One of today’s world's main challenges is access to a clean environment. The release of hazardous and toxic gases from burning fossil fuels is of critical concern due to these gases' destructive effects on the nearby atmosphere. Among these, acid rain is one of the most severe consequences of air pollution caused by sulfur dioxide (SO2) gas and still needs to be better addressed. One of the solutions is the adsorption-based technologies because of their ease of use, possible high adsorption capacity, minimum environmental impact, low cost, and efficient sorbate recovery possibilities. Gas separation via adsorption is not yet widely employed commercially since it needs regenerable, high-durable, high-performance, and cost-effective adsorbents. One of the common methods of absorbing acid gases is the use of amino absorbents that have disadvantages such as create many waste materials challenging to regenerate, wastewater, and waste gas. Therefore, incorporating amine groups on the surface of solids to overcome the problem of regeneration has attracted considerable attention in gas uptake. In this project, we proposed to functionalize nanocrystalline cellulose (NCC) using a solvent-free method to boost their SO2 interactions and thus their adsorption capability. Therefore, a commercial NCC material was modified using ethylenediamine (EDA) in green and straightforward amination approach in order to tune its surface basicity and obtain an efficient green-biobased adsorbent. Since the substitution process of amines with hydroxyl groups on the cellulose surface is carried out through dangerous halogen solvents, we used the solvent-free one-step method and investigated the synthetic parameters. Amination conditions of NCC adsorbents were optimized via the effects of the amination temperature, the amination time, and the amount of EDA on their physical properties and their performance for SO2 adsorption. The sorbents were characterized using attenuated total reflection-Fourier-transform infrared spectroscopy (ATR-FTIR), solid carbon nuclear magnetic resonance (13CNMR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and scanning electron microscopy- energy-dispersive X-ray spectroscopy (SEM-EDS) to see if EDA was incorporated into the NCC and investigate the changes in thermal stability of adsorbents by changing synthesis conditions. Sorbents were then tested for SO2 capture at the same conditions of room temperature (RT), atmospheric pressure, and a flow rate of 20 ml/min, which was selected based on previous studies to optimize flow rate in the same research group. The optimal conditions to create an effective sulfur dioxide adsorbent were found to be 70 oC for 8 hours of amination. At ideal conditions, the NCC modified had an SO2 adsorption capacity value of 0.030 mg/100 mg. The promising properties of EDA-NCC in terms of adsorption capacity (showing a significant increase in capacity when compared to the NCC at atmospheric pressure and ambient temperature) make them potential adsorbent candidates. In addition, the impacts of SO2 capture operating conditions on adsorption capacity were evaluated. By varying the adsorption temperature from room temperature to 60 °C and the feed flow rate from 10 to 30 ml min-1, fixed-bed breakthrough studies for SO2 adsorption onto NCC and modified-NCC adsorbent (prepared at 70oC, 3hr, and EDA/NCC=25) were carried out. Over the range of operating parameters studied, the greatest SO2 capacity and breakthrough time values were obtained with adsorbent at room temperature and 20 ml min-1 input flow rate. As expected, due to the exothermic nature of the adsorption process, the amount of SO2 adsorbed at equilibrium decreased with increasing temperature. It was also observed that as the flow rate increases, the breakthrough time decreases due to the higher flow rate of the feed gas was accompanied by the faster transport of the adsorbate molecules and leading to a shorter breakthrough time, as expected. Finally, another EDA functionalization method was tested, using a two-step method. First, cellulose was functionalized using citric acid (CA), and then the EDA was incorporated via carboxylic acid functional groups in the CA to obtain both amide and amine groups on the NCC’s surface. This approach aimed to compare EDA deposition on cellulose surface via a different method by adding one more functional group and evaluating their performance in SO2 gas adsorption. It was concluded that oxygenated functional groups and groups with low alkalinities, such as carboxylic acid and amide, can negatively affect gas adsorption. These results were concluded by comparing two adsorbents, one containing only amine groups and the other adsorbent containing amide and carboxylic acid groups in addition to the amine group, although the amine content of the two adsorbents was different. Future research will explore the mechanisms and capturing phenomena to improve capturing capacity and process applicability as well as the material optimal regeneration operating conditions.

Effective treatment of carbon fiber components to improve delamination resistance is vital to the application of such materials since delamination is one of the biggest concerns regarding the use of composites in the aerospace sector. Due to the significant application benefit gained from increased stiffness to density ratio with composite materials, innovative developments resulting in improved through-thickness strength have been on the rise. The inherent anisotropy of composite materials results in an added difficulty in designing structural elements that make use of such materials. Proposed techniques to improve the through-thickness strength of laminar composites are many and varied; however all share the common goal of improving inter-laminar bond strength. This research makes use of novel materials in the field of wet flocking and Z-pinning. Cellulose nanofibers (CNFs) have already demonstrated excellent mechanical properties in terms of stiffness and strength, originating at the nano-scale. These materials were introduced into the laminate while in a sol-gel suspension in an effort to improve load transfer between laminate layers. The effect of CNFs as lightweight renewable reinforcement for CFRPs will be investigated. Carbon nanotube (CNT) additives were also considered for their beneficial structural properties. / Master of Science

Nano-cellulose fibers/suspension has very high viscosity, its viscosity has to be lower before it can be applied in the paper coating recipe. For this purpose the adsorption behaviour of polyvinyl alcohol on nano-cellulose fibers were investigated using method developed by Zwick in 1960, based on the formation of PVA-iodide blue complex in the presence of boric acid. The experiments showed that the maximum adsorbed amount i.e. 0.13 g PVA/g NFC was obtained in a dispersion with 0.2 % PVA concentration. It should be possible to further increase the PVA adsorption as the adsorbed amount didn’t reach a saturation point where the PVA adsorption attained a constant value. It was also found that adsorption of PVA on NFC is time dependent. The absorbance measurement after four days of mixing PVA/NFC suspension showed only partially adsorption of PVA on nano-cellulose surface.  An equilibrium time of 10-13 days was needed for PVA to fully adsorb on nano-cellulose fibers surface. Another important observation was that PVA adsorption also depends on the concentration of nano-cellulose fibers. A lower concentration of NFC easily allows PVA to adsorb on its surface, as compared to higher NFC concentration. An important finding during the methodology development was the method to get rid of formation of flocs in the blue iodide complex solution; by slowly addition of reactants, especially the KI/I2 solution under continuous stirring around 60oC the tendency to flocs formation was suppressed.

[pt] Atualmente existe grande empatia da sociedade por produtos de origem renovável, devido à crescente conscientização da finitude dos recursos naturais. Um resíduo muito comum da agroindústria e gerado em grande escala, sendo majoritariamente descartado em lixões, é a casca de coco. Com o intuito de dar um aproveitamento a este resíduo, o presente trabalho experimentou diferentes metodologias para se isolar a nano celulose proveniente da fibra de coco e caracterizou os produtos das diferentes etapas do seu processo de extração. A metodologia que obteve os melhores resultados consistiu em deslignificar exaustivamente com NaOH até o licor remanescente não apresentar mais a coloração escura, lignina. Em seguida, foi realizado um tratamento com H2O2 e NaOH por duas vezes e a hidrólise com ácido sulfúrico. As etapas posteriores objetivaram a remoção do ácido através de seguidos ciclos de centrifugação com a remoção do sobrenadante acompanhado de diálise até que o meio externo atingisse pH neutro. A dispersão final da nano celulose em meio aquoso foi feita através do ultrassom. As caracterizações da celulose hidrolisada e dos produtos das etapas realizadas até o isolamento da mesma foram feitas por: análise térmica gravimétrica; por difração de raios X e por microscopia eletrônica de varredura. Ao final foram determinadas as estabilidades térmicas das nano celuloses obtidas, os seus respectivos índices de cristalinidade e o tamanho do cristal obtido e os efeitos dos diferentes tratamentos experimentados. A lignina teve sua estrutura química atestada por FTIR, a partir do efluente gerado durante o isolamento da nano celulose, o licor negro. / [en] Nowadays there is great empathy from society for products from renewable resources, due to growing awareness of the finiteness of natural resources. A very common residue of agribusiness and generated on a large scale, being largely discarded in landfills, is coconut shell. With the objective of giving a benefit to this residue, this work tried different methods to isolate the nanocellulose derived from coconut fiber and characterized the products of the different stages of the extraction process. The methodology, which achieved the best results, was the one which did the mercerization with NaOH until the remaining liquor does not look like a black liquor anymore. After that, the bleaching was made twice with H2O2 and NaOH and the hydrolysis was carried with sulfuric acid. Subsequent steps aimed to remove the acid from the fibers. The centrifugation was made and supernatant was removed, followed by dialysis until the external medium reached neutral pH. The final dispersion of nanocellulose in aqueous medium was performed using ultrasound. The characterizations of hydrolyzed cellulose and the products of the process steps was performed by TGA analysis; by X-ray diffraction and scanning electron microscopy. The thermal stabilities were determined from the obtained nanocellulose, their respective indices of crystallinity and crystal size achieved and the effects of the different treatments tested. The chemical structure of the generated effluent from the isolation of the nanocellulose black liquor was attested by FTIR.

[pt] A celulose é um biopolímero abundante, renovável e altamente biodegradável com produção no Brasil de aproximadamente 20 milhões de toneladas em 2017. A obtenção de nanocelulose a partir de diversas fontes e sua utilização em uma variedade de aplicações tem sido objeto de uma grande quantidade de pesquisas, visto suas propriedades diferenciadas e possibilidade de modificações, a partir de reações com outras substâncias orgânicas e inorgânicas. Entre as potenciais aplicações que a nanocelulose apresenta está o tratamento de água e efluentes, por processos como separação por membranas, troca iônica e adsorção. O principal processo de obtenção de nano cristais de celulose é a hidrólise ácida da região amorfa, restando em sua maior parte as regiões cristalinas. Os procedimentos mais aplicados para a produção de nano cristais de celulose consistem na reação de material celulósico puro com ácidos fortes com temperatura, agitação e tempo controlados. A nanocelulose cristalina (CNC) foi obtida através de hidrólise ácida com ácido sulfúrico (40 por cento) e então modificada com ácido cítrico (1,2M), CNC-Mod, para posterior caracterização e ensaio de adsorção de cátions metálicos. As amostras produzidas foram caracterizadas por técnicas como MEV-EDS, AFM, DRX, FTIR e TGA. Soluções de nitrato de cobalto (Co(NO3)2), cloreto de sódio (NaCl) e cloreto de mercúrio (HgCl2) foram colocadas em contato com amostras de celulose, CNC e CNC-Mod por um tempo máximo de 3h sendo o sólido e o sobrenadante separados. As amostras sólidas obtidas no processo de adsorção foram então submetidas a análises como DRX, MEV-EDS e TGA. Enquanto os sobrenadantes foram analisados por ICP-OES, os resultados indicam a ocorrência de adsorção para todas as amostras e cátions metálicos. / [en] Cellulose is an abundant, renewable and highly biodegradable biopolymer with production in Brazil of approximately 20 million tons in 2017. Obtaining nano-cellulose from different sources and using it in a variety of applications has been the subject of a great amount of research, given its differentiated properties and the possibility of modifications, based on reactions with other organic and inorganic substances. Among the potential applications that nanocellulose presents is the water and wastewater treatment, by processes such as membrane separation, ion exchange and adsorption. The main process for obtaining cellulose nanocrystals is the acid hydrolysis of the amorphous region, remaining more crystalline regions. The most applied production procedures for cellulose nanocrystals consist of the reaction of pure cellulosic material with strong acids with controlled temperature, stirring and time. The crystalline nano-cellulose (CNC) was obtained through acid hydrolysis with sulfuric acid (40 percent) and then modified with citric acid (1.2M), CNC-Mod, for further characterization and adsorption test of metal cations. The samples produced were characterized by techniques such as STEM-EDS, AFM, XRD, FTIR and TGA. Cobalt nitrate (Co(NO3)2), Sodium chloride (NaCl) and mercury chloride (HgCl2) solutions were placed in contact with cellulose, CNC and CNC-Mod samples for a maximum of 3 hours, then having the solid and supernatant separated. The solid samples obtained in the adsorption process were then subjected to analyzes such as XRD, STEM-EDS and TGA. While the supernatants were analyzed by ICP-OES and the results indicates the occurrence of adsorption for all samples and metallic cations.

Renewable lignocellulosic materials are promising green plastic alternatives to fossil fuel-based plastics. However, the hydrophilic nature and poor water resistance of lignocellulosic materials have hindered their practical applications. This study reports a facile metal-ion-modification (MIM) route, swelling with aqueous metal ion solutions, and drying to convert conventional hydrophilic paper and wood pulp into biodegradable hydrophobic paper and tableware without the addition of hydrophobic sizing chemicals/materials. Metal ions such as Fe3+ and Zr4+ can coordinate with pulp fibers’ polar groups (i.e., O.H., C=O, and COOH) that induce self-assembly of their surface fibrillated “hairy” cellulose nanofibrils to form a more compact structure with fewer available O.H. groups for water sorption. The formation of coordination bonds with polar groups (i.e., O.H., C=O, and COOH) decreases the surface energy of pulp fibers and increases their hydrophobicity and water resistance. Only ~3 mg of metal ions is needed to induce the wettability transition in 1 g of kraft pulp, resulting in hydrophobic paper and tableware with water contact angles (WCAs) of 120-140° and displayed wet tensile strengths of up to 9.5 MPa, and low water absorbency, which were comparable to synthetic polymer films. This MIM technique can be integrated into the existing paper-making process for the scalable production of hydrophobic papers and tableware, providing an alternative route for developing sustainable and biodegradable plastic counterparts. The MIM-induced lignocellulose hydrophobization mechanisms were elucidated using X-ray photoelectron spectroscopy (XPS), Fourier transforms infrared spectroscopy (FT-IR), and scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS), and density functional theory (DFT). Furthermore, this MIM technique was also evaluated for its applicability in wood treatment. The treatment effectively tunes the wood surface from hydrophilic to hydrophobic, enhancing its water resistance. The MIM treatment significantly improved the dimensional stability of SYP, red oak, and poplar. For example, the Fe3+ treatment reduced the tangential swelling of SYP, poplar, and red oak by 57%, 50%, and 40%, respectively. Overall, this eco-friendly and facile MIM method holds promise for developing sustainable and biodegradable alternatives to conventional plastics, contributing to a more environmentally friendly future.