Besra 2007

A review on fundamentals and applications
of electrophoretic deposition (EPD)

Laxmidhar Besra
a,
*
, Meilin Liu
b
a
Colloids and Materials Chemistry Group, Regional Research Laboratory (Council of Scientic and
Industrial Research), Bhubaneswar 751013, Orissa, India
b
School of Materials Science and Engineering, Georgia Institute of Technology,
771 Ferst Drive, Atlanta, GA 30332-0245, USA
Received 10 January 2006; accepted 5 July 2006
Abstract
This review encompasses the fundamental aspects of electrophoretic deposition technique, factors
inuencing the deposition process, kinetic aspects, types of EPD, the driving forces, preparation of
electrophoretic suspension, stability and control of suspension, mechanisms involved in EPD, mul-
ticomponent/composite deposition, drying of deposits obtained by EPD. Numerous applications
including coatings, nanoscale assembly, micropatterned thin lms, near shape ceramics and glasses,
solid oxide fuel cells, laminated or graded materials, hybrid materials, inltration in porous and
woven bre preforms for preparation of bre reinforced ceramic matrix composites, etc. have been
described. The use of mathematical modeling including kinetic equations for deposit formation and
volumetric particle concentration in the suspension, together with brief description of discrete ele-
ment modeling of EPD process is presented.
2006 Elsevier Ltd. All rights reserved.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2. Electrophoretic deposition definition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3. Factors influencing EPD. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
0079-6425/$ - see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.pmatsci.2006.07.001
*
Corresponding author. Tel.: +91 674 481 635; fax: +91 674 581 637.
E-mail address: ldbesra@rrlbhu.res.in (L. Besra).
Progress in Materials Science 52 (2007) 161
www.elsevier.com/locate/pmatsci
3.1. Parameters related to the suspension . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.1.1. Particle size. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.1.2. Dielectric constant of liquid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.1.3. Conductivity of suspension. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.1.4. Viscosity of suspension. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.1.5. Zeta potential . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.1.6. Stability of suspension . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.2. Parameters related to the process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.2.1. Effect of deposition time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.2.2. Applied voltage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.2.3. Concentration of solid in suspension . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.2.4. Conductivity of substrate. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
4. Kinetics of electrophoretic deposition. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
5. Role of polymer binders in EPD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
6. Importance of powder washing before EPD. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
7. Practical considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
8. Water-based EPD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
9. Non-aqueous EPD. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
10. Charge development on powder surface in suspension . . . . . . . . . . . . . . . . . . . . . . . . . . 19
10.1. Aqueous suspension. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
10.2. Non-aqueous suspension . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
11. Properties of suspension for EPD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
11.1. The electrical double layer and electrophoretic mobility. . . . . . . . . . . . . . . . . . . 21
11.2. DLVO theory and suspension stability. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
12. Mechanism of EPD process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
12.1. Flocculation by particle accumulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
12.2. Particle charge neutralization mechanism. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
12.3. Electrochemical particle coagulation mechanism. . . . . . . . . . . . . . . . . . . . . . . . 28
12.4. Electrical double layer (EDL) distortion and thinning mechanism . . . . . . . . . . . 29
13. Multi-component deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
14. Drying of deposits produced by EPD. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
15. Design of electrophoretic apparatus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
16. Deposition on non-conducting substrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
17. Application of EPD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
17.1. Assembly of nanoscale particles into nanostructures and micropatterned thin
films. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
17.2. Near shape manufacturing of complex-shaped glasses and ceramics . . . . . . . . . . 41
17.3. Solid oxide fuel cell (SOFC) fabrication. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
17.4. Laminated materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
17.5. Functionally graded materials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
17.6. Hybrid materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
17.7. Fibre reinforced ceramic matrix composites . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
18. Modeling of EPD process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
19. Concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
2 L. Besra, M. Liu / Progress in Materials Science 52 (2007) 161
1. Introduction
The electrophoretic deposition (EPD) technique with a wide range of novel applications
in the processing of advanced ceramic materials and coatings, has recently gained increas-
ing interest both in academia and industrial sector not only because of the high versatility
of its use with dierent materials and their combinations but also because of its cost-eec-
tiveness requiring simple apparatus. Electrophoretic deposition (EPD) has been known
since 1808 when the Russian scientist Ruess observed an electric eld induced movement
of clay particles in water. But the rst practical use of the techniques occurred in 1933
when the deposition of thoria particles on a platinum cathode as an emitter for electron
tube application was patented in USA. Although the basic phenomena involved in EPD
are well known and have been the subject of extensive theoretical and experimental
research, the EPD of ceramics was rst studied by Hamaker [1], and only in the 1980s
did the process receive attention in the eld of advanced ceramics. There is general agree-
ment in the scientic community that further R&D work needs to be done to develop a
full, quantitative understanding of the fundamental mechanisms of EPD to optimise the
working parameters for a broader use of EPD in materials processing. This paper presents
a review of electrophoretic deposition and its application in various elds of processing.
2. Electrophoretic deposition denition
Electrophoretic deposition (EPD) is one of the colloidal processes in ceramic produc-
tion and has advantages of short formation time, needs simple apparatus, little restriction
of the shape of substrate, no requirement for binder burnout as the green coating contains
few or no organics. Compared to other advanced shaping techniques, the EPD process is
very versatile since it can be modied easily for a specic application. For example, depo-
sition can be made on at, cylindrical or any other shaped substrate with only minor
change in electrode design and positioning. In particular, despite being a wet process,
EPD oers easy control of the thickness and morphology of a deposited lm through
simple adjustment of the deposition time and applied potential. In EPD, charged powder
particles, dispersed or suspended in a liquid medium are attracted and deposited onto a
conductive substrate of opposite charge on application of a DC electric eld. The term
electrodeposition is often used somewhat ambiguously to refer to either electroplating
or electrophoretic deposition, although it more usually refers to the former. Table 1
presents the distinction between the two processes [2].
The basic dierence between an electrophoretic deposition process (EPD) and an electro-
lytic deposition process (ELD) is that the former is based on the suspension of particles in a
solvent whereas the later is based on solution of salts, i.e., ionic species [3]. There can be two
types of electrophoretic deposition depending on which electrode the deposition occurs.
Whenthe particles are positivelycharged, the depositionhappens onthe cathode andthe pro-
cess is called cathodic electrophoretic deposition. The deposition of negatively charged par-
ticles onpositive electrode (anode) is termedas anodic electrophoretic deposition. By suitable
modication of the surface charge on the particles, any of the two mode of deposition is pos-
sible. Fig. 1 presents a schematic illustration of the two electrophoretic deposition process.
With regard to technological application the potential of electrophoretic deposition
(EPD) as a materials processing technique is being increasingly recognised by scientists
and technologists. In addition to its conventional applications in fabrication of wear
L. Besra, M. Liu / Progress in Materials Science 52 (2007) 161 3
resistant and anti-oxidant ceramic coatings, fabrication of functional lms for advanced
microelectronic devices and solid oxide fuel cells as well as in the development of novel
composites or bioactive coatings for medical implants, there has been increased interest
for its application in nanoscale assembly for advanced functional materials [4]. Electropho-
retic deposition also oers important advantages in the deposition of complex compounds
and ceramic laminates. The degree of stoichiometry in the electrophoretic deposit is con-
trolled by the degree of stoichiometry in the powder used. According to Sarkar and Nich-
olson [5], particle/electrode reactions are not involved in EPD, and ceramic particles do not
lose their charge on being deposited which can be shown from the observation that reversal
of the electric eld will strip of the deposited layer [6]. Therefore, it is important to use sim-
ilarly charged particles and similar solventbinderdispersant systems for gaining better
control of layer thickness. The principal driving force for electrophoretic deposition
(EPD) is the charge on the particle and the electrophoretic mobility of the particles in
the solvent under the inuence of an applied electric eld. The EPD technique has been
used successfully for thick lm of silica [7], nanosize zeolite membrane [8], hydroxyapatite
coating on metal substrate for biomedical applications [9,10], luminescent materials [11
13], high-T
c
superconducting lms [14,15], gas diusion electrodes and sensors [16,17],
multi-layer composites [18], glass and ceramic matrix composites by inltration of ceramic
particles onto bre fabrics [19], oxide nanorods [20], carbon nanotube lm[21], functionally
graded ceramics [22,23], layered ceramics [24], superconductors [25,26], piezoelectric mate-
rials [27], etc. Indeed, the only intrinsic disadvantages of EPD, compared with other colloi-
dal processes (e.g. dip and slurry coating), is that it cannot use water as the liquid medium,
because the application of a voltage to water causes the evolution of hydrogen and oxygen
gases at the electrodes which could adversely aect the quality of the deposits formed. How-
ever, given the numerous non-aqueous solvents that are available, this limitation is minor.
Table 1
Characteristics of electrodeposition techniques [2]
Property Electroplating Electrophoretic deposition
Moving species Ions Solid particles
Charge transfer on deposition Ion reduction None
Required conductance of liquid medium High Low
Preferred liquid Water Organic
Fig. 1. Schematic illustration of electrophoretic deposition process. (a) Cathodic EPD and (b) anodic EPD.
3. Factors inuencing EPD
The mechanism of EPD involve charged particles in a suspension being deposited onto
an electrode under the inuence of an applied electric eld. Two groups of parameters
determine the characteristics of this process; (i) those related to the suspension, and (ii)
those related to the process including the physical parameters such as the electrical nature
of the electrodes, the electrical conditions (voltage/intensity relationship, deposition time,
etc.).
For the EPD of particles, part of the current should be carried not only by the charged
particles but by free ions co-existing in the suspension. Therefore the amount of deposited
particle is not simply related to the current. However, the current carried by the free ions
could be ignored when the amount of free ions is negligible. Indeed the amount of free ions
is generally small in organic suspensions such as ketones. On the other hand, it is believed
that the accumulation of anionic and cationic charge at the electrodes during electropho-
resis suppresses the subsequent deposition rate. However the eect of accumulated ions are
negligible in the initial period.
The rst attempt to correlate the amount of particles deposited during EPD with dier-
ent inuencing parameters was described by Hamaker [1] and Avgustnik et al. [28]
Hamakers law relates the deposit yield (w) to the electric eld strength (E), the electropho-
retic mobility (l), the surface area of the electrode (A), and the particle mass concentration
in the suspension (C) through the following equation:
w =
Z
t
2
t
1
l E A C dt (1)
Avgustiniks law is based upon cylindrical, coaxial, electrodes and the electrophoretic
mobility has been expanded and is represented in terms of permittivity (e), the zeta poten-
tial (n), and the viscosity of the suspension (g)
w =
l E e n C t
3 ln(a=b) g
(2)
where l and a are the length and radius of the deposition electrode, respectively, b is the
radius of the coaxial counter electrode (b > a).
Biesheuval and Verweij [29] improved upon these classical equations and developed
more complex model of the deposition process by considering the presence of three distinct
phases namely (i) a solid phase (the deposit), (ii) a suspension phase, and (iii) a phase con-
taining little or no solid particles. The deposit phase and the particle-free liquid phase both
grow at the expense of the suspension phase. By considering the movement of the bound-
ary between the deposit and the suspension phase with time along with the continuity
equation and expression for velocity of particles in the suspension, Biesheuval and Verweij
[29] derived the following equation based on that of Avgustinik et al. [28]:
w =
2 p l l E C
d
ln(a=b)

/
s
/
d
/
s
t (3)
where /
s
and /
d
are the volumetric concentration of particles in suspension and deposit,
respectively, C
d
is the mass concentration of particles in the deposit, l is the electropho-
retic mobility (=en/6pg).
Ishihara et al. [30] and Chen and Liu [31] used the following equation for the weight (w)
of charged particles deposited per unit area of electrode in the initial period, ignoring the
charge carried by the free ions
w =
2
3
C e
0
e
r
n
1
g

E
L

t (4)
where C is the concentration of the particle, e
0
is the permittivity of vacuum, e
r
is the rel-
ative permittivity of the solvent, n is the zeta potential of the particles, g is the viscosity of
the solvent, E is the applied potential, L is the distance between the electrodes, and t is the
deposition time. The above equations, often termed as Hamaker equation, suggests that
the deposition weight of the charged particles under ideal electrophoretic deposition
depends on the above parameters. However, if the solvent, the particles, and the apparatus
for EPD are xed, the factors n, e
r
, g and L in the above equation are constant. Conse-
quently, the weight of the deposited particles (w) in the EPD method is a function of E,
t and C. Therefore, the mass of the deposited particles, namely, the thickness of the lms
can be readily controlled by the concentration of the suspension, applied potential, and
deposition time in the EPD method.
3.1. Parameters related to the suspension
Regarding the suspension properties, many parameters must be considered, such as the
physicochemical nature of both suspended particle and the liquid medium, surface prop-
erties of the powder, and the inuence of the type and concentration of the additives,
mainly dispersants.
3.1.1. Particle size
Although there is no general thumb rule to specify particle sizes suitable for electropho-
retic deposition, good deposition for a variety of ceramic and clay systems have been
reported to occur in the range of 120 lm [2]. But this does not necessarily mean that
deposition of particles outside this size range is not feasible. Recently, with increasing
thrust on nanostructured materials, the EPD technique is being viewed with more interest
for assembly of nanoparticles, and will be discussed in more detail in later section. It is
important that the particles remain completely dispersed and stable for homogeneous
and smooth deposition. For larger particles, the main problem is that they tend to settle
due to gravity. Ideally, the mobility of particles due to electrophoresis must be higher than
that due to gravity. It is dicult to get uniform deposition from sedimenting suspension of
large particles. Electrophoretic deposition from settling suspension will lead to gradient in
deposition, i.e., thinner above and thicker deposit at the bottom when the deposition elec-
trode is placed vertical. In addition, for electrophoretic deposition to occur with larger
particles, either a very strong surface charge must be obtained, or the electrical double
layer region must increase in size. Particle size has also been found to have a prominent
inuence on controlling the cracking of the deposit during drying. Sato et al. [4] investi-
gated the eect of YBa
2
Cu3O
7d
(YBCO) particle size reduction on crack formation
and their results are shown in Fig. 2. Crack in lms deposited from a suspension consisting
of relatively smaller particle (0.06 lm) was much less than that in lms deposited from the
suspension containing larger particles (3 lm). Hence, reduction in particle size improved
the morphology of the YBCO superconducting lm fabricated by electrophoretic deposi-
tion suggesting that it is a useful technique to minimize cracking of deposits.
3.1.2. Dielectric constant of liquid
Powers [32] investigated beta-alumina suspensions in numerous organic media and
determined the incidence of deposition as a function of the dielectric constant of the liquid
and the conductivity of the suspension. A sharp increase in conductivity with dielectric
constant was noted; which apparently refers to the liquid in their pure state. It should also
be noted that impurities, in particular water, aects the conductivity and that conductivity
of milled suspension is very dierent to that of pure liquid, as a consequence of dissociative
or adsorptive charging modes. Powers [32] obtained deposits only with liquid for which
the dielectric constant was in the range of 1225. With too low a dielectric constant, depo-
sition fails because of insucient dissociative power, whilst with a high dielectric constant,
the high ionic concentration in the liquid reduces the size of the double layer region and
consequently the electrophoretic mobility. Consequently, the ionic concentration in the
liquid must remain low, a condition favoured in liquids of low dielectric constant. The
Fig. 2. SEM images of YBCO lm electrophoretically deposited on silver electrode from its suspension in acetone
at 10 V for 180 s (lm A: mean particle size = 3 lm; lm B: mean particle size = 0.06 lm). The lms were sintered
at 945 C for 1 h and annealed at 500 C for 6 h [4].
dielectric constant is generally the product of relative dielectric constant and dielectric con-
stant in vacuum. Table 2 shows physical properties such as viscosity and relative dielectric
constant of some solvents [33].
3.1.3. Conductivity of suspension
Ferrari and Moreno [34], after a careful study proposed that the conductivity of the sus-
pension is a key factor and needs to be taken into account in EPD experiments. It has been
pointed out that if the suspension is too conductive, particle motion is very low, and if the
suspension is too resistive, the particles charge electronically and the stability is lost. They
observed increase in conductivity of the suspension with both temperature and with poly-
electrolyte (dispersant) concentration; but not all conductivity values were found useful for
electrophoretic deposition. They found the existence of a narrow band of conductivity
range at varying dispersant dosage and temperature, in which the deposit is formed. Con-
ductivity out of this region are not suitable for EPD, limiting the forming possibilities.
This suitable region of conductivity is however expected to be dierent for dierent sys-
tems. The margin of conductivity region suitable for EPD, however can be increased by
the applied current assuring the success of the EPD process [35].
3.1.4. Viscosity of suspension
In casting processes, the main controlling parameter is the viscosity. Rheological mea-
surements on concentrated slips give us a good idea about the optimum dispersing state
when adding dispersants. In EPD process, the solid loading is very low and the viscosity
cannot be used to evaluate the dispersion state [34,35]. But the desired properties in the
suspension vehicle are low viscosity, high dielectric constant and low conductivity.
3.1.5. Zeta potential
The zeta potential of particles is a key factor in the electrophoretic deposition process.
It is imperative to achieve a high and uniform surface charge of the suspended particles. It
plays a role in: (i) stabilization of the suspension by determining the intensity of repulsive
interaction between particles, (ii) determining the direction and migration velocity of
particle during EPD, (iii) determining the green density of the deposit. The overall stability
of a system depends on the interaction between individual particles in the suspension. Two
mechanisms aect this interaction, which are due to electrostatic and van der Waals forces.
The probability of coagulation of a disperse system depends on the interaction energy
resulting from this forces, and will be dealt with in detail later. A high electrostatic
Table 2
Physical properties of solvents [33]
Solvents Viscosity (cP) = 10
3
N s m
2
Relative dielectric constant
Methanol 0.557 32.63
Ethanol 1.0885 24.55
n-Propanol 1.9365 20.33
Iso-propanol 2.0439 19.92
n-Butanol 2.5875 17.51
Ethylene glycol 16.265 37.7
Acetone 0.3087 20.7
Acetylacetone 1.09 25.7
repulsion due to high particle charge is required to avoid particle agglomeration. The par-
ticle charge also aects the green density of the deposit. During formation of the deposit,
the particles become closer to each other and with increasing attraction force. If the par-
ticle charge is low, the particles would coagulate even for relative large inter-particle
distances, leading to porous, sponge-like deposits. On the contrary, if the particles have
a high surface charge during deposition they will repulse each other, occupying positions
which will lead to high particle packing density [36]. It is therefore very important to con-
trol the solids loading and concentration of solvents and additives in the EPD suspension
in order to reach the highest possible green density of the deposit. The zeta potential can
be controlled by a variety of charging agents such as acids, bases and specically adsorbed
ions or polyelectrolytes, to the suspension [37]. Thus there exists a variety of additives that
aect the charge magnitude and its polarity. These additives act by dierent mechanisms.
The main criteria for selection of a charging agent are the preferred polarity and deposi-
tion rate of the particles.
Chen et al. [38] found that the stability and deposition rates of alumina from its suspen-
sion in ethanol was maximum at pH value of 2.2 at which the positive zeta potential of
alumina was maximum (Fig. 3). However, under higher pH value of ~11, the suspensions
were less stable. This can be explained based on a charging mechanism recently proposed
by Wang et al. [39] on the alumina surface
AlOH
2
=
H
AlOH =
OH
AlO
H
2
O (5)
Under basic conditions such as pH ~11, AlOH tends to form AlO
; however, the presence

of water is prone to bring the above reaction towards the formation of AlOH
2
, rather
than the formation of AlO
, resulting in an absolute value of the zeta potential greater

at pH ~2 than at pH ~11. This led to high stability of suspension at lower pH than at
higher pH conditions.
Fig. 3. Zeta potential of Al
2
O
3
powder in ethanol [38].
Zarbov et al. [37] established that while the deposition rate is directly dependent on the
zeta potential, which is determined by the charging additive, the inuence of such an addi-
tive is exerted also by its eect on the ionic conductivity of the suspension. The ionic con-
ductivity determines the potential drop in the bulk of the suspension, which constitute the
driving force for the transfer of the particles to the electrode.
3.1.6. Stability of suspension
Electrophoresis is the phenomenon of motion of particles in a colloidal solution or sus-
pension in an electric eld, and generally occurs when the distance over which the double
layer charge falls to zero is large compared to the particle size. In this condition, the par-
ticles will move relative to the liquid phase when the electric eld is applied. Colloidal par-
ticles which are 1 lm or less in diameter, tend to remain in suspension for long periods due
to Brownian motion. Particles larger than 1 lm require continuous hydrodynamic agita-
tion to remain in suspension. The suspension stability is characterized by settling rate
and tendency to undergo or avoid occulation. Stable suspensions show no tendency to
occulate, settle slowly and form dense and strongly adhering deposits at the bottom of
the container. Flocculating suspensions settle rapidly and form low density, weakly adher-
ing deposits. If the suspension is too stable, the repulsive forces between the particles will
not be overcome by the electric eld, and deposition will not occur. According to some
models for electrophoretic deposition the suspension should be unstable in the vicinity
of the electrodes [5]. This local instability could be caused by the formation of ions from
electrolysis or discharge of the particles; these ions then cause occulation close to the elec-
trode surface. It is desirable to nd suitable physical/chemical parameters that characterize
a suspension suciently in order that its ability to deposit can be predicted. Most inves-
tigators use zeta potential or electrophoretic mobility, but these do not uniquely determine
the ability of a suspension to deposit. For example, in suspension of aluminium in alcohol
the addition of electrolyte causes no signicant change to the zeta potential, but deposits
can only be obtained in the presence of the electrolyte [40]. The stability of the suspension
is evidently its most signicant property, but this is a somewhat empirical property not
closely related to fundamental parameters.
3.2. Parameters related to the process
3.2.1. Eect of deposition time
Basu et al. [41] found that deposition rate for a xed applied eld decreases with
increased or prolonged deposition time. Similar observation was made by Chen and Liu
[31]. Fig. 4 shows a typical deposition characteristics of ZnO coating on copper electrode
at dierent applied potentials, with increasing time of deposition [42]. It is clearly evident
that the deposition is linear during the initial time of deposition. But as more and more
time is allowed, the deposition rate decreases and attains a plateau at very high deposition
times.
In a constant voltage EPD, this is expected because: while the potential dierence
between the electrodes is maintained constant, the electric eld inuencing electrophoresis
decreases (Fig. 5) with deposition time because of the formation of an insulating layer of
ceramic particles on the electrode surface [43]. But during the initial period of EPD, there
is generally a linear relationship between deposition mass and time.
3.2.2. Applied voltage
Normally the amount of deposit increases with increase in applied potential. Fig. 6
shows the weight of deposited hydroxyapatite on Ti
6
Al
4
V substrate from its suspension
in isopropyl alcohol. Although powders can be deposited more quickly if greater applied
elds are used, the quality of the deposit can suer. Basu et al. [41] found that more uni-
form lms are deposited at moderate applied elds (25100 V/cm), whereas the lm qual-
ity deteriorates if relatively higher applied elds (>100 V/cm) are used. Because the
formation of particulate lm on the electrode is a kinetic phenomenon, the accumulation
rate of the particles inuences their packing behaviour in coating. For a higher applied
eld, which may cause turbulence in the suspension, the coating may be disturbed by ows
in the surrounding medium, even during its deposition. In addition, particles can move so
Fig. 4. Relationship between deposit thickness and time of deposition for ZnO coatings on copper electrode at
dierent applied potential [42].
Fig. 5. Current density versus deposition time for deposition of hydroxyapatite at dierent applied voltages: (a)
50 V; (b) 100 V; (c) 200 V [43].
fast that they cannot nd enough time to sit in their best positions to form a close-packed
structure. Finally, in high eld situations, lateral motion of the particles once deposited,
also are restricted on the surface of the already deposited layer, because higher applied
potential exerts more pressure on particle ux and movement, the applied eld aects
the deposition rate and the structure of the deposit.
Negishi et al. [33] observed that the current density of n-propanol solvent in absence of
any powder, were proportional to applied voltage and it tend to unstable with increasing
applied voltages (Fig. 7). Such stability data serves as a good guideline for deciding the
deposition parameters and consequently the quality of deposit formed by EPD. It is con-
sidered that the unstable current density inuences the quality of deposition morphology.
Fig. 6. Weight of deposited hydroxyapatite on Ti
6
Al
4
V substrate versus applied voltage for dierent deposition
durations: (a) 30 s and (b) 120 s [43].
Fig. 7. Stability of current density of n-propanol for dierent applied voltages [33].
From the current density prole in Fig. 7, it is reasonable to suggest that the applied volt-
age should be less than 100 V in the case of n-propanol. It was observed that amount of
YSZ deposition from the n-propanol bath increased with increasing applied voltage. How-
ever, the deposit surface morphologies were found to be at at low voltages and it became
more rough with increasing applied voltage.
3.2.3. Concentration of solid in suspension
The volume fraction of solid in the suspension play an important role, particularly for
multi-component EPD. In some cases, although each of the particle species have same sign
of surface charge, they could deposit at dierent rates depending on the volume fraction of
solids in the suspension. If the volume fraction of solids is high, the powders deposit at an
equal rate. If however, the volume fraction of solids is low, the particles can deposit at
rates proportional to their individual electrophoretic mobility [44].
3.2.4. Conductivity of substrate
The uniformity and conductivity of substrate electrode is an important parameter crit-
ical to the quality of the deposition of green lm by EPD. Peng and Liu [45] observed that
low conductivity of the La
0.9
Sr
0.1
MnO
3
(LSM) substrate leads to non-uniform green lm
and slow deposition. Chen and Liu [31] noticed that when as pressed LSM or LSMYSZ
composite pellets were used as substrate for EPD, the deposition rate of YSZ was slow and
obtained lm was non-uniform. This was attributed to be due to the high resistance of the
substrates resulting from the binder added. When the pellets were red at 700 C for 0.5 h
to remove the binder, the conductivity of the substrates increased substantially. Conse-
quently, the green YSZ lm obtained was of high quality.
It is quite evident from the above discussion that the kinetics of electrophoretic depo-
sition and the quality of deposit formed is dependent on a large number of parameters. It
is required to have a careful control of these individual parameters during electrophoretic
deposition. However, many of the parameters are inter-related to one another. It is noted
that the quality of electrophoretic deposition heavily depends on the suspension conditions
[46]. In general, a well-dispersed stable suspension will provide a better deposition during
EPD compared to an unstable or agglomerated powder suspension. Zeta potential is an
important parameter that relates to suspension stability and mobility. It measures the
potential dierence between the particle surface and the shear layer plane formed by the
adsorbed ions. As zeta potential is closely related to the particles double layer thickness,
it hence provides information on the agglomeration of the particles in the suspension. In
general, the higher the absolute value of the measured zeta potential, the better is the dis-
persion of the particles in the suspension. Besides the stability criteria, it is also noted that
it is the ions in the suspension that are carrying most of the current when an electric eld is
generated during EPD [4,5], as a result, the electrical conductivity of the suspension also
plays an important role in the process. Fig. 8 shows the zeta potential and electrical con-
ductivity of lead zirconate titanate (PZT) suspension as a function of pH [46]. It can be
seen that as the pH value decreases from 7.5 (isoelectric point) to 4.5, the value of the zeta
potential increases. This is attributed to the adsorption of the H
+
ions onto the particle
surfaces which enhances the electrostatic repulsion force. However, as more H
+
ions are
added to the suspension, i.e., when pH value decreases from 4.5 to 2.0, the large amount
of positive ions results in the reduction of the double layer thickness and, hence, a decrease
in repulsive force between the particles. This will promote particle agglomeration and,
hence, give rise to poorer deposition results. At the alkaline range, similar phenomenon is
observed but with the adsorption of OH
ions in the suspension. It is, however, noted that

at the alkaline range, the zeta potential measured appeared to be much lower in absolute
magnitude compared to that at the acidic range. The ionic concentration not only aects
the zeta potential, but is also closely related to the suspension electrical conductivity. This
can be seen from Fig. 8 which shows that the electrical conductivity is low when the ionic
concentration in the suspension is low. However, as the ionic concentration in the suspen-
sion increases, the conductivity of the suspension increases rapidly. It is found that at high
ionic concentration, not only the rate of agglomeration will increase and form larger
agglomerates that have lower mobility, but also the large amount of free ions in the suspen-
sion may become the main current carrier and, hence, reduce the electrophoretic mobility of
the particles. The conductivity of suspension is also directly related to dielectric constant of
the suspending medium and it increases with increase in dielectric constant [32]. Hence the
choice of the suspension parameters needs to be made judiciously for preparation of a suit-
able EPD suspension. Once the parameters related to the suspension are xed, the process
parameters can be altered conveniently for attaining desired deposition. Obviously, the
most dominant parameters inuencing the electrophoretic deposition are the process
parameters such as applied voltage, deposition time and particle concentration in the sus-
pension. Invariably, high applied potential leads to higher deposition rate but care has to be
taken to ensure stable current density to obtain uniform deposit. Similarly, higher deposi-
tion rate is expected with increasing particle concentration and deposition time [44].
4. Kinetics of electrophoretic deposition
To make EPD process commercially more viable, a knowledge of the kinetics of EPD
process is necessary in order to (a) control and manipulate deposition rate, and (b) achieve
exibility in microstructural manipulation. Hamaker [1] observed a linear dependence of
the deposited weight or yield of the EPD with the amount of charge passed, and proposed
that the amount deposited is proportional to the concentration of the suspension, time of
Fig. 8. Zeta potential and conductivity of the PZT suspension at varying pH in aqueous media [46].
deposition, surface area of deposit, and the electric eld. EPD can be conducted under
constant current or constant voltage mode with either constant or changing concentration
(decreasing concentration of suspension) with deposition time. Sarkar et al. [47] demon-
strated the kinetic aspects of EPD through schematic plots (Fig. 9) of deposit weight
against time of deposition for four possible deposition conditions: curve A (constant-cur-
rent and constant-suspension concentration), curve B (constant-current but decreasing
suspension concentration), curve C (constant-voltage and constant-suspension concentra-
tion) and curve D (constant-voltage but decreasing suspension concentration). Except in
curve A where the rate of deposition is constant with time, the rate of deposition decreases
asymptotically with deposition time in either curve B, C, or D. After allowing for sucient
deposition time, the nal yield and rate of deposition are highest in curve A, followed by
curve B, C, and D, respectively. The eect of decreasing suspension concentration on the
reduction of the nal yield and rate of deposition is obvious during either constant-current
(curves A and B) or constant-voltage curve C and D) EPD. Comparison of curve A (con-
stant-current) and curve C (constant-voltage) clearly reveals that even if the suspension
concentration is kept constant during deposition in both of them, (a) the rate of deposition
was constant in curve A while it decreased asymptotically with time in curve C and (b)
nal yield was considerably higher in curve A than that in curve C. Thus the deviation
of curve A from curve C is not due to decreasing suspension concentration but is due
to a decrease of particle velocity as a function of deposition time. Such decrease in particle
velocity during constant-voltage EPD is due to the fact that deposited mass acts as a
shielding eect and has higher electrical resistance than the suspension from which depo-
sition takes place. Consequently, as the deposit grows with deposition time, the available
electrical driving force or voltage per unit length of suspension decreases with time.
5. Role of polymer binders in EPD
Polymer binders are common additives in ceramic processing. The EPD processing
employs binder only seldom or minimal. The role of binders in EPD processing is
Fig. 9. Schematic of EPD kinetics [47].
multifunctional. Polymer binders are used to obtain adherent deposits and prevent cracks.
Moreover, the adsorbed polymer can provide steric stabilization of suspension of ceramic
particles and reduce viscosity of the suspension. In EPD processing, charged polymer par-
ticles transport adsorbed polymer to the electrode surface, thus allowing the polymer bin-
der to be included in the deposit. This is in contrast to some other ceramic techniques,
where the entire dissolved polymer is included in the green body after solvent evaporation.
Therefore, the control of polymer adsorption is of paramount importance for electropho-
retic deposition. The amount of polymer adsorption depends on polymer concentration in
suspension and specic polymerparticle, polymersolvent, particlesolvent and particle
dispersant interactions. Good solvents are necessary in order to achieve high polymer con-
centration in solution. However, the polymer can be adsorbed on the surface of ceramic
particles when its solubility in the dispersion medium is low. Adsorption of polymer on
ceramic particles in poor solvent can result in bridging occulation. In contrast, good sol-
vents are important to achieve steric stabilization. Polymer stabilizing moieties, which
extend out from the particle surface must be well solvated in a good solvent. Therefore,
for electrophoretic deposition, it could be advantageous to use copolymers of a block
or graft type. Indeed, soluble polymers serve to anchor copolymer molecules to the particle
surface, whereas chains of soluble polymers enable steric stabilization.
6. Importance of powder washing before EPD
Successful EPD techniques requires a stable suspension wherein well dispersed particles
have a controlled surface charge. Thus the preparation of a particulate suspension with a
carefully dened chemistry before conducting EPD is essential. The rst step in suspension
preparation is powder washing to remove any residual impurities incorporated during
powder preparation. As an example, during preparation of yttria stabilized zirconia
(YSZ) powders (TZ-8YS) by co-precipitation technique using chloride precursors (e.g. zir-
conyl chloride, ZrOCl
2
), the solution contain residual surface chlorides which can be
tested by measuring specic conductivity of the supernatant of the dispersion. The conduc-
tivity of de-ionised water is about 0.04 lS/cm. Presence of Cl
ions can also be conrmed

by adding a small amount of silver nitrate (AgNO
3
) salt to the supernatant. If there is for-
mation of an insoluble precipitate (of AgCl) then there is residual chloride impurities in the
solution.
Removal of the Cl
ions and other impurities is very important because it can aect the
suspension stability, deposition characteristics and later, the sintering. Basu et al. [41]
found that unwashed powder led to unstable suspension which needed agitation every
510 min. When the suspension is settling constantly, during EPD, the unwashed powder
led to lower deposition yield, gradient in the EPD lm thickness (thinner coating at top,
thicker on bottom), a decrease of 1525% in overall green density of the as deposited
coating.
Basu et al. [41] accomplished removal of Cl
impurities from surface of the particles

using successive washing in de-ionised water because water easily participates in an ion-
exchange interaction between the impurities on the powder surface and the bulk solvent
in accordance with Eq. (6)
Cl (surface) +H
2
O (solvent) H
2
O (surface) +Cl
(solvent) (6)
A signicant reduction in conductivity of supernatant was observed on washing. In addi-
tion, washing the TZ-8YS powder eight times in de-ionised water was sucient to yield
reproducible behaviour during EPD.
7. Practical considerations
In view of the sensitivity of the electrophoretic mobility to factors such as chemical
environment and particle surface topography, and the need for suspension of marginal sta-
bility, it might be thought that a process based on electrophoretic deposition would be
inherently dicult to control. This situation is not helped by the shortcomings in funda-
mental understanding of electrophoretic deposition, and it is almost impossible to predict
whether suspensions will deposit electrophoretically. With any system, it is of course abso-
lutely necessary to avoid contamination by any impurity that can adversely inuence the
electrokinetic properties of the suspension; a stringent requirement, but one that should
perhaps be regarded as a strength rather than a weakness of the process. The EPD process
can deposit powder uniformly on a complicated shape electrode and, as a result, can pro-
duce geometrically complicated shapes. However, in the case of bulk ceramic, after shape
forming the substrate (depositing electrode) needs to be removed from the deposit. Com-
mercial applicability of EPD forming depends on the eective separation of the substrate
from the deposit. In the case of simple geometry, separation can be done after drying of
the deposit. For complicated shapes, a combustible substrate that can be removed during
the sintering process could be used. In the case of coatings, the sample often develops
cracking during drying and sintering and the successful application of EPD to this area
depends on overcoming this problem.
Another important area of concern is how to avoid cracking in the ceramic coating dur-
ing drying and sintering [48]. During drying and sintering, the coating densies, and as a
result shrinks, but the substrate typically does not change dimension. During this process,
the coating will develop tensile stress in it and these stresses will be relieved by the forma-
tion of cracks. There are several approaches that can be taken to avoid this cracking. Care-
ful control of the EPD process together with moderate control on drying may avoid the
formation of drying cracks. During sintering the coating typically has about 1015% linear
shrinkage. Traditionally, this sintering cracking is avoided by using a liquid phase during
sintering; a good example is glass enamel on a metal substrate. The enamel composition is
adjusted in such a way that its thermal expansion is closely matched with the substrate. As
a result it does not form cracks during cooling from the sintering temperature. This liquid
phase sintering is also equally eective in avoiding cracking in ber composite synthesis.
The second approach is to use a substrate that also shrinks during sintering. Recently, this
approach has been used, particularly in SOFC fabrication where typically a YSZ electro-
lyte is applied to a partially sintered or an unsintered anode substrate. During sintering,
both the substrate and coating shrink thereby avoiding cracks.
8. Water-based EPD
In general, the organic solvents are very popular as dispersing media in electrophoretic
deposition. Table 3 presents a summary of some solvents commonly used in electropho-
retic deposition. But the use of aqueous system has important advantages since they need
much lower voltage to be applied and the environmental problems associated with
organics are avoided [35]. Obviously, the use of water implies advantages such as higher
temperature-control during the process or a faster kinetics, in addition to important
health, environmental, and cost benets. These advantages promoted the interest in some
research groups in the 1990s to consider using aqueous EPD to process technical ceramics.
The water-based suspensions however causes a number of problems in electrophoretic
forming [63]. The main problems are related to electrochemical reaction in the electrodes
when current is passed through, which seriously aects the eciency of the process and the
uniformity of the deposit. First and foremost, there is a deviation in the deposition kinetics
from the linear Hamaker growth due to deviation in current density and powder concen-
tration [64]. The deviation from linearity could not be prevented even after controlling the
current density and powder concentration suggesting that there could be factors other
than those already discussed, which aect the aqueous EPD process. Electrolysis of water
occurs at low voltages, and gas evolution at the electrodes is inevitable at eld strengths
high enough to give reasonably short deposit times. This causes bubbles to be trapped
within the deposit unless special procedures are adopted, such as the use of absorbing
or porous electrode materials, or high speed chamber ows. Current densities are high,
leading to Joule heating of the suspension, and electrochemical attack of the deposit. Sec-
ondly, when metallic electrodes are used, the normal potential of the electrode is largely
overpassed. This facilitates oxidation of the electrodes and migration of metallic impurities
towards the slurry in the opposite direction to that of the migrating particles. In most
cases, these impurities are retained in the deposit as heterogeneities and/or residual poros-
ity, thus degrading its expected properties.
Another electrokinetic phenomena occurring in an aqueous EPD is water electroosmo-
sis, which consist of the movement of the liquid phase because of an external electric eld.
This could be helpful in EPD because it would accelerate drying of the deposit surface
Table 3
Solvents used for electrophoretic deposition
Sl. no. Solvent Deposited material Reference
1 Water Al
2
O
3
[34,35,49]
Al
2
O
3
/ZrO
2
[50]
2 Acetone YSZ [51]
La
1x
Sr
x
Ga
1y
Mg
y
O
3(x+y)/2
[52]
3 Acetoneethanol YSZ [45]
4 Acetylacetone YSZ [53]
[51]
5 Cyclohexane YSZ [51]
6 Isopropylalcohol Hydroxyapatite [54]
YBa
2
Cu
3
O
7x
[55]
7 Ethyl alcohol Al
2
O
3
, ZrO
2
[56]
8 Ethyl alcoholwater CeO
2
[57]
SnO
2
[58]
CaSiO
3
[59]
9 Ethyl alcoholacetylacetone MgO, Al
2
O
3
[60]
10 Glacial acetic acid PZT [27]
11 Dichloromethane b-alumina [61]
12 Methyl ethyl ketone (MEK) Al
2
O
3
[62]
13 Toluene-ethyl alcohol Al
2
O
3
[62]
which is in contact with the electrode. So, if the process were well controlled, demoulding
of the self-supported deposits would be easier. Contrarily, if the deposits were too thick, or
the process were too fast, crack formation would occur as a consequence of the drying gra-
dient. Therefore, an adequate control of the colloid chemistry of the particles in the slurry
is necessary.
9. Non-aqueous EPD
In general, organic liquids are superior to water as a suspension medium for electropho-
retic forming. While the generally lower dielectric constant in organic liquids limits the
charge on the particles as a result of the lower dissociating power, much higher eld
strengths can be used since the problems of electrolytic gas evolution, joule heating and
electrochemical attack of the electrodes are greatly reduced or non-existent. Moreover,
the organic liquids are preferred due to their higher density, good chemical stability and
low conductivity.
The electrolysis and gas evolution associated with aqueous EPD processing can be
avoided by using solvents of extremely high oxidationreduction potentials like benzene
or ketones. However, the electric charge on oxide particles in benzene or ketones will be
insucient for EPD as very small amounts of free ions exist in these solvents. Conse-
quently, a few hundreds of volts are required for EPD. It is reported that protons are
formed by a reaction between ketone and iodine. The reaction of iodine with acetone
can be represented by Eq. (7) [52]
CH
3
COCH
3
+2I
2
== ICH
2
COCH
2
I +2H
+2I
(7)
Similarly, the reaction between acetylacetone and iodine can be represented by the follow-
ing equation [51]:
CH
3
COCH
2
COCH
3
==
I
2
ICH
2
COCOCH
2
I 2I
2H
(8)
Adsorption of the formed protons onto the suspended particles will make them positively
charged. Application of a DC eld causes the positively charged particles to move towards
and deposit on the cathode.
The major problems associated with the use of organics are that higher voltages are
required. Moreover, the cost, toxicity and ammability of organic liquids warrants judi-
cious selection and practice of solvent reclamation in order to minimise these problems.
10. Charge development on powder surface in suspension
10.1. Aqueous suspension
Electrophoretic deposition relies on the capability of the powder to acquire an electric
charge in the liquid in which it is dispersed. In general when solid powder is dispersed in a
polar liquid, such as water, usually it results in the buildup of a charge at the solidliquid
interface [65]. The interfacial charge is a result of a range of mechanisms such as adsorp-
tion or orientation of dipolar molecules at the particle surface, electron transfer between
the solid and the liquid phase due to dierences in work function, selective adsorption of
ions onto the solid particle and dissociation of ions from the solid phase into the liquid.
For aqueous suspensions of ceramic powders, especially oxides, the role of protons as
charge determining ions has been clearly established in literature. Yates et al. [66] pro-
posed the following description of the interaction of surfaces of oxides with the liquid
through simple ionization reactions of surface groups:
SOH SO
(9)
SOH
2
SOHH
(10)
Later, the description was improved to account for the reaction of major electrolyte ions
with ionisable surface sites. The net charge as evident by the above reactions, is controlled
by pH and reaction constant for the respective dissociation reaction. The point of zero
charge (pzc) is the pH value where the surface concentration of (SO
) and (SOH
2
)
are equal. The surface charge is negative at pH > pH
pzc
and positive at pH < pH
pzc
.
10.2. Non-aqueous suspension
For non-aqueous media, however, the hydrogen concentration (pH) looses its validity
as a general measure for the acidity or alkalinity of a medium, and systematic information
on charging in these media is relatively scarce. Nonetheless, the necessity of a global
approach towards the behaviour of a solute in a series of solvents, such as its solubility,
redox potential or degree of ionization, has led to the development of donor numbers,
which express the tendency of a solvent to donate electrons [67]. The relative measure
of the alkalinity of a solvent is given by the enthalpy of its reaction with an arbitrarily cho-
sen reference acid. Ranking the relative degree of acidity of media can be performed by
using the acceptor number scale, which is a measure for the tendency of solvents to accept
electrons. Indeed, Labib and Williams [68] have shown that in the absence of water, the
sign of the charge on the surface of ceramic powders depend on the donor number of
the solvent, strongly suggesting that charging through electron exchange with the solvent
is possible. However, Wang et al. [39] found the surface charge characteristics on alumina
powder dispersed in ethanol to be analogous to the behaviour of oxides in water where a
mere adjustment in pH of ethanol by addition of acetic acid or tetra-methyl-ammonium-
hydroxide allowed control of the sign of the charge on alumina powder. Since in the EPD
processing, organic solvents are used more frequently than aqueous suspensions, this
observation on control of surface charge on ceramic powder through addition of acids
or bases to organic media serves as a valuable general guideline for suspension prepara-
tion. In reality, many organic solvents of technical quality do contain some residual water.
Although the evidence for the charging in non-aqueous media by electron transfer is inter-
esting from a theoretical point of view, for practical use in ceramic industry the require-
ment of working under absolutely dry conditions is far too expensive. To test how far
the observation of Wang et al. [39] for alumina can be generalized to ceramic processing,
Vandeperre et al. [67] measured the charging of a range of ceramic powders (oxides, car-
bides, nitrides and borides) by potentiometric titration and compared them with sign of
the electrophoretic mobility in an acidic and alkaline organic reference medium. Their
measurement showed that to a large extent the rationale for charging of ceramic powders
in water also applies to charging in non-aqueous media. Negishi et al. [69], while preparing
YSZ suspension in n-propanol, suggested that the small amount of residual water present
in commercial n-propanol used for preparation of YSZ suspension for EPD, generated H
+
ions and OH
ions by electrolytic dissociation. The zeta potential is inuenced by the

adsorption of the generated H
+
ions onto the YSZ in n-propanol bath leading to positive
charge on YSZ in n-propanol.
11. Properties of suspension for EPD
A key ingredient in most of the colloidal processing methods of ceramic forming includ-
ing electrophoretic deposition (EPD) is the achievement of a well stabilized, unagglomer-
ated, and homogeneous slurry. Through careful control of the interparticle forces,
colloidal suspensions can be prepared in the dispersed, weakly occulated or strongly oc-
culated states. A distinguishing feature of all colloidal system is that the contact area
between the particle surface and the dispersing liquid is large. As a result the interparti-
cle/surface forces strongly inuence suspension behavior. The colloidal stability is gov-
erned by the total interparticle potential energy. The dominating interparticle forces in
most ceramic system are: (i) the van der Waal attractive force, (ii) double layer (electro-
static) repulsive force, and (iii) steric (polymeric) forces. In order to obtain a well-stabilized
suspension, particles dispersed in the suspending medium must exhibit sucient repulsive
forces to oset the van der Waals attraction. These forces are better understood in terms of
electrical double layer and their interactions and will be discussed in the following section.
11.1. The electrical double layer and electrophoretic mobility
Most substances acquire surface electric charge when brought in contact with a polar
(e.g. aqueous) medium. It is now well recognised that the development of electrical charge
on colloids dispersed in water is due to: (i) surface group ionisation (controlled by the pH
of the dispersion media), (ii) dierential solubility of ions (e.g. silver iodide crystals are
sparingly soluble in water and silver ions dissolve preferentially to leave a negatively
charged surface), (iii) isomorphous replacement/lattice substitution (e.g. in kaolinite,
Si
4+
is replaced by Al
3+
to give negative charges), (iv) charged crystal surface fracturing
(crystals can reveal surfaces with diering properties), and (v) specic ion adsorption (sur-
factant ions may be specically adsorbed). This surface charge inuences the distribution
of nearby ions in the polar medium. The ions, which establish the surface charge, are
termed potential determining ions (pdi). These normally include ions of which the solid
is composed; hydrogen and hydroxyl ions, ions capable of forming complex or insoluble
salts with the solid surface species. Ions of opposite charge (counter-ions) are attracted
towards the surface and ions of like charge (co-ions) are repelled away from the surface.
This leads to the formation of a net electrical charge of one sign on one side of the inter-
face and a charge of opposite sign on the other side-giving rise to what is called the elec-
trical double layer. Fig. 10 shows the schematic of a typical electrical double layer [70].
The theoretical and practical aspects of electrical double layer have been recognised and
understood through a vast amount of available literature and a major eld of investigation
in modern colloid and interface science has been the search for a means to predict and
determine the exact distribution of electrical charges at or near the solidliquid interface.
A widely accepted model for the double layer is that due to Stern [71], later modied by
Graham [as cited in Ref. 72], in which a part of the counter-ion charge is located close to
the particle surface (Stern layer) and the remainder is distributed more broadly in the dif-
fuse double layer or lyosphere. The Stern layer is actually a hypothetical plane representing
the closest distance of approach of hydrated counter ions to the surface. A schematic rep-
resentation of the distribution of charge species and the potential drop across the double
layer in accordance with the Stern model is also represented in Fig. 10 [70].
The interaction between charged particles is governed predominantly by the overlap of
the diuse layer, and accordingly the potential most relevant to the interaction is the one
developed at the boundary between the Stern and diuse layer (w
d
) rather than the poten-
tial at the particle surface (w
0
). This potential dierence between Stern plane and the dif-
fuse layer is called the zeta potential (n) [73]. The potential (w) at a distance x from the
Stern plane may reasonably be represented by the following linear form of the Poisson
Boltzmann expression:
w = w
d
exp(jx) (11)
where j is the DebyeHuckle parameter [71] and has the unit of (length)
1
, 1/j is the dis-
tance at which the potential w drops to 1/e of its value at the Stern plane, w
d
, and this dis-
tance is called the double layer thickness or Debye length. The double layer thickness is of
great importance in colloid stability and for that matter in occulation: it controls the
range of the double layer interaction. The thickness is controlled by the concentration
and valence of ions in solution. A high concentration of ions (high ionic strength) in
the medium generally results in a decrease in the double layer thickness and consequent
decrease in the potential [74]. The thickness is commonly represented in the following
form:
1
j
=
ee
0
kT
e
2
P
i
n
i
z
2
i

1=2
(12)
Fig. 10. Schematic representation of the double layer and potential drop across the double layer (a) surface
charge, (b) Stern layer, (c) diuse layers of counter-ions [70].
where e is the electronic charge, n
i
is the concentration of ions with charge z
i
, e is the dielec-
tric constant of the liquid, and e
0
is the permittivity of a vacuum. For aqueous solutions at
25 C, the value of j (m
1
) is given by [71]
j = 2:3 10
9
X
n
i
z
2
i

1=2
(13)
where n
i
is the molar concentration and z
i
is the valence of ion i.
The potential at the slip plane, the n potential, determines the velocity (m) by which the
particles move under the inuence of an applied electric eld (E) and the electrophoretic
mobility (l) which is given by
l =
m
E
(14)
The motion of particles under the eect of electrophoretic forces has been rst addressed
by Smoluchowski [75] and subsequently by many others [7680]. Smoluchowski predicted
that a rigid spherical particle possessing an electric double layer and embedded in an
unbound ow eld would be forced to move if subjected to an electrical potential gradient.
The mobility of the particle depend linearly on the dielectric constant (or permittivity) of
the uid, the potential gradient, and the zeta potential of the particle and is inversely
proportional to the uid viscosity and is given by the following Henry equation:
l =
2
3
e
0
e
r
n
g
f (jr) (15)
where e
0
is the permittivity of vacuum, e
r
is the relative permittivity of the solvent, g is the
solvent viscosity, f(jr) is the Henry coecient, which depends on the relation between the
thickness of the double layer (1/j) and the core radius (r) of the particle. For a point
charge (jr 1, HuekelOnsager case) or a at surface (jr 1, Helmholtz Smoluchow-
ski case) this coecient is 3/2 and 1, respectively [81].
The ow elds with nite boundary conditions, the wall eects were accounted for by
Morrison and Stukel [79] and Keh and Anderson [80] (i.e., for the case of particle traveling
in close proximity to the containing boundaries of the ow eld). Keh and Anderson [80]
have shown that if electro-osmosis is disregarded, the particle would experience an increas-
ing drag force and reduced mobility. It was also shown that, due to the electric eld, the
insulating rigid walls would induce an electro-osmotic ow, its direction depending on the
sign of the zeta potential. For an open permeable structure, the electro-osmotic ow pos-
sesses a uniform velocity prole and a neutral particle immersed in the uid would be
dragged by the electro-osmotic ow and move with identical velocity. However, for an
impermeable structure though the induced electro-osmotic ow still exists it is non-uni-
form since a net zero mass ow must be observed inside the pore. Haber [82] investigated
the electrophoretic penetration and deposition of colloidal ceramic particles into an imper-
meable porous substrate. The substrate is immersed in a suspension containing the parti-
cles and positioned between two electrodes. An electric potential gradient between the
electrodes is used to drive the ceramic particles into the pores which are closed at the
far end not allowing uid permeation. Three driving mechanism for movement of the par-
ticles have been identied: (a) the hydrodynamic drag force exerted on the particles due to
the electro-osmotic ow of the solvent inside the pores, (b) the electrophoretic force
exerted on the particles, and (c) the Brownian force due to thermal uctuations of the
solvent molecules. It was shown that under these forces the particles may reach the walls of
the pore and short range van der Waals forces may cause their capturing and deposition
onto walls.
11.2. DLVO theory and suspension stability
An essential role in interpretation of particle deposition process is played by the state of
dispersion and stability of suspension [83]. The state of dispersion of particles in suspen-
sion or the suspension structure can be controlled via careful manipulation of the inter-
particle forces and their interactions. The Van der Waals force for any given colloidal
system is essentially independent of almost any changes made to the solution. (e.g. by
addition of electrolyte). Even the adsorption of a surfactant forming monolayer onto
the particle surface will have only a slight eect on the van der Waals attraction [84]. This
suggests that in order to change the stability of a colloidal solution it is necessary to alter
the electrostatic double-layer forces in the system. Particle aggregation occurs when the
attractive van der Waals force exceeds the repulsive electrostatic ones. A quantitative esti-
mate of the relationship between stability of suspension in terms of interparticle forces and
energies of interactions that exist between colloidal particles and other surfaces in a liquid
has been described by the classical DLVO theory established by Derjaguin and Landau
[85] and Verwey and Overbeek [86]. The colloidal stability as per this theory is based on
the perikinetic phenomenon, i.e., the liquid is assumed to be stationary and collisions occur
due to Brownian translational motion. It assumes that the eect of two forces is additive,
and by combining the eect of electrostatic repulsion (V
R
) and van der Waals attraction
(V
A
) between two particles, the following expression for the total interaction energy func-
tion (V
T
) has been presented by Hiemenz [87]. Although the theory is based on the simple
additivity of dispersion and electrostatic interactions, it has proved successful in predicting
basic features of colloid stability and particle deposition phenomena. According to this
theory, the stability of a colloidal system is determined by the total energy of interaction,
determined by sum of the electrical double layer repulsive forces (V
R
) and the van der
Waals attractive forces (V
A
) which the particles experience as they approach one another
V
TOTAL
= V
R
V
A
(16)
The electrostatic repulsive force (V
R
) in the above equation can be expressed as
V
R
=
eaw
d
2
ln1 exp(jD) (17)
where e is the dielectric constant of the liquid, a is the radius of the particle, w
d
is the sur-
face potential which is often represented by zeta potential of the particle, j is the reciprocal
of double layer thickness, and D is the distance of separation between two interacting par-
ticles. The van der Waals attractive energy V
A
can be represented as
V
A
=
aA
131
2D
f (P) (18)
where A
131
is the Hamaker constant for media 1 of which the particles are composed and
separated in a liquid media 3, and is given by
A
131
= (A
1=2
11
A
1=2
33
)
2
(19)
where A
11
and A
33
are the interactions of 1 and 3, respectively, in vacuum. The above equa-
tion implies that the interaction between similar materials in a liquid would always be
attractive in nature (positive Hamaker constant); whatever might be the values of A
11
and A
33
. However, for dierent materials 1 and 2 in liquid 3 (when A
11
> A
33
> A
22
), the
possibility of negative Hamaker constants and van der Waals repulsion arises. Although
the van der Waals repulsion may be important in wetting phenomena and in phase separa-
tion from polymer solutions, there is very little evidence of such eect in colloidal disper-
sions. Practically for all aqueous dispersions, Hamaker constants lie in the range of
0.3010.0 10
20
J. Biological, and other low density materials normally have quite low
values of Hamaker constants. Increasing the ionic strength can signicantly reduce the
eective Hamaker constant further. For materials with Hamaker constants greater than
10
20
J, the van der Waals interaction can be assumed to be essentially independent of
the ionic strength.
Although the Hamaker approach is mostly used for determination of interaction
between particles, it must often be corrected for retardation eects, which arise because
of the electromagnetic characteristics of the van der Waals dispersion forces. It is often
assumed that retardation becomes signicant at a much closer approach. The forces can
be predicted more rigorously by direct computation based on the information about elec-
tromagnetic properties of the media utilising the Lifshitz or macroscopic approach [88].
Schenkel and Kitchener [89] proposed a simple expression for the magnitude of this inter-
action, which takes into account the eect of retardation. The term f(P) in the equation for
V
A
is the retardation factor and is given by
f (P) =
1
1 1:77P
for P 6 0:5 (20)
f (P) =
2:45
5P

2:17
15P
2
0:59
P
3
for P > 0:5 (21)
The form of the equation for total interaction energy is such that the van der Waals attrac-
tion always dominates both at small and large interparticle separations. At intermediate
particle separations, the behaviour depends critically upon the ionic strength and hence
the electrolyte concentration of the medium. Depending on the ionic strengths, the total
potential energy of interaction versus interparticle distance as depicted in Fig. 11, shows
four classes of shapes with large variations in stability [90,91]. At very low ionic strengths,
the potential energy curve (Curve A) represents only strong and long range repulsive
forces producing a totally dispersed system. At a slightly higher but still low enough ionic
strengths, there appears a primary minimum and a maximum in the total interaction en-
ergy prole (curve B). But the energy is still repulsive in nature.
The maximum in the energy prole represents a potential energy barrier against close
approach of the two particles and is of great signicance in colloid stability. The main
points of consideration are: (i) the height of the energy barrier, and (ii) the depth of the
potential well (primary minimum) at very small distances. Fig. 11 clearly explains that even
if it is energetically favourable for the particles to come into close contact, the two collid-
ing particles would need to possess sucient energy to overcome this energy barrier for the
formation of an aggregate. The height of this energy barrier depends upon the magnitude
of w
d
(and n) and upon the range of repulsive forces. For highly charged surfaces in dilute
electrolyte (i.e., long Debye length) there is a strong and long range repulsion resulting in a
high energy barrier. When the maximum potential energy is quite large enough compared
to the thermal energy (k
B
T) of the particles, the system should be stable. The role of coag-
ulant or polymeric occulants is either to lower the energy barrier by reducing the electro-
static repulsion and hence making it easier for the particles to come close to one another,
or to introduce some forms of interaction thereby destabilising the suspension and pro-
moting solidliquid separation. Once the barrier has been overcome, the particles should
be held in a deep primary minimum from where escape would be very unlikely. In principle,
van der Waals attraction is innitely strong on contact of particles and the primary min-
imum should be of innite depth. However, short range eects limit the closeness of
approach and hence the depth of the primary minimum in some cases may be quite
shallow.
However, in the intermediate ionic strength, there appears a primary minimum, a pri-
mary maximum and a secondary minimum (curves C and D). The secondary minimum in
the potential energy curves is a characteristic feature at relatively large interparticle dis-
tance in a reasonably more concentrated electrolyte solution. When the minimum is mod-
erately deep, compared with the thermal energy (k
B
T), reversible occulation may easily
take place [92]. Re-dispersion from the secondary minimum is also possible by diluting
the electrolyte solution. For small particles, the high value of maximum potential energy,
prevent coagulation into the primary minimum; the secondary minimum is also never deep
enough for the aggregation to occur. However, for particles of larger radii and irregular
shapes, the eect on aggregation due to secondary minimum is more pronounced in com-
parison to perfectly spherical particles.
+
-
Primary
minimum
I
n
t
e
r
a
c
t
i
o
n

E
n
e
r
g
y
van der Waals attraction
Electrostatic repulsion, V
R
A
B C
D
E
Energy
Barrier, Eb
Secondary
minimum
Particle
separation
Fig. 11. Total potential energy versus interparticle distance curve between two particles showing four dierent
types of interactions: A = spontaneous dispersion of particles; B = no primary coagulation due to high energy
barrier; C, D = weak secondary minimum coagulation; E = fast coagulation into primary minimum [90,91].
The colloid particles experience no repulsive force in a medium of high ionic strength
and fall directly into the deep primary minimum (curve E). Under such circumstances, fast
coagulation occurs and the system is completely unstable.
In the original DLVO theory, only the van der Waals and electrostatic interactions were
considered. Now it has also been identied that in addition to these forces, another cate-
gory of physical interaction has to be considered in order to get a complete theory of col-
loidal stability. Stabilization of colloidal dispersions may also be inuenced by steric
stabilization and structural forces. These mechanisms become important when there are
hydrophilic macromolecules adsorbed or bounded to the particle surface. Stabilisation
is caused by the repulsion between these adsorbed macromolecules. A schematic illustra-
tion of electrostatic and steric stabilisation is shown in Fig. 12. The steric stabilization
forces are generally short-range force (<2 nm). Presence of these forces can also change
the shape of the potential well that controls the particlesubstrate interaction. Caution
must be exercised in using sterically stabilized suspension for electrophoretic deposition
because the surface properties of the particles are altered completely for which the electro-
phoretic mobility will be very dierent from those of electrostatically stabilized suspension.
In extreme cases when the sign of surface charge is reversed due to adsorbed polymer the
deposition may fail or could occur on the counter electrode.
12. Mechanism of EPD process
Although the electrophoretic deposition has been applied successfully for many
applications, the exact mechanisms that allow a deposit to be formed are still not entirely
clear [93]. Fukada et al. [94] gives a comprehensive account of mechanism of deposit
formation by EPD. Bouyer and Foissy [95] suggest that EPD is a two-step process. Under
the application of an electric eld, the particles in the suspension rst migrate to one of the
electrodes, depending on the particle charge, where they eventually deposit. The migration
step involves the bulk properties of the colloidal dispersion (bath conductivity, viscosity,
particle concentration, size distribution, and surface charge density) and the actual eld
strength in the bath. The deposition step proceeds by a complex superposition of
Fig. 12. Schematic illustration of electrostatic and steric stabilization of suspensions. (a) Electrostatic
stabilisation and (b) steric stabilisation.
electrochemical and aggregation phenomena. The production of dense and cohesive
deposit requires that the particles lose their charge at the electrode.
12.1. Flocculation by particle accumulation
The rst attempt to explain the phenomenon of EPD was made by Hamaker [1] and
Hamaker and Verwey [96]. They pointed out that successful EPD needs stable suspension.
They observed that an EPD suspension, when allowed to stand, produced a strongly
adhering sediment. Therefore, they suggested that the formation of deposit by electropho-
resis is akin to the formation of a sediment due to gravitation and that the primary func-
tion of the applied electric eld in EPD is to move the particles towards the electrode to
accumulate. The pressure exerted by the incoming particles enables particles next to the
deposit to overcome the interparticle repulsion. This mechanism is feasible when deposi-
tion does not occur at the electrode, i.e., deposition on a dialysis membrane [2]. It explains
deposits on porous membranes that are not electrodes. Vanderperre [97] noted that, when
the solids loading is increased, the zeta potential of the particle shifts towards the isoelec-
tric point. This observation supports this mechanism.
12.2. Particle charge neutralization mechanism
Grillon et al. [98] suggested that particles would neutralize upon contact with the depo-
sition electrode or the deposit and then become static. This mechanism is important for
single particles and monolayer deposits. It explains deposition of powders that charge
on salt addition to the suspension. This mechanism explains initial stage deposition from
very dilute suspensions but is invalid under the following conditions: (a) EPD for longer
times (thick deposits), (b) when particleelectrode processes are prevented, e.g. semi-per-
meable membrane induces deposition between the electrodes, and (c) when reactions occur
at the electrode which alter the pH thereabout.
12.3. Electrochemical particle coagulation mechanism
This mechanism implies reduction of the repulsive forces between particles. Koelmans
[99] calculated the expected increase in ionic strength next to an electrode and found
that the ionic strength was of the same order as required to occulate a suspension. In
his view, the interparticle repulsion decreases due to the increase in electrolyte concentra-
tion near the deposition electrode. This in turn lowers the zeta potential and induces
occulation of particles which collapse to deposit. Since a nite time is required for the
electrolyte concentration to build up near the electrode, one expects that deposition would
not occur before a certain time has passed. Koelmans [99] indeed found that MgCO
3
par-
ticles suspended in methanol gets collected on the electrode as soon as the potential was
applied, and that they remain there only after certain critical time after voltage was cut-
o. The magnitude of the critical time was found to be inversely proportional to the
applied voltage to the second power. Hence the critical time can be very short, which
explains why it is frequently not observed.
This mechanism is plausible when the electrode reactions generate OH
ions, e.g., sus-

pensions containing water. This mechanism is invalid when there is no increase of electro-
lyte concentration near the electrode.
12.4. Electrical double layer (EDL) distortion and thinning mechanism
The explanation for invalidation of electrochemical coagulation mechanism when there
is no increase of electrolyte concentration near the electrode, was oered by Sarkar and
Nicholson [5] by considering the movement of a positively charge oxide particle towards
the cathode in an EPD cell as shown in Fig. 13. When the particle lyosphere system (the
counter ions from liquid around the charged particle forms what is called diuse double
layer or lyosphere) moves, uid dynamics and applied electric eld will distort the double
layer envelope in a way such that it becomes thinner ahead, and wider behind the particle.
The cations in the liquid also move to the cathode along with the positively charged par-
ticle. The counter ions in the extended tail will tend to react with these accompanying
Fig. 13. Electrical double layer distortion and thinning mechanism for electrophoretic deposition [5].
cations in high concentration around them. As a result of this chemical reaction, the dou-
ble layer around the tail of the particle will thin so that the next incoming particle (which
has a thin leading double layer) can approach close enough for London Van der Waals
(LVDW) attractive force to dominate and induce coagulation/deposition. The distortion
of the double layer leading to coagulation is plausible considering the high concentration
of particles near the electrode (or high collision eciency). Secondly, this mechanism
works for incoming particles with thin double layer heads, coagulating with particles
already in the deposit.
13. Multi-component deposition
Unlike the electrophoretic deposition of single component, the deposition of two or
more components simultaneously from the same suspension is somewhat complex and
tricky. This is of special signicance during deposition of composite or hybrid materials.
Unless due care is taken to ensure similar ionic charge and density around each compo-
nent, multi-component deposition would not be possible [36]. The particles with a positive
surface charge would deposit on the cathode whereas the negatively charged particles will
tend to deposit on the anode. Addition of a suitable additive like dispersant will have an
important role to play in these cases. However, the choice of additives should be made in
such way that the resultant sign and magnitude of surface charge on the particles are com-
parable. In some cases, although each of the particle species have same sign of charge, they
could deposit at dierent rates depending on the volume fraction of solids in the suspen-
sion. If the volume fraction of solids is high, the powders deposit at an equal rate. If how-
ever, the volume fraction of solids is low, the particles can deposit at rates proportional to
their individual electrophoretic mobility [44].
Fig. 14. Characteristic electrophoretic deposition of various ceramic powders observed in mixed solution of
acetylacetone (Acac) and ethanol (EtOH) under conditions of d.c. electric eld of 300 V cm
1
, concentration of
dispersed powders of 2.5 g l
1
, and deposition time of 23 min. For deposition of ST, propanol was used [60].
Fig. 15. (a) Dependence of depositionyield onthe composition ratio of acetylacetone (Acac) toethanol (EtOH) in the
systemhydroxyapatite (Hap) andyttriastabilizedzirconia (YSZ). Mixedratios of YSZtoHapwere (d) 25%, ( ) 50%,
and ( ) 75%. (b) Simulated dependence of yield on composition ratio of acetylacetone (Acac) to ethanol (EtOH) [60].
Borner et al. [100] pointed out that the particles with higher mobility will deposit faster
at the beginning of the deposition process. However, it also depletes the suspension faster
and, due to the dependence of the deposition rate on local concentration, the rate of depo-
sition of the high mobility component slows down. Yamashita et al. [60] observed this
eect is prominent at longer deposition times during the deposition of zirconia/hydroxy-
apatite. They employed mixed solvents (ethanol and acetylacetone), for the deposition of a
variety of ceramic powders such as hydroxyapatite (HAp), barium titanate (BT), stron-
tium titanate (ST), yttria stabilized zirconia (YSZ), magnesia, alumina, lead zirconate tita-
nate (PZT), and their mixtures on platinum foil. They observed eective deposition of
hydroxyapatite from its suspension in ethyl alcohol (EtOH), but very rare coating from
its suspension in acetylacetone (Acac) (Fig. 14). Strontium titanate (ST) also deposited
well from its suspension in EtOH compared to acetylacetone. On the other hand the depo-
sition yield of both YSZ and MgO increased with an increase in the amount of Acac in the
mixed solution as shown in Fig. 14.
Fig. 15 demonstrates the dependence of the deposition yield on both the composition of
solution media and the mixed ratio of powders. With increase in the ratio of Acac to
EtOH, there is rst a steep decrease in the yield of HApYSZ mixture to a minimum, then
an increase to the maximum values, thereafter a decrease again to 0. With a smaller mixing
ratio of YSZ to Hap, larger yield was obtained in lower mixing region of Acac to EtOH
while higher YSZ to Hap resulted in a larger yield in a medium to high ratio of EtOH to
Acac. The use of mixed solution experimentally proved to be eective for control of the
composition of deposited layers. Their simulated results (via the additive rule), agreed
reasonably well for <70% acetylacetone (Fig. 15). At higher than 70%, the deposition of
mixed powders is limited even in higher YSZ content, although YSZ is deposited well
in Acetylacetone. This large dierence between simulated and observed results may sug-
gest the interference of HAp with the behaviour of YSZ powders or the absorption of acet-
ylacetone on YSZ.
14. Drying of deposits produced by EPD
Depositing ceramic or other powder on a metal (or a conductive substrate) by EPD is
relatively simple. But the most important factor is how to avoid cracking in the ceramic
coating during drying and sintering. There have been reports of cracking of the deposits
during sintering specially in the cases of thicker deposits. Therefore, a careful control of
the sintering parameters is necessary to combat this problem. It is important that substrate
and as-deposited lm be homogeneous on a micron scale; large variations in composition
or green density of the substrate or lm could lead to dierential densication and warping
of the sintered bilayer. During drying and sintering, the shrinkage of deposit/coating could
be substantially dierent from the substrate depending on the material properties and
composition. As a result, tensile/compressive stresses are developed in the coating/sub-
strate and are relieved by the formation and propagation of cracks that originate from
aws or defects in them.
The following scenarios are possible [101]: (a) the lm shrinks more than the substrate
thereby putting the lm in tension (Fig. 16a) and results in porosity in the lm on appli-
cation of a force/weight on the bilayer during sintering; (b) the substrate shrinks more
than the lm putting the lm in compression (Fig. 16b); and (c) the lm and the substrate
have identical shrinkage proles and the shrinkage matches exactly leading to a at bilayer
after ring (Fig. 16c).
There are several approaches that can be adopted to avoid cracking during drying.
Recently, Sarkar et al. [47] reviewed critical issues of electrophoretic deposition and out-
lined strategies to avoid cracking of the deposit during sintering. When a wet coating or
green body undergoes drying, the origin of stresses in it is due to capillary forces. Cracking
can be avoided by minimizing capillary stresses either by using a low surface tension sol-
vent, or avoiding ne pore structure in the coating. However, attention must also be paid
to the evaporation rate of the solvents. Peng and Liu [45] presented an account of this fact
during drying and sintering of YSZ lm deposited on porous La
0.9
Sr
0.1
MnO
3
(LSM) sub-
strates, from suspensions in acetone and ethanol. Acetone has small surface tension but
high evaporation rate; it dries too fast when the lm is taken out from the solvent, leading
to cracks in the green YSZ lms. Ethanol has slower evaporating rate, but its large surface
tension tends to pull the YSZ lm o the substrate as the sample is taken out from the
suspension. In order to overcome these problems, a mixture of acetone and ethanol were
used subsequently in their experiments.
Capillary stresses can also be removed altogether by adopting freeze/supercritical dry-
ing since in this process the solvent phase is sublimed. Furthermore, controlled slow drying
via adjustment of vapour pressure of solvent in the drying medium will help control the
capillary stresses and as a result, formation of drying cracks may be avoided. For aqueous
electrophoretic deposition, the use of a high humidity oven for drying is generally found to
prevent cracks.
Ceramic coatings typically suer about 1015% linear shrinkage during sintering. Tra-
ditionally cracking during sintering is avoided by using a liquid phase during sintering; a
good example is sintering of glass enamel on a metal substrate. The composition is
adjusted in such a way that its thermal expansion is closely matched with the substrate.
As a result, it does not form crack during cooling from the sintering temperature.
Fig. 16. Schematic of dierent possible conguration of bilayer consisting of substrate and deposit on shrinkage
due to drying and sintering: (a) lm shrinks more than substrate; (b) the shrinkage of lm and substrate matches
exactly; (c) the substrate shrinks more than the lm [101].
To avoid cracking during sintering, one can also use a substrate that also shrinks during
sintering. Recently, this approach has been used, particularly in solid oxide fuel cell
(SOFC) fabrication where typically an YSZ electrolyte is deposited on a partially sintered
or an unsintered NiOYSZ cermet anode substrate. During sintering, both the substrate
and the coating shrinks, thereby avoiding cracks. Furthermore, the compositions of the
substrate and coating are chosen such a way that their thermal expansion coecients
match to each other, minimizing any thermal stress and resultant cracking during cooling
from the sintering temperature.
The problem of cracking in electrolytic zirconia deposits which usually occurs upon
drying has recently been addressed by the use of polymer additives [102,103]. It was shown
[102] that poly(diallyldimethylammonium chloride) (PDDA) acts as a binder, providing
better adhesion of zirconia deposits and preventing cracking. An important nding was
that the amount of organic phase in the deposits could be changed by variation of PDDA
concentration in solutions. These results pave the way for EPD of thick lms.
15. Design of electrophoretic apparatus
The design and construction of an electrophoretic deposition facility is straightforward,
an attraction of the process being its exibility with regards to green shape geometry. Flat
plates, crucible shape, tubes of circular or rectangular cross-section of any size can be depos-
ited by means of appropriate design of the mandrel or forming electrode. Although the
equipment requirement for electrophoretic deposition are simple, a number of design fea-
tures are needed to be taken into consideration. The materials used in construction of the
chamber must be selected carefully to avoid neutralization of the charge on the suspended
particles. It also must be stable in the solvent or its vapour during the deposition process.
If the size of the particles are large and deposition times longer, then continuous agitation
may be necessary to avoid gravitational settling. Agitation can be achieved by magnetic stir-
ring or by continuous peristaltic pumping. The chamber geometry needs careful design to
ensure a uniform electric eld between the electrodes. The thickness prole of deposit can
be inuenced not only by the eld distribution but also by the owpattern of the suspension
in the chamber. For uniform eld distribution between the electrodes, the surface area of
counter electrode is generally made relatively larger than the deposition electrode.
To our knowledge, there is no specic commercial design of any electrophoretic depo-
sition apparatus. Dierent research groups have employed a variety of dierent designs
depending on the requirement of dierent shapes. Most of the designs are based on depo-
sition on at surfaces [10,104108] although some designs on deposition of tubular shapes
[69,107] have also been adopted. For tubular shape designs, sometimes, the container itself
acted as the counter electrode.
16. Deposition on non-conducting substrates
Conventionally, one of the pre-requisite for electrophoretic deposition is that the sub-
strate be electrically conducting, for which most EPD processes reported in the literature
are on metallic or carbon/graphite substrates. In some instances, the deposition substrate
has been subjected to heat treatments in reducing atmospheres [109] or sputtering of a con-
ducting coating such as platinum [110] to make it electrically conductive before EPD. Mat-
suda et al. [111] used a thin layer of graphite coating on one side of the non-conducting
NiOYSZ porous substrate before EPD. The YSZ lms were deposited on the reverse side
that did not contain the graphite layer. Such preparatory step, however, make the EPD
process more expensive. If it were possible to deposit on non-conducting substrates, then
the EPD process would be more attractive technology for application in wide spectrum of
materials processing. Recently, we reported electrophoretic deposition of YSZ lms on
NiOYSZ substrate which were previously deposited electrophoretically on thin discs of
carbon sheets [53]. The NiOYSZ deposit along with the carbon sheet substrate was trans-
ferred into a YSZ bath followed by constant voltage EPD for deposition of YSZ. The
deposition of YSZ was possible only when the NiOYSZ substrate was saturated with sol-
vent. No deposition was possible on completely dried substrates. The carbon sheets gets
burnt o during subsequent sintering stage leaving behind a porous NiOYSZ with a thin
and dense YSZ layer on it. In this paper, we present conditions under which electropho-
retic deposition of YSZ is made possible on non-conducting NiOYSZ substrates which
eliminates the need for heat treatment in reducing atmospheres or the need for coating
a conductive backing. The YSZ lm thus deposited was found suitable as electrolyte for
solid oxide fuel cell (SOFC) application. In some subsequent communications [112,113],
the EPD of YSZ particles on the non-conducting NiOYSZ substrate was made possible
through the use of an adequately porous substrate which facilitates availability of electric
eld near the substrate. The porous substrates when saturated with the solvent, helps in
establishing a conductive path between the electrical contact and the particles in suspen-
sion. Deposition was found to increase with increasing substrate porosity up to a certain
value. Higher the applied potential, more was the deposition. For a given applied poten-
tial, there exists a threshold porosity value above which deposition by EPD was possible
(Fig. 17). No deposition was possible on substrates with porosity below the threshold
value. The microstructure of YSZ lm thus deposited is shown in Fig. 18. SOFC con-
structed on bilayers of NiOYSZ/YSZ with YSZ layer thickness of 40 lm, exhibited open
circuit voltage (OCV) of 0.86 V and power density of 263.8 mW/cm
2
when tested with H
2
as fuel and ambient air as oxidant.
0
0.01
0.02
0.03
0.04
0.05
50 55 60 65 70 75 80
Porosity, %
D
e
p
o
s
i
t
e
d

w
e
i
g
h
t
,

g
m100 V, 3 min
25 V, 3 min
Fig. 17. Inuence of substrate porosity on electrophoretic deposition of YSZ on non-conducting NiOYSZ, from
its suspension in acetylacetone (deposition area: 1.0825 cm
2
).
17. Application of EPD
17.1. Assembly of nanoscale particles into nanostructures and micropatterned thin lms
The emerging elds of nanoscience and nanoengineering are leading to unprecedented
understanding and control over the fundamental building blocks of all physical matter.
Today, the nanophase engineering expands in a rapidly growing number of structural
Fig. 18. Surface (a) and cross-sectional SEM image of YSZ lm (b) deposited on NiOYSZ substrate
(porosity = 72.55%) at 100 V for 3 min and sintered at 1400 C for 2 h.
and functional materials, both inorganic and organic. The rising interest in nanostructured
materials is because they often exhibit new properties that are remarkably dierent from
those of bulk materials, allowing the manipulation of mechanical, electrical, magnetic,
optical, catalytic and electronic functions. The ability to fabricate materials and structures
with sub-micrometer and nanoscale features reliably and economically is of interest in
many areas of science and technology. Signicant and vigorous research eorts are
focused on controlling the assembly of inorganic and metallic nanoscopic particles
[114]. The production of materials with micrometer, submicrometer and nanoscale pattern
is of importance in a range of applications, such as photonic materials, high density mag-
netic data storage devices, microchip reactors, and biosensors. One method of preparing
such structures is through the assembly of colloidal and nanoparticles.
The creation of nanophase or cluster-assembled materials is usually based upon the cre-
ation of separated small clusters which are then fused into a bulk-like materials or as a thin
lm or even by embedding into a solid matrix, polymers or glass either in a disordered or
ordered array. One specic goal in these investigations has been to tailor the size, shape,
and geometrical arrangement of nanoscopic particles, clusters, and aggregates in an eort
to produce desired properties. Ordered assemblies of nanometer-sized particles are a class
of nanomaterials that provide exceptional potentials to achieve one-, two- and three-
dimensional structures for a wide variety of applications ranging from photonic devices
to memory devices, two-dimensional array of magnetic nanoparticles, or single electron
microelectronic devices, quantum-conned size tunable luminescence behaviour, coulom-
bic staircase eects, photonic band-gap responses, optimization of localized electromag-
netic surface enhancement phenomena, etc. In order to make full use of this potential
for materials engineering, it is important to identify and gain control over the relevant
growth and ordering parameters.
Conventionally, micropatterned assembly of colloidal or nanoparticles have been
produced with lithographically patterned electrodes, or micromoulds. Majority of these
methods suers from drawbacks such as: (i) slow kinetics of assembly (hours to days),
(ii) surface particle density is sometimes dicult to regulate, (iii) diculty in creating pat-
terned assembly over large area. These drawbacks are largely a consequence of dealing
with very small particles for which the colloidal forces, i.e., buoyancy, frictional, and cou-
lombic forces outweigh the gravitational force and act to keep the particles in suspension.
Consequently, the particle transport is governed solely by Brownian motion, resulting in
completely random particleparticle and particlesubstrate collision.
In an attempt to circumvent some of these limitations, recent studies have focused on
creating templated nanoparticle assemblies using methods such as microcontact printing
of self-assembled monolayers (SAMs) [115], nanoetching [116] and e-beam lithography
[117] to fabricate spatially and density controlled nanoparticle architectures.
Since the colloidal particles are usually charged, the concept of electrophoretic deposi-
tion utilizing a directional force (external electric eld) has generated signicant interest
recently for patterned assembly of nanoparticles [118]. EPD of nanoparticles was rst used
by Giersig and Mulvaney [119,120] to prepare ordered monolayers of gold nanoparticles.
Prior to that this method had only been used to produce 2D and 3D ordered structures of
latex particles, such as polystrene and silica [121,122]. It has now been put forward by
some researchers that the EPD method can be developed into a general method to prepare
2D and 3D ordered structures of nanoparticles by means of using sols that maintain col-
loidal stable on the electrode/sol interface; however, this conclusion is based on the work
done on micrometer-sized polystrene, silica particles, and nanometer-sized gold particles
and it requires further evidence. Tabellion and Clasen [123] investigated the deposition
structure of gold, silver and rare-earth carbonate nanoparticles by EPD and found that
the composition and surface condition as well as the size distribution of the particles
can aect the order of the particles in the monolayer. It was also observed that particles
having similar diameter tended to pack together to form more orderly packed area com-
pared to particles with wide size distribution. The ordering of Au nanoparticle thus
obtained for dierent deposition conditions are shown in Fig. 19.
As already discussed, the colloidal and nanoparticles tend to remain in suspension for
long periods due to Brownian motion. They maintain their Brownian motion even as they
arrive on the surface, i.e., they do not become immobilized on the surface at lower voltages
and require higher voltages to overcome Brownian motion for attachment to the surface.
Boehmer [124] illustrated this fact by in situ observation of submicron sized latex particles
on indium tin oxide (ITO) electrode during electrophoretic deposition. Strong two-dimen-
sional clustering of the particles on the electrode surface was observed upon application of
a potential similar to those of Tabellion and Clasen [123] shown in Fig. 19. Interactions
between particles were observed over distances of several particle diameters, especially
for interactions between single particle and clusters. Even clustercluster aggregation phe-
nomena were observed. Once the clusters are formed, they rapidly grow and the distance
over which they attract newly arrived particles on the surface increases. Particles arriving
at a cluster move around its periphery until they reach their most favourable position, i.e.,
a position where they may be incorporated into the already existing lattice. It was also
reported by Boehmer [124] that with increasing salt concentration, the deposition rate
decreases because the conductivity of the suspension increases and, consequently, the
potential drop across the suspension becomes smaller. The decrease in deposition/
Fig. 19. Transmission electron microscope (TEM) images of Au nanoparticles on carbon coated copper grid
formed by EPD at 20 C (a) at 100 mV cm
1
for 5 min, (b) at 500 mV cm
1
for 5 min [123].
aggregation of the particles at the electrode with increasing ionic strength does not agree
with the DLVO theory. So the clustering is not a consequence of DLVO type interaction
as proposed by Giersig and Mulvaney [119,120] for gold nanoparticles on graphite. Here
the interactions were long range, extending over one or more particle diameter, which is
much larger than the Debye length. Boehmer [124] suggested that over this long range
the distortion of the electric eld by the particles and hydrodynamic interaction is impor-
tant and has to be considered to formulate possible interpretation of such observation.
Hayward et al. [125] proposed that once the particles are close to the surface, where they
remain mobile, electro-hydrodynamic or electro-osmotic eects assemble them into arrays.
Particles can be permanently attached to the surface by increasing the attractive forces
between the particle and the electrode. When the attractive forces exceed that due to steric
repulsion, entry into the primary minimum creates a permanent bond. Li et al. [126] pre-
sented the results of electrophoretic deposition of ligand-stabilized silver nanoparticles
(LSSN) synthesized by photochemical reduction. Their results indicate that the synthesiz-
ing conditions of LSSN, such as irradiation time during synthesis, and the concentration
of surfactant used, had a dominant inuence on deposit quality. When the irradiation time
was 5 min, the deposited lm was in the form of individual nanoparticles. However when
the irradiation time was increased to 10 min, the deposited lm was in the form of single
crystal. Lower concentration of surfactant led to better quality single-crystal silver lm.
Higher deposition voltage led to coalescence of LSSN in the lm. One of the major prob-
lems encountered during the direct deposition of gold nanoparticles (e.g., by solvent evap-
oration technique) is the interparticle interaction leading to aggregation eects [127]. Upon
aggregation, the metal nanoparticles lose the surface plasmon absorbance that is charac-
teristic of individual gold nanoparticles. These lms usually exhibit blue colouration
caused by the red-shift in the absorption band. One way to overcome these interparticle
interactions is to functionalise the gold nanoparticles (for e.g. with thiols). Chandrasekh-
aran and Kamat [127] reported deposition of three-dimensional network of gold nanopar-
ticles on a nanostructured TiO
2
lm by electrophoretic deposition at DC electric eld
between 50 and 500 V. Fig. 20 shows the absorption spectra of gold lm cast on nano-
structured TiO
2
lm obtained after dierent time of deposition, recorded using a UV/
VIS spectrophotometer. At early stages of electrophoretic deposition, the absorption is
Fig. 20. Absorption spectra of gold lms cast on nanostructured TiO
2
lms. The spectra were recorded at time
intervals of (a) 0, (b) 2, (c) 10, (d) 18, (e) 26, (f) 34, (g) 46, (h) 50, (i) 58, and (j) 70 min. A dc electric eld of 100 V
was applied to OTE/TiO
2
electrode in contact with 2.5 mM gold colloidal suspension in toluene containing
2.4 mM of tetraoctylammonium bromide (TOAB). The inset shows the absorption spectrum of 0.3 mM of Au
colloids in toluene [119].
dominated mainly by the TiO
2
lm (spectra a and b in Fig. 20). With increasing deposi-
tion time, an increase in the absorption was noticed in the visible wavelength range
(spectra cj). The prominent absorption maximum seen at 516 nm arises from the surface
plasmon band gold nanoparticles. The increase in the absorption of the surface plasmon
band with time represents the deposition of gold nanoparticles. By controlling the concen-
tration of gold particles in the toluene suspending medium, and the applied voltage, it was
possible to control the thickness of gold lm without inducing aggregation eects.
Recently, several experimental studies have demonstrated that connement of colloid
and nanoparticles in a suitable width/area can signicantly enhance colloid and nanocrys-
tal growth to produce single-crystal or close-to-single crystal structure. Kumacheva et al.
[128] showed how transition from a disordered state to strongly ordered state occurs in
two-dimensional arrays of colloidal microspheres, following their connement to thinner
gaps. The connement induces disorder-order transition at a well dened width of the gap.
Mondispersed polymethyl methacrylate (PMMA) particles of 0.58 lm size were electro-
phoretically deposited onto a substrate patterned with an array of electro-conductive
grooves whose progressively diminishing width was either commensurate or incommensu-
rate with the dimensions of a discrete number of colloidal spheres. Their results indicated
no noticeable dierence in ordering between particles deposited on non-patterned sub-
strate and those deposited on patterned substrates with groove width exceeding ca.
7.5 lm. The structures of the colloidal array was essentially disordered with occasional
ordered domains not exceeding 20 lm
2
(Fig. 21a). Layering of the particle was observed
Fig. 21. SEM images showing PMMA particle arrays electrophoretically deposited on (a) non-patterned, and (b,
c) patterned indium tin oxide (ITO) surface. The width of the grooves are 5.5 lm for (a) and 4.2 lm for (b, c)
[128].
to occur parallel to the rib walls when the groove width was ca. 6.0 1.3 lm. A dramatic
enhancement in organisation of the particles in 2D hexagonal close-packed array was
observed for groove width less than 4.7 lm (Fig. 21(c)). Kumacheva et al. [128] have also
observed that at the beginning of the electrophoretic deposition process, the structures of
colloidal array in the groove are essentially random. However, as more particles reach the
electrode, reorganization of the particles happen in the groove by squeezing of the newly
arriving particles between the already deposited ones and follows a synergistic particle
rearrangement. This resulted in large scale particle ordering for assembly of the colloidal
spheres in 4.2 lm wide groove. A quantitative measure of planar packing density for 2D
array of particles in the groove as a function of the groove width showed oscillation with
some periodicity. The theoretical width of groove required to accommodate a discrete
number of close-packed hexagonal particles was found to be about 5 3% smaller than
the experimental values of groove widths providing strong microsphere ordering. This dis-
crepancy is presumably caused because of a larger eective particle diameter due to elec-
trostatic repulsion between the particles.
Recently an interesting but signicant development has taken place in preparation of
size tunable ordered array of nanostructures by colloid sphere and block polymer template
assisted electrophoretic deposition. In this approach, templates are rst made by coating a
lm of colloid spheres of polystrene latex or block co-polymers micelles on the substrates
by drop coating or spin coating followed by their self-assembly or subjecting the lm to
selective chemical etching, ozonation, or through exposure to UV light treatment. The
above treatments can selectively remove segments of the block polymer leading to devel-
opment of dierent structural patterns. The form of structural patterns can be varied by
suitable choice of block polymer. Nanoparticles of desired materials are then incorporated
into these templates by electrophoretic deposition. Rogach et al. [129] reported impregna-
tion of luminescent CdTe nanocrystals into such template made of polystrene latex spheres
deposited on indium tin oxide (ITO) coated glass substrate by electrophoretic deposition.
It is noted that electrophoretic deposition technique also opens the possibility of prepara-
tion of uniform coatings from photonic crystals on curved substances such as spheres,
which would be impossible by means of gravitational or centrifugal force. Fig. 22 shows
electrophoretic impregnation of CdSe nanoparticles into nanotrenches in templates
prepared from polystrene-block-poly(methyl methacrylate) (PS-b-PMMA) diblock
copolymers [130]. The quantum dots thus prepared by this method maintained its photo-
luminescence property within the nanostructure.
17.2. Near shape manufacturing of complex-shaped glasses and ceramics
Many recent reviews on ceramic processing have claried that most traditional forming
methods such as dry pressing followed by machining, slip casting, pressure casting, injec-
tion moulding, etc., suers from dierent inherent problems like introduction of heteroge-
neities during processing, slowness of the process, prohibitive cost to form complex
shapes, etc. The dry pressing for example, is a fast fabrication method attractive for large
scale production, but involves high pressure requirements, develops density gradient in the
ceramic body with inhomogeneous microstructure, and needs cost intensive machining to
obtain complex shaped objects. All the drain-casting techniques such as slip casting, pres-
sure casting and centrifugal casting involves a solidliquid separation process to form
dense green bodies. But these traditional drain casting methods are plagued by some
generic problems which include slowness of the process, dependence of the suspension
properties on ow of liquid, development of stress gradient which may also lead to
Fig. 22. TEM images of template with nanotrenches generated from lamellar PS-b-PMMA diblock copolymer
thin lm: (a) before deposition; (b) after 1 min deposition time with an electric eld strength of 0.4 V/cm; (c) after
10 min deposition time with an electric eld strength of 0.8 V/cm [130].
non-uniform densities in the green body and causes mass segregation because of dierence
in particle size and density.
The major problem confronting the injection moulding is the removal of binder which
normally constitute about 2530 wt.% polymer for a 50 vol.% solids. Binder burnout must
proceed at a slow rate (taking up to several days) to avoid problems with slumping and
crack formation. The polymer removal time increases drastically when the size of the green
body increases, making it dicult to produce parts with thick cross-sections.
Drying process also has a major inuence on the green microstructure and production
rate. Drying is a critical operation, which has to be controlled to avoid cracking and warp-
ing. Fast drying can cause cracks. Decreasing the drying rate results in increasing green
densities. During drying, transport of evaporating dispersing media can cause binder
and small particle migration to the surface. This can lead to additional problems during
burnout and sintering. These problems can be minimised or avoided when the binder con-
tent is low or the dispersing media is sublimated.
Another aspect of concern when casting submicron and nanosized powders is the
attainment of limited solid loading and hence green density due to the high surface area
of the particles. The low green density results in a high shrinkage during drying and sin-
tering. Thus sophisticated process control is necessary for larger and more complex-
shaped components. This makes near-shape manufacturing very complicated. One possi-
ble solution is to increase the green density signicantly. This can be achieved by combin-
ing powders with distinctly dierent particle size distribution, like mixture of nanosized
and microsized particles. It is important that no size dependent separation of the particles
occurs during shaping because this can result in inhomogeneous sintering behaviour and
distortion of the component.
Since the electrophoretic deposition process is not dependent on ow of liquid and also
uses little or no binder, it is being looked upon as a suitable method for fabrication of near
net shaped glasses and ceramics. Tabellion and Clasen [105] demonstrated that near-shape
manufacture of complex structures and large components is possible by EPD from aque-
ous suspension. The shaping of complex silica glass and zirconia components, like tubes or
structured parts were made by EPD. Three-dimensional shaped porous polymer moulds
were used as ion-permeable deposition surface (Fig. 23a). Fig. 23b shows the sintered zir-
conia components shaped by EPD on porous moulds and subsequent ring. To enable
near-shape manufacturing mixtures of nanosized and microsized particles were electro-
phoretically deposited. By combining nanosized powders with micrometer powders green
density could be increased signicantly and shrinkage could be minimized (<12%).
17.3. Solid oxide fuel cell (SOFC) fabrication
Solid oxide fuel cells (SOFCs) have attracted great attention as new electric power gen-
eration system because of their high energy conversion eciency, clean power generation,
reliability, modularity, fuel adaptability, noise-free, excellent long term stability and the
versatile nature of the technology for direct conversion of chemical energy to electrical
energy [131]. The potential of solid oxide fuel cells (SOFCs) to meet future electric power
demand, utilizing the current fuel resources, is well described in the literature [132,133]. In
general, an SOFC consists of a stack of multiple single fuel cells. A single SOFC cell in
turn comprises of a solid electrolyte layer with an oxidizer electrode (cathode) on one side
of the electrolyte and a fuel electrode (anode) on the other side. The electrodes are required
to be porous, or at least permeable to oxidizer at the cathode and fuel at the anode, while
the electrolyte layer is required to be dense so as to prevent leakage of gas across the layer.
While the existing SOFC technology has demonstrated much higher energy eciency with
minimal pollutant emission over conventional energy technologies, the cost of the current
SOFC systems is still prohibitive for wide commercial application. To be economically
competitive, the cost of the materials and fabrication must be dramatically reduced.
Yttria-stabilized zirconia (YSZ) is by far the most popular material used as SOFC elec-
trolyte because of its unique combination of properties such as high chemical and thermal
Fig. 23. Porous polymer moulds (a) and sintered zirconia component (b) shaped by EPD from aqueous
suspension of nano and microsized zirconia suspension [105].
stability and pure ionic conductivity over a wide range of conditions. Solid oxide fuel cells
based on YSZ have been developed for high operating temperature range of 9001000 C.
Such high operating temperature was advantageous as it was benecial for internal
reforming of fuels such as natural gas, promotes rapid electrocatalysis with non-precious
metals, and produces high quality byproduct heat for cogeneration, but it normally
induced some adverse inuence on the cell and/or stack stability due to degradation
[131,134]. Thus reducing the operating temperature of SOFC has been one of the hottest
issues for the commercialization of SOFC in the last 10 years. The motivation for reduced
operating temperature SOFCs to below 800 C or less includes reduction in the degrada-
tion of cell components, greater exibility in cell design, lower manufacturing cost by
broadening materials choices as cheap and readily available ferritic steel can be used for
the interconnector [135,136]. However, the electrolyte conductivity and electrode kinetics
drop signicantly with lowered operating temperature. This can be overcome by lowering
the electrolyte resistance (i.e., ohmic losses across the electrolyte can be minimized) either
by decreasing the electrolyte thickness or with alternative materials of higher ionic conduc-
tivity at lower temperatures. Although it has been proposed elsewhere that LaGaO
3
-based
oxides [137] and cerium oxide doped with gadolinium (GDC) [132,138] exhibits high oxide
ion conductivity to be useful as electrolytes in intermediate temperature SOFCs, the pro-
duction of thin lms from solid electrolytes still has been important for the development of
commercial SOFCs. Recently, considerable eorts have been directed by a number of
groups worldwide to reduced-temperature SOFCs based on thin lm electrolyte. Several
methods currently used for thin lm deposition vary greatly with respect to methodology
and result [139]. These methods include the physical vapour deposition (PVD) such as
sputtering, pulsed laser deposition, molecular beam epitaxy (MBE) [140], chemical vapour
deposition (CVD) or electrochemical vapour deposition methods (EVD) [141143], com-
bustion chemical vapour deposition (CCVD) [144], plasma technologies [145,146].
However, the PVD and CVD deposition methods ordinarily require sophisticated and
expensive equipment making them either undesirable or impracticable for implementation
in manufacturing environment. They are also plagued by high processing temperatures
and limitations on the materials from which the support anode is made.
To make thin lm solid oxide fuel cells more ecient and less expensive to fabricate,
improved method for forming the porous electrode and non-porous electrolyte used in
such devices are needed. The colloidal deposition routes have been proven to be simple
and less expensive processing method for many advanced ceramics [2]. The colloidal
method such as dipcoating, slipcasting, etc. though inexpensive are rather poor with
regard to controlling the deposition. Therefore, the development of alternative method
for the preparation of a thin, but gas tight electrolyte lm remains a challenging project.
Considering the vast elds of application, the EPD technique is being recognized to
hold a great potential for economic fabrication of thin, dense and gas tight electrolyte
as well as porous electrodes for SOFC applications. However, in spite of these promises,
there seems to be little application of EPD in SOFC technology as evident by the availabil-
ity of only a handful of related literature, possibly due to the lack of a viable EPD chem-
istry and process development for the application, or due to the need for more precise
process control and consequently the need for higher trained operators compared to the
other common production methods. To our knowledge, the rst published account of
using EPD for the production of zirconia electrolytes for SOFCs was reported by Ishihara
et al. [30,51,147,148]. In these studies, zirconia electrolyte lms were deposited on
platinum-coated-nickelCaO-stabilised ZrO
2
(NiYSZ) cermet anode and substrate of
porous Sr-doped LaMnO
3
(LSM) cathode form acetylacetone slurry, using at least six
deposition steps, each followed by a sintering step. Although it was possible to produce
thin and gas-tight YSZ lm with high cell performance, the method is not suitable for mass
production because the technique of multiple deposition and sintering steps is compli-
cated, time-consuming and inordinately expensive. In addition, without the multiple depo-
sition steps, a gas-tight electrolyte layer and acceptable fuel cell performance could not be
obtained. Following these reports, Basu et al. [41,149,150] attempted to use one step EPD
method to deposit dense YSZ electrolyte on a porous doped LaMnO
3
for tubular solid
oxide fuel cells. They used a carbon interlayer sputter deposited by high vacuum sputtering
apparatus on the porous doped LaMnO
3
substrate prior to deposition of YSZ by EPD.
On ring at 1250 C, the lm produced without carbon interlayer had more and larger
pores, a less even surface topology, and a less uniform grain size distribution, which
became more pronounced at 1300 C. The lower surface roughness and better packing
density of the coatings produced using graphite interlayers was attributed to the more-
controlled deposition and equipotential electric-eld distribution created on the porous
substrate when the interlayer is present. Although, the carbon interlayer approach pro-
duced reasonably good YSZ lm, it increases the cost of deposition. Peng and Liu [45]
and Chen and Liu [31] demonstrated that dense YSZ thin lms can be prepared on porous
La
0.85
Sr
0.15
MnO
3
(LSM) substrate (of solgel derived powder) by electrophoretic deposi-
tion, followed by sintering at 1250 C which is about 200 C lower than other lm depo-
sition approaches reported in literature. The densication of the YSZ lm at such low
temperature was due to the large shrinkage of the LSM substrate (using the solgel derived
powder) which greatly enhances the densication process. However, no report was made
of any fuel cell performance. Zhitomirsky and Petric [151,152] reported the electrophoretic
deposition of La
0.85
Sr
0.2
Ga
0.875
Mg
0.125
O
3x
(LSGM), La
0.8
Sr
0.2
Co
0.2
Fe
0.8
O
3d
(LSCF),
and (Ce
0.8
Gd
0.2
)O
1.9
(CGO) on Ni foils and NiYSZ substrate prepared by tape casting.
The goal of the work involved nding a common solventbinderdispersant system for
cathodic EPD of these materials. Although, ethyl alcohol, phosphate ester (PE) and poly-
vinyl butyral (PVB) were identied as suitable solvent, dispersant, and binder, respectively,
for electrophoretic deposition, the CGO and YSZ lm thus obtained were highly porous
even after sintering at 1400 C. Therefore, further optimization of the deposition process
and thermal treatment procedures are necessary in order to obtain dense deposits for
application as electrolytes in fuel cells. Self-supported dense lms of 4080 lm thickness
were fabricated from LSGM by EPD of those powders on graphite substrate followed
by sintering at high temperature [153]. But the sintering cycle required rst stage heating
to 800 C, holding for about 9 h, followed by further heating to 1500 C and curing for
10 h. Such long sintering cycles are not only energy intensive but also time consuming.
The SOFC constructed on the lms exhibited power densities of 0.34 and 0.50 W/cm
2
at 600 and 700 C, respectively. Will et al. [109] reported the EPD processing of thin zir-
conia electrolytes on porous anodic substrates (NiO/CeO
2
/ZrO
2
) which were prepared via
tape casting. In this study, emphasis was put on the kinetics of the deposition process
(including direct determination of the deposited layer thickness during EPD process)
and not on achieving optimal values of the SOFC for maximum performance. Since the
substrates for EPD are restricted to conductive materials, the NiO was reduced to metallic
Ni by heat treatment in 10% H
2
and 90% Ar at 700 C before the EPD experiments. The
SOFC consisting of the Ni-cermet anode, 20 lm zirconia layer processed via EPD, and a
Pt cathode of 50 nm sputter coated on it exhibited a power density of 200 mW/cm
2
at
0.5 A/cm
2
and 700 C in a 3 vol.% H
2
, 97 vol.% N
2
atmosphere saturated with water.
As evident from the literature above, a great deal still remains to be done for commer-
cial utilisation of electrophoretic deposition for solid oxide fuel cells. Preparation of con-
ducting substrate, selection of suitable solvent, development of a suitable EPD chemistry,
optimization of processing parameters for obtaining homogeneous, uniform and crack
free lms still remains an important subject of study.
Recently we reported electrophoretic deposition of YSZ lms on NiOYSZ substrate
which were previously deposited electrophoretically on thin discs of carbon sheets [53].
The NiOYSZ deposit along with the carbon sheet substrate was transferred into a
YSZ bath followed by constant voltage EPD for deposition of YSZ. The deposition of
YSZ was possible only when the NiOYSZ substrate was saturated with solvent. No depo-
sition was possible on completely dried substrates. The carbon sheets gets burnt o during
subsequent sintering stage leaving behind a porous NiOYSZ with a thin and dense YSZ
layer on it. Fig. 24 presents the NiOYSZ bilayer plus a layer of SOFC cathode painted
from a paste of LSMYSZ (50:50 mixture), after fuel cell testing with H
2
as fuel upto
800 C. The fuel cell performance is shown in Fig. 25.
17.4. Laminated materials
Layered materials can also be produced via EPD. When the desired thickness of the
rst layer is reached, the deposition electrode can be moved to a second suspension for
deposition of a layer of dierent composition. By changing back and forth, a layered mate-
rial is readily obtained. Nicholson et al. [154] have produced ZrO
2
/Al
2
O
3
laminates with
alumina layers as thin as 12 lm and zirconia layers of 2 lm from ethanol-based suspen-
sions. The boundaries between layers were straight and well dened showing that although
EPD can be fast process, good control of the growth of the layers can be obtained. The
same group also produced alumina/lanthanum laminates [155]. Ferrari et al. [156] and
Fischer et al. [50] produced alumina/zirconate laminates from aqueous suspensions. Hecht
et al. [157] prepared superconducting multilayer tapes of (Tl, Pb)-1233 on silver tapes.
Fig. 24. A cross-sectional view (SEM) of NiYSZ/YSZ/LSMYSZ after testing under H
2
atmosphere at 800 C
[53].
Vandeperre and Van der Biest [44] made a range of SiC-based interlayers. They also pro-
duced laminated SiC/graphite composite tubes [158], thus combining the ability of EPD to
produce laminated materials with the shaping capabilities of the process. Recently, You
et al. [159] reported the fabrication of SiC/TiC laminated structure by electrophoretic
deposition from acetone-based suspensions (Fig. 26).
17.5. Functionally graded materials
While layered materials are obtained by immersing the deposition electrode in dierent
baths, graded materials can also be made by gradually changing the composition of the
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
1.1
0 200 400 600 800 1000 1200 1400 1600
Current density (mA/cm
2
)
C
e
l
l

V
o
l
t
a
g
e

(
V
)
0
100
200
300
400
500
0 200 400 600 800 1000 1200 1400 1600
Current density (mA/cm
2
)
P
o
w
e
r

d
e
n
s
i
t
y

(
m
W
/
c
m
2
)
800
o
C
750
o
C
700
o
C
Fig. 25. Cell voltage and power densities as a function of operating current density for a SOFC with
conguration of NiO:YSZ (60:40 by weight)/YSZ/LSMYSZ (50:50 by weight) fuel cells [53].
Fig. 26. SiC/TiC laminated structure produced by constant-current electrophoretic deposition (solids load-
ing = 50 g/l, deposition time for each layer = 1 min) [159].
suspension from which EPD is carried out. Sarkar et al. [56] demonstrated the ability to
formgraded materials by slowly adding an ethanol-based suspension of an alumina powder
to an ethanol-based suspension of an yttria-stabilized zirconia powder during deposition. A
gradual increase in the alumina content of the deposit was observed. Later, the same group
also produced Al
2
O
3
/MoSi
2
- and Al
2
O
3
/Ni-graded materials [160,161]. Zhao et al. [162]
produced alumina-stabilized zirconia-graded rods from an acetone based suspension. Put
et al. [163] deposited nanocrystalline WC-Co composites with a gradient in cobalt content
by means of EPD of the green materials and subsequent pressure less sintering (Fig. 27). A
starting suspension containing 100 g/l WC-6Co in acetone/n-butylamine was pumped into
deposition cell by peristaltic pump. A second suspension containing 400 g/l WC-25Co was
added to the circulating suspension by another pump allowing to continuously change the
cobalt concentration from 6% upto 17% at the end, because some WC-6Co powder is still
present in the suspension at the end of the experiment.
17.6. Hybrid materials
Composites and inorganicorganic hybrid materials have been proven to exhibit supe-
rior properties than the conventional materials. Interesting applications of inorganic
organic hybrid materials have been reported for water-repellant coatings, optical
waveguides, dielectric lms and others [164,165]. Most of the hybrid materials are based
on organofunctional silanes, which contribute to the siloxane backbone and at the same
time play the role as a carrier of organic functions. The incorporation of various metallic
elements other than Si are being investigated to alter properties of the hybrid materials
[166,167]. To make full use of the properties derived from particles, it is important to con-
trol the arrangement of particles with high packing density in hybrid materials. The elec-
trophoretic deposition have been found to enable desired particle arrangement and
packing density with various shapes [5]. A necessary condition of controlling the deposi-
tion process is the same electrophoretic mobility of the two components in the suspension.
Ferrari et al. [168] reported the co-deposition of Al
2
O
3
/Y-TZP by electrophoretic deposi-
tion. The problem of poor adhesion and shape retention at the substrate that leads to low
density, cracking and heterogeneous surfaces were overcome by consolidating the deposits
Fig. 27. Backscattered SEM micrographs of WC-6Co/WC-25Co functionally graded materials obtained by
constant voltage electrophoretic deposition at 800 V. The second suspension was added after 1 min deposition
with rst suspension (d = distance from the low cobalt side) [163].
immediately by thermogelation of polysaccharides, which is introduced in the suspension.
Hadraba et al. [169] obtained homogeneous distribution of individual components of
Al
2
O
3
and ZrO
2
over the whole deposit cross-section (Fig. 28) by maintaining identical
electrophoretic mobility of Al
2
O
3
and ZrO
2
in isopropanol suspensions stabilized by
monochloroacetic acid.
17.7. Fibre reinforced ceramic matrix composites
Electrophoretic deposition (EPD) is a simple and cost-eective method for fabrication
of high-quality bre reinforced ceramic matrix composites. In this application, EPD is
used to inltrate preforms with tight two- or three-dimensional bre architectures using
nanosized ceramic particles. A recent comprehensive review article reveals the great variety
of conducting and non-conducting bre and matrix combinations that have been explored,
including SiC, carbon, and oxide ceramic bre architecture and silica, borosilicate glass,
stainless steel, alumina, zirconia, mullite hydroxyapatite, SiC and Si
3
N
4
matrices [170
172]. Kaya et al. [107] used EPD to inltrate preforms with tight bre weave architectures
using dierent anodized ceramic particles, including silica and boehemite sols, as well as
dual-component sols of mullite compositions. Fig. 29 shows the EPD inltrated Ni-coated
Fig. 28. Microstructure of Al
2
O
3
/ZrO
2
composite microstructure obtained by EPD [169].
Fig. 29. Ni-coated carbon bre perform inltrated with boehmite sol [170].
carbon bres reinforced alumina matrix composites containing 30 vol.% bre loading. The
Ni-coated carbon bre perform was fully inltrated with the boehmite sol even to regions
where the bres were nearly touching each other, leading to high quality deposit.
18. Modeling of EPD process
A distinct feature of electrophoretic deposition or any other colloidal processing of
ceramics is the large area of contact between the particles and the dispersing medium.
Hence interparticle (or surface) forces strongly inuences suspension behavior and powder
packing density during deposition/shaping. In EPD it has been suggested that the primary
function of the applied electric eld is to accelerate the charged particles towards the elec-
trode of opposite charge, the electrostatic force being the driving force. In the case of low
concentrated suspensions, the motion of particles is determined by equilibrium between
electrical and frictional forces and a constant drift velocity can be found. When the solid
load becomes higher close to the electrode surface, the mobility of individual particle will
be restricted and a collective pressure onto the particles closer to the electrode surface is
supposed to develop. The accumulated particles will be forced to occulate and form a
solid packing structure. Moreover local occulation near the electrode surface may be
induced by electrolytic reactions which gives rise to a distinct shift of the pH. Thus, if
deposition in an aqueous suspension occurs on a cathode, pH may be increased signi-
cantly to the basic region, which may cause particles stabilized in acidic conditions to oc-
culate. All these factors must be taken into account while developing model for EPD
process.
Mathematical modeling of constant voltage electrophoretic deposition from stirred sus-
pension was reported recently by Gonzalez-Cuenca et al. [173]. Based on the rst principle,
the inuence of deposit formation on deposit growth was implemented, which is a rene-
ment of the model described earlier by Biesheuvel and Verweij [29] and already presented
by Eq. (3). For a stirred suspension, concentration gradient ($/
s
) will not form and the
volumetric particle concentration in the suspension (/
s
) is given by an overall mass bal-
ance for the particles in the suspension
d(/
s
V )
dt
= /
s
dV
dt
V
d/
s
dt
= Au
d
f
d
(22)
where V is the volume of the suspension and A is the electrode surface area, u
d
is the
growth rate of the deposit, and f
d
is the deposit packing factor (unity minus porosity).
In the above equation, the mass density of liquid and the particles is assumed constant.
On substituting the overall mass balance for the entire suspension given by
dV
dt
= Au
d
(23)
in Eq. (22), the kinetic equation for volumetric particle concentration in the suspension
becomes
d/
s
dt
=
A
V
u
d
(/
d
/
s
) (24)
According to Zhang et al. [174] the kinetic equation for deposited weight (w) can be
expressed as an exponential function of time
dw(t)
dt
= w
0
k exp(kt) (25)
where
k =
A
V
en
4pg
(E DE) (26)
in which, w is the weight of the solid particle deposited on the electrode, k is the kinetic
constant, t is the deposition time, A is the area of the electrode, V is the volume of suspen-
sion, w
0
is the starting weight of the solid particle in the suspension, e is the dielectric con-
stant of the liquid, n is the zeta potential of the particle in the solvent, E is the applied DC
voltage, and DE is the voltage drop across the deposited layer. Wang et al. [42] suggested
that for uniform and dense packing of deposit as was the case for ZnO nanoparticles, it is
more convenient to use the deposited thickness (h) instead of the weight (w) to model the
deposition kinetics. The deposited weight as a function of h can be expressed as
w(t) = Ah(t)q (27)
where q is the density of the particle. By combining Eqs. (25) and (27), and assuming con-
stant density of deposit with time, Wang et al. [42] arrived at the following kinetic equation
for electrophoretic deposition:
dh(t)
dt
= k
/
exp(kt) (28)
and
k
/
=
kw
0
Aq
=
w
0
V q
en
4pg
(E DE) (29)
where k
/
has the unit of velocity (cm/s). For relatively short deposition time, a linear func-
tion for the deposited thickness and time is expected and Eq. (29) is simplied to the fol-
lowing form:
h(t) = k
/
t (30)
Cordelair and Greil [175] used discrete element method (DEM) to gain insight into the
kinetics determining particle packing and density gradient microstructure during deposi-
tion of colloidal ZrO
2
from aqueous suspension. In DEM, each particle is treated as an
individual element, each keeping its mass, radius and charge as a function of time and
location, as well as parameters from local suspension properties such as ionic concentra-
tion, Debye parameter, pH and electric eld strength. These data can be used to trace the
movement of each powder particle in the suspension and thus allow to predict the particle
packing behavior as derived from local suspension and particle properties. Depending on
pH, electrolyte concentration, current density and mass ow, the particle zone close to the
deposit layer mutually repel (stable state), weakly attract (occulated state) or strongly at-
tract (coagulated state) each other as shown schematically in Fig. 30. In the stable state the
particles form highly ordered deposit with a maximum packing density on the electrode
(Fig. 30a). Formation of regions where the particles are weakly bound to each other (in
the secondary minimum of the interaction energy function) characterises the occulated
state (Fig. 30b). These aggregates tend to form non-uniform packing structures. The
aggregation process of coagulated colloid (Fig. 30c) clusters can be viewed best as diusion
limited aggregation. Depending on the solid loading, large but deeply ssured clusters are
generated. The maximum possible packing density (hexagonal close packing) is generally
not achieved due to incorporation of packing defects.
Studies of electrodynamic particle aggregation during EPD both under steady [176] and
alternating [177] electric elds have been conducted recently, which have led to equations
for the time evolution of the probability of separation between deposited particles under
dierent conditions. The models are useful to explain the experimentally observed cluster-
ing of colloidal particles near an electrode in a DC electric eld by considering convection
by electro-osmotic ow about the particles [178]. Recently numerical simulations have
been used to model the buildup of a deposit of charged particles on an electrode during
EPD [179,180]. These studies provide insight into local variations of particle interaction
Fig. 30. Particle distribution structures in the Nerst layer (a) stable state, (b) occulated state, (c) coagulated state
[175].
processes during deposition, which can be used for optimization of EPD techniques. Sar-
kar et al. [181] observed that the deposition of silica particles on silicon wafer with time
was strikingly similar to nucleation and growth of silica particle layer with that of atomic
lm growth via molecular beam epitaxy. This indicates possible new directions for further
research as the equivalence between the two processes provides insight into the growth
kinetics of EPD lms and can be used for their microstructural optimization.
19. Concluding remarks
The electrophoretic deposition process has gained considerable interest in recent years
for fabrication of advanced materials. The process is simple, easy to use and cost-eective
method of deposition, which nds innumerable applications including thin and thick lm
deposition, layered ceramics, hybrid materials, bre reinforced composites as well as nano-
composites, nanoscale assembly of 2-D and 3-D ordered structures and micropatterned
thin lms. However, the process needs judicious choice of solvent media such that an
appreciable magnitude of surface charge is developed on the powder surface in the suspen-
sion to ensure stability of the suspension as well as facilitate high electrophoretic mobility.
Although the mechanisms are still completely not clear, the possibility of deposition on
non-conducting substrates opens up a whole new range of applications including gas sep-
aration sensors, thermal barrier coatings, etc. However, it requires further research in fun-
damental understanding of the mechanisms by appropriate modeling of the process,
charge development in non-aqueous suspension for proper control of suspension stability
and deposition. The non-aqueous suspensions are popular media for electrophoretic depo-
sition. But development of aqueous electrophoretic deposition will go a long way in reduc-
ing cost of deposition and also minimise environmental concerns associated with use of
non-aqueous suspensions.
Acknowledgements
This work was supported by the US Department of Energy SECA Core Technology
Program (under Award Number DE-FC26-02NT41572). One of the authors (L.B.) is
thankful to the Department of Science and Technology (DST), Govt. of India, for the
BOYSCAST fellowship (Award No. HR/BY/E-11/2003). Permission of the Director,
Regional Research Laboratory, Bhubaneswar, to publish this paper is duly acknowledged.
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A review on fundamentals and applications

of electrophoretic deposition (EPD)

; however, the presence

, resulting in an absolute value of the zeta potential greater

ions in the suspension. It is, however, noted that

ions can also be conrmed

impurities from surface of the particles

ions by electrolytic dissociation. The zeta potential is inuenced by the

ions, e.g., sus-

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