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 - Chan, Yin Yam A1 - Ma, C. A1 - Zhou, F. A1 - Hu, Y. A1 - Schartel, Bernhard T1 - A liquid phosphorous flame retardant combined with expandable graphite or melamine in flexible polyurethane foam N2 - A systematic series of flexible polyurethane foams (FPUF) with different concentrations of flame retardants, bis([dimethoxyphosphoryl]methyl) phenyl phosphate (BDMPP), and melamine (MA) or expandable graphite (EG) was prepared. The mechanical properties of the FPUFs were evaluated by a universal testing machine. The pyrolysis behaviors and the evolved gas analysis were done by thermogravimetric analysis (TGA) and TGA coupled with Fourier-transform infrared (TG-FTIR), respectively. The fire behaviors were studied by limiting oxygen index (LOI), UL 94 test for horizontal burning of cellular materials (UL 94 HBF), and cone calorimeter measurement. Scanning electronic microscopy (SEM) was used to examine the cellular structure's morphology and the postfire char residue of the FPUFs. LOI and UL 94 HBF tests of all the flame retarded samples show improved flame retardancy. BDMPP plays an essential role in the gas phase because it significantly reduces the effective heat of combustion (EHC). This study highlights the synergistic effect caused by the combination of BDMPP and EG. The measured char yield from TGA is greater than the sum of individual effects. No dripping phenomenon occurs during burning for FPUF-BDMPP-EGs, as demonstrated by the result of the UL 94 HBF test. EG performs excellently on smoke suppression during burning, as evident in the result of the cone calorimeter test. MA reduces the peak heat release rate (pHRR) significantly. The synergistic effect of the combination of BDMPP and EG as well as MA offers an approach to enhance flame retardancy and smoke suppression. KW - Bis([dimethoxyphosphoryl]methyl) phenyl phosphate KW - Expandable graphite KW - Flexible polyurethane foam KW - melamine KW - phosphorous flame retardant PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-541840 DO - https://doi.org/10.1002/pat.5519 SN - 1099-1581 VL - 33 IS - 1 SP - 326 EP - 339 PB - Wiley AN - OPUS4-54184 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Marti, J. A1 - Schartel, Bernhard A1 - Oñate, E. T1 - Simulation of the burning and dripping cables in fire using the particle finite element method N2 - The behavior of the cable jacket in fire characterized by the tendency to melt and drip constitutes a major source of fire hazard. The reason is that the melted material may convey the flame from one point to another, expanding fire and contributing to the fire load. In this article, the capability of a new computational strategy based on the particle finite element method for simulating a bench-scale cables burning test is analyzed. The use bench-scale test has been previously used to simulate the full-scale test described in EN 50399. As the air effect is neglected, a simple combustion model is included. The samples selected are two cables consisting of a copper core and differently flame retarded thermoplastic polyurethane sheets. The key modeling parameters were determined from different literature sources as well as experimentally. During the experiment, the specimen was burned under the test set-up condition recording the process and measuring the temperature evolution by means of three thermocouples. Next, the test was reproduced numerically and compared with a real fire test. The numerical results show that the particle finite element method can accurately predict the evolution of the temperature and the melting of the jacket. KW - Dripping behavior KW - Particle finite element method KW - Cables in fire KW - Fire behavior KW - Fire simulation KW - Cable bundle PY - 2022 DO - https://doi.org/10.1177/07349041211039752 SN - 0734-9041 VL - 40 IS - 1 SP - 3 EP - 25 PB - Sage AN - OPUS4-54185 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Tan, Yi A1 - Wachtendorf, Volker A1 - Kukofka, Tobias A1 - Klack, Patrick A1 - Ruder, J. A1 - Lin, Xuebao A1 - Schartel, Bernhard T1 - Degradation of flame retardance: A comparison of ethylene‐vinyl acetate and low‐density polyethylene cables with two different metal hydroxides N2 - The durability of flame retardancy is a challenge for cables over long lifetimes. The degradation of flame retardance is investigated in two kinds of exposures, artificial weathering and humidity. In this basic study, typical mineral flame retardants in two polymers frequently used in cable jackets are investigated to get the fundamental picture. Aluminum hydroxide (ATH) and magnesium hydroxide (MDH) are compared in ethylene‐vinyl acetate (EVA), and further in EVA and linear low‐density polyethylene (LLDPE) cables containing the same ATH. The changes in chemical structure at the surface are studied through attenuated total reflectance Fourier transform infrared spectroscopy (ATR‐FTIR), the formation of cracks, and changes in color are investigated. The cone calorimeter and a bench scale fire testing cable module are utilized to evaluate the fire behavior of the cables. Although the flame retardancy deteriorated slightly, it survived harsh exposure conditions for 2000 h. Compared to EVA/MDH and LLDPE/ATH, the fire behavior of EVA/ATH is the least sensitive. Taken together, all of the results converge to estimate that there will be no problem with flame retardancy performance, for materials subjected to natural exposure for several years; the durability of fire retardancy is questionable for longer periods, and thus requires further investigation. KW - Durability KW - Flame retardant KW - Aluminum hydroxide (ATH) KW - Magnesium hydroxide KW - Ethylene-vinyl acetate KW - Cables KW - Weathering PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-519573 DO - https://doi.org/10.1002/app.50149 VL - 138 IS - 14 SP - 50149 PB - Wiley AN - OPUS4-51957 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Daus, Lars-Hendrik A1 - Schartel, Bernhard A1 - Wachtendorf, Volker A1 - Mangelsdorf, R. A1 - Korzen, Manfred T1 - A chain is no stronger than its weakest link: Weathering resistance