Natural composites like wood are scale-integrated structures that range from molecular to the macroscopic scale. Inspired by this design, layer-by-layer (LbL) deposition technique was used to create lignocellulosic composites from isolated wood polymers namely cellulose and lignin, with a lamellar architecture. In the first phase of the study, adsorption of alkali lignin onto cationic surfaces was investigated using a quartz crystal microbalance with dissipation monitoring (QCM-D). Complete coverage of the cationic surface with alkali lignin occured at low solution concentration; large affinity coefficients were calculated for this system at differing pH levels. Adsorption studies with organosolv lignin in an organic solvent, and spectroscopic analysis of mixtures of cationic polymer with alkali lignin revealed a non-covalent interaction. The work demonstrated how noncovalent interactions could be exploited to molecular organize thin polyphenolic biopolymers on cationic surfaces. The second phase of the study examined the adsorption steps during the LbL assembly process to create novel lignocellulosic composites. LbL assembly was carried out using oxidized nanocellulose (NC) and lignin, along with a cationic polymer poly(diallyldimethylammonium chloride) (PDDA). QCM-D was used to follow the sequential adsorption process of the three different polymers. Two viscoelastic models, namely Johannsmann and Voigt, were respectively used to calculate the areal mass and thickness of the adsorbed layers. Atomic force microscopy studies showed a complete coverage of the surface with lignin in all the disposition cycles, however, surface coverage with NC was seen to increase with the number of layers. Free-standing composite films were obtained when the LbL process was carried out for 250 deposition cycles (500 bilayers) on a cellulose acetate substrate, following the dissolution of the substrate in acetone. Scanning electron microscopy of the cryo-fractured cross-sections showed a lamellar structure, and the thickness per adsorption cycle was estimated to be 17 nm. The third phase of the study investigated the effect of LbL ordering of the polymers versus a cast film composed of a blended mixture of the polymers, using dynamic mechanical analysis. A tan ï ¤ peak was observed in the 30 – 40 ºC region for both films, which was observed in the neat NC film. Heating of the samples under a compressive force produced opposite effects in the films, as the LbL films exhibited swelling, whereas the cast films showed densification. The apparent activation energy of this transition (65 – 80 kJ mol-1) in cast films, calculated based on the Arrhenius equation was found to be coincident to those reported for the ï ¢ transition of amorphous cellulose. The peak was seen to disappear in case of LbL films in the second heat, whereas it was recurring in case of cast films of the blended mixture, and neat NC films. Altogether, the together the work details a novel path to integrate an organized lignin and cellulose molecular structure, albeit modified from their native form, into a three-dimensional composite material. / Ph. D.

De nombreuses sources cellulosiques sont disponibles en Tunisie en grandes quantités. On trouve par exemple des déchets d'origines agricoles (tiges de vignes) et des déchets marins (Posidonia oceanica feuilles et pelotes). La valorisation de ces déchets peut donc présenter une activité économique intéressante permettant la production de nouveaux produits et de matériaux biosourcés, c'est-à-dire de produits obtenus à partir de la biomasse végétale. Ce travail porte sur la préparation, la caractérisation et l'application de la nanocellulose. En fait, différentes qualités de nanocellulose, à savoir des nanocristaux de cellulose (NCC) et des nanofibrilles de cellulose (NFC), ont été produites et caractérisées par diverses méthodes. L'objectif était de mieux comprendre la structure et la morphologie des nanofibres obtenues à partir des deux plantes. Enfin, divers nanocomposites ont été élaborés en utilisant soit des nanocristaux de cellulose ou des nanofibrilles de cellulose comme élément de renfort de matrices polymères de type polyacrylate. Les résultats obtenus ont été comparés à ceux reportés pour d'autres sources de plantes annuelles et de bois et montrent clairement que l'on peut considérer Posidonia oceanica et la tige de vigne comme une nouvelle source d'éléments de nanorenfort dans les applications nanocomposites. / Many cellulosic sources are available in Tunisia in large quantities such as agricultural waste (vine stems) and marine residues (Posidonia oceanica leaves and balls). Their valorization presents an interesting activity to produce new products and bio-based biomass materials. The present work deals with the preparation, characterization and application of nanocellulose. In fact, different qualities of nanocellulose, namely cellulose nanocrystals (CNC) and cellulose nanofibrils (CNF) were produced and characterized by various methods. The objective was to better understand the structure and morphology of the nanofibers obtained from both plants. Finally, various nanocomposites were prepared using the cellulose nanocrystals and cellulose nanofibrils as reinforcing element in polyacrylate polymer as matrix. The obtained results were compared with those reported for other sources such as annual plants and wood. It has been shown that nanocellulose from Posidonia oceanica and vine stem can be used as a new alternative nanoreinforcing source in nanocomposite applications.

