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Only the nano-scaled structure of the nanocomposite and the dispersion of nanoparticles within the polymer matrix harbor multifunctional potential including superior fire retardancy. Thus, this chapter focuses on the dispersion of nanoplates, based mainly on studies of layered silicates and graphene/graphene-related nanoplates. The nanostructure and properties of the nanocomposites are dependent mainly on thermodynamic and kinetic factors during preparation. Improving nano-dispersion often directly improves flame retardancy. Therefore, the modification of the nanoplates as well as the preparation of nanocomposites becomes very important to control this dispersion. The dispersion of nanoplates functions as a prerequisite for the formation of an efficient protective layer, changing the melt flow and dripping behavior, or the improvement of the char properties.
In this study, experimental determination and modelling investigations for the explosion regions of 1,3-dioxolane/inert gas/N2O and 1,3-dioxolane/inert gas/air mixtures were carried out and compared. The experimental measurements were carried out at 338 K and atmospheric pressure according to EN1839 method T using the inert gases N2, CO2, He and Ar. The results showed that the ratio of the lower explosion limit in N2O (LELN2O) to the lower explosion limit in air (LELair) is 0.52 and the ratio of the maximum oxygen content in air (MOCair) to the limiting oxidizer fraction in nitrous oxide (LOFN2O) is 0.36 ± 0.02 independent of the inert gas. When comparing the inert gas amount at the apex based on the pure oxidizing component, which is O2 in case of air, N2O-containing mixtures need less inert gas to reach the limiting oxidizer quantity whereas the efficiency of inert gases is in the same order. The coefficients of nitrogen equivalency however were found to differ to some extent. The explosion regions of 1,3-dioxolane/inert gas/oxidizer mixtures were modelled using the calculated adiabatic flame temperature profile (CAFTP) method as well as corrected adiabatic flame temperatures. The results indicate good agreement with experimental data for CO2, N2 and Ar- containing mixtures. The noticeable deviations that occur when He is the inert gas are due to the lacking transport data of that mixture.
Nowadays, various polymeric materials are used in E&E applications with sufficient flame retardance by adding rather different flame retardants. It doesn’t matter whether cables are used outdoor or are installed indoor as building products, the weathering exposures such as UV radiation, humidity and variation in temperature occur and influence the flame-retardant property. Recently, the lifetime of the flame retardance itself becomes an increasingly important factor. In this work, several devices were used to perform accelerated artificial ageing simulating different environment exposures.
The comprehensive and global understanding of the durability of flame retardance in dependence on the weathering or ageing conditions is still a matter of discussion. Therefore, the weathering resistance of various halogen-free fire-retarded polymers was investigated in this work. Polymeric systems with different kinds of fire retardants were chosen, including various fire retardant mechanisms. Ethylene Vinyl Acetate (EVA) blends with high amounts of inorganic flame retardant such as aluminum hydroxide (ATH), boehmite and synergists, which mainly dilutes the polymer resin work as heat sink and cooling agent, and enhance residue formation was examined. Thermoplastic Polyurethane (TPU) was modified with melamine cyanurate (MC), which mainly acts by changed melt flow and dripping behavior as well as fuel dilution. Additionally, aluminum diethylphosphinate and boehmite are induced as assistant flame retardant. Furthermore, glass fiber reinforced Polyamide 66 (PA) was investigated containing different kinds of aluminum diethylphosphinate based flame retardant mixtures, which acts by flame inhibition and additional char formation.
The degradation of the surface was analyzed after the different weathering conditions. Most of the specimens exhibited an intensive material degradation at the top surface accompanied by a distinct discoloration, e.g. getting darker or showing yellowing. The weathering of the EVA samples lead to numerous cracks (already) after 4000 h. The corresponding changes in the chemical structure was investigated by ATR FT-IR for all materials.
The flammability was investigated by cone calorimeter, UL-94 burning chamber, and oxygen index (LOI) using plate and bar specimens. The flame retardance of most of the materials studied degrades only slightly or were rather stable for the investigated exposure times. Interestingly, also some opposite results were found. EVA modified by different inorganic flame retardants such as ATH achieved higher LOI after exposing in the humidity chamber and the accelerated oxidation under water in the autoclaves. It is suggested that the particle size of ATH and boehmite plays an important role, when these flame retardants agglomerate at the surface during accelerated weathering.
Both materials, EVA and TPU, were also investigated as cable jackets. While EVA modified with inorganic flame retardants exhibits low-smoke and non-dripping fire behavior, TPU flame-retarded with MC yields cables with pronounced melt-dripping. Cone calorimeter tests were carried out using cable rafts of the size of 100 mm * 100 mm as well as our self-made cable module test, which simulates the vertical full-scale test of a bundle of cables at the bench-scale. Both methods were used to investigate the weathering resistance of the flame retardance in cables. The results of the cable module test for the flame-retarded EVA cables were only slightly affected even when a long time hydrothermal ageing was carried out. This is because of inorganic residue which just delays the fire growth but does not extinguish. However, for the flame-retarded TPU cable jackets, the cable module test exhibited an accelerated fire spread and a melt-dripping behavior which was promoted by weathering exposure.
Thermoplastic starch polymer blends as biodegradable materials are well known and used mainly as packaging material. In order to exploit new application fields for these materials, additional properties such as flame retardancy or increased mechanical strength are required. This work focuses on the flammability and fire behavior of a thermoplastic starch/polyester blend reinforced with natural fibers derived from Mexican industry processes wastes, such as keratin fibers from the tannery industry or coconut fibers[1]. Different fiber contents as well as combinations of varying contents of aluminum trihydroxide, expandable graphite or ammonium polyphosphate were tested in LOI, UL94, cone calorimeter and TG-FTIR in order to investigate and assess the concentration dependence of the fibers and flame retardants as well as synergistic effects between both components. In combination with ammonium polyphosphate, the coconut fibers induce a synergistic effect by reinforcing the char residue and creating a more stable heat barrier during forced flaming combustion in the cone calorimeter. Synergism is also observed in the oxygen test. The recycling of otherwise wasted material is a true challenge in material development, thus this work is a first step in the direction of sustainable and biodegradable materials.
ISO 10156:2010 contains a test method and a calculation method for flammability of gases and gas mixtures for the selection of cylinder valve outlets. The calculation method is used also to classify gas mixtures according to the national and international dangerous goods and dangerous substances regulations, e.g. according to the UN Recommendations on the Transport of Dangerous Goods (UN TDG) and the Globally Harmonized System of Classification and Labelling of Chemicals (UN GHS). The calculation method for gas mixtures requires substance parameters of the single components. These are the coefficients for the fire potential (Tci) and for inerting ability, the so-called nitrogen equivalence (Kk), which have been estimated conservatively by means of flammability data.
BAM checked Tci and Kk values of ISO 10156:1996 using three-component diagrams (Flammable gas-Inert-Air) of the CHEMSAFE® database. The experimental fundamentals and the principles of the calculation method are summarized in this paper. The revised data for Tci and Kk values were adopted in the tables of ISO 10156:2010.
Furthermore, subcategorization of flammable gases has been proposed by a UN working group and shall be implemented in the GHS in the meantime. The subcategorization requires the lower flammability limit (LFL) as an additional indicator. Therefore, a test method and a calculation method for LFL were proposed by BAM and have been implemented in the new draft of ISO/CD 10156:2016.
The calculation method for gas mixtures is based on Le Chatelier’s rule and was extended by using the Kk values for inert components in the mixture. The calculated LFLs of methane-inert gas mixtures were compared with experimental values for different types of inert gases. It could be shown that calculated LFLs are in good agreement with experimental values if the Kk values derived from three-component flammability diagrams are used. Although using the Kk values of ISO 10156:2010 leads to higher deviations, the results are still on the safe side.
The presentation will discuss the difference between EU and US standards for the determination of explosion (flammability) limits and limiting oxygen concentration. Small differences observed in measured values can be traced back to the different test apparatuses and criteria. The discrepancies can be much greater in the case of limiting oxygen concentration because of the high amount of inert gases and the corresponding low laminar burning velocities. The paper describes some examples and the influence of the chosen criteria on the results. The European and US standards use the criteria of flame propagation in open test vessels and of pressure rise in closed ones. The examples discussed show that flame propagation is still possible at very small pressure rise values, as observed much below the pressure rise criterion of usual standards. However, flame propagation in a process plant can cause an accident or explosion and must be avoided. Therefore, the flame propagation criterion is recommended to be used in chemical safety engineering. The European safety database CHEMSAFE contains expertevaluated safety data for cases where the determination method and criteria are known. Flammability characteristics based on the pressure rise criterion may suffice in certain cases, e.g. for explosion protection in closed vessels without any connecting pipes.
The presentation will discuss the difference between EU and US standards for the determination of explosion (flammability) limits and limiting oxygen concentration. Small differences observed in measured values can be traced back to the different test apparatuses and criteria. The discrepancies can be much greater in the case of limiting oxygen concentration because of the high amount of inert gases and the corresponding low laminar burning velocities. The paper describes some examples and the influence of the chosen criteria on the results. The European and US standards use the criteria of flame propagation in open test vessels and of pressure rise in closed ones. The examples discussed show that flame propagation is still possible at very small pressure rise values, as observed much below the pressure rise criterion of usual standards. However, flame propagation in a process plant can cause an accident or explosion and must be avoided. Therefore, the flame propagation criterion is recommended to be used in chemical safety engineering. The European safety database CHEMSAFE contains expert-evaluated safety data for cases where the determination method and criteria are known. Flammability characteristics based on the pressure rise criterion may suffice in certain cases, e.g. for explosion protection in closed vessels without any connecting pipes.
The presentation will discuss the difference between EU and US standards for the determination of explosion (flammability) limits and limiting oxygen concentration. Small differences observed in measured values can be traced back to the different test apparatuses and criteria. The discrepancies can be much greater in the case of limiting oxygen concentration because of the high amount of inert gases and the corresponding low laminar burning velocities. The paper describes some examples and the influence of the chosen criteria on the results. The European and US standards use the criteria of flame propagation in open test vessels and of pressure rise in closed ones. The examples discussed show that flame propagation is still possible at very small pressure rise values, as observed much below the pressure rise criterion of usual standards. However, flame propagation in a process plant can cause an accident or explosion and must be avoided. Therefore, the flame propagation criterion is recommended to be used in chemical safety engineering. The European safety database CHEMSAFE contains expert-evaluated safety data for cases where the determination method and criteria are known. Flammability characteristics based on the pressure rise criterion may suffice in certain cases, e.g. for explosion protection in closed vessels without any connecting pipes.
Nanotechnology is one of the key technologies of the 21st century. The exploitation of 'new' effects that arise from materials structured on the nano-scale has also been proposed successfully for flame retardancy of polymers since the end of the 90s. Of all of the approaches these include, at this time the use of nanocomposites offers the best potential for industrial application, also some other ideas are sketched, such as using electrospun nanofibers mats or layer-by-layer deposits as protection coatings, as well as sub-micrometer multilayer coatings as effective IR-mirrors. The general phenomena, inducing a flow limit in the pyrolysing melt and changing the fire residue, are identified in nanocomposites. Key experiments are performed such as quasi online investigation of the protection layer formation to understand what is going on in detail. The flame retardancy mechanisms are discussed and their impact on fire behaviour quantified. With the latter, the presentation pushes forward the state of the art. For instance, the heat shielding is experimentally quantified for a layered silicate epoxy resin nanocomposite proving that it is the only import mechanism controlling the reduction in peak heat release rate in the investigated system for different irradiations. The flame retardancy performance is assessed comprehensively illuminating not only the strengths but also the weak points of the concepts. Guidelines for materials development are deduced and discussed. Apart from inorganic fillers (layered silicate, boehmite, etc.) not only carbon nanoobjects such as multiwall carbon nanotubes, multilayer graphene and graphene are investigated, but also nanoparticles that are more reactive and harbor the potential for more beneficial interactions with the polymer matrix.
The use of coconut fiber (CF) agricultural waste was considered as an environmentally friendly and inexpensive alternative in flame retarded biocomposites. To decrease the high content of aluminum trihydrate (ATH) required, the thermal decomposition (thermogravimetry), flammability [oxygen index (LOI) and UL 94 test] and fire behavior (cone calorimeter) of a combination of CF and ATH were investigated in a commercial blend of thermoplastic starch (TPS) and cellulose derivatives. CF induced some charring activity, slightly decreasing the fire load and burning propensity in cone calorimeter test. ATH decomposes endothermically into water and inorganic residue. Significant fuel dilution as well as a pronounced residual protection layer reduces the fire hazards. Replacing a part of ATH with coconut fibers resulted in improved flame retardancy in terms of ignition, reaction to small flame, and flame-spread characteristics [heat release rate (HRR), fire growth rate (FIGRA), etc.]. The observed ATH and CF synergy opens the door to significant reduction of the ATH contents and thus to interesting flame retarded biocomposites.
Bisphenol A polycarbonate/acrylonitrile–butadiene–styrene (PC/ABS) with and without bisphenol A bis(diphenyl phosphate) (BDP) and 5 wt.% zinc borate (Znb) were investigated. The pyrolysis was studied by thermogravimetry (TG), TG-FTIR and NMR, the fire behaviour with a cone calorimeter applying different heat fluxes, LOI and UL 94. Fire residues were examined with NMR. BDP affects the decomposition of PC/ABS and acts as a flame retardant in the gas and condensed phases. The addition of Znb results in an additional hydrolysis of PC. The fire behaviour is similar to PC/ABS, aside from a slightly increased LOI and a reduced peak heat release rate, both caused by borates improving the barrier properties of the char. In PC/ABS + BDP + Znb, the addition of Znb yields a borate network and amorphous phosphates. Znb also reacts with BDP to form alpha-zinc phosphate and borophosphates that suppress the original flame retardancy mechanisms of BDP. The inorganic–organic residue formed provides more effective flame retardancy, in particular at low irradiation in the cone calorimeter, and a clear synergy in LOI, whereas for more developed fires BDP + Znb become less effective than BDP in PC/ABS with respect to the total heat evolved.