Measurement of thermal conductivity of thermally reactive materials for use in pyrolysis models

Pyrolysis models are used in the fire science field to simulate the thermal decomposition of materials. These models require knowledge of the kinetic and thermodynamic parameters of an assumed reaction mechanism, and the thermophysical properties of the virgin material and product species. Standard test methods exist for measuring the thermal conductivity of nonreactive materials, but to date no suitable method exists that is compatible with contemporary pyrolysis models and is applicable to thermally reactive materials. In the present study, a modified methodology was presented and evaluated to address this need. The methodology involves a preliminary assessment of thermal stability, followed by a series of tests including: thermogravimetric analysis, differential scanning calorimetry, and laser flash analysis. Once a reaction mechanism has been identified, gram-scale samples of the virgin and stable product species are isolated and independent measurements of thermal conductivity of those species are obtained. The methodology was applied to eucalyptus fiber hardboard, for which a complete set of property data for pyrolysis modeling was obtained. A pyrolysis experiment was then conducted, and that experiment was simulated using a pyrolysis model parameterized with the measured property data. Model predictions of the mass loss rate and temperature rise of a hardboard sample exposed to radiant heat flux of 35 and 60 kW m⁻² were found to be a good match to measurements. These results demonstrate the suitability of the property data, the pyrolysis model, and the utility of this approach. This work will serve as a basis for property determination in future pyrolysis studies.