Kasetsart J. (Nat. Sci.

) 42 : 357 - 361 (2008)

Phase Characterization of TiO2 Powder by XRD and TEM

Kheamrutai Thamaphat1*, Pichet Limsuwan1 and Boonlaer Ngotawornchai2

ABSTRACT

In this study, the commercial TiO2 nanopowder and micropowder of anatase phase and rutile
phase have been characterized by x-ray diffraction (XRD) and transmission electron microscopy (TEM).
XRD patterns of nano-TiO2 in rutile and anatase phases exhibit broad peaks whereas both phases of
micro-TiO2 demonstrate very sharp peaks. TEM images show that the grain size of TiO2 micropowders
and TiO2 nanopowders are 0.3-0.7 µm and 10 nm, respectively. The selected-area electron diffraction
patterns of TiO2 nanopowders in rutile and anatase phases are consistent with XRD results.
Key words: TiO2, anatase, rutile, micro and nanopowders, TEM, XRD

INTRODUCTION carbonic acid gas, and generation of hydrogen gas

(Zhang et al., 2000). In most of these cases, the
Titanium dioxide or titania (TiO2) was size of the TiO2 particles is an important factor
first produced commercially in 1923. It is obtained affecting the performance of the materials. It is
from a variety of ores. The bulk material of TiO2 not surprising; therefore, that much research has
is widely nominated for three main phases of rutile, been focused upon the reduction of the particle
anatase and brookite (Kim et al., 2005). Among size. Much effort has been devoted to the
them, the TiO2 exists mostly as rutile and anatase preparation of TiO2 nanopowders, including sol-
phases which both of them have the tetragonal gel route, homogeneous precipitation,
structures. However, rutile is a high-temperature hydrothermal methods, flame synthesis and
stable phase and has an optical energy band gap relatively new molten salts method (Bilik and
of 3.0 eV (415 nm), anatase is formed at a lower Plesch, 2007). They were usually found that
temperature with an optical energy band gap of different routes often produced different results.
3.2 eV (380 nm) and refractive index of 2.3 (Brady, Even for the same route, using different amount
1971). of the starting materials, the obtained powder size
TiO2 is mainly applied as pigments, is different (Li et al., 2002).
adsorbents, catalyst supports, filters, coatings, Consequently, phase and particle size are
photoconductors, and dielectric materials. In the important parameters that influence physical
recent years, TiO2 has been well known as a properties of material. Several techniques could
semiconductor with photocatalytic activities and be used for the investigation of them. However,
has a great potential for applications such as the particle size determination can be based on
environmental purification, decomposition of direct observation of particles by transmission

1 Department of Physics, Faculty of Science, King Mongkut’s University of Technology Thonburi, Bangkok 10140, Thailand.
2 Scientific and Technological Research Equipment Centre, Chulalongkorn University, Bangkok 10330, Thailand.
* Corresponding author, e-mail: [email protected]
358 Kasetsart J. (Nat. Sci.) 42(5)

electron microscopy (TEM) or scanning electron TEM with a JEOL JEM-2100 ultra high resolution
microscope techniques, in this case, we can also TEM operating at 160 kV.
receive the important information on the shape of
particles. Data on particle size can be obtained by RESULTS AND DISCUSSION
X-ray diffraction (XRD) technique as the particle
size is related to the diffraction peak broadening. XRD
It is important to note that TEM and XRD methods XRD patterns of nano-TiO2 and micro-
allow not only to measure the particle size, but TiO2 in rutile and anatase phases are shown in
also to identify crystalline phases. Figure 1 and Figure 2, respectively. In Figure 1,
XRD patterns exhibited strong diffraction peaks
MATERIALS AND METHODS at 27°, 36° and 55° indicating TiO2 in the rutile
phase. On the other hand, in Figure 2, XRD
Four commercial TiO2 samples used in patterns exhibited strong diffraction peaks at 25°
this experiment were provided by Aldrich: (i) and 48° indicating TiO2 in the anatase phase. All
99.7 % anatase, nanopowder; (ii) 99.8 % anatase, peaks are in good agreement with the standard
micropowder; (iii) 99.5 % rutile, nanopowder; (iv) spectrum (JCPDS no.: 88-1175 and 84-1286).
99.9 % rutile, micropowder. From Figure 1 and Figure 2, they were shown that
XRD measurements were performed on the diffraction pattern peak intensity of the TiO2
the Bruker D8 Advance diffractometer operating increases with increasing particles size. These
in the reflection mode with Cu-Kα radiation (35 results suggested that the nano-TiO2 powder is
kV, 30 mA) and diffracted beam monochromator, composed of irregular polycrystalline. Amorphous
using a step scan mode with the step of 0.075° revealed a broad pattern with low intensity;
(2θ) and 4 s per step. Diffraction patterns of both however, the effect of the amorphous materials on
anatase and rutile TiO2 powders were compared the broadening of the XRD patterns of nanosized
with reference to JCPDS database. Additionally, TiO2 is negligible.
the morphology of the powder was observed by

(110) (a) micropowders 0

(101) (a) micropowders

0
0

00

(211)
0
Intensity (a.u.)

0 (101)
Intensity (a.u.)

0 0
0
0 (200)
0 0
(301) 0
(004) (105) (211)
(111) (220)
0 (118)
(310) (112) (220)
(200) (210) (103)
(112)
(002) (116)

(b) nanopowders
(b) nanopowders

# JCPDS 88-1175
# JCPDS 84-1286

10 15 20 25 30 35 40 45 50 55 60 65 70 10 15 20 25 30 35 40 45 50 55 60 65 70
Degree (2θθ ) Degree (2 θ )

Figure 1 X-ray diffraction of rutile TiO2 (a) Figure 2 X-ray diffraction of anatase TiO2 (a)
micropowders and (b) nanopowders. micropowders and (b) nanopowders.
 Kasetsart J. (Nat. Sci.) 42(5) 359

TEM TEM bright field images of TiO 2

TEM was used to further examine the nanopowders in rutile and anatase phases are
particle size, crystallinity and morphology of shown in Figure (3b) and (4b), respectively. It can
samples. TEM bright field images of TiO 2 be estimated that the particle size of powders in
micropowders in rutile and anatase phases are Figure (3b) and (4b) are nanoscale with the grain
shown in Figure (3a) and (4a), respectively. It is size lese than 10 nm. The corresponding selected-
clearly seen that the TiO2 powders in rutile phase area electron diffraction (SAED) patterns of nano-
consist of both spherical and rod shapes but the TiO2 powders in rutile and anatase phases are
particle of TiO2 powders in anatase phase are shown in Figure (3c) and (4c), respectively. These
mostly spherical morphology. Furthermore, it can are in agreement with XRD results in Figure (1b)
be estimated that the particle size of samples in and (2b), respectively. In Figure (3c), the SAED
Figure (3a) and (4a) are microscale with the grain patterns of nano-TiO2 powders in rutile phase
size about 0.3-0.7 µm. shows spotty ring patterns without any additional

Figure 3 Images of rutile phase. (a) TEM image of micro-TiO2 powder; (b) TEM image of nano-TiO2
powder; (c) SAED pattern of nano-TiO2 powder and (d) HRTEM image of nano-TiO2 powder.
360 Kasetsart J. (Nat. Sci.) 42(5)

diffraction spots and rings of second phases, only one crystal lattice plane(110) with d-spacing
revealing their well crystalline. On the other hand, of 0.301 nm is obtained, whereas those of anatase
the SAED patterns of nano-TiO2 powders in give many crystal lattice planes with d-spacing of
anatase phase (Figure (4c) shows that the 0.313 nm for the plane (101).
brightness and intensity of polymorphic ring is
weak, so they are poorly crystallized and partly CONCLUSION
amorphous.
The crystallinity of nano-TiO2 powders In this work, a study has been carried out
can also be observed by phase-contrast images or on the identification of phase and particle size of
Moire patterns. Figure (3d) and (4d) show crystal TiO2 powders using XRD and TEM techniques.
lattice planes of nano-TiO2 in rutile and anatase All high purities samples were commercial TiO2.
phases, respectively. It is seen that, for rutile phase, From the results, X-ray diffraction patterns can

Figure 4 Images of anatase phase. (a) TEM image of micro-TiO2 powder; (b) TEM image of nano-
TiO2 powder; (c) SAED pattern of nano-TiO2 powder and (d) HRTEM image of nano-TiO2
powder.
 Kasetsart J. (Nat. Sci.) 42(5) 361

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