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Sacrifice Few to Save Many: Fire Protective Interlayers in Carbon- Fiber-Reinforced Laminates
(2024)
The fire protection of carbon-fiber-reinforced polymer (CFRP) laminates often relies on flame-retardant coatings, but in some applications, their efficacy may diminish upon direct fire exposure due to rapid pyrolysis. This study introduces an innovative approach by integrating protective interlayers within the laminate structure to enhance the fire resistance. Various materials, including ceramic composite WHIPOX, titanium foil, poly(etherimide) (PEI) foil, basalt fibers, rubber mat, and hemp fibers, were selected as protective interlayers. These interlayers were strategically placed within the laminate layout to form a sacrificial barrier, safeguarding the integrity of the composite. Bench-scale fire resistance tests were conducted, where fire (180 kW/m2) was applied directly to the one side of the specimen by a burner while a compressive load was applied at the same time. Results indicate significant prolongation of time to failure for CFRP laminates with protective interlayers, which is up to 10 times longer. This innovative approach represents a potential advance in fire protection strategies for CFRP laminates, offering improved resilience against fire-induced structural failure.
Several investigation groups have studied the flame-retardancy modes of action and properties of epoxy resins in the past; nevertheless, the selection of suitable flame retardants for epoxy resins remains challenging, and the transfer to fiber composites is difficult. The addition of flame retardants and glass fibers (GFs) to a polymeric system in a fire scenario changes the polymer's pyrolytic path and burning characteristics, reduces the heat released in the combustion, and suppresses the modes of action in the condensed and gas phase. In this study, the thermal analysis, flammability, fire behavior, residue analysis, fire stability, and quantification of modes of action of three different systems with three halogen-free flame retardants (melamine polyphosphate (MPP), ammonium polyphosphate (APP), and silane ammonium polyphosphate (SiAPP)) and three different types of GFs (unidirectional (UD), bidirectional (BD), and woven roving (WR)) will be compared with pure epoxy resin as a reference.
Revolutionizing our polymer industry for adaption to a sustainable carbon circular economy has become one of today’s most demanding challenges. Exploiting renewable resources to replace fossil-fuel—based plastics with biopolymers such as poly(lactic acid) (PLA) is inevitable while using waste streams as a raw material resource at least is promising. When it comes to using PLA as technical polymer, its high flammability must be addressed by flame retardants compatible with the thermoplastic processing of PLA and its compostability. This study proposes microalgae enriched with phosphorus from wastewater (P-Algae) as an elegant way towards a kind of sustainable organophosphorus flame retardant. The concept is demonstrated by investigating the processing, pyrolysis, flammability, and fire behavior of PLA/P-Algae, while varying the P-Algae content and comparing P-Algae with four alternative bio-fillers (phosphorylated lignin, biochar, thermally treated sewage sludge, and metal phytate) with different P-contents as meaningful benchmarks.
Efficient flame retardancy is often achieved only when applying synergistic multicomponent systems. Flame retardants are combined or used together with adjuvants or synergists to enhance their efficiency, reduce the amount required, or reduce the costs; fibers and fillers contribute to fire properties crucially. Although the main flame-retardant modes of action are known, the detailed scientific understanding usually falls short, when it comes to complex synergistic multicomponent systems, the important tiny optimizations, or quantifying in terms of specific fire properties. This paper tries to illuminate the concept of synergistic flame retardants. The need for the multicomponent approach and the main phenomena are described. Thought-provoking impulses are delivered on how the understanding of multicomponent systems promotes the evidence-based development of future flame retardant polymeric materials. Multicomponent systems are discussed in their capacity as general powerful strategy for achieving and optimizing flame retardant polymeric materials.
This paper is based mainly on the overall conclusions and concrete results of several projects performed in the group of the author. Thanks to my (former) students and co-operation partners in these projects. Thanks for financing to DFG (Scha 730/8-1 Scha 730/8-2, Br 3376/1-1, Scha 730/19-1), AiF IGF (438 ZN, 17833N/2, 19078 N/2), and BMBF (03X0111C, 01DN16040).
Replacing antimony trioxide (ATO) in flame retardant formulations is an urgent task due to its toxicity. There are indications that calcium hypophosphite (CaP) may be a promising replacement. This study investigates the decomposition, fire behavior, and smoke release of brominated flame-retarded acrylonitrile butadiene styrene (ABS) under various fire scenarios like ignition, developing fire and smoldering, while replacing ATO with CaP and CaP/talc. Adding 4 wt.-% of talc to CaP formulations showed beneficial effects on flammability due to changes in the viscosity and barrier properties. Synergism between 8 wt.-% talc and CaP improved the protective layer in the developing fire scenario, resulting in a ∼60 % decrease in the peak of heat release rate and reduction of ∼21 % in total smoke production (ref. ABS+Br+ATO). With a conventional index of toxicity (CIT) of below 0.75, ABS+Br+CaP passes the highest requirements according to EN 45545-2. Overall, the CaP/talc materials improve flame retardancy, show less smoke emission under forced flaming conditions, and prevent chronic intoxication and environmental pollution through smoke particles contaminated with antimony.
Die Präsentation gibt einen Überblick über die Arbeiten im German Pilot des EU-Projekts TREEADS. Es werden klein-, mittel- und großskalige Versuche an Waldboden mit einheimischer Vegetation durchgeführt. Begleitend werden numerische Untersuchungen durchgeführt, die eine Variation der Parameter, wie Bodenfeuchte, Temperaturen und Wind über die Experimente hinaus erlauben. Die gemessenen Materialparameter dienen als Input für die numerischen Berechnungen. Die numerischen Modelle werden mit den mittel- und großskaligen Experimenten validiert.
Weltweit stellen Waldbrände eine große Bedrohung für Umwelt, Wirtschaft und menschliches Leben dar. Der fortschreitende Klimawandel verstärkt Trockenheit und Dürre, wodurch die Größe und Intensität von Waldbränden sowie das daraus resultierende Gefahrenpotential zusätzlich erhöht werden. Um im Risikofall eine schnelle und effektive Waldbrandbekämpfung zu gewährleisten, sollen Einsatzkräfte in Zukunft von KI-basierten Ausbreitungsmodellen unterstützt werden.
Der Einsatz von maschinellem Lernen ermöglicht dabei schnelle und zielgerichtete Ausbreitungsvorhersagen in Echtzeit, die in den Prozess der Brandbekämpfung als zusätzliche Information einfließen können. Im Rahmen des durch das EU-Förderprogram Horizon 2020 finanzierte Projekt TREEADS wird ein solches Modell für Europa entwickelt.
Dazu wird mit verschiedenen Satellitendaten des Copernicus-Programms und der NASA ein auf räumlicher und zeitlicher Ebene aufgelöster Datensatz zu europäischen Waldbränden aufgebaut. Zu den erfassten Waldbränden werden wichtigen Faktoren, die Einfluss auf die Brandausbreitung haben, ergänzt. Dazu gehören das von Copernicus bereitgestellte, digitale Geländemodell Europas und verschiedene, von Sentinel-2 Messungen abgeleitete Informationen zu Vegetation und Landnutzung. Dieser 2D-Trainingsdatensatz zu realen Waldbränden wird durch die zeitlich hochaufgelösten, meteorologischen Reanalyse-Produkte – Copernicus European Regional ReAnalysis (CERRA) und ERA5-Land – vervollständigt und ist die Grundlage für ein Modell zur Ausbreitungsvorhersage von Waldbränden.
Methoden des Maschinellen Lernens können komplexe Muster in den gesammelten Daten erkennen und so zu einer verbesserten Vorhersage der Brandausbreitung beitragen. Die vielfältigen, von Copernicus bereitgestellten Daten sind dabei ein unabdingbarer Bestandteil des Modells, mit dem den Einsatzkräften ein zusätzliches Tool für den effizienten Einsatz ihrer limitierten Ressourcen zur Verfügung steht.
The dripping behaviour of polymers is often observed experimentally through the UL94 flammability standard test. In this work, polymeric dripping under fire is investigated numerically using particle finite element method. A parametric analysis was carried out to observe the influence of a single property on overall dripping behaviour via a UL94 vertical test model. Surrogates and property ranges were defined for variation of the following parameters: glass transition temperature (Tg), melting temperature (Tm), decomposition temperature (Td), density (ρ), specific heat capacity (Cp), apparent effective heat of combustion of the volatiles, char yield (μ), thermal conductivity (k), and viscosity (η). Polyamide, poly(ether ether ketone), poly(methyl methacrylate), and polysulfone were used as benchmarks. Simulated results showed that specific heat capacity, thermal conductivity, and char yield allied with viscosity were the properties that most influenced dripping behaviour (starting time and occurrence).
Mit der Abkehr von der Nutzung fossiler Rohstoffe rücken regenerative Energieträger immer weiter in den Focus. Neben klassischen Holzkohlen werden verstärkt so genannte Biokohlen produziert. Dieser Begriff findet Verwendung für mit Hilfe verschiedener Verfahren karbonisierte pflanzliche, tierische oder mikrobielle Ausgangsstoffe. Diese Kohlen werden zum Teil über weite Strecken zum Bestimmungsort transportiert (Überseetransporte) oder vor Verwendung für längere Zeit gelagert.
Häufig zeigen diese Kohlen ein kritisches Selbstentzündungsverhalten, wobei Einstufungstests (UN N.4 Test) versagen können. Ein negatives Testergebnis des UN N.4 Tests führte dabei in der Vergangenheit zur Nichteinstufung als selbsterhitzungsfähiger Stoff; in der Praxis entzündeten sich aber bereits vergleichsweise kleine Schüttungen (einige m³), z. B. beim Seetransport in Containern. Der Artikel geht auf dieses Problem ein und stellt Prüfverfahren vor. Aus den Ergebnissen durchgeführter Untersuchungen werden Empfehlungen für sicheren Transport und Lagerung abgeleitet.
Mit der Abkehr von der Nutzung fossiler Rohstoffe rücken regenerative Energieträger immer weiter in den Focus. Neben klassischen Holzkohlen werden verstärkt so genannte Biokohlen produziert. Dieser Begriff findet Verwendung für mit Hilfe verschiedener Verfahren karbonisierte pflanzliche, tierische oder mikrobielle Ausgangsstoffe. Diese Kohlen werden zum Teil über weite Strecken zum Bestimmungsort transportiert (Überseetransporte) oder vor Verwendung für längere Zeit gelagert.
Häufig zeigen diese Kohlen ein kritisches Selbstentzündungsverhalten, wobei Einstufungstests (UN N.4 Test) versagen können. Ein negatives Testergebnis des UN N.4 Tests führte dabei in der Vergangenheit zur Nichteinstufung als selbsterhitzungsfähiger Stoff; in der Praxis entzündeten sich aber bereits vergleichsweise kleine Schüttungen (einige m³), z. B. beim Seetransport in Containern. Der Artikel geht auf dieses Problem ein und stellt Prüfverfahren vor. Aus den Ergebnissen durchgeführter Untersuchungen werden Empfehlungen für sicheren Transport und Lagerung abgeleitet.
Biofuels, particularly biodiesel, have gained significant attention as an alternative to traditional fossil fuels in recent years. Unlike diesel, which contains hundreds of compounds, biodiesel only contains a few compounds in the C16-C18 carbon chain. However, the use of biodiesel in automobile and transportation applications can result in problems of degradation or even damage in materials. Among the commonly used polymer materials, fluorocarbon (FKM) shows excellent performance and high stability and compatibility towards oil, diesel, ethanol, and other chemicals. FKM is a family of fluorocarbon-based fluoroelastomer materials, which provide excellent high-temperature and chemical stability compared to other elastomers. As a result, FKM is widely used in chemical processes such as petroleum refining, where it is used for sealings, pumps, and other components.
Mechanical stress often accelerates the failure of polymer materials. The aim of this research is to study the interaction between the sealing material FKM and biofuels B10 (heating oil with 10% biodiesel). The mechanical stress test was carried out in a special apparatus. Both mechanical and non-mechanical stress tests were conducted on specimens at 20, 40, and 70 °C for 28 days to document changes in mass, volume, and tensile properties. Both increasing temperature and mechanical stress have a significant effect on the tensile strength of the FKM polymer when exposed to B10. The combination of increasing temperature and mechanical stress induced rupture within 2 h. It was also established that FKM polymer with pre-exposure in B10 survived longer during mechanical stress compared to specimens exposed only to air. With the support of infrared (IR) spectroscopy, we were able to confirm the penetration of B10 into the FKM polymer.
Holzkohlen im Seeverkehr - Selbstentzündung vermeiden, sichere Beförderungsbedingungen schaffen
(2024)
Mit der Abkehr von der Nutzung fossiler Rohstoffe rücken regenerative Energieträger immer weiter in den Focus. Neben klassischen Holz- und Pflanzenkohlen werden verstärkt so genannte Biokohlen produziert. Dieser Begriff findet Verwendung für mit Hilfe verschiedener Verfahren karbonisierte pflanzliche, tierische oder mikrobielle Ausgangsstoffe. Diese Kohlen werden zum Teil über weite Strecken zum Bestimmungsort transportiert (Überseetransporte) oder vor Verwendung für längere Zeit gelagert.
