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.     

Fire retardancy effect of phosphorus‐modified halloysite on polyamide‐11 nanocomposites

Halloysite nanotubes (HNTs) were successfully incorporated as flame retardants in polyamide‐11 (PA11) after their modification with methyl phosphonic acid. Fourier transform infrared spectroscopy, thermal gravimetric analysis (TGA) and pyrolysis–gas chromatography–mass spectrometry were used to evidence the functionalization of the clay. Raw and modified HNTs were then incorporated by melt mixing in PA11 at 20 wt%. Compositions containing both ammonium polyphosphate (APP) and HNTs were also prepared. TGA and pyrolysis combustion flow calorimeter exhibited enhancement in thermal stability upon incorporation of both raw and modified halloysite nanotubes while APP causes degradation at lower temperature. Cone calorimeter data showed that modified halloysite acts by forming an insulating barrier during the combustion, which limits heat and mass transfers. Moreover, elemental analysis of sample residues after cone test evidenced that a part of the phosphorus of the modified halloysite was transferred to the gaseous phase. These results suggest the full potential of halloysite as fire retardant agent for polyamides. POLYM. ENG. SCI., 59:526–534, 2019. © 2018 Society of Plastics Engineers     

Synthesis,characteristic of a novel flame retardant containing phosphorus and its application in poly(ethylene‐co‐vinyl acetate)

A novel flame retardant (SPDH) containing phosphorus was synthesized through the reaction of 10‐(2, 5‐dihydroxyphenyl)‐9, 10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO‐HQ) and synthesized intermediate product 3, 9‐dichloro‐2, 4, 8, 10‐tetraoxa‐3, 9‐diphosphaspiro(5.5)undecane‐3, 9‐dioxide (SPDPC). The structure and properties of SPDPC and SPDH were characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR) spectroscopy and thermogravimetric analysis (TGA). After blending with poly(ethylene‐co‐vinyl acetate) (EVA), the flame‐retardant properties of EVA/SPDH composites were estimated by cone calorimeter, limited oxygen index (LOI) and UL‐94 tests, whereas the thermal stabilities were investigated using TGA. The morphological microstructure of the char formed by EVA/SPDH composite after combustion in cone calorimeter was investigated by scanning electron microscopy (SEM). The results indicate that the flame retardant and thermal stability were improved by incorporation of SPDH. The rich foamy char layers were observed from the residues after combustion in a cone calorimeter, which exactly benefits the improvement of thermal stability and flame retardant property of materials. Copyright © 2010 John Wiley & Sons, Ltd.     

Development of a controlled‐atmosphere cone calorimeter

A controlled‐atmosphere cone calorimeter has been developed that overcomes many of the shortcomings of previously developed units. The new apparatus is a fully sealed ‘blow‐through’ system, which provides a full‐size chamber in which the combustion process can occur. Oxygen concentrations from 0%–20.95% are achieved while maintaining the required configuration and flow rates to meet standard cone calorimeter testing requirements. The apparatus was developed in order to obtain data on the burning of materials at reduced oxygen levels for modelling purposes. It is now being used in pyrolysis studies assisting in the determination of fundamental material flammability properties. Copyright © CSIRO Australia 2000     

Thermal and combustion behavior of ethylene‐vinyl acetate/aluminum trihydroxide/Fe‐montmorillonite composites

The flammability characterization and synergistic flame‐retardant effect of Fe‐montmorillonite (Fe‐OMT) in the ethylene‐vinyl acetate/aluminum hydroxide (EVA/ATH) compounds were studied using limiting oxygen index (LOI), UL‐94 test, cone calorimeter, microscale combustion calorimetry (MCC), and thermogravimetric analysis (TGA). The results showed that addition of Fe‐OMT increases the LOI value and improves the UL 94 rating. Cone calorimeter data indicate that the addition of Fe‐OMT greatly reduced the heat release rate and carbon monoxide production rate. Furthermore a compact char residue formed on the surface of the sample with a suitable of Fe‐OMT during the combustion. The MCC results indicate that addition of Fe‐OMT reduced the heat release rate and catalyzed the decomposition of EVA. The TGA data showed further evidence that Fe‐OMT can catalyze carbonization reactions. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Preparation and characterization of microcapsulated red phosphorus and its flame‐retardant mechanism in halogen‐free flame retardant polyolefins

