Materials Research Bulletin 38 (2003) 12831288

Preparation and characterization of solgel

derived ZnTiO3 nanocrystals
Shu Fen Wang, Feng Gu, Meng Kai Lu*, Chun Feng Song,
Su Wen Liu, Dong Xu, Duo Rong Yuan
State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, PR China
Received 28 June 2002; received in revised form 9 May 2003; accepted 21 May 2003

Abstract
Nanometer scale cubic ZnTiO3 has been synthesized by solgel method at a lower temperature (600 8C). X-ray
diffraction (XRD) analysis shows that the average crystalline size of the sample is
810 nm. The cubic to
hexagonal phase transition of ZnTiO3 is clearly observed from the XRD patterns of the sample. The thermal
behavior of the sample was characterized by the thermogravimetric/differenthermal analysis (TG/DTA), XRD
patterns, and the infrared spectra (IR). Transmission electron microscope (TEM) observations of the sample
reveal a high microstructural uniformity.
# 2003 Elsevier Ltd. All rights reserved.
Keywords: A. Nanostructures; B. Solgel synthesis

1. Introduction
Research on nanocrystallite materials has developed into a large interdisciplinary field in material
science. With the decreasing of the grain size, many novel and unusual mechanical, electrical, optical,
and magnetic properties can be obtained. The potential properties enhance the importance of nanometer
scale ATiO3 (A Ba, Sr, Ca, Pb) compound used as ferroelectric, semiconducting, and catalytic
materials. Extensive investigations have been made in this field focused on ATiO3 compounds [15].
However, there has not been much work on the preparation and characterization of ZnTiO3
nanocrystals, which can be used as white pigment and catalytic sorbents for the desulfurization of hot
coal gases [6,7]. Recent work has demonstrated that it can also be used as dielectric materials for
microwave devices and more preferably for low-temperature co-fired ceramics (LTCCs) [8,9]. As to the
preparation, the former researchers generally focused on such methods as solid-state reaction and
*

Corresponding author. Tel.: 86-531-8565403; fax: 86-531-8565403.

E-mail address: mklu@icm.sdu.edu.cn (M.K. Lu).
0025-5408/$ see front matter # 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0025-5408(03)00146-6

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precipitation [6,10]. This conventional method involves high calcining temperature and repeated cycles
of milling, resulting in the loss of the fine particle nature. Dulin and Rase used hydrothermal method to
obtain pure ZnTiO3 [11]. Here we report on an alternative method (solgel method) to prepare ZnTiO3
nanocrystals. The most distinctive advantage of this method is to provide homogeneous sols and gels at
a relatively low temperature. It is considered to be a promising way to produce chemically
homogeneous, high-purity and phase-pure powders. In this paper, we present preparation and
characterization of solgel derived ZnTiO3 nanocrystals for the first time. Furthermore, we analyze the
thermal behavior and TEM micrographs of the particles. The results show that the well-prepared
ZnTiO3 ultra-fine particles have the features of uniform dispersal and small particle size.

2. Experimental
2.1. Sample preparation
Precursor solutions for ZnTiO3 were prepared by the following method. Tetrbutylorthotitanate
(Ti(OC4H9)4) was dissolved in anhydrous ethanol. After stirring vigorously for about 30 min at room
temperature, a mixture of water and anhydrous ethanol was added dropwise to the above solution with a
burette. HNO3 was a catalyst. The molar ratio of Ti(OC4H9)4:C2H5OH:H2O was 1:25.4:1. The alkoxide
solution was kept stirring at room temperature for hydrolysis reaction for 2 h resulting in the TiO2 sol.
The solution of zinc acetate (Zn(CH3COO)22H2O) prepared with ethylene glycol (HOCH2CH2OH) as
a solvent was then added slowly into the TiO2 sol under stirring (Zn:Ti 1:1). White xerogel was
obtained by drying the gels at 110 8C for 5 h. Subsequently, the as-obtained xerogel was calcined at
600 8C for 1 h at weak oxidation atmosphere.
2.2. Apparatus
IR spectroscopy was performed by dispersion in potassium bromide using an American Ncolet FT-IR
20SX spectrometer ranging from 400 to 4000 cm1. Thermogravimetric analysis (TG) was conducted
using American Perkin-Elmer TGS-2 in air atmosphere over the temperature range 60780 8C at a
heating rate of 20 8C min1. The mass of the sample was 2.4039 mg. The differenthermal analysis
(DTA) of the sample was conducted with American Perkin-Elmer DTA1200. The curve of the sample
(8.40 mg) was obtained in air atmosphere at a heating rate of 20 8C min1 from 70 to 770 8C. A pure
aluminum cell was used as the reference. The X-ray powder diffraction patterns were recorded by using
Rigaku D/max-gA X-ray diffractometer with graphite monochromatized Cu Ka irradiation
). TEM studies were carried out using Japan JEM-100CX electron microscope.
(l 1:5418 A

