Ceramic films using cathodic electrodeposition

Ceramic Films Using Cathodic Electrodeposition

This article is one of eight papers to be presented exclusively on the web as part of the January 2000 JOM-e the
electronic supplement to JOM.
The following article appears as part of JOM-e, 52 (1) (2000),
http://www.tms.org/pubs/journals/JOM/0001/Zhitomirsky/Zhitomirsky-0001.html
JOM is a publication of The Minerals, Metals & Materials Society

Functional Coatings: Overview

I. Zhitomirsky

Electrodeposition is evolving as an important method in ceramic processing. Two
processes for forming ceramic films by cathodic electrodeposition are electrophoretic
deposition, in which suspensions of ceramic particles are used, and electrolytic
deposition, which is based on the use of metal salts solutions. Electrolytic deposition
enables the formation of thin ceramic films and nanostructured powders; electrophoretic
deposition is an important tool in preparing thick ceramic films and body shaping.

TABLE OF CONTENTS
●
●

INTRODUCTION
●

Electrophoresis was discovered in 1809 by Reuss of Moscow University. Many processes
●

1,2

based on electrophoretic deposition have been described, including deposition of thick
films, laminates, and body shaping. Some of these processes are in commercial use.
Significant interest has recently focused on cathodic electrodeposition, which offers

●

INTRODUCTION
CATHODIC ELECTROPHORETIC
DEPOSITION
CATHODIC ELECTROLYTIC
DEPOSITION
APPLICATIONS
References

3

important advantages for various applications; cathodic electrolytic deposition is a new
4

technique in ceramic processing that has been used to produce a variety of ceramic thin films.

3-22

Electrodeposition offers rigid control of film thickness, uniformity, and deposition rate and is especially attractive owing to
its low equipment cost and starting materials. Due to the use of an electric field, electrodeposition is particularly suited for
the formation of uniform films on substrates of complicated shape, impregnation of porous substrates, and deposition
on selected areas of the substrates. Two electrodeposition processes have been developed for forming ceramic
films: electrophoretic deposition (EPD)
are shown in Table I.

1-3

3,4

and electrolytic deposition (ELD) (Figure 1).

Features of the two processes

Table I. Electrophoretic and Electrolytic Deposition of Ceramic Materials
Electrophoretic Deposition

Electrolytic Deposition

Medium

Suspension

Solution

Moving Species

Particles

Ions or complexes

Electrode Reactions

None

Electrogeneration of OH- and
neutralization of cationic species

Preferred Liquid

Organic solvent

Mixed solvent (water-organic)

Required Conductivity of Liquid Low

High

Deposition Rate

3
1-10 µm/min

-3
10 -1 µm/min

Deposit Thickness*

3
1-10 µm

-3
10 -10 µm

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†

Deposit Uniformity

Limited by size of particles

On nm scale

Deposit Stoichiometry

Controlled by stoichiometry of
powders used for deposition

Can be controlled by use of precursors

*Controlled by variation of deposition time, voltage, or current density.
† Controlled by electric field.

CATHODIC ELECTROPHORETIC DEPOSITION
Electrophoretic deposition, a process in which ceramic particles, suspended in a liquid
medium, migrate in an electric field and deposit on an electrode, has been the subject of
1,2

considerable interest; review papers are now available. Electrophoretic deposition
offers important advantages in the deposition of complex compounds and ceramic
laminates. The degree of stoichiometry in the electrophoretic deposit is controlled by the
degree of stoichiometry in the powder used. According to Reference 1, particle/electrode
reactions are not involved in EPD, and ceramic particles do not lose their charge on being
deposited. The reversal of the electric field results in stripping-off the deposited layer.
Therefore, it is important to use similarly charged particles and similar solvent-binderdispersant systems for forming laminates of various ceramic materials and gaining better
control of layer thickness.

Figure 1. A schematic of electrolytic
deposition and electrophoretic deposition.

