TY - JOUR A1 - Krebs, N. A1 - Demleitner, M. A1 - Albuquerque, R.Q. A1 - Schartel, Bernhard A1 - Ruckdäschel, H. T1 - Bayesian Optimization of flame-retardant performance in a high-Tg epoxy resin system N2 - Polymeric materials are widely used due to their mechanical properties and cost-effectiveness, but their inherent flammability requires effective flame-retardant additives to meet safety standards. Optimizing multicomponent flame-retardant formulations is challenging due to the vast experimental space. This study applies Bayesian Optimization (BO) to optimize flame-retardant formulations in high glass transition temperature (Tg) epoxy resins. Aluminum diethyl phosphinate (AlPi) was systematically combined with three synergists: zinc stannate (ZnSt), a silicone-based additive (DowSil), and low-melting glass frits (Ceepree). BO-guided experimental design expanded from 16 initial formulations to a total of 28, minimizing the Maximum Average Rate of Heat Emission (MARHE) under the constraint of Total Smoke Production (TSP) < 17 m2 using the epsilon-constraint method. BO revealed non-linear synergistic interactions: ZnSt significantly reduced smoke production while AlPi effectively lowered heat release. The optimized formulation (BO7) achieved the lowest MARHE (122 kW/m2) while maintaining acceptable smoke levels, establishing a new Pareto front. The results demonstrate the effectiveness of BO in accelerating the development of synergistic, halogen-free flame-retardant polymer systems, offering a scalable and sustainable approach to polymer formulation design. KW - Machine learning KW - Epoxy resin KW - Bayesian optimization KW - Flame retardancy KW - Cone calorimeter PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-641070 DO - https://doi.org/10.1016/j.commatsci.2025.114210 SN - 0927-0256 SN - 1879-0801 VL - 260 SP - 1 EP - 9 PB - Elsevier AN - OPUS4-64107 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Shabir Mahr, Muhammad A1 - Hübert, Thomas A1 - Sabel, Martin A1 - Schartel, Bernhard A1 - Bahr, Horst A1 - Militz, H. T1 - Fire retardancy of sol-gel derived titania wood-inorganic composites N2 - Sol–gel technology was applied in tailoring novel wood-made-inorganic composites with improved thermal and fire properties. In practice, composites materials were prepared by impregnating pine sapwood wood with nano-scaled precursor solutions derived from titanium(IV) isopropoxide followed by a thermal curing process. Thermal and fire properties were evaluated by thermal analysis and cone calorimetry, whereas flammability was specified by oxygen index (LOI) and UL 94 test. Peak heat release rates were moderately reduced indicating fire retardance potential in terms of flame spread attributed to the appropriate protection layer action of the titania-based depositions. LOI (oxygen index) values of these composites were increased up to 38 vol.% in comparison to 23 vol.% for untreated wood. The flame retardancy performance depends on the fire scenario and is strongly influenced by wood loading and crackfree deposition of the titania layers inside the composite. PY - 2012 DO - https://doi.org/10.1007/s10853-012-6628-3 SN - 0022-2461 SN - 1573-4803 VL - 47 IS - 19 SP - 6849 EP - 6861 PB - Springer Science + Business Media B.V. CY - Norwell, Mass. AN - OPUS4-26235 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Shabir Mahr, Muhammad A1 - Hübert, Thomas A1 - Schartel, Bernhard A1 - Bahr, Horst A1 - Sabel, Martin A1 - Militz, H. T1 - Fire retardancy effects in single and double layered sol-gel derived TiO2 and SiO2-wood composites N2 - Sol–gel derived TiO2 and SiO2-wood inorganic composites are prepared by direct vacuum infiltration of silicon and titanium alkoxide based precursors in pine sapwood in one or two cycles followed by a controlled thermal curing process. The resulting flame retardancy effect is investigated under two different fire scenarios using cone calorimetry and oxygen index (LOI). Heat release rates (HRR) especially the values for the second peak, are reduced moderately for all single layered composites. This effect is more pronounced for double layered composites where HRR was reduced up to 40 % showing flame retardancy potential in developing fires. Beside this, smoke release was lowered up to 72 % indicating that these systems had less fire hazards compared to untreated wood, whereas no meaningful improvement is realized in terms of fire load (total heat evolved) and initial HRR increase. However impressively, the LOI of the composites were increased up to 41 vol% in comparison to 23 vol% for untreated wood displaying a remarkable flame retardancy against reaction to a small flame. An approximate linear interdependence among the fire properties and the material loading as well as fire residue was observed. A residual protection layer mechanism is proposed improving the residue properties for the investigated composites. KW - Wood KW - Sol-gel KW - Composite materials KW - Cone calorimeter KW - Fire retardance KW - Flammability PY - 2012 DO - https://doi.org/10.1007/s10971-012-2877-5 SN - 0928-0707 SN - 1573-4846 VL - 64 IS - 2 SP - 452 EP - 464 PB - Kluwer Academic Publ. CY - Dordrecht AN - OPUS4-27618 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Chacon Castro, Jose P. A1 - Schartel, Bernhard T1 - Translating Flame Retardant Strategies: Analogy from Polyolefins and Bisphenol A polycarbonates to Poly(limonene carbonate) N2 - Poly(limonene carbonate)—PLimC—offers a novel sustainable alternative to traditional polymers, as it is derived from renewable limonene and carbon dioxide as monomers. Proposing PLimC as a future technical polymer for applications in electrical and electronic (E&E) devices, construction, and transportation, PLimC must meet specific fire prevention standards to be deemed suitable. Starting from the chemical structure of PLimC, strategies in analogy to flame retarded bisphenol A polycarbonates (PC), PC blends, and polyolefins (PO) are investigated to identify the most effective route to enhance the flame resistance of PLimC. This study utilized four halogen-free flame-retardant (FR) systems: APP + pentaerythritol (standard intumescent system in PO), a phosphorus flame retardant+PTFE as anti-dripping agent (used in PC blends), metal hydroxide ATH (widely used in PO), and potassium sulfonate salt (specific solution for PC). Applying these FRs at typical PC, PC blends, and PO loadings, we aim to understand their effect on PLimC and evaluated the different flame-retardant routes. Our experimental evaluations focused on the thermal properties, flammability, and fire behavior of each system. ATH emerged as the most effective, reducing the effective heat of combustion from 29.3 MJ kg⁻¹ to 18.6 MJ kg⁻¹ and the total heat evolved from 95 to 55 MJ m⁻². It also resulted in an increase in the limiting oxygen index from 17.1 to 26 vol.-% O2, along with a UL 94 HB40 rating. The intumescent system also exhibited considerable flame retardancy, highlighting the similarity of PLimC’s fire behavior to that of PO rather than PC KW - Poly(limonene carbonate) KW - Flame retardancy KW - Sustainability KW - Intumescent systems KW - Metal hydroxides KW - Sulfonate salts KW - Phosphorus flame retardants PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-643257 DO - https://doi.org/10.1016/j.polymdegradstab.2025.111711 SN - 1873-2321 SN - 0141-3910 VL - 242 SP - 1 EP - 18 PB - Elsevier Ltd. AN - OPUS4-64325 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schartel, Bernhard T1 - Sustainability features future flame retardancy: Microalgae phosphorus-enriched in wastewater and polylimonencarbonate N2 - Rather environmentally friendly flame retardant bio-composites have become part of the state of the art. Using two illuminating examples the talk gives an outlook towards sustainability beyond “partly bio-carbon”. In waste water phosphorous-enriched microalgae are introduced as bio-based adjuvant in polylactide (PLA). The flame retardancy effect is discussed and compared with other novel bio-based additives. In a combination with a commercial flame retardant, half of the commercial flame retardant can be replaced without worsening the UL 94 classification V0. In the second example flame retardant routes for poly(limonene carbonate) are discussed. Poly(limonene carbonate) is synthesized with a bio-based monomer limonene oxide and CO2. A novel bio-based flame retardant melem phytate together with bio-based charring agents is proposed to realize a fully bio-based flame retardant poly(limonene carbonate). T2 - Fire Resistance in Plastics CY - Düsseldorf, Germany DA - 01.12.2025 KW - Poly(limonene carbonate) KW - Microalgae KW - Phosphorous flame retardants KW - Melem phytate KW - Waste water phosphorous PY - 2025 AN - OPUS4-65014 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Frasca, Daniele A1 - Schulze, Dietmar A1 - Wachtendorf, Volker A1 - Krafft, Bernd A1 - Rybak, Thomas A1 - Schartel, Bernhard T1 - Multilayer Graphene/Carbon Black/Chlorine Isobutyl Isoprene Rubber Nanocomposites N2 - High loadings of carbon black (CB) are usually used to achieve the properties demanded of rubber compounds. In recent years, distinct nanoparticles have been investigated to replace CB in whole or in part, in order to reduce the necessary filler content or to improve performance. Multilayer graphene (MLG) is a nanoparticle made of just 10 graphene sheets and has recently become commercially available for mass-product nanocomposites. Three phr (part for hundred rubbers) of MLG are added to chlorine isobutyl isoprene rubber (CIIR)/CB composites in order to replace part of the CB. The incorporation of just 3 phr MLG triples the Young’s modulus of CIIR; the same effect is obtained with 20 phr CB. The simultaneous presence of three MLG and CB also delivers remarkable properties, e.g. adding three MLG and 20 phr CB increased the hardness as much as adding 40 phr CB. A comprehensive study is presented, showing the influence on a variety of mechanical properties. The potential of the MLG/CB combination is illustrated to reduce the filler content or to boost performance, respectively. Apart from the remarkable mechanical properties, the CIIR/CB/MLG nanocomposites showed an increase in weathering resistance. KW - nanocomposites KW - rubber KW - multilayer graphene KW - carbon black PY - 2016 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-358569 DO - https://doi.org/10.3390/polym8030095 SN - 2073-4360 VL - 8 SP - 95 PB - MDPI CY - Basel, Switzerland AN - OPUS4-35856 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Kempel, Florian