Nanocellulose is an interesting natural material thatis gaining interest in the field of materials science, particularly nanocomposites. Depending on the disintegration route, nanocellulose can be isolated either in the form of long and flexible fibres (nanofibrillated cellulose, NFC), or stiff, rod-like crystals (cellulose nanocrystals, CNC). Nanocellulose can be utilized in nanocomposites either as a reinforcement element or as a network matrix due to its ability to form a strong network. In this thesis, nanocellulose based materials are prepared by evaporation of a liquid medium. The key step in this processing route is a good dispersion of the nanoparticles in the selected matrix. Therefore the importance of surface modification in order to ensure favourable nanocellulose dispersion is clarified in avariety of materials systems. In Paper I, poly(methyl methacrylate) (PMMA) based fibres prepared by electrospinning were reinforced with nanofibrillated cellulose. Native NFC appeared to show a good compatibility with PMMA matrix in the electrospinning solution and resulting fibres. Furthermore, a new method for mechanical testing of mats with random fibre orientation as well as aligned fibres was developed. In Paper II, commingled nanopaper structures with carbon nanotubes (CNTs) were prepared. Several surfactants were used to disperse hydrophobic CNTs in water. A nonylphenol phosphate ester (NPPE) was found to work well for both dispersing CNTs in water and providing compatibility with NFC through electrostatic repulsion between the phosphate ester groups of the surfactant and the carboxylate groups of NFC. In Paper III, a new water based route for functionalization of cellulose nanocrystals was developed. In this approach, inspired by organo-modified layered silicates, quaternary ammonium salts were adsorbed. It was demonstrated that different functionalities (alkyl, phenyl, glycidylor diallyl) can be introduced onto the cellulose and the dispersibility in organic solvents was studied. Subsequently, in Paper IV, nanocomposites with poly(vinyl acetate) (PVAc)were prepared. The effect of modification on the degree of dispersion of the CNC within the matrix was studied as well as the strong effects on the properties of the resulting nanocomposites. In Paper V, taking advantage of the entangled NFC network and the possibility to tailor the pore size and surface chemistry, lubricant-infused slippery films and coatings based on NFC were prepared for the first time. / <p>QC 20131016</p>

Submitted by Milena Rubi ( ri.bso@ufscar.br) on 2017-10-17T16:37:26Z No. of bitstreams: 1 SILVA_Barbara_2017.pdf: 2018251 bytes, checksum: 6dab58bc6d22c81d23f1cfb7011353bf (MD5) / Approved for entry into archive by Milena Rubi ( ri.bso@ufscar.br) on 2017-10-17T16:37:37Z (GMT) No. of bitstreams: 1 SILVA_Barbara_2017.pdf: 2018251 bytes, checksum: 6dab58bc6d22c81d23f1cfb7011353bf (MD5) / Approved for entry into archive by Milena Rubi ( ri.bso@ufscar.br) on 2017-10-17T16:37:47Z (GMT) No. of bitstreams: 1 SILVA_Barbara_2017.pdf: 2018251 bytes, checksum: 6dab58bc6d22c81d23f1cfb7011353bf (MD5) / Made available in DSpace on 2017-10-17T16:38:00Z (GMT). No. of bitstreams: 1 SILVA_Barbara_2017.pdf: 2018251 bytes, checksum: 6dab58bc6d22c81d23f1cfb7011353bf (MD5) Previous issue date: 2017-03-15 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / The application of cellulose nanofibrils to the production of composites has been studied and presents promising results, mainly due to the abundance of the material, which is of a renewable source, and to its low cost. However, the presence of the hydroxyl groups in their chain and their storage in aqueous solutions limits their application as reinforcement in nonpolar matrix composites. In this context, this work aimed to modify the wettability and adhesion properties of films of cellulose nanofibrils to apolar matrices, through plasma treatment. For this, nanocellulose films with thickness of 38 ? 8 ?m were produced by the casting method, from a suspension of nanofibrils in water. The atomic force microscopy characterization (AFM) of the suspended nanofibrils indicated that most of them have an average diameter of less than 75 nm. Each film obtained, after drying the suspension, was then cut into 13 samples with 2 x 1 cm, 12 of which were exposed to plasma and one stored as untreated. Three films were treated with oxygen plasma, with excitation power of 150 W, for 30 minutes and pressure of 0.1, 0.3 and 0.5 Torr. Another three films were treated with sulfur hexafluoride plasma at pressures of 0.1, 0.2 and 0.3 Torr, with a power of 150 W for 15 minutes. It was observed that weight loss was greater than 40% for the films treated with the most extreme conditions oxygen and sulfur hexafluoride. The results also showed that the treatments with sulfur hexafluoride promoted the reduction of the receptivity of the samples to the liquids, with contact angles of approximately 