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At least 19 records

Effects of a composite flame retardant system on the flame retardancy and mechanical performance of epoxy resin adhesive

Abstract A flame‐retarded epoxy resin (ER) adhesive with strong flame retardancy and adhesion performance was prepared. The coated ammonium polyphosphate (MFAPP), melamine (MEL), and organic montmorillonite (OMMT) were mixed to prepare a composite flame retardant. It was subsequently blended with a toughened ER thoroughly and then the mixture was cured with polyamide. The resultant ER adhesive thermosets achieved UL‐94 V‐0 rating during vertical burning test, and the limiting oxygen index value was as high as 31.6%. The shear strength of the ER adhesive was 27.9 MPa when 25 wt% MFAPP/MEL/OMMT was introduced. Compared with the pure adhesive, the flame retardant epoxy adhesive maintained outstanding adhesion performance because of the good compatibility between the composite flame retardant additives and the toughened ER adhesive. Cone calorimetry tests indicated that the release of heat and smoke were obviously declined with the incorporation of the composite flame retardant system in comparison to pure ER adhesive thermoset. The investigation of flame retardant mechanism revealed that the composite MFAPP/MEL/OMMT flame retardant system stimulated the generation of highly expanded, integral, and strong char layer and the formed char layer exerted superior insulation effect during combusiton. The present work provided an alternative approach to prepare flame retardant ER adhesive with the similar excellent adhesive performance.

Li, Sheng↗

Biobased Flame Retardants Towards Sustainable Building Materials with Low Embodied Carbon

Incorporation of fire retardants in different types of products is one of the essential steps in the material production process to minimize fire risk and meet fire safety requirements. A variety of commonly used flame retardants based on halogen, mineral, and other compounds has gained popularity due to their efficient flame-retardant behaviors. However, especially in the case of halides, there are numerous toxicity related issues and environmental pollution effects that have urged the building sector to deviate from their use and focus on the development of non-toxic alternatives. Therefore, to enhance the safety of flame retardants, the synthesis of flame retardants from waste feedstocks using phosphorous chemistry with a dual flame-retardant mechanism has been established. A range of waste feedstocks that include cardanol, vanillin, and gallic acids has been converted into a series of flame retardants using a one-step approach by incorporating phosphorous moieties into their structures. The established pathways allow to develop a range of flame-retardant materials by converting waste feedstocks into phosphorous-based materials with inherent flame retardancy. The introduction of abundant aromatic structures from biobased feedstocks enables high charring capabilities in materials in which these biobased flame retardants have been incorporated, increasing their char yields which significantly enhances the flame suppressing properties of the designed materials. Studies show that inclusion of phosphoric moieties into structures allows the displacement of flame enhancing radicals, by releasing non-flammable and non-toxic gases, therefore inhibiting the spread of fire in the gas phase. The resulting biobased flame retardants have been incorporated in wood substrates, foam insulation, and hemp fibers where the results show that only 1-5% of loading of biobased flame retardant suppressed the flame completely. This study represents a novel approach for the development of flame retardants with high performance while utilizing waste feedstocks as a source for their design.

Demchuk, Zoriana [ORNL] (ORCID:0000000326292235)↗

Thermal aging effects on crosslinked polyethylene cable insulation with decabromodiphenyl ether flame retardant alternative

