Materials Chemistry and Physics 78 (2002) 184188

Preparation and characterization of nano-TiO2 powder

Baorang Li , Xiaohui Wang, Minyu Yan, Longtu Li
Department of Materials Science and Engineering, State Key Laboratory of New Ceramics and Fine Processing, Tsinghua University, Beijing 100084, PR China Received 5 December 2001; received in revised form 18 March 2002; accepted 23 May 2002

Abstract This paper reports the results of an investigation aiming at nding what affects the grain size of nano-TiO2 powder during synthesis. Nano-sized TiO2 powders have been prepared by a solgel method. The crystalline structures and morphologies of the powder have been characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The result shows that the different preparation conditions such as concentration, pH value, calcination time and calcination temperature have a lot of inuences upon the properties of nano-TiO2 powders. The smallest grain size of TiO2 powder we have obtained is 6 nm by controlling the process conditions. 2002 Elsevier Science B.V. All rights reserved.
Keywords: Concentration; pH value; Calcination time; Calcination temperature; Nano-TiO2 powder

1. Introduction Since Gleiters report [1] on the nano-materials, more attention has been paid upon the research of nano-materials. Compared with the traditional materials, nano-phase materials processes unusual chemical, mechanical, optical, electrical and magnetic properties [2]. Titanium dioxide is mainly applied as pigments, adsorbents, and catalytic supports. In almost all of these cases, the size of the titanium dioxide particles is an important factor affecting the performance of the materials. It is not surprising, therefore, that much research has been focused upon the reduction of particle size. Solgel route is regarded as a good method to synthesize ultra-ne metallic oxide [3] and has been widely employed for preparing titanium dioxide particles [47]. It was usually found that different routes often produce different results. Even for the same route, using different amount of the starting materials the powder size obtained is different [8]. So it is regarded as necessary for us to investigate in detail the factors which may have important effect upon the particle size. In this paper, titanium dioxide nano-powders were prepared by the hydrolysis of tetra-n-butyl titanate. Using various techniques, including transmission electron microscopy (TEM), X-ray diffraction (XRD), powders obtained were studied in order to nd the possible elements of affecting the microstructures and grain size.
Corresponding author. E-mail address: libaorang99@mails.tsinghua.edu.cn (B. Li).

2. Experimental TiO2 nano-powders were prepared via a solgel method using tetra-n-butyl-titanate and deionized water as the starting materials. Concentrations (the volume ratio of tetra-n-butyl titanate:deionized water) are chosen as 1:2, 1:6, 1:12, 1:20, 1:50, 1:100. Tetra-n-butyl-titanate was dropped into deionized water while magnetic agitating continuously. In order to investigate the effect of the pH value upon the grain size, hydrochloric acid or aqueous ammonia were dropped into the solution to get gel with different pH values. The obtained gel was then dried at 105 C for several hours until it was turned into yellow block crystal. After ball milling the dried gel obtained was calcined at different temperatures for 2 h. X-ray powder diffraction (XRD) for the powders calcined at various temperatures were recorded on a D/max-RB diffractometer using Cu K radiation. The particle size was calculated using the Scherrer equation and conrmed by TEM which was performed on a H-800 electron microscope. 3. Results and discussion 3.1. Calcination temperature XRD patterns of TiO2 nano-powders calcined at different temperatures are shown in Fig. 1. It can be obviously seen from the XRD that partial crystallization appears just after drying and the phase structure of the powder calcined

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growth rate is given by Eq. (1) [10]: u = a0 v0 exp Q Fv 1 exp (1) KT KT where a0 is the particle diameter, v0 the atomic jump frequency, Q the activation energy for an atom to leave the matrix and attach itself to the growing phase, Fv the molar free energy difference between the two phases. For non-crystallization Fv KT, so Eq. (1) can be reduced to Eq. (2): Q (2) KT When the calcination temperature is high, the activation energy is very small, the growth rate is large. So the grain size increases very quickly as the increasing calcination temperature; when the calcination temperature is low, the activation energy is very large, respectively, the growth rate becomes slow. So the grain size increases very slowly as the calcination temperature increases. Fig. 3 shows a set of the typical TEM micrographs of the nano-TiO2 powders calcined at 350, 500 and u = a0 v0 exp

Fig. 1. The XRD curves of nanocrystalline TiO2 at different calcination temperatures while the calcination time is 2 h, concentration 1:6 and pH value 7.

at temperatures below 600 C is mainly of anatase type. The phase transformation from anatase to rutile occurred at about 600 C and completed at about 800 C while in Haro-Poniatowskis report [7], the presence of the rutile was at about 545550 C. The grain size of the powder as a function of calcination temperature is plotted in Fig. 2. Obviously, the grain size increases with the increasing calcination temperature. It grows slowly at low calcination temperatures and then becomes very fast at high calcination temperatures. This is similar to the result in Ref. [9] and can be explained as below. The

Fig. 2. The curve of grain size versus calcination temperatures while the calcination time is 2 h, concentration 1:6 and pH value 7.

Fig. 3. TEM micrographs of the nano-TiO2 powders calcined at different calcination temperatures: (A) 350; (B) 500; (C) 600 C.

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600 C. It is easily found that about 6 nm nano-TiO2 powders can be obtained at 350 C, 13 nm at 500 C, 36 nm at 600 C, which is coincident to the result of XRD as shown in Fig. 2. Because the grain size depends upon the temperature strongly, it is believed that grain size of TiO2 particles in the dried gel should be smaller than 6 nm. 3.2. Calcination time The effect of the calcination time upon the grain size of TiO2 powders is shown in Fig. 4. At low calcination temperatures the prolongation of calcination time has little inuence upon the particle size. But when the calcination temperature increases to 1000 C, the obvious inuence upon grain size was found as shown in Fig. 4c. At relatively high temperatures the calcination time seems to have greater effect upon the grain size. Just as shown in Fig. 1, when the calcination temperatures are 350, 500, 1000 C the total crystallization had been completed and the corresponding phase type is anatase or rutile. The calcination times effects upon the grain size was thought to be controlled mainly by diffusion. At this time the following equation is given [11]: u ( Dt)1/2 (3)

Fig. 5. Grain size change as a function of pH value while calcination temperature is 350 C, calcination time 2 h and the concentration 1:6.

3.3. pH value Effect of pH value upon the grain size is shown in Fig. 5. It is found that when the pH value is below 7 the value of grain size is almost constant, which means acid solution could restrain grain growth. When the pH value is beyond 7, however, the line goes up very quickly which indicates that a total alkali environment would enhance grain growth. In this paper nano-TiO2 powders were obtained mainly by controlling hydrolysis and condensation reactions of tetra-n-butyl-titanate. It is well known that acid is usually used to restrain hydrolysis while alkali can accelerate hydrolysis during reaction. When pH is beyond 7 which means environment do benet to accelerate hydrolysis, the large aggregated particles are formed and grain tend to grow quickly.

where u is the grain growth rate, D the diffusion coefcient, t the calcination time, the constant data. Compared with the low calcination temperature the diffusion coefcient at high calcination temperature is large. Huge drive force for diffusion is present. So the growth rate for the particle is fast at relatively high calcination temperatures and the grain size tends to change very greatly as the calcination time prolong.

Fig. 4. Grain size change as a function of the calcination time at different temperatures while the concentration is 1:6 and pH value 7: (a) 350; (b) 500; (c) 1000 C.

Fig. 6. The grain size of the nano-TiO2 as a function of concentration while calcination time is 2 h, the calcination temperature 350 C and pH value 7.

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Fig. 7. XRD of the nano-TiO2 dry-gel powder with different concentrations while calcination time is 2 h and pH value 7.

Fig. 9. XRD of the nano-TiO2 powder with different concentrations while the calcination temperature is 600 C, the calcination time 2 h, and pH value 7.

3.4. Concentration The grain size of the gel powder via different concentrations is shown in Fig. 6. It is obvious that the grain size do not grow up as the concentration changes. Therefore, the different concentrations may have little effects upon the grain size of the gel powder.

The gel powders with different concentrations were calcined at different temperatures. The patterns of XRD are shown in Figs. 79. It can be seen from Figs. 7 and 8 that below 400 C there are no obvious phase transformation difference with the different concentrations; however, when the calcination temperature increases further above 400 C as shown in Fig. 9, obvious phase transformation difference occurred. This behavior is very interesting. The fraction of rutile during phase transformation from anatase to rutile inuenced by the concentration is shown in Fig. 10. The phase

Fig. 8. XRD for nano-TiO2 with different concentrations while the calcination temperature is 400 C, the calcination time 2 h and pH value 7.

Fig. 10. The fraction of rutile of the nano-TiO2 powders with different concentrations at different calcination temperatures during phase transformation from anatase to rutile.

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transformations from anatase to rutile for the samples with different concentrations seemed to start at 400 C but was completed at different temperatures. For the concentrations chosen as 1:20 and 1:50, almost 90% of anatase phase have been transformed into rutile below about 600 C but for the concentrations chosen as 1:100 and 1:6, the same amount transformation of anatase phase were only completed at about 700 and 800 C, respectively. It seems that even the concentration has no obvious inuence upon the grain size of the gel as described above, but it really affects the phase transformation. However, further studies are needed for explained this phenomenon.

Different calcination time was found to produce different effects upon the grain size depending upon calcination temperature. The higher is the calcination temperature, the greater is the effect of calcination time upon the grain size. The most important behavior which is found for the rst time is that the phase transformation process of the nano-TiO2 from anatase to rutile was inuenced greatly by the concentration. References
[1] R. Birrnlyer, H. Gleiter, H.P. Klein, et al., Phys. Lett. A 102 (8) (1984) 365. [2] H. Gleiter, Prog. Mater. Sci. 33 (1989) 223. [3] S. Sakka, Am. Ceram. Soc. Bull. 64 (1985) 1463. [4] S. Doeuff, M. Henry, C. Sanchen, J. Livage, J. Non-Cryst. Solids 89 (1987) 206216. [5] H. Kumazuawa, H. Otsuki, E. Sada, J. Mater. Sci. Lett. 15 (1996) 839840. [6] D.C. Hague, M.J. Mayo, J. Am. Ceram. Soc. 77 (1994) 19571959. [7] E. Haro-Poniatowski, R. Rodriguez, O. Cano-Corona, J. Mater. Res. 9 (1994) 21022107. [8] C.U.I. Zoulin, J. Mater. Sci. Technol. 15 (1999) 7174. [9] W.F. Sullivan, S.S. Cole, J. Am. Ceram. Soc. 42 (1959) 127133. [10] D. Turnbull, Solid State Phys. 3 (1956). [11] H.B. Aaron, D. Fainstein, G.R. Kottter, J. Appl. Phys. 41 (1970) 4404.

4. Conclusions Nano-TiO2 powders have been prepared by solgel method successfully. By controlling the conditions properly, nano-TiO2 powders with the grain size less than 6 nm grain size of nano-TiO2 powders could be obtained. Among the elements which may have effect upon the grain size and microstructure of nano-TiO2 powders, the calcination temperature and pH value were found to be more effective compared with the calcination time and concentration. The grain size tends to increase with increasing temperature and the increase in pH value.