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How the change of contact angle occurs for an evaporating droplet: effect of
impurity and attached water films
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Jun Kwon Park,† Jeongeun Ryu,† Bonchull C. Koo, Sanghyun Lee and Kwan Hyoung Kang*
Received 28th October 2011, Accepted 11th September 2012
DOI: 10.1039/c2sm26559a

On a hydrophobic surface, the contact angle of an evaporating droplet decreases with time and
becomes much smaller than its receding contact angle; the rate of decrease is accelerated with time.
When we use impurity-concentrated water produced by partial distillation, the decrease in contact
angle is remarkably accelerated with time. In contrast, for purified water, the decrease in contact angle
is significantly reduced and the start of stage 3 is delayed. These results indicate that the submicron-
sized impurities cause the decrease in contact angle. Also, we found that a number of attached thin films
of water are generated around the periphery of impure droplets. We derived the contact angle equation
under the Cassie–Baxter model by regarding the water film as a heterogeneous layer. We compared the
theoretical model to the experimental data, and these results suggest that the attached film should be
considered as one of the direct causes for the large deviation from the Young’s angle of evaporating
droplets.

1 Introduction show a mixed mode, in which the contact line motion continues
and the contact angle is reduced.
Droplet evaporation has been the subject of constant study in It is typical that the droplets have three distinct stages during
physicochemical aspects related to various practical applications evaporation, but the detailed mechanism for such distinctions in
and industrial processes. These include spray cooling,1,2 DNA each stage is yet to be fully explained. Transition from stage 1 to
stretching,3–5 thin film deposition,6–10 and fabrication of stage 2 is due to the effect of contact angle hysteresis, as
patterned surfaces inspired by the coffee-stain phenomenon:11–13 explained by Picknett and Bexon.28 But, the mechanisms for the
DNA/RNA microarrays,14,15 ordering and assembling of small decrease in contact angle at stage 2 and the transition from
colloidal particles by evaporation,16–20 fabrication of micro- stage 2 to stage 3 are uncertain. Note that the contact angle at
lenses,21–23 and electronic devices fabricated through the ink-jet stages 2 and 3 becomes less than the receding angle. Such
printing method.24–27
Numerous investigations have been carried out to study the
evaporation rate and contact angle change for single isolated
evaporating droplets.28–41 Water droplets on a hydrophobic or a
nearly hydrophobic surface are known to commonly undergo
three evaporation stages until they completely evaporate and
disappear15,28,30,34,42–45 (see Fig. 1). At the initial stage (stage 1),
the contact line is pinned and the contact angle decreases due to
evaporation-induced volume change. As the contact line starts to
recede, stage 2 begins. At stage 2, the contact angle variation is
small (
5 ), and the contact line slowly recedes with a fairly
constant speed. Usually, the very small changes in contact angle
at stage 2 can be neglected and this stage is generally called the
constant contact angle mode. As the volume is reduced signifi-
cantly, close to 5% of initial volume, the contact angle starts to
decrease much faster, where stage 3 begins. At stage 3, droplets

Fig. 1 Three stages commonly observed during evaporation of a droplet

Department of Mechanical Engineering, Pohang University of Science and
Technology (POSTECH), San 31, Hyoja-dong, Pohang 790-784, South on a hydrophobic surface. The diamonds are for the contact angle and
Korea. E-mail: [email protected]; Fax: +82-54-279-5899; Tel: +82- the triangles are for the contact radius (water B). Time (t) is normalized
54-279-2187 with respect to the time for complete evaporation (t0) and contact radius
† These two authors contributed equally to this work. (r) is normalized with respect to the initial droplet radius (r0).

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behaviors were noted in the seventies28 but have drawn little deionized water generator (Direct-Q, Millipore). According to
attention until now. To the best of our knowledge, only the specifications, after processing with the deionizer more than 94%
following papers considered or even mentioned this problem. of the ions and more than 99% of the organic material (molecular
Bourges-Monnier and Shanahan30 conjectured that such a rapid weight > 200), bacteria, particulates and colloids were removed.
change of contact angle at stage 3 is due to the triple line The deionizer was also equipped with a filter that guaranteed that
anchoring phenomenon on local heterogeneous zones of the there remains less than one particulate greater than 220 nm per
substrate itself. Kim et al.43 investigated the mechanism of 1 mL. We used two kinds of water: one is before replacing the old
transition from stage 2 to stage 3, and suggested that the Mar- filter (water B), and the other is after the replacement (water A).
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angoni flow produced by the concentration gradient of (Data in Fig. 1 were obtained by using water B.) Aqueous
contaminant at the edge region of a droplet is responsible for the dispersion containing polystyrene particles with a diameter of
same rapid change in stage 3. While studying the fine structure of 3.1 mm (Interfacial Dynamics Corporation, aqueous dispersions
the triple line to understand the origin of the continuous spec- containing 8 wt% of particles) is used after being diluted to
trum of receding angles, Bormashenko et al.44 proposed that the 0.01 wt% by using the deionized water.
precursor film formed at the periphery of a micron-sized evap- An evaporating sessile droplet in still air was observed by using
orating droplet can affect the contact angle. The mechanism for a CCD camera (Infinity2-2M, Lumenera) with a 1280 
the small decrease in contact angle at stage 2 and the transition 1024 pixel array. We attached a long distance zoom lens (7
from stage 2 to stage 3 is still a mystery (see the recent review precision zoom lens, Edmund Optics) to the CCD camera. The
paper of Cazabat and Gu
ena46). Cazabat and Gu
ena mentioned contact angle of droplets was obtained by using software called
that the surface heterogeneity may be responsible for the rapid ImageJ, which can be downloaded from a public domain.47 We
decrease of both radius and contact angle in the last stage observed the three-phase contact line, during the receding
without providing any reasonable mechanism or reason. process, by using two kinds of microscopes: an inverted micro-
In our present work, as our first attempt to uncover the scope (Axiovert 200, Carl Zeiss) in phase contrast mode and an
mechanism underlying the contact angle change of evaporating upright microscope (MX51 optical microscope, Olympus). A
droplets, the morphological change at the contact line was scanning electron microscope (XL30S FEG, Philips Electron
observed using microscopes. When we used purified water, the Optics B.V.) was used to observe the substrate surface after the
decrease in contact angle throughout the evaporation process evaporation experiment. The contact angle was measured using
was significantly less than the decrease during evaporation of the side-view image of the droplet and the values of predicted and
impure water. Microscopic observations of impure water experimentally observed contact angles in this paper were aver-
revealed that thin-film type
10 mm-sized protrusions follow the aged by repeated measurements.
contact line during the evaporation process. We derived a
contact angle equation under the Cassie–Baxter model by
considering the attached film as a heterogeneous layer. The 3 Results and discussion
results show that the attached films can induce large decrease in 3.1 Effect of impurities
the contact angle as mentioned in a previous work.
We noted that stage 3 usually appears when the volume of
droplets reduces 100 times, which implies that the relative
2 Experiment concentration of impurities increases accordingly. Water B was
A conventional glass slide having a thickness of 0.7 mm was used concentrated 100 times to measure the effect of concentration on
as the base material for the substrate. On top of that, a Teflon the contact angle. We evaporated water B by mildly heating and
AF1600 layer of about 100 nm thickness was spin-coated to vacuuming the water chamber until the volume of water B
make the surface hydrophobic. The spin-coated Teflon surface
was examined using an AFM (VEECO Dimension 3100 Scan-
ning Probe Microscope, Veeco Instruments), and it showed quite
a smooth profile with the roughness of
0.4 nm (root-mean-
square). The hydrophobic SAM (self-assembled monolayer)
coating was done by dipping a polished silicon wafer and glass
wafer into a solution of 0.1% HDFS (heptadecafluoro-1,1,2,2-
tetra-hydrodecyl trimethoxysilane; Gelest Inc., Morrisville, PA,
USA) in n-hexane. The roughness of the hydrophobic SAM
coated silicon wafer and hydrophobic SAM coated glass wafer
was 0.25 nm and 0.72 nm, respectively. A deionized water droplet
of 5 mL (the base radius of which is about 1 mm) was placed with
a micropipette on the substrate. Measurement of contact angles
was carried out in a plain laboratory environment, and experi-
ments to investigate the origins of droplet impurities were per-
formed in two different clean rooms. The temperature and
humidity of ambient air were maintained at 25  1  C and 60  Fig. 2 Effect of impurity concentration. Hollow circles represent a
3% in the laboratory and at 21  1  C and 25  1% in clean droplet of 5 mL (water B) and filled circles represent a 100 times
rooms. We used the triple distilled water, obtained using a concentrated water droplet of water B.

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reduced to 1/100 of the initial volume. The concentration of inward movement of the contact line. Contact angles were
impurities increased 100 times as the volume of water decreased measured for 9 independent runs. Advancing angles for water A,
to 1/100. Fig. 2 shows the change of contact angle vs. relative water B, and tap water were 121.0  1.6 , 120.2  1.9 , and
concentration. The relative concentration was calculated based 116.8  0.8 , respectively, and receding angles for water A, water
on droplet volume; the initial concentration is 1. For 100 times B, and tap water were 116.5  1.0 , 115.7  0.9 , and 112.0 
concentrated droplets, stage 2 did not appear and directly moved 1.0 , respectively. Water A showed larger values of both
to stage 3 from stage 1 during evaporation. Furthermore, we also advancing and receding angles than tap water. The effect of
compared water A (deionized water with a fresh filter) with tap impurities in water on contact angle hysteresis at the early stage
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water (Fig. 3). In the case of water A, the start of stage 3 was of evaporation is truly interesting, but requires more systematic
delayed. Interestingly, the contact line started to recede with a experimentation to reach a concrete conclusion on this topic. The
larger receding angle than that for tap water in stage 1. We results in Fig. 2 and 3 imply that the impurities in water are
measured the contact angle hysteresis for water A, water B, and crucial factors involved in the decrease in contact angle of
tap water on the same substrate. Advancing angles were evaporating droplets.
measured after achieving outward displacement of the contact We examined the substrate surface after complete evaporation
line by slowly increasing the volume of droplet using a syringe of a water B droplet on a Teflon-coated surface using a SEM
pump, whereas the receding angles were measured after an (Fig. 4). After complete evaporation, a circular layer of residue
with a diameter of about 470 mm (Fig. 4c) remained. Small dots
surrounded the evaporation site where the remnant resided.
According to the SEM images, the number of dots per unit
surface area was roughly 100 times greater around the evapo-
ration sites than its surrounding area (fresh surface). The results
indicate that the particles were detached from the droplet during
the receding process of the contact line. Dots, which seem to
anchor the contact line, were also observed (Fig. 4e).
Previous works showed that the addition of microparticles in
an evaporating droplet augments the contact line pinning11,12 and
stick-slip motion of the contact line.48,49 Deegan et al.11,12 argued
that the initial roughness or chemical heterogeneities of the
substrate provide a foothold on which the contact line first sticks,
and then the accumulation of material at the contact line
strengthens the pinning. Moffat et al.48 also postulated that the
Fig. 3 Contact angle and normalized contact radius (r/r0) of an evap- temporal sticking of the contact line may be due to small-scale
orating droplet of 2 mL for water A (filtered with a fresh filter) and tap pinning of the triple line by deposited particles, or due to
water. increased effective viscosity caused by high, local nanoparticle

Fig. 4 SEM images of a substrate after an experimental run (water B). (a) Fresh surface. (b and c) Overview of a pile of the remnant. (d) Dots around
the pile of the remnant. (e) Enlarged view of a dot in (d).

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concentrations. As another method to suppress the decrease in increased with time (Fig. 5). Observation with an inverted
contact angle of an evaporating droplet, Eral et al.50 used AC microscope in the phase contrast mode revealed that a number of
electrowetting to generate internal flow fields, which prevented film-type protrusions, also what we call attached films, were
the accumulation of solutes along the contact line. generated at the contact line at stages 2 and 3 (Fig. 6 and 7).
The impurities may exist in the droplet itself ab initio. Other- These attached films were certainly distinguishable from the
wise, microparticle impurities may come from the air or from contact line modulations based on size and shape. Around the
chemical reactions with the substrate.51 To remove these micro- final stage of evaporation, attached films almost completely
particles, the deionized water B was re-filtered with a 200 nm disk surrounded the main droplet (Fig. 6b). Sizes of attached films
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filter. When we compare the sizes of the remnant piles, the were 10–60 mm. The films often detached from the main droplet
diameter of that for deionized water is only slightly greater than and formed a liquid patch, which occurred more frequently at the
that for re-filtered deionized water. To minimize the influx of final stage of evaporation (Fig. 7c and d). Although it is not
contaminants from ambient air, the evaporation experiment was clearly shown in Fig. 7, an interference pattern in the protrusions
carried out in a class 100 clean room. In addition, we separately appeared. The thickness of each attached film was estimated
examined whether the particles can be produced through unan- from a series of alternating bright and dark fringes using the
ticipated chemical reactions. To account for the reaction with relationship between destructive interference and the wavelength
Teflon, a clean uncoated slide glass was tested for comparison. of light in water, which was in the order of 100 nm. The number
Although the detailed pattern of the remnant in this case was of attached films increased when the droplet size reduced (Fig. 8).
somewhat different from that on the Teflon-coated surface, Note that the length of contact line is proportional to the droplet
similar scale of remnants were observed. Thus, we concluded that radius, and thus the number of attached films per unit length
the initial impurities in water are responsible for the decrease of significantly increased as a result of the reduction of droplet size.
contact angle of an evaporating droplet as shown in Fig. 1. Such contact line modulations and attached films can be
generated through localized pinning of the contact line, which
can be induced by the imperfections of the surface itself.52–54
3.2 Contact line modulation and protrusions
Contact line pinning causes elastic force to act on the moving
At stage 1, the contact line was pinned while the volume of contact line, which reduces the contact angle to a much smaller
droplet changed. As the contact line receded (at stage 2), the value than the receding contact angle. However, if the pinning
contact line began to modulate. The modulation amplitude and
wavelength were respectively in the order of 1–10 mm and 10–
100 mm. Contact line modulation of a droplet is represented by
wrinkling (weak distortion) of the water surface around its
contact line. The amplitude and total number of modulations

Fig. 6 Generation of attached films at the contact line observed using an

inverted microscope in phase contrast mode (water B) at (a) t/t0 ¼ 0.836
and (b) t/t0 ¼ 0.927. Scale bar ¼ 200 mm.

Fig. 5 Modulation of the contact line (water B) at (a) t/t0 ¼ 0.6, (b) t/t0 ¼ Fig. 7 Attached films observed using an upright microscope (water B)
0.7, (c) t/t0 ¼ 0.85, (d) t/t0 ¼ 0.9, (e) t/t0 ¼ 0.96, and (f) t/t0 ¼ 0.97. Scale at (a) t/t0 ¼ 0.889, (b) t/t0 ¼ 0.963, (c) t/t0 ¼ 0.926, and (d) 10 seconds
bar ¼ 200 mm. (Dt/t0 ¼ 0.003) after (c). Scale bar ¼ 100 mm.

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Fig. 8 Temporal change of number of attached films for two indepen- Fig. 10 Attached films observed using an upright microscope (aqueous
dent experimental runs (water B). dispersion containing 0.01 wt% of polystyrene particles of diameter
3.1 mm) at (a) t/t0 ¼ 0.912, (b) t/t0 ¼ 0.943, (c) t/t0 ¼ 0.958, and (d) t/t0 ¼
0.988. Scale bar ¼ 100 mm.
process was solely determined by the nature of the substrate, the
number of attached films per unit length of contact line should be
independent of time. However, the number of attached films per generate the attached films is beyond the scope of our
unit length of contact line increases as the droplet size decreases present work.
(Fig. 8). In the case of water A, the contact line modulations
and attached films are greatly reduced (Fig. 9), accounting for the 3.3 Modeling of the contact angle
above-mentioned absence of stage 2 for water A. Thus, the
impurities inside the droplet are conjectured to promote In this section, we attempted to quantitatively model the effect of
the contact line modulation and generation of attached films. We modulations and attached films on the contact angle. A localized
also observed attached films using aqueous dispersions con- defect (physical or chemical heterogeneity) on a substrate can
taining 0.01 wt% of polystyrene particles of diameter 3.1 mm somehow locally anchor a moving contact line, and cause the
(Fig. 10), and it showed similar results in the case of water B modulation of the contact line (see, e.g., Fig. 5a). The extra
confirming our conjecture. The interaction between the substrate line energy (s) due to the contact line modulation can be repre-
surface and impurities is of key importance in causing adsorption sented by
of impurity on the substrate and subsequent generation of 1 1
attached liquid films. To promote the pinning effect, impurities sz gLV h2 sin2 q ; (1)
4 L
with a substrate–impurity interfacial energy higher than the sum
of impurity–water interfacial energy and substrate–water inter- where gLV, h, and L indicate interfacial tension between air and
facial energy are preferred.55 Explaining the detailed process to water, the amplitude (the characteristic magnitude of the
distortion at the three-phase line), and the wavelength, respec-
tively.56 The measured amplitude and wavelength are in the order
of 1 mm and 10 mm, respectively. The resulting extra line energy
(line tension) is in the order of 108 to 109 J m1, which is too
small to account for such a large change in the contact angle in
the experiment.
Large scale attached films in Fig. 6 and 7 and the distortion of
the contact line are certainly distinct in size from the small-scale
modulations mentioned in Section 3.2. Here, we developed a
model to determine the receding contact angle considering the
change of surface energy of solid due to the attached film. In our
model, we regarded the attached liquid film as another solid
surface with different surface energy. As shown in Fig. 11a and b,
the contact angle q of a droplet on a heterogeneous surface can be
obtained by calculating the work (dW) done by moving the
contact line by an infinitesimal distance of dr as shown below,

dW ¼ 2pr{f1(gSV  gSL)1dr + f2(gSV  gSL)2dr  gLVdrcosq}(2)

Fig. 9 Attached films observed using an upright microscope (water A) at
(a) t/t0 ¼ 0.921, (b) t/t0 ¼ 0.937, (c) t/t0 ¼ 0.952, and (d) t/t0 ¼ 0.968. Scale where f1 and f2 are length ratios (length of the contact line
bar ¼ 100 mm. occupied by each species per total perimeter), and gSV and gSL

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are interfacial tensions between vapor and solid phases and

liquid and solid phases, respectively. In Fig. 11b, the hatched
region and the black region indicate the contact line displace-
ment of dr with local contact angles of q1 and q2, respectively.
Work is equal to zero at equilibrium, which leads to

cos q ¼ f1cos q1 + f2cos q2 (3)

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where q1 and q2 are the equilibrium contact angles of the droplet

on each species, and f1 and f2 are length ratios (length of the
contact line occupied by each species per total perimeter). Since
the receding velocity of the contact line is very slow during the
evaporation (capillary number
108), subsequent dissipation
at the moving contact line is negligible compared to other ener-
gies in our model.57,58 Thus, we ignored the effect of dissipation
on the moving contact line in our model. This equation is almost
the same with the Cassie–Baxter model.59 The only difference is
that, in our model, f1 and f2 are length ratios of each species along
the perimeter of the droplet, whereas, in the Cassie–Baxter
Fig. 11 (a) Edge of a droplet placed on a solid surface and (b) upper view
model, f1 and f2 are area ratios of each species on the solid
of a droplet placed on a chemically heterogeneous surface along the
perimeter of the contact line. (c) Calculation of f1 from the captured
surface. As mentioned in Section 3.2, the attached liquid film was
image in stage 3. Dashed line indicates the interface profile before the
movement of the contact line.