Decabromodiphenyl ether (decaBDE) has been extensively used as a flame retardant in several applications, including nuclear electrical cable insulation. However, decaBDE has been identified as a persistent, bioaccumulative and toxic (PBT) substance, leading to regulatory scrutiny. The Environmental Protection Agency (EPA) published a regulation on January 6, 2021, aimed at phasing out the manufacturing, processing, and distribution of decaBDE. This rule set a compliance deadline of March 8, 2021, for the manufacture and processing of decaBDE, and an extended deadline of January 6, 2023, for specific applications including wire and cable insulation in nuclear power generation facilities. In response to such regulations, RSCC, a major supplier of safety-related electrical cables and associated products to the U.S. nuclear industry updated the formula of their crosslinked polyethylene (XLPE) insulation to replace the historically used decaBDE flame retardant with an acceptable alternative. This change from the previous decaBDE-containing XLPE prompted interest in comparative performance of the two material formulations, especially with respect to characteristics relevant to safety-related function such as thermal and radiation resistance. RSCC graciously provided samples of wire insulated with the decaBDE-containing XLPE formulation and corresponding wire insulated with XLPE of the new formulation, containing a decaBDE alternative. In this work we compare characteristics of the two formulations and a previously produced commercial version of the RSCC decaBDE-containing XLPE insulation subjected to thermal aging at 150 °C and 165 °C. The comparison was focused on mechanical durability, thermal stability in the oxidative environment, and chemical structures. Briefly, • Tensile elongation at break (EAB) results showed loss of mechanical elasticity with longer aging time, as expected. Aging time dependence of EAB did not differ between the decaBDE-containing and decaBDE-alternative samples. • Subtle differences between the two materials can be detected from Fourier-transform infrared spectroscopy (FTIR) absorbance spectra in the range below 1700 cm -1 , are assumed to be related to decomposition of flame retardant additives during thermal aging. • The oxidation induction time (OIT) data seemed to show that the unaged decaBDE-containing XLPE material is more thermally stable than the unaged decaBDE-alternative material, but the discrepancy in OIT decreased with aging time and the OIT values of the two materials became similar starting with the 4 th day of aging at 165 °C. This thermal aging investigation confirmed that the mechanical durability, a key property monitored for cable qualification, was not significantly affected by the modification of the formulation with a decaBDE alternative flame-retardant system in the investigated thermal aging conditions. Further studies on the same sets of materials exposed to thermal and gamma radiation aging would further inform comparison of the materials safety-related function.

36 MATERIALS SCIENCE↗

PET waste- and bio-derived imine vitrimers for shape-memory, intrinsic flame-retardant, and recyclable carbon fiber composites

Developing circular multifunctional vitrimers and carbon fiber–reinforced polymers (CFRPs) that are simultaneously recyclable, mechanically robust, and intrinsically flame retardant remains a major challenge. Here, in this study, we report multifunctional vitrimers and their carbon fiber–reinforced vitrimer (CFRV) composites, where the vitrimer design integrates closed-loop recyclability, enhanced interfacial adhesion, and intrinsic flame retardancy within a single materials platform. The vitrimer matrix is synthesized from post-consumer polyethylene terephthalate (PET) waste and a vanillin-derived phosphorus-containing crosslinker, forming an imine-based network. The resulting vitrimer resin exhibits high tensile strength, thermal healability, repeated reprocessability, programmable shape memory, and rapid chemical depolymerization under mild conditions. Amine-functionalized carbon fibers significantly improve fiber–matrix interfacial bonding, yielding CFRVs with tensile strengths up to 789 MPa and complete recovery of structurally intact fibers after chemical recycling. The phosphorus-rich aromatic network further imparts intrinsic flame retardancy, enabling self-extinguishing behavior without external additives. This work advances a materials design paradigm for next-generation multifunctional, sustainable vitrimers and CFRVs, while simultaneously addressing the recycling challenges associated with both plastic and CFRP waste.

Bio-derived crosslinker↗

Consideration of Decabromodiphenyl Ether Flame Retardant in Thermal and Radiation Aging of Crosslinked Polyethylene Cable Insulation

Decabromodiphenyl ether (decaBDE) has been used as a flame-retardant additive in nuclear-grade electrical cable insulation. However, decaBDE has been identified as a persistent, bioaccumulative and toxic (PBT) substance, leading to regulatory scrutiny. On January 6, 2021, the Environmental Protection Agency (EPA) published a final rule to phase out decaBDE. The 2021 rule set a two-year compliance deadline for “processing and distribution in commerce of decaBDE for use in wire and cable insulation in nuclear power generation facilities.” In recognition of industry concerns following a sudden discontinuation of decaBDE-containing Class 1E wire and cable essential for nuclear power operations and the time needed for qualifying the individual components using the alternative insulation technology, an extended compliance deadline was set in the finalized amendments to the 2021 rule as published by the Environmental Appeals Board on November 12, 2024. The 2024 rule set the compliance deadline for processing and distributing decaBDE-containing wire and cable insulation until the end of the service life of these materials. Since decaBDE has long been relied upon as the flame retardant in one of the most common cross-linked polyethylene (XLPE) nuclear cable insulation formulations, RSCC Firewall III insulation, questions have naturally arisen regarding whether changes in cable performance might be expected for XLPE containing a decaBDE alternative, especially for safety-related cables that must perform their safety function in a design basis event such as a loss of coolant accident.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Flame retardant biogenic building insulation materials from hemp fiber

Biogenic thermal insulation materials are in high demand because of its carbon-sequestration nature. However, high flammability, moisture condensation, and relatively high thermal conductivity of biogenic material are major concerns for sustainable building applications. In this study, we report the fire-retardant cellulose xerogel insulation nanocomposites derived from hemp fiber recycling and silica xerogel, in which the boric acid treatment improves its fire retardancy. The as-prepared materials show a low thermal conductivity of 31.3 mW/m K, high flexural modulus of 665 MPa, hydrophobicity with the water contact angle of 115°, and fire retardancy with 30% weight loss over a period of burning time 10 min. Overall, this work provides an effective method for the synthesis of fire-retardant biogenic thermal insulation materials and shows a promising way for next-generation bio-based insulation materials.

36 MATERIALS SCIENCE↗

Flame-retardant cellulose-aerogel composite from agriculture waste for building insulation

Bio-based thermal insulation materials are in high demand due to their availability, reproducibility, and carbon-sequestration nature. However, high flammability, moisture condensation, and high thermal conductivity of biogenic material are major concerns for sustainable building applications. In this study, we report the fire-retardant cellulose aerogel insulation nanocomposites derived from wheat straw and silica aerogel, in which sodium bicarbonate improves its fire retardancy. We combined blended straw fibers and hammermilled straw fibers to create a structural hierarchy composite. The blended straw, with its longer and thicker size, served as reinforcement, while the hammermilled straw fibers acted as filler. This hierarchical structure was further integrated with aerogel for applications in green buildings. The as-prepared materials show a low thermal conductivity of 24.1 mW/m.K, high flexural modulus of 736 MPa, hydrophobicity with a water contact angle of 110.42°, and excellent fire retardancy. Altogether, this work provides an effective method for the synthesis of fire-retardant biogenic thermal insulation materials and shows a promising way for next-generation bio-based insulation materials.

36 MATERIALS SCIENCE↗

Chemical Recycling of Mixed Plastics and Valuable Metals in the Electronic Waste Using Solvent-Based Processing

Annually, 20-55 million tons of electronic waste (e-waste) is produced worldwide (5% of all municipal solid waste). Although e-waste embodies only 2% of America’s municipal waste, it accounts for a significantly larger proportion of the heavy metals and flame retardants present in the waste stream. Currently, less than 20% of all e-waste is recycled in the United States because the heterogeneity of the feedstock limits the opportunity for reuse in high value products and processing of the waste itself is often too costly to justify handling. To address this concern, the aims of this study are: 1) to identify the major plastic and metal compositions within electronic shredder residue (ESR), 2) to formulate solvents and processing conditions to separate 90% of the plastics targeted from consumer shred ESR, and 3) to develop a process design model to estimate the cost and energy efficiency of the proposed solvent-based processing. In this study, a pre-sorted heterogeneous ESR feedstock (one where aluminum, magnetic components, and hazardous battery materials removed by an e-waste recycling facility) was used, with the major compositions of the ESR characterized. It was found that 25 wt.% of the feedstock was composed of plastics, 6 wt.% rubber, 27 wt.% printed circuit boards, 23% wire, and the remainder metals and capacitors. Within the plastic portion, polystyrene (PS, 40 wt.%), acrylonitrile butadiene styrene (ABS, 25 wt.%), and styrene-acrylonitrile (SAN, 9wt.%) were identified to compose the majority of the screened plastics using Fourier transform infrared spectroscopy (FTIR). Next, selective solvents were screened using Hansen Solubility Parameter Theory (HSP) for dissolving PS and ABS. The pre-screening results show that methylene chloride (dichloromethane, DCM) and tetrahydrofuran (THF) are capable of dissolving the most PS and ABS, while methanol (MeOH) and ethylene glycol (EG) are capable of precipitating the most PS and ABS. These solvents were subsequently used to recover polymers and remove. flame retardants within the ESR feedstock. By optimizing the dissolution time and the solvents used, the highest polymer dissolution yield (99 wt.%%) was achieved using DCM for 48 hr. Both pre-screened anti-solvents (MeOH and EG) showed the highest polymer precipitation yield (71 wt.%). In terms of flame retardant removal rate, EG was found to have a high phosphorus-containing flame retardant removal rate (up to 98%). Characterization shows that the proposed solvent-based processing can preserve a high molecular weight fraction of the polymers and effectively remove flame retardants. Cost analysis indicates that the amount of the solvent/anti-solvent recovered after the reaction would play a critical role in reducing the operating costs. The energy analysis shows that the proposed solvent-based processes can save up to 60% of the embodied energy used to manufacture plastics used in electronics (PS and ABS were used for calculations). The results from this project prove the potential of solvent-based processing to produce secondary materials (plastics and metals) from e-waste for cross-industry reuse.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Applying Improved Optical Recognition with Machine Learning on Sorting Cu Impurities in Steel Scrap

