Mechanical behavior of biopolymer composite coatings on plastic films by depth-sensing indentation - A nanoscale study

Cesare Rovera; Carlo A Cozzolino; Masoud Ghaani; Davide Morrone; Richard T Olsson; Stefano Farris

doi:10.1016/j.jcis.2017.10.108

Mechanical behavior of biopolymer composite coatings on plastic films by depth-sensing indentation - A nanoscale study

J Colloid Interface Sci. 2018 Feb 15:512:638-646. doi: 10.1016/j.jcis.2017.10.108. Epub 2017 Oct 31.

Authors

Cesare Rovera¹, Carlo A Cozzolino¹, Masoud Ghaani¹, Davide Morrone², Richard T Olsson³, Stefano Farris⁴

Affiliations

¹ DeFENS, Department of Food, Environmental and Nutritional Sciences-Packaging Division, University of Milan, via Celoria 2, 20133 Milan, Italy.
² R&D srl Tecnologie dei Materiali, Galleria Gandhi, 2, 20017 Mazzo di Rho, Italy; Nanovea Inc., 6 Morgan, Ste 156, Irvine, CA 92618, USA.
³ Department of Fibre and Polymer Technology, School of Chemical Science and Engineering, KTH Royal Institute of Technology, Teknikringen 56, SE-100 44 Stockholm, Sweden.
⁴ DeFENS, Department of Food, Environmental and Nutritional Sciences-Packaging Division, University of Milan, via Celoria 2, 20133 Milan, Italy; INSTM, National Consortium of Materials Science and Technology, Local Unit University of Milan, via Celoria 2, 20133 Milan, Italy. Electronic address: stefano.farris@unimi.it.

PMID: 29102910
DOI: 10.1016/j.jcis.2017.10.108

Abstract

Fundamental physical behaviors of materials at the nanoscale level are crucial when local aspects govern the macroscale performance of nanocomposites, e.g., interface and surface phenomena. Because of the increasing interest in biopolymer nanocomposite coatings for many different applications (e.g., optical devices, displays/screens, and packaging), this work investigates the potential of nanoindentation as a method for clarifying the interplay between distinct phases (i.e., organic and inorganic) at local level in thin biopolymer films loaded with nanoparticles. The nanomechanical features of pullulan nanocomposite coatings laid on polyethylene terephthalate (PET) were quantified in terms of elastic modulus (E), hardness (H), and creep (C) through an instrumented indentation test composed of a loading-holding-unloading cycle. Colloidal silica (CS) and cellulose nanocrystals (CNCs) were used as spherical and rod-like nanoparticles, respectively. An overall reinforcing effect was shown for all nanocomposite coatings over the pristine (unfilled) pullulan coating. A size effect was also disclosed for the CS-loaded surfaces, with the highest E value recorded for the largest particles (8.19 ± 0.35 GPa) and the highest H value belonging to the smallest ones (395.41 ± 25.22 MPa). Comparing CS and CNCs, the addition of spherical nanoparticles had a greater effect on the surface hardness than cellulose nanowhiskers (353.50 ± 83.52 MPa and 321.36 ± 43.26 MPa, respectively). As for the elastic modulus, the addition of CS did not provide any improvement over both the bare and CNC-loaded pullulan coatings, whereas the coating including CNCs exhibited higher E values (p < .05). Finally, CS-loaded pullulan coatings were the best performing in terms of C properties, with an average indentation depth of 16.5 ± 1.85 nm under a load of ∼190 μN. These results are discussed in terms of local distribution gradients, surface chemistry of nanoparticles, and how nanoparticle aggregation occurred in the dry nanocomposite coatings.

Keywords: Aggregation; Biopolymer; Cellulose nanocrystals (CNCs); Coating; Interface; Nanocomposite; Nanoindentation; Phase separation; Pullulan; Surface.