Advances in Colloid and Interface Science 170 (2012) 67–86

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Advances in Colloid and Interface Science

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Evaporation of pure liquid sessile and spherical suspended drops: A review

H. Yildirim Erbil ⁎
Department of Chemical Engineering, Gebze Institute of Technology, Gebze 41400 Kocaeli, Turkey

a r t i c l e i n f o a b s t r a c t

Available online 8 January 2012 A sessile drop is an isolated drop which has been deposited on a solid substrate where the wetted area is
limited by a contact line and characterized by contact angle, contact radius and drop height. Diffusion-
Keywords: controlled evaporation of a sessile drop in an ambient gas is an important topic of interest because it plays
Drop evaporation a crucial role in many scientific applications such as controlling the deposition of particles on solid surfaces,
Contact angle in ink-jet printing, spraying of pesticides, micro/nano material fabrication, thin film coatings, biochemical
Diffusion
assays, drop wise cooling, deposition of DNA/RNA micro-arrays, and manufacture of novel optical and
Superhydrophobic
Liquid marbles
electronic materials in the last decades. This paper presents a review of the published articles for a period
of approximately 120 years related to the evaporation of both sessile drops and nearly spherical droplets
suspended from thin fibers. After presenting a brief history of the subject, we discuss the basic theory
comprising evaporation of micrometer and millimeter sized spherical drops, self cooling on the drop surface and
evaporation rate of sessile drops on solids. The effects of drop cooling, resultant lateral evaporative flux and
Marangoni flows on evaporation rate are also discussed. This review also has some special topics such as drop
evaporation on superhydrophobic surfaces, determination of the receding contact angle from drop evaporation,
substrate thermal conductivity effect on drop evaporation and the rate evaporation of water in liquid marbles.
© 2012 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
1.1. Importance of the subject . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
1.2. History of drop evaporation research . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
2. Basic theory of drop evaporation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
2.1. Evaporation of millimeter sized large spherical drops . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
2.2. Evaporation of micrometer sized small spherical droplets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
2.3. Self-cooling on the drop surface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
2.4. Evaporation of sessile drops on solid: experimental aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
2.5. Evaporation of sessile drops on solid: effect of the presence of the substrate to decrease the rate of drop evaporation [f(θ) factor] . . . . 73
2.6. Evaporation of sessile drops on solid: rate equations without using the f(θ) factor . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
3. Specific topics on drop evaporation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
3.1. Drop evaporation on superhydrophobic surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
3.2. Determination of receding contact angle from drop evaporation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
3.3. Substrate thermal conductivity effect on drop evaporation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
3.4. Evaporation of drops having low contact angles, lateral evaporative flux and Marangoni flow in an evaporating drop . . . . . . . . . . 82
3.5. Evaporation of water in liquid marbles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
4. General conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85

1. Introduction

1.1. Importance of the subject

⁎ Tel.: + 90 262 605 2114; fax: + 90 262 654 2731. The occurrence of liquid evaporation is a natural phenomena and
E-mail address: yerbil@gyte.edu.tr. liquid drops evaporate when the atmosphere in the immediate

0001-8686/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.cis.2011.12.006
68 H.Y. Erbil / Advances in Colloid and Interface Science 170 (2012) 67–86
vicinity of the drop is not saturated with the vapor of the liquid. In
addition, very small droplets may evaporate even in saturated vapor
conditions due to the vapor pressure increase inside the droplet
which arises from the surface curvature of the droplet (Kelvin's
effect). Evaporation of a drop in an ambient gas was considered
since Maxwell time mainly as a diffusion-controlled process [1].
Drop evaporation is an important topic of interest because it plays a
crucial role in many engineering applications such as spray drying,
fuel injection into combustion engines, medical care, controlling the
deposition of particles on solid surfaces, rapid cooling by drop wise
heat exchange and also occurs in natural processes such as rain, fog,
dew, snow formation and is used in meteorological estimates
[1–41]. The cycle of water in nature proceeds via the condensation
of water vapor on hygroscopic particles (nucleation condensation)
in the atmosphere with the formation of cloud droplets. The hygro-
scopic particles are produced by the evaporation of sea-spray and
from other sources. The rain drops are formed from these clouds and
fall freely to ground while losing some of their mass by evaporation.
All of these processes can be described by using simultaneous diffusive
and convective mass and heat transfer equations though they are
considerably complex. The reverse of drop evaporation is the droplet
growth in a medium supersaturated with the vapor of the liquid
by condensation. The absorption of gases on liquid aerosol parti-
cles is analogous to the condensation of vapor on liquid droplets
and can be described by the same equations derived for drop
evaporation.
A sessile drop is a drop which is deposited on a solid substrate
where the wetted area is limited by a contact line. Contact angles of
sessile drops on substrates are essentially used in the calculation of
the surface free energy of the solid surfaces. Sessile drops evaporate
with time and the initial contact angle decreases depending on the
vapor pressure of the liquid and external conditions in some
instances. Thus, the understanding of how evaporation influences
the contact angle of a sessile liquid drop in still air or in controlled
atmospheric conditions is very important in the wetting and surface
characterization processes [2–20]. Sessile drop evaporation processes
have important applications in ink-jet printing [21,22], spraying of
pesticides [23], micro/nano fabrication [24,25], thin film coatings
[26], biochemical assays [27], spray cooling [28], deposition of DNA/
RNA micro-arrays [29–33], and manufacture of novel optical and
electronic materials [34] in the last decades.
If some insoluble particles are also present in an evaporating drop
they deposit onto the substrate in a ring at the air/liquid/solid interface
because of the pinning of the drop. The control of the morphology and
size of stains after the evaporation of solution or dispersion drops is a
subject of intensive research in the last two decades after the pioneering
publications of Deegan and co-workers [35–37]. The possible reasons
for the pinning and shrinking of a sessile droplet on a solid during
evaporation process were also investigated [38,39]. Different stain
profiles are obtained when drops contain dissolved materials or dispersed
particles, where these small particles are deposited on a surface after the
complete drop evaporation. It is important to control the shape of these
stains based on the surface functionalities of the deposits and the
geometry of the stains depends on the interactions between liquid,
substrate and the particles. For example, a uniform particle distribution
and flat spots are desired for ink deposition, whereas a stretched individ-
ual particle is desired for the DNA deposition and ordered arrays of ring-
shaped deposits are desired for applications such as fabricating refractive
microlens using ink-jet printing [40], obtaining transparent conductive
coatings forming a 2-D array of interconnected silver nanoparticle rings
stabilized by polyacrylic acid [41], separation of particles according to
their sizes (nanochromatography) which is based on a particle-size
selection mechanism near the contact line of an evaporating droplet
[42] and detecting toxins of 2–200 ng samples of microcystin-LR from
freshwater algae by Raman spectroscopy [43]. The dynamics of dewetting
and evaporative drying are functions of the interaction between the
surface and the liquid [44,45]. Drying dynamics were found to be con-
trolled not only by the volatility of the liquid but also by the properties
of the wetting film left on the substrate [46].
The evaporation of a liquid drop is basically a simultaneous heat and
mass transfer operation in which heat for evaporation is transferred by
conduction and convection from warm air to the drop surface from
which the vapor is transferred by diffusion and convection back into
the air. Thus, drop evaporation subject also covers the conduction
heat transfer into the substrate, the convective heat transfer induced
by the surface tension gradients and the natural convection due to
the temperature gradients in the liquid drop. Self-cooling of the
drop surface is an important factor with the more volatile liquids or
with water when it is rapidly evaporating in a completely dry
medium.
The evaporation phenomena can generate temperature variations in
the vicinity of the solid surface and along the drop interface. For pure
liquid drops, the Marangoni effect which is the thermo-capillary
convection can produce instabilities at the interface. On the other
hand, if a drop is placed on a heated substrate, the large temperature
difference between the drop and the substrate is the source of these
thermo-convective instabilities, induced by both Marangoni and
buoyancy forces for this case. Infra-red thermography was used to
investigate the Marangoni and buoyancy convection in a hanging drop
of silicone oil and hydrocarbons [47]. The substrate temperature
distribution below the drop has also been measured using
thermo-chromic liquid crystals [48] and with IR thermography
[49]. The numerical simulations for the fluid flows inside a sessile
drop driven by the thermocapillary forces during the evaporation
process have been studied in the quasistationary limit, which
provide time dependent fluid convection, vapor diffusion and
temperature distribution in an axially symmetrical evaporating sessile
drop of capillary size [50].
The understanding of the diffusion controlled drop evaporation of
spherical drops in still air is the basic to the more complex problem of
evaporation of drops in moving air where convection is present.
Moreover, the geometry of the evaporating drop is very important
on the rate of drop evaporation and one can use the knowledge
gained from the evaporation of the completely spherical drops to
understand the geometry effects on the evaporation rate of other
three-dimensional shapes. On the other hand, multi-component
droplets which are formed by solvent mixtures evaporate in many
industrial applications. The understanding of the single component
drop evaporation will lead to the better investigation of the multi-
component droplet evaporation which is especially important for
the modeling of hydrocarbon fuel evaporation applications such as the
internal combustion engine. However, multi-component evaporation
is a much more complicated process because there is preferential
vaporization of the more volatile component followed by a period
where the evaporation rate is limited by the diffusion process in the
liquid phase [51,52]. Several authors have presented advanced droplet
evaporation models and investigated this phenomenon numerically
[53].
In summary, the understanding of the factors controlling the rate
of evaporation of sessile drops on a solid surface and also freely
suspending spherical droplets in still air or in controlled atmospheric
conditions is an important topic and now gaining broader audience
with the advent of nanotechnology in the last decade. The activity in
this field resulted in the rapid increase of the number of publications:
more than 360 papers per year were published in 2010 and 2011. The
number of citations approached to 4000 when the “droplet evapora-
tion” keyword was used to search the subject in expanded-SCI indexes.
The experimental situations are diverse and the aim of this review is the
presentation of the diffusion controlled evaporation of sessile drops on
a substrate and also freely suspending spherical droplets in still air in
simple physical terms as a basis to investigate more complex drop
evaporation problems and applications.
 H.Y. Erbil / Advances in Colloid and Interface Science 170 (2012) 67–86
1.2. History of drop evaporation research
Maxwell was the first to derive the basic drop evaporation equations
by diffusion in still air by considering the simplest case where a liquid
evaporates from a spherical bulb which is motionless relative to an
infinite uniform medium in an article on “Diffusion” under the heading
“Theory of the Wet Bulb Thermometer” written in 1877 for the
Encyclopedia Britannica [1]. Sreznevsky in Russia related Maxwell's
theoretical results to the evaporation of hemispherical drops resting
on a plane and showed that the rate of evaporation of a drop is
approximately proportional to the vapor pressure of the liquid
[2,54]. Morse measured the evaporation of spherical iodine drops
and determined that the rate of evaporation was proportional to the
radius of the sphere and not to its surface area in 1910 [55]. Langmuir
analyzed the results of Morse and showed that the rate of evaporation
should in fact be proportional to the radius of a spherical drop by
using the analogy between the diffusion and conduction heat transfer,
in 1918 [56]. Langmuir calculated the diffusivity of iodine vapor in air
from the evaporation rate and pointed out it is probable that the
calculated value of diffusion is somewhat low because the free diffusion
in all directions was hampered by the sphere resting on a flat surface
[56]. Later, Topley and Whytlaw-Gray calculated the diffusion coefficient
of hanging iodine spheres precisely from their evaporation rates in 1927
[57]. They used Stefan's general theory of diffusion equations [58,59] to
the case of slowly evaporating substances whose saturated vapor
pressure does not exceed about 1 mm Hg and derived equations for
the estimation of the correction for the self-cooling of the spheres during
evaporation [57].
On the other hand, evaporation of micrometer sized droplets was also
reported: Gudris and Kulikova in Russia investigated the evaporation of
micrometer sized water droplets in 1924 [60]. Nestle found that the
kinetics of evaporation of mμ-sized droplets in an atmosphere saturated
with the vapor of the liquid are different because of the increased vapor
pressure of the droplets [61]. Houghton [62] examined the evaporation
of mμ-sized water droplets applying the more general equations of
Jeffreys [63]. Houghton estimated the surface temperatures of the
water droplets and yielded a diffusion coefficient of nearly 30% too low
[62]. Woodland and Mack studied the evaporation rate of spherical
droplets of phthalates having radii of 0.7–2.0 mμ and calculated the
thickness of the saturated vapor films around the droplets [64].
Shereshefsky and Steckler carried out similar experiments by using
n-dibutyl phthalate of 0.5–3.0 mμ in radius and obtained precise results
[65].
Fuchs in Russia, developed a theory for droplets evaporating at
low pressures. He proposed that the diffusion process as not starting
directly at the surface of the evaporating sphere but from the surface
of an enveloping sphere having a larger radius where the mean free
path of the air molecules was added. The effect of this shell is
especially important for small micron-sized droplets because very few
molecules are present in this shell which is substantially a vacuous
space [66]. Bradley and co-workers studied the evaporation of less
volatile liquid droplets under vacuum down to 0.1 mm Hg pressure
and published 5 papers from 1946 to 1951 [67–71]. They determined
the rate of drop evaporation of phthalates and stearates having
0.5 mm radius by means of a microbalance under vacuum by using a
vessel having charcoal as adsorbing walls and determined that their
results were in good accordance with Fuchs' theory [67,68]. They also
determined the drop evaporation rate of C16–C18 straight-chain paraffin
hydrocarbons [69], rhombic sulfur [70] and straight-chain C16 fluoro-
carbons with the same method [71]. Johnson investigated the evapora-
tion of water drops suspended from small thermocouples by measuring
the surface temperatures and reported that Fuchs' theory adequately
describes the relationship between the difference in vapor density at
the surface of the drop and the surroundings with the difference of
temperatures due to surface cooling [72]. Monchick and Reiss measured
the rates of evaporation of 1 mμ sized sebacate droplets in a Millikan
69
oil-drop chamber and confirmed the Fuchs' theory for small droplets
[73].
The evaporation of large spherical drops was also investigated:
Langstroth et al. [74] determined the rate of evaporation of water
and other eight volatile organic liquid drops of 1–2 mm diameter in
still air and calculated drop surface temperatures using an expression
derived by equating rates of heat influx and loss by inserting the
known diffusion coefficient values. They suspended liquid drops of
1 mm diameter from the tip of glass fiber of 100 μm in diameter and
used spherical glass flasks having 20 mm internal diameter where
the inner walls of the flask were coated with absorbing material
such as charcoal for organic liquids and phosphorous pentoxide for
water. They found that the surface temperature of the more volatile
drops was significantly lower than their bulk drop temperature [74].
Ranz and Marshall investigated the factors influencing the rate of
evaporation of pure liquid drops in still air and at finite air velocities
and the heat transfer during drop evaporation [75–77]. Marshall
authored a chapter entitled “Evaporation from drops and sprays” in
“Atomization and Spray Drying” book [77]. Kinzer and Gunn investigated
the evaporation properties, temperature difference and thermal
relaxation-time of freely falling water drops that move at their terminal
velocities relative to the environmental air and reported that the surface
temperature of the freely falling drops having their diameters ranging
from 10 to 140 mμ are very close to the wet bulb temperature of the
ventilated medium [78]. Frisch investigated the diffusion-controlled
growth of an aerosol in a turbulent medium theoretically in order to
apply it to water droplet growth in a turbulent cloud [79].
In 1959, a monograph was translated from Russian to English
which was authored by N. A. Fuchs entitled “Evaporation and droplet
growth in gaseous media” [80]. This monograph was a major source
on both the millimeter and micrometer sized droplet evaporation,
citing 88 references and making thorough criticisms on the experimental
works carried out till 1959. Fuchs re-derived quasi-stationary drop
evaporation equations from the basic equations of Maxwell and Stefan.
He examined both drop evaporation in a vessel with or without
absorbing walls. He derived equations to calculate the fall in temperature
of both freely falling and hanging from a fiber droplets during evapora-
tion. He also examined the cases for quasi-stationary drop evaporation
equations moving relative to the medium and for non-stationary drop
evaporation [80]. Davis and co-workers investigated the unsteady-state
evaporation of dibutyl sebacate liquid droplets suddenly exposed to
CO2, N2 and He gases where a single submicron, charged aerosol droplet
was suspended in an electric field in the path of vertically polarized laser
beam [81]. The diffusion coefficients determined in that work by using
the Lennard–Jones potential function were in good agreement with the
previous literature data [82].
Meanwhile, the evaporation of sessile droplets on solid surfaces
was also reported: Mangel and Baer investigated the evaporation of
water drops from a hydrophobic Teflon surface in 1962 [83]. They
found that the contact angle decreased gradually until a constant
value was reached at the early stage of evaporation where the
liquid–solid contact area remained constant. Later, the liquid–solid
contact area gradually decreased while the drop shape and contact
angle would essentially constant for the remainder of the evaporation
process except for a short time interval near the end of evaporation
[83]. Wayner analyzed the data of Simon and Hsu [84] where wetting
dynamics of evaporating drops of water on copper surface was
reported and suggested that the decrease in contact angle of water
when the drop contact radius was constant is just a measure of the
change in liquid film pressure (adsorption in the thin film) [85].
In 1977, Picknett and Bexon published a very important paper on
sessile drop evaporation where they distinguished two pure modes of
evaporation: that at constant contact angle with diminishing contact
area and that at constant contact area with diminishing contact angle
[3]. A mixed type where the mode would change from one to the
other was also reported where the drop would either suddenly
70 H.Y. Erbil / Advances in Colloid and Interface Science 170 (2012) 67–86
change shape, an increase in contact angle occurs accompanying a
decrease in contact circle diameter, and sometimes both contact
angle and contact circle diameter would decrease together. They
recorded the mass profile of a slowly evaporating liquid (methyl
acetoacetate) drop in still air on a poly(tetrafluoroethylene) surface.
They developed a theory to predict the evaporation rate and residual
mass at any time in the life of the drop based on the spherical cap
geometry.
Picknett and Bexon pointed out that the presence of the solid
substrate below the evaporating drop hinders the evaporation and
derived equations to describe this effect. It is interesting to note
that although Picknett and Bexon were the first to report the effect
of the presence of solid substrate on the rate of drop evaporation;
Liebermann was the first to suggest that the calculated diffusion
coefficient should be divided by “ln 2” to correct the wall effects in his
paper which showed that air bubbles of dimension less than 1 μm
lodged on hydrophobic particles were not soluble in water in 1957
[86]. Liebermann's suggestion gives numerically the same results
obtained by Picknett and Bexon.
Publications in the field of sessile drop evaporation experiments,
theory and applications increased rapidly after 1980s. More than
350 papers were published on this subject in 2011 and the grouping
of those references into a number of categories is required and a
good understanding of the theory of drop evaporation is important
for any researcher in the field.
2. Basic theory of drop evaporation
Drop evaporation phenomenon is extremely complex under natural
conditions: The process is non-stationary and occurs in a medium with
unequal temperature and vapor concentration and the convective
circulation arises in the drops which prevents uniform temperature
gradients. In addition, the heat transfer between the medium and the
drops occur by three different mechanisms of conduction, convection
and radiation. If the drops are falling freely then they move irregularly
relative to the medium. Thus, a number of simplifying assumptions
have to be made by using a highly idealized model of the evaporation
process and consequently, the drop evaporation experiments should
be made under conditions where the effect of some factors can be
eliminated. “Quasi-stationary” drop evaporation and heat transfer are
considered for the initial theoretical analysis, where the rate of the
process at any given moment equals to the rate of the stationary process
with the boundary conditions obtaining at that moment. This will form
the basis of diffusion-controlled drop evaporation rate equations and
these equations can be used in more complex non-stationary evapora-
tion and heat transfer processes whenever required.
2.1. Evaporation of millimeter sized large spherical drops
Maxwell showed that the local evaporative flux is uniform at the
bulb surface of a thermometer due to the spherical symmetry when
a liquid evaporates from a spherical bulb which is motionless relative
to an infinite uniform medium [1]. The rate of diffusion and the rate of
heat conduction are equivalent processes so that mathematically
analogous equations can be applied to both phenomena. Maxwell
derived the general diffusion rate equation relating the concentration
of the vapor with the radial position by assuming that the vapor
concentration at the surface of the wet bulb, cS was equal to its
equilibrium concentration, i.e. the concentration of saturated vapor at
the temperature of the drop surface. Fuchs pointed out that this
assumption is valid when the drop radius is considerably greater than
the mean free path of the vapor molecules and in the case of stationary
evaporation, the rate of mass loss by evaporation was given as [80]:
dm 2 dc
− ¼ −4πR D
dt dR
where m is the mass (kg), t is the time (s), R is the radial distance from
the center of the droplet (m), D is the diffusion coefficient (m2/s) and c
is the concentration of the vapor (kg/m3). When droplets evaporate in
air, the gas phase is a mixture of vapor and air molecules and local
concentration equilibrium is achieved at the drop–air interface and
diffusion of vapor molecules is the rate-limiting process for drop evapo-
ration. If c∞ is the concentration of the drop at infinite distance from the
drop, then we have the following boundary conditions, c = cS when R =
RS and c = c∞ when R = ∞, then the integration of Eq. (1) gives the rate of
evaporation as:
dm
− ¼ 4πRS DðcS −c∞ Þ ð2Þ
dt
where RS is the radius of the spherical droplet from the center to the
surface and cS is the concentration of vapor at the sphere surface (at RS
distance). The vapor concentration will be equal to 0 at infinite distance
(c∞ = 0 for the liquid vapors other than water) and Eq. (2) becomes:


