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Chapter

Titanium Extraction Metallurgy

Developments and Control of
Impurity Elements
Chaganti R.V.S. Nagesh

Abstract

Titanium extraction metallurgy poses numerous challenges owing to a combina-

tion of various characteristics such as high chemical reactivity, high melting point,
strong affinity towards oxygen and nitrogen, pyrophoricity of nascent sponge. Kroll
process of magnesium reduction of has become the widely employed titanium sponge
production technology. Sodium reduction of TiCl4 known as Hunter’s process has also
been employed for the industrial production of titanium sponges for about two
decades. Subsequently quoting techno-economic reasons, the Hunter sponge plants
across the world have been closed. There have been several efforts over the years to
evolve an alternative to the Kroll process mainly to achieve a simple and cost and
energy-effective titanium extraction process. Control of impurity elements in the
titanium metal during the metal extraction process assumes greater importance as
thermodynamics does not favour any purification method to be employed for the
metal. This chapter brings out historical developments in titanium extraction metal-
lurgy and highlights recent developments as well to produce high-purity titanium
sponges required for titanium alloys for the end applications across various sectors.

Keywords: titanium, metal extraction, purity, quality control

1. Introduction

Titanium is an element with atomic number 22 and placed in the Group IV B of the
periodic table. Discovered by an English chemist, William Gregor in 1791, assumed its
name ‘titanium’ when a German chemist, M.H. Klaproth found it in 1795 as a new
element in the mineral rutile and called it ‘titanium’ (titans is the goddess of earth in
Greek). Titanium possesses a melting point of 1663°C and a density of 4.5 g/cm3.
Lightweight, high specific strength coupled with excellent corrosion resistance
resulted in titanium emerging as the structural material of choice for a variety of
applications in aerospace and many chemical industries. The titanium also has special
properties of body compatibility, non-magnetism and non-toxicity. Titanium has
different oxidation states and is highly reactive and forms alloys and compounds with
a large number of elements. It is because of the outer thin oxide film, the metal
exhibits superior corrosion resistance to a wide range of chemicals, seawater and
1
Titanium Alloys - Recent Progress in Design, Processing, Characterization, and Applications

aggressive media. The ability to form different types of attractive/lustrous shades of

colours on the surface on anodizing led to its use in artificial jewellery and various
types of eye-catching consumer durables.
Titanium exhibits allotropy and changes its crystal structure from hcp to bcc on
heating at 882°C. Important properties of titanium of interest for a material scientist/
metallurgist include its amenability to heat treatment to achieve tailor-made proper-
ties for different end applications. A large number of titanium alloys of type alpha,
alpha plus beta, beta and gamma phases are developed and put into use for various
types of applications up to a temperature of 550°C.
Titanium is plentifully available in nature. In the early days, it was referred to as ‘rare
metal’ mainly because of its limited usage on account of its expensive nature. Consti-
tuting about 0.63% of the earth’s crust, titanium is the ninth most abundant element and
fourth most abundant structural metal (after iron, magnesium and aluminium). The
two most important and widely available titanium minerals are ilmenite (FeOTiO2) and
rutile (TiO2). Ilmenite is subjected to chemical beneficiation or thermal smelting to
prepare synthetic rutile or titania slag, which contains increased TiO2 content.

