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At least 55 records · Page 3

Segmental Dynamics and Vitrification in Associating Copolymer Melts: Role of Cluster Formation, Microdomains, and Cross-Linking

A microscopic statistical mechanical theory of the structure, self-assembly, and activated segmental relaxation is employed to study associating copolymer melts with high attractive sticker fractions, local clustering, and disordered microphase ordering. The stickers are dynamically pinned in a manner that does not affect equilibrium structure which mimics the much slower physical bond breaking process or postassembly cross-linking of sticky monomers. Local sticker clustering and microdomain spatial correlations significantly modify the activated relaxation of nonstickers and glass transition temperature, T g . A re-entrant glass-melting feature is predicted as sticker attraction strength is initially increased corresponding to a speed up of segmental relaxation, and hence reduction of T g relative to the cross-linked homopolymer network. A mechanistic analysis reveals three competing effects: a purely kinetic slowing down of nonstickers down due to cross-linking, disordering of the nonsticker local cage and weakening of effective forces they experience due to sticker physical clustering, and a longer range impact of microdomain scale correlations that results in nonmonotonic dynamical effects. At high enough attraction strength, a qualitative change emerges corresponding to a sticker fraction dependent elevation of T g , which eventually surpasses that of the cross-linked homopolymer network. Dynamically, the new physics arises from a complex evolution of the amplitude of the collective elastic field that dresses the large amplitude mobile segment hopping within a coupled local-nonlocal description of the alpha relaxation. Furthermore, the results are qualitatively consistent with recent experiments on associating PDMS and PPG telechelics of fixed sticker fraction but with chemically different end groups of variable attraction strengths. Finally, possible tests using simulation and the influence of material or model specific interaction potentials and other real world complications are discussed.

Copolymers↗

Effect of sucrose on technetium and rhenium retention during vitrification of low-activity wastes

Sucrose (C 12 H 22 O 11 ) has been used in low-activity waste (LAW) melter feeds containing large fractions of nitrates, nitrites, or both because it facilitates foam suppression and denitration. This study focused on the effect of sucrose in LAW feeds on technetium (Tc) and rhenium (Re) retention. The amount of sucrose added in feeds was varied to differentiate the carbon-to-nitrogen mole ratio (C/N ratio). The results show that larger sucrose addition (higher C/N ratio) enhances Tc and Re retention. Reducing conditions induced by sucrose decomposition and early chemical reactions between sucrose and NaNO 3 /NaNO 2 are expected to increase Tc and Re retention. However, high sucrose addition decreased sulfur (S) retention slightly because sodium sulfate decomposes in reducing conditions at lower temperature. This early sulfate decomposition can affect Tc and Re retention partly because these species can be soluble in sulfate phases. This correlation indicates that the decrease of sulfate phases in the glass by early decomposition can reduce the solubility of Tc and Re in the sulfate phases, which may increase Tc and Re retention in the glass. In addition, continuous gas evolution and vigorous foaming at the foaming temperature range of 700–900°C may influence Tc and Re retention process interrupting retention or facilitating volatilization.

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Vitrification of High-Cr Glass in Research-Scale Melter

This test report describes the experimental results from a small-scale test using the research-scale melter (RSM) at Pacific Northwest National Laboratory to demonstrate processing of a high-Cr simulated feed stream, designated HLW-HCr-16. The RSM is a small, joule-heated melter capable of processing melter feed continuously. The melter is equipped with Inconel ® 693 electrodes, Monofrax ® K-3 refractory, and an Inconel 690 pour spout. An electric kiln surrounds the melter body and minimizes heat loss from the melter body during operation. The RSM is equipped with an offgas treatment system that employs quenching, wet scrubbing, and high-efficiency mist elimination. The glass-discharge section is heated to facilitate pouring of the glass. The melter is fitted with a melt cavity that is ~25 cm (10 in.) in diameter with a nominal glass depth of 8.9 cm (3.5 in.). The melter was operated with a target glass temperature of 1150°C and target plenum temperature between 550°C and 700°C for this test. The air bubbling rate was 4.2 L/min. Overall, during the continuous operation of the melter for ~ 103 hours, ~ 141 kg of glass was produced. At the conclusion of the test, the melter and exhaust lines were visually inspected for particulate deposition and corrosion. Entrained material had adhered to the underside of the melter lid and to the exhaust piping. Enrichments in elements such as Cl, F, B, K, Li, P, Na, and S were measured in these deposits through inductively coupled plasma–optical emission spectroscopy and X-ray fluorescence analysis. When the melter electrodes and air bubbler tube were removed from the glass in the RSM, the electrodes appeared discolored, but no significant loss of metal was observed. The processing of a high-Cr simulant, HLW-HCr-16, in the RSM produced glass at an average rate of 1.36 kg/h, equaling a melter-surface-area normalized glass generation rate of 654 kg/day/m 2 . The resulting glass met the toxicity characteristic leaching procedure requirement. Test results of crystallinity, electrical conductivity, and viscosity showed good processing properties of this high-Cr high-level waste glass. RSM offgas was also sampled and analyzed at periodic intervals during steady-state operating conditions. The total decontamination factor averaged by four sampling periods was 134. The concentrations of CO and NO x in emissions were 237 to 422 and 69 to 94 parts per million by volume, respectively.

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Vitrification of Hanford Tank 241-AP-101 Waste and Simulant

Hanford tank 241-AP-101 (referred to herein as AP-101) is the second Hanford radioactive tank waste planned to be processed and vitrified. A simulant version of AP 101 waste was formulated from the best-basis inventory (BBI) for the Hanford Tank 241-AP-101 liquid with an assumed target dilution of the waste from the BBI sodium molarity of 8.61 M to the desired 5.5 M Na. After the addition of glass-forming chemicals (GFCs), the simulant melter feed was processed in a non-radioactive, continuous laboratory-scale melter (CLSM) system. The AP-101 simulant melter feed was charged into the CLSM for 6.11 h of processing, which produced 6.55 kg of glass, for an average glass production rate of 2275 kg m 2 d -1 . Since there were no processing issues with the AP-101 simulant melter feed, AP-101 melter feed made with actual waste was then processed in a CLSM system built into a contamination area in a radioactive environment. The melting behavior characteristics appeared similar for both the simulant and waste melter feeds. The AP-101 waste melter feed was charged into the CLSM for 12.14 h of processing, which produced 8.75 kg of glass, for an average glass production rate of 1530 kg m 2 d -1 . During the AP-101 waste melter feed charging, the pump used to move the feed reached a maximum and it is believed that if the pump had a greater capacity, a greater average glass production rate could have been achieved. A constituent of interest present in low quantities in the AP-101 waste is 99 Tc or its non-radioactive surrogate, Re, added to the AP-101 simulant. Analysis for the quantities of 99 Tc and Re in the AP-101 glass product resulted in an average single-pass retention from the melter feed during relative chemical steady state of 55 ± 2 % for 99 Tc and 45 ± 2 % for Re. Compared to the processing of other melter feeds, the retention of 99 Tc in the AP-101 glass was greater than in both AP-107 and AP-105 glass, while the retention of Re in the AP-101 was less than in the AP-107 glass, but greater than in the AP-105 glass. A spike of I was added into the AP-101 melter feed that could be detected above the analysis detection limits. However, the iodine was only detectable above the ~6 ppm limit in one glass pour: the pour immediately following the burn off of the cold cap, where the I level reached ~30 ppm. This event was significant because the glass was poured immediately after burn off and thus it is presumed that the iodine had yet to volatilize from the glass melt while idling. It is recommended to perform future tests with I spikes at greater levels so that it can be detected in additional glass pours to determine if the expected 50 % retention of I used in the Kim et al. glass models can be confirmed. Offgas liquid samples were analyzed for acetonitrile, which was present at greater concentrations in CLSM liquids than in other scaled melter systems. This result was expected based on unique conditions with the CLSM system including a small plenum space leading to low residence time for offgas and the rapidity of offgas cooling upon exiting the CLSM vessel due to the location and environment. About 90 % of the total acetonitrile captured during both the AP-101 simulant and waste CLSM runs was found in the offgas condensate and demister liquids, thus it is recommended that only those liquids be sent for analysis if future testing to study the presence of acetonitrile in offgas products is desired.

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Vitrification of Hanford Tank 241-AP-105 Waste at 7 M Na and Equivalent Simulant

Hanford Site nuclear waste is to be vitrified at the Waste Treatment and Immobilization Plant (WTP), which is a part of the safe and efficient retrieval, treatment, and disposal mission of the U.S. Department of Energy Office of River Protection. Hanford tank 241-AP-105 (referred to herein as AP-105) is one of the initial Hanford radioactive tank wastes planned to be processed and vitrified. A portion of AP-105 waste was retrieved by Washington River Protection Solutions, LLC (WRPS) and transferred to Pacific Northwest National Laboratory (PNNL). The waste went through dilution by Columbia River water to reach a target sodium (Na) concentration of 7 M, solids filtration, and cesium removal by ion exchange. A glass composition was calculated from the Kim et al. glass models to satisfy the WTP baseline requirements based on the as-received sample and the target dilution to 7 M, from which a simulant was calculated and glass forming chemical (GFC) additions were determined to form a liquid/solids mixture called melter feed. To prepare for the processing of the 7 M Na AP-105 waste melter feed and learn about the production expectations, the melter feed simulant of 7 M Na AP-105 waste was processed in a non-radioactive, continuous laboratory-scale melter (CLSM) system.

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Corrosion Testing of Refractory in Contact with Molten Glasses Designed for Waste Vitrification

It is known that the predictive life of the refractory ceramic liner of nuclear waste glass melters is conservative, as demonstrated by performance of these materials such as in the Defense Waste Processing Facility (DWPF). The motivation for this task is to maximize the useful life of the melters that will be operated at the Waste Treatment and Immobilization Plant (WTP), which will in turn minimize procurement and disposal costs and melter outage times, as well as to identify maximum loadings in the waste glass of those species that corrode melter components. This task was initiated jointly with Pacific Northwest National Laboratory (PNNL) with the objective to develop a methodology and model to enable more accurate prediction of refractory service life under prototypic conditions from laboratory-scale material corrosion tests.

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Experience with Noble Metals During HLW Vitrification at FZK, Germany (Rev. 0)

The noble metals ruthenium (Ru), rhodium (Rh), and palladium (Pd) are present to various extents in defense and commercial high-level nuclear waste streams. Usually, their concentrations are higher in commercial waste. Ru, Rh, and Pd are sparingly soluble in silicate glass melts and they therefore form separate metal, oxide, or other phases. These phases are generally denser than the glass melt and tend to sediment to the bottom of the melter, where they form a "sludge" layer. Since the sludge layer has a higher electrical conductivity than the molten glass, accumulation of sludge can ultimately lead to electrical disruption of the operation of the melter. In addition, the sludge reduces the melt volume, which also changes the operational characteristics of the melter.

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Corrosion Testing of Bubbler Materials for LAW Vitrification (Rev. 0)

This work involved crucible-scale corrosion tests using coupons of selected materials in the baseline glass formulations for the seven LAW Sub-Envelopes. The tests were performed with Inconel 690 and MA 758; per the Test Plan, selected tests were also performed with a proprietary high temperature alloy supplied by SRTC. Coupons of these materials were tested for their corrosion resistance to LAW baseline glasses in two test series: the first series was with a baseline glass only, the second series was with a baseline glass and an added salt layer.

36 MATERIALS SCIENCE↗

Vitrification of Hanford Tank 241-AN-107 Waste and Equivalent Simulant

Hanford Site nuclear waste is to be vitrified at the Waste Treatment and Immobilization Plant (WTP), which is a part of the safe and efficient retrieval, treatment, and disposal mission of the U.S. Department of Energy Office of River Protection. Hanford tank 241-AN-107 (referred to herein as AN-107) is one of the initial Hanford radioactive tank wastes planned to be processed and vitrified. A portion of AN-107 waste was retrieved by Washington River Protection Solutions, LLC (WRPS) and transferred to Pacific Northwest National Laboratory (PNNL). Compared to previously received and vitrified wastes (AP-107, AP-105, and AP-105), the concentration of organics in AN-107 was greater by an order of magnitude, while the activity of radionuclides was multiple orders of magnitude greater.

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Modeling the Behavior of Noble Metals During HLW Vitrification in the DM1200 Melter

The noble metals ruthenium (Ru), rhodium (Rh), and palladium (Pd) are present to various extents in defense and commercial high-level nuclear waste streams. Usually, their concentrations are higher in commercial waste. Ru, Rh, and Pd are sparingly soluble in silicate glass melts and they therefore form separate metal, oxide, or other phases. These phases are generally denser than the glass melt and tend to sediment to the bottom of the melter, where they form a "sludge" layer. Since the sludge layer has a higher electrical conductivity than the molten glass, accumulation of sludge can ultimately lead to electrical disruption of the operation of the melter. In addition, the sludge reduces the melt volume, which also changes the operational characteristics of the melter. The noble metals sludge is a highly viscous mixture of melt and noble metal phases. The concentration of noble metals in the sludge may be 10 to 100 times higher than that in the drained glass.

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Vitrification Testing of HLW with High Phosphate

Projections of the number of high level waste (HLW) canisters to be produced in the Hanford Tank Waste Treatment and Immobilization Plant (WTP) (e.g., [1]) are based upon the inventory of the tank wastes, the anticipated performance of the sludge treatment processes, and current understanding of the capability of the borosilicate glass waste form. The WTP HLW melter design, unlike earlier Department of Energy (DOE) melter designs, incorporates a glass bubbler system. The bubblers create active glass pool mixing and thereby improve heat and mass transfer and glass melting rate. The WTP HLW melters each have a glass surface area of 3.75 m 2 and depth of ~1.1 m. The two melters in the HLW facility together are designed to produce up to 7.5 MT of glass per day at 100% availability. Further increases in HLW waste processing rates can potentially be achieved by optimization of the feed and glass formulations, increasing the melter operating temperature above 1150⁰C, and by increasing the waste loading in the glass product. Increasing the waste loading also has the added benefit of decreasing the number of canisters for storage.

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Corrosion Testing of Refractory in Contact with Molten Glasses Designed for Waste Vitrification - APPS1 Matrix Glasses

It is known that the predictive life of the refractory ceramic liner of nuclear waste glass melters is conservative, as demonstrated by performance of these materials such as in the Defense Waste Processing Facility (DWPF). The motivation for this task is to maximize the useful life of the melters that will be operated at the Waste Treatment and Immobilization Plant (WTP), which will in turn minimize procurement and disposal costs and melter outage times, as well as to identify maximum loadings in the waste glass of those species that corrode melter components. This task was initiated jointly with Pacific Northwest National Laboratory (PNNL) with the objective to develop a methodology and model to enable more accurate prediction of refractory service life under prototypic conditions from laboratory-scale material corrosion tests.

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Corrosion Testing of Refractory in Contact with Molten Glasses Designed for Waste Vitrification - HAL24 M1 Matrix Glasses

It is known that the predictive life of the refractory ceramic liner of nuclear waste glass melters is conservative, as demonstrated by performance of these materials such as in the Defense Waste Processing Facility (DWPF). The motivation for this task is to maximize the useful life of the melters that will be operated at the Waste Treatment and Immobilization Plant (WTP), which will in turn minimize procurement and disposal costs and melter outage times, as well as to identify maximum loadings in the waste glass of those species that corrode melter components. This task was initiated jointly with Pacific Northwest National Laboratory (PNNL) with the objective to develop a methodology and model to enable more accurate prediction of refractory service life under prototypic conditions from laboratory-scale material corrosion tests.

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Vitrification of Hanford Tank 241-AW-105 Waste and Equivalent Simulant

Hanford Site nuclear waste is to be vitrified at the Waste Treatment and Immobilization Plant (WTP), which is a part of the safe and efficient retrieval, treatment, and disposal mission of the U.S. Department of Energy - Hanford Field Office. A portion of Hanford tank 241-AW-105 (referred to herein as AW-105) waste was retrieved by Hanford Tank Waste Operations and Closure (H2C) and transferred to Pacific Northwest National Laboratory (PNNL). Compared to previously received and vitrified wastes (AP-107, AP-101, AN-107 and AP-105), the concentration of potassium in AW-105 was greater by an order of magnitude.

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