TY - JOUR A1 - Sut, Aleksandra A1 - Greiser, Sebastian A1 - Jäger, Christian A1 - Schartel, Bernhard T1 - Synergy in flame-retarded epoxy resin - Identification of chemical interactions by solid-state NMR N2 - The potential synergists aluminium diethylphosphinate (AlPi), boehmite (AlO(OH)) and melamine polyphosphate (MPP) were compared in flame-retardant epoxy resin (EP)/melamine poly(magnesium phosphate) (S600). The pyrolysis, the fire behaviour as well as the chemical interactions in the gas and condensed phases were investigated by various methods. Flammability was investigated by cone calorimeter and oxygen index (OI). The thermal and thermo-oxidative decomposition were studied by thermogravimetric analysis coupled with FTIR spectrometer. The special focus was on the Investigation of structural changes in the condensed phase via solid-state NMR of 27Al and 31P nuclei. By the comparison of epoxy resin with only one additive or with S600 in combination with AlPi, AlO(OH) or MPP, it was possible to calculate the synergy index. The best performance in terms of fire behaviour was observed for EP/S600/MPP with a PHRR (Peak heat release rate) of 208 kW m-2 due to slight synergy. In the case of THE (total heat evolved), clear synergy occurred for EP/S600/AlPi and EP/S600/AlO(OH). By solid-state NMR, different phosphates and aluminates were identified, indicating the chemical interactions between S600 and AlPi, AlO(OH) or MPP. The systematic multi-methodical approach yielded insight into the synergistic effects in the flame-retarded epoxy resin. KW - Synergy KW - Epoxy resin KW - Flame retardancy KW - Melamine poly(magnesium phosphate) KW - Solid-state NMR PY - 2017 DO - https://doi.org/10.1007/s10973-016-5934-4 SN - 1388-6150 SN - 1588-2926 VL - 128 IS - 1 SP - 141 EP - 153 PB - Springer AN - OPUS4-39298 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Sut, Aleksandra A1 - Greiser, Sebastian A1 - Jäger, Christian A1 - Schartel, Bernhard T1 - Synergy in flame retardant polymers: solid-state NMR identifying the chemistry behind it T2 - MoDeSt 2014 CY - Portorož, Slovenia DA - 2014-08-31 PY - 2014 AN - OPUS4-31413 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Sut, Aleksandra A1 - Greiser, Sebastian A1 - Jäger, Christian A1 - Schartel, Bernhard T1 - Solid-state NMR Identifying the Interactions in Flame Retardant Formulations T2 - 36th Discussion Meeting of the GDCh-Division of "Magnetic Resonance" CY - Berlin, Germany DA - 2014-09-29 PY - 2014 AN - OPUS4-32356 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Müller, Patrick A1 - Morys, Michael A1 - Sut, Aleksandra A1 - Jäger, Christian A1 - Illerhaus, Bernhard A1 - Schartel, Bernhard T1 - Melamine poly(zinc phosphate) as flame retardant in epoxy resin: Decomposition pathways, molecular mechanisms and morphology of fire residues N2 - Synergistic multicomponent systems containing melamine poly(metal phosphate)s have been recently proposed as flame retardants. This work focuses on the decomposition pathways, molecular mechanisms and morphology of the fire residues of epoxy resin (EP) flame retarded with melamine poly(zinc phosphate) (MPZnP) to explain the modes of action and synergistic effects with selected synergists (melamine polyphosphate (MPP) and AlO(OH), respectively). The total load of flame retardants was always 20 wt.