Sliding water droplets corrode Teflon-coated metal

Water droplets sliding across solid surfaces can acquire electric potentials of thousands of volts and thereby corrode non-conductive surfaces on metals when they discharge. That is the conclusion of researchers in Germany who say that the poorly-understood phenomenon warrants further investigation to help prevent corrosion of vulnerable outdoor equipment and cultural heritage sites.

Metal corrosion by water droplets is a serious economic and safety issue, and prevention begins with the proper understanding of the relevant processes. Conventional wisdom is that most corrosion is caused by a combination of physical abrasion by the motion of the droplets and chemical degradation from natural acids and anthropogenic pollutants in the water. The notion that electrochemistry might play a significant role in corrosion had not been seriously considered, says physical chemist Hans-Jürgen Butt of the Max Planck Institute for Polymer Research in Mainz.

Part of the reason, he believes, is that, until relatively recently, it was thought that the triboelectric effect (electrically charging objects by rubbing them together) did not work in liquids. “If you have a solid and you rub another insulating solid against it you get electron transfer – I think this has been known for more than 2500 years” he says. However, this relies on atomic-scale roughness of the surface to concentrate charge at specific points where bonds can be broken – and fluids cannot, by definition, be rough.

“If you take a water droplet and let it slide there is some mechanical force from surface tension, but that’s much too low,” says Butt. “There is no way you could generate enough energy locally to pick up an electron or to put an electron or an ion from the water onto the surface.” In the past 10 years, however, it has become increasingly clear that sliding droplets do become highly charged.

Sloping surfaces

In their present work Butt and colleagues deposited water droplets onto copper surfaces covered with 60 nm of Teflon. When they dropped droplets straight onto the surface, they observed no corrosion. They then deposited droplets first onto a variety of other sloped insulating surfaces such as plant leaves, PVC construction boards and the perfluorooctadecyltrichlorosilane (PFOTS) hydrophobic coating often used on window glass. The droplets ran down these surfaces and then fell onto the Teflon-coated copper. After around 3000 droplet impacts, atomic force microscopy and confocal microscopy revealed evidence that the droplets had corroded both the coating and the underlying copper.

The researchers believe that the droplets become positively charged as they slide down the sloping surface. As they fall onto the coating, the potential difference between the copper and the underlying copper can exceed 1 kV. This is greater than the dielectric breakdown strength of the coating, causing the droplet to discharge. This damages the coating and leaves the underlying metal vulnerable to further oxidation.

To test their hypothesis, the researchers measured charge movement within the copper surface, showing that negative charge flowed towards droplets dripping off insulating surfaces. They also used high-speed cameras to show that, whereas a drop deposited directly retained its spherical shape before impact, a dripping drop was drawn into a cone shape, producing a tip of positive charge that would increase its corrosive capacity.

Uncertain consequences

The practical implications of this are unclear. “Technical coatings on cars, ships etc. are typically 100 microns and thicker, so the process we describe is probably not of direct relevance,”says Butt. However, the phenomenon could be involved in the degradation of monuments and other outdoor historical objects. “We have evidence that surfaces change their properties when you slide charges over them, but the real consequences are not yet known,” explains Butt.

He says his own group is most clearly focused on understanding the fundamental physics involved. “We still don’t know why the heck there is such a charge separation: it’s energetically unfavourable, it should not happen, but it happens.” he says. “The one effect we describe here is, in a way, pretty trivial – everyone knows that if you have a high potential and it’s somehow grounded there is a breakthrough – but what happens at the surface with this deposited charge is not clear.”

Materials scientist Zhong Lin Wang of Georgia Institute of Technology in Atlanta was one of the first researchers to discover the triboelectric effect in liquids, and helped to develop the triboelectric nanogenerator used to quantify it. “The transferred electrons can be kicked back to the water solution, resulting in chemical reaction at the vicinity surface. This process, called contact-electro-catalysis, was first proposed in 2022, and is now an active field of research in chemistry, materials and environmental science.” He says. “[Butt and colleagues] show that the electrons transferred from the water droplet can ‘break’ the surface coating layer and lead to local oxidation. This is an interesting discovery.”

The research is described in Nature.

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