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Research progress on the extractive metallurgy of titanium and its alloys

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Research Progress on the Extractive Metallurgy of

Titanium and Its Alloys

Yulai Song, Zhihe Dou, Ting-an Zhang & Yan Liu

To cite this article: Yulai Song, Zhihe Dou, Ting-an Zhang & Yan Liu (2021) Research Progress on
the Extractive Metallurgy of Titanium and Its Alloys, Mineral Processing and Extractive Metallurgy
Review, 42:8, 535-551, DOI: 10.1080/08827508.2020.1793145

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MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW
2021, VOL. 42, NO. 8, 535–551
https://doi.org/10.1080/08827508.2020.1793145

Research Progress on the Extractive Metallurgy of Titanium and Its Alloys

a,b
Yulai Song , Zhihe Doua,b, Ting-an Zhang a,b
, and Yan Liua,b
a
School of Metallurgy, Northeastern University, Shenyang, Liaoning, P.R. China; bKey Laboratory of Ecological Metallurgy of Multi-metal Intergrown
Ores, Ministry of Education, Northeastern University, Shenyang, Liaoning, P.R. China

ABSTRACT KEYWORDS
Titanium ores are plentiful in the earth crust, and the corresponding metal content ranks as the fourth Titanium and its alloys; SHS;
among structural metals; the application of titanium metal is restricted for its high cost in spite of its excellent electrolysis; thermal
mechanical properties, corrosion, and oxidation resistance. Titanium metal was first produced with Hunter reduction; extractive
metallurgy
process yet this has been practically replaced by Kroll process which contains carbochlorination of rutile and
ilmenite to obtain TiCl4, followed by metallothermic reduction with magnesium. The complex procedure,
huge investment, and considerable energy consumption have markedly prevented the development of
titanium. Electrolysis has been proposed by Fray et al. in the early twenty-first century, developed and
derived by many other researchers, involving both anodic and cathodic process, use TiCl4 and titania as raw
materials. However, the efficiency and continuity issues remain inevitable, while self-propagating high-
temperature synthesis (SHS) seems a good alternative for its rapid, continuous, and controllable character­
istics. The extractive metallurgy of titanium and its alloy plays an important role in the effective utilization of
titanium. At present, there is a lack of the latest review on the extractive metallurgy technology of titanium
and its alloys. In this paper, the development status of extractive metallurgy of titanium and its alloys are
reviewed, and finally, the direction of extractive metallurgy of titanium and its alloys is prospected.

1. Introduction leanness in valuable minerals and insufficient methods avail­

able to handle such low-grade sands (Kalinnikov and Nikolaev
Due to the light weight, high specific strength, corrosion, and
2002). Nowadays, the increasing demand for lightweight and
oxidation resistance at elevated temperatures, titanium and its
high-strength alloys under certain applications has stimulated
alloys can be used as important high-temperature structural
the study of the low-cost preparation of titanium alloys.
materials and are widely used in aerospace, petrochemical,
Up to now, a large number of preparation methods have been
automobile, and metallurgical industries (Baker 2019; Cui
investigated to extract titanium and its alloys from their stable
et al. 2011; Elias et al. 2008; Kim et al. 2014; Kim and Kim
compounds, which could be mainly divided into two categories:
2018; Wu 2006). The titanium-bearing minerals were firstly
electrolysis and thermal reduction. In general, the former con­
discovered in the late eighteenth century, while until 120 years
tains the electrolysis of TiCl4 in molten salt (Fraser, Imam and
later, the pure titanium metal with only a few grams has been
Kosaka 2016; Fray 2008), the electrolysis of TiO2 in molten salt
produced through sodium-thermal reduction of high-purity
(Chen, Fray and Farthing 2000; Fray and Chen 2004; Hu et al.
TiCl4 under vacuum condition, which led the foundation for
2018; Ma et al. 2006), extracting sponge titanium using a solid
mass production. Nevertheless, titanium is usually associated
oxygen-permeable membrane (Zhao et al. 2005; Zou and Lu
with other metals in nature, such as iron and vanadium, so the
2010), TiO2 in-situ reduced by metal Ca obtained by electrolyz­
extractive metallurgy of titanium is usually accompanied by the
ing CaO in CaCl2 molten salt (Ono and Suzuki 2002; Suzuki
upgrading of titanium ore and the separation with associated
2005), and titanium prepared by the electrolytic-soluble anode
elements (Boyer, Welsch, and Collings 1994). To date, the
TiCxOy in molten salt (Jiao and Zhu 2007; Zhang et al. 2012),
main valuable ores under the current technological and eco­
while thermal reduction consists of magnesiothermic reduction
nomic conditions are rutile, leucoxene, and ilmenite.
(Kroll 1940), sodium-thermal reduction of TiCl4 (Hunter 1910),
According to the data released by U.S. Geological Survey
carbothermic reduction (Zhu et al. 2011), and self-propagating
(Gambogi 2020), world resources of anatase, ilmenite, and
high-temperature synthesis (SHS; Kamali, Razavizadeh and
rutile total more than 2 billion tons, in which ilmenite accounts
Hadavi 2007; Li et al. 2017b, 2017a; Merzhanov and
for about 89% of the world’s consumption of titanium miner­
Borovinskaya 1972, 2008; Zuhair and Umberto 1989), respec­
als; meanwhile, the world titanium sponge production reached
tively. Many researchers have devoted to exploring the elemen­
305,000 metric tons in 2019. With the continuous depletion of
tary mechanism of deoxidation and the corresponding mass
high-grade titanium ores and the increasing demand for TiO2,
transfer process in the past decades. Moreover, the smelting
the low-grade titanium sand has become an important source
procedure of titanium combined complex high temperature
for the production of ilmenite concentrate; however, the large-
and multiphase physicochemical process, the materials selection
scale utilization of the sand is disappointedly scarce, due to its
of electrode and equipment, process optimization, and the

CONTACT Zhihe Dou douzh@smm.neu.edu.cn School of Metallurgy, Northeastern University, Shenyang, Liaoning 110819, P.R. China
© 2020 Taylor & Francis Group, LLC
536 Y. SONG ET AL.
realization of production continuity are necessary to resolve
(Chen, Masazumi and Takeo 1987; Nagesh and Ramachandran
2007; Wang, Liu and Chen 2011; Zhang et al. 2016). Recently,
a novel Near-net Shape Electrochemical Metallization (NSEM)
process has been proposed to fabricate titanium components
from oxides (Dolganov et al. 2020). Through the comparison
between NSEM and conventional route, the comprehensive
impact of titanium production from the novel method on eco­
system, human health, and natural resources could be greatly
reduced. Looking at the overall situation of titanium metallurgy,
it is composed of the purification of raw materials, the conversion
efficiency of energy in extraction process, the utilization of valu­
able elements, and recycling of by-products (Fray 2008; Gao et al.
2018). At present, as for the extractive metallurgy of titanium,
Kroll process is still an irreplaceable metallurgical technology,
which is orientated toward large-scale, continuous, and auto­
mated direction after decades of development. Generally speak­
ing, the most profound impression of these products made with
titanium is of good performance, high cost, and uncommon in
daily life, which made them mainly be applied in the so-called
advanced high-technical fields. To enlarge the broad application
of titanium, great efforts are imperative to reduce the economic
consumption in the extractive process of titanium and its alloys.
In this paper, the research progress of extractive metallurgy of
titanium and its alloys is reviewed. Characteristics of each method
and the existing deficiency are also analyzed. Finally, the develop­
ment tendency of preparation methods for titanium and its alloys
is then prospected, which could help researchers on this subject to
understand the latest research status of titanium metallurgy.
2. Reduction of TiCl4
2.1. Thermal reduction of TiCl4 (Hunter/Kroll process)
Hunter process, as the earliest known successful way to obtain
titanium, was developed in 1910 and used liquid sodium as
reductant to reduce TiCl4 to achieve the purpose of acquiring
titanium. The products produced from Hunter process could
be used as the feedstock for titanium applied in the electronics
industry for its ample grade of purity (Hunter 1910). First, the
titanium-bearing ores were chlorinated at elevated tempera­
tures, which can transform TiO2 into TiCl4 solution in the
form of high valence ions and eliminate the possibility of
titanium reacting with oxygen and nitrogen in air. Then, the
TiCl4 prepared from chlorination process went through pur­
ification procedure to remove impurities that brought from
ores, and eventually purified into reactor with liquid sodium,
in which the main reactions can be divided into two categories:
one-step method and two-step process for the reduction of
TiCl4. After the exothermic reaction completed and the reactor
cooled to room temperature, the titanium with porous struc­
ture (titanium sponge) was removed, collected, and classified,
while the sodium chloride solution was sent to electrolysis
procedure to obtain sodium and chlorine for reduction and
carbochlorination process, respectively. The main reactions are
listed as follows:
Δ
TiO2 þ 2Cl2 þ 2C ¼ TiCl4 þ 2CO " (1)
Δ
TiCl4 þ 4Na ¼ 4NaCl þ Ti(One-step method) (2)
Δ
TiCl4 þ 2Na ¼ TiCl2 þ 2NaCl(Two-step method) (3a)
Δ
TiCl2 þ 2Na ¼ 2NaCl þ Ti(Two-step method) (3b)
electrolysis
2NaCl ) 2Na þ Cl2 " (4)
Due to the slight solubility in molten sodium chloride of
sodium, the electrolyte was made conductive and the reduction
process took place in the bulk of the molten sodium chloride to
nucleate fine particles of titanium suspended in the melts,
which was then settled out. However, the Hunter process had
gradually been superseded by the Kroll process for its costly
sodium reducant. Accompanied by the fact that the Deeside
Titanium plant operated the Hunter process in the UK closed
in the early 1990s, this procedure has been formally sealed up.
Compared with Hunter process, Kroll process characterized
with higher electrolytic efficiency, cyclic utilization of by-
products, which made it the prevailing method of preparing
titanium. Up to now, the vast majority of titanium in the world
is produced through this route, and the schematic chart is
detailed in Figure 1. In summary, this path mainly contains
four steps and two circulates: The former constitutes chlorina­
tion, magnesiothermic reduction, vacuum distillation, and
electrolysis of magnesium chloride, while the latter is com­
posed of cycling of magnesium and chloride, respectively.
Actually, the whole course is complicated with various phases
involved, which display a multiphase physicochemical process
consist of chemical reaction, adsorption, evaporation, conden­
sation, diffusion, dissolution, and crystallization. Meanwhile,
as the fact the reduction of high valence titanium compounds is
a stepwise process, to decrease the impurities exist in the final
products, excessive magnesium had to be added into the mag­
nesiothermic reduction process, which lead the low utilization
efficiency of magnesium. On the other hand, overemphasizing
the utilization efficiency of magnesium will lead to the increase
of low-valent titanium compounds in the products and pro­
longation of production cycle, which requires a compromise
between energy consumption, efficiency, and the quality of
product.
The microstructure of powder titanium produced via metal­
lothermic reduction of TiCl4 is shown in Figure 2 (Fang et al.
2018). The crystal size and powder morphology could be mod­
ified through the regulation of raw material ratio and experi­
mental conditions, the average particle size of 15–20 μm with
oxygen (0.19–0.58%, wt.), nitrogen, and chlorides (50 ppm).
Moreover, measures taken as the encouraging work dedicated
to reducing oxygen pick-up during water leaching and product
drying are expected to further reduce oxygen contamination.
The process is believed to have significant commercial poten­
tial for production of lower-cost titanium, especially for use in
powder metallurgy (PM) applications to produce near-net
shape products (Amarchand et al. 2001). In the future, efforts
should focus on the prevention of titanium lumps generation,
the lower impurities and higher uniformity of products, the
suitability for downstream powder metallurgical applications,
and the operation safety of molten salts (Vuuren, Oosthuizen
and Heydenrych 2011).

