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Water Condensation: A Multiscale Phenomenon

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 Review
Journal of
Copyright © 2014 American Scientific Publishers
Nanoscience and Nanotechnology
All rights reserved Vol. 14, 1859–1871, 2014
Printed in the United States of America www.aspbs.com/jnn

Water Condensation: A Multiscale Phenomenon

Kasper Risgaard Jensen1 , Peter Fojan1 , Rasmus Lund Jensen2 , and Leonid Gurevich1 ∗
1
Department of Physics and Nanotechnology, Aalborg University, Skjernvej 4A, 9220 Aalborg East, Denmark
2
Department of Civil Engineering, Aalborg University, Sohngaardsholmsvej 57, 9000 Aalborg, Denmark

The condensation of water is a phenomenon occurring in multiple situations in everyday life, e.g.,
when fog is formed or when dew forms on the grass or on windows. This means that this phe-
nomenon plays an important role within the different fields of science including meteorology, build-
ing physics, and chemistry. In this review we address condensation models and simulations with
the main focus on heterogeneous condensation of water. The condensation process is, at first,
described from a thermodynamic viewpoint where the nucleation step is described by the classical
nucleation theory. Further, we address the shortcomings of the thermodynamic theory in describing
the nucleation and emphasize the importance of nanoscale effects. This leads to the description of
condensation from a molecular viewpoint. Also presented is how the nucleation can be simulated
by use of molecular models, and how the condensation process is simulated on the macroscale
using computational fluid dynamics. Finally, examples of hybrid models combining molecular and
macroscale models for the simulation of condensation on a surface are presented.
Keywords: Water Condensation, Heterogeneous Nucleation, Hydrophilicity/Hydrophobicity,
Thermodynamics of Water Condensation, Water Condensation Modelling.

CONTENTS on which the phenomenon is relevant. That is, within each

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1859 branch is an attempt to model the condensation as simple
2. The Macroscopic Approach—Thermodynamics as possible without omitting important details. In reality
of Condensation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1859
2.1. Effect of the Liquid-Gas Interface—Homogeneous
the droplet growth during condensation is a multiscale pro-
Nucleation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1860 cess starting with assembly of just a few molecules and
2.2. Condensation on a Substrate—Heterogeneous ending with drops of macroscale dimensions.1
Nucleation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1861 In this review we present how condensation is described
2.3. Droplet Growth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1863
3. Nanoscopic Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1863
and modelled at different length scales ranging from
3.1. Nanoscopic Effects on the molecular to macroscale. Section 2 contains the macro-
Classical Nucleation Theory . . . . . . . . . . . . . . . . . . . . . . . 1863 scopic description of condensation, whereas nano- and
3.2. Nanoscopic Effects on the Contact Angle . . . . . . . . . . . . . 1863 microscopic effects on condensation are presented in
3.3. Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1865
Section 3. In Section 4 it is described how condensa-
4. The Molecular Approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1865
5. Simulation of Condensation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1867 tion appears from an atomic viewpoint. Following these
5.1. Drop Growth Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1867 sections it is discussed in Section 5 how condensation is
5.2. Nucleation Models—Molecular Modelling . . . . . . . . . . . . . 1867 simulated using different approaches.
5.3. Heat and Mass Transfer Models . . . . . . . . . . . . . . . . . . . . 1869
5.4. Simulation of the Solid–Liquid Interface . . . . . . . . . . . . . . 1869
6. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1870 2. THE MACROSCOPIC
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1870 APPROACH—THERMODYNAMICS OF
References and Notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1870
CONDENSATION
1. INTRODUCTION From a thermodynamics point of view, the phase transi-
Every science has developed different ways of describing tion at condensation is expected to occur when the chem-
condensation, depending on the context and length scale ical potential of the vapor phase exceeds the chemical
potential of the liquid phase. For water it occurs when
∗
Author to whom correspondence should be addressed. the relative humidity exceeds 100%. This condition can

J. Nanosci. Nanotechnol. 2014, Vol. 14, No. 2 1533-4880/2014/14/1859/013 doi:10.1166/jnn.2014.9108 1859

Water Condensation: A Multiscale Phenomenon Jensen et al.

be reached either when temperature is lowered below the
dew point temperature or when vapor pressure is increased
above the saturation vapor pressure, as can be seen in the
schematic phase diagram shown in Figure 1. In general
a phase transition depends on the physical properties of
the matter in question, such as enthalpy and volume of
transition of vaporization.2 This relatively simple approach
for defining the phase transition is often used when heat
and mass transfer models are used for the prediction of
condensation.3–9 However, this simplification does not take
into account that the phase transition is altered by surface
and substrate effects, as is described in the following
sections.
2.1. Effect of the Liquid-Gas
Interface—Homogeneous Nucleation
The transition from gas to liquid phase requires the for-
mation of an interface between the two phases. When
droplets are formed, as is the case in dew formation, two
terms add to the change of Gibbs energy, according to the
classical nucleation theory (CNT), and thereby determine
whether the droplet formation takes place. One term is the

Kasper Risgaard Jensen is a Ph.D. student at the Department of Physics and Nanotech-
nology, Aalborg University, Denmark. He graduated with a master’s degree in nanotech-
nology from Aalborg University in 2009. His doctoral research is mainly focussed on
experimental investigation of dropwise condensation.

Peter Fojan got his Ph.D. in Biotechnology at the University of Technology, Graz, Austria
in 1997. He initially worked on industrial genetics of eukaryotic organisms. During his
PostDoc time at Aalborg University at the Department of Biotechnology, he moved into
the area of protein physics and molecular modelling. With the startup of Nanotechnology
at AAU he moved to the Department of Physics and Nanotechnology where he became
an Associate Professor in 2009. His research interests are centered around biological and
small molecules and their interactions with cells and surfaces in general, for medical,
sensor applications and as antibacterial agents.

