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Capillary Surface
Interfaces
Robert Finn
A
nyone who has seen or felt a raindrop, under physical conditions, and failure of unique-
or who has written with a pen, observed ness under conditions for which solutions exist.
a spiderweb, dined by candlelight, or in- The predicted behavior is in some cases in strik-
teracted in any of myriad other ways ing variance with predictions that come from lin-
with the surrounding world, has en- earizations and formal expansions, sufficiently so
countered capillarity phenomena. Most such oc- that it led to initial doubts as to the physical va-
currences are so familiar as to escape special no- lidity of the theory. In part for that reason, exper-
tice; others, such as the rise of liquid in a narrow iments were devised to determine what actually oc-
tube, have dramatic impact and became scientific curs. Some of the experiments required
challenges. Recorded observations of liquid rise in microgravity conditions and were conducted on
thin tubes can be traced at least to medieval times; NASA Space Shuttle flights and in the Russian Mir
the phenomenon initially defied explanation and Space Station. In what follows we outline the his-
came to be described by the Latin word capillus, tory of the problems and describe some of the
meaning hair. current theory and relevant experimental results.
It became clearly understood during recent cen- The original attempts to explain liquid rise in a
turies that many phenomena share a unifying fea- capillary tube were based on the notion that the
ture of being something that happens whenever portion of the tube above the liquid was exerting
two materials are situated adjacent to each other a pull on the liquid surface. That, however, cannot
and do not mix. We will use the term capillary sur- be what is happening, as one sees simply by ob-
face to describe the free interface that occurs when serving that the surface fails to recede (or to change
one of the materials is a liquid and the other a liq- in any way) if the tube is cut off just above the in-
uid or gas. In physical configurations such as the terface. Further, changing the thickness of the
capillary tube, interfaces occur also between these walls has no effect on the surface, thus suggest-
materials and rigid solids; these latter interfaces ing that the forces giving rise to the phenomenon
yield in many cases the dominant influence for de-
can be significant only at extremely small dis-
termining the configuration.
tances (more precise analysis indicates a large por-
In this article we describe a number of such
tion of these forces to be at most molecular in
phenomena, notably some that were discovered
range). Thus, for a vertical tube the net attractive
very recently as formal consequences of the highly
forces between liquid and wall must by symmetry
nonlinear governing equations. These discoveries
be horizontal. It is this horizontal attraction that
include discontinuous dependence on the bound-
causes the vertical rise. Molecules being pulled to-
ary data, symmetry breaking, failure of existence
ward the walls force other molecules aside in all
Robert Finn is professor emeritus of mathematics at directions, resulting in a spread along the walls that
Stanford University. His e-mail address is finn@gauss. is only partly compensated by gravity. Liquid is
stanford.edu. forced upward along the walls, and cohesive forces
p
cos θ − k2 − sin2 θ
(7) u≈ .
kκr
On the other hand, if α + γ ≥ π /2 , then u(x, y)
is bounded, depending only on κ and on the size
of the domain covered by S near O :
Theorem 3. If u(x, y) satisfies (4) with κ > 0 in Ωδα
and if S meets the bounding wedge walls in an
angle γ such that α + γ ≥ π /2 , then
Existence and for example, for the water and acrylic plastic in-
Nonexistence; the terface in the Coburn experiment described above,
Canonical it is over 20◦. Such apparent anomalies of mea-
Proboscis surement have led to some questioning of “con-
The just-described con- tact angle” as a physical concept. The experimen-
currence of experimen- tal confirmation of discontinuous dependence on
tal results with predic- data at the critical opening in a wedge supports the
tion from the formal view that contact angle does have intrinsic physi-
theory provides a per- cal meaning; in addition it suggests a new method
suasive indication that for measuring the angle in particular cases. One
the Young-Laplace- need only place a drop of the liquid into a wedge
Gauss theory, beyond that is formed by vertical plates of the solid and
its aesthetic appeal, has initial opening sufficiently large that Theo-
also correctly describes rem 3 applies. The opening angle is then slowly de-
physical reality. The creased until the liquid jumps up in the corner to
physical validity of that a height above the bound given by (8). The crite-
theory has been ques- ria of Theorems 2 and 3 then determine γ.
tioned on the basis of For values of γ close to π /2 , remarkably good
ambiguities that occur agreement has been obtained in this way with the
in attempts to measure “equilibrium angle” measured under terrestial con-
contact angle. There are ditions. On the other hand, for values of γ close
experimental proce- to 0◦ , the physical changes occur in the immedi-
dures that give rise to ate neighborhood of O with an opening close to
reasonably repeatable π , and measurements become subject to experi-
measurements of what mental error. We thus seek domains in which the
may be described as an discontinuous behavior is manifested over a larger
“equilibrium angle”. set. We can do so in the context of a general the-
However, if one par- ory of independent mathematical interest, apply-
tially fills a vertical cir- ing to zero gravity configurations and determin-
cular cylinder with liq- ing criteria for existence and nonexistence of
uid (symmetrically) and solutions of (9), (5) in tubes of general piecewise
Figure 5. Liquids with different contact
then tries to move the smooth section Ω .
angle in acrylic plastic cylinders of
liquid upward by a pis- Let Γ be a curve in Ω cutting off a subdomain
hexagonal section during free fall.
ton at the bottom, the Ω∗ ⊂ Ω and subarc Σ∗ ⊂ Σ = ∂Ω , as in Figure 7.