Annually, 20–55 million tons of electronic waste (e-waste) is produced worldwide (5% of all municipal solid waste). Although e-waste embodies only 2% of America’s municipal waste, it accounts for a significantly larger proportion of the heavy metals and flame retardants present in the waste stream. Currently, less than 20% of all e-waste is recycled in the United States because the heterogeneity of the feedstock limits the opportunity for reuse in high value products and processing of the waste itself is often too costly to justify handling. To address this concern, the aims of this study are: 1) to identify the major plastic and metal compositions within electronic shredder residue (ESR), 2) to formulate solvents and processing conditions to separate 90% of the plastics targeted from consumer shred ESR, and 3) to develop a process design model to estimate the cost and energy efficiency of the proposed solvent-based processing. In this study, a pre-sorted heterogeneous ESR feedstock (one where aluminum, magnetic components, and hazardous battery materials removed by an e-waste recycling facility) was used, with the major compositions of the ESR characterized. It was found that 25 wt.% of the feedstock was composed of plastics, 6 wt.% rubber, 27 wt.% printed circuit boards, 23% wire, and the remainder metals and capacitors. Within the plastic portion, polystyrene (PS, 40 wt.%), acrylonitrile butadiene styrene (ABS, 25 wt.%), and styrene-acrylonitrile (SAN, 9wt.%) were identified to compose the majority of the screened plastics using Fourier transform infrared spectroscopy (FTIR). Next, selective solvents were screened using Hansen Solubility Parameter Theory (HSP) for dissolving PS and ABS. The pre-screening results show that methylene chloride (dichloromethane, DCM) and tetrahydrofuran (THF) are capable of dissolving the most PS and ABS, while methanol (MeOH) and ethylene glycol (EG) are capable of precipitating the most PS and ABS. These solvents were subsequently used to recover polymers and remove. flame retardants within the ESR feedstock. By optimizing the dissolution time and the solvents used, the highest polymer dissolution yield (99 wt.%%) was achieved using DCM for 48 hr. Both pre-screened anti-solvents (MeOH and EG) showed the highest polymer precipitation yield (71 wt.%). In terms of flame retardant removal rate, EG was found to have a high phosphorus-containing flame retardant removal rate (up to 98%). Characterization shows that the proposed solvent-based processing can preserve a high molecular weight fraction of the polymers and effectively remove flame retardants. Cost analysis indicates that the amount of the solvent/anti-solvent recovered after the reaction would play a critical role in reducing the operating costs. The energy analysis shows that the proposed solvent-based processes can save up to 60% of the embodied energy used to manufacture plastics used in electronics (PS and ABS were used for calculations). The results from this project prove the potential of solvent-based processing to produce secondary materials (plastics and metals) from e-waste for cross-industry reuse.

