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In this study, multicomponent flame retardant systems, consisting of Ammonium polyphosphate (APP), aluminum trihydroxide (ATH), and polyaniline (PANI), were used in ethylene propylene diene monomer (EPDM) rubber. The multicomponent system was designed to improve flame retardancy and the mechanical properties of the rubber compounds, while simultaneously reducing the amount of filler. PANI was applied at low loadings (7 phr) and combined with the phosphorous APP (21 phr) and the mineral flame retardant ATH (50 phr). A comprehensive study of six EPDM rubbers was carried out by systematically varying the fillers to explain the impact of multicomponent flame retardant systems on mechanical properties. The six EPDM materials were investigated via the UL 94, limiting oxygen index (LOI), FMVSS 302, glow wire tests, and the cone calorimeter, showing that multicomponent flame retardant systems led to improved fire performance.
In cone calorimeter tests the EPDM/APP/ATH/PANI composite reduced the maximum average rate of heat emission (MARHE) to 142 kW·m-2, a value 50% lower than that for the unfilled EPDM rubber. Furthermore, the amount of phosphorus in the residues was quantified and the mode of action of the phosphorous flame retardant APP was explained. The data from the cone calorimeter were used to determine the protective layer effect of the multicomponent flame retardant systems in the EPDM compounds.
Ethylene propylene diene monomer (EPDM) Rubbers with the flame retardants tris(2-ethylhexyl)phosphate, ammonium polyphosphate, polyaniline, and aluminum trihydroxide were prepared and analyzed in this study. The homogenous dispersion of the fillers in the rubber matrix was confirmed by scanning electron microscope. To investigate the interplay of the different flame retardants, the flame retardants were varied systematically. The comprehensive study sought combinations of flame retardants that allow high loadings of flame retardants without deterioration of the physical and mechanical properties of the EPDM rubber. The eight EPDM rubbers were investigated via thermogravimetric analysis and pyrolysis gas chromatography coupled with a mass spectrometer (Py GC/MS) to investigate the potential synergistic effects. In the Py-GC/MS experiments, 27 pyrolysis products were identified. Furthermore, UL 94, limiting oxygen index, FMVSS 302, glow wire tests, and cone calorimeter tests were carried out. In the cone calorimeter test the EPDM rubbers R-1AP and R-1/2P achieved an increase in residue at flameout of 76% and a reduction in total heat evolved of about 35%. Furthermore, the compounds R-1AP and R-1/2P achieved a reduction in MARHE to about 150 kW m−1, a reduction of over 50% compared to the unprotected rubber R.
The ubiquity of polymeric materials in daily life Comes with an increased fire risk, and sustained research into efficient flame retardants is key to ensuring the safety of the populace and material goods from accidental fires. Phosphorus, a versatile and effective element for use in flame retardants, has the potential to supersede the halogenated variants that are still widely used today: current formulations employ a variety of modes of action and methods of implementation, as additives or as reactants, to solve the task of developing flameretarding polymeric materials. Phosphorus-based flame retardants can act in both the gas and condensed phase during a fire. This Review investigates how current phosphorus chemistry helps in reducing the flammability of polymers, and addresses the future of sustainable, efficient, and safe phosphorus-based flame-retardants from renewable sources.
Polyamide 4.6 (PA46) is a high-heat-resistant polymer, but it has no dripping resistance under fire. Three commercial grades of PA46 are investigated under UL 94 vertical fire test conditions. Their performances are discussed based on the materials’ structural, thermal, and rheological properties. PA46 presents flaming drops, whereas dripping is prevented in the flame-retarded PA46.
Friction-modified PA46 has increased flaming dripping. Temperature profiles of the specimens under fire and the temperature of the drops are measured by thermocouples. A UL 94 vertical test configuration consisting of two flame applications is designed to assess the quantitative dripping behavior of the set of materials by the particle finite element method (PFEM). Polymer properties (activation energy and Arrhenius coefficient of decomposition, char yield, density, effective heat of combustion, heat of decomposition, specific heat capacity, and thermal conductivity) in addition to rheological responses in high temperatures are estimated and measured as input parameters for the simulations. The dripping behavior obtained by simulated materials corresponds with the experimental results in terms of time and drop size. A consistent picture of the interplay of the different phenomena controlling dripping under fire appears to deliver a better understanding of the role of different materials’ properties
Aluminum tris (diethylphosphinate) (AlPi) is known to have an efficient flame-retardant effect when used in poly(butadiene terephthalates) (PBT). Additionally, better flame-retardant effects can be achieved through the partial substitution of AlPi by boehmite in multi-component systems, which have been shown to be an effective synergist due to cooling effects and residue formation. Although the potential of beneficial effects is generally well known, the influence of particle sizes and behavior in synergistic compositions are still unknown. Within this paper, it is shown that the synergistic effects in flammability measured by limiting oxygen index (LOI) can vary depending on the particle size distribution used in PBT. In conducting thermogravimetric analysis (TGA) measurements, it was observed that smaller boehmite particles result in slightly increased char yields, most probably due to increased reactivity of the metal oxides formed, and they react slightly earlier than larger boehmite particles. This leads to an earlier release of water into the system enhancing the hydrolysis of PBT. Supported by Fourier transformation infrared spectroscopy (FTIR), we propose that the later reactions of the larger boehmite particles decrease the portion of highly flammable tetrahydrofuran in the gas phase within early burning stages. Therefore, the LOI index increased by 4 vol.% when lager boehmite particles were used for the synergistic mixture.