(Top) α + γ > π /2 . (Bottom)
contact line of liquid From the zero gravity equations (9) and (5) we ob-
α + γ < π /2 .
with solid does not im- tain, for the area |Ω∗ | and length |Σ∗ | ,
Z
mediately move, but in-
stead an increase in the (10) 2H|Ω∗ | = |Σ∗ | cos γ + ν · T u ds.
Γ
contact angle is ob-
served. The maximum The same procedure with Ω∗ = Ω yields
possible such angle be- |Σ| cos γ
fore motion sets in is (11) 2H = .
|Ω|
known as the “advanc-
In (10) we observe that
ing angle”. Corre-
spondingly, the small- |Du|
est such angle ob- (12) |ν · T u| ≤ q <1
1 + |Du|2
tainable before reverse
motion occurs is the
for any differentiable function u(x, y) . It follows
“receding angle”. The
that whenever there exists a solution to the
difference between ad-
problem, the functional Φ(Ω∗ ; γ) ≡ |Γ | −
vancing and receding
|Σ∗ | cos γ + 2H|Ω∗ | satisfies
angles is the “hysteresis
range”, which presum- (13) Φ(Ω∗ ; γ) > 0
ably arises due to fric-
tional resistance to mo- for all strict nonnull subsets Ω∗ ⊂ Ω cut off by
tion at the interface, smooth curves Γ, when H is determined by (11).
but could conceivably This inequality provides a necessary condition for
also reflect inadequacy existence of a solution.
Figure 6. Sketch of side view at edge in of the theory. This To make the condition sufficient, we appeal to
drop tower experiment, α + γ < π /2 . range can be very large; the properties of “Caccioppoli sets” in the BV
Figure 11. Spherical blobs in a wedge of opening 2α = 50◦ for three choices of data near boundary of E. (a) Data in E
near D− −
1 ; crossing the boundary into D1 yields continuous transition to a sphere with two caps removed.
+
(b) Data near D1 ; transition to boundary yields spread extending to infinity along edge. Transition across
boundary not possible. (c) Data near D± 2 ; transition across boundary yields fictitious drop realized physically as
drop on single plane.
Theorem 8. As one increases B1 = B2 to move from the supplementary orientation condition that the
the ellipse E to the region in the parameter space mean curvature vector is directed away from the
D− 1 , the free surface of the drop changes in topo- vertex, the surface is spherical.
logical character from a disk to a cylinder. The
If N > 3 , the surface need not be spherical. The
surface becomes a metric sphere with two caps re-
surfaces described in the Appendix of [6] have
moved at the places where the drop contacts the two
four vertices. A spherical drop in a wedge has two
plates. Figure 11a depicts a value of the parame-
vertices. We are led to:
ter shortly before the transition occurs. On ap-
proaching D+1 within E on the same line, the radius Conjecture. There exists no blob in a wedge, with
of the drop grows unboundedly, with the drop cov- N = 2 vertices and data in D±
2.
ering very thinly a long segment of L ; see Figure
11b. As either D− +
2 or D2 are entered from E on the Stability of Liquid Bridges I
line B1 = −B2 , the drop becomes a spherical cap
A substantial literature has developed in recent
lying on a single plate and not contacting the other
years on stability criteria for liquid bridges join-
plate; see Figure 11c.
ing two parallel plates separated by a distance h ,
As already mentioned, for data in D− +
1 or in D1
in the absence of gravity. Earlier papers considered
no drop in the wedge can exist even locally as a bridges joining prescribed circular rings, but more
graph over a plane orthogonal to L. Theorem 8 sug- recently the problem was studied with contact
gests that the same result should hold for D± 2
angle conditions on the two plates. The initial con-
data. The statement is here, however, less clear-cut; tributions to this latter problem, due to M.
