J Sol-Gel Sci Technol

DOI 10.1007/s10971-016-4009-0

ORIGINAL PAPER: FUNCTIONAL COATINGS, THIN FILMS AND MEMBRANES (INCLUDING DEPOSITION TECHNIQUES)

Deposition of (Ti, Ru)O2 and (Ti, Ru, Ir)O2 oxide coatings

prepared by solgel method on titanium
Mona Goudarzi1 Mohammad Ghorbani1,2

Received: 29 September 2015 / Accepted: 4 March 2016

Springer Science+Business Media New York 2016

Abstract Titanium anodes activated by noble metal Graphical Abstract

oxides possess a wide range of advantages and applica-
tions. Actually, coating of titanium anodes by highly con-
ductive oxides of noble metals (Ru, Ir) dramatically
increases the lifetime of these anodes. In this study, the
binary coating consisting of Ti and Ru and the ternary
coating consisting of Ti, Ru and Ir were prepared through
solgel method. After coating of the titanium substrate, the
corrosion behavior of coatings was studied by anodic
polarization and cyclic voltammetry tests. The lifetime of
anodes was determined using accelerated corrosion test.
The morphology of coatings was examined by field emis-
sion scanning electron microscopy and atomic force
microscopy. Phase analysis was done using X-ray diffrac-
tion. Results indicated that the microstructure of both
coatings is similar to cracked mud consisting of islands
separated by cracks, while the distribution of cracks in the
ternary coating is more uniform in terms of morphology.
The ternary coating is also more active in low overpoten-
tials, while ability of load transfer in the ternary coating is
reduced in high overpotentials.
Keywords Solgel  Titanium  Mixed metal oxide 
(Ti, Ru)O2  (Ti, Ru, Ir)O2  Accelerated corrosion test

1 Introduction

& Mohammad Ghorbani

Production of mixed metal oxide (MMO) anodes has been
ghorbani@sharif.edu optimized from 1970, in both terms, technology and
economy, for productions in chlorinealkali industry such
1
Department of Materials Science and Engineering, Sharif as sodium chlorate and sodium hypochlorite [14]. Opti-
University of Technology, P.O. Box 11155-9466, Tehran,
Iran
mizing this type of coatings reduces the price and increases
2
the lifetime of anodes. Successful development of cell
Institute for Nanoscience and Nanotechnology, Sharif
University of Technology, P.O. Box 11155-8639, Tehran,
membrane manufacturing technology in a larger scale leads
Iran to more optimized coatings in production of chlorine gas

