Series

Surface tension — the series

12 essays on one idea, from the one that introduces it to the one that assumes the rest.
  1. Surface at fixed volume. Four shapes of identical volume with their surface areas evaluated. The sphere's is the smallest at 4.836; the flattest shape drawn carries 1.91 times as much. Surface tension is an energy per unit area, so a free drop of liquid has an incentive to be the first of these and none at all to be any of the others.

    The skin that is not a skin

    A drop of water behaves as though it were wrapped in a stretched membrane, and there is no membrane. What there is instead is an energy cost per unit of surface, and almost everything the apparent skin does follows from a liquid trying to have less of one.

    part 1 · fluids
  2. The small bubble empties into the large one. Two soap bubbles of radius 4 mm and 12 mm joined by an open tube. The excess pressure inside each is 4γ/R — 72.8 Pa and 24.3 Pa — so the 4 mm bubble is at the higher pressure and blows itself into the other. The smaller a bubble gets the harder it pushes, so the process runs away rather than settling: there is no equilibrium anywhere except both bubbles equal.

    The small bubble blows up the big one

    Connect two soap bubbles of different size and the small one empties into the large one. Everybody expects the opposite, and the reason it happens is one equation with a radius in the denominator — which also means the process runs away rather than settling.

    part 2 · fluids
  3. Which wavelength wins. The growth rate of a disturbance on a liquid thread against kR, the circumference divided by the wavelength. Everything to the right of one decays; the maximum sits at kR = 0.697, which is a wavelength of 9.01 radii or 4.51 diameters. That number, and not a property of any particular liquid, is what sets the spacing of the drops a tap breaks into.

    The thread that cannot stay a thread

    A stream of water from a tap breaks into drops, and it does so at a spacing that is always about four and a half diameters. Nothing chooses that number — it is the wavelength that grows fastest out of a competition between all of them, and it can be computed before any water is poured.

    part 3 · fluids
  4. Two ways to weaken a surface. Surface tension is a property of a surface rather than a constant of a liquid, and this shows how far it moves. The steep curve is water with ethanol dissolved in it, against ethanol mole fraction, through nine measured points: two per cent of ethanol takes the tension from 72 to 56.4 mN/m, a fall of 22% for a change of composition small enough to taste and not to see. The initial slope is 837 mN/m per unit of mole fraction, because ethanol collects preferentially at the surface and a little of it covers a great deal of area. The gentle line is pure water against temperature, read on the same horizontal axis as degrees rather than fraction: about 0.15 mN/m per degree, so a difference of ten degrees across a surface is worth about a millinewton per metre. Neither dependence would be interesting if surfaces were uniform. What makes them matter is that a difference in tension across a surface is a force along it, and nothing in the liquid prevents such a difference from existing.

    The surface that pulls toward the stronger side

    Surface tension is usually treated as a constant of a liquid, and it is not — it depends on temperature and on what is dissolved, and a difference in it along a surface is a force along that surface — which drags the liquid underneath and needs no pressure difference at all.

    part 4 · fluids
  5. Where a drying drop loses its liquid. The rate at which liquid leaves the surface of a drying drop, against distance from the centre in units of the drop's radius, for 5 contact angles. The flux is not uniform, and it is not a property of the liquid: it is set by how vapour diffuses away from a lens-shaped object, which is the same boundary-value problem as the field around a charged lens and has the same answer — a power law in the distance from the rim, with an exponent that depends only on the contact angle. at 10° the exponent is 0.471, and the loss has doubled by 87.8 per cent of the way out, at 40° the exponent is 0.357, and the loss has doubled by 92.5 per cent of the way out, at 70° the exponent is 0.182, and the loss has doubled by 98.9 per cent of the way out, at 90° the exponent is 0.000 and the drop dries evenly everywhere, at 120° the exponent is -0.500 and the flux falls toward the rim. Below a right angle the flux diverges at the contact line; at exactly a right angle it is uniform; above it the edge is the slowest-drying part of the drop. Since a pinned edge must be resupplied from the interior, that sign decides which way the liquid inside the drop flows — and therefore whether everything suspended in it ends up in a ring at the rim or in a spot at the centre.

    The ring the drop leaves behind

    A drop of coffee dries into a ring rather than a disc, and nothing about coffee is responsible. The pattern is produced by a boundary condition — an edge that cannot move — and it survives replacing the coffee with anything else that will stay suspended.

    part 5 · fluids
  6. Two angles a film is not allowed to depart from. The two junctions Plateau's laws permit, drawn at the angles a balance of equal tensions requires. A soap film pulls equally in every direction along itself, so where films meet the pulls must sum to zero — and equal vectors summing to zero fixes the geometry completely. Three films can only meet along a line, at 120.0000° to one another, because three equal coplanar vectors sum to zero at 120° and at no other angle. Four such lines can only meet at a point, at 109.4712° — arccos(−1/3), the tetrahedral angle — for the same reason in three dimensions. Both numbers are found here by solving the balance rather than by drawing what is expected, and neither depends on the liquid, the temperature or the size of the foam. A junction of four films along a line, or of three lines at a point, is not merely unusual: the tensions cannot balance there, so it rearranges within milliseconds into the two arrangements drawn.

    The angles a film has no choice about

    A soap film pulls equally hard in every direction along itself, so wherever films meet the pulls have to sum to zero — and equal vectors summing to zero fixes the geometry completely. Three films meet at a hundred and twenty degrees and four edges at a hundred and nine point four seven, in every foam, of every liquid, at every scale, and nothing about the material appears in either number.

    part 6 · fluids
  7. One line decides whether it climbs for ever. The wetting condition for a corner, drawn as a map. The horizontal axis is the corner's half-angle and the vertical axis the liquid's contact angle with the walls; the diagonal is θ + α = 90°. Below it the meniscus in the corner curves into the liquid, the capillary pressure grows without bound as the corner narrows, and the liquid wicks along it indefinitely. Above it the curvature has the other sign and the liquid stays put. The boundary is tested by evaluating the meniscus a millionth of a degree either side of it at seventeen half-angles, and it wicks on one side and not the other every time. water on clean glass, right-angled corner: α = 45°, θ = 5° — wicks; water on glass, a 20° groove: α = 10°, θ = 40° — wicks; water on plastic, right-angled corner: α = 45°, θ = 75° — does not. A right-angled corner needs a contact angle under 45°, which water on clean glass has and water on most plastics does not.

    The corner a liquid never stops climbing

    A narrow tube lifts a liquid to a definite height because it has a smallest width. A corner has none, so the capillary suction it can develop is unbounded — and whether the liquid takes advantage is decided by a single inequality between the contact angle and the corner's own angle.

    part 7 · fluids
  8. The colours a draining film runs through, and the end of them. The fraction of light a free soap film reflects, against its thickness, at three wavelengths — 450, 550, 620 nm — computed from the sum over multiple reflections rather than from the two-beam approximation. The three curves peak at different thicknesses, which is why a draining film runs through a sequence of colours as it thins. Below about 11 nm every curve is under a tenth of a per cent and the film looks black. At zero thickness the reflectance is exactly zero, checked before the figure is drawn: the two surfaces reflect equally and half a cycle out of step, so a film much thinner than a wavelength cancels itself. That is the whole of why a black film is black. Nothing is absorbing; the film is there and has simply stopped being able to interfere constructively at any visible wavelength — which means the blackness is a measurement, and a film that has gone black is known to be thinner than about a tenth of a wavelength without anything being measured directly.

    The film that goes black before it bursts

    A soap film drains, runs through every interference colour, and then stops reflecting anything at all. The black patch is not a hole and not a film about to break: it is the thinnest and most stable state the arrangement has, held apart by a pressure between its two surfaces that only exists at distances of nanometres.

    part 8 · fluids
  9. Six cells of a two-dimensional foam, by number of sides. Cells of a two-dimensional soap froth with three to eight sides, each drawn with its films meeting three at a time at 120°, as surface tension requires. A hexagon can do that with straight sides. A cell with fewer than six sides cannot: to make its corners 120° its sides must bulge outward, so its gas is at higher pressure than its neighbours' and leaks out. A cell with more than six must have sides curving inward, lower pressure, and gains gas. The rate of change of area, in units of πκγ/3 where κ is the films' permeability, is n − 6: −3 for a triangle, +2 for an octagon.

    The bubble that grows by counting its sides

    A froth of soap bubbles squeezed between two sheets of glass coarsens over a few days: small cells vanish and large ones swell. The obvious guess is that size decides which cells win, as it does for two bubbles joined by a tube, where the small one always empties into the large one. In a froth it is wrong. John von Neumann showed in 1952 that a cell's area changes at a rate fixed entirely by how many sides it has — shrinking if fewer than six, growing if more — and not at all by how big it is. The proof is a single sum of angles.

    part 9 · fluids
  10. Water's surface tension, all the way to the critical point. The surface tension of water against its liquid vapour, from the international standard correlation, against temperature from 0 °C to the critical point at 373.946 °C. 20 °C: 72.7 mN/m; 100 °C: 58.9 mN/m; 200 °C: 37.7 mN/m; 300 °C: 14.4 mN/m; 370 °C: 0.4 mN/m. It falls almost in a straight line for most of the range and then bends down to reach zero exactly at the critical point, where liquid and vapour stop being two things. The bend is a power law, the gap to the critical temperature raised to 1.256.

    The tension that vanishes where the phases meet

    Surface tension is usually treated as a property of a liquid, like its density. It is a property of a boundary between two things, and it can only exist while there are two things. Heat water in a sealed tube and its surface tension falls steadily, then faster, and reaches exactly zero at 374 °C, where liquid and vapour stop being different. On the way the surface stops being a surface: the step in density spreads from a molecule's width to thousands, and the rate at which the tension dies turns out to be a number the whole family of critical points shares and the simplest theory gets wrong.

    part 10 · fluids
  11. A surface whose thickness depends on how much of it is looked at. The rms roughness of a water surface at 20 °C, in nanometres, against the size of the patch over which it is measured, from the thermal ripples that fit inside the patch — with gravity (solid) and without it (dashed) — for ripples down to a molecular wavelength of 0.6 nm. Over 10 nm the surface is 0.16 nm rough; over a micrometre, 0.26; over a millimetre, 0.36; and beyond a few millimetres gravity flattens the longest ripples and the roughness stops at 0.390 nm. In free fall it would keep growing as the square root of the logarithm: 0.43 nm over a metre. An X-ray reflectivity measurement sees the ripples smaller than its own coherence length, typically some micrometres, and reports a thickness of about a third of a nanometre — a number that belongs to the instrument as much as to the water.

    The surface whose thickness depends on the view

    The surface of a glass of water looks like a perfect plane, and over most distances it nearly is. But it is at room temperature, and every ripple it could carry — from a few molecules long to a few millimetres — is shaken by heat with its own share of thermal energy. The ripples are tiny, a fraction of a nanometre high, and they add up in an odd way: every factor of ten in wavelength contributes the same amount of roughness. So the thickness of a water surface has no single value. It depends logarithmically on how large a patch is looked at, until gravity stops it at a few millimetres, and the X-ray measurements that report a third of a nanometre are reporting a property of their own resolution as much as of the water.

    part 11 · fluids
  12. The film that thins too slowly. The thickness of the air film under a silicone-oil drop of radius 0.38 mm pressed onto its pool, against time, on logarithmic axes, by Reynolds's law: dh/dt ∝ −h³, so the film thins quickly at first and then ever more slowly, its thickness falling only as the inverse square root of time once it is thin. The shaded band is one bounce, 4.1 ms, in which the film falls from 10 µm to 1240 nm; the dashed line is the 100 nm at which van der Waals forces pull the surfaces together, reached after 0.65 s. The air does not have to be held up; it has only to be slow to leave, and the cube of the thickness makes it slower and slower the thinner it gets. A vibrating bath that lifts the drop off every few milliseconds refills the film each time.

    The drop that will not merge

    A drop of oil let fall onto a pool of the same oil ought to vanish into it at once: merging releases surface energy, and nothing holds the two apart. Instead it bounces. A film of air is trapped between drop and pool, and air, though it offers no strength at all, is slow to leave a gap a few micrometres thick: the film takes the better part of a second to drain to the hundred nanometres at which the surfaces can touch, while a bounce lasts four milliseconds. Shake the pool and the drop can bounce for ever, in rhythms that double as the shaking grows — and, near the pool's own instability, it starts to walk across the surface on the waves of its own making.

    part 12 · fluids

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