O presente trabalho apresenta resultados do estudo que objetivou desenvolver blendas poliméricas compostas por dois polimeros biodegradáveis, o poli (butileno succinato - co - adipato) (PBSA) copolímero de poliésteres alifáticos e a policaprolactona (PCL). O estudo desenvolveu a tecnologia para a incorporação de nanowhiskers de celulose (NWC) enxertados com PCL (NWC - g - PCL), com objetivo de melhorar a adesão nanowhisker/matrix, e otimizar as propriedades mecânicas destes polímeros. As composições utilizadas foram 30PCL/70PBSA e 50PCL/50PBSA (em % de massa), com 1, 3 e 5% de NWC - g - PCL. As blendas e compósitos foram preparadas na forma de filmes por evaporação de solvente clorofórmio (casting) e via extrusão e moldagem por injeção, e caracterizadas quanto a suas propriedades térmicas, mecânicas e morfológicas através de calorimetria exploratória diferencial (DSC), análise termogravimétrica (TGA) e análise termodinâmica mecânica (DMTA), ensaio mecânico de tração e microscopia eletrônica de varredura (MEV). Os resultados obtidos através das análises de espectroscopia no infravermelho (IV) e difração de raios-X (DRX) sugerem a enxertia de cadeias de PCL nos NWC. Os polímeros puros, na forma de filmes, obtidos por evaporação de solvente, apresentaram estabilidade térmica semelhantes com início de decomposição em 290°C e decomposição máxima em torno de 420°C. Os filmes dos compósitos apresentaram uma diminuição da estabilidade térmica com o aumento dos teores de NWC - g - PCL nas formulações. As curvas DSC apresentaram dois picos de fusão e de cristalização o que indica a imiscibilidade dos polímeros, as análises térmicas dos filmes, mostraram também um aumento no grau de cristalinidade conforme os teores de nanowhiskers enxertados aumentaram, isso para composição 30/70. No caso dos compósitos com composição 50/50 (PCL/PBSA) houve uma diminuição do grau de cristalinidade dos polímeros. A imiscibilidade dos polímeros nos filmes foi confirmada também através das análises DMTA onde dois picos distintos de tanδ foram encontrados, para as composições 30/70, próximos das temperaturas de transição vítrea dos dois polímeros. As mesmas composições processadas via extrusão, e corpos de prova moldados por injeção, apresentaram uma queda na estabilidade térmica detectada pelas análises TGA. Houve um aumento no grau de cristalinidade da PCL conforme maior quantidade de nanowhisker nos compósitos. A maior rigidez do material foi confirmada a partir dos ensaios mecânicos de tração, onde o módulo elástico aumentou aproximadamente duas vezes com o aumento da porcentagem de nanocargas nos compósitos, assim como a diminuição da porcentagem de alongamento e a resistência à tração não sofreu grandes alterações. / In this dissertation results of the study aimed to develop polymer blends composed of two biodegradable polymers, poly (butylene succinate - co - adipate) (PBSA) and aliphatic polyester polycaprolactone (PCL). The study developed the technology for the incorporation of cellulose nanowhiskers (NWC) grafted PCL (NWC - g - PCL), aiming to improve adherence nanowhisker / matrix, and improve mechanical properties of these polymers. The compositions used were 30PCL/70PBSA and 50PCL/50PBSA (in mass%), with 1, 3 and 5% of NWC - g - PCL. The blends and composites were prepared as films by evaporation of solvent chloroform (casting) and via extrusion and injection molding, and characterized their thermal, mechanical and morphological means of differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) mechanical and thermodynamic analysis (DMTA), mechanical tests and scanning electron microscopy (SEM). The results obtained by analysis of infrared spectroscopy (IR) and X -ray diffraction (XRD) suggest the grafting of PCL chains in the NWC. The pure polymers in the form of films obtained by solvent evaporation, showed similar thermal stability with decomposition onset at 290°C and decomposition maximum at around 420°C. The films of the composites showed a decrease in thermal stability with increased levels NWC - g - PCL in the formulations. The DSC curves show two melting peaks and crystallization which indicates immiscibility of the polymers, the thermal analysis of the film showed also an increase in degree of crystallinity as the content of grafted nanowhiskers increased, this composition to 30/70. In the case of composites with composition 50/50 (PCL / PBSA) there was a decrease in the degree of crystallinity of polymers. The immiscibility of the polymers in the film was also confirmed by analysis DMTA where tanδ two distinct peaks were found for compositions 30/70, close to the glass transition temperatures of the two polymers. The same compositions processed via extrusion, and specimens injection molded, showed a decrease in thermal stability detected by TGA analysis. There was an increase in the degree of crystallinity of the PCL as the largest quantity of nanowhisker composites. The rigidity of the material was confirmed from the tensile test, where the elastic modulus increased approximately twice the percentage increase of nanofiller in the composites, as well as the decrease in percentage elongation and tensile strength has not changed much.

Increasing emphasis has been placed on the use of renewable resources, on decreased reliance on petroleum in order to better utilize global energy needs. Biological structures available in nature have been a constant inspiration to the design and fabrication of the new line of functional biomaterials whose unique phenomena can be exploited in novel applications. In tissue engineering for example, a natural biomimetic material with close resemblance to the profile features existed in a native extracellular matrix could provide a temporary functional platform to regulate and control cellular interactions at a molecular level and to subsequently direct a tissue regeneration. However, the lack of rigidity of natural materials typically limits their mass production. One promising approach to address this shortcoming is to introduce a biomimetic composite material reinforced by high purity nanofibers found in nature. As an attractive reinforcing filler phase, cellulose nanowhiskers (CNWs) offer exceptional properties such as high aspect ratio, large interface area, and significant mechanical performance. As such, CNWs could integrate a viable nanofibrous porous candidate, resulting in superior structural diversity and functional versatility. Inspired by the fascinating properties of cellulose and its derivatives, we have designed two bio-inspired nanocomposite materials reinforced with CNWs in this work. The successful grafting of CNWs within the host matrix and their tendency to interconnect with one another through strong hydrogen bonding gave rise to the formation of a three-dimensional rigid percolating network, fact which imparted considerable mechanical strength and thermal stability to the entire structure with only a small amount of filler content, i.e. 3 wt.%. Also, the biocompatibility of the nanocomposite was probed by in-vitro incubation of human-bone-marrow-derived mesenchymal stem cells (MSCs), which resulted in the invasion and proliferation of MSCs around the nanocomposite at day 8 of culture. The green functional biomaterial with its unique features in this work could open new perspectives in the self-assembly of nanobiomaterial for tissue-engineered scaffolding, while it could make the design of the next generation of fully green functional biomaterial a reality.

Thesis (MSc)--Stellenbosch University, 2013. / ENGLISH ABSTRACT: The main aim of this study was to use poly (ethylene-co-vinyl alcohol) (EVOH) as vehicle to incorporate nanofillers into low density polyethylene (LDPE). For this purpose, chitin and cellulose nanowhiskers were prepared through a process of acid hydrolysis and then incorporated into different EVOH copolymers with varying ethylene contents by means of two different experimental methods, namely solution casting and electrospinning. The extremely small dimensions of nanowhiskers make it difficult to observe the degree of dispersion in the electrospun fibers using methods such as transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Fluorescence microscopy was therefore investigated as an alternative characterization technique to obtain better results with regard to tracking the filler dispersion. TEM analysis proved to be the most successful method for observing the dispersion of nanowhiskers for solution cast EVOH nanocomposites as well as electrospun EVOH nanocomposites. Clear differences between EVOH composites with low nanowhisker and high nanowhisker loading were observed in TEM images for these nanocomposites. Thermal analysis of solution cast as well as electrospun fibers were carried out using techniques such as differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). These results revealed changes in crystallization behaviour as well as changes in thermal stability of the EVOH nanocomposites compared to the pure polymer matrix. The incorporation of cellulose and chitin nanowhiskers indicated a general increase in percentage crystallization which probably resulted from the nanowhiskers acting as nucleating agents and therefore increasing the crystallization of most EVOH nanocomposites. The thermal stability is observed to increase as the cellulose nanowhisker loading is increased. This increase in thermal stability proved to be partly attributed to the presence of sulphuric acid which were not completely removed during dialysis of cellulose nanowhiskers. Neutralisation of cellulose nanowhiskers and the treatment with a strong base was therefore further investigated to improve degradation within the EVOH nanocomposites during thermal treatment. The last step in this study involved the incorporation of electrospun EVOH nanofibers containing cellulose nanowhiskers into LDPE in order to improve the mechanical properties. The tensile strength and Young’s modulus of these LDPE nanocomposites were seen to improve quite significantly while a decrease in elongation at break was observed. / AFRIKAANSE OPSOMMING: Die hoofdoel van hierdie studie was om poliëtileen (ko-viniel alkohol) (EVOH) as voertuig te gebruik om nanofillers in lae digtheid poliëtileen (LDPE) te inkorporeer. Kitien en sellulose nanokristalle is vir hierdie doel geproduseer deur middel van ʼn suurhidrolise proses en daarna in verskillende EVOH-kopolimere met verskillende etileeninhoude geïnkorporeer met behulp van twee verskillende eksperimentele metodes, naamlik ʼn drogings- en elektrospinproses. Die uiters klein dimensies van die nanokristalle maak dit uitdagend om die mate van verspreiding van die nanokristalle binne in die elekrogespinde vesels waar te neem m.b.v. metodes soos transmissieelektronmikroskopie (TEM) en skandeerelektronmikroskopie (SEM). Fluoressensie