Current Applied Physics 18 (2018) 477e483

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Current Applied Physics

journal homepage: www.elsevier.com/locate/cap

Central spot formed in dried coffee-water-mixture droplets: Inverse

coffee-ring effect
Ji Min Baek, Changhyun Yi, Joo Yull Rhee*
Department of Physics, Sungkyunkwan University, Suwon, South Korea

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

Article history: We have investigated the formation of central spot when coffee-water-mixture droplets are dried, which
Received 21 September 2017 is a reverse effect of the famous coffee-ring effect (CRE). Typically, the central spot is unnoticeable or
Received in revised form ignored even though it is significant. The ring-shaped stain is due to the capillary flow (CF). The CF is
14 December 2017
caused by the difference in the evaporation rates between the edge and the center of the droplet owing
Accepted 10 January 2018
to a temperature gradient. The same temperature gradient, however, causes the so-called Marangoni
Available online 2 February 2018
flow (MF). The MF is routinely ignored, particularly when the solvent is water. However, from experi-
ments, we found that, in addition to the ring-shaped stain formed by the CRE, central spot is formed.
Keywords:
Coffee-ring Effect
When the volume of a droplet of coffee-water mixture is
15 mL, the strongest central spot is formed We
Central-spot formation employed an improved enhanced heat-transfer model, in which the shape of the droplet was assumed to
Marangoni flow be spheroidal, to understand the effects of the MF on the central-spot formation. According to the model,
the formation of central spot can be explained, at least, semi-quantitatively. As a result of the existence of
a stagnation point, the direction of flow is changed. Furthermore, the dependence of its location on the
initial geometrical parameters of the droplet is very important. In addition, the effect of gravity was
investigated for pendant droplets. The central-spot formation is more prominent in pendant droplets
than in sessile droplets because the gravity enhances the MF in the pendant droplets, while it hinders the
MF in the sessile droplets.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction there exists a phenomenon opposite to the conventional CRE,

The famous coffee-ring effect (CRE) [1,2] occurs when a droplet
of a colloidal solution is dropped on a solid surface and dries,
resulting from the accumulation of nanometer-sized colloidal par-
ticles at the edge of the droplet, as shown in the left panel of Fig. 1.
This phenomenon is common to all colloidal solutions, and it ex-
hibits a significant impact on various fields of nanotechnology, for
instance, the ink-jet printing. Because paint and ink are colloidal
solutions, the CRE occurs when they are painted on a solid surface
and dried. The most important factor in painting is coating the color
evenly; however, the CRE hinders this process by moving the
colloidal particles to the edge. Nano-technology employing ink-jet-
printing technology runs into the same problem. It is difficult to
produce a thin film via ink-jet-printing technique with absolutely
uniform thickness because the CRE causes the nano-particles to
move to the edge. According to our current investigation, however,
* Corresponding author.
E-mail address: rheejy@skku.edu (J.Y. Rhee).
resulting in a noticeable central spot, as shown in the right panel of
Fig. 1. Hereafter we refer to this as an inverse CRE (iCRE). By
appropriately balancing the CRE and the iCRE, it is possible to
produce a perfectly flat thin film using the ink-jet-printing
technique.
The formation of stains at the edge of a droplet is relatively well
understood, however, the spot formed at the center, as clearly
observed in the right panel of Fig. 1, is typically ignored. It is
generally believed that the formation of the coffee-ring deposits
observed at the edge of drying droplets of coffee-water mixture
requires a pinned contact line and the capillary flow (CF) in a di-
rection toward the edge of the droplets [1,2]. There are a few re-
ports on the motion opposite to this outward motion or
suppression of CRE [3e6]. In fact, Weon and Je directly observed the
opposite motion of the particles [3]. The particles initially move
toward the edge by the CRE, and then the direction of motion is
reversed toward the center by a capillary force, thereby resulting in
the formation of multiple rings. This reverse motion has been
attributed to the variable sizes of the solute particles in the droplet.

