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At least 109 records · Page 6

Aging mechanisms of filled cross-linked polyethylene (XLPE) cable insulation material exposed to simultaneous thermal and gamma radiation

Thermal and simultaneous thermal and gamma radiation aging experiments were conducted on an industry grade cross-linked polyethylene (XLPE) cable insulation material, which is a composite material with XLPE as polymer matrix and various additives and fillers. Reverse engineering was conducted to identify and quantify the material composition given that this information was not revealed by the cable manufacture. Samples were then aged at temperatures of 60, 90, and 115 °C, exposed to gamma radiation for total doses of 0 to 324 kGy, and at dose rates of 0 to 540 Gy/h. Aging mechanisms were studied using various materials characterization techniques including pyrolysis gas chromatography mass spectrometry (Py-GCMS), differential scanning calorimetry (DSC), nuclear magnetic resonance spectroscopy (NMR), and gel-fraction tests. Results show that the flame-retardant components were decomposed into smaller molecules when the material was exposed to gamma radiation, while no changes were observed when the samples were aged thermally without gamma radiation. With exposure to gamma radiation, the crystalline phase of the XLPE were damaged by gamma radiation introducing defects in the crystals, resulting in smaller and less perfect crystals. The dominance of chain scission or chain reformation process largely depends on the chain mobility, which is decided by the aging temperature. Chain scission was seen to dominate when the material was exposed to gamma radiation at 60 °C. Chain cross-linking slightly dominated when the material was exposed to gamma radiation at 90 °C and became more dominant with exposure to gamma radiation at 115 °C. No significant change to the XLPE polymer matrix was observed when the samples were exposed to thermal aging without gamma radiation. Finally, antioxidant is more effective in protecting the XLPE polymer matrix under thermal aging, but less effective with sample exposure to gamma radiation.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Occupational and dietary differences in hydroxylated and methoxylated PBDEs and metals in plasma from Puget Sound, Washington, USA region volunteers

BACKGROUND: Electronic waste (E-waste) recycling is a rapidly growing occupation in the USA with the potential for elevated exposure to flame retardants and metals associated with electronic devices. We previously measured polybrominated diphenyl ethers (PBDEs) in plasma from E-waste workers and found them similar to non-E-waste workers. OBJECTIVES: This study focused on structurally related PBDE derivatives, the hydroxylated (OH-PBDEs) and methoxylated (MeO-PBDEs) forms along with metals known to occur in E-waste. Humans can metabolize PBDEs and some MeO-PBDEs into OH-PBDEs, which is a concern due to greater health risks associated with OH-PBDEs METHODS: We measured 32 different OH-PBDEs and MeO-PBDEs in plasma samples provided by 113 volunteers living in the greater Puget Sound region of Washington State, USA. We measured 14 metals in a subset of 10 E-waste and 10 non-E-waste volunteers. Volunteers were classified based on occupational and dietary habits: work outdoors and weekly consume = 5 seafood servings (outdoor), electronic waste recycling (E-waste) or non-specific indoor occupations (indoor). A two-week food consumption diary was obtained from each volunteer prior to blood sampling. RESULTS: OH-PBDEs were detected in all volunteers varying between 0.27 – 102 ng/g/g-lipid. The MeO-PBDEs were detected in most, but not all volunteers varying between 0 – 60.4 ng/g/g-lipid. E-waste recyclers had OH-PBDE and MeO-PBDE plasma levels that were similar to the indoor group. The outdoor group had significantly higher levels of MeO-PBDEs, but not OH-PBDEs. Comparison of plasma concentrations of BDE-47 with its known hydroxylated metabolites suggested OH-PBDE levels were likely determined by biotransformation and at least two subpopulations identified differing in their apparent rates of OH-PBDE formation. The metals analysis indicated no significant differences between E-waste workers and non-E-waste workers. CONCLUSIONS: Our results indicate E-waste workers do not have elevated plasma levels of these contaminants relative to non-E-waste workers with similar dietary habits.

