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Metal-phenolic network (MPN) foams are prepared using colloidal suspensions of tannin-containing cellulose nanofibers (CNFs) that are ice-templated and thawed in ethanolic media in the presence of metal nitrates. The MPN facilitates the formation of solid foams by air drying, given the strength and self-supporting nature of the obtained tannin-cellulose nanohybrid structures. The porous characteristics and (dry and wet) compression strength of the foams are rationalized by the development of secondary, cohesive metal-phenolic layers combined with a hydrogen bonding network involving the CNF. The shrinkage of the MPN foams is as low as 6% for samples prepared with 2.5-10% tannic acid (or condensed tannin at 2.5%) with respect to CNF content. The strength of the MPN foams reaches a maximum at 10% tannic acid (using Fe(III) ions), equivalent to a compressive strength 70% higher than that produced with tannin-free CNF foams. Overall, a straightforward framework is introduced to synthesize MPN foams whose physical and mechanical properties are tailored by the presence of tannins as well as the metal ion species that enable the metal-phenolic networking. Depending on the metal ion, the foams are amenable to modification according to the desired application.
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This work deals with the durability of a Pinus elliotti wood impregnated with alumina (Al2O3) particles. The samples were impregnated at three different Al2O3 weight fractions (c.a. 0.1%, 0.3% and 0.5%) and were then exposed to two wood-rot fungi, namely white-rot fungus (Trametes versicolor) and brown-rot fungus (Gloeophyllum trabeum). Thermal and chemical characteristics were evaluated by Fourier transform infrared spectroscopy (FT-IR) and thermogravimetric (TG) analyses. The wood which incorporated 0.3 wt% of Al2O3 presented a weight loss 91.5% smaller than the untreated wood after being exposed to the white-rot fungus. On the other hand, the highest effectiveness against the brown-rot fungus was reached by the wood treated with 5 wt% of Al2O3, which presented a mass loss 91.6% smaller than that of the untreated pine wood. The Al2O3-treated woods presented higher antifungal resistances than the untreated ones in a way that: the higher the Al2O3 content, the higher the thermal stability. In general, the impregnation of the Al2O3 particles seems to be a promising treatment for wood protection against both studied wood-rot fungi. Additionally, both FT-IR and TG results were valuable tools to ascertain chemical changes ascribed to fungal decay.
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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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Aerogels are 3-D nanostructures of non-fluid colloidal interconnected porous networks consisting of loosely packed bonded particles that are expanded throughout their volume by gas and exhibit ultra-low density and high specific surface area. Cellulose-based aerogels can be obtained from hydrogels through a drying process, replacing the solvent (water) with air and keeping the pristine three-dimensional arrangement. In this work, hybrid cellulose-based aerogels were produced and their potential for use as dressings was assessed. Nanofibrilated cellulose (NFC) hydrogels were produced by a co-grinding process in a stone micronizer using a kraft cellulosic pulp and a phenolic extract from Maclura tinctoria (Tajuva) heartwood. NFC-based aerogels were produced by freeze followed by lyophilization, in a way that the Tajuva extract acted as a functionalizing agent. The obtained aerogels showed high porosity (ranging from 97% to 99%) and low density (ranging from 0.025 to 0.040 g·cm-3), as well a typical network and sheet-like structure with 100 to 300 µm pores, which yielded compressive strengths ranging from 60 to 340 kPa. The reached antibacterial and antioxidant activities, percentage of inhibitions and water uptakes suggest that the aerogels can be used as fluid absorbers. Additionally, the immobilization of the Tajuva extract indicates the potential for dentistry applications.
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We report on the combination of cellulose nanofibrils (CNFs) and condensed tannins from Acacia mearnsii for the development of hybrid, functional films. The tannins are fractionated and concentrated in polyphenolics that are used for functional components in the hybrid materials. Cogrinding of wood fibers with the tannins in aqueous media allows simultaneous fiber deconstruction and in situ binding of tannins on the freshly exposed cellulosic surfaces. Hence, a tightly bound bicomponent system is produced, which is otherwise not possible if typical adsorption protocols are followed, mainly due to the extensive hydration typical of CNFs. A nonionic surfactant is used to tailor the cellulose-tannin interactions. The proposed strategy not only enables the incorporation of tannins with CNFs but also endows a high and prolonged antioxidant effect of films formed by filtration. Compared to tannin-free films, those carrying tannins are considerably more hydrophobic. In addition, they show selective absorption of ultraviolet light while maintaining optical transparency in the visible range. The proposed simple protocol for incorporating tannins and surfactants with CNFs is suitable to produce functional materials. This is possible by understanding associated interfacial phenomena in the context of sustainable materials within the concept of the circular bioeconomy.
Asunto(s)
Acacia , Taninos , Celulosa , Tensoactivos , MaderaRESUMEN
The effect of thermal treatments on physical and mechanical properties of rose gum and Sydney blue gum wood was evaluated. Wood samples were thermally modified in a combination: pre-treatment in an autoclave (127°C - 1h) and treatment in an oven (180-240°C - 4h); and only treatment in an oven at 180-240°C for 4h. Chemical changes in the structure of woods were evaluated through infrared spectroscopy. Evaluation of physical properties was performed through mass loss, specific gravity, equilibrium moisture content and dimensional stability tests. Surface changes were analyzed through apparent contact angle technique and static bending tests were carried out to evaluate the mechanical behavior. Use of pre-treatment in autoclave affected the properties analyzed, however oven, resulted in the highest changes on wood from both species. Chemical changes were related to the degradation of hemicelluloses. Moreover, a significant decrease of hygroscopicity and mechanical strength of thermally modified woods was observed, while specific gravity did not significantly change for either of the species studied. The best results of decrease of wettability were found in low temperatures, while dimensional stability increased as a function of temperature of exposure in oven. The highest loss of mechanical strength was observed at 240°C for both species.
