Development of fire‐retarded materials—Interpretation of cone calorimeter data

There is little consensus within the fire science community on interpretation of cone calorimeter data, but there is a significant need to screen new flammability modified materials using the cone calorimeter. This article is the result of several discussions aiming to provide guidance in the use and interpretation of cone calorimetry for those directly involved with such measurements. This guidance is essentially empirical, and is not intended to replace the comprehensive scientific studies that already exist. The guidance discusses the fire scenario with respect to applied heat flux, length scale, temperature, ventilation, anaerobic pyrolysis and set‐up represented by the cone calorimeter. The fire properties measured in the cone calorimeter are discussed, including heat release rate and its peak, the mass loss and char yield, effective heat of combustion and combustion efficiency, time to ignition and CO and smoke production together with deduced quantities such as FIGRA and MARHE. Special comments are made on the use of the cone calorimeter relating to sample thickness, textiles, foams and intumescent materials, and the distance of the cone heater from the sample surface. Finally, the relationship between cone calorimetry data and other tests is discussed. Copyright © 2007 John Wiley & Sons, Ltd.     

Experimental study on heat release rate measurement in tunnel fires

Knowledge about the heat release rate (HRR) is essential for studying tunnel fires. The standard method in ISO 9705 is widely applied to calculate the HRR of combustion by measuring the consumption of oxygen in a fire. However, the studies of HRR measurement in full‐scale tunnel fires are rare because of the complication and costs of large experiments. This paper presents a system based on the principle of oxygen consumption calorimetry for the measurement of HRR and total heat release (THR) of full‐scale fires in tunnels. A total of 22 fire experiments are performed in a large‐scale ventilated testing metro tunnel with dimension of 100.0 m × 5.5 m × 5.5 m to validate the reliability and effectiveness of this system. Firstly, four oil spray fire tests are conducted with nozzle flow of 106 L/h at (1 ± 0.1) MW HRR to calibrate the instrumentation. Then, 18 full‐scale fire tests using square diesel pools at five sizes (0.5, 1.0, 2.5, and 5.0 m²) and wood cribs as fire sources are carried out for the measurement of HRR and THR. Results provided by the comparison between the measured HRR and THR values of the fire tests and the theoretically calculated ones show that our system works effectively in the HRR measurement of full‐scale fires in tunnels.     

Combustion properties of Brazilian natural wood species

This paper investigates the combustion characteristics of 12 wood species natural to Brazil. A mass loss cone calorimeter was used to obtain the properties associated with (i) heat release rate (HRR), peak HRR, and total heat released; (ii) total mass loss and mass loss rate; (iii) average effective heat of combustion; and (iv) time to ignition, time of pyrolysis and temperature of ignition. The samples used in this work were as follows: (i) prepared in accordance to ISO 5660‐1:2002; (ii) oven dried; (iii) irradiated with a constant heat flux of 50 kW/m²; and (iv) exhibit wood fiber orientation in a plane orthogonal to the flux incidence. Finally, the paper explores the possibility of linking the obtained combustion properties with the density and classes of selected wood species. Copyright © 2014 John Wiley & Sons, Ltd.     

Enhancement of fire retardancy properties of glass fibre–reinforced polyesters composites

This paper presents the results of an experimental investigation on the fire retardancy properties of glass fibre–reinforced polyester (GFRP) composites with bisphenol‐A vinylester and isophthalic polyester as matrices and low electrical conductivity E‐glass fibres as reinforcement. The fire protection systems tested were alumina trihydrate (ATH), decabromodiphenyl ether (DBDE), and antimony trioxide (Sb₂O₃). A mass loss cone calorimeter was used to obtain the properties of heat release rate (HRR), peak HRR, total heat released, total mass loss, time to ignition, and time of combustion. Moreover, limiting oxygen index (LOI), UL‐94, and glow‐wire tests were also performed. The fire tests were carried out in order to investigate if the combination of ATH and DBDE could have “additive,” “antagonistic,” or “synergistic” effects on the flame retardant properties of the GFRP studied in this work. In addition, the influence of the ATH content variation on flame retardant properties was also evaluated. The results indicate that the sole addition of ATH at 47.7 phr could lead to the complete inhibition of the composites ignition, while the materials containing DBDE exhibit ignition and flame propagation in the cone calorimeter test.     

Correlations between pyrolysis combustion flow calorimetry and conventional flammability tests with halogen‐free flame retardant polyolefin compounds

Seven halogen‐free flame retardant (FR) compounds were evaluated using pyrolysis combustion flow calorimetry (PCFC) and cone calorimetry. Performance of wires coated with the compounds was evaluated using industry standard flame tests. The results suggest that time to peak heat release rate (PHRR) and total heat released (THR) in cone calorimetry (and THR and temperature at PHRR in PCFC) be given more attention in FR compound evaluation. Results were analyzed using flame spread theory. As predicted, the lateral flame spread velocity was independent of PHRR and heat release capacity. However, no angular dependence of flame spread velocity was observed. Thus, the thermal theory of ignition and flame spread, which assumes that ignition at the flame front occurs at a particular flame and ignition temperature, provides little insight into the performance of the compounds. However, results are consistent with a heat release rate greater than about 66kW/m² during flame propagation for sustained ignition of insulated wires containing mineral fillers, in agreement with a critical heat release rate criterion for burning. Mineral fillers can reduce heat release rate below the threshold value by lowering the flaming combustion efficiency and fuel content. A rapid screening procedure using PCFC is suggested by logistic regression of the binary (burn/no‐burn) results. Copyright © 2008 John Wiley & Sons, Ltd.     

Experimental study on polystyrene with intumescent flame retardants from different scale experiments

In this study, the fire performance and toxicity of intumescent flame retardant (IFR) polystyrene composites were investigated experimentally. Ammonium polyphosphate, pentaerythritol, and melamine were selected as IFR. The flammability of the polystyrene (PS) composites was evaluated by microscale combustion calorimetry and cone calorimetry and in the ISO Room. The results suggested that the thermal stability and the peak heat release rate of PS composites decreased with the increasing content of IFR. In the cone calorimeter and ISO 9705 testing, the carbon monoxide yield of PS composites also decreased markedly with the addition of IFR. Scanning electron microscope images show that the char from cone calorimetry testing was more compact and smoother than that from the ISO 9705 testing. The comparison between bench‐ and full‐scale tests demonstrated that the flammability and the toxicity of PS composites are decreased markedly due to the incorporation of the flame retardant, but considerable differences exist. Copyright © 2014 John Wiley & Sons, Ltd.     

蔓延规则材料聚苯乙烯板的热释放速率模型

在小尺寸ISO 9705锥形量热平台开展了多个尺寸聚苯乙烯薄板燃烧实验,燃烧时火焰从点燃角开始以相等的蔓延速度向未燃区域加速蔓延,呈扇形规则扩散。对实验测得的燃烧热释放速率结合燃烧过程分析发现,总释热量与材料面积呈良好的线性关系,且没有燃烧平台期的上升段释热量占总释热量比例约为77.83%。利用指数函数建立数学模型表达HRR曲线,涉及的燃烧热物理性能包括热释放速率峰值、峰值时间、燃烧释热量。以实验组10×10-1的峰值时间为参考时间,拟合得到上升阶段曲线表达式,无平台期的峰值及峰值时间可由上升阶段释热量与总释热量的关系计算得到。验证结果表明,该数学模型能够较好地预测燃烧蔓延规则的聚苯乙烯材料无平台期的燃烧热释放速率发展情况和描述含平台期的热释放速率变化过程。     

Optimization of the procedure to burn textile fabrics by cone calorimeter: Part I. Combustion behavior of polyester

The aim of this study was the optimization of cone calorimeter to determine the burning behavior of textile fabrics. In particular, the combustion behavior of commercial polyester textile fabrics with varying densities was studied in terms of time to ignition (TTI), heat release rate (HRR), and relative peak (pkHRR) were monitored. Reproducibility and repeatability of the data have been verified by the influence of instrument variable including incident heat flux, the temperature of ceramic backing pads and retaining grid used during sample mounting as well as sample weight (as the number of fabric layers), the density of textiles, and the relative humidity. A low reproducibility has been obtained when a wire grid was not used to stabilize samples during the tests. The effects of these variables on TTI and pkHRR were observed. Copyright © 2010 John Wiley & Sons, Ltd.     

A novel phosphorus-containing poly(lactic acid) toward its flame retardation

An inherently flame-retardant poly(lactic acid) (PLA) was synthesized via the chain-extending reactions of dihydroxyl terminated pre-poly(lactic acid) (pre-PLA), which was synthesized by direct polycondensation of l-lactic acid using 1,4-butanediol as initiator and stannous chloride (SnCl₂) as catalyst, using ethyl phosphorodichloridate as chain extender. The resulting phosphorus-containing poly(lactic acid) (PPLA) was characterized by gel permeation chromatography (GPC), ¹H and ³¹P nuclear magnetic resonance (¹H, ³¹P NMR) and homonuclear correlation spectroscopy (COSY) and inductively coupled plasma-mass (ICP). A comprehensive flame retardant property of PPLA was evaluated by microscale combustion calorimetry (MCC), limiting oxygen index (LOI), vertical burning test (UL-94) and cone calorimeter test (CCT). PPLA has excellent flame retardancy and also can be used as a flame retardant for commercial PLA. Only 5 wt.% of PPLA added into PLA can obtain good flame retardant properties. As the content of PPLA is further increased to 10 wt.%, PLA can have much better flame retardancy (LOI = 35 and UL-94 V-0 rating), lower peak heat release rate (pHRR) and longer ignition time (TTI) than neat PLA. All those results mean that this novel approach to impart flame retardancy to PLA is very effective.     

Combustion behavior characterization of major crops through cone calorimeter

Induced by extremely inflammable characteristic, fire accidents worldwide of crops frequently occur and give rise to loss of life and personal injury. Given this problem, combustion behavior characterization of four major crops was investigated by cone calorimeter. Results confirmed the less quantity of crops needed longer time to be ignited. Meanwhile, the linear relation between the inverse square of time to ignition and heat flux of crops was found. For heat release rate (HRR), it was demonstrated that more quantity of crops prolonged the heat release process. For instance, with heat flux of 50 kW/m², HRR values of 100 and 50 g soybean at 400 seconds were 212 and 40 kW/m². Besides, peak values of HRR (PHRR) were close with different mass, especially for corn. Interestingly, compared to less quantity, more quantity crops were harder to be ignited at same heat flux. In addition to soybean, PHRR and total heat release (THR) of crops was gradually increased with the increasing heat flux. Meanwhile, THR values of 100 g crops were lower than double THR of 50 g crops. The investigation of combustion behavior characteristic could guide the safety storage of crops, thus avoiding the occurrence of crops fire hazards.     

Ignition performance of new and used motor vehicle upholstery fabrics

This paper examines the standards for fire safety in transport systems and in particular the test method for the flammability of materials within passenger compartments of motor vehicles. The paper compares data from ignition tests conducted in the cone calorimeter and the FIST apparatus with tests conducted using the FMVSS 302 horizontal flame spread apparatus. Ten materials were selected as representative of those used as seat coverings of private and commercial passenger vehicles. The time to ignition of new and used materials subject to exposure heat fluxes between 20 kW/m² and 40 kW/m² was measured. The results from the ignition tests were analysed using thermally thick and thermally thin theoretical models. The critical heat flux for sustained piloted ignition was determined from the time to ignition data using the thermally thin approach. Derived ignition temperatures from both the thermally thick and thermally thin methods were compared with measurements using a thermocouple attached to the back surface of materials in selected tests. The flame spread rates in the FMVSS 302 apparatus were determined and a comparison was made between the performance of the materials in the flame spread apparatus, the cone calorimeter and the FIST. The results suggests that a critical heat flux criterion could be used to provide an equivalent pass/fail performance requirement to that specified by the horizontal flame spread test although further testing is needed to support this. Copyright © 2004 John Wiley & Sons, Ltd.     

A study of γ‐radiation‐crosslinked HDPE/EPDM composites as flame retardants

The dynamic flammability of flame‐retardant composites that consist of high‐density polyethylene (HDPE) and ethylene–propylene–diene rubber (EPDM) and other additives, and can be used as wire‐ and cable‐insulation materials, was studied before and after irradiation. The data for the heat‐release rate (HRR), the time to ignition, the specific extinction area and the concentrations of CO and CO₂ from the burning process of cone colorimeter tests were assessed. By blending HDPE with EPDM, the HRR of HDPE was reduced and the residue char of the composite increased. The HRR of HDPE/EPDM was further reduced and the residue char of HDPE/EPDM was further increased after irradiation. The oxygen index, mechanical properties, and thermal stability of the composites, and the morphology of the char formed in the cone calorimeter test, were also investigated. Copyright © 2004 Society of Chemical Industry     

Tensile and flammability properties of polypropylene‐based RTPO/clay nanocomposites for cable insulating material

Nanocomposites of polypropylene‐based RTPO with organically modified clays were prepared by melt compounding of three components, that is, polypropylene‐based RTPO, maleic anhydride‐grafted polypropylene oligomer (PPgMA), and organically modified clay. Their morphologies, tensile behaviors, and flammability properties were investigated. In the clay nanocomposites, the silicate layers were dispersed at the nanometer level, which was confirmed by X‐ray diffraction and transmission electron microscopy. The tensile yield strength of nanocomposites containing 10 wt % clay exhibited 2.8 times higher value compared with that of neat resin. The combustion behavior of the nanocomposites was evaluated by measuring the heat release rate (HRR) using cone calorimetry. The peak HRR was lowered greatly and the char yield was very high compared with those of neat resin. However, these flame retardant properties of clay are not sufficient as a flame retardant used alone in cable applications. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2375–2381, 2005     

Thermal and chemical analysis of flammability and combustibility of fir wood in cone calorimeter coupled to FTIR apparatus

This paper deals with the thermal degradation of fir wood in a cone calorimeter under well‐ventilated atmosphere used with a piloted ignition. The thermal and chemical sample decompositions were studied with heat fluxes varying from 15 to 60 kW m^?2. With the cone calorimeter results and equations found in literature, the significant parameters of fir wood sample flammability and combustibility were deduced from ignition time (t_ig), mass loss and gas analysis. These parameters are thermal response parameter, critical heat flux, ignition surface temperature, thermal thickness, mass loss rate, thermal inertia, effective heat of combustion, heat release rate, heat of gasification and others. Moreover, during each experiment, the main gaseous species emissions were continuously and simultaneously monitored. Furthermore, the solid degradation and combustion process for fir wood were described in details. Experimental results from cone calorimeter were compared with data found in literature, and generally, a quite good accordance was found between the both sets of results. Copyright © 2013 John Wiley & Sons, Ltd.     

Burning behaviors of selected chlorosilanes and SiH‐containing siloxanes

Chlorosilanes are silanes containing the Si‐Cl functional group and SiH‐containing siloxanes are siloxanes containing the Si‐H functional group. Some chlorosilanes and SiH‐containing siloxanes present potentially high fire or explosion hazards during handling, storage, transport and process operations. Cone calorimeter tests have been used to study the burning behaviors of selected chlorosilanes and SiH‐containing siloxanes at various incident heat fluxes to simulate pool fire burning. The peak heat release rate of a silicon intermediate obtained from the cone calorimeter at 15 kW/m² incident heat flux was very close to that measured by a relatively large‐scale field test. The flammability of monochlorosilanes was similar to that of organic hydrocarbons having comparable volatility. The flammability of chlorosilanes descends in the order of monochlorosilanes, dichlorosilanes and trichlorosilanes. SiH‐containing siloxanes ignited faster than non‐SiH‐containing siloxanes because of the reactive silicon‐hydrogen linkages. The ignition of SiH‐containing siloxanes was much more violent than the ignition of non‐SiH‐containing siloxanes. The SiH‐containing siloxanes exhibited a lower peak heat release rate, less total heat released and a lower peak smoke extinction coefficient compared with non‐SiH‐containing siloxanes having comparable volatility. Copyright © 2004 John Wiley & Sons, Ltd.     

Thermal degradation of epoxy resin/carbon fiber composites: Influence of carbon fiber fraction on the fire reaction properties and on the gaseous species release

The thermal degradation of epoxy resin/carbon fiber composites has been performed in ISO 5660 standard cone calorimeter using a piloted ignition. Two kinds of composites that differ by their volume fractions in carbon fiber (56 and 59 vol.%) were tested in this study. The cone calorimeter irradiance level was increased up to 75 kW m^?2 to characterize the carbon fiber volume fraction influence on the composite thermal degradation. Thus, main flammability and combustibility parameters were determined and calculated such as mass loss, mass loss rate, ignition time, thermal response parameter, ignition temperature, thermal inertia, and heat of gasification. As a result, all the characteristic parameters for the thermal resistance of composites were decreased when the carbon fiber volume fraction increased. Moreover, the main gaseous products (such as NO, CO, CO₂, HCN, H₂O, and lightweight hydrocarbons) emitted as well as the oxygen consumption during the composite thermal decomposition were also quantified simultaneously with a portable gas analyzer and a Fourier transform infrared spectrometer. The main species emission yields calculated from the gas analysis results increased slightly when the carbon fiber volume fraction was increased in the initial sample. The epoxy composite was represented as a sooty material with a significant production of soot particles during the combustion process. Furthermore, heat release rate, total heat release, and effective heat of combustion were calculated by using the oxygen consumption calorimetry technique. The results obtained showed that a small increasing of composite carbon fiber amount induced a sharp decrease of heat release rate and total heat release. Copyright © 2014 John Wiley & Sons, Ltd.     

Experimental study on fire properties of interior materials used in low‐floor light‐rail trains

In this work, cone calorimeter tests were conducted to investigate fire properties of interior materials (floor covering [FC], aluminum plate covered with paint [APCP], light diffuser [LD], and gel coat [GC]) used in low‐floor light‐rail trains. Ignition time (t_ig) of each material decreases with the increase of radiative heat flux. The decreasing order of the four samples by ignition time under the same radiative heat flux is LD > APCP > FC > GC. The heat release rate (HRR), peak value of HRR (PHRR), time from ignition to PHRR (t_p), fire growth rate index (FIGRA), and fire growth index (FGI) rise with the increasing radiative heat flux. For the FC, LD, and GC, single HRR peak is observed in the HRR history while three peaks are observed for APCP. For PHRR, LD > FC > APCP > GC, while for t_p, GC < FC < APCP < LD. Under most conditions, the FIGRA and FGI of the FC is the highest among the four materials. Results of this work are beneficial to evaluate fire hazard of low‐floor light‐rail train and determine the emphasis of fire prevention.     

A flammability performance comparison between synthetic and natural clays in polystyrene nanocomposites

Polymer‐clay nanocomposites are a newer class of flame retardant materials of interest due to their balance of mechanical, thermal and flammability properties. Much more work has been done with natural clays than with synthetic clays for nanocomposite flammability applications. There are advantages and disadvantages to both natural and synthetic clay use in a nanocomposite, and some of these, both fundamental and practical, will be discussed in this paper. To compare natural and synthetic clays in regards to polymer flammability, two clays were used. The natural clay was a US mined and refined montmorillonite, while the synthetic clay was a fluorinated synthetic mica. These two clays were used as inorganic clays for control experiments in polystyrene, and then converted into an organoclay by ion exchange with an alkyl ammonium salt. The organoclays were used to synthesize polystyrene nanocomposites by melt compounding. Each of the formulations was analysed by X‐ray diffraction (XRD), thermogravimetric analysis (TGA) and transmission electron microscopy (TEM). Flammability performance was measured by cone calorimeter. The data from the experiments show that the synthetic clay does slightly better at reducing the heat release rate (HRR) than the natural clay. However, all the samples, including the inorganic clay polystyrene microcomposites, showed a decreased time to ignition, with the actual nanocomposites showing the most marked decrease. The reason for this is postulated to be related to the thermal instability of the organoclay (via the quaternary alkyl ammonium). An additional experiment using a more thermally stable organoclay showed a time to ignition identical to that of the base polymer. Finally, it was shown that while polymer‐clay nanocomposites (either synthetic or natural clay based) greatly reduce the HRR of a material, making it more fire safe, they do not provide ignition resistance by themselves, at least, at practical loadings. Specifically, the cone calorimeter HRR curve data appear to support that these nanocomposites continue to burn once ignited, rather than self‐extinguish. Copyright © 2004 John Wiley & Sons, Ltd.     

Combustion behaviour of polyurethane flexible foams under Cone Calorimetry test conditions

The first part of this study focuses on the effect of cone calorimeter test variables on polyurethane flexible foam properties such as ignitability, heat release rate, effective heat of combustion and mass loss. Three of the main commercial foam types were used, i.e. conventional slabstock foams, high-resilience slabstock foams and all-MDI (methylene diphenyldiisocyanate) moulded foams. A decrease in heat flux (down to 40%) with increasing distance from the conical heater was measured. As a consequence, results were found to depend to a large extent on the thickness and the melting behaviour of the foam samples. To achieve a sufficiently constant and uniform heat flux exposure, sample thickness had to be limited to 25 mm. In addition, repeatability was found to be good under various conditions, with percentage standard deviations for effective heat of combustion, peak rate of heat release and mass loss below 10%. Levels of radiant flux above 25 kW m^?2 were found to be very severe to test flexible polyurethane foams. Under such conditions, foams that show large differences in combustion performance in small-scale flammability tests performed almost identically in the cone calorimeter. In the second part of this study the effects of foam variables, such as foam type, density and melamine content, are defined. These effects were clearly pronounced at radiant flux levels of 15–25 kWm^?2. Density was found to be the key variable in controlling ignition resistance. In addition, high-resilience slabstock foams and all-MDI moulded foams performed better than conventional slabstock foams of the same density. Melamine addition resulted in a delay of ignition for all three foam types and an incomplete combustion, decreased heat release and effective heat of combustion in HR-slabstock and all MDI moulded foams. However, melamine is not effective as a heat sink in conventional slabstock foams. The different performance of the foam types under study can be explained by a different melting behaviour.     

Comparison of cone and OSU calorimetric techniques to assess the flammability behaviour of fabrics used for aircraft interiors

Two test methods for measuring the heat release rate, HRR have been compared on fabric composites used for aircraft interior materials as side‐wall panels. These methods are based on the principles of direct measurement of the convective and radiant heat by thermopiles using an Ohio State University (OSU) calorimeter, and oxygen consumption using a cone calorimeter. It has been observed when tested by standard procedures, cone results at 35 kW/m² incident heat flux do not correlate with OSU results at the same heat flux. This is because in the cone calorimeter, the sample is mounted horizontally whereas the OSU calorimetric method requires vertical sampling with exposure to a vertical radiant panel. A further difference between the two techniques is the ignition source—in the cone it is spark ignition, whereas in the OSU it is flame ignition; hence, samples in the OSU calorimeter ignite more easily compared to those in the cone under the same incident heat fluxes. However, in this paper we demonstrate that cone calorimetric exposure at 50 kW/m² heat flux gives similar peak heat release results as the 35 kW/m² heat flux of OSU calorimeter, but significantly different average and total heat release values over a 2 min period. The performance differences associated with these two techniques are also discussed. Moreover, the effects of structure, i.e. type of fibres used in warp/weft direction and design of fabric are also analysed with respect to heat release behaviour and their correlation discussed. Copyright © 2005 John Wiley & Sons, Ltd.