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Low-density green polyethylene (LDGPE) composites reinforced with 5 wt% of bamboo fiber and 3 wt% of a compatibilizing agent (polyethylene grafted with maleic anhydride and tannin) were processed through extrusion and injection molding. Bamboo fiber, Bambusa Vulgaris, was characterized using Fourier-transform infrared spectroscopy (FTIR). The molded specimens were analyzed for their thermal, mechanical, and morphological properties. The estimated concentration was chosen to provide the best mechanical strength to the material studied. FTIR analysis of the fibers revealed the presence of groups characteristic of bamboo fiber and tannin. Differential scanning calorimetry revealed that both compatibilizing agents increased the matrix's degree of crystallinity. However, scanning electron microscopy (SEM) showed that, despite the presence of compatibilizing agents, there was no significant improvement in adhesion between the bamboo fibers and LDGPE.
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As air pollution escalates, the need for air filters increases. It is better that the filters used be based on natural fibers, such as non-wood fibers, which cause low damage to the environment. However, the short fiber lengths, low apparent densities, and high volumes of non-wood materials can make it challenging to prepare filter paper with the required mechanical and physical properties. In that context, this study focused on utilizing bamboo fibers to fabricate filter paper by employing the anthraquinone soda pulping method. The pulp underwent bleaching and oxidation processes, with the incorporation of cationic starch (CS) and polyvinyl alcohol (PVA) to enhance resistance properties, resulting in the creation of handmade filter papers. The findings revealed that the tear, burst, and tensile strength of filter paper increased with the oxidation and addition of CS and PVA. Air permeability increased with addition of PVA and combination of CS and PVA. FTIR demonstrated the conversion of hydroxyl groups in cellulose chains to carboxyl groups due to oxidation. SEM images illustrated alterations in the fiber structure post-oxidation treatment, with CS reducing pores while PVA and the CS-PVA combination enlarged pore size and enhanced porosity. The BET surface area surface area expanded with oxidation and the addition of the CS-PVA blend, indicating heightened filter paper porosity. Notably, the combined inclusion of CS and PVA not only augmented mechanical strength but also increased porosity while maintaining pore size.
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Fish protein hydrolysates were obtained from cultured rainbow trout (Oncorhynchus mykiss) viscera using commercial and endogenous enzymes. Two methods were employed for hydrolysis: acid autolysis (also known as silage) at room temperature for 10 days in acidic conditions, until total solubilisation, and enzymatic hydrolysis using Alcalase 2.4 LFG, Protana Prime, and the endogenous enzymes in the viscera. The effectiveness of both methods in releasing free amino acids (FAA) was assessed. After evaluating the results, the most effective enzymatic hydrolysis was optimized. The findings indicated that enzymatic hydrolysis with Alcalase, Protana Prime and endogenous enzymes combined for 7 h at a dose of 1% of protein, and a 7-day acid autolysis yielded the highest degree of hydrolysis (83.8% and 75.8%), a yield of FAA from viscera of 5.9% and 3.2%, and a yield of FAA from total protein of 71.3% and 52.5%, respectively. In conclusion, the use of commercial enzymes was more efficient in releasing amino acids, but endogenous enzymes showed a strong proteolytic capacity during acid autolysis, suggesting it also as a promising method to produce FAA-rich hydrolysates.
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Lignin has been overlooked and used as a waste for long due to its complex and partially hydrophobic structure. Many efforts have been carried out to overcome these deficiencies and apply it as a high-value product, which are insufficient to reach the full potential of lignin in various advanced applications, since they require with procedures for the obtaining of more specific and fine-tuned chemical structures. This work focuses on the obtaining of differently structured hydrophilic lignins derived both from Kraft and organosolv isolation processes. The chemical structures of the different lignin types were studied, and the effect of the structural differences in the modification processes and their subsequent properties analyzed, valorizing their potential application for diverse purposes. The carboxymethylation and sulfomethylation reactions were carried out with the aim of enhancing the polarity of the lignin samples, while the methylation reaction aimed to obtain lignins with higher stability. The physicochemical analyses of the samples, carried out by FTIR, GPC, 31P NMR, 13C NMR, and HSQC NMR, verified the effectiveness of the chemical reactions and conditions selected, obtaining lignins with lower hydroxyl content, due to their substitution and insertion of carboxymetyl, sulfomethyl and methyl groups, therefore obtaining more condensed, aromatic and oxygenated aromatic carbon structures. While the methylation reaction was the most efficient in substituting the OH groups, due to its non-selectivity, OL showed higher modification yields than KL. In terms of the thermal and morphological properties, analyzed by DLS and TGA respectively, it was observed that the modified samples showed lower Z potential values, along with higher conductivity, being the sulfomethylated organosolv lignin the one showing the best results, which was also the one with the smallest particle size and polydispersity index. Finally, all the modified samples showed higher T50% values, suggesting a better stability towards degradation.