A suspension for EPD is a complex system in which each component has a substantial
effect on deposition efficiency. There are two principal types of solvents used: water and
organic liquids. Organic liquids are superior to water as a suspension medium since the use of water-based suspensions
causes gas formation from the hydrolysis of water. In general, suspensions can be dispersed by electrostatic, steric,
or electrosteric stabilization mechanisms. Ceramic particles must be electrically charged to permit forming by
electrophoretic deposition. The charge on a colloidal particle could originate from various sources, such as from
adsorbed simple inorganic ions or from dispersants. A binder is also added to the liquid to increase the adherence and
strength of the deposited material and prevent cracking.
When testing a new ceramic material in the laboratory, polyvinyl butyral as a binder, phosphate ester as a dispersant, and
ethyl alcohol as a solvent were generally used. Experimental results presented in Reference 23 indicate that phosphate ester
is one of the most effective commercial dispersants, acting as a steric dispersant by anchoring the long chain molecules to
the particle surfaces. Moreover, phosphate ester is an effective electrostatic stabilizer, which charges the particles positively
23,24

in organic liquids by donating protons to the surface.

Table II. The Compositions of Suspensions (SP) and Solutions (SL) and Experimental Conditions for Constant-Current EPD
and ELD

Suspension or Solution
SP1

SP2
SP3

SL1
SL2

Additives

Material

100 g/l TiO

A
2
B

100 g/l YSZ

C

100 g/l Al O
2 3
5 mM TiCl

D
4

5 mM ZrOCl

Current density (mA/
2
cm )

E

Solvent

Temperature
(° C)

G
2.2 g/l PVB + 2.5 g/l
H
PE

Ethyl alcohol

20

0.1

G
H
3 g/l PVB + 3.5 g/l PE

Ethyl alcohol

20

0.3

G
2.3 g/l PVB + 2.7 g/l
H
PE

Ethyl alcohol

20

0.2

0.01 M H O
2 2

Methyl alcohol-water
(3:1 volume ratio)

1

20

-

water

20

20

I

2



SL3
SL4

F

5 mM Al(NO )
33
2.5 mM TiCl

D
+ 2.5
4

-

Ethyl alcohol-water
(19:1 volume ratio)

20

5

I

Methyl alcohol-water
(3:1 volume ratio)

1

20

I

Ethyl alcohol-water
(19:1 volume ratio)

20

10

0.02 M H O
2 2

E

mM ZrOCl

2

SL5

F

0.02M SnCl

4

0.15 M H O
2 2

A Cerac (-325 mesh)
B yttrium-stabilized zirconia (YSZ) ,TZ-8Y, Tosoh
C Venton, Alfa Division (-400 mesh)
D Merck
E Fluka Chemie AG
F Aldrich Chemical Company
G polyvinyl butyral, average M = 50,000-80,000, Aldrich Chemical Company
w
H phosphate ester, Emphos PS-21A, Witco
I 30 wt.% in water, Carlo Erba Reagenti

Suspensions for EPD are produced by breaking down agglomerates
and uniformly distributing a dispersing agent on the surfaces of the
ceramic particles. The particle deagglomeration is carried out by milling
and ultrasonic treatment. The preparation of suspensions is carried out in
two stages. The dispersant must be added before the binder to
prevent competitive adsorption. Figure 2a shows deposit weight versus
time dependencies for titania, zirconia, and alumina deposits obtained
from suspensions SP1, SP2, and SP3, respectively (Table II). It is seen
that deposit weight increases with time at a constant current density.
The experimental data presented in Figure 2a demonstrate a manner in which
the amount of deposited material can be controlled.
Experiments indicate that the ethyl alcohol-phosphate ester-polyvinyl
butyral system is an effective system for cathodic deposition of various
ceramic materials. This is especially important for deposition of
consecutive ceramic layers of controlled thickness in multilayer
processing. Problems related to the application of toxic solvents, the
chemical compatibility of powders and additives, and deposit contamination
and corrosion of electrodes could be eliminated or diminished.
Prepared suspensions exhibited high stability, and a relatively high
deposition rate could be achieved. Due to the use of an effective binder,
obtained deposits adhered well to the substrates and exhibited enhanced
stability against cracking.
The deposition rate depends on applied electric field, suspension
1,2,25-30

concentration, and electrophoretic mobility of articles.
When considering other possible factors that can influence the deposition yield,
it is important to note that a certain potential distribution needs to be achieved
in the electrophoretic cell in order to supply sufficient voltage at the
26

Figure 2. Deposit weight versus time for (atop) electrophoretic deposits obtained from
suspensions SP1-SP3 and (b-bottom)
electrolytic deposits obtained from solutions
SL1-SL3 at constant current regimes.

electrode interface and obtain high deposition rates. Such potential
distribution can be realized by adding an appropriate amount of phosphate
31-33

that uniformity and adhesion of
ester or electrolyte. It was shown
the deposits can be improved by the use of electrolytes. However, an increase
in the electrolyte concentration caused significant aggregation of
ceramic particles and their sedimentation.


31

Particle sedimentation resulted


in decreased suspension concentration and was accompanied by a decrease in the deposition rate.
process resulted in porous deposits that included a significant amount of agglomerates.

31

25,31

The deposition

It is in this regard that the

34,35

explains the existence of a critical electrolyte concentration (flocculation value) for coagulation,
DLVO theory
below which the suspension is stable and above which it is kinetically unstable. The flocculation value decreases with
the valence of the electrolyte ions of a charge opposite to that of the colloidal particles (rule of Schulze and Hardey).
Constant-current or constant-voltage regimes could be used for EPD. The electric field
drives ceramic particles toward the electrode and exerts a pressure on the deposited layer.
It is desirable to maintain a high potential difference between the anode and the cathode.
The use of high voltages has the advantage of smaller deposition times and higher deposit
thickness. It should be noted that in the case of relatively large particles (~1 µm) stirring
the suspension is usually performed to prevent settling. In this respect, higher voltages and
smaller deposition times are preferable, because shorter deposition times allow deposition
without stirring. It was demonstrated that electrophoretic phenomena have distinctive
features for relatively large particles (several micrometers) and for particles on a
25

submicrometer scale. A high electric field and stirring can induce aggregation and
sedimentation of submicrometer particles, detracting from the deposition process
efficiency. It should be noted that high electric fields bring about porosity in the
25

deposits.

The use of the electrophoretic process for the deposition of ceramic materials enables the
deposition of uniform coatings on substrates of complex shapes. Figure 3a shows hollow
alumina fiber obtained via the EPD of submicrometer alumina particles (Baikalox SM-8,
Baikowski Ceramic Aluminas) on a carbon fiber and sintering in air at 1,400°C. The
obtained deposit was uniform in diameter along the entire fiber length (5 cm). The
uniform deposition results from the insulating properties of the deposit and electric field
dependence of the deposition rate.

3,27,28

However, deposit uniformity is limited by the
3,27-29

The possibility to form Figure 3. SEM micrographs of (a-top)
particle size of the powders used for the deposition process.
multilayer structures with controlled layer thickness and sharp interfaces between the
hollow alumina fiber obtained via EPD and
layers has been demonstrated.

30

Such composites are attracting considerable interest due
1

to their advanced mechanical properties. In multilayer fibers obtained via EPD, crack
propagation can be deflected at the laminate interfaces.

27

sintered at 1,400°C and (b-bottom) green
zirconia deposit obtained via ELD on
carbon fiber felt ( photo courtesy of
Technimat, Lydall Technical Papers).

CATHODIC ELECTROLYTIC DEPOSITION
Electrolytic deposition produces ceramic materials and provides their deposition. In the cathodic electrodeposition
4

method, the following reactions are used to generate base at an electrode surface:
–

2H O + 2e <==> H + 2OH
2

NO

–

3

–

2

(1)
–

–

+ H O + 2e <==> NO
2

–

2

+2OH

–

(2)

–

O + 2H O + 4e <==> 4OH
2

(3)

2

4

Some other cathodic reactions available for the generation of base have been discussed in the literature. Reactions 1–

3 consume H O, generate OH , and increase the pH at the electrode.
2

In cathodic ELD, metal ions or complexes are hydrolyzed by


4-6

electrogenerated base (Figure 4a) to form oxide,

hydroxide,

7-10

or

11-15

deposits on cathodic substrates. Hydroxide and peroxide
peroxide
deposits can be converted to corresponding oxides by thermal
treatment. Hydrolysis reactions result in the accumulation of colloidal
particles near the electrode. Turning again to the DLVO theory of
34,35

it may be concluded that the formation of a deposit
colloidal stability,
is caused by flocculation introduced by the electrolyte. The coagulation
of colloidal particles near the cathode can be enhanced by the electric
25

field, electrohydrodynamic flows,
the formation of new particles.

36,37

and pressure resulting from

Cathodic ELD is governed by Faraday's law. The amount of the
deposited material can be controlled by varying deposition time or
current density. Figure 2b shows deposit weight versus time dependencies
for titania, zirconia, and alumina deposits obtained from solutions SL1, SL2,
and SL3, respectively (Table II). Turning to the data on the EPD of the
same materials (Figure 2a), it is seen that the deposition rate in EPD is
much faster (by about 1-2 orders of magnitude) than that in ELD (Figure
2b), resulting in higher deposit thickness (Table I).
The amount of material deposited from solution SL2 increased with time in

Figure 4. The (a-top) electrolytic deposition
a decelerating manner. This result is inconsistent with Faraday's law.
of ceramic particles and (b-bottom)
intercalation of cationic polyelectrolytes into Possible reasons for the deviation of experimental deposit weights
4,5,7
electrolytic deposits.

Owing to
from Faraday's law have been discussed in previous papers.
the use of ionic species instead of ceramic particles, electrolytic
3

deposition allows better control of the deposition rate and deposit uniformity. The deposits obtained via the
electrolytic process have lower particle sizes and exhibit higher sintering activity. Figure 3b shows an electrolytic
zirconia deposit on a carbon-fiber felt. Electrolytic deposition results in the formation of uniform deposits on substrates
4

of complex shape. Deposit uniformity is controlled by electric field.

Aqueous or mixed solvents can be used for electrolytic deposition. It should be noted that the adsorbed water in asprepared deposits leads to cementation of small particles to form aggregates. However, the deposition process needs a
certain amount of water for base generation and prevention of the formation of nonstoichiometric oxides.
The formation of oxide materials via corresponding hydroxides and peroxides constitute
two different chemical routes in electrodeposition. The peroxoprecursor method has been
designed in order to solve problems associated with cathodic electrolytic deposition of
TiO

11,12,17

2

and Nb O

13,15

2 5

from aqueous solutions. The major problem with the

electrodeposition of these oxides is related to the use of water for base generation
(Reactions 1-3). Titanium and niobium salts immediately react with water to form
precipitates.
11,12,17

by use of a titanium
The problem of titania electrodeposition was solved
peroxocomplex. The peroxocomplex of titanium is stable under certain conditions in
water and has a cationic character. Electrodeposition of TiO films is based on hydrolysis
2

of a peroxocomplex at the cathode and formation of hydrated peroxide. Oxide films were
obtained by thermal dehydration of the peroxoprecursors. As-prepared titania films and
powders were found to be amorphous. After thermal treatment at 400°C, peaks of an
anatase structure were observed (Figure 5). The feasibility of cathodic electrolytic
deposition of niobium-oxide films via the peroxoprecursor method has recently been
13,15

demonstrated.

This approach has been further expanded to electrodeposition of


11


SnO ; ZrTiO (Table II, Figure 5); and other individual oxides, complex compounds, and
2

4

4,8,14-20

composites.

The hydrogen-peroxide additive has a number of effects on the deposits, as discussed in
14-18

References 8 and 15. The important finding was that complex compounds
can be
deposited via the peroxoprecursor method. The results of titania and zirconia
electrodeposition indicate that the deposits remains amorphous up to ~300-350°

Figure 5. X-ray diffraction patterns of
deposits obtained from solutions (a) SL1, (b)
SL2, (c) SL4, and (d) SL5 and thermally
treated at 400°C (SL1, SL2, and SL5) and
700°C (SL4) for 1 h. (O--TiO , --ZrO2, -2
ZrTiO , D--SnO ).
4
2

8,11,12,17

At higher temperatures, crystallization of nanostructured titania and zirconia
C.
was observed (Figures 5 and 6).
ZrTiO has been deposited via the peroxoprecursor method.
4

14,17

It was established that

the use of a peroxoprecursor provides an equal deposition rate of the individual
components and allows a deposit of desired stoichiometry to be obtained. The deposits
obtained from mixed titanium and zirconium salts solutions in the presence of hydrogen
peroxide remained amorphous up to 600°C. This is in contrast to the experimental data on
the electrodeposition of individual components. ZrTiO crystallizes directly from the
4

amorphous phase, as shown in Figure 5. No peaks of individual components were
observed. It was concluded that obtained green deposits are not a simple mixture of
individual components, but have a complex nature. This approach has been further
expanded to the formation of other complex compounds, such as PZT and
BaTiO .

4,15,16,18

3

As pointed out in References 19 and 20, the peroxoprecursor method cannot be applied
for depositing such materials as RuO . Ruthenium species bring about the decomposition

Figure 6. Crystallite sizes of electrolytic
titania (anatase) deposits (solution SL1)
determined from x-ray data at different
temperatures.

2

of H O in solution, and the electrodeposition of RuO films was performed via a hydroxide precursor. SnO , ZrO ,
2 2

2

2

2

La O , PbO, and some other materials can be deposited via hydroxide or peroxide precursors. The important finding was
2 3

9,10,15,19,20

can be deposited via cathodic ELD. Electrolytic deposition of ceramic composites, such as
that composites
ZrO -Al O , Al O -Cr O3, Al O -TiO , and TiO -RuO , was performed via hydroxide or mixed hydroxide/
2

2 3

2 3

2

2 3

2

2

2

peroxide precursors.
The influence of additives on the deposition rate and morphology of
9,10,15,18

Deposit cracking associated
electrolytic deposits has been studied.
with drying shrinkage is a common problem among wet chemical methods
once thick coatings are formed. Oxide films deposited via hydroxide
and peroxide precursors exhibited cracking when deposit thickness
exceeded ~0.2-0.3 µm. The cracking problem was approached by
16,19,20

It should be noted that the most common
multiple deposition.
binders used in EPD are nonionic-type polymers (polyvinyl alcohol,
polyvinyl butyral, ethyl cellulose, and polyacrylamide). The polymeric
molecules adsorb onto the surfaces of ceramic particles. Positively
charged ceramic particles provide electrophoretic transport of the
polymeric molecules to form deposits on cathodic substrates. However,
the application of these polymers for electrolytic deposition presents
difficulties, as the formation of ceramic particles is achieved near the
electrode surface (Figure 4a). However, it is possible to perform
electrochemical intercalation of charged polyelectrolytes into
electrolytic deposits (Figure 4b). By using cationic polyelectrolytes, such as
poly(dimethyldiallylammonium chloride) (PDDA) or polyethylenimine
(PEI) with inherent binding properties, problems related to cracking



in electrolytic deposits could be diminished. Moreover, various
organoceramic nanocomposites, such as Y(OH) -PDDA, Zr(OH) -PDDA, and

Figure 7. The deposit weight of alumina
versus cetyltrimethylammonium bromide
concentration, 0.1 M Al(NO ) solution in
33

3

4

Y(OH) -PEI can be obtained via electrodeposition. The intercalation of
3

ethyl alcohol, deposition time 20 min.,
2
current density 5 mA/cm .

polymer particles is achieved by their adsorption on the surface of
colloidal particles, which are produced near the cathode and form a
cathodic deposit. In the cathodic electrolytic deposition process, the pH in
the bulk of solutions is low; whereas Reactions 1-3 result in a significant
increase of pH value near the cathode. Therefore, a negative charge of colloidal particles formed near the electrode surface
can be expected:
–

