Surface characterization of cross-linked elastomers by shear modulation force microscopy

Brominated poly(isobutylene-co-4-methylstyrene) (BIMS) is a synthetic terpolymer which can be stoichiometrically cross-linked by N,N′-dicinnamylidene-1,6-hexanediamine (DIAK). The degree of cross-links on bulk samples was determined by measuring the low frequency shear modulus with parallel plate method. The surface modulus of the same samples was measured using a new method, shear modulation force microscopy (SMFM). The moduli of the bulk sample and the surface were found to have the same scaling with the cross-link density, and good agreement with rubber elasticity theory was obtained in both cases. The SMFM was then used to monitor the cross-linking process, as a function of DIAK concentration and curing time, in thin films where standard rheological methods cannot be applied. The results show that in all cases the cross-linking reaction at the surface reaches saturation in less than 10 min as compared to at least 1 h in the bulk samples.