Synchronous modification of ZIF-67 with cyclomatrix polyphosphazene coating for efficient flame retardancy and mechanical reinforcement of epoxy resin.

Cyclomatrix polyphosphazenes have attracted widespread attention in the field of polymer flame retardancy. Nevertheless, the optimal manifestation of their distinctive structural attributes and flame-retardant properties necessitates a judicious selection of condensation monomers and synergistic templates during the fabrication of polyphosphazene flame retardants. In our previous studies, it was discovered that when ZIF-67 is functionalized with polyphosphazene, the by-product HCl from phosphazene polycondensation causes etching on ZIF-67. Based on this "synchronous etching" effect, a series of hybrid materials comprising cyclomatrix polyphosphazene and ZIF-67, denoted as ZIF-67@PDS (PDS, poly-(cyclotriphosphazene-co-4,4'-diaminodiphenyl sulfone)), ZIF-67@PBS (PBS, poly-(cyclotriphosphazene-co-Bisphenol A)), and ZIF-67@PZS (PZS, poly-(cyclotriphosphazene-co-4,4'-sulfonyldiphenol)), was synthesized utilizing DDS (4,4'-diaminodiphenyl sulfone), BPA (Bisphenol A), and BPS (4,4'-sulfonyldiphenol) monomers as precursors, respectively. Upon the incorporation of 2.0 wt.% of ZIF-67@PDS, ZIF-67@PBS, and ZIF-67@PZS, the flame retardant and mechanical characteristics of EP composites exhibited marked enhancement. The unique structural characteristics of hybrid and the synergistic effects of Co-P-N contribute to the improvement of comprehensive properties. Compared with pure EP, EP/ZIF-67@PZS has the best enhancement effect, and its pHRR, THR, and TSP decreased by 34.0%, 30.0%, and 40.5%, respectively. In terms of mechanical strength, ZIF-67@PZS also increases the flexural strength of EP by 37.42%. Relying on the "synchronous etching" effect, this study explores and verifies the effective combination of ZIF-67 and different types of polyphosphazenes, and obtains a series of ZIF-67-derived cyclomatrix polyphosphazene hybrids with different morphologies and properties in one step. It provides a new idea and strategy for the simultaneous modification of polyphosphazene materials and the preparation of multifunctional flame retardants in the future.

Preserving the Cellular Tissue Structure of Maize Pith Though Dry Fractionation Processes: A Key Point to Use as Insulating Agro-Materials.

Plant biomass has various compositions and structures at different scales (from the component organs to their constitutive tissues) to support its functional properties. Recovering each part of the plant without damaging its structure poses a challenge to preserving its original properties for differential dedicated end uses, and considerably increases its added value. In this work, an original combination of grinding based on shearing stress and separation based on particle size and density was successfully used to sort rind (65% w/w) and pith (35% w/w) from maize stem internodes. More than 97% of the rind was isolated. The pith alveolar structure was well preserved in coarse particles, making them suitable for insulation bio-based composite materials, a promising alternative to conventional nonbiodegradable insulation panels. Boards produced from the dry fractionated pith exhibited thermal conductivities like those produced from hand dissected pith, with values equal to 0.037 W·mK-1 and 0.039 W·mK-1, respectively. In the finest fraction (particle size <1 mm), the pith vascular bundles (around 300-400 µm in diameter) were dissociated from parenchyma cells and successfully isolated using a cutting-edge electrostatic separator. Their structures, which provide the plant structural support, make them potentially valuable for reinforcement in composite materials.