JOM, Vol. 71, No.

10, 2019
https://doi.org/10.1007/s11837-019-03597-3
 2019 The Minerals, Metals & Materials Society

COMPOSITION-PROCESSING-MICROSTRUCTURE-PROPERTY RELATIONSHIPS OF TITANIUM ALLOYS

Formation Mechanism and Distribution of Al and O

in the Ferrotitanium with Different Ti Contents Prepared
by Thermite Method

CHU CHENG,1,3 TING-AN ZHANG,2,4 and ZHI-HE DOU2

1.—School of Materials Science and Engineering, Henan University of Science and Technology,
Luoyang 471003, China. 2.—School of Metallurgy, Northeastern University, Shenyang 110819,
Liaoning, China. 3.—e-mail: cheng_chu_love@126.com. 4.—e-mail: zta2000@163.net

Ferrotitanium is used as a deoxidizer, a degassing agent and an alloying

element additive in the steel industry. The thermite method, as a way of
preparing ferrotitanium, has the advantages of abundant raw material re-
sources, low energy consumption, and low production costs. However, Al and
O impurities in ferrotitanium prepared by this method change greatly with its
Ti content. The distribution of Al and O residuals and their relationship with
the Ti content of the ferrotitanium prepared by the thermite method were
studied. The results show that Al and O residuals in the ferrotitanium pre-
pared by the thermite method are mainly caused by intermetallic compounds
and Al2O3 inclusion. The Al and O residuals are the quadric function of the Ti
content in the alloy prepared by thermite reduction. With increasing Ti con-
tent in the ferrotitanium, the amount of intermetallic compounds and Al2O3
inclusions both increase. When the Ti content in the alloy is lower than about
30%, the Al residual in the ferrotitanium prepared by the thermite method is
mainly caused by Fe-Al intermetallic compounds, while the O residual is
mainly caused by the Al2O3 inclusion. When the Ti content in the alloy is
higher than about 30%, the Al residual in the ferrotitanium prepared by the
thermite method is caused by Ti-Al intermetallic compounds and Al2O3
inclusion, while the O residual is mainly caused by a great number of Al2O3
inclusions and sub-oxides, such as Ti4Fe2O.

non-deformed Al2O3 inclusions are formed when Al

INTRODUCTION
Ferrotitanium is used as a deoxidizer, a degassing
agent and an alloying element additive in the steel
industry.1 It is a key additive in the smelting of
special steel and structural steel, which can reduce
the segregation of steel ingots and increase the
strength, corrosion resistance and stability of the
steel.2 Ferrotitanium with a Ti content less than
45.0% (low and medium ferrotitanium) is mainly
used as a deoxidizer, and its Al residual generally
needs to be controlled to less than 6.0–10.0%. Since
aluminum in the alloy can also participate in
deoxidation, the requirements of the Al and O
residuals are low. Ferrotitanium with a Ti content
ranging from 65.0% to 75.0% (high ferrotitanium) is
generally used as an alloying additive and as an
ultra-low oxygen special steel deoxidizer. However,
is used as a deoxidizer, which is harmful to the
fatigue resistance of the steel.3–5 Therefore, the Al
residual in the high ferrotitanium generally needs
to be controlled below 0.5–5.0%. The requirements
of the Al and O residuals here are extremely severe.
At present, ferrotitanium is mainly produced by
electrochemical reduction, remelting processes and
the thermite method. Electrochemical reduction is a
novel method for producing ferrotitanium and
receiving much attention.6 However, many prob-
lems in the process hinder industrial production.
The remelting process7 with Ti scrap and Fe as raw
materials has low Al and O residuals, but is
restricted by the availability of Ti scrap and high
production costs. Therefore, it is mainly used to
produce ferrotitanium with a Ti content ranging
from 65.0% to 75.0%. In the thermite method, Al is

3584 (Published online June 13, 2019)

Formation Mechanism and Distribution of Al and O in the Ferrotitanium with Different Ti
Contents Prepared by Thermite Method
used as the reductant and Al and O residuals are
inevitably introduced into the ferrotitanium
because of the incomplete reaction and slag–metal
separation. Ferrotitanium with a Ti content of less
than 45.0% that meets industrial demand can be
directly produced by this method but ferrotitanium
with a Ti content ranging from 65.0% to 75.0% that
meets industrial demand can not be directly pro-
duced because of the high Al and O residuals.
However, this method has the advantages of abun-
dant raw material resources, low energy consump-
tion, and low production costs. Therefore, in order to
produce high ferrotitanium by the thermite method,
many researchers have investigated the prepara-
tion and deoxidizing mechanism of ferrotitanium
based on the thermite method. Lai8 studied the
control of aluminum and silicon content in ferroti-
tanium prepared by the thermite method. The
results show that the particle size and ratio coeffi-
cient of aluminum powder, and the unit mass
reaction heat and feed rate of ingredients have a
great influence on the Al residuals of the alloy.
Chunarev9 conducted a feasibility study on the
preparation of high-titanium iron by the thermite
method using crude ore as the raw material. The
results showed that high ferrotitanium (60–70%)
with O content £ 5 wt.% could not be produced
directly by the out-of-furnace thermite method.
After refining with the addition of CaO-CaF2 slag,
ferrotitanium products with Ti, Al and O contents of
53.4%, 11.8% and 2.8% and of 65.7, 6.6% and 4.5%
were produced. It can be speculated that there is a
certain relationship between the Al and O residuals
in the ferrotitanium by the thermite method. In our
preliminary study, we studied the preparation of
ferrotitanium and deoxidation mechanisms by the
thermite method. The results show that the Al
residual exists in the form of Al2O3 and intermetal-
lic compounds, and that the O residual in the high
ferrotitanium exists in the form of oxides, such as
Al2O3, Fe2TiO4 and Ti2O.10,11 Al and O residuals in
the high ferrotitanium are more than 10%, which is
much higher than that in low ferrotitanium (less
than 5%).12,13 This shows that the Al and O
residuals have a lot to do with the Ti content of
the ferrotitanium. Therefore, for this paper, ferroti-
tanium products with different Ti contents were
prepared by an aluminothermic method. The distri-
bution of the Al and O residuals and their relation-
ship with Ti content of the ferrotitanium prepared
by the thermite method were studied.
EXPERIMENTAL
Materials
High-titanium slag (86.03% TiO2, particle size: £
3 mm; Panzhihua Iron & Steel Group, China), iron
concentrate (63.07% TFe, particle size: 0.1–0.5 mm;
Pilbara, Australia) and Fe2O3 (AR; Sinopharm
Chemical Reagent) were used as the raw materials.
The chemical composition of the raw materials is
3585
shown in Table SI. Aluminum powder (Al, 98.5%,
particle diameter: £ 3 mm; Jinzhou Metal, China)
was used as the reductant. KClO3 (99.5%, particle
diameter: £ 3 mm), CaO (99.5%, particle diame-
ter: £ 250 lm), and magnesium powder (99.5%,
particle diameter: 0–0.2 mm) were produced by
Sinopharm Chemical Reagent, China.
Experimental Methods
For preparing the raw materials before the exper-
iment, high-titanium slag, iron concentrate, Fe2O3
powder, CaO and KClO3 were heated in air in the
temperature range of 423–573 K for 24 h. The
ingredients were weighed in proportion (shown in
Table SII) and thoroughly mixed with Al powder in
a ball mill for 1 h, following which they were
preheated at 383 K for 1 h. The ingredients were
placed into a conical graphite reactor enclosed by a
magnesia lining with a volume of 10 L. Approxi-
mately 2–3 g of Mg powder was used as an easy
ignition agent placed on top of the ingredients. The
Mg powders were ignited to induce the SHS reaction
to obtain a high-temperature melt, which flowed
into the separator of the alloy and slag at the bottom
of the conical graphite reactor. About 1 min later,
the melt was cast into a graphite crucible enclosed
by a magnesia lining and cooled to room tempera-
ture. Samples of the alloy were collected. The
stoichiometric ratios of the Al powder (RAl) used as
a reductant for Ti-rich materials and Fe2O3 in
experiments were 1.0. The molar ratio of CaO/Al2O3
(RC/A) in the experiments were 0.2 (Al2O3 is a
combustion product of the SHS reaction in theoret-
ical stoichiometry).
Analysis Methods
The alloys were analyzed by x-ray diffractometry
(XRD; Model D8; Bruker, Germany; working condi-
tions: Cu Ka1, 40 kV, 40 mA). The oxygen contents
of the alloy samples were measured by an oxygen
and nitrogen hydrogen analyzer (Type G8; Bruker).
The compositions of the alloys were analyzed by
inductively coupled plasma atomic emission spec-
trometry (ICP; Optima 4300DV; Lehman, USA).
The microstructures of the alloy samples were
observed by a scanning electron microscope (SEM;
SU-8010; Hitachi, Japan) and an energy dispersive
spectrometer (EDS; Bruker).
RESULTS AND DISCUSSION
Chemical Composition
Table I shows the chemical compositions of the
ferrotitanium products with different Ti contents
prepared by the thermite method. The results show
that the Ti content of the ferrotitaniums 1–8
prepared by the thermite method ranges from
11.5% to 66.27%. The Ti content of the ferrotita-
nium using only high-titanium slag as raw material
is 66.27%, which indicates that it is not feasible to
3586 Cheng, Zhang, and Dou

Table I. Chemical compositions of ferrotitanium products with different Ti contents prepared by the
thermite method

No. Ti Fe Al Si Mn O S Others
1 11.50 78.24 3.72 2.86 0.29 0.032 0.038 Bal.
2 14.10 72.79 4.03 2.52 0.464 0.099 0.047 Bal.
3 26.00 65.46 5.39 2.16 0.70 0.181 0.04 Bal.
4 31.20 58.46 5.50 1.37 0.90 0.566 0.13 Bal.
5 45.89 36.08 7.08 0.89 0.96 4.6 0.32 Bal.
6 52.08 25.40 9.01 0.58 1.00 5.81 0.61 Bal.
7 60.24 16.61 10.25 0.46 1.05 8.38 0.78 Bal.
8 66.27 3.9 12.11 0.44 1.13 10 0.83 Bal.

contents in the alloy increase while the Si content

decreases with the increasing Ti content. The main
reasons are as follows. Table SI shows that the Mn
and S contents in the high-titanium slag is higher
but the Si content is lower than that in the titanium
concentrate. At the same time, with the increasing
Ti content, the ratio of high-titanium slag in the raw
materials increases while the ratio of the titanium
concentrate decreases (as shown in Table SII).

Fig. 1. The relationship between Ti and Al and O in the alloy
prepared by thermite reduction.
prepare high-ferrotitanium (Ti 65.0–75.0%) by
using the high-titanium slag as raw material. The
contents of Fe and Si in the alloy decrease with the
increasing Ti content, while the contents of Al, O,
Mn and S increase gradually. Figure 1 shows the
relationship between Ti and Al, and O in the alloy
prepared by thermite reduction. After fitting, Al and
O residues can be represented as:
yAl ¼ 3:67753  0:00118xTi þ 0:00189x2Ti
yO ¼ 0:40059  0:08725xTi þ 0:00359x2Ti ;
where x is the Ti content of the alloy prepared by the
thermite method.
It can be concluded that there are quadratic
relationships between the Al and O residuals and
the Ti content in the alloy prepared by thermite
reduction: the Al and O residuals in the alloy both
increase with the increasing Ti content. The Al and
O residuals both increase slowly when the Ti
content is lower than 30%, but they increase rapidly
when the titanium content is higher than 30%. The
Si, Mn, and S contents in the ferrotitanium alloy are
mainly introduced by impurities in the raw mate-
rials. In addition, Table I shows that the Mn and S
XRD Analysis
Figure S1 shows the XRD patterns of the ferroti-
tanium products with different Ti contents prepared
by the thermite method, indicating that obvious
diffraction peaks of Fe2Ti, AlFe3 and AlFe can be
observed when the Ti content in the alloy is lower
than 30%. However, with the increasing Ti content,
diffraction peaks of intermetallic compounds (such
as AlTi2, AlTi3 and Al2Ti3) and sub-oxides (such as
Ti3Fe3O, Ti4Fe2O, TiO, Ti3O and Ti6O) appear
successively. In addition, diffraction peaks of
Al2O3 can be observed. This indicates that, with
the increasing Ti content in the alloy, the phases of
the ferrotitanium alloy turn from phases containing
Fe into phases containing Ti, and the Ti-Al inter-
metallic compounds, titanium sub-oxides and Al2O3
inclusions all increase.
Al and O Distribution
Figure 2 shows the SEM images of the ferrotita-
nium products with different Ti contents prepared
by the thermite method, with the chemical compo-
sitions shown in Table I, Fig. 2a, b, and c indicates
that the size and amount of the Al2O3 inclusions are
both small when the Ti content in the alloy is lower
than 30%, which indicates a good metal–slag sepa-
ration. Figure 2d, e, f, g, and h indicates that the
amount of the Al2O3 inclusion becomes larger and
its morphology is complex and changeable with the
increasing Ti content when the Ti content in the
alloy is higher than 30%, which indicates that the
metal–slag separation is poor. The amount of Al2O3
inclusion in the ferrotitanium is mainly determined
by the effect of metal–slag separation during ther-
mite reduction.14,15 The reduction process of TiO2
Formation Mechanism and Distribution of Al and O in the Ferrotitanium with Different Ti 3587
Contents Prepared by Thermite Method

Fig. 2. SEM images of the alloys with different Ti contents prepared by the thermite method: (a) 1, (b) 2, (c) 3, (d) 4, (e) 5, (f) 6, (g) 7, (h) 8.
3588
Fig. 3. EDS analysis of the point M and P in the alloys with different Ti contents in Fig. 2: (a) point M, (b) point P.
obeys the theory of step-by-step reduction, and
titanium sub-oxides such as Ti3O5, Ti2O3 and TiO,
can be produced during the reduction process.16 At
the same time, research indicates that the lower the
valence state of Ti exists in the oxide, the more the
oxide can be reduced. With the increasing Ti content
in the ferrotitanium, the amount of intermetallic
compounds (such as Ti3Al, TiAl and AlFe) increase,
resulting in a shortage of the reducing agent Al,
thus causing the increase of high-melting-point
titanium sub-oxides in the slag. The melting-point
of the slag will be increased by high-melting-point
titanium sub-oxides resulting in poor metal–slag
separation and the increase of Al2O3 inclusions in
the alloy. In addition, with the increasing Ti content
in the ferrotitanium, the ratio of high-titanium slag
in the raw materials increase, which also results in
the increase of high-melting-point titanium sub-
oxides in the slag.17
Figure 3 shows the EDS analysis of the points M
and P in the alloys with different Ti contents in
Fig. 2. Figure 3a shows the content of the elements
in the matrix (M). When the Ti content in the alloy
is lower than 30%, the matrix is mainly composed of
Fe-based phases, and the Al residue in the matrix
combines with Fe forming Fe-Al intermetallic com-
pounds.18 However, when the Ti content in the alloy
is higher than 30%, the matrix is mainly composed
of Ti-Fe or Ti-based phases, and Al residue in the
matrix combines with Ti forming Ti-Al intermetallic
compounds or even precipitates Ti phases.19 Fig-
ure 3b shows the content of the elements in the
precipitated phase (P). When the Ti content in the
alloy is low, the precipitated phase is mainly Ti-Fe,
and Al is dissolved in Ti-Fe phase. When the Ti
content in the alloy is high, the precipitation phase
in the alloy is a Ti-Al intermetallic compound phase
and its amount increases with the increasing Ti
content. Comparing to the Al residual in the phases
in Fig. 3a and b, it is known that the Al residual
Cheng, Zhang, and Dou
when combined with Fe in the M phase is always
lower than that of being combined with Ti in the P
phase, which indicates that, compared to Fe, Al
more easily combines with Ti. After fitting, the Ti
content in the P phase can be represented as:
yTi ¼ 22:58375 þ 0:51998x
The Al residual in the P phase can be represented
as:
yAl ¼ 0:34166x3:24446
Combining the analysis results from Fig. 1 and
Fig. S1, it can be concluded that, when the Ti
content in the alloy is low, the Al residual in the
ferrotitanium prepared by the thermite method is
mainly caused by the Fe-Al intermetallic com-
pounds, while the O residual is mainly caused by
Al2O3 inclusions. When the Ti content in the alloy is
high, the Al residual in the ferrotitanium prepared
by the thermite method is caused by Ti-Al inter-
metallic compounds and Al2O3 inclusions, while the
O residual is mainly caused by a great number of
Al2O3 inclusions and sub-oxides, such as Ti4Fe2O.
CONCLUSION
1. Al and O residuals in ferrotitanium prepared by
the thermite method is mainly caused by inter-
metallic compounds and Al2O3 inclusions. The
Al and O residuals are the quadric functions of
the Ti content in the alloy prepared by thermite
reduction.
2. With increasing Ti content in the ferrotitanium,
the amount of intermetallic compounds (such as
Ti3Al, TiAl and AlFe) and Al2O3 inclusions both
increase. When the Ti content in the alloy is less
than 30%, the Al residual in the ferrotitanium
prepared by the thermite method is mainly
Formation Mechanism and Distribution of Al and O in the Ferrotitanium with Different Ti
Contents Prepared by Thermite Method
caused by Fe-Al intermetallic compounds, while
the O residual is mainly caused by Al2O3
inclusions. When the Ti content in the alloy is
higher than about 30%, the Al residual in the
ferrotitanium prepared by the thermite method
is caused by Ti-Al intermetallic compounds and
Al2O3 inclusions, while the O residuals are
mainly caused by a great number of Al2O3
inclusions and sub-oxides, such as Ti4Fe2O.
ACKNOWLEDGEMENTS
This research was supported by the National
Natural Science Foundation of China [51422403,
51504064], Fundamental Research Funds for the
Central Universities [N162505002] and the Na-
tional Basic Research Program of China [973 Pro-
gram, No. 2013CB632606].
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