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At least 865 records · Page 48

Stress Mapping in Glass-to-Metal Seals using Indentation Crack Lengths

Predicting the residual stress which develops during fabrication of a glass-to-metal compression seal requires material models that can accurately predict the effects of processing on the sealing glass. Validation of the predictions requires measurements on representative test geometries to accurately capture the interaction between the seal materials during a processing cycle required to form the seal, which consists of a temperature excursion through the glass transition temperature of the sealing glass. To this end, a concentric seal test geometry, referred to as a short cylinder seal, consisting of a stainless steel shell enveloping a commercial sealing glass disk has been designed, fabricated, and characterized as a model validation test geometry. To obtain data to test/validate finite element (FE) stress model predictions of this geometry, spatially-resolved residual stress was calculated from the measured lengths of the cracks emanating from radially positioned Vickers indents in the glass disk portion of the seal. The indentation crack length method is described, and the spatially-resolved residual stress determined experimentally are compared to FE stress predictions made using a nonlinear viscoelastic material model adapted to inorganic sealing glasses and an updated rate dependent material model for 304L stainless steel. The measurement method is a first to achieve a degree of success for measuring spatially resolved residual stress in a glass-bearing geometry and a favorable comparison between measurements and simulation was observed.

36 MATERIALS SCIENCE↗

Phase separation and crystallization of complex borosilicate melts for glass-ceramic waste forms

Waste loadings of reprocessed spent nuclear fuel vitrified into borosilicate glass can be increased by precipitating environmentally stable phases concentrated with waste components in a chemically stable glass matrix. The principal objective of this study was to characterize the development of crystalline powellite (CaMoO 4 and related phases) and oxyapatite (Ca 2 LN 8 Si 6 O 26 ) in borosilicate glass-ceramics and to determine how the formation of those phases affected its chemical durability. Borosilicate glasses provided by PNNL were re-melted and quenched at rates from over 300°C/s to ~0.05°C/s. Isothermal heat treatment experiments were conducted by quenching melts in a molten tin bath at various temperatures, holding for periods of time, and then quenching in a water bath. Analytical electron microscopy and x-ray diffraction provided information about the kinetics of the phase separation and crystallization processes responsible for microstructural development. Powellite and oxyapatite crystals formed during slower quench rates and longer isothermal times, and time-temperature-transformation (TTT) diagrams were developed from the latter experiments. A hot thermocouple test (HTT) system was built to rapidly quench melts and hold them at set times to provide supplementary TTT information, but that system was not as sensitive to the phase transformations as other tests. Corrosion tests were performed to understand how the individual phases in the glass-ceramic affect its overall chemical durability. Product consistency tests, performed at Missouri S&T and at Savannah River National Lab, provided release rates of major elements from samples as a function of cooling rate, and atomic force microscopy and profilometry measurements of surface topology determined the relative corrosion rates of the residual glass and oxyapatite phases. Faster dissolution rates were measured from samples cooled more slowly and these were explained by the greater fractions of B 2 O 3 in the residual glass phase after the formation of oxyapatite and powellite. Oxyapatite was found to be more durable than the residual glass.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Screening of Additional Candidate Low-Temperature Glasses for Technetium Recovered from Hanford Effluent Management Facility Evaporator Bottoms

In this annex to a previously reported study, a series of laboratory screening tests was conducted to identify low-temperature glasses that have significant potential for use in disposition of technetium from a Hanford Tank Waste Treatment & Immobilization Plant (WTP) secondary liquid waste stream. Specifically, a glass waste form is sought that would be suitable for on-site disposition of technetium, salts, and other species in a Tc-rich stream recovered by ion exchange from the future Effluent Management Facility (EMF) evaporator concentrate. In the current study, several additional candidate glasses were identified, and testing of previous candidates was extended to include the Toxicity Characteristic Leaching Procedure (TCLP). In non-radioactive testing with rhenium surrogate, new formulations incorporated a simulated ion exchange eluate at temperatures below 750 °C to produce an amorphous, or mixed crystalline-amorphous, product. Incorporation of technetium (NaTcO 4 )-containing simulated eluate was evaluated for two of these glasses. Technetium was not retained well in these glasses, confounding the previous conclusion that Tc volatilization during vitrification can be reduced by appropriate selection of low-temperature glasses. Preliminary data for additional low-temperature glass compositions and recommendations for future work are provided. This report is a deliverable associated with requisition 55068-004-03 NFE-17-0020 "Candidate Low-T Glass Waste Forms for EMF Bottoms On-Site Disposition Alternative."

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DFLAW Glass and Feed Qualifications for AP-107 to Support WTP Start-Up and Flow-Sheet Development (VSL-18R4500-1, Rev 0)

About 50 million gallons of high-level mixed waste is currently stored in underground tanks at The United States Department of Energy’s (DOE’s) Hanford site in the State of Washington. The Hanford Tank Waste Treatment and Immobilization Plant (WTP) will provide DOE’s Office of River Protection (ORP) with a means of treating this waste by vitrification for subsequent disposal. The tank waste will be separated into low- and high-activity waste fractions, which will then be vitrified respectively into Immobilized Low Activity Waste (ILAW) and Immobilized High Level Waste (IHLW) products. The ILAW product will be disposed in an engineered facility on the Hanford site while the IHLW product is designed for acceptance into the national deep geological disposal facility for high-level nuclear waste. The ILAW and IHLW products must meet a variety of requirements with respect to protection of the environment before they can be accepted for disposal. The Low Activity Waste (LAW) at Hanford will be vitrified in a Joule Heated Ceramic Melter (JHCM) to produce a stable product for safe disposal. Although present in relatively small amounts, a few key constituents in the LAW streams play particularly important roles. Sulfur, chlorine, and fluorine can have significant impacts on LAW glass formulation and waste loadings, while technetium and iodine are important for waste form performance, with technetium being the constituent of most concern with respect to waste disposal in the Integrated Disposal Facility (IDF). The IDF is designed to accept ILAW, secondary waste associated with ILAW production, and other on-site Hanford Non-Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA) waste. As a result of volatilization of these species during the vitrification process, they are also present in significant amounts in the liquid effluents from the off-gas treatment system. Understanding the fraction of each constituent incorporated in the LAW glass or in WTP liquid effluents is critical for assessing the performance of waste forms to be disposed in the IDF. Liquid effluents from the LAW vitrification process that are not recycled will likely be solidified to produce a secondary waste form that is not as chemically durable as glass. Therefore, understanding partitioning of the key constituents between the glass and non-glass waste forms is a significant factor in the Performance Assessment (PA) for the Hanford IDF. Clearly, it is preferable to incorporate as much of the technetium into the glass as possible because of the superior chemical durability of that waste form. The objective of the present work is to improve the understanding of the partitioning of technetium and other key waste constituents between the glass and non-glass waste forms.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Glass Crystallization Constraints for WTP LAW Operations: Assessment of Isothermal Treatments on Crystal Formation

Much work has been done to expand the glass composition region available for operation of the Hanford Tank Waste Treatment and Immobilization Plant. This includes the development of updated glass property-composition models as well as constraints. This report supports this effort by suggesting constraints for avoiding excessive, and likely detrimental, crystallization during melter operation while processing advanced low-activity glasses. The constraints target Cassiterite and ZrO 2 -containing phases (ZCP, e.g., Baddeleyite and Zircon) that can form when melter temperatures drop below 1100 °C. These types of crystals were found to be potentially detrimental during processing as they are denser than low-activity waste glass melts; with densities of 6.95 g/cm 3 for Cassiterite and 5.68 g/cm 3 for Baddeleyite (the most prevalent ZCP). Compared to melt densities of approximately 2.65 g/cm 3 . Thus, they have the potential to form during melter idling and settle to the bottom of the melter or inside the melter. If the crystals are present in appreciable amounts, they can result in blockages of the pour-spout riser, which impacts glass pouring and melter operation. Additionally, SnO 2 and ZrO 2 are added to glass formulations to improve glass durability. Their precipitation from the melt may reduce overall glass durability. Using previously acquired results and results from testing during this effort, the following constraints (Table S.1) were determined and are recommended to reduce the risk of forming crystals of the types and concentrations that are likely detrimental to melter operation.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Product Consistency Test Results for the LAW ML1 Glasses

This report summarizes the chemical analysis of Product Consistency Test (PCT) leachates received from Pacific Northwest National Laboratory (PNNL). The leachates are from a series of quenched simulated nuclear waste glasses designated Low-Activity Waste Machine Learning (LAW ML1) glasses that were designed and fabricated at PNNL. The reported data will be used in the development, validation, and implementation of enhanced property/composition models for waste glass vitrification at Hanford. The elemental release for the study glasses is reported as normalized concentration NCi. NCi of several elements was computed for both the target and measured glass compositions, which were similar, resulting in no significant differences. Several of the glasses exhibited NC B , NC Na , and/or NC Si values that were greater than the Waste Treatment Plant (WTP) low-activity waste constraint of 4 g/L. All reference glasses included with the study glasses had measurements that fell within the expected ranges.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Product Consistency Test Results for the HLW HAlG Glasses

This report summarizes the chemical analysis of Product Consistency Test leachates received from Pacific Northwest National Laboratory (PNNL). The leachates are from a series of quenched simulated nuclear waste glasses designated High-Level Waste High Aluminum Glass that were designed and fabricated at PNNL. The reported data is provided to be used in the development, validation, and implementation of enhanced property/composition models for waste glass vitrification at Hanford. The elemental release for the study glasses is reported as normalized concentration NCi. NCi of several elements was computed for both the target and measured glass compositions. Several of the glasses exhibited NC B , NC Li , and/or NC Na values that were greater than the Environmental Assessment (EA) benchmark values. Several of the leachates from approved reference material (ARM) glasses included with the study glasses had elemental concentrations greater than the expected ranges. Two water blanks contained measurable amounts of Si; measurements confirmed by rerun samples. One water blank also contained a measurable amount of Na.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

LAW Glass Formulation to Support Melter Runs with Simulants

The major objective of this work was to prepare and characterize glass formulations in order to develop and select formulations that are compliant with contractual and processing requirements to support melter tests with each of the LAW Sub-Envelopes. Glasses that cover composition ranges of interest were prepared and characterized to ensure that selected glass compositions can tolerate expected composition variations resulting from process errors without adversely affecting processing characteristics or product quality. Glass compositions that are expected to result during transitions from one waste stream to another were also prepared and characterized. Other objectives of the work included preparation and characterization of glasses with respect to the properties of interest, optimization of sulfate loading in the glasses, evaluation of ability to achieve waste loading limits, testing to demonstrate compatibility of glass melts with melter materials of construction, and identification of glass formulation issues with respect to contract specifications and processing requirements.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Enhanced HLW Glass Property-Composition Models – Phase 1 (Final Report)

In the present work, the previously compiled glass property-composition database for WTP HLW glasses has been updated with newly available data. The earlier evaluation of the baseline WTP models against the larger data sets, in terms of range of validity and prediction performance, has been used together with a review of the HLW glass data to identify gaps in the composition regions that need to be filled to support the development of expanded models. Subsequently, statistically-designed compositional matrices were developed to begin to fill these composition gaps. Crucible melts have been prepared for the matrix glasses and glass properties have been collected. Finally, preliminary models have been developed that are applicable to the expanded dataset. Additionally, the performance of the preliminary models have been reviewed to assess the relative advantages of developing one set of models for the entire HLW glass composition space or to developing separate models for discrete composition spaces. The longer-term objective of this multi-year task is to develop new glass property-composition models for PCT release, spinel crystallization (T 1% ), nepheline formation on CCC, TCLP Cd response, viscosity, and electrical conductivity to control glass compositions for HLW vitrification at Hanford.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Optimization of LAW Glass Former Additives

The primary objective of this work was to collect data to support processing Hanford LAW streams at higher rates through changes in mineralogy, forms, and grain sizes of the GFCs. This was achieved through assessment of LAW feeds with different GFCs by feed rheology testing, testing with a vertical gradient furnace (VGF) system to assess melt rates, and processing selected modified LAW feeds through a DM100 melter to measure glass production rates and processing behavior. A high waste loading glass formulation developed in earlier work [8] for an LAW composition specified by WTP was used for rheology, VGF, and melter testing. The glass composition, ORPLA20, is based on LAW tank AN-105; the glass has a waste loading of 31.4 wt% and a Na2O content of 24.0 wt%. Another high waste loading glass formulation developed in earlier work for an LAW composition specified by WTP was also used for VGF testing to investigate the effects of changes in GFCs on melt rate for a second waste and glass composition. That glass composition is ORPLD6, which is based on LAW tank AN-102; the glass has a waste loading of 25.9 wt% and a Na2O content of 22.0 wt%.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Enhanced HLW glass property-composition models - phase 3

During the present phase (Phase 3) of work to enhance and expand the HLW glass property-composition models, test data for 137 glasses were collected and incorporated into the combined WTP/ORP database. The new data include those collected on glasses from two statistically designed matrices to augment the moderate alumina region (the HLW16-MA matrix covering the region of 9 wt% < Al2O3 < 12 wt% with 16 glasses) and the ultra-high alumina region (the HLW16-UHA matrix covering the region of 26 wt% < Al2O3 < 29 wt% with 29 glasses). The addition of ORP glasses over the different phases of testing has significantly expanded the combined WTP/ORP database. The compiled data include glass compositions, PCT (B, Li and Na) releases, spinel T1%, electrical conductivity, viscosity, TCLP-Cd releases, and nepheline formation upon CCC. With the exception of the CCC spinel formation data – the CCC data will be used to support the further development of nepheline models for Hanford HLW glasses.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Comprehensive Isotopic and Elemental Analysis of a Multi-Oxide Glass By Multicollector ICP-MS in Isotope Substitution Studies

Multicollector ICP-MS was used to comprehensively analyze different types of isotopically-modified glass created in order to investigate the processes of glass corrosion in the water. The analytical methods were developed for the analyses of synthesized, isotopically-modified solid glass and the release of glass constituents upon contact with deionized water. To validate the methods, results from an acid digestion sample of the Analytical Reference Glass (ARG) showed good agreement when compared to data from multiple prior analyses on the same glass [Smith-1]. In this paper, we present the results of this comprehensive analysis from the acid digestion of six types of isotopically-modified glass and the release of glass constituents into water corrosion after one year of aqueous corrosion.

07 ISOTOPE AND RADIATION SOURCES↗

The kinetics of crystallization of molten binary and ternary oxide systems and their application to the origination of high modulus glass fibers

Emphasis on the consideration of glass formation on a kinetic process made it possible to think of glass compositions different from those normally employed in the manufacture of glass fibers. Approximately 450 new glass compositions were prepared and three dozen of these compositions have values for Young's modulus measured on bulk specimens greater than nineteen million pounds per square inch. Of the new glasses about a hundred could be drawn into fibers by mechanical methods at high speeds. The fiber which has a Young's modulus measured on the fiber of 18.6 million pounds per square inch and has been prepared in quantity as a monofilament (to date more than 150 million lineal feet of 0.2 to 0.4 mil fiber have been produced). This fiber has also been successfully incorporated both in epoxy and polyimide matrices. The epoxy resin composite has shown a modulus forty percent better than that achievable using the most common grade of competitive glass fiber, and twenty percent better than that obtainable with the best available grade of competitive glass fiber. Other glass fibers of even higher modulus have been developed.