is dus as ʼn moontlike alternatiewe karakteriserings tegniek bestudeer om beter resultate rakende die verspreiding van die nanokristalle te kan waarneem. In hierdie studie is gevind dat TEM-analise die suksesvolste metode was om die verspreiding van nanokristalle te bestudeer en dit geld vir beide die gedroogte en gespinde EVOH-nanosamestellings. Duidelike verskille is waargeneem vir monsters wat hoër en laer nanokristalinhoude gehad het. Saambondeling van die nanokristalle kom duideliker voor by dié wat ʼn hoër inhoud van nanokristalle bevat. Termiese analises van gedroogte EVOH-nanosamestellings en ook die gespinde nanosaamgestelde vesels is uitgevoer d.m.v. tegnieke soos differensieëlskandeerkalorometrie (DSC) en termiese-gravimetriese analise (TGA). Die resultate wat verkry is vanaf die bogenoemde tegnieke het bewys dat daar verandering in die kristallisasie, sowel as die degradasie temperatuur, van die EVOH-nanosamestelling is. Die byvoeging van sellulose en kitien nanokristalle het ʼn algemene verhoging in die persentasie kristallisasie van die EVOH-nanosamestelling te wee gebring. Die byvoeging van nanokristalle tree waarskynlik gedeeltelik op as kernvormings agent vir die EVOH-molekules. TGA analises toon dat die termiese stabiliteit van die EVOH-nanosamestelling verhoog met die byvoeging van nanokristalle. Die teenwoordigheid van die sulfaatgroepe wat nie heeltemal verwyder is tydens die wasproses nie, is bewys om gedeeltelik verantwoordelik te wees vir die verhoging in termiese stabiliteit van die EVOH-nanosamestellings. Die neutralisasie en behandeling van die nanokristalle met ʼn sterk basis is dus verder ondersoek om die degradasie van die EVOH-nanosamestellings tydens verhitting te verbeter. Die laaste stap in hierdie studie het behels dat elektrogespinde EVOH vesels wat verskillende hoeveelhede sellulose nanokristalle bevat, geïnkorporeer is in LDPE ten einde die meganiese eienskappe te verbeter. Die treksterkte en die Young’s modulus het met ʼn beduidendende hoeveelheid verbeter terwyl die verlenging by breekpunt verlaag het. / National Research Foundation

Thesis (MSc)--Stellenbosch University, 2014. / ENGLISH ABSTRACT: Polymer composites have been gaining more importance in our daily lives because of the favorable properties that can be provided by these types of material. A polymer composite consists of improved properties when compared to the individual polymers that it is compiled of. The reason that composites are better than the individual polymers is mainly because composites are a combination of all the bene cial properties from the individual materials that was used to make the polymer composite. High impact polypropylene (HiPP) is a complex copolymer that was developed to overcome the restrictions of polypropylene (PP). Although PP have excellent properties at lower temperatures, it loses these advantages at elevated temperatures. High impact polypropylene has a much better impact strength and is processable at high temperatures. High impact polypropylene has been studied in depth for its applications and its superior properties such as an improved impact strength. The tensile properties, after the incorporation of a nano ller, have however not been investigated to our knowledge. Nano llers have reinforcing abilities due to the nano-scale diameters. Particles that have sizes on a nanometer range are mostly devoid of defects. Nano llers that are biopolymers have additional advantages such that can consist of antimicrobial abilities, renewability, biocompatibility and biodegradability. Composites reinforced with chitin nanowhiskers (chnw) have shown to have valuable applications in the latest medical, industrial and environmental developments. Di erent loadings of chnw were incorporated into a HiPP matrix in order to investigate the e ects that this nano ller will have on the tensile properties of HiPP. There were two challenges that required attention during the incorporation of chnw into HiPP. The rst major challenge was the poor interaction that exist between chnw and HiPP due to the hydrophobic nature of the HiPP matrix and the hydrophilic nature of chnw. The second problem was the agglomeration that can occur because of the hydrogen bonding between the chnw that is caused by the structure of the chnw chains. In order to gain the best dispersion of chnw within the HiPP matrix it was necessary to use compatibilizers and di erent methods of incorporation. The two types of compatibilizers that were chosen to improve the compatibility between the HiPP matrix and chnw were polypropylenegraft- maleic anhydride (PPgMA) and poly(ethylene-co-vinyl alcohol)(EVOH). Injection molding is typically used to process HiPP and was chosen as one of the methods for incorporating chnw into the HiPP matrix. A second method of incorporation was used speci cally for the nancomposites containing EVOH known as electrospinning combined with meltpressing. Tensile testing, DSC, TGA and FTIR were used to investigate the changes in the mechanical and thermal properties of the nanocomposites. SEM and TEM were employed to investigate the morphology of the electrospun ber mats and to characterize the chnw. FTIR as well as TGA were used to characterize the chitin nanowhiskers and to identify the individual components within the nanocomposites after incorporation took place. The incorporation of chnw along with the compatibilizer did show improvement in some mechanical properties of the polymer matrix. However, the in uence that each type of compatiblizer had on this e ect varied depending on the content of the chnw and compatibilizer with regards to the polymer matrix.

Os revestimentos poliméricos podem atuar como uma barreira física entre os íons agressivos e o substrato metálico. Porém, uma exposição prolongada pode causar danos ao revestimento polimérico, conduzir a uma redução contínua do efeito barreira e por consequência a perda da proteção contra a corrosão. A utilização de nano materiais pode atuar aumentando o efeito barreira, proporcionando um aumento no caminho de difusão dos íons agressivos e água até o substrato metálico. Nanopartículas de celulose apresentam elevada cristalinidade e razão de aspecto, excelentes propriedades mecânicas e são proveniente de fonte renovável. Por outro lado, a polianilina (PAni) vem sendo utilizada em revestimentos devido a elevação do potencial de corrosão dos aços devido o seu comportamento redox que proporciona a formação de uma camada de óxidos estável no substrato metálico. A aderência do revestimento polimérico é fundamental para que este possa atuar como revestimento protetor contra a corrosão. Com isso, um pré-tratamento superficial a base de ácido hexafluorzircônico e a utilização de organosilanos na resina epóxi, podem ser utilizados melhorando as propriedades de proteção contra a corrosão e de aderência. O objetivo deste estudo consistiu na obtenção de nanowhiskers de celulose (CNW) por moagem ultrafina através da celulose microcristalina (MCC) para posterior utilização em revestimento polimérico a base de resina epóxi. A CNW foi utilizada funcionalizada ou não com PAni SE (polianilina na forma condutora – sal de esmeraldina) em comparação a MCC nas mesmas condições. Foi avaliada a incorporação de silano aminopropiltrietoxisilano (APS) na resina epóxi e a utilização de uma camada de conversão de zircônia (Zr) aplicada ao substrato metálico. Os revestimentos poliméricos foram avaliados quanto a propriedades mecânicas e à proteção contra a corrosão. As imagens da microscopia de transmissão (TEM) mostram que é possível a obtenção da CNW por meio do processo de moagem, apresentando melhor estabilidade térmica em comparação a MCC. Os revestimentos poliméricos utilizando o silano APS e a camada de conversão de Zr apresentaram as melhores propriedades físicas e mecânicas. A interação entre a carga de reforço, a resina epóxi e a superfície metálica é um fator determinante na eficiência do revestimento polimérico, pois de acordo com a análise de migração subcutânea, a superfície do aço carbono, após 1000 h de exposição, não apresentou corrosão superficial. Com relação à proteção contra a corrosão, quando incorporado a CNW funcionalizada com PAni SE ao revestimento epóxi com APS e a camada de Zr, este apresentou os melhores resultados como constatado nas análises de névoa salina e espectroscopia de impedância eletroquímica (EIS). / Polymeric coatings can act as a physical barrier between the aggressive ions and the metal substrate. However, prolonged exposure can cause damage to the polymer coating and conduct to a continuous reduction in the barrier effect and result in the loss of protection against corrosion. The use of nanomaterials may act by increasing the barrier effect and providing an increased diffusion path of aggressive ions and water to the metal substrate. Cellulose nanoparticles have high crystallinity and aspect ratio, excellent mechanical properties and are derived from renewable sources. On the other hand polyaniline (PAni) has been used in coatings due to the increase of the corrosion potential of the steel due to redox behavior that results in the formation of a stable oxide layer on the metallic substrate. The adhesion of the polymeric coating is essential so that it can act as a protective coating against corrosion. With this, a superficial pre-treatment based on hexafluorzircônico acid and the use of organosilanes in the epoxy resin, can be used to improve the protection against corrosion properties and adhesion. The objective of this study was to obtain cellulose nanowhiskers (CNW) for ultrafine grinding through microcrystalline cellulose (MCC) for subsequent use in the polymer coating based on epoxy resin. The CNW was used functionalized or not with PAni SE (polyaniline in the conductive form - emeraldine salt) compared with MCC under the same conditions. The incorporation of silane aminopropyltriethoxysilane (APS) was evaluated in the epoxy resin and the use of a zirconia conversion layer (Zr) applied to the metal substrate. The polymeric coatings were evaluated for mechanical properties and corrosion protection. Transmission microscopy (TEM) show that obtaining the CNW through the ultrafine grinding process is possible, resulting in better thermal stability compared with MCC. Polymeric coatings using APS silane and Zr conversion coating had the best physical and mechanical properties. The interaction between the reinforcing filler, the epoxy resin and the metal surface is a determining factor in the efficiency of the polymeric coating, because according to the subcutaneous migration analysis, carbon steel surface after 1000 h of exposure, showed no corrosion superficial. With regard to protection against corrosion, when incorporated CNW functionalized with PAni SE to epoxy coating with APS and the Zr layer, showed the best results as found in salt spray tests and electrochemical impedance spectroscopy (EIS).

Os revestimentos poliméricos podem atuar como uma barreira física entre os íons agressivos e o substrato metálico. Porém, uma exposição prolongada pode causar danos ao revestimento polimérico, conduzir a uma redução contínua do efeito barreira e por consequência a perda da proteção contra a corrosão. A utilização de nano materiais pode atuar aumentando o efeito barreira, proporcionando um aumento no caminho de difusão dos íons agressivos e água até o substrato metálico. Nanopartículas de celulose apresentam elevada cristalinidade e razão de aspecto, excelentes propriedades mecânicas e são proveniente de fonte renovável. Por outro lado, a polianilina (PAni) vem sendo utilizada em revestimentos devido a elevação do potencial de corrosão dos aços devido o seu comportamento redox que proporciona a formação de uma camada de óxidos estável no substrato metálico. A aderência do revestimento polimérico é fundamental para que este possa atuar como revestimento protetor contra a corrosão. Com isso, um pré-tratamento superficial a base de ácido hexafluorzircônico e a utilização de organosilanos na resina epóxi, podem ser utilizados melhorando as propriedades de proteção contra a corrosão e de aderência. O objetivo deste estudo consistiu na obtenção de nanowhiskers de celulose (CNW) por moagem ultrafina através da celulose microcristalina (MCC) para posterior utilização em revestimento polimérico a base de resina epóxi. A CNW foi utilizada funcionalizada ou não com PAni SE (polianilina na forma condutora – sal de esmeraldina) em comparação a MCC nas mesmas condições. Foi avaliada a incorporação de silano aminopropiltrietoxisilano (APS) na resina epóxi e a utilização de uma camada de conversão de zircônia (Zr) aplicada ao substrato metálico. Os revestimentos poliméricos foram avaliados quanto a propriedades mecânicas e à proteção contra a corrosão. As imagens da microscopia de transmissão (TEM) mostram que é possível a obtenção da CNW por meio do processo de moagem, apresentando melhor estabilidade térmica em comparação a MCC. Os revestimentos poliméricos utilizando o silano APS e a camada de conversão de Zr apresentaram as melhores propriedades físicas e mecânicas. A interação entre a carga de reforço, a resina epóxi e a superfície metálica é um fator determinante na eficiência do revestimento polimérico, pois de acordo com a análise de migração subcutânea, a superfície do aço carbono, após 1000 h de exposição, não apresentou corrosão superficial. Com relação à proteção contra a corrosão, quando incorporado a CNW funcionalizada com PAni SE ao revestimento epóxi com APS e a camada de Zr, este apresentou os melhores resultados como constatado nas análises de névoa salina e espectroscopia de impedância eletroquímica (EIS). / Polymeric coatings can act as a physical barrier between the aggressive ions and the metal substrate. However, prolonged exposure can cause damage to the polymer coating and conduct to a continuous reduction in the barrier effect and result in the loss of protection against corrosion. The use of nanomaterials may act by increasing the barrier effect and providing an increased diffusion path of aggressive ions and water to the metal substrate. Cellulose nanoparticles have high crystallinity and aspect ratio, excellent mechanical properties and are derived from renewable sources. On the other hand polyaniline (PAni) has been used in coatings due to the increase of the corrosion potential of the steel due to redox behavior that results in the formation of a stable oxide layer on the metallic substrate. The adhesion of the polymeric coating is essential so that it can act as a protective coating against corrosion. With this, a superficial pre-treatment based on hexafluorzircônico acid and the use of organosilanes in the epoxy resin, can be used to improve the protection against corrosion properties and adhesion. The objective of this study was to obtain cellulose nanowhiskers (CNW) for ultrafine grinding through microcrystalline cellulose (MCC) for subsequent use in the polymer coating based on epoxy resin. The CNW was used functionalized or not with PAni SE (polyaniline in the conductive form - emeraldine salt) compared with MCC under the same conditions. The incorporation of silane aminopropyltriethoxysilane (APS) was evaluated in the epoxy resin and the use of a zirconia conversion layer (Zr) applied to the metal substrate. The polymeric coatings were evaluated for mechanical properties and corrosion protection. Transmission microscopy (TEM) show that obtaining the CNW through the ultrafine grinding process is possible, resulting in better thermal stability compared with MCC. Polymeric coatings using APS silane and Zr conversion coating had the best physical and mechanical properties. The interaction between the reinforcing filler, the epoxy resin and the metal surface is a determining factor in the efficiency of the polymeric coating, because according to the subcutaneous migration analysis, carbon steel surface after 1000 h of exposure, showed no corrosion superficial. With regard to protection against corrosion, when incorporated CNW functionalized with PAni SE to epoxy coating with APS and the Zr layer, showed the best results as found in salt spray tests and electrochemical impedance spectroscopy (EIS).

Os revestimentos poliméricos podem atuar como uma barreira física entre os íons agressivos e o substrato metálico. Porém, uma exposição prolongada pode causar danos ao revestimento polimérico, conduzir a uma redução contínua do efeito barreira e por consequência a perda da proteção contra a corrosão. A utilização de nano materiais pode atuar aumentando o efeito barreira, proporcionando um aumento no caminho de difusão dos íons agressivos e água até o substrato metálico. Nanopartículas de celulose apresentam elevada cristalinidade e razão de aspecto, excelentes propriedades mecânicas e são proveniente de fonte renovável. Por outro lado, a polianilina (PAni) vem sendo utilizada em revestimentos devido a elevação do potencial de corrosão dos aços devido o seu comportamento redox que proporciona a formação de uma camada de óxidos estável no substrato metálico. A aderência do revestimento polimérico é fundamental para que este possa atuar como revestimento protetor contra a corrosão. Com isso, um pré-tratamento superficial a base de ácido hexafluorzircônico e a utilização de organosilanos na resina epóxi, podem ser utilizados melhorando as propriedades de proteção contra a corrosão e de aderência. O objetivo deste estudo consistiu na obtenção de nanowhiskers de celulose (CNW) por moagem ultrafina através da celulose microcristalina (MCC) para posterior utilização em revestimento polimérico a base de resina epóxi. A CNW foi utilizada funcionalizada ou não com PAni SE (polianilina na forma condutora – sal de esmeraldina) em comparação a MCC nas mesmas condições. Foi avaliada a incorporação de silano aminopropiltrietoxisilano (APS) na resina epóxi e a utilização de uma camada de conversão de zircônia (Zr) aplicada ao substrato metálico. Os revestimentos poliméricos foram avaliados quanto a propriedades mecânicas e à proteção contra a corrosão. As imagens da microscopia de transmissão (TEM) mostram que é possível a obtenção da CNW por meio do processo de moagem, apresentando melhor estabilidade térmica em comparação a MCC. Os revestimentos poliméricos utilizando o silano APS e a camada de conversão de Zr apresentaram as melhores propriedades físicas e mecânicas. A interação entre a carga de reforço, a resina epóxi e a superfície metálica é um fator determinante na eficiência do revestimento polimérico, pois de acordo com a análise de migração subcutânea, a superfície do aço carbono, após 1000 h de exposição, não apresentou corrosão superficial. Com relação à proteção contra a corrosão, quando incorporado a CNW funcionalizada com PAni SE ao revestimento epóxi com APS e a camada de Zr, este apresentou os melhores resultados como constatado nas análises de névoa salina e espectroscopia de impedância eletroquímica (EIS). / Polymeric coatings can act as a physical barrier between the aggressive ions and the metal substrate. However, prolonged exposure can cause damage to the polymer coating and conduct to a continuous reduction in the barrier effect and result in the loss of protection against corrosion. The use of nanomaterials may act by increasing the barrier effect and providing an increased diffusion path of aggressive ions and water to the metal substrate. Cellulose nanoparticles have high crystallinity and aspect ratio, excellent mechanical properties and are derived from renewable sources. On the other hand polyaniline (PAni) has been used in coatings due to the increase of the corrosion potential of the steel due to redox behavior that results in the formation of a stable oxide layer on the metallic substrate. The adhesion of the polymeric coating is essential so that it can act as a protective coating against corrosion. With this, a superficial pre-treatment based on hexafluorzircônico acid and the use of organosilanes in the epoxy resin, can be used to improve the protection against corrosion properties and adhesion. The objective of this study was to obtain cellulose nanowhiskers (CNW) for ultrafine grinding through microcrystalline cellulose (MCC) for subsequent use in the polymer coating based on epoxy resin. The CNW was used functionalized or not with PAni SE (polyaniline in the conductive form - emeraldine salt) compared with MCC under the same conditions. The incorporation of silane aminopropyltriethoxysilane (APS) was evaluated in the epoxy resin and the use of a zirconia conversion layer (Zr) applied to the metal substrate. The polymeric coatings were evaluated for mechanical properties and corrosion protection. Transmission microscopy (TEM) show that obtaining the CNW through the ultrafine grinding process is possible, resulting in better thermal stability compared with MCC. Polymeric coatings using APS silane and Zr conversion coating had the best physical and mechanical properties. The interaction between the reinforcing filler, the epoxy resin and the metal surface is a determining factor in the efficiency of the polymeric coating, because according to the subcutaneous migration analysis, carbon steel surface after 1000 h of exposure, showed no corrosion superficial. With regard to protection against corrosion, when incorporated CNW functionalized with PAni SE to epoxy coating with APS and the Zr layer, showed the best results as found in salt spray tests and electrochemical impedance spectroscopy (EIS).

Orientadora: Profa. Dra. Mariselma Ferreira / Tese (doutorado) - Universidade Federal do ABC, Programa de Pós-Graduação em Nanociências e Materiais Avançados, 2014. / O Brasil é um país com economia fundada na agroindústria, e por isso, é um grande produtor de celulose. Este estudo teve o objetivo de obter nanofibras de celulose proveniente de duas fontes vegetais: Curauá (Ananas erectifolius) e Fique (Furcraea andina). A escolha dessas plantas fibrosas justificou-se devido às suas características físico-químicas, alto teor de celulose, aspectos estratégicos de disponibilidade, e pioneirismo em aplicações biológicas. Duas metodologias de processamento foram utilizadas nas fibras, um puramente químico e outro químico-mecânico. O processo químico-mecânico consistiu de tratamentos de branqueamento, seguido de desfibrilação mecânica. Desses processos foram obtidas nanoestruturas celulósicas com morfologia de fibras e whiskers. A caracterização das nanofibras e nanowhiskers foi realizada através de ensaios físico-químicos (FTIR, DRX, TGA, número kappa, composição química e caracterização morfológica por MEV e MET). A biocompatibilidade foi testada através do comportamento citotóxico dos bionanomateriais em sistemas in vitro, pelos métodos diretos e indiretos de viabilidade celular por MTT, morfologia celular e adesão. As nanofibras assim como os nanowhiskers não apresentaram comportamento tóxico para as células do tipo Vero nas condições avaliadas. Os nanowhiskers de Curauá e Fique apresentaram maior teor de celulose em relação às nanofibras obtidas; todas as nanofibras apresentaram maior razão de aspecto que nanowhiskers; a maior resistência à tração máxima ocorreu com as nanofibras de Curauá, e foram necessários menor número de ciclos para ser desfibrilado; e uma etapa extra de branqueamento para obtenção de nanofibras e nanowhiskers a partir das fibras de Fique. Finalmente, foi comprovada a biocompatibilidade das nanofibras e nanowhiskers, possibilitando suas aplicações em vários setores biomédicos. / The Brazilian economy is funded on agribusiness and, therefore, is a big producer of cellulose. This study aimed to obtain cellulose nanofibers from two plants: Curauá (Ananas erectifolius) and Fique (Furcraea andina). The choice of these fibrous plants was justified due to its physical-chemistry characteristics, high cellulose content, strategic aspects of availability and the pioneering in biological applications. Two different methodologies to process the fibers were used, one strictly chemical and other chemicalmechanical. In that case, the chemical-mechanical process, consisted of bleaching treatments, followed by mechanical defibrillation. From those two processes, cellulosic nanostructures were obtained with morphology of fibers and whiskers. The characterization of nanofibers and nanowhiskers was performed by physical-chemical tests (FTIR, XRD, TGA, kappa number, chemical composition and morphological characterization by SEM and TEM). The biocompatibility was tested studying the cytotoxic behavior of the nanomateriais in in vitro systems, by the direct and indirect cell contact methods analyzed by cell viability using MTT, cell morphology and adhesion. The nanofibers as well as nanowhiskers did not exhibit citotoxicity behavior face to the Vero cells in the conditions studied. Nanowhiskers from Fique and Curaua showed higher cellulose content than all nanofibers obtained; nanofibers presented higher aspect ratio than nanowhiskers; nanofibers from Curauá got higher maximum tensile strength than nanofibers from Fique, besides requiring less number of cycles to be desfibrilated; one extra step of bleaching was needed to obtain nanofibers and nanowhisker from Fique fibers. Finally, it was proved the biocompatibility of nanofibers and nanowhiskers, enabling their applications in various biomedical sectors.

Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2018-04-11T19:34:25Z No. of bitstreams: 1 LucasRicardoFernandesFigueiredo_TESE.pdf: 6637394 bytes, checksum: 61ae8caa80c576775c523ad68f0527cc (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2018-04-12T22:55:55Z (GMT) No. of bitstreams: 1 LucasRicardoFernandesFigueiredo_TESE.pdf: 6637394 bytes, checksum: 61ae8caa80c576775c523ad68f0527cc (MD5) / Made available in DSpace on 2018-04-12T22:55:55Z (GMT). No. of bitstreams: 1 LucasRicardoFernandesFigueiredo_TESE.pdf: 6637394 bytes, checksum: 61ae8caa80c576775c523ad68f0527cc (MD5) Previous issue date: 2017-12-13 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES) / ?Adesivos verdes? t?m despertado grande interesse cient?fico e tecnol?gico como alternativa aos produtos comerciais convencionais, que em geral, liberam subst?ncias t?xicas e levam um longo per?odo de tempo para degradar. Entretanto, as propriedades mec?nicas limitadas e a r?pida degrada??o de alguns pol?meros biodegrad?veis limitam seu uso na maioria das aplica??es pr?ticas. No presente trabalho, comp?sitos foram preparados usando pol?meros biodegrad?veis e nanowhiskers de celulose (NWC) visando sua utiliza??o como adesivos para madeira. O objetivo da pesquisa foi estudar o efeito da adi??o dos nanowhiskers de celulose (NWC) nas propriedades mec?nicas e na degrada??o dos pol?meros. Os pol?meros biodegrad?veis sintetizados por policondensa??o ? base de glicerol e ?cidos foram poli (adipato de glicerol) - PGA, poli (maleato de glicerol) - PGM, poli (citrato de glicerol) - PGC, poli (ftalato de glicerol) - PGPh, poli (succinato de glicerol) PGSu e poli (sebacato de glicerol) - PGS. Al?m desses, copol?meros poli (glicerol succinato-co-maleato) - PGMSu, poli (glicerol succinato-co-adipato) - PGASu e poli (glicerol adipato-co-maleato) - PGMA foram tamb?m sintetizados. Nanowhiskers de celulose (NWC) foram adicionados aos pol?meros para avalia??o dos seus efeitos na melhoria das propriedades mec?nicas e no controle da taxa de degrada??o. Os materiais foram produzidos com a adi??o de 0, 5, 10 e 20% em peso de NWC. Os pol?meros puros e os comp?sitos foram analisados por Calorimetria Diferencial de Varredura (DSC), An?lise termogravim?trica (TGA), difra??o de Raios X (DRX) e espectroscopia Infravermelho por transformada de Fourier (FTIR). Juntas adesivas foram produzidas em corpos de prova de pinus (Pinus elliottii) e angelim (Vatairea heteroptera Ducke) e submetidas a degrada??o por envelhecimento acelerado e testes de cisalhamento sob tra??o. Juntas coladas produzidas com adesivos ? base de acetato de polivinila - PVAc e cianoacrilato foram tamb?m testadas, nas mesmas condi??es, para fins de compara??o. As an?lises t?rmicas indicaram que a maioria dos pol?meros biodegrad?veis ? base de glicerol testados s?o est?veis at? aproximadamente 260?C e a adi??o de NWC aumentou a estabilidade t?rmica (Tonset) de alguns pol?meros em 26?C at? 48?C, enquanto outros n?o foram afetados. As an?lises de superf?cie de fratura por microscopia eletr?nica de varredura (MEV) ap?s os testes de cisalhamento sugerem redu??o de ductilidade com a incorpora??o de NWC ao adesivo. As medidas de ades?o indicaram que os adesivos verdes desenvolvidos a partir de pol?meros de glicerol com 10 e 20% em peso de NWC apresentaram resist?ncia ao cisalhamento superior ao adesivo comercial ? base de PVAc. Os melhores resultados e resist?ncia ao cisalhamento foram obtidos para PGASu com 20% em peso de NWC (2,57 ? 0,36 MPa) e PGM com 20% em peso de NWC (2,33 ? 0,43 MPa), enquanto que a resist?ncia ao cisalhamento do acetato de polivinila - PVAc foi de 1,58 ? 0,18 MPa. O envelhecimento resultou em maior resist?ncia ao cisalhamento de alguns adesivos. A melhoria mais significativa foi obtida para PGMA com 20% em peso de NWC, que atingiu (3,89 ? 0,74 MPa) ap?s 250 h de envelhecimento, portanto, maior que a resist?ncia ao cisalhamento do cianoacrilato (3,12 ? 0,53 MPa). Em ?ltima an?lise, os resultados apresentados neste trabalho sugerem que a adi??o de nanowhiskers de celulose (NWC) ? uma abordagem vi?vel para ajustar as propriedades mec?nicas e degrada??o dos pol?meros biodegrad?veis. / ?Green adhesives? are of great scientific and technological interest as an alternative to conventional commercial products, which often release toxic substances and take long time to degrade. However, the poor mechanical properties and fast degradation of some biodegradable polymers limit their use in most practical applications. In the present work, novel biodegradable composites were prepared using biodegradable polymers and cellulose nanowhiskers (CNW) for their use as wood adhesives. The goal of the investigation was to study the effect of the addition of CNW on the mechanical properties and degradation of the polymers. The biodegradable polymers synthesized by polycondensation based on glycerol and acids were poly(glycerol adipate) - PGA, poly(glycerol maleate) - PGM, poly(glycerol citrate) - PGC, poly(glycerol phthalate) - PGPh, poly(glycerol succinate) - PGSu and poly(glycerol sebacate) - PGS. In addition, the copolymers synthesized were poly(glycerol succinate-co-maleate) - PGMSu, poly(glycerol succinate-co-adipate) ? PGASu and poly(glycerol adipate-co-maleate) ? PGMA. Cellulose nanowhiskers (CNW) were added to the polymers as an approach for improving the mechanical properties and controlling the degradation rate. Composites were produced with the addition of 0, 5, 10 and 20 wt.% of CNW. The neat polymers and composites were analyzed by Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TGA), X-ray diffraction (XRD), and Fourier Transform Infrared Spectroscopy (FTIR). Adhesively bonded joints were produced in test specimens of slash pine (Pinus elliottii) and angelim (Vatairea heteroptera Ducke) and subjected to accelerated aging and tested under shear by tensile loading. Bonded joints produced with polyvinyl acetate - PVAc and cyanoacrylate based adhesives were also tested under the same conditions for comparison purposes. Thermal analyses indicated that most of the biodegradable glycerol-based polymers tested are stable up to about 260?C and the addition of CNW increased the thermal stability (Tonset) of some polymers by 26?C up to 48?C, while others were not affected. Analyses of the fracture surfaces after the shear tests by Scanning Electron Microscopy (SEM) suggest less ductile fracture with the incorporation of CNW to the adhesive. The shear strengths of the green adhesives developed from glycerol with 10 and 20 wt.% CNW were greater than that of the commercial PVAc based adhesive. The best results of shear strengths were obtained for PGASu 20 wt.% CNW (2.57 ? 0.36 MPa) and PGM 20 wt.% CNW (2.33? 0.43 MPa), while the shear strength for polyvinyl acetate - PVAc was 1.58 ? 0.18 MPa. Aging improved the shear strength of some adhesives. The best result was obtained for PGMA 20 wt.% CNW, which reached (3.89 ? 0.74 MPa) after 250h of aging, thus greater than the shear strength of cyanoacrylate (3.12 ? 0.53 MPa). Ultimately, the results presented in this work suggest that the addition of cellulose nanowhiskers (CNW) is a viable approach to tailor mechanical properties and degradation of biodegradable polymers.

Cellulose nanowhiskers (CNWs) are high aspect ratio rod-like nanoparticles with diameters on the order of a few nanometers. For the very first time CNWs are demonstrated as a useful material for guided tissue engineering. Due to their nanoscale dimensions and high aspect ratio, highly oriented spin coated surfaces of CNWs are shown to direct the morphology and terminal differentiation of myoblasts, allowing the culture of skeletal muscle-like tissue with a more physiologically relevant structure.CNWs are prepared from cellulose extracted from the tunicate Ascidiella sp. using acid hydrolysis to prepare high aspect ratio particles with diameters of approximately 5 to 6 nm. A spin coating method is used to prepare sparsely adsorbed sub-monolayers of CNWs with a high degree of relative orientation. The surfaces have a mean feature height of only 5.5 nm and the degree of CNW adsorption and orientation is modulated by altering the preparation procedure. When C2C12 myoblasts are seeded to the surfaces, the cells adopt highly oriented morphologies induced by the CNWs via contact guidance. This is a demonstration of contact guidance on some of the smallest topographical features ever reported. Furthermore, the highly oriented CNWs promote fusion and terminal differentiation of the myoblasts to form multinucleated myotubes with a striking degree of parallel orientation.CNW surfaces are also shown to support the adhesion and spreading of human mesenchymal stem cells, inducing the adoption of highly oriented cell morphologies. The ability of hMSCs to undergo cell fusion with C2C12 myotubes highlights the great potential for tissue engineering human skeletal muscle, using CNWs to direct the structure of the tissue. The bioactivity and low cytotoxicity of CNWs, coupled with their low cost and simple production procedure, indicates that CNWs will be a useful material for tissue engineering and regenerative medicine.