Häufig zeigen diese Kohlen ein kritisches Selbstentzündungsverhalten, wobei Einstufungstests (UN N.4 Test) versagen können. Ein negatives Testergebnis des UN N.4 Tests führte dabei in der Vergangenheit zur Nichteinstufung als selbsterhitzungsfähiger Stoff; in der Praxis entzündeten sich aber bereits vergleichsweise kleine Schüttungen (einige m³), z. B. beim Seetransport in Containern. Ergebnisse eines Projektes zur systematischen Untersuchung verschiedener Pflanzenkohlen werden vorgestellt.
Mit der Abkehr von der Nutzung fossiler Rohstoffe rücken regenerative Energieträger immer weiter in den Focus. Neben klassischen Holzkohlen werden verstärkt so genannte Biokohlen produziert. Dieser Begriff findet Verwendung für mit Hilfe verschiedener Verfahren karbonisierte pflanzliche, tierische oder mikrobielle Ausgangsstoffe. Diese Kohlen werden zum Teil über weite Strecken zum Bestimmungsort transportiert (Überseetransporte) oder vor Verwendung für längere Zeit gelagert.
Häufig zeigen diese Kohlen ein kritisches Selbstentzündungsverhalten, wobei Einstufungstests (UN N.4 Test) versagen können. Ein negatives Testergebnis des UN N.4 Tests führte dabei in der Vergangenheit zur Nichteinstufung als selbsterhitzungsfähiger Stoff; in der Praxis entzündeten sich aber bereits vergleichsweise kleine Schüttungen (einige m³), z. B. beim Seetransport in Containern. Der Artikel geht auf dieses Problem ein, stellt Prüfverfahren vor und gibt Empfehlungen für sicheren Transport und Lagerung.
Mit der Abkehr von der Nutzung fossiler Rohstoffe rücken regenerative Energieträger immer weiter in den Focus. Neben klassischen Holzkohlen werden verstärkt so genannte Biokohlen produziert. Dieser Begriff findet Verwendung für mit Hilfe verschiedener Verfahren karbonisierte pflanzliche, tierische oder mikrobielle Ausgangsstoffe. Diese Kohlen werden zum Teil über weite Strecken zum Bestimmungsort transportiert (Überseetransporte) oder vor Verwendung für längere Zeit gelagert.
Häufig zeigen diese Kohlen ein kritisches Selbstentzündungsverhalten, wobei Einstufungstests (UN N.4 Test) versagen können. Ein negatives Testergebnis des UN N.4 Tests führte dabei in der Vergangenheit zur Nichteinstufung als selbsterhitzungsfähiger Stoff; in der Praxis entzündeten sich aber bereits vergleichsweise kleine Schüttungen (einige m³), z. B. beim Seetransport in Containern. Der Artikel geht auf dieses Problem ein, stellt Prüfverfahren vor und gibt Empfehlungen für sicheren Transport und Lagerung.
Combining buffing leather fibers from industrial waste streams with ammonium polyphosphate and bentonite clay is proposed as a flame-retardant additive for polypropylene. The paper addresses how they can be processed into attractive composites with the desired mechanical properties. Buffing leather fibers function as a multifunctional bio-filler and as a synergist for the flame retardant, resulting in fire retardancy successful enough to increase the oxygen index (LOI) by up to 7 vol.-% and to achieve a V0 UL 94 classification. Impressively reduced heat release rates are obtained in the cone calorimeter at 50 kW/m2 irradiation; for instance, the maximum average rate heat evolved (MARHE) drops from 765 to below 200 kW m 2. The synergistic effects are quantified and shown to be very strong for LOI and MARHE. This work opens the door to use waste buffing leather fibers as a promising multifunctional and synergistic bio-filler.