A1 - Hofmann-Böllinghaus, Anja A1 - Schartel, Bernhard A1 - Krause, Ulrich T1 - Investigations on a real fire case with downward fire spread in a family home T2 - 11th International symposium on fire protection CY - Leipzig, Germany DA - 2010-06-08 KW - Fire spread KW - Heat release rate KW - Fire simulation KW - Foam mattress PY - 2010 N1 - Geburtsname von Hofmann-Böllinghaus, Anja: Hofmann, A. - Birth name of Hofmann-Böllinghaus, Anja: Hofmann, A. SP - 1 EP - 12 AN - OPUS4-22354 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Kempel, Florian A1 - Schartel, Bernhard A1 - Hofmann-Böllinghaus, Anja A1 - Linteris, G.T. A1 - Lyon, R.E. A1 - Walters, R.N. A1 - Stoliarov, S.I. T1 - Numerical simulation of polymer materials in standard fire tests: Pyrolysis and the impact of residue formation T2 - Interflam 2010 - 12th International conference CY - Nottingham, UK DA - 2010-07-05 KW - Cone calorimeter KW - Poly(butylene terephtalate) PBT KW - FDS KW - ThermaKin PY - 2010 SN - 978-0-9541216-5-5 N1 - Geburtsname von Hofmann-Böllinghaus, Anja: Hofmann, A. - Birth name of Hofmann-Böllinghaus, Anja: Hofmann, A. VL - 1 SP - 451 EP - 462 PB - Interscience Communications CY - London, UK AN - OPUS4-21668 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Braun, Ulrike A1 - Sturm, Heinz A1 - Schartel, Bernhard T1 - Flame retardancy mechanisms of aluminium phosphinate in glass-fibre reinforced polyester T2 - Flame Retardants 2008 Conference CY - London, UK DA - 2008-02-12 PY - 2008 SN - 978-0-9556548-1-7 SP - 133 EP - 140 PB - Interscience Communications CY - London, UK AN - OPUS4-17785 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Braun, Ulrike A1 - Bahr, Horst A1 - Sturm, Heinz A1 - Schartel, Bernhard T1 - Flame retardancy mechanisms of metal phosphinates and metal phosphinates in combination with melamine cyanurate in glass-fiber reinforced poly(1,4-butylene terephthalate): the influence of metal cation N2 - The pyrolysis and fire behavior of glass-fiber reinforced poly(butylene terephthalate) (PBT/GF) with two different metal phosphinates as flame retardants in combination with and without melamine cyanurate (MC) were analyzed by means of thermogravimetry, thermogravimetry coupled with infrared spectroscopy, flammability, and cone calorimeter tests as well as scanning electron microscopy/energy dispersive X-ray spectroscopy and X-ray fluorescence spectroscopy. In PBT/GF, dosages of 13-20% of the halogen-free flame retardant aluminum phosphinate or aluminum phosphinate in combination with MC fulfill the requirements for electrical engineering and electronics applications (UL 94 = V-0; LOI > 42%), whereas the use of the same amount of zinc phosphinate or zinc phosphinate in combination with MC does not improve the fire behavior satisfactorily (UL 94 = HB; LOI = 27-28%). The performance under forced flaming conditions (cone calorimeter) is quite similar for both of the metal phosphinates. The use of aluminum and zinc salts results in similar flame inhibition predominantly due to the release of the phosphinate compounds in the gas phase. Both metal phosphinates and MC interact with the polymer changing the decomposition characteristics. However, part of the zinc phosphinate vaporizes as a complete molecule. Because of the different decomposition behavior of the metal salts, only the aluminum phosphinate results in a small amount of thermally stable carbonaceous char. In particular, the aluminum phosphinate-terephthalate formed is more stable than the zinc phosphinate-terephthalate. The small amount of char has a crucial effect on the thermal properties and mechanical stability of the residue and thus the flammability. KW - Flame retardance KW - Polyester KW - Phosphinates KW - Pyrolysis KW - Cone calorimeter PY - 2008 DO - https://doi.org/10.1002/pat.1147 SN - 1042-7147 SN - 1099-1581 VL - 19 IS - 6 SP - 680 EP - 692 PB - John Wiley & Sons, Ltd. CY - Chichester AN - OPUS4-17620 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schartel, Bernhard A1 - Weiß, André A1 - Sturm, Heinz A1 - Kleemeier, M. A1 - Hartwig, A. A1 - Vogt, C. A1 - Fischer, R.X. T1 - Layered silicate epoxy nanocomposites: formation of the inorganic-carbonaceous fire protection layer N2 - The layered silicate (LS) modification and processing parameters applied control the morphology of the LS/polymer composites. Here, increasing the surface area of the LS particles by using alternative drying processes increases dispersion towards a more typical nanocomposite morphology, which is a basic requirement for promising flame retardancy. Nevertheless, the morphology at room temperature does not act itself with respect to flame retardancy, but serves as a prerequisite for the formation of an efficient surface protection layer during pyrolysis. The formation of this residue layer was addressed experimentally for the actual pyrolysis region of a burning nanocomposite and thus our results are valid without any assumptions or compromises on the time period, dimension, surrounding atmosphere or temperature. The formation of the inorganic-carbonaceous residue is influenced by bubbling, migration, reorientation, agglomeration, ablation, and perhaps also delamination induced thermally and by decomposition, whereas true sintering of the inorganic particles was ruled out as an important mechanism. Multiple, quite different mechanisms are relevant during the formation of the residue, and the importance of each mechanism probably differs from one nanocomposite system to another. The main fire protection effect of the surface layer in polymer nanocomposites based on non-charring or nearly non-charring polymers is the increase in surface temperature, resulting in a substantial increase in reradiated heat flux (heat shielding). KW - Nanocomposite KW - Fire retardancy KW - Epoxy resin KW - Fire behavior KW - Flammability PY - 2011 DO - https://doi.org/10.1002/pat.1644 SN - 1042-7147 SN - 1099-1581 VL - 22 IS - 12 SP - 1581 EP - 1592 PB - John Wiley & Sons, Ltd. CY - Chichester AN - OPUS4-24916 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Tabaka, Weronika A1 - Timme, Sebastian A1 - Lauterbach, Tobias A1 - Medina, L. A1 - Berglund, L. A. A1 - Carosio, F. A1 - Duquesne, S. A1 - Schartel, Bernhard T1 - Bench-scale fire stability testing - Assessment of protective systems on carbon fibre reinforced polymer composites N2 - 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. KW - Fire stability KW - Bench-scale fire resistance KW - Carbon fibre reinforced polymer KW - Protective coatings PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-532401 DO - https://doi.org/10.1016/j.polymertesting.2021.107340 SN - 0142-9418 SN - 1873-2348 VL - 102 SP - 7340 PB - Elsevier CY - Amsterdam AN - OPUS4-53240 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Jauregui Rozo, Maria A1 - Sunder, S. A1 - Tabaka, Weronika A1 - Klaffke, Benjamin A1 - Ruckdäschel, H. A1 - Schartel, Bernhard T1 - Unveiling aluminum diethyl phosphinate dual identity: Transfer from epoxy resins to glass fiber-reinforced composites N2 - This study examines the transfer of the flame-retardant aluminum diethyl phosphinate (AlPi) from epoxy resins to composites and the impact of AlPi on fire behavior and fire stability. Further, the effects of different particle sizes and the addition of zinc hydroxy stannate (ZHS) and inorganic silicate (InSi) are investigated. The research provides a detailed analysis of the fire behavior, fire stability, pyrolysis, flame-retardant modes of action, and flame retardancy index. Interestingly, the particle sizes did not significantly affect the flammability, fire behavior, or fire stability in the systems investigated. AlPi acts primarily in the gas phase, releasing phosphorus that yields flame inhibition. Adding glass fibers (GFs) to the epoxy resin boosts the flame retardancy in the condensed phase, reducing the heat release rate (HRR), total heat release (THR), and peak heat release rate (PHRR) by about 60%. This improvement is largely due to replacing fuel and forming a protective layer during burning. Despite the differences between thermoset and composite, the study demonstrates an effective transfer of flame-retardant properties from epoxy resins to fiber-reinforced composites, significantly enhancing the flame retardancy performance in both material systems. KW - Aluminum diethyl phosphinate KW - Epoxy resins KW - Fire behavior KW - Fire stability KW - Gas-phase active KW - Glass fiber-reinforced composites KW - Particle sizes PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-643013 DO - https://doi.org/10.1002/pc.29911 SN - 1548-0569 SN - 0272-8397 VL - 46 IS - 14 SP - 12981 EP - 12999 PB - Wiley AN - OPUS4-64301 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Tabaka, Weronika A1 - Meinel, Dietmar A1 - Schartel, Bernhard T1 - Sacrifice Few to Save Many: Fire Protective Interlayers in Carbon- Fiber-Reinforced Laminates N2 - The fire protection of carbon-fiber-reinforced polymer (CFRP) laminates often relies on flame-retardant coatings, but in some applications, their efficacy may diminish upon direct fire exposure due to rapid pyrolysis. This study introduces an innovative approach by integrating protective interlayers within the laminate structure to enhance the fire resistance. Various materials, including ceramic composite WHIPOX, titanium foil, poly(etherimide) (PEI) foil, basalt fibers, rubber mat, and hemp fibers, were selected as protective interlayers. These interlayers were strategically placed within the laminate layout to form a sacrificial barrier, safeguarding the integrity of the composite. Bench-scale fire resistance tests were conducted, where fire (180 kW/m2) was applied directly to the one side of the specimen by a burner while a compressive load was applied at the same time. Results indicate significant prolongation of time to failure for CFRP laminates with protective interlayers, which is up to 10 times longer. This innovative approach represents a potential advance in fire protection strategies for CFRP laminates, offering improved resilience against fire-induced structural failure. KW - Composites in fire KW - Fire resistance KW - Fire retardant interlayers KW - Laminate design KW - Carbon fibre reinforced PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-601943 DO - https://doi.org/10.1021/acsomega.4c01408 SN - 2470-1343 VL - 9 IS - 22 SP - 23703 EP - 23712 PB - ACS AN - OPUS4-60194 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zirnstein, Benjamin A1 - Tabaka, Weronika A1 - Frasca, Daniele A1 - Schulze, Dietmar