Fig. 13 (a) Calculated f1 using captured images of an evaporating

droplet (aqueous dispersion containing 0.01 wt% of polystyrene particles
Fig. 12 (a) Calculated f1 using captured images of an evaporating of diameter 3.1 mm) for three independent experimental runs and (b)
droplet (water B) for three independent experimental runs, and (b) comparison between predicted and experimentally observed contact
comparison between predicted and experimentally observed contact angles. Blank symbols denote experimentally observed contact angles.
angles. Blank symbols denote experimentally observed contact angles. Solid symbols represent the contact angles predicted by the present
Solid symbols represent the contact angles predicted by the present model. model.

11894 | Soft Matter, 2012, 8, 11889–11896 This journal is ª The Royal Society of Chemistry 2012
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thin with a thickness of
100 nm. Thus, for the attached liquid surface roughness about 0.25 nm and a glass wafer coated with a
film, q1 was assumed to be 0 , while q2 was set to be the original hydrophobic SAM of surface roughness about 0.72 nm. For the
receding contact angle of 114 . f1 was calculated as the length droplet on the hydrophobic SAM coated silicon wafer, no
ratio of the contact line connected to the liquid film per total attached water film was observed around the periphery of the
perimeter from the captured image in stage 3, e.g., in Fig. 11c, f1 droplet and occurrence of stage 3 was significantly delayed
was calculated as (L1 + L2 + L3 + L4 + L5 + L6)/2pr (Fig. 12a). (Fig. 14a) compared to the result of water B on the Teflon-coated
Theoretical contact angles were obtained using the present model surface. Evaporating droplet of water B on the hydrophobic
for three independent experimental runs, and were compared to SAM coated glass wafer showed almost the same result as in the
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the experimentally observed contact angles (Fig. 12b). Since the case of the hydrophobic SAM coated silicon wafer except for the
species, concentration, and wettability of impurity in the water reduced receding contact angle (Fig. 14b). Thus, we confirm that
are not known, we repeated our experiments using aqueous generation of attached water films and subsequent occurrence of
dispersion of well-characterized polystyrene particles (Fig. 13). stage 3 are closely related to the interaction between the substrate
The contact angle of the polystyrene particle (q1) is 40 ,60 the surface and impurity as discussed in Section 3.2. Surface
diameter is 3.1 mm, and the concentration is 0.01 wt%. In both roughness directly affected the contact angle hysteresis but the
cases, theoretical results of contact angles and the fast decrease in influence of surface roughness on the generation of attached
stage 3 agreed with the experimental results, which suggests that water films and fast decrease of contact angle at stage 3 was not
the attached film should be considered as one of the direct causes distinguishable from the results in this study.
of the contact angle decrease. Deviation of theoretical and
experimental contact angles in the case of water B (Fig. 12) 4 Conclusions
would be further reduced if we use the precise value of q1.
To investigate the effect of surface roughness on the contact We demonstrated that the mild (at stage 2) and fast (at stage 3)
angle of an evaporating droplet, we evaporated water B on a decrease of contact angle of an evaporating water droplet on a
polished silicon wafer coated with a hydrophobic SAM of hydrophobic surface is caused by the impurities inside a droplet.
When we used impurity-concentrated water produced through
partial distillation, the rate of decrease in the contact angle
became much quicker; meanwhile, for purified water, the contact
angle decrease was reduced significantly. We observed that a
number of
10 mm-sized film-type protrusions (attached film)
appeared at the droplet’s periphery. Our contact angle equation,
derived on the basis of the Cassie–Baxter model, suggests that the
attached film should be considered as one of the direct causes of
the contact angle decrease. We expect that our work can be used
as a probe to understand and predict the contact-line dynamics
for several industrial applications and processes like evaporative
pattern formation, self-assembly, and electronic device fabrica-
tion via ink-jet printing in which contact-line dynamics is of
crucial importance.

Acknowledgements
This work was supported by the National Research Foundation
of Korea (NRF) grant no. R0A-2007-000-20098-0 funded by the
Korea government (MEST) and no. 20090083510 through
Multi-phenomena CFD Engineering Research Center.

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11896 | Soft Matter, 2012, 8, 11889–11896 This journal is ª The Royal Society of Chemistry 2012