Formation of 3D networks in polylactic acid by adjusting the cross-linking agent content with respect to processing variables: a simple approach

High-performance biodegradable polymers have attracted considerable attention over the years because of their eco-friendly nature. The effects of processing variables on the efficiency of crosslinking, and the rheological and thermal properties of cross-linked polylactic acid (XPLA) have not been comprehensively addressed yet. In this work, XPLA was prepared through solution casting followed by curing in an oven. Enhancements in properties could be quantified in terms of structural changes in 3D structure of XPLA by varying the amount of dicumyl peroxide (DCP) as a cross--linking agent and curing temperature and time. The XPLAs were characterized by differential scanning calorimetry, thermo-gravimetric analysis, swelling, and rheological techniques. The swelling data revealed an increase in gel fraction by 1.32% per 1 °C temperature rise in the range of 125–195 °C. The results were also indicative of an increase in gel faction by 0.32% per minute in the time range of 5–100 min. Maximum variation in gel fraction occurred at 195 °C with high peroxide content. At this temperature, the variation rate of gel content was about 14.99%. With gel formation evolution, especially at 85% completion stage, the melting point was vanished. Rheological measurements showed that the Newtonian plateau disappeared for the cross-linked samples, simultaneously with the onset of shear thinning and zero-shear viscosity, through which the molecular weight obtained by the Mark–Houwink equation shifted to lower frequencies. A mathematical model based on the Charlesby–Pinner equation was developed for predicting the gel content of the XPLA as a function of curing time and peroxide concentration. The Flory–Huggins parameter also changed during the cross-linking process as a function of cross-linking density. This study is focused on adjusting cross-linking density and processing factors, like temperature and time, to achieve an XPLA with desirable properties.