A1 - Schartel, Bernhard T1 - Graphene / hydrogenated acrylonitrile-butadiene rubber nanocomposites: Dispersion, curing, mechanical reinforcement, multifunctional filler N2 - Elastomers are usually mechanically reinforced with high loadings of carbon black (CB) to achieve the properties demanded; high amounts of mineral flame retardants are used to fulfill fire safety requirements. In this study, multilayer graphene (MLG), a nanoparticle made of only 10 graphene sheets, is applied in low loadings, 3 parts per hundred rubber (phr) to reduce the total amount of filler or boost performance in hydrogenated acrylonitrilebutadiene rubber (HNBR). In the HNBR/MLG nanocomposites, 3 phr MLG replaced 15 phr CB, 3 phr aluminum trihydroxide (ATH), or 15 phr CB + 3 phr ATH. The nanocomposites were prepared via master batch by ultrasonically assisted solution mixing and subsequent conventional two-roll milling. A comprehensive study is presented, illustrating the impact of MLG on curing and mechanical properties; e.g. replacing 2.5 phr ATH with 3 phr MLG increased the Young's modulus by over 60% and hardness by 10%, while improving flame retardancy, and reducing the total heat evolved by 10%. MLG is a multifunctional filler, as demonstrated by various enhancements in terms of the mechanical and flame retardancy properties of the rubber composites. KW - Nanocomposite KW - Rubber KW - Graphene PY - 2018 DO - https://doi.org/10.1016/j.polymertesting.2018.01.035 SN - 0142-9418 SN - 1873-2348 VL - 66 SP - 268 EP - 279 PB - Elsevier Ltd. AN - OPUS4-44457 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schartel, Bernhard T1 - Small but Great – Multifunctional Graphene in Rubber Nanocomposites N2 - A few layer/multilayer graphene (MLG) with a specific surface area of BET ≥ 250 m2/g is proposed as an efficient multifunctional nanofiller for rubbers. The preparation method, i.e., ultrasonically-assisted solution or latex premixing of master batches followed by conventional two-roll milling, strongly influences the dispersion in the elastomeric matrix and is fundamental for the final properties. When homogenously dispersed, single stacks of only approximately 10 graphene sheets, with an aspect ratio of ca. 35, work at low loadings, enabling the replacement of large amounts of carbon black (CB), an increase in efficiency, and a reduction in filler load. The appropriate preparation yielded nanocomposites in which just 3 phr are sufficient to significantly improve the rheological, curing, gas barrier properties, electrical and thermal conductivity, as well as mechanical properties of different rubbers, as shown for chlorine-Isobutylene-Isoprene rubber (CIIR), nitrile-butadiene rubber (NBR), natural rubber (NR), and styrene-butadiene rubber (SBR).[1-5] 3 phr of MLG tripled the Young’s modulus of CIIR, an effect equivalent to 20 phr of CB. The stronger interactions between MLG and NR or SBR also resulted in a reduction in the elongation at break by 20% and 50%, respectively, while the same parameter was hardly changed for CIIR/MLG and NBR/MLG. CIIR/MLG and NBR/MLG were stiffer but just as defomable than CIIR and NBR. The strong reinforcing effect of 3 phr MLG was confirmed by the increase of greater than 10 Shore A in hardness. MLG reduces gas permeability, increases thermal and electrical conductivities, and retards flammability. We investigated MLG also as a synergist for reducing the aluminium trihydrate loading in flame retardant hydrogenated acrylonitrile-butadiene (HNBR), polybutadiene chloroprene (BR/CR), and chlorosulfonated polyethylene rubber(CSM).[6-8] The higher the nanofiller concentration is, the greater the improvement in the properties. For instance, the permeability decreased by 30% at 3 phr of MLG, 50% at 5 phr and 60% at 10 phr, respectively. Moreover, the MLG nanocomposites improve stability of mechanical properties against the effects of weathering. In key experiments an increase in UV-absorption and a pronounced radical scavenging were proved as stabilizing mechanisms. In a nutshell, MLG is an efficient multifunctional nanofiller ready to be used for innovative rubber development. T2 - 34th PDDG Conference CY - Dubrovnik, Croatia DA - 11.06.2023 KW - Graphene KW - Nanocomposites KW - Reinforcement KW - Antioxydant KW - Flame retardant KW - Durability PY - 2023 AN - OPUS4-57693 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schartel, Bernhard T1 - Multifunctional Elastomer/Graphene Nanocomposites N2 - A few layer/multilayer graphene (MLG) with a specific surface area of BET=250 m2/g is proposed as an efficient multifunctional nanofiller for rubbers. The preparation method, i.e., ultrasonically-assisted solution mixing of master batches followed by two-roll milling, strongly influences the dispersion in the elastomeric matrix and is fundamental for the final properties. When homogenously dispersed, single stacks of only approximately 10 graphene sheets, with an aspect ratio of 34, work at low loadings, enabling the replacement of large amounts of carbon black (CB), an increase in efficiency, and a reduction in filler load. The appropriate preparation yielded nanocomposites in which just 3 phr are sufficient to significantly improve the rheological, curing, gas barrier properties, electrical and thermal conductivity, as well as mechanical properties of different rubbers, as shown for chlorine-Isobutylene-Isoprene rubber (CIIR), nitrile-butadiene rubber (NBR), natural rubber (NR), and styrene-butadiene rubber (SBR). 3 phr of MLG tripled the Young’s modulus of CIIR, an effect equivalent to 20 phr of CB. The stronger interactions between MLG and NR or SBR also resulted in a reduction in the elongation at break by 20% and 50%, respectively, while the same parameter was hardly changed for CIIR/MLG and NBR/MLG. CIIR/MLG and NBR/MLG were stiffer but just as defomable than CIIR and NBR. The strong reinforcing effect of 3 phr MLG was confirmed by the increase of greater than 10 Shore A in hardness. MLG reduces gas permeability, increases thermal and electrical conductivities, and retards flammability, the latter shown by the reduction in heat release rate in the cone calorimeter. We investigated MLG also as a synergist for reducing the aluminium trihydrate loading in flame retardant hydrogenated acrylonitrile-butadiene (HNBR), polybutadiene chloroprene (BR/CR), and chlorosulfonated polyethylene rubber(CSM). The higher the nanofiller concentration is, the greater the improvement in the properties. For instance, the permeability decreased by 30% at 3 phr of MLG, 50% at 5 phr and 60% at 10 phr, respectively. Moreover, the MLG nanocomposites improve stability of mechanical properties against the effects of weathering. In key experiments an increase in UV-absorption and a pronounced radical scavenging were proved as stabilizing mechanisms. In a nutshell, MLG is an efficient multifunctional nanofiller ready to be used for innovative rubber development. T2 - 19th European Polymer Congress, EPF 2022 CY - Prague, Czech Republic DA - 26.06.2022 KW - Graphene KW - Nanocomposite KW - Rubber KW - Elastomer PY - 2022 AN - OPUS4-55196 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Fichera, Mario Augusto A1 - Braun, Ulrike A1 - Schartel, Bernhard A1 - Sturm, Heinz A1 - Knoll, Uta A1 - Jäger, Christian T1 - Solid-state NMR investigations of the pyrolysis and thermo-oxidative decomposition products of a polystyrene/red phosphorus/magnesium hydroxide system N2 - Thermal, thermo-oxidative and fire residues of high impact polystyrene/magnesium hydroxide/red phosphorus (HIPS/Mg(OH)2/Pr) are investigated by solid-state NMR and compared with the results for the binary subsystem Mg(OH)2/Pr. The influences of oxygen, nitrogen and temperature are discussed. For a thermal decomposition and pyrolysis during combustion, the main pyrolysis of HIPS takes place while the remaining residue is a rather intact polymer, with a major share of the embedded Pr still present. Subsequently, mainly amorphous phosphates and a slight amount of crystalline Mg3(PO4)2 and Mg2P2O7 are formed at the highest temperatures. Only with increasing mass loss does the remaining polystyrene structure decompose and graphitic structures occur. The influence of oxygen on the decomposition mechanism is most obvious for the binary system Mg(OH)2/Pr. Pr vanishes more rapidly and crystalline, oxygen-rich magnesium phosphates are formed. In HIPS/Mg(OH)2/Pr systems the polymer acts as a barrier to reaction by the embedded particles, so that major characteristics of an anaerobic decomposition are found. Significant amounts of phosphorus are retained in the condensed phase through a reaction of Pr with Mg(OH)2 to mostly amorphous phosphates. This formation of amorphous inorganic magnesium phosphates can act as an additional physical barrier. This study outlines some advanced approaches for controlling the condensed-phase mechanisms of phosphorus and underlines that solid-state NMR is a most powerful tool for investigating the organic and inorganic residues. KW - HIPS KW - Red phosphorus KW - Magnesium hydroxide KW - Solid-state NMR KW - Flame retarded polymers PY - 2007 SN - 0165-2370 SN - 1873-250X VL - 78 IS - 2 SP - 378 EP - 386 PB - Elsevier CY - Amsterdam AN - OPUS4-14517 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Tabaka, Weronika A1 - Schartel, Bernhard T1 - Less is More: Optimised Fire Performance in Glass Fibre-reinforced Polybutylene Terephthalate Laminates with Concentrated Flame Retardant Top Layer N2 - To achieve optimum fire performance while maintaining mechanical integrity, flame retardants (FR) were strategically concentrated in the surface layer of a two-layer glass fibre-reinforced polybutylene terephthalate (PBT) laminate structure. Three potentially synergistic FR systems were selected to improve the fire performance of glass fibre-reinforced PBT: boehmite (AlOOH) with melamine polyzinc phosphate (MPZnP), aluminium diethyl phosphinates (AlPi) with melamine cyanurate (MC), and expandable graphite (EG) with melamine polyphosphate (MPP). Limited Oxygen Index (LOI) and UL-94 testing highlighted the influence of laminate architecture on flammability. The cone calorimeter results showed that increasing the FR concentration in the top layer significantly reduced both the peak heat release rate (PHRR) and the maximum average rate of heat emission (MARHE), with improvements depending on the specific FR system used. The laminate L-PBT/GF/AlOOH/MPZnP with a 2:2 thickness ratio showed outstanding performance, achieving a 45 % reduction in MARHE compared to composites with uniform FR distribution. This result showcases the superior thermal barrier properties and synergistic behaviour of AlOOH and MPZnP. The fire performance of laminates containing AlPi and MC was strongly influenced by the distribution and concentration of AlPi/MC. The EG/MPP system was found to be highly effective, forming a protective intumescent layer that significantly reduced both HRR and MARHE, demonstrating the effectiveness of strategically concentrating FR in the top layer. KW - Glass fibres KW - PBT KW - Flame retardants KW - Composites KW - Laminates KW - Fire behaviour KW - Flammability PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-626381 DO - https://doi.org/10.1016/j.jcomc.2025.100577 SN - 2666-6820 VL - 16 SP - 1 EP - 15 PB - Elsevier CY - Amsterdam AN - OPUS4-62638 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sturm, Heinz A1 - Schartel, Bernhard A1 - Weiß, André A1 - Braun, Ulrike T1 - SEM/EDX: Advanced investigation of structured fire residues and residue formation N2 - Heterogeneous, gradual or structured morphology of fire residues plays an important role in fire retardancy of polymers. A scanning electron microscope with an attached energy dispersive X-ray spectrometer (SEM/EDX) is highlighted as a powerful tool for the advanced characterization of such complex fire residues, since it offers high resolution in combination with both good depth of field and analysis of chemical composition. Two examples are presented: First, comprehensive SEM/EDX investigation on a complex structured fire residue of glass fibre reinforced polyamide 6,6 (PA 66-GF) flame retarded by diethylaluminium phosphinate, melamine polyphosphate and some zinc borate. A multilayered surface crust (thickness ~ 24 µm) covers a rather hollow area stabilized by GF glued together. The resulting efficient thermal insulation results in self-extinguishing before pyrolysis is completed, even under forced-flaming combustion. Second, sophisticated, quasi online SEM/EDX imaging of the formation of residual protection layer in layered silicate epoxy resin nanocomposites (LSEC). Burning specimens were quenched in liquid nitrogen for subsequent analyses. Different zones were distinguished in the condensed phase characterized by distinct processes such as melting and ablation of organic material, as well as agglomeration, depletion, exfoliation and reorientation of the LS. KW - Fire residue KW - SEM/EDX KW - Fire retardancy KW - PA 66 KW - Layered silicate KW - Diethylaluminium phosphinate PY - 2012 DO - https://doi.org/10.1016/j.polymertesting.2012.03.005 SN - 0142-9418 VL - 31 IS - 5 SP - 606 EP - 619 PB - Elsevier CY - Amsterdam AN - OPUS4-25802 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CHAP A1 - Böhning, Martin A1 - Frasca, Daniele A1 - Schulze, Dietmar A1 - Schartel, Bernhard ED - Yaragalla, S. ED - Kumar Mishra, R. ED - Thomas, S. ED - Kalarikkal, N. ED - Maria, H. J. T1 - Multilayer Graphene/Elastomer Nanocomposites N2 - Elastomers are usually reinforced by large amount of fillers like carbon black (CB) or silica in order to improve various mechanical properties, such as Young’s modulus, hardness, tear resistance, abrasion resistance, and gas barrier properties. In recent years, such improvements were also obtained by using nanoparticles at significantly lower filler loadings. Graphene is a twodimensional (2D) sheet of a thickness in the atomic scale, composed of a honeycomb structure of sp2 carbon atoms. Besides significant mechanical reinforcement, graphene harbors the potential to be used as a multifunctional filler, as it can also increase the conductivity and weathering stability of elastomer matrices. Ultraviolet (UV) irradiation and oxidative agents can lead to the degradation of elastomers due to a multistep photooxidative process, including the formation of radicals. Carbon-based fillers have an influence on these reactions, as they can absorb UV radiation and act as radical scavengers. This chapter summarizes the results of our larger project on multilayer graphene (MLG)/elastomer nanocomposites, previously published, which present a comprehensive case study of MLG as a multifunctional nanofiller in elastomer/graphene nanocomposites. Different elastomeric matrices are compared in order to demonstrate the outstanding impact of MLG as a general benefit. The dependency of this effect on concentration is discussed in detail. Taking into account the key role of dispersion, different mixing procedures are compared, evaluating a facile implementation of graphene nanocomposites into conventional rubber processing. Finally, the most probable commercial uses of MLG nanofillers in combination with conventional CB are studied. The nanocomposites were prepared in the kg scale in order to obtain enough specimens to investigate various properties of the uncured and vulcanized rubbers at the highest quality level, including rheology, curing, morphology, several mechanical properties, abrasion, conductivity, gas permeation, burning behavior, and weathering stability. The structure property relationships are asserted and questioned, for example, by investigating the radical scavenging ability or aspect ratio of the MLG. This chapter illustrates the state of the art of graphene/rubber nanocomposites targeted for commercial mass applications. KW - Nanocomposite KW - Graphene KW - Rubber KW - Reinforcement KW - Durability KW - Masterbatch KW - Gas Barrier Properties KW - Conductivity PY - 2019 SN - 978-0-12-817342-8 SP - 139 EP - 200 PB - Elsevier AN - OPUS4-47408 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schartel, Bernhard T1 - Flame Retardancy A Bunch of Thoughts N2 - The presentation gives an overview of actual research adtivities in the field of flame retardant polymers. Details are selected illuminating the scientific topic beyond the state of the art. Different concepts are illustrated with own results obtained in different Research projects over the last 15 years. T2 - public lecture at CIATEC CY - León, Guanajuato, México DA - 06.02.2019 KW - Flame retardant KW - Modes of action KW - Mechanisms KW - Fire testing KW - Pyrolysis KW - Calorimetry PY - 2019 AN - OPUS4-50078 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schneider, I. A1 - Kebelmann, Katharina A1 - Risse, S. A1 - Dieguez-Alonso, A. A1 - Schartel, Bernhard A1 - Strecker, C. A1 - Behrendt, F. T1 - Hydroliquefaction of Two Kraft Lignins in a Semibatch Setup under Process Conditions Applicable for Large-Scale Biofuel Production N2 - Hydroliquefaction is a possible pathway to produce liquid transportation fuels from solid feedstocks like coal or biomass. Though much effort has been put into the investigation of maximizing the oil yield using expensive catalysts and pasting oils in batch setups, little is known about how to commercialize the process. This work aims at the demonstration of lignin hydroliquefaction under conditions interesting for commercial operation. The results from hydroliquefaction experiments of two different lignin types using a cheap iron-based catalyst and anthracene oil as the pasting oil in a semibatch system are presented here. Oil yields of above 50% are reached without observing coke formation. Extensive analyses of the feedstocks and product oils were performed. The process supplies high-quality oil, while differences in the decomposition path of both lignin types are observed. An high heating value of 39 400 J/g and H/C and O/C ratios of up to 1.6 and 0.1, respectively, are detected for the produced bio-oils. KW - Lignin KW - Hydroliquefaction KW - Biofuel PY - 2019 DO - https://doi.org/10.1021/acs.energyfuels.9b02572 SN - 0887-0624 SN - 1520-5029 VL - 33 IS - 11 SP - 11057 EP - 11066 PB - ACS AN - OPUS4-50102 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Markwart, Jens C. A1 - Battig, Alexander A1 - Zimmermann, Lisa A1 - Wagner, Martin A1 - Fischer, Jochen A1 - Schartel, Bernhard A1 - Wurm, Frederik R. T1 - Systematically controlled decomposition mechanism in phosphorus flame retardants by precise molecular architecture: P−O vs P−N N2 - Flame retardants (FR) are inevitable additives to many plastics. Halogenated organics are effective FRs but are controversially discussed due to the release of toxic gases during a fire or their persistence if landfilled. Phosphorus-containing compounds are effective alternatives to halogenated FRs and have potential lower toxicity and degradability. In addition, nitrogencontaining additives were reported to induce synergistic effects with phosphorus-based FRs. However, no systematic study of the gradual variation on a single phosphorus FR containing both P−O and P−N moieties and their comparison to the respective blends of phosphates and phosphoramides was reported. This study developed general design principles for P−O- and P−N-based FRs and will help to design effective FRs for various polymers. We synthesized a library of phosphorus FRs that only differ in their P-binding pattern from each other and studied their decomposition mechanism in epoxy resins. Systematic control over the decomposition pathways of phosphate (PO(OR)3), phosphoramidate (PO(OR)2(NHR)), phosphorodiamidate (PO(OR)(NHR)2), phosphoramide (PO(NHR)3), and their blends was identified, for example, by reducing cis-elimination and the formation of P−N-rich char with increasing nitrogen content in the P-binding sphere. Our FR epoxy resins can compete with commercial FRs in most cases, but we proved that the blending of esters and amides outperformed the single molecule amidates/diamidates due to distinctively different decomposition mechanisms acting synergistically when blended. KW - Phosphorus KW - Flame retardants KW - Epoxies KW - Mechanistic study KW - Toxicity PY - 2019 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-481549 DO - https://doi.org/10.1021/acsapm.9b00129 SN - 2637-6105 VL - 1 IS - 5 SP - 1118 EP - 1128 PB - ACS AN - OPUS4-48154 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Krüger, Simone A1 - Schartel, Bernhard A1 - Schoch, Rebecca A1 - Schubert, Martina T1 - Holz-Kunststoff-Verbundwerkstoffe - Wie beeinflussen Flammschutzmittel die Rauchgaszusammensetzung im Brandfall? N2 - Der steigende Einsatz von Holz-Kunststoff-Verbundwerkstoffen (Wood Plastic Composite, WPC) erfordert das Wissen um seine spezifischen Eigenschaften, insbesondere dem Brand risiko. Dabei können Flammschutzmittel die Entflammbarkeit, Wärmeabgabe und die Brandausbreitung des Materials verringern. Deshalb sind der gezielte und effiziente Einsatz und die Kenntnis über die Wirkungsweise der Flammschutzmittel im WPC für den Brandschutz von enormer Bedeutung. Dazu gehört auch die Rauchentwicklung im Brandfall. Rauch beeinflusst aufgrund seiner Toxizität und seiner Sichttrübung die Fluchtmöglichkeit der betroffenen Personen. In der Rauchkammer nach ISO 5659-2 wird die Rauchentwicklung von flachen Werkstoffproben ermittelt. Die Rauchgastoxizität bzw. die Rauchgaszusammensetzung wird mithilfe der FTIR (Fourier Transformierte Infrarot)-Spektroskopie ermittelt. Frei werdende Partikel schädigen die Atemorgane und beeinflussen damit auch die Fluchtfähigkeit von Personen im Brandfall. Aussagen zur Partikelemission können mithilfe eines an die Rauchkammer gekoppelten Partikelanalysators getroffen werden. Im Rahmen dieser Arbeit wurden verschiedene flammgeschützte WPC-Systeme hinsichtlich ihres Rauchverhaltens in der Rauchkammer untersucht. Die Ergebnisse zu emittierten toxischen Gasen, Partikeln und zur Rauchentwicklung werden vorgestellt und in Abhängigkeit von den eingesetzten Flammschutzmitteln im WPC diskutiert. KW - Rauchgase KW - Holz-Kunststoff-Verbundwerkstoffe KW - Partikel KW - Flammschutz PY - 2019 DO - https://doi.org/10.1002/bate.201900020 VL - 96 SP - 1 EP - 12 PB - Wiley AN - OPUS4-48157 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zirnstein, Benjamin A1 - Schulze, Dietmar A1 - Schartel, Bernhard T1 - Mechanical and fire properties of multicomponent flame retardant EPDM rubbers using aluminum trihydroxide, ammonium polyphosphate, and polyaniline N2 - 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. KW - EPDM KW - Rubber KW - Flame retardant KW - Polyaniline KW - Aluminum trihydroxide (ATH) PY - 2019 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-482769 DO - https://doi.org/10.3390/ma12121932 SN - 1996-1944 VL - 12 IS - 12 SP - 1932, 1 EP - 22 PB - MDPI AN - OPUS4-48276 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sanchez-Olivares, G. A1 - Rabe, Sebastian A1 - Pérez-Chávez, R. A1 - Calderas, F. A1 - Schartel, Bernhard T1 - Industrial-waste agave fibres in flame-retarded thermoplastic starch biocomposites N2 - Flame-retarded biocomposites of thermoplastic starch and natural fibres are successfully processed according to state-of-the-art extrusion and injection moulding. Using agave fibres and henequen fibres recovered from local industrial waste is a convincing contribution to sustainability. A systematically varied set of biocomposites is investigated comprehensively, e.g. electron microscopy is used for characterizing the morphology, rheology for the melt viscosity, tensile and impact resistance for the mechanical properties, thermal analysis for the pyrolysis, UL 94 burning chamber and oxygen index for the flammability, and cone calorimeter for the fire behaviour. Achieving sufficient mechanical properties was not the goal in our pre-competitive study but may be tackled by adding compatibilizer in future. The combination of well-dispersed natural fibres, aluminium diethylphosphinate (AlPi) and a special silicone synergist (Si) is proposed as promising innovative route for V-classified biocomposites. The flame-retardancy modes of action in the gas phase (fuel dilution and flame inhibition) and in the condensed phase (charring, protective layer formation) are discussed in detail, as is the role of combining the ingredients. This work is a convincing proof of principle of how to prepare industrial-waste fibres biocomposites, to apply the synergistic combination of AlPi and Si for future flame-retarded technical polymer materials that are based on renewable resources and compostable. KW - Flame-retardant biocomposites KW - Natural fibre KW - Biopolymer KW - Sustainability KW - Industrial-waste fibres KW - Flammability PY - 2019 DO - https://doi.org/10.1016/j.compositesb.2019.107370 SN - 1359-8368 VL - 177 SP - 107370 PB - Elsevier Ltd. AN - OPUS4-48777 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Markwart, J. C. A1 - Battig, Alexander A1 - Kuckhoff, T. A1 - Schartel, Bernhard A1 - Wurm, F. R. T1 - First phosphorus AB2 monomer for flame-retardant hyperbranched polyphosphoesters: AB2vs. A2 + B3 N2 - Branched polymers are an important class of polymers with a high number of terminal groups, lower viscosity compared to their linear analogs and higher miscibility, which makes them especially interesting for flame retardant applications, where the flame retardants (FR) are blended with another polymer matrix. Hyperbranched polyphosphoesters (hbPPEs) are gaining more and more interest in the field of flame retardancy, as low molar mass FRs often have the disadvantage of blooming out or leaching, which is not desired in consumer products. Here, we present the first phosphorus-based AB2 monomer for the synthesis of hbPPEs and assess its flame-retardant performance in an epoxy resin compared to a hbPPE synthesized by an A2 + B3 approach. The hbPPE synthesized from an AB2 monomer exhibited a slightly higher performance compared to a similar hbPPE, which was prepared by A2 + B3 polyaddition, probably due to its higher phosphorus content. KW - Polyphosphoester KW - Hyperbranched KW - Flame retardant KW - Synthesis PY - 2019 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-497570 DO - https://doi.org/10.1039/c9py01156k SN - 1759-9962 VL - 10 IS - 43 SP - 5920 EP - 5930 PB - RSC AN - OPUS4-49757 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schartel, Bernhard T1 - Flammschutzmechanismen in der Kunststofftechnik N2 - The main flame retardant modes of action are known, nevertheless 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. T2 - VDI-Vortrag, AK “Kunststofftechnik” des VDI-Bezirksverein Nürnberg e.V. CY - Erlangen, Germany DA - 20.11.2019 KW - Modes of action KW - Flame retardancy KW - Charring KW - Flame inhibition KW - Fuel dilution KW - Protective layer PY - 2019 AN - OPUS4-49759 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Battig, Alexander A1 - Markwart, J. C. A1 - Wurm, F. R. A1 - Schartel, Bernhard T1 - Matrix matters: Hyperbranched flame retardants in aliphatic and aromatic epoxy resins N2 - We synthesized a library of phosphorus-based flame retardants (phosphates and phosphoramides of low and high molar mass) and investigated their behavior in two epoxy resins (one aliphatic and one aromatic). The pyrolytic and burning behavior of the two resins (via TGA, TG-FTIR, Hot stage FTIR, Py-GC/MS, PCFC, DSC, LOI, UL-94, Cone calorimeter) are analyzed and compared to the results of flame retardant (FR)-containing composites. A decomposition pathway incorporating the identified modes of action and known chemical mechanisms is proposed. The overlap of decomposition temperature (Tdec) ranges of matrix and FR determines the efficacy of the system. Low molar mass FRs strongly impact material properties like Tg but are very reactive, and high molar mass variants are more thermally stable. Varying PeO and PeN content of the FR affects decomposition, but the chemical structure of the matrix also guides FR behavior. Thus, phosphates afford lower fire load and heat release in aliphatic epoxy resins, and phosphoramides can act as additives in an aromatic matrix or a reactive FRs in aliphatic ones. The chemical structure and the structure-property relationship of both FR and matrix are central to FR performance and must be viewed not as two separate but as one codependent system. KW - Flame retardant KW - Phosphate KW - Phosphoramide KW - Epoxy resin KW - Hyperbranched polymer PY - 2019 DO - https://doi.org/10.1016/j.polymdegradstab.2019.108986 SN - 0141-3910 VL - 170 SP - 108986 PB - Elsevier Ltd. AN - OPUS4-49456 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Markwart, J. C. A1 - Battig, Alexander A1 - Velencoso, M. M. A1 - Pollok, D. A1 - Schartel, Bernhard A1 - Wurm, F. R. T1 - Aromatic vs. Aliphatic Hyperbranched Polyphosphoesters as Flame Retardants in Epoxy Resins N2 - The current trend for future flame retardants (FRs) goes to novel efficient halogen-free materials, due to the ban of several halogenated FRs. Among the most promising alternatives are phosphorus-based FRs, and of those, polymeric materials with complex shape have been recently reported. Herein, we present novel halogen-free aromatic and aliphatic hyperbranched polyphosphoesters (hbPPEs), which were synthesized by olefin Metathesis polymerization and investigated them as a FR in epoxy resins. We compare their efficiency (aliphatic vs. aromatic) and further assess the differences between the monomeric compounds and the hbPPEs. The decomposition and vaporizing behavior of a compound is an important factor in its flame-retardant behavior, but also the interaction with the pyrolyzing matrix has a significant influence on the performance. Therefore, the challenge in designing a FR is to optimize the chemical structure and its decomposition pathway to the matrix, with regards to time and temperature. This behavior becomes obvious in this study, and explains the superior gas phase activity of the aliphatic FRs. KW - Phosphorus KW - Metathesis KW - Dendritic KW - Cone calorimeter KW - Fire test PY - 2019 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-494535 DO - https://doi.org/10.3390/molecules24213901 SN - 1420-3049 VL - 24 IS - 21 SP - 3901 PB - MDPI AN - OPUS4-49453 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schartel, Bernhard T1 - Weathering resistance of halogen-free flame retardancy N2 - Whereas the degradation of flame retardant polymers has been discussed since decades, only more recently, the lifetime of the flame retardancy itself becomes an important factor, e.g. for cables used as building products. In this work, several kinds of accelerated artificial ageing tests are performed simulating different environmental exposures and thus highlighting different degradation mechanisms: artificial accelerated weathering, climatic chamber, water immersion, salt spray chamber, and autoclave test. The durability is expected to be different for different flame-retardant materials. Thus, various sets of halogen-free fire-retarded polymers were investigated: ethylene vinyl acetate (EVA) with aluminum hydroxide (ATH), boehmite and synergists, ester-based and ether-based thermoplastic polyurethane (TPU) with melamine cyanurate (MC), aluminum diethylphosphinate (AlPi), and boehmite, and glass fiber reinforced polyamide 66 (PA66) with AlPi-based mixtures. Intensive degradation of the surface was observed, e.g. yielding discoloration and yellowing, EVA showed cracking when weathered. Changes in chemical structure was investigated by ATR-FTIR. The flammability was investigated with the cone calorimeter, UL-94 