Orientador: Maria do Carmo Gonçalves / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-20T11:02:43Z (GMT). No. of bitstreams: 1 Taipina_MarciadeOliveira_M.pdf: 4509830 bytes, checksum: a4492786879a5c950122cf7b0b637caa (MD5) Previous issue date: 2012 / Resumo: Neste trabalho, a evolução da degradação da fibra de curuá submetida à hidrólise ácida foi acompanhada em diferentes tempos. Foi possível observar que a hidrólise se inicia por um processo de fibrilação, permitindo um maior acesso do ácido ao longo da estrutura da fibra. As micrografias obtidas das fibras embutidas sugeriram que o ataque ácido na célula vegetal se dá no sentido da lamela média a regiões mais internas da parede celular. Após apenas 10 minutos de hidrólise foi possível observar a exposição de nanocristais presos à parede celular, bem como aglomerados de nanocristais já isolados. Esses resultados também revelaram que há formação de nanocristais após um terço do tempo de hidrólise estabelecido pela literatura. Após 30 minutos de hidrólise os nanocristais de celulose se apresentavam isolados em sua maioria. Nanocristais de celulose foram obtidos a partir da hidrólise ácida da celulose proveniente de diferentes fontes, sendo elas algodão, curauá e celulose microcristalina. Os nanocristais apresentaram formato de agulha, com dimensões dependentes da fonte de celulose utilizada. A modificação da superfície dos nanocristais foi realizada com 3- isocianatopropiltrietoxissilano (IPTS). Resultados de análises de espectroscopia no infravermelho sugeriram a modificação de superfície dos nanocristais. O mapeamento de silício feito por ESI-TEM mostrou a presença do silício na superfície dos nanocristais. Como propósito secundário, foi feito o processamento de nanocompósitos com os nanocristais em matriz de PLA. Os nanocompósitos preparados com nanocristais obtidos por hidrólise ácida com HCl apresentaram um ganho mais significativo em propriedades mecânicas e os resultados evidenciaram a necessidade de modificação de superfície, bem como a escolha do ácido mais adequado para a hidrólise do material celulósico / Abstract: In this work, degradation evolution of curauá fiber, subjected to acid hydrolysis, was monitored at different times. It was observed that the hydrolysis is initiated by a fibrilation process, allowing the access of acid throughout the fiber structure. The cross-section micrographs of the embedded fibers suggested that the acid attack in plant cells takes place towards the middle lamella to the inner regions of the cell wall. Exposure of nanocrystals that attached to the cell wall, as well as, clusters of isolated nanocrystals were observed after only 10 minutes of hydrolysis. These results also showed the formation of nanocrystals after one third of the time established in literature for hydrolysis. The cellulose nanocrystals were completly isolated after 30 minutes of hydrolysis. Cellulose nanocrystals were obtained by acid hydrolysis of cellulose from different sources, such as cotton, curauá and cellulose microcrystalline. The nanocrystals showed a needle-like shape, with dimensions dependent on the cellulose source. The surface modification of nanocrystals was performed with 3-isocyanatepropyltriethoxysilane (IPTS). Results from infrared spectroscopy analysis suggested the surface modification of the nanocrystals. The silicon mapping made by ESI-TEM showed the presence of silicon on the surface of the nanocrystals. As a secondary purpose, the processing of nanocomposites with nanocrystals in a PLA matrix was carried out. The nanocomposites with nanocrystals obtained by acid hydrolysis with HCl showed a more significant improvement in mechanical properties and the results showed the need for surface modification as well as the most suitable choice of acid for the hydrolysis of cellulosic material / Mestrado / Físico-Química / Mestre em Química

Electrospinning is a fiber production method that has gained a special attention due to the simple setup and potential for the industry scale up to produce nanoregime polymer fibers. However, electrospun fibers have relatively poor mechanical properties, which could be improved by introducing reinforcing agents. Cellulose nanocrystals (CNCs) are a promising candidate for use as such fiber reinforcing phase due to nanoscale dimensions, excellent mechanical properties, abundance in nature, biocompatibility and renewability. The mechanical properties of reinforced fibers can be further improved by aligning them uniaxially. There are several reports available on aligning electrospun fibers and reinforcing them with CNCs. However, alignment of the reinforcing phase, such as CNCs, inside matrix is not studied extensively. The importance of aligning arises from different mechanical properties exhibited by the CNCs in longitudinal and transverse directions due to the high aspect ratio. This anisotropic nature of CNCs could be employed in nanocomposite fibers by aligning crystals along the fiber direction. In this study, the effect of the electric field modification on the alignment of CNCs in poly(vinyl) alcohol fibers was investigated. Fibers were collected using four different collector types, which also gave four different electric field configurations. Alignment of the reinforcing crystals in fibers with different degree of macroscopic orientation was studied using 2D XRD and polarized FT-IR. These studies confirm the alignment of both CNCs and PVA in uniaxially aligned fibers. Mechanical testing showed that improvement in alignment is directly related to the increase of the strength of the material. Aligned PVA-CNCs fibers had more than 100 times higher elastic modulus compared to non-aligned fibers. The rule of mixtures, Halpin-Tsai equation and orientation modified Cox’s equation were used to calculate theoretical values of elastic modulus and compare with experimental values. The comparison of between experimentally observed alignment of CNCs and theoretically predicted values shows that there is a potential for further improvement. The demonstrated improvements in the alignment of reinforcing phase could find applications, where well-aligned architectures are required, for example in uses as tissue engineering, scaffolds, membranes, microelectronic devices etc.

Ce travail de thèse a pour objectif d’élaborer de nouveaux revêtements composites en utilisant les nanocristaux de cellulose (NCC) comme additifs biosourcés. Pour pallier au problème d’incompatibilité entre les charges hydrophiles et les matrices hydrophobes, une méthode simple à partir des esters de vinyle a été développée pour fonctionnaliser la surface des NCC. Une étude préliminaire réalisée à partir de l’acétate de vinyle utilisé comme réactif modèle, a d’abord permis d’optimiser les conditions de réaction. Ce protocole expérimental a ensuite été étendu à d’autres esters de vinyle fonctionnels, confirmant le caractère polyvalent de la méthode. Les NCC non modifiés et acétylés ont été dispersés dans des matrices acryliques (latex) ou polyuréthane (réticulable), afin d’étudier leur impact sur les performances mécaniques et barrières des composites. Une amélioration des propriétés mécaniques et barrières à l’oxygène a pu être observée dans certains cas, mais l’acétylation de surface des NCC n’a pas conduit à de meilleures performances. Une solution bicouches constituée d’un film 100 % NCC acétyles recouvert de polymère a alors été envisagé et a d’augmenter fortement les propriétés barrières à l’oxygène des différents matériaux. Certains NCC fonctionnalisés ont également été dispersés dans une matrice polydiméthylsiloxane, potentiellement utilisable comme revêtement protecteur pour l’aérospatial. Une amélioration notable de la stabilité thermique et optique sous irradiations UV dans des conditions géostationnaires a alors été observée. / The objective of this research work consist in the elaboration of novel compositecoatings using cellulose nanocrystals (CNC) as biobased additives. To palliate the problem ofincompatibility between the hydrophilic filler and the hydrophobic matrices, a simple methodbased on vinyl esters was developed to functionalize the CNC surface. A preliminary studyperformed with vinyl acetate selected as model reactant first allowed optimizing the reactionconditions. This experimental protocol was subsequently extended to other functional vinylesters to confirm the versatility of the method. The unmodified and acetylated CNC weredispersed in acrylic polymers (latex) or polyurethane (cross-linked resin) matrices, to studytheir impact on the mechanical and barrier performances of the composites. An improvementof the mechanical and barrier properties could be observed in some cases, but the CNCacetylation did not improve further the performances. A bi-layer approach consisting in afilm of 100 % of acetylated CNC coated with the polymer was then envisaged, and allowedincreasing significantly the oxygen barrier properties of the different resins. Some of thefunctionalized CNC were incorporated into a polydimethylsiloxane matrix, for a potential useas protective aerospace coating. A significant improvement in thermal stability and in opticalstability under UV irradiation in geostationary conditions was then observed.

