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At least 19 records

Non-flammable elastomeric fiber from a fluorinated elastomer and containing an halogenated flame retardant

Flame retardant elastomeric compositions are described comprised of either spandex type polyurethane having incorporated into the polymer chain halogen containing polyols, conventional spandex type polyurethanes in physical admixture with flame retardant additives, or fluoroelastomeric resins in physical admixture with flame retardant additives. Methods are described for preparing fibers of the flame retardant elastomeric materials and articles of manufacture comprised of the flame retardant clastomeric materials and non elastic materials such as polybenzimidazoles, fiberglass, nylons, etc.

Howarth, J. T.↗

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↗

Process for spinning flame retardant elastomeric compositions

Flame retardant elastomeric compositions comprised of either spandex type polyurethane having halogen containing polyols incorporated into the polymer chain, conventional spandex type polyurethanes in physical admixture with flame retardant additives, or fluoroelastomeric resins in physical admixture with flame retardant additives were developed. Methods are described for preparing fibers of the flame retardant elastomeric materials and manufactured articles as well as nonelastic materials such as polybenzimidazoles, fiberglass, and nylons, for high oxygen environments.

Howarth, J. T.↗

Flame retardant spandex type polyurethanes

Flame retardant elastomeric compositions were developed, comprised of: (1) spandex type polyurethane having incorporated into the polymer chain, halogen containing polyols; (2) conventional spandex type polyurethanes in physical admixture flame retardant additives; and (3) fluoroelastomeric resins in physical admixture with flame retardant additives. Methods of preparing fibers of the flame retardant elastomeric materials are presented and articles of manufacture comprised of the elastomeric materials are mentioned.

Howarth, J. T.↗

Flame retardants

The use of flame retardants in plastics has grown only slightly in recent years and will probably grow slowly in the future. The reasons for this are slow economic growth and the absence of fundamentally new requirements for future fire prevention. The trends are toward the increasing use of easily handled, dust-free and well-dispersed flame retardant compounds and master batches; there are no spectacular new developments. In the future, questions of smoke evolution, toxicity and corrosiveness of combustion gases will become increasingly important, especially due to new regulations and rising requirements for environmental protection.

Troitzsch, J.↗

Flame Retardant Fibers for Human Space Exploration - Past, Present, and Future

The National Aeronautics and Space Administration (NASA) has led in the development of unique flame retardant fibers for human spaceflight since the beginning of the Apollo program. After the Apollo 1 fire which killed Command Pilot Virgil I 'Gus' Grissom, Senior Pilot Edward H. White II, and Pilot Roger B. Chaffee from cardiac arrest on January 27, 1967, the accident investigators found severe third degree burns and melted spacesuits on the astronauts bodies. NASA immediately initiated an extensive research program aimed at developing flame retardant and flame resistant fibers for the enriched oxygen atmosphere of the Apollo crew cabin. Fibers are flame retardant when they have been modified by chemical and thermal treatments. Fibers are flame resistant when they are made of inherently flame resistant materials (i.e. glass, ceramic, highly aromatic polymers). Immediately after this tragic accident, NASA funded extensive research in specifically developing flame retardant fibers and fabrics. The early developmental efforts for human spaceflight were for the outer layer of the Apollo spacesuit. It was imperative that non-flammable fabrics be used in a 100% oxygen environment. Owens-Corning thus developed the Beta fiber that was immediately used in the Apollo program and later in the Space Shuttle program. Aside from the urgent need for protective fabrics for the spacesuit, NASA also needed flame retardant fabrics for both clothing and equipment inside the spacecraft. From the mid-1960s to the early 1980's, NASA contracted with many companies to develop inherently flame retardant fibers and flame retardant finishes for existing fibers. Fluorocarbons and aromatic polyamides were the polymers of great interest for the development of new inherently flame retardant fibers for enriched oxygen environments. These enriched environments varied for different space programs. For example, the Apollo program requirements were for materials that would not support combustion in a 70%/30% oxygen/nitrogen environment at 6.3 pounds per square inch (psi). The Skylab program flammability requirements were set at 80%/20% oxygen/nitrogen ratios at 5 psi. While many fibers produced under several NASA contracts were never used, a few have become commercial products. The intent of this paper is to present the developmental history of some of these new or modified textile fibers. These developmental efforts are presented at various levels of details depending on the source of the historical records.

Orndoff, Evelyne↗

Shuttle Environmental Assurance: Brominated Flame Retardants - Concerns, Drivers, Potential Impacts and Mitigation Strategies

Brominated Flame Retardants (BFRs) are widely used in the manufacture of electrical and electronic components and as additives in formulations for foams, plastics and rubbers. The United States (US) and the European Union (EU)have increased regulation and monitoring of of targeted BFRs, such as Polybrominated Diphenyl Ethers (PBDEs) due to the bioaccumulative effects in humans and animals. In response, manufacturers and vendors of BFR-containing materials are changing flame-retardant additives, sometimes without notifying BFR users. In some instances, Deca-bromodiphenylether (Deca-BDE) and other families of flame retardants are being used as replacement flame retardants for penta-BDE and octa-BDE. The reformulation of the BFR-containing material typically results in the removal of the targeted PBDE and replacement with a non-PBDE chemical or non-targeted PBDE. Many users of PBDE -based materials are concerned that vendors will perform reformulation and not inform the end user. Materials performance such as flammability, adhesion , and tensile strength may be altered due to reformulation. The requalification of newly formulated materials may be required, or replacement materials may have to be identified and qualified. The Shuttle Enviornmental Assurance (SEA) team indentified a risk to the Space Shuttle Program associated with the possibility that targeted PBDEs may be replaced without notification. Resultant decreases in flame retardancy, Liquid Oxygen (LOX) compatibility, or material performance could have serious consequences.

Clark-Ingram, Marceia↗

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↗

Flame Retardant Fibers for Human Space Exploration - Past, Present, and Future

The National Aeronautics and Space Administration (NASA) has led the development of unique flame retardant fibers for the specific requirements of different space programs. Three of these fibers have greatly contributed to the safety of all the space missions since the Apollo program. Beta alumina-silica microfiber developed for the outer layer of the space suit after the Apollo 1 fire is no longer used and has been replaced by other glass fibers. Expanded polytetrafluoroethylene (e-PTFE) fiber used in the current spacesuit is mostly known today through its trade mark Gore-Tex®. Polybenzimidazole (PBI) filament fiber used in many applications from the Apollo to the Space Shuttle program is no longer available. More recently, TOR"TM" copolymer of polyimide fiber developed during the space shuttle program to resist the atomic oxygen present in Low Earth Orbit has been barely used. The high cost and narrow range of aeronautical and aerospace applications have, however, led to a limited production of these fibers. Only fibers that found niche markets survived. Yet, deep space exploration will require more of these inherently flame retardant fibers than what is available today. There is a need for new flame retardant fabrics inside the space vehicles as well as a need for logistics reduction for long term space missions. Materials like modacrylic and polyimide are good candidates for future flame retardant aerospace fabrics. New fabrics must be developed for astronauts' clothing, as well as crew quarters and habitat. Therefore, both staple and filament fibers of various linear densities are needed for a three years mission to Mars.

Orndoff, Evelyne↗

Lithium-Ion Electrolytes Containing Flame Retardant Additives for Increased Safety Characteristics

The invention discloses various embodiments of Li-ion electrolytes containing flame retardant additives that have delivered good performance over a wide temperature range, good cycle life characteristics, and improved safety characteristics, namely, reduced flammability. In one embodiment of the invention there is provided an electrolyte for use in a lithium-ion electrochemical cell, the electrolyte comprising a mixture of an ethylene carbonate (EC), an ethyl methyl carbonate (EMC), a fluorinated co-solvent, a flame retardant additive, and a lithium salt. In another embodiment of the invention there is provided an electrolyte for use in a lithium-ion electrochemical cell, the electrolyte comprising a mixture of an ethylene carbonate (EC), an ethyl methyl carbonate (EMC), a flame retardant additive, a solid electrolyte interface (SEI) film forming agent, and a lithium salt.

