Trans Indian Inst Met (2016) 69(5):999–1005

DOI 10.1007/s12666-015-0600-2

TECHNICAL PAPER

On Chemical Synthesis of Electrochemical Reduction of Titanium

Dioxide (TIO2) to Titanium Metal
G. Govinda Rajulu1 • M. Girish Kumar1 • B. Hari Babu2 • K. Srinivasa Rao1 •

Ch. R. V. S. Nagesh1

Received: 18 March 2015 / Accepted: 2 June 2015 / Published online: 19 January 2016
Ó The Indian Institute of Metals - IIM 2016

Abstract The process of electrochemical reduction of tita- 1 Introduction

nium dioxide to titanium metal has been studied in detail
through extensive experimentation in grams scale to For electrochemical reduction of titanium dioxide to tita-
5–8 kg scale. The objective of this study has been to describe nium, the FFC process [1] has been intensively explored by
the high temperature conversion process in terms of possible several researchers over the years, as the process has
chemical reactions involving species generally observed in immense potential for cost and energy effective production
the experimentation. Based on the measurements and exper- of the metal. The process involves high temperature
imental observations it was possible to describe the reduction (950 °C) molten salt electrolysis using TiO2 as cathode,
process in a thermodynamic point of view through a set of graphite as anode and calcium chloride as electrolyte.
chemical reactions involving various sub-oxides of titanium. Selection of calcium chloride as electrolyte is convincingly
explained in several reports as it acts as solvent and med-
Keywords Electrochemical reduction  Molten salts  ium for electrolysis of CaO that results in deposition of
Chemical synthesis  Titanium dioxide  calcium metal at TiO2 cathode [2–4] and liberation of CO/
Titanium suboxides CO2 at the anode. Thus, the overall reduction process is
expressed as
Abbreviations At cathode; TiO2 þ 4 e ¼ Ti þ 2O2 ð1Þ
DG Change in Gibbs free energy
0 At anode; C þ 2 O2  4e ¼ CO2 ðorÞ
DG Change in standard Gibbs free energy ð2Þ
E Emf 2C þ 2 O2  4e ¼ 2 CO
E0 Standard emf Extensive exploration of theoretical basis associated
n No of moles with the reduction process has been continuing over the
R Universal gas constant years for adequately explaining the reaction mechanism,
T Temperature in K influence of various operating conditions on kinetic aspects
F Faraday constant of the process [5, 6]. Based on cyclic voltametry and
K Equilibrium constant chronoamperometry and applying other advanced
techniques, attempts have been made to understand the
& G. Govinda Rajulu solid state transformations in TiO2 as the oxygen leaves the
govind.galam@gmail.com oxide in ionic form due to the applied DC voltage [7–10].
Ch. R. V. S. Nagesh While many studies postulate formation of suboxides of
nagesh@dmrl.drdo.in titanium during the reduction process [10], some also
1
Defence Metallurgical Research Laboratory, Hyderabad,
reported formation of calcium titanate as reaction
TS 500058, India intermediate [11, 12]. Studies on different TiO2 preforms
2
Department of Chemistry, Acharya Nagarjuna University,
and their treatment for its suitability for the reduction
Guntur, AP 522510, India process are also reported [13, 14]. In a recent review by

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Mohan Das [15], developments in the electrochemical
reduction process of TiO2, that have taken place over the
years on improved understanding of the process and
implications in the scale up of the process have
extensively covered.
Defence Metallurgical Research Laboratory (DMRL),
Hyderabad has been carrying out R&D on titanium
extraction by the electrochemical reduction of TiO2 and the
process feasibility in the scale of 3–5 kg could be estab-
lished [16–18]. Experimentation carried out initially on
gram scale and subsequently on 1 and 5–8 kg scale lead to
useful observations in developing improved understanding
of the process. This paper attempts to describe how the
conversion of TiO2 to titanium metal could be taking place
through a chemical synthesis and thermodynamic approach
substantiated by various experimental observations.
2 Conversion of TiO2 to Titanium—A
Thermodynamic Approach
In the electrochemical process of TiO2 reduction to tita-
nium, the overall reaction can be stated as,
TiO2 þ C ¼ Ti þ CO2 ;
though the physical contact of carbon and TiO2 does not
take place, it can be viewed as the initial phases of the
system (TiO2 and carbon) transforms into final phases of Ti
and CO/CO2 though there can be many intermediate
transformations/chemical reactions already proven to be
taking place. This is because the free energy change (DG)
associated with this transformation of initial species (TiO2
and C) into final species (Ti and CO/CO2) is independent
of intermediate changes/reactions. The theoretical mini-
mum emf required for this transformation can be obtained
as, -nFE = DG0 ? RT ln K. At 1200 K, the minimum
emf is determined as 0.64 V. Similarly as oxygen removal
commences when DC voltage is applied, the system can be
viewed to be consisting of sub-oxides of titanium viz.
Ti4O7, Ti3O5, Ti2O3 and TiO during various stages of the
reduction process. Table 1 lists various chemical reactions
probable under the conditions as discussed above. There
can also be a set of reactions where CO is by product
Table 1 Minimum emf required for the overall reactions for the conversion of TiO2 to suboxides and titanium metal
S. no. Chemical reaction
1 8TiO2 ? C = 2Ti4O7 ? CO2
2 16Ti4O7 ? C ? 2Ti = 22Ti3O5 ? CO2
3 7Ti3O5 ? C ? Ti = 11Ti2O3 ? CO2
4 3Ti2O3 ? C ? Ti = 7TiO ? CO2
5 2TiO ? C ? Ti = 3Ti ? CO2
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Trans Indian Inst Met (2016) 69(5):999–1005
instead of CO2, the thermodynamic possibility of such
reactions discussed in the later part of the paper. The values
of DG0 and minimum theoretical emf at 1200 K are also
determined using standard thermodynamic data [19] and
presented in the Table 1.
Alternatively, the electrochemical reduction process can
also place through calico-thermic reduction of TiO2/sub-
oxides of titanium, as calcium metal is deposited on the
TiO2 cathode due to electrolysis of CaO (formed as by-
product in the reduction of TiO2) dissolved in the elec-
trolyte. The values of standard free energy change deter-
mined for all the associated chemical reactions in the
temperature range 1000–1200 K are presented in Table 2.
As can be seen from the data, all the reactions associated
with the calico-thermic reduction of titanium sub-oxides
considered in the study, are thermodynamically feasible in
the experimental temperature range.
Thus, in both the cases of consideration viz. (i) initial
phases of TiO2/sub-oxides of titanium transforming to final
phases of titanium/sub-oxides of titanium and (ii) calcio-
thermic reduction of TiO2/titanium sub-oxides, the ther-
modynamic possibility of various chemical reactions
proposed herewith can be seen.
ð3Þ
3 Experimental Works
As mentioned earlier, feasibility of the process to prepare
titanium sponge of meltable grade in kg scale has been
established and current exercise relates to systematic analysis
of experimental data/observations to describe the reduction
process through a set of possible chemical reactions.
The electrochemical reduction process has been inves-
tigated through extensive experimentation conducted in
different batch scales of operation starting from a few
grams to 5–8 kg. High purity titanium dioxide powder is
taken into granule form (6–12 mm size) and sintered at
1000 °C. Electrolytic grade graphite has been used as
graphite. Several cell configurations were tried in order to
impart DC voltage effectively and achieve desired inter
electrode distance and proximity of granules to anode area.
Schematic of experimental set up employed for
100–200 g scale and 5–8 kg batches are shown in Fig. 1.
DG0 (J/mol) Min. emf required (V)
-863,178 0.369
-1,124,570 0.743
-1,103,396 0.117
-843,871 0.354
-525,832 0.446
Trans Indian Inst Met (2016) 69(5):999–1005 1001

Table 2 Free energy change determined for the chemical reactions associated with the calico-thermic reduction of TiO2 and sub-oxides of
titanium
S. no. Chemical reaction Temperature (K) DG of reaction (Joules)

1 4TiO2 ? Ca = Ti4O7 ? CaO 1000 -259,456

1100 -260,057
1200 -260,096
2 3Ti4O7 ? Ca = 4Ti3O5 ? CaO 1000 -239,628
1100 -241,289
1200 -242,080
3 2Ti3O5 ? Ca = 3Ti2O3 ? CaO 1000 -232,881
1100 -228,641
1200 -223,999
4 Ti2O3 ? Ca = 2TiO ? CaO 1000 -182,417
1100 -179,517
1200 -176,011
5 TiO ? Ca = Ti ? CaO 1000 -84,784
1100 -83,669
1200 -81,813

(-)
(a) (b)
(+)

(-) Argon in
Vent gases

Argon in
Vent gases

Graphite anode pipe (open)

Cathode TiO 2 granuales
Graphite anode pipe
Cathode basket

Molten CaCl2
TiO2 granuales
Molten CaCl2
Graphite anode
Graphite anode

Fig. 1 Schematic of experimental setups used in the experimentation a 100–200 g scale and b 3–5 kg scale

Typical experimental procedure followed has the fol-
lowing steps:
(a) Preparation of titanium dioxide dough by thorough
mixing of TiO2 powder (99.9 % purity) with 5 %
polyvinyl alcohol solution (binder) and using the
same to form regular sized granules in the size range
of 6–12 mm manually
(b) Sintering of granules in air at 1000 °C for 24 h for
consolidation and acquiring self strength
(c) Assembly of electrolytic cell system comprising
cathode basket, graphite anode, steel cathode in a
stainless steel reactor in which weighed quantity of
anhydrous calcium chloride is taken and melted under
argon gas cover, with the help of an electrical
resistance furnace
(d) Electrochemical treatment of the oxide granules at
high temperature under argon gas cover for a selected
period of time
Detailed description of the electrolytic treatment of the
oxide granules is as follows. The sintered granules are
taken into a stainless steel perforated basket which can be
vertically positioned with the help of a cathode lead rod in

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Table 3 Important parameters monitored during the experiment of 3–5 kg scale
S. no. Parameter
1 DC voltage
2 DC current
3 Furnace zone temperatures
4 CO2 detection (qualitative) through precipitation
in bubblers
5 Cathodic/anodic potentials
6 Electrolyte temperature, electrolyte level
7 Argon gas flow
Fig. 2 Photographs of a sintered TiO2 granules and b sponge granules
a stainless steel retort holding calcium chloride (elec-
trolyte). The experimental set up is heated to high tem-
perature (950–1000 °C) with the help of an electrical
resistance furnace. After melting calcium chloride the
cathode basket loaded with granules is immersed in the
electrolyte at a predetermined level and electrical connec-
tions to DC source are secured. Electrolysis is continued
for prescribed duration. During the electrolysis various
operating conditions are continuously monitored (Table 3)
to assess the progress of the reduction process. Identifica-
tion of CO2 in the vent gases from the retort by allowing
vent gases to flow through a baryta bubbler is practiced to
ensure that desirous reduction reactions are taking place. A
digital CO2 detector also put into use at selected time
intervals for quantitative measurement of CO2 content in
the out flowing gases. After the end of the experiment, the
setup is cooled under argon gas cover to room temperature.
Treated granules are subjected to a series of washings with
water and acidic solutions to separate the electrolyte
adhered to the granules. The granules are then dried at
room temperature and taken for characterization and
analysis by SEM, XRD, chemical analysis etc.
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Trans Indian Inst Met (2016) 69(5):999–1005
Range Frequency of logging/monitoring
3–5 V Continuous
60–300 A Continuous and manual recording
once in 15 min
970–980 °C Once in 30 min
– Continuous
– Once in 4 h
– Once in 6 h
0.1–0.2 cc/min Continuous
4 Results and Discussion
4.1 Characterization and Chemical Analysis
of the Product
Titanium sponge granules as obtained on electrochemical
reduction of titanium dioxide take shape of porous aggre-
gate of particulate matter. The washed product (granules)
generally can be classified into fully converted granules
and partially metallized granules, the relative proportion of
which determines the product yield of a given experiment.
Conversion of oxide to metal is first confirmed through
physical appearance and then through a spark test. Figure 2
shows photographs of sintered TiO2 granules before the
reduction process and sponge granules obtained on the
reduction process (3–5 kg scale). While the fully converted
granules are typically analyzed to find an oxygen content in
the range 500–2000 ppm, the partially converted granules
are found to contain as high as 5 wt% oxygen. The other
metallic elements such as Fe, Al, Si etc. are in the range of
300–500 ppm which are sourced from the starting oxide
material. After melting into button by inert gas arc melting,
Trans Indian Inst Met (2016) 69(5):999–1005 1003

Fig. 4 Variation of cathodic potential during experiment 3–5 kg

scale
Fig. 3 Variation of electrolysis current during experiment 3–5 kg
scale

the analysis typically showed a few hundred ppm of W in

addition to about 0.2 % oxygen.

4.2 Process Observations

Many observations made during the electrolysis time such

as variation of electrolysis current, changes in electrode
potentials, CO2 detection in the vent gases are found to be
very useful in understanding the behaviour of the electro-
chemical system. Typical variation of electrolysis current
(Fig. 3) during the time of electrolysis is characterized by
initial sluggishness followed by gradual rise to a peak value
and then gradually decreasing to a lowest value at the end
of the experiment. This is generally in agreement as the Fig. 5 Typical XRD spectrum of partially reduced granules (3–5 kg
scale)
quantity of oxygen to be removed from the starting mate-
rial gradually reduces to a lowest possible value as the
reduction progresses through formation of different sub-
oxides of titanium. Similarly there is a systematic variation
noticed in the electrode potentials. As can be seen in Fig. 4,
the variation of cathodic potential, after stabilization during
the initial period of electrolysis is seen gradually reducing
to lower value of around 1.2 V (at the end of the elec-
trolysis), which is much higher than the theoretical mini-
mum emf required for the conversion reactions of titanium
sub-oxides. This emf apparently meets the minimum the-
oretical emf requirement for the overall reactions (Table 1)
associated with the conversion of TiO2 to titanium metal
through various sub-oxide of titanium such as Ti4O7,
Ti3O5, Ti2O3, and TiO. Some of these sub-oxides are
detected by XRD in the partially reduced oxide granules as
shown in Fig. 5, while fully converted granules grossly
Fig. 6 Typical EDAX spot analysis of fully converted granule
showing titanium phase alone (Fig. 6).

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1004 Trans Indian Inst Met (2016) 69(5):999–1005

Fig. 7 Schematic of conversion 2- 2- 2-

O2- O O O
of TiO2 particulate into metal Ti4O7 Ti3O5 Ti2O3
through sub-oxides as the TiO2
oxygen is removed by TiO2 Ti4O7 Ti3O5
electrochemical action

2-
2-
O O
TiO Ti
Ti2O3 TiO Ti

Table 4 Free energy change for the chemical reactions associated with the electrochemical reduction of TiO2 and sub-oxides of titanium
Reaction steps Overall thermodynamic parameters
Initial phases Final phases Corresponding chemical reaction DG at 1200 K Theoretical
minimum emf

Step 1 TiO2, C Ti4O7, Ti, CO,CO2 4TiO2 ? C = Ti4O7 ? CO -3,227,174 0.391

Step 2 Ti4O7, Ti,C Ti3O5, Ti, CO,CO2 8Ti4O7 ? C ? Ti = 11Ti3O5 ? CO -1,223,786 0.578
Step 3 Ti3O5, Ti,C Ti2O3, Ti, CO,CO2 5Ti3O5 ? C ? Ti = 8Ti2O3 ? CO -1,175,570 0.199
Step 4 Ti2O3, Ti,C TiO, Ti, CO,CO2 2Ti2O3 ? C ? Ti = 5TiO ? CO -1,055,600 0.368
Step 5 TiO, Ti,C Ti, CO,CO2 TiO ? C ? Ti = 2Ti ? CO -867,204 0.859