–

M - OH + OH <==> M - O + H O
2

On the other hand, the electric field provides electrophoretic motion of
cationic polyelectrolytes toward the cathode. In this case, the adsorption
can be achieved via electrostatic attraction of oppositely charged
ceramic particles and polyelectrolytes. Cationic surfactants are of
considerable interest for application in ELD. Figure 7 shows that the
deposit weight of alumina increases with the increase of surfactant
concentration and remains relatively constant for concentrations higher
3

than 20 mg/dm . It is suggested that the surfactant acts like an
electrolyte in compressing the double layer of ceramic particles,
resulting in particle flocculation and increasing the deposition process
efficiency. The increase in yield of the deposit with increasing
concentration of surfactant could also be related to the retarded diffusion
–

of OH ions away from the cathode region.
Coating resistivity is a limiting factor of the ELD method for
development of thick films. As the coating process progresses, an
–

insulating layer is formed, which prevents OH generation. Some
individual oxides (RuO , IrO , SnO , and Cr O ) and composites
2

2

2

2 3

(RuO -TiO and Al O -Cr O ) exhibit high conductivity, and thick
2

2

2 3

2 3

4,7,15,19,20

deposits (up to ~10 µm) were obtained.
formed very thin deposits (up to 1-2 µm).

Insulating ceramics

References
1. P. Sarkar and P.S. Nicholson, "Electrophoretic Deposition (EPD):
Mechanisms, Kinetics, and Applications to Ceramics," J. Am. Ceram.
Soc., 79 (1996), pp. 1987-2002.
2. M.S.J. Gani, "Electrophoretic Deposition--A Review," Industrial
Ceramics, 14 (1994), pp. 163-174.
3. I. Zhitomirsky, "Electrophoretic and Electrolytic Deposition of
Ceramic Coatings on Carbon Fibers," J. Europ. Ceram. Soc., 18 (1998),
pp. 849-856.
4. I. Zhitomirsky and L. Gal-Or, "Electrochemical Coatings,"
Intermetallic and Ceramic Coatings, ed. Narenda B. Dahotre and T.S.
Sudarshan (New York: Marcel Dekker, 1999), pp. 83-145.
5. I. Zhitomirsky et al., "Electrochemical Preparation of PbO Films," J.
Mater. Sci. Lett., 14 (1995), pp. 807-810.
6. S. Peulon and D. Lincot, "Mechanistic Study of Cathodic
Electrodeposition of Zinc Oxide and Zinc Hydroxychloride Films from
Oxygenated Aqueous Zinc Chloride Solutions," J. Electrochem. Soc.,
145 (1998), pp. 864-874.
7. I. Zhitomirsky and L. Gal-Or, "Ruthenium Oxide Deposits Prepared
by Cathodic Electrosynthesis," Materials Letters, 31 (1997), pp. 155-


(4)

APPLICATIONS
There is a growing interest in
electrodeposition of various
1-22,38-59
ceramic materials.
Electrodeposition has been used
for the preparation of thin
4,6,16,40,42
(ELD
) and thick
1,2,38,39,41,43,44
(EPD
) films
16,38
of ferroelectric,
6,39
piezoelectric,
magnetic
40,41
materials,
42,43
superconductors,
and
4,44
The
semiconductors.
3,25,28
interest in EPD
and
45,46
ELD
for biomedical
applications stems from a
variety of reasons, such as the
possibility of deposition of
stoichiometric, high-purity
material to a degree not easily
achievable by other processing
techniques and the possibility of
forming coatings and bodies of
complex
3,28
shape.
1-3,47-49
EPD
and
3,4,21,22,50
ELD
are especially
attractive for the design of solid47
21,22,
oxide fuel cells,
solar
48
cells, electrochromic
49,50
devices,
microelectronic
1,2,4
devices,
fiber-reinforced
1,3,4
composites,
and


1,4
batteries.
Protective coatings
and electrode materials were
1,2,51,52
and
deposited via EPD
4,7,9,10,19,20,22
ELD.
Electrolytic TiO , RuO , SnO ,
2
2
2

159.
8. I. Zhitomirsky and L. Gal-Or, "Characterization of Zirconium,
Lanthanum and Lead Oxide Deposits Prepared by Cathodic
Electrosynthesis," J. Mater. Sci., 33 (1998), pp. 699-705.
9. R. Chaim et al., "Electrochemical Al O -ZrO Composite Coatings
2 3

2

on Non-Oxide Ceramic Substrates," J. Mater. Sci., 32 (1997), pp. 389400.
10. I. Zhitomirsky et al., "Electrochemical Al O -Cr O Alloy Coatings
2 3

Nb O , and composite
2 5

2 3

4,7,12,13,15,19,20
films
are of
considerable interest for
fabrication of dimensionally
stable anodes, supercapacitors,
and for other electrochemical
4
and catalytic applications.
Substantial interest in
38,43,53
54,55
and ELD
EPD
has evolved for the deposition
of oriented and patterned films.
One of the important
56
capabilities provided by EPD
57
and ELD is the ability to
achieve particle impregnation
into a porous substrate and
composite consolidation. EPD
has been demonstrated as a
suitable technique for the
fabrication of laminar ceramic
27,30
composites,
functionally
58
gradiented composites,
hollow fibers and coated
3
59
fibers, phosphor screens,
and shaping of ceramic
1,2
bodies. Electrolytic
deposition can be considered as
an important tool in the
formation of nanostructured
4,8,12,17
Other
materials.
applications of electrophoretic
and electrolytic films are
discussed in References 1, 2,
and 4.

on Non-Oxide Ceramic Substrates," J. Mater. Sci., 32 (1997), pp. 52055213.
11. I. Zhitomirsky et al., "Electrodeposition of Ceramic Films from NonAqueous and Mixed Solutions," J. Mater. Sci., 30 (1995), pp. 53075312.
12. I. Zhitomirsky, "Cathodic Electrosynthesis of Titania Films and
Powders," NanoStructured Materials, 8 (1997), pp. 521-528.
13. I. Zhitomirsky, "Electrolytic Deposition of Niobium Oxide Films,"
Mater. Letters, 35 (1998), pp. 188-193.
14. I. Zhitomirsky, L. Gal-Or, and S. Klein, "Electrolytic Deposition of
ZrTiO Films," J. Mater. Sci. Lett., 14 (1995), pp. 60-62.
4

15. I. Zhitomirsky, "Electrolytic Deposition of Oxide Films in Presence
of Hydrogen Peroxide," J. Europ. Ceram. Soc.,19 (1999), pp. 25812587.
16. I. Zhitomirsky, A. Kohn, and L. Gal-Or, "Cathodic Electrosynthesis
of PZT Films," Mater. Lett., 25 (1995), pp. 223-227.
17. I. Zhitomirsky and L. Gal-Or, "Cathodic Electrosynthesis of
Ceramic Deposits," J. Europ. Ceram. Soc., 16 (1996), pp. 819-824.
18. I. Zhitomirsky et al., "Electrolytic PZT Films," J. Mater. Sci., 32
(1997), pp. 803-807.
19. I. Zhitomirsky, "Electrolytic TiO -RuO Deposits," J. Mat. Sci., 34
2

2

(1999), pp. 2441-2447.
20. I. Zhitomirsky, "Cathodic Electrosynthesis of Titanium and
Ruthenium Oxides," Mater. Lett., 33 (1998), pp. 305-310.
21. H. Konno et al., "Electrochemical Formation of A-Site Substituted
Perovskite La M CrO Oxide Coatings," Electrochimica Acta, 37
1-x x

3

(1992), pp. 2421-2426.
22. H. Konno, M. Tokita, and R. Furuichi, "Formation of Perovskite
Structure La Ca CrO Films with Electrodeposition," J. Electrochem.
1-x

x

3

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2 3


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2

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Igor Zhitomirsky is with the Department of Materials Science and Engineering, McMaster University.
For more information, contact I. Zhitomirsky, Department of Materials Science and Engineering,
McMaster University, 1280 Main Street West, Hamilton, Ontario, Canada, L8S 4L7; fax (905) 528-9295; email zhitom@mcmaster.ca.

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