Microcapsulated red phosphorus (MRP), with a melamine–formaldehyde resin coating layer, was prepared by two‐step coating processes. The physical and chemical properties of MRP were characterized by Fourier‐transform infrared spectroscopy (FTIR), X‐ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM) and other measurements. The flame retardant action and mechanism of MRP in the halogen‐free flame retardant (HFFR) polyolefins (PO) blends have been studied using cone calorimeter, limiting oxygen index (LOI), thermogravimetric analysis (TGA) and dynamic FTIR spectroscopy. The results show that the MRP, which is coated with melamine–formaldehyde resin, has a higher ignition point, a considerably lower amount of phosphine evolution and of water absorption compared with red phosphorus (RP) itself. The data observed by cone calorimeter, LOI and TGA measurements from the PO/HFFR blends demonstrated that the MRP can decrease the heat release rate and effective heat of combustion, and increase the thermostability and LOI values of PO materials. The dynamic FTIR results revealed the flame‐retardant mechanism that RP can promote the formation of charred layers with the P–O and P–C complexes in the condensed phase during burning of polymer materials. Copyright © 2003 Society of Chemical Industry     

Ignition and combustion of low‐density polyimide foam

The ignition, flaming and smoldering combustion of low‐density polyimide foam have been studied using a cone calorimeter. Low‐density polyimide foam exhibits a high ignition resistance. The minimum heat flux for the ignition of flaming combustion ranges from 48 to 54 kW/m². This minimum heat flux also indicates the heat flux for transition from smoldering to flaming combustion. The flaming combustion results show that the heat release rate of low‐density polyimide foam is very low even at a high incident heat flux of 75 kW/m². The smoldering combustion results show that the smoldering of low‐density polyimide foam becomes significant when the incident heat flux is greater than 30 kW/m². The smoldering combustion of low‐density polyimide foam cannot be self‐sustaining when the external heat source is removed. Copyright © 2003 John Wiley & Sons, Ltd.     

The influence of carbon‐based fillers on the flammability of polypropylene‐based co‐extruded wood‐plastic composite

Comparative analysis of the effect of carbon‐based fillers with different particle sizes and morphologies on the flammable properties of a co‐extruded wood‐plastic composite is performed. Five carbon‐based fillers, namely carbon black, carbon nanotubes, graphite, expandable graphite, and carbon fibers were loaded into the shell layer of the composite. The flammability was characterized by using the cone calorimeter technique. The nanosized fillers, carbon black and carbon nanotubes, had a larger impact on the peak of the heat release rate, decreasing it by 16% and 17%, respectively. The samples with graphite, expandable graphite, and carbon fibers, decreased the peak of the heat release rate by 10%, 6%, and 11%, respectively. The total heat release decreased slightly for all the samples, except for the carbon fibers–wood‐plastic composite. The effective heat of combustion decreased also slightly, and carbon monoxide production increased for all the studied composites. Copyright © 2015 John Wiley & Sons, Ltd.     

Cone calorimeter analysis of UL‐94 V‐rated plastics

Cone calorimeter analysis was conducted on 18 thermoplastics with different UL‐94 vertical burn test (V) ratings. Ratings varied from V‐0 to no rating (NR), and the types of thermoplastics included were polycarbonate (PC), acrylonitrile–butadiene–styrene (ABS), PC/ABS blends, high‐impact polystyrene (HIPS), polypropylene (PP), and poly(vinyl chloride) (PVC). Our analysis of the cone calorimeter data found that there were correlations between UL‐94 V rating and some cone calorimeter measurements (peak heat release rate (HRR) average and HRR at 60 s) and no relationship for other measurements (time to ignition and total heat release). However, no precise correlation was found due to significant differences in flame retardant mechanism and polymer fuel energy values. In this paper, we seek to explain further why a broad quantitative relationship between UL‐94 V and cone calorimeter remains elusive, and also to show how the cone calorimeter can be used to understand why a material passes or fails a particular UL‐94 V rating. Copyright © 2006 John Wiley & Sons, Ltd.     

