Colloid Polym Sci
https://doi.org/10.1007/s00396-017-4204-8
ORIGINAL CONTRIBUTION
Steady/unsteady electroosmotic flow through nanochannel
filled with electrolyte solution surrounded by an immiscible
liquid
Santanu Saha1 · Partha P. Gopmandal1 · H. Ohshima2
Received: 24 June 2017 / Revised: 16 September 2017 / Accepted: 26 September 2017
© Springer-Verlag GmbH Germany 2017
Abstract This article deals with the electroosmotic flow
through nanochannel filled with electrolyte solution sur-
rounded by an immiscible oil layer where the fluid is
driven by either DC or AC electric field. The walls of the
nanochannel are considered to bear a constant negative sur-
face charge. Additional mobile ions with positive polarity
are present in the surface oil layer. The electrostatic poten-
tial can be obtained from the nonlinear Poisson-Boltzmann
equation. With the known electric potential, we calculate
the axial velocity distribution from the unsteady Stokes
equation. The effects of intrinsic parameters on the overall
electrostatic behavior as well as velocity distribution are dis-
cussed in a great detail. We identify several interesting key
features of the flow distributions under externally applied
DC or AC electric field. For lower range of Debye-Huckel
parameter, the overlap of adjacent electric double layers sig-
nificantly affects the flow profile. In addition for externally
applied sinusoidal AC electric field, a finite settling time is
required to diffuse the momentum of the fluid from the adja-
cent region of the channel wall to the bulk fluid. As a result,
a phase shift between the applied electric field and veloc-
ity field may occur. Under AC electric field, the oscillatory
behavior of the axial velocity is further investigated.
Keywords Electroosmotic flow · Oil layer · DC or AC
electric field · Phase shift
 Partha P. Gopmandal
partha@nitp.ac.in
1 Department of Mathematics, National Institute of Technology
Patna, Patna 800005, India
2 Faculty of Pharmaceutical Sciences, Tokyo University
of Science, Noda, Chiba, Japan
Introduction
Electroosmotic flow (EOF) is one of the fundamental elec-
trokinetic phenomena which refers the motion of ionized
liquid relative to the stationary charged surface under the
influence of an external electric field (Hunter [1], White-
sides and Stroock [2]). The EOF offers much smaller
resistance in comparison with the pressure-driven flow and
resembles a plug-like velocity profile (Masliyah and Bhat-
tacharjee [3]). It has wide variety of applications ranging
from chemical, pharmaceutical, and life sciences industries,
to name a few. So far, therefore, a huge body of literature
is available on the EOF through micro/nano-fluidic devices
(Patankar and Hu [4], Ghosal [5], Bhattacharyya et al. [6],
Park et al. [7], Talapatra and Chakraborty [8]).
In addition, many investigations on the two-phase EOF
involving two immiscible liquids through micro/nano-
fluidic devices have been made (Yang and Ooi [9], Gao et al.
[10], Wang et al. [11]). One interesting key feature of two-
phase EOF is the formation of electric double layer (EDL)
along the liquid-liquid interface. With the applications rang-
ing from industries for pharmaceutical and biomedicine,
chemical engineering (Salim et al. [12]), now the two-
phase EOF through nanochannel are at the focus of growing
scientific interest (Movahed et al. [13]). The concept of two-
phase EOF can also be used to drag a low EO-mobility
liquid (e.g., oil, ethanol, etc.) by a high EO-mobility liquid
(e.g., water) (Brask et al. [14], Watanabe et al. [15]).
In the recent years, the transient EOF under AC elec-
tric field have drawn a great interest to the worldwide
researchers due to its versatile application, for example,
mixing of ionized solutions (Oddy et al. [16]), DNA
hybridization (Wong et al. [17]), dielectrophoretic particle
separation on Lab-on-Chip devices (Hughes [18]), enhance-
ment of flow through ion exchange membranes (Barragan

