TY - JOUR A1 - Tomiak, F. A1 - Schartel, Bernhard A1 - Wolf, M. A1 - Drummer, D. T1 - Particle Size Related Effects of Multi-Component Flame-Retardant Systems in poly(butadiene terephthalate) N2 - Aluminum tris (diethylphosphinate) (AlPi) is known to have an efficient flame-retardant effect when used in poly(butadiene terephthalates) (PBT). Additionally, better flame-retardant effects can be achieved through the partial substitution of AlPi by boehmite in multi-component systems, which have been shown to be an effective synergist due to cooling effects and residue formation. Although the potential of beneficial effects is generally well known, the influence of particle sizes and behavior in synergistic compositions are still unknown. Within this paper, it is shown that the synergistic effects in flammability measured by limiting oxygen index (LOI) can vary depending on the particle size distribution used in PBT. In conducting thermogravimetric analysis (TGA) measurements, it was observed that smaller boehmite particles result in slightly increased char yields, most probably due to increased reactivity of the metal oxides formed, and they react slightly earlier than larger boehmite particles. This leads to an earlier release of water into the system enhancing the hydrolysis of PBT. Supported by Fourier transformation infrared spectroscopy (FTIR), we propose that the later reactions of the larger boehmite particles decrease the portion of highly flammable tetrahydrofuran in the gas phase within early burning stages. Therefore, the LOI index increased by 4 vol.% when lager boehmite particles were used for the synergistic mixture. KW - Flame retardants KW - Aluminum diethylphosphinate KW - Boehmite KW - Poly(butadiene terephthalates) (PBT) KW - Mechanical properties PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-509286 DO - https://doi.org/10.3390/polym12061315 SN - 2073-4360 VL - 12 IS - 6 SP - 1315 PB - MDPI AN - OPUS4-50928 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Morys, Michael A1 - Häßler, Dustin A1 - Krüger, Simone A1 - Schartel, Bernhard A1 - Hothan, Sascha T1 - Beyond the standard time-temperature curve: Assessment of intumescent coatings under standard and deviant temperature curves N2 - Nowadays there are intumescent coatings available for diverse applications. There is no established assessment of their protection performance besides the standard time-temperature curve, but natural fire scenarios often play an important role. A reliable straightforward performance-based assessment is presented. The effective thermal conductivity per thickness is calculated based on intermediate-scale fire tests. The optimum thermal insulation, the time to reach it, and the time until contingent failure of the coating are used for an assessment independent of the heating curve. The procedure was conducted on four different commercially intumescent coatings for steel construction, one solvent-based, one waterborne, one epoxy-based, and a bandage impregnated with a waterborne coating. The performance was studied under four different but similar shaped heating curves with different maximum temperatures (standard time-temperature curve, hydrocarbon curve and two self-designed curves with reduced temperature). The thermal protection performance is crucially affected by the residue morphology. Therefore, a comprehensive morphology analysis, including micro-computed tomography and scanning electron microscopy, was conducted on small-scale residues (7.5 x 7.5 cm2). Two different types of inner structures and the residue surface after different heat exposures were discussed in terms of their influence on thermal protection performance. KW - Intumescence KW - Coating KW - Computed tomography KW - Small scale KW - Heating curves KW - Residue morphology PY - 2020 DO - https://doi.org/10.1016/j.firesaf.2020.102951 SN - 0379-7112 VL - 112 SP - 102951 PB - Elsevier Ltd. AN - OPUS4-50334 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CHAP A1 - Schartel, Bernhard A1 - Kebelmann, Katharina ED - Hu, Y. ED - Wang, X. T1 - Fire testing for the development of flame retardant polymeric materials N2 - Flame retarded polymeric materials are used in various applications in which a certain fire behavior is demanded. Protection goals are defined, such as limited flammability in terms of hindered sustained ignition or limited contribution to a fire, and these protection levels are tested with defined specimens or components in defined fire scenarios, that is to say, different fire tests. Passing a specific fire test by meeting whatever its demands is often the most important development goal, so the parameters of the different fire tests vary widely to emphasize different fire properties. Some fire tests are used to screen or provide a general assessment of flame retardant polymers during development, while other fire tests and tailored experiments are performed to address special phenomena or understand the flame retardancy modes of action. For all fire testing, the devil is in the details – demanding know-how and crucial efforts to manage the quality of investigations and advanced interpretation. This chapter aims to offer a structured overview of all these aspects. KW - Fire testing KW - Flame retardant KW - Fire retardant KW - Flammability KW - Ignition KW - Oxygen index KW - Cone calorimeter KW - UL 94 KW - Developing fire KW - Uncertainty KW - Fire resistance PY - 2020 SN - 978-1-138-29578-7 SP - 35 EP - 55 PB - CRC Press AN - OPUS4-50236 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 - Sulfur's role in the flame retardancy of thio-ether–linked hyperbranched polyphosphoesters in epoxy resins N2 - Hyperbranched polyphosphoesters are promising multifunctional flame retardants for epoxy resins. These polymers were prepared via thiol-ene polyaddition reactions. While key chemical transformations and modes of actions were elucidated, the role of sulfur in the chemical composition remains an open question. In this study, the FR-performance of a series of phosphorus-based flame retardant additives with and without sulfur (thioethers or sulfones) in their structure are compared. The successful synthesis of thio-ether or sulfone-containing variants is described and verified by 1H and 31P NMR, also FTIR and MALDI-TOF. A decomposition process is proposed from pyrolytic evolved gas analysis (TG-FTIR, Py-GC/MS), and flame retardancy effect on epoxy resins is investigated under pyrolytic conditions and via fire testing in the cone calorimeter. The presence of sulfur increased thermal stability of the flame retardants and introduced added condensed phase action. Likely, Sulfur radical generation plays a key role in the flame-retardant mode of action, and sulfones released incombustible SO2. The results highlight the multifunctionality of the hyperbranched polymer, which displays better fire performance than its low molar mass thio-ether analogue due to the presence of vinyl groups and higher stability than its monomer due to the presence of thio-ether groups. KW - Phosphoester KW - Hyperbranched KW - Sulfur KW - Thio-ether KW - Flame retardant KW - Epoxy resin PY - 2020 DO - https://doi.org/10.1016/j.eurpolymj.2019.109390 SN - 0014-3057 VL - 122 SP - 109390 PB - Elsevier Ltd. AN - OPUS4-50238 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Turski Silva Diniz, Analice A1 - Huth, Christian A1 - Schartel, Bernhard T1 - Dripping and decomposition under fire: Melamine cyanurate vs. glass fibres in polyamide 6 N2 - Manipulating the melt dripping of thermoplastics makes a fire scenario more or less dangerous. Yet, a detailed understanding of this phenomenon has remained a question mark in studies of the flammability of plastics. In this work, the individual and collective impacts of additives on the dripping behaviour of polyamide 6 (PA6) were studied. A set of materials compounded with melamine cyanurate (MCA) and glass fibre (GF) was investigated. Under UL 94 vertical test conditions, the dripping during first and second ignition was quantified and investigated in detail. The number, size and temperature of the drops were addressed, and the materials and their drops evaluated with respect to such aspects as their averaged molecular weight, thermal decomposition and rheological properties. PA6 with V-2 classification improved to V-0 with the addition of MCA, and achieved HB in the presence of GF. PA6/GF/MCA achieved V-2. Non-flaming drops of PA6/MCA consisted of oligomeric fragments. Flaming drops of PA6/GF showed a more pronounced decomposition of PA6 and an increased GF content. The dripping behaviour of PA6/GF/MCA can be understood as a combination of the influence of both additives. The results showed nicely that dripping under fire is neither a straightforward material property nor a simple additive influence, but the complex response of the material influenced by the interaction and competition of different phenomena. KW - Dripping KW - UL 94 KW - Polyamide 6 KW - Melamine cyanurate KW - Glass fibre KW - Flame retardant PY - 2020 DO - https://doi.org/10.1016/j.polymdegradstab.2019.109048 SN - 0141-3910 VL - 171 SP - 109048 PB - Elsevier Ltd. AN - OPUS4-50239 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zirnstein, Benjamin A1 - Schulze, Dietmar A1 - Schartel, Bernhard T1 - Combination of phosphorous flame retardants and aluminum trihydrate in multicomponent EPDM composites N2 - Ethylene propylene diene monomer (EPDM) Rubbers with the flame retardants tris(2-ethylhexyl)phosphate, ammonium polyphosphate, polyaniline, and aluminum trihydroxide were prepared and analyzed in this study. The homogenous dispersion of the fillers in the rubber matrix was confirmed by scanning electron microscope. To investigate the interplay of the different flame retardants, the flame retardants were varied systematically. The comprehensive study sought combinations of flame retardants that allow high loadings of flame retardants without deterioration of the physical and mechanical properties of the EPDM rubber. The eight EPDM rubbers were investigated via thermogravimetric analysis and pyrolysis gas chromatography coupled with a mass spectrometer (Py GC/MS) to investigate the potential synergistic effects. In the Py-GC/MS experiments, 27 pyrolysis products were identified. Furthermore, UL 94, limiting oxygen index, FMVSS 302, glow wire tests, and cone calorimeter tests were carried out. In the cone calorimeter test the EPDM rubbers R-1AP and R-1/2P achieved an increase in residue at flameout of 76% and a reduction in total heat evolved of about 35%. Furthermore, the compounds R-1AP and R-1/2P achieved a reduction in MARHE to about 150 kW m−1, a reduction of over 50% compared to the unprotected rubber R. KW - EPDM KW - Rubber KW - Aluminum hydroxide (ATH) KW - Phosphorous flame retardant PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-502859 DO - https://doi.org/10.1002/pen.25280 SN - 1548-2634 VL - 60 IS - 2 SP - 267 EP - 280 PB - Wiley AN - OPUS4-50285 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Rabe, Sebastian A1 - Klack, Patrick A1 - Bahr, Horst A1 - Schartel, Bernhard T1 - Assessing the fire behavior of woods modified by N-methylol crosslinking, thermal treatment, and acetylation N2 - Wood products are often treated by different techniques to improve their longevity when used as building materials. Most of the time, the goal is to increase their resistance to weathering effects, deformations in material dimensions or biotic decomposition. These wood treatment techniques have a significant impact on pyrolysis and burning behavior. The general effects of three different common wood treatments on flame retardancy were investigated by comparing treated woods with their untreated counterparts and with other kinds of wood. While the acetylation of beech leads to a slightly increased fire hazard, the thermal treatment of wood and crosslinking of cellulose microfibrils dimethyloldihydroxy-ethyleneurea show a limited flame retarding effect. Switching to woods with a higher lignin content, and thus higher char yield, however, results in a more pronounced improvement in flame retardancy performance. This article delivers a comprehensive and balanced assessment of the general impact of different wood modifications on the fire behavior. Further, it is a valuable benchmark for assessing the flame retardancy effect of other wood modifications. KW - Acetylation KW - Cone claorimeter KW - DMDHEU KW - Heat of combustion KW - Thermal treatment KW - Wood modification PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-507397 DO - https://doi.org/10.1002/fam.2809 SN - 1099-1018 SN - 0308-0501 VL - 44 IS - 4 SP - 530 EP - 539 PB - Wiley Online Libary AN - OPUS4-50739 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ma, S. A1 - Xiao, Y. A1 - Zhou, F. A1 - Schartel, Bernhard A1 - Chan, Yin Yam A1 - Korobeinichev, O. P. A1 - Trubachev, S. A. A1 - Hu, W. A1 - Ma, C. A1 - Hu, Y. T1 - Effects of novel phosphorus-nitrogen-containing DOPO derivative salts on mechanical properties, thermal stability and flame retardancy of flexible polyurethane foam N2 - In this work, a series of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) derivative salts containing phosphorus and nitrogen were synthesized, and their effects on mechanical properties, thermal stability and flame retardancy of flexible polyurethane foam (FPUF) were investigated. Studies have shown that the addition of DOPO derivatives will increase the tensile strength, compression set, and compression hardness of FPUF, but it will lead to a decrease in elongation at break. Thermogravimetric analysis showed that the initial decomposition temperature of FPUF containing DOPO derivatives was reduecd, but the char reside was significantly improved. A series of combustion tests indicated that the addition of DOPO derivative salts can improve the flame retardancy of FPUF, of which 10-hydroxy-9,10-dihydro-9-oxa-10 phosphaphenanthrene-10-oxide dicyandiamide salt (D-DICY) exhibited the best flame retardancy. When the load of D-DICY was 20 phr, the limiting oxygen index (LOI) of foam reached 24.5%, and the peak heat release rate and total heat release were decreased by 55.7% and 52.9%, respectively. Furthermore, based on the analysis of the gas phase combustion products and the char residue of the condensed phase, the possible flame retardant mechanism was proposed. KW - Flexible polyurethane foam KW - DOPO derivative salts KW - Mechanical properties KW - Thermal stability KW - Flame retardancy PY - 2020 DO - https://doi.org/10.1016/j.polymdegradstab.2020.109160 SN - 0141-3910 VL - 177 SP - 109160 PB - Elsevier Ltd. AN - OPUS4-50740 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Raschpichler, C. A1 - Goroncy, C. A1 - Langer, B. A1 - Antonsson, E. A1 - Wassermann, B. A1 - Graf, C. A1 - Klack, Patrick A1 - Lischke, T. A1 - Rühl, E. T1 - Surface Properties and Porosity of Silica Particles Studied by Wide-Angle Soft X-ray Scattering N2 - Wide-angle soft X-ray scattering on free silica particles of different porosity prepared in a beam is reported. The explored q region is mostly dominated by features due to surface roughness and bulk porosity. A comprehensive experimental and theoretical analysis of silica particles of different porosity is presented for various incident photon energies. A correlation analysis, based on the theory of Porod, is used to test the validity of exact Mie theory in different pore density limits. The ability of the discrete dipole scattering model (DDSCAT) to resolve local effects, caused by various pore distributions, is discussed. Characteristic differences between the soft X-ray scattering patterns of the particle samples of different surface properties and porosity are detected. For all mentioned cases, it was confirmed that the effective radius concept of the Guinier model can be successfully extended to Mie theory and DDSCAT in describing the additive contributions of the primary particles, including a thin inhomogeneous solvent-rich surface shell and empty bulk pores. Close agreement, within ±15%, between the calculated and observed pore sizes and porosity values is reached. The influence of pores is alternatively described either in terms of secondary Mie scattering, which is modulated by the local internal electrical field within the particles, or by an independent Mie scattering process induced by the incident field on isolated pores. It is found that for the typical pore/particle size ratios the latter approach presents the best choice. KW - Wide-Angle Soft X‑ray Scattering KW - Silica KW - Porosity PY - 2020 DO - https://doi.org/10.1021/acs.jpcc.0c04308 SN - 1932-7447 SN - 1932-7455 VL - 124 SP - 16663 EP - 16674 AN - OPUS4-51089 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Häßler, Dustin A1 - Häßler, M. A1 - Hothan, Sascha A1 - Krüger, Simone T1 - Reaktive Brandschutzsysteme auf Stahlbauteilen mit doppelt gekrümmter Oberfläche N2 - Reaktive Brandschutzsysteme können die Feuerwiderstandsdauer von Stahlbauteilen signifikant erhöhen. Im Brandfall schäumt das reaktive Brandschutzsystem auf und bildet um das Stahlbauteil eine thermische Schutzschicht aus. Dadurch wird die Erwärmung des Stahls verlangsamt und der temperaturbedingte Festigkeitsverlust verzögert. Reaktive Brandschutzsysteme werden überwiegend in drei Bereichen angewendet: Hochbau, Offshore bzw. maritimer Sektor sowie Tank- bzw. Behälterbau. Insbesondere bei Stahltanks und -behältern sind häufig einfach oder auch doppelt gekrümmte Bauteiloberflächen anzutreffen. Aufgrund des meist begrenzten seitlichen Expansionsvermögens von reaktiven Brandschutzsystemen kann es bei Bauteilen mit konvexer Oberflächenkrümmung zu einer Intensivierung der Rissbildung im Schaum kommen, wodurch sich häufig die thermische Schutzwirkung verschlechtert. Da zum Thema des Einflusses der Oberflächenkrümmung auf die Leistungsfähigkeit reaktiver Brandschutzsysteme bisher kaum Untersuchungen vorliegen, wurden exemplarisch zwei Tankböden mit zwei verschiedenen Trockenschichtdicken eines reaktiven Brandschutzsystems einer Brandprüfung unterzogen. Bei gleicher Trockenschichtdicke des reaktiven Brandschutzsystems zeigten die Tankböden eine wesentlich schnellere Erwärmung als ebene Stahlplatten mit vergleichbarem Profilfaktor. Die Brandprüfungen und die Ergebnisse zum Einfluss der Oberflächenkrümmung werden im Beitrag ausführlich vorgestellt und diskutiert. KW - Brandschutz KW - Stahl KW - Reaktive Brandschutzsysteme KW - Behälter KW - Intumeszierende Beschichtung PY - 2020 DO - https://doi.org/10.1002/stab.201900095 VL - 89 IS - 9 SP - 794 EP - 800 PB - Ernst & Sohn Verlag CY - Berlin AN - OPUS4-51242 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Günther, Martin A1 - Lorenzetti, A. A1 - Schartel, Bernhard T1 - From Cells to Residues: Flame-Retarded Rigid Polyurethane Foams N2 - Rigid polyurethane foams (RPUFs) exhibit short times to ignition as well as rapid flame spread and are therefore considered to be hazardous materials. This paper focuses on the fire phenomena of RPUFs, which were investigated through a multimethodological approach. Water-blown polyurethane (PUR) foams without flame retardants (FRs) as well as waterblown PUR foams containing triethyl phosphate as a gas phase-active FR were examined. The aim of this study is to clarify the influence of the FR on the fire phenomena during combustion of the foams. Additionally, materials’ densitieswere varied to range from 30 to 100 kg/m3. Thermophysical properties were studied bymeans of thermogravimetry; fire behavior and flammability were investigated via cone calorimeter and limiting Oxygen index, respectively. During the cone calorimeter test, the temperature development inside the burning specimens was monitored with thermocouples, and cross sections of quenched specimens were examined visually, giving insight into the morphological changes during combustion. The present paper delivers a comprehensive study, illuminating phenomena occurring during foam combustion and the influence of a FR active in the gas phase. The superior fire performance of flameretarded PUR foams was found to be based on flame inhibition, and on increased char yield leading to a more effective protective layer. It was proven that in-depth absorption of radiation is a significant factor for estimation of time to ignition. Cross sections investigated with the electron scanning microscope exhibited a pyrolysis front with an intact foam structure underneath. The measurement of temperature development inside burning specimens implied a shift of burning behavior towards that of non-cellular materials with rising foam density. KW - Polyurethane KW - Rigid foams KW - Fire behavior PY - 2020 DO - https://doi.org/10.1080/00102202.2019.1634060 SN - 0010-2202 SN - 1563-521X VL - 192 IS - 12 SP - 2209 EP - 2237 PB - Taylor & Francis AN - OPUS4-51483 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -