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The flame retardant effect of zinc sulphide (ZnS) in plasticised poly(vinyl chloride) (PVC-P) materials was investigated. PVC-P containing different combinations of additives such as 5% ZnS, 5% of antimony oxide (Sb2O3) and 5% of mixtures based on Sb2O3 and ZnS were compared. The thermal degradation and the combustion behaviour were studied using thermogravimetry (TG), coupled with FTIR (TG-FTIR) or with mass spectroscopy (TG-MS), and a cone calorimeter, respectively. A detailed and unambiguous understanding of the decomposition and release of the pyrolysis products was obtained using both TG-MS and TG-FTIR. The influence of ZnS, Sb2O3 and the corresponding mixtures on the thermal decomposition of PVC-P was demonstrated. Synergism was observed for the combination of the two additives. The combustion behaviour (time to ignition, heat release, smoke production, mass loss, CO production) was monitored versus external heat fluxes between 30 and 75 kW m-2 with the cone calorimeter. Adding 5% of ZnS has no significant influence on the fire behaviour of PVC-P materials beyond a dilution effect, whereas Sb2O3 works as an effective fire retardant. Synergism of ZnS and Sb2O3 allows the possibility of replacing half of Sb2O3 by ZnS to reach equivalent fire retardancy.
The influence of different organobentonites on the decomposition and the combustion behaviour of an epoxy resin were examined. The epoxy resin is a cationically polymerised cycloaliphatic epoxy resin flexibilised with poly(tetrahydrofuran) (PTHF), with hydroxyl endgroups. The bentonite was modified with either an ammonium or a phosphonium salt. The thermal decomposition of the PTHF induced by the initiator, used for the cationic polymerisation, did neither take place for the nanocomposite based on the ammonium bentonite nor for that based on the phosphonium bentonite. This improved decomposition characteristic lead to a larger time to ignition for both kinds of nanocomposites compared to the not modified polymer, which is not the case for other polymer/clay nanocomposites described in the literature. The fire behaviour was investigated using limiting oxygen index (LOI), a horizontal burner test and a cone calorimeter. The forced flaming conditions in the cone calorimeter were varied using different external heat fluxes between 30 and 70 kW · m-2. The fire behaviour of the nanocomposites was improved in comparison to the polymer, and phosphonium bentonite was superior to ammonium bentonite. The main mechanism is a barrier formation resulting in a reduction of the fire growth rate, which was more pronounced in the case of high external heat fluxes.
Polymeric nanocomposites are discussed as one of the most promising advanced materials whose nanoscale effects can be exploited for industry. Layered silicate polypropylene-graft-maleic anhydride nanocomposites are investigated as a model to clarify the potential of such materials in terms of fire retardancy. The nanostructure is characterized using transmission electron microscopy (TEM) and shear viscosity. The fire behavior is characterized using different external heat fluxes in cone calorimeter, limiting oxygen index and UL 94 classification. A comprehensive fire behavior characterization is presented which enables an assessment of the materials’ potential with respect to different fire scenarios and fire tests. The influence of morphology and the active mechanisms are discussed, such as barrier formation and changed melt viscosity. To our knowledge, it is the first attempt to illuminate the concept’s strengths, such as the reduction of flame spread, and weaknesses, such as the lack of influence on ignitability, in a clear, comprehensive and detailed manner.
On the thermal behaviour and thermo-oxidative stability of liquid crystalline triphenylene compounds
(1999)
Columnar discotic materials are considered for applications in the area of photoconductivity and light-emitting diodes. A major requirement is their stability at elevated temperatures and in the presence of oxygen. The thermal and thermo-oxidative behaviour of discotic triphenylene derivatives was investigated by us using various methods, in particular by chemiluminescence (CL), UV-vis absorption spectroscopy and in situ thermogravimetry-mass spectroscopy (TG-MS). Various degradation processes are described for increasing temperature, and their influences on functional properties are discussed.
Polarized fluorescence and orientational order parameters of a liquid-crystalline conjugated polymer
(1999)
We report a study of the orientational order of aligned thin films of the liquid crystalline conjugated polymer poly(9,9-dioctylfluorene). Steady state polarized fluorescence measurements were used to determine the orientational order parameter <P2> and <P4>. The influence of intermolecular and intramolecular excitation energy transfer on the degree of polarization is discussed. The role of film morphology is also examined by comparison of the results for glassy and crystalline films.
The thermo-oxidative degradation of a polymeric optical cable is investigated by chemiluminescence, The results are reliable and reproducible. Two distinct processes are reported marked by a peak and a plateau behavior versus the time, respectively. Both processes are ruled by thermally activated processes. Beside the dependencies of temperature and time, the influence of absorbed water is discussed. Chemiluminescence is proposed as a promising candidate for a suitable testing method assessing the thermo-oxidative stability of plastic optical fibers and cables. it requires not more than a simple one-day testing procedure and has the advantage that it can be carried out even within the lo cv temperature ranges of the cables' intended use.
Conjugated polymers based on 1,4-phenylenevinylene units are very promising materials for applications as light-emitting diodes. A major requirement is their stability at elevated temperatures of operation. The thermo-oxidative behaviour of a soluble poly(1,4-phenylenevinylene) derivative, poly[2,5-bis(2-ethylhexyloxy)-1,4-phenylene vinylene], was investigated by using chemiluminescence and UVVis absorption spectroscopy. Extremely sensitive chemiluminescence is successfully applied since even minor chemical changes could lead to a considerable loss of photo- and electro-optical properties. Various degradation processes are described as a function of time and temperature and their influences on functional properties are discussed. The investigated material does not show sufficient thermo-oxidative stability within the temperature range of intended use in contact with air. For industrial application, direct contact with oxygen during processing and operation has to be avoided.
The thermal decomposition and the fire behavior of glass fiber reinforced polyamide 66 (PA-66) and high impact polystyrene (HIPS) containing red phosphorus (P4) were investigated. For glass fiber reinforced PA-66, P4 promotes char formation in the condensed phase. Barrier effects and the reduction of combustible volatiles were identified as fire retardancy mechanisms. For HIPS, P4 acts in the gas phase, mainly trapping radicals. The heat release per mass loss polymer is reduced due to an incomplete combustion.