Sustainable Barrier System via Self-Assembly of Colloidal Montmorillonite and Cross-linking Resins on Nanocellulose Interfaces

Cellulose nanofibrils (CNFs) are able to form strong oxygen-barrier films suitable for food packaging but lack the needed water resistance in comparison to plastics. Desired water barrier quality can be achieved by applying mineral additives within the nanofibrils network. In current contribution, a sustainable hybrid system with an improved water barrier function is proposed by incorporating colloidal montmorillonite nanoclay (MMT) and two cross-linking agents, namely, polyamidoamine epichlorohydrin (PAE) and Acrodur thermoset acrylic resin (ACR) into CNF interfaces. Continuous matrices were produced via evaporation-induced self-assembly of colloidal building blocks followed by appropriate heat-curing regime to impart internal cross-linking. The development of chromophore functionalities and formation of ester motifs on the hybrid matrix (with no evidence of degradation) were detected by Fourier-transform infrared (FT-IR) spectroscopy. Intercalation of clay, solely, reduced the water vapor transmission rate (WVTR) to some extent; however, a more remarkable decline (by 60%) was observed upon the curing and cross-linking process. In fact, combination of clay platelets and cross-linkers contributed to a denser film structure and restricted water passage. Also, an excellent resistance to oil and grease was observed in all the studied films (Kit number of 11). A reduction in tensile strengths and resistance to cracking at fold was noted and ascribed to MMT interference in cellulose interchain hydrogen bonds. This however was counteracted by the introduction of cross-linkers, apparently by aiding stress transfer within the matrix. MMT imparted a limited elevation in the surface free energy, pointing out to an induced hydrophilicity; however, surface energy values declined markedly upon using cross-linkers. Finally, thermal stability of hybrids was adversely affected, compared to neat CNFs. Our study suggests the potential utilization of low-cost, sustainable biobarrier films for application in food/drug packaging, where low permeation of moisture is highly desirable.