Electrokinetic Energy Conversion by Microchannel

Array: Electrical Analogy, Experiments and Electrode

Polarization

Abraham Mansouria, Subir Bhattacharjeeb, and Larry W. Kostiukc*

a - Department of Mechanical Engineering
American University in Dubai
Dubai, UAE 28282
b Water Planet Engineering
721 S Glasgow Ave, Inglewood, CA 90301, United States
c - Department of Mechanical Engineering
University of Alberta
Edmonton, Alberta, T2G 2G8
CANADA
*Corresponding Author
Telephone: 780-492-3450
Fax: 780-492-2200
E-mail: Larry.Kostiuk@ualberta.ca

Type of Article: Full Length

Abstract:
This paper takes a system-wide perspective of electrokinetic energy conversion devices
based on an array of microchannels to help understanding their operation. The approach taken
was a combination of developing an electrical analogy and conducting experiments.
The electrical analogy included current sources for the convection current, resistors for the
conduction current, a capacitor for accumulating the partitioned ions, resistors for ion transport
in the reservoirs, diodes and capacitors for the electrochemistry and polarization at the
electrodes, and a simple external resistive load. The number of parallel channels profoundly
affected the summative resistive and capacitive characteristics of the array, and highlights the
differences between a single channel and an array of channels, especially in the transient
responses and the role of the electrodes.
The electrical analogy was solved by Laplace Transforms to demonstrate a rich and varied
response that such a system exhibits to a step change in flow in relation to relative magnitudes of
the various resistors and capacitors. Experiments were conducted on a structured glass
microchannel array with approximately three million channels (10 m diameter pore size) with
aqueous KCl as the working fluid and tested a variety of electrodes. Besides providing data for
in-situ resistances and capacitances, in particular for the electrodes, keys aspects of the
experimental results were interpreted using the electrical analogy.
Results include the potential challenges in interpretation of externally measured potentials
and currents as streaming potentials and streaming currents, respectively, measuring the
resistances and capacitances of electrodes by novel methodologies, and using the electrical
analogy quantitatively to explore maximizing electrokinetic energy conversion in the steady
state.

Introduction
Electrokinetic energy conversion devices, i.e., systems that convert hydrostatic potential
energy to electrical power by tapping into phenomena related to streaming current (SC) and
streaming potential (SP) at the micro- or nano- scales, have received increasing attention in
recent years [1-5]. The vast majority of these studies have been performed on single channels
where theoretical and experimental results were compared and recommendations given as to how
to build such energy conversion devices to be more efficient. It is generally assumed that the
results associated with single channel studies can be readily adapted to situations involving an
array of parallel channels. This parallel geometry would result in higher output power and
potentially create a macro electrokinetic conversion device that would be usable for practical
situations [4-6].
Within this context, a macro-electrokinetic energy conversion device based on structured
porous media was reported where electrode position within the upstream and downstream
reservoirs, and electrode polarization became key aspects of design optimization [7]. Recently,
Chang et al., advanced the understanding of one of these issues by developing a more
comprehensive theoretical model for the effects of the resistivity of the fluid in the reservoirs for
a micrometer-length nano-channel in an electrokinetic energy conversion systems [8]. To the
best of the authors knowledge, the theory or modeling of electrokinetic energy conversion
devices have yet to include the effects of the electrodes and their polarization. This polarization
phenomenon appears to be unavoidable in high-power electrokinetic energy conversion devices,
such as micro- or nano-channel arrays, due to the relatively high flux of electrochemical
reactions occurring at the electrodes [7,9]. Also unexplored, and theoretically cumbersome, are
the effects of the external load when modeling electrokinetic energy conversion devices.

If based rigorously on governing principles, a model that captures all this physics would
involve the significant complexities associated with solving a coupled set of partial differential
equations, i.e., Navier-Stokes (incompressible fluid flow), Poisson-Nernst-Planck (ion
transports), Butler-Volmer (kinetics of electrons exchange at the surface of electrodes), and
Kirchoffs Laws (external circuit). This brute-force approach to modeling, especially if solved
for a transient case, would likely afford limited physical understanding to help interpretation of
experimental data, and provide little insight into design options to optimize performance. An
alternative approach, which simplifies the physics while providing a means to visualize the basic
processes, could be to develop an electrical analogy to model the transient interactions between
the electrokinetic flow, electrodes and external circuit [7,9].
A byproduct of developing such an electrical analogy would be to help interpret
experimental data to characterize interfacial properties, such as the -potential. Interest in this
quantity comes from the analysis of the electric and compositional fields in a quiescent fluid
reservoir that is in contact with a solid surface, as well as SC and SP phenomena resulting from
pressure-driven flows [10,15-22]. The models that relate SC and SP to the -potential are
historically based on single, infinite long, channels under steady conditions, which may not be
appropriate for an array of channels, and therefore have implications for estimates of the potential in porous media or membranes.
Hence, the primary objective of this paper is to propose and validate an electrical analogy
of an electrokinetic system for the purpose of energy conversion with flow through an array of
finite length microchannels between two reservoirs. Besides the channel flow, the model will
include the physical processes occurring at the electrodes (i.e., electrolysis and polarization)
placed within the reservoirs and that associated with the external electric circuit that connects the

electrodes together. A complementary objective of this paper is to exploit this electrical analogy
to provide a more sound interpretation of attempts to measure the SC or SP for microchannel
arrays by having an external circuit of either zero or infinite resistance, respectively.
The paper is organized as follows: In the first section, the electrical analogy is developed
and then analyzed by a Laplace transform method to provide a framework for understand such
systems. In the subsequent section, an experimental apparatus is described that is used to collect
data for different aqueous working fluids (i.e., altering the salt concentration), electrodes (i.e.,
altering their materials and sizes, as well as their locations within the reservoirs), and the type of
measurement (i.e., trans-capillary potential and external current in either steady-state or transient
conditions). Finally, the experimental results are presented and interpreted with the aid of the
electrical analogy for the general case of energy conversion, as well as the specific cases of the
external circuit being either zero or infinite resistance.

Electrical Analogy of a Microchannel Array

In order to create a robust electrical analogy for comparison with experimental results it
is necessary to define the problem carefully. Figure 1 shows the problem geometry as an array of
parallel straight finite-length microchannels of constant cross-sectional area that separate two
semi-infinite reservoirs. The working fluid is an electrically neutral bulk solvent containing a
multitude of ionic species as solutes. The properties of the substrate material that makes up the
channels and fluid are such that in a no-flow state an electrical double layer (EDL) develops at
their interface. The characteristic cross-stream dimension of the microchannel falls into the
regime that develops a trans-capillary potential under pressure driven flow. The nature of the
flow through the microchannels being considered could be steady, transient or periodic and
include the possibility to reverse flow. Lastly, electrodes are placed in the two reservoirs to
facilitate electrokinetic energy conversion, as well as to simulate typical experimental data
collection systems for measuring either the electrical potential difference across the electrodes or
the current flow through an external circuit. Initially, a model of such a system is developed for
a single microchannel connecting the reservoirs, and then expanded to consider an array of
independent parallel microchannels that share common end conditions, geometry and interfacial
properties.

Figure 1: Schematic of microchannel array that separate two reservoirs. L and R

represent the left and right hand extremes of the channels, respectively, of length L, and
electrodes placed a distance of xe from the channel ends and connected through an external load.

Modeling the Flow in a Microchannel as a Current Source

In developing an electrical analogy for microchannel flow it is helpful to first consider
the mechanistic aspects of transitioning from no-flow to flow for the transport of the solvent and
solutes without consideration of the electrodes. When a pressure difference is applied across the
two reservoirs flow is initiated. The bulk fluid in the upstream reservoir, which is electrically
neutral and uniform in composition, begins to move towards the channel inlet. As the various
positively and negatively charged solutes approach the channel inlet their relative motion is
affected by interacting with the channels EDL, while the solvents motion is essentially
unaffected. This partitioning of co- and counter-ions results in an imbalance in the flow rate of
negative and positive ions into the channel. The convection of the bulk flow in the channel
moves the solvent and charged solutes along the length of the microchannel, and thereby
establishes a current associated with each solute species. As a result, the analogous component to
the hydrodynamic convection of the various ions takes on the form of a current source.
If the flow were from left to right, the flux of positively charged solutes would be current
in that direction, while the transport of negatively charged solutes would be current in the
opposite direction.

This convection current, in amperes, associated with the mth chemical

j
species in the jth channel of the array ( I conv,m
) can be calculated by integrating the local bulk

velocity ( v ) and species molar density ( nm ) weighted by the valance of the species ( zm ) over
the cross-sectional area of one of the microchannels ( A ), such that
j
I conv,m

where F is Faradays constant.

zm
F

n v dA
m

(1)

Figure 2 shows schematically the concurrent convective currents of all M solute species,
which when summed together creates the net convection current in that channel:
M

j
conv

j
I conv,m

(2)

m1

For the specific case of M = 2 and the valance on these two solutes being symmetric and
unity, a model previously proposed for the convection current through a single channel with a
uniform cross-sectional area was given by [11]
j
I conv

pA
f ( a)
L

(3)

where , , , p, and L are the permittivity and viscosity of the fluid, -potential,
pressure difference across the channel, and channel length, respectively, while f(a) is a function
of the inverse Debeye length () and channel radius (a). In the limit of a >> 1, f(a) = 1 and
Smoluchowskis equation is recovered.

Figure 2: Electrical analogy of the convective currents associated with M different

charged solutes being transported by the bulk flow in the jth single channel of a microchannel
array.

Accumulation of Charge and Conduction Current

The imbalance in the convection of charged species through the microchannel results in
the relative depleting of counter-ion solutes near the channel entrance and their subsequent
accumulation near the channel exit (the opposite being true for the co-ion solutes).

This

changing spatial distribution of net free charge density, relative to the no-flow situation,
manifests itself into an evolving electrical potential field with a magnitude determined by the
integration of the Poisson-Boltzmann equation from the upstream reservoir (usually defined as
ground). If the integration is performed all the way to the downstream reservoir, the outcome is
the trans-capillary potential difference. It is important to note that once removed from the
vicinity of the channels inlet and outlet the compositions in the reservoirs remain uniform, so
there is no further contribution to this integration and the bulk of the reservoirs are also uniform
in potential. As the concentrations of the various solutes and the electrical potential become nonuniform across the length of the microchannel, each of the solute species experiences its own
diffusion and migration transport, which completes the Nernst-Plank perspective of the channel
flows.
The direction of diffusion and migration flux of each solute is opposite to their net
convective flux. Given the relative magnitude of concentration and electrical gradients, along
with their respective diffusion coefficients, there is evidence to suggest that the diffusion
component can be neglected in favor of a simplified model that only includes migration of
charged species [12]. Since the migration of each solute is driven by the electric field, this
process is collectively referred to as the conduction current and is typically split into two parallel
paths. One path is associated solely with transport within the microchannels fluid, while the
other path is associated with the charge movement along the solid-fluid interface.

In an electrical analogy, the relative accumulation or depletion of charge of the various

solute species, which are separated by the length of the channel, is represented by a capacitor.
As the charge difference develops across the analogous capacitor, the trans-capillary electrical
potential difference is created.

To capture the migration of current, which is linearly

proportional to this trans-capillary potential difference, resistive elements for each species are
added to the analogy. Including these capacitive and resistive elements into the electrical
analogy results in the schematic shown in Figure 3.

Figure 3: Electrical analogy for the jth channel of a microchannel array for M solute
species where the current sources represent the solutes convection current, the
accumulation/depletion (charge separation) of solutes are represented by a single capacitor, and
conduction current of the various solutes are represented by resistors.

A model for the analogous capacitor has been previously proposed and was based on the
geometric similarities between a parallel plate capacitor and the observation that the charge
separation in the flow occurs across channels with parallel ends [12].

In that case, the

capacitance for a single circular microchannel is solely a function of geometry and permittivity,
while the hydrodynamics, electrostatics, -potential and mass transfer have essentially negligible
effects. The functional form of the capacitance for the jth channel was given as

CCj KC

(4)

where KC is a constant that has been shown to be ~3 [12].

Since each solute species has its own mobility their transport is treated separately. The
model for the resistive elements of a channel for each solute species in the dilute limit (i.e., no
interaction between the transport of different solutes) is given by
j
RC,m

RF,m RS,m
RF,m RS,m

(5)

where RF,m and RS,m are the resistances associated with the individual species transport
through the bulk of the fluid in the channel and that along the solid-fluid interface, respectively,
and given by

RF,m

RS,i

L
A F,m

L
P S,m

(6)

(7)

where F,m is the conductivity of the mth species within the bulk fluid, P is the perimeter
of the channel, and S,m is the surface conductance of the mth species on the fluid-solid interface.
An important feature of the model shown in Figure 3 is that all the various solute current
sources and resistors for the conduction current, as well as the capacitor, are connected together
between two common nodes (L and R). That is, a singular electric field, created by all the
species, is overlaid onto each species to cause their migration. A physical consequence of this
electrical connection is that there is no species-by-species balance between their individual
convection, accumulation and conduction because the electric field is shared. Given the multispecies nature of the charge carriers in the flow, the current produced from one species
convection and its accumulation will be responded to by the conduction back through another
species resistor. The source or sink of any imbalance in each solute becomes the reservoirs.
Consequently, this model facilitates the possibility that the two reservoirs, if not infinite, can
evolve to having different species concentrations. Support for this observation has been observed
in the filtration of multi-component salts [11].

Electrodes and External Load to Produce Electric Power

In the previous sub-sections an analogy was developed that models a trans-capillary
potential difference and the internal currents, the next elements to consider are those needed to
tap into this potential and use the electrical power externally. As shown in Figure 1, a pair of
electrodes is located in the bulk of the reservoirs and they are connected through an external
finite resistive load (though in principle, any type of resistive-capacitive-inductive load could be
used). The physical processes invoked in this situation are the transport of the various charged
species either toward or away from an electrode, and the electrochemistry at the electrode
surface to support the flow of electrons in the external circuit. The driving force for the transport
of each solute relative to the solvent is the electric potential differences between what was
established near the ends of channel and the electrode surfaces. Any solute that migrates to be in
the vicinity of the electrode, but does not readily react, will contribute to the effective
polarization of the electrode and thereby affect the rates of migration of every species because all
solutes share the common electric field.
The migration of solute across the portion of the reservoir from the end of a single
channel to the electrode is modeled similar to the conduction current as a resistor, but given the
geometry shown in Figure 1 results in

RR,m

Bxe
A F,m

(8)

where B is the blockage ratio of the microchannel array. This model assumes this
migration is essentially one dimensional, which creates the image that the size of the electrodes
is of the same magnitude as the microchannel array and that edge effects are negligible. As

depicted in Figure 1, a symmetric spacing of the electrode was chosen, so that xe is the same on
both sides, but this did not have to be the case.
The physical processes that need to be modeled in the electrical analogy involve the
accumulation of each solute next to the electrode surface and the possibility of a threshold
potential difference to exist between the electrode and the surrounding fluid before various
solutes can react.

The accumulation of ions near the electrode surfaces is modeled by a

capacitive element. With the accumulation of the ions near the surface, an electrical potential
difference across the fluid-electrode interface will develop on a time scale associated with
species migration. If that potential difference exceeds the threshold voltage difference require for
electrochemical reactions, then oxidation will occur at the anode (A) and reduction will occur at
the cathode (C). Depending on the sign of the trans-capillary potential difference (which can be
changed by changing the flow direction), current can flow in either direction from the electrodes.
Therefore, along with the accumulation of charge in the boundary layer of the electrode, the
electrical analogy for each solute at one of the electrode is modeled as two parallel diodes with
opposite polarities in parallel with the capacitor [13]. Unlike the previous elements in the
analogy, the characteristics of the diodes and capacitor no longer scale with a particular channel,
and therefore simply designated as DE,m and CE , respectively. The assumption is also made that
the two electrodes are the same material and have the same characteristics, but this does not have
to be the case.
The current density versus over-potential could be modeled by the Butler-Volmer
equation for such electrodes. Typically, for a given electrolyte concentration, the current density
for non-polarizable electrode is quite high, while for polarizable electrodes the current densities
are lower. Figure 4 is a schematic of the proposed model. It is worth noting that the circuit is

divided into two parts based on the whether the charge carriers are ions or electrons, and the
interface is the surface of the electrodes (between points E1 and E2, and A/C).

Figure 4. Proposed electrical analogy for a single channel of a microchannel array,

electrodes and an external resistive circuit. The circuit is divided into two parts based on the
whether the charge carriers are ions or electrons at the surfaces of the electrodes (between points
E1 and E2, and A/C). RR is the bulk electrical resistance for solute migration between the
channel ends and the electrodes. Electrodes are modeled as two parallel diodes with opposite
polarities and a capacitor in parallel. Rext is the external resistive load where the generated
electrical power is used. It is worth noting the extremes of this external load can represent ideal
measurement devices such as a voltmeter ( R ext ) or an ammeter ( R ext 0 ), and will connect
experimental measurements to this proposed model.

Moving from a Single Channel to an Array of Channels

An array of channels replicates the proposed electrical analogy between the E1 and E2
nodes. Given that all the channels and the migration pathways between channel ends and the
electrodes are assumed to be identical, the circuits can all be connected at the respective E1, L,
R, and E2 planes. Connecting identical resistors and capacitors in parallel is straightforward:
(9)

j
RC,i
RC,i
J

CC JCCj

(10)

j
RR,i
J

(11)

RR,i

where J is the number channels in the array. As a result, the electrical analogy is
unchanged in structure, just the magnitude of the resistors and capacitors between the E1 and E2
nodes have changed. Given that J can be large (e.g., the experiments presented later has
J = 3,437,500) there can be a considerable change in the relative magnitude of these components
with respect to each other, as well as compared to the resistive and capacitive characteristics
associated with the electrodes. This shifting of relative magnitudes of in component
characteristics in the origins of the differences between single channel systems and arrays.

At this stage of model development it is worth having a qualitative discussion of the

transient response such a system has to a step change in flow from no-flow to its eventually

steady state. Initially, the two reservoirs would be in equilibrium with each other and an EDL
would exist at the solid-liquid interfaces of the channel material. With the onset of the flow, the
various current sources begin to displace the free-charges, and that distortion of charge creates a
trans-capillary potential difference on a hydrodynamic time scale. There are now two ways the
charged solutes can respond to this evolving trans-capillary potential difference. One is to
migrate back through the channel and the other is associated with the electrodes, which also
sense the developing potential difference between the reservoirs. The potential difference across
the external load will induce motion in the conductors free electrons and create a potential
difference between the electrodes and the bulk of the fluid in their reservoir. This potential
difference will cause the charged solutes to migrate either toward or away from the electrodes.
These various migration processes, either through the channel or in the fluid bulk, occur on a
much slower time scale than the hydrodynamics. Depending on the effective Peclet Number of
the system, the conduction currents and migration through the bulk respond to this growing
potential difference. The imbalance in the convective and migration currents continues until one
of the threshold potential differences is reached at the electrode surfaces and electrolysis begins
to support a sustained current through the external load. Since not all the charged solutes
attracted to the electrodes will react at the available potential difference they will just accumulate
next to the electrode causing its polarization and screening its potential from other solutes that
would migrate in order to react. These processes (i.e., increasing trans-capillary potential due to
local depletion/accumulation of charged solutes at the channels ends, increasing migration
through the channel, migration to the electrodes, and electrolysis at the electrodes) eventually
bring the fluxes into balance and steady state is approached.

Simplifying the Electrical Analogy

In order to provide a more quantitative insight into electrokinetic energy conversion it is
worth simplifying the electrical analogy that was shown in Figure 4. One simplification worth
considering is to reduce the number of solutes to a single dominant cation and anion pair that
will undergo electrochemical reactions, and give these ions the same transport properties so that
the channel can be a single current source and a single effective resistor for the conduction
current. The second simplification is to assume the existence of non-reacting electrodes with
very low over-potentials in the Bulter-Volmer equation. With those simplifications, the electrical
analogy can be reduced to that shown in Figure 5, but the implications of having the various
cations and anions acting independently (especially those that do not participate in
electrochemical reactions) should not be forgotten.

Figure 5. Electrical analogy of a single channel electrokinetic power generation system

and electrodes associated with external circuits. Diodes were replaced with resistive elements in
situation where over-potential needed for reactions is small.

Circuit analyses in Laplace transform domain

The approach used to analyze the transient and steady state characteristics resulting from
the simplified electrical analogy (Figure 5) is to view the circuit in Laplace space. This approach
treats all the elements as impedances, which follow Kirchhoffs current and voltage laws. As a
result, sets of impedances in series can be re-order without affecting the behavior of the whole
system, and this was used to combine the two electrodes into a single set of elements. Figure 6
shows the final version of the simplified equivalent electrical analogy (that takes advantage of
the symmetry assumed of the two electrodes and their placement), which can then be readily
solved. It should be noted that the reservoir and external resistances were not combined because
in the experimental section a model ammeter and voltmeter replace only the external resistance,
so they must remain separate.
Based on Figure 6, the current in the external circuit can be written as

I ext (s) I conv (s)Y (s)

(12)

where Y(s) is the Laplace function:

Y (s)

RC RC RE,T CE,T s
s2 s

(13)

and the constants are given as

RC CC RE,T CE,T RR,T Rext

RC CC RE,T RR,T Rext CE,T RE,T (RC RR,T Rext )

(14)

(15)

 RC RE,T RR,T Rext

(16)

Remembering that the hydrodynamic time scale associated with the convection current is
very short compared to the diffusion time scales, the convection current associated with suddenly
turning-on the flow is considered to be a step function with a magnitude equal to that at steady
flow (i.e., I conv (s) I conv / s ), and the solution in the time domain becomes
t

( )
t
t
1
I ext (t) I conv A B exp cosh Dsinh

2
2

(17)

( )
t
t
1
Vext (t) I conv RC 1 A B exp cosh Dsinh

2
2

(18)

where

RC

(19)

RC

(20)

RE,T CE,T

2 / 4 2
1

(21)

and 1 and 2 are the time constants given by

(22)

2 / 4

(23)

The above expressions provide a general solution to the expected transient response of
the system shown in either Figure 5 or 6 when subjected to a step change from no-flow to flow.
In the following experimental section some special cases were considered, so it is worth reducing
these expressions in order that they align to those experiments. In particular, a unique geometry
was created where the gap between the ends of the channel and the electrodes was reduced to
essentially zero (i.e., xe 0 , which in turn means RR,T 0 ), and these electrode were shorted
with an ammeter so that Rext 0 , which allows the above expressions to be simplified. With
those resistors becoming negligible, then 0 and allows considerable simplification of the
above expressions such that the external current is given by:
t

( )
I ext (t) I conv A E exp

(24)

As for Vext (t) , this would now represent the potential difference between the reservoirs
(i.e., not that between the anode and cathode materials which have reaction occurring), which, if
it was to be measured, would require a separate set of electrodes connected by a voltmeter of
infinite resistance, such that
t

( )
Vext (t) I conv RC 1 A E exp

RC

(25)

(26)

RC

RC RE,T CE,T

(27)

R R

E,T C (CC CE,T )

RE,T RC

(28)

and in the expanded version, Equations 24 and 25 become:

t
R
C
RC ( )
E,T
C

I ext (t) I conv

exp
RC RE,T CC CE,T RC RE,T

RC
Vext (t) I conv RC 1
R

RE,T

t
C
RC ( )
E,T

exp

CC CE,T RC RE,T

(29)

(30)

Building on these previous assumptions, there are four other special cases worth
exploring and these have to do with relative magnitudes of the resistors and capacitors associated
with the channels and the electrodes. The magnitude of the resistors and capacitors can be
altered by orders of magnitude changing the geometry, materials and solute concentration used in
the system.
Case I) CE,T CC
I ext (t) I conv

t
( )
RC
RC RE,T
exp : I ext (t 0) I conv : I ext (t ) I conv
1
RC RE,T RC
RC RE,T

(31a)

t
( )
RC RE,T
RC RE,T
1 exp : Vext (t 0) 0 : Vext (t ) I conv
RC RE,T
RC RE,T

(31b)

Vext (t) I conv

RE,T RC CE,T
RE,T RC

(31c)

Case II) CC CE,T

I ext (t) I conv

Vext (t) I conv

t
( )
RC
RC
1 exp : I ext (t 0) 0 : I ext (t ) I conv
RC RE,T
RC RE,T

t
( )
R R
RC RE,T RC
exp : Vext (t 0) I conv RC : Vext (t ) I conv C E,T
1
RC RE,T
RC RE,T RE,T

(32a)

(32b)

RE,T RC CC
RE,T RC

(32c)

Case III) RE,T RC

I ext (t) I conv

t
( )
CE,T
CE,T
: I ext (t ) 0
exp : I ext (t 0) I conv
CC CE,T
CC CE,T

(33a)

t
C
( )
CC :
C
Vext (t ) I conv RC
Vext (t) I conv RC
exp : Vext (t 0) I conv RC
CC CE,T
CC CE,T

(33b)

RC (CC CE,T )

(33c)

( )
CE,T
CC
: I ext (t ) I conv
I ext (t) I conv 1
exp : I ext (t 0) I conv
CC CE,T
CC CE,T

(34a)

C
( t )
C

c
c
Vext (t) I conv RC
: Vext (t ) 0
exp : Vext (t 0) I conv RC
C

C
C

C
C
C
E,T
E,T

(34b)

RE,T (CC CE,T )

(34c)

Case IV) RC RE,T

The richness of the possible outcomes of a step change in flow rate can be seen in that the initial
external current or initial reservoir voltage difference can either be zero or finite, and these
current and voltages can either rise or fall to a steady state value that is either zero or finite.
Also, the initial current or voltage can be set by the capacitances in the system and/or the
resistance associated with the channels, but as expected the steady state quantities are
independent of the capacitances. These observations will be used in discussions of the
experimental results to identify which case appears to apply, as well as to calculate the
magnitude of the effective capacitances of the electrodes from measured transient responses in
the external current.

Figure 6: Simplified electrical analogy of a microchannel array with one cation and one anion
with the same properties (excepted charge) as solutes and symmetric cathode and anode
electrodes shown in Laplace space.

Experimental Section
Materials
The key materials used in the experiments are the glass microchannel array (GMA), the
working fluid that was pumped through the channels, and the electrodes used to either measure
voltage or to act as surfaces for electrochemical reactions.
The GMA was made of lead silicate glass (Burle Electro-Optics, Sturbridge,
Massachusetts) and consisted of approximately 3,437,500 straight, circular microchannels with a
pore size of 10 m diameter. The thickness, effective diameter, and porosity were 2 mm, 25 mm
and 45%, respectively.
The working fluid for all the experiments was deionized ultra-filtered (DIUF) water
obtained from a water purification system (Millipore Simplicity, 18.2 M/cm), and the KCl
electrolyte solutions were made by adding appropriate amount of KCl powder to the DIUF
water.
Electrodes placed in the reservoirs upstream and downstream of the GMA were
platinized platinum (i.e., platinum black), silver or gold. The platinized platinum represents a
standard high-quality electrode typically used in these kinds of measurements. Since other
investigators have used silver electrodes [5], they were included in this study to provide some
comparative data with respect to electrode material. Also, both faces of the GMA were coated
with a 100 nm layer of gold, which were supported by adhesion layers of nichrome. In reference
to Figure 1, these gold layers are located at the L and R planes, while the location of the
platinum and silver electrodes are located at E1 and E2. The platinized platinum electrodes
had relatively higher surface areas compare to silver electrodes.
electrodes are provided in Table 1.

The particulars of these

Table 1: Characteristics of Reservoir Electrodes

Designation
Platinum*
Silver

Material
99.9% Pt gauze from
wire (Alfa Asesar,
MA, USA)
Silver

Mesh Type
45 Mesh woven
Micro mesh

Wires
0.198 mm
diameter

Diameter (mm)
25

Not
25
Available
Gold
Gold
Deposited
Not
25
Applicable
*Prepared by electro-deposition at 50 mV from 2 % chloro-platinic acid in 1M HCl

Experimental Apparatus
The details of the experimental apparatus have been described elsewhere [7] and only an
overview is provided here. The GMA was clamped between two acrylic cylindrical chambers
with an internal diameter of 25 mm and length of 36 mm, which acted as reservoirs, and sealed
in place with Teflon O-rings. A diaphragm pump (Shurflo Inc., USA) provided a constant flow
rate (0.72 liter/minute) of working fluid. The piping system, consisting of two quarter-turn 3-way
valves, was arranged to allow the flow to be switched rapidly (~0.2 s) in direction through the
GMA (i.e., either L to R or R to L). The supply and discharge reservoirs of the working fluid
were both open to the atmosphere. A differential pressure transducer (PX26-030DV, OMEGA
Inc., USA) was connected across taps in the acrylic chambers to monitor the pressure difference
across the GMA. Each of these chambers also had a 1 mm circular co-axial port at their ends,
which was designed to allow a non-conductive hollow rod to be inserted into the reservoir
without leaking. The platinum and silver electrodes were mounted on the ends of these rods, so
that they could be placed from 1 to 36 mm from the faces of the GMA. A wire was inserted
through the inside of each rod, sealed and butt-welded to the electrode to provide an external
electrical connection to these electrodes. Separate wires were butt-welded to the gold electrodes
and the coated leads passed to the outside of the chambers. All these external leads could then
connected through an external resistive load for power generation, or used to measure the voltage
or current characteristics across the electrodes. An electrometer (Keithley Instruments Inc.,
Model 6517A) was used to measure either the electrical potential or the electrical current. The
experimental data were logged on a computer through a Labview (National Instruments)
interface. The response times of the electrometer in the current mode (time constant on the order

of 0.1 second) and data acquisition system were adequate to capture the behavior of the system,
and data acquisition was performed at 10 Hz.
Before each experiment, all samples, apparatus, pump and connections were rinsed and
washed with deionized water. To avoid any contamination or initial electrode polarization the
experimental protocol by Elimelech et al. [14] was employed and involved flushing the
microchannel array with deionized water in both directions for a period of about 2 minutes to
remove any trapped air bubbles. For each of the electrodes location, at least six measurements
were performed to insure repeatability of results.

Results and Discussions

This particular experimental apparatus allows for altering the flow direction, electrode
type, electrode location, and working fluid, as well as a whether the electrodes are connected to a
voltmeter, ammeter or finite external resistive load, so there are many experiments opportunities
available. A few of these options are explored experimentally and the results interpreted
qualitatively with the aid of the electrical analogy shown in Figure 5, or quantitatively with
Equations 24 and 25.
Data will first be presented for the relatively simple cases of measuring the steady state
trans-capillary potential difference when R ext and then the steady state external current
when R ext 0 using the electrodes in the reservoirs. An observation of these steady state
measurements is that the external current was highly dependent on electrode material,
concentration of salt in the DIUF, and the placement of the electrodes relative to the channel
ends.
Recognizing the advantage from a power generation perspective of having access to
higher external currents, the experiments then focus on extracting current from the gold
electrodes (located at the inlet and outlet planes of the channels). In this arrangement, the
unsteady external current with R ext 0 was measured, which left the ability to monitor the
potential difference between the reservoirs with the other electrodes. The form of the
unsteadiness was done first by following the transient response to a step change in flow from the
no-flow case, and then through a series of flow reversals.
Those previous experiments allowed estimates to be made of the various resistive and
capacitive elements in that analogy. Using those estimates, the relatively complex nature of

steady state electrokinetic power generation is described in terms of the magnitude of the
external load and the polarization that occurs at the electrodes.

Steady-State Trans-Capillary Potential when R ext ) OR External Current when R ext 0 )

Figure 7 shows the measured trans-capillary potential difference when the external
resistance is replaced by a voltmeter ( R ext ) and the external current when the external
resistance is replaced by an ammeter ( R ext 0 ) employing either the platinum and silver mesh
electrodes for 1 mM KCl at identical steady-state flow rates.

The trans-capillary potential

difference is invariant to electrode placement and electrode material. With reference to Figure 5,
the open-circuit created by replacing the external resistance with a voltmeter results in I ext 0
and the analogous collapses to that shown in Figure 8 since all capacitor are not active elements.
Without current flowing through the resistors representing the fluid in the reservoirs or the
surfaces of the electrodes all of the potentials on either side of the GMA are the same. It was
only through these resistors that the dependencies of electrode placement and material would be
introduced, so with their removal these dependencies no longer exist. Furthermore, once steady
state is achieved, this trans-capillary potential difference is the SP, and if all the microchannel
were identical then this SP is the same as for single microchannel experiencing the same pressure
difference as the array.
In contrast, the measured external current depends strongly on the electrode location and
the type of electrode. With reference to Figure 5 and noting that once the system is in steady
state all the capacitors become inactive, the circuit can be simplified and is redrawn in Figure 9.
This simplified circuit provides a couple of key insights. First, since all the resistors are in
series, it is possible to gauge the relative magnitudes of the resistors associated with the bulk

reservoir fluid ( RR ) and the electrodes ( RE ), while the channels resistance ( RC ) remain constant.
The external current can be changed by an order of magnitude by changing the placement of the
electrodes, so obviously RR cannot, in general, be neglected but does become diminishing small
the closer the electrodes are placed to the ends of the channels. (Depositing of gold on the ends
of the GMA to act as electrodes was intended to reduce its resistance to approximately zero.) At
the highest external currents (i.e., when the electrode were placed 1 mm from the channel ends),
the current measured with the platinum electrodes was three times that of the silver electrodes.
At lower currents (i.e., when the bulk fluid resistance was large), the reduction associated with
using silver electrodes was only 20%. One interpretation of why the silver electrode resistance is
higher than the platinum is due its lower surface area. This area ratio between the different
electrodes should be the same for all measurement locations, but whether that difference is
important in setting the measured external current depends on the other resistances in series.
Second, from a macroscopic level the shorting of the anode and cathode for these measurements
look like SC measurements, but inspection of Figure 9 reveals that since current flows through
both RR and RE , then the steady-state trans-capillary potential difference is non-zero and the
conduction current through RC is non-zero. Therefore, these measured external currents cannot
be interpreted as the SC.
Figure 10 compares the measured external current ( R ext 0 ) for the 0.04 and 1 mM KCl
using the platinum electrodes. The external current for the 1 mM KCl is higher due to a lower
bulk reservoir fluid resistance (Equation 8), which also explains the divergence in the measured
external current as the distance the ends of the channels to the electrodes was increased.

Streaming Potential (V)

External Current (A)

10
1 mM KCl- Pt black
1 mM KCl- Silver mesh
1

(a)
0.1

10

100

1000

100

(b)
10

10

100

Electrodes distance from array (mm)

Figure 7 External currents and streaming potential measurements across the GMA for
1mM KCl electrolyte solution. The experiments were performed for electrolyte solutions in
identical flow rates using either the platinum or silver electrodes.

Figure 8: The resulting electrical analogy for steady state when the external resistive load
is replaced by a voltmeter

Figure 9: The resulting electrical analogy for steady state when the external resistive load
is replaced by an ammeter
1000

External Current (A)

1 mM KCl
0.04 mM KCl

100

10

10

100

Electrodes (Pt black) distance from array (mm)

Figure 10: External current measurements in GMA. The experiments were performed for
0.04 and 1 mM KCl solutions in identical flow field conditions using platinized platinum
electrodes

Steady-State and Transient Trans-Capillary Potential when R ext AND R R,T 0

In the previous section, it was not possible to quantify the magnitude of any of the
resistors or capacitors because single resistive elements could not be isolated and capacitive
aspects can only be seen during transients. To effectively remove the two reservoir resistances
from the problem, the gold electrodes were used to extract current by placing an ammeter across
their leads (i.e., R ext 0 for the gold electrodes), and then the potential difference between the
two reservoir could be measured by placing a voltmeter across the leads of the reservoir
electrodes (i.e., R ext for the platinum electrodes). It is worth noting that since no current is
drawn through the reservoir electrodes then the measured potential is representative of the bulk
and not dependent on electrode placement or material. The electrical analogy to this new
configuration of the experimental apparatus is shown in Figure 11.
In this arrangement, a relationship between RC and RE can easily be developed in terms
of the measured steady-state trans-capillary potentials when the anode and cathode are either
shorted (i.e., VRext 0 when ammeter in Figure 11 is connected) or held as an open-circuit (i.e.,

VRext SP when the ammeter in Figure 11 is disconnected, such that:

Rext0

RE,T 2RE RC
SP VRext0

(35)

Where RE,T is the total electrode resistance associated with the combined resistances at
the anode and cathode surfaces, and RC can be estimated from Equation 5.

Under the

assumption of RS being large compared to RF for the electrolytes of interest, then values for RC

for this GMA and RE for the deposited gold electrodes were calculated and listed in Table 2.
The estimated RE,T values in Table 2 are relatively small due to large surface area of gold
electrode in comparison with electrodes normally used with single microchannel experiments.

Figure 11: The resulting electrical analogy for the general response of the system for a
single electrolyte when the gold electrodes were connected through an ammeter (though for
some experiments it was disconnected to measure the SP) and the reservoir electrodes were
connected through a voltmeter.

TABLE 2: Estimations of resistance and capacitance of GMA and gold electrodes based on
proposed electrical analogy. RR,T was assumed to be zero since there is no reservoir fluid
between the channel exits and the electrode, RC was estimated from Equation 6, RE,T was
estimated from measurements and Equation 35, CC was estimated from Equation 4 and 10,
was estimated from the measured decay in external current following a step change in flow, and
CE,T was estimated from Equation 29.
KCl Concentration

RR,T
RC
RE,T
CE,T
CC
(mM)

(s)

nF

0.05

7185

6666

0.51

147

0.28

0.1

3133

9375

0.4

170

0.28

0.5

1102

10555

0.25

251

0.28

In order to gain insight in the capacitive elements associated with the GMA and the
electrodes it is necessary to conduct transient experiments. Figure 12 shows typical results
recorded on the same setup as the steady-state experiments, but now the flow was periodically
reversed. The key observations of the current measured by an ammeter placed between the gold
electrodes are the sudden spike in current either when the flow is turned on or reversed, followed
by the decay in current towards a finite value at steady state. In these cases, the first spike, going
from no-flow to flow, was smaller in amplitude than those associated with flow-reversals, and
this is attributed to the different initial conditions that would have existed at the time the flow
was altered. Prior to the flow being turned on, the electrical and compositional fields would have
been set by the EDL, while at the time of the flow reversals these field are in a considerably
difference condition. After the first current spike and its subsequent decay, all successive
responses to the flow reversals were remarkably repeatable.
Given that the measured current spikes at t 0 then decreases in magnitude to a non-zero
steady-state shows that these experiments have characteristics similar to Case I, as described by
Equations 31a-c. This case is defined as having CE,T CC , and the time constant associated
with the decay in current can be used to estimate CE,T . These values for the capacitance of the
electrodes have been added to Table 2. If the capacitance of the channels are estimated by
Equations 4 and 10, which have also been added to Table 2, then it shows that there is six orders
of magnitude difference between CC and CE,T .
A final feature regarding Figure 12 is that as the concentration of solute increases the
measured external current approached zero as the system decays to steady state. With reference
to Equations 31a in the limit of t and focusing on the relative magnitudes of resistances, the
steady-state current can be pushed closer to zero by increasing RE,T relative to RC . There are

two contributing affects that could lead to this outcome. First, the conductive of the working
fluid has been increased to a point where the channel resistance for conduction current becomes
smaller. Second, the presence of high concentrations of solutes near the electrodes surfaces has
increased the effective electrode polarization so that electrode resistance becomes larger. Using a
more extreme solute concentration of 1 mM KCl there was no steady state current recorded,
which causes Cases I and III too become the same (i.e., CE,T CC and RE ,T RC ). It is also
worth noting that if the external current at t 0 could be resolved accurately, then it would
represent the SC (Equation 31a).
At the other extreme, Figure 13 shows the external current measurements when 0 M KCl
was pumped through the GMA. In this case, using only DIUF as the working fluid, the dominant
cation/anion pair for transport switches from K+/Cl- to H+/OH-, so care must be taken in
interpreting and comparing these data sets. The external current in this case is initially small and
rises to a final steady state value, which would suggestion characteristics closer to either Case II
or IV. From Table 2 it is observed that an order of magnitude drop in KCL concentration (0.5 to
0.05 mM) caused a modest change in the ratio of capacitances, but an order of magnitude rise in
the ratio of resistance.

If the assumption is made that this trend continues down to the

concentration of ions in DIUF water this subsequently pushes the system into a regime where

RC RE,T , which is Case IV. The small initial external current suggests that the relative
magnitudes of the capacitances have also changed for this working fluid (i.e., CC CE,T ), which
is Case II. In either event, the steady state current would be representative of the SC.
Furthermore, the small overshoot in the maximum current shown in Figure 13 may be
indicative that this situation does not fall neatly into any of the extreme cases and would require
analysis through the more general Equations 17 and 18. The rise and fall in current does not

fitted well with a single exponential, and this lack of simple capacitive behavior has been
observed by Conde et al. in a single microchannel geometry [18].

(a)

(b)

Figure 12. Measurement of current by connecting an ammeter across gold electrodes

deposited on the faces of the GMA. Electrolyte solutions of 0.05 and 0.1 mM KCl were pumped
through the GMA in alternating flow directions.

Figure. 13 Measured current by gold electrodes electrodes across GMA with electrolyte solution
of 0 M KCl

In electrochemistry, the current that flows to and from electrodes are divided in two
categories, Faradic (deals with the transfer of electrons) and non-Faradic (deals with the charging
of interface). Within the electrical analogy these aspects are captured by the resistive and
capacitive elements associated with the electrodes, respectively. In a given situation, both of
these currents can exist concurrently or alone. In our experiments, for electrolyte solutions listed
in Table 2, the gold electrode has shown to embody both characteristics. Initially, the system
appears Faradic with initially high currents then followed by a rapid decay as a double layer
develops at the interface of the gold electrodes and electrolyte solution (non-Faradic).
In case of using DIUF water, redox reactions at gold electrodes are extremely fast and
electrons are easily transferred across the electrode-electrolyte interface. As a result, in this case
it is hard to observe the capacitive behavior of the electrodes. This electrolyte solution
maximizes electric double layer thickness and has implication for power output of these devices
when used for energy conversion. The thinner the electric double layer thickness is at electrode
electrolyte interface (i.e., in high electrolyte concentrations), the larger is the double layer
capacitance of NGEs as evidenced by results presented in Table 2. Our findings are also in
excellent agreement with typical double layer capacitance ranging from 10 to 40 F/cm2.

Modeling Steady State Electrokinetic Power Generation with Electrode Polarization

We now have the properties and sub-models needed to exploit the electrical analogy as an
electrokinetic energy conversion system. The external power (P) developed from such a system
2
can be estimated from Equation 17 (i.e., P I ext
Rext ), which in steady state ( t ), electrodes

located at the channel ends ( RR,T 0 ), and a 1 becomes:

 pA

P
L

(36)

RC2 Rext

R E ,T Rext

The effects of polarization in the form of a Faradic resistance across the electric double
layer at the electrode surface on electrokinetic energy conversion is readily seen in the
denominator of the above expression.

This term only has a negative impact on power

generation, but it is worth noting that its importance is diminished as either RC or Rext are made
relatively large. For a fixed geometry, RC can be made large by reducing the concentration of
the solute, and the in the limit of RC RE,T the maximum power generation occurs when

RC Rext .
In order to quantitatively examine the impacts of changing the concentration of the solute
in the working fluid and the magnitude of the external resistance, certain parameters can be held
constant.

These fixed parameters were selected to be relevant to the above experimental

apparatus, working fluid, and applied pressure difference, where 0.025V , p 200, 000 Pa ,
J 3, 437, 500 , A 7.85x1011m2, 0.001Pa s , L 0.002 m , and 7.08x10 10 F/m , while RC ,

and RE,T remain functions of solute concentration. Figure 14 shows the predicted electrokinetic
energy conversion for the KCl solutions listed in Table 2 and for DIUF water. Interestingly, the
steady state power generation can be reduced by three orders of magnitude by changing the
working fluid from 0 mM KCl to 0.5 mM KCl.

It has previously been reported that the

maximum efficiency of this experimental setup was 1.3% when fresh DIUF water was used and
had reduced to 0.002% for 0.1mM KCl solutions. Exploiting the transient characteristics where
the external current is large near t 0 , or non-resistive loads, for power generation has yet to be
explored.

Figure 14. Output power of electrokinetic energy conversation device in steady state
predicted by electrical analogy for a range of KCl concentration for a GMA with gold electrodes
located at the ends of the channels. As the elctrolyte concentration increase, NGEs becomes
more polarized and electrial resistance of electordes increase to the extend that no power can be
recorded for a highly concetrated electrodes.

Conclusions:
This paper takes a system-wide perspective of electrokinetic energy conversion devices
based on an array of microchannels to help understanding their operation. This perspective
includes the pressure driven flow through the microchannels that partition ionic species to create
convection currents and trans-capillary potential difference, the role of the reservoir in terms of
electrode placement upstream and downstream of the channels, the capacitive and resistive
characteristics of electrodes (e.g., their polarization), and an external resistive load.

The

approach taken to help in this understanding is a combination of developing an electrical analogy

for the whole system and conducting experiments on a glass microchannel array.
The electrical analogy was first developed for a single channel and with the possibility of
multiple solutes. The model included a current source for the convection current, resistors for
the conduction current, a capacitor for accumulating the partitioned ions, resistors for ion
transport within the reservoirs, diodes and capacitors for the electrochemistry and polarization at
the electrodes, and a simple external resistive load. The expansion of the analogy to include any
number of parallel channels showed how arrays of channels (through the sum of resistive and
capacitive elements) could be significantly different from the behavior of a single channel. The
resistance to conduction current drops in proportion to the number of channels, while the
capacitance of the array increases in proportion to the number of channels. Single channel results
should not be extrapolated to arrays of channels, especially in the transient responses and the role
of the electrodes when external current is being produced.
The electrical analogy was then simplified for a single dominant anion/cation pair and the
case of small over-potentials at the electrodes. This simplified model was solved by Laplace
Transforms to demonstrate a rich and varied response that such a system exhibits to a step

change in flow depending on the relative magnitude of the various resistors and capacitors.
These system responses showed the possibilities of spikes in either external current or voltage at
the time of the step change in flow, as well as how they decay to steady state (Equations 29
32).
Experiments were conducted on a 25 mm diameter glass microchannel array having
approximately 3,437,500 straight, circular microchannels with a pore size of 10 m diameter and
a channel length of 2 mm. The working fluid was either DIUF water with either no solute added
or KCl added to create concentrations from 0.05 to 1mM. The electrodes were either meshes of
platinum-black or silver, or gold that was deposited on the ends of the microchannel array. A
variety of experiments were conducted measure external current or trans-capillary potential
difference in either steady state or a series of flow reversals.

Besides providing data for

resistances and capacitances, in particular for the electrodes, keys aspects of the experimental
results were interpreted with the electrical analogy.
The trans-capillary potential difference measured by electrodes placed in the reservoirs
upstream and downstream of the microchannel array in steady state flow can be easily
interpreted as the stream potential, and is independent of the type and placement of the
electrodes.
The external current measured by electrodes placed in the reservoirs upstream and
downstream of the microchannel array in steady state flow is not the streaming current, and is
highly dependent on the type and placement of the electrodes. The amount of current going
through a shorted external circuit is affected by the resistances in the channel and that associated
with transporting the solutes from the ends of the channels to the electrodes, as well as the area
and nature of the electrodes. For any electrode type, the highest external currents were measured

when the spacing between channel ends and the electrode were minimized. To eliminate the
resistance associated with transport in the reservoir, the gold deposited on the channel ends were
used as electrodes to isolate other electrical elements for quantification.
The resistances of the gold electrodes for different solute concentrations were quantified by
a methodology that involved measuring and comparing the trans-capillary potential difference by
electrodes in the reservoirs when the gold electrodes were either shorted or left as an open
circuit. At high salt concentrations the resistance of the electrode dominated over the resistance
of the channels, while the opposite was true for DIUF water.
The capacitances of the gold electrodes for different solute concentrations were quantified
by a methodology that involved estimating the time constant of the systems external current as it
approach steady state from a sudden change in flow direction. For any of the salt concentrations
tested, the capacitance of the electrode was approximately six order of the magnitude greater
than the microchannels array, and therefore the system was easily represented by a single time
constant of how the diffusive transport slowly responds to a step change in hydrodynamics. For
the DIUF water case, the results were quite different, showing a rise in current to steady state and
its form not being well described by a single exponential. This different behavior was speculated
to be related to the change in the dominant charge carrying species from K+/Cl- to H+/OH-.
Once all the resistors and capacitors of the electrical analogy were estimated, the system
response to electrokinetic energy conversion was explored. The steady state case was considered
to examine the effects of altering the external resistive load and the concentration of KCl. The
highest electrical power produced was for DIUF water (reduced by three orders of magnitude
with 0.5mM KCl) and when the external resistive load equaled the sum of the internal
resistances.

Acknowledgements:
Financial support for this work was provided by the Natural Science and Engineering Research
of Canada

References
1. Osterle J. F. (1964), J. Appl. Mech., 31, 161.
2. Morrison F. A. and Osterle J. F. (1965), J. Chem. Phys., 43, 21112115
3. Pennathur S., Eijkel J. C. T., and Van den Berg A. (2007), Lab Chip, 7, 1234
4. Heyden F. H. J., Bonthuis D. J., Stein D., Meyer C. and Dekker C. (2007),Nano Lett., 7(4), 1022.
5. Yang J., Lu F., Kostiuk L. W. and Kwok D. Y. (2003), J. Micromech. Microeng., 13, 963.
6. Siria, A., Poncharal, P., Biance, A. L., Fulcrand, R., Blase, X., Purcell, S. T., & Bocquet, L.
(2013), Nature, 494(7438), 455-458.
7. Mansouri, A., Bhattacharjee, S., & Kostiuk, L. (2012), Lab Chip, 12(20), 4033-4036.
8. Chang, C. C., & Yang, R. J. (2010), Microfluidics and Nanofluidics, 9(2-3), 225-24
9. Mansouri, A., Kostiuk, L. W., & Bhattacharjee, S. (2008), Journal of Physical Chemistry C,
112(42), 16192-16195.
10. Mansouri A., Scheuerman C., Kwok D. Y., Kostiuk L. W. and Bhattacharjee S. (2005), J.
Colloid Interface Sci., 292, 567.
11. Masliyah, J. H., & Bhattacharjee, S. (2006). Electrokinetic and colloid transport phenomena.
John Wiley & Sons.
12. Mansouri A., Kostiuk L.W. and Bhattacharjee S., (2007), J. Phys. Chem. B, 111, 12834.
13. Kirby, B. J., & Hasselbrink, E. F. (2004). Electrophoresis, 25(2), 187-202.
14. Elimelech M., Chen W. H., and Waypa J. J. Desalination, 95:269, 1994.
15. Van der Heyden F. H. J., Stein D. and Dekker C., (2005), Phys. Rev. Lett., 95, 116104.
16. Gillespie D.(2012), Nano Lett., 12, 1410.

17. Daiguji H., Yang P., Szeri A. J. and Majumdar A., Nano Lett.,(2004), 12, 2315.
18. Martins, D. C., V. Chu, D. M. F. Prazeres, and J. P. Conde, Microfluidics and nanofluidics 15,
no. 3 (2013): 361-376.
19. Y. Ren and D. Stein, Nanotechnology, 2008, 19, 195707.
20. Y. Xie, J.D. Sherwwod, L. Shui,A. v. d. Berg and J. C. T. Eijkel, Lab Chip, 2011, 11, 4006.
21. F. H. J. Heyden, D. J. Bonthuis, D. Stein, C. Meyer and C. Dekker, Nano Lett., 2006, 6(10),
2232
22. Mansouri, A., Scheuerman, C., Bhattacharjee, S., Kwok, D. Y., & Kostiuk, L. W. (2005).
ASME 3rd International Conference on Microchannels and Minichannels (pp. 541-549).