et al. [19]), to name a few. EOF under AC electric field
has major advantage over DC EOF. For example, the EOF
under DC electric field may produce gas bubbles and they
may block the flow passage, while bubble formation is sup-
pressed under AC electric field. A combined theoretical and
experimental study on EOF through narrow confinement
under an axially applied AC electric field has been made by
Oddy et al. [16]. Based on nonlinear Poisson-Boltzmann-
Stokes model, Dutta and Beskok [20] studied analytically
the EOF induced by an applied sinusoidal AC electric field.
The study on EOF through curved microtube driven by an
external DC or AC electric field has been made by Luo [21].
Transient behavior of two-phase EOF through narrow con-
finements has been reported by Su et al. [22], Gao et al. [23].
It may be noted that the oil layer surrounding an aqueous
stream is related to the limiting situation of an aqueous flow
around a very large oil emulsion or the static or dynamic
electrophoretic mobility of a very large oil particle in an
aqueous solution.
All the existing studies on the two-phase EOF under DC
or AC electric field, the surface layer of low EO-mobility
liquid is considered to be electrically neutral. While in sev-
eral biological system, the low EO-mobility liquid (e.g.,
lipid monolayer) may bear additional free mobile ions,
which may affects the overall electrostatic properties across
the interface between the low and high EO-mobility liquids
(Ohshima et al. [24]). Recently, Gopmandal and Ohshima
[25] studied extensively the EOF through electrolyte col-
umn surrounded by an oil layer which carries additional
mobile ions. They have shown that the presence of addi-
tional mobile ions within the surface oil layer may affect
the overall flow modulation through a narrow confinement
with uncharged wall. On the other hand to provide a more
practical physical model for EOF through nanochannel, one
need to consider the effect of wall charge density on the
overall flow distribution. It may be noted that most of the
surfaces made-up with dielectric material and when it is in
Fig. 1 Schematic of the present
situation
Colloid Polym Sci
contact with electrolyte solution, it can acquires a nonzero
surface charge (Stein et al. [26], Prakash et al. [27]). The
wall charge plays an important role to tune the transport
selectivity of ionic species through narrow confinements
(Yang et al. [28]).
In this study, we have considered a realistic model for
EOF through nanochannel driven by either DC or AC elec-
tric field. The nanochannel is filled with high EO-mobility
electrolyte solution and is surrounded by a low EO-mobility
oil layer. The channel wall is considered to bear a negative
surface charge density and an additional mobile ion with
positive polarity is present in the surface oil layer. Due to
difference in permittivity of the low EO-mobility oil layer
and high EO-mobility electrolyte solution, the penetration
of electrolyte ions across the oil layer-electrolyte inter-
face occurs through a discontinuous manner with non-unit
ion partition coefficient. The mathematical model adopted
here is based on nonlinear Poisson-Boltzmann equation for
potential distribution and unsteady Stokes equation for fluid
flow. The present study applies a numerical approach to
solve the coupled system of governing equations and are
validated with the analytical solution of the corresponding
linearised model. We analyze the most important depen-
dencies of the flow distributions on the key parameters
governing the problem.
Problem formulation
In this article, we have considered the EOF through
nanochannel of height 2h under an externally applied DC
or AC electric field (Fig. 1). The nanochannel is filled
with electrolyte solution surrounded by an immiscible liquid
layer of thickness δ(< h). The channel walls are considered
to bear a constant negative surface charge density σ . The
permittivity, viscosity, and density of the electrolyte media
and the immiscible liquid layer are considered to be f ,
Colloid Polym Sci

μf , ρf and d , μd , ρd , respectively. The immiscible liquid angular frequency with ω = 2πf , where f is the applied
is considered to be dielectric oil and may bear additional frequency of the AC electric field. The governing equation
mobile ions (with valence z), for example, ions adsorbed for the axial velocity component (u(y, t)) can be determined
with surfactant molecules such as anionic AOT or cationic from the following unsteady Stokes equation as
peptides. In addition, the oil layer as well as the electrolyte
⎧
medium contains binary symmetric electrolyte ions. ⎨ μd ∂ 2 u + ρ c Eext = ρd ∂u 0 < x ≤ δ
We assume both the electrolyte ions and additional ∂y 2 d ∂t
(4)
charges present in the oil phase follows the Boltzmann ⎩ μf ∂ 2 u2 + ρ c Eext = ρf ∂u δ < x ≤ h
∂y f ∂t
distribution and are given by
⎧   The appropriate boundary conditions for the axial velocity
⎪
⎪ n (y) = b n exp ∓ F φ(y)
;
⎪
⎪ ± ± 0
 RT
u are given by
⎪
⎪
⎪
⎨ Nδ exp −zF φ(y)
RT
nd (y) =  δ  −zF φ(y)  :0<y≤δ ⎧
exp

dy

(1) ⎪
⎪ u|0 = 0,
⎪
⎪
0 RT
⎪
⎨ μ du | − = μ du | + ,
⎪
⎪ n± (y) = n0 exp ∓ FRT φ(y)
;
⎪
⎪
d dy y=δ f dy y=δ
(5)
⎪
⎩ n (y) = 0 ⎪ u| = u|
:δ<y≤h ⎪ y=δ − y=δ ,
+
d ⎪
⎩ du | = 0
dy h
Here, b± are the ion partition coefficients of the electrolyte
ions with n± (δ−) = b± n± (δ+), where n± and nd are the Introducing the scales h, φ0 (= RT /F ), n0 , UH S (=
concentration of the electrolyte ions and additional mobile εf E0 φ0 /μf ) and τ (=h/UH S ) for the y-coordinate, poten-
ion present within the oil layer with bulk molar concentra- tial, concentration of ionic species, velocity, and time,
tions n0 and N, respectively. Here, F , R, and T are the respectively. With these the scaled potential and velocity
Faraday constant, gas constat, and absolute temperature, equations are given as
respectively. A detailed derivation of concentration distri-
bution of additional mobile ions within the oil layer can be 2
d 2 φ̄ − (κh)
2εr ρ̄d , 0 < ȳ ≤ δ̄
c
found elsewhere (Gopmandal and Ohshima [25]). = 2 (6)
d ȳ 2 − (κh)
2 ρ̄f , δ̄ < ȳ ≤ 1
c
The equilibrium electric potential relative to the bulk
electrolyte can be determined through the Poisson equation
as follows and
⎧ c
d 2φ ⎨ ρd (y) : 0 < x ≤ δ
(κh)2 ρr ∂ ū
− 2 = ρfcεd(y) (2) ∂ 2 ū − μ1r 2 Ēext ρ̄d + Re μr ∂ t¯ ,
c 0 < ȳ ≤ δ̄
dy ⎩ :δ<x≤h = 2 (7)
∂ ȳ 2 − (κh)
2 Ēext ρ̄f + Re ∂ t¯ δ̄ < ȳ ≤ 1
εf c ∂ ū

where ρdc (y) = F [n+ (y) − n− (y) + znd (y)] and ρfc (y) =
where variables with ‘bar’ represents the corre-
F [n+ (y) − n− (y)] are the space charge density of the oil
sponding

non-dimensional values. Here,
 ρ̄dc =
layer and electrolyte medium, respectively. For the sake of
simplicity, we consider the half depth of the channel as com- b+ exp(−φ̄) − b− exp(φ̄) + zβN
n0 exp(−zφ̄) and

putational domain. The boundary conditions for φ(y) are ρ̄f = exp(−φ̄) − exp(φ̄) are scaled charge densities with
c

⎧ dφ
⎪
⎪ εd dy |0 = −σ, δ̄
⎪
⎨ dφ − β=
εd dy |δ = εf dφ dy |δ + ,
δ̄
exp(−zφ̄)d ȳ
(3) 0
⎪
⎪ φ| − = φ| + ,
⎪
⎩ dφ
δ δ
dy | h = 0 The permittivity, density, and viscosity ratio are given by
εr = εd /εf , ρr = ρd /ρf , and μr = μd /μf , respec-
For a pure EOF, we ignore the pressure gradient along tively. The Debye layer thickness κ −1 is defined as κ −1 =

the axial direction. The fluid inside the nanochannel flows εf φ0 /2F n0 . The scaled electric field, scaled by E0 , is
under the application of either DC and AC electric field. given by Ēext = 1 (for DC electric field) or Ēext = sin(ω̄t¯
Hence the axial electric field is given by Eext = E0 (for DC (for AC electric field), where ω̄ represent the scaled angu-
electric field) or Eext = E0 sin (ωt) (for AC electric field). lar frequency with ω̄ = 2πf h/UH S . The nondimensional
Here, E0 is the applied electric field strength and ω is the parameter Re = ρf UH S h/μf is the Reynolds Number.
 Colloid Polym Sci

The Eqs. 6 and 7 are solved subject to the scaled bound- [30], Hsu et al. [31]). Since oil layer is of low dielectric con-
ary conditions given by stant and it corresponds the value of ion partition coefficient
⎧ to be less than unity (Ohshima et al. [24]). The free addi-
⎪ d φ̄
d ȳ |0 = −σ̄ ,
⎪ tional ions present in the surface oil layer are considered to
⎪
⎪
⎨ be cationic in nature with z = 1. The viscosities and den-
εr dd φ̄ȳ |δ̄ − = dd φ̄ȳ |δ̄ + ,
(8) sities of the CHB solvent and the electrolyte media are set
⎪
⎪ φ̄|δ̄ − = φ̄|δ̄ + ,
⎪
⎪ to 2.269 and 1 mPa s, and 1.33 and 1 g/cm3 , respectively
⎩ d φ̄ | = 0
d ȳ 1 (Leunissen [29]). The height of the channel (2h) is taken
to be 20 nm with oil layer thickness δ = 0.25h. The con-
and centration of bulk electrolyte is varied from low to high so
⎧ that the Debye-Huckel parameter κh ranges from 1 to 100.
⎪
⎪ ū|0 = 0,
⎪
⎨ μ d ū | − = d ū | + ,
In the subsequent sections, we present some representative
r d ȳ δ̄ d ȳ δ̄
(9) results of this rigorous study with the above set of physical
⎪
⎪ ū| − = ū| δ̄ ,
+ parameters.
⎪ δ̄
⎩ d ū | = 0
d ȳ 1

Here, σ̄ denotes the scaled surface charge density with σ̄ = Results and discussions
σ h/εd φ0 .
The governing equation for induced potential (6) is a non- Before presenting the results, we first validate our computed
linear equation. We solve the Eq. 6 subject to the boundary solution for the potential and velocity field with the cor-
condition (8) iteratively through a second-order central dif- responding analytical solution based on low potential limit
ference scheme. The iterations are continued until the abso- and under a DC electric field. If the thickness of the sur-
lute difference between two successive iterates becomes face oil layer δ is much greater than the Debye length (κ −1
smaller than the tolerance limit 10−6 . With the known ), i.e., κδ >> 1, then the potential deep inside the surface
potential, we have solved iteratively the unsteady Stokes layer approaches to the Donnan potential φDON (Ohshima
equation (7) with the specified boundary conditions (9). An [32]). Under this assumption, the concentration distribution
implicit first-order scheme is used to discretize the time of the additional mobile ion present in the surface oil layer
derivative and a second-order central difference scheme is is given by (Gopmandal and Ohshima [25])
used for the spatial derivative. The discretized equation is
 
solved by a line-by-line iterative method along with the −zF [φ(y) − φDON ]
successive-over-relaxation (SOR) technique. Initially, iter- nd (y) = N exp (10)
RT
ation procedure starts with a guess value of the velocity
and the iterations are continued until the absolute difference
where the Donnan potential is given by (Ohshima [32])
between two successive iterations becomes smaller than the
tolerance limit 10−6 . ⎡  ⎤
It may be noted that under Debye-Huckel limit, one can  2
RT ⎣ zN zN b− ⎦
obtain the closed form solution of the electric potential. φDON =− ln − + +
F 2b+ n0 2b+ n0 b+
In addition under DC electric field, a closed form solu-
tion of the axial velocity can also be derived. The detailed (11)
derivation of analytical solution for EDL-induced electric
potential and axial velocity are shown later to this article. Under a small potential limit (i.e., |φ̄| << 1), the
We validate our numerical solution with the corresponding non-dimensional linearised Poisson-Boltzmann and Stokes
Debye-Huckel solution under DC electric field. Of course equations under a DC electric field can be written as
here, we present the numerical results by considering much
larger ranges of the parameter space. 
d 2 φ̄ P 2 φ̄ − Q : 0 ≤ ȳ ≤ δ̄
The wall charge density (σ ) is considered to be nega- = (12)
tive and its value can ranges up to −50 mC/m2 (Stein et al. d ȳ 2 R 2 φ̄ : δ̄ ≤ ȳ ≤ 1
[26], Prakash et al. [27]). The electrolyte media is consid-
ered to be high dielectric constant liquid, such as water and
(f /0 = 80), where 0 is the permittivity of free space. In ⎧
d 2 ū ⎨
the current study, we consider the oil present in the surface εr d 2 φ̄
μr d ȳ 2 : 0 < ȳ ≤ δ̄
layer as oily organic solvent cyclohexyl bromide (CHB) = (13)
d ȳ 2 ⎩ d 2 φ̄
: δ̄ < ȳ ≤ 1
with d /0 = 7.9 (Leunissen [29], Yethiraj and Blaaderen d ȳ 2
Colloid Polym Sci


  
where P = (κh)2
b+ + b− + z2 βN
, Q = where A = B − Pσ̄ , B = aa22 aa64 −a 3 a5
−a1 a5 , C = D exp (−2R)
2εr n0  

 a1 a6 −a3 a4
(κh) 2 zβN and D = a2 a4 −a1 a5 . Here
b + − b− + , R = κh. Here, the value of β
2εr n0 ⎧ 
can be approximated by exp (zφ̄DON ), where φ̄DON is the ⎪
⎪ a1 = εrRP exp (P δ̄) − exp (−P δ̄)
⎪
⎪
scaled Donnan potential, scaled by φ0 . The closed form ⎪
⎪ a2 = exp {R(δ̄ − 2)} − exp (−R δ̄)
⎪
⎨ a = εr σ̄ exp (P δ̄)
solution of Eq. 12 subject to the boundary conditions (8) 3 R (15)
can be obtained as ⎪
⎪ a4 = exp (P δ̄) + exp (−P δ̄)
⎪
⎪
⎪ a5 = exp
⎪ {R(δ̄ − 2)} + exp (−R δ̄)
 Q ⎩ a =  σ̄ exp (P δ̄) − Q
⎪
A exp (P ȳ) + B exp (−P ȳ) + : 0 < ȳ ≤ δ̄ 6 P P2
φ̄ = P2
C exp (R ȳ) + D exp (−R ȳ) : δ̄ < ȳ ≤ 1 With known potential given in Eq. 14, the axial velocity
(14) can be obtained as

⎧ εr 
⎪
⎪ A{exp (P ȳ) − 1} + B{exp (−P ȳ) − 1} : 0 < ȳ ≤ δ̄
⎨ 
μr 
  
εr Q εr
ū = − μ
r A + B + P2 + C exp (R ȳ) +  μr − 1 exp (R δ̄) + (16)
⎪
⎪
⎩ D exp (−R ȳ) + εr − 1 exp (−R δ̄) : δ̄ < ȳ ≤ 1
μr

In Fig. 2, we present the induced potential and axial dis-
tribution for different values of partition coefficient of the
electrolyte ions (b = b± = 10−4 , 10−3 , 10−2 , 10−1 ). The
corresponding analytical solutions are also shown. The con-
centration of bulk electrolyte solution is considered to be
high (n0 = 104 mM) so that κδ(= 25.66) becomes much
greater than 1. It is clear from Fig. 2 that our numerical
results based on nonlinear model agree well with the corre-
sponding analytical solution at higher values of ion partition
coefficient. It may be noted that the neutralization of the
charge enclosed in the surface oil layer increases with the
increase in ion partition coefficient and it leads to a rela-
tively low effective charge enclosed in the oil layer. As a
result, the magnitude of the induced potential as well as the
axial velocity decreases with the increase in b and hence the
computed solution matches well with corresponding ana-
lytical solution at higher values of b. On the other hand,
a small discrepancy is found for lower range of b as the
charge neutralization due to ion penetration inside the oil
layer is less significant at lower values of b. In addition, we
have also shown the induced potential and the axial distri-
bution (Fig. 3) for different values of concentration of bulk
electrolyte (n0 ). The results in Fig. 3 are shown for higher
value of b(= 10−1 ) where the charge neutralization is sig-
nificant. We found comparable results for strong electrolyte,
while a large discrepancy occurs for low electrolyte con-
centration where the oil layer engulfed by thick EDL (i.e.,
κ −1 ∼ O(δ)). Thus the analytical solution based on low
potential limit for the induced potential and hence the axial
velocity under DC electric field are valid for higher values
of ion partition coefficient and strong electrolyte solution
for which κ −1 << δ. Below, we present the numerical
results without imposing any restriction on the parameters
governing the flow physics.

Fig. 2 a Induced potential and 1.2 0.01

b axial velocity are shown for
fixed value of concentration of 1 0
bulk electrolyte (n0 =104 mM)
Analytical Model -0.01
and mobile ion present in the oil 0.8 Numerical Model
layer (N = 10 mM). The -0.02
b
channel walls are considered to 0.6
be uncharged. The results are
φ

| | -0.03
presented for four different 0.4
values of partition coefficients -0.04
Analytical Model
of electrolyte ions (b+ = b− = 0.2 b
Numerical Model
-0.05
10−1 , 10−2 , 10−3 , 10−4 ). The
corresponding analytical 0 -0.06
solutions obtained from
linearised model are also -0.2 -0.07
0 0.25 0.5
__ 0.75 1 0 0.25 0.5 0.75 1
indicated __
y y
(a) (b)
 Colloid Polym Sci

Fig. 3 a Induced potential and 1.2 0.1

b axial velocity are shown for
n0
fixed value of ion partition 1
coefficient (b+ = b− = 10−1 ) 0
Analytical Model
and concentration of mobile ion 0.8 Numerical Model
present in the oil layer
-0.1
(N = 10 mM). The channel walls 0.6

u
φ
are considered to be uncharged. | |
The results are presented for 0.4
-0.2
four different values of bulk
n0
electrolyte concentration. The 0.2
corresponding analytical -0.3
solutions obtained from 0 Analytical Model
Numerical Model
linearised model are also
indicated -0.2 -0.4
0 0.25 _
0.5 0.75 1 0 0.25 _
0.5 0.75 1
y y
(a) (b)

Electric potential distribution σ = −10 mC/m2 , N = 10 mM, and b = b± = 10−1 . The

In Fig. 4a–d, we present the dependence of EDL induced
electric potential on the key parameters governing the
problem. The results are shown in Fig. 4a for different
values of bulk electrolyte concentration (n0 ) with fixed
results are presented for low to strong electrolyte concen-
tration (n0 ) so that the Debye-Huckel parameter κh ranges
from 1.02 to 102. For increasing values of bulk electrolyte
concentration, we found a decrease in magnitude of the
induced electric potential. For large value of κh (i.e., for

Fig. 4 The dependence of 2 2

induced potential on all the key
n0
parameters is shown. The results
are shown in a for different 0 0
values of bulk electrolyte
concentration (n0 ) with fixed |σ|
-2
σ = −10 mC/m2 , N = 10 mM -2
σ = 0 C/m2
and b = b± = 10−1 ; b for
φ

| |
σ = - 1 mC/m
2

σ = - 10 mC/m 2
different values of wall charge n0 = 10 mM -4 σ = - 50 mC/m
2

density (σ ) with fixed N =

2
-4 n0 = 10 mM
3
n0 = 10 mM
10 mM, n0 = 102 mM and 4
n0 = 10 mM

b = b± = 10−1 ; c for different -6

values of concentration of -6
mobile ion within oil layer (N)
with fixed σ = −10 mC/m2 , 0 0.25 _
0.5 0.75 1 0 0.25 0.5
_ 0.75 1
n0 = 102 mM and y y
b = b± = 10−1 ; d for different
values of ion partition
(a) (b)
coefficient (b = b± ) with fixed
2
σ = −10 mC/m2 , n0 = 102 mM 2
and N = 10 mM 0 b
N
-2
0
-4
φ
φ

| |
-6

-2 b= 10-1
-2
-8 b= 5 x 10
N=0.5 mM
b= 10-2
N=1 mM b= 10
-3

N=10 mM
N=50 mM -10
N=100 mM

-4 -12
0 0.25 0.5
_ 0.75 1 0 0.25 _
0.5 0.75 1
y y
(c) (d)
Colloid Polym Sci
strong electrolyte concentration), the Debye layer becomes
thinner and it leads to a strong shielding effect. As a result,
more counterions are confined within the thin EDL and it
leads to decrease in net effective wall charge. As a result,
the magnitude of the electric potential across the channel
decreases for increasing κh (i.e., increasing n0 ).
In Fig. 4b, c, we have shown the effect of wall charge
density and additional charges present in the surface oil
layer on the EDL induced electric potential with fixed n0 =
102 mM and b = b± = 10−1 . As expected, the surface
charge modifies the potential distribution across the chan-
nel and its magnitude increases with the increase in the
value of wall charge density. Since the charges within the
oil layer and along the channel wall are opposite in nature,
a change in sign in the potential distribution may occur
(Fig. 4b). It is also clear from Fig. 4c that the opposite
charges within the oil layer tries to nullify the effect of wall
charge and decreases the magnitude of the wall potential
with the increasing values of concentration of the addi-
tional mobile charges within the oil layer. In addition, a sign
change in the potential distribution can also be achieved by
changing the concentration of the additional mobile charges
within the oil layer (Fig. 4c). On the other hand, the partition
coefficient of the electrolyte ions has also a significant role
on the modification of the EDL-induced potential which we
have shown extensively in Fig. 4d. The results are presented
here for four different values of b± with fixed σ , N and n0 .
The penetration of the ions inside the oil layer increases with
the increasing values of ion partition coefficient. As a result,
more counterion are confined near the charged wall and it
results a decrease in the effective wall charge. In addition for
increasing values of in b± increases the counterion conden-
sation effect and it results a decrease in net effective charge
inside the oil layer. Due to combined effect of these two, the
magnitude of the potential across the channel reduces with
the increase in ion partition coefficient.
Fig. 5 a Time evolution of axial 0.25
velocity along the center of the
channel. b The axial velocity are
0.2
shown at different values of
scaled time. The results are
0.15
presented here for fixed value of
n0 = 102 mM, σ = −10 mC/m2 ,
uc
N = 10 mM and b = b± = 10−1 | 0.1
0.05
0
-0.05
0 0.05 _ 0.1
t y
(a)
Velocity distribution
In this section, we have presented the effect of the intrinsic
parameters on the overall flow behavior. First, we present
the results under DC electric field and subsequently the
results are shown under sinusoidal AC electric field.
Under DC electric field
Here, we present the transient behavior of the EOF induced
by applied DC electric field. The strength of the DC field
applied along the axial direction is considered to be E0 =
103 V/m. In Fig. 5a, we present the time evolution of the
axial velocity along the central line of the channel (ūc ). In
addition in Fig. 5b, we have presented the axial velocity
component across the channel at different time. From the
results presented in Fig. 5, it is clear that the flow evolves
through a transient response to reach a steady state situation.
It may be noted that at the initial stage of the application of
electric field, the fluid adjacent to the channel wall response
immediately. As the time elapses, the momentum of the
fluid gradually diffuses from the EDL to the bulk region
(Fig. 5) and after some transient time, the axial velocity
reaches to a constant steady state value.
In Fig. 6, we present the results of the axial velocity com-
ponent at a steady state situation. The results are presented
here for a similar set parameters chosen in Fig. 4. In Fig. 6a,
we have shown the effect of electrolyte concentration on the
overall flow modulation. For increasing values of n0 , the
magnitude of the EDL-induced potential decreases (Fig. 4a)
and it results a decrease in axial velocity component across
the channel (Fig. 6a). A plug-like velocity profile can be
achieved for strong electrolyte solution. In Fig. 6b, c, we
present the relative importance of the wall charge density
(σ ) and the concentration of additional mobile ions within
the oil layer (N). Since the wall charge and the charges
_
t_ =0.0005
t=
_ 0.006
0.2 t= 0.015
_
t_ =0.04
t = 0.05
0.15
u
|
0.1
0.05
0
0.15 0 0.2 0.4 0.6 0.8 1
(b)
 Colloid Polym Sci

Fig. 6 The dependence of axial 0.6 0.6

σ = 0 mC/m
2
n0 = 10 mM
velocity on all the key n0 = 102 mM σ = - 1 mC/m 2
parameters are shown. The 0.5
3
n0 = 10 mM 0.5 σ = - 10 mC/m
2

n0 = 104 mM σ = - 50 mC/m 2
results are presented here for a 0.4
similar set of parameters as 0.4
shown in Fig. 4a–d 0.3
0.3 |σ|

u
| | 0.2
0.2
0.1
0.1
0

0 -0.1
n0
-0.1 -0.2
0 0.25 0.5
__ 0.75 1 0 0.25 _
0.5 0.75 1
y y
(a) (b)
0.8
0.2 0.7

0.6
0.1
N 0.5

0 0.4

u
u

| |
N=0.5 mM
N=1 mM 0.3
b
N=10 mM
-0.1 N=50 mM 0.2
N=100 mM
0.1 -1
-0.2 b = 10
b = 5 x10-2
0 b = 10
-2

b = 10-3
-0.3 -0.1
0.5 _
0 0.25 _ 0.75 0 0.25 0.5 0.75 1
y y
(c) (d)

enclosed within the oil layer are opposite in nature and
hence a change in sign of the axial velocity component
may occur (Fig. 6b). On the other hand, the distribution of
axial velocity components across the channel becomes more
interesting for increasing values of concentration of addi-
tional mobile ions (N ) within the oil layer (Fig. 6c). For
lower values of N, the value of the axial velocity component
is positive throughout the channel. With the increase in the
value of N, the axial velocity component remains positive
within the surface oil layer, while its value becomes nega-
tive at the bulk electrolyte. In Fig. 6d, we have shown the
effect of ion partition coefficient on the axial velocity for the
fixed value of the other parameters. With the increase in the
value of ion partition coefficient decreases the magnitude of
the EDL-induced potential and it leads to a decrease in the
value of axial velocity across the channel.
In Fig. 7, we have shown extensively the dependence of
overall flow rate on the pertinent parameters. To provide
a quantitative measurement, we present the average axial
1
velocity, defined as ūavg = 0 ū(ȳ)d ȳ. In Fig. 7a–c, we
present the variation of ūavg with κh (by varying electrolyte
concentration for a fixed channel height) for different val-
ues of (i) σ (Fig. 7a), (ii) concentration of additional mobile
ion within oil layer (Fig. 7b), and (iii) ion partition coeffi-
cient (Fig. 7c). In each case, we found that the average flow
rate (ūavg ) attains a local maxima depending on the choice
of κh. A similar observation has been reported by Haywood
et al. [33] for EOF through parallel plate nanochannel. For
lower range of κh (i.e., thick EDL), the adjacent EDLs may
overlap and it results a nonzero value of net mobile charge
along the center of the channel and it results a nonzero
induced potential thereat (see inset figures). If we decrease
the value of κh from its critical value where the average flow
rate attains its maximum value, the EDL-induced potential
along the channel center becomes nonzero and it results
the occurrence of such a local maxima. The existence of
such a maximum value of the average flow rate is impor-
tant in micro/nano-fluidic applications [34]. On the other
hand for higher values of κh, the effect of σ and N signifi-
cantly diminishes and results a decrease in surface potential
that leads to a decrease in magnitude of the average flow
rate (Fig. 7a,b). On the other hand for increasing values of
Colloid Polym Sci

σ = 0 mC/m
2
0.8 N = 1 mM b = 10-1
σ = -1 mC/m 2 0.4 N = 10 mM 0.8 b = 10
-2

σ = -10 mC/m
2
-3
N = 20 mM b = 10
0.6 σ = -50 mC/m 2 N = 50 mM b = 10
-4

σ = -100 mC/m
2
N = 100 mM
0.2 0.6
0.4
|σ|
0.2 0 0.4

uavg
N

uavg
uavg

b
0 | 0.2
| | -0.2
-0.2
0
-0.4
-0.4
-0.2
-0.6 -0.6
-0.4
0 1 2 0 1 2
10
0
10
1
10
2
10 10 10 10 10 10
κh κh κh
(a) (b) (c)
Fig. 7 Variation of average axial velocity with κh for different val- coefficient with fixed σ = −10 mC/m2 , and N = 10 mM. The inset
ues of a surface charge density (σ ) with fixed N = 10 mM, and figures corresponds the variation of EDL-induced potential along the
b = b± = 10−1 . b Concentration of mobile ion within oil layer (N) central line of the channel (φ̄c )
with fixed σ = −10 mC/m2 , and b = b± = 10−1 . c Ion partition

ion partition coefficient increases charge neutralization and low to high frequency of the applied AC electric field. When
it leads to a reduction in magnitude of average flow rate a periodic sinusoidal AC electric field applied, the flow
(Fig. 7c). behavior goes through a transient phase and finally reaches
at a stable periodic oscillations. A finite time is required for
Under AC electric field diffusion of momentum from the regions close to the chan-
nel wall (i.e., EDL) to the bulk fluid. In addition, when the
Keeping the flow distribution under applied DC field in AC electric field reverses its direction, the bulk fluid along
mind, here we present some representative results of the the center of the channel oscillates during a period of tran-
velocity distribution under an applied AC electric field. The sient response and finally the bulk fluid reverse its direction.
applied electric field along the axis of the channel is con- From the results presented in Fig. 8, it is clear that the tran-
sidered to be Eext = E0 sin(ωt) with the angular frequency sient behavior of the velocity profile strongly depends on the
given by ω = 2πf , where the amplitude and the cycle frequency of the applied AC electric field. For low applied
period of the applied AC electric field are E0 and 1/f , frequency (Fig. 8a), the time required to reach a steady
respectively. In order to present the results, we consider the periodic oscillation is almost zero and the flow profile oscil-
value of E0 as 103 V/m and frequency of the AC electric lates in a similar manner as that of the applied electric field
field (f ) is varied from 10 to 4000 Hz. without having any phase shift. On the other hand for high
In Fig. 8, we present the time evolution of the axial veloc- frequency, the time required for the momentum diffusion
ity at the bulk liquid (along the center of the channel) for is much greater than oscillation time period. At the initial
Maximum Overshoot

