Filtern
Dokumenttyp
Schlagworte
- Flame retardance (5)
- Fire retardancy (4)
- Nanocomposites (4)
- Cone calorimeter (3)
- Epoxy resin (3)
- Composites (2)
- Cone Calorimeter (2)
- Flame retardancy (2)
- Flammability (2)
- High performance polymers (2)
Most of the polymeric materials used are easy to ignite and show extensive flame spread along their surfaces. Apart from extensive heat release rates, their short time to ignition (tig), in particular, is a key fire hazard. Preventing ignition eliminates fire hazards completely. Protection layers that shift tig by more than an order of magnitude are powerful flame retardancy approaches presenting an alternative to the usual flame retardancy concepts.
Coatings are proposed that consist of a three-layer system to ensure adhesion to the substrate, acting as an infrared (IR) mirror and protecting against oxidation. The IR-mirror layer stack is realised by physical vapour deposition in the sub-micrometre (<1 µm) range, reducing heat absorption by up to an order of magnitude. Not only is the ease of ignition diminished (tig is increased by several minutes), the flame spread and fire growth indices are also remarkably reduced to as little as 1/10 of the values of the uncoated polymers open for further optimization. Sub-micrometre thin IR-mirror coatings yielding surface absorptivity <0.1 are proposed as a novel and innovative flame retardancy approach.
Nanocomposites of bisphenol A polycarbonate with 2, 4, 6, and 15 wt% multiwall carbon nanotubes (MWNT) and their use in fire retardancy are investigated. Their thermal behavior and pyrolysis are characterized using thermogravimetry, differential scanning calorimeter, oscillatory shear rheology, and dynamic mechanical analysis. The flammability is addressed using LOI and UL 94; the fire behavior, with a cone calorimeter using different irradiation. With increasing MWNT content the storage modulus is increased (10-20%) and melt viscosity increases by several orders of magnitude, particularly for low shear rates. The melt flow, dripping, and deformation during fire are hindered, which influences UL 94 and cone calorimeter results. The peak heat release rate is reduced up to 40-50% due to an improved barrier for small amounts (2 wt%) of MWNT and for low irradiation, whereas the effect is reduced for increasing irradiation and nearly vanishes for increasing filling. Adjuvant but also deleterious mechanisms result in the complex dependency on the MWNT content. Significant flame retardancy effects are specific and limited to only some fire properties. This study allows the materials' potential for implementation in different fire scenarios and tests to be assessed and provides insight into active mechanisms.
A comparative evaluation of systematically tailored chemical structures of various phosphorus-containing aminic hardeners for epoxy resins was carried out. In particular, the effect of the oxidation state of the phosphorus in the hardener molecule on the curing behavior, the mechanical, thermomechanical, and hot-wet properties of a cured bifunctional bisphenol-A based thermoset is discussed. Particular attention is paid to the comparative pyrolysis of neat cured epoxy resins containing phosphine oxide, phosphinate, phosphonate, and phosphate (with a phosphorus content of about 2.6 wt %) and of the fire behavior of their corresponding carbon fiber-reinforced composites. Comparatively faster curing thermosetting system with an enhanced flame retardancy and adequate processing behavior can be formulated by taking advantage of the higher reactivity of the phosphorus-modified hardeners. For example, a combination of the high reactivity and of induced secondary crosslinking reactions leads to a comparatively high Tg when curing the epoxy using a substoichiometric amount of the phosphinate-based hardener. The overall mechanical performance of the materials cured with the phosphorus-containing hardeners is comparable to that of a 4,4-DDS-cured reference system. While the various phosphorus-containing hardeners in general provide the epoxy-based matrix with enhanced flame retardancy properties, it is the flame inhibition in the gas phase especially that determines the improvement in fire retardancy of carbon fiber-reinforced composites. In summary, the present study provides an important contribution towards developing a better understanding of the potential use of such phosphorus-containing compounds to provide the composite matrix with sufficient flame retardancy while simultaneously maintaining its overall mechanical performance on a suitable level.
The pyrolysis of an epoxy resin and the fire behavior of corresponding carbon fiber-reinforced composites, both flame-retarded with either 10-ethyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide or 1,3,5-tris[2-(9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide-10-)ethyl]1, 3,5-triazine-2,4,6(1H,3H,5H)-trione, are investigated. The different fire retardancy mechanisms are discussed, and their influence on the fire properties assessed, in particular for flammability (limiting oxygen index, UL 94) and developing fires (cone calorimeter with different external heat fluxes of 35, 50, and 70 kW m-2). Adding the flame retardants containing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide affects the fire behavior by both condensed phase and gas phase mechanisms. Interactions between the additives and the epoxy resin result in a change in the decomposition pathways and an increased char formation. The release of phosphorous products results in significant flame inhibition. The fire properties achieved are thus interesting with respect to industrial exploration.
Thermal, thermo-oxidative and fire residues of high impact polystyrene/magnesium hydroxide/red phosphorus (HIPS/Mg(OH)2/Pr) are investigated by solid-state NMR and compared with the results for the binary subsystem Mg(OH)2/Pr. The influences of oxygen, nitrogen and temperature are discussed. For a thermal decomposition and pyrolysis during combustion, the main pyrolysis of HIPS takes place while the remaining residue is a rather intact polymer, with a major share of the embedded Pr still present. Subsequently, mainly amorphous phosphates and a slight amount of crystalline Mg3(PO4)2 and Mg2P2O7 are formed at the highest temperatures. Only with increasing mass loss does the remaining polystyrene structure decompose and graphitic structures occur. The influence of oxygen on the decomposition mechanism is most obvious for the binary system Mg(OH)2/Pr. Pr vanishes more rapidly and crystalline, oxygen-rich magnesium phosphates are formed. In HIPS/Mg(OH)2/Pr systems the polymer acts as a barrier to reaction by the embedded particles, so that major characteristics of an anaerobic decomposition are found. Significant amounts of phosphorus are retained in the condensed phase through a reaction of Pr with Mg(OH)2 to mostly amorphous phosphates. This formation of amorphous inorganic magnesium phosphates can act as an additional physical barrier. This study outlines some advanced approaches for controlling the condensed-phase mechanisms of phosphorus and underlines that solid-state NMR is a most powerful tool for investigating the organic and inorganic residues.
A systematic and comparative evaluation of the pyrolysis of halogen-free flame-retarded epoxy resins containing phosphine oxide, phosphinate, phosphonate, and phosphate (phosphorus contents around 2.6 wt.%) and the fire behaviour of their carbon fibre composites is presented. Decomposition pathways are proposed based on the thermal analysis (TG), TG coupled with evolved gas analysis (TG-FTIR), kinetics and analysis of the residue with FTIR and XPS. All organophosphorus-modified hardeners containing phenoxy groups lead to a reduced decomposition temperature and mass loss step for the main decomposition of the cured epoxy resin. With increasing oxidation state of the phosphorus the thermally stable residue increases, whereas the release of phosphorus-containing volatiles decreases. The flammability of the composites was investigated with LOI and UL 94 and the fire behaviour for forced-flaming conditions with cone calorimeter tests performed using different irradiations. The flame retardancy mechanisms are discussed. With increasing oxidation state of the phosphorus additional charring is observed, whereas the flame inhibition, which plays the more important role for the performance of the composites, decreases. The processing and the mechanical performance (delamination resistance, flexural properties and interlaminar bonding strength) of the fibre-reinforced composites containing phosphorus were maintained at a high level and, in some cases, even improved. The potential for optimising flame retardancy while maintaining mechanical properties is highlighted in this study.
Barrier formation and increasing the melt viscosity are addressed as the two main general fire retardancy mechanisms of polymer nanocomposites. They result in specific impacts on fire properties that consequentially cause varying flame retardancy efficiency in different fire tests. The barrier formation retards mainly flame spread (peak of heat release rate) in developing fires, but does not reduce fire load (total heat evolved), ignitability or flammability (limiting oxygen index, UL 94). Furthermore, this flame retardancy effect increases with increasing irradiation and vanishes with decreasing irradiation. The increased melt viscosity prevents dripping, which is beneficial or disadvantageous depending on the fire test used. In some test, it become the dominant influence, transforming self-extinguishing samples into flammable materials or causing wicking. Advantages and the limits are sketched comprehensively for exploiting the main general fire retardancy mechanisms of polymer nanocomposites. It is concluded that barrier formation and changing the melt viscosity in nanocomposites are not sufficient for most applications, but must be accompanied by additional mechanisms in special systems or in combination with other flame retardants.
In 1996, R. T. K. Baker, and N. M. Rodriguez claimed to have synthesized a new type of carbon nanofiber material capable of storing large amounts of hydrogen at room temperature and pressures above 100 bar, thus making it a powerful candidate for a very efficient energy storage system in mobile applications. Consequently, many scientists all over the world tried to test and verify these findings, however, with partly inconsistent results. We present here for the first time independent hydrogen storage measurements for several types of nanofibers, both synthesized by our group following precisely the specifications given in the literature as well as original samples supplied by Rodriguez and Baker for this study. The hydrogen storage capacities at room temperature and pressures up to 140 bar were quantified independently by gravimetric and volumetric methods, respectively. No significant hydrogen storage capacity has been detected for all carbon nanofibers investigated.
Summary: The decomposition of novel phosphorus-containing poly(oxyphenylene-sulfonyl-phenylene-oxy-diphenyl phenylene phosphine oxide) (PSU_I), 2,5-dihydroxy-1-biphenylene-phosphine oxide based polysulfone (PSU_II), poly(sulfonyl-diphenylphenylene phosphonate) (PSU_P) and bisphenol A-based polysulfone (PSU) is studied. The influence of the chemical structure, charring and phosphorus release is discussed based on the mass loss, kinetics and products. The pyrolysis and fire behaviour of blends with epoxy resin (EP) are studied. For EP-PSU_II, phosphorus initiates water elimination and changes the decomposition pathway of EP. The fire behaviour of EP-PSU shows some improvements, whereas the heat release rate is crucially reduced for EP-PSU_II due to simultaneous char formation and flame inhibition.