Die vorliegende Arbeit ist eine Untersuchung, inwieweit die Herstellung eines kartonbasierter POCT mit Kapillaren zum Transport von Flüssigkeiten mit Hilfe von Nanocellulose und additiv gefertigten Prägewerkzeugen möglich ist. Die Nanocellulose wurde von RISE aus Schweden zur Verfügung gestellt. Rheologische Untersuchungen ergaben, dass diese mit Hilfe eines Bingham-Modells beschrieben werden können und einer Fließgrenze unterliegen. Die Nanocellulose wurde mit Hilfe der konventionellen direkten Druckverfahren Flexo-, Tief- und Siebdruck auf verschiedene Kartonsorten aufgetragen. Der Flexo- und Tiefdruck erwies sich aufgrund einer Saffman-Taylor-Instabilität als ungeeignet zur Erzeugung von homogenen Schichten. Verschiedene Untersuchungen zeigten, dass mit Hilfe des Siebdrucks unter Verwendung eines Siebs mit sehr hoher Nassfarbschichtdicke die besten Ergebnisse erzielt werden konnten. Die Nutzung von offenen Kapillaren in POCT erfordert einen möglichst geringen Kontaktwinkel. Durch das Applizieren von Nanocellulose konnte sowohl der Kontaktwinkel des Kartons auf einen geeigneten Wert reduziert werden als auch das Penetrationsverhalten insofern verändert werden, dass die Penetration einer aufgetragenen Flüssigkeit zunächst in der Nanocellulose stattfindet. Die Penetration in den Karton selbst wurde durch die Nanocellulose stark verzögert. Die Funktionalität von offenen Kapillaren konnte im Rahmen dieser Arbeit aufgrund von mangelnder Herstellgenauigkeit der additiven Fertigung und begrenzter Kartonauswahl nicht erreicht werden. Allerdings konnten mit Hilfe einer Folienkaschierung funktionelle geschlossene Kapillaren erzeugt werden, welche einen Flüssigkeitstransport durch Kapillarkräfte über eine Distanz von 25 mm ohne Penetration in den Karton ermöglichen. Dies zeigt, dass die Herstellung und Nutzung von kartonbasierten POCT theoretisch möglich ist.:Abbildungsverzeichnis X Tabellenverzeichnis XIV Abkürzungsverzeichnis XV Symbolverzeichnis XVI 1 Einleitung 19 2 Ziele 23 3 Theoretische Grundlagen 25 3.1 Nanomaterial 25 3.2 Cellulose 26 3.3 Nanocellulose 27 3.3.1 Cellulose Nanofibrillen (CNF) 28 3.3.2 Cellulose Nanokristalle (CNC) 30 3.3.3 Carboxymethyl-Cellulose (CMC) 31 3.4 Rheologie 31 3.4.1 Eigenschaften von Suspensionen mit Nanopartikeln 32 3.4.2 Bingham-Fluide 32 3.5 Druckverfahren 34 3.5.1 Siebdruck 34 3.5.2 Tiefdruck 36 3.5.3 Flexodruck 37 3.6 Prägen 38 3.7 Microfluidic Devices und Kapillaren 39 3.7.1 Geschlossene Kapillaren 40 3.7.2 Offene Kapillaren 41 3.8 Ultraschallmessung des Penetrationsverhaltens 42 4 Materialien 45 4.1 Nanocellulose 45 4.2 Druckformen 45 4.3 Bedruckstoff 46 5 Rheologische Untersuchungen der Nanocellulose 49 5.1 Vorgehensweise 49 5.1.1 Viskositätsmessung 49 5.1.2 Erfassung der Strukturerholung 50 5.2 Ergebnisse 50 5.2.1 Viskosität 50 5.2.2 Strukturerholung 52 5.2.3 Vergleich mit konventionellen Druckverfahren 53 6 Explorative Studie 55 6.1 Druckversuche 55 6.1.1 Siebdruck 55 6.1.2 Flexo- und Tiefdruck 56 6.2 Vorgehensweise der Auswertung 57 6.3 Ergebnisse und Diskussion der Druckversuche 59 6.3.1 Visuelle Homogenität der Oberfläche 59 6.3.2 Einfluss auf Bedruckstoff 62 6.3.3 Rauheit 63 6.3.4 Kontaktwinkel 65 6.3.5 Wasserfestigkeit 66 6.3.6 Penetrationsverhalten 66 6.4 Prägewerkzeuge und -versuche 73 6.5 Ergebnisse und Diskussion der Prägeversuche 76 6.6 Erkenntnisse der explorativen Studie 79 7 Weiterentwickelte Studie 81 7.1 Vorgehensweise 81 7.2 Ergebnisse 82 7.2.1 Siebdruck 83 7.2.2 Vollprägung 85 7.2.3 Reliefprägung 90 7.3 Erkenntnisse der weiterentwickelten Studie 91 7.4 Empfehlungen für weitere Studien 93 8 Zusammenfassung und Ausblick 95 Literaturverzeichnis XCVII Anhänge / The present work is an investigation into the potential of fabricating a cardboard-based POCT with capillaries for transporting fluids using nanocellulose and additive manufactured embossing tools. The nanocellulose was provided by RISE from Sweden. Rheological studies showed that they can be described using a Bingham model and are subject to a yield point. The nanocellulose was applied to various types of cardboard using the conventional direct printing processes of flexographic, gravure and screen printing. Flexo and gravure printing proved unsuitable for producing homogeneous layers due to a Saffman-Taylor instability. Various investigations showed that screen printing using a screen with a very high wet ink film thickness