0.02
0.003

0.01 Peak 0.002

uc

|
uc

Bandwidth

0.001
0

Settling Time
0
-0.01

0 0.003 0.006 0.009 0 0.003 0.006 0.009 0.012 0.015

t (sec) t (sec)
(a) (b) (c)
Fig. 8 Time evolution of the axial velocity along the central line are N = 10 mM, and b = b± = 10−1 . In Fig. a, the green dotted lines
shown for different values of frequency a f = 10 Hz, b f = 1000 Hz, represents the corresponding scaled electric field
and c f = 4000 Hz with fixed n0 = 102 mM, σ = −10 mC/m2 ,

Fig. 9 Dependence of a phase 360
shift of transient velocity
response relative to the applied 300
electric field and b maximum
magnitude of axial velocity on
240
the frequency of applied electric
field. Results are presented here
Φο
for fixed n0 = 102 mM, 180
σ = −10 mC/m2 , N =10 mM
and b = b± = 10−1 120
60
0
1 2
10 10
f (Hz)
(a)
stage of the application of sinusoidal AC electric field, the
fluid starts to move along the positive axial direction. As the
time elapse, the electric field changes its direction immedi-
ately due to small oscillation time period for high frequency.
However, due to finite settling time required for momen-
tum diffusion, the fluid at the center of the channel does not
respond immediately to the electric field imposed on it. As
a result the fluid along the center of the channel initially
continues to accelerate along the positive axial direction
until the momentum diffusion along the negative direction
reaches (Fig. 8b-c) and then settle down to its oscillatory
behavior after a period of transient response.
In general, it can be seen from the results presented
in Fig. 8 that the flow velocity lags behind the electric
field with a nonzero phase shift. In addition, the magni-
tude of the peak of periodic oscillations of the flow velocity
(i.e., max(|ūavg |)) also depends strongly on the applied
frequency. In Fig. 9a, b, we have shown extensively the
dependence of the phage shift () between the applied elec-
tric field and velocity distribution as well as the maximum
peak value of the average axial velocity on the applied fre-
quency (f ). The results are presented here for three different
values of ion partition coefficient with fixed values of σ ,
N and n0 . Since a finite settling time is required to reach
and settled at a stable periodic situations, the flow veloc-
ity lags behind that of the applied electric field and the
phase lag increases with the increasing values of applied
frequency (Fig. 9a). On the other hand, it is clear from
Fig. 9b that the maximum peak value of the average flow
rate decreases with the increasing values of applied fre-
quency. At a higher values of frequency, due to finite fluid
inertia effect, the flow velocity cannot respond fast enough
in developing an equivalent amount of flow across the chan-
nel and results a decrease in overall flow rate. A similar
finding has been observed by Chakraborty and Ray [35] for
circular microchannel under applied sinusoidal AC electric
Colloid Polym Sci
0.6
b = 10
-1
b = 10-2
-4
b = 10
0.4
max( |uavg|)
|
0.2
-1
b = 10
-2
b = 10
b = 10
-4
0
3 1 2 3
10 10 10 10
f (Hz)
(b)
field. In addition we found that the ion partition coefficient
increases the phase lag and decreases the maximum peak
value of the average flow rate.
Conclusion
In the present article, we have studied extensively the
steady/unsteady EOF through nanochannel filled with elec-
trolyte solution surrounded by an oil layer. Here, we have
considered the EOF induced either by an external DC or
AC electric field. The surface charge distributed along the
channel wall and the net charge entrapped within the dielec-
tric oil layer due to presence of additional mobile ions are
considered to be opposite in nature. A simplified mathemat-
ical model based on Poisson-Boltzmann-Stokes equations is
used to analyze the potential distribution and hence the flow
behavior by considering non-unit partition coefficient of the
electrolyte ions. For DC electric field, we have shown that
a steady-state velocity profile can be achieved after some
transient time. At steady state, the average axial velocity
may attain a local maxima for a critical value of the Debye-
Huckel parameter. On the other hand, for AC electric field,
the magnitude of the axial velocity as well as the phase
shift between the electric field and the flow profile, are both
frequency-dependent. Higher values of applied frequency
increases the phase shift and decreases the average veloc-
ity across the channel. These results, therefore, provides a
broader physical insight associated with the EOF through
nanochannel filled with electrolyte solution surrounded by
an oil layer.
Funding The authors (PPG & SS) acknowledges the financial sup-
port received from the Science and Engineering Research Board
(SERB), Department of Science & Technology, Government of India,
through the project grant (File no. YSS/2015/000468).
Colloid Polym Sci
Compliance with ethical standards
Conflict of interests The authors declare that they have no conflict
of interest.
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