1. 1 CNRS GDR « Feux » – Corte 6 th to 8 th June 2007 Polyurethane Foam Pyrolysis and Combustion in Cone Calorimeter – Analysis of released heat and gases Lucas BUSTAMANTE VALENCIA Directors: Eric GUILLAUME LNE division Comportement au Feu Thomas ROGAUME Laboratoire de Combustion et de Détonique, UPR 9028 CNRS

2. 2 Cone Calorimeter Line of Gas Data transmission Gas Evacuation Sampling line at 150 °C FTIR FTIR data Oxygen, CO and CO 2 analyser Cone Calorimeter data Scheme of apparatus distribution Camera FIDPump FID data and temperatures register

3. 3 PF “perfect” heat exchange balance in thermally-stable conditions

4. 4 ElementMean (%) Molar Mass (g/mol) Molar proportion (mol) Coefficients C61.9712.015.161.00 H8.501.018.431.63 O22.4616.001.400.27 N5.8814.010.420.08 S< 0.232.06 Cl< 10 ppm35.45 Total98.8118.62 Density 20.87 kg/m 3 PF chemical composition (elemental analyse) Normalised mass evolution with time in non-flaming condition - 30 kW/m²

5. 5 SMLR vs incident heat flux Specific mass-loss rate Where: Specific mass-loss rate (kg/sּm² ) Incident heat flux (kW/m²) Reflected heat flux (kW/m²) Vaporisation enthalpy (kJ/kg) Specific mass-loss rate until 180 s * Fire protection engineering – SFPE 2nd Ed. ParameterCalculatedLiterature Vaporisation enthalpy (kJ/kg)4,6922400* Reflected heat flux (kW/m²)4.7316 - 19*

6. 6 Where: Ignition time (s) Incident heat flux (kW/m²) Critical heat flux, is also found in literature as (kW/m²) Thermal Response Parameter (kW·s 1/2 /m²) Ignition time vs incident heat flux

7. 7 Where: Thermal conductivity (kW/m K) PF density (kg/m 3 ) Specific heat at constant pressure (kJ/kgּK) Thermal Parameters Where: h c Coefficient of convective transfer = 15  2 W/m² ּK T ig Temperature of the surface at ignition To Laboratory temperature = 293  1 K Material emissivity = (0.9  0.07) Stephan Boltzmann constant = 5.67x10 -8 W/m 2 ּK 4 * Fire protection engineering – SFPE 2nd Ed. (Data obtained in flammability Apparatus) ** Fire protection engineering – SFPE 2nd Ed. ParameterCalculatedLiterature Thermal Response Parameter (kWּs 1/2 ּm -2 )75.23 55 - 221* Critical Heat Flux (kWּm -2 ) – Experimental9.00 13 - 40* Ignition Temperature (°C)275 280** Thermal Inertia ρλCp (kJ 2 ּs -1 ּm -4 ּK -2 )0.09

8. 8 Where: Thornton factor = 13.1MJ/kgO 2 Initial environment concentration of the species A (1) Environment oxygen mole fraction (1) Concentration of the species A at the time t (1) Exhaust duct volume flow (l/s) Heat Release Rate

9. 9 Source LNE data base Temperature measurement 10 mm 30 mm T2 T1 Aluminium foil Polyurethane foam Thermocouples location - K type

10. 10 Heating rate of the Polyurethane Foam Evolution of the internal temperature of sample Time-lag between the thermocouples for given temperatures Temperature at a Heat Flux of 30 kW/m 2 Nonflaming condition

11. 11 Heating rate of the Polyurethane Foam Evolution of the internal temperature of the PF Time-lag between the thermocouples for given temperatures Temperature at a Heat Flux of 40 kW/m 2 Flaming condition

12. 12 Evolution of the internal temperature of the PF Temperature at a Heat Flux of 35 kW/m 2 Nonflaming to flaming condition The ignition temperature measured = 320 °C and 350 °C. The LNE Fire Data Base (Data No. 3329) = 280 °C. (We do not know which was the method for determinate it).

13. 13 Analysed Chemical Compounds FTIR = Fourier Transform Infrared Spectroscopy (FTIR) FID = Flame Ionisation Detector ND = Non Dispersive Analyser Concentr. (ppm) < LoD < LoQ < LoD < LoQ < LoD < LoQ < LoD Gas nameFormula LoD (ppm) LoQ (ppm) Method Carbon monoxideCO 1.183.93 FTIR - ND Carbon dioxideCO 2 22.6475.47 FTIR - ND Nitric oxideNO 2.227.40 FTIR WaterH2O N/D FTIR Total hydrocarbons 0.1 0.33 FID Sulphur dioxideSO 2 1.123.73 FTIR AmmoniaNH 3 1.755.83 FTIR Hydrogen chlorideHCl 1.545.13 FTIR MethaneCH 4 4.7515.83 FTIR Nitrous oxideN2ON2O 0.531.77 FTIR Nitrogen dioxideNO 2 1.976.57 FTIR EthyleneC2H4C2H4 21.1370.43 FTIR AcetyleneC2H2C2H2 5.2817.60 FTIR Hydrogen cyanideHCN 1.424.73 FTIR FormaldehydeHCHON/D FTIR

14. 14 10 kW/m 2 CO 2 release during PF combustion 30 kW/m 2 50 kW/m 2

15. 15 10 kW/m 2 CO release during PF combustion 30 kW/m 2 50 kW/m 2

16. 16 10 kW/m 2 NO release during PF combustion 30 kW/m 2 50 kW/m 2

17. 17 10 kW/m 2 H 2 O release during PF combustion 30 kW/m 2 50 kW/m 2

18. 18 CO 2, CO, H 2 O and NO yield CO 2 and H 2 O yieldCO and NO yield Where: Yb Yield of the chemical gas b (mg/g) Δt Time between data (s) V Volume flow in the cone calorimeter exhaust (l/min) MWb Molar mass of the gas b (g/mol) Vmol·b Molar volume of the gas b (l/mol) m Mass of the PF sample (g) xb,i Concentration of the gas b at the time i A « real » combustion equation for ventilated fires

19. 19 THC release in nonflame condition at 30 kW/m 2 THC release during PF combustion THC release in flame condition at 30 kW/m 2 THC release in flame in function of heat flux

20. 20 4 HRR and gases off during combustion at 30kW/m 2 123

21. 21 Thank you ! lucas.bustamante@lne.fr

22. 22 Background Slides

23. 23 The instruments and the measurements INSTRUMENTMEASUREMENT Cone CalorimeterThermal properties and fire behaviour of PF Fourier Transform Infrared Spectroscopy (FTIR) Chemical species leaked during pyrolysis and combustion Exhaust gas temperature measurement Exhaust gas temperature used for molar correction of gas-off Inner Polyurethane Foam temperature Measurement of the inner temperature of the foam during degradation Flame Ionisation Detection (FID) Total hydrocarbons production CameraEvaluation of foam degradation

24. 24 Scheme of the PhD research work