Degradation kinetics of PLA/hemp biocomposites: Tradeoff between nucleating action and pro-hydrolytic effect of natural fibers
Libera Vitiello, Sabrina Carroccio, Veronica Ambrogi, Edoardo Podda, Giovanni Filippone, Martina Salzano de Luna
Abstract
Natural fibers are not only a sustainable alternative to synthetic reinforcement materials, but can also be used to produce truly sustainable biocomposites with fast degradation kinetics. Indeed, due to their hygroscopicity, lignocellulosic fibers allow water and/or degrading organisms from the external environment to penetrate inside the host matrix and trigger its hydrolysis. The latter is the rate-limiting step for the degradation of bio-polyesters, which exhibit unacceptably slow degradation kinetics at ambient temperature and humidity. However, fibers also promote crystallization of the host matrix and thus slow down its degradation kinetics. To better understand and potentially control the degradation kinetics of biocomposites, here we investigate the ability of hemp shives, a hygroscopic by-product of hemp fiber production, to accelerate the hydrolysis of poly (lactic acid) (PLA). The degradation kinetics and degree of crystallinity of PLA are monitored in water and mature compost as a function of fiber content, which was varied across the percolation threshold (Φc) to study the effect of fiber interconnectivity. Above Φc, the fibers accelerate PLA hydrolysis in water despite their nucleating effect. Conversely, in compost the shielding effect of fiber-induced crystallinity prevails, and the fibers eventually slow down the degradation kinetics of PLA.