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Nanocomposites based on components from nature, which can be recycled are of great interest in new materials for sustainable development. The range of properties of nacre-inspired hybrids of 1D cellulose and 2D clay platelets are investigated in nanocomposites with improved nanoparticle dispersion in the starting hydrocolloid mixture. Films with a wide range of compositions are prepared by capillary force assisted physical assembly (vacuum-assisted filtration) of TEMPO-oxidized cellulose nanofibers (TOCN) reinforced by exfoliated nanoclays of three different aspect ratios: saponite, montmorillonite and mica. X-ray diffraction and transmission electron micrographs show almost monolayer dispersion of saponite and montmorillonite and high orientation parallel to the film surface. Films exhibit ultimate strength up to 573 MPa. Young's modulus exceeds 38 GPa even at high MTM contents (40-80 vol%). Optical transmittance, UV-shielding, thermal shielding and fire-retardant properties are measured, found to be very good and are sensitive to the 2D nanoplatelet dispersion., (Copyright © 2021. Published by Elsevier Ltd.)

Cellulose from wood fibers can be modified for use in flame-retardant composites as an alternative to halogen-based compounds. For this purpose, sulfite dissolving pulp fibers have been chemically modified by phosphorylation, and the resulting material has been used to prepare cellulose nanofibrils (CNF) that have a width of approximately 3 nm. The phosphorylation was achieved using (NH4)2HPO4 in the presence of urea, and the degree of substitution by phosphorus was determined by X-ray photoelectron spectroscopy, conductometric titration, and nuclear magnetic resonance spectroscopy. The presence of phosphate groups in the structure of CNF has been found to noticeably improve the flame retardancy of this material. The nanopaper sheets prepared from phosphorylated CNF showed self-extinguishing properties after consecutive applications of a methane flame for 3 s and did not ignite under a heat flux of 35 kW/m2, as shown by flammability and cone calorimetry measurements, respectively.

The toxicity of the most efficient fire retardant additives is a major problem for polymeric materials. Cellulose nanofiber (CNF)/clay nanocomposites, with unique brick-and-mortar structure and prepared by simple filtration, are characterized from the morphological point of view by scanning electron microscopy and X-ray diffraction. These nanocomposites have superior fire protection properties to other clay nanocomposites and fiber composites. The corresponding mechanisms are evaluated in terms of flammability (reaction to a flame) and cone calorimetry (exposure to heat flux). These two tests provide a wide spectrum characterization of fire protection properties in CNF/montmorrilonite (MTM) materials. The morphology of the collected residues after flammability testing is investigated. In addition, thermal and thermo-oxidative stability are evaluated by thermogravimetric analyses performed in inert (nitrogen) and oxidative (air) atmospheres. Physical and chemical mechanisms are identified and related to the unique nanostructure and its low thermal conductivity, high gas barrier properties and CNF/MTM interactions for char formation.

Graphical abstract Highlights • Chitosan and phosphorylated cellulose nanofibrils are layer-by-layer assembled. • The assembly produces an exoskeleton on the complex structure of flexible foams. • Intermolecular ionic interactions result in impressive mechanical properties. • The coating prevents foam collapsing and reduces heat release rates. • Unique compositional and structural features result in synergistic interactions. Abstract The layer-by-layer (LbL) assembly of chitosan (CH) and phosphorylated cellulose nanofibrils (P-CNF) is presented as a novel, sustainable and efficient fire protection system for polyurethane foams. The assembly yields a linearly growing coating where P-CNF is the main component and is embedded in a continuous CH matrix. This CH/P-CNF system homogenously coats the complex 3D structure of the foam producing a nano-exoskeleton that displays excellent mechanical properties increasing the modulus of the foam while maintaining its ability of being cyclically deformed. During combustion the CH/P-CNF exoskeleton efficiently prevents foam collapse and suppresses melt dripping while reducing the heat release rate peak by 31% with only 8% of added weight. The coating behavior during combustion is investigated and correlated to the observed performances. Physical and chemical mechanisms are identified and related to the unique composition and structure of the coating imparted by the LbL assembly. [ABSTRACT FROM AUTHOR]

Wood is one of the most sustainable, esthetically pleasing and environmentally benign engineering materials, and is often used in structures found in buildings. Unfortunately, the fire hazards related to wood are limiting its application. The use of transparent cellulose nanofiber (CNF)/clay nanocomposites, with unique brick-and-mortar structure, is proposed as a sustainable and efficient fire protection coating for wood. Fire performance was assessed by cone calorimetry. When exposed to the typical 35 kW/m² heat flux of developing fires, the time to ignition of coated wood samples increased up to about 4 1/2 min, while the maximum average rate of heat emission (MARHE) was decreased by 46% thus significantly reducing the potential fire threat from wood structures. [ABSTRACT FROM AUTHOR]

Nanostructured materials are difficult to prepare rapidly and at large scale. Melt-processed polymer-clay nanocomposites are an exception, but the clay content is typically below 5 wt%. An approach for manufacturing of microfibrillated cellulose (MFC)/kaolinite nanocomposites is here demonstrated in pilot-scale by continuous production of hybrid nanopaper structures with thickness of around 100 μm. The colloidal nature of MFC suspensions disintegrated from chemical wood fiber pulp offers the possibility to add kaolinite clay platelet particles of nanoscale thickness. For initial lab scale optimization purposes, nanocomposite processing (dewatering, small particle retention etc) and characterization (mechanical properties, density etc) were investigated using a sheet former (Rapid Köthen). This was followed by a continuous fabrication of composite paper structures using a pilot-scale web former. Nanocomposite morphology was assessed by scanning electron microscopy (SEM). Mechanical properties were measured in uniaxial tension. The fire retardancy was evaluated by cone calorimetry. Inorganic hybrid composites with high content of in-plane oriented nanocellulose, nanoclay and wood fibers were successfully produced at pilot scale. Potential applications include fire retardant paperboard for semi structural applications and as reinforcement mats in molded thermoset biocomposites. [ABSTRACT FROM AUTHOR]