Rasmus Lund Jensen got his Ph.D. in Civil Engineering from Aalborg University,
Denmark in 2005. He has been involved in research in air distribution and ventilation for
more than 10 years as well as in development of building thermal simulation tools. He is
the leader of the laboratory for Energy and Indoor Environment at Aalborg University and
has as such been heavily involved in the development and quality assurance of measure-
ment techniques and setups to measure energy use and indoor environment in the building
environment.

Leonid Gurevich got his Ph.D. in Physics at the Institute of Solid State Physics
(Chernogolovka, Russia) in 1994. He initially worked on high-Tc superconductors but
during his postdoc stay at Delft University of Technology became excited about nanotech-
nology and the possibility of charge transport through a single molecule. Since 2005 he has
been an Associate Professor at Aalborg University. His research interests are focused on
molecular electronics, biosensors, functional surfaces and nanofabrication. Surface modi-
fication and functionalization is one of his most essential tools interfusing all these fields.

1860 J. Nanosci. Nanotechnol. 14, 1859–1871, 2014

Jensen et al.
Figure 1. Schematic phase diagram of water. Condensation is the phase
transition from gas to liquid phase.
negative contribution from the volumetric Gibbs energy,
Gv , which favors the transition, whereas the other term
is an unfavorable positive contribution originated from the
surface Gibbs energy, which is also called interfacial free
energy or surface tension, . The change in Gibbs energy
is shown in Eq. (1), where V is the liquid volume and S is
the liquid surface area, R is the drop radius, and  is the
surface tension of a planar surface.
4R3
G = −VGV + S = − GV + 4R2 
3 Nucleation
This expression has a maximum at G/R = 0 where:
3
16
Gcr =
3GV 2
and the drop radius equals the critical radius Rcr = −2 /
GV , see Figure 2. This means that droplets smaller than
the critical size are unstable and will evaporate whereas
larger droplets will grow. Hence, a nucleus with a size
above the critical size is needed to facilitate condensation,
Figure 2. Schematic change in Gibbs free energy at droplet formation
as a function of droplet radius.
J. Nanosci. Nanotechnol. 14, 1859–1871, 2014
Water Condensation: A Multiscale Phenomenon
wherefore the condensation is said to be initiated by
nucleation.10 11 That is, the water may be kept in the kinet-
ically stabilized metastable gas phase as the convex cur-
vature of the liquid surface imposes an energy barrier,
Gcr , for the vapor-to-liquid phase transition. Therefore
the gas phase should be supersaturated in order to initiate
condensation.12
The surface influence is also manifested in the Kelvin
equation (Eq. (3)). It states that the curvature of the droplet
surface gives rise to a difference in vapor pressure com-
pared to a flat surface, as:
pc = p e2Vm /rRT (3)
where pc is the vapor pressure in the presence of the
curved surface, p is the vapor pressure without a curved
surface,  is the liquid–vapor surface tension, Vm is the
molar volume of the liquid phase, r is the radius of cur-
vature, R is the gas constant, and T is the temperature.2
From Eq. (3) it is observed that the smaller the radius of a
droplet the higher is the increase in vapor pressure caused
by the surface curvature. It also appears from the equation
that condensation may actually occur above the dew point
temperature/below saturation vapor pressure if a concave
liquid surface is formed e.g., in the cavities on a rough
surface.13
2.2. Condensation on a Substrate—Heterogeneous
(1)
Nucleation on a substrate is said to be heterogeneous,
whereas the nucleation by spontaneously formed drops
above the critical size is called homogenous.11 The sub-
(2)
strate affects the nucleation process by lowering the energy
barrier of heterogeneous nucleation compared to that of
homogeneous nucleation.2 10
According to the CNT the energy barrier of condensa-
tion with heterogeneous nucleation depends on the wetting
properties of the substrate, where the wetting properties are
characterized by the contact angle, , between substrate
and liquid, see Figure 3.10 11 14–16 When the contact angle
is 0 the solid surface is fully wetted by the liquid, which
forms a film, whereas the liquid is completely repelled by
the surface when the contact angle is 180 and the liquid
forms a whole sphere on the surface. If it is assumed that
a droplet forms a spherical cap on a plane solid substrate
the energy barrier of nucleation becomes:17
3
16
Gcr het = f  (4)
3GV 2
where the geometric factor, f  , is:
1
f  = (5)
2 − 3 cos + cos3 /4
From Eqs. (4) and (5) it can be seen that the energy barrier
for heterogeneous nucleation is always lower than the bar-
rier for homogeneous nucleation, and in fact this can be
1861
Water Condensation: A Multiscale Phenomenon Jensen et al.

Figure 3. Schematics of gas–solid (GS ), liquid–solid (LS ), and gas–

liquid () surface tensions at the contact line of a drop on a solid sub-
strate. The contact angle of the drop is .

generalized to the cases where the substrate is not planar.16

The nucleation process is thermally activated, and there-
fore the nucleation rate, J , exhibits the Arrhenius behavior:
 
