Studies in the Vulcanization of Rubber. V. Dielectric Constant and Power Factor of Vulcanized Rubber
Abstract 1. Power factor and dielectric constant data have been given for vulcanized rubber samples tested over a wide range of composition, temperature, and frequency. 2. The real identity of the agents responsible for the peculiar dielectric behavior is not known. It seems probable that these agents are the rubber-sulfur molecules themselves. because the effects increase, under proper conditions, directly with per cent combined sulfur. 3. The effect of increasing sulfur content on the dielectric behavior is complex; it modifies not only these supposed agents themselves, but also the stiffness of their environment. Moreover, at a given sulfur content the agents are not identical but differ widely in relaxation time, and therefore in ability to respond; and with progressive addition of sulfur, the rubber does not increase continuously in stiffness, but, at a composition which depends on the temperature, passes rather abruptly from a soft to a hard state. 4. The temperature at which the transition from one state to the other occurs increases almost linearly with the sulfur content from −90° to +90° C. 5. In the soft state the behavior of vulcanized rubber with respect to compressibility, thermal expansion, dielectric constant, and power factor, and probably other properties, resembles that of a viscous liquid; in the hard state, that of a solid. 6. Rubber with less than 2 per cent combined sulfur shows low dielectric constant and power factor over the whole temperature and frequency range investigated; hard rubber, only at room temperature, where its rigidity restricts the response to the field. 7. Hard rubber, although not an electret, can hold an electric charge for 24 hours or more. The low dielectric constants of high-sulfur rubber samples found in measurements with a ballistic galvanometer were due to the disparity between its period of about one second and the long discharge periods of the samples. This led to the idea of dipole compensation shown to be incorrect by the high temperature results. 8. At temperatures sufficiently high to permit free response, the dielectric constant increases with sulfur content over the whole range. 9. If a dipole mechanism is involved, addition of sulfur to more than half the double bonds does not cause the dipole moment of the molecules to vanish owing to compensation. 10. The power factor of vulcanized rubber sheets decreases on stretch. 11. The data neither prove nor disprove a dipole mechanism. A critical experiment to settle this question is still wanting.