Schultz, Irvin↗

Chemically Controllable Porous Polymer–Nanocrystal Composites with Hierarchical Arrangement Show Substrate Transport Selectivity

Functional organic–inorganic hybrid materials with tunable properties are useful across many application areas, ranging from gas storage to electronics, flame retardants, separations, and catalysis. Combining polymers, with a suite of functional groups and conformational flexibility, and inorganic nanoparticles, with tunable surface chemistry and composition, yields hybrids with novel functional properties. Specifically, in catalysis, control of the electronic environment at a metal interface is paramount in determining the catalytic properties. In this contribution, we describe a modular process to prepare porous polymer–nanocrystal (NC) composites in a hierarchical, multilayered synthesis, in which multiple parameters can be accurately tuned: polymer functional groups and the corresponding pore structure, the polymer layer thickness, and the NC size, shape, and composition. This process provides for a variety of controlled materials with high surface area, tunable chemistry, and thermal and chemical stabilities. Furthermore, we demonstrate their utility for shape- and size-selective catalytic conversions both in oxidation and hydrogenation reactions, where they show increased selectivity by orders of magnitude compared to conventional polymer-supported metal catalysts. In light of the high degree of control in the composite structure, this method allows for the design and realization of catalysts for several reactions and reaction environments and for nanomaterials with other applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Review on Preprocessing Strategies, Deactivation, Thermal Safety, and Future Perspectives in Lithium-Ion Battery Recycling

The rapid growth in the use of lithium-ion batteries (LIBs) in electric vehicles, consumer electronics, and renewable energy storage has made effective end-of-life management essential. Recycling LIBs is critical not only for resource recovery and environmental protection but also for ensuring safety and economic viability. This review focuses on the preprocessing technologies that precede typical recovery processes, including disassembly, sorting, discharging, electrolyte removal, dismantling, thermal treatment, separation, and flotation. These steps play a foundational role in determining the efficiency, safety, and environmental impact of LIB recycling. LIBs pose substantial fire and explosion risks due to residual charge, flammable electrolytes, and reactive materials. The conditions and successive progression of the exothermic reactions which lead to thermal runaway has been discussed. It also explores secure deactivation techniques such as external circuit discharge, saline immersion, and thermomechanical methods, alongside fire prevention strategies including the use of flame retardants, elimination of oxidants, and reduction of heat generation and accumulation. Challenges and future directions are outlined, highlighting the need for standardized designs, automation, and safer, more sustainable recycling infrastructure. Furthermore, this review is distinguished by its focused analysis of preprocessing and deactivation steps, with particular attention to the thermal safety engineering aspects of LIB recycling.

Battery deactivation↗

Suspect and Nontarget Screening for Contaminants of Emerging Concern in an Urban Estuary

This study used suspect and nontarget screening with high-resolution mass spectrometry to characterize the occurrence of contaminants of emerging concern (CECs) in the nearshore marine environment of Puget Sound (WA). In total, 87 non-polymeric CECs were identified; those confirmed with reference standards (45) included pharmaceuticals, herbicides, vehicle-related compounds, plasticizers, and flame retardants. Eight polyfluoroalkyl substances were detected; perfluorooctanesulfonic acid (PFOS) concentrations were as high as 72-140 ng/L at one location. Low levels of methamphetamine were detected in 41% of the samples. Transformation products of pesticides were tentatively identified, including two novel transformation products of tebuthiuron. While a hydrodynamic simulation, analytical results, and dilution calculations demonstrated the prevalence of wastewater effluent to nearshore marine environments, the identity and abundance of selected CECs revealed the additional contributions from stormwater and localized urban and industrial sources. For the confirmed CECs, risk quotients were calculated based on concentrations and predicted toxicities, and eight CECs had risk quotients >1. Dilution in the marine estuarine environment lowered the risks of most wastewater-derived CECs, but dilution alone is insufficient to mitigate risks of localized inputs. These findings highlighted the necessity of suspect and nontarget screening and revealed the importance of localized contamination sources in urban marine environments.

