Reduced water vapour sorption in cellulose nanocomposites with starch matrix

The effects of microfibrillated cellulose nanofibers from wood on the moisture sorption kinetics (30% RH) of glycerol plasticized and pure high-amylopectin starch films were studied. The presence of a nanofiber network (70 wt% cellulose nanofibers) reduced the moisture uptake to half the value of the pure plasticized starch film. The swelling yielded a moisture concentration-dependent diffusivity. Quite surprisingly, the moisture diffusivity decreased rapidly with increasing nanofiber content and the diffusivity of the neat cellulose network was, in relative terms, very low. It was possible to describe the strong decrease in zero-concentration diffusivity with increasing cellulose nanofiber/matrix ratio, simply by assuming only geometrical blocking using the model due to Aris. The adjusted model parameters suggested a “simplified” composite structure with dense nanofiber layers oriented in the plane of the film. Still, also constraining effects on swelling from the high modulus/hydrogen bonding cellulose network and reduced amylopectin molecular mobility due to strong starch–cellulose molecular interactions were suggested to contribute to the reductions in moisture diffusivity.