dV
−ρL ¼ 4πRS D cS ð3Þ
dt
where V is the volume and ρL is the density of the drop liquid.
In many experimental studies of droplet evaporation, the drop
was kept in the center of a spherical vessel with absorbing walls, at
which the vapor concentration is constant as cB at RB which is the
radius of hollow sphere. After introducing the appropriate boundary
conditions, the integration of Eq. (1) gives the rate of evaporation as:
dm ðc −c Þ
− ¼ 4πRS RB D S B ð4Þ
dt ðRB −RS Þ
where RS is the radius of the spherical droplet from the center to the
surface, cS is the concentration of vapor at the sphere surface (at RS
distance) and cB is the concentration of the vapor at RB distance. In
practice, RS is small in comparison with RB and Eq. (4) can be
simplified.
In summary, there are four possibilities according to experimental
conditions: (i) an organic liquid drop evaporates in a cell having
adsorbing materials at the cell wall and Eq. (4) is used for this case,
(ii) an organic liquid drop evaporates in a large cell without any
adsorbing materials and no air convection currents inside the cell
and Eq. (3) can be used for this case, since c∞ = 0; (iii) a water drop
evaporates in a small cell where practically no humidity is present
using suitable water absorbing materials such as phosphorous
pentoxide etc. at the cell walls and all the water vapor evaporated
from the drop is also adsorbed very rapidly, and Eq. (3) can be used
for this case since c∞ = 0; and (iv) a water drop evaporates in a
large cell without any adsorbing materials inside the cell, and
Eq. (2) can be used for this case instead of Eq. (3) because water
vapor is always present in a humid medium and will restrict the drop
evaporation rate. co is taken as the actual water vapor concentration
in the medium at this temperature. Water drop evaporates as long as
cS > co and the rate of evaporation is usually small for this case.
If we assume that the vapor is to obey the ideal gas law, then it is
possible to express the vapor concentration, c using the measured
vapor pressure of the liquid at this temperature:
M Pv
c¼ ð5Þ
RT
where M is the molecular weight, P v is the vapor pressure of the evap-
orating liquid, ℜ is the gas constant and T is the absolute temperature
in Kelvins. When Eqs. (3) and (5) are combined, one obtains:
dm 4πM D P vS
ð1Þ − ¼ RS ð6Þ
dt RT
 H.Y. Erbil / Advances in Colloid and Interface Science 170 (2012) 67–86 71

where PSv is the water vapor pressure at the drop surface which of a sphere is [dm = 4 ρL π R 2dR] and when this is combined with
is equal to the saturated water vapor pressure of the medium, Eq. (3) one obtains for the cases under air:
(PSv = Povs) according to Maxwell assumption if we neglect the cooling

of the drop surface. Eq. (6) is also called as “Langmuir equation” since it dR DðcS −co Þ
− ¼ : ð12Þ
was first derived by Langmuir in 1918 [56]. A correction term for the dt R ρL
vapor pressure from Stefan's general diffusion theory should be
included in Eq. (6) if the vapor pressure of the liquid is not very Since, we know [dR 2 = 2R dR] from calculus, Eq. (12) converts into
small due to the presence of vapor molecules in the medium [57–59]: !
0 1 dR2 2 DðcS −co Þ
− ¼ : ð13Þ
dt ρL
dm 4π M D P T BB 1 C
C
− ¼ lnB v CRS ð7Þ
dt RT @ P A When Eq. (13) is integrated, one obtains:
1− S
PT
2 2 2 DðcS −co Þ
Ri −R ¼ t ð14Þ
where PT is the total pressure of the atmosphere between the spherical ρL
drop and the adsorbent which is usually around 760 mm Hg. It is
easily seen that Eq. (7) reduces to Eq. (6) when applied for small values where Ri is the initial radius of the spherical drop from center to
of the ratio PSv/PT (It is calculated that there is only 1.3% deviation for surface and R 2 is the drop radius as the linear function of time, t.
20 mm Hg and 3.4% deviation for 50 mm Hg saturation vapor pressure). The experiments performed in open air conditions show that
Regarding to evaporating of water drops in a humid medium, (cS − R 2 ∝ (tfinal − t) for macroscopic droplets where R is larger than a few
c∞) term in Eq. (2) can be expressed from Eq. (5) as: mμ [54–56,80]. Since, the surface area of a spherical drop is given as
[A = 4 π R 2] and the derivative of area with respect to the radius of
M  v v the sphere is [dA = 8 π R dR] and by combining this with Eq. (12) we
ðcS −c∞ Þ ¼ P −P o ð8Þ
RT S can write:

where Pov is the vapor pressure at Ro distance (the actual water vapor

dA 8 πDðcS −co Þ
pressure of the medium). The relative humidity (RH) in the medium − ¼ : ð15Þ
dt ρL
is defined as:
When Eq. (15) is integrated, one obtains:
P vo
RH≡ vs ð9Þ 8 πDðcS −co Þ
Po Ai −A ¼ t ð16Þ
ρL

where Ai is the initial surface area of the spherical drop. Thus, A is a

By combining Eqs. (8) and (9), and considering PSv = Povs by linear function of time, t. However, in some experiments, the radius
neglecting the cooling of the drop surface, one obtains: of the droplet, R was kept constant by injecting the appropriate of

vs 
liquid volume as lost by evaporation during the experiment with a
M Po suitable syringe where dR/dt is zero and −(dm/dt) is measured
ðcS −co Þ ¼ ð1−RHÞ: ð10Þ
RT where Eq. (4) is generally used for such cases.
On the other hand, since R ¼ ð3m=4π ρL Þ =3 for an absolutely
1

When Eqs. (10) and (2) are combined, the rate of water drop spherical shape, then integration of Eq. (6) gives:
evaporation in a humid medium can be expressed as:
 
2=3 2=3
m2 −m1
2=3
4π 2 M D P vS


 − ¼ : ð17Þ
dV M P vs
o ðt 2 −t 1 Þ 3 1=3
ρ RT
−ρL ¼ 4πRS D ð1−RH Þ: ð11Þ L
dt RT
Eq. (17) indicates that a plot of m 2/3 by time can be used to find the
product of diffusion coefficient and vapor pressure (D PSv). In addition,
As both seen in Eqs. (3) and (11), the rate of evaporation is if the initial mass of the drop at time t = 0 is mi, then the half-life of the
proportional to the radius of the spherical drop. Thus, large drops drop, t½ which is the time taken to lose half the initial drop mass can
evaporate faster than small drops. However, strictly speaking, the be calculated as:
evaporation of a drop cannot be a stationary process since the radius 
2=3
and hence the rate of evaporation is constantly decreasing during the 1