Tian, Zhenyu↗

High-Temperature-Performance Cyanate Ester Composites with Carboranes

Cyanate ester (CE) is an important class of materials among high-temperature performance thermosets. It is used in aerospace launch vehicles, heat sinks, booms, and trusses of satellites etc. due to its high glass transition temperatures (>220°C), excellent thermal stability, and low flammability. Current approaches to improve the thermal stability of CE include incorporation of siloxanes or phosphorus- based flame retardants (PFRs). In this work, we have explored boron-based hydroxy (PD) and epoxy (EP) functionalized carborane additives to improve the thermal properties of CE. Carborane fillers were solvent blended at various mass loadings in the resin and cured to study their effect on thermal properties. PD and EP carboranes react with CE to form iminocarbonate and oxazolidinone linkages respectively. Cure kinetics studies at different wt% loadings explained that carboranes catalyze the curing reaction by reducing curing activation energy by about 54% and 26% for 10 wt% loadings of PD and EP carboranes respectively. In addition, carborane-filled cyanate ester (CE) nanocomposites demonstrate an exceptionally high thermal stability as compared to the pristine resin in air and inert environment. Our thermogravimetric analysis (TGA) experiments show that the ultimate char yield of the resin can be increased from 0% to as high as 76% and 82% with 30 wt% PD and EP carborane loading respectively at 1000 °C in air. The initial degradation temperature T d;5 of the composites decreased with increasing carborane loadings in both air and argon. For instance, T d;5 for CE was 465 and 471.6 °C in argon and air while that for P20 was 437.4 and 452.1 °C. Modulated TGA studies gave evidence of the effect of carboranes on degradation kinetics and the mechanism of the resin in air and inert environment. The effect of bonding between carboranes and CE at various loadings on the thermal expansion of the matrix was also studied using Thermomechanical Analyzer (TMA). PD carborane reduced the T g for P20 to about 225 °C while CE had T g >350 °C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hierarchical Biogenic-Based Thermal Insulation Foam

Biogenic-based foam, renowned for its sustainable and eco-friendly properties, is emerging as a promising thermal insulating material with the potential to significantly enhance energy efficiency and sustainability in building applications. However, its relatively high thermal conductivity, large-pore configurations, and energy-intensive manufacturing processes hinder its widespread use. Here, we report on the scalable, one-pot synthesis of biogenic foams achieved by integrating recycled paper pulp and in situ nanoporous silica formation, resulting in a hierarchical structure comprising both micropores and nanopores. Ambient solvent-exchange drying can preserve the pore structure by reducing the capillary forces during the drying process. The resulting flame-retardant and hydrophobic foam exhibits low density (0.110 g/cm 3 ), ideal porosity (70.69%), excellent thermal conductivity (0.033 W/(m·K)), and impressive compressive strength (1.48 MPa at 80% strain). Furthermore, this recyclable biogenic foam, with its hierarchical pore structure and environmental durability, shows great potential for energy-efficient building applications.

36 MATERIALS SCIENCE↗

Ultralight and fire-extinguishing current collectors for high-energy and high-safety lithium-ion batteries

Inactive components and safety hazards are two critical challenges in realizing high-energy lithium-ion batteries. Metal foil current collectors with high density are typically an integrated part of lithium-ion batteries yet deliver no capacity. Meanwhile, high-energy batteries can entail increased fire safety issues. Here we report a composite current collector design that simultaneously minimizes the ‘dead weight’ within the cell and improves fire safety. An ultralight polyimide-based current collector (9 μm thick, specific mass 1.54 mg cm-2) is prepared by sandwiching a polyimide embedded with triphenyl phosphate flame retardant between two superthin Cu layers (~500 nm). Compared to lithium-ion batteries assembled with the thinnest commercial metal foil current collectors (~6 µm), batteries equipped with our composite current collectors can realize a 16-26% improvement in specific energy and rapidly self-extinguish fires under extreme conditions such as short circuits and thermal runaway.

