* To whom correspondence should be addressed E-mail: aymenma@hotmail.

com
New development of Anodic Electrocatalysts for Chloral-Alkali
industry.
SARFARAZ HUSSAIN
a
, M. ZIA-UL-HAQ
a
, ASHRAF DOGAR
a
, AYMEN MANZOOR AHMED
a
*, SHAHZAD ZAFAR
b

a Department of Chemical Engineering, NFC Institute of Engineering & Fertilizer Research.
b Department of Chemical Engineering, University of Engineering and Technology.
Abstract
Anodic Electrocatalysts are developed by
using a titanium substrate coated with
different compositions of mixed oxides of
ruthenium-titanium mixed oxides,
ruthenium-titanium-tin mixed oxides and
ruthenium-titanium-iridium mixed oxides.
Such types of anodes are used in caustic
chlorine cells, chlorate cells, sea water
electrolysis and similar applications. The
performance of electrocatalysts is
evaluated by different electrochemical
techniques, like voltammetry;
measurement of current efficiency, etc.
whereas its durability is gauged by standard
life test technique.
Anodes of all above mentioned
types are prepared and exposed to different
analysis, like, measurement of coating
thickness, studying coating morphology
with microscope, identifying the presence
of RuO2, TiO2, IrO2 and SnO2 in coating film
and analyzing shape of individual crystal by
XRD, performing voltammetry test,
accelerated life test and current efficiency
test of each type of anode. The processing
variables used to alter the properties are
composition coating.
Anode specimens of three major
types of DSA coatings (widely used in
electrochemical industry) are prepared and
examined regarding performance and
stability. It is concluded that all three types
are almost equally good regarding
electrolytic activity. However, the coating
composition of 15% RuO2 : 15% IrO2 : 70%
TiO2 is the best due to its maximum life. The
Electrolyzer containing anode plates of

coating composition of 15% RuO2 : 15% IrO2
: 70% TiO2 impart excellent results when
examined for currency efficiency.
Keywords: Electrode, XRD, DSA, Accelerated
life test.
1. Introduction
The electrode upon which oxidation occurs
in an electrochemical cell is called Anode.
The design and selection of the parameters
of anodes have traditionally been the result
of optimization of fixed and operating costs
of anode. Most of the materials used in
anode fabrication are characteristically
expensive. However, higher costs are
justified by enhanced performance and
reduced operational cost. An additional
consideration in the selection of an
appropriate anode is that it should be
environment-friendly.
Before 1965, the entire brine
electrolysis industry was using graphite
anodes. The use of these anodes was
abounded because graphite anodes were
consumable.
After 1965, the brine electrolysis industry
switched over to the use of Dimensionally
Stable Anodes (DSA) due to their following
main advantages over graphite anodes:
Lower power consumption;
Long anode life;
Cleaner products of electrolysis;
Elimination of environmentally
harmful materials;
More consistent and stable cell
room operation;
Reduction in labor.
Commercially Dimensionally Stable
Anodes (DSA) was first introduced in USA by
Electrode Corporation and then were jointly
developed by Diamond Shamrock-Oronzio
De Nora. Italy.
The DSAs are coated with expensive
coating materials. Main types of DSA
coatings used in electrochemical industries
are:
Ruthenium oxide based coating;
Iridium oxide based coatings;
Mixed ruthenium-iridium oxides
coatings;
Platinum-Iridium coatings;
Ternary system of coatings.

The formulation of coating solution
varies in each case while coating process
parameters remain the same. The work
presented in this paper concerns with
ruthenium oxide based coatings.
2. Experimental Work
In this experimental work, different
ruthenium oxide based coatings for DSA
were prepared and allowed to undergo
through different non-destructive testing
and electrochemical analysis in order to
seek optimum coating composition.
Both binary and ternary oxide systems were
tired. In binary system, Ruthenium-titanium
mixed oxide coatings whereas in ternary
system, Indium-Ruthenium and Titanium di-
oxide and Ruthenium-Titanium and Stannic
oxide coatings were investigated.
Process parameters (chemical etching
temperature and time, baking temperature
and time, annealing temperature and time
and loading of noble metals) for all types of
coating compositions were kept fixed.
2.1 Process Description
The coating of DSA involves the following
five stages:
1. Preparation of titanium substrate;
2. Application of coating solution to
substrate;
3. Baking of painted substrate;
4. Annealing;
5. Inspection of coated anodes.
These stages are shown as:

Figure 1: Block Diagram of the Process.
Stage (1): Preparation of Substrate
A specimen of titanium sheet (Chinese
standard: TA2) having grain size 40~60 m
was selected. The sheet was ground with
sand paper for the removal of foreign
matter. For verification of grain size,
metallography of titanium sheet was

performed with an optical metallurgical
microscope. Typical micrograph are shown
in Figure (2)
The ground specimen were etched
with oxalic acid (10% w/w) at 800
o
C for
three hours.
Stage (2): Application of coating solution to
substrate
The surface of specimens was painted with
a coating solution having specific
formulation.
Stage (3): Baking of painted substrate
The painted specimen were dried with hot
air at temperature from 50~600C, and were
baked in presence of excess air at 4500C in
a furnace for 10 minutes.
The specimen were cooled and
painted again. The process of painting
drying baking and cooling was repeated
until desired thickness of ruthenium metal
was obtained.
Stage (4): Annealing
Finally the specimen were heated at temper
of 4500
o
C for one hour and were gradually
cool down to ambient temperature. This
process is called Annealing. Detail of
prepared specimens are given in table (1).
Stage (5): Inspection of Coated Anodes
The inspection of anodes was carried out in
order to serve the following two purposes
a) Coating quality and material
identifications;
b) Performance of anode.

Figure 2: Typical metallographs.

Table (1): Detail of Prepared Specimens.


a. Quality & Thickness of coating and
identification of Material
The coated specimens were inspected with
optical metallurgical microscope for the
verification of coating morphology and
measurements of coating thickness. The
coated specimens were also inspected for
the identification of compounds/elements
and for the study of crystal structure with
XRD. Details of each analysis given in the
following paragraphs:
Study of Coating Morphology
The coating morphology of the prepared
anodes was studied with help of optical
metallurgical microscope. Typical
micrographs of different anodes are shown
in figure (2).
All the three micrographs show a
characteristic micro-cracked surface. These
cracks is occurred early in the coating
because solvent evaporated from the
surface and left a gel of unreacted
Ruthenium, Iridium, Tin and Titanium
compounds. Further, as the coating was
baked at higher temperatures, these cracks
increased in size because of the volume
contraction of the gel.
The establishment of cracks
increased the surface area several times
than the geometrical area as shown in
figure (2).
The increased surface area
contributes to low chlorine discharge
potential of these coatings and hence
providing a large number of catalytic sites
for gas evolution while minimizing
concentration polarization.

Measurements of Coating Thickness
The coating thickness of different
specimens was measured by using optical
metallurgical microscope. Micrographs of
different specimens are shown below:
o Micrograph of specimen # 28 in
Figure (3-a), showing a coating
thickness of 14.63m.
o Micrograph of specimen # 46 in
Figure (3-b), showing a coating of
4.8m.

o Micrograph of specimen # 54 in
Figure (3-c), showing coating of
6.3m.

Identification of Elements and
Compounds
Different specimens were analyzed by X-ray
diffractor for the identification of elements
and compounds in coating solution and for
the study of structure of solid solution. XRD
peaks of different specimen are shown in
figures (4). The compounds and elements
present in the coatings of the three
specimens as identified by the XRD
technique are given in table (2).

Figure (2-a): Micrograph of specimen 27.

Figure (2-b): Micrograph of specimen 45.

Figure (2-c): Micrograph of specimen 53.

Figure (3-a): Micrograph of specimen 28.


Figure (3-b): Micrograph of specimen 46.

Figure (3-c): Micrograph of specimen 54.


Figure (4-a): XRD peaks of specimen # 46.


Figure (4-b): XRD peaks of specimen # 54.


Figure (4-c): XRD peaks of specimen # 28.

Table (2): Identification of Compounds and
Elements in Coatings by XRD Technique.


b. Performance of anode
Voltammetry, Accelerated Life Test and
Current Efficiency Measurement techniques
were used to evaluate the performance of
anodes.

o Voltammetry
The technique of voltammetry was used to
establish the performance of anodes. The
voltammetry setup is given in figure (5).

o Accelerated Life Test
In the accelerated life test, the test
specimen of DSA is electrolyzed in saturated
brine solution (260~290 g\l of NaCl) under
constant current (operating current density
3 kA\m
2
) and terminal voltage. The voltage
across the working and reference
electrodes and recorded until the critical
value of 1.4 V, where corrosion of coating
within a few hours. The result of this test is
shown in figure (6). From the figure, it is
clear voltage increased sharply and test
specimen broke down.
In this test, it is observed that the cell
voltage decreased slowly at first (cause by
the activation of the inner surface in the
porous anode), then the voltage remain
unchanged for a long period of time and
finally steeply at the end of a service life.
The solution was circulated by a
sealed pump in order to keep the
composition of solution uniform. The pH of
solution was also maintained between 6~7.
Continuous tests stimulating
industrial conditions certainly provide
reliable data on anode durability but
require 2-3 years per test. Keeping this fact
in view, the following method was
employed:
The test anode was operated at a
high current density (30 kA\m
2
) at room
temperature in dilute brine (30 g\l). These
conditions give a potential greater than the
critical value of 1.4 V, where corrosion of
coating occurs within a few hours. The
result of this test is shown in figure (6).
From this figure it is clear that specimens#
53 have a maximum life and hence it is the
best.

o Current Efficiency Measurement
The fabricated anodes were installed in a
pilot plant of capacity 1.3 kg of sodium
chlorate per day. The plant was operated at
the same current density as in actual
operation (2.2 kA\m
2
, 85C). Setup for
current efficiency measurement is shown in
figures (7).
After operating the plant for 34
hours the current efficiency was calculated
as follows:
1. Theoretical production of sodium
chlorate (by Faraday Laws of
electrolysis): 1848g
2. Actual production of pilot plant:
1742g
3. Therefore, current efficiency: 94.2%

Figure (5): Voltammetry setup.


Figure (6): Accelerated life test.


Figure (7): Setup for current efficiency
measurements.

Conclusions
From the results of the experimental work
on the development of Ruthenium oxide
based coatings for the Dimensionally Stable
Anodes, it can be concluded that:
1. The coating having the following
composition exhibit larger Accelerated
Life and higher Current Efficiency than
the remaining two coatings:

a. Ruthenium oxide 15%
b. Iridium dioxide 15%
c. Titanium dioxide 70%
2. The Titanium sheet without any coating
is not a suitable anode for the electro
chemical industry.

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