%. The decomposition pathways were investigated in detail via thermogravimetric Analysis coupled with Fourier transform infrared spectroscopy. The fire residues were investigated via elemental analysis und solid-state nuclear magnetic resonance spectroscopy. The morphology of intumescent fire residues was investigated via micro-computed tomography and scanning electron microscopy. EP + (MPZnP + MPP) formed a highly voluminous residue that showed structural features of both EP + MPZnP and EP + MPP, resulting in a highly effective protection layer. EP + (MPZnP + AlO(OH)) preserved the entire quantity of phosphorus content during combustion due to the Formation of Zn₂P₂O₇ and AlPO₄. KW - Melamine poly(metal phosphate) KW - Flame retardancy KW - Epoxy resin KW - Solid-state NMR KW - Micro-computed tomography KW - Fire residue PY - 2016 DO - https://doi.org/10.1016/j.polymdegradstab.2016.06.023 SN - 0141-3910 VL - 130 SP - 307 EP - 319 PB - Elsevier AN - OPUS4-36863 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Langfeld, Kirsten A1 - Wilke, Antje A1 - Sut, Aleksandra A1 - Greiser, Sebastian A1 - Ulmer, B. A1 - Andrievici, V. A1 - Limbach, P. A1 - Bastian, Martin A1 - Schartel, Bernhard T1 - Halogen-free fire retardant styrene-ethylene-butylene-styrene-based thermoplastic elastomers using synergistic aluminium diethylphosphinate-based combinations N2 - Multicomponent flame retardant systems containing aluminum diethylphosphinate in thermoplastic styrene–ethylene–butylene–styrene elastomers are investigated (oxygen index, UL 94, cone calorimeter, and mechanical testing). Solid-state nuclear magnetic resonance, scanning electron microscopy, and elemental analysis illuminate the interactions in the condensed phase. Thermoplastic styrene–ethylene–butylene–styrene elastomers are a challenge for flame retardancy (peak heat release rate at 50 kW m-2 > 2000 kW m-2, oxygen index = 17.2 vol%, no UL-94 horizontal burn rating) since it burns without residue and with a very high effective heat of combustion. Adding aluminum diethylphosphinate results in efficient flame inhibition and improves the reaction to small flame, but it is less effective in the cone calorimeter. Its efficacy levels off for amounts >~25 wt%. As the most promising synergistic system, aluminum diethylphosphinate/melamine polyphosphate was identified, combining the main gas action of aluminum diethylphosphinate with condensed phase mechanisms. The protection layer was further improved with several adjuvants. Keeping the overall flame retardant content at 30 wt%, aluminum diethylphosphinate/melamine polyphosphate/titanium dioxide and aluminum diethylphosphinate/melamine polyphosphate/boehmite were the best approaches. An oxygen index of up to 27 vol% was achieved and a horizontal burn rating in UL 94 with immediate self-extinction; peak heat release rate decreased by up to 85% compared to thermoplastic styrene–ethylene–butylene–styrene elastomers, to <300 kW m-2. KW - Flame retardancy KW - Aluminium phosphinate KW - Thermoplastic elastomers KW - Cone calorimetry KW - Flammability PY - 2015 DO - https://doi.org/10.1177/0734904114565581 SN - 0734-9041 SN - 1530-8049 VL - 33 IS - 2 SP - 157 EP - 177 PB - Sage CY - London AN - OPUS4-32692 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Sut, Aleksandra A1 - Müller, Patrick A1 - Greiser, Sebastian A1 - Jäger, Christian A1 - Schartel, Bernhard T1 - Advanced analysis of flame retarded epoxy resin/melamine poly(metal phosphate)/synergist systems N2 - Synergistic multicomponent systems containing melamine poly(metal phosphate) have been proposed as flame retardants. The potential synergists: aluminium diethylphosphinate (AlPi), boehmite (AlO(OH)) and melamine polyphosphate (MPP) were compared in flame retardant epoxy resin (EP)/melamine poly(magnesium phosphate) (MMgP) and EP/melamine poly(zinc phosphate) (MZnP). A multi-methodical approach was used to investigate the pyrolysis, fire residues, flame retardant modes of action, and synergistic effects. The decomposition and the fuel released into the gas phase were investigated by thermogravimetry coupled with Fourier transform infrared spectroscopy (TG-FTIR). A detailed analysis of the condensed phase was done by FTIR and comprehensive solid-state nuclear magnetic resonance spectroscopy (NMR). The fire behaviour was investigated by the cone calorimeter and the morphology of the fire residues with micro-computed tomography (µCT) and scanning electron microscopy (SEM). The best performance is observed for EP/MMgP/MPP and EP/MZnP/MPP based on a synergistic effect between the flame retardants. Particular the formation of a highly voluminous fire residue plays a major role and is stabilized by the interaction between the flame retardants. As a result highly effective protection layer was formed which led to the interesting results. T2 - Recent Advances in Flame Retardancy of Polymeric Materials, Flame 2017 CY - Boston, MA, USA DA - 11.06.2017 KW - Flame retardant KW - Solid state NMR KW - Melamine poly(metal phosphate) KW - Synergist KW - TG-FTIR PY - 2017 AN - OPUS4-40768 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Sut, Aleksandra A1 - Greiser, Sebastian A1 - Jäger, Christian A1 - Schartel, Bernhard T1 - Solid-state NMR Identifying the Chemistry in Multicomponent Flame-retarded Polyolefin Systems N2 - Understanding of the interaction in multicomponent flame-retarded polymeric system is crucial to obtain the best performance at the possible lowest load of additives. In this work, polyolefine based systems are investigated by solid state NMR and cone calorimetry. As a polymer matrix thermoplastic elastomer based on styrene (TPE-S) was chosen. Different combination of additives was investigated in order to identify the chemistry occurring during the pyrolysis. As additives aluminium diethylphosphinate (AlPi), ammonium polyphosphate, zinc borate (ZB), poly(phenylene oxide) (PPO), magnesium hydroxide (MH) and dimethyl- methylvinyl siloxane (Si) were used. Fire residues remained after the cone calorimeter test were analyzed by solid state NMR (31P, 27Al, 13C, 11B, 29Si). The formation of different phosphates and aluminates was identified, indicating the chemical interaction between the additives. Detailed investigation delivered meaningful insights into the chemistry controlling flame retardancy. T2 - Recent Advances in Flame Retardancy of Polymeric Materials, Flame 2017 CY - Boston, MA, USA DA - 11.06.2017 KW - Solid-state NMR KW - Flame retardancy KW - Cone calorimeter KW - Aluminium diethylphosphinate KW - Zinc borate KW - Multicomponent systems PY - 2017 AN - OPUS4-40769 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Sut, Aleksandra A1 - Metzsch-Zilligen, E. A1 - Großhauser, M. A1 - Pfaendner, R. A1 - Schartel, Bernhard T1 - Thermoplastic polyurethane - How thespecific two-stage decompositioncontrols its fire behavior N2 - Thermoplastic polyurethanes (TPUs) are one of the major classes of thermoplastic elastomers used in the cable and wire industry. Due to their chemical structure, they are considered as linear block copolymers with alternating hard and soft segments. This specific structure is not only responsible for the excellent mechanical properties of TPU like high tensile strength or abrasion resistance, but it also influences the pyrolysis and burning behavior. TPU is a highly flammable polymer which forms liquid pool fires or burning drops which results in intensive flame spread. Because of that, TPU often does not meet the strict requirements for indoor applications given by the cable market. Under thermal stress, TPU decomposes in a specific way. At first, the hard segments decompose and the material becomes soft and melts. Subsequently, pool fires are formed and melted material burns extensively. There are not many works addressing this problem in detail especially in terms of suitable flame retardant solutions. It is crucial to understand at which stage the flame retardants are working and how they affect the thermal decomposition of TPU. Hence, the focus of this work was put on the identification of the reactions occurring during each stage of TPU decomposition and the contribution of released products to the effective heat of combustion (EHC). Moreover, the detailed analysis of the melt dripping behavior was performed to better understand the influence of the decomposition degree on the