Old cellulose for new multifunctional networks

Dissertação para obtenção do Grau de Doutor em Ciência e Engenharia de MateriaisCellulose is considered to be the most abundant and renewable natural polymer on earth. It is the main component of plant cells. The exploration of the utility and applications of this material and its derivatives has never stopped since human´s birth. It is well known that cellulose based materials can generate films and fibers, which can be, for instance, produced from cellulosic solutions. The Cellulose rich chemical structure allows different behaviors of the polymer in solution, which is the driving force for diverse films and fibers features. The main goal of this work is the manufacture and characterization of new application of the renewable cellulosic-based materials, which are at the origin of stimuli-responsive and/or functional soft films and fibers. The several materials obtained have in common the main chain cellulose backbone but present different liquid crystalline properties. Firstly rheology coupled to nuclear magnetic resonance techniques (rheo-NMR) were used to characterize a cellulose-water based liquid crystalline solution in order to establish structure/properties relationships, which were the basis to improve the design of films and fibers produced in the framework of this work. The results achieved were at the origin of a paper published in Macromolecules. Then films were produced and due to their structure and enhanced mechanical properties, different applications were realized by producing cellulosic gratings, which mimic the periodic structures that can be found in some petals of plants and a soft cellulose moisture motor was built for the first time. Two manuscripts were published, one related to the grating mimics, in Macromolecular Chemistry and Physics, and the other one dedicated to the mechanical properties and the bending of a cellulosic film controlled by moisture action in Scientific Reports (Nature Publishing Group). Concerning cellulosic fibers, two methods were selected to fabricate micro/nano networks. In order to produce suspended aligned arrays, electrospinning was chosen due to its versatility. On the obtained nano/micro cylinders, nematic and cholesteric droplets were threaded producing necklaces of liquid crystal beads for the first time. The fiber changes not only the topology of the droplet but also distorts its spherical shape to an approximately ellipsoidal droplet. An additional cylindrical surface with planar anchoring along the droplet’s long axis was also added. Designing nematic and cholesteric liquid crystal microdroplets on thin long threads opened new routes to produce fiber waveguides decorated with complex microresonators. Two Soft Matter scientific papers were published based on this work (One was chosen as the cover of that issue). Finally, nano-fibers produced by cellulose acid hydrolises were prepared and a new electro-optical sensor was built up and characterized and the results published in Liquid Crystals journal. Throughout this work Landau-de-Gennes theory was used in order to interpret and understand some of the experimental results achieved.Portuguese Science and Technology Foundation - SFRH/BD/63574/2009, PTDC/CTM/099595/2008, PTDC/CTM-POL/1484/2012, PTDC/CTM/101776/2008, PTDC/FIS/110132/2009, and PEst- C/CTM/LA0025/2011 (Strategic Project - LA 25-2011-2012