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Carbon black, multiwall carbon nanotubes, expanded graphite, multilayer graphene and graphene are compared comprehensively as flame retardants in nanocomposites to each other. Different polymer matrices are investigated as well as changing the concentration of the carbon fillers. Distinct combinations of graphene with conventional flame retardants are investigated. Phenomena and mechanisms are identified controlling the pyrolysis and fire behavior. The viscosity of the nanocomposites and their thermal conductivity as well are dramatically changed compared to the polymers influencing the time to ignition and flammability. During pyrolysis graphene functioned as inert filler and formed a residual protective layer reducing the peak heat release rate.
The influence of graphene on the effectivity of various conventional halogen-free flame retardants depends strongly on their modes of action. The addition of a small amount of graphene to an intumescent flame retardant poly(propylene) led to an improvement in the cone calorimeter. The further increase of graphene content gained deceleration of swelling and a decrease of the final height of the intumescent layer. In combination with metal hydroxide, 1 wt% graphene closed the macroscopic surface structure and densified the microscopic structure of the fire residues tremendously. Due to this improved residue structure, metal hydroxides and graphene showed synergistic cooperation in terms of oxygen index and UL 94 classification (HB/V-1 to V-0).
The fire behaviour of carbon fibre (CF) reinforced polymers differs in comparison to polymers. Fibres behave often inert with respect to pyrolysis, they change the melt flow and dripping behaviour, the heat absorption and transfer, the amount and properties of the fire residue and so on. Flame and fire retardancy concepts are needed not only suitable for the different fire protection goals typical for each application, but also tailored for composites. This field is illuminated by examples taken from different projects carried out in the group of the author in the recent years. The examples target on different applications through achieving reduction in reaction to fire controlling the fire risks (flammability, heat release) in the beginning and development of a fire and investigating the fire stability, when a severe flame is directly applied (key property in fully developed fires). Approaches to halogen-free flame retardancy in CF reinforced thermosets are presented as well as building up a bench and an intermediate scale testing of composites in fire applying mechanical load (up to 1 MN compression) and direct flame exposure (180 kW/m2) simultaneously. Indeed, e.g. we have investigated the fire stability of stringer reinforced shell components taken out from the fuselage of an aircraft.
The understanding of fire behaviour, fire resistance, and fire retardant modes of action in composites is a promising basis for target-oriented development. The role of flame inhibition, charring, and protective layer formation is discussed. Successful concepts are presented for fire retardancy tailored for different application as well as general guidelines for future development. Different phosphorus flame retardants are proposed to achieve halogen-free flame retardancy with respect to ignition and developing fires. Different protective approaches are sketched for addressing the fire stability of composites that is the most important fire risk for the fire resistance in structural applications.
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.
Advanced analysis of flame retarded epoxy resin/melamine poly(metal phosphate)/synergist systems
(2017)
Synergistic multicomponent systems containing melamine poly(metal phosphate) have been proposed as flame retardants. 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) (MMgP) and EP/melamine poly(zinc phosphate) (MZnP). A multi-methodical approach was used to investigate the pyrolysis, fire residues, flame retardant modes of action, and synergistic effects. The decomposition and the fuel released into the gas phase were investigated by thermogravimetry coupled with Fourier transform infrared spectroscopy (TG-FTIR). A detailed analysis of the condensed phase was done by FTIR and comprehensive solid-state nuclear magnetic resonance spectroscopy (NMR). The fire behaviour was investigated by the cone calorimeter and the morphology of the fire residues with micro-computed tomography (µCT) and scanning electron microscopy (SEM). The best performance is observed for EP/MMgP/MPP and EP/MZnP/MPP based on a synergistic effect between the flame retardants. Particular the formation of a highly voluminous fire residue plays a major role and is stabilized by the interaction between the flame retardants. As a result highly effective protection layer was formed which led to the interesting results.
Benefits of hyperbranched structure:
Molecular weight, miscibility, number of FR groups, end-group functionalization, glass transition temperature, decreased PBT.
Examples of hyperbranched FRs:
Charring agent, silicone, triazine, etc.