produced the best results. The use of open capillaries in POCT requires the lowest possible contact angle. By applying nanocellulose, it was possible to reduce the contact angle of the cardboard to a suitable value and to change the penetration behavior in that the penetration of an applied liquid first takes place in the nanocellulose. Penetration into the cardboard itself was greatly delayed by the nanocellulose. The functionality of open capillaries could not be achieved in this work due to lack of manufacturing accuracy of additive manufacturing and limited cardboard selection. However, functional closed capillaries could be created using film lamination, allowing fluid transport by capillary forces over a distance of 25 mm without penetration into the cardboard. This shows that the production and use of cardboard-based POCT is theoretically possible.:Abbildungsverzeichnis X Tabellenverzeichnis XIV Abkürzungsverzeichnis XV Symbolverzeichnis XVI 1 Einleitung 19 2 Ziele 23 3 Theoretische Grundlagen 25 3.1 Nanomaterial 25 3.2 Cellulose 26 3.3 Nanocellulose 27 3.3.1 Cellulose Nanofibrillen (CNF) 28 3.3.2 Cellulose Nanokristalle (CNC) 30 3.3.3 Carboxymethyl-Cellulose (CMC) 31 3.4 Rheologie 31 3.4.1 Eigenschaften von Suspensionen mit Nanopartikeln 32 3.4.2 Bingham-Fluide 32 3.5 Druckverfahren 34 3.5.1 Siebdruck 34 3.5.2 Tiefdruck 36 3.5.3 Flexodruck 37 3.6 Prägen 38 3.7 Microfluidic Devices und Kapillaren 39 3.7.1 Geschlossene Kapillaren 40 3.7.2 Offene Kapillaren 41 3.8 Ultraschallmessung des Penetrationsverhaltens 42 4 Materialien 45 4.1 Nanocellulose 45 4.2 Druckformen 45 4.3 Bedruckstoff 46 5 Rheologische Untersuchungen der Nanocellulose 49 5.1 Vorgehensweise 49 5.1.1 Viskositätsmessung 49 5.1.2 Erfassung der Strukturerholung 50 5.2 Ergebnisse 50 5.2.1 Viskosität 50 5.2.2 Strukturerholung 52 5.2.3 Vergleich mit konventionellen Druckverfahren 53 6 Explorative Studie 55 6.1 Druckversuche 55 6.1.1 Siebdruck 55 6.1.2 Flexo- und Tiefdruck 56 6.2 Vorgehensweise der Auswertung 57 6.3 Ergebnisse und Diskussion der Druckversuche 59 6.3.1 Visuelle Homogenität der Oberfläche 59 6.3.2 Einfluss auf Bedruckstoff 62 6.3.3 Rauheit 63 6.3.4 Kontaktwinkel 65 6.3.5 Wasserfestigkeit 66 6.3.6 Penetrationsverhalten 66 6.4 Prägewerkzeuge und -versuche 73 6.5 Ergebnisse und Diskussion der Prägeversuche 76 6.6 Erkenntnisse der explorativen Studie 79 7 Weiterentwickelte Studie 81 7.1 Vorgehensweise 81 7.2 Ergebnisse 82 7.2.1 Siebdruck 83 7.2.2 Vollprägung 85 7.2.3 Reliefprägung 90 7.3 Erkenntnisse der weiterentwickelten Studie 91 7.4 Empfehlungen für weitere Studien 93 8 Zusammenfassung und Ausblick 95 Literaturverzeichnis XCVII Anhänge

Die vorliegende Arbeit ist eine Untersuchung, inwieweit die Herstellung eines kartonbasierter POCT mit Kapillaren zum Transport von Flüssigkeiten mit Hilfe von Nanocellulose und additiv gefertigten Prägewerkzeugen möglich ist. Die Nanocellulose wurde von RISE aus Schweden zur Verfügung gestellt. Rheologische Untersuchungen ergaben, dass diese mit Hilfe eines Bingham-Modells beschrieben werden können und einer Fließgrenze unterliegen. Die Nanocellulose wurde mit Hilfe der konventionellen direkten Druckverfahren Flexo-, Tief- und Siebdruck auf verschiedene Kartonsorten aufgetragen. Der Flexo- und Tiefdruck erwies sich aufgrund einer Saffman-Taylor-Instabilität als ungeeignet zur Erzeugung von homogenen Schichten. Verschiedene Untersuchungen zeigten, dass mit Hilfe des Siebdrucks unter Verwendung eines Siebs mit sehr hoher Nassfarbschichtdicke die besten Ergebnisse erzielt werden konnten. Die Nutzung von offenen Kapillaren in POCT erfordert einen möglichst geringen Kontaktwinkel. Durch das Applizieren von Nanocellulose konnte sowohl der Kontaktwinkel des Kartons auf einen geeigneten Wert reduziert werden als auch das Penetrationsverhalten insofern verändert werden, dass die Penetration einer aufgetragenen Flüssigkeit zunächst in der Nanocellulose stattfindet. Die Penetration in den Karton selbst wurde durch die Nanocellulose stark verzögert. Die Funktionalität von offenen Kapillaren konnte im Rahmen dieser Arbeit aufgrund von mangelnder Herstellgenauigkeit der additiven Fertigung und begrenzter Kartonauswahl nicht erreicht werden. Allerdings konnten mit Hilfe einer Folienkaschierung funktionelle geschlossene Kapillaren erzeugt werden, welche einen Flüssigkeitstransport durch Kapillarkräfte über eine Distanz von 25 mm