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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).
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.
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.
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.
Produkte, Bauteile und Konstruktionen im Transport- und Bauwesen bestehen mehr und mehr aus Klebverbunden. Allein die Menge des verwendeten Klebstoffes oder die Anzahl geklebter Verbindungen schließen für eine verlässliche Betrachtung und Bewertung der Brandrisiken aus, deren Beitrag zur Brandentstehung, Flammenausbreitung oder Feuerwiderstand von Baugruppen und Konstruktionen zu vernachlässigen. Anforderungen an die Leistungsbeschreibungen von flammgeschützten Klebstoffen bzw. Haftklebebändern werden definiert, oft ohne ein ausreichendes Verständnis der Beiträge von Klebverbunden zum Brandverhalten der Bauteile zu haben. Der Vortrag beleuchtet diese Problematik und stellt die verschiedenen komplexen Anforderungen aus dem Brandschutz in Hinblick auf Auswahlkriterien und Entwicklungsziele für flammgeschützte Klebstoffe dar. Dabei ist dieser Transfer des Brandverhaltens, sprich der Systemantwort einer Komponente oder Bauteils in einem spezifischen Brandszenario, in Materialeigenschaften des Klebstoffes eine intrinsische und anspruchsvolle Herausforderung. Im abgeschlossenen IGF-Projekt Nr. 20762 N (Forschungsvereinigung DECHEMA) haben wir für Klebebänder eine systematisch-wissenschaftliche Studie durchgeführt und aussagekräftige Erkenntnisse zu Verfügung gestellt. Die Untersuchungen zur Entflammbarkeit zu Brandbeginn, zur Flammenausbreitung (Wärmeentwicklung) im sich entwickelnden Brand und zum Feuerwiderstand im Vollbrand machen die sehr unterschiedlichen Einflüsse von Klebverbunden, d. h. auch die unterschiedlichen Anforderungen an die Modifikation der Klebebänder, deutlich. Die thermische Analyse verschiedener Klebstoffe zusammen mit den Brandtest freistehender Haftklebebänder, an einseitig geklebten Substraten und an Klebverbundprobekörpern skizzieren eindrucksvoll die komplexen Zusammenhänge zwischen Materialeigenschaften der Klebebänder und dem Brandverhalten von Klebverbunden. Der Vergleich von verschiedenen Substraten wie Stahlbleche, Holz, Mineralwolle und verschiedene Polymermaterialien belegt darüber hinaus, dass der Einfluss der Klebverbindungen auf das Brandverhalten der Klebverbunde substratspezifisch ist. Gerade der Vergleich zwischen Holz, Polymethylmethacrylat (PMMA) und Bisphenol A Polycarbonat (PC) liefert überraschend unterschiedliche Ergebnisse. Die Variation der Klebstoffe und Trägermaterialien der Klebebänder skizziert die verschiedenen Möglichkeiten für die Materialentwicklung. Abhängig vom Material und Brandszenario können Klebverbunde im Vergleich zu gleich dicken Probekörpern aus demselben Substrat sowohl eine deutliche Erhöhung der Brandrisiken, ein praktisch unverändertes Brandverhalten oder eine Reduktion des Brandrisikos hervorrufen. Grundsätzlich kann keine Lösung bzw. kein Tape gefunden werden, die mit allen Substraten einen guten Brandschutz gewährleistet. Substrate, Carrier und Klebstoff müssen nicht nur aufeinander abgestimmt werden, sondern auch auf das Brandszenario, in welchem der Verbund eine gute Performance liefern soll.Das IGF-Projekt (20762) der Forschungsgemeinschaft (DECHEMA Deutsche Gesellschaft für Chemische Technik und Biotechnologie e V, Theodor Heuss Allee 25, 60486 Frankfurt am Main) wurde durch die AiF im Rahmen des Programms „Förderung der Industriellen Gemeinschaftsforschung (IGF)” des Bundesministeriums für Wirtschaft und Klimaschutz aufgrund eines Beschlusses des Deutschen Bundestages gefördert.
In the processing of nanocomposites, high shear stresses at elevated tempera-tures orient two-dimensional nanoparticles like graphene. This orientationleads to anisotropic mechanical, thermal or barrier properties of the nanocom-posite. This anisotropy is addressed in this study by comparing graphene (few-layer graphene, FLG) with a nanoscaled carbon black (nCB) at a filler contentof 3 phr, by varying the vulcanization, and by comparing different FLG con-tents. Transmission electron microscopy gives insight into the qualitative ori-entation in the nanocomposite with FLG or nCB. The storage moduli paralleland normal to the orientation reveal the direction dependency of reinforce-ment through dynamic mechanical analysis (DMA). Dimensional swellingmeasurements show a restriction of the expansion parallel to the FLG orienta-tion, and an increased expansion normal to the orientation. The vulcanizationsystem and crosslinking determine the respective level of property values, andhigher crosslinking densities increase the anisotropy in DMA resulting invalues of up to 2.9 for the quantified anisotropy factor. With increasing FLGcontent, the anisotropy increases. A comparison of the results reveals swellingmeasurements as the most suitable method for the determination of anisot-ropy. Compared to recent literature, the presented processing induces higheranisotropy, leading to higher reinforcing effects in the direction of orientation
The impact of phosphorus-containing flame retardants (FR) on rigid polyisocyanurate (PIR) foams is studied by systematic variation of the chemical structure of the FR, including non-NCO-reactive and NCO-reactive dibenzo[d,f][1,3,2]dioxaphosphepine 6-oxide (BPPO)- and 9,10 dihydro-9-oxa-10 phosphaphenanthrene-10-oxide (DOPO)-containing compounds, among them a number of compounds not reported so far. These PIR foams are compared with PIR foams without FR and with standard FRs with respect to foam properties, thermal decomposition, and fire behavior. Although BPPO and DOPO differ by just one oxygen atom, the impact on the FR properties is very significant: when the FR is a filler or a dangling (dead) end in the PIR polymer network, DOPO is more effective than BPPO. When the FR is a subunit of a diol and it is fully incorporated in the PIR network, BPPO delivers superior results.
Main message: Sustainability, or in other words, exploiting environmental conservation for the economic welfare and prosperity for all, would revolutionise the plastics industry were it to become predominant practice as a linear, fossil-fuel–based economy is switched to a carbon circular economy. Food for though is given by dint of a critical overview of the current trends in sustainable flame-retardant polymeric materials.
Introduction:
Transforming the plastics industry into a carbon circular economy over the next 30 years requires an immediate revolution entailing the development of cutting-edge materials and the planning of future industrial production plants. Hence, the innovative field of flame-retardant polymeric materials should lend its strength to drive this challenge. Visionary solutions are proposed to inspire us, while the implementation of economically feasible concepts can take us forward into the future.
Experimental The synthesis, processing, polymer analysis, thermal analysis, and investigation of fire behaviour from our own research are performed according to the state of the art, mostly in accordance with the pertinent ISO standards. Indeed, some of our equipment is part of the accredited lab; for the other methods we fulfil equivalent quality standards in terms of maintenance, calibration, participation in round robins, etc. Work steps such as the synthesis or preparation of new materials are usually outsourced or done with partners that have the relevant core competence. The talk also presents examples from other groups whose experimental is described in the corresponding scientific papers.
Results and Discussion An overview of current trends towards producing sustainable, flame-retardant polymeric materials is presented, using examples from the literature and by sketching our own projects performed in recent years. The examples are structured along a common theme leading from the use of old and new natural materials with some intrinsic flame retardancy, via flame-retardant biopolymers and biocomposites, to using renewable sources for flame retardants with the objective of exploiting natural sources available as industrial waste streams. Natural flame retardants and adjuvants are highlighted, although the status of most may be assessed as merely motivating our vision. Nevertheless, there are natural material streams finding their way into polymer mass production as fillers, adjuvants, polymers, or renewable educt sources. Natural substances originating from industrial waste streams open the door to sustainable solutions, because they are often available at low cost and avoid competition for land with farming or virgin forests. Aside from this main topic, remarks will address the recycling of flame-retarded polymeric materials; vitrimers are mentioned as a potential material for recyclable thermosets. At the end of the day, only convincing property profiles will prevail both for exploiting renewable sources and circular design, including cost effectiveness, sufficient availability, consistent quality, processibility, mechanical properties, and flame retardancy. However, sustainability must not be merely tolerated as an additional demand, but should instead be recognized as a solution, because sustainability aspires to ensure our economic welfare now and in the future.
Acknowledgement:
The examples shown from own project were supported by funding grants: BMBF WTZ: 01DN16040, DFG Scha 730/19-1, VW-Stiftung: Experiment No: 97437, DFG Scha 730/20-1, BMBF KMU Innovativ 031B1289B.
Only the nano-scaled structure of the nanocomposite and the dispersion of nanoparticles within the polymer matrix harbor multifunctional potential including superior fire retardancy. Thus, this chapter focuses on the dispersion of nanoplates, based mainly on studies of layered silicates and graphene/graphene-related nanoplates. The nanostructure and properties of the nanocomposites are dependent mainly on thermodynamic and kinetic factors during preparation. Improving nano-dispersion often directly improves flame retardancy. Therefore, the modification of the nanoplates as well as the preparation of nanocomposites becomes very important to control this dispersion. The dispersion of nanoplates functions as a prerequisite for the formation of an efficient protective layer, changing the melt flow and dripping behavior, or the improvement of the char properties.
Polyamide 4.6 (PA46) is a high-heat-resistant polymer, but it has no dripping resistance under fire. Three commercial grades of PA46 are investigated under UL 94 vertical fire test conditions. Their performances are discussed based on the materials’ structural, thermal, and rheological properties. PA46 presents flaming drops, whereas dripping is prevented in the flame-retarded PA46.
Friction-modified PA46 has increased flaming dripping. Temperature profiles of the specimens under fire and the temperature of the drops are measured by thermocouples. A UL 94 vertical test configuration consisting of two flame applications is designed to assess the quantitative dripping behavior of the set of materials by the particle finite element method (PFEM). Polymer properties (activation energy and Arrhenius coefficient of decomposition, char yield, density, effective heat of combustion, heat of decomposition, specific heat capacity, and thermal conductivity) in addition to rheological responses in high temperatures are estimated and measured as input parameters for the simulations. The dripping behavior obtained by simulated materials corresponds with the experimental results in terms of time and drop size. A consistent picture of the interplay of the different phenomena controlling dripping under fire appears to deliver a better understanding of the role of different materials’ properties