3. Results and discussion

3.1. XRD pattern of the samples
Fig. 1 shows the XRD patterns of the samples with different heat-treated temperatures. Characteristic
diffraction peaks of cubic ZnTiO3 can be observed from the diffraction pattern of the sample obtained

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Fig. 1. XRD patterns of nanocrystal ZnTiO3 obtained at different heat-treated temperature.

at 500 8C. The pattern of the sample obtained at 600 8C consistent with the reference pattern, presents
diffraction peaks that are associated with the complete crystalline phase of cubic ZnTiO3. No peaks
related to hexagonal phase are observed. From the XRD analysis, it can also be observed that the
crystallization of the cubic ZnTiO3 increased with the increasing of heat-treated temperature from 500
to 600 8C. As the temperature increased to 800 8C, several peaks related to the crystalline phase of
hexagonal ZnTiO3 appears, although the cubic crystals are still dominant. It is revealed that a cubic to
hexagonal transformation occurs slowly in the process. This transformation temperature is lower than
that reported by Yamaguchi et al. [12].
The average crystalline size of the ZnTiO3 particles estimated from the XRD line using Debye
Scherrer formula (d 0:9l/b cos y) is
810 nm.
3.2. Thermal behavior
Fig. 2 shows the TG/DTA curves of the sample obtained at 600 8C. The DTA curve reveals two
exothermic peaks at 210350 and 430530 8C, respectively and an endothermic peak at 350430 8C.
The weight loss occurs in three main stages. The first weight loss below 340 8C can be attributed to the
combustion of the organic residues corresponding to a sharp exothermic peak at 210350 8C in DTA
curve. The second step that occurs in the temperature range 340410 8C results from the
dehydroxylation of TiOH into TiO2 as corroborated by a significant endothermic peak in the DTA

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Fig. 2. TG/DTA curves of nanocrystal ZnTiO3 obtained at 600 8C.

curve. The final weight loss between 410 and 540 8C indicates the crystallization of cubic ZnTiO3,
which can also be observed from the XRD pattern.
3.3. Characterization of the IR spectra
Fig. 3 shows the IR spectrum of the sample (600 8C). In the range 12001600 cm1, two weak bands
are observed. The band at about 1450 cm1 corresponds to the COH bending vibration. The one at
1619 cm1 is assigned to the d(OH) bending vibration. Bands below 800 cm1 are due to the TiO
stretching vibration. This result is consistent with the data reported by Shabalin, which indicates that
the compound characterizes by octahedral TiO6 groups [13]. From the IR spectrum, we can observe that

Fig. 3. IR spectra of nanocrystal ZnTiO3 obtained at 600 8C.