Figure 1. Schematic chart of Kroll/Hunter process (M stands for Mg/Na, x = 2, 1).
Figure 2. SEM image of powder titanium produced via metallothermic reduction
of TiCl4.
2.2. Clean preparation of titanium by coupled Kroll
method with in-situ pyrolysis reduction magnesium
smelting process
The electrolyze of MgCl2 by-product produced in classical
Kroll process needs extensive investment on equipment and
enormous power consumption, which led to most of plants in
China trend to directly depose them as waste, along which
valuable components and heat carried by them were comple­
tely wasted. Under this background, Zhang et al. (2011) had
proposed a novel clean production process called in-situ pyr­
olysis reduction magnesium smelting, which can be briefly
described as the molten MgCl2 produced by reduction distilla­
tion is directly oxidized with oxygen injection and pyrolyzed to
obtain high-purity MgO and chlorine. For the enterprises with
the whole process of Kroll process, the MgO can be reduced
through thermal magnesium smelting and then the products
would be returned back to TiCl4 reduction, while the chlorine
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 537
be utilized in boiling chlorination. Obviously, compared with
the electrolysis process, the efficiency of thermal process is
significantly improved, on the premise of realizing the novel
Mg-Ti combination and cyclic utilization in the preparation
procedure of sponge titanium. The short clean production
process of sponge titanium based on the new cycle of MgCl2
is shown in Figure 3 (Niu et al. 2014).
Niu et al. (2013, 2014) had systematically investigated the
oxidation and pyrolysis process of molten MgCl2, and appro­
priate operation conditions were determined, with pyrolysis
temperature 1200°C, oxygen partial pressure 0.1 MPa, and
time 50 min, respectively. The pyrolysis rate of molten MgCl2
can reach 99.99% and the chlorine content in the product is 26
ppm under the optimum conditions. The microstructure of the
obtained MgO powders showing an irregular hexahedral shape
has an average diameter of 1 μm with uniform size distribution,
good dispersity, high crystallinity, and purity. The dynamic
study of pyrolysis reaction shows that this reaction is controlled
by chemical reaction at the initial stage of reaction.
Moreover, Lyu et al. (2019) have studied the influence of the
granule morphology of MgO particles on the yield of pyrolysis
products. Wang et al. (2014) have designed the pyrolysis device
for molten MgCl2. He et al. (2019) have studied the velocity
and concentration fields in the reactor for the pyrolysis of
gaseous MgCl2 and O2 by numerical and physical simulation,
which could provide the available data support for the novel
clean production process of titanium sponge, and the products
could be applied for the fabrication of titanium-related com­
ponents. At present, the in-situ pyrolysis reduction magnesium
smelting process is still remaining in laboratory stage, and long
time needed to be transformed into industrialization.
2.3. Electrolysis of TiCl4
Trace back to the 1950s, Wilhelm Kroll predicted that an
electrolytic route would replace his metallothermic process
538 Y. SONG ET AL.
Figure 3. New flow sheet of technological process for titanium sponge production.
within 15 years; however, more than half century passed but his
prediction has yet to come true. Retrospect the history of
aluminum industry, which showed that the transform from
a metallothermic route to the electrolysis of alumina dissolved
in cryolite promoted the industry from being boutique to mass
production. Encouraged by the background of alumina pro­
duction, some researchers tried to electrolyze TiCl4 that fused
in chloride solution of alkali or alkaline earth metal to prepare
titanium metal. The schematic diagram of the whole electro­
lysis process is shown in Figure 4.
For the different affinity to oxygen with titanium and alu­
minum, in order to prevent titanium from being oxidized
again, the process should be carried out in an argon atmo­
sphere. Throughout the electrolysis process, the chloride ions
Figure 4. Schematic diagram of electrolysis.
move to anode under the electric field and lose electrons to
generate chlorine then overflow, while the titanium ions
approach to the vicinity of cathode to get electronics to gen­
erate titanium metal attached to cathode. With the electrolysis
process proceeding, the concentration of TiCl4 in electrolyte
gradually decreases, and the titanium layer precipitated to
cathode continuous densification, which needs TiCl4 to be
injected into the electrolyte later. Moreover, it has been con­
firmed very difficult to plate out solid planar deposits of metals
from molten salts as the solid deposits usually nucleate and
grow as dendrites. The principle of electrolysis of TiCl4 is
simple as depositing solid titanium at cathode and evolving
chlorine at anode. However, the actual process is more com­
plicated with the limited solubility of TiCl4 in molten salts for

its considerable vapor pressure; thus, the fresh TiCl4 is needed
to be continuously added into the electrolyte. In alternative
methods, Ginatta and Orsello (1987) have attempted to elec­
trolyze titanium salts to produce molten titanium by dissolving
TiCl4 in a mixed fluoride-chloride-based melt. The reaction is
certificated as the following processes:
The dissolution process:
3CaF2 þ KCl þ TiCl4 ¼ TiKCaF6 þ 2CaCl2 þ 1=2Cl2 " (5)
The electrolysis process:
TiKCaF6 þ 2CaCl2 ¼ Ti þ 3CaF2 þ KCl þ 3=2Cl2 " (6)
After the reaction completed, the liquid titanium can be either
tapped or solidified and drawn from the cell together with
some solidified electrolyte (Ginatta 2004). There exist lots of
characteristics in this procedure over these for production of
solid titanium, including complete separation of titanium from
electrolyte without taking additional separation techniques and
much shorter distance between the two electrodes as the unne­
cessary space retained for dendritic growth of the deposit.
Furthermore, the progress is so challenging that the reactivity
of molten titanium which may necessitate very expensive
refractories and much more important, the containment of
molten salts is also extremely difficult for its fluxility at these
very high temperatures. So, the bulk extraction of titanium
through the electrolysis of TiCl4 still needs long time to realize.
3. Reduction of TiO2
3.1. Electrolysis of TiO2 (FFC process)
Until 2000, an epochal research on extraction of titanium
through electrolysis of TiO2 was published in Nature, which
is called FFC process. It was deemed to be a green technol­
ogy characterized with low consumption and free of pollu­
tion, and also considered as a promising route to prepare
titanium over significant periods of time. The diagram of
FFC process is presented in Figure 5 (Chen, Fray and
Farthing 2000), the left cell shows two pellets placed at the
bottom of a titanium or graphite crucible which also func­
tions as the cathodic current collector. This arrangement
resembles a basket electrode that can be removed from the
cell after electrolysis, allowing filtration of molten salt. While
Figure 5. Electrolytic cells for the reduction of TiO2 pellets.
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 539
the two pellets in the right cell are threaded onto a Kanthal
wire (current collector) and suspended in the molten salt.
This type of assembled electrode can also be removed from
the cell easily after electrolysis. The electrode reactions are
listed as follows:
Anode :2O2 þ C ¼ CO2 þ 4e (7)
Cathode :TiO2 þ 4e ¼ Ti þ 2O2 (8)
The independent operating module for FFC method contains
mixed compression molding of raw materials involving TiO2
and additive agent, sintering, electrolysis, and the crush of final
products. In the course of electrolysis, O2- was ionized from TiO2
under the presence of external electric field, and directionally
move to the anode inside the melts then oxidized to release oxygen,
which reacts with the anode carbon to produce CO2 (or CO) to
release. Correspondingly, the remaining titanium ions in the cath­
ode gain electrons to generate titanium metal, along with the
electrolytic reaction proceeding, the cathode TiO2 continuously
transits to titanium metal until the entire reaction is completed.
The FFC process used TiO2 as raw material, which got rid of
the chlorination process to produce TiCl4, could obviously
simplify the procedure. More importantly, the cheap titania
precursors including titania dust, solid metatitanic acid, and
titanium-rich slag could theoretically be used as initial ingre­
dients, with the addition of other metallic oxides to prepare
corresponding alloys. Owing to the surprising results of the
reduction process of mixed oxides, the final products of the
alloy powders are not the mechanical mixing of elemental
elements, but with a homogenous alloy in respect of elements
that form solid solutions or a mixture of the phases predicted
by the phase diagram (Fray 2008). Meanwhile, some metallic
impurities in the titanium-rich slag, such as aluminum and
manganese, were found to be partly or completely removed
after electrolysis for the difference of electronegativity, which
makes it possible to utilize low-grade and mixed ores. Figure 6
shows the SEM image of the microstructure of titanium metal
reduced through FFC process. Compared with Kroll process,
the FFC process has the merits of short process, the prefabri­
cated electrodes make the semi-continuous production, the
quality improvement of the products with a much lower con­
tent of oxygen, which can be lowered as a few hundred parts
per million. Furthermore, no contamination occurs for the
540 Y. SONG ET AL.
Figure 6. SEM image of the microstructure of titanium reduced through FFC
process.
absence of chlorine generation in the whole process. Schwandt
(2013) has studied the electro-deoxidation mechanism of TiO2
to titanium metal and emphasized the importance of the com­
position of the electrolyte and its interplay with the other
components of the electrolytic cell. Natsui et al. (2020) have
developed an in situ observation technique of the TiO2 inter­
facial behavior in molten LiCl-KCl electrolysis and presented
two characteristic variations of the thin TiO2 electrode surface
by tracking through the high-speed digital microscopy syn­
chronized with the electrochemical measurement. However,
the mechanism of deoxidation is still ambiguous including
the concrete steps of reaction, the impacts on the formation
process of O2- and the diffusion of products and reactants.
Besides, the suitable parameters for electrolysis as well as the
equipment complication and process continuation are also
a necessary solution to overcome.
3.2. Calciothermic reduction (OS process)
The OS process, firstly proposed by two Japanese researchers:
Ono and Suzuki (Ono and Suzuki 2002), is used to achieve the
reduction of TiO2 to titanium metal by calcium obtained from
the electrolysis of CaO in molten salt; therefore, it is also called
as calciothermic reduction. The difference in decomposition
voltage between CaO and CaCl2 supplied the feasibility of this
method. Once the cell voltage was controlled higher than the
decomposition voltage of CaO (1.66 V) and simultaneously
lower than that of CaCl2 (3.2 V), extra ingredients containing
mixture of TiO2 particles and pure calcium are set as trigger
agent to initiate the calciothermic reaction. The electrolysis and
reduction were integrated into one equipment, as is shown in
Figure 7. Basic concept of cell design (a) and products obtained from OS process (b).
Figure 7. There exist two major processes in this pathway:
firstly, elemental calcium generated through electrolysis of
CaO dissolved in molten CaCl2. However, this proved difficult
as the precipitated calcium dissolved immediately inside the
salts (Ferro et al. 1997, 1998; Kipouros and Sharma 1990), for
the solubility is 3.9% (mole fraction) calcium in CaCl2 at
1173 K (Dosaj, Aksaranan and Morris 1975; Fischbach 1985;
Staffansson and Sichen 1992), which resulted in raising the
electronic conductivity of the melt and lowering the current
efficiency. Then, the CaCl2 solution contained the dissolved
calcium was transferred to the reduction zone under the gra­
dient of concentration with the dissolved calcium reduces the
TiO2 to form calcia and titanium metal. It was noted that while
the container holding the slurry of TiO2 was in contact with the
electrode, the reduction progress was much faster than the
suspended TiO2 in the melts and the oxides were only reduced
to the suboxides (Suzuki, Teranuma and Ono 2003). As the
reaction is controlled by many factors, such as diffusion and
chemical reaction, the restrictive step is usually diffusion,
including the approach of reactants to the reaction zone and
the departure of the products. In extreme conditions, when the
container in direct contact with the cathode, the arrangement
is very similar to the FFC process.
The applied carbon anode resulted in the formation of
carbon sludges, as with the FFC process. To overcome this
problem, Susuki and his coworkers (Suzuki 2008; Suzuki,
Teranuma and Ono 2003) used an yttria-stabilized zirconia
(YSZ) membrane to prevent the carbonate ions reaching the
anode. Unfortunately, YSZ can be reduced by the calcium
dissolved in the electrolyte.
Apart from the reduction of TiO2, Yamaguchi et al. (2007a,
2007b) had tried to use TiCl4 as the source of titanium and this
is reduced by the calcium produced in an electrochemical cell.
Certainly, to overcome the inherent low current efficiency of
electrowinning cells for calcium, innovative high electrolyte
flow cells are proposed. Moreover, appropriate measures
should be taken to stabilize the composition of electrolyze to
form the stable cell circumstance to improve electrolysis
efficiency.
3.3. Solid-oxide-membrane (SOM) process
An environmental SOM technology emerged as a short proce­
dure that can efficiently synthesize metal and alloy directly

from their oxide ores with minimum feed-material preparation
and produce oxygen or water vapor as the major by-product
(Pal, Woolley and Kenney 2001). This method is to fuse metal
oxide into molten salt system with low melting point and high
solubility, which usually used a system composed of MCln-
MFn, and M represents alkali or alkaline earth metal. By con­
trolling the ions that participated in electrode reaction, the
metal oxides are involved in the cathode reaction, and graphite
is used as the cathode material. The porous cermet (YSZ)
coated with permeable membranes on the surface of the
anode is used to isolate the anode from the electrolyte so that
only oxygen is the anion involved in the reaction. In addition,
in the process of electrolysis, hydrogen is also introduced into
the anode, and the final product of the reaction is water, with
the schematic diagram is presented in Figure 8.
The SOM technology has successfully extracted magnesium
metal in a much energy-saving and environmental-friendly
than conventional route, including metallothermic reduction
at high temperatures (1873 K) involving expensive metal
reductant (FeSi) or electrolysis from a halide electrolyte bath.
In 2005, Zhao et al. (2005) in Shanghai University have
extracted titanium sponge in laboratory through SOM, there­
after, compounds including Ti-Si (Zou and Lu 2010; Zou et al.
2010), Ti-Fe (Chen, Li, and Lu 2012; Ye et al. 2011), and Ti-Al
(Li et al. 2017) have been produced at laboratory scale. This is
a considerable advantage over the Kroll process and opens up
the opportunity to synthesize alloys that are difficult to produce
conventionally such as those with vastly different densities,
melting points, or vapor pressures.
3.4. Electrolysis of soluble TiCxOy composite anode (USTB
method)
Anodic dissolution of Ti2+ from Ti-O-C composite anodes,
firstly described in the 1950s, has been developed by MER
Figure 8. The SOM process for metal (Me) production by direction reduction of its oxides.
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 541
Corporation using the combination of cost-affordable titania-
rich feedstocks and a cheap source of carbon to produce
titanium metal, which is known as MER process (Withers
and Loutfy 2011). The composite anode contains a complex
reduced TiO2 compound, such as TixOy-C; titanium ions are
released into the electrolyte and deposited as solid titanium on
the cathode, while a composite mixture of CO-CO2 is evolved
at the anode. Similarly, another novel process for producing
high-purity titanium has been developed by Zhu and his cow­
orkers at University of Science and Technology Beijing (USTB)
through electrorefining titanium oxycarbide solid solution
(Jiao and Zhu 2006), and the schematic diagram is shown in
Figure 9.
It is well known that high-purity titanium can be obtained
on the cathode through electrorefining with titanium carbide
(TiC) is used as a consumable anode (Popov, Kimble and
White 1991). By controlling the temperature and the amount
of carbon, various reduced oxides of titanium can be prepared
and these include Magnelli phases (TinO2n-1), anosorite (Ti3
O5), titanium sesquioxide (Ti2O3), hongquite (TiO), and tita­
nium carbide (TiC). However, carbon from the anode would
remain in the electrolyte during electrolysis, which led to the
contamination of final products and altered the constituent of
electrolyte. While in the USTB procedure, measures are taken
in eliminating remained carbon by means of incorporating an
oxide component into the anode. Titanium oxycarbide, for
instance, TiC0.5O0.5, which has the property of high conductiv­
ity, can be utilized as an anode material, similar to the anodes
used in aluminum industry. When TiC0.5O0.5 was used as the
anode in a molten salt bath, CO was evolved with titanium
leaving the anode as titanium ions, diffusing into electrolyte
and then moved to the cathode before being deposited to form
titanium with low oxygen content (Jiao and Zhu 2006, 2007).
Titanium monoxide (TiO) and carbide (TiC) form a series of
solid solutions TiCxO1-x, where x is located in a wide range of
542 Y. SONG ET AL.
Figure 9. Schematic diagram of the USTB process.
0–1. It was surprisingly found that the solid solutions of this
titanium oxycarbide series (TiCxO1-x) were all metallically con­
ductive. Therefore, it is possible to use such solid solutions as
anode material for titanium electrolysis.
Under certain conditions, TiCl4 can be generated at the anode
but this can be returned to the electrolyte so as to not lose any of
titanium. It is also possible to produce alloys through this tech­
nique by introducing corresponding oxides into the anode
which will be chlorinated but when fed back into the electrolyte,
will be electrolyzed. The feasibility of USTB process based on the
low-cost controllable preparation of anode materials, the stable
dissolution of anode in electrolysis and the stable deposition of
titanium on cathode. With the suggested anode and cathode
current efficiencies of 93.5% and 89%, respectively, the USTB
process is viable and extremely cost-effective, which potentially
drops the cost of titanium to near that of aluminum (Jiao and
Zhu 2006). Furthermore, the use of soluble electrodes can realize
continuous production with short flow, low energy consump­
tion, and environmental protection. It can extract titanium metal
and its alloys directly from the ore containing titanium-bearing
oxides, which can provide a novel way for the development of
various low-grade ore resources.
3.5. Self-propagating high-temperature synthesis
SHS, firstly discovered by Merzhanov et al. in 1967, has two
different reaction modes including plane wave propagation
Figure 10. Schematic illustration of the typical thermite-SHS process.
and thermal explosion (Biswas 2005; Merzhanov 2004),
which was usually used as an effective method to prepare
high melting point metals or alloys that are difficult to acquire
through a popular route. The principle for extracting metals or
alloys from their ores (usually oxides) by means of the chemical
reduction of these oxides with reducing agents, usually carbon
or other metals, has been put into industrial use basically since
the Bronze Age. Among these pyrometallurgical reductions, as
they are known in chemical metallurgy, reductions with alu­
minum, referred to as thermite reaction, occupy a prominent
class. The schematic illustration of the typical thermite-SHS
process is displayed in Figure 10. The term “Thermite” (ety­
mologically probably a contraction between thermal and dyna­
mite, on account of the most violent generation of lots and lots
of heat during the process) actually originally specifically refers
to the reaction of iron oxide with aluminum powder during
which liquid iron and liquid alumina are formed in a most
spectacular fashion. For the rapid reaction process and remark­
able heat release, external caloric supplement can usually be left
out, in whole or apart. Recently, SHS or coupled methods have
been applied in the extractive metallurgy field of titanium
(Choi, Choi and Sohn 2017) and its alloys including Ti-6Al-
4V (Cheng et al. 2017; Nersisyan et al. 2014), Ti-Fe (Cheng
et al. 2019a, 2019c, 2019d; Cheng, Zhang and Dou 2019b;
Pourabdoli et al. 2007; Wang et al. 2019), Ti-V-Fe (Wang
et al. 2012), Ti-Al (Kamali, Razavizadeh and Hadavi 2007),
and rare-earth transition-metal intermetallic compounds
(Mcdonald et al. 2010).
From the standpoint of metallurgical view, the oxides used
as raw materials can significantly reduce the cost of the alloy.
However, due to the structural change and phase evolution
accompanied by oxide reduction process, the alloy and metal­
lurgical slag will be effectively separated to achieve the purpose
of purification. In order to obtain the slag with good fluidity for
the separation between alloy and slag, it is necessary to select
the appropriate slag type, and this requires the addition of
other compounds, which leads to a decrease in the adiabatic
temperature (Tad). According to the SHS criterion proposed by
Merzhanov (2004), when Tad is lower than 1800 K, the SHS
reaction cannot be carried out spontaneously, so additional
heat supply is needed to maintain the reaction process of
system. Due to the high melting point of titanium and its
good reactivity with oxygen, carbon, and nitrogen, how to
maintain the fluidity of molten melts at smelting temperatures
with a suitable class of slag seems a challenging issue.
Nowadays, many researches on mold material for casting tita­
nium alloys have been investigated (Fan et al. 2019a), the

interface reaction between melts and mold material, and the
contamination of inclusions are primary reasons for the low
mechanical property of casting titanium alloys, which hindered
the applications of casting titanium alloys.
3.6. Two-stage thermite reduction
Recently, Zhao, Feng and Wang (2017b, 2017c) have proposed
a two-stage thermite reduction process using Na2TiF6 for fab­
rication of powder Ti and its bulk Ti-Al intermetallics, with
fluotitanate as raw material, reduced by aluminum under
a vacuum condition, the detailed flow is presented in Figure
11. As for the preparation of Ti-Al alloys, different types of
intermetallics including TiAl, Ti3Al, and TiAl3 can be acquired
from various raw materials ratio located in the first step. The
incomplete reactant, titanium-containing cryolite, can be
further reduced by the excess aluminum addition, the whole
two-stage thermite reduction process demonstrated
a continuous and cyclic route with all outputs of Ti-Al inter­
metallics and cryolite. The Al and O contents of the milled Ti
powder (particle size less than 74 μm) obtained after reduction
were 0.18 wt.% and 0.35 wt.%, respectively (Zhao, Wang, and
Feng 2017c). Simultaneously, after second-stage reduction, the
Ti contents of the clean cryolite decreased to approximately 20
ppm, the high-efficiency extraction of Ti presents a simple,
eco-friendly, effective, and promising path forward in the
development of the titanium metallurgy industry, and displays
potential industrial applications, especially for the utilization of
fluotitanate.
4. Preparation of titanium alloy by the combination
of Kroll and smelting process
Although there exist many advantages in the electrolytic synth­
esis of titanium and its alloys, upon large-scale preparation, the
productivity and electrolyte composition fluctuation are still
a key problem to overcome. Then, a promising route for
fabrication of titanium alloys mainly through the blending-
briquetting-sintering-demolding-machining process has been
Figure 11. Two-stage thermite process of Ti-Al alloys production.
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 543
proposed, which uses titanium sponge and master alloy as raw
materials, usually called as PM process. Primitively, the PM
process contains two major routes of Blending Elements (BE)
and Pre-alloy (PA), through which could content the applica­
tion in parts with less rigorous mechanical properties, such as
piston, exhaust shaft, and ossature. With the gradually expand­
ing application fields, some up-markets including aerospace
and petrochemical as well as military, especially for the large
thrust–weight ratio engine fields have claimed the unsurpassed
performances, which needs the coordinates among composi­
tion, texture, and compactness. So, the components made
through the traditional hot-press sintering method cannot
meet the needs of the current industrial complex conditions.
Then, many modified PM processes including Metal Injection
Molding (Dehghan-Manshadi et al. 2017), Electron Beam
Melting (EBM) (Murr et al. 2009), Selective Laser Melting
(Kobryn and Semiatin 2001), Hot Isostatic Pressing (HIP)
(Ma 2010) and others (Baufeld, Biest and Gault 2010;
Kottman et al. 2015; Weston and Jackson 2017) have been
proposed. For the requirements of densification and unifor­
mity for commercial parts, EBM has been regarded as the
comparatively high-efficient and flexible production method
for titanium components, while HIP was usually used as one of
the post-processing media to eliminate the defects formed in
the synthesis process (Tetsui et al. 2005), pores and stress were
included.
Nowadays, other technologies include Vacuum Arc
Remelting (VAR), Plasma Arc Melting (PAM), and Electron
Beam Cold Hearth Melting (EBCHM) are also developed for
production of titanium alloys, which are diagrammatically
presented in Figure 12 (Güthera et al. 2018; Taylor and
Pirzada 1993). For the high efficiency in rapid melting and
solidification process at the presence of ultra-high current
with various ingot scales, before the much more appropriate
approach’s determination, it can be anticipated that in the long
future, the main route for preparation of titanium alloy is
smelting under vacuum for its characterization with high effi­
ciency, technical maturity, and the established production
system.
544 Y. SONG ET AL.
Figure 12. Basic production technologies for production of titanium alloy.
Generally, the local superheat and fine vacuum condition
required for EBHCM process may result in the loss of alloying
elements like Al, Cr, or Mn, which present a high specific
equilibrium evaporation pressure in smelting process
(Güthera et al. 2018). For the difficulty in taking available
countermeasures to sufficiently compensate such evaporation
losses, the EBCHM process is generally abandoned for its fail­
ure in composition uniformity. With respect to VAR process,
the consumable electrode actually covers the molten pool and
hinder evaporated atoms. Besides, the evaporation can be sub­
stantially suppressed by the pressure of plasma arc, the eva­
poration losses during PAM processing are fairly small and, if
needed, can be compensated by a suitable surplus of the
affected element in the initial feedstock. Therefore, both VAR
and PAM can supply enough homogeneity of ingot materials
through the regulation of melting parameters.
As one of the most promising preparation methods for the
synthesis of titanium alloy, VAR process is not flawless. When
the melting point and density of alloy components differ
greatly, the high melting point block would prone to fall into
molten pool under high temperatures before melting, which
caused potential risk for production. Moreover, the density
difference usually leads to the segregation of the smelted pro­
ducts, which need at least 2–3 times overturn smelting to
eliminate these effects, and increased the energy consumption.
From the perspective of reducing preparation cost, the main
direction of energy saving is to reduce the smelting times and
use the basically uniform ingot as the raw material.
5. Low-cost clean preparation technology for
titanium and its alloys
Up to now, huge investment on extractive metallurgy of tita­
nium has been adopted, while the Kroll method is still the only
way for industrial application; meanwhile, the complex pro­
cess, high energy consumption, and chlorine corrosion to
equipment had hindered the widespread application of tita­
nium. Electrolysis seems an epochal progress on the applica­
tion of titanium extraction; however, the corresponding status
on current efficiency, industrial-scale production, the electrode
preparation, and continuous revolution also need to be
improved. Then, the metallothermic reduction based on SHS
has been gradually paid attention to its characterization with
concise flow, high production efficiency, and the wide adapt­
ability to raw materials. According to the law of phase trans­
formation and the phase thermodynamic equilibrium
concentration evolution in the reduction process of TiO2,
a novel idea of multi-stage deep reduction procedure to pre­
pare titanium and its alloys has been put forward by Zhang
et al. (Cheng et al. 2019a, , 2019d, 2017; Cheng, Zhang and Dou
2019b; Dou et al. 2014; Fan et al. 2019b, 2020; Song et al. 2019,
2020; Zhang et al. 2013,) in Northeastern University, China. At
present, ultra-low oxygen high ferrotitanium, TiAl master
alloy, powder titanium, and titanium alloy have been success­
fully prepared.
5.1. Powder extraction by multistage deep reduction and
acid leaching process
Due to the intrinsic technical bottlenecks exist in the prepara­
tion of metallic titanium powder by conventional thermal
reduction of TiO2 with calcium, magnesium, or other metals,
for their practical differences in electronegativity characteris­
tics, such as the technology of preparing titanium metal by
magnesiothermal reduction TiO2 has been unable to break the
deoxidation limit of 2 wt.% (Zhang et al. 2017, 2020), combin­
ing multistage deep reduction and acid leaching or the integra­
tion of thermal reduction with electrolysis may supply an
efficient way to the extraction of titanium. According to the
different affinity between different valence metal ions and
electrons, the concept of “multistage reduction” is put forward,
in which different valence oxides are reduced by reducing
agents with different electronegativity. First, aluminum or
magnesium with weak electronegativity was used as reducing
agent to reduce TiO2 moderately to obtain the low-valent
titanium oxide precursors (LTP) with nonstoichiometric
ratio. Then, the LTP were further reduced by another reducing
agent with more electronegative than aluminum and

