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.

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 (T_1max) 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.

Environmentally benign layer-by-layer (LbL) deposition was used to obtain flame-retardant and antimicrobial cotton. Cotton was coated with 8, 10, and 12 phytic acid (PA) and chitosan (CH)-urea bilayers (BL) and then immersed into copper (II) sulfate (CuSO₄) solution. Our findings were that 12 BL of PA/CH-urea + Cu²⁺ were able to stop flame on cotton during vertical flammability testing (VFT) with a limiting oxygen index (LOI) value of 26%. Microscale combustion calorimeter (MCC) data showed a reduction of peak heat release rates (pHRR) of more than 61%, while the reduction of total heat release (THR) was more than 54%, relative to untreated cotton. TG-IR analysis of 12 BL-treated cotton showed the release of water, methane, carbon dioxide, carbon monoxide, and aldehydes, while by adding Cu²⁺ ions, the treated cotton produces a lower amount of methane. Treated cotton also showed no levoglucosan. The intumescent behavior of the treatment was indicated by the bubbled structure of the post-burn char. Antibacterial testing showed a 100% reduction of Klebsiella pneumoniae and Staphylococcus aureus. In this study, cotton was successfully functionalized with a multifunctional ecologically benign flame-retardant and antibacterial nanocoating, by means of LbL deposition.

In an effort to impart antimicrobial behavior to cotton using renewable and environmentally benign components, fabric was treated using layer-by-layer (LbL) assembly. Alternating layers of phytic acid (PA) and chitosan (CH) were deposited from water. Cotton coated with four and eight bilayers (BLs) of anionic PA and cationic CH, with and without adding copper (II) sulfate (CuSO₄) into the CH solution, was evaluated in accordance with the American Association of Textile Chemists and Colorists (AATCC) TM 100-2019 test method. Gram-positive Staphylococcus aureus and gram-negative Klebsiella pneumoniae were used to determine whether the addition of copper salt into a CH network improves antibacterial efficacy. The copper ions were successfully incorporated into the CH network formed using LbL assembly onto cotton fibers. The location of deposited copper ions was determined with electron microscopy. Just four BLs of PA/CH–copper (II) sulfate kill 100% of gram-positive and gram-negative bacteria and add only 5.2 wt% to the fabric. This nanocoating provides a unique opportunity to impart antibacterial behavior to textiles without harming the environment.