25 ENERGY STORAGE↗

Influence of functional additives, fillers, and pigments on thermal and catalytic pyrolysis of polyethylene for waste plastic upcycling

Pyrolysis offers a relatively green and economical method to convert waste plastics into valuable chemicals and fuels without the need for harmful solvents, toxic chemicals, or costly high-pressure reactors. Despite its popularity among chemical upcycling technologies, industrial adoption suffers from feedstock heterogeneity, low-quality products, and catalyst deactivation. Most plastics in our daily lives are formulated with functional additives, fillers, and colorants. These additives remaining in end-of-life waste streams increase feedstock heterogeneity, creating a challenging issue in recycling plastics. Still, the potential impacts of additives on the chemical upcycling of plastics have been poorly understood. In this study, polyethylene compounded with a range of widely used additives (antioxidants, stabilizers, pigments, fillers, slip agents, and flame retardants) was subjected to both thermal pyrolysis and catalytic pyrolysis in different catalyst-to-feedstock contact modes. It showed that many inorganic additives, such as talc, kaolin, CaCO 3 , TiO 2 , carbon black, and zinc stearate, facilitated polymer decomposition during pyrolysis, increasing light hydrocarbons while also promoting aromatic and carbon residue formation. Conversely, antioxidants and stabilizers inhibited depolymerization, favoring heavier hydrocarbons. During catalytic pyrolysis with HZSM-5 zeolite, additives strongly enhanced aromatic and catalytic coke formation, especially when there was direct contact between plastics and catalysts. Although certain additives seem beneficial in the short term by promoting polymer cracking and improving the selectivity of aromatics, the transport of the additives and their degradation products and increased carbon coking can contaminate products, deactivate or modify catalysts, and foul reactors. These findings address a critical knowledge gap in effectively converting waste plastics via a greener route.

42 ENGINEERING↗

Solvent-mediated contaminant removal from plastic waste using thermodynamic modeling

Plastics recycling is hindered by the compositional complexity of plastic waste, which can include numerous polymer components as well as low concentrations of additives and non-intentionally added substances. These latter small-molecule species, which we collectively refer to as contaminants, can harm human health and will build up in recycled plastic causing environmental and downstream processing challenges if not removed. In this work, we present molecular modeling approaches using the COnductor-like Screening MOdel for Real Solvents (COSMO-RS) to guide the selection of solvents that are capable of removing targeted contaminants from plastic waste. By considering the thermodynamic partitioning of contaminant species between a solvent phase and polymer phase, we identify guidelines for solvent selection to promote either the low-temperature extraction of contaminants from plastic waste or the removal of contaminants as part of a dissolution-based plastics recycling process. We present four case studies to illustrate the application of the computational approach to the removal of brominated flame retardants, phthalates, and selected perfluoroalkyl substances, and compare to both literature and newly collected experimental data to illustrate model prediction accuracy. Furthermore, the case studies highlight the capability of the modeling approach to help design recycling processes that explicitly account for contaminant removal, thereby increasing product purity during dissolution-based recycling or facilitating chemical recycling of contaminant-free plastics.

Zhou, Panzheng [University of, Wisconsin, Madison,↗

Organo-catalyzed deamination of polystyrene sulfonamide for diverse post-polymerization modification of styrenic polymers

Post-polymerization modification allows for the incorporation of functional groups that would otherwise be incompatible with polymerization conditions, enhancing synthetic efficiency and facilitating the creation of complex polymer architectures for specialized applications, such as biomedical devices, electronics, and advanced coatings. Herein, we report a method inspired by late-stage functionalization of small molecules for the post-polymerization modification of aromatic polymers, specifically polystyrene (PS), under mild reaction conditions. First, PS was converted to polystyrene sulfonamide (PSSNH 2 ) with an 85% yield using established procedures. PSSNH 2 was subsequently transformed into a reactive sulfinate by deamination using an N-heterocyclic carbene (NHC) catalyst and benzaldehyde. The catalytic process was optimized by varying catalysts, solvents, bases, temperatures, and reaction times. The highest degree of deamination was 88% with a bicyclic NHC and K 2 CO 3 base in DMSO for 18 hours at 120 °C. The reactive sulfinate was then treated with various functional reagents, resulting in a library of aromatic polymers with different substituents with high degrees of functionalization ranging from 74% to 98%. Similarly, we modified expanded PS waste with trifluorobutyl iodide with a degree of functionalization of 72%, highlighting a new avenue for plastic upgrading. This approach could be used to rapidly generate functionalized polymers from PS with potential applications, including antibacterial properties and flame retardancy.