viscosity. The use of melamine cyanurate (MC) in combination with other additives was reported to be a promising flame retardant solution for TPU, especially in cable jacket applications. Hence, the combinations of MC with various flame retardants were used in TPU (Elastollan® 1185A10) and were investigated in terms of fire behavior, flammability, pyrolysis and decomposition products. As flame retardants, common ones were used including aluminum trihydrate (ATH), melamine polyphosphate (MPP), or aluminum diethylphosphinate (AlPi). Moreover, commercial product TPU-FR (Elastollan® 1185A10FHF) was investigated as a reference. T2 - 10th International Conference on Modification, Degradation and Stabilization of Polymers, MoDeSt2018 CY - Tokyo, Japan DA - 02.09.2018 KW - Thermoplastic polyurethane KW - Decomposition KW - Two-stage burning KW - Effective heat of combustion KW - Pyrolysis KW - Melt dripping KW - Pool fire KW - Melamine cyanurate PY - 2018 AN - OPUS4-45969 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 - Rapid mass calorimeter as a high-throughput screening method for the development of flame-retarded TPU N2 - The rapid mass calorimeter (RMC) was used as a screening tool based on accelerated fire testing to assess flame-retarded thermoplastic polyurethane (TPU). The reliability of RMC results was proven with the cone calorimeter as reference fire test. The influence of melamine cyanurate (MC) concentration on the fire performance of TPU was investigated, along with some flame-retardant combinations such as MC with aluminium diethylphosphinate (AlPi), aluminium trihydrate (ATH), and melamine polyphosphate (MPP). The two-stage burning behaviour of TPU was investigated in detail; the first stage corresponds mainly to the hard segments' decomposition and has a much lower effective heat of combustion (EHC) than the second stage, in which mainly the soft segments decompose and an intensive liquid pool fire is observed in the cone calorimeter set-up. In addition to fire testing with the cone calorimeter, RMC, and UL 94 flammability tests, the decomposition of the materials was investigated using thermogravimetric analysis coupled with infrared spectrometry (TGeFTIR). TPU/MC/AlPi shows the most promising results, achieving V-0 classification in UL 94 and reducing the extreme peak heat release rate (PHRR) of the liquid pool fire from 3154 kW/m2 to 635 kW/m2. Using MC/AlPi/MPP enhances the latter PHRR reduction further. The decomposition products identified in the gas phase via TGeFTIR reveal specific MCeAlPi eMPP interactions, as they differ from products seen in systems with MC/AlPi or MC/MPP. Correlations between RMC and cone calorimeter results were examined and presented in the final part of the paper. Several characteristics correlate strongly, pointing out that RMC is a reliable high-throughput fire testing method to screen multicomponent flame-retardant solutions in TPU. KW - Thermoplastic polyurethane KW - Flame retardancy KW - Rapid mass calorimeter KW - High throughput screening PY - 2018 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-456982 SN - 0141-3910 SN - 1873-2321 VL - 156 SP - 43 EP - 58 PB - Elsevier Ltd. AN - OPUS4-45698 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 - CONF A1 - Sut, Aleksandra A1 - Greiser, Sebastian A1 - Jäger, Christian A1 - Schartel, Bernhard T1 - Solid-state NMR Identifying the Chemistry Behind Synergy in Flame Retardant Polymers T2 - FRPM 2015, 15th European Meeting on Fire Retardancy and Protection of Materials CY - Berlin, Germany DA - 2015-06-22 PY - 2015 AN - OPUS4-33625 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sut, Aleksandra A1 - Greiser, Sebastian A1 - Jäger, Christian A1 - Schartel, Bernhard T1 - Interactions in multicomponent flame-retardant polymers: Solid-state NMR identifying the chemistry behind it N2 - Distinct approaches are used to reduce the fire risks of polymers, a