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At least 451 records · Page 25

Glass formulation and lab-scale testing of glasses designed for in-can Melter and in-container Vitrification of high-assay low-enriched uranium aqueous polishing Raffinate waste

Glasses were designed for processing a nuclear waste from aqueous polishing of high-assay low-enriched uranium using either In-Can Melter (ICM) or GeoMelt® In-Container Vitrification™ (ICV) technologies, which operate at temperatures of T p ≤ 1100 °C and T p ≤ 1450 °C, respectively. Due to the different operating conditions, the melt and glass properties were optimized differently for each technology. Each glass was designed to optimize for maximum waste loading while simultaneously satisfying processing (e.g., crystallization, viscosity, and conductivity) and product quality (e.g., durability, hazard characteristic, and crystal content) constraints. Here, the raffinate waste contains high nitric acid (4 M) and low total solids (9 g·L -1 ) concentrations. Feed preparation processes were tested to facilitate concentration and nitrate destruction/removal while controlling redox of the melter feed. A successful feed process including sugar addition and spray-drying was performed to generate an adequate melter feed for ICV processing.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Response of complex networks to compression: Ca, La, and Y aluminoborosilicate glasses formed from liquids at 1 to 3 GPa pressures

Aluminoborosilicate glasses containing relatively high field strength modifiers (Ca, La, and Y) have been compressed at pressures up to 3 GPa and near the glass transition temperature (T{sub g}) and quenched to room temperature at high pressure followed by decompression. Structural changes were quantified with high-resolution {sup 27}Al and {sup 11}B MAS nuclear magnetic resonance at 14.1–18.8 T. The changes with pressure in Al and B coordinations in the recovered samples are quite large with more than 50% decreases in tetrahedral aluminum ({sup IV}Al) and 200%-300% increases in tetrahedral boron ({sup IV}B). Glasses with higher field strength modifiers (La and Y) contain more high coordinated aluminum ({sup V,V} {sup I}Al) at all pressures studied. More high coordinated boron also correlates with higher field strength modifier if all three compositions are compared on an isothermal basis. Although lowering fictive temperature and increasing pressure both increase Al and B coordinations, our study shows that the actual mechanisms for structural changes are most probably different for temperature and pressure effects. Using a rough thermodynamic model to extrapolate to higher pressures, it appears that a simple non-bridging oxygen (NBO) consumption mechanism is not sufficient to convert all the aluminum to octahedral and boron to tetrahedral coordination, suggesting other mechanisms for structural changes could occur at high pressure as NBO becomes depleted.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Novel Rotating Flexure-Test Technique for Brittle Materials with Circular Geometries

The four-point bend test is one of the simplest and often the preferred flexural strength evaluation method for brittle materials. In this loading mode, fracture often initiates from a critical surface (or subsurface) flaw when subjected to a tensile stress state. However, if the critical flaw exists on the compression side of the test specimen, it may not activate to grow a crack and hence the resulting flexural strength will be higher than the true value. The goal of this study is to measure the true flexural strength of a solid or hollow cylindrical brittle specimen by ensuring that failure occurs at its weakest point by rotating along its longitudinal axis, thereby exposing and activating its critical surface flaw during a four-point bend test. A novel test fixture has been designed and fabricated, and the true flexural strengths of cylindrical brittle and quasi-brittle tubular specimens have been measured and compared to existing experimental data obtained through traditional four-point bend tests. In this work, experimental results showcase the orientation dependance on flexural strength for various materials. Additionally, similarities between experimental findings and those available in literature, including observations of fracture surfaces and relationships between surface roughness and material strength, are discussed.

36 MATERIALS SCIENCE↗

Effect of the tetrahedral groups on the optical properties of LaBRO{sub 5} (R = Si and Ge): A first-principles study

As potential candidates for deep-UV nonlinear optical (NLO) crystals, borosilicates and borogermanates, which contain NLO-active groups such as B-O, Si-O, and Ge-O groups, have fascinated many material scientists' research enthusiasm. In this paper, the electronic structures and optical properties of two isostructural noncentrosymmetric crystals LaBRO{sub 5} (R = Si and Ge) have been studied by the first-principles method. Combined with the analyses of the SHG-density and the localized electron-density difference, contributions of the constituent tetrahedra to the total NLO responses are investigated. Eventually, BO{sub 4} and GeO{sub 4} groups give nearly equal contributions to the SHG effect of LaBGeO{sub 5}, but for LaBSiO{sub 5}, SiO{sub 4} groups express stronger SHG response than that of BO{sub 4}. Such interesting conclusion is consistent with the distortion index analyses and dipole moment.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Adsorptive Capture of Iodide by Metal-Organic Framework from Off-Gas Condensate Simulate

Millions of gallons of liquid nuclear wastes generated due to nuclear weapon development during the Cold War are in tank storage at several Department of Energy (DOE) sites across the country. DOE is responsible for disposal of the tank nuclear waste and clean-up of the contaminated sites. These efforts are complex and challenging technically and are costly financially, with the predicted overall cost reaching $377 billion over the next few decades [1]. The current practice of nuclear waste treatment and tank closure is to separate high-level waste (HLW) and low-level waste (LLW) [2]. The HLW is then vitrified into a borosilicate-based glass waste form [3], while the LLW is immobilized into cementitious grout or vitrified into glass [4]. However, these treatment processes have met unsolved technical problems

Jiang, Junhua [Savannah River National Laboratory ↗

Preliminary ILAW Formulation Algorithm Description (Rev. 1)

The U.S. Department of Energy (DOE), Office of River Protection (ORP), has contracted with Bechtel National, Inc. (BNI) to design, construct, and commission the Hanford Tank Waste Treatment and Immobilization Plant (WTP) at the Hanford Site (DOE 2000). This plant is designed to operate for 40 years and treat roughly 50 million gallons of mixed hazardous high-level waste (HLW) stored in 177 underground tanks at the Hanford Site. The process involves separating the high-level and low-activity waste (LAW) fractions through filtration, leaching, Cs ion exchange, and precipitation. Each fraction will be separately vitrified into borosilicate waste glass. This report documents the initial algorithm for use by Hanford WTP in batching LAW and glass-forming chemicals (GFCs) in the LAW melter feed preparation vessel (MFPV). Algorithm inputs include the chemical analyses of the pretreated LAW in the concentrate receipt vessel (CRV), the volume of the MFPV heel, and the compositions of individual GFCs. In addition to these inputs, uncertainties in the LAW composition and processing parameters are included in the algorithm.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Simple Check Valves for Microfluidic Devices

A simple design concept for check valves has been adopted for microfluidic devices that consist mostly of (1) deformable fluorocarbon polymer membranes sandwiched between (2) borosilicate float glass wafers into which channels, valve seats, and holes have been etched. The first microfluidic devices in which these check valves are intended to be used are micro-capillary electrophoresis (microCE) devices undergoing development for use on Mars in detecting compounds indicative of life. In this application, it will be necessary to store some liquid samples in reservoirs in the devices for subsequent laboratory analysis, and check valves are needed to prevent cross-contamination of the samples. The simple check-valve design concept is also applicable to other microfluidic devices and to fluidic devices in general. These check valves are simplified microscopic versions of conventional rubber- flap check valves that are parts of numerous industrial and consumer products. These check valves are fabricated, not as separate components, but as integral parts of microfluidic devices. A check valve according to this concept consists of suitably shaped portions of a deformable membrane and the two glass wafers between which the membrane is sandwiched (see figure). The valve flap is formed by making an approximately semicircular cut in the membrane. The flap is centered over a hole in the lower glass wafer, through which hole the liquid in question is intended to flow upward into a wider hole, channel, or reservoir in the upper glass wafer. The radius of the cut exceeds the radius of the hole by an amount large enough to prevent settling of the flap into the hole. As in a conventional rubber-flap check valve, back pressure in the liquid pushes the flap against the valve seat (in this case, the valve seat is the adjacent surface of the lower glass wafer), thereby forming a seal that prevents backflow.

