Fundamental Equations of Surface Science

Young

γ SL − γ SV 0 + γ LV cosθ = 0
liquid gas (vapor)
θ
solid

Young-Laplace Kelvin

2γLV r 𝑃 !"#$% 2𝛾𝑉

ΔP = 𝑅𝑇𝑙𝑛 =
r 𝑃 !"#$%
!
𝑟
P = total pressure

Pvapor = vapor pressure over flat 0 and curved surface

V = molar volume
 Hydrophilic surface

Hydrophobic defect
Wenzel-Cassie
 R

smaller R, larger 𝜹
Critical drop radius

R < R* Small drop Wenzel

R > R* Large drop Cassie

If h large (or p and h both small) R* small, Cassie more robust

Annu. Rev. Mater. Res. 2008. 38:71–99

 Evaporation

R
 Energy transition between Cassie and Wenzel

Strong variation in slope and high special

frequency of pillars stabilizes the metastable
Cassie state (e. g. Lotus)

David and Neumann, Colloids and

Surfaces A 2013, 425, 51
 Cassie equation for heterogeneous surfaces

cosθ c = f1 cosθ1 + f2 cosθ 2

Cassie-Baxter on porous surface

cosθ c = f1 cosθ1 − f2
f2 fraction of open area

Ex: water proofing fabrics birds

 And if drops smaller than 1 mm?
Wenzel Young-Laplace
Space between barbs 0.2 mm
Cassie Laplace pressure 140 Pa
Wetting

Keratin contact angle 72o

Contact angle on heterogeneous surfaces

cosθ c = f1 cosθ1 + f2

Large values of (r + d)/r

large f2 and small f1 values
increasing the apparent contact angle
Oil wetting
 Lotus effect 14 2 Roughness-Induced Superomniphobic Surfaces: Lessons from Nature

Wax makes the surface hydrophobic

Hierarchical structure makes it superhydrophobic
Low contact angle hysteresis promotes roll off

http://lotusleafeffect.org/

Fig. 2.2 SEM micrographs (shown at three magnifications) of Lotus (Nelumbo nucifera) leaf
surface which consists of microstructure formed by papillose epidermal cells covered with 3D
epicuticular wax tubules on surface, which create nanostructure, and image of water droplet sitting
on the Lotus leaf (Bhushan et al., 2009b)

Contact angle hysteresis is a measure of energy dissipation during the flow of a droplet
along a solid surface.
Low contact angle hysteresis results in a very low water roll-off angle, which denotes the
angle to which a surface may be tilted for roll-off of water drops
Fig. 2.3 Schematic and wetting of the four different surfaces. The largest contact area between
the droplet and the surface is given in flat and microstructured surfaces, but is reduced in
nanostructured surfaces and is minimized in hierarchical structured surfaces
Low water roll-off angle: important in liquid flow applications such as in micro-
/nanochannels and surfaces with self-cleaning ability. It has been reported that all superhydrophobic and self-cleaning leaves consist of
an intrinsic hierarchical structure (Koch et al., 2008, 2009a). Hierarchical structure
provides air pocket formation, leading to the lowest contact area of an applied
water droplet (Fig. 2.3), resulting in the reduction of contact angle hysteresis,
tilt angle, and adhesive force responsible for self-cleaning, low adhesion, and
antifouling (Bhushan and Jung, 2008, 2011; Nosonovsky and Bhushan, 2008a;
Bhushan et al., 2009b; Bixler and Bhushan, 2012).
Other examples of biological objects include water striders (Gerris remigis)
(Gao and Jiang, 2004) and mosquito (Culex pipiens) eyes (Gao et al., 2007).
Their hierarchical structures are responsible for superhydrophobicity. Duck feathers
 Rose Petals (rosea Rehd)

Superhydrophobic
High contact angle hysteresis

Rose petal’s microstructures have a larger pitch value than the Lotus leaf
Liquid is allowed to impregnate between the microstructure but partially penetrates into
the nanostructure (Cassie-impregnating wetting regime), in which the wetted surface
area is less than that in the Wenzel regime but greater than that in the Cassie–Baxter
regime
 Superhydrophobicity with adhesion
Rose petal Chinese Kafir petal