Poly(methyl methacrylate)/montmorillonite nanocomposites prepared with a novel reactive phosphorus–nitrogen‐containing monomer of N‐(2‐(5,5‐dimethyl‐1,3,2‐dioxaphosphinyl‐2‐ylamino)ethyl)‐ acrylamide and its thermal and flame retardant properties

A novel reactive phosphorus–nitrogen‐containing monomer, N‐(2‐(5,5‐dimethyl‐1,3,2‐dioxaphosphinyl‐2‐ylamino)ethyl)‐acrylamide (DPEAA), was synthesize and characterized. Flame retardant poly(methyl methacrylate)/organic‐modified montmorillonite (PMMA‐DPEAA/OMMT) nanocomposites were prepared by in situ polymerization by incorporating methyl methacrylate, DPEAA, and OMMT. The results from X‐ray diffraction and transmission electron microscopy (TEM) showed that exfoliated PMMA‐DPEAA/OMMT nanocomposites were formed. Thermal stability and flammability properties were investigated by thermogravimetric analysis, cone calorimeter, and limiting oxygen index (LOI) tests. The synergistic effect of DPEAA and montmorillonite improved thermal stability and reduced significantly the flammability [including peak heat release rates (PHRR), total heat release, average mass loss rate, etc.]. The PHRR of PMMA‐DPEAA/OMMT was reduced by about 40% compared with pure PMMA. The LOI value of PMMA‐DPEAA/OMMT reached 27.3%. The morphology and composition of residues generated after cone calorimeter tests were investigated by scanning electronic microscopy (SEM), TEM, and energy dispersive X‐ray (EDX). The SEM and TEM images showed that a compact, dense, and uniform intumescent char was formed for PMMA‐DPEAA/OMMT nanocomposites after combustion. The results of EDX confirmed that the carbon content of the char for PMMA‐DPEAA/OMMT nanocomposites increased obviously by the synergistic effect of DPEAA and montmorillonite. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Thermal behaviors and flame‐retardancy of styrene–ethylene–butadiene–styrene–block copolymer containing various additives

The thermal behaviors and the flame‐retardancy of styrene–ethylene–butadiene–styrene–block copolymer containing various additives were studied. The combustion was measured by the Underwriter laboratory (UL) test and cone calorimeter test and thermogravimetric analysis and program‐mass spectroscopy were applied to analyze the thermal behaviors. The blend with halogen additives showed the best result in the UL test. However, the blend with red‐phosphorous was the best in the cone calorimeter test. As the styrene sequence in the copolymer tended to degradate at a lower temperature, the major scission products spouted out from the polymer surface originated from polystyrene. The shorter the ignition times of the blends with red‐phosphorous were, the lower the peak heat release rates were. It was an interesting phenomenon because it suggested that the chemical structure of the residue changed to more stable polymers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 156–161, 2007     

Assessing the performance of intumescent coatings using bench‐scaled cone calorimeter and finite difference simulations

A method was developed to assess the heat insulation performance of intumescent coatings. The method consists of temperature measurements using the bench‐scaled experimental set‐up of a cone calorimeter and finite difference simulation to calculate the effective thermal conductivity dependent on time/temperature. This simulation procedure was also adapted to the small scale test furnace, in which the standard time–temperature curve is applied to a larger sample and thus which provides results relevant for approval. Investigations on temperature and calculated effective thermal conduction were performed on intumescent coatings in both experimental set‐ups using various coating thicknesses. The results correspond to each other as well as showing the limits of transferability between both fire tests. It is shown that bench‐scaled cone calorimeter tests are a valuable tool for assessing and predicting the performance of intumescent coatings in larger tests relevant for approval. The correlation fails for processes at surface temperatures above 750°C, which are not reached in the cone calorimeter, but are attained in the small scale furnace set‐up. Copyright © 2006 John Wiley & Sons, Ltd.     

Comparative study on thermal decomposition and combustion behavior of glass‐fiber reinforced poly(1,4‐butylene terephthalate) composites containing trivalent metal (Al,La, Ce) hypophosphite

High fire hazards of glass‐fiber reinforced polymer composites have greatly limited their development and application. To reduce their flammability, the composites have to be treated with flame retardants. This work examines the use of three trivalent metal (Al, La, Ce) hypophosphites as halogen‐free flame retardants for glass‐fiber reinforced poly(1,4‐butylene terephthalate) (GRPBT) composites. The aim of this study is to quantitatively investigate the effect of metal hypophosphites on the thermal decomposition and combustion behavior of GRPBT composites by means of cone calorimeter and thermogravimetry coupled with Fourier transform infrared spectroscopy (TG‐FTIR) techniques. The peak heat release rate and total smoke production of GRPBT/cerium hypophosphite (CHP) composite evaluated by cone calorimeter are reduced, respectively, by around 76 and 44% compared to the results of GRPBT. The volatilized esters measured by TG‐FTIR in the decomposition of GRPBT/CHP are decreased by about 69%. The results showed that rare earth hypophosphites can effectively inhibit the thermal decomposition and combustion behaviors of GRPBT in comparison with aluminum hypophosphite. POLYM. COMPOS., 34:1832–1839, 2013. © 2013 Society of Plastics Engineers     

Fire performance of brominated and halogen‐free flame retardants in glass‐fiber reinforced poly(butylene terephthalate)

This paper investigates the effects of brominated and halogen‐free fire retardants on the fire performance of glass‐fiber (GF) reinforced poly(butylene terephthalate) (PBT). Brominated polystyrene was used as the brominated fire retardant, whereas aluminum diethylphosphinate with/without nanoclay as halogen‐free fire retardants (HFFRs). Tests were conducted by using thermogravimetric analysis, limiting oxygen index (LOI), UL94, and the cone calorimeter. Thermogravimetric analysis results show that decomposition of GF plus PBT (PBT + GF) starts earlier in the presence of all fire retardants (FRs). In the cone calorimeter, all FRs reduce significantly the heat release rate (HRR) compared with PBT + GF, with brominated polystyrene achieving lowest HRR primarily because bromine released in the pyrolysis gases inhibits combustion. Brominate polystyrene does not, however, affect the mass loss rate. Aluminum diethylphosphinate alone has significant effects on reduction of both HRR and mass loss rate, which become considerably more when combined with nanoclay. It was also found that the combustion efficiency of the brominated polystyrene compound is much lower than that of HFFRs, indicating that brominated polystyrene has higher gas phase flame retardant efficiency compared with HFFRs because the bromine radicals released during degradation of brominated polystyrene effectively quench the chemical reactions of the pyrolysis gases due to degradation of PBT.     

Study of using aluminum hypophosphite as a flame retardant for low‐density polyethylene

Aluminum hypophosphite (AHP) was first used to improve the flame retardance of low‐density polyethylene (LDPE). The flame‐retardant properties of LDPE composites were investigated by the limiting oxygen index, vertical burning test (UL‐94), microscale combustion calorimetry, and cone calorimeter tests. The results showed that the incorporation of AHP could improve the flame retardancy of LDPE dramatically, the limiting oxygen index of LDPE containing 50 phr AHP reached 27.5%, and the UL‐94 could pass V‐0 rating. The cone calorimeter test results indicated that PP/AHP composite exhibited superior performance, and the heat release rate and the total heat release of composites were significantly reduced. In addition, the strength of the char was improved with the load of AHP increased. The structure of the char was researched by Fourier transform infrared spectrometry (FTIR) and scanning electron microscope‐energy dispersive spectrometer, and the results revealed that AHP promoted the formation of compact char layer. The TG‐FTIR analyses proved that AHP could react with LDPE to reduce the production of olefin in gas phase. Moreover, the structure of P–O–C was found, and the effective mechanism of AHP in LDPE composites was also hypothesized in this work.     

Smoke suppression properties of epoxy crosslinked structure and intumescent fire retardant in epoxy‐based intumescent fire‐retardant coating

In this article, the smoke production behaviors of crosslinked epoxy/polyamide resin (EP/PA) and intumescent fire retardant (IFR) in epoxy‐based intumescent fire‐retardant coating (IFR‐EP) have been investigated using cone calorimeter, smoke density instrument, and thermogravimetric analysis and Fourier transform infrared spectroscopic measurement. The static and dynamic smoke production behaviors of EP/PA and IFR‐EP indicate that the IFR has an excellent smoke suppression effect on EP/PA by forming protective char layer in the late combustion stage, while the epoxy crosslinked structure in IFR‐EP can enhance the thermal stability and reduce smoke production in the early combustion stage. In addition, according to the discussion of pyrolysis gas products, the IFR can effectively suppress the production of toxic and inflammable gases during the combustion process. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43912.     

Characterization of highly under‐ventilated fires using the cone calorimeter

The cone calorimeter, originally designed with an ‘open configuration‘, may be used in combination with a closed‐combustion chamber in order to test specimens in oxygen‐depleted atmospheres (air vitiation effect) or in fuel‐rich combustion (ventilation effect). However, highly under‐ventilated conditions are not achievable, as a consequence of an overconsumption of oxygen due to the incomplete confinement of the flame and imperfections in the air tightness of the combustion volume. In this work, these issues were solved by lowering the combustion zone, in order to fit a 600 mm chimney on the top of the controlled‐atmosphere chamber, and further improving the sealing of the whole setup. n‐Heptane was used as a reference fuel, and its combustion properties were determined in under‐ventilated conditions. The yields of main combustion species correlated well with the global equivalence ratio, for values of Φ up to three. The use of a Fourier‐transform infrared spectrometer allowed further refinement of the total unburned‐fraction composition. The relative concentration of species like methane, ethylene, or acetylene was shown to be relatively constant over the range of under‐ventilated conditions. Copyright © 2015 John Wiley & Sons, Ltd.     

A polymeric flame retardant and surfactant‐free montmorillonite nanocomposites: Preparation and exfoliation mechanism discussion

A polymeric flame retardant (PDEPD) and various amounts of sodium montmorillonite (Na‐MMT) nanocomposites with exfoliation structure were prepared via one‐step polycondensation, attempting to prepare flame‐retardant nanocomposites. The nanocomposites exhibited high thermal stability at high temperature. Based on several comparative studies, we investigated and proposed the possible exfoliation mechanism of Na‐MMT in PDEPD substrate. The microscale combustion calorimeter and cone calorimeter results showed the PDEPD/Na‐MMT nanocomposites could significantly improve the flame retardancy of polystyrene and polyurethane elastomer (TPU), especially the TPU matrix. This study provides new viewpoint for preparing flame‐retardant nanocomposites without surfactants. POLYM. COMPOS., 35:167–173, 2014. © 2013 Society of Plastics Engineers     

Phosphorus‐Containing Polymer Flame Retardants for Aliphatic Polyesters

Polyesters with 9,10‐dihydro‐9‐oxy‐10‐phosphaphenanthrene‐10‐oxide‐containing comonomers are synthesized aiming to improve the flame retardancy of aliphatic polyesters such as poly(butylene succinate) and poly(butylene sebacate). The influence of the chemical structure on the thermal decomposition and pyrolysis is examined using a combination of thermogravimetric analysis (TGA), TGA‐Fourier transform infrared (FTIR) spectroscopy, pyrolysis‐gas chromatography/mass spectrometry, and microscale combustion flow calorimetry. Thermal decomposition pathways are derived and used to select suitable candidates as flame retardants for PBS. The fire behavior of the selected polymers is evaluated by forced‐flaming combustion in a cone calorimeter. The materials show two modes of action for flame retardancy: strong flame inhibition due to the release of a variety of molecules combined with charring in the solid state.     

Synthesis,Characterization, and Energetic Properties of N‐Rich Salts of the 4,5‐Dicyano‐2H‐1,2,3‐triazole Anion

The synthesis and characterization of the 4,5‐dicyano‐2H‐1,2,3‐triazole anion in its 5‐aminotetrazole, 1,5‐diaminotetrazole, and 1,5‐diamino‐4‐methyl‐tetrazole salts are reported. All compounds were characterized by IR, ¹H NMR, and ¹³C NMR spectroscopy, as well as elemental analyses. Their thermal decompositions were investigated by TG‐DSC. The densities, combustion heats, and sensitivity properties were tested. Additionally, enthalpies of formation, detonation pressures, detonation velocities, and heats of detonation were calculated. The compounds have potential application in the energetic materials field.