ohne Penetration in den Karton ermöglichen. Dies zeigt, dass die Herstellung und Nutzung von kartonbasierten POCT theoretisch möglich ist.:Abbildungsverzeichnis X Tabellenverzeichnis XIV Abkürzungsverzeichnis XV Symbolverzeichnis XVI 1 Einleitung 19 2 Ziele 23 3 Theoretische Grundlagen 25 3.1 Nanomaterial 25 3.2 Cellulose 26 3.3 Nanocellulose 27 3.3.1 Cellulose Nanofibrillen (CNF) 28 3.3.2 Cellulose Nanokristalle (CNC) 30 3.3.3 Carboxymethyl-Cellulose (CMC) 31 3.4 Rheologie 31 3.4.1 Eigenschaften von Suspensionen mit Nanopartikeln 32 3.4.2 Bingham-Fluide 32 3.5 Druckverfahren 34 3.5.1 Siebdruck 34 3.5.2 Tiefdruck 36 3.5.3 Flexodruck 37 3.6 Prägen 38 3.7 Microfluidic Devices und Kapillaren 39 3.7.1 Geschlossene Kapillaren 40 3.7.2 Offene Kapillaren 41 3.8 Ultraschallmessung des Penetrationsverhaltens 42 4 Materialien 45 4.1 Nanocellulose 45 4.2 Druckformen 45 4.3 Bedruckstoff 46 5 Rheologische Untersuchungen der Nanocellulose 49 5.1 Vorgehensweise 49 5.1.1 Viskositätsmessung 49 5.1.2 Erfassung der Strukturerholung 50 5.2 Ergebnisse 50 5.2.1 Viskosität 50 5.2.2 Strukturerholung 52 5.2.3 Vergleich mit konventionellen Druckverfahren 53 6 Explorative Studie 55 6.1 Druckversuche 55 6.1.1 Siebdruck 55 6.1.2 Flexo- und Tiefdruck 56 6.2 Vorgehensweise der Auswertung 57 6.3 Ergebnisse und Diskussion der Druckversuche 59 6.3.1 Visuelle Homogenität der Oberfläche 59 6.3.2 Einfluss auf Bedruckstoff 62 6.3.3 Rauheit 63 6.3.4 Kontaktwinkel 65 6.3.5 Wasserfestigkeit 66 6.3.6 Penetrationsverhalten 66 6.4 Prägewerkzeuge und -versuche 73 6.5 Ergebnisse und Diskussion der Prägeversuche 76 6.6 Erkenntnisse der explorativen Studie 79 7 Weiterentwickelte Studie 81 7.1 Vorgehensweise 81 7.2 Ergebnisse 82 7.2.1 Siebdruck 83 7.2.2 Vollprägung 85 7.2.3 Reliefprägung 90 7.3 Erkenntnisse der weiterentwickelten Studie 91 7.4 Empfehlungen für weitere Studien 93 8 Zusammenfassung und Ausblick 95 Literaturverzeichnis XCVII Anhänge / The present work is an investigation into the potential of fabricating a cardboard-based POCT with capillaries for transporting fluids using nanocellulose and additive manufactured embossing tools. The nanocellulose was provided by RISE from Sweden. Rheological studies showed that they can be described using a Bingham model and are subject to a yield point. The nanocellulose was applied to various types of cardboard using the conventional direct printing processes of flexographic, gravure and screen printing. Flexo and gravure printing proved unsuitable for producing homogeneous layers due to a Saffman-Taylor instability. Various investigations showed that screen printing using a screen with a very high wet ink film thickness produced the best results. The use of open capillaries in POCT requires the lowest possible contact angle. By applying nanocellulose, it was possible to reduce the contact angle of the cardboard to a suitable value and to change the penetration behavior in that the penetration of an applied liquid first takes place in the nanocellulose. Penetration into the cardboard itself was greatly delayed by the nanocellulose. The functionality of open capillaries could not be achieved in this work due to lack of manufacturing accuracy of additive manufacturing and limited cardboard selection. However, functional closed capillaries could be created using film lamination, allowing fluid transport by capillary forces over a distance of 25 mm without penetration into the cardboard. This shows that the production and use of cardboard-based POCT is theoretically possible.:Abbildungsverzeichnis X Tabellenverzeichnis XIV Abkürzungsverzeichnis XV Symbolverzeichnis XVI 1 Einleitung 19 2 Ziele 23 3 Theoretische Grundlagen 25 3.1 Nanomaterial 25 3.2 Cellulose 26 3.3 Nanocellulose 27 3.3.1 Cellulose Nanofibrillen (CNF) 28 3.3.2 Cellulose Nanokristalle (CNC) 30 3.3.3 Carboxymethyl-Cellulose (CMC) 31 3.4 Rheologie 31 3.4.1 Eigenschaften von Suspensionen mit Nanopartikeln 32 3.4.2 Bingham-Fluide 32 3.5 Druckverfahren 34 3.5.1 Siebdruck 34 3.5.2 Tiefdruck 36 3.5.3 Flexodruck 37 3.6 Prägen 38 3.7 Microfluidic Devices und Kapillaren 39 3.7.1 Geschlossene Kapillaren 40 3.7.2 Offene Kapillaren 41 3.8 Ultraschallmessung des Penetrationsverhaltens 42 4 Materialien 45 4.1 Nanocellulose 45 4.2 Druckformen 45 4.3 Bedruckstoff 46 5 Rheologische Untersuchungen der Nanocellulose 49 5.1 Vorgehensweise 49 5.1.1 Viskositätsmessung 49 5.1.2 Erfassung der Strukturerholung 50 5.2 Ergebnisse 50 5.2.1 Viskosität 50 5.2.2 Strukturerholung 52 5.2.3 Vergleich mit konventionellen Druckverfahren 53 6 Explorative Studie 55 6.1 Druckversuche 55 6.1.1 Siebdruck 55 6.1.2 Flexo- und Tiefdruck 56 6.2 Vorgehensweise der Auswertung 57 6.3 Ergebnisse und Diskussion der Druckversuche 59 6.3.1 Visuelle Homogenität der Oberfläche 59 6.3.2 Einfluss auf Bedruckstoff 62 6.3.3 Rauheit 63 6.3.4 Kontaktwinkel 65 6.3.5 Wasserfestigkeit 66 6.3.6 Penetrationsverhalten 66 6.4 Prägewerkzeuge und -versuche 73 6.5 Ergebnisse und Diskussion der Prägeversuche 76 6.6 Erkenntnisse der explorativen Studie 79 7 Weiterentwickelte Studie 81 7.1 Vorgehensweise 81 7.2 Ergebnisse 82 7.2.1 Siebdruck 83 7.2.2 Vollprägung 85 7.2.3 Reliefprägung 90 7.3 Erkenntnisse der weiterentwickelten Studie 91 7.4 Empfehlungen für weitere Studien 93 8 Zusammenfassung und Ausblick 95 Literaturverzeichnis XCVII Anhänge

A proposta deste trabalho busca avaliar a obtenção da celulose a partir do bagaço de cana-de-açúcar, os meios de obtenção da nanocelulose a partir da celulose por ultrasonicação, bem como a análise das propriedades do nanocompósito EVA/nanocelulose por meio do estudo das propriedades físicas e químicas do nanocompósito e do EVA puro. Inicialmente foi obtida celulose a partir das fibras de bagaço de cana-de-açúcar por meio de métodos químicos de deslignificação e branqueamento. A hidrólise ácida permitiu a obtenção de nanoestruturas de celulose em meio aquoso e o método de sonicação em solução com água/DMF/etanol se mostrou eficiente para melhor controle do tamanho e dispersão das nanoestruturas de celulose. As nanoestruturas de celulose foram caracterizadas por espalhamento dinâmico de luz (DLS), microscopia eletrônica de transmissão (TEM), difração de Raio X (DRX), análise termogravimétrica (TGA) e espectroscopia vibracional de absorção no infravermelho com transformada de Fourier (FTIR). Os resultados mostraram tamanho inferior à 100nm, cristalinidade superior à 70% e decomposição térmica se iniciando por volta de 185°C para as partículas de nanocelulose. Na segunda parte do trabalho foram processados filmes flexíveis de: EVA puro, EVA com 1% de nanocelulose e EVA com 3% de nanocelulose. Os filmes processados foram analisados por calorimetria exploratória diferencial (DSC), análise termogravimétrica, ensaio mecânico de resistência à tração e microscopia eletrônica de varredura (MEV). Os dados de resistência à tração e módulo Young exibiram um aumento dos valores de resistência dos compósitos de EVA/NC em relação ao EVA puro. O compósito EVA/NC não apresentou partículas aglomeradas. A ausência de aglomerados no compósito está relacionada ao reforço mecânico conferido ao material processado. / The aim of this work is to evaluate the production of cellulose from sugarcane bagasse, the means of obtaining nanocellulose from cellulose by ultrasonication, as well as the analysis of the properties of the nanocomposite EVA/nanocellulose by studying the physical properties and chemical properties of nanocomposite and pure EVA. Initially, cellulose was obtained from the sugarcane bagasse fibers by means of chemical delignification and bleaching methods. The acid hydrolysis allowed to obtain cellulose nanoparticles in aqueous medium and the sonication method in water / DMF / ethanol solution proved efficient for better control of the size and dispersion of the cellulose nanoparticles. Cellulose nanoparticles were characterized by dynamic light scattering (DLS), transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA) and infrared Fourier transform infrared spectroscopy (FTIR) ). The results showed size less than 100nm, crystallinity greater than 70% and thermal decomposition starting at about 185°C for the nanocellulose particles. In the second part of the work, flexible films of: pure EVA, EVA with 1% of nanocellulose and EVA with 3% of nanocellulose were processed. The processed films were analyzed by differential scanning calorimetry (DSC), thermogravimetric analysis, mechanical tensile strength test and scanning electron microscopy (SEM). The tensile strength data and Young modulus showed an increase in the EVA/NC composite strength values over pure EVA. The EVA/NC composite showed no agglomerated particles. The absence of agglomerates in the composite is related to the mechanical reinforcement given to the processed material.

