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The durability of flame retardancy is a challenge for cables over long lifetimes. The degradation of flame retardance is investigated in two kinds of exposures, artificial weathering and humidity. In this basic study, typical mineral flame retardants in two polymers frequently used in cable jackets are investigated to get the fundamental picture. Aluminum hydroxide (ATH) and magnesium hydroxide (MDH) are compared in ethylene‐vinyl acetate (EVA), and further in EVA and linear low‐density polyethylene (LLDPE) cables containing the same ATH. The changes in chemical structure at the surface are studied through attenuated total reflectance Fourier transform infrared spectroscopy (ATR‐FTIR), the formation of cracks, and changes in color are investigated. The cone calorimeter and a bench scale fire testing cable module are utilized to evaluate the fire behavior of the cables. Although the flame retardancy deteriorated slightly, it survived harsh exposure conditions for 2000 h. Compared to EVA/MDH and LLDPE/ATH, the fire behavior of EVA/ATH is the least sensitive. Taken together, all of the results converge to estimate that there will be no problem with flame retardancy performance, for materials subjected to natural exposure for several years; the durability of fire retardancy is questionable for longer periods, and thus requires further investigation.
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.
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.
Phosphorus-based flame retardants were incorporated into different, easily preparable matrices, such as polymeric thermoset resins and paraffin as a proposed model for polyolefins and investigated for their flame retardancy performance. The favored mode of action of each flame retardant was identified in each respective system and at each respective concentration. Thermogravimetric analysis was used in combination with infrared spectroscopy of the evolved gas to determine the pyrolysis behavior, residue formation and the release of phosphorus species. Forced flaming tests in the cone calorimeter provided insight into burning behavior and macroscopic residue effects. The results were put into relation to the phosphorus content to reveal correlations between phosphorus concentration in the gas phase and flame inhibition performance, as well as phosphorus concentration in the residue and condensed phase activity. Total heat evolved (fire load) and peak heat release rate were calculated based on changes in the effective heat of combustion and residue, and then compared with the measured values to address the modes of action of the flame retardants quantitatively. The quantification of flame inhibition, charring, and the protective layer effect measure the non-linear flame retardancy effects as functions of the phosphorus concentration. Overall, this screening approach using easily preparable polymer systems provides great insight into the effect of phosphorus in different flame retarded polymers, with regard to polymer structure, phosphorus concentration, and phosphorus species.
Carbon fibre (CF) and glass fibre (GF) reinforced polymers are used for diverse applications demaning flame and fire retardancy in the fire scenarios ignition, developing fire and fully developed fire. The fire behaviour of composites differs from polymers, since fibres behave often inert with respect to pyrolysis, change the melt flow / dripping behaviour, the heat absorption and transfer, the amount and properties of the fire residue. Concepts are needed suitable for the different fire protection goals, but also tailored for composites. The field is illuminated by examples carried out in the group of the author in the recent years. Approaches to halogen-free flame retardancy in GF reinforced thermoplastics and CF reinforced thermosets are presented as well as building up a bench and intermediate scale testing of composites in fire applying mechanical load and direct flame exposure simultaneously. The understanding of fire behaviour and flame retardancy modes of action in composites is a promising basis for target-oriented development.
The main flame retardant modes of action are well known, but in practise the detailed scientific understanding usually falls short, when it comes to modern multicomponent systems, the important tiny optimizations, or quantifying in terms of specific fire properties. This talk delivers thought-provoking impulses, picking up some overseen details as well as raising basic questions. A detailed scientific insight in flame retardant modes of action much more than an overview is presented.
Melt flow and dripping of polymeric materials can be both beneficial and detrimental during fire. It reduces flame spread and result in extinction, as mass and heat are removed from the actual pyrolysis zone. In contrast, melt flow and dripping can provide an additional ignition source, additional process of flame spread and has the potential to start a pool fire. In the vertical UL 94 test, a well adjusted dripping behaviour of flame retarded polypropylene (PP-FR) resulted in a non-flaming dripping V-0 classification. For the polymer samples and their drops collected in UL 94, the decomposition and viscosity was investigated. Particle finite element method (PFEM) was successfully used to simulate the material behaviour in the UL 94 test and increased the understanding of the complex behaviour of polymeric materials during fire.
Der Vortrag gibt einen Überblick über die Thematik der flammgeschützten Polyurethanwerkstoffe, d.h. thermoplastisches und elastomeres Polyurethan (TPU, PUR), PUR Hard- und Weichschäume, 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 verschiedene Brandtests zu bestehen. Die Pyrolyse und das Brandverhalten von PUR und PUR-Schäumen sowie der flammgeschützten Varianten wird diskutiert. Die gängigen Flammschutzmittel(-kombinationen) für PUR Hard- und Weichschaum sowie thermoplastisches und elastomeres PUR werden zusammengefasst.
Synergy in flame-retarded epoxy resin - Identification of chemical interactions by solid-state NMR
(2017)
The potential synergists aluminium diethylphosphinate (AlPi), boehmite (AlO(OH)) and melamine polyphosphate (MPP) were compared in flame-retardant epoxy resin (EP)/melamine poly(magnesium phosphate) (S600). The pyrolysis, the fire behaviour as well as the chemical interactions in the gas and condensed phases were investigated by various methods. Flammability was investigated by cone calorimeter and oxygen index (OI). The thermal and thermo-oxidative decomposition were studied by thermogravimetric analysis coupled with FTIR spectrometer. The special focus was on the Investigation of structural changes in the condensed phase via solid-state NMR of 27Al and 31P nuclei. By the comparison of epoxy resin with only one additive or with S600 in combination with AlPi, AlO(OH) or MPP, it was possible to calculate the synergy index. The best performance in terms of fire behaviour was observed for EP/S600/MPP with a PHRR (Peak heat release rate) of 208 kW m-2 due to slight synergy. In the case of THE (total heat evolved), clear synergy occurred for EP/S600/AlPi and EP/S600/AlO(OH). By solid-state NMR, different phosphates and aluminates were identified, indicating the chemical interactions between S600 and AlPi, AlO(OH) or MPP. The systematic multi-methodical approach yielded insight into the synergistic effects in the flame-retarded epoxy resin.