FORMATION OF SURFACE-STRUCTURE IN VULCANIZATES AND SURFACE-STRUCTURE CHANGES IN AIR

The formation theory of surface structure during vulcanization was developed on the basis of an interfacial concept. The theory showed the chemical compositions of polar and nonpolar components on the vulcanizate surface to be determined as an excess interfacial free energy between rubber compounds and molds decreases. The surface free energies of molds reflected clearly the corresponding surface free energy of vulcanizates prepared from copolymers and polar polymers. Nonpolar polymers were not influenced by the surface free energies of molds. The surface free energies of vulcanizates decreased slightly with the concentration of network chains owing to the entropy of rubber segments. The surface free energies of molds affected the chemical compositions at the topmost surface region to the upper surface region on vulcanizates. NDR Vulcanizates with high surface free energy increased the contact angle of water after standing in dry air. In the dry air environment, topmost surface layer nitrile groups were buried in the bulk of NBR vulcanizates and butadiene units subsequently overturn to the topmost layer. In this case, the vulcanizate surface chemical composition was influenced only at the topmost surface region. ESCA spectra N-1s peak intensities on NBR vulcanlzates was consistent with these observation.