Smart, Marshall C.↗

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↗

Lithium-Ion Electrolytes Containing Phosphorous-Based, Flame-Retardant Additives

Future NASA missions aimed at exploring Mars, the Moon, and the outer planets require rechargeable batteries that can operate over a wide temperature range (-60 to +60 C) to satisfy the requirements of various applications. In addition, many of these applications will require improved safety, due to their use by humans. Currently, the state-of-the-art lithium-ion (Li-ion) system has been demonstrated to operate over a wide range of temperatures (-40 to +40 C); however, abuse conditions can often lead to cell rupture and fire. The nature of the electrolyte can greatly affect the propensity of the cell/battery to catch fire, given the flammability of the organic solvents used within. Li-ion electrolytes have been developed that contain a flame-retardant additive in conjunction with fluorinated co-solvents to provide a safe system with a wide operating temperature range. Previous work incorporated fluorinated esters into multi-component electrolyte formulations, which were demonstrated to cover a temperature range from 60 to +60 C. This work was described in Fluoroester Co-Solvents for Low-Temperature Li+ Cells (NPO-44626), NASA Tech Briefs, Vol. 33, No. 9 (September 2009), p. 37; and Optimized Li-Ion Electrolytes Con tain ing Fluorinated Ester Co-Solvents (NPO-45824), NASA Tech Briefs, Vol. 34, No. 3 (March 2010), p. 48. Other previous work improved the safety characteristics of the electrolytes by adding flame-retardant additives such as triphenyl phosphate (TPhPh), tri-butyl phosphate (TBuPh), triethyl phosphate (TEtPh), and bis(2,2,2-trifluoroethyl) methyl phosphonate (TFMPo). The current work involves further investigation of other types of flame-retardant additives, including tris(2,2,2-trifluoroethyl) phosphate, tris(2,2,2-trifluoroethyl) phosphite, triphenylphosphite, diethyl ethylphosphonate, and diethyl phenylphosphonate added to an electrolyte composition intended for wide operating temperatures. In general, many of the formulations investigated in this study displayed good performance over a wide temperature range, good cycle life characteristics, and are expected to have improved safety characteristics, such as low flammability. Of the electrolytes studied, 1.0 M LiPF6 in EC+EMC+DEP (20:75:5 v/v %) and 1.0 M LiPF6 in EC+EMC+DPP (20:75:5 v/v %) displayed the best operation at low temperatures, whereas the electrolyte containing triphenylphosphite displayed the best cycle life performance compared to the baseline solution. It is anticipated that further improvements can be made to the life characteristics with the incorporation of a SET promoters (such as VC, vinylene carbonate), which will likely inhibit the decomposition of the flame-retardant additives.

Smart, Marshall C.↗

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↗

Polyfunctional epoxies - Different molecular weights of brominated polymeric additives as flame retardants in graphite composites

The imparting of flame retardancy to graphite-reinforced composites without incurring mechanical property deterioration is investigated for the case of an experimental, trifunctional epoxy resin incorporating brominated polymeric additives (BPAs) of the diglycidyl type. Such mechanical properties as flexural strength and modulus, and short beam shear strength, were measured in dry and in hot/wet conditions, and the glass transition temperature, flammability, and water absorption were measured and compared with nonbromilated systems. Another comparison was made with a tetrafunctional epoxy system. The results obtained are explained in terms of differences in the polymeric backbone length of the bromine carrier polymer. BPAs are found to be a reliable bromine source for fire inhibition in carbon-reinforced composites without compromise of mechanical properties.

Nir, Z.↗

Flame Retardant Epoxy Resins

As part of a program to develop fire resistant exterior composite structures for future subsonic commercial aircraft, flame retardant epoxy resins are under investigation. Epoxies and their curing agents (aromatic diamines) containing phosphorus were synthesized and used to prepare epoxy formulations. Phosphorus was incorporated within the backbone of the epoxy resin and not used as an additive. The resulting cured epoxies were characterized by thermogravimetric analysis, propane torch test, elemental analysis and microscale combustion calorimetry. Several formulations showed excellent flame retardation with phosphorous contents as low as 1.5% by weight. The fracture toughness of plaques of several cured formulations was determined on single-edge notched bend specimens. The chemistry and properties of these new epoxy formulations are discussed.

Thompson, C. M.↗

A new brominated polymeric additive for flame retardant glass-filled polybutylene terephthalate

Attention is called to the undesirable effects (poor ultraviolet light stability and blooming) sometimes introduced by brominated flame retarders. A brominated polymeric additive (BPA) with little or none of these undesirable side effects is compared with decabromobiphenyl oxide (DBBPO). The additive bears the product name F-2300. It is found to be more easily dispersed than DBBPO. The F-2300 is as effective as the DBBPO in the oxygen index test. The improved efficiency of the F-2300 may be explained by its better dispersion in polybutylene terephthalate (PBT). Glass-filled PBT containing F-2300 is found to be more resistant to UV degradation than DBBPO-containing formulas. Formulations with F-2300 therefore have a longer useful outdoor life. F-2300 is a diglycidyl-type polymer containing 50 percent aromatically bound bromine. Its melting point is 112 C, and it is stable up to 372 C. It is pointed out that since its melts at a relatively low temperature, it can be introduced into the formulation as a large agglomerate and still be dispersed evenly throughout the polymer.

Nir, Z.↗