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- 2021 (14) (entfernen)
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- Flame retardant (5)
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Eingeladener Vortrag
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To curtail flammability risks and improve material properties, flame retardants (FRs) and fillers are mixed into rubbers. High loadings of aluminum trihydroxide (ATH) and carbon black (CB) are the most used FRs and reinforcing additive, respectively, in rubbers. To reduce loading without losing mechanical properties, partial substitution of ATH as well as CB by low amounts of multilayer graphene (MLG) nanoparticles is investigated. The high aspect ratio MLG is made of ten graphene sheets. In polybutadiene/chloroprene (BR/CR) nanocomposites 3 phr MLG replaced 15 phr CB and/or 3 phr ATH. Material and mechanical properties as well as fire behavior of the nanocomposites are compared to BR/CR with 20 phr CB both with and without 50 phr ATH. MLG appears as a promising nanofiller to improve the functional properties: replacement of CB improved rheological, curing, and mechanical properties; substitution of ATH improved nanocomposite properties without affecting flame retardancy.
A rigid aromatic phosphorus-containing hyperbranched flame retardant structure is synthesized from 10-(2,5 dihydroxyphenyl)-10H-9-oxa-
10-phosphaphenanthrene-10-oxide (DOPO-HQ), tris(4-hydroxyphenyl)phosphine oxide (THPPO), and 1,4-terephthaloyl chloride (TPC). The resulting poly-(DOPO-HQ/THPPO-terephthalate) (PDTT) is implemented as a flame retardant into an epoxy resin (EP) at a 10 wt% loading. The effects on EP are compared with those of the monomer DOPO-HQ and triphenylphosphine oxide (OPPh3) as low molar mass flame retardants. The glass transition temperature, thermal decomposition, flammability (reaction to small flame), and burning behavior of the thermosets are investigated using differential scanning calorimetry, thermogravimetric analysis, pyrolysis combustion flow calorimetry, UL 94-burning chamber testing, and cone calorimeter measurements.
Although P-contents are low at only 0.6 wt%, the study aims not at attaining V-0, but at presenting a proof of principle: Epoxy resinswith PDTT show promising fire performance, exhibiting a 25% reduction in total heat evolved (THE), a 30% reduction in peak heat release rate (PHRR) due to flame inhibition (21% reduction in effective heat of combustion (EHC)), and an increase in Tg at the same time. This study indicates that rigid aromatic hyperbranched polymeric structures offer a promising route toward multifunctional flame retardancy.
Leather is among the most ancient, widely used materials worldwide. Industrial-scale leather production produces large quantities of organic waste attained during shaving and buffing steps during processing. In this study, leather wastes (LW) are used as fillers in flame retarded polymer composites. LW is investigated as a multifunctional bio-filler that enhances the fire performance of flame retarded poly(ethylene–vinyl acetate) (EVA) containing phosphorus flame retardants (P-FRs) ammonium polyphosphate (APP) or a melamine-encapsulated APP (eAPP). Using LW from tanneries as adjuvants to enhance P-FRs in EVA reduces industrial wastes that otherwise require costly waste management solutions. Materials are characterized multi-methodically via mechanical tests, electron microscopy, rheology, thermogravimetric analysis, evolved gas analysis, and condensed phase FTIR, also reaction-to-small-flames and cone calorimeter tests. EVA containing 10 wt-% LW and 20 wt-% P-FRs achieve 20% reductions in fire loads versus EVA, and up to 10% reduction in effective heats of combustion versus EVA with equal (30 wt-%) P-FR loadings. Enhanced char stabilization of EVA composites with LW and P-FRs lowered peaks of heat release rates up to 53% compared to EVA, and up to 40% compared to equal P-FRs loadings. Synergisms between LW and P-FRs in EVA are quantified. A chemical decomposition mechanism is proposed.
A phosphorous soybean-oil–based polyol was derived via epoxidation and ring opening reaction as an alternative to petrochemical-based polyol for the synthesis of flexible polyurethane foams (FPUFs). 5-wt.% and 10-wt.% of expandable graphite (EG) were added to further improve flame retardancy. The mechanical properties (tensile strength and compression stress) of the foams were investigated. Thermogravimetric analysis (TGA) coupled with Fourier-transform infrared (FTIR) were conducted to evaluate the pyrolysis; limiting oxygen index (LOI), UL 94 and cone calorimeter were performed to analyze the fire performance of the foams; smoke density chamber was used to investigate the smoke released during burning. When 10-wt.% of EG was used, the flame retardancy of the foams was much enhanced due to the synergistic effect between phosphorus and EG. The char yield was three times higher (54wt.%). The fire load MARHE approached 100 kWm−2, half of the value expected for a superposition. The combination of phosphorous polyols and EG is proposed as strategy for future flame retarded FPUFs.
A systematic approach was used to investigate the weathering-induced degradation of a common water–based intumescent coating. In this study, the coatings are intended for humid indoor applications on steel substrates. The coating contains ammonium polyphosphate, pentaerythritol, melamine, and polyvinyl acetate. By replacing each ingredient with a less water-soluble substance, the most vulnerable substances, polyvinyl acetate and pentaerythritol, were identified. Furthermore, the weathering resistance of the system was improved by exchanging the ingredients. The coatings were stressed by artificial weathering tests and evaluated by fire tests. Thermogravimetry and Fourier-transform infrared spectroscopy were used to study the thermal decomposition. This study lays the foundation for the development of a new generation of water-based intumescent coatings.
Efficient flame retardancy is often achieved only when applying multicomponent systems. Flame retardants are combined or used together with adjuvants or synergists; fibres and fillers contribute to fire properties crucially. Multicomponent systems are discussed in their capacity as general and powerful strategy for achieving and optimizing flame retardant polymeric materials.
Überblick über die Herausforderungen, Anforderungen und Lösungswege für den Flammschutz von Polyurethanwerkstoffen (thermoplastisches und elastomeres Polyurethan (TPU, PUR), PUR Hard- und Weichschäume, PIR, PUR Coatings). Die Werkstoffcharakteristika wie Pyrolyse, effektive Verbrennungswärme, Rückstandsausbeute, Verarbeitungsparameter und kg-Preis definieren die Anforderungen an Flammschutzlösungen. Der Flammschutz ist spezifisch für das Material ausgelegt, aber auch für die verschiedenen Anwendungen (Automobilbau, Schienenfahrzeuge, Bauwesen, Elektrotechnik, usw.), d.h. um spezielle Brandtests zu bestehen. Die Pyrolyse und das Brandverhalten von PUR und PUR-Schäumen sowie der flammgeschützten Varianten wird diskutiert. Die gängigen Flammschutzmittel(-kombinationen) werden zusammengefasst und mit Beispielen belegt.
The Burning of Plastics
(2021)
The burning of a polymer is a physico–chemical process strongly influenced by the coupling of a chemical reaction – oxidation of fuel – in the gas phase with a chemical decomposition reaction – pyrolysis – in the condensed phase via heat and mass transfer. The heat and mass flux control the intensity of fire and the ablation of fuel. Indeed, the temperature profile as a function of time may be one of the most important responses of a specimen to understand its burning behavior. Further, several physical phenomena, such as the heat absorption of the materials, thermal conductivity, and also melt flow and dripping, play a major role in determining ignition, flammability, and fire behavior. The burning of a polymer is very complex. The various phenomena interact with each other, e. g., pyrolysis also influences the viscosity of the melt, and, thus, whether dripping or charring results in a protective layer, increasing the shielding effect of the residual protective layer. Only a detailed and comprehensive description opens the door to a well-founded understanding of the burning behavior of polymeric materials.
Die Forderung, dass der Flammschutz von Kunststoffen nicht nur zum bei der Herstellung der jeweiligen Produkte, sondern auch über die gesamte Einsatzdauer im geforderten Maß wirksam ist, stellt eine große Aufgabe dar. Ferner ist die Anforderung für viele Produkte in der Praxis neu, da bisher vor allem der Einfluss der Flammschutzmittel auf die Stabilität der Polymerwerkstoffe, nicht aber die Stabilität des Flammschutzes untersucht wurde. Das Langzeitverhalten halogenfreier Systeme ist bis heute wenig untersucht, insbesondere weil Phosphor- und Stickstoff-basierte Systeme die oxidative Beständigkeit von Polymeren weniger zu beeinflussen scheinen als halogenhaltige FSM. Die Frage, wie zuverlässig der Flammschutz wirkt, wenn Kunststoffe einige Jahre im Innen- und Außenbereich im Einsatz sind und dabei wechselnden Beanspruchungen ausgesetzt waren, wurde bislang nur vereinzelt untersucht. Mögliche Auswirkungen von Witterungseinflüssen auf flammgeschützte Polymerwerkstoffe sind, dass die Flammschutzmittel selbst abbauen, ausgewaschen werden, oder auch durch Wechselwirkung mit den eingesetzten Additiven oder mit den Alterungsprodukten der Polymermatrix in ihrer Wirkung nachlassen. Hier bestand großer Forschungsbedarf, um an den Punkt zu gelangen, die Beständigkeit der Flammschutzeigenschaften eines Produktes über seine gesamte Lebensdauer zuverlässig garantieren zu können. Diese Fragestellung greift das durchgeführte Forschungsvorhaben auf.
Ziel war die Untersuchung der Langzeitstabilität der Flammschutzwirkung von halogenfrei flammgeschützten Polymerwerkstoffen unter diversen Witterungseinflüssen. Dazu wurden die Schädigungsmechanismen der Polymerwerkstoffe und der Flammschutzmittel sowie die auftretenden Wechselwirkungen analysiert, um ein Verständnis für die ablaufenden Prozesse zu entwickeln und Empfehlung für die Reduzierung der Alterung zu erarbeiten. Gegenstand der Untersuchungen waren anwendungsrelevante Flammschutz-Konzepte, die miteinander verglichen wurden. Die Erarbeitung von Struktur-Eigenschafts-Beziehungen ermöglichte die Beschreibung der Empfindlichkeiten und den Vergleich zwischen den Systemen. Darauf basierend wurden für die FSM spezifische Leitlinien für die Optimierung der Langzeitstabilität des Flammschutzes erstellt.