Effect of the slurry properties on the homogeneity of

alumina deposits obtained by aqueous electrophoretic

deposition
R. Moreno*, B. Ferrari
Instituto de Ceramica y Vidrio, CSIC, Ctra. Valencia, km 24.300, 28500, Arganda del Rey, Madrid, Spain
(Refereed)
Received 14 June 1999; accepted 12 August 1999
Abstract
Electrophoretic deposition (EPD) has been used to obtain self-supported alumina substrates
from aqueous slurries. The uniformity of the nal deposit is a function of the colloidal properties
of the slurry. In this work, the conductivity and the solid content of the slurries are related to the
deposition kinetics and the characteristics of the green compacts. The solid content is demonstrated
to increase the experimental conductivity margins for suitable deposition. In addition, the more
concentrated the slurry is, the lower the contamination of the deposit when metallic electrodes are
used. 2000 Elsevier Science Ltd. All rights reserved.
Keywords: A. Ceramics; A. Oxides; A. Interfaces; D. Defects
1. Introduction
A critical aspect in the manufacturing of a ceramic product is the selection of a simple,
low-cost fabrication procedure that allows the obtention of uniform materials of the desired
geometry and shape, with fewer and smaller defects. In recent years, an important effort has
been devoted by ceramists to study in depth the principles of colloidal science. The colloidal
* Corresponding author.
E-mail address: rmoreno@icv.csic.es (R. Moreno).
Pergamon Materials Research Bulletin 35 (2000) 887897
0025-5408/00/$ see front matter 2000 Elsevier Science Ltd. All rights reserved.
PII: S0025- 5408( 00) 00288- 9
approach to ceramics has been demonstrated to provide higher microstructural uniformity
and reliability, improving the material performance for more severe applications.
Colloidal-forming techniques include some well-established methods for producing com-
plex shaped parts, such as slip casting and pressure casting, or thin sheets for substrates, such
as tape casting, as well as more recent self-hardening methods, such as direct coagulation
casting, low pressure injection molding, and gel casting. In all of these methods, a basic
requirement that determines the product properties is the preparation of a well-dispersed,
concentrated slip [14]. Each method requires the use of specic processing additives in
order to improve the stability of the slurry and the subsequent forming operations [5,6].
Nowadays, many technological devices increasingly demand new materials with complex
structures, such as ceramic laminates and functionally graded materials, ber-reinforced
composites, etc. In most cases, metal/ceramic composites could satisfy the necessities of new
technologies. In this context, the preparation of protective ceramic coatings onto metals has
received great attention. For this purpose, different technologies have been developed, such
as the currently available vapor deposition processes and plasma sputtering. However, these
methodologies are expensive and present important limitations for producing thick coatings
and for effectively coating complex shapes.
The colloidal approach offers a suitable alternative for the preparation of these coatings by
means of the electrophoretic deposition process (EPD). This method allows thin or thick
ceramic coatings to be produced on complex shapes as well as self-supported parts, by
applying an external dc eld to the slurry, which promotes the migration of particles
(electrophoresis) and the subsequent deposition onto the oppositely charged electrode. The
increasing interest aroused by EPD is due to its three important advantages: (1) versatility,
since it allows self-supported shaped materials and coatings [710]; (2) low cost of the
process, which only needs a power supplier and an electrophoretic cell containing the
electrodes; and (3) reliability, which can be increased by accurate control of the process
kinetics.
EPD kinetics follows a simple equation proposed by Hamaker [11] (Eq. (1)), which relates
the deposited mass per unit area (m) with the slurry properties (concentration C and
electrophoretic mobility u
e
) and the physical and electrical xed conditions (electric eld E
and deposition time t).
m Cu
e
Et (1)
The electrophoretic mobility of the particles is proportional to the zeta potential () and to
some liquid media properties (dielectric constant and viscosity ), as determined by Eq. (2)
[12]:
u
e

1.5
(2)
The electrophoresis phenomenon has been known since 1850 [13]. However, the EPD of
ceramics was rst studied by Hamaker in 1940 [11], and only in the 80s did the process
receive attention in the eld of advanced ceramics. A literature review revealed that 80% of
the published works on EPD of advanced ceramics [14,15] reported the use of organic
888 R. Moreno, B. Ferrari / Materials Research Bulletin 35 (2000) 887897
solvents. Obviously, the use of water implies advantages, such as a higher-temperature
control during the process or a faster kinetics, in addition to important health, environmental,
and cost benets. These advantages most likely promoted the interest of some research
groups in the 90s to consider using aqueous EPD to process technical ceramics [7,9,10,
1621].
Aqueous EPD, however, has important limitations [22]. The main problems are related to
electrochemical reactions in the electrodes when a current is passed through, which seriously
decreases the efciency of the process and the uniformity of the deposit. Firstly, water
electrolysis promotes the formation of H
2
and O
2
that can be retained as pores in the ceramic
deposit. Secondly, when metallic electrodes are used, the normal potential of the metal is
largely overpassed. This facilitates the oxidation of the electrode and the 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 porosity, thus degrading its expected properties.
Another electrokinetic phenomena occurring in aqueous EPD is water electroosmosis,
which consists of the movement of the liquid phase because of an external electric eld. This
could be helpful in EPD, because it would accelerate the drying of the deposit surface in
contact with the electrode, so, if the process were well controlled, demolding of self-
supported deposits would be easier. Contrarily, if the deposit were too thick or the process
were too fast, crack formation could occur as a consequence of the drying gradient.
Adequate control of the colloid chemistry of the particles in the slurry can signicantly
reduce the effects of these problems. The aim of this work was to analyze the benets and
problems of using water in the production of self-supported deposits or coatings of advanced
ceramics, focusing the properties of the colloidal suspensions, especially the solid content.
2. Experimental
A commercial -Al
2
O
3
powder (Alcoa A16SG, USA) was used. Aqueous slurries with
different solid loadings (5, 10, and 20 wt%) were prepared in water, as described elsewhere
[16]. A commercial carbonic anionic acid based polyelectrolyte (Dolapix CE64, Zschimmer-
Schwarz, Germany) at different concentrations (05 wt% referred to solids) was added to
stabilize the slurries. The effect of colloidal parameters, such as zeta potential, conductivity,
and solid loading, on EPD performance was studied.
To generalize the obtained results, a metallic conductor (Zn) and a semiconductor
(graphite) electrode were used, with surfaces of 7.07 and 6.25 cm
2
, respectively.
The cell geometry and the electrical conditions were kept constant for each system
suspension/electrode. After checking different experimental conditions for each system, the
following were selected: a current density of 6.4 mA cm
2
for 10 min, for a suitable EPD
onto graphite electrodes, and that of 2.8 mA cm
2
, for a deposition time up to 30 min, when
using Zn as electrode. In all cases, a constant stirring was maintained to avoid powder
sedimentation and bubbling effects. Fig. 1 schematically shows the electrophoretic cell used.
A thermal bath was used for controlled temperature tests. The conductivity was measured
889 R. Moreno, B. Ferrari / Materials Research Bulletin 35 (2000) 887897
with a conductivity meter (WTW model LF320), and zeta potential data were obtained on 20
wt% slurries, using a Micromeritics mass transport analyzer.
The deposits obtained were dried at room conditions for 24 h, after which their weight and
thickness were measured. Chemical analysis of some of the dried green deposits was
performed by direct solid-sample analysis, using the inductively coupled plasma atomic
emission spectrometry technique with laser ablation (LA-ICP-AES). This technique is based
on laser irradiation of a solid sample introduced into an ablation chamber, promoting the
fusionvaporizationatomizationionization of the sample. The vapor is carried by an Ar
current and solidies as micronic and submicronic particles, which are then analyzed by a
plasma spectrometer. A prolonged irradiation makes the penetration, and therefore the
analysis of the sample, to be deeper. The spectrum proles were obtained taking into account
that 1 pulse corresponds to the analysis of 10 m of sample in depth, assuming that the
packing density is constant within the deposit. A frequency quadrupled Nd:YAG laser
operating at 266 nm (Cetac Technologies, LSX-100) coupled to and ICP-AES instrument
(Perkin-Elmer, Optima 3000DV) were used. The Zn detection with the ICP spectrometer was
performed using the emission line located at 213.856 nm. The in-depth contamination
proles were determined by irradiating the samples from the face in contact with the
electrode and from the opposite face. The number of applied pulses was high enough to
completely cross the samples. The effect of the variation of the solid content and the slurry
conductivity on the resulting contamination prole was studied.
Green densities were measured by Archimedes method in mercury. Green self-supported
Fig. 1. Scheme of the experimental device used for temperature controlled EPD tests.
890 R. Moreno, B. Ferrari / Materials Research Bulletin 35 (2000) 887897
samples were sintered at 1550C/2h in air. The microstructure was observed by SEM on
polished and thermally etched surfaces.
3. Results and discussion
3.1. Viability of the aqueous EPD vs slurry conductivity
As described by Eq. (1), the deposited mass per unit area depends on the powder
concentration and the electrophoretic mobility of the slurry. The concentration of powder
in EPD suspensions is low compared with that in other colloidal suspensions (usually
510 wt%) [3,4], and a priori it affects proportionally the quantity of powder to be
deposited, but without affecting any other EPD parameter. Contrarily, particle mobility
is directly related to slurry stability and thus affects all the EPD variables.
Maintaining the particles dispersed throughout the medium is a major problem in colloidal
slurries, like those used for EPD, because of the attractive Van der Waals forces developed
as particles approach each other. Stabilization of the slurry requires the action of repulsive
forces dominating over the attractive ones; therefore, particles must be completely sur-
rounded by the medium, to avoid contact among them. These repulsive interactions can be
originated by three different general mechanisms, referred to as electrostatic, steric, and
electrosteric [5]. They are based on the addition of electrolytes able to change the charge of
the double layer, the adsorption of long-chain polymers onto the particle surface, and the
adsorption of charged polymers onto the particle surface, respectively. The last case was
employed for stabilizing the suspensions tested in this work.
The electrophoretic rate (Eq. (3)) decreases with the density of the electric eld, that is,
when the charge at the particle surface increases [23]. Consequently, the deposition process
depends on two opposite tendencies. EPD must be performed considering a compromise
between high particle mobility and low particle charge per unit weight, and, hence, the
concentration of deocculant should be the minimum necessary to avoid unstabilization
since an excess could result in increased charge per unit weight.
v
e
u
e
E (3)
To determine the deposition limits related to the deocculant system, Al
2
O
3
slurries (5 wt%)
with deocculant contents up to 5 wt% were tested using Zn working electrodes. The
conductivity of the slurries and the thickness and the mass per unit area of the obtained
deposits are plotted in Fig. 2. There is a minimum below which no deposit is formed (0.3
wt%) due to the lack of stability. The deposited mass decreases when an extremely high
amount of deocculant is added to the slurry (5 wt%). The deocculant in excess does not
contribute to the dispersion, but effects an increase in slurry conductivity from 175 S cm
1
for an addition of 0.4 wt%, to 1150 S cm
1
for an addition of 5 wt%. Hence, the deposition
decreases with the electric eld.
This effect is drastic when using graphite electrodes. In this system, the deposition limits
can be experimentally determined. Al
2
O
3
slurries (5 wt%) with 0.20.6 wt% deocculant
891 R. Moreno, B. Ferrari / Materials Research Bulletin 35 (2000) 887897
concentrations were tested applying a current density of 6.4 mA cm
2
for 10 min and keeping
the work temperature constant during the tests. As was demonstrated in a previous work [16],
the increase of voltage during the test is associated with the formation of a homogeneous
growing deposit. An increased voltage also means a higher particle packing of the deposit.
Fig. 3 plots the measured conductivity of 5 and 10 wt% slurries as a function of temperature.
The continuous lines represent the conductivity of two reference suspensions with exact
concentrations of deocculant (0.3 and 0.4 wt%) for each solid loading. The concentration
of deocculant can be estimated by measuring its conductivity. Full points represent the
slurry conductivities that produce a uniform coating after EPD, while the void points
correspond to those slurries that did not form an homogeneous deposit onto graphite.
Fig. 2. Evolution of thickness and weight per unit area of Al
2
O
3
deposits obtained onto Zn substrates as a function
of deocculant concentration.
Fig. 3. Conductivity/temperature relationship of 5 and 10 wt% Al
2
O
3
slurries with different amounts of
deocculant. Full symbols (I) correspond to EPD tests performed by applying 6.4 mA cm
2
for 10 min, which
produced deposit. Void symbols () correspond to EPD test performed under similar conditions where no deposit
could be obtained. The continuous lines represent the conductivity of 5 and 10 wt% slurries with 0.3 and 0.4 wt%
deocculant each. The dashed lines in the plots of both solid contents limit the regions of successful deposition
onto graphite.
892 R. Moreno, B. Ferrari / Materials Research Bulletin 35 (2000) 887897
Optimal slurry conditions correspond to a 0.4 wt% deocculant addition, which has a zeta
potential of 50 mV. From these suspensions, the highest voltage increases were registered
during EPD tests for both solid loadings. Furthermore, a clear region for successful depo-
sition can be plotted, so that deposition does not occur outside of these limits. The minimum
limit is determined by the stability of the slurry and the maximum limit is dened by the
intensity of the electric eld able to promote the particle motion and deposition. Al
2
O
3
slurries with 0.2 wt% deocculant have a zeta potential close to zero [16]; therefore, the
particles do not migrate. Al
2
O
3
slurries with 0.6 wt% deocculant, on the other hand, have
high enough zeta potentials, but their conductivities are so high that the intensity of the
applied electric eld decreases, decreasing the electrophoretic rate and deposition possibil-
ities.
These results demonstrate that slurry conductivity is another important parameter that can
be used for controlling the viability of EPD. This property had not received due attention in
EPD literature, but it is a very simple way to follow slurry behavior. Otherwise, the
deocculant is the major factor responsible for the measured suspension conductivity and its
control allows determination of the dispersing conditions and a priori knowledge of whether
a deposit will be formed or not.
3.2. The effect of the solid loading
Another important slurry parameter is solid loading. This parameter is usually considered
not to affect EPD, except for the fact that the higher the quantity of solids in the suspension,
the higher the quantity of powder deposited. However, present experimental results demon-
strate that the solid content can be a powerful tool for controlling the EPD process and the
characteristics of the shaped materials. As shown in Fig. 3, the region dening the optimal
conductivity/temperature working zone is broader for more concentrated slurries; thus, it
becomes easier to control the deocculant weight added when solid content increases.
Furthermore, the green characteristics of deposits obtained after applying 6.4 mA cm
2
for
10 min largely depend on the solid content of the slurry, as summarized in Table 1. The green
density increased from 53% to 59% theoretical. This means that when all the other process-
ing parameters are maintained constant, the packing density directly increases with the solid
content. Thus, the general consideration that concentration does not affect the characteristics
of the deposit can be discussed. The theoretically predicted linear increase of the deposited
Table 1
Green density, thickness, and weight per unit area of the deposits obtained by applying 6.4 mA cm
2
for 10
min from 5 and 10 wt% Al
2
O
3
slurries
Green deposit characteristics Solid content
5 wt% 10 wt%
Thickness (mm) 2.13 2.23
Density (g cm
3
) 2.11 (53.2%) 2.34 (59%)
Weight per unit area (mg cm
2
) 450 520
893 R. Moreno, B. Ferrari / Materials Research Bulletin 35 (2000) 887897
mass was not reached. This suggests that it is necessary to take into consideration the
variation of all colloidal properties of the slurry.
When a metallic electrode was used, the system notably changed and other interesting
variables appeared. Dispersed aqueous Al
2
O
3
slurries (those with 0.4 wt% deocculant) were
used for deposition onto Zn electrodes. No changes in the potential during the process were
detected in this case. Considering what happened in the case of the graphite electrodes, one
would expect that a deposit would not be formed. However, successive EPD tests produced
deposits. This apparent contradiction suggests that the growing deposit behaves like a
conductive layer. This can only occur if metallic impurities are moving through the deposit.
These metallic impurities must be originated as a consequence of the corrosion of the Zn
electrode when a current is applied.
Direct chemical analysis using laser ablation inductively coupled plasma (LA-ICP-AES)
demonstrated that Zn inclusions were present in the green deposits and diffused from the
surface in contact with the electrode towards the bulk, up to a maximum distance of about
500 m [24]. Fig. 4 shows a general picture of the cross section of a sintered Al
2
O
3
thick
deposit prepared using a Zn electrode. A high heterogeneity with a large residual porosity,
due to metallic contamination, is observed. The contamination prole of Zn across the green
deposit can be drawn. It strongly depends not only on the imposed electrical conditions
(applied current density and deposition time), but also on the slurry characteristics, such as
the conductivity (in other terms, the concentration of deocculant) and unexpectedly, the
solid content.
Fig. 5 shows the deposited mass per unit area as a function of deposition time for EPD
tests performed applying 2.8 mA cm
2
for 1 to 30 min with Al
2
O
3
slurries containing 5 and
20 wt% solids. The slurries were always dispersed with 0.4 wt% deocculant. The less
concentrated followed linear Hamaker behavior [11], but the concentrated one soon deviated
from this behavior. The total quantity of deposited mass for 20 wt% slurries was about 11%
the total suspended powder. This is too low to be directly responsible for the observed
Fig. 4. SEM micrograph of a sintered Al
2
O
3
thick lm deposited onto a Zn substrate, applying 2.8 mA cm
2
for
30 min.
894 R. Moreno, B. Ferrari / Materials Research Bulletin 35 (2000) 887897
deviation from the linear behavior, since the total loss of mass in the 5 wt% slurry after
consecutive EPD tests was 32% and the kinetics maintained linearity [14].
A uniform deposit as thick as 500 m was obtained from 20 wt% slurries for 5 min
deposition time. For 5 wt% slurries, the packing density was slightly lower and the deposit
growth was slower.
Considering that the major contribution to slurry conductivity is due to the deocculant,
the conductivity of 20 wt% slurries (600 S cm
1
) is three times higher than that of 5 wt%
slurries (183 S cm
1
). Thus, applying the same current density, the electric eld generated
on the concentrated slurry is lower. This could be the reason why the deposit formation
cannot maintain for a long time the proportionality predicted by Hamaker equation (Eq. (1))
related to the solid concentration.
The green deposits obtained at 2.8 mA cm
2
after 20 min EPD using slurries containing
5 and 20 wt% solids were analyzed by LA-ICP-AES. Fig. 6 shows the indepth prole
Fig. 5. Weight per unit area deposited onto Zn vs. time, obtained from the 5 and 20 wt% Al
2
O
3
suspensions, with
a 0.4 wt% deocculant, applying 2.8 mA cm
2
for deposition times between 1 and 30 min.
Fig. 6. Zn emission intensity proles vs. the analysis depth of the Al
2
O
3
deposit obtained applying 2.8 mA cm
2
for 20 min from 5 and 20 wt% slurries.
895 R. Moreno, B. Ferrari / Materials Research Bulletin 35 (2000) 887897
obtained from analyzing the samples from the surface in contact with the electrode during the
EPD test. An increased solid loading has a noticeable effect on the contamination prole,
strongly reducing the signal intensity, which is nearly constant and very low. High slurry
conductivities developed low electric eld intensities, decreasing the oxidation rate of the
electrode and limiting motion of ionic impurities due to the quantity of big particles moving
in the opposite direction. Since, for short times, the deposit growing kinetics is much higher,
migration of impurities is hindered. In this way, metallic contamination is negligible at 20
wt%. In fact, when the concentrated slurry was considered, a voltage increase of 7 V was
measured between electrodes. Thus, the Al
2
O
3
deposit is not conductive. According to these
results, the solid contents of the slurry has much more inuence on the obtention of a
contamination-free deposit than was previously suspected.
4. Conclusions
The colloidal properties of the slurry determine both the viability of the EPD process and
the properties of the deposit. The slurry conductivity has been shown to be a critical
parameter capable of predicting whether the deposit will be obtained or not. The solid content
has been proven to affect EPD much more than had been suspected. By controlling this, it
is possible to modify the growing kinetics, to expand the experimental ranging conditions for
successful EPD tests, and even to reduce contamination in the deposit when the coated shape
is a metallic material.
Acknowledgments
The authors thanks to CICYT (Spain) for the concession of a research grant (MAT97-0676).
Dr. J. C. Farinas is greatly acknowledged for analytical tests and helpful discussions.
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