Improving the fire performance and smoke suppression of expandable polystyrene foams by coating with multi-dimensional carbon nanoparticles

Expandable graphite (EG) and modified multi-wall carbon nanotubes (ATH-MWNT) were introduced to expandable polystyrene (EPS) foams in order to improve its fire performance. The fire performance of EPS foams was evaluated by limiting the oxygen index (LOI), vertical burning (UL-94), and cone calorimetry tests. The results showed that the presence of 14.3% EG and 4.1% ATH-MWNT increased the LOI value from 18.0 to 30.3%, upgraded the UL-94 rating from no rating to V-0, completely eliminated melt dripping, and significantly decreased the peak heat release rate from 933 to 177 kW/m². Thermal analysis indicated that the thermal stability and char formation were improved by the presence of flame retardants. The char morphology was characterized by scanning electronic microscopy (SEM). It was suggested that the presence of EG and ATH-MWNT could form integrated char layers during combustion, which was beneficial to the formation of an intumescent protective char structure.     

Grafting modification bamboo kraft lignin and its performance in rigid polyurethane foams

In order to improve the efficiency of intumescent flame retardant (IFR), bamboo kraft lignin (BKL) was chemically functionalized by grafting melamine (MEL) and diethyl phosphite (DEP) and used for rigid polyurethane (RPU) foam. The BKL, MEL, and DEP in IFR system were used as char forming agent, gas, and acid source, respectively. The FTIR and XPS results indicated that the nitrogen (N) and phosphorus (P) containing BKL was successfully synthesized. The limiting oxygen index (LOI) value of N-BKL and N/P-BKL RPU foams were higher than BKL RPU foam, suggesting that N-BKL and N/P-BKL improved flame retardancy of the foams. The total heat release (THR), heat release rate (HRR), effective heat of combustion (EHC), and fire growth rate (FIGRA) values of N-BKL and N/P-BKL RPU foams were much lower than that of BKL RPU foam. The flame retardancy index value of N/P-BKL RPU foams was higher comparing to N-BKL RPU foam. These results indicated that the synergistic interaction between N containing compound of MEL and P containing compound of DEP led to the improvement flame retardant properties. Comparing to BKL RPU foam, the N/P-BKL RPU foam increased 74°C of maximum weight loss temperature and decreased 18.1 wt% of mass loss, indicating enhanced thermal stability. The morphology of char after cone calorimeter testing showed the N/P-BKL RPU foam presented more continuous and compact char residues, which could reduce heat and mass transfer, protecting underlying materials from further combustion in a fire, thus resulting in good flame retardancy and thermal stability properties. This work suggests a promising route to enhancing the flame-retardant performance of RPU foam using nontoxic and more environmentally friendly grafted bamboo lignin.     

Combustion behaviour of fabric and polyurethane flexible foam mock-up combinations under Cone Calorimetry test conditions

The relative contributions of fabric and foam on important fire hazard parameters as measured in the cone calorimeter were determined for various mock-up combinations. Three commercial types of high-resilience PU flexible slabstock foams, representing a wide range of combustion performance, were combined with three different fabrics: polyester, polypropylene and combustion-modified cotton. Total heat release of the combinations correspond well with the value calculated from the individual components and is determined by the density and effective heat of combustion of the components, and the foam/fabric weight ratio. The foams show a smaller variation in effective heat of combustion than the fabrics. Covering of PU flexible foams with a fabric results in general in a delay of ignition and peak rate of heat release. Performance of the mock-ups is mainly determined by the fabric but is also influenced by the quality of the foam.     

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.     

Relationship between the thermal degradation chemistry and flammability of commercial flexible polyurethane foams

In this article, we report the use of a variety of analytical methods, in particular, solid‐state ¹H‐NMR and ¹³C‐NMR to characterize the relationship between the condensed‐phase chemistry and burning behavior as determined by a series of combustion tests for two commercially derived flexible polyurethane foams, one combustion‐modified. The combustion tests showed that the foams met several regulatory requirements in terms of their fire performance, whether or not they were combustion‐modified. Both foams passed the MV SS 302 and CAL 117 small‐flame tests. The nonmodified foam failed the Crib 5 test, but this test had a much larger ignition source. The particular problem with the nonmodified foam was melt drip into the flame zone. This led to a steady maintenance of the fuel feed and a rapid escalation of the fire. In contrast, the combustion‐modified foam showed little melt drip and self‐extinguished. Thermal analysis data for the two foams showed that melamine acted in part as an endothermic heat sink. This alone did not account for the much reduced melt flow and drip of the combustion‐modified foam, but the solid‐state ¹H‐NMR data clearly showed that the molecular mobility of the combustion char from combustion‐modified foam was lower than the unmodified foam char, which indicated that the flame‐retardant formulation in the combustion‐modified foam acted by a condensed‐phase mechanism. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3024–3033, 2006     

