Journal of Alloys and Compounds 585 (2014) 75–77

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Journal of Alloys and Compounds

journal homepage: www.elsevier.com/locate/jalcom

Letter

A new highly efficient method for the synthesis of rutile TiO2

Guo Chen a,⇑, Jin Chen a, Zengkai Song a, C. Srinivasakannan b, Jinhui Peng a,1
a
Key Laboratory of Unconventional Metallurgy, Ministry of Education, Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology,
Kunming 650093, PR China
b
Chemical Engineering Program, The petroleum Institute, Abu Dhabi, P.O. Box 253, United Arab Emirates

a r t i c l e i n f o a b s t r a c t

Article history: A new highly efficient method has been developed for the synthesis of the synthesis of rutile TiO2 from
Received 29 July 2013 titania slag. High quality of rutile TiO2 were obtained by carrying out the synthesis in conventional heat-
Accepted 6 September 2013 ing method. The thermal stability, crystal structures and molecular structures of rutile TiO2 and titania
Available online 19 September 2013
slag before and after treatment were characterized using TG/DTA, XRD and Raman, respectively. The
results of TG/DTG showed roasting temperature range of 850–1000 °C was used in the further research
Keywords: work in order to transform from anatase TiO2 to rutile TiO2. The XRD results demonstrate that a rutile
Phase transformation
TiO2 with high crystallinity was prepared. With increasing roasting temperature, the intensity of Raman
Rutile TiO2
Anatase TiO2
vibrations bands of anatase TiO2 decrease, and the intensity of Raman vibrations bands of rutile TiO2
Titania slag increase. Based on the mention results, this method can be applied effectively and efficiently way for both
titania slag utilization and rutile TiO2 preparation.
Ó 2013 Elsevier B.V. All rights reserved.

1. Introduction In recent years, several researchers have published the preparation

Titanium dioxide occurs naturally in three crystalline forms:
anatase, brookite and rutile [1]. These crystals are essentially pure
titanium dioxide but usually contain small amounts of impurities,
such as iron, which gives a dark color [2]. They are also of different
crystal habit, rutile forms slender, prismatic crystals which are fre-
quently twinned, but anatase usually occurs in near regular octa-
hedral [3]. TiO2 is manufactured by the chloride or sulfate
processes, in which ilmenite is used as raw materials [4–6]. This
was because of ilmenite is an economically important and interest-
ing mineral [7,8]. Ilmenite can be upgraded to a synthetic rutile by
direct leaching with hydrochloric acid [9]. The leaching time can be
shortened by the use of high temperature and pressure, but the
synthetic rutile thus yielded is fine grained and would require
agglomeration before being useable in fluid-bed chlorinators
[10]. Similar direct leaching processes for producing synthetic ru-
tile have been patented [11]. Consequently, the increasing use of
the chloride process for producing titanium dioxide pigments has
motivated a search for a more abundant and cheaper raw material
than the presently used rutile resources. Since available resources
of high grade natural rutile tend to diminish, the shortage of
natural rutile has encouraged researchers to find an efficient
method to convert anatase in titania slag to synthetic rutile [12].
⇑ Corresponding author: Tel./fax: +86 871 65138997.
E-mail addresses: guochen@kmust.edu.cn (G. Chen), jhpeng@kmust.edu.cn (J.
Peng).
1
Co-corresponding author.
methods and applications of titania slag [13]. Guo et al. investi-
gated the Ti2O3 was successfully disintegrated from Fe3Ti3O10 of
titania slag through a new route. The results demonstrate that
the titania slag is oxidized at lower temperature [14].
In the present work, rutile TiO2 was prepared from titania slag
under roasting processing. The thermal stability, crystal structures
and molecular structures of titania slag before and after roasting
were mainly studied and analyzed by thermogravimetry and dif-
ferential thermal analysis (TG/DTG), X-ray diffraction (XRD), and
Raman spectroscopy techniques, respectively.
2. Experimental
2.1. Materials
In the present study, titania slag was obtained from Kunming city, Yunnan
province, China. The chemical compositions of titania slag were listed in Table 1.
From the XRD in Fig. 2(a), titania slag mainly contains Fe3Ti3O10 (JCPDS card No.
43-1011) and anatase TiO2 (JCPDS card No. 21-1272), in addition, a minor amount
of rutile TiO2 (JCPDS card No. 65-0191) was present. It can be seen from Fig. 3(a)
that the Raman peaks at 155.2, 195.8, 393.7, 515.5 and 637.3 cm1 which are di-
rectly attributable to anatase, Ti3O5, and Ti2O3, respectively.
2.2. Characterization
TG/DTG of differential thermal analysis for oxidation of titania slag were ob-
tained at a heating rate of 10 °C/min in high purity N2 gas (up to 99.99%) at a flow
rate of 30 ml/min, with a thermal gravimetric analyzer (NETZSCH STA 409, Ger-
many). The crystal structure of titania slag were characterized before and after
roasting processing by XRD (D/Max 2200, Rigaku, Japan) at a continuously scanning
rate of 0.25 deg/min, with 2h ranging from 5° to 100°. The voltage and anode

0925-8388/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jallcom.2013.09.056
76 G. Chen et al. / Journal of Alloys and Compounds 585 (2014) 75–77

current operated were 35 kV and 20 mA, respectively. The Raman spectra of titania 105
slag were performed before and after roasting at room temperature using a confocal
microprobe Raman system (Renishaw Ramascope System 1000, UK) with an air- (b)
cooled charge-coupled device (CCD) detector. A 514-nm argon laser was used for 104 0.12
excitation.

2.3. Procedure 103

0.08
Prior to the use, 100 g of titania slag was loaded on a ceramics boat which was
placed inside a stainless steel tubular reactor. Then the samples were heated to
102
120 °C at a heating rate of 5 °C/min in the drying oven and held at this temperature
for 120 min. After drying, the samples were cooled to room temperature. The sam- 0.04
ple holder is placed inside the muffle furnace (YFX12/16Q-YC, Shanghai, China) and
heated to 1050 °C at a heating rate of 15 °C/min and held at this temperature for 101
(a)
60 min. The temperature of the raw materials during roasting process is monitored
using a thermocouple inserted into the samples. After finishing the roasting pro- 0.00
cess, the roasted raw materials are naturally cooled to room temperature in the 100
furnace.
0 200 400 600 800 1000 1200

3. Results and discussion

Fig. 1. TG/DTG curves of titania slag: (a) DTG; (b) TG.
The TG/DTG measurement of titania slag was performed, and
the results are shown in Fig. 1. According to Fig 1(a), DTA curve
analyses show the two exothermic peaks at 477.2 °C and
8000 R
837.2.0 °C. An endothermic peak observed at 578.0 °C on the DTA M-Fe 3Ti3O 10
curve indicates the decomposition reaction of Fe3Ti3O10 as follows: 7000 A-Anatase
R-Rutile
Fe3 Ti3 O10 ! 3TiO2 ðAnataseÞ þ Fe3 O4 ð1Þ 6000 R
R
Intensity/CPS

At 850.0 °C, anatase TiO2 transforms to rutile TiO2 as shown in R

Eq. (2)
5000
M A M (b)
4000
TiO2 ðAnataseÞ ! TiO2 ðRutileÞ ð2Þ M,A
3000
The TG curve of sample show the weight loss processing was
observed between 25 °C and 400.0 °C, due to the dehydration of 2000
A
chemically bonded water in the sample, and the weight gain pro- M
1000 M R M
cessing was recorded in a temperature range from 400.0 °C to R R (a)
1100.0 °C, respectively. The weight gain ratio corresponding to this 0
roasting stage is 2.99%, which there are oxidation reductions of 0 20 40 60 80 100

low-valent titanium of titania slag were occurred, according to 2-Theta/deg

the following equation:
Fig. 2. XRD of titania slag before and after roasting: (a) titania slag; (b) rutile TiO2.
2Ti2 O3 þ O2 ¼ 4TiO2 ð3Þ

DGT ¼ 754909:8 þ 185:831T; J=mol

444.1 610.0
4000

2Ti3 O5 þ O2 ¼ 6TiO2 ð4Þ

242.9
Intensity/Counts

DGT ¼ 736235:6 þ 161:58T; J=mol 3000

(b)
Based on the above results, a roasting temperature range of
850–1000 °C was used in the further research work in order to 2000 637.3
transform from anatase TiO2 to rutile TiO2. 155.2
The crystal structures of titania slag before and after roasting
processing is characterized by XRD and the results are illustrated 393.7
1000
195.8 515.5
in Fig. 2. It can be found from Fig. 2(b) that the diffraction peaks
of rutile TiO2 gradually broadened and their intensities increased (a)
under roasting processing. The rutile TiO2 has the strongest
200 400 600 800 1000
preferential orientation of (1 1 0) plane at 2h = 27.44°. Compared
with the untreated raw materials, the second and third strong pref- -1
Raman shift/cm
erential orientation of (1 0 1) and (2 1 1) planes of rutile TiO2 pre-
Fig. 3. Raman spectra of titania slag before and after roasting: (a) titania slag; (b)
pared were observed at 2h = 36.09° and 2h = 54.33°, respectively.
rutile TiO2.
The XRD pattern of treated sample matches both the Bragg-posi-
tion and intensity of rutile TiO2 (JCPDS card No. 65-0191), which
demonstrates that a rutile TiO2 with high crystallinity was pre-
pared. The transformation of anatase to rutile in TiO2 is influenced
Table 1
Chemical composition of titania slag. by several experimental conditions, such as roasting temperature,
particle size and synthetic method of dioxide.
Material TiO2 Ti2O3 FeO SiO2 MgO S P C
The Raman spectrum of titania slag before and after roasting
Mass% 72.33 17.79 5.26 2.57 2.30 0.049 0.014 0.049 processing were characterized using Raman spectroscopy, and
 G. Chen et al. / Journal of Alloys and Compounds 585 (2014) 75–77
the result is shown in Fig. 3. It can be seen from Fig. 3(a) that the
bands at 393.7, 515.5 and 637.3 cm1 are due to the anatase TiO2
crystalline phase, which corresponded to the Raman active modes:
B1g, A1g and Eg, respectively. The band at 155.2 cm1 is due to the
symmetric stretching vibrations of symmetric stretching of Ti3O5.
The band at 195.8 cm1 is due to the wagging vibrations of O–
Ti–O bonds of Ti2O3. It can be seen from Fig. 3(b) that the peaks
at 242.9, 441.0 and 610.0 cm1 which are due to rutile TiO2. It
can be seen from Fig. 3(b) that the intensity of the band at 242.9,
441.0 and 610.0 cm1 in Raman spectra of rutile TiO2 prepared oc-
curs at 1050 °C for 60 min. With increasing roasting temperature,
the intensity of Raman vibrations bands of anatase TiO2 decrease,
the intensity of Raman vibrations bands of Ti3O5 and the intensity
of Raman vibrations bands of Ti2O3 disappears. And the intensity of
Raman vibrations bands of rutile TiO2 increase and the peaks indi-
vidually redshifts to low-wave number after roasting.
4. Conclusion
The present study attempts to utilize titania slag to prepare ru-
tile TiO2 during roasting process. The thermal stability, crystal
structures and molecular structures of titania slag before and after
roasting processing were characterized by thermogravimetry and
differential thermal analysis, X-ray diffraction and Raman spec-
troscopy techniques, respectively. DTA curve show that the two
exothermic peaks at 477.2 °C and 837.2.0 °C, which will corre-
sponding to the processing of decomposition reaction of Fe3Ti3O10
and anatase TiO2 transforms to rutile TiO2, respectively. The XRD
results demonstrate that a rutile TiO2 with high crystallinity was
prepared. The Raman results indicate that the intensity of Raman
vibrations bands of rutile TiO2 increase and the peaks individually
77
redshifts to low-wave number after roasting. Based on the results,
this method can be applied effectively and efficiently way for both
titania slag utilization and rutile TiO2 preparation.
Acknowledgements
The authors acknowledge the financial supports from the Na-
tional Scientific Foundation of China (No: 51090385), the Interna-
tional S&T Cooperation Program of China (No: 2012DFA70570),
Specialized Research Fund for the Doctoral Program of Higher Edu-
cation (No: 20125314120014) and the Applied Foundation Fund of
Yunnan Province of China (No: 2012FD015).
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