Sunflower petal

Langmuir 2008, 24, 4114

Rose Petals

8.3 Fabrication of Surfaces with High and Low Adhesion 203

Fig. 8.1 (a) Optical micrographs and (b) SEM micrographs of two roses which have different
adhesion properties on its petals—Rosa Hybrid Tea cv. Bairage (Rosa cv. Bairage) and Rosa
Hybrid Tea cv. Showtime (Rosa cv. Showtime) (Bhushan and Her, 2010)

8.2 Characterization of Two Kinds of Rose Petals and Their

Underlying Mechanisms

Two kinds of rose petals with superhydrophobicity were studied by Bhushan and
Her (2010). One is Rosa Hybrid Tea cv. Bairage for surfaces with high adhesion,
and the other is Rosa Hybrid Tea cv. Showtime for low adhesion, referred to as
Rosa cv. Bairage and Rosa cv. Showtime, respectively. Figure 8.1 shows optical and
SEM micrographs of two rose petals. In Fig. 8.9 Schematic illustrations of droplets on hierarchical structure with two nanostructures. As
antheir
example,study, to get stable
mass of n-hexatriacontane changessamples, they (regimes A and B
the density of nanostructure 2

air-dried the petals for SEM measurement.underlying

Kochsubstrate
et al.(Bhushan
(2008) reported that during
in Fig. 8.8a). Nanostructures play an important role in contact formation between water and
and Her, 2010)
the measurement of real petals using SEM, loss of water from the cell occurred,
leading to shrinkage on the hierarchical (0:1
micro-
!g=mmand 2 nanostructures
/. Droplets on petals
on the surface (regime B1 / haveina high contact angle
ı ı
a high vacuum chamber. The specimen shown in the right image 2 in Fig. 8.2 has
(164 ) with low contact angle hysteresis (3 ), and trapped air pockets can be seen.
When n-hexatriacontane (0:2 !g=mm / is applied on a microstructure (105 !m
Nosonovsky and Bhushan, Green Tribology 2012
Shark skin
Oleophobic surfaces for self-cleaning and
antifouling from biological contaminants
Hydrodynamic, self-cleaning, antifouling

Shark skin-inspired experimental vinyl sawtooth

riblets have been developed by 3M Corp:3 %
when 70 % drag reduction if Airbus plane surface
covered by these sheets.
Speedo FastSkin® racing swimsuit.

Michael Phelps
28 Medals

Swimsuit made of a knitted super-stretch nylon/elastane/

polyester fabric (flexskin) that has V-shaped ridges and a denticle
surface print. In water this means that water is sucked closer to
the body and then passes over the swimmer far more effectively.
Fouling and antifouling topography
 Phalarope

As the beak scissors open and shut, each movement propels the water droplet one
step closer to the bird's mouth

Force between the beak and the droplets of water pushes the food from the tip:
contact angle hysteresis

Dependence on the shape of the beak and how fast the drop moves. The fastest it can
move is about 1 meter per second. Long, narrow beaks work best

Capillary ratchet also depends strongly on "wettability". (how well a liquid spreads out
to wet a surface, rather than forming droplets). Oil wets more than water. So if the
beak has oil on it from a spill, the capillary ratchet won't work and the bird can't feed
https://www.youtube.com/watch?v=heEUPbxmYgQ
172 RUBEGAAND OBST [Auk, Vol. 110

oo o c•4

The time-dependent beak geometry

couples with contact angle hysteresis
to propel the drop upward
First known example where droplet
motion is enabled rather than
resisted by contact angle hysteresis
B

•0• O0 ß o- 002 00 0 9•

Nature's design: microfluidic devices

in which this mechanism could be
exploited for directed droplet
transport, allowing for controlled
stepwise motion of microliter
E
droplets
Fig. 2. Surface-tensionprey transportby Red-neckedPhalarope.Numbers acrosstop of frames indicate
time in 0.001-sincrements.This previously unknown feeding mechanismusessurfacetension of water to
rapidly transportprey from bill tip to mouth without useof suctionor tonguemovementsby bird. After bird
seizesprey with bill tips (frames A-B), transport of prey along bill is accomplishedby rapid mandibular https://sora.unm.edu/sites/default/files/journals/auk/v11
spreading(framesC-F). This motion, by increasingfree surfaceareaof drop that surroundsprey and adheres
to bird's bill, drivesdrop up bill and into the bird's mouth. Note presenceof prey in drop, as evidencedby 0n02/p0169-p0178.pdf
brine shrimp eyesvisible in frame C.
 DROPLET-BASED MICROFLUIDICS

M. Im et al., IEEE, 2009