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At least 613 records · Page 34

Curved lattices of crystals formed in glass

Atomic arrangements systemically deviating from the classic definition of single crystal lattice have been known in spherulites for over a century. However, their unusual curved lattice could not be exploited for useful applications due to their uncontrolled orientations and lattice curvatures. Heating of glass with focused laser, electron or x-ray beam has yielded well-defined conditions for forming single crystal architectures. Furthermore, by controlling the conditions of irradiation and confinement by glass matrix for a given system, desired lattice curvature (rotations and twists) can be reproducibly introduced into these crystals. Here, we review several examples of laser-fabricated crystals with curved lattices in glass using a common coordinate system, which helps to establish correlations between processing parameters and lattice curvature. Here, the mechanisms of lattice deformations are discussed along with potential methods to control the orientation of the initially formed seeds that determine the lattice orientations of the end product. The recent developments of laser-fabrication of single crystal architecture in glass with controlled heating profile appear promising for engineering the curvature of their lattices.

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Major to trace element imaging and analysis of iron age glasses using stage scanning in the analytical dual beam microscope (tandem)

Dark and clear silicate glasses formed during an iron age vitrification event ≈ 1500 years ago at the Broborg hillfort near Uppsala, Sweden have been analyzed using a scanning electron microscope equipped with a micro-X-ray fluorescence (μXRF) spectrometer. Correlated µXRF and electron beam-induced energy dispersive spectrometry (EDS) X-ray maps were collected via stage-scanning at constant velocity. This coupled procedure represents a new approach for the cultural heritage community to conduct analytical studies of archaeometric specimens composed of metal, ceramic, or mixed inorganic/organic materials, where major and trace element compositions are registered in space for areas up to the centimeter-length scale at micrometer-scale resolution. Overview images were used to select areas for EDS beam scan maps correlated with multispectral cathodoluminescence (CL) imaging and co-located quantitative EDS and μXRF point analysis. Fe, Ca, Mg, Ti, P, Mn, Zr, Zn, and Y are enriched in the dark glass, while Si, Al, K, Na, Ba, Sr, Rb, and Ga are enriched in the clear glass. Unmelted material is comprised predominately of quartz (SiO 2 ) along with trace apatite (Ca 5 (PO 4 ) 3 [Cl,OH]) and zircon (ZrSiO 4 ). Multivariate statistical analysis was used to measure the area fractions of high variance components while lower variance components represented phase mixtures. Differences between calculated melt viscosities for the glass compositions are consistent with field and laboratory observations. Coupled large area EDS and μXRF imaging shows significant promise for informed selection of higher spatial resolution and higher sensitivity follow-up studies, e.g., those performed using synchrotron analysis.

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Summary Report for the Analysis of the Sludge Batch 7b (Macrobatch 9) DWPF Pour Stream Glass Sample for Canister S04023

In order to comply with the Defense Waste Processing Facility (DWPF) Waste Form Compliance Plan for Sludge Batch 7b, Savannah River National Laboratory (SRNL) personnel characterized the Defense Waste Processing Facility (DWPF) pour stream (PS) glass sample collected while filling canister S04023. This report summarizes the results of the compositional analysis for reportable oxides and radionuclides and the normalized Product Consistency Test (PCT) results. The PCT responses indicate that the DWPF produced glass that is significantly more durable than the Environmental Assessment glass. Results and further details are documented in SRNL-STI-2013-00462, Revision 1 “Analysis of the DWPF Sludge Batch 7b (Macrobatch 9) Pour Stream Glass Sample.”

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Composition Measurements of the LAW ALG Glasses

This report provides the results from the chemical analyses of glass compositions for the Low-Activity Waste Algorithm study glasses, a series of simulated nuclear waste glasses designed and fabricated at Pacific Northwest National Laboratory. These data will be used in the development, validation, and implementation of enhanced property/composition models for waste glass vitrification at Hanford.

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Product Consistency Test Results for the LAW ALG Glasses

This report provides the results of the Product Consistency Test leachates from the Low-Activity Waste Algorithm glasses, a series of simulated nuclear waste glasses designed and fabricated at the Pacific Northwest National Laboratory. The series included quenched and canister centerline cooled versions of the glasses. These data will be used in the development, validation, and implementation of enhanced property/composition models for waste glass vitrification at Hanford.

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Nepheline Crystallization Studies and the Structural Integrity of the Residual (SIR) - FY 2022 Study Glasses

In FY22 a set of 367 HLW glasses with compositions representative of the Waste Treatment and Immobilization Plant (WTP) processing region were aggregated and analyzed with the Structural Integrity of the Residual (SIR) model developed by the Savannah River National Laboratory (SRNL). An additional 12 glasses targeting 27 – 37 wt % alumina (in glass) and at waste loadings up to ~70 wt % were fabricated and added to the database. Collectively, this data set was analyzed with regression statistics and partitioning functions to reveal correlations between boron release and the chemical composition. FY22 results indicate that the SIR theoretical alkali-silicate precipitation term, Al 2 O 3 and B 2 O 3 concentration, and SIR computed non-bridging oxygen are significant predictors of chemical durability. A statistical model using the SIR parameters was shown to have greater overall accuracy than the nepheline discriminator model while maintaining false predictions of pour durability below 1%. In FY23, we will continue this work to focus on refining the SIR with glass compositions that challenge the SIR correlation terms, namely the theoretical crystalline precipitation and non-bridging oxygen terms.

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Analysis of DWPF Sludge Batch 6 (Macrobatch 7) Pour Stream Glass Samples

The Defense Waste Processing Facility (DWPF) began processing Sludge Batch 6 (SB6), also referred to as Macrobatch 7 (MB7), in June 2010. SB6 is a blend of the heel of Tank 40 from Sludge Batch 5 (SB5), H-Canyon Np transfers and SB6 that was transferred to Tank 40 from Tank 51. SB6 was processed using Frit 418. During processing of each sludge batch, the DWPF is required to take at least one glass sample to meet the objectives of the Glass Product Control Program and to complete the necessary Production Records so that the final glass product may be disposed of at a Federal Repository. Four pour stream glass samples and two Melter Feed Tank (MFT) slurry samples were collected while processing SB6. The samples were transferred to the Savannah River National Laboratory (SRNL) where they were analyzed.

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Time-Temperature-Transformation (TTT) Diagram for a Sludge Batch 9 Glass Composition Based on Coupled-Operation with the Salt Waste Processing Facility

The amorphous structure of a glass waste form has the potential to rearrange into crystalline phases at temperatures between the liquidus temperature and the glass transition temperature (Tg). Certain phases that can form will be detrimental to the durability of the glass and it is important to know the conditions that promote devitrification. The canister-centerline-cooling (CCC) profile is used to replicate the area within the center of the Defense Waste Processing Facility (DWPF) canister with the slowest cooling during the initial cool down after pouring, which has the greatest potential for crystallization. Other time-temperature conditions that cause significant changes in either phase structure or phase composition are identified by a time-temperature-transformation (TTT) study. The phase stability of a waste form must be determined as a part of the Waste Acceptance Product Specifications (WAPS) if it is to eventually be stored in a geologic repository. This requires the creation of a TTT diagram and analysis of the Tg, as defined by the Department of Energy (DOE). The previous TTT study for a DWPF glass waste form was completed in 2010 prior to coupled operation with the Salt Waste Processing Facility (SWPF). SWPF transfers two high activity waste streams to DWPF for vitrification: a cesium-containing strip effluent and a stream containing monosodium titanate/sludge solids. These SWPF streams were first transferred to DWPF for vitrification during Sludge Batch 9 (SB9) in 2021. The impact of these SWPF streams on crystallization behavior was not determined in previous studies and the need for data to satisfy WAPS Specification 1.4 for SB9 was identified.

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The Origin of Anomalous Density Behavior of Silica Glass

The anomalous density–temperature relationship of vitreous silica with low hydroxyl content is explained by the formation of medium-range ordering structure in the glass transition process. The ordered medium-range structure has the shape of a “nanoflake” and consists of two layers of SiO 4 tetrahedra, bonded by O atoms located in the middle of the structure. The nanoflakes interact with their surrounding structures through both covalent chemical bonds and van der Waals bonds. In the formation of the van der Waals bonds, the orientation of SiO 4 tetrahedra can change, which results in an increase in distance between the nanoflakes and their surrounding structures. Thus, there is a slight volume enlargement associated with the formation of nanoflakes. Since the nanoflakes’ formation starts at a temperature near 1480 °C, and the population of the nanoflakes grows continuously as temperature decreases until about 950 °C, the bulk volume of silica glass increases in the temperature range from about 1480 °C to 950 °C. Therefore, the density anomaly of silica glass can be explained as a byproduct of forming of medium-range ordering structure in the silica glass transition.

