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The transesterification of cellulose with vinyl esters in ionic liquid media is suggested as a prospective environmentally friendly alternative to conventional esterification. In this study, various long-chain cellulose esters (laurate, myristate, palmitate, and stearate) with a degree of substitution (DS) up to 1.8 have been synthesized in novel distillable ionic liquid, [mTBNH][OAC]. This IL has high dissolving power towards cellulose, which can improve homogeneous transesterification. Additionally, [mTBNH][OAC] has durability towards recycling and can be regenerated and re-used again for the next cycles of esterification. DMSO is used as a co-solvent because of its ability to speed up mass transport due to lower solvent viscosity. The optimization of the reaction parameters, such as co-solvent content, temperature (20-80 °C), reaction time (1-5 h), and a molar ratio of reactants (1-5 eq. AGU) is reported. It was found that within studied reaction conditions, DS increases with increasing reaction time, temperature, and added vinyl esters. Structure analysis using FTIR, 1H, and 13C NMR after acylation revealed the introduction of the alkyl chains into cellulose for all studied samples. The results also suggested that the substitution order of the OH group is C7-O6 > C7-O2 > C7-O3. Unique, complex thermal and rheological investigation of the cellulose esters shows the growth of an amorphous phase upon the degree of substitution. At the same time, the homogeneous substitution of cellulose with acyl chains increases the melt viscosity of a material. Internal plasticization in cellulose esters was found to be the mechanism for the melt processing of the material. Long-chain cellulose esters show the potential to replace commonly used externally plasticized cellulose derivatives.
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This article investigates the effects of combining a novel protic ionic liquid-based fire retardant (FR) with alkalized hemp fiber. A pivotal importance of this study refers to the hydrophilic properties and limits regarding poor thermal resistance of green composites where standard guidelines for fire risks are crucial. Although it is well-studied that alkalization is essential for green composite's moisture and mechanical durability, research on the flammability of such a combined treatment for natural fiber-reinforced biopolymer composites is lacking. The alkaline treatment used in the current study follows a process already studied as optimal, particularly for the selected hemp fiber. The fire performance was examined using a bench scale approach based on self and piloted ignition from cone calorimeter tests. The result from the Fourier-transform infrared analysis of the hemp fiber confirms phosphorylation following the fire-retardant treatment, which was visible from the morphological examination with scanning electron microscope. The presence of FR in the composites led to impactful moisture sorption. However, the FR composites demonstrated an enhanced response to fire, indicating potential use as a Class B standard for building construction, and hazard level 3 (HL3) classification as an interior material in vehicles, provided the problem of high emission of smoke is mitigated.
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Thermoplastic cellulose esters are promising materials for bioplastic packaging. For that usage, it is important to understand their mechanical and surface wettability properties. In this study, a series of cellulose esters are prepared, such as laurate, myristate, palmitate, and stearate. The aim of the study is to investigate the tensile and surface wettability properties of the synthesized cellulose fatty acid esters to understand their suitability as a bioplastic packaging material. Cellulose fatty acid esters are first synthesized from microcrystalline cellulose (MCC), then dissolved in pyridine solution, and after the solvent cast into thin films. The cellulose fatty acid ester acylation process is characterized by the FTIR method. Cellulose esters hydrophobicity is evaluated with contact angle measurements. The mechanical properties of the films are tested with the tensile test. For all the synthesized films, FTIR provides clear evidence of acylation by showing the presence of characteristic peaks. Films' mechanical properties are comparable to those of generally used plastics such as LDPE and HDPE. Furthermore, it appears that with an increase in the side-chain length, the water barrier properties showed improvement. These results show that they could potentially be suitable materials for films and packaging materials.
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This research investigates an effective alkali (NaOH) treatment and fire-retardant coating to produce biocomposites from frost-retted hemp fiber and PLA. The fiber surface treatment with various NaOH concentrations was investigated throughout a range of soaking times. The results show that the extracted non-cellulosic fiber content increases with treatment duration and NaOH concentration, while the fraction of targeted components removed remains nearly unchanged after soaking for 1, 2, and 4 h with a 5 wt.% NaOH solution. At the composite level, the treatment with 5 wt.% NaOH solution for 1 h emerged as the most efficient, with tensile strength, Young's modulus, flexural strength, and flexural modulus of 89.6 MPa, 9.1 GPa, 121.6 MPa, and 9.6 GPa, respectively, using 30 wt.% fibrous reinforcement. The fire performance of the examined batches of biocomposites improved significantly with the novel fire-retardant (Palonot F1) coating. However, the tensile strength notably decreased, while the flexural properties showed only a slight reduction. In most cases, the biocomposites with the alkali-treated hemp fiber had delayed ignition during the 5 min exposure to the cone heater. The findings in this work contribute to studies that will be required to give design guidelines for sustainable building options.
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The authors wish to make the following two corrections to this paper [...].
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The effects of surface pretreatment (water and alkali) and modification with silane on moisture sorption, water resistance, and reaction to fire of hemp fiber reinforced polylactic acid (PLA) composites at two fiber loading contents (30 and 50 wt.%) are investigated in this work. Moisture adsorption was evaluated at 30, 50, 75 and 95% relative humidity, and water resistance was determined after a 28-day immersion period. The cone calorimetry technique was used to investigate response to fire. The fiber surface treatment resulted in the removal of cell wall components, which increased fiber individualization and homogeneity as shown in scanning microscopic pictures of the composite cross-section. Although the improved fiber/matrix bonding increased the composite's water resistance, the different fiber treatments generated equal moisture adsorption results for the 30 wt.% reinforced composites. Overall, increasing the fiber amount from 30 to 50 wt.% increased the composite sensitivity to moisture/water, mainly due to the availability of more hydroxyl groups and to the development of a higher pore volume, but fire protection improved due to a reduction in the rate of thermal degradation induced by the reduced PLA content. The new Oswin's model predicted the composite adsorption isotherm well. The 30 wt.% alkali and silane treated hemp fiber composite had the lowest overall adsorption (9%) while the 50 wt.% variant produced the highest ignition temperature (181 ± 18 °C).
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This study investigated the effect of hemp fiber pretreatments (water and sodium hydroxide) combined with silane treatment, first on the fiber properties (microscale) and then on polylactide (PLA) composite properties (macroscale). At the microscale, Fourier transform infrared, thermogravimetric analysis, and scanning electron microscopy investigations highlighted structural alterations in the fibers, with the removal of targeted components and rearrangement in the cell wall. These structural changes influenced unitary fiber properties. At the macroscale, both pretreatments increased the composites' tensile properties, despite their negative impact on fiber performance. Additionally, silane treatment improved composite performance thanks to higher performance of the fibers themselves and improved fiber compatibility with the PLA matrix brought on by the silane couplings. PLA composites reinforced by 30 wt.% alkali and silane treated hemp fibers exhibited the highest tensile strength (62 MPa), flexural strength (113 MPa), and Young's modulus (7.6 GPa). Overall, the paper demonstrates the applicability of locally grown, frost-retted hemp fibers for the development of bio-based composites with low density (1.13 to 1.23 g cm-3).
