Self-Assembled Monolayers of a Fluorinated Phosphonic Acid as a Protective Coating on Aluminum

Molecules. 2024 Feb 3;29(3):706. doi: 10.3390/molecules29030706.

Abstract

Aluminum (Al) placed in hot water (HW) at 90 °C is roughened due to its reaction with water, forming Al hydroxide and Al oxide, as well as releasing hydrogen gas. The roughened surface is thus hydrophilic and possesses a hugely increased surface area, which can be useful in applications requiring hydrophilicity and increased surface area, such as atmospheric moisture harvesting. On the other hand, when using HW to roughen specified areas of an Al substrate, ways to protect the other areas from HW attacks are necessary. We demonstrated that self-assembled monolayers (SAMs) of a fluorinated phosphonic acid (FPA, CF3(CF2)13(CH2)2P(=O)(OH)2) derivatized on the native oxide of an Al film protected the underneath metal substrate from HW attack. The intact wettability and surface morphology of FPA-derivatized Al subjected to HW treatment were examined using contact angle measurement, and scanning electron microscopy and atomic force microscopy, respectively. Moreover, the surface and interface chemistry of FPA-derivatized Al before and after HW treatment were investigated by time-of-flight secondary ion mass spectrometry (ToF-SIMS), verifying that the FPA SAMs were intact upon HW treatment. The ToF-SIMS results therefore explained, on the molecular level, why HW treatment did not affect the underneath Al at all. FPA derivatization is thus expected to be developed as a patterning method for the formation of hydrophilic and hydrophobic areas on Al when combined with HW treatment.

Keywords: covalent bonding; fluorinated phosphonic acid (FPA); hot water (HW) treatment; native oxide layer of aluminum; self-assembled monolayers (SAMs); surface and interface chemistry; surface morphology; surface roughening; time-of-flight secondary ion mass spectrometry (ToF-SIMS); water contact angle (CA).