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Fig. 4. TEM micrographs of nanocrystal ZnTiO3 obtained at 600 8C.

after calcining at 600 8C most of the organic contents in the precursor powder disappeared, which is in
good agreement with the thermal behavior analysis mentioned earlier.
3.4. TEM analysis
Fig. 4 shows the representative TEM micrographs of the powder calcined at 600 8C. It can be
observed that the specimen are nearly spherical and of uniform grain size with limited aggregation. It
has a narrow particle-size distribution ranging between 8 and 10 nm.
The synthesis of single-phase ZnTiO3 is generally difficult due to the cubic-to-hexagonal
transformation and the decomposition into Zn2TiO4 and TiO2 (rutile) at temperature above 945 8C
[10]. The choice of heat treatment temperature for the sample was made on the base of their TG and
DTA analysis. According to the TG/DTA curve, we chose 500 8C as the first heat-treated temperature
and obtained the phase-pure cubic ZnTiO3 at 600 8C, which is lower than 765 8C reported by
Yamaguchi et al. [12].
The solgel technique using metal alkoxides as precursors is based on inorganic polymerization
reaction in which various metal alkoxides, e.g. M(OR)x and M0 (OR)y are hydrolyzed to produce
macromolecular networks containing MOM0 linkages [4]. According to this, we can assume a model to
describe the process as follows: (1) Hydrolysis: tetrbutylorthotitanate is hydrolyzed to the transparent
Ti(OH)4 sol gradually in the system. (2) Syneresis: reaction of adjacent OH groups or between OH and
OC4H9 groups occurs to form the TiOTi bonds and TiO bonds. Then Zn ions are dispersed into the
framework of the sol. This process ensures a homogeneous mixing of Zn ions and TiO2 sol at a molecular
level. It also reduces the diffusion distances between Zn ions and TiO6 octahedral. Therefore, this method
allows nano-level compositional control and makes crystallization at a relatively low temperature. The
lowering of the heat-treated temperature can greatly reduce the agglomeration of the ZnTiO3
nanoparticles. Thus, single-phase nanocrystal ZnTiO3 at a relatively low temperature was obtained.

4. Conclusion
ZnTiO3 nanoparticles have been obtained using solgel method. Complete crystallization of cubic
phase ZnTiO3 occurs at 600 8C. The cubic-to-hexagonal transformation occurs slowly. Thermal

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analysis shows that thermal behavior occurs in three major steps including combustion of the organic
content, the dehyroxylation of TiOH into TiO2 and the crystallization of cubic ZnTiO3. Resulting
particles are uniform dispersed as evidenced by the TEM images and XRD patterns. The diameter is
about 810 nm.

References
[1] P.S. Pizani, E.R. Leite, F.M. Pontes, E.C. Paris, J.H. Rangel, E.J.H. Longo, P. Delega, J.A. Varela, Appl. Phys. Lett. 77
(2000) 824.
[2] X.Z. Ding, Z.Z. Qi, Y.Z. He, J. Mater. Sci. Lett. 14 (1995) 21.
[3] G. Pfaff, Chem. Mater. 6 (1994) 58.
[4] M. Veith, S. Mathur, N. Lecerf, V. Huch, T. Decker, J. Sol-Gel Sci. Tech. 15 (2000) 145.
[5] J. Robertson, W.L. Warren, B.A. Tuttle, D. Dimos, D.M. Smyth, Appl. Phys. Lett. 63 (1993) 1519.
[6] H.W. Yao, R.B. Feng, Mining Safety Environ. Protect. 28 (2001) 20.
[7] R.P. Gupta, S.K. Gangwal, S.C. Jain, US Patent No. 5,714,431 (1998).
[8] H.T. Kim, J.D. Byun, Y. Kim, Mater. Res. Bull. 33 (1998) 963.
[9] H.T. Kim, Y. Kim, M. Valant, D. Suvorov, J. Am. Ceram. Soc. 84 (2001) 1081.
[10] S.F. Bartram, R.A. Slepetys, J. Am. Ceram. Soc. 44 (1961) 493.
[11] F.H. Dulin, D.E. Rase, J. Am. Ceram. Soc. 43 (1960) 125.
[12] O. Yamaguchi, M. Morimi, H. Kawabata, K. Shimizu, J. Am. Ceram. Soc. 70 (1987) C-97.
[13] B.G. Shabalin, Mineral. Zh. 4 (1982) 54.