classification, and oxygen index (LOI). The flame retardancy of most of the materials studied degraded only slightly for the investigated exposure times. EVA/ATH achieved an improved LOI due to flame retardants agglomeration at the surface. Sets of materials, based on EVA and TPU, were also investigated as cable jackets. While flame retarded EVA exhibited no dripping during burning, TPU flame-retarded with MC cables showed pronounced melt-dripping. Cone calorimeter tests were carried out using cable rafts as well as our self-made cable module test, simulating a vertical bundle of cables at the bench scale. The comparison of different fire tests, different exposure conditions, and different materials carved out the specific degradation phenomena with respect to each of these parameters. Most of this work was supported by the IGF Project (18926 N) of the Fördergemeinschaft für das Süddeutsche Kunststoff-Zentrum e.V., supported by the AiF within the framework of the program “Förderung der Industriellen Gemeinschaftsforschung (IGF)” of the German Federal Ministry for Economic Affairs and Energy based on a decision of the Deutschen Bundestag. T2 - 33rd Polymer Degradation Discussion Group Conference (PDDG-2019) CY - St. Julian, Malta DA - 01.09.2019 KW - Weathering resistance KW - Durability KW - Flame retardancy PY - 2019 AN - OPUS4-49020 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rabe, Sebastian A1 - Sánchez-Olivares, G. A1 - Pérez-Chávez, R. A1 - Schartel, Bernhard T1 - Natural keratin and coconut fibres from industrial wastes in flame retarded thermoplastic starch biocomposites N2 - Natural keratin fibres derived from Mexican tannery waste and coconut fibres from coconut processing waste were used as fillers in commercially available, biodegradable thermoplastic starch-polyester blend to obtain sustainable biocomposites. The morphology, rheological and mechanical properties as well as pyrolysis, flammability and forced flaming combustion behaviour of those biocomposites were investigated. In order to open up new application areas for these kinds of biocomposites, ammonium polyphosphate (APP) was added as a flame retardant. Extensive flammability and cone calorimeter studies revealed a good flame retardance effect with natural fibres alone and improved effectiveness with the addition of APP. In fact, it was shown that replacing 20 of 30 wt. % of APP with keratin fibres achieved the same effectiveness. In the case of coconut fibres, a synergistic effect led to an even lower heat release rate and total heat evolved due to reinforced char residue. This was confirmed via scanning electron microscopy of the char structure. All in all, these results constitute a good approach towards sustainable and biodegradable fibre reinforced biocomposites with improved flame retardant properties. KW - Biomaterials KW - Biodegradable KW - Calorimetry KW - Composites KW - Flame retardance PY - 2019 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-472518 DO - https://doi.org/10.3390/ma12030344 SN - 1996-1944 VL - 12 IS - 3 SP - 344, 1 EP - 24 PB - MDPI AN - OPUS4-47251 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sut, Aleksandra A1 - Metzsch-Zilligen, E. A1 - Großhauser, M. A1 - Pfaendner, R. A1 - Schartel, Bernhard T1 - Synergy between melamine cyanurate, melamine polyphosphate and aluminum diethylphosphinate in flame retarded thermoplastic polyurethane N2 - 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. KW - Thermoplastic polyurethane KW - Synergy KW - Melamine cyanurate KW - Melamine polyphosphate KW - Aluminum diethylphosphinate KW - Rapid mass calorimeter PY - 2019 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-472523 DO - https://doi.org/10.1016/j.polymertesting.2019.01.001 SN - 0142-9418 VL - 74 SP - 196 EP - 204 PB - Elsevier Ltd. AN - OPUS4-47252 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Yin, Huajie A1 - Sypaseuth, Fanni D. A1 - Schubert, M. A1 - Schoch, R. A1 - Bastian, M. A1 - Schartel, Bernhard T1 - Routes to halogen‐free flame‐retardant polypropylene wood plastic composites N2 - Developing halogen‐free flame retardants with reasonably high efficiency, which thus function at limited loadings in polypropylene‐based wood/plastic composites (WPC), is still a challenge. Cost‐effective flame‐retarded WPC have been identified as a way to open the door to an interesting, broader spectrum of application in the building and transportation sectors. This work imparts a systematic comprehensive understanding and assessment of different basic routes to halogen‐free flame‐retarded WPC, taking into account economic and environmental considerations. Cheap, halogen‐free single‐component flame retardants and their multicomponent systems are investigated at reasonable filling grades of 20 wt%. The basic routes of promising synergistic multicomponent systems are discussed, and their potential and Limits assessed. Optimizing the consistency of fire residue; closing the surface of inorganic‐organic residual layers; the thermal stabilization and design of the residue, eg, synergistic combination of ammonium polyphosphate and expandable graphite; and the combination of different flame‐retardant mechanisms, eg, intumescence and flame inhibition, are proposed as promising routes to boost the flame‐retardant efficiency. KW - Flammability KW - Halogen‐free KW - Multicomponent systems KW - Polypropylene KW - Wood plastic composite (WPC) PY - 2019 DO - https://doi.org/10.1002/pat.4458 SN - 1099-1581 SN - 1042-7147 VL - 30 IS - 1 SP - 187 EP - 202 PB - Wiley AN - OPUS4-46909 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schartel, Bernhard A1 - Humphrey, J.K. A1 - Gibson, A.G. A1 - Hörold, Andreas A1 - Trappe, Volker A1 - Gettwert, V. T1 - Assessing the structural integrity of carbon-fibre sandwich panels in fire: Bench-scale approach N2 - The fire resistance of lightweight sandwich panels (SW) with carbon fibre/epoxy skins and a poly(methacryl imide) (PMI) foam core is investigated in compression under direct application of a severe flame (heat flux=200 kW m−2). A bench-scale test procedure was used, with the sample held vertically. The epoxy decomposition temperature was quickly exceeded, with rapid flash-over and progressive core softening and decomposition. There is a change in failure mode depending on whether the load is greater or less than 50% of the unexposed failure load, or in other words if one or two skins carry the load. At high loads, failure involved both skins with a single clear linear separation across each face. There is an inflection in the failure time relationship in the ∼50% load region, corresponding to the time taken for heat to be transmitted to the rear face, along with a change in the rear skin failure mode from separation to the formation of a plastic hinge. The integrity of the carbon front face, even with the resin burnt out, and the low thermal diffusivity of the core, both play key roles in prolonging rear face integrity, something to be borne in mind for future panel design. Intumescent coatings prolong the period before failure occurs. The ratio of times to failure with and without protection is proposed as a measure of their effectiveness. Apart from insulation properties, their adhesion and stability under severe fire impact play a key role. KW - Carbon fibres KW - Sandwich KW - Structural composites KW - Fracture KW - High-temperature properties KW - Surface treatments PY - 2019 DO - https://doi.org/10.1016/j.compositesb.2018.11.077 SN - 1359-8368 VL - 164 SP - 82 EP - 89 PB - Elsevier AN - OPUS4-46908 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schartel, Bernhard T1 - Digging in the dirt: Using natural fibers from industrial waste in flame retarded thermoplastic starch biocomposites N2 - To exploit application fields beyond packaging for biodegradable materials, flame retardancy and increased mechanical strength are usually required. This work focuses on the flammability of a thermoplastic starch/polyester blend reinforced with natural fibers derived from Mexican industry processes wastes, such as keratin fibers from the tannery industry, coconut fibers (coconut industry), and agave tequilana fibers and henequen fibers from tequila industry. Different fiber contents as well as combinations of varying contents of aluminum trihydroxide, expandable graphite, aluminum diethylphosphinate or ammonium polyphosphate are investigated. It is the goal to propose sustainable waste fibers as adjuvants improving the flame retardancy. This work provides the proof of principle for sustainable biodegradable flame retarded biocomposites. T2 - Flame 2018, 30th Annual Conference on Recent Advances in Flame Retardancy of Polymeric Materials CY - San Antonio, TX, USA DA - 19.05.2019 KW - biocomposite KW - sustainable KW - natural fibers KW - renewable KW - industrial waste KW - sustainability KW - thermoplastic starch KW - flame retardant PY - 2019 AN - OPUS4-48143 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zirnstein, Benjamin A1 - Schulze, Dietmar A1 - Schartel, Bernhard T1 - The impact of polyaniline in phosphorus flame retardant ethylene-propylene-diene-rubber (EPDM) N2 - Usually elastomers are loaded with high amounts of flame retardants to fulfill fire safety requirements. In this study the potential char precursor polyaniline (PANI) and the established fire retardant pentaerythritol (PER) were implemented in ethylene-propylene-diene monomer rubber (EPDM). PANI and PER were used in low loadings (7 phr) and combined with two phosphorous flame retardants, Ammonium polyphosphate (APP) and a piperazine-pyrophosphate/phosphoric acid compound (FP), to boost their performance. A comprehensive study is presented, explaining the impact of PANI on curing and mechanical properties, including compensation for the plasticizer-like effect of APP in EPDM, and improved flame retardancy. In the cone calorimeter test, the combination of EPDM/FP/PANI reduced the effective heat of combustion by 20%. All nine EPDM rubber compounds were investigated with the LOI and UL 94 tests, cone calorimeter, FMVSS 302 and glow wire testing to quantify fire performance. The PANI containing EPDM rubbers, EPDM/APP/PANI and EPDM/FP/PANI outperformed the corresponding PER containing, EPDM/APP/PER and EPDM/FP/PER rubbers in various tests. Moreover, the study investigated the impact of PANI and PER on the mode of action of the phosphorus species and showed that the addition of PANI increased the amount of phosphorus in the condensed phase. To receive a broader understanding of the flame retardant mode of action of PANI in combination with APP and FP, calculations were carried out to estimate the impact of PANI on the protective layer effect. KW - EPDM KW - Rubber KW - Flame retardant KW - Polyaniline KW - Pentaerythritol PY - 2019 DO - https://doi.org/10.1016/j.tca.2019.01.019 SN - 0040-6031 VL - 673 SP - 92 EP - 104 PB - Elsevier B.V. AN - OPUS4-47503 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schartel, Bernhard T1 - Flame Retardant Polyurethane: An Old, an Actual, and a Future Challenge N2 - This paper is based mainly on the results of two different projects performed in the group of the author recently (2016-2019). The three external partners involved in these two projects are competent in the preparation of FPUF (ICL IP America), RPUF (Department of Industrial Engineering, Padova University), and TPU (Fraunhofer-Institut für Betriebsfestigkeit und Systemzuverlässigkeit LBF, Darmstadt) as well as for the specimen preparation. Systematically varied sets of materials were prepared as the key basic for scientific discussion, varying the kind and combination of flame retardant, PUR structure, density, and blowing agent. A multimethodical approach based on thermogravimetry (TGA), TGA coupled with evolved gas analysis (TGA-FTIR) and pyrolysis GC-MS was used for investigating the pyrolysis. The flammability was addressed using oxygen index (OI) and testing in UL 94 burning chamber in vertical and horizontal set-up. The fire behaviour was addressed by using a cone calorimeter. Beyond these methods according to the state of the art, key experiments were performed. We addressed the dripping and the two-stage burning of TPU using a self-designed apparatus and specific data evaluation, the foam burning through quenching burning samples, using different special sample holders, and measuring temperature profiles within the burning foams. The investigation is made round by intensive analysis of the fire residues, such as comprehensive investigation of the morphology. Result on the pyrolysis (TGA-FTIR, Pyrolysis-GC/MS), flammability (UL 94, LOI), and fire behaviour (cone calorimeter) of TPU and flame retardant TPUs are shown. We discuss in detail the characteristic of PUR decomposition: the low tendency to char, and the specific two step decomposition and how these characteristics control the regimes in fire behaviour. We demonstrate that the different burning regimes are controlled by different pyrolysis products and effective heat of combustions. The resulting formation of pool fires as well as the formation of dripping is discussed in detail. The latter quite important to understand the flame retardancy applied with respect to achieve the UL 94 classification V0 nondripping or V0 non-flaming dripping. Rigid and flexible PUR foams and their flame retarded versions are investigated for different densities. Water and pentane-blown foams are compared as well as PUR and polyisocyanurate-polyurethane (PIR) foams. Horizontal testing in the cone calorimeter is used and the vertical foam specimen holder as well. Self-designed set-ups within the cone calorimeter enable a better inside in the pyrolysis front running through the foam samples as well as the development of the temperature gradient inside the foam during the fire test. The morphology change during burning was characterised by the means of quenching burning foams with liquid nitrogen and investigating the cross sections with scanning electron microscope. In sum, a rather comprehensive study was performed to work out the principle fire phenomena controlling the fire behaviour of PUR foams in a very systematic and significant way. Promising flame retardancy approaches are discussed. The importance of either combining the drain of fuel and flame inhibition or charring into an effective protection layer/multicellular structure is underlined. This contribution focusses the general conclusions and trends. It tries to increase the understanding of the specific and demanding challenge to develop flame retardant PUR materials. T2 - Interflam 2019, 15th International Interflam Conference CY - Egham, UK DA - 01.07.2019 KW - Polyurethane KW - Flame retardant KW - Dripping KW - Flammability KW - Pool fire KW - Pyrolysis KW - Decomposition KW - Foams PY - 2019 AN - OPUS4-48557 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schartel, Bernhard T1 - Understanding flame retardant modes of action: a wellspring for evidence-based development N2 - 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 T2 - FRPM 2019, 17th European Meeting on Fire Retardant Polymeric Materials CY - Turku, Finland DA - 26.06.2019 KW - Flame retardant KW - Modes of action KW - Fire behaviour PY - 2019 AN - OPUS4-48551 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Lenz, J. A1 - Pospiech, D. A1 - Paven, M. A1 - Albach, R. W. A1 - Günther, Martin A1 - Schartel, Bernhard A1 - Voit, B. T1 - Improving the Flame Retardance of Polyisocyanurate Foams by Dibenzo[d,f][1,3,2]dioxaphosphepine 6-Oxide-Containing Additives N2 - A series of new flame retardants (FR) based on dibenzo[d,f][1,3,2]dioxaphosphepine 6-oxide (BPPO) incorporating acrylates and benzoquinone were developed previously. In this study, we examine the fire behavior of the new flame retardants in polyisocyanurate (PIR) foams. The foam characteristics, thermal decomposition, and fire behavior are investigated. The fire properties of the foams containing BPPO-based derivatives were found to depend on the chemical structure of the substituents. We also compare our results to state-of-the-art non-halogenated FR such as triphenylphosphate and chemically similar phosphinate, i.e. 9,10-dihydro-9-oxa-10- phosphaphenanthrene-10-oxide (DOPO), based derivatives to discuss the role of the phosphorus oxidation state. KW - Polyisocyanurate KW - Dibenzo[d,f][1,3,2]dioxaphosphepine 6-oxide KW - Phospha-Michael addition KW - Flame retardant KW - Foams PY - 2019 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-485590 DO - https://doi.org/10.3390/polym11081242 SN - 2073-4360 VL - 11 IS - 8 SP - Article 1242 PB - MDPI AN - OPUS4-48559 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Battig, Alexander A1 - Markwart, J. C. A1 - Wurm, F. R. A1 - Schartel, Bernhard T1 - Hyperbranched phosphorus flame retardants: multifunctional additives for epoxy resins N2 - We successfully synthesized multifunctional P-based hyperbranched polymeric flame retardants (hb-FRs) with varying oxygen-to-nitrogen (O : N) content and characterized them via 1H and 31P NMR and GPC. Their miscibility in epoxy resins (EP) and impact on glass-transition temperatures (Tg) were determined via differential scanning calorimetry (DSC). Using thermogravimetric and evolved gas Analysis (TGA, TG-FTIR), pyrolysis gas chromatography/mass spectrometry (Py-GC-MS), hot stage FTIR, flammability tests UL-94 and LOI, fire testing via cone calorimetry, residue analysis via scanning electron microscopy (SEM) and elemental analysis, detailed decomposition mechanisms and modes of action are proposed. hb-polymeric FRs have improved miscibility and thermal stability, leading to high FR performance even at low loadings. Polymeric, complex FRs increase flame retardancy, mitigate negative effects of low molecular weight variants, and can compete with commercial aromatic FRs. The results illustrate the role played by the chemical structure in flame retardancy and highlight the potential of hb-FRs as multifunctional additives. KW - Flame retardant KW - Hyperbranched PY - 2019 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-486589 DO - https://doi.org/10.1039/c9py00737g SN - 1759-9962 SN - 1759-9954 VL - 10 IS - 31 SP - 4346 EP - 4358 PB - RSC AN - OPUS4-48658 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wagner, Jan A1 - Häfner, P. A1 - Reimann, H.-A. A1 - Schartel, Bernhard T1 - Valorization of Natural Fibers in Flame Retarded Poly(lactic acid) N2 - Extensive research has explored natural fiber reinforced composites, typically focusing on a single fiber within a polymer matrix. Comprehensive comparisons across different natural fibers in the same polymer, which are critical for industrial material selection, remain limited. This work presents a systematic comparison of untreated hemp, flax, and sisal fibers incorporated at varying fiber lengths and loadings into flame retarded poly(lactic acid) (PLA). Fire behavior, thermal, and mechanical responses were investigated through thermogravimetry, UL 94, and cone calorimetry, alongside crystallinity, molecular weight (MW), and microstructural analysis. Fiber incorporation reduced the peak heat release rate (pHRR) by up to 30 % in 30 wt% hemp, attributed to protective layer formation, but increased flammability in UL 94. A phytic acid melamine salt combined with expandable graphite and 20 wt% hemp produced incomplete combustion at 50 kW/m², raising char residue from 4 to 24 wt% and halving pHRR. Petrella plots revealed that fiber addition alone lowered fire load and flashover propensity as effectively as phytic acid melamine; with hemp, phytic acid and expendable graphite, the flashover hazard and fire load were halved. MW was preserved while crystallinity and modulus increased with fiber content. Hemp delivered the most consistent reinforcement, while optimized processing enabled flax and sisal to improve stiffness. Performance gains were strongest when individual fibers were dispersed via optimized processing, preventing bundle fracture under load. Plasma modification of the fibers improved the maximum tensile strength in the composites. A practical guide is provided for valorizing natural fibers in PLA composites, demonstrating routes to bio-based, compostable materials with improved fire safety and mechanical performance suitable for industrial processing. KW - Poly(lactic acid) KW - Hemp KW - Sisal KW - Flax KW - Flame retardant KW - Phytic acid PY - 2026 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-653038 DO - https://doi.org/10.1016/j.mtcomm.2025.114575 SN - 2352-4928 VL - 50 SP - 1 EP - 41 PB - Elsevier Ltd. AN - OPUS4-65303 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dittrich, Bettina A1 - Wartig, K.