Burning rate of solid wood measured in a heat release rate calorimeter

Burning rate is a key factor in modeling fire growth and fire endurance of wood structures. This study investigated the burning rate of selected wood materials as determined by heat release, mass, loss and charring rates. Thick samples of redwood, southern pine, red oak and basswood were tested in a heat release rate calorimeter. Results on ignitability and average heat release, mass loss and charring rates are reported for a heat flux range between 15 and 55 kw m^?2. In this range, burning rate increased linearly with heat flux. Burning rate was very species dependent. Heat release rate was related to mass loss by effective heat of combustion, which also increased with heat flux. Charring rate was related to mass loss rate and original wood density. Important char property data such as yield, density and contraction are reported. A simplified calculation method is proposed for calculating mass loss rate and charring rate based on heat release rate.     

Lightweight,Elastomeric, and Flame‐Retardant Foams from Expanded Chlorinated Polymers

Intrinsically flame‐retardant polymers based on lightweight and elastomeric microcellular foams are successfully prepared from flexible chlorinated polyethylene (CPE)/chlorinated polyvinylchloride (CPVC) compounds through compression molding foaming technology. The incorporation of CPVC to CPE at once improves the foam characteristics, and enhances the mechanical and fire performances. Due to the plausible intermolecular and intramolecular crosslinking among the polymer chains, the dense network structure of CPE/CPVC with enhanced strength results in increased cell size, reduced cell density, and improved dimensional stability of CPE/CPVC foams (CCFs). These improvements are noticed to be enhanced with increasing CPVC content in the CCF. Also, the flame‐retardant properties of the foams (i.e., limiting oxygen index and cone calorimeter combustion) are found to be increased with the increase of CPVC content. For instance, a highly flame‐retardant CCF at CPE/CPVC ratio of 60/40 shows a shorter combustion period, as derived from the respective heat release rate vs time curve. Corresponding peaks of heat release rate, total heat release rate, peak of mass loss rate, total smoke release, and char residue are recorded to be 8.4%, 5.8%, 3.0%, 6.6%, and 1000.1% of those recorded for the pristine CPE foam.     

Apparatus for the vertical orientation cone calorimeter testing of flexible polyurethane foams

Of concern to regulators and fire safety engineers is how flexible polyurethane foam drips and flows during burning. Specifically, flexible polyurethane foam forms a burning ‘pool’ of liquid as the foam decomposes, which can lead to accelerated flashover events. To fully study this phenomenon where the ‘pool fire’ accelerates heat release, large‐scale tests like the furniture calorimeter (American Society of Testing and Materials (ASTM) E1537) are used, and no small‐scale technique exists. In this paper, we present our work in developing a new sample holder that works with a bench‐scale heat release test, the cone calorimeter (ASTM E1354). The holder was built upon designs developed by the National Institute of Standards and Technology, which placed the foam in a cage in a vertical orientation during cone calorimeter testing. In this paper, we show the schematics for this test apparatus, as well as results obtained with this apparatus on four different flexible foams (shape memory and high‐density foam, flame retarded and non‐flame retarded). We compare the results from the vertical testing with that obtained via traditional horizontal ASTM E1354 testing. The advantages and disadvantages of this new apparatus are discussed in this paper. Copyright © 2014 John Wiley & Sons, Ltd.     

A flame‐retardant composite foam: foaming polyurethane in melamine formaldehyde foam skeleton

A composite foam, polyurethane–melamine formaldehyde (PU/MF) foam, was prepared through foaming PU resins in the three‐dimensional netlike skeleton of MF foam. The chemical structure, morphology, cell size and distribution, flame retardancy, thermal properties and mechanical properties of such composite foam were systematically investigated. It was found that the PU/MF foam possessed better fire retardancy than pristine PU foam and achieved self‐extinguishment. Moreover, no melt dripping occurred due to the contribution of the carbonized MF skeleton network. In order to further improve the flame retardancy of the composite foam, a small amount of a phosphorus flame retardant (ammonium polyphosphate) and a char‐forming agent (pentaerythritol) were incorporated into the foam, together with the nitrogen‐rich MF, thus constituting an intumescent flame‐retardant (IFR) system. Owing to the IFR system, the flame‐retardant PU/MF foam can generate a large bulk of expanded char acting as an efficient shielding layer to hold back the diffusion of heat and oxygen. As a result, the flame‐retardant PU/MF foam achieved a higher limiting oxygen index of 31.2% and exhibited immediate self‐extinguishment. It exhibited significantly reduced peak heat release rate and total heat release, as well as higher char residual ratio compared to PU foam. Furthermore, the composite foam also showed obviously improved mechanical performance in comparison with PU foam. Overall, the present investigation provided a new approach for fabricating a polymer composite foam with satisfactory flame retardancy and good comprehensive properties. © 2018 Society of Chemical Industry     

The effect of the trimerization catalyst on the thermal stability and the fire performance of the polyisocyanurate‐polyurethane foam

In this work, 3 currently used trimerization catalysts, TMR‐2 (quaternary ammonium), K‐15 (potassium octoate), and PU‐1792 (potassium acetate) were used to produce rigid polyisocyanurate (PIR) foams with certain amounts of isocyanurate contents. The results from Fourier transform infrared (FTIR) quantitative analysis showed that PU‐1792 had the highest catalytic efficiency in isocyanurate formation. Then, the effect of different amounts of PU‐1792 catalyst on isocyanurate ring output was further investigated, and the result showed that the highest amount of isocyanurate ring formation could be attained by the 5 pphp of PU‐1792 catalyst. It was also found that the increased amount of isocyanurate ring could result in reduced cell size, improved compressive strength, and lowered thermal conductivity of PIR foam. The results from thermogravimetric analysis (TGA) and cone calorimeter (CONE) test revealed that the thermal stability and fire performance of PIR foam could be improved with the increased amount of isocyanurate ring. Furthermore, the CONE test indicated that the smoke production of PIR foam decreased approximately 51.7% in comparison to the reference polyurethane (PU) foam, and the SEM image of char morphology showed that the char of PIR foam was more compact than PU foam.     

Highly flame‐retardant bio‐based polyurethanes using novel reactive polyols

Poor flame retardancy of polyurethanes (PU) is a global issue as it limits their applications particularly in construction, automobile, and household appliances industries. The global challenge of high flammability of PU can be addressed by incorporating flame‐retardant materials. However, additive flame‐retardants are non‐compatible and depreciate the properties of PU. Hence, reactive flame‐retardants (RFR) based on aliphatic (Ali‐1 and Ali‐2) and aromatic (Ar‐1 and Ar‐2) structured bromine compounds were synthesized and used to prepare bio‐based PU using limonene dimercaptan. The aromatic bromine containing foams showed higher close cell content (average 97 and 100%) and compressive strength (230 and 325 kPa) to that of aliphatic bromine containing foams. Similar behavior was observed for a horizontal burning test where with a low concentration of bromine (5 wt %) in the foams for Ar‐1 and Ar‐2 displayed a burning time of 12.5 and 11.8 s while, Ali‐1 and Ali‐2 displayed burning time of 25.7 and 37 s, respectively. Neat foam showed a burning time of 74 s. The percentage weight loss for neat PU foam was 26.5%, while foams containing 5 wt % bromine in Ali‐1, Ali‐2, Ar‐1, and Ar‐2 foams displayed weight loss of 11.3, 14, 7.9, and 14%, respectively. Our results suggest that flame retardant PU foams could be prepared effectively by using RFR materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46027.     

Bi-phase flame-retardant effect of hexa-phenoxy-cyclotriphosphazene on rigid polyurethane foams containing expandable graphite

The flame-retardant rigid polyurethane (PU) foams with hexa-phenoxy-cyclotriphosphazene/expandable graphite (HPCP/EG) were prepared through box-foaming in our laboratory. The flame retardancy of PU foams was characterized using the limiting oxygen index and cone calorimeter. The results show that the incorporation of HPCP into the PU foams containing EG enhanced flame retardancy. The main degradation process of HPCP in PU foams was investigated by pyrolysis gas chromatography/mass spectroscopy. HPCP during combustion generated phenoxyl and PO₂ free radicals, which could quench the flammable free radicals produced by the matrix and hamper the free radical chain reaction of combustion. This observation shows that HPCP produced a gas-phase flame-retardant effect in this specimen. Additionally, micro-morphology, elemental composition and content of residual char of the flame-retardant PU foams after the cone calorimeter test were also characterized using scanning electron microscope and energy dispersive X-ray microanalyser. The results exhibit that the partial phosphorus from HPCP remained in the residual char, and HPCP significantly enhanced the strength and compatibility of the char layer formed by the PU foams containing EG. These results indicate the important function of HPCP in condensed phase. Thus, HPCP exhibited gas-phase and condensed-phase flame-retardant effects on the PU/EG foams.     

聚丙烯膨胀成炭行为对裂解燃烧过程的影响

对膨胀阻燃聚丙烯材料在锥形量热仪试验条件下的燃烧过程进行了研究，分析了材料膨胀成炭行为对裂解燃烧过程的影响。测量了纯聚丙烯及膨胀阻燃聚丙烯在膨胀燃烧过程中的质量损失速率、热释放速率和炭层膨胀高度随时间变化规律。分析了膨胀高度、膨胀速度、炭层结构对裂解燃烧的影响。结果表明，随着膨胀阻燃剂添加量的增加，膨胀升高的速度有加快的趋势；随着外部辐射功率的加大，膨胀速度加快。聚丙烯材料的炭层整体性越强，炭层结构越致密，阻隔效果越好，热释放速率越低。通过对材料膨胀成炭过程的理论分析也验证了膨胀高度（或膨胀速度）和炭层的结构都对裂解燃烧过程有很大的影响。     

Toward an understanding of how red phosphorus and expandable graphite enhance the fire resistance of expandable polystyrene foams

Flame retardant expandable polystyrene (EPS) foams were prepared by coating method. Red phosphorus (RP) and expandable graphite (EG) were chosen as the flame retardants to be coated on the surface of expanded PS beads. By the presence of 33 phr RP/EG with a mass ratio of 1:1, the limiting oxygen index of EPS foam could reach up to 26.9%, with V-0 rating obtained in UL-94 test. The peak heat release rate could also decrease to 180.67 kW/m², which was 72.9% lower than that of neat EPS sample. Thermogravimetric analysis revealed an obvious increase of thermal stability and residue char amount by the presence of RP and EG. From the observation and analysis of char residue, it could be proposed that there existed a significant synergistic effect between RP and EG. RP could be oxidized and further react with graphite by the presence of oxygen at high temperature, forming isolated char layer and releasing nonflammable gases. Moreover, P radicals were generated at high temperature and could capture the radicals formed during the combustion of polystyrene and eliminate the burning chain reactions.     

Effects of variations in incident heat flux when using cone calorimeter test data for prediction of full‐scale heat release rates of polyurethane foam

The development of methods to predict full‐scale fire behaviour using small‐scale test data is of great interest to the fire community. This study evaluated the ability of one model, originally developed during the European Combustion Behaviour of Upholstered Furniture (CBUF) project, to predict heat release rates. Polyurethane foam specimens were tested in the furniture calorimeter using both centre and edge ignition locations. Input data were obtained using cone calorimeter tests and infrared video‐based flame area measurements. Two particular issues were investigated: how variations in incident heat flux in cone calorimeter tests impact heat release rate predictions, and the ability of the model to predict results for different foam thicknesses. Heat release rate predictions showed good agreement with experimental results, particularly during the growth phase of the fire. The model was more successful in predicting results for edge ignition tests than for centre ignition tests and in predicting results for thinner foams. Results indicated that because of sensitivity of the burning behaviour to foam specimen geometry and ignition location, a single incident heat flux could not be specified for generating input for the CBUF model. Potential methods to determine appropriate cone calorimeter input for various geometries and ignition locations are discussed. Copyright © 2014 John Wiley & Sons, Ltd.     

Flame‐retardant mechanism of expandable polystyrene foam with a macromolecular nitrogen–phosphorus intumescent flame retardant

Expandable polystyrene (EPS) foam is largely used as the thermally insulating external wall in buildings and constructions, but it is extremely flammable because of the presence of almost 98% air into its porous structure, its high surface‐area‐to‐mass ratio, and its elemental composition. Lots of serious fire disasters caused by EPS foam have posed great threats to people's properties and lives in recent years. Thus, a halogen‐free, flame‐retardant EPS is urgently needed, and its preparation is still a global challenge. To solve the problem that it is easy for EPS foam to form melt dripping and difficult for it to generate a char layer during the combustion process, a macromolecular nitrogen–phosphorus intumescent flame retardant (MNP) was selected to prepare flame‐retardant EPS foam and good mechanical and flame‐retardant properties were obtained. The scanning electron microscopy characterization revealed that MNP could penetrate into the gap between the beads, and a thin physical coating layer formed on the surface of the bead. The data from the thermogravimetry–Fourier transform infrared test indicated that a nitrogenous noncombustible gas was generated by the pyrolysis of MNP. When the MNP content increased to 30%, the limiting oxygen index and the smoking density rate of the EPS–MNP foam were 28.8 and 23.6, respectively, and a UL94 V‐0 classification was achieved. In addition, the heat‐release rate, total heat‐release, smoke produce rate, and carbon dioxide production of the EPS–MNP foams all decreased obviously; this was attributed to the flame‐retardant effects of MNP in both the condensed and gas phases. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44356.     

酚醛泡沫的燃烧行为及阻燃研究进展

酚醛泡沫因兼具优异的保温性能和阻燃性能在工程领域得到广泛应用,但其经高温燃烧后质量残留率很低,炭层疏松、强度低,离开火焰后还易出现阴燃现象。目前有关酚醛泡沫燃烧行为的研究大多集中在如何进一步提高酚醛泡沫塑料的阻燃等级或在改善其脆性的同时不降低固有的阻燃性能,还未见关于酚醛泡沫燃烧全过程行为的综述报道。文章介绍了酚醛泡沫在明火燃烧和阴燃状态的燃烧行为,分析了影响酚醛泡沫燃烧行为的因素,并总结了现有酚醛泡沫阻燃研究的进展。目前酚醛泡沫的燃烧行为及阻燃研究主要集中在泡沫的明火燃烧,对酚醛泡沫阴燃问题的研究重视不足,缺乏针对酚醛泡沫燃烧全过程的行为和机理探究。因此,提出应加大对酚醛泡沫阴燃行为的研究投入,注重对酚醛泡沫燃烧全过程的机理探索与阻燃方案研究,设计并研发出解决酚醛泡沫燃烧全过程问题的有效途径。     

酚醛泡沫的燃烧行为及阻燃研究进展

酚醛泡沫因兼具优异的保温性能和阻燃性能在工程领域得到广泛应用,但其经高温燃烧后质量残留率很低,炭层疏松、强度低,离开火焰后还易出现阴燃现象。目前有关酚醛泡沫燃烧行为的研究大多集中在如何进一步提高酚醛泡沫塑料的阻燃等级或在改善其脆性的同时不降低固有的阻燃性能,还未见关于酚醛泡沫燃烧全过程行为的综述报道。文章介绍了酚醛泡沫在明火燃烧和阴燃状态的燃烧行为,分析了影响酚醛泡沫燃烧行为的因素,并总结了现有酚醛泡沫阻燃研究的进展。目前酚醛泡沫的燃烧行为及阻燃研究主要集中在泡沫的明火燃烧,对酚醛泡沫阴燃问题的研究重视不足,缺乏针对酚醛泡沫燃烧全过程的行为和机理探究。因此,提出应加大对酚醛泡沫阴燃行为的研究投入,注重对酚醛泡沫燃烧全过程的机理探索与阻燃方案研究,设计并研发出解决酚醛泡沫燃烧全过程问题的有效途径。     

阻燃聚氨酯软质泡沫塑料中氯含量的测定

叙述了阻燃聚氨酯软质泡沫塑料中氯含量的测定方法:在助燃剂存在下,氧瓶燃烧使聚氨酯软质泡沫塑料中的有机氯转化为HCl,用稀NaOH吸收,使用硫氰酸汞分光光度法测定聚氨酯软质泡沫塑料中阻燃剂的氯含量。该方法简单快捷、精确度高,回收率为99.64%～102.41%。     

Flame retardancy of different‐sized expandable graphite particles for high‐density rigid polyurethane foams

The effects of expandable graphite (EG) of different particle sizes, on the fire‐retardant properties of high‐density rigid polyurethane foam (RPUF) (0.45 g cm^?3) were studied. Samples of EG with different particle sizes were obtained by pulverization in an ultra‐high‐speed mixer for 4 and 13 min, respectively. It was shown that as received (EG0) and 4 min pulverized EG (EG4) efficiently improved the fire‐retardant properties of RPUF composites, while 13 min pulverized EG (EG13) did not. The char of the burned composites filled with EG0 and EG4 covered the whole surface of the samples and formed a complete physical barrier. This barrier material prevented combustible gases from feeding the flame and also isolated oxygen efficiently from the burning material. EG13 did not produce enough char to cover the whole surface of the burning sample, resulting in poor fire‐retardant property of the RPUF composites. Thermal degradation tests of the foams by thermogravimetric analysis indicated that EG showed negligible effects on the thermal stability of the RPUFs. Copyright © 2006 Society of Chemical Industry