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The recently approved EU Construction Products Regulation (CPR) applies to cables as construction products.
The difficulty of predicting the fire performance of cables with respect to propagation of flame and contribution to fire hazards is well known. The new standard EN 50399 describes a full-scale test method for the classification of vertically mounted bunched cables according to CPR. Consideration of the material, time, and thus cost requires an alternative bench-scale fire test, which finds strong demand for Screening and development purposes. The development of such a bench-scale fire test to assess the fire Performance of multiple vertically mounted cables is described. A practical module for the cone calorimeter is proposed, simulating the fire scenario of the EN 50399 on the bench scale. The efficacy of this module in predicting full-scale CPR test results is shown for a set of 20 different optical cables. Key properties such as peak heat release rate (PHRR), fire growth rate (FIGRA), and flame spread are linked to each other by factors of around 5. In a case study, the bench-scale test designed was used to investigate the influence of the main components on the fire behaviour of a complex optical cable.
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.
Flexible polyurethane foams with densities of 40 ± 2 kg m−3 were prepared by combining different ecofriendly fillers such as layered double hydroxides (LDH) and kraft lignin (a byproduct of the pulp and paper industry) with a phosphorous polyol (E560) in order to study their effect on the mechanical performance and fire behavior of the foams. Two series of foams were prepared, some containing lignin or LDH separately, and some with a combination of both: one of the series was prepared without E560 (0E foam series) and the other with 5 parts per hundred of E560 polyol (5E series). The use of fillers resulted in increased viscosity of the reactive mixture, requiring higher blowing agent content in order to hold the density of the foams constant. It was observed that urea phase segregation was favored in the series of 0E foams due to their lower viscosity than the 5E series. This had consequent effects on the resilience, compression force deflection and compression set of these foams. In terms of fire behavior it was observed that while the limiting oxygen index decreased, cone calorimeter results showed that the combination of lignin, LDH and E560 decreased the heat release of the foams. In addition, the combination of fillers and E560 contributed to increase the viscosity of the pyrolysis products, preventing the dripping of the molten polymer, which is a key factor in flame propagation towards adjacent objects in fire scenarios.
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.
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.
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.
An experimental and numerical investigation of the effect of bisphenol A bis(diphenyl phosphate) (BDP) and polytetrafluoroethylene (PTFE) on the fire behaviour of bisphenol A polycarbonate/acrylonitrile butadiene styrene (PC/ABS) in the vertical UL 94 scenario is presented. Four PC/ABS blends were discussed, which satisfy different UL 94 classifications due to the competing effects of gasification, charring, flame inhibition and melt flow/dripping. For numerical investigation, the particle finite element method (PFEM) is used. Its capability to model the complex fire behaviour of polymers in the UL 94 is analysed. The materials' properties are characterised, in particular the additives impact on the dripping behaviour during thermal exposure. BDP is an efficient plasticiser; adding PTFE prevents dripping by causing a flow limit. PFEM simulations reproduce the dripping and burning behaviour, in particular the competition between gasification and dripping. The thermal impact of both the burner and the flame is approximated taking into account flame inhibition, charring and effective heat of combustion. PFEM is a promising numerical tool for the investigation of the fire behaviour of polymers, particularly when large deformations are involved. Not only the principal phenomena but also the different UL 94 classifications and the extinction times are well predicted.
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.
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.
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.
Distinct approaches are used to reduce the fire risks of polymers, a key issue for many industrial applications. Among the variety of approaches, the use of synergy in halogen-free multicomponent systems is one of the most auspicious. To optimize the composition of such flame-retardant systems it is essential to understand the mechanisms and the corresponding chemistry in the condensed phase. In this work different methods are used, including cone calorimeter, thermogravimetry (TG), and TG-FTIR, with the main focus on the solid-state NMR analysis of the solid residues. The structural changes in the condensed phase of two thermoplastic elastomer systems based on copolymer styrene-ethylene-butadiene-styrene (TPE-S) were investigated: TPE-S/aluminium diethylphosphinate (AlPi)/magnesium hydroxide (MH) and TPE-S/AlPi/zinc borate (ZB)/poly(phenylene oxide) (PPO). Strong flame inhibition is synergistically combined with protective layer formation. 13C-, 27Al-, 11B- and 31P MAS NMR (magic angle spinning nuclear magnetic resonance) experiments using direct excitation with a single pulse and 1H31P cross-polarization (CP) were carried out as well as double resonance techniques. Magnesium phosphates were formed during the pyrolysis of TPE-S/AlPi/MH, while for the system TPE-S/AlPi/ZB/PPO zinc phosphates and borophosphates were observed. Thus, the chemistry behind the chemical interaction was characterized unambiguously for the investigated systems.
In addition to the acid source, charring agent, and blowing agent, the binder is a crucial part of an intumescent coating. Its primary task is to bind all compounds, but it also acts as a carbon source and influences the foaming process. A series of intumescent coatings based on five different binders was investigated in terms of insulation, foaming, mechanical impact resistance, and residue morphology. The Standard Time-Temperature modified Muffle Furnace (STT MuFu+ ) was used for the bench-scale fire resistance tests and provided data on temperature and residue thickness as well as well-defined residues. The residue morphology was analyzed by nondestructive m-computed tomography and scanning electron microscopy. A moderate influence of the binder on insulation performance was detected in the set of coatings investigated, whereas the foaming dynamics and thickness achieved were affected strongly. In addition, the inner structure of the residues showed a rich variety. High expansion alone did not guarantee good insulation. Furthermore, attention was paid to the relation between the microstructure transition induced by carbon loss due to thermo-oxidation of the char and the development of the thermal conductivity and thickness of the coatings during the fire test.
Intumescent coatings have been used for fire protection of steel for decades, but there is still a need for improvement and adaptation. The key parameters of such coatings in a fire Scenario are thermal insulation, foaming dynamics, and cohesion. The fire resistance tests, large furnaces applying the standard time temperature (STT) curve, demand coated full‐scale components or intermediate‐scale specimen. The STT Mufu+ (standard time temperature muffle furnace+) approach is presented. It is a recently developed bench‐scale testing method to analyze the performance of intumescent coatings. The STT Mufu+ provides vertical testing of specimens with reduced specimen size according to the STT curve. During the experiment, the foaming process is observed with a high‐temperature endoscope. Characteristics of this technique like reproducibility and resolution are presented and discussed. The STT Mufu+ test is highly efficient in comparison to common tests because of the reduced sample size. Its potential is extended to a superior research tool by combining it with advanced residue analysis (μ‐computed tomography and scanning electron microscopy) and mechanical testing. The benefits of this combination are demonstrated by a case study on 4 intumescent coatings. The evaluation of all collected data is used to create performance‐based rankings of the tested coatings.
Thermal insulation and mechanical resistance play a crucial role for the performance of an intumescent coating. Both properties depend strongly on the morphology and morphological development of the foamed residue. Small amounts (4 wt%) of fiberglass, clay and a copper salt, respectively, are incorporated into an intumescent coating to study their influence on the morphology and Performance of the residues. The bench scale fire tests were performed on 75 x 75 x 2 mm³ coated steel plates according to the standard time–temperature curve in the Standard Time Temperature Muffle Furnace+ (STT Mufu+). It provided information about foaming dynamics (expansion rates) and thermal insulation. Adding the copper salt halved the expansion height, whereas the clay and fiberglass Change the height of the residue only moderately. The time to reach 500 °C was improved by 31% for clay and 15% for the other two fillers. Nondestructive micro computed tomography is used to assess the inner structure of the residues. A transition of the residue from a black, carbonaceous foam with closed cells into an inorganic, residual open cell sponge occurs at high temperatures. This transition is due to a loss of carbon; the change in microstructure is analyzed by scanning electron microscopy. Additional mechanical tests are performed and interpreted with respect to the results of the morphology analysis. Adding clay or copper salt improved the mechanical resistance tested by a factor 4. The additives significantly influence the thickness and foaming Dynamics as well as the inner structure of the residues, whereas their influence on insulation Performance is moderate. In conclusion, different modes of action are observed to achieve similar insulation performance during the fire test.
A series of flexible polyurethane foams (FPUFs) were prepared with single and different combinations of flame retardants and additives. Expandable graphite (EG), phosphorous polyol (OP), copper (II) oxide (CuO), and/or castor oil (CAS) were added to FPUF during the foam preparation in a one-step process. The purpose of the study is to evaluate the synergistic effects of the flame retardants, additives, and the presence of bio-based content on the mechanical properties, flame retardancy, and smoke behavior of FPUFs. The combination of 10 wt % EG and 5 wt % OP in FPUF significantly improves the char yield. In the cone calorimeter experiment, the char yield is nearly three times higher than that with 10 wt % EG alone. The smoke behavior is additionally evaluated in a smoke density chamber (SDC). Comparing the samples with a single flame retardant, 10 wt % EG in FPUF considerably reduces the amount of smoke released and the emission of toxic gases. Replacing the amount of 10 wt % polyether polyol in FPUF with CAS maintains the physical and mechanical properties and fire behavior and enhances the bio-based content. The presence of 0.1 wt % CuO in FPUF effectively reduces the emission of hydrogen cyanide. As a result, this study proposes a multicomponent flame retardant strategy for FPUF to enhance the biomass content and address the weaknesses in flame retardancy, smoke, and toxic gas emissions. A starting point is disclosed for future product development.
Polyamide 4.6 (PA46) is a high-heat-resistant polymer, but it has no dripping resistance under fire. Three commercial grades of PA46 are investigated under UL 94 vertical fire test conditions. Their performances are discussed based on the materials’ structural, thermal, and rheological properties. PA46 presents flaming drops, whereas dripping is prevented in the flame-retarded PA46.
Friction-modified PA46 has increased flaming dripping. Temperature profiles of the specimens under fire and the temperature of the drops are measured by thermocouples. A UL 94 vertical test configuration consisting of two flame applications is designed to assess the quantitative dripping behavior of the set of materials by the particle finite element method (PFEM). Polymer properties (activation energy and Arrhenius coefficient of decomposition, char yield, density, effective heat of combustion, heat of decomposition, specific heat capacity, and thermal conductivity) in addition to rheological responses in high temperatures are estimated and measured as input parameters for the simulations. The dripping behavior obtained by simulated materials corresponds with the experimental results in terms of time and drop size. A consistent picture of the interplay of the different phenomena controlling dripping under fire appears to deliver a better understanding of the role of different materials’ properties
The addition of nanoparticles as reinforcing fillers in elastomers yields nanocomposites with unique property profiles, which opens the door for various new application fields. Major factors influencing the performance of nanocomposites are studied by varying the type and shape of nanoparticles and their dispersion in the natural rubber matrix. The industrial applicability of these nanocomposites is put into focus using two types of graphene and a nanoscale carbon black, all commercially available, and scalable processing techniques in the form of a highly filled masterbatch production via latex premixing by simple stirring or ultrasonically assisted dispersing with surfactant followed by conventional two-roll milling and hot pressing. Different processing and measurement methods reveal the potential for possible improvements: rheology, curing behavior, static and dynamic mechanical properties, swelling, and fire behavior. The aspect ratio of the nanoparticles and their interaction with the surrounding matrix prove to be crucial for the development of superior nanocomposites. An enhanced dispersing method enables the utilization of the improvement potential at low filler loadings (3 parts per hundred of rubber [phr]) and yields multifunctional rubber nanocomposites: two-dimensional layered particles (graphene) result in anisotropic material behavior with strong reinforcement in the in-plane direction (157% increase in the Young's modulus). The peak heat release rate in the cone calorimeter is reduced by 55% by incorporating 3 phr of few-layer graphene via an optimized dispersing process.
In the processing of nanocomposites, high shear stresses at elevated tempera-tures orient two-dimensional nanoparticles like graphene. This orientationleads to anisotropic mechanical, thermal or barrier properties of the nanocom-posite. This anisotropy is addressed in this study by comparing graphene (few-layer graphene, FLG) with a nanoscaled carbon black (nCB) at a filler contentof 3 phr, by varying the vulcanization, and by comparing different FLG con-tents. Transmission electron microscopy gives insight into the qualitative ori-entation in the nanocomposite with FLG or nCB. The storage moduli paralleland normal to the orientation reveal the direction dependency of reinforce-ment through dynamic mechanical analysis (DMA). Dimensional swellingmeasurements show a restriction of the expansion parallel to the FLG orienta-tion, and an increased expansion normal to the orientation. The vulcanizationsystem and crosslinking determine the respective level of property values, andhigher crosslinking densities increase the anisotropy in DMA resulting invalues of up to 2.9 for the quantified anisotropy factor. With increasing FLGcontent, the anisotropy increases. A comparison of the results reveals swellingmeasurements as the most suitable method for the determination of anisot-ropy. Compared to recent literature, the presented processing induces higheranisotropy, leading to higher reinforcing effects in the direction of orientation
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.
Rigid polyurethane foams (RPUFs) exhibit short times to ignition as well as rapid flame spread and are therefore considered to be hazardous materials. This paper focuses on the fire phenomena of RPUFs, which were investigated through a multimethodological approach. Water-blown polyurethane (PUR) foams without flame retardants (FRs) as well as waterblown PUR foams containing triethyl phosphate as a gas phase-active FR were examined. The aim of this study is to clarify the influence of the FR on the fire phenomena during combustion of the foams. Additionally, materials’ densitieswere varied to range from 30 to 100 kg/m3. Thermophysical properties were studied bymeans of thermogravimetry; fire behavior and flammability were investigated via cone calorimeter and limiting Oxygen index, respectively. During the cone calorimeter test, the temperature development inside the burning specimens was monitored with thermocouples, and cross sections of quenched specimens were examined visually, giving insight into the morphological changes during combustion.
The present paper delivers a comprehensive study, illuminating phenomena occurring during foam combustion and the influence of a FR active in the gas phase. The superior fire performance of flameretarded PUR foams was found to be based on flame inhibition, and on increased char yield leading to a more effective protective layer. It was proven that in-depth absorption of radiation is a significant factor for estimation of time to ignition. Cross sections investigated with the electron scanning microscope exhibited a pyrolysis front with an intact foam structure underneath. The measurement of temperature development inside burning specimens implied a shift of burning behavior towards that of non-cellular materials with rising foam density.