0020-1685/05/4106- © 2005 Pleiades Publishing, Inc.

0639

Inorganic Materials, Vol. 41, No. 6, 2005, pp. 639–645. Translated from Neorganicheskie Materialy, Vol. 41, No. 6, 2005, pp. 733–739.
Original Russian Text Copyright © 2005 by Mendoza-López, Avilés-Arellano, Pérez-Robles, Manzano-Ramirez, Vorobiev, Pérez-Bueno.

1. INTRODUCTION
The production of ceramic coatings by electro-
phoretic deposition (EPD) [1] is recent compared to the
electrolytic deposition (ELD). Since EPD was discov-
ered in 1809, the process has had a wide number of
applications. Electrophoresis is defined as the motion
of charged particles inside a fluid due to an applied
electric field. In a dc electric field, the migration of the
particles causes an accumulation around the opposite
charged electrode. Using appropriate conditions, parti-
cles in a suspension will become attached to each other,
and on the substrate, by van der Waals attraction or
chemical bonds, forming a solid deposit. This deposit
can be consolidated, with high densities, to form struc-
tures which have many applications, e.g., sensors and
actuators [2]. It is necessary to remark that EPD process
needs a high control in all the parameters involved
(concentration, voltage, current intensity, and others).
Although for aqueous systems, the process exists only
for ideal cases because nonfaradaic processes take
place, which causes water hydrolysis, changes in poten-
tial and concentration of suspensions, etc. [3]. Due to
mentioned phenomena, ELD can take place. It has been
established that the EPD process works well with parti-
cle sizes in the range of 1 to 10

µ

m suspended in a polar
solvent and presents many advantages in relation to
other coating techniques. Thickness and morphology of
deposits can be controlled by electrochemical parame-
ters and relatively uniform deposits on substrates with
complex shapes are obtained. Moreover, deposition
rates are higher than those obtained using other meth-
ods. Additionally, equipment of low cost is required [4].
The EPD process is applied for deposition of polymers,
ceramics, semiconductors, superconductors, etc. In
general for the EPD process, suspensions with a typical
content of solids about 5 to 20 wt % are used. Normally,
it is not possible to establish the difference between
EPD and ELD processes; but it is possible to have a
combination of them in aqueous suspensions (for ELD
there are ions, electrogeneration of OH



, and neutraliza-
tion of cationic species). The presence of charged colloi-
dal particles of great size denotes the possibility of coex-
istence of both processes, but the conductivity could be
the difference, if it is high we have an ELD process, but
if it is low, EPD will be the principal process.
In this work, under electric field, aqueous SiO

2

-
based formulation was used to coat stainless steel
sheets, which were used as working electrodes. Also,
nonconductive glass slides substrates were coated by
dipping in an electric field and characterized using dif-
ferent techniques.
2. EXPERIMENTAL
Coatings were prepared from an aqueous SiO

2

sus-
pension consisting of a mixture of colloidal silica,

Mechanisms Involved in the Deposition
of Coatings from Aqueous Colloidal Suspensions
of Silica in an Electric Field

M. L. Mendoza-López*, L. M. Avilés-Arellano*, J. F. Pérez-Robles*,
A. Manzano-Ramirez*, Y. V. Vorobiev*, and J. J. Pérez-Bueno**

* Centro de Investigación y de Estudios Avanzados del I.P.N. Unidad Querétaro, Libramiento Norponiente no. 2000,
Fracc. Real de Juriquilla, Santiago de Querétaro, Qro. C.P. 76230 Mexico
** Centro de Investigación y Desarrollo Tecnológico en Electroquímica, Parque Tecnológico Querétaro-Sanfandila,
A.P. 060, C.P.76700, Pedro Escobedo, Querétaro, Mexico
e-mail: vorobiev@arcos.qro.cinvestav.mx

Received October 14, 2004

Abstract

—Although several processes have been developed to obtain ceramic coatings, many of them are com-
plex, and expensive equipment is required. As an alternative process, in this work, electrodeposition was used
to deposit silica on stainless steel substrates. The properties of commercial silica were changed by adding some
chemical compounds. Potassium hydroxide was added to promote, in a controllable way, the formation of a sil-
icate network to obtain good adherence on metallic substrates. The addition of reagents caused controlled desta-
bilization on suspension and promoted the formation of clusters. The application of an electric field to obtain
coatings allowed the orientation of charged particles and, hence, the properties of the deposited material to be
modified. Electrokinetic parameters, electrical response, and GDS profiles were measured to determine the
influence of electric field on the coatings.

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MENDOZA-LÓPEZ

et al

.

water, potassium hydroxide as a catalyst, and sodium
metasilicate (Na

2

SiO

3

· 5H

2

O) as a silica source and
particle modifier. The aqueous colloidal silica, used as
a raw material, contains 30 wt % of SiO

2

with an aver-
age particle size of 13 nm. The aqueous suspension was
prepared according to the following procedure: 50 ml
of colloidal silica was mixed for 5 min with 70 ml of
distilled water using mechanical stirring. After that,
2.4 g of KOH (Baker) was added to the first suspension
under mechanical stirring for 10 min. In a separate ves-
sel, 11.25 g of sodium metasilicate (Baker) was dis-
solved in 60 ml of distilled water. This solution was
mixed with the suspension of colloidal silica for 20 min
using mechanical stirring to form the starting materials.
The as-prepared suspension had a solids content of
13.75 wt % and a conductivity of 25.36 mS/cm, mea-
sured in a Zeta Probe (in dc) by Colloid Dynamics.
Experiments were carried out using an electrical
source with variable voltage ranging from 1.5 to 45 V
and current intensities from 2 to 230 mA. A 50 ml cylin-
drical vessel was used as the container for the suspen-
sion. Sheets of stainless steel (

2.5

×

4.2

×

0.2

cm) and
graphite (diameter of 4.0 mm and length of 4.2 cm, with
a resistivity of 0.2



cm) were used as the anode and
cathode, respectively. The former was the working
electrode, and the latter was the counter electrode
because it is an inert material and an excellent electrical
conductor. Glass slides, used as substrates, were put
between the electrodes, which were separated by a dis-
tance of 5 cm. A schematic representation of the depo-
sition cell, with some details, is shown in Fig. 1. Glass
substrates were coated by dipping and applying an elec-
tric field of 1 and 2 V/cm, respectively, for 10, 20, 30,
40, 50, and 60 s. Then, the substrates were removed at
a rate of 1.28 cm/s and dried at 60

°

C for 15 min in an
oven. After that the coatings were annealed at 100

°

C
for 15 min. The distribution of different species as a
function of pH was calculated using MINTEQA 2 soft-
ware (National Exposure Research Laboratory, EPA,
USA). The particle size distribution was determined
using Beckman Coulter LS32 equipment with a range
of 0.01

µ

m to 1000

µ

m. Scanning electron-microscopic
(SEM) images were taken by a Philips Model XL30
ESEM, and surface chemical analysis was carried out
by EDS.
The Glow Discharge-Optical Emission Spectrome-
ter (GDS 700 V, 20 mA, 7 torr) was used to obtain qual-
itative and quantitative depth profiling, which allows
one to analyze a sample in a continuous way from tens
of nanometers up to above one hundred microns.
3. RESULTS AND DISCUSSION

3.1. Distribution Diagrams for Species
and Surface Charge

Working with aqueous suspensions using an electric
field, the first step was to know which species were
present in the system and, therefore, would be respon-
sible for surface charge on colloidal particles. So, in
this work, the concentration of charged species was
determined as a function of pH using MINTEQA2 soft-
ware. In this simulation, the user selects only the basic
species for a particular problem. In the case of colloidal
silica, silicic acid, H

4

SiO

4

(or Si(OH)

4

) is used as the
starting point. A suspension of colloidal silica and
sodium metasilicate were used as the silica source. Par-
ticles in colloidal silica suspensions consist of small
rounded particles formed by a three-dimensional net-
work of tetrahedra with silicon in the center of them,
bound to four oxygen atoms. Sodium metasilicate was
added to give transparency and promote adhesion of the
SiO

2

coating to the substrate. Colloidal silica has a net
negative charge, which is explained as follows. Accord-
ing to Iler [5], silica particles, in the presence of water,
will adsorb water molecules on the exposed surface.
This gives place to surface groups, Si(OH)

4

, and under
basic conditions, the OH



groups will form ,
releasing water. Also, it is known that the introduction
of any alkali metal (as ion M

+

) into the silica structure
produces significant structural changes. In pure SiO

2

,
all the oxygens are bound to two silicon atoms, where
oxygen forms bridges between neighboring silicon
atoms. The incorporation of an alkali ion M

+

splits the
oxygen bridging bonds and each M

+

ion gets attached
to a neighboring Si

4+

ion, forming



Si

–é–å

structures
[6]. The addition of a small percentage of randomly dis-
tributed alkali metals will break up the SiO

2

structure
into chains, cross-linked among each other, forming an
entangled structure. This effect, together with the ion-
ization of water on the surface of silica particles, causes
the appearance of charged surfaces in silica systems. As
a consequence, at pH 11.6, is the main species
responsible for the net surface charge, polarization,
and, therefore, electrophoretic movement, according to
Sjöberg [7]. In agreement with the above, in Fig. 2, the
distribution of species as a function of pH and in the
presence of an alkali metal is shown. The stabilization
HSiO
3

H
3
SiO
4


3
.
7

c
m
2.5 cm 2.5 cm

Fig. 1.

Electrodeposition cell. From left to right: stainless
steel electrode, glass substrate, and graphite electrode.

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MECHANISMS INVOLVED IN THE DEPOSITION OF COATINGS 641

of suspensions prepared in this work is related to repul-
sion among the exposed charged groups on particle sur-
faces.

3.2. Electrokinetic Measurements and Stability
of Colloidal Suspensions

In the table, the electrokinetic parameters of com-
mercial silica and the suspension used in the experi-
mental work are presented. The increase in pH is due to
metasilicate and KOH additions. The increase in con-
ductivity was promoted for the addition of KOH, K

+

,
and OH



ions, and Na

2

O was introduced as sodium
metasilicate. From the table, the decreasing effect on
dynamic mobility indicates an increase in particle size.
This fact is supported by measurements, particle size,
and kappa factor. The presence of opposite charges on
silanol groups, which can produce hydrogen bonds on
the surface of small clusters, promotes the interaction
among them to form large clusters. The particles grew
up and, after 30 days, the average particle size was
31.5

µ

m, as can be seen from the particle size distribu-
tions in Fig. 3. For comparison, Fig. 3 displays the par-
ticle size distribution for freshly prepared suspensions,
which shows an average particle size of 87 nm. The
change in the kappa factor is related to the thickness of
the ionic atmosphere around the particles, which at the
same time depends on the radius of the particles.
According to Henry’s expression [8, 9], the kappa fac-
tor depends on electrokinetic parameters such as
dynamic mobility, conductivity, and zeta potential.
From the expression of Hückel [9], for 1 >

κ

, it is con-
sidered that the thickness of the ionic atmosphere is
greater than the particle size and, therefore, there is a
high screen effect. So, there is a small interaction
among particles as in the case of stable commercial sus-
pensions of silica. The effect of surface and structure
modifiers added to the suspension is to shrink the ionic
atmosphere and decrease the interparticle screen effect.
This promotes the approaching among particles when
they are deposited on a substrate to form coatings. The
Smulochowski equation [9] is applied in this case.
Also, the difference in zeta potential values means a
reduction in the distance among particles of the suspen-
sion. This was expected because the prepared suspen-
sions present a higher conduction value, a higher
shrinkage of the double layer and a larger particle size
than commercial silica. In summary, the modified
structure of silica particles promotes the production of
clusters with surface groups exposed, which causes the
above reduction in the thickness of the double layer
around silica particles.

3.3. Preparation and Characterization of Coatings

Coatings were prepared from suspensions taking into
account properties of the solution. In the first part of
experiments, an aqueous suspension prepared from col-
loidal silica was used alone to coat substrates, but the
adherence was poor. This can be explained by the
absence of arrangement of the charged groups. For this
reason, a suspension was prepared according to the pro-
cedure described earlier. On the other hand, an impor-
tant aspect that is necessary to know, working with EPD
or ELD, is the electrical response of suspensions. In
order to obtain deposits, it is necessary to have a system

0.5
0
6

C
o
n
c
e
n
t
r
a
t
i
o
n
,

M

pH
7 8 9 10 11 12 13 14
1.0
1.5
2.0
H

4

SiO

4

H

3

SiO

4


H

2

SiO

4
–2

Fig. 2.

Distribution of species for hydrous silica. Molar con-
centration vs. pH.