of water-based intumescent coatings for steel applications N2 - A systematic approach was used to investigate the weathering-induced degradation of a common water–based intumescent coating. In this study, the coatings are intended for humid indoor applications on steel substrates. The coating contains ammonium polyphosphate, pentaerythritol, melamine, and polyvinyl acetate. By replacing each ingredient with a less water-soluble substance, the most vulnerable substances, polyvinyl acetate and pentaerythritol, were identified. Furthermore, the weathering resistance of the system was improved by exchanging the ingredients. The coatings were stressed by artificial weathering tests and evaluated by fire tests. Thermogravimetry and Fourier-transform infrared spectroscopy were used to study the thermal decomposition. This study lays the foundation for the development of a new generation of water-based intumescent coatings. KW - Intumescence KW - Fire resistance KW - Fire protective coatings KW - Weathering KW - Thermogravimetric analyses PY - 2021 DO - https://doi.org/10.1177/0734904120961064 SN - 0734-9041 SN - 1530-8049 VL - 39 IS - 1 SP - 72 EP - 102 PB - SAGE AN - OPUS4-52015 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Günther, Martin A1 - Lorenzetti, A. A1 - Schartel, Bernhard T1 - Fire Phenomena of Rigid Polyurethane Foams N2 - Rigid polyurethane foams (RPUFs) typically exhibit low thermal inertia, resulting in short ignition times and rapid flame spread. In this study, the fire phenomena of RPUFs were investigated using a multi-methodological approach to gain detailed insight into the fire behaviour of pentaneand water-blown polyurethane (PUR) as well as pentane-blown polyisocyanurate Polyurethane (PIR) foams with densities ranging from 30 to 100 kg/m3. Thermophysical properties were studied using thermogravimetry (TG); flammability and fire behaviour were investigated by means of the limiting oxygen index (LOI) and a cone calorimeter. Temperature development in burning cone calorimeter specimens was monitored with thermocouples inside the foam samples and visual investigation of quenched specimens’ cross sections gave insight into the morphological changes during burning. A comprehensive investigation is presented, illuminating the processes taking place during foam combustion. Cone calorimeter tests revealed that in-depth absorption of radiation is a significant factor in estimating the time to ignition. Cross sections examined with an electron scanning microscope (SEM) revealed a pyrolysis front with an intact foam structure underneath, and temperature measurement inside burning specimens indicated that, as foam density increased, their burning behaviour shifted towards that of solid materials. The superior fire performance of PIR foams was found to be based on the cellular structure, which is retained in the residue to some extent. KW - Foam KW - Polyurethane KW - Fire behaviour KW - Flammability PY - 2018 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-465577 DO - https://doi.org/10.3390/polym10101166 SN - 2073-4360 VL - 10 IS - 10 SP - 1166-1 EP - 1166-22 PB - MDPI AN - OPUS4-46557 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 - 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 - 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 - 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 - 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 - 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 - 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 - 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 - 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 - 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 - Hupp, Vitus A1 - Schartel, Bernhard A1 - Flothmeier, K. A1 - Hartwig, A. T1 - Pyrolysis and flammability of phosphorus based flame retardant pressure sensitive adhesives and adhesive tapes N2 - Pressure-sensitive adhesive tapes are used in a variety of applications such as construction, aircrafts, railway vehicles, and ships, where flame retardancy is essential. Especially in these applications, phosphorus-based flame retardants are often chosen over halogenated ones due to their advantages in terms of toxicity. Although there are pressure-sensitive adhesives with phosphorus flame retardants available on the market, their flame-retardant modes of action and mechanisms are not entirely understood. This research article provides fundamental pyrolysis research of three phosphorus-based flame retardants that exhibit different mechanisms in a pressuresensitive adhesive matrix. The flame-retardants modes of action and mechanisms of a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) derivate, an aryl phosphate, and a self-synthesized, covalently bonded DOPO derivate (copolymerized) are investigated. The blended DOPO derivate is volatilized at rather low temperatures while the covalently bonded DOPO derivate decomposes together with the polymer matrix at the same temperature. Both DOPO derivates release PO radicals which are known for their flame inhibition. The aryl phosphate decomposes at higher temperatures, releases small amounts of aryl phosphates into the gas phase, and acts predominantly the condensed phase. The aryl phosphate acts as precursor for phosphoric acid and improves the charring of the pressure sensitive adhesive matrix. All flame retardants enhance the flammability of the adhesives depending on their individual mode of action while the covalently bonded flame retardant additionally improves the mechanical properties at elevated temperatures making it a promising future technology for pressure-sensitive adhesives. KW - Pyrolysis of flame retardant KW - Pyrolysis gas chromatography KW - Mass spectrometry KW - Phosphorus flame retardant KW - Decomposition mechanism KW - Flame retardant pressure sensitive adhesives KW - Flame retardancy PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-607192 DO - https://doi.org/10.1016/j.jaap.2024.106658 SN - 0165-2370 SN - 1873-250X VL - 181 SP - 1 EP - 31 PB - Elsevier B.V. AN - OPUS4-60719 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -