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Eingeladener Vortrag
- nein (67)
Die Präsenz von Mikroplastik in aquatischen Ökosystemen ist ein globales Problem und steht zunehmend im Fokus der Öffentlichkeit. In mehreren Studien konnten Anreicherungen hydrophober, organischer Schadstoffe an MP nachgewiesen werden. Der Einfluss des Alterungszustandes der MP-Partikel auf das Sorptionsverhalten von hydrophoben organischen Substanzen ist nicht hinreichend geklärt.
Ziel der vorliegenden Arbeit war die Untersuchung des Sorptionsverhaltens von Schadstoffen mit Bedeutung für limnische Gewässer an künstlich gealterten Partikeln relevanter Polymere. Das Modell verwendete die Aromaten Benzol, Toluol, Ethylbenzol und Xylol (BTEX) sowie Etherverbindungen. Diese Substanzen sind oder waren Bestandteile in unterschiedlichen Kraftstoffen und finden sich daher in vielen aquatischen Ökosystemen weltweit. Als Sorbentien kamen teilkristallines Polypropylen (PP) und amorphes Polystyrol (PS) in Form von Industriepellets zum Einsatz. Die Pellets wurden jeweils sowohl unbehandelt als auch mittels UV-Bestrahlung künstlich gealtert verwendet und mikroskopisch sowie mittels XPS, FTIR und DSC charakterisiert. Die Alterung führte bei PS zu einer verringerten Sorptionskapazität, während bei PP keine Veränderung im Sorptionsverhalten beobachtet wurde.
Flame retardancy mechanisms of aluminium phosphinate in glass fiber reinforced thermoplastics
(2008)
The flame retardancy of poly(butylene terephthalate) (PBT) containing aluminium diethlyphosphinate (AlPi) and/or nanometric metal oxides such as TiO2 or Al2O3 was investigated. In particular the different active flame retardancy mechanisms were discovered. Thermal analysis, evolved gas analysis (TG-FTIR), flammability tests (LOI, UL 94), cone calorimeter measurements and chemical analyses of residues (ATR-FTIR) were used. AlPi acts mainly in the gas phase through the release of diethylphosphic acid, which provides flame inhibition. Part of AlPi remains in the solid phase reacting with the PBT to phosphinate-terephthalate salts that decompose to aluminium phosphate at higher temperatures. The metal oxides interact with the PBT decomposition and promote the formation of additional stable carbonaceous char in the condensed phase. A combination of metal oxides and AlPi gains the better classification in the UL 94 test thanks to the combination of the different mechanisms.
The fire retardancy mechanism of aluminium diethyl phosphinate (AlPi) and AlPi in combination with melamine polyphosphate (MPP) was investigated in glass-fibre reinforced polyamide 6 (PA6/GF) by analysing the pyrolysis, flammability and fire behaviour. AlPi in PA6/GF-AlPi partly vaporises as AlPi and partly decomposes to volatile diethylphosphinic acid (subsequently called phosphinic acid) and aluminium phosphate residue. In fire a predominant gas-phase action was observed, but the material did not reach a V-0 classification for the moderate additive content used. For the combination of both AlPi and MPP in PA6/GF-AlPi-MPP a synergistic effect occurred, because of the reaction of MPP with AlPi. Aluminium phosphate is formed in the residue and melamine and phosphinic acid are released in the gas phase. The aluminium phosphate acts as a barrier for fuel and heat transport, whereas the melamine release results in fuel dilution and the phosphinic acid formation in flame inhibition. The higher amount of aluminium phosphate in PA6/GF-AlPi-MPP stabilised the residue in flammability tests in comparison to PA6/GF-AlPi, so that this material achieved a V-0 classification in the UL 94 test.
Influence of weathering on the stability of flame retardancy in polymeric materials for outdoor use
(2009)
Flame retardancy mechanisms of phosphorus containing epoxy resins: effects of oxidation state
(2006)
Bench scale performance based cone calorimeter investigations were conducted on glass fibre reinforced polyamide 66 (PA-66) and high impact polystyrene (HIPS) materials. Red phosphorus and magnesium hydroxide were used as fire retardants. Dilution, heat sink, barrier and charring mechanisms are considered to be active in the condensed phase. Dilution, cooling and flame poisoning mechanisms are discussed for the gas phase. Cone calorimeter data are used to give a comprehensive fire behaviour assessment in terms of the propensity to cause a quick growing fire and of the propensity to cause a fire of long duration. The external heat flux is varied between 30 and 75 kW/m2 so that the results for combustion behaviour and flame retardancy, respectively, are valid for different fire scenarios and fire tests. Results on the intrinsic contribution of the steady heat release rate per unit area reveal information about the flammability behaviour. UL 94 results are predicted in close correspondence to UL 94 experiments.
The fire retardancy mechanisms of aluminium diethylphosphinate in combination with melamine polyphosphate and zinc borate was analysed in glass-fibre reinforced polyamide 6,6. The influence of phosphorus compounds on the polyamide decomposition pathways was characterized using thermal analysis (TG), evolved gas analysis (TGFTIR), and FTIRATR analysis of the residue. The Lewis acidbase interactions between the flame retardants, the amide unit, and the metal ions control the decomposition. The flammability (LOI, UL 94) and performance under forced-flaming conditions (cone calorimeter using different irradiations) were investigated. Fire residues were analysed with FTIRATR, SEMEDX, and NMR. Aluminium phosphinate in polyamide 6,6 acts mainly by flame inhibition. Melamine polyphosphate shows some fuel dilution and a significant barrier effect. Using a combination of aluminium phosphinate and melamine polyphosphate results in some charring and a dominant barrier effect. These effects are improved in the presence of zinc borate due to the formation of boronaluminium phosphates instead of aluminium phosphates.
The influence of weathering on the fire retardancy of polymers is investigated by means of a cone calorimeter test, before and after artificial weathering. The surface degradation was monitored using different techniques (ATR–FTIR, microscopy, colour measurement). Different kinds of polymeric materials were chosen, all as they are used in practice: polycarbonate (PC) blends, polyamide (PA) and polypropylene (PP) flame-retarded with arylphosphate, melamine cyanurate (MC) and intumescent formulation based on ammonium polyphosphate (APP), respectively.
All samples show material degradation at the surface due to weathering. No significant weathering influence occurs on the flame retardancy when it is a bulk property, as was observed for aryl phosphates in PC blends and MC in PA. When the fire retardancy is dominated by a surface mechanism, dependence on the duration of weathering is detected: for intumescent formulations based on ammonium APP in PP, a worsening in the formation of the intumescent network was observed.
The pyrolysis and flammability of phosphonium-modified layered silicate epoxy resin nanocomposites (EP/LS) were evaluated when LS was combined with two flame retardants, melamine borate (MB) and ammonium polyphosphate (APP), that also act via a surface protection layer. Thermogravimetry (TG), TG coupled with Fourier Transform Spectroscopy (TG-FTIR), oxygen index (LOI), UL 94 burning chamber (UL 94) and cone calorimeter were used. The glassy coating because of 10 wt % MB during combustion showed effects in the cone calorimeter test similar to nanodispersed LS, and somewhat better flame retardancy in flammability tests, such as LOI and UL 94. Adding APP to EP resulted in intumescent systems. The fire retardancy was particularly convincing when 15 wt % APP was used, especially for low external heat flux, and thus, also in flammability tests like LOI and UL 94. V0 classification is achieved when 15 wt % APP is used in EP. The flame retardancy efficiency of the protection layers formed does not increase linearly with the MB and APP concentrations used. The combination of LS with MB or APP shows antagonism; thus the performance of the combination of LS with MB or APP, respectively, was disappointing. No optimization of the carbonaceous-inorganic surface layer occurred for LS-MB. Combining LS with APP inhibited the intumescence, most probably through an increase in viscosity clearly above the value needed for intumescent behavior.