Scripta Metallurgica et Materialia,Vol. 32, No.

6, pp, 873-877, 1995 Copyright 0 1995 Elsevier Science Ltd Printed in the USA. All rights reserved 0956-716X/95 $9.50 t .OO

GROWTH OF RUTILE CRYSTALLITES DURING THE INITIAL STAGE OF ANATASE-TO-RUTILE TRANSFORMATION IN PURE TITANIA AND IN TITANIA-ALUMINA NANOCOMPOSITES

Krishnankutty-Nair

P. Kumar

Institute of Mineral Industry, Technical University of Denmark, DK-2800 Lyngby, Denmark (Received September 7, 1994) (Revised October 14,1994) 1. Introduction Anatase-to-rutile transformation in titania system is a metastable-to-stable irreversible transformation [I ,2]. Transformations of this type are very important both from a scientific as well as from a technological point of view. It has been recently shown that sintering of titania during the anatase-to-rutile transformation is an effective way to achieve near theoretical densities at temperatures as low as 600C [3]. On the other hand, if the objective is to use titania for catalyst support or membrane applications this transformation should be prevented or at least retarded to stabilize the initial pore-structure [2,4-6]. This enhancement in sintering (porosity reduction) is an example of the well known Hedvall effect [7]. During almost all solid state transformations, atoms are more mobile than usual and this will enhance the mass transport rate and enhances solid state sintering. Many technologically interesting systems are metastable in the as prepared form when prepared through solution-sol-gel routes. Zirconia (tetragonal-to-monoclinic transformation) and alumina (transition alumina-to-a-alumina) are some other examples. It has been generally observed that [2,8] the rutile crystallites are much larger than their precursor anatase crystallites in the initial stage of transformation. However, no possible explanation for this behaviour is given in these studies. In this paper, an explanation based on the thermodynamics and kinetics of nucleation-growth type of transformations is given for the observed difference between the crystallite sizes of anatase and rutile phases during the initial stage of thse phase transformation. Two situations are considered here, pure titania and the titania phase in the titania-alumina nanocomposites. It is postulated that the critical nuclei size of Wile phase may be much larger than the transforming anatase particles. 2. Experimental Titania samples were prepared from a titania sol synthesised by the hydrolysis of titanium isopropoxide with water. Titania-50 wt% alumina nanocomposites were prepared by mixing appropriate amounts of titania and alumina sols. Alumina sol was prepared by the hydrolysis of aluminum sec. butoxide. The pure sol and mixed sols were dried to get the precursor gels, which were then subjected to further calcination treatments under isothermal or nonisothermal conditions. The gels were heated at temperatures ranging from 390 to 1000C. For isothermal experiments the samples were introduced into a preheated furnace kept at the required temperature and taken out after different soaking times. The nonisothermal experiments were performed by heating the samples with a rate of 100%/h and kept at the top temperature for five minutes and then furnace cooled. The details of sample preparation are given elsewhere [2]. X-ray diffraction patterns were recorded using CuK, radiation in the step-scan mode with a 26 range of 23 to 46. The scanning was performed in steps of 0.015 26 with an interval of 10 sec. Crystallite size and the

Present address: Shell Research BV, Amsterdam, The Netherlands.

873

874

ANATASE-TO-RUTILE

TRANSFORMATION

Vol. 32,

No.6

relative amounts of anatase and rutile phase present were calculated from the (101) reflection of anatase and the (110) reflection of rutile.The crystallite size of anatase and rutile phases were calculated using the Scherrer relationship:

where B,,, is the width of the peak at half maximum and ). is the wave length of Cu K,. The value of K may vary from 0.9 to 1.4 depending on many factors including the shape of the primary crystallite. The width of the peak at half maximum was calculated after correcting for instrumental and wave length related broadenings. In this study a value of 1.38 is assumed for K. The crystallite sizes calculated with this value of K are in good agreement with the sizes calculated from FE-SEM micrographs 191. The fraction of rutile present in the composites after various heat treatments were calculated using the equation given below [lo]:

IO Time

100

10001oooo

(mwd

1 wR= 1+0.8(/J/j

(2)

45

25

W, is the weight fraction of rutile while I, and I, are the X-ray integrated intensities of (101) reflection of anatase and (110) reflection of rutile respectively. The integrated intensity was calculated after correcting for instrumental and wave length related broadenings.

,* u
60 op 40 /-d pA 20 +___b_*---10

loo

1om1oaoo

Tme

hm)

Typical examples of the crystallite sizes of anatase and rutile with soaking time for sol-gel derived titania samples, calcined at 390, 430, and 47OC, are given in Fig.1. Both crystallite sizes and fraction of rutile present in the samples are plotted against the soaking time. In the case of 390C heated samples, up to about 500 min only anatase phase is present. After 500 min detectable amounts of rutile is present in the samples. As soon as the rutile crystallites are formed the sizes are at least 30 nm higher than that of the anatase crystallites within the same sample. The same trend can be seen with the sample heated at 430C also. A similar difference in the size between anatase and rutile crystallites has also been observed with field emission scanning electron microscopy [3]. In the case of samples calcined at 47OC, the difference in size between the anatase and futile crystallites are slightly smaller compared with the 390C data. Crystallite size versus calcination temperature of pure titania and of the titania phase of the nanocomposite containing 80% alumina is given in Fig.2. All the samples were calcined with a heating rate of lOOC/h for five minutes at the top temperature. Curves a and I Fig. 1 Crystallite size and rutile content of pure Mania samples heat trafed at 390, 430 and 470C for different times.

Vol. 32, No. 6

ANATASE-TO-RUTILE

TRANSFORMATION

875

b represent the crystallite sizes, of anatase and rutile phases respectively, of pure titania. At 390C there is very little rutile present, therefore the crystallite size of the rutile phase is not indicated in the figure. By 500% the anatase crystallites have grown to about 25 nm and the transformed Wile phase has crystallite size of about 51 nm. Above 600C the difference in size between anatase and rutile crystallites are becoming less significant, 50 and 55 nm respectively. By 700C the sample contains only rutile phase with an average crystallite size of about 57 nm. The curves c and d represent the crystallite sizes of Mania phases in the nanocomposite. Up to about 700C the Mania part of the composite contains only anatase phase. At 800C both anatase and rutile are present and the crystallites are about 15 and 35 nm respectively. At 1000C the average grain size of anatase and Wile phases are about 40 and 75 nm re: sctivelv.

60

40

20

0 300

500

700

900

1100

1300

Temperature
L

in (Cl

Fl9.2 crysta,r/ite size versus calcmatron tempearture for pure t/tan/a (a anu 0) ana tne tltania pnase c . the titania-alumina nanocomposites (c anu a).

_-

. .

A possible explanation for the above mentioned differences in crystallite sizes can be given based on the thermodynamics and kinetics of anatase-to-Wile transformation. It is a metastable-to-stable transformation and there is no equilibrium transformation temperature. At all temperatures above absolute zero, rutile phase is the stable phase (lower volume free energy). A schematic temperature free energy diagram is given in Fig.3. The total free energy change, G in any nucleation-growth type of transformations can be expressed as follows: (3) where r is the radius of the embryo. 9, is the difference in volume free energy (per unit volume) and is

876

ANATASE-TO-RUTILE TRANSFORMATION

Vol. 32, No. 6

always +ve (energy released during the transformation) and g, is the energy (per unit area) required to create a new surface and will always be -ve. gB is another free energy term (per unit volume), which takes into account of the effects due to nanostructural and mechanical environment of the transforming embryo. For example residual stresses or a rigid inclusions present in the samples. ge can either be +ve or -ve depending on the factors contributing to it. In the case of anatase-to-rutile transformation ge will be -ve if external compressive stresses are not present. This is because during the anatase-to-rutile transformation there is a volume decrease of about 8%. However, if an external compressive stress is present, as in the case of hot pressing or sinter-forging, g, can be less negative or even be positive (assisting the transformation). An embryo of size r will become stable only when it reaches a critical size r,. If every thing else is constant rc will depend only on the volume free energy released and the energy required to create a new surface. The size of the critical nuclei can be expressed as below [l1,121:

rc= -2-

9*
9,+9,

(4)

