Tree Periderm‐Inspired Roughening via a Sacrificial Surface Layer for Ultradurable Multifunctional Protective Aramid Fabrics

ABSTRACT Fire, water, and ice pose persistent challenges to personal protective materials used in harsh environments. Integrating water repellency, ice resistance, antimicrobial activity, and flame retardancy into a single fabric remains particularly difficult for chemically inert aramid fabrics widely employed in firefighting protective clothing. Here, we develop a tree periderm‐inspired sacrificial surface roughening strategy for the fabrication of ultradurable multifunctional aramid fabrics. Through a proton donor‐assisted deprotonation process, surface protons are selectively extracted from aramid fibers, triggering controlled molecular dissociation and hierarchical surface reconstruction. This process generates a rough sacrificial outer layer supported by a mechanically robust inner core, analogous to the protective architecture of natural tree periderm. The resulting structure minimizes liquid‐solid contact and endows the fabric with ultradurable superhydrophobicity and icephobicity, while preserving the intrinsic flame retardancy, breathability, and mechanical integrity of the aramid substrate. The treated fabric maintains its functionality after 500 h of UV irradiation, 500 h of thermal aging at 200°C, and 1000 cycles of abrasion and tape‐peeling tests. In addition, it exhibits > 99% antimicrobial efficiency against E. coli , S. aureus , and C. albicans , even after 400 laundering cycles. This work establishes a bioinspired surface‐engineering strategy for creating ultradurable multifunctional protective textiles for extreme environments.