This work investigates the compositional and nanostructural variability of celluloses isolated from plants and the impact of the variability in the production of cellulose nanocrystals. A variable set of cellulose isolated from plants were generated starting with a range of feedstocks (coconut fiber, sisal fiber, eucalyptus sawdust, pine sawdust, sugarcane rind and sugarcane pith), applying a range of cellulose isolation processes (acetossolv, liquid hot water, alkaline, and liquid hot water + alkaline) and adding commercial cellulose (eucalyptus kraft pulp, dissolving pulp, and microcrystalline cellulose) as reference materials. The nanostructural characteristics were evaluated by calorimetric thermoporometry, X-ray diffraction, and moisture sorption isotherms. Composition was evaluated by standard wet chemical analysis and insights on functional groups were obtained by infrared spectroscopy. The cellulose nanocrystals were produced by acid hydrolysis with sulfuric acid and characterized by atomic force microscopy and X-ray diffraction. The measured parameters of the isolated celluloses were spread, showing we could achieve a highly diverse set of substrates. Significant correlations between measured variables across the sample set, indicating possible unforeseen multivariate relations among cellulose features. For example, we could show that cellulose monolayer hydration is determined by both hemicelluloses content (compositional parameter) as well as cellulose crystal width (structural parameter). Cellulose nanocrystals were successfully produced, although in some cases such as for the acetossolv pulps the acid conditions were too aggressive and oxidized the substrates. Finally, some quantitative correlations were seen between the parameters of cellulose substrates and the resulting cellulose nanocrystals. These results supply the first hints about how the nanostructural variability of isolated cellulose can influence the cellulose nanocrystals produced from them. / Este trabalho investiga a variabilidade composicional e nanoestrutural de celuloses isoladas de plantas e o seu impacto na variabilidade na produção de nanocristais de celulose. Um conjunto variável de celuloses isoladas de plantas foi gerado a partir de uma série de matérias-primas (fibra de coco, sisal, serragem de eucalipto, serragem de pinheiro, casca de cana e miolo de cana), aplicando uma série de processos de isolamento de celulose (hidrotérmico, alcalino, hidrotérmico + alcalino e acetosolve) e adicionando celuloses comerciais (polpa kraft de eucalipto, polpa para dissolução e celulose microcristalina) como materiais de referência. As características nanoestruturais foram avaliadas por termoporometria calorimétrica, difração de raios X e isotermas de sorção de umidade. A composição foi avaliada por análise química húmida padrão e os conhecimentos sobre grupos funcionais foram obtidos por espectroscopia de infravermelhos. Os nanocristais de celulose foram produzidos por hidrólise ácida com ácido sulfúrico e caracterizados por microscopia de força atômica e difração de raios-X. Os parâmetros medidos das celuloses isoladas foram distribuídos, demonstrando que poderíamos alcançar um conjunto altamente diversificado de substratos. Correlações significativas entre as variáveis medidas foram observadas em todo o conjunto amostral, indicando possíveis relações multivariadas imprevistas entre as características da celulose. Por exemplo, poderíamos demonstrar que a monocamada de hidratação de celulose é determinada tanto pelo conteúdo de hemiceluloses (parâmetro de composição) quanto pela largura do cristal de celulose (parâmetro estrutural). Os nanocristais de celulose foram produzidos com sucesso, embora em alguns casos, como nas polpas acetosolve, as condições ácidas fossem muito agressivas e oxidassem os substratos. Finalmente, algumas correlações quantitativas foram observadas entre os parâmetros dos substratos de celulose e os nanocristais de celulose resultantes. Estes resultados fornecem as primeiras dicas sobre como a variabilidade nanoestrutural da celulose isolada pode influenciar os nanocristais de celulose produzidos a partir deles.

This work investigates the compositional and nanostructural variability of celluloses isolated from plants and the impact of the variability in the production of cellulose nanocrystals. A variable set of cellulose isolated from plants were generated starting with a range of feedstocks (coconut fiber, sisal fiber, eucalyptus sawdust, pine sawdust, sugarcane rind and sugarcane pith), applying a range of cellulose isolation processes (acetossolv, liquid hot water, alkaline, and liquid hot water + alkaline) and adding commercial cellulose (eucalyptus kraft pulp, dissolving pulp, and microcrystalline cellulose) as reference materials. The nanostructural characteristics were evaluated by calorimetric thermoporometry, X-ray diffraction, and moisture sorption isotherms. Composition was evaluated by standard wet chemical analysis and insights on functional groups were obtained by infrared spectroscopy. The cellulose nanocrystals were produced by acid hydrolysis with sulfuric acid and characterized by atomic force microscopy and X-ray diffraction. The measured parameters of the isolated celluloses were spread, showing we could achieve a highly diverse set of substrates. Significant correlations between measured variables across the sample set, indicating possible unforeseen multivariate relations among cellulose features. For example, we could show that cellulose monolayer hydration is determined by both hemicelluloses content (compositional parameter) as well as cellulose crystal width (structural parameter). Cellulose nanocrystals were successfully produced, although in some cases such as for the acetossolv pulps the acid conditions were too aggressive and oxidized the substrates. Finally, some quantitative correlations were seen between the parameters of cellulose substrates and the resulting cellulose nanocrystals. These results supply the first hints about how the nanostructural variability of isolated cellulose can influence the cellulose nanocrystals produced from them. / Este trabalho investiga a variabilidade composicional e nanoestrutural de celuloses isoladas de plantas e o seu impacto na variabilidade na produção de nanocristais de celulose. Um conjunto variável de celuloses isoladas de plantas foi gerado a partir de uma série de matérias-primas (fibra de coco, sisal, serragem de eucalipto, serragem de pinheiro, casca de cana e miolo de cana), aplicando uma série de processos de isolamento de celulose (hidrotérmico, alcalino, hidrotérmico + alcalino e acetosolve) e adicionando celuloses comerciais (polpa kraft de eucalipto, polpa para dissolução e celulose microcristalina) como materiais de referência. As características nanoestruturais foram avaliadas por termoporometria calorimétrica, difração de raios X e isotermas de sorção de umidade. A composição foi avaliada por análise química húmida padrão e os conhecimentos sobre grupos funcionais foram obtidos por espectroscopia de infravermelhos. Os nanocristais de celulose foram produzidos por hidrólise ácida com ácido sulfúrico e caracterizados por microscopia de força atômica e difração de raios-X. Os parâmetros medidos das celuloses isoladas foram distribuídos, demonstrando que poderíamos alcançar um conjunto altamente diversificado de substratos. Correlações significativas entre as variáveis medidas foram observadas em todo o conjunto amostral, indicando possíveis relações multivariadas imprevistas entre as características da celulose. Por exemplo, poderíamos demonstrar que a monocamada de hidratação de celulose é determinada tanto pelo conteúdo de hemiceluloses (parâmetro de composição) quanto pela largura do cristal de celulose (parâmetro estrutural). Os nanocristais de celulose foram produzidos com sucesso, embora em alguns casos, como nas polpas acetosolve, as condições ácidas fossem muito agressivas e oxidassem os substratos. Finalmente, algumas correlações quantitativas foram observadas entre os parâmetros dos substratos de celulose e os nanocristais de celulose resultantes. Estes resultados fornecem as primeiras dicas sobre como a variabilidade nanoestrutural da celulose isolada pode influenciar os nanocristais de celulose produzidos a partir deles.

To meet the predicted increase in demand for energy storage in tomorrow's society, the development of inexpensive, flexible, lightweight and sustainable energy-storage materials is essential. In this respect, devices based on electroactive organic molecules, such as conducting polymers, are highly interesting. The aim of this thesis was to evaluate the use of nanocellulose as a matrix material in composites of cellulose and the electroactive polymer polypyrrole (PPy), and the use of these composites in all-polymer paper-based energy-storage devices.   Pyrrole was polymerized using FeCl3 onto cellulose nanofibers in the form of a hydrogel. The resulting PPy-coated fibers were washed with water and dried into a high surface area, conductive paper material. Variations in the drying technique provided a way of controlling the porosity and the surface area of wood-based cellulose nanofibers, as the properties of the cellulose were found to have a large influence on the composite structure. Different nanocellulose fibers, of algal and wood origin, were evaluated as the reinforcing phase in the conductive composites. These materials had conductivities of 1–6 S/cm and specific surface areas of up to 246 m2/g at PPy weight fractions around 67%.   Symmetrical supercapacitor devices with algae-based nanocellulose-PPy electrodes and an aqueous electrolyte showed specific charge capacities of around 15 mAh/g and specific capacitances of around 35 F/g, normalized with respect to the dry electrode weight. Potentiostatic charging of the devices was suggested as a way to make use of the rapid oxidation and reduction processes in these materials, thus minimizing the charging time and the effect of the IR drop in the device, and ensuring charging to the right potential. Repeated charging and discharging of the devices revealed a 10–20% loss in capacity over 10 000 cycles. Upon up-scaling of the devices, it was found that an improved cell design giving a lower cell resistance was needed in order to maintain high charge and discharge rates.   The main advantages of the presented concept of nanocellulose-PPy-based electrical energy storage include the eco-friendly raw materials, an up-scalable and potentially cost-effective production process, safe operation, and the controllable porosity and moldability offered by the nanocellulose fiber matrix. Integrating energy storage devices into paper could lead to un- precedented opportunities for new types of consumer electronics. Future research efforts should be directed at increasing the energy density and improving the stability of this type of device as well as advancing the fundamental understanding of the current limitations of these properties.

Papers are coated in order to improve the properties of the surface, to improve printability and to include new functionalities like barriers properties. Typical coating formulation contains a high number of components, some are made from minerals and others are manufactured from petroleum. The barrier properties of today's paper based packages are plastics and/or aluminum             foil. Environmentally friendly substitutie of these nonrenewable materials are needed.  Nanocellulose is a promising material                 and of a growing interest as an alternative to petroleum-based materials, since nanocellulose films/coatings have been shown to have excellent mechanical and barrier properties.   This project aimed to evaluate nanocellulose in combination with minerals in paper coatings. The project had two approaches. One was to evaluate the barrier properties of MFC coatings with mineral included. The second part was about coatings for           printing matters, and evaluation of the possibility to replace petroleum-based binders in the coating color with MFC. Barrier properties were evaluated by measuring the air permeability of the coatings. The properties of the coating affecting the         printability in offset printing examined was the surface energy, the gloss, the roughness of the coatings, the strength and the offset ink setting.   Carboxymethylated nanocellulose formed denser films and had superior barrier properties compared with enzymatically pretreated nanocellulose. Adding of minerals did not affect the barrier properties of the MFC coatings to a significant extent.         Therefore, minerals cannot be added to enhance the barrier but it can be added to reduce the cost of the coating process without losing any barrier properties.                                 The print quality depends on how the ink interacts with the coating. These coatings did have a relatively high surface energy, which is preferable for printing with waterborne ink. It was also shown that the absorption abilities increased when the amount of MFC was increased. However, offset printing demands high surface strength and addition of MFC in the coating color                     drastically decreased the strength. This means that the coatings produced in this work are not strong enough and thereby not           suitable for offset printing. However other printing technologies put lower demand on surface strength and are still possible.

Nanocellulose has received considerable interest during the last decade because it is renewable and biodegradable, and has excellent mechanical properties, nanoscale dimensions and wide functionalization possibilities. It is considered to be a unique and versatile platform on which new functional materials can be based. This thesis focuses on nanocellulose from wood (NFC) and from Cladophora algae (CNC), functionalized with surface charges or coated with the conducting polymer polypyrrole (PPy), aiming to study the influence of synthesis processes on structural and electrochemical properties of such materials and assess their biocompatibility. The most important results of the work demonstrated that 1) CNC was oxidized to the same extent using electrochemical TEMPO-mediated oxidation as with conventional TEMPO processes, which may facilitate easier reuse of the reaction medium; 2) NFC and CNC films with or without surface charges were non-cytotoxic as assessed by indirect in vitro testing. Anionic TEMPO-CNC films promoted fibroblast adhesion and proliferation in direct in vitro cytocompatibility testing, possibly due to its aligned fibril structure; 3) Rinsing of PPy-coated nanocellulose fibrils, which after drying into free-standing porous composites are applicable for energy storage and electrochemically controlled ion extraction, significantly degraded the PPy coating, unless acidic rinsing was employed. Only minor degradation was observed during long-term ambient storage; 4) Variations in the drying method as well as type and amount of nanocellulose offered ways of tailoring the porosities of nanocellulose/PPy composites between 30% and 98%, with increments of ~10%. Supercritical CO2-drying generated composites with the largest specific surface area yet reported for nanocellulose/conducting polymer composites (246 m2/g). The electrochemical oxidation rate was found to be controlled by the composite porosity; 5) In blood compatibility assessments for potential hemodialysis applications, heparinization of CNC/PPy composites was required to obtain thrombogenic properties comparable to commercial hemodialysis membranes. The pro-inflammatory characteristics of non-heparinized and heparinized composites were, to some extent, superior to commercial membranes. The heparin coating did not affect the solute extraction capacity of the composite. The presented results are deemed to be useful for tuning the properties of systems based on the studied materials in e.g. energy storage, ion exchange and biomaterial applications.