-A. A1 - Mülhaupt, R. A1 - Schartel, Bernhard T1 - Flame-retardancy properties of intumescent ammonium poly(phosphate) and mineral filler magnesium hydroxide in combination with graphene N2 - Thermally reduced graphite oxide (TRGO), containing only four single carbon layers on average, was combined with ammonium polyphosphate (APP) and magnesium hydroxide (MH), respectively, in polypropylene (PP). The nanoparticle's influence on different flame-retarding systems and possible synergisms in pyrolysis, reaction to small flame, fire behavior and mechanical properties were determined. TRGO has a positive effect on the yield stress, which is decreased by both flame-retardants and acts as a synergist with regard to Young's modulus. The applicability and effects of TRGO as an adjuvant in combination with conventional flame-retardants depends strongly on the particular flame-retardancy mechanism. In the intumescent system, even small concentrations of TRGO change the viscosity of the pyrolysing melt crucially. In case of oxygen index (OI) and UL 94 test, the addition of increasing amounts of TRGO to PP/APP had a negative impact on the oxygen index and the UL 94 classification. Nevertheless, systems with only low amounts (≤1 wt%) of TRGO achieved V-0 classification in the UL 94 test and high oxygen indices (>31 vol%). TRGO strengthens the residue structure of MH and therefore functions as a strong synergist in terms of OI and UL 94 classification (from HB to V-0). KW - Graphene KW - Intumescence KW - Ammonium polyphosphate KW - Magnesium hydroxide KW - Synergy KW - Polypropylene PY - 2014 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-320685 DO - https://doi.org/10.3390/polym6112875 SN - 2073-4360 VL - 6 IS - 11 SP - 2875 EP - 2895 PB - MDPI CY - Basel AN - OPUS4-32068 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rabe, Sebastian A1 - Chuenban, Yuttapong A1 - Schartel, Bernhard T1 - Exploring the Modes of Action of Phosphorus-Based Flame Retardants in Polymeric Systems N2 - 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. KW - Flame retardants KW - Flame inhibition KW - Cone calorimeter KW - Aluminum diethyl phosphinate KW - Polyester KW - PMMA KW - Epoxy resin KW - Red phosphorus KW - BDP PY - 2017 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-402731 DO - https://doi.org/10.3390/ma10050455 SN - 1996-1944 VL - 10 IS - 5 SP - 455, 1 EP - 455, 23 PB - MDPI AN - OPUS4-40273 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Matzen, Melissa A1 - Kandola, B. A1 - Huth, Christian A1 - Schartel, Bernhard T1 - Influence of flame retardants on the melt dripping behaviour of thermoplastic polymers N2 - Melt flow and dripping of the pyrolysing polymer melt can be both a benefit and a detriment during a fire. In several small-scale fire tests addressing the ignition of a defined specimen with a small ignition source, well-adjusted melt flow and dripping are usually beneficial to pass the test. The presence of flame retardants often changes the melt viscosity crucially. The influence of certain flame retardants on the dripping behaviour of four commercial polymers, poly(butylene terephthalate) (PBT), polypropylene (PP), polypropylene modified with ethylene-propylene rubber (PP-EP) and polyamide 6 (PA 6), is analysed based on an experimental monitoring of the mass loss due to melt dripping, drop size and drop temperature as a function of the furnace temperature applied to a rod-shaped specimen. Investigating the thermal transition (DSC), thermal and thermo-oxidative decomposition, as well as the viscosity of the polymer and collected drops completes the investigation. Different mechanisms of the flame retardants are associated with their influence on the dripping behaviour in the UL 94 test. Reduction in decomposition temperature and changed viscosity play a major role. A flow limit in flame-retarded PBT, enhanced decomposition of flame-retarded PP and PP-EP and the promotion of dripping in PA 6 are the salient features discussed. KW - Fire retardant KW - Viscosity KW - Melt dripping KW - Reaction-to-small-flame KW - UL 94 PY - 2015 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-338941 DO - https://doi.org/10.3390/ma8095267 SN - 1996-1944 VL - 8 IS - 9 SP - 5621 EP - 5646 PB - MDPI CY - Basel AN - OPUS4-33894 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Tang, S. A1 - Wachtendorf, Volker A1 - Klack, Patrick A1 - Qian, Lijun A1 - Dong, Y. A1 - Schartel, Bernhard T1 - Enhanced flame-retardant effect of montmorillonite/phosphaphenanthrene compound in an epoxy thermoset N2 - 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 KW - Flame retardant KW - Nanocomposite KW - DOPO KW - Thermoset KW - Epoxy resin KW - TG-FTIR PY - 2017 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-388865 DO - https://doi.org/10.1039/c6ra25070j SN - 2046-2069 VL - 7 IS - 2 SP - 720 EP - 728 AN - OPUS4-38886 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Daus, Lars-Hendrik A1 - Korzen, Manfred A1 - Schartel, Bernhard T1 - High-throughput fire tests and weathering-induced degradation behaviour of intumescent coatings N2 - In this work, the weathering-induced degradation of intumescent coatings was investigated by a systematic and comprehensive approach. A mechanism is revealed that is proposed to be responsible for the loss of function of intumescent coatings induced by weathering. First, the thermal decomposition of artificially weathered intumescent coatings was examined. To get a better understanding of the weathering and ageing phenomena, the degradation behaviour of the single ingredients during the weathering process was investigated, as well as their chemical and physical interactions. For the systematic approach, the materials that are essential for intumescence (ammonium polyphosphate, pentaerythritol, titanium dioxide, melamine and the binder) are treated with moisture, elevated temperature and UV radiation. Thermogravimetry (TG) and IR spectroscopy were used to compare the initial samples with their different grades of weathering. We demonstrate that ammonium polyphosphate, melamine and the binder are mainly responsible for the ageing process. Further, it was demonstrated that TG and IR spectroscopy are suitable measuring methods to detect the effects of weathering on intumescent coatings. Finally, a small-scale fire test procedure is introduced. Based on the reduction of the sample size, up to 50 samples can be tested in a single fire test. The results of this fire test have the same quality as the results from standard intermediate fire tests corresponding to DIN 4102-8. T2 - 3rd European Symposium on Fire Safety Science CY - Nancy, France DA - 12.09.1018 KW - Weathering KW - Intumescent coatings KW - High-Throughput Fire Tests PY - 2018 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-472023 UR - http://iopscience.iop.org/article/10.1088/1742-6596/1107/3/032014/pdf DO - https://doi.org/10.1088/1742-6596/1107/3/032014 VL - 1107 SP - 032014 PB - IOP Publishing CY - Bristol AN - OPUS4-47202 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dudziak, Mateusz A1 - Dural, Esra A1 - Dey, R. A1 - Ullrich, M. S. A1 - Huth, Christian A1 - Thomson, C. A1 - Schartel, Bernhard T1 - Together We Can: Synergistic Flame Retardancy by Melamine Polyphosphate and Phosphorylated Microalgae in Polylactide Biocomposites N2 - A strategy for enhancing the sustainable flame retardancy of polylactide (PLA) composites by partially replacing melamine polyphosphate (MPP), a commercial flame retardant proposed for PLA, with wastewater polyphosphate-enriched microalgae (P-Algae) has been explored. The incorporation of P-Algae at a 1:1 ratio with MPP leads to a notable synergistic effect, surpassing the expected additive behavior of the individual components. Comprehensive characterization encompassing thermogravimetric analysis coupled with FTIR, pyrolysis combustion flow calorimeter (PCFC), cone calorimeter, oxygen index (LOI), UL-94 tests, and rheological measurements—demonstrates that the presence of this biomaterial can significantly enhance flame retardant performance. Replacing 50% of MPP with P-Algae in PLA resulted in a 17% reduction in peak heat release rate (pHRR) and maintained a V-0 rating in UL-94 testing. The use of P-Algae does not compromise the flame retardancy of PLA but rather contributes positively, offering a promising path toward more sustainable flame-retardant systems. By leveraging naturally derived biomass, this approach aligns with the growing demand for novel eco-friendly technologies in polymer engineering. Insights into an innovative renewable additive as a functional and effective component in flame-retardant biocomposites have been achieved. KW - Flame retardancy KW - Melamine polyphosphate KW - Phosphorus- enriched microalgae KW - Polylactide PLA KW - Synergism PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-640539 DO - https://doi.org/10.1002/pat.70350 SN - 1099-1581 SN - 1042-7147 VL - 36 IS - 9 SP - e70350 PB - John Wiley & Sons Ltd. AN - OPUS4-64053 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Watolla, Marie-Bernadette A1 - Gluth, Gregor A1 - Sturm, Patrick A1 - Rickard, W.D.A. A1 - Krüger, Simone A1 - Schartel, Bernhard T1 - Intumescent geopolymer-bound coatings for fire protection of steel N2 - The passive fire protection of steel structures and other load-bearing components will continue to gain importance in future years. In the present contribution, novel intumescent aluminosilicate (geopolymer-bound) composites are proposed as fire-protective coatings on steel. Steel plates coated with these materials were exposed to the standard temperature-time curve as defined in ISO 834 – 1:1999. The coatings partially foamed during curing and expanded further during thermal exposure, demonstrating their intumescent characteristic.Thermogravimetryandoscillatory rheometry determined that the intumescent behavior is attributed to a transition to a viscous state (loss factor > 1) in the temperature range of major water release, differing from conventional geopolymers. XRD and SEM images showed that the coatings had characteristics of ceramic or glass-ceramic foams after fire resistance testing, suggesting superior performance under challenging conditions. The thickness of the coatings influenced their foaming and intumescent behavior and thus the time for the coated steel plates to reach 500 °C. A number of additives were also studied with the best performance obtained from samples containing sodium tetraborate.Acoating of just 6mmwas able to delay the time it takes for a steel substrate to reach 500 °C to more than 30 minutes. KW - Geopolymers KW - Fire protection KW - Intumescence KW - Coatings KW - Fire resistance PY - 2017 UR - https://www.ceramic-science.com/articles/all-articles.html?article_id=100558 DO - https://doi.org/10.4416/JCST2017-00035 VL - 8 IS - 3 (Topical issue: Geopolymers) SP - 351 EP - 364 PB - Göller Verlag CY - Baden-Baden AN - OPUS4-42139 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -