Comment On "Bioinspired Reversible Switch Between Underwater Superoleophobicity/Superaerophobicity And Oleophilicity/Uaerophilicity And Improved Antireflective Property On The Nanosecond Laser-Ablated Superhydrophobic Titanium Surfaces"

ACS APPLIED MATERIALS & INTERFACES(2021)

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Abstract
Laser-textured surfaces enabling reversible wettability switching and improved optical properties are gaining importance in cutting-edge applications, including self-cleaning interfaces, tunable optical lenses, microfluidics, and lab-on-chip systems. Fabrication of such surfaces by combining nanosecond-laser texturing and low-temperature annealing of titanium Ti-6Al-4V alloy was demonstrated by Lian et al. in ACS Appl. Mater. Inter. 2020, 12 (5), 6573-6580. However, it is difficult to agree with (i) their contradictory explanation of the wettability transition due to low-temperature annealing and (ii) their theoretical description of the optical behavior of the laser-textured titanium surface. This comment provides an alternative view-supported by both experimental results and theoretical investigation-on how the results by Lian et al. could be interpreted more correctly. The annealing experiments clarify that controlled contamination is crucial in obtaining consistent surface wettability alterations after low-temperature annealing. Annealing of laser-textured titanium at 100 degrees C in contaminated and contaminant-free furnaces leads to completely different wettability transitions. Analysis of the surface chemistry by XPS and ToF-SIMS reveals that (usually overlooked) contamination with hydrophobic polydimethylsiloxane (PDMS) may arise from the silicone components of the furnace. In this case, a homogeneous thin PDMS film over the entire surface results in water repellency (contact angle of 161 degrees and roll-off angle of 15 degrees). In contrast, annealing under the same conditions but in a contaminant-free furnace preserves the initial superhydrophilicity, whereas the annealing at 350 degrees C turns the hydrophobicity "off". The theoretical calculations of optical properties demonstrate that the laser-induced oxide layer formed during the laser texturing significantly influences the surface optical behavior. Consequently, the interference of light reflected by the air-oxide and the oxide-metal interfaces should not be neglected and enables several advanced approaches to exploit such optical properties.
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Key words
laser surface engineering, wettability, laser oxidation, thin-film interference, volatile organic compounds, polydimethylsiloxane, surface contamination
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