60º for water and 50º for diiodomethane. The profilometry technique revealed that the roughness of the films varied after the treatment with oxygen and sulfur hexafluoride, but the high error bars impede a definitive conclusion on the tendency of these variations. The X-ray diffraction analysis (XRD) indicated no significant change in the crystallinity of the samples with the treatments. In the Fourier Transform Infrared absorption spectra (FTIR), a C-F bonding related peak appeared for the 0.3 Torr sulfur hexafluoride treated sample, indicating the presence of fluorine in that sample. The scanning electron microscopy (SEM) allowed the visualization of the changes in the topography of the films, due to the etching processes resulting from the action of the plasma and the films ruptures caused by the high removal of surface material. In order to test the incorporation of treated films into composites using polyolefins as the matrix, polyethylene pellets were solubilized in xylene for the production of composite films. The treated and untreated nanocellulose films were placed in Petri dish jointly to the polyethylene films still dissolved and left at room temperature. After drying, adhesion between the films was tested through the adhesive tape test, resulting in class-zero adherence, according to the technical standard. It is believed that the lack of adhesion is a result of the composite production method that should be optimized for future work, in order to provide a better investigation of the effects of plasma on the surface properties of the film of cellulose nanofibrils. / A aplicação de nanofibrilas de celulose à produção de compósitos vem sendo estudada e apresenta resultados promissores, principalmente devido à abundância do material, que é de fonte renovável, e ao seu baixo custo. Contudo, a presença dos grupos hidroxila em sua cadeia e o seu armazenamento em soluções aquosas impede sua aplicação como reforço em compósitos de matrizes apolares. Nesse contexto, esse trabalho buscou modificar as propriedades de molhabilidade e aderência de filmes de nanofibrilas de celulose a matrizes apolares, através de tratamento a plasma. Para isso, filmes de nanocelulose com espessura de 38 ? 8 ?m foram produzidos pelo método de casting, a partir de uma suspensão de nanofibrilas em água. A caracterização por microscopia de força atômica (AFM) das nanofibrilas em suspensão indicou que a maior parte destas apresenta diâmetro médio inferior a 75 nm. Cada filme obtido, após a secagem da suspensão, foi então cortado em 13 amostras de 2 x 1 cm, sendo 12 destas expostas ao plasma e uma armazenada como não tratada. Três filmes foram tratados com plasma de oxigênio, com potência de excitação de 150 W, por 30 minutos e pressão de 0,1, 0,3 e 0,5 Torr. Outros três filmes foram tratados com plasma de hexafluoreto de enxofre, nas pressões 0,1, 0,2 e 0,3 Torr, com potência de 150 W por 15 minutos. Observou-se que houve perda de massa superior a 40% para os filmes tratados com as condições mais extremas de oxigênio e hexafluoreto de enxofre. Os resultados demonstraram também que os tratamentos com hexafluoreto de enxofre promoveram a diminuição da receptividade a líquidos das amostras, com ângulos de contato de aproximadamente 60º para água e 50º para o diiodometano. A técnica de perfilometria revelou que a rugosidade dos filmes variou após o tratamento com oxigênio e hexafluoreto de enxofre, porém as elevadas barras de erro impediram uma conclusão definitiva sobre a tendência dessas variações. As análises de difração de raios X (DRX) indicaram não haver alteração significativa na cristalinidade das amostras com os tratamentos. Nos espectros de absorção no infravermelho por transformada de Fourier (FTIR), foi observado o surgimento de um pico relacionado à ligação C-F para a amostra tratada com 0,3 Torr de hexafluoreto de enxofre, que indica a presença de flúor nessa amostra. As análises de microscopia eletrônica de varredura (MEV) permitiram visualizar as alterações na topografia dos filmes, devido aos processos de ecthing decorrentes da ação do plasma e os rompimentos ocasionados pela elevada remoção de material da superfície. A fim de testar a incorporação dos filmes tratados em compósitos que utilizam poliolefinas como matriz, pellets de polietileno foram solubilizados em xileno para produção de filmes compósitos. Os filmes de nanocelulose tratados e não tratados foram dispostos em placa de Petri junto aos filmes de polietileno ainda dissolvidos e deixados em temperatura ambiente. Depois de secos, a adesão entre os filmes foi testada através do teste de fita-cola, resultado em adesão classe zero, conforme a norma técnica. Acredita-se que a falta de adesão é resultado do método de produção do compósito que deve ser otimizado para trabalhos futuros, com o objetivo de proporcionar uma melhor investigação dos efeitos do plasma sobre as propriedades da superfície do filme de nanofibrilas de celulose.

