Cellulose nanowhiskers from coconut husk fibers: Effect of preparation conditions on their thermal and morphological behavior

Cellulose nanowhiskers were prepared by sulfuric acid hydrolysis from coconut husk fibers which had previously been submitted to a delignification process. The effects of preparation conditions on the thermal and morphological behavior of the nanocrystals were investigated. Cellulose nanowhisker suspensions were characterized by Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), thermogravimetric analysis (TGA) and X-ray diffraction. Results showed that it was possible to obtain ultrathin cellulose nanowhiskers with diameters as low as 5 nm and aspect ratio of up to 60. A possible correlation between preparation conditions and particle size was not observed. Higher residual lignin content was found to increase thermal stability indicating that by controlling reaction conditions one can tailor the thermal properties of the nanowhiskers. Published by Elsevier Ltd.

Effect of Surfactants on the Structure and Morphology of Magnesium Borate Hydroxide Nanowhiskers Synthesized by Hydrothermal Route

Magnesium borate hydroxide (MBH) nanowhiskers were synthesized using a one step hydrothermal process with different surfactants. The effect surfactants have on the structure and morphology of the MBH nanowhiskers has been investigated. The X-ray diffraction profile confirms that the as-synthesized material is of single phase, monoclinic MgBO2(OH). The variations in the size and shape of the different MBH nanowhiskers have been discussed based on the surface morphology analysis. The annealing of MBH nanowhiskers at 500 °C for 4 h has significant effect on the crystal structure and surface morphology. The UV–vis absorption spectra of the MBH nanowhiskers synthesized with and without surfactants show enhanced absorption in the low-wavelength region, and their optical band gaps were estimated from the optical band edge plots. The photoluminescence spectra of the MBH nanowhiskers produced with and without surfactants show broad emission band with the peak maximum at around 400 nm, which confirms the dominant contribution from the surface defect states.

Mannans as film formers and emulsion stabilizers

Mannans are abundant plant polysaccharides found in the endosperm of certain leguminous seeds (guar gum galactomannan, GG; locust bean gum galactomannan, LBG), in the tuber of the konjac plant (konjac glucomannan, KGM), and in softwoods (galactoglucomannan, GGM). This study focused on the effects of the chemical structure of mannans on their film-forming and emulsion-stabilizing properties. Special focus was on spruce GGM, which is an interesting new product from forest biorefineries. A plasticizer was needed for the formation of films from mannans other than KGM and the optimal proportion was 40% (w/w of polymers) glycerol or sorbitol. Galactomannans with lower galactose content (LBG, modified GG) produced films with higher elongation at break and tensile strength. The mechanical properties of GG-based films were improved by decreasing the degree of polymerization of the polysaccharide with moderate mannanase treatments. The improvement of mechanical properties of GGM-based films was sought by blending GGM with each of poly(vinyl alcohol) (PVOH), corn arabinoxylan (cAX), and KGM. Adding other polymers increased the elongation at break of GGM blend films. The tensile strength of films increased with increasing amounts of PVOH and KGM, but the effect of cAX was the opposite. Dynamic mechanical analysis showed two separate loss modulus peaks for blends of GGM and PVOH, but a single peak for all other films. Optical and scanning electron microscopy confirmed good miscibility of GGM with cAX and KGM. In contrast, films blended from GGM and PVOH showed phase separation. GGM and KGM were mixed with cellulose nanowhiskers (CNW) to form composite films. Addition of CNW to KGM-based films induced the formation of fiberlike structures with lengths of several millimeters. In GGM-based films, rodlike structures with lengths of tens of micrometers were formed. Interestingly, the notable differences in the film structure did not appear to be related to the mechanical and thermal properties of the films. Permeability properties of GGM-based films were compared to those of films from commercial mannans KGM, GG, and LBG. GGM-based films had the lowest water vapor permeability when compared to films from other mannans. The oxygen permeability of GGM films was of the same magnitude as that of commercial polyethylene / ethylene vinyl alcohol / polyethylene laminate film. The aroma permeability of GGM films was low. All films were transparent in the visible region, but GGM films blocked the light transmission in the ultraviolet region of the spectra. The stabilizing effect of GGM on a model beverage emulsion system was studied and compared to that of GG, LBG, KGM, and cAX. In addition, GG was enzymatically modified in order to examine the effect of the degree of polymerization and the degree of substitution of galactomannans on emulsion stability. Use of GGM increased the turbidity of emulsions both immediately after preparation and after storage of up to 14 days at room temperature. GGM emulsions had higher turbidity than the emulsions containing other mannans. Increasing the storage temperature to +45 ºC led to rapid emulsion breakdown, but a decrease in storage temperature increased emulsion stability after 14 days. A low degree of polymerization and a high degree of substitution of the modified galactomannans were associated with a decrease in emulsion turbidity.

Two-step Synthesis of MoS2 Nanotubes using Shock Waves with Lead as Growth Promoter

A new two-step procedure for the synthesis of MoS2 nanotubes using lead as a growth promoter is reported. In the first step, molybdenum suboxide nanowhiskers containing a small amount of lead atoms were created by exposing a pressed MoS2+Pb mixture to highly compressed shock-heated argon gas, with estimated temperatures exceeding 9900 K. In the second step, these molybdenum suboxide nanowhiskers served as templates for the sulfidization of the oxide into MoS2 nanotubes (by using H2S gas in a reducing atmosphere at 820 degrees C). Unlike the case of WS2 nanotubes, the synthesis of a pure phase of MoS2 nanotubes from molybdenum oxide has proven challenging, due mostly to the volatile nature of the latter at the high requisite reaction temperatures (>800 degrees C). In contrast, the nature and apparent reaction mechanism of the method reported herein are amenable to future scale-up. The high-temperature shockwave system should also facilitate the synthesis of new nanostructures from other layered materials.

Caracterização e utilização do resíduo de palha de milho para obtenção de nanocelulose

Esta Dissertação discorre sobre a pesquisa de caracterização de palha de milho e a sua utilização como matéria prima para a obtenção de nanocelulose. Segundo o IBGE, este resíduo agrícola foi produzido no Brasil, no ano de 2013, em cerca de seis milhões de toneladas. As amostras deste resíduo lignocelulósico utilizadas neste trabalho foram coletadas na forma cotidiana de descarte mais frequentemente encontrada em supermercados e feiras livres. Procedeu-se, então, ao beneficiamento mecânico, beneficiamento químico (mercerização e branqueamento) e hidrólise ácida dessas amostras, o que produziu os seguintes materiais: palha de milho beneficiada mecanicamente, palha de milho beneficiada quimicamente e nanocelulose. Cada um destes materiais foi caracterizado, conforme o tipo, por menos ou mais dos seguintes ensaios: determinação de densidade, determinação de umidade, determinação do teor de cinzas, resistência à tração, determinação do teor de extraíveis, determinação do teor de holocelulose, determinação do teor de hemicelulose, determinação do teor de alfacelulose, determinação do teor de lignina, análise termogravimétrica (TGA), espectroscopia por infravermelho por transformada de Fourier (FTIR), índice de cristalinidade por difração de raios-x (CrI), medição do tamanho de partícula por espalhamento de luz dinâmico (DLS), morfologia por microscopia eletrônica de varredura (SEM) e determinação do rendimento dos produtos de hidrólise. Nesta pesquisa também se estudou, empregando a técnica de planejamento de experimento fatorial com ponto central, a influência dos fatores razão fibra/ácido e tempo da reação na obtenção da nanocelulose, conseguida com êxito em todos os experimentos executados com a palha de milho que foi branqueada de forma efetiva neste trabalho

Biocompósitos poliméricos obtidos a partir da fração lignocelulósica e amilácea do caroço de manga (mangifera indica), Tommy atkins

This employment has the function the utilization of mango seeds Tommy Atkins, like starch source to obtain biopolymers and fibers source and nanowhiskers cellulose also, that will be use like reinforcing fillers in micro and nanobiocomposites polymeric. The fibers in natura removed from tegument mango seed were characterized, as weel as the treated fibers and nanowhiskers of cellulose extracted from them. The starch extracted from seed s almond showed a good performance (32%) and a high purity. The chemicals analyzes, of crystallinity and morphological of the fibers in natura, treated fibers and nanowhiskers of cellulose confirmed the efficacy of the chemical treatement performed to remove amorphous constituents (hemicellulose and lignina). The thermoplastic starch (TPS) obtained from two sources, corn starch and starchy material mango, was produced in a twin screw extruder with compositon mass of 62,5% of starch, 9,4% of water and 28,1% of glycerol. The starch material mango was the main objective of this work for the production of biodegradable materials, and the starch corn was utilized during the production stage to evaluate the processability of the starch and use as parameter for comparison, according of being a conventional source for obtaining conventional comercial starch. The incorporation of fibers (6% in mass) and nanowhiskers cellulose (1% in mass) in matrix of TPS to obtain composite and nanocomposite, respectively, it was performed in single screw extruder. The biocomposites and bionanocomposites polymeric were obtained and the TPS from starchy material mango presented better results of thermal and mechanicals properties when compared to TPS corn starch. Concludes that the sediment generated of the agroindustrial processing mango used presents potencial to producing of biodegradables materials

Sleeving nanocelluloses by admicellar polymerization

This investigation reports the first application of admicellar polymerization to cellulose nanofibers in the form of bacterial cellulose, microfibrillated cellulose, and cellulose nanowhiskers using styrene and ethyl acrylate. The success of this physical sleeving was assessed by SEM, FTIR, and contact angle measurements, providing an original and simple approach to the modification of cellulose nanofibers in their pristine aqueous environment. © 2013 The Authors. Published by Elsevier Inc.

Obtenção e caracterização de nanocompósitos de borracha natural reforçada com nanofibras de celulose recobertas com polianilina

Pós-graduação em Ciência dos Materiais - FEIS

Band structure calculations of InP wurtzite/zinc-blende quantum wells

Semiconductor nanowhiskers (NWs) made of III-V compounds exhibit great potential for technological applications. Controlling the growth conditions, such as temperature and diameter, it is possible to alternate between zinc-blende (ZB) and wurtzite (WZ) crystalline phases, giving origin to the so called polytypism. This effect has great influence in the electronic and optical properties of the system, generating new forms of confinement to the carriers. A theoretical model capable to accurately describe electronic and optical properties in these polytypical nanostructures can be used to study and develop new kinds of nanodevices. In this study, we present the development of a wurtzite/zinc-blende polytypical model to calculate the electronic band structure of nanowhiskers based on group theory concepts and the k.p method. Although the interest is in polytypical superlattices, the proposed model was applied to a single quantum well of InP to study the physics of the wurtzite/zinc-blende polytypism. By the analysis of our results, some trends can be predicted: spatial carriers' separation, predominance of perpendicular polarization (xy plane) in the luminescence spectra, and interband transition blueshifts with strain. Also, a possible range of values for the wurtzite InP spontaneous polarization is suggested. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4767511]

Edible films from alginate-acerola puree reinforced with cellulose whiskers

Fruit purees, combined or not with polysaccharides, have been used in some studies to elaborate edible films. The present study was conducted to evaluate tensile properties and water vapor barrier of alginate-acerola puree films plasticized with corn syrup, and to study the influence of cellulose whiskers from different origins (cotton fiber or coconut husk fiber, the latter submitted to one- or multi-stage bleaching) on the film properties. The whiskers improved the overall tensile properties (except by elongation) and the water vapor barrier of the films. The films with coconut whiskers, even those submitted only to a one-stage bleaching, presented similar properties to those of films with cotton whiskers, despite the low compatibility between the matrix and the remaining lignin in coconut whiskers. This was probably ascribed to a counterbalancing effect of the higher aspect ratios of the coconut whiskers. (C) 2011 Elsevier Ltd. All rights reserved.

Synthesis, characterization and crystallization of bionanocomposites based on PLLA, PCL and nanocellulose

In recent years, environmental concerns and the expected shortage in the fossil reserves have increased further development of biomaterials. Among them, poly(lactide) PLA possess some potential properties such as good ability process, excellent tensile strength and stiffness equivalent to some commercial petroleum-based polymers (PP, PS, PET, etc.). This biobased polymer is also biodegradable and biocompatible However, one great disadvantage of commercial PLA is slow crystallization rate, which restricts its use in many fields. Using of nanofillers is viewed as an efficient strategy to overcome this problem. In this thesis, the effect of bionanofillers in neat PLA and in blends of poly (L-lactide)(PLA)/poly(ε-Caprolactone) (PCL) has been investigated. The used nanofillers are: poly(L-lactide-co-ε-caprolactone) and poly(L-lactide-b-ε-caprolactone) grafted on cellulose nanowhiskers and neat cellulose nanowhiskers (CNW). The grafting reaction of poly(L-lactide-co-caprolactone) and poly (L-lactide-b-caprolactone) on the nanocellulose has been performed by the grafting from technique. In this way the polymerization reaction it is directly initiated on the substrate surface. The condition of the reaction were chosen after a temperature and solvent screening. By non-isothermal an isothermal DSC analysis the effect of bionanofillers on PLA and 80/20 PLA/PCL was evaluated. Non-isothermal DSC scans show a nucleating effect of the bionanofillers on PLA. This effect is detectable during PLA crystallization from the glassy state. Cold crystallization temperature is reduced upon the addition of the poly(L-lactide-b-caprolactone) grafted on cellulose nanowhiskers that is most performing bionanofiller in acting as a nucleating agent. On the other hand, DSC isothermal analysis on the overall crystallization rate indicate that cellulose nanowhiskers are best nucleating agents during isothermal crystallization from the melt state. In conclusion, nanofillers have different behavior depending on the processing conditions. However, the efficiency of our nanofillers as nucleating agent was clearly demonstrated in both isothermal as in non-isothermal condition.

Biocompósitos poliméricos obtidos a partir da fração lignocelulósica e amilácea do caroço de manga (mangifera indica), Tommy atkins

This employment has the function the utilization of mango seeds Tommy Atkins, like starch source to obtain biopolymers and fibers source and nanowhiskers cellulose also, that will be use like reinforcing fillers in micro and nanobiocomposites polymeric. The fibers in natura removed from tegument mango seed were characterized, as weel as the treated fibers and nanowhiskers of cellulose extracted from them. The starch extracted from seed s almond showed a good performance (32%) and a high purity. The chemicals analyzes, of crystallinity and morphological of the fibers in natura, treated fibers and nanowhiskers of cellulose confirmed the efficacy of the chemical treatement performed to remove amorphous constituents (hemicellulose and lignina). The thermoplastic starch (TPS) obtained from two sources, corn starch and starchy material mango, was produced in a twin screw extruder with compositon mass of 62,5% of starch, 9,4% of water and 28,1% of glycerol. The starch material mango was the main objective of this work for the production of biodegradable materials, and the starch corn was utilized during the production stage to evaluate the processability of the starch and use as parameter for comparison, according of being a conventional source for obtaining conventional comercial starch. The incorporation of fibers (6% in mass) and nanowhiskers cellulose (1% in mass) in matrix of TPS to obtain composite and nanocomposite, respectively, it was performed in single screw extruder. The biocomposites and bionanocomposites polymeric were obtained and the TPS from starchy material mango presented better results of thermal and mechanicals properties when compared to TPS corn starch. Concludes that the sediment generated of the agroindustrial processing mango used presents potencial to producing of biodegradables materials