Shrestha, Tulaja [Univ. of Delaware, Newark, DE (U↗

Temperature Dependence of FDR Response for Thermally Aged Low-Voltage Cables

Frequency Domain Reflectometry (FDR) has attracted significant attention for use in nuclear power plants (NPPs) for non-destructive cable health monitoring. However, cable aging detection using FDR faces challenges due to its high sensitivity to environmental factors such as temperature, vibrations, proximity to other cables, and so on. This work aims to evaluate the influence of measurement temperature on the FDR reflected signal in a low voltage cable undergoing accelerated thermal aging. A 100 ft long multi-core low-voltage unshielded power cable insulated with flame retardant ethylene propylene rubber (FR-EPR) and covered by a chloro-polyethylene (CPE) jacket was selected for this study. The cable was energized during aging by a 480 VAC 3-phase motor, and a 30 ft mid-section of this cable was routed through an air circulating oven held at 140 °C for up to an effective aging time of 62 days. FDR measurements were taken periodically with the oven on (at 140 °C) and with the oven off (at 22 °C). A comparative analysis of data collected at both temperatures showed that the FDR response was strongly dependent on measurement temperature. FDR measurements at ambient temperature showed large peaks corresponding to impedance changes in the aged section of the cable after 3 days of aging. These peaks continued to rise steadily with increasing aging time. However, for measurements taken at 140 °C, slowly rising peaks in the oven region (aged section) were observed only after a lead time of 23 days of aging. This work highlights the importance of measurement temperature on the performance of FDR as a condition monitoring tool for aging cables.

Sriraman, Aishwarya↗

Computational Evaluation of Thermal Response of Open-Cell Foam With Circular Pore (Computional Evaluation of Thermal Response of Open-Cell Foam with Circular Pore)

The evaluation of effective material properties in heterogeneous materials (e.g., composites or multicomponent structures) critically relevant to a wide spectrum of applications, including nuclear power, electronic packaging, flame retardants, hypersonics, and gas turbine power. The work described in this paper is centered around the numerical assessment of the thermal behavior of porous materials obtained from finite element thermal modeling and simulation. Here, two-dimensional, steady state analyses were performed on unit cells with centered, circular pores using a second order accurate Galerkin finite element method (FEM). The effective thermal conductivities of the porous systems were examined, encompassing a range of porosities from 4.9% to 60.1%. The geometries of the models were generated based on ordered circular pores for each modeled porosity level. The system response quantity (SRQ) under investigation was the dimensionless effective thermal conductivity across the unit cell. The dimensionless effective thermal conductivity was compared across all simulated cases, producing a trend between porosity and effective thermal conductivity. In the presented investigation, the method of manufactured solutions (MMS) was used to perform code verification, and the grid convergence index (GCI) was employed to estimate discretization uncertainty as solution verification. Code verification concluded an approximately second order accurate Galerkin FEM solver. It was found that the introduction of porosity to the unit cell material structure reduces effective thermal conductivity, as anticipated. Numerical results obtained in this study are compared to an analytical solution and to a sample of empirical data.

36 MATERIALS SCIENCE↗

High-Safety Electrolytes for Lithium-Ion Batteries : Is non-flammability of electrolyte overrated in the overall safety performance of lithium ion batteries?

It has been widely considered that the flammability of the liquid electrolyte is one of the most influential factors that determine the safety of lithium ion batteries (LIBs). Following this consideration, a completely non-flammable electrolyte was designed and adopted to graphite||LiFePO 4 (Gr||LFP) batteries. Contrary to the conventional understanding, the completely non-flammable electrolyte with phosphorus-containing solvents exhibits inferior safety performance in commercial Gr||LFP batteries, in comparison to the flammable conventional LiPF 6 -organocarbonate electrolyte. Mechanistic studies identify the exothermic reactions between the electrolyte (especially the flame retarding phosphate solvent) and the charged electrodes as the “culprit” behind such a counterintuitive phenomenon. The discovery emphasizes the importance of reducing the electrolyte reactivity when designing safe electrolytes, as well as the necessity of evaluating safety performances of electrolyte on a battery level.