Pressure sensitive adhesives (PSAs) are polymeric materials with versatile applications in industrial and consumer products such as protective films, product labels, masking tape, and sticky notes, to name a few applications. World demand for emulsion–based products is on the rise due to worldwide legislation on solvent emissions. In order to completely replace emulsion-based PSAs with their solvent-based counterpart, the property modification of emulsion-based PSAs is required. The use of nanomaterials to modify polymer properties is well established. The aim of this thesis was to use cellulose nanocrystals (CNCs) as property modifiers for emulsion-based PSAs. CNCs are recognized as a highly efficient reinforcement nanofiller. Owing to their environmentally friendly characteristics, low density, high aspect ratio, non-toxicity, and abundant availability, the application of CNCs in composite materials is gaining increasing attention. In this thesis, the inclusion of CNCs in emulsion-based PSAs was carried out through in situ emulsion polymerization and blending technique. To the best of our knowledge, there is limited information about the synthesis of CNC/PSAs nanocomposites via in situ emulsion polymerization and the evaluation of their mechanical performance. The addition of CNCs to the polymerization formulation caused latex instability due to the negatively charged surfaces of the CNCs. After numerous attempts to overcome the stability issues, a stable polymerization formulation and protocol were developed. CNC/PSAs were synthesized via in situ seeded-semi batch emulsion polymerization, which is a common commercial production pathway for PSAs. The mechanical performance of the resulting PSA nanocomposite films, namely, shear strength, tack, and peel strength, was evaluated at several CNC loadings. All three PSA adhesive properties were simultaneously enhanced with increasing CNC loading. The inclusion of CNCs into the films increased their hydrophilicity. Consequently, the PSA films’ improved wettability on a stainless steel substrate imparted greater tack and peel strength. The blending of the CNCs with a base latex also led to improved adhesive properties. However, the property modification through blending was not as effective as that for the CNC/PSA films synthesized via in situ emulsion polymerization. Thus, CNCs are safe nanomaterials that have been shown to provide remarkable property enhancement of emulsion-based PSA films at low loadings (1wt%).

Thin film Nanocomposite (TFN) membranes are a relatively new class of high-performance semipermeable membranes for Reverse Osmosis (RO) applications. Large scale applications of TFN membranes have not been achieved yet due to the high production cost of the nanoparticles, agglomeration of the nanoparticles in the thin polyamide matrix of the membrane, and leaching out of typically toxic inorganic nanoparticles into the downstream. In this work, these challenges are addressed by incorporation of two different nanofillers: Cellulose NanoCrystals (CNC), and surface functionalized Halloysite NanoTubes (HNT). Amine groups, carboxylic acid groups, and the first generation of poly(amidoamine) (PAMAM) dendrimers were used for functionalization of the HNT. CNC and HNT are environmentally friendly, low/non-toxic, abundant, and inexpensive nanoparticles with a unique size, and chemical properties. TFN membranes were synthesized via in situ interfacial polymerization of m-phenylenediamine (MPD) with trimesoyl chloride (TMC) and the nanoparticles. The control Thin Film Composite (TFC) membranes, and CNC and HNT based TFN membranes were characterized by Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), X-Ray Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), Fourier Transform Infrared spectroscopy (FTIR) and contact angle measurements. The antifouling capacity of CNC based membranes was investigated with a solution of Bovine Serum Albumin (BSA) as the fouling agent. Also, the leachability of the HNT from the membranes was examined by shaking the membranes in a batch incubator for 48 h, and then tracing the leached out HNT using Inductively Coupled Plasma Mass Spectrometry (ICP-MS). Separation characteristics of the membranes were studied by desalination of synthetic brackish water with a cross flow RO filtration system. It was revealed that incorporation of functionalized HNT enhanced the permeate flux without sacrificing the salt rejection (99.1 % ± 0.1 %). Also, incorporation of 0.1% (w/v) CNC doubled the permeate flux (from 30 to 63 L/m2.h at 20 bar) without compromising the salt rejection (97.8%). At the same time, leaching out of HNT from the TFN membranes was decreased as a result of the HNT functionalization and formation of covalent bonds with the TMC. Also, antifouling properties of the CNC-TFN membranes were 11% improved in comparison with control TFC membrane.

Orientador: Maria do Carmo Gonçalves / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-27T15:15:24Z (GMT). No. of bitstreams: 1 Leite_LilianeSamaraFerreira_M.pdf: 4562587 bytes, checksum: 0ee5828360fc15cbd08b98c4070e5bd3 (MD5) Previous issue date: 2015 / Resumo: Nesse trabalho, nanocristais de celulose (CNC) foram obtidos por hidrólise de fibras de algodão, utilizando-se três diferentes ácidos: ácido sulfúrico, clorídrico e fosfórico. Micrografias obtidas por microscopia eletrônica de varredura (SEM) e transmissão (TEM) confirmaram que as condições de hidrólise empregadas foram adequadas para isolar seus nanocristais. No entanto, foi também possível observar a presença de uma pequena fração de fibras não totalmente hidrolisadas em todas as amostras analisadas. Imagens de microscopia óptica por luz polarizada (PLM) revelaram que o processo de secagem por liofilização dos CNC conduz à formação de aglomerados com dimensões micrométricas. Modificações químicas nas superfícies dos CNC, empregando-se ácido acético e cloreto de hexanoíla, foram conduzidas com o objetivo de diminuir o seu caráter hidrofílico. As modificações foram confirmadas por espectroscopia na região do infravermelho e por imagens de PLM das suspensões dos CNC. Compósitos de acetato de celulose (CA), reforçados com CNC, foram preparados por extrusão, utilizando-se dois procedimentos para a incorporação da carga na matriz: mistura direta e masterbatch, sendo esse último conduzido na tentativa de evitar a etapa de liofilização, onde ocorre a formação de aglomerados de nanocristais. Ensaios mecânicos mostraram que não houve aumento significativo nas propriedades mecânicas para os compósitos preparados por mistura direta. Entretanto, compósitos preparados por masterbatch apresentaram aumento no módulo de Young em torno de 5% e 14%, para composições contendo 10 e 15 % nanocristais em massa, respectivamente. Esses resultados evidenciam a importância das condições de hidrólise para obtenção das nanopartículas, como também da escolha do método de preparação do compósito de forma a promover a menor formação de aglomerados e melhor dispersão da carga na matriz / Abstract: In this work, cotton fiber cellulose nanocrystals (CNC) were obtained by acid hydrolysis using three different acids: sulfuric acid, hydrochloric acid and phosphoric acid. Scanning (SEM) and transmission (TEM) electron micrographs confirmed that the acid hydrolysis conditions used were efficient to isolate their nanocrystals. However, in all samples analyzed, it was possible to observe the presence of some partially hydrolyzed fibers. Polarized Light Microscopy (PLM) showed that the freeze-drying process led to the formation of small CNC agglomerates with micron dimensions. CNC surface functionalization was carried out with the purpose of reducing the hydrophilic character, by using acetic acid and hexanoyl chloride. Chemical modifications at the surface were confirmed by infrared spectroscopy and the hydrophilic character decrease was confirmed by PLM images of the functionalized CNC. Cellulose acetate composites, reinforced with CNC, were obtained by melt extrusion using two techniques for the introduction of reinforcing agent: direct mixing and masterbatch. The latter were carried out prevent CNC agglomeration formation due to the freeze-drying process. Mechanical tests showed that there was no significant increase in of the composites prepared by direct mixing mechanical properties. However, composites prepared from masterbatch showed a 5% and 14% increase in Young's modulus for 10 and 15 wt% CNC content, respectively. These results show the importance of the hydrolysis conditions on the nanoparticle synthesis, as well as the choice of an appropriate reinforcing agent load method so as to avoid agglomeration and increase load dispersion in the matrix / Mestrado / Mestra em Química

京都大学 / 0048 / 新制・課程博士 / 博士(農学) / 甲第22081号 / 農博第2373号 / 新制||農||1073(附属図書館) / 学位論文||R1||N5235(農学部図書室) / 京都大学大学院農学研究科森林科学専攻 / (主査)教授 矢野 浩之, 教授 和田 昌久, 教授 辻井 敬亘 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

Polymeric materials are widely used in diverse applications. However, a major weakness in the majority of the thermoplastic polymers is their lack of ability to resist fire. Most of the chemicals and additives currently used to improve fire retardancy have deleterious effects on the environment. This research focuses on developing an environmentally safe and effective fire-retardant system for high density polyethylene (HDPE), using cellulose nanocrystals (CNCs) and zinc oxide (ZnO). The effect of CNCs coated with nano ZnO has been investigated for improving the fire resistance properties of the HDPE. Improved dispersion of CNCs into HDPE matrix was achieved by employing maleic anhydride as a coupling agent. It was found that addition of CNCs-ZnO can introduce a reasonable level of flame retardancy in HDPE matrix in addition to improving the maximum tensile strength and elongation at break.

<div>Nature has evolved efficient strategies to make materials with hierarchical internal structure that often exhibit exceptional mechanical properties. One such example is found in cellulose, which has achieved a high order of functionality and mechanical properties through a hierarchical structure with an exceptional control from the atomic level all the way to the macroscopic level. Cellulose is present in a wide variety of living species (trees, plants, algae, bacteria, tunicates), and provides the base reinforcement structure used by organisms for high mechanical strength, high strength-to-weight ratio, and high toughness. Additionally, being the most abundant organic substance on earth, cellulose has been used by our society as an engineering material for thousands of years, and are prolific within our society, as demonstrated by the enormity of the world-wide industries in cellulose derivatives, paper/packaging, textiles, and forest products.</div><div><br></div><div><div>More recently, a new class of cellulose base particles are being extracted from plants/trees, cellulose nanocrystals (CNCs), which are spindle-shaped nano-sized particles (3 ̶ 20 nm in width and 50 ̶ 500 nm in length) that are distinct from the more traditional cellulose materials currently used (e.g. molecular cellulose and wood pulp). They offer a new combination of particle morphology, properties and chemical functionalities that enable CNCs for use in applications that were once thought impossible for cellulosic materials.</div></div><div><br></div><div><div>CNCs have shown utility in many engineering applications, for example, biomedical, nanocomposites, barrier/separation membranes and cementitious materials. To gain greater insight as to how best use CNCs in various engineering application areas, a comprehensive understanding of the mechanics of CNCs is needed. The characterization of the mechanical properties of nanomaterials via experimental testing has always been challenging due to their small size, resulting in large uncertainties related to testing near sensitivity limits of a given technique, the same is true when characterizing CNCs. For CNCs, to help offset limitations in experimental testing, numerical modeling has been useful in predicting the mechanical properties of CNCs. We present a continuum-based structural model to study the mechanical behavior of cellulose nanocrystals (CNCs), and analyze the effect of bonded and non-bonded interactions on the mechanical properties under various loading conditions. In particular, this model assumes the uncoupling between the bonded and nonbonded interactions and their behavior is obtained from atomistic simulations.</div></div><div><br></div><div><div>For large deformations and when there is interaction and dynamics of many particles involved, continuum models could become as expensive as MD simulations. In addition, it has been shown that traditional material models in the continuum mechanics context, cannot model all the mechanical properties of CNC, especially for large deformation. To overcome these setbacks and to be able to model real size of CNC, 50-1000 nm, and/or to increase the number of particles involved in the simulation, a so called ‘‘coarse-grained’’ (CG) model for mechanical and interfacial properties of CNC is proposed. The proposed CG model is based on both mechanical properties and crystal-crystal interactions. Parametrization of the model is carried out in comparison with all-atom (AA) molecular dynamics and experimental results of some specific mechanical and interfacial tests.</div></div><div><br></div><div><div>Subsequently, verification is done with other tests. Finally, we analyze the effect of interface properties on the mechanical performance of CNC-based materials including, bending of a CNC bundle, tensile load and fracture in bioinspired structure of CNCs such as staggered brick-and-mortar and Bouligand structures of interest.</div></div>

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