magnesium, such as calcium. Eventually, the reduced products
were purified to obtain titanium or titanium alloy. To release
the treatment burden of products after each reduction process,
acid leaching procedures were taken into consideration to
remove the by-product (MgO) but retain the LTP. The flow
chart is shown in Figure 13.
The multistage reduction process overcomes the thermody­
namic equilibrium limit of deoxidation of titanium oxides by
a single metal (aluminum/magnesium/calcium) and insuffi­
cient theoretical limitations of kinetic conditions. High-purity
titanium powder with a final oxygen content of only 0.21 wt.%
and purity greater than 99.0 wt.% can be obtained through this
method, and the commensurable product is shown in Figure
14. The reduction degree and mechanism of TiO2 during the
primary magnesiothermal reaction and deoxidation mechan­
ism of primary reduction products in different deep reduction
modes were investigated (Fan et al. 2019b, 2020), which found
that calcium or magnesium was used as a reducing agent, either
SHS mode or traditional high-temperature thermal reduction
(HTTR) mode could be used for the reduction reaction. With
an incomplete primary reduction of TiO2, the LTP (TiOx,
x < 1) can be exclusively obtained, with the main components
in LTP such as Ti2O and TiO0.376. Moreover, after acid leach­
ing process, the deep deoxidation reduction (DDR) product
contains 0.21 pct oxygen, which is considerably much lower
than 4.01 pct oxygen obtained without acid leaching. Due to
the high activity of Ti, measures taken to isolate the Ti metal
and operation circumstance would greatly decrease the oxygen
content uptake in the post-processing (Distl, Dehm and Stein
2020; Vuuren, Oosthuizen and Heydenrych 2011), such as
drying the argon flow presented in the smelting process with
hot Ti filings (Witusiewicz et al. 2009). Furthermore, the total
amount of calcium and magnesium impurities (0.249 wt.%) in
the DDR product was also significantly reduced by the deep
reduction of the primary reduction product without acid leach­
ing (0.436 wt.%) (Fan et al. 2019b). The preparation of LTP
eliminates the problem that Ti-O-Me composite titanate by-
products formed in strong reducing atmosphere in traditional
direct reduction process. The enlarge test has been completed
on semi-industrialization and the detailed parameters, the sta­
bility and continuity need to be further improved, which may
Figure 13. Flow chart of Ti/Ti alloys powder preparation by multistage deep reduction and acid leaching process.
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 545
supply another conspicuous progress in titanium industry.
Nowadays, the 200 t/a titanium powder industrial demonstra­
tion line was successfully put into operation on December 8,
2019. This route solved the problem that traditional metal­
lothermic reduction cannot completely reduce TiO2 to directly
prepare titanium and its alloys, which can reduce the produc­
tion cost of titanium by about 30%, and lay an industrial
foundation for low-cost clean preparation and application of
titanium materials.
5.2. As-cast alloys prepared by thermite-SHS and depth
injection calcium vapor reduction process
Up to now, the preparation of Ti-based alloy is mainly through
PM and ingot metallurgy (IM) with titanium sponge and
master alloy as raw materials (Paul et al. 2013), while the
huge amounts of energy consumption in chlorination process
for production of titanium sponge have greatly restricted the
application of titanium alloy. As the fourth most abundant
element in the earth’s crust, unfortunately, the high cost of
the Kroll process inhibits its widespread use, which made it the
almost highest noble element among structural metals. Ever
since the excellent properties of titanium were found, efforts
have been committed to how to effectively reduce the cost of
extractive metallurgy of titanium, and develop new alloys with
superior properties to expand the scope of application.
According to the cost of production of titanium, to reduce
the cost usually through two aspects: the cost of raw materials
and extraction process, while the latter is a combination of
manpower, energy, equipment investment, and maintenance,
which can be effectively improved over the measures including
simplifying production technology. The cost of the alloy can be
greatly reduced by using oxide as raw material through ther­
mite-SHS process.
The preparation of titanium alloys by thermite reduction of
TiO2 has sufficient thermodynamic conditions, while lots of Ti-
Al intermetallics formed in the reduction process, which
results in the excess aluminum content than the standard in
the final product. Therefore, how to achieve the theoretical
breakthrough of titanium alloys preparation by metallothermic
reduction is vital to realize the clean preparation of titanium.
546 Y. SONG ET AL.
Figure 14. SEM image of titanium powder produced from multistage deep
reduction and acid leaching process.
To overcome the excess aluminum that exist in titanium alloy,
multistage reduction with different reducants was adopted to
acquire low aluminum and oxygen content titanium alloys, and
the main technical route is shown in Figure 15.
A certain alloy can be prepared by direct thermite reduction
of the existing initial mixed minerals. When the alloy compo­
nents are insufficient, a small amount of alloy components can
be appropriately added, and greatly reduces the preparation
cost. This is also the concept of preparing alloy directly from
minerals, which is also called the integration of metallurgy and
materials preparation process. The short process can greatly
reduce the cost of material preparation and improve the
Figure 15. Flow chart of titanium alloy preparation by multi-stage deep reduction.
market competitiveness of materials. Based on the multistage
deep reduction technology, TiAl alloy ingot of 20 kg scale with
oxygen content about 1.09 wt.% was successfully prepared
(Song et al. 2019, 2020). Moreover, an as-cast TiAl intermetal­
lic ingot was prepared through the uple of SHS and cold
crucible levitation melting (CCLM), as is shown in Figure 16.
Furthermore, Cheng et al. (2019a, 2019b, 2019c, 2019d, 2020)
have studied the occurrence mechanism and distribution form
of sulfur and oxygen as well as the mass transfer in slag–metal
interaction procedure of low-oxygen high titanium ferroalloy
prepared by multistage deep reduction, and certificates an
effective way for low-cost preparation of titanium alloy.
Moreover, compared with the cycle of magnesium and chlorine
requiring high energy consumption in Kroll process, the effec­
tive utilization of chemical heat in SHS process can greatly
reduce the energy consumption, and get rid of high complex­
ity, discontinuity, and the corrosion to equipment.
6. Comprehensive analysis of titanium metallurgy
6.1. Comparison of different extractive processes
It took about 2 centuries between the discovery and prepara­
tion of titanium, while approximately 40 years later come into
industrial production. To date, about 20 novel processes have
been investigated as possible low-cost routes for titanium fab­
rication, measures taken as to convert these batch processes
into continuous procedures, reduce raw material cost, and
adopt new technology are necessary. A summary of the main
processes for preparation of titanium and its alloys is presented
in Table 1.
Among these methods, electrolysis seems to be the most
promising route for preparation of high-purity titanium/tita­
nium alloy with a uniform composition, on the premise of
some issues must be solved, including the fluctuation of elec­
trolyte composition, solubility, continuity, and current effi­
ciency. Meanwhile, the multistage deep reduction combined
with acid leaching process displays potential in low-cost pre­
paration of powder titanium/titanium alloy with high effi­
ciency, eco-friendly, and continuous operation. The thermite-
SHS and depth injection calcium vapor reduction process also
shows a competitive direction for preparation of as-cast alloys.
Furthermore, the recently proposed NSEM process has also
presented excellent potential in the micro-flow of preparation
of titanium alloy components. However, most of these pro­
cesses are at laboratory or pilot plant stage and it will take
several years before it is known whether one of them will
replace Kroll process.
6.2. Implications for theory and practice
For titanium metallurgy, metal titanium and its alloys are
obtained from titanium-bearing minerals through mining,
beneficiation, and smelting, which is a high-temperature het­
erogeneous physical-chemical process involving oxidation and
reduction. With the decrease of high-quality deposits, complex
mineral resources need to be effectively utilized, while the
progress of beneficiation technology provides the possibility
for the development of low-grade ore (Butterman 1988; Chen
 MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 547

Figure 16. The photograph and microstructure of as-cast TiAl intermetallic ingot: (a) photograph, (b) SEM image and (c) TEM image.

Table 1. Process for preparation of titanium and its alloys.

Process Features Advantages Disadvantages References
Hunter Molten Na as the reductant, high- Ti product with less oxygen
Labor-intensive batch process; Hunter 1910; Fang et al. 2018
process purity TiCl4 as raw materials content and metallic heterogeneous exothermic
impurities can be used in reactions;
electronic industry low productivity, energy-
intensive, expensive sodium
reductant
Kroll process Molten Mg as the reductant, high- Ti product with less oxygen Labor-intensive batch process; Kroll 1940; Fraser, Imam and Kosaka
purity TiCl4 as raw materials content and metallic heterogeneous exothermic 2016; Fray 2008
impurities, cost-effective reactions; low productivity,
than Hunter process energy-intensive
Electrolysis KCl–LiCl electrolyte graphite anode; Fewer steps; continuous Redox cycling and handling very Ginatta and Orsello 1987; Natsui et al.
process steel cathode; TiO2 or K2Ti6O13 feed operation; no TiCl4 and reactive dendritic products 2020; Zhao et al. 2016, Zhao et al.
metallic involvement 2017a
OS process TiO2 powder cathode graphite rod Direct reduction from TiO2 Existence of free carbon Ono and Suzuki 2002; Suzuki 2005
anode Ca reluctant and molten CaCl2 powder as feed in a single contaminating the Ti product
cell by the formation of TiC
FFC process Pre-formed porous TiO2 pellet as the Simple, rapid and better Slow O2 diffusion; costly for the Chen, Fray and Farthing 2000; Ma et al.
cathode; inert anode for O2 current efficiency; potential TiO2 pellet feed 2006; Hu et al. 2018; Fray and Chen
evolution; molten CaCl2 continuous operation 2004
SOM process SOM technology used as a short Oxygen or water vapor as the Low efficiency; unstable current Pal, Woolley and Kenney 2001; Zhao
procedure, Oxide ores as raw major by-product, alloys can et al. 2005; Zou et al. 2010; Li et al.
materials be directly obtained 2017
Armstrong TiCl4 vapor is fed directly into the Continuous operation, Highly residual impurities, Fray 2008, Araci, Mangabhai and
process sodium stream for reaction possible to produce alloy expensive sodium reductant Akhtar 2015
powders
EMR process The electrolysis of calcium chloride to High current efficiency Complex operations, costly Abiko, Park and Okabe 2004; Fray 2008
give calcium but instead on using it investment
directly, combined with liquid nickel
or copper
Preform TiO2 and Ca are mixed and heated to High reduction efficiency Difficult to scale up for the Okabe, Oda and Mitsuda 2004.
reduction elevated temperatures to complete difficulty in facilitating
process the reduction a homogeneous
(PRP) reaction
MER process Cost-affordable titania-rich feedstocks Electrochemical dissolution of Carbon contamination, Withers and Loutfy 2011
TiO2 anode, no TiCl4 and composition fluctuation of
metallic involvement electrolyte
USTB method Electrorefining titanium oxycarbide Low-cost preparation of TiCxOy Jiao and Zhu 2006, Jiao and Zhu 2007
solid solution anode; continuous process;
high-purity titanium
(>99.9%)
SHS process Rapid and efficient exothermic reaction Low demand for raw materials, Uncontrollable process Nersisyan et al. 2014; Cheng et al.
high efficiency 2017; Wang et al. 2012; Kamali,
Razavizadeh and Hadavi 2007;
Mcdonald et al. 2010
Two-stage Na2TiF6 as raw materials, vacuum No pollution, direct Batch process Zhao, Feng and Wang 2017b, Zhao,
thermite condition preparation of alloy Wang and Feng 2017c; Zhao and
process Feng 2017
Multistage Combination of reduction and acid No pollution; can prepare Ti/Ti Fan et al. 2019b, Fan et al. 2020; Zhang
deep leaching, different metal reducant alloy powder; short and et al. 2010, Zhang et al. 2013, Zhang
reduction continuous process et al. 2014; Dou et al. 2014
548 Y. SONG ET AL.
et al. 2013; Gueguin and Cardarelli 2007; Sundaram, Taneja
and Sridhar Rao 1992; Tripathy, Ramamurthy and Kumar
2010), accompanied with the advance in the extractive tech­
nology of titanium (Nguyen and Lee 2019; Reddy and Saji
2002; Zhang 2014). In addition to the traditional route of
metal extraction – material preparation, innovative techniques
are also encouraged to broaden the comprehensive application
of titanium, such as NSEM process (Dolganov et al. 2020) and
directly screen printed TiO2 coatings (Schwandt and Fray
2007). Due to the remarkable chemical stability, high-grade
TiO2 is still recommended as the raw material for preparation
of titanium and its alloys, while some challenging issues such as
redox cycling, feeding, kinetics, control heat balance have to be
resolved before scaling-up to commercial applications (Zhang,
Zhu and Cheng 2011), the upgrading of titanium ores is neces­
sary to be processed.
7. Concluding remarks
About nearly 2.5 centuries have passed since the discovery of
titanium, while the application history are only 100 years due to
the difficulty for extractive metallurgy of titanium in an effective
way. With comparison among these methods including Hunter,
Kroll, electrolysis, SHS, and so on, electrolysis as the most pro­
found progress to prepare high-purity titanium, due to the pre­
paration of electrodes, the time-consuming reaction process and
the formation of corrosive by-products, lots of modifications had
been made including electrolytes and feedstock, the current devel­
opment of electrolysis will still be limited. Kroll process will still be
the main method to prepare titanium for a long time. For the
current principle is to reduce the preparation cost, the extractive
metallurgy of titanium and its alloys need the combination of
various methods including pyrometallurgy, hydrometallurgy,
and electrolysis, such as the couple of the multistage reduction of
titania with different reducing agents and leaching process. High-
purity titanium powder (purity: >99 wt.%; Oxygen: ≤0.21 wt.%)
and TiAl alloy (Oxygen: 1.09 wt.%) have been successively pre­
pared at laboratory scale, and the industrial tests are carried out.
Meanwhile, the SHS process characterized with short flow and
high efficiency can be used for mass production. In general,
compared with electrolysis, SHS is a very competitive method to
prepare titanium and its alloys, while it will be taken several years
before any new process is in commercial production and compet­
ing with the Kroll process.
Disclosure statement
The authors declare that they have no conflict of interest.
Funding
This research was financially supported by the National Natural Science
Foundation of China [U1702253, U1908225]; Fundamental Research
Funds for the Central Universities [N170908001, N182515007,
N2025004].
ORCID
Yulai Song http://orcid.org/0000-0001-8545-4842
Ting-an Zhang http://orcid.org/0000-0002-9934-4713
References
Abiko, T., I. Park, and T. H. Okabe. 2004. In Ti-2003 science and technol­
ogy, ed. G. Lutjering and J. Albrecht, 253–60. Weinheim: Wiley-VCH.
Amarchand, S., T. R. Ramamohan, and P. Ramakrishnan. 2001. Synthesis
of fine titanium powders via solution route. Mineral Processing and
Extractive Metallurgy Review 22 (1):279–85. doi:10.1080/
08827509808962502.
Araci, K., D. Mangabhai, and K. Akhtar. 2015. Production of titanium by
the Armstrong process. Titanium Powder Metallurgy 9: 149–62.
Baker, T. N. 2019. Titanium microalloyed steels. Ironmaking &
Steelmaking 46 (1):1–55. doi:10.1080/03019233.2018.1446496.
Baufeld, B., O. Biest, and R. Gault. 2010. Additive manufacturing of
Ti-6Al-4V components by shaped metal deposition: Microstructure
and mechanical properties. Materials & Design 31:S106–S110.
doi:10.1016/j.matdes.2009.11.032.
Biswas, A. 2005. Porous NiTi by thermal explosion mode of SHS:
Processing, mechanism and generation of single phase
microstructure. Acta Materialia 53 (5):1415–25. doi:10.1016/j.
actamat.2004.11.036.
Boyer, R., G. Welsch, and E. Collings. 1994. Materials properties hand­
book: Titanium alloys. Materials Park: ASM International.
Butterman, W. C. 1988. Current status of the specialty metals. Mineral
Processing and Extractive Metallurgy Review 3 (1–4):69–86.
doi:10.1080/08827508808952616.
Chen, C. Y., J. Li, and X. Lu. 2012. Extraction of Ti and Ti alloy from
titaniferous residue using SOM process. Advanced Materials Research
550-553:1811–16. doi:10.4028/www.scientific.net/AMR.550-553.1811.
Chen, G. S., O. Masazumi, and O. Takeo. 1987. Electrochemical studies of
titanium ions (Ti4+) in equimolar KCl-NaCl molten salts with 1 wt% K2
TiF6. Electrochimica Acta 32 (11):1637–42. doi:10.1016/0013-4686(87)
90017-X.
Chen, G. Z., D. Fray, and T. Farthing. 2000. Direct electrochemical
reduction of titanium dioxide to titanium in molten calcium chloride.
Nature 407 (6802):361–64. doi:10.1038/35030069.
Chen, L., S. Wen, G. Xu, and H. Xie. 2013. A novel process for titanium
sand by magnetic separation and gravity concentration. Mineral
Processing and Extractive Metallurgy Review 34 (3):139–50.
doi:10.1080/08827508.2011.623749.
Cheng, C., Z. H. Dou, and T.-A. Zhang. 2020. Mechanism of melt separa­
tion in preparation of low-oxygen high titanium ferroalloy prepared by
multistage and deep reduction. Metals 10 (3):309. doi:10.3390/
met10030309.
Cheng, C., Z. H. Dou, T.-A. Zhang, Y. Liu, and L. P. Niu. 2019a.
Distribution and control mechanism of Al and O residuals in ferroti­
tanium prepared by aluminothermic reduction with insufficient Al.
JOM 71 (2):809–14. doi:10.1007/s11837-018-3212-6.
Cheng, C., Z. H. Dou, T.-A. Zhang, J. M. Su, H. J. Zhang, Y. Liu, and
L. P. Niu. 2019c. Sulfur distribution in preparation of high titanium
ferroalloy by thermite method with different CaO additions. Rare
Metals 38:793–99. doi:10.1007/s12598-018-1170-3.
Cheng, C., Z. H. Dou, T.-A. Zhang, J. M. Su, H. J. Zhang, Y. Liu, and
L. P. Niu. 2019d. Oxygen content of high ferrotitanium prepared by
thermite method with different melt separation temperatures. Rare
Metals 38 (9):892–98. doi:10.1007/s12598-019-01218-1.
Cheng, C., Z. H. Dou, T.-A. Zhang, H. J. Zhang, X. Yi, and J. M. Su. 2017.
Synthesis of as-cast Ti-Al-V alloy from titanium-rich material by ther­
mite reduction. JOM 69 (10):1818–1523. doi:10.1007/s11837-017-2467-
7.
Cheng, C., T.-A. Zhang, and Z. H. Dou. 2019b. Formation mechanism and
distribution of Al and O in the ferrotitanium with different Ti contents
prepared by thermite method. JOM 71 (10):3584–89. doi:10.1007/
s11837-019-03597-3.
Choi, K., H. Choi, and I. Sohn. 2017. Understanding the magnesiothermic
reduction mechanism of TiO2 to produce Ti. Metallurgical and
Materials Transactions B 48 (2):922–32. doi:10.1007/s11663-016-
0912-6.

Cui, C. X., B. Hu, L. Zhao, and S. Liu. 2011. Titanium alloy production
technology, market prospects and industry development. Materials &
Design 32 (3):1684–91. doi:10.1016/j.matdes.2010.09.011.
Dehghan-Manshadi, A., M. Bermingham, M. Dargusch, D. StJohn, and
M. Qian. 2017. Metal injection moulding of titanium and titanium
alloys: Challenges and recent development. Powder Technology
319:289–301. doi:10.1016/j.powtec.2017.06.053.
Distl, B., G. Dehm, and F. Stein. 2020. Effect of oxygen on
high-temperature phase equilibria in ternary Ti-Al-Nb alloys.
Zeitschrift fur Anorganische und Allgemeine Chemie 646:1–7.
Dolganov, A., M. Bishop, M. Tomatis, G. Chen, and D. Hu. 2020.
Environmental assessment of the near-net-shape electrochemical
metallisation process and the Kroll-electron beam melting process for
titanium manufacture. Green Chemistry 22 (6):1952–67. doi:10.1039/
C9GC04036F.
Dosaj, V., C. Aksaranan, and D. Morris. 1975. Thermodynamic properties
of the calcium + calcium chloride system measured by an electroche­
mical technique. Journal of the Chemical Society, Faraday Transactions
1: Physical Chemistry in Condensed Phases 71:1083–98. doi:10.1039/
f19757101083.
Dou, Z. H., T.-A. Zhang, Z. M. Zhang, C. Wang, Y. Liu, G. Z. Lv, J. C. He,
and X. L. Jiang. 2014. A method of preparation of ferrotitanium alloy
based on aluminothermic self-propagating injection depth reduction.
China patent CN201410345901.4.
Elias, C. N., J. Lima, R. Valiev, and M. Meyers. 2008. Biomedical applica­
tions of titanium and its alloys. JOM 60 (3):46–49. doi:10.1007/s11837-
008-0031-1.
Fan, J. L., L. Liang, Z. Liu, Y. Li, Y. Li, H. Gao, S. Wu, Y. Wang, and
X. Wang. 2019a. Recent research and development of mould materials
for casting TiAl alloys. Materials Science and Technology 35 (8):891–99.
doi:10.1080/02670836.2019.1598667.
Fan, S. G., Z. H. Dou, T.-A. Zhang, Y. Liu, and L. P. Niu. 2019b.
Deoxidation mechanism in reduced titanium powder prepared by
multistage deep reduction of TiO2. Metallurgical and Materials
Transactions B 50 (1):282–90. doi:10.1007/s11663-018-1466-6.
Fan, S. G., Z. H. Dou, T.-A. Zhang, B. W. Zhang, and L. P. Niu. 2020.
Direct preparation of titanium powder by multistage deep reduction.
Rare Metal Materials and Engineering 49 (3):1020–23.
Fang, Z. Z., J. D. Paramore, P. Sun, K. R. Chandran, Y. Zhang, Y. Xia,
F. Cao, M. Koopman, and M. Free. 2018. Powder metallurgy of tita­
nium–past, present, and future. International Materials Reviews 63
(7):407–59. doi:10.1080/09506608.2017.1366003.
Ferro, P. D., B. Mishra, D. Olson, and W. Averill. 1997. Application of
ceramic membrane in molten salt electrolysis of CaO-CaCl2. Waste
Management 17 (7):451–61. doi:10.1016/S0956-053X(97)10051-4.
Ferro, P. D., B. Mishra, D. Olson, and W. Averill. 1998. Electrolytic
extraction of calcium from calcium oxide. Transactions of the Indian
Institute of Metals 51:69–77.
Fischbach, H. 1985. Thermodynamic data for liquid Ca-CaF2 and Ca-
CaCl2 slags. Steel Research: Process Metallurgy 56 (7):365–68.
doi:10.1002/srin.198500649.
Fraser, H. L., M. Imam, and Y. Kosaka. 2016. Electrolytic Ti powder
production from ore source. 2015 world conference on titanium, 61.
San Diego: John Wiley & Sons.
Fray, D. J. 2008. Novel methods for the production of titanium.
International Materials Reviews 53 (6):317–25. doi:10.1179/
174328008X324594.
Fray, D. J., and G. Chen. 2004. Reduction of titanium and other metal
oxides using electrode oxidation. Materials Science and Technology 20
(3):295–300. doi:10.1179/026708304225012242.
Gambogi, J. 2020. Mineral commodity summaries: Titanium statistics and
information, M. George. U.S. Geological Survey. Reston: National
Minerals Information Center.
Gao, F., Z. Nie, D. Yang, B. Sun, Y. Liu, X. Gong, and Z. Wang. 2018.
Environmental impacts analysis of titanium sponge production using
Kroll process in China. Journal of Cleaner Production 174:771–79.
doi:10.1016/j.jclepro.2017.09.240.
Ginatta, M. V. 2004. In Ti-2003 science and technology, ed. G. Lutjering
and J. Albrecht, 237–44. Weinheim: Wiley-VCH.
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 549
Ginatta, M. V., and G. Orsello. 1987. Plant for the electrolytic production
of reactive metals in molten salt baths. US Patent US4670121 A.
Gueguin, M., and F. Cardarelli. 2007. Chemistry and mineralogy of tita­
nia-rich slags. Part 1—Hemo-ilmenite, sulphate, and upgraded titania
slags. Mineral Processing and Extractive Metallurgy Review 28 (1):1–58.
doi:10.1080/08827500600564242.
Güthera, V., M. Allen, J. Klose, and H. Clemens. 2018. Metallurgical
processing of titanium aluminides on industrial scale. Intermetallics
103:12–22. doi:10.1016/j.intermet.2018.09.006.
He, Z. Y., X. Li, L. P. Niu, and T.-A. Zhang. 2019. Simulation study on flow
field of sponge titanium by product magnesium chloride in high tem­
perature gas phase oxidation reactor. Titanium Industry Progress 36
(4):36–42.
Hu, D., A. Dolganov, M. Ma, B. Bhattacharya, M. Bishop, and G. Chen.
2018. Development of the Fray-Farthing-Chen cambridge process:
Towards the sustainable production of titanium and its alloys. JOM
70 (2):129–37. doi:10.1007/s11837-017-2664-4.
Hunter, M. A. 1910. Metallic titanium. Journal of the American Chemical
Society 32 (3):330–36. doi:10.1021/ja01921a006.
Jiao, S. Q., and H. Zhu. 2006. Novel metallurgical process for titanium
production. Journal of Materials Research 21 (9):2172–75. doi:10.1557/
jmr.2006.0268.
Jiao, S. Q., and H. Zhu. 2007. Electrolysis of Ti2CO solid solution prepared
by TiC and TiO2. Journal of Alloys and Compounds 438 (1–2):243–46.
doi:10.1016/j.jallcom.2006.08.016.
Kalinnikov, V. T., and A. I. Nikolaev. 2002. Titanium-rare metal minerals
of the Kola Peninsula–a source of both conventional and new materials.
Mineral Processing and Extractive Metallurgy Review 22 (4–6):453–62.
doi:10.1080/08827500208547424.
Kamali, A. R., H. Razavizadeh, and S. Hadavi. 2007. A new process for
titanium aluminides production from TiO2. Journal of Materials
Science & Technology 23 (3):367–72.
Kim, S. W., J. Hong, Y. Na, J. Yeom, and S. Kim. 2014. Development of
TiAl alloys with excellent mechanical properties and oxidation
resistance. Materials & Design 54:814–19. doi:10.1016/j.
matdes.2013.08.083.
Kim, Y. W., and S. Kim. 2018. Advances in gammalloy
materials-processes-application technology: Successes, dilemmas, and
future. JOM 70 (4):553–60. doi:10.1007/s11837-018-2747-x.
Kipouros, G. J., and R. Sharma. 1990. Electrolytic regeneration of the
neodymium oxide reduction - spent salt. Journal of the
Electrochemical Society 137 (11):3333–38. doi:10.1149/1.2086218.
Kobryn, P. A., and S. Semiatin. 2001. The laser additive manufacture of
Ti-6Al-4V. JOM 53 (9):40–42. doi:10.1007/s11837-001-0068-x.
Kottman, M., S. Zhang, J. McGuffin-Cawley, P. Denney, and
B. Narayanan. 2015. Laser hot wire process: A novel process for
near-net shape fabrication for high-throughput applications. JOM 67
(3):622–28. doi:10.1007/s11837-014-1288-1.
Kroll, W. J. 1940. The production of ductile titanium. Journal of the
Electrochemical Society 78 (1):35–47. doi:10.1149/1.3071290.
Li, J., X. Lu, S. Yang, L. Ma, E. Wu, J. Hou, C. Li, T. Wang, and B. Li.
2017b. Preparation of Ti-Al-xFe-ySi alloy from electro-titanium slag by
electro-aluminothermic reduction. Non-ferrous Metals: Smelting Part
8:25–29.
Li, J., X. Lu, S. Yang, E. Wu, J. Hou, C. Li, Q. Lai, and L. Ma. 2017a.
Theoretical and experimental research on preparation of Ti-Al alloy by
electric aluminothermic reduction. Iron Steel Vanadium Titanium 38
(5):46–52.
Li, S. S., X. Zou, K. Zheng, X. Lu, Q. Xu, C. Chen, and Z. Zhou. 2017.
Direct production of TiAl3 from Ti/Al-containing oxides precursors by
solid oxide membrane (SOM) process. Journal of Alloys and
Compounds 727:1243–52. doi:10.1016/j.jallcom.2017.08.213.
Lyu, C., L. Niu, Q. Zhao, and W. Wang. 2019. Influence of the granule
morphology of MgO particles on the yield of pyrolysis products.
Journal of Northeastern University: Natural Science 40 (11):1579–83.
Ma, M., D. Wang, W. Wang, X. Hu, X. Jin, and G. Chen. 2006. Extraction
of titanium from different titania precursors by the FFC Cambridge
process. Journal of Alloys and Compounds 420 (1–2):37–45.
doi:10.1016/j.jallcom.2005.10.048.
550 Y. SONG ET AL.
Ma, Q. 2010. Cold compaction and sintering of titanium and its alloys for
near-net-shape or preform fabrication. International Journal of Powder
Metallurgy 46 (5):29–44.
Mcdonald, J. P., M. Rodriguez, E. Jones, and D. Adams. 2010. Rare-earth
transition-metal intermetallic compounds produced via
self-propagating, high-temperature synthesis. Journal of Materials
Research 25 (4):718–27. doi:10.1557/JMR.2010.0091.
Merzhanov, A. G. 2004. The chemistry of self-propagating
high-temperature synthesis. Journal of Materials Chemistry 14
(12):1779–86. doi:10.1039/b401358c.
Merzhanov, A. G., and I. Borovinskaya. 1972. Self-propagating
high-temperature synthesis of inorganic compounds. Doklady
Akademii Nauk Sssr 204 (2):366–69.
Merzhanov, A. G., and I. Borovinskaya. 2008. Historical retrospective of
SHS: An autoreview. International Journal of Self-propagating High-
temperature Synthesis 17 (4):242–65. doi:10.3103/S1061386208040079.
Murr, L. E., S. Quinones, S. Gaytan, M. Lopez, A. Rodela, E. Martinez,
D. Hernandez, F. Medina, and R. Wicker. 2009. Microstructure and
mechanical behavior of Ti-6Al-4V produced by rapid-layer manufac­
turing, for biomedical applications. Journal of the Mechanical Behavior
of Biomedical Materials 2 (1):20–32. doi:10.1016/j.jmbbm.2008.05.004.
Nagesh, C. R., and C. Ramachandran. 2007. Electrochemical process of
titanium extraction. Transactions of Nonferrous Metals Society of China
17 (2):429–33. doi:10.1016/S1003-6326(07)60110-1.
Natsui, S., T. Sudo, R. Shibuya, H. Nogami, T. Kikuchi, and R. Suzuki.
2020. Visualization of TiO2 reduction behavior in molten salt
electrolysis. Metallurgical and Materials Transactions B 51 (1):11–15.
doi:10.1007/s11663-019-01733-7.
Nersisyan, H. H., H. Won, C. Won, A. Jo, and J. Kim. 2014. Effective
two-step method for producing Ti-6Al-4V alloy particles with various
morphologies. Powder Technology 254:57–62. doi:10.1016/j.
powtec.2014.01.005.
Nguyen, T. H., and M. S. Lee. 2019. A review on the recovery of titanium
dioxide from ilmenite ores by direct leaching technologies. Mineral
Processing and Extractive Metallurgy Review 40 (4):231–47.
doi:10.1080/08827508.2018.1502668.
Niu, L. P., T.-A. Zhang, W. B. Wang, A. P. Zhou, and H. Huang. 2014.
New Mg-Ti combination based on the pyrolysis of molten magnesium
chloride. Rare Metal Materials and Engineering 43 (12):3138–42.
Niu, L. P., T.-A. Zhang, A. P. Zhou, G. Z. Lv, and J. C. He. 2013.
Preparation and characterization of magnesia powder by direct pyro­
lysis process of molten magnesium chloride. The Chinese Journal of
Nonferrous Metals 23 (6):1732–38.
Okabe, T. H., T. Oda, and Y. Mitsuda. 2004. Titanium powder production
by preform reduction process (PRP). Journal of Alloys and Compounds
364 (1–2):156–63. doi:10.1016/S0925-8388(03)00610-8.
Ono, K., and R. O. Suzuki. 2002. A new concept for producing Ti sponge:
Calciothermic reduction. JOM 54 (2):59–61. doi:10.1007/BF02701078.
Pal, U. B., D. Woolley, and G. Kenney. 2001. Emerging SOM technology
for the green synthesis of metals from oxides. JOM 53 (10):32–35.
doi:10.1007/s11837-001-0053-4.
Paul, J. D. H., U. Lorenz, M. Oehring, and F. Appel. 2013. Up-scaling the
size of TiAl components made via ingot metallurgy. Intermetallics
32:318–28. doi:10.1016/j.intermet.2012.08.006.
Popov, B. N., M. Kimble, and R. White. 1991. Electrochemical behaviour
of titanium (II) and titanium (III) compounds in molten lithium
chloride/potassium chloride eutectic melts. Journal of Applied
Electrochemistry 21:351–57. doi:10.1007/BF01020221.
Pourabdoli, M., S. Raygan, H. Abdizadeh, and K. Hanaei. 2007. A new
process for the production of ferrotitanium from titania slag. Canadian
Metallurgical Quarterly 46 (1):17–24. doi:10.1179/cmq.2007.46.1.17.
Reddy, M. L. P., and J. Saji. 2002. Solvent extraction of tetravalent titanium
with organophosphorus extractants. Mineral Processing and Extractive
Metallurgy Review 23 (3–4):199–227. doi:10.1080/08827500306892.
Schwandt, C. 2013. Understanding the electro-deoxidation of titanium
dioxide to titanium metal via the FFC-Cambridge process. Mineral
Processing and Extractive Metallurgy 122 (4):213–18. doi:10.1179/
0371955313Z.00000000071.
Schwandt, C., and D. J. Fray. 2007. Preparation of titanium coatings on
steel through electro reduction of plasma sprayed and screen printed
titanium dioxide deposits. Ironmaking & Steelmaking 34 (3):225–30.
doi:10.1179/174328107X167968.
Song, Y. L., Z. H. Dou, T.-A. Zhang, and Y. Liu. 2019. A novel continuous
and controllable method for fabrication of as-cast TiAl alloy. Journal of
Alloys and Compounds 789:266–75. doi:10.1016/j.jallcom.2019.03.050.
Song, Y. L., Z. H. Dou, T.-A. Zhang, Y. Liu, and L. P. Niu. 2020.
Preparation of TiAl master alloy by metallothermic reduction. Rare
Metal Materials and Engineering 49 (3):1015–19.
Staffansson, L.-I., and D. Sichen. 1992. A thermodynamic study of the Ca-
CaF2, Ca-CaCl2, Ca-CaBr2 and Ca-CaI2 systems. Scandinavian Journal
of Metallurgy 21:165–71.
Sundaram, C. V., A. K. Taneja, and C. H. Sridhar Rao. 1992. Technology
trends in the extractive metallurgy of zirconium, titanium, tantalum
and niobium. Mineral Processing and Extractive Metallurgy Review 10
(1):239–65. doi:10.1080/08827509208914088.
Suzuki, R. O. 2005. Calciothermic reduction of TiO2 and in situ electro­
lysis of CaO in the molten CaCl2. Journal of Physics and Chemistry of
Solids 66 (2–4):461–65. doi:10.1016/j.jpcs.2004.06.041.
Suzuki, R. O. 2008. International round table on titanium production in
molten salts, 20–26. Cologne, Germany.
Suzuki, R. O., K. Teranuma, and K. Ono. 2003. Calciothermic reduction of
titanium oxide and in-situ electrolysis in molten CaCl2. Metallurgical and
Materials Transactions B 34B:287–95. doi:10.1007/s11663-003-0074-1.
Taylor, P. R., and S. A. Pirzada. 1993. Plasma technology in extractive and
process metallurgy. Mineral Processing and Extractive Metallurgy
Review 12 (2–4):257–69. doi:10.1080/08827509508935260.
Tetsui, T., R. Nagasaki, D. Nagasaki, and J. Nagasaki. 2005. Titanium
aluminum intermetallic compound based alloy and method of fabricat­
ing a product from the alloy. US Patent EP1308529B1.
Tripathy, S. K., Y. Ramamurthy, and C. R. Kumar. 2010. Modeling of
high-tension roll separator for separation of titanium bearing minerals.
Powder Technology 201 (2):181–86. doi:10.1016/j.powtec.2010.04.005.
Vuuren, D. S. V., S. Oosthuizen, and M. Heydenrych. 2011. Titanium
production via metallothermic reduction of TiCl4 in molten salt:
Problems and products. Journal of the South African Institute of
Mining and Metallurgy 111:141–48.
Wang, B., K. Liu, and J. Chen. 2011. Reaction mechanism of preparation
of titanium by electro-deoxidation in molten salt. Transactions of
Nonferrous Metals Society of China 21 (10):2327–31. doi:10.1016/
S1003-6326(11)61016-9.
Wang, B., K. Liu, J. Chen, T. Gao, and J. He. 2012. Preparation of V-Ti-Fe
master alloys by metallothermic reduction method. Transactions of
Nonferrous Metals Society of China 22 (6):1507–12. doi:10.1016/
S1003-6326(11)61348-4.
Wang, W. B., L. Niu, T. Zhang, G. Lv, and A. Zhou. 2014. Design and
study on pyrolysis device for molten magnesium chloride. Journal of
Materials and Metallurgy 13 (4):293–97.
Wang, Z. Y., J. Zhang, Z. Liu, G. Wang, K. Jiao, K. Li, and T. Yang. 2019.
Production of ferrotitanium alloy from titania slag based on alumi­
nothermic reduction. Journal of Alloys and Compounds 810:151969.
doi:10.1016/j.jallcom.2019.151969.
Weston, N. S., and M. Jackson. 2017. FAST-forge - a new cost-effective
hybrid processing route for consolidating titanium powder into near
net shape forged components. Journal of Materials Processing
Technology 243:335–46. doi:10.1016/j.jmatprotec.2016.12.013.
Withers, J. C., and R. Loutfy. 2011. Thermal and electrochemical process
for metal production. US Patent US7410562 B2.
Witusiewicz, V. T., A. Bondar, U. Hecht, and T. Velikanova. 2009. The
Al-B-Nb-Ti system: IV. Experimental study and thermodynamic
re-evaluation of the binary Al-Nb and ternary Al-Nb-Ti systems.
Journal of Alloys and Compounds 472 (1–2):133–61. doi:10.1016/j.
jallcom.2008.05.008.
Wu, X. H. 2006. Review of alloy and process development of TiAl alloys.
Intermetallics 14 (10–11):1114–22. doi:10.1016/j.intermet.2005.10.019.
Yamaguchi, M., T. Ogasawara, and H. Ichihashi. 2007b. In Proc. 11th
world conf. on ‘Titanium’, ed. M. Ninomi et al., Vol. 1, 147–50. Kyoto,
Japan.
Yamaguchi, M., Y. Ono, S. Kosemura, W. Kagobayashi, and T. Tanenaka.
2007a. In Proc. 11th world conf. on ‘Titanium’, ed. M. Ninomi et al. Vol.
1, 143–46. Kyoto, Japan.

Ye, X. S., X. Lu, C. Li, W. Ding, X. Zou, Y. Gao, and Q. Zhong. 2011.
Preparation of Ti-Fe based hydrogen storage alloy by SOM method.
International Journal of Hydrogen Energy 36 (7):4573–79. doi:10.1016/j.
ijhydene.2010.04.098.
Zhang, L. L., S. Wang, S. Jiao, K. Huang, and H. Zhu. 2012. Electrochemical
synthesis of titanium oxycarbide in a CaCl2 based molten salt.
Electrochimica Acta 75 (30):357–59. doi:10.1016/j.electacta.2012.05.013.
Zhang, T.-A., Z. H. Dou, Y. Liu, G. Z. Lv, L. P. Niu, Q. Y. Zhao, and
J. C. He. 2011. A magnesium and chlorine recycling method of pre­
paration of titanium sponge. China patent CN 201110104639.
Zhang, T.-A., Z. H. Dou, G. Z. Lv, Y. Liu, Q. Y. Zhao, Z. M. Zhang, and
X. L. Jiang. 2013. Cleaner production method for preparing superfine
powder through self-propagating metallurgy method. China patent
CN201310380803.4.
Zhang, T.-A., Z. H. Dou, Z. S. Yin, H. G. Tang, L. P. Niu, Y. Liu, G. Z. Lv,
and J. C. He. 2010. Method for preparing high-titanium iron by
step-by-step metal thermal reduction. China patent
CN201010514572.3.
Zhang, T.-A., Z. H. Dou, Z. M. Zhang, Y. Liu, G. Z. Lv, and J. C. He.
2014. A direct preparation method of titanium based on alumi­
nothermic reduction injection depth reduction. China patent
CN201410345905.2.
Zhang, W. S., Z. W. Zhu, and C. Y. Cheng. 2011. A literature review of
titanium metallurgical processes. Hydrometallurgy 108:177–88.
doi:10.1016/j.hydromet.2011.04.005.
Zhang, Y. 2014. Recovery of titanium from titanium bearing blast furnace
slag by sulphate melting. Canadian Metallurgical Quarterly 53
(4):440–43. doi:10.1179/1879139514Y.0000000136.
Zhang, Y., Z. Fang, Y. Xia, Z. Huang, H. Lefler, T. Zhang, P. Sun, M. Free,
and J. Guo. 2016. A novel chemical pathway for energy efficient pro­
duction of Ti metal from upgraded titanium slag. Chemical Engineering
Journal 286:517–27. doi:10.1016/j.cej.2015.10.090.
Zhang, Y., Z. Fang, Y. Xia, P. Sun, B. Devener, M. Free, H. Lefler, and
S. Zheng. 2017. Hydrogen assisted magnesiothermic reduction of TiO2.
Chemical Engineering Journal 308:299–310. doi:10.1016/j.cej.2016.09.066.
Zhang, Y., W. Lu, P. Sun, Z. Fang, S. Qiao, Y. Zhang, and S. Zheng. 2020.
Deoxygenation of Ti metal: A review of processes in literature.
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MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 551
International Journal of Refractory Metals and Hard Materials
91:105270. doi:10.1016/j.ijrmhm.2020.105270.
Zhao, K., and N. X. Feng. 2017. A new two-stage aluminothermic reduction
process for preparation of Ti/Ti-Al alloys. In Rare metal technology, eds. H.
Kim, S. Alam, N. Neelameggham, H. Oosterhof, T. Ouchi, X.
Guan, 167–75. Switzerland: Springer, Cham. doi:10.1007/978-3-319-
51085-9_17.
Zhao, K., N. X. Feng, and Y. W. Wang. 2017b. Fabrication of Ti-Al
intermetallics by a two-stage aluminothermic reduction process using
Na2TiF6. Intermetallics 85:156–62. doi:10.1016/j.intermet.2017.02.016.
Zhao, K., Y. W. Wang, and N. X. Feng. 2017c. Cleaner production of Ti
powder by a two-stage aluminothermic reduction process. JOM 69
(10):1795–800. doi:10.1007/s11837-017-2337-3.
Zhao, K., Y. W. Wang, J. P. Peng, Y. Di, X. Z. Deng, and N. X. Feng. 2017a.
Electrochemical preparation of titanium and titanium–copper alloys
with K2Ti6O13 in KF–KCl melts. Rare Metals 36 (6):1–6. doi:10.1007/
s12598-016-0708-5.
Zhao, K., Y. W. Wang, J. P. Peng, Y. Di, K. R. Liu, and N. X. Feng. 2016.
Formation of Ti or TiC nanopowder from TiO2 and carbon powders by
electrolysis in molten NaCl-KCl. RSC Advance 6:8644–50. doi:10.1039/
C5RA23063B.
Zhao, Z. G., X. Lu, W. Ding, and G. Zhou. 2005. A new technology using
SOM to produce titanium sponge. Shanghai Metals 27 (2):40–43.
Zhu, F. L., H. Yuan, Q. Yu, B. Yang, B. Xu, and Y. Dai. 2011. Behavior of
titanium dioxide in alumina carbothermic reduction-chlorination pro­
cess in vacuum. Transactions of Nonferrous Metals Society of China 21
(8):1855–59. doi:10.1016/S1003-6326(11)60941-2.
Zou, X. L., and X. Lu. 2010. Preparation of titanium alloy by direct
reduction of Ti-bearing blast furnace slag. The Chinese Journal of
Nonferrous Metals 20 (9):1829–35.
Zou, X. L., X. Lu, C. Li, and Z. Zhou. 2010. A direct electrochemical route
from oxides to Ti-Si intermetallics. Electrochimica Acta 55
(18):5173–79. doi:10.1016/j.electacta.2010.04.032.
Zuhair, A. M., and A. Umberto. 1989. Self-propagating exothermic reac­
tions: The synthesis of high-temperature materials by combustion.
Materials Science Reports 3 (7–8):277–365. doi:10.1016/0920-2307(89)
90001-7.