Hydrangea‐Inspired Multi‐Scale Hybrids: Rational In Situ Assembly of Nickel Phyllosilicates on Polyphosphazene Microspheres to Fabricate Highly Robust, Toughened and Wear‐Resistant Epoxy Composites

ABSTRACT Epoxy resin (EP) is widely used in machinery and electronics but suffers from marked brittleness and poor wear resistance, which limits its further application under high‐speed and heavy‐load conditions. To address this issue, hydrangea‐inspired multi‐scale hybrid particles were rationally designed, with polyphosphazene microspheres (PZM) serving as the substrate and nickel phyllosilicates (NiPS) nanosheets as the decorations. The as‐synthesized multi‐scale PZM@NiPS hybrids, combining the organic flexibility of PZM and the inorganic rigidity of NiPS, were incorporated into EP matrix at various mass fractions to fabricate a series of composites. Results indicate that the decorated inorganic nanosheets endow PZM@NiPS with a significantly rough surface, contributing to well‐bonded interfaces and homogeneous dispersion; these features collectively enhance the mechanical performance of EP/PZM@NiPS composites. When 0.5 wt.% PZM@NiPS is added, the tensile strength, fracture elongation and fracture energy increase by 7.92%, 29.8%, and 180.2%, respectively; however, Shore D hardness increases steadily with PZM@NiPS content. Wet‐sliding tests confirm that PZM@NiPS plays a significant positive role in improving wear resistance, and the minimum wear rate of 2.19 × 10 ⁻⁶ mm ³ /Nm is achieved at a filler content of 1 wt.%, which is a significant reduction of approximately 48.18% compared with pure resin. Finally, the wear mechanism of the EP/PZM@NiPS composites is proposed based on detailed characterization and analysis. This work provides a promising “three‐in‐one” strategy that enables polymer composites to maintain high hardness while avoiding increased brittleness, thereby offering a novel pathway for the development and application of high‐performance polymer‐based friction materials suitable for harsh service environments.