key issue for many industrial applications. Among the variety of approaches, the use of synergy in halogen-free multicomponent systems is one of the most auspicious. To optimize the composition of such flame-retardant systems it is essential to understand the mechanisms and the corresponding chemistry in the condensed phase. In this work different methods are used, including cone calorimeter, thermogravimetry (TG), and TG-FTIR, with the main focus on the solid-state NMR analysis of the solid residues. The structural changes in the condensed phase of two thermoplastic elastomer systems based on copolymer styrene-ethylene-butadiene-styrene (TPE-S) were investigated: TPE-S/aluminium diethylphosphinate (AlPi)/magnesium hydroxide (MH) and TPE-S/AlPi/zinc borate (ZB)/poly(phenylene oxide) (PPO). Strong flame inhibition is synergistically combined with protective layer formation. 13C-, 27Al-, 11B- and 31P MAS NMR (magic angle spinning nuclear magnetic resonance) experiments using direct excitation with a single pulse and 1H–31P cross-polarization (CP) were carried out as well as double resonance techniques. Magnesium phosphates were formed during the pyrolysis of TPE-S/AlPi/MH, while for the system TPE-S/AlPi/ZB/PPO zinc phosphates and borophosphates were observed. Thus, the chemistry behind the chemical interaction was characterized unambiguously for the investigated systems. KW - Synergy KW - Solid-state NMR KW - Flame retardancy KW - SEBS KW - Aluminium diethylphosphinate KW - Magnesium hydroxide KW - Zinc borate KW - Poly(phenylene) oxide PY - 2015 DO - https://doi.org/10.1016/j.polymdegradstab.2015.08.018 SN - 0141-3910 SN - 1873-2321 VL - 121 SP - 116 EP - 125 PB - Applied Science Publ. CY - London AN - OPUS4-34306 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sut, Aleksandra A1 - Greiser, Sebastian A1 - Jäger, Christian A1 - Schartel, Bernhard T1 - Aluminium diethylphosphinate versus ammonium polyphosphate: A comprehensive comparison of the chemical interactions during pyrolysis in flame-retarded polyolefine/poly(phenylene oxide) N2 - A systematic comparison of chemical interactions and fire behaviour is presented for the thermoplas-tic elastomer (block copolymer styrene-ethylene-butadiene-styrene) (TPE-S)/diethyl- and methylvinylsiloxane (Si)/poly(phenylene oxide) (PPO), flame-retarded with aluminium diethylphosphinate (AlPi)and with ammonium polyphosphate (APP), respectively. TPE-S/APP/Si/PPO performed better in the conecalorimeter test (reduction in peak heat release rate from 2042 to 475 kW m−2), but TPE-S/AlPi/Si/PPO inthe flammability tests (oxygen index (OI) and UL 94). This difference was caused by the different modes ofaction of APP (more in the condensed phase) and AlPi (mainly in the gas phase). Thermogravimetry cou-pled with Fourier transform infrared spectroscopy (TG-FTIR) was used to analyse the mass loss and theevolved gas products, while a Linkam hot-stage cell to investigate the decomposition in the condensedphase. Moreover, a detailed analysis of the fire residues was done using solid-state NMR.13C MAS NMRshowed that both flame-retarded compositions form graphite-like amorphous carbonaceous char, orig-inating from PPO.31P MAS NMR and29Si MAS NMR delivered important information about interactionbetween phosphorus and the siloxane. For TPE-S/AlPi/Si/PPO aluminium phosphate and silicon dioxideoccurred, while also silicophosphate was produced in TPE-S/APP/Si/PPO. The direct comparison of two ofthe most prominent halogen-free flame retardants containing phosphorus delivered meaningful insightsinto the modes of action and molecular mechanisms controlling flame retardancy. KW - Aluminium diethylphosphinate KW - Ammonium polyphosphate KW - Flame retardancy KW - Solid-state NMR KW - SEBS PY - 2016 SN - 0040-6031 SN - 1872-762X VL - 640 SP - 74 EP - 84 PB - Elsevier AN - OPUS4-37802 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -