TY - JOUR A1 - Sunder, S. A1 - Jauregui Rozo, Maria A1 - Deshpande, H. A1 - Neyer, A. A1 - Papaiya, V. A1 - Meinel, Dietmar A1 - Schartel, Bernhard A1 - Ruckdäschel, H. T1 - Char to the Rescue: Processing and Transfer of Flame-Retardant Epoxy Resins, Adjusting the Fire Behavior and Post-Fire Structural Integrity of Glass Fiber Composites N2 - Epoxy (EP) glass fiber reinforced composites (GFRCs) are extensively used in structural applications due to their excellent thermal and mechanical properties, but their inherent flammability limits fire-safe deployment. While numerous studies examine the flame retardancy of resins or individual composite systems, comprehensive studies evaluating simultaneous improvements in flame retardancy and post-fire mechanical integrity, specifically through prepreg processing, remain challenging. This study investigates the effectiveness and transferability of phosphorus-based flame retardant (FR) systems to diglycidyl ether of bisphenol A (DGEBA) and EP novolac resin matrices and their corresponding bidirectional glass fiber composites via prepregs. The FRs are chosen based on varying modes of action: ammonium polyphosphate with inorganic silicate (APP/InSi) primarily acts in the condensed phase (CP), and aluminum diethyl phosphinate with zinc hydroxystannate (AldietPO2/ZHS) is known to demonstrate both gas-phase (GP) and CP activity. Fire residues are tailored to compensate for structural defects from fire exposure. EP novolac, with higher aromaticity and cross-linking, possesses better inherent flame resistance compared to DGEBA. The novolac composites containing AldietPO2/ZHS simultaneously showed the highest retention of flexural properties after fire exposure and the best fire safety index. The experimental values of the post-fire flexural properties in the composites calibrated damage parameters in two theoretical models. KW - Composites KW - DGEBA KW - Epoxy novolac KW - Post-fire KW - Prepregs PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-643752 DO - https://doi.org/10.1002/pol.20250692 SN - 2642-4169 SN - 2642-4150 VL - 63 IS - 20 SP - 4295 EP - 4309 PB - Wiley AN - OPUS4-64375 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sunder, S. A1 - Jauregui Rozo, Maria A1 - Inasu, S. A1 - Meinel, Dietmar A1 - Schartel, Bernhard A1 - Ruckdäschel, H. T1 - Effect of Ammonium Polyphosphate/Silicate Content on the Postfire Mechanics of Epoxy Glass-Fiber Composites Using Facile Chocolate Bar-Inspired Structures N2 - This study investigates the postfire mechanical properties of epoxy glass-fiber reinforced composites (EP GFRCs) using increasing concentrations of ammonium polyphosphate (APP) and inorganic silicate (InSi) to modify the char and fire residue. A facile chocolate bar-inspired structure was introduced for fire exposure and subsequent flexural testing of the GFRCs. The resin matrix used here was a diglycidyl ether of bisphenol-A (DGEBA) resin, cured with dicyandiamide (DICY), and accelerated by Urone. The microstructures of the degraded composites after three-point bending tests, were evaluated using scanning electron microscopy (SEM) and x-ray computed tomography (XCT) imaging. A previous study showed that increasing the APP and InSi content significantly enhanced flame retardancy, via improved char formation under fire conditions. However, flexural properties and fire resistance were adversely affected after fire exposure, highlighting a trade-off effect. Fiber breakage and delamination of the composites increased upon failure with increasing APP + InSi content in the composite due to unconsolidated char. The experimental values for the postfire flexural mechanics were in good agreement with the two-layer model proposed in literature. This paper presents a preliminary basis for postfire mechanical testing of epoxy composites for use in fire-safe structures, using a combination of standardized testing norms. KW - Flame retardants KW - Post-fire KW - Epoxy KW - Gass fiber composites KW - Prepregs PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-627176 DO - https://doi.org/10.1002/fam.3280 SN - 0308-0501 SN - 1099-1018 VL - 49 IS - 3 SP - 329 EP - 346 PB - Wiley AN - OPUS4-62717 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sunder, S. A1 - Jauregui Rozo, Maria A1 - Inasu, S. A1 - Schartel, Bernhard A1 - Ruckdäschel, H. T1 - A systematic investigation of the transfer of polyphosphate/inorganic silicate flame retardants from epoxy resins to layered glass fiber-reinforced composites and their post-furnace flexural properties N2 - The systematic transfer of solvent-free, additive flame retardant (FR) formulations from epoxy resins to glass fiber-reinforced epoxy composites (GFRECs) through prepregs is difficult. Additionally, obtaining data on their post-fire mechanics is often challenging. Utilizing melamine polyphosphate (MPP), ammonium polyphosphate (APP), and silane-coated ammonium polyphosphate (SiAPP) FRs with low-melting inorganic silicates (InSi) in an 8:2 proportion and 10% loading by weight in a diglycidyl ether of bisphenol A (DGEBA) resin, a systematic investigation of the processing properties, room-temperature mechanics, and temperature-based mechanics of the systems was performed. The resin was cured with a dicyandiamide hardener (DICY) and a urone accelerator. The results revealed no substantial impact of these FRs at the current loading on the resin's glass transition temperature or processability. However, the fire residues from cone calorimetry tests of the composites containing FRs were found to be only 15-20% of the thickness of the resins, implying a suppression of intumescence upon transfer. At room temperature, the decrease in the flexural modulus for the composites containing FRs was negligible. Exposure of the composites in a furnace at 400°C as a preliminary study before ignition tests was shown to cause significant flexural moduli reductions after 2.5 min of exposure and complete delamination after 3 min making further testing unviable. This study emphasizes the need for future research on recovering modes of action upon transfer of FR formulations from resins to composites. Based on the challenges outlined in this investigation, sample adaptation methods for post-fire analysis will be developed in a future study. KW - DGEBA KW - Prepregs KW - Glass fiber-reinforced composites KW - Post-fire testing PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-605239 DO - https://doi.org/10.1002/pc.28416 SN - 1548-0569 SN - 0272-8397 VL - 45 IS - 10 SP - 9389 EP - 9406 PB - Wiley AN - OPUS4-60523 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sunder, S. A1 - Jauregui Rozo, Maria A1 - Inasu, S. A1 - Schartel, Bernhard A1 - Ruckdäschel, H. T1 - Investigating the changing dynamics of processing, temperature-based mechanics, and flame retardancy in the transfer of ammonium polyphosphate/inorganic silicate flame retardants from epoxy resins to glass fiber composites N2 - Although numerous investigations study the improvement of flame retardancy of epoxy resins using additives, maintaining the flame retardant (FRs) modes of action present in the resins upon transfer to composites is challenging. In this study, ammonium polyphosphate (APP) and inorganic silicate (InSi) are loaded at 10%, 30%, and 50% by weight, in a diglycidyl ether of bisphenol A (DGEBA) resin cured with dicyandiamide and transferred to bidirectional (BD) glass fiber (GF) composites. Although a 50% loading of the FRs impacts the curing kinetics of the resin system, the effect on the glass transition temperature of the resin system remains negligible compared to reactive FRs in the state of the art integrated into the resin's chemical structure. Increasing the FR content improved the heat release characteristics in both the resins and composites. However, the charring mode of action is completely suppressed in the formulation with 10% APP + InSi. A 30% concentration of the FRs restored the charring action in the composite and the GFs provide increased protective layer action upon transfer to the composites. This study highlights the importance of accounting for the changing dynamics related to processing and flame retardancy upon transferring FRs from resins to composites. KW - Composites KW - Flame retardance KW - Resins KW - Synthesis and processing techniques PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-610484 DO - https://doi.org/10.1002/app.55988 SN - 1097-4628 VL - 141 IS - 39 SP - 1 EP - 18 PB - Wiley CY - New York, NY AN - OPUS4-61048 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Sunder, S. A1 - Jauregui Rozo, Maria A1 - Inasu, S. A1 - Schartel, Bernhard A1 - Ruckdäschel, H. T1 - Correction to "Investigating the changing dynamics of processing, temperature‐based mechanics, and flame retardancy in the transfer of ammonium polyphosphate/inorganic silicate flame retardants from epoxy resins to glass fiber composites" N2 - This is a corrigendum to the original article "Investigating the changing dynamics of processing, temperature-based mechanics, and flame retardancy in the transfer of ammonium polyphosphate/inorganic silicate flame retardants from epoxy resins to glass fiber composites" that was published in the "Journal of applied polymer science", vol. 141 (2024), article no. e55988. PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-622687 DO - https://doi.org/10.1002/app.56329 SN - 1097-4628 VL - 141 IS - 48 SP - 1 PB - Wiley CY - New York, NY AN - OPUS4-62268 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Sunder, S. A1 - Jauregui Rozo, Maria A1 - Schartel, Bernhard A1 - Ruckdäschel, H. T1 - Adapting intumescent/low-melting glass flame-retardant formulations for transfer to glass-fiber-reinforced composites and post-fire mechanical analysis N2 - The residual post-fire mechanical properties of fiber-reinforced epoxy composites are influenced by their fire residues after burning. This study uses intumescent/low-melting glass flame retardants to tailor fire residues in epoxy resin. Processibility of prepregs and their quality are analysed for transfer of the flame-retardant epoxy resins to layered glass-fiber reinforced composites. Minimal effects were found on the pre-fire flexural strengths of the composites due to low loading of the flame retardants. However, when transferred to glass-fiber reinforced composites, the fire residues diminish significantly. Further studies are required to improve theoretical and experimental estimations of the post-fire mechanics of the composites. T2 - SAMPE Europe Conference 2023 CY - Madrid, Spain DA - 03.10.2023 KW - Fire residue KW - Prepregs KW - Mechanics KW - Lightweight materials KW - Composites KW - Flame retardancy PY - 2023 SP - 1 EP - 7 AN - OPUS4-59138 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Sunder, Sruthi A1 - Jauregui Rozo, Maria A1 - Ruckdäschel, Holger A1 - Schartel, Bernhard T1 - Investigating the trade-off effects of inorganic phosphate/silicate flame retardant content on the fire performance and post-fire flexural mechanics of epoxy/glass fiber composites N2 - Considering the existing challenges involved in the transfer of flame retardant (FR) formulations from epoxy (EP) resins to glass fiber reinforced composites (GFRCs), obtaining data on the post-fire flexural properties of such composites is even more challenging as this involves balancing test parameters with potential composite delamination. In this study, solvent-free FR additives: ammonium polyphosphate (APP), and inorganic silicate (InSi) were added at 10, 30% and 50% w/w loading to a Bisphenol A diglycidyl ether (DGEBA)-dicyandiamide (DICY)-Urone resin matrix. These resin formulations were transferred to bidirectional (BD) glass fiber composites via prepregs. A novel, but facile approach was developed to prepare the composite samples for furnace tests at 400 oC. The composites were also subjected to fire exposure at different heat fluxes and times via a bench-scale test and subsequently tested via three-point bending. At approximately 3.5% P content, the FRs significantly improve the fire performance of both the resins and composites. However, they also degrade the systems’ pre- and postfire flexural modulus and strength. Therefore, improving the flame-retardant mode of action of the FRs in the composites, contrastingly reduces their structural integrity post-fire leading to a trade-off effect. T2 - ECCM21 – 21st European Conference on Composite Materials CY - Nantes, France DA - 02.07.2024 KW - Flame retardants KW - Post-fire KW - Epoxy KW - Glass fiber composites KW - Prepregs PY - 2024 SP - 1 EP - 7 AN - OPUS4-60788 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Sunder, Sruthi A1 - Jauregui Rozo, Maria A1 - Ruckdäschel, Holger A1 - Schartel, Bernhard T1 - Adapting intumescent/low-melting glass flame-retardant formulations for transfer to glass-fiber-reinforced composites and postfiremechanical analysis N2 - The residual post-fire mechanical properties of fiber-reinforced epoxy (EP) composites are influenced by their fire residues after burning. This study uses intumescent/low-melting glass flame retardants (FRs) to tailor fire residues in epoxy resin. Processibility of prepregs, and their quality are analysed for transfer of the flame-retardant epoxy resins to layered glass-fiber reinforced composites (GFRCs). Minimal effects were found on the pre-fire flexural strengths of the composites due to low loading of the FRs. However, when transferred to GFRCS, the fire residues diminish significantly. Process, testing, and material adaptations are required to improve theoretical and experimental estimations of the post-fire mechanics of the composites. T2 - SAMPE Europe Conference 2023 Madrid - Spain CY - Madrid, Spain DA - 03.10.2023 KW - Fire residue KW - Prepregs KW - Mechanics PY - 2023 AN - OPUS4-60789 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 - 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 - 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 -