TY - JOUR A1 - Schartel, Bernhard A1 - Günther, Martin T1 - Flame retardancy of polyurethanes N2 - Polyurethanes (PU) represent one of the most versatile classes of plastics. They are processed and used as thermoplastic, elastomer, and thermoset. The requirements regarding flammability are correspondingly versatile. Depending on the material and the field of application, specific fire tests have to be fulfilled. This paper describes the different concepts used to fulfil these requirements by choosing the right raw materials and flame retardants. KW - Polyurethane KW - Flame retardant KW - Foam KW - Flammability KW - Pyrolysis KW - Cone calorimeter PY - 2020 VL - 17 IS - 1 SP - 44 EP - 48 PB - Dr. Gupta AN - OPUS4-50737 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schartel, Bernhard A1 - Perret, Birgit A1 - Dittrich, Bettina A1 - Ciesielski, M. A1 - Krämer, J. A1 - Müller, P. A1 - Altstädt, V. A1 - Zang, L. A1 - Döring, M. T1 - Flame retardancy of polymers: the role of specific reactions in the condensed phase N2 - Condensed-phase mechanisms play a major role in fire-retardant polymers. Generations of development have followed the concept of charring to improve fire properties. Whereas the principal reactions are believed to be known, the specific description for multicomponent systems is lacking, as is the picture across different systems. A two-step approach is proposed in general, and also presented in greater detail. The second step covers the specific reactions controlling charring, whereas the actual reactants are provided in the preceding step. This model consistently incorporates the variety of structure–property relationships reported. A comprehensive case study is presented on seven phosphorus flame retardants in two epoxy resins to breathe life into the two-step approach. KW - Charring KW - Epoxy KW - Flame retardancy KW - Pyrolysis KW - Thermogravimetric analysis (TGA) PY - 2016 DO - https://doi.org/10.1002/mame.201500250 SN - 1438-7492 SN - 1439-2054 VL - 301 IS - 1 SP - 9 EP - 35 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-35273 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CHAP A1 - Schartel, Bernhard ED - Troitzsch, J. ED - Antonatus, E. T1 - The Burning of Plastics N2 - The burning of a polymer is a physico–chemical process strongly influenced by the coupling of a chemical reaction – oxidation of fuel – in the gas phase with a chemical decomposition reaction – pyrolysis – in the condensed phase via heat and mass transfer. The heat and mass flux control the intensity of fire and the ablation of fuel. Indeed, the temperature profile as a function of time may be one of the most important responses of a specimen to understand its burning behavior. Further, several physical phenomena, such as the heat absorption of the materials, thermal conductivity, and also melt flow and dripping, play a major role in determining ignition, flammability, and fire behavior. The burning of a polymer is very complex. The various phenomena interact with each other, e. g., pyrolysis also influences the viscosity of the melt, and, thus, whether dripping or charring results in a protective layer, increasing the shielding effect of the residual protective layer. Only a detailed and comprehensive description opens the door to a well-founded understanding of the burning behavior of polymeric materials. KW - Fire behaviour KW - Plastics KW - Pyrolysis KW - Decomposition KW - Ignition KW - Smoldering KW - Flame spread KW - Steady burning KW - Fire load KW - Fire resistance PY - 2021 SN - 978-1-56990-762-7 SP - 23 EP - 52 PB - Hanser CY - Munich ET - 4th Edition AN - OPUS4-52684 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wahab, M. A. A1 - Kebelmann, Katharina A1 - Schartel, Bernhard A1 - Griffiths, G. T1 - Improving bio-oil chemical profile of seaweeds through anaerobic fermentation pre-treatment N2 - Biomass pre-treatments for bio-oil quality improvement are mainly based on thermal and chemical methods which are costly and hence reduce the sustainability of pyrolysis-based refineries. In this paper, anaerobic digestion (AD) and dark fermentation (DF) are proposed as alternative ‘green’ pre-treatments to improve this situation. For this purpose, three seaweeds namely Sargassum polycystum, (Phaephyta), Gracilaria tenuistipitata, (Rhodophyta) and Ulva reticulata, (Chlorophyta) with high ash and oxygen contents were pre-treated to improve their composition and structure prior to pyrolysis. The results reveal that both biological pre-treatments affected, positively, the composition and structure of the seaweed biomass with AD pre-treatment reducing N and S contents by 86% and 63%, respectively. DF was more efficient in terms of ash and moisture reduction with 25% and 70%, respectively. In addition, oxygen (O) reduction by 27% was observed after DF which was evidenced by FTIR spectroscopy indicating the reduction of most oxygen-containing functional groups in the biomass. On the other hand, the carbon (C) content increased in DF pre-treated seaweeds up to 42%, almost two times higher relative content than C in the raw seaweed. The changes in the composition of pre-treated seaweeds resulted in changes in their thermal degradation and the volatile profiles produced during pyrolysis. Interestingly, anhydrosugars and furans which account for some 70% (by area) in raw seaweeds markedly declined or become undetectable after DF pre-treatment and correspondingly more acetic acid and hydrocarbons were produced while after AD more aromatics with high toluene content (ca.17%) were generated. The results indicate that biooil with profiles more similar to petroleum-based composition i.e. rich in hydrocarbons and low in anhydrosugars, N and S can be generated by AD and DF pre-treatments and opens up the possibility of these approaches to effect cost reduction in the overall generation of bio-based fuels. KW - Anaerobic digestion KW - Dark fermentation KW - Pyrolysis KW - Seaweeds KW - Thermogravimetric analysis KW - Pyrolysis volatiles PY - 2021 DO - https://doi.org/10.1016/j.enconman.2021.114632 SN - 0196-8904 VL - 245 SP - 1 EP - 12 PB - Elsevier CY - Amsterdam AN - OPUS4-53136 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schartel, Bernhard T1 - Thermal Decomposition Features Flame Retardancy N2 - INTRODUCTION: Most polymeric materials in most fire scenarios burn based on an anaerobe pyrolysis feeding the flame with fuel. Understanding the thermal decomposition in the condensed phase is key to tailor flame retardancy. Adjusting the decomposition temperature of flame retardant and polymer as well as providing the desired chemical structure for specific reactions determine the molecular mechanisms and thus the flame-retardant modes of action. Hereby, it is not only charring in the condensed phase and radical scavenging in the gas phase, but also physicochemical and physical effects such as melt flow and protective layer formation. This paper delivers thought-provoking impulses on how the understanding of the pyrolysis can be used for evidenced-based development and optimization of flame-retardant polymeric materials. Some rather overseen details are picked up as well as rethinking of concepts memorized long ago is encouraged to discover something new. The talk tries to fill some gaps between flame-retardant mechanisms, flame-retardant modes of action, and fire performance. EXPERIMENTAL: Materials - This paper deduces its conclusions from results of several research projects performed in the working group of the author. For a detailed description of the materials, their compounding, and the preparation of test specimens please go for the comprehensive description in the original papers.[1-10] Methods - A multi-methodical approach based on thermogravimetry (TGA), TGA coupled with evolved gas analysis (TGA-FTIR), hot stage FTIR, pyrolysis GC/MS, and residue analysis was used for investigating the pyrolysis. The flammability in the fire scenario ignition was addressed using oxygen index (OI) and testing in the UL 94 burning chamber. The fire behaviour in developing fires was investigated using a cone calorimeter. Additional efforts complete the studies, such as other fire tests, advanced analysis of the fire residue, melt rheology, or particle finite element simulations (PFEM). Tailored and self-designed experiments and advanced data evaluation described fire phenomena or modes of action. For a detailed description of the experimental the reader is relegated to the original papers.[1-10] RESULTS AND DISCUSSION: One important aspect in achieving, adjusting, and optimising flame retardancy is exploiting specific chemical reactions in the condensed phase between the pyrolyzing polymer and the flame retardant at the right place, time, and temperature.[1-3] At the same time, these reactions of partly decomposed or hydrolysed flame retardants in the condensed phase competes with releasing as volatile into the gas phase. Based on three comparisons this field is illuminated in detail: reactive phosphine oxide, phosphinate, phosphonate, and phosphate are compared in the same epoxy resins evaluating the influence of the oxidation state,[1] different phosphorous flame retardants in different epoxy resins underlining the specific reactions between the partly decomposed or hydrolysed flame retardant and the partly decomposed polymer,[3] and the comparison of three aryl phosphates with different volatility highlights the competition of chemical reaction in the condensed phase and gasification.[2] Any fire residue reduces fire risks, when the release of hydrocarbon fuel into the gas phase is replaced by storing fuel in the condensed phase as carbonaceous char. Thus, charring describing crosslinking, dehydration, aromatization, and graphitization is the flame retardancy mechanisms, whereas charring describing the reduction in fire load the flame-retardant mode of action. The phenomenon charring belongs to a complete pyrolysis or complete pyrolysis step; the char yield indicates the amount of fuel stored in the residue. Further, any fire residue works as protective layer. The barrier properties depend on the physical properties of the residue but not necessarily on its amount.[4] Usually, a residue design such as a tailored morphology of the fire residue is demanded. The mass loss rate and heat release rate are reduced. The main mechanisms are heat shielding and thermal insulation.[5] Sometimes the protective layer is good enough to cause incomplete pyrolysis due to extinguishing before the pyrolysis front went through the whole sample.[6.7] Analogous to charring also incomplete pyrolysis can result in efficient reduction in fire load. Proper data evaluation and key experiments are used to sort out and understand these different phenomena. Flame retardant polyurethane foams passing the heat release and smoke toxicity requirements of EN 45545 are discussed as evidence-based development using charring and incomplete pyrolysis due to an efficient protective layer.[7,8] The thermal decomposition into liquid intermediate products increases crucially the melt flow during burning,[9] whereas charring and the ablation of the polymer matrix increasing the content of fillers yield melt viscosities enlarged by orders of magnitude.[10] Violent burning of some polymers at the end of a cone calorimeter test can be understood as pyrolysis enabling a pool fire. The understanding of the thermal decomposition of the polymeric material harbours the explanation of non-flaming dripping extinguishing the flame via sufficient cooling, retreat effects preventing ignition, and efficient nondripping flame retardancy. This paper leads the audience from chemistry over complex macroscopic fire phenomena of physicochemical nature to fire performance. Thought-provoking impulses are given how the scientific understanding of the pyrolysis in the condensed phase can be used for research and evidenced-based development of future flame-retardant polymeric materials. Acknowledgement: The talk uses results from distinct projects; thus, thanks go to the German Research Foundation DFG SCHA 730/6-1, SCHA 730/8, SCHA 730/10-1, and Scha 730/19-1, Bayer MaterialScience AG, and the BMWi (BMWK) AiF: IGF No.: 19078 N/2 for financial support. Many thanks to former working group members U. Braun, Y. Y. Chan, B. Perret, S. Rabe, K. H. Richter, A. Weiß, and G. Wu, and to our co-operation partners A. Hartwig (IFAM), M. Döring and M. Ciesielski (at that time KIT), and J. M. Marti (CIMNE) as well. T2 - 11th Conference of the Modification, Degradation, Stabilization of Polymers, MoDeSt 2024 CY - Palermo, Italy DA - 01.09.2024 KW - Flame retardants KW - Decomposition KW - Modes of action KW - Mechanisms KW - Charring KW - Flame inhibition KW - Dripping KW - Protective layer KW - Pyrolysis PY - 2024 AN - OPUS4-60960 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schartel, Bernhard A1 - Wilkie, Charles A. A1 - Camino, Giovanni T1 - Recommendations on the scientific approach to polymer flame retardancy: Part 1—Scientific terms and methods N2 - The correct use of scientific terms, performing experiments accurately, and discussing data using unequivocal scientific concepts constitute the basis for good scientific practice. The significance and thus the