Journal
, 82 [11] 303136 (1999)
Role of Ionic Depletion in Deposition during Electrophoretic Deposition
Ceramic Research Group, Department of Materials Science and Engineering, McMaster University,
A model is developed for deposition during the electropho-
retic deposition (EPD) process. It suggests that ions that
move with the charged particles in suspension are depleted
at the depositing electrode, locally changing the pH toward
the isoelectric point (pHiep) to give coagulation. The varia-
tion of zeta () potential is modeled via chemical-equi-
librium and surface-adsorption isotherms. The model suc-
cessfully fits the experimental data for Al2O3 particles in
ethanol when the Freundlich surface-adsorption isotherm
is assumed. Calculations predict the co-ion concentration
gradient as a function of location within the suspension,
and the deposition time and its role in the coagulatoin pro-
cess during EPD.
I. Introduction
I N ELECTROPHORETIC DEPOSITION (EPD), colloidal, charged
particles deposit from a stable suspension onto an oppositely
charged electrode upon application of a dc electric field. It is a
facile and precise technique to synthesize monoliths and com-
posites from nanoscale to several millimeters thickness. It can
also produce complex geometries and functionally graded ma-
terials (FGM).1 Sarkar and Nicholson2 recently reviewed the
mechanisms and kinetics of EPD and the application thereof to
ceramics.
Most significant in the EPD of laminates is the high perfec-
tion of the microstructures produced, particularly the inter-
faces.3 There are five methods of ceramic laminate production.
Four involve natural forces (capillary suction, centrifugal
force); slip-casting utilizes capillary forces, pressure- or
vacuum-casting adds pressure or suction, and centrifugal-
casting uses centrifugal force. In tape-casting, the shear action
of the doctor blade lays up the polymeric chains and produces
tapes of 50% organic material. The fifth method, EPD, in-
volves electrohydrodynamic and electrochemical forces in low-
concentration suspensions (<5 vol% solids). EPD from a low-
concentration suspension is possible because every particle in
the suspension can be deposited.
In slip-, centrifugal-, or pressure-casting, the liquid is in-
duced to move and carries the particles with it. The casting
(deposition) process involves the liquid moving, carrying the
ions through the building cast. The flight of ions reduces the
zeta () potential and the particles coagulate. In contrast, in
EPD the particles move while the liquid remains approximately
motionless. Deposition during EPD involves a different mecha-
nism and is the subject of this work. The liquid in EPD expe-
riences no bulk force; the ions and the particles do. It will be
shown that the mandatory pre-step to deposition, i.e., particle
coagulation, is the result of local pH change of the suspension
due to ionic discharge.
J. A. Lewiscontributing editor
Manuscript No. 190095. Received June 22, 1998; approved May 25, 1999.
*Member, American Ceramic Society.
**Fellow, American Ceramic Society.
To whom correspondence should be addressed.
3031
J. Am. Ceram. Soc.
Debnath De* and Patrick S. Nicholson**,
Hamilton, Ontario, Canada L8S 4L7
Several explanations of particle coagulation during EPD
have been advanced. Koelmans and Overbeek4,5 proposed that
the increase of electrolyte concentration caused by electro-
chemical reactions at one of the electrodes induces particle
coagulation. Shimbo et al.6 suggested that polymerization of
adsorbed hydroxides produced by secondary processees at the
depositing electrode causes the particles to adhere. Mizuguchi
et al.7 hold that charge neutralization of particles upon touching
the electrode brings them together. Brown and Salt8 calculated
the minimum deposition field strength required for oxide par-
ticles in organic media (25500 Vcm1) but found actual ex-
perimental values are 510 times less. Hamaker and Ver-
wey9,10 explained this discrepancy in terms of a pressure
generated by accumulated particles causing deposition. This
explanation is doubtful since Giersig and Mulvaney11 recently
deposited a monolayer of gold particles by EPD at the rela-
tively low field strength of 0.55 mVcm1. Since particles can
deposit on either the cathode or the anode, depending on their
surface charge sign, and noble metals and carbon can be de-
posited, hydroxide formation and polymerization explanations
are not plausible.2
The deposition process during EPD has not been satisfacto-
rily explained. It was thought that the particles simply dis-
charge to give current passage and the now-neutral particles
coagulate. To investigate whether current passage during EPD
is due to discharge of particles, Sarkar and Nicholson2 per-
formed a dialysis membrane experiment in an Al2O3 suspen-
sion. They separated the deposition cathode from the suspen-
sion by a dialysis membrane permeable only to ions. They
observed a dense deposit on the surface of the membrane and
current passage in the system via ionic discharge. Thus, the
majority charge in EPD is carried by the ions of the system and
the current passage is the result of their discharge.2 This ob-
servation rules out paticle/electrode reactions as the major pro-
cess. Sarkar and Nicholson2 suggested that, during electropho-
resis of the particles, the shear force between the envelope of
double-layer around a particle and the bulk fluid streamlines
the double-layer, thinner ahead and wider-behind, the particle.
Thus, the potential varies around the particle, lower at the
leading edge and higher at the trailing edge. Sarkar and Nich-
olson2 speculated that the cations (termed co-ions) in an Al2O3
suspension, which move with the positively charged Al2O3
particles toward the cathode, are in excess and react chemically
with the counterions of the extended double-layer tail, thus
reducing its thickness and facilitating particle coagulation.
However, Sarkar and Nicholson2 presented no data to support
their mechanism of particle coagulation.
As the cations carry the majority current to the cathode, their
concentration in the vicinity of the cathode must decrease be-
cause of discharge. This situation is counter to the Sarkar and
Nicholson2 mechanism, and thus, the real coagulation process
must include a decrease of concentration of the co-ions as a
function of position and time in the EPD cell.
II. Theory
Figure 1 illustrates EPD from a colloidal, stable, suspension
of positively charged particles. The electrical double-layers
3032 Journal of the American Ceramic SocietyDe and Nicholson Vol. 82, No. 11

around the electrodes of the EPD cell extend to the outer Helm-
holtz plane (OHP)12 (where the excess charge density of a layer
of solvated ions in the solution counterbalances the excess
charge density of the electrode). Thus, a solvated ion can ap-
proach the OHP around an electrode. Upon application of a dc
field during the EPD of positively charged particles, the par-
ticles and the co-ions move toward the cathode and the coun-
terions move to the anode. The particles coagulate to form a
dense, compact, green deposit at the cathode.
The net surface charge on oxide particles and its sign depend
on the pH of the suspension for both aqueous and nonaqueous
suspensions. H+ and/or OH react with the surface hydroxyl
groups on powders-in-air and charge the surfaces, i.e.,
(XOH)0surface + H+ (XOH2)+surface (at low pH) (1)
(XOH)0surface + OH (XO)surface + H2O (at high pH)
(2)
These equilibria are assumed in the present work.
In particular, Al2O3 particles in acidic ethanol suspension are
considered (Fig. 1); i.e., H+ are the co-ions and OH the coun-
terions. The atmosphere of ions around a charged particle is
called its double-layer. On moving, portions of the double-
layers shear off and the new potential between the bulk so-
lution and the shear-plane is the potential.
DLVO (Derjaguin, Landau, Verwey, and Overbeek) theory
quantifies the total interaction energy barrier, VT, between two
spheres and their double-layers (radius R, separated by dis-
tance h) as
64RkT20C*0 AR
VT = exp h
12h
where
0 = tanh
Ze0
4kT
and C*0 is the bulk concentration (number of molecules/m3)13
of a symemtric (Z:Z) electrolyte. k is Boltzmanns constant, T
is the absolute temperature, e is the charge on an electron, and
0 and r are the dielectric permittivity of a vacuum and the
relative dielectric permittivity of the solvent respectively. ,
0, and A are the double-layer thickness, the surface potential,
and the Hamaker constant of the separating medium, respec-
tively.
The total interaction energy barrier, VT, is a result of com-
petition between the repulsive (first term in Eq. (3)) and Lon-
don van der Waals (LVDW) attractive forces (the second
term). The attractive energy follows a power law and is short-
interface (x 0) involves activation-energy12 as also does the
charge transfer process in the second step of Eq. (4). If the
charge transfer process is at virtual equilibrium, the process
will be controlled by the rate of diffusion of H+ from the bulk
to the OHP.
If the charge transfer reaction at the electrode consumes H+,
the [H+] at the solution/electrode interface will drop below the
bulk value. Thus, current passage generates a [H+] gradient.
The total flux14 of ions of type i with valence Zi via diffusion
and electric field E, in a medium moving with velocity v, is
DiFZiCiE
jitotal = Civ Di grad Ci + (5)
RT
where Di is the ion diffusion coefficient, F Faradays constant,
R the universal gas constant, T the absolute temperature of the
solution, and Ci the concentration of ions of type i. The first,
second, and third terms on the right-hand side represent the
flux due to convection or movement of the medium, diffusion,
and electrical migration or drift of the ions in the electrical field
E, respectively. Neglecting thermal diffusion effects and as-
suming Di is independent of concentration, and the bulk of the
binary electrolyte solution is electrically neutral, i.e., ZcCc
ZaCa (subscript c and a represent the cation and anion,
respectively), a mass balance15 on an infinitesimal volume of a
binary electrolyte solution gives
C
+ v grad C = DeffC (6)
t
where Deff DcDa(Zc + Za)/(ZcDc + ZaDa), the effective dif-
(3)
fusion coefficient, C = Cc/Za Ca/Zc, the concentration, and
t is the time. If v 0, the convective terms in Eq. (6) can be
neglected and, for semi-infinite linear diffusion in the region
between x 0 and x (as shown in Fig. 1), Eq. (6) can be
rewritten as
C 2C
= Deff 2 (7)
t x
Equation (7) dictates the variation of concentration of the ions
as a function of time and position in the electrolyte solution
during electrophoresis. The electrical field enters the calcula-
tion via the boundary condition on this equation.
At time t 0, concentration is everywhere that of the bulk
(C = Cbulk). The boundary conditions12 needed to solve Eq. (7)
are
C = Cbulk at x = (8)

range. As the separation distance increases, the repulsive en-
ergy dominates and an energy barrier against particle coagula- C I
jc,totalx=0 = Deff == at x = 0 (9)
tion develops. This barrier must be lowered during the x x=0 ZcF
deposition step of EPD; i.e., the values must be reduced if
deposition is to occur. where I is the dc current density (constant with time). The flow
When a constant dc current is applied across an EPD cell, the of counterions (anions) through the interface between the cath-
free energy is no longer uniform nor minimum everywhere. ode and the electrolyte at x 0 is zero. The diffusion flux of
The resulting free-energy gradient sets up a drift (flux) of ions cations at this interface is constant, i.e., for time t < 0, flux
in a preferred direction (e.g., H+ toward the cathode in Fig. 1). 0 and for time t > 0, flux , a constant.
This flux results in flow of charge in the electrolytic solution. The analytical solution12 of Eq. (7) with these boundary
In the absence of this drift, the electrodes would soon run out conditions is
of ions for the necessary charge-transfer reactions.
Sarkar and Nicholson2 considered positively-charged Al2O3
particles moving in an acidic, ethanol suspension. Under con-
C = Cbulk

0.5
Deff

2
t

0.5

exp
x2
4Deff t

stant-current conditions they found H+ carry the current (Fig.
1). Thus, the charge transfer reaction at the cathode is x x2 0.5

H+ + e 21H2. H+ must be supplied by the bulk solution to 0.5

1 erf (10)
Deff 4Deff t
the cathode interface, so the charge transfer process involves
two steps: Setting x 0 in Eq. (10),
H x+ = H +x = 0 +e

transport process charge transfer 1
2H2 (4) 2I t
Cx=0 = Cc,bulk (11)
ZcF Deff
Subscript x0 corresponds to the OHP (see Fig. 1). The trans-
port of H+ from the bulk (x ) to the electrode solution This is Sands equation and determines the [H+] at x 0 as a
November 1999 Role of Ionic Depletion in Deposition during Electrophoretic Deposition 3033

function of time, once constant current passes in the EPD cell.
Since this implies Cx0 decreases from the bulk value, Cc,bulk,
with time t, there must be a time (which will be termed the
transition time, ), at which the concentration, Cx0, reaches
zero. can be determined by setting Cx0 0 in Eq. (11), i.e.,
ZcF
0.5 = C
2I c,bulk
Deff (12)
When the bulk cation concentration is small but the current
density is large, is small, i.e., seconds or less.12 Bockris and
Reddy12 argued that, when is more than a few seconds
(achieved through proper manipulation of Cc,bulk and I ), the
constant depletion of cations at the cathode causes the density
of the electrolyte at the cathode to be different from the bulk
nXO nXO
YXO = =
nXO + nXOH+2 + nXOH nt
where n is the number of sites on the surface occupied by the
group involved and nt the total number of active sites on the
surface. In Eqs. (13) and (14), the logarithmic terms account
for the contribution from entropy-of-mixing of groups confined
to the surface and e0 is the electrostatic contribution to the
free energy.
At equilibrium and when the particles attain the point of zero
charge (pzc) (particle surface has no net charge), each of G1,
G2, and the surface potential (0) becomes zero. Assuming
the isoelectric point (iep) coincides with the pzc in an Al2O3
suspension in ethanol, at pHiep, YXO YXOH . Taking T
+
2

value; i.e., natural convection will occur before a high value 298 K, Eqs. (13) and (14) then result in

is reached. Electrolyte flow will occur to correct this density
difference, thus destroying the initial hydrostatic equilibrium.12 0.059 CH+,bulk COH,bulk YXO
0 = log log + log
Generally, natural convection arises because of temperature 2 CH+,bulkiep COH,bulkiep YXOH+2
gradients. Though direct experimental evidence of natural con- (15)
vection due to a density gradient has been reported,15,16 it
remains unproven in an EPD cell. A layer of electrolyte adja- where the units of surface potential (0) are volts.
cent to the electrode will remain stagnant12 and pure diffusion The last term of Eq. (15) is the ratio of the mole fractions of
will prevail. Thus, for low values, the diffusion layer thick- XO and XOH+2 groups. To determine this, a surface adsorp-
ness increases initially, reaches a maximum at , whereupon it tion model is required. The mole fraction of the surface group
is reduced by natural convection. is a measure of the amount of that group adsorbed if (a) all
The concentration profile of cations at low values gives surface sites have the same activity for adsorption,17 (b) there
valuable information vis-a-vis the maximum [H+] attainable is no interaction between the adsorbed groups, (c) the rate of
at any position during EPD. Detectable bulk movement of liq- adsorption per site is independent of the amount adsorbed, (d)
uid was not observed in the present work nor has it been re- all adsorption occurs by the same mechanism, and (e) the ex-
ported. Thus, it is assumed that, for low , natural convection tent of surface adsorption is less than one complete monomo-
is not appreciable and Cx=0 reaches a steady-state value close to lecular layer. The Freundlich isotherm15 is appropriate for
zero during EPD. these assumptions and can be used to fit the experimental data
Competition between the equilibria of Eqs. (1) and (2) will over a range of concentration, i.e.,
determine the effective surface charge on oxide particles via
the pH of the suspension. If H+ and OH possess different YXO = BOHCOH,bulk1 OH (16a)
equilibrium adsorption affinities for the surface hydroxyl
groups, the relative [H+] and [OH] in the bulk will dictate the
net charge on the particles. The short-range chemical interac- YXOH+2 = BHCH+,bulk1 H (16b)
tions between the ions in the solution and the particle-surface
hydroxyl groups can be described by conventional chemical where BOH, BH, OH, and H are constants. Using YXO

equilibrium when the ionic contributions due to the presence of YXOH at the iep in Eq. (16)
+
2

electrical interfaces are included13 in the equilibria. The chemi-

cal equilibrium calculations must include (1) the change in
surface charge density (and hence in free energy of the elec-
trical double layer), due to association of ionic species with the
surface hydroxyl groups, and (2) the entropy-of-mixing contri-
bution to the free energy resulting from confinement of the
XOH, XOH+2, and XO groups to the particle surface. The
chemical potentials () of H+ and OH in solution at equilib-
rium are equal to their respective values on the surface and the
ions compete for the adsorption sites of the surface hydroxyl
groups. The free energy change for Eq. (1) is
YXOH+2
G1 = 01 + e0 kT ln CH+,bulk + kT ln (13)
YXOH
where

01 = XOH+,surface XOH,surface
0
H+,bulk
0 0
2

Similarly, for Eq. (2)

YXO
G2 = 02 e0 kT ln COH,bulk + kT ln (14)
YXOH
where

02 = XO,surface XOH,surface OH,bulk

0 0 0

The parameter Y in Eqs. (13) and (14) is the mole fraction of

surface groups; e.g., for surface group XO Fig. 1. Schematic of the electrophoretic deposition (EPD) process.
3034 Journal of the American Ceramic SocietyDe and Nicholson Vol. 82, No. 11

Table I. Values of Input Parameters Used in the Model

Input variables Value
2
Current density, I (Am ) 2.0
Diffusion coefficient of cation, Dc (m2s1) 9.31 109
Diffusion coefficient of anion, Da (m2s1) 5.3 109
Valency of cation, Zc (dimensionless) 1
Valency of anion, Za (dimensionless) 1
Suspension pH (dimensionless) 4.0
Dielectric permittivity of vacuum,
0 (CV1m1) 8.854 1012
Relative dielectric permittivity of
solvent, r (dimensionless) 24.3
Temperature, T (K) 298
Boltzmanns constant, k (JK1) 1.38 1023
Faradays constant, F (Ckgequiv1) 9.652 107
Radius of Al2O3 particle, R (m) 0.11 106
Hamaker constant for ethanol, A (J) 4.2 1020
Charge of an electron, e (C) 1.602 1019
Suspension pH at point of zero
charge (pzc), pHpzc (dimensionless) 7.15
Value of constant, , in Eq. (17)
(dimensionless) 2.7
Fig. 3. Profile of suspension pH as a function of time t and distance
(x).

YXO
= 10 pHpHiep (17)
YXOH+2
where ( 1/H + 1/OH) is an adjustable parameter and pH
is the bulk value of the solution. The Langmuir adsorption
isotherm (the extent of surface coverage by a group is directly
proportional to its bulk concentration) would give H and OH
equal to 1 and thus 2. The variation of surface potential
(0) as a function of the bulk concentration of H+ and OH ions
is thus described by Eqs. (15) and (17).
III. Results and Discussion
The values of the parameters used in the computation that
follows are given in Table I.
Sarkar and Nicholson2 reported that at pH 4.0, Al2O3 par-
ticles have a zeta potential () 80 mV and their suspension in
ethanol is stable. Since the Al2O3 particles are positively
charged at pH 4.0, the co-ion is H+. Equation (10) is used to
compute the variation of [H+] as a function of time and position
in the EPD cell (Fig. 2). [H+] decreases from the bulk toward
the cathode as it is depleted (Eq. (4)). Figure 2 also shows that,
after time t > 0, the gradient of [H+] remains the same at the
cathode (x0), implying constant flux conditions (the bound-
ary condition of Eq. (9)).
The [H+] decreases continuously toward zero at the cathode
(x 0) until is reached ( 0.124 s). This small value of
facilitates pure diffusion of co-oins before natural convection
starts. The maximum diffusion layer thickness, i.e., the maxi-
mum distance (x) from the cathode over which [H+] differs
from the bulk, is 100 m, i.e., 500 times the particle diam-
eter (0.22 m). Figure 3 shows the corresponding variation of
suspension pH as a function of time and position. This dem-
onstrates that, at t > 0, as H+ are depleted, the suspension pH
increases toward the cathode from the bulk value. Figure 3 also
shows that the pH at the cathode is maximum (7) near . (It
must be noted vis-a-vis Figs. 2 and 3, the computation is car-
ried out to 0.99 since the pH at the cathode (x 0) becomes
indeterminate when [H+] becomes zero.)
The results of the surface adsorption model (Eqs. (15) and
(17)) as a function of pH in ethanol are shown in Fig. 4 and
compared with the experimental data of Sarkar and Nicholson.2
The ionic concentration in an organic medium such as ethanol,
with a low dielectric permittivity, is low, and this results in a
slow decrease of potential with distance, 2 i.e., a thick
lyosphere. As a result, 0 can be assumed; i.e., 0 can be
replaced by in Eq. (15).
In the fitting of the surface adsorption model to the experi-
mental data of Sarkar and Nicholson2 in Fig. 4, the suspension
pH at the iep (pHiep) of Al2O3 particles is taken as 7.15. Figure
4 clearly shows that the agreement between the experimental

Fig. 2. Profile of co-ion (H+) concentration as a function of time t Fig. 4. Variation of zeta potential () of particles as a function of
and distance (x). Transition time, 0.124 s. suspension pH.
November 1999 Role of Ionic Depletion in Deposition during Electrophoretic Deposition
data of Sarkar and Nicholson2 and Eq. (15) (neglecting the last
term on the right-hand side) is poor. Fitting via a Langmuir-
type model ( 2) improves the fit and suggests that a valid
adsorption model must be chosen. Agreement is best for the
Freundlich isotherm ( 2.7) and this is included in Eq. (15).
Disagreement at the two pH extremes (4 < pH < 6 and 8 < pH
< 10) is due to surface saturation; i.e., all of the sites on the
surface are occupied and this situation violates one of the as-
sumptions of the model. Since the surface is completely cov-
ered at both extremes, there will be no change of potential
with suspension pH.
Figure 3 shows that the suspension pH increases from its
bulk value of 4 to 7.15 (at the iep) with increasing time and
cathode approach. The surface charge density (strongly depen-
dent on the suspension pH (see Eqs. (1) and (2))) decreases as
the suspension pH increases from 6 to 7.15 and the 0 (or for
ethanol) also decreases (Fig. 4).
Both Eq. (3) and the versus suspension pH data of Sarkar
and Nicholson2 in Fig. 4 were used to calculate the total inter-
action energy (VT) versus Al2O3 interparticle (assumed spheri-
cal) separation distance (h) (Fig. 5). As decreases (suspension
pH 6 to 7.15), the height of the primary energy barrier against
coagulation decreases.
IV. Proposed Mechanism of Deposit Coagulation
during EPD
The speculated mechanism of Sarkar and Nicholson2 that
states that excess H+ reacts chemically with the counterions in
the extended double-layer, thus reducing its thickness and fa-
cilitating particle coagulation, is not correct. [H+] decreases
toward the cathode because of the continuous depletion (dis-
charge) of H+ in the cathodic reaction of an EPD cell.
Figure 6 delineates the probable steps involved in particle
coagulation and deposition during the EPD process. In the bulk
(denoted by A in Fig. 6), the suspension pH is 4.0 and Al2O3
particles have the highest potential of 80 mV. As a result,
Al2O3 particles are well-dispersed because of ionic stabiliza-
tion and the energy barrier for particle coagulation is maxi-
mum. The distorted double-layers around the Al2O3 particles
are due to shear action of the fluid during the electrophoretic
motion of the particles. As the Al2O3 particles move from their
equilibrium bulk position toward the cathode where H+ is dis-
charged and depleted under the action of imposed electrical
field, they traverse a region (approximately 500 times the par-
ticle diameter and denoted by B in Fig. 6) of increasing sus-
pension pH, shown in Fig. 3. During the migration of the Al2O3
particles through this region of increasing suspension pH (re-
Fig. 5. Variation of total interaction energy, VT, as a function of zeta
potential () of particles and distance of separation (h) between the
particles.
3035
Fig. 6. Proposed mechanism for particle coagulation during EPD.
gion B), their surface charge density, and hence potential (see
Fig. 4) and energy barrier for particle coagulation (see Fig. 5),
decrease. Near the cathode (denoted by C in Fig. 6), the sus-
pension pH approaches 7.15 (pHiep of Al2O3 particles), as
shown in Fig. 3. As a result, the potential (see Fig. 4) and
energy barrier against particle coagulation (see Fig. 5) of the
Al2O3 particles are reduced near the cathode, facilitating co-
agulation and deposition.
This involvement of co-ion (H+) concentration in the po-
tential of particles as a function of location within the suspen-
sion and deposition time is unique to the EPD process of ce-
ramic shaping.
V. Conclusions
It is demonstrated that, during the EPD of Al2O3 from etha-
nol (pH 4), the discharge-depletion of cations (H+) at the cath-
ode induces the suspension pH to increase locally toward 7.15
(pHiep of Al2O3) and the potential of the particles to de-
crease and thus facilitate coagulation. Chemical-equilibrium
calculations involving the Freundlich surface adsorption iso-
therm track the change in the potential satisfactorily and
DLVO theory calculations illustrate that such a lowering of the
potential facilitates particle coagulation.
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