Gcr
J = J0 exp − (6)
kB T
where J0 is a kinetic constant and kB is the Boltzmann
constant.10 This shows that the reduction of the nucleation
energy barrier of heterogeneous nucleation also entails a
higher nucleation rate. When the contact angle is 180 the
energy barriers of homogeneous and heterogeneous con-
densation are equal. The lower energy barrier and thereby Figure 4. Environmental scanning electron microscope (ESEM) images
higher nucleation rate on hydrophilic surfaces, compared of water condensation on surface with hydrophilic and hydrophobic paths
to hydrophobic surfaces, has been examined experimen- with a width of 25 m. The water contact angle on the hydrophilic
tally by Varanasi et al.18 On a surface with alternating regions is ∼ 25 , whereas it is ∼ 110 on the hydrophobic regions. In the
first image (a) the surface is dry whereafter the humidity is increased
hydrophilic and hydrophobic paths they observe prefer-
(b)–(h) until droplets are observed. The drops are observed to form
ential nucleation on the hydrophilic regions, as can be preferably on the hydrophilic paths. Reprinted with permission from [18],
observed in Figure 4. Similarly, Na and Webb19 found K. K. Varanasi et al., Appl. Phys. Lett. 95, 094101 (2009). © 2009,
that the supersaturation required for nucleation depends on American Institute of Physics.
the contact angle, as the surfaces with low contact angle
require lower levels of supersaturation for nucleation to introduced a roughness factor, r, given by the actual sur-
occur, as compared to the surfaces with high contact angle. face area divided by the geometrical plane surface area,
The question is then, what determines the contact angle of into the interfacial tension balance in Eq. (7):22
the liquid drop on the solid substrate.
When condensation takes place on a substrate, two more cos rough = r cos flat (8)
interfaces are created in addition to the liquid–gas inter-
face; namely the solid–liquid and the solid-gas interfaces. Wenzel’s modification is based on the assumption that liq-
By balancing forces along the contact line, as presented uid penetrates into the depressions of rough surfaces. From
in the Young equation in Eq. (7) and in Figure 3, it fol- the modification it appears that a hydrophilic substrate
lows that at thermodynamic equilibrium the contact angle will become more hydrophilic when roughened, whereas
on a smooth surface is determined by the gas–solid (GS ), a hydrophobic substrate will become more hydrophobic.
liquid–solid (LS ), and gas–liquid () surface tensions.20 This is for instance illustrated by experiments performed
by Klemm et al.11 23 by roughening of glass. According to
GS − LS their experiments, increased roughness of the hydrophilic
cos = (7)
 glass results in water vapor condensation taking place at
higher temperatures.23
That is, the contact angle of dew on a substrate is deter-
To describe the situation where the liquid does not pen-
mined by the surface energy of the substrate, which is
etrate the depressions of a rough hydrophobic surface and
directly related to the chemical composition of the sur-
air is trapped in the depressions the following equation
face. It can be observed from Eq. (7) that when GS < LS
derived by Cassie and Baxter for calculating the contact
the contact angle is > 90 , and in this case the surface
angle on chemically heterogeneous surfaces, het , can be
is designated as hydrophobic. Contrarily, the surface is
used.24
called hydrophilic when GS < LS and the contact angle
cos het = f1 cos 1 + f2 cos 2 (9)
is < 90 . The highest water contact angle attainable on a
smooth surface is reported to be around 120 .21 However, Here, f1 and f2 are the fractional areas of surface type 1
the contact angle is also affected by the roughness of the and 2, respectively, and 1 and 2 are the local contact
surface, as was initially recognized by Wenzel. He has angles on surface type 1 and 2, respectively. When Eq. (9)

1862 J. Nanosci. Nanotechnol. 14, 1859–1871, 2014

Jensen et al.
is used to describe the situation where air is trapped in
the depressions under a drop on a rough surface, hence

2 = 180 , the equation reduces to:
cos rough = f1 cos 1 − f2 (10)
with f1 being the fractional area of fluid contact and f2 the
fractional area of air-liquid contact underneath the droplet,
both normalized by the geometrical plane surface area.
It is now generally accepted that heterogeneous conden-
sation is initiated by nucleation. However, another model
where the condensation is initiated from a thin film on a
substrate does also exist.1 This will, though, not be further
considered in this review. According to Merikanto et al.25
the nucleation step is the limiting step in a phase transition.
2.3. Droplet Growth
When describing droplet growth patterns on a substrate
the process is normally divided into three stages of which
nucleation is the first one. In the second stage of the pro-
cess the droplets grow primarily by diffusion of vapor from
the surroundings, and in the third stage the drop growth is
mainly caused by coalescence.10 14 26
The growth of an isolated droplet is governed by diffu-
sion. This mechanism can encompass both diffusion of sin-
gle molecules from the gas phase and diffusion of clusters
and adsorbed molecules along the substrate surface.14 26
Experimental studies by Leach et al.27 show that smaller
droplet growth primarily occurs by diffusion of adsorbed
water along the substrate surface, whereas larger droplets
grow mainly by diffusion of vapor from the gas phase. The
diffusion is driven by the concentration gradient around
the droplet caused by the fact that the droplet acts as a
mass sink, and in fact this may lower the vapor pressure
sufficiently to prevent nucleation within a certain perime-
ter around already existing drops. In the diffusion regime
the droplet size distribution is approximately monodisperse
and the increase of the mean drop radius follows a power
law with an exponent of 1/3.14 26
When droplets have grown so large by diffusion that
their perimeters come into contact with each other the
droplets coalesce. The coalescence typically starts when
the drops cover more than 30% of the substrate, which
means that the transition from the diffusion to the coales-
cence growth stage occurs faster at lower contact angles.28
In contrary to the growth by diffusion, the coalescence
by itself does not increase the mass of condensate on
the surface. However, it releases the substrate surface that
becomes available for growth of a new generation of
droplets by nucleation and diffusion, and with time the
droplet size distribution on the surface becomes highly
polydisperse. In this growth regime the ratio between
dry and wet surface areas saturates at the wet area frac-
tion of approximately 55%, and the growth of the mean
drop radius follows a power law with an exponent of
unity.10 14 29 However, according to Leach et al.27 the wet
J. Nanosci. Nanotechnol. 14, 1859–1871, 2014
Water Condensation: A Multiscale Phenomenon
area at saturation varies depending on the liquid contact
angle on the substrate. On an inclined surface the largest
drops will eventually slide off due to gravity, whereby sur-
face is also released for growth of new droplets.1 30 In this
case, the condensation process is cyclic.
3. NANOSCOPIC EFFECTS
As stated above, the initial nucleation step of condensation
is the limiting step in a phase transition. Therefore it is also
notable that even though the condensation process may
be considered from a macroscopic perspective the initial
step occurs on the nanoscale where bulk properties and
assumptions are not necessarily valid. In general, surface
effects become increasingly important compared to volume
effects at decreasing droplet sizes.
3.1. Nanoscopic Effects on the
Classical Nucleation Theory
The CNT, which is commonly used for the description of
the initial step of phase transition, is reported to be inac-
curate at the nanoscale.25 31 It is reported by Merikanto
et al.25 that the modelling of small clusters as bulk liq-
uid, in accordance with the CNT, introduces an error to
the calculated energy barrier of nucleation at cluster sizes
below 8 to 50 molecules, depending on temperature and
molecule species. Likewise, Prestipino et al.31 and Ghosh
and Ghosh32 have introduced corrections to the CNT by
assuming a nonsharp interface. Thereby they have obtained
a more accurate description of the surface tension and
liquid density dependences on cluster size, whereby the
energy barrier of nucleation is reduced compared to the
CNT. This has also been demonstrated in molecular dynam-
ics (MD) simulation by Toxvaerd,33 which shows that the
solid–liquid and liquid–vapor interfaces cannot be sepa-
rated for nuclei consisting of ∼ 100 molecules. Therefore
the surface tensions on nanoscale become smaller than the
bulk surface tensions. Furthermore, the simulations show
that the vapor density near the surface is enhanced, which
should be taken into account in the CNT. The use of molec-
ular simulations may be considered as a way of avoiding
inaccuracies of the CNT. However, this is not necessarily
providing more accurate results relative to the CNT when
compared to experimental results.16
3.2. Nanoscopic Effects on the Contact Angle
The Wenzel and Cassie-Baxter equations presented above
describe the contact angle of a fluid on a rough sur-
face in the states where liquid, respectively, penetrates
or does not penetrate the depressions of the surface.
It has been suggested to use the Wenzel equation in
the hydrophilic region and the Cassie-Baxter equation in
the hydrophobic region.34 However, according to other
authors it is not unambiguously described by macroscopic
parameters which of the two states are occupied under
which conditions.35 The energetically most favorable of the
1863
Water Condensation: A Multiscale Phenomenon
Wenzel and Cassie-Baxter states is the one with the lowest
apparent contact angle. However, this does not mean that
a drop will attain this state as the state initially attained
depends on how the drop is formed on the surface, and
an activation energy barrier is present between the two
states.36 37 The presence of an activation barrier between
the Wenzel and Cassie-Baxter states renders it possible
for the states to be metastable, and actually the Cassie-
Baxter to Wenzel transition is irreversible according to
Nosonovsky and Bhushan.38 For instance, experiments by
Cheng and Rodak39 and Xiao et al.40 have shown that some
rough surfaces, which are normally designated as superhy-
drophobic, only carry this characteristic when water drops
of macroscopic size are deposited on the surfaces. When
instead water condensed on the surfaces the contact angles
were well below 90 . This has been explained by the pres-
ence of condensed water in the depressions of the rough
surfaces, whereby the fractional area of air-liquid contact
beneath the droplet has been reduced.
3.2.1. The Three-Phase Contact Line
It has been argued by Gao and McCarthy41 that only rough-
ness at the three-phase contact line of a drop on a surface
is relevant when determining the liquid contact angle, and
therefore it is incorrect when the surface roughness of the
liquid–solid contact area is used in the Wenzel and Cassie-
Baxter equations. This is, however, only relevant on sur-
faces where the surface roughness is non-uniform or where
the characteristic dimension of the surface roughness is
comparable to the drop size.42 43 In cases where either of
the two applies, the local surface roughness at the three-
phase contact line should be used in the Wenzel and Cassie-
Baxter equations to obtain the local contact angle.38 44 It
is noteworthy that the small droplets formed in the initial
stages of dew formation actually have a size comparable to
the characteristic dimension of the surface roughness.
3.2.2. Line Tension
One of the parameters neglected when describing the con-
tact angle by the Young equation, and thereby also when
describing the nucleation rate by the CNT, is the line ten-
sion acting along the three phase contact line of a droplet,
analogous to surface tension acting at the surface between
two phases.45–49 That is, the line tension is a consequence
of an imbalance of intermolecular forces in the junction
of the three phases. The line tension typically amounts to
10−10 to 10−6 N and it has high influence on the contact
angle of nano- and submicron droplets, whereas the drops
with macroscopic dimensions are not significantly affected
by the line tension.45 46 The effect of the line tension, ,
on the contact angle has been introduced through the mod-
ified Young equation:45 49
cos = cos − k (11)
 the surface heterogeneity and topography, the nucleation
where  is the contact angle described by Eq. (7) and
k is the geodesic curvature of the three-phase contact line.
1864
Jensen et al.
A consequence of the influence of line tension is that
the contact angle depends on the drop size, as appears
from Eq. (11).45 46 49–51 Measurements by Cao et al.52
show that the contact angle is drastically reduced for
micrometer or submicrometer sized droplets on hydropho-
bic surfaces, which correlates well with results presented
by Barberis and Capurro50 showing that at the nanoscale
the contact angle increases with increasing droplet size.
However, through theoretical models it has been shown
that the contact angle can both increase or decrease with
increasing droplet size depending on the line tension,47
surface heterogeneity,53 and surface roughness.54 In respect
to CNT, the inclusion of line tension can theoretically
make homogeneous nucleation more thermodynamically
favorable than heterogeneous nucleation.47
3.2.3. Contact Angle Hysteresis
According to Tadmor,55 the line energy is a function of
surface irregularities, which gives rise to contact angle hys-
teresis. That is, when a drop advances on a surface the
contact angle is higher than when a drop recedes on the
same surface despite the fact that the macroscopic interfa-
cial energies are the same.56 Microscale roughness is one
of the irregularities contributing to contact angle hysteresis
as the roughness locally disturbs the shape of the spheri-
cal cap anticipated in the Young equation and CNT. Due
to pinning of the three-phase contact line the microscale
roughness makes a range of contact angles energetically
favorable, in addition to those described by the Wenzel
and Cassie-Baxter equations.35 38 55 Furthermore, adhesion
hysteresis38 and microscale chemical heterogeneity55 con-
tributes to the contact angle hysteresis. However, contact
angle hysteresis is also observed on smooth homogeneous
solid substrates. According to Starov12 this is caused by
the fact that at any contact angle between the receding
and the advancing ones the droplet is in slow “micro-
scopic” motion and therefore it is not in equilibrium, as
required for the Young equation to be valid. When the
contact angle is below or above the receding or advancing
contact angles, respectively, the droplet motion becomes
“macroscopic.”
3.2.4. Nucleation Sites
The surface heterogeneity and roughness give rise to local
variations on a surface. In this respect the surface het-
erogeneity may be caused by both internal effects, such
as local variations in chemical composition and rough-
ness, and by external effects, such as adsorption of water
vapor and contaminants.19 57 58 This creates nucleation
sites where nucleation is particularly favorable, as has
been shown in experiments by Mu et al.59 According
to their experiments the nucleation site density is higher
on surfaces with higher fractal dimensions. Apart from
site density also depends on the minimum droplet radius,
which, in turn, depends on the surface subcooling.60 Even
J. Nanosci. Nanotechnol. 14, 1859–1871, 2014
Jensen et al.
though the nucleation rate is expected to be higher on
hydrophilic than on hydrophobic surfaces according to
CNT, Leach et al.27 have not observed significant differ-
ences in the nucleation densities between surfaces with
the contact angles of 60 and 100 . However, their mea-
surements may not be entirely reliable since the effects
of surface topography and heterogeneity have not been
controlled.
3.3. Adsorption
Characterization of a substrate from a macroscopic point
of view, as discussed in Section 2,2, requires knowledge
of the surface tensions. The latter may vary locally due to
chemical and topographical heterogeneity of the substrate,
as described above. Besides that, another effect to consider
in this respect is adsorption of water on the substrate. The
adsorption of water molecules on a surface is controlled
by surface forces; such as Van der Waals forces, hydrogen
bonding, electrostatic forces, and steric forces.12 That is,
the water molecules are bound to the surface and there-
fore this water does not possess the characteristics of bulk
liquid.
At ambient conditions the gas–solid surface tension is
always affected by adsorption of water molecules from the
air, as
GS = GS
0
1 −  + GSa
(12)
with being the fraction of solid surface covered by
0
adsorbed water molecules, GS is the surface tension
a
of the bare solid surface, and GS the surface ten-
sion of the surface covered entirely by adsorbed water.12
Furthermore, the fraction of solid surface covered by
adsorbed water molecules depends on the vapor pressure,
which also makes GS a function of the vapor pressure.
On hydrophilic surfaces the adsorption of water lowers
the gas–solid surface tension which results in adsorption
of a thin water film on the solid. This results in the
formation of a smooth transition zone between a liquid
droplet and the adsorbed liquid film on such surface, as
illustrated in Figure 5. The profile in the transition zone
is governed by surface forces, resulting in the so-called
disjoining or Derjaguin’s pressure.12 On the contrary,
adsorption of water on hydrophobic surfaces increases the
surface tension. Adsorption still occurs on hydrophobic
surfaces as long as the contact angle is lower than 180 ,
though, in general, to a lower extent than on hydrophilic
surfaces.12 46 61 Measurements by Cao et al.52 have shown
that nanometer-sized droplets of water are adsorbed on
hydrophobic surfaces at ambient conditions where the rel-
ative humidity is much lower than 100%, indicating that
the physics at the nanometer scale cannot be ignored when
considering condensation. According to their measure-
ments, adsorption of water on hydrophobic surfaces pri-
marily occurs on surface defects, which act as nucleation
centers. This is consistent with the measurements by James
et al.61 showing that the macroscopic contact angle is not
J. Nanosci. Nanotechnol. 14, 1859–1871, 2014
Water Condensation: A Multiscale Phenomenon
Figure 5. Schematics of the transition from macroscale droplet to
nanoscale film. Reprinted with permission from [12], V. M. Starov, Adv.
Colloid Interface Sci. 161, 139 (2010). © 2010, Elsevier.
necessarily directly related to the molecular adsorption
of water on surfaces covered by different self-assembled
monolayers. However, according to Furuta et al.62 the con-
tact angle of water on a hydrophobic surface decreases
with decreasing temperature due to an increase in water
adsorption which renders the surface more hydrophilic.
The ordered structure of adsorbed liquid on a solid sur-
face also influences the interfacial energy transport effi-
ciency at the solid–liquid interface. At the interface there
is a thermal resistance, known as the Kapitza resistance,
due to the mismatch between the properties of the solid
and the liquid. MD simulations have revealed that the
Kapitza resistance depends on the wetting properties of
the solid, as the stronger adsorption and thereby also more
ordered liquid on wetting interfaces reduces the Kaptiza
resistance, whereas it is increased on non-wetting inter-
faces where the adsorbed liquid is less ordered at the inter-
face. The simulations have been made both for a general
case of a Lennard-Jones fluid on a Lennard-Jones solid63
and for a specific case of water on different self-assembled
monolayers.64 The simulations by Xue et al.63 also showed
that the thermal conductivity in the structured liquid was
indistinguishable from that of bulk liquid.
The effects described in Section 3, all show that a sub-
strate cannot be characterized solely by the macroscopic
contact angle determined from surface tension and sur-
face roughness. First of all, the surface tension and surface
roughness vary locally on the surface, and their effects on
the contact angle depend on drop size. Secondly, several
other parameters affect the contact angle. To summarize
the discussion of condensation theory presented until now
in this review, the condensation process is very complex
and it involves phenomena on several length scales rang-
ing from the atomic scale at nucleation to the macro scale
where drops will slide off an inclined surface.
4. THE MOLECULAR APPROACH
As opposed to the macroscopic approach presented above,
the condensation process can also be described from
a molecular viewpoint, i.e., based on the interactions
between individual molecules. Two methods are com-
monly used for the description; namely, MD or Monte
1865
Water Condensation: A Multiscale Phenomenon Jensen et al.

Carlo (MC) methods.65 In the MD calculation Newton’s

equations are solved to obtain the trajectories of individ-
ual molecules in the system. This requires the descrip-
tion of intermolecular forces, such as Van der Waals
forces, electrostatic forces, hydrogen bonding, and steric
interactions etc. by an intermolecular potential. From a
classical approach the intermolecular potential of unpolar-
ized molecules, such as argon, is often described by the
Lennard-Jones potential, as follows:16
 6  12
A B
VLJ = − + (13)
r r
The first term describes the attractive Van der Waals
forces, whereas the second term describes the Pauli repul-
sion originating from the Pauli exclusion principle of
electrons.66 However, this description is not sufficient for
molecules with an inherent dipole moment, such as water.
In these cases, the dipole character of water needs to be
considered as a permanent positive charge on the oxy-
gen atom and permanent negative charges on the hydrogen
atoms.67 The interaction between charges is described by
the Coulomb potential between point charges, as follows:68
1 q1 q2
VCoulomb = (14)
4 0 r

where q1 and q2 are the interacting charges separated

by the distance r, and 0 is the vacuum permittivity.
According to Molinero and Moore,69 around hundred ver-
sions of the intermolecular potential of water exist, with
the most popular ones being SPC,70 SPC/E,67 TIP3P,71
TIP4P,71 and TIP5P.72 All these water models treat the
water molecules as rigid molecules. However, the popular
potentials all include the electrostatic term, which is long-
ranged and therefore computationally heavy, to obtain a
correct description of the hydrogen bonds in water. There-
fore, in order to improve computational efficiency other
simpler potentials have been developed. The monatomic
water (mW) model presented by Molinero and Moore69 is
an example of such an improved system, where the electro-
static term is replaced by a short-range term, which favors
tetrahedral configurations of the water molecules. The
description of intermolecular potentials may also be done
by applying a quantum mechanical approach, whereby the
description is actually at the electron level.16
Additionally, in the case of condensation on a sub-
strate, the intermolecular potentials between the substrate
molecules and the forces between molecules of the sub-
strate and water molecules must be known.57
When knowing the intermolecular potentials in a system
it is possible to calculate the movement of the individ-
ual molecules within a certain time interval by MD when
the initial positions and velocities of the molecules are
known. Hereby, it is possible to calculate e.g., how the
condensation process progresses in time and the nanoscale
effects discussed in the previous sections are inherent.
However, it is computationally very heavy due to the need
Figure 6. (A) Nucleation onset pressure as a function of temperature
for argon at a nucleation rate of 107 s−1 cm−3 calculated from differ-
ent models (CNT, SC-CNT, RKK, MC simulation-based) and measured
experimentally, and (B) nucleation rates for water as a function of super-
saturation. Reprinted with permission from [25], J. Merikanto et al., Phys.
Rev. Lett. 98, 145702 (2007). © 2007, The American Physical Society.
to calculate the movement of the individual particles, and
as the time steps need to be in the femtosecond range.65 73
For instance, Nagayama and Tsuruta74 75 has used MD
simulations in the study of condensation coefficients of
argon and water.
In comparison to MD, the MC approach for modelling
of condensation at the molecular scale is computationally
less heavy, and the method is widely used for simulation
of condensation.25 57 76–78 Figure 6 shows an example of
results from MC simulations by Merikanto et al.25 com-
pared to results obtained from CNT and two modified
versions of CNT (SC-CNT79 and RKK80 ). The simulation
results are furthermore compared with results from nucle-
ation pulse experiments.81 82
The first flow scheme for an MC method was presented
by Metropolis et al.65 From an initial configuration of
molecular positions a new configuration is generated by
random displacement of a molecule in the initial configu-
ration. Hereafter the potential energies of the old and new
configurations, calculated by intermolecular potentials, are
compared, and if the new configuration has a lower energy
it is accepted whereafter it is used as basis for generation

