THE use of thermogravimetric data to evaluate kinetic parameters of solid-state reactions involving weight loss (or gain) has been investigated by a number of workers1–4. Freeman and Carroll2 have stated some of the advantages of this method over conventional isothermal studies. To these reasons may be added the advantage of using one single sample for investigation. However, the importance of procedural details, such as crucible geometry, heating rate, pre-history of sample, and particle size, on the parameters has yet to be fully investigated. It is also necessary to ensure accurate temperature measurement, both for precision and also to detect any departure from a linear heating rate due to endo- or exo-thermic reactions. (The effect of these may be largely eliminated by the use of small samples.) In our present work (using a Stanton HT–D thermobalance) the sample temperature is measured directly by means of a thermocouple the bead of which is positioned in or near the sample, depending on crucible design, the wires of which run down a twin-bore rise rod. The connexion between the end of the thermocouple wires on the balance arm and the terminal block is made by 0.001 in. platinum and platinum/rhodium wires5. It has been shown that these wires do not affect the performance of the balance but act merely as a subsidiary damping. From the terminal block compensated cable leads to the cold junction and a potentiometric arrangement for direct measurement of the thermocouple output.

Kinetic Parameters from Thermogravimetric Data

A new method of obtaining the kinetic parameters from thermogravimetric curves has been proposed. The method is simple and applicable to reactions which can not be analyzed by other methods. The effect of the heating rate on thermogravimetric curves has been elucidated, and the master curve of the experimental curves at different heating rates has been derived. The applications of the method to the pyrolyses of calcium oxalate and nylon 6 have been shown ; the results are in good agreement with the reported values. The applicability of the method to other types of thermal analyses has been discussed, and the method of the conversion of the data to other conditions of temperature change has been suggested. From these discussions, the definition of the thermal stability of materials has been criticized.

A New Method of Analyzing Thermogravimetric Data

ICTAC Kinetics Committee recommendations for performing kinetic computations on thermal analysis data

A technique was devised for obtaining rate laws and kinetic parameters which describe the thermal degradation of plastics from TGA data. The method is based on the inter-comparison of experiments which were performed at different linear rates of heating. By this method it is possible to determine the activation energy of certain professes without knowing the form of the kinetic equation. This technique was applied to fiberglass-reinforced CTL 91-LD phenolic resin, where the rate law - (1/we)(dw/dt) = 1018e−55,000/RT [(w - wf)/w0,]5, nr.−1, was found to apply to a major part of the degradation. The equation was successfully tested by several techniques, including a comparison with constant temperature data that were available in the literature. The activation energy was thought to be correct within 10 kcal.

Kinetics of thermal degradation of char-forming plastics from thermogravimetry. Application to a phenolic plastic

A New Analysis of Thermogravimetric Traces.

Thermogravimetric data are generally more extensive than are comparable isothermal aging data, and therefore afford preliminary kinetic information in greater abundance. The kinetic analysis of the thermogram, by use of either its exact equation or a more convenient approximation formula, is straightforward in cases of volatilization via simple kinetics. Application of the analytical procedure to the thermogram for the zero-order volatilization of octamethylcyclotetrasiloxane yielded an estimate of 11.65 kcal./mole as the average heat of vaporization in the temperature range of 80 to 145°C. The apparent activation energy for the first-order pyrolytic volatilization of 200-mg. samples of pulverized polytetrafluoroethylene was estimated to be 66 to 68 kcal./mole in the temperature range of 520 to 610°C.

Kinetic analysis of thermogravimetric data

Equations are given for estimating equivalent isothermal life from thermogravimetric data and for estimating the apparent activation energy for volatilization even though the nature of the kinetic process is unknown. Illustrative data for polytetrafluoroethylene are presented. The importance of using sample temperatures, rather than furnace temperatures, is noted.

C. D. Doyle

Papers

Kinetic analysis of thermogravimetric data

Estimating isothermal life from thermogravimetric data