2=3 m2=3
i − mi ρL 1=3 R T
evaporation. Nevertheless, since the density of the liquid, ρL is much 3 2
t 1=2 ¼ ð18Þ
higher than cS, then the evaporation process can be regarded as 4π 2M D P vS
quasi-stationary, [80] i.e. it can be assumed that the rate of evaporation
at a given moment is expressed by Eqs. (3) or (11). Thus, the rate of However, one must be careful for the application of Eqs. (17) and
drop evaporation in air or a gaseous media is proportional to the radius (18) to the real experimental conditions, because there are differences
of the drop and not to the surface area of the drop contrary to the case of the temperature effects on the parameters which are given in these
where evaporation occurs into a full vacuum with purely kinetic equations: The diffusion constant, D is dependent on the ambient
control. For the second case, drop evaporation rate varies with the temperature. The saturation vapor pressure, PSv = Povs is dependent on
drop area which is proportional with R2. Since drop volume V varies the surface temperature of the drop and not on the ambient (air)
with R 3, then R decreases linearly with current time, where temperature. Surface temperature was generally less than ambient
R ∝ (tfinal − t) where tfinal is the time where the drop disappears. This temperature due to cooling of the drop surface during evaporation,
was observed in vacuum but not under air [80]. especially for liquids having high vapor pressures where latent heat
The volume of a spherical drop is given as [V = (4/3)π R 3] by transfers more rapidly. The liquid density, ρL is dependent on the
geometry and the derivative of the mass with respect to the radius (average) bulk drop temperature which is different from both the
72 H.Y. Erbil / Advances in Colloid and Interface Science 170 (2012) 67–86
ambient and the drop surface temperatures (it is usually between
them since there is a temperature gradient inside the drop). Therefore,
one must be careful to judge the effect of the temperature dependencies
of these physical quantities while using the equations derived for
evaporation rate of the drops.
2.2. Evaporation of micrometer sized small spherical droplets
All the above equations are successful in describing the evaporation
of millimeter sized large drops at rest whose radii are large compared to
the mean free path of the environmental fluid. However, when the radii
of the small droplets become comparable to the mean free path of the
environmental air the above equations must be modified to allow for
the fact that the rate of transport of vapor per unit area through the
surface layer is always finite. The theory for this case has been
developed by Fuchs [66,80] and others have investigated the matter
experimentally [57,67–71,74]. Fuchs showed that the diffusion process
during evaporation starts from the surface of an enveloping sphere
having a larger radius of (RS + Δ) where the mean free path of the air
molecules was added and not from directly at the surface of the evapo-
rating sphere [66,80]. The effect of this shell is especially important for
small micron-sized droplets because very few molecules are present
in this shell which is substantially a vacuous space. The correction factor
for this case is given as:
dm 4π RS DðcS −co Þ
− ¼
dt D RS
þ Mλ D P vS
RS υ α RS þ Δ
where, υ is a quarter of1 the mean absolute velocity of the vapor
molecules υ ¼ ðk T=2πmÞ =2 , [k = Boltzmann constant, T = temperature
and m = mass of a single diffusing molecule]; α is the vaporization
coefficient of the liquid which is equal to the fraction of molecules
hitting the surface to condense at equilibrium, and Δ = distance
between collisions which is the mean distance from the surface of the
drop at which the evaporating molecules suffer their first collision
with other molecules. It is clear that Δ is the thickness of the layer
adjacent to the surface where the vapor molecules move unhindered
as in a vacuum. It is possible to calculate (υ, α and Δ) values from the
kinetic theory of gases. Eq. (19) was also used for large drop evaporations
for the cases where evaporation coefficient, α was very small [67–71].
Drop evaporation rate of very small droplets in an atmosphere
saturated with the vapor of the liquid is also different because of
the effect of increased vapor pressure of the small droplets. The
vapor pressure inside a micrometer or sub-mμ sized liquid droplet,
PSv is higher than that of a planar flat surface, Pflat v
because of the
curvature present. Kelvin equation for spherical droplets is given
below:
P vS 2γM
ln ¼ ð20Þ
P vflat R TρL
where γ is the surface tension of the liquid droplet.
2.3. Self-cooling on the drop surface
The evaporation of a liquid drop is a simultaneous heat and mass
transfer operation in which heat for evaporation is transferred by
conduction and convection from warm air to the drop surface and
converted to latent heat and the vapor on the surface is transferred
by diffusion and convection back into the air. The rate of heat and
mass transfer is a function of drop diameter, temperature, relative
humidity, and transport properties of the air surrounding each drop.
The magnitude of the self-cooling can be calculated by using the
energy balance and the rate of heat flow to the drop surface from
the adjacent air is equal to the heat being rendered latent by the
evaporative mass transfer. The instantaneous rate at which the
spherical drop is absorbing heat is:



dQ dm
− ¼− λ ð21Þ
dt taken dt i
where λ is the latent heat of vaporization (J/kg). Heat can reach the
drop in four ways: by conduction through the air, by conduction
through the drop carrier fibers where the liquid drop is hanged
from a fiber, by convection of air currents and by radiation. For
simplicity, air convection and radiation effects are prevented and
neglected during drop evaporation experiments and conduction
through the drop carrier fibers is also neglected sometimes by using
very low heat conducting materials and only sensible heat transfer
by conduction through the air is considered. The instantaneous rate
of sensible heat transfer from air to the spherical drop is given with
constant thermal conductivity of the gas film surrounding the evapo-
rating drop, kf, as:


dQ
¼ 4π RS kf ðT Air −T S Þ ð22Þ
dt given
where TAir and TS are the temperatures of the ambient air and drop
surface respectively and kf = kair (J/°K m s) is usually assumed. Since,
dQtaken = −dQgiven then by equating Eqs. (21) and (22) and combining
with Eq. (6), one obtains:
ð19Þ
ðT Air −T S Þ ¼ ð23Þ
R T mean
Air kf
mean
TAir is the mean value of absolute air temperature between TAir and TS
and the magnitude of the drop cooling, ΔT = TAir − TS can be calculated.
Thus, the rate of heat and mass transfer is a function of temperature,
droplet radius, relative humidity and transport properties of the air
surrounding each droplet. It is assumed that liquid molecules migrate
from the droplet interior at a rate great enough to maintain surface
saturation. Fuchs pointed out that heat conduction through the drop
carrier fibers cannot be neglected if metal wires are used [80]. When
water drop evaporates, the wet-bulb temperature which is cooler
than the medium temperature represents the droplet temperature.
When cooling occurs at the drop surface, the PSv term in Eq. (8) which
is the water vapor pressure at the drop surface cannot be taken as
equal to the actual saturated water vapor pressure of the medium at
the medium temperature, but instead it is equal to the saturated
water vapor pressure at the drop surface temperature (PSv = PSvs) and
thus Eqs. (10) and (11) cannot be used. However, it is possible to find
the PSvs value from the published water vapor pressure tables [87] when
the drop surface temperature is measured or calculated. Afterwards,
Eq. (11) becomes:



dV M vs vs
−ρL ¼ 4π RS D P S −ðRHÞP o ð24Þ
dt RT
where Povs is the saturated water vapor pressure of the medium at the
medium temperature. On the other hand, diffusion coefficient, D is
also temperature dependent and when the variation of the absolute
temperature differences is large, the equation below is generally used
[88]:

1:75
T1
D1 ¼ D2 ð25Þ
T2
Most of the researchers in the field assumed that the surface
temperature of a slowly evaporating drop reaches to a temperature
very close to the surrounding gas temperature in the published literature,
because of the experimental difficulties of measuring the actual drop
surface temperature. However, considerable surface cooling was also
 H.Y. Erbil / Advances in Colloid and Interface Science 170 (2012) 67–86 73


reported in some publications [73–77] and only Houghton corrected the θ
h ¼ r b tan ð30Þ
water drop temperatures by using wet and dry-bulb temperature data 2
[62]. In general, thermal effects are always important because of the
poor thermal conductivity of drop surroundings.
Thus, a spherical cap shaped drop can be characterized by using
2.4. Evaporation of sessile drops on solid: experimental aspects any two of the above four parameters.

The global evolutions of the drop shape are usually deduced from
the drop visualization with a CCD camera in various experimental
studies after a drop of controlled volume is deposited on the substrate
from a syringe. When a liquid drop is sufficiently small and surface
tension dominates over gravity, the drop forms a spherical cap
shape. A spherical cap shape can be characterized by four different
parameters, the drop height (h), the contact radius (rb), the radius
of the sphere forming the spherical cap (RS), and the contact angle
(θ) as given in Fig. 1. By geometry, the relationships between the
two radii, the contact angle and the volume of the spherical cap
(Vsph) at any instant in time are:
r b ¼ RS sinθ
and
2.5. Evaporation of sessile drops on solid: effect of the presence of the
substrate to decrease the rate of drop evaporation [f(θ) factor]
Picknett and Bexon pointed out that the presence of the solid
substrate below the evaporating drop hinders the evaporation [3]. If
we compare the drop evaporation rate of a fully spherical drop sitting
on a substrate having a contact angle of 180° with the evaporation
rate of a hanging fully spherical drop surrounded by free space, the
latter would evaporate faster because of the lack of the solid plane
wall preventing the vapor which can diffuse downward direction.
When the horizontal solid surface is taken into account, the rate of
volume decrease by time is given as [3]:
ð26Þ


dV c 4π RS D
− ¼ ðcS −c∞ Þf ðθÞ ð31Þ
dt ρL

1 where t is the time (s), D is the diffusion coefficient (m 2/s), cS is the

3 V sph =3
RS ¼ ð27Þ concentration of vapor at the sphere surface (at RS distance) (kg/m3),
πβ
c∞ is the concentration of the vapor at infinite distance (R∞ distance)
(kg/m3), ρL is the density of the drop substance (kg/m3) and f (θ) is a
where, function of contact angle of the spherical cap.
Picknett and Bexon derived an equation for this situation by defining
2 3
β ¼ ð1− cosθÞ ð2 þ cosθÞ ¼ 2−3 cosθ þ cos θ: ð28Þ the C (capacitance) factor which is a function of contact angle of the
spherical cap using the analogy between the diffusive flux and electro-
static potential. They expressed C as a function of contact angle, θ and
The height of the spherical cap above the supporting solid surface
radius of curvature, R and converted the problem of determining the
is related to the two radii and the contact angle by:
evaporation rate of a sessile drop to a problem of evaluating the
capacitance of an isolated conducting body of the same size and shape
h ¼ RS ð1− cosθÞ ð29Þ as the drop as a equiconvex lens [3]. Their solution resulted in:


1 C
f ðθÞ ¼ ð32Þ
2 RS

where C is the capacitance of the equiconvex lens, which can be

obtained by using stream functions, however Picknett and Bexon
applied Snow's finite series [89] to relate apex angle to capacitance by
an empirical polynomial to facilitate easier calculations [3]. They
provided two polynomial fits to the capacitance factor in Eq. (5). For
0 ≤ θ b 0.175 rad (0≤ θ b 10°):

C 2 3
¼ 0:6366 θ þ 0:09591 θ −0:06144 θ ð33Þ
RS

and for 0.175 ≤ θ ≤ π rad (10° ≤ θ b 180°),

C 2 3 4
¼ 0:00008957 þ 0:6333 θ þ 0:116 θ −0:08878 θ þ 0:01033 θ ð34Þ
RS

Picknett and Bexon indicated that the differences between the

values obtained from finite series and those from Snow's formula
are in all cases less than 0.2% and are generally less than 0.1% [3]. In
order to perform the integration, the general Eq. (3) is written in
terms of Vsph and β,

Fig. 1. A sessile drop on a substrate: A spherical cap drop shape can be characterized by


dV sph 4π D 3 V sph 1=3 1=3
four different parameters, the drop height (h), the contact radius (rb), the radius of the − ¼ ðcS −c∞ Þf ðθÞ ¼ K V c f ðθÞ ð35Þ
sphere forming the spherical cap (RS), and the contact angle (θ). dt ρL πβ
74 H.Y. Erbil / Advances in Colloid and Interface Science 170 (2012) 67–86
where
4π2=3 31=3 DðcS −c∞ Þ
K¼ ð36Þ
1
=3 :
ρL β
K is a constant independent of time and volume. Eq. (35) can be
readily integrated between Vci (initial) when t → 0 and Vc when t → t:
2=3 2=3 2
Vc ¼ V ci − K f ðθÞ t ð37Þ
3
Eq. (35) can be integrated analytically for the “constant contact
angle evaporation mode” giving the total life-time of the drop and it
is possible to construct a linear Vc2/3 − t plot for the given Vc2/3 and θ
values and compare it with the experimental data. However, such
integration is not possible for the “constant contact area evaporation
mode” and only numerical solutions can be calculated [3].
Coutant and Penski determined that experimental and theoretically
predicted values by using Picknett and Bexon equation agree quite well
for ethylbenzene, water, and mesitylene sessile drops [90]. Later, Baines
and James expressed the f(θ) factor in terms of the Sherwood number,
which is the dimensionless mass transfer ratio of convective and
diffusive coefficients, Sh ¼ K L=D where K is the mass transfer coefficient
(m/s), D is the diffusion constant (m2/s) and L is the length (m). They
recast the Coutant and Penski data using the dimensionless Sherwood
and Peclet numbers and concluded that there is broad but reasonable
agreement between theory and experiment for sessile drop evaporation
both in still and moving air [91].
Shanahan and Bourges-Monnier published drop evaporation studies
by monitoring the evaporation of large drops of water and n-decane
(3–5 mm 3) on polyethylene, epoxy resin and TEFLON, both in saturated
vapor atmosphere and in open air [7,8]. They obtained direct measure-
ments of the change of θ, h and rb with time. They have shown the
existence of 4 distinct stages in the evaporation process in open air
conditions: In the initial stage, which corresponds to a saturated vapor
atmosphere, the contact radius, rb, remains constant while contact
angle, θ and drop height, h, decrease. In the second stage, which corre-
sponds to a non-saturated atmosphere same things happen but the
evaporation rate increases. In the third stage, which follows for smooth
surfaces, h and rb diminish concomitantly, thus maintaining θ more or
less constant. This stage does not exist on rough surfaces. In the final
stage, the drop disappears in an irregular fashion with h, rb and θ
tending to zero. This step is difficult to follow experimentally. For the
drop evaporation corresponding to the second stage, they derived a
diffusive evaporation model based on spherical cap geometry to explain
the process and to calculate the diffusion coefficient of the liquid vapor
in air [8].
Erbil, McHale and Newton studied the evaporation of n-butanol,
toluene, n-nonane and n-octane drops on polytetrafluoroethylene
surface, which occurs with constant contact angle mode and an initial
angle of less than 90° by applying video microscopy and digital image
analysis techniques as a continuation of Shanahan's work in 2002
[92]. The decrease of the square of the drop contact radius and the
square of the drop height were found to be linear with time for
most of the cases. Eq. (37) which contains f(θ) parameter showing
the decrease of the drop evaporation rate due to the presence of the
horizontal solid surface under the drop was derived for the first
time depending on the lens capacitance parameter of Picknett and
Bexon and the different versions of this equation in the literature
[3,7–9] were discussed. It was shown that Picknett and Bexon [3]
derived the exact solution and Rowan et al. [9] derived an approximate
solution by assuming the vapor concentration gradient (dc/dR) to be
radially outward and equal to (c∞ − cS)/RS. After performing the integral
they found:
ð1− cosθÞ
f ðθÞRowan ¼ : ð38Þ
2 [8] is represented by the dashed lines and the solid line at r.
Although this solution is approximate, it is a closed-form solution
which gives good results around θ = 90°.
Meanwhile, Bourges-Monnier and Shanahan also assumed that
the diffusion of liquid vapor from the liquid drop into the surrounding
atmosphere is purely radial, but they obtained a self-consistent
solution for the concentration gradient (dc/dR) [8]. They did so by
considering a spherical cap shell of surface area, ALV = f (R′,θ′) defined
by a co-ordinate system (R′,θ′) based on the center of the drop,
through which vapor diffuses. Their approximation to the concentra-
tion gradient therefore began with:
dc k k
¼− ¼− ð39Þ
dR ALV 2πR′2 ð1− cosθ′Þ
where k is a constant. Since, (RS cos θ) = (R′ cos θ′) by geometry, then
it is possible to integrate Eq. (39) and, using the boundary conditions
for the concentration at the drop surface and far removed from the
drop, to calculate the value of k in a self-consistent manner. The
model of Bourges-Monnier and Shanahan [8] gives:
cosθ
f ðθÞShanahan ¼ − : ð40Þ
2 lnð1− cosθÞ
The solution of Bourges-Monnier and Shanahan is remarkably
consistent with the exact solution of Picknett and Bexon except for
small angles where it has a singularity and diverges. The physical
origin of the difference between Eqs. (38) and (40), for f(θ) parameter
can be most clearly seen for the limiting case of θ = 180°, which
corresponds to a fully spherical drop. Eq. (38) then accurately reduces
to the known result for the evaporation of a fully spherical drop
surrounded by free space. However, for sessile drops while θ = 180°
corresponds to a fully spherical drop, that drop is in contact with a
plane wall rather than being surrounded by free space into which
vapor can diffuse. It is this case, which the Picknett and Bexon solution,
Eq. (34) describes and which is more accurately approximated by
Eq. (40) than Eq. (38). At 180° the exact solution, Eq. (32), gives
fPicknett(θ) = 0.694 while Eq. (40) gives fShanahan (θ) = 0.721 and
Eq. (38) gives fRowan (θ) = 1. The difference between Eq. (32) and the
two approximate solutions, Eqs. (38) and (40) reduces as the angle
reduces from 180° and at 90° all three solutions are the same numerically.
Below 90° the difference between the exact and the approximate
solutions increases with Eq. (40) being the more accurate approximation
for much of the angular range.
In summary, McHale and coworkers [9] assumed that vapor
molecules escape from a curved surface only at a radial direction
thus the effective diffusion area is ALV as shown in Fig. 2. Then the
area can be written as ALV = 2π r 2(1 − cos θ) and ∇ 2c = 0. The
model of McHale and coworkers neglects the evaporation flux at the
Fig. 2. Geometry of a sessile drop and diffusion area on a substrate: The solid line at the
distance r from the center of the curvature represents the diffusion area modeled by
McHale and coworkers [9]. The diffusion area modeled by Shanahan and coworkers
 H.Y. Erbil / Advances in Colloid and Interface Science 170 (2012) 67–86
drop edge, which can be greater than that from the area far from the
edge as given by Hu and Larson [16]. Meanwhile, Bourges-Monnier
and Shanahan [8] suggested a model in which the effective diffusion
area entirely compasses the drop area as also shown in Fig. 2. Then
the effective diffusion area and f(θ) factor are given by ALV = 2π r 2(1−
R cos θ/r) and f(θ) = − cos θ/[2 ln(1 − cos θ)] respectively. This model
incorporates the diffusion area excluded by Ref. [9], thus the calculated
evaporation rate is greater than that by the model of McHale and
coworkers. However, the increase of the radial distance leads to the
increase of the central angle of the spherical cap in the model of
Bourges-Monnier and Shanahan. This implies redistribution of
vapor molecules in the azimuthal direction, contradictory to the
assumption of pure radial density gradient. The evaporation rate
modeled by Ref. [8] gives the maximum rate possible as long as the
drop remains to be a part of a sphere. The major difference
between the models indicated in Refs [8] and [9] comes from how
to treat the evaporation around the drop edge where the liquid
meets the solid.
The diffusive evaporation model containing the f(θ) factor can be
successfully applied to very small droplets. Arcamone et al. monitored
the evaporation of femtoliter sessile droplets of glycerol having
diameters in the 1 μm range, with highly sensitive nanomechanical
mass sensors and very good fit was obtained between experiment
and theory when f(θ) parameter was used [93]. Meanwhile, Butt
and co-workers investigated the non-equilibrium effects due to
microscopic drop evaporation by using the f(θ) parameter [94].
They indicated that a sessile drop is usually not in thermodynamic
equilibrium because it will evaporate due to the presence of the
curved liquid surface its vapor pressure is slightly higher than that
of the vapor even in saturated vapor atmosphere. They used small
water droplets deposited onto hydrophobized micro-fabricated sili-
con AFM cantilevers and showed that a drop can be in thermodynamic
equilibrium with its surrounding only in a small, closed system and
the evaporation time of a water drop of 10 μm 3 initial volume from a
surface with which it forms a contact angle of 60° cannot exceed
740 s, even at 100% RH by using the f(θ) parameter in their evaporation
experiments [94]. In another study, Butt and co-workers [95] investi-
gated the evaporation dynamics of sessile liquid drops in still air with
constant contact radius similar to Refs. [3] and [16]. They showed that
the total evaporation time for the pinned drops is proportional to V2/3
as in the non-pinned case. Then, they provided two approximations
for the initial contact angles below 90° which allow predicting the
evaporation dynamics easily. They derived a linear approximation by
combining Eqs. (8), (26) and (31) to obtain,


dV 4π DΔP r b M f ðθÞ
¼− ð41Þ
dt ρL R T sinθ
Eq. (41) is suitable for small initial contact angles with a maximum
relative deviation of 1% for the contact angles below 30°. Its integra-
tion is not possible analytically for constant rb because the contact
angle and thus f(θ) and sinθ are changing during the drop evaporation.
However, Butt and co-workers realized that [ f(θ)/sin θ] term
depends only moderately on the contact angle; it increases from 0.64
at θ = 0° to 1.0 at θ = 90°. In order to derive a linear approximation,
they add a dimensionless constant, α, i.e. time-independent factor into
the above equation. Then Eq. (41) becomes:


dV 4π DΔP r b M f ðθ=α Þ
¼− ð42Þ
dt ρL R T sinðθ=α Þ
leading to a linear volume decrease,
4π DΔP rb M f ðθ=α Þ
V ðt Þ ¼ V o − t ð43Þ
ρL R T sinðθ=α Þ
75
α = 1.6 was found to give a good fit to experimental data in the whole
range of initial contact angles up to 90° by a numerical optimization
method. They also provided a non-linear algebraic approximation
with a maximum relative error 0.3% [95].
Graf and coworkers investigated the evaporation dynamics of
single and multiple water microdroplets on self-assembled mono-
layers of dialkyl disulfides on gold [96]. They showed that the static
contact angle decreases linearly with increasing molar ratio or with
increasing length of the hydroxyl-terminated alkyl chains in the
monolayer. All possible evaporation modes were observed during
the evaporation of the sessile droplets. The droplets were initially
pinned but later evaporated with constant contact angle after a
time, which was characteristic for the SAM used. The authors used
Eqs. (35) and (42) and determined that the single droplet stayed
pinned longer with increasing surface hydrophilicity, and thus its surface
area stayed large longer and the time for complete evaporation
decreased. The total evaporation time depends on the initial droplet
volume to a power of 2/3, and the time-dependence of the actual droplet
area compared to V2/3 is a good measure for it. However, for the complete
evaporation of many droplets with different initial volumes, they
determined a deviation from the standard evaporation model where a
power-law dependence on the total evaporation time with an exponent
different from 1.5 between 1.40 and 1.61. They explained this deviation
with the presence of a liquid precursor film around the droplet, which
either enhances or decelerates evaporation [96].
Liu and Bonaccurso studied the evaporation of very small micro-
droplets of pure liquids and mixtures by using a microcantilever
sensor [97]. They deposited water, water/ethanol mixture and
dimethylformamide microdroplets with diameters 10–80 μm onto
hydrophobized silicon microcantilevers whose bending and resonance
frequency were monitored during drop evaporation. This is a new
non-imaging technique that allows the precise measurement of the
drop mass and the calculation of the radius, and the contact angle by
combining the inclination and the resonance frequency data of the
cantilever. They showed that the microscopic water droplets evaporate
similarly to large millimeter sized water drops according to the [mo2/3 −
m2/3] ∝ t law containing the f(θ) factor on hydrophobic surfaces.
However, this law was not followed at the very beginning first
200 ms, and the valid law was [mo − m] ∝ t which was likely due to
the contact angle hysteresis: the angle changes from the advancing to
the receding while the drop loses mass due to evaporation. Meanwhile,
microdroplets of DMF evaporate somehow “in between” the two ideal
laws on similar surfaces: [mo2/3 − m2/3] ∝ t and [mo − m] ∝ t. This was
probably due to both contact angle and radius decreasing during
evaporation. The evaporation of mixtures of water/ethanol droplets
also confirmed previous results with millimeter sized drops, however
the authors realized that traces of ethanol remain in the drop until
complete drying due to its strong adsorption to the solid surface despite
its vapor pressure is larger than that of water. The authors proposed
that cantilevers are an ideal tool for sensing the preferential adsorption
of even monomolecular films of molecules present in a droplet [97].
2.6. Evaporation of sessile drops on solid: rate equations without using
the f(θ) factor
Although, the effect of the f(θ) factor is known in the literature after
the publication of Picknett and Bexon paper in 1977 [3], numerous
research reports were published on drop evaporation ignoring this
factor. In 1989 Birdi et al. reported the mass loss of water drops placed
on glass by evaporation [4]. The experimental data were obtained by
direct measurement of the variation of the mass of droplets with time
rather than the observation of contact angles. They reported constant
contact radius drop evaporation mode with diminishing contact angle
and the rate of evaporation for different sized drops was dependent
on the initial radius of the liquid–solid interface, rb. A model based on
the diffusion of vapor across the boundary of a spherical cap drop was
76 H.Y. Erbil / Advances in Colloid and Interface Science 170 (2012) 67–86
considered to explain their data [4]. In 1993, Birdi and Vu reported the
mass and contact diameter of water and n-octane drops placed on
glass and Teflon and found that two regimes can be observed during
drop evaporation on these substrates. In the first case, with θ b 90°, the
evaporation rates were found to be linear and the contact radius
constant. In the second case, with θ > 90°, the evaporation rate was
non-linear, the contact radius decreased and the contact angle
remained constant [6].
McHale and coworkers examined the change in the profile of
small water droplets on polymethylmethacrylate (PMMA) due to
evaporation in open air [9]. The drops maintained a constant contact
radius over much of the evaporation time. Measurements of θ and the
drop height, h with time in the regime of constant contact radius, rb
valid for initial contact angle b 90° were reported. They pointed out
that the model of Birdi and Vu [4,6] did not distinguish between the
two principal radii of curvature occurring at the contact line: these
two radii do not have the same values. McHale and coworkers
extended the model to a two-parameter spherical cap geometry
where the drop evaporation rate is directly proportional with drop
height, h:
dV
¼ −λh ð44Þ
dt
where, λ is the single factor to combine various constants,
λ = 2π D(c∞ − co)/ρL. By incorporating the experimentally observed
constant value of the contact radius, they were able to explain why
the experimentally observed change in contact angle should appear
linear in time [9].
Later, McHale and coworkers examined the rapid evaporation of
three different alcohol microdroplets on PMMA (θ b 90°) where the
evaporation is dominated by an initial stage with constant contact
radius, rb and decreasing contact angle, θ [11]. In another paper, they
monitored the evaporation of water droplets on Teflon (θ > 90°)
where the evaporation is dominated by an initial stage with constant
contact angle and decreasing rb [98]. They applied their earlier
model based on diffusion across the liquid–vapor interface [9], but
with an assumption of constant contact angle rather than constant
base radius using spherical cap geometry. This is the expected
behavior for an ideal system with equilibrium between liquid, solid
and vapor, where there is no difference between advancing and receding
contact angles. The authors argued that a small variation of contact angle
is expected, but that the contact angle is the slow variable compared to
the contact radius and they therefore derived the time dependence of
contact radius [98]:
2 2 4 DðcS −c∞ Þ sin2 θ
r b ¼ r bi − t ð45Þ
ρL ð1− cosθÞð2 þ cosθÞ
which can be used as an indication of constant θ evaporation mode when
fitted by the experimental data.
Sessile drops are usually flattened and oblate ellipsoid shapes are
obtained when gravity or some other distortions happen. Erbil and
Meric applied ellipsoidal cap geometry in order to compare the
differences between surface area, drop volume and evaporation
rates between the spherical and ellipsoidal cap geometry approaches
in 1997 [12]. Mathematical expressions for an ellipsoidal cap drop
resting on a solid surface having three parameters, rb, h, and θ were
used. The volume of the ellipsoidal cap can be evaluated by rotating
the ellipse curve about the y-axis resulting in:
π r b h ð2 r b tanθ−hÞ
V¼ : ð46Þ
3 tanθ
A vapor diffusion model of a drop based on three-parameter
ellipsoidal cap geometry was also developed similar to Ref. [9] and
the volume decrease by drop evaporation using the ellipsoidal
diffusion model becomes:


dV 2 D π hðc∞ −cS Þ 1 a −1 e a −1 ðb−hÞe a
− ¼ þ tan − tan ð47Þ
dt ρL 2 2he b b2
where a and b are the semi-axis lengths of the ellipse profile in the x
and y directions and e is the eccentricity which is geometrically
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
defined as [e≡ b2 −a2 =b]. Erbil and Meric used Rowan et al.'s [9]
data for the change of θ, rb and h with time for small water droplets
on PMMA polymer for the diffusive evaporation model calculations.
When the three-parameter ellipsoidal cap model was used, the
surface area and volume of the drop show almost complete linear
time dependence for most of the data [12]. The same approach was
later applied as a three-parameter pseudo-spherical cap geometry
model in 1998 [13]. In this paper, it is indicated that the classical
spherical cap geometry has a deficiency, so that it is a two-
parameter model requiring only two variables of the three measurable
parameters θ, rb, and h. When all three experimental data are used to
express the diffusion behavior, the spherical cap geometry is insuffi-
cient because this geometry must assume that h must obey Eqs.
((29), (30)), which generally does not fit the experimental data. In
addition, when the three different equation sets of the classical two-
parameter spherical cap geometry are used to calculate the volume
and the surface area of the drops, three different results are obtained,
a point which has always been neglected before in the existing
literature. Erbil and Meric proposed a new pseudospherical cap model
to overcome this deficiency using the parameter α, as given below:


