Stress Relaxation of Natural and Synthetic Rubber Stocks

Abstract

Abstract 1. The complete decay of stress in the rubbers studied, held at constant elongation, appeared to involve the rupturing of a definite bond, either at some point along the molecular chain or at the cross-linking bond put in by vulcanization. In the case of a Hevea rubber gum stock the data could be fitted very well by ordinary reaction-rate theory, leading to the conclusion that the free energy of activation required for breaking the bond is 30.4 kcal. per mole of bonds. This result was found to be practically independent of the elongation, and of the presence of carbon black in a Hevea rubber tread stock. This is to be compared to a strength of about 90 kcal. per mole for the C—C bond. 2. In the case of other rubbers (Buna-S, Butaprene-N, Neoprene-GN, and Butyl) the activation free energy for breaking the bond did not vary by more than ±2.0 kcal. per mole from that of Hevea rubber. However, these differences were quite definite. For example, the relaxation of stress in GR-S was slower than in Hevea; a small difference in energy corresponding to a 2:1 ratio in the respective times of decay. 3. The effect of temperature on the relaxation of stress appeared to be of the general type characteristic of chemical reactions. By use of the ordinary formula for expressing rate of reaction in terms of energy of activation, one could predict very closely the behavior of the stress-log time curves at different temperatures. 4. Natural rubber and GR-S vulcanized with paraquinone dioxime and lead dioxide showed relaxation curves very similar to those of the sulfur vulcanized stocks. 5. Relaxation experiments in an ordinary air atmosphere and in an atmosphere of commercial nitrogen showed no appreciable differences. 6. Examination of stretched rubber bands in which the stress had decayed nearly completely (at 100° C) gave no evidences of gross oxidation, such as would make the rubber bands sticky or hard, or of surface deterioration. At higher temperatures, however, the rubber could be observed getting sticky, and then brittle. Specimens in which the stress had completely decayed showed very low tensile strength (by hand test). 7. Antioxidant added to a sulfur-stabilized Buna-S stock caused a definite retardation of the rate of relaxation. 8. Comparison of the results of these experiments with previously recorded observations in the literature indicated that the chemical reaction which ruptured the rubber structure and caused the decay of stress in these experiments (and concomitantly a lowering of tensile strength) was an oxidation of the rubber by small amounts of oxygen, the reaction rate being independent of the oxygen pressure in the range between that present in an ordinary air atmosphere and in a commercial nitrogen atmosphere. 9. The tests suggested a convenient and accurate laboratory method of determining the oxidizability of natural and synthetic rubber stock designed for service.