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Progress in Understanding the Origins of Excellent Corrosion Resistance in Metallic Alloys: From Binary Polycrystalline Alloys to Metallic Glasses and High Entropy Alloys

Some of the factors responsible for good corrosion resistance of select polycrystalline and emerging alloys in chloride solutions are discussed with a goal of providing some perspectives on the current status and future directions. Traditional metallic glass alloys, single phase high entropy alloys (HEAs), early metallic glasses, and high entropy metallic glasses are all emerging corrosion-resistant alloys (CRAs) that utilize traditional strategies for improved corrosion resistance as well as take advantage of some other novel beneficial attributes. These materials enjoy many degrees of freedom as far as choice of both composition and structure, providing great flexibility in the pursuit of superior corrosion resistance. The new materials depart from classical solvent-solute type polycrystalline binary or ternary alloys. Thus, such emerging materials provide significant opportunities to achieve even greater improvements in corrosion resistance in harsh environments. Several examples of the unique corrosion properties of selected materials in the context of modern theories of corrosion are discussed herein. Discussion is restricted to solid-solution binary or ternary polycrystalline alloys, several metallic glass alloys, and single phase HEAs. A common feature of many CRAs is that composition and microstructure often affect both passivity and resistance to localized corrosion that can be divided into initiation, stabilization, and propagation stages. Enormous complexities in protective oxide structures and chemistries and the large number of combinatorial possibilities in newer materials such as HEAs preclude trial-and-error approaches and perhaps even combinatorial experimental design. Computational materials methodologies will be required in the search for new corrosion-resistant alloys in these material classes. The search must consider the best scientific insights available regarding how major and minor alloy additions, as well as various microstructural attributes, contribute to corrosion mitigation. Additional scientific insights, as they emerge, will enable choices beyond the reliance on high concentrations of alloying elements that are known to affect passivity breakdown and pit stabilization. A challenge is to connect the “basic attributes” of an alloy with its properties. The strength of this connection will likely require new scientific principles enabling deep multiphysics insights in order to link feature(s) such as composition and metallurgical phases to the desired corrosion properties. Application of data informatics will likely also play a role given the plethora of variables that are important in corrosion and the difficulty in assessing all relationships. Here, the opportunity exists to accelerate the design of emerging materials for high corrosion resistance.

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Chemistry and particle track studies of Apollo 14 glasses.

The abundance and the composition of Apollo 14 glasses have been studied. Glass particles were analyzed for Si, Ti, Al, Fe, Mn, Mg, Na, and K by electron microprobe analysis. The refractive indices of 26 particles were determined by the oil immersion method. Track analyses have been carried out in order to determine the uranium content and the radiation history of glass particles. The proper identification of galactic and solar flare nuclei tracks makes it possible to estimated residence times of the glass particles in the top layer of the lunar soil.

Glass, B. P.↗

Major element compositions of Luna 20 glass particles.

Major element analyses of nineteen Luna 20 glass particles indicate that most of the Luna 20 glasses have Al2O3 contents greater than 21 wt % and compositions similar to Apollo 16 and Luna 20 rocks and soils. Three of the glass particles have low Al2O3 (less than 13 wt %) and high FeO (greater than 18 wt %) contents and were probably derived from one of the adjacent maria. The low glass content of the Luna 20 soil indicates that it is relatively young or less mature than most mare soils that have been studied.

Glass, B. P.↗

Sintering of lunar glass and basalt

Experiments were conducted to study the sintering behavior of glass and basalt lunar soil simulants. The degree of sintering was assessed by compressive strength testing and microanalysis. Both crushed glass and basalt sinter significantly at 1000 C, with the basalt attaining its maximum strength at 1100 C. Initial sintering occurs in less than 15 min, and the degree of sintering does not increase significantly with time after about 30 min. Glass sinters more readily than crystalline material. Sintering and devitrification both occur on a time scale of minutes in the heated glass, but sintering is apparently more rapid. The processes of sintering and oxygen release by hydrogen reduction of lunar soil are synergistic, and could be combined to produce two extremely useful products at a lunar base.

Compressive strength↗

(abstract) Undercooling Studies of the Bulk Metallic Glass Forming Zr(sub 41.2)Ti(sub 13.8)Cu(sub 12.5)Ni(sub 10.0)Be(sub 22.5) Alloy During Containerless Electrostatic Levitation Processing

Bulk glass forming metallic alloys have long been desired for technological applications and for investigation into liquid undercooling, solidification processes, and thermophysical properties. A glass forming alloy Zr(sub 41.2)Ti(sub 13.8)Cu(sub 12.5)Ni(sub 10.0)Be(sub 22.5) was used to investigate the thermal treatments affecting undercooling and vitrification. The experiments were performed using the high temperature high vacuum electrostatic levitator at JPL. A sample approximately 3 mm in diameter was melted, superheated, undercooled, and solidified while levitated in high vacuum. The results show that when the sample was held above its melting temperature for a sufficient period of time to dissolve oxides and then cooled faster than a critical cooling rate, it undercooled to the glass transition temperature, T(sub g), and formed a glassy alloy. The required critical cooling rate for metallic glass formation was obtained to be between 0.9 K per second and 1.2 K per second for the 42.4 mg sample.

