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At least 343 records · Page 19

Evaluation of Sludge Solids Returns Impacts on Sludge Batch 10 Flammability, Glass Quality, and Glass Processability

The Savannah River National Laboratory (SRNL) is currently preparing to return ≤ 20 kgs of sludge solids collected over time from Tank Farm characterization activities and demonstrations of the Defense Waste Processing Facility (DWPF) flowsheets (nitric-formic and nitric-glycolic). These sludge solids will be transported and added to Tank 51 which is currently preparing Sludge Batch (SB) 10. DWPF plans to operate the under the nitric-glycolic flowsheet for the processing of SB10. The hydrogen generation rate for the nitric-glycolic flowsheet is 0.024 lb h -1 . The addition of ≤20 kg of sludge solids returns to SB 10 does not have an impact on flammability in the DWPF Chemical Process Cell (CPC) or glass quality and processability. The relatively low mass of the addition (≤20 kg) is insufficient to detect a significant analytical change to the expected SB 10 compositions.

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Comment on Comment on “Anomalous structural recovery in the near glass transition range in a polymer glass: Data revisited in light of temperature variability in vacuum oven‐based experiments”*

Abstract Cangialosi, Alegría, and Colmenero have made a comment on a paper of ours [Polym. Eng. Sci. 2022:1–13], in which we discussed the concern that the enthalpy recovery data reported by Cangialosi and co‐workers [Phys. Rev. Lett. 2013;111(9):095701] for polystyrene aged up to 15 K below glass transition temperature was anomalous and contradicted existing experimental results from the literature over a similar range of aging conditions. Their response shifts the focus away from the raised questions about their experimental results and attempts to invalidate the data that we cited in support of our argument. Here we respond to the comment and add additional analysis that suggests the structural recovery response of glassy materials exhibits smooth behavior over the full range of measurements, up to 7 or 8 logarithmic decades. We do this by referring to the work on the intrinsic isotherm down‐jump and memory responses of poly(vinyl acetate) between 40°C and 15°C over six logarithmic decades by Kovacs [Fortsch. Hochpolym. Fo. 1963;3(1/2):394–508], the small‐strain tensile creep of poly(vinyl chloride) quenched from 90°C to 40°C (approximately 40°C below T g ) over seven logarithmic decades from Struik [Polym Eng. Sci., 1977;17:165–173], and the volume recovery behavior for aging times up to 3 months in a temperature range between 95°C and −50°C by Greiner and Schwarzl [Rheol. Acta. 1984;23(4):378–395]. We also add discussion that an isothermal aging procedure using a vacuum oven is highly vulnerable to temperature errors due to the problem of good temperature control when the heat transfer mechanism is primarily radiative.

Jin, Shuang↗

Design, Synthesis, and Characterization of Polymer Precursors to Li x PON and Li x SiPON Glasses: Materials That Enable All-Solid-State Batteries (ASBs)

LiPON-like glasses that form lithium dendrite impenetrable interfaces between lithium battery components are enabling materials that may replace liquid electrolytes permitting production of all-solid-state batteries (ASBs). Unfortunately, to date, such materials are introduced only via gas-phase deposition. Furthermore, we demonstrate the design and synthesis of easily scaled, lowtemperature, low-cost, solution-processable inorganic polymers containing LiPON/LiSiPON elements. OPCl 3 and hexachlorophosphazene [Cl 2 P=N] 3 provide starting points for elaboration using MNH 2 (M = Li/Na) or (Me 3 Si)NH followed by reaction with controlled amounts of LiNH 2 to produce oligomers/polymers with molecular weights (MWs) ≈1–2 kDa characterized by multinuclear NMR, gel permeation chromatography (GPC), thermogravimetric analysis (TGA), Fourier-transform infrared (FTIR), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and matrix-assisted laser desorption/ ionization (MALDI)-time-of-flight (ToF) offering stabilities to 150–200 °C and ceramic yields (800 °C) of 50–60%. 7 Li NMR suggests that precursor-bound Li + dissociates easily, beneficial for electrochemical applications. XPS shows higher N/P ratios (1–3) than via gas-phase methods (<1) correlating N/P ratios, 7 Li shifts, and Li + conductivities. Li 2 SiPHN offers the highest ambient conductivity of 3 × 10 –1 mS cm –1 at 400 °C/2 h/N 2 .

36 MATERIALS SCIENCE↗

Self-Consistent Theory for Structural Relaxation, Dynamic Bond Exchange Times, and the Glass Transition in Polymeric Vitrimers

Here, we formulate a statistical mechanical theory for how dynamic bond exchange influences the activated hopping-driven relaxation of Kuhn segments in dynamically cross-linked networks or vitrimers over a wide range of temperatures and cross-link densities. The key new methodological aspect is to address in a self-consistent manner the dynamic consequences of bond exchange on the Kuhn segmental alpha relaxation, and vice versa. The predicted temperature dependence of the segmental alpha time of vitrimers at high temperatures remains the same as that of permanent networks, but at lower temperatures, a significant acceleration of relaxation occurs due to bond exchanges. From a mechanistic perspective, the vitrimer local cage barrier is very weakly affected by bond exchange, while the collective elastic barrier contribution decreases significantly in the deeply supercooled regime. The vitrimer glass transition temperature is predicted to grow linearly with the square root of the cross-link density, as previously found for permanent networks. Material-specific chemical effects such as cross-linker size relative to that of the normal Kuhn segment or special attraction of a cross-linker with polymers are crudely considered based on model calculations. The theory is quantitatively applied to recent experiments on dry ethylene vitrimers. Good agreements are found including that the bond exchange time follows an Arrhenius law at high enough temperatures but upward non-Arrhenius deviations emerge in the deeply supercooled regime, and a collapsed master curve of the segment alpha time exists over a wide range of cross-link densities and temperatures. Possible extensions to treat dynamic heterogeneity effects and penetrant transport in vitrimers are briefly discussed.

chemical calculations↗

Determination of heat conductivity of waste glass feed and its applicability for modeling the batch-to-glass conversion

The heat conductivity of reacting melter feed affects the heat transfer and conversion process in the cold cap (the reacting feed floating on molten glass). To investigate it, we simulated the feed conditions and morphology in the cold-cap by preparing “fast-dried slurry blocks”, formed by rapidly evaporating water from feed slurry poured onto a 200°C surface. A heat conductivity meter was used to measure heat conductivity of samples cut from the fast-dried slurry blocks, samples of a cold cap retrieved from a laboratory-scale melter, and loose dry powder feed samples. Our study indicates that the heat conductivity of the feed in the cold cap is significantly higher than that of loose dry powder feed, resulting from the feed solidification during the water evaporation from the feed slurry. To assess the heat transfer at higher temperatures when feed turns into foam, we developed a theoretical model that predicts the foam heat conductivity based on morphology data from in-situ X-ray computed tomography. The implications for the mathematical modeling of the cold cap are discussed.

Hujova, Miroslava↗

FY2017 ILAW Glass SPFT Testing for Disposal at IDF: Glass IDF21-EC14

About 50 million gallons of high-level mixed waste is currently stored in underground tanks at The United States Department of Energy’s (DOE’s) Hanford site in the State of Washington. The Hanford Tank Waste Treatment and Immobilization Plant (WTP) will provide DOE’s Office of River Protection (ORP) with a means of treating this waste by vitrification for subsequent disposal. The tank waste will be separated into low- and high-activity waste fractions, which will then be vitrified respectively into Immobilized Low Activity Waste (ILAW) and Immobilized High Level Waste (IHLW) products. The ILAW product will be disposed in an engineered facility – the Integrated Disposal Facility (IDF) – on the Hanford site, while the IHLW product is designed for deep geological disposal in a national facility for high level nuclear waste. The ILAW and IHLW products must meet a variety of requirements with respect to protection of the environment before they can be accepted for disposal. The objective of the work described in this report is to perform testing, data collection, and analyses for the ILAW glass product for subsequent use in the performance assessment (PA) of the IDF to assess potential environmental risks associated with long-term storage.

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