2. Emergence of titanium extraction metallurgy

Extractive metallurgy of titanium is complicated due to the high melting point,

high chemical reactivity and pyrophoric nature (catches fire under frictional forces)
of nascent titanium metal. Vacuum or inter-gas atmosphere is essential for producing
titanium metal. Historically preparation of pure titanium metal from the oxide con-
centrate has been a challenging task. Early efforts to prepare the metal directly from
its oxide had been futile because of the large amount of oxygen retained in the
product. Oxygen, nitrogen, carbon and iron are the most important impurity elements
in titanium, which adversely affect the ductility and mechanical properties of the
metal. Realizing the implications of preparing the metal directly from the oxide, early
efforts shifted the focus to attempt metal separation from a non-oxygen-bearing
compound. Thus, chloride metallurgy came into existence where a metal chloride is
prepared by high-temperature chlorination of metal oxide and subsequently the metal
chloride is reduced/electrolysed to prepare the metal.
In 1910, Hunter developed sodium reduction of titanium tetrachloride (TiCl4) to
prepare high-purity titanium metal. The process was later on extensively studied and
developed by Imperial Chemical Industries, UK, for industrial implementation. Some
industries based on this process in UK and Japan had been operating till the early 90s.
In 1925, van Arkel and de Boer developed the process of dissociation of titanium
iodide (TiI4) on a tungsten filament to produce high-purity titanium metal. In 1937,
W J Kroll worked on magnesium reduction of TiCl4 to produce high-purity metal and
patented the process. The Kroll process was subsequently developed by the US Bureau
of Mines for industrial-scale implementation. Simultaneously in the former USSR and
Japan also similar developments took place. Fused salt electrolysis of TiCl4 to prepare
titanium was extensively studied by Dow Howmet USA, Reactive Metals Inc., UK,
and Electrochemica Marco Ginatta, Italy, and pilot scale plants had been operating
based on this process till recently. These three processes viz. Hunter process of sodium
reduction, Kroll process of magnesium reduction and fused salt electrolysis of TiCl4
are proven and are considered to be established methods of titanium sponge produc-
tion. In all three processes, nascent metal formed is in the form of a porous aggregate
of titanium metal particulates and termed as ‘titanium sponge’. Titanium sponge is the
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Titanium Extraction Metallurgy Developments and Control of Impurity Elements
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basic raw material for the manufacture of titanium/titanium alloys, which takes place
through vacuum arc melting of sponge into ingot followed by conventional metal
working techniques to obtain the desired product for end use. A detailed description
of the processes along with historical developments in metal extraction is well
documented in the literature [1–3]. Some of the experiences gained in the Kroll
titanium sponge technology development program [4] successfully conducted at the
Defence Metallurgical Research Laboratory, Hyderabad, India, are shared in this
presentation.
Subsequently, there have been several efforts the world over to develop a simple,
energy and cost-effective and environmentally friendly titanium extraction process.
Most of these efforts focus to cut down the process steps, evolving a continuous
process and/or directly obtaining titanium from TiO2. The majority of these advanced
processes result in titanium powder, which can be utilized in preparing the desired
products through additive manufacturing or 3D printing.

3. Established methods of titanium sponge production

As discussed, the preparation of TiCl4 is an essential step in the production of

titanium sponges. TiCl4 is mainly prepared by high-temperature carbo-chlorination
of titanium mineral concentrate (rutile/beneficiated ilmenite) in a fluidized bed-type
refractory lined furnace at a temperature of about 1000°C. The tetrachloride
obtained on chlorination is relatively impure containing chlorides of other metals
such as Fe, Sn, Si, Al, V. TiCl4 is an aggressive chemical and readily reacts with
atmospheric moisture and hydrolyzes forming thick fumes of HCl and oxy-chloride.
Hence, handling and purification of TiCl4 is hazardous and to be carried out cau-
tiously. Before using for the production of titanium sponge, TiCl4 is to be purified
sufficiently, which is generally done by employing fractional distillation and precip-
itation techniques.
Thus, the established methods of titanium sponge production essentially involve
the process steps (Figure 1) of chlorination of beneficiated ilmenite or rutile in the
presence of carbon at a temperature of about 950C to produce TiCl4, purification
of the tetrachloride by fractional distillation to obtain high-purity TiCl4 followed
by either sodium reduction (Hunter process) or magnesium (Kroll process). Alter-
natively, titanium sponge can also be produced by fused salt electrolysis of TiCl4
in LiCl-KCl melt. A brief description of these three processes is provided in the
sequel before a discussion is taken up on ‘control of impurity elements’ in the
product.