1866 J. Nanosci. Nanotechnol. 14, 1859–1871, 2014

Jensen et al.
of another configuration change in the iteration process.
If, on the contrary, the new configuration has a higher
energy than the old one it is compared with a random
number to determine if it is accepted or rejected as basis
for the next configuration change. The process is iterated
until an equilibrium state is achieved. An ensemble of con-
figurations is obtained from the MC method whereby it is
possible to calculate equilibrium properties by sampling.
That is, the MC method is stochastic in nature as opposed
to the deterministic MD method.65
5. SIMULATION OF CONDENSATION
The dynamic simulation of heterogeneous condensation is
not a trivial task, as illustrated by the condensation theory
outlined above. In principle, it is required to combine sev-
eral models in order to simulate the phase change occur-
ring in a multiscale condensation process. The core of the
simulation is suggested to be the growth models describ-
ing the different regimes of drop growth in condensation.
That is, nucleation, diffusion, and coalescence, and addi-
tionally drop slide-off on inclined surfaces should be mod-
elled. To simulate the nucleation correctly it is envisaged
that the nucleation model should be coupled to a surface
model describing the distribution of nucleation sites on
the substrate. That is, the surface model should describe
the substrate heterogeneity. The driving force in condensa-
tion is provided by temperature and humidity differences.
Therefore coupling of a heat and mass transfer model to
the droplet growth models is essential for the simulation
of condensation.
5.1. Drop Growth Models
In literature there has been focus on dropwise conden-
sation as the heat transfer coefficient of dropwise con-
densation is usually an order of magnitude higher than
that for filmwise condensation, which is caused by the
enhanced slide-off from hydrophobic surfaces compared
to hydrophilic ones.1 58 To a great extent this interest has
driven the research in drop growth where the higher heat
transfer coefficient may be utilized in the design of steam
condensers etc. One of the major challenges in the mod-
elling of drop growth lies within the fact that the phe-
nomenon is multiscale, ranging from the atomic scale at
nucleation to the macroscale at drop slide-off from inclined
surfaces.27 Numerous references describing the individual
regimes of droplet growth can be found in the literature.
However, only one model describing the entire growth
process from nucleation to slide-off has been found. The
model, developed by Sikarwar et al.1 83 consists of a loop
for simulation of condensation by diffusion running in par-
allel with a loop for simulation of coalescence. In the
model it is assumed that the initial nucleation site density
is 109 m−2 and that any free nucleation site is instanta-
neously occupied by a nucleus of smallest possible stable
size. The radius of these nuclei, rmin , has been obtained
J. Nanosci. Nanotechnol. 14, 1859–1871, 2014
Water Condensation: A Multiscale Phenomenon
from thermodynamic considerations by Rose60 as pre-
sented in Eq. (15).
2Tw
rmin = (15)
hLV · L · TV − Tw 
Here, Tw and TV are the wall and vapor temperatures,
respectively, hLV is the latent heat of condensation, and
L is the liquid density. According to this description the
minimum drop size is depending on the liquid properties
and wall subcooling. As stated in Section 3.2.4 and has
been pointed out by Sikarwar et al. the nucleation site
density depends on the surface roughness59 and surface
subcooling.60
In the model by Sikarwar et al. the growth of individual
drops is described by:1
dr 4Tt 1−rmin /r 1−cos
= · · (16)
dt L ·hLV 2/hi +r/kl 2−3cos +cos3
where Tt is the total temperature drop made up of tem-
perature drops due to resistance of interfacial heat trans-
fer, resistance of thermal conduction, and resistance due to
droplet curvature. The total temperature drop will balance
the subcooling. hi is the interfacial heat transfer coefficient
and kl is the thermal conductivity of the liquid. Coales-
cence is considered, as drops that make contact are antici-
pated to coalesce instantaneously, whereby the coalescing
drops form a new drop with volume conserved and located
at the weighted center of mass. The critical drop size at
slide-off from an inclined substrate surface is obtained in
the model by setting up the balance of forces acting on
the drops with gravity favoring sliding and surface tension
preventing it. Likewise, a maximum drop size is given, as
drops larger than this size will fall off the surface due to
gravity when the surface is inclined more than 90 com-
pared to horizontal. In the expressions for critical and max-
imum drop sizes the contact angle hysteresis is also taken
into consideration.
Figure 7 shows pictures from experiments compared to
simulation results of Sikarwar et al.1 83
5.2. Nucleation Models—Molecular Modelling
The nucleation of a droplet during condensation involves
relatively few molecules, and the nucleus size is in the
nanoscale realm where continuum models do not apply.
Therefore, molecular modelling is an obvious choice for
simulation of the nucleation step of condensation.
For instance Mokshin and Galimzyanov84 have simu-
lated homogeneous nucleation of water by MD using the
mW model. From these simulations they have been able
to calculate surface tension, nucleation rate, and critical
cluster size etc. The calculated surface tension matches
experimental data well, whereas the nucleation rate and
critical cluster size are only compared with other models,
showing that the mW model gives higher nucleation rate
(Fig. 8) and higher critical cluster size as compared to the
1867
Water Condensation: A Multiscale Phenomenon
Figure 7. Dropwise condensation on a substrate. Left images show the steps of condensation observed experimentally, and right images show
simulation results of Sikarwar et al. (2012) for the steps. Reprinted with permission from [1], B. S. Sikarwar et al., Heat Transfer Eng. 33, 301 (2012).
© 2012, Taylor & Francis Ltd.
CNT. This illustrates one of the challenges in modelling
nucleation; namely, the fact that the phenomenon is hard
to examine experimentally, as e.g., the critical nucleus
consists of less than 100 water molecules, wherefore
experimental data for comparison are scarce.85 However,
experimental measurements of the nucleation rate do exist,
as for instance the measurements by Viisanen et al.86 who
Figure 8. Nucleation rate as a function of temperature calculated from
MD simulations using different intermolecular potentials of water, and
from the CNT. Reprinted with permission from [84], A. V Mokshin
and B. N. Galimzyanov, J. Phys. Chem. B 116, 11959 (2012). © 2012,
American Chemical Society.
1868
Jensen et al.
have used the nucleation pulse technique for measuring the
rates of homogeneous nucleation of water at different tem-
peratures. The measurements have shown that the CNT did
not provide a good fit to the experimental data, though the
technique has been later questioned by Winter et al.85 as
the nucleation rate measurements by the nucleation pulse
technique require that nuclei have grown to a detectable
size. An experimental study of heterogeneous nucleation
has been conducted by Lauri et al.87 using environmental
scanning electron microscopy (ESEM) showing that CNT
overestimates the supersaturation required for nucleation
onset. However, this technique also suffers from the fact
that nuclei of critical size are too small to be observed
and therefore the nuclei must grow before they become
detectable.
The failure of the CNT at very small cluster sizes has
also been demonstrated by Merikanto et al.25 who has used
molecular MC simulations to show that the CNT fails at
small cluster sizes in the range of 8–50 molecules depend-
ing on temperature and molecules in question. MC simu-
lations by Winter et al.76 85 show that inclusion of the line
tension in the Young equation increases the accuracy of the
