目的 构筑一种兼具抗冻性、弱冰黏附性与耐磨性的多功能复合型防冰涂层,并揭示ZnCl2、甘油与 PVDF协同调控水凝胶界面的行为机理。方法 以AAm/DMAPS/AA构建水凝胶骨架,通过Zn2+-羧基/羟基配位与多重氢键构筑动态网络,辅以甘油调控结合水结构以提升低温润滑性,并采用云滴法将 NMP 溶解的PVDF均匀嵌入凝胶中形成疏水微相。系统开展SEM、FTIR、拉曼、AFM、DSC等结构表征,并通过冻结延迟测试、冰黏附力测试、拉伸测试、自修复实验和耐磨循环评估材料的功能性能。结果 所制备复合涂层在-20 ℃实现10~15 min的液滴冻结延迟,表现出显著抗结霜能力;在-20至-45 ℃区间保持极低的冰黏附力,且经历150次磨损循环后仍能保持稳定脱冰性能;涂层具有约450%的断裂伸长率和超过750 kPa的拉伸强度,同时具备良好的自修复能力与结构耐久性。结论 Zn2+-氢键动态网络、甘油诱导的弱润滑层与PVDF疏水微相的协同作用共同促进不可冻结水的富集与准液体润滑层（QLL）的形成,使所得复合水凝胶兼具抗冻、防冰和耐磨特性。本文提出的多尺度协同构筑策略为开发高性能、耐久型防冰涂层提供了新的材料体系与设计思路,并具有广泛的低温工程应用潜力。
Abstract
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.
关键词
防冰涂层 /
复合水凝胶 /
Zn2+配位网络 /
PVDF疏水微相
Key words
anti-icing coating /
composite hydrogel /
Zn2+ coordination network /
PVDF hydrophobic microphase
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基金
国家自然科学基金（52266001）; 河南省科技攻关项目（262102321183,252102320373）; 河南省自然科学基金（262300420069）; 河南理工大学博士基金资助项目（B2021-37）
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