Bacon, J. F.↗

Determining and analyzing the strength and impact resistance of high modulus glass

A number of new glass compositions have been prepared with increased emphasis on compositions without beryllia. Glass preparations have been much more broadly based and have included the eutectic glass fields, and the mullite-rare earth glass systems. Of the new glasses, the best non-toxic composition is UARL 472 with a bulk modulus of only 18.20 million psi. A second experimental glass, UARL 417, was chosen for research in making large quantities of fiber in monofilament form. Tests of these UARL 417 epoxy resin samples in comparison to similar composites made with the DuPont organic fiber, PRD-49-1, show that the UARL composites have a compressive strength 41/2 times higher and a specific compressive strength at least 21/2 times greater. Much of the research effort attempted to answer the question of why a given glass should have an impact strength superior to other glasses. No definitive answer to the question was found.

Bacon, J. F.↗

Study of recrystallization and devitrification of lunar glass

The technique of differential thermal analysis (DTA) was applied to the study of the Apollo 17 orange soil (74220,63) and the Apollo 16 glass coated anorthite (64455,21). These glasses show accentuated exotherms of strain relief in the annealing range which is indicative of rapid cooling. These are amenable to interpretation by comparison to the known history of synthetic glasses. Synthetic glasses were prepared whose similarity in behavior between the lunar glasses and their synthetic analogs is striking. Approximate rates of cooling of the lunar glasses were determined from comparative DTA of lunar and synthetic glasses and from the determination of the relation of strain relief in the annealing range to quench rate. At higher temperatures the glasses show exotherms of crystallization. The crystallization products associated with the exothermic reactions have been identified by X-ray diffraction and the surface morphologies developed by strain relief and crystallization have been characterized with scanning electron microscopy.

Ulrich, D. R.↗

Oxide glass processing in space

The experimental work performed thus far has resulted in the preparation of new glass compositions not reported heretofore in the open literature. Recent experiments which have resulted in the formation of 1/4-inch-diameter glass samples from two compositions, suggest that containerless melting and cooling as envisioned for space operations is of real technological significance. To date studies of space glasses have by choice been confined to oxide glasses only. It is felt that the applications for such glasses are more readily predictable than for the other materials, and that many of the principles that will evolve from a study of oxide glasses, which can be melted in air, permit a more direct approach to non-oxide materials in the future. The compositions being studied are all very simple in terms of traditional glass practices, none of them containing more than three major constituents. Future efforts should be concerned with more complex compositions, both to cover a broader range of optical properties and to enhance glass-forming tendencies.

Happe, R. A.↗

High modulus high temperature glass fibers

The search for a new high-modulus, high-temperature glass fiber involved the preparation of 500 glass compositions lying in 12 glass fields. These systems consisted primarily of low atomic number oxides and rare-earth oxides. Direct optical measurements of the kinetics of crystallization of the cordierite-rare earth system, for example, showed that the addition of rare-earth oxides decreased the rate of formation of cordierite crystals. Glass samples prepared from these systems proved that the rare-earth oxides made large specific contributions to the Young's modulus of the glasses. The best glasses have moduli greater than 21 million psi, the best glass fibers have moduli greater than 18 million psi, and the best glass fiber-epoxy resin composites have tensile strengths of 298,000 psi, compressive strengths of at least 220,000 psi, flexural strengths of 290,000 psi, and short-beam shear strengths of almost 17,000 psi.

Bacon, J. F.↗

Lunar glass compositions - Apollo 16 core sections 60002 and 60004

Approximately 500 glasses between 1 mm and 125 microns in size have been analyzed from fourteen samples from the Apollo 16 core sections 60002 and 60004. The majority of glasses have compositions comparable to those found in previous studies of lunar surface soils; however, two new and distinct glass compositions that are probably derived in part from mare material occur in the core samples. The major glass composition in all samples is that of Highland Basalt glass, but it also appears that high-K Fra Mauro Basalt (KREEP) glass is more common at the Apollo 16 site than was previously thought. The relative abundance of glasses within the core samples is random in distribution: each sample is characterized by a particular assemblage and distribution of the constituent glass compositions.

Meyer, H. O. A.↗