This research on vulcanization illuminates the structure-property relationship of hard rubber with prolonging vulcanization. At the early stage of curing, polysulfur reacts with styrene-butadiene rubber (SBR) macromolecules to form chemical crosslink, as evidenced by the significant increase of modulus during vulcanization. The chemical crosslink is followed by a large amount of interchain attraction, which is due to the modification of SBR macromolecules by combined sulfur. The combined sulfur is formed by the reaction of sulfur atom with SBR backbone, which improves the polarity of SBR macromolecules since sulfur is polar. The influences of chemical crosslink and interchain attraction on the mechanical properties, thermal properties, dynamic mechanical properties, and fracture morphology were analyzed. (C) 2007 Wiley Periodicals, Inc.