Defence of doctoral thesis: Alexandros Alexakis – Nanolatexes: a versatile toolbox for cellulose modification
KTH | WWSC
The defense is taking place at room Kollegiesalen, KTH campus and online via Zoom.
Opponent: Assistant Prof. Justin Zoppe, Polytechnic University of Catalonia
Supervisor: Professor Eva Malmström, KTH
Cellulosic materials are widely used in our everyday lives, ranging from paperand packaging to biomedical applications. However, in most applications, cellulose must coexist with hydrophobic polymers which can be challenging due to its hydrophilic character. This has encouraged the exploration of chemical and physical modifications of cellulose.
The projects included in this thesis focus on the physical modification of cellulosic materials with tailor-made, highly versatile colloidal nanoparticles synthesized in water, called nanolatexes. Their synthesis is based on the combination of the reversible addition-fragmentation chain transfer (RAFT) polymerization with polymerization-induced self-assembly (PISA). The bridging of these techniques results in the formation of amphiphilic diblock copolymers which self-assemble in water forming a variety of morphologies. Spheres, worms and vesicles with pH-responsive shell polymers were prepared to investigate the parameters that tune these morphological transitions. Less investigated parameters such as the chemical composition of the RAFT agent were studied which resulted in the formation of bimodal nanolatexes with opal-like characteristics in a reproducible manner.
A fundamental investigation of the parameters that govern the adsorption of cationically charged nanolatexes onto silica and regenerated TEMPO-oxidized cellulose model surfaces was also performed. The combination of gravimetric and a reflectometric techniques revealed the complexity of that model surface. Both the size and the charge density of the nanolatexes were found to influence their adsorption. The information gained from this study was implemented in the preparation of cellulose nanofibril (CNF)-nanocomposites with low contents of nanolatexes. It was found that when the nanolatex content was below 1 wt% the mechanical profile of the CNF-nanocomposites was improved.
Finally, wood-based components were used to replace fossil-based monomers in nanolatexes. They were readily adsorbed onto cellulose filter papers and annealed, thus demonstrating their film formation capacity. Nanolatexes comprised of a wood-based shell polymer have a promising high-end application profile, as showcased by their interactions with Cu(II) ions, where nanolatexes prevented the formation of Cu(II) ion aggregates.
The results summarized in this thesis add to the understanding on physical modification of cellulose and are envisaged to further promote the utilization of wood-based monomers in the production of the polymers for high-end applications.