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Lignina , Lignina/química , Espectroscopia de Ressonância Magnética , Tamanho da PartículaRESUMO
In this work, biobased rigid polyurethane foams (PUFs) were developed with the aim of achieving thermal and fireproofing properties that can compete with those of the commercially available products. First, the synthesis of a biopolyol from a wood residue by means of a scaled-up process with suitable yield and reaction conditions was carried out. This biopolyol was able to substitute completely the synthetic polyols that are typically employed within a polyurethane formulation. Different formulations were developed to assess the effect of two flame retardants, namely, polyhedral oligomeric silsesquioxane (POSS) and amino polyphosphate (APP), in terms of their thermal properties and degradation and their fireproofing mechanism. The structure and the thermal degradation of the different formulations was evaluated via Fourier Transformed Infrared Spectroscopy (FTIR) and thermogravimetric analysis (TGA). Likewise, the performance of the different PUF formulations was studied and compared to that of an industrial PUF. From these results, it can be highlighted that the addition of the flame retardants into the formulation showed an improvement in the results of the UL-94 vertical burning test and the LOI. Moreover, the fireproofing performance of the biobased formulations was comparable to that of the industrial one. In addition to that, it can be remarked that the biobased formulations displayed an excellent performance as thermal insulators (0.02371-0.02149 W·m-1·K-1), which was even slightly higher than that of the industrial one.
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Posidonia oceanica balls (POB), a kind of seagrass, are a significant environmental issue since they are annually discharged onto beaches. Their current usefulness limits interest in their management and enhances the environmental problem. Therefore, in this research, the potential of this lignocellulosic biomass was studied from a holistic biorefinery point of view. To this end, an in-depth study was carried out to select the best pathway for the integral valorization of POBs. First, an autohydrolysis process was studied for the recovery of oligosaccharides. Then, a delignification stage was applied, where, in addition to studying different delignification methods, the influence of the autohydrolysis pre-treatment was also investigated. Finally, cellulose nanofibers (CNFs) were obtained through a chemo-mechanical treatment. The results showed that autohydrolysis not only improved the delignification process and its products, but also allowed the hemicelluloses to be valorized. Acetoformosolv delignification proved to be the most successful in terms of lignin and cellulose properties. However, alkaline delignification was able to extract the highest amount of lignin with low purity. CNFs were also successfully produced from bleached solids. Therefore, the potential of POB as a feedstock for a biorefinery was confirmed, and the pathway should be chosen according to the requirements of the desired end products.
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Mitigating the effect of climate change toward a sustainable development is one of the main challenges of our century. The emission of greenhouse gases, especially carbon dioxide (CO2), is a leading cause of the global warming crisis. To address this issue, various sustainable strategies have been formulated for CO2 capture. Renewable nanocellulose aerogels have risen as a highly attractive candidate for CO2 capture thanks to their porous and surface-tunable nature. Nanocellulose offer distinctive characteristics, including significant aspect ratios, exceptional biodegradability, lightweight nature, and the ability for chemical modification due to the abundant presence of hydroxyl groups. In this review, recent research studies on nanocellulose-based aerogels designed for CO2 absorption have been highlighted. The state-of-the-art of nanocellulose-based aerogel has been thoroughly assessed, including their synthesis, drying methods, and characterization techniques. Additionally, discussions were held about the mechanisms of CO2 adsorption, the effects of the porous structure, surface functionalization, and experimental parameters. Ultimately, this synthesis review provides an overview of the achieved adsorption rates using nanocellulose-based aerogels and outlines potential improvements that could lead to optimal adsorption rates. Overall, this research holds significant promise for tackling the challenges of climate change and contributing to a more sustainable future.
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Bio-polyols, produced by liquefying lignin with polyhydric alcohols, offer a promising alternative to conventional polyols for polyurethane production. To enhance the sustainability on the production of these bio-polyols, this study proposes the use of crude glycerol and microwave-assisted liquefaction as substitutes for conventional methods and commercial glycerol. This approach reduces the energy requirements of the reaction while also adding value to this by-product. The synthesis of bio-polyols with suitable properties to produce elastic and rigid polyurethane was carried out using previously optimised reaction conditions. Organosolv lignins obtained from Eucalyptus globulus and Pinus radiata were employed, using polyethylene glycol and crude glycerol as solvents and sulphuric acid as a catalyst. Several parameters of the bio-polyols were analysed, including hydroxyl number (IOH), acid number (An), and functionality (f), suggesting that the bio-polyols were suitable for polyurethane synthesis. Bio-polyols formulated to produce rigid polyurethanes exhibited IOH values of 554 and 383 (mg KOH/g), An values of 1.91 and 4.21 (mg KOH/g), and functionalities of 4.16 and 3.14 for Eucalyptus globulus and Pinus radiata lignin. In the case of bio-polyols for elastic polyurethanes, the values were 228 and 173 (mg KOH/g) (IOH), 20.94 and 25.09 (mg KOH/g) (An), and functionalities of 3.51 and 2.08.