θ
h ¼ α r b tan ð48Þ
2
The variation of contact angle by time was derived as:
dθ ð1 þ α Þλ
¼− ð1 þ cosθÞ sinθ ð49Þ
dt 2α π r 2b
where λ = 2 π D (c∞ − co)/ρL as derived in Ref. [9]. A vapor diffusion
model for the drop depending on the two-parameter pseudospherical
cap geometry is also developed:
½
2α 1− cosθ 2λðt−cÞ
F ðθ; α Þ ¼ lnð tan θ =2 Þ þ ¼− ð50Þ
ð1 þ α Þ sin2 θ π r 2b
where t is time, and c is the integration constant. When α = 1, then
F(θ;α) reduces to the F(θ) expression of Ref. [9]. h values as calculated
from Eqs. ((48), (50)) via θ fit the experimental data of Ref. [9] on the
evaporation rate of water sessile drops resting on PMMA polymer
better than those calculated from the classical two-parameter
spherical cap model [13].
Later, Erbil, McHale and coworkers [99] examined the reasons for
the flattening of evaporating water drops (θ b 90°) where the evapo-
ration is dominated by constant contact radius and decreasing θ.
Normally, at equilibrium, the smaller the drop, the more it is possible
to neglect the gravity and the more the profile is expected to conform
a spherical shape. In contrast, more flattening of the drop profile is
obtained experimentally during the drop evaporation. It was shown
that a singular flow progressively develops within the drop during
evaporation which creates a pressure gradient to result in more
flattening of the profile as the drop size reduces. The authors developed
a single image sequencing (SIS) method to determine whether droplets
of fluids are spherical or ellipsoidal and determine the elliptical
deviations from optically recorded droplet profiles [99].
SIS method was later improved into volume single image sequencing
method (V-SIS) and successfully applied to analysis of shape distortions
in sessile drops in a subsequent paper [100]. A simultaneous side and
 H.Y. Erbil / Advances in Colloid and Interface Science 170 (2012) 67–86
planar view video microscopy system has been used to examine the
relationship between contact angle and drop shape and the relationship
between the drop ellipticity and drop asymmetry. Experimentally
observed profiles have been analyzed for large and small drops of
water evaporating from poly(ethylene terephthalate), PMMA, Teflon,
and glass substrates. The planar view shows that deviations from a
circular shape often occur in the latter stages of evaporation but these
are not apparent from a side view observation of the droplet. As drops
evaporated and reduced in size, an increase in drop asymmetry was ob-
served in some cases, and this was attributed to surface heterogeneity.
Complementary experiments were performed with two orthogonal side
view profiles of drops of glycerine on the same substrates including
grooved glass surface which confirmed that side view profiles of a drop
could provide apparently good symmetric side view profiles conforming
to an approximate spherical cap, while the planar view of the drop
showed clear and strong asymmetry. Thus one should be careful when
using only side view profiles of evaporating droplets and the use of both
side and plan view cameras is recommended [100].
Erbil derived an equation to determine the initial peripheral
contact angle of sessile water drops on PMMA from the rate of evap-
oration [14,101].


dV ðD ΔP v ÞM
¼− ðA sinθi Þ
dt ρL R T r b i
The initial peripheral contact angle, θi so obtained was regarded as
the average of all the various θ's existing along the circumference of
the drop which is not unduly influenced by irregularities at a given
point on the surface. For this purpose, the product of diffusion coeffi-
cient and vapor pressure, DPv was found experimentally from the rate
of evaporation of the fully spherical liquid droplets in a medium
having the same RH and temperature conditions. Very good fit was
obtained by using the experimental data of Ref. [9] but the proposed
method is very sensitive to the evaporation rate and needs the precise
measurement of RH [14]. Erbil applied the same approach to
methylacetoacetate drops on Teflon substrates [101] using the exper-
imental data of Ref. [3]. A more developed form of Eq. (51) was used:
6V i MðD ΔP v Þ−2ð−dm=dt ÞR T r 2b
cosθi ¼
ð−dm=dt ÞR T r2b −6V i M ðD ΔP v Þ
and the value of the peripheral θi was found to deviate by only 3.5%
from the reported tangential θ which was measured experimentally.
The magnitude of the evaporative flux at the drop edges was also
studied (see also Section 3.4). Hu and Larson experimentally investi-
gated the evaporation of a sessile droplet with a pinned contact line
for the case of contact angle less than 90° applying both the analytic
theory and numerical computation, using the finite element method
[16]. They found both that the net evaporation rate from the droplet
remains almost constant with time for a small initial contact angle
(θ b 40°), even though the evaporation flux becomes more strongly
singular at the edge of the droplet as the contact angle decreases
during evaporation. They derived an approximate evaporation rate
expression:
dm  
2
− ¼ π r b D cS ð1−RHÞ 0:27θ þ 1:30
dt
which agrees well with the theoretical results given by Picknett and
Bexon [3] for any initial contact angle, θ between 0° and 90° with θ
in radians. The approximate expression was also compared with
droplet evaporation data from the literature, and good agreement
was found without any parameter fitting [16]. They also indicated
that the evaporation flux increases along the droplet surface, as one
moves from the center top of the droplet to the contact line at the
edge, where the flux is theoretically infinite. Hu and Larson's results
77
did not fit with the prediction of the model presented by Ref. [8]
because the former authors assume that the vapor concentration
gradient is uniform along the surface of the sessile droplet and is set
by the radius of curvature of the droplet surface, which becomes infinite
when the droplet becomes flat, leading to zero evaporation flux [8]. The
analysis given in Hu–Larson's paper was important and cited many
times in the existing literature (see also Section 3.4).
Yu and coworkers carried out a systematic study on the effect of
contact angle on drop evaporation rate by using self-assembled
monolayers (SAMs) [102]. They studied the pinning and shrinking
behavior of water microdroplets evaporating from SAMs of n-
decanethiol and 11-mercaptoundecanol on gold. The authors sug-
gested that the application of SAMs exhibits at least three advantages
for wetting and evaporation studies: (i) the monolayer films fully cover
the surfaces with highly oriented and closely packed molecules;
(ii) they introduce no changes in substrate roughness but controlled
chemical heterogeneity on the surface; (iii) the surface energy can be
tuned as a function of the relative concentrations of the components.
They reported that θ remained constant with time for all mixed SAM
surfaces, while the corresponding contact area decreased (shrinked),
after an approximate contact angle decrease of 10° and the evaporation
invariably follows an identical trend, namely from constant contact area
to constant contact angle mode, that is, from “pinning” to “shrinking”
ð51Þ
regardless of the magnitude of the initial contact angle. The authors
suggested that the origin of the evaporation mode switching was the
existence of contact angle hysteresis, Δθ on a real surface [102]. This
hypothesis was supported by the fact that the Δθ observed in the
evaporation curves matches the contact angle hysteresis of the SAMs
determined by direct measurement of the advancing and receding
contact angles. They studied the correlation between wetting properties
and evaporation rates on these model surfaces. The volume of water
microdroplets decreases nonlinearly as a function of the evaporation
time for each SAM surface and it is obvious that the more hydrophilic
the surface (i.e., the smaller the initial contact angle), the faster the
observed evaporation rate is. It was determined that V2/3 versus time
plots for water microdroplets on all SAM surfaces are linear for the entire
time period [102].
The following year, Yu and coworkers extended the water micro-
droplet evaporation studies to conventional surfaces such as silicon
ð52Þ wafers, polycarbonate, and Teflon to investigate the effect of surface
roughness at the molecular level [103]. They determined that the
more hydrophilic a surface, the faster is the evaporation rate. They
also found that surface chemical heterogeneity does not contribute
to contact angle hysteresis in mixed SAMs and surface roughness
plays a dominant role in the evaporation process so that the variations
in roughness, even at the molecular scale, result in changes in the
wetting hysteresis and, therefore, the timing for the evaporation
mode switching [103].
Rafailovich and coworkers [17] investigated the factors controlling
drop evaporation constant, λ given in Ref. [9] and the calculation of
Hildebrand solubility parameters via sessile drops evaporation
[104]. When Eqs. (26), (29) and (44) are combined one obtains:


dV πDM ð1− cosθÞ  v v
¼− 2r P S −P o ð54Þ
dt ρL R T b sinθ
ð53Þ
Rafailovich and coworkers indicated that equilibrium would be
established very fast within the very limited surface region of the
drop and assumed that PSv is the saturated vapor pressure of the liquid
at the studying temperature, which is controlled by the intermolecu-
lar forces in the liquid. The saturated vapor pressure of a liquid is the
partial pressure exerted by vapor molecules that are in equilibrium
with the condensed state and is determined by the intermolecular
cohesive energy in the liquid, which is linked to the heat of vaporiza-
tion, ΔHvap. The relationship between the saturated vapor pressure,
78 H.Y. Erbil / Advances in Colloid and Interface Science 170 (2012) 67–86
PSv, and the heat of vaporization is given by the well-known Clausius–
Clapeyron equation:
v ΔH vap
lnP S ¼ − þ K1
RT
where K1 is the value of ln PSv when ΔHvap = 0. Thus, K1 is a universal
constant that is independent of the particular liquid. By combining
Eqs. (54) and (55) and assuming Pov = 0 one obtains,



dV 2π D M ΔH vap
¼− h exp − þ K1
dt ρL R T RT
[Eq. (56) can be valid only for liquids other than water because
Pov = 0 cannot be assumed for any humid medium where water
vapor is present]. Eq. (56) can be written as:


πDM ΔH vap
ln½−ðdV=dt Þ=2 h ¼ ln þ − þ K1
ρL R T RT
Rafailovich and coworkers monitored the drop evaporation of meth-
anol, ethanol, butanol, acetone and water on octadecyltrichlorosilane
covered silicon surface, Teflon, parafilm and poly(dimethylsiloxane)
substrates and concluded that the diffusion is mainly controlled by D
of the liquid and is not sensitive to temperature and liquid composition,
whereas ΔHvap regulates the drop evaporation [17]. In a subsequent
paper, Rafailovich and coworkers extended this approach to determine
Hildebrand solubility parameters of the drop liquids via ΔHvap values
obtained by sessile drop evaporation [104]. Later, they studied the
evaporation kinetics of droplets containing DNA as a function of DNA
concentration [31]. They found that the drops containing very low
DNA concentrations dried by maintaining a constant base, whereas
those with high concentration dried with a constant θ. DNA chains
were distributed in isolated patches along the liquid–vapor interface
of the droplet for low concentrations. Liquid surface was covered with
a solid shell of DNA at high concentrations [31].
Rafailovich and coworkers applied their drop evaporation-
Hildebrand solubility parameter approach to the dewetting of the
three-phase contact line on solids [105]. They suggested that water
adsorption by the substrate is inevitable for a water sessile droplet
evaporating on a substrate. Surfaces composed of different materials
differed in their adsorbing power with respect to water, affecting
the evaporation behavior of droplets. The liquid drop loss would be
accelerated when the liquid molecules absorb onto the substrate
surface. In this case, the total disappearing rate of the droplet
(−dm/dt) would contain both the evaporation part (−dmevap/dt)
and the adsorption part (− dmads/dt). They calculated the trace liquid
absorbing rate onto the substrate by comparing the conditions to
droplets evaporating on the non-absorbing surfaces and proposed
that this adsorption is accompanied by the pinning of the meniscus
to substrates. When the threshold adsorption density is reached, a
liquid drop dewets the substrate [105]. This interesting approach
seems to be very speculative and needs experimental confirmation
with independent adsorption experiments.
New experimental methods to monitor very small droplet evapo-
ration were introduced after 2000s. Joyce et al. applied quartz crystal
microbalance (QCM) for the first time to the study of sessile drop
evaporation by using a homologous series of light alcohols: methanol,
ethanol, 2-propanol, 1-butanol, 1-pentanol from the surface of an
oscillating quartz crystal [106]. The modes of droplet evaporation,
associated with constant contact area and constant θ, are identifiable
from the observed frequency responses. The authors concluded that
QCM holds much potential as a tool for the analysis of sessile droplet
evaporation [106]. McHale and coworkers investigated the evaporation
of small droplets of water using simultaneous QCM frequency measure-
ments and video-microscopy [107]. The authors showed that QCM data
could be interpreted in terms of an evaporation sequence involving
pinned contact area and retreating contact line periods, that absolute
frequency changes related to droplet position on the electrode. In a
subsequent paper, McHale and coworkers applied QCM measurements
ð55Þ
to the evaporation of water and colloidal suspension droplets in 2004
[108].
Bonaccurso and Butt monitored the evaporation of water drops
with contact radii of 20 μm experimentally by depositing them onto
atomic force microscope (AFM) cantilevers and measuring the deflec-
tion versus time [109]. Experimental results indicate that evaporation
of the last thin layer of water is significantly slower than the rest of
ð56Þ
the drop, which can be due to surface forces. It is shown that an
AFM cantilever can be used to analyze the evaporation of a water
drop with high sensitivity and time resolution by recording the canti-
lever inclination versus time. They also studied the transition in the
evaporation kinetics of water microdroplets on both hydrophilic
and hydrophobic surfaces where water drops with diameters of
20–60 μm (5–110 ng) were sprayed by a home-built inkjet device
ð57Þ
onto the upper face of a rectangular silicon cantilever which was
previously subjected to hydrophobization or hydrophilization
treatments. They determined that the evaporation law of water
drops on hydrophobic silicon surfaces to be “m 2/3 ∝ t” similar to
large drops [109]. On the other hand, Butt and coworkers showed
that the evaporation law was “m ∝ t” for hydrophilic surfaces and
the initial evaporation rate was more than double on the hydrophilic
surfaces than that of the hydrophobic surfaces for the same sized
droplets [110].
Later Ondarcuhu and coworkers extended their previous work
[93] and studied the evaporation of femtoliter sessile droplets using
an AFM probe with an aperture at its apex, to deposit nanodroplets
with volumes in the femtoliter range on a surface [111]. They
obtained the time evolutions of the mass of evaporating glycerol
droplets with initial volumes ranging from 0.2 to 20 fl. The droplet
mass decreases nonlinearly, with a slowing down of the evaporation
rate along the process and obeys to “m 2/3 ∝ t” law similar to large
drops [111].
Meanwhile, Nakajima and coworkers investigated the evaporation
and sliding of water droplets on smooth and nanoscale rough
fluoroalkylsilane coatings having chemical heterogeneity [112]. Drop
evaporation behaviors on these two coatings were nearly identical for
microliter-scale water droplets however differed when nanoliter-scale
droplets were used. Both the evaporation behavior of nanoliter-scale
droplets and sliding velocity of microliter-scale droplets were affected
by nanoscale surface heterogeneity. The authors attributed that this
effect was due to line tension effects at the three-phase contact lines
of these small droplets having larger Laplace pressure inside and
depends on both the period for the pinning of the three-phase contact
line and the degree of droplet shape change [112]. In a subsequent
paper, they related these differences to the magnitude and sign
variation of line tension against water droplets and concluded that the
evaporation behavior of sub-nanoliterscale droplets is affected by the
line tension more remarkably than that of microliter droplets [113].
Lee et al. studied the evaporation of sessile water droplets from
hydrophobic and hydrophilic nanoporous microcantilevers composed
of anodic aluminum oxide having well-defined hexagonal nanopores
by measuring the changes in the resonance frequency and deflection
of each cantilever [114]. Both of the constant rb and θ characteristic
regimes were found during evaporation, indicating that the nanopores
did not affect the evaporation dynamics. However, the permeation of
water into the hydrophilic nanopores resulted in quite different
responses from the hydrophobic cantilevers. In addition, the cantilever
bent downward in the final stages of evaporation due to the disjoining
pressure [114].
On the other hand, Panwar et al. investigated the evaporation of
very large water drops (15–90 μl) on glass and polycarbonate surfaces
and observed that the rb remains constant throughout the progress of
 H.Y. Erbil / Advances in Colloid and Interface Science 170 (2012) 67–86
evaporation and in the case of water-glass system, θ angle decreases
almost linearly with time while showing a considerable departure
from linearity in water–polycarbonate system [115]. It was found
that water evaporated more rapidly on glass giving an initial contact
angle of 45–50° than on polycarbonate which had an initial contact
angle of 72–75°. It was found that the evaporation rates are directly
proportional to contact radii, rb for these large drops. Since rb was
found to be constant during evaporation, Panwar et al. derived the
simple relationship of dθ/dt from the chain rule:
 