Systematic study of effect of chemical surrounding and impact of Complex shape of phosphorus-based hyperbranched polymers on flame retardant efficacy in epoxy resins.
The need to develop effective flame retardants that retain polymer properties and are safe for consumers and the environment is a continuous challenge for material scientists. While halogenated flame retardants were once commonplace, the shift to non-halogenated materials has steadily progressed due to concerns over impact on health and the environment. One prominent group of flame retardants has become a viable alternative for halogenated materials, namely phosphorus-based flame retardants. The chemical versatility of phosphorus-based flame retardants and the ability to work as reactive or additive compounds makes them ideally suited for modern materials. There exists a trend toward complex, polymeric, and multifunction flame retardants, as these materials show greater flame retardancy performance than low molecular weight counterparts and affect material properties to a much lesser extent.
One group of organophosphorus flame retardants that shows great potential for high-performance polymers like epoxy resins are hyperbranched phosphorus-based polymers. These additives exhibit great miscibility with the polymer matrix and a significantly decreased diffusion through the material, which greatly reduce leaching or blooming out of the matrix. Moreover, the material’s thermal stability remains intact at elevated temperatures due to its low impact on the glass transition temperature. Finally, following market trends and legislation such as the guidelines for the Restriction of Hazardous Substances Directive implemented by REACH (Registration, Evaluation, Authorization and Restriction of Chemicals) in the EU, these macromolecules are non-accumulating, non-toxic and have a lower risk of leeching or blooming from the matrix, further reducing environmental impact.
The work presented herein focusses on two distinct parts studying hyperbranched polymeric flame retardants and their corresponding monomeric compounds.
The first part, involving the low molecular weight components, investigated the role of the chemical surrounding of phosphorus in terms of flame retardant efficacy. Here, a systematic variance of the surrounding of phosphorus was investigated: by changing the ratio of oxygen to nitrogen (4:0 until 1:3), four materials, namely phosphoester (4:0), phosphoramidate (3:1), phosphorodiamidate (2:2), and phosphoramide (1:3), were synthesized, characterized, and finally added to Bisphenol A based epoxy resins (10 wt.-% loading). Pyrolysis investigations showed that low molecular weight components volatize at lower temperatures than the polymer matrix. Additionally, cone calorimeter measurements and TGA-FTIR investigations show trends in respect to FR efficacy in pyrolysis and full flaming conditions.
The second part involves the hyperbranched variants of the monomeric counterparts and investigates the role of complex shape on flame retardant efficacy. By comparing the low to the high molecular weight compounds, the influence of the complex shape becomes apparent and can be quantified. Cone calorimeter measurements show an increase in flame retardancy for some materials, while for others, the mode of action is altered.
By implementing a multi-methodical approach, various flame retardancy aspects, from pyrolysis behavior in the gas and condensed phase, to ignitability / reaction-to-small-flame performance, to action in forced flammability experiments, are identified and quantified, allowing for a clearer understanding of the behavior in fire of these novel flame retardants. By comprehending the roles of chemical composition and complex shape, it opens the path for new and effective multifunctional, polymeric flame retardants with decreased PBT, higher miscibility, and low impact on Tg.
This work is funded by the Deutsche Forschungsgemeinschaft (DFG: SCHA 730/15-1; WU 750/8-1).
Elastomers are used in a wide range of automotive and railway applications. However, a severe drawback of most rubbers are their high flammability. Therefore, flame retardants (FRs) are added to improve the performance in fire. Generally, rubber composites are filled with high amounts of mineral fillers such as aluminium trihydroxide (ATH) to fulfil fire safety regulations. These high loadings may cause deterioration of the physical properties of the material. This work shows the implementation of two new strategies to achieve the modern demands on non-toxic FRs and the reduction of fillers.
The first approach was the implementation of multilayer graphene (MLG), acting as a multifunctional filler, reinforcing agent and FR. The study presents filler combinations with a systematic variation of the fillers carbon black (CB), MLG and ATH. The nanocomposites were prepared via master batch by an ultrasonically assisted solution mixing. Afterwards the master batch was compounded into the rubber in a two-roll milling. MLG substituted high amounts of the conventional filler CB, leading to reduced filler loadings and a consistent improvement in curing, mechanical and FR properties.
The second strategy was the combination of phosphorous-containing FRs with a potential new polymeric char promoting agent polyaniline (PANI). Char promoting additives such as pentaerythritol (PER) improve the effectiveness of the FR system. The combination of ammonium polyphosphate (APP) with PER was successfully investigated for natural and styrene-butadiene rubber composites. This work investigates the flame retardancy of the combination of FRs with PANI and its capability to act as a char/barrier promoter in EPDM.
The morphology of the rubbers and homogenously dispersion of MLG was investigated via scanning/transmission electron microscope (SEM/TEM) micrographs. Rheological and mechanical measurements assessed the influence of the fillers on the physical properties of the rubber composites. Characterization via thermogravimetric analysis (TGA) led to a broader understanding of the decomposition. In order to determine the flame retardancy effect of these materials, a multi-methodical approach was selected. Limiting oxygen index (LOI) and UL-94 were used to quantify the flammability of the rubber composites. The cone calorimeter provided information about the fire behaviour in forced flaming conditions. Residues were investigated via elementary analysis and XPS to clarify the composition of the remaining material. Glow-Wire and FMVSS 302 tests revealed significant results in terms of flame retardancy. The flame retardancy investigation of rubber composites, combinations of ATH with MLG and ATH with phosphorous-containing FRs, broaden the horizons of rubber flame retardancy solutions. By examining alternate FR formulations and their effect on mechanical and physical properties of the rubber, new insight into the range of applicable additives for rubber composites may be won.
Although the main flame retardant modes of action are known, 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. The description of the flame retardant modes of action remains usually vague and fragmentary. This talk tries to deliver thought-provoking impulses how the understanding of the fire behaviour and flame retardancy can be utilized to direct the development of future flame retardant polymer products. Some overseen details are picked up as well as rethinking of concepts memorised long ago is encouraged to discover something new. Furthermore, the talk tries to fill the gap between flame retardant modes of action and fire performance constituting a product. This talk promotes the evidence-based development of flame retardant polymers
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.
As a potential substitute for currently used halogenated flame retardants we explored the synthesis of dibenzo[d,f][1,3,2]dioxaphosphepine 6-oxide (BPPO) and derivatives. BPPO is a cyclic phosphonate and was synthesized by a simple, three-component condensation using 2,2´-biphenol, phosphorus trichloride and water by improving a procedure given by Natchev. Subsequently, BPPO was employed in phospha-Michael additions in line with the known synthesis of DOPO-compounds to double bonds. These reactions result in novel phosphorus-containing compounds with flame retardant activíty. The chemical structure of the unsaturated compounds was systematically varied yielding non-reactive flame retardants (without functional groups) from acrylates and diesters, and reactive (with functional groups) flame retardants from p-benzoquinone. The use of the phosphonate BPPO and its derivatives as flame retarding additives has not been described yet. The BPPO ring is highly reactive. Therefore, it is supposed that it mainly acts in the gas phase.
The new phosphonates were applied as additives for improving the flame retardancy of rigid PUR/PIR foams with triethyl phosphate (TEP) as plasticizer. The foam characteristics like density, cell integrity, pore size and mechanical properties were investigated. The burning properties of the foams were analyzed in the vertical flame spread according to DIN 4102 and by cone calorimetry. The relevant parameters depended on the phosphorus content, which is illustrated for PIR foams with ethyl 3-(6-oxidodibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)propanoate (X, Z = H; Y = OEt; EA-BPPO) as FR additive.
At comparable P-content, the EA-BPPO additive reached the PHHR-values of the benchmark foam with TEP and triphenyl phosphate as FR additive. With increased P-content the values were further reduced. TML and MARHE parameters showed a similar tendency. The FR additives dispersed well in the formulation and had no significant influence on foam density, cell integrity and pore size compared to the reference sample.