Filtern
Erscheinungsjahr
Dokumenttyp
- Zeitschriftenartikel (218) (entfernen)
Schlagworte
- Flame retardancy (51)
- Flame retardant (26)
- Flammability (25)
- Flame retardance (22)
- Cone calorimeter (20)
- Epoxy resin (20)
- Nanocomposites (19)
- Fire retardancy (17)
- Pyrolysis (16)
- Nanocomposite (15)
Organisationseinheit der BAM
- 7.5 Technische Eigenschaften von Polymerwerkstoffen (73)
- 7 Bauwerkssicherheit (72)
- 7.3 Brandingenieurwesen (4)
- 6 Materialchemie (3)
- 7.1 Baustoffe (2)
- 5 Werkstofftechnik (1)
- 5.3 Polymere Verbundwerkstoffe (1)
- 6.0 Abteilungsleitung und andere (1)
- 6.3 Strukturanalytik (1)
- 6.6 Physik und chemische Analytik der Polymere (1)
Paper des Monats
- ja (2)
Tailored crosslinking in elastomers is crucial for their technical applications. The incorporation of nanoparticles with high surface-to-volume ratios not only leads to the formation of physical networks and influences the ultimate performance of nanocomposites, but it also affects the chemical crosslinking reactions. The influence of few-layer graphene (FLG) on the crosslinking behavior of natural rubber is investigated. Four different curing systems, two sulfur-based with different accelerator-to-sulfur ratios, and two peroxide-based with different peroxide concentrations, are combined with different FLG contents. Using differential scanning calorimetry (DSC), vulcametry (MDR) and swelling measurements, the results show an accelerating effect of FLG on the kinetics of the sulfur-based curing systems, with an exothermic reaction peak in DSC shifted to lower temperatures and lower scorch and curing times in the MDR. While a higher accelerator-to-sulfur ratio in combination with FLG leads to reduced crosslinking densities, the peroxide crosslinkers are hardly affected by the presence of FLG. The good agreement of crosslink densities obtained from the swelling behavior confirms the suitability of vulcameter measurements for monitoring the complex vulcanization process of such nanocomposite systems in a simple and efficient way. The reinforcing effect of FLG shows the highest relative improvements in weakly crosslinked nanocomposites.
Leather is considered a luxury good when used in seating and upholstery. To improve safety, flame retardancy in leather is usually achieved through various finishing processes such as spray or roller coating. These treatments require processing steps that cost time and are laborintensive. One avenue to achieving flame retardancy in leather is to add flame retardants during the tanning process. However, the influence on flame retardancy exerted by specific intumescent additives specifically added during leather tanning has yet to be investigated. This work explores the roles played by intumescent additive compounds in flame retarding leather when they are added during tanning instead of applied as a coating. Via a systematic investigation of various compound mixtures, the flame retardant effects in the condensed and the gas phases are elucidated. The results show a strong impact of melamine in the gas phase and of polyphosphates in the condensed phase. Their impact was quantified in fire and smoke analysis, showing a 14% reduction in the peak of heat release rate, strongly reduced burning lengths, and a 20% reduction in total smoke release compared to nontreated leather. These results illuminate the key role played by specific compounds in the flame retardancy of leather, particularly when they are added specifically during the tanning process instead of being applied as a coating.
This method has great potential to reduce processing steps, lower costs, and improve material safety.
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.
The characteristic influences of increasing concentrations of graphene, expanded graphite (EG), carbon black (CB), and multiwall carbon nanotubes (MWNT) are investigated on pyrolysis, reaction to small flame, burning behavior, and on electrical, thermal, and rheological properties of flame retarded polypropylene (PP-FR). The property-concentration dependency is different for the various material properties, as threshold, linear, and leveling off functions were observed. Increasing concentrations of carbon nanoparticles resulted in a decrease in the electrical resistivity of the polymer by crossing the percolation threshold. The developing nanoparticle network changes melt flow behavior for small shear rates, increases thermal conductivity and therefore, affects the UL 94 classification and oxygen index. The onset temperature of PP decomposition is shifted to temperatures up to 37°C higher; the peak heat release rate is reduced by up to 74% compared to PP-FR. Both effects leveled off with increasing particle concentration. Among the four carbon nanomaterials tested, graphene presents superior influence on composite properties over the tested concentration range and outperforms commercial CB, MWNT, and EG. POLYM. COMPOS., 36:12301241, 2015.
As most of polymeric materials are inherently flammable, flame retardants (FR) are commonly used to reduce their fire risks. Nevertheless, these flame retardant materials are often detrimental to smoke parameters like specific optical density or smoke toxicity. The influence of several smoke suppressants (SP)-zinc stannate, zinc phosphate, titanium oxide and hydrotalcite-were investigated with respect to flame retardancy, smoke emission, particle emission and smoke toxicity in a diethyl aluminum phosphinate (AlPi) flame retardant polyamide 6.6 (PA6.6). It was shown that the interaction between SP, FR and polymer is crucial for smoke and fire properties and can change the mode of action of the FR as well the decomposition mechanism of the polymer. Small amounts of SP show less effect on forced flaming behavior and the optical density, but they can influence flammability and the particle size distribution of the soot particles. The flame retardancy was significantly enhanced by 5 wt.-% zinc stannate in PA6.6 under forced flaming conditions. The charring mechanism was improved, and the mode of action of AlPi switched from the gas to the condensed phase. This resulted of in a reduced PHRR and TSP and an increase in residue yield. The smoke toxicity and optical density were reduced in the smoke density chamber as well. The smoke particles shifted to smaller sizes as the time in the pyrolytic zone increased. The formation of a dense char is assumed to be the key factor to enhance smoke suppression and flame retardancy properties.
Two different numerical simulation tools, Fire Dynamic Simulator (FDS) and ThermaKin, are investigated with respect to their capability to predict the mass loss rate of polymer materials exposed to different fires. For validation, gasification apparatus and cone calorimeter tests are conducted. The main focus is on the influence of residue formation. Therefore, poly (butylene terephthalate) (PBT) and PBT reinforced with glass fibres (PBT-GF) are investigated and compared. PBT decomposes almost completely, while PBT-GF forms residue. The materials are characterised in order to provide suitable input parameters. Additionally the total incident heat flux to the sample is measured. With accurate input parameters, FDS and ThermaKin predicted the pyrolysis behaviour of PBT very well. Only some limitations are identified regarding the residue-forming PBT-GF. Both numerical simulation tools demonstrate a high value regarding the assessment of parameters' relative impacts and thus the evaluation of optimisation routes in polymer and composite development.
Layered silicate epoxy nanocomposites: formation of the inorganic-carbonaceous fire protection layer
(2011)
The layered silicate (LS) modification and processing parameters applied control the morphology of the LS/polymer composites. Here, increasing the surface area of the LS particles by using alternative drying processes increases dispersion towards a more typical nanocomposite morphology, which is a basic requirement for promising flame retardancy. Nevertheless, the morphology at room temperature does not act itself with respect to flame retardancy, but serves as a prerequisite for the formation of an efficient surface protection layer during pyrolysis. The formation of this residue layer was addressed experimentally for the actual pyrolysis region of a burning nanocomposite and thus our results are valid without any assumptions or compromises on the time period, dimension, surrounding atmosphere or temperature. The formation of the inorganic-carbonaceous residue is influenced by bubbling, migration, reorientation, agglomeration, ablation, and perhaps also delamination induced thermally and by decomposition, whereas true sintering of the inorganic particles was ruled out as an important mechanism. Multiple, quite different mechanisms are relevant during the formation of the residue, and the importance of each mechanism probably differs from one nanocomposite system to another. The main fire protection effect of the surface layer in polymer nanocomposites based on non-charring or nearly non-charring polymers is the increase in surface temperature, resulting in a substantial increase in reradiated heat flux (heat shielding).
The pyrolysis and fire behavior of glass-fiber reinforced poly(butylene terephthalate) (PBT/GF) with two different metal phosphinates as flame retardants in combination with and without melamine cyanurate (MC) were analyzed by means of thermogravimetry, thermogravimetry coupled with infrared spectroscopy, flammability, and cone calorimeter tests as well as scanning electron microscopy/energy dispersive X-ray spectroscopy and X-ray fluorescence spectroscopy. In PBT/GF, dosages of 13-20% of the halogen-free flame retardant aluminum phosphinate or aluminum phosphinate in combination with MC fulfill the requirements for electrical engineering and electronics applications (UL 94 = V-0; LOI > 42%), whereas the use of the same amount of zinc phosphinate or zinc phosphinate in combination with MC does not improve the fire behavior satisfactorily (UL 94 = HB; LOI = 27-28%). The performance under forced flaming conditions (cone calorimeter) is quite similar for both of the metal phosphinates. The use of aluminum and zinc salts results in similar flame inhibition predominantly due to the release of the phosphinate compounds in the gas phase. Both metal phosphinates and MC interact with the polymer changing the decomposition characteristics. However, part of the zinc phosphinate vaporizes as a complete molecule. Because of the different decomposition behavior of the metal salts, only the aluminum phosphinate results in a small amount of thermally stable carbonaceous char. In particular, the aluminum phosphinate-terephthalate formed is more stable than the zinc phosphinate-terephthalate. The small amount of char has a crucial effect on the thermal properties and mechanical stability of the residue and thus the flammability.
Heterogeneous, gradual or structured morphology of fire residues plays an important role in fire retardancy of polymers. A scanning electron microscope with an attached energy dispersive X-ray spectrometer (SEM/EDX) is highlighted as a powerful tool for the advanced characterization of such complex fire residues, since it offers high resolution in combination with both good depth of field and analysis of chemical composition. Two examples are presented: First, comprehensive SEM/EDX investigation on a complex structured fire residue of glass fibre reinforced polyamide 6,6 (PA 66-GF) flame retarded by diethylaluminium phosphinate, melamine polyphosphate and some zinc borate. A multilayered surface crust (thickness ~ 24 µm) covers a rather hollow area stabilized by GF glued together. The resulting efficient thermal insulation results in self-extinguishing before pyrolysis is completed, even under forced-flaming combustion. Second, sophisticated, quasi online SEM/EDX imaging of the formation of residual protection layer in layered silicate epoxy resin nanocomposites (LSEC). Burning specimens were quenched in liquid nitrogen for subsequent analyses. Different zones were distinguished in the condensed phase characterized by distinct processes such as melting and ablation of organic material, as well as agglomeration, depletion, exfoliation and reorientation of the LS.
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.
A mono-component intumescent flame retardant named ethylenediamine-modified ammonium polyphosphate (MAPP) is used in polyethylene-octene elastomer (POE). Insight into the flame-retardant mechanisms of the MAPP is provided from a new perspective. The fire performance of POE/MAPP composites is investigated by oxygen index (OI) and vertical burning (UL-94) tests. POE Composite containing 35 wt% MAPP achieves a V-0 rating, and its OI is 29.3 vol%. The thermogravimetric Analysis (TGA) and Fourier transform infrared spectra (FTIR) confirm that the incorporation of ethylenediamine changes the thermal decomposition of APP, mainly resulting in the formation of char layer with a thermally stable structure. Cone calorimeter analysis revealed the flame-retardant modes of action of MAPP in POE under forced-flaming conditions. Quantitative analysis illustrates that both the residue due to charring and the fuel dilution/flame Inhibition resulting from the release of incombustible products/ phosphorus species decrease the total heat release (fire load) by 20e28%. The residue increases linearly with increasing MAPP content, whereas the reduction in effective heat of combustion levels off. Moreover, the flame-retardant effect resulting from the protective properties of the char is discovered to be the dominant mode of action (up to 85% reduction) with respect to the peak heat release rate, leading to the excellent flame retardancy of POE/MAPP.
The usage of concepts in scientific communication is critical to our ability to inform the reader about work that has been performed. The significance and thus the quality of scientific discussion rely on the precise use of concepts. In this second part of a two-part paper, concerning the scientific basis of polymer fire retardancy, the proper use of concepts is addressed. Distinct concepts in flame retardancy are discussed, such as fire residue, the correlation of fire performance with char yield according to van Krevelen, catalysis, and wicking. Synergy is discussed in detail, as well as approaches to quantify it, due to its importance for flame retardant polymers. The preceding first paper (part 1) discussed the proper use of scientific terms, thermal analysis, and fire testing. Thus, together these two papers support the community by offering recommendations and addressing some of the most relevant points. They encourage to review scientific practice in the field of flame retardancy of polymers.
Fire stability of glass-fibre sandwich panels: The influence of core materials and flame retardants
(2017)
Fire resistance has become a key property for structural lightweight sandwich components in aviation, shipping, railway vehicles, and construction. The development of future composite materials and components demands adequate test procedures for simultaneous application of compression and fully developed fire. Therefore an intermediate-scale approach (specimen size = 500 mm x 500 mm) is applied with compressive loads (up to 1 MN) and direct application of a burner to one side of the specimens, as established in aviation for severe burn-through tests. The influence of different core structures (polyvinylchloride foam, polyisocyanorate foam reinforced by stitched glass bridges, and balsa wood) was investigated for glass-fibre-reinforced sandwich specimens with and without flame retardants applied on the fabrics, in the matrix, and on surface for each specimen at the same time. Times to failure were increased up to a factor of 4. The intumescent coating prolongs the time to failure significantly.
What is more, using the intrinsic potential of the front skin together with the core to protect a load bearing back skin in sandwich panels, the design of the core – here using the wood core – is the most promising approach.
The effects of reducing specimen size on the fire behavior of polymeric materials were investigated by means of the rapid mass calorimeter, a high-throughput Screening instrument. Results from the rapid mass calorimeter were compared with those from the cone calorimeter. Correlation coefficients between the different measures of each method and between the two methods are discussed to elucidate the differences and similarities in the two methods. Materials with characteristic heat release rate (HRR) curves in the cone calorimeter were evaluated in detail. The rapid mass calorimeter produces valuable and interpretable results with HRR curve characteristics similar to cone calorimeter results. Compared to cone calorimeter measurements, material savings of 96% are achieved, while maintaining the Advantages of a macroscopic fire test.
Low amounts (<7.5 wt%) of organically modified layered silicate (LS) as well as large amounts (>10 wt%) of spherical amorphous SiO2 (sSiO2) has been used successfully as adjuvants in commercial polymeric materials flame retarded with metal hydroxide. The combination of LS and SiO2 is investigated in different thermoplastics with respect to their fire behavior, particular to overcome the restrictions in maximum and minimum filler contents know for the single additives. The aim was to check the potential of combinations of the inert fillers in absence of a real fire retardant. The combination of LS and sSiO2 harbors the potential for flame retardancy effects close to superposition or even synergy, due to an improved structure of the fire residue. LS-sSiO2 combinations are proposed to work as adjuvants superior to LS and sSiO2 in flame retarded polymeric materials.
Der steigende Einsatz von Holz-Kunststoff-Verbundwerkstoffen (Wood Plastic Composite, WPC) erfordert das Wissen um seine spezifischen Eigenschaften, insbesondere dem Brand risiko.
Dabei können Flammschutzmittel die Entflammbarkeit, Wärmeabgabe und die Brandausbreitung des Materials verringern.
Deshalb sind der gezielte und effiziente Einsatz und die Kenntnis über die Wirkungsweise der Flammschutzmittel im WPC für den Brandschutz von enormer Bedeutung. Dazu gehört auch die Rauchentwicklung im Brandfall. Rauch beeinflusst aufgrund seiner Toxizität und seiner Sichttrübung die Fluchtmöglichkeit der betroffenen Personen. In der Rauchkammer nach ISO 5659-2 wird die Rauchentwicklung von flachen Werkstoffproben ermittelt. Die Rauchgastoxizität bzw. die Rauchgaszusammensetzung wird mithilfe der FTIR (Fourier Transformierte Infrarot)-Spektroskopie ermittelt. Frei werdende Partikel schädigen die Atemorgane und beeinflussen damit auch die Fluchtfähigkeit von Personen im Brandfall. Aussagen zur Partikelemission können mithilfe eines an die Rauchkammer gekoppelten Partikelanalysators getroffen werden. Im Rahmen dieser Arbeit wurden verschiedene flammgeschützte WPC-Systeme hinsichtlich ihres Rauchverhaltens in der Rauchkammer untersucht. Die Ergebnisse zu emittierten toxischen Gasen, Partikeln und zur Rauchentwicklung werden vorgestellt und in Abhängigkeit von den eingesetzten Flammschutzmitteln im WPC diskutiert.
Polyurethane (PU) bilden eine der vielseitigsten Klassen der Polymerwerkstoffe. Kein anderer Kunststoff wird sowohl als Thermoplast, als Elastomer wie auch als Duroplast verarbeitet und eingesetzt. Entsprechend vielfältig sind auch die Anforderungen an den Flammschutz. Je nach Material und Anwendung müssen spezifische Brandnormen erfüllt werden. Der vorliegende Aufsatz gibt einen Überblick über die verfügbaren Ansätze, um durch geeignete Auswahl der Rohstoffe und der Flammschutzmittel diese verschiedensten Anforderungen an das Brandverhalten zu erfüllen.
Polyurethanes (PU) represent one of the most versatile classes of plastics. They are processed and used as thermoplastic, elastomer, and thermoset. The requirements regarding flammability are correspondingly versatile. Depending on the material and the field of application, specific fire tests have to be fulfilled. This paper describes the different concepts used to fulfil these requirements by choosing the right raw materials and flame retardants.
A phosphorous soybean-oil–based polyol was derived via epoxidation and ring opening reaction as an alternative to petrochemical-based polyol for the synthesis of flexible polyurethane foams (FPUFs). 5-wt.% and 10-wt.% of expandable graphite (EG) were added to further improve flame retardancy. The mechanical properties (tensile strength and compression stress) of the foams were investigated. Thermogravimetric analysis (TGA) coupled with Fourier-transform infrared (FTIR) were conducted to evaluate the pyrolysis; limiting oxygen index (LOI), UL 94 and cone calorimeter were performed to analyze the fire performance of the foams; smoke density chamber was used to investigate the smoke released during burning. When 10-wt.% of EG was used, the flame retardancy of the foams was much enhanced due to the synergistic effect between phosphorus and EG. The char yield was three times higher (54wt.%). The fire load MARHE approached 100 kWm−2, half of the value expected for a superposition. The combination of phosphorous polyols and EG is proposed as strategy for future flame retarded FPUFs.
Valorizing “non-vegan” bio-fillers: Synergists for phosphorus flame retardants in epoxy resins
(2022)
Sustainable, biogenic flame retardant adjuvants for epoxy resins are receiving increased focus. Zoological products like insects, bone meal, and eggshells are available in large quantities, but remain uninvestigated as functional fillers to epoxy resins, although they are potential synergists to flame retardants. The efficacy and flame retardancy of “non-vegan” additives in combination with flame retardants is investigated and the fire behavior and thermal decomposition of bio-sourced epoxy resin composites is characterized. By comparing the fire performance of composites containing flame retardants or fillers at varying loadings (5, 10, and 20%), their role as synergists that enhance the function of organophosphorus flame retardants in bio-epoxy composites is identified and quantified. Peak heat release rates were 44% lower in composites containing both filler and flame retardant versus those containing only flame retardants, and fire loads were reduced by 44% versus the pure resin, highlighting the ability of “non-vegan” fillers to function as synergists.