https://doi.org/10.1016/j.cap.2018.01.007
1567-1739/© 2018 Elsevier B.V. All rights reserved.
478 J.M. Baek et al. / Current Applied Physics 18 (2018) 477e483
Fig. 1. Photos of typical coffee stain after drying a droplet of coffee-water mixture.
Moreover, Yunker et al. [7] reported that the CRE can be suppressed
by shape-dependent capillary interactions. If the suspended solute
particles have a spherical shape, then the CRE dominates and ring-
shaped deposits are formed, whereas the elliptical particles leave
no ring-shaped deposits after drying if they are evenly dispersed.
Hu and Larson [8] argued that the formation of ring-shaped de-
posits requires not only the CF and the pinned contact line but also
the suppression of the so-called Marangoni flow (MF). Although
they clearly observed the formation of a central spot in a 10-mL
droplet of octane-containing poly(methyl methacrylate) particles
(1 g/100 mL) deposited on a glass coverslip coated with per-
fluorolauric acid (see Fig. 2(b) of Ref. [8]), any discussion on this
central spot was not provided. They also developed a theoretical
model to describe the recirculatory motion of solute particles due
to the MF [9]. The MF in an evaporating water droplet was directly
observed, though the droplet was not sessile, but pendant [10]. It is
clear that the central flow, as well as the well-known outward flow,
should be studied in more detail.
In this paper, we report the results of the semi-quantitative
investigation of the formation of the central spot when the drop-
lets of the coffee-water mixture are dried. We were able to eluci-
date the factors that determine the formation of the central spot
through slight modifications of an existing model for the formation
of a stagnation point (SP) [10] and the MF [9] to be more realistic.
The MF plays an important role of the formation of central spot for
sessile droplets and the gravity enhances the MF for pendant
droplets, resulting in an enhanced central-spot formation.
2. Experimental
The coffee powder used in this study was a commercially
Fig. 2. Photo of a pure-water droplet obtained by using a drop-shape analyzer.
available instant coffee (Kanu® Colombia Dark-Roast Americano by
Maxim®). A 1.6-g stick of coffee powder was mixed with 100 g of
warm water and then cooled to room temperature. The substrate
was a transparent acrylic plate. A micro pipette, which could con-
trol the volume of fluid up to 1 mL, was used for volume control. We
prepared droplets with 7 different volumes: 10, 12, 14, 16, 18, 20,
and 22 mL. Drying did not occur under completely controlled con-
ditions, however, it was performed in a laboratory with well-
circulating air, and the temperature and the relative humidity
were 17  26+ C and 65  75%, respectively. The strength of the
central spot is predominantly determined by the geometrical pa-
rameters of the initial shape of the droplets.
To analyze the shape of the droplet, such as the radius and
contact angle, we captured a side-view picture of the droplet and
measured them using the side-view picture. We tried to use a drop-
shape analyzer, however, owing to the limitation of the equipment
that only a pure water droplet should be used, it was not possible to
use the data obtained by using the drop-shape analyzer. Although
we were not able to use the data obtained by using the drop-shape
analyzer, a typical photo of a pure water droplet is presented in
Fig. 2 to verify that the shape of the droplet is not spherical cap. If
the shape of the droplet is a spherical cap, its volume is


ph 3R2 þ h2
V¼ ;
6
where h is the height of the spherical cap at the center and R is the
radius of the base of the droplet. The height of the spherical cap at
the center is given by
R R q
h¼  ¼ R tan ;
sin q tan q 2
where q is the contact angle. Using the data obtained from the
drop-shape analyzer, R ¼ 1:885 mm and q ¼ 76:81+ , the calculated
height of the droplet is h ¼ 1:494 mm, which is slightly larger than
the height obtained from the drop-shape analyzer (h ¼ 1:46 mm),
and the calculated volume of the droplet is V ¼ 10:08 mL, which is
slightly smaller than the volume obtained from the drop-shape
analyzer (V ¼ 10:11 mL). Therefore, we can notice that the shape
of pure water droplet is almost a spherical cap. On the contrary, the
droplet of coffee-water mixture with similar volume has signifi-
cantly larger radius (2.28 mm) and significantly smaller contact
angle ð56:17+ Þ. It implies that the shape of the droplet of coffee-
water mixture is strongly distorted from the spherical cap and
should be considered as spheroidal.
An optical technique was employed for measuring the density of
the coffee stain. The photos of the top view of the dried coffee stains
were considered, and the density of the stains was obtained by
 J.M. Baek et al. / Current Applied Physics 18 (2018) 477e483 479

measuring the brightness of the pixels in the radial direction from

the center. A typical result is presented in Fig. 3. We used the
software called “ImageJ,” which is a public domain, Java-based
image processing program developed at the National Institutes of
Health. The density of a coffee stain is high where the brightness is
low. The brightness -vs. -pixel number plot should be inverted to
obtain the density of a coffee stain. We assumed that the density
was proportional to the brightness.
3. Theoretical models
3.1. Marangoni effect
Deegan et al. [1,2] discovered that the CRE primarily occurs by
the CF. By associating the concentration of water vapor with the
constant potential and the evaporation flux Js , the following rela-
tion can be obtained
Js ðr; tÞ
ðR  rÞl ;
where l ¼ ðp  2qÞ=ð2p  2qÞ, R is the radius of the droplet and r is
the distance from the center, assuming that the shape of the droplet
is a spherical cap. With an approximation
h i
Js ðr; tÞzJa f ðlÞ 1  ðr=RÞl ;
we can obtain the velocity of the fluid. According to this result, the
evaporation rate on the surface of the droplet varies depending on
the distance from the center. The farther the distance from the
center, the greater the water evaporation. As a consequence, the
surface temperature differs accordingly.
However, Hu and Larson [8,9,11] used the finite-element
method (FEM) to solve the equation, and claimed that the above
equation is not quite correct. While Deegan et al. solved the Laplace
equation directly, Hu and Larson solved it numerically using the
FEM. By comparing the results of the FEM and the experiments, Hu
and Larson [12] found that
 h r i2 l
Js ¼ J0 1 
R
where l ¼ 0:5  q=p and
Dð1  HÞcV    p2

2
J0 ¼ 0:27q þ 1:30 0:6381  0:2239 q  ;
R 4
(4)
where D is the vapor diffusivity, cV is the saturation concentration
and H is the relative humidity of the ambient air.
The MF occurs with an increase in the surface-tension gradient.
As the fluid in the region with stronger surface tension pulls that in
the region with lower surface tension, the fluid flows from the
weaker side to the stronger side. This phenomenon can be observed
during the evaporation of droplets of various fluids. The so-called
‘tears of wine’ is a typical example. The differences of evaporation
rate and that of heat conduction from the substrate result in a
temperature gradient on the surface of the droplet, and the tem-
perature gradient induces a surface-tension gradient. The MF in
evaporating water droplets was typically considered to be negli-
gible. Hu and Larson [12] showed experimentally that the MF is
considerably weak in an evaporating water droplet. Although the
theoretical Marangoni number for a drying water droplet is
(1) approximately 1000, the theoretical flow field can only be matched
to the experimental one by reducing the 100-fold Marangoni
number, to approximately 8. They argued that the considerable
reduction in the apparent Marangoni number is due to surfactant
contaminants [13]. However, in our experiment the formation of a
central spot, which might have resulted from a non-negligible MF,
(2) is evident. Furthermore, Kita et al. [14] recently observed the MF in
a pure water drop via infrared thermography.
In modeling the MF we closely followed the same steps used by
Hu and Larson [8,9] but applied a slight modification by utilizing a
more realistic shape for the droplet. By analyzing the geometrical
parameters of the droplets we found that the shape of a droplet was
not perfectly spherical but spheroidal because the initial contact-
line radius of the droplet is very close to or slightly larger than
the so-called capillary length. As detailed discussion on the deri-
vation of the MF for spherical-cap droplets is already available [8,9]
we will not repeat the details. Instead, we will provide the final
result for the spheroidal-cap droplets directly. By applying the
lubrication theory to the Stokes equation the radial velocity profile
ur ðzÞ at each value of r is parabolic in z, which is the distance from
the interface between the substrate and the droplet,
(3)
ur ¼ Az2 þ Bz; (5)
where

3ur 3
A¼ 2 þ Uðr; tÞ (6)
2h ðr; tÞ 2hðr; tÞ

and

B ¼ Uðr; tÞ  2Ahðr; tÞ (7)

with

1 ds _
hð0; tÞ ~r 2lðqÞJ0 ðqÞ~r
Uðr; tÞ≡ þ   pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi þ
(8)
m dr R a  b~ a2  ~r 2
r 1  ~r2 lþ1
w

Fig. 3. Inverted brightness-vs.-pixel number plot of a droplet with a volume of 14 mL
obtained by optical analysis.
and hðr; tÞ being the height of the droplet's surface at time t and r,
_
hð0; tÞ being the time derivative of the height at the center of the
droplet, s being the surface tension, m being the viscosity of water,
rw being the mass density of water, ~r≡r=R, b≡b=tan ~ q and
qffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2
a≡ b~ þ 1, and b being the ratio of the major (minor) axis to the
minor (major) axis of the ellipse, if b > 1 ðb < 1Þ. The ellipse can be
480 J.M. Baek et al. / Current Applied Physics 18 (2018) 477e483

obtained by cutting the droplet with a plane perpendicular to the 3.2. Stagnation point
substrate and passing through the central highest point of the
droplet. If b > 1 ðb < 1Þ the shape of the droplet is prolate (oblate) The existence of the SP, at which the surface flow, the surface-
spheroidal cap. The depth-averaged velocity is tension gradient and the surface-temperature gradient change
their directions, is crucial for the simultaneous formation of the
2 pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi 3 central spot and the ring-shaped stain; in other words, the coex-
1 R 1 4 
2 l a 2 ~ r2  b ~
istence of the CRE and iCRE. Xu and Luo [10] observed an inward
ur ¼ 1  ~r    5; (9)
4 tf  t ~r a  b~ flow inside an evaporating water droplet, which can be attributed
to the fact that some of the colloid particles changes their direction
of movement near the edge of the droplet. They developed a
where tf is the drying time.
theoretical model for the existence of the SP by assuming that the
An empirical formula for the temperature dependence of the
convexity of the droplet surface changes at the edge and by sub-
surface tension is given by Refs. [15,16].
sequently applying the heat-transfer model. Again, we slightly
modified their model with a realistic shape for the droplet.
2=3
sVmol ¼ ks ½Tc  Ti ðrÞ; (10) The heat flux through the liquid film is given as

T0  Ti ðxÞ
where Vmol is the molar volume of the fluid (water in our case), Tc is Qcond ¼ k ; (13)
the critical temperature, at which the surface tension vanishes, Ti is hðxÞ
the temperature at the vapor-liquid interface, and ks is a constant
where xð≡R  rÞ. The latent heat flux of the phase change at the
valid for almost all substances. It implies that the factors deter-
interface is written as
mining the surface tension are the molar volume and ½Tc  Ti ðrÞ.
Because the addition of coffee powder to water does not alter the sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
 2
volume and mass significantly, we can presume that the molar dh
Qevap ¼ HJðxÞ 1 þ : (14)
volume is relatively insensitive to the concentration of coffee. dx
Therefore, Tc , which depends on the concentration, is the most
important factor determining the surface tension. In Eq. (8) the By balancing Qcond and Qevap , we can obtain
surface-tension gradient, not the surface tension itself, is relevant sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
 2
to the radial velocity, implying that Tc is irrelevant to the radial T  Ti ðxÞ dh
k 0 ¼ HJðxÞ 1þ : (15)
velocity. In other words, the radial velocity is determined by the hðxÞ dx
temperature profile, which is independent of concentration
because the factors determining J0 are also independent of con- Xu and Luo [10] have found the SP as
centration. Among the factors determining the radial velocity, rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
therefore, only the viscosity depends on the concentration. Ac- 2l
x0 ¼ h R ; (16)
cording to Eq. (5) of Ref. [17], the viscosity increases by
8% with 2l 0 0
addition of 1.6 g of coffee to 100 g of water. Therefore, use of data for
pure water in the simulation may cause insignificant error. where h0 is the thickness of the adsorbed film. Here, the concave
In the region not too close to the edge, Ti is part of the surface near the edge was assumed to be parabolic with
a radius of curvature of R0 . The SP is evidently independent of the
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi size and shape of the droplet. It only depends on the shape of the
 
H dhðxÞ 2 concave part at the edge.
Ti ðxÞ ¼ T0  JðxÞhðxÞ 1þ ; (11) We slightly modified the model proposed by Xu and Luo to
k dx
obtain the more exact dependence of the SP on the shape of the
convex part of the droplet. We assumed that the convex part of the
where JðxÞ ¼ J0 ðR2  x2 Þl with l ¼ 0:5  q=p and
droplet is spheroidal and incorporated the derivative of the height
0sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi 1 with respect to the position x, which is
b 2 R2 R
hðxÞ ¼ b@ þ R2  x2  A dh x
tan2 q tanq ¼ (17)
dx R0

for general spheroidal shape of water droplet. Here, we substitute x or,

for r. The temperature can be rewritten as sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi sffiffiffiffiffiffiffiffiffiffiffiffiffiffi
 2
dh x2
0 sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi 1 1þ ¼ 1 þ 2: (18)
bHJ0 R2l @ r2  R2 Aqffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi

ffi dx R0
Ti ðxÞ ¼ T0 
l 1  r2 þ b2  1 x 2 :
k R 2  x2 r2  x2 For the evaporation flux we used Eq. (3) as
(12)  h r i2 l
J ¼ J0 1  ¼ J0 R2l xl ð2R  xÞl : (19)
The parameters used in the simulation are summarized in R
Table 1.
Therefore, the temperature at the vapor-liquid interface is
We have numerically found the tangential speed as a function of
the radial distance under various conditions. As can be seen in  sffiffiffiffiffiffiffiffiffiffiffiffiffiffi
HJ0 R2l x2 x2
Fig. 4, the tangential speed increases as the radius of the droplet Ti ðxÞ ¼ T0  h0 þ 1 þ 2: (20)
increases and both b and the contact angle decrease. Among the kxl ð2R  xÞl 2R0 R0
radius of the droplet, the contact angle and b, the tangential speed
dTi

is most sensitive to the contact angle. The condition dx
¼ 0 requires
x¼x0
 J.M. Baek et al. / Current Applied Physics 18 (2018) 477e483 481

Table 1
Parameters used in the simulation.

Parameter Notation Value Units

Diffusivity of water vapor D 2.61105 m2/s

Saturation concentration of water vapor cV 2.32105 kg/m3
Thermal conductivity of water k 0.610512 J/m s K
Constant for the surface tension of water ks 2.1 107 J/K mol2/3
Molar volume of water Vmol 1.8 105 m3/mol
Latent heat of water H 2.2541 106 J/kg

Fig. 4. Tangential component of fluid speed (a) with different radii for the droplet and b and q fixed, (b) with different values of b and the radius of the droplet and q fixed, and (c)
with different values for q0 s and b and the radius of the droplet fixed.

follows
2
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi3
d 4 2R0 h0 þ x
2 R20 þ x2 h i h
0¼ 5 f 0 ðxÞ ¼ R4 8ð3  lÞ~
x3  5ð3  2lÞ~ x4 þ R4 4ð2  lÞR~2~
0x
dx xl ð2R  xÞl i h

qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi ~2~
 6ð1  lÞR þ R4 b 4ð1  lÞ~
x  3ð1  2lÞ~
2
0x x2
2R0 h0 þ x2 R20 þ x2 2R0 h0 þ x2 R20 þ x2 i
¼ l þ l ~2 ;
xlþ1 ð2R  xÞl xl ð2R  xÞlþ1 þ 2lR 0 (25)
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi

R20 þ x2 x 2R0 h0 þ x2 ~ ≡R =R.

þ2 þ qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi : (21) where ~
x≡x=R and R 0 0 If ~
x<1 then x3 > ~
~ x4 ,
xl1 ð2R  xÞl R20 þ x2 xl ð2R  xÞl 3  l ¼ 2:5 þ q=p > 0, 3  2l ¼ 2 þ 2q=p > 0, and 8ð3  lÞ
5ð3  2lÞ ¼ 2l þ 9 > 0. Therefore, the first bracket is positive for
This implies that ~
x < 1. A very similar argument can be applied for the other two
brackets. It is, therefore, evident that the derivative is positive in the
      range of 0 < x < R, and f ðxÞ is monotonously increasing. As
0 ¼ lð2R  xÞ b þ x2 R20 þ x2 þ lx b þ x2 R20 þ x2
    f ð0Þ ¼ 2bRlR20 < 0 and f ðRÞ ¼ 3R5 þ 2R20 R3 þbR3 > 0, there is only
þ 2x2 ð2R  xÞ R20 þ x2 þ x2 ð2R  xÞ b þ x2 ; one solution, which is the solution we seek in the range of 0 < x < R.
It should be noted here that the location of the SP depends on the
(22) size of the droplet, unlike the model proposed by Xu and Luo [10].
The existence of the SP manifests the balance between the CRE and
where b≡2R0 h0 . Then, the above equation becomes iCRE, and the location of the SP is crucial for determining the
relative strength of the iCRE to the CRE. As a consequence, the
f ðxÞ≡ð2l  3Þx5 þ 2Rð3  lÞx4 þ 2R20 ðl  1Þx3  2RR20 ðl  2Þx2 location of the SP is crucial to determine the strength of the central
h i
spot.
þ b ð2l  1Þx3  2Rðl  1Þx2 þ 2lR20 x  2RlR20
¼0 4. Results and discussion
(23)
By using the results of optical analyses it is clear that the for-
To check the number of roots that may exists in the region of mation of a central spot strongly depends on the volume of the
0 < x < R, we should obtain the derivative droplet. To show this result more clearly, we estimated the ratio of
the amount of coffee particles in the central spot to that in the edge,
f 0 ðxÞ ¼ 5ð2l  3Þx4 þ 8Rð3  lÞx3 þ 6R20 ðl  1Þx2  4RR20 ðl  2Þ assuming that the optical density is proportional to the mass
h i
density. The ratio was obtained by finding the areas under the
þ 3b ð2l  1Þx2  4Rðl  1Þx þ 2lR20
curve, typically shown in Fig. 3, by numerical integration. As shown
¼0 in Fig. 5, the formation of a central spot becomes enhanced as the
(24) volume of the droplet increases up to 15 mL. Further increase of the
volume of the droplet to a value greater than 15 mL leads to the
It is evident that f 0 ð0Þ ¼ 2blR20 > 0. We rewrite the derivative as reduction of the strength of the central spot.
482 J.M. Baek et al. / Current Applied Physics 18 (2018) 477e483
Fig. 5. Ratio of the amount of coffee particles in the central spot to that in the edge for
both sessile and pendant droplets. Lines are guides for the eyes only.
During the process of evaporation, there are 4 factors that can
influence the movement of colloidal particles: the CF, diffusion,
geometric parameters of droplet, and the MF. The CF, influenced by
the shape of the droplet, is always directed toward the edge of the
droplet when the contact angle is less than 90 . The CF is the pri-
mary factor for the formation of the well-known coffee-ring stain.
When colloidal particles accumulate at the edge, a concentration
gradient is built up between the center and the edge of the droplet.
Therefore, diffusion occurs from high- (edge) to low-concentration
(center) regions. As diffusion causes the particles to move to the
center, it might be considered as the reason for the central-spot
formation. Once the central spot is formed, however, the situation
should be reversed. If the diffusion is the dominant factor that
determines the movement of solute particles, neither ring-shaped
stain nor central spot can be formed. Rather, perfectly uniform
stain should be formed. In our experiment, both the ring-shaped
stain and the central spot are clearly formed, so that the diffusion
cannot be the cause of the central-spot formation.
Weon and Je [3] found that the motion of the particles, which is
initially toward the edge owing to the CRE is reversed toward the
center by a capillary force. The reversal effect occurs when the
capillary force prevails over the outward coffee-ring flow. As the
droplet evaporates, the contact angle decreases, and the large-sized
particles move toward the center. Following this theory, however,
colloidal particles receive different strengths depending on their
size. Therefore, when a coffee droplet evaporates, the distribution
of the size of the coffee particles should be clear. Although we did
not carefully analyze the distribution of the size of coffee particles
in both the edge stain and the central spot, we doubt to conclude
that the size distribution of the coffee particles is the primary cause
of the central-spot formation because the typical size distribution
for instant coffee particles [18] more or less follows a normal dis-
tribution with sizes ranging from 0.5 to 1.5 mm. Furthermore, we
were not able to observe the clear difference between the size of
coffee particle at the edge and those at the center.
We found the position of the SP by numerically solving Eq. (21),
to understand the central-spot formation more precisely. Fig. 6
displays SPs as a function of b and q. It is clear that the SP moves
toward the center with an increase in b and decrease in q, thereby
implying that the formation of the central spot is more significant.
As can be seen in Fig. 7, the SP moves toward the center of the
droplet with an increase in the radius of the droplet, although the
dependence of the SP on the radius is considerably weak.
Furthermore, the relative position of SP, x=R, decreases as R in-
creases (see Table 2). It implies that SP moves farther away from the
center as R increases. Therefore, it is clear that the radius of the
droplet is not the primary factor that determines the intensity of
the central spot.
As the evaporation progressed, the contact angle decreases
because the contact line is pinned. This indicates that the SP moves
toward the center of the droplet as the evaporation proceeds.
Furthermore, both R0 and h0 also increase. From Fig. 7, it is evident
that the SPs may move towards the center of the droplet as
b≡2R0 h0 increases. As the dependence of the SP on the contact
angle and b is considerably more sensitive than the radius of the
droplet, the SP will move towards the center of the droplet as the
evaporation progresses. At the initial stage of evaporation there are
no temperature gradients. Therefore, there are no SPs or the MFs. As
the evaporation progresses, a concave surface appears at the edge
of the droplet, resulting in the emergence of SPs and, as a conse-
quence, the MF occurs. Because droplets with larger volume have
considerable amounts of coffee particles, it is reasonable to assume
that the larger the radius of the droplet, the greater the amount of
coffee particles piled up at the edge. As a result, a flattened area
appears owing to the piled-up coffee particles. Moreover, this part
increases more rapidly in a larger droplet, implying that b increases
more rapidly for larger droplets than that for smaller ones, because
both R0 and h0 increase. This indicates that a larger central spot is
formed in larger droplets if the volume is smaller than
15 mL.
Although the position of the SP depends on the contact angle, the
initial contact angle is nearly independent of the volume of the
droplet. Therefore, the initial contact angle is not a primary factor
that determines the central-spot formation. If the volume is larger
than
15 mL, then the central-spot formation becomes weak. This
point will be explained later.
Although the tangential speed slightly increases with the radius
of the contact line, it is not sufficient to explain the strength of the
central spot. We measured the radius of the droplet and the contact
angle to understand the experimental results more thoroughly. The
results are summarized in Table 2. The last column (b) was gener-
ated based on the fact that the volume of a droplet can be given by
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2 2 1
V¼ pbr3  pbr2 r2  R2  pbR2 r2  R2
3 3 3
  2 3=2 
2 b 2b3 b
¼ pbR3 þ1   ; (26)
3 tan q
2 3 tan q tan q
3

Fig. 6. Stagnation points as a function of b and q with R ¼ 1 mm.

 J.M. Baek et al. / Current Applied Physics 18 (2018) 477e483
Fig. 7. Stagnation points as a function of R with q ¼ 0:1 rad and b ¼ 1010 m2.
Table 2
Measured radius of contact line and the contact angle.
Volume (mL) Radius (mm) Contact angle ( )
10 2.280 56.17
12 2.441 55.12
14 2.561 55.31
16 2.631 57.08
18 2.803 52.75
20 2.914 53.82
22 3.038 53.33
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
where r≡R b2 þ 1. The calculated values for b are listed in the
tan2 q
last column of Table 2. b is smaller than 1 for all prepared droplets,
implying that the shape of droplet is an oblate spheroidal cap. This
is due to the effect of gravity because the radius of a droplet is close
to or greater than the capillary length of water, 2.7 mm. The radius
of a droplet increases almost linearly as the volume increases, while
the contact angle is almost independent of radius. Consequently, it
is clear that b increases as the radius of the contact line increases up
to
18 mL and then decreases. The initial increase in the volume
makes the SP located farther away from the edge, resulting in an
increase in the strength of the central spot if the volume is smaller
than
15 mL. The weakening of the strength of the central spot, if
the volume is larger than 15
mL, can be explained by two facts.
The first one is that b has a maximum when the volume is
18 mL.
It implies that the droplet becomes more spherical as the volume
increases up to
18 mL, but it becomes more oblate if the volume is
larger than
18 mL, resulting in a difficult situation for the central-
spot formation. The second one is that the SP moves farther away
from the edge, while the distance from the center increases more
rapidly because the radius of the droplet increase almost linearly
with volume, thereby resulting in more difficulty to move the
coffee particles to the center. These two facts, therefore, result in a
reduction of the strength of the central spot.
The gravity hinders the MF for the sessile drop, because the MF
moves upward, and, as a result, the gravity reduces the iCRE and the
strength of the central spot. However, the situation is reversed for
the pendant drop. In other words, the gravity helps the MF for the
pendant drop because the MF moves downward, and, as a result,
the gravity is expected to enhance the iCRE and the strength of the
central spot. This speculation is clearly evidenced in Fig. 5. The red
solid-circle symbol apparently shows that the maximum strength
of the central spot is located at higher volume for the pendant drop
than that for the sessile drop. Furthermore, the strength of the
483
maximum for the pedant drop is also larger than that for the sessile
drop. These effects of the gravity are another manifestation of the
existence of the iCRE and the MF in a droplet of coffee-water
mixture and the MF as the origin of the central-spot formation.
5. Summary
We investigated the formation of a central spot for a droplet of
coffee-water mixture. We clearly observed the formation of a
central spot, as well as the well-known coffee-ring stain. The
central-pot formation is stronger for droplets with larger contact-
line radius or, equivalently, larger initial volume if the volume is
smaller than 15 mL. Further increase of the volume results in a
reduction of the strength of the central spot. After considering the
various factors that might affect the formation of the central spot, it
was concluded that the Marangoni effect, owing to the temperature
gradient and, consequently, the surface-tension gradient, is the
strongest candidate for the origin of the central-spot formation.
Moreover, the existence of the SP and the dependence of its loca-
tion on the initial geometrical parameters of the droplet are very
important. The most significant factors that determine the intensity
b of central spot are the ratio of the minor axis to the major axis,
0.804
assuming that the shape of the droplet is spheroidal, and the
0.805 contact angle. In addition, the gravity plays an important role,
0.829 particularly for pendant droplets. The gravity reduces the strength
0.844 of the central spot for the sessile drop, while the gravity enhances
0.909
the strength of the central spot for the pendant drop. These effects
0.822
0.955 of the gravity are another manifestation of the existence of the MF
in a droplet of coffee-water mixture and the MF as the origin of the
central-spot formation.
References
[1] R.D. Deegan, O. Bakajin, T.F. Dupont, G. Huber, S.R. Nagel, T.A. Witten, Capillary
flow as the cause of ring stains from dried liquid drops, Nature 389 (1997)
827e829.
[2] R.D. Deegan, O. Bakajin, T.F. Dupont, G. Huber, S.R. Nagel, T.A. Witten, Contact
line deposits in an evaporating drop, Phys. Rev. E 62 (2000) 756e765.
[3] B.M. Weon, J.H. Je, Capillary force repels coffee-ring effect, Phys. Rev. E 82
(2010), 015305.
[4] T. Xu, M.L. Lam, T.H. Chen, Discrete element model for suppression of coffee-
ring effect, Sci. Rep. 7 (2017) 42817.
[5] Y. Ooi, I. Hanasaki, D. Mizumura, Y. Matsuda, Suppressing the coffee-ring ef-
fect of colloidal droplets by dispersed cellulose nanofibers , Sci. Technol. Adv.
Mater. 18 (1) (2017) 316e324.
[6] A. Marin, R. Liepelt, M. Rossi, C.J. Kahler, Surfactant-driven flow transitions in
evaporating droplets, Soft Matter 12 (2016) 1593e1600.
[7] P.J. Yunker, T. Still, M.A. Lohr, A.G. Yodh, Suppression of the coffee-ring effect
by shape-dependent capillary interactions, Nature 476 (2011) 308e311.
[8] H. Hu, R.G. Larson, Marangoni effect reverses coffee-ring depositions, J. Phys.
Chem. B 110 (2006) 7090e7094.
[9] H. Hu, R.G. Larson, Analysis of the effects of Marangoni stresses on the
microflow in an evaporating sessile droplet, Langmuir 21 (9) (2005a)
3972e3980.
[10] X. Xu, J. Luo, Marangoni flow in an evaporating water droplet, Appl. Phys. Lett.
91 (12) (2007), 124102.
[11] H. Hu, R.G. Larson, Analysis of the microfluid flow in an evaporating sessile
droplet, Langmuir 21 (9) (2005b) 3963e3971.
[12] H. Hu, R.G. Larson, Evaporation of a sessile droplet on a substrate, J. Phys.
Chem. B 106 (6) (2002) 1334e1344.
[13] R. Savino, D. Paterna, N. Favaloro, Buoyancy and Marangoni effects in an
evaporating drop, J. Thermophys. Heat Transf. 16 (4) (2002) 562e574.
[14] Y. Kita, A. Askounis, M. Kohno, Y. Takata, J. Kim, K. Sefiane, Induction of
Marangoni convection in pure water drops, Appl. Phys. Lett. 109 (17) (2016),
171602.
[15] R. Eo€ tvo
€s, Ueber den Zusammenhang der Oberfla €chenspannung der Flüssig-
keiten mit ihrem Molecularvolumen, Ann. Phys. 263 (3) (1886) 448e459.
[16] S.R. Palit, Thermodynamic interpretation of the Eo € tvo
€s constant, Nature 177
(1956) 1180.
 a
[17] V. Sobolík, R. Zitn , V. Tovcigrecko, M. Delgado, K. Allaf, Viscosity and elec-
trical conductivity of concentrated solutions of soluble coffee, J. Food Eng. 51
(2) (2002) 93e98.
[18] Shimadzu Corporation, Measurement of particle size distribution of canned
coffee. http://www.shimadzu.com/an/powder/support/beginner/qn50420000
00kera-att/csc066.pdf, 2015. (Accessed 12 October 2015).