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Handbook of Nanoelectrochemistry

DOI 10.1007/978-3-319-15207-3_7-1
# Springer International Publishing Switzerland 2015

Electrophoretic Deposition (EPD): Fundamentals and Applications from


Nano- to Micro-Scale Structures
Pouya Amrollahia, Jerzy S. Krasinskib, Ranji Vaidyanathana, Lobat Tayebia,c* and Daryoosh Vashaeeb,d*
a
Helmerich Advanced Technology Research Center, School of Material Science and Engineering, Oklahoma State University,
Tulsa, OK, USA
b
Helmerich Advanced Technology Research Center, School of Electrical and Computer Engineering, Oklahoma State
University, Tulsa, OK, USA
c
Department of Developmental Sciences, Marquette University School of Dentistry, Milwaukee, WI, USA
d
Electrical and Computer Engineering Department, North Carolina State University, Raleigh, NC, USA

Abstract
EPD is a technique where charged particles in a stable colloidal suspension are moved through the liquid
due to electric eld and deposited on an oppositely charged conductive substrate, forming the intended
material or device. EPD enables fabrication of a wide range of structures from traditional to advanced
materials, from nanometric thin lms to a fraction of 1 mm thick lms, and from porous scaffolds to
highly compact coatings. These structures include different compositions with complex shapes and
structures which can be formed in a relatively short experimentation time by simple apparatus. This
review presents the fundamentals, mechanisms, and characteristics of EPD along with its past and recent
applications.

Keywords
Electrophoretic deposition (EPD); Ceramic materials; Biomedical materials; Thermoelectric materials;
Materials fabrication

Introduction
Electrophoretic deposition (EPD) is a material processing technique using deposition of charged particles
in a stable colloidal suspension on a conductive substrate, acting as one of the two oppositely charged
electrodes in the EPD cell. The deposited particles form the intended material or device [1]. Both
alternating current (AC) and direct current (DC) electrical elds have been applied in EPD process,
although DC elds are more common [13]. Highly versatile application, simple apparatus and equipment, short processing time, cost effectiveness, facile modication, desirable dense packing of particles in
the nal piece, high quality of the microstructures produced, easy production of geometrically complicated shapes and simple control of the thickness and morphology have made EPD an interesting technique
both in academia and industry [1, 4]. In EPD, the state of particles in suspension and their evolution during
the process can be controlled and manipulated. Moreover, appropriate and accurate choice of processing
variables could enable production of dense and homogeneous or porous microstructures. A combustible
substrate that can be removed by further heating in sintering process is used for fabricating complicated
*Email: lobat.tayebi@marquette.edu
*Email: dvashae@ncsu.edu
Page 1 of 27

Handbook of Nanoelectrochemistry
DOI 10.1007/978-3-319-15207-3_7-1
# Springer International Publishing Switzerland 2015

Fig. 1 Four steps of EPD; (a) dispersion, (b) electrochemical charging, (c) electrophoresis and (d) deposition

shapes. But for coatings, the operator needs to be very cautious about possible cracks due to drying and
sintering. These thermally derived cracks are the impartible nature of the technique and the quality of the
nal surface depends on overcoming this problem.
This process was discovered by Bose in a liquid-siphon experiment during the 1740s [5] and has been
known since Ruess observed the movement of clay particles in water under an electrical eld [6]. The rst
practical use of this technique was done by Harsanyi [7] in 1927 in order to deposit thoria (thorium
(IV) oxide) and tungsten on a platinum cathode as an emitter for electron tube applications. The rst largescale application of EPD dates back to early 1950s, when the scientists used this method to make
insulating Al2O3 layers on cathode heaters in vacuum tubes [8].
An EPD cell contains four different parts: working electrodes (substrate and counter electrode),
colloidal suspension, and power supply (AC or DC).
Despite the fact that many mechanisms have been proposed for EPD, there are several unquestionable
characteristics to distinguish EPD from other similar deposition-based techniques. As it can be seen in
Fig. 1, (a) colloidal particles are well dispersed and able to move freely and independently in solvent
suspension, (b) electrochemical equilibrium of the solvent is responsible for particles surface charge,
(c) particles move electrophoretically in the bulk of the suspension to the oppositely charged electrode
(substrate), and (d) the substrate is covered by a neutralized, rmly deposited layer of particles. Therefore,
EPD is a technique where moving species are solid particles, required conductance of the liquid medium is
low, and the organic liquids are preferred. In EPD, the liquid stays motionless while particles and ions
move under the electrostatic force [4].
Like in any other system, it is absolutely essential to avoid contamination or impurity that can
unfavorably inuence the properties of the process and/or resulting materials. As the characteristics of
the resulting materials are highly dependent on stability of suspension and control on surface charge,

Page 2 of 27

Handbook of Nanoelectrochemistry
DOI 10.1007/978-3-319-15207-3_7-1
# Springer International Publishing Switzerland 2015

Fig. 2 Suppression of bubbles by applying constant current pulses (a-alumina deposited on stainless steel substrates)
(Reprinted from Besra et al. [11], Copyright (2009), with permission from Elsevier)

powder washing multiple times before preparation of a particulate suspension is mandatory in order to
eliminate the residual impurities caused by the powder preparation procedure [9].
Generally, it is preferred to use organic liquids as the suspending medium in an EPD cell even though
they are dangerous, expensive, and unfriendly to the environment. However, in aqueous EPD, one needs
much lower voltage, we have more control on temperature, and deposition takes place faster. Also, water
is much more environmental friendly. Unfortunately, electrolysis of water generates gas bubbles that
drastically compromise the quality of the deposited layer. It has been reported that application of short
voltage pulses in an aqueous EPD system can suppress the bubble incorporation [10, 11]. Figure 2
demonstrates complete suppression of bubbles during aqueous electrophoresis of a-alumina thin lm,
deposited on stainless steel (316 L) substrate by applying periodically pulsed voltage. As can be seen,
bubble-free deposits were obtained at pulses equal to or shorter than 5 m. It has also been reported that
constant current rather than constant voltage depositions are more efcient and can provide better control
over the EPD process.
Table 1 lists selected signicant applications of EPD in various elds.
EPD process involves four steps. First, a stable suspension of particles is needed. Since the particles
only need to be stable within the time frame between dispersing to depositing processes, which can be as
short as a few minutes, various stabilization techniques may be utilized such as low concentration, proper
charging of the particles, polymer depletion, polyelectrolyte, block copolymer, and homopolymer
adsorption [72]. In electrostatic technique, creation of an energy barrier between 10 and 15 kT prevents
the particles from attaching to each other. In polymer depletion, a concentration of soluble polymer which
cannot be adsorbed to the particle surfaces is used to prevent them from sticking together. Other polymeric
stabilization methods necessitate a polymer where one side of it can be attached to the particle, while the
other side is dissolved in the solvent [72]. As the second step, a solvent able to enable ionic charge is
required where adsorption/dissolution equilibria for a positive and negative ion are different. The next
step is electrophoretic migration of particles under the inuence of electric eld. During electrochemical
charging of particles, the solvent must be able to dissolve ions; because a solvent with no or a minute
concentration of dissolved ions drastically increase the required voltage across the cell. Electrochemical
reactions at the electrodes guarantee the change in the valence of ions in order to prevent ions from
screening the electric eld at the electrode surface. Moreover, absence of these reactions would lead to fast
migration of ions to oppositely charged electrodes after applying a voltage. The last step is deposition of
particles on one of the electrodes. As there are various mechanisms for both stabilizing and destabilizing
of the particles (in the rst and fourth steps), there is no single mechanism for EPD.

Page 3 of 27

Handbook of Nanoelectrochemistry
DOI 10.1007/978-3-319-15207-3_7-1
# Springer International Publishing Switzerland 2015

Table 1 Applications of EPD


No.
1

Category
Oriented ceramic materials

Multilayered composites

3
4
5

Thermoelectric thick lms


Particle size separation
Deposition of nanotubes

6
7
8

Solar cells
Reinforced composites
Thick lm optical modulators

Batteries and electrochemical


capacitors

10

Solid oxide fuel cells

11
12

Corrosion-resistant coatings
Catalyst support and molecular
sieves
Sensors
Piezoelectric materials
Biomedical materials

13
14
15

Application
Fabricating crystalline oriented thick lms
Textured TiO2
Textured alumina
Multi-layered alumina
Fabricating functionally gradient, multi-layer composites and
sandwich structures
Si-Ge thick-lms
SnO2 particles
Graphene synthesis
SiO2/CNT composites
CNT/TiO2 composites
MnO2/CNT composites
Fe3O4/CNT composites
Hydroxyapatite/CNT composites
Bioactive glass/CNT composites
Dye sensitized solar cells
SiC ber reinforced composites
WO3 nano rods
ZnO thin lms
Lithium ion batteries
Super-capacitors
Y2O3-stabilized ZrO2
Perovskite structures
CeO2 lms
Gd2O3
Silica hybrid coatings
PPy coated tubes

References
[6, 12, 13]
[1416]
[17, 18]
[19]
[2022]
[23]
[24]
[2527]
[28]
[29, 30]
[31]
[32]
[3335]
[36, 37]
[38, 39]
[40]
[41]
[42]
[43]
[44]
[4548]
[49]
[50]
[51]
[52]
[53]

Gas sensors
PZT actuators
Forming biocompatible layers
Porous scaffolds
Bacteria
Corrosion protection of implants

[5457]
[58, 59]
[6069]
[35]
[70]
[71]

Mechanisms of EPD
There are several mechanisms by which the particles come together and form a rigid solid structure.
Combining them with the abovementioned dispersing techniques leads to different EPD mechanisms
although the exact mechanisms which allow deposition of particles on the substrate are still not
completely understood.
It has been suggested that EPD should be considered as a two-step process, where particles rst migrate
to the substrate due to the applied electric eld (the particles lose their charge at the electrode surface) and
then after complex electrochemical reactions and aggregation the deposited layer is formed.

Page 4 of 27

Handbook of Nanoelectrochemistry
DOI 10.1007/978-3-319-15207-3_7-1
# Springer International Publishing Switzerland 2015

Table 2 Different mechanisms of EPD [72]


(a) Particle stabilization at substrate
Low number density
Electrostatic
Polymer depletion
Homo-polymer adsorption
Poly-electrolyte
Block co-polymer

(b) EPD layer formation mechanisms


Densication
Direct electrostatic force
Electro-sedimentary
Ion depletion enhanced electrostatic
Desorption of neutral/charged polymer
Charge reduction/neutralization
Squeezing out
Bridging occulation

Electrophoretic motion of the particles is stopped by the substrate and the density of the particles will
keep increasing there, due to accumulation. If those particles agglomerate, a low-density deposit may
form which is difcult to dry without cracking. In this mechanism, there is no guarantee that the thickness
of the layer remains uniform all over the substrate; since the nonuniformity of the electric eld can lead to
a very nonuniform deposit.
If the applied electric eld is powerful enough (around several hundred volts per cm), it is also possible
that deposition takes place via suppressing the electrostatic repulsion with the electric eld. In this
mechanism, the electrical force gradient has to be low in order to make an even deposit [73, 74], although
some irregularities may occur due to strong electroconvection.
The next approach is occulation of the particles by electrosedimentation [72]. It was found that a
stable suspension can produce strongly adhering sediment. Sediment is formed in the innermost layer of
the particles due to gravitation plus the pressure made by electrically induced ow of particles to the
substrate. Although the density of the deposited layer is very good, the charge of the layer confronts the
electrochemical charge of the solvent and acts as the driving force reducing the electrophoretic force in the
layer. This instability can cause convection within the layer of particles before they are deposited on the
substrate [75, 76].
Decrease in total ionic concentration around the substrate can raise the voltage gradient and, by quelling
the convection, conduction occurs between unbalanced ions as a consequence. This effect results in
raising the voltage gradient to mega volts per meter. These layers are very convectively unstable.
Preservation of the surface charge of the particles results in a very strong compacting force that can
make a powerful leveling effect when it is accompanied by high voltage gradient. This mechanism leads
to forming very even thin layer [77].
On the contrary, it has also been reported that an increase in ionic concentration at the substrate makes
the electrostatic boundary layer of particles thinner and thinner until they become unstable and the deposit
is formed [78].
The particles may lose their charge and neutralize after contacting the substrate and make a thin deposit.
This mechanism continues until the deposited layer gets thick, the particlesubstrate interactions are
stopped, or the pH level changes around the substrate [72].
It has been reported that repulsive forces between the particles can be reduced only when the electrode
reactions generate (OH) ions [4]. The calculated amount of ionic strength around the substrate was
sufcient for occulation of the suspension. Interparticle repulsion decreases when near-substrate electrolyte concentration is increased. Consequently, the zeta potential is lowered and occulation of particles
is induced.
In the case of polymers, it has been reported that when electrophoretic force brings the particles
together, branches of a copolymer can be detached from one particle and attach to a neighbor particle and
make a polymer bridge that holds these particles together [72]. Another deposition mechanism for
Page 5 of 27

Handbook of Nanoelectrochemistry
DOI 10.1007/978-3-319-15207-3_7-1
# Springer International Publishing Switzerland 2015

Table 3 Parameters governing EPD


Suspension parameters
Particle size
Dielectric constant, conductivity and viscosity
Zeta potential
Stability
Concentration of solids

Process parameters
Applied electric eld
Deposition time
Conductivity of the substrate

polymers is called squeezing out, where a constant stable electrophoretic force brings two polymers into
contact and deposit. Furthermore, in some cases, changing the solvent ionic composition leads to an
alteration in particle surface potential and polymer particles can be stabilized [72]. Table 2 summarizes the
mechanisms through which (a) particles stabilize at the substrate and (b) EPD takes place.

Process Variables
There are two sets of parameters which can affect both EPD process and the resulting specimen: rst,
parameters that control the status and quality of suspension, and then the parameters which qualify the
whole process, such as electrical parameters. When the rst group is xed, the latter can be manipulated
for gaining favorable deposition. Table 3 summarizes the possible parameters that can be manipulated in
order to get the desired properties and quality in the deposited lm.

Suspension Parameters
Particle Size
Uniformity of the deposited layer is tightly tied to whether or not the particles remain stable and dispersed
throughout the whole process, because, motionless and accumulated particles lead to the formation of
gradient in deposition. In case of larger particles, there is always a competition between the gravity and
electrophoresis forces. The rst one result in sedimentation of the powder while the latter deposits the
particles on the substrate. In this situation, when EPD is completed, surface charge is highly increased
and/or the electrical double layer region is thickened.
Dielectric Constant, Conductivity, and Viscosity of Suspension
It has been reported that the dielectric constant of the liquids must be in the range of 1225 for deposition
to happen [1]. In liquids with dielectric constants less than 12, lack of dissociative power stalls the
deposition, while in liquids with dielectric constants higher than 25, electrophoresis is halted by the
reduction in size of the double layer region, caused by high ionic concentration.
Impurities can also change the conductivity of the suspension. Moreover, the method used for
preparing the suspension also affects the conductivity drastically. A highly resistive suspension leads to
instability because electronically originated charge forms in the particles. On the other hand, proper
adjustment of temperature and dispersant concentration can raise the conductivity. Research has shown
that, for each exact dispersant concentration and each temperature, there is a narrow conductivity range
which enhances the deposition process [79]. Generally, an ideal suspension has high dielectric constant,
low conductivity and low viscosity. Table 4 shows viscosity and relative dielectric constant of some
popular solvents [80], ordered from best to worst. Methanol and acetone are the rst two best solvents.
However, comparing these two, methanol has higher dielectric constant while acetone has a viscosity of

Page 6 of 27

Handbook of Nanoelectrochemistry
DOI 10.1007/978-3-319-15207-3_7-1
# Springer International Publishing Switzerland 2015

Table 4 Physical properties of solvents


Solvents
Acetone
Methanol
Water
Ethanol
Acetylacetone
n-Propanol
Iso-propanol
n-Butanol
Ethylene glycol

Viscosity cP 103 N:s:m2


0.3087
0.557
0.890
1.0885
1.09
1.9365
2.0439
2.5875
16.265

Relative dielectric constant


20.7
32.63
78.2
24.55
25.7
20.33
19.92
17.51
37.7

almost half of methanol. Therefore, acetone can be considered as the best solvent for making an ideal
suspension.
Zeta Potential
Zeta potential governs several key parameters in EPD, such as the density of the deposit, particle direction
and speed, and the repulsive interactions between the particles which determine the stability of the
suspension. Generally, a high surface charge is needed not only to avoid particle agglomeration but
also to enable formation of a dense highly packed deposit. Zeta potential manipulation is done through
addition of acids, bases, and adsorbed ions.
Stability of Suspension
Finding the best state of stability of the suspension is a matter of compromise. When the suspension is
stable, occulation does not happen and a thick adherent material deposits at the bottom of the cell due to
sedimentation. Too much stability disables EPD, because a high electric eld is needed to defeat the
repulsive forces between particles. Conversely, a occulating suspension just forms thin nonadhering
deposits.
Concentration of Solids in Suspension
High concentrations of solids in suspension enable uniform and even deposition rates, while low
concentrations lead to deposition rates proportional to electrophoretic mobility of each particle [81].

Process Parameters
Effect of Applied Electric Field
As there are both intended particles and free ions in the suspension, a portion of the electric eld, which is
the driving force of EPD, is carried by the free ions and the eld efciency is compromised. However,
when we cannot limit the presence of free ions, the amount of current carried by them is insignicant.
Ideally, the applied electric eld must be totally spent on advancement of the electrophoresis in a stablecurrent manner, because the deposition increases in direct relation with raising the applied potential.
While too low elds are not capable of triggering the electrophoresis, with too high applied electrical
elds, the quality of the deposits is sacriced. It has been suggested that the best quality of deposits are
gained at moderate applied elds. Moreover, a high electric eld can cause turbulence in the suspension,
which compromises the quality of the resulting deposit. Also, it increases the speed of the particles and
consequently they cannot have the chance to be seated in the best position, which makes the formation of a
dense close-packed structure impossible [82].
Page 7 of 27

Handbook of Nanoelectrochemistry
DOI 10.1007/978-3-319-15207-3_7-1
# Springer International Publishing Switzerland 2015

Effect of Deposition Time


In EPD, the deposition rate starts with a linear relationship to time and then it lowers as time goes on, until
the deposit is thick enough to interrupt the conductance and the deposition rate reaches plateau at high
deposition times.
Conductivity of Substrate
In EPD, the quality of the deposited lm is strongly dependent on the conductivity of the substrate. Low
conductivity of the substrate leads to both slow deposition and nonuniformity of the deposit [47].

Applications
Oriented Ceramic Materials
EPD has been given special attention as the leading ceramic electrodeposition technique in the last
decades [13, 83]. This technique has revolutionized advanced ceramic materials processing both in
academia and industry. In ceramic industries, thin ceramic lms can be achieved from colloidal suspensions. In recent years, the attractive characteristics of EPD have made it a potential alternative approach
for many purposes in several elds. For example, EPD has been reported as a promising technique for
fabricating crystalline oriented thick lms [6, 12, 13, 16]. Titanium oxide, which has three crystallographic polymorphs (anatase, rutile, and brookite), has been widely used in different areas due to its
remarkable optical characteristics. In another study [14], it has been shown that EPD in a strong magnetic
eld enables taking advantage of magnetic anisotropy of materials with asymmetric crystalline structures
to produce layers of aligned crystalline magnetic particles. The crystal anisotropy produces the driving
force (DF) of this magnetic alignment and it is described by Eq. 1 [15],
DF DxVB2 =2m0

(1)

where Dx is the difference between susceptibilities parallel and perpendicular to the magnetic principal
axis, V is the volume of the material, B is the applied magnetic eld, and m0 is the permeability in a
vacuum. Figure 3 depicts a schematic view of the EPD cell in this investigation.
TiO2 powder was sonicated in distilled water at pH 5.5, and then polyethylenimine (PEI) was added to
improve stability of the suspension. PEI modied the zeta potential of the powder. The EPD was done in
presence of magnetic eld at current density of 2.7 mA/cm2. As a result, the magnetic eld xes the

Fig. 3 Schematic view of EPD under high magnetic eld; (a) suspension, (b) magnetic orientation and (c) preferred deposition
(Reprinted from Uchikoshi et al. [16], Copyright (2004), with permission from Elsevier)
Page 8 of 27

Handbook of Nanoelectrochemistry
DOI 10.1007/978-3-319-15207-3_7-1
# Springer International Publishing Switzerland 2015

Fig. 4 XRD pattern of the top and side planes of deposited anatase (Reprinted from Uchikoshi et al. [14], Copyright (2006),
with permission from Elsevier)

Fig. 5 SEM image of cross-section of diamond/diamond laminates (Reprinted from Dzepina et al. [22], Copyright (2013),
with permission from Elsevier)

orientation of each particle and the crystalline structure of polycrystalline TiO2 can be controlled
[14]. Figure 4 shows the XRD pattern of the top and side planes of the deposited anatase.
a-alumina is an interesting engineering material [17]. Possibility of fabrication of textured alumina by
EPD was also investigated [18]. High purity ne a-alumina and hexagonal alumina platelets as matrix
powder and template were used. The matrix powder was milled for 24 h in ethanol and 0.5 vol%
de-ionized water. Platelets were then added to the suspension with n-butylamine and Dolapix Ce-64
(Dolapix is an anionic polyelectrolyte dispersant that contains ammonium salt of polymethacrylic acid
[84]) in order to negatively charge and disperse the particles. The pH of the suspension was at 11.5 for the
whole 450-s duration of the procedure. As a result, (001) alumina texture was obtained.