quality of scientific communication rely on the proper use of terms and methods. It is the aim of this two-part article to support the community with recommendations for discussing the flame retardancy of polymers by addressing some of the most relevant points. The first article (part one of two) clarifies some scientific terms and, in some cases, such as for ‘‘pyrolysis,’’ ‘‘thermal decomposition,’’ and ‘‘fire resistance,’’ critically discusses their definitions in the field of fire science. Several comments are made on proper fire testing and thermal analysis, including some thoughts on uncertainty in fire testing. The proper use of distinct concepts in flame retardancy is discussed briefly in the subsequent second article (part two). This article tries to Balance imparting background on the subject with recommendations. It encourages to check scientific practice with respect to communication and applying methods. KW - Pyrolysis KW - Fire testing KW - Char KW - Flame retardant KW - Flammability KW - Fire property PY - 2016 DO - https://doi.org/10.1177/0734904116675881 SN - 0734-9041 SN - 1530-8049 VL - 34 IS - 6 SP - 447 EP - 467 PB - SAGE AN - OPUS4-38115 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schartel, Bernhard T1 - Born in fire to kill fire – graphene in flame retardant nanocomposites N2 - Carbon black, multiwall carbon nanotubes, expanded graphite, multilayer graphene and graphene are compared comprehensively as flame retardants in nanocomposites to each other. Different polymer matrices are investigated as well as changing the concentration of the carbon fillers. Distinct combinations of graphene with conventional flame retardants are investigated. Phenomena and mechanisms are identified controlling the pyrolysis and fire behavior. The viscosity of the nanocomposites and their thermal conductivity as well are dramatically changed compared to the polymers influencing the time to ignition and flammability. During pyrolysis graphene functioned as inert filler and formed a residual protective layer reducing the peak heat release rate. The influence of graphene on the effectivity of various conventional halogen-free flame retardants depends strongly on their modes of action. The addition of a small amount of graphene to an intumescent flame retardant poly(propylene) led to an improvement in the cone calorimeter. The further increase of graphene content gained deceleration of swelling and a decrease of the final height of the intumescent layer. In combination with metal hydroxide, 1 wt% graphene closed the macroscopic surface structure and densified the microscopic structure of the fire residues tremendously. Due to this improved residue structure, metal hydroxides and graphene showed synergistic cooperation in terms of oxygen index and UL 94 classification (HB/V-1 to V-0). T2 - Rudolstädter Kunststoff-Tag CY - Rudolstadt, Germany DA - 12.10.2016 KW - Graphene KW - Nanocomposite KW - Flame retardant KW - Flammability KW - Pyrolysis PY - 2016 AN - OPUS4-38116 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schartel, Bernhard T1 - Flame and fire retardancy of polymer composites used in aviation N2 - The fire behaviour of carbon fibre (CF) reinforced polymers differs in comparison to polymers. Fibres behave often inert with respect to pyrolysis, they change the melt flow and dripping behaviour, the heat absorption and transfer, the amount and properties of the fire residue and so on. Flame and fire retardancy concepts are needed not only suitable for the different fire protection goals typical for each application, but also tailored for composites. This field is illuminated by examples taken from different projects carried out in the group of the author in the recent years. The examples target on different applications through achieving reduction in reaction to fire controlling the fire risks (flammability, heat release) in the beginning and development of a fire and investigating the fire stability, when a severe flame is directly applied (key property in fully developed fires). Approaches to halogen-free flame retardancy in CF reinforced thermosets are presented as well as building up a bench and an intermediate scale testing of composites in fire applying mechanical load (up to 1 MN compression) and direct flame exposure (180 kW/m2) simultaneously. Indeed, e.g. we have investigated the fire stability of stringer reinforced shell components taken out