90 research outputs found
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Melting of foaming batches: Nuclear waste glass
A simple model is presented for the rate of melting of a batch blanket in an electric glassmelting furnace. The melting process is assumed to be jointly controlled by the heat transfer from the pool of molten glass and the batch-to-glass conversion kinetics. Factors affecting the melting rate in the conversion-controlled regime are discussed. Attention is paid to gas evolution from redox reactions in waste glass batches and component accumulation within the blanket. It is suggested that the high rate of the blanket-free melting in a mechanically agitated furnace is made possible by increasing the rate of melt surface renewal. 27 refs
The Effects Of Mixing Multi-component HLW Glasses On Spinel Crystal Size
The Hanford Waste Treatment and Immobilization Plant will vitrify radioactive waste into borosilicate glass. The high-level waste (HLW) glass formulations are constrained by processing and property requirements, including restrictions aimed at avoiding detrimental impacts of spinel crystallization in the melter. To understand the impact of glass chemistry on crystallization, two HLW glasses precipitating small (∼5 μm) spinel crystals were individually mixed and melted with a glass that precipitated large (∼45 μm) spinel crystals in ratios of 25, 50, and 75 wt.%. The size of spinel crystals in the mixed glasses varied from 5 to 20 μm. Small crystal size was attributed to: (1) high concentrations of nuclei due to the presence of ruthenium oxide and (2) chromium oxide aiding high rates of nucleation. Results from this study indicate that the spinel crystal size can be controlled using chromium oxide and/or noble metal concentrations in the melt, even in complex mixtures like HLW glasses. Smaller crystals tend to settle more slowly than larger crystals, therefore smaller crystals would be more acceptable in the melter without a risk of failure. Allowing higher concentrations of spinel-forming waste components in the waste glass enables glass compositions with higher waste loading, thus increasing plant operational flexibility. An additional benefit to the presence of chromium oxide in the glass composition is the potential for the oxide to protect melter walls against corrosion
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First-order model for durability of Hanford waste glasses as a function of composition
Two standard chemical durability tests, the static leach test MCC-1 and product consistency test PCT, were conducted on simulated borosilicate glasses that encompass the expected range of compositions to be produced in the Hanford Waste Vitrification Plant (HWVP). A first-order empirical model was fitted to the data from each test method. The results indicate that glass durability is increased by addition of Al{sub 2}O{sub 3}, moderately increased by addition of ZrO{sub 2} and SiO{sub 2}, and decreased by addition of Li{sub 2}O, Na{sub 2}O, B{sub 2}O{sub 3}, and MgO. Addition of Fe{sub 2}O{sub 3} and CaO produce an indifferent or reducing effect on durability according to the test method. This behavior and a statistically significant lack of fit are attributed to the effects of multiple chemical reactions occurring during glass-water interaction. Liquid-liquid immiscibility is suspected to be responsible for extremely low durability of some glasses
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Foaming of E-Glass II (Report for G Plus Project for PPG)
In a previous study, the effect of the furnace atmosphere on E glass foaming was investigated with the specific goal to understand the impact of increased water content on foaming in oxy-fired furnaces. The present study extended the previous study and focused on the effect of glass batch chemical composition on E-glass foaming. The present study also included reruns of foam tests performed in a previous study, which resulted in the same trend: the foaming extent increased nearly linearly with the heating rate and no foam was produced when CO2 + 55% H2O atmosphere was introduced at 300°C. It was shown that the lack of foaming in the test with CO2 + 55% H2O atmosphere introduced at 300°C was caused by a loss of sulfate at T <1250°C because of higher water content at the early stages of melting. The tests with new batches in the present study showed that replacing quicklime with limestone tend to decrease foaming, possibly caused by increased sulfate loss during early stages of melting in the batch with limestone. The batches where Na2SO4 was replaced with NaNO3, NaNO3 + CeO2, or CeO2, produced only very limited foaming regardless of the replacing components. As expected, the foaming extent increased as the sulfate content in the batch increased. The results of the present study suggest that foaming can be reduced by using limestone over quicklime and by decreasing the sulfate addition to a minimum required for refining
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Kinetics of Cold-Cap Reactions for Vitrification of Nuclear Waste Glass Based on Simultaneous Differential Scanning Calorimetry - Thermogravimetry (DSC-TGA) and Evolved Gas Analysis (EGA)
For vitrifying nuclear waste glass, the feed, a mixture of waste with glass-forming and modifying additives, is charged onto the cold cap that covers 90?100% of the melt surface. The cold cap consists of a layer of reacting molten glass floating on the surface of the melt in an all-electric, continuous glass melter. As the feed moves through the cold cap, it undergoes chemical reactions and phase transitions through which it is converted to molten glass that moves from the cold cap into the melt pool. The process involves a series of reactions that generate multiple gases and subsequent mass loss and foaming significantly influence the mass and heat transfers. The rate of glass melting, which is greatly influenced by mass and heat transfers, affects the vitrification process and the efficiency of the immobilization of nuclear waste. We studied the cold-cap reactions of a representative waste glass feed using both the simultaneous differential scanning calorimetry-thermogravimetry (DSC-TGA) and the thermogravimetry coupled with gas chromatography-mass spectrometer (TGA-GC-MS) as complementary tools to perform evolved gas analysis (EGA). Analyses from DSC-TGA and EGA on the cold-cap reactions provide a key element for the development of an advanced cold-cap model. It also helps to formulate melter feeds for higher production rate
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EFFECT OF MELTER-FEED-MAKEUP ON VITRIFICATION PROCESS
Increasing the rate of glass processing in the Hanford Tank Waste Treatment and Immobilization Plant (WTP) will allow shortening the life cycle of waste cleanup at the Hanford Site. While the WTP melters have approached the limit of increasing the rate of melting by enhancing the heat transfer rate from molten glass to the cold cap, a substantial improvement can still be achieved by accelerating the feed-to-glass conversion kinetics. This study investigates how the feed-to-glass conversion process responds to the feed makeup. By identifying the means of control of primary foam formation and silica grain dissolution, it provides data needed for a meaningful and economical design of large-scale experiments aimed at achieving faster melting
Exploratory research in alternative raw material sources and reformulation for industrial soda-lime-silica glass batch
For energy saving and CO2 emissions reduction, in addition to extending the range of suitable raw material sources for glass manufacture, compositional reformulation, and alternative raw materials have been studied in the context of industrial container and float‐type soda‐lime‐silica (SLS) glasses. Lithium, potassium, and boron were applied to modify benchmark glass compositions. Reformulation impacts on key glass properties including the viscosity‐temperature relationship, thermal expansion, liquidus temperature, forming behavior and color. Compared to the benchmark glass, representative of commercial SLS glasses, melting temperatures (taken as temperatures corresponding to log (viscosity/dPa·s) = 2) of reformulated glasses are reduced by 11°C‐55°C. Investigation of four industrial by‐products (seashell waste, eggshell waste, biomass ash, and rice husk ash), and their potential suitability as alternative glass batch raw materials, was also conducted. Seashell waste and biomass ash were successfully introduced into representative green glass formulations
Effect of network connectivity on behavior of synthetic Broborg Hillfort glasses
There is wide industrial interest in developing robust models of long-term (>100 years) glass durability. Archeological glass analogs, glasses of similar composition, and alteration conditions to those being tested for durability can be used to evaluate and inform such models. Two such analog glasses from a 1500-year-old vitrified hillfort near Uppsala, Sweden have previously been identified as potential analogs for low concentration Fe-bearing aluminosilicate nuclear waste glasses. However, open questions remain regarding the melting environment from which these historic glasses were formed and the effect of these conditions on their chemical durability. A key factor to answering the previous melting and durability questions is the redox state of Fe in the starting and final materials. Past work has shown that the melting conditions of a glass-forming melt may influence the redox ratio value (Fe+3/∑Fe), a measure of a glass's redox state, and both melting conditions and the redox ratio may influence the glass alteration behavior. Synthetic analogs of the hillfort glasses have been produced using either fully oxidized or reduced Fe precursors to address this question.
In this study, the melting behavior, glass transition temperature, oxidation state, network structure, and chemical durability of these synthesized glass analogs is presented. Resulting data suggests that the degree of network connectivity as impacted by the oxidation state of iron impacted the behavior of the glass-forming melt but in this case does not affect the chemical durability of the final glass. Glasses with a lower degree of melt connectivity were found to have a lower viscosity, resulting in a lower glass transition temperature and softening temperature, as well as in a lower temperature of foam onset and temperature of foam maximum. This lower degree of network connectivity most likely played a more significant role in accelerating the conversion of batch chemicals into glass than the presence of water vapor in the furnace's atmosphere. Future work will focus on using the results from this work with outcomes from other aspects of this project to evaluate long-term glass alteration models
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Bulk Vitrification Castable Refractory Block Protection Study
Bulk vitrification (BV) was selected for a pilot-scale test and demonstration facility for supplemental treatment to accelerate the cleanup of low-activity waste (LAW) at the Hanford U.S. DOE Site. During engineering-scale (ES) tests, a small fraction of radioactive Tc (and Re, its nonradioactive surrogate) were transferred out of the LAW glass feed and molten LAW glass, and deposited on the surface and within the pores of the castable refractory block (CRB). Laboratory experiments were undertaken to understand the mechanisms of the transport Tc/Re into the CRB during vitrification and to evaluate various means of CRB protection against the deposition of leachable Tc/Re. The tests used Re as a chemical surrogate for Tc. The tests with the baseline CRB showed that the molten LAW penetrates into CRB pores before it converts to glass, leaving deposits of sulfates and chlorides when the nitrate components decompose. Na2O from the LAW reacts with the CRB to create a durable glass phase that may contain Tc/Re. Limited data from a single CRB sample taken from an ES experiment indicate that, while a fraction of Tc/Re is present in the CRB in a readily leachable form, most of the Tc/Re deposited in the refractory is retained in the form of a durable glass phase. In addition, the molten salts from the LAW, mainly sulfates, chlorides, and nitrates, begin to evaporate from BV feeds at temperatures below 800 C and condense on solid surfaces at temperatures below 530 C. Three approaches aimed at reducing or preventing the deposition of soluble Tc/Re within the CRB were proposed: metal lining, sealing the CRB surface with a glaze, and lining the CRB with ceramic tiles. Metal liners were deemed unsuitable because evaluations showed that they can cause unacceptable distortions of the electric field in the BV system. Sodium silicate and a low-alkali borosilicate glaze were selected for testing. The glazes slowed down molten salt condensate penetration, but did little to reduce the penetration of molten salt. Out of several refractory tile candidates, only greystone and fused-cast alumina-zirconia-silica (AZS) refractory remained intact and well bonded to the CRB after firing to 1000 C. The deformation of the refractory-tile composite was avoided by prefiring the greystone tile to 800 C. Condensed vapors did not penetrate the tiles, but Re salts condensed on their surface. Refractory corrosion tests indicated that a 0.25-inch-thick greystone tile would not corrode during a BV melt. Tiles can reduce both vapor penetration and molten salt penetration, but vapor deposition above the melt line will occur even on tiles. The Tc/Re transport scenario was outlined as follows. At temperatures below 700 C, molten ionic salt (MIS) that includes all the Tc/Re penetrates, by capillarity, from the feed into the CRB open porosity. At approximately 750 C, the MIS decomposes through the loss of NOx, leaving mainly sulfate and chloride salts. The Na2O formed in the decomposition of the nitrates reacts with insoluble grains in the feed and with the aluminosilicates in the CRB to form more viscous liquids that reduce further liquid penetration into the CRB. At 800 to 1000 C, a continuous glass phase traps the remains of the MIS in the form of inclusions in the bulk glass melt. At 1000 to 1200 C, the salt inclusions in the glass slowly dissolve but also rise to the surface. The Tc/Re salts also evaporate from the free surface of the glass melt that is rapidly renewed by convective currents. The vapors condense on cooler surfaces in the upper portion of the CRB, the box lid, and the off-gas system
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Bulk Vitrification Performance Enhancement: Refractory Lining Protection Against Molten Salt Penetration
Bulk vitrification (BV) is a process that heats a feed material that consists of glass-forming solids and dried low-activity waste (LAW) in a disposable refractory-lined metal box using electrical power supplied through carbon electrodes. The feed is heated to the point that the LAW decomposes and combines with the solids to generate a vitreous waste form. This study supports the BV design and operations by exploring various methods aimed at reducing the quantities of soluble Tc in the castable refractory block portion of the refractory lining, which limits the effectiveness of the final waste form
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