4.3 Comparison of Results of Small Scale and 5 kg
Scale
With increased scale of operation from grams scale to 5 kg,
the dimensions and key parameters of cell configuration
inadvertently changes for achieving required operating
conditions of current densities, inter electrode distance,
increased cathode basket size to accommodate increased
quantities. As pure TiO2 constitutes about 40 wt% of oxy-
gen, a 100 g scale experiment needs to accommodate about
180 g of the oxide. Hence different cell configurations
needed to be tried in the course of experimentation. While
general observations of electrolysis current variation, elec-
trode potentials etc. are similar with increased scale of
operation, electrolysis time, the yield and purity of metal in
the scaled up batches is significantly different. The oxygen
content in the partially reduced granules is found to be
higher in the scaled up batches in addition to lower yield of
the higher purity metal. However, modelling of the kinetics
of cell reactions and optimization of the process conditions
are being attempted to address these technological issues.
4.4 Chemical Synthesis of the Reduction Process
Based on the experimental observations on system beha-
viour in terms of variation of electrode potentials, elec-
trolysis current, detection of CO2 in the vent gases and
characterization of the partially/fully converted granules, it
has become possible to generate an improved
understanding of reduction reactions/phenomenon associ-
ated with the bulk conversion process. When the titanium
dioxide particulate (aggregate/powder) experience a mini-
mum DC voltage of 2.6 V, its conversion to metal through
chemical reactions of calciothermic reduction is adequately
explained as,
4TiO2 þ Ca ¼ Ti4 O7 þ CaO ð4Þ
3Ti4 O7 þ Ca ¼ 4Ti3 O5 þ CaO ð5Þ
2Ti3 O5 þ Ca ¼ 3Ti2 O3 þ CaO ð6Þ
Ti2 O3 þ Ca ¼ 2TiO þ CaO ð7Þ
TiO þ Ca ¼ Ti þ CaO ð8Þ
However, the progress of these reactions, do depend on
wetting of TiO2 particulate by the electrolyte and removal
of high melting by-product CaO from the reaction sites
which is possible by dissolution of CaO in the electrolyte
(CaCl2 has solubility of over 15 wt% for CaO at 1200 K).
Further, the rate of dissolution of CaO in the electrolyte
should be corresponding to the rate of deposition of
calcium metal on the oxide.
Alternatively the conversion process of titanium oxide
to titanium metal can also be perceived to be taking place
through oxygen transportation from the oxide in ionic form
through electrolyte to anode wherein it is liberated as CO/
CO2. As already reported by Liu et al. [20] and others,
oxygen removal from the oxide is also possible at a voltage
below 2.6 V, the decomposition voltage of CaO. In such a
case, the oxygen ion that is generated at the TiO2

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Trans Indian Inst Met (2016) 69(5):999–1005
particulate on application of DC voltage (less than 3.2 V,
the decomposition voltage of CaCl2), is transported to
anode under the influence of applied voltage. The oxygen
transportation is explained through formation highly con-
ducting magneli phases (certain sub-oxides of titanium) in
the oxide. The drastic fall in the electrical resistivity of
TiO2 on heating to high temperature to about 10-2 X-m
[17], is usually attributed to the formation of highly con-
ducting sub-oxides of titanium. Thus under the conditions
of purely oxygen removal from the oxide through ionic
transportation, the conversion process of TiO2 to titanium
metal (described by the overall reaction, TiO2 ? 2-
C = Ti ? 2 CO) through suboxides can be described by
the following overall reactions, the thermodynamic feasi-
bility of which is already checked as discussed in Sect. 2
brought out above.
4TiO2 þ C ¼ Ti4 O7 þ CO ð9Þ
8Ti4 O7 þ C þ Ti ¼ 11Ti3 O5 þ CO ð10Þ
5Ti3 O5 þ C þ Ti ¼ 8Ti2 O3 þ CO ð11Þ
2Ti2 O3 þ C þ Ti ¼ 5TiO þ CO ð12Þ
2TiO þ 2C þ Ti ¼ 3Ti þ 2CO ð13Þ
Under actual experimental conditions, both phenomena
of calciothermic reduction and oxygen ion transportation
could be taking place simultaneously and the conversion of
TiO2 particulate could undergo transformations (as
illustrated in Fig. 7 and Table 4) to titanium sub-oxides
and eventually to titanium metal. Actual state of reduction
status of a given oxide particulate might depend on local
conditions such as wetting by electrolyte, temperature, emf
imparted etc. It becomes practically complicated to impart
conditions for complete conversion of oxide granules
especially in large scale batches and it is commonly seen
that many granules from the scaled up batches, are found to
contain significant amounts of oxygen possibly in the form
of unreduced sub-oxides. It may also to be noted that
partially reduced oxide particulate might be consisting of
more than one sub-oxide of titanium.
5 Conclusions
The process of electrochemical reduction of TiO2 to tita-
nium metal has been closely examined under different
scales of operation. Based on the extensive measurements/
1005
observation made during experimentation, an attempt has
been made to explain the electrochemical reduction process
through a set of possible chemical reactions associated with
the conversion process.
Acknowledgments Authors wish to express their deep sense of
gratitude to Dr. Amol A. Gokhale, Distinguished Scientist & Director,
DMRL for the constant support and encouragement extended to this
developmental activity and according permission to publish this
paper. Authors wish to acknowledge DRDO for providing funding to
this R&D work on development of the electrochemical reduction
process for titanium extraction.
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