Nas últimas décadas observou-se tanto o crescimento das preocupações ambientais e de sustentabilidade. Neste contexto, surgiu o conceito de biorrefinaria. No Brasil, uma das principais lavouras agroindustriais é a produção de cana-de-açúcar. A indústria sucroalcooleira já atua como um modelo de biorrefinaria tendo a possibilidade de produção de açúcar de etanol e ainda de energia elétrica. Contudo, existe grande potencialidade de produtos de originários de biomassa vegetal. Alguns exemplos das potencialidades são: (i) a utilização dos açúcares da fração polissacarídica para produção de etanol; (ii) produção de polpa e papel; (iii) produção de nanomateriais entre outras. Assim, este trabalho se propõe a buscar e aplicar tecnologias e processos voltados a utilização da cana-de-açúcar para a obtenção de produtos variados. O primeiro processo utilizado é a separação das frações casca e miolo da cana-de-açúcar: na casca existe uma baixa quantidade de células de armazenamento de açúcar e uma maior proporção de fibras estruturais ademais, da epiderme extrai-se a cera; na fração miolo concentra-se a maior parte do caldo rico em sacarose, pela elevada quantidade de células de parênquima. Visando elevar a concentração de sacarídeos para a produção de etanol estudou-se a realização de um processo hidrotérmico usando o próprio suco da cana-de-açúcar para a extração de açúcares da fração de hemiceluloses. Observou-se que para a reação hidrotérmica em meio neutro na faixa de temperaturas estudada (110 a 130°C) cerca de 95% dos sacarídeos são conservados. Contudo, nestas condições reacionais a preservação de massa de hemiceluloses também se mantém nesta faixa, assim verificou-se que o uso de um catalizador ácido permitiria uma conservação de sacarídeos similar e aceleraria a reação de remoção de hemiceluloses. Usando processos similares aos usados na indústria de papel e celulose obteve-se dois materiais celulósicos das frações casca e miolo de cana-de-açúcar com características físico-mecânicas diferenciadas. Apesar do maior teor de células de parênquima no miolo original, observou-se que o papel desta fração apresentou resultados promissores com propriedades similares ao de papeis comerciais. A partir destas polpas, obteve-se dois materiais celulósicos nanofibrilados distintos, sendo o material da casca dúctil e o de miolo mais rígido (maior módulo de Young) e ao mesmo tempo mais frágil (menor alongamento para a ruptura). Verificou-se ainda que a partir dessas polpas celulósicas pode-se produzir nanocristais de celulose II usando um processo de hidrólise e solubilização com ácido sulfúrico seguido de reprecipitação. Desenvolveu-se o processo de produção de nanocristais de celulose I usando água subcrítica associado ou não a CO2. Este processo tem o potencial de substituir a atual produção de nanocristais de celulose visto que neste utiliza-se somente água (com ou sem CO2) para promover a hidrólise em oposição ao método clássico que usa elevadas concentrações de ácido sulfúrico permitindo uma economia financeira e produzindo menor volume de resíduos. / In the last decades environmental concerns and sustainability have grown. In this context, the biorefinery concept arose. In Brazil, one of the leading agro-industrial crops is the production of sugarcane. The sugar industry is already a model of a biorefinery because of the possibility of producing ethanol, sugar and even electricity. However, plant biomass still has a great potential to produce new materials and chemicals. Some of the capabilities are: (i) the use of the sugars from the polysaccharide fraction aiming the ethanol production; (ii) the production of pulp and paper; (iii) production of nanomaterials, among others. This work aims to seek and apply technologies and processes to obtain different products from sugarcane. The first used is the separation of the rind and core fractions of sugarcane: in the rind there is a low amount of sugar storage cells and a higher proportion of structural fibers, and also wax from the epidermis; the core fraction concentrates the majority of the sucrose rich broth as consequence of the high quantity of parenchyma cells. In order to increase the concentration of saccharides a hydrothermal process was studied using the own juice of sugar cane to extract sugars from the hemicellulose fraction. It was observed that for the hydrothermal reaction in neutral medium in the temperature range studied (110 to 130 °C) of about 95% saccharides are conserved. However, in these reaction conditions the hemicellulose preservation is also kept in this range, so it was found that the use of an acid catalyst allow similar saccharides recovery and accelerate the hemicellulose removal. Using similar procedures to those of the pulp and paper industry two cellulosic materials with differentiated physical and mechanical characteristics were obtained from the rind and core fractions of sugarcane. Although most parenchyma content in the original core material, it was observed that this fraction showed promising results with properties similar to commercial papers. From these pulps, two different nanofibrillated cellulosic materials were obtained, being the rind material a ductile material and the core a rigid (higher Young\'s modulus) and brittle (lower elongation at break) one. It was also found that from these pulps cellulose II nanocrystals can be produced using a process of hydrolysis and solubilization with sulfuric acid followed by a reprecipitation process. The production of cellulose I nanocrystals through processes using subcritical water with or without CO2 were developed. These processes have the potential to replace the current nanocrystals production since only water is used (with or without CO2) to promote the hydrolysis, compared to the traditional method, which uses high concentrations of sulfuric acid, thus enabling economical saves and producing less amount of wastes.

