The duplex treatments of metal surfaces combining laser‐assisted functionalization and chemical modification attract a growing interest in view of better control of functional properties such as wettability. Patterned titanium oxides layers of different nature and roughness are produced in ambient atmosphere on a titanium surface using a nanosecond 532 nm Nd:YAG laser. Standalone lines and hatched surfaces obtained with different laser parameters are characterized by scanning electronic microscopy coupled with EDS analysis, micro‐Raman, XRD and X‐ray photoelectron spectroscopy (XPS). A set of surfaces having featureless and saw‐tooth morphologies of different roughnesses is modified with octylphosphonic acid (OPA). The effect of surface roughness on the efficiency of OPA grafting is investigated using XPS. It is found that the organic load on the chemically modified surfaces increases with surface roughness. The apparent thickness of the OPA layers is estimated using a standard uniform overlap model and considering the correction due to the corrugated appearance of the laser‐treated surfaces. The wetting properties of the surfaces before and after chemical modification are compared. The laser‐treated surfaces show superhydrophilic behavior consistent with Wenzel model. On the other hand, the chemically modified surfaces demonstrate a strong increase in hydrophobicity along with the roughness increase, in agreement with the Cassie–Baxter model.
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