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482 records · Page 27

Effect of chlorine and chromium on sulfur solubility in low-activity waste glass

According to an empirical sulfur solubility model developed from over 200 simulated low-activity waste (LAW) glasses, chlorine and chromium show strong effects on lowering sulfur solubility in glass. This work was aimed at understanding the mechanism behind the negative effect of chlorine and chromium on sulfur solubility. A simplified LAW glass was prepared and saturated by sodium sulfate, sodium chloride, and sodium chromate salts as single components and as mixtures with different ratios at 25 mol%, 50 mol%, and 75 mol% of sulfate mixed with chloride or chromate. A crucible-scale salt-saturation was performed by mixing the crushed glass powder with an excess amount of salts, melting at 1150 °C for one hour, and quenching. Three mixing-melting-quenching cycles were applied to determine saturation concentrations of sulfur, chromium, and chlorine incorporated into the simplified LAW glass. The glass compositions were analyzed by inductively coupled plasma–atomic emission spectroscopy, ion chromatography, and X-ray emission spectroscopy. It is proposed that the negative effect of chlorine and chromium on sulfur solubility can be explained based on the simple hypothesis that sulfur, chlorine, and chromium are present in the glass as anions competing for the voids or interstitial sites of the glass matrix, and that their solubility strongly depends on the effective size of corresponding anions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Conversion of Nuclear Waste to Molten Glass: Cold-Cap Reactions in Crucible Tests

The feed-to-glass conversion, which comprises complex chemical reactions and phase transitions, occurs in the cold-cap zone during nuclear waste vitrification. Knowledge of the chemistry and physics of feed-to-glass conversion will help us control the conversion path by changing the melter feed makeup to maximize the glass production rate. To investigate the conversion process, we analyzed heat-treated samples of a simulated high-level waste feed using X-ray diffraction, electron probe microanalysis – wavelength dispersive X-ray spectroscopy, leaching tests, and residual anion analysis. Feed dehydration, gas evolution, and borate phase formation occurred at temperatures below 700 °C before the emerging glass-forming melt was completely connected. Above 800 °C, intermediate aluminosilicate phases and quartz particles were gradually dissolving in the continuous borosilicate melt, which expanded into transient foam. Knowledge of the chemistry and physics of feed-to-glass conversion will help us control the conversion path by changing the melter feed makeup to maximize the glass production rate.

Cold-cap↗

Crucible Melter Simulation in Nek5000

Nuclear tank waste at the Hanford site is slated for vitrification in large scale refractory-lined melters to transform it into a stable borosilicate waste form suitable for long-term storage or disposal. Molten glass corrodes the refractory lining over time at a rate correlated to the velocity of molten glass against the refractory-lined wall. To properly design a melter and plan for maintenance, it is necessary to accurately model the glass flow and find the correlation between flow velocity and corrosion rate. This modeling was started in STAR-CCM+ CFD software and is being continued in Nek5000 for its fast-running and quick turnaround code. This poster explains the basic process of reconstructing the geometry, fluid properties, and heating of test melters in Nek5000. The geometry is imported from a mesh file and boundary conditions assigned based on surface IDs. The fluid properties are set in the .par and .usr case files. The heating of the actual crucibles in joule heating with electrodes but simulated in Nek5000 with a volumetric heat source term. This volumetric heat source is fit to the actual heating profile with piecewise polynomials and exponentials. Basic results and verification methods are explained in the poster, as well as further work that must be done to complete modeling.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Atomically Bonded Transparent Superhydrophobic Coatings

Maintaining clarity and avoiding the accumulation of water and dirt on optically transparent surfaces such as US military vehicle windshields, viewports, periscope optical head windows, and electronic equipment cover glasses are critical to providing a high level of visibility, improved survivability, and much-needed safety for warfighters in the field. Through a combination of physical vapor deposition techniques and the exploitation of metastable phase separation in low-alkali borosilicate, a novel technology was developed for the fabrication of optically transparent, porous nanostructured silica thin film coatings that are strongly bonded to glass platforms. The nanotextured films, initially structurally superhydrophilic, exhibit superior superhydrophobicity, hence antisoiling ability, following a simple but robust modification in surface chemistry. The surfaces yield water droplet contact angles as high as 172°. Moreover, the nanostructured nature of these coatings provides increased light scattering in the UV regime and reduced reflectivity (i.e., enhanced transmission) over a broad range of the visible spectrum. In addition to these functionalities, the coatings exhibit superior mechanical resistance to abrasion and are thermally stable to temperatures approaching 500°C. The overall process technology relies on industry standard equipment and inherently scalable manufacturing processes and demands only nontoxic, naturally abundant, and inexpensive base materials. Such coatings, applied to the optical components of current and future combat equipment and military vehicles will provide a significant strategic advantage for warfighters. The inherent self-cleaning properties of such superhydrophobic coatings will also mitigate biofouling of optical windows exposed to high-humidity conditions and can help decrease repair/replacement costs, reduce maintenance, and increase readiness by limiting equipment downtime.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Optical Evaluation of Digital Micromirror Devices (DMDs) with UV-Grade Fused Silica, Sapphire, and Magnesium Fluoride Windows and Longterm Reflectance of Bare Devices

Digital micromirror devices (DMDs) are commercial micro-electromechanical systems, consisting of millions of mirrors which can be individually addressed and tilted into one of two states (+/-12deg). These devices were developed to create binary patterns in video projectors, in the visible range. Commercially available DMDs are hermetically sealed and extremely reliable. Recently, DMDs have been identified as an alternative to microshutter arrays for space-based multi-object spectrometers (MOS). Specifically, the MOS at the heart of the proposed Galactic Evolution Spectroscopic Explorer (GESE) uses the DMD as a reprogrammable slit mask. Unfortunately, the protective borosilicate windows limit the use of DMDs in the UV and IR regimes, where the glass has insufficient throughput. In this work, we present our efforts to replace standard DMD windows with custom windows made from UV-grade fused silica, low-absorption optical sapphire (LAOS) and magnesium fluoride (MgF2). We present transmission measurements of the antireflection coated windows and the reflectance of bare (window removed) DMDs. Furthermore, we investigated the long-term stability of the DMD reflectance and experiments for coating DMD active area with a layer of pure aluminum (Al) to boost reflectance performance in the UV spectral range (200−400 nm).

reflectance↗

Optical Evaluation of DMDs with UV-Grade FS, Sapphire, MgF2 Windows and Reflectance of Bare Devices

Digital Micro-mirror Devices (DMDs) have been identified as an alternative to microshutter arrays for space-based multi-object spectrometers (MOS). Specifically, the MOS at the heart of a proposed Galactic Evolution Spectroscopic Explorer (GESE) that uses the DMD as a reprogrammable slit mask. Unfortunately, the protective borosilicate windows limit the use of DMDs in the UV and IR regimes, where the glass has insufficient throughput. In this work, we present our efforts to replace standard DMD windows with custom windows made from UV-grade fused silica, Low Absorption Optical Sapphire (LAOS) and magnesium fluoride. We present reflectance measurements of the antireflection coated windows and a reflectance study of the DMDs active area (window removed). Furthermore, we investigated the long-term stability of the DMD reflectance and recoating device with fresh Al coatings.

Quijada, Manuel A.↗

The S solubility of Cr and Al containing simulated low-activity waste glass

Here, the presence of sulfur-containing molten salt phases during vitrification is a particular problem which can be detrimental to the melter. Borosilicate compositions were designed to explore both the effects of a fixed amount of Cr, as Cr 2 O 3 or Na 2 CrO 4 , and the impact of Al 2 O 3 , on sulfur solubility as determined by progressively adding elemental S. The NABS series (with Al 2 O 3 ) has a higher SO 3 solubility of ~3.5 mol% while the NBS series (without Al 2 O 3 ) has a SO 3 solubility of ~2 mol%. Crystalline Cr 2 O 3 formed in the NABS series upon the addition of S but is not present in the NBS series. At the highest S addition, a separate salt phase always forms, and was identified as Na 2 (S,Cr)O 4 via electron dispersive spectroscopy, ultraviolet-visible spectroscopy, x-ray diffraction, and thermal analysis. Magic angle spinning nuclear magnetic resonance identified no change in the B coordination in either series as S is added, suggesting that the Na is scavenged from other locations, such as the Si sites, to charge compensate sulfate, whether in the glass or in the salt. The Cr precursor identity did not affect the observed overall behavior regarding sulfur, but did impact Cr redox as identified with Raman spectroscopy.

