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How Things Get Wet

New Mathematical Formula Sets

Wetting Theory Straight

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

 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 thousand-
thousandth 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.

 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

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

 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.

 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.

 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."

 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.

 "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.

 "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).

 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.

 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.

 "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.

 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 .

 "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.

 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.

Potential Applications

 Dr Parry acknowledged the blue-skies nature of the

research, but highlighted a couple of potential
 "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.

 "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."