123

and sodium hydroxide. Replacing RuO2 with IrO2 usually
neutralizes the dissolution of ruthenium oxide in alkaline
environments at the anodes surface and can form cell
membrane [5, 6]. Selection of suitable materials for cor-
rosion resistant is currently one of the important goals of
researches. These materials must meet the corrosion
problems in various industries, such as industrial chlorine
alkali, chemical processes, electrolysis processes and fuel
cells. A lot of researches had been done on this case. Most
of them focusing on applied coatings on anode surface [7
11]. The use of titanium-based anodes in chlorinealkali
industry is inevitable in order to provide good electrocat-
alytic activity for reduction reaction of chlorine (low
overpotential) and chemical and mechanical stability [12,
13]. This type of anodes usually contains a titanium sub-
strate with a noble metal oxide coating [14]. Much atten-
tion has been paid to Ti/RuO2 system because of the
excellent stability of electrocatalytic properties and also
prevention from passivation of titanium by the oxide
coating in this system [15, 16].
The microstructure of MMO anodes is similar to that of
cracked dried clay [1217]. Cracks play three primary
roles in these coatings: a place to release chlorine,
increasing the active surface area and a channel for dif-
fusing oxygen and inactivating titanium substrate. The
first two factors increase the efficiency and performance of
anodes. But the third factor reduces the electrochemical
performance of anodes since the effect of third factor is
more significant than other factors. The number of cracks
should be optimal to maintain a stable active surface [17].
Therefore, the presence of crack at the used anodes for
release of chlorine gas and oxygen gas is essential, but it
is of great importance to increase compactness and uni-
formity of the coating to prevent the penetration of oxy-
gen into the substrate surface because cracks can provide
the channel for oxygen to result in the passivation of
titanium substrate.
The aim of this work is to investigate (Ti, Ru)O2 and
(Ti, Ru, Ir)O2 oxide coatings. For this purpose, the oxide
coatings were applied on titanium by solgel method.
Then, the coatings were investigated.
2 Experimental procedures
2.1 Materials
Commercial pure titanium foils (grade 2) were used as
substrate. Titanium tetraisopropoxide (TTIP), RuCl33H2O
and IrCl33H2O (Merck) were used as starting materials for
solgel process. Hydrochloric acid (HCl) 37 % (Merck)
solution was used for chemical cleaning of titanium foils
prior to solgel process.
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2.2 Sol preparation
In order to provide the TiO2 sol, wateracid mixture was
stabilized at 70 C and this temperature was kept
throughout all the experiment, together with continuous
stirring. TTIP was added next, which formed a clear sol
after 2 h. The clear sol was cooled to room temperature.
The RuO2 sol was prepared by the addition of solid
RuCl33H2O to stirred boiling water to form dispersed solid
phase. This solution was kept at the boiling temperature for
6 h. The IrO2 sol was prepared by dissolving IrCl33H2O in
boiling water for 6 h, too. The obtained TiO2, RuO2 and
IrO2 sols were mixed with continuous stirring for 6 h at
ambient temperature. Then, the sol (Ru/Ir/Ti molar ratio of
40:20:40) was ready for running the solgel process.
2.3 Solgel process
The dipping process was conducted for 1 min and at
ambient temperature. Afterward, the coatings were dried at
100 C in oven for 30 min. The dipping and drying were
repeated in six steps and finally annealed at 450 C for 2 h
with the heating rate of 5 C/min. After annealing was
finished, samples cooled with the rate of 50 C/min in the
furnace.
2.4 Evaluation of coatings
The surface morphology of coatings was observed by
means of a field emission scanning electron microscope
(FESEM, S-4160 scanning electron microscope) and
atomic force microscopy (AFM, DUALSCPETM C26).
Then, the thickness of coatings was observed by means of a
field emission scanning electron microscope (FESEM,
S-4160 Scanning Electron Microscope).
Phase analysis was performed using X-ray diffraction
(XRD), and the adhesion of coatings to titanium substrate
was evaluated in accordance with ASTM D3359.
Electrochemical behavior of the samples was studied
using polarization and cyclic voltammetry tests in 1M
H2SO4, 0.5M NaCl and 0.5M NaCl ? 1M H2SO4 solutions
at ambient temperature with a scanning rate of 5 and
20 mV/s, respectively. For this purpose, a platinum elec-
trode and a saturated calomel electrode (SCE) were used as
counter and reference electrodes, respectively. All poten-
tials were measured against a reference electrode.
The samples were subjected to an accelerated corro-
sion test (ACT) with a constant high current density in a
dilute chloride solution in order to provide information
about the stability and the lifetime of electrode. To
perform this test, an electrochemical cell containing a
platinum counter electrode and a reference electrode
(SCE) was used. 0.5M NaCl solution was used at
J Sol-Gel Sci Technol
ambient temperature. The constant current density of
1.2 A/cm2 was applied. The potential-time curves were
recorded by a digital multimeter (Fluke 187 and 189).
3 Results and discussion
Figure 1 shows the surface morphology and the thickness
of (Ti, Ru)O2 and (Ti, Ru, Ir)O2 oxide coatings on titanium
