Reevaluation of the adhesion between cellulose materials using macro spherical beads and flat model surfaces.

Interactions between dry cellulose were studied using model systems, cellulose beads, and cellulose films, using custom-built contact adhesion testing equipment. Depending on the configuration of the substrates in contact, Polydimethylsiloxane (PDMS) film, cellulose films spin-coated either on PDMS or glass, the interaction shows three distinct processes. Firstly, molecular interlocking is formed between cellulose and cellulose when there is a soft PDMS thin film backing the cellulose film. Secondly, without backing, no initial attraction force between the surfaces is observed. Thirdly, a significant force increase, ∆F, is observed during the retraction process for cellulose on glass, and there is a maximum in ∆F when the retraction rate is increased. This is due to the kinetics of a contacting process occurring in the interaction zone between the surfaces caused by an interdigitation of a fine fibrillar structure at the nano-scale, whereas, for the spin-coated cellulose surfaces on the PDMS backing, there is a more direct adhesive failure. The results have generated understanding of the interaction between cellulose-rich materials, which helps design new, advanced cellulose-based materials. The results also show the complexity of the interaction between these surfaces and that earlier mechanisms, based on macroscopic material testing, are simply not adequate for molecular tailoring.

Centrifuge fractionation during purification of cellulose nanocrystals after acid hydrolysis and consequences on their chiral self-assembly.

The inherent colloidal dispersity (due to length, aspect ratio, surface charge heterogeneity) of CNCs, when produced using the typical traditional sulfuric acid hydrolysis route, presents a great challenge when interpreting colloidal properties and linking the CNC film nanostructure to the helicoidal self-assembly mechanism during drying. Indeed, further improvement of this CNC preparation route is required to yield films with better control over the CNC pitch and optical properties. Here we present a modified CNC-preparation protocol, by fractionating and harvesting CNCs with different average surface charges, rod lengths, aspect ratios, already during the centrifugation steps after hydrolysis. This enables faster CNC fractionation, because it is performed in a high ionic strength aqueous medium. By comparing dry films from the three CNC fractions, discrepancies in the CNC self-assembly and structural colors were clearly observed. Conclusively, we demonstrate a fast protocol to harvest different populations of CNCs, that enable tailored refinement of structural colors in CNC films.

Interfacial Engineering of Soft Matter Substrates by Solid-State Polymer Adsorption.

Polymer coating to substrates alters surface chemistry and imparts bulk material functionalities with a minute thickness, even in nanoscale. Specific surface modification of a substate usually requires an active substrate that, e.g., undergoes a chemical reaction with the modifying species. Here, we present a generic method for surface modification, namely, solid-state adsorption, occurring purely by entropic strive. Formed by heating above the melting point or glass transition and subsequent rinsing of the excess polymer, the emerging ultrathin (<10 nm) layers are known in fundamental polymer physics but have never been utilized as building blocks for materials and they have never been explored on soft matter substrates. We show with model surfaces as well as bulk substrates, how solid-state adsorption of common polymers, such as polystyrene and poly(lactic acid), can be applied on soft, cellulose-based substrates. Our study showcases the versatility of solid-state adsorption across various polymer/substrate systems. Specifically, we achieve proof-of-concept hydrophobization on flexible cellulosic substrates, maintaining irreversible and miniscule adsorption yet with nearly 100% coverage without compromising the bulk material properties. The method can be considered generic for all polymers whose Tg and Tm are below those of the to-be-coated adsorbed layer, and whose integrity can withstand the solvent leaching conditions. Its full potential has broad implications for diverse materials systems where surface coatings play an important role, such as packaging, foldable electronics, or membrane technology.