4. The Hunter process

In this Hunter process, TiCl4 is reduced with sodium metal and the following
chemical reaction represents the reduction process:

TiCl4 þ 4Na ¼ Ti þ 4NaCl, ∆Ho 800C ¼ 653:7 kJ=mole: (1)

The reduction process is conducted in an inert gas atmosphere using a steel cruci-
ble. TiCl4 is fed into the reaction crucible, which is holding a bed of molten sodium.
The temperature of reduction needs to be precisely controlled within the small range
3
Titanium Alloys - Recent Progress in Design, Processing, Characterization, and Applications

Figure 1.
Process flow diagram for established methods of titanium sponge production.

of melting point of NaCl (801C) and boiling point of sodium metal (887C) for ensur-
ing a smooth reduction process. The main product of the titanium sponge needs to be
separated from adhered by-product (NaCl) and leftover reductant (sodium), which is
done by water leaching of the reaction product Later on, however, the process
underwent several modifications and improvements compared to the method origi-
nally employed by Hunter. Nippon Soda, Japan and Deeside Titanium, UK-operated
titanium sponge production plants employing this process. However, the process has
several setbacks such as very high exothermic heat generation, highly reactive species,
very close window of process operating parameters, difficulty in recovering by-
product/effluent disposal, etc., in addition to the hazardous nature of handling
sodium. Currently, no industry is operating in the world based on this process for
titanium sponge production.
4
Titanium Extraction Metallurgy Developments and Control of Impurity Elements
DOI: http://dx.doi.org/10.5772/intechopen.108618

5. The Kroll process

The Kroll process of magnesio-thermic reduction of TiCl4 to produce titanium

sponge is represented by the following chemical reaction.
TiCl4 þ 2Mg ¼ Ti þ 2MgCl2 , ∆Ho 800C ¼ 325 kJ=mole: (2)

The reaction takes place between liquid magnesium and gaseous TiCl4 (boiling point
136C) forming solid titanium. There is a possibility of a large number of reactions
involving also lower chlorides of titanium viz. TiCl3 and TiCl2 as presented in Table 1.
The standard enthalpy and entropy changes of the reactions which indicate the ther-
modynamic possibility and exothermic/endothermic nature of reactions are presented
in the table. The overall reduction reaction is highly exothermic and necessitates exter-
nal cooling of the reactor for controlling the reaction temperature.
Physico-chemical aspects of reaction chemistry and some aspects of reaction
mechanism and titanium sponge formation in a Kroll reduction reactor are discussed
in detail in the literature [5, 6]. Also, phase equilibria in the system, Mg-Ti-Cl over a
wide temperature range of 500–2000°C, were studied. The extent to which a given
reaction would occur is influenced by several factors such as temperature, the physical
state of the reactants, mutual solubilities of the substances, surface and interfacial
phenomena, reaction kinetics and heat and mass transfer in the system.
From a thermodynamic analysis of various possible reactions involved in the
magnesio-thermic reduction of TiCl4, the following inferences were drawn:

• When gaseous TiCl4 reacts with liquid magnesium, reduction of TiCl4 to TiCl2 is
the most probable.

• When gaseous TiCl4 reacts with magnesium vapour, reactions that result in the
formation of TiCl2 and TiCl3 are the most probable.

• Formation of magnesium sub-chloride (MgCl) is also a possibility at high

temperatures. MgCl is unstable under normal conditions but is identified in the
gaseous phase at high temperatures.

• Among the secondary reactions of TiCl4 with titanium, the reaction forming
TiCl2 is the most probable.