levitation vitrification↗

Mechanical Properties of a High Lead Glass Used in the Mars Organic Molecule Analyzer

The elastic constants, strength, fracture toughness, slow crack growth parameters, and mirror constant of a high lead glass supplied as tubes and funnels were measured using ASTM International (formerly ASTM, American Society for Testing and Materials) methods and modifications thereof. The material exhibits lower Young's modulus and slow crack growth exponent as compared to soda-lime silica glass. Highly modified glasses exhibit lower fracture toughness and slow crack growth exponent than high purity glasses such as fused silica.

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Observations in Fracture Toughness Testing of Glasses and Optical Ceramics

Fracture toughness is a critical structural design parameter and an excellent metrics to rank materials. Itdetermines fracture strength by way of the flaws, both inherent and induced, and defines the endpoint of the slow crackgrowth curve. The fracture toughness of structural and optical ceramics, and glasses as measured by several techniques is compared. When good metrology is employed, the results are very comparable with two exceptions: materials exhibiting crack growth resistance and those with a low SCG exponents. For materials with R-curves, the result is a function of extension and can be minimized with short cracks. For materials with low SCG exponents, such as glasses, elimination of the corrosive media andor increasing the stress intensity rate minimizes effects. A summary of values is given, and it appears that highly modified glasses exhibit lower fracture toughness and slow crack growth exponent than high purity glasses such as fused silica.

fracture toughness↗

Computationally-Aided Design of a Small-Scale Radioactive Waste Glass Melter

To provide mission support to the Hanford Waste Immobilization and Treatment Plant for the vitrification of legacy nuclear tank waste, a reduced-scale vitrification pilot system is being designed to process simulated and actual radioactive tank wastes. The tank waste will be separated into high-level waste (HLW) and low-activity waste (LAW) fractions, where the majority by mass (~90%) is LAW and by activity (>95%) is HLW. The first tank waste to be processed at the WTP will be LAW. Since Hanford tank waste and the resultant melter feed compositions are known to vary widely, pilot-scale operations are essential to identify potential problems, provide needed data, confirm assumptions, and determine impacts to full-scale melters and off-gas systems from these different feeds. In addition, the reduced-scale melter system must be capable of quickly providing results to operations without the typically high costs of radioactive operations and provide an engineering platform in close proximity to local operations staff. The objective is to produce similar process conditions to those encountered in the full-scale LAW melters and minimize the volume of radioactive waste necessary for the evaluations. To this end, melter design features are being explored to increase production without significantly increasing surface area, melter glass volumes or compromising data quality. In support of these objectives, a set of computational fluid dynamic models have been developed to provide insight into the flow patterns within these small melters and evaluate design features to increase production without significantly increasing glass inventory. Computed velocities were evaluated at the interface between the cold cap and the molten glass pool and within the bulk glass pool. A method was developed to correlate results to an estimated melt rate and down-select design features that produce the highest gains.

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Computationally Aided Design of a Small-Scale Waste-Glass Melter - 20452

To provide mission support to the WTP for the vitrification of legacy nuclear tank waste at the Hanford site, a reduced-scale vitrification pilot system is being designed to process simulated and actual radioactive tank wastes. The waste stored in underground tanks will be separated into HLW and LAW fractions, where the majority is LAW by mass (approximately 90%) and HLW by activity (greater than 95%). The first tank waste to be processed at the WTP will be LAW. Because Hanford tank waste and the resultant melter feed compositions are known to vary widely, pilot-scale operations are essential to identify potential problems, provide needed data, confirm assumptions, and determine impacts to full-scale melters and off-gas systems from these different feeds. In addition, the reduced-scale melter system must be capable of quickly providing results to operations without the typically high cost of full-scale radioactive operations and to provide an engineering platform in close proximity to local operations staff. The objectives of this computational modeling effort are to produce process conditions like those encountered in the WTP LAW melters and to minimize the volume of radioactive waste necessary for the evaluations. To this end, melter design features are being explored to increase production without significantly increasing surface area or melter-glass volumes or compromising data quality. In support of these objectives, a set of computational fluid dynamic models was developed to provide insight into the flow patterns within these small melters and evaluate design features to increase production without significantly increasing glass inventory. Computed velocities were evaluated at the interface between the cold cap and the molten-glass pool and within the bulk-glass pool. Since melt rate correlates with the velocity underneath the cold cap, this information can be used to select design features that produce the highest gains. (authors)

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