Abstract Nanocellulose is envisioned as one of the key product innovations of future biorefineries, since it can potentially function in numerous high-end applications and replace many current petroleum-based products due to its superior properties, abundance and renewable nature. The main difficulty hindering the industrial upscaling of nanocellulose is the lack of feasible techniques for processing cellulose fibres on a nanoscale. At the same time, ongoing research efforts have concentrated on charting the suitability of nanocellulose for various novel applications. The chemical functionalization of cellulose is currently regarded as a significant step for both enhancing nanocellulose fabrication and increasing its value as a product by virtue of its adjustable surface properties. This thesis reports on the surface functionalization of cellulosic fibres by means of two new chemical pre-treatments based on periodate oxidation and sequential chlorite oxidation or reductive amination for use in the fabrication of nanocelluloses. The properties of the resulting nanocelluloses were characterized and their applicability to novel film structures was investigated. Both nanoporous thin films for composite membranes and self-standing barrier films were manufactured and studied for their suitability in water purification and packaging applications, respectively. The oxidation of cellulose to 2,3-dicarboxylic acid cellulose (DCC) significantly enhanced the nanofibril production as only 1-4 passes through the homogenizer were required for disintegration of the fibres down to nano-scale. The fabricated DCC-nanofibrils had both high optical transmittance and viscosity comparable to that of TEMPO-oxidized cellulose nanofibrils. DCC-nanofibrils with a carboxyl content of 1.75 mmol/g showed a potential for functioning as a nanoporous thin-film membrane layer in ultrafiltration tests. The second pre-treatment introduced an acid-free fabrication of amphiphilic cellulose nanocrystals (CNCs) with uniform width and length into nanocellulose production for the first time. Reaction conditions of periodate oxidation were presumed to be one of the key factors to impact the formation of either CNCs or cellulose nanofibrils. The butylamino-functionalized CNCs were used to fabricate barrier films that showed good mechanical strength and high resistance to permeation by oxygen even at elevated relative humidity. / Tiivistelmä Yksi metsäteollisuuden viimeisimmistä tuoteinnovaatiosta on nanoselluloosa, jolle on esitetty lukuisia uusia sovellusmahdollisuuksia sekä potentiaalia toimia korvaavana raaka-aineena öljypohjaisille tuotteille sen erinomaisten materiaaliominaisuuksien sekä globaalin saatavuuden ja uusiutuvuuden takia. Nanoselluloosan teollista hyödyntämistä on kuitenkin hidastanut kustannustehokkaiden valmistusmenetelmien puuttuminen. Samanaikaisesti on tehty laaja-alaista tutkimustyötä nanoselluloosan soveltuvuudesta uusiin käyttökohteisiin. Selluloosan kemiallista funktionalisointia pidetään tällä hetkellä yhtenä lupaavimpana menetelmänä tehostamaan sekä nanoselluloosan valmistusta että tuomaan lisäarvoa nanokuiduille, joiden pintaominaisuuksia voidaan muokata. Tässä työssä tutkittiin selluloosakuitujen funktionalisointia perjodaattihapetukseen sekä kloriittihapetukseen tai pelkistävään aminointiin perustuen ja nanoselluloosan valmistusta esikäsitellystä selluloosasta. Työssä tutkittiin erityisesti valmistettujen nanoselluloosien ominaisuuksia ja selvitettiin niiden soveltuvuutta uudentyyppisiin filmirakenteisiin. Filmirakenteita muokkaamalla tehtiin nanohuokoisia komposiittimembraaneita vedenpuhdistukseen sekä barrier-filmejä pakkausmateriaaleihin. Selluloosan hapetus 2,3-dikarboksyylihapposelluloosaksi tehosti nanoselluloosan valmistusta huomattavasti ja kuidut saatiin hajotettua 1-4 läpäisyllä homogenisaattorissa. Valmistetut DCC-nanofibrillit olivat optisesti läpinäkyviä sekä niiden viskositeetti oli yhtä korkea kuin aiemmin raportoiduilla TEMPO-hapetettuilla nanofibrilleillä. Ultrasuodatuskokeissa DCC-nanofibrilleistä pystyttiin muodostamaan nanohuokoinen kerros membraaninpinnalle, jota on mahdollista käyttää vedenpuhdistuksessa. Pelkistävällä aminointiesikäsittelyllä selluloosakuiduista onnistuttiin ensimmäistä kertaa valmistamaan kooltaan yhdenmukaisia amfifiilisiä selluloosananokiteitä ilman yleisesti käytettyä happohydrolyysiä. Siten työssä nanoselluloosien valmistukseen käytetyn perjodaattihapetuksen havaittiin soveltuvan sekä selluloosananokiteiden että selluloosananofibrillien valmistukseen. Butyyliamino-funktionalisoiduista selluloosananokiteistä valmistetut barrier-filmit olivat mekaanisesti vahvoja ja ne ehkäisivät hapenläpäisyä jopa korkeassa ilmankosteudessa.

Předkládaná dizertační práce se zabývá novým způsobem přípravy biodegradabilních polyuretanů (PU) a jejich modifikací biologicky aktivními celulózovými nanokrystaly. Literární rešerše se zaměřuje na bioresorbovatelné PU v tkáňovém inženýrství. Shrnuje příklady těchto PU elastomerů, skafoldů (nosičů buněk) i injektovatelných PU společně se způsoby biodegradace na netoxické produkty. Poslední část je zaměřena na nanocelulózu, která si získala pozornost díky svým pozoruhodným fyzikálním (velký specifický povrch, mechanické vlastnosti) a biologickým (biokompatibilita, biodegradabilita a nízká toxicita) vlastnostem jako materiál pro biomedicínu. V experimentální části byly charakterizovány amfifilní biodegradovatelné polyuretanové filmy (bio-PU) syntetizované bez použití rozpouštědla polyadiční reakcí z hydrofilního poly(ethylenglykolu) (PEG) a hydrofobního poly(e-kaprolaktonu) (PCL) jako makrodiolů společně s hexamethylen diizokyanátem. Připravené bio-PU filmy byly charakterizovány pro různé poměry jak mezi PEG/PCL, tak i mezi NCO/OH reagujícími skupinami (izokyanátový poměr). Bio-PU filmy projevily markantní nárůst mechanických vlastností při hmotnostním poměru PEG/PCL rovnému nebo menšímu než 20/80 díky vzniku krystalických domén PCL. Přítomnost PEGu zvyšovala schopnost bio-PU filmu absorbovat vodu i urychlila jeho hydrolytickou degradaci. Oproti tomu nižší absorpční schopnost a delší čas hydrolytické degradace materiálu způsobil vyšší izokyanátový poměr, a tedy i vyšší síťová hustota. Třetí část práce se zabývá přípravou polyuretanových nanokompozitů unikátní metodou bez použití rozpouštědla za využití bio-PU matrice a celulózových nanokrystalů buď nemodifikovaných, nebo povrchově roubovaných PEGem. Strukturní analýza prokázala, že přítomnost tyčinkovitých nanočástic způsobuje imobilizaci polymerních segmentů, v důsledku čehož se zvýšila tuhost a křehkost materiálu. Nastavením vhodného poměru mezi PEG/PCL, množstvím izokyanátu, či přídavkem modifikovaného nanoplniva může být bio-PU materiál "ušit na míru" s vhodnými mechanickými (houževnatost, tažnost) a fyzikálními (botnání, degradace) vlastnostmi. Díky přípravě bez použití rozpouštědla by mohly být připravené materiály využity v regenerativní medicíně např. jako cévní štěpy.

This disseration covers the processing and characterization of nanocellulose polymer composites. In this disseration, two fiber spinning methods were developed to create high stiffness nanocomposite fibers from renewably-sourced materials and the properties of these nanocomposites were evaluated. Additionally, bulk nanocomposites were created and some of the properties of these materials, for different types of nanoparticles, are also discussed. Evaluation of nanocellulose as a nucleation agent in poly(lactic acid) is also presented for very small concentrations of nanocelluloses in a plasticized polymer.

Modified nanocellulose have distinctive qualities and have drawn a lot of interest from a variety of fields. It is a natural, sustainable product that is manufactured from plant-based materials like wood and other renewable resources. It is also biodegradable. It is a possible material for battery separators because of its great mechanical strength, flexibility, and ability to create a stable and consistent membrane. Due to the cost of using it as a membrane, it has been investigated in this work to see if it can be coated onto a substrate and used as battery separator. In this work sulfonated cellulose nanofibrils (SCNF) has been used to be coated on kraft paper and inkjet paper using a rod coater. Parameters like concentration, thickness and substrates have been varied in this experiment. Viscosity was measured using Brookfield instrument to measure the viscosity for 0,5% SCNF and 1,5% SCNF. The coating was carried out using a rod coater and varying between two rods to influence the thickness, the coating used concentrations of 0,5% SCNF and 1,5% SCNF and two different substrates, kraft paper and inkjet paper. Thickness was determined to study the effect of the variation in rod. The mechanical strength was tested on the coated paper substrates and compared the results to the noncoated substrates as reference, the mechanical strength showed an improvement with the coated SCNF substrates. Permeance through the Gurley method was studied in order to understand how the coated substrates behaves compared to the noncoated. Contact angle was determined as well to understand the wettability of the coated substrates and how they would behave as separators in zinc ion batteries. The contact angle decreased with increasing concentration of the SCNF which is a result of the sulfonate groups. Cross sections were analyzed using SEM to study the influence of the coating to the substrates. Ionic conductivity was also tested to evaluate the possibility of the coated substrates as separators.

Cellulose nanocrystals (CNCs) are bio-based nanoparticles with the ability to stabilize oil and water emulsions thanks to their intermediate wettability and nanometric size. These and other types of particle-stabilized emulsions, commonly referred to as Pickering emulsions, are of great academic and industrial interest due to their superior stability against drop coalescence compared to classical surfactant-stabilized emulsions. In addition, the presence of a densely packed layer of particles at the oil-water interface is expected to impact the encapsulation ability of the emulsion droplets opening up for the possibility to use these systems to modulate the release of active substances in the context of oral or topical delivery formulations used in pharmaceutical and cosmetic applications. In these types of applications, the use of emulsions with nano-sized drops is advantageous due to their longtermcolloidal stability, improved dermal and mucosal transport of actives, improved bioavailability and greater aesthetic appeal and skin feel. This study had two main objectives. The first one was to explore to possibility to produce o/w emulsions with submicron-size drops by means of microfluidization using a combination of CNCs and hydroxypropyl methylcellulose (HPMC), a surface-active cellulose derivative that has been shown to have the ability to modify the wettability of CNCs (thereby enhancing their ability to adsorb at the oil/water interface). An important aspect of this first part of the study also involved gaining better understanding on the separate contributions of CNCs and HPMC to the properties of the resulting emulsions. The second objective of the work was to assess the performance of selected o/w CNC/HPMC compared to that of surfactant-stabilised emulsions in terms of their ability to deliver lutein, a hydrophobic prototype active of interest for topical delivery applications. / Cellulosa-nanokristaller (CNC) är biobaserade nanopartiklar med förmågan att stabilisera emulsioner av olja i vatten (o/w) tack vare deras medelhöga vätbarhet och storlek i nanometerskalan. Dessa och andra typer av partikelstabiliserade emulsioner, så kallade Pickering-emulsioner, är av stort akademiskt och industriellt intresse på grund av deras överlägsna stabilitet mot droppkoalescens jämfört med klassiska tensidstabiliserade emulsioner. Det tätt packade skiktet av partiklar vid gränsytan mellan olja och vatten påverkar också inkapslingsförmågan hos emulsionsdropparna vilket kan utnyttjas för att reglera frisättning av aktiva substanser i läkemedel eller kosmetiska produkter. I dessa typer av applikationer är användningen av emulsioner med droppar i nano-storlek fördelaktig på grund av deras långsiktiga kolloidala stabilitet, förbättrad hud- och slemhinnetransport, förbättrad biotillgänglighet och hudkänsla. Denna studie hade två huvudmål. Det första var att undersöka möjligheten att producera o/w emulsioner med droppar av submikron-storlek med hjälp av mikrofluidisering och genom att använda en kombination av CNC och hydroxypropylmetylcellulosa (HPMC), ett ytaktivt cellulosa-derivat som har visat sig ha förmågan att modifiera vätbarheten hos CNC och därigenom förbättra dess förmåga att adsorbera vid olja/vatten-gränsytan. En viktig aspekt av denna första del av studien var att få bättre förståelse för hur CNC och HPMC var för sig påverkar egenskaperna hos emulsionerna. Det andra målet med arbetet var att bedöma prestandan hos o/w CNC/HPMC-emulsioner för frisättning av lutein, ett hydrofob aktivt ämne, och jämföra med tensidstabiliserade emulsioner. / nanocellulosa, hydroxipropylmetylcellulosa, Pickering emulsioner, microfluidization, drogleverans

This thesis deals with processing of nanocellulose originating from pulps, with focus on mechanical pulp fibres and fines fractions. The nanocellulose materials produced within this research project were tested for different purposes ranging from strength additives in paper and paperboard products, via composite films to foam materials. TAPPI (Technical Association of Pulp &amp; Paper Industry) has recently suggested a standard terminology and nomenclature for nanocellulose materials (see paper I). In spite of that we have decided to use the terms nano-ligno-cellulose (NLC), microfibrillated cellulose (MFC), nanofibrillated cellulose (NFC) and nanocellulose (NC) in this thesis . It is well-known that mainly chemical pulps are used as starting material in nanocellulose production. However, chemical pulps as bleached sulphite and bleached kraft are quite expensive. One more cost-effective alternative can be to use fibres or fines fractions from thermo-mechanical pulp (TMP) and chemi-thermomechanical pulp (CTMP).   In paper II-IV, fractionation has been used to obtain fines fractions that can easily be mechanically treated using homogenisation. The idea with this study was to investigate the possibility to use fractions of low quality materials from fines fractions for the production of nanocellulose. The integration of a nanocellulose unit process in a high-yield pulping production line has a potential to become a future way to improve the quality level of traditional products such as paper and paperboard grades.   Paper III describes how to utilise the crill measurement technique as a tool for qualitative estimation of the amount of micro- and nano-material produced in a certain process. The crill values of TMP- and CTMP-based nanocelluloses were measured as a function of the homogenisation time. Results showed that the crill values of both TMP-NLC and CTMP-NLC correlated with the homogenisation time. In Paper V pretreating methods, hydrogen peroxide and TEMPO are evaluated. Crill measurement showed that hydrogen peroxide pretreatment (1% and 4%) and mechanical treatment time did not improve fibrillation efficiency as much as expected. However, for TEMPO-oxidised nanocelluloses, the crill value significantly increased with both the TEMPO chemical treatment and mechanical treatment time. In paper V-VII TEMPO-mediated oxidation systems (TEMPO/NaBr/NaClO) are applied to these fibres (CTMP and Sulphite pulp) in order to swell them so that it becomes easy to disrupt the fibres into nanofibres with mechanical treatment.   The demand for paperboard and other packaging materials are steadily increasing. Paper strength properties are crucial when the paperboard is to withstand high load. A solution that are investigated in papers IV and VI, is to use MFC as an alternative paper strength additive in papermaking. However, if one wish to target extremely higher strength improvement results, particularly for packaging paperboards, then it would be fair to use MFC or cationic starch (CS). In paper VI CS or TEMPO-based MFC was used to improve the strength properties of CTMP-based paperboard products. Results here indicate significant strength improvement with the use of different levels of CS (i.e., 20 and 10 kg t–1) and 5% MFC. The strengthening impact of 5% MFC was approximately equal to that of 10 kg t–1 of CS.   In paper VII, NFC and nanographite (NG) was used when producing composite films with enhanced sheet-resistance and mechanical properties. The films produced being quite stable, flexible, and bendable. Realising this concept of NFC-NG composite film would create new possibilities for technological advancement in the area of high-yield pulp technology.  Finally, in paper VIII, a new processing method for nanocellulose is introduced  where an organic acid (i.e., formic acid) is used. This eco-friendly approach has shown to be successful, a nanocellulose with a uniform size distribution has been produced. / <p>Vid tidpunkten för disputationen var följande delarbeten opublicerade: delarbete 5 och 7 inskickade, delarbete 6 och 8 manuskript.</p><p>At the time of the doctoral defence the following papers were unpublished: paper 5 and 7 submitted, paper 6 and 8 manuscripts.</p>

Atualmente, o Brasil é o maior fabricante de celulose branqueada de eucalipto do mundo. Geralmente as fibras virgens de Eucalyptus spp. são utilizadas na fabricação de papéis para imprimir, tissue e especiais. Papéis para embalagens, tipicamente Kraftliners, precisam de uma grande resistência mecânica e são produzidos principalmente a partir de pastas Kraft de coníferas não branqueadas. Por outro lado, nanoceluloses fabricadas a partir de biomassa são consideradas um dos materiais sustentáveis mais interessantes para o século, com excelentes propriedades como baixa densidade, elevadas propriedades mecânicas, alta hidrofilicidade, grande área superficial com reatividade química e elevado valor econômico. Desde 2012 o uso de nanoceluloses na fabricação de papel ganhou impulso. As nanoceluloses têm sido adicionadas em pastas mecânicas e Kraft branqueadas para fabricação do papel, incrementando notavelmente as suas propriedades mecânicas, mas há preocupações sobre a diminuição da drenabilidade, da porosidade e da opacidade do papel. Poucos estudos foram desenvolvidos visando a aplicação de nanoceluloses em fibras não branqueadas, ainda que tenham aplicações em pastas branqueadas e/ou mecânicas. Portanto, o presente trabalho visa desenvolver o uso de nanoceluloses para melhorar as propriedades mecânicas em fibras não branqueadas. Em primeiro lugar, tomaram-se os finos primários do branqueamento de celulose de Pasta Kraft de Eucalipto como a matéria-prima para produzir dois tipos de nanocelulose. A celulose microfibrilada (MFC) é produzida diretamente por homogeneização mecânica utilizando equipamento Masuko. A celulose nanofibrilada (CNF) é produzida por oxidação mediada por TEMPO e homogeneizada por GEA. Em segundo lugar, selecionaram-se com as fibras virgens de Pasta Kraft Marrom de Pinho (PKPM) com número Kappa 36,1 e Pasta Kraft de Eucalipto Não Branqueada (PKEP), obtida na saída de estágio de deslignificação com oxigênio, com número Kappa 9,21, e todas as fibras foram refinadas até atingir o mesmo grau Shopper-Riegler (33±1 SR). Os experimentos com PKPM são conduzidas como uma referência a papéis Kraftliners tradicionais, com ou sem nanocelluloses. Também obteve folhas manuais com pasta branqueada Kraft de eucalipto, adicionando nanoceluloses, para compreender o efeito da lignina presente em PKEP. A receita e os aditivos químicos aplicados aqui são os mesmos que na produção industrial. Os principais resultados são: o uso de CNF (ou MFC) e agentes químicos, separadamente, na pasta PKEP, aumenta as resistências mecânicas dos papéis, no entanto, quando aplicadas CNF (ou MFC) em PKMP sem aditivos químicos, as resistências à tração e a estouro diminuem, e a resistência ao rasgo permanece constante. Como a terceira parte do estudo, delineamento de experimentos