dissolution rate compared to the diffusion rate, the gradual polymerization and densification of the altered layer is significantly delayed compared to models M1 and M2. Models M1 and M2 were found to be appropriate models only for glasses with high release rates such as simple borosilicate glasses with low ZrO2 content.

borosilicates↗
DOE OSTI2017

Nanoscale imaging of alteration layers of corroded international simple glass particles using ToF-SIMS

Glass particles with dimensions typically ranging from tens to hundreds of microns are often used in glass corrosion research in order to accelerate testing. Two-dimensional and three-dimensional nanoscale imaging techniques are badly needed to characterize the alteration layers at the surfaces of these corroded glass particles. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) can provide a lateral resolution as low as ~100 nm, and, compared to other imaging techniques, is sensitive to elements lighter than carbon. In this work, we used ToF-SIMS to characterize the alteration layers of corroded international simple glass (ISG) particles. At most particle surfaces, inhomogeneous or no alteration layers were observed, indicating that the thickness of the alterations layers may be too thin to be observable by ToF-SIMS imaging. Relatively thick (e.g., 1-10 microns) alteration layers were inhomogeneously distributed at a small portion of surfaces. More interestingly, some large-size (tens of microns) glass particles were fully altered. Above observations suggest that weak attachment and the defects on ISG particle surfaces play an important role in ISG glass corrosion.

alteration layer↗
DOE OSTI2016

Cooling rate dependence of structural order in Al{sub 90}Sm{sub 10} metallic glass

The atomic structure of Al{sub 90}Sm{sub 10} metallic glass is studied using molecular dynamics simulations. By performing a long sub-T{sub g} annealing, we developed a glass model closer to the experiments than the models prepared by continuous cooling. Using the cluster alignment method, we found that “3661” cluster is the dominating short-range order in the glass samples. The connection and arrangement of “3661” clusters, which define the medium-range order in the system, are enhanced significantly in the sub-T{sub g} annealed sample as compared with the fast cooled glass samples. Unlike some strong binary glass formers such as Cu{sub 64.5}Zr{sub 35.5}, the clusters representing the short-range order do not form an interconnected interpenetrating network in Al{sub 90}Sm{sub 10,} which has only marginal glass formability.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2017

Predictive modeling of crystal accumulation in high-level waste glass melters processing radioactive waste

The effectiveness of HLW vitrification is limited by precipitation/accumulation of spinel crystals [(Fe, Ni, Mn, Zn)(Fe, Cr)2O4] in the glass discharge riser of Joule-heated ceramic melters during idling. These crystals do not affect glass durability; however, if accumulated in thick layer, they can clog the melter and prevent discharge of molten glass into canisters. To address this problem, an empirical model was developed that can predict thicknesses of accumulated layers as a function of glass composition. This model predicts well the accumulation of single crystals and/or small-scale agglomerates, but, excessive agglomeration observed in high-Ni-Fe glass resulted in an under-prediction of accumulated layers, which gradually worsen over time as an increased number of agglomerates formed. Accumulation rate of ~53.8 ± 3.7 µm/h determined for this glass will result in ~26 mm thick layer in 20 days of melter idling.

Crystal accumulation↗
DOE OSTI2020

A general mechanism for gel layer formation on borosilicate glass under aqueous corrosion

Mineral and glass dissolution is a scientific topic deeply investigated but incompletely understood and of a great interest for the geochemical and materials science communities. If the interfacial dissolution/reprecipitation mechanism seems to be applicable to most of silicate minerals, the debate remains open concerning glass. Here we studied two model glasses, a ternary borosilicate (CJ1) and the same glass doped with 4.1 mol% of Al2O3 (CJ2). The two glasses were altered at 90°C, pH 9, and in conditions far and close to saturation with respect to amorphous silica, to determine the initial and residual rates. Moreover, a specific experiment was conducted for a short duration with a solution highly enriched with 18O and 29Si isotopes to understand how passivating gels form. SEM, TEM and ToF-SIMS characterization, along with Monte Carlo simulations were used to understand the rate limiting reactions at play and infer the role of Al. We show that Al yields a slower matrix dissolution in dilute conditions. However, it slows down he formation and the maturation of the passivating gel and favors alteration by partial hydrolysis of Si and Al entities followed by in-situ reorganization/relaxation into a porous network. Unexpectedly, CJ1 experienced both interfacial dissolution/reprecipitation and partial hydrolysis followed by in situ reorganization of the silicate network during the course of a single experiment. This study offers a unified concept that can pave the way for the future development of a predictive kinetic model based on a detailed description of bond breaking and bond forming as a function of glass composition and alteration conditions.

Gin, Stephane↗
DOE OSTI2022

Designing Glass and Crystalline Phases of Metal–Bis(acetamide) Networks to Promote High Optical Contrast

Owing to their high tunability and predictable structures, metal–organic materials offer a powerful platform to study glass formation and crystallization processes and to design glasses with unique properties. In this work, we report a novel series of glass-forming metal–ethylenebis(acetamide) networks that undergo reversible glass and crystallization transitions below 200 °C. The glass-transition temperatures, crystallization kinetics, and glass stability of these materials are readily tunable, either by synthetic modification or by liquid-phase blending, to form binary glasses. Pair distribution function (PDF) analysis reveals extended structural correlations in both single and binary metal–bis(acetamide) glasses and highlights the important role of metal–metal correlations during structural evolution across glass–crystal transitions. Notably, the glass and crystalline phases of a Co–ethylenebis(acetamide) binary network feature a large reflectivity contrast ratio of 4.8 that results from changes in the local coordination environment around Co centers. These results provide new insights into glass–crystal transitions in metal–organic materials and have exciting implications for optical switching, rewritable data storage, and functional glass ceramics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