Hydrogel-based anti-icing coatings have attracted increasing interest due to their intrinsic softness and hydration-mediated icephobicity; however, simultaneously achieving long-term antifreezing stability, low ice adhesion, mechanical robustness, wear resistance, and self-healing capability remains a critical challenge. This study reports a multifunctional anti-icing hydrogel coating featuring a hierarchically regulated water state and a dynamically adaptive polymer network, enabled by the synergistic coupling of ionic coordination, zwitterionic hydration, and phase-separated fluoropolymer reinforcement. The hydrogel network is constructed by copolymerizing acrylamide (AAm), acrylic acid (AA), and the zwitterionic monomer 3-(dimethyl-(2-methacryloyloxyethyl) ammonium propane sulfonate) (DMAPS) with N,N'methylenebisacrylamide (MBAA) as a crosslinker and I2959 as a photoinitiator. Zinc chloride (ZnCl2) and glycerol are incorporated as dual antifreezing regulators to modulate water-polymer interactions and introduce reversible ionic coordination and hydrogen-bonding networks. To further enhance structural stability and mechanical durability, polyvinylidene fluoride (PVDF) dissolved in N-methyl-2-pyrrolidone (NMP) is introduced via a cloud-point-induced phase separation strategy, generating an interpenetrated hydrogel-PVDF hybrid architecture. The precursor solutions are deposited by low-speed spin coating and subject to controlled pre-cooling at -15 ℃ and -25 ℃ under 60% relative humidity to directly evaluate the antifreezing behavior during gel formation. SEM, FTIR, Raman, AFM, DSC and other structural characterizations are systematically carried out, and the functional properties of the materials are evaluated by freezing delay test, ice adhesion test, tensile test, self-healing experiment and wear resistance cycle. Differential scanning calorimetry (DSC) reveals a pronounced suppression of the freezing temperature and a significant increase in non-freezable bound water content after the introduction of ZnCl2, glycerol, and DMAPS. The asymmetric enthalpy evolution during cooling and heating cycles further indicates restricted ice nucleation and inhibited crystal growth, demonstrating that the antifreezing performance originates from regulated water confinement rather than simple freezing-point depression. Raman spectroscopy confirms strengthened hydrogen-bond interactions and altered water molecular environments, as evidenced by the redistribution of O—H stretching bands and the emergence of characteristic PVDF β-phase vibrations, indicating effective phase separation and interfacial coupling between the hydrogel matrix and PVDF domains. Atomic force microscopy (AFM) mapping shows that the incorporation of ZnCl2 and glycerol significantly reduces local modulus heterogeneity and enhances energy dissipation at the microscale, while preserving a compliant surface layer favorable for stress relaxation at the ice-gel interface. SEM observations further reveal a heterogeneous but well-integrated microstructure, where PVDF-rich domains act as mechanically reinforcing skeletons embedded within the hydrated polymer network, effectively suppressing crack propagation and structural collapse during freeze-thaw cycling. The obtained composite coating achieves a 10-15 min droplet freezing delay at -20 ℃, showing a significant anti-frosting ability; very low ice adhesion is maintained in the range of -20 to -45 ℃, and stable de-icing performance can be maintained after 150 wear cycles. In terms of mechanics, the coating has an elongation at break of about 500% and a tensile strength of more than 11 kPa, as well as considerable self-healing ability and structural durability. The synergistic effect of the Zn2+-hydrogen bond dynamic network, the glycerol-induced weak lubricating layer and the PVDF hydrophobic microphase promotes the enrichment of non-frozen water and the formation of a quasi-liquid lubricating layer (QLL), so that the obtained composite hydrogel has the characteristics of frost resistance, anti-icing and wear resistance. The multi-scale collaborative construction strategy proposed in this study provides a new material system and design idea for the development of high-performance and durable anti-icing coatings, and has broad potential for low-temperature engineering applications.
Key words
anti-icing coating /
composite hydrogel /
Zn2+ coordination network /
PVDF hydrophobic microphase
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Funding
The National Natural Science Foundation of China (52266001); The Science and Technology Research Project of Henan Province (262102321183; 252102320373); Natural Science Foundation of Henan Province (262300420069); Doctoral Fund Project of Henan Polytechnic University (B2021-37)
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