36 MATERIALS SCIENCE↗

The corrosion of UK vitrified waste during disposal

The UK's vitrified high-level-waste (HLW) is destined to be disposed of in a deep geological disposal facility (GDF). Contact with groundwater will be the process by which radionuclides are released during 100,000+ years of disposal. Understanding the mechanisms and kinetics of glass dissolution allow models and predictions to be made on the long-term fate of the disposed HLW. Current standard laboratory scale experimental methodologies may be unrepresentative of the geological disposal environment. Aim: Provide insight into the dissolution behaviour of alkali-alumino-borosilicate UK vitrified waste in geological disposal environments. A 'cyclic vapor-static' dissolution methodology is proposed, capturing expected temporal behaviour. This will elucidate dissolution kinetics and mechanisms, optimize the base glass composition, waste loading content and generate significant, pragmatic disposal performance assessment data. Variants of three glasses to be investigated: waste-loaded MW25 and ZnCa MW28, and the ZnCa MW base. Preliminary Results: Suggests drying process decreases the chemical durability of the glass. Addition of ZnCa to UK HLW improves chemical durability. Increased waste-loading improves chemical durability. Banded structure in altered glass possibly attributed to dissolution/reprecipitation of secondary phases). Conclusion - Further Work: Cyclic vapor-static dissolution methodology may elucidate dissolution behaviour expected within a UK GDF. Potential to provide beneficial, pragmatic data for the performance assessment to implement geological disposal. Fundamental mechanisms to be understood.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Method for repair of thin glass coatings

A method of repairing cracks or damaged areas in glass, in particular, glass coatings provided on tile. The method includes removing the damaged area using a high speed diamond burr drilling out a cavity that extends slightly into the base material of the tile. All loose material is then cleaned from the drilled out cavity and the cavity is filled adjacent the upper surface of the coating with a filler material including chopped silica fibers mixed with a binder. The filler material is packed into the cavity and a repair coating is applied by means of a brush or sprayed thereover. The repair includes borosilicate suspended in solution. Heat is applied at approximately 2100 F. for approximately five minutes for curing the coating, causing boron silicide particles of the coating to oxidize forming a very fluid boron-oxide rich glass which reacts with the other frits to form an impervious, highly refractory layer.

Holt, J. W.↗

Piezocomposite Actuator Arrays for Correcting and Controlling Wavefront Error in Reflectors

Three reflectors have been developed and tested to assess the performance of a distributed network of piezocomposite actuators for correcting thermal deformations and total wave-front error. The primary testbed article is an active composite reflector, composed of a spherically curved panel with a graphite face sheet and aluminum honeycomb core composite, and then augmented with a network of 90 distributed piezoelectric composite actuators. The piezoelectric actuator system may be used for correcting as-built residual shape errors, and for controlling low-order, thermally-induced quasi-static distortions of the panel. In this study, thermally-induced surface deformations of 1 to 5 microns were deliberately introduced onto the reflector, then measured using a speckle holography interferometer system. The reflector surface figure was subsequently corrected to a tolerance of 50 nm using the actuators embedded in the reflector's back face sheet. Two additional test articles were constructed: a borosilicate at window at 150 mm diameter with 18 actuators bonded to the back surface; and a direct metal laser sintered reflector with spherical curvature, 230 mm diameter, and 12 actuators bonded to the back surface. In the case of the glass reflector, absolute measurements were performed with an interferometer and the absolute surface was corrected. These test articles were evaluated to determine their absolute surface control capabilities, as well as to assess a multiphysics modeling effort developed under this program for the prediction of active reflector response. This paper will describe the design, construction, and testing of active reflector systems under thermal loads, and subsequent correction of surface shape via distributed peizeoelctric actuation.

