Capillarity — the series · Illustrated Physics

Four tubes, four heights. Water in tubes of radius 0.2, 0.4, 0.8, 1.6 mm, with each meniscus drawn as the spherical cap a 20° contact angle forces and each height computed from it. The narrowest rises 70 mm and the widest 9 mm — in inverse proportion to the radius, with nothing about the glass or the volume of water entering it.

How high water will climb

Water rises up a narrow tube against gravity, and the narrower the tube the higher it goes. The height is set by a curved surface pulling on a circumference while gravity pulls on an area, and the two scale differently — which is the whole of it.

part 1 · fluids

One volume of liquid, several solids. 4 drops of the same 5 µL of liquid, on 4 solids it meets at 20°, 60°, 90°, 140°. Each is the spherical cap that volume and that angle force, so the footprint radius is computed rather than chosen: 20° gives 2.61 mm, 60° gives 1.71 mm, 90° gives 1.34 mm, 140° gives 0.69 mm. At every contact line the three interfacial tensions are drawn to scale, and only their horizontal components balance — γsv = γsl + γlv cos θ. The vertical pull of the liquid surface is taken up by the solid, which is why the angle belongs to three interfaces at once and to no single liquid: change the solid and nothing about the water has changed.

The angle a liquid makes with what it sits on

Everything capillarity does — climbing, beading, wicking, waterproofing — is the sign and size of one cosine, and that cosine belongs to three interfaces at once rather than to the water. Change the solid and nothing about the water has changed, yet the same five microlitres goes from a footprint 2.61 mm across to one of 0.69 mm.

part 2 · fluids

A pore that lifts 100 m has to be 0.1 µm or finer. Capillary rise against pore radius, both logarithmic, for a liquid of surface tension 72.8 mN/m at a contact angle of 20°. The relation is a straight line of slope −1 — halve the pore and double the rise — and the two horizontal marks are the height in question, 100 m, and the 10.3 m that one atmosphere supports. 0.01 µm lifts 1394.7 m; 0.1 µm lifts 139.5 m; 1 µm lifts 13.9 m; 5 µm lifts 2.8 m; 20 µm lifts 69.7 cm; 50 µm lifts 27.9 cm. The conducting vessels of a tree are tens of microns across and lift under a metre; the pores in the membranes between them are tens of nanometres and would lift kilometres. Those are the same expression at two scales, and only one of them is a pipe.

The column that is pulled, not pushed

A capillary fine enough to lift a hundred metres is far too fine to carry any flow, and one wide enough to carry the flow lifts under a metre. Neither is how the water gets up a tree. The column is under tension — an absolute pressure of −0.88 MPa at the top, which a gas cannot have — held together by cohesion and prevented from tearing by pores a few tens of nanometres across.

part 3 · fluids

The pore size the air decides. The largest pore radius that holds condensed water in equilibrium with air at a given relative humidity, for water at 25 °C, on a logarithmic radius axis. A concave meniscus lowers the vapour pressure over it by exp(−2γVₘ/rRT), so a pore whose meniscus would be tighter than a radius set by the humidity is in equilibrium only when full. The upper curve is the emptying condition, through a hemispherical meniscus with two curvatures; the lower is the filling condition, through the cylindrical film that lines a pore before it closes, with one — so the same pore fills at a higher humidity than it empties at. At 50% humidity a pore empties below 1.51 nm and fills below 0.76 nm; at 90% humidity a pore empties below 9.96 nm and fills below 4.98 nm; at 99% humidity a pore empties below 104 nm and fills below 52 nm. The radii run from molecular at low humidity to a tenth of a micrometre at 99 per cent, and every one was checked by putting it back into the vapour-pressure relation.

The pore that fills from dry air

Water condenses when the air is saturated — on a flat surface. Over a curved one the vapour pressure is different, higher over a drop and lower over a meniscus, and in a pore a few nanometres across it is low enough that the pore fills with liquid from air at half humidity. The water it holds is under a tension of a hundred megapascals, and the pore empties at a lower humidity than it filled at, for a reason that needs no roughness at all.

part 4 · fluids

An angle set by a voltage. The contact angle of water on a fluoropolymer coating with a rest angle of 115°, against the voltage across the coating, for coatings 1 and 3 µm thick with a relative permittivity of 1.93. The Lippmann–Young law cos θ = cos θ₀ + ε₀εᵣV²/2dγ makes the cosine rise as the square of the voltage, so the curve is symmetric about zero volts and steepest where the angle is near 90°. For 1 µm the law reaches complete wetting at 110 V; for 3 µm the law reaches complete wetting at 191 V. It does not get there. In most reported experiments the angle stops falling somewhere in the shaded band and then stays put however high the voltage is raised — contact-angle saturation — and why is still argued: charge trapped in the insulator, ionisation of the air at the sharp edge of the drop, and the thermodynamic stability of the contact line have all been proposed and none accounts for every case.

The angle a voltage can set

A contact angle is treated as a fact about three materials — a solid, a liquid and the air — fixed the moment they are chosen. Put a voltage across a micrometre of insulator under a drop and the angle falls as the square of the voltage, with nothing about the materials changed. Drops can be steered across a chip with no pump, and a lens can focus with no moving part. The law that describes it is exact in its model, and real surfaces stop obeying it at an angle nobody has fully explained.

part 5 · fluids