A phosphaphenanthrene and triazinetrione group containing flame retardant (TAD) is combined with organically modified montmorillonite (OMMT) in epoxy resin thermosets (EP) to improve the performance of the flame-retardant system. When only 1 wt% OMMT/4 wt% TAD is introduced into the EP, the limited oxygen index (LOI) rises from 26% to 36.9% and a V-0 rating is achieved in a UL 94 test. The decomposition and pyrolysis products in the gas phase and condensed phase were characterized using thermogravimetry-Fourier transform infrared spectroscopy (TG-FTIR). The influence on the decomposition of EP, such as the increase in char yield, is limited with the incorporation of OMMT; a large amount of the phosphorus is released into the gas phase. The flame-retardant effect evaluation based on cone calorimeter data testified that OMMT improves the protective-barrier effect of the fire residue of OMMT/TAD/EP on the macroscopic scale, while TAD mainly causes flame inhibition. The fire residues showed a corresponding macroscopic appearance (digital photo) and microstructure (scanning electron microscope [SEM] results). The protective barrier effect of OMMT and the flame-inhibition effect of TAD combined to exert a superior flame-retardant effect, resulting in sufficient flame-retardant performance of OMMT/TAD/EP
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.
Fire resistance testing of components made of carbon fibre reinforced polymers (CFRP) usually demands intermediate-scale or full-scale testing. A bench-scale test is presented as a practicable and efficient method to assess how different fire protective systems improve the structural integrity of CFRPs during fire. The direct flame of a fully developed fire was applied to one side of the CFRP specimen, which was simultaneously loaded with compressive force. Three different approaches (film, non-woven, and coatings) were applied: paper with a thickness in the range of μm consisting of cellulose nanofibre (CNF)/clay nanocomposite, nonwoven mats with thickness in the range of cm and intumescent coatings with a thickness in the range of mm. The uncoated specimen failed after just 17 s. Protection by these systems provides fire stability, as they multiply the time to failure by as much as up to 43 times. The reduced heating rates of the protected specimens demonstrate the reduced heat penetration, indicating the coatings’ excellent heat shielding properties. Bench-scale fire stability testing is shown to be suitable tool to identify, compare and assess different approaches to fire protection.
The rapid mass calorimeter (RMC) was used as a screening tool based on accelerated fire testing to assess flame-retarded thermoplastic polyurethane (TPU). The reliability of RMC results was proven with the cone calorimeter as reference fire test. The influence of melamine cyanurate (MC) concentration on the fire performance of TPU was investigated, along with some flame-retardant combinations such as MC with aluminium diethylphosphinate (AlPi), aluminium trihydrate (ATH), and melamine polyphosphate (MPP). The two-stage burning behaviour of TPU was investigated in detail; the first stage corresponds mainly to the hard segments' decomposition and has a much lower effective heat of combustion (EHC) than the second stage, in which mainly the soft segments decompose and an intensive liquid pool fire is observed in the cone calorimeter set-up. In addition to fire testing with the cone calorimeter, RMC, and UL 94 flammability tests, the decomposition of the materials was investigated using thermogravimetric analysis coupled with infrared spectrometry (TGeFTIR). TPU/MC/AlPi shows the most promising results, achieving V-0 classification in UL 94 and reducing the extreme peak heat release rate (PHRR) of the liquid pool fire from 3154 kW/m2 to 635 kW/m2. Using MC/AlPi/MPP enhances the latter PHRR reduction further. The decomposition products identified in the gas phase via TGeFTIR reveal specific MCeAlPi eMPP interactions, as they differ from products seen in systems with MC/AlPi or MC/MPP. Correlations between RMC and cone calorimeter results were examined and presented in the final part of the paper. Several characteristics correlate strongly, pointing out that RMC is a reliable high-throughput fire testing method to screen multicomponent flame-retardant solutions in TPU.
The multicomponent flame retardant system of melamine polyphosphate (MPP), melamine cyanurate (MC) and aluminum diethylphosphinate (AlPi) is proposed and investigated for thermoplastic polyurethane (TPU). The synergy between those additives and the resulting superior fire performance are discussed. Systematically varied sets of flame retarded TPU with various MPP/MC/AlPi ratios were investigated in terms of fire behavior, pyrolysis products and mechanical properties. The total amount of the additives was always 30 wt.-%. Further, the influence of various AlPi concentrations was investigated. The optimal MPP:MC ratio was determined while keeping the amount of AlPi constant. The combination of 8 wt.-% MPP, 12 wt.-% MC and 10 wt.-% is proposed as the most promising halogen free flame retardant formulation for TPU, because it yielded a reduction in PHRR from 2660 kW/m2 (TPU) to 452 kW/m2 and enabled V-0 classification in the UL 94 test. Combinations of MPP and MC as well a high concentration of AlPi are beneficial for the mechanical properties e.g. tensile strength and elongation at break of the formulations and could be a strong competitor to commercial flame retarded TPUs.