S.No. Reaction ΔGo1100K ΔHo1100K

1 ½ TiCl4(g) + Mg (l) = ½ Ti(s) + MgCl2(l) 155.8 214.1

2 ½ TiCl4(g) + ¼ Mg(l) = ½ TiCl3(g) + ¼ MgCl2(l) 38.1 45.1

3 ½ TiCl4(g) + ½ Mg(l) = ½ TiCl2(s/l) + ½ MgCl2(l) 168.7 90.3

4 2/3 TiCl3(g) + 1/3 Mg(l) = 2/3 TiCl2(s/l) + 1/3 MgCl2(l) 60.3 174.2

5 TiCl2(l) + Mg(l) = Ti(s) + MgCl2(l) 130.9 90.7

6 ½ TiCl4(g) + 1/6 Ti (s) = 2/3 TiCl3(g) 8.2 20.6

7 ½ TiCl4(g) + ½ Ti(s) = TiCl2(s/l) 24.9 123.4

8 2/3 TiCl3(g) + 1/3 Ti(s) = TiCl2(s/l) 16.7 144.0

Table 1.
List of possible reactions in the Mg-Ti-Cl system.

5
Titanium Alloys - Recent Progress in Design, Processing, Characterization, and Applications

The reduction process is carried out in a steel/stainless steel crucible/reactor

under an argon gas atmosphere. It is a batch process and based on the batch size,
the required quantity of magnesium is taken into the reactor and heated to 780°C.
TiCl4 is then pumped into the reactor from the top closure of the reactor. The
temperature of reduction is maintained in the range 780–830°C by removing
exothermic heat through the circulation of air around the outer surface of the
reactor. Titanium particulate formed in the reduction process tends to agglomerate
in sizeable pieces along the reactor’s inner wall and grown pieces fall and are
collected at the perforated bottom plate of the reactor vessel. The reaction by-
product MgCl2 (which melts at 712°C) is liquid under reactor conditions and being
heavier than molten magnesium moves down paving the way for liquid magne-
sium to ascend to the top surface. MgCl2 collected at the bottom of the reactor is
periodically withdrawn from the reactor for accommodating the increased volume
of the titanium sponge. The titanium sponge grows as a cylindrical cake inside the
reactor. It is inevitable that some amounts of magnesium metal and magnesium
chloride get entrapped in the pores of the sponge during their transportation
through the sponge during the process. To compensate the loss of reductant
(magnesium metal) that is entrapped in the pores, usually 50–60% excess (more
than the stoichiometric requirement) magnesium is used in the sponge production
campaigns. After completion of the reduction process, the sponge cake comprises
un-reacted magnesium metal and magnesium chloride, which are entrapped in the
pores of the titanium sponge.
Vacuum distillation of the reduced mass is carried out by taking out the
reaction crucible containing the reduced mass into another reactor (Figure 2)
and heated to about 1000°C under a dynamic vacuum of the order of 5–
10 x 10 3 mbar, to distil out Mg/MgCl2 resulting in titanium sponge freed from the
entrapants. The basic principle in the vacuum distillation process is that at 1000°C,
the vapour pressure of Mg and MgCl2 is higher whereas the vapour pressure of
titanium is very insignificant. However, there are practical issues in the optimization
of principle parameters of the distillation process such as distillation soak, tempera-
ture, monitoring of vacuum as fall in the vacuum inside the process reactor is
overlapped with atmospheric leaks into the system. However, a realistic time of
distillation time could be assessed through simultaneous observation of vacuum fluc-
tuations in the process reactor/condenser vessel and electrical energy consumption
pattern of heating of the reactor with reduced mass. After cooling to room tempera-
ture under vacuum/argon gas, the sponge cake is ejected out of the reactor at room
temperature carefully employing appropriate equipment/tooling. Figure 3 shows a
photograph of a 3 MT sponge cake produced at the DMRL titanium research centre.
Any burnt or coloured particulates (formed due to oxidation) are manually removed
before the cake is further handled and processed to prepare 2–25 mm size material for
taking up ingot melting.
The Kroll process has several advantages over the other two processes of sodium
reduction and fused salt electrolysis in terms of scaling up product purity, and ame-
nability to recycle magnesium metal from the by-product (MgCl2) through electroly-
sis. Over the years there have been several technological advancements that taken
place in the Kroll technology as mentioned below:

• Enlargement of batch size (from 2 to 4 MT at the beginning of the industry to 8–

12 MT at present). Increased batch size is advantageous for enhanced
productivity and high-quality yield.
6
Titanium Extraction Metallurgy Developments and Control of Impurity Elements
DOI: http://dx.doi.org/10.5772/intechopen.108618

Figure 2.
Schematic of reactors for reduction and vacuum distillation processes in the conventional Kroll process.

• Combined process technology (wherein reduction and vacuum distillation

processes are conducted in a single reactors assembly system (Figure 4). This
significantly cuts down energy requirement and total cycle time of a production
batch.

• Recycling of by-product MgCl2 by fused salt electrolysis in multipolar cells to

regenerate magnesium metal and chlorine for captive consumption in an
integrated titanium sponge plant.

• Advanced process instrumentation and AI techniques for process control, sponge

sorting, etc.

• Evolution of different types of reactor materials, innovative sponge quality

evaluation techniques and so on.

7
Titanium Alloys - Recent Progress in Design, Processing, Characterization, and Applications

Figure 3.
A 3 MT titanium sponge cake produced at DMRL titanium experimental facility by combined process technology.

Figure 4.
Schematic arrangement of reactors in the combined process technology: (a) side by side and (b) one over the other.

8
Titanium Extraction Metallurgy Developments and Control of Impurity Elements
DOI: http://dx.doi.org/10.5772/intechopen.108618

6. Fused salt electrolysis of TiCl4

Electrolytic processes of metal extraction have many advantages such as sim-

plicity, scope for producing high-purity metal and amenable to semi-continuous/
continuous process operations and so on. Efforts on titanium metal extraction by
fused salt electrolysis concept are very old and several researchers put in efforts to
develop the same. Initially, electrolysis of TiO2 in molten electrolytes of alkali
borates and phosphates was pursued by International Research Inc., USA. However,
there were many technical issues such as higher operating temperatures, corrosive
electrolytes, product contamination by oxygen and difficulty in purifying the prod-
uct. Subsequently, fused salt electrolysis of TiCl4 in LiCl-KCl bath was considered
to be more viable and extensively studied simultaneously by Imperials Chemicals
Inc., UK, Dow Howmet and Reactive Metals Inc., USA, and Ginatta Marco, Italy.
Consistent and sustained efforts put in by GTT, Italy, on Pilot plant studies of the
electrolysis technology led to further development of the technology for industrial
implementation [6, 7]. It is learnt that the multi-valency of titanium, covalent
bonding in TiCl4 (characterized by solubility limitation) and control of product
purity have been found to be major challenges in working out a commercial model
of the cell.
Among the three processes as discussed above, the Kroll process withstood the
test of time and has been the predominant method of titanium sponge produc-
tion the world over. Though the electrolytic process is thought to be a potential
alternative to the Kroll process, to date, it remained at pilot scale operations
only.

7. World production of titanium sponge

Major titanium sponge-producing countries have been the USA, Japan, Russia,
Kazakhstan, Ukraine, UK, and China. In the UK, production was closed down in the
early ‘90s. In India, a small capacity (500 MT/year) titanium sponge plant was
established with the technology developed at DMRL and has been producing titanium
sponges since 2012 for meeting domestic needs. Recently, Saudi Arabia started a
15,000 MT/year capacity titanium sponge plant.
The present world production capacity for titanium sponge is placed at 3,50,000
MT per annum and China is contributing about 50% of the total [8]. It is to be noted
that. the Kroll process is used in the entire world production.

8. Control of impurity elements in the Kroll process

In view of the wide application of the Kroll process for titanium sponge produc-
tion, this chapter envisages to bring in a detailed discussion on the quality control
aspects pertaining to this titanium extraction method. As already mentioned, titanium
is highly reactive and the thermodynamics of the titanium-based systems do not
permit any purification method that can be implemented for purifying sponge. Only
control of impurities is a solution for preparing high-purity sponge. The important
impurity elements in titanium sponge that adversely affect its properties are O, N, C,
Fe, H, Ni, Cr, Mg and chlorides. Among this H impurity, Mg and chlorides are
generally not of serious concern as they are driven out during the ingot melting.
9
Titanium Alloys - Recent Progress in Design, Processing, Characterization, and Applications

However, Mg and chloride contents are to be kept at a minimum to improve the shelf
life of the sponge (before it is taken up for ingot melting).
The following are the major factors that influence the quality/purity of titanium
sponge produced by the Kroll process:

• Purity of raw materials and other consumables (TiCl4, Mg, argon gas, etc.)

• Cleanliness and pressure tightness of the reactor assembly

• Process operating conditions (Reduction temperature, TiCl4 feed rate, exposure

of reduced mass, order of vacuum and vacuum distillation soak, overall cycle
time, etc.)

• Reactor material

• Care taken during sponge cake handling and size reduction processing to prevent
contamination of sponge from equipment and tooling

• Sponge storage before melting

Mastery of high-purity titanium sponge production lies in all the above parame-
ters. For example, though the raw materials are of high purity, other parameters
mentioned above tend to cause impurity elements to join the sponge. In Table 2,
various parameters that act as a source of various impurity elements are listed. In
general, sponge material adjacent to the wall gets contamination by diffusion of an
impurity element from reactor material and the content of that reduces towards the
inner mass. The bottom portion of the sponge cake is highly contaminated due to
diffusion of impurity elements from the false bottom plate of the reactor and also, all
the impurity elements present in magnesium metal transfer into the sponge before the
metal ascends to the top of the liquid surface inside the reactor. The top portions of
the sponge are enriched with oxygen and chloride due to atmospheric leaks from the
nozzles of the reactor lid and entrainment of the last distilled chloride material. Based
on the experimental data involving analysis of the large number of samples collected

S.No. Parameter Source of impurity elements

1. Reactor material Fe, C, O

Carbon steel Ni, Fe, Cr
Austenitic stainless steel Cr, Fe
Ferritic chromium steel

2. Raw materials O, Fe, Si, Sn, etc.

TiCl4 Fe, Al, Si, etc.
Magnesium

3. Cleanliness & pressure tightness of reactor assembly O, N, H

4. Process operating conditions Fe, O, N, chloride

5. Equipment & tooling for sponge cake processing C, Si, O, Fe

6. Sponge storage O, N

Table 2.
Sources of impurities in the Kroll process of titanium sponge production.

10
Titanium Extraction Metallurgy Developments and Control of Impurity Elements
DOI: http://dx.doi.org/10.5772/intechopen.108618

from various sites across the sponge cake, a general pattern of impurities distribution
is known. Typical distribution of impurity elements in titanium sponge is schemati-
cally shown in Figure 5. Thus, the sponge in the central regions/core assumes the
highest purity and is separately harnessed while processing/size reduction of the
sponge cake to prepare homogenous quality lots of very high purity. All titanium
sponge producers evolve and follow systematic procedures for grading and quality
evaluation of sponge cakes and prepare uniform quality sponge lots in finished size,
which is suitable for subsequent ingot melting of Ti/Ti alloys [9].
Implementation of all quality control measures in titanium sponge production
results in higher purity of the product with enhanced yield. It is claimed that industry
giants prepare high pure sponges of 5 N (five nines, i.e., 99.999% Ti) and supply them
for critical & electronic applications [10]. Similarly, sponge with very low iron and
nickel (Fe + 3 Ni ≤ 120 ppm) is regularly prepared for the manufacture of critical
aero-engine components.
Though ASTM MD 120 provides complete specifications on titanium sponge
purity, it is advisable to consider sponges of much more purity for aerospace applica-
tions, in view of the high sensitivity of mechanical properties of titanium with respect
to the impurity elements especially O, N, C and iron. Major sponge producers across
the globe specify their own standards. MIDHANI is the major manufacturing unit of
titanium and titanium alloys in India. In Table 3, MIDHANI, Japanese (SHOWA) and
Russian specifications of high-purity titanium sponge are presented and a comparison
is made with ASTM specification. Analysis of the best sponge produced at the DMRL
research centre is also included in the table. The Brinnel Hardness Number (BHN) of a
machined button melted out of a sponge sample acts as a very informative indicator of
the purity of the sponge. Hence, a mention of BHN of the sponge is always found in
the titanium sponge specifications.

Figure 5.
Typical distribution of impurity elements in a titanium sponge cake.

11
Titanium Alloys - Recent Progress in Design, Processing, Characterization, and Applications

Impurity element CIS TG-90 SHOWA ASTM DMRL lot MIDHANI

S-90 MD 120 L001/2 K

O 0.040 0.060 0.100 0.032 0.080

N 0.020 0.010 0.015 0.003 0.015

C 0.030 0.020 0.020 0.006 0.015

Fe 0.060 0.030 0.120 0.018 0.050

Ni NS NS NS <0.005 0.050

Cr NS NS NS 0.009 NS

Mg 0.080 0.045 0.080 0.004 0.080

Chloride 0.080 0.080 0.120 0.005 0.100

H NS 0.002 0.001 0.002 NS

Ti (by difference) 99.6 99.8 99.6 99.8 99.6

BHN 80–90 90 120 82 100

Table 3.
Specifications of high-purity titanium sponge—different standards (content in wt%).

9. Trends in the development of alternate titanium extraction processes

The Kroll process technology though widely found acceptance has been used for
industrial-scale production of titanium sponges. It has the demerits of being highly
capital and labour-intensive, having higher energy consumption and higher cost of
production. Improvements over the years in technology implementation have reached
stagnation. Established titanium giants too claim an energy requirement of as high as
30–32 kWh/kg of sponge. However, the process has been sustaining as there is no
alternative method of sponge production is evolved so far. Worldwide over there have
been several efforts and intensive research continuing on alternate processes of tita-
nium metal extraction. During the last 2–3 decades, very encouraging developments
have been taking place with a few new extractions processes taken forward to even
pilot-scale production. Various process technologies that are being tried out for low-
cost production of titanium sponge are summarized by Kraft [11].
It is well known that titanium metal usage is restricted mainly because of higher costs.
The new alternate titanium metal extraction process mainly aims at bringing down the
energy requirement and cost of production. The approach for the same mainly consists of
simplifying the process flow sheet by cutting down the number of unit operations, direct
production of end components by combining the extraction and forming processes, etc.
Thus, the processes lead to the direct production of Ti/Ti alloy powders followed by near
net shape forming/3D printing (Figure 6) assuming greater importance and are on the
way of emerging as viable alternate titanium production methods.
The following innovative processes are mentioned worthy in this context and are
on the verge of adaptation for industrial-scale metal production.

9.1 The FFC (Fray Farthing & Chen) process

Titanium metal preparation directly from TiO2 by a novel electrochemical reduction

process was successfully developed and patented by Fray, Farthing and Chen of Cam-
bridge University, UK in 1999 [12, 13]. The process essentially involves cathodic

12
Titanium Extraction Metallurgy Developments and Control of Impurity Elements
DOI: http://dx.doi.org/10.5772/intechopen.108618

Figure 6.
Current trends in the development of alternate titanium metal extraction processes.

treatment of various types of TiO2 pre-forms at high temperatures (950–980°C) in an

argon gas atmosphere using molten calcium chloride as electrolyte and graphite as an
anode. When DC voltage is applied, oxygen of the TiO2 cathode is removed and
transported through the electrolyte to the anode where CO/CO2 is formed and let out.
After the process, the sponge is subjected to water/acid leaching for removing adhered
electrolyte material. Since the discovery of the process several developments/advance-
ments has been taking place for an improved understanding of the mechanism of metal-
lization, scaling up, enhanced product purity, applying process for alloy preparation and
exploiting the principle for other possible metal oxides, etc. Basic research carried out at
DMRL attempted to bring in an improved understanding of the reaction mechanism and
the importance of monitoring CO2 content in the vent gases [14, 15]. Excellent reviews
by Mohan Das [16, 17] bring out details of developments that have been taking place in
the FFC process over the years. Metalysis, UK, reportedly works on pilot-scale studies of
the process and even exploring industrial-scale implementation [18, 19] .

10. Armstrong process

The Armstrong process is based on the sodium reduction of TiCl4 (Hutner’s process)
with many advancements brought in to produce high-quality titanium powder particles
13
Titanium Alloys - Recent Progress in Design, Processing, Characterization, and Applications

in a continuous manner. The process technology was developed by researchers experi-

enced in handling molten sodium at International Titanium Powder LLC, IL, USA [20].
The process technology has been demonstrated for producing pure titanium powder as
well as standard titanium alloy powders. Basically, the process involves the reduction of
TiCl4 vapour, which is injected into a molten pool of sodium in a titanium reactor. The
product of titanium powder and sodium chloride is leached with water to remove the
salt. Any excess sodium metal in the product is separated by distillation.

11. OS process

Calciothermic reduction of TiO2 with several process improvements to obviate the

theoretical and practical difficulties encountered in the conventional calico-thermic
reduction has been constantly pursued by Ono & Suzuki of Kyoto University, Japan.
In the OS process, TiO2 is fed to molten calcium/CaCl2 bath and the reduction process
is continued with the dissolution of the reduction by-product CaO in the calcium
chloride. Continuous supply of the reductant, calcium metal is ensured by in situ
electrolysis of CaO that is generated as a by-product. Pilot plant scale studies were
reportedly carried out to study and establish the feasibility of continuous production
of titanium metal powder [21].

12. CSIRO process

Commonwealth Scientific and Industrial Research Organization (CSIRO), Austra-

lia, pursued and experimented on gaseous phase reduction of TiCl4 vapour with
magnesium metal vapour (with the same reaction basis as the Kroll process) in a
fluidized bed reactor [22]. The reaction by-product, MgCl2 and un-reacted magne-
sium metal are removed by vacuum distillation, while high-purity titanium powder
can be continuously withdrawn from the reactor. Based on the successful develop-
ment of the process for continuous production of titanium powder, it is being taken
forward to pilot-scale testing.
There are many other processes of titanium metal extraction that have been in
experimentation and pursued on a lab scale. The processes include the metal hydride
reduction process (MHR process) wherein TiO2 is reduced by calcium hydride, elec-
tronically mediated reduction process (EMR) wherein TiO2 is reduced by calcium metal
without any contact of a reductant, hydrogen-assisted magnesium reduction of TiO2
process, high temperature fused salt electrolysis of TiO2 using metallic anode (being
pursued by MIT, USA), combined magnesium thermal reduction of TiCl4 electro-slag
melting, etc., which promise a way ahead in the pursuit of evolving an alternated
process of titanium metal extraction. A recent review on titanium production methods
[23] covers many efforts that are being put in for developing a new process of titanium
metal extraction. Thus, titanium extraction metallurgy provides a large scope for trying
out different types of processes and techniques for producing the metal.

Acknowledgements

Author wishes to express sincere thanks and gratitude to Dr.G.Madhusudhan

Reddy, Outstanding Scientist and Director, DMRL for according approval for the
14
Titanium Extraction Metallurgy Developments and Control of Impurity Elements
DOI: http://dx.doi.org/10.5772/intechopen.108618

publication of this chapter on titanium extraction metallurgy developments. This rich

experience gained by the author in the area of development & demonstration of Kroll
titanium sponge production technology has been possible only because of the collec-
tive efforts of a large number of scientists, expert technical personnel and supporting
staff involved in the program at DMRL. Financial support provided by DRDO, DAE
and ISRO during various stages of development, demonstration and transfer of tech-
nology to the industry is gratefully acknowledged.

Author details

Chaganti R.V.S. Nagesh

Defence Metallurgical Research Laboratory, Hyderabad, India

*Address all correspondence to: [email protected]

© 2022 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of
the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0),
which permits unrestricted use, distribution, and reproduction in any medium, provided
the original work is properly cited.
15
Titanium Alloys - Recent Progress in Design, Processing, Characterization, and Applications

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