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Eingeladener Vortrag
- nein (6)
Synergistic multicomponent systems containing melamine poly(metal phosphate)s have been recently proposed as flame retardants. This work focuses on the decomposition pathways, molecular mechanisms and morphology of the fire residues of epoxy resin (EP) flame retarded with melamine poly(zinc phosphate) (MPZnP) to explain the modes of action and synergistic effects with selected synergists (melamine polyphosphate (MPP) and AlO(OH), respectively). The total load of flame retardants was always 20 wt.%. The decomposition pathways were investigated in detail via thermogravimetric Analysis coupled with Fourier transform infrared spectroscopy. The fire residues were investigated via elemental analysis und solid-state nuclear magnetic resonance spectroscopy. The morphology of intumescent fire residues was investigated via micro-computed tomography and scanning electron microscopy.
EP + (MPZnP + MPP) formed a highly voluminous residue that showed structural features of both EP + MPZnP and EP + MPP, resulting in a highly effective protection layer. EP + (MPZnP + AlO(OH)) preserved the entire quantity of phosphorus content during combustion due to the Formation of Zn₂P₂O₇ and AlPO₄.
Wesentlich für das Sicherheitsniveau und damit die nachhaltige Wettbewerbsfähigkeit des Technologiestandortes Deutschland ist der Brandschutz in Industrieanlagen, in Gebäuden und im Transportwesen. Der vorbeugende bauliche Brandschutz hat u. a. das Ziel, die Brand- und Rauchausbreitung im Brandfall für eine gewisse Zeit zu behindern, damit die erforderlichen Lösch- und Rettungsarbeiten durchgeführt werden können. Dies geschieht u.a. durch Anforderungen an die Feuerwiderstandsfähigkeit brandbeanspruchter Bauteile. Der Feuerwiderstand eines Bauteils ist die Fähigkeit während eines angegebenen Zeitraums in einer genormten Feuerwiderstandsprüfung bezüglich mechanischer Stabilität und/oder thermischer Isolierung nicht zu versagen. Reaktive Brandschutzbeschichtungen erhöhen für viele Bauteile sehr effektiv den Feuerwiderstand. Die Beschichtungen und die Brandprüfungen müssen jedoch an die immer komplexeren Anwendungen und/oder extremeren Anforderungen angepasst und weiterentwickelt werden. Aktuelle Forschungsschwerpunkte liegen dabei in der Entwicklung neuer Materialien (z.B. Geopolymere, keramisierende Beschichtungen, silikonbasierte Beschichtungen) für extreme Brandszenarien (extreme Temperaturen, lange Beanspruchungszeiten) und in der Realisierung komplexer Funktionalitäten (komplexe Geometrien, bewegliche Komponenten) sowie in der Entwicklung neuer Testmethoden (Feuerwiderstand als bench-scale Tests, kostengünstiges Screening, Feuerwiderstand in extremen Brandszenarien). Die Entwicklung geht dabei weg von der präskriptiven Bewertung hin zur leistungsorientierten (performance-based) Bewertung in individuellen Brandszenarien oder von komplexen Bauteilen. Im Rahmen dieser Arbeit werden Lösungsansätze für die neuen Herausforderungen an die reaktiven Brandschutzsysteme unter Extrembedingungen und deren Testmöglichkeiten vorgestellt und diskutiert. Im Mittelpunkt stehen dabei neu entwickelte bench-scale Testmethoden zum Screening von neuen Beschichtungsmaterialien sowie zur Beurteilung spezieller bzw. materialspezifischer Aspekte des Feuerwiderstands unter Extrembedingungen.
Research and development of flame retarded polymeric materials generate a strong demand for bench-scale fire testing saving costs, time, and material. Hereby the good correlation to the fire tests mandatory for later products is the key challenge. Three examples are presented for tailored bench-scale fire test set-ups based on recent projects in my working group:
- STT MuFu+: A bench-scale set-up was designed to investigate intumescent coatings protecting steel. An electric oven was modified, so that the standard time temperature curve is applied to a 75 mm x 75 mm coated steel plate. The plate is tested in a vertical position the temperature increase is measured at its back. A high temperature endoscope is used for online observation of the intumescence. Perfect fire residues are produced ready for further investigation.
- Rapid Mass Calorimeter: A bench-scale set-up was designed to speed up cone calorimeter testing. Specimen size reduction and using a modified mass loss calorimeter deliver crucial reduction in time and material needed for screening materials. More than 70 different materials, polymers and flame retarded polymers, have been used to understand the meaning of the results and to check the correlation with cone calorimeter results.
- Bench-scale Cable Testing Module: A bench-scale set-up was designed to screen cables with respect to their performance in the large scale test (EN 50399). A module is proposed replacing the cone heater and balance in the cone calorimeter. Thus the whole set-up of the cone calorimeter is used determining the heat release by means of oxygen consumption, whereas the novel cable module become cheap and easy. A good correlation to EN 50399 was observed indicating the module being an excellent screening tool for the development of flame retardant cables.
The three examples show how close tailored bench-scale testing comes to simulate the performance in larger mandatory fire tests. Proper bench-scale approaches are used for reliable inexpensive assessment when screening novel materials and products.
Acknowledgements
Thanks go to Michael Morys, who has elaborated the STT MuFu+ in his PhD, and Sebastian Rabe, who has elaborated the Rapid Mass Calorimeter in his PhD. Thanks go to Corning Optical Communications (Emanuela Gallo and Waldemar Stöcklein) for the joint project developing the Bench-scale Cable Testing Module. Thanks go to Patrick Klack elaborating the cable module.
Rubbers are usually reinforced with a high content (> 40 phr) of carbon black (CB) and silica. In recent years several nanofillers have been proposed, including expanded graphite/graphene. Extremely low loading of nanoparticles can considerably improve the properties. In this contribution multilayer graphene (MLG) is investigated as efficient nanofiller for rubbers. MLG has a BET specific surface area of 250 m2/g. Compared to a single graphene sheet, the MLG used constitutes only approximately 10 graphene sheets.
When homogenously dispersed, it works at low loadings enabling the replacement of CB, increase in efficiency, or reduction in filler concentration. Actually the appropriate preparation yielded nanocomposites in which just 3 phr are sufficient to significantly improve the rheological, curing and mechanical properties of different rubbers, as shown for Chlorine-Isobutylene-Isoprene Rubber (CIIR), Nitrile-Butadiene Rubber (NBR), Natural Rubber (NR), and Styrene-Butadiene Rubber (SBR).
A mere 3 phr of MLG tripled the Young’s modulus of CIIR, an effect equivalent to 20 phr of carbon black. Similar equivalents are observed for MLG/CB mixtures. MLG reduces gas permeability, increases thermal and electrical conductivities, and retards fire behavior. The higher the nanofiller concentration is (3 phr, 5 phr, and 10 phr was investigated), the greater the improvement in the properties of the nanocomposites. Moreover, the MLG nanocomposites improve stability of mechanical properties against weathering. An increase in UV-absorption as well as a pronounced radical scavenging are proposed and were proved experimentally. To sum up, MLG is interesting as multifunctional nanofiller and seems to be quite ready for rubber development.
Multilayer Graphene (MLG), a nanoparticle with a specific surface of BET = 250 m²/g and thus made of only approximately 10 graphene sheets, is proposed as a nanofiller for rubbers. When homogenously dispersed, it works at low loadings enabling the replacement of carbon black (CB), increase in efficiency, or reduction in filler concentration. Actually the appropriate preparation yielded nanocomposites in which just 3 phr are sufficient to significantly improve the rheological, curing and mechanical properties of different rubbers, as shown for Chlorine-Isobutylene-Isoprene Rubber (CIIR), Nitrile-Butadiene Rubber (NBR), Natural Rubber (NR), and Styrene-Butadiene Rubber (SBR). A mere 3 phr of MLG tripled the Young’s modulus of CIIR, an effect equivalent to 20 phr of carbon black. Similar equivalents are observed for MLG/CB mixtures. MLG reduces gas permeability, increases thermal and electrical conductivities, and retards fire behavior. The later shown by the reduction in heat release rate in the cone calorimeter. The higher the nanofiller concentration is (3 phr, 5 phr, and 10 phr was investigated), the greater the improvement in the properties of the nanocomposites. Moreover, the MLG nanocomposites improve stability of mechanical properties against weathering. An increase in UV-absorption as well as a pronounced radical scavenging are proposed and were proved experimentally. To sum up, MLG is interesting as a multifunctional nanofiller and seems to be quite ready for rubber development.
The functionalization of a natural sodium montmorillonite (MMT) with (3-glycidyloxypropyl)trimethoxysilane by a silylation procedure is presented, and its use as nanofiller in the melt compounding of low density polyethylene (LDPE) nanocomposites. In particular, the effects on the thermal stability and flame retardant properties of melt compounded LDPE nanocomposites are analyzed, with and without magnesium hydroxide (MH) as an additional conventional flame retardant. The purpose was to investigate possible synergistic effects between the two inorganic fillers on fire behavior. The obtained organosilylated clay showed higher interlayer spacing than the original MMT and good thermal stability, higher than that of many commercial organoclays modified with alkylammonium salts. Its addition to LDPE allowed the production of hybrids with nanoscale dispersion of the filler, as demonstrated by X-ray diffraction. The simultaneous presence of MH, which strongly interacts with the nanoclay, hindered intercalation of the polymer chains between the clay galleries and clay layer exfoliation within the LDPE resin.
The investigation of the thermal and burning behavior of the LDPE nanocomposites indicated that the organosilylated clay alone shows only a limited residual protection layer effect. In combination with MH the nanocomposites have a small adverse effect on the reaction to small flame as measured by the Oxygen index and UL 94 testing, and, surprisingly, no effect on the peak heat release rate in the cone calorimeter. The quality of the fire residue was lacking on the microscopic scale. The ternary LDPE/MH/ organoclay systems investigated did not open the door to reducing MH content in halogen-free flame retardant LDPE yet, but demand further research.
Multilayer graphene/chlorine-isobutene-isoprene rubber nanocomposites: the effect of dispersion
(2016)
Multilayer graphene (MLG) is composed of approximately 10 sheets of graphene. It is a promising nanofiller just starting to become commercially available. The Dispersion of the nanofiller is essential to exploit the properties of the nanocomposites and is dependent on the preparation method. In this study, direct incorporation of 3 parts per hundred of rubber (phr) MLG into chlorine-isobutene- isoprene rubber (CIIR) on a two-roll mill did not result in substantial enhancement of the material properties. In contrast, by pre-mixing the MLG (3 phr) with CIIR using an ultrasonically assisted solution mixing procedure followed by two-roll milling, the properties (rheological, curing, and mechanical) were improved substantially compared with the MLG/CIIR nanocomposites mixed only on the mill. The Young’s moduli of the nanocomposites mixed in solution increased by 38%. The CIIR/MLG nanocomposites produced via solution showed superior durability against weathering exposure.
Multilayer Graphene (MLG), a nanoparticle with a specific surface of BET = 250 m2/g and thus made of only approximately 10 graphene sheets, is proposed as a nanofiller for rubbers. When homogenously dispersed, it works at low loadings enabling the replacement of carbon black (CB), increase in efficiency, or reduction in filler concentration. Actually the appropriate preparation yielded nanocomposites in which just 3 phr are sufficient to significantly improve the rheological, curing and mechanical properties of different rubbers, as shown for Chlorine-Isobutylene-Isoprene Rubber (CIIR), Nitrile-Butadiene Rubber (NBR), Natural Rubber (NR), and Styrene-Butadiene Rubber (SBR). A mere 3 phr of MLG tripled the Young’s modulus of CIIR, an effect equivalent to 20 phr of carbon black. Similar equivalents are observed for MLG/CB mixtures. MLG reduces gas permeability, increases thermal and electrical conductivities, and retards fire behavior. The later shown by the reduction in heat release rate in the cone calorimeter. The higher the nanofiller concentration is (3 phr, 5 phr, and 10 phr was investigated), the greater the improvement in the properties of the nanocomposites. Moreover, the MLG nanocomposites improve stability of mechanical properties against weathering. An increase in UV-absorption as well as a pronounced radical scavenging are proposed and were proved experimentally. To sum up, MLG is interesting as a multifunctional nanofiller and seems to be quite ready for rubber development.
Intermediate-scale testing is indispensable when investigating the fire resistance under simultaneous compressive load of components made of glass- and carbon-fibre-reinforced composites (GFRP and CFRP). BAM is successfully operating an intermediate-scale test stand, developed for a specimen size of 500 mm x 500 mm (1000 mm). The fire resistance in terms of fire stability of CFRP and GFRP sandwiches are investigated, e.g. at 20 % of their compressive failure load at room temperature. Times to failure increase by up to a factor of 4 due to intumescent coatings. For GFRP sandwiches, different core structures with and without additional flame retardants show an astonishing impact on time to failure. CFRP shell structures are investigated on the intermediate scale with and without stringer reinforcements, resulting in completely different mechanical failure behaviour in the ultimate load test as opposed to the fire resistance test. The stringers become the only load-carrying part, while the shell acts as a protective layer. Thus the design exploiting this self-protection potential, i.e. the residue of the front skin protecting the load-bearing structure, is highlighted as a most promising route to enhance the fire resistance of lightweight materials.
Intermediate-scale testing is indispensable when investigating the fire resistance under simultaneous compressive load of components made of glass- and carbon-fibre-reinforced composites (GFRP and CFRP). BAM is successfully operating an intermediate-scale test stand, developed for a specimen size of 500 mm x 500 mm (1000 mm). The fire resistance in terms of fire stability of CFRP and GFRP sandwiches are investigated, e.g. at 20 % of their compressive failure load at room temperature. Times to failure increase by up to a factor of 4 due to intumescent coatings. For GFRP sandwiches, different core structures with and without additional flame retardants show an astonishing impact on time to failure. CFRP shell structures are investigated on the intermediate scale with and without stringer reinforcements, resulting in completely different mechanical failure behaviour in the ultimate load test as opposed to the fire resistance test. The stringers become the only load-carrying part, while the shell acts as a protective layer. Thus the design exploiting this self-protection potential, i.e. the residue of the front skin protecting the load-bearing structure, is highlighted as a most promising route to enhance the fire resistance of lightweight materials.