Electrokinetic parameters of commercial silica and prepared suspension
ç
Conductivity,
mS/cm
Dynamic mobility,
SI

×

10

–8

Zeta potential, mV Kappa, nm

–1

Commercial silica 10.08 9.154 –2.372 –42.404 0.93
Working suspension 11.84 25.36 –1.262 –17.72 1.404

V
o
l
u
m
e

p
e
r
c
e
n
t

10
8
6
4
2
0 0.1 0.2 0.3 0.4 20 40 60 80 100 120140

Particle size

,

µ

m

Fig. 3.

Particle size distribution: (a) freshly prepared sus-
pension; (b) suspension 30 days after preparation.

(a) (b)

642

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2005

MENDOZA-LÓPEZ

et al

.

with high resistance and a continuous medium and to
know how these parameters vary with time. For the sus-
pensions prepared in this work, the current intensity did
not change at low electric fields, but at high fields an
increase in current intensity was observed and, at the
same time, the resistance decreased. The change in cur-
rent was accompanied by liberation of gases on the sur-
face of electrodes and this is clear evidence that a reac-
tion takes place inside the suspension, generating some
products. The gas liberation and the increase in the cur-
rent intensity can be attributed to the electrolysis of
water, with the oxidation reaction at the anode,

2

H

2

O



O

2

(

g

) + 4

H

+

+ 4

e



, and reduction at the cath-
ode, H

+

(

aq

) +

e



1/2

H

2

(

g

)

. Thus, the total reaction
is given by

2

H

2

O

(

l

) 2

H

2

(

g

) +

O

2

(

g

)

[10]. These
reactions must be avoided keeping the conductivity as

low as possible. According to the electrical response of
suspensions, the current intensities used were 80 and
339 mA for electric field strengths of 1 and 2 V/cm,
respectively. In order to characterize the type of depos-
its, stainless steel was used as the anode. An electric
field of 1 V/cm was selected because the deposition rate
was acceptable. The quantitative depth profiles were
obtained using the glow discharge spectrometer (GDS).
In Figs. 4a and 4b the element profiles, by GDS, are
shown as a function of depth for coatings obtained on
steel substrates by immersion only and by immersion
applying and electric field of 1 V/cm for 30 s and drying
at 100

°

C. From these two figures it can be observed
some variations in oxygen and silicon concentrations;
but in general, when the amount of silicon is increased
the quantity of oxygen is decreased and vice versa. This

10
0 20

W
e
i
g
h
t

p
e
r
c
e
n
t
Depth, nm

(b)
40 60 80 100 120 140
ë
Si
O
Fe
Cr
Ni
(ii)
(i)
20
30
40
50
60
0
250
500
750
1000

I
n
t
e
n
s
i
t
y
,


Current, mA



×

10

Vacuum, torr



×

10

2

Voltage, V

10
0

W
e
i
g
h
t

p
e
r
c
e
n
t

(a)
40 80 120 160
ë
Si
O
Fe
Cr
Ni
(ii)
(i)
20
30
40
50
60
0
250
500
750
1000

I
n
t
e
n
s
i
t
y
,


Current, mA



×

10

Vacuum, torr



×

10

2

Voltage, V

200

Fig. 4.

(a) Analysis for coatings by dipping; (b) analysis for coatings by dipping in an electric field, 1 V/cm for 30 s. (i) Voltage,
current intensity, and vacuum during the measurements; (ii) quantitative depth profiles.

a
r
b
.

u
n
i
t
s
a
r
b
.

u
n
i
t
s

INORGANIC MATERIALS

Vol. 41 No. 6 2005
MECHANISMS INVOLVED IN THE DEPOSITION OF COATINGS 643
phenomenon can be explained in the following way.
According to Zarzycki [11], when a network modifier,
such as Na
2
O, is added to SiO
2
, the additional oxygens
participate in the network and cause the rupture of a
specific number of bonds. A Si–O–Si bond is broken
and the added oxygen saturates the unsatisfied bond of
one Si and from this two Si–O

are formed. The two
negative charges on the oxygen are compensated by the
nearby presence of a pair of Na
+
cations ensuring the
electrostatic neutrality of the ensemble. The Si–O–Si
bridge rupture mechanism leads to a loosened network
structure with two types of oxygens: an oxygen bonded
to two Si is called a bridging oxygen, and an oxygen
bonded to one Si is called a nonbridging oxygen. From
this way the increase in oxygen at certain depth in coat-
ings can be attributed to an increase in the amount of
nonbridging oxygen. Tetrahedra in the case of non-
bridging oxygen are charged and can be arranged in an
alternate way to decrease repulsions. Thus, in coatings
deposited by dipping, it is observed a natural arrange-
ment of charged and noncharged species. This effect is
enhanced in the case of coatings deposited by applying
an electric field, as can be seen from Fig. 4b. According
to GDS measurements, the increase in oxygen on the
surface of coatings can be attributed to sodium carbon-
ate formed due to the presence of alkali added (Na
2
O
and K
2
O), as explained later. GDS analysis reveals that
in the interface there is a great amount of bridging oxy-
gen for the coatings obtained by dipping only and non-
bridging oxygen in the presence of a field was pro-
moted to the interface. In the presence of a field, ori-
ented charged clusters adhere to the surface by wan der
Waals forces. The thickness of coatings on metallic
substrates is smaller than 150 nm because of two fac-
tors: low extraction rate and low viscosity of the sus-
pension.
The appearance and morphology of coatings depos-
ited on glass slides using the cell arrangement proposed
by Tabellion [12], where the substrate is put between
the electrodes to deposit the charged clusters, were
homogeneous. The coatings were homogeneous, with
an average thickness of 540 nm. The coatings were
aged at room temperature in order to promote the for-
mation of soluble sodium and potassium carbonates on
the surface by reaction of alkali oxides with atmo-
spheric CO
2
which appear after a week of preparation.
When coatings were elaborated only by dipping,
with no field, SEM showed the presence of deposited
salts on the surface without any defined shape, with
small sizes and a random distribution (Fig. 5a). On the
other hand, by applying an electric field, deposited salts
on the surface of coatings have preferential orientation
and grow up superimposed with defined shapes like
needles, as illustrated in Fig. 5b. Chemical analysis of
those salts showed a high content of sodium in the most
exposed part, which decreases near the matrix (Figs. 6a,
6b). Also from qualitative chemical analysis by SEM
and GDS, in Fig. 6a, it is observed a certain concentra-
tion of carbon. This indicates that the salts in this case
are a mix of carbonates and silicates of sodium and
potassium. A lixiviation process, with water at room
temperature, was applied to coatings to observe indi-
(c)
Magn Det WD 10 µm
3500x SE 5.0
(b)
Acc.V Magn Det WD 10 µm
25.0 kV 3500x SE 5.2 0.9 Torr
(a)
Magn Det WD 10 µm
3500x SE 4.9
Fig. 5. (a) Coating by the dipping method, thermally treated
at 100°C for 15 min, showing irregular salts on the surface.
(b) SEM micrograph of a coating by EPD method, 60 s with
5 V, thermally treated at 100°C for 15 min. (c) Coating with
dissolution process for 90 min.
644
INORGANIC MATERIALS Vol. 41 No. 6 2005
MENDOZA-LÓPEZ et al.
rectly the cohesion among clusters, due to the presence
of the formed salts. It was possible to promote a
homogenous removal of salts from the surface, result-
ing in a uniform coating as illustrated in Fig 5c.
According to experimental results, the thickness of
coatings is approximately constant and independent of
the electric field used in this work.
4. CONCLUSIONS
It was possible to obtain coatings with both applying
an electric field and modifying the SiO
2
network by
adding potassium hydroxide. The adherence to sub-
strates was improved using sodium metasilicate. The
addition of these reagents promotes the formation of
small clusters that agglomerate to produce larger clus-
ters.
The presence of alkali oxides (Na
2
O and K
2
O) pro-
motes the breakage of SiOSi, generating nonbridging
oxygen, and increases the ionic surface charge, so the
electric conductivity of suspensions rises.
The electrokinetic parameters of suspensions show
that an orientation of charged particles occurred during
deposition, facilitating the formation of coatings with
smaller repulsion among particles. This allows alkali
oxides to be exposed on the surface, where they react
with atmospheric CO
2
, generating soluble carbonates,
which can be eliminated easily.
The presence of an electric field, to promote SiO
2
deposits, increases the amount of silicon inside the
matrix, which means that there is an increase in the
amount of bridging oxygen. This generates coatings
with low solubility in water at room temperature. Coat-
ings obtained by applying an electric field have a stable
structure compared with coatings obtained only by dip-
ping. In the latter coatings, nonbridging oxygen is
present in the whole matrix and, therefore, they have
high solubility in cold water.
ACKNOWLEDGMENTS
We thanks CONCyTEQ for the financial support to
accomplish the present work and José Eleazar Urbina
for the SEM analyses.
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