in fact, recent joint work of P. Concus, J. McCuan, Athanassenas and to T. I. Vogel, were for contact
and the author [6] shows that capillary surfaces angles γ1 = γ2 = π /2 for which a bridge exists as
with data in D± 2 can exist locally as graphs. The
a circular cylinder, and established that every sta-
matter may be related to the presence of vertices, ble configuration is a cylinder with volume
in a sense introduced in [5]. There a blob of liquid V ≥ h3 /π. A consequence is that instability occurs
topologically a ball was considered, resting on a at half the value of h that is indicated in classical
system of planes, each of which it meets in a pre- work of Plateau and of Rayleigh on stability of liq-
scribed angle. Points at which intersection lines of uid columns. The discrepancy arises because of the
the planes meet the surface of the blob are called use here of a contact angle condition, rather than
vertices. This concept extends also to configura- the Dirichlet condition employed by those authors.
tions in which the intersection point is not clearly It was later shown by Vogel and this author that
defined, as can occur for data in D± the same inequality holds regardless of contact an-
2 . The follow-
ing results are proved, for a configuration with N gles. The most complete results on stability of
vertices, and for which all data on intersecting such bridges are due to Lianmin Zhou in her 1996
planes that it contacts lie in E : Stanford University dissertation; Zhou established
in the general case of equal contact angles γ on the
Theorem 9. If N ≤ 2 , then either N = 0 and the blob plates that regardless of γ there is a unique sta-
consists either of a spherical ball or a spherical cap ble bridge if the volume exceeds a critical Vγ . In
resting on a plane, or else N = 2 and the blob forms 1997 Zhou also obtained the striking result that
a spherical drop in a wedge. If N = 3, then the blob for unequal contact angles, the stability set in
covers the corner point of a trihedral angle; under terms of a defining parameter can be disconnected.
Figure 12. For given volume, uniqueness holds in cylindrical tube for any section Ω ; also drop on plane is
unique. But uniqueness fails in tube with curved bottom.
With regard to interpretation of these and also of data on any set of linear Hausdorff measure zero
earlier results, see the editor’s note following her on ∂Ω have no effect on the solution within Ω ; this
1997 paper and the later clarifying papers by behavior holds without growth condition on the so-
Große-Brauckmann and by Vogel. The stability cri- lutions considered. Finn and Hwang showed if κ > 0
teria just described should also be interpreted in (positive gravity) then the stated result can be ex-
the context of the comments directly following: tended to unbounded domains of any form, with-
out conditions at infinity. In the case of equations
Stability of Liquid Bridges II (9), (5) (zero gravity), uniqueness can fail for un-
Stable liquid bridges joining parallel plates are ro- bounded domains.
tationally symmetric but are in general not spher- A liquid blob resting on a planar support sur-
ical. The meridional sections (profiles) of these face is also uniquely determined by its volume
surfaces were characterized by Delaunay in 1841 and contact angle, although the known proof pro-
as the “roulades” of conic sections, and yield the ceeds along very different lines from the one for
sphere as a limiting case. We obtain, however, the the statement above. We may ask whether unique-
result [6]: Every nonspherical tubular bridge join- ness will persist during a continuous (convex) de-
ing parallel plates is unstable, in the sense that it formation of the plane to a tube. The negative an-
changes discontinuously with infinitesimal tilting of swer can be seen from Figure 12. If the tube on the
either plate. In the earlier stability results, tilting right is filled from the bottom until nearly the
of the plates was not contemplated. maximum height of the conical portion with a liq-
From another point of view, there is the re- uid making contact angle 45◦, then a horizontal sur-
markable 1997 result of McCuan: face will result. But if it is filled to a very large
height, then a curved meniscus appears. Removal
Theorem 10. If the data (B1 , B2 ) are not in D−
1 , then of liquid can then lead to two distinct surfaces with
there is no embedded tubular bridge joining inter-
identical volumes and contact angles.
secting plates.
This line of thought can be carried further:
It should be noted here that data in D−
1 are ex- Capillary surfaces are characterized as station-
actly those for which tubular bridges that are met- ary configurations for the functional consisting
rically spheres are possible (cf. Theorem 8 above). of the sum of their mechanical (gravitational and
It is not known whether nonspherical embedded surface) energies. In any gravity field and for any
bridges can occur in that case. H. C. Wente gave γ, “exotic” containers can be constructed that yield
an example of a nonspherical immersed bridge, an entire continuum of stationary interfaces for fluid
with contact angle π /2 on both plates (and thus configurations with the container as support sur-
with data in E ). face, all with the same volume and the same me-
chanical energy. This can be done in a rotation-
Exotic Containers; Symmetry Breaking ally symmetric container, so that all the surface
For solutions of (3), (5) in a bounded domain Ω with interfaces have the same rotational symmetry,
given κ ≥ 0 , uniqueness for prescribed fluid vol- that no other symmetric capillary interfaces exist,
ume and contact angle can be established under and in addition so that energy can be decreased
much weaker conditions than are needed for lin- by a smooth asymmetric deformation of one of
ear equations. In fact, arbitrary changes of the the surfaces. Thus, none of the interfaces in the