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Glicerol , Lignina , Poliuretanos , PolímerosRESUMO
Thermal management protects against external agents and increases the lifetime and performance of the devices in which it is implemented. Because of their ability to store and release a high amount of energy at a nearly constant temperature, phase change materials (PCMs) are promising thermoregulatory materials. Thus, the manufacture of PVDF fibers containing PCMs has advantages since PVDF is already used in elements that are susceptible to thermal management as a binder in batteries or as a base material for fabrics. This work presents a simple, versatile, in situ, cost-effective, and easy-to-scale-up method to produce PVDF-based fibers containing paraffin RT-28HC for thermal management. To achieve that goal, the microfluidic approach of coaxial flows was simplified to gravity-aided laminar jet injection into a bulk fluid, where fibers were produced by the solvent extraction mechanism. With this methodology, hollow PVDF fibers and core-shell PVDF fibers containing paraffin RT-28HC have been produced. The proposed approach resulted in fibers with up to 98 J/g of latent heat, with a hierarchical porous structure. SEM study of the fiber morphology has shown that PCM is in the form of slugs along the fibers. Such PCM distribution is maintained until the first melting cycle, when molten PCM spreads within the fiber under capillary forces, which was observed by an infrared camera. Manufactured composite fibers have shown low thermal conductivity and high elasticity, which suggest their potential application as a thermal insulation material with thermal buffer properties. Leakage tests revealed outstanding retention capacity with only 3.5% mass loss after 1000 melting/crystallization cycles. Finally, tensile tests were carried out to evaluate the mechanical properties of the fibers before and after thermal cycling.
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An efficient and smart synthesis of bis-α-ketoamides has been disclosed. The desired products have been obtained through a Passerini multicomponent reaction using biobased aldehydes, acetic acid and bis-isocyanides (prepared from the corresponding biobased diamides), followed by a deprotection/oxidation step. The effect of the synthesized compounds on the crystallization behavior of poly(l-lactide) (PLLA) has been investigated by differential scanning calorimetry (DSC) in non-isothermal conditions. Among all the synthesized compounds, only a few are able to meaningfully enhance the nucleation of PLLA, as confirmed by a shift of the polymer crystallization peak temperature towards higher values. With the research of active polymer nucleating agents being mostly empirical, the combinatorial synthetic approach proposed herein, coupled with the possibility of a small scale mixing procedure, can potentially represent a useful strategy for the discovery of new efficient biobased polymer additives.
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Hydrogels have become one of the potential polymers used with great performance for many issues and can be promoted as biomaterials with highly innovative characteristics and different uses. Gelatin is obtained from collagen, a co-product of the meat industry. Thus, converting wastes such as cartilage, bones, and skins into gelatin would give them added value. Furthermore, biodegradability, non-toxicity, and easy cross-linking with other substances can promote polymers with high performance and low cost for many applications, turning them into sustainable products with high acceptance in society. Gelatin-based hydrogels have been shown to be useful for different applications with important and innovative characteristics. For instance, these hydrogels have been used for biomedical applications such as bone reconstruction or drug delivery. Furthermore, they have also shown substantial performance and important characteristics for remediation for removing pollutants from water, watercourse, and effluents. After its uses, gelatin-based hydrogels can easily biodegrade and, thus, can be sustainably used in the environment. In this study, gelatin was shown to be a potential polymer for hydrogel synthesis with highly renewable and sustainable characteristics and multiple uses.
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In recent years, the considerable importance of healthcare and the indispensable appeal of curative issues, particularly the diagnosis of diseases, have propelled the invention of sensing platforms. With the development of nanotechnology, the integration of nanomaterials in such platforms has been much focused on, boosting their functionality in many fields. In this direction, there has been rapid growth in the utilisation of nanocellulose in sensors with medical applications. Indeed, this natural nanomaterial benefits from striking features, such as biocompatibility, cytocompatibility and low toxicity, as well as unprecedented physical and chemical properties. In this review, different classifications of nanocellulose-based sensors (biosensors, chemical and physical sensors), alongside some subcategories manufactured for health monitoring, stand out. Moreover, the types of nanocellulose and their roles in such sensors are discussed.
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Técnicas Biossensoriais , Nanoestruturas , Nanoestruturas/toxicidade , Nanoestruturas/química , NanotecnologiaRESUMO
This study investigated composition and toxicity of Thyme EOs against two main stored grain insect pests. Carvacrol was distinguished as a major compound (78.34%). In laboratory tests, EOs applied by both direct contact and fumigant tests was more toxic to L. serricorne than T. castaneum. The EOs were also tested combined with two Tunisian Diatomaceous earths (DEs) against T. castaneum. The LC50 was 6.28 µL/L air for natural preparation EO/R1, 5.90 µL/L air for EO/R2 and 121.17 for crude EOs by fumigant test, respectively. While, contact test revealed that natural DEs; dust act as an insecticide with 'LC50' values of 3.22 and 0.29 µL/cm2f or R1 and R2, respectively. Moreover, a significant difference was noted between crude EO, EO/R1 and EO/R2. Overall, the enhancement of the Tunisian DEs' insecticidal activity by its mix with EOs may be a promising active substance as a stored grain protectant.
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Besouros , Inseticidas , Óleos Voláteis , Animais , Inseticidas/farmacologia , Óleos Voláteis/farmacologia , Terra de Diatomáceas/farmacologia , Controle de PragasRESUMO
The goal of this study is to assess Ziziphus lotus's potential for producing carboxymethylcellulose adsorption membranes with the ability to adsorb methyl green from wastewaters by the revalorization of its cellulosic fraction. The cellulose from this feedstock was extracted by an alkaline process and TAPPI standard technique T 203 cm-99 and afterwards they were carboxymethylated. The obtained carboxymethylcelluloses were deeply characterized, being observed that the carboxymethylcellulose produced from the alkaline cellulose presented the higher solubility due to its lower crystallinity degree (53.31 vs. 59.4%) and its higher substitution degree (0.85 vs. 0.74). This carboxymethylcellulose was cross-linked with citric acid in an aqueous treatment in order to form an adsorption membrane. The citric acid provided rigidity to the membrane and although it was hydrophilic it was not soluble in water. By evaluating the potential of the produced membrane for the removal of pollutant dyes from wastewater, it was observed that the adsorption membrane prepared from the carboxymethylcellulose's produced from the Ziziphus lotus was able to remove 99% of the dye, methyl green, present in the wastewater. Thus, this work demonstrates the potential of the Ziziphus lotus for the production of a novel and cost-effective carboxymethylcellulose adsorption membrane with high capacity to treat wastewaters.
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The use of lignocellulosic fillers in rigid polyurethane foams (RPUFs) has been receiving great attention due to their good mechanical and insulation properties and the high sustainable appeal of the obtained cellular polymers, although high water uptakes are found in most of these systems. To mitigate this detrimental effect, RPUFs filled with wood flour (2.5% wt) were fabricated with the addition of furfuryl alcohol (FA) to create a polymer grafted with the wood filler. Two concentrations of FA (10 wt% and 15 wt%) were investigated in relation to the wood flour, and the RPUFs were characterized for cell morphology, density, compressive properties, thermal stability, and water uptake. The introduction of wood flour as a filler decreased the cell size and increased the anisotropy index of the RPUFs and, in addition to that, the FA grafting increased these effects even more. In general, there were no significant changes in both mechanical and thermal properties ascribed to the incorporation of the fillers. On the other hand, a reduction of up to 200% in water uptake was ascribed to the FA-treated fillers.
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Flame-resistant materials are key components in buildings and several other engineering applications. In this study, flame retardancy and thermal stability were conferred to a highly flammable technical thermoplastic-polypropylene (PP)-upon compositing with a carbonaceous tannin-based particulate (CTP). Herein, we report on a straightforward, facile, and green approach to prepare self-extinguishing thermoplastic composites by thermoblending highly recalcitrant particulate. The thermal stability and mechanical properties of the composites are tethered to the CTP content. We demonstrate that the addition of up to 65 wt% of CTP improved the viscoelastic properties and hydrophobicity of the PP, whereas having marginal effects on bulk water interactions. Most importantly, compositing with CTP remarkably improved the thermal stability of the composites, especially over 300 °C, which is an important threshold associated with the combustion of volatiles. PP-CTP composites demonstrated great capacity to limit and stop fire propagation. Therefore, we offer an innovative route towards thermally resistant and self-extinguishing PP composites, which is enabled by sustainable tannin-based flame retardants capable of further broadening the technical range of commodity polyolefins to high temperature scenarios.
