When applying electron or gamma irradiation to poly-3-hydroxybutyrate (P3HB), main chain scissions are the dominant material reactions. Though propositions have been made that crosslinking in the amorphous phase of P3HB occurs under irradiation, a conclusive method to achieve controlled additive free irradiation crosslinking has not been shown and no mechanism has been derived to the best of our knowledge. By applying irradiation in a molten state at 195 °C and doses above 200 kGy, we were able to initiate crosslink reactions and achieved gel formation of up to 16%. The gel dose Dgel was determined to be 200 kGy and a range of the G values, the number of scissions and crosslinks for 100 eV energy deposition, is given. Rheology measurements, as well as size exclusion chromatography (SEC), showed indications for branching at doses from 100 to 250 kGy. Thermal analysis showed the development of a bimodal peak with a decrease in the peak melt temperature and an increase in peak width. In combination with an increase in the thermal degradation temperature for a dose of 200 kGy compared to 100 kGy, thermal analysis also showed phenomena attributed to branching and crosslinking.
Keywords: G values; biopolyesters; chain branching; chain scissioning; crosslinking; e-beam; elevated temperatures; gel dose; gel point; irradiation; melt; molten state; poly-3-hydroxybutyrate.