Controlled degradation of epoxy networks: analysis of crosslink density and glass transition temperature changes in thermally reworkable thermosets

The characteristics of networks formed in cured ‘reworkable’ epoxy thermosets capable of controlled thermal degradation were studied. Dynamic mechanical thermal analysis, swelling measurements, and glass transition temperature measurements were used to obtain information regarding the time and temperature dependence of the crosslink densities of these materials. By applying isothermal conditions, networks containing up to 36 mol% non-degradable components could be completely degraded, i.e. progress from a network of infinite molecular weight to a finite one with zero crosslink density. Percolation theory was used to facilitate the interpretation of these results. The degradation behavior of the reworkable thermosets were well-described by gel degradation theory, i.e. the reverse of the gelation process, and the experimental results were in good agreement with calculated values obtained by replacing the extent of reaction, p, in Macosko and Millerʹs branching theory with the extent of degradation, 1−p.