25 ENERGY STORAGE↗

Advances in Carbon Capture and Use (CCU) Technologies: A Comprehensive Review and CO2 Mitigation Potential Analysis

One of society’s major current challenges is carbon dioxide emissions and their consequences. In this context, new technologies for carbon dioxide (CO2) capture have attracted much attention. One of these is carbon capture and utilization (CCU). This work focuses on the latest trends in a holistic approach to carbon dioxide capture and utilization. Absorption, adsorption, membranes, and chemical looping are considered for CO2 capture. Each CO2 capture technology is described, and its benefits and drawbacks are discussed. For the use of carbon dioxide, various possible applications of CCU are described, starting with the utilization of carbon dioxide in agriculture and proceeding to the conversion of CO2 into fuels (catalytic processes), chemicals (photocatalytic processes), polymers, and building supplies. For decades, carbon dioxide has been used in industrial processes, such as CO2-enhanced oil recovery, the food industry, organic compound production (such as urea), water treatment, and, therefore, the production of flame retardants and coolants. There also are several new CO2-utilization technologies at various stages of development and exploitation, such as electrochemical conversion to fuels, CO2-enhanced oil recovery, and supercritical CO2. At the end of this review, future opportunities are discussed regarding machine learning (ML) and life cycle assessment (LCA).

Peres, Christiano B.↗

Structure and Anharmonicity of α- and β -Sb 2 O 3 at Low Temperature

Antimony oxides are important materials for catalysis and flame-retardant applications. The two most common phases, α-Sb 2 O 3 (senarmontite) and β-Sb 2 O 3 (valentinite), have been studied extensively. Specific focus has been placed recently on their lattice dynamics properties and how they relate to the α-β phase transformation and their potential anharmonicity. However, there has not been any direct investigation of anharmonicity in these systems, and a surprising lack of low-temperature structural information has prevented further study. Here, we report the powder neutron diffraction data of both phases of Sb 2 O 3 , as well as structural information. α-Sb 2 O 3 behaved as expected, but β-Sb 2 O 3 revealed a small region of zero thermal expansion along the c axis. Additionally, while the β phase matched well with reported atomic displacement parameters, the α phase displayed a marked deviation. This data will enable further investigations into these systems.

36 MATERIALS SCIENCE↗

A Comparative Multi-System Approach to Characterizing Bioactivity of Commonly Occurring Chemicals

A 2019 retrospective study analyzed wristband personal samplers from fourteen different communities across three different continents for over 1530 organic chemicals. Investigators identified fourteen chemicals (G14) detected in over 50% of personal samplers. The G14 represent a group of chemicals that individuals are commonly exposed to, and are mainly associated with consumer products including plasticizers, fragrances, flame retardants, and pesticides. The high frequency of exposure to these chemicals raises questions of their potential adverse human health effects. Additionally, the possibility of exposure to mixtures of these chemicals is likely due to their co-occurrence; thus, the potential for mixtures to induce differential bioactivity warrants further investigation. This study describes a novel approach to broadly evaluate the hazards of personal chemical exposures by coupling data from personal sampling devices with high-throughput bioactivity screenings using in vitro and non-mammalian in vivo models. To account for species and sensitivity differences, screening was conducted using primary normal human bronchial epithelial (NHBE) cells and early life-stage zebrafish. Mixtures of the G14 and most potent G14 chemicals were created to assess potential mixture effects. Chemical bioactivity was dependent on the model system, with five and eleven chemicals deemed bioactive in NHBE and zebrafish, respectively, supporting the use of a multi-system approach for bioactivity testing and highlighting sensitivity differences between the models. In both NHBE and zebrafish, mixture effects were observed when screening mixtures of the most potent chemicals. Observations of BMC-based mixtures in NHBE (NHBE BMC Mix) and zebrafish (ZF BMC Mix) suggested antagonistic effects. In this study, consumer product-related chemicals were prioritized for bioactivity screening using personal exposure data. High-throughput high-content screening was utilized to assess the chemical bioactivity and mixture effects of the most potent chemicals.

60 APPLIED LIFE SCIENCES↗

Halogenation of microcapsule walls

Procedure for halogenation of confining walls of both gelatin and gelatin-phenolic resin capsules is similar to that used for microencapsulation. Ten percent halogen content renders capsule wall nonburning; any higher content enhances flame-retardant properties of selected internal phase material. Halogenation decreases permeability of wall material to encapsulated materials.

Davis, T. R.↗