teve a configuração composto central com o ponto central em 1% de CNF (ou MFC) e 1% de agentes químicos (polímero+amido+cola), e seus pontos axiais foram 0,3%-1,7% de CNF (ou MFC), e 0,15%-0,85% de agentes químicos. O ponto ótimo de equilíbrio dos índices de rasgo (mN.m2/g) /estouro (kPa.m2/g) /tração (N.m/g) de (10,00/2,25/36,56 para CNF e 12,88/4,25/57,62 para MFC), obteve-se com a adição de 1,03% de CNF e 0,65% de amido, ou com a adição de menos de 0,01% de MFC e de 1% de amido. Finalmente, foram aplicadas CNF ou MFC por impregnação direta no centro da direção-z, considerando que o papel tem forças que interagem em 3D. Os resultados mostram que a PKEP atinge a qualidade do Kraftliner de pinus obtendo um índice de tração de 52,58 N.m/g utilizando 1% de CNF, ou 47,40 N.m/g utilizando 1% de MFC. Também, o custo de utilização do CNF ou MFC na fabricação do papel é avaliado, resultando em estimativas de 0,9494 US$/kg ou 0,3036 US$/kg, com a adição de 1% de CNF ou 1% de MFC, respectivamente, em pasta PKEP. Este trabalho mostra que a aplicação de nanocelulose em Kraftliner tradicional com fibras de pinus com todos os agentes químicos não tem vantagens reais. No entanto, o uso de CNF e MFC tecnicamente e economicamente tem vantagens superiores em pasta Kraft de eucalipto não branqueada (e deslignificada com oxigênio), obtendo-se propriedades superiores às de fibras longas. / Nowadays, Brazil is the largest manufacturer of Bleached Eucalyptus Kraft Pulp in the world. Mostly the Eucalyptus spp. virgin fibres are used in papermaking to manufacture printing, tissue and specialty papers. Packaging papers, typically Kraftliners, have high demands for mechanical strength and are made mostly from Unbleached Softwood Kraft Pulp. Other side, nanocelluloses from biomass are considered one of the most interesting sustainable materials for the Century, with excel properties such as low density, high mechanical properties, high hydrophilicity, large surface area with chemical reactivity and high economic value. Since 2012 the use of nanocellulose in papermaking experienced a great momentum. Nanocelluloses are added in bleached or mechanical pulp in papermaking to increase significantly the mechanical properties, but there are concerns about the decreasing of the drainability, the porosity and the opacity of the paper. A very few studies were developed on the application of nanocelluloses in an unbleached Kraft pulp, even there are its applications on bleached pulps and mechanical pulps. Therefore, the present work aims to develop the application of nanocelluloses to increase the mechanical properties of the unbleached fibers, specifically for Kraftliners, and show the way to replace the softwood fibers with the low-cost hardwood fibers. Firstly, the primary fines from bleaching area of Eucalyptus Kraft pulp, obtained from an industrial residue, was the raw material for nanocellulose production of two nanocelluloses. The microfibrillated celluloses (MFC) are produced with direct mechanical homogenization using Masuko. The nanofibrillated cellulose (NCF) is produced with oxidation mediated by TEMPO and homogenization using GEA. Secondly, as virgin fibers were selected the Unbleached Pine Kraft Pulp (USKP) with Kappa number 36.1 and the Unbleached Eucalyptus Kraft Pulp (UEKP) just after the oxygen delignification stage with the Kappa number 9.21. All the fibres (USKP and UEKP) was refining at the same Shopper-Riegler (33±1 SR). USKP experiments are conducted as reference to traditional Kraftliners, with or without nanocelluloses. Also the virgin bleached Eucalyptus Kraft pulp with nanocelluloses addition for the handsheet paper helps to understand the role of lignin in UEKP. The recipe and chemicals applied here are the same of the industrial production. The main results are: the use CNF (or MFC) and chemical agents, separately, in UEKP, promote the mechanical resistances, however when applied CNF (or MFC) in UPKP without chemicals, the tensile and burst properties decreased and tear remains constant. As the third group of the study, the design of the experiments was conducted in the star configuration with centre point as 1% CNF (or MFC) and 1.00% chemical agents (polymers+starch+chemical agents) and, the axial points were 0.3%-1.7% NCF (or MFC) and 0.15%-0.85 of chemical agents. The optimum point from the balanced tear (mN.m2/g) /burst (kPa.m2/g) /tensile (N.m/g) index point of view with 10.00/2.25/36.56 for (1.03% CNF and 0.65% starch) and 12.88/4.25/57.62 for (<0.001% MFC and 1% starch). Finally, it is applied here the direct impregnation of the center of z-direction with 1% of CNF and MFC, considering that the paper has 3D interacting forces. The results show that the UEKP reaches the pinus Kraftliner quality with 52.58 N.m/g (Tensile Index) using 1% CNF or 47.40 N.m/g using 1% MFC. Also, the cost of use CNF or MFC in papermaking is evaluated, resulting in the estimates of 0.9494 US$/kg or 0.3036 US$/kg, the addition of 1% CNF or 1% MFC in UEKP. This work shows that the application of nanocellulose in traditional Kraftliner with pinus fibres with all chemical agents has no real advantages. However, the use of CNF and MFC technically and economically has superior advantages in Eucalyptus unbleached (and oxygen delignified) Kraft pulp, resulting in such properties superior to those of long fibres.