NEWS & VIEWS

SURFACE CHEMISTRY

Fakir droplets
Looking through a window on a rainy day may generate feelings
other than melancholy. Curiosity, for example: isnt it remarkable
that water droplets stick to the pane rather than sliding down?

DAVID QUR is in the Laboratoire de Physique de la considering so-called superhydrophobic surfaces.

Matire Condense, Collge de France, 75005 Paris, France. On a superhydrophobic surface a small water drop
e-mail:quere@ext.jussieu.fr remains quasi-spherical: the internal angle is very large,
which dramatically lowers the contact area between the

T
he apparent stickiness of water droplets is caused by drop and the solid surface3,thereby greatly increasing the
small defects that are always present on the surface of internal contact angle (Fig.1b).These slightly flattened
a solid,and that pin the leading edge of a downward- spherical drops are the result of a combination of
moving drop.In this position,the internal contact angle chemistry and physics: the surface is both hydrophobic
(Fig.1a) the drop makes with the solid surface is larger in and rough,and the roughness enhances the
the downward direction than upwards,generating a gra- hydrophobicity4.Two processes are thought to contribute
dient of curvature and thus a gradient of pressure that to this phenomenon: first,a rough material has a higher
opposes the force of gravity1.Thiscapillary forceof the surface area than a smooth one,which increases its
drop scales linearly with the diameter,whereas gravity hydrophobicity (Wenzel model)5; second,air can be
scales with its cube.So only drops smaller than a charac- trapped in the roughness,which also enhances its
teristic length (called the capillary length),of the order of hydrophobicity because the drop is then partially sitting
one millimetre,can stick to window-panes.For certain on air (Cassie model)6,7.In general,the second process
surfaces it would be helpful to avoid this adhesive dominates the observed behaviour.
behaviour,for example,to eliminate the blurring of our This is worth knowing when designing a
window-panes and car windshields.In a recent issue of superhydrophobic solid: the surface must be coated with
Langmuir,Yoshimitsu et al.2 discuss this question by a texture in which air is likely to remain trapped when it
comes into contact with water.It has been shown,for
example,that surfaces decorated with spikes or posts
exhibit superhydrophobic behaviour: the water drops
behave as fakirs are supposed to do on a bed of nails: sit
Figure 1 Behaviour of water a comfortably on top of the posts7.In their study,
drops on different surfaces. Yoshimitsu et al.decorated flat solids with square pillars
a,Water drop wetting a normal of about 100 m across (Fig.1c),which allows them to
surface forms a low internal observe directly the sitting-on-air regime.They also
Internal
contact angle. b, Non-wetting, contact angle showed that it is possible to switch from the Wenzel to the
quasi-spherical drop forms a Cassie regime,for example by varying the heights of
high internal contact angle on a Normal surface individual posts,or by changing the weight of the drop: if
superhydrophobic surface. the fakir is too fat,he gets impaled on the posts!
c, Drop on a solid surface b The fakir regime has another interesting feature:
decorated with pillars.The entire because the substrate supporting the drop consists
surface is coated with a water- mainly of air,the usual surface defects are largely replaced
repellent agent, and the space by a defect-free cushion of air.This significantly decreases
between the pillars is filled with the capillary forces making the drop stick to the surface6.
air.Yoshimitsu et al.2 observe Increased angle Overall,this situation not only dramatically increases the
that the drop can sit happily on internal contact angle,but also greatly reduces the
top of these pillars the so- possible fluctuations in this angle both of these effects
called fakir regime Superhydrophobic surface reduce the adhesion of the drop.By studying the
corresponding to an apparent transition between the fakir regime and the impaled one,
contact angle larger than 150 c Yoshimitsu et al.confirm that the fakir regime generates
(superhydrophobic behaviour). surfaces that water drops will slide across more easily2.
mm

If the pillar height is shortened, The authors also consider the effect of varying the
0.7

the water contact angle structure of the textured surface in the fakir regime.
decreases, because air is no On surfaces made from pillars or grooves but having
longer trapped below the drop. similar contact angles the authors observe different
50 m sliding behaviour.They find that the water drops have the
148 m least adhesion on surfaces having grooves that are parallel
to the direction of motion.But,the drops stick less to
100 m
pillars than to grooves that are oriented perpendicular to
the direction of the moving drop.These observations

14 nature materials | VOL 1 | SEPTEMBER 2002 | www.nature.com/naturematerials

2002 Nature Publishing Group


stress the importance of the choice of surface structure
for achieving an efficient hydrophobic substrate.
The most likely explanation involves the effect of the
surface structure on the movement of the contact line
the boundary line around the drop where all three phases
(solid,water and air) are in contact.Grooves that are
perpendicular to the direction of the sliding drop present
more of an obstacle to the moving contact line than the
parallel grooves,whereas the pillar structure (which
combines both perpendicular and parallel grooves but in
shorter discontinuous segments) presents an
intermediate obstacle.So sometimes it may be more
effective to consider the behaviour of the contact line
when designing superhydrophobic surfaces,rather than
always looking for the highest possible contact angle.
Many questions remain about these super-
hydrophobic surfaces.On the one hand,how will a
reduction in the size of the posts or grooves affect the
superhydrophobic behaviour? In practical terms,it can
be important to reach submicrometre scales to ensure
that coatings remain transparent.On the other hand,a
COMPUTATIONAL MATERIALS SCIENCE
Nanoscale plasticity
How does plastic deformation of polycrystalline materials
with grain sizes less than 100 nm look at the atomic scale?
A large-scale molecular dynamics simulation of nanocrystalline
aluminium reveals some surprising behaviour.
KARSTEN W. JACOBSEN
AND JAKOB SCHITZ
are at the Center for Atomic-scale Materials Physics, Department
of Physics, Technical University of Denmark, DK-2800 Kongens
Lyngby, Denmark.
e-mail: kwj@fysik.dtu.dk; schiotz@fysik.dtu.dk
U
nderstanding the plastic deformation of crystalline
materials is a longstanding challenge in materials
science a challenge that is not only of scientific
interest but has implications for constructing materials
with specific mechanical properties.Since the 1930s,it has
been known that the key to unlocking the secrets of plastic
deformation lies in the behaviour of dislocations line
defects in the crystalline lattice.But dislocation behaviour
has turned out to be very complex,involving multiple
mechanisms for the generation and annihilation of these
defects.Furthermore,collective phenomena may result
from mutual interactions between dislocations,and from
interactions between dislocations and other defects such
as grain boundaries.The intricate interplay between
dislocation and grain boundaries has a new twist for
nanocrystalline materials,where the small grains put
severe limitations on the dislocation behaviour.In this
issue,Yamakov et al.1 address the problem of dislocation
behaviour and plastic deformation in nanocrystalline
aluminium using state-of-the-art molecular-dynamics
nature materials | VOL 1 | SEPTEMBER 2002 | www.nature.com/naturematerials
NEWS & VIEWS
quasi-spherical drop behaves quite remarkably on such
textured solids.Its friction as it moves,for example,is
much smaller than for a drop on an ordinary solid3,
where most of the friction takes place in the region of the
contact line.On a superhydrophobic solid,however,
drops seem to move over a dynamic film of air which
makes the friction comparable to that experienced by a
raindrop falling in air.But what happens if these textured
solids are fully immersed in a pool of water? Will the
water still slide on them? Except for a few controversial
studies,this question still remains open,and designers of
boats and swimsuits impatiently await an answer.
References
1. Dussan V, E. B. & Chow, R. T. P. J. Fluid Mech. 137, 129 (1983).
2. Yoshimitsu, Z., Nakajima, A., Watanabe, T. & Hashimoto, K. Langmuir 18,
58185822 (2002).
3. Mahadevan, L. & Pomeau, Y. Phys. Fluids 11, 24492453 (1999).
4. Onda, T., Shibuichi, S., Satoh, N. & Tsujii, K. Langmuir 12, 21252127 (1996).
5. Wenzel, R. N. Ind. Eng. Chem. 28, 988994 (1936).
6. Dettre, R. H. & Johnson, R. E. Adv. Chem. Ser. 43, 136144 (1963).
7. Bico, J., Marzolin.C. & Qur, D. Europhys. Lett. 47, 220226 (1999).
simulations.They show that the behaviour of nanocrys-
talline aluminium is likely to differ significantly from the
known behaviour of the coarse-grained material.
Nanocrystalline metals have been of interest for
some time because of their enhanced hardness.For a
given material,the hardness increases in an inversely
proportional manner to the square root of the grain size
the HallPetch relation thereby enhancing the
hardness of a 20-nm-grained nanocrystal by an order of
magnitude compared with a typical coarse-grained
material2.This enhanced hardness arises from the
restrictions that grain boundaries impose on dislocation
behaviour.Dislocations are,to a large extent,confined to
operate within single grains,and small grains therefore
limit both the generation and mobility of dislocations,
making deformation more difficult.The grain
boundaries not only act as obstacles for dislocations,but
may also play an active role in the deformation process,
both as sources of dislocations and through sliding
processes or diffusion events occurring at the
boundaries.However,because of the difficulty of directly
observing grain boundary and dislocation processes in
such small grains,the exact role of grain boundaries in
the deformation behaviour of nanocrystalline materials
has remained an open question.
In their paper,Yamakov et al.1 use a parallel computer
to simulate the atomic-level deformation of model
15
2002 Nature Publishing Group