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Increase in industrial activities has been arising a severe concern about water pollution caused by heavy metal ions (HMIs), such us lead (Pb2+), cadmium (Cd2+) or mercury (Hg2+). The presence of substantial amounts of these ions in the human body is harmful and can cause serious diseases. Hence, the detection of HMIs in water is of great importance. As technological advances have developed, some conventional methods have become obsolete due to some methodological disadvantages, giving way to a second generation that uses novel sensors. Recently, nanocellulose, as a biocompatible material, has drawn a remarkable attraction for developing sensors owing to its extraordinary physical and chemical properties. This review pays a special attention to the different dimensional nanocellulose-based sensors devised for HMIs recognition. What is more, different sensing techniques (optical and electrochemical), sensing mechanisms and the roles of nanocellulose in such sensors are discussed.
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Mercúrio , Metais Pesados , Cádmio/química , Humanos , Íons/química , Mercúrio/química , Metais Pesados/química , Água/químicaRESUMO
A series of novel chitosan/tannin/montmorillonite (Cs/Tn/MMT) films were synthesised by loading different (from 0.2 to 0.5 wt%) and MMT (from 0.5 to 1.5 wt%) ratios, to be used as promising low-cost biosorbents for methyl orange (MO) removal from aqueous media. The prepared films were characterised using different techniques such as x-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), water contact angle, optical properties, colourimetric measurement, porosity, swelling and thickness. The effects of various parameters, i.e. initial MO concentration, adsorbent dose, pH and temperature, were studied. The Cs/Tn0.2/MMT1 film showed a high removal efficiency of 95.62% and maximum adsorption capacity of 57.37 mg/g under the optimum adsorption conditions (initial methyl orange concentration 60 mg/L, pH 7 and 25 °C). The adsorption kinetic followed the pseudo second order kinetic model and the experimental data were a good fit for the Langmuir isotherm indicating a homogeneous and monolayer adsorption process. The thermodynamic parameters suggested physical adsorption and exothermic behaviour. Consequently, Cs/Tn/MMT films showed effective potential for the uptake of anionic dyes.
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Quitosana , Poluentes Químicos da Água , Adsorção , Compostos Azo , Bentonita/química , Quitosana/química , Corantes/química , Concentração de Íons de Hidrogênio , Cinética , Espectroscopia de Infravermelho com Transformada de Fourier , Taninos , Termodinâmica , Água , Poluentes Químicos da Água/químicaRESUMO
Walnut kernels represent no more than 50-60% of the total weight of the fruit, so the sum of walnut shells generated every year is immense. Nonetheless, these shells could be further valorised for the extraction of their main constituents following a biorefinery scheme. Hence, the objective of this work was an integral valorisation of walnut shells, which involved a sequential organosolv delignification (200 °C, 90 min, 70/30 v/v EtOH/H2O, LSR 6:1) and several posterior non-isothermal hydrothermal treatments (180, 195 and 210 °C, LSR 8:1). Moreover, the spent solids after the aforementioned treatments were evaluated as possible sources of cellulose nanocrystals. The results showed that the sequential organosolv delignifications presented relative lignin yields up to 60%, which leaded to lignins that just differed on their molecular weight distributions. The hydrothermal treatments were efficient for the removal of still present hemicelluloses (14.7-71.8%), and permitted a successful cellulose nanocrystal obtaining whereas the spent solid from the delignification stages did not. Thus, this study presented an innovative strategy for the integral valorisation of walnut shells.
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Juglans , Celulose , Etanol , Hidrólise , LigninaRESUMO
Chitosan films lack various important physicochemical properties and need to be supplemented with reinforcing agents to bridge the gap. Herein, we have produced chitosan composite films supplemented with copolymerized (with polyacrylonitrile monomers) cellulose nanofibers and diatomite nanocomposite at different concentrations. The incorporation of CNFs and diatomite enhanced the physicochemical properties of the films. The mechanical characteristics and hydrophobicity of the films were observed to be improved after incorporating the copolymerized CNFs/diatomite composite at different concentrations (CNFs: 1%, 2% and 5%; diatomite: 10% and 30%). The antioxidant activity gradually increased with an increasing concentration (1-5% and 10-30%) of copolymerized CNFs/diatomite composite in the chitosan matrix. Moreover, the water solubility decreased from 30% for chitosan control film (CH-0) to 21.06% for films containing 30% diatomite and 5% CNFs (CNFs-D30-5). The scanning electron micrographs showed an overall uniform distribution of copolymerized CNFs/diatomite composite in the chitosan matrix with punctual agglomerations.