Multilayered Composites
Another group reported enhanced mechanical properties in textured, multilayered alumina produced via
EPD [19]. It has also been reported that EPD is capable of fabricating functionally gradient and multilayer
composites and sandwich structures [2022]. Functionally graded materials are advanced composite
Page 9 of 27

Handbook of Nanoelectrochemistry
DOI 10.1007/978-3-319-15207-3_7-1
# Springer International Publishing Switzerland 2015

b
160 m

substrate

Si0.8Ge0.2 film

200 m

Si80Ge20
Thick Film

Silicon Substrate

Fig. 6 (a) SEM image and (b) photograph of Si80Ge20 EPD coating sintered on silicon substrate (Reprinted from
Nozariasbmarz et al. [23], Copyright (2013), with permission from Elsevier)

materials which consist of different layers with different mechanical properties and are able to alleviate
problems associated with interfaces of different materials [85, 86]. Polycrystalline diamond has wide
applications in for cutting and grinding in machining, mining and oil industries. Researchers have been
successful in electrophoresis of diamond powder which was rst acid washed and then boiled and rinsed
in HCl solution and distilled water. Figure 5 shows a SEM image of diamond/diamond laminates formed
by electrophoretic deposition of diamond powders with different concentrations in HCl solution. Directcurrent EPD on tungsten carbide substrates was conducted at a constant voltage of 1.5 for 7.5 min for each
layer [22]. Due to the high accuracy of EPD [1], sandwich-structured materials can be fabricated after
several steps in both single-bath and multi-baths experiments [22].

Thermoelectric Thick Films


Recently our research group has been successful in improving the thermoelectric power factor of SiGe
thick lms through electrophoresis of elemental Si and Ge powders [23]. For a highly efcient thermoelectric device, the resistance of the ohmic contact must be much smaller than the resistance of the
thermoelectric element. Therefore, the length of the device must be bigger than the ratio of the specic
ohmic contact resistance to the resistivity of the thermoelectric material. Computational simulation
studies show that a thickness of more than a few tens of micrometers is needed to satisfy this criterion
[87]. The small heights of the thermoelectric legs introduce complexity for making simultaneous
electrical contacts to the entire thermoelectric array. Even a small height variation in one leg can lead to
open circuit failure of the whole module. EPD has shown great capabilities in making lms with
thicknesses from submicron to hundreds of micron, while maintaining the composition of the starting
materials with stoichiometric ratios. In that project, our group prepared Si80Ge20 powder via milling and
then sonicated the resulting material in acetone for 2 h in order to avoid any agglomeration and achieve a
homogeneously dispersed colloidal solution. Silicon wafer was used as the substrate and it was etched in
buffered oxide etch solution for 2 min, and then washed with deionized water to remove the native SiO2.
The process was carried out in a custom-made cell under a constant voltage of 30 V at room temperature.
After that, the sample was dried at room temperature and then cold pressed under 30 MPa pressure.
Afterward, the coated substrate was sintered for 3 h at 1200  C in nitrogen atmosphere. Figure 6 shows a
SEM image and a photograph of Si80Ge20 layered on silicon substrate. Formation of dense and uniform
layers of Si80Ge20 can be seen in Fig. 6a, while Fig. 6b shows the overall uniformity of the thick lms.
Seebeck coefcient and electrical conductivity measurements from the room temperature to 950  C
showed that the thermoelectric power factor of Si80Ge20 thick lm is approximately
1:9  103 W:m1 :K2 , which is an order of magnitude larger than the previously achieved values for
thin lms of this material.

Page 10 of 27

Handbook of Nanoelectrochemistry
DOI 10.1007/978-3-319-15207-3_7-1
# Springer International Publishing Switzerland 2015

Fig. 7 Deposition of (a) particles on CNTs, (b) CNTs on particles, and (c) co-deposition of CNTs and particles (Reprinted
from Boccaccini et al. [25], Copyright (2010), with permission from Elsevier)

Particle Size Separation


Particle size separation is another capacity of EPD [24]. In one investigation, two parallel nonconductive
electrodes were attached to borosilicate glass by gold paste. SnO2 particles were dispersed in pure acetone
and alternating-current EPD was done at 40 V for 10 min. It has been shown that increasing the frequency
of the AC eld leads to narrowing of the size distribution curve [24].

Deposition of Nanotubes
EPD has been used to improve carbon nanotubes (CNTs), to make CNT-composites, and for graphene
synthesis [2527]. Various composites including SiO2/CNT [28], CNT/TiO2 [29, 30], MnO2/CNT [31],
Fe3O4/CNT [32], hydroxyapatite/CNT [3335], and bioactive glass/CNT composites [36, 37] have been
made using homogeneous dispersion of CNTs in an appropriate solvent. Fibers coated with single-walled
CNTs, which can be used for extracting phenols from aqueous solutions, have also been prepared by
electrophoresis of a suspension of CNTs in dimethylformamide at a constant voltage of 40 V for 10 s [88].
Figure 7 shows different outcomes of EPD made CNT/ceramic nanocomposites. Depending on the
conditions sometimes ceramic or metallic particles are deposited on CNTs, in other cases CNTs are
coagulated onto particles, and it is also possible to achieve simultaneous deposition of CNTs and particles.

Dye Sensitized Solar Cells


Efcient dye sensitized solar cells (DSSCs) can be made through multiple EPDs [38, 39]. DSSCs are
photovoltaic devices with high conversion efciency [89] and their properties were modied after EPD at
constant voltage of 10 V for 20 15-s cycles at 25  C and further annealing (Fig. 8a). Figure 8b shows the
enhanced efciency of these cells by increasing the number of the layers.

SiC Fiber Reinforced Composites


SiC-ber-reinforced composites have a great potential to be used for fusion reactors due to their
remarkable resistance against neutron ux [90, 91]. EPD production of these composites [40] led to the
idea that the quality and density obtained in this procedure is highly correlated with the zeta potential of
the charged particles. The experiment was conducted at constant voltage of 60 V for 5 min under DC

Page 11 of 27

Handbook of Nanoelectrochemistry
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# Springer International Publishing Switzerland 2015

Fig. 8 (a) SEM image of cross-section of fabricated DSSC after annealing at 500  C, (b) the effect of number of layers on
thickness (T) and efciency (E) of EPD fabricated DSSCs (Reprinted from Hamadanian et al. [39], Copyright (2013), with
permission from Elsevier)

electrical eld. It has also been demonstrated that addition of both cationic deocculant and Dolapix
(a common deocculant and dispersant in ceramic industry) and adjusting the pH around 9 improved the
resulting properties.

Thick Film Optical Modulators


WO3 is used for optical modulation due to its electrochromic color [92]. Although hydrothermal process
is the most popular technique for the synthesis of tungsten oxide [93], it needs several additional steps to
complete the procedure; EPD has the signicant advantage of having control over the whole process via
manipulating pH level, process duration, and electrical power [41]. In the experiment, nanorods of WO3
were dispersed in deionized water with a pH level of around 6.77. Indium tin oxide glass (ITO-glass is a
transparent conductive solid solution of In2O3 and SnO2) was used as the working electrode with positive
charge, and the process was done at a constant current of 0.8 mA/cm2. Successful EPD of transparent ZnO
thin lms has also been reported recently [42].

Batteries and Electrochemical Capacitors

The ability of producing thick lms by EPD has made it interesting for application in lithium batteries [43]
which currently are the most favorable portable energy source in electronic devices [94]. High power and
long life cycle of electrochemical capacitors, which operate via taking advantage of the double layer
formed at the interface of electrode and electrolyte [95], have made them a promising choice for energy
storage applications [96, 97]. The supercapacitor performance was signicantly improved through EPD
of hydrous ruthenium oxide particles with polytetrauoroethylene (PTFE is a highly hydrophobic
synthetic polymer) [44]. A schematic sketch of electrophoresis of these to particles can be seen in
Fig. 9a; while Fig. 9b shows the increase in specic capacitance of electrodes coated with these materials
as a function of loading weight for hydrous ruthenium oxide electrodes.
Manganese oxide coatings for supercapacitor applications were also produced by electrophoresis
[98]. The experiment was carried out under DC electrical eld at a constant voltage of 100 V for
20 min. Manganese oxide particles were dispersed in ethanol suspension by sonication and graphite
electrodes were utilized.

Solid Oxide Fuel Cells (SOFCs)


Solid oxide fuel cells (SOFCs) have played a crucial leading role in power generation. Many scientists
believe that SOFCs can revolutionize the future of science and technology due to the cells clean operation
and efciency. As it can be understood from the name, the difference between a SOFC and a conventional
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Fig. 9 (a) EPD by adding PTFE, (b) specic capacitance versus loading weight (Reprinted from Jang et al. [44], Copyright
(2006), with permission from Elsevier)

fuel cell is that the rst one uses a solid ion conductive ceramic as the electrolyte, while the latter works
with liquid electrolytes [99]. The electronic conductivity of the dense electrolyte of a SOFC at the working
temperature of approximately 6001000  C should be low [100]. Generally, in SOFCs, the cathode is
exposed to open air or oxygen and oxygen is reduced to an oxygen anion. Then the oxygen anions travel
through the electrolyte to the anode where hydrogen molecules or hydrocarbons are oxidized at the
operating temperatures [101]. Lanthanum strontium gallium magnesium oxides (LSGMs), Lanthanum
strontium cobalt ferrites (LSCFs), yttria stabilized zirconia (YSZ), and ceria gadolinium oxides (CGOs)
which have remarkable long-term stability and strong mechanical properties are the most popular
materials for electrolyte, while lanthanum strontium manganite (LSM), Ni foil, Ni/ZrO2 cermet, and
Ni/YSZ substrates are used as cathodes and anodes [102, 103]. There are several challenges in fabrication
of SOFCs such as their high operating temperatures and high layer thickness [104]. There are two possible
approaches to solve these issues. First, as the operating temperature is completely dependent on the nature
of the electrolyte material, there is always a possibility to nd better materials with higher ion conductivity
at lowered temperatures (500800  C) [105]. Second, it is known that reducing the thickness of the lm
can also lower the operating temperatures [106]. EPD has been widely exploited to fabricate SOFCs in the
last two decades [45, 46, 4951]. EPD is able to fabricate complex shapes, prepare both dense and porous
lms, and allows codeposition of different source materials. Figure 10 shows the SEM images of the
surface and the cross section of a positive electrolyte negative cell [48].
Preparation of YSZ on LSM and LSM/YSZ substrates through EPD was carried out by a constantvoltage method [107]. Another research group successfully produced well-distributed LSGM lms with

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Fig. 10 SEM image of the sintered EPD lms of positive-electrolyte-negative (NiOYSZ/YSZ/LSCF) in a SOFC; (a) crosssection and (b) surface (Reprinted from Jia et al. [48], Copyright (2006), with permission from Elsevier)

good adhesion to platinum substrate from a suspension in a mixture of acetone and ethanol [108]. The
right selection of solvent, dispersant, and binder is of great importance in electrophoresis of ceramic
laminates to be used in SOFCs. In one experiment, they found the best properties using ternary selection
of ethyl alcohol, phosphate ester, and polyvinyl butyral as solvent, dispersant, and binder,
respectively [109].

Corrosion-Resistant Coatings

EPD is one of the most promising techniques for fabricating thick lms, which may be applied to increase
the corrosion resistance of metals. Corrosion-resistant coatings have been used for protecting different
substrates that suffer from weak corrosion resistance [110112]. Silica hybrid coatings have provided
both excellent mechanical and corrosion resistance properties, they have drawn much attention in the last
decade and EPD was commonly used to make corrosion protective coatings [52, 113115]. One study
compared corrosion behavior of silica hybrid coatings made by dipping with these made by EPD
[52]. Stainless steel and graphite electrodes were used as the substrate and counter electrode, respectively.
Temperature was maintained at 5  C during the whole procedure. EPD coatings were thicker than dipped
coatings and had more enhanced corrosion resistance.

