Effect of Morphology and Size of Halloysite Nanotubes on Functional Pectin Bionanocomposites for Food Packaging Applications

Pectin bionanocomposite films filled with various concentrations of two different types of halloysite nanotubes were prepared and characterized in this study as potential films for food packaging applications. The two types of halloysite nanotubes were long and thin (patch) (200-30 000 nm length) and short and stubby (Matauri Bay) (50-3000 nm length) with different morphological, physical, and dispersibility properties. Both matrix (pectin) and reinforcer (halloysite nanotubes) used in this study are considered as biocompatible, natural, and low-cost materials. Various characterization tests including Fourier transform infrared spectroscopy, field emission scanning electron microscopy, release kinetics, contact angle, and dynamic mechanical analysis were performed to evaluate the performance of the pectin films. Exceptional thermal, tensile, and contact angle properties have been achieved for films reinforced by patch halloysite nanotubes due to the patchy and lengthy nature of these tubes, which form a bird nest structure in the pectin matrix. Matauri Bay halloysite nanotubes were dispersed uniformly and individually in the matrix in low and even high halloysite nanotube concentrations. Furthermore, salicylic acid as a biocidal agent was encapsulated in the halloysite nanotubes lumen to control its release kinetics. On this basis, halloysite nanotubes/salicylic acid hybrids were dispersed into the pectin matrix to develop functional biofilms with antimicrobial properties that can be extended over time. Results revealed that shorter nanotubes (Matauri Bay) had better ability for the encapsulation of salicylic acid into their lumen, while patchy structure and longer tubes of patch halloysite nanotubes made the encapsulation process more difficult, as they might need more time and energy to be fully loaded by salicylic acid. Moreover, antimicrobial activity of the films against four different strains of Gram-positive and Gram-negative bacteria indicated the effective antimicrobial properties of pectin/halloysite functionalized films and their potential to be used for food packaging applications.