Willis, Peter A.↗

Slopes To Prevent Trapping of Bubbles in Microfluidic Channels

The idea of designing a microfluidic channel to slope upward along the direction of flow of the liquid in the channel has been conceived to help prevent trapping of gas bubbles in the channel. In the original application that gave rise to this idea, the microfluidic channels are parts of micro-capillary electrophoresis (microCE) devices undergoing development for use on Mars in detecting compounds indicative of life. It is necessary to prevent trapping of gas bubbles in these devices because uninterrupted liquid pathways are essential for sustaining the electrical conduction and flows that are essential for CE. The idea is also applicable to microfluidic devices that may be developed for similar terrestrial microCE biotechnological applications or other terrestrial applications in which trapping of bubbles in microfluidic channels cannot be tolerated. A typical microCE device in the original application includes, among other things, multiple layers of borosilicate float glass wafers. Microfluidic channels are formed in the wafers, typically by use of wet chemical etching. The figure presents a simplified cross section of part of such a device in which the CE channel is formed in the lowermost wafer (denoted the channel wafer) and, according to the present innovation, slopes upward into a via hole in another wafer (denoted the manifold wafer) lying immediately above the channel wafer. Another feature of the present innovation is that the via hole in the manifold wafer is made to taper to a wider opening at the top to further reduce the tendency to trap bubbles. At the time of reporting the information for this article, an effort to identify an optimum technique for forming the slope and the taper was in progress. Of the techniques considered thus far, the one considered to be most promising is precision milling by use of femtosecond laser pulses. Other similar techniques that may work equally well are precision milling using a focused ion beam, or a small diamond-tipped drill bit.

Greer, Harold E.↗

Low Melting Temperature Glass for Immobilisation of Contaminated Zeolitic Ion Exchangers from Fukushima - 16494

The clean-up of the Fukushima Daiichi site continues to generate large volumes of spent adsorbents which need to be disposed of permanently, one of the candidates is a low temperature immobilisation process to avoid volatilising radioactive Cs and Sr species. To this end an immobilisation process with a maximum temperature of 600 deg. C was developed by sintering model waste with glass frit to form a dense Glass Composite Material (GCM) wasteform. A zeolitic model wasteform, chabazite, was sintered with two lead-based glass compositions, lead borosilicate (PBS) and a lead borate (PB) glass composition, at a maximum temperature of 600 deg. C. Full encapsulation of the zeolitic wasteform was achieved for waste-loadings up to 40 wt.% in PBS and 30 wt.% in PB in all cases, with both GCM systems showing foaming. PBS GCM formation was successful at a maximum of 600 deg. C, while the PB GCM formation was shown to be possible at a maximum temperature of 550 deg. C. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Effect of iron redox ratio on the structures of boroaluminosilicate glasses

Iron oxide is commonly found in natural or industrial glass compositions and can exist as ferrous (Fe 2+ ) or ferric (Fe 3+ ) species, with their ratios depending on glass composition, temperature, pressure and the redox reactions during the glass forming process. The iron redox ratio plays an important role on silicate glass structures and consequently various properties. This work aims to study the effect of iron oxide, and particularly the iron redox ratio, on the structures of borosilicate and boroaluminosilicate glasses using molecular dynamics simulations with newly developed iron potential parameters that are compatible with the borosilicate potentials. The results provide detailed cation coordination states of both iron species and the effect of redox ratio on boron coordination and other structural features. Particularly, competition for charge compensating modifier cations (such as Na + ) among the fourfold-coordinated cations such as B 3+ , Al 3+ , and Fe 3+ is investigated by calculating the cation–cation pair distribution functions and coordination preferential ratios. The results show that the trivalent ferric ions, with a shorter Fe–O bond distance and better defined first coordiation shell with mainly four-fold coordination, act as a glass former whereas the divalent ferrous ions mainly play the role of glass modifier. The ferrous/ferric ratio (Fe 2+ /Fe 3+ ) was found to affect the glass chemistry and hence glass properties by regulating the amount of four-coordinated boron, the fraction of non-briding oxygen and other features. Finally, the results are compared with available experimental data to gain insights of the complex structures and charge compensation schemes of the glass system.

