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- Flame retardancy (5)
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Revolutionizing our polymer industry for adaption to a sustainable carbon circular economy has become one of today’s most demanding challenges. Exploiting renewable resources to replace fossil-fuel—based plastics with biopolymers such as poly(lactic acid) (PLA) is inevitable while using waste streams as a raw material resource at least is promising. When it comes to using PLA as technical polymer, its high flammability must be addressed by flame retardants compatible with the thermoplastic processing of PLA and its compostability. This study proposes microalgae enriched with phosphorus from wastewater (P-Algae) as an elegant way towards a kind of sustainable organophosphorus flame retardant. The concept is demonstrated by investigating the processing, pyrolysis, flammability, and fire behavior of PLA/P-Algae, while varying the P-Algae content and comparing P-Algae with four alternative bio-fillers (phosphorylated lignin, biochar, thermally treated sewage sludge, and metal phytate) with different P-contents as meaningful benchmarks.
To ensure fire safety, polymers are filled with flame retardants and smoke suppressants. To meet the highest requirements, it is essential to understand the decomposition of those polymeric materials. This study reveals interactions between polymer, smoke suppressants, and flame retardants, and discusses their impact on the materials’ flame retardancy, smoke emission, smoke toxicity, and particle emission in conventional loadings to provide deeper general understanding. Low melting oxide glass, melem, spherical silica, sepiolite, melamine polyphosphate, and boehmite in an aluminum diethylphosphinate flame-retarded polyamide 6.6 were investigated. All smoke suppressants improve the protective layer and act as an adjuvant. Silica and melem performed best under forced flaming conditions. Spherical silica reduces the peak of heat release rate by 39% and the total heat evolved by 14%, whereas 10 wt% melem lowers the total smoke production by 41%. Melem alters the mode of action of aluminum diethylphosphinate from gas to more condensed phase activity. This change reduces flame inhibition and hence smoke toxicity, but further improves the protective layer due to charring reactions in the decomposition mechanism. In addition, the sizes of the smoke particles decrease because of the prolonged time in the pyrolytic zone. This study highlights that interactions between polymer, flame retardants, and smoke suppressants can significantly determine the smoking and burning behavior.
Replacing antimony trioxide (ATO) in flame retardant formulations is an urgent task due to its toxicity. There are indications that calcium hypophosphite (CaP) may be a promising replacement. This study investigates the decomposition, fire behavior, and smoke release of brominated flame-retarded acrylonitrile butadiene styrene (ABS) under various fire scenarios like ignition, developing fire and smoldering, while replacing ATO with CaP and CaP/talc. Adding 4 wt.-% of talc to CaP formulations showed beneficial effects on flammability due to changes in the viscosity and barrier properties. Synergism between 8 wt.-% talc and CaP improved the protective layer in the developing fire scenario, resulting in a ∼60 % decrease in the peak of heat release rate and reduction of ∼21 % in total smoke production (ref. ABS+Br+ATO). With a conventional index of toxicity (CIT) of below 0.75, ABS+Br+CaP passes the highest requirements according to EN 45545-2. Overall, the CaP/talc materials improve flame retardancy, show less smoke emission under forced flaming conditions, and prevent chronic intoxication and environmental pollution through smoke particles contaminated with antimony.
Pressure-sensitive adhesive tapes are used in several industrial applications such as con-struction, railway vehicles and the automotive sector,where the burning behavior is ofcrucial importance. Flame retarded adhesivetapes are developed and provided, however,often without considering the interaction of adhesive tapes and the bonded materialsduring burning nor the contribution of the tapes to fire protection goal of the bondedcomponents in distinct fire tests. This publication delivers an empirical comprehensiveknowledge how adhesive tapes and their flame retardancy effect the burning behaviorof bonded materials. With a special focus on the interaction between the single compo-nents, one flame retarded tape and one tapewithout flame retardant are examined inscenarios of emerging and developing fires, along with their bonds with the commonmaterials wood, zinc-plated steel, mineral wool, polycarbonate, and polymethylmethacry-late. The flame retardant significantly improved the flame retardancy of the tape as afree-standing object and yielded a V-2 rating in UL 94 vertical test and raised the OxygenIndex by 5 vol.%. In bonds, or rather laminates, the investigations prove that the choiceof carrier and substrates are the factors with the greatest impact on the fire propertiesand can change the peak of heat release rate and the maximum average rate of heatemission up to 25%. This research yielded a good empirical overall understanding of thefire behavior of adhesive tapes and bonded materials. Thus, it serves as a guide for tapemanufacturers and applicants to develop tapes and bonds more substrate specific.
Several investigation groups have studied the flame-retardancy modes of action and properties of epoxy resins in the past; nevertheless, the selection of suitable flame retardants for epoxy resins remains challenging, and the transfer to fiber composites is difficult. The addition of flame retardants and glass fibers (GFs) to a polymeric system in a fire scenario changes the polymer's pyrolytic path and burning characteristics, reduces the heat released in the combustion, and suppresses the modes of action in the condensed and gas phase. In this study, the thermal analysis, flammability, fire behavior, residue analysis, fire stability, and quantification of modes of action of three different systems with three halogen-free flame retardants (melamine polyphosphate (MPP), ammonium polyphosphate (APP), and silane ammonium polyphosphate (SiAPP)) and three different types of GFs (unidirectional (UD), bidirectional (BD), and woven roving (WR)) will be compared with pure epoxy resin as a reference.
Combining buffing leather fibers from industrial waste streams with ammonium polyphosphate and bentonite clay is proposed as a flame-retardant additive for polypropylene. The paper addresses how they can be processed into attractive composites with the desired mechanical properties. Buffing leather fibers function as a multifunctional bio-filler and as a synergist for the flame retardant, resulting in fire retardancy successful enough to increase the oxygen index (LOI) by up to 7 vol.-% and to achieve a V0 UL 94 classification. Impressively reduced heat release rates are obtained in the cone calorimeter at 50 kW/m2 irradiation; for instance, the maximum average rate heat evolved (MARHE) drops from 765 to below 200 kW m 2. The synergistic effects are quantified and shown to be very strong for LOI and MARHE. This work opens the door to use waste buffing leather fibers as a promising multifunctional and synergistic bio-filler.
Efficient flame retardancy is often achieved only when applying synergistic multicomponent systems. Flame retardants are combined or used together with adjuvants or synergists to enhance their efficiency, reduce the amount required, or reduce the costs; fibers and fillers contribute to fire properties crucially. Although the main flame-retardant modes of action are known, the detailed scientific understanding usually falls short, when it comes to complex synergistic multicomponent systems, the important tiny optimizations, or quantifying in terms of specific fire properties. This paper tries to illuminate the concept of synergistic flame retardants. The need for the multicomponent approach and the main phenomena are described. Thought-provoking impulses are delivered on how the understanding of multicomponent systems promotes the evidence-based development of future flame retardant polymeric materials. Multicomponent systems are discussed in their capacity as general powerful strategy for achieving and optimizing flame retardant polymeric materials.
This paper is based mainly on the overall conclusions and concrete results of several projects performed in the group of the author. Thanks to my (former) students and co-operation partners in these projects. Thanks for financing to DFG (Scha 730/8-1 Scha 730/8-2, Br 3376/1-1, Scha 730/19-1), AiF IGF (438 ZN, 17833N/2, 19078 N/2), and BMBF (03X0111C, 01DN16040).
Lecture-like introduction in the topic. Fundamental aspects are discussed: Burning of polymers, fire risks, pyrolysis, combustion in the flame, physical chemistry of ignition, flame spread and steady state burning, flame retardancy mechanisms and groups of flame retardants, fire hazards (smoke, toxic products) and environmental concerns, fire testing.
Sacrifice Few to Save Many: Fire Protective Interlayers in Carbon- Fiber-Reinforced Laminates
(2024)
The fire protection of carbon-fiber-reinforced polymer (CFRP) laminates often relies on flame-retardant coatings, but in some applications, their efficacy may diminish upon direct fire exposure due to rapid pyrolysis. This study introduces an innovative approach by integrating protective interlayers within the laminate structure to enhance the fire resistance. Various materials, including ceramic composite WHIPOX, titanium foil, poly(etherimide) (PEI) foil, basalt fibers, rubber mat, and hemp fibers, were selected as protective interlayers. These interlayers were strategically placed within the laminate layout to form a sacrificial barrier, safeguarding the integrity of the composite. Bench-scale fire resistance tests were conducted, where fire (180 kW/m2) was applied directly to the one side of the specimen by a burner while a compressive load was applied at the same time. Results indicate significant prolongation of time to failure for CFRP laminates with protective interlayers, which is up to 10 times longer. This innovative approach represents a potential advance in fire protection strategies for CFRP laminates, offering improved resilience against fire-induced structural failure.
The dripping behaviour of polymers is often observed experimentally through the UL94 flammability standard test. In this work, polymeric dripping under fire is investigated numerically using particle finite element method. A parametric analysis was carried out to observe the influence of a single property on overall dripping behaviour via a UL94 vertical test model. Surrogates and property ranges were defined for variation of the following parameters: glass transition temperature (Tg), melting temperature (Tm), decomposition temperature (Td), density (ρ), specific heat capacity (Cp), apparent effective heat of combustion of the volatiles, char yield (μ), thermal conductivity (k), and viscosity (η). Polyamide, poly(ether ether ketone), poly(methyl methacrylate), and polysulfone were used as benchmarks. Simulated results showed that specific heat capacity, thermal conductivity, and char yield allied with viscosity were the properties that most influenced dripping behaviour (starting time and occurrence).