from the fuselage of an aircraft. The understanding of fire behaviour, fire resistance, and fire retardant modes of action in composites is a promising basis for target-oriented development. The role of flame inhibition, charring, and protective layer formation is discussed. Successful concepts are presented for fire retardancy tailored for different application as well as general guidelines for future development. Different phosphorus flame retardants are proposed to achieve halogen-free flame retardancy with respect to ignition and developing fires. Different protective approaches are sketched for addressing the fire stability of composites that is the most important fire risk for the fire resistance in structural applications. T2 - 7th EASN International Conference on Innovation in European Aeronautics Research CY - Warsaw, Poland DA - 26.09.2017 KW - Composite in Fire KW - Carbon fibre reinforced composite KW - Epoxy resin KW - Stringer reinforced shells KW - Fire stability KW - Flammability KW - Sandwich panels KW - Intumescence KW - Pyrolysis KW - Flame retardant PY - 2017 AN - OPUS4-42433 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schartel, Bernhard A1 - Weiß, André T1 - Temperature inside burning polymer specimens: Pyrolysis zone and shielding N2 - On the basis of two examples, temperature measurements are proposed within burning polymer specimen during the cone calorimeter test; especially to gain deeper insight into the actual pyrolysis conditions and flame retardancy mechanism. The heating and pyrolysis within a poly(methyl methacrylate) specimen were characterized, discussing the characteristic maximum heating rates (165-90°Cmin-1 decreasing with depth within the specimen and >275°Cmin-1 at the initial surface), pyrolysis temperature (454-432°C decreasing in accordance with decreasing heating rates), thickness of the pyrolysis zone (0.5-1.3 mm) and its velocity (1.2-2.1 mm min-1) as a function of sample depth and burning time. Thermally thick behaviour corresponds to a pyrolysis zone thickness of 0.74 mm and a velocity of 1.51 mm min-1 and occurs until the remaining specimen thickness is less than 8 mm. The shielding effect against radiation occurring in a layered silicate epoxy resin nanocomposite was investigated. It is the main flame retardancy effect of the silicate-carbon surface layer formed under fire. The reradiation from the hot surface is increased by a factor of around 4-5 when an irradiance of 70kWm-2 is applied. The energy impact into the pyrolysis zone is crucially reduced, resulting in a reduction of fuel production and thus heat release rate. KW - Cone calorimeter KW - Pyrolysis KW - Nanocomposite KW - Poly(methyl methacrylate) KW - Pyrolysis zone KW - Pyrolysis front KW - Shielding effect PY - 2010 DO - https://doi.org/10.1002/fam.1007 SN - 0308-0501 SN - 1099-1018 VL - 34 IS - 5 SP - 217 EP - 235 PB - Heyden CY - London AN - OPUS4-21724 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Perret, Birgit A1 - Schartel, Bernhard A1 - Stöß, K. A1 - Ciesielski, M. A1 - Diederichs, J. A1 - Döring, M. A1 - Krämer, J. A1 - Altstädt, V. T1 - A new halogen-free flame retardant based on 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide for epoxy resins and their carbon fiber composites for the automotive and aviation industries N2 - The pyrolysis and fire behavior of halogen-free flame-retarded DGEBA/DMC, RTM6 and their corresponding 60 vol.-% carbon fibers (CF) composites were investigated. A novel phosphorous compound (DOPI) was used. Its action is dependent on the epoxy matrix. DGEBA/DMC and DOPI decompose independently of each other. Only flame inhibition occurs in the gas phase. RTM6 shows flame inhibition and a condensed phase interaction increasing charring. Both mechanisms decrease with increasing irradiance, whereas in RTM6-CF charring is suppressed at low ones. RTM6+DOPI shows a higher LOI (34.2%) than DGEBA/DMC+DOPI and a V-0 classification in UL 94. Adding CF only enhances the LOI, DOPI+CF leads to a superposition in LOI for DGEBA/DMC-CF+DOPI (31.8%, V-0) and a synergism for RTM6-CF+DOPI (47.7%, V-0). KW - Composites KW - Flame retardancy KW - Glass transition KW - Pyrolysis KW - Thermosets PY - 2011 DO - https://doi.org/10.1002/mame.201000242 SN - 1438-7492 SN - 1439-2054 VL - 296 IS - 1 SP - 14 EP - 30 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-22957 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -