TY - JOUR A1 - Brehme, Sven A1 - Köppl, T. A1 - Schartel, Bernhard A1 - Fischer, O. A1 - Altstädt, V. A1 - Pospiech, D. A1 - Döring, M. T1 - Phosphorus polyester - an alternative to low-molecular-weight flame retardants in poly(butylene terephthalate)? N2 - Pyrolysis, fire behaviour and mechanical properties of a blend of poly(butylene terephthalate) (PBT) with a phosphorus polyester (PET-P-DOPO) are investigated and compared with PBT/aluminium diethylphosphinate (AlPi-Et) composites. The PBT/PET-P-DOPO is immiscible and exhibits gas-phase and condensed-phase activity, whereas AlPi-Et in PBT results mainly in flame inhibition. Only higher loadings of AlPi-Et yield significant condensed-phase activity. Using the same phosphorus content, PBT/PET-P-DOPO and PBT/AlPi-Et exhibit similar reductions in fire load (22%) and flame spread (17% assessed by fire growth rate, FIGRA), compared with PBT. In contrast to AlPi-Et, the addition of PET-P-DOPO does not decrease the tensile strength of PBT. Thus, PET-P-DOPO is an interesting alternative to low-molecular-weight flame retardants. KW - Aluminium phosphinate KW - Blends KW - 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide KW - Flame retardance KW - Polyesters PY - 2012 DO - https://doi.org/10.1002/macp.201200072 SN - 1022-1352 SN - 1521-3935 VL - 213 IS - 22 SP - 2386 EP - 2397 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-26982 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Despinasse, Marie-Claire A1 - Schartel, Bernhard T1 - Influence of the structure of aryl phosphates on the flame retardancy of polycarbonate/acrylonitrile-butadiene-styrene N2 - The impact of the chemical structure of four different aryl bisphosphates on the flame retardancy of bisphenol A polycarbonate/acrylonitrile–butadiene–styrene blends (PC/ABS) was investigated. The impact of the bridging unit was studied, by comparing bisphenol A bis(diphenyl phosphate) BDP with biphenyl bis(diphenyl phosphate) BBDP and hydroquinone bis(diphenyl phosphate) HDP; as well as the influence of an aromatic substitution by comparing BBDP with biphenyl bis (di-2,6-xylyl phosphate) BBXP. The blends were investigated in terms of pyrolysis (thermogravimetry TG, TG coupled with Fourier transformed infrared spectroscopy (FTIR) and mass spectrometry (MS)) and fire performance (cone calorimeter, LOI, UL 94). The decomposition temperature of the flame retardant is a main parameter enabling a condensed phase interaction with PC decomposition products. The phosphate esters reacting with phenolic groups during pyrolysis were shown to increase cross-linking and reduce the hydrolysis/alcoholysis of the carbonate group. Variation of the aromatic substitution with the use of biphenyl bis (di-2,6-xylyl phosphate) led to reduced performance, highlighting the importance of the reactivity of the flame retardant with the decomposing PC. KW - Bisphenol A polycarbonate/acrylonitrile–butadiene–styrene (PC/ABS) KW - Flame retardancy KW - Flammability KW - Phosphate esters KW - Pyrolysis PY - 2012 DO - https://doi.org/10.1016/j.polymdegradstab.2012.07.005 SN - 0141-3910 SN - 1873-2321 VL - 97 IS - 12 SP - 2571 EP - 2580 PB - Applied Science Publ. CY - London AN - OPUS4-26969 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gallo, Emanuela A1 - Schartel, Bernhard A1 - Acierno, Domenico A1 - Cimino, F. A1 - Russo, P. T1 - Tailoring the flame retardant and mechanical performances of natural fiber-reinforced biopolymer by multi-component laminate N2 - The potential of a multi-component laminate composite material in terms of improved flame retardancy and adequate mechanical performance is discussed. A double-layer system based on a biodegradable polyhydroxyalkanoates blend was obtained by compression molding. A thin halogen-free flame-retarded layer was located at the top of a kenaf-fiber-reinforced core. Kenaf fibers acted as a carbonization compound promoting charring and building up a superficial insulating layer that protected the material throughout combustion. The impact of different skin/core thickness on the thermal and fire properties was investigated. Synergistic flame retardancy occurs in the cone calorimeter. Chemical and fire investigations confirmed a changed pyrolysis behavior in multicomponent materials. Promising results are obtained in terms of mechanical performance: higher flexural and impact properties were observed in the single fiber-reinforced layer. KW - A. Fibres KW - A. Layered structures KW - D. Thermal analysis KW - D. Mechanical testing PY - 2013 DO - https://doi.org/10.1016/j.compositesb.2012.07.005 SN - 1359-8368 VL - 44 IS - 1 SP - 112 EP - 119 PB - Elsevier CY - Oxford [u.a.] AN - OPUS4-26741 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Köppl, T. A1 - Brehme, Sven A1 - Pospiech, D. A1 - Fischer, O. A1 - Wolff-Fabris, F. A1 - Altstädt, V. A1 - Schartel, Bernhard A1 - Döring, M. T1 - Influence of polymeric flame retardants based on phosphorus-containing polyesters on morphology and material characteristics of poly(butylene terephthalate) N2 - Flame retarded poly(butylene terephthalate) (PBT) is required for electronic applications and is mostly achieved by low molar mass additives so far. Three phosphorus-containing polyesters are suggested as halogen-free and polymeric flame retardants for PBT. Flame retardancy was achieved according to cone calorimeter experiments showing that the peak heat release rate and total heat evolved were reduced because of flame inhibition and condensed-phase activity. The presented polymers containing derivatives of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide form immiscible blend systems with PBT. Shear-rheology shows an increase in storage moduli at low frequencies. This is proposed as quantitative measure for the degree of phase interaction. The phase structure of the blends depends on the chemical structure of the phosphorus polyester and was quite different, depending also on the viscosity ratio between matrix and second phase. A lower viscosity ratio leads to two types of phases with spherical and additionally continuous droplets. Addition of the flame retardants showed no influence on the dielectric properties but on the mechanical behavior. The polymeric flame retardants significantly diminish the impact strength because of several reasons: (1) high brittleness of the phosphorus polyesters themselves, (2) thermodynamic immiscibility, and (3) weak phase adhesion. By adding a copolymer consisting of the two base polymers to the blend, an improvement of impact strength was obtained. The copolymer particularly acts as compatibilizer between the phases and therefore leads to a smaller phase size and to a stronger phase adhesion due to the formation of fibrils. KW - Polyesters KW - Blends KW - Miscibility KW - Rheology KW - Flame retardance PY - 2013 DO - https://doi.org/10.1002/app.38520 SN - 0021-8995 SN - 1097-4628 VL - 128 IS - 5 SP - 3315 EP - 3324 PB - Wiley InterScience CY - Hoboken, NJ AN - OPUS4-27957 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gallo, Emanuela A1 - Sánchez-Olivares, G. A1 - Schartel, Bernhard T1 - Flame retardancy of starch-based biocomposites - aluminium hydroxide-coconut fiber synergy N2 - 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. KW - Biocomposites KW - Flammability KW - Starch KW - Aluminium hydroxide KW - Coconut fiber PY - 2013 SN - 0032-2725 VL - 58 IS - 5 SP - 395 EP - 402 PB - Industrial chemistry research inst CY - Warszawa, Poland AN - OPUS4-28513 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Despinasse, Marie-Claire A1 - Schartel, Bernhard T1 - Aryl phosphate-aryl phosphate synergy in flame-retarded bisphenol A polycarbonate/acrylonitrile-butadiene-styrene N2 - The pyrolysis and fire performance of bisphenol A polycarbonate/acrylonitrile-butadiene-styrene (PC/ABS) flame-retarded by a mixture of two aryl bisphosphates were investigated by thermogravimetry-coupled with FTIR, oxygen index (LOI), UL 94 and cone calorimeter. Both flame retardants, bisphenol A bis (diphenyl phosphate) BDP and hydroquinone bis (diphenyl phosphate) HDP, show gas-phase and condensed-phase actions. When mixed together at different ratios, a synergy is observed in terms of pyrolysis and fire residues as well as in effective heat of combustion (THE/ML). The synergisms were quantified and confirmed mathematically by the evaluation of the synergistic effect index (SE). All LOI values for the flame-retarded blends are between 29% and 32%, as opposed to 23% for PC/ABS, and UL94 testing results in V-0 at 1.6 mm instead of HB. Investigations on the binary system BDP + HDP reveal that BDP and HDP interact with each other, yielding stable intermediate products which are proposed to increase the thermal stability of the PC/ABS + BDP/HDP blends. Oligomeric phosphate esters are presumed to form via transesterification. KW - Flame retardancy KW - PC/ABS KW - Pyrolysis KW - Aryl phosphate KW - Synergy KW - Combustion PY - 2013 DO - https://doi.org/10.1016/j.tca.2013.04.006 SN - 0040-6031 SN - 1872-762X VL - 563 SP - 51 EP - 61 PB - Elsevier B.V. CY - Amsterdam AN - OPUS4-28515 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dittrich, Bettina A1 - Wartig, K.-A. A1 - Hofmann, D. A1 - Mülhaupt, R. A1 - Schartel, Bernhard T1 - Flame retardancy through carbon nanomaterials: carbon black, multiwall nanotubes, expanded graphite, multi layer graphene and graphene in polypropylene N2 - Herein we investigate the influence of carbon additives with different particle sizes and shapes on the flame retardancy and mechanical properties of isotactic polypropylene. Thermally reduced graphite oxide (TRGO) and multi-layer graphene (MLG250), consisting of few graphene layers, are compared with spherical, tubular and platelet-like carbon fillers such as carbon black (CB), multiwall nanotubes (MWNT) and expanded graphite (EG). The different morphologies control the dispersion of the carbon particles in PP and play a key role in structure–property relationships. Uniformly dispersed CB, MLG250 and TRGO shift the onset temperature of PP decomposition to temperatures around 30 °C higher, induce a flow limit in the composites' melt viscosity and change drastically their fire behaviour. The prevented dripping and significantly increased heat absorption result in decreased time to ignition and hardly any change in the reaction to a small flame. Under forced-flaming conditions reductions in the peak heat release rate of up to 74% are achieved due to the formation of a protective layer of residue during combustion. The described effects of carbon nanomaterials on the properties of PP composites are most pronounced for well-exfoliated graphenes, making them preferable to less exfoliated, micron-sized expanded graphite or conventional spherical and tubular carbon nanoparticles. KW - Polypropylene KW - Flame retardancy KW - Nanocomposites KW - Graphene KW - Carbon nanomaterials KW - Thermally reduced graphite oxide PY - 2013 DO - https://doi.org/10.1016/j.polymdegradstab.2013.04.009 SN - 0141-3910 SN - 1873-2321 VL - 98 IS - 8 SP - 1495 EP - 1505 PB - Applied Science Publ. CY - London AN - OPUS4-28638 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dittrich, Bettina A1 - Wartig, K.-A. A1 - Hofmann, D. A1 - Mülhaupt, R. A1 - Schartel, Bernhard T1 - Carbon black, multiwall carbon nanotubes, expanded graphite and functionalized graphene flame retarded polypropylene nanocomposites N2 - Herein, we examine the influence of adding functionalized graphene (FG), distinct expanded graphites and carbon nanofillers such as carbon black and multiwall carbon nanotubes on mechanical properties, morphology, pyrolysis, response to small flame and burning behavior of a V-2 classified flame-retarded polypropylene (PP). Among carbon fillers, FG and multilayer graphene (MLG) containing fewer than 10 layers are very effectively dispersed during twin-screw extrusion and account for enhanced matrix reinforcement. In contrast to the other fillers, no large agglomerates are detected for PP-FR/FG and PP-FR/MLG, as verified by electron microscopy. Adding FG to flame-retardant PP prevents dripping due to reduced flow at low shear rates and shifts the onset of thermal decomposition to temperatures 40°C higher. The increase in the onset temperature correlates with the increasing specific surface areas (BET) of the layered carbon fillers. The reduction of the peak heat release rate by 76% is attributed to the formation of effective protection layers during combustion. The addition of layered carbon nanoparticles lowers the time to ignition. The presence of carbon does not change the composition of the evolved pyrolysis gases, as determined by thermogravimetric analysis combined with online Fourier-transformed infrared measurements. FG and well-exfoliated MLG are superior additives with respect to spherical and tubular carbon nanomaterials. KW - Graphene KW - Flame retardancy KW - Nanocomposites KW - Polypropylene KW - Carbon nanoparticles PY - 2013 DO - https://doi.org/10.1002/pat.3165 SN - 1042-7147 SN - 1099-1581 VL - 24 IS - 10 SP - 916 EP - 926 PB - John Wiley & Sons, Ltd. CY - Chichester AN - OPUS4-29337 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Lorenzetti, A. A1 - Besco, S. A1 - Hrelja, D. A1 - Roso, M. A1 - Gallo, Emanuela A1 - Schartel, Bernhard A1 - Modesti, M. T1 - Phosphinates and layered silicates in charring polymers: The flame retardancy action in polyurethane foams N2 - Nanocomposites of a charring polymer (like polyurethane foam) filled with aluminum phosphinate (AlPi) with or without melamine cyanurate (MelCy) have been prepared by microwave processing and their thermal stability and fire behavior have been studied. Results on the interaction between flame retardants and layered silicates were provided as well as detailed investigation of the char strength, which has been carried out using a suitably developed method based on dynamic-mechanic analysis. Generally, the thermo-oxidative stability in presence of layered silicates was higher than the counterparts even if an additive rather than synergic effect took place; however, in some cases the interaction between clays and phosphinate led to a significant decrease of weight residue. In nitrogen the residue amounts were about the same but a higher amount of phosphorus was retained in the solid phase in presence of clays. Cone calorimeter results showed that the use of phosphinates led to a decrease of the PHRR; further addition of clays did not reduce the PHRR owing to the worse quality of char layer as demonstrated by the char strength test. However, it has been shown that the partial substitution of aluminum phosphinate with melamine cyanurate gave improved results: the AlPi–MelCy filled foams showed similar pHRR and THE but lower TSR and higher char strength than AlPi filled foams. It was also confirmed that phosphinate acted by flame inhibition but its action was depressed by the use of nanoclays owing to their interaction. KW - Phosphinate KW - Nanocomposite KW - Polyurethane KW - Interaction KW - Flame retardant PY - 2013 DO - https://doi.org/10.1016/j.polymdegradstab.2013.08.002 SN - 0141-3910 SN - 1873-2321 VL - 98 IS - 11 SP - 2366 EP - 2374 PB - Applied Science Publ. CY - London AN - OPUS4-29281 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hörold, Andreas A1 - Schartel, Bernhard A1 - Trappe, Volker A1 - Korzen, Manfred A1 - Naumann, Maurice T1 - Structural integrity of sandwich structures in fire: an intermediate-scale approach N2 - A test set-up in intermediate scale was conceived to investigate the structural integrity of materials under fire. The task was to develop a realistic test scenario targeting component-like behaviour. Carbon-fibre-reinforced sandwich specimens (500 X 500 X 20 mm) were used to examine failure mechanisms, times to failure and critical failure loads under compression. Fire tests were performed with fully developed fire applied to one side of the specimen by an oil burner. In a first test series, the applied load was varied, but the fully developed fire remained unchanged. In general, times to failure were short. Decreased load levels resulted in prolonged times to failure and led to a different failure mechanism. Results obtained in the test series were compared with a bench-scale study (150 X 150 X 20 mm) investigating identical material. The comparison clearly revealed the influence of size on the time to failure and the load-bearing capacity. KW - Fire testing KW - Structural integrity KW - Carbon-fibre-reinforced plastics KW - Fully developed fire KW - Composites PY - 2013 DO - https://doi.org/10.1080/15685543.2013.816620 SN - 0927-6440 SN - 1568-5543 VL - 20 IS - 9 (Special Issue: ECCM15: Part 3) SP - 741 EP - 759 PB - VSP CY - Zeist AN - OPUS4-29647 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -