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Abstract
Rheometers are usually run under isothermal conditions for the cure of rubbers, in spite of the following drawbacks: three experiments at least are necessary at different temperatures selected within a narrow temperature window, and it takes some time for thermal equilibrium to establish between the rubber sample initially at room temperature and the dies. In scanning mode, the dies of the rheometer and the sample should be heated from room temperature up to the selected final temperature at a constant rate. The effect of the value given to the heating rate, which is the main factor in this new method, is especially studied, as well as the quality of the contact between the dies and the sample. The rubber used in the present study is a natural rubber vulcanised with 2% sulphur with a low enthalpy. The kinetic parameters of this cure reaction have been previously determined by isothermal rheometry, and the enthalpy measured by calorimetry. The state of cure–temperature curves in scanning mode have been calculated using a numerical model taking into account the conduction heat transfer through the rubber, the coefficient of heat transfer at the die–rubber interface, and the kinetics of the heat evolved from the cure reaction with the enthalpy. The kinetic parameters are determined from the state of cure–temperature curves, which are similar to the torque–temperature curves, using a least squares method. The values of the kinetic parameters obtained by this last calculation, based on the mathematical treatment of these curves, are the same as those introduced for obtaining these curves using the numerical model. Thus, whatever the heating rate, ranging from 2 to 10 K min –1 , and the value of the coefficient of heat transfer at the die–rubber interface expressing the quality of the contact, in scanning mode the moving die rheometer (MDR) can be used to determine the kinetics of the cure of rubbers.