ISSN:
0022-3832
Keywords:
Chemistry
;
Polymer and Materials Science
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
Tensile strengths of natural rubber samples quantitatively crosslinked with decamethylene dis-methyl azodicarboxylate have been determined. The proportion of the azo vulcanizing agent was varied 80-fold, the fraction p of cross-linked units in the products ranging from 0.10x 10-2 to 8.0 x 10-2. In spite of the small dimensions of the test specimen (cross section 0.10 in. by about 0.005 in.), the average error for a single observation is similar to that obtained in conventional testing procedures applied to specimens vulcanized with sulfur and accelerators. Deviations from the mean for 262 tests on 15 different cures are well represented by a Gaussian error function; a slight intimation of skewness is evident only at the extremities of the distribution of deviations. These results are incompatible with the commonly held view that rupture of the sample takes place at the “weakest link” in the series of flaws inevitably occurring along the specimen. It would appear that the ability to withstand tensile stress (applied in a specified manner) is an inherent characteristic of the bulk material. The rapid increase in tensile strength with the degree of crosslinking p for small values of this quantity is consistent with the conclusion, previously reached in the investigation of the physical properties of butyl rubber (6) that the tensile strength is directly related to the fraction of the structure which is permanently oriented by stretching. At higher degrees of cross-linking (at ρ x 100 = 1.0 to 1.5, depending on the molecular weight of the rubber) the tensile strength passes through a maximum and then declines steadily to quite low values for higher ρ's. This adverse effect of higher degrees of cross-linking is believed to result from the diminished elongation at which crystallization sets in and, hence, the smaller fraction of the network elements sufficiently oriented to participate in crystallite formation. Modification of up to 7% of the isoprene units of the rubber with the monofunctional compound, ethyl azodicarboxylate, depresses the tensile strength of the disazo vulcanized rubber relatively little. Evidently, the limited extent to which these modified (or copolymer) chains may enter into crystallization is adequate to bring about high tensile strength. Lack of direct correlation between modulus and tensile strength for rubbers vulcanized with various sulfur-accelerator combinations can only be explained by assuming that conventional vulcanization processes are accompanied to varying degrees by chain scission reactions. When vulcanized rubber is “over-cured,” or heat aged, chain scission becomes excessive.
Additional Material:
5 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/pol.1949.120040402
