Fire Science
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Eingeladener Vortrag
- nein (25)
Der Beitrag versucht sich an der Herausforderung, trotz beschränktem zeitlichen Rahmen einen ansprechenden Spagat zwischen umfangreichem Überblick und wissenschaftlichem Verständnis und so eine unabhängige und unparteiliche Einführung in Thematik flammgeschützte PUR-Schäume zu geben. Er kann sicherlich nicht individuelle Antworten oder konkrete Entwicklungsziele wie neue Rezepturvorschläge liefern, aber hofft zum Hintergrund und als Handwerkzeugs für das Aufstellen und Überdenken von Entwicklungsstrategien beizutragen.
Small and large-scale tests have been carried out Pressure vessel – to improve numerical modelling Different types of fire must be distinguished Modelling of vessels were discussed Test configuration has been developed to see what happens in the vessel First results encourage us to continue the Research Thermohydraulics needs further work (boundary layers).
Die Erkenntnisse zu reaktiven Brandschutzsystemen (RBS) werden kontinuierlich erweitert, was sich in der Entwicklung neuer Produkte und der Ausweitung des durch technische Regelungen abgedeckten Anwendungsbereichs äußert. Der hier vorliegende Beitrag konzentriert sich auf die Verwendung von RBS auf Stahlkonstruktionen. In den vergangenen zehn Jahren wurden, abgesichert durch neue Erkenntnisse aus der Forschung, die Anwendung auf Stahlzuggliedern mit offenem Profil präzisiert und im Rahmen allgemeiner bauaufsichtlicher Zulassungen (abZ) neu geregelt. Ferner wurde die Grundlage geschaffen, die Anwendung von RBS auf Zuggliedern mit kreisrundem Vollprofil zu bewerten und auf Basis der abZ zu ermöglichen.
Neben einer umfassenden Darstellung der aktuellen nationalen und europäischen Regelungen zu RBS, werden technologische Besonderheiten und deren Einfluss auf den Regelungsinhalt im Beitrag thematisiert.
In der jüngsten Vergangenheit stellt sich mit zunehmender Dringlichkeit die Frage nach der Bewertung der Dauerhaftigkeit von RBS für lange Zeiträume, wobei damit Nutzungsdauern weit jenseits der in den nationalen und europäischen Regelungen bereits etablierten 10 Jahre gemeint sind. In diesem Zusammenhang ist zu klären, wie der Feuerwiderstand von Konstruktionen zu bewerten ist, die bereits über lange Zeiträume mit RBS versehen sind. Nicht zuletzt stellt sich die Frage nach der Dauerhaftigkeit der Systeme selbst und adäquaten Prüfverfahren zu deren Beantwortung. Neue und bereits etablierte Ansätze werden vorgestellt und diskutiert.
Der Beitrag schließt mit einer Darstellung der aktuellen Forschung. Neben den Forschungsaktivitäten zur Dauerhaftigkeit sind hier insbesondere Untersuchungen zur Anwendung und Bewertung von RBS auf Grundlage von Naturbränden und extremen Brandereignissen genannt. Neuste Untersuchungen befassen sich auch mit der Anwendung von RBS auf
komplexen Geometrien wie auch auf anderen Substraten wie Beton, Aluminium und faserverstärkten Kunststoffen sowie hybriden Werkstoffen. Die hybriden Werkstoffe aus der Kombination von Metallen und Verbundwerkstoffen sind derzeit vorwiegend im Behälter-, Fahrzeug- und Flugzeugbau anzutreffen. Auch die bereits vor Jahrzehnten begonnenen Aktivitäten zur Entwicklung rechnerischer Verfahren zur Beurteilung der Wirkungsweise von RBS werden in der aktuellen Forschung fortgeführt und weiterentwickelt.
Benefits of hyperbranched structure:
Molecular weight, miscibility, number of FR groups, end-group functionalization, glass transition temperature, decreased PBT.
Examples of hyperbranched FRs:
Charring agent, silicone, triazine, etc.
Systematic study of effect of chemical surrounding and impact of Complex shape of phosphorus-based hyperbranched polymers on flame retardant efficacy in epoxy resins.
In continuation of a preceding test series involving sole LPG vehicle tanks, three passenger cars equipped with identical toroidal steel LPG tanks were set on fire. The tanks were installed in the space normally reserved for the spare tyre, in the car boot. No safety device was installed on the tank, in order to force critical failure of the cylinder. Two of the cars were equipped with a tank filled with liquefied propane to a level of 20% (5.3 kg), the third one was filled completely (25.5 kg). The partially filled tanks failed critically within a time period of more than 20 min after the initiation of the fire. The fully-filled tank did not rupture; the propane was released continuously through a small leak that appeared during the fire. Comprehensive equipment was used to procure measurement data, enabling an analysis of potential consequences and hazards to humans and infrastructure within the vehicle surroundings. The inner status of the tank (pressure, temperature of the liquid phase and the steel casing), the development of the fire (temperature inside and around the vehicle) and the pressure induced in the near-field in case of tank rupture were recorded. The results were analysed in detail and compared against the data gained in tests involving sole, but identical LPG tanks.
Thermoplastic polyurethane - How thespecific two-stage decompositioncontrols its fire behavior
(2018)
Thermoplastic polyurethanes (TPUs) are one of the major classes of thermoplastic elastomers used in the cable and wire industry. Due to their chemical structure, they are considered as linear block copolymers with alternating hard and soft segments. This specific structure is not only responsible for the excellent mechanical properties of TPU like high tensile strength or abrasion resistance, but it also influences the pyrolysis and burning behavior. TPU is a highly flammable polymer which forms liquid pool fires or burning drops which results in intensive flame spread. Because of that, TPU often does not meet the strict requirements for indoor applications given by the cable market.
Under thermal stress, TPU decomposes in a specific way. At first, the hard segments decompose and the material becomes soft and melts. Subsequently, pool fires are formed and melted material burns extensively. There are not many works addressing this problem in detail especially in terms of suitable flame retardant solutions. It is crucial to understand at which stage the flame retardants are working and how they affect the thermal decomposition of TPU. Hence, the focus of this work was put on the identification of the reactions occurring during each stage of TPU decomposition and the contribution of released products to the effective heat of combustion (EHC). Moreover, the detailed analysis of the melt dripping behavior was performed to better understand the influence of the decomposition degree on the viscosity.
The use of melamine cyanurate (MC) in combination with other additives was reported to be a promising flame retardant solution for TPU, especially in cable jacket applications. Hence, the combinations of MC with various flame retardants were used in TPU (Elastollan® 1185A10) and were investigated in terms of fire behavior, flammability, pyrolysis and decomposition products. As flame retardants, common ones were used including aluminum trihydrate (ATH), melamine polyphosphate (MPP), or aluminum diethylphosphinate (AlPi). Moreover, commercial product TPU-FR (Elastollan® 1185A10FHF) was investigated as a reference.
Elastomers are used in a wide range of automotive and railway applications. However, a severe drawback of most rubbers are their high flammability. Therefore, flame retardants (FRs) are added to improve the performance in fire. Generally, rubber composites are filled with high amounts of mineral fillers such as aluminium trihydroxide (ATH) to fulfil fire safety regulations. These high loadings may cause deterioration of the physical properties of the material. This work shows the implementation of two new strategies to achieve the modern demands on non-toxic FRs and the reduction of fillers.
The first approach was the implementation of multilayer graphene (MLG), acting as a multifunctional filler, reinforcing agent and FR. The study presents filler combinations with a systematic variation of the fillers carbon black (CB), MLG and ATH. The nanocomposites were prepared via master batch by an ultrasonically assisted solution mixing. Afterwards the master batch was compounded into the rubber in a two-roll milling. MLG substituted high amounts of the conventional filler CB, leading to reduced filler loadings and a consistent improvement in curing, mechanical and FR properties.
The second strategy was the combination of phosphorous-containing FRs with a potential new polymeric char promoting agent polyaniline (PANI). Char promoting additives such as pentaerythritol (PER) improve the effectiveness of the FR system. The combination of ammonium polyphosphate (APP) with PER was successfully investigated for natural and styrene-butadiene rubber composites. This work investigates the flame retardancy of the combination of FRs with PANI and its capability to act as a char/barrier promoter in EPDM.
The morphology of the rubbers and homogenously dispersion of MLG was investigated via scanning/transmission electron microscope (SEM/TEM) micrographs. Rheological and mechanical measurements assessed the influence of the fillers on the physical properties of the rubber composites. Characterization via thermogravimetric analysis (TGA) led to a broader understanding of the decomposition. In order to determine the flame retardancy effect of these materials, a multi-methodical approach was selected. Limiting oxygen index (LOI) and UL-94 were used to quantify the flammability of the rubber composites. The cone calorimeter provided information about the fire behaviour in forced flaming conditions. Residues were investigated via elementary analysis and XPS to clarify the composition of the remaining material. Glow-Wire and FMVSS 302 tests revealed significant results in terms of flame retardancy. The flame retardancy investigation of rubber composites, combinations of ATH with MLG and ATH with phosphorous-containing FRs, broaden the horizons of rubber flame retardancy solutions. By examining alternate FR formulations and their effect on mechanical and physical properties of the rubber, new insight into the range of applicable additives for rubber composites may be won.
The need to develop effective flame retardants that retain polymer properties and are safe for consumers and the environment is a continuous challenge for material scientists. While halogenated flame retardants were once commonplace, the shift to non-halogenated materials has steadily progressed due to concerns over impact on health and the environment. One prominent group of flame retardants has become a viable alternative for halogenated materials, namely phosphorus-based flame retardants. The chemical versatility of phosphorus-based flame retardants and the ability to work as reactive or additive compounds makes them ideally suited for modern materials. There exists a trend toward complex, polymeric, and multifunction flame retardants, as these materials show greater flame retardancy performance than low molecular weight counterparts and affect material properties to a much lesser extent.
One group of organophosphorus flame retardants that shows great potential for high-performance polymers like epoxy resins are hyperbranched phosphorus-based polymers. These additives exhibit great miscibility with the polymer matrix and a significantly decreased diffusion through the material, which greatly reduce leaching or blooming out of the matrix. Moreover, the material’s thermal stability remains intact at elevated temperatures due to its low impact on the glass transition temperature. Finally, following market trends and legislation such as the guidelines for the Restriction of Hazardous Substances Directive implemented by REACH (Registration, Evaluation, Authorization and Restriction of Chemicals) in the EU, these macromolecules are non-accumulating, non-toxic and have a lower risk of leeching or blooming from the matrix, further reducing environmental impact.
The work presented herein focusses on two distinct parts studying hyperbranched polymeric flame retardants and their corresponding monomeric compounds.
The first part, involving the low molecular weight components, investigated the role of the chemical surrounding of phosphorus in terms of flame retardant efficacy. Here, a systematic variance of the surrounding of phosphorus was investigated: by changing the ratio of oxygen to nitrogen (4:0 until 1:3), four materials, namely phosphoester (4:0), phosphoramidate (3:1), phosphorodiamidate (2:2), and phosphoramide (1:3), were synthesized, characterized, and finally added to Bisphenol A based epoxy resins (10 wt.-% loading). Pyrolysis investigations showed that low molecular weight components volatize at lower temperatures than the polymer matrix. Additionally, cone calorimeter measurements and TGA-FTIR investigations show trends in respect to FR efficacy in pyrolysis and full flaming conditions.
The second part involves the hyperbranched variants of the monomeric counterparts and investigates the role of complex shape on flame retardant efficacy. By comparing the low to the high molecular weight compounds, the influence of the complex shape becomes apparent and can be quantified. Cone calorimeter measurements show an increase in flame retardancy for some materials, while for others, the mode of action is altered.
By implementing a multi-methodical approach, various flame retardancy aspects, from pyrolysis behavior in the gas and condensed phase, to ignitability / reaction-to-small-flame performance, to action in forced flammability experiments, are identified and quantified, allowing for a clearer understanding of the behavior in fire of these novel flame retardants. By comprehending the roles of chemical composition and complex shape, it opens the path for new and effective multifunctional, polymeric flame retardants with decreased PBT, higher miscibility, and low impact on Tg.
This work is funded by the Deutsche Forschungsgemeinschaft (DFG: SCHA 730/15-1; WU 750/8-1).
The individual and collective impacts of additives in melt dripping behaviour were studied under UL 94 vertical test conditions. A set of polyamide 6 (PA6) based materials compounded with melamine cyanurate (MCA) – a ˝dripping agent˝ – and glass fibre (GF) – a ˝non-dripping agent˝ - was investigated in detail. Dripping quantification was carried out during first and second ignition. The materials and their drops were investigated with respect to thermal decomposition, melt viscosity, and others properties. PA6 with V-2 classification improves to V-0 when MCA is added; and is worsened to HB in presence of glass fibre. Together, PA6/GF/MCA achieved V-2. The non-flaming drops of PA6/MCA are formed by oligomeric fragments. The flaming drops of PA6/GF contain a high amount of glass fibre. The dripping behaviour of PA6/GF/MCA under fire is a complex response of the specimen, but not explained by an easy superposition of the materials’ properties. The dripping behaviour is influenced by the interaction and concurrence of the different phenomena.
Elastomers, such as hydrogenated acrylonitrile-butadiene rubber (HNBR) are usually mechanically reinforced with high loadings of carbon black (CB) to achieve the properties demanded; high amounts of mineral flame retardants are used to fulfill fire safety requirements. These high filler loadings sometimes cause deterioration of the physical properties of the material. In this study, multilayer graphene (MLG), a nanoparticle made of only 10 graphene sheets, is applied in low loadings (3 phr) to reduce the total amount of filler or boost performance.1,2,3 In former studies nanofiller achieved increased flame retardancy at very low lowdings.4,5,6 The dispersion of the nanofiller is essential for the properties of the nanocomposites.7 The nanocomposites were prepared via master batch by an ultrasonically assisted solution mixing and subsequent conventional two-roll milling.
SEM and TEM micrographs and rheological measurements revealed that the MLG nanoparticles were well dispersed in the HNBR matrix. In the HNBR nanocomposites, 3 phr MLG replaced 15 phr CB, 3 phr ATH or 15 phr CB + 3 phr ATH and achieved large consistent improvement in curing, rheological and mechanical properties of the HNBR. The nanocomposites with partial replaced CB reduced the filler loading up to 60% without any deterioration of the properties. The HNBR/MLG nanocomposites achieved an even higher Young’s modulus, hardness and thermal conductivity. MLG achieved advanced flame retardancy by improving the protection layer. The layer is created during the burning phase and acted as an afterglow suppressor. This study proposed the combination of ATH with MLG as a promising approach to reduce the amount of filler, in addition to improving the mechanical properties and fire performance of HNBR rubbers.
After introducing into the activities and competence of BAM in the field of fire science, several aspects of successful and tailored flame retardancy of polyolefins are discussed. The talk gives an overview of the works relevant for developing flame retardant polyolefins performed in the working group flame retardancy of polymers. The hypothesis of conservation of effective heat of combustion is proposed. The role of charring, inert fillers, protection layer, and intumescence is assessed for flame retarded polyolefins. Distinct routes of optimization sketched. Examples of controlling the dripping and melt flow to obtain the desired fire behaviour are discussed. Finally the cable modul for the cone calorimeter is presented.
Steel tension rod systems consist of tension rods, fork connectors and associated intersection or connecting plates. They are used for truss systems, bracings or suspensions owing to slender design and increased economic efficiency. In case of fire, beside the tension rods themselves, the connection parts require appropriate fire protection. The use of intumescent fire protection coatings prevents a rapid heating of the steel and helps to ensure the load-carrying capacity of the structures. Because the connection components of the tension rod systems feature surface curvature as well as a complex geometry, high demand is placed on the intumescence and thermal protection effectiveness of the reactive fire protection coatings. Experimental studies were carried out to investigate the performance of intumescent coatings applied to the components of tension rod systems. The examined aspects include the foaming and cracking behaviour of the intumescent coatings, the influence of different dry film thicknesses (DFT), the heating rate of the steel connecting parts in comparison to the tension rods, as well as the mounting orientation of the tension rods together with their associated fork connectors. The results show that a decrease in the surface curvature and/or an increase in the mass concentration of the steel components lead to a lower heating rate of the steel. Moreover, the performance of the intumescent coating on tension rod systems is influenced by the mounting orientation of the steel components.
From halogenated flame retardants to non-halogenated to nanocomposites, each milestone in flame retardancy research led to an increase in performance and safety. With the rise of ceramic precursors in flame retardants, a new field of applications in extreme fire scenarios has become accessible. Intumescent coatings combined with precursors for ceramics show a high temperature transition to a ceramic foam, which provides much better fire resistance than conventional coatings at temperatures beyond 1200°C. Even a protection at 2000 °C for several minutes can be achieved. Combining the expansion property of traditional intumescent coatings with a ceramification at high temperatures leads to high-performance coatings, whose unique properties may prove useful for emergency insulation systems for re-entry bodies in the aerospace industry or special fire protection applications.
In this study, the protection performance in extreme fire conditions, the development of the expansion and the following ceramic transition of a high-performance coating are investigated. To this end, a small scale high-performance burner setup was created. The coated (2.5/4 mm) steel plates (75 x 75 x 2 mm) were exposed to direct flame treatment of a propane-oxygen-burner controlled by two flow controllers. During the test, temperatures above of 1800 °C were reached and steel and flame temperature were recorded. Fire tests of different durations (1, 2.5, 5, 10 and 20 min) were performed. The residues of the different development stages were analysed with non-destructive µ-computed tomography and scanning electron microscopy. The 3D images of the computed tomography provide an insight into the developing cell structure and state of ceramification of the residues.
The demands for modern flame retardants are higher than ever: a flame retardant must function effectively in a certain polymer matrix and avoid critical alterations to the material’s properties. Ideally, a flame retardant additive should be easily miscible and show no sign of leaching or blooming from the matrix. Additionally, the flame retardant should be non-toxic, non-accumulating and biocompatible. Hyperbranched polymers are a promising group of multifunctional flame retardants which fulfill these demands: their complex shape enables high miscibility and avoids leaching or blooming, while their high molecular weight potentially increases biocompatibility and lowers accumulation and toxicity. Moreover, they exhibit a low impact on polymer properties and a good flame retardant performance.
This work examines the efficacy and mode of action of phosphorus-based hyperbranched polymeric flame retardants in bisphenol A-based epoxy matrices. To investigate the effect of the complex shape, the hyperbranched polymers are compared to their corresponding monomeric variants. Furthermore, the materials are synthesized to contain systematically varying oxygen-to-nitrogen ratios, allowing for new insight into what role the chemical surrounding of phosphorous plays in flame retardant efficacy.
Using a multi-methodical approach, including thermogravimetric analysis coupled with Fourier transform infrared spectroscopy (FTIR), hot stage FTIR, micro combustion calorimetry, differential scanning calorimetry, oxygen index (LOI), UL-94 tests and cone calorimetry experiments, the decomposition mechanisms and the flame retardant modes of action of these flame retardants in epoxy resins are investigated, shedding new light on the chemistry of flame retardancy.
Intumescent coatings for fire protection offer advantages over (non-intumescent) cementitious coatings and boards regarding speed of construction, architectural aesthetics, sometimes costs, and other features. However, conventional organic intumescent coatings as well as soluble silicate (waterglass) coatings form foams with low mechanical stability, and the latter coatings generally suffer from low resistance against humidity. Therefore, the search for novel intumescent coatings for more demanding conditions (e.g., abrasive environments) is a necessity in the context of steadily increasing requirements of society and industry.
In this contribution, we present results on intumescent aluminosilicate coatings for fire protection that form foams with significantly increased mechanical strength. Two base formulations, a metakaolin/silica-based mix, adapted from Krivenko et al., and a silica/corundum-based mix, developed at Curtin University, as well as formulations modified with additives (Al(OH)3, Mg(OH)2, B2O3, Na2B4O7), were applied to steel plates (75 mm × 75 mm) and exposed to simulated fire conditions (fire curve according to ISO 834-1:1999). Temperature-time curves were recorded to assess the degree at which the coatings insulated the substrate. In addition, XRD, TG, oscillatory rheometry, and SEM were employed to characterise the coatings.
The coatings were observed to partly expand during hardening due to H2 formation. When the hardened coatings were exposed to elevated temperatures they intumesced as expected, with the degree and nature of expansion dependent on the formulation. Oscillatory rheometry provided insights into the intumescent processes in an apparently brittle material. It revealed that the hardened aluminosilicate coatings became viscous (loss factor > 1) at 75–225 °C, in the temperature range of major water release, as opposed to a “standard” metakaolin-based geopolymer, which continued to behave as a solid. This explains the intumes¬cent behavior of the coatings, i.e. further expansion and foam formation. Microstructural analysis confirmed pore expansion and coalescence; XRD showed that the phases formed after heating (max. temperature ~840 °C) were of ceramic-type.
The fire protection (defined here as the time for the steel substrate to reach the critical temperature of 500 °C) depended mainly on the thick¬ness of the fully expanded coating, i.e. after intumescence. An alumino¬silicate coating free of additives with an original thickness of 12 mm was able to protect the steel for >30 min. The addition of 10 % anhydrous borax (Na2B4O7) caused a significant improvement, such that an original coating thickness of only 6 mm was sufficient to protect the steel for ~30 min. This was caused by the formation of sodium metaborate dihydrate (NaB(OH)4) in the coating that led to a significantly extended dehydration plateau in the temperature-time curve at ~100 °C during the fire exposure.
A preliminary analysis has been presented on the advantages for Mexico to migrate the cargo from trucking to railways. While the approach is highly unrealistic, it describes interesting figures that should animate the interest of Mexico to develop its railway infrastructure. Adverse situations due to the topographic characteristics of the mostly populated area of Mexico. The data presented in this paper suggest that the building of railway infrastructure is economically feasible.
Thermoplastic starch polymer blends as biodegradable materials are well known and used mainly as packaging material. In order to exploit new application fields for these materials, additional properties such as flame retardancy or increased mechanical strength are required. This work focuses on the flammability and fire behavior of a thermoplastic starch/polyester blend reinforced with natural fibers derived from Mexican industry processes wastes, such as keratin fibers from the tannery industry or coconut fibers[1]. Different fiber contents as well as combinations of varying contents of aluminum trihydroxide, expandable graphite or ammonium polyphosphate were tested in LOI, UL94, cone calorimeter and TG-FTIR in order to investigate and assess the concentration dependence of the fibers and flame retardants as well as synergistic effects between both components. In combination with ammonium polyphosphate, the coconut fibers induce a synergistic effect by reinforcing the char residue and creating a more stable heat barrier during forced flaming combustion in the cone calorimeter. Synergism is also observed in the oxygen test. The recycling of otherwise wasted material is a true challenge in material development, thus this work is a first step in the direction of sustainable and biodegradable materials.