Environmentally Friendly Method and Mechanism for Transforming the Hydrophobic Properties of Metals via Nanosecond Laser Processing

Nanosecond laser direct writing (NDLW) is an advanced surface processing technique that utilizes high-energy nanosecond pulsed lasers to induce localized modifications on metallic materials. Due to its ability to precisely control surface morphology through mechanisms such as laser ablation, photothermal, and photochemical reactions, NDLW has been widely adopted in the fabrication of microscale surface structures. When applied to polished metal substrates, NDLW typically results in a highly (super)hydrophilic surface due to the formation of oxides and increased surface roughness. However, these laser-induced surfaces can undergo further wettability transformation toward (super)hydrophobicity through post-treatment strategies that are environmentally friendly and free of chemical modifiers. In recent years, there has been growing interest in developing green, sustainable methods to regulate surface wettability, especially for applications in aerospace, biomedical engineering, and energy systems. These applications demand robust, durable, and multifunctional surface properties, including anti-icing, self-cleaning, antibacterial, and drag-reduction functionalities. Unlike traditional chemical modification methods that involve hazardous fluorinated compounds or silanes, emerging approaches focus on physically driven processes such as air exposure, thermal annealing, and secondary laser treatments to modify surface chemistry and energy without introducing environmental burdens. This paper provides a comprehensive overview of the theoretical basis of wettability, including classical models such as the Young, Wenzel, and Cassie-Baxter models, and elaborates on the role of surface roughness and surface energy in determining hydrophobic or hydrophilic behavior. Special attention is given to the mechanisms by which nanosecond laser processing induces micro / nano-hierarchical structures and alters surface states on metals such as titanium, aluminum, stainless steel, and copper. Subsequent to NDLW, environmental exposure often results in gradual absorption of low-surface-energy organic compounds from ambient air. This spontaneous aging process, albeit slow (often taking weeks), transforms laser-textured metal surfaces into superhydrophobic states, as confirmed by contact angle measurements and surface chemical analyses using XPS. To accelerate this transition, low-temperature annealing has been widely studied. Heating laser-treated samples in air at moderate temperatures (100–200 ℃) significantly shortens the hydrophilic-to-hydrophobic transition period by facilitating the decomposition and adsorption of airborne hydrocarbons and by reducing the concentration of polar hydroxyl groups on the surface. Another effective and scalable method involves secondary laser treatment. This technique enhances the complexity and dual-scale nature of the surface textures, leading to a more stable Cassie-Baxter state. Furthermore, advanced laser interference strategies, such as direct laser interference patterning (DLIP), can precisely fabricate periodic structures, improving water repellency and surface durability. Hybrid techniques like combining NDLW with ion implantation have demonstrated superior performance. For instance, post-laser carbon ion implantation not only modifies surface energy but also improves mechanical robustness and corrosion resistance, enabling the formation of long-lasting superhydrophobic surfaces suitable for harsh environments. The findings reviewed in this study demonstrate that nanosecond laser-based surface texturing, followed by eco-friendly post-treatments, offers a versatile and sustainable route to engineer functional metallic surfaces without relying on hazardous chemicals. The resulting superhydrophobic surfaces exhibit excellent durability, tunable wettability, and enhanced environmental compatibility. In conclusion, this work outlines the fundamental mechanisms, recent advancements, and technological trends in the field of laser-induced wettability engineering on metallic substrates. It highlights the synergy between laser-generated microstructures and environmentally benign surface modifications, providing a valuable reference for future research and industrial applications aimed at achieving high-performance and sustainable surface functionalities.