piezoelectric actuation↗

Polarized 3He gas circulating technologies for neutron analyzers

We outline our project to develop a circulating polarized helium-3 system for developing of large, quasi-continuously operating neutron analyzers. The project consisted of four areas: 1) Development of robust external cavity narrowed diode laser output with spectral line width < 0.17 nm and power of 2000 W. 2) Development of large glass polarizing cells using cell surface treatments to obtain long relaxation lifetimes. 3) Refinements of the circulation system with an emphasis on gas purification and materials testing. 4) Design/fabrication of a new polarizer system. 5) Preliminary testing of the new polarizer. 1. Developed Robust High-Power Narrowed Laser The optical configuration of the laser was discussed in the proposal and will be reviewed in the body of this report. The external cavity is configured to mutually lock the wavelength of five 10-bar laser stacks. All the logistical milestones were been met and critical subsystems- laser stack manifold and power divider, external laser cavity, and output telescope- were assembled and tested at low power. Each individual bar is narrowed to ~0.05 nm; when combined the laser has a cumulative spectral width of 0.17 nm across the entire beam due to variations of the bars central wavelength by +/- 0.1 nm, which is similar to that of Volume Bragg Grating narrowed laser bars. This configuration eliminates the free-running “pedestal” that occurs in other external cavity diode lasers. The full-scale laser was completed in 2016 and was used in both the older and newer helium polarizers. This laser was operated at 75% power for periods of up to 8 hours. Once installed, the spectrum became slightly broader (~.25 nm) at full power; this is likely due to very slight misalignments that occurred during handling. 2. Developed the processes to create uniform sintered sol-gel coatings. Our work on cell development comprised: 1) Production of large GE180 cells and explore different means of cell preparation, and 2) Development of apply sol-gel coatings to the interior of both borosilicate and aluminosilicate cells. We applied six sol-gel coatings. By modifying the mixture and developing procedures to drain and dry the cell, we produced visually uniform coatings on the interior of the cells. We now have perfected that process as described below in our report. We were able to accelerate the testing of cells using an ex situ method that avoids installing each cell into a polarizer. In the project’s last year, we conducted 38 external tests of 8 different cells. We also installed two sol-gel coated cells in our polarizers. We created cell with long ex situ relaxation lifetimes, one of which exceeded 40 hours. However, when installed in the polarizer the measured lifetime is 8 hours or less. 3. Demonstrated cycling of polarized gas and ex situ cell testing We are now cycling polarized gas from the polarizer to glass vessels and back. This has allowed us, for the first time, to make ex situ T1 measurements of polarizing cells without installing them into the polarizer itself. This has greatly improved our productivity in producing cells and evaluating our cell preparation processes. We continued development of the gas handling system in parallel with fabricating new polarizer. The integrated system was tested by the end of 2016. We now regularly cycle gas into and out of the polarizer. 4. Completed new polarizer infrastructure and control systems. We completed the new polarizer infrastructure in November 2016. The polarizer subsystems are 1) the frame, 2) the oil flow system, 3) the gas handling system, 4) the pressure vessel, with embedded solenoid, 5) cell mounting hardware with heat spreaders, and 6) electrical power and instrumentation. 5. Carried out initial tests of polarizer. We completed initial testing of the polarizer in April and May of 2017. These tests were carried out for periods up to 6 hours with laser power between 750 and 1300 Watts. The laser performed well and the polarization with asymptotic to 45 percent, which was below expectations. This low value resulted from a stationary thermal inversion in the cell that caused most of the laser power to be absorbed near the laser inlet window and deprived the lower portions of the cell of pumping laser light. Possible solutions to this problem include enhanced cooling of the cell near the laser entry and slight detuning of the laser. 6. Ongoing work. Our polarizer development efforts are ongoing to pursue our interest in neutron analyzers, nuclear targets, and providing helium for medical imaging. Current tests in the pipeline include: 1. Testing cooling enhancements to improve laser penetration of spectrally narrow lasers; 2. Testing of a cell with isolation valves that minimizes diffusive contact with gas handling hardware during polarization; 3. Testing of smaller hybrid cells with reduced alkali loading; 4. Producing polarized helium-3 for MRI imaging at the University of Missouri.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Summary Of Cold Crucible Vitrification Tests Results With Savannah River Site High Level Waste Surrogates

The cold crucible inductive melting (CCIM) technology successfully applied for vitrification of low- and intermediate-level waste (LILW) at SIA Radon, Russia, was tested to be implemented for vitrification of high-level waste (HLW) stored at Savannah River Site, USA. Mixtures of Sludge Batch 2 (SB2) and 4 (SB4) waste surrogates and borosilicate frits as slurries were vitrified in bench- (236 mm inner diameter) and full-scale (418 mm inner diameter) cold crucibles. Various process conditions were tested and major process variables were determined. Melts were poured into 10L canisters and cooled to room temperature in air or in heat-insulated boxes by a regime similar to Canister Centerline Cooling (CCC) used at DWPF. The products with waste loading from ~40 to ~65 wt.% were investigated in details. The products contained 40 to 55 wt.% waste oxides were predominantly amorphous; at higher waste loadings (WL) spinel structure phases and nepheline were present. Normalized release values for Li, B, Na, and Si determined by PCT procedure remain lower than those from EA glass at waste loadings of up to 60 wt.%.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