2 morphology on the pinning force of evaporating water droplets and
dθ ð−dV=dt Þ cos θ þ 2 cosθ þ 1
¼ : ð58Þ
dt π r 3b
It is possible to obtain θ as a function of time by integrating
Eq. (58) from the pre-determined constant evaporation rate. Theoretical
θ versus t curves fit the experimental results well [115].
Meanwhile, the effect of the atmosphere around the droplets was
also investigated on the drop evaporation rate. Shanahan studied the
condition of equilibrium for an evaporating sessile droplet in an
atmosphere saturated with its vapor [116]. He pointed out that the
meniscus curvature is an ingredient in equilibrium vapor pressure,
and the former depends on drop height, albeit very weakly for small
drops, due to hydrostatic pressure. Shanahan's paper became a
subject of dispute between several scientists: The conclusion of
Shanahan's paper was rejected by Meunier and Bonn who suggested
that such an approach will violate the second law of thermodynamics
and pointed out that the Kelvin equation in the presence of gravity
shows that the vapor pressure is independent of the drop height
and consequently a sessile drop can be perfectly in equilibrium with
its vapor [117]. Della Volpe and Siboni [118] commented on both
Shanahan's and Meunier and Bonn's papers and claimed that Shanahan's
analysis [116] is formally correct, but no liquid evaporation and vapor
condensation occur at different locations of the drop. A pressure gradient
actually exists within the vapor phase, and this does not contradict the
absence of evaporation/condensation since the pressure gradient is
precisely due to the gravitational field. They stated that Ref. [117] is
right in claiming that the liquid drop in the presence of its vapor and
subjected to a uniform gravitational field may actually reach equilibrium,
but their argument is formally incorrect [118].
Letellier et al. revisited the subject and examined the conditions of
liquid–vapor equilibrium, in an open system, for sessile drops of pure
liquid or solution on a substrate [119]. They stated that the liquids
constituting the sessile drops cannot be supposed to be pure in an
open system, because they are in contact with the gases of the
environment which will dissolve in the solvent according to Henry's
Law. The addition of a solute (molecule or electrolyte) into this pure
solvent leads to a decrease of the chemical potential of the liquid
(colligative properties) and this effect is opposite to that caused by
the presence of a curvature of the liquid–vapor interface in a drop
which increases the chemical potential of the liquid. Thus, it is likely
that the vapor pressure in equilibrium above the drop is equal, if
not lower, to the vapor pressure of the liquid in unlimited phase in
the usual experimental conditions. The authors concluded that, in
an open system in which the gases of the atmosphere are soluble at
such concentrations, the liquid–vapor equilibrium must be realized
[119]. Cioulachtjian et al. attempted to underline the effect of the
gas surrounding the water drop during its evaporation on flat Si
wafer in order to give some new physical elements for the drop evap-
oration modeling. The authors determined that both initial contact
angle and the rate of drop evaporation were affected by the presence
of the water vapor in the cell [120].
Chan and Pierce reported a gravimetric method as a viable tool for
studying the de-pinning process without using a video imaging
system [121]. They indicated that typical gravimetric evaporative
mass loss versus time data has two regimes: a long, linear regime
79
followed by a short, non-linear regime and most of the researchers
extract only the evaporation rate of a droplet from the linear regime
but discard or ignore the non-linear regime. They plotted the evapo-
rative mass-loss data simultaneously with the change in surface area
exposed to the substrate and observed that the transition from linear
to non-linear regimes occurs at the same time the contact area begins
to shrink. They measured the de-pin time with gravimetric data [121].
Zhang et al. studied the evaporation modes of water droplets on
polydimethylsiloxane spherical cap micron-arrays with gradually
increasing height between 0 and 1.5 μm [122]. The effect of surface
it was found that the increase in height of the spherical caps on the
substrate enhances the pinning force and the higher pinning force
can pin the contact line longer and force the droplet to evaporate
with the constant rb mode before θ reaches a certain value. At the
transition point, the contact line begins to shrink, and the evaporation
mode converts into the constant θ since the pinning force is no longer
strong enough. They assumed that the receding θ should be the same
as the transition θ and developed a model to predict the critical
pinning force [122].
3. Specific topics on drop evaporation
3.1. Drop evaporation on superhydrophobic surfaces
In 2005, McHale and coworkers investigated the 1–2 mm diameter
water droplet evaporation on a superhydrophobic patterned surface
having an initial contact angle above 150° [123]. The patterns consist
of tall and circular pillars (5–15 μm diameter) of SU-8 photoresist
arranged in square lattice such that the center-to-center separation
between pillars is 20–30 μm. Experiments show that water droplets
initially evaporate in a pinned contact area mode on these SU-8 textured
surfaces, before the contact line recedes in a stepwise fashion jumping
from pillar to pillar. The initial phase of evaporation corresponds to
the droplet evaporating while suspended across the tops of the pillars
(i.e., a Cassie–Baxter state). In some cases, but not all, a collapse of the
droplet into the pillar structure occurs abruptly and the contact area is
then completely pinned for the remainder of the evaporation period.
This part of evaporation corresponds to a Wenzel state. The pinned
contact line phase of evaporation (constant rb mode) has been analyzed
quantitatively using a model depending on the diffusion of vapor into
the surrounding atmosphere. For this purpose, the equation given
below was derived by using a related polynomial expression valid for
the contact angle range of 90–180°:
−0:721171 2
þ 0:164791 lnð1 þ uÞ þ 0:113804u þ 0:044559u
1þu
−2 D Δc t
¼ þ HPB ðθo Þ ð59Þ
ρL r 2b
where u(t) = cos θ(t) and the constant HPB(θo) is a constant of integra-
tion and represents the function evaluated at the contact angle for the
initial time t = 0. The experiments were well described by the above
model including the f(θ) factor, and this allows a simple method for
the estimation of the diffusion constant-vapor concentration difference
product (i.e., DΔc) and hence the coefficient of diffusion D [123].
Xu and coworkers studied the evaporation of 3 and 5 μl sessile
water droplets on superhydrophobic natural lotus and hierarchically
structured biomimetic lotus-leaf-like polycarbonate surfaces [124].
They applied the three-parameter ellipsoidal cap geometry of Erbil
and Meric [12] and found that the three-phase contact line is almost
pinned and contact angle decreases down to its complete vanishing
during the whole evaporation process on these hierarchically struc-
tured superhydrophobic surfaces. There were two stages for both
superhydrophobic natural lotus and hierarchically structured poly-
carbonate surfaces where the critical angle between the two stages
80 H.Y. Erbil / Advances in Colloid and Interface Science 170 (2012) 67–86
also happens at about 140°. The authors attributed this behavior to
the penetration of water vapor into the rough structure and the
relative strong interaction between water and botanic wax, resulting
in a high adhesion [124]. In a subsequent paper, Xu and coworkers
applied the ellipsoidal and spherical cap model based on the constant
contact area mode [125]. The data obtained from evaporation exper-
iments on the superhydrophobic polycarbonate, PMMA and fluorine-
end-capped PMMA/polyurethane blend surfaces fit the models well.
It was observed that the ellipsoidal cap model conforms to the
experimental θ and h values better than the spherical cap model
because of the effects of gravity, triple-phase line tension causing
the shape distortions of the droplets. The surface roughness was
found to have a great effect on the surface wetting behavior, but
also has a profound influence on the mode of water evaporation on
the surface [125].
Hayes and coworkers [126] studied the evaporative properties and
pinning strength of water and aqueous sinapic acid solution droplets
on the laser-ablated hydrophilic spots between 250 and 2000 μm in
diameter on superhydrophobic Si-nanowire surfaces which was
previously hydrophobized by perfluorooctyltrichlorosilane. Sliding
angle measurements were taken to determine the pinning strength
and the results showed a linear relationship between increasing
laser-ablated hydrophilic spot diameter and pinning strength [126].
Jung and Bhushan investigated the wetting behavior during evapo-
ration and condensation of water microdroplets on superhydrophobic
patterned surfaces [127]. They studied the effect of droplet size on θ
by evaporation using droplets with radii ranging from 300 to 700 μm
on silicon surfaces patterned with pillars of two different diameters
and heights with varying pitch values. The authors proposed a criterion
where the transition from Cassie–Baxter regime to Wenzel regime
occurs when the droop of the droplet sinking between two asperities
is larger than the depth of the cavity. They showed that the distance
between the pillars should be reduced enough to improve the ability
of the droplet to resist sinking. In addition, the authors used an environ-
mental scanning electron microscopy (ESEM) to form smaller droplets
of about 20 μm radius and measure θ on the patterned surfaces. The
authors reported that when the distance between pillars increases,
then the contact area between the patterned surface and the droplet
decreases resulting in a decrease in θ hysteresis [127].
In a similar study, Quere and coworkers investigated the transition
of water drops from “Fakir state” where the drop sits on the tops of
the pillars (Cassie state) to the impaled state (Wenzel state) where
the drop sinks on patterns having dilute pillars made by photolithog-
raphy and deep reactive ion etching on silicon surfaces [128]. The
authors monitored the evaporation of water drops on sufficiently
dilute pillars and observed that the wetting state changes as the
drop becomes smaller than a critical value, and this was interpreted
as a transition between the fakir and impaled states. In the fakir
state, θ was high (there is mainly air below the drop), and θ hysteresis
was low (owing to a reduced solid/liquid contact). In the impaled
state, θ was close to the one on a flat hydrophobic surface and the θ
hysteresis was large, (owing to the strong pinning of the contact
line on the pillars). This transition was driven by the drop size, but
surprisingly it was found that the drops impaling inside the texture
were the small ones and this was interpreted geometrically, by
considering the curvature of the liquid/vapor pockets below the
drop: if the impaled state is of lower energy than the fakir one, once
a contact is generated on the “bottom” surface, it should propagate,
and this contact can be initiated by the bending of these interfaces
as the drop gets smaller. This transition can thus be avoided provided
that the pillars are long enough [128].
Anantharaju et al. studied the transition from pinned to moving
triple line for evaporating drops on patterned surfaces over a range
of heterogeneity length scales and solid area fractions [129]. The
surface topology was generated by a uniform arrangement of square
pillars or square holes. Four distinct phases of evaporation were
observed: (i) saturation phase, (ii) pinned triple line phase, (iii) moving
triple line phase and (iv) mixed phase. It was found that pinned and
moving triple line phases are the two distinct phases of evaporation
that existed for all substrate characteristics. The evaporation proceeds
with a linear decrease of surface area in both phases. The dimensionless
evaporation rate constant is found to be higher during the moving triple
line phase in comparison with the pinned triple line phase. This is due to
the fact that roughness amplifies the surface hydrophobicity character-
istics and hence causes a higher average θ during the evaporation
process. The energy barriers associated with the stick–slip motion of
the drop were calculated and found that the slip distance was of the
order of the center spacing between the pillars and that the energy
barrier was of the same order of magnitude as the line tension reported
in the literature. In addition, the triple line topology was found to have
no effect on the evaporation rate constant [129].
Choi and Kim studied the droplet evaporation of water and
protein solution on nanostructured superhydrophobic surfaces of
varying heights [130]. The surfaces were covered with well-ordered
dense-array silicon, needle-like sharp-tip post structures in a fixed
nanometric pitch (periodicity) but varying heights of 100, 300 and
500 nm. The pattern periodicity was maintained to be 230 nm and
structural tips were all sharpened to be less than 10 nm in a tip
apex radius of curvature. It was determined that short nanopost
structures with a gradual slope did not exhibit superhydrophobicity,
following a wetting (Wenzel) state. In contrast, tall and slender
nanostructures with a steep slope exhibited great superhydrophobicity
(>170°), following a dewetting (Cassie) state independent of the
structural heights. The pure water droplet on the tall nanostructures
maintained the dewetted state throughout the evaporation with two
distinctive stages: an initial pinning stage of an almost constant contact
diameter and the remainder a slip-and-jump stage of continuous
decrease in the contact diameter. The transition from the Cassie to
Wenzel state occurs around 130–135° where θ decreases rapidly [130].
Kulinich and Farzaneh investigated the effect of θ hysteresis of the
substrate on evaporation of water droplet from the polymeric super-
hydrophobic surfaces [131]. The authors reported the water drop
evaporation from disordered (i.e. opposed to regularly patterned)
superhydrophobic surfaces with very low values of θ hysteresis.
They prepared a suspension made of ZrO2 nanopowder with an average
size of 20–30 nm which was previously coated with a perfluoroalkyl
methacrylic copolymer to coat on the aluminum test plates. They deter-
mined that the constant θ evaporation mode normally associated with
hydrophobic surfaces dominates on the low-hysteresis surface while
the constant contact diameter mode normally associated with
hydrophilic surfaces dominates on the high-hysteresis surfaces. Water
droplets were observed to evaporate slower on the surface with low θ
hysteresis. This was attributed to the fact that high θ values were
sustained on the low-hysteresis surface for much longer periods of
time, and the evaporation rate of such droplets is likely to be suppressed
in the area close to the contact line so that local saturation vapor is
generated near the contact line which hinders evaporation [131].
Shin and coworkers compared the sessile water droplet evapora-
tion rate on hydrophilic, hydrophobic and superhydrophobic surfaces
made of glass, octadecyltrichlorosilane and alkylketene dimer coated
surfaces respectively using the digital image analysis technique [132].
The drop evaporation rates were decreased with the increase of
surface hydrophobicity. Surprisingly, the droplet evaporation on the
alkylketene dimer coated superhydrophobic surface did not show three
distinct stages and there was no pinning section during evaporation
[132].
In a subsequent paper, Shin and coworkers studied the evaporation
and wetting dynamics of sessile water droplets on submicron-scale
patterned hydrophobic surfaces having 4.2 μm height silicon post
arrays [133]. Top diameter of posts was 200 nm, pitch was 600 nm,
and distribution was hexagonal packing. θ values exhibited three
distinct stages during evaporation in the flat (non-patterned)
 H.Y. Erbil / Advances in Colloid and Interface Science 170 (2012) 67–86
hydrophobic PDMS surface case; however it decreased linearly for
those in the patterned silicon post array surface case. While the
volume and the initial θ were kept constant at 1 μl and around 107°,
the evaporation rate of water drop on the patterned posts was much
higher than that of on the flat PDMS. The initial wetting diameter of
the droplets on the patterned surface remains unchanged until the
portion of the droplet above the posts completely dries out for
90% of the total evaporation time. Both the droplet contact line
and θ rapidly decreased, and the water trapped within the post
array abruptly evaporated during the last 10% of evaporation time
[133].
Erbil and Cansoy investigated the range of applicability of the
Wenzel and Cassie–Baxter (CB) equations to estimate the initial
water θ on superhydrophobic surfaces and concluded that the use of
the Wenzel equation was found to be wrong for most of the 166
results published in the literature and the CB equation should be
applied with caution to predict the initial θ on superhydrophobic
surfaces. In this analysis, the partial contact of the drop with the top
solid surface, and also the penetration of the drop in between the
pillars were considered [134].
Later, Cansoy, Erbil and coworkers studied the effect of pattern
size and geometry on the use of CB equation for superhydrophobic
surfaces of 36 patterned samples made of square and 24 of cylindrical
pillars which were prepared by applying the deep reactive ion etching
(DRIE) technique on Si wafers and subsequent hydrophobization
where pillar side lengths and diameters were varied between 8 and
100 μm while the height of pillars was kept nearly constant between
30 and 34 μm. They reported that there were large positive deviations
from the CB equation to predict the initial θ. In order to obtain a
minimum deviation from the CB equation, the patterns should be
coated with a hydrophobic material, the patterned samples should
contain cylindrical rather than the square pillars and the separation
distance between the pillars should be larger than the pillar diameter
and large pillars instead of small ones should be used [135].
Varnik and coworkers studied the evaporation of small droplets
on superhydrophobic substrates by applying computer simulations
for the case of droplets that are of comparable size to the surface
asperities based on the free-energy lattice Boltzmann method and
proposed a simple three-dimensional analytical free-energy model
[136]. Similar to findings given in Ref. [123], they showed that there
exists a further metastable wetting state where the droplet is
immersed into the texture to a finite depth, yet not touching the
bottom of the substrate in addition to the well-known CB and Wenzel
states. The droplet sinks down to a finite depth, where the force of the
Laplace pressure in the spherical cap (pushing the liquid into the
grooves) is compensated by the repulsive force in the hydrophobic
capillary. They pointed out that drop evaporation can induce a transi-
tion from CB to the Wenzel state in the published literature and the
mechanism for this effect is easy to understand: as the droplet
decreases in size, the curvature of the droplet surface grows and
consequently the lower part of the surface bulges more strongly.
Therefore, if the pillar distance is large and the pillars are not too
high, the droplet eventually touches the bottom substrate, thus
initiating the transition toward the more stable Wenzel state. However,
there is currently no definite conclusion in the literature about what
happens to an evaporating droplet that is suspended on pillars which
are so tall that no contact between liquid and bottom substrate is
possible. The authors proposed that in the course of evaporation, the
droplet either reaches a critical size and impales in the texture or
remains in the CB state. If the droplet becomes unstable, it first sinks
down to the local minimum of the free energy, but then rises again
toward the top of the pillars and consequently, it always attains a CB
state at the end of the evaporation process. The penetration depth of a
droplet in the impaled state decreases with the droplet size in such a
way that very small droplets are always located close to the top of the
surface texture [136].
81
McHale and co-workers were the first to investigate the gradient
topographies for superhydrophobic surfaces without alteration of
the surface chemistry and discussed their potential for use in micro-
fluidics and sensor applications [137]. Varnik and coworkers extended
their simulation studies to the case of large drops on the so-called
gradient substrates including the change of wettability (chemical
gradient) or topography (roughness gradient). They showed that
while the motion of a droplet on a perfectly flat substrate upon the
action of a chemical gradient appears to be a natural consequence of
the considered situation, the behavior of a droplet on a gradient of
topography is less obvious [138].
Lohse and coworkers studied the wetting transitions during water
droplet evaporation on patterned PDMS surfaces having square pillar
microstructures [139]. The width of the pillars was 5 μm, separation
distance between the pillars was 5 μm and the pillar height was
varied between 6, 10 and 20 μm to investigate the geometric effect on
the wetting transition. They experimentally monitored simultaneous
side and bottom views observed using an inverted microscope of
evaporating water droplets placed on hydrophobic micropatterns.
They reported that the shape of the droplet base at the critical point is
mostly circular for tall micropillars (h= 10 and 20 μm). Polygonal or
irregular base shapes were seen for short pillars (h= 6 μm). The
wetting transition occurs when the water droplet size decreases to a
few hundreds of micrometers in radius for the present patterned
surfaces. During the transition, the initial “Fakir” droplet jumps into
the then energetically favorable Wenzel state. The critical radius was
predicted by an interfacial energy argument which fits the experimen-
tal results well [139]. Lohse and coworkers also investigated the evapo-
ration of water droplets on superhydrophobic carbon nanofiber
substrates [140]. The contact line remained pinned throughout almost
the entire experiment. The initial θ was as high as 150°, and since it
decreases to 0° during evaporation, a very large range of θ could be
studied. The authors concluded that in their experiments the evapora-
tion was quasistatic and diffusion-driven, and thermal effects play no
role. They obtained good agreement of their experimental data with
the theoretical model of Ref. [141]. The quasi-steady model predicted
the experimental data surprisingly well even during the brief de-
pinning phase. If the radius change takes place on a longer time scale
than the diffusion, then a pinned contact line is not a stringent require-
ment for the applicability of the quasi-steady evaporation model. In
contrast, for droplets evaporating on complete wetting substrates, a
quasi-static droplet profile can no longer be assumed and viscous effects
influence the evolution of θ angle over time [142].
3.2. Determination of receding contact angle from drop evaporation
Erbil, McHale and coworkers applied video microscopy to follow
the time dependent evaporation of water sessile drops in order to
determine the receding contact angles, θr on PMMA and polyethylene
terephthalate (PET) surfaces [15]. θr was found to be 54–64° for
PMMA and 64–66° for PET depending on the initial drop size. The
average contact angle hysteresis was 23.5 and 19.5 ± 1.5° respectively.
θa and θr were also determined by the needle–syringe and the inclined
plane methods for comparison. The discrepancies from the mean of
the maximum and minimum θ results of both the needle-syringe
and the inclined plane methods were larger than expected for both
polymer surfaces. A general trend was seen with samples giving a
larger hysteresis also producing a larger discrepancy for all the
samples. It was determined that the major cause of this discrepancy
was the variation of the rate of liquid introduction and withdrawal
with the syringe in the needle–syringe method where the syringe
was applied manually. It was proposed that the drop evaporation
method allows a rate of liquid withdrawal which minimizes (or
standardizes) the linear rate of retreat effect on θr measurement. In
addition, a standard procedure ordering a constant rate of liquid
delivery and withdrawal in the needle–syringe method was proposed
82 H.Y. Erbil / Advances in Colloid and Interface Science 170 (2012) 67–86
in order to compare the results of the θ on the same polymer types in
independent laboratories. It was calculated that a discrepancy of 11–
15% from the mean of θa was present for the same kinds of polymers
by the needle–syringe method. The literature values and the experi-
mental results of the inclined plane methods given in this publication
showed even worse discrepancies from the mean for both advancing
and receding angles. The drop size effect on the contact angle seems
to be the major cause of this discrepancy [15]. Since, the measurement
of the precise value of θr on a solid is always difficult, several
researchers used the drop evaporation method to determine θr after
Ref. [15] was published [101,120,121,124,131,139,142–153].
Meanwhile, Cazabat and coworkers [18,46] investigated the
evaporation rate of drops of pure, completely wetting liquids giving
very low θ for the case where no pinning of the contact line was
occurring. It was shown that the observed dynamics is controlled by
the volatility of the liquid, as expected, but also by the properties of
the wetting film left on the substrate. θr increases with the volatility
and decreases if the thickness of the wetting film increases [18,46].
Yu and coworkers reported that the variations in roughness, even at
the molecular scale, result in changes in the wetting hysteresis and,
therefore, the timing for the evaporation mode switching indicating
the importance of θr determination [102].
3.3. Substrate thermal conductivity effect on drop evaporation
Various experimental studies have demonstrated that the droplet
evaporation process is a combination of the interaction among the
coupled fluid dynamics, surface chemistry, and heat transfer. Sefiane
and coworkers investigated the role of the thermal properties of the
substrates on drop evaporation [154–159]. The authors proposed
[154] that the cooling effect on a sessile drop surface during evapora-
tion can be linked to the thermal properties of the substrate contrary
to the case that the cooling effect can only be determined by the
evaporation rate for the isolated spherical drops of 4–12 mg in mass
as studied by Erbil and Dogan [160]. Sefiane and coworkers used
four different substrates of polytetrafluoroethylene, (a machinable
glass ceramic), titanium and aluminum in their experiments which
were coated with a 3 μm thick aluminum layer to give all the four
substrates the same wettability by liquids. Both the mass and profile
of water, methanol and acetone droplets having initial volumes ranging
from 0.5 to 8.0 μl were monitored and miniature thermocouples were
used to measure the temperature in the gas phase as well as inside
the drop at different locations. The evaporation rates obtained from
the drop profiles and weight loss by using a microbalance were found
to be consistent. It was found that the evaporation rate has a linear
dependency on the droplet base radius. The surface temperature of
the droplets decreases rapidly at the very moment of the drop deposi-
tion and then it increases afterwards until it reaches a steady state. No
surface cooling was measured for Al coated Al or Ti substrates but a
maximum cooling of 1.6° was measured on Al coated PTFE substrate.
The authors found that the evaporation rate was higher for the
substrates with higher thermal conductivity and this difference was
found to be more important for the larger drops having larger contact
area with the substrate. They pointed out that a drop surface unavoid-
ably cools when evaporating from a thermally insulating substrate
due to the latent heat of vaporization, however the drop cooling was
negligible for the drops located on a good thermal conducting substrate
because the energy required for evaporation is brought in this case by
conduction from the ambient air as well as thermal conduction through
the substrate [154].
Sefiane and coworkers developed a mathematical model for the
quasi-steady diffusion-limited evaporation of a thin axisymmetric
sessile droplet of liquid with a pinned contact line to include the
effect of evaporative cooling on the saturation concentration of
vapor at the free surface of the droplet, and the dependence of the
coefficient of diffusion of vapor in the atmosphere on the atmospheric
pressure [155]. The new equation was similar to Hu–Larson equation
Eq. (53) given in Ref. [16] and the total evaporation rate for a thin
droplet, specifically at the limit of θ → 0 was given as:
dm
− ¼ 4r b D cS ð1−RHÞðT a Þ ð60Þ
dt
where, it is assumed that the temperature of the un-wetted surface of
the substrate was equal to the atmospheric value Ta. Eq. (60) gives a
good fit [149] with the experimental results of Ref. [154]. The authors
showed that in the special case of θ = π/2, Eq. (60) becomes
[156,157],
dm
− ¼ 2π rb D cS ð1−RH ÞðT a Þ ð61Þ
dt
by combining the Newton's law of cooling on the un-wetted surface
of the substrate and the buoyancy of water vapor in the atmosphere
concepts to the previously developed model. Sefiane and coworkers
also investigated the effect of changing the atmosphere by using
helium, nitrogen, and carbon dioxide gases at reduced pressure
from 40 to 1000 mbar on the water sessile droplet evaporation and
found that reducing the atmospheric pressure increases the diffusion
coefficient of water vapor in the atmosphere and hence increases the
drop evaporation rate [158].
Sefiane and coworkers further extended their theory by developing
an expression which accounts for thermal effects associated with evap-
orative cooling that leads to a reduction in the rate of evaporation,
which was not accounted for in the current isothermal diffusion
theories [159]. Meanwhile, Ristenpart et al. studied the influence of sub-
strate conductivity on thermal Marangoni flow during drop evaporation
and showed that the occurrence of recirculation depends on the relative
thermal conductivities of the liquid and the substrate as well as θ [161].
3.4. Evaporation of drops having low contact angles, lateral evaporative
flux and Marangoni flow in an evaporating drop
Marangoni in 1878 [162,163] and Pearson in 1958 [164] have
derived the theory for surface-tension-driven (Marangoni) convection.
Schwartz and Tejada extensively review the literature on the process of
the attainment of equilibrium for a sessile drop shortly after being
placed on a solid. They also include the effects of roughness of the
solid on the drop outflow and tested the extant theory [165]. O'Brien
and Saville studied the liquid drop evaporation by laser interferometry
[166]. They monitored water, toluene, methanol, and diethyl ether
droplets having very small θ on glass. They reported that convection
occurs in the liquid drop and in the opposite direction in its vapor.
Deegan and coworkers [35–37] developed a theoretical model for the
evaporation of a pinned liquid droplet. In particular, they show that
how evaporation drives a radially outwards flow within the droplet
which can cause any dispersed solids to form a ring stain the so called
“coffee-stain” near the contact line as the droplet dries. The control of
the morphology and size of stains after the evaporation of solution or
dispersion drops is a popular subject and this fact motivated many
researchers to investigate the lateral evaporative flux in drops especial
having low θ.
Erbil and coworkers investigated the evaporation of thick nonane,
octane, toluene and butanol films on PMMA, PET, and glass substrates
by video microscopy [167]. The evaporation rates of these sessile
drops were compared with the evaporation rates of the fully spherical
liquid drops in the same experimental chamber under similar condi-
tions. Both the decrease in the liquid–vapor area of the hanging drops
and liquid–solid contact area of liquid films in the last stages of evap-
oration were found to be linear with time. The linearity of the areal
rate of change of the films implies that the evaporation of the films
occurs with the constant θ mode. For the same substrate, the rate of
area decrease is dependent to the order of increasing vapor pressure
 H.Y. Erbil / Advances in Colloid and Interface Science 170 (2012) 67–86
of the film liquid, and for the same liquid drop on different substrates,
the higher thermal conductivity of the substrate results in a higher
rate of area decrease of the liquid film [167].
Cazabat and coworkers pointed out that the complexity of the drop
evaporation problem is due to the interplay between evaporation,
hydrodynamic flow, contact line pinning, disjoining pressure for thin
films, gravity for thick ones, and Marangoni flows if temperature or
