A Time Effect in the Rapid Elongation of Rubber
Abstract It has already been pointed out elsewhere (Monatshefte für Chemie 72, 32 (1938); Rubber Chem. Tech. 12, 64(1939)) that the difference between the adiabatic and isothermal stress-strain curves of rubber is too great to be explained on a thermodynamic basis alone. It was suggested that the position of the adiabatic curves might be governed by the fact that the rate of stretching itself has a decisive effect on the behavior of the chains of molecules during stretching. To throw light on this phenomenon, stress-strain curves were obtained, by means of the stretching apparatus already described in the paper mentioned, at various rates of elongation which still fell within the range of adiabatic stretching. The operation was carried out in such a way that a chronometer started electrically when the rubber began to elongate, and stopped again when the rubber reached an elongation of 450 per cent. With the aid of this contrivance, stress-strain curves were obtained at rates corresponding to 0.68, 2.5, 5.7 and 9.1 seconds' elapsed time for the stretching. For comparison, an isotherm was obtained by loading rubber strips of the same dimensions with various weights. A vulcanizate containing 2 per cent of combined sulfur was used as experimental material. The temperature was 13° C. The results of these measurements are shown graphically in Fig. 1. It may be seen that the adiabatic curve corresponding to the highest rate of elongation has the least steep ascent, i.e., at the highest rate of elongation the stress is greatest at a given elongation. With increase in the time of stretching, the curves approach nearer and nearer to the isothermal stress-strain curve. This would seem to prove that the rate of elongation plays an important part, wholly independent of any thermodynamic effects. Perhaps during rapid stretching there is actual rupture of chains which are still coiled and which mutually obstruct the smooth course of the stress-strain curve. It can also be seen from the position of the curves that the decisive effect shown by the time factor is of the order of seconds, since the difference between the curves corresponding to 0.68 and 2.5 seconds is very small, whereas the difference between the curves corresponding to 2.5 and 5.7 seconds appears to be considerable.