36 MATERIALS SCIENCE↗

Ruthenium solubility and its impact on the crystallization behavior and electrical conductivity of MoO 3 -containing borosilicate-based model high-level nuclear waste glasses

The present study focuses on investigating the solubility of RuO 2 in a borosilicate-based model high-level waste glass and understanding its impact on the crystallization behavior and electrical conductivity of the resulting vitrified waste forms. The solubility limit of RuO 2 in the investigated glass composition has been determined to be 460 ppm by weight. The higher concentration of RuO 2 results in sub-micron sized Ru-rich inclusions in the glassy matrix, which eventually agglomerate to form needle-like and polyhedral RuO 2 crystals. It is observed that RuO 2 selectively promotes the crystallization of the rare-earth apatite phase over the powellite phase. The as-synthesized RuO 2 -containing glasses exhibit semiconducting behavior with a similar level of electrical conductivity below the glass transition. Here, the percolation of non-uniformly distributed RuO 2 inclusions may result in a formation of short-range low-resistive conduction pathways in the host glass matrix leading to an apparent metallic-like behavior of selected thin samples with the highest ruthenium content.

36 MATERIALS SCIENCE↗

Corrosion behavior of Monofrax K-3 refractory in borosilicate-based model low activity waste glass melts

Owing to its good chemical and thermal durabilities at high temperatures, Monofrax K-3 refractory is widely used in nuclear waste vitrification as a lining material in melting vessels. However, the corrosion of K-3 refractory during the vitrification of nuclear waste is a serious problem because it affects the melter's safety, performance, and lifetime. Therefore, in the present study, we have focused on unearthing the impact of glass network formers, such as SiO 2 , B 2 O 3 , and Al 2 O 3 , in a model nuclear waste glass composition on the corrosion of Monofrax K-3 refractory. The corrosion tests have been performed per ASTM C621 at 1150°C for 5 days. The dimensional measurements on corroded K-3 refractory suggest that Al 2 O 3 and SiO 2 tend to reduce the refractory corrosion (neck loss), with the effect of Al 2 O 3 being significant. A corroded region on the K-3 refractory at the melt–refractory interface is observed. The corrosion occurs via a coupling of the melt infiltration induced by a capillary effect and the dissolution of Al, Mg, and Fe components from K-3 into the melt through chemical reactions. A Cr-rich layer is retained on the glass contact surface of the corroded K-3 refractory.

36 MATERIALS SCIENCE↗

Fluorine Limits and Impacts in High-Level Waste Glass Compositions

The impact of elevated fluorine (F) content on Hanford high-level waste (HLW) glasses has not previously been studied in detail. This effort represents the first systematic study to determine what F concentration limits should be used for the design of alkali-borosilicate-based Hanford Waste Treatment and Immobilization Plant (WTP) HLW glasses, and to document the technical basis for that limit. If alkali borosilicate glass made from Hanford HLW can accommodate a large amount of F, the large capital costs for complex sludge washing facilities may be avoided, as would much of the operational costs and negative schedule impacts associated with handling the large volumes of water required to dissolve these salts. In order to determine a limit for F in likely HLW glass compositions, an evaluation was conducted on glasses with F ≤ 0.90 mass% from previous nuclear waste glass studies. The collected dataset contains 239 glasses (232 HLW glasses and 7 LAW glasses) including 109 glasses with 0.9 ≤ F mass% ≤ 2.5, 116 with 2.5 < F mass% ≤ 8.0, and 14 with F mass% ≥ 8 (max. F mass% = 17.42). The collected composition and property data were analyzed to determine the basis for the F tolerance, i.e. the maximum F concentration that can be processed without potential issues. Fluorine volatility, product consistency test (PCT) response, liquidus temperature (T L ), glass melt viscosity, and crystallinity have been investigated. No limits for F concentration can be made based on F volatility, T L , or glass melt viscosity, because the data show that high F in glasses do not indicate, with high probability, being restricted by those property constrains. However, crystallinity and PCT response were used to estimate the F tolerance. The results show that glasses with high F (≥ 0.90 mass%) are more likely to form large fractions of F-containing crystal phases which may increase PCT responses, i.e. decrease the glass durability. Based on the results of crystallinity and PCT data, the F tolerance of 4.5 mass% is estimated. There is no evidence of other glass components, such as calcium oxides and alkali metal oxides have combined impacts with F on the glass properties. Overall, the available high-F glass data is limited, especially in the designed HLW glass composition regions. Future work on formulation and testing of HLW glasses with F ≥ 0.9 mass% will close the data gaps and expand operational flexibility with respect to the fluoride tolerances. Volatility of F from melters and corrosion of materials in contact with glass melts are important for processing of high-F wastes; yet no test data are currently available. It is recommended tests be conducted to address these two potential issues.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

