Influence of gas emission on heat transfer in porous ceramics

It is known that thermal diffusivity, a, of several types of porous ceramic and refractory materials decreases with decreasing gas pressure. However, a of several ceramics (e.g., magnesite refractories with porosity about 25%) measured in vacuum by the monotonous heating exceeds the comparable data registered at atmospheric pressure. A similar effect was found for thermal diffusivity of several insulating materials. However, for some porous ceramics this phenomenon is absent or less prominent. It had been known that several heterogeneous physico-chemical processes take place on pore surfaces of ceramic materials. These processes include heterogeneous chemical reactions accompanied by emission of gaseous products. It had been conjectured that these processes affect thermophysical properties of ceramic materials, especially during fast heating or cooling. In this paper we substantiate this conjecture. Namely, we develop a quantitative model for the apparent thermal diffusivity, as measured by the nonstationary monotonous heating method. It takes into account the emission and adsorption of the gas on the opposite pore sides along the temperature gradient, the diffusive gas motion inside the pores and its removal from the pores due to the material gas permeability. The effect of these processes is shown to produce an additional heat flux inside the pore or crack and, hence, to increase the measured thermal diffusivity. In the presence of the passive gas, the rates of gas emission and its transport within the pore are significantly reduced, which leads to diminution of the effect of gas emission-adsorption on the heat transfer across the pore. Consequently, we show that this leads to a situation (observed in experiment) where thermal diffusivity of a material measured at high temperature in vacuum may exceed the comparable property at atmospheric pressure. When the reaction terminates due to the full conversion of the available solid reactant, the additional heat flow due to the gas emission and adsorption terminates, and the measured thermal diffusivity decreases. The rates of gas removal and of chemical conversion depend on the amount of reactant available within the specimen and on the heating rate. We show that as a result of this, the measured thermophysical properties depend on the material thermal history and heating parameters, and, hence, cannot be regarded as true material properties. (C) 2002 Elsevier Science Ltd. All rights reserved.