This article presents a three-dimensional pyrolysis model that is capable of simultaneously predicting the back surface temperature profiles, the mass loss, and the heat release rate of an intumescent-based flame-retardant polymer composite. The model is based on mass and energy conservation, heat transfer equations in porous media, and a moving boundary condition (expansion rate) to mimic the thermal expansion of the intumescent material. The strength of this model lies in the extensive experimental effort to measure input parameters. These parameters were determined through microscale tests (thermogravimetric analysis, differential scanning calorimetry, pyrolysis combustion flow calorimetry, transient plane source, and parallel plate rheometry). A long glass-fiber reinforced flame-retardant polypropylene was employed as intumescent material to develop and to validate the model. Validation of the model done on cone calorimetry data showed that all curves were well captured (temperature/time curve, heat release rate, and mass loss rate).
AlsabriATahirFAl-GhamdiSG. Environmental impacts of polypropylene (PP) production and prospects of its recycling in the GCC region. Mater Today Proc2022; 56: 2245–2251.
2.
HsissouRSeghiriRBenzekriZ, et al. Polymer composite materials: a comprehensive review. Compos Struct2021; 262: 113640.
3.
AlongiJHanZBourbigotS. Intumescence: tradition versus novelty. A comprehensive review. Prog Polym Sci2015; 51: 28–73.
4.
BourbigotSSarazinJBensabathT, et al. Intumescent polypropylene: reaction to fire and mechanistic aspects. Fire Saf J2019; 105: 261–269.
CaminoGCostaL. Thermal degradation of polymer-fire retardant mixtures: part IV-mechanism of fire retardancy in polypropylene-chlorinated paraffin mixtures. Polym Degrad Stab1982; 4(3): 167–171.
7.
CaminoGCostaLTrossarelliL. Thermal degradation of polymer-fire retardant mixtures: part III-degradation products of polypropylene-chlorinated paraffin mixtures. Polym Degrad Stab1982; 4(2): 133–144.
8.
CaminoGCostaLTrossarelliL. Thermal degradation of polymer-fire retardant mixtures-Part II: mechanism of interaction in polypropylene-chlorinated paraffin mixtures. Polym Degrad Stab1982; 4(1): 39–49.
9.
BourbigotS. Intumescence-based flame retardant. In: WilkieCAMorganAB (eds) Fire retardancy of polymeric materials. 3rd ed.Boca Raton, FL: CRC Press, 2024, pp. 116–146.
10.
BensabathTSarazinJJimenezM, et al. Intumescent polypropylene: interactions between physical and chemical expansion. Fire Mater2021; 45: 387–395.
11.
JimenezMDuquesneSBourbigotS. Intumescent fire protective coating: toward a better understanding of their mechanism of action. Thermochim Acta2006; 449(1–2): 16–26.
12.
StoliarovSIDingY. Pyrolysis model parameterization and fire growth prediction: the state of the art. Fire Saf J2023; 140: 103905.
13.
GirardinBFontaineGDuquesneS, et al. Measurement of kinetics and thermodynamics of the thermal degradation for flame retarded materials: application to EVA/ATH/NC. J Anal Appl Pyrolysis2017; 124: 130–148.
14.
NyazikaTJimenezMSamynF, et al. Pyrolysis modeling, sensitivity analysis, and optimization techniques for combustible materials: a review. J Fire Sci2019; 37: 377–433.
15.
CoimbraASarazinJBourbigotS, et al. A pyrolysis model for the thermal decomposition of low-density polyethylene blended with ammonium polyphosphate and pentaerythritol. Fire Saf J2023; 139: 103813.
16.
FleurotteMAuthierOBourbigotS, et al. Sensitivity analysis applied to the pyrolysis of charring and non-charring materials under a cone calorimeter. J Fire Sci2022; 40(6): 405–443.
17.
FleurotteMDebenestGAuthierO, et al. Modelling of the swelling behaviour of a fire retarded material under a cone calorimeter. J Fire Sci2023; 41(4): 136–166.
18.
StoliarovSICrowleySLyonRE, et al. Prediction of the burning rates of non-charring polymers. Combust Flame2009; 156(5): 1068–1083.
19.
StoliarovSISafronavaNLyonRE. The effect of variation in polymer properties on the rate of burning. Fire Mater2009; 33(6): 257–271.
20.
LiJStoliarovSI. Measurement of kinetics and thermodynamics of the thermal degradation for non-charring polymers. Combust Flame2013; 160(7): 1287–1297.
21.
LyonRESafronavaN. A comparison of direct methods to determine n-th order kinetic parameters of solid thermal decomposition for use in fire models. J Therm Anal Calorim2013; 114: 213–227.
22.
TranchardPSamynFDuquesneS, et al. Modelling behaviour of a carbon epoxy composite exposed to fire: part II-comparison with experimental results. Materials2017; 10(5): 470.
23.
TranchardPSamynFDuquesneS, et al. Modelling behaviour of a carbon epoxy composite exposed to fire: part I-characterisation of thermophysical properties. Materials2017; 10(5): 1494–1419.
24.
CoimbraASarazinJBourbigotS, et al. A semi-global reaction mechanism for the thermal decomposition of low-density polyethylene blended with ammonium polyphosphate and pentaerythritol. Fire Saf J2022; 133: 103649.
25.
DingYMcKinnonMBStoliarovSI, et al. Determination of kinetics and thermodynamics of thermal decomposition for polymers containing reactive flame retardants: application to poly(lactic acid) blended with melamine and ammonium polyphosphate. Polym Degrad Stab2016; 129: 347–362.
26.
MullerMBourbigotSDuquesneS, et al. Investigation of the synergy in intumescent polyurethane by 3D computed tomography. Polym Degrad Stab2013; 98(9): 1638–1647.
27.
ZhangFZhangJWangY. Modeling study on the combustion of intumescent fire-retardant polypropylene. Express Polym Lett2007; 1(3): 157–165.
28.
GriffinGJ. The modeling of heat transfer across intumescent polymer coatings. J Fire Sci2010; 28(3): 249–277.
29.
LucheriniAHidalgoJPToreroJL, et al. Numerical heat transfer model for swelling intumescent coatings during heating. Int J Therm Sci2023; 184: 107922.
30.
CirpiciBKWangYCRogersBD, et al. A theoretical model for quantifying expansion of intumescent coating under different heating conditions. Polym Eng Sci2016; 56(7): 798–809.
31.
LucheriniAMalukC. Assessing the onset of swelling for thin intumescent coatings under a range of heating conditions. Fire Saf J2019; 106: 1–12.
32.
WilsonMTDlugogorskiBZKennedyEM. Uniformity of radiant heat fluxes in cone calorimeter. Fire Saf Sci2003; 7: 815–826.
33.
NyazikaTJimenezMSamynF, et al. Modeling heat transfers across a silicone-based intumescent coating. In: 3rd European symposium on fire safety science (eds BouletPMerciBVan HeesP), Nancy, 12–14 September 2018, pp. 1–6. Bristol: Institute of Physics Publishing.
34.
KangSKwonMChoiJY, et al. Thermal boundaries in cone calorimetry testing. Coatings2019; 9: 629.
35.
ParkerWJJenkinsRJButlerCP, et al. Flash method of determining thermal diffusivity, heat capacity, and thermal conductivity. J Appl Phys1961; 32(9): 1679–1684.
36.
GustafssonSE. Transient plane source techniques for thermal conductivity and thermal diffusivity measurements of solid materials. Rev Sci Instrum1991; 62(3): 797–804.
37.
GeoffroyLDavesneALBellayerS, et al. 3D printed sandwich materials filled with hydrogels for extremely low heat release rate. Polym Degrad Stab2020; 179: 109269.
38.
GeoffroyLDavesneALParentF, et al. Combining low-emissivity thin coating and 3D-printed original designs for superior fire-protective performance. ACS Omega2020; 5: 27857–27863.
BugajnyMLe BrasMBourbigotS. New approach to the dynamic properties of an intumescent material. Fire Mater1999; 23(1): 49–51.
41.
JimenezMDuquesneSBourbigotS. Multiscale experimental approach for developing high-performance intumescent coatings. Ind Eng Chem Res2006; 45(13): 4500–4508.
42.
StaggsJCreweRButlerR. A theoretical and experimental investigation of intumescent behaviour in protective coatings for structural steel. Chemical Engineering Science2012; 71: 239–251.
43.
LiJStoliarovSI. Measurement of kinetics and thermodynamics of the thermal degradation for charring polymers. Polym Degrad Stab2014; 106: 2–15.
44.
HendersonJBWiecekTE. A mathematical-model to predict the thermal response of decomposing, expanding polymer composites. J Compos Mater1987; 21(4): 373–393.
45.
ZhangJDelichatsiosMABourbigotS. Experimental and numerical study of the effects of nanoparticles on pyrolysis of a polyamide 6 (PA6) nanocomposite in the cone calorimeter. Combust Flame2009; 156(11): 2056–2062.
