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.

Devido à preocupação com o meio ambiente e o volume crescente de resíduos plástico em aterros sanitários, os polímeros biodegradáveis estão sendo estudados extensivamente. Um deles é o PLA. Apesar de possuir propriedades comparáveis a polímeros commodities e polímeros de engenharia, ainda é necessário melhorar certas características do PLA, como resistência ao impacto. Para isso, a nanocelulose (NC) pode ser usada sem alterações significativas na biodegradação polimérica. Este estudo teve como objetivo obter a nanocelulose, caracteriza-la e incorpora-la ao poli(ácido láctico) (PLA), assim como, estudar as propriedades térmicas, morfológicas e mecânicas do compósito obtido. A NC foi obtida por hidrólise ácida utilizando ácido fosfórico e posteriormente foi silanizada com três silanos distintos. As nanopartículas foram caracterizadas por Birrefringência, Microscopia Eletrônica de Transmissão (MET), Termogravimetria (TG), Potencial Zeta, Espectroscopia Vibracional de Absorção no Infravermelho com Transformada de Fourier (FTIR) e Difração de Raio X (DRX). Com as imagens obtidas pelo MET foi possível medir o tamanho das partículas de NC. E então obter a razão de aspecto de 82 e o limite de percolação de 1,1% em massa, confirmando a morfologia de nanofibra. De acordo as analises TG\'s, a presença de NC silanizada aumentou o início da degradação térmica. Os compósitos, contendo 3% em massa de NC, foram obtidos por fusão em câmara de mistura e moldados por injeção. Os compósitos foram caracterizados por FTIR, Cromatografia de Permeação em Gel (GPC), TG, Calorimetria Exploratória Diferencial (DSC), Microscopia Eletrônica de Varredura (MEV-FEG), Impacto e Tração. As análises dos compósitos mostraram que a NC atuou como agente de nucleação, facilitando a cristalização do PLA, além de a NC ter atuado como reforço na matriz polimérica melhorando as propriedades mecânicas. / Due to concern for the environment and the growing volume of plastic waste in landfills, biodegradable polymers are being studied extensively. One of them is the PLA. Despite properties comparable to commodities polymers and engineering polymers, it is still necessary to improve certain characteristics of PLA, such as impact resistance. For this, the nanocelulose (CN) can be used without significant changes on the polymeric biodegradation. This study aimed to obtain nanocelulose, characterizes it and incorporates it to polylactic acid (PLA), even as, studies of thermal, morphological and mechanical properties of the composites processed. The CN was obtained by acid hydrolysis using phosphoric acid and it was, subsequently, silanized with three different silanes. The nanoparticles were characterized by Birefringence, Transmission Electron Microscopy (TEM), Thermogravimetry (TG), Zeta Potential, Spectroscopy Absorption Vibrational Infrared Fourier Transform (FTIR) and X-Ray Diffraction (XRD). By images taken by TEM was possible to measure the size of particles CN. So, obtain the aspect ratio of 82 and the percolation limit of 1.1 wt%, demonstrating morphology of nanofiber. According to TG analysis, the beginning of thermal degradation increased when CN Pure was compared with modified CN. The composite, containing 3 wt% CN, were obtained by melt in mixing chamber and then injection molded. The composites were characterized by FTIR, Gel Permeation Chromatography (GPC), TG, Differential Scanning Calorimetry (DSC), Scanning Electron Microscopy (SEM), Impact and Tensile Strength. The results showed that the CN acts as a nucleating agent in PLA, facilitating the crystallization and acts as reinforcement in polymer matrix to improve the mechanical properties.

Environmental concerns arising from the use of non-degradable plastics have resulted in search for suitable substitutes. The thesis deals with new nanostructured composites based on reinforcement of nanocellulose whiskers in "green" polymers such as xylan. Since the reinforcement filler and the matrix are both biobased and are thereby environmental friendly. Xylan incorporated with cellulose whiskers films provided with improved water and oxygen barrier properties. It appears that the high degree of crystallinity of cellulose whiskers, dense composite structure formed by the whiskers and rigidly hydrogen-bonded cellulose whiskers can cause cellulose whiskers to form integrated matrix which contribute to substantial benefit in the overall reduction of transmission rate. The spectral data obtained for the NCW/xylan nanocomposite films showed that the amount of xylan adsorbed to cellulose increases with the addition of NCW in the matrix. In addition, NMR T2 relaxation experiments studies were conducted to investigate the change in the nature of carbohydrate-water interactions as a result of NCW incorporation. These results facilitated an improved understanding of the mechanisms involved in the superior barrier and mechanical properties of xylan-whisker nanocomposite films. XRD studies show that when a xylan-whisker nanocomposite films is formed the mixing occurs on the atomic scale and NCW loading increases the matrix crystallinity.