CNT for describing the free energy of droplet formation
at heterogeneous nucleation. Examples of snapshots from
the simulations of Winter et al. are shown in Figure 9.
MD simulations of a Lennard-Jones fluid by Inci and
Bowles88 have shown that the heterogeneous nucleation
on nanosized seed particles is well described by the CNT
with respect to the critical nucleus size, whereas the energy
J. Nanosci. Nanotechnol. 14, 1859–1871, 2014
Jensen et al.
Figure 9. Snapshots of MC simulations by Winter et al. (2009) of het-
erogeneous condensation with contact angles of ∼ 58 (left) and 90
(right). Reprinted with permission from [85], D. Winter et al., J. Phys.:
Condens. Matter 21, 464118 (2009). © 2009, Institute of Physics.
barrier of nucleation, and thereby the nucleation rate, is
overestimated by CNT. For a comprehensive review on
molecular simulations and other models of nucleation the
reader can refer to the book by Vehkamäki.16
5.3. Heat and Mass Transfer Models
Simulation of heat and mass transfer is often done based
on numerical solving of the governing equations of fluid
dynamics; namely the mass, momentum, and energy equa-
tions founded on the assumption of mass conservation,
Newton’s second law, and the first law of thermodynamics,
respectively.89 This method takes each phase into account
as a continuum described by their respective macroscopic
properties. Through the governing equations it is possi-
ble to describe the heat transfer, which can occur by the
mechanisms of conduction, convection, and radiation,90
and analogously it is possible to describe the mass transfer
by diffusion and convection. In the case of water con-
densation on a solid substrate three different domains are
identified. These are the vapor flow domain, the water
flow domain, and the solid domain.91 In this instance, the
problem of dew formation on a surface is essentially a
conjugate fluid-solid heat and mass transfer problem in
the presence of a phase changing fluid layer on the solid
surface.92
The modelling of condensation by heat and mass trans-
fer models alone has been attempted by several authors,
and it is a common assumption that condensation will
occur when the temperature gets below the dew point
temperature.4 5 7 8 93 94 In these models nucleation as such
is not considered and it is implicitly anticipated that the
condensation forms a film on a completely wetted sub-
strate. In the simplest models only steady state heat trans-
fer by conduction is modelled, whereas convective and
radiative heat transfer are considered by conversion of
these to an equivalent conductive heat transfer.8 95 A more
advanced steady state model has been presented by Bong
et al.7 where both conductive and convective heat trans-
fer are considered with a k– turbulence model used for
the convection. Though, radiative heat transfer and mass
transfer are not considered in this model, and furthermore
J. Nanosci. Nanotechnol. 14, 1859–1871, 2014
Water Condensation: A Multiscale Phenomenon
the absolute humidity is anticipated not to vary in space
in both the models mentioned above. Firstly, steady state
methods are more inaccurate to predict the condensation
risk compared to transient methods.96 Secondly, dynami-
cal simulation of the development of condensation requires
a transient model, and mass transfer cannot be ignored,
meaning that temperature and humidity may vary both
in time and space.4 A transient model including conduc-
tive and convective heat transfer and diffusive and con-
vective mass transfer has been made by Liu et al.4 The
model includes local variations in temperature and abso-
lute humidity and defines condensation rate from the local
supersaturation of vapor and the moisture transfer coef-
ficient, which is again calculated from the heat transfer
coefficient. This is based on an assumption of heat and
mass transfer analogy, and eliminates the need to solve the
mass diffusion equation.91 However, according to Croce
et al.91 the assumption is not always valid. The model of
Liu et al. illustrates another problem of obtaining an accu-
rate model; namely the issue of modelling turbulent flow
accurately. Though, the accuracy of turbulence models is
outside the scope of this review, and it will therefore not
be further discussed.
A transient heat and mass transfer model taking some
substrate effects into consideration has been produced
by Croce et al.91 92 97 98 In their model they distinguish
between filmwise and dropwise condensation for the cal-
culation of heat flux to the substrate and they find that
calculation of the condensation rate from the mass diffu-
sion equation is more accurate than using the heat and
mass transfer analogy.91 Furthermore, the latent heat of
condensation is included in the model and it is found to
be an important factor in the simulation of condensation
and evaporation with natural convection.
In all of the mentioned models it is assumed that con-
densation occurs when the temperature gets below the dew
point temperature, whereby the effect of the substrate, as
is part of the nucleation theory, is neglected. Furthermore,
a detailed resolution of the liquid–gas interface cannot be
obtained by CFD due to the macroscopic nature of this
approach. This is caused by the fact that the continuum
assumption breaks down at nanoscale.99 100
5.4. Simulation of the Solid–Liquid Interface
In the simulation by Gu et al.101 who have simulated film-
wise condensation of argon on a cooled substrate, the
interface is simulated at the nanoscale by MD and this is
coupled to a direct simulation MC approach for simulation
of bulk gas flow tangential to the substrate surface in order
to capture the interfacial details. However, the MD part of
the simulation only includes the Lennard-Jones potential
to calculate the interaction between molecules, which is an
oversimplification for a realistic water simulation. Further-
more, only filmwise condensation on a perfect crystalline
surface is modelled and nucleation sites are not taken into
consideration.
1869
Water Condensation: A Multiscale Phenomenon
Another hybrid model for the condensation of argon on
a platinum substrate has been developed by Sun et al.99
which combines MD simulation at the interface, where
microscopic phenomena mainly exist, with finite volume
methods for simulation of heat transfer and fluid flow
in the bulk gas phase, where the continuum assumption
applies. Again, the MD simulation only uses a Lennard-
Jones potential to describe the interaction between argon
molecules and a perfectly crystalline surface. Due to the
lack of inherent dipole moments in this system the results
cannot be ported directly to water systems.
6. CONCLUSION
The condensation process is a multiscale phenomenon, as
drop sizes span from molecular scale to typically mil-
limeter scale during their growth starting with nucleation
and ending with slide-off on inclined surfaces. In litera-
ture, the condensation process has been thoroughly stud-
ied, and modelled at both the molecular scale and the
macroscale. However, to the best of our knowledge a holis-
tic model of condensation, spanning the entire process,
does not exist. This may be considered as a natural con-
sequence of the fact that the molecular models used to
describe nucleation become too complex and computation-
ally heavy when larger drops are considered, and the con-
tinuum models used to describe larger drops are inaccurate
if they are applied to the nanometer-sized droplets consid-
ered in the nucleation. The solution to this issue may be
the development of hybrid models, however the level of
details necessary for describing the interface is a critical
and highly debated issue.
Acknowledgments: The authors would like to thank
Eirik Bjørn for insightful discussions. This work was sup-
ported by DOVISTA and The Danish Agency of Science
Technology and Innovation.
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Received: 30 July 2013. Accepted: 18 August 2013.
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