Thermal degradation of lignin in nitrogen atmosphere is evaluated by linear heating and isothermal tests. While linear heating suggests that thermal decomposition in the 200–400 °C range mainly consists of a single step, a careful analysis of isothermal tests points to different lignin fractions having different stabilities. This is an important point for practical predictions, since kinetics obtained as if the degradations at different temperatures were the same would lack practical utility. Instead, stairway type tests are proposed to evaluate the degradation rates and sample quantities involved at the temperatures of interest.

In spite of the many studies performed, there is not yet a kinetic model to predict the thermal degradation of cellulose in isothermal and nonisothermal conditions for the full extent of conversion. A model proposed by the authors was tested on non-oxidising thermogravimetric data. The method consisted of initially fitting several isothermal and non-isothermal curves, then obtaining a critical temperature and an energy barrier from the set of fittings that resulted from different experimental conditions. While the critical temperature, approximately 226 °C, represented the minimum temperature for the degradation process, the degradation rate at a given temperature was related to both the critical temperature and the energy barrier. These results were compared with those observed in other materials. The quality of fittings obtained was superior to any other reported to date, and the results obtained from each single curve were in line with each other. The peak area. Represents the amount of sample involved in each transformation process, in linear heating conditions Fitting parameter, related to the peak shape in linear heating conditions. If =1, then is 4 times the maximum transformation rate per unit of sample mass KeywordsThe time elapsed from the beginning of the experiment to the instant where the maximum mass loss rate is observed, in linear heating experiments Fitting parameter related to the peak asymmetry ( =1 for a symmetric peak) yiso(t) Transformation rate, as a function of time, in isothermal conditionsThe peak area. Represents the amount of sample involved in each transformation process, in isothermal conditions

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A kinetic model is proposed to fit isothermal thermogravimetric data obtained from cellulose in an inert atmosphere at different temperatures. The method used here to evaluate the model involves two steps: (1) fitting of single time-derivative thermogravimetric curves (DTG) obtained at different temperatures versus time, and (2) fitting of the rate parameter values obtained at different temperatures versus temperature. The first step makes use of derivative of logistic functions. For the second step, the dependence of the rate factor on temperature is evaluated. That separation of the curve fitting from the analysis of the rate factor resulted to be very flexible since it proved to work for previous crystallization studies and now for thermal degradation of cellulose.