substrate. In fact, the structure is dependent on the coating
composition [18]. The microstructure of both coatings is
similar to cracked mud consisting of islands separated by
cracks, with a uniform crack (Fig. 1a, b). The island border
zone appears brighter than the bulk of islands, which is
usually assigned to edge segregation of titanium oxide.
This effect is more pronounced for (Ti, Ru)O2 than for (Ti,
Ru, Ir)O2 coating, which indicates more uniform compo-
sition of the ternary coating. Indeed, the binary coating is
heterogeneous, containing agglomerates while the ternary
coating possesses more compact and smooth structure. In
the other words, the distribution of cracks in the ternary
coating is more uniform.
The surface fraction of crack was calculated using
Clemex Vision software. The surface fraction of crack at
(Ti, Ru)O2 and (Ti, Ru, Ir)O2 oxide coatings was about 10
Fig. 1 Scanning electron
micrographs and the thickness
of (Ti, Ru)O2 coating (a, c) and
(Ti, Ru, Ir)O2 coating (b, d) on
titanium
and 18 %, respectively. Furthermore, the most surface
fraction was observed in (Ti, Ru, Ir)O2 coating.
The cross section of the binary and ternary coatings
displays a uniform thickness of roughly 1.86 and 1.94 lm,
respectively (Fig. 1c, d).
The surface appearance of the oxide coatings on titanium
is shown in AFM 3D surface micrographs (Fig. 2). The
topography of the binary coating surface shows that surface
of coating is not uniform and shows a high surface rough-
ness (Fig. 2a). It was also observed that in the ternary
coating, the topography of coating surface becomes more
uniform. The average surface roughness (Ra) at the binary
and ternary coatings was 125 and 98.2 nm, respectively.
The adhesion of coatings to the substrate was also minimum
rating 4 A when tested in accordance with ASTM D3359.
Figure 3 shows the results of X-ray diffraction spectrum
from the coated samples surface. As shown in Fig. 3, the
binary coating is formed by metallic titanium and two
phases of rutile TiO2 and RuO2, while the ternary coating is
formed by metallic titanium and two phases of rutile TiO2
and (Ru, Ir)O2. In other words, RuO2 and IrO2 exist in the
ternary coating as (Ru, Ir)O2 solid solution due to the high
solubility of these two oxides.
Polarization curves for (Ti, Ru)O2 and (Ti, Ru, Ir)O2
coatings on titanium in 0.5M NaCl, 1M H2SO4 and 0.5M
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Fig. 2 AFM micrographs on titanium for: a the binary coating and b the ternary coating
Fig. 3 X-ray diffraction spectrum for titanium with the binary and
ternary oxide coatings
NaCl ? 1M H2SO4 solutions are shown in Figs. 4 and 5.
As shown in Fig. 4 and Table 1, the emission of oxygen
gas is begun at more positive potentials in 1M H2SO4
solution and the Tafel slope is about 0.18 V in this region.
With the entry of chlorine into the 1M H2SO4 solution, the
reaction of chlorine gas emissions is initiated in fewer
potentials and the Tafel slope is about 0.10 V indicating
high activity of the oxide coatings for this reaction. The
curve slope in 0.5M NaCl solution is calculated 0.12 V,
compared with the curve slope in 0.5M NaCl ? 1M H2SO4
solution, which is the result of different reaction mecha-
nisms. In solutions containing proton and chlorine, protons
are involved in active sites oxidation which create suit-
able sites for adsorption of chlorine gas. The reaction of
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Fig. 4 Polarization curves for (Ti, Ru, Ir)O2 coating on titanium in
(1) 1M H2SO4, (2) 0.5M NaCl ? 1M H2SO4 and (3) 0.5M NaCl
solutions
chlorine gas emission in such circumstances occurs in less
overpotentials as compared with NaCl solution [19].
Comparing Figs. 4, 5 and Table 1, it is observed that the
polarization curve changes are similar in the binary and
ternary coatings. The ternary coatings are more active in
low overpotentials, and currents for the ternary coating are
higher in 0.5M NaCl ? 1M H2SO4. They are prone to
decrease in ability to load transfer compared with the
binary coating in high overpotentials. This reduction is also
more visible in favorable solution for oxygen emission due
to low ability of oxygen compared with chlorine [18, 19]
since overpotentials for oxygen emission tend to be more
than overpotentials for chlorine. Their electrocatalytic
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Fig. 5 Polarization curves for (Ti, Ru)O2 coating on titanium in (1)
1M H2SO4, (2) 0.5M NaCl ? 1M H2SO4 and (3) 0.5M NaCl
solutions
Table 1 Potential of chlorine release and Tafel slope for (Ti, Ru)O2 and (Ti, Ru, Ir)O2 oxide coatings on titanium in different solutions
Solution (Ti, Ru, Ir)O2 oxide coating
Ba (V/decade) Potential of chlorine release (V)
1M H2SO4 0.18 1.24
1M H2SO4 ? 0.5 M NaCl 0.10 1.12
0.5M NaCl 0.12 0.98
property in such electrodes for oxygen emission is lower
than chlorine gas, meaning that oxygen is emitted more
slowly than chlorine gas.
Cyclic voltammetry curves of the binary and ternary
oxide coatings on titanium in 0.5M NaCl, 1M H2SO4 and
1M H2SO4 ? 0.5M NaCl solutions are shown in Fig. 6.
Capacitive behavior is the same for the binary and ternary
coatings in solutions containing proton. A broad reversible
peak is observed surrounding 0.60 V potential in solutions
containing protons (1M H2SO4 and 1M H2SO4 ? 0.5M
NaCl), which is because of oxidationreduction evolution
of ruthenium with the participation of protons. In fact, a
broad peak is visible in the potential ranging from 0.30 to
0.60 V and a small peak is visible in the potential rang-
ing from 0.60 to 0.80 V. According to researches, the
observed peaks can be attributed to oxidationreduction
processes Ru2O3/RuO2(Ru3?/Ru4?) and Ru2O3/Ru(Ru3?/Ru),
respectively. The broad peak in the potential range of
0.300.60 V is likely related to surface reactions sur-
rounding the entire surface of electrode [20]. In fact, the
electrode in potential range between hydrogen and oxygen
reactions is acting like a capacitor that load carrier protons
with change of the potential into cathodic values are enter
and by reversing the direction of potential are exit [20, 21].
The oxygen release begins in 1.10 V potential, and in
Fig. 6 Cyclic voltammetry curves for (Ti, Ru)O2 and (Ti, Ru, Ir)O2
oxide coatings on titanium in (1) 1M H2SO4, (2) 1M H2SO4 ? 0.5M
NaCl and (3) 0.5M NaCl
(Ti, Ru)O2 oxide coating
Ba (V/decade) Potential of chlorine release (V)
0.09 0.57
0.07 0.44
0.08 0.29
potentials more positive than 1.147 V, the oxidation of
RuO2 to RuO3 and RuO4 was took place. The oxidation of
RuO2 to RuO3 is the first step in the dissolution of the
active element, assuming that the amount of titanium in the
coating exists in oxidation state \?4 (non-stoichiometry
TiO2) and titanium with capacity \?4 can revitalize RuO3
in the form of stable RuO2 [21].
Because of less capacitive ability of IrO2 than RuO2,
voltammetric currents for the ternary coatings are lower in
NaCl electrolyte. Oxidationreduction evolution on surface
with the participation of protons is prevented because of
the lack of them. An increase in the anodic current in
voltagrams relating electrolytes containing chlorine ions
can be observed in potentials more positive than 1.15 V,
which is related to the initiation of chlorine gas emission
reaction. Increase is followed by the appearance of a
cathodic species which is dedicated to chlorine species
disposal. Potential increases with increasing the chlorine
ion concentration. The parts of the coating containing
segregation TiO2 (island edges) are areas with weak con-
ductivity, hence considered for semiconductor or insulating
properties. The flow is preferably carried by ions fill in
cavities in these areas. The total resistance of coating is
dependent on the electrolyte resistance. TiO2 existing in the
coating layer provides properties for the release of chlorine
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Fig. 7 Potential-time curves versus time for the binary and ternary
coatings on titanium in 0.5M NaCl solution
and increases the electrode lifetime and corrosion resis-
tance [11, 18, 22].
ACT results for the binary and ternary coatings in 0.5M
NaCl solution are indicated the time dependence on the
potential at constant current density in Fig. 7. As there is
little amount of oxygen produced in anodes and insignifi-
cant compared with produced chlorine, the anodes lifetime
will increase by reducing of the amount of oxygen in
chlorine gas [23]. Two reasons are suggested for the anode
electrocatalytic activity to diminish [24]:
1. Simultaneous electrochemical oxidation of ruthenium
species in the coating which form soluble products
entering electrolyte.
2. The formation of TiO2 insulating layer in substrate and
coating interface that grows through titanium substrate
oxidation by oxidizing elements such as chlorine and
especially oxygen.
Since IrO2 is more stable during the simultaneous emission
of oxygen and chlorine, anodes with the ternary coating
have a longer lifetime than anodes with the binary coating.
An experimental interpretation for more stability of the
binary and ternary coatings is presented as follows [19]:
RuO2 dissolution reaction and oxygen emission go for-
ward in parallel. RuO2 dissolution mechanism is as follows:
(1) RuO2 ? H2O ? RuO2 - OH ? H? ? e-
(2) RuO2 OH $ RuO3 ? H? ? e-
(3) RuO3 ? H2O $ RuO3 - OH ? H? ? e-
(4) RuO3 OH $ RuO4 ? H? ? e-
While proposed mechanism suggests that for oxygen
emission reaction stages (3) and (4) have to be replaced by
the following reaction:
(5) 2RuO3 $ 2RuO2 ? O2
Stage (1) and (2) are same for both reactions. Step (1) is the
rate determining stage. The species are decomposed later in
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(3)(5) stages and or produce oxygen or RuO4 that are
soluble in acidic solutions. Thus, with the presence of IrO2
in the coating, oxygen emission takes place mainly in IrO2
active sites preventing decomposition reactions on RuO2
active sites and causing significant increase in the coating
lifetime (Fig. 7).
4 Conclusions
The binary and ternary coatings of (Ti, Ru)O2 and (Ti, Ru,
Ir)O2 were prepared on the surface of titanium through sol
gel method, and their electrochemical properties were
studied in 1M H2SO4, 0.5M NaCl and 1M H2SO4 ? 0.5M
NaCl solutions. Results indicated that when iridium oxide
is present in the coating, oxygen emission significantly
takes place in active sites of iridium oxide. This prevents
decomposition reactions on active sites of ruthenium oxide
and significantly increases the lifetime of the coating. The
ternary coating is also more active in low overpotentials
and more prone to disability of load transfer in high
overpotentials.
Acknowledgments The authors would like to express the appreci-
ation to the Iran National Science Foundation for financial support.
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