Catalyst Support and Molecular Sieves


Porous ceramics are used as catalyst supports and molecular sieves due to their corrosion resistance and
high temperature stability. In order to broaden and modify the range of their application, coatings are
applied all over the outer and inner surface of these ceramics. Pore size and surface functionality must be
controlled too in order to improve their properties. EPD makes possible embedding strong and uniform
coatings on complex-shaped materials [116, 117], such as coating the inner surface of porous foams and
tubes. Near-200 mm layer of alumina particles was deposited onto the inner surface of porous alumina tube
via electrophoresis at a constant voltage of 100 V under DC electrical eld, using polypyrrole-coated glass
and stainless steel as the substrate and the counter electrode, respectively [53]. Figure 11 shows SEM
images of the inner wall of the noncoated and Ppy-coated tubes.

Sensors
Gas sensors, with high sensitivity, capability of real-time detection, and economic efciency, are widely
used in industry [118]. EPD has greatly contributed in generating both new original and modied

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Fig. 11 (a) Porous alumina tubes, and SEM images of the inner wall of (b) Ppy-coated and (c) noncoated tubes (Reprinted
from Kreethawate et al. [53], Copyright (2010), with permission from Elsevier)

Anodic oxide

A1

AAO/A1

Porous layer
Barrier
layer

EPD

Ag
paste
Sensor fabrication
Gas sensing test

GZOAAO / A1

Fig. 12 Schematic sketch of fabricating gas sensor via EPD (Reprinted from Han et al. [57], Copyright (2010), with
permission from Elsevier)
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Fig. 13 Microstructure of piezoelectric functionally graded monomorph actuator; (a) plate, (b) cross-section, (c) PZT surface,
and (d) PZT1 surface (Reprinted from Chen et al. [58], Copyright (2004), with permission from Elsevier)

production routes for production of common gas sensor lms [54]. Figure 12 depicts a schematic sketch of
the process of fabricating a gas sensor with anodic aluminum oxide (AAO)/Al substrate and SEM image
of gas sensors fabricated with a current density of 90 mAcm2. It is noteworthy that an insulator support
has to be used between the gas sensing lm and the conductive substrate, in order to avoid of a short
circuiting between these two layers [55].
Al-Cr-Fe conductive substrate was electrophoretically coated by zinc oxide in construction of one of
the sensors [56]. Another sensor was constructed using aqueous electrophoretic deposition of aluminum
oxide on aluminum substrate [57].

Piezoelectric Actuators
Piezoelectric actuators (PAs) use voltage-induced size changes of ferroelectrics for highly accurate
mechanical actuators. A good PA provides high forces at low voltages. In addition, low sintering
temperature and high Curie temperature and high piezoelectric constant are very importatnt [119,
120]. PAs are utilized in a wide range of applications, from optical to aerospace industries
[121123]. PAs suffer from weak mechanical properties at both low and high temperatures and their
efciency is highly dependent on the continuity and uniformity of their structures. EPD has been proven
to successfully solve these shortcomings due to its intrinsic properties. Two versions of piezoelectric
actuators based on Pb-Zr-Ti-Bi-Fe-Ba-Cu-W oxides (PZT1 and PZT in Fig. 17) were tested in functionally graded structures with silver coated electrodes (Fig. 13) [58]. The results conrmed formation of a
piezoelectric actuator.
In another investigation, EPD was used to deposit piezoelectric layer on a graphite rod from a
suspension containing doped piezoelectric material (Fig. 14) [59]. The graphite rods were removed
from the spiral shape, resulting in complex shape PA actuators that would be very difcult to make
using traditional methods. The studies showed that EPD is a promising method in production of PAs.

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Fig. 14 Image of piezoelectric actuators made by deposition on graphite rods (Reprinted from Chen et al. [59], Copyright
(2008), with permission from Elsevier)

Biomedical Applications
EPD has many interesting characteristics for biomedical applications, such as simplicity, cost efciency,
high production rate, low processing temperature, full controllability, ability to form complex shapes and
structures, and low processing temperature [13].
Forming Biocompatible Layers
In general, metallic biomaterials which are widely used as prosthesis and implants have one important
shortcoming which is their bioinert nature [62]. Overcoming this problem, EPD can form bioactive
ceramic coatings [124]. Amongst all, electrophoresis of hydroxyapatite (HA) and bioactive glass
(BG) has been vastly investigated by scientists [6062, 125, 126].
HA (Ca10(PO4)6(OH)2) is a crystalline mineral that has very similar chemical composition to bone and
teeth tissue and as it has excellent biocompatibility, osteoconductivity, and bioactivity; it is widely used as
hip replacements and dental implants [6365, 127]. Processing HA via a powder route has many
difculties, for example, sintering must be done at relatively high temperatures, which may sacrice
the biocompatibility and decompose the favorable HA structure [66]. It was demonstrated that electrophoresis of thermal-sprayed HA powders in ethanol suspension at a pH of 5, using graphite and stainless
steel electrodes, leads to successful preparation of porous hydroxyapatite scaffold (Fig. 15a) [35]. In
comparison to salt leaching and microsphere burn out, which are the two popular routes for fabrication of
porous scaffolds, EPD has the advantages of needing no additives or binders and being a simpler process,
although the costs of preparing large components are higher. As HA has poor mechanical properties, its
applications are mostly in coating and composites with metallic substrates and matrices. Deposition of
submicron HA in the form of a thick coating by EPD has been reported (Fig. 15b) [128]. Ethanol
suspension and ultrasonic agitation was used in order to disperse the thermal-plasma-sprayed HA
particles. EPD process was carried out at pH value of 35 and under current density of
0.051.5 mA/cm2 for 90 s. Carbon rod and stainless steel cylinder were used as the substrate and the
counterelectrode, respectively. Recently, another group has studied the formation of HA nanocomposite
coatings in alcohols [129]. In their investigation, two 316 L stainless steel plates were used as electrodes
and the experiment was carried out at voltages of 20 and 60 V/cm for up to 10 min. The quality of
HA-chitosan nanocomposites were tested in alcoholic suspensions using methanol, ethanol, and
isopropanol. Results revealed that the adsorption of chitosan on HA nanoparticles showed its highest
and lowest levels, in isopropanol and methanol, respectively.

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Fig. 15 (a) Interconnectivity of porous HA scaffold fabricated (Reprinted from Ma et al. [35], Copyright (2003), with
permission from Elsevier), (b) dense, uniform and crack-free HA tube both prepared by EPD (Reprinted from Wang
et al. [128], Copyright (2002), with permission from Elsevier)

Fig. 16 Alginate/BG composite deposited on Ti wire (Reprinted from Zhitomirsky et al. [68], Copyright (2009), with
permission from Elsevier)

BG (FDA approved composition of a mixture of SiO2, CaO, Na2O, and P2O5) is a surface reactive glass
biomaterial with a very good biocompatibility [130]. The deciencies of both BG and some metallic
implants (which are low corrosion resistance and low biocompatibility [131],) were eliminated by coating
BG on the metallic implants. Figure 16 shows deposited BG composite on Ti wire. In one study, BG was
electrophoretically deposited on 316 L stainless steel substrate in a mixture of ethanol and triethanolamine
as the suspension at constant voltages of 30, 60, and 90 V/cm2. They have also reported that the layer acts
as a barrier layer in articial saliva [69]. In another study, EPD of BG/polymer composite coatings were
made at a constant voltage range of 1030 V and a pH level of 11 [68].
Moreover, EPD has helped to develop novel bioactive composites. For example, wollastonite (CaSiO3)
particles were deposited into porous alumina and porous ultrahigh molecular weight polyethylene in a
suspension of iodine and acetone at a constant voltage of 1000 V for 60 min. In the procedure,
accumulation of wollastonite particles occurred near the cathode surface [67].

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Fig. 17 Confocal laser scanning microscope image of electrophoretically deposited bacteria after 2400 s (Reprinted from
Neirinck et al. [70], Copyright (2009), with permission from Elsevier)

EPD of Bacteria
In addition, EPD of bacterial cells was carried out and the interesting results of the investigation have
opened new windows to electrophoresis of inorganic materials [70]. In that investigation, a mixture of
demineralized water and sucrose (C12H22O11) was used as. The experiment was done under AC eld at a
constant voltage of 100 Vand a frequency of 25 Hz for 10 min. Confocal laser scanning microscope image
(Fig. 17) demonstrated that both live Gram-positive and Gram-negative bacteria were successfully
deposited; however, the viability of the bacteria cells was compromised after the deposition.
Corrosion Protection of Implants
Magnesium alloys have an outstanding strength to weight ratio, suitable biodegradability and nontoxicity
which make them appropriate candidates for implants. The major drawback for these alloys is their low
corrosion resistance in the body. EPD has been shown to be useful in forming corrosion resistant coatings
on magnesium bio implants [71]. AZ91 Mg alloy bioimplants were coated by nanostructured akermanite
(Ca2MgSi2O7) to improve the corrosion resistance of these implants. Akermanite nano powders were
suspended and then ultrasonically dispersed in methanol and immediately deposited electrophoretically
on micro arc oxidized (MAOed) AZ91 Mg alloy substrates. EPD process was carried out at constant
voltage of 100 V for 3 min. The resulting samples were then immersed in simulated body uid (SBF) to

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500 m

Corrosion rate (mg/cm2/hr)

b 0.6

AZ91
MAO
Akermanite coat

0.5
0.4
0.3
0.2
0.1
0
0

100

200
300
400
500
Immersion time (hours)

600

700

Fig. 18 (a) Cross-section view of the SEM morphology of nal sample. (b) Corrosion rate of AZ91, MAO and akermanite
coated samples immersed in SBF (Reprinted from Razavi et al. [71], Copyright (2014), with permission from Elsevier)

study the corrosion rate. Figure 18a shows SEM morphology of AZ91 after MAO and coating with
akermanite; Fig. 18b demonstrates the comparative results of the immersion test for studying the
corrosion behavior of AZ91 before and after being assisted by MAO and coating. As can be seen, the
corrosion rate has been signicantly reduced after applying MAO and akermanite coating. It is noteworthy that the porous coating has been made intentionally in order to enhance biological xations of the
living tissue to the implant.

Conclusion
Electrophoretic deposition (EPD) is a versatile processing technique, with remarkable characteristics such
as cost effectiveness, simple equipment, offering relatively short processing time and easy modication.
EPD was proven to be useful for production of geometrically complicated shapes, and full controllability
of the thickness and morphology, and it has gained considerable attention in the last few decades. Deep
understanding of EPD mechanisms along with appropriate process variables can lead to efcient
fabrication of the intended piece. This technique is capable of fabricating both micro- and nano-structured
ceramics, which can be used in a wide range of applications such as biomedical, optical, and corrosion
protection. It has also found applications in production of carbon nano tubes, fuel cells, sensors, and
actuators. Although EPD has been studied for more than 50 years, there are still opportunities for novel
applications and material advancements based on EPD due to its exceptional characteristics.

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Acknowledgment
This study is partially based upon work supported by Air Force Ofce of Scientic Research (AFOSR)
High Temperature Materials program under grant no. FA9550-10-1-0010, Oklahoma Center for
Advancement of Science and Technology (grant no. AR131-054 8161 and grant no. AR131-049) and
the National Science Foundation (NSF) under grant no. 0933763.

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