How Things Get Wet

New Mathematical Formula Sets Wetting Theory Straight

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Understanding the precise interaction between liquids and surfaces is important for a number of areas, including the chemical industry and new nanotechnologies.

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Fundamental mathematical research exposes the limits of nature in controlling molecules on a surface . Recent advances have allowed scientists and engineers to 'sculpt' the surfaces of solids at the scale of a nanometre - just one thousandthousandth of a milimetre. Now researchers have demonstrated that by precisely varying the shape of the surface, one can force fluids to behave in entirely novel ways.
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A mathematical formula is used to explain how the relationship between the liquid and the surface changes as one wets the other. Previous formulas have all failed to explain what scientists found when they conducted experiments in this field, and have become increasingly complicated and technical.

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Their new understanding may allow engineers to unlock new ways to control microfluidic processes, vital in so-called 'labson-chips' and perhaps lead to super-repellent surfaces of great value in chip-making industries.

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London’s Imperial College Department of Mathematics, author of the new paper, Professor Andrew Parry has devised and tested a new way to explain this process . His formula takes into account fluctuations in the drop of liquid between the solid surface it sits on and the air above it, which have not been included in any previous formula.

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Parry have shown that as surface geometry changes from a flat wall, via a wedge or parabolic shape to two walls facing each other (as in a capillary tube), the intermolecular forces of attraction are switched off and the influence of geometry is switched on. The behaviours discovered subtly and smoothly link the phenomena of wetting and capillary condensation.
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Dr Andrew Parry explains how their research took shape. "We were motivated by the recent experimental advances made in manufacturing surfaces that are sculpted to a given shape, or decorated with different chemicals, at the near atomic scale."

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Our approach was to look at something that had been ignored by almost everyone else working in this field. We wanted to know how different surface geometry could affect the way that liquid is adsorbed at the surface.

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"We imagined a clearly-sighted watchmaker who can bend or polish glass how he wants, forming any shape with it," said Dr Parry. "We then imagined that starting with a single flat wall he continuously changed the morphology by bending the surface more and more acutely until he finished with two walls facing each other and connected together at the bottom.
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"Into this hypothetical system we put a gas under a controlled temperature and pressure so that it is very close to becoming its liquid. As we changed the glass surface we studied the way in which the adsorption properties of the liquid changed, and how we go from what is called a second-order phase transition (known as wetting, which occurs on the flat wall) to a first-order one (capillary condensation, which occurs between the parallel walls).

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Parry was astonished to discover that from the very simple theory a great richness of intermediate surface adsorption behaviour emerged - what Dr Parry dubs the surface equivalents of "missing links", which facilitate the change from wetting to condensation.

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Dr Parry's own 'Eureka!' moment occurred in April this year as he walked across Battersea bridge in London one morning. He realised that the mathematical solutions to the equations describing the adsorption of liquid on the solid surface had a simple geometrical interpretation. Understanding the liquid structure was analogous to an 'arcade' game of dropping pennies into shaped slots.
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"It was as if our imaginary watchmaker is turning off the atomic forces of Nature and turning on the effects of geometry. Of course the way that the geometry affects the amount of adsorption is very subtle, but in a very real way the sculptor is beginning to play God!", he said.

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A particularly fundamental and fascinating behaviour emerged around the shape of the parabola. As the vapour pressure increased, and the gas changed to liquid, they found that instead of filling up continuously from the bottom, as a beaker of water would from a tap, the geometry forced the system to remain dry until a threshold pressure is reached .
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"Geometry alone had stopped the formation of any liquid - it had induced a drought. Only if the pressure continues to rise, past the threshold, would any liquid form on the bottom. We called the point at which the water would fill the parabola shape normally, the Moses transition." Dr Parry said.

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The researchers found that as they made the walls of the two planes of glass steeper, becoming closer to parallel to each other, the behaviour became even more profoundly strange. At a critical value, they found that two pools, or menisci, of liquid formed in the corners of the shape, but again not on the bottom. As pressure rose further the menisci extended in size and eventually merged into one central meniscus.
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Potential Applications

Dr Parry acknowledged the blue-skies nature of the research, but highlighted a couple of potential applications. "Microfluidic systems work by steering small amounts of liquid along tiny channels on a chip. Instead of having to chemically arrange it one could conceivably sculpt the chip to control fluid flow and place tiny amounts of liquid in particular points simply by varying the pressure of the gas above it," said Dr Parry.
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"Or perhaps you could make computer chips that repelled liquid. In a chip manufacturing clean-room, great efforts are taken to eliminate contamination in the air. If you could sculpt the surface to be super-repellent then you've already got a clean chip."

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