To ensure fire safety, polymers are filled with flame retardants and smoke suppressants. To meet the highest requirements, it is essential to understand the decomposition of those polymeric materials. This study reveals interactions between polymer, smoke suppressants, and flame retardants, and discusses their impact on the materials’ flame retardancy, smoke emission, smoke toxicity, and particle emission in conventional loadings to provide deeper general understanding. Low melting oxide glass, melem, spherical silica, sepiolite, melamine polyphosphate, and boehmite in an aluminum diethylphosphinate flame-retarded polyamide 6.6 were investigated. All smoke suppressants improve the protective layer and act as an adjuvant. Silica and melem performed best under forced flaming conditions. Spherical silica reduces the peak of heat release rate by 39% and the total heat evolved by 14%, whereas 10 wt% melem lowers the total smoke production by 41%. Melem alters the mode of action of aluminum diethylphosphinate from gas to more condensed phase activity. This change reduces flame inhibition and hence smoke toxicity, but further improves the protective layer due to charring reactions in the decomposition mechanism. In addition, the sizes of the smoke particles decrease because of the prolonged time in the pyrolytic zone. This study highlights that interactions between polymer, flame retardants, and smoke suppressants can significantly determine the smoking and burning behavior.
AbstractThe increasing threat of forest fires on a global scale is not only a matter of concern due to the potential harm they may cause to both human and animal life but also due to their significant role in exacerbating climate change. In light of these circumstances, one might inquire as to whether forest soil can self‐ignite and, if so, under what conditions and at what temperatures this phenomenon may occur. This question is being addressed in the German pilot “Fire science of wildfires and safety measures” of the EU project TREEADS, and the first results are presented below. The importance of basic research into the self‐ignition of forest soil cannot be underestimated, as it provides crucial knowledge to prevent forest fires and protect human and animal health. Furthermore, mitigating the occurrence of forest fires can also play a role in reducing greenhouse gas emissions, contributing to global efforts to combat climate change. The procedure of the hot storage test is an effective means of determining whether a material can self‐ignite. During the investigation of six soil samples, it was found that five of them were indeed capable of self‐ignition. In addition to determining whether the material ignites, the modified hot storage test also analyzed the resulting smoke gases and measured their concentration. The research question of whether regional forest soil is capable of self‐ignition can be answered with yes based on these initial tests. Further experiments are needed to determine if self‐ignition causes forest fires.
Understanding the susceptibility to spalling of concrete members in case of fire is important to evaluate the residual load-bearing capacity. The investigations of the spalling phenomenon of a concrete mixture using real scale members are necessary but expensive to carry out. Reducing the specimen size leads to an increase of boundary effects that can result in a reduced spalling or absence of spalling. In this study, fire tests were carried out on unrestrained, single-sided exposed, cuboid shaped specimens (0.6 m x 0.6 m x 0.29 m) as well as unrestrained and steel ring restrained cylindrical specimens (Ø = 0.47 m, h = 0.29 m), which induce different boundary conditions. These fire tests were carried out on two ordinary concrete mixtures. The two mixtures differ only in the type of aggregates (quartz gravel and basalt grit) and were used to investigate the influence of the thermal expansion of the aggregate on the spalling behaviour of the concrete. The results show a significant increase of
the spalling depth due to the restrained thermal expansion achieved by the applied steel rings. Additionally, the type of aggregate has a direct influence on the spalling behaviour of a concrete mixture. The reduction of the boundary effects by the steel rings recreate the test conditions in the centre of a large concrete member. Thus, this type of specimen is suitable to determine the susceptibility to spalling of a material (screening-tests) as preliminary investigations to full scale fire tests.
Pressure-sensitive adhesive tapes are used in several industrial applications such as con-struction, railway vehicles and the automotive sector,where the burning behavior is ofcrucial importance. Flame retarded adhesivetapes are developed and provided, however,often without considering the interaction of adhesive tapes and the bonded materialsduring burning nor the contribution of the tapes to fire protection goal of the bondedcomponents in distinct fire tests. This publication delivers an empirical comprehensiveknowledge how adhesive tapes and their flame retardancy effect the burning behaviorof bonded materials. With a special focus on the interaction between the single compo-nents, one flame retarded tape and one tapewithout flame retardant are examined inscenarios of emerging and developing fires, along with their bonds with the commonmaterials wood, zinc-plated steel, mineral wool, polycarbonate, and polymethylmethacry-late. The flame retardant significantly improved the flame retardancy of the tape as afree-standing object and yielded a V-2 rating in UL 94 vertical test and raised the OxygenIndex by 5 vol.%. In bonds, or rather laminates, the investigations prove that the choiceof carrier and substrates are the factors with the greatest impact on the fire propertiesand can change the peak of heat release rate and the maximum average rate of heatemission up to 25%. This research yielded a good empirical overall understanding of thefire behavior of adhesive tapes and bonded materials. Thus, it serves as a guide for tapemanufacturers and applicants to develop tapes and bonds more substrate specific.