Vitrimerization of crosslinked elastomers: a mechanochemical approach for recycling thermoset polymers
Recycling and reprocessing of crosslinked EVA through Vitrimerization.
Bandegi, Alireza↗
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Circularity in polymers: addressing performance and sustainability challenges using dynamic covalent chemistries
The circularity of current and future polymeric materials is a major focus of fundamental and applied research, as undesirable end-of-life outcomes and waste accumulation are global problems that impact our society. The recycling or repurposing of thermoplastics and thermosets is an attractive solution to these issues, yet both options are encumbered by poor property retention upon reuse, along with heterogeneities in common waste streams that limit property optimization. Dynamic covalent chemistry, when applied to polymeric materials, enables the targeted design of reversible bonds that can be tailored to specific reprocessing conditions to help address conventional recycling challenges. In this review, we highlight the key features of several dynamic covalent chemistries that can promote closed-loop recyclability and we discuss recent synthetic progress towards incorporating these chemistries into new polymers and existing commodity plastics. Next, we outline how dynamic covalent bonds and polymer network structure influence thermomechanical properties related to application and recyclability, with a focus on predictive physical models that describe network rearrangement. Finally, we examine the potential economic and environmental impacts of dynamic covalent polymeric materials in closed-loop processing using elements derived from techno-economic analysis and life-cycle assessment, including minimum selling prices and greenhouse gas emissions. Throughout each section, we discuss interdisciplinary obstacles that hinder the widespread adoption of dynamic polymers and present opportunities and new directions toward the realization of circularity in polymeric materials.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Early-stage oxidation and subsequent damage of the used nuclear fuel extractant TODGA; electron pulse radiolysis and theoretical insights
Radiation induced damage of extractant molecules is a well-known phenomenon responsible for reducing efficiency and increasing the waste and cost of reprocessing used nuclear fuel (UNF). As such, understanding early-stage (pico- to nanoseconds) radiation-induced reaction mechanisms is essential for informing the design of next generation extractants with enhanced radiation robustness. Here, in this work, we utilized picosecond and nanosecond electron pulse radiolysis experiments to probe the early-stage radioactive environment experienced by the organic phase extractant N,N,N',N'-tetraoctyldiglycolamide (TODGA), proposed for separating highly radioactive trivalent minor actinides (specifically americium and curium) from the trivalent lanthanides. Using comparisons to the similar ionization potential (IP) solute p-xylene, this work determined the mechanism of reaction with the ionized diluent (i.e., n-dodecane radical cation, DD˙ + ) is hole transfer to produce TODGA˙ + . At high TODGA concentrations (>100 mM), the majority of this transfer occurs faster than 10 ps via the capture of DD˙ + holes prior to their solvation with a C 37 = 300 mM. The surviving solvated holes were captured with k = (2.38 ± 0.15) × 10 10 M -1 s -1 . Attempts at subsequent hole transfer to lower IP solutes found that only 10% of holes were transferred, indicating bond rupture of TODGA˙ + occurs within 2.6 ns at 200 mM TODGA. Possible reaction pathways for the rapid decomposition of TODGA˙ + were explored using a combination of experiments and density functional theory (DFT) calculations.
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
Polyhydroxyalkanoates in emerging recycling technologies for a circular materials economy
Circular polymer systems, specifically polyesters operating through chemical and biological technologies, are approaching a critical moment of industrial adoption and scale-up feasibility. At the same time, polyhydroxyalkanoate (PHA) production, scale-up, and resulting material development is converging toward commodity applications. The current PHA end-of-life philosophy, however, focalizes leveraging inherent biodegradability to circumvent plastic waste accumulation. If indeed a substantial replacement of incumbent single-use plastics with PHA alternatives is to be met in commercial manufacture, we emphasize the importance of linking PHA development with feasible polymer recycling technologies. In other words, a PHA materials economy is significantly more carbon- and cost-favorable when efficient mechanical (reprocessing), chemical (deconstruction, depolymerization), or biological (enzymatic) recycling is prioritized over biodegradation or composting. In this perspective, we discuss strategies for PHA recyclable-by-design principles, guidable by developing machine learning tools, as well as material compatibility with closed-loop recycling technologies. Additionally, we posit compelling life-cycle assessment incentives for adopting polymer reclamation over competing pathways. Ultimately, we hope this narrative further inspires the alignment between PHA design with growing calls for a circular material economy.
36 MATERIALS SCIENCE↗
Review of iodine behavior from nuclear fuel dissolution to environmental release
During nuclear fuel reprocessing, radioiodine, can be released.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Elemental analysis of air-sensitive frozen molten salt samples using an inert transfer chamber for LIBS/LA-ICP-TOF-MS analysis
A novel inert sample transfer system was developed and employed to enable, for the first time, the analysis of air-sensitive salt samples in a two-volume ablation cell using simultaneous laser-induced breakdown spectroscopy (LIBS) and laser ablation (LA)-inductively coupled plasma (ICP)-time-of-flight (TOF)-mass spectrometry (MS) analysis. Molten salts are of growing interest as a medium for advanced nuclear reactors and nuclear fuel reprocessing technologies continue to be developed around their use. However, compositional analysis of molten salt samples can be challenging because of their air-sensitive nature and varying solubilities leading to inaccurate measurements when digested. LA-based analysis provides an alternate method to digestion and can provide rapid elemental information with little sample preparation. In this study, LIBS and LA-ICP-TOF-MS were used to analyze the Ce content in frozen salt samples taken from a series of electrochemical experiments. Calibrations were built for each technique, and the resulting limits of detection for Ce were estimated to be 107 and 58 µg g −1 for LIBS and LA-ICP-TOF-MS, respectively. Test samples from the electrochemical experiments were analyzed using these calibrations. The results matched bulk digestion-based ICP-optical emission spectroscopy values, and daily trends in Ce concentration changes were identified. Additionally, the LIBS and LA-ICP-TOF-MS analysis was demonstrated for identifying microgram per gram levels of components and detecting trace contaminants. The impurities detected by LIBS included Al, Mg, Ca, and Na. The impurities detected by LA-ICP-TOF-MS included W, Ag, Al, Fe, Ni, Mo, Nd, Sm, Th, and U.
Andrews, Hunter B. [Oak Ridge National Laboratory ↗
Tandem CO 2 valorisation to polycarbonate vitrimer and ethylene carbonate
The need for renewably sourced polymers has intensified with the worsening of global challenges such as emissions and plastic pollution. Here, we report a CO 2 -based poly(cyclohexene carbonate) (PCHC) vitrimer cured with zinc stearate that directly addresses both issues. Enhanced zinc dispersion within the network enabled faster curing and reprocessing than possible with zinc acetate systems, while maintaining consistent T g and mechanical integrity across multiple cycles. The vitrimer undergoes rapid glycolysis in ethylene glycol, valorisation into ethylene carbonate with up to 97% yield without additional catalyst. When applied to carbon fibre-reinforced polymers (CFRPs), applying this strategy enabled the development of sustainable CO 2 -based CFRP that can undergo full resin valorisation and recovery of clean, damage-free fibres. Collectively, this tandem CO 2 valorisation strategy—from vitrimer synthesis to fibre-reinforced composites and subsequent chemical valorisation—establishes multiple recycling and valorisation pathways and provides a promising routte for carbon capture and utilization as well as material recycling.
36 MATERIALS SCIENCE↗
The discovery of a radio galaxy of at least 5 Mpc
Context. Giant radio galaxies (GRGs, or colloquially ‘giants’) are the Universe’s largest structures generated by individual galaxies. They comprise synchrotron-radiating active galactic nucleus ejecta and attain cosmological (megaparsec-scale) lengths. However, the main mechanisms that drive their exceptional growth remain poorly understood. Aims. To deduce the main mechanisms that drive a phenomenon, it is usually instructive to study extreme examples. If there exist host galaxy characteristics that are an important cause for GRG growth, then the hosts of the largest GRGs are likely to possess them. Similarly, if there exist particular large-scale environments that are highly conducive to GRG growth, then the largest GRGs are likely to reside in them. For these reasons, we aim to perform a case study of the largest GRG available. Methods. We reprocessed the LOFAR Two-Metre Sky Survey DR2 by subtracting compact sources and performing multi-scale CLEAN de-convolutions at 60" and 90" resolution. The resulting images constitute the most sensitive survey yet for radio galaxy lobes, whose diffuse nature and steep synchrotron spectra have allowed them to evade previous detection attempts at higher resolution and shorter wavelengths. We visually searched these images for GRGs. Results. We have discovered Alcyoneus, a low-excitation radio galaxy with a projected proper length l p = 4.99 ± 0.04 Mpc. Both its jets and lobes are detected at very high significance, and the SDSS-based identification of the host, at spectroscopic redshift z spec = 0.24674 ± 6 × 10 -5 , is unambiguous. The total luminosity density at ν = 144 MHz is L ν = 8 ± 1 × 10 25 W Hz -1 , which is below average, though near median (percentile 45 ± 3%) for GRGs. The host is an elliptical galaxy with a stellar mass M* = 2.4 ± 0.4 × 10 11 M ⊙ and a super-massive black hole mass M• = 4 ± 2 × 10 8 M ⊙ , both of which tend towards the lower end of their respective GRG distributions (percentiles 25 ± 9% and 23 ± 11%). The host resides in a filament of the Cosmic Web. Through a new Bayesian model for radio galaxy lobes in three dimensions, we estimate the pressures in the megaparsec-cubed-scale northern and southern lobes to be P min,1 = 4.8 ± 0.3 × 10 -16 Pa and P min,2 = 4.9 ± 0.6 × 10 -16 Pa, respectively. The corresponding magnetic field strengths are B min,1 = 46 ± 1 pT and B min,2 = 46 ± 3 pT. Conclusions. We have discovered what is in projection the largest known structure made by a single galaxy – a GRG with a projected proper length l p = 4.99 ± 0.04 Mpc. The true proper length is at least l min = 5.04 ± 0.05 Mpc. Beyond geometry, Alcyoneus and its host are suspiciously ordinary: the total low-frequency luminosity density, stellar mass, and super-massive black hole mass are all lower than, though similar to, those of the medial GRG. Thus, very massive galaxies or central black holes are not necessary to grow large giants, and, if the observed state is representative of the source over its lifetime, neither is high radio power. A low-density environment remains a possible explanation. The source resides in a filament of the Cosmic Web, with which it might have significant thermodynamic interaction. The pressures in the lobes are the lowest hitherto found, and Alcyoneus therefore represents the most promising radio galaxy yet to probe the warm–hot inter-galactic medium.
79 ASTRONOMY AND ASTROPHYSICS↗
Performance of the Belle II Conditions Database
The Belle II experiment at KEK observed its first collisions in the summer of 2018. Processing the large amounts of data that will be produced requires conditions data to be readily available to systems worldwide in a fast and efficient manner that is straightforward for both the user and maintainer. This was accomplished by relying on industry-standard tools and methods: the conditions database is built as an HTTP REST service using tools such as Swagger for the API interface development, Payara for the Java EE application server, and Squid for the caching proxy. This article presents the design of the Belle II conditions database production environment as well as details about the capabilities and performance during both Monte Carlo campaigns and data reprocessing.
Wood, Lynn S.↗
Actinide oxide dissolution in tributyl phosphate
An alternative to dissolving used nuclear fuel (UNF) in an acidic solution during reprocessing is direct dissolution in an organic solution, which would eliminate an aqueous dissolution step, decrease the amount of nitrate needed, and reduce the facility size. The flowsheet for this potentially less expensive alternative is first to voloxidize the UNF to remove fission product gases and form an oxide. After voloxidation, the UNF is then dissolved in an organic solution containing an extractant mixed with an aliphatic diluent and pre-equilibrated with nitric acid. The organic solution then goes through a solvent extraction process to recover the uranium and/or other desired radionuclides. This work qualitatively studied the dissolution of actinide oxides (UO2, NpO2, and PuO2) in tributyl phosphate using UV-Vis-NIR absorbance spectroscopy to ascertain dissolution behavior. Initial studies included material that is otherwise difficult to dissolve in only nitric acid, specifically CeO2, that is sometimes used as a dissolution surrogate for PuO2. This work confirmed that CeO2, NpO2, and PuO2 are difficult to dissolve in 30 vol% TBP-dodecane pre-equilibrated with 10 M HNO3 and will readily dissolve when co-precipitated with U (i.e., the mixed oxides U-Ce, U-Np, and U-Pu), surrogates for voloxidized nuclear fuel.
Gogolski, Jarrod [Savannah River National Laborato↗
Low-pass spectral analysis of time-resolved serial femtosecond crystallography data
Low-pass spectral analysis (LPSA) is a recently developed dynamics retrieval algorithm showing excellent retrieval properties when applied to model data affected by extreme incompleteness and stochastic weighting. In this work, we apply LPSA to an experimental time-resolved serial femtosecond crystallography (TR-SFX) dataset from the membrane protein bacteriorhodopsin (bR) and analyze its parametric sensitivity. While most dynamical modes are contaminated by nonphysical high-frequency features, we identify two dominant modes, which are little affected by spurious frequencies. The dynamics retrieved using these modes shows an isomerization signal compatible with previous findings. We employ synthetic data with increasing timing uncertainty, increasing incompleteness level, pixel-dependent incompleteness, and photon counting errors to investigate the root cause of the high-frequency contamination of our TR-SFX modes. By testing a range of methods, we show that timing errors comparable to the dynamical periods to be retrieved produce a smearing of dynamical features, hampering dynamics retrieval, but with no introduction of spurious components in the solution, when convergence criteria are met. Using model data, we are able to attribute the high-frequency contamination of low-order dynamical modes to the high levels of noise present in the data. Finally, we propose a method to handle missing observations that produces a substantial dynamics retrieval improvement from synthetic data with a significant static component. Reprocessing of the bR TR-SFX data using the improved method yields dynamical movies with strong isomerization signals compatible with previous findings.
59 BASIC BIOLOGICAL SCIENCES↗
Processing behavior evolution of recycled polypropylene: An integrated experimental and Computer-Aided engineering simulation study
Polypropylene (PP) comprises 21% of global plastics production and 18% of plastics waste, yet less than 1% of solid-waste PP is recycled in the United States (U.S.), representing significant environmental and economic challenges. Mechanical recycling, the most prevalent recycling method, subject's materials to thermomechanical stresses, which typically degrade polymer properties, affecting the quality of polymer products. This study replicates the impact of mechanical recycling through multiple extrusion cycles to examine the effects on PP's processing behavior. Dynamic scanning calorimetry (DSC) measurements showed stable melting behavior across all processing conditions, while crystallization analysis exhibited consistent shifts in kinetic parameters. Rheological characterization demonstrated progressive viscosity reductions through successive cycles, particularly pronounced at elevated reprocessing temperatures. Here, the integration of this experimental data into injection molding simulations showed that recycled PP maintains viable processing characteristics. Our findings establish quantitative correlations between processing history and material behavior, enabling optimization of processing parameters directly rather than relying on trial-and-error approaches. While these results reflect idealized recycling conditions with minimal contamination, they provide a framework for understanding fundamental property evolution during mechanical recycling.
42 ENGINEERING↗
Methanediol from cloud-processed formaldehyde is only a minor source of atmospheric formic acid
Atmospheric formic acid is severely underpredicted by models. A recent study proposed that this discrepancy can be resolved by abundant formic acid production from the reaction ( 1 ) between hydroxyl radical and methanediol derived from in-cloud formaldehyde processing and provided a chamber-experiment-derived rate constant, k 1 = 7.5 × 10 −12 cm 3 s −1 . High-level accuracy coupled cluster calculations in combination with E,J -resolved two-dimensional master equation analyses yield k 1 = (2.4 ± 0.5) × 10 −12 cm 3 s −1 for relevant atmospheric conditions ( T = 260–310 K and P = 0–1 atm). We attribute this significant discrepancy to HCOOH formation from other molecules in the chamber experiments. More importantly, we show that reversible aqueous processes result indirectly in the equilibration on a 10 min. time scale of the gas-phase reaction HCHO + H 2 O ⇌ HOCH 2 OH (2) with a HOCH 2 OH to HCHO ratio of only ca . 2%. Although HOCH 2 OH outgassing upon cloud evaporation typically increases this ratio by a factor of 1.5–5, as determined by numerical simulations, its in-cloud reprocessing is shown using a global model to strongly limit the gas-phase sink and the resulting production of formic acid. Based on the combined findings in this work, we derive a range of 1.2–8.5 Tg/y for the global HCOOH production from cloud-derived HOCH 2 OH reacting with OH. The best estimate, 3.3 Tg/y, is about 30 times less than recently reported. The theoretical equilibrium constant K eq (2) determined in this work also allows us to estimate the Henry’s law constant of methanediol (8.1 × 10 5 M atm −1 at 280 K).
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Suppression of pair beam instabilities in a laboratory analogue of blazar pair cascades
The generation of dense electron–positron pair beams in the laboratory can enable direct tests of theoretical models of γ-ray bursts and active galactic nuclei. We have successfully achieved this using ultrarelativistic protons accelerated by the Super Proton Synchrotron at (CERN). In the first application of this experimental platform, the stability of the pair beam is studied as it propagates through a meter-length plasma, analogous to TeV γ-ray-induced pair cascades in the intergalactic medium. It has been argued that pair beam instabilities disrupt the cascade, thus accounting for the observed lack of reprocessed GeV emission from TeV blazars. If true, this would remove the need for a moderate strength intergalactic magnetic field to explain the observations. We find that the pair beam instability is suppressed if the beam is not perfectly collimated or monochromatic, hence the lower limit to the intergalactic magnetic field inferred from γ-ray observations of blazars is robust.
blazar jets↗
Adsorption of Radioactive Iodine Using Nanocarbon on ETS-10 as Adsorbent
Here, laboratory-synthesized nanocarbon pelletized with titanosilicate (ETS-10) as a support matrix has been investigated for the capture of radioactive iodine present as methyl iodide (CH 3 I) in the off-gas streams produced during aqueous reprocessing of used nuclear fuel. The mass fraction of carbon in the sorbent matrix was 0.10. The effects of residence time and CH 3 I concentration were investigated using a continuous flow column setup to quantify the adsorption and desorption capacities of adsorbent under dynamic conditions from an air stream containing CH 3 I present at concentrations representative of those expected in the off-gas streams. Air with CH 3 I gas as a source in the column resulted in quantifiable CH 3 I adsorption with 0.98 mg/g of adsorption capacity. Laboratory-made nanocarbons had a larger adsorption capacity than those of the other carbons reported in the literature. Additionally, the adsorption capacity of nanocarbon on ETS-10 is compared to that of nanocarbon coated on cordierite in previous studies.
ETS-10↗
Calculations of enrichment cascade performance using enrichment probabilities – a new method
A new method for calculating the performance of uranium enrichment cascades is presented. The method assigns a unique “enrichment probability” for each isotope to move up or down from the basic enrichment unit, allowing independent material balance calculations for each isotope. The formulation is much simpler than previous methods, which rely on isotopic ratios, and this method can be used when previous methods fail. This method gives the same results as published cases for 235 U enrichment and also gives good agreement with published data on minor isotopes. Some comparisons with measured data and other calculations are given. One case shows that the maximum 235 U enrichment that can be obtained by enrichment of reprocessed uranium (0.02% 234 U initial) is 82%. Another example shows a large difference in the minor isotopic content of material enriched in batches compared to continuous enrichment.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Extraction Behavior of Ln(III) ions by T2EHDGA/n-dodecane from Nitric acid and Sodium Nitrate Solutions
The diglycolamide extractant, T2EHDGA, has proven promising for the separation of lanthanides and minor actinides in high-level nuclear waste reprocessing. This neutral extractant has shown significant extraction capacity for HNO3 into the non-polar organic phase, along with hyper-stoichiometric nitrate dependence on extraction of trivalent f-elements. The transport behavior of T2EHDGA/n-dodecane toward trivalent lanthanides is not well understood. This work found a significant increase in distribution measurements for Eu(III) extracted from aqueous HNO3 media as compared to NaNO3. The extraction of Eu(III) from HNO3 results in a different thermodynamic product than predicted by classic solvent extraction of 3:1 ligand-metal complex as observed with NaNO3 in FTIR and UV-vis spectroscopy. Experimental distribution measurements in conjunction with the solvent extraction modeling program, SXLSQI, suggest participation of 1- to 2 HNO3 molecules in the Eu(III)/T2EHDGA complex when extracted from HNO3 media, indicative of a mechanism change responsible for the enhanced extraction behavior toward lanthanides in the presence of HNO3.
Campbell, Emily L.↗
In Situ Monitoring and Kinetic Analysis of the Extraction of Nitric Acid by Tributyl Phosphate in n-Dodecane using Raman Spectroscopy
Understanding the fundamental rates of transfer and complex formation is crucial in maintaining optimal efficiency and effectivity in solvent extraction. Methodologies to effectively analyze solvent extraction systems are lacking in that they are commonly off-line. Thus, a method to effectively investigate solvent extraction systems in a Lewis cell using in situ Raman spectroscopy paired with chemometric modelling has been developed to allow for on-line analysis and monitoring. Kinetic parameters of interfacial mass transfer for the extraction of nitric acid by tributyl phosphate, a process crucial to used nuclear fuel reprocessing, were measured in by spectroscopic monitoring of both phases simultaneously in a two-phase solvent extraction system. Resulting concentration data, derived from a chemometric model using Raman spectra as the base set, allowed for the calculation of kinetic parameters in the system when paired with extraction time. The forward and reverse interfacial mass transfer coefficients, kf and kr, were determined for solutions that were process relevant and of pro-cess interest, where kf was calculated as 5.3 (± 0.3) × 10-3 cm min 1 and kr was calculated as 2.9 (± 0.2) × 10-2 cm min-1. The information obtained regarding solvent extraction parameters and transfer can be applied in the further study of systems of higher complexity involving complex formation and their transfer across a liquid:liquid interface.
extraction, interfacial transport, Lewis Cell, Liq↗