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A detailed review of recent developments of layer-by-layer (LbL) deposition as a promising approach to reduce flammability of the most widely used fibers (cotton, polyester, polyamide and their blends) is presented. LbL deposition is an emerging green technology, showing numerous advantages over current commercially available finishing processes due to the use of water as a solvent for a variety of active substances. For flame-retardant (FR) purposes, different ingredients are able to build oppositely charged layers at very low concentrations in water (e.g., small organic molecules and macromolecules from renewable sources, inorganic compounds, metallic or oxide colloids, etc.). Since the layers on a textile substrate are bonded with pH and ion-sensitive electrostatic forces, the greatest technological drawback of LbL deposition for FR finishing is its non-resistance to washing cycles. Several possibilities of laundering durability improvements by different pre-treatments, as well as post-treatments to form covalent bonds between the layers, are presented in this review.
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In this study, the natural dye was extracted from Spartium junceum L. (SJL) flowers and applied on cellulose (cotton) and protein (wool) fabric. Fabrics were pre-mordant with alum prior to the dyeing process. Considering the global requirements on zero waste and green policy, the dyeing process was intended to be as much as possible environmentally friendly but still effective. Therefore, mordant concentration was optimized due to the reduction of the negative impact. The efficiency of the dyeing process was investigated by examination of fabrics' color characteristics and colorfastness to washing properties. In this paper, we have proved that the extracted dye from Spartium junceum L. is an acidic dye (mordant dye) which is more applicable for the treatment of wool fabrics. In this paper, it was proved that phytochemicals responsible for coloring are part of the flavonoids group. The UV absorption spectra of extracted dye show 4 bands in the region of λmax 224, 268, 308 and 346 nm which are ascribed to bands characteristic for flavonoids. Wool fabric pre-mordant with 3% alum and dyed shows great chromatic (C*) properties where C* value is in a range from 47.76 for unwashed samples to 47.50 for samples after 5 washing cycles and color hue (h°) is in a range 82.13 for unwashed samples to 81.52 for samples after 5 washing cycles. The best result regarding the colorfastness properties is shown by the wool sample treated with 3% alum after 5 washing cycles (total difference in color (Delta E*) = 0.87). These results confirm that metal (Al) from alum mordant make strong chemical bonds with wool substrate and dye since Delta E* values decrease in comparison to Delta E* values of the cotton samples treated the same way. The results revealed it is possible to reduce the concentration of mordant up to 3% and obtain satisfactory results regarding the colorfastness. Nevertheless, future research will go in the direction of replacing synthetic mordant with a more environmentally friendly one.
RESUMO
This paper summarizes the results obtained in the course of the development of a specific group of biocomposites with high functionality of flame retardancy, which are environmentally acceptable at the same time. Conventional biocomposites have to be altered through different modifications, to be able to respond to the stringent standards and environmental requests of the circular economy. The most commonly produced types of biocomposites are those composed of a biodegradable PLA matrix and plant bast fibres. Despite of numerous positive properties of natural fibres, flammability of plant fibres is one of the most pronounced drawbacks for their wider usage in biocomposites production. Most recent novelties regarding the flame retardancy of nanocomposites are presented, with the accent on the agents of nanosize (nanofillers), which have been chosen as they have low or non-toxic environmental impact, but still offer enhanced flame retardant (FR) properties. The importance of a nanofiller's geometry and shape (e.g., nanodispersion of nanoclay) and increase in polymer viscosity, on flame retardancy has been stressed. Although metal oxydes are considered the most commonly used nanofillers there are numerous other possibilities presented within the paper. Combinations of clay based nanofillers with other nanosized or microsized FR agents can significantly improve the thermal stability and FR properties of nanocomposite materials. Further research is still needed on optimizing the parameters of FR compounds to meet numerous requirements, from the improvement of thermal and mechanical properties to the biodegradability of the composite products. Presented research initiatives provide genuine new opportunities for manufacturers, consumers and society as a whole to create a new class of bionanocomposite materials with added benefits of environmental improvement.
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Chemically bleached cotton fabric was treated with phytic acid (PA), chitosan (CH) and urea by means of layer-by-layer (LbL) deposition to impart flame retardant (FR) behavior using only benign and renewable molecules. Samples were treated with 8, 10, 12 and 15 bilayers (BL) of anionic PA and cationic CH, with urea mixed into the aqueous CH solution. Flammability was evaluated by measuring limiting oxygen index (LOI) and through vertical flame testing. LOI values are comparable to those obtained with commercial flame-retardant finishes, and applying 10 or more bilayers renders cotton self-extinguishing and able to pass the vertical flame test. Microscale combustion calorimeter (MCC) measurements show the average reduction of peak heat release rate (pHRR) of all treated fabrics of ~61% and the reduction of total heat release (THR) of ~74%, in comparison to untreated cotton. Decomposition temperatures peaks (T1max) measured by thermogravimetric analyzer (TG) decreased by approximately 62 °C, while an average residue at 650 °C is ~21% for 10 and more bilayers. Images of post-burn char indicate that PA/CH-urea treatment is intumescent. The ability to deposit such a safe and effective FR treatment, with relatively few layers, makes LbL an alternative to current commercial treatments.
RESUMO
Enzymatic modification, using a protease from Bacillus licheniformis (Subtilisin A), was carried out on polyamide 6.6 (PA6.6) fabric to make it more amenable to water-based nanocoatings used to impart electrical conductivity. The modified PA6.6 fibers exhibit a smoother surface, increased hydrophilicity due to more carboxyl and amino groups, and larger ζ-potential relative to unmodified polyamide. With its improved hydrophilicity and surface functionality, the modified textile is better able to accept a water-based nanocoating, composed of multiwalled carbon nanotubes (MWCNT) stabilized by sodium deoxycholate (DOC) and poly(diallyldimethylammonium chloride) (PDDA), deposited via layer-by-layer assembly. Relative to unmodified fabric, the enzymatically modified fibers exhibit lower sheet resistance as a function of PDDA/MWCNT-DOC bilayers deposited. This relatively green technique could be used to impart a variety of useful functionalities to otherwise difficult-to-treat synthetic fibers like polyamide.