concentration gradients develop during the process [168]. They
observed that drying dynamics is controlled not only by the volatility
of the completely wetting liquid drop but also by the properties of the
wetting film left on the substrate in the situation in which the droplet
shrinks all the way until it disappears [46]. Cazabat and coworkers
reported experiments performed with alkanes on bare and grafted
silicon wafers. It is shown that the short-range part of the interaction
is not significant with respect to the dynamics but provides indirect
evidence of the presence of a mesoscopic evaporating film left on the
substrate ahead of the receding contact line [18]. They proposed that
when drops of alkanes spread on oxidized silicon wafers and mica,
the system will be an example of the simple situation of a pure,
completely wetting liquid with no specific interactions with the
substrate which must recede without pinning with a very small θ.
No significant temperature gradient can develop in such thin, flat
drops and therefore, pinning, gravity, and Marangoni flow will play
no role. θ reported in their work were very small (1–17°) and the
drops recede and shrink in a way which is completely determined
by evaporation and hydrodynamic flow.
The authors indicated that the comparison between the experi-
mental results and the theoretical ones shows that their model
works very well when no film is present around the evaporating
drop and when θ is very small. They estimated that θ would decrease
in their model when the hydrodynamical contributions were
neglected, however they pointed out that these conclusions become
questionable when θ is large because the assumption of an isothermal
receding motion is weakened and the sign of the thermal gradient is
not obvious [168,169]. In addition, the direction of surface tension
gradient is not clear in these conditions because one may expect
that as the evaporation rate is very large at the edges and they
might well be colder than the whole drop, in which case the surface
tension gradient would be directed outward. On the contrary, if we
assume that the bottom of the drop is in thermal equilibrium with
the substrate and that the heat diffusion is very fast, a stationary
field of temperatures is achieved, with the center of the drop colder
than the edges, which are at the temperature of the substrate. Then
the surface tension gradient is directed inward, and the drop is
supposed to recede faster. The authors cannot decide which one is
correct because of the experimental restrictions [168,169]. Cazabat
and Guena later published an extensive review on this subject in
2010 [170].
Hu and Larson performed numerical computations using a finite-
element method to obtain a simple approximation to the total mass
flux from the droplet as a function of the contact angle [16].
Subsequently Hu and Larson [171] carried out further numerical
calculations in order to investigate the flow within the droplet, and
later generalized this analysis to include thermocapillary (Marangoni)
effects [172]. They found that thermocapillary effects drive a recircula-
tion flow within the droplet at larger θ's, whereas the flow is always
radially outwards at smaller θ's due to the absence of thermocapillary
effects [172]. Hu and Larson showed that sufficiently strong thermoca-
pillary effects can suppress the formation of a ring stain as a droplet
containing dispersed solids evaporates [173]. Friend and coworkers
investigated internal micro-flow in an evaporating droplet [174].
They reported that the differences of the volume change and the
evaporation rate between the center and the edge region cause the
flow. They also calculated the velocity of the micro-fluid flow as a
function of the distance from the contact line using equations derived
by Deegan [37]. Fischer pointed out that the manner in which the
83
liquid evaporates from the droplet should significantly affect the
flow of fluid inside the droplet and he showed that either an outward
flow toward the contact line or an inward flow toward the center of
the droplet can be induced, depending on the evaporative driving
force using lubrication theory [175].
Analysis of literature results leads to an assumption that evapora-
tion mostly occurs at the triple line. Hegseth et al. visualized the fluid
flow inside the drop, by charging the ethanol drop with polystyrene
particles [176]. Chang and Velev investigated the convective flows
inside the droplets with the use of polymer microrod tracers
suspended within the evaporating droplet and a circular one-
directional hydrodynamic flow was observed [177]. Meanwhile,
Zhang and Chao have used a laser shadowgraphy method to visualize
the fluid flow [178]. Savino and Fico studied the Marangoni and
buoyancy convection in a hanging drop of silicone oil and hydrocarbons
using infra-red thermography [47,179]. Kang et al. studied the visuali-
zation of the flow inside an evaporating droplet using the ray tracing
method [180]. The authors applied correction methods based on the
ray tracing technique and the velocity mapping method was found to
be superior, because it was more convenient and recovers a greater
number of velocity vectors, compared with the image restoration
method [180].
The number of publications on the lateral evaporative flux
increased after 2004 [32,98,181–192]. The subject becomes a major
field with the increase of the papers aiming to control the geometry
of the insoluble stains obtained by drop evaporation; however this
special topic is out of the scope of our review. Plawsky et al. published
an important review on the effects of surface topography, surface
chemistry, and fluid physics on evaporation at the contact line
[193]. They focused on the phase change that occur at the contact
line, where three phases meet and showed that three interrelated
phenomena that can affect a phase-change process: (1) the surface
potential, (2) the shape of the liquid–vapor interface, and (3) the
resulting fluid flow. They concluded that much work remains to be
done to develop tailored surfaces for any particular liquid–solid
combination although great strides have been made [193]. In another
interesting publication, Dhavaleswarapu et al. reported their findings
on the evaporation of low θ water droplets from glass surface where
droplet profiles measured by both interferometry and goniometry
where the authors suggested that the temperature differences were
too weak to induce a Marangoni flow in their system [194].
3.5. Evaporation of water in liquid marbles
Liquid marbles are formed when hydrophobic grains self-organize
on the liquid–vapor interface of a hydrophilic liquid. They are non-
stick droplets encapsulated by micro- or nanometrically scaled particles.
They can be used as micro-reactors, micro-pumps, pH, gas and water
pollution sensors, also in powder encapsulation operations and in
wear-free micromachines, such as electromechanical actuators and
valves. Quere and Aussillous created “liquid marbles” for the first time
by coating water and glycerol droplets with micrometer-sized
(5–30 μm) hydrophobic powders [195,196]. They initially used hydro-
phobized lycopodium (spores of moss plant) as the coating powder
and these hydrophobic particles encapsulate the droplet and prevent
the liquid from contacting surfaces that it encounters. The force needed
to move these marbles on solid surfaces is extremely small because of
the removal of liquid–solid contact. An inclination angle of only a few
degrees makes the liquid marble roll on most surfaces. Larger marbles
roll more slowly than smaller ones because of their larger contact area,
which increases more rapidly than the volume as the size of the marble
increases.
The manipulation of liquid marbles using gravitational, electrostatic,
or magnetic fields was studied recently [195–198]. Liquid marbles are
also used in “dry water” applications [199,200]. McHale and coworkers
studied the electrowetting of liquid marbles [201–203]. Bormashenko
84 H.Y. Erbil / Advances in Colloid and Interface Science 170 (2012) 67–86
and co-workers also studied floating and sliding of liquid marbles
[204,205]. Liquid marbles are promising candidates to be applied in
the biomedical and genetic analysis fields where very small amounts
of materials must be analyzed in short durations so that 2D microflui-
dics and lab-on-a-chip methods are used. However, there is a need for
chemically inert liquid marbles, which can be used sufficiently long
periods. It was reported that undesired rapid evaporation of the liquid
marble usually occurs [198,201,206–208]. Evaporation control is impor-
tant in both genetic analysis and in special processes where the powder
will be used after the liquid is completely evaporated at the target. The
lifetime of a liquid marble depends on the size and type of hydrophobic
powder and also the liquid used to form it. If the liquid is very volatile, it
evaporates easily, and the liquid marble will deform very quickly as the
liquid evaporates, and finally, it will collapse.
Bhosale et al. studied the effect of the particle coating of a liquid
marble to reduce the diffusion-controlled evaporation rate of the
encapsulated liquid compared to a pure droplet [207]. They used
water-based liquid marbles made of mμ-sized poly (tetrafluoroethylene)
powder (diameter of 7 to 12 mμ) and fumed silica powder in the form of
aggregates of 200–500 nm long chains of 3.27 nm beads treated with
either hexamethyldisilazane (HMDS) or dimethyldichlorosilane
(DCMS) [207]. The resistance to diffusion during evaporation was high-
est for HMDS treated fumed silica marbles and this appeared to be
related to more limited aggregation occurring than with DCMS treated
fumed silica. The authors pointed out that the solute concentration in
the liquid marble would vary from an extremely dilute limit up to its
solubility limit during the evaporation process. The authors demonstrated
a procedure to manufacture solid polyelectrolyte microspheres and also
studied the physical processes occurring inside the marble and found
that the morphology of the marble could be undergoing phase transitions
which are reflected in the decreasing water diffusivity coefficient
measurement during this evaporation process [208].
Meanwhile, Erbil and Dandan show that the liquid marbles can be
successfully synthesized from chemically inert graphite micropowder
by encapsulating water droplets [209]. Since graphite is composed of
pure carbon; insensitive to chemical reactions and stable at room
temperature; extremely resistant to acids, bases, and oxidation;
biocompatible; nonstick; and having self-lubrication, antifouling,
and superior electric and thermal conductivity properties; these
liquid marbles may be used in many industrial applications. The useful
lifetimes of liquid marbles in constant relative humidity and tempera-
ture conditions in a closed chamber were also determined [209]. The
evaporation rates of graphite liquid marbles were compared with
the rates of pure water droplets in the same conditions, and it
was found that they had nearly twice the lifetime of pure water
droplets. The presence of chemically inert graphite micropowder
retards the evaporation of water within the liquid marble so that
these marbles have enough life-time to retain their spherical
shape under normal atmospheric conditions for many industrial
applications [209].
Later, Tosun and Erbil determined the evaporation rate of liquid
marbles made of PTFE micropowders [210]. Evaporation rates of
PTFE marbles were compared with the rates of pure water droplets
and it was found that PTFE liquid marbles have longer life-time
than water droplets and longevity increases with the increase of RH
of the evaporating medium. PTFE water marbles have a life-time of
26–60 min to retain their spherical shape under normal atmospheric
condition. Water vapor diffusion process was impeded by the presence
of the self-organized hydrophobic PTFE aggregates on the water–air
interface which reduced the evaporation rate of pure water from 25 to
45%. The barrier effect of PTFE microparticles at the water–air interface
was more effective when water was evaporating slowly in a medium
having high relative humidity (RH). The reason is the low escaping
tendency of water molecules in a high RH medium due to the low
driving energy which results in slow evaporation of water molecules
through the skin of liquid marble [210].
Doganci et al. investigated the evaporation rates of liquid marbles
stabilized by graphite particles from aqueous surfactant solutions
[211]. They prepared liquid marbles by encapsulating graphite micro-
powder on aqueous sodium dodecyl sulfate (SDS) droplets and deter-
mined their total evaporation and buckling periods in a closed
chamber having constant RH and temperature. The evaporation
rates of graphite liquid marbles obtained from SDS solutions were
compared with the rates of graphite liquid marbles obtained by
using pure water and also with aqueous SDS droplets in the same
conditions and it was determined that the buckling time increased
from 1500 s to 7500 s with the addition of SDS in water up to 0.8 mM.
It was reported that SDS adsorption improves the dimensional stability
of the marble dome during evaporation. However, surfactant-coated
graphite particles were too hydrophilic for liquid marble stabilization
and no liquid marble forms above the 0.9 mM SDS concentration
[211]. As a continuation of this research, Doganci et al. studied the
diffusion-controlled evaporation of 11 different concentrated SDS
solution drops placed on a hydrophobic substrate (TEFLON-FEP) in a
closed chamber having constant RH [212]. The initial contact angle,
decreased from 104 ± 2° down to 68° ± 1° due to the adsorption of
SDS both at the water–air and the solid–water interfaces. An equation
was developed for the comparison of the evaporation rates of drops
having different initial θ on the same substrate. It was found that the
addition of SDS did not alter the drop evaporation rate considerably
for the first 1200 s for all the SDS concentrations. The main difference
was found to be the change of the mode of drop evaporation by varying
the SDS concentration. Constant θ mode was operative up to 80 mM
SDS concentration, whereas constant contact area mode was operative
after 200 mM SDS concentration due to rapid drop pining on the
substrate [212].
Bormashenko published a review on liquid marbles outlining
10 years of experience gained by various groups in the study of liquid
marbles [213]. McHale and Newton published another review recently
on the principles and applications of liquid marbles where they
discussed how liquid marbles can be created, their fundamental proper-
ties and their transport and potential uses [214].
4. General conclusion
The understanding of the factors controlling the rate of evaporation
of sessile drops on a solid surface in still air or in controlled atmospheric
conditions is an important topic and now gaining broader audience
with the advent of nanotechnology in the last decade with a rapid
increase of the number of publications in this field. In this review, we
discussed the basic theory comprising the evaporation of millimeter
and micrometer sized spherical drops, self cooling on the drop surface
and the effects of the initial contact angle, substrate heat conductivity,
drop cooling, and also the resultant lateral evaporative flux and
Marangoni flows during sessile drop evaporation. The basic knowledge
is essential to understand the facts of the more practical applications of
sessile drop evaporation in industry such as controlling the deposition
of particles and DNA/RNA microarrays on solid surfaces, in ink-jet
printing, spraying of pesticides, micro/nano material fabrication,
biochemical assays, and manufacture of novel optical and electronic
materials.
While reviewing the published articles, we realized that it should
be more appropriate to define the value of initial θ and the absence or
presence of heat transfer through the substrate under the drop in
articles on this topic. For example, when a liquid completely wets a
surface giving very small θ's (sometimes less than 10°) then the
topic of this research cannot be considered as “drop evaporation”
because the strong interaction between the solid and liquid will inter-
fere the evaporation process and the application of the standard θ
based diffusion equations cannot be applied. The same applies when
heat is supplied beneath the drop contact area because negligible
drop surface cooling occurs in this situation. The lateral evaporative
 H.Y. Erbil / Advances in Colloid and Interface Science 170 (2012) 67–86 85

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