It may be reasonable to think that the primary particle (crystallite) size of anatase is smaller than the critical nuclei size of rutile. This may be one of the reasons behind the high chance of obtaining the metastable phase when prepared through solution-sol-gel routes. In solution-sol-gel synthesis the primary particle size of the as precipitated phase is in the nanometre range, usually 4 to 10 nm. This size is most probably below the critical nuclei size of the stable phase. During the metastable-to-stable transformation, crystallites should grow to the critical nuclei size before the transformation can proceed. This critical-nuclei-size-effect may be causing the large differences in the size between anatase and rutile crystallites in the initial stage of the transformation. We can see from Fig.3 that g, increases with temperature, and from equation (4) it can be shown that this increase in g, will decrease the critical nuclei size, if every thing else is constant. This follows that, if the large difference between the anatase and rutile crystallites is a critical-nuclei-size-effect, then this difference should decrease if the transformation is taking place at higher temperatures or under applied compressive stress. This is in fact the case with the nanocomposites where the transformation takes place at a temperature that is about 3OOC higher than in the case of pure titania. Therefore the critical nuclei size of titania phase in the nanocomposite is expected to be lower than that for the pure titania. From Fig.2 we can clearly see that in the case nanocomposites the difference between anatase and rutile crystallites in the initial stage of the transformation is smaller than that of the difference in pure titania.

GV

T-

ig.3 Schematic representation of free Additional evidence in this direction comes from a recent energy change with temperature in the study on the thermal stability of titania [13]. It has been anatase-futile system. noticed in their study that unlike the general observation, the sizes of anatase and rutile particles are not appreciably different in the initial stage of transformation. This may be simply due to the fact that the titania prepared in their study started transforming at a higher temperature compared with the present study [13]. The higher the temperature at which transformation takes place the higher the gV The higher the g, lower the rC More evidence for the critical-nuclei-size-effect comes from a recent sinter-forging study [14,15]. Sinter-

Vol. 32, No. 6

ANATASE-TO-RUTILE

TRANSFORMATION

817

forged samples gave smaller rutile crystallites compared with the samples sintered without the application of pressure. Applied pressure increases the magnitude of ge and hence decreases r, (equation (4)). This observation again reinforces the assumption that the critical nuclei size of rutile phase is larger than the precursor anatase phase. This has important consequences in developing fine grained dense ceramics as well as in developing porous nanostructured materials if the precursor is in the metastable form. Research is in progress to device techniques to control the critical-nuclei-size-effect.

References RD. Sha.nnon and J.A. Pask, J. Am. Ceram., Sot. 48, 391 (1965). K-N. P. Kumar, K. Keizer, A.J. Burggraaf, J. Mat. Chem., 3, 1141 (1993). K-N.P. Kumar, K. Keizer, A.J. Burggraaf, T. Okubo, H. Nagamoto, & S. Morooka, Nature (London), 358, 48 (1992). K-N. P. Kumar, K. Keizer and A.J. Burggraaf, J. Mater. Chem., 3, 917 (1993). [41 K-N.P. Kumar, K. Keizer, A.J. Burggraaf, T. Okubo, and H. Nagamoto, J. Mat. Chem., 3,923 (1993). [51 K-N.P. Kumar, K. Keizer and A.J. Burggraaf, Mater. Sci. Let., 13 (1994) 59 J.A. Hedvall and P.S. Sjoman, 2. El. Chem., 37, Sl30 (1931). ;;; Y-S. Lin, C-H. Chang and R. Gopalan, Ind. Eng. Chem. Res., 33, 860 (1994). K-N.P. Kumar, Ph.D. Thesis, University of Twente, 7500 AE Enschede, The Netherlands, 1993. ;:; [lOI Robert A.. Spurr and Howard Myers, Anal. Chem., 29 [5], 760 (1957). R.J. Borg and G.J. Dienes, The Physical Chemistry of Solids, pp 521, Academic Press, Inc., New illI York, 19!32. [121 K-N.P. Kumar, K. Keizer, A.J. Burggraaf, T. Okubo, and H. Nagamoto, J. Mat. Chem., 3, 1151 (1993). 1131 G. W. Koebrugge, L. Winnubst and A.J. Burggraaf, J. Mater. Chem., 3 [ii], 1095 (1993). 1141 M.J. Mayo, Paper presented at the NATO-AS1 meeting on Mechanical Properties and Behaviour of Materials, Having Ultrafine Microstructure, June 29- July 10, 1992, Vimeiro, Portugal. 1151 DC. Hague and M.J. Mayo, NanoStructured Materials, 3, 61 (1993).