Designing Optimal Super-liquid-repellent Surfaces

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by Jack R. Panter (j.r.panter@durham.ac.uk) and Halim Kusumaatmaja (halim.kusumaatmaja@durham.ac.uk), both Durham University, UK

Superomniphobic surfaces efficiently shed all liquids. This makes them universal anti-fouling coatings with transformative potential in the food, packaging, and medical industries, as well as in lab-on-a-chip and water purification technologies. However, the complex surface structures required have posed considerable challenges to both experimental and theoretical analyses of their wetting properties, slowing the development of optimal designs for practical applications. In our article [1], we develop computational techniques to comprehensively survey three key wetting properties required for high operational performance, before simultaneously optimizing these properties to produce application-specific designs. We demonstrate this methodology by designing ideal surface textures for droplet microfluidics and sustainable water purification membranes.

The Doubly Reentrant Geometry

The so-called “doubly reentrant geometry” is at the frontier of superomniphobic design. This mushroom-shaped surface protrusion can suspend liquids on top of the structure over an air layer. This minimises interactions between the liquid and solid, so that liquids can be shed very easily from the surface. The overhanging cap means that even highly pressurised, highly wetting liquids can be suspended in this way. In order to manufacture such complex surface structures (the overhanging cap geometry is particularly challenging to achieve), a range of innovative fabrication techniques are beginning to be deployed, such as multi-step lithography, the fluidization of polymer micropillars, and 3D printing [2-5].

Despite recent advances in fabrication techniques, optimizing the surface design for real-world use remains a substantial challenge. In many applications, three wetting properties must be optimized: the contact angle hysteresis, a measure of liquid mobility; the minimum energy breakdown barrier, the ease in which liquid displaces the air layer and when superomniphobic properties are lost; and the critical pressure, the maximum maintainable liquid pressure on the surface. Each individual wetting property has a complex dependence on the structural design. It is not possible to design a surface texture which optimizes each property individually, as they are coupled antagonistically by structural parameters. Therefore, an optimal design is produced by considering all three properties simultaneously.

The doubly reentrant surface geometry couples the three key wetting properties antagonistically. These properties are: the contact angle hysteresis (top), minimum energy pathway to failure (left), and critical breakdown pressure (right). Optimal design can only be achieved through a simultaneous balance between all three. Copyright: Durham University
The doubly reentrant surface geometry couples the three key wetting properties antagonistically. These properties are: the contact angle hysteresis (top), minimum energy pathway to failure (left), and critical breakdown pressure (right). Optimal design can only be achieved through a simultaneous balance between all three. Copyright: Durham University

Our Approach

We overcome these challenges by first performing large-scale, systematic surveys of each wetting property across the structural parameter range, finding multiple competing mechanisms. We then develop new analytical models to describe these mechanisms, and test previously proposed models. From the critical pressure survey, we find that previous models grossly overestimate the distance the liquid sags underneath the cap, meaning previously fabricated surface structures were substantially taller (and mechanically weaker) than necessary. From the minimum energy barrier survey, we find doubly reentrant geometries are prone to failure through condensation, but also show how to counteract this.

Second, we combine the individual surveys to simultaneously optimize the surface texture. This optimization is also performed using a genetic algorithm, a method of evolutionary design, speeding up this process by up to 10,000×. We demonstrate the power of this strategy by designing structures which overcome the challenges faced by two emerging applications: surfaces enabling versatile digital microfluidics, and energy-efficient water purification via membrane distillation. Strikingly, the optimized doubly reentrant structure for water purification closely matches the natural occurrence of this surface on the skin of the springtail arthropod. Like the purification membrane, the springtail’s skin has adapted to allow gaseous exchange while resisting fouling by liquid contaminants.

Overall, the designs we produce are able to meet multiple wetting property requirements simultaneously, for optimum application performance. Looking to the future, we believe this versatile and efficient simulation strategy will be a powerful tool for the practical realization of structured surfaces with special wettability.

References

[1] J. R. Panter, Y. Gizaw & H. Kusumaatmaja, Sci. Adv. 5, eaav7328 (2019)

[2] X. Liu et al., Adv. Mater. 30, e1800103 (2018)

[3] J. Choi et al., ACS Nano 11, 7821 (2017)

[4] G.-T. Yun at al., Sci. Adv. 4, eaat4978 (2018)

[5] T. Liu, C.-J. Kim, Science 346, 1096 (2014)

Jack R. Panter (left) and Halim Kusumaatmaja from Durham University, UK. Copyright: authors
Jack R. Panter (left) and Halim Kusumaatmaja from Durham University, UK. Copyright: authors
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