New techniques for fusion bonding and replication for large glass reflectors

Lightweight, space-deployable glass honeycomb telescope primary mirror structures are produced by a novel method which involves the heating to softening temperature of many borosilicate or silica glass tube sections that are packed to form a honeycomb matrix and filled with a high expansion coefficient refractory sand. The close packed tubes yield a hexagonal-cell honeycomb. Attention is given to the results of an experiment in which a highly refractory master was used to shape a honeycomb of less refractory glass, employing a 1-micron thick, vacuum-deposited gold coating as a parting layer between the two.

Angel, J. R. P.↗

Efficient neutron production from sub-nanosecond laser pulse accelerating deuterons on target front side

Neutron-producing experiments have been carried out on the Prague Asterix Laser System. At the fundamental wavelength of 1.315 μm, the laser pulse of a 600 J energy and 300 ps duration was focused on a thick deuterated-polyethylene target. Neutron yields reached (4.1 ± 0.8) × 10{sup 8} at the peak intensity of ≈3 × 10{sup 16 }W/cm{sup 2}. A more detailed analysis of neutron time-of-flight signals showed that a significant fraction of neutron yields was produced both by the {sup 2}H(d,n){sup 3}He reaction and by other neutron-producing reactions. Neutron energies together with delayed neutron and gamma emission showed that MeV deuterons escaped from a laser-produced plasma and interacted ≈50 ns later with a borosilicate blast-shield glass. In order to increase DD neutron yields and to characterize deuteron beams via nuclear reactions, a secondary deuterated polyethylene target was used in a pitcher-catcher scheme at the target front side. In this experimental arrangement, the neutron yield reached (2.0 ± 0.5) × 10{sup 9} with the peak neutron fluence of (2.5 ± 0.5) × 10{sup 8 }n/sr. From the neutron yield, it was calculated that the secondary target was bombarded by 2 × 10{sup 14} deuterons in the 0.5–2.0 MeV energy range. The neutron yield of 2 × 10{sup 9} at the laser energy of 600 J implied the production efficiency of 3 × 10{sup 6 }n/J. A very important result is that the efficient neutron production was achieved with the low contrast, sub-nanosecond laser pulse of the intensity of 10{sup 16 }W/cm{sup 2}. The latter parameters can be achieved in a rep-rate mode more easily than ultra-high intensities and contrasts.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Vacuum Strength of Two Candidate Glasses for a Space Observatory

The strengths of two candidate glass types for use in a space observatory were measured. Samples of ultra-low expansion glass (ULE) and borosilicate (Pyrex) were tested in air and in vacuum at room temperature (20 C) and in vacuum after being heated to 200 C. Both glasses tested in vacuum showed an increase in strength over those tested in air. However, there was no statistical difference between the strength of samples tested in vacuum at room temperature and those tested in vacuum after heating to 200 C.

Manning, T. a.↗

Glass Compositions and Properties of Enhanced Waste Glass with High Alumina Content for High-Level Waste

This report documents the work performed to collect critical property data on high-level waste (HLW) glasses with high alumina content. This report covers the experimental results of thermal, physical, chemical, and electrical properties of 46 high alumina (15 to 30 wt%) borosilicate waste-glass compositions with one duplicate for a total of 47 glasses. These experimental results are essential for developing property-composition models for the future operation of the Waste Treatment and Immobilization Plant (WTP) currently under construction at the Hanford Site in Richland, Washington. Pacific Northwest National Laboratory (PNNL) was requested by the U.S. Department of Energy’s Office of River Protection to provide expert evaluation and experimental work in support of the vitrification technology development program.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Vacuum Strength of Two Candidate Glasses for a Space Observatory

The strengths of two candidate glass types for use in a space observatory were measured. Samples of ultra-low expansion glass (ULE) and borosilicate (Pyrex) were tested in air and in vacuum at room temperature (20 degrees C) and in vacuum after being heated to 200 degrees C. Both glasses tested in vacuum showed a significant increase in strength over those tested in air. However, there was no statistical difference between the strength of samples tested in vacuum at room temperature and those tested in vacuum after heating to 200 degrees C.

Manning, Timothy Andrew↗