36 MATERIALS SCIENCE↗

Compressible battery foams to prevent cascading thermal runaway in Li-ion pouch batteries

Lithium-ion battery packs require thermal management to achieve optimum life and safety. This is becoming crucial for battery packs composed of high-energy-density cells. Pouch cells themselves achieve highest packaging efficiency but require additional structural support and thermal management when grouped into modules, especially under abusive conditions such as thermal runaway. Novel foam battery pads have demonstrated to cushion volume changes of pouch cells and are reengineered in this study to mitigate cell-to-cell thermal runaway propagation. The compressible pads are made of polyurethane foams incorporating flame-retardant additives or coatings, including intumescent and fire wall materials. Here their performances were evaluated by conducting nail penetration tests on modules composed of pouch cells at 100% state of charge (SOC), with the foams placed in between the cells. Experimental results show cascading thermal runaway was considerably delayed by polyurethane foams incorporating flame-retardant additives or coatings. Complete prevention of cascading failure was achieved with dense polyurethane foams with multilayered coatings of both fire wall and intumescent materials.

25 ENERGY STORAGE↗

Identifying Performance Advantaged Biobased Chemicals Utilizing Bioprivileged Molecules

Two technology areas were advanced; a) novel molecules with improved performance in the end use application of organic corrosion inhibitors and flame retardant nylon polymers and b) development of a systematic process for identifying biomass-derived molecules with improved performance in end use applications. In total 17 novel organic corrosion inhibitors were identified that had significantly better performance than the commercial reference organic corrosion inhibitor and 7 novel nylons were synthesized with improved flame retardant properties relative to standard nylon-6,6. While an end-to-end systematic process for identifying biomass-derived molecules with improved end use performance was not completed, important progress was made computational tools for mining chemical structures from the literature and databases as well as establishing reaction network generation algorithms to aid in the discovery of novel molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemical Recycling of Mixed Plastics in Electronic Waste Using Solvent-Based Processing

Currently, less than 20% of electronic waste (E-waste) produced in the U.S. is recycled. To improve the recycling rate of E-waste, the study aimed to: (1) identify the major plastics found within electronic shredder residue (ESR), (2) design solvents and processing conditions capable of separating out 90% of the plastic in ESR, and (3) estimate the energy efficiency of the solvent-based process developed. Preliminary screening showed 25 wt.% of the ESR was composed of plastics, with two polymers dominating the sorted plastic fraction—polystyrene (PS, 40 wt.%) and acrylonitrile butadiene styrene (ABS, 25 wt.%). Subsequently, solvents and anti-solvents were screened using Hansen Solubility Parameter Theory for PS, ABS, and ESR dissolution. The pre-screening results showed dichloromethane (DCM) and tetrahydrofuran (THF) as the most effective solvents for PS and ABS, with methanol (MeOH) and ethylene glycol (EG) as the most effective anti-solvents. By optimizing the dissolution time and the solvents used, the highest polymer dissolution yield (99 wt.%) was achieved using DCM for 48 h. Both MeOH and EG precipitated 71 wt.% of the polymer fraction of ESR. EG removed more phosphorus containing flame retardants (94 wt.%) than MeOH (69 wt.%). Energy analysis indicated that the solvent-based processes could save 25–60% of the embodied energy for PS and ABS. Characterization showed that the solvent-based processing could preserve the high molecular weight fraction of the polymers while removing flame retardants at the same time. The results from this study prove the potential of solvent-based processing to produce secondary plastic materials from E-waste for cross-industry reuse.

Anderson, Lester↗

Identifying Performance Advantaged Biobased Chemicals Utilizing Bioprivileged Molecules (Final Report)

Two technology areas were advanced; a) novel molecules with improved performance in the end use application of organic corrosion inhibitors and flame retardant nylon polymers and b) development of a systematic process for identifying biomass-derived molecules with improved performance in end use applications. In total 17 novel organic corrosion inhibitors were identified that had significantly better performance than the commercial reference organic corrosion inhibitor and 7 novel nylons were synthesized with improved flame retardant properties relative to standard nylon-6,6. While an end-to-end systematic process for identifying biomass-derived molecules with improved end use performance was not completed, important progress was made computational tools for mining chemical structures from the literature and databases as well as establishing reaction network generation algorithms to aid in the discovery of novel molecules.

36 MATERIALS SCIENCE↗